Stable Zr-based polyoxometalate as a green catalyst for selective oxidation of aniline
Liang, Zhijie; Yao, Yiqing; Ding, Yuyang; Wang, Haifeng; Li, Huafeng; Feng, Gang; Chemical Communications  (2026) –; doi:10.1039/D5CC06298E

data_7135284
_publ_section_title
;
 Stable Zr-based polyoxometalate as a green catalyst for selective
 oxidation of aniline
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D5CC06298E
_journal_year                    2026
_chemical_formula_moiety
'O11.833 P0.333 W3 Zr0.5, 3(C2 N0.5), 0.083(O), 0.028[], 0.25[], 0.139[], 0.222[], 0.028[], 0.028[], 0.139[]'
_chemical_formula_sum            'C6 N1.5 O11.917 P0.333 W3 Zr0.5'
_chemical_formula_weight         891.193
_space_group_crystal_system      trigonal
_space_group_IT_number           166
_space_group_name_Hall           '-R 3 2"'
_space_group_name_H-M_alt        'R -3 m :H'
_symmetry_Int_Tables_number      166
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-10-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-10-15 deposited with the CCDC.	2025-11-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            36
_cell_length_a                   22.6915(1)
_cell_length_b                   22.6915(1)
_cell_length_c                   39.2399(2)
_cell_measurement_reflns_used    85801
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      59.7990
_cell_measurement_theta_min      2.1570
_cell_volume                     17497.86(14)
_computing_cell_refinement       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.116a 64-bit (release 22-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.116a (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  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9942
_diffrn_measured_fraction_theta_max 0.9945
_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     45.00 120.00   0.50    0.05    --   37.33 179.00 -30.00  150
  2  \w      3.00 113.00   0.50    0.05    --   37.33  77.00 150.00  220
  3  \w      3.00  95.00   0.50    0.05    --   37.33  77.00  30.00  184
  4  \w     -6.00 159.00   0.50    0.50    --   78.88 -15.00  -5.00  330
  5  \w     -4.00  69.00   0.50    0.50    --   78.88 -30.00 -30.00  146
  6  \w     -4.00  69.00   0.50    0.50    --   78.88 -30.00-120.00  146
  7  \w      0.00  77.00   0.50    0.50    --   78.88 -45.00-150.00  154
  8  \w     44.00 120.00   0.50    0.05    --   37.33-179.00 -60.00  152
  9  \w     -8.00  82.00   0.50    0.05    --   37.33 -99.00 -60.00  180
 10  \w    -69.00   2.00   0.50    0.50    --  -80.44  30.00 -60.00  142
 11  \w    -65.00  -6.00   0.50    0.05    --  -39.14  57.00 120.00  118
 12  \w     -5.00  36.00   0.50    0.05    --  -39.14  57.00 120.00   82
 13  \w     22.00  63.00   0.50    0.27    --   78.13 -77.00-120.00   82
 14  \w     35.00 109.00   0.50    0.27    --   78.13-125.00  30.00  148
 15  \w    127.00 153.00   0.50    0.27    --   78.13 125.00  30.00   52
 16  \w     33.00 104.00   0.50    0.27    --   78.13-125.00-120.00  142
 17  \w    -79.00 -32.00   0.50    0.27    --  -80.32  77.00 120.00   94
 18  \w   -156.00-125.00   0.50    0.27    --  -80.32-125.00 -90.00   62
 19  \w   -112.00 -33.00   0.50    0.27    --  -80.32 125.00 120.00  158
 20  \w    -68.00  -4.00   0.50    0.27    --  -80.32  30.00-180.00  128
 21  \w   -110.00 -25.00   0.50    0.27    --  -80.32 125.00 -90.00  170
 22  \w    -79.00 -31.00   0.50    0.27    --  -80.32  77.00  90.00   96
 23  \w    -94.00 -48.00   0.50    0.27    --  -80.32   0.00-180.00   92
 24  \w   -166.00-106.00   0.50    0.27    --  -80.32   0.00-180.00  120
 25  \w      2.00 111.00   0.50    0.05    --   36.95  77.00 -90.00  218
 26  \w   -114.00 -12.00   0.50    0.05    --  -39.14 -57.00 -90.00  204
 27  \w   -125.00 -44.00   0.50    0.05    --  -39.14 179.00  30.00  162
 28  \w   -114.00 -12.00   0.50    0.05    --  -39.14 -57.00  60.00  204
 29  \w   -120.00  -7.00   0.50    0.05    --  -39.14 -38.00 -60.00  226
 30  \w   -114.00  -4.00   0.50    0.05    --  -39.14 -77.00-150.00  220
 31  \w     44.00  83.00   0.50    0.27    --   78.13  77.00-150.00   78
