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_7226717
_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
'2(Ni O40 P W11), 5(C30 H24 N6 Ni), 1.08(H2 O)'
_chemical_formula_sum            'C150 H120 N30 Ni7 O81.08 P2 W22'
_chemical_formula_weight         8157.64
_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   mixed
_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                 97.407(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.977(3)
_cell_length_b                   16.7308(17)
_cell_length_c                   44.363(4)
_cell_measurement_reflns_used    14684
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.54
_cell_measurement_theta_min      1.41
_cell_volume                     21328(4)
_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)'
_computing_structure_solution    'SHELXS-2014 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device_type  'Bruker APEX area-detector diffractometer'
_diffrn_measurement_method       '\f and \w scan'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0642
_diffrn_reflns_av_unetI/netI     0.0918
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -57
_diffrn_reflns_number            64496
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.519
_diffrn_reflns_theta_min         1.408
_exptl_absorpt_coefficient_mu    12.510
_exptl_absorpt_correction_T_max  0.5206
_exptl_absorpt_correction_T_min  0.2248
_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    2.541
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle-shaped
_exptl_crystal_F_000             14931
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.471
_refine_diff_density_min         -2.115
_refine_diff_density_rms         0.470
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.991
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1399
_refine_ls_number_reflns         24104
_refine_ls_number_restraints     960
_refine_ls_restrained_S_all      0.975
_refine_ls_R_factor_all          0.1051
_refine_ls_R_factor_gt           0.0549
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0738P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1261
_refine_ls_wR_factor_ref         0.1471
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14684
_reflns_number_total             24104
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6ra19257b2.cif
_cod_data_source_block           1
_cod_database_code               7226717
_shelx_estimated_absorpt_t_max   0.521
_shelx_estimated_absorpt_t_min   0.225
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Shared sites
{W11, Ni11}
{Ni1, W12}
3. Uiso/Uaniso restraints and constraints
Ni4 \\sim N14 \\sim C71 \\sim C67 \\sim C70 \\sim C68 \\sim C58 \\sim N14A
\\sim N13A \\sim N13B \\sim N15 \\sim N16 \\sim C69 \\sim C59 \\sim C76 \\sim
C72 \\sim C78 \\sim C81 \\sim C86 \\sim C84 \\sim C65 \\sim CXF \\sim C62 \\sim
C60 \\sim C75 \\sim C73 \\sim C77 \\sim C80 \\sim C85 \\sim C82 \\sim C1AA
\\sim CXE \\sim C61 \\sim C74 \\sim C79 \\sim C83 \\sim C0AA: within 2A with
sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(W11) = Uanis(Ni11)
Uanis(Ni1) = Uanis(W12)
4. Rigid body (RIGU) restrains
 Ni2, C2, C4, C5, N9, C7, C10, N4, C36, C39, C18, C25, N7, N10, N11, N12, C22,
 C24, C31, C21, C33, C49, C90, C6, C56, C30, C45, C47, C54, C87, C55, C57, C89,
 C34, C38, C50, C88
 with sigma for 1-2 distances of 0.0001 and sigma for 1-3 distances of 0.0001
 Ni3, C1, C11, C12, N1, C44, N6, C9, C8, C40, C17, C13, N2, N3, N5, N8, C29,
 C16, C28, C14, C20, C23, C41, C15, C26, C46, C35, C27, C19, C52, C53, C48, C42,
  C43, C32, C3, C37
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(Ni11)=Sof(W12)=1-FVAR(1)
 Sof(W11)=Sof(Ni1)=FVAR(1)
 Fixed Sof: N14(0.5) C71(0.5) H71(0.5) C70(0.5) H70(0.5) C69(0.5) H69(0.5)
 C68(0.5) H68(0.5) C67(0.5) N14A(0.5) C76(0.5) H76(0.5) C75(0.5) H75(0.5)
 C74(0.5) H74(0.5) C73(0.5) H73(0.5) C72(0.5) N13B(0.5) C86(0.5) H86(0.5)
 C85(0.5) H85(0.5) C83(0.5) H83(0.5) C82(0.5) H82(0.5) C84(0.5) C78(0.5)
 C77(0.5) H77(0.5) C79(0.5) H79(0.5) C80(0.5) H80(0.5) C81(0.5) H81(0.5)
 N15(0.5) C65(0.5) C1AA(0.5) H1AA(0.5) C0AA(0.5) H0AA(0.5) CXE(0.5) HXE(0.5)
 CXF(0.5) HXF(0.5) N16(0.5) C58(0.5) C59(0.5) H59(0.5) C60(0.5) H60(0.5)
 C61(0.5) H61(0.5) C62(0.5) H62(0.5) O6W(0.54) H6WA(0.54) H6WB(0.54) N13A(0.5)
 Fixed Uiso: H71(0.05) H70(0.05) H69(0.05) H68(0.05) H76(0.05) H75(0.05)
 H74(0.05) H73(0.05) H86(0.05) H85(0.05) H83(0.05) H82(0.05) H77(0.05)
 H79(0.05) H80(0.05) H81(0.05) H1AA(0.05) H0AA(0.05) HXE(0.05) HXF(0.05)
 H59(0.05) H60(0.05) H61(0.05) H62(0.05)
6.a Riding coordinates:
 O6W(H6WA,H6WB)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34),
 C35(H35), C36(H36), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42),
  C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C48(H48), C52(H52),
 C53(H53), C54(H54), C71(H71), C70(H70), C69(H69), C68(H68), C76(H76), C75(H75),
  C74(H74), C73(H73), C86(H86), C85(H85), C83(H83), C82(H82), C77(H77),
 C79(H79), C80(H80), C81(H81), C1AA(H1AA), C0AA(H0AA), CXE(HXE), CXF(HXF),
 C59(H59), C60(H60), C61(H61), C62(H62), C55(H55), C50(H50), C87(H87), C49(H49),
  C56(H56), C89(H89), C88(H88), C57(H57)
6.c Fitted hexagon refined as free rotating group:
 N14(C71,C70,C69,C68,C67), N14A(C76,C75,C74,C73,C72), N13B(C86,C85,C83,C82,
 C84), N15(C65,C1AA,C0AA,CXE,CXF), N16(C58,C59,C60,C61,C62), N11(C90,C55,C50,
 C87,C49), N12(C56,C89,C88,C57,C6)
;
_shelx_fab_checksum              76684
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'