# Electronic Supplementary Material (ESI) for Sustainable Energy & Fuels.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_nr15013
_database_code_depnum_ccdc_archive 'CCDC 1507845'
_audit_update_record             
;
2016-10-03 deposited with the CCDC.
2017-01-30 downloaded from the CCDC.
;
_audit_creation_date             2015-12-11
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2015.11.10 svn.r3248 for OlexSys, GUI svn.r5133)
;
_shelxl_version_number           2014/6
_chemical_name_common            ?
_chemical_name_systematic        '1-Methylpyridinium iodobismuthate'
_chemical_formula_moiety         'Bi I4, C6 H8 N'
_chemical_formula_sum            'C6 H8 Bi I4 N'
_chemical_formula_weight         810.71
_chemical_melting_point          ?
_chemical_oxdiff_formula         'C20 H32 N4 Bi2 I10'
_chemical_oxdiff_usercomment     '@120 K Me-Py-1'
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'

_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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   7.7618(5)
_cell_length_b                   14.0412(8)
_cell_length_c                   13.1959(8)
_cell_angle_alpha                90
_cell_angle_beta                 92.959(6)
_cell_angle_gamma                90
_cell_volume                     1436.24(15)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    6531
_cell_measurement_temperature    120.00
_cell_measurement_theta_max      30.3020
_cell_measurement_theta_min      4.1260
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    20.836
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89487
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    3.749
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1384
_exptl_crystal_recrystallization_method 
'The material was recrystallised from a mixture of ethanol and water by solvent layering'
_exptl_crystal_size_max          0.0925
_exptl_crystal_size_mid          0.0617
_exptl_crystal_size_min          0.058
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_unetI/netI     0.0917
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            7443
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.967
_diffrn_reflns_theta_min         2.901
_diffrn_reflns_v_R_equivalents   ?
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00
_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 0.958
_diffrn_measurement_details      
;
#__ type_ start__ end____ width___ exp.time_
  1 omega -103.00  -55.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.6872  178.0000   60.0000 48

#__ type_ start__ end____ width___ exp.time_
  2 omega  -20.00   27.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.6872  -99.0000  -30.0000 47

#__ type_ start__ end____ width___ exp.time_
  3 omega  -20.00   27.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.6872  -99.0000   60.0000 47

#__ type_ start__ end____ width___ exp.time_
  4 omega  -20.00   27.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.6872  -99.0000 -120.0000 47

#__ type_ start__ end____ width___ exp.time_
  5 omega -103.00  -55.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.6872  178.0000  -30.0000 48

#__ type_ start__ end____ width___ exp.time_
  6 omega  -65.00   62.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       16.2497  -19.0000  -60.0000 127

#__ type_ start__ end____ width___ exp.time_
  7 omega   35.00  106.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       16.2497  178.0000   90.0000 71

#__ type_ start__ end____ width___ exp.time_
  8 omega   35.00  106.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       16.2497  178.0000  -30.0000 71

#__ type_ start__ end____ width___ exp.time_
  9 omega  -10.00   92.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       16.2497   38.0000 -150.0000 102

#__ type_ start__ end____ width___ exp.time_
 10 omega  -30.00   47.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       16.2497   19.0000  120.0000 77
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_UB_11      -0.0777978000
_diffrn_orient_matrix_UB_12      0.0182711000
_diffrn_orient_matrix_UB_13      0.0182000000
_diffrn_orient_matrix_UB_21      0.0015935000
_diffrn_orient_matrix_UB_22      -0.0357103000
_diffrn_orient_matrix_UB_23      0.0380635000
_diffrn_orient_matrix_UB_31      0.0481534000
_diffrn_orient_matrix_UB_32      0.0307176000
_diffrn_orient_matrix_UB_33      0.0334024000
loop_
_diffrn_oxdiff_twin_id
_diffrn_oxdiff_twin_ratio
_diffrn_oxdiff_twin_reflns_isolated
_diffrn_oxdiff_twin_reflns_overlapped
1 0.5300 7579 18941
2 0.4700 7529 18941

