Towards a comprehensive understanding of visible-light photogeneration of hydrogen from water using cobalt(ii) polypyridyl catalysts
Khnayzer, R. S.; Thoi, V. S.; Nippe, M.; King, A. E.; Jurss, J. W.; El Roz, K. A.; Long, J. R.; Chang, C. J.; Castellano, F. N.; Energy & Environmental Science 7 (2014) 1477–; doi:10.1039/c3ee43982h

data_1514144
_publ_section_title
;
 Towards a comprehensive understanding of visible-light photogeneration of
 hydrogen from water using cobalt(ii) polypyridyl catalysts
;
_journal_issue                   4
_journal_name_full               'Energy &amp; Environmental Science'
_journal_page_first              1477
_journal_paper_doi               10.1039/c3ee43982h
_journal_volume                  7
_journal_year                    2014
_chemical_formula_moiety         'C28 H22 Co F6 N6, 2(C F3 O3 S), 1.5(C2 H3 N)'
_chemical_formula_sum            'C33 H26.5 Co F12 N7.5 O6 S2'
_chemical_formula_weight         975.17
_chemical_name_common            '[Co(bpy(PYCF3)2)(MeCN)(OTf)](OTf)'
_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             2013-07-21
_audit_creation_method
;
  Olex2 1.2
  (compiled Apr 23 2013 17:59:47, GUI svn.r4466)
;
_cell_angle_alpha                62.683(2)
_cell_angle_beta                 83.145(2)
_cell_angle_gamma                83.634(2)
_cell_formula_units_Z            4
_cell_length_a                   16.288(3)
_cell_length_b                   16.463(3)
_cell_length_c                   17.020(3)
_cell_measurement_reflns_used    7991
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      2.3397
_cell_measurement_theta_min      24.9409
_cell_volume                     4017.8(13)
_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    DIAMOND
_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 0.983
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'QUAZAR multilayer mirrors'
_diffrn_radiation_source         'microfocus sealed tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1058
_diffrn_reflns_av_unetI/netI     0.1338
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            52419
_diffrn_reflns_theta_full        25.45
_diffrn_reflns_theta_max         25.45
_diffrn_reflns_theta_min         1.26
_exptl_absorpt_coefficient_mu    0.640
_exptl_absorpt_correction_T_max  0.9271
_exptl_absorpt_correction_T_min  0.8990
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.612
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1968
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.625
_refine_diff_density_min         -0.659
_refine_diff_density_rms         0.117
_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     1123
_refine_ls_number_reflns         14642
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.1652
_refine_ls_R_factor_gt           0.0780
_refine_ls_shift/su_max          0.033
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1263P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1962
_refine_ls_wR_factor_ref         0.2459
_reflns_number_gt                7506
_reflns_number_total             14642
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c3ee43982h2.cif
_cod_data_source_block           2
_cod_original_cell_volume        4017.8(10)
_cod_original_formula_sum        'C33 H26.50 Co F12 N7.50 O6 S2'
_cod_database_code               1514144
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(F7A) = Uanis(F7) = Uanis(F7B) = Uanis(F8A) = 
Uanis(F8) = Uanis(F8B) = Uanis(F9A) = Uanis(F9) = Uanis(F9B)
3. Others
 Fixed Sof: F7(0.5) F8(0.5) F9(0.5) F8B(0.25) F8A(0.25) F7B(0.25) F9A(0.25)
 F7A(0.25) F9B(0.25)
4.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C11(H11), C12(H12),
 C14(H14), C16(H16), C17(H17), C19(H19), C29(H29), C30(H30), C31(H31), C32(H32),
  C35(H35), C36(H36), C37(H37), C39(H39), C40(H40), C42(H42), C44(H44),
 C45(H45), C47(H47)
4.b Idealised Me refined as rotating group:
 C2S(H2SA,H2SB,H2SC), C4S(H4SA,H4SB,H4SC), C6S(H6SA,H6SB,H6SC), C22(H22A,H22B,
 H22C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C50(H50A,H50B,H50C), C58(H58A,
 H58B,H58C), C60(H60A,H60B,H60C)
;