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_7250934
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-29
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7311)
;
_audit_update_record
;
2025-08-17 deposited with the CCDC.	2025-10-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.421(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.5689(9)
_cell_length_b                   9.4070(4)
_cell_length_c                   17.1548(11)
_cell_measurement_reflns_used    3846
_cell_measurement_temperature    343.01(10)
_cell_measurement_theta_max      61.2290
_cell_measurement_theta_min      2.8060
_cell_volume                     2536.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.129a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.129a 64-bit (release 29-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.129a (Rigaku OD, 2024)'
_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)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      343.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.932
_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     38.00  67.00   0.50    0.30    --   86.44 -77.00 -90.00   58
  2  \w     49.00  75.00   0.50    0.30    --   86.44 -77.00 -30.00   52
  3  \w     52.00  77.00   0.50    0.30    --   93.56 -77.00  30.00   50
  4  \w     45.00  70.00   0.50    0.30    --   93.56 -77.00  90.00   50
  5  \w     37.00  77.00   0.50    0.30    --   86.44 -77.00 120.00   80
  6  \w     37.00  72.00   0.50    0.30    --   86.44 -77.00  60.00   70
  7  \w     14.00  42.00   0.50    0.30    --   58.72 -70.00  27.00   56
  8  \w      1.00  35.00   0.50    0.30    --   51.65 -70.00  27.00   68
  9  \w     34.00  59.00   0.50    0.30    --   86.44 -70.00  27.00   50
 10  \w     41.00  66.00   0.50    0.30    --   93.56 -70.00  27.00   50
 11  \w     12.00  38.00   0.50    0.30    --   58.72 -61.00 -60.00   52
 12  \w     46.00  72.00   0.50    0.30    --   93.56 -77.00-120.00   52
 13  \w     49.00  77.00   0.50    0.30    --   93.56 -77.00-150.00   56
 14  \w     -2.00  23.00   0.50    0.30    --   58.72 -45.00-150.00   50
 15  \w     -9.00  16.00   0.50    0.30    --   51.65 -45.00 -30.00   50
 16  \w     -2.00  23.00   0.50    0.30    --   58.72 -45.00   0.00   50
 17  \w     87.00 142.00   0.50    0.30    --   86.44  61.00 150.00  110
 18  \w     92.00 118.00   0.50    0.30    --   58.72  45.00 120.00   52
 19  \w     61.00  89.00   0.50    0.30    --   58.72  45.00 120.00   56
 20  \w     88.00 143.00   0.50    0.30    --   86.44  61.00  90.00  110
 21  \w    100.00 148.00   0.50    0.30    --   93.56  45.00  60.00   96
 22  \w     85.00 127.00   0.50    0.30    --   86.44  45.00  30.00   84
 23  \w     87.00 135.00   0.50    0.30    --   86.44  45.00 -90.00   96
 24  \w    119.00 144.00   0.50    0.30    --   93.56 111.00   0.00   50
 25  \w    103.00 149.00   0.50    0.30    --   93.56 111.00 -30.00   92
 26  \w    104.00 132.00   0.50    0.30    --   93.56 111.00 -90.00   56
 27  \w    -54.00 -28.00   0.50    0.30    --  -77.03  77.00-150.00   52
 28  \w    -48.00 -23.00   0.50    0.30    --  -77.03  61.00  30.00   50
 29  \w    -48.00 -23.00   0.50    0.30    --  -77.03  61.00 -30.00   50
 30  \w    -46.00 -21.00   0.50    0.30    --  -77.03  61.00 120.00   50
 31  \w    -54.00 -28.00   0.50    0.30    --  -77.03  70.00 159.00   52
 32  \w    -58.00 -33.00   0.50    0.30    --  -59.45  70.00 159.00   50
 33  \w    -26.00   0.00   0.50    0.30    --  -51.17  70.00 159.00   52
 34  \w    -26.00   0.00   0.50    0.30    --  -51.17  45.00-120.00   52
 35  \w    -26.00   0.00   0.50    0.30    --  -59.45  45.00-150.00   52
 36  \w   -133.00 -82.00   0.50    0.30    --  -77.03 -61.00-120.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0362410000
_diffrn_orient_matrix_UB_12      0.0710443000
_diffrn_orient_matrix_UB_13      -0.0848806000
_diffrn_orient_matrix_UB_21      0.0492211000
_diffrn_orient_matrix_UB_22      0.1370775000
_diffrn_orient_matrix_UB_23      0.0344179000
_diffrn_orient_matrix_UB_31      0.0765965000
_diffrn_orient_matrix_UB_32      -0.0546284000
_diffrn_orient_matrix_UB_33      -0.0239445000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0754
_diffrn_reflns_av_unetI/netI     0.0649
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            17860
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.156
_diffrn_reflns_theta_min         2.811
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.719
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.26375
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.129a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.680
_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         0.383
_refine_diff_density_min         -0.420
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.983
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     422
_refine_ls_number_reflns         4818
_refine_ls_number_restraints     636
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1232
_refine_ls_R_factor_gt           0.0721
_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^)+(0.1586P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2238
_refine_ls_wR_factor_ref         0.2747
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2150
_reflns_number_total             4818
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00814j2.cif
_cod_data_source_block           gn-250118-sc1-343k_autored
_cod_depositor_comments
'Adding full bibliography for 7250934--7250936.cif.'
