A Keggin-type polyoxometalate-based metal–organic complex as a highly efficient heterogeneous catalyst for the selective oxidation of alkylbenzenes
Wang, Yue; Xu, Na; Zhang, Yue; Zhang, Tong; Zhang, Zhong; Li, Xiao-Hui; Wang, Xiu-Li; Dalton Transactions  (2022) –; doi:10.1039/D1DT03823K

data_7709333
_publ_section_title
;
 A Keggin-type polyoxometalate-based metal--organic complex as a highly
 efficient heterogeneous catalyst for the selective oxidation of
 alkylbenzenes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT03823K
_journal_year                    2022
_chemical_formula_moiety         'C10 H16 Cu5.821 N12 O48 P W11.179, H4 O2'
_chemical_formula_sum            'C10 H32 Cu5.83 N12 O56 P W11.18'
_chemical_formula_weight         3673.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-C 2y'
_space_group_name_H-M_alt        'C 1 2/m 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-12-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-12-11 deposited with the CCDC.	2021-12-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.584(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.8596(13)
_cell_length_b                   19.9924(13)
_cell_length_c                   11.5815(9)
_cell_measurement_reflns_used    3247
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      25.127
_cell_measurement_theta_min      1.628
_cell_volume                     2868.1(4)
_computing_cell_refinement       'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT+ Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015a)'
_diffrn_ambient_temperature      296.15
_diffrn_detector                 'charge-coupled device (CCD) area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker APEX II'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX II Quazar'
_diffrn_measurement_method       '0.5\% \w and 0.5\% \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       'Bruker APEX II'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0413
_diffrn_reflns_av_unetI/netI     0.0448
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            10715
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.327
_diffrn_reflns_theta_min         1.825
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    24.584
_exptl_absorpt_correction_T_max  0.87
_exptl_absorpt_correction_T_min  0.86
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Krause et al., 2015) was used for absorption correction.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    4.254
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3271
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.580
_refine_diff_density_min         -1.559
_refine_diff_density_rms         0.278
_refine_ls_extinction_coef       0.000094(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     259
_refine_ls_number_reflns         3679
_refine_ls_number_restraints     57
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0441
_refine_ls_R_factor_gt           0.0353
_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^)+(0.0257P)^2^+38.3900P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0723
_refine_ls_wR_factor_ref         0.0753
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3199
_reflns_number_total             3679
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt03823k2.cif
_cod_data_source_block           1
_cod_database_code               7709333
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.084
_shelx_estimated_absorpt_t_min   0.067
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Shared sites
{W4, Cu4}
3. Uiso/Uaniso restraints and constraints
O9B \\sim O9A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O17B \\sim O17A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
O11B \\sim O11A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(O11B) \\sim Ueq, Uanis(O9B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O17B) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O15) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O17A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(W4) = Uanis(Cu4)
4. Rigid body (RIGU) restrains
 P1, O15, O16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(Cu4)=1-FVAR(1)
 Sof(W4)=FVAR(1)
 Sof(O9B)=1-FVAR(2)
 Sof(O9A)=FVAR(2)
 Sof(O17B)=1-FVAR(3)
 Sof(O17A)=FVAR(3)
 Sof(O11B)=1-FVAR(4)
 Sof(O11A)=FVAR(4)
 Fixed Sof: O15(0.5) O16(0.5) H3WA(0.5) H3WB(0.5)
6.a Riding coordinates:
 O3W(H3WA,H3WB)
6.b Rotating group:
 O1W(H1WA,H1WB)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              95636
_shelx_hkl_checksum              91592
_shelx_fab_checksum              98932
_olex2_submission_special_instructions 'No special instructions were received'