# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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_new
_database_code_depnum_ccdc_archive 'CCDC 1438097'
_audit_update_record             
;
2015-11-20 deposited with the CCDC.
2016-02-15 downloaded from the CCDC.
;



_audit_creation_method           SHELXL-97

_chemical_name_systematic        
;

 ?

;

_chemical_name_common            ?

_chemical_melting_point          ?

_chemical_formula_moiety         ' 	C44 H60 N8 O6 Ti2 '

_chemical_formula_sum            ' 	C44 H60 N8 O6 Ti2 '

_chemical_formula_weight         892.74



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'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'



_symmetry_cell_setting           Monoclinic

_symmetry_space_group_name_H-M   C2/c

_symmetry_space_group_name_Hall  '-C 2yc '


loop_

_symmetry_equiv_pos_as_xyz








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



_cell_length_a                   11.1634(4)

_cell_length_b                   24.5170(9)

_cell_length_c                   17.6569(6)

_cell_angle_alpha                90.00

_cell_angle_beta                 94.8010(10)

_cell_angle_gamma                90.00

_cell_volume                     4815.6(3)

_cell_formula_units_Z            4

_cell_measurement_temperature    298(2)

_cell_measurement_reflns_used    7041

_cell_measurement_theta_min      2.40

_cell_measurement_theta_max      28.29



_exptl_crystal_description       Rectangular

_exptl_crystal_colour            metallic

_exptl_crystal_size_max          0.35

_exptl_crystal_size_mid          0.25

_exptl_crystal_size_min          0.15

_exptl_crystal_density_meas      ?

_exptl_crystal_density_diffrn    1.231

_exptl_crystal_density_method    'not measured'

_exptl_crystal_F_000             1888

_exptl_absorpt_coefficient_mu    0.383

_exptl_absorpt_correction_type   multi-scan

_exptl_absorpt_correction_T_min  0.8775

_exptl_absorpt_correction_T_max  0.9447

_exptl_absorpt_process_details   'SADABS (Bruker,2004)'



_exptl_special_details           
;

 ?

;



_diffrn_ambient_temperature      298(2)

_diffrn_radiation_wavelength     0.71073

_diffrn_radiation_type           MoK\a

_diffrn_radiation_source         'fine-focus sealed tube'

_diffrn_radiation_monochromator  graphite

_diffrn_measurement_device_type  'Bruker APEXII CCD area detector'

_diffrn_measurement_method       'phi and omega scans'

_diffrn_detector_area_resol_mean ?

_diffrn_standards_number         ?

_diffrn_standards_interval_count ?

_diffrn_standards_interval_time  ?

_diffrn_standards_decay_%        ?

_diffrn_reflns_number            17890

_diffrn_reflns_av_R_equivalents  0.0217

_diffrn_reflns_av_sigmaI/netI    0.0249

_diffrn_reflns_limit_h_min       -12

_diffrn_reflns_limit_h_max       12

_diffrn_reflns_limit_k_min       -32

_diffrn_reflns_limit_k_max       32

_diffrn_reflns_limit_l_min       -16

_diffrn_reflns_limit_l_max       23

_diffrn_reflns_theta_min         1.66

_diffrn_reflns_theta_max         28.30

_reflns_number_total             5380

_reflns_number_gt                4212

_reflns_threshold_expression     >2sigma(I)



_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'SHELXL-97 (Sheldrick, 2008)'




_refine_special_details          
;

 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     
'calc w=1/[σ²(Fo²)+(0.0502P)²+4.7177P] where P=(Fo²+2Fc²)/3'

_atom_sites_solution_primary     direct

_atom_sites_solution_secondary   difmap

_atom_sites_solution_hydrogens   geom

_refine_ls_hydrogen_treatment    mixed

_refine_ls_extinction_method     none

_refine_ls_extinction_coef       ?

_refine_ls_number_reflns         5380

_refine_ls_number_parameters     279

_refine_ls_number_restraints     0

_refine_ls_R_factor_all          0.0538

_refine_ls_R_factor_gt           0.0384

_refine_ls_wR_factor_ref         0.1113

_refine_ls_wR_factor_gt          0.1006

_refine_ls_goodness_of_fit_ref   1.022

_refine_ls_restrained_S_all      1.022

_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_symmetry_multiplicity

_atom_site_calc_flag

_atom_site_refinement_flags

_atom_site_disorder_assembly

_atom_site_disorder_group




























































C1 C 0.6748(2) 0.24567(10) 0.26755(12) 0.0570(6) Uani 1 1 d . . .
C2 C 0.7044(2) 0.21863(8) 0.19828(10) 0.0429(5) Uani 1 1 d . . .
C3 C 0.7717(2) 0.17173(8) 0.20197(10) 0.0428(5) Uani 1 1 d . . .
C4 C 0.8244(2) 0.14735(9) 0.26919(11) 0.0542(6) Uani 1 1 d . . .
C5 C 0.82141(19) 0.09813(7) 0.12523(10) 0.0399(4) Uani 1 1 d . . .
H5 H 0.8522 0.0816 0.1701 0.048 Uiso 1 1 calc R . .
C6 C 0.82388(18) 0.06709(7) 0.05676(10) 0.0364(4) Uani 1 1 d . . .
C7 C 0.84806(19) 0.01097(8) 0.06528(12) 0.0430(5) Uani 1 1 d . . .
H7 H 0.8652 -0.0034 0.1137 0.052 Uiso 1 1 calc R . .
C8 C 0.84677(19) -0.02290(7) 0.00355(12) 0.0432(5) Uani 1 1 d . . .
C9 C 0.82429(19) 0.00044(8) -0.06813(12) 0.0449(5) Uani 1 1 d . . .
H9 H 0.8241 -0.0224 -0.1102 0.054 Uiso 1 1 calc R . .
C10 C 0.80202(19) 0.05570(8) -0.08109(11) 0.0407(4) Uani 1 1 d . . .
C11 C 0.80121(17) 0.08980(7) -0.01663(10) 0.0348(4) Uani 1 1 d . . .
C12 C 0.7825(3) 0.07807(10) -0.16257(12) 0.0597(6) Uani 1 1 d . . .
C13 C 0.7851(4) 0.03305(13) -0.22265(15) 0.1061(13) Uani 1 1 d . . .
H13A H 0.7223 0.0072 -0.2159 0.159 Uiso 1 1 calc R . .
H13B H 0.8615 0.0149 -0.2172 0.159 Uiso 1 1 calc R . .
H13C H 0.7732 0.0489 -0.2724 0.159 Uiso 1 1 calc R . .
C14 C 0.6647(3) 0.10864(17) -0.17485(17) 0.1120(14) Uani 1 1 d . . .
H14A H 0.5995 0.0846 -0.1660 0.168 Uiso 1 1 calc R . .
H14B H 0.6549 0.1219 -0.2261 0.168 Uiso 1 1 calc R . .
H14C H 0.6651 0.1388 -0.1402 0.168 Uiso 1 1 calc R . .
C15 C 0.8867(4) 0.11711(13) -0.17558(17) 0.0940(11) Uani 1 1 d . . .
H15A H 0.8720 0.1344 -0.2242 0.141 Uiso 1 1 calc R . .
H15B H 0.9605 0.0969 -0.1742 0.141 Uiso 1 1 calc R . .
H15C H 0.8927 0.1444 -0.1364 0.141 Uiso 1 1 calc R . .
C16 C 0.8696(2) -0.08337(8) 0.01221(15) 0.0581(6) Uani 1 1 d . . .
H16A H 0.9538 -0.0905 0.0101 0.087 Uiso 1 1 calc R . .
H16B H 0.8247 -0.1026 -0.0282 0.087 Uiso 1 1 calc R . .
H16C H 0.8449 -0.0954 0.0602 0.087 Uiso 1 1 calc R . .
C17 C 0.4677(3) 0.12124(10) 0.04627(19) 0.0729(8) Uani 1 1 d . . .
H17 H 0.3933 0.1409 0.0306 0.087 Uiso 1 1 calc R . .
C18 C 0.4706(4) 0.07240(15) 0.0001(4) 0.171(3) Uani 1 1 d . . .
H18A H 0.4651 0.0823 -0.0526 0.256 Uiso 1 1 calc R . .
H18B H 0.4041 0.0493 0.0097 0.256 Uiso 1 1 calc R . .
H18C H 0.5446 0.0532 0.0127 0.256 Uiso 1 1 calc R . .
C19 C 0.4702(5) 0.1114(2) 0.1289(3) 0.178(3) Uani 1 1 d . . .
H19A H 0.5368 0.0882 0.1447 0.268 Uiso 1 1 calc R . .
H19B H 0.3966 0.0942 0.1404 0.268 Uiso 1 1 calc R . .
H19C H 0.4787 0.1456 0.1555 0.268 Uiso 1 1 calc R . .
C20 C 0.97173(18) 0.23015(8) 0.06605(11) 0.0425(5) Uani 1 1 d . . .
H20 H 0.9644 0.1938 0.0882 0.051 Uiso 1 1 calc R . .
C21 C 1.0629(2) 0.22657(10) 0.00810(15) 0.0616(6) Uani 1 1 d . . .
H21A H 1.0346 0.2019 -0.0316 0.092 Uiso 1 1 calc R . .
H21B H 1.1378 0.2135 0.0321 0.092 Uiso 1 1 calc R . .
H21C H 1.0745 0.2620 -0.0131 0.092 Uiso 1 1 calc R . .
C22 C 1.0074(2) 0.26880(11) 0.12988(15) 0.0670(7) Uani 1 1 d . . .
H22A H 1.0204 0.3044 0.1096 0.101 Uiso 1 1 calc R . .
H22B H 1.0800 0.2562 0.1572 0.101 Uiso 1 1 calc R . .
H22C H 0.9444 0.2705 0.1637 0.101 Uiso 1 1 calc R . .
N1 N 0.66400(17) 0.23804(6) 0.13092(9) 0.0435(4) Uani 1 1 d . . .
H1 H 0.6247 0.2682 0.1274 0.052 Uiso 1 1 calc R . .
N2 N 0.78003(15) 0.14734(6) 0.13036(8) 0.0358(3) Uani 1 1 d . . .
N3 N 0.6481(3) 0.26720(11) 0.32020(12) 0.0900(8) Uani 1 1 d . . .
N4 N 0.8699(3) 0.12547(10) 0.32093(12) 0.0852(8) Uani 1 1 d . . .
O1 O 0.78401(13) 0.14392(5) -0.02271(7) 0.0388(3) Uani 1 1 d . . .
O2 O 0.56565(13) 0.15553(5) 0.03155(8) 0.0473(3) Uani 1 1 d . . .
O3 O 0.85350(11) 0.24550(5) 0.03074(7) 0.0336(3) Uani 1 1 d . . .
Ti1 Ti 0.69711(3) 0.194286(12) 0.033167(16) 0.03131(10) 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

































