 32  \w     44.00 154.00   0.50    0.27    --   78.13  77.00 -60.00  220
 33  \w     49.00 154.00   0.50    0.27    --   78.13  61.00 120.00  210
 34  \w   -156.00 -51.00   0.50    0.27    --  -80.32 -61.00  30.00  210
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0068269000
_diffrn_orient_matrix_UB_12      0.0020794000
_diffrn_orient_matrix_UB_13      -0.0339460000
_diffrn_orient_matrix_UB_21      0.0642810000
_diffrn_orient_matrix_UB_22      0.0135330000
_diffrn_orient_matrix_UB_23      0.0035019000
_diffrn_orient_matrix_UB_31      -0.0215019000
_diffrn_orient_matrix_UB_32      -0.0667644000
_diffrn_orient_matrix_UB_33      -0.0003664000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34050
_diffrn_reflns_av_R_equivalents  0.0924
_diffrn_reflns_av_unetI/netI     0.0193
_diffrn_reflns_Laue_measured_fraction_full 0.9942
_diffrn_reflns_Laue_measured_fraction_max 0.9945
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            126048
_diffrn_reflns_point_group_measured_fraction_full 0.9942
_diffrn_reflns_point_group_measured_fraction_max 0.9945
_diffrn_reflns_theta_full        53.5427
_diffrn_reflns_theta_max         54.99
_diffrn_reflns_theta_min         2.19
_diffrn_source                   GaK/a
_exptl_absorpt_coefficient_mu    23.925
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.24650
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.116a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    3.045
_exptl_crystal_description       block
_exptl_crystal_F_000             13262.150
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_platon_squeeze_details
;
TITL yj_auto          R -3 m       R = 0.04
CELL   22.6915   22.6915   39.2399     90.00     90.00    120.00
SPGR R-3m
Q101 1.000 1.001 0.023 !       3.49 eA-3
C102 0.998 0.302 0.016 !       3.21 eA-3
C103 0.999 0.313 0.477 !       2.99 eA-3
C104 1.001 0.687 0.523 !       2.99 eA-3
C105 0.610 0.390 0.343 !       2.78 eA-3
C106 0.780 0.391 0.343 !       2.78 eA-3
Q107 1.000 0.503 0.078 !       2.74 eA-3
Q108 1.001 0.101 0.498 !       2.72 eA-3
Q109 0.876 0.966 0.983 !       2.58 eA-3
Q110 0.281 0.563 0.234 !       2.25 eA-3
Q111 1.000 1.000 0.500 !       2.09 eA-3
Q112 0.047 0.946 0.118 !       1.99 eA-3
Q113 0.070 0.145 0.406 !       1.97 eA-3
Q114 0.335 0.169 0.218 !       1.95 eA-3
Q115 0.421 0.455 0.087 !       1.75 eA-3
Q116 0.500 0.688 0.476 !       1.68 eA-3
Q117 0.008 0.078 0.414 !       1.64 eA-3
C118 1.000 0.187 0.500 !       1.61 eA-3
C119 1.000 0.187-0.001 !       1.55 eA-3
Q120 0.165 0.643 0.312 !       1.53 eA-3
Q121 0.055 0.528 0.218 !       1.49 eA-3
C122 0.735 0.562 0.344 !       1.48 eA-3
Q123 0.883 0.671 0.977 !       1.48 eA-3
Q124 0.952 0.604 0.594 !       1.45 eA-3
Q125 0.501 0.472 0.944 !       1.41 eA-3
Q126 0.510 0.492 0.208 !       1.39 eA-3
Q127 0.484 0.967 0.586 !       1.39 eA-3
C128 0.118 0.686 0.163 !       1.38 eA-3
Q129 0.501 0.500 0.030 !       1.36 eA-3
Q130 0.195 0.693 0.860 !       1.33 eA-3
Q131 0.524 0.844 0.337 !       1.30 eA-3
Q132 0.328 0.821 0.312 !       1.29 eA-3
Q133 0.312 0.521 0.329 !       1.28 eA-3
Q134 0.235 0.839 0.398 !       1.19 eA-3
Q135 0.422 0.578 0.180 !       1.15 eA-3
Q136 0.548 0.454 0.077 !       1.13 eA-3
Q137 0.438 0.217 0.258 !       1.13 eA-3
Q138 0.251 0.844 0.095 !       1.09 eA-3
Q139 0.319 0.156 0.424 !       1.06 eA-3
Q140 0.876 0.594 0.248 !       0.99 eA-3
Q141 0.336 0.669 0.311 !       0.97 eA-3
Q142 0.189 0.178 0.172 !       0.95 eA-3
Q143 0.236 0.157 0.477 !       0.93 eA-3
Q144 0.561 0.437 0.431 !       0.91 eA-3
C145 0.677 0.120 0.321 !       0.88 eA-3
Q146 0.866 0.936 0.093 !       0.85 eA-3
Q147 1.000 0.996 0.570 !       0.81 eA-3
Q148 0.454 0.719 0.937 !       0.81 eA-3
Q149 1.000 1.000 0.234 !       0.81 eA-3
Q150 0.489 0.076 0.417 !       0.77 eA-3
Q151 0.654 0.953 0.002 !       0.77 eA-3
Q152 0.176 0.921 0.925 !       0.76 eA-3
Q153 0.697 0.922 0.258 !       0.73 eA-3
Q154 0.462 0.343 0.670 !       0.71 eA-3
Q155 0.795 0.402 0.086 !       0.71 eA-3
