# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2023

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_CsMHyPbI6_295k
_database_code_depnum_ccdc_archive 'CCDC 2269853'
loop_
_audit_author_name
_audit_author_address
'Dawid Drozdowski'
;Institute of Low Temperature and Structure Research Polish Academy of Sciences
Poland
;
_audit_update_record             
;
2023-06-14 deposited with the CCDC.	2023-10-23 downloaded from the CCDC.
;
_audit_creation_date             2023-06-14
_audit_creation_method           
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'I6 Pb, 2(Cs), 2(C N2)'
_chemical_formula_sum            'C2 Cs2 I6 N4 Pb'
_chemical_formula_weight         1314.47
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Cs2 C2 N4 Pb I6'
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cs Cs -0.3680 2.1192 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pb Pb -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           64
_space_group_name_H-M_alt        'C m c e'
_space_group_name_Hall           '-C 2bc 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y+1/2, z+1/2'
'-x, y+1/2, -z+1/2'
'x, -y, -z'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1, z+1/2'
'-x+1/2, y+1, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x, y-1/2, -z-1/2'
'x, -y-1/2, z-1/2'
'-x, y, z'
'-x+1/2, -y+1/2, -z'
'x+1/2, y, -z-1/2'
'x+1/2, -y, z-1/2'
'-x+1/2, y+1/2, z'

_cell_length_a                   15.154(5)
_cell_length_b                   13.629(4)
_cell_length_c                   11.444(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2363.6(13)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    10874
_cell_measurement_temperature    295.00(10)
_cell_measurement_theta_max      29.0080
_cell_measurement_theta_min      2.9580
_shelx_estimated_absorpt_T_max   0.411
_shelx_estimated_absorpt_T_min   0.123
_exptl_absorpt_coefficient_mu    17.996
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25241
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    3.694
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             2200
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.06
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0377
_diffrn_reflns_av_unetI/netI     0.0119
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            23004
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.361
_diffrn_reflns_theta_min         2.685
_diffrn_ambient_temperature      295.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6249
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -78.00 -32.00   1.00   25.00    --   13.31 178.00 -30.00   46
  2  ω    -92.00  18.00   1.00   25.00    --  -14.40 -57.00 -30.00  110
  3  ω    -92.00  18.00   1.00   25.00    --  -14.40 -57.00-150.00  110
  4  ω    -47.00  64.00   1.00   25.00    --  -14.40  57.00 120.00  111
  5  ω     32.00 104.00   1.00   25.00    --   13.31-178.00 120.00   72
  6  ω    -23.00  97.00   1.00   25.00    --   13.31  77.00 150.00  120
  7  ω   -107.00 -35.00   1.00   25.00    --  -14.40-178.00  90.00   72
  8  ω    -73.00   4.00   1.00   25.00    --  -14.40 124.00 -98.00   77
  9  ω    -86.00 -53.00   1.00   25.00    --  -14.40 146.00  66.00   33
 10  ω    -47.00  64.00   1.00   25.00    --  -14.40  57.00 -60.00  111
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0348559000
_diffrn_orient_matrix_UB_12      -0.0188531000
_diffrn_orient_matrix_UB_13      0.0347446000
_diffrn_orient_matrix_UB_21      0.0310071000
_diffrn_orient_matrix_UB_22      0.0156222000
_diffrn_orient_matrix_UB_23      -0.0425526000
_diffrn_orient_matrix_UB_31      0.0037581000
_diffrn_orient_matrix_UB_32      0.0459112000
_diffrn_orient_matrix_UB_33      0.0287352000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1169
_reflns_number_total             1260
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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 (Sheldrick, 2015)'
_refine_diff_density_max         1.124
_refine_diff_density_min         -2.538
_refine_diff_density_rms         0.162
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     46
_refine_ls_number_reflns         1260
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0265
_refine_ls_R_factor_gt           0.0241
_refine_ls_restrained_S_all      1.083
_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)+(0.0326P)²+27.0295P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0664
_refine_ls_wR_factor_ref         0.0677
_refine_special_details          ?
_olex2_refinement_description    
;
1. Shared sites
{C1, N1}
2. Uiso/Uaniso restraints and constraints
Uanis(C1) = Uanis(N1)
3. Others
 Fixed Sof: N1(0.5) C1(0.5) N2(0.25) N2A(0.25)
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
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
Pb1 Pb 0.500000 0.500000 0.500000 0.03372(14) Uani 1 4 d S T P . .
I2 I 0.500000 0.61633(4) 0.74388(5) 0.03638(16) Uani 1 2 d S T P . .
I1 I 0.34347(3) 0.35915(3) 0.59308(4) 0.04894(16) Uani 1 1 d . . . . .
Cs1 Cs 0.250000 0.60932(6) 0.750000 0.0697(2) Uani 1 2 d S T P . .
N1 N 0.4180(6) 0.1272(6) 0.4203(7) 0.066(2) Uani 0.5 1 d . . P . .
C1 C 0.4180(6) 0.1272(6) 0.4203(7) 0.066(2) Uani 0.5 1 d . . P . .
N2 N 0.500000 0.1803(12) 0.4512(16) 0.057(5) Uani 0.5 2 d S T P A 1
N2A N 0.500000 0.1348(11) 0.3492(15) 0.055(5) Uani 0.5 2 d S T P A 2

