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_7250260
_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         'C6 H12 N2.902 P1.098, 3(B F4), 0.5(H8 N2)'
_chemical_formula_sum            'C6 H16 B3 F12 N3.9 P1.1'
_chemical_formula_weight         437.28
_space_group_crystal_system      tetragonal
_space_group_IT_number           86
_space_group_name_Hall           '-P 4bc'
_space_group_name_H-M_alt        'P 42/n :2'
_atom_sites_solution_hydrogens   mixed
_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            4
_cell_length_a                   10.4847(3)
_cell_length_b                   10.4847(3)
_cell_length_c                   14.8469(7)
_cell_measurement_reflns_used    3636
_cell_measurement_temperature    391
_cell_measurement_theta_max      30.1080
_cell_measurement_theta_min      2.3810
_cell_volume                     1632.10(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (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      391
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.824
_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    -62.00  47.00   0.25    3.00    --   13.22 -74.00   1.00  436
  2  \w     48.00  96.00   0.25    3.00    --   13.22 178.00 -90.00  192
  3  \w    -21.00   4.00   0.25    3.00    --   13.22  77.00   0.00  100
;
_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      0.0510816000
_diffrn_orient_matrix_UB_12      0.0224767000
_diffrn_orient_matrix_UB_13      -0.0270483000
_diffrn_orient_matrix_UB_21      0.0106133000
_diffrn_orient_matrix_UB_22      0.0504450000
_diffrn_orient_matrix_UB_23      0.0308689000
_diffrn_orient_matrix_UB_31      0.0431089000
_diffrn_orient_matrix_UB_32      -0.0390312000
_diffrn_orient_matrix_UB_33      0.0244480000
_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  0.0121
_diffrn_reflns_av_unetI/netI     0.0141
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.824
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            7333
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.824
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.183
_diffrn_reflns_theta_min         2.378
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.305
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44067
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
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    1.780
_exptl_crystal_description       block
_exptl_crystal_F_000             875
_exptl_crystal_size_max          0.233
_exptl_crystal_size_mid          0.216
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.336
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     198
_refine_ls_number_reflns         2002
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0796
_refine_ls_R_factor_gt           0.0638
_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^)+(0.1334P)^2^+0.3795P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1990
_refine_ls_wR_factor_ref         0.2220
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1439
_reflns_number_total             2002
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00177c2.cif
_cod_data_source_block           p-bf4_391k
_cod_depositor_comments
'Adding full bibliography for 7250254--7250270.cif.'
_cod_original_cell_volume        1632.10(11)
_cod_original_sg_symbol_H-M      'P 42/n'
_cod_original_formula_sum        'C6 H16 B3 F12 N3.90 P1.10'
_cod_database_code               7250260
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C6H18N4PB4F12
_chemical_oxdiff_usercomment     35
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups, All F(H,H,H,H)
  groups
2. Restrained distances
 N1-H1A = N1-H1B = N1-H1C = N1-H1D
 1.06 with sigma of 0.02
 H1A-H1B = H1A-H1C = H1A-H1D = H1B-H1C = H1B-H1D = H1C-H1D
 1.75 with sigma of 0.04
3. Others
 Sof(H1BC)=Sof(H1BD)=Sof(H4A)=Sof(H4B)=Sof(N2)=1-FVAR(1)
 Sof(P1)=Sof(H1AA)=Sof(H1AB)=Sof(H2A)=Sof(H2B)=FVAR(1)
 Sof(F2)=Sof(F3)=Sof(F8)=Sof(F5)=1-FVAR(2)
 Sof(F1)=Sof(F6)=Sof(F4)=Sof(F7)=FVAR(2)
 Sof(F9)=Sof(F11)=1-FVAR(3)
 Sof(F10)=Sof(F12)=FVAR(3)
 Fixed Sof: H3A(0.5) H3B(0.5) H1A(0.5) H1B(0.5) H1C(0.5) H1D(0.5)
4.a Ternary CH refined with riding coordinates:
 N3(H3)
4.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C1(H1AA,H1AB), C1(H1BC,H1BD), C2(H2A,H2B), C4(H4A,H4B)
;
_shelx_res_checksum              50156
_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 4.393
_oxdiff_exptl_absorpt_empirical_full_min 0.503