Synthesis, crystallographic study and solid-state properties of metal-free perovskites with P-atom containing A-site cations
Matsuda, Yumi; Asai, Rentaro; Moriguchi, Jumpei; Akutagawa, Tomoyuki; Masuya-Suzuki, Atsuko; Tsunashima, Ryo; CrystEngComm 27 (2025) 2824–2829; doi:10.1039/D5CE00177C

data_7250254
_publ_section_title
;
 Synthesis, crystallographic study and solid-state properties of
 metal-free perovskites with P-atom containing A-site cations
;
_journal_issue                   18
_journal_name_full               CrystEngComm
_journal_page_first              2824
_journal_page_last               2829
_journal_paper_doi               10.1039/D5CE00177C
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         '3(I), C6 H14 N3 P, H4 N'
_chemical_formula_sum            'C6 H18 I3 N4 P'
_chemical_formula_weight         557.91
_space_group_crystal_system      orthorhombic
_space_group_IT_number           64
_space_group_name_Hall           '-C 2ac 2'
_space_group_name_H-M_alt        'C m c e'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-01-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-17 deposited with the CCDC.	2025-04-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   14.1583(4)
_cell_length_b                   14.4657(4)
_cell_length_c                   14.2413(3)
_cell_measurement_reflns_used    6138
_cell_measurement_temperature    298
_cell_measurement_theta_max      30.6570
_cell_measurement_theta_min      2.4720
_cell_volume                     2916.76(13)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_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      298
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.990
_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    -78.00 -23.00   0.25    0.25    --   -5.68 -62.00 134.00  220
  2  \w    -14.00  21.00   0.25    0.25    --    6.15 -97.00  39.00  140
  3  \w    -17.00  40.00   0.25    0.25    --    6.15 -99.00-120.00  228
;
_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      -0.0024914000
_diffrn_orient_matrix_UB_12      -0.0313885000
_diffrn_orient_matrix_UB_13      -0.0381969000
_diffrn_orient_matrix_UB_21      0.0470066000
_diffrn_orient_matrix_UB_22      -0.0143646000
_diffrn_orient_matrix_UB_23      0.0091359000
_diffrn_orient_matrix_UB_31      -0.0171270000
_diffrn_orient_matrix_UB_32      -0.0348105000
_diffrn_orient_matrix_UB_33      0.0306548000
_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  0.0197
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            6393
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         2.469
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.516
_exptl_absorpt_correction_T_max  0.36921
_exptl_absorpt_correction_T_min  0.35719
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Spherical absorption correction
using equivalent radius and absorption coefficient.
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    2.541
_exptl_crystal_description       sphere
_exptl_crystal_F_000             2048
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.17
_exptl_crystal_size_rad          0.109
_refine_diff_density_max         0.612
_refine_diff_density_min         -0.551
_refine_diff_density_rms         0.088
_refine_ls_extinction_coef       0.00064(3)
_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   1.136
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_matrix_type           full
_refine_ls_number_parameters     115
_refine_ls_number_reflns         1542
_refine_ls_number_restraints     9
_refine_ls_restrained_S_all      1.142
_refine_ls_R_factor_all          0.0177
_refine_ls_R_factor_gt           0.0170
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0216P)^2^+5.4840P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0436
_refine_ls_wR_factor_ref         0.0439
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1499
_reflns_number_total             1542
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00177c2.cif
_cod_data_source_block           p-i_298k
_cod_depositor_comments
'Adding full bibliography for 7250254--7250270.cif.'
_cod_original_sg_symbol_Hall     '-C 2bc 2'
_cod_database_code               7250254
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C6H18N4I3P
_chemical_oxdiff_usercomment     'solid solution 7-3'
_shelx_estimated_absorpt_t_max   0.404
_shelx_estimated_absorpt_t_min   0.254
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All N(H,H,H,H,H,H,H,H,H,H,H) groups
2. Restrained distances
 C1-H1B = C1-H1A
 1.09 with sigma of 0.02
 N1-H1E = N1-H1C = N1-H1D
 1.06 with sigma of 0.02
 H1A-H1B
 1.78 with sigma of 0.04
 P1-H1A = P1-H1B
 1.7 with sigma of 0.04
 H1E-H1C = H1E-H1D = H1C-H1D
 1.75 with sigma of 0.04
3. Others
 Fixed Sof: P1(0.5) C1(0.5) N2(0.5) H1A(0.5) H1B(0.5)
;
_shelx_res_checksum              89916
_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 2.362
_oxdiff_exptl_absorpt_empirical_full_min 0.506