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_7720013
_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
'0.5(C75 H97 Mn2 N6 O5), 0.5(C72 H93 Mn2 N4 O5), F6 P, 0.5(C3 H4 N2), [+ solvents]0.5[CH3CN], 1[CH3CN]'
_chemical_formula_sum            'C78 H102.5 F6 Mn2 N7.5 O5.5 P'
_chemical_formula_weight         1488.02
_chemical_name_systematic        BP_Mn4_NaPz
_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             2025-08-01
_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                105.2620(10)
_cell_angle_beta                 95.1030(10)
_cell_angle_gamma                113.6180(10)
_cell_formula_units_Z            4
_cell_length_a                   17.5632(4)
_cell_length_b                   21.6143(4)
_cell_length_c                   23.7547(5)
_cell_measurement_reflns_used    9759
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      68.12
_cell_measurement_theta_min      3.54
_cell_volume                     7775.8(3)
_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 0.997
_diffrn_measured_fraction_theta_max 0.995
_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  0.0615
_diffrn_reflns_av_unetI/netI     0.0564
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            149365
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.311
_diffrn_reflns_theta_min         3.542
_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    3.401
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5749
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1018 before and 0.0523 after correction.
The Ratio of minimum to maximum transmission is 0.7634.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       needle
_exptl_crystal_F_000             3144
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.338
_refine_diff_density_min         -0.785
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1831
_refine_ls_number_reflns         28362
_refine_ls_number_restraints     412
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.1010
_refine_ls_R_factor_gt           0.0759
_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^)+(0.1196P)^2^+12.1933P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2048
_refine_ls_wR_factor_ref         0.2188
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23159
_reflns_number_total             28362
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02844b2.cif
_cod_data_source_block           cu_pyrazole_mn_0m_a
_cod_original_cell_volume        7775.7(3)
_cod_original_sg_symbol_H-M      P-1
_cod_original_formula_sum        'C78 H102.50 F6 Mn2 N7.50 O5.50 P'
_cod_database_code               7720013
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O3_2-H3 = O5_1-H5
 1.1 with sigma of 0.02
 O5_1-H5 = O3_2-H3
 0.8 with sigma of 0.02
 C30_2-C29_2 = C31_2-C29_2 = C32_2-C29_2
 1.5 with sigma of 0.02
 N2_4-N1_4 \\sim N1_4-C1_4 \\sim C2_4-C1_4 \\sim C2_4-C3_4 \\sim N2_4-C3_4
 with sigma of 0.02
 C1_4-N2_4 \\sim N1_4-C3_4
 with sigma of 0.02
 C31_2-C30_2 \\sim C31_2-C32_2
 with sigma of 0.02
 P1_5-F5_5 \\sim P1_5-F4_5 \\sim P1_5-F2_5 \\sim P1_5-F3_5 \\sim P1_5-F6_5
\\sim P1_5-F1_5
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N1_4 \\sim N2_4 \\sim C1_4 \\sim C3_4 \\sim C2_4: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
C31_2 \\sim C29_2 \\sim C30_2 \\sim C32_2: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
F6_5 \\sim F1_5 \\sim P1_5 \\sim F2_5 \\sim F3_5 \\sim F4_5 \\sim F5_5 \\sim
F7_5 \\sim F8_5 \\sim P2_5 \\sim F9_5 \\sim F10_5 \\sim F11_5 \\sim F12_5:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C71_2) \\sim Ueq, Uanis(C72_2) \\sim Ueq, Uanis(C70_2) \\sim Ueq,
Uanis(C30_2) \\sim Ueq, Uanis(C32_2) \\sim Ueq, Uanis(C29_2) \\sim Ueq,
Uanis(C31_2) \\sim Ueq, Uanis(C34_1) \\sim Ueq, Uanis(C33_1) \\sim Ueq,
Uanis(C35_1) \\sim Ueq, Uanis(C36_1) \\sim Ueq: with sigma of 0.01 and sigma
for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C29_2, C31_2, C30_2, C32_2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N2_4, N1_4, C1_4, C3_4, C2_4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 F6_5, F1_5, P1_5, F2_5, F3_5, F4_5, F5_5, F7_5, F8_5, P2_5, F9_5, F10_5,
 F11_5, F12_5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(F8)=Sof(P2)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F7)=Sof(F12)=1-FVAR(1)
 Sof(F1)=Sof(P1)=Sof(F2)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C58(H58), C51(H51), C54(H54), C57(H57), C64(H64), C62(H62), C22(H22), C7(H7),
 N6(H6), C73(H73), C41(H41), C39(H39), C55(H55), C56(H56), C3(H3), C6(H6A),
 C75(H75), C74(H74), C26(H26), C28(H28), C11(H11), C13(H13), C4(H4), C5(H5),
 C28(H28), C7(H7), C22(H22), C3(H3), C6(H6), C13(H13), C11(H11), C58(H58),
 C43(H43), C26(H26), C4(H4), C5(H5), C42(H42), C39(H39), C47(H47), C45(H45),
 C62(H62), C64(H64), C41(H41), C40(H40), C3(H3), N2(H2), C1(H1), C2(H2A)
6.b Idealised Me refined as rotating group:
 C71(H71A,H71B,H71C), C70(H70A,H70B,H70C), C72(H72A,H72B,H72C), C46(H46A,H46B,
 H46C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C68(H68A,H68B,H68C), C66(H66A,
 H66B,H66C), C67(H67A,H67B,H67C), C31(H31A,H31B,H31C), C30(H30A,H30B,H30C),
 C32(H32A,H32B,H32C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C48(H48A,H48B,H48C), C36(H36A,
 H36B,H36C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C21(H21A,H21B,H21C),
 C20(H20A,H20B,H20C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C20(H20A,H20B,
 H20C), C19(H19A,H19B,H19C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C35(H35A,
 H35B,H35C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C15(H15A,H15B,H15C),
 C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C55(H55A,H55B,H55C), C68(H68A,H68B,
 H68C), C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C30(H30A,H30B,H30C), C53(H53A,H53B,H53C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C), C72(H72A,H72B,H72C), C71(H71A,H71B,H71C), C70(H70A,H70B,
 H70C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              57906
_shelx_fab_checksum              72280
_olex2_submission_special_instructions 'No special instructions were received'