A Non-Heme Diiron Complex for (Electro)catalytic Reduction of Dioxygen: Tuning the Selectivity through Electron Delivery.
Wang, Lianke; Gennari, Marcello; Cantú Reinhard, Fabián G; Gutiérrez, Javier; Morozan, Adina; Philouze, Christian; Demeshko, Serhiy; Artero, Vincent; Meyer, Franc; de Visser, Sam P.; Duboc, Carole; Journal of the American Chemical Society 141 (2019) 8244–8253; doi:10.1021/jacs.9b02011

data_4127229
_publ_section_title
;
 A Non-Heme Diiron Complex for (Electro)catalytic Reduction of Dioxygen:
 Tuning the Selectivity through Electron Delivery.
;
_journal_issue                   20
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8244
_journal_page_last               8253
_journal_paper_doi               10.1021/jacs.9b02011
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety
'C76 H61 Fe2 N4 S4, 1.5(C2 H3 N), B F4, 0.5(C4 H9 O)'
_chemical_formula_sum            'C81 H70 B F4 Fe2 N5.5 O0.5 S4'
_chemical_formula_weight         1455.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-03-16
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.54(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.999(3)
_cell_length_b                   17.341(4)
_cell_length_c                   25.848(5)
_cell_measurement_reflns_used    80198
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.500
_cell_measurement_theta_min      2.349
_cell_volume                     6874(3)
_computing_cell_refinement       EvalCCD
_computing_data_collection       Collect
_computing_data_reduction        EvalCCD
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_type            'APEX II'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker-AXS-enraf-nonius KappaAPEXII'
_diffrn_measurement_method       'Phi and omega scans'
_diffrn_radiation_collimation    'Montel optic'
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  'Multilayer mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0545
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            80198
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_min         2.349
_diffrn_source                   'Incoatec ISG250'
_diffrn_source_target            Mo
_diffrn_source_type              'Microfocus sealed tube'
_exptl_absorpt_coefficient_mu    0.606
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.392906
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2004/1 (Bruker,2004) was used for absorption correction.
R(int) was 0.1966 before and 0.0576 after correction.
The Ratio of minimum to maximum transmission is 0.3929.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_description       plate
_exptl_crystal_F_000             3022
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.741
_refine_diff_density_min         -0.692
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.144
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     954
_refine_ls_number_reflns         15697
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      1.162
_refine_ls_R_factor_all          0.0620
_refine_ls_R_factor_gt           0.0440
_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^)+(0.0297P)^2^+7.5854P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0990
_refine_ls_wR_factor_ref         0.1121
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12769
_reflns_number_total             15697
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b02011_si_002.cif
_cod_data_source_block           Fe2SH
_cod_depositor_comments          'Adding full bibliography for 4127229.cif.'
_cod_original_formula_sum        'C81 H70 B F4 Fe2 N5.50 O0.50 S4'
_cod_database_code               4127229
_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 S(H) groups
2. Restrained distances
 C84-C83
 1.5 with sigma of 0.02
 C83-O1
 1.5 with sigma of 0.02
 O1-C82
 1.5 with sigma of 0.02
 C82-C81
 1.5 with sigma of 0.02
 C79-C80
 1.5 with sigma of 0.02
 C84-O1
 2.5 with sigma of 0.02
 C83-C82
 2.5 with sigma of 0.02
 O1-C81
 2.5 with sigma of 0.02
 H4-S4
 1.13 with sigma of 0.02
3. Rigid bond restraints
 B1, F2A, F4A, F3A, F1, F4B, F3B, F2B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C77, C78, N5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O1, C81, C82, C83, C84
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N6, C79, C80
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
B1 \\sim F2A \\sim F4A \\sim F3A \\sim F1 \\sim F4B \\sim F3B \\sim F2B: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C77 \\sim C78 \\sim N5: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
O1 \\sim C81 \\sim C82 \\sim C83 \\sim C84: within 1.7A with sigma of 0.04 and
sigma for terminal atoms of 0.08
N6 \\sim C79 \\sim C80: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
5. Others
 Sof(F4B)=Sof(F3B)=Sof(F2B)=1-FVAR(1)
 Sof(F2A)=Sof(F4A)=Sof(F3A)=FVAR(1)
 Fixed Sof: C79(0.5) N6(0.5) C80(0.5) H80A(0.5) H80B(0.5) H80C(0.5) C81(0.5)
 H81A(0.5) H81B(0.5) H81C(0.5) C84(0.5) H84A(0.5) H84B(0.5) H84C(0.5) C83(0.5)
 H83A(0.5) H83B(0.5) O1(0.5) C82(0.5) H82(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C19(H19A,H19B), C46(H46A,H46B), C8(H8A,H8B), C83(H83A,H83B)
6.b Aromatic/amide H refined with riding coordinates:
 C28(H28), C10(H10), C22(H22), C2(H2), C76(H76), C48(H48), C70(H70), C26(H26),
 C1(H1), C50(H50), C39(H39), C60(H60), C25(H25), C38(H38), C12(H12), C49(H49),
 C73(H73), C32(H32), C40(H40), C37(H37), C23(H23), C11(H11), C34(H34), C16(H16),
  C55(H55), C24(H24), C66(H66), C17(H17), C31(H31), C64(H64), C72(H72),
 C43(H43), C15(H15), C53(H53), C69(H69), C74(H74), C5(H5), C36(H36), C3(H3),
 C61(H61), C68(H68), C42(H42), C41(H41), C63(H63), C4(H4A), C35(H35), C75(H75),
 C54(H54), C29(H29), C62(H62), C67(H67), C30(H30), C82(H82)
6.c Idealised Me refined as rotating group:
 C78(H78A,H78B,H78C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C), C84(H84A,H84B,
 H84C)
;
_shelx_res_checksum              10137
_shelx_hkl_checksum              38999
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'