C1 N3 1.131(3) . ?
C1 C2 1.453(3) . ?
C2 N1 1.325(3) . ?
C2 C3 1.372(3) . ?
C3 N2 1.409(2) . ?
C3 C4 1.412(3) . ?
C4 N4 1.142(3) . ?
C5 N2 1.298(2) . ?
C5 C6 1.431(3) . ?
C5 H5 0.9300 . ?
C6 C7 1.408(2) . ?
C6 C11 1.414(2) . ?
C7 C8 1.369(3) . ?
C7 H7 0.9300 . ?
C8 C9 1.393(3) . ?
C8 C16 1.510(3) . ?
C9 C10 1.393(3) . ?
C9 H9 0.9300 . ?
C10 C11 1.413(2) . ?
C10 C12 1.538(3) . ?
C11 O1 1.344(2) . ?
C12 C14 1.513(4) . ?
C12 C13 1.533(3) . ?
C12 C15 1.539(4) . ?
C13 H13A 0.9600 . ?
C13 H13B 0.9600 . ?
C13 H13C 0.9600 . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?
C16 H16A 0.9600 . ?
C16 H16B 0.9600 . ?
C16 H16C 0.9600 . ?
C17 O2 1.420(3) . ?
C17 C18 1.450(4) . ?
C17 C19 1.477(5) . ?
C17 H17 0.9800 . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 O3 1.461(2) . ?
C20 C22 1.500(3) . ?
C20 C21 1.505(3) . ?
C20 H20 0.9800 . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
C22 H22A 0.9600 . ?
C22 H22B 0.9600 . ?
C22 H22C 0.9600 . ?
N1 Ti1 2.0912(16) . ?
N1 H1 0.8600 . ?
N2 Ti1 2.2047(15) . ?
O1 Ti1 1.8972(13) . ?
O2 Ti1 1.7466(14) . ?
O3 Ti1 1.9145(12) 7_655 ?
O3 Ti1 2.1538(13) . ?
Ti1 O3 1.9145(12) 7_655 ?
Ti1 Ti1 3.2343(6) 7_655 ?



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































































































































N3 C1 C2 177.6(3) . . ?
N1 C2 C3 119.18(17) . . ?
N1 C2 C1 120.49(19) . . ?
C3 C2 C1 120.30(18) . . ?
C2 C3 N2 112.97(16) . . ?
C2 C3 C4 125.61(18) . . ?
N2 C3 C4 121.36(18) . . ?
N4 C4 C3 176.0(3) . . ?
N2 C5 C6 125.85(17) . . ?
N2 C5 H5 117.1 . . ?
C6 C5 H5 117.1 . . ?
C7 C6 C11 120.07(17) . . ?
C7 C6 C5 116.53(17) . . ?
C11 C6 C5 123.39(16) . . ?
C8 C7 C6 121.23(18) . . ?
C8 C7 H7 119.4 . . ?
C6 C7 H7 119.4 . . ?
C7 C8 C9 117.61(17) . . ?
C7 C8 C16 121.63(19) . . ?
C9 C8 C16 120.76(19) . . ?
C8 C9 C10 124.40(18) . . ?
C8 C9 H9 117.8 . . ?
C10 C9 H9 117.8 . . ?
C9 C10 C11 117.16(18) . . ?
C9 C10 C12 120.64(17) . . ?
C11 C10 C12 122.18(17) . . ?
O1 C11 C10 122.04(16) . . ?
O1 C11 C6 118.40(15) . . ?
C10 C11 C6 119.51(16) . . ?
C14 C12 C13 108.9(3) . . ?
C14 C12 C10 111.3(2) . . ?
C13 C12 C10 112.4(2) . . ?
C14 C12 C15 109.2(3) . . ?
C13 C12 C15 106.6(2) . . ?
C10 C12 C15 108.2(2) . . ?
C12 C13 H13A 109.5 . . ?
C12 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C12 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C12 C14 H14A 109.5 . . ?
C12 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C12 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C12 C15 H15A 109.5 . . ?
C12 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C12 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
C8 C16 H16A 109.5 . . ?
C8 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
C8 C16 H16C 109.5 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
O2 C17 C18 109.4(3) . . ?
O2 C17 C19 109.0(3) . . ?
C18 C17 C19 114.9(4) . . ?
O2 C17 H17 107.8 . . ?
C18 C17 H17 107.8 . . ?
C19 C17 H17 107.8 . . ?
C17 C18 H18A 109.5 . . ?
C17 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C17 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C17 C19 H19A 109.5 . . ?
C17 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C17 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
O3 C20 C22 109.34(17) . . ?
O3 C20 C21 111.29(17) . . ?
C22 C20 C21 113.3(2) . . ?
O3 C20 H20 107.6 . . ?
C22 C20 H20 107.6 . . ?
C21 C20 H20 107.6 . . ?
C20 C21 H21A 109.5 . . ?
C20 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C20 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C20 C22 H22A 109.5 . . ?
C20 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C20 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
C2 N1 Ti1 119.10(13) . . ?
C2 N1 H1 120.4 . . ?
Ti1 N1 H1 120.4 . . ?
C5 N2 C3 120.52(16) . . ?
C5 N2 Ti1 124.04(12) . . ?
C3 N2 Ti1 114.96(12) . . ?
C11 O1 Ti1 132.61(11) . . ?
C17 O2 Ti1 167.87(17) . . ?
C20 O3 Ti1 131.42(11) . 7_655 ?
C20 O3 Ti1 123.11(10) . . ?
Ti1 O3 Ti1 105.16(6) 7_655 . ?
O2 Ti1 O1 95.91(7) . . ?
O2 Ti1 O3 101.76(6) . 7_655 ?
O1 Ti1 O3 109.51(5) . 7_655 ?
O2 Ti1 N1 94.95(7) . . ?
O1 Ti1 N1 153.70(7) . . ?
O3 Ti1 N1 91.55(6) 7_655 . ?
O2 Ti1 O3 176.59(6) . . ?
O1 Ti1 O3 85.32(5) . . ?
O3 Ti1 O3 74.84(6) 7_655 . ?
N1 Ti1 O3 85.24(6) . . ?
O2 Ti1 N2 91.50(6) . . ?
O1 Ti1 N2 82.26(5) . . ?
O3 Ti1 N2 160.97(6) 7_655 . ?
N1 Ti1 N2 73.57(6) . . ?
O3 Ti1 N2 91.81(5) . . ?
O2 Ti1 Ti1 141.75(5) . 7_655 ?
O1 Ti1 Ti1 98.24(4) . 7_655 ?
O3 Ti1 Ti1 40.00(4) 7_655 7_655 ?
N1 Ti1 Ti1 87.75(5) . 7_655 ?
O3 Ti1 Ti1 34.84(3) . 7_655 ?
N2 Ti1 Ti1 125.50(4) . 7_655 ?



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

























































































N3 C1 C2 N1 33(7) . . . . ?
N3 C1 C2 C3 -145(7) . . . . ?
N1 C2 C3 N2 -5.2(3) . . . . ?
C1 C2 C3 N2 172.9(2) . . . . ?
N1 C2 C3 C4 177.6(2) . . . . ?
C1 C2 C3 C4 -4.4(4) . . . . ?
C2 C3 C4 N4 -176(100) . . . . ?
N2 C3 C4 N4 7(4) . . . . ?
N2 C5 C6 C7 -166.7(2) . . . . ?
N2 C5 C6 C11 12.0(3) . . . . ?
C11 C6 C7 C8 -1.9(3) . . . . ?
C5 C6 C7 C8 176.8(2) . . . . ?
C6 C7 C8 C9 1.9(3) . . . . ?
C6 C7 C8 C16 -178.5(2) . . . . ?
C7 C8 C9 C10 -0.6(3) . . . . ?
C16 C8 C9 C10 179.8(2) . . . . ?
C8 C9 C10 C11 -0.7(3) . . . . ?
C8 C9 C10 C12 177.8(2) . . . . ?
C9 C10 C11 O1 178.10(18) . . . . ?
C12 C10 C11 O1 -0.4(3) . . . . ?
C9 C10 C11 C6 0.7(3) . . . . ?
C12 C10 C11 C6 -177.8(2) . . . . ?
C7 C6 C11 O1 -176.95(18) . . . . ?
C5 C6 C11 O1 4.4(3) . . . . ?
C7 C6 C11 C10 0.5(3) . . . . ?
C5 C6 C11 C10 -178.10(19) . . . . ?
C9 C10 C12 C14 125.1(3) . . . . ?
C11 C10 C12 C14 -56.5(3) . . . . ?
C9 C10 C12 C13 2.6(4) . . . . ?
C11 C10 C12 C13 -179.0(3) . . . . ?
C9 C10 C12 C15 -114.9(2) . . . . ?
C11 C10 C12 C15 63.6(3) . . . . ?
C3 C2 N1 Ti1 3.0(3) . . . . ?
C1 C2 N1 Ti1 -175.05(17) . . . . ?
C6 C5 N2 C3 173.76(19) . . . . ?
C6 C5 N2 Ti1 2.1(3) . . . . ?
C2 C3 N2 C5 -167.49(19) . . . . ?
C4 C3 N2 C5 9.9(3) . . . . ?
C2 C3 N2 Ti1 4.9(2) . . . . ?
C4 C3 N2 Ti1 -177.74(17) . . . . ?
C10 C11 O1 Ti1 140.72(16) . . . . ?
C6 C11 O1 Ti1 -41.9(3) . . . . ?
C18 C17 O2 Ti1 -112.4(8) . . . . ?
C19 C17 O2 Ti1 14.1(9) . . . . ?
C22 C20 O3 Ti1 72.2(2) . . . 7_655 ?
C21 C20 O3 Ti1 -53.8(2) . . . 7_655 ?
C22 C20 O3 Ti1 -115.21(17) . . . . ?
C21 C20 O3 Ti1 118.86(16) . . . . ?
C17 O2 Ti1 O1 102.2(7) . . . . ?
C17 O2 Ti1 O3 -146.4(7) . . . 7_655 ?
C17 O2 Ti1 N1 -53.8(7) . . . . ?
C17 O2 Ti1 O3 -146.7(10) . . . . ?
C17 O2 Ti1 N2 19.9(7) . . . . ?
C17 O2 Ti1 Ti1 -146.4(7) . . . 7_655 ?
C11 O1 Ti1 O2 -47.84(17) . . . . ?
C11 O1 Ti1 O3 -152.55(16) . . . 7_655 ?
C11 O1 Ti1 N1 66.1(2) . . . . ?
C11 O1 Ti1 O3 135.35(17) . . . . ?
C11 O1 Ti1 N2 42.87(16) . . . . ?
C11 O1 Ti1 Ti1 167.79(16) . . . 7_655 ?
C2 N1 Ti1 O2 89.99(17) . . . . ?
C2 N1 Ti1 O1 -24.1(3) . . . . ?
C2 N1 Ti1 O3 -168.07(16) . . . 7_655 ?
C2 N1 Ti1 O3 -93.42(16) . . . . ?
C2 N1 Ti1 N2 -0.12(15) . . . . ?
C2 N1 Ti1 Ti1 -128.24(16) . . . 7_655 ?
C20 O3 Ti1 O2 -173.9(10) . . . . ?
Ti1 O3 Ti1 O2 0.4(11) 7_655 . . . ?
C20 O3 Ti1 O1 -62.61(13) . . . . ?
Ti1 O3 Ti1 O1 111.67(6) 7_655 . . . ?
C20 O3 Ti1 O3 -174.28(16) . . . 7_655 ?
Ti1 O3 Ti1 O3 0.0 7_655 . . 7_655 ?
C20 O3 Ti1 N1 92.81(13) . . . . ?
Ti1 O3 Ti1 N1 -92.90(7) 7_655 . . . ?
C20 O3 Ti1 N2 19.47(13) . . . . ?
Ti1 O3 Ti1 N2 -166.25(6) 7_655 . . . ?
C20 O3 Ti1 Ti1 -174.28(16) . . . 7_655 ?
C5 N2 Ti1 O2 74.74(17) . . . . ?
C3 N2 Ti1 O2 -97.36(14) . . . . ?
C5 N2 Ti1 O1 -21.02(16) . . . . ?
C3 N2 Ti1 O1 166.88(14) . . . . ?
C5 N2 Ti1 O3 -150.77(18) . . . 7_655 ?
C3 N2 Ti1 O3 37.1(3) . . . 7_655 ?
C5 N2 Ti1 N1 169.46(18) . . . . ?
C3 N2 Ti1 N1 -2.64(13) . . . . ?
C5 N2 Ti1 O3 -106.05(16) . . . . ?
C3 N2 Ti1 O3 81.85(14) . . . . ?
C5 N2 Ti1 Ti1 -115.65(15) . . . 7_655 ?
C3 N2 Ti1 Ti1 72.25(14) . . . 7_655 ?



