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_7719900
_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         'C38 H66 Fe N6 S2, 2(Cl O4), C H4 O'
_chemical_formula_sum            'C39 H69.99 Cl2 Fe N6 O9 S2'
_chemical_formula_weight         957.80
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-05
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-10-18 deposited with the CCDC.	2025-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.671(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.1064(3)
_cell_length_b                   17.0368(4)
_cell_length_c                   19.4289(4)
_cell_measurement_reflns_used    36787
_cell_measurement_temperature    180
_cell_measurement_theta_max      70.94
_cell_measurement_theta_min      3.45
_cell_volume                     4664.23(18)
_computing_cell_refinement
;
X-Area Recipe 1.37.0.0 (STOE, 2021)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.186.0 (STOE, 2022)
;
_computing_data_reduction
;
X-Area Integrate 2.5.3.0 (STOE, 2021)
X-Area LANA 2.7.5.0 (STOE, 2022)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material
;
STOE & Cie GmbH, X-Area, software package for collecting single-crystal or
multi-domain crystal data on STOE area-detector diffractometers, for image 
processing, for the correction and scaling of reflection intensities and 
for outlier rejection, version 2.1, Darmstadt 2022
;
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      180
_diffrn_detector                 Pilatus300K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 300K'
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_details
;
 1603 frames, detector distance = 60 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0173
_diffrn_reflns_av_unetI/netI     0.0157
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            30056
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         71.025
_diffrn_reflns_theta_min         3.452
_diffrn_source                   'GeniX 3D HF Cu'
_diffrn_source_current           0.600
_diffrn_source_power             0.030
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    4.952
_exptl_absorpt_correction_T_max  0.0589
_exptl_absorpt_correction_T_min  0.0233
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens in: F. R. Ahmed (Editor), "Crystallographic Computing", Munksgaard,
Copenhagen (1970), 255 - 270. Afterwards scaling of reflection intensities was
performed within STOE LANA. J. Koziskova, F. Hahn, J. Richter, J. Kozisek, Acta
Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Finally a spherical absorption correction was done within STOE LANA.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.364
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2040
_exptl_crystal_size_rad          0.141
_refine_diff_density_max         0.442
_refine_diff_density_min         -0.342
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     613
_refine_ls_number_reflns         8768
_refine_ls_number_restraints     149
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0417
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0565P)^2^+2.3904P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0962
_refine_ls_wR_factor_ref         0.0996
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7827
_reflns_number_total             8768
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02350e15.cif
_cod_data_source_block           sv-2138
_cod_database_code               7719900
_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, All N(H) groups, All O(H) groups
2. Restrained distances
 O9-C39
 1.42 with sigma of 0.02
 O9A-C39A
 1.42 with sigma of 0.02
 O9B-C39B
 1.42 with sigma of 0.02
 C39-O9 \\sim C39A-O9A \\sim C39B-O9B
 with sigma of 0.02
 Cl2-O5 \\sim Cl2-O6 \\sim Cl2-O8 \\sim Cl2-O7
 with sigma of 0.02
 Cl1A-O5A \\sim Cl1A-O8A \\sim Cl1A-O7A \\sim Cl1A-O6A
 with sigma of 0.02
 O5-O6 \\sim O5-O8 \\sim O5-O7 \\sim O6-O8 \\sim O6-O7 \\sim O8-O7
 with sigma of 0.02
