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_7250916
_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         'C54 H34 Co N6, 2(B F4), C2 H3 N'
_chemical_formula_sum            'C56 H37 B2 Co F8 N7'
_chemical_formula_weight         1040.47
_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     dual
_audit_creation_date             2024-11-22
_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                 104.323(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.6941(4)
_cell_length_b                   16.9594(4)
_cell_length_c                   19.7961(5)
_cell_measurement_reflns_used    19646
_cell_measurement_temperature    100
_cell_measurement_theta_max      30.9580
_cell_measurement_theta_min      2.1360
_cell_volume                     4779.9(2)
_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_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.806
_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  15.00   0.50    1.91    --    5.55 -62.00 -87.00   52
  2  \w      0.00  48.00   0.50    1.91    --    5.55  62.00  50.00   96
  3  \w     -6.00  71.00   0.50    1.91    --    5.55  57.00 -60.00  154
  4  \w    -18.00  36.00   0.50    1.91    --    5.55 -99.00 120.00  108
  5  \w    -18.00  29.00   0.50    1.91    --   -1.33 -99.00  90.00   94
  6  \w    -18.00  29.00   0.50    1.91    --   -1.33 -99.00 -90.00   94
;
_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      -0.0147683000
_diffrn_orient_matrix_UB_12      0.0288622000
_diffrn_orient_matrix_UB_13      0.0209633000
_diffrn_orient_matrix_UB_21      -0.0475596000
_diffrn_orient_matrix_UB_22      -0.0095260000
_diffrn_orient_matrix_UB_23      -0.0155680000
_diffrn_orient_matrix_UB_31      0.0008866000
_diffrn_orient_matrix_UB_32      -0.0287315000
_diffrn_orient_matrix_UB_33      0.0261849000
_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  0.0437
_diffrn_reflns_av_unetI/netI     0.0412
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.806
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            53980
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.806
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.374
_diffrn_reflns_theta_min         1.966
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.438
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57330
_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            'dull dark brown'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_description       block
_exptl_crystal_F_000             2124
_refine_diff_density_max         0.743
_refine_diff_density_min         -0.576
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     704
_refine_ls_number_reflns         12690
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0706
_refine_ls_R_factor_gt           0.0435
_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^)+(0.0468P)^2^+2.7599P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1023
_refine_ls_wR_factor_ref         0.1153
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9150
_reflns_number_total             12690
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra08657k2.cif
_cod_data_source_block           241121_co(2napht-ethynyl-try)(bf4)_100k_2
_cod_database_code               7250916
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Co  N  C H B F'
_chemical_oxdiff_usercomment     100K
_reflns_odcompleteness_completeness 99.94
_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. Others
 Fixed Sof: F8(0.5) F10(0.5) F12(0.5) F6(0.5) F9(0.5) F11(0.5) F7(0.5) F5(0.5)
3.a Aromatic/amide H refined with riding coordinates:
 C54(H54), C34(H34), C4(H4), C28(H28), C7(H7), C39(H39), C46(H46), C27(H27),
 C31(H31), C19(H19), C3(H3), C30(H30), C41(H41), C1(H1), C29(H29), C9(H9),
 C42(H42), C40(H40), C12(H12), C47(H47), C36(H36), C2(H2), C15(H15), C52(H52),
 C20(H20), C14(H14), C25(H25), C13(H13), C49(H49), C24(H24), C22(H22), C50(H50),
  C51(H51), C23(H23)
3.b Idealised Me refined as rotating group:
 C55(H55A,H55B,H55C)
;
_shelx_res_checksum              26169
_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 1.371
_oxdiff_exptl_absorpt_empirical_full_min 0.603