#------------------------------------------------------------------------------
#$Date: 2026-03-05 13:19:58 +0100 (Thu 05 de Mar de 2026) $
#$Revision: 304869 $
#$URL: svn://www.crystallography.net/cod/cif/1/57/61/1576135.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_1576135
loop_
_publ_author_name
'Balvanz, Adam'
'Pournara, Anastasia'
'Reynolds, Robert P.'
'Meza, Patricia E.'
'Malliakas, Christos D.'
'Fletcher, Jared D.'
'Seshadri, Ram'
'Dravid, Vinayak P.'
'Kanatzidis, Mercouri G.'
_publ_section_title
;
 Tuning optical properties and local lone-pair off-centering in "hollow"
 FA₁₋ₓ {en} ₓ Pb
 <sub>η-y</sub> Sn y Br₃
 perovskites.
;
_journal_issue                   1
_journal_name_full               'Chemical science'
_journal_page_first              526
_journal_page_last               543
_journal_paper_doi               10.1039/d5sc01841b
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'Br3 Pb0.84 Sn0.16, 4(C0.25 N0.5)'
_chemical_formula_sum            'C Br3 N2 Pb0.84 Sn0.16'
_chemical_formula_weight         472.79
_space_group_crystal_system      cubic
_space_group_IT_number           221
_space_group_name_Hall           '-P 4 2 3'
_space_group_name_H-M_alt        'P m -3 m'
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-23
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-02-21 deposited with the CCDC.	2025-10-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   5.9577(13)
_cell_length_b                   5.9577(13)
_cell_length_c                   5.9577(13)
_cell_measurement_reflns_used    4825
_cell_measurement_temperature    295
_cell_measurement_theta_max      28.66
_cell_measurement_theta_min      2.70
_cell_volume                     211.46(8)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      295
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_radiation_type           AgK\a
_diffrn_radiation_wavelength     0.56083
_diffrn_reflns_av_R_equivalents  0.0150
_diffrn_reflns_av_unetI/netI     0.0072
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            1319
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        19.664
_diffrn_reflns_theta_max         28.383
_diffrn_reflns_theta_min         2.698
_diffrn_source                   'AXO Agk\a'
_exptl_absorpt_coefficient_mu    16.858
_exptl_absorpt_correction_T_max  0.1397
_exptl_absorpt_correction_T_min  0.0969
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(μ₂-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    3.713
_exptl_crystal_description       irregular
_exptl_crystal_F_000             202
_exptl_crystal_size_max          0.210
_exptl_crystal_size_mid          0.195
_exptl_crystal_size_min          0.175
_refine_diff_density_max         0.865
_refine_diff_density_min         -1.417
_refine_diff_density_rms         0.180
_refine_ls_extinction_coef       0.081(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/1 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.336
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     9
_refine_ls_number_reflns         148
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.323
_refine_ls_R_factor_all          0.0267
_refine_ls_R_factor_gt           0.0263
_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/[σ²(Fo²)+(0.0401P)²+0.1385P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0750
_refine_ls_wR_factor_ref         0.0751
_reflns_Friedel_coverage         0.000
_reflns_number_gt                147
_reflns_number_total             148
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            d5sc01841b2.cif
_cod_data_source_block           full
_cod_depositor_comments
'Adding full bibliography for 1576135--1576153.cif.'
_cod_original_cell_volume        211.46(14)
_cod_database_code               1576135
_shelx_shelxl_version_number     2018/1
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_olex2_refinement_description
;
1. Shared sites
{Pb, Sn}
2. Restrained distances
 C_$1-N_$1
 1.45 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(N) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(Pb) = Uanis(Sn)
4. Others
 Fixed Sof: Pb(0.0175) Sn(0.00333) N(0.041667)
;
_shelx_res_file
;
TITL full_a.res in Pm-3m
    full.res
    created by SHELXL-2018/1 at 09:48:03 on 23-Oct-2024
REM Old TITL full_a.res in Pm-3m
REM SHELXT solution in Pm-3m
REM R1 0.266, Rweak 0.118, Alpha 0.044, Orientation as input
REM Formula found by SHELXT: Pb Br3
CELL 0.56083 5.9577 5.9577 5.9577 90 90 90
ZERR 1 0.0013 0.0013 0.0013 0 0 0
LATT 1
SYMM -X,-Y,+Z
SYMM -X,+Y,-Z
SYMM +X,-Y,-Z
SYMM +Z,+X,+Y
SYMM +Z,-X,-Y
SYMM -Z,-X,+Y
SYMM -Z,+X,-Y
SYMM +Y,+Z,+X
SYMM -Y,+Z,-X
SYMM +Y,-Z,-X
SYMM -Y,-Z,+X
SYMM +Y,+X,-Z
SYMM -Y,-X,-Z
SYMM +Y,-X,+Z
SYMM -Y,+X,+Z
SYMM +X,+Z,-Y
SYMM -X,+Z,+Y
SYMM -X,-Z,-Y
SYMM +X,-Z,+Y
SYMM +Z,+Y,-X
SYMM +Z,-Y,+X
SYMM -Z,+Y,+X
SYMM -Z,-Y,-X
SFAC Br C N Pb Sn
DISP Br 0.1872 1.6557 5339.1
DISP C 0.0013 0.0009 7.4
DISP N 0.003 0.002 11.7
DISP Pb -1.0526 6.9588 22729.8
DISP Sn -1.129 0.9349 3177.2
UNIT 3 1 2 0.84 0.16
EQIV $1 1+X,+Y,+Z
EADP Pb Sn
DFIX 1.45 C_$1 N_$1
ISOR N
EXYZ Pb Sn