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
Pb1 0.0339(3) 0.0345(2) 0.0327(2) -0.00445(17) 0.000 0.000
I2 0.0401(3) 0.0372(3) 0.0319(3) -0.0047(2) 0.000 0.000
I1 0.0476(3) 0.0446(3) 0.0546(3) 0.0038(2) 0.0079(2) -0.00973(19)
Cs1 0.0427(4) 0.0692(5) 0.0973(6) 0.000 0.0118(4) 0.000
N1 0.074(6) 0.061(5) 0.064(5) -0.001(4) 0.001(4) -0.001(4)
C1 0.074(6) 0.061(5) 0.064(5) -0.001(4) 0.001(4) -0.001(4)
N2 0.092(15) 0.037(9) 0.042(9) -0.005(7) 0.000 0.000
N2A 0.093(15) 0.035(8) 0.038(9) 0.007(7) 0.000 0.000

_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
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
Pb1 I2 3.2098(10) . ?
Pb1 I2 3.2099(10) 9_666 ?
Pb1 I1 3.2322(8) 9_666 ?
Pb1 I1 3.2321(8) . ?
Pb1 I1 3.2322(8) 4_566 ?
Pb1 I1 3.2322(8) 12_655 ?
C1 N2 1.480(12) . ?
C1 N2A 1.488(12) . ?

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
I2 Pb1 I2 180.0 . 9_666 ?
I2 Pb1 I1 89.609(19) 9_666 12_655 ?
I2 Pb1 I1 90.391(19) 9_666 4_566 ?
I2 Pb1 I1 90.391(19) 9_666 9_666 ?
I2 Pb1 I1 89.609(19) 9_666 . ?
I2 Pb1 I1 89.609(19) . 4_566 ?
I2 Pb1 I1 89.609(19) . 9_666 ?
I2 Pb1 I1 90.390(18) . . ?
I2 Pb1 I1 90.391(19) . 12_655 ?
I1 Pb1 I1 180.0 12_655 4_566 ?
I1 Pb1 I1 94.43(3) . 12_655 ?
I1 Pb1 I1 85.57(3) . 4_566 ?
I1 Pb1 I1 85.57(3) 9_666 12_655 ?
I1 Pb1 I1 94.43(3) 9_666 4_566 ?
I1 Pb1 I1 180.0 . 9_666 ?
N1 N2 C1 114.0(12) 12_655 . ?
N1 N2A C1 113.1(13) 12_655 . ?

_shelx_res_file                  
;
TITL csmhypbi_295k_a.res in Cmca
    csmhypbi_295k.res
    created by SHELXL-2018/3 at 11:20:46 on 14-Jun-2023
REM Old TITL CsMHyPbI_295K in Cmce
REM SHELXT solution in Cmca
REM R1 0.095, Rweak 0.005, Alpha 0.010, Orientation as input
REM Formula found by SHELXT: C6 I6 Cs2 Pb
CELL 0.71073 15.1544 13.6292 11.4437 90 90 90
ZERR 4 0.005 0.004 0.004 0 0 0
LATT 7
SYMM -X,0.5-Y,0.5+Z
SYMM -X,0.5+Y,0.5-Z
SYMM +X,-Y,-Z
SFAC C Cs I N Pb
UNIT 8 8 24 16 4
EADP C1 N1
EXYZ C1 N1

L.S. 40 0 0
PLAN  5
SIZE 0.06 0.14 0.2
TEMP 21.85(10)
CONF
CONN 0 Cs1
list 4
MORE -1
fmap 2 53
acta
SHEL 10 0.8
OMIT 2 0 0
REM <olex2.extras>
REM <HklSrc "%.\\CsMHyPbI_295K.hkl">
REM </olex2.extras>

