# Supplementary Information (SI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2024

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

data_exp_663_S0E0_L064
_database_code_depnum_ccdc_archive 'CCDC 2373766'
loop_
_audit_author_name
_audit_author_address
'Jeremiah Tidey'
;University of Warwick
United Kingdom
;
_audit_update_record             
;
2024-07-26 deposited with the CCDC.	2024-10-20 downloaded from the CCDC.
;

# start Validation Reply Form
_vrf_PLAT341_exp_663_S0E0_L064   
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............       0.04 Ang.  
RESPONSE: Data are from electron diffraction and, although multiple diffraction
 effects have been handled as far as possible using Olex2 N-beam refinement,
 there remain significant sources of uncertainty and propagating errors in the
 experiment. These include, for example, lense aberations and engineering
 effects which propagate to make unit cell parameters poorly defined.
;
# end Validation Reply Form


_audit_creation_date             2024-07-26
_audit_creation_method           
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_chemical_formula_moiety         'C6 H4 Cl2 N2 Ni S'
_chemical_formula_sum            'C6 H4 Cl2 N2 Ni S'
_chemical_formula_weight         265.777
_chemical_oxdiff_formula         'Ni Cl2 C6 H4 N2 O'
_chemical_oxdiff_usercomment     
'2024NCS0083, S009256, EMMJCA, Matt Cliffe sample - light grind on holey carbon at RT'
loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
_atom_type_scat_dispersion_source
C 0.00000 0.00000 0.60000 0.13600 0.54700 1.22500 40.93800 0.37400 3.27800
13.01300 0.00000 'Custom 4-Gaussian' custom
Cl 0.00000 0.00000 1.23200 0.34100 0.89300 2.39100 33.61200 0.33900 2.62500
11.09500 0.00000 'Custom 4-Gaussian' custom
H 0.00000 0.00000 0.12900 0.03600 0.12700 0.23600 37.73700 0.55300 3.77200
13.51800 0.00000 'Custom 4-Gaussian' custom
N 0.00000 0.00000 0.48200 0.13500 0.51900 1.07500 31.52600 0.32400 2.60700
10.01700 0.00000 'Custom 4-Gaussian' custom
Ni 0.00000 0.00000 1.89000 0.58200 1.87000 2.22100 65.30500 0.37300 3.00900
16.91700 0.00000 'Custom 4-Gaussian' custom
S 0.00000 0.00000 1.39000 0.34800 0.91500 2.50600 40.16900 0.36500 2.89000
13.04300 0.00000 'Custom 4-Gaussian' custom

_diffrn_oxdiff_scatteringfactors_ed 
'UCLA (2022) https://srv.mbi.ucla.edu/faes/data'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           51
_space_group_name_H-M_alt        'P m m a'
_space_group_name_Hall           '-P 2a 2a'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 x+1/2,-y,-z
3 -x,y,-z
4 -x+1/2,-y,z
5 -x,-y,-z
6 -x-1/2,y,z
7 x,-y,z
8 x-1/2,y,-z

_symmetry_Int_Tables_number      51
_cell_length_a                   12.67(7)
_cell_length_b                   3.55(11)
_cell_length_c                   8.87(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     399(13)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    1250
_cell_measurement_theta_max      1.1190
_cell_measurement_theta_min      0.0800
_cell_measurement_temperature    293(5)
_exptl_absorpt_coefficient_mu    0.000
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64349
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.121a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_description       'irregular, submicron grain'
_exptl_crystal_density_diffrn    2.214
_exptl_crystal_F_000             86.036
_diffrn_ambient_temperature      293(5)
_diffrn_reflns_av_R_equivalents  0.1099
_diffrn_reflns_av_unetI/netI     0.0864
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 1.0000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            3886
_diffrn_reflns_point_group_measured_fraction_full 1.0000
_diffrn_reflns_point_group_measured_fraction_max 1.0000
_diffrn_reflns_theta_full        0.8629
_diffrn_reflns_theta_max         1.13
_diffrn_reflns_theta_min         0.08
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-ED
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 1.0000
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -70.00  65.00   0.25    1.00    --    0.00   0.00   0.00  540
;
_diffrn_measurement_device       'electron diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy-ED, HyPix-ED, electron source at 200keV'
_diffrn_measurement_method       'continuous rotation electron diffraction'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0007780946
_diffrn_orient_matrix_UB_12      -0.0047333764
_diffrn_orient_matrix_UB_13      -0.0017719861
_diffrn_orient_matrix_UB_21      0.0016925294
_diffrn_orient_matrix_UB_22      -0.0001337861
_diffrn_orient_matrix_UB_23      -0.0014754796
_diffrn_orient_matrix_UB_31      0.0006762693
_diffrn_orient_matrix_UB_32      -0.0052486296
_diffrn_orient_matrix_UB_33      0.0016427274
_diffrn_oxdiff_ac6_digest_hkl_ed 
;
53a838aa50d2b538fb182826c8606408925d3f
;
_diffrn_oxdiff_digest_creation   
;
CAP 1.171.43.121a, AC 1.5-ac6-020
;
_diffrn_oxdiff_digest_dyn_ed     
;
614d788dc182f712c6b9aad9fab84f97e7ea73
;
_diffrn_radiation_monochromator  none
_diffrn_radiation_probe          electron
_diffrn_radiation_type           electron
_diffrn_radiation_wavelength     0.02510
_diffrn_source                   'electron diffractometer'
_diffrn_source_type              'JEOL JSM-2300ED, LaB6'
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              19
_reflns_limit_h_min              -19
_reflns_limit_k_max              5
_reflns_limit_k_min              -5
_reflns_limit_l_max              13
_reflns_limit_l_min              -13
_reflns_number_gt                967
_reflns_number_total             1510
_reflns_threshold_expression     I>=2u(I)
_computing_cell_refinement       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_collection       
'CrysAlisPro system (CCD 43.106a 64-bit (release 01-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_structure_refinement  
'olex2.refine 1.5-ac6-020 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         5.7582
_refine_diff_density_min         -2.1453
_refine_diff_density_rms         0.5173
_refine_ls_d_res_high            0.6389
_refine_ls_d_res_low             8.8703
_refine_ls_goodness_of_fit_ref   1.5416
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    2
_refine_ls_number_parameters     48
_refine_ls_number_reflns         890
_refine_ls_number_restraints     66
_refine_ls_R_factor_all          0.1478
_refine_ls_R_factor_gt           0.1214
_refine_ls_restrained_S_all      1.5080
_refine_ls_shift/su_max          -0.0006
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0600P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2743
_refine_ls_wR_factor_ref         0.2826
_refine_special_details          
;
 Given the history of the sample, there was ambiguity over the identity of site
 S1, i.e., whether purely S or disordered S / O. A model of the latter state is
 also obtainable, but O content refines to only a few percent in this dataset.
 In other datasets collected, up to 15% O can be obtained, but without any
 significant impact on the fit to the data (despite a significant increase in
 the number of variable parameters) and with decreased model stability. As a 
 consequence, a model comprising solely S at this position is chosen.

