# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1558745'
_audit_update_record             
;
2017-07-17 deposited with the CCDC.
2017-09-08 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H9 Bi S3'
_chemical_formula_sum            'C12 H9 Bi S3'
_chemical_formula_weight         458.35

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'
S S 0.1246 0.1234 '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'

_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3 :H'
_space_group_name_Hall           '-R 3'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'

_cell_length_a                   9.459(2)
_cell_length_b                   9.459(2)
_cell_length_c                   26.619(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     2062.4(12)
_cell_formula_units_Z            6
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    775
_cell_measurement_theta_min      3.9330
_cell_measurement_theta_max      28.1645

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.214
_exptl_crystal_F_000             1272
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.03
_exptl_absorpt_coefficient_mu    13.249
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.39548
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.46 (release 27-08-2009 CrysAlis171 .NET)
(compiled Aug 27 2009,17:19:36)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Oxford Gemini S'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            1931
_diffrn_reflns_av_unetI/netI     0.0591
_diffrn_reflns_av_R_equivalents  0.0424
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_theta_min         3.945
_diffrn_reflns_theta_max         28.177
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.862
_diffrn_measured_fraction_theta_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.862
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.862
_diffrn_reflns_point_group_measured_fraction_full 0.994
_reflns_number_total             983
_reflns_number_gt                620
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.46 (release 27-08-2009 CrysAlis171 .NET)
(compiled Aug 27 2009,17:19:36)
;
_computing_cell_refinement       
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.46 (release 27-08-2009 CrysAlis171 .NET)
(compiled Aug 27 2009,17:19:36)
;
_computing_data_reduction        
;
CrysAlisPro, Oxford Diffraction Ltd.,
Version 1.171.33.46 (release 27-08-2009 CrysAlis171 .NET)
(compiled Aug 27 2009,17:19:36)
;
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/6 (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)+(0.0467P)²] 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_number_reflns         983
_refine_ls_number_parameters     68
_refine_ls_number_restraints     76
_refine_ls_R_factor_all          0.0615
_refine_ls_R_factor_gt           0.0386
_refine_ls_wR_factor_ref         0.0844
_refine_ls_wR_factor_gt          0.0807
_refine_ls_goodness_of_fit_ref   0.856
_refine_ls_restrained_S_all      0.866
_refine_ls_shift/su_max          0.002
_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
C1 C 1.3579(9) -0.5157(9) 0.5570(3) 0.0786(18) Uani 1 1 d D U . . .
C3 C 1.4327(13) -0.6424(12) 0.6209(4) 0.112(3) Uani 1 1 d D U . . .
H3 H 1.4821 -0.6512 0.6500 0.134 Uiso 1 1 calc R U . A 1
C4 C 1.3312(14) -0.7637(14) 0.5909(4) 0.123(3) Uani 1 1 d D U . . .
H4 H 1.3037 -0.8713 0.5968 0.147 Uiso 1 1 calc R U . B 1
C2 C 1.451(5) -0.493(4) 0.5988(10) 0.105(9) Uani 0.634(11) 1 d D U P C 1
H2 H 1.5204 -0.3897 0.6121 0.126 Uiso 0.634(11) 1 calc R U P C 1
S1 S 1.2602(11) -0.7142(7) 0.5446(3) 0.111(2) Uani 0.634(11) 1 d D U P C 1
C2' C 1.291(8) -0.680(3) 0.552(2) 0.127(18) Uani 0.366(11) 1 d D U P C 2
H2' H 1.2244 -0.7358 0.5246 0.153 Uiso 0.366(11) 1 calc R U P C 2
S1' S 1.4721(19) -0.4634(16) 0.6071(5) 0.096(3) Uani 0.366(11) 1 d D U P C 2
Bi1 Bi 1.3333 -0.3333 0.50952(2) 0.0768(3) Uani 1 3 d S TU P C .

