A Noble-Metal-Free, Tetra-nickel Polyoxotungstate Catalyst for Efficient Photocatalytic Hydrogen Evolution.
Lv, Hongjin; Guo, Weiwei; Wu, Kaifeng; Chen, Zheyuan; Bacsa, John; Musaev, Djamaladdin G.; Geletii, Yurii V.; Lauinger, Sarah M.; Lian, Tianquan; Hill, Craig L.; Journal of the American Chemical Society 136 (2014) 14015–; doi:10.1021/ja5084078

data_4122671
_publ_section_title
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 A Noble-Metal-Free, Tetra-nickel Polyoxotungstate Catalyst for Efficient
 Photocatalytic Hydrogen Evolution.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14015
_journal_paper_doi               10.1021/ja5084078
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety
'H4 Na6 Ni4 O86 P2 W17.22, 4(K), 0.78(W), 16(O)'
_chemical_formula_sum            'H68 K4 Na6 Ni4 O102 P2 W18'
_chemical_formula_weight         5600.96
_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   difmap
_atom_sites_solution_primary     iterative
_audit_creation_date             2014-07-21
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_cell_angle_alpha                82.4668(16)
_cell_angle_beta                 88.9589(16)
_cell_angle_gamma                75.5820(15)
_cell_formula_units_Z            1
_cell_length_a                   11.5861(16)
_cell_length_b                   12.2589(17)
_cell_length_c                   16.041(2)
_cell_measurement_reflns_used    9974
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      30.031
_cell_measurement_theta_min      2.174
_cell_volume                     2187.3(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.1-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      110(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_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  0.0382
_diffrn_reflns_av_unetI/netI     0.0499
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            27964
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.029
_diffrn_reflns_theta_min         1.815
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    24.786
_exptl_absorpt_correction_T_max  0.2249
_exptl_absorpt_correction_T_min  0.0074
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1284 before and 0.0553 after correction.
The Ratio of minimum to maximum transmission is 0.0329.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    4.252
_exptl_crystal_description       prism
_exptl_crystal_F_000             2500
_exptl_crystal_recrystallization_method
'The material was recrystallised from water by slow evaporation'
_exptl_crystal_size_max          0.432
_exptl_crystal_size_mid          0.172
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.737
_refine_diff_density_min         -2.441
_refine_diff_density_rms         0.369
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     677
_refine_ls_number_reflns         12611
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0444
_refine_ls_R_factor_gt           0.0362
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0399P)^2^+21.9968P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0893
_refine_ls_wR_factor_ref         0.0938
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10917
_reflns_number_total             12611
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5084078_si_002.cif
_cod_data_source_block           hj-060314
_cod_depositor_comments          'Adding full bibliography for 4122671.cif.'
_cod_database_code               4122671
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Restrained distances
 O16W_$1-H1WB
 1.85 with sigma of 0.005
 O1W-H1WA = O1W-H1WB
 0.975 with sigma of 0.005
 H1WA-H1WB
 1.52 with sigma of 0.01
 O23_$1-H1WA
 2.07 with sigma of 0.01
2. Uiso/Uaniso restraints and constraints
Uanis(O19W) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O14W) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(W7B) = Uanis(W7)
Uanis(W9B) = Uanis(W9)
Uanis(W5B) = Uanis(W5)
Uanis(W8B) = Uanis(W8)
Uanis(O6) = Uanis(W1B)
Uanis(W6B) = Uanis(W6)
Uanis(W4B) = Uanis(W4)
Uanis(O19W) = Uanis(O18W)
3. Rigid body (RIGU) restrains
 O19W, O18W
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Others
 Sof(W1)=Sof(W2)=Sof(W3)=1-FVAR(1)
 Sof(W1B)=Sof(W2B)=Sof(W3B)=FVAR(1)
 Sof(W5)=1-FVAR(2)
 Sof(W5B)=FVAR(2)
 Sof(W6)=1-FVAR(3)
 Sof(W6B)=FVAR(3)
 Sof(W8)=1-FVAR(4)
 Sof(W8B)=FVAR(4)
 Sof(W9)=1-FVAR(5)
 Sof(W9B)=FVAR(5)
 Sof(W7)=1-FVAR(6)
 Sof(W7B)=FVAR(6)
 Sof(O18W)=1-FVAR(7)
 Sof(O19W)=FVAR(7)
 Sof(W4)=1-FVAR(8)
 Sof(W4B)=FVAR(8)
 Fixed Sof: Na3(0.5)
;
_shelx_res_checksum              68580
_shelx_hkl_checksum              63007
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_original_sample_id HJ-06314
_olex2_submission_special_instructions 'No special instructions were received'