Anderson-type polyoxometalate-based metal–organic framework as an efficient heterogeneous catalyst for selective oxidation of benzylic C–H bonds
Tan, Hong-Ru; Zhou, Xiang; Gong, Tengfei; You, Hanqi; Zheng, Qi; Zhao, Sheng-Yin; Xuan, Weimin; RSC Advances 14 (2024) 364–372; doi:10.1039/D3RA07120K

data_7247946
_publ_section_title
;
 Anderson-type polyoxometalate-based metal--organic framework as an
 efficient heterogeneous catalyst for selective oxidation of benzylic C--H
 bonds
;
_journal_issue                   1
_journal_name_full               'RSC Advances'
_journal_page_first              364
_journal_page_last               372
_journal_paper_doi               10.1039/D3RA07120K
_journal_volume                  14
_journal_year                    2024
_chemical_formula_moiety         'C20 H44 Cr2 Cu4 Mo12 N12 O57, 4.395(H2O)'
_chemical_formula_sum            'C20 H52.78 Cr2 Cu4 Mo12 N12 O61.39'
_chemical_formula_weight         2951.18
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-12-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-12-08 deposited with the CCDC.	2023-12-12 downloaded from the CCDC.
;
_cell_angle_alpha                106.760(4)
_cell_angle_beta                 110.599(4)
_cell_angle_gamma                105.352(4)
_cell_formula_units_Z            1
_cell_length_a                   10.2257(9)
_cell_length_b                   14.3320(16)
_cell_length_c                   14.3731(14)
_cell_measurement_reflns_used    8727
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      25.323
_cell_measurement_theta_min      2.780
_cell_volume                     1723.2(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'APEX 4 (Bruker)'
_computing_data_reduction        'SAINT V8.40B (?, 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
;
%$getVar(solution_reference_short)%
;
_diffrn_ambient_temperature      150.0
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'Bruker SMART CCD 1K area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART CCD 1K area detector'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1220
_diffrn_reflns_av_unetI/netI     0.1013
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            44837
_diffrn_reflns_point_group_measured_fraction_full 0.949
_diffrn_reflns_point_group_measured_fraction_max 0.942
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.462
_diffrn_reflns_theta_min         2.148
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    3.736
_exptl_absorpt_correction_T_max  0.7428
_exptl_absorpt_correction_T_min  0.6702
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1972 before and 0.1002 after correction.
The Ratio of minimum to maximum transmission is 0.9023.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    2.844
_exptl_crystal_description       plate
_exptl_crystal_F_000             1414
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.005
_exptl_crystal_size_min          0.002
_refine_diff_density_max         1.279
_refine_diff_density_min         -1.570
_refine_diff_density_rms         0.234
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.44(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1007
_refine_ls_number_reflns         12055
_refine_ls_number_restraints     5312
_refine_ls_restrained_S_all      0.867
_refine_ls_R_factor_all          0.0587
_refine_ls_R_factor_gt           0.0506
_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^)+(0.0347P)^2^+4.7856P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1169
_refine_ls_wR_factor_ref         0.1251
_reflns_Friedel_coverage         0.898
_reflns_Friedel_fraction_full    0.900
_reflns_Friedel_fraction_max     0.891
_reflns_number_gt                10657
_reflns_number_total             12055
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ra07120k2.cif
