A homochiral polar molecular piezoelectric material with phase transition and high piezoelectricity precisely designed by cyanomethyl group substitution
Yang, Shu-Jing; Bai, Yong-Ju; Qi, Jun-Chao; Huang, Xiao-Yun; Shen, Xin; Lu, Yan-Zi; Xia, Zhang-Tian; Lv, Hui-Peng; Liao, Wei-Qiang; CrystEngComm 26 (2024) 2883–2890; doi:10.1039/D4CE00023D

data_7248611
_publ_section_title
;
 A homochiral polar molecular piezoelectric material with phase transition
 and high piezoelectricity precisely designed by cyanomethyl group
 substitution
;
_journal_issue                   22
_journal_name_full               CrystEngComm
_journal_page_first              2883
_journal_page_last               2890
_journal_paper_doi               10.1039/D4CE00023D
_journal_volume                  26
_journal_year                    2024
_chemical_absolute_configuration S
_chemical_formula_moiety         'Cl O4, C9 H15 N4'
_chemical_formula_sum            'C9 H15 Cl N4 O4'
_chemical_formula_weight         278.70
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-23
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-12-22 deposited with the CCDC.	2024-04-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.654(7)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.8528(6)
_cell_length_b                   7.5471(7)
_cell_length_c                   9.7043(8)
_cell_measurement_reflns_used    4176
_cell_measurement_temperature    297.99(10)
_cell_measurement_theta_max      30.4020
_cell_measurement_theta_min      2.1650
_cell_volume                     642.60(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.79a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      297.99(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 0.867
_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    -13.00  24.00   0.50    1.03    --   -5.29 -99.00-180.00   74
  2  \w    -32.00  -7.00   0.50    1.03    --   -5.29 -86.00-142.00   50
  3  \w    -78.00   3.00   0.50    1.03    --   -5.29 -37.00 -30.00  162
  4  \w    -18.00  62.00   0.50    1.03    --   -5.29  19.00 -60.00  160
  5  \w    -27.00  10.00   0.50    1.03    --   -5.29  86.00 -23.00   74
  6  \w     -2.00  39.00   0.50    1.03    --    5.29  37.00-150.00   82
  7  \w     42.00  70.00   0.50    1.03    --    5.29  37.00-150.00   56
  8  \w    -13.00  26.00   0.50    1.03    --    5.29 -86.00-142.00   78
  9  \w    -18.00  38.00   0.50    1.03    --    5.29 -99.00 120.00  112
 10  \w     -8.00  12.00   0.50    1.03    --    5.29  86.00 -23.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0297372000
_diffrn_orient_matrix_UB_12      0.0867993000
_diffrn_orient_matrix_UB_13      -0.0043529000
_diffrn_orient_matrix_UB_21      -0.0315503000
_diffrn_orient_matrix_UB_22      0.0242784000
_diffrn_orient_matrix_UB_23      0.0607482000
_diffrn_orient_matrix_UB_31      0.0682655000
_diffrn_orient_matrix_UB_32      -0.0265628000
_diffrn_orient_matrix_UB_33      0.0415323000
_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  0.0453
_diffrn_reflns_av_unetI/netI     0.0534
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.867
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            9594
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.798
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.645
_diffrn_reflns_theta_min         2.117
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.311
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66704
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.79a (Rigaku Oxford Diffraction, 2022)
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    1.440
_exptl_crystal_description       block
_exptl_crystal_F_000             292
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.382
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 686 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     193
_refine_ls_number_reflns         3179
_refine_ls_number_restraints     79
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.1077
_refine_ls_R_factor_gt           0.0754
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1306P)^2^+0.1856P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2139
_refine_ls_wR_factor_ref         0.2412
_reflns_Friedel_coverage         0.724
_reflns_Friedel_fraction_full    0.971
_reflns_Friedel_fraction_max     0.720
_reflns_number_gt                2051
_reflns_number_total             3179
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce00023d2.cif
_cod_data_source_block           ysj-220930-2-298k_auto
_cod_depositor_comments
'Adding full bibliography for 7248609--7248611.cif.'
_cod_database_code               7248611
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Cl'
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.970
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Restrained distances
 C2-C1 = C1A-C2A
 1.461 with sigma of 0.00001
 C3-C4
 1.5 with sigma of 0.0001
 C5-C6 = C7-C4
 1.54 with sigma of 0.00001
 N3-C7 = N3-C6 = N2-C5 = N2-C4
 1.47 with sigma of 0.0001
2. Rigid bond restraints
 C2, C2A, C1A, C1, N1, N1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
N2 \\sim C2 \\sim C2A \\sim C1 \\sim N1: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.01 within 2A
4. Rigid body (RIGU) restrains
 C2A, C2, C1, N1, N2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N1A, N1, C1, C1A, C2, C2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(C2A)=Sof(H2AA)=Sof(H2AB)=1-FVAR(1)
 Sof(C2)=Sof(H2A)=Sof(H2B)=FVAR(1)
 Sof(N1A)=1-FVAR(2)
 Sof(N1)=FVAR(2)
 Fixed Sof: C1(0.5) C1A(0.5)
6.a Ternary CH refined with riding coordinates:
 N3(H3), C4(H4)
6.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C6(H6A,H6B), C2(H2A,H2B), C5(H5A,H5B), C2A(H2AA,H2AB)
6.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C)
;
_shelx_res_checksum              19822
_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 2.268
_oxdiff_exptl_absorpt_empirical_full_min 0.331