 The effects of multiple scattering are handled using Olex2 N-beam approach,
 based upon consideration of 20 beams, an Sg-based integration of 0.02 degrees
 with step-size 0.001. Weights are fixed at 0.06 and thickness is refined with
 frame scales being updated until convergence was obained.

 H atoms are placed geometrically and constrained to neutron bond lengths.

 All atoms are treated anisotropically in the presence of relatively soft rigid
 bond restraints, made marginally tighter for Ni1-Cl1 to stabilise Cl1 Uij, and
 including similarity restrains on C-H bonds to improve sense of H Uij.
;
_olex2_refinement_description    
;
1. Uiso/Uaniso restraints and constraints
C4 \\sim H4: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C5 \\sim H5: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.006 and sigma for 1-3 distances of 0.006
 Ni1, Cl1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C4(H4)
;
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
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_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_group
Ni1 Ni 0.5 1.0 0.5 0.0182(6) Uani 1.000000 4 S TU P .
Cl1 Cl 0.5528(2) 0.5 0.3301(3) 0.0220(7) Uani 1.000000 2 S TU P .
C3 C 0.3051(4) 1.0 0.2640(6) 0.0240(17) Uani 1.000000 2 S TU P .
N2 N 0.3450(4) 1.0 0.4072(6) 0.0245(14) Uani 1.000000 2 S TU P .
C5 C 0.3048(5) 1.0 -0.0064(7) 0.037(2) Uani 1.000000 2 S TU P .
H5 H 0.3461(5) 0.9999999999999999 -0.1133(7) 0.088(16) Uani 1.000000 2 RS TU P
.
C4 C 0.3632(5) 1.0 0.1265(6) 0.0313(17) Uani 1.000000 2 S TU P .
H4 H 0.4487(5) 0.9999999999999998 0.1255(6) 0.074(14) Uani 1.000000 2 RS TU P .
S1 S 0.25 1.0 0.5207(5) 0.0359(13) Uani 1.000000 4 S TU P 4


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
Ni1 Cl1 2.42(4) . ?
Ni1 Cl1 2.42(4) 3_656 ?
Ni1 Cl1 2.42(4) 3_666 ?
Ni1 Cl1 2.42(4) 1_565 ?
Ni1 N2 2.129(12) . ?
Ni1 N2 2.129(12) 3_656 ?
C3 C3 1.397(13) 4_575 ?
C3 N2 1.367(14) . ?
C3 C4 1.425(13) . ?
N2 S1 1.570(10) 4_575 ?
C5 C5 1.388(14) 4_575 ?
C5 H5 1.0830 . ?
C5 C4 1.393(13) . ?
C4 H4 1.0830 . ?

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
Cl1 Ni1 Cl1 94.17(10) 1_565 . ?
Cl1 Ni1 Cl1 180.0 3_656 1_565 ?
Cl1 Ni1 Cl1 85.83(10) 3_656 . ?
Cl1 Ni1 Cl1 180.0 3_666 . ?
Cl1 Ni1 Cl1 85.83(10) 3_666 1_565 ?
Cl1 Ni1 Cl1 94.17(10) 3_656 3_666 ?
N2 Ni1 Cl1 89.18(12) . 3_656 ?
N2 Ni1 Cl1 90.82(12) . . ?
N2 Ni1 Cl1 90.82(12) 3_656 3_656 ?
N2 Ni1 Cl1 89.18(12) 3_656 1_565 ?
N2 Ni1 Cl1 90.82(12) . 1_565 ?
N2 Ni1 Cl1 90.82(12) 3_656 3_666 ?
N2 Ni1 Cl1 89.18(12) 3_656 . ?
N2 Ni1 Cl1 89.18(12) . 3_666 ?
N2 Ni1 N2 180.0 . 3_656 ?
Ni1 Cl1 Ni1 94.17(10) 1_545 . ?
C4 C3 N2 127.1(5) . . ?
C3 N2 Ni1 134.5(4) . 3_656 ?
S1 N2 Ni1 117.4(3) 4_575 3_656 ?
S1 N2 C3 108.2(4) 4_575 . ?
C4 C5 H5 118.9(3) . . ?
C5 C4 C3 116.7(6) . . ?
H4 C4 C3 121.6(3) . . ?
H4 C4 C5 121.6(3) . . ?
N2 S1 N2 100.2(5) . 4_575 ?

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
Ni1 N2 C3 C3 -180.0 3_656 . . 4_575 ?
Ni1 N2 C3 C3 -180.0 . . . 4_575 ?
Ni1 N2 C3 C4 0.0 3_656 . . . ?
Ni1 N2 C3 C4 0.0 . . . . ?
Ni1 N2 S1 N2 180.0 . . 4_575 4_575 ?
Ni1 N2 S1 N2 -180.0 2_476 4_575 . . ?
C3 C3 N2 S1 0.0 . 4_575 4_575 . ?
C3 C3 C4 C5 0.0 4_575 . . . ?
C3 N2 S1 N2 0.0 . . 4_575 4_575 ?
C3 C4 C5 C5 -0.0 . . . 4_575 ?


