# Electronic Supplementary Material (ESI) for CrystEngComm.
# This journal is © The Royal Society of Chemistry 2022

####################################################################### 
# 
# 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_S_RT
_database_code_depnum_ccdc_archive 'CCDC 2181247'
loop_
_audit_author_name
_audit_author_address
'Prof. R. Boomishankar'
;Professor in Chemistry, IISER Pune
India
;
_audit_update_record             
;
2022-06-22 deposited with the CCDC.	2022-08-11 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C18 H28 Bi Br5 N2'
_chemical_formula_weight         880.95

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'
Bi Bi -4.1077 10.2566 '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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

_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+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   8.016(3)
_cell_length_b                   15.184(7)
_cell_length_c                   21.635(9)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2633.4(19)
_cell_formula_units_Z            4
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    4654
_cell_measurement_theta_min      4.135
_cell_measurement_theta_max      25.022

_exptl_crystal_description       rod
_exptl_crystal_colour            white
_exptl_crystal_density_meas      2.222
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.222
_exptl_crystal_F_000             1632
_exptl_transmission_factor_min   0.429
_exptl_transmission_factor_max   0.565
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_exptl_absorpt_coefficient_mu    14.288
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            62591
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_av_R_equivalents  0.1010
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         3.024
_diffrn_reflns_theta_max         25.022
_diffrn_reflns_theta_full        25.022
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             4648
_reflns_number_gt                4198
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.751
_reflns_Friedel_fraction_max     1.000
_reflns_Friedel_fraction_full    1.000

_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.
;

