# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2022

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mk31mk
_database_code_depnum_ccdc_archive 'CCDC 2174864'
loop_
_audit_author_name
_audit_author_address
'Marvin Koneczny'
;TU Braunschweig
Germany
;
_audit_update_record             
;
2022-05-25 deposited with the CCDC.	2022-07-08 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        
1-(Adamantyl)-3-(2,4,6-trimethylphenyl)-imidazolin-2-yliden
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C22 H28 N2'
_chemical_formula_sum            'C22 H28 N2'
_chemical_formula_weight         320.46

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   13.5173(4)
_cell_length_b                   10.3836(2)
_cell_length_c                   12.8450(4)
_cell_angle_alpha                90
_cell_angle_beta                 95.869(2)
_cell_angle_gamma                90
_cell_volume                     1793.45(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    51352
_cell_measurement_theta_min      2.4420
_cell_measurement_theta_max      44.9350

_exptl_crystal_description       plate
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.187
_exptl_crystal_F_000             696
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.279
_exptl_crystal_size_mid          0.211
_exptl_crystal_size_min          0.143
_exptl_absorpt_coefficient_mu    0.069
_exptl_absorpt_correction_T_min  0.88245
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.800
_oxdiff_exptl_absorpt_empirical_full_max 1.264
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       'ω scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            134137
_diffrn_reflns_av_unetI/netI     0.0287
_diffrn_reflns_av_R_equivalents  0.0485
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         2.478
_diffrn_reflns_theta_max         44.855
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             14658
_reflns_number_gt                11061
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       ?
_computing_cell_refinement       'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_structure_solution    
'SHELXT-2014/5 (G. M. Sheldrick, Acta Cryst., 2015, A71, 3-8)'
_computing_structure_refinement  
'SHELXL-2018/3 (G. M. Sheldrick, Acta Cryst. (2008), A64, 112-122)'
_computing_molecular_graphics    ?
_computing_publication_material  
'OLEX2 v1.2 (O. V. Dolomanov et al., J. Appl. Cryst., 2009, 42, 339-341)'
_refine_special_details          
;
 All C-H hydrogens, except H atoms in methyl groups, were placed in 
 idealised positions and refined using a riding model, with a common U 
 restrained to be 1.2 times the equivalent isotropic displacement 
 parameter of the parent atom. Methyl hydrogens were located in 
 difference synthesis. Methyl groups were idealized and refined as rigid
 groups allowed to rotate but not tip. 

 Refinement of F² against ALL reflections.  The weighted R-factor
 wR and goodness of fit S are based on F², conventional R-factors R 
 are based on F, with F set to zero for negative F². The threshold
 expression of F² > 2sigma(F²) is used only for calculating
 R-factors(gt) etc. and is not relevant to the choice of reflections 
 for refinement.  R-factors based on F² are statistically about twice
 as large as those based on F, and R- factors based on ALL data will be
 even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0764P)²+0.1110P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         14658
_refine_ls_number_parameters     220
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0624
_refine_ls_R_factor_gt           0.0441
_refine_ls_wR_factor_ref         0.1381
_refine_ls_wR_factor_gt          0.1296
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_restrained_S_all      1.066
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.52084(3) 0.57274(3) 0.28084(3) 0.01241(6) Uani 1 1 d . . . . .
N2 N 0.66318(3) 0.57811(3) 0.22364(3) 0.01205(6) Uani 1 1 d . . . . .
C1 C 0.59568(3) 0.65715(4) 0.26348(3) 0.01210(6) Uani 1 1 d . . . . .
C2 C 0.54103(4) 0.44638(4) 0.25250(4) 0.01555(7) Uani 1 1 d . . . . .
H2 H 0.499777 0.373031 0.257539 0.019 Uiso 1 1 calc R U . . .
C3 C 0.63138(4) 0.45009(4) 0.21645(4) 0.01573(7) Uani 1 1 d . . . . .
H3 H 0.666517 0.379362 0.191107 0.019 Uiso 1 1 calc R U . . .
C4 C 0.43286(3) 0.60831(4) 0.32711(3) 0.01186(6) Uani 1 1 d . . . . .
C5 C 0.44089(3) 0.65511(4) 0.43013(3) 0.01324(7) Uani 1 1 d . . . . .
C6 C 0.35324(4) 0.67805(5) 0.47613(4) 0.01579(7) Uani 1 1 d . . . . .
H6 H 0.357599 0.706989 0.546610 0.019 Uiso 1 1 calc R U . . .
C7 C 0.25953(4) 0.65981(5) 0.42180(4) 0.01651(8) Uani 1 1 d . . . . .
C8 C 0.25450(3) 0.61888(5) 0.31791(4) 0.01608(7) Uani 1 1 d . . . . .
H8 H 0.191244 0.609956 0.278963 0.019 Uiso 1 1 calc R U . . .
C9 C 0.33995(3) 0.59070(4) 0.26965(4) 0.01369(7) Uani 1 1 d . . . . .
C10 C 0.54017(4) 0.67935(5) 0.49107(4) 0.01870(8) Uani 1 1 d . . . . .
H10A H 0.581676 0.602151 0.489270 0.028 Uiso 1 1 calc R U . . .
H10B H 0.530478 0.699907 0.563792 0.028 Uiso 1 1 calc R U . . .
H10C H 0.573054 0.751771 0.459847 0.028 Uiso 1 1 calc R U . . .
C11 C 0.16632(4) 0.68263(6) 0.47443(5) 0.02461(10) Uani 1 1 d . . . . .
H11A H 0.184187 0.700380 0.548915 0.037 Uiso 1 1 calc R U . . .
H11B H 0.124004 0.605881 0.466825 0.037 Uiso 1 1 calc R U . . .
H11C H 0.130201 0.756463 0.441750 0.037 Uiso 1 1 calc R U . . .
C12 C 0.33127(4) 0.54064(5) 0.15903(4) 0.01958(9) Uani 1 1 d . . . . .
H12A H 0.381647 0.581938 0.120582 0.029 Uiso 1 1 calc R U . . .
H12B H 0.264894 0.560199 0.124626 0.029 Uiso 1 1 calc R U . . .
H12C H 0.341609 0.447217 0.159923 0.029 Uiso 1 1 calc R U . . .
C13 C 0.76026(3) 0.62019(4) 0.19369(3) 0.01140(6) Uani 1 1 d . . . . .
C14 C 0.77186(3) 0.76592(4) 0.20788(4) 0.01730(8) Uani 1 1 d . . . . .
H14A H 0.767261 0.788947 0.282018 0.021 Uiso 1 1 calc R U . . .
H14B H 0.717724 0.810807 0.164475 0.021 Uiso 1 1 calc R U . . .
C15 C 0.87294(4) 0.80863(5) 0.17529(5) 0.02273(10) Uani 1 1 d . . . . .
H15 H 0.879776 0.903972 0.184387 0.027 Uiso 1 1 calc R U . . .
C16 C 0.95631(4) 0.74152(6) 0.24488(6) 0.02464(11) Uani 1 1 d . . . . .
H16A H 0.952230 0.764957 0.319024 0.030 Uiso 1 1 calc R U . . .
H16B H 1.021804 0.769702 0.225088 0.030 Uiso 1 1 calc R U . . .
C17 C 0.94562(4) 0.59515(5) 0.23122(4) 0.01927(8) Uani 1 1 d . . . . .
H17 H 0.999852 0.550859 0.276490 0.023 Uiso 1 1 calc R U . . .
C18 C 0.84407(4) 0.55179(5) 0.26258(4) 0.01634(7) Uani 1 1 d . . . . .
H18A H 0.839284 0.572801 0.337073 0.020 Uiso 1 1 calc R U . . .
H18B H 0.837163 0.457372 0.253913 0.020 Uiso 1 1 calc R U . . .
C19 C 0.76865(4) 0.58525(5) 0.07861(4) 0.01580(7) Uani 1 1 d . . . . .
H19A H 0.761178 0.491021 0.069041 0.019 Uiso 1 1 calc R U . . .
H19B H 0.714719 0.628075 0.033377 0.019 Uiso 1 1 calc R U . . .
C20 C 0.88001(4) 0.77435(6) 0.06016(6) 0.02591(11) Uani 1 1 d . . . . .
H20A H 0.826401 0.818317 0.015321 0.031 Uiso 1 1 calc R U . . .
H20B H 0.944739 0.803365 0.038859 0.031 Uiso 1 1 calc R U . . .
C21 C 0.95346(4) 0.56073(5) 0.11623(5) 0.02047(9) Uani 1 1 d . . . . .
H21A H 0.947874 0.466300 0.106722 0.025 Uiso 1 1 calc R U . . .
H21B H 1.018928 0.588272 0.095947 0.025 Uiso 1 1 calc R U . . .
C22 C 0.87005(4) 0.62818(6) 0.04656(4) 0.02019(9) Uani 1 1 d . . . . .
H22 H 0.874832 0.604972 -0.028310 0.024 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
N1 C1 1.3739(5) . ?
N1 C2 1.3960(6) . ?
N1 C4 1.4312(5) . ?
N2 C1 1.3651(5) . ?
N2 C3 1.3973(6) . ?
N2 C13 1.4710(5) . ?
C2 C3 1.3503(7) . ?
C2 H2 0.9500 . ?
C3 H3 0.9500 . ?
C4 C9 1.4022(6) . ?
C4 C5 1.4034(6) . ?
C5 C6 1.3974(6) . ?
C5 C10 1.5040(7) . ?
C6 C7 1.3952(7) . ?
C6 H6 0.9500 . ?
C7 C8 1.3955(7) . ?
C7 C11 1.5082(7) . ?
C8 C9 1.3965(6) . ?
C8 H8 0.9500 . ?
C9 C12 1.5062(7) . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 C14 1.5302(6) . ?
C13 C19 1.5376(6) . ?
C13 C18 1.5382(6) . ?
C14 C15 1.5349(7) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 C16 1.5324(9) . ?
C15 C20 1.5335(10) . ?
C15 H15 1.0000 . ?
C16 C17 1.5351(8) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C17 C21 1.5337(8) . ?
C17 C18 1.5370(7) . ?
C17 H17 1.0000 . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?
C19 C22 1.5369(7) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 C22 1.5321(9) . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?
C21 C22 1.5351(8) . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?
C22 H22 1.0000 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1 N1 C2 112.98(4) . . ?
C1 N1 C4 124.04(4) . . ?
C2 N1 C4 122.93(4) . . ?
C1 N2 C3 112.57(4) . . ?
C1 N2 C13 124.59(3) . . ?
C3 N2 C13 122.82(3) . . ?
N2 C1 N1 102.06(3) . . ?
C3 C2 N1 105.69(4) . . ?
C3 C2 H2 127.2 . . ?
N1 C2 H2 127.2 . . ?
C2 C3 N2 106.70(4) . . ?
C2 C3 H3 126.6 . . ?
N2 C3 H3 126.6 . . ?
C9 C4 C5 121.35(4) . . ?
C9 C4 N1 119.03(4) . . ?
C5 C4 N1 119.57(4) . . ?
C6 C5 C4 118.07(4) . . ?
C6 C5 C10 120.10(4) . . ?
C4 C5 C10 121.84(4) . . ?
C7 C6 C5 122.08(4) . . ?
C7 C6 H6 119.0 . . ?
C5 C6 H6 119.0 . . ?
C6 C7 C8 118.20(4) . . ?
C6 C7 C11 120.79(5) . . ?
C8 C7 C11 121.01(5) . . ?
C7 C8 C9 121.78(4) . . ?
C7 C8 H8 119.1 . . ?
C9 C8 H8 119.1 . . ?
C8 C9 C4 118.42(4) . . ?
C8 C9 C12 120.19(4) . . ?
C4 C9 C12 121.38(4) . . ?
C5 C10 H10A 109.5 . . ?
C5 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C5 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C7 C11 H11A 109.5 . . ?
C7 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C7 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C9 C12 H12A 109.5 . . ?
C9 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C9 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
N2 C13 C14 110.23(3) . . ?
N2 C13 C19 109.68(3) . . ?
C14 C13 C19 109.34(4) . . ?
N2 C13 C18 109.67(4) . . ?
C14 C13 C18 109.13(4) . . ?
C19 C13 C18 108.77(4) . . ?
C13 C14 C15 109.66(4) . . ?
C13 C14 H14A 109.7 . . ?
C15 C14 H14A 109.7 . . ?
C13 C14 H14B 109.7 . . ?
C15 C14 H14B 109.7 . . ?
H14A C14 H14B 108.2 . . ?
C16 C15 C20 110.02(5) . . ?
C16 C15 C14 109.36(5) . . ?
C20 C15 C14 109.93(5) . . ?
C16 C15 H15 109.2 . . ?
C20 C15 H15 109.2 . . ?
C14 C15 H15 109.2 . . ?
C15 C16 C17 109.18(4) . . ?
C15 C16 H16A 109.8 . . ?
C17 C16 H16A 109.8 . . ?
C15 C16 H16B 109.8 . . ?
C17 C16 H16B 109.8 . . ?
H16A C16 H16B 108.3 . . ?
C21 C17 C16 109.02(5) . . ?
C21 C17 C18 109.61(4) . . ?
C16 C17 C18 109.65(4) . . ?
C21 C17 H17 109.5 . . ?
C16 C17 H17 109.5 . . ?
C18 C17 H17 109.5 . . ?
C17 C18 C13 109.81(4) . . ?
C17 C18 H18A 109.7 . . ?
C13 C18 H18A 109.7 . . ?
C17 C18 H18B 109.7 . . ?
C13 C18 H18B 109.7 . . ?
H18A C18 H18B 108.2 . . ?
C22 C19 C13 110.15(4) . . ?
C22 C19 H19A 109.6 . . ?
C13 C19 H19A 109.6 . . ?
C22 C19 H19B 109.6 . . ?
C13 C19 H19B 109.6 . . ?
H19A C19 H19B 108.1 . . ?
C22 C20 C15 109.06(4) . . ?
C22 C20 H20A 109.9 . . ?
C15 C20 H20A 109.9 . . ?
C22 C20 H20B 109.9 . . ?
C15 C20 H20B 109.9 . . ?
H20A C20 H20B 108.3 . . ?
C17 C21 C22 109.64(4) . . ?
C17 C21 H21A 109.7 . . ?
C22 C21 H21A 109.7 . . ?
C17 C21 H21B 109.7 . . ?
C22 C21 H21B 109.7 . . ?
H21A C21 H21B 108.2 . . ?
C20 C22 C21 109.56(5) . . ?
C20 C22 C19 109.10(4) . . ?
C21 C22 C19 109.48(4) . . ?
C20 C22 H22 109.6 . . ?
C21 C22 H22 109.6 . . ?
C19 C22 H22 109.6 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C3 N2 C1 N1 0.10(5) . . . . ?
C13 N2 C1 N1 -178.35(4) . . . . ?
C2 N1 C1 N2 -0.20(5) . . . . ?
C4 N1 C1 N2 177.33(4) . . . . ?
C1 N1 C2 C3 0.23(6) . . . . ?
C4 N1 C2 C3 -177.33(4) . . . . ?
N1 C2 C3 N2 -0.16(5) . . . . ?
C1 N2 C3 C2 0.04(6) . . . . ?
C13 N2 C3 C2 178.52(4) . . . . ?
C1 N1 C4 C9 119.88(5) . . . . ?
C2 N1 C4 C9 -62.82(6) . . . . ?
C1 N1 C4 C5 -62.63(6) . . . . ?
C2 N1 C4 C5 114.66(5) . . . . ?
C9 C4 C5 C6 3.03(6) . . . . ?
N1 C4 C5 C6 -174.39(4) . . . . ?
C9 C4 C5 C10 -177.54(4) . . . . ?
N1 C4 C5 C10 5.03(6) . . . . ?
C4 C5 C6 C7 -2.09(7) . . . . ?
C10 C5 C6 C7 178.48(4) . . . . ?
C5 C6 C7 C8 -0.82(7) . . . . ?
C5 C6 C7 C11 178.64(5) . . . . ?
C6 C7 C8 C9 2.93(7) . . . . ?
C11 C7 C8 C9 -176.53(5) . . . . ?
C7 C8 C9 C4 -2.02(7) . . . . ?
C7 C8 C9 C12 177.03(5) . . . . ?
C5 C4 C9 C8 -1.04(7) . . . . ?
N1 C4 C9 C8 176.39(4) . . . . ?
C5 C4 C9 C12 179.92(4) . . . . ?
N1 C4 C9 C12 -2.64(6) . . . . ?
C1 N2 C13 C14 -3.16(6) . . . . ?
C3 N2 C13 C14 178.54(4) . . . . ?
C1 N2 C13 C19 -123.60(4) . . . . ?
C3 N2 C13 C19 58.10(5) . . . . ?
C1 N2 C13 C18 117.01(5) . . . . ?
C3 N2 C13 C18 -61.29(5) . . . . ?
N2 C13 C14 C15 -179.42(4) . . . . ?
C19 C13 C14 C15 -58.77(5) . . . . ?
C18 C13 C14 C15 60.08(5) . . . . ?
C13 C14 C15 C16 -60.94(6) . . . . ?
C13 C14 C15 C20 59.94(6) . . . . ?
C20 C15 C16 C17 -60.42(6) . . . . ?
C14 C15 C16 C17 60.42(6) . . . . ?
C15 C16 C17 C21 60.21(6) . . . . ?
C15 C16 C17 C18 -59.79(6) . . . . ?
C21 C17 C18 C13 -60.18(5) . . . . ?
C16 C17 C18 C13 59.46(6) . . . . ?
N2 C13 C18 C17 179.79(4) . . . . ?
C14 C13 C18 C17 -59.37(5) . . . . ?
C19 C13 C18 C17 59.84(5) . . . . ?
N2 C13 C19 C22 -179.72(4) . . . . ?
C14 C13 C19 C22 59.29(5) . . . . ?
C18 C13 C19 C22 -59.78(5) . . . . ?
C16 C15 C20 C22 59.94(6) . . . . ?
C14 C15 C20 C22 -60.55(6) . . . . ?
C16 C17 C21 C22 -60.41(5) . . . . ?
C18 C17 C21 C22 59.62(6) . . . . ?
C15 C20 C22 C21 -59.57(5) . . . . ?
C15 C20 C22 C19 60.27(6) . . . . ?
C17 C21 C22 C20 60.33(6) . . . . ?
C17 C21 C22 C19 -59.27(6) . . . . ?
C13 C19 C22 C20 -60.13(6) . . . . ?
C13 C19 C22 C21 59.76(5) . . . . ?

_refine_diff_density_max         0.606
_refine_diff_density_min         -0.314
_refine_diff_density_rms         0.058


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: toluene/n-hexane -40°C'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mk24mk2
_database_code_depnum_ccdc_archive 'CCDC 2174874'
loop_
_audit_author_name
_audit_author_address
'Marvin Koneczny'
;TU Braunschweig
Germany
;
_audit_update_record             
;
2022-05-25 deposited with the CCDC.	2022-07-08 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C50 H68 Cl2 N6 Ti, C H2 Cl2'
_chemical_formula_sum            'C51 H70 Cl4 N6 Ti'
_chemical_formula_weight         956.83

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   16.9882(3)
_cell_length_b                   18.0462(2)
_cell_length_c                   18.3671(3)
_cell_angle_alpha                90
_cell_angle_beta                 116.512(2)
_cell_angle_gamma                90
_cell_volume                     5038.71(15)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    63042
_cell_measurement_theta_min      2.9060
_cell_measurement_theta_max      77.4850

_exptl_crystal_description       needle
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_F_000             2032
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.135
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.051
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-4 -5 11 0.0397
-9 -2 -2 0.0242
8 7 -7 0.0402
1 -12 -1 0.0441
-3 11 4 0.0638
6 -2 6 0.0372
7 -8 1 0.0354
4 4 -11 0.0390
-10 1 1 0.0123
11 1 -7 0.0383
10 1 0 0.0362
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-4.1072 -4.6182 10.9456 -0.8845 0.4212 0.2008
-8.9365 -1.6161 -1.7742 0.5191 0.8482 -0.1057
7.9737 7.3472 -6.9387 0.4737 -0.8712 0.1291
1.3144 -11.6222 -0.5009 -0.4850 0.2316 -0.8433
-2.6267 11.0236 3.7971 0.2539 -0.1215 0.9596
5.5487 -1.9790 6.3703 -0.8749 -0.4757 0.0906
6.9942 -7.6757 1.0090 -0.7304 -0.3966 -0.5561
4.1893 4.3159 -11.0741 0.8790 -0.4186 -0.2283
-10.3749 0.7726 1.4371 0.4198 0.8815 0.2159
10.8642 0.8932 -6.9151 0.0738 -0.9352 -0.3464
10.0274 0.6691 -0.4232 -0.4291 -0.9007 -0.0676
_exptl_absorpt_coefficient_mu    3.694
_exptl_absorpt_correction_T_min  0.58339
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.21a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.594
_oxdiff_exptl_absorpt_empirical_full_max 1.632
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;

_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_special_details   ?

