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_7719808
_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 H15 Fe N9 S3, 3(C12 H4 N4)'
_chemical_formula_sum            'C54 H27 Fe N21 S3'
_chemical_formula_weight         1121.99
_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   mixed
_audit_creation_date             2025-01-06
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-03-25 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.304(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   33.6774(11)
_cell_length_b                   9.8498(3)
_cell_length_c                   15.4982(5)
_cell_measurement_reflns_used    6740
_cell_measurement_temperature    229.99(13)
_cell_measurement_theta_max      32.9980
_cell_measurement_theta_min      3.6470
_cell_volume                     5087.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 42.67a (release 29-08-2022))'
_computing_data_reduction        'CrysAlisPro 1.171.43.137a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.992
_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    -42.00  30.00   0.50   72.17    --   13.10 -83.00  21.00  144
  2  \w     -9.00  21.00   0.50   72.17    --  -13.57  83.00 142.00   60
  3  \w    -39.00 -13.00   0.50   72.17    --  -13.57  83.00 142.00   52
  4  \w     51.00  85.00   0.50   72.17    --   13.10 178.00 -60.00   68
  5  \w    -25.00   7.00   0.50   72.17    --  -13.57 -77.00 -30.00   64
  6  \w    -19.00  59.00   0.50   72.17    --  -13.57  19.00 120.00  156
  7  \w    -23.00  12.00   0.50   72.17    --  -13.57 -83.00  21.00   70
;
_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      -0.0184522000
_diffrn_orient_matrix_UB_12      -0.0097520000
_diffrn_orient_matrix_UB_13      -0.0277388000
_diffrn_orient_matrix_UB_21      -0.0029090000
_diffrn_orient_matrix_UB_22      -0.0620209000
_diffrn_orient_matrix_UB_23      0.0214778000
_diffrn_orient_matrix_UB_31      -0.0101965000
_diffrn_orient_matrix_UB_32      0.0352542000
_diffrn_orient_matrix_UB_33      0.0301552000
_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  0.0226
_diffrn_reflns_av_unetI/netI     0.0267
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       44
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            22209
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.280
_diffrn_reflns_theta_min         3.353
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.482
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.637
_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    1.465
_exptl_crystal_description       needle
_exptl_crystal_F_000             2288
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.68
_exptl_crystal_size_mid          0.272
_exptl_crystal_size_min          0.173
_refine_diff_density_max         0.400
_refine_diff_density_min         -0.478
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     492
_refine_ls_number_reflns         6273
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.1047
_refine_ls_R_factor_gt           0.0812
_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^)+(0.0757P)^2^+15.5600P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2181
_refine_ls_wR_factor_ref         0.2311
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4475
_reflns_number_total             6273
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02365c2.cif
_cod_data_source_block           structure1_230K
_cod_database_code               7719808
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         FeC54N21S3H27
_chemical_oxdiff_usercomment     'black rod, solvent MeCN, rcn ratio 1:1.5'
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.735
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups, All N(H,H) groups
2. Shared sites
{N5A, C1B}
{C9, N5B}
{C10, N2}
3. Restrained distances
 C6-C7
 1.38 with sigma of 0.01
 S2-C6
 1.73 with sigma of 0.01
 C8-C7
 1.38 with sigma of 0.01
 S2-C8
 1.73 with sigma of 0.01
 C3-C2
 1.38 with sigma of 0.01
 C3-C1
 1.38 with sigma of 0.01
 C4-C3B
 1.38 with sigma of 0.01
 C3B-C5
 1.38 with sigma of 0.01
 S1A-C4
 1.73 with sigma of 0.01
 S1A-C5
 1.73 with sigma of 0.01
 S1B-C1
 1.73 with sigma of 0.01
 S1B-C2
 1.73 with sigma of 0.01
 C8-H8
 0.94 with sigma of 0.01
4. Restrained planarity
 N3, C3B, C4, C5, C9
 with sigma of 0.1
 N4, N5A, C1, C2, C3
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Uanis(C10) = Uanis(N2)
Uanis(C9) = Uanis(N5B)
Uanis(N5A) = Uanis(C1B)
Uanis(S2) = Uanis(C7)
Uanis(C3B) = Uanis(C3)
Uanis(S1B) = Uanis(S1A)
Uanis(N7A) = Uanis(N7B)
Uanis(C11A) = Uanis(C11B)
Uanis(C10A) = Uanis(C10B)
Uanis(C9A) = Uanis(C9B)
Uanis(N6A) = Uanis(N6B)
Uanis(C12B) = Uanis(C12A)
Uanis(C17A) = Uanis(C17B)
Uanis(C16A) = Uanis(C16B)
Uanis(C15A) = Uanis(C15B)
Uanis(C14A) = Uanis(C14B)
Uanis(C13A) = Uanis(C13B)
Uanis(C18A) = Uanis(C18B)
Uanis(C20A) = Uanis(C20B)
Uanis(N9A) = Uanis(N9B)
Uanis(N8A) = Uanis(N8B)
Uanis(C19A) = Uanis(C19B)
6. Others
 Sof(S1B)=Sof(C3B)=Sof(H3B)=1-FVAR(1)
 Sof(S1A)=Sof(C3)=Sof(H3)=FVAR(1)
 Sof(N5B)=Sof(H5B)=Sof(C1B)=Sof(H1B)=1-FVAR(2)
 Sof(N5A)=Sof(H5A)=Sof(C9)=Sof(H9)=FVAR(2)
 Sof(N6B)=Sof(N7B)=Sof(N8B)=Sof(N9B)=Sof(C9B)=Sof(C10B)=Sof(C11B)=Sof(C12B)=
 Sof(C13B)=Sof(H13B)=Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(C16B)=Sof(H16B)=
 Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(C19B)=Sof(C20B)=1-FVAR(3)
 Sof(N6A)=Sof(N7A)=Sof(N8A)=Sof(N9A)=Sof(C9A)=Sof(C10A)=Sof(C11A)=Sof(C12A)=
 Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(C16A)=Sof(H16A)=
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(C19A)=Sof(C20A)=FVAR(3)
 Fixed Sof: S2(0.5) N2(0.5) H2A(0.5) N10(0.5) N11(0.5) N12(0.5) N13(0.5)
 C7(0.5) H7(0.5) C10(0.5) H10(0.5) C21(0.5) C22(0.5) C23(0.5) C24(0.5) C25(0.5)
 H25(0.5) C26(0.5) H26(0.5) C27(0.5) C28(0.5) H28(0.5) C29(0.5) H29(0.5)
 C30(0.5) C31(0.5) C32(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 N2(H2A), N5A(H5A), N5B(H5B), C1B(H1B), C2(H2), C3(H3), C3B(H3B), C5(H5),
 C7(H7), C9(H9), C10(H10), C13A(H13A), C13B(H13B), C14A(H14A), C14B(H14B),
 C16A(H16A), C16B(H16B), C17A(H17A), C17B(H17B), C25(H25), C26(H26), C28(H28),
 C29(H29)
;
_shelx_res_checksum              33408
_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 2.090
_oxdiff_exptl_absorpt_empirical_full_min 0.620