# Electronic Supplementary Material (ESI) for Faraday Discussions.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_mig211s_sq
_database_code_depnum_ccdc_archive 'CCDC 1530874'
_audit_update_record             
;
2017-02-03 deposited with the CCDC.
2017-02-22 downloaded from the CCDC.
;
_audit_creation_date             2017-01-23
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_shelx_SHELXL_version_number     2016/6
_chemical_name_common            Zr6O4(OH)4(bpydc)5.64(NiBr2)5.64
_chemical_name_systematic        ?
_chemical_formula_moiety         
'C67.68 H33.84 Br11.28 N11.28 Ni5.64 O30.56 Zr6'
_chemical_formula_sum            
'C67.68 H33.84 Br11.28 N11.28 Ni5.64 O30.56 Zr6'
_chemical_formula_weight         3277.67
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0060 0.0030
'ANOMDisVal Program in PLATON Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7-13'
H H 0.0000 0.0000
'ANOMDisVal Program in PLATON Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7-13'
Br Br -2.3750 3.5370
'ANOMDisVal Program in PLATON Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7-13'
N N 0.0100 0.0050
'ANOMDisVal Program in PLATON Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7-13'
Ni Ni 0.2480 1.6440
'ANOMDisVal Program in PLATON Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7-13'
O O 0.0180 0.0100
'ANOMDisVal Program in PLATON Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7-13'
Zr Zr -1.2060 0.8400
'ANOMDisVal Program in PLATON Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7-13'

_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      cubic
_space_group_IT_number           205
_space_group_name_H-M_alt        'P a -3'
_space_group_name_Hall           '-P 2ac 2ab 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
'z, x, y'
'z+1/2, -x+1/2, -y'
'-z+1/2, -x, y+1/2'
'-z, x+1/2, -y+1/2'
'y, z, x'
'-y, z+1/2, -x+1/2'
'y+1/2, -z+1/2, -x'
'-y+1/2, -z, x+1/2'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'x, -y-1/2, z-1/2'
'-x-1/2, y-1/2, z'
'-z, -x, -y'
'-z-1/2, x-1/2, y'
'z-1/2, x, -y-1/2'
'z, -x-1/2, y-1/2'
'-y, -z, -x'
'y, -z-1/2, x-1/2'
'-y-1/2, z-1/2, x'
'y-1/2, z, -x-1/2'

_cell_length_a                   26.2758(8)
_cell_length_b                   26.2758(8)
_cell_length_c                   26.2758(8)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     18141.3(17)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9070
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.806
_cell_measurement_theta_min      2.366
_shelx_estimated_absorpt_T_max   0.735
_shelx_estimated_absorpt_T_min   0.735
_exptl_absorpt_coefficient_mu    6.130
_exptl_absorpt_correction_T_max  0.735
_exptl_absorpt_correction_T_min  0.606
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2014/5 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.0923 before and 0.0708 after correction.
The Ratio of minimum to maximum transmission is 0.8244.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'yellow green'
_exptl_crystal_colour_primary    'yellow green'
_exptl_crystal_density_diffrn    1.199
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       octahedral
_exptl_crystal_F_000             6224
_exptl_crystal_size_max          0.0536
_exptl_crystal_size_mid          0.0536
_exptl_crystal_size_min          0.0536
_exptl_special_details           
;
X-ray diffraction analyses were performed on single crystals coated with
 Paratone-N oil and mounted on MiTeGen loops. Crystals were frozen at a
 temperature of 100 K by an Oxford Cryosystems Cyrostream using N₂ during
 the experiments. Data was collected at Beamline 11.3.1 at the Advanced
 Light Source, Lawrence Berkeley National Laboratory using synchrotron
 radiation (lamda = 0.7749 angstrom) on a Bruker D8 diffractometer
equipped with a Bruker PHOTON100 CMOS detector.