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            122767
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_av_R_equivalents  0.0647
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.907
_diffrn_reflns_theta_max         77.812
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             10633
_reflns_number_gt                9560
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_structure_solution    
'SHELXT-2014/5 (G. M. Sheldrick, Acta Cryst., 2015, A71, 3-8)'
_computing_structure_refinement  
'SHELXL-2018/3 (G. M. Sheldrick, Acta Cryst., 2008, A64, 112-122)'
_computing_molecular_graphics    ?
_computing_publication_material  
'OLEX2 v1.2 (O. V. Dolomanov et al., J. Appl. Cryst., 2009, 42, 339-341)'
_refine_special_details          
;
 All C-H hydrogens, except H atoms in methyl groups, were placed in 
 idealised positions and refined using a riding model, with a common U 
 restrained to be 1.2 times the equivalent isotropic displacement 
 parameter of the parent atom. Methyl hydrogens were located in 
 difference synthesis. Methyl groups were idealized and refined as rigid
 groups allowed to rotate but not tip. 
 The N-H hydrogen was refined freely.

 Refinement of F² against ALL reflections.  The weighted R-factor
 wR and goodness of fit S are based on F², conventional R-factors R 
 are based on F, with F set to zero for negative F². The threshold
 expression of F² > 2sigma(F²) is used only for calculating
 R-factors(gt) etc. and isnot relevant to the choice of reflections 
 for refinement.  R-factors based on F² are statistically about twice
 as large as those based on F, and R- factors based on ALL data will be
 even larger.

