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_7710079
_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
_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                94.1510(10)
_cell_angle_beta                 97.9760(10)
_cell_angle_gamma                90.8420(10)
_cell_formula_units_Z            1
_cell_length_a                   7.78170(10)
_cell_length_b                   7.79720(10)
_cell_length_c                   18.2458(3)
_cell_measurement_reflns_used    3203
_cell_measurement_temperature    360
_cell_measurement_theta_max      24.73
_cell_measurement_theta_min      2.23
_cell_volume                     1093.14(3)
_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
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'multiwire proportional'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0300
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            32515
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.997
_diffrn_reflns_theta_min         2.261
_exptl_absorpt_coefficient_mu    1.492
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95459
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrysAlisPro 1.171.40.39a (Rigaku OD, 2019)'
_exptl_crystal_colour            'metallic light colourless'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.600
_exptl_crystal_description       plate
_exptl_crystal_F_000             532
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.973
_refine_diff_density_min         -0.312
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 3517 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.025(15)
_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     549
_refine_ls_number_reflns         10307
_refine_ls_number_restraints     201
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0329
_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^)+(0.0399P)^2^+0.0692P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0794
_refine_ls_wR_factor_ref         0.0838
_reflns_Friedel_coverage         0.947
_reflns_Friedel_fraction_full    0.963
_reflns_Friedel_fraction_max     0.946
_reflns_number_gt                8362
_reflns_number_total             10307
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00592a2.cif
_cod_data_source_block           2_htp
_cod_database_code               7710079
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.755
_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. Uiso/Uaniso restraints and constraints
Cl3B \\sim Cl4 \\sim Cl5B \\sim Cl6B \\sim Cl7B \\sim Cl8B \\sim Cl9B \\sim Cl
\\sim Cl1 \\sim Cl7A \\sim Cl8A \\sim Cl3A \\sim Cl5A \\sim Cl9A \\sim Cl6A
\\sim Cl2: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
within 2A
3. Rigid body (RIGU) restrains
 Cl4, Cd1B, Cl3B, Cl5B, Cl6B, Cl9B, Cl, Cd2B, Cl8B, Cl7B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1, Cd2A, Cd1A, Cl7A, Cl8A, Cl3A, Cl5A, Cl9A, Cl6A, Cl2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: Cd1B(0.8) Cd2B(0.8) Cl3B(0.8) Cl4(0.8) Cl5B(0.8) Cl6B(0.8)
 Cl7B(0.8) Cl8B(0.8) Cl9B(0.8) Cl(0.8) Cl1(0.2) Cd2A(0.2) Cl7A(0.2) Cl8A(0.2)
 Cl3A(0.2) Cl5A(0.2) Cl9A(0.2) Cl6A(0.2) Cl2(0.2) Cd1A(0.2)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C2(H2), C29(H29), C20(H20)
5.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C1(H1D,H1E), C28(H28A,H28B), C19(H19A,H19B)
5.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C9(H9), C7(H7), C6(H6), C8(H8), C14(H14), C16(H16), C15(H15),
 C17(H17), C18(H18), C36(H36), C34(H34), C35(H35), C32(H32), C33(H33), C23(H23),
  C26(H26), C27(H27), C24(H24), C25(H25)
5.d Idealised Me refined as rotating group:
 N2(H2A,H2B,H2C), N1(H1A,H1B,H1C), C12(H12A,H12B,H12C), N4(H4A,H4B,H4C),
 C30(H30A,H30B,H30C), C3(H3A,H3B,H3C), N3(H3D,H3E,H3F), C21(H21A,H21B,H21C)
;
_olex2_submission_special_instructions 'No special instructions were received'