Synthesis, structures and catalytic properties of two organic-inorganic hybrid polyoxometalates built from {Ni<sub>6</sub>PW<sub>9</sub>} units.
Gao, Shuang; Wang, Zhen-Wen; Yang, Guo-Yu; Dalton transactions (Cambridge, England : 2003) 55 (2026) 3733–3738; doi:10.1039/d5dt03040d

data_7720024
_publ_section_title
;
 Synthesis, structures and catalytic properties of two organic-inorganic
 hybrid polyoxometalates built from {Ni<sub>6</sub>PW<sub>9</sub>} units.
;
_journal_issue                   9
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              3733
_journal_page_last               3738
_journal_paper_doi               10.1039/d5dt03040d
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C12 H20 N4 Ni6 O46 P W9, C4 H16 N4 Ni, 3(O)'
_chemical_formula_sum            'C16 H36 N8 Ni7 O49 P W9'
_chemical_formula_weight         3221.12
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-09-28
_audit_creation_method
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Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
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_audit_update_record
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2025-10-27 deposited with the CCDC.	2026-02-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.4167(12)
_cell_length_b                   13.7245(18)
_cell_length_c                   35.498(5)
_cell_measurement_reflns_used    3568
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      25.7920
_cell_measurement_theta_min      3.7590
_cell_volume                     6536.5(14)
_computing_cell_refinement
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
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_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
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_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4159
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.923
_diffrn_measurement_details
;
  1 omega  -18.00   31.00   1.0000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4112   57.0000   30.0000 49

  2 omega   -8.00   58.00   1.0000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4112   38.0000 -180.0000 66

  3 omega   -9.00   74.00   1.0000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4112   57.0000   60.0000 83

  4 omega  -18.00   45.00   1.0000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4112   57.0000 -120.0000 63

  5 omega  -47.00   30.00   1.0000   45.0000
omega____ theta____ kappa____ phi______ frames
    -       10.4112  -57.0000 -120.0000 77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0049732000
_diffrn_orient_matrix_UB_12      -0.0508636000
_diffrn_orient_matrix_UB_13      -0.0029233000
_diffrn_orient_matrix_UB_21      0.0153035000
_diffrn_orient_matrix_UB_22      -0.0059004000
_diffrn_orient_matrix_UB_23      0.0189971000
_diffrn_orient_matrix_UB_31      -0.0503860000
_diffrn_orient_matrix_UB_32      -0.0068147000
_diffrn_orient_matrix_UB_33      0.0054577000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1403
_diffrn_reflns_av_unetI/netI     0.1901
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.923
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_number            59252
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.877
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.677
_diffrn_reflns_theta_min         3.335
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    17.854
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88194
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35h (release 09-02-2015 CrysAlis171 .NET)
(compiled Feb  9 2015,16:26:32)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    3.273
_exptl_crystal_description       block
_exptl_crystal_F_000             5828
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.446
_refine_diff_density_min         -2.970
_refine_diff_density_rms         0.452
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.15(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.982
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     801
_refine_ls_number_reflns         16247
_refine_ls_number_restraints     5790
_refine_ls_restrained_S_all      0.841
_refine_ls_R_factor_all          0.1465
_refine_ls_R_factor_gt           0.0665
_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^)+(0.0424P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1171
_refine_ls_wR_factor_ref         0.1497
_reflns_Friedel_coverage         0.742
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.823
_reflns_number_gt                9187
_reflns_number_total             16247
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt03040d2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7720023--7720024.cif.'
_cod_database_code               7720024
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.268
_shelx_estimated_absorpt_t_min   0.268
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.85307
 0.14693
2. Restrained distances
 C11-C10 = C9-C8 = C33-C13 = C15-C14
 1.52 with sigma of 0.01
 C11-N4 = C10-N3 = C9-N2 = C8-N1 = C15-N8 = C14-N7 = C33-N5 = C13-N6
 1.47 with sigma of 0.01
 C2-C1
 1.52 with sigma of 0.001
 C4-C16
 1.5 with sigma of 0.001
 C13-C33 = C15-C14
 1.51 with sigma of 0.001
 C9-C8 = C11-C10
 1.51 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
O1 \\sim O2 \\sim O3 \\sim O4 \\sim O5 \\sim O6 \\sim O7 \\sim O8 \\sim O9
\\sim O10 \\sim O11 \\sim O12 \\sim O13 \\sim O14 \\sim O15 \\sim O16 \\sim O17
\\sim O18 \\sim O19 \\sim O20 \\sim O21 \\sim O22 \\sim O23 \\sim O24 \\sim O25
\\sim O26 \\sim O27 \\sim O28 \\sim O29 \\sim O30 \\sim O31 \\sim O32 \\sim O33
\\sim O34 \\sim O35 \\sim O36 \\sim O37 \\sim O38 \\sim O39 \\sim O40 \\sim O41
\\sim O42 \\sim O1W \\sim O2W \\sim O3W \\sim O4W \\sim O7W \\sim O6W \\sim
O5W: within 8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 8A
N1 \\sim N2 \\sim N3 \\sim N4 \\sim N5 \\sim N6 \\sim N7 \\sim N8: within 8A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 8A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C16 \\sim C13 \\sim C14 \\sim C15 \\sim C33: within
8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 8A
Uanis(O2) \\sim Ueq, Uanis(O33) \\sim Ueq, Uanis(O6W) \\sim Ueq, Uanis(O7W)
\\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(O16) \\sim Ueq, Uanis(O36) \\sim Ueq,
Uanis(O35) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C7) \\sim
Ueq, Uanis(O42) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C9)
\\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(O4W) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(N2) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(N8) \\sim Ueq, Uanis(O3W)
\\sim Ueq, Uanis(O2W) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(P1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B), N3(H3A,H3B), N4(H4A,H4B), C8(H8A,H8B), C9(H9A,H9B),
 C10(H10A,H10B), C11(H11A,H11B), N5(H5A,H5B), N6(H6A,H6B), N7(H7A,H7B), N8(H8C,
 H8D), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C33(H33A,H33B)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7)
4.c Fitted hexagon refined as free rotating group:
 C2(C3,C4,C5,C6,C7)
4.d Idealised tetrahedral OH refined as rotating group:
 O42(H42)
;
_shelx_res_checksum              36209
_shelx_fab_checksum              25176
_olex2_submission_special_instructions 'No special instructions were received'