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_7720012
_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         'C42 H52 F5 Mn N2 O3, C3 H6 O, 1[H2O]'
_chemical_formula_sum            'C45 H60 F5 Mn N2 O5'
_chemical_formula_weight         858.89
_chemical_name_systematic        Mn1_PhONa
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-30
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-08-30 deposited with the CCDC.	2025-12-10 downloaded from the CCDC.
;
_cell_angle_alpha                64.452(2)
_cell_angle_beta                 75.527(2)
_cell_angle_gamma                87.510(2)
_cell_formula_units_Z            2
_cell_length_a                   11.7342(3)
_cell_length_b                   14.6513(4)
_cell_length_c                   15.2022(4)
_cell_measurement_reflns_used    6503
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      68.05
_cell_measurement_theta_min      3.56
_cell_volume                     2277.01(11)
_computing_cell_refinement       'SAINT V8.41 (?, 2016)'
_computing_data_reduction        'SAINT V8.41 (?, 2016)'
_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      100.00
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.987
_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           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0470
_diffrn_reflns_av_unetI/netI     0.0495
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            23108
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.311
_diffrn_reflns_theta_min         3.555
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.902
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6631
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1041 before and 0.0537 after correction.
The Ratio of minimum to maximum transmission is 0.8805.
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    1.253
_exptl_crystal_description       block
_exptl_crystal_F_000             908
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.440
_refine_diff_density_min         -0.694
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     528
_refine_ls_number_reflns         8240
_refine_ls_number_restraints     20
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0535
_refine_ls_R_factor_gt           0.0440
_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^)+(0.0675P)^2^+0.6080P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1141
_refine_ls_wR_factor_ref         0.1204
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6948
_reflns_number_total             8240
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02844b2.cif
_cod_data_source_block           cu_phona_acetone_h2o_0m_a
_cod_original_sg_symbol_H-M      P-1
_cod_database_code               7720012
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.594
_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
2. Restrained distances
 C3_2-C2_2 \\sim C2_2-C1_2
 with sigma of 0.02
 C1_2-O1_2 \\sim C3_2-O1_2
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C2_2, O1_2, C1_2, C3_2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4.a Ternary CH refined with riding coordinates:
 C1(H1), C6(H6)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B)
4.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C11(H11), C13(H13), C22(H22), C26(H26), C28(H28)
4.d Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C),
 C36(H36A,H36B,H36C), C1(H1A,H1B,H1C), C3(H3A,H3B,H3C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              2418
_shelx_fab_checksum              83045
_olex2_submission_special_instructions 'No special instructions were received'