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0950
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            178387
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        29.806
_diffrn_reflns_theta_max         29.806
_diffrn_reflns_theta_min         2.160
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 10.42
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker D8 with PHOTON100 CMOS detector'
_diffrn_measurement_method       'φ and ω shutterless scans'
_diffrn_radiation_monochromator  'silicon 111'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.8856
_diffrn_source                   'Advanced Light Source station 11.3.1'
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4250
_reflns_number_total             4662
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_refine_diff_density_max         1.044
_refine_diff_density_min         -0.677
_refine_diff_density_rms         0.148
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.151
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     278
_refine_ls_number_reflns         4662
_refine_ls_number_restraints     705
_refine_ls_R_factor_all          0.0715
_refine_ls_R_factor_gt           0.0651
_refine_ls_restrained_S_all      1.127
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1011P)²+163.0712P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2002
_refine_ls_wR_factor_ref         0.2046
_refine_special_details          
;The compound is isostructural with Zr6O4(OH)4(bpdc)6 or UiO-67. Unmetalated, 
it has a spacegroup of Fm-3m. Upon metalation, the space group changes to Pa-3. 
This loss of symmetry produces twin domains which can be accounted for by a 
2-fold rotation about a face diagonal and refined as a 2-component twin. 

All non-hydrogen atoms were refined anisotropically.
All other hydrogen atoms on carbon atoms were placed geometrically and constrained.
Hydrogens on the disordered water/hydroxides and mu3-hydroxides were not found, so they
were omitted from the refinement but not the formula. All hydrogen atoms were refined 
using the riding model.
 
This metal-organic framework is derived from Zr6O4(OH)4(bpdc)6 or UiO-66 which has been
known to have structural defects where 1/12 to 1/2 of the linkers are absent. 
Therefore the linker occupancy was allowed to refine freely. In this case 94% of the 
ligand was determined to be present, with 100% of the 2,2'-bipyridine sites metalated. 
When the ligand is not present, water/hydroxide is known to replace it in the cluster. 
These, however, could not be modeled in the structure due to their disorder and low occupancy.
The (bpy)NiBr2 complexes were found to be disordered over two positions. Free refinement of 
the occupancies of the two positions resulted in an occupancies of 64% and 30%. 
The (bpy)NiBr2 complexes with an occupancy of 64% were found to be in two coordination
geometries, which were assigned to be pseudooctahedral, 52% occupancy with one Br-
ligand trans to a bipyridine nitrogen and another Br- ligand cis to the bipyridine nitrogens, 
and trigonal bipyramidal, 12% occupancy with the two Br- ligands on the equatorial sites.
The (bpy)NiBr2 complexes with an occupancy of 30% were found to be in pseudooctahedral with
with one Br- ligand trans to a bipyridine nitrogen and another Br- ligand cis to the 
bipyridne nitrogens. Although coordinated solvent molecules likely occupy the sites necessary 
to complete the Ni coordination spheres in these complex, these could not be modeled due to 
their low occupancy and weak scattering in comparison to the Br- ligands.
Displacement parameter (RIGU and SIMU), distance (SADI), and geometric (FLAT) restaints were 
used to model the linker-NiBr2 complexes which are disordered over the two positions and
multiple coordination geometries, while ddisplacement parameter restraints (RIGU and SIMU)
were used to model the disordered mu3-hydroxo and mu-oxo ligands on the zirconium inorganic
cluster. Disorder of residual solvent within the pores of the crystal was extensive and could 
not be modeled. Consequently, the unassigned electron density was accounted for using SQUEEZE 
as implemented in the PLATON interface. Refinement before SQUEEZE was applied gave an 
R1 of 10.10% (wR2 = 32.24%), while applying SQUEEZE resulted in an R1 of 6.51% (wR2 = 20.46%)., Twin,SQUEEZE
;
_vrf_THETM01_mig211s_sq          
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: Due to weak scattering at high resolution, a 
sin(theta)/lamda > 0.575 could not be achieved. The data was
integrated to a resolution limit (0.89 angstrom) where I/sigma > 3
and Rint < 0.35.