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_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)+(0.0209P)²+8.4113P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 1634 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.027(7)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         4648
_refine_ls_number_parameters     241
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0448
_refine_ls_R_factor_gt           0.0348
_refine_ls_wR_factor_ref         0.0764
_refine_ls_wR_factor_gt          0.0720
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_restrained_S_all      1.123
_refine_ls_shift/su_max          0.003
_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
Bi1 Bi 0.57067(5) 0.60950(3) 0.50837(2) 0.02802(13) Uani 1 1 d . . . . .
Br1 Br 0.5399(2) 0.64728(10) 0.63704(6) 0.0502(4) Uani 1 1 d . . . . .
Br2 Br 0.28515(16) 0.50819(9) 0.50798(8) 0.0474(4) Uani 1 1 d . . . . .
Br3 Br 0.61726(17) 0.62106(9) 0.37519(6) 0.0415(3) Uani 1 1 d . . . . .
Br4 Br 0.8598(2) 0.72936(10) 0.51667(9) 0.0609(5) Uani 1 1 d . . . . .
Br5 Br 0.78334(19) 0.47297(10) 0.51813(8) 0.0580(5) Uani 1 1 d . . . . .
N31 N 0.4545(14) 0.3896(8) 0.8944(5) 0.049(3) Uani 1 1 d . . . . .
H31A H 0.4129 0.3355 0.8904 0.074 Uiso 1 1 calc R U . . .
H31B H 0.4320 0.4099 0.9321 0.074 Uiso 1 1 calc R U . . .
H31C H 0.5645 0.3880 0.8889 0.074 Uiso 1 1 calc R U . . .
N41 N 0.3846(17) 0.3581(8) 0.1298(5) 0.060(4) Uani 1 1 d . . . . .
H41A H 0.4256 0.3040 0.1253 0.091 Uiso 1 1 calc R U . . .
H41B H 0.3904 0.3866 0.0939 0.091 Uiso 1 1 calc R U . . .
H41C H 0.2787 0.3549 0.1419 0.091 Uiso 1 1 calc R U . . .
C11 C 0.428(3) 0.2854(12) 0.6032(8) 0.083(6) Uani 1 1 d . . . . .
H11A H 0.3455 0.2400 0.6005 0.124 Uiso 1 1 calc R U . . .
H11B H 0.5371 0.2602 0.5974 0.124 Uiso 1 1 calc R U . . .
H11C H 0.4083 0.3287 0.5717 0.124 Uiso 1 1 calc R U . . .
C12 C 0.420(2) 0.3286(10) 0.6659(7) 0.054(4) Uani 1 1 d . . . . .
C13 C 0.314(2) 0.2953(11) 0.7121(8) 0.060(5) Uani 1 1 d . . . . .
H13 H 0.2512 0.2451 0.7042 0.072 Uiso 1 1 calc R U . . .
C14 C 0.3029(18) 0.3354(10) 0.7686(7) 0.049(4) Uani 1 1 d . . . . .
H14 H 0.2298 0.3123 0.7978 0.058 Uiso 1 1 calc R U . . .
C15 C 0.3955(16) 0.4086(9) 0.7839(6) 0.039(3) Uani 1 1 d . . . . .
C16 C 0.3768(18) 0.4494(9) 0.8467(7) 0.045(4) Uani 1 1 d . . . . .
H16 H 0.2572 0.4528 0.8558 0.054 Uiso 1 1 calc R U . . .
C17 C 0.449(2) 0.5408(10) 0.8550(7) 0.063(5) Uani 1 1 d . . . . .
H17A H 0.5672 0.5390 0.8491 0.095 Uiso 1 1 calc R U . . .
H17B H 0.4244 0.5615 0.8960 0.095 Uiso 1 1 calc R U . . .
H17C H 0.3995 0.5800 0.8253 0.095 Uiso 1 1 calc R U . . .
C18 C 0.501(2) 0.4412(10) 0.7384(7) 0.051(4) Uani 1 1 d . . . . .
H18 H 0.5676 0.4900 0.7470 0.061 Uiso 1 1 calc R U . . .
C19 C 0.510(2) 0.4017(11) 0.6795(7) 0.052(4) Uani 1 1 d . . . . .
H19 H 0.5793 0.4260 0.6495 0.062 Uiso 1 1 calc R U . . .
C21 C 0.425(3) 0.2707(13) 0.4289(9) 0.093(6) Uani 1 1 d . . . . .
H21A H 0.3685 0.3127 0.4546 0.140 Uiso 1 1 calc R U . . .
H21B H 0.5362 0.2618 0.4441 0.140 Uiso 1 1 calc R U . . .
H21C H 0.3655 0.2159 0.4296 0.140 Uiso 1 1 calc R U . . .
C22 C 0.432(2) 0.3048(10) 0.3637(7) 0.054(4) Uani 1 1 d . . . . .
C23 C 0.360(2) 0.2627(10) 0.3138(9) 0.065(5) Uani 1 1 d . . . . .
H23 H 0.3020 0.2106 0.3206 0.077 Uiso 1 1 calc R U . . .
C24 C 0.371(2) 0.2953(10) 0.2539(8) 0.059(4) Uani 1 1 d . . . . .
H24 H 0.3179 0.2658 0.2219 0.071 Uiso 1 1 calc R U . . .
C25 C 0.4595(16) 0.3701(9) 0.2418(6) 0.040(3) Uani 1 1 d . . . . .
C26 C 0.4841(18) 0.4067(11) 0.1773(7) 0.052(4) Uani 1 1 d . . . . .
H26 H 0.6022 0.3999 0.1667 0.063 Uiso 1 1 calc R U . . .
C27 C 0.440(3) 0.5032(11) 0.1706(7) 0.076(5) Uani 1 1 d . . . . .
H27A H 0.4706 0.5231 0.1300 0.114 Uiso 1 1 calc R U . . .
H27B H 0.4998 0.5368 0.2010 0.114 Uiso 1 1 calc R U . . .
H27C H 0.3224 0.5109 0.1765 0.114 Uiso 1 1 calc R U . . .
C28 C 0.535(2) 0.4128(10) 0.2913(7) 0.051(4) Uani 1 1 d . . . . .
H28 H 0.5961 0.4638 0.2840 0.061 Uiso 1 1 calc R U . . .
C29 C 0.521(2) 0.3820(11) 0.3506(7) 0.058(4) Uani 1 1 d . . . . .
H29 H 0.5719 0.4128 0.3827 0.069 Uiso 1 1 calc R U . . .