WGHT    0.032600   27.029501
FVAR       0.07404
PB1   5    0.500000    0.500000    0.500000    10.25000    0.03391    0.03452 =
         0.03272   -0.00445    0.00000    0.00000
I2    3    0.500000    0.616328    0.743884    10.50000    0.04006    0.03719 =
         0.03188   -0.00474    0.00000    0.00000
I1    3    0.343468    0.359152    0.593080    11.00000    0.04761    0.04460 =
         0.05462    0.00384    0.00789   -0.00973
CS1   2    0.250000    0.609320    0.750000    10.50000    0.04267    0.06919 =
         0.09733    0.00000    0.01184    0.00000
N1    4    0.418045    0.127209    0.420315    10.50000    0.07374    0.06133 =
         0.06354   -0.00090    0.00078   -0.00065
C1    1    0.418045    0.127209    0.420315    10.50000    0.07374    0.06133 =
         0.06354   -0.00090    0.00078   -0.00065
PART 1
N2    4    0.500000    0.180324    0.451248    10.25000    0.09211    0.03694 =
         0.04199   -0.00526    0.00000    0.00000
PART 2
N2A   4    0.500000    0.134755    0.349242    10.25000    0.09330    0.03546 =
         0.03752    0.00695    0.00000    0.00000
HKLF 4




REM  csmhypbi_295k_a.res in Cmca
REM wR2 = 0.0677, GooF = S = 1.083, Restrained GooF = 1.083 for all data
REM R1 = 0.0241 for 1169 Fo > 4sig(Fo) and 0.0265 for all 1260 data
REM 46 parameters refined using 0 restraints

END

WGHT      0.0327     27.0697

REM Highest difference peak  1.124,  deepest hole -2.538,  1-sigma level  0.162
Q1    1   0.2205  0.5731  0.6908  11.00000  0.05    1.12
Q2    1   0.3218  0.4000  0.5756  11.00000  0.05    0.55
Q3    1   0.5000  0.1260  0.3192  10.50000  0.05    0.52
Q4    1   0.3628  0.3638  0.6497  11.00000  0.05    0.51
Q5    1   0.5000  0.2280  0.4232  10.50000  0.05    0.38
;
_shelx_res_checksum              15078
_olex2_date_sample_data_collection 2023-04-14
_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 3.115
_oxdiff_exptl_absorpt_empirical_full_min 0.717
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_CsMHyPbBr6_295K
_database_code_depnum_ccdc_archive 'CCDC 2269854'
loop_
_audit_author_name
_audit_author_address
'Dawid Drozdowski'
;Institute of Low Temperature and Structure Research Polish Academy of Sciences
Poland
;
_audit_update_record             
;
2023-06-14 deposited with the CCDC.	2023-10-23 downloaded from the CCDC.
;
_audit_creation_date             2023-06-14
_audit_creation_method           
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Br6 Pb, 2(Cs), 2(C N2)'
_chemical_formula_sum            'C2 Br6 Cs2 N4 Pb'
_chemical_formula_weight         1032.53
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cs Cs -0.3680 2.1192 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pb Pb -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           64
_space_group_name_H-M_alt        'C m c e'
_space_group_name_Hall           '-C 2bc 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y+1/2, z+1/2'
'-x, y+1/2, -z+1/2'
'x, -y, -z'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1, z+1/2'
'-x+1/2, y+1, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x, y-1/2, -z-1/2'
'x, -y-1/2, z-1/2'
'-x, y, z'
'-x+1/2, -y+1/2, -z'
'x+1/2, y, -z-1/2'
'x+1/2, -y, z-1/2'
'-x+1/2, y+1/2, z'

