Exploring the magnetic anisotropy and slow relaxation in heterometallic Co<sup>II</sup>-Ln<sup>III</sup>-Co<sup>II</sup> complexes: from synthesis to <i>ab initio</i> insights.
Samanta, Sukhendu Bikash; Roy, Soumalya; Konieczny, Piotr; Pełka, Robert; Baran, Stanisław; Himchan, Mo; Dey, Atanu; Lee, Junseong; Das, Sourav; Dalton transactions (Cambridge, England : 2003) 54 (2025) 16492–16507; doi:10.1039/d5dt02024g

data_7719631
_publ_section_title
;
 Exploring the magnetic anisotropy and slow relaxation in heterometallic
 Co<sup>II</sup>-Ln<sup>III</sup>-Co<sup>II</sup> complexes: from
 synthesis to <i>ab initio</i> insights.
;
_journal_issue                   44
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16492
_journal_page_last               16507
_journal_paper_doi               10.1039/d5dt02024g
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C42 H42 Cl2 Co2 N6 O8 Tb, C H Cl3, Cl, C H4 O'
_chemical_formula_sum            'C44 H47 Cl6 Co2 N6 O9 Tb'
_chemical_formula_weight         1293.35
_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
_audit_creation_date             2025-08-21
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-08-22 deposited with the CCDC.	2025-10-07 downloaded from the CCDC.
;
_cell_angle_alpha                91.112(7)
_cell_angle_beta                 96.846(6)
_cell_angle_gamma                95.016(7)
_cell_formula_units_Z            4
_cell_length_a                   11.3017(13)
_cell_length_b                   19.388(2)
_cell_length_c                   23.433(2)
_cell_measurement_reflns_used    2606
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      25.40
_cell_measurement_theta_min      2.26
_cell_volume                     5076.1(9)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.983
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2322
_diffrn_reflns_av_unetI/netI     0.3210
_diffrn_reflns_Laue_measured_fraction_full 0.983
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            60926
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.490
_diffrn_reflns_theta_min         1.055
_exptl_absorpt_coefficient_mu    2.398
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6250
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/2 (Bruker,2014/2) was used for absorption correction.
wR2(int) was 0.1253 before and 0.0760 after correction.
The Ratio of minimum to maximum transmission is 0.8387.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.692
_exptl_crystal_description       block
_exptl_crystal_F_000             2584
_exptl_crystal_size_max          0.067
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.033
_refine_diff_density_max         1.209
_refine_diff_density_min         -1.189
_refine_diff_density_rms         0.182
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.974
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1281
_refine_ls_number_reflns         18247
_refine_ls_number_restraints     114
_refine_ls_restrained_S_all      0.976
_refine_ls_R_factor_all          0.2448
_refine_ls_R_factor_gt           0.0823
_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^)+(0.0305P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1139
_refine_ls_wR_factor_ref         0.1584
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7239
_reflns_number_total             18247
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02024g2.cif
_cod_data_source_block           compound-3
_cod_depositor_comments
'Adding full bibliography for 7719627--7719631.cif.'
_cod_database_code               7719631
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.856
_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
2. Uiso/Uaniso restraints and constraints
Uanis(O17) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl9) \\sim Ueq, Uanis(Cl9A) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(Cl8)
\\sim Ueq, Uanis(Cl7A) \\sim Ueq, Uanis(Cl8A) \\sim Ueq, Uanis(Cl13) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C86) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C61) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(Cl12) \\sim Ueq, Uanis(Cl11) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(Cl10)
\\sim Ueq, Uanis(Cl7) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
3. Others
 Fixed Sof: Cl9A(0.5) Cl8(0.5) Cl7A(0.5) H87A(0.5) H87(0.5) Cl12(0.5) H88(0.5)
 H88A(0.5) Cl7(0.5) Cl8A(0.5) Cl9(0.5) Cl13(0.5)
4.a Ternary CH refined with riding coordinates:
 C87(H87A), C87(H87), C88(H88), C88(H88A)
4.b Aromatic/amide H refined with riding coordinates:
 C61(H61), C13(H13A), C53(H53), C9(H9), C73(H73), C18(H18), C26(H26), C32(H32),
  C42(H42), C45(H45), C64(H64), C47(H47), C54(H54), C70(H70), C34(H34),
 C51(H51), C49(H49), C75(H75), C4(H4), C2(H2), C37(H37), C7(H7A), C60(H60),
 C3(H3), C62(H62), C48(H48), C59(H59), C5(H5A), C10(H10), C28(H28), C68(H68),
 C56(H56), C11(H11), C40(H40), C72(H72), C23(H23), C30(H30), C35(H35), C55(H55),
  C74(H74), C36(H36), C21(H21), C41(H41), C43(H43), C24(H24), C15(H15A),
 C16(H16A), C66(H66), C67(H67), C29(H29), C17(H17), C22(H22)
4.c Idealised Me refined as rotating group:
 C94(H94A,H94B,H94C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C83(H83A,H83B,
 H83C), C77(H77A,H77B,H77C), C145(H14A,H14B,H14C), C79(H79A,H79B,H79C),
 C78(H78A,H78B,H78C), C80(H80A,H80B,H80C), C86(H86A,H86B,H86C)
4.d Idealised tetrahedral OH refined as rotating group:
 O8(H8), O7(H7), O14(H14), O5(H5), O13(H13), O15(H15), O16(H16), O6(H6),
 O85(H85), O17(H17A)
;
_shelx_res_checksum              88781
_shelx_hkl_checksum              29304
_olex2_submission_special_instructions 'No special instructions were received'