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_1547669
_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 H39 Fe2 N8 Ni2 O4 S4, 0.36(H2 O), 2(C H2 Cl2), 1.77(B F4)'
_chemical_formula_sum
'C22 H43.73 B1.77 Cl4 F7.08 Fe2 N8 Ni2 O4.36 S4'
_chemical_formula_weight         1143.02
_chemical_name_systematic
;
 ?
;
_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   mixed
_audit_block_doi                 10.5517/ccdc.csd.cc142wjm
_audit_creation_date             2015-01-23
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.10.22 svn.r3046 for OlexSys, GUI svn.r4928)
;
_audit_update_record
;
2015-01-24 deposited with the CCDC.
2017-10-12 downloaded from the CCDC.
;
_cell_angle_alpha                99.860(2)
_cell_angle_beta                 104.520(3)
_cell_angle_gamma                105.715(2)
_cell_formula_units_Z            2
_cell_length_a                   11.6249(9)
_cell_length_b                   14.1066(11)
_cell_length_c                   14.2931(11)
_cell_measurement_reflns_used    9973
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      37.148
_cell_measurement_theta_min      2.657
_cell_volume                     2111.1(3)
_computing_cell_refinement       'SAINT v8.27A (Bruker, 2012)'
_computing_data_reduction        'SAINT v8.27A (Bruker, 2012)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      110(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.964
_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  0.0448
_diffrn_reflns_av_unetI/netI     0.0352
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            120215
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         38.680
_diffrn_reflns_theta_min         1.523
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.076
_exptl_absorpt_correction_T_max  0.8685
_exptl_absorpt_correction_T_min  0.3427
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0938 before and 0.0484 after correction.
The Ratio of minimum to maximum transmission is 0.3946.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.798
_exptl_crystal_description       block
_exptl_crystal_F_000             1158
_exptl_crystal_size_max          0.708
_exptl_crystal_size_mid          0.499
_exptl_crystal_size_min          0.146
_refine_diff_density_max         1.504
_refine_diff_density_min         -0.973
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     597
_refine_ls_number_reflns         23189
_refine_ls_number_restraints     238
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0651
_refine_ls_R_factor_gt           0.0410
_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^)+(0.0607P)^2^+1.7770P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1102
_refine_ls_wR_factor_ref         0.1255
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17077
_reflns_number_total             23189
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03378h2.cif
_cod_data_source_block           temp
_cod_database_code               1547669
_shelxl_version_number           2014-3
_shelx_estimated_absorpt_t_max   0.751
_shelx_estimated_absorpt_t_min   0.321
_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 O(H,H) groups
2. Restrained distances
 Cl3S-C1T \\sim Cl3S-C1S \\sim Cl2S-C1S \\sim Cl2T-C1T
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Cl3S \\sim C1S \\sim Cl2S \\sim C1T \\sim Cl2T: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.02
B2 \\sim F5 \\sim F6 \\sim F7 \\sim F8 \\sim B2A \\sim F5A \\sim F6A \\sim F7A
\\sim F8A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 Cl3S, C1S, Cl2S, C1T, Cl2T
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 B2, F5, F6, F7, F8, B2A, F5A, F6A, F7A, F8A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Same fragment restrains
{B2, F5, F6, F7, F8} sigma for 1-2: 0.01, 1-3: 0.04
as
{B2A, F5A, F6A, F7A, F8A}
6. Others
 Sof(C1T)=Sof(H1TA)=Sof(H1TB)=Sof(Cl2T)=1-FVAR(1)
 Sof(C1S)=Sof(H1SA)=Sof(H1SB)=Sof(Cl2S)=FVAR(1)
 Sof(B2A)=Sof(F5A)=Sof(F6A)=Sof(F7A)=Sof(F8A)=0.77*(1-FVAR(3))
 Sof(B2)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=0.77*FVAR(3)
 Fixed Sof: O9(0.25) H9C(0.25) H9D(0.25) O5(0.11418) H5C(0.11418) H5D(0.11418)
7.a Free rotating group:
 O9(H9C,H9D), O5(H5C,H5D)
7.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B),
 C8(H8A,H8B), 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), C1S(H1SA,H1SB), C5S(H5SA,
 H5SB), C1T(H1TA,H1TB)
;
_shelx_res_checksum              95613
_olex2_submission_special_instructions 'No special instructions were received'