_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.342
_oxdiff_exptl_absorpt_empirical_full_min 0.816
loop_
_restr_RIGU_atom_site_label_1
_restr_RIGU_atom_site_label_2
_restr_RIGU_target_weight_param
_restr_RIGU_U13_diff
_restr_RIGU_U23_diff
_restr_RIGU_U33_diff
Ni1 Cl1 0.006000 -0.000553 -0.003410 -0.002394
Ni1 Cl1 0.001000 -0.000553 -0.003410 -0.002394
Ni1 C3 0.006000 0.000224 -0.000347 -0.005169
Ni1 N2 0.006000 -0.001817 0.004702 0.001367
Ni1 S1 0.006000 -0.000070 -0.001200 -0.000155
Cl1 N2 0.006000 0.002056 -0.008616 0.001762
C3 N2 0.006000 0.002994 0.003223 -0.002848
C3 C5 0.006000 0.003444 -0.003444 0.002883
C3 C4 0.006000 -0.002867 0.003350 0.006781
C3 H4 0.006000 -0.001018 0.001818 -0.004332
C3 S1 0.006000 -0.002850 -0.002981 -0.011965
N2 C4 0.006000 0.002162 -0.002171 0.011090
N2 S1 0.006000 -0.001298 -0.002024 -0.007015
C5 H5 0.006000 -0.006319 0.007221 -0.002674
C5 C4 0.006000 -0.002842 -0.003356 -0.000703
C5 H4 0.006000 0.001075 0.001991 -0.003784
H5 C4 0.006000 0.010715 0.010771 0.010521
C4 H4 0.006000 0.000024 -0.002712 0.002470

loop_
_restr_U_similar_atom_site_label_1
_restr_U_similar_atom_site_label_2
_restr_U_similar_weight_param
C5 H5 0.0800
C4 H4 0.0800

####################################################################### 
# 
# 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_emmjca2
_database_code_depnum_ccdc_archive 'CCDC 2377919'
loop_
_audit_author_name
_audit_author_address
'Stephen P. Argent'
;University of Nottingham
United Kingdom
;
_audit_update_record             
;
2024-08-16 deposited with the CCDC.	2024-10-20 downloaded from the CCDC.
;
_nottingham_internal_coll_name   EMMJCA
_nottingham_internal_coll_number 19395
_nottingham_internal_coll_client EM/MJC
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_frame_time 60.00
_nottingham_internal_coll_frame_width 1.00
_nottingham_internal_coll_user   pczmjc1
_nottingham_internal_coll_date   24/03/2023
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVA, PL13110002'
_nottingham_internal_NCS_number  ?
_nottingham_internal_process_date 26/01/2024
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 26/01/2024
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 30/07/2024
_nottingham_internal_refinement_user pczspa
_nottingham_internal_self_archive_date ?
_nottingham_internal_self_validation_date ?
_nottingham_internal_self_validation_user ?
_nottingham_internal_validation_date 30/07/2024
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date ?
_refine_special_details          
;
The structure has been solved and refined in space group P4(2)bc with
 an asymmetric unit containing one complete benzoxadiazole ligand, one 
 chloride ligand and half a nickel(II) cation. The PLATON tool ADDSYM 
 suggests the presence of a new (pseudo) centre of symmetry and 
 alternative centrosymmetric space group P4(2)mbc. An attempt was made
 to solve and refine the structure in P4(2)mbc with an asymmetric unit
 containing half a benzoxadiazole ligand disordered over a symmetry
 element, half a chloride ligand and quarter of a nickel(II) cation.
 The centrosymmetric solution featuring disordered overlapping
 benzoxadiazole ligand reflected a structure with the same connectivity 
 as the non-centrosymmetric one, however, with a larger R1 value
 (P42(2)bc R1=%5.07 vs P4(2)mbc R1=%10.40). The Hooft parameter
 of 0.6(9) calculated for the weak data with a low resolution limit
 does not allow any conclusions to be drawn about the absolute 
 configuration, if any, of the structure. The alternative disordered 
 solution in centrosymmetric space group P4(2)mbc indicates that the 
 presence of inversion twinning is possible. Refining this P4(2)bc structure
 as an inversion twin with a fixed or refined twin fraction did not result
 in a lower R1 value so was not pursued. The very small crystal diffracted
 weakly with a data resolution limit of 1.20 %A, resulting in a low data
 to parameter ratio of 3.63. The structure could only be refined with
 anisotropic displacement parameters by way of applying rigid bond 
 and similarity restraints on the atoms of the benzoxadiazole ligand
 atoms (RIGU, SIMU). The anisotropic displacement parameter of carbon
 C7 was restrained to have more isotropic character (ISOR). The geometry
 of the benzoxadiazole ligand was restrained to be planer (FLAT). Irregular
 bond lengths around the phenyl ring of the ligand are likely a consequence
 of the weak data and ambiguity about symmetry discussed above. Attempts to
 restrain the benzoxadiazole ligand geometry to more reasonable and 
 symmetrical values resulted in poor refinement convergence and distorted
 anisotropic displacement ellipsoids. It was decided to leave the geometry
 unrestrained and note that no detailed conclusions can be drawn from the
 ligand geometry other than the binding mode, connectivity and gross 
 conformation of the structure.
;
_vrf_PLAT090_emmjca2             
;
PROBLEM: Poor Data / Parameter Ratio (Zmax > 18) ........       2.37 Note  
RESPONSE:
 The very small crystal diffracted weakly with data resolution limit of
 1.20 %, resulting in a low data to parameter ration of 3.63. The structure
 could only be refined with anisotropic displacement parameters by way of
 applying rigin bond and similarity restraints on those of the benzoxadiazole
 ligand atoms (RIGU, SIMU). The anisotropic displacement parameter of carbon
 C7 was restrained to have more isotropic character (ISOR). The geometry of
 the benzoxadiazole ligand was restrained to be planer (FLAT). 
;
_vrf_PLAT111_emmjca2             
;
PROBLEM: ADDSYM Detects New (Pseudo) Centre of Symmetry .        100 %Fit  
RESPONSE:
 The structure has been solved and refined in space group P4(2)bc with an
 asymmetric unit containing one complete benzoxadiazole ligand, one chloride
 ligand and half a nickel(II) cation. The PLATON tool ADDSYM suggests the
 presence of a new (pseudo) centre of symmetry and alternative
 centrosymmetric space group P4(2)mbc. An attempt to solve and refine the
 structure in P4(2)mbc with an asymmetric unit containing half a benzoxadiazole
 ligand disordered over a symmetry element, half a chloride ligand and quarter
 of a nickel(II) cation. The centrosymmetric solution featuring disordered
 overlapping benzoxadiazole ligand reflected a structure with the same
 connectivity as the non-centrosymmetric one, however, with a larger R1 value
 (P42(2)bc R1=%5.07 vs P4(2)mbc R1=%10.40).
;
_vrf_PLAT113_emmjca2             
;
PROBLEM: ADDSYM Suggests Possible Pseudo/New  Space Group    P42/mbc Check 
RESPONSE:
 The structure has been solved and refined in space group P4(2)bc with an
 asymmetric unit containing one complete benzoxadiazole ligand, one chloride
 ligand and half a nickel(II) cation. The PLATON tool ADDSYM suggests the
 presence of a new (pseudo) centre of symmetry and alternative
 centrosymmetric space group P4(2)mbc. An attempt to solve and refine the
 structure in P4(2)mbc with an asymmetric unit containing half a benzoxadiazole
 ligand disordered over a symmetry element, half a chloride ligand and quarter
 of a nickel(II) cation. The centrosymmetric solution featuring disordered
 overlapping benzoxadiazole ligand reflected a structure with the same
 connectivity as the non-centrosymmetric one, however, with a larger R1 value
 (P42(2)bc R1=%5.07 vs P4(2)mbc R1=%10.40).
;
_vrf_PLAT341_emmjca2             
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............       0.03 Ang.  
RESPONSE:
The geometry of the benzoxadiazole ligand was restrained to be planer
 (FLAT). Irregular bond lengths around the phenyl ring of the ligand are
 likely a consequence of the weak data and ambiguity about missing symmetry
 discussed above. Attempts to restrain the benzoxadiazole ligand geometry to
 more reasonable and symmetrical values resulted in poor refinement convergence
 and distorted anisotropic displacement ellipsoids. It was decided to leave the
 geometry unrestrained and note that no detailed conclusions can be drawn from
 the ligand geometry other than the binding mode, connectivity and gross
 conformation of the structure.
;
_vrf_STRVA01_emmjca2             
;
PROBLEM: Flack test results are meaningless.
RESPONSE:
 The Hooft parameter of 0.6(9) calculated for the weak data with a low
 resolution limit does not allow any conclusions to be drawn about the
 absolute configuration, if any, of the structure. The alternative disordered
 solution in centrosymmetric space group P4(2)mbc indicates that the presence
 of inversion twinning is possible. Refining this P4(2)bc structure as an
 inversion twin with a fixed or refined twin fraction did not result in a
 lower R1 value so was not pursued.
;
_vrf_THETM01_emmjca2             
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.550
RESPONSE:
 The very small crystal diffracted weakly with data resolution limit
 of 1.20 %, resulting in a low data to parameter ration of 3.63.
;
_audit_creation_date             2024-08-08
_audit_creation_method           
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        'nickel dichloride bis 2,1,3-benzoxadiazole'
_chemical_formula_moiety         'C12 H8 Cl2 N4 Ni O2'
_chemical_formula_sum            'C12 H8 Cl2 N4 Ni O2'
_chemical_formula_weight         369.83
_chemical_absolute_configuration unk
_chemical_melting_point          ?
_chemical_oxdiff_formula         C12H10Cl2N4NiO2
_chemical_oxdiff_usercomment     
'EMMJCA #19395 GVA-2045 EM/MJC fomblin oil on micromount'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ni Ni -3.0029 0.5091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      tetragonal
_space_group_IT_number           106
_space_group_name_H-M_alt        'P 42 b c'
_space_group_name_Hall           'P 4c -2ab'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-y, x, z+1/2'
'y, -x, z+1/2'
'x+1/2, -y+1/2, z'
'-x+1/2, y+1/2, z'
'-y+1/2, -x+1/2, z+1/2'
'y+1/2, x+1/2, z+1/2'