 O5A-O8A \\sim O5A-O7A \\sim O5A-O6A \\sim O8A-O7A \\sim O8A-O6A \\sim O7A-O6A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Cl1A \\sim O6A \\sim O7A \\sim O5A \\sim O8A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Cl2 \\sim O8 \\sim O6 \\sim O7 \\sim O5: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C39) = Uanis(C39A) = Uanis(C39B)
Uanis(O9) = Uanis(O9A) = Uanis(O9B)
4. Rigid body (RIGU) restrains
 Cl1A, O6A, O7A, O5A, O8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl2, O8, O6, O7, O5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(O9)+Sof(H9)+Sof(C39)+Sof(H39A)+Sof(H39B)+Sof(H39C)]+1*[Sof(O9A)+
 Sof(H9AA)+Sof(C39A)+Sof(H39D)+Sof(H39E)+Sof(H39F)]+1*[Sof(O9B)+Sof(H9BA)+
 Sof(C39B)+Sof(H39G)+Sof(H39H)+Sof(H39I)]=1 with esd of 0.001
 Sof(Cl1A)=Sof(O6A)=Sof(O7A)=Sof(O5A)=Sof(O8A)=1-FVAR(1)
 Sof(Cl2)=Sof(O8)=Sof(O6)=Sof(O7)=Sof(O5)=FVAR(1)
 Sof(O9)=Sof(H9)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=FVAR(2)
 Sof(O9A)=Sof(H9AA)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=FVAR(3)
 Sof(O9B)=Sof(H9BA)=Sof(C39B)=Sof(H39G)=Sof(H39H)=Sof(H39I)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C27(H27A,H27B), C12(H12A,H12B), C24(H24A,H24B), C7(H7A,H7B),
 C15(H15A,H15B), C25(H25A,H25B), C22(H22A,H22B), C13(H13A,H13B), C10(H10A,H10B),
  C30(H30A,H30B), C9(H9A,H9B)
6.b Me refined with everything fixed:
 C39(H39A,H39B,H39C), C39A(H39D,H39E,H39F), C39B(H39G,H39H,H39I)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C19(H19), C21(H21), C5(H5)
6.d Tetrahedral OH refined with riding coordinates:
 O9B(H9BA)
6.e Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), C36(H36A,H36B,H36C), C34(H34A,H34B,H34C), C32(H32A,H32B,
 H32C), C14(H14A,H14B,H14C), C26(H26A,H26B,H26C), C8(H8A,H8B,H8C), C38(H38A,
 H38B,H38C), C23(H23A,H23B,H23C), C29(H29A,H29B,H29C), C33(H33A,H33B,H33C),
 C11(H11A,H11B,H11C)
6.f Idealised tetrahedral OH refined as rotating group:
 O9(H9), O9A(H9AA)
;
_shelx_res_checksum              64401
_shelx_hkl_checksum              62015
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '60.0 mm'
_stoe_detector_pixelsize_x       '0.172 mm'
_stoe_detector_pixelsize_y       '0.172 mm'
_stoe_detector_size_x            '8.4 cm'
_stoe_detector_size_y            '10.6 cm'
_stoe_evaluation_integration_a   4.3
_stoe_evaluation_integration_b   0.5
_stoe_evaluation_integration_ems 0.018
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 6
_stoe_evaluation_lana_bos_l_odd_max 3
_stoe_evaluation_lana_completeness 97.2
_stoe_evaluation_lana_dxs_max_order -
_stoe_evaluation_lana_dys_max_order -
_stoe_evaluation_lana_fs_max_order 8
_stoe_evaluation_lana_max_2theta_available 142.1
_stoe_evaluation_lana_max_2theta_desired 142.1
_stoe_evaluation_lana_mean_redundancy 3.4
_stoe_evaluation_lana_number_refls_after_or 30807
_stoe_evaluation_lana_number_refls_outliers 6344
_stoe_evaluation_lana_number_refls_total 37151
_stoe_evaluation_lana_number_refls_unique 9077
_stoe_evaluation_lana_number_refls_written 30807
_stoe_evaluation_lana_or_c1      0.035
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      0.7
_stoe_evaluation_lana_point_group 2/m
_stoe_evaluation_lana_table
;
2Theta          13.7   28.9   44.1   59.3   74.5   89.7  104.9  120.1  135.3
<Resolution>    5.43   2.98   2.04   1.56   1.25   1.09   0.97   0.89   0.84
N(total)         224    965   1916   2455   5954   7979   7879   6695   3084
<Redundancy>     2.7    3.0    2.8    2.3    3.8    4.3    3.9    3.3    2.3
Complet. [%%]    98.7   99.3   99.3   96.7   98.8  100.0   99.9   99.4   85.0
<I/sigma>      359.6  182.7  106.2   53.5   27.1   19.6   13.9   11.1   10.3
R(int)         0.008  0.009  0.010  0.014  0.022  0.022  0.031  0.039  0.049
;
_stoe_measurement_identifier     SV-2138
_stoe_measurement_max_exposure_per_frame '15.0 s'
_stoe_measurement_mean_exposure_per_frame '13.7 s'
_stoe_measurement_min_exposure_per_frame '10.0 s'
_stoe_measurement_total_exposure_time '6.1 h'
_stoe_measurement_total_frame_number 1603
_stoe_measurement_total_run_number 16
_stoe_measurement_tube_power     '30.0 W'