# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_nr16005x2
_database_code_depnum_ccdc_archive 'CCDC 1536017'
_audit_update_record             
;
2018-04-11 deposited with the CCDC.
2018-04-24 downloaded from the CCDC.
;
_audit_creation_date             2018-04-10
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2018.04.03 svn.r3497 for OlexSys, GUI svn.r5486)
;
_shelx_SHELXL_version_number     2018/3
loop_
_audit_author_email
g.s.nichol@ed.ac.uk
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Bi2 I9, 3(C3 H4 N S)'
_chemical_formula_sum            'C9 H12 Bi2 I9 N3 S3'
_chemical_formula_weight         1818.46
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C3 H4 N1 S1 Bi1 I4'
_chemical_oxdiff_usercomment     '@ 250 K THB'
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'
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'
S S 0.1246 0.1234 '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           57
_space_group_name_H-M_alt        'P b c m'
_space_group_name_Hall           '-P 2c 2b'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x, -y+1/2, -z'
'-x, -y, -z'
'x, y, -z-1/2'
'x, -y-1/2, z-1/2'
'-x, y-1/2, z'

_cell_length_a                   9.8257(2)
_cell_length_b                   14.6666(3)
_cell_length_c                   23.2957(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     3357.13(11)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    28557
_cell_measurement_temperature    250.0
_cell_measurement_theta_max      28.8850
_cell_measurement_theta_min      3.4310
_shelx_estimated_absorpt_T_max   0.692
_shelx_estimated_absorpt_T_min   0.189
_exptl_absorpt_coefficient_mu    18.937
_exptl_absorpt_correction_T_max  0.7908
_exptl_absorpt_correction_T_min  0.1888
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1102 before and 0.0979 after correction. The Ratio of minimum to maximum transmission is 0.2387. The λ/2 correction factor is Not present.'
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    3.598
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             3112
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
-9 -13 13 0.0564
-12 10 5 0.0473
-2 20 -8 0.0328
11 9 -13 0.0426
11 -13 -2 0.0556
0 -20 9 0.0566
0 1 33 0.0104
0 -1 -33 0.0104

_exptl_crystal_recrystallization_method 
'The material was recrystallised from a mixture of ethanol and water by solvent layering'
_exptl_crystal_size_max          0.132
_exptl_crystal_size_mid          0.099
_exptl_crystal_size_min          0.021
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
-9.3244 -12.9047 13.0351 -0.1623 0.5504 0.8189
-12.1050 9.6072 4.6457 0.1611 -0.5386 0.8270
-1.5825 19.9044 -8.0777 0.2841 -0.9570 -0.0589
11.1920 9.1868 -12.7107 0.1059 -0.3611 -0.9265
10.8146 -12.8421 -2.1669 -0.2040 0.6837 -0.7007
-0.0658 -19.8357 9.2876 -0.2796 0.9426 0.1827
0.0001 0.9999 33.0014 -0.9478 -0.0920 0.3241
-0.0001 -0.9999 -33.0014 0.9478 0.0920 -0.3241

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0961
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            96745
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.347
_diffrn_reflns_theta_max         25.347
_diffrn_reflns_theta_min         2.712
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      250.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -20.00  31.00   0.50   20.00    --   -9.27 -99.00  90.00  102
  2  ω    -26.00  89.00   0.50   20.00    --   10.68  19.00-180.00  230
  3  ω    -59.00  37.00   0.50   20.00    --   10.68 -57.00   0.00  192
  4  ω    -20.00  51.00   0.50   20.00    --   10.68 -99.00 -30.00  142
  5  ω    -20.00  51.00   0.50   20.00    --   10.68 -99.00-120.00  142
  6  ω    -59.00  37.00   0.50   20.00    --   10.68 -57.00-180.00  192
  7  ω    -59.00  37.00   0.50   20.00    --   10.68 -57.00  60.00  192
  8  ω    -20.00  31.00   0.50   20.00    --   -9.27 -99.00 150.00  102
  9  ω    -79.00  17.00   0.50   20.00    --   -9.27 -57.00 -90.00  192
 10  ω    -20.00  31.00   0.50   20.00    --   -9.27 -99.00 -30.00  102
 11  ω    -20.00  31.00   0.50   20.00    --   -9.27 -99.00-180.00  102
 12  ω    -49.00  -1.00   0.50   20.00    --   -9.27  99.00  55.00   96
 13  ω    -20.00  51.00   0.50   20.00    --   10.68 -99.00-180.00  142
 14  ω    -41.00  65.00   0.50   20.00    --   -9.27  77.00-150.00  212
 15  ω    -82.00  13.00   0.50   20.00    --   -9.27 -38.00 120.00  190
 16  ω    -20.00  51.00   0.50   20.00    --   10.68 -99.00 -90.00  142
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford DIffraction SuperNova'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0237657000
_diffrn_orient_matrix_UB_12      0.0007186000
_diffrn_orient_matrix_UB_13      -0.0287407000
_diffrn_orient_matrix_UB_21      0.0057614000
_diffrn_orient_matrix_UB_22      -0.0481609000
_diffrn_orient_matrix_UB_23      -0.0013296000
_diffrn_orient_matrix_UB_31      -0.0679328000
_diffrn_orient_matrix_UB_32      -0.0043238000
_diffrn_orient_matrix_UB_33      0.0099508000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_diffrn_special_details          ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3086
_reflns_number_total             3158
_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 1.171.38.43h (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43h (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43h (Rigaku OD, 2015)'
_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    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.562
_refine_diff_density_min         -2.199
_refine_diff_density_rms         0.246
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.332
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     134
_refine_ls_number_reflns         3158
_refine_ls_number_restraints     67
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0590
_refine_ls_restrained_S_all      1.339
_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)+117.9315P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1151
_refine_ls_wR_factor_ref         0.1159
_refine_special_details          
;
Compound THB crystallized as dark red block and dark red plate-shaped crystals.  Despite their apparant good quality, diffraction from the block crystals (NR16005x1) was very poor.  The crystals shattered when flash-cooled at 120, 150 and 200 K.  At 250 K diffraction was reasonable but diffraction from the plate-shaped crystals was much better and it is the structure from a plate crystal which is presented here.One of the thiazolium cations (N1/S1), and the Bi2I9 unit, lies on a crystallographic mirror plane.  In the case of the thiazolium it causes the nitrogen and sulfur atoms to be interchanged by substitional disorder.  The second thiazolium cation was modelled using a whole-molecule disorder model.  A search of the CSD shows that almost all thiazoliuim/thiazole models are disordered!  In this case electron density plots showed that two large peaks were located within bonding distance of each other.  Each peak was assumed to be the sulfur atom, disordered over two sites, and the rest of the ring was built from that starting point.  Once the rings had been established, with reasonable geometry, it was necessary to fix the coordinates and displacement parameters in place with AFIX 1 to prevent some of the atoms shifting uncontrollably (even with RIGU/SADI restraints) and to prevent some from becoming non-positive definite.