_cell_length_a                   14.1275(19)
_cell_length_b                   14.1275(19)
_cell_length_c                   6.8620(14)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1369.6(5)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    1668
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      44.1260
_cell_measurement_theta_min      4.3870
_shelx_estimated_absorpt_T_max   0.945
_shelx_estimated_absorpt_T_min   0.714
_exptl_absorpt_coefficient_mu    5.731
_exptl_absorpt_correction_T_max  0.968
_exptl_absorpt_correction_T_min  0.837
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.63a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'light green'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.794
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             744
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
5 1 0 0.0049
-5 -1 0 0.0049
0 1 0 0.0059
0 -1 0 0.0059
-1 5 -4 0.0230
1 -5 4 0.0230

_exptl_crystal_size_max          0.063
_exptl_crystal_size_mid          0.014
_exptl_crystal_size_min          0.01
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
4.9926 0.9970 0.0021 0.4844 0.2706 -0.0254
-4.9926 -0.9970 -0.0021 -0.4844 -0.2706 0.0254
0.0015 1.0006 0.0005 -0.0267 0.0861 -0.0614
-0.0015 -1.0006 -0.0005 0.0267 -0.0861 0.0614
-0.9747 5.0187 -3.9939 -0.0164 -0.0649 -1.0539
0.9747 -5.0187 3.9939 0.0164 0.0649 1.0539

