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_4518125
_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         'C54 H60 Cu2 N30 O4, O40 Si W12, 2(O)'
_chemical_formula_sum            'C54 H72 Cu2 N30 O46 Si W12'
_chemical_formula_weight         4238.78
_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             2020-06-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                110.467(5)
_cell_angle_beta                 104.354(5)
_cell_angle_gamma                96.738(5)
_cell_formula_units_Z            1
_cell_length_a                   12.358(5)
_cell_length_b                   13.960(5)
_cell_length_c                   15.641(5)
_cell_measurement_reflns_used    5219
_cell_measurement_temperature    296
_cell_measurement_theta_max      50.000
_cell_measurement_theta_min      1.953
_cell_volume                     2386.4(15)
_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 0.998
_diffrn_measured_fraction_theta_max 0.985
_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     0.71069
_diffrn_reflns_av_R_equivalents  0.0316
_diffrn_reflns_av_unetI/netI     0.0653
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            18021
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.240
_diffrn_reflns_theta_max         28.546
_diffrn_reflns_theta_min         1.598
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    14.944
_exptl_absorpt_correction_T_max  0.50
_exptl_absorpt_correction_T_min  0.052
_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            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    2.949
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1922
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         3.069
_refine_diff_density_min         -5.921
_refine_diff_density_rms         0.261
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     738
_refine_ls_number_reflns         11986
_refine_ls_number_restraints     202
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0776
_refine_ls_R_factor_gt           0.0527
_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^)+(0.0567P)^2^+22.7038P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1262
_refine_ls_wR_factor_ref         0.1408
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8779
_reflns_number_total             12163
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            sc0c05459_si_002.cif
_cod_data_source_block           compound_3
_cod_database_code               4518125
_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
2. Restrained distances
 C16-C17 = C17-C18 = C18-C19 = C19-C20 = C20-C21
 1.5 with sigma of 0.02
 C16'-C17' = C17'-C18' = C18'-C19' = C19'-C20' = C20'-C21'
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C7 \\sim C8 \\sim C9 \\sim C9': within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.005
C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C16' \\sim C17'
\\sim C18' \\sim C19' \\sim C20' \\sim C21': within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.01
Uanis(C20') \\sim Ueq, Uanis(O16) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(O14)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C16')=Sof(H16C)=Sof(H16D)=Sof(C17')=Sof(H17C)=Sof(H17D)=Sof(C18')=
 Sof(H18C)=Sof(H18D)=Sof(C19')=Sof(H19C)=Sof(H19D)=Sof(C20')=Sof(H20C)=
 Sof(H20D)=Sof(C21')=Sof(H21C)=Sof(H21D)=1-FVAR(1)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=
 Sof(H18B)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(C21)=
 Sof(H21A)=Sof(H21B)=FVAR(1)
 Sof(C9')=Sof(H9'A)=Sof(H9'B)=1-FVAR(2)
 Sof(C9)=Sof(H9A)=Sof(H9B)=FVAR(2)
 Fixed Sof: O1(0.5) O2(0.5) O3(0.5) O4(0.5)
5.a Riding coordinates:
 C9'(H9'A,H9'B)
5.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C16(H16A,H16B), C17(H17A,H17B),
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C16'(H16C,
 H16D), C17'(H17C,H17D), C18'(H18C,H18D), C19'(H19C,H19D), C20'(H20C,H20D),
 C21'(H21C,H21D)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12), C14(H14),
 C24(H24), C25(H25), C26(H26), C27(H27)
;
_shelx_res_checksum              93860
_shelx_hkl_checksum              10292
_olex2_submission_special_instructions 'No special instructions were received'