The H/F substitution strategy can achieve large spontaneous polarization in 1D hybrid perovskite ferroelectrics.
Liu, Jiu-Yang; Lun, Meng-Meng; Wang, Zhi-Jie; Li, Jun-Yi; Ding, Kun; Fu, Da-Wei; Lu, Hai-Feng; Zhang, Yi; Chemical science 15 (2024) 16612–16617; doi:10.1039/d4sc03571b

data_1572605
_publ_section_title
;
 The H/F substitution strategy can achieve large spontaneous polarization
 in 1D hybrid perovskite ferroelectrics.
;
_journal_issue                   40
_journal_name_full               'Chemical science'
_journal_page_first              16612
_journal_page_last               16617
_journal_paper_doi               10.1039/d4sc03571b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         '0.5(Br6 Pb2), C10 H15 F N'
_chemical_formula_sum            'C10 H15 Br3 F N Pb'
_chemical_formula_weight         615.15
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-04-23 deposited with the CCDC.	2024-09-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.299(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   23.5064(18)
_cell_length_b                   8.9668(5)
_cell_length_c                   6.8118(4)
_cell_measurement_reflns_used    3513
_cell_measurement_temperature    420.0(2)
_cell_measurement_theta_max      30.5050
_cell_measurement_theta_min      3.4480
_cell_volume                     1420.74(16)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      420.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.841
_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    -75.00  -1.00   0.50    0.60    --   -5.53 -62.00 111.00  148
  2  \w    -22.00  65.00   0.50    0.60    --   -5.53  62.00-110.00  174
  3  \w    -64.00   1.00   0.50    0.60    --   -5.53 -57.00 -30.00  130
  4  \w    -53.00  -1.00   0.50    0.60    --   -5.53 -57.00-180.00  104
  5  \w      3.00  29.00   0.50    0.60    --    4.83 -99.00-180.00   52
  6  \w    -14.00  14.00   0.50    0.60    --    4.83 -99.00 -90.00   56
  7  \w    -16.00 -10.00   0.50    0.60    --    4.83 -99.00  60.00   12
;
_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      -0.0116056042
_diffrn_orient_matrix_UB_12      -0.0527036000
_diffrn_orient_matrix_UB_13      -0.0227109000
_diffrn_orient_matrix_UB_21      0.0171875938
_diffrn_orient_matrix_UB_22      -0.0588069000
_diffrn_orient_matrix_UB_23      0.0202998000
_diffrn_orient_matrix_UB_31      -0.1031475108
_diffrn_orient_matrix_UB_32      -0.0038646000
_diffrn_orient_matrix_UB_33      0.0014568000
_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  0.0219
_diffrn_reflns_av_unetI/netI     0.0170
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.841
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            7598
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.841
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.677
_diffrn_reflns_theta_min         2.434
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    20.298
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48178
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
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    2.876
_exptl_crystal_description       needle
_exptl_crystal_F_000             1112
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         2.792
_refine_diff_density_min         -2.758
_refine_diff_density_rms         0.435
_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     225
_refine_ls_number_reflns         1856
_refine_ls_number_restraints     659
_refine_ls_restrained_S_all      0.924
_refine_ls_R_factor_all          0.1039
_refine_ls_R_factor_gt           0.0852
_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^)+(0.1928P)^2^+25.6249P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2754
_refine_ls_wR_factor_ref         0.3068
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1103
_reflns_number_total             1856
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03571b2.cif
_cod_data_source_block           (3-F-BTAB)PbBr3-420k
_cod_depositor_comments
'Adding full bibliography for 1572604--1572606.cif.'
