# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_1

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C14 H13 N2 S2 Tl'
_chemical_formula_weight         477.75

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'
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'
Tl Tl -2.8358 9.6688 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   Pbca

loop_
_symmetry_equiv_pos_as_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                   10.929(3)
_cell_length_b                   9.981(4)
_cell_length_c                   27.219(7)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2968.9(14)
_cell_formula_units_Z            8
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    8946
_cell_measurement_theta_min      2.86
_cell_measurement_theta_max      27.49

_exptl_crystal_description       needle
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.06
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.138
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1792
_exptl_absorpt_coefficient_mu    11.148
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSPACK, Oxford Diffraction Ltd'
_exptl_absorpt_correction_T_min  0.811
_exptl_absorpt_correction_T_max  1.000

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_standards_number         n/a
_diffrn_measurement_device       'Oxford Diffaction X-Calibur System'
_diffrn_measurement_method       '321 frames, counting time 10 s.'
_diffrn_standards_interval_count n/a
_diffrn_standards_interval_time  n/a
_diffrn_standards_decay_%        n/a
_diffrn_reflns_number            8946
_diffrn_reflns_av_R_equivalents  0.1129
_diffrn_reflns_av_sigmaI/netI    0.1045
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.86
_diffrn_reflns_theta_max         27.49
_reflns_number_total             3314
_reflns_number_gt                1739
_reflns_threshold_expression     >2sigma(I)


_computing_data_collection       'Crysalis, Oxford Diffraction'
_computing_cell_refinement       'Crysalis, Oxford Diffraction'
_computing_data_reduction        'Crysalis, Oxford Diffraction'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    PLATON(Spek,2004)