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
C1 0.084(5) 0.084(4) 0.078(4) 0.004(3) 0.009(3) 0.050(4)
C3 0.114(7) 0.135(6) 0.107(6) 0.025(4) 0.013(5) 0.077(5)
C4 0.137(8) 0.108(6) 0.137(7) 0.021(5) 0.018(5) 0.072(5)
C2 0.121(16) 0.100(8) 0.100(11) 0.002(6) -0.012(11) 0.060(8)
S1 0.128(5) 0.084(3) 0.126(4) -0.005(3) -0.003(3) 0.057(3)
C2' 0.16(4) 0.092(8) 0.127(17) -0.004(8) -0.03(2) 0.064(11)
S1' 0.100(7) 0.112(6) 0.082(5) 0.005(4) -0.007(4) 0.056(5)
Bi1 0.0790(3) 0.0790(3) 0.0723(4) 0.000 0.000 0.03949(14)

_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
C1 C2' 1.36(2) . ?
C1 C2 1.365(19) . ?
C1 S1' 1.630(11) . ?
C1 S1 1.659(9) . ?
C1 Bi1 2.243(7) . ?
C3 C4 1.331(13) . ?
C3 C2 1.46(3) . ?
C3 S1' 1.584(13) . ?
C3 H3 0.9300 . ?
C4 C2' 1.47(3) . ?
C4 S1 1.581(11) . ?
C4 H4 0.9300 . ?
C2 H2 0.9300 . ?
C2' H2' 0.9300 . ?
Bi1 C1 2.243(7) 3_865 ?
Bi1 C1 2.243(7) 2_635 ?

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
C2' C1 S1' 107.0(15) . . ?
C2 C1 S1 107.0(13) . . ?
C2' C1 Bi1 130.6(16) . . ?
C2 C1 Bi1 129.9(13) . . ?
S1' C1 Bi1 122.4(6) . . ?
S1 C1 Bi1 123.0(4) . . ?
C4 C3 C2 106.2(11) . . ?
C4 C3 S1' 117.8(8) . . ?
C4 C3 H3 126.9 . . ?
C2 C3 H3 126.9 . . ?
C3 C4 C2' 103.3(13) . . ?
C3 C4 S1 116.2(9) . . ?
C3 C4 H4 121.9 . . ?
S1 C4 H4 121.9 . . ?
C1 C2 C3 115(2) . . ?
C1 C2 H2 122.7 . . ?
C3 C2 H2 122.7 . . ?
C4 S1 C1 95.8(6) . . ?
C1 C2' C4 116(2) . . ?
C1 C2' H2' 121.9 . . ?
C4 C2' H2' 121.9 . . ?
C3 S1' C1 95.6(7) . . ?
C1 Bi1 C1 91.3(2) 3_865 2_635 ?
C1 Bi1 C1 91.3(2) 3_865 . ?
C1 Bi1 C1 91.3(2) 2_635 . ?

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
S1' C3 C4 C2' 1(4) . . . . ?
C2 C3 C4 S1 -2(2) . . . . ?
S1 C1 C2 C3 -3(3) . . . . ?
Bi1 C1 C2 C3 178.6(13) . . . . ?
C4 C3 C2 C1 3(3) . . . . ?
C3 C4 S1 C1 0.5(12) . . . . ?
C2 C1 S1 C4 1(2) . . . . ?
Bi1 C1 S1 C4 -179.9(6) . . . . ?
S1' C1 C2' C4 2(6) . . . . ?
Bi1 C1 C2' C4 -179(2) . . . . ?
C3 C4 C2' C1 -2(6) . . . . ?
C4 C3 S1' C1 -0.1(14) . . . . ?
C2' C1 S1' C3 -1(4) . . . . ?
Bi1 C1 S1' C3 179.8(6) . . . . ?

_refine_diff_density_max         1.579
_refine_diff_density_min         -0.603
_refine_diff_density_rms         0.142

