# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2024

####################################################################### 
# 
# 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_lst216_1
_database_code_depnum_ccdc_archive 'CCDC 2337531'
loop_
_audit_author_name
_audit_author_address
'Antoine Dupe'
;University of Graz
Austria
;
_audit_update_record             
;
2024-05-13 deposited with the CCDC.	2024-05-23 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT971_lst216_1            
;
PROBLEM: Check Calcd Resid. Dens.  0.76Ang From W1              3.61 eA-3
RESPONSE: The large positive density is close to the heavy W atom
;
# Added during the CSD deposition process: Monday 13 May 2024 03:38 PM
# end Validation Reply Form

_audit_creation_date             2024-05-13
_audit_creation_method           
;
Olex2 1.5-ac6-019
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6920)
;
_shelx_SHELXL_version_number     2019/3
_audit_author_email              antoine.dupe@uni-graz.at
_chemical_name_common            ?
_chemical_name_systematic        
tricarbonyl-dibromo-bis(3,5-dimethyl-1H-pyrazole)-tungsten
_chemical_formula_moiety         'C13 H16 Br2 N4 O3 W'
_chemical_formula_sum            'C13 H16 Br2 N4 O3 W'
_chemical_formula_weight         619.97
_chemical_melting_point          ?
_chemical_oxdiff_formula         C13H16Br2N4O3W
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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/n 1'
_space_group_name_Hall           '-P 2yn'
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                   10.5949(2)
_cell_length_b                   14.4051(3)
_cell_length_c                   11.7972(3)
_cell_angle_alpha                90
_cell_angle_beta                 91.105(2)
_cell_angle_gamma                90
_cell_volume                     1800.16(7)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    60547
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      33.1300
_cell_measurement_theta_min      2.2000
_shelx_estimated_absorpt_T_max   0.381
_shelx_estimated_absorpt_T_min   0.198
_exptl_absorpt_coefficient_mu    10.874
_exptl_absorpt_correction_T_max  0.02646
_exptl_absorpt_correction_T_min  0.00914
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.104a (Rigaku Oxford Diffraction, 2023)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.288
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             1160
_exptl_crystal_preparation       ?
_exptl_crystal_recrystallization_method 'recrystallized in DCM / heptane'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.11
_exptl_crystal_size_rad          0.400
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1121
_diffrn_reflns_av_unetI/netI     0.0281
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            95310
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.280
_diffrn_reflns_theta_min         2.232
_diffrn_ambient_environment      ?
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 ?
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -99.59   4.41   1.00   20.00    --  -21.24 -73.76-154.25  104
  2  ω    -99.59   4.41   1.00   20.00    --  -21.24 -73.76 -34.25  104
  3  ω    -53.58  19.42   1.00   20.00    --  -21.24  88.88-152.23   73
  4  ω    -53.58  19.42   1.00   20.00    --  -21.24  88.88 -32.23   73
  5  ω    -53.58  19.42   1.00   20.00    --  -21.24  88.88  87.77   73
  6  ω    -99.59   4.41   1.00   20.00    --  -21.24 -73.76  25.75  104
  7  ω    -99.59   4.41   1.00   20.00    --  -21.24 -73.76 145.75  104
  8  ω    -53.58  19.42   1.00   20.00    --  -21.24  88.88 -92.23   73
  9  φ     -9.83 350.17   1.00   20.00  58.62 -21.24  30.17    --   360
 10  ω    -53.58  19.42   1.00   20.00    --  -21.24  88.88  27.77   73
 11  ω    -53.58  19.42   1.00   20.00    --  -21.24  88.88 147.77   73
 12  ω    306.42 307.42   1.00   20.00    --  -21.24  88.88 147.77    1
 13  φ   -332.86  27.14   1.00   20.00   7.24 -21.24 -77.15    --   360
 14  ω    -99.59   4.41   1.00   20.00    --  -21.24 -73.76 -94.25  104
 15  ω    -99.59   4.41   1.00   20.00    --  -21.24 -73.76  85.75  104
 16  φ   -350.17   9.83   1.00   20.00  -7.37 -21.24 -30.17    --   360
 17  ω    -85.59  20.41   1.00   20.00    --   -6.24 -73.76 115.75  106
;
_diffrn_measurement_device       ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_radiation_monochromator  'multilayer monochromator'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'Incoatec microfocus sealed tube'
_diffrn_source_type              ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3787
_reflns_number_total             4465
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_data_collection       'APEX2 (Bruker, 2014)'
_computing_data_reduction        'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac6-019 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-019 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         3.696
_refine_diff_density_min         -1.029
_refine_diff_density_rms         0.180
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         4465
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0428
_refine_ls_R_factor_gt           0.0343
_refine_ls_restrained_S_all      1.053
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0524P)²+1.1396P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0824
_refine_ls_wR_factor_ref         0.0860
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-H2 = N4-H4
 0.88 with sigma of 0.001
3.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C11(H11)
3.b Idealised Me refined as rotating group:
 C4(H41,H42,H43), C8(H81,H82,H83), C9(H91,H92,H93), C13(H131,H132,H133)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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
W1 W 0.62270(2) 0.63908(2) 0.68970(2) 0.02936(8) Uani 1 1 d . . . . .
Br1 Br 0.53536(5) 0.58306(4) 0.88580(4) 0.03502(12) Uani 1 1 d . . . . .
Br2 Br 0.39673(5) 0.59332(3) 0.60004(4) 0.03247(12) Uani 1 1 d . . . . .
C1 C 0.7638(5) 0.6749(4) 0.7927(4) 0.0346(11) Uani 1 1 d . . . . .
O1 O 0.8482(4) 0.6907(3) 0.8528(4) 0.0445(9) Uani 1 1 d . . . . .
C2 C 0.7830(5) 0.5998(4) 0.6192(5) 0.0395(12) Uani 1 1 d . . . . .
O2 O 0.8782(4) 0.5794(3) 0.5791(4) 0.0537(11) Uani 1 1 d . . . . .
C3 C 0.6362(5) 0.5022(4) 0.6905(4) 0.0335(11) Uani 1 1 d . . . . .
O3 O 0.6361(4) 0.4213(3) 0.6913(3) 0.0429(9) Uani 1 1 d . . . . .
N1 N 0.5302(4) 0.7761(3) 0.7223(3) 0.0321(9) Uani 1 1 d . . . . .
N2 N 0.4571(4) 0.8162(3) 0.6374(4) 0.0357(10) Uani 1 1 d D . . . .
H2 H 0.437(5) 0.783(2) 0.577(2) 0.031(14) Uiso 1 1 d D . . . .
C4 C 0.5985(6) 0.8254(4) 0.9187(5) 0.0425(13) Uani 1 1 d . . . . .
H41 H 0.568195 0.768049 0.953512 0.064 Uiso 1 1 calc R U . . .
H42 H 0.580819 0.878092 0.968509 0.064 Uiso 1 1 calc R U . . .
H43 H 0.689662 0.820944 0.907300 0.064 Uiso 1 1 calc R U . . .
C5 C 0.5325(5) 0.8395(4) 0.8067(5) 0.0353(11) Uani 1 1 d . . . . .
C6 C 0.4613(6) 0.9176(4) 0.7743(5) 0.0425(13) Uani 1 1 d . . . . .
H6 H 0.447177 0.971526 0.818608 0.051 Uiso 1 1 calc R U . . .
C7 C 0.4155(5) 0.9010(4) 0.6653(5) 0.0401(12) Uani 1 1 d . . . . .
C8 C 0.3406(6) 0.9602(4) 0.5847(6) 0.0526(16) Uani 1 1 d . . . . .
H81 H 0.394984 1.008891 0.554231 0.079 Uiso 1 1 calc R U . . .
H82 H 0.270297 0.988786 0.624628 0.079 Uiso 1 1 calc R U . . .
H83 H 0.307527 0.921781 0.522364 0.079 Uiso 1 1 calc R U . . .
N3 N 0.6424(4) 0.7090(3) 0.5223(3) 0.0319(9) Uani 1 1 d . . . . .
N4 N 0.6044(4) 0.6670(3) 0.4229(4) 0.0337(9) Uani 1 1 d D . . . .
H4 H 0.573(5) 0.6104(13) 0.419(5) 0.044(18) Uiso 1 1 d D . . . .
C9 C 0.7711(6) 0.8457(4) 0.5766(5) 0.0404(13) Uani 1 1 d . . . . .
H91 H 0.705099 0.880903 0.614608 0.061 Uiso 1 1 calc R U . . .
H92 H 0.828416 0.888702 0.538960 0.061 Uiso 1 1 calc R U . . .
H93 H 0.818687 0.808858 0.632709 0.061 Uiso 1 1 calc R U . . .
C10 C 0.7119(5) 0.7824(3) 0.4904(4) 0.0301(10) Uani 1 1 d . . . . .
C11 C 0.7163(5) 0.7867(4) 0.3723(4) 0.0333(10) Uani 1 1 d . . . . .
H11 H 0.759285 0.831531 0.328390 0.040 Uiso 1 1 calc R U . . .
C12 C 0.6459(5) 0.7130(4) 0.3321(4) 0.0346(11) Uani 1 1 d . . . . .
C13 C 0.6107(6) 0.6855(5) 0.2133(5) 0.0467(14) Uani 1 1 d . . . . .
H131 H 0.610253 0.617636 0.207210 0.070 Uiso 1 1 calc R U . . .
H132 H 0.672346 0.711206 0.160965 0.070 Uiso 1 1 calc R U . . .
H133 H 0.526550 0.709612 0.193935 0.070 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
W1 Br1 2.6347(5) . ?
W1 Br2 2.6810(5) . ?
W1 C1 1.976(5) . ?
W1 C2 1.988(6) . ?
W1 C3 1.976(6) . ?
W1 N1 2.240(4) . ?
W1 N3 2.230(4) . ?
C1 O1 1.154(6) . ?
C2 O2 1.160(7) . ?
C3 O3 1.166(7) . ?
N1 N2 1.380(5) . ?
N1 C5 1.351(7) . ?
N2 H2 0.8800(10) . ?
N2 C7 1.342(7) . ?
C4 H41 0.9800 . ?
C4 H42 0.9800 . ?
C4 H43 0.9800 . ?
C4 C5 1.497(7) . ?
C5 C6 1.403(8) . ?
C6 H6 0.9500 . ?
C6 C7 1.386(8) . ?
C7 C8 1.494(8) . ?
C8 H81 0.9800 . ?
C8 H82 0.9800 . ?
C8 H83 0.9800 . ?
N3 N4 1.372(6) . ?
N3 C10 1.347(6) . ?
N4 H4 0.8800(10) . ?
N4 C12 1.341(7) . ?
C9 H91 0.9800 . ?
C9 H92 0.9800 . ?
C9 H93 0.9800 . ?
C9 C10 1.495(7) . ?
C10 C11 1.397(7) . ?
C11 H11 0.9500 . ?
C11 C12 1.377(7) . ?
C12 C13 1.496(7) . ?
C13 H131 0.9800 . ?
C13 H132 0.9800 . ?
C13 H133 0.9800 . ?

