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_7709734
_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         'C54 H48 N18 Ni2 S4, 2[CH4O], 2[H2O]'
_chemical_formula_sum            'C54 H48 N18 Ni2 S4'
_chemical_formula_weight         1194.76
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-06
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   34.235(5)
_cell_length_b                   34.235(5)
_cell_length_c                   20.889(4)
_cell_measurement_reflns_used    46038
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.285
_cell_measurement_theta_min      1.125
_cell_volume                     24483(7)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Arinax MD2S/Pilatus 6M'
_diffrn_measurement_method       'rotating crystal'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.700
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0127
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            131080
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        24.285
_diffrn_reflns_theta_max         24.285
_diffrn_reflns_theta_min         1.125
_exptl_absorpt_coefficient_mu    0.771
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       prism
_exptl_crystal_F_000             9888
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.491
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.055
_refine_ls_extinction_coef       0.000074(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     766
_refine_ls_number_reflns         10311
_refine_ls_number_restraints     764
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0643
_refine_ls_R_factor_gt           0.0543
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1044P)^2^+20.1051P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1631
_refine_ls_wR_factor_ref         0.1736
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8320
_reflns_number_total             10311
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00154c2.cif
_cod_data_source_block           ad_148mic_5_c5
_cod_original_cell_volume        24483(9)
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               7709734
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C33D) \\sim Ueq, Uanis(C32D) \\sim Ueq: with sigma of 0.05 and sigma for
terminal atoms of 0.05
Uanis(C36C) \\sim Ueq, Uanis(C35D) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(C23C)=Sof(H23C)=Sof(C22C)=Sof(H22C)=Sof(C21C)=Sof(H21C)=Sof(C20C)=
 Sof(H20C)=Sof(C19C)=Sof(H19C)=Sof(C18C)=1-FVAR(1)
 Sof(C23B)=Sof(H23B)=Sof(C22B)=Sof(H22B)=Sof(C21B)=Sof(H21B)=Sof(C20B)=
 Sof(H20B)=Sof(C19B)=Sof(H19B)=Sof(C18B)=FVAR(1)
 Sof(C36C)=Sof(H36C)=Sof(C35D)=Sof(H35D)=Sof(H34B)=Sof(C33D)=Sof(H33D)=
 Sof(C32D)=Sof(H32D)=1-FVAR(2)
 Sof(C36B)=Sof(H36B)=Sof(C33C)=Sof(H33C)=Sof(C32C)=Sof(H32C)=Sof(H34C)=
 Sof(C35C)=Sof(H35C)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C8A(H8A), C8B(H8B)
5.b Aromatic/amide H refined with riding coordinates:
 C19A(H19A), C20A(H20A), C21A(H21A), C22A(H22A), C23A(H23A), C26A(H26A),
 C27A(H27A), C29A(H29A), C30A(H30A), C32A(H32A), C33A(H33A), C34A(H34A),
 C35A(H35A), C36A(H36A), C23B(H23B), C22B(H22B), C21B(H21B), C20B(H20B),
 C19B(H19B), C26B(H26B), C27B(H27B), C29B(H29B), C30B(H30B), C36B(H36B),
 C23C(H23C), C22C(H22C), C21C(H21C), C20C(H20C), C19C(H19C), C33C(H33C),
 C32C(H32C), C36C(H36C), C35D(H35D), C34C(H34C), C34C(H34B), C33D(H33D),
 C32D(H32D), C35C(H35C)
5.c Fitted hexagon refined as free rotating group:
 C23B(C22B,C21B,C20B,C19B,C18B), C23C(C22C,C21C,C20C,C19C,C18C), C31C(C36C,
 C35D,C34C,C33D,C32D)
5.d Idealised Me refined as rotating group:
 C16A(H16A,H16B,H16C), C17A(H17A,H17B,H17C), C24A(H24A,H24B,H24C), C16B(H16D,
 H16E,H16F), C17B(H17D,H17E,H17F), C24B(H24D,H24E,H24F)
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_smtbx_masks_special_details
;
A solvent mask was calculated and 888 electrons were 
found in a volume of 4428\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 2[CH4O], 2[H2O] per Formula Unit 
which account for 896 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              49254
_shelx_fab_checksum              59694
_olex2_submission_special_instructions 'No special instructions were received'