Crystal Structures, Magnetic Properties, and Redox Behaviors of Carboxylato-Bridged Mn(II) Complexes with Ditopic Ligands Featuring N3-Coordination Sites
Sugiyama, Junya; Umemoto, Yusuke; Sato, Sota; Yoneda, Ko; Koikawa, Masayuki; Chemistry 6 (2024) 601–617; doi:10.3390/chemistry6040036

data_1572289
_publ_section_title
;
 Crystal Structures, Magnetic Properties, and Redox Behaviors of
 Carboxylato-Bridged Mn(II) Complexes with Ditopic Ligands Featuring
 N3-Coordination Sites
;
_journal_issue                   4
_journal_name_full               Chemistry
_journal_page_first              601
_journal_page_last               617
_journal_paper_doi               10.3390/chemistry6040036
_journal_volume                  6
_journal_year                    2024
_chemical_formula_moiety
'C74 H92 Mn4 N12 O14, C78 H94 Mn4 N12 O16, 6(F6 P), 12(H2 O)'
_chemical_formula_sum            'C152 H210 F36 Mn8 N24 O42 P6'
_chemical_formula_weight         4354.77
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-15
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.229(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   24.719(5)
_cell_length_b                   20.878(5)
_cell_length_c                   18.209(4)
_cell_measurement_reflns_used    23808
_cell_measurement_temperature    113
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      3.0
_cell_volume                     9323(4)
_computing_cell_refinement
;
CrystalClear-SM Expert 2.0 r16 (Rigaku, 2014)
;
_computing_data_collection
;
CrystalClear-SM Expert 2.0 r16 (Rigaku, 2014)
;
_computing_data_reduction
;
CrystalClear-SM Expert 2.0 r16 (Rigaku, 2014)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      113.00
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.981
_diffrn_measurement_device
;
AFC11 (Right): Eulerian 3 circle
;
_diffrn_measurement_device_type
;
Rigaku Saturn724+ (4x4 bin mode)
;
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0626
_diffrn_reflns_av_unetI/netI     0.0658
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            74634
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.518
_diffrn_reflns_theta_min         3.019
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.691
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.826
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.551
_exptl_crystal_description       prism
_exptl_crystal_F_000             4480
_exptl_crystal_size_max          0.61
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.292
_refine_diff_density_min         -0.984
_refine_diff_density_rms         0.097
_refine_ls_extinction_coef       0.00203(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1279
_refine_ls_number_reflns         21041
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0805
_refine_ls_R_factor_gt           0.0581
_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^)+(0.0796P)^2^+4.9136P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1459
_refine_ls_wR_factor_ref         0.1644
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15473
_reflns_number_total             21041
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            Complex3.cif
_cod_data_source_block           mn4tpxn
_cod_database_code               1572289
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.874
_shelx_estimated_absorpt_t_min   0.678
_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) groups, All O(H,H) groups
2. Restrained distances
 O7-H7
 0.85 with sigma of 0.01
 Mn2-H7
 2.756106 with sigma of 0.02
 C37-H7
 1.906825 with sigma of 0.02
 Mn1-H3A \\sim Mn1-H3B
 with sigma of 0.02
 P4-F14 \\sim P4-F14A
 with sigma of 0.02
 P4-F15 \\sim P4-F15A
 with sigma of 0.02
 P4-F16 \\sim P4-F16A
 with sigma of 0.02
 P4-F17 \\sim P4-F17A
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 F2, F3, F4, F5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(F14A)=Sof(F15A)=Sof(F16A)=Sof(F17A)=1-FVAR(1)
 Sof(F14)=Sof(F15)=Sof(F16)=Sof(F17)=FVAR(1)
5.a Free rotating group:
 O3(H3A,H3B), O16(H16A,H16B), O17(H17A,H17B), O18(H18A,H18B), O19(H19A,H19B),
 O20(H20C,H20D), O21(H21A,H21B)
5.b Rotating group:
 O4(H4A,H4B), O12(H12A,H12B)
5.c Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C12(H12C,H12D), C13(H13A,H13B), C20(H20A,H20B), C26(H26A,H26B),
 C32(H32A,H32B), C43(H43A,H43B), C49(H49A,H49B), C50(H50A,H50B), C57(H57A,H57B),
  C63(H63A,H63B), C69(H69A,H69B)
5.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7A), C8(H8), C9(H9), C10(H10), C15(H15A),
 C16(H16), C17(H17), C18(H18), C21(H21), C22(H22), C23(H23), C24(H24), C27(H27),
  C28(H28), C29(H29), C30(H30), C38(H38), C39(H39), C40(H40), C41(H41),
 C44(H44), C45(H45), C46(H46), C47(H47), C52(H52), C53(H53), C54(H54), C55(H55),
  C58(H58), C59(H59), C60(H60), C61(H61), C64(H64), C65(H65), C66(H66), C67(H67)
5.e Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C71(H71A,H71B,
 H71C), C73(H73A,H73B,H73C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C)
5.f Idealised tetrahedral OH refined as rotating group:
 O15(H15)
;
_shelx_res_checksum              34461
_shelx_hkl_checksum              26422
_olex2_submission_original_sample_id mn4tpxn
_olex2_submission_special_instructions 'No special instructions were received'