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_4122067
_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
'2(C14 H8 Br2 Co0.5 S2), C4 H8 O, 0.5(C4 O), C16 H36 N'
_chemical_formula_sum            'C50 H60 Br4 Co N O1.5 S4'
_chemical_formula_weight         1205.80
_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                112.136(3)
_cell_angle_beta                 103.601(3)
_cell_angle_gamma                93.658(3)
_cell_formula_units_Z            2
_cell_length_a                   8.9456(5)
_cell_length_b                   17.3494(11)
_cell_length_c                   18.6580(12)
_cell_measurement_reflns_used    9264
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      25.4329
_cell_measurement_theta_min      2.3767
_cell_volume                     2569.4(3)
_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  0.0440
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            101411
_diffrn_reflns_theta_full        25.49
_diffrn_reflns_theta_max         25.49
_diffrn_reflns_theta_min         2.11
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    3.644
_exptl_absorpt_correction_T_max  0.7120
_exptl_absorpt_correction_T_min  0.1380
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.559
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1220
_exptl_crystal_size_max          0.9
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.941
_refine_diff_density_min         -1.048
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     560
_refine_ls_number_reflns         9476
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0450
_refine_ls_R_factor_gt           0.0345
_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^)+(0.0314P)^2^+5.4099P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0771
_refine_ls_wR_factor_ref         0.0819
_reflns_number_gt                7995
_reflns_number_total             9476
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja5019755_si_002.cif
_cod_data_source_block           NBu4[1Br]
_cod_depositor_comments
'Adding full bibliography for 4122065--4122071.cif.'
_cod_original_formula_sum        'C50 H60 Br4 Co N O1.50 S4'
_cod_database_code               4122067
_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 C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C5S) = Uanis(O2S) = Uanis(C7S) = Uanis(C8S) = Uanis(C6S)
3. Others
 Fixed Sof: O2S(0.5) C5S(0.5) C6S(0.5) C7S(0.5) C8S(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C1S(H1SA,H1SB), C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB), C29(H29A,
 H29B), C30(H30A,H30B), C31(H31A,H31B), C33(H33A,H33B), C34(H34A,H34B),
 C35(H35A,H35B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C41(H41A,H41B),
  C42(H42A,H42B), C43(H43A,H43B)
4.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13), C15(H15), C16(H16),
 C18(H18), C19(H19), C21(H21), C22(H22), C24(H24), C25(H25), C27(H27), C28(H28)
4.c Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C36(H36A,H36B,H36C), C40(H40A,H40B,H40C), C44(H44A,H44B,
 H44C)
;