_cell_length_a                   14.280(4)
_cell_length_b                   12.876(4)
_cell_length_c                   10.772(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1980.7(11)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    10054
_cell_measurement_temperature    295.00(10)
_cell_measurement_theta_max      29.2380
_cell_measurement_theta_min      3.1210
_shelx_estimated_absorpt_T_max   0.113
_shelx_estimated_absorpt_T_min   0.062
_exptl_absorpt_coefficient_mu    24.227
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54149
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    3.463
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1768
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.16
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0397
_diffrn_reflns_av_unetI/netI     0.0124
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            19560
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.365
_diffrn_reflns_theta_min         2.848
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6249
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -78.00 -32.00   1.00   15.00    --   13.31 178.00 -90.00   46
  2  ω    -46.00  65.00   1.00   15.00    --  -14.40  37.00 -60.00  111
  3  ω    -47.00  64.00   1.00   15.00    --  -14.40  57.00   0.00  111
  4  ω    -92.00  18.00   1.00   15.00    --  -14.40 -57.00   0.00  110
  5  ω    -25.00  30.00   1.00   15.00    --  -14.40 -99.00 -90.00   55
  6  ω    -14.00  65.00   1.00   15.00    --   13.31-112.00 -76.00   79
  7  ω    -66.00  45.00   1.00   15.00    --   13.31 -37.00  60.00  111
  8  ω    -50.00  70.00   1.00   15.00    --  -14.40  77.00  90.00  120
  9  ω    -25.00  30.00   1.00   15.00    --  -14.40 -99.00  90.00   55
 10  ω    -25.00   0.00   1.00   15.00    --  -14.40 -99.00-180.00   25
 11  ω    -25.00  30.00   1.00   15.00    --  -14.40 -99.00 150.00   55
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0421608000
_diffrn_orient_matrix_UB_12      -0.0119966000
_diffrn_orient_matrix_UB_13      0.0317435000
_diffrn_orient_matrix_UB_21      0.0245826000
_diffrn_orient_matrix_UB_22      -0.0357168000
_diffrn_orient_matrix_UB_23      0.0381052000
_diffrn_orient_matrix_UB_31      0.0092446000
_diffrn_orient_matrix_UB_32      0.0401686000
_diffrn_orient_matrix_UB_33      0.0433352000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                998
_reflns_number_total             1048
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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  (Sheldrick, 2015)'
_refine_diff_density_max         1.354
_refine_diff_density_min         -1.371
_refine_diff_density_rms         0.122
_refine_ls_extinction_coef       0.00124(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     47
_refine_ls_number_reflns         1048
_refine_ls_number_restraints     15
_refine_ls_R_factor_all          0.0200
_refine_ls_R_factor_gt           0.0182
_refine_ls_restrained_S_all      1.115
_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)+(0.0163P)²+16.8275P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0445
_refine_ls_wR_factor_ref         0.0453
_refine_special_details          ?
_olex2_refinement_description    
;
1. Shared sites
{N1, C1}
2. Uiso/Uaniso restraints and constraints
Uanis(N1) = Uanis(C1)
3. Rigid body (RIGU) restrains
 N2A, N1, N2, N1, C1, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: N1(0.5) C1(0.5) N2(0.25) N2A(0.25)
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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
Pb1 Pb 0.500000 0.500000 0.500000 0.02401(12) Uani 1 4 d S T P . .
Cs1 Cs 0.250000 0.61047(4) 0.750000 0.05206(17) Uani 1 2 d S T P . .
Br2 Br 0.500000 0.61688(5) 0.74215(6) 0.02742(16) Uani 1 2 d S T P . .
Br1 Br 0.34479(4) 0.36077(4) 0.59215(5) 0.03973(15) Uani 1 1 d . . . . .
N1 N 0.4140(4) 0.1283(4) 0.4215(5) 0.0504(13) Uani 0.5 1 d . . P . .
C1 C 0.4140(4) 0.1283(4) 0.4215(5) 0.0504(13) Uani 0.5 1 d . . P . .
N2 N 0.500000 0.1841(8) 0.4540(10) 0.032(2) Uani 0.5 2 d S T P . .
N2A N 0.500000 0.1353(9) 0.3477(11) 0.044(3) Uani 0.5 2 d S T P . .

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
Pb1 0.02189(18) 0.02733(19) 0.02283(18) -0.00477(13) 0.000 0.000
Cs1 0.0285(3) 0.0570(3) 0.0706(4) 0.000 0.0105(2) 0.000
Br2 0.0291(3) 0.0310(3) 0.0222(3) -0.0020(2) 0.000 0.000
Br1 0.0378(3) 0.0383(3) 0.0431(3) 0.0026(2) 0.0063(2) -0.0083(2)
N1 0.063(3) 0.043(3) 0.045(3) 0.004(2) 0.000(3) -0.006(2)
C1 0.063(3) 0.043(3) 0.045(3) 0.004(2) 0.000(3) -0.006(2)
N2 0.055(6) 0.019(5) 0.021(4) 0.006(4) 0.000 0.000
N2A 0.074(7) 0.031(6) 0.027(5) 0.007(4) 0.000 0.000

_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
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
Pb1 Br2 3.0115(11) . ?
Pb1 Br2 3.0115(11) 9_666 ?
Pb1 Br1 3.0186(8) 4_566 ?
Pb1 Br1 3.0186(8) 12_655 ?
Pb1 Br1 3.0186(8) . ?
Pb1 Br1 3.0186(8) 9_666 ?
N1 N2 1.466(8) . ?
N1 N2A 1.466(8) . ?

