Additive-free selective oxidation of aromatic alcohols with molecular oxygen catalyzed by a mixed-valence polyoxovanadate-based metal–organic framework
Tian, Hongrui; Li, Runhan; Miao, Jun; Liu, Shuxia; Wang, Fengfeng; Zheng, Zhiping; Dalton Transactions  (2023) –; doi:10.1039/D3DT01403G

data_7713228
_publ_section_title
;
 Additive-free selective oxidation of aromatic alcohols with molecular
 oxygen catalyzed by a mixed-valence polyoxovanadate-based metal--organic
 framework
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT01403G
_journal_year                    2023
_chemical_formula_moiety
'C28 H28 Cd N8 O72 V30, 2(Cl), 3(H2 O), 5(C14 H16 N4)'
_chemical_formula_sum            'C98 H114 Cd Cl2 N28 O75 V30'
_chemical_formula_weight         4595.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-01-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2022-02-01 deposited with the CCDC.	2023-06-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 121.786(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   46.762(3)
_cell_length_b                   12.8284(9)
_cell_length_c                   29.674(2)
_cell_measurement_reflns_used    9644
_cell_measurement_temperature    296
_cell_measurement_theta_max      24.77
_cell_measurement_theta_min      2.61
_cell_volume                     15131.1(18)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_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  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      296
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_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  0.1306
_diffrn_reflns_av_unetI/netI     0.0725
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       55
_diffrn_reflns_limit_h_min       -55
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            82167
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.085
_diffrn_reflns_theta_max         25.085
_diffrn_reflns_theta_min         2.208
_exptl_absorpt_coefficient_mu    2.028
_exptl_absorpt_correction_T_max  0.655
_exptl_absorpt_correction_T_min  0.649
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'dull dark violet'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.017
_exptl_crystal_description       block
_exptl_crystal_F_000             9080
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.21
_refine_diff_density_max         2.078
_refine_diff_density_min         -0.561
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1059
_refine_ls_number_reflns         13417
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0982
_refine_ls_R_factor_gt           0.0482
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0464P)^2^+81.3948P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0990
_refine_ls_wR_factor_ref         0.1188
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8682
_reflns_number_total             13417
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt01403g2.cif
_cod_data_source_block           1
_cod_original_cell_volume        15131.0(18)
_cod_database_code               7713228
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.675
_shelx_estimated_absorpt_t_min   0.664
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C38) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(N38) \\sim Ueq, Uanis(C40)
\\sim Ueq, Uanis(N51) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(N50) \\sim Ueq,
Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(N49) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O39) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: O39(0.5) H39A(0.5) H39B(0.5)
4.a Riding coordinates:
 O37(H37A,H37B), O39(H39A,H39B)
4.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C32(H32A,H32B), C11(H11A,H11B), C18(H18A,H18B), C27(H27A,H27B),
 C41(H41A,H41B), C48(H48A,H48B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C6(H6), C7(H7), C9(H9), C10(H10), C33(H33), C34(H34),
 C36(H36), N25(H25), N26(H26), C13(H13), C14(H14), C16(H16), C17(H17), C19(H19),
  C20(H20), C21(H21), C22(H22), C23(H23), C37(H37), N8(H8), C24(H24), C29(H29),
 C30(H30), C31(H31), C35(H35), N50(H50), N51(H51), C25(H25A), C38(H38),
 C40(H40), C43(H43), C44(H44), C45(H45), C47(H47), C50(H50A), C52(H52), C53(H53)
;
_shelx_res_checksum              60907
_shelx_hkl_checksum              51174
_olex2_submission_special_instructions 'No special instructions were received'