_diffrn_measured_fraction_theta_max 0.899

_diffrn_reflns_theta_full        25.00

_diffrn_measured_fraction_theta_full 0.936

_refine_diff_density_max         0.276

_refine_diff_density_min         -0.229

_refine_diff_density_rms         0.046

_vrf_PLAT029_new                 
;
PROBLEM: _diffrn_measured_fraction_theta_full Low .......      0.936 Note  
RESPONSE: Even though crystal data was collected up to 0.73 \%A 
resolution, the crystal (the largest available) still 
diffracted quite weakly at high angle. On repeated recrystallisation
we could get only small sized crystals.

;
####################################################################### 
# 
# 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_DMNZR
_database_code_depnum_ccdc_archive 'CCDC 1438098'
_audit_update_record             
;
2015-11-20 deposited with the CCDC.
2016-02-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C48 H68 Cl4 N8 O6 Zr2'
_chemical_formula_weight         1177.34

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'
Zr Zr -2.9673 0.5597 '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'

_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                   9.9338(13)
_cell_length_b                   11.1209(15)
_cell_length_c                   14.560(2)
_cell_angle_alpha                106.403(6)
_cell_angle_beta                 91.013(7)
_cell_angle_gamma                108.188(6)
_cell_volume                     1456.0(4)
_cell_formula_units_Z            1
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    6834
_cell_measurement_theta_min      2.8
_cell_measurement_theta_max      25.1

_exptl_crystal_description       block
_exptl_crystal_colour            brown
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_F_000             608
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.150
_exptl_absorpt_coefficient_mu    0.591
_shelx_estimated_absorpt_T_min   0.866
_shelx_estimated_absorpt_T_max   0.917
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.721
_exptl_absorpt_correction_T_max  0.834
_exptl_absorpt_process_details   'SADABS (Bruer, 1999)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Sealed tube'
_diffrn_measurement_device_type  'Bruker axs kappa apex2 CCD Diffractometer'
_diffrn_measurement_method       'ω and φ scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            15810
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.023
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_full        24.998
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measured_fraction_theta_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_point_group_measured_fraction_full 0.962
_reflns_number_total             4933
_reflns_number_gt                4096
_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       'APEX2 (Bruker, 2004)'
_computing_cell_refinement       'APEX2/SAINT (Bruker, 2004)'
_computing_data_reduction        'SAINT/XPREP (Bruker, 2004)'
_computing_structure_solution    'SIR92 (Altornare et al., 1993)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    
'ORTEP3 (Farrugia, 1997) and Mercury (Bruno et al., 2002)'
_computing_publication_material  'SHELXL-2014 (Sheldrick, 2014)'

_refine_special_details          ?
_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+2.2679P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_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         4933
_refine_ls_number_parameters     356
_refine_ls_number_restraints     156
_refine_ls_R_factor_all          0.0640
_refine_ls_R_factor_gt           0.0483
_refine_ls_wR_factor_ref         0.1496
_refine_ls_wR_factor_gt          0.1281
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_restrained_S_all      1.158
_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
C1 C 0.8490(5) 0.9201(4) 0.7101(3) 0.0375(9) Uani 1 1 d . . . . .
C2 C 0.7955(5) 1.0007(4) 0.6718(3) 0.0447(10) Uani 1 1 d . . . . .
C3 C 0.7820(6) 0.9743(5) 0.5728(4) 0.0572(13) Uani 1 1 d . . . . .
H3 H 0.7481 1.0285 0.5472 0.069 Uiso 1 1 calc R U . . .
C4 C 0.8163(6) 0.8710(6) 0.5090(3) 0.0601(14) Uani 1 1 d . . . . .
C5 C 0.8646(6) 0.7910(5) 0.5470(3) 0.0563(13) Uani 1 1 d . . . . .
H5 H 0.8870 0.7208 0.5060 0.068 Uiso 1 1 calc R U . . .
C6 C 0.8812(5) 0.8129(4) 0.6468(3) 0.0438(10) Uani 1 1 d . . . . .
C7 C 0.9368(6) 0.7252(5) 0.6799(3) 0.0497(12) Uani 1 1 d . . . . .
H7 H 0.9608 0.6617 0.6327 0.060 Uiso 1 1 calc R U . . .
C8 C 0.7589(6) 1.1195(5) 0.7378(4) 0.0535(12) Uani 1 1 d . . . . .
C9 C 0.6516(7) 1.0726(7) 0.8047(5) 0.0827(19) Uani 1 1 d . . . . .
H9A H 0.6937 1.0378 0.8465 0.124 Uiso 1 1 calc R U . . .
H9B H 0.5679 1.0045 0.7670 0.124 Uiso 1 1 calc R U . . .
H9C H 0.6257 1.1462 0.8427 0.124 Uiso 1 1 calc R U . . .
C10 C 0.6933(11) 1.1862(8) 0.6792(5) 0.117(3) Uani 1 1 d . . . . .
H10A H 0.6739 1.2604 0.7222 0.176 Uiso 1 1 calc R U . . .
H10B H 0.6060 1.1235 0.6423 0.176 Uiso 1 1 calc R U . . .
H10C H 0.7589 1.2165 0.6364 0.176 Uiso 1 1 calc R U . . .
C11 C 0.8931(7) 1.2212(6) 0.7974(5) 0.0773(18) Uani 1 1 d . . . . .
H11A H 0.9591 1.2537 0.7556 0.116 Uiso 1 1 calc R U . . .
H11B H 0.9355 1.1810 0.8349 0.116 Uiso 1 1 calc R U . . .
H11C H 0.8701 1.2937 0.8398 0.116 Uiso 1 1 calc R U . . .
C12 C 0.7979(9) 0.8480(7) 0.4009(4) 0.088(2) Uani 1 1 d . . . . .
H12A H 0.8663 0.9199 0.3853 0.131 Uiso 1 1 calc R U . . .
H12B H 0.7032 0.8437 0.3813 0.131 Uiso 1 1 calc R U . . .
H12C H 0.8124 0.7660 0.3678 0.131 Uiso 1 1 calc R U . . .
C13 C 1.0176(5) 0.6338(4) 0.7869(3) 0.0445(11) Uani 1 1 d . . . . .
C14 C 1.0381(5) 0.6434(4) 0.8825(3) 0.0429(10) Uani 1 1 d . . . . .
C15 C 1.0545(7) 0.5413(5) 0.7127(4) 0.0623(15) Uani 1 1 d . . . . .
C16 C 1.1054(6) 0.5590(5) 0.9101(4) 0.0553(12) Uani 1 1 d . . . . .
C17 C 0.7823(6) 0.9798(6) 1.1081(4) 0.0575(13) Uani 1 1 d . . . . .
H17 H 0.8245 1.0541 1.1667 0.069 Uiso 1 1 calc R U . . .
C18 C 0.6647(7) 1.0087(8) 1.0653(6) 0.088(2) Uani 1 1 d . . . . .
H18A H 0.7020 1.0905 1.0500 0.132 Uiso 1 1 calc R U . . .
H18B H 0.5964 1.0165 1.1105 0.132 Uiso 1 1 calc R U . . .
H18C H 0.6192 0.9378 1.0076 0.132 Uiso 1 1 calc R U . . .
C19 C 0.7393(7) 0.8576(7) 1.1384(5) 0.084(2) Uani 1 1 d . . . . .
H19A H 0.6964 0.7816 1.0832 0.127 Uiso 1 1 calc R U . . .
H19B H 0.6719 0.8636 1.1845 0.127 Uiso 1 1 calc R U . . .
H19C H 0.8219 0.8485 1.1672 0.127 Uiso 1 1 calc R U . . .
C20 C 0.5683(7) 0.6433(7) 0.8739(6) 0.0852(19) Uani 1 1 d . . . . .
H20 H 0.5220 0.6651 0.9323 0.102 Uiso 1 1 calc R U . . .
C21 C 0.4809(9) 0.6530(10) 0.7956(7) 0.128(3) Uani 1 1 d . . . . .
H21A H 0.4684 0.7385 0.8138 0.192 Uiso 1 1 calc R U . . .
H21B H 0.3894 0.5848 0.7838 0.192 Uiso 1 1 calc R U . . .
H21C H 0.5277 0.6421 0.7382 0.192 Uiso 1 1 calc R U . . .
C22 C 0.5825(11) 0.5125(7) 0.8637(9) 0.145(4) Uani 1 1 d . . . . .
H22A H 0.6210 0.4837 0.8046 0.217 Uiso 1 1 calc R U . . .
H22B H 0.4904 0.4495 0.8628 0.217 Uiso 1 1 calc R U . . .
H22C H 0.6452 0.5189 0.9171 0.217 Uiso 1 1 calc R U . . .
N1 N 1.0008(5) 0.7324(4) 0.9492(3) 0.0490(10) Uani 1 1 d . . . . .
N2 N 0.9569(4) 0.7251(3) 0.7683(3) 0.0409(8) Uani 1 1 d . . . . .
N3 N 1.1607(6) 0.4964(6) 0.9354(4) 0.0847(16) Uani 1 1 d . . . . .
N4 N 1.0823(8) 0.4679(6) 0.6504(4) 0.105(2) Uani 1 1 d . . . . .
O1 O 0.8718(3) 0.9430(3) 0.8052(2) 0.0420(7) Uani 1 1 d . . . . .
O2 O 0.8932(3) 0.9798(3) 1.0453(2) 0.0373(6) Uani 1 1 d . . . . .
O3 O 0.7068(3) 0.7409(3) 0.8918(2) 0.0543(8) Uani 1 1 d . . . . .
Zr1 Zr 0.89572(4) 0.85922(4) 0.90664(3) 0.03530(17) Uani 1 1 d . . . . .
C23 C 0.2999(18) 0.684(2) 0.5476(14) 0.151(5) Uani 0.585(12) 1 d D U P A 1
H23A H 0.2718 0.6023 0.5653 0.181 Uiso 0.585(12) 1 calc R U P A 1
H23B H 0.2389 0.6715 0.4906 0.181 Uiso 0.585(12) 1 calc R U P A 1
C24 C 0.4531(16) 0.7243(16) 0.5317(11) 0.132(4) Uani 0.585(12) 1 d D U P A 1
H24A H 0.5152 0.7320 0.5867 0.159 Uiso 0.585(12) 1 calc R U P A 1
H24B H 0.4832 0.8062 0.5148 0.159 Uiso 0.585(12) 1 calc R U P A 1
Cl1 Cl 0.2939(6) 0.8254(6) 0.6476(5) 0.122(2) Uani 0.585(12) 1 d D U P A 1
Cl2 Cl 0.4414(15) 0.5819(13) 0.4311(9) 0.227(5) Uani 0.585(12) 1 d D U P A 1
C23' C 0.356(3) 0.689(3) 0.5677(14) 0.171(6) Uani 0.415(12) 1 d D U P A 2
H23C H 0.4521 0.7126 0.5492 0.205 Uiso 0.415(12) 1 calc R U P A 2
H23D H 0.3510 0.6445 0.6169 0.205 Uiso 0.415(12) 1 calc R U P A 2
C24' C 0.232(2) 0.6018(15) 0.4735(12) 0.141(5) Uani 0.415(12) 1 d D U P A 2
H24C H 0.1936 0.6559 0.4459 0.169 Uiso 0.415(12) 1 calc R U P A 2
H24D H 0.1558 0.5297 0.4849 0.169 Uiso 0.415(12) 1 calc R U P A 2
Cl1' Cl 0.2931(17) 0.8217(15) 0.6003(11) 0.197(5) Uani 0.415(12) 1 d D U P A 2
Cl2' Cl 0.3689(16) 0.5505(11) 0.4101(7) 0.159(4) Uani 0.415(12) 1 d D U P A 2
H1 H 1.007(5) 0.722(5) 1.001(4) 0.050(14) Uiso 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
C1 O1 1.337(5) . ?
C1 C2 1.401(6) . ?
C1 C6 1.415(6) . ?
C2 C3 1.382(7) . ?
C2 C8 1.548(6) . ?
C3 C4 1.398(7) . ?
C3 H3 0.9300 . ?
C4 C5 1.365(7) . ?
C4 C12 1.520(7) . ?
C5 C6 1.402(6) . ?
C5 H5 0.9300 . ?
C6 C7 1.442(6) . ?
C7 N2 1.299(6) . ?
C7 H7 0.9300 . ?
C8 C11 1.508(9) . ?
C8 C9 1.528(8) . ?
C8 C10 1.530(7) . ?
C9 H9A 0.9600 . ?
C9 H9B 0.9600 . ?
C9 H9C 0.9600 . ?
C10 H10A 0.9600 . ?
C10 H10B 0.9600 . ?
C10 H10C 0.9600 . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C12 H12A 0.9600 . ?
C12 H12B 0.9600 . ?
C12 H12C 0.9600 . ?
C13 C14 1.372(6) . ?
C13 C15 1.407(7) . ?
C13 N2 1.414(5) . ?
C14 N1 1.326(6) . ?
C14 C16 1.444(6) . ?
C15 N4 1.139(7) . ?
C16 N3 1.140(6) . ?
C17 O2 1.444(5) . ?
C17 C18 1.475(8) . ?
C17 C19 1.486(8) . ?
C17 H17 0.9800 . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C20 O3 1.426(7) . ?
C20 C21 1.468(10) . ?
C20 C22 1.471(10) . ?
C20 H20 0.9800 . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
C22 H22A 0.9600 . ?
C22 H22B 0.9600 . ?
C22 H22C 0.9600 . ?
N1 Zr1 2.203(4) . ?
N1 H1 0.80(5) . ?
N2 Zr1 2.359(3) . ?
O1 Zr1 2.003(3) . ?
O2 Zr1 2.090(3) . ?
O2 Zr1 2.233(3) 2_777 ?
O3 Zr1 1.893(3) . ?
Zr1 O2 2.233(3) 2_777 ?
Zr1 Zr1 3.5257(9) 2_777 ?
C23 C24 1.488(16) . ?
C23 Cl1 1.837(14) . ?
C23 H23A 0.9700 . ?
C23 H23B 0.9700 . ?
C24 Cl2 1.798(14) . ?
C24 H24A 0.9700 . ?
C24 H24B 0.9700 . ?
C23' C24' 1.671(18) . ?
C23' Cl1' 1.732(18) . ?
C23' H23C 0.9700 . ?
C23' H23D 0.9700 . ?
C24' Cl2' 1.808(17) . ?
C24' H24C 0.9700 . ?
C24' H24D 0.9700 . ?