_diffrn_oxdiff_twin_integration_method simultaneous
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_diffrn_special_details          ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                5413
_reflns_number_total             7443
_reflns_special_details          
;
 _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, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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         2.285
_refine_diff_density_min         -1.785
_refine_diff_density_rms         0.372
_refine_ls_extinction_coef       0.00018(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   0.924
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     112
_refine_ls_number_reflns         7443
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0659
_refine_ls_R_factor_gt           0.0427
_refine_ls_restrained_S_all      0.924
_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)+(0.0317P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0750
_refine_ls_wR_factor_ref         0.0784
_refine_special_details          
;
The crystal used was a non-merohedral twin. CrysAlisPro was used to deconvolute and integrate the twin, with twin law [1 0 0 / 0 -1 0 / -0.1727 0 -1] and refined twin scale factor 0.4523(7). The crystal used was also strongly absorbing of X-ray and CrysAlisPro was used to provide an appropriate correction.Despite this some of the C ellipsoids were uneven; the RIGU command was used to apply a restraint to all six atoms of the pyridine ring.


#===============================================================================
The Following Improvement and Query ALERTS were generated - (Acta-Mode) <<<
#===============================================================================
     Format: alert-number_ALERT_alert-type_alert-level text
 
342_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0165 Ang.
906_ALERT_3_C Large K value in the Analysis of Variance ......      3.205 Check

Not significant

#===============================================================================
004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.15 Ratio
794_ALERT_5_G Tentative Bond Valency for Bi1     (III)   .....       3.04 Note
802_ALERT_4_G CIF Input Record(s) with more than 80 Characters          4 Info

Not significant


870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed ..          ! Info

See above 

910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          2 Report
912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        302 Note
931_ALERT_5_G Found Twin Law ( 0 0  1)[       ] Estimated BASF       0.39 Check

See above

#===============================================================================


;


_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.5477(7) 0.4523(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5)
3.b Idealised Me refined as rotating group:
 C6(H6a,H6b,H6c)
;
_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 0.24940(6) 0.41008(3) 0.50940(3) 0.01074(10) Uani 1 1 d . . . . .
I1 I 0.41156(9) 0.27866(5) 0.65572(5) 0.01560(17) Uani 1 1 d . . . . .
I2 I -0.05978(9) 0.43405(4) 0.64714(5) 0.01422(16) Uani 1 1 d . . . . .
I3 I 0.08964(9) 0.25510(5) 0.39078(5) 0.01630(16) Uani 1 1 d . . . . .
I4 I 0.56330(8) 0.40992(5) 0.37260(5) 0.01381(16) Uani 1 1 d . . . . .
N1 N 0.7953(11) 0.1068(6) 0.5658(7) 0.017(2) Uani 1 1 d . . . . .
C1 C 0.7999(14) 0.0126(7) 0.5554(8) 0.020(3) Uani 1 1 d . . . . .
H1 H 0.8548 -0.0255 0.6070 0.024 Uiso 1 1 calc R . . . .
C2 C 0.7264(15) -0.0287(8) 0.4714(9) 0.025(3) Uani 1 1 d . . . . .
H2 H 0.7255 -0.0961 0.4649 0.029 Uiso 1 1 calc R . . . .
C3 C 0.6529(16) 0.0272(8) 0.3954(9) 0.029(3) Uani 1 1 d . . . . .
H3 H 0.6049 -0.0012 0.3350 0.035 Uiso 1 1 calc R . . . .
C4 C 0.6493(15) 0.1242(9) 0.4071(9) 0.027(3) Uani 1 1 d . . . . .
H4 H 0.5986 0.1637 0.3553 0.032 Uiso 1 1 calc R . . . .
C5 C 0.7206(12) 0.1637(7) 0.4956(8) 0.014(2) Uani 1 1 d . . . . .
H5 H 0.7163 0.2305 0.5064 0.017 Uiso 1 1 calc R . . . .
C6 C 0.8855(14) 0.1510(7) 0.6568(8) 0.019(2) Uani 1 1 d . . . . .
H6A H 0.8025 0.1878 0.6944 0.029 Uiso 1 1 calc GR . . . .
H6B H 0.9769 0.1934 0.6350 0.029 Uiso 1 1 calc GR . . . .
H6C H 0.9361 0.1010 0.7006 0.029 Uiso 1 1 calc GR . . . .