_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.1059P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3314
_refine_ls_number_parameters     172
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1387
_refine_ls_R_factor_gt           0.0809
_refine_ls_wR_factor_ref         0.2278
_refine_ls_wR_factor_gt          0.1891
_refine_ls_goodness_of_fit_ref   0.951
_refine_ls_restrained_S_all      0.951
_refine_ls_shift/su_max          0.005
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Tl1 Tl 0.58059(6) 0.16540(6) 0.50851(2) 0.0749(3) Uani 1 1 d . . .
N14 N 0.2815(9) 0.0960(10) 0.6233(4) 0.054(3) Uani 1 1 d . . .
S11 S 0.4955(3) -0.0064(3) 0.59473(12) 0.0563(8) Uani 1 1 d . . .
S13 S 0.3172(4) 0.1202(4) 0.52791(12) 0.0666(10) Uani 1 1 d . . .
C23 C 0.4427(12) 0.2463(15) 0.6955(6) 0.071(4) Uani 1 1 d . . .
H23 H 0.4898 0.2276 0.6679 0.085 Uiso 1 1 calc R . .
C22 C 0.3420(13) 0.1682(12) 0.7058(5) 0.057(3) Uani 1 1 d . . .
C27 C 0.2757(15) 0.1979(16) 0.7491(4) 0.069(4) Uani 1 1 d . . .
H27 H 0.2092 0.1456 0.7583 0.082 Uiso 1 1 calc R . .
C26 C 0.3114(16) 0.3060(16) 0.7774(5) 0.078(5) Uani 1 1 d . . .
H26 H 0.2657 0.3272 0.8052 0.094 Uiso 1 1 calc R . .
C25 C 0.4085(15) 0.3812(16) 0.7667(7) 0.074(4) Uani 1 1 d . . .
H25 H 0.4310 0.4524 0.7868 0.088 Uiso 1 1 calc R . .
C24 C 0.4744(13) 0.3509(15) 0.7252(7) 0.077(5) Uani 1 1 d . . .
H24 H 0.5423 0.4027 0.7172 0.092 Uiso 1 1 calc R . .
C21 C 0.3073(12) 0.0533(12) 0.6728(4) 0.057(3) Uani 1 1 d . . .
H21A H 0.3737 -0.0112 0.6723 0.068 Uiso 1 1 calc R . .
H21B H 0.2357 0.0090 0.6862 0.068 Uiso 1 1 calc R . .
C12 C 0.3592(10) 0.0730(12) 0.5857(4) 0.051(3) Uani 1 1 d . . .
C31 C 0.1681(10) 0.1689(11) 0.6173(4) 0.052(3) Uani 1 1 d . . .
H31A H 0.1776 0.2296 0.5897 0.062 Uiso 1 1 calc R . .
H31B H 0.1557 0.2233 0.6464 0.062 Uiso 1 1 calc R . .
C32 C 0.0532(10) 0.0870(12) 0.6089(4) 0.041(3) Uani 1 1 d . . .
C37 C 0.0525(13) -0.0269(15) 0.5861(6) 0.067(4) Uani 1 1 d . . .
H37 H 0.1275 -0.0597 0.5753 0.081 Uiso 1 1 calc R . .
C33 C -0.0559(11) 0.1368(14) 0.6229(6) 0.068(4) Uani 1 1 d . . .
H33 H -0.0603 0.2187 0.6391 0.082 Uiso 1 1 calc R . .
C34 C -0.1607(13) 0.0656(17) 0.6131(7) 0.083(5) Uani 1 1 d . . .
H34 H -0.2371 0.0989 0.6219 0.100 Uiso 1 1 calc R . .
N36 N -0.0481(12) -0.1033(12) 0.5765(5) 0.073(3) Uani 1 1 d . . .
C35 C -0.1499(16) -0.0547(18) 0.5902(6) 0.083(5) Uani 1 1 d . . .
H35 H -0.2206 -0.1040 0.5842 0.100 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
Tl1 S13 2.961(4) . ?
Tl1 N36 2.980(12) 7_665 ?
Tl1 S11 3.051(3) . ?
Tl1 S13 3.218(4) 5_656 ?
Tl1 S11 3.333(3) 5_656 ?
Tl1 S13 3.500(4) 3_556 ?
Tl1 Tl1 3.7707(15) 5_656 ?
N14 C12 1.348(14) . ?
N14 C21 1.443(14) . ?
N14 C31 1.447(13) . ?
S11 C12 1.705(12) . ?
S11 Tl1 3.333(3) 5_656 ?
S13 C12 1.706(12) . ?
S13 Tl1 3.218(4) 5_656 ?
S13 Tl1 3.500(4) 3_456 ?
C23 C24 1.37(2) . ?
C23 C22 1.377(18) . ?
C23 H23 0.9300 . ?
C22 C27 1.415(17) . ?
C22 C21 1.504(16) . ?
C27 C26 1.38(2) . ?
C27 H27 0.9300 . ?
C26 C25 1.33(2) . ?
C26 H26 0.9300 . ?
C25 C24 1.37(2) . ?
C25 H25 0.9300 . ?
C24 H24 0.9300 . ?
C21 H21A 0.9700 . ?
C21 H21B 0.9700 . ?
C31 C32 1.515(15) . ?
C31 H31A 0.9700 . ?
C31 H31B 0.9700 . ?
C32 C37 1.296(17) . ?
C32 C33 1.348(15) . ?
C37 N36 1.363(17) . ?
C37 H37 0.9300 . ?
C33 C34 1.374(18) . ?
C33 H33 0.9300 . ?
C34 C35 1.36(2) . ?
C34 H34 0.9300 . ?
N36 C35 1.269(18) . ?
N36 Tl1 2.980(12) 7_655 ?
C35 H35 0.9300 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
S13 Tl1 N36 83.8(3) . 7_665 ?
S13 Tl1 S11 58.75(9) . . ?
N36 Tl1 S11 85.5(3) 7_665 . ?
S13 Tl1 S13 104.92(9) . 5_656 ?
N36 Tl1 S13 156.8(3) 7_665 5_656 ?
S11 Tl1 S13 81.08(9) . 5_656 ?
S13 Tl1 S11 80.51(9) . 5_656 ?
N36 Tl1 S11 149.6(3) 7_665 5_656 ?
S11 Tl1 S11 107.75(8) . 5_656 ?
S13 Tl1 S11 53.50(8) 5_656 5_656 ?
S13 Tl1 S13 149.53(6) . 3_556 ?
N36 Tl1 S13 77.9(3) 7_665 3_556 ?
S11 Tl1 S13 141.85(9) . 3_556 ?
S13 Tl1 S13 101.41(6) 5_656 3_556 ?
S11 Tl1 S13 103.70(8) 5_656 3_556 ?
S13 Tl1 Tl1 55.56(8) . 5_656 ?
N36 Tl1 Tl1 134.3(2) 7_665 5_656 ?
S11 Tl1 Tl1 57.33(6) . 5_656 ?
S13 Tl1 Tl1 49.36(8) 5_656 5_656 ?
S11 Tl1 Tl1 50.42(6) 5_656 5_656 ?
S13 Tl1 Tl1 147.75(7) 3_556 5_656 ?
C12 N14 C21 122.4(10) . . ?
C12 N14 C31 122.7(10) . . ?
C21 N14 C31 114.9(10) . . ?
C12 S11 Tl1 84.0(5) . . ?
C12 S11 Tl1 83.2(4) . 5_656 ?
Tl1 S11 Tl1 72.25(8) . 5_656 ?
C12 S13 Tl1 86.9(4) . . ?
C12 S13 Tl1 86.9(4) . 5_656 ?
Tl1 S13 Tl1 75.08(9) . 5_656 ?
C12 S13 Tl1 129.0(4) . 3_456 ?
Tl1 S13 Tl1 125.08(12) . 3_456 ?
Tl1 S13 Tl1 135.30(12) 5_656 3_456 ?
C24 C23 C22 121.0(15) . . ?
C24 C23 H23 119.5 . . ?
C22 C23 H23 119.5 . . ?
C23 C22 C27 117.4(14) . . ?
C23 C22 C21 120.8(12) . . ?
C27 C22 C21 121.8(12) . . ?
C26 C27 C22 118.9(14) . . ?
C26 C27 H27 120.6 . . ?
C22 C27 H27 120.6 . . ?
C25 C26 C27 122.9(14) . . ?
C25 C26 H26 118.6 . . ?
C27 C26 H26 118.6 . . ?
C26 C25 C24 118.3(16) . . ?
C26 C25 H25 120.8 . . ?
C24 C25 H25 120.8 . . ?
C23 C24 C25 121.5(14) . . ?
C23 C24 H24 119.3 . . ?
C25 C24 H24 119.3 . . ?
N14 C21 C22 112.4(10) . . ?
N14 C21 H21A 109.1 . . ?
C22 C21 H21A 109.1 . . ?
N14 C21 H21B 109.1 . . ?
C22 C21 H21B 109.1 . . ?
H21A C21 H21B 107.8 . . ?
N14 C12 S11 121.4(9) . . ?
N14 C12 S13 118.9(8) . . ?
S11 C12 S13 119.7(7) . . ?
N14 C31 C32 117.1(10) . . ?
N14 C31 H31A 108.0 . . ?
C32 C31 H31A 108.0 . . ?
N14 C31 H31B 108.0 . . ?
C32 C31 H31B 108.0 . . ?
H31A C31 H31B 107.3 . . ?
C37 C32 C33 117.0(12) . . ?
C37 C32 C31 123.4(11) . . ?
C33 C32 C31 119.5(11) . . ?
C32 C37 N36 126.0(13) . . ?
C32 C37 H37 117.0 . . ?
N36 C37 H37 117.0 . . ?
C32 C33 C34 119.5(14) . . ?
C32 C33 H33 120.3 . . ?
C34 C33 H33 120.3 . . ?
C35 C34 C33 118.3(14) . . ?
C35 C34 H34 120.9 . . ?
C33 C34 H34 120.9 . . ?
C35 N36 C37 115.9(14) . . ?
C35 N36 Tl1 111.9(11) . 7_655 ?
C37 N36 Tl1 130.4(9) . 7_655 ?
N36 C35 C34 123.3(17) . . ?
N36 C35 H35 118.4 . . ?
C34 C35 H35 118.4 . . ?

