Spin-Crossover Semiconductors Based on Homoleptic Tris-Diimine Fe(II) Complexes with Fractionally Charged TCNQ•δ- Anions
Amanyazova, Botagoz; Shatruk, Michael; Yergeshbayeva, Sandugash; Choi, Eun Sang; Erkasov, Rakhmetulla; Dalton Transactions  (2025) –; doi:10.1039/D5DT02365C

data_7719809
_publ_section_title
;
 Spin-Crossover Semiconductors Based on Homoleptic Tris-Diimine Fe(II)
 Complexes with Fractionally Charged TCNQ&#x2022;\d- Anions
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D5DT02365C
_journal_year                    2025
_chemical_formula_moiety         'C18 H12 Fe N6 S6, 3(C12 H4 N4)'
_chemical_formula_sum            'C54 H24 Fe N18 S6'
_chemical_formula_weight         1173.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-13
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-03-25 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.703(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   33.1267(8)
_cell_length_b                   9.9158(2)
_cell_length_c                   15.8990(4)
_cell_measurement_reflns_used    16748
_cell_measurement_temperature    229.99(10)
_cell_measurement_theta_max      33.5150
_cell_measurement_theta_min      3.4470
_cell_volume                     5147.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 42.74a 64-bit (release 17-11-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      229.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_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    -13.00  38.00   0.50   78.74    --   11.39-102.00-143.00  102
  2  \w    -24.00  32.00   0.50   78.74    --   11.39 -77.00 -30.00  112
  3  \w     -1.00  58.00   0.50   78.74    --   11.39  57.00 150.00  118
  4  \w     -1.00  42.00   0.50   78.74    --   11.39 -99.00  60.00   86
  5  \w     -7.00  42.00   0.50   78.74    --   11.39 -99.00-180.00   98
  6  \w     -7.00  31.00   0.50   78.74    --   11.39 -99.00  30.00   76
  7  \w    -18.00  32.00   0.50   78.74    --   11.39 -77.00-120.00  100
  8  \w    -24.00  25.00   0.50   78.74    --   11.39 -77.00 -60.00   98
  9  \w    -19.00   9.00   0.50   78.74    --  -12.02 -77.00 120.00   56
 10  \w    -25.00   9.00   0.50   78.74    --  -12.02 -77.00-150.00   68
 11  \w    -59.00   1.00   0.50   78.74    --  -12.02 -57.00 -30.00  120
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0009455000
_diffrn_orient_matrix_UB_12      0.0319241000
_diffrn_orient_matrix_UB_13      0.0395611000
_diffrn_orient_matrix_UB_21      -0.0207156000
_diffrn_orient_matrix_UB_22      0.0177067000
_diffrn_orient_matrix_UB_23      -0.0148393000
_diffrn_orient_matrix_UB_31      -0.0064480000
_diffrn_orient_matrix_UB_32      -0.0615292000
_diffrn_orient_matrix_UB_33      0.0162433000
_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  0.0524
_diffrn_reflns_av_unetI/netI     0.0315
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       47
_diffrn_reflns_limit_h_min       -47
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            45635
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.508
_diffrn_reflns_theta_min         3.290
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.596
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.481
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.137a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.514
_exptl_crystal_description       plate
_exptl_crystal_F_000             2384
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.246
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.707
_refine_diff_density_min         -0.494
_refine_diff_density_rms         0.072
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     486
_refine_ls_number_reflns         7852
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0644
_refine_ls_R_factor_gt           0.0492
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0727P)^2^+3.5356P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1276
_refine_ls_wR_factor_ref         0.1373
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6090
_reflns_number_total             7852
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02365c2.cif
_cod_data_source_block           structure2_230K
_cod_database_code               7719809
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         FeC54H30N12S6
_chemical_oxdiff_usercomment
'[Fe(4bt)3](TCNQ)3, same xtal as for 100K, sam orientation'
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.819
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C10B-N4B
 1.137 with sigma of 0.01
 C10-N4
 1.137 with sigma of 0.01
 C2-S1B
 1.73 with sigma of 0.01
 S1B-C1
 1.73 with sigma of 0.01
 S1-C1
 1.73 with sigma of 0.01
 S1-C2
 1.73 with sigma of 0.01
 C5-S2B
 1.73 with sigma of 0.01
 S2B-C6
 1.73 with sigma of 0.01
 S2-C5
 1.73 with sigma of 0.01
 S2-C6
 1.73 with sigma of 0.01
 C5-S2B \\sim S2B-C6
 with sigma of 0.02
 C5-S2 \\sim S2-C6
 with sigma of 0.02
 C17B-C16B \\sim C16B-C15B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(S1B) = Uanis(S1)
Uanis(C10) = Uanis(C10B)
Uanis(N4) = Uanis(N4B)
Uanis(C16) = Uanis(C16B)
Uanis(C15) = Uanis(C15B)
Uanis(N6B) = Uanis(N6)
Uanis(S2B) = Uanis(S2)
Uanis(C14B) = Uanis(C14)
Uanis(C13B) = Uanis(C13)
Uanis(C20) = Uanis(C20B)
Uanis(C18B) = Uanis(C18)
Uanis(C17B) = Uanis(C17)
Uanis(C19) = Uanis(C19B)
Uanis(C21) = Uanis(C21B)
Uanis(N7) = Uanis(N7B)
Uanis(C11) = Uanis(C11B)
Uanis(C12) = Uanis(C12B)
Uanis(N5) = Uanis(N5B)
4. Others
 Sof(C19B)=Sof(N7B)=Sof(C11B)=Sof(C12B)=Sof(C21B)=Sof(C17B)=Sof(H17B)=
 Sof(C18B)=Sof(H18B)=Sof(C13B)=Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(H15B)=
 Sof(C16B)=Sof(N5B)=Sof(C10B)=Sof(N4B)=Sof(N6B)=Sof(C20B)=1-FVAR(1)
 Sof(N4)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(N6)=Sof(N7)=Sof(C16)=Sof(C13)=
 Sof(C11)=Sof(C20)=Sof(C10)=Sof(C19)=Sof(C18)=Sof(H18)=Sof(C21)=Sof(C17)=
 Sof(H17)=Sof(C12)=Sof(N5)=FVAR(1)
 Sof(S1B)=1-FVAR(2)
 Sof(S1)=FVAR(2)
 Sof(S2B)=1-FVAR(3)
 Sof(S2)=FVAR(3)
 Fixed Sof: N8(0.5) C27(0.5) H27(0.5) C23(0.5) C29(0.5) H29(0.5) C25(0.5)
 C22(0.5) N9(0.5) C24(0.5) C31(0.5) N10(0.5) N11(0.5) C28(0.5) C33(0.5)
 C32(0.5) C26(0.5) H26(0.5) C30(0.5) H30(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C6(H6), C18(H18), C8(H8), C27(H27), C7(H7), C29(H29),
 C5(H5), C1(H1), C17(H17), C2(H2), C17B(H17B), C18B(H18B), C14B(H14B),
 C15B(H15B), C26(H26), C30(H30)
;
_shelx_res_checksum              95271
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.992
_oxdiff_exptl_absorpt_empirical_full_min 0.606