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_4122068
_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         'C28 H16 Br4 Co S4, 2(C16 H36 N)'
_chemical_formula_sum            'C60 H88 Br4 Co N2 S4'
_chemical_formula_weight         1344.13
_chemical_name_systematic
;
 ? 
;
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 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                90.00
_cell_angle_beta                 108.792(3)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   17.0015(10)
_cell_length_b                   20.7933(11)
_cell_length_c                   18.6110(9)
_cell_measurement_reflns_used    9873
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      23.9379
_cell_measurement_theta_min      2.1997
_cell_volume                     6228.6(6)
_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 0.994
_diffrn_measured_fraction_theta_max 0.994
_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  0.1247
_diffrn_reflns_av_unetI/netI     0.1015
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            82978
_diffrn_reflns_theta_full        25.41
_diffrn_reflns_theta_max         25.41
_diffrn_reflns_theta_min         1.41
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    3.013
_exptl_absorpt_correction_T_max  0.7138
_exptl_absorpt_correction_T_min  0.4651
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.433
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2772
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.876
_refine_diff_density_min         -0.507
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     652
_refine_ls_number_reflns         11419
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.1157
_refine_ls_R_factor_gt           0.0524
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0434P)^2^+8.1403P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0994
_refine_ls_wR_factor_ref         0.1190
_reflns_number_gt                6936
_reflns_number_total             11419
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5019755_si_002.cif
_cod_data_source_block           '[NBu4]2[1Br]'
_cod_depositor_comments
'Adding full bibliography for 4122065--4122071.cif.'
_cod_database_code               4122068
_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
2. Uiso/Uaniso restraints and constraints
Uanis(C36B) = Uanis(C36A)
3. Others
 Fixed Sof: H35A(0.64) H35B(0.64) H35C(0.36) H35D(0.36) C36A(0.64) H36A(0.64)
 H36B(0.64) H36C(0.64) C36B(0.36) H36D(0.36) H36E(0.36) H36F(0.36)
4.a Secondary CH2 refined with riding coordinates:
 C38(H38A,H38B), C41(H41A,H41B), C31(H31A,H31B), C37(H37A,H37B), C30(H30A,
 H30B), C39(H39A,H39B), C29(H29A,H29B), C33(H33A,H33B), C57(H57A,H57B),
 C58(H58A,H58B), C50(H50A,H50B), C46(H46A,H46B), C45(H45A,H45B), C49(H49A,H49B),
  C47(H47A,H47B), C43(H43A,H43B), C59(H59A,H59B), C51(H51A,H51B), C42(H42A,
 H42B), C34(H34A,H34B), C53(H53A,H53B), C54(H54A,H54B), C35(H35A,H35B),
 C35(H35C,H35D), C55(H55A,H55B)
4.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C18(H18), C6(H6), C4(H4), C20(H20), C11(H11), C10(H10), C24(H24),
 C7(H7), C13(H13), C25(H25), C3(H3), C17(H17), C27(H27), C14(H14), C28(H28)
4.c Idealised Me refined as rotating group:
 C60(H60A,H60B,H60C), C52(H52A,H52B,H52C), C44(H44A,H44B,H44C), C32(H32A,H32B,
 H32C), C48(H48A,H48B,H48C), C56(H56A,H56B,H56C), C36A(H36A,H36B,H36C),
 C40(H40A,H40B,H40C), C36B(H36D,H36E,H36F)
;