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_7250914
_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(C46 H30 Co N6), 4(B F4), H2 O, C H4 O, O'
_chemical_formula_sum            'C93 H66 B4 Co2 F16 N12 O3'
_chemical_formula_weight         1864.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   mixed
_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                 98.318(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.8745(15)
_cell_length_b                   41.277(7)
_cell_length_c                   23.237(4)
_cell_measurement_reflns_used    6030
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.2660
_cell_measurement_theta_min      2.2200
_cell_volume                     8422(2)
_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_temperature      100.35
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Saturn 724'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0495
_diffrn_reflns_av_unetI/netI     0.0558
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       53
_diffrn_reflns_limit_k_min       -53
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            65413
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.481
_diffrn_reflns_theta_min         3.086
_exptl_absorpt_coefficient_mu    0.490
_exptl_absorpt_correction_T_max  0.9855
_exptl_absorpt_correction_T_min  0.8289
_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    1.471
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3800
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.887
_refine_diff_density_min         -0.438
_refine_diff_density_rms         0.065
_refine_ls_abs_structure_details
;
 Flack x determined using 5636 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1194
_refine_ls_number_reflns         19220
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0769
_refine_ls_R_factor_gt           0.0642
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0932P)^2^+0.4367P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1614
_refine_ls_wR_factor_ref         0.1731
_reflns_Friedel_coverage         0.989
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                15837
_reflns_number_total             19220
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ra08657k2.cif
_cod_data_source_block           shelxl
_cod_database_code               7250914
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.828
_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, All O(H) groups, All O(H,H) groups
2. Restrained distances
 H93C-H15
 1.9 with sigma of 0.02
 H15-H93C
 2.2 with sigma of 0.02
3. Others
 Fixed Sof: F4(0.5) F16(0.5) F18(0.5) F5(0.5)
4.a Free rotating group:
 O4(H4A,H4B)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C7(H7), C9(H9), C12(H12), C13(H13), C14(H14),
 C15(H15), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C30(H30), C32(H32),
  C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C35(H35), C36(H36),
 C37(H37), C38(H38), C27(H27), C24(H24), C25(H25), C26(H26), C84(H84), C83(H83),
  C82(H82), C81(H81), C78(H78), C76(H76), C73(H73), C72(H72), C71(H71),
 C70(H70), C92(H92), C91(H91), C90(H90), C89(H89), C88(H88), C47(H47), C48(H48),
  C49(H49), C50(H50), C53(H53), C55(H55), C58(H58), C59(H59), C60(H60),
 C61(H61), C69(H69), C68(H68), C67(H67), C66(H66), C65(H65)
4.c Idealised Me refined as rotating group:
 C93(H93A,H93B,H93C)
4.d Idealised tetrahedral OH refined as rotating group:
 O1(H1A)
;
_shelx_res_checksum              45564
_olex2_submission_special_instructions 'No special instructions were received'