_cod_database_code               7250934
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.623
_shelx_estimated_absorpt_t_min   0.476
_diffrn_oxdiff_digest_hkl
;
43c4e79c97d2741e8927469fb4f3ff8f2ae5f4
;
_olex2_refinement_description
;
1. Restrained distances
 N2-C15 = C14-C13 = C14A-C13A = C16A-C14A = C12A-C13A = C16-C14 = N2-C11 = C6-
 C8 = C11-C9 = N2A-C10A = C11A-C9A = C10-C12
 2.5 with sigma of 0.02
 C6A-C4A
 2.5 with sigma of 0.02
 C6A-C1A
 2.5 with sigma of 0.02
 C8A-C6A
 2.5 with sigma of 0.02
 C8-C7 = C6-C7 = C2-C1 = C2-C3 = C3-C4 = C15-C16 = C15A-C16A = C15A-C14A = C15-
 C14 = C9A-C10A = C11A-C10A = C12A-C11A = C10-C9 = C10-C11 = C12-C11
 1.5 with sigma of 0.02
 C8A-C7A = C6A-C7A = N1A-C6A = N1A-C5A = N1A-C1A = N1A-C4A = C3A-C4A = C2A-C3A
 = C2A-C1A
 1.5 with sigma of 0.02
 C7A-N1A
 2.5 with sigma of 0.02
 C6A-C5A
 2.5 with sigma of 0.02
 C3A-C1A
 2.5 with sigma of 0.02
 C4-C2
 2.5 with sigma of 0.02
 C1A-C4A
 2.5 with sigma of 0.02
 C3-N1
 2.5 with sigma of 0.02
 C2A-C4A
 2.5 with sigma of 0.02
 C6-C7 = C8-C7
 1.53 with sigma of 0.01
 C9A-C13A
 2.5 with sigma of 0.02
 N2A-C15A
 2.5 with sigma of 0.02
 N2-C12 = N2A-C13A = N2A-C12A = N2-C9 = N2-C13 = N2A-C9A = N2A-C14A = N2-C14 =
 N1-C1 = N1-C4 = N1-C6 = N1-C5
 1.49 with sigma of 0.02
 C12A-C10A = C12A-C9A
 2.5 with sigma of 0.02
 C6-C7 \\sim C8-C7
 with sigma of 0.02
 C4-C6 \\sim C6-C1
 with sigma of 0.02
 Br2A-Zn1 \\sim Br4A-Zn1 \\sim Br1A-Zn1 \\sim Br3A-Zn1
 with sigma of 0.02
 C9-C14 \\sim C14-C12
 with sigma of 0.02
 Br3-Zn1 \\sim Br2-Zn1 \\sim Br1-Zn1 \\sim Br4-Zn1 \\sim Br4A-Zn1A \\sim
Br3A-Zn1A \\sim Br1A-Zn1A ~
 Br2A-Zn1A
 with sigma of 0.02
 C9A-C14A \\sim C14A-C12A
 with sigma of 0.02
2. Rigid bond restraints
 C3, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C1, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C7, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C5, N1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 N1, C6
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 N2A, C13A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C15A, C16A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C15, C16
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C15A, C14A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 N2, C9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C10, C9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C13, N2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3. Uiso/Uaniso restraints and constraints
C8A \\sim N1A \\sim C5A \\sim C1A \\sim C4A \\sim C6A \\sim C2A \\sim C3A \\sim
C7A: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C6 \\sim C2 \\sim N1 \\sim C5 \\sim C4 \\sim C1 \\sim C3 \\sim C7 \\sim C8:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
N2 \\sim C13 \\sim C12 \\sim C9 \\sim C14 \\sim C11 \\sim C10 \\sim C15 \\sim
C16: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C4 \\sim N1 \\sim C6 \\sim C1 \\sim C5 \\sim C14 \\sim N2 \\sim C12 \\sim C12A
\\sim C9 \\sim N2A \\sim C14A \\sim C13 \\sim C9A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C6 \\sim N1 \\sim C5 \\sim C1 \\sim C4: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C9A \\sim N2A \\sim C13A \\sim C12A \\sim C15A \\sim C11A \\sim C10A \\sim C14A
