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_7061754
_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
'4(C22 H12 Co N12 O4), 2(C36 H24 Co N6), 6(C4 H9 N O), 7(H2 O)'
_chemical_formula_sum            'C184 H164 Co6 N66 O29'
_chemical_formula_weight         4117.38
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-05-24 deposited with the CCDC.	2022-08-22 downloaded from the CCDC.
;
_cell_angle_alpha                82.777(2)
_cell_angle_beta                 75.137(2)
_cell_angle_gamma                83.919(2)
_cell_formula_units_Z            1
_cell_length_a                   16.2176(4)
_cell_length_b                   17.0260(3)
_cell_length_c                   17.2151(3)
_cell_measurement_reflns_used    16619
_cell_measurement_temperature    213.99(11)
_cell_measurement_theta_max      76.0690
_cell_measurement_theta_min      2.5950
_cell_volume                     4544.47(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      213.99(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.958
_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    -22.00  14.00   0.50    0.10    --  -46.62  19.00  30.00   72
  2  \w    -56.00  17.00   0.50    0.10    --  -46.62  87.00 105.00  146
  3  \w     -1.00  29.00   0.50    0.10    --  -46.62  19.00 -90.00   60
  4  \w    -39.00  22.00   0.50    0.10    --  -46.62  37.00-120.00  122
  5  \w    -55.00 -29.00   0.50    2.50    -- -102.00 125.00-120.00   52
  6  \w    -54.00 -29.00   0.50    2.50    -- -102.00  77.00-180.00   50
  7  \w    -63.00 -29.00   0.50    2.50    -- -102.00 125.00-180.00   68
  8  \w   -104.00 -74.00   0.50    2.50    -- -102.00  77.00-180.00   60
  9  \w   -117.00 -81.00   0.50    2.50    -- -102.00 125.00-120.00   72
 10  \w   -115.00 -85.00   0.50    2.50    -- -102.00 125.00-180.00   60
 11  \w   -152.00-108.00   0.50    2.50    -- -102.00 -15.00-150.00   88
 12  \w   -171.00-102.00   0.50    2.50    -- -102.00 -87.00 -11.00  138
 13  \w   -119.00 -76.00   0.50    0.10    --  -46.62-125.00  30.00   86
 14  \w   -106.00 -71.00   0.50    0.10    --  -46.62-125.00 120.00   70
 15  \w    -17.00  74.00   0.50    0.10    --   46.62 -87.00 -11.00  182
 16  \w     22.00  68.00   0.50    0.10    --   46.62 -99.00  90.00   92
 17  \w     36.00  72.00   0.50    2.50    --  106.69 -61.00   0.00   72
 18  \w     75.00 127.00   0.50    2.50    --  106.69 -87.00 -11.00  104
 19  \w     71.00 114.00   0.50    2.50    --  106.69-125.00-150.00   86
 20  \w     35.00  74.00   0.50    2.50    --  106.69 -94.00 -60.00   78
 21  \w     50.00 113.00   0.50    2.50    --  106.69-125.00   0.00  126
 22  \w     36.00  93.00   0.50    2.50    --  106.69 -94.00-150.00  114
 23  \w     39.00  71.00   0.50    2.50    --  106.69 -61.00-120.00   64
 24  \w     41.00  98.00   0.50    2.50    --  106.69 -94.00 -90.00  114
 25  \w     38.00 114.00   0.50    2.50    --  106.69-125.00  30.00  152
 26  \w     36.00  72.00   0.50    2.50    --  106.69 -61.00  60.00   72
 27  \w     89.00 146.00   0.50    2.50    --  106.69  15.00  30.00  114
 28  \w    153.00 178.00   0.50    2.50    --  106.69  15.00  30.00   50
 29  \w    139.00 165.00   0.50    2.50    --  106.69  87.00 105.00   52
 30  \w    127.00 152.00   0.50    2.50    --  106.69 125.00 120.00   50
 31  \w     96.00 122.00   0.50    2.50    --  106.69 125.00 120.00   52
 32  \w     81.00 138.00   0.50    2.50    --  106.69  87.00 105.00  114
 33  \w     94.00 177.00   0.50    2.50    --  106.69  45.00  60.00  166
 34  \w     96.00 166.00   0.50    2.50    --  106.69  30.00 -30.00  140
 35  \w     90.00 131.00   0.50    2.50    --  106.69  61.00-120.00   82
 36  \w    -20.00  44.00   0.50    0.10    --   46.62 -37.00  30.00  128
 37  \w    -29.00   5.00   0.50    0.10    --   46.62 -19.00  90.00   68
 38  \w   -104.00 -79.00   0.50    2.50    -- -102.00  87.00 105.00   50
 39  \w    -65.00 -33.00   0.50    2.50    -- -102.00  61.00  90.00   64
 40  \w    -60.00 -35.00   0.50    2.50    -- -102.00 125.00  60.00   50
 41  \w   -117.00 -68.00   0.50    2.50    -- -102.00 125.00  60.00   98