#===============================================================================
The Following Improvement and Query ALERTS were generated - (Acta-Mode) <<<
#===============================================================================
     Format: alert-number_ALERT_alert-type_alert-level text

161_ALERT_4_C Missing or Zero s.u. (esd) on x-coordinate for .        C3A Check
161_ALERT_4_C Missing or Zero s.u. (esd) on x-coordinate for .        C5A Check
161_ALERT_4_C Missing or Zero s.u. (esd) on x-coordinate for .        C4A Check
161_ALERT_4_C Missing or Zero s.u. (esd) on x-coordinate for .        N2A Check
162_ALERT_4_C Missing or Zero s.u. (esd) on y-coordinate for .        C3A Check
162_ALERT_4_C Missing or Zero s.u. (esd) on y-coordinate for .        C5A Check
162_ALERT_4_C Missing or Zero s.u. (esd) on y-coordinate for .        C4A Check
162_ALERT_4_C Missing or Zero s.u. (esd) on y-coordinate for .        N2A Check
163_ALERT_4_C Missing or Zero s.u. (esd) on z-coordinate for .        C3A Check
163_ALERT_4_C Missing or Zero s.u. (esd) on z-coordinate for .        C5A Check
163_ALERT_4_C Missing or Zero s.u. (esd) on z-coordinate for .        C4A Check
163_ALERT_4_C Missing or Zero s.u. (esd) on z-coordinate for .        N2A Check
242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         C1 Check
242_ALERT_2_C Low    'MainMol' Ueq as Compared to Neighbors of         C2 Check
342_ALERT_3_C Low Bond Precision on  C-C Bonds ...............      0.013 Ang.

Discussed above

420_ALERT_2_C D-H Without Acceptor      N1       --H1        .     Please Check
420_ALERT_2_C D-H Without Acceptor      N2       --H2        .     Please Check
431_ALERT_2_C Short Inter HL..A Contact I6       ..S1        .       3.58 Ang.
906_ALERT_3_C Large K Value in the Analysis of Variance ......     11.402 Check
906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.406 Check
972_ALERT_2_C Check Calcd Resid. Dens.  1.53A   From S1             -2.32 eA-3
977_ALERT_2_C Check Negative Difference Density on H1               -0.49 eA-3
977_ALERT_2_C Check Negative Difference Density on H1A              -0.41 eA-3
977_ALERT_2_C Check Negative Difference Density on H3               -0.39 eA-3
977_ALERT_2_C Check Negative Difference Density on H5               -0.48 eA-3
977_ALERT_2_C Check Negative Difference Density on H2AA             -0.47 eA-3
977_ALERT_2_C Check Negative Difference Density on H5A              -0.53 eA-3

Noted. Both thiazolium cations are severely disordered.

