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_7061755
_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)'
_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   mixed
_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                77.0300(10)
_cell_angle_beta                 80.5910(10)
_cell_angle_gamma                72.9510(10)
_cell_formula_units_Z            2
_cell_length_a                   11.53950(10)
_cell_length_b                   15.21920(10)
_cell_length_c                   28.7586(2)
_cell_measurement_reflns_used    28674
_cell_measurement_temperature    373.0(3)
_cell_measurement_theta_max      71.6810
_cell_measurement_theta_min      3.0860
_cell_volume                     4679.56(7)
_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      373
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.980
_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    -70.00 -18.00   0.50    0.10    --    0.00 -64.00 -50.00  104
  2  \w    -12.00  73.00   0.50    0.78    --   55.56 -64.00 -50.00  170
  3  \w     30.00  91.00   0.50    0.78    --   55.56-125.00 -60.00  122
  4  \w     46.00 111.00   0.50    0.78    --   55.56-125.00-150.00  130
  5  \w     77.00 105.00   0.50    4.11    --  111.11-111.00 -60.00   56
  6  \w     82.00 108.00   0.50    4.11    --  111.11-111.00   0.00   52
  7  \w     72.00 107.00   0.50    4.11    --  111.11-111.00  90.00   70
  8  \w     73.00 105.00   0.50    4.11    --  111.11-111.00 120.00   64
  9  \w     43.00  71.00   0.50    4.11    --  111.11 -63.00  60.00   56
 10  \w     27.00  53.00   0.50    4.11    --  111.11 -50.00  90.00   52
 11  \w     30.00  74.00   0.50    4.11    --  111.11 -63.00  90.00   88
 12  \w     19.00  44.00   0.50    0.78    --   55.56 -37.00 150.00   50
 13  \w     22.00  65.00   0.50    4.11    --  111.11-111.00  90.00   86
 14  \w     27.00  98.00   0.50    4.11    --  111.11-111.00  60.00  142
 15  \w     29.00  54.00   0.50    4.11    --  111.11 -64.00 -50.00   50
 16  \w     38.00 105.00   0.50    4.11    --  111.11 -91.00 -30.00  134
 17  \w     67.00 108.00   0.50    4.11    --  111.11-111.00-120.00   82
 18  \w     61.00 108.00   0.50    4.11    --  111.11-111.00-180.00   94
 19  \w     47.00  88.00   0.50    4.11    --  111.11 -91.00-180.00   82
 20  \w     29.00  77.00   0.50    4.11    --  111.11 -63.00-180.00   96
 21  \w     30.00  76.00   0.50    4.11    --  111.11 -63.00-150.00   92
 22  \w     27.00  59.00   0.50    4.11    --  111.11 -50.00 -60.00   64
 23  \w     30.00  62.00   0.50    4.11    --  111.11 -63.00 -90.00   64
 24  \w     24.00  62.00   0.50    4.11    --  111.11-111.00-120.00   76
 25  \w     24.00  50.00   0.50    4.11    --  111.11-111.00 -60.00   52
 26  \w     23.00 100.00   0.50    4.11    --  111.11-111.00 -30.00  154
 27  \w     23.00  48.00   0.50    4.11    --  111.11-111.00-180.00   50
 28  \w    129.00 173.00   0.50    4.11    --  111.11  50.00   0.00   88
 29  \w    111.00 137.00   0.50    4.11    --  111.11 111.00 -60.00   52
 30  \w    113.00 138.00   0.50    0.78    --   55.56 125.00-150.00   50
 31  \w     92.00 134.00   0.50    4.11    --  111.11 178.00-120.00   84
 32  \w     79.00 133.00   0.50    0.78    --   55.56 125.00   0.00  108
 33  \w     94.00 168.00   0.50    4.11    --  111.11 111.00  30.00  148
 34  \w    111.00 146.00   0.50    4.11    --  111.11 178.00   0.00   70
 35  \w    100.00 126.00   0.50    4.11    --  111.11 111.00  90.00   52
 36  \w     72.00 167.00   0.50    4.11    --  111.11  64.00  86.00  190
 37  \w     72.00 163.00   0.50    4.11    --  111.11  63.00  30.00  182
 38  \w     76.00 119.00   0.50    4.11    --  111.11  50.00   0.00   86
 39  \w     27.00 125.00   0.50    0.78    --   55.56  64.00  86.00  196
 40  \w     61.00  86.00   0.50    4.11    --  111.11 178.00   0.00   50