_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
Bi1 Br5 2.6923(16) . ?
Bi1 Br2 2.7578(15) . ?
Bi1 Br1 2.8529(19) . ?
Bi1 Br3 2.9108(18) . ?
Bi1 Br4 2.9523(16) . ?
Bi1 Br4 3.0229(17) 4_466 ?
Br4 Bi1 3.0229(17) 4_566 ?
N31 C16 1.509(17) . ?
N31 H31A 0.8900 . ?
N31 H31B 0.8900 . ?
N31 H31C 0.8900 . ?
N41 C26 1.495(18) . ?
N41 H41A 0.8900 . ?
N41 H41B 0.8900 . ?
N41 H41C 0.8900 . ?
C11 C12 1.51(2) . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C12 C19 1.36(2) . ?
C12 C13 1.40(2) . ?
C13 C14 1.37(2) . ?
C13 H13 0.9300 . ?
C14 C15 1.377(19) . ?
C14 H14 0.9300 . ?
C15 C18 1.390(19) . ?
C15 C16 1.501(19) . ?
C16 C17 1.51(2) . ?
C16 H16 0.9800 . ?
C17 H17A 0.9600 . ?
C17 H17B 0.9600 . ?
C17 H17C 0.9600 . ?
C18 C19 1.41(2) . ?
C18 H18 0.9300 . ?
C19 H19 0.9300 . ?
C21 C22 1.51(2) . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
C22 C23 1.38(2) . ?
C22 C29 1.40(2) . ?
C23 C24 1.39(2) . ?
C23 H23 0.9300 . ?
C24 C25 1.36(2) . ?
C24 H24 0.9300 . ?
C25 C28 1.391(18) . ?
C25 C26 1.51(2) . ?
C26 C27 1.51(2) . ?
C26 H26 0.9800 . ?
C27 H27A 0.9600 . ?
C27 H27B 0.9600 . ?
C27 H27C 0.9600 . ?
C28 C29 1.37(2) . ?
C28 H28 0.9300 . ?
C29 H29 0.9300 . ?