_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 2.9098(8) . ?
Bi1 I2 3.1027(9) . ?
Bi1 I2 3.3029(7) 3_566 ?
Bi1 I3 2.9195(8) . ?
Bi1 I4 3.1063(8) . ?
Bi1 I4 3.2699(7) 3_666 ?
I2 Bi1 3.3029(7) 3_566 ?
I4 Bi1 3.2699(7) 3_666 ?
N1 C1 1.330(12) . ?
N1 C5 1.332(13) . ?
N1 C6 1.494(13) . ?
C1 H1 0.9500 . ?
C1 C2 1.352(15) . ?
C2 H2 0.9500 . ?
C2 C3 1.374(17) . ?
C3 H3 0.9500 . ?
C3 C4 1.372(17) . ?
C4 H4 0.9500 . ?
C4 C5 1.382(15) . ?
C5 H5 0.9500 . ?
C6 H6A 0.9800 . ?
C6 H6B 0.9800 . ?
C6 H6C 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
I1 Bi1 I2 90.07(2) . . ?
I1 Bi1 I2 177.14(2) . 3_566 ?
I1 Bi1 I3 92.31(2) . . ?
I1 Bi1 I4 93.43(2) . . ?
I1 Bi1 I4 90.44(2) . 3_666 ?
I2 Bi1 I2 87.79(2) . 3_566 ?
I2 Bi1 I4 88.60(2) . 3_666 ?
I2 Bi1 I4 173.79(2) . . ?
I3 Bi1 I2 94.30(2) . . ?
I3 Bi1 I2 89.74(2) . 3_566 ?
I3 Bi1 I4 176.00(2) . 3_666 ?
I3 Bi1 I4 90.69(2) . . ?
I4 Bi1 I2 87.620(19) 3_666 3_566 ?
I4 Bi1 I2 88.54(2) . 3_566 ?
I4 Bi1 I4 86.25(2) . 3_666 ?
Bi1 I2 Bi1 92.21(2) . 3_566 ?
Bi1 I4 Bi1 93.75(2) . 3_666 ?
C1 N1 C5 122.5(9) . . ?
C1 N1 C6 118.8(9) . . ?
C5 N1 C6 118.6(8) . . ?
N1 C1 H1 120.0 . . ?
N1 C1 C2 120.0(10) . . ?
C2 C1 H1 120.0 . . ?
C1 C2 H2 120.2 . . ?
C1 C2 C3 119.6(10) . . ?
C3 C2 H2 120.2 . . ?
C2 C3 H3 120.2 . . ?
C4 C3 C2 119.7(11) . . ?
C4 C3 H3 120.2 . . ?
C3 C4 H4 120.5 . . ?
C3 C4 C5 118.9(11) . . ?
C5 C4 H4 120.5 . . ?
N1 C5 C4 119.2(10) . . ?
N1 C5 H5 120.4 . . ?
C4 C5 H5 120.4 . . ?
N1 C6 H6A 109.5 . . ?
N1 C6 H6B 109.5 . . ?
N1 C6 H6C 109.5 . . ?
H6A C6 H6B 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?

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
N1 C1 C2 C3 2.4(18) . . . . ?
C1 N1 C5 C4 -2.0(15) . . . . ?
C1 C2 C3 C4 -2.4(18) . . . . ?
C2 C3 C4 C5 0.2(17) . . . . ?
C3 C4 C5 N1 2.0(16) . . . . ?
C5 N1 C1 C2 -0.2(16) . . . . ?
C6 N1 C1 C2 -176.8(10) . . . . ?
C6 N1 C5 C4 174.6(10) . . . . ?

loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
_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
0 5 1 0.0290 -0.0069 4.9986 1.0036 0.1101 -0.1403 0.1867
0 4 5 0.0292 -0.0084 3.9999 5.0014 0.1648 0.0475 0.2895
1 4 -5 0.0214 0.9973 4.0013 -4.9939 -0.0954 -0.3314 0.0041
0 1 -5 0.0177 0.0021 0.9984 -4.9976 -0.0729 -0.2259 -0.1362
0 -1 5 0.0440 -0.0021 -0.9984 4.9976 0.0729 0.2259 0.1362
5 2 0 0.0487 4.9924 2.0190 0.0081 -0.3514 -0.0638 0.3027
2 -4 -5 0.0308 2.0063 -3.9920 -4.9988 -0.3200 -0.0445 -0.1930
4 -2 -5 0.0378 4.0018 -1.9848 -4.9946 -0.4385 -0.1129 -0.0351
-4 3 5 0.0315 -4.0030 2.9845 4.9954 0.4569 0.0772 0.0658
0 -4 -5 0.0292 0.0084 -3.9999 -5.0014 -0.1648 -0.0475 -0.2895
-5 -2 1 0.0397 -4.9930 -2.0188 0.9915 0.3696 0.1019 -0.2693
3 -5 4 0.0426 3.0005 -4.9855 3.9987 -0.2517 0.3350 0.1249
3 3 5 0.0405 2.9898 3.0121 5.0046 -0.0865 0.0877 0.4037
-3 2 -5 0.0292 -2.9961 1.9862 -5.0007 0.1784 -0.2660 -0.2503
0 -5 -1 0.0290 0.0069 -4.9986 -1.0036 -0.1101 0.1403 -0.1867