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1107
_diffrn_reflns_av_unetI/netI     0.0799
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       5
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            2409
_diffrn_reflns_point_group_measured_fraction_full 0.859
_diffrn_reflns_point_group_measured_fraction_max 0.859
_diffrn_reflns_theta_full        39.895
_diffrn_reflns_theta_max         39.895
_diffrn_reflns_theta_min         4.426
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 4.2207
_diffrn_detector_type            'Agilent Diffraction Titan S2 detector'
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     11.00  36.00   1.00   60.00    --   43.12  82.00 -94.57   25
  2  ω     55.00  88.00   1.00   60.00    --   43.12  57.00 -90.00   33
  3  ω     17.00  43.00   1.00   60.00    --   43.12  71.00-140.87   26
  4  ω     55.00  81.00   1.00   60.00    --   43.12  71.00-140.87   26
  5  ω     20.00  45.00   1.00   60.00    --   43.12  55.00  23.73   25
  6  ω     53.00  79.00   1.00   60.00    --   43.12  55.00  23.73   26
  7  ω     20.00  57.00   1.00   60.00    --   43.12  44.00   1.00   37
  8  ω     62.00  95.00   1.00   60.00    --   43.12  44.00   1.00   33
  9  ω     87.00 112.00   1.00   60.00    --   43.12  42.00  92.80   25
 10  ω     16.00  42.00   1.00   60.00    --   43.12  69.00  57.36   26
 11  ω     44.00 111.00   1.00   60.00    --   43.12  69.00  57.36   67
 12  ω     25.00  89.00   1.00   60.00    --   43.12  45.00 124.86   64
 13  ω      4.00  67.00   1.00   60.00    --   43.12 -57.00-180.00   63
 14  ω     59.00 122.00   1.00   60.00    --   43.12-178.00 120.00   63
 15  ω     64.00  90.00   1.00   60.00    --   43.12 178.00-120.00   26
 16  ω    106.00 131.00   1.00   60.00    --   43.12 178.00-120.00   25
 17  ω     11.00  41.00   1.00   60.00    --   43.12  82.00  85.65   30
 18  ω     35.00 100.00   1.00   60.00    --   43.12-139.00 -58.00   65
 19  ω     16.00  41.00   1.00   60.00    --   43.12  78.00 -43.49   25
 20  ω     19.00  76.00   1.00   60.00    --   43.12 -99.00-180.00   57
 21  ω     14.00  39.00   1.00   60.00    --   43.12  77.00-137.30   25
 22  ω     12.00  37.00   1.00   60.00    --   43.12  79.00   2.78   25
 23  ω     21.00  50.00   1.00   60.00    --   43.12 -57.00 -30.00   29
 24  ω     30.00  97.00   1.00   60.00    --   43.12-131.00 116.00   67
 25  ω     13.00  47.00   1.00   60.00    --   43.12 -19.00 -30.00   34
 26  ω    -19.00  13.00   1.00   60.00    --   43.12 -38.00 -60.00   32
 27  ω     39.00  64.00   1.00   60.00    --   43.12 -38.00 -60.00   25
 28  ω    -27.00  29.00   1.00   60.00    --   43.12 -38.00  90.00   56
 29  ω    -18.00  25.00   1.00   60.00    --   43.12 -77.00-180.00   43
 30  ω    -17.00  38.00   1.00   60.00    --   43.12 -77.00 -60.00   55
 31  ω      6.00  31.00   1.00   60.00    --   43.12 -99.00 150.00   25
 32  ω     21.00  46.00   1.00   60.00    --   43.12  57.00 -90.00   25
 33  ω    -47.00 -35.00   1.00   60.00    --  -44.83 -65.00  29.90   12
;
_diffrn_measurement_device       'κ-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova, Titan S2'
_diffrn_measurement_method       'ω scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1024063000
_diffrn_orient_matrix_UB_12      -0.0267882000
_diffrn_orient_matrix_UB_13      -0.0545555000
_diffrn_orient_matrix_UB_21      0.0369973000
_diffrn_orient_matrix_UB_22      0.0858969000
_diffrn_orient_matrix_UB_23      0.1151648000
_diffrn_orient_matrix_UB_31      0.0071161000
_diffrn_orient_matrix_UB_32      -0.0614744000
_diffrn_orient_matrix_UB_33      0.1848955000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_reflns_Friedel_coverage         0.530
_reflns_Friedel_fraction_full    0.693
_reflns_Friedel_fraction_max     0.693
_reflns_number_gt                214
_reflns_number_total             352
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_computing_data_collection       
'CrysAlisPro system (CCD 41.123a (release 20-01-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         0.332
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.079
_refine_ls_abs_structure_details 
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.0(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     96
_refine_ls_number_reflns         352
_refine_ls_number_restraints     211
_refine_ls_R_factor_all          0.0944
_refine_ls_R_factor_gt           0.0507
_refine_ls_restrained_S_all      0.810
_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)+(0.0552P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1000
_refine_ls_wR_factor_ref         0.1217
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained planarity
 C10, C11, C6, C7, C8, C9
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim N3 \\sim N5 \\sim O4:
within 2.5A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2.5A
Uanis(C7) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 C6, C7, C8, C9, C10, C11, N3, N5, O4
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
5.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
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
Ni1 Ni 0.000000 0.500000 0.5611(19) 0.0255(19) Uani 1 2 d S T P . .
Cl2 Cl 0.0823(12) 0.4182(12) 0.315(3) 0.026(2) Uani 1 1 d . . . . .
N3 N 0.1009(13) 0.6072(13) 0.567(8) 0.032(4) Uani 1 1 d . U . . .
O4 O 0.1972(12) 0.5868(10) 0.569(6) 0.034(4) Uani 1 1 d . U . . .
N5 N 0.2512(12) 0.6691(14) 0.571(9) 0.036(4) Uani 1 1 d . U . . .
C6 C 0.1891(19) 0.7394(18) 0.572(7) 0.035(4) Uani 1 1 d . U . . .
C7 C 0.0978(15) 0.702(2) 0.567(8) 0.033(4) Uani 1 1 d . U . . .
C8 C 0.0195(17) 0.7685(15) 0.565(8) 0.039(4) Uani 1 1 d . U . . .
H8 H -0.044280 0.748417 0.579430 0.046 Uiso 1 1 calc R U . . .
C9 C 0.0426(17) 0.8589(17) 0.543(6) 0.043(5) Uani 1 1 d . U . . .
H9 H -0.007255 0.902241 0.517496 0.051 Uiso 1 1 calc R U . . .
C10 C 0.1384(16) 0.8971(16) 0.554(9) 0.040(4) Uani 1 1 d . U . . .
H10 H 0.148542 0.963608 0.554665 0.048 Uiso 1 1 calc R U . . .
C11 C 0.2136(16) 0.8360(15) 0.564(7) 0.040(4) Uani 1 1 d . U . . .
H11 H 0.277379 0.857149 0.566390 0.048 Uiso 1 1 calc R U . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Ni1 Cl2 2.355(18) . ?
Ni1 Cl2 2.390(18) 8_455 ?
Ni1 Cl2 2.355(18) 2_565 ?
Ni1 Cl2 2.390(18) 7 ?
Ni1 N3 2.081(17) 2_565 ?
Ni1 N3 2.081(17) . ?
N3 O4 1.390(18) . ?
N3 C7 1.34(2) . ?
O4 N5 1.391(17) . ?
N5 C6 1.33(2) . ?
C6 C7 1.39(3) . ?
C6 C11 1.41(3) . ?
C7 C8 1.45(3) . ?
C8 H8 0.9500 . ?
C8 C9 1.33(3) . ?
C9 H9 0.9500 . ?
C9 C10 1.46(3) . ?
C10 H10 0.9500 . ?
C10 C11 1.37(3) . ?
C11 H11 0.9500 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
Cl2 Ni1 Cl2 88.2(8) . 2_565 ?
Cl2 Ni1 Cl2 92.60(16) 2_565 8_455 ?
Cl2 Ni1 Cl2 86.6(8) 7 8_455 ?
Cl2 Ni1 Cl2 179.2(8) . 8_455 ?
Cl2 Ni1 Cl2 92.60(16) . 7 ?
Cl2 Ni1 Cl2 179.2(8) 2_565 7 ?
N3 Ni1 Cl2 91.9(15) 2_565 2_565 ?
N3 Ni1 Cl2 91.9(15) . . ?
N3 Ni1 Cl2 87.9(15) . 8_455 ?
N3 Ni1 Cl2 87.9(15) 2_565 7 ?
N3 Ni1 Cl2 89.7(14) 2_565 . ?
N3 Ni1 Cl2 90.5(15) . 7 ?
N3 Ni1 Cl2 89.7(14) . 2_565 ?
N3 Ni1 Cl2 90.5(15) 2_565 8_455 ?
N3 Ni1 N3 178(4) 2_565 . ?
Ni1 Cl2 Ni1 92.60(16) . 7_554 ?
O4 N3 Ni1 121.3(14) . . ?
C7 N3 Ni1 134.9(17) . . ?
C7 N3 O4 103.8(17) . . ?
N3 O4 N5 111.3(15) . . ?
C6 N5 O4 105.2(18) . . ?
N5 C6 C7 109(2) . . ?
N5 C6 C11 124(3) . . ?
C7 C6 C11 126(3) . . ?
N3 C7 C6 110(2) . . ?
N3 C7 C8 132(2) . . ?
C6 C7 C8 118(2) . . ?
C7 C8 H8 122.1 . . ?
C9 C8 C7 116(2) . . ?
C9 C8 H8 122.1 . . ?
C8 C9 H9 117.3 . . ?
C8 C9 C10 125(3) . . ?
C10 C9 H9 117.3 . . ?
C9 C10 H10 120.4 . . ?
C11 C10 C9 119(2) . . ?
C11 C10 H10 120.4 . . ?
C6 C11 H11 122.5 . . ?
C10 C11 C6 115(2) . . ?
C10 C11 H11 122.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Ni1 N3 O4 N5 180(4) . . . . ?
Ni1 N3 C7 C6 -180(5) . . . . ?
Ni1 N3 C7 C8 0(11) . . . . ?
N3 O4 N5 C6 0(6) . . . . ?
N3 C7 C8 C9 -172(6) . . . . ?
O4 N3 C7 C6 -1(7) . . . . ?
O4 N3 C7 C8 180(5) . . . . ?
O4 N5 C6 C7 -1(6) . . . . ?
O4 N5 C6 C11 -177(4) . . . . ?
N5 C6 C7 N3 1(6) . . . . ?
N5 C6 C7 C8 -179(5) . . . . ?
N5 C6 C11 C10 176(5) . . . . ?
C6 C7 C8 C9 8(7) . . . . ?
C7 N3 O4 N5 0(7) . . . . ?
C7 C6 C11 C10 1(4) . . . . ?
C7 C8 C9 C10 -11(7) . . . . ?
C8 C9 C10 C11 9(6) . . . . ?
C9 C10 C11 C6 -3(3) . . . . ?
C11 C6 C7 N3 177(5) . . . . ?
C11 C6 C7 C8 -4(7) . . . . ?