_cod_database_code               1572605
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N F Pb Br'
_shelx_estimated_absorpt_t_max   0.581
_shelx_estimated_absorpt_t_min   0.178
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1-C7
 1.36 with sigma of 0.02
 F2-C17
 1.36 with sigma of 0.02
 N1-C4 = N1-C1 = N1-C2 = N1-C3
 1.5 with sigma of 0.01
 N2-C14 = N2-C12 = N2-C13 = N2-C11
 1.5 with sigma of 0.01
 C15-C14
 1.51 with sigma of 0.01
 F1-C8 = F1-C6
 2.35 with sigma of 0.04
 F2-C18 = F2-C16
 2.35 with sigma of 0.04
 C5-N1
 2.458 with sigma of 0.04
 N2-C15
 2.458 with sigma of 0.01
 N1-C4 \\sim N1-C1 \\sim N1-C2 \\sim N1-C3
 with sigma of 0.02
 C3-C4 \\sim C1-C4 \\sim C1-C2 \\sim C3-C2 \\sim C2-C4 \\sim C1-C3
 with sigma of 0.02
 N2-C14 \\sim N2-C13 \\sim N2-C12 \\sim N2-C11
 with sigma of 0.02
 C4-C10 \\sim C6-C4
 with sigma of 0.02
 C14-C11 \\sim C14-C13 \\sim C11-C13 \\sim C12-C11 \\sim C14-C12 \\sim C12-C13
 with sigma of 0.02
 C16-C14 \\sim C14-C20
 with sigma of 0.02
3. Restrained planarity
 C4, F1, C7, C8, C9, C10, C5, C6
 with sigma of 0.01
 C14, C17, C18, C19, C20, C15, C16, F2
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C14 \\sim C15 \\sim N2 \\sim C20 \\sim C16 \\sim C13 \\sim C11 \\sim C12 \\sim
C19 \\sim C17 \\sim C18 \\sim F2 \\sim C10 \\sim N1 \\sim C4 \\sim C2 \\sim C3
\\sim C1 \\sim C5 \\sim C6 \\sim C9 \\sim C7 \\sim C8 \\sim F1: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C20) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(N2)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(N1) \\sim Ueq,
Uanis(C4) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C5) \\sim
Ueq, Uanis(C10) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(F1) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 C8, N1, C4, C2, C3, C1, C5, C10, C6, C9, C7, F1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F2, C14, C15, N2, C20, C16, C13, C11, C12, C19, C17, C18
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Fixed Sof: Br1(0.5) Br2(0.5) Br3(0.5) N1(0.25) C4(0.25) H4A(0.25) H4B(0.25)
 C2(0.25) H2A(0.25) H2B(0.25) H2C(0.25) C3(0.25) H3A(0.25) H3B(0.25) H3C(0.25)
 C14(0.25) H14A(0.25) H14B(0.25) F1(0.25) C7(0.25) C6(0.25) H6(0.25) C5(0.25)
 C10(0.25) H10(0.25) C9(0.25) H9(0.25) C8(0.25) H8(0.25) F2(0.25) C16(0.25)
 H16(0.25) C15(0.25) C20(0.25) H20(0.25) C19(0.25) H19(0.25) C18(0.25)
 H18(0.25) C17(0.25) N2(0.25) C13(0.25) H13A(0.25) H13B(0.25) H13C(0.25)
 C11(0.25) H11A(0.25) H11B(0.25) H11C(0.25) C12(0.25) H12A(0.25) H12B(0.25)
 H12C(0.25) C1(0.25) H1A(0.25) H1B(0.25) H1C(0.25)
7.a Riding coordinates:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C13(H13A,H13B,H13C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C1(H1A,H1B,H1C)
7.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C14(H14A,H14B)
7.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C10(H10), C9(H9), C8(H8), C16(H16), C20(H20), C19(H19), C18(H18)
7.d Fitted hexagon refined as free rotating group:
 C7(C6,C5,C10,C9,C8), C16(C15,C20,C19,C18,C17)
;
_shelx_res_checksum              24173
_shelx_hkl_checksum              83686
_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 1.764
_oxdiff_exptl_absorpt_empirical_full_min 0.620