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_7719365
_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 H4 O), 2(C H2 Cl2), (C2 H6 O), (C H4 O)'
_chemical_formula_sum            'C73 H106 Cl4 Co3 N4 O14'
_chemical_formula_weight         1582.20
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-11
_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                64.187(2)
_cell_angle_beta                 65.083(2)
_cell_angle_gamma                72.5950(10)
_cell_formula_units_Z            1
_cell_length_a                   13.0935(2)
_cell_length_b                   13.6028(2)
_cell_length_c                   13.6458(2)
_cell_measurement_reflns_used    27277
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      28.9930
_cell_measurement_theta_min      3.0070
_cell_volume                     1964.25(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.29d (Rigaku OD, 2017)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(10)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.907
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -61.00  50.00   0.50    7.13    --    7.10 -82.00 120.00  222
  2  \w    -60.00  50.00   0.50    7.13    --    7.10 -82.00-150.00  220
  3  \w    -53.00  50.00   0.50    7.13    --    7.10 -82.00-120.00  206
  4  \w    -63.00  49.00   0.50    7.13    --    7.10 -82.00  90.00  224
  5  \w    -62.00  49.00   0.50    7.13    --    7.10 -82.00   0.00  222
  6  \w    -59.00  50.00   0.50    7.13    --    7.10 -82.00 -30.00  218
  7  \w    -63.00  35.00   0.50    7.13    --   -7.50 -82.00 150.00  196
  8  \w     10.00  35.00   0.50    7.13    --   -7.50 -82.00  60.00   50
  9  \w     10.00  35.00   0.50    7.13    --   -7.50 -82.00 -30.00   50
 10  \w    -53.00 -13.00   0.50    7.13    --   -7.50 -82.00 -30.00   80
 11  \w    -62.00   1.00   0.50    7.13    --   -7.50 -82.00 -60.00  126
 12  \w    -58.00  -6.00   0.50    7.13    --   -7.50 -82.00  60.00  104
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0378
_diffrn_reflns_av_unetI/netI     0.0446
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.907
_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       -17
_diffrn_reflns_number            54187
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.859
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.959
_diffrn_reflns_theta_min         2.837
_exptl_absorpt_coefficient_mu    0.824
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92935
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.29d (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.338
_exptl_crystal_description       block
_exptl_crystal_F_000             833
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.390
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 6840 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.039(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     845
_refine_ls_number_reflns         17917
_refine_ls_number_restraints     296
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0403
_refine_ls_R_factor_gt           0.0345
_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^)+(0.0394P)^2^+0.1545P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0792
_refine_ls_wR_factor_ref         0.0816
_reflns_Friedel_coverage         0.894
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.811
_reflns_number_gt                15913
_reflns_number_total             17917
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01060h2.cif
_cod_data_source_block           1-s
_cod_original_cell_volume        1964.25(7)
_cod_database_code               7719365
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNOCo
_shelx_estimated_absorpt_t_max   0.908
_shelx_estimated_absorpt_t_min   0.761
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C62-C61 = C65-C64 = C64-C63
 1.37 with sigma of 0.02
 C62-C63
 1.38 with sigma of 0.02
 C61-C60 = C60-C65
 1.36 with sigma of 0.02
 C62-C64
 2.38 with sigma of 0.04
 C61-C65
 2.36 with sigma of 0.04
 C62-C60 = C60-C64 = C65-C63
 2.37 with sigma of 0.04
 C62-C61 \\sim C61-C60 \\sim C60-C65 \\sim C65-C64 \\sim C64-C63 \\sim C63-C62
 with sigma of 0.02
 C62-C64 \\sim C62-C60 \\sim C64-C60 \\sim C65-C61 \\sim C65-C63 \\sim C63-C61
 with sigma of 0.04
 C21-C60 \\sim C21-C60A
 with sigma of 0.02
 C60-C61 \\sim C60A-C61A
 with sigma of 0.02
 C60-C65 \\sim C60A-C65A
 with sigma of 0.02
 C61-C62 \\sim C61A-C62A
 with sigma of 0.02
 C62-C63 \\sim C62A-C63A
 with sigma of 0.02
 C63-C64 \\sim C63A-C64A
 with sigma of 0.02
 C64-C65 \\sim C64A-C65A
 with sigma of 0.02
 C21-C61 \\sim C21-C61A
 with sigma of 0.04
 C21-C65 \\sim C21-C65A
 with sigma of 0.04
 C60-C62 \\sim C60A-C62A
 with sigma of 0.04
 C60-C64 \\sim C60A-C64A
 with sigma of 0.04
 C61-C63 \\sim C61A-C63A
 with sigma of 0.04
 C61-C65 \\sim C61A-C65A
 with sigma of 0.04
 C62-C64 \\sim C62A-C64A
 with sigma of 0.04
 C63-C65 \\sim C63A-C65A
 with sigma of 0.04
3. Restrained planarity
 C60, C61, C62, C63, C64, C65
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
C60 \\sim C65 \\sim C64 \\sim C63 \\sim C62 \\sim C61: within 1.7A with sigma
of 0.01 and sigma for terminal atoms of 0.002 within 1.7A
C62A \\sim C63A \\sim C61A \\sim C64A \\sim C65A \\sim C60A: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.002 within 1.7A
Uanis(C60A) = Uanis(C60)
Uanis(C63A) = Uanis(C63)
5. Rigid body (RIGU) restrains
 C60, C61, C62, C63, C64, C65
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C60, C65, C64, C63, C62, C61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C60A, C65A, C63A, C64A, C62A, C61A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H21A)=Sof(C62A)=Sof(H62A)=Sof(C61A)=Sof(H61A)=Sof(C60A)=Sof(C65A)=
 Sof(H65A)=Sof(C64A)=Sof(H64A)=Sof(C63A)=Sof(H63A)=1-FVAR(1)
 Sof(H21)=Sof(C60)=Sof(C61)=Sof(H61)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=
 Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C8(H8), C10(H10), C19(H19), C21(H21), C21(H21A)
7.b Secondary CH2 refined with riding coordinates:
 N2(H2A,H2B), N4(H4A,H4B), C9(H9A,H9B), C11(H11A,H11B), C20(H20A,H20B),
 C22(H22A,H22B)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C14(H14), C16(H16), C18(H18), C34(H34), C35(H35),
 C36(H36), C37(H37), C38(H38), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44),
  C55(H55), C56(H56), C57(H57), C58(H58), C59(H59), C61(H61), C62(H62),
 C63(H63), C64(H64), C65(H65), C62A(H62A), C61A(H61A), C65A(H65A), C64A(H64A),
 C63A(H63A)
7.d Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C45(H45A,H45B,H45C), C47(H47A,
 H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C66(H66A,H66B,H66C), C68(H68A,H68B,
 H68C), C67(H67A,H67B,H67C)
7.e Idealised tetrahedral OH refined as rotating group:
 O12(H12), O11(H11)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 133 electrons were 
found in a volume of 475\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2(CH2Cl2), 1(CH4O), 1(C2H6O) per Formula Unit 
which account for 128 electrons 
per unit cell.
;
_shelx_res_checksum              71173
_shelx_hkl_checksum              51331
_shelx_fab_checksum              66457
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.174
_oxdiff_exptl_absorpt_empirical_full_min 0.818