Computational and Experimental Study of the Mechanism of Hydrogen Generation from Water by a Molecular Molybdenum-Oxo Electrocatalyst
Eric J. Sundstrom; Xinzheng Yang; V. Sara Thoi; Hemamala I. Karunadasa; Christopher J. Chang; Jeffrey R. Long; Martin Head-Gordon; Journal of the American Chemical Society 134 (2012) 5233–5242; doi:10.1021/ja210949r

data_4117701
_publ_section_title
;
 Computational and Experimental Study of the Mechanism of Hydrogen
 Generation from Water by a Molecular Molybdenum-Oxo Electrocatalyst
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5233
_journal_page_last               5242
_journal_paper_doi               10.1021/ja210949r
_journal_volume                  134
_journal_year                    2012
_chemical_formula_sum            'C68 H44 F12 Mo2 N13 O14 S4'
_chemical_formula_weight         1815.28
_chemical_name_systematic
; 
 ? 
;
_space_group_IT_number           36
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  'C 2c -2'
_symmetry_space_group_name_H-M   'C m c 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   14.9441(10)
_cell_length_b                   22.0350(15)
_cell_length_c                   22.0108(14)
_cell_measurement_reflns_used    9769
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      136.593
_cell_measurement_theta_min      7.147
_cell_volume                     7248.0(8)
_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_publication_material  CIFTAB
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'HELIOS multilayer mirrors'
_diffrn_radiation_source         'microfocus rotating anode'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0213
_diffrn_reflns_av_sigmaI/netI    0.0333
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            23362
_diffrn_reflns_theta_full        68.32
_diffrn_reflns_theta_max         68.32
_diffrn_reflns_theta_min         3.57
_diffrn_standards_interval_count 0
_diffrn_standards_interval_time  0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.840
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6398
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'Blessing, 1995'
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.664
_exptl_crystal_description       parallelepiped
_exptl_crystal_F_000             3644
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.790
_refine_diff_density_min         -0.686
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.022(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.273
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     563
_refine_ls_number_reflns         6205
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.273
_refine_ls_R_factor_all          0.0306
_refine_ls_R_factor_gt           0.0299
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0511P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0820
_refine_ls_wR_factor_ref         0.0825
_reflns_number_gt                6084
_reflns_number_total             6205
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja210949r_si_002_1.cif
_cod_data_source_block           hk209a
_cod_database_code               4117701