\\sim C16A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Zn1 \\sim Br3A \\sim Br2 \\sim Br4 \\sim Br1A \\sim Br1 \\sim Br4A \\sim Br2A
\\sim Br3: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Uanis(C13) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C11A) \\sim Ueq, Uanis(C9A)
\\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C12A) \\sim Ueq, Uanis(N2A) \\sim Ueq,
Uanis(C14A) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C3)
\\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C2) \\sim Ueq: with
sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C6A) \\sim Ueq, Uanis(N1A) \\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C1A)
\\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C3A) \\sim Ueq,
Uanis(C7A) \\sim Ueq, Uanis(C8A) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(Br3A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C7) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(N1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Br2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N1A) \\sim Ueq, Uanis(C8A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4. Others
 Sof(Br4A)=Sof(Br2A)=Sof(Br1A)=Sof(Br3A)=Sof(Zn1A)=1-FVAR(1)
 Sof(Zn1)=Sof(Br4)=Sof(Br1)=Sof(Br3)=Sof(Br2)=FVAR(1)
 Sof(N2A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C12A)=Sof(H12C)=
 Sof(H12D)=Sof(C9A)=Sof(H9C)=Sof(H9D)=Sof(C15A)=Sof(H15C)=Sof(H15D)=Sof(C11A)=
 Sof(H11C)=Sof(H11D)=Sof(C10A)=Sof(H10C)=Sof(H10D)=Sof(C14A)=Sof(H14C)=
 Sof(H14D)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(2)
 Sof(N2)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C12)=Sof(H12A)=Sof(H12B)=
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=
 Sof(H15B)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(C16)=
 Sof(H16A)=Sof(H16B)=Sof(H16C)=FVAR(2)
 Sof(N1A)=Sof(C5A)=Sof(H5D)=Sof(H5E)=Sof(H5F)=Sof(C1A)=Sof(H1C)=Sof(H1D)=
 Sof(C4A)=Sof(H4C)=Sof(H4D)=Sof(C6A)=Sof(H6C)=Sof(H6D)=Sof(C2A)=Sof(H2C)=
 Sof(H2D)=Sof(C3A)=Sof(H3C)=Sof(H3D)=Sof(C7A)=Sof(H7C)=Sof(H7D)=Sof(C8A)=
 Sof(H8D)=Sof(H8E)=Sof(H8F)=1-FVAR(3)
 Sof(N1)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C1)=
 Sof(H1A)=Sof(H1B)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C3)=
 Sof(H3A)=Sof(H3B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=
 FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C2(H2A,H2B), C1(H1A,H1B), C7(H7A,H7B), C9(H9A,H9B), C14(H14A,
 H14B), C4(H4A,H4B), C15(H15A,H15B), C3(H3A,H3B), C6(H6A,H6B), C11(H11A,H11B),
 C10(H10A,H10B), C12A(H12C,H12D), C9A(H9C,H9D), C15A(H15C,H15D), C11A(H11C,
 H11D), C10A(H10C,H10D), C14A(H14C,H14D), C1A(H1C,H1D), C4A(H4C,H4D), C6A(H6C,
 H6D), C2A(H2C,H2D), C3A(H3C,H3D), C7A(H7C,H7D)
5.b Me refined with riding coordinates:
 C13(H13A,H13B,H13C), C16(H16A,H16B,H16C), C13A(H13D,H13E,H13F), C16A(H16D,
 H16E,H16F)
5.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), C5A(H5D,H5E,H5F), C8A(H8D,H8E,H8F)
;
_shelx_res_checksum              42751
_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 4.119
_oxdiff_exptl_absorpt_empirical_full_min 0.358