N-donor flexible ligands constructed polyoxometalate-based metal-organic frameworks as multifunctional electrocatalyts
Zhou, Qian; Yao, Jinzhen; Sun, Jing; Li, Xiao; Bao, Siqi; Su, Zhong-Min; CrystEngComm  (2022) –; doi:10.1039/D2CE00077F

data_7244531
_publ_section_title
;
 N-donor flexible ligands constructed polyoxometalate-based metal-organic
 frameworks as multifunctional electrocatalyts
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D2CE00077F
_journal_year                    2022
_chemical_formula_moiety         'C32 H54 N24 Ni2 O42 Si W12'
_chemical_formula_sum            'C32 H54 N24 Ni2 O42 Si W12'
_chemical_formula_weight         3798.70
_chemical_name_systematic        '[Ni2(btbu)4(H2O)2(SiW12O40)]'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-24
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2022-01-05 deposited with the CCDC.	2022-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.122(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.438(2)
_cell_length_b                   16.716(3)
_cell_length_c                   17.383(3)
_cell_measurement_reflns_used    4299
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      25.127
_cell_measurement_theta_min      1.628
_cell_volume                     3533.6(10)
_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 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0438
_diffrn_reflns_av_unetI/netI     0.0459
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            20127
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.108
_diffrn_reflns_theta_max         25.108
_diffrn_reflns_theta_min         1.709
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.35
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           45.0
_exptl_absorpt_coefficient_mu    20.086
_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    3.570
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3416
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.473
_refine_diff_density_min         -1.594
_refine_diff_density_rms         0.284
_refine_ls_extinction_coef       0.000062(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.276
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     549
_refine_ls_number_reflns         6274
_refine_ls_number_restraints     225
_refine_ls_restrained_S_all      1.257
_refine_ls_R_factor_all          0.0675
_refine_ls_R_factor_gt           0.0563
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+141.1489P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1039
_refine_ls_wR_factor_ref         0.1072
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5348
_reflns_number_total             6274
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2ce00077f2.cif
_cod_data_source_block           11
_cod_original_cell_volume        3533.7(12)
_cod_database_code               7244531
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.108
_shelx_estimated_absorpt_t_min   0.086
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O20) \\sim Ueq, Uanis(O21) \\sim Ueq, Uanis(O18) \\sim Ueq, Uanis(O17)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O23) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17,
 C18, N1, N2, N3, N4, N5, N6, N7, N8, N9, N10, N11, N12
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Fixed Sof: O17(0.5) O18(0.5) H10A(0.5) H10B(0.5) H10C(0.5) H10D(0.5) O20(0.5)
 O21(0.5) C15(0.5) H15A(0.5) H15B(0.5) C16(0.5) H16A(0.5) H16B(0.5) C17(0.5)
 H17A(0.5) H17B(0.5) C18(0.5) H18A(0.5) H18B(0.5)
5.a Rotating group:
 O1(H1A,H1B)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C10(H10C,H10D), C12(H12A,H12B),
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B),
  C18(H18A,H18B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), N11(H11), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C11(H11A)
;
_shelx_res_checksum              5312
_shelx_hkl_checksum              66156
_olex2_submission_special_instructions 'No special instructions were received'