 Due to crystal decomposition data had to be cut accordingly. Differend
 methods such as 'Sample Decay' in CrysAlisPro were tried but cutting
 the data yielded the best results. Therefore some reflections are 
 missing.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0905P)²+4.5090P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         10633
_refine_ls_number_parameters     567
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0606
_refine_ls_R_factor_gt           0.0561
_refine_ls_wR_factor_ref         0.1649
_refine_ls_wR_factor_gt          0.1599
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_restrained_S_all      1.411
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.72787(2) 0.33256(2) 0.23590(2) 0.02450(12) Uani 1 1 d . . . . .
Cl1 Cl 0.79568(4) 0.23312(3) 0.21134(4) 0.03737(15) Uani 1 1 d . . . . .
Cl2 Cl 0.59952(4) 0.34853(3) 0.11804(3) 0.03457(14) Uani 1 1 d . . . . .
N1 N 0.69878(12) 0.30740(11) 0.31558(11) 0.0274(4) Uani 1 1 d . . . . .
N2 N 0.75211(12) 0.23844(10) 0.43928(11) 0.0264(4) Uani 1 1 d . . . . .
N3 N 0.61295(12) 0.27136(11) 0.38528(12) 0.0277(4) Uani 1 1 d . . . . .
N4 N 0.79952(12) 0.41162(10) 0.25430(12) 0.0276(4) Uani 1 1 d . . . . .
N5 N 0.79843(12) 0.54365(11) 0.25327(12) 0.0297(4) Uani 1 1 d . . . . .
N6 N 0.91747(12) 0.49062(11) 0.25895(12) 0.0294(4) Uani 1 1 d . . . . .
C1 C 0.68816(14) 0.27597(12) 0.37453(13) 0.0255(4) Uani 1 1 d . . . . .
C2 C 0.71697(16) 0.21098(14) 0.48944(14) 0.0317(5) Uani 1 1 d . . . . .
H2 H 0.747441 0.183279 0.538052 0.038 Uiso 1 1 calc R U . . .
C3 C 0.63209(16) 0.23100(13) 0.45619(14) 0.0321(5) Uani 1 1 d . . . . .
H3 H 0.591644 0.219641 0.477310 0.038 Uiso 1 1 calc R U . . .
C4 C 0.84039(14) 0.22472(13) 0.45024(14) 0.0282(4) Uani 1 1 d . . . . .
C5 C 0.86210(17) 0.15239(14) 0.43709(16) 0.0352(5) Uani 1 1 d . . . . .
C6 C 0.94771(18) 0.14066(15) 0.44773(19) 0.0420(6) Uani 1 1 d . . . . .
H6 H 0.964907 0.092493 0.439568 0.050 Uiso 1 1 calc R U . . .
C7 C 1.00770(17) 0.19769(15) 0.46986(18) 0.0412(6) Uani 1 1 d . . . . .
H7 H 1.065255 0.188768 0.475475 0.049 Uiso 1 1 calc R U . . .
C8 C 0.98484(15) 0.26806(14) 0.48401(15) 0.0335(5) Uani 1 1 d . . . . .
H8 H 1.027428 0.306563 0.500246 0.040 Uiso 1 1 calc R U . . .
C9 C 0.90045(14) 0.28336(12) 0.47485(13) 0.0273(4) Uani 1 1 d . . . . .
C10 C 0.79518(18) 0.08934(15) 0.41098(19) 0.0427(6) Uani 1 1 d . . . . .
H10 H 0.756994 0.098194 0.438679 0.051 Uiso 1 1 calc R U . . .
C11 C 0.7359(3) 0.0917(2) 0.3216(2) 0.0643(9) Uani 1 1 d . . . . .
H11A H 0.770384 0.082375 0.291669 0.096 Uiso 1 1 calc R U . . .
H11B H 0.708249 0.140622 0.306904 0.096 Uiso 1 1 calc R U . . .
H11C H 0.690341 0.053630 0.307664 0.096 Uiso 1 1 calc R U . . .
C12 C 0.8364(3) 0.01305(18) 0.4384(2) 0.0642(9) Uani 1 1 d . . . . .
H12A H 0.789993 -0.023455 0.428540 0.096 Uiso 1 1 calc R U . . .
H12B H 0.876868 0.014399 0.496632 0.096 Uiso 1 1 calc R U . . .
H12C H 0.868767 -0.000823 0.407712 0.096 Uiso 1 1 calc R U . . .
C13 C 0.87539(15) 0.35861(12) 0.49590(14) 0.0278(4) Uani 1 1 d . . . . .
H13 H 0.816032 0.371822 0.451850 0.033 Uiso 1 1 calc R U . . .
C14 C 0.93877(16) 0.42088(13) 0.50098(16) 0.0342(5) Uani 1 1 d . . . . .
H14A H 0.917411 0.467936 0.512076 0.051 Uiso 1 1 calc R U . . .
H14B H 0.942204 0.424399 0.449231 0.051 Uiso 1 1 calc R U . . .
H14C H 0.997298 0.410183 0.544898 0.051 Uiso 1 1 calc R U . . .
C15 C 0.86779(19) 0.35389(15) 0.57554(16) 0.0385(6) Uani 1 1 d . . . . .
H15A H 0.925108 0.340775 0.619949 0.058 Uiso 1 1 calc R U . . .
H15B H 0.824482 0.315924 0.570706 0.058 Uiso 1 1 calc R U . . .
H15C H 0.848911 0.401946 0.587061 0.058 Uiso 1 1 calc R U . . .
C16 C 0.52411(14) 0.29906(13) 0.32737(14) 0.0290(5) Uani 1 1 d . . . . .
C17 C 0.49398(15) 0.26093(14) 0.24509(15) 0.0324(5) Uani 1 1 d . . . . .
H17A H 0.493066 0.206588 0.252030 0.039 Uiso 1 1 calc R U . . .
H17B H 0.535782 0.272141 0.222501 0.039 Uiso 1 1 calc R U . . .
C18 C 0.40152(16) 0.28807(18) 0.18595(18) 0.0436(6) Uani 1 1 d . . . . .
H18 H 0.382248 0.263247 0.132009 0.052 Uiso 1 1 calc R U . . .
C19 C 0.33668(17) 0.26928(17) 0.2210(2) 0.0465(7) Uani 1 1 d . . . . .
H19A H 0.276675 0.285698 0.182884 0.056 Uiso 1 1 calc R U . . .
H19B H 0.335351 0.215050 0.228533 0.056 Uiso 1 1 calc R U . . .
C20 C 0.36624(17) 0.30845(16) 0.3025(2) 0.0435(6) Uani 1 1 d . . . . .
H20 H 0.324177 0.296519 0.325281 0.052 Uiso 1 1 calc R U . . .
C21 C 0.45905(16) 0.28098(15) 0.36209(17) 0.0354(5) Uani 1 1 d . . . . .
H21A H 0.478151 0.305483 0.415539 0.042 Uiso 1 1 calc R U . . .
H21B H 0.457765 0.226826 0.370082 0.042 Uiso 1 1 calc R U . . .
C22 C 0.52618(16) 0.38334(14) 0.31762(18) 0.0364(5) Uani 1 1 d . . . . .
H22A H 0.568922 0.396323 0.296652 0.044 Uiso 1 1 calc R U . . .
H22B H 0.544923 0.407733 0.371073 0.044 Uiso 1 1 calc R U . . .
C23 C 0.40438(18) 0.37207(19) 0.1758(2) 0.0519(8) Uani 1 1 d . . . . .
H23A H 0.445854 0.384111 0.153043 0.062 Uiso 1 1 calc R U . . .
H23B H 0.345307 0.390148 0.137241 0.062 Uiso 1 1 calc R U . . .
C24 C 0.43376(18) 0.41049(16) 0.2579(2) 0.0485(7) Uani 1 1 d . . . . .
H24 H 0.435210 0.465291 0.250539 0.058 Uiso 1 1 calc R U . . .
C25 C 0.3689(2) 0.39239(17) 0.2926(2) 0.0538(8) Uani 1 1 d . . . . .
H25A H 0.387906 0.416953 0.346025 0.065 Uiso 1 1 calc R U . . .
H25B H 0.309582 0.410868 0.255402 0.065 Uiso 1 1 calc R U . . .
C26 C 0.83600(14) 0.47538(12) 0.25573(13) 0.0263(4) Uani 1 1 d . . . . .
C27 C 0.85456(16) 0.59949(14) 0.25375(17) 0.0367(5) Uani 1 1 d . . . . .
H27 H 0.843571 0.651244 0.251909 0.044 Uiso 1 1 calc R U . . .
C28 C 0.92729(16) 0.56716(14) 0.25728(16) 0.0352(5) Uani 1 1 d . . . . .
H28 H 0.977037 0.592190 0.258447 0.042 Uiso 1 1 calc R U . . .
C29 C 0.70671(14) 0.55331(12) 0.23180(15) 0.0291(5) Uani 1 1 d . . . . .
C30 C 0.64926(15) 0.56532(12) 0.14967(15) 0.0306(5) Uani 1 1 d . . . . .
C31 C 0.55987(16) 0.57365(13) 0.12950(15) 0.0330(5) Uani 1 1 d . . . . .
H31 H 0.518694 0.582630 0.074603 0.040 Uiso 1 1 calc R U . . .
C32 C 0.53116(15) 0.56889(13) 0.18901(16) 0.0343(5) Uani 1 1 d . . . . .
H32 H 0.470138 0.573252 0.174134 0.041 Uiso 1 1 calc R U . . .
C33 C 0.58993(15) 0.55785(13) 0.26995(16) 0.0325(5) Uani 1 1 d . . . . .
H33 H 0.568821 0.555578 0.309866 0.039 Uiso 1 1 calc R U . . .
C34 C 0.67960(15) 0.55006(13) 0.29340(15) 0.0305(5) Uani 1 1 d . . . . .
C35 C 0.68080(17) 0.57084(14) 0.08465(15) 0.0355(5) Uani 1 1 d . . . . .
H35 H 0.743828 0.555007 0.109442 0.043 Uiso 1 1 calc R U . . .
C36 C 0.62899(19) 0.51960(15) 0.01222(16) 0.0410(6) Uani 1 1 d . . . . .
H36A H 0.630851 0.468812 0.031807 0.061 Uiso 1 1 calc R U . . .
H36B H 0.655271 0.520956 -0.025626 0.061 Uiso 1 1 calc R U . . .
H36C H 0.567738 0.536322 -0.015776 0.061 Uiso 1 1 calc R U . . .
C37 C 0.6762(2) 0.65082(16) 0.05558(19) 0.0473(7) Uani 1 1 d . . . . .
H37A H 0.614784 0.667242 0.029474 0.071 Uiso 1 1 calc R U . . .
H37B H 0.700696 0.653639 0.016396 0.071 Uiso 1 1 calc R U . . .
H37C H 0.710265 0.682855 0.102231 0.071 Uiso 1 1 calc R U . . .
C38 C 0.74769(16) 0.54205(15) 0.38209(15) 0.0354(5) Uani 1 1 d . . . . .
H38 H 0.796244 0.509991 0.383240 0.042 Uiso 1 1 calc R U . . .
C39 C 0.71236(18) 0.50601(16) 0.43653(16) 0.0405(6) Uani 1 1 d . . . . .
H39A H 0.665771 0.537075 0.437980 0.061 Uiso 1 1 calc R U . . .
H39B H 0.760129 0.500737 0.491703 0.061 Uiso 1 1 calc R U . . .
H39C H 0.688448 0.457008 0.414927 0.061 Uiso 1 1 calc R U . . .
C40 C 0.78736(19) 0.61766(17) 0.41697(18) 0.0473(7) Uani 1 1 d . . . . .
H40A H 0.810368 0.640646 0.382041 0.071 Uiso 1 1 calc R U . . .
H40B H 0.835260 0.611213 0.471886 0.071 Uiso 1 1 calc R U . . .
H40C H 0.741845 0.649538 0.419315 0.071 Uiso 1 1 calc R U . . .
C41 C 0.98117(15) 0.43415(14) 0.25879(15) 0.0308(5) Uani 1 1 d . . . . .
C42 C 0.93788(17) 0.38679(15) 0.18141(16) 0.0373(6) Uani 1 1 d . . . . .
H42A H 0.919530 0.418709 0.132710 0.045 Uiso 1 1 calc R U . . .
H42B H 0.884931 0.361948 0.179283 0.045 Uiso 1 1 calc R U . . .
C43 C 1.0042(2) 0.32847(18) 0.1821(2) 0.0517(8) Uani 1 1 d . . . . .
H43 H 0.976222 0.296747 0.132393 0.062 Uiso 1 1 calc R U . . .
C44 C 1.0853(2) 0.3675(2) 0.1837(2) 0.0584(9) Uani 1 1 d . . . . .
H44A H 1.127732 0.330157 0.183131 0.070 Uiso 1 1 calc R U . . .
H44B H 1.067520 0.399225 0.134940 0.070 Uiso 1 1 calc R U . . .
C45 C 1.12837(19) 0.41487(19) 0.2608(2) 0.0512(8) Uani 1 1 d . . . . .
H45 H 1.180764 0.440692 0.261428 0.061 Uiso 1 1 calc R U . . .
C46 C 1.06199(17) 0.47299(16) 0.25966(18) 0.0415(6) Uani 1 1 d . . . . .
H46A H 1.043755 0.504653 0.210784 0.050 Uiso 1 1 calc R U . . .
H46B H 1.089661 0.505022 0.308366 0.050 Uiso 1 1 calc R U . . .
C47 C 1.01100(16) 0.38588(15) 0.33488(16) 0.0375(5) Uani 1 1 d . . . . .
H47A H 0.959454 0.360959 0.335624 0.045 Uiso 1 1 calc R U . . .
H47B H 1.038852 0.417260 0.384102 0.045 Uiso 1 1 calc R U . . .
C48 C 1.0326(2) 0.28012(17) 0.2585(2) 0.0574(9) Uani 1 1 d . . . . .
H48A H 0.980521 0.255034 0.257878 0.069 Uiso 1 1 calc R U . . .
H48B H 1.074129 0.241558 0.258585 0.069 Uiso 1 1 calc R U . . .
C49 C 1.15767(19) 0.3674(2) 0.3368(2) 0.0598(9) Uani 1 1 d . . . . .
H49A H 1.185275 0.399004 0.385877 0.072 Uiso 1 1 calc R U . . .
H49B H 1.201592 0.330568 0.338455 0.072 Uiso 1 1 calc R U . . .
C50 C 1.0769(2) 0.32766(19) 0.3353(2) 0.0527(8) Uani 1 1 d . . . . .
H50 H 1.095480 0.295542 0.384591 0.063 Uiso 1 1 calc R U . . .
Cl3 Cl 0.63455(14) 0.42897(9) 0.56917(10) 0.1238(6) Uani 1 1 d . . . . .
Cl4 Cl 0.47387(10) 0.36215(10) 0.56367(8) 0.1106(4) Uani 1 1 d . U . . .
C99 C 0.5891(3) 0.3610(2) 0.6059(2) 0.0786(12) Uani 1 1 d . . . . .
H99A H 0.613256 0.366908 0.665598 0.094 Uiso 1 1 calc R U . . .
H99B H 0.607911 0.311917 0.595408 0.094 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 N1 1.7995(19) . ?
Ti1 N4 1.8068(19) . ?
Ti1 Cl1 2.2835(7) . ?
Ti1 Cl2 2.3042(7) . ?
N1 C1 1.304(3) . ?
N2 C1 1.378(3) . ?
N2 C2 1.393(3) . ?
N2 C4 1.443(3) . ?
N3 C1 1.380(3) . ?
N3 C3 1.398(3) . ?
N3 C16 1.492(3) . ?
N4 C26 1.302(3) . ?
N5 C26 1.379(3) . ?
N5 C27 1.385(3) . ?
N5 C29 1.437(3) . ?
N6 C26 1.386(3) . ?
N6 C28 1.393(3) . ?
N6 C41 1.488(3) . ?
C2 C3 1.340(3) . ?
C2 H2 0.9500 . ?
C3 H3 0.9500 . ?
C4 C9 1.398(3) . ?
C4 C5 1.406(3) . ?
C5 C6 1.394(4) . ?
C5 C10 1.526(4) . ?
C6 C7 1.376(4) . ?
C6 H6 0.9500 . ?
C7 C8 1.386(4) . ?
C7 H7 0.9500 . ?
C8 C9 1.394(3) . ?
C8 H8 0.9500 . ?
C9 C13 1.524(3) . ?
C10 C11 1.495(5) . ?
C10 C12 1.525(4) . ?
C10 H10 1.0000 . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 C15 1.527(3) . ?
C13 C14 1.530(3) . ?
C13 H13 1.0000 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?
C16 C17 1.526(3) . ?
C16 C22 1.534(3) . ?
C16 C21 1.537(3) . ?
C17 C18 1.537(3) . ?
C17 H17A 0.9900 . ?
C17 H17B 0.9900 . ?
C18 C23 1.531(5) . ?
C18 C19 1.542(4) . ?
C18 H18 1.0000 . ?
C19 C20 1.522(5) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 C25 1.529(4) . ?
C20 C21 1.546(4) . ?
C20 H20 1.0000 . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?
C22 C24 1.540(4) . ?
C22 H22A 0.9900 . ?
C22 H22B 0.9900 . ?
C23 C24 1.528(5) . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C24 C25 1.534(4) . ?
C24 H24 1.0000 . ?
C25 H25A 0.9900 . ?
C25 H25B 0.9900 . ?
C27 C28 1.342(4) . ?
C27 H27 0.9500 . ?
C28 H28 0.9500 . ?
C29 C30 1.400(3) . ?
C29 C34 1.400(3) . ?
C30 C31 1.401(3) . ?
C30 C35 1.515(3) . ?
C31 C32 1.384(4) . ?
C31 H31 0.9500 . ?
C32 C33 1.386(4) . ?
C32 H32 0.9500 . ?
C33 C34 1.393(3) . ?
C33 H33 0.9500 . ?
C34 C38 1.527(3) . ?
C35 C37 1.529(4) . ?
C35 C36 1.534(4) . ?
C35 H35 1.0000 . ?
C36 H36A 0.9800 . ?
C36 H36B 0.9800 . ?
C36 H36C 0.9800 . ?
C37 H37A 0.9800 . ?
C37 H37B 0.9800 . ?
C37 H37C 0.9800 . ?
C38 C39 1.523(4) . ?
C38 C40 1.530(4) . ?
C38 H38 1.0000 . ?
C39 H39A 0.9800 . ?
C39 H39B 0.9800 . ?
C39 H39C 0.9800 . ?
C40 H40A 0.9800 . ?
C40 H40B 0.9800 . ?
C40 H40C 0.9800 . ?
C41 C47 1.529(4) . ?
C41 C46 1.535(3) . ?
C41 C42 1.536(3) . ?
C42 C43 1.538(4) . ?
C42 H42A 0.9900 . ?
C42 H42B 0.9900 . ?
C43 C48 1.535(5) . ?
C43 C44 1.535(4) . ?
C43 H43 1.0000 . ?
C44 C45 1.532(4) . ?
C44 H44A 0.9900 . ?
C44 H44B 0.9900 . ?
C45 C49 1.519(5) . ?
C45 C46 1.533(4) . ?
C45 H45 1.0000 . ?
C46 H46A 0.9900 . ?
C46 H46B 0.9900 . ?
C47 C50 1.533(4) . ?
C47 H47A 0.9900 . ?
C47 H47B 0.9900 . ?
C48 C50 1.532(5) . ?
C48 H48A 0.9900 . ?
C48 H48B 0.9900 . ?
C49 C50 1.538(4) . ?
C49 H49A 0.9900 . ?
C49 H49B 0.9900 . ?
C50 H50 1.0000 . ?
Cl3 C99 1.738(5) . ?
Cl4 C99 1.754(5) . ?
C99 H99A 0.9900 . ?
C99 H99B 0.9900 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Ti1 N4 116.99(9) . . ?
N1 Ti1 Cl1 107.96(7) . . ?
N4 Ti1 Cl1 107.48(6) . . ?
N1 Ti1 Cl2 107.90(6) . . ?
N4 Ti1 Cl2 110.66(7) . . ?
Cl1 Ti1 Cl2 105.19(3) . . ?
C1 N1 Ti1 167.13(17) . . ?
C1 N2 C2 109.87(18) . . ?
C1 N2 C4 125.06(18) . . ?
C2 N2 C4 124.90(19) . . ?
C1 N3 C3 108.64(19) . . ?
C1 N3 C16 125.77(18) . . ?
C3 N3 C16 125.40(18) . . ?
C26 N4 Ti1 167.65(18) . . ?
C26 N5 C27 110.04(19) . . ?
C26 N5 C29 123.14(18) . . ?
C27 N5 C29 124.9(2) . . ?
C26 N6 C28 108.83(19) . . ?
C26 N6 C41 125.27(19) . . ?
C28 N6 C41 125.78(19) . . ?
N1 C1 N2 125.61(19) . . ?
N1 C1 N3 128.7(2) . . ?
N2 C1 N3 105.69(18) . . ?
C3 C2 N2 107.1(2) . . ?
C3 C2 H2 126.4 . . ?
N2 C2 H2 126.4 . . ?
C2 C3 N3 108.7(2) . . ?
C2 C3 H3 125.7 . . ?
N3 C3 H3 125.7 . . ?
C9 C4 C5 123.3(2) . . ?
C9 C4 N2 118.6(2) . . ?
C5 C4 N2 118.1(2) . . ?
C6 C5 C4 117.0(2) . . ?
C6 C5 C10 121.0(2) . . ?
C4 C5 C10 122.0(2) . . ?
C7 C6 C5 121.1(2) . . ?
C7 C6 H6 119.4 . . ?
C5 C6 H6 119.4 . . ?
C6 C7 C8 120.5(2) . . ?
C6 C7 H7 119.7 . . ?
C8 C7 H7 119.7 . . ?
C7 C8 C9 121.2(2) . . ?
C7 C8 H8 119.4 . . ?
C9 C8 H8 119.4 . . ?
C8 C9 C4 116.9(2) . . ?
C8 C9 C13 122.3(2) . . ?
C4 C9 C13 120.7(2) . . ?
C11 C10 C12 111.9(3) . . ?
C11 C10 C5 111.5(2) . . ?
C12 C10 C5 113.7(2) . . ?
C11 C10 H10 106.4 . . ?
C12 C10 H10 106.4 . . ?
C5 C10 H10 106.4 . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C10 C12 H12A 109.5 . . ?
C10 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C10 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C9 C13 C15 110.24(19) . . ?
C9 C13 C14 113.66(19) . . ?
C15 C13 C14 109.91(19) . . ?
C9 C13 H13 107.6 . . ?
C15 C13 H13 107.6 . . ?
C14 C13 H13 107.6 . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C13 C15 H15A 109.5 . . ?
C13 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C13 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
N3 C16 C17 109.90(18) . . ?
N3 C16 C22 110.29(19) . . ?
C17 C16 C22 110.3(2) . . ?
N3 C16 C21 108.60(19) . . ?
C17 C16 C21 109.25(19) . . ?
C22 C16 C21 108.49(19) . . ?
C16 C17 C18 109.9(2) . . ?
C16 C17 H17A 109.7 . . ?
C18 C17 H17A 109.7 . . ?
C16 C17 H17B 109.7 . . ?
C18 C17 H17B 109.7 . . ?
H17A C17 H17B 108.2 . . ?
C23 C18 C17 108.9(2) . . ?
C23 C18 C19 109.7(2) . . ?
C17 C18 C19 109.3(2) . . ?
C23 C18 H18 109.7 . . ?
C17 C18 H18 109.7 . . ?
C19 C18 H18 109.7 . . ?
C20 C19 C18 108.9(2) . . ?
C20 C19 H19A 109.9 . . ?
C18 C19 H19A 109.9 . . ?
C20 C19 H19B 109.9 . . ?
C18 C19 H19B 109.9 . . ?
H19A C19 H19B 108.3 . . ?
C19 C20 C25 111.0(3) . . ?
C19 C20 C21 109.4(2) . . ?
C25 C20 C21 109.1(2) . . ?
C19 C20 H20 109.1 . . ?
C25 C20 H20 109.1 . . ?
C21 C20 H20 109.1 . . ?
C16 C21 C20 109.4(2) . . ?
C16 C21 H21A 109.8 . . ?
C20 C21 H21A 109.8 . . ?
C16 C21 H21B 109.8 . . ?
C20 C21 H21B 109.8 . . ?
H21A C21 H21B 108.2 . . ?
C16 C22 C24 109.2(2) . . ?
C16 C22 H22A 109.8 . . ?
C24 C22 H22A 109.8 . . ?
C16 C22 H22B 109.8 . . ?
C24 C22 H22B 109.8 . . ?
H22A C22 H22B 108.3 . . ?
C24 C23 C18 110.0(2) . . ?
C24 C23 H23A 109.7 . . ?
C18 C23 H23A 109.7 . . ?
C24 C23 H23B 109.7 . . ?
C18 C23 H23B 109.7 . . ?
H23A C23 H23B 108.2 . . ?
C23 C24 C25 109.6(3) . . ?
C23 C24 C22 109.8(2) . . ?
C25 C24 C22 109.2(3) . . ?
C23 C24 H24 109.4 . . ?
C25 C24 H24 109.4 . . ?
C22 C24 H24 109.4 . . ?
C20 C25 C24 109.0(2) . . ?
C20 C25 H25A 109.9 . . ?
C24 C25 H25A 109.9 . . ?
C20 C25 H25B 109.9 . . ?
C24 C25 H25B 109.9 . . ?
H25A C25 H25B 108.3 . . ?
N4 C26 N5 125.44(19) . . ?
N4 C26 N6 129.3(2) . . ?
N5 C26 N6 105.24(18) . . ?
C28 C27 N5 107.5(2) . . ?
C28 C27 H27 126.3 . . ?
N5 C27 H27 126.3 . . ?
C27 C28 N6 108.4(2) . . ?
C27 C28 H28 125.8 . . ?
N6 C28 H28 125.8 . . ?
C30 C29 C34 123.7(2) . . ?
C30 C29 N5 117.6(2) . . ?
C34 C29 N5 118.7(2) . . ?
C29 C30 C31 117.0(2) . . ?
C29 C30 C35 122.5(2) . . ?
C31 C30 C35 120.5(2) . . ?
C32 C31 C30 120.5(2) . . ?
C32 C31 H31 119.8 . . ?
C30 C31 H31 119.8 . . ?
C31 C32 C33 121.1(2) . . ?
C31 C32 H32 119.4 . . ?
C33 C32 H32 119.4 . . ?
C32 C33 C34 120.7(2) . . ?
C32 C33 H33 119.6 . . ?
C34 C33 H33 119.6 . . ?
C33 C34 C29 117.1(2) . . ?
C33 C34 C38 122.9(2) . . ?
C29 C34 C38 120.0(2) . . ?
C30 C35 C37 110.9(2) . . ?
C30 C35 C36 112.1(2) . . ?
C37 C35 C36 110.2(2) . . ?
C30 C35 H35 107.8 . . ?
C37 C35 H35 107.8 . . ?
C36 C35 H35 107.8 . . ?
C35 C36 H36A 109.5 . . ?
C35 C36 H36B 109.5 . . ?
H36A C36 H36B 109.5 . . ?
C35 C36 H36C 109.5 . . ?
H36A C36 H36C 109.5 . . ?
H36B C36 H36C 109.5 . . ?
C35 C37 H37A 109.5 . . ?
C35 C37 H37B 109.5 . . ?
H37A C37 H37B 109.5 . . ?
C35 C37 H37C 109.5 . . ?
H37A C37 H37C 109.5 . . ?
H37B C37 H37C 109.5 . . ?
C39 C38 C34 114.1(2) . . ?
C39 C38 C40 109.6(2) . . ?
C34 C38 C40 110.2(2) . . ?
C39 C38 H38 107.6 . . ?
C34 C38 H38 107.6 . . ?
C40 C38 H38 107.6 . . ?
C38 C39 H39A 109.5 . . ?
C38 C39 H39B 109.5 . . ?
H39A C39 H39B 109.5 . . ?
C38 C39 H39C 109.5 . . ?
H39A C39 H39C 109.5 . . ?
H39B C39 H39C 109.5 . . ?
C38 C40 H40A 109.5 . . ?
C38 C40 H40B 109.5 . . ?
H40A C40 H40B 109.5 . . ?
C38 C40 H40C 109.5 . . ?
H40A C40 H40C 109.5 . . ?
H40B C40 H40C 109.5 . . ?
N6 C41 C47 109.46(18) . . ?
N6 C41 C46 109.6(2) . . ?
C47 C41 C46 108.7(2) . . ?
N6 C41 C42 109.56(19) . . ?
C47 C41 C42 110.8(2) . . ?
C46 C41 C42 108.69(19) . . ?
C41 C42 C43 109.1(2) . . ?
C41 C42 H42A 109.9 . . ?
C43 C42 H42A 109.9 . . ?
C41 C42 H42B 109.9 . . ?
C43 C42 H42B 109.9 . . ?
H42A C42 H42B 108.3 . . ?
C48 C43 C44 109.2(3) . . ?
C48 C43 C42 109.1(2) . . ?
C44 C43 C42 109.5(3) . . ?
C48 C43 H43 109.7 . . ?
C44 C43 H43 109.7 . . ?
C42 C43 H43 109.7 . . ?
C45 C44 C43 109.1(2) . . ?
C45 C44 H44A 109.9 . . ?
C43 C44 H44A 109.9 . . ?
C45 C44 H44B 109.9 . . ?
C43 C44 H44B 109.9 . . ?
H44A C44 H44B 108.3 . . ?
C49 C45 C44 111.1(3) . . ?
C49 C45 C46 109.6(2) . . ?
C44 C45 C46 108.9(3) . . ?
C49 C45 H45 109.1 . . ?
C44 C45 H45 109.1 . . ?
C46 C45 H45 109.1 . . ?
C45 C46 C41 109.7(2) . . ?
C45 C46 H46A 109.7 . . ?
C41 C46 H46A 109.7 . . ?
C45 C46 H46B 109.7 . . ?
C41 C46 H46B 109.7 . . ?
H46A C46 H46B 108.2 . . ?
C41 C47 C50 109.8(2) . . ?
C41 C47 H47A 109.7 . . ?
C50 C47 H47A 109.7 . . ?
C41 C47 H47B 109.7 . . ?
C50 C47 H47B 109.7 . . ?
H47A C47 H47B 108.2 . . ?
C50 C48 C43 110.4(3) . . ?
C50 C48 H48A 109.6 . . ?
C43 C48 H48A 109.6 . . ?
C50 C48 H48B 109.6 . . ?
C43 C48 H48B 109.6 . . ?
H48A C48 H48B 108.1 . . ?
C45 C49 C50 108.8(3) . . ?
C45 C49 H49A 109.9 . . ?
C50 C49 H49A 109.9 . . ?
C45 C49 H49B 109.9 . . ?
C50 C49 H49B 109.9 . . ?
H49A C49 H49B 108.3 . . ?
C48 C50 C47 108.8(2) . . ?
C48 C50 C49 110.2(3) . . ?
C47 C50 C49 108.9(3) . . ?
C48 C50 H50 109.7 . . ?
C47 C50 H50 109.7 . . ?
C49 C50 H50 109.7 . . ?
Cl3 C99 Cl4 114.9(2) . . ?
Cl3 C99 H99A 108.5 . . ?
Cl4 C99 H99A 108.5 . . ?
Cl3 C99 H99B 108.5 . . ?
Cl4 C99 H99B 108.5 . . ?
H99A C99 H99B 107.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N4 Ti1 N1 C1 -112.9(8) . . . . ?
Cl1 Ti1 N1 C1 8.4(8) . . . . ?
Cl2 Ti1 N1 C1 121.6(8) . . . . ?
N1 Ti1 N4 C26 -109.7(8) . . . . ?
Cl1 Ti1 N4 C26 128.7(8) . . . . ?
Cl2 Ti1 N4 C26 14.4(8) . . . . ?
Ti1 N1 C1 N2 40.0(9) . . . . ?
Ti1 N1 C1 N3 -138.6(7) . . . . ?
C2 N2 C1 N1 -178.8(2) . . . . ?
C4 N2 C1 N1 -3.2(3) . . . . ?
C2 N2 C1 N3 0.0(2) . . . . ?
C4 N2 C1 N3 175.62(19) . . . . ?
C3 N3 C1 N1 178.6(2) . . . . ?
C16 N3 C1 N1 3.5(4) . . . . ?
C3 N3 C1 N2 -0.2(2) . . . . ?
C16 N3 C1 N2 -175.3(2) . . . . ?
C1 N2 C2 C3 0.2(3) . . . . ?
C4 N2 C2 C3 -175.5(2) . . . . ?
N2 C2 C3 N3 -0.3(3) . . . . ?
C1 N3 C3 C2 0.3(3) . . . . ?
C16 N3 C3 C2 175.4(2) . . . . ?
C1 N2 C4 C9 74.9(3) . . . . ?
C2 N2 C4 C9 -110.1(3) . . . . ?
C1 N2 C4 C5 -106.3(3) . . . . ?
C2 N2 C4 C5 68.6(3) . . . . ?
C9 C4 C5 C6 -1.6(4) . . . . ?
N2 C4 C5 C6 179.7(2) . . . . ?
C9 C4 C5 C10 179.4(2) . . . . ?
N2 C4 C5 C10 0.7(4) . . . . ?
C4 C5 C6 C7 -0.2(4) . . . . ?
C10 C5 C6 C7 178.8(3) . . . . ?
C5 C6 C7 C8 1.5(5) . . . . ?
C6 C7 C8 C9 -1.2(4) . . . . ?
C7 C8 C9 C4 -0.5(4) . . . . ?
C7 C8 C9 C13 175.4(2) . . . . ?
C5 C4 C9 C8 1.9(4) . . . . ?
N2 C4 C9 C8 -179.4(2) . . . . ?
C5 C4 C9 C13 -174.1(2) . . . . ?
N2 C4 C9 C13 4.6(3) . . . . ?
C6 C5 C10 C11 -98.6(3) . . . . ?
C4 C5 C10 C11 80.4(3) . . . . ?
C6 C5 C10 C12 29.1(4) . . . . ?
C4 C5 C10 C12 -152.0(3) . . . . ?
C8 C9 C13 C15 -105.4(3) . . . . ?
C4 C9 C13 C15 70.4(3) . . . . ?
C8 C9 C13 C14 18.5(3) . . . . ?
C4 C9 C13 C14 -165.7(2) . . . . ?
C1 N3 C16 C17 59.2(3) . . . . ?
C3 N3 C16 C17 -115.2(2) . . . . ?
C1 N3 C16 C22 -62.6(3) . . . . ?
C3 N3 C16 C22 123.0(2) . . . . ?
C1 N3 C16 C21 178.6(2) . . . . ?
C3 N3 C16 C21 4.3(3) . . . . ?
N3 C16 C17 C18 178.67(19) . . . . ?
C22 C16 C17 C18 -59.5(2) . . . . ?
C21 C16 C17 C18 59.6(3) . . . . ?
C16 C17 C18 C23 59.6(3) . . . . ?
C16 C17 C18 C19 -60.2(3) . . . . ?
C23 C18 C19 C20 -58.7(3) . . . . ?
C17 C18 C19 C20 60.6(3) . . . . ?
C18 C19 C20 C25 59.5(3) . . . . ?
C18 C19 C20 C21 -60.9(3) . . . . ?
N3 C16 C21 C20 -179.4(2) . . . . ?
C17 C16 C21 C20 -59.5(3) . . . . ?
C22 C16 C21 C20 60.8(3) . . . . ?
C19 C20 C21 C16 60.6(3) . . . . ?
C25 C20 C21 C16 -60.9(3) . . . . ?
N3 C16 C22 C24 -179.8(2) . . . . ?
C17 C16 C22 C24 58.7(3) . . . . ?
C21 C16 C22 C24 -61.0(3) . . . . ?
C17 C18 C23 C24 -60.0(3) . . . . ?
C19 C18 C23 C24 59.5(3) . . . . ?
C18 C23 C24 C25 -59.9(3) . . . . ?
C18 C23 C24 C22 60.1(3) . . . . ?
C16 C22 C24 C23 -58.8(3) . . . . ?
C16 C22 C24 C25 61.4(3) . . . . ?
C19 C20 C25 C24 -59.9(3) . . . . ?
C21 C20 C25 C24 60.7(3) . . . . ?
C23 C24 C25 C20 59.2(3) . . . . ?
C22 C24 C25 C20 -61.1(4) . . . . ?
Ti1 N4 C26 N5 41.6(9) . . . . ?
Ti1 N4 C26 N6 -137.6(7) . . . . ?
C27 N5 C26 N4 -178.5(2) . . . . ?
C29 N5 C26 N4 -13.4(4) . . . . ?
C27 N5 C26 N6 0.9(3) . . . . ?
C29 N5 C26 N6 165.9(2) . . . . ?
C28 N6 C26 N4 178.5(2) . . . . ?
C41 N6 C26 N4 2.1(4) . . . . ?
C28 N6 C26 N5 -0.8(3) . . . . ?
C41 N6 C26 N5 -177.2(2) . . . . ?
C26 N5 C27 C28 -0.6(3) . . . . ?
C29 N5 C27 C28 -165.3(2) . . . . ?
N5 C27 C28 N6 0.1(3) . . . . ?
C26 N6 C28 C27 0.5(3) . . . . ?
C41 N6 C28 C27 176.8(2) . . . . ?
C26 N5 C29 C30 -90.8(3) . . . . ?
C27 N5 C29 C30 72.0(3) . . . . ?
C26 N5 C29 C34 89.0(3) . . . . ?
C27 N5 C29 C34 -108.2(3) . . . . ?
C34 C29 C30 C31 -0.6(3) . . . . ?
N5 C29 C30 C31 179.2(2) . . . . ?
C34 C29 C30 C35 178.1(2) . . . . ?
N5 C29 C30 C35 -2.0(3) . . . . ?
C29 C30 C31 C32 -0.9(3) . . . . ?
C35 C30 C31 C32 -179.7(2) . . . . ?
C30 C31 C32 C33 1.8(4) . . . . ?
C31 C32 C33 C34 -1.0(4) . . . . ?
C32 C33 C34 C29 -0.5(3) . . . . ?
C32 C33 C34 C38 176.6(2) . . . . ?
C30 C29 C34 C33 1.4(3) . . . . ?
N5 C29 C34 C33 -178.5(2) . . . . ?
C30 C29 C34 C38 -175.8(2) . . . . ?
N5 C29 C34 C38 4.4(3) . . . . ?
C29 C30 C35 C37 -107.2(3) . . . . ?
C31 C30 C35 C37 71.5(3) . . . . ?
C29 C30 C35 C36 129.1(2) . . . . ?
C31 C30 C35 C36 -52.1(3) . . . . ?
C33 C34 C38 C39 28.7(3) . . . . ?
C29 C34 C38 C39 -154.3(2) . . . . ?
C33 C34 C38 C40 -95.0(3) . . . . ?
C29 C34 C38 C40 82.0(3) . . . . ?
C26 N6 C41 C47 -63.0(3) . . . . ?
C28 N6 C41 C47 121.2(3) . . . . ?
C26 N6 C41 C46 177.9(2) . . . . ?
C28 N6 C41 C46 2.1(3) . . . . ?
C26 N6 C41 C42 58.7(3) . . . . ?
C28 N6 C41 C42 -117.1(2) . . . . ?
N6 C41 C42 C43 -179.8(2) . . . . ?
C47 C41 C42 C43 -58.9(3) . . . . ?
C46 C41 C42 C43 60.5(3) . . . . ?
C41 C42 C43 C48 58.9(3) . . . . ?
C41 C42 C43 C44 -60.6(3) . . . . ?
C48 C43 C44 C45 -58.9(4) . . . . ?
C42 C43 C44 C45 60.5(4) . . . . ?
C43 C44 C45 C49 60.4(4) . . . . ?
C43 C44 C45 C46 -60.4(4) . . . . ?
C49 C45 C46 C41 -60.6(3) . . . . ?
C44 C45 C46 C41 61.1(3) . . . . ?
N6 C41 C46 C45 179.2(2) . . . . ?
C47 C41 C46 C45 59.6(3) . . . . ?
C42 C41 C46 C45 -61.1(3) . . . . ?
N6 C41 C47 C50 -179.8(2) . . . . ?
C46 C41 C47 C50 -60.2(3) . . . . ?
C42 C41 C47 C50 59.2(3) . . . . ?
C44 C43 C48 C50 59.0(3) . . . . ?
C42 C43 C48 C50 -60.7(3) . . . . ?
C44 C45 C49 C50 -59.5(3) . . . . ?
C46 C45 C49 C50 60.9(3) . . . . ?
C43 C48 C50 C47 60.5(3) . . . . ?
C43 C48 C50 C49 -58.8(3) . . . . ?
C41 C47 C50 C48 -59.0(3) . . . . ?
C41 C47 C50 C49 61.1(3) . . . . ?
C45 C49 C50 C48 58.3(3) . . . . ?
C45 C49 C50 C47 -61.0(3) . . . . ?