;
_vrf_PLAT307_mig211s_sq          
;
PROBLEM: Isolated Metal Atom found in Structure (Unusual)       Ni1A Check 
RESPONSE: The bipyridine linker and Br- ligands are clearly coordinated 
to Ni1A in the structure. This may be an error in checkCIF that results 
from the polymeric nature of the structure.
;
_vrf_PLAT213_mig211s_sq          
;
PROBLEM: Atom C2              has ADP max/min Ratio .....        4.1 prolat
RESPONSE: The rotation of the metalated linkers in and out of plane causes 
disorder that results in the prolate shape of the ADPs.
;
_vrf_PLAT250_mig211s_sq          
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        5.7 Note  
RESPONSE: Rotational disorder of the linkers out of plane probably result
in the large average tensor.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.500(2) 0.500(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Restrained distances
 C5-C4 \\sim C11-C10
 with sigma of 0.02
 C12-C11 \\sim C5-C6
 with sigma of 0.02
 N2-C12 \\sim N1-C6
 with sigma of 0.02
 N1-C2 \\sim N2-C8
 with sigma of 0.02
 C2-C3 \\sim C9-C8
 with sigma of 0.02
 C10-C12 \\sim C6-C4
 with sigma of 0.02
 C10-C8 \\sim C4-C2
 with sigma of 0.02
 C6-C4 \\sim C12-C10
 with sigma of 0.02
 C12-C8 \\sim C6-C2
 with sigma of 0.02
 C4-C2 \\sim C10-C8
 with sigma of 0.02
 C5-N1 \\sim N2-C11
 with sigma of 0.02
 N1-C3 \\sim N2-C9
 with sigma of 0.02
 C5-C3 \\sim C11-C9
 with sigma of 0.02
4. Restrained planarity
 N1, C1, C2, C3, C4, C5, C6, C12
 with sigma of 0.1
 N2, C6, C7, C8, C9, C10, C11, C12
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
O3 \\sim O4 \\sim O5 \\sim O6 \\sim N1 \\sim N2 \\sim C1 \\sim C2 \\sim C3
\\sim C4 \\sim H4 \\sim C5 \\sim H5 \\sim C6 \\sim C7 \\sim C8 \\sim H8 \\sim
C9 \\sim C10 \\sim H10 \\sim C11 \\sim H11 \\sim C12: within 2.6A with sigma of
0.04 and sigma for terminal atoms of 0.08
Ni1A \\sim Br1B \\sim Br2B \\sim Ni1B \\sim Br5A \\sim Br4A \\sim Br1A \\sim
Br2A \\sim Br3A: within 2.6A with sigma of 0.04 and sigma for terminal atoms of
0.08
O1A \\sim O2A \\sim O1B \\sim O2B: within 2.5A with sigma of 0.01 and sigma for
terminal atoms of 0.02
6. Rigid body (RIGU) restrains
 O3, O4, O5, N1, N2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, O4, O5, O6, N1, N2, C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Ni1A, Br1B, Br2B, Ni1B, Br1A, Br2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Ni1A, Br1B, Br2B, Ni1B, Br4A, Br1A, Br2A, Br3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Ni1A, Br1B, Br2B, Ni1B, Br5A, Br4A, Br1A, Br2A, Br3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1A, O2A, O1B, O2B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Fixed Sof: O3(0.94) O4(0.94) O5(0.94) O6(0.94) N1(0.94) N2(0.94) C1(0.94)
 C2(0.94) H2(0.94) C3(0.94) C4(0.94) H4(0.94) C5(0.94) H5(0.94) C6(0.94)
 C7(0.94) C8(0.94) H8(0.94) C9(0.94) C10(0.94) H10(0.94) C11(0.94) H11(0.94)
 C12(0.94) Ni1A(0.64) O1A(0.5) O2A(0.16667) Br1B(0.3) Br2B(0.3) Ni1B(0.3)
 O1B(0.5) O2B(0.16667) Br4A(0.12) Br5A(0.12) Br1A(0.52) Br2A(0.4) Br3A(0.12)
8.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C8(H8), C10(H10), C11(H11)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_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
Zr1 Zr 0.48614(3) 0.09207(3) 0.01152(3) 0.0135(3) Uani 1 1 d . . . . .
