Thermal responsive cation flipping and dielectric constant in an organic–inorganic hybrid crystal
Wang, Lei; Hu, Wei-Yu; Zhou, Hua-Qing; Li, Wang; Zhang, Shi-Yong; Wang, Zhong-Xia; CrystEngComm 27 (2025) 7170–7177; doi:10.1039/D5CE00814J

data_7250935
_publ_section_title
;
 Thermal responsive cation flipping and dielectric constant in an
 organic--inorganic hybrid crystal
;
_journal_issue                   44
_journal_name_full               CrystEngComm
_journal_page_first              7170
_journal_page_last               7177
_journal_paper_doi               10.1039/D5CE00814J
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'Br4 Zn, 2(C8 H18 N)'
_chemical_formula_sum            'C16 H36 Br4 N2 Zn'
_chemical_formula_weight         641.48
_chemical_name_systematic        (PrMeNC4H8)2[ZnBr4]
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-08-17
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-08-17 deposited with the CCDC.	2025-10-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.239(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.120(4)
_cell_length_b                   9.3802(6)
_cell_length_c                   17.127(2)
_cell_measurement_reflns_used    8657
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      71.5880
_cell_measurement_theta_min      2.8830
_cell_volume                     2445.1(7)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0756
_diffrn_reflns_av_unetI/netI     0.0722
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            17610
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.155
_diffrn_reflns_theta_min         2.903
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    9.046
_exptl_absorpt_correction_T_max  3.497
_exptl_absorpt_correction_T_min  0.316
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.43.129a (Rigaku Oxford Diffraction, 2024)'
_exptl_crystal_density_diffrn    1.743
_exptl_crystal_description       block
_exptl_crystal_F_000             1264
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.613
_refine_diff_density_min         -0.808
_refine_diff_density_rms         0.102
_refine_ls_extinction_coef       0.00077(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     371
_refine_ls_number_reflns         4715
_refine_ls_number_restraints     370
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.0848
_refine_ls_R_factor_gt           0.0613
_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^)+(0.1003P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1731
_refine_ls_wR_factor_ref         0.1910
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3195
_reflns_number_total             4715
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00814j2.cif
_cod_data_source_block           273k-new
_cod_depositor_comments
'Adding full bibliography for 7250934--7250936.cif.'
_cod_original_cell_volume        2445.2(7)
_cod_database_code               7250935
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.613
_shelx_estimated_absorpt_t_min   0.465
_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. Restrained distances
 C16-C15
 1.51 with sigma of 0.02
 C7A-C8A = C7A-C6A = C2A-C1A = C3A-C2A
 1.51 with sigma of 0.02
 C3A-C4A = C3A-C2A = C1-C2 = C3-C4 = C2A-C1A = C3-C2
 1.51 with sigma of 0.02
 C2A-C1A = C3A-C2A
 1.51 with sigma of 0.01
 C7-C6 = C7-C8
 1.51 with sigma of 0.02
 N1-C1 = N1-C5A = N1-C4 = N1-C1A = N1-C4A = N1-C5
 1.49 with sigma of 0.02
 N1-C6A = N1-C1A = N1-C4A
 1.49 with sigma of 0.02
 C4A-C3A
 1.51 with sigma of 0.02
 N1-C4A = N1-C1A
 1.49 with sigma of 0.02
 N1-C1A = N1-C4A = N1-C6A
 1.49 with sigma of 0.02
 N1-C2A