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 C1 C2 121.5(4) . . ?
O1 C1 C6 119.0(4) . . ?
C2 C1 C6 119.4(4) . . ?
C3 C2 C1 117.8(4) . . ?
C3 C2 C8 120.7(4) . . ?
C1 C2 C8 121.5(4) . . ?
C2 C3 C4 123.9(4) . . ?
C2 C3 H3 118.1 . . ?
C4 C3 H3 118.1 . . ?
C5 C4 C3 117.7(4) . . ?
C5 C4 C12 121.5(5) . . ?
C3 C4 C12 120.7(5) . . ?
C4 C5 C6 121.2(4) . . ?
C4 C5 H5 119.4 . . ?
C6 C5 H5 119.4 . . ?
C5 C6 C1 119.9(4) . . ?
C5 C6 C7 116.9(4) . . ?
C1 C6 C7 123.1(4) . . ?
N2 C7 C6 127.2(4) . . ?
N2 C7 H7 116.4 . . ?
C6 C7 H7 116.4 . . ?
C11 C8 C9 109.3(5) . . ?
C11 C8 C10 108.4(5) . . ?
C9 C8 C10 107.9(5) . . ?
C11 C8 C2 109.4(4) . . ?
C9 C8 C2 110.2(4) . . ?
C10 C8 C2 111.6(4) . . ?
C8 C9 H9A 109.5 . . ?
C8 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
C8 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
C8 C10 H10A 109.5 . . ?
C8 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C8 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C8 C11 H11A 109.5 . . ?
C8 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C8 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C4 C12 H12A 109.5 . . ?
C4 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C4 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C14 C13 C15 123.1(4) . . ?
C14 C13 N2 114.7(4) . . ?
C15 C13 N2 122.2(4) . . ?
N1 C14 C13 120.3(4) . . ?
N1 C14 C16 120.3(4) . . ?
C13 C14 C16 119.4(4) . . ?
N4 C15 C13 177.6(6) . . ?
N3 C16 C14 177.2(6) . . ?
O2 C17 C18 110.6(4) . . ?
O2 C17 C19 111.1(4) . . ?
C18 C17 C19 115.4(5) . . ?
O2 C17 H17 106.4 . . ?
C18 C17 H17 106.4 . . ?
C19 C17 H17 106.4 . . ?
C17 C18 H18A 109.5 . . ?
C17 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C17 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C17 C19 H19A 109.5 . . ?
C17 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C17 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
O3 C20 C21 111.1(6) . . ?
O3 C20 C22 109.3(6) . . ?
C21 C20 C22 116.8(8) . . ?
O3 C20 H20 106.4 . . ?
C21 C20 H20 106.4 . . ?
C22 C20 H20 106.4 . . ?
C20 C21 H21A 109.5 . . ?
C20 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C20 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C20 C22 H22A 109.5 . . ?
C20 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C20 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
C14 N1 Zr1 120.1(3) . . ?
C14 N1 H1 112(4) . . ?
Zr1 N1 H1 127(4) . . ?
C7 N2 C13 118.9(4) . . ?
C7 N2 Zr1 126.9(3) . . ?
C13 N2 Zr1 114.1(3) . . ?
C1 O1 Zr1 143.6(3) . . ?
C17 O2 Zr1 132.2(3) . . ?
C17 O2 Zr1 118.5(3) . 2_777 ?
Zr1 O2 Zr1 109.22(11) . 2_777 ?
C20 O3 Zr1 174.8(4) . . ?
O3 Zr1 O1 98.41(14) . . ?
O3 Zr1 O2 96.98(13) . . ?
O1 Zr1 O2 112.24(11) . . ?
O3 Zr1 N1 96.42(16) . . ?
O1 Zr1 N1 144.85(14) . . ?
O2 Zr1 N1 97.26(13) . . ?
O3 Zr1 O2 167.75(12) . 2_777 ?
O1 Zr1 O2 86.41(12) . 2_777 ?
O2 Zr1 O2 70.78(11) . 2_777 ?
N1 Zr1 O2 85.72(14) . 2_777 ?
O3 Zr1 N2 93.47(14) . . ?
O1 Zr1 N2 76.91(11) . . ?
O2 Zr1 N2 164.79(12) . . ?
N1 Zr1 N2 70.52(14) . . ?
O2 Zr1 N2 98.60(12) 2_777 . ?
O3 Zr1 Zr1 133.71(11) . 2_777 ?
O1 Zr1 Zr1 100.65(9) . 2_777 ?
O2 Zr1 Zr1 36.74(8) . 2_777 ?
N1 Zr1 Zr1 91.59(11) . 2_777 ?
O2 Zr1 Zr1 34.04(7) 2_777 2_777 ?
N2 Zr1 Zr1 131.82(10) . 2_777 ?
C24 C23 Cl1 102.2(11) . . ?
C24 C23 H23A 111.3 . . ?
Cl1 C23 H23A 111.3 . . ?
C24 C23 H23B 111.3 . . ?
Cl1 C23 H23B 111.3 . . ?
H23A C23 H23B 109.2 . . ?
C23 C24 Cl2 97.2(10) . . ?
C23 C24 H24A 112.3 . . ?
Cl2 C24 H24A 112.3 . . ?
C23 C24 H24B 112.3 . . ?
Cl2 C24 H24B 112.3 . . ?
H24A C24 H24B 109.9 . . ?
C24' C23' Cl1' 94.5(12) . . ?
C24' C23' H23C 112.8 . . ?
Cl1' C23' H23C 112.8 . . ?
C24' C23' H23D 112.8 . . ?
Cl1' C23' H23D 112.8 . . ?
H23C C23' H23D 110.3 . . ?
C23' C24' Cl2' 87.4(10) . . ?
C23' C24' H24C 114.1 . . ?
Cl2' C24' H24C 114.1 . . ?
C23' C24' H24D 114.1 . . ?
Cl2' C24' H24D 114.1 . . ?
H24C C24' H24D 111.3 . . ?