O3 O 0.4068(3) 0.1232(3) 0.0051(3) 0.0273(17) Uani 0.94 1 d . U . . .
O4 O 0.3556(2) 0.0546(3) -0.0112(3) 0.0253(16) Uani 0.94 1 d . U . . .
O5 O 0.1226(3) 0.4114(3) -0.0285(3) 0.0314(18) Uani 0.94 1 d . U . . .
O6 O 0.0538(3) 0.3575(3) -0.0276(3) 0.0281(17) Uani 0.94 1 d . U . . .
N1 N 0.2908(4) 0.2221(4) -0.0140(5) 0.068(4) Uani 0.94 1 d D U . . .
N2 N 0.2216(4) 0.2919(4) -0.0211(5) 0.065(3) Uani 0.94 1 d D U . . .
C1 C 0.3642(4) 0.1012(4) -0.0077(5) 0.033(2) Uani 0.94 1 d . U . . .
C2 C 0.3280(4) 0.1885(4) -0.0080(5) 0.056(4) Uani 0.94 1 d D U . A .
H2 H 0.360508 0.200342 0.002565 0.067 Uiso 0.94 1 calc R . . . .
C3 C 0.3216(5) 0.1366(4) -0.0166(7) 0.060(4) Uani 0.94 1 d D U . A .
C4 C 0.2751(5) 0.1199(5) -0.0319(9) 0.087(5) Uani 0.94 1 d D U . . .
H4 H 0.270837 0.085545 -0.042291 0.104 Uiso 0.94 1 calc R U . . .
C5 C 0.2329(6) 0.1535(5) -0.0325(10) 0.097(5) Uani 0.94 1 d D U . A .
H5 H 0.198844 0.141458 -0.033998 0.116 Uiso 0.94 1 calc R U . . .
C6 C 0.2445(5) 0.2063(5) -0.0307(6) 0.077(4) Uani 0.94 1 d D U . A .
C7 C 0.1013(5) 0.3683(5) -0.0300(4) 0.035(2) Uani 0.94 1 d . U . A .
C8 C 0.1874(4) 0.3302(4) -0.0217(5) 0.059(4) Uani 0.94 1 d D U . A .
H8 H 0.199078 0.363669 -0.014791 0.071 Uiso 0.94 1 calc R U . . .
C9 C 0.1362(5) 0.3231(5) -0.0320(5) 0.060(3) Uani 0.94 1 d D U . . .
C10 C 0.1195(5) 0.2739(5) -0.0409(7) 0.088(5) Uani 0.94 1 d D U . A .
H10 H 0.084149 0.267300 -0.044922 0.105 Uiso 0.94 1 calc R U . . .
C11 C 0.1545(5) 0.2339(5) -0.0439(7) 0.090(5) Uani 0.94 1 d D U . . .
H11 H 0.144294 0.200779 -0.054067 0.108 Uiso 0.94 1 calc R U . A .
C12 C 0.2055(5) 0.2446(5) -0.0313(6) 0.077(4) Uani 0.94 1 d D U . A .
