Electronic effects of substituents on the catalytic conversion of thiolates to alcohols by carboxylate bridged nonheme binuclear Fe(II) and Co(II) complexes.
Chakraborty, Anuj Baran; Hazra, Rajib; Mukherjee, Srimayee; Majumdar, Amit; Dalton transactions (Cambridge, England : 2003) 55 (2026) 1335–1348; doi:10.1039/d5dt02420j

data_7720548
_publ_section_title
;
 Electronic effects of substituents on the catalytic conversion of
 thiolates to alcohols by carboxylate bridged nonheme binuclear Fe(II) and
 Co(II) complexes.
;
_journal_issue                   3
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              1335
_journal_page_last               1348
_journal_paper_doi               10.1039/d5dt02420j
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C86 H75 Co2 F2 N11 O3, 2(B F4), 2(C2 H3 N)'
_chemical_formula_sum            'C90 H81 B2 Co2 F10 N13 O3'
_chemical_formula_weight         1722.15
_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
_audit_creation_date             2025-05-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-09-16 deposited with the CCDC.	2025-12-15 downloaded from the CCDC.
;
_cell_angle_alpha                90.995(3)
_cell_angle_beta                 105.600(4)
_cell_angle_gamma                91.867(4)
_cell_formula_units_Z            2
_cell_length_a                   13.9956(7)
_cell_length_b                   15.4261(6)
_cell_length_c                   21.4618(7)
_cell_measurement_reflns_used    12671
_cell_measurement_temperature    130(2)
_cell_measurement_theta_max      25.4780
_cell_measurement_theta_min      1.9540
_cell_volume                     4458.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      130(2)
_diffrn_detector                 'PHOTON II Detector'
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -99.91  13.09   1.00    5.00    --  -15.95 -59.25 173.08  113
  2  \w    -59.55  22.45   1.00    5.00    --  -15.95  83.74 -29.95   82
  3  \w    -99.91  13.09   1.00    5.00    --  -15.95 -59.25  71.08  113
  4  \w    -59.55  22.45   1.00    5.00    --  -15.95  83.74-134.95   82
;
_diffrn_measurement_device       'Bruker D8VENTURE with PHOTON II Detector'
_diffrn_measurement_method       'phi, omega and kappa scan'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0234595000
_diffrn_orient_matrix_UB_12      -0.0371206000
_diffrn_orient_matrix_UB_13      0.0151858000
_diffrn_orient_matrix_UB_21      0.0219360000
_diffrn_orient_matrix_UB_22      0.0253898000
_diffrn_orient_matrix_UB_23      0.0284319000
_diffrn_orient_matrix_UB_31      -0.0417292000
_diffrn_orient_matrix_UB_32      -0.0097683000
_diffrn_orient_matrix_UB_33      0.0118023000
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0895
_diffrn_reflns_av_unetI/netI     0.0985
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            41765
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.682
_diffrn_reflns_theta_min         1.969
_diffrn_source_type              Micro-focus
_exptl_absorpt_coefficient_mu    0.448
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89967
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'reddish pink'
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1780
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.812
_refine_diff_density_min         -0.962
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1064
_refine_ls_number_reflns         16710
_refine_ls_number_restraints     77
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0902
_refine_ls_R_factor_gt           0.0718
_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^)+(0.1184P)^2^+0.6254P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1982
_refine_ls_wR_factor_ref         0.2187
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12274
_reflns_number_total             16710
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02420j2.cif
_cod_data_source_block           sol1
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               7720548
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O Co B F'
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.908
_reflns_odcompleteness_completeness 98.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.63
_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
 F8-B2 \\sim F9B-B2 \\sim F9A-B2 \\sim F10A-B2 \\sim F10B-B2 \\sim F7B-B2 \\sim
F7A-B2
 with sigma of 0.02
 C76B-C71 \\sim C76B-C75B \\sim C75B-C74B \\sim C74B-C73B \\sim C73B-C72B \\sim
C72B-C71 \\sim C76A-
 C71 \\sim C76A-C75A \\sim C75A-C74A \\sim C74A-C73A \\sim C73A-C72A
 with sigma of 0.02
 C91-C90A \\sim C91-C90B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F8) = Uanis(F7A) = Uanis(F7B) = Uanis(F9A) = Uanis(F9B) = Uanis(F10A) =
Uanis(F10B)
Uanis(C71) = Uanis(C72B) = Uanis(C73B) = Uanis(C74B) = Uanis(C75B) =
Uanis(C76B) = Uanis(C72A) = Uanis(C73A) = Uanis(C74A) = Uanis(C75A) =
Uanis(C76A)
Uanis(C91) = Uanis(C90B) = Uanis(C90A)
4. Others
 Sof(C72B)=Sof(H72B)=Sof(C73B)=Sof(H73B)=Sof(C74B)=Sof(H74B)=Sof(C75B)=
 Sof(H75B)=Sof(C76B)=Sof(H76B)=Sof(F7B)=Sof(F9B)=Sof(F10B)=Sof(C90B)=Sof(H90D)=
 Sof(H90E)=Sof(H90F)=1-FVAR(1)
 Sof(C72A)=Sof(H72A)=Sof(C73A)=Sof(H73A)=Sof(C74A)=Sof(H74A)=Sof(C75A)=
 Sof(H75A)=Sof(C76A)=Sof(H76A)=Sof(F7A)=Sof(F9A)=Sof(F10A)=Sof(C90A)=Sof(H90A)=
 Sof(H90B)=Sof(H90C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C26(H26A,H26B), C43(H43A,H43B), C44(H44A,H44B),
 C61(H61A,H61B)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C20(H20),
 C21(H21), C22(H22), C23(H23), C24(H24), C30(H30), C31(H31), C32(H32), C33(H33),
  C34(H34), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C48(H48),
 C49(H49), C50(H50), C51(H51), C52(H52), C55(H55), C56(H56), C57(H57), C58(H58),
  C59(H59), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69), C72A(H72A),
 C72B(H72B), C73A(H73A), C73B(H73B), C74A(H74A), C74B(H74B), C75A(H75A),
 C75B(H75B), C76A(H76A), C76B(H76B), C81(H81), C82(H82), C83(H83)
5.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C25(H25A,H25B,H25C), C42(H42A,H42B,H42C), C60(H60A,H60B,
 H60C), C77(H77A,H77B,H77C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C),
 C90A(H90A,H90B,H90C), C90B(H90D,H90E,H90F)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              24605
_shelx_hkl_checksum              61579
_shelx_fab_checksum              87828
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.416
_oxdiff_exptl_absorpt_empirical_full_min 0.649