_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.784
_oxdiff_exptl_absorpt_empirical_full_min 0.775
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: ethanol'
####################################################################### 
# 
# 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_exp_659_S0E0_L07_twin1_hklf5
_database_code_depnum_ccdc_archive 'CCDC 2373767'
loop_
_audit_author_name
_audit_author_address
'Jeremiah Tidey'
;University of Warwick
United Kingdom
;
_audit_update_record             
;
2024-07-26 deposited with the CCDC.	2024-10-20 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT082_exp_659_S0E0_L07_twin1_hklf5 
;
PROBLEM: High R1 Value ..................................       0.16 Report
RESPONSE: Data are from electron diffraction of a non-merohedral rotation twin
 treated in the kinematic approximation. This actually constitutes a very good
 agreement in such a case.
;
_vrf_PLAT084_exp_659_S0E0_L07_twin1_hklf5 
;
PROBLEM: High wR2 Value (i.e. > 0.25) ...................       0.44 Report
RESPONSE: Data are from electron diffraction of a non-merohedral rotation twin
 treated in the kinematic approximation and this constitutes a very typical
 agreement in such a case.
;
_vrf_PLAT149_exp_659_S0E0_L07_twin1_hklf5 
;
PROBLEM: s.u. on the   beta    Angle is Too Large .......       0.15 Degree
RESPONSE: In current electron diffraction instruments, there remain significant
 sources of uncertainty and propagating errors in the experiment. Of particular
 note here are lense aberations and factors implicit to the engineering of the
 goniometer and rotation drive which make unit cell parameters poorly defined.
;
_vrf_PLAT341_exp_659_S0E0_L07_twin1_hklf5 
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............       0.03 Ang.  
RESPONSE: Data are from electron diffraction of a non-merohedral rotation twin
 treated in the kinematic approximation. These considerations already contribute
 to a large uncertainty in bond precision. In addition, there remain significant
 sources of uncertainty and propagating errors in the experiment. These include,
 for example, lense aberations and engineering effects which propagate to make
 unit cell parameters poorly defined.
;
# end Validation Reply Form