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
Br1 W1 Br2 86.849(17) . . ?
C1 W1 Br1 79.30(15) . . ?
C1 W1 Br2 164.95(16) . . ?
C1 W1 C2 71.9(2) . . ?
C1 W1 N1 89.58(18) . . ?
C1 W1 N3 110.13(18) . . ?
C2 W1 Br1 126.70(15) . . ?
C2 W1 Br2 121.90(17) . . ?
C2 W1 N1 134.7(2) . . ?
C2 W1 N3 70.30(19) . . ?
C3 W1 Br1 73.55(14) . . ?
C3 W1 Br2 79.67(14) . . ?
C3 W1 C1 101.8(2) . . ?
C3 W1 C2 69.9(2) . . ?
C3 W1 N1 155.46(19) . . ?
C3 W1 N3 116.52(18) . . ?
N1 W1 Br1 87.54(11) . . ?
N1 W1 Br2 83.91(10) . . ?
N3 W1 Br1 162.99(11) . . ?
N3 W1 Br2 81.92(11) . . ?
N3 W1 N1 78.63(16) . . ?
O1 C1 W1 176.2(5) . . ?
O2 C2 W1 177.9(6) . . ?
O3 C3 W1 175.8(5) . . ?
N2 N1 W1 119.1(3) . . ?
C5 N1 W1 136.1(3) . . ?
C5 N1 N2 104.7(4) . . ?
N1 N2 H2 118(3) . . ?
C7 N2 N1 112.7(4) . . ?
C7 N2 H2 129(3) . . ?
H41 C4 H42 109.5 . . ?
H41 C4 H43 109.5 . . ?
H42 C4 H43 109.5 . . ?
C5 C4 H41 109.5 . . ?
C5 C4 H42 109.5 . . ?
C5 C4 H43 109.5 . . ?
N1 C5 C4 124.1(5) . . ?
N1 C5 C6 109.8(5) . . ?
C6 C5 C4 126.1(5) . . ?
C5 C6 H6 126.5 . . ?
C7 C6 C5 106.9(5) . . ?
C7 C6 H6 126.5 . . ?
N2 C7 C6 105.9(5) . . ?
N2 C7 C8 122.5(5) . . ?
C6 C7 C8 131.6(5) . . ?
C7 C8 H81 109.5 . . ?
C7 C8 H82 109.5 . . ?
C7 C8 H83 109.5 . . ?
H81 C8 H82 109.5 . . ?
H81 C8 H83 109.5 . . ?
H82 C8 H83 109.5 . . ?
N4 N3 W1 121.8(3) . . ?
C10 N3 W1 131.5(3) . . ?
C10 N3 N4 105.1(4) . . ?
N3 N4 H4 124(4) . . ?
C12 N4 N3 111.8(4) . . ?
C12 N4 H4 123(4) . . ?
H91 C9 H92 109.5 . . ?
H91 C9 H93 109.5 . . ?
H92 C9 H93 109.5 . . ?
C10 C9 H91 109.5 . . ?
C10 C9 H92 109.5 . . ?
C10 C9 H93 109.5 . . ?
N3 C10 C9 120.9(5) . . ?
N3 C10 C11 110.0(4) . . ?
C11 C10 C9 129.1(5) . . ?
C10 C11 H11 126.8 . . ?
C12 C11 C10 106.3(5) . . ?
C12 C11 H11 126.8 . . ?
N4 C12 C11 106.8(4) . . ?
N4 C12 C13 122.6(5) . . ?
C11 C12 C13 130.5(5) . . ?
C12 C13 H131 109.5 . . ?
C12 C13 H132 109.5 . . ?
C12 C13 H133 109.5 . . ?
H131 C13 H132 109.5 . . ?
H131 C13 H133 109.5 . . ?
H132 C13 H133 109.5 . . ?

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
W1 N1 N2 C7 -175.2(4) . . . . ?
W1 N1 C5 C4 -7.0(9) . . . . ?
W1 N1 C5 C6 174.8(4) . . . . ?
W1 N3 N4 C12 -168.3(4) . . . . ?
W1 N3 C10 C9 -14.3(7) . . . . ?
W1 N3 C10 C11 165.9(4) . . . . ?
N1 N2 C7 C6 -0.9(7) . . . . ?
N1 N2 C7 C8 176.6(5) . . . . ?
N1 C5 C6 C7 -0.8(7) . . . . ?
N2 N1 C5 C4 178.4(5) . . . . ?
N2 N1 C5 C6 0.2(6) . . . . ?
C4 C5 C6 C7 -178.9(6) . . . . ?
C5 N1 N2 C7 0.5(6) . . . . ?
C5 C6 C7 N2 1.0(7) . . . . ?
C5 C6 C7 C8 -176.2(7) . . . . ?
N3 N4 C12 C11 1.4(6) . . . . ?
N3 N4 C12 C13 -175.9(5) . . . . ?
N3 C10 C11 C12 0.3(6) . . . . ?
N4 N3 C10 C9 -179.6(5) . . . . ?
N4 N3 C10 C11 0.5(6) . . . . ?
C9 C10 C11 C12 -179.5(5) . . . . ?
C10 N3 N4 C12 -1.2(6) . . . . ?
C10 C11 C12 N4 -1.0(6) . . . . ?
C10 C11 C12 C13 176.0(6) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 5.827
_oxdiff_exptl_absorpt_empirical_full_min 0.262
####################################################################### 
# 
# 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_ad08
_database_code_depnum_ccdc_archive 'CCDC 2355110'
loop_
_audit_author_name
_audit_author_address
'Antoine Dupe'
;University of Graz
Austria
;
_audit_update_record             
;
2024-05-13 deposited with the CCDC.	2024-05-23 downloaded from the CCDC.
;
_audit_creation_date             2024-05-13
_audit_creation_method           
;
Olex2 1.5-ac6-019
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6920)
;
_shelx_SHELXL_version_number     2019/3
_audit_author_email              antoine.dupe@uni-graz.at
_chemical_name_common            ?
_chemical_name_systematic        
"fac-tricarbonyl-dibromo-(1-(1-iminoethyl)-3,5-dimethylpyrazole-N,N')-tungsten(II) chloroform solvate"
_chemical_formula_moiety         'C10 H11 Br2 N3 O3 W, C H Cl3'
_chemical_formula_sum            'C11 H12 Br2 Cl3 N3 O3 W'
_chemical_formula_weight         684.26
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C11 H12 N3 O3 Cl3 Br2 W1 '
_chemical_oxdiff_usercomment     LST370
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'
O O 0.0106 0.0060 '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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   9.2942(2)
_cell_length_b                   10.3885(2)
_cell_length_c                   11.1039(2)
_cell_angle_alpha                63.402(2)
_cell_angle_beta                 75.4980(10)
_cell_angle_gamma                79.6940(10)
_cell_volume                     925.34(4)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    22411
_cell_measurement_temperature    99.97(18)
_cell_measurement_theta_max      33.2630
_cell_measurement_theta_min      2.1960
_shelx_estimated_absorpt_T_max   0.377
_shelx_estimated_absorpt_T_min   0.137
_exptl_absorpt_coefficient_mu    11.007
_exptl_absorpt_correction_T_max  0.514
_exptl_absorpt_correction_T_min  0.150
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.107a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'light orange'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.456
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             636
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
13 2 1 0.0585
-13 -2 -1 0.0517
4 14 12 0.0981
-2 -14 -12 0.1034
12 6 10 0.0981
-12 -5 -11 0.0773
-5 -12 1 0.0835
5 12 -1 0.0996
9 -8 0 0.0807
-7 11 2 0.0874
0 -5 -15 0.0922
4 7 16 0.1244