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
Br2 Pb1 Br2 180.0 . 9_666 ?
Br2 Pb1 Br1 90.69(2) 9_666 9_666 ?
Br2 Pb1 Br1 89.32(2) . 4_566 ?
Br2 Pb1 Br1 90.68(2) . . ?
Br2 Pb1 Br1 89.31(2) 9_666 12_655 ?
Br2 Pb1 Br1 89.32(2) 9_666 . ?
Br2 Pb1 Br1 90.69(2) 9_666 4_566 ?
Br2 Pb1 Br1 89.32(2) . 9_666 ?
Br2 Pb1 Br1 90.68(2) . 12_655 ?
Br1 Pb1 Br1 180.0 12_655 4_566 ?
Br1 Pb1 Br1 85.51(3) 9_666 12_655 ?
Br1 Pb1 Br1 94.49(3) 9_666 4_566 ?
Br1 Pb1 Br1 180.0 . 9_666 ?
Br1 Pb1 Br1 85.51(3) . 4_566 ?
Br1 Pb1 Br1 94.49(3) . 12_655 ?
N2 N1 N2A 52.9(6) . . ?
N1 N2 N1 113.9(8) . 12_655 ?
N1 N2A N1 113.8(9) . 12_655 ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
N2 N1 N2A N1 40.1(8) . . . 12_655 ?
N2A N1 N2 N1 -40.2(8) . . . 12_655 ?

_shelx_res_file                  
;
TITL MHyCsPbBr_01_295_00 in Cmce
    mhycspbbr_01_295_00.res
    created by SHELXL-2018/3 at 11:22:51 on 14-Jun-2023
REM Cmce (#64, found as Ccme in ba-c setting)
CELL 0.71073 14.279893 12.876158 10.772031 90 90 90
ZERR 4 0.004 0.004 0.004 0 0 0
LATT 7
SYMM -X,0.5-Y,0.5+Z
SYMM -X,0.5+Y,0.5-Z
SYMM +X,-Y,-Z
SFAC Br C Cs N Pb
UNIT 24 8 8 16 4
EADP N1 C1
RIGU N2A N1 N2 N1 C1 C1
EXYZ N1 C1

L.S. 40
PLAN  5
SIZE 0.16 0.22 0.26
TEMP 21.85(10)
CONF
FREE N2 N2A
CONN 0 Cs1
list 4
MORE -1
fmap 2 53
acta
SHEL 10 0.8
OMIT 2 0 0
REM <olex2.extras>
REM <HklSrc "%.\\MHyCsPbBr_01_295_00.hkl">
REM </olex2.extras>

WGHT    0.016300   16.827499
EXTI    0.001239
FVAR       0.81637
PB1   5    0.500000    0.500000    0.500000    10.25000    0.02189    0.02733 =
         0.02283   -0.00477    0.00000    0.00000
CS1   3    0.250000    0.610473    0.750000    10.50000    0.02852    0.05704 =
         0.07061    0.00000    0.01045    0.00000
BR2   1    0.500000    0.616876    0.742154    10.50000    0.02910    0.03098 =
         0.02218   -0.00203    0.00000    0.00000
BR1   1    0.344788    0.360770    0.592151    11.00000    0.03778    0.03831 =
         0.04310    0.00256    0.00629   -0.00832
N1    4    0.413978    0.128315    0.421540    10.50000    0.06320    0.04310 =
         0.04498    0.00388   -0.00045   -0.00563
C1    2    0.413978    0.128315    0.421540    10.50000    0.06320    0.04310 =
         0.04498    0.00388   -0.00045   -0.00563
N2    4    0.500000    0.184124    0.454022    10.25000    0.05504    0.01943 =
         0.02070    0.00611    0.00000    0.00000
N2A   4    0.500000    0.135316    0.347741    10.25000    0.07413    0.03090 =
         0.02743    0.00668    0.00000    0.00000
HKLF 4




REM  MHyCsPbBr_01_295_00 in Cmce
REM wR2 = 0.0453, GooF = S = 1.121, Restrained GooF = 1.115 for all data
REM R1 = 0.0182 for 998 Fo > 4sig(Fo) and 0.0200 for all 1048 data
REM 47 parameters refined using 15 restraints

