Where is the Unpaired-Electron Density? A Combined Experimental and Theoretical Finding on Geometric and Electronic Structures of Co(III) and Mn(IV) Complexes of Unsymmetrical Non-innocent Pincer ONS Ligand
Mukherjee, Chandan; Sarkar, Prasenjit; Sarmah, Amrit; Dalton Transactions  (2022) –; doi:10.1039/D2DT01868C

data_7711454
_publ_section_title
;
 Where is the Unpaired-Electron Density? A Combined Experimental and
 Theoretical Finding on Geometric and Electronic Structures of Co(III) and
 Mn(IV) Complexes of Unsymmetrical Non-innocent Pincer ONS Ligand
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01868C
_journal_year                    2022
_chemical_formula_moiety         'C40 H48 Mn N2 O2 S2'
_chemical_formula_sum            'C40 H48 Mn N2 O2 S2'
_chemical_formula_weight         707.86
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-09-12
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-09-14 deposited with the CCDC.	2022-09-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.952(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.3127(10)
_cell_length_b                   18.3726(8)
_cell_length_c                   10.8905(5)
_cell_measurement_reflns_used    20446
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.3810
_cell_measurement_theta_min      3.2690
_cell_volume                     4138.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXL-2018/3 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0387
_diffrn_reflns_av_unetI/netI     0.0519
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            18488
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.997
_diffrn_reflns_theta_max         24.997
_diffrn_reflns_theta_min         2.938
_exptl_absorpt_coefficient_mu    0.452
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44486
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.136
_exptl_crystal_description       block
_exptl_crystal_F_000             1500
_exptl_crystal_recrystallization_method 'dichloromethane and acetonitrile'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.271
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     452
_refine_ls_number_reflns         7267
_refine_ls_number_restraints     471
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0669
_refine_ls_R_factor_gt           0.0492
_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^)+(0.0543P)^2^+1.5405P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1220
_refine_ls_wR_factor_ref         0.1305
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5494
_reflns_number_total             7267
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01868c2.cif
_cod_data_source_block           platon_sqd
_cod_original_sg_symbol_H-M      P21/c
_cod_database_code               7711454
_shelx_shelxl_version_number     2019/1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C25-C31 \\sim C25-C31A
 with sigma of 0.02
 C34-C33 \\sim C34A-C33A
 with sigma of 0.04
 C31-C34 \\sim C31A-C34A
 with sigma of 0.02
 C33-C32 \\sim C33A-C32A
 with sigma of 0.04
 C31-C33 \\sim C31A-C33A
 with sigma of 0.02
 C31-C32 \\sim C31A-C32A
 with sigma of 0.02
 C34-C32 \\sim C34A-C32A
 with sigma of 0.04
 C25-C34 \\sim C25-C34A
 with sigma of 0.04
 C25-C33 \\sim C25-C33A
 with sigma of 0.04
 C25-C32 \\sim C25-C32A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C31A) = Uanis(C31)
Uanis(C34A) = Uanis(C34)
Uanis(C33) = Uanis(C33A)
Uanis(C32) = Uanis(C32A)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C31A)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C34A)=Sof(H34D)=
 Sof(H34E)=Sof(H34F)=Sof(C32A)=Sof(H32D)=Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(C31)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C33)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C16(H16), C17(H17), C4(H4), C19(H19), C18(H18), C40(H40), C26(H26),
 C24(H24), C37(H37), C39(H39), C38(H38)
6.b Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C12(H12A,H12B,H12C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C),
 C29(H29A,H29B,H29C), C28(H28A,H28B,H28C), C10(H10A,H10B,H10C), C14(H14A,H14B,
 H14C), C30(H30A,H30B,H30C), C34(H34A,H34B,H34C), C33(H33A,H33B,H33C), C32(H32A,
 H32B,H32C), C33A(H33D,H33E,H33F), C34A(H34D,H34E,H34F), C32A(H32D,H32E,H32F)
;
_shelx_res_checksum              65181
_shelx_hkl_checksum              81800
_shelx_fab_checksum              70632
_olex2_submission_special_instructions 'No special instructions were received'