_olex2_date_sample_data_collection 2015-12-02
_olex2_date_sample_submission    2015-11-23
_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 Me-Py-1
_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.5477(7)
2 0.4523(7)

####################################################################### 
# 
# 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_nr16001
_database_code_depnum_ccdc_archive 'CCDC 1507844'
_audit_update_record             
;
2016-10-03 deposited with the CCDC.
2017-01-30 downloaded from the CCDC.
;
_audit_creation_date             2016-02-04
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2015.11.10 svn.r3248 for OlexSys, GUI svn.r5133)
;
_chemical_name_common            ?
_chemical_name_systematic        'pyridinium iodobismuthate'
_chemical_formula_moiety         '0.5(Bi2 I8), C5 H6 N'
_chemical_formula_sum            'C5 H6 Bi I4 N'
_chemical_formula_weight         796.69
_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'
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'

_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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   12.6997(3)
_cell_length_b                   28.3198(6)
_cell_length_c                   7.7160(2)
_cell_angle_alpha                90
_cell_angle_beta                 95.2880(10)
_cell_angle_gamma                90
_cell_volume                     2763.27(11)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    4251
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.145
_cell_measurement_theta_min      2.747
_shelx_estimated_absorpt_T_max   0.260
_shelx_estimated_absorpt_T_min   0.063
_exptl_absorpt_coefficient_mu    21.656
_exptl_absorpt_correction_T_max  0.431
_exptl_absorpt_correction_T_min  0.170
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1437 before and 0.0617 after correction.
 The Ratio of minimum to maximum transmission not present.
 The λ/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.1395 before and 0.0624 after correction.
 The Ratio of minimum to maximum transmission is 0.40.
 The λ/2 correction factor is Not present

Final HKLF 4 output contains 32593 reflections, Rint = 0.0701
 (18008 with I > 3sig(I), Rint = 0.0570)
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    3.830
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             2704
_exptl_crystal_recrystallization_method 
'The material was recrystallised from a mixture of ethanol and water by crystallized during reaction'
_exptl_crystal_size_max          0.285
_exptl_crystal_size_mid          0.213
_exptl_crystal_size_min          0.085
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  ?
_diffrn_reflns_av_unetI/netI     0.0571
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            9303
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.313
_diffrn_reflns_theta_min         1.438
_diffrn_ambient_temperature      150
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.933
_diffrn_measurement_device_type  'Bruker SMART APEXII diffractometer'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_source_current           30
_diffrn_source_voltage           50
_diffrn_special_details          ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                7345
_reflns_number_total             9303
_reflns_special_details          
;
 _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       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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         3.098
_refine_diff_density_min         -2.356
_refine_diff_density_rms         0.479
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         6271
_refine_ls_number_restraints     72
_refine_ls_R_factor_all          0.0859
_refine_ls_R_factor_gt           0.0634
_refine_ls_restrained_S_all      1.098
_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)+(0.0744P)²+170.4960P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1650
_refine_ls_wR_factor_ref         0.1785
_refine_special_details          
;
The crystals began to decompose within seconds when removed from the mother liquor, although there are no residual peaks corresponding to solvent in a difference map. The crystal used was a non-merohedral twin. The two twin components were identified with CELL_NOW (twin law -1 0 -0.3 / 0 -1 0 / 0 0 1), refined twin scale factor 0.4799(17). The two pyridinium cations were refined using a displacement ellipsoid similarity restraint to control the size and shape of the ellipsoids (irregular shape a likely consequence of the combination of twinning and significant absorption and contribution to the diffraction by bismuth and iodide.