_refine_diff_density_max         0.813
_refine_diff_density_min         -1.177
_refine_diff_density_rms         0.069



#=============================================================================
# end of cif data for "mk24mk2" (6b)
#=============================================================================
#=============================================================================
# end of combined cif file
#=============================================================================
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: dichloromethane/n-hexane'
_chemical_properties_physical    
'Sample sufferred radiation damage upon longer exposition to the X-ray beam'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mk26mk
_database_code_depnum_ccdc_archive 'CCDC 2174870'
loop_
_audit_author_name
_audit_author_address
'Marvin Koneczny'
;TU Braunschweig
Germany
;
_audit_update_record             
;
2022-05-25 deposited with the CCDC.	2022-07-08 downloaded from the CCDC.
;

# start Validation Reply Form
_vrf_PLAT601_mk26mk              
;
PROBLEM: Unit Cell Contains Solvent Accessible VOIDS of .   209 Ang**3
RESPONSE:  A solvent mask was calculated and 66 electrons were found in
 a volume of 231\%A^3^ in 1 void per unit cell. This is consistent with
 the presence of 0.5[CH2Cl2], 0.25[C6H14] per Asymmetric Unit which 
 account for 67 electrons per unit cell. 
 As a reason, why the molecules could not be refined satisfactorly,
 may be modulation. This could be supported by 'smeared' reflexes 
 along the c* axis (see SI).
;
_vrf_PLAT097_mk26mk              
;
PROBLEM: Large Reported Max.  (Positive) Residual Density   2.30 eA-3
RESPONSE: May be caused by by the not resolvable modulation.
;
# end Validation Reply Form

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         
'C25 H34 Cl3 N3 Ti, C H2 Cl2, 0.5[CH2Cl2], 0.25[C6H14]'
_chemical_formula_sum            'C26 H36 Cl5 N3 Ti'
_chemical_formula_weight         615.73

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   9.8202(4)
_cell_length_b                   13.2868(6)
_cell_length_c                   14.4204(7)
_cell_angle_alpha                63.091(5)
_cell_angle_beta                 81.445(4)
_cell_angle_gamma                76.358(4)
_cell_volume                     1628.59(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    22749
_cell_measurement_theta_min      2.1240
_cell_measurement_theta_max      32.5100

_exptl_crystal_description       'fragment of block'
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.256
_exptl_crystal_F_000             640
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.05
_exptl_absorpt_coefficient_mu    0.691
_exptl_absorpt_correction_T_min  0.88732
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.21a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.827
_oxdiff_exptl_absorpt_empirical_full_max 1.207
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       'ω scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            43682
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_av_R_equivalents  0.0215
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         2.137
_diffrn_reflns_theta_max         32.385
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.842
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.842
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.842
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             9833
_reflns_number_gt                8302
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       ?
_computing_cell_refinement       'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_structure_solution    
'SHELXT-2014/5 (G. M. Sheldrick, Acta Cryst., 2015, A71, 3-8)'
_computing_structure_refinement  
'SHELXL-2018/3 (G. M. Sheldrick, Acta Cryst. (2008), A64, 112-122)'
_computing_molecular_graphics    ?
_computing_publication_material  
'OLEX2 v1.2 (O. V. Dolomanov et al., J. Appl. Cryst., 2009, 42, 339-341)'
_refine_special_details          
;All C-H hydrogens, except H atoms in methyl groups, were placed in 
 idealised positions and refined using a riding model, with a common U 
 restrained to be 1.2 times the equivalent isotropic displacement 
 parameter of the parent atom. Methyl hydrogens were located in 
 difference synthesis. Methyl groups were idealized and refined as rigid
 groups allowed to rotate but not tip. 
 The N-H hydrogen was refined freely.

 Refinement of F² against ALL reflections.  The weighted R-factor
 wR and goodness of fit S are based on F², conventional R-factors R 
 are based on F, with F set to zero for negative F². The threshold
 expression of F² > 2sigma(F²) is used only for calculating
 R-factors(gt) etc. and isnot relevant to the choice of reflections 
 for refinement.  R-factors based on F² are statistically about twice
 as large as those based on F, and R- factors based on ALL data will be
 even larger.

 A solvent mask was calculated and 66 electrons were found in a volume
 of 231Å³ in 1 void per unit cell. This is consistent with the
 presence of 0.5[CH2Cl2], 0.25[C6H14] per Asymmetric Unit which account
 for 67 electrons per unit cell. 
 As a reason, why the molecules could not be refined satisfactorly,
 may be modulation. This could be supported by 'smeared' reflexes 
 along the c* axis (see SI).,SQUEEZE
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0806P)²+2.0844P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         9833
_refine_ls_number_parameters     320
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0667
_refine_ls_R_factor_gt           0.0581
_refine_ls_wR_factor_ref         0.1618
_refine_ls_wR_factor_gt          0.1560
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_restrained_S_all      1.030
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 1.00198(4) 0.04564(3) 0.19925(3) 0.02648(10) Uani 1 1 d . . . . .
Cl1 Cl 1.09226(6) 0.20698(5) 0.13083(5) 0.03787(14) Uani 1 1 d . . . . .
Cl2 Cl 1.04516(7) -0.05217(6) 0.36966(5) 0.04195(15) Uani 1 1 d . . . . .
Cl3 Cl 1.09949(6) -0.07064(6) 0.12331(5) 0.04155(15) Uani 1 1 d . . . . .
N1 N 0.82221(18) 0.08213(15) 0.18635(14) 0.0251(3) Uani 1 1 d . . . . .
N2 N 0.62347(18) 0.23480(14) 0.14817(14) 0.0242(3) Uani 1 1 d . . . . .
N3 N 0.58242(17) 0.06673(14) 0.18053(13) 0.0213(3) Uani 1 1 d . . . . .
C1 C 0.6855(2) 0.12302(16) 0.17397(16) 0.0219(4) Uani 1 1 d . . . . .
C2 C 0.4819(2) 0.24863(18) 0.13747(18) 0.0270(4) Uani 1 1 d . . . . .
H2 H 0.414766 0.318186 0.119341 0.032 Uiso 1 1 calc R U . . .
C3 C 0.4567(2) 0.14486(18) 0.15759(17) 0.0255(4) Uani 1 1 d . . . . .
H3 H 0.368229 0.128361 0.156233 0.031 Uiso 1 1 calc R U . . .
C4 C 0.6958(2) 0.32506(16) 0.13000(16) 0.0230(4) Uani 1 1 d . . . . .
C5 C 0.7075(2) 0.34847(19) 0.21343(17) 0.0275(4) Uani 1 1 d . . . . .
C6 C 0.7729(2) 0.44006(19) 0.19158(18) 0.0296(4) Uani 1 1 d . . . . .
H6 H 0.784316 0.457924 0.246403 0.036 Uiso 1 1 calc R U . . .
C7 C 0.8213(2) 0.50502(18) 0.09189(19) 0.0298(4) Uani 1 1 d . . . . .
H7 H 0.862798 0.568330 0.078552 0.036 Uiso 1 1 calc R U . . .
C8 C 0.8098(2) 0.47863(17) 0.01099(18) 0.0280(4) Uani 1 1 d . . . . .
H8 H 0.844442 0.523550 -0.057134 0.034 Uiso 1 1 calc R U . . .
C9 C 0.7478(2) 0.38660(16) 0.02875(17) 0.0252(4) Uani 1 1 d . . . . .
C10 C 0.6552(3) 0.2770(2) 0.32355(19) 0.0393(6) Uani 1 1 d . . . . .
H10 H 0.598455 0.225539 0.320021 0.047 Uiso 1 1 calc R U . . .
C11 C 0.7767(5) 0.2015(3) 0.3919(3) 0.0672(11) Uani 1 1 d . . . . .
H11A H 0.827162 0.145030 0.366702 0.101 Uiso 1 1 calc R U . . .
H11B H 0.740884 0.161454 0.463765 0.101 Uiso 1 1 calc R U . . .
H11C H 0.840548 0.249312 0.389671 0.101 Uiso 1 1 calc R U . . .
C12 C 0.5614(4) 0.3508(4) 0.3727(2) 0.0621(10) Uani 1 1 d . . . . .
H12A H 0.618238 0.392954 0.387482 0.093 Uiso 1 1 calc R U . . .
H12B H 0.516606 0.301386 0.437756 0.093 Uiso 1 1 calc R U . . .
H12C H 0.489191 0.405527 0.324599 0.093 Uiso 1 1 calc R U . . .
C13 C 0.7364(3) 0.35608(17) -0.05923(17) 0.0287(4) Uani 1 1 d . . . . .
H13 H 0.715502 0.276754 -0.027278 0.034 Uiso 1 1 calc R U . . .
C14 C 0.8733(3) 0.3555(3) -0.1254(2) 0.0418(6) Uani 1 1 d . . . . .
H14A H 0.896318 0.432496 -0.157738 0.063 Uiso 1 1 calc R U . . .
H14B H 0.862316 0.333434 -0.179728 0.063 Uiso 1 1 calc R U . . .
H14C H 0.949126 0.300252 -0.081067 0.063 Uiso 1 1 calc R U . . .
C15 C 0.6150(3) 0.4380(2) -0.12710(19) 0.0336(5) Uani 1 1 d . . . . .
H15A H 0.529034 0.439607 -0.083060 0.050 Uiso 1 1 calc R U . . .
H15B H 0.601540 0.411434 -0.177793 0.050 Uiso 1 1 calc R U . . .
H15C H 0.636461 0.515462 -0.163974 0.050 Uiso 1 1 calc R U . . .
C16 C 0.6041(2) -0.05702(16) 0.20324(15) 0.0202(3) Uani 1 1 d . . . . .
C17 C 0.6679(2) -0.13226(18) 0.30921(16) 0.0268(4) Uani 1 1 d . . . . .
H17A H 0.603410 -0.120046 0.364454 0.032 Uiso 1 1 calc R U . . .
H17B H 0.757833 -0.111336 0.310012 0.032 Uiso 1 1 calc R U . . .
C18 C 0.6927(3) -0.25919(19) 0.32955(19) 0.0372(5) Uani 1 1 d . . . . .
H18 H 0.735840 -0.308940 0.398340 0.045 Uiso 1 1 calc R U . . .
C19 C 0.5524(3) -0.2912(2) 0.3310(2) 0.0431(6) Uani 1 1 d . . . . .
H19A H 0.488706 -0.280581 0.387237 0.052 Uiso 1 1 calc R U . . .
H19B H 0.567479 -0.373029 0.344794 0.052 Uiso 1 1 calc R U . . .
C20 C 0.4859(3) -0.2150(2) 0.22586(19) 0.0329(5) Uani 1 1 d . . . . .
H20 H 0.393837 -0.235613 0.227166 0.039 Uiso 1 1 calc R U . . .
C21 C 0.4624(2) -0.08795(18) 0.20446(17) 0.0262(4) Uani 1 1 d . . . . .
H21A H 0.419350 -0.038544 0.136514 0.031 Uiso 1 1 calc R U . . .
H21B H 0.397948 -0.074804 0.259267 0.031 Uiso 1 1 calc R U . . .
C22 C 0.7009(2) -0.07571(18) 0.11600(16) 0.0246(4) Uani 1 1 d . . . . .
H22A H 0.657467 -0.026642 0.048132 0.030 Uiso 1 1 calc R U . . .
H22B H 0.791821 -0.053944 0.112723 0.030 Uiso 1 1 calc R U . . .
C23 C 0.7915(3) -0.2766(2) 0.2436(2) 0.0402(6) Uani 1 1 d . . . . .
H23A H 0.810641 -0.358661 0.257714 0.048 Uiso 1 1 calc R U . . .
H23B H 0.881688 -0.254777 0.242279 0.048 Uiso 1 1 calc R U . . .
C24 C 0.7248(3) -0.2025(2) 0.1376(2) 0.0341(5) Uani 1 1 d . . . . .
H24 H 0.789232 -0.215348 0.081750 0.041 Uiso 1 1 calc R U . . .
C25 C 0.5839(3) -0.2342(2) 0.1397(2) 0.0363(5) Uani 1 1 d . . . . .
H25A H 0.598602 -0.315798 0.152846 0.044 Uiso 1 1 calc R U . . .
H25B H 0.541035 -0.186059 0.071552 0.044 Uiso 1 1 calc R U . . .
Cl4 Cl 0.36251(10) 0.08290(9) 0.42863(7) 0.0635(2) Uani 1 1 d . . . . .
Cl5 Cl 0.19960(16) 0.31391(10) 0.31644(14) 0.1044(5) Uani 1 1 d . . . . .
C99 C 0.1949(4) 0.1670(3) 0.3911(3) 0.0555(8) Uani 1 1 d . . . . .
H99A H 0.154232 0.139344 0.350096 0.067 Uiso 1 1 calc R U . . .
H99B H 0.132985 0.157303 0.454191 0.067 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 N1 1.7316(18) . ?
Ti1 Cl3 2.2415(8) . ?
Ti1 Cl2 2.2510(7) . ?
Ti1 Cl1 2.2531(7) . ?
N1 C1 1.330(3) . ?
N2 C1 1.362(2) . ?
N2 C2 1.381(3) . ?
N2 C4 1.440(2) . ?
N3 C1 1.363(2) . ?
N3 C3 1.385(3) . ?
N3 C16 1.491(2) . ?
C2 C3 1.350(3) . ?
C2 H2 0.9500 . ?
C3 H3 0.9500 . ?
C4 C5 1.398(3) . ?
C4 C9 1.398(3) . ?
C5 C6 1.398(3) . ?
C5 C10 1.520(3) . ?
C6 C7 1.380(3) . ?
C6 H6 0.9500 . ?
C7 C8 1.387(3) . ?
C7 H7 0.9500 . ?
C8 C9 1.397(3) . ?
C8 H8 0.9500 . ?
C9 C13 1.522(3) . ?
C10 C11 1.513(5) . ?
C10 C12 1.524(5) . ?
C10 H10 1.0000 . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 C15 1.528(3) . ?
C13 C14 1.529(4) . ?
C13 H13 1.0000 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?
C16 C17 1.527(3) . ?
C16 C21 1.537(3) . ?
C16 C22 1.537(3) . ?
C17 C18 1.539(3) . ?
C17 H17A 0.9900 . ?
C17 H17B 0.9900 . ?
C18 C23 1.525(4) . ?
C18 C19 1.530(4) . ?
C18 H18 1.0000 . ?
C19 C20 1.531(4) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 C25 1.533(4) . ?
C20 C21 1.537(3) . ?
C20 H20 1.0000 . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?
C22 C24 1.533(3) . ?
C22 H22A 0.9900 . ?
C22 H22B 0.9900 . ?
C23 C24 1.538(4) . ?
C23 H23A 0.9900 . ?
C23 H23B 0.9900 . ?
C24 C25 1.531(4) . ?
C24 H24 1.0000 . ?
C25 H25A 0.9900 . ?
C25 H25B 0.9900 . ?
Cl4 C99 1.761(4) . ?
Cl5 C99 1.760(4) . ?
C99 H99A 0.9900 . ?
C99 H99B 0.9900 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Ti1 Cl3 110.07(7) . . ?
N1 Ti1 Cl2 108.78(7) . . ?
Cl3 Ti1 Cl2 107.52(3) . . ?
N1 Ti1 Cl1 109.40(6) . . ?
Cl3 Ti1 Cl1 111.84(3) . . ?
Cl2 Ti1 Cl1 109.17(3) . . ?
C1 N1 Ti1 173.03(15) . . ?
C1 N2 C2 109.25(16) . . ?
C1 N2 C4 125.10(17) . . ?
C2 N2 C4 125.58(17) . . ?
C1 N3 C3 108.57(16) . . ?
C1 N3 C16 125.21(16) . . ?
C3 N3 C16 126.15(16) . . ?
N1 C1 N2 124.35(17) . . ?
N1 C1 N3 128.75(18) . . ?
N2 C1 N3 106.86(16) . . ?
C3 C2 N2 107.26(18) . . ?
C3 C2 H2 126.4 . . ?
N2 C2 H2 126.4 . . ?
C2 C3 N3 108.05(17) . . ?
C2 C3 H3 126.0 . . ?
N3 C3 H3 126.0 . . ?
C5 C4 C9 123.46(18) . . ?
C5 C4 N2 118.57(19) . . ?
C9 C4 N2 117.95(18) . . ?
C6 C5 C4 116.8(2) . . ?
C6 C5 C10 120.9(2) . . ?
C4 C5 C10 122.25(19) . . ?
C7 C6 C5 121.3(2) . . ?
C7 C6 H6 119.4 . . ?
C5 C6 H6 119.4 . . ?
C6 C7 C8 120.54(19) . . ?
C6 C7 H7 119.7 . . ?
C8 C7 H7 119.7 . . ?
C7 C8 C9 120.6(2) . . ?
C7 C8 H8 119.7 . . ?
C9 C8 H8 119.7 . . ?
C8 C9 C4 117.26(19) . . ?
C8 C9 C13 121.0(2) . . ?
C4 C9 C13 121.74(18) . . ?
C11 C10 C5 110.9(2) . . ?
C11 C10 C12 109.8(2) . . ?
C5 C10 C12 112.4(2) . . ?
C11 C10 H10 107.8 . . ?
C5 C10 H10 107.8 . . ?
C12 C10 H10 107.8 . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C10 C12 H12A 109.5 . . ?
C10 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C10 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C9 C13 C15 110.52(18) . . ?
C9 C13 C14 112.1(2) . . ?
C15 C13 C14 110.6(2) . . ?
C9 C13 H13 107.8 . . ?
C15 C13 H13 107.8 . . ?
C14 C13 H13 107.8 . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C13 C15 H15A 109.5 . . ?
C13 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C13 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
N3 C16 C17 109.98(15) . . ?
N3 C16 C21 109.44(16) . . ?
C17 C16 C21 109.21(16) . . ?
N3 C16 C22 108.40(15) . . ?
C17 C16 C22 111.06(17) . . ?
C21 C16 C22 108.71(16) . . ?
C16 C17 C18 108.97(17) . . ?
C16 C17 H17A 109.9 . . ?
C18 C17 H17A 109.9 . . ?
C16 C17 H17B 109.9 . . ?
C18 C17 H17B 109.9 . . ?
H17A C17 H17B 108.3 . . ?
C23 C18 C19 109.9(2) . . ?
C23 C18 C17 109.31(19) . . ?
C19 C18 C17 109.3(2) . . ?
C23 C18 H18 109.4 . . ?
C19 C18 H18 109.4 . . ?
C17 C18 H18 109.4 . . ?
C18 C19 C20 109.55(19) . . ?
C18 C19 H19A 109.8 . . ?
C20 C19 H19A 109.8 . . ?
C18 C19 H19B 109.8 . . ?
C20 C19 H19B 109.8 . . ?
H19A C19 H19B 108.2 . . ?
C19 C20 C25 109.3(2) . . ?
C19 C20 C21 109.75(19) . . ?
C25 C20 C21 109.52(19) . . ?
C19 C20 H20 109.4 . . ?
C25 C20 H20 109.4 . . ?
C21 C20 H20 109.4 . . ?
C16 C21 C20 109.18(18) . . ?
C16 C21 H21A 109.8 . . ?
C20 C21 H21A 109.8 . . ?
C16 C21 H21B 109.8 . . ?
C20 C21 H21B 109.8 . . ?
H21A C21 H21B 108.3 . . ?
C24 C22 C16 109.39(17) . . ?
C24 C22 H22A 109.8 . . ?
C16 C22 H22A 109.8 . . ?
C24 C22 H22B 109.8 . . ?
C16 C22 H22B 109.8 . . ?
H22A C22 H22B 108.2 . . ?
C18 C23 C24 110.0(2) . . ?
C18 C23 H23A 109.7 . . ?
C24 C23 H23A 109.7 . . ?
C18 C23 H23B 109.7 . . ?
C24 C23 H23B 109.7 . . ?
H23A C23 H23B 108.2 . . ?
C25 C24 C22 109.27(19) . . ?
C25 C24 C23 110.0(2) . . ?
C22 C24 C23 108.63(18) . . ?
C25 C24 H24 109.6 . . ?
C22 C24 H24 109.6 . . ?
C23 C24 H24 109.6 . . ?
C24 C25 C20 109.43(18) . . ?
C24 C25 H25A 109.8 . . ?
C20 C25 H25A 109.8 . . ?
C24 C25 H25B 109.8 . . ?
C20 C25 H25B 109.8 . . ?
H25A C25 H25B 108.2 . . ?
Cl5 C99 Cl4 112.37(18) . . ?
Cl5 C99 H99A 109.1 . . ?
Cl4 C99 H99A 109.1 . . ?
Cl5 C99 H99B 109.1 . . ?
Cl4 C99 H99B 109.1 . . ?
H99A C99 H99B 107.9 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C2 N2 C1 N1 177.5(2) . . . . ?
C4 N2 C1 N1 0.3(3) . . . . ?
C2 N2 C1 N3 -0.7(2) . . . . ?
C4 N2 C1 N3 -177.85(19) . . . . ?
C3 N3 C1 N1 -177.5(2) . . . . ?
C16 N3 C1 N1 -0.4(3) . . . . ?
C3 N3 C1 N2 0.6(2) . . . . ?
C16 N3 C1 N2 177.68(17) . . . . ?
C1 N2 C2 C3 0.5(3) . . . . ?
C4 N2 C2 C3 177.7(2) . . . . ?
N2 C2 C3 N3 -0.1(3) . . . . ?
C1 N3 C3 C2 -0.3(2) . . . . ?
C16 N3 C3 C2 -177.34(19) . . . . ?
C1 N2 C4 C5 -92.4(3) . . . . ?
C2 N2 C4 C5 90.9(3) . . . . ?
C1 N2 C4 C9 89.1(2) . . . . ?
C2 N2 C4 C9 -87.6(3) . . . . ?
C9 C4 C5 C6 1.2(3) . . . . ?
N2 C4 C5 C6 -177.20(19) . . . . ?
C9 C4 C5 C10 -177.5(2) . . . . ?
N2 C4 C5 C10 4.2(3) . . . . ?
C4 C5 C6 C7 1.0(3) . . . . ?
C10 C5 C6 C7 179.7(2) . . . . ?
C5 C6 C7 C8 -1.9(4) . . . . ?
C6 C7 C8 C9 0.7(3) . . . . ?
C7 C8 C9 C4 1.4(3) . . . . ?
C7 C8 C9 C13 -179.2(2) . . . . ?
C5 C4 C9 C8 -2.4(3) . . . . ?
N2 C4 C9 C8 176.01(18) . . . . ?
C5 C4 C9 C13 178.3(2) . . . . ?
N2 C4 C9 C13 -3.4(3) . . . . ?
C6 C5 C10 C11 -71.4(3) . . . . ?
C4 C5 C10 C11 107.1(3) . . . . ?
C6 C5 C10 C12 51.9(3) . . . . ?
C4 C5 C10 C12 -129.5(3) . . . . ?
C8 C9 C13 C15 -78.5(3) . . . . ?
C4 C9 C13 C15 100.8(2) . . . . ?
C8 C9 C13 C14 45.5(3) . . . . ?
C4 C9 C13 C14 -135.2(2) . . . . ?
C1 N3 C16 C17 59.8(2) . . . . ?
C3 N3 C16 C17 -123.6(2) . . . . ?
C1 N3 C16 C21 179.75(18) . . . . ?
C3 N3 C16 C21 -3.7(3) . . . . ?
C1 N3 C16 C22 -61.8(2) . . . . ?
C3 N3 C16 C22 114.8(2) . . . . ?
N3 C16 C17 C18 -178.57(18) . . . . ?
C21 C16 C17 C18 61.3(2) . . . . ?
C22 C16 C17 C18 -58.6(2) . . . . ?
C16 C17 C18 C23 59.3(2) . . . . ?
C16 C17 C18 C19 -61.0(3) . . . . ?
C23 C18 C19 C20 -59.9(3) . . . . ?
C17 C18 C19 C20 60.0(3) . . . . ?
C18 C19 C20 C25 60.7(3) . . . . ?
C18 C19 C20 C21 -59.4(3) . . . . ?
N3 C16 C21 C20 178.94(17) . . . . ?
C17 C16 C21 C20 -60.6(2) . . . . ?
C22 C16 C21 C20 60.7(2) . . . . ?
C19 C20 C21 C16 59.6(2) . . . . ?
C25 C20 C21 C16 -60.4(2) . . . . ?
N3 C16 C22 C24 179.99(17) . . . . ?
C17 C16 C22 C24 59.1(2) . . . . ?
C21 C16 C22 C24 -61.1(2) . . . . ?
C19 C18 C23 C24 58.6(2) . . . . ?
C17 C18 C23 C24 -61.4(3) . . . . ?
C16 C22 C24 C25 60.9(2) . . . . ?
C16 C22 C24 C23 -59.1(2) . . . . ?
C18 C23 C24 C25 -58.3(2) . . . . ?
C18 C23 C24 C22 61.2(3) . . . . ?
C22 C24 C25 C20 -60.1(3) . . . . ?
C23 C24 C25 C20 59.1(3) . . . . ?
C19 C20 C25 C24 -60.3(2) . . . . ?
C21 C20 C25 C24 60.0(3) . . . . ?

