Halogen engineering tuned band gap and structural phase transition in lead iodide hybrid perovskite semiconductors
Hu, Hui-Yi; Xu, Ya-Xin; Yuan, Shu-Ting; Ma, Jing-Yang; Xia, Guang; Shi, Shu-Ting; Zhou, Zi-Xiong; Yuan, Jin-Bin; Yu, Li-De; New Journal of Chemistry 49 (2025) 600–604; doi:10.1039/D4NJ04595E

data_7063571
_publ_section_title
;
 Halogen engineering tuned band gap and structural phase transition in
 lead iodide hybrid perovskite semiconductors
;
_journal_issue                   2
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              600
_journal_page_last               604
_journal_paper_doi               10.1039/D4NJ04595E
_journal_volume                  49
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'I6 Pb2, 2(C8 H14 Br N O)'
_chemical_formula_sum            'C16 H28 Br2 I6 N2 O2 Pb2'
_chemical_formula_weight         1616
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-08-13
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2024-08-27 deposited with the CCDC.	2024-12-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9058(10)
_cell_length_b                   8.0790(4)
_cell_length_c                   23.1217(11)
_cell_measurement_reflns_used    6812
_cell_measurement_temperature    286.9(3)
_cell_measurement_theta_max      30.5440
_cell_measurement_theta_min      2.2770
_cell_volume                     3344.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_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      286.9(3)
_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 0.817
_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    -50.00  -6.00   0.50    0.80    --   -5.38 -76.00  57.00   88
  2  \w    -18.00  26.00   0.50    0.80    --   -5.38 -99.00 -60.00   88
  3  \w     -6.00  32.00   0.50    0.80    --    4.75 -87.00 -47.00   76
  4  \w    -18.00  37.00   0.50    0.80    --    4.75 -99.00-180.00  110
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0189643000
_diffrn_orient_matrix_UB_12      0.0351272000
_diffrn_orient_matrix_UB_13      -0.0126245000
_diffrn_orient_matrix_UB_21      0.0591161000
_diffrn_orient_matrix_UB_22      0.0066708000
_diffrn_orient_matrix_UB_23      0.0220414000
_diffrn_orient_matrix_UB_31      0.0620681000
_diffrn_orient_matrix_UB_32      -0.0171197000
_diffrn_orient_matrix_UB_33      -0.0171521000
_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  0.0695
_diffrn_reflns_av_unetI/netI     0.0814
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.817
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            20563
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.762
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.742
_diffrn_reflns_theta_min         2.097
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    17.996
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.12310
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    3.209
_exptl_crystal_description       block
_exptl_crystal_F_000             2824
_refine_diff_density_max         7.542
_refine_diff_density_min         -4.192
_refine_diff_density_rms         0.667
_refine_ls_abs_structure_details
;
 Flack x determined using 1816 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(7)
_refine_ls_extinction_coef       0.00119(16)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.983
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     272
_refine_ls_number_reflns         10445
_refine_ls_number_restraints     219
_refine_ls_restrained_S_all      0.971
_refine_ls_R_factor_all          0.0975
_refine_ls_R_factor_gt           0.0712
_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^)+(0.1408P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1972
_refine_ls_wR_factor_ref         0.2136
_reflns_Friedel_coverage         0.676
_reflns_Friedel_fraction_full    0.981
_reflns_Friedel_fraction_max     0.692
_reflns_number_gt                5503
_reflns_number_total             10445
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj04595e2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7063569--7063571.cif.'
_cod_database_code               7063571
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C  H O N  Br Pb I'
_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 O(H) groups
2. Restrained distances
 C15-C10 = C9-C10 = C11-C9 = C13-C11 = C14-C12 = C9-C12 = C3-C6 = C2-C5 = C4-
 C7 = C4-C1 = C2-C1 = C3-C1
 1.54 with sigma of 0.0002
 O1-C2
 1.45 with sigma of 0.02
3. Rigid bond restraints
 C8, N1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C4, C7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
C10 \\sim N2 \\sim C15 \\sim C16 \\sim C14 \\sim C13 \\sim Br1 \\sim C12 \\sim
C11 \\sim O2 \\sim C9: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
O1: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(Br2) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C6) \\sim
Ueq, Uanis(C7) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4)
\\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(O1) \\sim Ueq,
Uanis(O2) \\sim Ueq, Uanis(N2) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C10) \\sim Ueq,
Uanis(Br1) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C9)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5.a Riding coordinates:
 O2(H2a), O1(H1a), C2(H2)
5.b Ternary CH refined with riding coordinates:
 C1(H1), C10(H10), C9(H9)
5.c Secondary CH2 refined with riding coordinates:
 C6(H6a,H6b), C12(H12a,H12b), C7(H7a,H7b), C5(H5a,H5b), C15(H15a,H15b),
 C11(H11a,H11b), C14(H14a,H14b), C4(H4a,H4b), C3(H3a,H3b), C13(H13a,H13b)
5.d Aromatic/amide H refined with riding coordinates:
 C16(H16), C8(H8)
;
_shelx_res_checksum              97842
_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 3.933
_oxdiff_exptl_absorpt_empirical_full_min 0.435