High-Tc Fe-based ferroelectric compound with large spontaneous polarization and narrow bandgap
Tan, Yu-Xin; Ying, Ting-Ting; Fan, Xiao-Wei; Huang, Yan-Le; Wan, Ming-Yang; Wang, Fang-Xin; Li, Qiao-Lin; Wang, Meng-Na; New Journal of Chemistry 47 (2023) 20619–20625; doi:10.1039/D3NJ03461E

data_7062853
_publ_section_title
;
 High-Tc Fe-based ferroelectric compound with large spontaneous
 polarization and narrow bandgap
;
_journal_issue                   44
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              20619
_journal_page_last               20625
_journal_paper_doi               10.1039/D3NJ03461E
_journal_volume                  47
_journal_year                    2023
_chemical_formula_moiety         'Br4 Fe, C6 H16 N'
_chemical_formula_sum            'C6 H16 Br4 Fe N'
_chemical_formula_weight         477.69
_space_group_crystal_system      orthorhombic
_space_group_IT_number           36
_space_group_name_Hall           'C 2c -2'
_space_group_name_H-M_alt        'C m c 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-05-12 deposited with the CCDC.	2023-10-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6868(4)
_cell_length_b                   12.6059(6)
_cell_length_c                   13.3890(6)
_cell_measurement_reflns_used    3479
_cell_measurement_temperature    219.99(10)
_cell_measurement_theta_max      27.4470
_cell_measurement_theta_min      2.8350
_cell_volume                     1466.16(12)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      219.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.896
_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    -18.00  69.00   0.50    1.93    --   -5.46  28.00  65.00  174
  2  \w    -26.00  33.00   0.50    1.93    --    5.00  94.00-131.00  118
  3  \w    -18.00  50.00   0.50    1.93    --   -5.46  19.00-180.00  136
  4  \w    -18.00  28.00   0.50    1.93    --   -5.46 -99.00-120.00   92
  5  \w    -18.00  39.00   0.50    1.93    --    5.00 -99.00  60.00  114
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0292517000
_diffrn_orient_matrix_UB_12      0.0519869000
_diffrn_orient_matrix_UB_13      -0.0071205000
_diffrn_orient_matrix_UB_21      -0.0076872000
_diffrn_orient_matrix_UB_22      -0.0060467000
_diffrn_orient_matrix_UB_23      -0.0524296000
_diffrn_orient_matrix_UB_31      -0.0758497000
_diffrn_orient_matrix_UB_32      0.0206594000
_diffrn_orient_matrix_UB_33      0.0025668000
_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  0.0290
_diffrn_reflns_av_unetI/netI     0.0270
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.896
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            8141
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.812
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.539
_diffrn_reflns_theta_min         2.848
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    11.892
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55489
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic brownish brown'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    2.164
_exptl_crystal_description       block
_exptl_crystal_F_000             900
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.487
_refine_diff_density_min         -0.296
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 619 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.019(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     159
_refine_ls_number_reflns         1930
_refine_ls_number_restraints     127
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0385
_refine_ls_R_factor_gt           0.0285
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0221P)^2^+1.3672P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0523
_refine_ls_wR_factor_ref         0.0543
_reflns_Friedel_coverage         0.745
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.722
_reflns_number_gt                1617
_reflns_number_total             1930
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3nj03461e2.cif
_cod_data_source_block           1_LTP_auto
_cod_depositor_comments
'Adding full bibliography for 7062852--7062853.cif.'
_cod_database_code               7062853
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C N H Fe Br '
_shelx_estimated_absorpt_t_max   0.200
_shelx_estimated_absorpt_t_min   0.200
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C4 \\sim N7 \\sim C3A \\sim C2A \\sim C6: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C8) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C1) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 C1, N1, C3, C2, C006
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1, C5, C7B, C006, C8, C2, C3
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N7, C1, C7A, C2A, C4, C3A, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3A, N7, C4, C2A, C6
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: N1(0.25) C006(0.25) H00A(0.25) H00B(0.25) H00C(0.25) C2(0.25)
 H2A(0.25) H2B(0.25) C3(0.25) H3A(0.25) H3B(0.25) N7(0.25) C2A(0.25) H2AA(0.25)
 H2AB(0.25) C3A(0.25) H3AA(0.25) H3AB(0.25) C6(0.25) H6A(0.25) H6B(0.25)
 H6C(0.25) C1(0.25) H1A(0.25) H1B(0.25) H1C(0.25) C4(0.25) H4A(0.25) H4B(0.25)
 H4C(0.25) C5(0.25) H5A(0.25) H5B(0.25) H5C(0.25) C8(0.25) H8A(0.25) H8B(0.25)
 H8C(0.25) C7B(0.25) H7BA(0.25) H7BB(0.25) H7BC(0.25) C7A(0.25) H7AA(0.25)
 H7AB(0.25) H7AC(0.25)
5.a Riding coordinates:
 C1(H1A,H1B,H1C), C8(H8A,H8B,H8C), C7A(H7AA,H7AB,H7AC)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C2A(H2AA,H2AB), C3A(H3AA,H3AB)
5.c Idealised Me refined as rotating group:
 C006(H00A,H00B,H00C), C6(H6A,H6B,H6C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C),
 C7B(H7BA,H7BB,H7BC)
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.426
_oxdiff_exptl_absorpt_empirical_full_min 0.791