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_4518124
_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, C34 H52 Cu2 N20 O8, 4(H2 O)'
_chemical_formula_sum            'C34 H60 Cu2 N20 O52 Si W12'
_chemical_formula_weight         3942.39
_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     dual
_audit_creation_date             2020-07-21
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.05.22 svn.r1d9e7f8d for OlexSys, GUI svn.r6132)
;
_cell_angle_alpha                67.243(2)
_cell_angle_beta                 66.628(2)
_cell_angle_gamma                87.759(2)
_cell_formula_units_Z            1
_cell_length_a                   12.2804(11)
_cell_length_b                   12.5014(11)
_cell_length_c                   14.7202(14)
_cell_measurement_reflns_used    6140
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      25.127
_cell_measurement_theta_min      1.628
_cell_volume                     1895.4(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      296.15
_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 0.999
_diffrn_measured_fraction_theta_max 0.987
_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           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_unetI/netI     0.0641
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            13911
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.370
_diffrn_reflns_theta_min         1.823
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           40.0
_exptl_absorpt_coefficient_mu    18.802
_exptl_absorpt_correction_T_max  0.87
_exptl_absorpt_correction_T_min  0.86
_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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    3.454
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1780
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.563
_refine_diff_density_min         -3.895
_refine_diff_density_rms         0.359
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.161
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     733
_refine_ls_number_reflns         9372
_refine_ls_number_restraints     537
_refine_ls_restrained_S_all      1.142
_refine_ls_R_factor_all          0.0745
_refine_ls_R_factor_gt           0.0592
_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^)+72.2568P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1265
_refine_ls_wR_factor_ref         0.1340
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7719
_reflns_number_total             9372
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc0c05459_si_002.cif
_cod_data_source_block           compound_2
_cod_database_code               4518124
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.54
_shelx_estimated_absorpt_t_min   0.21
_exptl_absorpt_special_details   BLOCK
_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
 O5WA-H5WC = O5WA-H5WD
 0.85 with sigma of 0.02
 O5WB-H5WA = O5WB-H5WB
 0.85 with sigma of 0.02
 H5WC-H5WD
 1.34 with sigma of 0.04
 H5WA-H5WB
 1.34 with sigma of 0.04
 Cu1-H4WA \\sim Cu1-H4WB
 with sigma of 0.02
 Cu1-H4WC \\sim Cu1-H4WD
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(W6B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O4WA) \\sim Ueq, Uanis(O4WB) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C12) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3) \\sim Ueq, Uanis(C10) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O5WB) \\sim Ueq, Uanis(O5WA) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 O24, W1, O15, O40, O36, O30, O3, O6, O35, O8, O39, O11, O25, W2, Si1, O2, O13,
  O10, O37, O7, O38, O33, O22, O23, W3, W4, O12, O16, O17, O27, O34, O4, O18,
 O21, O28, O32, W5, O9, O20, O31, W6A, W6B, O5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 W6B, W1, O15, O40, O36, O30, O3, O6, O35, O39, O8, O11, O24, O25, W2, Si1, O2,
  O13, O7, O10, O37, O38, O33, O22, O23, W3, W4, O32, O12, O27, O16, O17, O34,
 O4, O18, O21, O28, W5, O9, O20, O31, W6A, O5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: W6A(0.9) O3(0.5) O6(0.5) O7(0.5) O8(0.5) O10(0.5) O11(0.5)
 O13(0.5) O15(0.5) O16(0.5) O17(0.5) O18(0.5) O4WB(0.5) H4WA(0.5) H4WB(0.5)
 O20(0.5) O21(0.5) O22(0.5) O23(0.5) O24(0.5) O25(0.5) O28(0.5) O30(0.5)
 O31(0.5) O32(0.5) O33(0.5) O34(0.5) O35(0.5) O36(0.5) O37(0.5) O38(0.5)
 O39(0.5) O27(0.5) W6B(0.1) O4WA(0.5) H4WC(0.5) H4WD(0.5) O40(0.5) O5WB(0.5)
 H5WA(0.5) H5WB(0.5) O5WA(0.5) H5WC(0.5) H5WD(0.5)
6.a Free rotating group:
 O4WB(H4WA,H4WB), O4WA(H4WC,H4WD), O6W(H6WA,H6WB)
6.b Rotating group:
 O1W(H1WA,H1WB), O2W(H2WA,H2WB), O3W(H3WA,H3WB)
6.c Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B)
6.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C9(H9), C11(H11), C12(H12), C13(H13)
;
_shelx_res_checksum              26958
_shelx_hkl_checksum              13118
_olex2_submission_special_instructions 'No special instructions were received'