Isomeric effects of Al<sub>13</sub> Keggin clusters as catalyst support on oxidation reactions.
Tateno, Atsunobu; Zhou, Wei; Gao, Ailing; Weng, Zhewei; Ogiwara, Naoki; Uchida, Sayaka; Nanoscale 17 (2025) 25010–25014; doi:10.1039/d5nr03696h

data_1576094
_publ_section_title
;
 Isomeric effects of Al<sub>13</sub> Keggin clusters as catalyst support
 on oxidation reactions.
;
_journal_issue                   43
_journal_name_full               Nanoscale
_journal_page_first              25010
_journal_page_last               25014
_journal_paper_doi               10.1039/d5nr03696h
_journal_volume                  17
_journal_year                    2025
_chemical_formula_moiety
'1.9(Al Mo6 O24), Al13 H24 O40, 6.7(H2 O), 0.4(Cl), 32[H2O]'
_chemical_formula_sum            'Al14.9 Cl0.4 H101.4 Mo11.4 O124.3'
_chemical_formula_weight         3600.754
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_audit_creation_date             2025-10-14
_audit_creation_method
;
Olex2 1.5-dev
(compiled 2025.10.02 svn.r20e3d319 for OlexSys, GUI svn.r7233)
;
_audit_update_record
;
2025-10-21 deposited with the CCDC.	2025-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                82.003(2)
_cell_angle_beta                 75.767(2)
_cell_angle_gamma                69.210(3)
_cell_formula_units_Z            2
_cell_length_a                   14.3281(4)
_cell_length_b                   14.4893(4)
_cell_length_c                   26.9716(6)
_cell_measurement_reflns_used    20007
_cell_measurement_temperature    153.15
_cell_measurement_theta_max      29.4460
_cell_measurement_theta_min      2.3630
_cell_volume                     5065.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-dev (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      153.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'Rigaku HyPix-6000 area detector'
_diffrn_measured_fraction_theta_full 0.9989
_diffrn_measured_fraction_theta_max 0.9648
_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    -56.00 -29.00   0.50   46.32    --    5.00  45.00 150.00   54
  2  \w     12.00  73.00   0.50   46.32    --  -14.60  45.00  -6.09  122
  3  \w   -104.00  59.00   0.50   46.32    --  -14.60  45.00 120.00  326
  4  \w    -28.00  -1.00   0.50   46.32    --  -14.60  45.00  -6.09   54
  5  \w    -72.00 -45.00   0.50   46.32    --  -14.60  45.00  30.00   54
  6  \w    -26.00  74.00   0.50   46.32    --  -14.60  45.00  30.00  200
  7  \w    -92.00 -62.00   0.50   46.32    --  -14.60  45.00  90.00   60
  8  \w    -43.00   9.00   0.50   46.32    --  -14.60  45.00  90.00  104
  9  \w   -104.00  74.00   0.50   46.32    --  -14.60  45.00 175.49  356
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0554
_diffrn_reflns_av_unetI/netI     0.0621
_diffrn_reflns_Laue_measured_fraction_full 0.9989
_diffrn_reflns_Laue_measured_fraction_max 0.9648
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            83908
_diffrn_reflns_point_group_measured_fraction_full 0.9989
_diffrn_reflns_point_group_measured_fraction_max 0.9648
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         29.00
_diffrn_reflns_theta_min         2.23
_exptl_absorpt_coefficient_mu    1.655
_exptl_absorpt_correction_T_max  0.39464
_exptl_absorpt_correction_T_min  0.38021
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
Spherical absorption correction
using equivalent radius and absorption coefficient.
