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_7720011
_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
'Cl O4, C72 H106 Mn2 N4 O5, 2(C6 H6), [+ solvents]4[CH3CN]'
_chemical_formula_sum            'C84 H118 Cl Mn2 N4 O9'
_chemical_formula_weight         1473.15
_chemical_name_systematic        BP_5
_space_group_crystal_system      orthorhombic
_space_group_IT_number           20
_space_group_name_Hall           'C 2c 2'
_space_group_name_H-M_alt        'C 2 2 21'
_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                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.8329(2)
_cell_length_b                   30.9457(4)
_cell_length_c                   14.1235(2)
_cell_measurement_reflns_used    9995
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      68.17
_cell_measurement_theta_min      2.75
_cell_volume                     8231.14(18)
_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 2019/3 (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 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  0.0337
_diffrn_reflns_av_unetI/netI     0.0375
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            33393
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.295
_diffrn_reflns_theta_min         2.747
_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    3.231
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6437
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1001 before and 0.0672 after correction.
The Ratio of minimum to maximum transmission is 0.8547.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'reddish brown'
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.189
_exptl_crystal_description       needle
_exptl_crystal_F_000             3156
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.242
_refine_diff_density_min         -0.309
_refine_diff_density_rms         0.080
_refine_ls_abs_structure_details
;
 Flack x determined using 2944 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.2940(13)
_refine_ls_extinction_coef       0.00016(4)
_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   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     522
_refine_ls_number_reflns         7492
_refine_ls_number_restraints     625
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0621
_refine_ls_R_factor_gt           0.0599
_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^)+(0.0966P)^2^+21.9160P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1600
_refine_ls_wR_factor_ref         0.1617
_reflns_Friedel_coverage         0.811
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                7129
_reflns_number_total             7492
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02844b2.cif
_cod_data_source_block           cu_bp_5_0m_a
_cod_database_code               7720011
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.738
_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
 Cl2-O3 = Cl2-O4 = Cl2-O5 = Cl2-O6
 1.5 with sigma of 0.02
 C34B_1-C33_1 \\sim C34A-C33_1 \\sim C35A-C33_1 \\sim C35B_1-C33_1 \\sim
C36A-C33_1 \\sim C36B_1-
 C33_1
 with sigma of 0.02
 Cl2-O3 \\sim Cl2-O4 \\sim Cl2-O5 \\sim Cl2-O6
 with sigma of 0.02
 O3-O5 \\sim O4-O6 \\sim O3-O6 \\sim O4-O5 \\sim O3-O4 \\sim O5-O6
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C34A \\sim C35A \\sim C36A \\sim C35B_1 \\sim C36B_1 \\sim C34B_1: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C1_2 \\sim C2_2 \\sim C3_2 \\sim C4_2 \\sim C5_2 \\sim C6_2: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Cl2 \\sim O3 \\sim O4 \\sim O5 \\sim O6: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
O3 \\sim O4 \\sim O5 \\sim O6: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(O6) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O5) \\sim Ueq, Uanis(O3) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C1_2, C2_2, C3_2, C4_2, C5_2, C6_2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 Cl2, O3, O4, O5, O6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, O4, O5, O6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C35A)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36A)=Sof(H36A)=Sof(H36B)=
 Sof(H36C)=Sof(C34B)=Sof(H34A)=Sof(H34B)=Sof(H34C)=1-FVAR(1)
 Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C35B)=Sof(H35A)=Sof(H35B)=
 Sof(H35C)=Sof(C36B)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(1)
 Fixed Sof: Cl2(0.5) O3(0.5) O4(0.5) O5(0.5) O6(0.5)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C6(H6)
6.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C11(H11), C22(H22), C26(H26), C28(H28), C1(H1), C2(H2),
 C3(H3), C4(H4), C5(H5), C6(H6)
6.d Idealised Me refined as rotating group:
 C34A(H34A,H34B,H34C), C35A(H35A,H35B,H35C), C36A(H36A,H36B,H36C), 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), C35B(H35A,H35B,H35C), C36B(H36A,H36B,H36C),
 C34B(H34A,H34B,H34C)
;
_shelx_res_checksum              73066
_olex2_submission_special_instructions 'No special instructions were received'