L.S. 60
PLAN  2
TEMP 21.85
CONF
list 4
MORE -1
fmap 2
acta
OMIT -2 57
REM <olex2.extras>
REM <HklSrc "%.\\Full.hkl">
REM </olex2.extras>

WGHT    0.040100    0.138500
EXTI    0.080518
FVAR       0.86427
PART 1
PB    4    0.500000    0.500000    0.500000    10.01750    0.03895    0.03895 =
         0.03895    0.00000    0.00000    0.00000
SN    5    0.500000    0.500000    0.500000    10.00333    0.03895    0.03895 =
         0.03895    0.00000    0.00000    0.00000
BR    1    0.000000    0.500000    0.500000    10.06250    0.03717    0.10791 =
         0.10791    0.00000    0.00000    0.00000

C     2    0.000000    0.000000    0.000000    10.02083    0.15832    0.15832 =
         0.15832    0.00000    0.00000    0.00000
N     3    0.236324    0.000000    0.000000    10.04167    0.10099    0.19910 =
         0.19910    0.00000    0.00000    0.00000
HKLF 4




REM  full_a.res in Pm-3m
REM R1 =  0.0263 for     147 Fo > 4sig(Fo)  and  0.0267 for all     148 data
REM      9 parameters refined using      7 restraints

END

WGHT      0.0401      0.1385

REM Highest difference peak  0.865,  deepest hole -1.417,  1-sigma level  0.180
Q1    1   0.5000  0.0000  0.0000  10.06250  0.05    0.86
Q2    1   0.5000  0.4269  0.3502  10.50000  0.05    0.67
;
_shelx_res_checksum              81822
_olex2_submission_special_instructions 'No special instructions were received'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, -z'
'-y, -x, -z'
'y, -x, z'
'-y, x, z'
'x, z, -y'
'-x, z, y'
'-x, -z, -y'
'x, -z, y'
'z, y, -x'
'z, -y, x'
'-z, y, x'
'-z, -y, -x'
'-x, -y, -z'
'x, y, -z'
'x, -y, z'
'-x, y, z'
'-z, -x, -y'
'-z, x, y'
'z, x, -y'
'z, -x, y'
'-y, -z, -x'
'y, -z, x'
'-y, z, x'
'y, z, -x'
'-y, -x, z'
'y, x, z'
'-y, x, -z'
'y, -x, -z'
'-x, -z, y'
'x, -z, -y'
'x, z, y'
'-x, z, -y'
'-z, -y, x'
'-z, y, -x'
'z, -y, -x'
'z, y, x'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Pb Pb 0.500000 0.500000 0.500000 0.0389(3) Uani 0.84 48 d S T P . 1
Sn Sn 0.500000 0.500000 0.500000 0.0389(3) Uani 0.1599 48 d S T P . 1
Br Br 0.000000 0.500000 0.500000 0.0843(6) Uani 1 16 d S T P . 1
C C 0.000000 0.000000 0.000000 0.16(4) Uani 1 48 d S T P . 1
N N 0.236(3) 0.000000 0.000000 0.17(4) Uani 0.3334 8 d S TU P A 1
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Pb 0.0389(3) 0.0389(3) 0.0389(3) 0.000 0.000 0.000
Sn 0.0389(3) 0.0389(3) 0.0389(3) 0.000 0.000 0.000
Br 0.0372(6) 0.1079(10) 0.1079(10) 0.000 0.000 0.000
C 0.16(4) 0.16(4) 0.16(4) 0.000 0.000 0.000
N 0.10(6) 0.20(7) 0.20(7) 0.000 0.000 0.000
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Br Br 0.1872 1.6557 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0013 0.0009 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0030 0.0020 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pb Pb -1.0526 6.9588 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Sn Sn -1.1290 0.9349 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
Br Pb Br 90.0 9_556 . ?
Br Pb Br 90.0 1_655 5_565 ?
Br Pb Br 90.0 1_655 9 ?
Br Pb Br 90.0 9_556 1_655 ?
Br Pb Br 180.0 9_556 9 ?
Br Pb Br 180.0 . 1_655 ?
Br Pb Br 90.0 5_565 9 ?
Br Pb Br 90.0 9_556 5 ?
Br Pb Br 180.0 5 5_565 ?
Br Pb Br 90.0 . 5 ?
Br Pb Br 90.0 . 9 ?
Br Pb Br 90.0 1_655 5 ?
Br Pb Br 90.0 5 9 ?
Br Pb Br 90.0 9_556 5_565 ?
Br Pb Br 90.0 . 5_565 ?
Pb Br Pb 180.0 1_455 . ?
N C N 180.0 33 9 ?
N C N 90.0 25 29 ?
N C N 180.0 25 . ?
N C N 90.0 33 25 ?
N C N 90.0 33 . ?
N C N 90.0 9 25 ?
N C N 90.0 29 . ?
N C N 90.0 33 5 ?
N C N 180.0 5 29 ?
N C N 90.0 9 5 ?
N C N 90.0 9 . ?
N C N 90.0 25 5 ?
N C N 90.0 5 . ?
N C N 90.0 33 29 ?
N C N 90.0 9 29 ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Pb Br 2.9789(6) 9_556 ?
Pb Br 2.9789(6) 5_565 ?
Pb Br 2.9789(6) 5 ?
Pb Br 2.9789(6) . ?
Pb Br 2.9788(6) 1_655 ?
Pb Br 2.9789(6) 9 ?
C N 1.408(19) 33 ?
C N 1.408(19) 29 ?
C N 1.408(19) 5 ?
C N 1.408(19) 9 ?
C N 1.408(19) . ?
C N 1.408(19) 25 ?
