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_7719812
_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
'C8.929 H4.953 Fe0.5 N3.988 S1.988, C9.071 H7.047 Fe0.5 N5.012 S1.012, 3(C12 H4 N4)'
_chemical_formula_sum            'C54 H24 Fe N21 S3'
_chemical_formula_weight         1118.97
_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             2025-01-07
_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                 98.048(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   33.5745(8)
_cell_length_b                   9.7164(2)
_cell_length_c                   15.4349(3)
_cell_measurement_reflns_used    11964
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      33.6750
_cell_measurement_theta_min      3.5010
_cell_volume                     4985.63(19)
_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      90(2)
_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    -41.00 -15.00   0.50   72.50    --   13.10 -85.00  24.00   52
  2  \w    -31.00  21.00   0.50   72.50    --  -13.73  85.00 143.00  104
  3  \w    -41.00  11.00   0.50   72.50    --  -13.73 -85.00  24.00  104
  4  \w     -8.00  23.00   0.50   72.50    --   13.10  77.00-120.00   62
  5  \w     51.00  87.00   0.50   72.50    --   13.10 178.00 -30.00   72
  6  \w     12.00  38.00   0.50   72.50    --   13.10 -85.00  24.00   52
  7  \w    -25.00   9.00   0.50   72.50    --  -13.73 -77.00-120.00   68
  8  \w    -33.00  24.00   0.50   72.50    --  -13.73  77.00-120.00  114
  9  \w    -25.00   4.00   0.50   72.50    --  -13.73 -77.00  90.00   58
 10  \w    -33.00  25.00   0.50   72.50    --  -13.73  77.00  30.00  116
 11  \w    -24.00   1.00   0.50   72.50    --  -13.73 -77.00-180.00   50
;
_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      0.0181103000
_diffrn_orient_matrix_UB_12      -0.0065976000
_diffrn_orient_matrix_UB_13      0.0294640000
_diffrn_orient_matrix_UB_21      0.0037328000
_diffrn_orient_matrix_UB_22      -0.0643928000
_diffrn_orient_matrix_UB_23      -0.0189599000
_diffrn_orient_matrix_UB_31      0.0106541000
_diffrn_orient_matrix_UB_32      0.0337510000
_diffrn_orient_matrix_UB_33      -0.0304222000
_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  0.0289
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            32796
_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         29.573
_diffrn_reflns_theta_min         3.380
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.492
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.581
_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            'dark black'
_exptl_crystal_density_diffrn    1.491
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             2276
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.318
_exptl_crystal_size_mid          0.123
_exptl_crystal_size_min          0.081
_refine_diff_density_max         0.444
_refine_diff_density_min         -0.489
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     529
_refine_ls_number_reflns         6996
_refine_ls_number_restraints     442
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.1131
_refine_ls_R_factor_gt           0.0971
_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^)+(0.0227P)^2^+35.5674P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2035
_refine_ls_wR_factor_ref         0.2097
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5545
_reflns_number_total             6996
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02365c2.cif
_cod_data_source_block           structure1_90K
_cod_database_code               7719812
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         FeC54N21S3H27
_chemical_oxdiff_usercomment     'black rods, solvent MeCN, rxn ratio 1:1.5'
_shelx_estimated_absorpt_t_max   0.961
_shelx_estimated_absorpt_t_min   0.859
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2. Restrained distances
 C8B-C9B
