Slow magnetic relaxation and spin crossover behavior in two mixed-valence Co(ii)/Co(iii) complexes
Huang, You-Lin; Zhong, Yun-Jing; Ye, Hua-Jian; Li, You-Hong; Kuang, Xiao-Man; Ouyang, Zhi-Jian; Chen, Wen-Bin; Yang, Meng; Dong, Wen; New Journal of Chemistry 46 (2022) 17720–17725; doi:10.1039/D2NJ03051A

data_7061757
_publ_section_title
;
 Slow magnetic relaxation and spin crossover behavior in two mixed-valence
 Co(ii)/Co(iii) complexes
;
_journal_issue                   37
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              17720
_journal_page_last               17725
_journal_paper_doi               10.1039/D2NJ03051A
_journal_volume                  46
_journal_year                    2022
_chemical_formula_moiety
'C30 H22 Co N6, 2(C22 H12 Co N12 O4), 4[C4H9NO], 1[2H2O]'
_chemical_formula_sum            'C90 H84 Co3 N34 O13'
_chemical_formula_weight         2026.70
_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             2022-08-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-08-19 deposited with the CCDC.	2022-08-22 downloaded from the CCDC.
;
_cell_angle_alpha                77.2450(5)
_cell_angle_beta                 80.0214(6)
_cell_angle_gamma                73.2019(7)
_cell_formula_units_Z            2
_cell_length_a                   11.42884(11)
_cell_length_b                   15.20373(10)
_cell_length_c                   28.11736(15)
_cell_measurement_reflns_used    38466
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.6220
_cell_measurement_theta_min      3.0930
_cell_volume                     4530.34(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.969
_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    107.00 147.00   0.50    0.64    --  106.06  45.00  30.00   80
  2  \w     98.00 178.00   0.50    0.64    --  106.06  18.00  71.00  160
  3  \w     98.00 135.00   0.50    0.64    --  106.06  30.00 150.00   74
  4  \w     39.00 121.00   0.50    0.16    --   45.87  18.00  71.00  164
  5  \w     91.00 178.00   0.50    0.64    --  106.06  15.00   0.00  174
  6  \w     90.00 162.00   0.50    0.64    --  106.06  61.00 -90.00  144
  7  \w     65.00  91.00   0.50    0.64    --  106.06 -77.00 -60.00   52
  8  \w     34.00  73.00   0.50    0.64    --  106.06 -61.00-180.00   78
  9  \w     33.00  58.00   0.50    0.64    --  106.06 -77.00 -60.00   50
 10  \w     34.00  73.00   0.50    0.64    --  106.06 -61.00-150.00   78
 11  \w     37.00  71.00   0.50    0.64    --  106.06 -77.00   0.00   68
 12  \w     41.00  71.00   0.50    0.64    --  106.06 -61.00  60.00   60
 13  \w     33.00  63.00   0.50    0.64    --  106.06 -61.00  90.00   60
 14  \w     33.00  65.00   0.50    0.64    --  106.06 -61.00 150.00   64
 15  \w     34.00 107.00   0.50    0.64    --  106.06 -77.00  60.00  146
 16  \w    -25.00   0.00   0.50    0.16    --   45.87 -18.00 -96.00   50
 17  \w     36.00  99.00   0.50    0.64    --  106.06 -94.00   0.00  126
 18  \w     59.00 117.00   0.50    0.64    --  106.06-133.00   3.36  116
 19  \w     49.00 112.00   0.50    0.64    --  106.06-125.00 -60.00  126
 20  \w     67.00 111.00   0.50    0.64    --  106.06-125.00 -90.00   88
 21  \w     39.00 103.00   0.50    0.64    --  106.06-125.00-120.00  128
 22  \w     34.00  99.00   0.50    0.64    --  106.06-125.00-180.00  130
 23  \w    103.00 147.00   0.50    0.64    --  106.06-173.00 -97.03   88
 24  \w     72.00  97.00   0.50    0.64    --  106.06 -94.00 -90.00   50
 25  \w     36.00 106.00   0.50    0.64    --  106.06 -94.00  60.00  140
 26  \w     28.00  86.00   0.50    0.16    --   45.87-125.00 -30.00  116
 27  \w     63.00  88.00   0.50    0.16    --   45.87-125.00-180.00   50
 28  \w     36.00  71.00   0.50    0.16    --   45.87-125.00 120.00   70
 29  \w    -61.00 -14.00   0.50    0.16    --  -45.87  57.00-180.00   94
 30  \w     -2.00  24.00   0.50    0.16    --  -45.87  57.00-180.00   52
