A Series of Polyoxometalate-Based Metal‒Bis(pyridyl-tetrazole) Complexes with High Electrocatalytic Activity for Hydrogen Evolution Reaction in Alkaline and Acid Media
Wang, Xiu-Li; Tian, Yuan; Chang, Zhi-Han; Lin, Hongyan; ACS Sustainable Chemistry & Engineering  (2020) –; doi:10.1021/acssuschemeng.0c05459

data_4518123
_publ_section_title
;
 A Series of Polyoxometalate-Based Metal--Bis(pyridyl-tetrazole) Complexes
 with High Electrocatalytic Activity for Hydrogen Evolution Reaction in
 Alkaline and Acid Media
;
_journal_name_full               'ACS Sustainable Chemistry &amp; Engineering'
_journal_paper_doi               10.1021/acssuschemeng.0c05459
_journal_year                    2020
_chemical_formula_moiety         'O40 Si W12, C48 H56 Cu2 N30 O4, 2(H2 O)'
_chemical_formula_sum            'C48 H60 Cu2 N30 O46 Si W12'
_chemical_formula_weight         4154.63
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2020-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                111.6420(10)
_cell_angle_beta                 103.2660(10)
_cell_angle_gamma                101.5800(10)
_cell_formula_units_Z            1
_cell_length_a                   12.2209(8)
_cell_length_b                   14.4974(9)
_cell_length_c                   14.8694(10)
_cell_measurement_reflns_used    6140
_cell_measurement_temperature    296
_cell_measurement_theta_max      50.000
_cell_measurement_theta_min      1.953
_cell_volume                     2261.7(3)
_computing_cell_refinement       'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_molecular_graphics    'OLEX2 (Dolomanov et al., 2009)'
_computing_publication_material  'OLEX2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2015b)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      296
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX II'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Quazar'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       'Bruker APEX II'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_av_unetI/netI     0.0562
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            16636
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.336
_diffrn_reflns_theta_min         1.563
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    15.764
_exptl_absorpt_correction_T_max  0.043
_exptl_absorpt_correction_T_min  0.032
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    3.050
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1886
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         3.634
_refine_diff_density_min         -5.798
_refine_diff_density_rms         0.377
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.118
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     642
_refine_ls_number_reflns         11200
_refine_ls_number_restraints     805
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0850
_refine_ls_R_factor_gt           0.0688
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0243P)^2^+134.0443P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1488
_refine_ls_wR_factor_ref         0.1569
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9177
_reflns_number_total             11291
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc0c05459_si_002.cif
_cod_data_source_block           compound_1
_cod_database_code               4518123
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.54
_shelx_estimated_absorpt_t_min   0.21
_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 O(H,H) groups
2. Restrained distances
 H24a-H25b
 1.9 with sigma of 0.04
 H18a-H3Wa
 1.95 with sigma of 0.04
3. Rigid bond restraints
 Si1, O23, O24, O20, O21
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
O1 \\sim O2W \\sim O3 \\sim O1W \\sim O5 \\sim O6 \\sim O7 \\sim O8 \\sim O9
\\sim O10 \\sim O11 \\sim O12 \\sim O13 \\sim O14 \\sim O15 \\sim O16 \\sim O17
\\sim O18 \\sim O19 \\sim O20 \\sim O21 \\sim O22 \\sim O23 \\sim O24 \\sim
O3W: within 3.8A with sigma of 0.008 and sigma for terminal atoms of 0.001
Uanis(Si1) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
5. Rigid body (RIGU) restrains
 Cu1, O2W, N1, O1W, N2, N3, C6, C13, C8, C15, C1, C2, C12, C16, C10, C7, C4,
 C14, C5, C9, C11, C20, C3, C17, N5, N13, N7, N12, N4, N9, N10, N14, N11, N6,
 N8, N15, C18, C23, C19, C21, C24, C25, C22
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: O20(0.5) O21(0.5) O23(0.5) O24(0.5) C24(0.5) C25(0.5)
7.a Free rotating group:
 O3W(H3Wa,H3Wb)
7.b Rotating group:
 O2W(H2Wa,H2Wb), O1W(H1Wa,H1Wb)
7.c Secondary CH2 refined with riding coordinates:
 C18(H18a,H18b), C19(H19a,H19b), C21(H21a,H21b), C22(H22a,H22b), C24(H24a,
 H24b), C25(H25a,H25b)
7.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C5(H5), C6(H6), C7(H7), C8(H8), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C20(H20)
7.e Fitted pentagon refined as free rotating group:
 N12(C11,N7,N11,N6), N15(N8,N4,C3,N9)
;
_shelx_res_checksum              31199
_shelx_hkl_checksum              40865
_olex2_submission_special_instructions 'No special instructions were received'