Biomimics of [FeFe]-hydrogenases incorporating redox-active ligands: synthesis, redox properties and spectroelectrochemistry of diiron-dithiolate complexes with ferrocenyl-diphosphines as Fe4S4 surrogates
Orton, Georgia R. F.; Ghosh, Shishir; Alker, Lucy; Sarker, Jagodish C.; Pugh, David; Richmond, Michael G.; Hartl, František; Hogarth, Graeme; Dalton Transactions  (2022) –; doi:10.1039/D2DT00419D

data_7710489
_publ_section_title
;
 Biomimics of [FeFe]-hydrogenases incorporating redox-active ligands:
 synthesis, redox properties and spectroelectrochemistry of
 diiron-dithiolate complexes with ferrocenyl-diphosphines as Fe4S4
 surrogates
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00419D
_journal_year                    2022
_chemical_formula_moiety         'C40 H32 Fe3 O4 P2 S2'
_chemical_formula_sum            'C40 H32 Fe3 O4 P2 S2'
_chemical_formula_weight         870.26
_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   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-07-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2022-02-09 deposited with the CCDC.	2022-06-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.043(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4691(8)
_cell_length_b                   11.0407(4)
_cell_length_c                   22.8109(10)
_cell_measurement_reflns_used    4936
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      68.5990
_cell_measurement_theta_min      4.4850
_cell_volume                     3744.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.113a (Rigaku OD, 2021)'
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.951
_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     17.00  67.00   0.50   11.18    --    0.00  20.00  60.00  100
  2  \w    -83.00  12.00   0.50   11.18    --    0.00  20.00  60.00  190
  3  \w    -79.00 -50.00   0.50   44.74    --  -90.00  57.00  67.54   58
  4  \w   -102.00  -2.00   0.50   44.74    --  -90.00  59.00  13.67  200
  5  \w   -166.00 -71.00   0.50   44.74    --  -90.00  49.00-180.00  190
  6  \w   -120.00 -93.00   0.50   44.74    --  -90.00  59.00  91.39   54
  7  \w   -113.00 -80.00   0.50   44.74    --  -90.00  30.00 -90.00   66
  8  \w   -174.00-146.00   0.50   44.74    --  -90.00  30.00 -90.00   56
  9  \w   -178.00  -2.00   0.50   44.74    --  -90.00  58.00 161.77  352
 10  \w   -178.00-107.00   0.50   44.74    --  -90.00  58.00  60.21  142
 11  \w   -140.00-114.00   0.50   44.74    --  -90.00  59.00  13.67   52
 12  \w   -178.00-127.00   0.50   44.74    --  -90.00  59.00  91.39  102
 13  \w   -105.00  -2.00   0.50   44.74    --  -90.00  59.00 101.47  206
 14  \w    -86.00 -10.00   0.50   44.74    --  -90.00  59.00  91.39  152
 15  \w   -178.00-153.00   0.50   44.74    --  -90.00  59.00  36.92   50
 16  \w   -175.00-150.00   0.50   44.74    --  -90.00  59.00 101.47   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0194381000
_diffrn_orient_matrix_UB_12      0.1370112000
_diffrn_orient_matrix_UB_13      0.0051164000
_diffrn_orient_matrix_UB_21      -0.0782065000
_diffrn_orient_matrix_UB_22      0.0184817000
_diffrn_orient_matrix_UB_23      0.0287444000
_diffrn_orient_matrix_UB_31      0.0652281000
_diffrn_orient_matrix_UB_32      -0.0189416000
_diffrn_orient_matrix_UB_33      0.0638981000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0755
_diffrn_reflns_av_unetI/netI     0.0756
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.951
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            21109
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.273
_diffrn_reflns_theta_min         3.096
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.381
_exptl_absorpt_correction_T_max  0.885
_exptl_absorpt_correction_T_min  0.640
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.113a (Rigaku Oxford Diffraction, 2021)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.544
_exptl_crystal_description       plate
_exptl_crystal_F_000             1776
_exptl_crystal_size_max          0.152
_exptl_crystal_size_mid          0.081
_exptl_crystal_size_min          0.023
_refine_diff_density_max         1.353
_refine_diff_density_min         -0.735
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     460
_refine_ls_number_reflns         6780
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0941
_refine_ls_R_factor_gt           0.0722
_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^)+(0.0946P)^2^+14.1085P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1740
_refine_ls_wR_factor_ref         0.1864
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5227
_reflns_number_total             6780
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00419d2.cif
_cod_data_source_block           Compound_3
_cod_database_code               7710489
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C40H32O4FeP2S2
_chemical_oxdiff_usercomment     'orange kite plate'
_shelx_estimated_absorpt_t_max   0.780
_shelx_estimated_absorpt_t_min   0.277
_reflns_odcompleteness_completeness 96.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C6(H6A,H6B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26),
  C27(H27), C28(H28), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34),
 C36(H36), C37(H37), C38(H38), C39(H39), C40(H40)
;
_shelx_res_checksum              10044
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.870
_oxdiff_exptl_absorpt_empirical_full_min 0.554