Mixed-valence linear CoIII2Co<sup>II</sup> complexes with easy-axis magnetic anisotropy: Experimental and theoretical investigation.
Ahmed, Naushad; Kalita, Pankaj; Nabi, Rizwan; Guizouarn, Thierry; Pointillart, Fabrice; Zhang, Xiaoguang; Chandrasekhar, Vadapalli; Dalton transactions (Cambridge, England : 2003) 54 (2025) 12648–12657; doi:10.1039/d5dt01060h

data_7719364
_publ_section_title
;
 Mixed-valence linear CoIII2Co<sup>II</sup> complexes with easy-axis
 magnetic anisotropy: Experimental and theoretical investigation.
;
_journal_issue                   33
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              12648
_journal_page_last               12657
_journal_paper_doi               10.1039/d5dt01060h
_journal_volume                  54
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety
'C66 H84 Co3 N4 O10, 2(C H2 Cl2), C2 H6 O, 4(C H4 O)'
_chemical_formula_sum            'C74 H110 Cl4 Co3 N4 O15'
_chemical_formula_weight         1614.24
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-12
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-06-23 deposited with the CCDC.	2025-07-18 downloaded from the CCDC.
;
_cell_angle_alpha                64.280(4)
_cell_angle_beta                 64.970(5)
_cell_angle_gamma                72.665(5)
_cell_formula_units_Z            1
_cell_length_a                   13.099(2)
_cell_length_b                   13.535(2)
_cell_length_c                   13.677(2)
_cell_measurement_reflns_used    9959
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.43
_cell_measurement_theta_min      2.24
_cell_volume                     1959.9(5)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296(2)
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.983
_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  0.0517
_diffrn_reflns_av_unetI/netI     0.0655
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            59435
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.684
_diffrn_reflns_theta_min         1.687
_exptl_absorpt_coefficient_mu    0.828
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6377
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1153 before and 0.0702 after correction.
The Ratio of minimum to maximum transmission is 0.8552.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.368
_exptl_crystal_description       block
_exptl_crystal_F_000             851
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.494
_refine_diff_density_min         -0.720
_refine_diff_density_rms         0.135
_refine_ls_abs_structure_details
;
 Flack x determined using 6743 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.059(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     979
_refine_ls_number_reflns         19683
_refine_ls_number_restraints     138
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0861
_refine_ls_R_factor_gt           0.0671
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1329P)^2^+3.9039P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1995
_refine_ls_wR_factor_ref         0.2181
_reflns_Friedel_coverage         0.977
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.961
_reflns_number_gt                16059
_reflns_number_total             19683
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01060h2.cif
_cod_data_source_block           1-r
_cod_database_code               7719364
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9632(9)
