# Electronic Supplementary Material (ESI) for Nanoscale.
# This journal is © The Royal Society of Chemistry 2024

####################################################################### 
# 
# 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_PEROVRT
_database_code_depnum_ccdc_archive 'CCDC 2345493'
loop_
_audit_author_name
_audit_author_address
'Leonardo Lo Presti'
;Universita degli Studi di Milano
Italy
;
_audit_update_record             
;
2024-04-03 deposited with the CCDC.	2024-06-03 downloaded from the CCDC.
;
#------------------ SUBMISSION DETAILS --------------------------------------#
_audit_creation_method           SHELXL-2017/1

#------------------ Start Validation Reply Form ----------------------------#
_vrf_PLAT074_PEROVRT             
;
PROBLEM: Occupancy Parameter = 0.0 for ..................       CENT Check 
RESPONSE:  Following to Elbaz et al. Nano Lett. 2017, 17, 3, 1727--1732,
 the position of methylamonium was stabilized by placing a dummy
 He atom ("CENT") at the origin and restraining the N-dummy and C-dummy 
 distances to 0.75 \%A each. This was necessary as the MA cation
 is highly disorderd (Wyckoff multiplicity of 48).  
;
_vrf_PLAT088_PEROVRT             
;
PROBLEM: Poor Data / Parameter Ratio ....................       5.35 Note   
RESPONSE:  This is due to the very high symmetry of this system, which 
 results in 91 symmetry-independent reflections only. Data collections up
 to a resolution higher than the Cu-sphere are needed to improve the 
 data-to-parameter ratio. In any case, the quality of the present crystal
 structure determination is higher than that reported in previous 
 crystallographic studies (e.g. Elbaz et al. Nano Lett. 2017, 17, 3, 1727-
 -1732).  
;
_vrf_PLAT936_PEROVRT             
;
PROBLEM: The Embedded .res File Includes a DAMP Command .     1000.0 Report
RESPONSE: Due to the relatively poor data-to-parameter ratio and the high
 correlations, a moderate DAMP command is necessary to avoid instabilities
 in the least-squares procedure. 
;
#------------------ End of Validation Reply Form ----------------------------#
#------------------ CHEMICAL INFORMATION ------------------------------------#

_chemical_name_systematic        'Methylamonium bromide lead perovskite'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C H6 Br3 N Pb'
_chemical_formula_sum            'C H6 Br3 N Pb'
_chemical_formula_weight         478.92

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'
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'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
He He 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      cubic
_space_group_IT_number           221
_space_group_name_H-M_alt        'P m -3 m'
_space_group_name_Hall           '-P 4 2 3'

_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.
;

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'

_cell_length_a                   5.9175(3)
_cell_length_b                   5.9175(3)
_cell_length_c                   5.9175(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     207.21(3)
_cell_formula_units_Z            1
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2692
_cell_measurement_theta_min      3.44
_cell_measurement_theta_max      29.92

_exptl_crystal_description       rod
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             206
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.450
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.075
_exptl_absorpt_coefficient_mu    34.716
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.1385
_exptl_absorpt_correction_T_max  0.4326
_exptl_absorpt_process_details   'Sadabs (Bruker, 2007/4)'
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Sealed X-ray tube'
_diffrn_measurement_device_type  'Bruker AXS smart APEX II'
_diffrn_measurement_method       ω-scan
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3164
_diffrn_reflns_av_unetI/netI     0.0063
_diffrn_reflns_av_R_equivalents  0.0245
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         3.442
_diffrn_reflns_theta_max         30.162
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             91
_reflns_number_gt                91
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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.

