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_7063570
_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         'I3 Pb, C8 H15 I N O'
_chemical_formula_sum            'C8 H15 I4 N O Pb'
_chemical_formula_weight         856.00
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'I 2y'
_space_group_name_H-M_alt        'I 1 2 1'
_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                 94.908(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.0496(4)
_cell_length_b                   9.9774(5)
_cell_length_c                   21.0802(13)
_cell_measurement_reflns_used    4932
_cell_measurement_temperature    301.18(10)
_cell_measurement_theta_max      29.4080
_cell_measurement_theta_min      1.9760
_cell_volume                     1686.83(16)
_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      301.18(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.796
_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  31.00   0.50    0.50    --    4.91 -84.00 108.00  138
  2  \w    -18.00   8.00   0.50    0.50    --    4.91 -99.00  60.00   52
  3  \w    -18.00  30.00   0.50    0.50    --    4.91 -99.00 -30.00   96
  4  \w    -10.00  19.00   0.50    0.50    --   -5.54 -99.00-120.00   58
  5  \w     25.00  78.00   0.50    0.50    --    4.91  37.00-120.00  106
  6  \w     -7.00  21.00   0.50    0.50    --    4.91  37.00-120.00   56
  7  \w    -14.00  11.00   0.50    0.50    --    4.91  84.00-131.00   50
;
_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      0.0412896000
_diffrn_orient_matrix_UB_12      0.0613867000
_diffrn_orient_matrix_UB_13      0.0077689000
_diffrn_orient_matrix_UB_21      0.0567753000
_diffrn_orient_matrix_UB_22      -0.0129742000
_diffrn_orient_matrix_UB_23      -0.0231925000
_diffrn_orient_matrix_UB_31      -0.0537945000
_diffrn_orient_matrix_UB_32      0.0334135000
_diffrn_orient_matrix_UB_33      -0.0232854000
_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  0.0431
_diffrn_reflns_av_unetI/netI     0.0605
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.796
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            8167
_diffrn_reflns_point_group_measured_fraction_full 0.940
_diffrn_reflns_point_group_measured_fraction_max 0.701
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.014
_diffrn_reflns_theta_min         1.939
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    17.304
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53635
_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    3.371
_exptl_crystal_description       block
_exptl_crystal_F_000             1488
_refine_diff_density_max         1.279
_refine_diff_density_min         -1.620
_refine_diff_density_rms         0.301
_refine_ls_abs_structure_details
;
 Flack x determined using 1152 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     137
_refine_ls_number_reflns         5414
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.009
_refine_ls_R_factor_all          0.0476
_refine_ls_R_factor_gt           0.0375
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0458P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0927
_refine_ls_wR_factor_ref         0.0966
_reflns_Friedel_coverage         0.676
_reflns_Friedel_fraction_full    0.873
_reflns_Friedel_fraction_max     0.596
_reflns_number_gt                3208
_reflns_number_total             5414
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj04595e2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7063569--7063571.cif.'
_cod_database_code               7063570
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pb C H N O 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
 C6-C2 = C7-C3 = C5-C4 = C8-C5 = C8-C7 = C8-C6
 1.54 with sigma of 0.0001
3.a Riding coordinates:
 O1(H1)
3.b Ternary CH refined with riding coordinates:
 C5(H5), C8(H8)
3.c Secondary CH2 refined with riding coordinates:
 C4(H4a,H4b), C3(H3a,H3b), C7(H7a,H7b), C2(H2a,H2b), C1(H1a,H1b), C6(H6a,H6b)
;
_shelx_res_checksum              75714
_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 1.754
_oxdiff_exptl_absorpt_empirical_full_min 0.640