_diffrn_measured_fraction_theta_max 0.972
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         1.863
_refine_diff_density_min         -3.054
_refine_diff_density_rms         0.261
_database_code_depnum_ccdc_archive 'CCDC 1031503'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_2

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C13 H12 N3 S2 Tl'
_chemical_formula_weight         478.75

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'
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'
Tl Tl -2.8358 9.6688 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   Pbca

loop_
_symmetry_equiv_pos_as_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                   10.8429(14)
_cell_length_b                   9.9762(17)
_cell_length_c                   27.222(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2944.6(7)
_cell_formula_units_Z            8
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    8799
_cell_measurement_theta_min      3.53
_cell_measurement_theta_max      27.49

_exptl_crystal_description       needle
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.160
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1792
_exptl_absorpt_coefficient_mu    11.242
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSPACK, Oxford Diffraction Ltd'

_exptl_absorpt_correction_T_min  0.923
_exptl_absorpt_correction_T_max  1.000

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_standards_number         n/a
_diffrn_measurement_device       'Oxford Diffaction X-Calibur System'
_diffrn_measurement_method       '321 frames, counting time 10 s.'
_diffrn_standards_interval_count n/a
_diffrn_standards_interval_time  n/a
_diffrn_standards_decay_%        n/a
_diffrn_reflns_number            8799
_diffrn_reflns_av_R_equivalents  0.0932
_diffrn_reflns_av_sigmaI/netI    0.0947
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_theta_min         3.53
_diffrn_reflns_theta_max         27.49
_reflns_number_total             3266
_reflns_number_gt                2108
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Crysalis, Oxford Diffraction'
_computing_cell_refinement       'Crysalis, Oxford Diffraction'
_computing_data_reduction        'Crysalis, Oxford Diffraction'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    PLATON(Spek,2004)



_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0703P)²+12.5957P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3266
_refine_ls_number_parameters     172
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1160
_refine_ls_R_factor_gt           0.0724
_refine_ls_wR_factor_ref         0.1902
_refine_ls_wR_factor_gt          0.1697
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_restrained_S_all      1.079
_refine_ls_shift/su_max          0.000
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Tl1 Tl 0.58409(6) 0.66528(5) 0.48879(2) 0.0594(3) Uani 1 1 d . . .
S11 S 0.4934(2) 0.4884(3) 0.40465(12) 0.0403(7) Uani 1 1 d . . .
S13 S 0.3162(3) 0.6187(4) 0.47232(12) 0.0491(8) Uani 1 1 d . . .
C12 C 0.3542(9) 0.5691(11) 0.4143(4) 0.032(2) Uani 1 1 d . . .
N14 N 0.2795(8) 0.5930(9) 0.3773(3) 0.031(2) Uani 1 1 d . . .
C21 C 0.3029(10) 0.5533(12) 0.3261(4) 0.037(3) Uani 1 1 d . . .
H21A H 0.2278 0.5160 0.3125 0.044 Uiso 1 1 calc R . .
H21B H 0.3649 0.4832 0.3259 0.044 Uiso 1 1 calc R . .
C22 C 0.3449(10) 0.6637(12) 0.2942(4) 0.036(3) Uani 1 1 d . . .
C23 C 0.4486(11) 0.7411(14) 0.3034(5) 0.044(3) Uani 1 1 d . . .
H23 H 0.4971 0.7227 0.3308 0.053 Uiso 1 1 calc R . .
C24 C 0.4804(13) 0.8443(14) 0.2728(6) 0.057(4) Uani 1 1 d . . .
H24 H 0.5521 0.8930 0.2785 0.069 Uiso 1 1 calc R . .
C25 C 0.4079(13) 0.8750(15) 0.2344(6) 0.054(4) Uani 1 1 d . . .
H25 H 0.4298 0.9471 0.2146 0.065 Uiso 1 1 calc R . .
N26 N 0.3058(13) 0.8065(13) 0.2234(4) 0.064(3) Uani 1 1 d . . .
C27 C 0.2763(13) 0.7051(15) 0.2537(5) 0.051(3) Uani 1 1 d . . .
H27 H 0.2039 0.6585 0.2470 0.061 Uiso 1 1 calc R . .
C31 C 0.1636(9) 0.6702(11) 0.3826(4) 0.033(2) Uani 1 1 d . . .
H31A H 0.1535 0.7268 0.3539 0.039 Uiso 1 1 calc R . .
H31B H 0.1706 0.7284 0.4110 0.039 Uiso 1 1 calc R . .
C32 C 0.0488(10) 0.5837(12) 0.3884(4) 0.034(3) Uani 1 1 d . . .
C33 C -0.0601(11) 0.6354(14) 0.3721(6) 0.052(4) Uani 1 1 d . . .
H33 H -0.0636 0.7186 0.3567 0.062 Uiso 1 1 calc R . .
C34 C -0.1663(11) 0.5583(14) 0.3793(6) 0.062(4) Uani 1 1 d . . .
H34 H -0.2425 0.5901 0.3688 0.075 Uiso 1 1 calc R . .
C35 C -0.1581(12) 0.4360(14) 0.4019(6) 0.057(4) Uani 1 1 d . . .
H35 H -0.2293 0.3846 0.4051 0.068 Uiso 1 1 calc R . .
N36 N -0.0505(11) 0.3865(12) 0.4198(5) 0.059(3) Uani 1 1 d . . .
C37 C 0.0492(11) 0.4622(13) 0.4122(5) 0.044(3) Uani 1 1 d . . .
H37 H 0.1243 0.4304 0.4239 0.052 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
Tl1 N36 2.921(13) 7_665 ?
Tl1 S13 2.976(4) . ?
Tl1 S11 3.054(3) . ?
Tl1 S13 3.212(4) 5_666 ?
Tl1 S11 3.387(3) 5_666 ?
Tl1 S13 3.478(3) 3_566 ?
Tl1 Tl1 3.8174(12) 5_666 ?
S11 C12 1.731(11) . ?
S11 Tl1 3.387(3) 5_666 ?
S13 C12 1.706(12) . ?
S13 Tl1 3.212(4) 5_666 ?
S13 Tl1 3.478(3) 3_466 ?
C12 N14 1.313(13) . ?
N14 C31 1.481(13) . ?
N14 C21 1.471(14) . ?
C21 C22 1.475(16) . ?
C22 C27 1.395(16) . ?
C22 C23 1.386(16) . ?
C23 C24 1.37(2) . ?
C24 C25 1.34(2) . ?
C25 N26 1.335(19) . ?
N26 C27 1.343(18) . ?
C31 C32 1.522(15) . ?
C32 C33 1.363(16) . ?
C32 C37 1.375(17) . ?
C33 C34 1.399(17) . ?
C34 C35 1.369(19) . ?
C35 N36 1.357(18) . ?
N36 C37 1.335(16) . ?
N36 Tl1 2.921(12) 7_655 ?