_shelxl_version_number           2014/6

_shelx_res_file                  
;
TITL EXP_093 in R-3
CELL  0.71073   9.4586   9.4586  26.6186   90.000   90.000  120.000
ZERR     6.00   0.0022   0.0022   0.0101    0.000    0.000    0.000
LATT   3
SYMM  - Y,   X - Y,   Z
SYMM  - X + Y, - X,   Z
SFAC  C    H    S    BI
UNIT  72   54   18   6
MERG   2
OMIT    -2   2  20
OMIT     2   3  11
SADI C1 S1  C1 S1'  C4 S1  C3 S1'
SADI C3 C4  C1 C2  C1 C2'
SADI C2 C3  C2' C4
RIGU
FMAP   2
PLAN   25
ACTA
BOND   $H
CONF
L.S.   4
WGHT    0.046700
FVAR       1.00525   0.63377
C1    1    1.357862   -0.515726    0.557033    11.00000    0.08386    0.08407 =
         0.07815    0.00386    0.00914    0.04968
C3    1    1.432694   -0.642425    0.620860    11.00000    0.11443    0.13489 =
         0.10679    0.02518    0.01348    0.07729
AFIX  43
H3    2    1.482086   -0.651212    0.649982    11.00000   -1.20000
AFIX   0
C4    1    1.331244   -0.763655    0.590905    11.00000    0.13705    0.10778 =
         0.13684    0.02074    0.01779    0.07153
AFIX  43
H4    2    1.303695   -0.871339    0.596844    11.00000   -1.20000
AFIX   0
PART    1
C2    1    1.450919   -0.492549    0.598776    21.00000    0.12139    0.10009 =
         0.09998    0.00238   -0.01170    0.05999
AFIX  43
H2    2    1.520355   -0.389686    0.612108    21.00000   -1.20000
AFIX   0
S1    3    1.260193   -0.714244    0.544644    21.00000    0.12843    0.08396 =
         0.12596   -0.00475   -0.00271    0.05718
PART    2
C2'   1    1.291394   -0.679701    0.551601   -21.00000    0.16298    0.09245 =
         0.12733   -0.00380   -0.02618    0.06425
AFIX  43
H2'   2    1.224440   -0.735767    0.524551   -21.00000   -1.20000
AFIX   0
S1'   3    1.472090   -0.463366    0.607143   -21.00000    0.09952    0.11196 =
         0.08188    0.00474   -0.00707    0.05619
PART    0
BI1   4    1.333333   -0.333333    0.509515    10.33333    0.07898    0.07898 =
         0.07231    0.00000    0.00000    0.03949
HKLF    4

REM  EXP_093 in R-3
REM R1 =  0.0386 for     620 Fo > 4sig(Fo)  and  0.0615 for all     983 data
REM     68 parameters refined using     76 restraints

END

WGHT      0.0467      0.0000

REM Highest difference peak  1.579,  deepest hole -0.603,  1-sigma level  0.142
Q1    1   1.3333 -0.3333  0.5471  10.33333  0.05    1.58
Q2    1   1.3333 -0.3333  0.4709  10.33333  0.05    1.49
Q3    1   1.2298 -0.4428  0.5144  11.00000  0.05    0.68
Q4    1   1.3698 -0.4125  0.5075  11.00000  0.05    0.67
Q5    1   1.2534 -0.7912  0.5750  11.00000  0.05    0.43
Q6    1   1.0000 -1.0000  0.5288  10.33333  0.05    0.38
Q7    1   1.4119 -0.5964  0.6304  11.00000  0.05    0.35
Q8    1   1.3541 -0.5048  0.5924  11.00000  0.05    0.35
Q9    1   1.3421 -0.8134  0.5477  11.00000  0.05    0.34
Q10   1   1.3530 -0.2505  0.4355  11.00000  0.05    0.33
Q11   1   1.3131 -0.4514  0.5794  11.00000  0.05    0.33
Q12   1   1.6667 -0.6667  0.6753  10.33333  0.05    0.32
Q13   1   1.3526 -0.7293  0.6132  11.00000  0.05    0.31
Q14   1   1.1748 -0.8253  0.5888  11.00000  0.05    0.30
Q15   1   1.3606 -0.5825  0.5298  11.00000  0.05    0.30
Q16   1   1.6482 -0.5035  0.6258  11.00000  0.05    0.29
Q17   1   1.2004 -0.8185  0.4942  11.00000  0.05    0.29
Q18   1   1.4374 -0.4051  0.6117  11.00000  0.05    0.28
Q19   1   1.4206 -0.7018  0.6043  11.00000  0.05    0.28
Q20   1   1.5009 -0.4702  0.6553  11.00000  0.05    0.27
Q21   1   1.3251 -0.8908  0.5641  11.00000  0.05    0.27
Q22   1   1.3905 -0.8132  0.6723  11.00000  0.05    0.26
Q23   1   1.4828 -0.4888  0.5650  11.00000  0.05    0.24
Q24   1   1.6345 -0.2399  0.5718  11.00000  0.05    0.23
Q25   1   1.5764 -0.4348  0.5861  11.00000  0.05    0.22
;
_shelx_res_checksum              57820