#===============================================================================
The Following Improvement and Query ALERTS were generated - (Acta-Mode) <<<
#===============================================================================
     Format: alert-number_ALERT_alert-type_alert-level text
 
213_ALERT_2_B Atom N2              has ADP max/min Ratio .....        4.4 prolat

See above, RIGU was used.

250_ALERT_2_B Large U3/U1 Ratio for Average U(i,j) Tensor ....        5.9 Note
342_ALERT_3_B Low Bond Precision on  C-C Bonds ...............    0.06875 Ang.
#===============================================================================
213_ALERT_2_C Atom C10             has ADP max/min Ratio .....        3.8 prolat
250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.1 Note
368_ALERT_2_C Short   C(sp2)-C(sp2) Bond  C9     -   C10    ..       1.23 Ang.
420_ALERT_2_C D-H Without Acceptor       N2     --  H2A    ...     Please Check

The location of the N atom was decided primarily by assessing the quality of the displacement ellipsoids.  However, as noted above, this was not easy as the RIGU card in SHELXL was needed to prevent most atom sites becoming non-positive definite.

#===============================================================================
003_ALERT_2_G Number of Uiso or Uij Restrained non-H Atoms ...         12 Report
004_ALERT_5_G Polymeric Structure Found with Maximum Dimension          1 Info
007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          2 Report
042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
083_ALERT_2_G SHELXL Second Parameter in WGHT  Unusually Large     170.50 Why ?
764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.17 Ratio
794_ALERT_5_G Tentative Bond Valency for Bi1     (III)   .....       3.12 Note
794_ALERT_5_G Tentative Bond Valency for Bi2     (III)   .....       3.07 Note
804_ALERT_5_G Number of ARU-Code Packing Problem(s) in PLATON           4 Info
860_ALERT_3_G Number of Least-Squares Restraints .............         72 Note
870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed ..          ! Info

Noted

#===============================================================================
 


;

_vrf_PLAT213_nr16001             
;
PROBLEM: Atom C10             has ADP max/min Ratio .....        3.8 prolat
RESPONSE: Please see the _refine_special_details section of the CIF.
;