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
Br5 Bi1 Br2 95.52(6) . . ?
Br5 Bi1 Br1 97.64(5) . . ?
Br2 Bi1 Br1 92.49(5) . . ?
Br5 Bi1 Br3 92.45(5) . . ?
Br2 Bi1 Br3 97.88(4) . . ?
Br1 Bi1 Br3 164.77(5) . . ?
Br5 Bi1 Br4 88.44(6) . . ?
Br2 Bi1 Br4 174.63(5) . . ?
Br1 Bi1 Br4 83.37(5) . . ?
Br3 Bi1 Br4 85.54(5) . . ?
Br5 Bi1 Br4 172.48(5) . 4_466 ?
Br2 Bi1 Br4 89.25(6) . 4_466 ?
Br1 Bi1 Br4 87.93(5) . 4_466 ?
Br3 Bi1 Br4 81.12(5) . 4_466 ?
Br4 Bi1 Br4 87.19(4) . 4_466 ?
Bi1 Br4 Bi1 157.98(7) . 4_566 ?
C16 N31 H31A 109.5 . . ?
C16 N31 H31B 109.5 . . ?
H31A N31 H31B 109.5 . . ?
C16 N31 H31C 109.5 . . ?
H31A N31 H31C 109.5 . . ?
H31B N31 H31C 109.5 . . ?
C26 N41 H41A 109.5 . . ?
C26 N41 H41B 109.5 . . ?
H41A N41 H41B 109.5 . . ?
C26 N41 H41C 109.5 . . ?
H41A N41 H41C 109.5 . . ?
H41B N41 H41C 109.5 . . ?
C12 C11 H11A 109.5 . . ?
C12 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C12 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C19 C12 C13 117.5(15) . . ?
C19 C12 C11 121.7(16) . . ?
C13 C12 C11 120.8(16) . . ?
C14 C13 C12 121.1(15) . . ?
C14 C13 H13 119.5 . . ?
C12 C13 H13 119.5 . . ?
C13 C14 C15 122.6(14) . . ?
C13 C14 H14 118.7 . . ?
C15 C14 H14 118.7 . . ?
C14 C15 C18 116.5(13) . . ?
C14 C15 C16 119.8(12) . . ?
C18 C15 C16 123.6(13) . . ?
C15 C16 N31 109.3(11) . . ?
C15 C16 C17 116.6(12) . . ?
N31 C16 C17 108.3(12) . . ?
C15 C16 H16 107.4 . . ?
N31 C16 H16 107.4 . . ?
C17 C16 H16 107.4 . . ?
C16 C17 H17A 109.5 . . ?
C16 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C16 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?
C15 C18 C19 121.2(14) . . ?
C15 C18 H18 119.4 . . ?
C19 C18 H18 119.4 . . ?
C12 C19 C18 121.1(14) . . ?
C12 C19 H19 119.4 . . ?
C18 C19 H19 119.4 . . ?
C22 C21 H21A 109.5 . . ?
C22 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C22 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C23 C22 C29 116.3(14) . . ?
C23 C22 C21 123.8(16) . . ?
C29 C22 C21 119.8(16) . . ?
C24 C23 C22 122.4(15) . . ?
C24 C23 H23 118.8 . . ?
C22 C23 H23 118.8 . . ?
C25 C24 C23 120.6(15) . . ?
C25 C24 H24 119.7 . . ?
C23 C24 H24 119.7 . . ?
C24 C25 C28 117.6(14) . . ?
C24 C25 C26 123.4(13) . . ?
C28 C25 C26 118.9(13) . . ?
N41 C26 C25 112.6(13) . . ?
N41 C26 C27 106.7(13) . . ?
C25 C26 C27 114.4(12) . . ?
N41 C26 H26 107.6 . . ?
C25 C26 H26 107.6 . . ?
C27 C26 H26 107.6 . . ?
C26 C27 H27A 109.5 . . ?
C26 C27 H27B 109.5 . . ?
H27A C27 H27B 109.5 . . ?
C26 C27 H27C 109.5 . . ?
H27A C27 H27C 109.5 . . ?
H27B C27 H27C 109.5 . . ?
C29 C28 C25 121.9(14) . . ?
C29 C28 H28 119.0 . . ?
C25 C28 H28 119.0 . . ?
C28 C29 C22 121.0(14) . . ?
C28 C29 H29 119.5 . . ?
C22 C29 H29 119.5 . . ?

_refine_diff_density_max         1.483
_refine_diff_density_min         -1.306
_refine_diff_density_rms         0.172

# start Validation Reply Form
_vrf_PLAT035_1_S_RT              
;
PROBLEM: _chemical_absolute_configuration Info  Not Given     Please Do !  
RESPONSE: absolute configuration has not been established by anomalous
        dispersion effects in diffraction measurements on the crystal.  
        The enantiomer has been assigned by reference to an unchanging  
        chiral centre in the synthetic procedure.
;
_vrf_PLAT342_1_S_RT              
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.02056 Ang.  
RESPONSE: this is likely related to the presence of heavy Bismuth atoms.
;
# end Validation Reply Form



####################################################################### 
# 
# 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_S_LT
_database_code_depnum_ccdc_archive 'CCDC 2181248'
loop_
_audit_author_name
_audit_author_address
'Prof. R. Boomishankar'
;Professor in Chemistry, IISER Pune
India
;
_audit_update_record             
;
2022-06-22 deposited with the CCDC.	2022-08-11 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C18 H28 Bi Br5 N2'
_chemical_formula_weight         880.95