 2.5 with sigma of 0.02
 C1A-C6A
 2.5 with sigma of 0.02
 C9A-C10A = C10A-C11A = C9-C10 = C11-C10 = C12A-C11A = C12-C11
 1.51 with sigma of 0.02
 N1-C3A
 2.5 with sigma of 0.02
 C15A-C14A = C15A-C16A = C16-C15 = C14-C15
 1.51 with sigma of 0.02
 C15A-C16A
 1.51 with sigma of 0.02
 N1-C5A
 1.49 with sigma of 0.02
 N2-C14A = N2-C14
 1.49 with sigma of 0.02
 N2-C12A = N2-C12 = N2-C9 = N2-C9A
 1.49 with sigma of 0.02
 C5-C6
 2.5 with sigma of 0.02
 C8-C6
 2.5 with sigma of 0.02
 N1-C6A
 1.49 with sigma of 0.02
 N1-C6
 1.49 with sigma of 0.02
 C6-C4
 2.5 with sigma of 0.02
 C1-C4 \\sim C4-C5
 with sigma of 0.02
 Br3-Zn1 \\sim Br3A-Zn1 \\sim Br2A-Zn1 \\sim Br2-Zn1
 with sigma of 0.02
 Br4-Zn1 \\sim Br4A-Zn1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N1 \\sim C4A \\sim C6A \\sim C1A \\sim C5A \\sim C5 \\sim C4 \\sim C1 \\sim C6
\\sim C3A \\sim C7A \\sim C2A \\sim C3 \\sim C2 \\sim C7 \\sim C8A \\sim C8:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C11A \\sim C10: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(C3A) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of
0.05 and sigma for terminal atoms of 0.1
Uanis(C9A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C16A) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C13)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C12) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C11A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C15A) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(Br2A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Fixed Sof: Br4A(0.52513) Br3A(0.52513) Br2A(0.52513) C4A(0.38852)
 H4C(0.38852) H4D(0.38852) C10(0.56845) H10A(0.56845) H10B(0.56845) C9(0.56845)
 H9A(0.56845) H9B(0.56845) C11(0.56845) H11A(0.56845) H11B(0.56845)
 C15(0.56845) H15A(0.56845) H15B(0.56845) C6A(0.32988) H6C(0.32988)
 H6D(0.32988) C1A(0.38852) H1C(0.38852) H1D(0.38852) C12(0.56845) H12A(0.56845)
 H12B(0.56845) C14(0.56845) H14A(0.56845) H14B(0.56845) Br2(0.47487)
 Br3(0.47487) Br4(0.47487) C16(0.56845) H16A(0.56845) H16B(0.56845)
 H16C(0.56845) C14A(0.43155) H14C(0.43155) H14D(0.43155) C15A(0.43155)
 H15C(0.43155) H15D(0.43155) C16A(0.43155) H16D(0.43155) H16E(0.43155)
 H16F(0.43155) C10A(0.43155) H10C(0.43155) H10D(0.43155) C9A(0.43155)
 H9C(0.43155) H9D(0.43155) C12A(0.43155) H12C(0.43155) H12D(0.43155)
 C11A(0.43155) H11C(0.43155) H11D(0.43155) C8A(0.32988) H8D(0.32988)
 H8E(0.32988) H8F(0.32988) C7A(0.32988) H7C(0.32988) H7D(0.32988) C2A(0.38852)
 H2C(0.38852) H2D(0.38852) C3A(0.38852) H3C(0.38852) H3D(0.38852) C5A(0.38852)
 H5D(0.38852) H5E(0.38852) H5F(0.38852) C5(0.61148) H5A(0.61148) H5B(0.61148)
 H5C(0.61148) C4(0.61148) H4A(0.61148) H4B(0.61148) C2(0.61148) H2A(0.61148)
 H2B(0.61148) C1(0.61148) H1A(0.61148) H1B(0.61148) C3(0.61148) H3A(0.61148)
 H3B(0.61148) C6(0.67012) H6A(0.67012) H6B(0.67012) C7(0.67012) H7A(0.67012)
 H7B(0.67012) C8(0.67012) H8A(0.67012) H8B(0.67012) H8C(0.67012)
5.a Secondary CH2 refined with riding coordinates:
 C4A(H4C,H4D), C10(H10A,H10B), C9(H9A,H9B), C11(H11A,H11B), C15(H15A,H15B),
 C6A(H6C,H6D), C1A(H1C,H1D), C12(H12A,H12B), C14(H14A,H14B), C14A(H14C,H14D),
 C15A(H15C,H15D), C10A(H10C,H10D), C9A(H9C,H9D), C12A(H12C,H12D), C11A(H11C,
 H11D), C7A(H7C,H7D), C2A(H2C,H2D), C3A(H3C,H3D), C4(H4A,H4B), C2(H2A,H2B),
 C1(H1A,H1B), C3(H3A,H3B), C6(H6A,H6B), C7(H7A,H7B)
5.b Me refined with riding coordinates:
 C13(H13A,H13B,H13C), C16(H16A,H16B,H16C), C16A(H16D,H16E,H16F), C8A(H8D,H8E,
 H8F), C5A(H5D,H5E,H5F), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              83538
_olex2_submission_special_instructions 'No special instructions were received'