_audit_creation_date             2024-07-26
_audit_creation_method           
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_chemical_formula_moiety         'C6 H4 Cl2 N2 Ni O'
_chemical_formula_sum            'C6 H4 Cl2 N2 Ni O'
_chemical_formula_weight         249.710
_chemical_oxdiff_formula         'Ni Cl2 C6 H4 N2 O'
_chemical_oxdiff_usercomment     
'2024NCS0083, S009256, EMMJCA, Matt Cliffe sample - light grind on holey carbon at RT'
loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
_atom_type_scat_dispersion_source
C 0.00000 0.00000 0.60000 0.13600 0.54700 1.22500 40.93800 0.37400 3.27800
13.01300 0.00000 'Custom 4-Gaussian' custom
Cl 0.00000 0.00000 1.23200 0.34100 0.89300 2.39100 33.61200 0.33900 2.62500
11.09500 0.00000 'Custom 4-Gaussian' custom
H 0.00000 0.00000 0.12900 0.03600 0.12700 0.23600 37.73700 0.55300 3.77200
13.51800 0.00000 'Custom 4-Gaussian' custom
N 0.00000 0.00000 0.48200 0.13500 0.51900 1.07500 31.52600 0.32400 2.60700
10.01700 0.00000 'Custom 4-Gaussian' custom
Ni 0.00000 0.00000 1.89000 0.58200 1.87000 2.22100 65.30500 0.37300 3.00900
16.91700 0.00000 'Custom 4-Gaussian' custom
O 0.00000 0.00000 0.39200 0.14400 0.51100 0.93700 25.67500 0.30600 2.27200
8.27000 0.00000 'Custom 4-Gaussian' custom

_diffrn_oxdiff_scatteringfactors_ed 
'UCLA (2022) https://srv.mbi.ucla.edu/faes/data'
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_H-M_alt        'P 1 2/c 1'
_space_group_name_Hall           '-P 2yc'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -x,y,-z+1/2
3 -x,-y,-z
4 x,-y,z-1/2

_symmetry_Int_Tables_number      13
_cell_length_a                   3.52(7)
_cell_length_b                   8.96(9)
_cell_length_c                   12.17(8)
_cell_angle_alpha                90
_cell_angle_beta                 93.05(15)
_cell_angle_gamma                90
_cell_volume                     383(9)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    705
_cell_measurement_theta_max      1.0220
_cell_measurement_theta_min      0.0990
_cell_measurement_temperature    293(5)
_exptl_absorpt_coefficient_mu    0.000
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87465
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.43.121a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_description       'irregular, submicron grain'
_exptl_crystal_density_diffrn    2.166
_exptl_crystal_F_000             79.686
_diffrn_ambient_temperature      293(5)
_diffrn_reflns_av_R_equivalents  0.1561
_diffrn_reflns_av_unetI/netI     0.1104
_diffrn_reflns_Laue_measured_fraction_full 0.9815
_diffrn_reflns_Laue_measured_fraction_max 0.9462
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            1836
_diffrn_reflns_point_group_measured_fraction_full 0.9815
_diffrn_reflns_point_group_measured_fraction_max 0.9462
_diffrn_reflns_theta_full        0.8629
_diffrn_reflns_theta_max         1.03
_diffrn_reflns_theta_min         0.08
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-ED
_diffrn_measured_fraction_theta_full 0.9815
_diffrn_measured_fraction_theta_max 0.9462
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -70.00  70.00   0.25    0.25    --    0.00   0.00   0.00  560
;
_diffrn_measurement_device       'electron diffractometer'
_diffrn_measurement_device_type  
'XtaLAB Synergy-ED, HyPix-ED, electron source at 200keV'
_diffrn_measurement_method       'continuous rotation electron diffraction'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0016296000
_diffrn_orient_matrix_UB_12      0.0018558000
_diffrn_orient_matrix_UB_13      -0.0014940000
_diffrn_orient_matrix_UB_21      -0.0025315000
_diffrn_orient_matrix_UB_22      -0.0020708000
_diffrn_orient_matrix_UB_23      -0.0012228000
_diffrn_orient_matrix_UB_31      -0.0064847000
_diffrn_orient_matrix_UB_32      0.0003296000
_diffrn_orient_matrix_UB_33      0.0007318000
_diffrn_radiation_monochromator  none
_diffrn_radiation_probe          electron
_diffrn_radiation_type           electron
_diffrn_radiation_wavelength     0.02510
_diffrn_source                   'electron diffractometer'
_diffrn_source_type              'JEOL JSM-2300ED, LaB6'
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              4
_reflns_limit_h_min              -4
_reflns_limit_k_max              12
_reflns_limit_k_min              -12
_reflns_limit_l_max              17
_reflns_limit_l_min              -17
_reflns_number_gt                1479
_reflns_number_total             1836
_reflns_threshold_expression     I>=2u(I)
_computing_cell_refinement       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_collection       
'CrysAlisPro system (CCD 43.106a 64-bit (release 01-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_structure_refinement  
'olex2.refine 1.5-ac6-020 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_refine_diff_density_max         1.3754
_refine_diff_density_min         -1.2734
_refine_diff_density_rms         0.3134
_refine_ls_d_res_high            0.6992
_refine_ls_d_res_low             8.9611
_refine_ls_extinction_coef       21403(3253)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.7474
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    2
_refine_ls_number_parameters     61
_refine_ls_number_reflns         1836
_refine_ls_number_restraints     36
_refine_ls_R_factor_all          0.1782
_refine_ls_R_factor_gt           0.1621
_refine_ls_restrained_S_all      1.7300
_refine_ls_shift/su_max          0.0005
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.2P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4313
_refine_ls_wR_factor_ref         0.4444
_refine_special_details          
;
 Data are refined as a twin with a refined batch scale factor.

 The effects of multiple scattering are handled as an average using an
 extinction correction (EXTI).

 H atoms are placed geometrically and constrained to neutron bond lengths.

 Non-H atoms are treated anisotropically in the presence of a default rigid
 bond restraint. H atoms are treated isotropically with riding Uiso.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.567(8)
 0.433(8)
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5)
;
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
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_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
Ni1 Ni 1.0 1.0 0.5 0.0172(8) Uani 1.000000 2 S TU P
Cl1 Cl 0.5112(7) 0.8366(3) 0.55947(19) 0.0195(9) Uani 1.000000 1 . U .
O1 O 1.0 0.9783(7) 0.25 0.0182(14) Uani 1.000000 2 S TU P
N2 N 0.9830(15) 0.8930(6) 0.3419(4) 0.0204(13) Uani 1.000000 1 . U .
C3 C 0.9875(16) 0.7528(7) 0.3077(4) 0.0179(13) Uani 1.000000 1 . U .
C4 C 0.963(2) 0.6149(7) 0.3682(5) 0.0266(15) Uani 1.000000 1 . U .
H4 H 0.935(2) 0.6128(7) 0.4563(5) 0.076(15) Uiso 1.000000 1 R . .
C5 C 0.977(2) 0.4872(7) 0.3074(5) 0.0294(16) Uani 1.000000 1 . U .
H5 H 0.953(2) 0.3810(7) 0.3490(5) 0.082(16) Uiso 1.000000 1 R . .


