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_7709735
_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         '2(C H Cl3), C56 H50 N16 Ni2 S4'
_chemical_formula_sum            'C58 H52 Cl6 N16 Ni2 S4'
_chemical_formula_weight         1431.51
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -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                92.547(2)
_cell_angle_beta                 105.088(3)
_cell_angle_gamma                108.429(3)
_cell_formula_units_Z            2
_cell_length_a                   11.3032(11)
_cell_length_b                   15.1971(8)
_cell_length_c                   19.9582(12)
_cell_measurement_reflns_used    9225
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30.028
_cell_measurement_theta_min      2.450
_cell_volume                     3110.2(4)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL n/a (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0568
_diffrn_reflns_av_unetI/netI     0.0309
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            175196
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.089
_diffrn_reflns_theta_min         1.896
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.051
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.6794
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1086 before and 0.0663 after correction.
The Ratio of minimum to maximum transmission is 0.9107.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.529
_exptl_crystal_description       block
_exptl_crystal_F_000             1468
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         2.267
_refine_diff_density_min         -2.276
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     775
_refine_ls_number_reflns         18233
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0540
_refine_ls_R_factor_gt           0.0426
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0389P)^2^+6.3035P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1009
_refine_ls_wR_factor_ref         0.1057
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14962
_reflns_number_total             18233
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00154c2.cif
_cod_data_source_block           mo_ad190_k2_4_p-1
_cod_database_code               7709735
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.921
_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. Restrained distances
 Cl2B-C1 \\sim Cl2A-C1
 with sigma of 0.01
 Cl4B-C2 \\sim Cl4A-C2
 with sigma of 0.01
 Cl1A-C1 \\sim Cl1B-C1
 with sigma of 0.01
 Cl6B-C2 \\sim Cl6A-C2
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uiso(Cl6B) = Uiso(Cl6A)
Uiso(Cl2A) = Uiso(Cl2B)
Uiso(Cl4B) = Uiso(Cl4A)
Uiso(Cl1A) = Uiso(Cl1B)
4. Others
 Sof(H1B)=Sof(Cl2B)=Sof(Cl1A)=1-FVAR(1)
 Sof(H1A)=Sof(Cl1B)=Sof(Cl2A)=FVAR(1)
 Sof(H2A)=Sof(Cl4B)=Sof(Cl6A)=1-FVAR(2)
 Sof(H2B)=Sof(Cl6B)=Sof(Cl4A)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C8A(H8A), C8B(H8B), C2(H2A), C2(H2B)
5.b Aromatic/amide H refined with riding coordinates:
 C19A(H19A), C19B(H19B), C20A(H20A), C20B(H20B), C21A(H21A), C21B(H21B),
 C22A(H22A), C22B(H22B), C23A(H23A), C23B(H23B), C26A(H26A), C26B(H26B),
 C27A(H27A), C27B(H27B), C28A(H28A), C28B(H28B), C29A(H29A), C29B(H29B),
 C30A(H30A), C30B(H30B), C32A(H32A), C32B(H32B), C33A(H33A), C33B(H33B),
 C34A(H34A), C34B(H34B), C35A(H35A), C35B(H35B), C36A(H36A), C36B(H36B)
5.c Idealised Me refined as rotating group:
 C16A(H16A,H16B,H16C), C16B(H16D,H16E,H16F), C17A(H17A,H17B,H17C), C17B(H17D,
 H17E,H17F), C24A(H24A,H24B,H24C), C24B(H24D,H24E,H24F)
;
_shelx_res_checksum              58648
_olex2_submission_special_instructions 'No special instructions were received'