Unusual symmetry breaking in high-temperature enantiomeric ferroelectrics with large spontaneous polarization
Li, Yu-Kong; Ying, Ting-Ting; Zhang, Hao; Tan, Yu-Hui; Tang, Yun-Zhi; Wang, Fang-Xin; Wan, Ming-Yang; Dalton Transactions  (2022) –; doi:10.1039/D2DT00592A

data_7710078
_publ_section_title
;
 Unusual symmetry breaking in high-temperature enantiomeric ferroelectrics
 with large spontaneous polarization
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00592A
_journal_year                    2022
_chemical_formula_moiety         'Cd2 Cl8, 4(C9 H14 N)'
_chemical_formula_sum            'C36 H56 Cd2 Cl8 N4'
_chemical_formula_weight         1053.24
_chemical_name_systematic        1
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-03-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-03-19 deposited with the CCDC.	2022-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                94.1890(10)
_cell_angle_beta                 97.9310(10)
_cell_angle_gamma                90.9170(10)
_cell_formula_units_Z            1
_cell_length_a                   7.78440(10)
_cell_length_b                   7.80520(10)
_cell_length_c                   18.2463(2)
_cell_measurement_reflns_used    16575
_cell_measurement_temperature    360.0(4)
_cell_measurement_theta_max      29.7860
_cell_measurement_theta_min      2.2460
_cell_volume                     1094.70(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      360(2)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.859
_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     12.00  52.00   0.50    0.05    --    8.00-115.00 161.91   80
  2  \w    -51.00 -25.00   0.50    0.05    --    8.30 -37.00  90.00   52
  3  \w     45.00  72.00   0.50    0.05    --    8.30  77.00 -90.00   54
  4  \w    -10.00  43.00   0.50    0.05    --    8.30 -99.00-150.00  106
  5  \w     -8.00  18.00   0.50    0.05    --    8.30  77.00 -90.00   52
  6  \w     -3.00  23.00   0.50    0.05    --    8.30 -37.00  90.00   52
  7  \w    -17.00  43.00   0.50    0.05    --    8.30 -99.00  90.00  120
  8  \w    -64.00  23.00   0.50    0.05    --    8.30 -37.00   0.00  174
  9  \w     -8.00  43.00   0.50    0.05    --    8.30 -99.00 -60.00  102
 10  \w    -80.00   3.00   0.50    0.05    --   -8.69 -77.00 -90.00  166
 11  \w    -24.00  18.00   0.50    0.05    --   -8.69  37.00 -60.00   84
 12  \w    -73.00 -24.00   0.50    0.05    --   -8.69 -57.00   0.00   98
 13  \w    -80.00   2.00   0.50    0.05    --   -8.69 -77.00  90.00  164
 14  \w    -72.00   3.00   0.50    0.05    --   -8.69 -37.00  90.00  150
 15  \w    -24.00  60.00   0.50    0.05    --   -8.69  37.00-150.00  168
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0265
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.859
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            31044
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.791
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.744
_diffrn_reflns_theta_min         2.260
_exptl_absorpt_coefficient_mu    1.490
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86906
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.39a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.598
_exptl_crystal_description       block
_exptl_crystal_F_000             532
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.946
_refine_diff_density_min         -0.397
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 3906 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.022(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     447
_refine_ls_number_reflns         11780
_refine_ls_number_restraints     130
_refine_ls_restrained_S_all      1.097
_refine_ls_R_factor_all          0.0434
_refine_ls_R_factor_gt           0.0327
_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^)+(0.0329P)^2^+0.2347P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0774
_refine_ls_wR_factor_ref         0.0819
_reflns_Friedel_coverage         0.842
_reflns_Friedel_fraction_full    0.961
_reflns_Friedel_fraction_max     0.723
_reflns_number_gt                9463
_reflns_number_total             11780
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00592a2.cif
_cod_data_source_block           l_htp
_cod_database_code               7710078
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.878
_shelx_estimated_absorpt_t_min   0.807
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N4-C9
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C4 \\sim C9 \\sim N4 \\sim C7 \\sim C6 \\sim C8 \\sim C1 \\sim C5 \\sim C2
\\sim C3: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
4. Rigid body (RIGU) restrains
 N4, C9, C7, H7, C6, C8, C1, C5, H8A, H8B, H8C, C2, H1, H5, C4, H2, C3, H4, H3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5.a Ternary CH refined with riding coordinates:
 C35(H35), C26(H26), C7(H7), C17(H17)
5.b Secondary CH2 refined with riding coordinates:
 C28(H28A,H28B), C37(H37A,H37B), C18(H18A,H18B), C9(H9A,H9B)
5.c Aromatic/amide H refined with riding coordinates:
 C25(H25), C24(H24), C33(H33), C34(H34), C30(H30), C32(H32), C31(H31),
 C23(H23), C22(H22), C21(H21), C11(H11), C2(H2), C1(H1), C5(H5), C4(H4), C3(H3),
  C12(H12), C13(H13), C16(H16), C14(H14)
5.d Fitted hexagon refined as free rotating group:
 C2(C1,C6,C5,C4,C3)
5.e Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), N2(H2A,H2B,H2C), N1(H1A,H1B,H1C), C27(H27A,H27B,H27C),
 N4(H4A,H4B,H4C), N3(H3A,H3B,H3C), C19(H19A,H19B,H19C), C8(H8A,H8B,H8C)
;
_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
;