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
Ni1 Cl1 2.40(3) 3_776 ?
Ni1 Cl1 2.40(3) 3_676 ?
Ni1 Cl1 2.40(3) 1_655 ?
Ni1 Cl1 2.40(3) . ?
Ni1 N2 2.148(13) 3_776 ?
Ni1 N2 2.148(13) . ?
O1 N2 1.359(9) 2_755 ?
O1 N2 1.359(9) . ?
N2 C3 1.324(14) . ?
C3 C3 1.411(13) 2_755 ?
C3 C4 1.444(13) . ?
C4 H4 1.0830 . ?
C4 C5 1.365(13) . ?
C5 C5 1.415(15) 2_755 ?
C5 H5 1.0830 . ?

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
Cl1 Ni1 Cl1 180.0 . 3_776 ?
Cl1 Ni1 Cl1 94.21(10) 3_676 3_776 ?
Cl1 Ni1 Cl1 94.21(10) . 1_655 ?
Cl1 Ni1 Cl1 180.0 3_676 1_655 ?
N2 Ni1 Cl1 89.33(15) . 3_776 ?
N2 Ni1 Cl1 91.00(15) 3_776 1_655 ?
N2 Ni1 Cl1 90.67(15) . . ?
N2 Ni1 Cl1 89.00(15) . 1_655 ?
N2 Ni1 Cl1 90.67(15) 3_776 3_776 ?
N2 Ni1 Cl1 89.33(15) 3_776 . ?
N2 Ni1 Cl1 91.00(15) . 3_676 ?
N2 Ni1 Cl1 89.00(15) 3_776 3_676 ?
N2 Ni1 N2 180.0 3_776 . ?
N2 O1 N2 111.6(6) . 2_755 ?
O1 N2 Ni1 119.1(4) 2_755 . ?
C3 N2 Ni1 134.9(4) . . ?
C3 N2 O1 105.8(5) . 2_755 ?
C3 C3 N2 108.4(3) 2_755 . ?
C4 C3 N2 130.5(5) . . ?
H4 C4 C3 122.1(3) . . ?
C5 C4 C3 115.9(5) . . ?
C5 C4 H4 122.1(3) . . ?
C5 C5 C4 123.0(4) 2_755 . ?
H5 C5 C4 118.5(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
Ni1 N2 O1 N2 175.06(5) . . 2_755 2_755 ?
Ni1 N2 O1 N2 175.06(5) 4_575 2_755 . . ?
Ni1 N2 C3 C3 -173.5(7) . . . 2_755 ?
Ni1 N2 C3 C3 -173.5(7) 3_776 . . 2_755 ?
Ni1 N2 C3 C4 8.0(8) 3_776 . . . ?
Ni1 N2 C3 C4 8.0(8) . . . . ?
O1 N2 C3 C3 0.7(5) . . . 2_755 ?
O1 N2 C3 C3 0.7(5) . 2_755 2_755 . ?
O1 N2 C3 C4 -177.7(4) . . . . ?
O1 N2 C3 C4 -177.7(4) 2_755 . . . ?
N2 C3 C3 N2 -0.9(3) . . 2_755 2_755 ?
N2 C3 C3 C4 177.7(6) . . 2_755 2_755 ?
N2 C3 C4 C5 -179.8(7) . . . . ?
C3 C3 C4 C5 2.0(9) 2_755 . . . ?
C3 C4 C5 C5 1.4(8) . . . 2_755 ?
C4 C5 C5 C4 -3.2(8) . . 2_755 2_755 ?


_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.585
_oxdiff_exptl_absorpt_empirical_full_min 0.558
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
loop_
_restr_RIGU_atom_site_label_1
_restr_RIGU_atom_site_label_2
_restr_RIGU_target_weight_param
_restr_RIGU_U13_diff
_restr_RIGU_U23_diff
_restr_RIGU_U33_diff
Ni1 Cl1 0.004000 -0.002094 -0.000439 -0.001855
Ni1 O1 0.004000 0.001148 0.002761 -0.005243
Ni1 N2 0.004000 0.000327 -0.000451 -0.002097
Ni1 C3 0.004000 -0.001476 -0.000301 -0.001094
Cl1 N2 0.004000 -0.002130 0.002146 -0.000010
O1 N2 0.004000 -0.005528 0.003978 0.000733
O1 C3 0.004000 -0.001748 0.006306 -0.010468
N2 C3 0.004000 -0.000146 -0.001322 -0.000310
N2 C4 0.004000 -0.000707 0.004927 -0.001368
C3 C4 0.004000 -0.002161 0.000008 0.002899
C3 C5 0.004000 0.003594 0.004252 -0.000136
C4 C5 0.004000 0.000465 0.000539 0.002831

loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
_oxdiff_twin_reflns_isolated
_oxdiff_twin_reflns_overlapped
_twin_individual_twin_lattice_type
_twin_individual_twin_matrix_11
_twin_individual_twin_matrix_12
_twin_individual_twin_matrix_13
_twin_individual_twin_matrix_21
_twin_individual_twin_matrix_22
_twin_individual_twin_matrix_23
_twin_individual_twin_matrix_31
_twin_individual_twin_matrix_32
_twin_individual_twin_matrix_33
1 0.567(8) 1727 1508 ref 1.0000 0.0000 0.0000 0.0000 1.0000 0.0000 0.0000
0.0000 1.0000
2 0.433(8) 1731 1508 nmt -0.9998 -0.0004 -0.0001 0.0014 -1.0003 -0.0008 0.3504
-0.0017 0.9991

_twin_special_details            
;
Component 2 rotated by 179.9636° 
around [-0.00 -0.00 1.00] (reciprocal) or [0.17 -0.00 0.98] (direct)
;