_cod_data_source_block           p1
_cod_database_code               7247946
_shelx_shelxl_version_number     2018/3
_publ_section_exptl
;
Any special experimental details
;
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.964
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.56(3)
 0.44(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H52 of O52, {H54A,H54B} of O54, H49 of O49
 At 1.5 times of:
  {H56A,H56B} of O56, H20 of O20, H22 of O22, H24 of O24, {H50A,H50B} of O50,
  H47 of O47, H45 of O45, {H51A,H51B} of O51, H43 of O43, {H48A,H48B} of O48,
  {H53A,H53B} of O53, {H62A,H62B} of O62, {H55A,H55B} of O55, {H60A,H60B} of
  O60, {H58A,H58B} of O58, {H59A,H59B} of O59, {H57A,H57B} of O57, H23 of O23,
  H44 of O44, H42 of O42, H46 of O46, H21 of O21, H19 of O19
3. Restrained distances
 H56A-H59A
 2.1 with sigma of 0.02
 H59A-O57
 2.1 with sigma of 0.02
 H56A-H59B
 2.1 with sigma of 0.02
 O49-H49
 0.87 with sigma of 0.02
 H57A-O59
 2.1 with sigma of 0.02
 H52-O52
 0.87 with sigma of 0.02
 H59A-H57A
 2.2 with sigma of 0.02
 O55-H55A = O55-H55B
 0.87 with sigma of 0.02
 H16_$1-H62B
 2.1 with sigma of 0.02
 O54-H54B = O54-H54A
 0.87 with sigma of 0.02
 H54A-H60A
 2.1 with sigma of 0.02
 H60B-H62A
 2.1 with sigma of 0.02
 H62A-H60B
 2.1 with sigma of 0.02
 H60A-H54A
 2.12 with sigma of 0.02
 H58A-H56B
 2.12 with sigma of 0.02
 H53A-O25
 2.2 with sigma of 0.02
 H53A-O41
 2.2 with sigma of 0.02
 H58B-H56B
 2.12 with sigma of 0.02
 H53A-H57B
 2.11 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
O23 \\sim O21 \\sim O19 \\sim O39 \\sim O44 \\sim O46 \\sim O42 \\sim O18 \\sim
O12 \\sim O33 \\sim O37 \\sim O49 \\sim O36 \\sim O2 \\sim O6 \\sim O29 \\sim
O40 \\sim O61 \\sim O16 \\sim O7 \\sim O17 \\sim O15 \\sim O25 \\sim O14 \\sim
O31 \\sim O8 \\sim O52 \\sim O56 \\sim O10 \\sim O51 \\sim O20 \\sim O45 \\sim
O13 \\sim O26 \\sim O27 \\sim O4 \\sim O22 \\sim O35 \\sim O38 \\sim O5 \\sim
O50 \\sim O43 \\sim O47 \\sim O24 \\sim O11 \\sim O48 \\sim O3 \\sim O41 \\sim
O32 \\sim O28 \\sim O55 \\sim O34 \\sim O1 \\sim O9 \\sim O30 \\sim O57 \\sim
O53 \\sim O59 \\sim O62 \\sim O54 \\sim O60 \\sim O58: within 6.4A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 6.4A
Uanis(O23) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(N11) \\sim Ueq, Uanis(N9) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(O19)
\\sim Ueq, Uanis(O24) \\sim Ueq, Uanis(O47) \\sim Ueq: with sigma of 0.001 and
sigma for terminal atoms of 0.002
Uanis(C18) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C14) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O48) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N5) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
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
 Sof(O62)=Sof(H62A)=Sof(H62B)=FVAR(1)
 Fixed Sof: H23(0.5) H44(0.5) H43(0.5) H24(0.5)
7.a Riding coordinates:
 O49(H49), O52(H52), O56(H56A,H56B), O54(H54A,H54B)
7.b Free rotating group:
 O53(H53A,H53B), O59(H59A,H59B), O62(H62A,H62B), O60(H60A,H60B), O58(H58A,H58B)
7.c Rotating group:
 O51(H51A,H51B), O50(H50A,H50B), O48(H48A,H48B), O55(H55A,H55B), O57(H57A,H57B)
7.d Ternary CH refined with riding coordinates:
 O23(H23), O21(H21), O19(H19), O44(H44), O46(H46), O42(H42), O20(H20),
 O45(H45), O22(H22), O43(H43), O47(H47), O24(H24)
7.e Aromatic/amide H refined with riding coordinates:
 C19(H19A), C20(H20A), C18(H18), C14(H14), C15(H15), C16(H16), C5(H5), C6(H6),
 C8(H8), C4(H4), C1(H1), C10(H10), C2(H2), C12(H12), C11(H11), C9(H9)
7.f Fitted hexagon refined as free rotating group:
 C18(C13,C14,C15,C16,C17), C5(C6,C7,C8,C3,C4)
;
_shelx_res_checksum              69709
_shelx_hkl_checksum              39140
_olex2_submission_special_instructions 'No special instructions were received'