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
N36 Tl1 S13 84.2(2) 7_665 . ?
N36 Tl1 S11 85.1(3) 7_665 . ?
S13 Tl1 S11 58.83(8) . . ?
N36 Tl1 S13 157.0(3) 7_665 5_666 ?
S13 Tl1 S13 103.92(8) . 5_666 ?
S11 Tl1 S13 81.13(8) . 5_666 ?
N36 Tl1 S11 149.5(3) 7_665 5_666 ?
S13 Tl1 S11 79.41(8) . 5_666 ?
S11 Tl1 S11 107.51(7) . 5_666 ?
S13 Tl1 S11 53.27(8) 5_666 5_666 ?
N36 Tl1 S13 79.5(3) 7_665 3_566 ?
S13 Tl1 S13 148.09(6) . 3_566 ?
S11 Tl1 S13 145.01(8) . 3_566 ?
S13 Tl1 S13 101.69(5) 5_666 3_566 ?
S11 Tl1 S13 101.49(8) 5_666 3_566 ?
N36 Tl1 Tl1 134.1(2) 7_665 5_666 ?
S13 Tl1 Tl1 54.75(7) . 5_666 ?
S11 Tl1 Tl1 57.78(7) . 5_666 ?
S13 Tl1 Tl1 49.17(7) 5_666 5_666 ?
S11 Tl1 Tl1 49.73(6) 5_666 5_666 ?
S13 Tl1 Tl1 146.32(7) 3_566 5_666 ?
C12 S11 Tl1 84.2(4) . . ?
C12 S11 Tl1 82.2(4) . 5_666 ?
Tl1 S11 Tl1 72.49(7) . 5_666 ?
C12 S13 Tl1 87.1(4) . . ?
C12 S13 Tl1 88.2(4) . 5_666 ?
Tl1 S13 Tl1 76.08(8) . 5_666 ?
C12 S13 Tl1 129.5(4) . 3_466 ?
Tl1 S13 Tl1 124.31(12) . 3_466 ?
Tl1 S13 Tl1 133.61(12) 5_666 3_466 ?
N14 C12 S13 120.5(8) . . ?
N14 C12 S11 120.4(9) . . ?
S13 C12 S11 119.1(6) . . ?
C12 N14 C31 123.0(9) . . ?
C12 N14 C21 124.8(9) . . ?
C31 N14 C21 112.2(9) . . ?
N14 C21 C22 114.2(9) . . ?
C27 C22 C23 114.3(12) . . ?
C27 C22 C21 121.5(11) . . ?
C23 C22 C21 124.1(11) . . ?
C24 C23 C22 120.9(14) . . ?
C25 C24 C23 119.9(13) . . ?
N26 C25 C24 122.9(13) . . ?
C25 N26 C27 116.5(13) . . ?
N26 C27 C22 125.5(13) . . ?
N14 C31 C32 114.1(9) . . ?
C33 C32 C37 119.3(11) . . ?
C33 C32 C31 117.4(11) . . ?
C37 C32 C31 123.1(10) . . ?
C32 C33 C34 117.4(12) . . ?
C35 C34 C33 120.0(12) . . ?
C34 C35 N36 122.7(12) . . ?
C37 N36 C35 115.8(12) . . ?
C37 N36 Tl1 128.9(9) . 7_655 ?
C35 N36 Tl1 113.5(9) . 7_655 ?
N36 C37 C32 124.7(12) . . ?

_diffrn_measured_fraction_theta_max 0.969
_diffrn_reflns_theta_full        27.49
_diffrn_measured_fraction_theta_full 0.969
_refine_diff_density_max         1.472
_refine_diff_density_min         -1.999
_refine_diff_density_rms         0.249
_database_code_depnum_ccdc_archive 'CCDC 1031504'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_3

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C15 H13 N2 O2 S2 Tl'
_chemical_formula_weight         521.76

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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Tl Tl -2.8358 9.6688 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P21/c

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y-1/2, z-1/2'

_cell_length_a                   15.7835(8)
_cell_length_b                   10.7720(5)
_cell_length_c                   9.8639(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 101.993(4)
_cell_angle_gamma                90.00
_cell_volume                     1640.45(13)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    7538
_cell_measurement_theta_min      3.31
_cell_measurement_theta_max      27.50

_exptl_crystal_description       needle
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.113
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             984
_exptl_absorpt_coefficient_mu    10.107
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSPACK, Oxford Diffraction Ltd'

_exptl_absorpt_correction_T_min  0.923
_exptl_absorpt_correction_T_max  1.000

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_standards_number         n/a
_diffrn_measurement_device       'Oxford Diffaction X-Calibur System'
_diffrn_measurement_method       '321 frames, counting time 10 s.'
_diffrn_standards_interval_count n/a
_diffrn_standards_interval_time  n/a
_diffrn_standards_decay_%        n/a
_diffrn_reflns_number            7538
_diffrn_reflns_av_R_equivalents  0.0448
_diffrn_reflns_av_sigmaI/netI    0.0756
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_theta_min         3.31
_diffrn_reflns_theta_max         27.50
_reflns_number_total             3614
_reflns_number_gt                2562
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Crysalis, Oxford Diffraction'
_computing_cell_refinement       'Crysalis, Oxford Diffraction'
_computing_data_reduction        'Crysalis, Oxford Diffraction'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    PLATON(Spek,2004)


