A Ni-added polyoxometalate: synthesis, structure and catalytic performance
Zhang, Zheng-Ge; Wang, Zhen-Wen; Wang, Yu; Chen, Juan; Wang, Yue-Lin; Yang, Guo-Yu; CrystEngComm 27 (2025) 1879–1886; doi:10.1039/D5CE00060B

data_7249951
_publ_section_title
;
 A Ni-added polyoxometalate: synthesis, structure and catalytic
 performance
;
_journal_issue                   13
_journal_name_full               CrystEngComm
_journal_page_first              1879
_journal_page_last               1886
_journal_paper_doi               10.1039/D5CE00060B
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety
'B2 Cs1.5 H4 K2 Na2 Ni6 O89 Si2 W20, Na Ni O6, K, H2 K N0.5, 6(O)'
_chemical_formula_sum            'B2 Cs1.5 H47 K4 N0.5 Na3 Ni7 O101 Si2 W20'
_chemical_formula_weight         6219.56
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-10 deposited with the CCDC.	2025-02-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   37.466(3)
_cell_length_b                   14.8831(9)
_cell_length_c                   18.3908(16)
_cell_measurement_reflns_used    4008
_cell_measurement_temperature    298
_cell_measurement_theta_max      25.3590
_cell_measurement_theta_min      3.6660
_cell_volume                     10254.9(14)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4159
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -84.00 -19.00   1.00   75.00    --  -12.12 152.00 -12.00   65
  2  \w    -56.00 -31.00   1.00   75.00    --  -12.12 122.00-172.00   25
  3  \w    -40.00 -15.00   1.00   75.00    --  -12.12  57.00 -30.00   25
  4  \w    -11.00  60.00   1.00   75.00    --  -12.12  57.00 -30.00   71
  5  \w    -22.00  36.00   1.00   75.00    --  -12.12  77.00-120.00   58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0157015000
_diffrn_orient_matrix_UB_12      -0.0055096000
_diffrn_orient_matrix_UB_13      0.0210970000
_diffrn_orient_matrix_UB_21      -0.0104096000
_diffrn_orient_matrix_UB_22      -0.0164342000
_diffrn_orient_matrix_UB_23      0.0293346000
_diffrn_orient_matrix_UB_31      0.0018955000
_diffrn_orient_matrix_UB_32      -0.0443787000
_diffrn_orient_matrix_UB_33      -0.0135097000
_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  0.1205
_diffrn_reflns_av_unetI/netI     0.1001
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -35
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            53930
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         3.367
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    24.415
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.36695
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    4.028
_exptl_crystal_description       block
_exptl_crystal_F_000             10892
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         3.930
_refine_diff_density_min         -2.785
_refine_diff_density_rms         0.494
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     700
_refine_ls_number_reflns         9384
_refine_ls_number_restraints     1953
_refine_ls_restrained_S_all      0.999
_refine_ls_R_factor_all          0.1215
_refine_ls_R_factor_gt           0.0728
_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^)+(0.0076P)^2^+1021.4955P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1292
_refine_ls_wR_factor_ref         0.1423
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6265
_reflns_number_total             9384
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00060b2.cif
_cod_data_source_block           zzg0320
_cod_depositor_comments          'Adding full bibliography for 7249951.cif.'
_cod_original_cell_volume        10254.9(13)
_cod_original_formula_sum        'B2 H47 Cs1.50 K4 N0.50 Na3 Ni7 O101 Si2 W20'
_cod_database_code               7249951
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.792
_shelx_estimated_absorpt_t_min   0.792
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All N(H,H,H,H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 O48-B1 = O48-B1
 1.371 with sigma of 0.01
 O9W_$4-H47
 2.1 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O1 \\sim O1W \\sim O2 \\sim O3 \\sim O3W \\sim O4 \\sim O4W \\sim O5 \\sim O5W
\\sim O6 \\sim O6W \\sim O7 \\sim O7W \\sim O8 \\sim O8W \\sim O9 \\sim O9W
\\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 O43 \\sim O44 \\sim O45 \\sim O46 \\sim O47 \\sim O48 \\sim O49
\\sim O50 \\sim N1 \\sim O10W: within 4.8A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 4.8A
Uanis(O11W) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Na1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O2W) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Si2) \\sim Ueq, Uanis(Si1) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
4. Others
 Fixed Sof: Cs2(0.25) O1W(0.5) O3W(0.5) N1(0.25) H1A(0.25) H1B(0.25) H1C(0.25)
 H1D(0.25)
5.a Riding coordinates:
 N1(H1A), N1(H1B,H1C,H1D)
5.b Tetrahedral OH refined with riding coordinates:
 O47(H47), O48(H48)
;
_shelx_res_checksum              40138
_shelx_hkl_checksum              17497
_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 1.912
_oxdiff_exptl_absorpt_empirical_full_min 0.629