#===============================================================================
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Shared sites
{C3, S2A}
3. Restrained distances
 C2-C2_$1 = C5A-C4A = C5-C4
 1.35 with sigma of 0.02
 N1-C2 = N2A-C4A = N2-C4
 1.37 with sigma of 0.02
 N1-C1 = N2-C3 = N2A-C3A
 1.3 with sigma of 0.02
 S1-C1 = S2-C3 = S2A-C3A
 1.69 with sigma of 0.02
 S1-C2 = S2-C5 = S2A-C5A
 1.68 with sigma of 0.02
 C1-C2 = C4-C3 = C4A-C3A
 2.18 with sigma of 0.04
4. Restrained planarity
 S2, N2, C3, C4, C5
 with sigma of 0.1
 S2A, N2A, C3A, C4A, C5A
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(N1) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C3) = Uanis(S2A)
Uanis(S2A) = Uanis(C3)
6. Rigid body (RIGU) restrains
 S1, N1, C1, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2, N2, C3, C4, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S2A, N2A, C3A, C4A, C5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, N1, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(S2A)=Sof(C3A)=Sof(H3A)=Sof(C5A)=Sof(H5A)=Sof(C4A)=Sof(H4A)=Sof(N2A)=
 Sof(H2AA)=1-FVAR(1)
 Sof(S2)=Sof(N2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=FVAR(1)
 Fixed Sof: S1(0.5) N1(0.5) H1(0.5) H1A(0.25) H1B(0.25) H2A(0.5) H2B(0.5)
8.a Everything fixed:
 C3A, C5A, C4A, N2A
8.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1A), C1(H1B), C2(H2A), C2(H2B), N2(H2), C3(H3), C3A(H3A), C4(H4),
 C5(H5), C5A(H5A), C4A(H4A), N2A(H2AA)
;
_atom_sites_solution_hydrogens   geom
_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
Bi1 Bi 0.25138(6) 0.43436(4) 0.65793(2) 0.03005(17) Uani 1 1 d . . . . .
I1 I 0.01500(15) 0.49287(10) 0.750000 0.0372(3) Uani 1 2 d S T P . .
I2 I 0.43550(15) 0.54489(10) 0.750000 0.0378(4) Uani 1 2 d S T P . .
I3 I 0.28166(15) 0.27046(10) 0.750000 0.0359(3) Uani 1 2 d S T P . .
I4 I 0.21577(13) 0.59687(8) 0.58395(5) 0.0474(3) Uani 1 1 d . . . . .
I5 I 0.06473(12) 0.32467(8) 0.58609(5) 0.0473(3) Uani 1 1 d . . . . .
I6 I 0.49556(11) 0.37114(8) 0.59485(5) 0.0433(3) Uani 1 1 d . . . . .
S1 S 0.7597(15) 0.2944(14) 0.6887(6) 0.079(4) Uani 0.5 1 d D U . A 1
N1 N 0.756(5) 0.282(5) 0.7098(13) 0.10(2) Uani 0.5 1 d D U . A 2
H1 H 0.726792 0.282906 0.674507 0.120 Uiso 0.5 1 calc R . . A 2
C1 C 0.6805(19) 0.3193(16) 0.750000 0.049(6) Uani 1 2 d DS TU P . .
H1A H 0.593810 0.346440 0.750000 0.059 Uiso 0.5 2 calc RS T P A 1
H1B H 0.603355 0.357212 0.750000 0.059 Uiso 0.5 2 calc RS T P A 2
C2 C 0.8806(13) 0.2416(10) 0.7214(4) 0.039(4) Uani 1 1 d D U . . .
H2A H 0.949389 0.211498 0.700655 0.046 Uiso 0.5 1 calc R . . A 1
H2B H 0.947146 0.219925 0.695761 0.046 Uiso 0.5 1 calc R . . A 2
S2 S 0.7539(12) 0.5729(8) 0.8534(5) 0.111(4) Uani 0.754(16) 1 d D U . B 1
S2A S 0.6286(10) 0.6291(7) 0.8823(4) 0.063(4) Uani 0.246(16) 1 d D U . B 2
N2 N 0.6439(19) 0.6203(14) 0.9387(7) 0.072(7) Uani 0.754(16) 1 d D U . B 1
H2 H 0.588660 0.644741 0.963540 0.086 Uiso 0.754(16) 1 calc R . . B 1
C3 C 0.6286(10) 0.6291(7) 0.8823(4) 0.063(4) Uani 0.754(16) 1 d D U . B 1
H3 H 0.559500 0.661198 0.863086 0.076 Uiso 0.754(16) 1 calc R . . B 1
C3A C 0.605690 0.620760 0.953040 0.000 Uiso 0.2462 1 d D U . B 2
H3A H 0.531455 0.644726 0.973538 0.000 Uiso 0.246(16) 1 calc R . . B 2
C4 C 0.754(3) 0.5693(19) 0.9542(9) 0.081(10) Uani 0.754(16) 1 d D U . B 1
H4 H 0.776619 0.558715 0.992862 0.098 Uiso 0.754(16) 1 calc R . . B 1
C5 C 0.830(2) 0.5350(17) 0.9107(9) 0.068(8) Uani 0.754(16) 1 d D U . B 1
H5 H 0.907477 0.497960 0.913067 0.082 Uiso 0.754(16) 1 calc R . . B 1
C5A C 0.774750 0.571690 0.886150 0.097 Uiso 0.2462 1 d D U . B 2
H5A H 0.829665 0.558859 0.854112 0.116 Uiso 0.246(16) 1 calc R . . B 2
C4A C 0.805900 0.545570 0.940230 0.000 Uiso 0.2462 1 d D U . B 2
H4A H 0.883288 0.512129 0.951161 0.000 Uiso 0.246(16) 1 calc R . . B 2
N2A N 0.708100 0.575290 0.975630 0.000 Uiso 0.2462 1 d D U . B 2
H2AA H 0.712093 0.564895 1.012359 0.000 Uiso 0.246(16) 1 calc R . . B 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
Bi1 0.0328(3) 0.0313(3) 0.0260(3) 0.0000(2) -0.0015(2) -0.0013(2)
I1 0.0328(7) 0.0398(8) 0.0391(7) 0.000 0.000 0.0024(6)
I2 0.0417(8) 0.0401(8) 0.0316(7) 0.000 0.000 -0.0160(7)
I3 0.0496(8) 0.0291(7) 0.0289(7) 0.000 0.000 0.0062(6)
I4 0.0595(7) 0.0365(6) 0.0461(6) 0.0093(5) -0.0021(5) 0.0063(5)
I5 0.0500(6) 0.0510(7) 0.0410(6) -0.0076(5) -0.0058(5) -0.0172(5)
I6 0.0379(5) 0.0477(6) 0.0443(6) -0.0026(5) 0.0046(5) 0.0001(5)
S1 0.071(8) 0.083(9) 0.081(10) -0.006(8) -0.021(7) 0.012(7)
N1 0.081(19) 0.16(5) 0.06(2) -0.01(2) -0.022(16) 0.07(3)
C1 0.017(10) 0.038(13) 0.093(18) 0.000 0.000 0.001(8)
C2 0.035(7) 0.036(8) 0.045(8) 0.006(7) 0.007(7) 0.004(7)
S2 0.126(9) 0.104(8) 0.103(8) -0.004(6) 0.047(7) 0.010(7)
S2A 0.068(8) 0.060(8) 0.061(6) 0.001(6) 0.003(6) 0.000(6)
N2 0.078(13) 0.083(16) 0.053(8) 0.016(10) 0.054(9) 0.024(11)
C3 0.068(8) 0.060(8) 0.061(6) 0.001(6) 0.003(6) 0.000(6)
C4 0.103(18) 0.11(2) 0.031(10) -0.027(12) -0.010(11) 0.032(16)
C5 0.053(14) 0.066(18) 0.086(16) -0.003(13) 0.020(12) 0.020(12)