 1.38 with sigma of 0.01
 C9B-N4B
 1.34 with sigma of 0.01
 C7A-C8A = C8A-C9A
 1.38 with sigma of 0.01
 C9A-C8A \\sim C8A-C7A
 with sigma of 0.02
3. Restrained planarity
 C9B, N4B, C7B, C8A, C8B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N4A \\sim C7A \\sim N3B \\sim C8A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C25 \\sim N9 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim N10 \\sim C29 \\sim
C28 \\sim C26 \\sim C27 \\sim C30 \\sim C32 \\sim C31 \\sim N12 \\sim N11:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C3B \\sim N1B \\sim C1B \\sim S1B \\sim C2B: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
N4B \\sim C7B \\sim S2B \\sim C8B \\sim C9B: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C3A) = Uanis(C2B)
Uanis(C8A) = Uanis(S2B)
Uanis(C7B) = Uanis(C7A)
Uanis(S1A) = Uanis(C5B)
Uanis(N3A) = Uanis(C3B)
Uanis(N3) = Uanis(C6A)
Uanis(C4A) = Uanis(C4B)
Uanis(C2A) = Uanis(S1B)
Uanis(C1A) = Uanis(C1B)
Uanis(C6B) = Uanis(C5A)
Uanis(C9B) = Uanis(N3B)
Uanis(N1A) = Uanis(N1B)
Uanis(N2A) = Uanis(N2B)
Uanis(C13A) = Uanis(C13B)
Uanis(C11A) = Uanis(C11B)
Uanis(C12A) = Uanis(C12B)
Uanis(N6A) = Uanis(N6B)
Uanis(C10A) = Uanis(C10B)
Uanis(N5A) = Uanis(N5B)
Uanis(N8B) = Uanis(N8A)
Uanis(C21B) = Uanis(C21A)
Uanis(C19B) = Uanis(C19A)
Uanis(C20B) = Uanis(C20A)
Uanis(N7B) = Uanis(N7A)
Uanis(C16A) = Uanis(C16B)
Uanis(C17B) = Uanis(C17A)
Uanis(C18A) = Uanis(C18B)
Uanis(C15A) = Uanis(C15B)
Uanis(C14A) = Uanis(C14B)
Uanis(Fe1B) = Uanis(Fe1A)
Uanis(N4B) = Uanis(N4A)
5. Rigid body (RIGU) restrains
 N4B, C7B, C8A, C8B, C9B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4A, C7A, N3B, C8A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N2B, N3, C6B, C5B, C4B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N2A, C6A, C5A, S1A, C4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22, N9, C21, C23, C24, N10, C29, C25, C28, C26, C27, C30, C32, C31, N12, N11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2A, C1A, N1A, N3A, C3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3B, N1B, C1B, S1B, C2B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7B, S2B, C8B, C9B, N4B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Fe1B(0.25) S1B(0.49409) S1A(0.50591) N1B(0.50591) N4A(0.5)
 N2A(0.50591) C14A(0.62207) H14A(0.62207) C15A(0.62207) H15A(0.62207)
 C13A(0.62207) C1A(0.50591) C17A(0.62207) H17A(0.62207) C18A(0.62207)
 H18A(0.62207) C4B(0.49409) C11A(0.62207) N3(0.49409) H3(0.49409) C3A(0.50591)
 H3A(0.50591) C8B(0.5) H8B(0.5) C9B(0.5) C7A(0.5) C12A(0.62207) C5A(0.50591)
 H5A(0.50591) N6A(0.62207) C2A(0.50591) H2A(0.50591) C5B(0.49409) H5B(0.49409)
 C6A(0.50591) N6B(0.37793) C13B(0.37793) N3B(0.5) H3B(0.5) C18B(0.37793)
 H18B(0.37793) C15B(0.37793) H15B(0.37793) C14B(0.37793) H14B(0.37793)
 C12B(0.37793) C11B(0.37793) N3A(0.50591) H3AA(0.50591) N5B(0.37793)
 C10B(0.37793) N5A(0.62207) C10A(0.62207) C17B(0.37793) H17B(0.37793) N9(0.5)
 C21(0.5) C23(0.5) N10(0.5) C22(0.5) C24(0.5) C29(0.5) H29(0.5) C25(0.5)
 H25(0.5) C28(0.5) H28(0.5) C27(0.5) C26(0.5) H26(0.5) C30(0.5) C32(0.5)
 N12(0.5) C31(0.5) N11(0.5) C16A(0.62207) C20A(0.62207) C21A(0.62207)
 C19A(0.62207) N8A(0.62207) N7A(0.62207) C21B(0.37793) C20B(0.37793)
 N8B(0.37793) N7B(0.37793) C16B(0.37793) C19B(0.37793) C6B(0.49409)
 H6B(0.49409) N2B(0.49409) N1A(0.49409) C1B(0.49409) C3B(0.49409) C4A(0.50591)
 C2B(0.49409) H2B(0.49409) Fe1A(0.25) N4B(0.5) C8A(0.5) H8A(0.5) S2B(0.5)
 C7B(0.5) C9A(0.5) H9A(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C14A(H14A), C15A(H15A), C17A(H17A), C18A(H18A), N3(H3), C3A(H3A), C8B(H8B),
 C5A(H5A), C2A(H2A), C5B(H5B), N3B(H3B), C18B(H18B), C15B(H15B), C14B(H14B),
 N3A(H3AA), C17B(H17B), C29(H29), C25(H25), C28(H28), C26(H26), C6B(H6B),
 C2B(H2B), C8A(H8A), C9A(H9A)
;
_shelx_res_checksum              62157
_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 1.494
_oxdiff_exptl_absorpt_empirical_full_min 0.592