Q156 0.508 0.345 0.030 !       0.70 eA-3
Q157 0.828 0.660 0.290 !       0.70 eA-3
Q158 0.219 0.709 0.492 !       0.69 eA-3
Q159 0.101 0.202 0.319 !       0.68 eA-3
Q160 0.289 0.780 0.180 !       0.68 eA-3
Q161 0.314 0.634 0.248 !       0.67 eA-3
Q162 0.859 0.715 0.226 !       0.65 eA-3
Q163 0.164 0.836 0.454 !       0.64 eA-3
Q164 0.706 0.352 0.507 !       0.64 eA-3
Q165 0.656 0.342 0.422 !       0.64 eA-3
Q166 0.235 0.621 0.547 !       0.63 eA-3
Q167 0.867 0.732 0.646 !       0.62 eA-3
Q168 0.492 0.132 0.157 !       0.61 eA-3
C169 0.697 0.082 0.324 !       0.61 eA-3
Q170 0.633 0.266 0.244 !       0.60 eA-3
Q171 0.789 0.522 0.163 !       0.59 eA-3
Q172 0.133 0.267 0.711 !       0.58 eA-3
Q173 0.445 0.751 0.282 !       0.58 eA-3
Q174 0.320 0.560 0.095 !       0.58 eA-3
Q175 0.196 0.804 0.382 !       0.58 eA-3
Q176 0.149 0.798 0.444 !       0.57 eA-3
Q177 0.055 0.113 0.960 !       0.57 eA-3
Q178 0.640 0.359 0.086 !       0.57 eA-3
Q179 0.885 0.892 0.404 !       0.56 eA-3
Q180 0.563 0.710 0.126 !       0.56 eA-3
Q181 0.119 0.616 0.327 !       0.56 eA-3
Q182 0.890 0.837 0.335 !       0.55 eA-3
Q183 0.296 0.705 0.353 !       0.55 eA-3
Q184 0.383 0.715 0.742 !       0.55 eA-3
Q185 0.117 0.313 0.133 !       0.55 eA-3
Q186 0.891 0.780 0.217 !       0.55 eA-3
Q187 0.719 0.438 0.977 !       0.55 eA-3
Q188 0.013 0.103 0.104 !       0.54 eA-3
Q189 0.218 0.834 0.164 !       0.54 eA-3
Q190 0.578 0.265 0.077 !       0.54 eA-3
Q191 0.516 0.761 0.234 !       0.54 eA-3
Q192 0.015 0.953 0.272 !       0.54 eA-3
Q193 0.352 0.352 0.001 !       0.54 eA-3
Q194 0.211 0.758 0.077 !       0.53 eA-3
Q195 0.851 0.209-0.001 !       0.52 eA-3
Q196 0.757 0.104 0.251 !       0.52 eA-3
Q197 0.493 0.506 0.710 !       0.52 eA-3
Q198 0.703 0.235 0.406 !       0.52 eA-3
Q199 0.922 0.528 0.304 !       0.51 eA-3
;
_refine_diff_density_max         2.5553
_refine_diff_density_min         -1.5785
_refine_diff_density_rms         0.2227
_refine_ls_d_res_high            0.8183
_refine_ls_d_res_low             17.5711
_refine_ls_extinction_coef       0.0000020(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0320
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_constraints    0
_refine_ls_number_parameters     253
_refine_ls_number_reflns         4006
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.0215
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0347
_refine_ls_shift/su_max          0.0007
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0296P)^2^+1041.1983P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0860
_refine_ls_wR_factor_ref         0.0866
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              24
_reflns_limit_h_min              0
_reflns_limit_k_max              13
_reflns_limit_k_min              0
_reflns_limit_l_max              47
_reflns_limit_l_min              -47
_reflns_number_gt                3885
_reflns_number_total             4006
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5cc06298e2.cif
_cod_data_source_block           yj_auto_sq
_cod_original_sg_symbol_H-M      'R -3 m'
_cod_database_code               7135284
_olex2_refinement_description
;
1. Restrained distances
 C4-C4_$1
 2.4 with sigma of 0.02
 C3-C3_$2 = N1-C1
 1.48 with sigma of 0.02
 N1-C3 = N1-C3_$2
 1.48 with sigma of 0.02
 C3_$2-C3
 2.8 with sigma of 0.02
2. Rigid bond restraints
 C3, N1, C2, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.002
 C6, N2, C5, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.002
 C7, N3, C9, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.002
3. Uiso/Uaniso restraints and constraints
C5 \\sim N2 \\sim C6 \\sim C4: within 2A with sigma of 0.008 and sigma for
terminal atoms of 0.004 within 2A
C8 \\sim N3 \\sim C7 \\sim C9: within 2A with sigma of 0.008 and sigma for
terminal atoms of 0.004 within 2A
C3 \\sim N1 \\sim C2 \\sim C1: within 2A with sigma of 0.008 and sigma for
terminal atoms of 0.004 within 2A
;
_platon_squeeze_void_probe_radius 1.20
_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 4.056
_oxdiff_exptl_absorpt_empirical_full_min 0.423