_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 I1 3.2758(12) . ?
Bi1 I2 3.2405(12) . ?
Bi1 I3 3.2354(12) . ?
Bi1 I4 2.9619(12) . ?
Bi1 I5 2.9585(12) . ?
Bi1 I6 2.9624(12) . ?
S1 C1 1.668(15) . ?
S1 C2 1.610(15) . ?
N1 H1 0.8700 . ?
N1 C1 1.314(19) . ?
N1 C2 1.388(19) . ?
C1 H1A 0.9400 . ?
C1 H1B 0.9400 . ?
C2 C2 1.334(17) 6_557 ?
C2 H2A 0.9400 . ?
C2 H2B 0.9400 . ?
S2 C3 1.628(12) . ?
S2 C5 1.627(17) . ?
S2A C3A 1.667(10) . ?
S2A C5A 1.667(10) . ?
N2 H2 0.8700 . ?
N2 C3 1.329(15) . ?
N2 C4 1.366(17) . ?
C3 H3 0.9400 . ?
C3A H3A 0.9400 . ?
C3A N2A 1.3169 . ?
C4 H4 0.9400 . ?
C4 C5 1.352(18) . ?
C5 H5 0.9400 . ?
C5A H5A 0.9400 . ?
C5A C4A 1.3519 . ?
C4A H4A 0.9400 . ?
C4A N2A 1.3392 . ?
N2A H2AA 0.8700 . ?

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 Bi1 I1 80.30(3) . . ?
I3 Bi1 I1 79.97(3) . . ?
I3 Bi1 I2 83.20(3) . . ?
I4 Bi1 I1 94.96(4) . . ?
I4 Bi1 I2 92.78(4) . . ?
I4 Bi1 I3 173.97(4) . . ?
I4 Bi1 I6 93.38(4) . . ?
I5 Bi1 I1 94.20(4) . . ?
I5 Bi1 I2 172.99(3) . . ?
I5 Bi1 I3 91.60(4) . . ?
I5 Bi1 I4 92.02(4) . . ?
I5 Bi1 I6 92.94(4) . . ?
I6 Bi1 I1 168.82(3) . . ?
I6 Bi1 I2 91.88(4) . . ?
I6 Bi1 I3 91.25(4) . . ?
Bi1 I1 Bi1 81.80(4) . 6_557 ?
Bi1 I2 Bi1 82.89(4) . 6_557 ?
Bi1 I3 Bi1 83.05(4) 6_557 . ?
C2 S1 C1 92.5(11) . . ?
C1 N1 H1 118.8 . . ?
C1 N1 C2 122(3) . . ?
C2 N1 H1 118.8 . . ?
S1 C1 S1 117.9(14) 6_557 . ?
S1 C1 H1A 121.0 . . ?
S1 C1 H1A 121.0 6_557 . ?
N1 C1 S1 15(3) 6_557 6_557 ?
N1 C1 S1 104.9(19) . 6_557 ?
N1 C1 N1 91(3) 6_557 . ?
N1 C1 H1B 134.5 6_557 . ?
N1 C1 H1B 134.5 . . ?
S1 C2 H2A 120.9 . . ?
N1 C2 H2B 129.4 . . ?
C2 C2 S1 118.2(6) 6_557 . ?
C2 C2 N1 101.2(13) 6_557 . ?
C2 C2 H2A 120.9 6_557 . ?
C2 C2 H2B 129.4 6_557 . ?
C5 S2 C3 100.3(10) . . ?
C3A S2A C5A 91.5(5) . . ?
C3 N2 H2 123.1 . . ?
C3 N2 C4 113.8(16) . . ?
C4 N2 H2 123.1 . . ?
S2 C3 H3 127.0 . . ?
N2 C3 S2 106.0(11) . . ?
N2 C3 H3 127.0 . . ?
S2A C3A H3A 125.4 . . ?
N2A C3A S2A 109.2(3) . . ?
N2A C3A H3A 125.4 . . ?
N2 C4 H4 121.9 . . ?
C5 C4 N2 116.2(19) . . ?
C5 C4 H4 121.9 . . ?
S2 C5 H5 128.1 . . ?
C4 C5 S2 103.8(16) . . ?
C4 C5 H5 128.1 . . ?
S2A C5A H5A 123.6 . . ?
C4A C5A S2A 112.8(3) . . ?
C4A C5A H5A 123.6 . . ?
C5A C4A H4A 125.7 . . ?
N2A C4A C5A 108.6 . . ?
N2A C4A H4A 125.7 . . ?
C3A N2A C4A 117.8 . . ?
C3A N2A H2AA 121.1 . . ?
C4A N2A H2AA 121.1 . . ?

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
C1 S1 C2 C2 -4.1(15) . . . 6_557 ?
C1 N1 C2 C2 9(8) . . . 6_557 ?
C2 S1 C1 S1 7(3) . . . 6_557 ?
C2 N1 C1 N1 -12(11) . . . 6_557 ?
S2A C3A N2A C4A -0.1(4) . . . . ?
S2A C5A C4A N2A -0.7(4) . . . . ?
N2 C4 C5 S2 1(3) . . . . ?
C3 S2 C5 C4 -1(2) . . . . ?
C3 N2 C4 C5 -1(3) . . . . ?
C3A S2A C5A C4A 0.6(6) . . . . ?
C4 N2 C3 S2 -0.1(17) . . . . ?
C5 S2 C3 N2 0.6(12) . . . . ?
C5A S2A C3A N2A -0.3(5) . . . . ?
C5A C4A N2A C3A 0.5 . . . . ?