_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0423P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3614
_refine_ls_number_parameters     199
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0816
_refine_ls_R_factor_gt           0.0506
_refine_ls_wR_factor_ref         0.1069
_refine_ls_wR_factor_gt          0.0958
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_restrained_S_all      0.996
_refine_ls_shift/su_max          0.000
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Tl1 Tl 0.01721(2) 1.08287(3) 0.33997(3) 0.05649(16) Uani 1 1 d . . .
S13 S 0.05435(14) 0.81194(19) 0.3979(2) 0.0498(5) Uani 1 1 d . . .
C12 C 0.1532(5) 0.8557(6) 0.4874(6) 0.0300(15) Uani 1 1 d . . .
S11 S 0.16487(13) 0.99476(16) 0.57425(19) 0.0397(5) Uani 1 1 d . . .
N14 N 0.2228(4) 0.7808(5) 0.4913(5) 0.0294(12) Uani 1 1 d . . .
C21 C 0.3091(4) 0.8096(6) 0.5688(7) 0.0352(16) Uani 1 1 d . . .
H21A H 0.3319 0.7381 0.6243 0.042 Uiso 1 1 calc R . .
H21B H 0.3055 0.8778 0.6316 0.042 Uiso 1 1 calc R . .
C22 C 0.3710(5) 0.8444(6) 0.4775(7) 0.0317(15) Uani 1 1 d . . .
C23 C 0.4464(5) 0.7788(7) 0.4835(8) 0.0468(19) Uani 1 1 d . . .
H23 H 0.4595 0.7102 0.5414 0.056 Uiso 1 1 calc R . .
C24 C 0.5019(5) 0.8173(8) 0.4018(9) 0.051(2) Uani 1 1 d . . .
C25 C 0.4832(6) 0.9171(8) 0.3150(8) 0.050(2) Uani 1 1 d . . .
C26 C 0.4080(6) 0.9830(8) 0.3032(9) 0.054(2) Uani 1 1 d . . .
H26 H 0.3951 1.0502 0.2432 0.064 Uiso 1 1 calc R . .
C27 C 0.3516(5) 0.9434(7) 0.3870(8) 0.0435(19) Uani 1 1 d . . .
H27 H 0.2994 0.9851 0.3816 0.052 Uiso 1 1 calc R . .
C29 C 0.6111(7) 0.8472(10) 0.2937(12) 0.083(3) Uani 1 1 d . . .
H29A H 0.6652 0.8868 0.3368 0.100 Uiso 1 1 calc R . .
H29B H 0.6215 0.7961 0.2178 0.100 Uiso 1 1 calc R . .
C31 C 0.2167(5) 0.6669(6) 0.4097(7) 0.0378(18) Uani 1 1 d . . .
H31A H 0.2699 0.6570 0.3763 0.045 Uiso 1 1 calc R . .
H31B H 0.1699 0.6762 0.3293 0.045 Uiso 1 1 calc R . .
C32 C 0.2013(5) 0.5500(6) 0.4854(7) 0.0317(16) Uani 1 1 d . . .
C33 C 0.2279(6) 0.4383(7) 0.4429(8) 0.049(2) Uani 1 1 d . . .
H33 H 0.2581 0.4351 0.3713 0.059 Uiso 1 1 calc R . .
C34 C 0.2097(6) 0.3307(8) 0.5068(9) 0.061(3) Uani 1 1 d . . .
H34 H 0.2271 0.2541 0.4785 0.074 Uiso 1 1 calc R . .
C35 C 0.1660(6) 0.3381(8) 0.6119(8) 0.057(2) Uani 1 1 d . . .
H35 H 0.1525 0.2649 0.6526 0.068 Uiso 1 1 calc R . .
N36 N 0.1418(5) 0.4455(6) 0.6589(7) 0.058(2) Uani 1 1 d . . .
C37 C 0.1593(6) 0.5491(7) 0.5935(8) 0.049(2) Uani 1 1 d . . .
H37 H 0.1418 0.6248 0.6238 0.058 Uiso 1 1 calc R . .
O28 O 0.5805(4) 0.7710(7) 0.3938(8) 0.088(2) Uani 1 1 d . . .
O30 O 0.5483(5) 0.9380(6) 0.2432(7) 0.0682(18) Uani 1 1 d . . .


_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
Tl1 N36 2.934(7) 4_575 ?
Tl1 S13 3.008(2) . ?
Tl1 S11 3.0715(19) . ?
Tl1 S13 3.234(2) 3_576 ?
Tl1 S11 3.269(2) 3_576 ?
Tl1 S13 3.4306(19) 2 ?
Tl1 Tl1 3.7634(6) 3_576 ?
S13 C12 1.692(7) . ?
S13 Tl1 3.234(2) 3_576 ?
S13 Tl1 3.4306(19) 2_545 ?
C12 N14 1.358(8) . ?
C12 S11 1.716(7) . ?
S11 Tl1 3.269(2) 3_576 ?
N14 C21 1.450(8) . ?
N14 C31 1.460(8) . ?
C21 C22 1.507(9) . ?
C21 H21A 0.9700 . ?
C21 H21B 0.9700 . ?
C22 C23 1.375(10) . ?
C22 C27 1.384(9) . ?
C23 C24 1.372(10) . ?
C23 H23 0.9300 . ?
C24 O28 1.353(9) . ?
C24 C25 1.367(11) . ?
C25 C26 1.368(12) . ?
C25 O30 1.382(10) . ?
C26 C27 1.401(10) . ?
C26 H26 0.9300 . ?
C27 H27 0.9300 . ?
C29 O30 1.408(12) . ?
C29 O28 1.442(10) . ?
C29 H29A 0.9700 . ?
C29 H29B 0.9700 . ?
C31 C32 1.510(9) . ?
C31 H31A 0.9700 . ?
C31 H31B 0.9700 . ?
C32 C37 1.368(9) . ?
C32 C33 1.368(9) . ?
C33 C34 1.379(10) . ?
C33 H33 0.9300 . ?
C34 C35 1.361(11) . ?
C34 H34 0.9300 . ?
C35 N36 1.333(10) . ?
C35 H35 0.9300 . ?
N36 C37 1.346(9) . ?
N36 Tl1 2.934(7) 4_576 ?
C37 H37 0.9300 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N36 Tl1 S13 83.43(14) 4_575 . ?
N36 Tl1 S11 85.76(15) 4_575 . ?
S13 Tl1 S11 57.98(5) . . ?
N36 Tl1 S13 155.89(16) 4_575 3_576 ?
S13 Tl1 S13 105.94(4) . 3_576 ?
S11 Tl1 S13 80.98(5) . 3_576 ?
N36 Tl1 S11 150.15(16) 4_575 3_576 ?
S13 Tl1 S11 81.36(5) . 3_576 ?
S11 Tl1 S11 107.25(4) . 3_576 ?
S13 Tl1 S11 53.90(5) 3_576 3_576 ?
N36 Tl1 S13 79.97(14) 4_575 2 ?
S13 Tl1 S13 148.35(3) . 2 ?
S11 Tl1 S13 145.83(5) . 2 ?
S13 Tl1 S13 100.07(3) 3_576 2 ?
S11 Tl1 S13 100.30(5) 3_576 2 ?
N36 Tl1 Tl1 133.86(14) 4_575 3_576 ?
S13 Tl1 Tl1 55.71(4) . 3_576 ?
S11 Tl1 Tl1 56.05(4) . 3_576 ?
S13 Tl1 Tl1 50.23(4) 3_576 3_576 ?
S11 Tl1 Tl1 51.21(3) 3_576 3_576 ?
S13 Tl1 Tl1 146.16(4) 2 3_576 ?
C12 S13 Tl1 87.2(2) . . ?
C12 S13 Tl1 85.6(2) . 3_576 ?
Tl1 S13 Tl1 74.06(4) . 3_576 ?
C12 S13 Tl1 134.0(2) . 2_545 ?
Tl1 S13 Tl1 122.98(7) . 2_545 ?
Tl1 S13 Tl1 132.75(7) 3_576 2_545 ?
N14 C12 S13 120.2(5) . . ?
N14 C12 S11 120.2(5) . . ?
S13 C12 S11 119.7(4) . . ?
C12 S11 Tl1 84.7(2) . . ?
C12 S11 Tl1 84.1(2) . 3_576 ?
Tl1 S11 Tl1 72.75(4) . 3_576 ?
C12 N14 C21 123.6(5) . . ?
C12 N14 C31 121.5(6) . . ?
C21 N14 C31 114.7(5) . . ?
N14 C21 C22 113.1(5) . . ?
N14 C21 H21A 109.0 . . ?
C22 C21 H21A 109.0 . . ?
N14 C21 H21B 109.0 . . ?
C22 C21 H21B 109.0 . . ?
H21A C21 H21B 107.8 . . ?
C23 C22 C27 119.8(6) . . ?
C23 C22 C21 120.6(6) . . ?
C27 C22 C21 119.6(6) . . ?
C22 C23 C24 118.2(7) . . ?
C22 C23 H23 120.9 . . ?
C24 C23 H23 120.9 . . ?
O28 C24 C25 109.5(7) . . ?
O28 C24 C23 128.8(8) . . ?
C25 C24 C23 121.6(8) . . ?
C24 C25 C26 122.2(8) . . ?
C24 C25 O30 111.2(8) . . ?
C26 C25 O30 126.6(8) . . ?
C25 C26 C27 116.0(7) . . ?
C25 C26 H26 122.0 . . ?
C27 C26 H26 122.0 . . ?
C22 C27 C26 122.2(7) . . ?
C22 C27 H27 118.9 . . ?
C26 C27 H27 118.9 . . ?
O30 C29 O28 109.0(7) . . ?
O30 C29 H29A 109.9 . . ?
O28 C29 H29A 109.9 . . ?
O30 C29 H29B 109.9 . . ?
O28 C29 H29B 109.9 . . ?
H29A C29 H29B 108.3 . . ?
N14 C31 C32 115.3(5) . . ?
N14 C31 H31A 108.4 . . ?
C32 C31 H31A 108.4 . . ?
N14 C31 H31B 108.4 . . ?
C32 C31 H31B 108.4 . . ?
H31A C31 H31B 107.5 . . ?
C37 C32 C33 117.6(7) . . ?
C37 C32 C31 123.1(6) . . ?
C33 C32 C31 119.4(6) . . ?
C32 C33 C34 119.5(8) . . ?
C32 C33 H33 120.2 . . ?
C34 C33 H33 120.2 . . ?
C35 C34 C33 119.0(8) . . ?
C35 C34 H34 120.5 . . ?
C33 C34 H34 120.5 . . ?
N36 C35 C34 123.0(8) . . ?
N36 C35 H35 118.5 . . ?
C34 C35 H35 118.5 . . ?
C35 N36 C37 116.8(7) . . ?
C35 N36 Tl1 113.5(5) . 4_576 ?
C37 N36 Tl1 127.5(5) . 4_576 ?
N36 C37 C32 124.1(7) . . ?
N36 C37 H37 118.0 . . ?
C32 C37 H37 118.0 . . ?
C24 O28 C29 105.8(7) . . ?
C25 O30 C29 104.4(7) . . ?