_exptl_crystal_recrystallization_method 'recrystallized in chloroform'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.11
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
12.8284 1.5816 0.7629 -0.5590 0.1942 0.8061
-12.8196 -1.5168 -0.7076 0.5626 -0.1955 -0.8033
3.6709 13.6518 11.5608 0.6690 -0.2385 0.7039
-1.8641 -13.5742 -11.5780 -0.7569 0.2691 -0.5956
11.7720 6.0722 10.0568 0.0495 0.3561 0.9331
-11.5783 -4.9357 -10.5550 -0.0622 -0.4545 -0.8886
-5.0484 -11.5975 1.4459 0.0957 0.7511 -0.6532
5.1596 11.6208 -1.3290 -0.0948 -0.7443 0.6611
9.1074 -8.4196 -0.3358 -0.6260 0.7324 0.2678
-6.6288 11.0293 2.2128 0.6500 -0.7593 -0.0308
-0.1341 -4.8665 -15.1280 -0.8524 -0.4652 -0.2386
4.1605 7.4309 15.5839 0.7280 0.3987 0.5578

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0438
_diffrn_reflns_av_unetI/netI     0.0343
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            28243
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.506
_diffrn_reflns_theta_min         2.270
_diffrn_ambient_environment      ?
_diffrn_ambient_temperature      99.97(18)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -69.00   5.00   0.50    0.50    --   13.37 -19.00 120.00  148
  2  ω    -69.00   5.00   0.50    0.50    --   13.37 -19.00  30.00  148
  3  ω    -69.00   5.00   0.50    0.50    --   13.37 -19.00 -90.00  148
  4  ω    -69.00   1.00   0.50    0.50    --   13.37 -19.00 -30.00  140
  5  ω     42.00  90.00   0.50    0.50    --   13.37 178.00-180.00   96
  6  ω    -69.00   5.00   0.50    0.50    --   13.37 -19.00-180.00  148
  7  ω    -23.00  28.00   0.50    0.50    --  -15.09 -99.00 -60.00  102
  8  ω    -23.00  28.00   0.50    0.50    --  -15.09 -99.00-180.00  102
  9  ω    -93.00   9.00   0.50    0.50    --  -15.09 -57.00  90.00  204
 10  ω    -93.00   9.00   0.50    0.50    --  -15.09 -57.00  90.00  204
 11  ω    -23.00  57.00   0.50    0.50    --   13.37 -99.00  90.00  160
 12  ω     24.00  86.00   0.50    0.50    --   13.37-146.00  20.00  124
 13  ω     13.00  74.00   0.50    0.50    --   13.37-126.00-172.00  122
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 100'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0489675000
_diffrn_orient_matrix_UB_12      0.0193641000
_diffrn_orient_matrix_UB_13      0.0505531000
_diffrn_orient_matrix_UB_21      0.0203089000
_diffrn_orient_matrix_UB_22      -0.0671001000
_diffrn_orient_matrix_UB_23      0.0521553000
_diffrn_orient_matrix_UB_31      0.0586576000
_diffrn_orient_matrix_UB_32      0.0314335000
_diffrn_orient_matrix_UB_33      0.0051436000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5172
_reflns_number_total             5632
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.43.107a (Rigaku OD, 2024)'
_computing_data_collection       
'CrysAlisPro system (CCD 43.92a 64-bit (release 05-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.107a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-019 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-019 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         0.756
_refine_diff_density_min         -0.964
_refine_diff_density_rms         0.146
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     215
_refine_ls_number_reflns         5632
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0267
_refine_ls_R_factor_gt           0.0230
_refine_ls_restrained_S_all      1.038
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0136P)²+0.8592P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0444
_refine_ls_wR_factor_ref         0.0452
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C11(H11)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6)
2.c Idealised Me refined as rotating group:
 C4(H41,H42,H43), C8(H81,H82,H83), C9(H91,H92,H93)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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
W1 W 0.35001(2) 0.52653(2) 0.28199(2) 0.01270(3) Uani 1 1 d . . . . .
Br1 Br 0.27150(3) 0.31321(3) 0.25088(3) 0.02181(6) Uani 1 1 d . . . . .
Br2 Br 0.28911(3) 0.70239(3) 0.03429(3) 0.01793(6) Uani 1 1 d . . . . .
C1 C 0.1265(3) 0.5562(3) 0.3243(3) 0.0194(6) Uani 1 1 d . . . . .
O1 O -0.0010(2) 0.5751(2) 0.3423(2) 0.0258(5) Uani 1 1 d . . . . .
C2 C 0.3032(3) 0.5677(3) 0.4453(3) 0.0184(6) Uani 1 1 d . . . . .
O2 O 0.2768(2) 0.5862(3) 0.5440(2) 0.0256(5) Uani 1 1 d . . . . .
C3 C 0.4051(3) 0.3513(3) 0.4418(3) 0.0188(6) Uani 1 1 d . . . . .
O3 O 0.4370(2) 0.2513(2) 0.5338(2) 0.0264(5) Uani 1 1 d . . . . .
N1 N 0.4829(2) 0.7081(2) 0.2168(2) 0.0135(4) Uani 1 1 d . . . . .
N2 N 0.6314(2) 0.6924(2) 0.1576(2) 0.0141(4) Uani 1 1 d . . . . .
C4 C 0.8559(3) 0.8459(4) 0.0368(3) 0.0244(6) Uani 1 1 d . . . . .
H41 H 0.922754 0.777579 0.096872 0.037 Uiso 1 1 calc R U . . .
H42 H 0.874493 0.944802 0.014212 0.037 Uiso 1 1 calc R U . . .
H43 H 0.874214 0.832369 -0.047820 0.037 Uiso 1 1 calc R U . . .
C5 C 0.6982(3) 0.8197(3) 0.1084(3) 0.0173(5) Uani 1 1 d . . . . .
C6 C 0.5909(3) 0.9147(3) 0.1375(3) 0.0177(5) Uani 1 1 d . . . . .
H6 H 0.602537 1.012151 0.115979 0.021 Uiso 1 1 calc R U . . .
C7 C 0.4588(3) 0.8427(3) 0.2055(3) 0.0168(5) Uani 1 1 d . . . . .
C8 C 0.3114(3) 0.9029(3) 0.2575(3) 0.0223(6) Uani 1 1 d . . . . .
H81 H 0.233435 0.883608 0.223870 0.033 Uiso 1 1 calc R U . . .
H82 H 0.313284 1.007369 0.224806 0.033 Uiso 1 1 calc R U . . .
H83 H 0.290662 0.857312 0.358148 0.033 Uiso 1 1 calc R U . . .
N3 N 0.5723(3) 0.4807(3) 0.1830(3) 0.0170(5) Uani 1 1 d . . . . .
H3 H 0.596(4) 0.414(4) 0.168(4) 0.026(10) Uiso 1 1 d . . . . .
C9 C 0.8350(3) 0.5325(3) 0.0886(3) 0.0212(6) Uani 1 1 d . . . . .
H91 H 0.863225 0.603137 -0.006612 0.032 Uiso 1 1 calc R U . . .
H92 H 0.848773 0.435217 0.092198 0.032 Uiso 1 1 calc R U . . .
H93 H 0.897866 0.538243 0.144732 0.032 Uiso 1 1 calc R U . . .
C10 C 0.6760(3) 0.5644(3) 0.1426(3) 0.0153(5) Uani 1 1 d . . . . .
C11 C -0.1816(3) 1.0118(3) 0.3986(4) 0.0263(6) Uani 1 1 d . . . . .
H11 H -0.200424 0.958961 0.501004 0.032 Uiso 1 1 calc R U . . .
Cl1 Cl -0.35325(9) 1.09119(9) 0.34769(10) 0.03397(18) Uani 1 1 d . . . . .
Cl2 Cl -0.05792(11) 1.14586(10) 0.34838(10) 0.0377(2) Uani 1 1 d . . . . .
Cl3 Cl -0.10183(9) 0.88782(11) 0.32918(12) 0.0421(2) Uani 1 1 d . . . . .