_refine_diff_density_max         2.297
_refine_diff_density_min         -1.603
_refine_diff_density_rms         0.088



_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: dichloromethane/n-hexane -30°C'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mk22mk
_database_code_depnum_ccdc_archive 'CCDC 2174871'
loop_
_audit_author_name
_audit_author_address
'Marvin Koneczny'
;TU Braunschweig
Germany
;
_audit_update_record             
;
2022-05-25 deposited with the CCDC.	2022-07-08 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C27 H33 Cl2 N3 Ti'
_chemical_formula_sum            'C27 H33 Cl2 N3 Ti'
_chemical_formula_weight         518.36

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2191 1.8069 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   9.97590(10)
_cell_length_b                   11.30190(10)
_cell_length_c                   22.11580(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2493.48(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    47896
_cell_measurement_theta_min      3.9950
_cell_measurement_theta_max      77.4290

_exptl_crystal_description       trapezoid
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.381
_exptl_crystal_F_000             1088
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.228
_exptl_crystal_size_mid          0.126
_exptl_crystal_size_min          0.072
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
0 1 14 0.0673
0 -1 -14 0.0582
6 0 0 0.1144
0 -7 1 0.0547
3 -6 4 0.0885
5 5 3 0.0849
-3 -6 -2 0.0764
0 -5 10 0.0674
0 5 -10 0.0272
6 3 0 0.1009
-6 -3 0 0.0989
0 7 5 0.0171
0 -7 -5 0.0539
5 -5 0 0.1056
-5 5 0 0.0787
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-0.0938 0.7925 14.2672 0.1231 0.9377 -0.3249
-0.1335 -0.8076 -14.2623 -0.1216 -0.9258 0.3579
6.4651 0.4368 0.0025 -0.0425 -0.3294 -0.9432
0.0310 -7.3066 1.2914 0.9898 -0.1297 0.0584
3.0671 -6.2065 3.5181 0.8868 -0.1166 -0.4472
4.7106 4.8085 2.9171 -0.5798 0.0752 -0.8113
-3.4052 -6.1838 -1.6392 0.7858 -0.1024 0.6100
0.0136 -5.3531 9.8194 0.8673 0.4714 -0.1602
-0.1315 5.3224 -9.8788 -0.8644 -0.4698 0.1790
5.8758 3.0856 0.1156 -0.3934 -0.2147 -0.8940
-5.8762 -3.0848 -0.1174 0.3932 0.2146 0.8940
0.1607 6.8718 5.0068 -0.8308 0.5087 -0.2256
-0.0913 -6.8814 -4.9650 0.8330 -0.5100 0.2147
4.9007 -4.7957 0.0223 0.6481 -0.3960 -0.6505
-4.9070 4.7874 -0.0325 -0.6472 0.3955 0.6518
_exptl_absorpt_coefficient_mu    5.029
_exptl_absorpt_correction_T_min  0.670
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.21a (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.778
_oxdiff_exptl_absorpt_empirical_full_max 1.431
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            53498
_diffrn_reflns_av_unetI/netI     0.0141
_diffrn_reflns_av_R_equivalents  0.0323
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_theta_min         3.998
_diffrn_reflns_theta_max         77.473
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             5264
_reflns_number_gt                5221
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.758
_reflns_Friedel_fraction_max     0.989
_reflns_Friedel_fraction_full    1.000

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;

_computing_data_collection       'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_structure_solution    
'SHELXT-2014/5 (G. M. Sheldrick, Acta Cryst., 2015, A71, 3-8)'
_computing_structure_refinement  
'SHELXL-2018/3 (G. M. Sheldrick, Acta Cryst., 2008, A64, 112-122)'
_computing_molecular_graphics    ?
_computing_publication_material  
'OLEX2 v1.2 (O. V. Dolomanov et al., J. Appl. Cryst., 2009, 42, 339-341)'
_refine_special_details          
;All C-H hydrogens, except H atoms in methyl groups, were placed in 
 idealised positions and refined using a riding model, with a common U 
 restrained to be 1.2 times the equivalent isotropic displacement 
 parameter of the parent atom. Methyl hydrogens were located in 
 difference synthesis. Methyl groups were idealized and refined as rigid
 groups allowed to rotate but not tip. 
 The N-H hydrogen was refined freely.

 Refinement of F² against ALL reflections.  The weighted R-factor
 wR and goodness of fit S are based on F², conventional R-factors R 
 are based on F, with F set to zero for negative F². The threshold
 expression of F² > 2sigma(F²) is used only for calculating
 R-factors(gt) etc. and isnot relevant to the choice of reflections 
 for refinement.  R-factors based on F² are statistically about twice
 as large as those based on F, and R- factors based on ALL data will be
 even larger.