_diffrn_measured_fraction_theta_max 0.960
_diffrn_reflns_theta_full        27.50
_diffrn_measured_fraction_theta_full 0.960
_refine_diff_density_max         1.948
_refine_diff_density_min         -1.669
_refine_diff_density_rms         0.179
_database_code_depnum_ccdc_archive 'CCDC 1031505'
#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_4

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C18 H17 Fe N2 S2 Tl'
_chemical_formula_weight         585.68

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'
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'
Tl Tl -2.8358 9.6688 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   Pcab

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y+1/2, z+1/2'
'x+1/2, -y, -z+1/2'
'-x+1/2, y+1/2, -z'
'-x, -y, -z'
'x, y-1/2, -z-1/2'
'-x-1/2, y, z-1/2'
'x-1/2, -y-1/2, z'

_cell_length_a                   9.6634(8)
_cell_length_b                   10.5339(14)
_cell_length_c                   37.350(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     3802.0(7)
_cell_formula_units_Z            8
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    25154
_cell_measurement_theta_min      3.06
_cell_measurement_theta_max      30.00

_exptl_crystal_description       needle
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    2.046
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2224
_exptl_absorpt_coefficient_mu    9.450
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSPACK, Oxford Diffraction Ltd'

_exptl_absorpt_correction_T_min  0.778
_exptl_absorpt_correction_T_max  1.000



_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_standards_number         n/a
_diffrn_measurement_device       'Oxford Diffaction X-Calibur System'
_diffrn_measurement_method       '321 frames, counting time 10 s.'
_diffrn_standards_interval_count n/a
_diffrn_standards_interval_time  n/a
_diffrn_standards_decay_%        n/a
_diffrn_reflns_number            25154
_diffrn_reflns_av_R_equivalents  0.0897
_diffrn_reflns_av_sigmaI/netI    0.0715
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -43
_diffrn_reflns_limit_l_max       52
_diffrn_reflns_theta_min         3.06
_diffrn_reflns_theta_max         30.00
_reflns_number_total             5537
_reflns_number_gt                3740
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Crysalis, Oxford Diffraction'
_computing_cell_refinement       'Crysalis, Oxford Diffraction'
_computing_data_reduction        'Crysalis, Oxford Diffraction'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    PLATON(Spek,2004)


_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;


_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0538P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         5537
_refine_ls_number_parameters     217
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0876
_refine_ls_R_factor_gt           0.0523
_refine_ls_wR_factor_ref         0.1275
_refine_ls_wR_factor_gt          0.1137
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_restrained_S_all      1.006
_refine_ls_shift/su_max          0.004
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group

