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_1572290
_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
'C76 H98 Mn4 N12 O12, 2(C4 H8 O), 2(C24 H20 B), 1[C4H8O]'
_chemical_formula_sum            'C136 H162 B2 Mn4 N12 O15'
_chemical_formula_weight         2446.15
_chemical_name_systematic        Mn4_tpon2
_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             2024-07-15
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_cell_angle_alpha                99.904(3)
_cell_angle_beta                 101.628(4)
_cell_angle_gamma                96.449(4)
_cell_formula_units_Z            1
_cell_length_a                   9.257(2)
_cell_length_b                   18.174(4)
_cell_length_c                   19.196(4)
_cell_measurement_reflns_used    9277
_cell_measurement_temperature    113
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      3.1
_cell_volume                     3079.7(11)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      113
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.962
_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  0.0276
_diffrn_reflns_av_unetI/netI     0.0510
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            25676
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.474
_diffrn_reflns_theta_min         3.056
_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    0.470
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.909
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_description       Chip
_exptl_crystal_F_000             1292
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.522
_refine_diff_density_min         -0.576
_refine_diff_density_rms         0.084
_refine_ls_extinction_coef       0.0240(14)
_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   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     788
_refine_ls_number_reflns         13566
_refine_ls_number_restraints     75
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0740
_refine_ls_R_factor_gt           0.0582
_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^)+(0.0822P)^2^+3.6569P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1493
_refine_ls_wR_factor_ref         0.1673
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10676
_reflns_number_total             13566
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            Complex2.cif
_cod_data_source_block           Mn4tpon2
_cod_original_cell_volume        3079.7(12)
_cod_database_code               1572290
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.912
_shelx_estimated_absorpt_t_min   0.912
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H36A,H36B,H36C} of C36, All C(H,H) groups
 At 1.5 times of:
  {H34A,H34B,H34C} of C34, {H38A,H38B,H38C} of C38
2. Restrained distances
 O8-C67 = O8-C70
 1.44 with sigma of 0.02
 C67-C68 = C69-C70
 1.53 with sigma of 0.02
 C68-C69
 1.54 with sigma of 0.02
 O8-C68 = O8-C69 = C67-C69 = C68-C70
 2.38 with sigma of 0.04
 C67-C68 \\sim C68-C69 \\sim C69-C70
 with sigma of 0.02
 O8-C67 \\sim O8-C70
 with sigma of 0.02
 O8-C68 \\sim O8-C69
 with sigma of 0.04
 C68-C70 \\sim C67-C69
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O8 \\sim C67 \\sim C68 \\sim C69 \\sim C70: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 O8, C67, C68, C69, C70
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O8(0.5) C67(0.5) H67A(0.5) H67B(0.5) C68(0.5) H68A(0.5) H68B(0.5)
 C69(0.5) H69A(0.5) H69B(0.5) C70(0.5) H70A(0.5) H70B(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B),
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B),
  C26(H26A,H26B), C32(H32A,H32B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,
 H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B),
 C70(H70A,H70B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C10(H10), C21(H21),
 C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29), C30(H30), C40(H40),
  C41(H41), C42(H42), C43(H43), C44(H44), C46(H46), C47(H47), C48(H48),
 C49(H49), C50(H50), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C58(H58),
  C59(H59), C60(H60), C61(H61), C62(H62)
6.c Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C)
;
_shelx_res_checksum              18606
_shelx_hkl_checksum              507
_olex2_submission_original_sample_id Mn4tpon2
_olex2_submission_special_instructions 'No special instructions were received'