 42  \w   -117.00 -30.00   0.50    2.50    -- -102.00 125.00 120.00  174
 43  \w   -174.00-124.00   0.50    2.50    -- -102.00 -61.00 -60.00  100
 44  \w   -174.00 -86.00   0.50    2.50    -- -102.00 -94.00  60.00  176
 45  \w   -163.00-137.00   0.50    2.50    -- -102.00 -94.00  90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0816315000
_diffrn_orient_matrix_UB_12      0.0568691000
_diffrn_orient_matrix_UB_13      0.0099075000
_diffrn_orient_matrix_UB_21      0.0478970000
_diffrn_orient_matrix_UB_22      0.0594724000
_diffrn_orient_matrix_UB_23      -0.0670325000
_diffrn_orient_matrix_UB_31      -0.0275451000
_diffrn_orient_matrix_UB_32      -0.0399625000
_diffrn_orient_matrix_UB_33      -0.0638113000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0945
_diffrn_reflns_av_unetI/netI     0.0905
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            62426
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.978
_diffrn_reflns_theta_min         2.624
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.957
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39065
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.25a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.504
_exptl_crystal_description       block
_exptl_crystal_F_000             2124
_exptl_crystal_size_max          0.086
_exptl_crystal_size_mid          0.023
_exptl_crystal_size_min          0.016
_refine_diff_density_max         1.260
_refine_diff_density_min         -0.509
_refine_diff_density_rms         0.093
_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     1340
_refine_ls_number_reflns         18417
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0973
_refine_ls_R_factor_gt           0.0759
_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^)+(0.1414P)^2^+0.3008P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2015
_refine_ls_wR_factor_ref         0.2247
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13431
_reflns_number_total             18417
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj03051a2.cif
_cod_data_source_block           dj-15-2-20190304
_cod_depositor_comments
'Adding full bibliography for 7061754--7061757.cif.'
_cod_database_code               7061754
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.675
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H15A,H15B} of O15, {H12A,H12B} of O12
 At 1.5 times of:
  All C(H,H,H) groups, {H16A,H16B} of O16, {H13A,H13B} of O13, {H14A,H14B} of
  O14, All C(H,H,H,H,H,H) groups, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O13) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: O15(0.5) H15A(0.5) H15B(0.5) H96A(0.5) H96B(0.5) H96C(0.5)
 H96D(0.5) H96E(0.5) H96F(0.5) H97A(0.5) H97B(0.5) H97C(0.5) H97D(0.5)
 H97E(0.5) H97F(0.5) H99A(0.5) H99B(0.5) H99C(0.5) H99D(0.5) H99E(0.5)
 H99F(0.5) O18(0.5) N34(0.5) C95(0.5) O17(0.5) N33(0.5) C98(0.5) O13(0.4)
 H13A(0.4) H13B(0.4) O14(0.6) H14A(0.6) H14B(0.6)
4.a Riding coordinates:
 O12(H12A,H12B), O15(H15A,H15B), O13(H13A,H13B), O14(H14A,H14B)
4.b Free rotating group:
 O16(H16A,H16B)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4A), C5(H5), C6(H6), C8(H8), C14(H14), C15(H15), C16(H16),
 C17(H17), C19(H19), C25(H25), C26(H26), C27(H27), C28(H28), C30(H30), C36(H36),
  C37(H37), C38(H38), C39(H39), C41(H41), C45(H45), C46(H46), C47(H47),
 C49(H49), C50(H50), C52(H52), C53(H53), C54(H54), C57(H57), C58(H58), C59(H59),
  C61(H61), C62(H62), C64(H64), C65(H65), C66(H66), C69(H69), C70(H70),
 C71(H71), C73(H73), C74(H74), C76(H76), C77(H77), C78(H78)
4.d Idealised Me refined as rotating group:
 C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C84(H84A,H84B,H84C), C90(H90A,H90B,
 H90C), C91(H91A,H91B,H91C), C94(H94A,H94B,H94C), C96(H96A,H96B,H96C), C96(H96D,
 H96E,H96F), C97(H97A,H97B,H97C), C97(H97D,H97E,H97F), C99(H99A,H99B,H99C),
 C99(H99D,H99E,H99F)
4.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O4(H4), O6(H6A), O8(H8A)
;
_shelx_res_checksum              22091
_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 2.817
_oxdiff_exptl_absorpt_empirical_full_min 0.395