Tl Tl 0.33487(3) 0.58713(3) 0.508376(9) 0.04309(12) Uani 1 1 d . . .
Fe1 Fe 0.36467(9) 0.47531(9) 0.69647(3) 0.0317(2) Uani 1 1 d . . .
S11 S 0.52787(16) 0.49951(14) 0.56822(5) 0.0313(3) Uani 1 1 d . . .
S13 S 0.38115(17) 0.30890(17) 0.52387(5) 0.0362(4) Uani 1 1 d . . .
C43 C 0.2679(6) 0.4681(6) 0.64775(18) 0.0314(14) Uani 1 1 d . . .
H43 H 0.2755 0.5265 0.6292 0.038 Uiso 1 1 calc R . .
C44 C 0.1695(6) 0.4709(7) 0.6758(2) 0.0365(16) Uani 1 1 d . . .
H44 H 0.1009 0.5320 0.6787 0.044 Uiso 1 1 calc R . .
C45 C 0.1923(6) 0.3653(7) 0.6988(2) 0.0372(16) Uani 1 1 d . . .
H45 H 0.1430 0.3463 0.7195 0.045 Uiso 1 1 calc R . .
C46 C 0.3044(6) 0.2943(6) 0.68437(19) 0.0348(15) Uani 1 1 d . . .
H46 H 0.3391 0.2189 0.6937 0.042 Uiso 1 1 calc R . .
C42 C 0.3546(5) 0.3579(6) 0.65325(16) 0.0245(12) Uani 1 1 d . . .
C41 C 0.4721(6) 0.3184(6) 0.62946(16) 0.0266(12) Uani 1 1 d . . .
H41A H 0.5375 0.3879 0.6274 0.032 Uiso 1 1 calc R . .
H41B H 0.5198 0.2469 0.6402 0.032 Uiso 1 1 calc R . .
N14 N 0.4237(4) 0.2827(4) 0.59357(14) 0.0228(10) Uani 1 1 d . . .
C12 C 0.4415(5) 0.3564(5) 0.56455(16) 0.0229(12) Uani 1 1 d . . .
C31 C 0.3408(5) 0.1656(5) 0.59271(17) 0.0236(12) Uani 1 1 d . . .
H31A H 0.2755 0.1710 0.5730 0.028 Uiso 1 1 calc R . .
H31B H 0.2880 0.1598 0.6147 0.028 Uiso 1 1 calc R . .
C32 C 0.4257(6) 0.0453(6) 0.58842(17) 0.0279(13) Uani 1 1 d . . .
C37 C 0.5489(6) 0.0441(6) 0.56933(18) 0.0326(14) Uani 1 1 d . . .
H37 H 0.5815 0.1203 0.5600 0.039 Uiso 1 1 calc R . .
N36 N 0.6232(6) -0.0613(5) 0.56365(18) 0.0393(14) Uani 1 1 d . . .
C35 C 0.5727(7) -0.1704(7) 0.5764(2) 0.0447(18) Uani 1 1 d . . .
H35 H 0.6210 -0.2450 0.5718 0.054 Uiso 1 1 calc R . .
C34 C 0.4530(7) -0.1776(6) 0.5960(2) 0.0439(18) Uani 1 1 d . . .
H34 H 0.4228 -0.2552 0.6049 0.053 Uiso 1 1 calc R . .
C33 C 0.3778(7) -0.0687(6) 0.6023(2) 0.0375(16) Uani 1 1 d . . .
H33 H 0.2966 -0.0716 0.6157 0.045 Uiso 1 1 calc R . .
C51 C 0.5676(8) 0.5224(10) 0.7023(2) 0.060(3) Uani 1 1 d . . .
H51 H 0.6396 0.4967 0.6874 0.072 Uiso 1 1 calc R . .
C52 C 0.5209(8) 0.4575(9) 0.7332(2) 0.058(2) Uani 1 1 d . . .
H52 H 0.5559 0.3820 0.7423 0.070 Uiso 1 1 calc R . .
C53 C 0.4089(7) 0.5311(9) 0.7475(2) 0.054(2) Uani 1 1 d . . .
H53 H 0.3588 0.5114 0.7680 0.064 Uiso 1 1 calc R . .
C54 C 0.3876(9) 0.6359(8) 0.7260(3) 0.058(2) Uani 1 1 d . . .
H54 H 0.3202 0.6978 0.7294 0.069 Uiso 1 1 calc R . .
C55 C 0.4864(10) 0.6330(9) 0.6977(3) 0.065(3) Uani 1 1 d . . .
H55 H 0.4959 0.6928 0.6795 0.077 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
Tl N36 2.919(6) 8_565 ?
Tl S13 3.0207(19) . ?
Tl S11 3.0539(17) . ?
Tl S13 3.1907(17) 5_666 ?
Tl S11 3.2828(18) 5_666 ?
Tl S13 3.3564(16) 4_556 ?
Tl Tl 3.7345(6) 5_666 ?
Fe1 C45 2.031(6) . ?
Fe1 C54 2.031(8) . ?
Fe1 C51 2.034(7) . ?
Fe1 C42 2.036(6) . ?
Fe1 C55 2.036(8) . ?
Fe1 C44 2.038(6) . ?
Fe1 C53 2.040(8) . ?
Fe1 C46 2.045(6) . ?
Fe1 C43 2.047(6) . ?
Fe1 C52 2.047(8) . ?
S11 C12 1.728(6) . ?
S11 Tl 3.2828(18) 5_666 ?
S13 C12 1.703(6) . ?
S13 Tl 3.1907(17) 5_666 ?
S13 Tl 3.3564(16) 4_546 ?
C43 C44 1.415(9) . ?
C43 C42 1.446(8) . ?
C44 C45 1.422(11) . ?
C45 C46 1.423(9) . ?
C46 C42 1.427(9) . ?
C42 C41 1.500(8) . ?
C41 N14 1.468(8) . ?
N14 C12 1.345(7) . ?
N14 C31 1.471(7) . ?
C31 C32 1.518(8) . ?
C32 C37 1.388(8) . ?
C32 C33 1.389(9) . ?
C37 N36 1.339(8) . ?
N36 C35 1.336(9) . ?
N36 Tl 2.919(6) 8_665 ?
C35 C34 1.370(9) . ?
C34 C33 1.378(9) . ?
C51 C55 1.414(13) . ?
C51 C52 1.415(12) . ?
C52 C53 1.435(11) . ?
C53 C54 1.381(12) . ?
C54 C55 1.425(12) . ?