_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
W1 Br1 2.6369(3) . ?
W1 Br2 2.6707(3) . ?
W1 C1 2.010(3) . ?
W1 C2 1.973(3) . ?
W1 C3 1.988(3) . ?
W1 N1 2.185(2) . ?
W1 N3 2.164(2) . ?
C1 O1 1.148(3) . ?
C2 O2 1.156(3) . ?
C3 O3 1.141(3) . ?
N1 N2 1.387(3) . ?
N1 C7 1.329(4) . ?
N2 C5 1.382(3) . ?
N2 C10 1.391(4) . ?
C4 H41 0.9800 . ?
C4 H42 0.9800 . ?
C4 H43 0.9800 . ?
C4 C5 1.490(4) . ?
C5 C6 1.359(4) . ?
C6 H6 0.9500 . ?
C6 C7 1.412(4) . ?
C7 C8 1.491(4) . ?
C8 H81 0.9800 . ?
C8 H82 0.9800 . ?
C8 H83 0.9800 . ?
N3 H3 0.77(4) . ?
N3 C10 1.273(4) . ?
C9 H91 0.9800 . ?
C9 H92 0.9800 . ?
C9 H93 0.9800 . ?
C9 C10 1.487(4) . ?
C11 H11 1.0000 . ?
C11 Cl1 1.763(3) . ?
C11 Cl2 1.769(3) . ?
C11 Cl3 1.751(3) . ?

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
Br1 W1 Br2 87.574(9) . . ?
C1 W1 Br1 78.78(8) . . ?
C1 W1 Br2 78.13(8) . . ?
C1 W1 N1 119.12(10) . . ?
C1 W1 N3 160.52(10) . . ?
C2 W1 Br1 129.35(8) . . ?
C2 W1 Br2 126.67(8) . . ?
C2 W1 C1 74.64(11) . . ?
C2 W1 C3 70.66(12) . . ?
C2 W1 N1 77.43(10) . . ?
C2 W1 N3 124.83(10) . . ?
C3 W1 Br1 76.39(8) . . ?
C3 W1 Br2 162.17(8) . . ?
C3 W1 C1 105.78(12) . . ?
C3 W1 N1 114.04(9) . . ?
C3 W1 N3 82.62(11) . . ?
N1 W1 Br1 152.66(6) . . ?
N1 W1 Br2 77.26(6) . . ?
N3 W1 Br1 86.43(7) . . ?
N3 W1 Br2 88.74(6) . . ?
N3 W1 N1 70.82(9) . . ?
O1 C1 W1 176.9(3) . . ?
O2 C2 W1 177.4(3) . . ?
O3 C3 W1 179.6(2) . . ?
N2 N1 W1 116.35(16) . . ?
C7 N1 W1 137.16(18) . . ?
C7 N1 N2 106.1(2) . . ?
N1 N2 C10 115.7(2) . . ?
C5 N2 N1 110.4(2) . . ?
C5 N2 C10 133.2(2) . . ?
H41 C4 H42 109.5 . . ?
H41 C4 H43 109.5 . . ?
H42 C4 H43 109.5 . . ?
C5 C4 H41 109.5 . . ?
C5 C4 H42 109.5 . . ?
C5 C4 H43 109.5 . . ?
N2 C5 C4 126.3(3) . . ?
C6 C5 N2 106.1(2) . . ?
C6 C5 C4 127.6(3) . . ?
C5 C6 H6 126.1 . . ?
C5 C6 C7 107.7(2) . . ?
C7 C6 H6 126.1 . . ?
N1 C7 C6 109.7(2) . . ?
N1 C7 C8 123.0(2) . . ?
C6 C7 C8 127.4(3) . . ?
C7 C8 H81 109.5 . . ?
C7 C8 H82 109.5 . . ?
C7 C8 H83 109.5 . . ?
H81 C8 H82 109.5 . . ?
H81 C8 H83 109.5 . . ?
H82 C8 H83 109.5 . . ?
W1 N3 H3 124(3) . . ?
C10 N3 W1 122.5(2) . . ?
C10 N3 H3 113(3) . . ?
H91 C9 H92 109.5 . . ?
H91 C9 H93 109.5 . . ?
H92 C9 H93 109.5 . . ?
C10 C9 H91 109.5 . . ?
C10 C9 H92 109.5 . . ?
C10 C9 H93 109.5 . . ?
N2 C10 C9 120.0(2) . . ?
N3 C10 N2 114.4(2) . . ?
N3 C10 C9 125.6(3) . . ?
Cl1 C11 H11 108.4 . . ?
Cl1 C11 Cl2 110.58(18) . . ?
Cl2 C11 H11 108.4 . . ?
Cl3 C11 H11 108.4 . . ?
Cl3 C11 Cl1 110.63(18) . . ?
Cl3 C11 Cl2 110.32(18) . . ?

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
W1 N1 N2 C5 173.76(16) . . . . ?
W1 N1 N2 C10 2.2(3) . . . . ?
W1 N1 C7 C6 -171.8(2) . . . . ?
W1 N1 C7 C8 7.6(4) . . . . ?
W1 N3 C10 N2 -4.8(3) . . . . ?
W1 N3 C10 C9 172.6(2) . . . . ?
N1 N2 C5 C4 -179.3(3) . . . . ?
N1 N2 C5 C6 0.2(3) . . . . ?
N1 N2 C10 N3 1.5(3) . . . . ?
N1 N2 C10 C9 -176.0(2) . . . . ?
N2 N1 C7 C6 0.8(3) . . . . ?
N2 N1 C7 C8 -179.9(2) . . . . ?
N2 C5 C6 C7 0.3(3) . . . . ?
C4 C5 C6 C7 179.7(3) . . . . ?
C5 N2 C10 N3 -167.6(3) . . . . ?
C5 N2 C10 C9 14.8(4) . . . . ?
C5 C6 C7 N1 -0.7(3) . . . . ?
C5 C6 C7 C8 180.0(3) . . . . ?
C7 N1 N2 C5 -0.6(3) . . . . ?
C7 N1 N2 C10 -172.2(2) . . . . ?
C10 N2 C5 C4 -9.7(5) . . . . ?
C10 N2 C5 C6 169.7(3) . . . . ?

_olex2_date_sample_data_collection 2024-01-11
_olex2_date_sample_submission    2024-01-09
_olex2_exptl_crystal_mounting_method 'mounted on a glass fiber'
_olex2_submission_original_sample_id LST370
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.406
_oxdiff_exptl_absorpt_empirical_full_min 0.759
####################################################################### 
# 
# 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_ad07_2
_database_code_depnum_ccdc_archive 'CCDC 2337533'
loop_
_audit_author_name
_audit_author_address
'Antoine Dupe'
;University of Graz
Austria
;
_audit_update_record             
;
2024-05-13 deposited with the CCDC.	2024-05-23 downloaded from the CCDC.
;
_audit_creation_date             2024-05-13
_audit_creation_method           
;
Olex2 1.5-ac6-019
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6920)
;
_shelx_SHELXL_version_number     2019/3
_audit_author_email              antoine.dupe@uni-graz.at
_chemical_name_common            ?
_chemical_name_systematic        
'(mu-3,5-dimethylpyrazolyl)-bis((mu2-hydroxo)-(3,5-dimethyl-1H-pyrazole,N)-(eta2-ethyne)-carbonyl)-di-tungsten bromide chloroform 1:1 solvate'
_chemical_formula_moiety         'C21 H29 N6 O4 W2, Br, C H Cl3'
_chemical_formula_sum            'C22 H30 Br Cl3 N6 O4 W2'
_chemical_formula_weight         996.48
_chemical_absolute_configuration ?
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C22 H29 N6 O4 Cl3 Br1 W2 '
_chemical_oxdiff_usercomment     LST363
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'
Br Br -0.2901 2.4595 '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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_H-M_alt        'P 21 21 2'
_space_group_name_Hall           'P 2 2ab'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x+1/2, y+1/2, -z'
'x+1/2, -y+1/2, -z'

_cell_length_a                   7.85700(10)
_cell_length_b                   15.9287(3)
_cell_length_c                   12.3215(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1542.06(4)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    30210
_cell_measurement_temperature    100.00(13)
_cell_measurement_theta_max      33.4320
_cell_measurement_theta_min      2.0860
_shelx_estimated_absorpt_T_max   0.655
_shelx_estimated_absorpt_T_min   0.320
_exptl_absorpt_coefficient_mu    9.047
_exptl_absorpt_correction_T_max  0.877
_exptl_absorpt_correction_T_min  0.415
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.106a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'dark violet'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.146
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             940
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
0 -1 1 0.0437
-1 -2 0 0.0863
-1 -1 -1 0.0982
0 -2 1 0.0404
1 1 2 0.0495
0 2 -1 0.0107
0 1 2 0.0458
1 -2 1 0.0433
0 1 -2 0.0212
2 1 -1 0.0286
-2 -1 1 0.1067
0 -1 -2 0.0242
0 -2 -1 0.0258