_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.5201(17) 0.4799(17)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
3. Rigid body (RIGU) restrains
 N1, C1, C2, C3, C4, C5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10, C9, C8, C7, C6, N2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1A), C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C9(H9), C8(H8),
 C7(H7), C6(H6), N2(H2A)
;
_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 1.99247(7) 0.54443(3) 1.74910(12) 0.0194(2) Uani 1 1 d . . . . .
I1 I 1.84043(15) 0.61108(7) 1.5854(3) 0.0402(5) Uani 1 1 d . . . . .
I2 I 2.13906(13) 0.54387(5) 1.4441(2) 0.0245(4) Uani 1 1 d . . . . .
I3 I 2.14273(13) 0.46237(6) 1.9442(2) 0.0265(4) Uani 1 1 d . . . . .
I4 I 2.13078(16) 0.61718(7) 1.9080(3) 0.0398(5) Uani 1 1 d . . . . .
Bi2 Bi 1.49999(7) 0.70468(3) 1.19322(13) 0.0205(2) Uani 1 1 d . . . . .
I5 I 1.63843(14) 0.71145(6) 1.5414(2) 0.0290(4) Uani 1 1 d . . . . .
I6 I 1.35981(13) 0.70894(5) 0.8402(2) 0.0252(4) Uani 1 1 d . . . . .
I7 I 1.64791(15) 0.63480(6) 1.0825(3) 0.0351(4) Uani 1 1 d . . . . .
I8 I 1.35792(14) 0.63300(6) 1.3170(3) 0.0313(4) Uani 1 1 d . . . . .
N1 N 2.048(3) 0.6654(11) 1.319(4) 0.061(7) Uani 1 1 d . U . . .
H1 H 2.0777 0.6373 1.3285 0.073 Uiso 1 1 calc R . . . .
C1 C 2.103(4) 0.7038(13) 1.388(7) 0.072(11) Uani 1 1 d . U . . .
H1A H 2.1706 0.7001 1.4506 0.086 Uiso 1 1 calc R . . . .
C2 C 2.060(3) 0.7455(14) 1.367(6) 0.067(10) Uani 1 1 d . U . . .
H2 H 2.1008 0.7721 1.4072 0.080 Uiso 1 1 calc R . . . .
C3 C 1.963(3) 0.7528(14) 1.291(6) 0.061(9) Uani 1 1 d . U . . .
H3 H 1.9331 0.7836 1.2866 0.073 Uiso 1 1 calc R . . . .
C4 C 1.906(3) 0.7141(11) 1.219(6) 0.061(9) Uani 1 1 d . U . . .
H4 H 1.8377 0.7179 1.1584 0.073 Uiso 1 1 calc R . . . .
C5 C 1.954(3) 0.6697(12) 1.239(5) 0.053(7) Uani 1 1 d . U . . .
H5 H 1.9168 0.6425 1.1945 0.063 Uiso 1 1 calc R . . . .
C10 C 2.434(5) 0.5813(19) 1.746(5) 0.095(11) Uani 1 1 d . U . . .
H10 H 2.3975 0.6106 1.7395 0.114 Uiso 1 1 calc R . . . .
C9 C 2.389(5) 0.5464(18) 1.799(7) 0.103(12) Uani 1 1 d . U . . .
H9 H 2.3250 0.5503 1.8513 0.124 Uiso 1 1 calc R . . . .
C8 C 2.427(5) 0.5053(19) 1.785(6) 0.098(12) Uani 1 1 d . U . . .
H8 H 2.3863 0.4779 1.8034 0.117 Uiso 1 1 calc R . . . .
C7 C 2.532(5) 0.502(2) 1.743(6) 0.097(12) Uani 1 1 d . U . . .
H7 H 2.5639 0.4716 1.7504 0.117 Uiso 1 1 calc R . . . .
C6 C 2.588(5) 0.5367(19) 1.694(6) 0.103(12) Uani 1 1 d . U . . .
H6 H 2.6584 0.5332 1.6616 0.124 Uiso 1 1 calc R . . . .
N2 N 2.536(4) 0.5794(15) 1.694(4) 0.096(10) Uani 1 1 d . U . . .
H2A H 2.5664 0.6054 1.6617 0.115 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
Bi1 I1 2.9047(19) . ?
Bi1 I2 3.2872(17) 3_968 ?
Bi1 I2 3.1326(19) . ?
Bi1 I3 3.2830(18) . ?
Bi1 I3 3.0556(19) 3_969 ?
Bi1 I4 2.904(2) . ?
I2 Bi1 3.2873(17) 3_968 ?
I3 Bi1 3.0556(19) 3_969 ?
Bi2 I5 3.2379(19) 4_575 ?
Bi2 I5 3.078(2) . ?
Bi2 I6 3.116(2) . ?
Bi2 I6 3.2877(18) 4_576 ?
Bi2 I7 2.9105(19) . ?
Bi2 I8 2.9338(19) . ?
I5 Bi2 3.2379(18) 4_576 ?
I6 Bi2 3.2878(18) 4_575 ?
N1 H1 0.8800 . ?
N1 C1 1.37(5) . ?
N1 C5 1.31(5) . ?
C1 H1A 0.9500 . ?
C1 C2 1.30(5) . ?
C2 H2 0.9500 . ?
C2 C3 1.33(6) . ?
C3 H3 0.9500 . ?
C3 C4 1.40(5) . ?
C4 H4 0.9500 . ?
C4 C5 1.40(5) . ?
C5 H5 0.9500 . ?
C10 H10 0.9500 . ?
C10 C9 1.23(7) . ?
C10 N2 1.39(7) . ?
C9 H9 0.9500 . ?
C9 C8 1.27(7) . ?
C8 H8 0.9500 . ?
C8 C7 1.40(8) . ?
C7 H7 0.9500 . ?
C7 C6 1.30(7) . ?
C6 H6 0.9500 . ?
C6 N2 1.38(7) . ?
N2 H2A 0.8800 . ?

