A new {P4Mo6}-based complex as a highly efficient heterogeneous catalyst for the oxidation of alkylbenzenes under mild conditions
Liu, Xiaodong; Xu, Na; Liu, Xiaohui; Guo, Yanyan; Wang, Xiuli; CrystEngComm 26 (2024) 364–369; doi:10.1039/D3CE01031G

data_7247813
_publ_section_title
;
 A new {P4Mo6}-based complex as a highly efficient heterogeneous catalyst
 for the oxidation of alkylbenzenes under mild conditions
;
_journal_issue                   3
_journal_name_full               CrystEngComm
_journal_page_first              364
_journal_page_last               369
_journal_paper_doi               10.1039/D3CE01031G
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety
'H11 Mn4 Mo12 Na O69 P8, 5(C7 H7 N2), 2(H2 O), [+ solvents]'
_chemical_formula_sum            'C35 H59 Mn3.5 Mo12 N10 O71 P8'
_chemical_formula_weight         3347.25
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-08-06
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-08-07 deposited with the CCDC.	2023-12-01 downloaded from the CCDC.
;
_cell_angle_alpha                97.426(2)
_cell_angle_beta                 105.699(2)
_cell_angle_gamma                93.950(2)
_cell_formula_units_Z            2
_cell_length_a                   14.7317(13)
_cell_length_b                   15.1925(14)
_cell_length_c                   20.7026(19)
_cell_measurement_reflns_used    9843
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      28.36
_cell_measurement_theta_min      2.29
_cell_volume                     4397.0(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX3 Ver. 2016.5-0 (Bruker-AXS, 2016)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      273.15
_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 0.988
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w 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  0.0158
_diffrn_reflns_av_unetI/netI     0.0294
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            24984
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.034
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           40.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.401
_exptl_absorpt_correction_T_max  0.8619
_exptl_absorpt_correction_T_min  0.4427
_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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.528
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3237
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_refine_diff_density_max         2.226
_refine_diff_density_min         -1.316
_refine_diff_density_rms         0.152
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1330
_refine_ls_number_reflns         15287
_refine_ls_number_restraints     286
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0452
_refine_ls_R_factor_gt           0.0396
_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^)+(0.0256P)^2^+49.8035P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0946
_refine_ls_wR_factor_ref         0.0979
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13400
_reflns_number_total             15287
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ce01031g2.cif
_cod_data_source_block           1
_cod_depositor_comments          'Adding full bibliography for 7247813.cif.'
_cod_original_formula_sum        'C35 H59 Mn3.50 Mo12 N10 O71 P8'
_cod_database_code               7247813
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H69C,H69D} of O69A, All N(H) groups
 At 1.5 times of:
  All O(H,H,H,H,H,H,H,H) groups, {H73A,H73B} of O73, {H2AA,H2AB} of O2A,
  {H33A,H33B} of O33, {H2A,H2B} of O2, {H65A,H65B} of O65, {H67A,H67B} of O67,
  {H17A,H17B} of O17, {H69A,H69B} of O69, {H35A,H35B} of O35, {H15A,H15B} of
  O15, {H53A,H53B} of O53
2. Restrained distances
 O1-H1 = O16-H16 = O26-H26 = O4-H4 = O20-H20 = O18-H18
 0.85 with sigma of 0.02
 Mn2-H67A \\sim Mn2-H67B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Mn2 \\sim O2 \\sim O2A \\sim Mn1 \\sim O59 \\sim O69 \\sim O69A \\sim Mn3 \\sim
O33 \\sim O63 \\sim O67 \\sim O31: within 3A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3A
O73 \\sim O67 \\sim Mn6 \\sim O63 \\sim Mn2 \\sim O59: within 3A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 3A
Uanis(O2A) \\sim Ueq, Uanis(O69) \\sim Ueq, Uanis(O69A) \\sim Ueq: with sigma
of 0.001 and sigma for terminal atoms of 0.002
Uanis(O74) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O67) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C7, C2, N9, C31, C15, N2, C33, C29, C17
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(O67)=Sof(H67A)=Sof(H67B)=1-FVAR(1)
 Sof(O73)=Sof(H73A)=Sof(H73B)=FVAR(1)
 Sof(O74)=Sof(H74A)=Sof(H74B)=1-FVAR(2)
 Sof(O33)=Sof(H33A)=Sof(H33B)=FVAR(2)
 Sof(O69A)=Sof(H69C)=Sof(H69D)=1-FVAR(3)
 Sof(O69)=Sof(H69A)=Sof(H69B)=FVAR(3)
 Sof(O2)=Sof(H2A)=Sof(H2B)=1-FVAR(4)
 Sof(O2A)=Sof(H2AA)=Sof(H2AB)=FVAR(4)
 Fixed Sof: Mn2(0.7) Mn3(0.5) Mn1(0.25) Mn6(0.05)
6.a Riding coordinates:
 O15(H15A,H15B), O67(H67A,H67B), O17(H17A,H17B), O69(H69A,H69B), O35(H35A,
 H35B), O69A(H69C,H69D), O73(H73A,H73B), O74(H74A,H74B)
6.b Rotating group:
 O53(H53A,H53B), O2(H2A,H2B), O65(H65A,H65B), O33(H33A,H33B), O2A(H2AA,H2AB)
6.c Aromatic/amide H refined with riding coordinates:
 N1(H1A), N4(H4A), N6(H6), N8(H8), N10(H10), N5(H5A), N3(H3A), N7(H7), C1(H1B),
  C4(H4B), C22(H22), C24(H24), C26(H26A), C28(H28), C30(H30), C32(H32),
 C34(H34), C35(H35), C9(H9), C19(H19), C5(H5), C21(H21), C11(H11), C23(H23),
 C3(H3), C25(H25), C13(H13), C27(H27), C29(H29), C17(H17), C15(H15), C31(H31),
 N2(H2), N9(H9A), C33(H33)
6.d Fitted hexagon refined as free rotating group:
 C29(C17,C15,C7,C2,C31)
;
_shelx_res_checksum              31957
_olex2_submission_special_instructions 'No special instructions were received'