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
O1 C1 C2 C3 176.7(4) . . . . ?
C6 C1 C2 C3 -2.6(7) . . . . ?
O1 C1 C2 C8 -0.6(7) . . . . ?
C6 C1 C2 C8 -179.8(4) . . . . ?
C1 C2 C3 C4 1.1(8) . . . . ?
C8 C2 C3 C4 178.4(5) . . . . ?
C2 C3 C4 C5 0.7(9) . . . . ?
C2 C3 C4 C12 179.7(6) . . . . ?
C3 C4 C5 C6 -0.9(9) . . . . ?
C12 C4 C5 C6 -179.9(6) . . . . ?
C4 C5 C6 C1 -0.6(8) . . . . ?
C4 C5 C6 C7 -178.3(5) . . . . ?
O1 C1 C6 C5 -176.9(4) . . . . ?
C2 C1 C6 C5 2.4(7) . . . . ?
O1 C1 C6 C7 0.7(7) . . . . ?
C2 C1 C6 C7 179.9(5) . . . . ?
C5 C6 C7 N2 -178.0(5) . . . . ?
C1 C6 C7 N2 4.4(8) . . . . ?
C3 C2 C8 C11 -113.4(5) . . . . ?
C1 C2 C8 C11 63.8(6) . . . . ?
C3 C2 C8 C9 126.4(6) . . . . ?
C1 C2 C8 C9 -56.4(6) . . . . ?
C3 C2 C8 C10 6.6(8) . . . . ?
C1 C2 C8 C10 -176.3(6) . . . . ?
C15 C13 C14 N1 -179.8(5) . . . . ?
N2 C13 C14 N1 0.6(7) . . . . ?
C15 C13 C14 C16 2.4(8) . . . . ?
N2 C13 C14 C16 -177.2(4) . . . . ?
C13 C14 N1 Zr1 3.0(6) . . . . ?
C16 C14 N1 Zr1 -179.2(3) . . . . ?
C6 C7 N2 C13 -177.8(5) . . . . ?
C6 C7 N2 Zr1 4.4(7) . . . . ?
C14 C13 N2 C7 178.4(4) . . . . ?
C15 C13 N2 C7 -1.2(7) . . . . ?
C14 C13 N2 Zr1 -3.5(5) . . . . ?
C15 C13 N2 Zr1 176.9(4) . . . . ?
C2 C1 O1 Zr1 159.3(4) . . . . ?
C6 C1 O1 Zr1 -21.5(7) . . . . ?
C18 C17 O2 Zr1 -63.8(6) . . . . ?
C19 C17 O2 Zr1 65.8(6) . . . . ?
C18 C17 O2 Zr1 112.2(5) . . . 2_777 ?
C19 C17 O2 Zr1 -118.2(4) . . . 2_777 ?
Cl1 C23 C24 Cl2 -178.0(12) . . . . ?
Cl1' C23' C24' Cl2' 141.7(16) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C17 H17 N2 0.98 2.63 3.452(7) 141.4 2_777
C23 H23A N4 0.97 2.59 3.40(2) 142.1 1_455

_refine_diff_density_max         1.351
_refine_diff_density_min         -0.688
_refine_diff_density_rms         0.086

####################################################################### 
# 
# 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_dmn
_database_code_depnum_ccdc_archive 'CCDC 1438099'
_audit_update_record             
;
2015-11-20 deposited with the CCDC.
2016-02-15 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C44 H60 Hf2 N8 O6, 2(C H Cl3)'
_chemical_formula_sum            'C46 H62 Cl6 Hf2 N8 O6'
_chemical_formula_weight         1392.7

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'
Hf Hf -0.5830 6.1852 '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'

_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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'

_cell_length_a                   9.6702(3)
_cell_length_b                   10.9556(3)
_cell_length_c                   14.5845(4)
_cell_angle_alpha                108.4480(10)
_cell_angle_beta                 90.6828(11)
_cell_angle_gamma                101.2321(10)
_cell_volume                     1433.15(7)
_cell_formula_units_Z            1
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    9861
_cell_measurement_theta_min      2.51
_cell_measurement_theta_max      28.33

_exptl_crystal_description       Block
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.614
_exptl_crystal_F_000             688
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.220
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    3.948
_shelx_estimated_absorpt_T_min   0.477
_shelx_estimated_absorpt_T_max   0.694
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.477
_exptl_absorpt_correction_T_max  0.694
_exptl_absorpt_process_details   'SADABS (Bruker,2012)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            21435
_diffrn_reflns_av_unetI/netI     0.0220
_diffrn_reflns_av_R_equivalents  0.0173
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.004
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measured_fraction_theta_full 0.965
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_Laue_measured_fraction_full 0.965
_diffrn_reflns_point_group_measured_fraction_max 0.816
_diffrn_reflns_point_group_measured_fraction_full 0.793
_reflns_number_total             8227
_reflns_number_gt                7715
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.644
_reflns_Friedel_fraction_max     0.639
_reflns_Friedel_fraction_full    0.621

_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 ? 
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0229P)²+1.5102P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_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_abs_structure_details 
; 
 Flack x determined using 2962 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.497(10)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         8227
_refine_ls_number_parameters     637
_refine_ls_number_restraints     5
_refine_ls_R_factor_all          0.0228
_refine_ls_R_factor_gt           0.0201
_refine_ls_wR_factor_ref         0.0490
_refine_ls_wR_factor_gt          0.0474
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_restrained_S_all      1.054
_refine_ls_shift/su_max          0.021
_refine_ls_shift/su_mean         0.033