Ni1A Ni 0.29570(18) 0.29625(18) 0.0061(2) 0.0685(13) Uani 0.64 1 d . U . A 1
O1A O 0.4495(6) 0.0284(6) 0.0404(6) 0.016(3) Uani 0.5 1 d . U . . 1
O2A O 0.4487(5) 0.0513(5) -0.0513(5) 0.014(4) Uani 0.5 3 d S TU P . 1
Br1B Br 0.2874(3) 0.3142(5) 0.0722(4) 0.139(4) Uani 0.3 1 d . U . A 2
Br2B Br 0.3916(3) 0.3066(3) -0.0253(5) 0.122(4) Uani 0.3 1 d . U . A 2
Ni1B Ni 0.2974(4) 0.3009(4) -0.0247(4) 0.054(2) Uani 0.3 1 d . U . A 2
O1B O 0.4329(6) 0.0381(6) 0.0515(6) 0.017(3) Uani 0.5 1 d . U . . 2
O2B O 0.4605(5) 0.0395(5) -0.0395(5) 0.017(4) Uani 0.5 3 d S TU P . 2
Br4A Br 0.2988(6) 0.3991(8) -0.0150(12) 0.097(7) Uani 0.12 1 d . U . A 3
Br5A Br 0.2557(10) 0.2671(10) 0.0908(8) 0.114(6) Uani 0.12 1 d . U . A 3
Br1A Br 0.3004(2) 0.38782(17) 0.0261(3) 0.104(2) Uani 0.52 1 d . U . A 5
Br2A Br 0.3391(5) 0.3042(3) -0.0771(5) 0.195(5) Uani 0.4 1 d . U . A 5
Br3A Br 0.3787(11) 0.2878(10) 0.056(2) 0.194(11) Uani 0.12 1 d . U . A 5


_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
Zr1 O3 2.245(7) . ?
Zr1 O4 2.218(7) 6 ?
Zr1 O5 2.211(7) 19_656 ?
Zr1 O6 2.257(7) 4 ?
Zr1 O1A 2.073(17) . ?
Zr1 O1A 2.031(17) 24_656 ?
Zr1 O1A 2.081(16) 6 ?
Zr1 O2A 2.200(9) . ?
Zr1 O1B 2.251(17) . ?
Zr1 O1B 2.255(15) 6 ?
Zr1 O1B 2.266(17) 24_656 ?
Zr1 O2B 2.040(4) . ?
O3 C1 1.305(13) . ?
O4 C1 1.246(14) . ?
O5 C7 1.265(14) . ?
O6 C7 1.282(15) . ?
N1 C2 1.329(13) . ?
N1 C6 1.359(15) . ?
N1 Ni1A 2.021(11) . ?
N1 Ni1B 2.095(14) . ?
N2 C8 1.346(13) . ?
N2 C12 1.340(15) . ?
N2 Ni1A 2.078(11) . ?
N2 Ni1B 2.009(14) . ?
C1 C3 1.476(16) . ?
C2 H2 0.9500 . ?
C2 C3 1.391(15) . ?
C3 C4 1.360(18) . ?
C4 H4 0.9500 . ?
C4 C5 1.417(16) . ?
C5 H5 0.9500 . ?
C5 C6 1.421(17) . ?
C6 C12 1.437(19) . ?
C7 C9 1.503(16) . ?
C8 H8 0.9500 . ?
C8 C9 1.385(16) . ?
C9 C10 1.385(19) . ?
C10 H10 0.9500 . ?
C10 C11 1.399(17) . ?
C11 H11 0.9500 . ?
C11 C12 1.407(17) . ?
Ni1A Br4A 2.76(2) . ?
Ni1A Br5A 2.58(3) . ?
Ni1A Br1A 2.466(6) . ?
Ni1A Br2A 2.474(11) . ?
Ni1A Br3A 2.55(3) . ?
Br1B Ni1B 2.584(14) . ?
Br2B Ni1B 2.479(12) . ?

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
O3 Zr1 O6 122.1(3) . 4 ?
O3 Zr1 O1B 141.2(4) . 24_656 ?
O3 Zr1 O1B 140.3(5) . 6 ?
O3 Zr1 O1B 71.8(5) . . ?