 31  \w    -20.00  29.00   0.50    0.16    --  -45.87  19.00-150.00   98
 32  \w    -40.00  28.00   0.50    0.16    --  -45.87  37.00 -60.00  136
 33  \w    -19.00  25.00   0.50    0.16    --  -45.87  18.00  71.00   88
 34  \w   -107.00 -80.00   0.50    0.64    -- -102.00 108.00  53.22   54
 35  \w   -108.00 -83.00   0.50    0.64    -- -102.00 109.00  77.69   50
 36  \w    -65.00 -34.00   0.50    0.64    -- -102.00 125.00 120.00   62
 37  \w    -54.00 -29.00   0.50    0.64    -- -102.00 108.00  53.22   50
 38  \w    -75.00 -35.00   0.50    0.64    -- -102.00 125.00   0.00   80
 39  \w   -111.00 -85.00   0.50    0.64    -- -102.00 125.00   0.00   52
 40  \w   -122.00 -31.00   0.50    0.64    -- -102.00 139.00 -97.03  182
 41  \w   -118.00 -43.00   0.50    0.16    --  -45.87 -18.00 -96.00  150
 42  \w   -168.00 -96.00   0.50    0.64    -- -102.00 -18.00 -96.00  144
 43  \w   -165.00 -86.00   0.50    0.64    -- -102.00 -15.00-180.00  158
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0381
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            63932
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.853
_diffrn_reflns_theta_min         3.087
_exptl_absorpt_coefficient_mu    4.952
_exptl_absorpt_correction_T_max  0.372
_exptl_absorpt_correction_T_min  0.277
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.486
_exptl_crystal_description       block
_exptl_crystal_F_000             2094
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.542
_refine_diff_density_min         -0.434
_refine_diff_density_rms         0.070
_refine_ls_extinction_coef       0.00033(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1259
_refine_ls_number_reflns         18529
_refine_ls_number_restraints     452
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0504
_refine_ls_R_factor_gt           0.0466
_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^)+(0.0721P)^2^+4.2986P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1293
_refine_ls_wR_factor_ref         0.1320
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16900
_reflns_number_total             18529
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj03051a2.cif
_cod_data_source_block           co2-100k
_cod_depositor_comments
'Adding full bibliography for 7061754--7061757.cif.'
_cod_database_code               7061757
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.437
_shelx_estimated_absorpt_t_min   0.318
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 Co3-O7 \\sim Co3-O7A
 with sigma of 0.02
 O7-C66 \\sim O7A-C66A
 with sigma of 0.02
 O8-C72 \\sim O8A-C72A
 with sigma of 0.02
 C1X-C65 \\sim C1Y-C65A
 with sigma of 0.02
 C1X-C69 \\sim C1Y-C69A
 with sigma of 0.02
 C1X-C73 \\sim C1Y-C73A
 with sigma of 0.02
 C65-C66 \\sim C65A-C66A
 with sigma of 0.02
 C66-C67 \\sim C66A-C67A
 with sigma of 0.02
 C67-C68 \\sim C67A-C68A
 with sigma of 0.02
 C68-C69 \\sim C68A-C69A
 with sigma of 0.02
 C69-C70 \\sim C69A-C70A
 with sigma of 0.02
 C70-C71 \\sim C70A-C71A
 with sigma of 0.02
 C71-C72 \\sim C71A-C72A
 with sigma of 0.02
 C72-C73 \\sim C72A-C73A
 with sigma of 0.02
 Co3-C65 \\sim Co3-C65A
 with sigma of 0.04
 Co3-C66 \\sim Co3-C66A
 with sigma of 0.04
 O7-C65 \\sim O7A-C65A
 with sigma of 0.04
 O7-C67 \\sim O7A-C67A
 with sigma of 0.04
 O8-C71 \\sim O8A-C71A
 with sigma of 0.04
 O8-C73 \\sim O8A-C73A
 with sigma of 0.04
 N29-C65 \\sim N29-C65A
 with sigma of 0.04
 C1X-C66 \\sim C1Y-C66A
 with sigma of 0.04
 C1X-C68 \\sim C1Y-C68A
 with sigma of 0.04
 C1X-C70 \\sim C1Y-C70A
 with sigma of 0.04
 C1X-C72 \\sim C1Y-C72A
 with sigma of 0.04
 C65-C67 \\sim C65A-C67A
 with sigma of 0.04
 C65-C69 \\sim C65A-C69A
 with sigma of 0.04
 C65-C73 \\sim C65A-C73A
 with sigma of 0.04
 C66-C68 \\sim C66A-C68A
 with sigma of 0.04
 C67-C69 \\sim C67A-C69A
 with sigma of 0.04
 C68-C70 \\sim C68A-C70A
 with sigma of 0.04
 C69-C71 \\sim C69A-C71A