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
C1 C -0.0550(17) 0.0886(18) -0.1747(12) 0.033(4) Uani 1 1 d . . . . .
C2 C -0.1182(18) 0.1669(17) -0.2106(11) 0.033(4) Uani 1 1 d . . . . .
C3 C -0.128(2) 0.141(2) -0.3113(15) 0.052(5) Uani 1 1 d . . . . .
H3 H -0.1721 0.1933 -0.3356 0.062 Uiso 1 1 calc R U . . .
C4 C -0.077(2) 0.046(2) -0.3747(13) 0.043(5) Uani 1 1 d . . . . .
C5 C -0.0126(19) -0.0307(19) -0.3420(12) 0.043(5) Uani 1 1 d . . . . .
H5 H 0.0238 -0.0967 -0.3856 0.051 Uiso 1 1 calc R U . . .
C6 C 0.0019(19) -0.0121(19) -0.2372(12) 0.034(4) Uani 1 1 d . . . . .
C7 C 0.0609(19) -0.0947(18) -0.2096(11) 0.035(4) Uani 1 1 d . . . . .
H7 H 0.0986 -0.1538 -0.2584 0.042 Uiso 1 1 calc R U . . .
C8 C 0.1370(19) -0.2028(16) -0.1005(12) 0.034(4) Uani 1 1 d . . . . .
C9 C 0.198(2) -0.294(2) -0.1783(14) 0.044(5) Uani 1 1 d . . . . .
C10 C 0.1420(18) -0.2058(18) -0.0076(12) 0.038(4) Uani 1 1 d . . . . .
C11 C 0.1959(19) -0.306(2) 0.0129(14) 0.051(5) Uani 1 1 d . . . . .
C12 C -0.185(2) 0.289(2) -0.1436(14) 0.050(5) Uani 1 1 d . . . . .
C13 C -0.275(3) 0.239(3) -0.0739(19) 0.116(10) Uani 1 1 d . . . . .
H13A H -0.3057 0.3105 -0.0276 0.174 Uiso 1 1 calc R U . . .
H13B H -0.2209 0.1987 -0.0406 0.174 Uiso 1 1 calc R U . . .
H13C H -0.3565 0.1744 -0.1092 0.174 Uiso 1 1 calc R U . . .
C14 C -0.064(3) 0.393(2) -0.0911(19) 0.114(10) Uani 1 1 d . . . . .
H14A H -0.0121 0.4284 -0.1361 0.171 Uiso 1 1 calc R U . . .
H14B H -0.0025 0.3569 -0.0594 0.171 Uiso 1 1 calc R U . . .
H14C H -0.0967 0.4621 -0.0435 0.171 Uiso 1 1 calc R U . . .
C15 C -0.281(2) 0.330(2) -0.1967(15) 0.070(5) Uani 1 1 d . . . . .
H15A H -0.3480 0.2548 -0.2369 0.105 Uiso 1 1 calc R U . . .
H15B H -0.2294 0.3749 -0.2367 0.105 Uiso 1 1 calc R U . . .
H15C H -0.3304 0.3889 -0.1523 0.105 Uiso 1 1 calc R U . . .
C16 C -0.092(2) 0.029(2) -0.4816(12) 0.053(5) Uani 1 1 d . . . . .
H16A H -0.0250 -0.0199 -0.5148 0.079 Uiso 1 1 calc R U . . .
H16B H -0.0750 0.1139 -0.4901 0.079 Uiso 1 1 calc R U . . .
H16C H -0.1862 -0.0178 -0.5078 0.079 Uiso 1 1 calc R U . . .
C17 C 0.2411(18) 0.2200(17) 0.3934(11) 0.031(4) Uani 1 1 d . . . . .
C18 C 0.3155(19) 0.1392(18) 0.4290(13) 0.039(4) Uani 1 1 d . . . . .
C19 C 0.3205(19) 0.167(2) 0.5296(12) 0.038(4) Uani 1 1 d . . . . .
H19 H 0.3641 0.1153 0.5555 0.046 Uiso 1 1 calc R U . . .
C20 C 0.263(2) 0.270(2) 0.5966(14) 0.046(5) Uani 1 1 d . . . . .
C21 C 0.201(2) 0.3479(18) 0.5555(13) 0.040(4) Uani 1 1 d . . . . .
H21 H 0.1651 0.4168 0.5959 0.048 Uiso 1 1 calc R U . . .
C22 C 0.1922(19) 0.3264(18) 0.4599(13) 0.034(4) Uani 1 1 d . . . . .
C23 C 0.1234(18) 0.4208(18) 0.4251(13) 0.031(4) Uani 1 1 d . . . . .
H23 H 0.0880 0.4836 0.4725 0.038 Uiso 1 1 calc R U . . .
C24 C 0.0443(18) 0.5196(18) 0.3254(12) 0.034(4) Uani 1 1 d . . . . .
C25 C -0.014(2) 0.603(2) 0.3964(15) 0.046(5) Uani 1 1 d . . . . .
C26 C 0.0495(17) 0.5205(16) 0.2318(13) 0.037(4) Uani 1 1 d . . . . .
C27 C -0.0123(19) 0.6204(15) 0.2045(12) 0.039(4) Uani 1 1 d . . . . .
C28 C 0.371(2) 0.037(2) 0.3621(13) 0.049(5) Uani 1 1 d . . . . .
C29 C 0.248(2) -0.0788(17) 0.3037(14) 0.072(6) Uani 1 1 d . . . . .
H29A H 0.1930 -0.1132 0.3480 0.108 Uiso 1 1 calc R U . . .
H29B H 0.2860 -0.1473 0.2598 0.108 Uiso 1 1 calc R U . . .
H29C H 0.1879 -0.0467 0.2676 0.108 Uiso 1 1 calc R U . . .
C30 C 0.471(2) 0.085(3) 0.2922(13) 0.073(7) Uani 1 1 d . . . . .
H30A H 0.4162 0.0894 0.2388 0.109 Uiso 1 1 calc R U . . .
H30B H 0.5322 0.0237 0.2683 0.109 Uiso 1 1 calc R U . . .
H30C H 0.5278 0.1701 0.3264 0.109 Uiso 1 1 calc R U . . .
C31 C 0.463(3) -0.027(3) 0.4221(19) 0.107(9) Uani 1 1 d . . . . .
H31A H 0.5329 0.0409 0.4664 0.160 Uiso 1 1 calc R U . . .
H31B H 0.5091 -0.0890 0.3775 0.160 Uiso 1 1 calc R U . . .
H31C H 0.4010 -0.0722 0.4576 0.160 Uiso 1 1 calc R U . . .
C32 C 0.272(2) 0.295(2) 0.7061(14) 0.072(7) Uani 1 1 d . . . . .
H32A H 0.1883 0.2471 0.7231 0.108 Uiso 1 1 calc R U . . .
H32B H 0.2815 0.3875 0.7398 0.108 Uiso 1 1 calc R U . . .
H32C H 0.3533 0.2667 0.7240 0.108 Uiso 1 1 calc R U . . .
C33 C 0.324(2) 0.166(2) 0.0056(14) 0.058(6) Uani 1 1 d . . . . .
H33A H 0.4108 0.1928 0.0479 0.070 Uiso 1 1 calc R U . . .
H33B H 0.3226 0.0779 -0.0386 0.070 Uiso 1 1 calc R U . . .
C34 C 0.327(3) 0.256(3) -0.051(2) 0.105(10) Uani 1 1 d . . . . .
H34A H 0.2352 0.2409 -0.0827 0.158 Uiso 1 1 calc R U . . .
H34B H 0.3951 0.2398 -0.0983 0.158 Uiso 1 1 calc R U . . .
H34C H 0.3529 0.3448 -0.0081 0.158 Uiso 1 1 calc R U . . .
C35 C -0.1289(19) 0.1509(18) 0.2172(13) 0.042(5) Uani 1 1 d . . . . .
H35A H -0.2170 0.1241 0.1767 0.051 Uiso 1 1 calc R U . . .
H35B H -0.1244 0.2389 0.2618 0.051 Uiso 1 1 calc R U . . .
C36 C -0.125(2) 0.059(3) 0.2725(15) 0.075(7) Uani 1 1 d . . . . .
H36A H -0.1186 -0.0262 0.2286 0.112 Uiso 1 1 calc R U . . .
H36B H -0.2090 0.0506 0.3061 0.112 Uiso 1 1 calc R U . . .
H36C H -0.0434 0.0916 0.3187 0.112 Uiso 1 1 calc R U . . .
C37 C -0.3300(19) -0.158(2) -0.0198(17) 0.079(7) Uani 1 1 d . . . . .
C38 C -0.311(3) -0.279(2) -0.001(3) 0.22(2) Uani 1 1 d . . . . .
H38A H -0.3848 -0.3517 -0.0371 0.329 Uiso 1 1 calc R U . . .
H38B H -0.3148 -0.2671 0.0669 0.329 Uiso 1 1 calc R U . . .
H38C H -0.2209 -0.2977 -0.0211 0.329 Uiso 1 1 calc R U . . .
C39 C -0.4395(17) -0.097(2) 0.010(2) 0.186(15) Uani 1 1 d . . . . .
H39A H -0.5226 -0.1611 0.0100 0.280 Uiso 1 1 calc R U . . .
H39B H -0.4576 -0.0502 -0.0329 0.280 Uiso 1 1 calc R U . . .
H39C H -0.4152 -0.0356 0.0747 0.280 Uiso 1 1 calc R U . . .
C40 C -0.346(2) -0.205(3) -0.1297(10) 0.182(14) Uani 1 1 d . . . . .
H40A H -0.2615 -0.2318 -0.1546 0.273 Uiso 1 1 calc R U . . .
H40B H -0.3629 -0.1354 -0.1519 0.273 Uiso 1 1 calc R U . . .
H40C H -0.4248 -0.2788 -0.1522 0.273 Uiso 1 1 calc R U . . .
C41 C 0.507(2) 0.482(2) 0.2418(17) 0.072(7) Uani 1 1 d . . . . .
C42 C 0.499(5) 0.604(4) 0.292(5) 0.48(5) Uani 1 1 d . . . . .
H42A H 0.4135 0.6229 0.2700 0.723 Uiso 1 1 calc R U . . .
H42B H 0.5790 0.6645 0.2814 0.723 Uiso 1 1 calc R U . . .
H42C H 0.4981 0.6144 0.3594 0.723 Uiso 1 1 calc R U . . .
C43 C 0.561(4) 0.504(5) 0.156(2) 0.28(3) Uani 1 1 d . . . . .
H43A H 0.5007 0.4451 0.1008 0.424 Uiso 1 1 calc R U . . .
H43B H 0.6548 0.4876 0.1508 0.424 Uiso 1 1 calc R U . . .
H43C H 0.5623 0.5931 0.1604 0.424 Uiso 1 1 calc R U . . .
C44 C 0.600(4) 0.443(5) 0.286(7) 0.53(6) Uani 1 1 d . . . . .
H44A H 0.5522 0.3730 0.3081 0.801 Uiso 1 1 calc R U . . .
H44B H 0.6477 0.5149 0.3401 0.801 Uiso 1 1 calc R U . . .
H44C H 0.6674 0.4108 0.2414 0.801 Uiso 1 1 calc R U . . .
C45 C 0.7437(19) 0.5069(16) 0.5732(12) 0.072(6) Uani 1 1 d . . . . .
H45 H 0.7412 0.5641 0.5337 0.086 Uiso 1 1 calc R U . . .
C46 C 0.448(2) 0.807(2) 0.6462(18) 0.105(9) Uani 1 1 d . . . . .
H46 H 0.4434 0.7506 0.6869 0.126 Uiso 1 1 calc R U . . .
Cl1 Cl 0.7564(10) 0.3543(8) 0.4986(7) 0.158(4) Uani 1 1 d . . . . .
Cl2 Cl 0.8656(10) 0.5871(9) 0.6690(7) 0.160(4) Uani 1 1 d . . . . .
Cl3 Cl 0.5784(8) 0.4800(10) 0.6202(7) 0.121(3) Uani 1 1 d . . . . .
Cl4 Cl 0.6074(10) 0.8175(12) 0.5985(9) 0.164(4) Uani 1 1 d . . . . .
Cl5 Cl 0.4085(8) 0.9574(7) 0.7139(6) 0.129(3) Uani 1 1 d . . . . .
Cl6 Cl 0.2985(7) 0.7498(9) 0.5622(5) 0.0994(17) Uani 1 1 d . . . . .
Hf1 Hf -0.00737(2) 0.02499(2) 0.01763(2) 0.0308(2) Uani 1 1 d . . . . .
Hf2 Hf 0.19388(2) 0.28894(2) 0.20250(2) 0.02969(19) Uani 1 1 d . . . . .
N1 N 0.0749(15) -0.1062(15) -0.1190(10) 0.035(4) Uani 1 1 d . . . . .
N2 N 0.253(2) -0.3570(19) -0.2346(15) 0.070(5) Uani 1 1 d . . . . .
N3 N 0.248(2) -0.382(2) 0.0359(15) 0.070(6) Uani 1 1 d . . . . .
N4 N 0.0870(18) -0.1193(15) 0.0595(11) 0.039(4) Uani 1 1 d D . . . .
N5 N 0.1098(13) 0.4224(14) 0.3410(10) 0.029(3) Uani 1 1 d . . . . .
N6 N -0.057(2) 0.677(2) 0.4610(13) 0.069(5) Uani 1 1 d . . . . .
N7 N -0.051(2) 0.6982(19) 0.1871(14) 0.062(5) Uani 1 1 d . . . . .
N8 N 0.1004(18) 0.4294(17) 0.1630(11) 0.046(4) Uani 1 1 d D . . . .
O1 O -0.0337(14) 0.1126(13) -0.0798(8) 0.038(3) Uani 1 1 d . . . . .
O2 O 0.2228(13) 0.1986(13) 0.2983(8) 0.036(3) Uani 1 1 d . . . . .
O3 O 0.2017(11) 0.1607(10) 0.0653(7) 0.032(3) Uani 1 1 d . . . . .
O4 O -0.0122(10) 0.1511(11) 0.1579(7) 0.035(3) Uani 1 1 d . . . . .
O5 O -0.1962(12) -0.0768(13) 0.0051(9) 0.043(3) Uani 1 1 d . . . . .
O6 O 0.3788(14) 0.3827(14) 0.2156(10) 0.050(3) Uani 1 1 d . . . . .
H1N H 0.113(6) 0.458(6) 0.113(3) 0.007(14) Uiso 1 1 d D . . . .
H2N H 0.137(9) -0.098(10) 0.114(4) 0.08(4) Uiso 1 1 d 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
C1 O1 1.330(19) . ?
C1 C2 1.37(2) . ?
C1 C6 1.40(3) . ?
C2 C3 1.40(3) . ?
C2 C12 1.64(3) . ?
C3 C4 1.33(3) . ?
C3 H3 0.9300 . ?
C4 C5 1.33(3) . ?
C4 C16 1.51(2) . ?
C5 C6 1.48(2) . ?
C5 H5 0.9300 . ?
C6 C7 1.32(3) . ?
C7 N1 1.37(2) . ?
C7 H7 0.9300 . ?
C8 C10 1.37(3) . ?
C8 N1 1.41(2) . ?
C8 C9 1.47(2) . ?
C9 N2 1.11(2) . ?
C10 N4 1.33(2) . ?
C10 C11 1.41(3) . ?
C11 N3 1.18(3) . ?
C12 C15 1.42(3) . ?
C12 C14 1.48(3) . ?
C12 C13 1.51(3) . ?
C13 H13A 0.9600 . ?
C13 H13B 0.9600 . ?
C13 H13C 0.9600 . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?
C16 H16A 0.9600 . ?
C16 H16B 0.9600 . ?
C16 H16C 0.9600 . ?
C17 O2 1.336(19) . ?
C17 C22 1.43(2) . ?
C17 C18 1.45(2) . ?
C18 C19 1.40(2) . ?
C18 C28 1.43(3) . ?
C19 C20 1.45(3) . ?
C19 H19 0.9300 . ?
C20 C21 1.40(3) . ?
C20 C32 1.53(3) . ?
C21 C22 1.34(2) . ?
C21 H21 0.9300 . ?
C22 C23 1.54(2) . ?
C23 N5 1.24(2) . ?
C23 H23 0.9300 . ?
C24 C25 1.36(3) . ?
C24 C26 1.37(3) . ?
C24 N5 1.41(2) . ?
C25 N6 1.17(3) . ?
C26 N8 1.35(2) . ?
C26 C27 1.50(2) . ?
C27 N7 1.09(2) . ?
C28 C30 1.55(3) . ?
C28 C29 1.57(3) . ?
C28 C31 1.63(3) . ?
C29 H29A 0.9600 . ?
C29 H29B 0.9600 . ?
C29 H29C 0.9600 . ?
C30 H30A 0.9600 . ?
C30 H30B 0.9600 . ?
C30 H30C 0.9600 . ?
C31 H31A 0.9600 . ?
C31 H31B 0.9600 . ?
C31 H31C 0.9600 . ?
C32 H32A 0.9600 . ?
C32 H32B 0.9600 . ?
C32 H32C 0.9600 . ?
C33 C34 1.47(3) . ?
C33 O3 1.48(2) . ?
C33 H33A 0.9700 . ?
C33 H33B 0.9700 . ?
C34 H34A 0.9600 . ?
C34 H34B 0.9600 . ?
C34 H34C 0.9600 . ?
C35 O4 1.43(2) . ?
C35 C36 1.49(3) . ?
C35 H35A 0.9700 . ?
C35 H35B 0.9700 . ?
C36 H36A 0.9600 . ?
C36 H36B 0.9600 . ?
C36 H36C 0.9600 . ?
C37 C39 1.37(3) . ?
C37 O5 1.39(2) . ?
C37 C38 1.48(3) . ?
C37 C40 1.52(3) . ?
C38 H38A 0.9600 . ?
C38 H38B 0.9600 . ?
C38 H38C 0.9600 . ?
C39 H39A 0.9601 . ?
C39 H39B 0.9601 . ?
C39 H39C 0.9601 . ?
C40 H40A 0.9600 . ?
C40 H40B 0.9600 . ?
C40 H40C 0.9600 . ?
C41 C44 1.30(3) . ?
C41 C42 1.33(4) . ?
C41 C43 1.42(3) . ?
C41 O6 1.44(2) . ?
C42 H42A 0.9636 . ?
C42 H42B 0.9633 . ?
C42 H42C 0.9635 . ?
C43 H43A 0.9602 . ?
C43 H43B 0.9602 . ?
C43 H43C 0.9602 . ?
C44 H44A 1.0423 . ?
C44 H44B 1.0479 . ?
C44 H44C 1.0494 . ?
C45 Cl2 1.701(17) . ?
C45 Cl1 1.71(2) . ?
C45 Cl3 1.76(2) . ?
C45 H45 0.9800 . ?
C46 Cl4 1.69(2) . ?
C46 Cl5 1.75(2) . ?
C46 Cl6 1.76(2) . ?
C46 H46 0.9800 . ?
Hf1 O5 1.919(11) . ?
Hf1 O1 1.989(12) . ?
Hf1 O4 2.082(11) . ?
Hf1 N4 2.206(14) . ?
Hf1 O3 2.218(10) . ?
Hf1 N1 2.310(14) . ?
Hf1 Hf2 3.4882(3) . ?
Hf2 O6 1.855(14) . ?
Hf2 O2 1.995(11) . ?
Hf2 O3 2.061(8) . ?
Hf2 N8 2.147(16) . ?
Hf2 O4 2.202(10) . ?
Hf2 N5 2.348(14) . ?
N4 H2N 0.87(3) . ?
N8 H1N 0.87(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
O1 C1 C2 121.5(16) . . ?
O1 C1 C6 117.8(15) . . ?
C2 C1 C6 120.3(16) . . ?
C1 C2 C3 118.0(16) . . ?
C1 C2 C12 124.1(15) . . ?
C3 C2 C12 117.8(17) . . ?
C4 C3 C2 124.6(19) . . ?
C4 C3 H3 117.7 . . ?
C2 C3 H3 117.7 . . ?
C5 C4 C3 118.9(17) . . ?
C5 C4 C16 121.7(18) . . ?
C3 C4 C16 119.4(19) . . ?
C4 C5 C6 120.8(17) . . ?
C4 C5 H5 119.6 . . ?
C6 C5 H5 119.6 . . ?
C7 C6 C1 124.6(16) . . ?
C7 C6 C5 118.0(16) . . ?
C1 C6 C5 117.3(17) . . ?
C6 C7 N1 129.3(17) . . ?
C6 C7 H7 115.4 . . ?
N1 C7 H7 115.4 . . ?
C10 C8 N1 117.6(15) . . ?
C10 C8 C9 121.6(16) . . ?
N1 C8 C9 120.8(16) . . ?
N2 C9 C8 175(2) . . ?
N4 C10 C8 118.7(16) . . ?
N4 C10 C11 121.8(15) . . ?
C8 C10 C11 119.4(17) . . ?
N3 C11 C10 175(2) . . ?
C15 C12 C14 115(2) . . ?
C15 C12 C13 104.3(18) . . ?
C14 C12 C13 111(2) . . ?
C15 C12 C2 113.7(16) . . ?
C14 C12 C2 105.9(16) . . ?
C13 C12 C2 107.3(18) . . ?
C12 C13 H13A 109.5 . . ?
C12 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C12 C13 H13C 109.3 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C12 C14 H14A 109.5 . . ?
C12 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C12 C14 H14C 109.4 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C12 C15 H15A 109.6 . . ?
C12 C15 H15B 109.4 . . ?
H15A C15 H15B 109.5 . . ?
C12 C15 H15C 109.4 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
C4 C16 H16A 109.5 . . ?
C4 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
C4 C16 H16C 109.4 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
O2 C17 C22 119.5(16) . . ?
O2 C17 C18 120.2(15) . . ?
C22 C17 C18 120.2(15) . . ?
C19 C18 C28 125.4(17) . . ?
C19 C18 C17 114.5(16) . . ?
C28 C18 C17 120.1(16) . . ?
C18 C19 C20 124.9(17) . . ?
C18 C19 H19 117.5 . . ?
C20 C19 H19 117.6 . . ?
C21 C20 C19 115.9(16) . . ?
C21 C20 C32 122.0(19) . . ?
C19 C20 C32 122.0(17) . . ?
C22 C21 C20 122.3(17) . . ?
C22 C21 H21 118.8 . . ?
C20 C21 H21 118.9 . . ?
C21 C22 C17 121.9(16) . . ?
C21 C22 C23 116.5(16) . . ?
C17 C22 C23 121.6(16) . . ?
N5 C23 C22 127.2(16) . . ?
N5 C23 H23 116.4 . . ?
C22 C23 H23 116.4 . . ?
C25 C24 C26 124.7(16) . . ?
C25 C24 N5 123.2(15) . . ?
C26 C24 N5 112.1(15) . . ?
N6 C25 C24 176(2) . . ?
N8 C26 C24 121.9(16) . . ?
N8 C26 C27 119.4(16) . . ?
C24 C26 C27 118.5(15) . . ?
N7 C27 C26 176(2) . . ?
C18 C28 C30 114.0(19) . . ?
C18 C28 C29 110.1(18) . . ?
C30 C28 C29 110.8(17) . . ?
C18 C28 C31 109.5(16) . . ?
C30 C28 C31 106.8(18) . . ?
C29 C28 C31 105.2(19) . . ?
C28 C29 H29A 109.4 . . ?
C28 C29 H29B 109.6 . . ?
H29A C29 H29B 109.5 . . ?
C28 C29 H29C 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?
C28 C30 H30A 109.5 . . ?
C28 C30 H30B 109.4 . . ?
H30A C30 H30B 109.5 . . ?
C28 C30 H30C 109.5 . . ?
H30A C30 H30C 109.5 . . ?
H30B C30 H30C 109.5 . . ?
C28 C31 H31A 109.4 . . ?
C28 C31 H31B 109.5 . . ?
H31A C31 H31B 109.5 . . ?
C28 C31 H31C 109.5 . . ?
H31A C31 H31C 109.5 . . ?
H31B C31 H31C 109.5 . . ?
C20 C32 H32A 109.4 . . ?
C20 C32 H32B 109.5 . . ?
H32A C32 H32B 109.5 . . ?
C20 C32 H32C 109.5 . . ?
H32A C32 H32C 109.5 . . ?
H32B C32 H32C 109.5 . . ?
C34 C33 O3 113.6(19) . . ?
C34 C33 H33A 108.9 . . ?
O3 C33 H33A 108.9 . . ?
C34 C33 H33B 108.9 . . ?
O3 C33 H33B 108.8 . . ?
H33A C33 H33B 107.7 . . ?
C33 C34 H34A 109.5 . . ?
C33 C34 H34B 109.5 . . ?
H34A C34 H34B 109.5 . . ?
C33 C34 H34C 109.5 . . ?
H34A C34 H34C 109.5 . . ?
H34B C34 H34C 109.5 . . ?
O4 C35 C36 109.7(15) . . ?
O4 C35 H35A 109.7 . . ?
C36 C35 H35A 109.7 . . ?
O4 C35 H35B 109.7 . . ?
C36 C35 H35B 109.7 . . ?
H35A C35 H35B 108.2 . . ?
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 . . ?
C39 C37 O5 115.0(19) . . ?
C39 C37 C38 124(2) . . ?
O5 C37 C38 103.2(16) . . ?
C39 C37 C40 106(2) . . ?
O5 C37 C40 105.2(17) . . ?
C38 C37 C40 101(2) . . ?
C37 C38 H38A 109.5 . . ?
C37 C38 H38B 109.3 . . ?
H38A C38 H38B 109.5 . . ?
C37 C38 H38C 109.6 . . ?
H38A C38 H38C 109.5 . . ?
H38B C38 H38C 109.5 . . ?
C37 C39 H39A 109.3 . . ?
C37 C39 H39B 109.8 . . ?
H39A C39 H39B 109.5 . . ?
C37 C39 H39C 109.3 . . ?
H39A C39 H39C 109.5 . . ?
H39B C39 H39C 109.4 . . ?
C37 C40 H40A 109.6 . . ?
C37 C40 H40B 109.4 . . ?
H40A C40 H40B 109.5 . . ?
C37 C40 H40C 109.4 . . ?
H40A C40 H40C 109.5 . . ?
H40B C40 H40C 109.5 . . ?
C44 C41 C42 110(4) . . ?
C44 C41 C43 110(4) . . ?
C42 C41 C43 99(3) . . ?
C44 C41 O6 109(2) . . ?
C42 C41 O6 118(3) . . ?
C43 C41 O6 109(2) . . ?
C41 C42 H42A 110.1 . . ?
C41 C42 H42B 109.5 . . ?
H42A C42 H42B 109.1 . . ?
C41 C42 H42C 110.0 . . ?
H42A C42 H42C 109.0 . . ?
H42B C42 H42C 109.0 . . ?
C41 C43 H43A 109.5 . . ?
C41 C43 H43B 109.4 . . ?
H43A C43 H43B 109.5 . . ?
C41 C43 H43C 109.6 . . ?
H43A C43 H43C 109.5 . . ?
H43B C43 H43C 109.5 . . ?
C41 C44 H44A 119.1 . . ?
C41 C44 H44B 120.0 . . ?
H44A C44 H44B 98.0 . . ?
C41 C44 H44C 120.2 . . ?
H44A C44 H44C 97.2 . . ?
H44B C44 H44C 97.3 . . ?
Cl2 C45 Cl1 119.3(12) . . ?
Cl2 C45 Cl3 107.3(11) . . ?
Cl1 C45 Cl3 103.9(9) . . ?
Cl2 C45 H45 108.6 . . ?
Cl1 C45 H45 108.6 . . ?
Cl3 C45 H45 108.6 . . ?
Cl4 C46 Cl5 115.4(15) . . ?
Cl4 C46 Cl6 116.1(15) . . ?
Cl5 C46 Cl6 97.8(10) . . ?
Cl4 C46 H46 109.0 . . ?
Cl5 C46 H46 109.0 . . ?
Cl6 C46 H46 109.0 . . ?
O5 Hf1 O1 98.1(6) . . ?
O5 Hf1 O4 97.2(5) . . ?
O1 Hf1 O4 111.1(5) . . ?
O5 Hf1 N4 93.2(6) . . ?
O1 Hf1 N4 148.6(5) . . ?
O4 Hf1 N4 96.3(5) . . ?
O5 Hf1 O3 167.6(5) . . ?
O1 Hf1 O3 88.5(5) . . ?
O4 Hf1 O3 70.6(3) . . ?
N4 Hf1 O3 86.3(5) . . ?
O5 Hf1 N1 98.4(5) . . ?
O1 Hf1 N1 77.5(5) . . ?
O4 Hf1 N1 160.9(4) . . ?
N4 Hf1 N1 72.0(5) . . ?
O3 Hf1 N1 93.2(4) . . ?
O5 Hf1 Hf2 133.9(4) . . ?
O1 Hf1 Hf2 100.4(4) . . ?
O4 Hf1 Hf2 36.7(3) . . ?
N4 Hf1 Hf2 92.4(4) . . ?
O3 Hf1 Hf2 33.9(2) . . ?
N1 Hf1 Hf2 126.7(4) . . ?
O6 Hf2 O2 95.9(6) . . ?
O6 Hf2 O3 96.6(5) . . ?
O2 Hf2 O3 108.3(5) . . ?
O6 Hf2 N8 95.7(6) . . ?
O2 Hf2 N8 149.3(5) . . ?
O3 Hf2 N8 98.5(5) . . ?
O6 Hf2 O4 167.8(5) . . ?
O2 Hf2 O4 87.1(5) . . ?
O3 Hf2 O4 71.3(3) . . ?
N8 Hf2 O4 87.5(6) . . ?
O6 Hf2 N5 99.2(5) . . ?
O2 Hf2 N5 78.9(5) . . ?
O3 Hf2 N5 161.8(4) . . ?
N8 Hf2 N5 71.2(5) . . ?
O4 Hf2 N5 92.9(4) . . ?
O6 Hf2 Hf1 133.5(4) . . ?
O2 Hf2 Hf1 99.9(4) . . ?
O3 Hf2 Hf1 36.9(3) . . ?
N8 Hf2 Hf1 92.4(5) . . ?
O4 Hf2 Hf1 34.4(3) . . ?
N5 Hf2 Hf1 126.6(3) . . ?
C7 N1 C8 123.1(15) . . ?
C7 N1 Hf1 124.0(12) . . ?
C8 N1 Hf1 112.8(11) . . ?
C10 N4 Hf1 118.9(11) . . ?
C10 N4 H2N 109(7) . . ?
Hf1 N4 H2N 122(7) . . ?
C23 N5 C24 117.8(15) . . ?
C23 N5 Hf2 127.2(12) . . ?
C24 N5 Hf2 114.9(10) . . ?
C26 N8 Hf2 119.5(12) . . ?
C26 N8 H1N 107(4) . . ?
Hf2 N8 H1N 130(4) . . ?
C1 O1 Hf1 142.1(12) . . ?
C17 O2 Hf2 142.0(11) . . ?
C33 O3 Hf2 125.0(10) . . ?
C33 O3 Hf1 125.7(9) . . ?
Hf2 O3 Hf1 109.1(4) . . ?
C35 O4 Hf1 126.6(9) . . ?
C35 O4 Hf2 124.5(10) . . ?
Hf1 O4 Hf2 109.0(4) . . ?
C37 O5 Hf1 170.8(14) . . ?
C41 O6 Hf2 165.5(12) . . ?