 Refined as a 2-component inversion twin.,Twin
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0258P)²+0.9166P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.434(5)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         5264
_refine_ls_number_parameters     302
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0227
_refine_ls_R_factor_gt           0.0218
_refine_ls_wR_factor_ref         0.0513
_refine_ls_wR_factor_gt          0.0504
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_restrained_S_all      1.033
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Ti1 Ti 0.23702(3) 0.64777(3) 0.40476(2) 0.01229(7) Uani 1 1 d . . . . .
Cl1 Cl 0.02023(4) 0.70721(4) 0.38338(2) 0.01978(10) Uani 1 1 d . . . . .
Cl2 Cl 0.35065(4) 0.82643(4) 0.40539(2) 0.02134(10) Uani 1 1 d . . . . .
N1 N 0.29424(15) 0.58545(14) 0.33571(7) 0.0156(3) Uani 1 1 d . . . . .
N2 N 0.47407(16) 0.47328(14) 0.29249(7) 0.0165(3) Uani 1 1 d . . . . .
N3 N 0.31254(16) 0.52601(14) 0.23077(7) 0.0149(3) Uani 1 1 d . . . . .
C1 C 0.35350(18) 0.53185(16) 0.28999(8) 0.0148(3) Uani 1 1 d . . . . .
C2 C 0.5078(2) 0.43253(17) 0.23517(8) 0.0186(4) Uani 1 1 d . . . . .
H2 H 0.586405 0.389897 0.224524 0.022 Uiso 1 1 calc R U . . .
C3 C 0.4082(2) 0.46480(17) 0.19762(8) 0.0177(4) Uani 1 1 d . . . . .
H3 H 0.404112 0.448462 0.155525 0.021 Uiso 1 1 calc R U . . .
C4 C 0.54922(18) 0.45131(17) 0.34682(8) 0.0156(3) Uani 1 1 d . . . . .
C5 C 0.53239(18) 0.34292(17) 0.37597(8) 0.0163(3) Uani 1 1 d . . . . .
C6 C 0.60593(19) 0.32249(16) 0.42854(8) 0.0167(4) Uani 1 1 d . . . . .
H6 H 0.595311 0.249517 0.449318 0.020 Uiso 1 1 calc R U . . .
C7 C 0.69495(19) 0.40691(17) 0.45139(9) 0.0167(4) Uani 1 1 d . . . . .
C8 C 0.70991(18) 0.51355(17) 0.42044(9) 0.0171(4) Uani 1 1 d . . . . .
H8 H 0.770907 0.570990 0.435497 0.020 Uiso 1 1 calc R U . . .
C9 C 0.63754(18) 0.53809(16) 0.36791(9) 0.0166(4) Uani 1 1 d . . . . .
C10 C 0.4386(2) 0.24990(18) 0.35119(10) 0.0224(4) Uani 1 1 d . . . . .
H10A H 0.348701 0.283651 0.346643 0.034 Uiso 1 1 calc R U . . .
H10B H 0.435070 0.182679 0.379137 0.034 Uiso 1 1 calc R U . . .
H10C H 0.471263 0.223013 0.311721 0.034 Uiso 1 1 calc R U . . .
C11 C 0.7734(2) 0.38221(18) 0.50830(9) 0.0204(4) Uani 1 1 d . . . . .
H11A H 0.854219 0.337095 0.498218 0.031 Uiso 1 1 calc R U . . .
H11B H 0.717874 0.336275 0.536344 0.031 Uiso 1 1 calc R U . . .
H11C H 0.798928 0.457191 0.527331 0.031 Uiso 1 1 calc R U . . .
C12 C 0.6505(2) 0.65563(18) 0.33638(9) 0.0217(4) Uani 1 1 d . . . . .
H12A H 0.570321 0.703328 0.344220 0.032 Uiso 1 1 calc R U . . .
H12B H 0.659859 0.642792 0.292762 0.032 Uiso 1 1 calc R U . . .
H12C H 0.729746 0.697266 0.351647 0.032 Uiso 1 1 calc R U . . .
C13 C 0.18367(18) 0.57496(16) 0.20673(8) 0.0136(3) Uani 1 1 d . . . . .
C14 C 0.06631(19) 0.52343(16) 0.24256(8) 0.0161(3) Uani 1 1 d . . . . .
H14A H 0.076187 0.543715 0.285884 0.019 Uiso 1 1 calc R U . . .
H14B H 0.066165 0.436145 0.238804 0.019 Uiso 1 1 calc R U . . .
C15 C -0.06636(19) 0.57358(17) 0.21839(9) 0.0174(4) Uani 1 1 d . . . . .
H15 H -0.142457 0.540964 0.242652 0.021 Uiso 1 1 calc R U . . .
C16 C -0.0837(2) 0.53814(18) 0.15223(9) 0.0235(4) Uani 1 1 d . . . . .
H16A H -0.169479 0.569667 0.136488 0.028 Uiso 1 1 calc R U . . .
H16B H -0.085572 0.450842 0.148630 0.028 Uiso 1 1 calc R U . . .
C17 C 0.0337(2) 0.58840(19) 0.11555(9) 0.0224(4) Uani 1 1 d . . . . .
H17 H 0.023384 0.565283 0.072154 0.027 Uiso 1 1 calc R U . . .
C18 C 0.1674(2) 0.53964(18) 0.13997(8) 0.0202(4) Uani 1 1 d . . . . .
H18A H 0.168732 0.452359 0.136199 0.024 Uiso 1 1 calc R U . . .
H18B H 0.242832 0.571967 0.116007 0.024 Uiso 1 1 calc R U . . .
C19 C 0.18450(18) 0.71054(16) 0.21182(8) 0.0145(3) Uani 1 1 d . . . . .
H19A H 0.260638 0.743366 0.188514 0.017 Uiso 1 1 calc R U . . .
H19B H 0.195258 0.734187 0.254645 0.017 Uiso 1 1 calc R U . . .
C20 C -0.06530(18) 0.70905(17) 0.22374(8) 0.0157(4) Uani 1 1 d . . . . .
H20A H -0.150989 0.741595 0.208469 0.019 Uiso 1 1 calc R U . . .
H20B H -0.055670 0.732212 0.266689 0.019 Uiso 1 1 calc R U . . .
C21 C 0.05172(19) 0.75940(16) 0.18688(8) 0.0163(4) Uani 1 1 d . . . . .
H21 H 0.051752 0.847649 0.190148 0.020 Uiso 1 1 calc R U . . .
C22 C 0.0356(2) 0.72383(18) 0.12064(9) 0.0220(4) Uani 1 1 d . . . . .
H22A H 0.110878 0.756170 0.096593 0.026 Uiso 1 1 calc R U . . .
H22B H -0.048989 0.756797 0.104411 0.026 Uiso 1 1 calc R U . . .
C23 C 0.3599(2) 0.5410(2) 0.47547(9) 0.0246(4) Uani 1 1 d . . . . .
H23 H 0.452589 0.529679 0.467456 0.029 Uiso 1 1 calc R U . . .
C24 C 0.3039(2) 0.6344(2) 0.50875(9) 0.0262(5) Uani 1 1 d . . . . .
H24 H 0.352029 0.696533 0.527905 0.031 Uiso 1 1 calc R U . . .
C25 C 0.1644(3) 0.6200(2) 0.50874(10) 0.0326(6) Uani 1 1 d . . . . .
H25 H 0.100850 0.670572 0.527590 0.039 Uiso 1 1 calc R U . . .
C26 C 0.1358(2) 0.5167(2) 0.47563(11) 0.0333(5) Uani 1 1 d . . . . .
H26 H 0.048948 0.485720 0.467895 0.040 Uiso 1 1 calc R U . . .
C27 C 0.2558(3) 0.46755(18) 0.45618(10) 0.0295(5) Uani 1 1 d . . . . .
H27 H 0.265417 0.396439 0.433687 0.035 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ti1 N1 1.7758(16) . ?
Ti1 Cl1 2.3135(5) . ?
Ti1 Cl2 2.3156(5) . ?
Ti1 C23 2.325(2) . ?
Ti1 C27 2.340(2) . ?
Ti1 C26 2.382(2) . ?
Ti1 C24 2.399(2) . ?
Ti1 C25 2.431(2) . ?
N1 C1 1.319(2) . ?
N2 C1 1.374(2) . ?
N2 C2 1.390(2) . ?
N2 C4 1.438(2) . ?
N3 C1 1.374(2) . ?
N3 C3 1.388(2) . ?
N3 C13 1.497(2) . ?
C2 C3 1.345(3) . ?
C2 H2 0.9500 . ?
C3 H3 0.9500 . ?
C4 C5 1.394(3) . ?
C4 C9 1.398(3) . ?
C5 C6 1.394(3) . ?
C5 C10 1.510(3) . ?
C6 C7 1.398(3) . ?
C6 H6 0.9500 . ?
C7 C8 1.394(3) . ?
C7 C11 1.508(3) . ?
C8 C9 1.396(3) . ?
C8 H8 0.9500 . ?
C9 C12 1.506(3) . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 C14 1.529(3) . ?
C13 C19 1.537(2) . ?
C13 C18 1.538(2) . ?
C14 C15 1.536(3) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 C16 1.527(3) . ?
C15 C20 1.536(3) . ?
C15 H15 1.0000 . ?
C16 C17 1.534(3) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C17 C22 1.535(3) . ?
C17 C18 1.541(3) . ?
C17 H17 1.0000 . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?
C19 C21 1.537(2) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 C21 1.533(3) . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?
C21 C22 1.528(3) . ?
C21 H21 1.0000 . ?
C22 H22A 0.9900 . ?
C22 H22B 0.9900 . ?
C23 C27 1.396(3) . ?
C23 C24 1.403(3) . ?
C23 H23 0.9500 . ?
C24 C25 1.401(3) . ?
C24 H24 0.9500 . ?
C25 C26 1.408(4) . ?
C25 H25 0.9500 . ?
C26 C27 1.388(4) . ?
C26 H26 0.9500 . ?
C27 H27 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Ti1 Cl1 103.88(5) . . ?
N1 Ti1 Cl2 101.17(5) . . ?
Cl1 Ti1 Cl2 101.87(2) . . ?
N1 Ti1 C23 101.72(7) . . ?
Cl1 Ti1 C23 141.37(6) . . ?
Cl2 Ti1 C23 100.98(6) . . ?
N1 Ti1 C27 92.69(8) . . ?
Cl1 Ti1 C27 115.27(7) . . ?
Cl2 Ti1 C27 135.79(6) . . ?
C23 Ti1 C27 34.83(9) . . ?
N1 Ti1 C26 117.09(9) . . ?
Cl1 Ti1 C26 85.35(6) . . ?
Cl2 Ti1 C26 138.25(7) . . ?
C23 Ti1 C26 57.17(8) . . ?
C27 Ti1 C26 34.17(9) . . ?
N1 Ti1 C24 135.23(8) . . ?
Cl1 Ti1 C24 118.29(6) . . ?
Cl2 Ti1 C24 85.00(6) . . ?
C23 Ti1 C24 34.52(8) . . ?
C27 Ti1 C24 57.14(8) . . ?
C26 Ti1 C24 56.49(8) . . ?
N1 Ti1 C25 149.07(8) . . ?
Cl1 Ti1 C25 87.26(6) . . ?
Cl2 Ti1 C25 104.64(7) . . ?
C23 Ti1 C25 56.90(7) . . ?
C27 Ti1 C25 56.76(8) . . ?
C26 Ti1 C25 33.99(9) . . ?
C24 Ti1 C25 33.71(8) . . ?
C1 N1 Ti1 170.28(14) . . ?
C1 N2 C2 109.57(15) . . ?
C1 N2 C4 124.97(15) . . ?
C2 N2 C4 125.35(15) . . ?
C1 N3 C3 108.84(15) . . ?
C1 N3 C13 125.18(15) . . ?
C3 N3 C13 125.96(15) . . ?
N1 C1 N3 128.31(17) . . ?
N1 C1 N2 125.66(17) . . ?
N3 C1 N2 105.99(15) . . ?
C3 C2 N2 107.13(16) . . ?
C3 C2 H2 126.4 . . ?
N2 C2 H2 126.4 . . ?
C2 C3 N3 108.47(16) . . ?
C2 C3 H3 125.8 . . ?
N3 C3 H3 125.8 . . ?
C5 C4 C9 122.54(17) . . ?
C5 C4 N2 118.37(16) . . ?
C9 C4 N2 119.08(17) . . ?
C6 C5 C4 117.88(17) . . ?
C6 C5 C10 120.88(17) . . ?
C4 C5 C10 121.23(17) . . ?
C5 C6 C7 121.52(18) . . ?
C5 C6 H6 119.2 . . ?
C7 C6 H6 119.2 . . ?
C8 C7 C6 118.73(18) . . ?
C8 C7 C11 120.95(18) . . ?
C6 C7 C11 120.32(17) . . ?
C7 C8 C9 121.68(18) . . ?
C7 C8 H8 119.2 . . ?
C9 C8 H8 119.2 . . ?
C8 C9 C4 117.65(17) . . ?
C8 C9 C12 121.09(17) . . ?
C4 C9 C12 121.23(17) . . ?
C5 C10 H10A 109.5 . . ?
C5 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C5 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C7 C11 H11A 109.5 . . ?
C7 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C7 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C9 C12 H12A 109.5 . . ?
C9 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C9 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
N3 C13 C14 109.44(14) . . ?
N3 C13 C19 109.75(15) . . ?
C14 C13 C19 110.25(15) . . ?
N3 C13 C18 109.59(15) . . ?
C14 C13 C18 108.54(15) . . ?
C19 C13 C18 109.24(15) . . ?
C13 C14 C15 109.81(15) . . ?
C13 C14 H14A 109.7 . . ?
C15 C14 H14A 109.7 . . ?
C13 C14 H14B 109.7 . . ?
C15 C14 H14B 109.7 . . ?
H14A C14 H14B 108.2 . . ?
C16 C15 C14 109.54(16) . . ?
C16 C15 C20 109.64(16) . . ?
C14 C15 C20 109.58(15) . . ?
C16 C15 H15 109.4 . . ?
C14 C15 H15 109.4 . . ?
C20 C15 H15 109.4 . . ?
C15 C16 C17 108.85(16) . . ?
C15 C16 H16A 109.9 . . ?
C17 C16 H16A 109.9 . . ?
C15 C16 H16B 109.9 . . ?
C17 C16 H16B 109.9 . . ?
H16A C16 H16B 108.3 . . ?
C16 C17 C22 109.87(17) . . ?
C16 C17 C18 110.08(16) . . ?
C22 C17 C18 108.67(17) . . ?
C16 C17 H17 109.4 . . ?
C22 C17 H17 109.4 . . ?
C18 C17 H17 109.4 . . ?
C13 C18 C17 109.56(15) . . ?
C13 C18 H18A 109.8 . . ?
C17 C18 H18A 109.8 . . ?
C13 C18 H18B 109.8 . . ?
C17 C18 H18B 109.8 . . ?
H18A C18 H18B 108.2 . . ?
C13 C19 C21 109.11(15) . . ?
C13 C19 H19A 109.9 . . ?
C21 C19 H19A 109.9 . . ?
C13 C19 H19B 109.9 . . ?
C21 C19 H19B 109.9 . . ?
H19A C19 H19B 108.3 . . ?
C21 C20 C15 109.53(15) . . ?
C21 C20 H20A 109.8 . . ?
C15 C20 H20A 109.8 . . ?
C21 C20 H20B 109.8 . . ?
C15 C20 H20B 109.8 . . ?
H20A C20 H20B 108.2 . . ?
C22 C21 C20 109.40(16) . . ?
C22 C21 C19 109.88(15) . . ?
C20 C21 C19 109.38(15) . . ?
C22 C21 H21 109.4 . . ?
C20 C21 H21 109.4 . . ?
C19 C21 H21 109.4 . . ?
C21 C22 C17 109.52(16) . . ?
C21 C22 H22A 109.8 . . ?
C17 C22 H22A 109.8 . . ?
C21 C22 H22B 109.8 . . ?
C17 C22 H22B 109.8 . . ?
H22A C22 H22B 108.2 . . ?
C27 C23 C24 108.1(2) . . ?
C27 C23 Ti1 73.19(12) . . ?
C24 C23 Ti1 75.65(12) . . ?
C27 C23 H23 125.9 . . ?
C24 C23 H23 125.9 . . ?
Ti1 C23 H23 117.2 . . ?
C25 C24 C23 107.9(2) . . ?
C25 C24 Ti1 74.40(13) . . ?
C23 C24 Ti1 69.83(11) . . ?
C25 C24 H24 126.0 . . ?
C23 C24 H24 126.0 . . ?
Ti1 C24 H24 121.4 . . ?
C24 C25 C26 107.3(2) . . ?
C24 C25 Ti1 71.89(12) . . ?
C26 C25 Ti1 71.06(13) . . ?
C24 C25 H25 126.3 . . ?
C26 C25 H25 126.3 . . ?
Ti1 C25 H25 122.4 . . ?
C27 C26 C25 108.6(2) . . ?
C27 C26 Ti1 71.29(13) . . ?
C25 C26 Ti1 74.95(13) . . ?
C27 C26 H26 125.7 . . ?
C25 C26 H26 125.7 . . ?
Ti1 C26 H26 119.8 . . ?
C26 C27 C23 108.0(2) . . ?
C26 C27 Ti1 74.54(13) . . ?
C23 C27 Ti1 71.98(11) . . ?
C26 C27 H27 126.0 . . ?
C23 C27 H27 126.0 . . ?
Ti1 C27 H27 119.3 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C3 N3 C1 N1 177.47(18) . . . . ?
C13 N3 C1 N1 -4.1(3) . . . . ?
C3 N3 C1 N2 -0.3(2) . . . . ?
C13 N3 C1 N2 178.08(16) . . . . ?
C2 N2 C1 N1 -177.36(18) . . . . ?
C4 N2 C1 N1 6.2(3) . . . . ?
C2 N2 C1 N3 0.5(2) . . . . ?
C4 N2 C1 N3 -175.89(17) . . . . ?
C1 N2 C2 C3 -0.5(2) . . . . ?
C4 N2 C2 C3 175.87(18) . . . . ?
N2 C2 C3 N3 0.3(2) . . . . ?
C1 N3 C3 C2 0.0(2) . . . . ?
C13 N3 C3 C2 -178.37(17) . . . . ?
C1 N2 C4 C5 95.1(2) . . . . ?
C2 N2 C4 C5 -80.8(2) . . . . ?
C1 N2 C4 C9 -85.9(2) . . . . ?
C2 N2 C4 C9 98.3(2) . . . . ?
C9 C4 C5 C6 0.9(3) . . . . ?
N2 C4 C5 C6 179.88(16) . . . . ?
C9 C4 C5 C10 -178.52(17) . . . . ?
N2 C4 C5 C10 0.5(3) . . . . ?
C4 C5 C6 C7 -0.6(3) . . . . ?
C10 C5 C6 C7 178.81(18) . . . . ?
C5 C6 C7 C8 -0.1(3) . . . . ?
C5 C6 C7 C11 -179.88(17) . . . . ?
C6 C7 C8 C9 0.6(3) . . . . ?
C11 C7 C8 C9 -179.63(17) . . . . ?
C7 C8 C9 C4 -0.4(3) . . . . ?
C7 C8 C9 C12 177.46(17) . . . . ?
C5 C4 C9 C8 -0.4(3) . . . . ?
N2 C4 C9 C8 -179.41(16) . . . . ?
C5 C4 C9 C12 -178.23(17) . . . . ?
N2 C4 C9 C12 2.8(3) . . . . ?
C1 N3 C13 C14 -55.2(2) . . . . ?
C3 N3 C13 C14 122.93(19) . . . . ?
C1 N3 C13 C19 65.9(2) . . . . ?
C3 N3 C13 C19 -115.96(19) . . . . ?
C1 N3 C13 C18 -174.12(17) . . . . ?
C3 N3 C13 C18 4.0(2) . . . . ?
N3 C13 C14 C15 179.76(15) . . . . ?
C19 C13 C14 C15 58.95(19) . . . . ?
C18 C13 C14 C15 -60.67(19) . . . . ?
C13 C14 C15 C16 61.48(19) . . . . ?
C13 C14 C15 C20 -58.8(2) . . . . ?
C14 C15 C16 C17 -60.0(2) . . . . ?
C20 C15 C16 C17 60.2(2) . . . . ?
C15 C16 C17 C22 -60.1(2) . . . . ?
C15 C16 C17 C18 59.5(2) . . . . ?
N3 C13 C18 C17 179.12(16) . . . . ?
C14 C13 C18 C17 59.6(2) . . . . ?
C19 C13 C18 C17 -60.6(2) . . . . ?
C16 C17 C18 C13 -59.7(2) . . . . ?
C22 C17 C18 C13 60.6(2) . . . . ?
N3 C13 C19 C21 179.90(14) . . . . ?
C14 C13 C19 C21 -59.47(19) . . . . ?
C18 C13 C19 C21 59.7(2) . . . . ?
C16 C15 C20 C21 -60.4(2) . . . . ?
C14 C15 C20 C21 59.84(19) . . . . ?
C15 C20 C21 C22 59.73(19) . . . . ?
C15 C20 C21 C19 -60.67(19) . . . . ?
C13 C19 C21 C22 -59.98(19) . . . . ?
C13 C19 C21 C20 60.13(19) . . . . ?
C20 C21 C22 C17 -59.5(2) . . . . ?
C19 C21 C22 C17 60.6(2) . . . . ?
C16 C17 C22 C21 60.0(2) . . . . ?
C18 C17 C22 C21 -60.5(2) . . . . ?
C27 C23 C24 C25 -1.4(2) . . . . ?
Ti1 C23 C24 C25 65.17(15) . . . . ?
C27 C23 C24 Ti1 -66.55(14) . . . . ?
C23 C24 C25 C26 0.4(2) . . . . ?
Ti1 C24 C25 C26 62.63(15) . . . . ?
C23 C24 C25 Ti1 -62.19(14) . . . . ?
C24 C25 C26 C27 0.7(3) . . . . ?
Ti1 C25 C26 C27 63.85(16) . . . . ?
C24 C25 C26 Ti1 -63.17(16) . . . . ?
C25 C26 C27 C23 -1.5(2) . . . . ?
Ti1 C26 C27 C23 64.70(14) . . . . ?
C25 C26 C27 Ti1 -66.23(16) . . . . ?
C24 C23 C27 C26 1.8(2) . . . . ?
Ti1 C23 C27 C26 -66.40(15) . . . . ?
C24 C23 C27 Ti1 68.20(14) . . . . ?

_refine_diff_density_max         0.242
_refine_diff_density_min         -0.226
_refine_diff_density_rms         0.043


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: toluene/n-hexane'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mk17mk
_database_code_depnum_ccdc_archive 'CCDC 2174866'
loop_
_audit_author_name
_audit_author_address
'Marvin Koneczny'
;TU Braunschweig
Germany
;
_audit_update_record             
;
2022-05-25 deposited with the CCDC.	2022-07-08 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C25 H37 N3 Si'
_chemical_formula_sum            'C25 H37 N3 Si'
_chemical_formula_weight         407.66

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   9.7011(4)
_cell_length_b                   24.1407(8)
_cell_length_c                   10.2311(4)
_cell_angle_alpha                90
_cell_angle_beta                 99.776(4)
_cell_angle_gamma                90
_cell_volume                     2361.24(16)
_cell_formula_units_Z            4
_cell_measurement_temperature    103(1)
_cell_measurement_reflns_used    14286
_cell_measurement_theta_min      2.6150
_cell_measurement_theta_max      46.7860

_exptl_crystal_description       irregular
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.147
_exptl_crystal_F_000             888
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.701
_exptl_crystal_size_mid          0.591
_exptl_crystal_size_min          0.469

loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-4 30 -4 0.3469
-5 -30 5 0.2681
0 -34 -2 0.2743
-12 16 6 0.3260
-12 -17 4 0.3291
4 -24 -10 0.2739
-8 -21 -6 0.2639
-5 -16 -11 0.2540
6 -17 -12 0.2781
0 18 12 0.2374
-9 -12 -8 0.2475
1 8 14 0.2381
-13 4 -1 0.2974
-8 -3 -10 0.2369
6 -2 -14 0.2762
1 -3 14 0.2388
-2 14 -12 0.2704
3 19 -12 0.2669
8 13 -12 0.2739
2 -23 10 0.2541
10 21 -7 0.2518
-2 -33 4 0.2622
-3 33 -1 0.3467
10 23 1 0.2595
3 -30 -7 0.2806
-9 21 7 0.3285
5 24 8 0.2426
-1 -25 -9 0.2532
-11 -15 -3 0.2852
1 25 9 0.2551
11 9 6 0.2587
9 2 9 0.2312
-9 -2 -9 0.2383
7 -6 11 0.2374
12 -9 3 0.3406
-9 8 -9 0.2651
0 -13 13 0.2476
4 -24 8 0.2752
-1 -21 11 0.2576
2 -20 11 0.2513
-1 -19 12 0.2450
-8 -9 12 0.3548
-2 7 -13 0.2312
-3 -23 11 0.2414
11 22 -1 0.2491
9 26 0 0.2503
13 10 -3 0.3160
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-4.3460 29.7444 -4.4499 -0.8231 0.3905 -0.4125
-5.1247 -29.9925 5.0038 0.9680 -0.1270 -0.2166
0.2725 -33.7266 -1.9229 0.9424 0.1763 0.2843
-11.5543 15.9395 5.7492 -0.2453 -0.0482 -0.9682
-11.6316 -17.2906 4.0011 0.6893 0.1266 -0.7134
4.3332 -23.7987 -9.8864 0.5376 0.5700 0.6214
-8.3052 -20.5762 -5.8382 0.6564 0.6920 -0.3004
-4.6762 -15.8160 -10.7745 0.4296 0.9030 -0.0090
5.7530 -16.8884 -11.8280 0.3048 0.6450 0.7007
0.2656 17.5781 12.1231 -0.4069 -0.8571 -0.3160
-8.9491 -11.8844 -7.9328 0.4007 0.8399 -0.3660
0.9211 7.8152 13.6394 -0.1254 -0.9646 -0.2321
-13.1638 3.8503 -1.1492 0.0663 0.4892 -0.8697
-8.2326 -3.0124 -9.8094 0.1224 0.9297 -0.3474
6.2359 -2.1144 -13.7387 -0.1388 0.7349 0.6638
1.2191 -3.0315 13.8860 0.1817 -0.9730 -0.1420
-1.9547 14.2029 -12.4097 -0.4780 0.8783 -0.0091
3.4378 19.2804 -11.7715 -0.6935 0.6558 0.2983
7.6629 12.8425 -11.8529 -0.5701 0.5377 0.6212
2.0249 -23.4963 9.7051 0.7201 -0.6825 0.1252
9.5438 21.4789 -6.5163 -0.7997 0.1030 0.5916
-2.2824 -32.5722 3.7704 0.9915 -0.1296 0.0092
-2.8899 33.0053 -1.2123 -0.9103 0.1200 -0.3961
9.5906 23.1687 1.2804 -0.7854 -0.4287 0.4466
3.3102 -29.5176 -6.7760 0.7403 0.4014 0.5393
-9.4255 20.9156 7.1469 -0.4059 -0.2184 -0.8875
4.5418 24.1477 8.0209 -0.6876 -0.7260 -0.0092
-1.3217 -25.3216 -9.1615 0.6665 0.7029 0.2484
-11.2374 -14.9722 -3.1360 0.5598 0.5931 -0.5787
0.6200 25.3819 9.3371 -0.6569 -0.6926 -0.2979
10.8759 8.8293 5.8427 -0.3576 -0.7547 0.5500
8.7722 2.4455 9.2894 -0.1180 -0.9107 0.3958
-8.9427 -2.2794 -9.1139 0.1171 0.9040 -0.4112
6.7305 -6.3961 10.8806 0.1757 -0.9391 0.2952
12.0621 -8.9660 3.3992 0.1134 -0.5981 0.7934
-9.0080 7.6358 -8.5997 -0.1605 0.8551 -0.4930
0.1779 -12.9809 13.1094 0.4738 -0.8713 -0.1281
4.4170 -24.0641 8.1539 0.6901 -0.6525 0.3131
-1.2519 -21.4430 11.1867 0.7197 -0.6821 -0.1298
1.6239 -20.4622 10.9438 0.6493 -0.7585 0.0563
-1.0251 -18.6108 12.0384 0.6426 -0.7515 -0.1493
-8.2081 -8.9362 12.2098 0.4693 -0.5509 -0.6901
-2.4435 7.4508 -13.2008 -0.2850 0.9583 0.0193
-2.6617 -22.9580 10.5989 0.7780 -0.5951 -0.2015
10.5006 21.6109 -0.6976 -0.7698 -0.3212 0.5516
8.7884 25.5940 0.4936 -0.8496 -0.3539 0.3910
13.0197 10.1708 -3.2510 -0.4997 -0.2098 0.8404
_exptl_absorpt_coefficient_mu    0.115
_exptl_absorpt_correction_T_min  0.942
_exptl_absorpt_correction_T_max  0.961
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.21a (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.839
_oxdiff_exptl_absorpt_empirical_full_max 1.353
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_diffrn_ambient_temperature      103(1)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_measurement_device_type  'Oxford Diffraction Xcalibur, Eos'
_diffrn_measurement_method       'ω scan'
_diffrn_detector_area_resol_mean 16.1419
_diffrn_reflns_number            121520
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_av_R_equivalents  0.0726
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.291
_diffrn_reflns_theta_max         36.316
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             11433
_reflns_number_gt                9186
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_structure_solution    
'SHELXT-2014/5 (G. M. Sheldrick, Acta Cryst., 2015, A71, 3-8)'
_computing_structure_refinement  
'SHELXL-2018/3 (G. M. Sheldrick, Acta Cryst. (2008), A64, 112-122)'
_computing_molecular_graphics    ?
_computing_publication_material  
'OLEX2 v1.2 (O. V. Dolomanov et al., J. Appl. Cryst., 2009, 42, 339-341)'
_refine_special_details          
;
 All H atoms were placed in idealised positions and refined using a riding
 model, with a common U restrained to be 1.2 (1.5 for methyl groups) times
 the equivalent isotropic displacement parameter of the parent atom.
 Ordered methyl groups were treated as rigid bodies and allowed to 
 rotate around the E-CH3 bond.