_shelx_res_file                  
;
TITL nr16005x2_a.res in Pbcm
    nr16005x2.res
    created by SHELXL-2018/3 at 14:17:06 on 10-Apr-2018
REM Old TITL nr16005x2 in Pbcm #57
REM SHELXT solution in Pbcm
REM R1 0.133, Rweak 0.011, Alpha 0.031, Orientation as input
REM Formula found by SHELXT: C2 N8 I9 Bi2
CELL 0.71073 9.8257 14.6666 23.2957 90 90 90
ZERR 4 0.0002 0.0003 0.0004 0 0 0
LATT 1
SYMM -X,-Y,0.5+Z
SYMM -X,0.5+Y,0.5-Z
SYMM +X,0.5-Y,-Z
SFAC C H Bi I N S
UNIT 36 48 8 36 12 12
EQIV $1 +X,+Y,1.5-Z
DFIX 1.35 C2 C2_$1 C5A C4A C5 C4
DFIX 1.37 N1 C2 N2A C4A N2 C4
DFIX 1.3 N1 C1 N2 C3 N2A C3A
DFIX 1.69 S1 C1 S2 C3 S2A C3A
DFIX 1.68 S1 C2 S2 C5 S2A C5A
DANG 2.18 C1 C2 C4 C3 C4A C3A
FLAT S2 N2 C3 C4 C5
FLAT S2A N2A C3A C4A C5A
RIGU S1 N1 C1 C2
RIGU S2 N2 C3 C4 C5
RIGU S2A N2A C3A C4A C5A
RIGU C1 N1 C2
ISOR N2A C4A C5A
ISOR N1
EADP C3 S2A
EADP S2A C3
EXYZ C3 S2A

L.S. 16
PLAN  1
SIZE 0.021 0.099 0.132
TEMP -23.15
FREE S2 C4
FREE N1 N1_$1
BOND $H
list 4
MORE -1
CONF
fmap 2
acta 52
REM <olex2.extras>
REM <HklSrc "%.\\nr16005x2.hkl">
REM </olex2.extras>

WGHT    0.000000  117.931503
FVAR       0.07406   0.75376
BI1   3    0.251376    0.434364    0.657930    11.00000    0.03282    0.03130 =
         0.02605    0.00003   -0.00152   -0.00129
I1    4    0.015000    0.492869    0.750000    10.50000    0.03276    0.03985 =
         0.03906    0.00000    0.00000    0.00240
I2    4    0.435502    0.544887    0.750000    10.50000    0.04171    0.04012 =
         0.03165    0.00000    0.00000   -0.01598
I3    4    0.281658    0.270460    0.750000    10.50000    0.04957    0.02909 =
         0.02894    0.00000    0.00000    0.00621
I4    4    0.215770    0.596866    0.583954    11.00000    0.05947    0.03650 =
         0.04611    0.00935   -0.00214    0.00635
I5    4    0.064727    0.324672    0.586088    11.00000    0.05000    0.05103 =
         0.04097   -0.00762   -0.00584   -0.01718
I6    4    0.495557    0.371141    0.594848    11.00000    0.03795    0.04774 =
         0.04432   -0.00259    0.00458    0.00014
PART 1
S1    6    0.759732    0.294406    0.688657    10.50000    0.07131    0.08300 =
         0.08139   -0.00648   -0.02112    0.01231
PART 0
PART 2
N1    5    0.756013    0.282082    0.709757    10.50000    0.08077    0.15521 =
         0.06489   -0.01327   -0.02214    0.06667
AFIX  43
H1    2    0.726792    0.282906    0.674507    10.50000   -1.20000
AFIX   0
PART 0
C1    1    0.680454    0.319268    0.750000    10.50000    0.01667    0.03791 =
         0.09264    0.00000    0.00000    0.00138
PART 1
AFIX  43
H1A   2    0.593810    0.346440    0.750000    10.25000   -1.20000
AFIX  43
PART 0
PART 2
H1B   2    0.603355    0.357212    0.750000    10.25000   -1.20000
AFIX   0
PART 0
C2    1    0.880625    0.241558    0.721363    11.00000    0.03497    0.03612 =
         0.04511    0.00556    0.00671    0.00433
PART 1
AFIX  43
H2A   2    0.949389    0.211498    0.700655    10.50000   -1.20000
AFIX  43
PART 0
PART 2
H2B   2    0.947146    0.219925    0.695761    10.50000   -1.20000
AFIX   0

PART 0
PART 1
S2    6    0.753869    0.572872    0.853354    21.00000    0.12557    0.10424 =
         0.10315   -0.00402    0.04707    0.00965

PART 0
PART 2
S2A   6    0.628577    0.629078    0.882331   -21.00000    0.06803    0.06041 =
         0.06099    0.00107    0.00314    0.00034

PART 0
PART 1
N2    5    0.643887    0.620283    0.938741    21.00000    0.07832    0.08288 =
         0.05338    0.01595    0.05373    0.02437
AFIX  43
H2    2    0.588660    0.644741    0.963540    21.00000   -1.20000
AFIX   0
C3    1    0.628577    0.629078    0.882331    21.00000    0.06803    0.06041 =
         0.06099    0.00107    0.00314    0.00034
AFIX  43
H3    2    0.559500    0.661198    0.863086    21.00000   -1.20000
AFIX   1

PART 0
PART 2
C3A   1    0.605690    0.620760    0.953040   -21.00000    0.00000
AFIX  43
H3A   2    0.531455    0.644726    0.973538   -21.00000   -1.20000
AFIX   0

PART 0
PART 1
C4    1    0.754289    0.569321    0.954198    21.00000    0.10286    0.10994 =
         0.03145   -0.02701   -0.00964    0.03224
AFIX  43
H4    2    0.776619    0.558715    0.992862    21.00000   -1.20000
AFIX   0
C5    1    0.829610    0.535006    0.910719    21.00000    0.05334    0.06599 =
         0.08613   -0.00338    0.01984    0.02001
AFIX  43
H5    2    0.907477    0.497960    0.913067    21.00000   -1.20000
AFIX   1

PART 0
PART 2
C5A   1    0.774750    0.571690    0.886150   -21.00000    0.09672
AFIX  43
H5A   2    0.829665    0.558859    0.854112   -21.00000   -1.20000
AFIX   1
C4A   1    0.805900    0.545570    0.940230   -21.00000    0.00000
AFIX  43
H4A   2    0.883288    0.512129    0.951161   -21.00000   -1.20000
AFIX   1
N2A   5    0.708100    0.575290    0.975630   -21.00000    0.00000
AFIX  43
H2AA  2    0.712093    0.564895    1.012359   -21.00000   -1.20000
AFIX   0
HKLF 4




