Catalytic fate of structurally characterized manganese(iii)–salen complexes towards efficient transformation of primary amides to amines or nitriles using hydrosilane
Bandopadhyay, Nilaj; Paramanik, Krishnendu; Sarkar, Gayetri; Chatterjee, Souvik; Roy, Suvojit; Panda, Subhra Jyoti; Purohit, Chandra Shekhar; Biswas, Bhaskar; Das, Hari Sankar; New Journal of Chemistry 47 (2023) 9414–9420; doi:10.1039/D3NJ01183F

data_7062423
_publ_section_title
;
 Catalytic fate of structurally characterized manganese(iii)--salen
 complexes towards efficient transformation of primary amides to amines or
 nitriles using hydrosilane
;
_journal_issue                   19
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              9414
_journal_page_last               9420
_journal_paper_doi               10.1039/D3NJ01183F
_journal_volume                  47
_journal_year                    2023
_chemical_formula_moiety
'2(C16 H18 Mn N2 O4), C32 H32 Mn2 N4 O6, 4(C F3 O3 S), 2(H2 O)'
_chemical_formula_sum            'C68 H72 F12 Mn4 N8 O28 S4'
_chemical_formula_weight         2025.33
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-04-07 deposited with the CCDC.	2023-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.3410(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.65610(10)
_cell_length_b                   21.2356(2)
_cell_length_c                   14.03270(10)
_cell_measurement_reflns_used    19908
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.3620
_cell_measurement_theta_min      3.7560
_cell_volume                     4044.52(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.52a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.52a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.52a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.9977
_diffrn_measured_fraction_theta_max 0.9825
_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    -84.00  -2.00   0.50    0.17    --  -38.50 120.00-111.00  164
  2  \w   -107.00 -21.00   0.50    0.17    --  -38.50 154.00  47.00  172
  3  \w     43.00 103.00   0.50    0.17    --   49.56-154.00   7.00  120
  4  \w     37.00  62.00   0.50    0.17    --   49.56-120.00 165.00   50
  5  \w     84.00 110.00   0.50    0.29    --  111.00-154.00   7.00   52
  6  \w    100.00 152.00   0.50    0.29    --  111.00 120.00-111.00  104
  7  \w     91.00 123.00   0.50    0.29    --  111.00 154.00  47.00   64
  8  \w     73.00 109.00   0.50    0.29    --  111.00-120.00 165.00   72
  9  \w    -49.00  24.00   0.50    0.17    --  -38.50  57.00   0.00  146
 10  \w   -102.00 -20.00   0.50    0.17    --  -38.50 -71.00  65.87  164
 11  \w     51.00 116.00   0.50    0.17    --   49.56  37.00  90.00  130
 12  \w     98.00 164.00   0.50    0.29    --  111.00  61.00-120.00  132
 13  \w     53.00 106.00   0.50    0.29    --  111.00 -94.00-180.00  106
 14  \w    112.00 176.00   0.50    0.29    --  111.00  30.00  60.00  128
 15  \w     95.00 121.00   0.50    0.29    --  111.00 -61.00 120.00   52
 16  \w    140.00 173.00   0.50    0.29    --  111.00  45.00   0.00   66
 17  \w     43.00 104.00   0.50    0.29    --  111.00 -94.00 -30.00  122
 18  \w     45.00 113.00   0.50    0.29    --  111.00 -30.00  90.00  136
 19  \w     70.00 109.00   0.50    0.29    --  111.00-111.00 -30.00   78
 20  \w    105.00 144.00   0.50    0.29    --  111.00  15.00   0.00   78
 21  \w     59.00 114.00   0.50    0.29    --  111.00 -30.00-180.00  110
 22  \w     68.00 104.00   0.50    0.29    --  111.00 -94.00-150.00   72
 23  \w     48.00  87.00   0.50    0.29    --  111.00 -61.00 120.00   78
 24  \w     84.00 109.00   0.50    0.29    --  111.00-111.00-150.00   50
 25  \w     65.00 123.00   0.50    0.29    --  111.00 -61.00 -60.00  116
 26  \w     63.00  97.00   0.50    0.29    --  111.00 -94.00  60.00   68
 27  \w     83.00 109.00   0.50    0.29    --  111.00-111.00 -90.00   52
 28  \w    115.00 176.00   0.50    0.29    --  111.00  77.00 150.00  122
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0397062000
_diffrn_orient_matrix_UB_12      -0.0641391000
_diffrn_orient_matrix_UB_13      -0.0382711000
_diffrn_orient_matrix_UB_21      0.0911729000
_diffrn_orient_matrix_UB_22      -0.0328699000
_diffrn_orient_matrix_UB_23      0.0522462000
_diffrn_orient_matrix_UB_31      -0.0547402000
_diffrn_orient_matrix_UB_32      -0.0082293000
_diffrn_orient_matrix_UB_33      0.0894835000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            36119
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.580
_diffrn_reflns_theta_min         3.792
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.938
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56929
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.52a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.663
_exptl_crystal_description       plate
_exptl_crystal_F_000             2064
_exptl_crystal_preparation       'As per the reaction scheme'
_exptl_crystal_recrystallization_method 'Slow evaporation'
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.21
_refine_diff_density_max         0.755
_refine_diff_density_min         -0.494
_refine_diff_density_rms         0.075
_refine_ls_extinction_coef       0.00131(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     574
_refine_ls_number_reflns         8636
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0369
_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^)+(0.0478P)^2^+3.8651P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0921
_refine_ls_wR_factor_ref         0.0934
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8105
_reflns_number_total             8636
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj01183f2.cif
_cod_data_source_block           sjp-n-11_auto
_cod_depositor_comments
'Adding full bibliography for 7062422--7062423.cif.'
_cod_database_code               7062423
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         ' C H N O Mn '
_chemical_oxdiff_usercomment     'LIGHT BROWN PLATE'
_shelx_estimated_absorpt_t_max   0.324
_shelx_estimated_absorpt_t_min   0.208
_diffrn_oxdiff_digest_frames
;
01d74188cd3916469fbe835c73cc0534b500042c976
;
_diffrn_oxdiff_digest_hkl
;
011302786935d1fa32d7b6147bc3645fa0fe24
;
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All O(H) groups, All O(H,H) groups
2. Restrained distances
 Mn2-H7A \\sim Mn2-H7B
 with sigma of 0.02
 Mn1-H4A \\sim Mn1-H4B
 with sigma of 0.02
3.a Free rotating group:
 O4(H4A,H4B), O7(H7A,H7B), O8(H8C,H8D)
3.b Rotating group:
 O3(H3A)
3.c Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C8(H8A,H8B), C24(H24A,H24B), C25(H25A,H25B)
3.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3), C15(H15), C13(H13), C10(H10), C14(H14), C4(H4), C7(H7),
 C16(H16), C2(H2), C19(H19), C23(H23), C21(H21), C30(H30), C26(H26), C29(H29),
 C20(H20), C18(H18), C28(H28), C31(H31)
;
_shelx_res_checksum              3654
_olex2_exptl_crystal_mounting_method 'Mounted on the loop'
_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 1.401
_oxdiff_exptl_absorpt_empirical_full_min 0.816