_exptl_crystal_preparation       ?
_exptl_crystal_recrystallization_method 'recrystallized in chloroform'
_exptl_crystal_size_max          0.163
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.051
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
-0.0000 -1.0000 1.0000 0.0347 0.0194 0.0610
-1.0000 -2.0000 0.0000 0.1109 0.0593 -0.0168
-1.0000 -1.0000 -1.0000 0.0762 0.0399 -0.0777
0.0000 -2.0000 1.0000 0.0506 0.0596 0.0717
1.0000 1.0000 2.0000 -0.0574 -0.0606 0.1280
-0.0000 2.0000 -1.0000 -0.0506 -0.0596 -0.0717
-0.0000 1.0000 2.0000 0.0216 -0.0817 0.0899
1.0000 -2.0000 1.0000 -0.0285 0.0807 0.1098
-0.0000 1.0000 -2.0000 -0.0535 0.0013 -0.1113
2.0000 1.0000 -1.0000 -0.1928 0.0228 0.0153
-2.0000 -1.0000 1.0000 0.1928 -0.0228 -0.0153
0.0000 -1.0000 -2.0000 -0.0216 0.0817 -0.0899
0.0000 -2.0000 -1.0000 0.0130 0.1012 -0.0289

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0221
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            48614
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.501
_diffrn_reflns_theta_min         2.090
_diffrn_ambient_environment      ?
_diffrn_ambient_temperature      100.00(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -23.00  57.00   0.50    2.00    --   13.37 -99.00  90.00  160
  2  ω     42.00  90.00   0.50    2.00    --   13.37 178.00 120.00   96
  3  ω     39.00  92.00   0.50    2.00    --   13.37-178.00 -30.00  106
  4  ω    -39.00  63.00   0.50    2.00    --  -15.09  57.00   0.00  204
  5  ω    -93.00   9.00   0.50    2.00    --  -15.09 -57.00  90.00  204
  6  ω    -46.00  56.00   0.50    2.00    --  -15.09  77.00 -30.00  204
  7  ω    -93.00   9.00   0.50    2.00    --  -15.09 -57.00-150.00  204
  8  ω    -23.00  28.00   0.50    2.00    --  -15.09 -99.00  60.00  102
  9  ω    -69.00   5.00   0.50    2.00    --   13.37 -19.00 150.00  148
 10  ω    -23.00  57.00   0.50    2.00    --   13.37 -99.00-120.00  160
 11  ω    -23.00   6.00   0.50    2.00    --   13.37 -99.00 120.00   58
 12  ω    -93.00   9.00   0.50    2.00    --  -15.09 -57.00 -30.00  204
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 100'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0790687000
_diffrn_orient_matrix_UB_12      -0.0159031000
_diffrn_orient_matrix_UB_13      0.0187739000
_diffrn_orient_matrix_UB_21      0.0211040000
_diffrn_orient_matrix_UB_22      -0.0402009000
_diffrn_orient_matrix_UB_23      -0.0207602000
_diffrn_orient_matrix_UB_31      0.0381301000
_diffrn_orient_matrix_UB_32      -0.0106858000
_diffrn_orient_matrix_UB_33      0.0502926000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_reflns_Friedel_coverage         0.759
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                4558
_reflns_number_total             5144
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_data_collection       
'CrysAlisPro system (CCD 43.92a 64-bit (release 05-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-019 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-019 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         1.330
_refine_diff_density_min         -0.743
_refine_diff_density_rms         0.120
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.505(14)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     203
_refine_ls_number_reflns         5144
_refine_ls_number_restraints     43
_refine_ls_R_factor_all          0.0280
_refine_ls_R_factor_gt           0.0220
_refine_ls_restrained_S_all      1.059
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0218P)²+1.2202P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0457
_refine_ls_wR_factor_ref         0.0471
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.495(14)
 0.505(14)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C12-Cl1 = C12-Cl3 = C12-Cl2
 1.78 with sigma of 0.02
 N2-H21
 0.88 with sigma of 0.0001
 C12-Cl1 \\sim C12-Cl3 \\sim C12-Cl2
 with sigma of 0.02
 Cl1-Cl3 \\sim Cl3-Cl2 \\sim Cl2-Cl1
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl2 \\sim Cl3 \\sim C12: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 Cl1, Cl2, Cl3, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Cl1(0.5) Cl2(0.5) Cl3(0.5) C12(0.5) H12(0.5)
7.a Ternary CH refined with riding coordinates:
 C12(H12)
7.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C6(H6), C11(H111)
7.c Idealised Me refined as rotating group:
 C4(H41,H42,H43), C8(H81,H82,H83), C9(H91,H92,H93)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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
W1 W 0.49814(4) 0.60493(2) 0.73322(2) 0.01690(5) Uani 1 1 d . . . . .
O1 O 0.6523(4) 0.5039(4) 0.6997(2) 0.0211(5) Uani 1 1 d . . . . .
H11 H 0.753(6) 0.510(4) 0.689(4) 0.020(13) Uiso 1 1 d . . . . .
O3 O 0.8045(6) 0.7210(3) 0.7862(3) 0.0376(10) Uani 1 1 d . . . . .
N1 N 0.5003(10) 0.62121(18) 0.5589(3) 0.0252(7) Uani 1 1 d . . . . .
N2 N 0.3677(5) 0.5861(3) 0.5007(3) 0.0301(10) Uani 1 1 d D . . . .
H21 H 0.2818(7) 0.5655(7) 0.5380(7) 0.07(2) Uiso 1 1 d D . . . .
N3 N 0.5070(10) 0.54349(18) 0.8893(2) 0.0175(6) Uani 1 1 d . . . . .
C1 C 0.2794(9) 0.6696(4) 0.7571(8) 0.0272(16) Uani 1 1 d . . . . .
H1 H 0.158819 0.665124 0.756031 0.033 Uiso 1 1 calc R U . . .
C2 C 0.4048(8) 0.7208(3) 0.7746(4) 0.0295(11) Uani 1 1 d . . . . .
H2 H 0.434451 0.776625 0.794221 0.035 Uiso 1 1 calc R U . . .
C3 C 0.6917(9) 0.6782(4) 0.7649(8) 0.0251(14) Uani 1 1 d . . . . .
C4 C 0.7586(8) 0.7022(4) 0.5145(5) 0.0412(15) Uani 1 1 d . . . . .
H41 H 0.729179 0.749427 0.561913 0.062 Uiso 1 1 calc R U . . .
H42 H 0.813788 0.723473 0.448632 0.062 Uiso 1 1 calc R U . . .
H43 H 0.836632 0.664378 0.552654 0.062 Uiso 1 1 calc R U . . .
C5 C 0.6023(7) 0.6561(3) 0.4847(4) 0.0287(11) Uani 1 1 d . . . . .
C6 C 0.5355(9) 0.6423(3) 0.3799(4) 0.0333(19) Uani 1 1 d . . . . .
H6 H 0.583813 0.660121 0.313085 0.040 Uiso 1 1 calc R U . . .
C7 C 0.3887(9) 0.5985(3) 0.3931(4) 0.0356(13) Uani 1 1 d . . . . .
C8 C 0.2546(10) 0.5688(4) 0.3151(5) 0.0473(18) Uani 1 1 d . . . . .
H81 H 0.259463 0.602658 0.248723 0.071 Uiso 1 1 calc R U . . .
H82 H 0.142041 0.574757 0.348531 0.071 Uiso 1 1 calc R U . . .
H83 H 0.274692 0.509721 0.297096 0.071 Uiso 1 1 calc R U . . .
C9 C 0.5251(17) 0.6607(3) 1.0224(4) 0.053(3) Uani 1 1 d . . . . .
H91 H 0.610171 0.688424 0.976522 0.080 Uiso 1 1 calc R U . . .
H92 H 0.558409 0.665947 1.098732 0.080 Uiso 1 1 calc R U . . .
H93 H 0.413997 0.687391 1.011436 0.080 Uiso 1 1 calc R U . . .
C10 C 0.5140(14) 0.5697(3) 0.9925(3) 0.0333(13) Uani 1 1 d . . . . .
C11 C 0.500000 0.500000 1.0593(5) 0.054(2) Uani 1 2 d S T P . .
H111 H 0.500001 0.499999 1.136417 0.065 Uiso 1 2 calc R U P . .
Br1 Br 1.000000 0.500000 0.57275(5) 0.03930(15) Uani 1 2 d S T P . .
Cl1 Cl 0.9460(4) 0.4919(5) 0.8812(2) 0.0549(11) Uani 0.5 1 d D U P A -1
Cl2 Cl 1.0665(5) 0.6155(2) 1.0289(3) 0.0552(9) Uani 0.5 1 d D U P A -1
Cl3 Cl 1.0586(5) 0.4424(2) 1.0942(3) 0.0612(10) Uani 0.5 1 d D U P A -1
C12 C 1.0874(12) 0.5113(7) 0.9867(6) 0.029(3) Uani 0.5 1 d D U P A -1
H12 H 1.205545 0.503504 0.958360 0.034 Uiso 0.5 1 calc R U P A -1


