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_4130754
_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         'C16 H23 Fe N2 Ni O2 S2, C H2 Cl2, B F4'
_chemical_formula_sum            'C17 H25 B Cl2 F4 Fe N2 Ni O2 S2'
_chemical_formula_weight         625.78
_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
_audit_creation_date             2016-03-07
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2015.11.10 svn.r3248 for OlexSys, GUI svn.r5133)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.472(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.3624(5)
_cell_length_b                   20.4468(11)
_cell_length_c                   14.1835(8)
_cell_measurement_reflns_used    1917
_cell_measurement_temperature    110.15
_cell_measurement_theta_max      59.278
_cell_measurement_theta_min      4.324
_cell_volume                     2417.8(2)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      110.15
_diffrn_measured_fraction_theta_full 0.832
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0506
_diffrn_reflns_av_unetI/netI     0.0881
_diffrn_reflns_Laue_measured_fraction_full 0.832
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            5402
_diffrn_reflns_point_group_measured_fraction_full 0.832
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         60.828
_diffrn_reflns_theta_min         3.801
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    9.879
_exptl_absorpt_correction_T_max  0.752
_exptl_absorpt_correction_T_min  0.471
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0883 before and 0.0529 after correction.
 The Ratio of minimum to maximum transmission is 0.63.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.1022 before and 0.0559 after correction.
 The Ratio of minimum to maximum transmission is 0.63.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 23156 reflections, Rint = 0.1134
 (5799 with I > 3sig(I), Rint = 0.0495)
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.719
_exptl_crystal_description       block
_exptl_crystal_F_000             1272
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.991
_refine_diff_density_min         -0.619
_refine_diff_density_rms         0.131
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     324
_refine_ls_number_reflns         5402
_refine_ls_number_restraints     310
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.1127
_refine_ls_R_factor_gt           0.0747
_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^)+(0.0626P)^2^+12.5922P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1579
_refine_ls_wR_factor_ref         0.1771
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3920
_reflns_number_total             5402
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b06461_si_004.cif
_cod_data_source_block           Ni-Fe"+
_cod_database_code               4130754
_shelxl_version_number           2014/6
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6172(18) 0.3828(18)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 F1-B1 \\sim F1A-B1A \\sim F2-B1 \\sim F2A-B1A \\sim F4A-B1A \\sim F4-B1 \\sim
F3A-B1A \\sim F3-B1
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F1-F4 \\sim F2-F3 \\sim F2-F4 \\sim F3-F4 \\sim
F1A-F2A \\sim F1A-F3A \\sim F1A-F4A ~
 F2A-F3A \\sim F2A-F4A \\sim F3A-F4A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
B1 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim B1A \\sim F1A \\sim F2A \\sim F3A
\\sim F4A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(B1) = Uanis(B1A)
Uanis(F1) = Uanis(F1A)
5. Rigid body (RIGU) restrains
 B1, F1, F2, F3, F4, B1A, F1A, F2A, F3A, F4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(B1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=1-FVAR(1)
 Sof(B1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=FVAR(1)
7.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), C17(H17A,H17B)
7.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16)
;
_shelx_res_checksum              66367
_shelx_hkl_checksum              16860
_olex2_submission_special_instructions 'No special instructions were received'