Mononuclear FeII and Heterobinuclear FeIINiII Thiolate Complexes Derived from a Compartmental Hexaazadithiophenolato Ligand: Synthesis, Structure and Properties
Stephan, Vanessa; Zocher, Christian; Börner, Martin; Klose, Jennifer; Fuhrmann, Daniel; Kersting, Berthold; Dalton Transactions  (2025) –; doi:10.1039/D5DT02350E

data_7719899
_publ_section_title
;
 Mononuclear FeII and Heterobinuclear FeIINiII Thiolate Complexes Derived
 from a Compartmental Hexaazadithiophenolato Ligand: Synthesis, Structure
 and Properties
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT02350E
_journal_year                    2025
_chemical_formula_moiety         'C40 H67 Fe N6 Ni O2 S2, C24 H20 B, C2 H3 N'
_chemical_formula_sum            'C66 H90 B Fe N7 Ni O2 S2'
_chemical_formula_weight         1202.93
_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             2021-02-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2024-10-18 deposited with the CCDC.	2025-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                108.791(4)
_cell_angle_beta                 92.255(4)
_cell_angle_gamma                107.496(3)
_cell_formula_units_Z            2
_cell_length_a                   13.3261(6)
_cell_length_b                   15.6750(8)
_cell_length_c                   16.9825(7)
_cell_measurement_reflns_used    27132
_cell_measurement_temperature    180
_cell_measurement_theta_max      26.59
_cell_measurement_theta_min      1.78
_cell_volume                     3166.3(3)
_computing_cell_refinement       'X-Area Recipe 1.33.0.0 (STOE, 2015)'
_computing_data_collection       'X-Area WinXpose 2.0.22.0 (STOE, 2016)'
_computing_data_reduction
;
X-Area Integrate 1.77.0.0 (STOE, 2019)
X-Area LANA 1.77.1.0 (STOE, 2019)
;
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      180
_diffrn_detector                 'image plate (34 cm diameter / schwenk)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            'STOE Imaging Plate'
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.957
_diffrn_measurement_details
;
 283 frames, detector distance = 110 mm
;
_diffrn_measurement_device       '2-circle diffractometer'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter, multiple pinhole'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0379
_diffrn_reflns_av_unetI/netI     0.0497
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            22706
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.347
_diffrn_reflns_theta_min         2.036
_diffrn_source
'sealed X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_current           0.000
_diffrn_source_power             0.000
_diffrn_source_voltage           0
_exptl_absorpt_coefficient_mu    0.641
_exptl_absorpt_correction_T_max  0.8890
_exptl_absorpt_correction_T_min  0.6935
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.262
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1284
_exptl_crystal_size_max          0.427
_exptl_crystal_size_mid          0.236
_exptl_crystal_size_min          0.227
_refine_diff_density_max         0.526
_refine_diff_density_min         -0.567
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     797
_refine_ls_number_reflns         12364
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0697
_refine_ls_R_factor_gt           0.0428
_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^)+(0.0588P)^2^+0.5772P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1003
_refine_ls_wR_factor_ref         0.1090
_reflns_d_resolution_high        0.801
_reflns_d_resolution_low         14.002
_reflns_Friedel_coverage         0.000
_reflns_limit_h_max              16
_reflns_limit_h_min              -14
_reflns_limit_k_max              15
_reflns_limit_k_min              -19
_reflns_limit_l_max              21
_reflns_limit_l_min              -21
_reflns_number_gt                8827
_reflns_number_total             12366
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02350e15.cif
_cod_data_source_block           shelx
_cod_database_code               7719899
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.771
_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. Shared sites
{Ni2, Fe1}
{Ni1, Fe2}
3. Restrained distances
 C31-C32 \\sim C31-C33 \\sim C31-C34
 with sigma of 0.02
 C35-C36 \\sim C35-C37 \\sim C35-C38
 with sigma of 0.02
 C31-C32A \\sim C31-C33A \\sim C31-C34A
 with sigma of 0.02
 C36-C37 \\sim C36-C38 \\sim C37-C38
 with sigma of 0.02
 C32A-C33A \\sim C32A-C34A \\sim C33A-C34A
 with sigma of 0.02
 C35-C36A \\sim C35-C37A \\sim C35-C38A
 with sigma of 0.02
 C36A-C37A \\sim C36A-C38A \\sim C37A-C38A
 with sigma of 0.02
 C32-C33 \\sim C32-C34 \\sim C33-C34
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(Ni1) = Uanis(Fe2)
Uanis(Ni2) = Uanis(Fe1)
5. Others
 Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=Sof(C36A)=Sof(H36D)=Sof(H36E)=
 Sof(H36F)=Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=1-FVAR(1)
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(1)
 Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=Sof(C33A)=Sof(H33D)=Sof(H33E)=
 Sof(H33F)=Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(2)
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(2)
 Fixed Sof: Ni1(0.5) Fe1(0.5) Fe2(0.5) Ni2(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C22(H22A,H22B), C25(H25A,H25B), C27(H27A,H27B), C15(H15A,H15B),
 C30(H30A,H30B), C24(H24A,H24B), C9(H9A,H9B), C10(H10A,H10B), C28(H28A,H28B),
 C12(H12A,H12B), C13(H13A,H13B)
6.b Aromatic/amide H refined with riding coordinates:
 C42(H42), C46(H46), C45(H45), C3(H3), C5(H5), C44(H44), C58(H58), C54(H54),
 C21(H21), C48(H48), C64(H64), C63(H63), C19(H19), C57(H57), C56(H56), C60(H60),
  C55(H55), C52(H52), C43(H43), C62(H62), C61(H61), C51(H51), C50(H50), C49(H49)
6.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C23(H23A,H23B,H23C), C8(H8A,H8B,H8C), C29(H29A,H29B,
 H29C), C40(H40A,H40B,H40C), C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C34(H34A,
 H34B,H34C), C32(H32A,H32B,H32C), C38(H38A,H38B,H38C), C33(H33A,H33B,H33C),
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C65(H65A,H65B,H65C), C38A(H38D,H38E,
 H38F), C36A(H36D,H36E,H36F), C37A(H37D,H37E,H37F), C32A(H32D,H32E,H32F),
 C33A(H33D,H33E,H33F), C34A(H34D,H34E,H34F)
;
_shelx_res_checksum              3196
_shelx_hkl_checksum              1629
_olex2_submission_special_instructions 'No special instructions were received'