A Matrix of Heterobimetallic Complexes for Interrogation of Hydrogen Evolution Reaction Electrocatalysts
Ghosh, Pokhraj; Ding, Shengda; Chupik, Rachel B.; Quiroz, Manuel; Hsieh, Chung-Hung; Bhuvanesh, Nattamai; Hall, Michael B.; Darensbourg, Marcetta Y.; Chem. Sci.  (2017) –; doi:10.1039/C7SC03378H

data_1547670
_publ_section_title
;
 A Matrix of Heterobimetallic Complexes for Interrogation of Hydrogen
 Evolution Reaction Electrocatalysts
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC03378H
_journal_year                    2017
_chemical_formula_moiety         'C20 H40 Fe N6 Ni2 O2 S4, B F4'
_chemical_formula_sum            'C20 H40 B F4 Fe N6 Ni2 O2 S4'
_chemical_formula_weight         784.90
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -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)
;
_audit_update_record
;
2017-07-28 deposited with the CCDC.
2017-10-12 downloaded from the CCDC.
;
_cell_angle_alpha                88.197(2)
_cell_angle_beta                 72.322(2)
_cell_angle_gamma                80.263(2)
_cell_formula_units_Z            2
_cell_length_a                   8.5324(11)
_cell_length_b                   13.8268(18)
_cell_length_c                   13.8581(18)
_cell_measurement_reflns_used    9952
_cell_measurement_temperature    150
_cell_measurement_theta_max      27.503
_cell_measurement_theta_min      2.542
_cell_volume                     1534.9(3)
_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      150
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0310
_diffrn_reflns_av_unetI/netI     0.0255
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            28965
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.552
_diffrn_reflns_theta_min         1.495
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.008
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6362
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/3 (Bruker,2014/3) was used for absorption correction.
wR2(int) was 0.0688 before and 0.0415 after correction.
The Ratio of minimum to maximum transmission is 0.8533.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.698
_exptl_crystal_description       plate
_exptl_crystal_F_000             810
_exptl_crystal_size_max          0.471
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.014
_refine_diff_density_max         2.025
_refine_diff_density_min         -0.449
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     445
_refine_ls_number_reflns         6997
_refine_ls_number_restraints     503
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0359
_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^)+(0.0556P)^2^+1.3483P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0981
_refine_ls_wR_factor_ref         0.1050
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5842
_reflns_number_total             6997
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03378h2.cif
_cod_data_source_block           nidacoox
_cod_database_code               1547670
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.972
_shelx_estimated_absorpt_t_min   0.451
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
2. Restrained distances
 C20A-C19A \\sim C20-C19
 with sigma of 0.02
 S4-C20A \\sim S4-C20
 with sigma of 0.02
 N4-C19 \\sim N4-C19A
 with sigma of 0.02
 C5-C4A \\sim C5-C4 \\sim C4A-C3 \\sim C4-C3 \\sim C8-C7A \\sim C7A-C6 \\sim
C7-C6 \\sim C8-C7
 with sigma of 0.02
 B1-F1 \\sim B1-F2 \\sim B1-F3 \\sim B1-F4 \\sim B1A-F1A \\sim B1A-F2A \\sim
B1A-F3A \\sim B1A-F4A
 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
3. 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
C3 \\sim C4 \\sim C4A \\sim C5 \\sim C6 \\sim C7 \\sim C7A \\sim C8: within 2A
with sigma of 0.005 and sigma for terminal atoms of 0.01
S4 \\sim N4 \\sim C20 \\sim C20A \\sim C19 \\sim C19A: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
4. 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
 C3, C4, C4A, C5, C6, C7, C7A, C8
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 S4, N4, C20, C20A, C19, C19A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H5AA)=Sof(H5AB)=
 Sof(H6BC)=Sof(H6BD)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H8BC)=Sof(H8BD)=1-FVAR(1)
 Sof(H3BC)=Sof(H3BD)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H5BC)=Sof(H5BD)=Sof(H6AA)=
 Sof(H6AB)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H8AA)=Sof(H8AB)=FVAR(1)
 Sof(C19A)=Sof(H19C)=Sof(H19D)=Sof(C20A)=Sof(H20C)=Sof(H20D)=1-FVAR(2)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=FVAR(2)
 Sof(B1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=1-FVAR(3)
 Sof(B1)=Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3AA,H3AB), C3(H3BC,H3BD), C4A(H4AA,H4AB),
 C4(H4A,H4B), C5(H5AA,H5AB), C5(H5BC,H5BD), C6(H6AA,H6AB), C6(H6BC,H6BD),
 C7(H7A,H7B), C7A(H7AA,H7AB), C8(H8AA,H8AB), C8(H8BC,H8BD), C9(H9A,H9B),
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B),
  C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,
 H19B), C20(H20A,H20B), C19A(H19C,H19D), C20A(H20C,H20D)
;
_shelx_res_checksum              59799
_olex2_submission_special_instructions 'No special instructions were received'