Crystallographic Evidence of a Trinuclear (salen)Manganese(IV/III/IV)-μ-Oxo Formed during Catalytic C(sp3)–H Oxidation Reactions
Paul, Bhaswati; Dabare, Kusalvin; Bocarsly, Joshua D.; Mills, L. Reginald; Dalton Transactions  (2026) –; doi:10.1039/D5DT02844B

data_7720010
_publ_section_title
;
 Crystallographic Evidence of a Trinuclear
 (salen)Manganese(IV/III/IV)-\m-Oxo Formed during Catalytic C(sp3)--H
 Oxidation Reactions
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT02844B
_journal_year                    2026
_chemical_formula_moiety         'C16 H18 Mn N2 O4, F6 P, C2 H3 N'
_chemical_formula_sum            'C18 H21 F6 Mn N3 O4 P'
_chemical_formula_weight         543.29
_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             2025-08-14
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.22 svn.r631f81ec for OlexSys, GUI svn.r7248)
;
_audit_update_record
;
2025-08-30 deposited with the CCDC.	2025-12-10 downloaded from the CCDC.
;
_cell_angle_alpha                102.9360(10)
_cell_angle_beta                 94.3530(10)
_cell_angle_gamma                91.086(2)
_cell_formula_units_Z            2
_cell_length_a                   6.9874(3)
_cell_length_b                   12.2254(6)
_cell_length_c                   13.3032(6)
_cell_measurement_reflns_used    4213
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      25.44
_cell_measurement_theta_min      2.57
_cell_volume                     1103.62(9)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.00
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            17939
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.595
_diffrn_reflns_theta_min         2.047
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.752
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6977
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0480 before and 0.0402 after correction.
The Ratio of minimum to maximum transmission is 0.9358.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.635
_exptl_crystal_description       needle
_exptl_crystal_F_000             552
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.013
_refine_diff_density_min         -0.462
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     301
_refine_ls_number_reflns         5095
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0647
_refine_ls_R_factor_gt           0.0388
_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^)+(0.0394P)^2^+0.6392P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0838
_refine_ls_wR_factor_ref         0.0926
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3763
_reflns_number_total             5095
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02844b2.cif
_cod_data_source_block           bp_1_0m_a
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               7720010
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.840
_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 C(H,H,H) groups, All O(H,H) groups
2.a Rotating group:
 O4(H4A,H4B), O3(H3A,H3B)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C10(H10), C3(H3), C8(H8), C7(H7), C5(H5), C14(H14), C12(H12),
 C6(H6), C13(H13)
2.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C)
;
_shelx_res_checksum              74031
_olex2_submission_special_instructions 'No special instructions were received'