REM  nr16005x2_a.res in Pbcm
REM wR2 = 0.1159, GooF = S = 1.332, Restrained GooF = 1.339 for all data
REM R1 = 0.0590 for 3086 Fo > 4sig(Fo) and 0.0609 for all 3158 data
REM 134 parameters refined using 67 restraints

END

WGHT      0.0000    117.9841

REM Highest difference peak  1.562,  deepest hole -2.199,  1-sigma level  0.246
Q1    1   0.8189  0.5350  0.8859  11.00000  0.05    1.56
;
_shelx_res_checksum              86905
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method 
'The crystal was mounted on a MITIGEN holder in Paratone oil.'
_olex2_submission_original_sample_id THB
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
;
_oxdiff_exptl_absorpt_empirical_full_max 2.287
_oxdiff_exptl_absorpt_empirical_full_min 0.609
####################################################################### 
# 
# 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_nr16007_refinalized_fi
_database_code_depnum_ccdc_archive 'CCDC 1561659'
_audit_update_record             
;
2018-04-09 deposited with the CCDC.
2018-04-24 downloaded from the CCDC.
;
_audit_creation_date             2018-03-06
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2018.02.02 svn.r3481 for OlexSys, GUI svn.r5470)
;
_shelx_SHELXL_version_number     2018/1
loop_
_audit_author_email
g.s.nichol@ed.ac.uk
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Bi I4, C3 H5 N2 S'
_chemical_formula_sum            'C3 H5 Bi I4 N2 S'
_chemical_formula_weight         817.73
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C3 H5 N2 S Bi I4'
_chemical_oxdiff_usercomment     '@ 120 K ANB'
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'
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'
S S 0.1246 0.1234 '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                   18.5429(4)
_cell_length_b                   7.53048(19)
_cell_length_c                   19.1421(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2672.94(12)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    17194
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      30.9170
_cell_measurement_theta_min      3.6100
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    22.546
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.474
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.43h (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    4.064
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       cylinder
_exptl_crystal_F_000             2784
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
1 0 5 0.0594
-1 0 -5 0.0594
-1 3 -5 0.1844
1 3 5 0.2273
0 -5 1 0.2527
5 0 -1 0.0378
-5 0 1 0.0378

_exptl_crystal_size_length       0.500
_exptl_crystal_size_max          0.506
_exptl_crystal_size_mid          0.119
_exptl_crystal_size_min          0.076
_exptl_crystal_size_rad          0.100
loop_
_exptl_oxdiff_crystal_face_indexfrac_h
_exptl_oxdiff_crystal_face_indexfrac_k
_exptl_oxdiff_crystal_face_indexfrac_l
_exptl_oxdiff_crystal_face_x
_exptl_oxdiff_crystal_face_y
_exptl_oxdiff_crystal_face_z
1.0050 -0.0008 4.9910 0.0533 -0.1794 0.0262
-1.0050 0.0008 -4.9910 -0.0533 0.1794 -0.0262
-0.9887 2.9969 -4.9891 -0.0731 0.2139 0.2531
1.0212 2.9952 4.9928 0.0336 -0.1449 0.3054
-0.0257 -4.9934 0.9953 0.0361 -0.0941 -0.4606
4.9902 -0.0024 -1.0026 0.1867 0.0539 0.0065
-4.9902 0.0024 1.0026 -0.1867 -0.0539 -0.0065

_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0749
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            53117
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.295
_diffrn_reflns_theta_min         3.059
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.967
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):
  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -20.00  27.00   1.00    5.00    --  -13.24 -99.00-120.00   47
  2  ω    -87.00  18.00   1.00    5.00    --  -13.24 -77.00-180.00  105
  3  ω    -40.00  57.00   1.00    5.00    --  -13.24  57.00  90.00   97
  4  ω    -40.00  57.00   1.00    5.00    --  -13.24  57.00-180.00   97
  5  ω    -20.00  27.00   1.00    5.00    --  -13.24 -99.00 -90.00   47
  6  ω    -83.00  13.00   1.00    5.00    --  -13.24 -57.00 -60.00   96
  7  ω    -22.00  93.00   1.00    5.00    --   14.65  19.00  60.00  115
  8  ω     35.00 101.00   1.00    5.00    --   14.65 178.00 -30.00   66
  9  ω      2.00  27.00   1.00    5.00    --   14.65 -57.00 120.00   25
 10  ω     -9.00  18.00   1.00    5.00    --   14.65 -57.00  30.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford DIffraction SuperNova'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0380218000
_diffrn_orient_matrix_UB_12      -0.0068131000
_diffrn_orient_matrix_UB_13      0.0030307000
_diffrn_orient_matrix_UB_21      0.0034394000
_diffrn_orient_matrix_UB_22      0.0115340000
_diffrn_orient_matrix_UB_23      -0.0366355000
_diffrn_orient_matrix_UB_31      0.0023162000
_diffrn_orient_matrix_UB_32      0.0931836000
_diffrn_orient_matrix_UB_33      0.0047929000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3740
_reflns_number_total             4210
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_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 1.171.38.43h (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43h (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43h (Rigaku OD, 2015)'
_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    ?
_refine_diff_density_max         3.179
_refine_diff_density_min         -2.474
_refine_diff_density_rms         0.354
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.110
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     101
_refine_ls_number_reflns         4210
_refine_ls_number_restraints     36
_refine_ls_R_factor_all          0.0499
_refine_ls_R_factor_gt           0.0412
_refine_ls_restrained_S_all      1.111
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0217P)²+44.7064P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0769
_refine_ls_wR_factor_ref         0.0802
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All N(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
N5 \\sim S1 \\sim N2 \\sim C1 \\sim C2 \\sim C3: within 2A with sigma of 0.001
and sigma for terminal atoms of 0.002
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3)
3.b Idealised Me refined as rotating group:
 N5(H5A,H5B,H5C)
;
_atom_sites_solution_hydrogens   geom
_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
Bi1 Bi 0.45202(2) 0.25252(4) 0.45081(2) 0.01162(7) Uani 1 1 d . . . . .
I1 I 0.52973(3) -0.08801(6) 0.39530(2) 0.01436(10) Uani 1 1 d . . . . .
I2 I 0.30762(3) 0.09840(7) 0.44327(3) 0.02012(12) Uani 1 1 d . . . . .
I3 I 0.61132(2) 0.41381(6) 0.48618(3) 0.01658(11) Uani 1 1 d . . . . .
I5 I 0.46493(3) 0.38366(7) 0.30607(3) 0.02062(12) Uani 1 1 d . . . . .
N5 N 0.3602(4) 0.8021(12) 0.2987(4) 0.0326(11) Uani 1 1 d . U . . .
H5A H 0.374957 0.915293 0.290264 0.049 Uiso 1 1 calc GR . . . .
H5B H 0.398936 0.728081 0.298193 0.049 Uiso 1 1 calc GR . . . .
H5C H 0.338464 0.796929 0.341339 0.049 Uiso 1 1 calc GR . . . .
S1 S 0.22246(12) 0.7710(3) 0.25847(13) 0.0287(4) Uani 1 1 d . U . . .
N2 N 0.3330(4) 0.6893(11) 0.1855(4) 0.0270(6) Uani 1 1 d . U . . .
C1 C 0.3136(5) 0.7526(12) 0.2498(5) 0.0282(6) Uani 1 1 d . U . . .
C2 C 0.2721(5) 0.6505(12) 0.1455(5) 0.0279(7) Uani 1 1 d . U . . .
H2 H 0.274988 0.600926 0.099989 0.034 Uiso 1 1 calc R . . . .
C3 C 0.2097(5) 0.6882(13) 0.1761(5) 0.0286(6) Uani 1 1 d . U . . .
H3 H 0.163812 0.671453 0.155045 0.034 Uiso 1 1 calc R . . . .

