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_7250917
_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
'2(C62 H38 Co N6), 4(B F4), 6(C2 H3 N), C3 H3 N'
_chemical_formula_sum            'C139 H97 B4 Co2 F16 N19'
_chemical_formula_weight         2498.45
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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                90
_cell_angle_beta                 107.921(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   20.3553(6)
_cell_length_b                   14.0557(4)
_cell_length_c                   22.6261(6)
_cell_measurement_reflns_used    20781
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      29.8700
_cell_measurement_theta_min      2.1950
_cell_volume                     6159.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.786
_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     30.00  75.00   0.50   23.86    --    5.39  70.00  43.00   90
  2  \w    -12.00  14.00   0.50   23.86    --    5.39  70.00  43.00   52
  3  \w    -18.00  29.00   0.50   23.86    --   -1.48 -99.00-120.00   94
  4  \w     -2.00  34.00   0.50   23.86    --    5.39 -99.00 150.00   72
  5  \w     -3.00  23.00   0.50   23.86    --    5.39 -99.00 -60.00   52
  6  \w    -17.00  35.00   0.50   23.86    --    5.39 -99.00  60.00  104
  7  \w    -42.00  17.00   0.50   23.86    --    5.39 -70.00 -87.00  118
;
_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      -0.0103589000
_diffrn_orient_matrix_UB_12      0.0369524000
_diffrn_orient_matrix_UB_13      0.0166021000
_diffrn_orient_matrix_UB_21      -0.0348581000
_diffrn_orient_matrix_UB_22      -0.0149009000
_diffrn_orient_matrix_UB_23      -0.0123258000
_diffrn_orient_matrix_UB_31      0.0043804000
_diffrn_orient_matrix_UB_32      -0.0309927000
_diffrn_orient_matrix_UB_33      0.0256420000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.786
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            61255
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.786
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.303
_diffrn_reflns_theta_min         2.171
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.354
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27932
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
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    1.347
_exptl_crystal_description       plate
_exptl_crystal_F_000             2564
_refine_diff_density_max         1.357
_refine_diff_density_min         -0.761
_refine_diff_density_rms         0.106
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     820
_refine_ls_number_reflns         15849
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.1142
_refine_ls_R_factor_gt           0.0804
_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^)+(0.1598P)^2^+6.8351P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2330
_refine_ls_wR_factor_ref         0.2624
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10956
_reflns_number_total             15849
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra08657k2.cif
_cod_data_source_block           241128_co(anttpy)(bf4)_auto
_cod_database_code               7250917
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Co C H N F B'
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H63B-H16
 2 with sigma of 0.02
 H65C_$1-H18_$2
 2.2 with sigma of 0.02
 H63B_$3-H16_$3
 2.2 with sigma of 0.02
3. Rigid bond restraints
 C71
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C71: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 within
1.7A
Uanis(C71) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(N9) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. Rigid body (RIGU) restrains
 C71
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: F1(0.5) C72(0.5) H72A(0.5) H72B(0.5) H72C(0.5) F4(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C29(H29), C24(H24), C7(H7), C27(H27), C54(H54), C61(H61), C56(H56), C51(H51),
 C12(H12), C30(H30), C9(H9), C4(H4), C1(H1), C22(H22), C52(H52), C28(H28),
 C3(H3), C2(H2), C53(H53), C60(H60), C15(H15), C13(H13), C14(H14), C58(H58),
 C16(H16), C59(H59), C45(H45), C19(H19), C35(H35), C17(H17), C40(H40), C44(H44),
  C43(H43), C38(H38), C18(H18), C36(H36), C42(H42), C37(H37)
7.b Idealised Me refined as rotating group:
 C72(H72A,H72B,H72C), C65(H65A,H65B,H65C), C67(H67A,H67B,H67C), C63(H63A,H63B,
 H63C)
;
_shelx_res_checksum              19164
_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 1.780
_oxdiff_exptl_absorpt_empirical_full_min 0.448