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'
Bi Bi -4.1077 10.2566 '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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

_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+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   7.903(2)
_cell_length_b                   14.943(4)
_cell_length_c                   21.449(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2533.0(12)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    4482
_cell_measurement_theta_min      4.078
_cell_measurement_theta_max      25.027

_exptl_crystal_description       rod
_exptl_crystal_colour            white
_exptl_crystal_density_meas      2.310
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.310
_exptl_crystal_F_000             1632
_exptl_transmission_factor_min   0.414
_exptl_transmission_factor_max   0.552
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_exptl_absorpt_coefficient_mu    14.854
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            74531
_diffrn_reflns_av_unetI/netI     0.0775
_diffrn_reflns_av_R_equivalents  0.2107
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         2.916
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_full        25.027
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             4478
_reflns_number_gt                3779
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.748
_reflns_Friedel_fraction_max     1.000
_reflns_Friedel_fraction_full    1.000

_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.
;

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+48.8892P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.12(2)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         4478
_refine_ls_number_parameters     242
_refine_ls_number_restraints     72
_refine_ls_R_factor_all          0.0773
_refine_ls_R_factor_gt           0.0545
_refine_ls_wR_factor_ref         0.0933
_refine_ls_wR_factor_gt          0.0846
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_restrained_S_all      1.094
_refine_ls_shift/su_max          0.001
_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
Bi1 Bi 0.92434(9) 0.39129(5) 0.50821(3) 0.01123(18) Uani 1 1 d . . . . .
Br1 Br 0.9489(3) 0.35112(14) 0.63694(9) 0.0208(5) Uani 1 1 d . . . . .
Br2 Br 1.2193(2) 0.48936(13) 0.50892(10) 0.0203(5) Uani 1 1 d . . . . .
Br3 Br 0.7220(3) 0.53428(14) 0.51650(11) 0.0251(5) Uani 1 1 d . . . . .
Br4 Br 0.8795(3) 0.37797(13) 0.37495(9) 0.0173(5) Uani 1 1 d . . . . .
Br5 Br 0.6247(2) 0.27703(13) 0.51582(11) 0.0247(5) Uani 1 1 d . . . . .
N11 N 0.449(2) 0.3896(12) 0.3940(6) 0.020(4) Uani 1 1 d . . . . .
H11D H 0.5630 0.3905 0.3894 0.030 Uiso 1 1 calc R U . . .
H11E H 0.4098 0.3329 0.3878 0.030 Uiso 1 1 calc R U . . .