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
Bi1 0.00760(12) 0.01592(13) 0.01133(14) 0.00029(10) 0.00003(9) 0.00000(9)
I1 0.0144(2) 0.0180(2) 0.0106(2) -0.00001(17) 0.00122(16) 0.00212(17)
I2 0.0083(2) 0.0265(3) 0.0256(3) 0.0007(2) -0.00026(18) -0.00388(18)
I3 0.0071(2) 0.0184(2) 0.0243(3) -0.00470(19) -0.00009(17) 0.00102(17)
I5 0.0217(3) 0.0276(3) 0.0125(2) 0.0056(2) 0.00045(18) 0.0028(2)
N5 0.025(2) 0.038(2) 0.035(2) -0.001(2) 0.0002(19) 0.0072(19)
S1 0.0195(9) 0.0350(10) 0.0317(11) 0.0050(9) 0.0055(8) 0.0059(8)
N2 0.0185(12) 0.0326(13) 0.0297(14) 0.0037(12) 0.0047(11) 0.0050(12)
C1 0.0194(11) 0.0341(12) 0.0310(13) 0.0036(11) 0.0044(10) 0.0057(11)
C2 0.0199(13) 0.0334(14) 0.0305(14) 0.0043(12) 0.0040(12) 0.0047(12)
C3 0.0200(12) 0.0342(13) 0.0315(13) 0.0048(11) 0.0039(11) 0.0051(11)

_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 I1 3.2134(5) 5_656 ?
Bi1 I1 3.1275(5) . ?
Bi1 I2 2.9219(5) . ?
Bi1 I3 3.0246(5) 5_666 ?
Bi1 I3 3.2648(5) . ?
Bi1 I5 2.9511(6) . ?
N5 H5A 0.9100 . ?
N5 H5B 0.9100 . ?
N5 H5C 0.9100 . ?
N5 C1 1.327(12) . ?
S1 C1 1.705(9) . ?
S1 C3 1.711(10) . ?
N2 C1 1.368(12) . ?
N2 C2 1.395(12) . ?
C2 H2 0.9500 . ?
C2 C3 1.327(12) . ?
C3 H3 0.9500 . ?

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
I1 Bi1 I1 86.955(14) . 5_656 ?
I1 Bi1 I3 87.630(14) . . ?
I1 Bi1 I3 81.844(14) 5_656 . ?
I2 Bi1 I1 94.573(16) . . ?
I2 Bi1 I1 89.349(15) . 5_656 ?
I2 Bi1 I3 89.644(15) . 5_666 ?
I2 Bi1 I3 170.804(17) . . ?
I2 Bi1 I5 99.254(17) . . ?
I3 Bi1 I1 89.749(15) 5_666 5_656 ?
I3 Bi1 I1 174.613(16) 5_666 . ?
I3 Bi1 I3 87.686(14) 5_666 . ?
I5 Bi1 I1 85.297(15) . . ?
I5 Bi1 I1 168.842(16) . 5_656 ?
I5 Bi1 I3 97.347(17) . 5_666 ?
I5 Bi1 I3 89.817(16) . . ?
Bi1 I1 Bi1 93.046(14) . 5_656 ?
Bi1 I3 Bi1 92.314(14) 5_666 . ?
H5A N5 H5B 109.5 . . ?
H5A N5 H5C 109.5 . . ?
H5B N5 H5C 109.5 . . ?
C1 N5 H5A 109.5 . . ?
C1 N5 H5B 109.5 . . ?
C1 N5 H5C 109.5 . . ?
C1 S1 C3 91.0(5) . . ?
C1 N2 C2 110.7(7) . . ?
N5 C1 S1 123.6(7) . . ?
N5 C1 N2 124.2(8) . . ?
N2 C1 S1 112.1(7) . . ?
N2 C2 H2 122.6 . . ?
C3 C2 N2 114.8(9) . . ?
C3 C2 H2 122.6 . . ?
S1 C3 H3 124.3 . . ?
C2 C3 S1 111.3(8) . . ?
C2 C3 H3 124.3 . . ?