 According to Elbaz et al. Nano Lett. 2017, 17, 3, 1727--1732,
 the position of methylamonium was stabilized by placing a dummy
 He atom at the origin and restraining the N-dummy and C-dummy 
 distances to 0.75 Å each. This was necessary as the MA cation
 is highly disorderd (Wyckoff multiplicity of 48).  
;

_computing_data_collection       'SAINT+ (Bruker AXS, Madison (USA) 1994-1996)'
_computing_cell_refinement       'SAINT+ (Bruker AXS, Madison (USA) 1994-1996)'
_computing_data_reduction        'SAINT+ (Bruker AXS, Madison (USA) 1994-1996)'
_computing_structure_solution    'SHELXS-2013/1 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2017/1 (Sheldrick, 2017)'
_computing_molecular_graphics    
'DIAMOND v3.2k (Brandenburg,Bonn,DE, 1997-2014)'
_computing_publication_material  ?
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0247P)²+0.0125P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_extinction_coef       0.0327(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         90
_refine_ls_number_parameters     17
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0106
_refine_ls_R_factor_gt           0.0106
_refine_ls_wR_factor_ref         0.0305
_refine_ls_wR_factor_gt          0.0305
_refine_ls_goodness_of_fit_ref   1.271
_refine_ls_restrained_S_all      1.271
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

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 0.02580(6) Uani 1 48 d S T P . .
Br2 Br 0.500000 0.500000 0.000000 0.0979(4) Uani 1 16 d S T P . .
N1 N -0.066(18) 0.112(16) 0.030(17) 0.039(8) Uani 0.0208 1 d G . P A -1
H1A H -0.101755 0.185651 -0.096604 0.059 Uiso 0.0208 1 d G U P A -1
H1B H 0.023687 0.198059 0.114166 0.059 Uiso 0.0208 1 d G U P A -1
H1C H -0.191313 0.079793 0.106001 0.059 Uiso 0.0208 1 d G U P A -1
C2 C 0.05(2) -0.098(16) -0.03(2) 0.039(8) Uani 0.0208 1 d G . P A -1
H2A H 0.093666 -0.175560 0.107752 0.059 Uiso 0.0208 1 d G U P A -1
H2B H 0.184713 -0.063406 -0.114231 0.059 Uiso 0.0208 1 d G U P A -1
H2C H -0.046672 -0.192563 -0.116344 0.059 Uiso 0.0208 1 d G U P A -1
CENT He 0.000000 0.000000 0.000000 0.020 Uiso 0 1 d S U P B -2


_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 2.95875(15) 9_565 ?
Pb1 Br2 2.95875(15) . ?
Pb1 Br2 2.95875(15) 1_556 ?
Pb1 Br2 2.95875(15) 5 ?
Pb1 Br2 2.95875(15) 5_655 ?
Pb1 Br2 2.95875(15) 9 ?
N1 C2 1.4644 . ?
N1 H1A 0.8897 . ?
N1 H1B 0.8900 . ?
N1 H1C 0.8893 . ?
C2 H2A 0.9597 . ?
C2 H2B 0.9598 . ?
C2 H2C 0.9607 . ?

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 90.0 9_565 . ?
Br2 Pb1 Br2 90.0 9_565 1_556 ?
Br2 Pb1 Br2 180.0 . 1_556 ?
Br2 Pb1 Br2 90.0 9_565 5 ?
Br2 Pb1 Br2 90.0 . 5 ?
Br2 Pb1 Br2 90.0 1_556 5 ?
Br2 Pb1 Br2 90.0 9_565 5_655 ?
Br2 Pb1 Br2 90.0 . 5_655 ?
Br2 Pb1 Br2 90.0 1_556 5_655 ?
Br2 Pb1 Br2 180.0 5 5_655 ?
Br2 Pb1 Br2 180.0 9_565 9 ?
Br2 Pb1 Br2 90.0 . 9 ?
Br2 Pb1 Br2 90.0 1_556 9 ?
Br2 Pb1 Br2 90.0 5 9 ?
Br2 Pb1 Br2 90.0 5_655 9 ?
Pb1 Br2 Pb1 180.0 1_554 . ?
C2 N1 H1A 109.4 . . ?
C2 N1 H1B 109.5 . . ?
H1A N1 H1B 109.5 . . ?
C2 N1 H1C 109.5 . . ?
H1A N1 H1C 109.5 . . ?
H1B N1 H1C 109.5 . . ?
N1 C2 H2A 109.5 . . ?
N1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
N1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?


_refine_diff_density_max         0.694
_refine_diff_density_min         -0.489
_refine_diff_density_rms         0.096


_exptl_crystal_recrystallization_method 
'inverse temperature crystallization from dimethylformamide (DMF)'