H11F H 0.4209 0.4079 0.4332 0.030 Uiso 1 1 calc R U . . .
N21 N 0.875(2) 0.1440(11) 0.3687(8) 0.024(4) Uani 1 1 d . . . . .
H21D H 0.8978 0.2035 0.3658 0.036 Uiso 1 1 calc R U . . .
H21E H 0.8988 0.1246 0.4080 0.036 Uiso 1 1 calc R U . . .
H21F H 0.7638 0.1342 0.3602 0.036 Uiso 1 1 calc R U . . .
C11 C 0.446(3) 0.5416(13) 0.3553(9) 0.026(5) Uani 1 1 d . . . . .
H11A H 0.4096 0.5807 0.3212 0.039 Uiso 1 1 calc R U . . .
H11B H 0.5696 0.5364 0.3550 0.039 Uiso 1 1 calc R U . . .
H11C H 0.4091 0.5670 0.3952 0.039 Uiso 1 1 calc R U . . .
C12 C 0.369(3) 0.4512(12) 0.3472(9) 0.018(5) Uani 1 1 d . . . . .
H12 H 0.2456 0.4556 0.3565 0.022 Uiso 1 1 calc R U . . .
C13 C 0.390(2) 0.4106(13) 0.2826(9) 0.014(5) Uani 1 1 d . U . . .
C14 C 0.498(3) 0.4441(15) 0.2381(10) 0.019(5) Uani 1 1 d . . . . .
H14 H 0.5672 0.4943 0.2478 0.023 Uiso 1 1 calc R U . . .
C15 C 0.509(3) 0.4056(16) 0.1791(10) 0.030(6) Uani 1 1 d . . . . .
H15 H 0.5813 0.4312 0.1485 0.036 Uiso 1 1 calc R U . . .
C16 C 0.414(3) 0.3288(14) 0.1646(10) 0.028(6) Uani 1 1 d . . . . .
C17 C 0.305(3) 0.2944(14) 0.2105(9) 0.020(5) Uani 1 1 d . . . . .
H17 H 0.2394 0.2427 0.2019 0.024 Uiso 1 1 calc R U . . .
C18 C 0.294(3) 0.3349(13) 0.2672(9) 0.017(5) Uani 1 1 d . U . . .
H18 H 0.2191 0.3108 0.2974 0.020 Uiso 1 1 calc R U . . .
C19 C 0.421(4) 0.2866(15) 0.1009(9) 0.033(6) Uani 1 1 d . . . . .
H19A H 0.3054 0.2799 0.0845 0.049 Uiso 1 1 calc R U . . .
H19B H 0.4742 0.2277 0.1038 0.049 Uiso 1 1 calc R U . . .
H19C H 0.4864 0.3248 0.0728 0.049 Uiso 1 1 calc R U . . .
C21 C 0.945(3) -0.0053(14) 0.3306(10) 0.032(6) Uani 1 1 d . U . . .
H21A H 0.8259 -0.0170 0.3207 0.048 Uiso 1 1 calc R U . . .
H21B H 0.9678 -0.0233 0.3737 0.048 Uiso 1 1 calc R U . . .
H21C H 1.0174 -0.0396 0.3022 0.048 Uiso 1 1 calc R U . . .
C22 C 0.982(2) 0.0941(14) 0.3230(8) 0.016(4) Uani 1 1 d . U . . .
H22 H 1.1027 0.1041 0.3344 0.019 Uiso 1 1 calc R U . . .
C23 C 0.956(2) 0.1298(13) 0.2572(9) 0.018(4) Uani 1 1 d . U . . .
C24 C 0.865(3) 0.2074(14) 0.2434(10) 0.024(5) Uani 1 1 d . U . . .
H24 H 0.8098 0.2395 0.2759 0.028 Uiso 1 1 calc R U . . .
C25 C 0.855(3) 0.2372(15) 0.1835(10) 0.025(5) Uani 1 1 d . U . . .
H25 H 0.7924 0.2903 0.1752 0.031 Uiso 1 1 calc R U . . .
C26 C 0.931(3) 0.1933(13) 0.1343(9) 0.022(4) Uani 1 1 d . U . . .
C27 C 1.020(3) 0.1148(15) 0.1482(9) 0.023(5) Uani 1 1 d . U . . .
H27 H 1.0730 0.0820 0.1156 0.027 Uiso 1 1 calc R U . . .
C28 C 1.032(3) 0.0855(15) 0.2075(9) 0.023(5) Uani 1 1 d . U . . .
H28 H 1.0942 0.0325 0.2157 0.028 Uiso 1 1 calc R U . . .
C29 C 0.924(4) 0.2283(16) 0.0683(9) 0.037(6) Uani 1 1 d . U . . .
H29A H 0.8662 0.1847 0.0417 0.055 Uiso 1 1 calc R U . . .
H29B H 1.0394 0.2379 0.0528 0.055 Uiso 1 1 calc R U . . .
H29C H 0.8622 0.2851 0.0676 0.055 Uiso 1 1 calc R U . . .


