An organic-inorganic hybrid ferroelastic with a near-room-temperature phase transition.
Bai, Yong-Ju; Qi, Jun-Chao; Hou, Ya-Ru; Xia, Zhang-Tian; Shen, Xin; Peng, Hang; Lu, Yan-Zi; Qin, Yan; Lv, Hui-Peng; Liao, Wei-Qiang; Dalton transactions (Cambridge, England : 2003) 54 (2025) 2386–2392; doi:10.1039/d4dt03193h

data_7717703
_publ_section_title
;
 An organic-inorganic hybrid ferroelastic with a near-room-temperature
 phase transition.
;
_journal_issue                   6
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2386
_journal_page_last               2392
_journal_paper_doi               10.1039/d4dt03193h
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C16 H28 N4 O2, Br4 Zn'
_chemical_formula_sum            'C16 H28 Br4 N4 O2 Zn'
_chemical_formula_weight         693.43
_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     iterative
_audit_creation_date             2024-11-10
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-11-12 deposited with the CCDC.	2024-12-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.232(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.8689(5)
_cell_length_b                   10.2058(2)
_cell_length_c                   20.2127(4)
_cell_measurement_reflns_used    17670
_cell_measurement_temperature    297.98(10)
_cell_measurement_theta_max      76.3450
_cell_measurement_theta_min      2.3360
_cell_volume                     5038.60(18)
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      297.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.970
_diffrn_measured_fraction_theta_max 0.939
_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     47.00 100.00   0.50    0.10    --  108.36 -94.00 -90.00  106
  2  \w     70.00 104.00   0.50    0.10    --  108.36-125.00  30.00   68
  3  \w     44.00  70.00   0.50    0.10    --  108.36-125.00  90.00   52
  4  \w     55.00 105.00   0.50    0.10    --  108.36 -94.00 150.00  100
  5  \w     42.00  67.00   0.50    0.10    --  108.36 -61.00  90.00   50
  6  \w     46.00  72.00   0.50    0.10    --  108.36 -61.00  30.00   52
  7  \w     78.00 104.00   0.50    0.10    --  108.36 -77.00 -90.00   52
  8  \w     49.00  75.00   0.50    0.10    --  108.36 -77.00 -90.00   52
  9  \w     35.00  72.00   0.50    0.10    --  108.36 -61.00-150.00   74
 10  \w     35.00 106.00   0.50    0.10    --  108.36 -77.00-180.00  142
 11  \w     39.00  70.00   0.50    0.10    --  108.36 -61.00  60.00   62
 12  \w     37.00 119.00   0.50    0.11    --   45.20  44.00  -3.00  164
 13  \w    -13.00  12.00   0.50    0.11    --   45.20 -44.00-154.00   50
 14  \w    -19.00  28.00   0.50    0.11    --   45.20 -19.00-150.00   94
 15  \w     96.00 178.00   0.50    0.10    --  108.36  44.00  -3.00  164
 16  \w    -24.00  32.00   0.50    0.11    --  -45.20  19.00 150.00  112
 17  \w    -69.00 -28.00   0.50    0.10    -- -102.00  61.00  30.00   82
 18  \w    -68.00 -28.00   0.50    0.10    -- -102.00  61.00   0.00   80
 19  \w    -36.00  19.00   0.50    0.11    --  -45.20  44.00  -3.00  110
 20  \w    -64.00 -32.00   0.50    0.10    -- -102.00  61.00-150.00   64
 21  \w    -69.00 -29.00   0.50    0.10    -- -102.00  61.00-180.00   80
 22  \w   -154.00-129.00   0.50    0.10    -- -102.00 -44.00-154.00   50
 23  \w   -175.00-126.00   0.50    0.10    -- -102.00 -61.00 -60.00   98
 24  \w   -113.00 -84.00   0.50    0.10    -- -102.00 -61.00 -60.00   58
 25  \w   -111.00 -32.00   0.50    0.11    --  -45.20 -44.00-154.00  158
 26  \w   -106.00 -67.00   0.50    0.10    -- -102.00 125.00  60.00   78
 27  \w    -62.00 -36.00   0.50    0.10    -- -102.00 125.00  60.00   52
;
_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      -0.0084680000
_diffrn_orient_matrix_UB_12      0.0155128000
_diffrn_orient_matrix_UB_13      0.0715667000
_diffrn_orient_matrix_UB_21      -0.0527089000
_diffrn_orient_matrix_UB_22      -0.0824469000
_diffrn_orient_matrix_UB_23      -0.0265500000
_diffrn_orient_matrix_UB_31      0.0335597000
_diffrn_orient_matrix_UB_32      -0.1254939000
_diffrn_orient_matrix_UB_33      0.0262864000
_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  0.0512
_diffrn_reflns_av_unetI/netI     0.0412
_diffrn_reflns_Laue_measured_fraction_full 0.970
_diffrn_reflns_Laue_measured_fraction_max 0.939
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            34496
_diffrn_reflns_point_group_measured_fraction_full 0.970
_diffrn_reflns_point_group_measured_fraction_max 0.939
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.626
_diffrn_reflns_theta_min         3.619
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.931
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52932
_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    1.828
_exptl_crystal_description       plate
_exptl_crystal_F_000             2704
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.702
_refine_diff_density_min         -1.275
_refine_diff_density_rms         0.167
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     497
_refine_ls_number_reflns         9960
_refine_ls_number_restraints     320
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0959
_refine_ls_R_factor_gt           0.0826
_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^)+(0.0100P)^2^+70.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1724
_refine_ls_wR_factor_ref         0.1775
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7681
_reflns_number_total             9960
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt03193h2.cif
_cod_data_source_block           EE_BPHDZnBr4_RTP
_cod_depositor_comments
'Adding full bibliography for 7717703--7717704.cif.'
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               7717703
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Zn Br'
_shelx_estimated_absorpt_t_max   0.469
_shelx_estimated_absorpt_t_min   0.268
_reflns_odcompleteness_completeness 99.64
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 C31-C30 = C32-C31 = C30-C29 = C28-C29 = C15-C16 = C15-C14 = C13-C14 = C13-C12
 = C4-C5 = C2-C1 = C3-C2 = C4-C3 = C20-C21 = C19-C20 = C19-C18 = C18-C17
 1.54 with sigma of 0.01
 Br1B-Zn1 \\sim Br1A-Zn1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 Br1B, Br1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5, C1, C2, C3, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Sof(Br1B)=1-FVAR(1)
 Sof(Br1A)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 N4(H4), N5(HB), N1(H1), N8(HC)
6.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C29(HH,HI), C5(H5A,H5B), C21(HJ,HK), C16(H16A,H16B), C1(H1A,
 H1B), C14(H14A,H14B), C17(HL,HM), C2(H2A,H2B), C15(H15A,H15B), C30(HN,HO),
 C13(H13A,H13B), C3(H3A,H3B), C31(HP,HQ), C4(H4A,H4B), C20(HR,HS), C28(HT,HU),
 C32(HV,HW), C18(HX,HY), C19(HZ,H5)
6.c Aromatic/amide H refined with riding coordinates:
 N7(H), N6(HA), N2(H2), N3(H3), C24(HD), C23(HE), C8(H8), C10(H10), C9(H9),
 C7(H7), C25(HF), C26(HG)
;
_shelx_res_checksum              42345
_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 3.201
_oxdiff_exptl_absorpt_empirical_full_min 0.520