Diastereomeric dinickel(ii) complexes with non-innocent bis(octaazamacrocyclic) ligands: isomerization, spectroelectrochemistry, DFT calculations and use in catalytic oxidation of cyclohexane
Dobrov, Anatolie; Darvasiová, Denisa; Zalibera, Michal; Bučinský, Lukáš; Jelemenská, Ingrid; Rapta, Peter; Shova, Sergiu; Dumitrescu, Dan G.; Andrade, Marta A.; Martins, Luísa M. D. R. S.; Pombeiro, Armando J. L.; Arion, Vladimir B.; Dalton Transactions  (2022) –; doi:10.1039/D2DT00154C

data_7709733
_publ_section_title
;
 Diastereomeric dinickel(ii) complexes with non-innocent
 bis(octaazamacrocyclic) ligands: isomerization, spectroelectrochemistry,
 DFT calculations and use in catalytic oxidation of cyclohexane
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00154C
_journal_year                    2022
_chemical_formula_moiety         'C56 H50 N16 Ni2 S4, 1.6[CHCl3]'
_chemical_formula_sum            'C56 H50 N16 Ni2 S4'
_chemical_formula_weight         1192.78
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-05
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-02-09 deposited with the CCDC.	2022-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.972(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.5994(11)
_cell_length_b                   14.0392(14)
_cell_length_c                   21.2185(17)
_cell_measurement_reflns_used    4371
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      29.758
_cell_measurement_theta_min      2.349
_cell_volume                     3099.7(5)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.700
_diffrn_reflns_av_R_equivalents  0.1549
_diffrn_reflns_av_unetI/netI     0.0773
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            47122
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.835
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.313
_exptl_absorpt_coefficient_mu    0.760
_exptl_absorpt_correction_T_max  0.4932
_exptl_absorpt_correction_T_min  0.4175
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0986 before and 0.0846 after correction.
The Ratio of minimum to maximum transmission is 0.8465.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.278
_exptl_crystal_description       block
_exptl_crystal_F_000             1236
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     355
_refine_ls_number_reflns         5708
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0707
_refine_ls_R_factor_gt           0.0459
_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/[\s^2^(Fo^2^)+(0.0464P)^2^+0.4384P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1061
_refine_ls_wR_factor_ref         0.1160
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4063
_reflns_number_total             5708
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00154c2.cif
_cod_data_source_block           andokk3_p21n
_cod_database_code               7709733
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.970
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C8(H8)
2.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C26(H26), C27(H27),
 C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
2.c Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C24(H24A,H24B,H24C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 192 electrons were 
found in a volume of 710\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 1.6[CHCl3] per Formula Unit 
which account for 186 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              99262
_shelx_fab_checksum              25236
_olex2_submission_special_instructions 'No special instructions were received'