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 I2 90.43(6) . 3_968 ?
I1 Bi1 I2 95.38(6) . . ?
I1 Bi1 I3 173.92(6) . . ?
I1 Bi1 I3 88.82(6) . 3_969 ?
I2 Bi1 I2 88.16(5) . 3_968 ?
I2 Bi1 I3 88.87(5) . . ?
I3 Bi1 I2 175.53(5) 3_969 . ?
I3 Bi1 I2 90.28(5) 3_969 3_968 ?
I3 Bi1 I2 85.35(5) . 3_968 ?
I3 Bi1 I3 86.83(5) 3_969 . ?
I4 Bi1 I1 94.27(7) . . ?
I4 Bi1 I2 173.34(6) . 3_968 ?
I4 Bi1 I2 86.70(6) . . ?
I4 Bi1 I3 94.53(6) . 3_969 ?
I4 Bi1 I3 90.30(6) . . ?
Bi1 I2 Bi1 91.84(5) . 3_968 ?
Bi1 I3 Bi1 93.17(5) 3_969 . ?
I5 Bi2 I5 89.12(5) . 4_575 ?
I5 Bi2 I6 86.36(5) . 4_576 ?
I5 Bi2 I6 84.75(5) 4_575 4_576 ?
I5 Bi2 I6 174.21(5) . . ?
I6 Bi2 I5 86.60(5) . 4_575 ?
I6 Bi2 I6 89.36(5) . 4_576 ?
I7 Bi2 I5 90.34(6) . 4_575 ?
I7 Bi2 I5 88.07(6) . . ?
I7 Bi2 I6 95.85(6) . . ?
I7 Bi2 I6 172.62(6) . 4_576 ?
I7 Bi2 I8 93.32(6) . . ?
I8 Bi2 I5 94.47(6) . . ?
I8 Bi2 I5 174.96(6) . 4_575 ?
I8 Bi2 I6 91.93(5) . 4_576 ?
I8 Bi2 I6 89.57(5) . . ?
Bi2 I5 Bi2 94.36(5) . 4_576 ?
Bi2 I6 Bi2 92.66(5) . 4_575 ?
C1 N1 H1 119.3 . . ?
C5 N1 H1 119.3 . . ?
C5 N1 C1 121(3) . . ?
N1 C1 H1A 120.7 . . ?
C2 C1 N1 119(5) . . ?
C2 C1 H1A 120.7 . . ?
C1 C2 H2 118.1 . . ?
C1 C2 C3 124(4) . . ?
C3 C2 H2 118.1 . . ?
C2 C3 H3 120.7 . . ?
C2 C3 C4 119(4) . . ?
C4 C3 H3 120.7 . . ?
C3 C4 H4 121.5 . . ?
C5 C4 C3 117(4) . . ?
C5 C4 H4 121.5 . . ?
N1 C5 C4 120(4) . . ?
N1 C5 H5 119.8 . . ?
C4 C5 H5 119.8 . . ?
C9 C10 H10 118.8 . . ?
C9 C10 N2 122(6) . . ?
N2 C10 H10 118.8 . . ?
C10 C9 H9 119.3 . . ?
C10 C9 C8 121(8) . . ?
C8 C9 H9 119.3 . . ?
C9 C8 H8 121.4 . . ?
C9 C8 C7 117(6) . . ?
C7 C8 H8 121.4 . . ?
C8 C7 H7 117.3 . . ?
C6 C7 C8 125(6) . . ?
C6 C7 H7 117.3 . . ?
C7 C6 H6 123.8 . . ?
C7 C6 N2 112(7) . . ?
N2 C6 H6 123.8 . . ?
C10 N2 H2A 120.0 . . ?
C6 N2 C10 120(5) . . ?
C6 N2 H2A 120.0 . . ?

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
N1 C1 C2 C3 5(8) . . . . ?
C1 N1 C5 C4 1(6) . . . . ?
C1 C2 C3 C4 -5(7) . . . . ?
C2 C3 C4 C5 3(6) . . . . ?
C3 C4 C5 N1 -2(6) . . . . ?
C5 N1 C1 C2 -3(7) . . . . ?
C10 C9 C8 C7 13(8) . . . . ?
C9 C10 N2 C6 3(6) . . . . ?
C9 C8 C7 C6 -10(8) . . . . ?
C8 C7 C6 N2 2(7) . . . . ?
C7 C6 N2 C10 1(6) . . . . ?
N2 C10 C9 C8 -11(8) . . . . ?

_shelx_SHELXL_version_number     2014/7
_olex2_date_sample_data_collection 2016-02-02
_olex2_date_sample_submission    2016-01-11
_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 'Tianyue Li (syringe)'
_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.5201(17)
2 0.4799(17)

