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_7250265
_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(Br), C6 H14 N3 P, H4 N'
_chemical_formula_sum            'C6 H18 Br3 N4 P'
_chemical_formula_weight         416.94
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_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            4
_cell_length_a                   13.8322(8)
_cell_length_b                   9.9354(7)
_cell_length_c                   9.7055(8)
_cell_measurement_reflns_used    2159
_cell_measurement_temperature    382
_cell_measurement_theta_max      26.0390
_cell_measurement_theta_min      2.9150
_cell_volume                     1333.81(16)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      382
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.789
_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    -64.00  11.00   0.25    2.20    --   -5.68 -59.00  26.00  300
  2  \w    -16.00  39.00   0.25    2.20    --    6.15 -99.00   0.00  220
;
_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      -0.0066044498
_diffrn_orient_matrix_UB_12      0.0708513981
_diffrn_orient_matrix_UB_13      -0.0040553171
_diffrn_orient_matrix_UB_21      0.0517739282
_diffrn_orient_matrix_UB_22      0.0085582234
_diffrn_orient_matrix_UB_23      0.0356244016
_diffrn_orient_matrix_UB_31      0.0512061300
_diffrn_orient_matrix_UB_32      0.0004374725
_diffrn_orient_matrix_UB_33      -0.0366492789
_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  0.0449
_diffrn_reflns_av_unetI/netI     0.0654
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.789
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            5572
_diffrn_reflns_point_group_measured_fraction_full 0.766
_diffrn_reflns_point_group_measured_fraction_max 0.579
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.584
_diffrn_reflns_theta_min         2.934
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    9.167
_exptl_absorpt_correction_T_max  0.240
_exptl_absorpt_correction_T_min  0.106
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.076
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.17
_refine_diff_density_max         2.596
_refine_diff_density_min         -1.127
_refine_diff_density_rms         0.377
_refine_ls_abs_structure_details
;
 Flack x determined using 457 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.10(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     158
_refine_ls_number_reflns         2368
_refine_ls_number_restraints     11
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1106
_refine_ls_R_factor_gt           0.0870
_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^)+(0.1440P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1889
_refine_ls_wR_factor_ref         0.2076
_reflns_Friedel_coverage         0.391
_reflns_Friedel_fraction_full    0.507
_reflns_Friedel_fraction_max     0.344
_reflns_number_gt                1723
_reflns_number_total             2368
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00177c2.cif
_cod_data_source_block           382k_rt1_inv
_cod_depositor_comments
'Adding full bibliography for 7250254--7250270.cif.'
_cod_database_code               7250265
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C6H18N3Br3P
_shelx_estimated_absorpt_t_max   0.305
_shelx_estimated_absorpt_t_min   0.208
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups, All Br(H,H,H,H) groups
2. Restrained distances
 N1-H1E = N1-H1D = N1-H1F = N1-H1C
 1.03 with sigma of 0.02
 H1E-H1D = H1E-H1F = H1E-H1C = H1D-H1F = H1D-H1C = H1F-H1C
 1.75 with sigma of 0.04
3. Others
 Sof(Br2A)=1-FVAR(1)
 Sof(Br2)=FVAR(1)
 Fixed Sof: Br3(0.75) Br4(0.25)
4.a Ternary CH refined with riding coordinates:
 N3(H3), N4(H4)
4.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C3(H3A,H3B), C5(H5A,H5B), C2(H2A,H2B), C4(H4A,H4B), C1(H1A,H1B)
;
_shelx_res_checksum              33672
_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 1.871
_oxdiff_exptl_absorpt_empirical_full_min 0.584