_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
Bi1 Br3 2.675(2) . ?
Bi1 Br2 2.754(2) . ?
Bi1 Br1 2.832(2) . ?
Bi1 Br4 2.887(2) . ?
Bi1 Br5 2.924(2) . ?
Bi1 Br5 3.017(2) 4_556 ?
Br5 Bi1 3.017(2) 4_456 ?
N11 C12 1.50(2) . ?
N11 H11D 0.9100 . ?
N11 H11E 0.9100 . ?
N11 H11F 0.9100 . ?
N21 C22 1.49(2) . ?
N21 H21D 0.9100 . ?
N21 H21E 0.9100 . ?
N21 H21F 0.9100 . ?
C11 C12 1.49(3) . ?
C11 H11A 0.9800 . ?
C11 H11B 0.9800 . ?
C11 H11C 0.9800 . ?
C12 C13 1.52(3) . ?
C12 H12 1.0000 . ?
C13 C14 1.38(3) . ?
C13 C18 1.40(3) . ?
C14 C15 1.39(3) . ?
C14 H14 0.9500 . ?
C15 C16 1.41(3) . ?
C15 H15 0.9500 . ?
C16 C17 1.40(3) . ?
C16 C19 1.51(3) . ?
C17 C18 1.36(3) . ?
C17 H17 0.9500 . ?
C18 H18 0.9500 . ?
C19 H19A 0.9800 . ?
C19 H19B 0.9800 . ?
C19 H19C 0.9800 . ?
C21 C22 1.52(3) . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C22 C23 1.52(3) . ?
C22 H22 1.0000 . ?
C23 C28 1.39(3) . ?
C23 C24 1.40(3) . ?
C24 C25 1.36(3) . ?
C24 H24 0.9500 . ?
C25 C26 1.38(3) . ?
C25 H25 0.9500 . ?
C26 C27 1.40(3) . ?
C26 C29 1.51(3) . ?
C27 C28 1.35(3) . ?
C27 H27 0.9500 . ?
C28 H28 0.9500 . ?
C29 H29A 0.9800 . ?
C29 H29B 0.9800 . ?
C29 H29C 0.9800 . ?

