Immobilization of Keggin Polyoxovanadoniobate in Crystalline Solids as Effective Heterogeneous Catalysts towards Selective Oxidation of Benzyl-Alkanes
Hu, Jufang; Dong, Jing; Huang, Xianqiang; Chi, Yingnan; Lin, Zhengguo; Li, Jikun; Yang, Song; Ma, Hongwei; Hu, Changwen; Dalton Trans.  (2017) –; doi:10.1039/C7DT01122A

data_7043257
_publ_section_title
;
 Immobilization of Keggin Polyoxovanadoniobate in Crystalline Solids as
 Effective Heterogeneous Catalysts towards Selective Oxidation of
 Benzyl-Alkanes
;
_journal_name_full               'Dalton Trans.'
_journal_paper_doi               10.1039/C7DT01122A
_journal_year                    2017
_chemical_formula_moiety
'4(C4 H16 Cu N4 2+), 2(C4 H20 Cu N4 O2 2+), Nb12 O42 P V2 10-, 2(O H 1-), 11(H2 O)'
_chemical_formula_sum            'C24 H128 Cu6 N24 Nb12 O59 P V2'
_chemical_formula_weight         3326.51
_space_group_crystal_system      tetragonal
_space_group_IT_number           128
_space_group_name_Hall           '-P 4 2n'
_space_group_name_H-M_alt        'P 4/m n c'
_symmetry_space_group_name_Hall  '-P 4 2n'
_symmetry_space_group_name_H-M   'P 4/m n c'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-06-04
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-06-05 deposited with the CCDC.
2017-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.5498(3)
_cell_length_b                   14.5498(3)
_cell_length_c                   22.9484(11)
_cell_measurement_reflns_used    9005
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.06
_cell_measurement_theta_min      2.800
_cell_volume                     4858.1(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0657
_diffrn_reflns_av_unetI/netI     0.0231
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            48594
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.370
_diffrn_reflns_theta_min         1.657
_exptl_absorpt_coefficient_mu    2.939
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6700
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.0769 before and 0.0547 after correction. The Ratio of minimum to maximum transmission is 0.8985. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.274
_exptl_crystal_description       block
_exptl_crystal_F_000             3278
_refine_diff_density_max         0.792
_refine_diff_density_min         -0.986
_refine_diff_density_rms         0.127
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     185
_refine_ls_number_reflns         2563
_refine_ls_number_restraints     138
_refine_ls_restrained_S_all      1.105
_refine_ls_R_factor_all          0.0652
_refine_ls_R_factor_gt           0.0489
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0398P)^2^+40.1219P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1132
_refine_ls_wR_factor_ref         0.1216
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2023
_reflns_number_total             2563
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7dt01122a2.cif
_cod_data_source_block           1
_cod_database_code               7043257
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups, All N(H,H,H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 N4-C4 = C3-N3
 1.4 with sigma of 0.02
 C4-C3
 1.5 with sigma of 0.02
 N4-C3 = C4-N3
 2.4 with sigma of 0.02
 C2A-N2 = N2-C2
 1.4 with sigma of 0.02
 C1-N1 = N1-C1A
 1.4 with sigma of 0.02
 C2A-C1A = C2-C1
 1.5 with sigma of 0.02
 H13B-O12_$2
 2.6 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C2) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C2A)
\\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(N1) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(O13) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C3, Cu2, N4, N3, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, Cu1, N1, N2, C2A, C1A, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13, Cu2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H1BC)=Sof(H1BD)=Sof(H2BD)=Sof(H2BC)=Sof(C2A)=Sof(H2AC)=Sof(H2AD)=Sof(C1A)=
 Sof(H1AC)=Sof(H1AD)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H1AA)=Sof(H1AB)=
 Sof(H2AA)=Sof(H2AB)=FVAR(1)
 Fixed Sof: O3(0.5) N4(0.5) H4A(0.5) H4B(0.5) N3(0.5) H3A(0.5) H3B(0.5)
 C4(0.5) H4C(0.5) H4D(0.5) C3(0.5) H3C(0.5) H3D(0.5) O13(0.5) H13A(0.5)
 H13B(0.5)
6.a Rotating group:
 O13(H13A,H13B)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), N1(H1AA,H1AB), N1(H1BC,H1BD), N2(H2AA,H2AB),
 N2(H2BD,H2BC), N4(H4A,H4B), N3(H3A,H3B), C4(H4C,H4D), C3(H3C,H3D), C2A(H2AC,
 H2AD), C1A(H1AC,H1AD)
;
_shelx_res_checksum              24151
_shelx_fab_checksum              58901
_shelx_shelxl_version_number     2016/6
_olex2_submission_special_instructions 'No special instructions were received'