A 3D rigid Mn-MOF heterogeneous catalyst for thioether oxidation, cyanosilylation and Knoevenagel condensation
Liu, Han-Fu; Hu, Zhi-Rong; Wu, Tai-Xue; Hao, Hong-Mei; Li, Hai-Ye; Huang, Fu-Ping; CrystEngComm 27 (2025) 1307–1314; doi:10.1039/D4CE01075B

data_7249804
_publ_section_title
;
 A 3D rigid Mn-MOF heterogeneous catalyst for thioether oxidation,
 cyanosilylation and Knoevenagel condensation
;
_journal_issue                   9
_journal_name_full               CrystEngComm
_journal_page_first              1307
_journal_page_last               1314
_journal_paper_doi               10.1039/D4CE01075B
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C18 H14 Mn2 N8 O4'
_chemical_formula_sum            'C18 H14 Mn2 N8 O4'
_chemical_formula_weight         516.25
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-03-28
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2024-09-04 deposited with the CCDC.	2025-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   21.6779(8)
_cell_length_b                   21.6779(8)
_cell_length_c                   12.6682(5)
_cell_measurement_reflns_used    2059
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.2540
_cell_measurement_theta_min      4.2200
_cell_volume                     5155.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9784
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.909
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     35.00  94.00   1.00   45.00    --   17.77 178.00 -30.00   59
  2  \w    -41.00  49.00   1.00   45.00    --  -19.57  57.00 150.00   90
  3  \w     -8.00  88.00   1.00   45.00    --   17.77  38.00-120.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0154167000
_diffrn_orient_matrix_UB_12      -0.0372079000
_diffrn_orient_matrix_UB_13      -0.0080201000
_diffrn_orient_matrix_UB_21      -0.0316949000
_diffrn_orient_matrix_UB_22      -0.0057514000
_diffrn_orient_matrix_UB_23      0.0250933000
_diffrn_orient_matrix_UB_31      -0.0136232000
_diffrn_orient_matrix_UB_32      0.0031000000
_diffrn_orient_matrix_UB_33      -0.0494039000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0459
_diffrn_reflns_av_unetI/netI     0.0568
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.909
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            8753
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.909
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.759
_diffrn_reflns_theta_min         3.255
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.142
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86723
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light colourless'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.496
_exptl_crystal_description       block
_exptl_crystal_F_000             2340
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.127
_refine_diff_density_min         -0.514
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     146
_refine_ls_number_reflns         2713
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0769
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0474P)^2^+15.9024P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1178
_refine_ls_wR_factor_ref         0.1325
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1937
_reflns_number_total             2713
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce01075b2.cif
_cod_data_source_block           20200531-hfp-wtx-20191231-20-ln-lin-mnbbbb_sq
_cod_depositor_comments          'Adding full bibliography for 7249804.cif.'
_cod_original_cell_volume        5155.6(4)
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               7249804
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.894
_shelx_estimated_absorpt_t_min   0.726
_reflns_odcompleteness_completeness 99.15
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Rigid bond restraints
 O1, C1
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C5(H5), C6(H6)
3.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C)
;
_shelx_res_checksum              31942
_shelx_hkl_checksum              54005
_shelx_fab_checksum              83718
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.196
_oxdiff_exptl_absorpt_empirical_full_min 0.903