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 C2 C3 S1 -1.4(11) . . . . ?
C1 S1 C3 C2 0.0(8) . . . . ?
C1 N2 C2 C3 2.4(12) . . . . ?
C2 N2 C1 N5 -179.3(9) . . . . ?
C2 N2 C1 S1 -2.3(10) . . . . ?
C3 S1 C1 N5 178.4(9) . . . . ?
C3 S1 C1 N2 1.4(7) . . . . ?

_shelx_res_file                  
;
TITL NR16007_refinalized_fi in Pbca #61
    nr16007_refinalized_fi.res
    created by SHELXL-2018/1 at 11:49:30 on 06-Mar-2018
REM reset to Pbca #61
CELL 0.71073 18.542935 7.530483 19.142049 90 90 90
ZERR 8 0.000408 0.00019 0.000552 0 0 0
LATT 1
SYMM 0.5-X,-Y,0.5+Z
SYMM 0.5+X,0.5-Y,-Z
SYMM -X,0.5+Y,0.5-Z
SFAC C H Bi I N S
UNIT 24 40 8 32 16 8
SIMU 0.001 0.002 2 N5 > C3
L.S. 16
PLAN  20
TEMP -153
LIST 4
BOND
HTAB
CONF
fmap 2
acta
bond $h
more -1
REM <olex2.extras>
REM <HklSrc "%.\\NR16007_refinalized_fi.hkl">
REM </olex2.extras>
WGHT    0.021700   44.706402
FVAR       0.74453
BI1   3    0.452024    0.252519    0.450814    11.00000    0.00760    0.01592 =
         0.01133    0.00029    0.00003    0.00000
I1    4    0.529731   -0.088007    0.395299    11.00000    0.01442    0.01803 =
         0.01063   -0.00001    0.00122    0.00212
I2    4    0.307623    0.098400    0.443270    11.00000    0.00830    0.02648 =
         0.02556    0.00070   -0.00026   -0.00388
I3    4    0.611322    0.413813    0.486176    11.00000    0.00711    0.01836 =
         0.02426   -0.00470   -0.00009    0.00102
I5    4    0.464928    0.383655    0.306070    11.00000    0.02171    0.02764 =
         0.01251    0.00557    0.00045    0.00282
N5    5    0.360153    0.802115    0.298743    11.00000    0.02456    0.03833 =
         0.03499   -0.00086    0.00016    0.00720
AFIX 137
H5A   2    0.374957    0.915293    0.290264    11.00000   -1.50000
H5B   2    0.398936    0.728081    0.298193    11.00000   -1.50000
H5C   2    0.338464    0.796929    0.341339    11.00000   -1.50000
AFIX   0
S1    6    0.222461    0.770980    0.258469    11.00000    0.01945    0.03502 =
         0.03171    0.00496    0.00551    0.00587
N2    5    0.333004    0.689256    0.185491    11.00000    0.01853    0.03265 =
         0.02974    0.00370    0.00465    0.00502
C1    1    0.313645    0.752603    0.249804    11.00000    0.01938    0.03410 =
         0.03098    0.00362    0.00436    0.00570
C2    1    0.272062    0.650480    0.145541    11.00000    0.01990    0.03337 =
         0.03052    0.00432    0.00403    0.00469
AFIX  43
H2    2    0.274988    0.600926    0.099989    11.00000   -1.20000
AFIX   0
C3    1    0.209680    0.688231    0.176146    11.00000    0.01996    0.03422 =
         0.03148    0.00476    0.00390    0.00509
AFIX  43
H3    2    0.163812    0.671453    0.155045    11.00000   -1.20000
AFIX   0
HKLF 4
REM  NR16007_refinalized_fi in Pbca #61
REM R1 =  0.0412 for    3740 Fo > 4sig(Fo)  and  0.0499 for all    4210 data
REM    101 parameters refined using     36 restraints
END
WGHT      0.0217     44.7023
REM Instructions for potential hydrogen bonds
HTAB N5 I5
EQIV $3 x, y+1, z
HTAB N5 I2_$3
EQIV $4 x-1/2, y+1, -z+1/2
HTAB C3 I1_$4
REM Highest difference peak  3.179,  deepest hole -2.474,  1-sigma level  0.354
Q1    1   0.4557  0.1437  0.4504  11.00000  0.05    3.18
Q2    1   0.4551  0.3616  0.4511  11.00000  0.05    2.97
Q3    1   0.4871  0.2544  0.4498  11.00000  0.05    2.34
Q4    1   0.4510  0.3342  0.4756  11.00000  0.05    2.10
Q5    1   0.4634  0.2769  0.3085  11.00000  0.05    1.97
Q6    1   0.2373  0.6749  0.1547  11.00000  0.05    1.85
Q7    1   0.3076  0.0125  0.4819  11.00000  0.05    1.76
Q8    1   0.4186  0.2533  0.4517  11.00000  0.05    1.75
Q9    1   0.5348  0.0150  0.3917  11.00000  0.05    1.71
Q10   1   0.4297  0.3923  0.3105  11.00000  0.05    1.68
Q11   1   0.3062 -0.0091  0.4361  11.00000  0.05    1.68
Q12   1   0.1974  0.7144  0.2077  11.00000  0.05    1.66
Q13   1   0.4619  0.3000  0.3383  11.00000  0.05    1.64
Q14   1   0.6097  0.5288  0.4881  11.00000  0.05    1.57
Q15   1   0.6138  0.5012  0.4526  11.00000  0.05    1.53
Q16   1   0.4891 -0.0880  0.3933  11.00000  0.05    1.52
Q17   1   0.5270 -0.1959  0.3923  11.00000  0.05    1.51
Q18   1   0.6131  0.3019  0.4831  11.00000  0.05    1.47
Q19   1   0.4671  0.4918  0.3018  11.00000  0.05    1.40
Q20   1   0.5290 -0.0202  0.4289  11.00000  0.05    1.39
;
_shelx_res_checksum              48768
_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 5.198
_oxdiff_exptl_absorpt_empirical_full_min 0.528
