# Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2021

####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 2046397'
loop_
_audit_author_name
_audit_author_address
Liyezhan
;Fujian Institute of Research on the Structure of Matter
China
;
_audit_update_record             
;
2020-11-25 deposited with the CCDC.	2021-02-05 downloaded from the CCDC.
;
_audit_creation_date             2020-11-24
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        γ-MPAPB
_chemical_formula_moiety         '0.5(Br8 Pb2), 2(C4 H12 N O)'
_chemical_formula_sum            'C8 H24 Br4 N2 O2 Pb'
_chemical_formula_weight         707.12
_chemical_melting_point          ?
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'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 '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'
O O 0.0106 0.0060 '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           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'x+1/2, -y+1/2, -z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, y, -z-1/2'
'-x-1/2, y-1/2, z'
'x, -y-1/2, z-1/2'

_cell_length_a                   8.1685(10)
_cell_length_b                   29.085(5)
_cell_length_c                   8.169
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1940.7(4)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    2079
_cell_measurement_temperature    272(2)
_cell_measurement_theta_max      49.012
_cell_measurement_theta_min      5.579
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    16.924
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear whiteish white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    2.420
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1790
_diffrn_reflns_av_unetI/netI     0.1000
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            9366
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        24.993
_diffrn_reflns_theta_max         24.993
_diffrn_reflns_theta_min         2.801
_diffrn_ambient_temperature      271.94
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1191
_reflns_number_total             1703
_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       ?
_computing_data_collection       ?
_computing_data_reduction        ?
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_refine_diff_density_max         1.363
_refine_diff_density_min         -2.939
_refine_diff_density_rms         0.345
_refine_ls_extinction_coef       0.0019(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   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     81
_refine_ls_number_reflns         1703
_refine_ls_number_restraints     8
_refine_ls_R_factor_all          0.0917
_refine_ls_R_factor_gt           0.0656
_refine_ls_restrained_S_all      1.065
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0947P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1537
_refine_ls_wR_factor_ref         0.1754
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C1
 1.48 with sigma of 0.02
 C2-C1 = C2-C3
 1.53 with sigma of 0.02
 O1-C3 = O1-C4
 1.44 with sigma of 0.02
 N1-C2
 2.3 with sigma of 0.02
 C1-C3
 2.4 with sigma of 0.02
 C3-C4
 2.2 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C1(H1D,H1E), C2(H2A,H2B)
3.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C)
3.c Idealised Me refined as rotating group:
 N1(H1A,H1B,H1C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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 0.000000 0.000000 0.0398(4) Uani 1 2 d S T P . .
Br2 Br 0.80040(17) 0.01740(5) -0.20007(17) 0.0575(5) Uani 1 1 d . . . . .
Br1 Br 0.4657(2) 0.09954(6) 0.0718(2) 0.0699(6) Uani 1 1 d . . . . .
N1 N 1.0509(19) 0.0864(5) 0.0305(16) 0.070(4) Uani 1 1 d D . . . .
H1A H 0.994581 0.064641 -0.021172 0.084 Uiso 1 1 calc GR . . . .
H1B H 1.003499 0.092568 0.126102 0.084 Uiso 1 1 calc GR . . . .
H1C H 1.152910 0.076788 0.047512 0.084 Uiso 1 1 calc GR . . . .
O1 O 0.9819(19) 0.2254(4) -0.082(2) 0.114(5) Uani 1 1 d D . . . .
C3 C 0.881(3) 0.1936(5) -0.156(3) 0.142(11) Uani 1 1 d D . . . .
H3A H 0.918061 0.187531 -0.266547 0.170 Uiso 1 1 calc R . . . .
H3B H 0.769926 0.205297 -0.160912 0.170 Uiso 1 1 calc R . . . .
C1 C 1.054(2) 0.1302(6) -0.075(3) 0.145(12) Uani 1 1 d D . . . .
H1D H 1.135219 0.151899 -0.035716 0.174 Uiso 1 1 calc R . . . .
H1E H 1.075378 0.123134 -0.188925 0.174 Uiso 1 1 calc R . . . .
C2 C 0.886(3) 0.1476(7) -0.051(3) 0.167(12) Uani 1 1 d D . . . .
H2A H 0.865075 0.153960 0.063923 0.200 Uiso 1 1 calc R . . . .
H2B H 0.805761 0.125679 -0.090062 0.200 Uiso 1 1 calc R . . . .
C4 C 0.942(4) 0.2688(5) -0.144(4) 0.178(14) Uani 1 1 d D . . . .
H4A H 1.011449 0.291592 -0.094280 0.267 Uiso 1 1 calc R . . . .
H4B H 0.958744 0.269094 -0.260526 0.267 Uiso 1 1 calc R . . . .
H4C H 0.829938 0.275669 -0.120193 0.267 Uiso 1 1 calc R . . . .


_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 2.9861(13) 6 ?
Pb1 Br2 2.9913(13) . ?
Pb1 Br2 2.9861(13) 2_655 ?
Pb1 Br2 2.9914(13) 5_655 ?
Pb1 Br1 2.9672(17) . ?
Pb1 Br1 2.9672(17) 5_655 ?
N1 C1 1.535(16) . ?
O1 C3 1.377(15) . ?
O1 C4 1.400(14) . ?
C3 C2 1.589(17) . ?
C1 C2 1.477(18) . ?

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 180.00(7) 6 2_655 ?
Br2 Pb1 Br2 180.0 . 5_655 ?
Br2 Pb1 Br2 88.337(15) 2_655 5_655 ?
Br2 Pb1 Br2 88.337(15) 6 . ?
Br2 Pb1 Br2 91.663(15) 6 5_655 ?
Br2 Pb1 Br2 91.663(15) 2_655 . ?
Br1 Pb1 Br2 91.17(5) . . ?
Br1 Pb1 Br2 91.17(5) 5_655 5_655 ?
Br1 Pb1 Br2 86.86(5) 5_655 2_655 ?
Br1 Pb1 Br2 88.83(5) 5_655 . ?
Br1 Pb1 Br2 93.14(5) . 2_655 ?
Br1 Pb1 Br2 86.86(5) . 6 ?
Br1 Pb1 Br2 88.83(5) . 5_655 ?
Br1 Pb1 Br2 93.14(5) 5_655 6 ?
Br1 Pb1 Br1 180.0 . 5_655 ?
Pb1 Br2 Pb1 150.17(6) 2_654 . ?
C3 O1 C4 108.1(14) . . ?
O1 C3 C2 108.2(16) . . ?
C2 C1 N1 101.2(13) . . ?
C1 C2 C3 104.0(15) . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N1 H1A Br2 0.89 2.56 3.430(16) 167.1 . yes
N1 H1B Br1 0.89 2.50 3.345(14) 159.8 6_656 yes
N1 H1C Br2 0.89 3.03 3.538(12) 117.8 5_755 yes
N1 H1C Br1 0.89 2.65 3.426(16) 146.7 1_655 yes
C4 H4B O1 0.96 2.64 3.60(4) 175.1 8_565 yes

_olex2_submission_special_instructions 'No special instructions were received'
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Hydrobromic acid aqueous solution'