_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
W1 O1 2.139(5) 2_665 ?
W1 O1 2.056(5) . ?
W1 N1 2.163(3) . ?
W1 N3 2.159(3) . ?
W1 C1 2.025(7) . ?
W1 C2 2.051(5) . ?
W1 C3 1.956(6) . ?
O1 H11 0.81(5) . ?
O3 C3 1.149(7) . ?
N1 N2 1.383(7) . ?
N1 C5 1.338(7) . ?
N2 H21 0.88000(14) . ?
N2 C7 1.350(6) . ?
N3 N3 1.390(6) 2_665 ?
N3 C10 1.340(5) . ?
C1 H1 0.9500 . ?
C1 C2 1.298(9) . ?
C2 H2 0.9500 . ?
C4 H41 0.9800 . ?
C4 H42 0.9800 . ?
C4 H43 0.9800 . ?
C4 C5 1.478(8) . ?
C5 C6 1.411(7) . ?
C6 H6 0.9500 . ?
C6 C7 1.358(9) . ?
C7 C8 1.502(8) . ?
C8 H81 0.9800 . ?
C8 H82 0.9800 . ?
C8 H83 0.9800 . ?
C9 H91 0.9800 . ?
C9 H92 0.9800 . ?
C9 H93 0.9800 . ?
C9 C10 1.499(7) . ?
C10 C11 1.387(6) . ?
C11 H111 0.9500 . ?
Cl1 C12 1.738(8) . ?
Cl2 C12 1.747(11) . ?
Cl3 C12 1.734(9) . ?
C12 H12 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
O1 W1 O1 69.66(14) . 2_665 ?
O1 W1 N1 84.81(15) 2_665 . ?
O1 W1 N1 83.66(17) . . ?
O1 W1 N3 79.78(16) 2_665 . ?
O1 W1 N3 78.77(17) . . ?
N3 W1 N1 159.77(12) . . ?
C1 W1 O1 158.0(2) . . ?
C1 W1 O1 88.3(2) . 2_665 ?
C1 W1 N1 95.1(3) . . ?
C1 W1 N3 97.4(3) . . ?
C1 W1 C2 37.1(2) . . ?
C2 W1 O1 125.5(2) . 2_665 ?
C2 W1 O1 164.8(2) . . ?
C2 W1 N1 98.16(18) . . ?
C2 W1 N3 101.43(18) . . ?
C3 W1 O1 162.1(2) . 2_665 ?
C3 W1 O1 92.8(2) . . ?
C3 W1 N1 96.9(3) . . ?
C3 W1 N3 93.9(3) . . ?
C3 W1 C1 109.1(3) . . ?
C3 W1 C2 72.0(3) . . ?
W1 O1 W1 105.65(13) . 2_665 ?
W1 O1 H11 122(5) . . ?
W1 O1 H11 132(5) 2_665 . ?
N2 N1 W1 117.5(4) . . ?
C5 N1 W1 137.2(5) . . ?
C5 N1 N2 105.3(4) . . ?
N1 N2 H21 117.2(8) . . ?
C7 N2 N1 111.0(4) . . ?
C7 N2 H21 131.4(8) . . ?
N3 N3 W1 116.71(10) 2_665 . ?
C10 N3 W1 134.9(3) . . ?
C10 N3 N3 108.3(3) . 2_665 ?
W1 C1 H1 143.7 . . ?
C2 C1 W1 72.5(4) . . ?
C2 C1 H1 143.7 . . ?
W1 C2 H2 144.8 . . ?
C1 C2 W1 70.4(4) . . ?
C1 C2 H2 144.8 . . ?
O3 C3 W1 178.3(8) . . ?
H41 C4 H42 109.5 . . ?
H41 C4 H43 109.5 . . ?
H42 C4 H43 109.5 . . ?
C5 C4 H41 109.5 . . ?
C5 C4 H42 109.5 . . ?
C5 C4 H43 109.5 . . ?
N1 C5 C4 122.3(5) . . ?
N1 C5 C6 109.8(5) . . ?
C6 C5 C4 127.9(5) . . ?
C5 C6 H6 126.7 . . ?
C7 C6 C5 106.7(4) . . ?
C7 C6 H6 126.7 . . ?
N2 C7 C6 107.2(5) . . ?
N2 C7 C8 119.8(6) . . ?
C6 C7 C8 132.9(5) . . ?
C7 C8 H81 109.5 . . ?
C7 C8 H82 109.5 . . ?
C7 C8 H83 109.5 . . ?
H81 C8 H82 109.5 . . ?
H81 C8 H83 109.5 . . ?
H82 C8 H83 109.5 . . ?
H91 C9 H92 109.5 . . ?
H91 C9 H93 109.5 . . ?
H92 C9 H93 109.5 . . ?
C10 C9 H91 109.5 . . ?
C10 C9 H92 109.5 . . ?
C10 C9 H93 109.5 . . ?
N3 C10 C9 122.5(4) . . ?
N3 C10 C11 108.1(4) . . ?
C11 C10 C9 129.3(4) . . ?
C10 C11 C10 107.1(5) 2_665 . ?
C10 C11 H111 126.4 . . ?
C10 C11 H111 126.4 2_665 . ?
Cl1 C12 Cl2 109.4(6) . . ?
Cl1 C12 H12 108.0 . . ?
Cl2 C12 H12 108.0 . . ?
Cl3 C12 Cl1 112.0(5) . . ?
Cl3 C12 Cl2 111.2(5) . . ?
Cl3 C12 H12 108.0 . . ?

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
W1 N1 N2 C7 -177.7(4) . . . . ?
W1 N1 C5 C4 -3.5(9) . . . . ?
W1 N1 C5 C6 177.1(4) . . . . ?
W1 N3 C10 C9 -2.8(18) . . . . ?
W1 N3 C10 C11 174.1(5) . . . . ?
N1 N2 C7 C6 -0.3(6) . . . . ?
N1 N2 C7 C8 -177.1(5) . . . . ?
N1 C5 C6 C7 0.6(6) . . . . ?
N2 N1 C5 C4 178.6(5) . . . . ?
N2 N1 C5 C6 -0.7(6) . . . . ?
N3 N3 C10 C9 -178.4(10) 2_665 . . . ?
N3 N3 C10 C11 -1.5(13) 2_665 . . . ?
N3 C10 C11 C10 0.6(5) . . . 2_665 ?
C4 C5 C6 C7 -178.7(6) . . . . ?
C5 N1 N2 C7 0.6(6) . . . . ?
C5 C6 C7 N2 -0.2(6) . . . . ?
C5 C6 C7 C8 176.1(6) . . . . ?
C9 C10 C11 C10 177.2(15) . . . 2_665 ?

_olex2_date_sample_data_collection 2023-12-22
_olex2_date_sample_submission    2023-12-21
_olex2_exptl_crystal_mounting_method 'mounted on a glass fiber'
_olex2_submission_original_sample_id LST363
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.404
_oxdiff_exptl_absorpt_empirical_full_min 0.750
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.495(14)
2 0.505(14)

