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_7063569
_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 H15 Cl N O)'
_chemical_formula_sum            'C16 H30 Cl2 I6 N2 O2 Pb2'
_chemical_formula_weight         1529.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 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                 98.576(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.8334(5)
_cell_length_b                   17.2270(7)
_cell_length_c                   8.0612(3)
_cell_measurement_reflns_used    6023
_cell_measurement_temperature    301.20(10)
_cell_measurement_theta_max      30.8660
_cell_measurement_theta_min      2.1000
_cell_volume                     1624.93(11)
_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      301.20(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 0.802
_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    -20.00  20.00   0.50    0.46    --   -5.38 -80.00 -36.00   80
  2  \w    -29.00  -3.00   0.50    0.46    --   -5.38  80.00  86.00   52
  3  \w    -18.00  14.00   0.50    0.46    --   -5.38 -99.00-150.00   64
  4  \w    -15.00  23.00   0.50    0.46    --   -5.38 -99.00 -90.00   76
  5  \w    -18.00  29.00   0.50    0.46    --    4.75 -99.00-120.00   94
  6  \w    -14.00  35.00   0.50    0.46    --    4.75 -99.00 -60.00   98
  7  \w    -17.00  27.00   0.50    0.46    --    4.75 -99.00  90.00   88
;
_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      0.0342806000
_diffrn_orient_matrix_UB_12      -0.0320555000
_diffrn_orient_matrix_UB_13      -0.0261859000
_diffrn_orient_matrix_UB_21      -0.0818681000
_diffrn_orient_matrix_UB_22      -0.0150047000
_diffrn_orient_matrix_UB_23      -0.0169738000
_diffrn_orient_matrix_UB_31      -0.0059898000
_diffrn_orient_matrix_UB_32      0.0210450000
_diffrn_orient_matrix_UB_33      -0.0519822000
_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  0.0519
_diffrn_reflns_av_unetI/netI     0.0608
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.802
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            15633
_diffrn_reflns_point_group_measured_fraction_full 0.901
_diffrn_reflns_point_group_measured_fraction_max 0.681
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.805
_diffrn_reflns_theta_min         2.104
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    16.228
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.13570
_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    3.125
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.058
_refine_diff_density_min         -1.284
_refine_diff_density_rms         0.229
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.045(11)
_refine_ls_extinction_coef       0.00151(11)
_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   0.954
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         10170
_refine_ls_number_restraints     28
_refine_ls_restrained_S_all      0.952
_refine_ls_R_factor_all          0.0532
_refine_ls_R_factor_gt           0.0368
_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^)+(0.0366P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0832
_refine_ls_wR_factor_ref         0.0882
_reflns_Friedel_coverage         0.649
_reflns_Friedel_fraction_full    0.795
_reflns_Friedel_fraction_max     0.553
_reflns_number_gt                5256
_reflns_number_total             10170
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj04595e2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7063569--7063571.cif.'
_cod_database_code               7063569
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Pb I C H N O Cl'
_shelx_estimated_absorpt_t_max   0.294
_shelx_estimated_absorpt_t_min   0.246
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.955(11)
 0.045(11)
2. 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
3. Restrained distances
 O18-C00L = O16-C17
 1.45 with sigma of 0.002
 C00L-C00D = C00K-C00E = C00M-C00L = C00M-C00K = C18-C00H = C18-C00M = C17-
 C00F = C19-C00O = C17-C00N = C1-C00N = C1-C00J = C00O-C00N
 1.54 with sigma of 0.0002
4. Rigid bond restraints
 O18, C00L
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Uiso/Uaniso restraints and constraints
O18 \\sim C00L \\sim C17 \\sim O16: within 2A with sigma of 0.1 and sigma for
terminal atoms of 0.2 within 2A
6.a Riding coordinates:
 O16(H16)
6.b Ternary CH refined with riding coordinates:
 C00L(H00L), C00M(H00M), C00N(H00s), C17(H17)
6.c Secondary CH2 refined with riding coordinates:
 C00D(H00a,H00b), C00E(H00c,H00d), C00F(H00k,H00n), C00G(H00o,H00p), C00H(H00e,
 H00f), C00I(H00g,H00h), C00J(H00q,H00r), C00K(H00i,H00j), C00O(H00t,H00u),
 C18(H18a,H18b), C19(H19a,H19b), C1(H1a,H1b)
6.d Idealised tetrahedral OH refined as rotating group:
 O18(H18)
;
_shelx_res_checksum              26189
_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 5.151
_oxdiff_exptl_absorpt_empirical_full_min 0.525