 with sigma of 0.04
 C69-C73 \\sim C69A-C73A
 with sigma of 0.04
 C70-C72 \\sim C70A-C72A
 with sigma of 0.04
 C71-C73 \\sim C71A-C73A
 with sigma of 0.04
 Co3-O5 \\sim Co3-O5A
 with sigma of 0.02
 O5-C55 \\sim O5A-C55A
 with sigma of 0.02
 O6-C61 \\sim O6A-C61A
 with sigma of 0.02
 N24-C54 \\sim N24-C54A
 with sigma of 0.02
 C54-C55 \\sim C54A-C55A
 with sigma of 0.02
 C54-C63 \\sim C54A-C63A
 with sigma of 0.02
 C55-C56 \\sim C55A-C56A
 with sigma of 0.02
 C56-C57 \\sim C56A-C57A
 with sigma of 0.02
 C57-C58 \\sim C57A-C58A
 with sigma of 0.02
 C58-C59 \\sim C58A-C59A
 with sigma of 0.02
 C58-C63 \\sim C58A-C63A
 with sigma of 0.02
 C59-C60 \\sim C59A-C60A
 with sigma of 0.02
 C60-C61 \\sim C60A-C61A
 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
 Co3-C55 \\sim Co3-C55A
 with sigma of 0.04
 O5-C54 \\sim O5A-C54A
 with sigma of 0.04
 O5-C56 \\sim O5A-C56A
 with sigma of 0.04
 O6-C60 \\sim O6A-C60A
 with sigma of 0.04
 O6-C62 \\sim O6A-C62A
 with sigma of 0.04
 N24-C55 \\sim N24-C55A
 with sigma of 0.04
 N24-C63 \\sim N24-C63A
 with sigma of 0.04
 C54-C56 \\sim C54A-C56A
 with sigma of 0.04
 C54-C58 \\sim C54A-C58A
 with sigma of 0.04
 C54-C62 \\sim C54A-C62A
 with sigma of 0.04
 C55-C57 \\sim C55A-C57A
 with sigma of 0.04
 C55-C63 \\sim C55A-C63A
 with sigma of 0.04
 C56-C58 \\sim C56A-C58A
 with sigma of 0.04
 C57-C59 \\sim C57A-C59A
 with sigma of 0.04
 C57-C63 \\sim C57A-C63A
 with sigma of 0.04
 C58-C60 \\sim C58A-C60A
 with sigma of 0.04
 C58-C62 \\sim C58A-C62A
 with sigma of 0.04
 C59-C61 \\sim C59A-C61A
 with sigma of 0.04
 C59-C63 \\sim C59A-C63A
 with sigma of 0.04
 C60-C62 \\sim C60A-C62A
 with sigma of 0.04
 C61-C63 \\sim C61A-C63A
 with sigma of 0.04
3. Rigid body (RIGU) restrains
 O7, C69, C73, O8, C71, C68, C1X, C70, C65, C72, C66, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N30A, C70A, C66A, O7A, C72A, O8A, C69A, C1Y, C71A, C65A, C73A, C67A, C68A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O6A, C55A, O5A, C56A, C57A, C63A, C58A, C54A, C59A, C60A, C61A, C62A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O5, C60, C58, O6, C62, C54, C59, C55, C61, C56, C57, C63
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: O5(0.5) O6(0.5) H6(0.5) O7(0.5) O8(0.5) H8(0.5) C1X(0.5) C54(0.5)
 C55(0.5) C56(0.5) H56(0.5) C57(0.5) H57(0.5) C58(0.5) C59(0.5) H59(0.5)
 C60(0.5) H60(0.5) C61(0.5) C62(0.5) H62(0.5) C63(0.5) C65(0.5) C66(0.5)
 C67(0.5) H67(0.5) C68(0.5) H68(0.5) C69(0.5) C70(0.5) H70(0.5) C71(0.5)
 H71(0.5) C72(0.5) C73(0.5) H73(0.5) O7A(0.5) O8A(0.5) H8A(0.5) C1Y(0.5)
 C65A(0.5) C67A(0.5) H67A(0.5) C68A(0.5) H68A(0.5) C69A(0.5) C70A(0.5)
 H70A(0.5) C71A(0.5) H71A(0.5) C72A(0.5) C73A(0.5) H73A(0.5) C66A(0.5) O6A(0.5)
 H6A(0.5) C55A(0.5) C56A(0.5) H56A(0.5) C57A(0.5) H57A(0.5) C58A(0.5) C59A(0.5)
 H59A(0.5) C60A(0.5) H60A(0.5) C61A(0.5) C62A(0.5) H62A(0.5) C63A(0.5) O5A(0.5)
 C54A(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8B), C9(H9), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C23(H23),
  C24(H24), C27(H27), C28(H28), C29(H29), C30(H30), C34(H34), C35(H35),
 C37(H37), C38(H38), C40(H40), C45(H45), C46(H46), C48(H48), C49(H49), C51(H51),
  C56(H56), C57(H57), C59(H59), C60(H60), C62(H62), C67(H67), C68(H68),
 C70(H70), C71(H71), C73(H73), C67A(H67A), C68A(H68A), C70A(H70A), C71A(H71A),
 C73A(H73A), C56A(H56A), C57A(H57A), C59A(H59A), C60A(H60A), C62A(H62A)
5.b Idealised tetrahedral OH refined as rotating group:
 O2(H2A), O4(H4A), O6(H6), O8(H8), O8A(H8A), O6A(H6A)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 438 electrons were 
found in a volume of 1480\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 4[C4H9NO], 1[H2O] per Formula Unit 
which account for 418 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              71955
_shelx_fab_checksum              52698
_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
;