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
O1 C1 C2 C3 175.4(17) . . . . ?
C6 C1 C2 C3 2(3) . . . . ?
O1 C1 C2 C12 -5(3) . . . . ?
C6 C1 C2 C12 -178.9(17) . . . . ?
C1 C2 C3 C4 -1(3) . . . . ?
C12 C2 C3 C4 179(2) . . . . ?
C2 C3 C4 C5 0(3) . . . . ?
C2 C3 C4 C16 -179.1(18) . . . . ?
C3 C4 C5 C6 1(3) . . . . ?
C16 C4 C5 C6 179.6(18) . . . . ?
O1 C1 C6 C7 8(3) . . . . ?
C2 C1 C6 C7 -177.9(19) . . . . ?
O1 C1 C6 C5 -175.2(16) . . . . ?
C2 C1 C6 C5 -1(3) . . . . ?
C4 C5 C6 C7 177(2) . . . . ?
C4 C5 C6 C1 0(3) . . . . ?
C1 C6 C7 N1 3(3) . . . . ?
C5 C6 C7 N1 -173.4(18) . . . . ?
N1 C8 C10 N4 1(3) . . . . ?
C9 C8 C10 N4 179.0(17) . . . . ?
N1 C8 C10 C11 176.4(16) . . . . ?
C9 C8 C10 C11 -5(3) . . . . ?
C1 C2 C12 C15 -162(2) . . . . ?
C3 C2 C12 C15 17(3) . . . . ?
C1 C2 C12 C14 71(3) . . . . ?
C3 C2 C12 C14 -109(2) . . . . ?
C1 C2 C12 C13 -47(3) . . . . ?
C3 C2 C12 C13 132(2) . . . . ?
O2 C17 C18 C19 -176.6(16) . . . . ?
C22 C17 C18 C19 6(3) . . . . ?
O2 C17 C18 C28 1(3) . . . . ?
C22 C17 C18 C28 -176.5(19) . . . . ?
C28 C18 C19 C20 -180(2) . . . . ?
C17 C18 C19 C20 -2(3) . . . . ?
C18 C19 C20 C21 -1(3) . . . . ?
C18 C19 C20 C32 -179.9(19) . . . . ?
C19 C20 C21 C22 2(3) . . . . ?
C32 C20 C21 C22 -180(2) . . . . ?
C20 C21 C22 C17 2(3) . . . . ?
C20 C21 C22 C23 -179.2(18) . . . . ?
O2 C17 C22 C21 176.4(17) . . . . ?
C18 C17 C22 C21 -6(3) . . . . ?
O2 C17 C22 C23 -2(3) . . . . ?
C18 C17 C22 C23 175.1(17) . . . . ?
C21 C22 C23 N5 176.7(19) . . . . ?
C17 C22 C23 N5 -5(3) . . . . ?
C25 C24 C26 N8 -175.4(18) . . . . ?
N5 C24 C26 N8 6(3) . . . . ?
C25 C24 C26 C27 0(3) . . . . ?
N5 C24 C26 C27 -178.5(14) . . . . ?
C19 C18 C28 C30 -128(2) . . . . ?
C17 C18 C28 C30 55(2) . . . . ?
C19 C18 C28 C29 107(2) . . . . ?
C17 C18 C28 C29 -71(2) . . . . ?
C19 C18 C28 C31 -9(3) . . . . ?
C17 C18 C28 C31 174(2) . . . . ?
C6 C7 N1 C8 177.9(19) . . . . ?
C6 C7 N1 Hf1 0(3) . . . . ?
C10 C8 N1 C7 -178.6(17) . . . . ?
C9 C8 N1 C7 3(3) . . . . ?
C10 C8 N1 Hf1 -1(2) . . . . ?
C9 C8 N1 Hf1 -178.9(13) . . . . ?
C8 C10 N4 Hf1 0(2) . . . . ?
C11 C10 N4 Hf1 -176.0(14) . . . . ?
C22 C23 N5 C24 -179.2(17) . . . . ?
C22 C23 N5 Hf2 -3(3) . . . . ?
C25 C24 N5 C23 -6(3) . . . . ?
C26 C24 N5 C23 173.3(17) . . . . ?
C25 C24 N5 Hf2 178.0(15) . . . . ?
C26 C24 N5 Hf2 -3.1(19) . . . . ?
C24 C26 N8 Hf2 -6(2) . . . . ?
C27 C26 N8 Hf2 178.5(13) . . . . ?
C2 C1 O1 Hf1 155.4(16) . . . . ?
C6 C1 O1 Hf1 -31(3) . . . . ?
C22 C17 O2 Hf2 23(3) . . . . ?
C18 C17 O2 Hf2 -153.9(15) . . . . ?
C34 C33 O3 Hf2 -85(2) . . . . ?
C34 C33 O3 Hf1 90(2) . . . . ?
C36 C35 O4 Hf1 87.8(17) . . . . ?
C36 C35 O4 Hf2 -92.5(17) . . . . ?
C44 C41 O6 Hf2 119(7) . . . . ?
C42 C41 O6 Hf2 -9(8) . . . . ?
C43 C41 O6 Hf2 -120(6) . . . . ?
O2 Hf2 O6 C41 -98(6) . . . . ?
O3 Hf2 O6 C41 152(6) . . . . ?
N8 Hf2 O6 C41 53(6) . . . . ?
O4 Hf2 O6 C41 158(5) . . . . ?
N5 Hf2 O6 C41 -19(6) . . . . ?
Hf1 Hf2 O6 C41 152(5) . . . . ?

