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_7719810
_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             2025-01-07
_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                 99.860(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   33.4089(10)
_cell_length_b                   9.8946(4)
_cell_length_c                   15.9778(6)
_cell_measurement_reflns_used    4997
_cell_measurement_temperature    298.0(4)
_cell_measurement_theta_max      28.4480
_cell_measurement_theta_min      3.5690
_cell_volume                     5203.7(3)
_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      air
_diffrn_ambient_temperature      298.0(4)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.967
_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    -77.00   5.00   0.50  125.73    --   -4.49 -35.00 -80.00  164
  2  \w    -11.00  64.00   0.50  125.73    --   -4.49  35.00  76.00  150
  3  \w     -7.00  27.00   0.50  125.73    --   -4.49 -99.00 -30.00   68
  4  \w    -25.00  17.00   0.50  125.73    --   -4.49 -77.00-150.00   84
;
_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      -0.0184211000
_diffrn_orient_matrix_UB_12      0.0320951000
_diffrn_orient_matrix_UB_13      0.0049996000
_diffrn_orient_matrix_UB_21      -0.0064297000
_diffrn_orient_matrix_UB_22      -0.0007011000
_diffrn_orient_matrix_UB_23      -0.0446986000
_diffrn_orient_matrix_UB_31      -0.0091277000
_diffrn_orient_matrix_UB_32      -0.0641036000
_diffrn_orient_matrix_UB_33      0.0030516000
_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  0.0556
_diffrn_reflns_av_unetI/netI     0.0475
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            19052
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.483
_diffrn_reflns_theta_min         3.445
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.590
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.702
_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    1.497
_exptl_crystal_description       needle
_exptl_crystal_F_000             2384
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.298
_exptl_crystal_size_mid          0.279
_exptl_crystal_size_min          0.101
_refine_diff_density_max         0.431
_refine_diff_density_min         -0.379
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     486
_refine_ls_number_reflns         5774
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0867
_refine_ls_R_factor_gt           0.0583
_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^)+(0.0756P)^2^+5.4426P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1478
_refine_ls_wR_factor_ref         0.1658
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4000
_reflns_number_total             5774
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02365c2.cif
_cod_data_source_block           structure2_295K
_cod_database_code               7719810
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'Fe C30 H30 N12 S6'
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.844
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C2-S1B \\sim C2-S1A
 with sigma of 0.02
 C1-S1A \\sim S1A-C2
 with sigma of 0.02
 C5-S2B \\sim S2B-C6
 with sigma of 0.02
 C5-S2A \\sim S2A-C6
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(S1B) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(S1A) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(S2A) = Uanis(S2B)
Uanis(S1B) = Uanis(S1A)
Uanis(C14A) = Uanis(C14B)
Uanis(N4B) = Uanis(N4A)
Uanis(C10B) = Uanis(C10A)
Uanis(C11B) = Uanis(C11A)
Uanis(C12B) = Uanis(C12A)
Uanis(N5B) = Uanis(N5A)
Uanis(C13B) = Uanis(C13A)
Uanis(C15B) = Uanis(C15A)
Uanis(C16A) = Uanis(C16B)
Uanis(C17A) = Uanis(C17B)
Uanis(C18A) = Uanis(C18B)
Uanis(C19B) = Uanis(C19A)
Uanis(C20A) = Uanis(C20B)
Uanis(C21B) = Uanis(C21A)
Uanis(N6A) = Uanis(N6B)
Uanis(N7A) = Uanis(N7B)
4. Others
 Sof(S1B)=1-FVAR(1)
 Sof(S1A)=FVAR(1)
 Sof(S2B)=1-FVAR(2)
 Sof(S2A)=FVAR(2)
 Sof(C16B)=Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(H18B)=Sof(C13B)=Sof(N7B)=
 Sof(C15B)=Sof(H15B)=Sof(N5B)=Sof(C21B)=Sof(C20B)=Sof(C11B)=Sof(C14B)=Sof(H14B)=
 Sof(C10B)=Sof(N6B)=Sof(C12B)=Sof(N4B)=Sof(C19B)=1-FVAR(3)
 Sof(C14A)=Sof(H14A)=Sof(N4A)=Sof(C15A)=Sof(H15A)=Sof(N7A)=Sof(N6A)=Sof(C13A)=
 Sof(C11A)=Sof(C10A)=Sof(C18A)=Sof(H18A)=Sof(C21A)=Sof(C20A)=Sof(C19A)=
 Sof(C12A)=Sof(N5A)=Sof(C16A)=Sof(C17A)=Sof(H17A)=FVAR(3)
 Fixed Sof: C28(0.5) C27(0.5) H27(0.5) C29(0.5) H29(0.5) C31(0.5) N10(0.5)
 N11(0.5) C33(0.5) C32(0.5) C30(0.5) H30(0.5) C25(0.5) C26(0.5) H26(0.5)
 C23(0.5) C24(0.5) N8(0.5) C22(0.5) N9(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C14A(H14A), C15A(H15A), C18A(H18A), C6(H6), C17B(H17B), C9(H9), C8(H8),
 C5(H5), C1(H1), C2(H2), C18B(H18B), C15B(H15B), C14B(H14B), C17A(H17A),
 C27(H27), C29(H29), C30(H30), C26(H26)
;
_shelx_res_checksum              69827
_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 3.201
_oxdiff_exptl_absorpt_empirical_full_min 0.452