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_7720023
_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         'C34 H81 N18 Ni13 O89 P2 W18, 8(O)'
_chemical_formula_sum            'C34 H80 N18 Ni13 O97 P2 W18'
_chemical_formula_weight         6427.62
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-11-23
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-11-27 deposited with the CCDC.	2026-02-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.5520(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.83580(10)
_cell_length_b                   18.15750(10)
_cell_length_c                   31.8458(2)
_cell_measurement_reflns_used    63524
_cell_measurement_temperature    164(30)
_cell_measurement_theta_max      77.5940
_cell_measurement_theta_min      2.7570
_cell_volume                     12625.75(12)
_computing_cell_refinement       'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.140a (Rigaku OD, 2024)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      164(30)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.957
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     90.00 175.00   0.50    0.30    --  106.45 125.00   0.00  170
  2  \w     35.00  67.00   0.50    0.30    --  106.45 -57.00 -30.00   64
  3  \w     34.00  60.00   0.50    0.30    --  106.45 -57.00   0.00   52
  4  \w     34.00  61.00   0.50    0.30    --  106.45 -52.00  17.00   54
  5  \w     50.00 106.00   0.50    0.30    --  106.45 -99.00  90.00  112
  6  \w     11.00  37.00   0.50    0.10    --   45.99 -52.00  17.00   52
  7  \w     50.00 107.00   0.50    0.10    --   45.99  52.00 163.00  114
  8  \w     94.00 163.00   0.50    0.30    --  106.45  52.00 163.00  138
  9  \w    144.00 170.00   0.50    0.30    --  106.45  38.00  90.00   52
 10  \w     96.00 124.00   0.50    0.30    --  106.45  38.00  90.00   56
 11  \w    119.00 178.00   0.50    0.30    --  106.45  19.00 -60.00  118
 12  \w    138.00 176.00   0.50    0.30    --  106.45  38.00-120.00   76
 13  \w    105.00 131.00   0.50    0.30    --  106.45  38.00-120.00   52
 14  \w    -12.00  27.00   0.50    0.10    --  -45.99  52.00 163.00   78
 15  \w    -24.00  30.00   0.50    0.10    --  -45.99  19.00 150.00  108
 16  \w    -24.00  27.00   0.50    0.10    --  -45.99  19.00 -60.00  102
 17  \w    -37.00 -11.00   0.50    0.10    --  -45.99  38.00-120.00   52
 18  \w    -64.00 -31.00   0.50    0.30    -- -104.00  57.00-120.00   66
 19  \w    -64.00 -31.00   0.50    0.30    -- -104.00  57.00 -60.00   66
 20  \w    -61.00 -31.00   0.50    0.30    -- -104.00  57.00 -30.00   60
 21  \w    -63.00 -31.00   0.50    0.30    -- -104.00  57.00   0.00   64
 22  \w    -58.00 -33.00   0.50    0.30    -- -104.00  57.00 120.00   50
 23  \w    -57.00 -31.00   0.50    0.30    -- -104.00  52.00 163.00   52
 24  \w   -175.00 -91.00   0.50    0.30    -- -104.00 -38.00  90.00  168
 25  \w   -175.00-150.00   0.50    0.30    -- -104.00 -52.00  17.00   50
 26  \w   -173.00-145.00   0.50    0.30    -- -104.00 -99.00-180.00   56
 27  \w   -121.00 -87.00   0.50    0.30    -- -104.00 -99.00-180.00   68
 28  \w   -117.00 -38.00   0.50    0.10    --  -45.99 -52.00  17.00  158
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0233039000
_diffrn_orient_matrix_UB_12      0.0007864000
_diffrn_orient_matrix_UB_13      -0.0458275000
_diffrn_orient_matrix_UB_21      -0.0518578000
_diffrn_orient_matrix_UB_22      -0.0533920000
_diffrn_orient_matrix_UB_23      0.0117903000
_diffrn_orient_matrix_UB_31      -0.0417262000
_diffrn_orient_matrix_UB_32      0.0659436000
_diffrn_orient_matrix_UB_33      0.0100821000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0599
_diffrn_reflns_av_unetI/netI     0.0508
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            97375
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.812
_diffrn_reflns_theta_min         2.023
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    32.592
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35226
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.140a (Rigaku Oxford Diffraction, 2024)
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    3.381
_exptl_crystal_description       block
_exptl_crystal_F_000             11648
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.727
_refine_diff_density_min         -2.493
_refine_diff_density_rms         0.346
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1641
_refine_ls_number_reflns         25787
_refine_ls_number_restraints     962
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0453
_refine_ls_R_factor_gt           0.0400
_refine_ls_shift/su_max          0.017
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0653P)^2^+83.3859P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1109
_refine_ls_wR_factor_ref         0.1145
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22679
_reflns_number_total             25787
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt03040d2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7720023--7720024.cif.'
_cod_database_code               7720023
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ni O W'
_chemical_oxdiff_usercomment     'Ni O W'
_shelx_estimated_absorpt_t_max   0.139
_shelx_estimated_absorpt_t_min   0.059
_diffrn_oxdiff_ac3_digest_hkl    41fd8be04642e8c11f74ed5e875950f89f06b4
_olex2_refinement_description
;
1. Restrained distances
 C16-C17
 1.52 with sigma of 0.001
 C16-N9 = C17-N10
 1.47 with sigma of 0.01
2. Rigid bond restraints
 O39, O57, O65, O83, N10, C9, C12, C13, C16, C17, C18, C19
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
3. Uiso/Uaniso restraints and constraints
O39 \\sim O57 \\sim O65 \\sim O83 \\sim N10 \\sim C9 \\sim C12 \\sim C13 \\sim
C16 \\sim C17 \\sim C18 \\sim C19: within 2A with sigma of 0.002 and sigma for
terminal atoms of 0.004 within 2A
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34: 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 \\sim N9
\\sim N10 \\sim N11 \\sim N12 \\sim N13 \\sim N14 \\sim N15 \\sim N16 \\sim N17
\\sim N18: within 8A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 8A
Uanis(C9) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(O39) \\sim Ueq, Uanis(O83) \\sim Ueq, Uanis(N10) \\sim Ueq, Uanis(O57)
\\sim Ueq, Uanis(O65) \\sim Ueq: with sigma of 0.002 and sigma for terminal
atoms of 0.004
Uanis(C17) \\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), N5(H5A,H5B), N6(H6A,H6B),
 N7(H7A,H7B), N9(H9A,H9B), N10(H10A,H10B), N11(H11A,H11B), N12(H12A,H12B),
 N13(H13A,H13B), N14(H14A,H14B), N15(H15A,H15B), N16(H16A,H16B), N17(H17A,H17B),
  N18(H18A,H18B), C8(H8D,H8E), C9(H9C,H9D), C10(H10C,H10D), C11(H11C,H11D),
 C12(H12C,H12D), C13(H13C,H13D), C14(H14C,H14D), C15(H15C,H15D), C16(H16C,H16D),
  C17(H17C,H17D), C18(H18C,H18D), C19(H19A,H19B), C27(H27A,H27B), C28(H28A,
 H28B), C29(H29A,H29B), C30(H30A,H30B), C33(H33A,H33B), C34(H34A,H34B)
4.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C22(H22), C24(H24), C26(H26)
4.c Idealised Me refined as rotating group:
 N8(H8A,H8B,H8C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              31364
_shelx_fab_checksum              40029
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.382
_oxdiff_exptl_absorpt_empirical_full_min 0.615