END

WGHT      0.0163     16.8276

REM Highest difference peak  1.354,  deepest hole -1.371,  1-sigma level  0.122
Q1    1   0.2274  0.5803  0.7018  11.00000  0.05    1.35
Q2    1   0.2357  0.6379  0.7612  11.00000  0.05    0.74
Q3    1   0.3824  0.1264  0.3660  11.00000  0.05    0.50
Q4    1   0.5000  0.2203  0.4205  10.50000  0.05    0.50
Q5    1   0.3681  0.1506  0.3819  11.00000  0.05    0.47
;
_shelx_res_checksum              75366
_olex2_date_sample_data_collection 2023-03-07
_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 1.339
_oxdiff_exptl_absorpt_empirical_full_min 0.675
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_CsMHyPbBr3I3_295k
_database_code_depnum_ccdc_archive 'CCDC 2269855'
loop_
_audit_author_name
_audit_author_address
'Dawid Drozdowski'
;Institute of Low Temperature and Structure Research Polish Academy of Sciences
Poland
;
_audit_update_record             
;
2023-06-14 deposited with the CCDC.	2023-10-23 downloaded from the CCDC.
;
_audit_creation_date             2023-06-14
_audit_creation_method           
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Br3 I3 Pb, 2(Cs), 2(C N2)'
_chemical_formula_sum            'C2 Br3 Cs2 I3 N4 Pb'
_chemical_formula_weight         1173.50
_chemical_melting_point          ?
_chemical_oxdiff_formula         'Cs2 Pb Br3 I3 C2 N4 '
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cs Cs -0.3680 2.1192 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
I I -0.4742 1.8119 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Pb Pb -3.3944 10.1111 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           64
_space_group_name_H-M_alt        'C m c e'
_space_group_name_Hall           '-C 2bc 2'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y+1/2, z+1/2'
'-x, y+1/2, -z+1/2'
'x, -y, -z'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1, z+1/2'
'-x+1/2, y+1, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x, y-1/2, -z-1/2'
'x, -y-1/2, z-1/2'
'-x, y, z'
'-x+1/2, -y+1/2, -z'
'x+1/2, y, -z-1/2'
'x+1/2, -y, z-1/2'
'-x+1/2, y+1/2, z'

_cell_length_a                   14.666(4)
_cell_length_b                   13.245(4)
_cell_length_c                   10.986(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2134.1(12)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    19657
_cell_measurement_temperature    295.00(10)
_cell_measurement_theta_max      29.1360
_cell_measurement_theta_min      3.5520
_shelx_estimated_absorpt_T_max   0.143
_shelx_estimated_absorpt_T_min   0.073
_exptl_absorpt_coefficient_mu    21.208
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39607
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    3.652
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1984
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.15
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0335
_diffrn_reflns_av_unetI/netI     0.0080
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            41673
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.370
_diffrn_reflns_theta_min         2.778
_diffrn_ambient_temperature      295.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6249
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -19.00  91.00   1.00   11.00    --   13.39  57.00 -30.00  110
  2  ω    -23.00  97.00   1.00   11.00    --   13.39  77.00  30.00  120
  3  ω    -78.00 -32.00   1.00   11.00    --   13.39 178.00  30.00   46
  4  ω    -89.00 -11.00   1.00   11.00    --  -14.56 148.00  66.26   78
  5  ω   -106.00  77.00   1.00   11.00    --  -14.56   0.00  90.00  183
  6  ω    -94.00  17.00   1.00   11.00    --  -14.56 -37.00  60.00  111
  7  ω    -54.00  39.00   1.00   11.00    --  -14.56  87.00 -13.47   93
  8  ω    -73.00   5.00   1.00   11.00    --  -14.56 123.00-167.66   78
  9  ω     13.00  87.00   1.00   11.00    --   13.39-149.00 129.00   74
 10  ω     35.00 106.00   1.00   11.00    --   13.39 178.00 -60.00   71
 11  ω    -79.00 105.00   1.00   11.00    --   13.39   0.00-180.00  184
 12  ω    -79.00 105.00   1.00   11.00    --   13.39   0.00-150.00  184
 13  ω    -79.00 105.00   1.00   11.00    --   13.39   0.00-120.00  184
 14  ω   -105.00 -32.00   1.00   11.00    --  -14.56 178.00-150.00   73
 15  ω    -79.00  59.00   1.00   11.00    --   13.39   0.00 -90.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0220725000
_diffrn_orient_matrix_UB_12      -0.0029827000
_diffrn_orient_matrix_UB_13      -0.0573464000
_diffrn_orient_matrix_UB_21      0.0429292000
_diffrn_orient_matrix_UB_22      0.0051178000
_diffrn_orient_matrix_UB_23      0.0290754000
_diffrn_orient_matrix_UB_31      0.0028985500
_diffrn_orient_matrix_UB_32      -0.0532169500
_diffrn_orient_matrix_UB_33      0.0060140000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1097
_reflns_number_total             1139
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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  (Sheldrick, 2015)'
_refine_diff_density_max         0.875
_refine_diff_density_min         -1.282
_refine_diff_density_rms         0.170
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.125
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     46
_refine_ls_number_reflns         1139
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0239
_refine_ls_R_factor_gt           0.0228
_refine_ls_restrained_S_all      1.125
_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)+(0.0331P)²+16.3684P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0612
_refine_ls_wR_factor_ref         0.0619
_refine_special_details          ?
_olex2_refinement_description    
;
1. Shared sites
{Br1, I1}
{N1, C1}
2. Uiso/Uaniso restraints and constraints
Uanis(Br1) = Uanis(I1)
Uanis(N1) = Uanis(C1)
3. Rigid body (RIGU) restrains
 N2, N2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Fixed Sof: Br1(0.25) I1(0.75) N1(0.5) C1(0.5) N2(0.25) N2A(0.25)
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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
Pb1 Pb 0.500000 0.500000 0.500000 0.02911(12) Uani 1 4 d S T P . .
Cs1 Cs 0.250000 0.60821(5) 0.750000 0.05665(18) Uani 1 2 d S T P . .
Br1 Br 0.34255(3) 0.35802(3) 0.59377(4) 0.04495(14) Uani 0.25 1 d . . P . .
Br2 Br 0.500000 0.61645(6) 0.73815(6) 0.03495(18) Uani 1 2 d S T P . .
I1 I 0.34255(3) 0.35802(3) 0.59377(4) 0.04495(14) Uani 0.75 1 d . . P . .
N1 N 0.4177(6) 0.1252(5) 0.4234(7) 0.0681(19) Uani 0.5 1 d . . P . .
C1 C 0.4177(6) 0.1252(5) 0.4234(7) 0.0681(19) Uani 0.5 1 d . . P . .
N2 N 0.500000 0.1807(9) 0.4527(11) 0.033(3) Uani 0.5 2 d S T P A 1
N2A N 0.500000 0.1379(14) 0.3523(19) 0.070(5) Uani 0.5 2 d S T P A 2