O4 Zr1 O3 75.2(3) 6 . ?
O4 Zr1 O6 76.0(3) 6 4 ?
O4 Zr1 O1B 72.7(5) 6 6 ?
O4 Zr1 O1B 140.9(5) 6 . ?
O4 Zr1 O1B 141.1(4) 6 24_656 ?
O5 Zr1 O3 77.0(3) 19_656 . ?
O5 Zr1 O4 119.9(3) 19_656 6 ?
O5 Zr1 O6 75.7(3) 19_656 4 ?
O5 Zr1 O1B 71.7(5) 19_656 24_656 ?
O5 Zr1 O1B 72.2(4) 19_656 . ?
O5 Zr1 O1B 140.2(5) 19_656 6 ?
O6 Zr1 O1B 71.4(4) 4 24_656 ?
O1A Zr1 O3 142.1(5) 6 . ?
O1A Zr1 O3 142.1(5) 24_656 . ?
O1A Zr1 O3 83.7(4) . . ?
O1A Zr1 O4 84.7(4) 6 6 ?
O1A Zr1 O4 143.3(5) . 6 ?
O1A Zr1 O4 142.4(5) 24_656 6 ?
O1A Zr1 O5 140.5(5) 6 19_656 ?
O1A Zr1 O5 82.9(5) . 19_656 ?
O1A Zr1 O5 82.9(5) 24_656 19_656 ?
O1A Zr1 O6 82.1(5) 6 4 ?
O1A Zr1 O6 140.4(5) . 4 ?
O1A Zr1 O6 82.4(5) 24_656 4 ?
O1A Zr1 O1A 94.6(8) . 6 ?
O1A Zr1 O1A 62.0(6) 24_656 . ?
O1A Zr1 O1A 61.9(6) 24_656 6 ?
O1A Zr1 O2A 71.0(6) . . ?
O1A Zr1 O2A 70.9(6) 6 . ?
O1A Zr1 O2A 107.3(6) 24_656 . ?
O1A Zr1 O1B 70.4(7) 6 24_656 ?
O1A Zr1 O1B 109.3(6) . 6 ?
O1A Zr1 O1B 14.3(6) 24_656 24_656 ?
O1A Zr1 O1B 14.8(5) 6 6 ?
O1A Zr1 O1B 70.4(7) . 24_656 ?
O1A Zr1 O1B 71.4(7) 24_656 6 ?
O2A Zr1 O3 72.9(4) . . ?
O2A Zr1 O4 74.2(4) . 6 ?
O2A Zr1 O5 141.8(2) . 19_656 ?
O2A Zr1 O6 141.1(2) . 4 ?
O2A Zr1 O1B 76.4(5) . 6 ?
O2A Zr1 O1B 121.6(7) . 24_656 ?
O1B Zr1 O6 71.3(5) 6 4 ?
O1B Zr1 O6 140.5(5) . 4 ?
O1B Zr1 O1B 77.2(5) . 24_656 ?
O1B Zr1 O1B 77.1(5) 6 24_656 ?
O1B Zr1 O1B 124.1(7) . 6 ?
O2B Zr1 O3 83.7(5) . . ?
O2B Zr1 O4 85.1(6) . 6 ?
O2B Zr1 O6 141.3(2) . 4 ?
O2B Zr1 O1A 62.6(6) . 6 ?
O2B Zr1 O1B 71.0(4) . . ?
O2B Zr1 O1B 107.7(8) . 24_656 ?
O2B Zr1 O1B 71.0(5) . 6 ?
C1 O3 Zr1 130.9(6) . . ?
C1 O4 Zr1 131.2(7) . 12_554 ?
C7 O5 Zr1 131.6(7) . 22_565 ?
C7 O6 Zr1 130.2(7) . 4_455 ?
C2 N1 C6 119.6(10) . . ?
C2 N1 Ni1A 124.3(8) . . ?
C2 N1 Ni1B 127.7(8) . . ?