 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0684P)²+0.4004P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         11433
_refine_ls_number_parameters     268
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0601
_refine_ls_R_factor_gt           0.0457
_refine_ls_wR_factor_ref         0.1258
_refine_ls_wR_factor_gt          0.1173
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_restrained_S_all      1.040
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Si1 Si 0.68470(2) 0.63312(2) 0.77023(2) 0.01160(5) Uani 1 1 d . . . . .
N1 N 0.52494(7) 0.61821(3) 0.68522(7) 0.01410(11) Uani 1 1 d . . . . .
N2 N 0.35018(7) 0.68988(3) 0.63524(8) 0.01449(11) Uani 1 1 d . . . . .
N3 N 0.27788(7) 0.60432(3) 0.64982(7) 0.01253(11) Uani 1 1 d . . . . .
C1 C 0.39915(8) 0.63605(3) 0.66040(8) 0.01140(11) Uani 1 1 d . . . . .
C2 C 0.20490(9) 0.69080(3) 0.61322(10) 0.01872(15) Uani 1 1 d . . . . .
H2 H 0.148504 0.721989 0.595712 0.022 Uiso 1 1 calc R U . . .
C3 C 0.16080(8) 0.63834(3) 0.62187(10) 0.01721(14) Uani 1 1 d . . . . .
H3 H 0.068097 0.626798 0.611038 0.021 Uiso 1 1 calc R U . . .
C4 C 0.43653(8) 0.73734(3) 0.62981(8) 0.01341(12) Uani 1 1 d . . . . .
C5 C 0.45438(9) 0.77445(3) 0.73601(9) 0.01477(13) Uani 1 1 d . . . . .
C6 C 0.53759(10) 0.82102(3) 0.72865(10) 0.01978(15) Uani 1 1 d . . . . .
H6 H 0.552280 0.845672 0.799515 0.024 Uiso 1 1 calc R U . . .
C7 C 0.59915(10) 0.83155(4) 0.61812(11) 0.02280(17) Uani 1 1 d . . . . .
C8 C 0.57684(10) 0.79423(4) 0.51278(10) 0.02164(17) Uani 1 1 d . . . . .
H8 H 0.616774 0.801271 0.438006 0.026 Uiso 1 1 calc R U . . .
C9 C 0.49620(9) 0.74657(4) 0.51641(9) 0.01703(14) Uani 1 1 d . . . . .
C10 C 0.38309(10) 0.76546(4) 0.85396(10) 0.02045(15) Uani 1 1 d . . . . .
H10A H 0.286322 0.775643 0.831334 0.031 Uiso 1 1 calc R U . . .
H10B H 0.427402 0.787866 0.926626 0.031 Uiso 1 1 calc R U . . .
H10C H 0.390086 0.727120 0.879164 0.031 Uiso 1 1 calc R U . . .
C11 C 0.68707(15) 0.88275(5) 0.61273(17) 0.0400(3) Uani 1 1 d . . . . .
H11A H 0.628435 0.912810 0.575544 0.060 Uiso 1 1 calc R U . . .
H11B H 0.756741 0.875668 0.558473 0.060 Uiso 1 1 calc R U . . .
H11C H 0.732013 0.892354 0.700760 0.060 Uiso 1 1 calc R U . . .
C12 C 0.47337(12) 0.70628(5) 0.40335(10) 0.02521(18) Uani 1 1 d . . . . .
H12A H 0.519579 0.672002 0.430779 0.038 Uiso 1 1 calc R U . . .
H12B H 0.510952 0.721275 0.329908 0.038 Uiso 1 1 calc R U . . .
H12C H 0.374967 0.699745 0.376944 0.038 Uiso 1 1 calc R U . . .
C13 C 0.27666(7) 0.54435(3) 0.67967(7) 0.01038(11) Uani 1 1 d . . . . .
C14 C 0.34522(9) 0.53384(3) 0.82421(8) 0.01521(13) Uani 1 1 d . . . . .
H14A H 0.441216 0.546835 0.838276 0.018 Uiso 1 1 calc R U . . .
H14B H 0.295326 0.554138 0.883408 0.018 Uiso 1 1 calc R U . . .
C15 C 0.34221(10) 0.47164(4) 0.85499(9) 0.01893(15) Uani 1 1 d . . . . .
H15 H 0.386744 0.465165 0.947067 0.023 Uiso 1 1 calc R U . . .
C16 C 0.18996(10) 0.45172(4) 0.83549(9) 0.01961(15) Uani 1 1 d . . . . .
H16A H 0.187091 0.412559 0.856093 0.024 Uiso 1 1 calc R U . . .
H16B H 0.139457 0.471740 0.894666 0.024 Uiso 1 1 calc R U . . .
C17 C 0.12153(9) 0.46174(3) 0.69153(8) 0.01496(13) Uani 1 1 d . . . . .
H17 H 0.024143 0.449120 0.678704 0.018 Uiso 1 1 calc R U . . .
C18 C 0.12507(8) 0.52379(3) 0.66031(8) 0.01412(12) Uani 1 1 d . . . . .
H18A H 0.080190 0.530313 0.569456 0.017 Uiso 1 1 calc R U . . .
H18B H 0.073927 0.544166 0.718360 0.017 Uiso 1 1 calc R U . . .
C19 C 0.35466(9) 0.51184(3) 0.58589(8) 0.01387(12) Uani 1 1 d . . . . .
H19A H 0.450737 0.524569 0.596158 0.017 Uiso 1 1 calc R U . . .
H19B H 0.310640 0.518205 0.494709 0.017 Uiso 1 1 calc R U . . .
C20 C 0.42224(10) 0.44008(4) 0.76164(11) 0.02158(16) Uani 1 1 d . . . . .
H20A H 0.422747 0.400815 0.781814 0.026 Uiso 1 1 calc R U . . .
H20B H 0.518383 0.452855 0.774045 0.026 Uiso 1 1 calc R U . . .
C21 C 0.35198(10) 0.44971(3) 0.61752(9) 0.01758(14) Uani 1 1 d . . . . .
H21 H 0.402687 0.429222 0.557915 0.021 Uiso 1 1 calc R U . . .
C22 C 0.20055(10) 0.42931(3) 0.59911(9) 0.01777(14) Uani 1 1 d . . . . .
H22A H 0.155829 0.434610 0.507731 0.021 Uiso 1 1 calc R U . . .
H22B H 0.198821 0.390082 0.619330 0.021 Uiso 1 1 calc R U . . .
C23 C 0.67414(10) 0.66645(4) 0.93362(9) 0.01908(15) Uani 1 1 d . . . . .
H23A H 0.638303 0.703411 0.918995 0.029 Uiso 1 1 calc R U . . .
H23B H 0.765731 0.667767 0.986699 0.029 Uiso 1 1 calc R U . . .
H23C H 0.612969 0.645258 0.978870 0.029 Uiso 1 1 calc R U . . .
C24 C 0.79395(9) 0.67904(4) 0.68127(9) 0.01879(15) Uani 1 1 d . . . . .
H24A H 0.794616 0.664706 0.593852 0.028 Uiso 1 1 calc R U . . .
H24B H 0.887859 0.680195 0.729493 0.028 Uiso 1 1 calc R U . . .
H24C H 0.755356 0.715752 0.674855 0.028 Uiso 1 1 calc R U . . .
C25 C 0.78054(9) 0.56562(4) 0.80102(9) 0.01780(14) Uani 1 1 d . . . . .
H25A H 0.728844 0.541139 0.848680 0.027 Uiso 1 1 calc R U . . .
H25B H 0.871485 0.572112 0.852367 0.027 Uiso 1 1 calc R U . . .
H25C H 0.790318 0.549073 0.717765 0.027 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Si1 N1 1.6824(7) . ?
Si1 C24 1.8730(9) . ?
Si1 C23 1.8736(9) . ?
Si1 C25 1.8760(9) . ?
N1 C1 1.2783(10) . ?
N2 C2 1.3891(11) . ?
N2 C1 1.3925(10) . ?
N2 C4 1.4261(10) . ?
N3 C3 1.3915(10) . ?
N3 C1 1.3926(10) . ?
N3 C13 1.4798(10) . ?
C2 C3 1.3445(12) . ?
C4 C5 1.3961(12) . ?
C4 C9 1.3995(12) . ?
C5 C6 1.3935(12) . ?
C5 C10 1.5051(13) . ?
C6 C7 1.3890(15) . ?
C7 C8 1.3932(16) . ?
C7 C11 1.5080(14) . ?
C8 C9 1.3953(13) . ?
C9 C12 1.4988(14) . ?
C13 C18 1.5328(11) . ?
C13 C19 1.5348(11) . ?
C13 C14 1.5362(11) . ?
C14 C15 1.5353(12) . ?
C15 C20 1.5320(15) . ?
C15 C16 1.5339(13) . ?
C16 C17 1.5285(12) . ?
C17 C22 1.5301(13) . ?
C17 C18 1.5333(11) . ?
C19 C21 1.5355(11) . ?
C20 C21 1.5335(14) . ?
C21 C22 1.5304(13) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 Si1 C24 115.03(4) . . ?
N1 Si1 C23 111.59(4) . . ?
C24 Si1 C23 107.49(4) . . ?
N1 Si1 C25 106.72(4) . . ?
C24 Si1 C25 106.89(4) . . ?
C23 Si1 C25 108.90(4) . . ?
C1 N1 Si1 142.67(6) . . ?
C2 N2 C1 110.48(6) . . ?
C2 N2 C4 124.56(7) . . ?
C1 N2 C4 124.95(7) . . ?
C3 N3 C1 109.91(6) . . ?
C3 N3 C13 125.80(6) . . ?
C1 N3 C13 123.94(6) . . ?
N1 C1 N2 129.45(7) . . ?
N1 C1 N3 126.54(7) . . ?
N2 C1 N3 103.99(6) . . ?
C3 C2 N2 107.43(7) . . ?
C2 C3 N3 108.17(7) . . ?
C5 C4 C9 121.93(7) . . ?
C5 C4 N2 118.77(7) . . ?
C9 C4 N2 119.25(7) . . ?
C6 C5 C4 118.17(8) . . ?
C6 C5 C10 120.60(8) . . ?
C4 C5 C10 121.22(7) . . ?
C7 C6 C5 121.64(9) . . ?
C6 C7 C8 118.67(8) . . ?
C6 C7 C11 120.24(11) . . ?
C8 C7 C11 121.09(11) . . ?
C7 C8 C9 121.79(9) . . ?
C8 C9 C4 117.78(8) . . ?
C8 C9 C12 121.64(9) . . ?
C4 C9 C12 120.58(8) . . ?
N3 C13 C18 109.34(6) . . ?
N3 C13 C19 110.44(6) . . ?
C18 C13 C19 108.52(6) . . ?
N3 C13 C14 110.06(6) . . ?
C18 C13 C14 108.66(6) . . ?
C19 C13 C14 109.78(6) . . ?
C15 C14 C13 109.81(6) . . ?
C20 C15 C16 109.98(8) . . ?
C20 C15 C14 109.22(7) . . ?
C16 C15 C14 109.35(8) . . ?
C17 C16 C15 109.07(7) . . ?
C16 C17 C22 109.47(7) . . ?
C16 C17 C18 109.51(7) . . ?
C22 C17 C18 109.87(7) . . ?
C13 C18 C17 110.15(6) . . ?
C13 C19 C21 109.87(6) . . ?
C15 C20 C21 109.54(7) . . ?
C22 C21 C20 109.28(7) . . ?
C22 C21 C19 109.80(7) . . ?
C20 C21 C19 109.27(7) . . ?
C17 C22 C21 109.30(7) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C24 Si1 N1 C1 -86.61(11) . . . . ?
C23 Si1 N1 C1 36.18(12) . . . . ?
C25 Si1 N1 C1 155.03(10) . . . . ?
Si1 N1 C1 N2 40.88(16) . . . . ?
Si1 N1 C1 N3 -140.58(9) . . . . ?
C2 N2 C1 N1 -179.94(9) . . . . ?
C4 N2 C1 N1 1.36(14) . . . . ?
C2 N2 C1 N3 1.27(9) . . . . ?
C4 N2 C1 N3 -177.43(7) . . . . ?
C3 N3 C1 N1 -179.96(8) . . . . ?
C13 N3 C1 N1 6.50(13) . . . . ?
C3 N3 C1 N2 -1.12(9) . . . . ?
C13 N3 C1 N2 -174.66(7) . . . . ?
C1 N2 C2 C3 -0.97(11) . . . . ?
C4 N2 C2 C3 177.74(8) . . . . ?
N2 C2 C3 N3 0.23(11) . . . . ?
C1 N3 C3 C2 0.58(11) . . . . ?
C13 N3 C3 C2 173.97(8) . . . . ?
C2 N2 C4 C5 76.48(11) . . . . ?
C1 N2 C4 C5 -105.00(9) . . . . ?
C2 N2 C4 C9 -100.98(10) . . . . ?
C1 N2 C4 C9 77.55(11) . . . . ?
C9 C4 C5 C6 -1.81(12) . . . . ?
N2 C4 C5 C6 -179.20(7) . . . . ?
C9 C4 C5 C10 176.64(8) . . . . ?
N2 C4 C5 C10 -0.74(12) . . . . ?
C4 C5 C6 C7 1.51(13) . . . . ?
C10 C5 C6 C7 -176.96(9) . . . . ?
C5 C6 C7 C8 -0.24(14) . . . . ?
C5 C6 C7 C11 179.20(10) . . . . ?
C6 C7 C8 C9 -0.81(14) . . . . ?
C11 C7 C8 C9 179.76(10) . . . . ?
C7 C8 C9 C4 0.51(13) . . . . ?
C7 C8 C9 C12 -179.50(9) . . . . ?
C5 C4 C9 C8 0.83(12) . . . . ?
N2 C4 C9 C8 178.20(7) . . . . ?
C5 C4 C9 C12 -179.16(8) . . . . ?
N2 C4 C9 C12 -1.79(12) . . . . ?
C3 N3 C13 C18 6.12(11) . . . . ?
C1 N3 C13 C18 178.63(7) . . . . ?
C3 N3 C13 C19 125.47(9) . . . . ?
C1 N3 C13 C19 -62.02(9) . . . . ?
C3 N3 C13 C14 -113.16(9) . . . . ?
C1 N3 C13 C14 59.35(9) . . . . ?
N3 C13 C14 C15 179.39(7) . . . . ?
C18 C13 C14 C15 59.69(9) . . . . ?
C19 C13 C14 C15 -58.85(9) . . . . ?
C13 C14 C15 C20 59.79(9) . . . . ?
C13 C14 C15 C16 -60.61(9) . . . . ?
C20 C15 C16 C17 -59.52(10) . . . . ?
C14 C15 C16 C17 60.41(10) . . . . ?
C15 C16 C17 C22 60.37(9) . . . . ?
C15 C16 C17 C18 -60.14(10) . . . . ?
N3 C13 C18 C17 -179.69(6) . . . . ?
C19 C13 C18 C17 59.79(8) . . . . ?
C14 C13 C18 C17 -59.54(8) . . . . ?
C16 C17 C18 C13 60.30(9) . . . . ?
C22 C17 C18 C13 -59.97(9) . . . . ?
N3 C13 C19 C21 -179.73(7) . . . . ?
C18 C13 C19 C21 -59.89(8) . . . . ?
C14 C13 C19 C21 58.73(8) . . . . ?
C16 C15 C20 C21 59.25(9) . . . . ?
C14 C15 C20 C21 -60.76(9) . . . . ?
C15 C20 C21 C22 -59.53(9) . . . . ?
C15 C20 C21 C19 60.63(9) . . . . ?
C13 C19 C21 C22 60.30(9) . . . . ?
C13 C19 C21 C20 -59.54(9) . . . . ?
C16 C17 C22 C21 -61.21(9) . . . . ?
C18 C17 C22 C21 59.08(9) . . . . ?
C20 C21 C22 C17 60.53(9) . . . . ?
C19 C21 C22 C17 -59.31(9) . . . . ?