 0.0368(9)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
3. Restrained distances
 O15-C1A
 1.42 with sigma of 0.02
 C1A-C1B
 1.51 with sigma of 0.02
 O15-C1B
 2.37 with sigma of 0.04
 C59-C64 \\sim C74-C75
 with sigma of 0.02
 C59-C60 \\sim C74-C71
 with sigma of 0.02
 C59-C21 \\sim C74-C21
 with sigma of 0.02
 C64-C63 \\sim C75-C76
 with sigma of 0.02
 C63-C62 \\sim C76-C69
 with sigma of 0.02
 C62-C61 \\sim C69-C70
 with sigma of 0.02
 C61-C60 \\sim C70-C71
 with sigma of 0.02
 C59-C63 \\sim C74-C76
 with sigma of 0.04
 C59-C61 \\sim C74-C70
 with sigma of 0.04
 C64-C62 \\sim C75-C69
 with sigma of 0.04
 C64-C60 \\sim C75-C71
 with sigma of 0.04
 C64-C21 \\sim C75-C21
 with sigma of 0.04
 C63-C61 \\sim C76-C70
 with sigma of 0.04
 C62-C60 \\sim C69-C71
 with sigma of 0.04
 C60-C21 \\sim C71-C21
 with sigma of 0.04
 O15-C1A \\sim O15A-C72
 with sigma of 0.02
 C1A-C1B \\sim C72-C1C
 with sigma of 0.02
 O15-C1B \\sim O15A-C1C
 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
O15 \\sim C1A \\sim C1B: within 1.7A with sigma of 0.002 and sigma for terminal
atoms of 0.004 within 1.7A
O15A \\sim C72 \\sim C1C: within 1.7A with sigma of 0.002 and sigma for
terminal atoms of 0.008 within 1.7A
Uanis(C60) = Uanis(C61) = Uanis(C62) = Uanis(C63) = Uanis(C64)
Uanis(C74) = Uanis(C59)
5. Rigid body (RIGU) restrains
 C59, C64, C63, C62, C61, C60
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C74, C75, C76, C69, C70, C71
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O15, C1A, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O15A, C72, C1C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H21a)=Sof(C74)=Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76)=Sof(C69)=Sof(H69)=
 Sof(C70)=Sof(H70)=Sof(C71)=Sof(H71)=1-FVAR(1)
 Sof(H21)=Sof(C59)=Sof(C64)=Sof(H64)=Sof(C63)=Sof(H63)=Sof(C62)=Sof(H62)=
 Sof(C61)=Sof(H61)=Sof(C60)=Sof(H60)=FVAR(1)
 Sof(O15A)=Sof(H15A)=Sof(C72)=Sof(H72a)=Sof(H72b)=Sof(C1C)=Sof(H1Ca)=Sof(H1Cb)=
 Sof(H1Cc)=1-FVAR(2)
 Sof(O15)=Sof(H15)=Sof(C1A)=Sof(H1Aa)=Sof(H1Ab)=Sof(C1B)=Sof(H1Ba)=Sof(H1Bb)=
 Sof(H1Bc)=FVAR(2)
7.a Riding coordinates:
 O14(H14a), C2S(H2Sa,H2Sb,H2Sc)
7.b Ternary CH refined with riding coordinates:
 C8(H8), C10(H10), C19(H19), C21(H21a), C21(H21)
7.c Secondary CH2 refined with riding coordinates:
 N2(H2a,H2b), N4(H4a,H4b), C9(H9a,H9b), C11(H11a,H11b), C20(H20a,H20b),
 C22(H22a,H22b), C4S(H4Sa,H4Sb), C5S(H5Sa,H5Sb), C1A(H1Aa,H1Ab), C72(H72a,H72b)
7.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C14(H14), C16(H16), C18(H18), C40(H40), C41(H41),
 C42(H42), C43(H43), C44(H44), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38),
  C58(H58), C57(H57), C56(H56), C55(H55), C54(H54), C75(H75), C76(H76),
 C69(H69), C70(H70), C71(H71), C64(H64), C63(H63), C62(H62), C61(H61), C60(H60)
7.e Idealised Me refined as rotating group:
 C30(H30a,H30b,H30c), C31(H31a,H31b,H31c), C32(H32a,H32b,H32c), C26(H26a,H26b,
 H26c), C27(H27a,H27b,H27c), C28(H28a,H28b,H28c), C51(H51a,H51b,H51c), C50(H50a,
 H50b,H50c), C52(H52a,H52b,H52c), C48(H48a,H48b,H48c), C47(H47a,H47b,H47c),
 C46(H46a,H46b,H46c), C66(H66a,H66b,H66c), C65(H65a,H65b,H65c), C1S(H1Sa,H1Sb,
 H1Sc), C67(H67a,H67b,H67c), C68(H68a,H68b,H68c), C1B(H1Ba,H1Bb,H1Bc), C1C(H1Ca,
 H1Cb,H1Cc)
7.f Idealised tetrahedral OH refined as rotating group:
 O13(H13), O11(H11), O12(H12), O15(H15), O15A(H15A)
;
_shelx_res_checksum              46280
_shelx_hkl_checksum              91538
_olex2_submission_special_instructions 'No special instructions were received'