 41  \w     50.00 142.00   0.50    4.11    --  111.11 178.00 -90.00  184
 42  \w     47.00  86.00   0.50    4.11    --  111.11 178.00-120.00   78
 43  \w    -39.00  62.00   0.50    0.10    --    0.00  64.00  86.00  202
 44  \w    -17.00   9.00   0.50    0.78    --  -55.56  64.00  86.00   52
 45  \w    -37.00  26.00   0.50    0.78    --  -55.56  37.00  60.00  126
 46  \w    -25.00  26.00   0.50    0.78    --  -55.56  19.00 -60.00  102
 47  \w    -14.00  11.00   0.50    0.78    --  -55.56  19.00 -90.00   50
 48  \w    -34.00   7.00   0.50    0.78    --  -55.56  37.00-150.00   82
 49  \w    -54.00 -19.00   0.50    4.11    -- -102.00  50.00-180.00   70
 50  \w   -111.00 -85.00   0.50    4.11    -- -102.00 -50.00 -90.00   52
 51  \w   -122.00 -18.00   0.50    0.78    --  -55.56 -64.00 -50.00  208
 52  \w    -64.00 -31.00   0.50    4.11    -- -102.00  64.00  86.00   66
 53  \w    -75.00 -47.00   0.50    4.11    -- -102.00 178.00 150.00   56
 54  \w   -119.00 -94.00   0.50    4.11    -- -102.00 178.00 150.00   50
 55  \w   -110.00 -40.00   0.50    4.11    -- -102.00 178.00 -90.00  140
 56  \w    -93.00 -68.00   0.50    0.10    --    0.00 178.00-180.00   50
 57  \w   -144.00-118.00   0.50    4.11    -- -102.00 178.00 -90.00   52
 58  \w    -31.00  12.00   0.50    0.78    --   55.56 -37.00 150.00   86
 59  \w   -129.00 -82.00   0.50    4.11    -- -102.00-111.00   0.00   94
 60  \w   -116.00 -89.00   0.50    4.11    -- -102.00-111.00  60.00   54
 61  \w   -149.00 -87.00   0.50    0.78    --  -55.56 -99.00  30.00  124
 62  \w   -164.00 -91.00   0.50    4.11    -- -102.00 -64.00 -50.00  146
 63  \w   -155.00-129.00   0.50    4.11    -- -102.00-111.00  60.00   52
 64  \w   -171.00-137.00   0.50    4.11    -- -102.00 -50.00 -90.00   68
;
_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  0.0306
_diffrn_reflns_av_unetI/netI     0.0333
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            54432
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.964
_diffrn_reflns_theta_min         3.092
_exptl_absorpt_coefficient_mu    4.794
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.43913
_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    1.438
_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         0.264
_refine_diff_density_min         -0.422
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1039
_refine_ls_number_reflns         18002
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0516
_refine_ls_R_factor_gt           0.0469
_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^)+(0.0979P)^2^+0.5127P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1438
_refine_ls_wR_factor_ref         0.1479
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15825
_reflns_number_total             18002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj03051a2.cif
_cod_data_source_block           co-373k_sq
_cod_depositor_comments
'Adding full bibliography for 7061754--7061757.cif.'
_cod_original_cell_volume        4679.57(7)
_cod_database_code               7061755
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.447
_shelx_estimated_absorpt_t_min   0.327
_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.a Riding coordinates:
 O8(H8A)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), 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)
2.c Idealised tetrahedral OH refined as rotating group:
 O2(H2A), O4(H4A), O6(H6)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 423 electrons were 
found in a volume of 1601\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 4[C4H9NO], [H2O] per Formula Unit 
which account for 424 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              25106
_shelx_fab_checksum              32947
_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
;