Hemilabile Bridging Thiolates as Proton Shuttles in Bioinspired H<sub>2</sub> Production Electrocatalysts.
Ding, Shengda; Ghosh, Pokhraj; Lunsford, Allen M.; Wang, Ning; Bhuvanesh, Nattamai; Hall, Michael B.; Darensbourg, Marcetta Y.; Journal of the American Chemical Society 138 (2016) 12920–12927; doi:10.1021/jacs.6b06461

data_4130755
_publ_section_title
;
 Hemilabile Bridging Thiolates as Proton Shuttles in Bioinspired
 H<sub>2</sub> Production Electrocatalysts.
;
_journal_issue                   39
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12920
_journal_page_last               12927
_journal_paper_doi               10.1021/jacs.6b06461
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C15 H23 Fe2 N3 O2 S2, C0.4 H0.8 Cl0.8, B F4'
_chemical_formula_sum            'C15.4 H23.8 B Cl0.8 F4 Fe2 N3 O2 S2'
_chemical_formula_weight         573.96
_space_group_crystal_system      orthorhombic
_space_group_IT_number           43
_space_group_name_Hall           'F 2 -2d'
_space_group_name_H-M_alt        'F d d 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2014-07-21
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2013.09.17 svn.r2790 for OlexSys, GUI svn.r4601)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   23.578(3)
_cell_length_b                   30.074(4)
_cell_length_c                   12.5159(17)
_cell_measurement_reflns_used    9938
_cell_measurement_temperature    150.15
_cell_measurement_theta_max      29.529
_cell_measurement_theta_min      2.195
_cell_volume                     8875(2)
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELX, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      150.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0377
_diffrn_reflns_av_unetI/netI     0.0318
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            27819
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.669
_diffrn_reflns_theta_min         1.963
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.643
_exptl_absorpt_correction_T_max  0.7459
_exptl_absorpt_correction_T_min  0.6083
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0782 before and 0.0613 after correction.
The Ratio of minimum to maximum transmission is 0.8155.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.718
_exptl_crystal_description       block
_exptl_crystal_F_000             4669
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.059
_refine_diff_density_min         -0.354
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 2520 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.023(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         5949
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.057
_refine_ls_R_factor_all          0.0314
_refine_ls_R_factor_gt           0.0292
_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^)+(0.0434P)^2^+12.3908P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0776
_refine_ls_wR_factor_ref         0.0793
_reflns_Friedel_coverage         0.865
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.917
_reflns_number_gt                5644
_reflns_number_total             5949
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b06461_si_004.cif
_cod_data_source_block           Fe-Fe'+
_cod_original_formula_sum        'C15.40 H23.80 B Cl0.80 F4 Fe2 N3 O2 S2'
_cod_database_code               4130755
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.827
_shelx_estimated_absorpt_t_min   0.656
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C1S) = Uanis(Cl2S)
3. Others
 Fixed Sof: Cl2S(0.8) C1S(0.4) H(0.4) HA(0.4)
4.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C1S(H,HA)
4.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16)
;
_shelx_res_checksum              93627
_shelx_hkl_checksum              47090