_refine_diff_density_max         0.696
_refine_diff_density_min         -0.444
_refine_diff_density_rms         0.066
_vrf_PLAT213_dmn                 
;
PROBLEM: Atom C42             has ADP max/min Ratio .....        5.1 prolat
RESPONSE: ...
;
_vrf_PLAT222_dmn                 
;
PROBLEM: Large Non-Solvent    H    Uiso(max)/Uiso(min) ..       10.0 Ratio 
RESPONSE: This alarm is due to the elongated ADPs of carbon 
atoms which suggest that these are probably disordered 
In particular, C42 and C43 are disordered between two orientations. 

;
_vrf_PLAT242_dmn                 
;
PROBLEM: Low       Ueq as Compared to Neighbors for .....        C41 Check 
RESPONSE: This alarm is due to the elongated ADPs of carbon 
atoms which suggest that these are probably disordered 
In particular, C42 and C43 are disordered between two orientations. 

;
_vrf_PLAT412_dmn                 
;
PROBLEM: Short Intra XH3 .. XHn     H42B   ..  H43C    ..       1.68 Ang.  
RESPONSE: This alarm is due to the elongated ADPs of carbon 
atoms which suggest that these are probably disordered 
In particular, C42 and C43 are disordered between two orientations. 
;
_vrf_PLAT721_dmn                 
;
PROBLEM: Bond    Calc     0.96000, Rep     1.04230 Dev...       0.08 Ang.  
RESPONSE: This alarm is due to the elongated ADPs of carbon 
atoms which suggest that these are probably disordered 
In particular, C42 and C43 are disordered between two orientations. 

;
_vrf_PLAT722_dmn                 
;
PROBLEM: Angle   Calc      109.00, Rep      119.10 Dev...      10.10 Degree
RESPONSE: This alarm is due to the elongated ADPs of carbon 
atoms which suggest that these are probably disordered 
In particular, C42 and C43 are disordered between two orientations.
;
# end Validation Reply Form

_shelxl_version_number           2014-3