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
Pb1 0.02412(19) 0.0337(2) 0.0295(2) -0.00370(13) 0.000 0.000
Cs1 0.0362(3) 0.0616(4) 0.0721(4) 0.000 0.0135(3) 0.000
Br1 0.0403(3) 0.0455(2) 0.0492(3) 0.00138(17) 0.00753(18) -0.00921(17)
Br2 0.0323(4) 0.0432(4) 0.0294(3) -0.0032(3) 0.000 0.000
I1 0.0403(3) 0.0455(2) 0.0492(3) 0.00138(17) 0.00753(18) -0.00921(17)
N1 0.079(5) 0.062(4) 0.063(4) -0.001(3) -0.007(4) -0.002(4)
C1 0.079(5) 0.062(4) 0.063(4) -0.001(3) -0.007(4) -0.002(4)
N2 0.048(8) 0.025(6) 0.027(6) -0.004(5) 0.000 0.000
N2A 0.076(13) 0.063(11) 0.071(12) 0.029(9) 0.000 0.000

_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
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
Pb1 Br1 3.1512(7) . ?
Pb1 Br1 3.1513(7) 12_655 ?
Pb1 Br1 3.1513(7) 4_566 ?
Pb1 Br1 3.1513(7) 9_666 ?
Pb1 Br2 3.0371(11) . ?
Pb1 Br2 3.0371(11) 9_666 ?
N1 N2 1.450(10) . ?
N1 N2A 1.448(13) . ?

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
Br1 Pb1 Br1 180.0 . 9_666 ?
Br1 Pb1 Br1 180.0 4_566 12_655 ?
Br1 Pb1 Br1 85.76(3) 9_666 12_655 ?
Br1 Pb1 Br1 94.24(3) 9_666 4_566 ?
Br1 Pb1 Br1 94.24(3) . 12_655 ?
Br1 Pb1 Br1 85.76(3) . 4_566 ?
Br2 Pb1 Br1 91.23(2) 9_666 4_566 ?
Br2 Pb1 Br1 91.23(2) . . ?
Br2 Pb1 Br1 88.77(2) . 9_666 ?
Br2 Pb1 Br1 88.77(2) . 4_566 ?
Br2 Pb1 Br1 91.23(2) 9_666 9_666 ?
Br2 Pb1 Br1 88.77(2) 9_666 . ?
Br2 Pb1 Br1 88.77(2) 9_666 12_655 ?
Br2 Pb1 Br1 91.23(2) . 12_655 ?
Br2 Pb1 Br2 180.0 9_666 . ?
N1 N2 N1 112.8(10) 12_655 . ?
N1 N2A N1 113.1(14) 12_655 . ?

