Observation of spin-crossover behaviour in Co(ii)-terpyridine complexes possessing π-conjugated substations
Soejima, Keita; Sekine, Yoshihiro; Miyake, Kanta; Kiba, Kota; Yamaguchi, Yuito; Zenno, Hikaru; Hayami, Shinya; RSC Advances 15 (2025) 35892–35898; doi:10.1039/D4RA08657K

data_7250915
_publ_section_title
;
 Observation of spin-crossover behaviour in Co(ii)-terpyridine complexes
 possessing \p-conjugated substations
;
_journal_issue                   43
_journal_name_full               'RSC Advances'
_journal_page_first              35892
_journal_page_last               35898
_journal_paper_doi               10.1039/D4RA08657K
_journal_volume                  15
_journal_year                    2025
_chemical_formula_moiety         'C66 H38 Co N6, 3(C H Cl3), 2(B F4)'
_chemical_formula_sum            'C69 H41 B2 Cl9 Co F8 N6'
_chemical_formula_weight         1505.68
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-04
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-12-05 deposited with the CCDC.	2025-09-15 downloaded from the CCDC.
;
_cell_angle_alpha                105.877(2)
_cell_angle_beta                 105.286(2)
_cell_angle_gamma                99.921(2)
_cell_formula_units_Z            2
_cell_length_a                   10.9464(2)
_cell_length_b                   17.5374(3)
_cell_length_c                   18.3393(3)
_cell_measurement_reflns_used    18018
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.3390
_cell_measurement_theta_min      2.0360
_cell_volume                     3151.14(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.15 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.15 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.15 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.991
_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    -11.00  34.50   0.50   44.72    --   20.00  54.00  75.99   91
  2  \w     44.00 109.00   0.50   44.72    --   20.00  54.00  75.99  130
  3  \w    -73.00  11.00   0.50   44.72    --   20.00  54.00 -30.00  168
  4  \w     16.00  42.00   0.50   44.72    --   20.00  54.00 -30.00   52
  5  \w     68.00 106.00   0.50   44.72    --   20.00  54.00 -30.00   76
  6  \w    -74.00 107.50   0.50   44.72    --   20.00  54.00-150.00  363
  7  \w    -74.00 -49.00   0.50   44.72    --   20.00  54.00 145.96   50
  8  \w    -71.00  57.00   0.50   44.72    --   20.00  54.00 -90.00  256
  9  \w    -70.00  11.00   0.50   44.72    --   20.00  54.00  30.00  162
 10  \w     81.00 106.00   0.50   44.72    --   20.00  54.00  30.00   50
 11  \w    -65.00   0.50   0.50   44.72    --   20.00  54.00   0.00  131
 12  \w    -73.00   0.00   0.50   44.72    --   20.00  54.00 120.00  146
 13  \w    -66.00  29.50   0.50   44.72    --   20.00  54.00-180.00  191
 14  \w    -68.00 -41.00   0.50   44.72    --   20.00  54.00-120.00   54
 15  \w     -7.00  18.00   0.50   44.72    --   20.00  54.00-120.00   50
 16  \w     79.00 105.00   0.50   44.72    --   20.00  54.00-120.00   52
 17  \w    -66.00  46.50   0.50   44.72    --   20.00  54.00 -60.00  225
 18  \w    -67.00 -41.00   0.50   44.72    --   20.00  54.00  75.99   52
;
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Rigaku Saturn724+ (2x2 bin mode)'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0405501000
_diffrn_orient_matrix_UB_12      -0.0405485000
_diffrn_orient_matrix_UB_13      -0.0212937000
_diffrn_orient_matrix_UB_21      0.0158889000
_diffrn_orient_matrix_UB_22      -0.0097137000
_diffrn_orient_matrix_UB_23      0.0358658000
_diffrn_orient_matrix_UB_31      -0.0543331000
_diffrn_orient_matrix_UB_32      0.0127056000
_diffrn_orient_matrix_UB_33      0.0084870000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0532
_diffrn_reflns_av_unetI/netI     0.0527
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            53048
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.999
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.728
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82913
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.15 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.587
_exptl_crystal_description       block
_exptl_crystal_F_000             1518
_refine_diff_density_max         1.058
_refine_diff_density_min         -0.981
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     856
_refine_ls_number_reflns         12781
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.0668
_refine_ls_R_factor_gt           0.0472
_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^)+(0.0331P)^2^+4.2957P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0976
_refine_ls_wR_factor_ref         0.1048
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10055
_reflns_number_total             12781
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra08657k2.cif
_cod_data_source_block           241024_co(pyrene-terpy)(bf4)
_cod_original_cell_volume        3151.13(10)
_cod_database_code               7250915
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C Co H B F N'
_chemical_oxdiff_usercomment     100K
_diffrn_oxdiff_ac4_digest_frames
;
017e7cfce4e94bec7b4ef9aa474d5928ed02299914e
;
_diffrn_oxdiff_ac4_digest_hkl
;
0139d5a9f99e9873ece776c034a1c51e8a9675
;
_reflns_odcompleteness_completeness 99.10
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C67(H67), C68(H68), C69(H69)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C12(H12), C7(H7), C19(H19), C20(H20), C45(H45), C47(H47), C14(H14),
 C32(H32), C1(H1), C46(H46), C4(H4), C2(H2), C3(H3), C15(H15), C22(H22),
 C58(H58), C13(H13), C23(H23), C48(H48), C65(H65), C35(H35), C27(H27), C59(H59),
  C42(H42), C34(H34), C33(H33), C25(H25), C55(H55), C26(H26), C40(H40),
 C37(H37), C56(H56), C66(H66), C60(H60), C36(H36), C52(H52), C53(H53)
;
_shelx_res_checksum              97267
_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 1.170
_oxdiff_exptl_absorpt_empirical_full_min 0.868