Solvent-assisted mechanochemical crystallization of the metal-free perovskite solid solution (H<sub>2</sub>dabco, H<sub>2</sub>hmta)NH<sub>4</sub>(BF<sub>4</sub>)<sub>3</sub>.
Moriguchi, Jumpei; Koga, Tomoe; Tsunoji, Nao; Nishihara, Sadafumi; Akutagawa, Tomoyuki; Masuya-Suzuki, Atsuko; Tsunashima, Ryo; Chemical communications (Cambridge, England) 60 (2024) 12181–12184; doi:10.1039/d4cc04010d

data_7133932
_publ_section_title
;
 Solvent-assisted mechanochemical crystallization of the metal-free
 perovskite solid solution (H<sub>2</sub>dabco,
 H<sub>2</sub>hmta)NH<sub>4</sub>(BF<sub>4</sub>)<sub>3</sub>.
;
_journal_issue                   84
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              12181
_journal_page_last               12184
_journal_paper_doi               10.1039/d4cc04010d
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         '3(B F4), 2(C3 H7 N2), H4 N'
_chemical_formula_sum            'C6 H18 B3 F12 N5'
_chemical_formula_weight         420.68
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a :2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-23
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-05-30 deposited with the CCDC.	2024-08-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   14.3261(2)
_cell_length_b                   14.3261(2)
_cell_length_c                   28.6549(8)
_cell_measurement_reflns_used    15663
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      30.8100
_cell_measurement_theta_min      2.4650
_cell_volume                     5881.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.115a (Rigaku OD, 2021)'
_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      N~2~
_diffrn_ambient_temperature      100.01(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 1.000
_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    -21.00  60.00   0.25   30.00    --   -5.57  67.00-134.00  324
  2  \w    -70.00  10.00   0.25   30.00    --   -5.57 -67.00  91.00  320
  3  \w    -17.00  29.00   0.25   30.00    --   -5.57 -99.00 -60.00  184
  4  \w     -4.00  77.00   0.25   30.00    --    6.51  38.00 -30.00  324
  5  \w    -17.00  41.00   0.25   30.00    --    6.51 -99.00-180.00  232
;
_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      -0.0231013000
_diffrn_orient_matrix_UB_12      -0.0257438000
_diffrn_orient_matrix_UB_13      -0.0177010000
_diffrn_orient_matrix_UB_21      -0.0432736000
_diffrn_orient_matrix_UB_22      0.0195229000
_diffrn_orient_matrix_UB_23      0.0070130000
_diffrn_orient_matrix_UB_31      0.0066841000
_diffrn_orient_matrix_UB_32      0.0374918000
_diffrn_orient_matrix_UB_33      -0.0158359000
_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  0.0469
_diffrn_reflns_av_unetI/netI     0.0205
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            30780
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.342
_diffrn_reflns_theta_min         1.589
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.222
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.896
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.115a (Rigaku Oxford Diffraction, 2021)
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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.901
_exptl_crystal_description       block
_exptl_crystal_F_000             3392
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.299
_refine_diff_density_min         -0.405
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     249
_refine_ls_number_reflns         2998
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0347
_refine_ls_R_factor_gt           0.0301
_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^)+(0.0449P)^2^+5.4985P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0843
_refine_ls_wR_factor_ref         0.0874
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2606
_reflns_number_total             2998
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc04010d2.cif
_cod_data_source_block           h-bf4_112k
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               7133932
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C6H18N3B3F12
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.978
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups, All N(H,H,H,H) groups
2. Others
 Fixed Sof: H1A(0.5) H1B(0.5) H4A(0.5) H4B(0.5) H5A(0.5) H5B(0.5) H8A(0.5)
 H8B(0.5)
3.a Ternary CH refined with riding coordinates:
 N1(H1), N4(H4)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B)
;
_shelx_res_checksum              75210
_shelx_hkl_checksum              69704
_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 3.807
_oxdiff_exptl_absorpt_empirical_full_min 0.338