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    2.361
_exptl_crystal_description       block
_exptl_crystal_F_000             3516.860
_exptl_crystal_recrystallization_method
'Crystallized from aqueous solution (the crystal is insoluble in water)'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.11
_exptl_crystal_size_rad          0.4
_platon_squeeze_details
;
TITL exp_222_a.res in P-1
CELL   14.3281   14.4893   26.9716     82.00     75.77     69.21
SPGR P-1
C101 0.619 0.189 0.462 !      11.66 eA-3
C102 0.842 0.199 0.293 !      11.19 eA-3
Q103 0.638 0.997 0.318 !      11.09 eA-3
C104 0.672 0.828 0.425 !      10.77 eA-3
C105 0.417 0.205 0.474 !      10.14 eA-3
C106 0.658 0.182 0.359 !       9.90 eA-3
C107 0.173 0.912 0.045 !       9.27 eA-3
Q108 0.419 0.077 0.403 !       8.68 eA-3
Q109 0.983 0.933 0.159 !       8.58 eA-3
C110 0.126 0.075 0.247 !       7.96 eA-3
C111 0.602 0.048 0.070 !       7.42 eA-3
Q112 0.485 0.263 0.010 !       7.24 eA-3
Q113 0.814 0.949 0.025 !       7.20 eA-3
Q114 0.394 0.402 0.069 !       6.95 eA-3
Q115 0.765 0.970 0.088 !       6.75 eA-3
Q116 0.406 0.306 0.164 !       6.68 eA-3
C117 0.326 0.111 0.172 !       6.34 eA-3
Q118 0.946 0.113 0.033 !       6.24 eA-3
C119 0.171 0.189 0.120 !       6.24 eA-3
Q120 0.015 0.107 0.178 !       6.07 eA-3
Q121 0.552 0.097 0.188 !       6.01 eA-3
Q122 0.480 0.333 0.203 !       5.26 eA-3
C123 0.801 0.079 0.238 !       4.96 eA-3
C124 0.854 0.091 0.087 !       4.88 eA-3
Q125 0.571 0.894 0.104 !       4.87 eA-3
C126 0.557 0.115 0.149 !       4.67 eA-3
C127 0.641 0.183 0.042 !       4.56 eA-3
Q128 0.203 0.236 0.115 !       4.51 eA-3
C129 0.438 0.842 0.063 !       4.48 eA-3
Q130 0.526 0.438 0.055 !       4.29 eA-3
Q131 0.436 0.396 0.322 !       4.05 eA-3
C132 0.641 0.277 0.123 !       4.02 eA-3
C133 0.436 0.120 0.065 !       3.84 eA-3
Q134 0.463 0.255 0.415 !       3.76 eA-3
C135 0.955 0.016 0.012 !       3.61 eA-3
Q136 0.109 0.892 0.073 !       3.52 eA-3
C137 0.862 0.077 0.118 !       3.43 eA-3
Q138 0.634 0.309 0.139 !       3.40 eA-3
C139 0.473 0.579 0.039 !       3.31 eA-3
Q140 0.577 0.933 0.289 !       3.29 eA-3
Q141 0.175 0.232 0.150 !       3.14 eA-3
C142 0.537 1.005 0.398 !       3.10 eA-3
Q143 0.217 0.730 0.492 !       3.10 eA-3
C144 0.401 0.633 0.037 !       2.88 eA-3
C145 0.354 0.011 0.014 !       2.78 eA-3
C146 0.440 0.779 0.072 !       2.69 eA-3
Q147 0.753 0.200 0.041 !       2.63 eA-3
Q148 1.005 0.524 0.415 !       2.59 eA-3
C149 0.703 0.138 0.210 !       2.54 eA-3
C150 0.500 0.500 0.000 !       2.53 eA-3
C151 0.530 0.109 0.079 !       2.51 eA-3
Q152 0.953 0.645 0.494 !       2.43 eA-3
C153 0.411 0.342 0.102 !       2.39 eA-3
C154 0.218 0.042 0.155 !       2.28 eA-3
Q155 0.541 0.140 0.218 !       2.26 eA-3
C156 0.719 0.141 0.165 !       2.26 eA-3
Q157 0.065 0.254 0.483 !       2.25 eA-3
Q158 0.702 0.220 0.044 !       2.21 eA-3
Q159 0.516 0.864 0.021 !       2.18 eA-3
C160 0.451 0.184 0.173 !       2.11 eA-3
Q161 0.253 0.911 0.243 !       2.09 eA-3
Q162 0.329 0.080 0.202 !       2.08 eA-3
C163 0.282 0.954 0.068 !       2.04 eA-3
Q164 0.315 0.051 0.188 !       2.02 eA-3
Q165 0.766 0.428 0.407 !       2.02 eA-3
Q166 0.391 0.514 0.404 !       2.00 eA-3
Q167 0.859 0.159 0.218 !       2.00 eA-3
C168 0.235 0.012 0.126 !       1.99 eA-3
Q169 0.955 0.922 0.019 !       1.99 eA-3
C170 0.060 0.964 0.013 !       1.96 eA-3
Q171 0.851 0.605 0.411 !       1.94 eA-3
Q172 0.856 0.050 0.405 !       1.93 eA-3
Q173 0.706 0.032 0.106 !       1.93 eA-3
Q174 0.808 0.050 0.139 !       1.91 eA-3
C175 0.988 1.000 0.079 !       1.89 eA-3
Q176 0.438 0.435 0.292 !       1.88 eA-3
Q177 0.191 0.968 0.125 !       1.88 eA-3
Q178 0.220 0.147 0.414 !       1.87 eA-3
Q179 0.988 0.166 0.376 !       1.87 eA-3
Q180 0.709 0.921 0.006 !       1.86 eA-3
C181 0.372 0.717 0.057 !       1.85 eA-3
C182 0.078 0.046 0.167 !       1.84 eA-3