####################################################################### 
# 
# 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_lst225-1
_database_code_depnum_ccdc_archive 'CCDC 2337532'
loop_
_audit_author_name
_audit_author_address
'Antoine Dupe'
;University of Graz
Austria
;
_audit_update_record             
;
2024-05-13 deposited with the CCDC.	2024-05-23 downloaded from the CCDC.
;
_audit_creation_date             2024-05-13
_audit_creation_method           
;
Olex2 1.5-ac6-019
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6920)
;
_shelx_SHELXL_version_number     2019/3
_audit_author_email              antoine.dupe@uni-graz.at
_chemical_name_common            ?
_chemical_name_systematic        
"carbonyl-bromo-(eta2-ethyne)-(1-(1-iminoethyl)-3,5-dimethylpyrazole-N,N')-(3,5-dimethylpyrazole-N)-tungsten(II) bromide"
_chemical_formula_moiety         'C15 H21 Br N5 O W, Br'
_chemical_formula_sum            'C15 H21 Br2 N5 O W'
_chemical_formula_weight         631.04
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C15 H21 N5 O1 Br2 W1 '
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'
Br Br -0.2901 2.4595 '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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
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                   11.3229(3)
_cell_length_b                   8.0358(2)
_cell_length_c                   21.4613(5)
_cell_angle_alpha                90
_cell_angle_beta                 95.852(2)
_cell_angle_gamma                90
_cell_volume                     1942.56(8)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    79649
_cell_measurement_temperature    100.04(10)
_cell_measurement_theta_max      38.3610
_cell_measurement_theta_min      1.8250
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    10.073
_exptl_absorpt_correction_T_max  0.04752
_exptl_absorpt_correction_T_min  0.02273
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.104a (Rigaku Oxford Diffraction, 2023)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    2.158
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1192
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_exptl_crystal_size_rad          0.400
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0911
_diffrn_reflns_av_unetI/netI     0.0212
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            159843
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.508
_diffrn_reflns_theta_min         1.908
_diffrn_ambient_environment      ?
_diffrn_ambient_temperature      100.04(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    248.17 352.54   1.20   20.00    --  -33.28 -73.76-130.25   87
  2  ω    248.17 352.54   1.20   20.00    --  -33.28 -73.76  76.75   87
  3  ω    -65.09  18.91   1.20   20.00    --  -33.28  88.88 -32.23   70
  4  ω    248.17 352.54   1.20   20.00    --  -33.28 -73.76 -28.25   87
  5  ω    -65.09  18.91   1.20   20.00    --  -33.28  88.88-137.23   70
  6  ω    248.17 352.54   1.20   20.00    --  -33.28 -73.76 127.75   87
  7  ω    -65.09  18.91   1.20   20.00    --  -33.28  88.88  69.77   70
  8  ω    -65.09  18.91   1.20   20.00    --  -33.28  88.88 171.77   70
  9  φ     -9.83 350.17   1.20   20.00  46.58 -33.28  30.17    --   300
 10  ω    -83.03  23.79   1.20   20.00    --   -3.28 -73.76  25.75   89
 11  ω    -65.09  18.91   1.20   20.00    --  -33.28  88.88 -86.23   70
 12  ω    248.17 352.54   1.20   20.00    --  -33.28 -73.76  25.75   87
 13  ω    -65.09  18.91   1.20   20.00    --  -33.28  88.88 120.77   70
 14  ω    -65.09  18.91   1.20   20.00    --  -33.28  88.88  18.77   70
 15  ω    248.17 352.54   1.20   20.00    --  -33.28 -73.76 -79.25   87
 16  ω    -98.03   8.79   1.20   20.00    --  -18.28 -73.76-154.25   89
 17  φ   -332.86  27.14   1.20   20.00  -4.81 -33.28 -77.15    --   300
 18  ω    -98.03   8.77   1.20   20.00    --  -18.28 -73.76  25.75   89
 19  ω    -98.03   8.77   1.20   20.00    --  -18.28 -73.76 115.75   89
 20  φ   -350.17   9.83   1.20   20.00 -19.42 -33.28 -30.17    --   300
 21  ω    -98.03   8.79   1.20   20.00    --  -18.28 -73.76 -64.25   89
 22  ω    248.17 352.54   1.20   20.00    --  -33.28 -73.76 178.75   87
 23  ω    -83.03  23.79   1.20   20.00    --   -3.28 -73.76 115.75   89
 24  ω    -83.03  23.79   1.20   20.00    --   -3.28 -73.76-154.25   89
 25  ω    -45.07  55.73   1.20   20.00    --   34.38 -58.90 -74.89   84
;
_diffrn_measurement_device       ?
_diffrn_measurement_device_type  'Bruker APEXII CCD'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_radiation_monochromator  'multilayer monochromator'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'Incoatec microfocus sealed tube'
_diffrn_source_type              ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5101
_reflns_number_total             5931
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_data_collection       'APEX2 (Bruker, 2014)'
_computing_data_reduction        'CrysAlisPro 1.171.43.104a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac6-019 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-019 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         1.579
_refine_diff_density_min         -0.681
_refine_diff_density_rms         0.136
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     230
_refine_ls_number_reflns         5931
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0342
_refine_ls_R_factor_gt           0.0259
_refine_ls_restrained_S_all      1.043
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0304P)²+1.5057P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0544
_refine_ls_wR_factor_ref         0.0571
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N2-H21 = N5-H5
 0.88 with sigma of 0.001
3.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C6(H6), C11(H11)
3.b Idealised Me refined as rotating group:
 C4(H41,H42,H43), C8(H81,H82,H83), C9(H91,H92,H93), C13(H131,H132,H133),
 C15(H151,H152,H153)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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
W1 W 0.22555(2) 0.22545(2) 0.38083(2) 0.02008(4) Uani 1 1 d . . . . .
Br1 Br 0.21550(3) 0.55442(4) 0.38126(2) 0.02265(7) Uani 1 1 d . . . . .
O3 O -0.0215(2) 0.2506(3) 0.30195(14) 0.0387(6) Uani 1 1 d . . . . .
N1 N 0.3293(2) 0.2668(3) 0.30370(12) 0.0237(5) Uani 1 1 d . . . . .
N2 N 0.4501(2) 0.2435(3) 0.31137(12) 0.0239(5) Uani 1 1 d D . . . .
H21 H 0.485(3) 0.193(4) 0.3447(11) 0.044(12) Uiso 1 1 d D . . . .
N3 N 0.1593(2) 0.2594(3) 0.47017(12) 0.0222(5) Uani 1 1 d . . . . .
N4 N 0.2408(2) 0.3238(3) 0.51659(12) 0.0207(5) Uani 1 1 d . . . . .
N5 N 0.3773(2) 0.2709(3) 0.44992(13) 0.0223(5) Uani 1 1 d D . . . .
H5 H 0.4523(11) 0.250(5) 0.446(2) 0.044(13) Uiso 1 1 d D . . . .
C1 C 0.1710(3) -0.0112(4) 0.36006(16) 0.0315(7) Uani 1 1 d . . . . .
H1 H 0.110643 -0.077536 0.338364 0.038 Uiso 1 1 calc R U . . .
C2 C 0.2714(3) -0.0139(4) 0.39543(16) 0.0300(7) Uani 1 1 d . . . . .
H2 H 0.330235 -0.085270 0.415704 0.036 Uiso 1 1 calc R U . . .
C3 C 0.0716(3) 0.2422(4) 0.32930(17) 0.0288(7) Uani 1 1 d . . . . .
C4 C 0.1869(3) 0.3887(5) 0.21826(16) 0.0330(7) Uani 1 1 d . . . . .
H41 H 0.134534 0.291297 0.214503 0.049 Uiso 1 1 calc R U . . .
H42 H 0.192855 0.436176 0.176644 0.049 Uiso 1 1 calc R U . . .
H43 H 0.154162 0.472144 0.245037 0.049 Uiso 1 1 calc R U . . .
C5 C 0.3072(3) 0.3376(4) 0.24659(14) 0.0254(6) Uani 1 1 d . . . . .
C6 C 0.4126(3) 0.3572(4) 0.21936(15) 0.0280(7) Uani 1 1 d . . . . .
H6 H 0.421093 0.404024 0.179420 0.034 Uiso 1 1 calc R U . . .
C7 C 0.5020(3) 0.2961(4) 0.26117(15) 0.0242(6) Uani 1 1 d . . . . .
C8 C 0.6320(3) 0.2842(4) 0.25689(16) 0.0291(7) Uani 1 1 d . . . . .
H81 H 0.671262 0.241148 0.296436 0.044 Uiso 1 1 calc R U . . .
H82 H 0.663556 0.394783 0.248747 0.044 Uiso 1 1 calc R U . . .
H83 H 0.646934 0.208791 0.222666 0.044 Uiso 1 1 calc R U . . .
C9 C -0.0567(3) 0.1988(5) 0.45828(18) 0.0331(8) Uani 1 1 d . . . . .
H91 H -0.080458 0.272537 0.422822 0.050 Uiso 1 1 calc R U . . .
H92 H -0.119829 0.195399 0.486273 0.050 Uiso 1 1 calc R U . . .
H93 H -0.042934 0.086521 0.442768 0.050 Uiso 1 1 calc R U . . .
C10 C 0.0549(3) 0.2630(4) 0.49331(16) 0.0251(6) Uani 1 1 d . . . . .
C11 C 0.0678(3) 0.3315(4) 0.55390(16) 0.0285(7) Uani 1 1 d . . . . .
H11 H 0.006522 0.347260 0.580473 0.034 Uiso 1 1 calc R U . . .
C12 C 0.1853(3) 0.3712(4) 0.56743(15) 0.0243(6) Uani 1 1 d . . . . .
C13 C 0.2417(3) 0.4608(4) 0.62346(15) 0.0272(6) Uani 1 1 d . . . . .
H131 H 0.301910 0.389254 0.645896 0.041 Uiso 1 1 calc R U . . .
H132 H 0.181013 0.489011 0.651184 0.041 Uiso 1 1 calc R U . . .
H133 H 0.279166 0.562947 0.610202 0.041 Uiso 1 1 calc R U . . .
C14 C 0.3603(3) 0.3133(4) 0.50503(14) 0.0204(6) Uani 1 1 d . . . . .
C15 C 0.4558(3) 0.3494(4) 0.55648(15) 0.0260(6) Uani 1 1 d . . . . .
H151 H 0.533458 0.327488 0.541789 0.039 Uiso 1 1 calc R U . . .
H152 H 0.445349 0.277937 0.592527 0.039 Uiso 1 1 calc R U . . .
H153 H 0.451244 0.466363 0.568903 0.039 Uiso 1 1 calc R U . . .
Br2 Br 0.63515(3) 0.10528(4) 0.42919(2) 0.02356(7) Uani 1 1 d . . . . .


