Assembly of polyoxometalates and Ni-bpy cationic units into the molecular core‒shell structures as the bifunctional electrocatalysts
Wang, Chun-Jie; Yao, shuang; Chen, Yi-Zhen; Zhang, Zhi-Ming; Wang, Enbo; RSC Adv.  (2016) –; doi:10.1039/C6RA19257B

data_7226718
_publ_section_title
;
 Assembly of polyoxometalates and Ni-bpy cationic units into the molecular
 core--shell structures as the bifunctional electrocatalysts
;
_journal_name_full               'RSC Adv.'
_journal_paper_doi               10.1039/C6RA19257B
_journal_year                    2016
_chemical_formula_moiety         'C20 H16 B N4 Ni O41 W12, 1.5(C30 H24 N6 Ni)'
_chemical_formula_sum            'C65 H52 B N13 Ni2.5 O41 W12'
_chemical_formula_weight         4034.98
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_symmetry_space_group_name_Hall  '-C 2yc'
_symmetry_space_group_name_H-M   'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-09-30
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2016.09.27 svn.r3342 for OlexSys, GUI svn.r3563)
;
_audit_update_record
;
2016-10-04 deposited with the CCDC.
2016-10-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.006(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   46.643(3)
_cell_length_b                   14.3057(8)
_cell_length_c                   25.9696(14)
_cell_measurement_reflns_used    14553
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      28.317
_cell_measurement_theta_min      1.68
_cell_volume                     17328.5(17)
_computing_cell_refinement       auto
_computing_data_collection       auto
_computing_data_reduction        auto
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX CCD area-detector'
_diffrn_measurement_method       '\f and \w scan'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0823
_diffrn_reflns_av_unetI/netI     0.0928
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -62
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            65021
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.683
_exptl_absorpt_coefficient_mu    16.482
_exptl_absorpt_correction_T_max  0.392
_exptl_absorpt_correction_T_min  0.1293
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSCOR by T.Higashi 8 March, 1995'
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    3.093
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             14592
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.07
_refine_diff_density_max         2.414
_refine_diff_density_min         -3.116
_refine_diff_density_rms         0.349
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1188
_refine_ls_number_reflns         15238
_refine_ls_number_restraints     1002
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0671
_refine_ls_R_factor_gt           0.0442
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0533P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1008
_refine_ls_wR_factor_ref         0.1108
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11421
_reflns_number_total             15238
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ra19257b2.cif
_cod_data_source_block           2
_cod_original_cell_volume        17328.3(17)
_cod_original_formula_sum        'C65 H52 B N13 Ni2.50 O41 W12'
_cod_database_code               7226718
_shelx_estimated_absorpt_t_max   0.392
_shelx_estimated_absorpt_t_min   0.129
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(N13) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C65)
\\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C60) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(N9) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C63)
\\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C39) \\sim Ueq: with sigma of 0.0001 and
sigma for terminal atoms of 0.0002
Uanis(Ni3) \\sim Ueq, Uanis(O38) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C32) \\sim Ueq,
Uanis(C35) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C48) \\sim Ueq,
Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C57)
\\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C63) \\sim Ueq,
Uanis(C64) \\sim Ueq, Uanis(N7) \\sim Ueq, Uanis(N8) \\sim Ueq, Uanis(N9) \\sim
Ueq, Uanis(N12) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
3. Rigid body (RIGU) restrains
 Ni3, O38, C6, C11, C16, C30, C32, C35, C37, C38, C39, C44, C45, C48, C53, C54,
  C56, C57, C59, C61, C63, C64, N7, N8, N9, N12, O17
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Ni1, N2, N3, N4, N5, N6, N10, C2, C13, C3, C36, C5, C21, C8, C15, C12, C31,
 C19, C27, C4, C25, C42, C28, C18, C34, C14, C23, C41, C51, C9, C50, C10, C46,
 C20, C17, C33, C40
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Ni2, N1, N11, N13, C1, C7, C22, C24, C52, C60, C43, C26, C29, C49, C58, C62,
 C47, C55, C65
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O32, B1, O39, O1, O9
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26),
  C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C33(H33), C34(H34),
 C36(H36), C38(H38), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45),
  C46(H46), C47(H47), C48(H48), C49(H49), C50(H50), C51(H51), C53(H53),
 C54(H54), C55(H55), C56(H56), C59(H59), C61(H61), C32(H32), C57(H57), C63(H63),
  C64(H64), C58(H58), C65(H65), C62(H62), C60(H60)
4.b Fitted hexagon refined as free rotating group:
 N9(C32,C57,C63,C64,C39), N13(C52,C58,C65,C62,C60)
;
_shelx_fab_checksum              63812
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'