C183 0.926 0.093 0.195 !       1.84 eA-3
Q184 0.733 0.967 0.053 !       1.82 eA-3
Q185 0.249 0.818 0.054 !       1.82 eA-3
Q186 0.750 0.189 0.206 !       1.82 eA-3
C187 0.465 0.186 0.053 !       1.79 eA-3
C188 0.249 0.079 0.201 !       1.77 eA-3
Q189 0.606 0.108 0.242 !       1.77 eA-3
Q190 0.950 0.216 0.410 !       1.77 eA-3
C191 0.434 0.220 0.140 !       1.75 eA-3
Q192 0.460 0.176 0.236 !       1.75 eA-3
Q193 0.077 0.330 0.138 !       1.75 eA-3
Q194 0.122 0.153 0.134 !       1.74 eA-3
Q195 0.692 0.831 0.056 !       1.74 eA-3
Q196 0.325 0.863 0.289 !       1.73 eA-3
Q197 0.065 0.730 0.007 !       1.73 eA-3
Q198 0.285 0.907 0.404 !       1.73 eA-3
Q199 0.324 0.750 0.415 !       1.72 eA-3
;
_refine_diff_density_max         4.2194
_refine_diff_density_min         -1.6986
_refine_diff_density_rms         0.3464
_refine_ls_d_res_high            0.7330
_refine_ls_d_res_low             9.1334
_refine_ls_extinction_coef       0.00050(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0480
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    80
_refine_ls_number_parameters     1127
_refine_ls_number_reflns         26005
_refine_ls_number_restraints     834
_refine_ls_restrained_S_all      1.0307
_refine_ls_R_factor_all          0.1014
_refine_ls_R_factor_gt           0.0799
_refine_ls_shift/su_max          -0.0008
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0661P)^2^+116.3159P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1957
_refine_ls_wR_factor_ref         0.2075
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              19
_reflns_limit_h_min              -18
_reflns_limit_k_max              19
_reflns_limit_k_min              -19
_reflns_limit_l_max              36
_reflns_limit_l_min              0
_reflns_number_gt                19840
_reflns_number_total             26005
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5nr03696h2.cif
_cod_data_source_block           exp_222_sq
_cod_depositor_comments          'Adding full bibliography for 1576094.cif.'
_cod_original_formula_sum        'H101.4 Al14.9 Cl0.4 Mo11.4 O124.3'
_cod_database_code               1576094
_diffrn_oxdiff_digest_hkl
;
016f8c991e3da40cba011f9233cfd5b4bbc61f
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All O(H,H) groups
2. Shared sites
{Cl3, O1a}
{Cl4, O1b}
{Cl1, O1c}
{Cl5, O1d}
3. Restrained distances
 H3Wa-O308
 1 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O41 \\sim O43 \\sim O42: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
Uiso(Cl3) = Uiso(O1a)
Uiso(Cl4) = Uiso(O1b)
Uiso(Cl1) = Uiso(O1c)
Uiso(Cl5) = Uiso(O1d)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Mo20(0.8) Mo21(0.8) Mo22(0.8) Al20(0.4) O200(0.8) O201(0.8)
 O202(0.8) O203(0.8) O204(0.8) O205(0.8) O206(0.8) O208(0.8) O209(0.8)
 O210(0.8) O211(0.8) O297(0.8) Cl3(0.1) Cl4(0.1) Cl1(0.1) Cl5(0.1) O1a(0.1)
 H1aa(0.1) H1ab(0.1) O1b(0.1) H1ba(0.1) H1bb(0.1) O1c(0.1) H1ca(0.1) H1cb(0.1)
 O1d(0.1) H1da(0.1) H1db(0.1) O41(0.7) O43(0.3) O42(0.3) H41a(0.7) H41b(0.7)
 H41a(0.7) H41b(0.7) H42a(0.3) H42b(0.3) H43a(0.3) H43b(0.3)
7.a Riding coordinates:
 O3W(H3Wa,H3Wb), O1a(H1aa,H1ab), O1b(H1ba,H1bb), O1c(H1ca,H1cb), O1d(H1da,
 H1db), O41(H41a,H41b), O42(H42b,H42a), O43(H43a,H43b)
7.b Free rotating group:
 O5W(H5Wa,H5Wb), O4W(H4Wa,H4Wb), O1W(H1Wa,H1Wb), O2W(H2Wa,H2Wb)
7.c Rotating group:
 O8(H8a,H8b), O9(H9a,H9b), O10(H10a,H10b), O14(H14a,H14b), O15(H15a,H15b),
 O16(H16a,H16b), O20(H20a,H20b), O21(H21a,H21b), O22(H22a,H22b), O26(H26a,H26b),
  O27(H27a,H27b), O35(H35a,H35b)
;
_platon_squeeze_special_details
;
A solvent mask was calculated and 653 electrons were 
found in a volume of 1453\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
32 water per Formula Unit which account for 640 electrons 
per unit cell.
;
_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 1.271
_oxdiff_exptl_absorpt_empirical_full_min 0.804