Mechanism of the electrocatalytic reduction of protons with diaryldithiolene cobalt complexes.
Letko, Christopher S.; Panetier, Julien A.; Head-Gordon, Martin; Tilley, T. Don; Journal of the American Chemical Society 136 (2014) 9364–9376; doi:10.1021/ja5019755

data_4122066
_publ_section_title
;
 Mechanism of the electrocatalytic reduction of protons with
 diaryldithiolene cobalt complexes.
;
_journal_issue                   26
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9364
_journal_page_last               9376
_journal_paper_doi               10.1021/ja5019755
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety         'C56 H32 Br8 Co2 S8, C16 H36 N'
_chemical_formula_sum            'C72 H68 Br8 Co2 N S8'
_chemical_formula_weight         1960.89
_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   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-08-11
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                106.109(2)
_cell_angle_beta                 106.605(2)
_cell_angle_gamma                91.902(2)
_cell_formula_units_Z            1
_cell_length_a                   10.5253(6)
_cell_length_b                   11.7370(6)
_cell_length_c                   16.2361(9)
_cell_measurement_reflns_used    9968
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.3540
_cell_measurement_theta_min      2.5596
_cell_volume                     1832.79(18)
_computing_cell_refinement       'Bruker APEX2 v. 2009.1'
_computing_data_collection       'Bruker APEX2 v. 2009.1'
_computing_data_reduction        'Bruker APEX2 v. 2009.1'
_computing_molecular_graphics    WINGX
_computing_publication_material  OLEX2
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_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  0.0416
_diffrn_reflns_av_unetI/netI     0.0493
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            26482
_diffrn_reflns_theta_full        25.39
_diffrn_reflns_theta_max         25.39
_diffrn_reflns_theta_min         1.37
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    5.083
_exptl_absorpt_correction_T_max  0.6048
_exptl_absorpt_correction_T_min  0.3877
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.777
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             969
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.679
_refine_diff_density_min         -0.877
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     468
_refine_ls_number_reflns         6653
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0574
_refine_ls_R_factor_gt           0.0350
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0280P)^2^+1.9499P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0662
_refine_ls_wR_factor_ref         0.0731
_reflns_number_gt                5104
_reflns_number_total             6653
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5019755_si_002.cif
_cod_data_source_block           NBu4[1Br]2
_cod_depositor_comments
'Adding full bibliography for 4122065--4122071.cif.'
_cod_original_cell_volume        1832.79(17)
_cod_database_code               4122066
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Others
 Fixed Sof: C28(0.5) H28A(0.5) H28B(0.5) C28A(0.5) H28C(0.5) H28D(0.5)
 C29(0.5) H29A(0.5) H29B(0.5) C29A(0.5) H29C(0.5) H29D(0.5) C30(0.5) H30A(0.5)
 H30B(0.5) C30A(0.5) H30C(0.5) H30D(0.5) C31(0.5) H31A(0.5) H31B(0.5) H31C(0.5)
 C31A(0.5) H31D(0.5) H31E(0.5) H31F(0.5) C32(0.5) H32A(0.5) H32B(0.5) C32A(0.5)
 H32C(0.5) H32D(0.5) H33C(0.5) H33D(0.5) H33A(0.5) H33B(0.5) C34(0.5) H34A(0.5)
 H34B(0.5) C34A(0.5) H34C(0.5) H34D(0.5) H35D(0.5) H35E(0.5) H35F(0.5)
 H35A(0.5) H35B(0.5) H35C(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C28A(H28C,H28D), C29(H29A,H29B), C29A(H29C,H29D), C30(H30A,
 H30B), C30A(H30C,H30D), C32(H32A,H32B), C32A(H32C,H32D), C33(H33C,H33D),
 C33(H33A,H33B), C34(H34A,H34B), C34A(H34C,H34D)
3.b Me refined with riding coordinates:
 C35(H35D,H35E,H35F), C35(H35A,H35B,H35C)
3.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13), C14(H14), C15(H15),
 C17(H17), C18(H18), C20(H20), C21(H21), C23(H23), C24(H24), C26(H26), C27(H27)
3.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C31A(H31D,H31E,H31F)
;