_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
W1 Br1 2.6461(3) . ?
W1 N1 2.151(3) . ?
W1 N3 2.146(3) . ?
W1 N5 2.183(3) . ?
W1 C1 2.035(4) . ?
W1 C2 2.009(3) . ?
W1 C3 1.972(4) . ?
O3 C3 1.155(4) . ?
N1 N2 1.374(4) . ?
N1 C5 1.351(4) . ?
N2 H21 0.8800(10) . ?
N2 C7 1.347(4) . ?
N3 N4 1.387(3) . ?
N3 C10 1.329(4) . ?
N4 C12 1.368(4) . ?
N4 C14 1.402(4) . ?
N5 H5 0.8800(11) . ?
N5 C14 1.264(4) . ?
C1 H1 0.9500 . ?
C1 C2 1.301(5) . ?
C2 H2 0.9500 . ?
C4 H41 0.9800 . ?
C4 H42 0.9800 . ?
C4 H43 0.9800 . ?
C4 C5 1.492(5) . ?
C5 C6 1.390(5) . ?
C6 H6 0.9500 . ?
C6 C7 1.373(5) . ?
C7 C8 1.488(5) . ?
C8 H81 0.9800 . ?
C8 H82 0.9800 . ?
C8 H83 0.9800 . ?
C9 H91 0.9800 . ?
C9 H92 0.9800 . ?
C9 H93 0.9800 . ?
C9 C10 1.494(5) . ?
C10 C11 1.406(5) . ?
C11 H11 0.9500 . ?
C11 C12 1.371(5) . ?
C12 C13 1.488(4) . ?
C13 H131 0.9800 . ?
C13 H132 0.9800 . ?
C13 H133 0.9800 . ?
C14 C15 1.493(4) . ?
C15 H151 0.9800 . ?
C15 H152 0.9800 . ?
C15 H153 0.9800 . ?

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 W1 Br1 82.84(7) . . ?
N1 W1 N5 92.47(10) . . ?
N3 W1 Br1 81.43(7) . . ?
N3 W1 N1 159.36(10) . . ?
N3 W1 N5 72.20(10) . . ?
N5 W1 Br1 82.06(7) . . ?
C1 W1 Br1 157.26(10) . . ?
C1 W1 N1 98.82(12) . . ?
C1 W1 N3 100.87(12) . . ?
C1 W1 N5 120.36(12) . . ?
C2 W1 Br1 165.18(10) . . ?
C2 W1 N1 96.62(12) . . ?
C2 W1 N3 95.20(12) . . ?
C2 W1 N5 83.17(12) . . ?
C2 W1 C1 37.54(14) . . ?
C3 W1 Br1 84.13(9) . . ?
C3 W1 N1 94.52(13) . . ?
C3 W1 N3 97.07(12) . . ?
C3 W1 N5 163.61(12) . . ?
C3 W1 C1 73.12(14) . . ?
C3 W1 C2 110.65(14) . . ?
N2 N1 W1 120.12(19) . . ?
C5 N1 W1 134.2(2) . . ?
C5 N1 N2 104.9(3) . . ?
N1 N2 H21 122(3) . . ?
C7 N2 N1 111.8(3) . . ?
C7 N2 H21 126(3) . . ?
N4 N3 W1 114.95(18) . . ?
C10 N3 W1 137.9(2) . . ?
C10 N3 N4 106.0(3) . . ?
N3 N4 C14 115.7(2) . . ?
C12 N4 N3 110.5(2) . . ?
C12 N4 C14 133.5(3) . . ?
W1 N5 H5 127(3) . . ?
C14 N5 W1 119.7(2) . . ?
C14 N5 H5 113(3) . . ?
W1 C1 H1 144.9 . . ?
C2 C1 W1 70.1(2) . . ?
C2 C1 H1 144.9 . . ?
W1 C2 H2 143.8 . . ?
C1 C2 W1 72.3(2) . . ?
C1 C2 H2 143.8 . . ?
O3 C3 W1 176.4(3) . . ?
H41 C4 H42 109.5 . . ?
H41 C4 H43 109.5 . . ?
H42 C4 H43 109.5 . . ?
C5 C4 H41 109.5 . . ?
C5 C4 H42 109.5 . . ?
C5 C4 H43 109.5 . . ?
N1 C5 C4 124.2(3) . . ?
N1 C5 C6 110.0(3) . . ?
C6 C5 C4 125.8(3) . . ?
C5 C6 H6 126.5 . . ?
C7 C6 C5 107.0(3) . . ?
C7 C6 H6 126.5 . . ?
N2 C7 C6 106.4(3) . . ?
N2 C7 C8 123.0(3) . . ?
C6 C7 C8 130.6(3) . . ?
C7 C8 H81 109.5 . . ?
C7 C8 H82 109.5 . . ?
C7 C8 H83 109.5 . . ?
H81 C8 H82 109.5 . . ?
H81 C8 H83 109.5 . . ?
H82 C8 H83 109.5 . . ?
H91 C9 H92 109.5 . . ?
H91 C9 H93 109.5 . . ?
H92 C9 H93 109.5 . . ?
C10 C9 H91 109.5 . . ?
C10 C9 H92 109.5 . . ?
C10 C9 H93 109.5 . . ?
N3 C10 C9 122.9(3) . . ?
N3 C10 C11 110.0(3) . . ?
C11 C10 C9 127.1(3) . . ?
C10 C11 H11 126.4 . . ?
C12 C11 C10 107.1(3) . . ?
C12 C11 H11 126.4 . . ?
N4 C12 C11 106.4(3) . . ?
N4 C12 C13 125.8(3) . . ?
C11 C12 C13 127.7(3) . . ?
C12 C13 H131 109.5 . . ?
C12 C13 H132 109.5 . . ?
C12 C13 H133 109.5 . . ?
H131 C13 H132 109.5 . . ?
H131 C13 H133 109.5 . . ?
H132 C13 H133 109.5 . . ?
N4 C14 C15 119.8(3) . . ?
N5 C14 N4 115.1(3) . . ?
N5 C14 C15 125.2(3) . . ?
C14 C15 H151 109.5 . . ?
C14 C15 H152 109.5 . . ?
C14 C15 H153 109.5 . . ?
H151 C15 H152 109.5 . . ?
H151 C15 H153 109.5 . . ?
H152 C15 H153 109.5 . . ?

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
W1 N1 N2 C7 -171.7(2) . . . . ?
W1 N1 C5 C4 -9.5(5) . . . . ?
W1 N1 C5 C6 169.7(2) . . . . ?
W1 N3 N4 C12 168.13(19) . . . . ?
W1 N3 N4 C14 -17.5(3) . . . . ?
W1 N3 C10 C9 15.7(5) . . . . ?
W1 N3 C10 C11 -165.4(2) . . . . ?
W1 N5 C14 N4 1.2(4) . . . . ?
W1 N5 C14 C15 -179.5(2) . . . . ?
N1 N2 C7 C6 0.5(4) . . . . ?
N1 N2 C7 C8 -179.5(3) . . . . ?
N1 C5 C6 C7 0.1(4) . . . . ?
N2 N1 C5 C4 -179.0(3) . . . . ?
N2 N1 C5 C6 0.2(4) . . . . ?
N3 N4 C12 C11 1.9(3) . . . . ?
N3 N4 C12 C13 -173.5(3) . . . . ?
N3 N4 C14 N5 10.7(4) . . . . ?
N3 N4 C14 C15 -168.7(3) . . . . ?
N3 C10 C11 C12 0.3(4) . . . . ?
N4 N3 C10 C9 -178.1(3) . . . . ?
N4 N3 C10 C11 0.9(3) . . . . ?
C4 C5 C6 C7 179.2(3) . . . . ?
C5 N1 N2 C7 -0.4(3) . . . . ?
C5 C6 C7 N2 -0.3(4) . . . . ?
C5 C6 C7 C8 179.6(3) . . . . ?
C9 C10 C11 C12 179.2(3) . . . . ?
C10 N3 N4 C12 -1.8(3) . . . . ?
C10 N3 N4 C14 172.7(3) . . . . ?
C10 C11 C12 N4 -1.3(4) . . . . ?
C10 C11 C12 C13 174.0(3) . . . . ?
C12 N4 C14 N5 -176.5(3) . . . . ?
C12 N4 C14 C15 4.1(5) . . . . ?
C14 N4 C12 C11 -171.1(3) . . . . ?
C14 N4 C12 C13 13.4(5) . . . . ?

_olex2_date_sample_data_collection 2023-02-22
_olex2_date_sample_submission    2023-02-21
_olex2_submission_original_sample_id LST225
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.742
_oxdiff_exptl_absorpt_empirical_full_min 0.482
