Tetramethylbenzidine–TetrafluoroTCNQ (TMB–TCNQF4): A Narrow-Gap Semiconducting Salt with Room-Temperature Relaxor Ferroelectric Behavior
Canossa, Stefano; Ferrari, Elena; Sippel, Pit; Fischer, Jonas K. H.; Pfattner, Raphael; Frison, Ruggero; Masino, Matteo; Mas-Torrent, Marta; Lunkenheimer, Peter; Rovira, Concepció; Girlando, Alberto; The Journal of Physical Chemistry C 125 (2021) 25816–25824; doi:10.1021/acs.jpcc.1c07131

data_1565531
_publ_section_title
;
 Tetramethylbenzidine--TetrafluoroTCNQ (TMB--TCNQF4): A Narrow-Gap
 Semiconducting Salt with Room-Temperature Relaxor Ferroelectric Behavior
;
_journal_issue                   46
_journal_name_full               'The Journal of Physical Chemistry C'
_journal_page_first              25816
_journal_page_last               25824
_journal_paper_doi               10.1021/acs.jpcc.1c07131
_journal_volume                  125
_journal_year                    2021
_chemical_formula_moiety         'C12 F4 N4, C16 H20 N2'
_chemical_formula_sum            'C28 H20 F4 N6'
_chemical_formula_weight         516.505
_chemical_name_systematic
'tetramethylbenzidine tetrafluorotetracyanoquinodimethane'
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_symmetry_Int_Tables_number      11
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-17 deposited with the CCDC.	2021-07-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.247(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.6095(1)
_cell_length_b                   22.9174(5)
_cell_length_c                   8.3274(2)
_cell_measurement_reflns_used    11500
_cell_measurement_temperature    150.0
_cell_measurement_theta_max      29.08
_cell_measurement_theta_min      2.55
_cell_volume                     1190.87(5)
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.3 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.9986
_diffrn_measured_fraction_theta_max 0.9921
_diffrn_measurement_device_type  'ELETTRA XRD1'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.7
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_Laue_measured_fraction_full 0.9986
_diffrn_reflns_Laue_measured_fraction_max 0.9921
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            21041
_diffrn_reflns_point_group_measured_fraction_full 0.9986
_diffrn_reflns_point_group_measured_fraction_max 0.9921
_diffrn_reflns_theta_full        24.8346
_diffrn_reflns_theta_max         29.08
_diffrn_reflns_theta_min         2.55
_exptl_absorpt_coefficient_mu    0.107
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
'CrysAlisPro 1.171.40.26a (Rigaku Oxford Diffraction, 2018) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.'
_exptl_crystal_colour            'dull black'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.440
_exptl_crystal_description       needle
_exptl_crystal_F_000             532.146
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.5477
_refine_diff_density_min         -0.3304
_refine_diff_density_rms         0.0740
_refine_ls_d_res_high            0.7200
_refine_ls_d_res_low             7.8620
_refine_ls_goodness_of_fit_ref   1.0540
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    15
_refine_ls_number_parameters     174
_refine_ls_number_reflns         3386
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0540
_refine_ls_R_factor_all          0.0698
_refine_ls_R_factor_gt           0.0509
_refine_ls_shift/su_max          0.0001
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0773P)^2^+0.3133P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1394
_refine_ls_wR_factor_ref         0.1530
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              8
_reflns_limit_h_min              -9
_reflns_limit_k_max              30
_reflns_limit_k_min              0
_reflns_limit_l_max              11
_reflns_limit_l_min              0
_reflns_number_gt                2503
_reflns_number_total             3386
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            jp1c07131_si_003.cif
_cod_data_source_block           TMB-TCNQF4_150K
_cod_database_code               1565531
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C6(H6)
2.b X=CH2 refined with riding coordinates:
 N3(H3a,H3b)
2.c Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C2(H2a,H2b,H2c)
;
_olex2_exptl_crystal_mounting_method 'kapton loop (Fomblyn Oil)'
_olex2_submission_original_sample_id
'tetramethylbenzidine tetrafluorotetracyanoquinodimethane'
_olex2_submission_special_instructions 'No special instructions were received'