Effect of pressure and temperature on the structure and optical properties of two-dimensional lead iodide perovskites
Drushliak, Viktoriia; Szafrański, Marek; Chemical Communications 61 (2025) 8019–8022; doi:10.1039/D5CC01232E

data_7134443
_publ_section_title
;
 Effect of pressure and temperature on the structure and optical
 properties of two-dimensional lead iodide perovskites
;
_journal_issue                   44
_journal_name_full               'Chemical Communications'
_journal_page_first              8019
_journal_page_last               8022
_journal_paper_doi               10.1039/D5CC01232E
_journal_volume                  61
_journal_year                    2025
_chemical_formula_sum            'C H6 Cs I4 N3 Pb'
_chemical_formula_weight         907.79
_chemical_name_systematic        'Cesium guanidinium lead tetraiodide'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           58
_space_group_name_Hall           '-P 2 2n'
_space_group_name_H-M_alt        'P n n m'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     heavy
_audit_creation_date             2024-10-24
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-03-03 deposited with the CCDC.	2025-04-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.820(11)
_cell_length_b                   12.0233(6)
_cell_length_c                   11.6046(6)
_cell_measurement_pressure       3150000(30000)
_cell_measurement_reflns_used    3256
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.6510
_cell_measurement_theta_min      1.7710
_cell_volume                     2486.3(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3200
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.359
_diffrn_measured_fraction_theta_max 0.282
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \f    -35.00  19.75   0.75   70.00   0.00 -30.00   0.00    --    73
  2  \f    140.00 200.00   0.75   70.00   0.00 -30.00   0.00    --    80
  3  \f    160.00 217.00   0.75   70.00   0.00  30.00   0.00    --    76
  4  \f    -20.00  34.75   0.75   70.00   0.00  30.00   0.00    --    73
  5  \w    -24.00  24.00   0.75   70.00    --   30.00  39.46 -12.90   64
  6  \w    -24.00  24.00   0.75   70.00    --   30.00  39.46 167.10   64
  7  \w    -50.00  10.00   0.75   70.00    --  -30.00  39.46 167.10   80
  8  \w    -50.00  10.00   0.75   70.00    --  -30.00  39.46 -12.90   80
  9  \w    -64.00  -8.50   0.75   70.00    --  -30.00  81.40 -28.90   74
 10  \w    -64.00  -8.50   0.75   70.00    --  -30.00  81.40 151.10   74
 11  \w    -19.00   8.00   0.75   70.00    --   30.00  81.40 151.10   36
 12  \w    -19.00   8.00   0.75   70.00    --   30.00  81.40 -28.90   36
 13  \w    -43.00 -21.25   0.75   70.00    --   30.00 134.60 -56.90   29
 14  \w    -43.00 -21.25   0.75   70.00    --   30.00 134.60 123.10   29
 15  \w    -90.00 -36.00   0.75   70.00    --  -30.00 134.60 123.10   72
 16  \w    -90.00 -36.00   0.75   70.00    --  -30.00 134.60 -56.90   72
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0386491000
_diffrn_orient_matrix_UB_12      0.0100152000
_diffrn_orient_matrix_UB_13      0.0088476000
_diffrn_orient_matrix_UB_21      -0.0083187000
_diffrn_orient_matrix_UB_22      0.0285559000
_diffrn_orient_matrix_UB_23      0.0520928000
_diffrn_orient_matrix_UB_31      0.0030000000
_diffrn_orient_matrix_UB_32      -0.0507363000
_diffrn_orient_matrix_UB_33      0.0310317000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0378
_diffrn_reflns_av_unetI/netI     0.0212
_diffrn_reflns_Laue_measured_fraction_full 0.359
_diffrn_reflns_Laue_measured_fraction_max 0.282
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            10302
_diffrn_reflns_point_group_measured_fraction_full 0.359
_diffrn_reflns_point_group_measured_fraction_max 0.282
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.722
_diffrn_reflns_theta_min         2.439
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    26.343
_exptl_absorpt_correction_T_max  0.231
_exptl_absorpt_correction_T_min  0.090
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model (Absorb Angel (2004) J. Appl. Cryst. 37:486-492)
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    4.850
_exptl_crystal_description       plate
_exptl_crystal_F_000             3056
_exptl_crystal_preparation       'mounted in a diamond-anvil cell '
_exptl_crystal_size_max          0.176
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.044
_refine_diff_density_max         0.672
_refine_diff_density_min         -0.660
_refine_diff_density_rms         0.149
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.216
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     81
_refine_ls_number_reflns         955
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.216
_refine_ls_R_factor_all          0.0611
_refine_ls_R_factor_gt           0.0335
_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^)+(0.0238P)^2^+37.0116P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0752
_refine_ls_wR_factor_ref         0.0854
_reflns_Friedel_coverage         0.000
_reflns_number_gt                617
_reflns_number_total             955
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01232e2.cif
_cod_data_source_block           CsGPbI4_3_15
_cod_depositor_comments
'Adding full bibliography for 7134427--7134444.cif.'
_cod_original_cell_volume        2486.4(16)
_cod_database_code               7134443
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.390
_shelx_estimated_absorpt_t_min   0.090
_exptl_absorpt_special_details
; 
Data were collected at room temperature and pressure of 3.15(3) GPa
(3150000 kPa). 
Pressure was determined by monitoring the shift of the ruby
R1-fluorescence line.
"_diffrn_measured_fraction_theta_full" value is low, because 
the access to the reciprocal space is restricted due to the use of
the diamond anvil cell.
;
_exptl_oxdiff_absorpt_process_details
;
Gaussian integration over a grid
of 16 x 16 x 16 points =  4096 total grid points
  Based upon method of Burnham (1966)

 Data corrected for diamond-anvil cell absorption
 Note that exptl_absorpt_correction_tmin and _tmax
 the total correction factors applied to the intensities
 The individual factors are: 
         range of dac transmission factors (min-max)      0.694     0.726
         range of gasket transmission (min-max)           0.470     1.000
         range of P media transmission (min-max)          1.000     1.000

 thickness of diamond anvil 1:  8.000 mm, mu =  0.0200 mm-1
       thickness of platten 1:  0.000 mm, mu =  0.0000 mm-1

 thickness of diamond anvil 2:  8.000 mm, mu =  0.0200 mm-1
       thickness of platten 2:  0.000 mm, mu =  0.0000 mm-1

    Gasket shadowing corrections were made based upon
    Gasket thickness = 300.0 microns, radius = 161.0 microns
    Gasket absorption coeff =        30.30 mm-1
    REFLECTION WAS CONSIDERED TOTALLY OBSCURED IF 
 FRACTION CRYSTAL ILLUMINATED WAS LESS THAN 0.00

    Non-absorbing pressure medium
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All N(H) groups, All N(H,H) groups
2. Others
 Fixed Sof: H12A(0.5) H12B(0.5)
 Fixed X: H22(0.55893)
 Fixed Y: H22(0.12215)
 Fixed Z: H22(0.062429)
3.a X=CH2 refined with riding coordinates:
 N11(H11A,H11B), N12(H12A,H12B), N21(H21A,H21B)
;
_shelx_res_checksum              51164
_shelx_hkl_checksum              21869
_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 1.421
_oxdiff_exptl_absorpt_empirical_full_min 0.575