C6 N1 Ni1A 115.9(8) . . ?
C6 N1 Ni1B 109.5(8) . . ?
C8 N2 Ni1A 126.0(9) . . ?
C8 N2 Ni1B 125.0(9) . . ?
C12 N2 C8 118.6(10) . . ?
C12 N2 Ni1A 114.5(8) . . ?
C12 N2 Ni1B 114.3(8) . . ?
O3 C1 C3 114.3(10) . . ?
O4 C1 O3 127.5(10) . . ?
O4 C1 C3 118.1(10) . . ?
N1 C2 H2 118.6 . . ?
N1 C2 C3 122.9(11) . . ?
C3 C2 H2 118.6 . . ?
C2 C3 C1 120.1(11) . . ?
C4 C3 C1 121.6(11) . . ?
C4 C3 C2 118.3(10) . . ?
C3 C4 H4 119.8 . . ?
C3 C4 C5 120.3(13) . . ?
C5 C4 H4 119.8 . . ?
C4 C5 H5 121.9 . . ?
C4 C5 C6 116.1(13) . . ?
C6 C5 H5 121.9 . . ?
N1 C6 C5 120.1(11) . . ?
N1 C6 C12 115.3(10) . . ?
C5 C6 C12 122.1(11) . . ?
O5 C7 O6 129.0(10) . . ?
O5 C7 C9 116.0(11) . . ?
O6 C7 C9 114.9(11) . . ?
N2 C8 H8 118.3 . . ?
N2 C8 C9 123.3(11) . . ?
C9 C8 H8 118.3 . . ?
C8 C9 C7 118.7(12) . . ?
C10 C9 C7 123.4(11) . . ?
C10 C9 C8 117.8(11) . . ?
C9 C10 H10 120.0 . . ?
C9 C10 C11 120.0(12) . . ?
C11 C10 H10 120.0 . . ?
C10 C11 H11 121.2 . . ?
C10 C11 C12 117.6(13) . . ?
C12 C11 H11 121.2 . . ?
N2 C12 C6 115.0(10) . . ?
N2 C12 C11 122.2(11) . . ?
C11 C12 C6 122.7(11) . . ?
N1 Ni1A N2 78.3(4) . . ?
N1 Ni1A Br4A 153.2(8) . . ?
N1 Ni1A Br5A 85.0(7) . . ?
N1 Ni1A Br1A 177.1(5) . . ?
N1 Ni1A Br2A 83.2(4) . . ?
N1 Ni1A Br3A 96.0(7) . . ?
N2 Ni1A Br4A 90.7(5) . . ?
N2 Ni1A Br5A 84.2(7) . . ?
N2 Ni1A Br1A 100.0(4) . . ?
N2 Ni1A Br2A 97.6(5) . . ?
N2 Ni1A Br3A 166.6(11) . . ?
Br5A Ni1A Br4A 118.4(8) . . ?
Br1A Ni1A Br2A 94.8(3) . . ?
Br1A Ni1A Br3A 86.2(6) . . ?
Br2A Ni1A Br3A 93.7(12) . . ?
Zr1 O1A Zr1 113.6(8) . 12_554 ?
Zr1 O1A Zr1 116.9(7) 18_655 . ?
Zr1 O1A Zr1 116.5(8) 18_655 12_554 ?
Zr1 O2A Zr1 104.4(6) 12_554 6 ?
Zr1 O2A Zr1 104.4(6) 12_554 . ?
Zr1 O2A Zr1 104.4(6) 6 . ?
N1 Ni1B Br1B 89.6(6) . . ?
N1 Ni1B Br2B 98.3(5) . . ?
N2 Ni1B N1 78.2(5) . . ?
N2 Ni1B Br1B 82.5(5) . . ?
N2 Ni1B Br2B 176.0(7) . . ?
Br2B Ni1B Br1B 95.7(5) . . ?