_refine_diff_density_max         0.671
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.066


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: n-hexane -27°C'
_chemical_properties_physical    Moisture-sensitive
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_mk18mk
_database_code_depnum_ccdc_archive 'CCDC 2174867'
loop_
_audit_author_name
_audit_author_address
'Marvin Koneczny'
;TU Braunschweig
Germany
;
_audit_update_record             
;
2022-05-25 deposited with the CCDC.	2022-07-08 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C22 H29 N3'
_chemical_formula_sum            'C22 H29 N3'
_chemical_formula_weight         335.48

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z-1/2'
'-x-1/2, y-1/2, z'

_cell_length_a                   16.6873(2)
_cell_length_b                   11.37240(10)
_cell_length_c                   19.4505(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3691.21(7)
_cell_formula_units_Z            8
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    30942
_cell_measurement_theta_min      4.5530
_cell_measurement_theta_max      77.5170

_exptl_crystal_description       'fragment of trapezoid'
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.207
_exptl_crystal_F_000             1456
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.108
_exptl_crystal_size_mid          0.101
_exptl_crystal_size_min          0.099
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
9 -1 -7 0.0638
10 3 0 0.0566
10 2 4 0.0575
3 -7 5 0.0552
0 0 13 0.0546
-4 -7 4 0.0562
2 -7 -3 0.0558
9 4 -3 0.0589
11 -1 0 0.0638
1 -7 0 0.0532
-9 0 -8 0.0521
9 2 7 0.0594
0 -7 4 0.0518
-5 2 -10 0.0613
6 1 10 0.0615
2 -4 10 0.0590
-3 -1 -12 0.0539
-3 -6 5 0.0542
-10 -1 -3 0.0410
-6 6 -2 0.0464
0 7 -1 0.0450
1 0 -13 0.0435
2 7 0 0.0416
-6 0 11 0.0465
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
8.7831 -1.2237 -7.0825 -0.8785 -0.4776 0.0093
9.6074 3.4083 0.2100 -0.3392 -0.7132 -0.6135
9.9048 1.9942 3.8011 -0.1173 -0.8971 -0.4261
3.1319 -6.5586 4.5152 0.1023 -0.5532 0.8267
-0.3344 0.0793 12.6192 0.9028 -0.4300 0.0089
-4.0287 -6.5342 3.5529 0.3318 0.0608 0.9414
2.2731 -6.9921 -3.0415 -0.3995 -0.2182 0.8904
8.8113 3.9947 -2.7092 -0.5039 -0.5306 -0.6816
10.6663 -1.2593 0.4086 -0.4300 -0.9028 -0.0090
1.3758 -7.3199 0.3239 -0.1298 -0.2748 0.9527
-8.5990 0.1411 -7.6729 -0.1815 0.9766 0.1156
8.5608 1.7420 7.1341 0.1697 -0.9148 -0.3664
0.1307 -7.0710 3.6427 0.1586 -0.2897 0.9439
-5.3294 2.4406 -10.1737 -0.4630 0.8510 -0.2478
6.2872 0.9478 10.1500 0.4658 -0.8572 -0.2195
1.5136 -4.0428 10.4262 0.6181 -0.5851 0.5250
-3.3415 -1.2951 -11.8007 -0.7086 0.6720 0.2150
-3.3292 -6.2992 5.3373 0.4314 -0.0557 0.9004
-10.4488 -1.0286 -2.8210 0.2214 0.9254 0.3075
-5.9825 6.0085 -2.2808 0.1660 0.6909 -0.7036
0.3188 7.3697 -0.6543 0.0369 0.1509 -0.9879
1.4043 -0.3715 -12.5025 -0.9428 0.3332 0.0124
1.9625 7.2576 -0.3632 -0.0123 0.0052 -0.9999
-5.7532 0.1287 10.6955 0.9928 0.0788 0.0903
_exptl_absorpt_coefficient_mu    0.545
_exptl_absorpt_correction_T_min  0.793
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.40.21a (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_oxdiff_exptl_absorpt_empirical_full_min 0.887
_oxdiff_exptl_absorpt_empirical_full_max 1.239
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_measurement_device_type  
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       'ω scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            41369
_diffrn_reflns_av_unetI/netI     0.0114
_diffrn_reflns_av_R_equivalents  0.0255
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_theta_min         4.547
_diffrn_reflns_theta_max         77.613
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3865
_reflns_number_gt                3652
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_cell_refinement       'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.21a(Rigaku OD, 2018)'
_computing_structure_solution    
'SHELXT-2014/5 (G. M. Sheldrick, Acta Cryst., 2015, A71, 3-8)'
_computing_structure_refinement  
'SHELXL-2018/3 (G. M. Sheldrick, Acta Cryst., 2008, A64, 112-122)'
_computing_molecular_graphics    ?
_computing_publication_material  
'OLEX2 v1.2 (O. V. Dolomanov et al., J. Appl. Cryst., 2009, 42, 339-341)'
_refine_special_details          
;All C-H hydrogens, except H atoms in methyl groups, were placed in 
 idealised positions and refined using a riding model, with a common U 
 restrained to be 1.2 times the equivalent isotropic displacement 
 parameter of the parent atom. Methyl hydrogens were located in 
 difference synthesis. Methyl groups were idealized and refined as rigid
 groups allowed to rotate but not tip. 
 The N-H hydrogen was refined freely.

 Refinement of F² against ALL reflections.  The weighted R-factor
 wR and goodness of fit S are based on F², conventional R-factors R 
 are based on F, with F set to zero for negative F². The threshold
 expression of F² > 2sigma(F²) is used only for calculating
 R-factors(gt) etc. and isnot relevant to the choice of reflections 
 for refinement.  R-factors based on F² are statistically about twice
 as large as those based on F, and R- factors based on ALL data will be
 even larger.,NH hydrogen was refined freely
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0494P)²+1.8808P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3865
_refine_ls_number_parameters     233
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0429
_refine_ls_R_factor_gt           0.0408
_refine_ls_wR_factor_ref         0.1038
_refine_ls_wR_factor_gt          0.1015
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_restrained_S_all      1.043
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.64242(6) 0.68809(8) 0.53409(5) 0.0192(2) Uani 1 1 d . . . . .
H1 H 0.5966(10) 0.7063(13) 0.5563(8) 0.030(4) Uiso 1 1 d . . . . .
N2 N 0.64889(5) 0.53456(8) 0.62033(5) 0.0172(2) Uani 1 1 d . . . . .
N3 N 0.74358(5) 0.53892(8) 0.54191(5) 0.0163(2) Uani 1 1 d . . . . .
C1 C 0.67454(6) 0.59674(9) 0.56292(5) 0.0159(2) Uani 1 1 d . . . . .
C2 C 0.69959(7) 0.43865(9) 0.63213(6) 0.0181(2) Uani 1 1 d . . . . .
H2 H 0.694206 0.381944 0.667695 0.022 Uiso 1 1 calc R U . . .
C3 C 0.75698(7) 0.44142(9) 0.58422(5) 0.0169(2) Uani 1 1 d . . . . .
H3 H 0.799579 0.386552 0.579672 0.020 Uiso 1 1 calc R U . . .
C4 C 0.57833(6) 0.55963(10) 0.65904(5) 0.0165(2) Uani 1 1 d . . . . .
C5 C 0.57921(7) 0.65079(10) 0.70719(6) 0.0182(2) Uani 1 1 d . . . . .
C6 C 0.51212(7) 0.66531(10) 0.74899(6) 0.0204(2) Uani 1 1 d . . . . .
H6 H 0.511438 0.727458 0.781620 0.024 Uiso 1 1 calc R U . . .
C7 C 0.44607(7) 0.59102(10) 0.74412(6) 0.0216(2) Uani 1 1 d . . . . .
C8 C 0.44578(7) 0.50478(10) 0.69330(6) 0.0219(2) Uani 1 1 d . . . . .
H8 H 0.399843 0.456211 0.688222 0.026 Uiso 1 1 calc R U . . .
C9 C 0.51100(7) 0.48772(10) 0.64967(6) 0.0197(2) Uani 1 1 d . . . . .
C10 C 0.65109(7) 0.72949(11) 0.71537(6) 0.0249(3) Uani 1 1 d . . . . .
H10A H 0.699970 0.684538 0.705909 0.037 Uiso 1 1 calc R U . . .
H10B H 0.652931 0.759851 0.762494 0.037 Uiso 1 1 calc R U . . .
H10C H 0.647182 0.795310 0.683024 0.037 Uiso 1 1 calc R U . . .
C11 C 0.37710(8) 0.60224(13) 0.79374(7) 0.0311(3) Uani 1 1 d . . . . .
H11A H 0.387310 0.553146 0.834212 0.047 Uiso 1 1 calc R U . . .
H11B H 0.327569 0.576345 0.771294 0.047 Uiso 1 1 calc R U . . .
H11C H 0.371577 0.684503 0.807967 0.047 Uiso 1 1 calc R U . . .
C12 C 0.50933(8) 0.39553(11) 0.59398(7) 0.0273(3) Uani 1 1 d . . . . .
H12A H 0.530005 0.429159 0.551113 0.041 Uiso 1 1 calc R U . . .
H12B H 0.454100 0.368810 0.586941 0.041 Uiso 1 1 calc R U . . .
H12C H 0.542789 0.328702 0.607676 0.041 Uiso 1 1 calc R U . . .
C13 C 0.79239(6) 0.57217(9) 0.48132(5) 0.0153(2) Uani 1 1 d . . . . .
C14 C 0.82259(7) 0.69919(10) 0.48930(6) 0.0187(2) Uani 1 1 d . . . . .
H14A H 0.776391 0.753294 0.493629 0.022 Uiso 1 1 calc R U . . .
H14B H 0.855395 0.705885 0.531531 0.022 Uiso 1 1 calc R U . . .
C15 C 0.87320(7) 0.73358(10) 0.42637(6) 0.0219(2) Uani 1 1 d . . . . .
H15 H 0.892108 0.816549 0.431540 0.026 Uiso 1 1 calc R U . . .
C16 C 0.94565(7) 0.65150(11) 0.42062(6) 0.0251(3) Uani 1 1 d . . . . .
H16A H 0.979333 0.658385 0.462323 0.030 Uiso 1 1 calc R U . . .
H16B H 0.978551 0.673711 0.380301 0.030 Uiso 1 1 calc R U . . .
C17 C 0.91589(7) 0.52458(11) 0.41272(6) 0.0236(3) Uani 1 1 d . . . . .
H17 H 0.962992 0.470566 0.409096 0.028 Uiso 1 1 calc R U . . .
C18 C 0.86506(7) 0.48967(10) 0.47552(6) 0.0202(2) Uani 1 1 d . . . . .
H18A H 0.846554 0.407400 0.470529 0.024 Uiso 1 1 calc R U . . .
H18B H 0.897905 0.495063 0.517785 0.024 Uiso 1 1 calc R U . . .
C19 C 0.74152(7) 0.56175(10) 0.41571(5) 0.0184(2) Uani 1 1 d . . . . .
H19A H 0.722154 0.479960 0.410464 0.022 Uiso 1 1 calc R U . . .
H19B H 0.694310 0.614167 0.419076 0.022 Uiso 1 1 calc R U . . .
C20 C 0.82139(7) 0.72316(10) 0.36138(6) 0.0230(2) Uani 1 1 d . . . . .
H20A H 0.774754 0.776614 0.364951 0.028 Uiso 1 1 calc R U . . .
H20B H 0.853142 0.746477 0.320608 0.028 Uiso 1 1 calc R U . . .
C21 C 0.79234(7) 0.59621(11) 0.35307(6) 0.0217(2) Uani 1 1 d . . . . .
H21 H 0.759170 0.589625 0.310427 0.026 Uiso 1 1 calc R U . . .
C22 C 0.86502(7) 0.51434(11) 0.34747(6) 0.0252(3) Uani 1 1 d . . . . .
H22A H 0.846757 0.432124 0.341584 0.030 Uiso 1 1 calc R U . . .
H22B H 0.897540 0.536134 0.306856 0.030 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
N1 C1 1.2966(14) . ?
N1 H1 0.902(16) . ?
N2 C1 1.3893(14) . ?
N2 C2 1.3993(14) . ?
N2 C4 1.4264(13) . ?
N3 C1 1.3881(14) . ?
N3 C3 1.3988(14) . ?
N3 C13 1.4816(13) . ?
C2 C3 1.3367(16) . ?
C2 H2 0.9500 . ?
C3 H3 0.9500 . ?
C4 C5 1.3972(16) . ?
C4 C9 1.4015(16) . ?
C5 C6 1.3935(15) . ?
C5 C10 1.5050(16) . ?
C6 C7 1.3919(17) . ?
C6 H6 0.9500 . ?
C7 C8 1.3926(17) . ?
C7 C11 1.5074(16) . ?
C8 C9 1.3936(16) . ?
C8 H8 0.9500 . ?
C9 C12 1.5078(17) . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 C19 1.5373(14) . ?
C13 C18 1.5373(14) . ?
C13 C14 1.5378(14) . ?
C14 C15 1.5377(15) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 C16 1.5315(17) . ?
C15 C20 1.5359(16) . ?
C15 H15 1.0000 . ?
C16 C17 1.5342(17) . ?
C16 H16A 0.9900 . ?
C16 H16B 0.9900 . ?
C17 C22 1.5313(17) . ?
C17 C18 1.5392(15) . ?
C17 H17 1.0000 . ?
C18 H18A 0.9900 . ?
C18 H18B 0.9900 . ?
C19 C21 1.5353(15) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 C21 1.5314(16) . ?
C20 H20A 0.9900 . ?
C20 H20B 0.9900 . ?
C21 C22 1.5329(17) . ?
C21 H21 1.0000 . ?
C22 H22A 0.9900 . ?
C22 H22B 0.9900 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1 N1 H1 109.1(10) . . ?
C1 N2 C2 110.02(9) . . ?
C1 N2 C4 125.23(9) . . ?
C2 N2 C4 124.63(9) . . ?
C1 N3 C3 109.57(9) . . ?
C1 N3 C13 124.72(9) . . ?
C3 N3 C13 125.62(9) . . ?
N1 C1 N3 126.53(10) . . ?
N1 C1 N2 128.91(10) . . ?
N3 C1 N2 104.55(9) . . ?
C3 C2 N2 107.48(9) . . ?
C3 C2 H2 126.3 . . ?
N2 C2 H2 126.3 . . ?
C2 C3 N3 108.32(9) . . ?
C2 C3 H3 125.8 . . ?
N3 C3 H3 125.8 . . ?
C5 C4 C9 121.91(10) . . ?
C5 C4 N2 119.56(10) . . ?
C9 C4 N2 118.46(10) . . ?
C6 C5 C4 118.07(10) . . ?
C6 C5 C10 120.55(10) . . ?
C4 C5 C10 121.36(10) . . ?
C7 C6 C5 121.64(11) . . ?
C7 C6 H6 119.2 . . ?
C5 C6 H6 119.2 . . ?
C6 C7 C8 118.58(10) . . ?
C6 C7 C11 120.65(11) . . ?
C8 C7 C11 120.76(11) . . ?
C7 C8 C9 121.85(11) . . ?
C7 C8 H8 119.1 . . ?
C9 C8 H8 119.1 . . ?
C8 C9 C4 117.75(11) . . ?
C8 C9 C12 121.32(11) . . ?
C4 C9 C12 120.93(10) . . ?
C5 C10 H10A 109.5 . . ?
C5 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C5 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C7 C11 H11A 109.5 . . ?
C7 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C7 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C9 C12 H12A 109.5 . . ?
C9 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C9 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
N3 C13 C19 109.70(8) . . ?
N3 C13 C18 109.65(8) . . ?
C19 C13 C18 109.13(9) . . ?
N3 C13 C14 109.85(8) . . ?
C19 C13 C14 109.70(9) . . ?
C18 C13 C14 108.79(9) . . ?
C15 C14 C13 109.79(9) . . ?
C15 C14 H14A 109.7 . . ?
C13 C14 H14A 109.7 . . ?
C15 C14 H14B 109.7 . . ?
C13 C14 H14B 109.7 . . ?
H14A C14 H14B 108.2 . . ?
C16 C15 C20 109.70(10) . . ?
C16 C15 C14 109.67(9) . . ?
C20 C15 C14 109.05(9) . . ?
C16 C15 H15 109.5 . . ?
C20 C15 H15 109.5 . . ?
C14 C15 H15 109.5 . . ?
C15 C16 C17 108.98(9) . . ?
C15 C16 H16A 109.9 . . ?
C17 C16 H16A 109.9 . . ?
C15 C16 H16B 109.9 . . ?
C17 C16 H16B 109.9 . . ?
H16A C16 H16B 108.3 . . ?
C22 C17 C16 109.51(10) . . ?
C22 C17 C18 109.42(10) . . ?
C16 C17 C18 109.97(10) . . ?
C22 C17 H17 109.3 . . ?
C16 C17 H17 109.3 . . ?
C18 C17 H17 109.3 . . ?
C13 C18 C17 109.61(9) . . ?
C13 C18 H18A 109.7 . . ?
C17 C18 H18A 109.7 . . ?
C13 C18 H18B 109.7 . . ?
C17 C18 H18B 109.7 . . ?
H18A C18 H18B 108.2 . . ?
C21 C19 C13 109.51(9) . . ?
C21 C19 H19A 109.8 . . ?
C13 C19 H19A 109.8 . . ?
C21 C19 H19B 109.8 . . ?
C13 C19 H19B 109.8 . . ?
H19A C19 H19B 108.2 . . ?
C21 C20 C15 109.75(9) . . ?
C21 C20 H20A 109.7 . . ?
C15 C20 H20A 109.7 . . ?
C21 C20 H20B 109.7 . . ?
C15 C20 H20B 109.7 . . ?
H20A C20 H20B 108.2 . . ?
C20 C21 C22 109.25(10) . . ?
C20 C21 C19 109.37(9) . . ?
C22 C21 C19 109.78(10) . . ?
C20 C21 H21 109.5 . . ?
C22 C21 H21 109.5 . . ?
C19 C21 H21 109.5 . . ?
C17 C22 C21 109.48(9) . . ?
C17 C22 H22A 109.8 . . ?
C21 C22 H22A 109.8 . . ?
C17 C22 H22B 109.8 . . ?
C21 C22 H22B 109.8 . . ?
H22A C22 H22B 108.2 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C3 N3 C1 N1 -177.38(11) . . . . ?
C13 N3 C1 N1 -0.72(17) . . . . ?
C3 N3 C1 N2 2.38(11) . . . . ?
C13 N3 C1 N2 179.04(9) . . . . ?
C2 N2 C1 N1 177.52(11) . . . . ?
C4 N2 C1 N1 1.40(18) . . . . ?
C2 N2 C1 N3 -2.23(12) . . . . ?
C4 N2 C1 N3 -178.34(10) . . . . ?
C1 N2 C2 C3 1.26(12) . . . . ?
C4 N2 C2 C3 177.41(10) . . . . ?
N2 C2 C3 N3 0.27(12) . . . . ?
C1 N3 C3 C2 -1.70(12) . . . . ?
C13 N3 C3 C2 -178.33(10) . . . . ?
C1 N2 C4 C5 -79.73(14) . . . . ?
C2 N2 C4 C5 104.70(12) . . . . ?
C1 N2 C4 C9 103.25(13) . . . . ?
C2 N2 C4 C9 -72.32(14) . . . . ?
C9 C4 C5 C6 3.30(16) . . . . ?
N2 C4 C5 C6 -173.62(9) . . . . ?
C9 C4 C5 C10 -178.29(10) . . . . ?
N2 C4 C5 C10 4.79(16) . . . . ?
C4 C5 C6 C7 0.77(16) . . . . ?
C10 C5 C6 C7 -177.65(10) . . . . ?
C5 C6 C7 C8 -3.84(17) . . . . ?
C5 C6 C7 C11 174.96(11) . . . . ?
C6 C7 C8 C9 2.99(17) . . . . ?
C11 C7 C8 C9 -175.81(11) . . . . ?
C7 C8 C9 C4 0.87(16) . . . . ?
C7 C8 C9 C12 -178.84(11) . . . . ?
C5 C4 C9 C8 -4.10(16) . . . . ?
N2 C4 C9 C8 172.85(10) . . . . ?
C5 C4 C9 C12 175.61(10) . . . . ?
N2 C4 C9 C12 -7.43(16) . . . . ?
C1 N3 C13 C19 -61.48(13) . . . . ?
C3 N3 C13 C19 114.65(11) . . . . ?
C1 N3 C13 C18 178.70(9) . . . . ?
C3 N3 C13 C18 -5.17(14) . . . . ?
C1 N3 C13 C14 59.18(13) . . . . ?
C3 N3 C13 C14 -124.69(11) . . . . ?
N3 C13 C14 C15 -179.97(9) . . . . ?
C19 C13 C14 C15 -59.31(11) . . . . ?
C18 C13 C14 C15 59.99(11) . . . . ?
C13 C14 C15 C16 -60.59(12) . . . . ?
C13 C14 C15 C20 59.57(12) . . . . ?
C20 C15 C16 C17 -59.87(12) . . . . ?
C14 C15 C16 C17 59.88(12) . . . . ?
C15 C16 C17 C22 60.46(12) . . . . ?
C15 C16 C17 C18 -59.81(12) . . . . ?
N3 C13 C18 C17 -179.78(9) . . . . ?
C19 C13 C18 C17 60.04(12) . . . . ?
C14 C13 C18 C17 -59.63(12) . . . . ?
C22 C17 C18 C13 -60.19(12) . . . . ?
C16 C17 C18 C13 60.13(12) . . . . ?
N3 C13 C19 C21 -179.97(9) . . . . ?
C18 C13 C19 C21 -59.82(11) . . . . ?
C14 C13 C19 C21 59.28(11) . . . . ?
C16 C15 C20 C21 59.76(12) . . . . ?
C14 C15 C20 C21 -60.37(12) . . . . ?
C15 C20 C21 C22 -59.48(12) . . . . ?
C15 C20 C21 C19 60.70(12) . . . . ?
C13 C19 C21 C20 -59.90(12) . . . . ?
C13 C19 C21 C22 59.95(12) . . . . ?
C16 C17 C22 C21 -60.77(12) . . . . ?
C18 C17 C22 C21 59.84(12) . . . . ?
C20 C21 C22 C17 60.03(12) . . . . ?
C19 C21 C22 C17 -59.90(12) . . . . ?

_refine_diff_density_max         0.280
_refine_diff_density_min         -0.283
_refine_diff_density_rms         0.044