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
Br3 Bi1 Br2 94.63(7) . . ?
Br3 Bi1 Br1 98.36(7) . . ?
Br2 Bi1 Br1 92.83(7) . . ?
Br3 Bi1 Br4 92.72(7) . . ?
Br2 Bi1 Br4 98.40(6) . . ?
Br1 Bi1 Br4 163.53(6) . . ?
Br3 Bi1 Br5 88.77(7) . . ?
Br2 Bi1 Br5 174.94(7) . . ?
Br1 Bi1 Br5 82.95(7) . . ?
Br4 Bi1 Br5 85.16(6) . . ?
Br3 Bi1 Br5 172.43(7) . 4_556 ?
Br2 Bi1 Br5 90.01(7) . 4_556 ?
Br1 Bi1 Br5 87.35(6) . 4_556 ?
Br4 Bi1 Br5 80.67(6) . 4_556 ?
Br5 Bi1 Br5 87.01(3) . 4_556 ?
Bi1 Br5 Bi1 154.49(8) . 4_456 ?
C12 N11 H11D 109.5 . . ?
C12 N11 H11E 109.5 . . ?
H11D N11 H11E 109.5 . . ?
C12 N11 H11F 109.5 . . ?
H11D N11 H11F 109.5 . . ?
H11E N11 H11F 109.5 . . ?
C22 N21 H21D 109.5 . . ?
C22 N21 H21E 109.5 . . ?
H21D N21 H21E 109.5 . . ?
C22 N21 H21F 109.5 . . ?
H21D N21 H21F 109.5 . . ?
H21E N21 H21F 109.5 . . ?
C12 C11 H11A 109.5 . . ?
C12 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C12 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C11 C12 N11 107.9(17) . . ?
C11 C12 C13 115.2(17) . . ?
N11 C12 C13 108.7(15) . . ?
C11 C12 H12 108.3 . . ?
N11 C12 H12 108.3 . . ?
C13 C12 H12 108.3 . . ?
C14 C13 C18 117.7(18) . . ?
C14 C13 C12 123.5(18) . . ?
C18 C13 C12 118.7(17) . . ?
C13 C14 C15 121(2) . . ?
C13 C14 H14 119.4 . . ?
C15 C14 H14 119.4 . . ?
C14 C15 C16 120(2) . . ?
C14 C15 H15 119.8 . . ?
C16 C15 H15 119.8 . . ?
C17 C16 C15 118.0(19) . . ?
C17 C16 C19 120(2) . . ?
C15 C16 C19 122(2) . . ?
C18 C17 C16 120(2) . . ?
C18 C17 H17 119.9 . . ?
C16 C17 H17 119.9 . . ?
C17 C18 C13 122.4(19) . . ?
C17 C18 H18 118.8 . . ?
C13 C18 H18 118.8 . . ?
C16 C19 H19A 109.5 . . ?
C16 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C16 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C22 C21 H21A 109.5 . . ?
C22 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C22 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
N21 C22 C21 108.1(17) . . ?
N21 C22 C23 111.0(16) . . ?
C21 C22 C23 114.5(16) . . ?
N21 C22 H22 107.7 . . ?
C21 C22 H22 107.7 . . ?
C23 C22 H22 107.7 . . ?
C28 C23 C24 117.1(19) . . ?
C28 C23 C22 119.0(18) . . ?
C24 C23 C22 123.8(18) . . ?
C25 C24 C23 120(2) . . ?
C25 C24 H24 120.0 . . ?
C23 C24 H24 120.0 . . ?
C24 C25 C26 123(2) . . ?
C24 C25 H25 118.7 . . ?
C26 C25 H25 118.7 . . ?
C25 C26 C27 117.1(19) . . ?
C25 C26 C29 122(2) . . ?
C27 C26 C29 120.6(19) . . ?
C28 C27 C26 120(2) . . ?
C28 C27 H27 119.8 . . ?
C26 C27 H27 119.8 . . ?
C27 C28 C23 123(2) . . ?
C27 C28 H28 118.7 . . ?
C23 C28 H28 118.7 . . ?
C26 C29 H29A 109.5 . . ?
C26 C29 H29B 109.5 . . ?
H29A C29 H29B 109.5 . . ?
C26 C29 H29C 109.5 . . ?
H29A C29 H29C 109.5 . . ?
H29B C29 H29C 109.5 . . ?

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
N11 H11D Br4 0.91 2.53 3.435(17) 174.8 .
N11 H11E Br1 0.91 2.82 3.657(18) 154.0 4_456
N11 H11F Br2 0.91 2.58 3.403(15) 150.6 1_455
N21 H21D Br4 0.91 2.62 3.499(17) 163.3 .
N21 H21E Br2 0.91 2.84 3.518(17) 131.9 4_456
N21 H21E Br5 0.91 2.83 3.379(18) 119.9 4_556
N21 H21F Br1 0.91 2.50 3.371(17) 160.7 4_456

_refine_diff_density_max         1.481
_refine_diff_density_min         -1.522
_refine_diff_density_rms         0.308

# start Validation Reply Form
_vrf_RINTA01_1_S_LT              
;
PROBLEM: The value of Rint is greater than 0.18
RESPONSE: the high Rint value is a consequence of the relatively low quality
of the diffraction data as the crystal develops some cracks at low temperature.
;
_vrf_PLAT035_1_S_LT              
;
PROBLEM: _chemical_absolute_configuration Info  Not Given     Please Do !  
RESPONSE: absolute configuration has not been established by anomalous
        dispersion effects in diffraction measurements on the crystal.  
        The enantiomer has been assigned by reference to an unchanging  
        chiral centre in the synthetic procedure.
;
_vrf_PLAT342_1_S_LT              
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............       0.03 Ang.  
RESPONSE: this is likely related to the presence of heavy Bismuth atoms.
;
# end Validation Reply Form