_shelx_res_file                  
;
TITL csmhypbbri_295k_c.res in Cmca
    csmhypbbri_295k.res
    created by SHELXL-2018/3 at 11:20:32 on 14-Jun-2023
REM Old TITL CsMHyPbBrI_295K in Cmce
REM SHELXT solution in Cmca: R1 0.133, Rweak 0.025, Alpha 0.011
REM <I/s> 0.987 for 103 systematic absences, Orientation as input
REM Formula found by SHELXT: C6 Br8 Pb
CELL 0.71073 14.666138 13.24541 10.985975 90 90 90
ZERR 4 0.004 0.004 0.004 0 0 0
LATT 7
SYMM -X,0.5-Y,0.5+Z
SYMM -X,0.5+Y,0.5-Z
SYMM +X,-Y,-Z
SFAC Br C Cs I N Pb
UNIT 12 8 8 12 16 4
EADP Br1 I1
EADP N1 C1
RIGU N2 N2A
EXYZ Br1 I1
EXYZ N1 C1

L.S. 40
PLAN  5
SIZE 0.15 0.19 0.26
TEMP 21.85(10)
CONF
CONN 0 Cs1
LIST 4
MORE -1
fmap 2
acta
SHEL 10 0.8
OMIT 1 3 1
OMIT 2 2 1
OMIT 0 2 3
REM <olex2.extras>
REM <HklSrc "%.\\CsMHyPbBrI_295K.hkl">
REM </olex2.extras>

WGHT    0.033100   16.368399
FVAR       0.90841
PB1   6    0.500000    0.500000    0.500000    10.25000    0.02412    0.03375 =
         0.02946   -0.00370    0.00000    0.00000
CS1   3    0.250000    0.608206    0.750000    10.50000    0.03623    0.06157 =
         0.07215    0.00000    0.01355    0.00000
BR1   1    0.342549    0.358016    0.593768    10.25000    0.04025    0.04545 =
         0.04915    0.00138    0.00753   -0.00921
BR2   1    0.500000    0.616452    0.738148    10.50000    0.03226    0.04323 =
         0.02936   -0.00318    0.00000    0.00000
I1    4    0.342549    0.358016    0.593768    10.75000    0.04025    0.04545 =
         0.04915    0.00138    0.00753   -0.00921
N1    5    0.417666    0.125193    0.423379    10.50000    0.07925    0.06164 =
         0.06337   -0.00133   -0.00745   -0.00224
C1    2    0.417666    0.125193    0.423379    10.50000    0.07925    0.06164 =
         0.06337   -0.00133   -0.00745   -0.00224
PART 1
N2    5    0.500000    0.180693    0.452719    10.25000    0.04813    0.02520 =
         0.02654   -0.00350    0.00000    0.00000
PART 2
N2A   5    0.500000    0.137865    0.352326    10.25000    0.07591    0.06258 =
         0.07091    0.02850    0.00000    0.00000
HKLF 4




REM  csmhypbbri_295k_c.res in Cmca
REM wR2 = 0.0619, GooF = S = 1.125, Restrained GooF = 1.125 for all data
REM R1 = 0.0228 for 1097 Fo > 4sig(Fo) and 0.0239 for all 1139 data
REM 46 parameters refined using 0 restraints

END

WGHT      0.0331     16.3689

REM Highest difference peak  0.875,  deepest hole -1.282,  1-sigma level  0.170
Q1    1   0.5000  0.4436  0.5017  10.50000  0.05    0.87
Q2    1   0.5483  0.5000  0.5000  10.50000  0.05    0.87
Q3    1   0.2299  0.5700  0.6939  11.00000  0.05    0.58
Q4    1   0.5000  0.5837  0.7756  10.50000  0.05    0.54
Q5    1   0.3790  0.1750  0.4610  11.00000  0.05    0.49
;
_shelx_res_checksum              28104
_olex2_date_sample_data_collection 2023-04-11
_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 1.953
_oxdiff_exptl_absorpt_empirical_full_min 0.683
