A wheel-shaped Zr-substituted phosphotungstate [{Zr(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub>}<sub>3</sub> (PO<sub>4</sub>)(P<sub>6</sub>W<sub>39</sub>O<sub>150</sub>)]<sup>39-</sup> with tunable proton conduction properties.
Yang, Dongsheng; Liu, Lihua; Zhang, Yunfan; Zhang, Miao; Ma, Pengtao; Wang, Jingping; Niu, Jingyang; Chemical communications (Cambridge, England) 60 (2024) 3043–3046; doi:10.1039/d4cc00216d

data_7132716
_publ_section_title
;
 A wheel-shaped Zr-substituted phosphotungstate
 [{Zr(C<sub>2</sub>O<sub>4</sub>)<sub>2</sub>}<sub>3</sub>
 (PO<sub>4</sub>)(P<sub>6</sub>W<sub>39</sub>O<sub>150</sub>)]<sup>39-</sup>
 with tunable proton conduction properties.
;
_journal_issue                   22
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              3043
_journal_page_last               3046
_journal_paper_doi               10.1039/d4cc00216d
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety
'C12 K16 Na10.5 O204 P7 W39 Zr3, 2(C4 H12 N), 7(O), [7(H2O)]'
_chemical_formula_sum            'C20 H38 K16 N2 Na10.5 O218 P7 W39 Zr3'
_chemical_formula_weight         12321.61
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-10-26 deposited with the CCDC.	2024-02-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   22.6518(5)
_cell_length_b                   22.6518(5)
_cell_length_c                   75.9558(19)
_cell_measurement_reflns_used    9202
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.180
_cell_measurement_theta_min      2.337
_cell_volume                     33751.8(14)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'Bruker SMART'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8 VENTURE PHOTON II'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  'Helios multilayer optic'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0502
_diffrn_reflns_av_unetI/netI     0.0425
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       90
_diffrn_reflns_limit_l_min       -90
_diffrn_reflns_number            186155
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.099
_diffrn_reflns_theta_max         25.099
_diffrn_reflns_theta_min         2.227
_diffrn_source_type              Microfocus
_exptl_absorpt_coefficient_mu    20.458
_exptl_absorpt_correction_T_max  0.0479
_exptl_absorpt_correction_T_min  0.0220
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0879 before and 0.0702 after correction. The Ratio of minimum to maximum transmission is 0.1776. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    3.600
_exptl_crystal_description       block
_exptl_crystal_F_000             32259
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.240
_refine_diff_density_min         -1.192
_refine_diff_density_rms         0.262
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.045(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.138
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2787
_refine_ls_number_reflns         39932
_refine_ls_number_restraints     299
_refine_ls_restrained_S_all      1.140
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0399
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0235P)^2^+690.0632P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0907
_refine_ls_wR_factor_ref         0.0916
_reflns_Friedel_coverage         0.847
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                38444
_reflns_number_total             39932
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc00216d2.cif
_cod_data_source_block           2294441
_cod_depositor_comments          'Adding full bibliography for 7132716.cif.'
_cod_original_cell_volume        33751.8(17)
_cod_original_formula_sum        'C20 H38 K16 N2 Na10.50 O218 P7 W39 Zr3'
_cod_database_code               7132716
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.373
_shelx_estimated_absorpt_t_min   0.193
_diffrn_source_source            'Incoatc Ius 3.0 '
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.955(9)
 0.045(9)
2. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N1-C13 = N1-C14 = N1-C15 = N1-C16
 1.5 with sigma of 0.01
 N2-C17 = N2-C18 = N2-C19 = N2-C20 = C11-C12
 1.5 with sigma of 0.01
 C12-O174
 1.3 with sigma of 0.01
 O15-O35W
 2.65 with sigma of 0.02
 C13-C14 \\sim C13-C15 \\sim C13-C16 \\sim C14-C15 \\sim C14-C16 \\sim C15-C16
 with sigma of 0.02
 C17-C18 \\sim C17-C19 \\sim C17-C20 \\sim C18-C19 \\sim C18-C20 \\sim C19-C20
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C16 \\sim N1: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C20 \\sim N2: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
C17 \\sim N2: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
O175 \\sim C11 \\sim O166: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02
O174 \\sim C12 \\sim C11 \\sim O166: within 1.7A with sigma of 0.005 and sigma
for terminal atoms of 0.01
C5 \\sim O119 \\sim O141: within 1.4A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C6 \\sim O59 \\sim O35: within 1.4A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C1 \\sim O3 \\sim O150: within 1.4A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O7W \\sim Na3: within 2.6A with sigma of 0.01 and sigma for terminal atoms of
0.02
O23W \\sim K16: within 3A with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(Na10) \\sim Ueq, Uanis(O10W) \\sim Ueq, Uanis(O11W) \\sim Ueq,
Uanis(O22W) \\sim Ueq, Uanis(O23W) \\sim Ueq, Uanis(O24W) \\sim Ueq,
Uanis(O32W) \\sim Ueq, Uanis(O34W) \\sim Ueq, Uanis(O172) \\sim Ueq,
Uanis(O173) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq,
Uanis(O12W) \\sim Ueq, Uanis(O13W) \\sim Ueq, Uanis(O15W) \\sim Ueq,
Uanis(O35W) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(O7W) \\sim Ueq, Uanis(O136)
\\sim Ueq, Uanis(O30W) \\sim Ueq, Uanis(O6W) \\sim Ueq, Uanis(O174) \\sim Ueq,
Uanis(C12) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O5W) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5.a Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,
 H16B,H16C)
;
_smtbx_masks_special_details
;
 Highly disordered solvent was located in the structures.
 Reflection contributions from this solvent were removed
 using program OLEX2, function MSAKS, which determined
 there to be 407.7 electrons in 3519.8 \%A^3^ removed per unit cell. 
 This is consistent with the presence of 7[H2O] per formula unit
 which account for 420 electrons.
 Therefore, there are about 7[H2O] molecules
 were added to the chemical formulas.
 Thus all reported items that derive from the molecular formula
 (<i>e.g.</i>, <i>F</i>(000), density, molecular weight,
 <i>etc</i>.) are inconsistent with the calculated values.
;
_shelx_res_checksum              10679
_shelx_hkl_checksum              18452
_shelx_fab_checksum              61239
_olex2_submission_special_instructions 'No special instructions were received'