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
N36 Tl S13 82.99(11) 8_565 . ?
N36 Tl S11 83.23(13) 8_565 . ?
S13 Tl S11 58.41(4) . . ?
N36 Tl S13 154.37(13) 8_565 5_666 ?
S13 Tl S13 106.14(4) . 5_666 ?
S11 Tl S13 81.65(4) . 5_666 ?
N36 Tl S11 150.89(13) 8_565 5_666 ?
S13 Tl S11 80.64(4) . 5_666 ?
S11 Tl S11 107.88(4) . 5_666 ?
S13 Tl S11 54.48(4) 5_666 5_666 ?
N36 Tl S13 83.27(12) 8_565 4_556 ?
S13 Tl S13 146.73(3) . 4_556 ?
S11 Tl S13 148.52(5) . 4_556 ?
S13 Tl S13 99.24(3) 5_666 4_556 ?
S11 Tl S13 97.59(4) 5_666 4_556 ?
C45 Fe1 C54 122.8(3) . . ?
C45 Fe1 C51 157.7(4) . . ?
C54 Fe1 C51 68.5(4) . . ?
C45 Fe1 C42 69.4(3) . . ?
C54 Fe1 C42 160.3(3) . . ?
C51 Fe1 C42 106.2(3) . . ?
C45 Fe1 C55 159.8(4) . . ?
C54 Fe1 C55 41.0(3) . . ?
C51 Fe1 C55 40.7(4) . . ?
C42 Fe1 C55 122.7(3) . . ?
C45 Fe1 C44 40.9(3) . . ?
C54 Fe1 C44 109.0(3) . . ?
C51 Fe1 C44 159.7(4) . . ?
C42 Fe1 C44 69.0(2) . . ?
C55 Fe1 C44 124.2(4) . . ?
C45 Fe1 C53 107.2(3) . . ?
C54 Fe1 C53 39.6(3) . . ?
C51 Fe1 C53 68.2(3) . . ?
C42 Fe1 C53 157.8(3) . . ?
C55 Fe1 C53 67.8(4) . . ?
C44 Fe1 C53 123.7(3) . . ?
C45 Fe1 C46 40.9(2) . . ?
C54 Fe1 C46 158.1(3) . . ?
C51 Fe1 C46 121.7(3) . . ?
C42 Fe1 C46 40.9(2) . . ?
C55 Fe1 C46 158.5(3) . . ?
C44 Fe1 C46 68.4(3) . . ?
C53 Fe1 C46 122.3(3) . . ?
C45 Fe1 C43 69.1(3) . . ?
C54 Fe1 C43 124.3(3) . . ?
C51 Fe1 C43 122.9(3) . . ?
C42 Fe1 C43 41.5(2) . . ?
C55 Fe1 C43 108.3(3) . . ?
C44 Fe1 C43 40.5(3) . . ?
C53 Fe1 C43 159.5(3) . . ?
C46 Fe1 C43 68.8(3) . . ?
C45 Fe1 C52 121.6(4) . . ?
C54 Fe1 C52 68.4(4) . . ?
C51 Fe1 C52 40.6(3) . . ?
C42 Fe1 C52 120.7(3) . . ?
C55 Fe1 C52 68.5(4) . . ?
C44 Fe1 C52 159.0(4) . . ?
C53 Fe1 C52 41.1(3) . . ?
C46 Fe1 C52 105.8(3) . . ?
C43 Fe1 C52 158.1(3) . . ?
C12 S11 Tl 84.9(2) . . ?
C12 S11 Tl 83.3(2) . 5_666 ?
Tl S11 Tl 72.12(4) . 5_666 ?
C12 S13 Tl 86.4(2) . . ?
C12 S13 Tl 86.63(18) . 5_666 ?
Tl S13 Tl 73.86(4) . 5_666 ?
C12 S13 Tl 137.6(2) . 4_546 ?
Tl S13 Tl 120.96(5) . 4_546 ?
Tl S13 Tl 129.67(6) 5_666 4_546 ?
C44 C43 C42 107.5(6) . . ?
C44 C43 Fe1 69.4(4) . . ?
C42 C43 Fe1 68.8(3) . . ?
C43 C44 C45 109.1(5) . . ?
C43 C44 Fe1 70.1(3) . . ?
C45 C44 Fe1 69.2(4) . . ?
C44 C45 C46 107.5(6) . . ?
C44 C45 Fe1 69.8(4) . . ?
C46 C45 Fe1 70.1(3) . . ?
C45 C46 C42 108.7(6) . . ?
C45 C46 Fe1 69.0(4) . . ?
C42 C46 Fe1 69.2(3) . . ?
C46 C42 C43 107.2(5) . . ?
C46 C42 C41 127.6(5) . . ?
C43 C42 C41 125.2(6) . . ?
C46 C42 Fe1 69.9(4) . . ?
C43 C42 Fe1 69.7(4) . . ?
C41 C42 Fe1 127.0(4) . . ?
N14 C41 C42 111.8(5) . . ?
C12 N14 C41 123.2(5) . . ?
C12 N14 C31 122.4(5) . . ?
C41 N14 C31 114.1(5) . . ?
N14 C12 S13 120.4(4) . . ?
N14 C12 S11 120.1(5) . . ?
S13 C12 S11 119.5(3) . . ?
N14 C31 C32 114.1(4) . . ?
C33 C32 C37 118.0(6) . . ?
C37 C32 C31 121.7(6) . . ?
C33 C32 C31 120.2(5) . . ?
N36 C37 C32 123.3(6) . . ?
C35 N36 C37 117.4(6) . . ?
C35 N36 Tl 115.3(4) . 8_665 ?
C37 N36 Tl 124.4(5) . 8_665 ?
N36 C35 C34 123.1(6) . . ?
C35 C34 C33 119.4(7) . . ?
C34 C33 C32 118.6(6) . . ?
C55 C51 C52 108.7(8) . . ?
C55 C51 Fe1 69.8(5) . . ?
C52 C51 Fe1 70.2(4) . . ?
C51 C52 C53 106.5(9) . . ?
C51 C52 Fe1 69.2(5) . . ?
C53 C52 Fe1 69.2(4) . . ?
C54 C53 C52 109.1(8) . . ?
C54 C53 Fe1 69.8(5) . . ?
C52 C53 Fe1 69.7(5) . . ?
C53 C54 C55 108.3(8) . . ?
C53 C54 Fe1 70.5(5) . . ?
C55 C54 Fe1 69.7(5) . . ?
C51 C55 C54 107.4(9) . . ?
C51 C55 Fe1 69.6(5) . . ?
C54 C55 Fe1 69.3(4) . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        30.00
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         2.437
_refine_diff_density_min         -2.308
_refine_diff_density_rms         0.226
_database_code_depnum_ccdc_archive 'CCDC 1031506'