Zr1 O1B Zr1 101.4(6) 12_554 18_655 ?
Zr1 O1B Zr1 101.5(6) . 18_655 ?
Zr1 O1B Zr1 101.0(6) . 12_554 ?
Zr1 O2B Zr1 116.8(4) 12_554 6 ?
Zr1 O2B Zr1 116.8(4) 12_554 . ?
Zr1 O2B Zr1 116.8(4) 6 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Zr1 O3 C1 O4 13.7(18) . . . . ?
Zr1 O3 C1 C3 -169.3(10) . . . . ?
Zr1 O4 C1 O3 -14.4(19) 12_554 . . . ?
Zr1 O4 C1 C3 168.7(10) 12_554 . . . ?
Zr1 O5 C7 O6 6.7(19) 22_565 . . . ?
Zr1 O5 C7 C9 -169.6(7) 22_565 . . . ?
Zr1 O6 C7 O5 -7.1(19) 4_455 . . . ?
Zr1 O6 C7 C9 169.2(7) 4_455 . . . ?
O3 C1 C3 C2 -4(2) . . . . ?
O3 C1 C3 C4 177.7(17) . . . . ?
O4 C1 C3 C2 173.4(13) . . . . ?
O4 C1 C3 C4 -5(3) . . . . ?
O5 C7 C9 C8 13.0(16) . . . . ?
O5 C7 C9 C10 -170.8(13) . . . . ?
O6 C7 C9 C8 -163.8(12) . . . . ?
O6 C7 C9 C10 12.4(17) . . . . ?
N1 C2 C3 C1 -178.1(10) . . . . ?
N1 C2 C3 C4 0(2) . . . . ?
N1 C6 C12 N2 7.6(18) . . . . ?
N1 C6 C12 C11 -175.1(14) . . . . ?
N2 C8 C9 C7 178.0(10) . . . . ?
N2 C8 C9 C10 2(2) . . . . ?
C1 C3 C4 C5 170(2) . . . . ?
C2 N1 C6 C5 12(2) . . . . ?
C2 N1 C6 C12 174.4(9) . . . . ?
C2 C3 C4 C5 -8(3) . . . . ?
C3 C4 C5 C6 17(4) . . . . ?
C4 C5 C6 N1 -19(3) . . . . ?
C4 C5 C6 C12 179.7(18) . . . . ?
C5 C6 C12 N2 169.5(17) . . . . ?
C5 C6 C12 C11 -13(2) . . . . ?
C6 N1 C2 C3 -2.3(15) . . . . ?
C7 C9 C10 C11 177.9(12) . . . . ?
C8 N2 C12 C6 178.9(9) . . . . ?
C8 N2 C12 C11 1.6(18) . . . . ?
C8 C9 C10 C11 -6(2) . . . . ?
C9 C10 C11 C12 8(2) . . . . ?
C10 C11 C12 N2 -6(2) . . . . ?
C10 C11 C12 C6 177.1(12) . . . . ?
C12 N2 C8 C9 0.6(17) . . . . ?
Ni1A N1 C2 C3 172.3(14) . . . . ?
Ni1A N1 C6 C5 -162.9(15) . . . . ?
Ni1A N1 C6 C12 -0.6(15) . . . . ?
Ni1A N2 C8 C9 -168.5(11) . . . . ?
Ni1A N2 C12 C6 -10.8(15) . . . . ?
Ni1A N2 C12 C11 171.9(12) . . . . ?
Ni1B N1 C2 C3 -159.7(14) . . . . ?
Ni1B N1 C6 C5 173.3(15) . . . . ?
Ni1B N1 C6 C12 -24.4(14) . . . . ?
Ni1B N2 C8 C9 163.2(12) . . . . ?
Ni1B N2 C12 C6 14.5(16) . . . . ?
Ni1B N2 C12 C11 -162.8(13) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.500(2)
2 0.500(2)





_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
