# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is © The Royal Society of Chemistry 2003

data_global

_journal_coden_Cambridge         177

loop_
_publ_author_name
'Tatsuro Imakubo'

_publ_contact_author_name        'Dr Tatsuro Imakubo'
_publ_contact_author_address     
;
RIKEN
2-1, Hirosawa
Wako
Saitama
351-0198
JAPAN
;

_publ_contact_author_email       IMAKUBO@POSTMAN.RIKEN.GO.JP

_publ_requested_journal          'Organic & Biomolecular Chemistry'

_publ_section_title              
;
Synthesis and Properties of Hetero-halogenated TTFs
;

data_compound_2
_database_code_CSD               219243

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
4-Chloro[1,3]dithiole-2-thione
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C3 H Cl S3'
_chemical_formula_weight         168.67

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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P2(1)/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                   4.0483(10)
_cell_length_b                   10.844(3)
_cell_length_c                   13.748(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 97.190(5)
_cell_angle_gamma                90.00
_cell_volume                     598.8(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    295(2)
_cell_measurement_reflns_used    3548
_cell_measurement_theta_min      2.40
_cell_measurement_theta_max      28.34

_exptl_crystal_description       prism
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.60
_exptl_crystal_size_mid          0.40
_exptl_crystal_size_min          0.20
_exptl_crystal_density_meas      0
_exptl_crystal_density_diffrn    1.871
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             336
_exptl_absorpt_coefficient_mu    1.543
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
;
?
;

_diffrn_ambient_temperature      295(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean 8.366
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            4173
_diffrn_reflns_av_R_equivalents  0.0223
_diffrn_reflns_av_sigmaI/netI    0.0227
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         2.40
_diffrn_reflns_theta_max         28.34
_reflns_number_total             1479
_reflns_number_gt                1364
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.0496P)²+0.5343P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         1479
_refine_ls_number_parameters     64
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0403
_refine_ls_R_factor_gt           0.0378
_refine_ls_wR_factor_ref         0.1112
_refine_ls_wR_factor_gt          0.1098
_refine_ls_goodness_of_fit_ref   1.170
_refine_ls_restrained_S_all      1.170
_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
S2 S 0.41125(19) 0.34827(6) 0.48469(5) 0.0405(2) Uani 1 1 d . . .
Cl1 Cl 0.7817(2) 0.13671(7) 0.57984(6) 0.0544(2) Uani 1 1 d . . .
S3 S 0.3927(2) 0.24700(7) 0.29005(5) 0.0482(2) Uani 1 1 d . . .
S1 S 0.0781(2) 0.49129(8) 0.31562(6) 0.0513(2) Uani 1 1 d . . .
C2 C 0.5985(7) 0.2056(3) 0.4736(2) 0.0397(6) Uani 1 1 d . . .
C1 C 0.2828(7) 0.3682(3) 0.3606(2) 0.0379(5) Uani 1 1 d . . .
C3 C 0.5910(8) 0.1588(3) 0.3840(2) 0.0455(6) Uani 1 1 d . . .
H3 H 0.6869 0.0831 0.3727 0.055 Uiso 1 1 calc R . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
S2 0.0517(4) 0.0347(3) 0.0347(3) -0.0025(2) 0.0044(3) 0.0005(3)
Cl1 0.0661(5) 0.0485(4) 0.0478(4) 0.0120(3) 0.0045(3) 0.0074(3)
S3 0.0624(5) 0.0484(4) 0.0341(4) -0.0057(3) 0.0073(3) -0.0048(3)
S1 0.0535(4) 0.0477(4) 0.0505(4) 0.0101(3) -0.0021(3) 0.0025(3)
C2 0.0442(13) 0.0338(12) 0.0416(14) 0.0036(11) 0.0075(11) -0.0019(10)
C1 0.0377(12) 0.0379(13) 0.0377(13) 0.0010(10) 0.0029(10) -0.0080(10)
C3 0.0567(16) 0.0354(13) 0.0462(15) -0.0028(11) 0.0141(13) 0.0007(12)

_geom_special_details            
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix.  The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry.  An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
S2 C1 1.733(3) . ?
S2 C2 1.738(3) . ?
Cl1 C2 1.724(3) . ?
S3 C3 1.723(3) . ?
S3 C1 1.725(3) . ?
S1 C1 1.650(3) . ?
C2 C3 1.329(4) . ?

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
C1 S2 C2 96.02(14) . . ?
C3 S3 C1 97.46(14) . . ?
C3 C2 Cl1 125.3(2) . . ?
C3 C2 S2 117.5(2) . . ?
Cl1 C2 S2 117.21(17) . . ?
S1 C1 S3 123.92(17) . . ?
S1 C1 S2 123.00(17) . . ?
S3 C1 S2 113.08(16) . . ?
C2 C3 S3 116.0(2) . . ?

_diffrn_measured_fraction_theta_max 0.985
_diffrn_reflns_theta_full        28.34
_diffrn_measured_fraction_theta_full 0.985
_refine_diff_density_max         0.371
_refine_diff_density_min         -0.366
_refine_diff_density_rms         0.107

data_ClIPS
_database_code_CSD               219244

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C8 H2 Cl I N2 S2 Se2'
_chemical_formula_weight         510.51

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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Se Se -0.0929 2.2259 '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'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   Pn

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

_cell_length_a                   6.7584(15)
_cell_length_b                   4.0939(9)
_cell_length_c                   22.946(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 97.097(4)
_cell_angle_gamma                90.00
_cell_volume                     630.0(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1559
_cell_measurement_theta_min      3.06
_cell_measurement_theta_max      28.25

_exptl_crystal_description       needle
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.60
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.02
_exptl_crystal_density_meas      0
_exptl_crystal_density_diffrn    2.691
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             468
_exptl_absorpt_coefficient_mu    8.833
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_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_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean 8.366
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            2464
_diffrn_reflns_av_R_equivalents  0.0264
_diffrn_reflns_av_sigmaI/netI    0.0484
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       3
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_theta_min         1.79
_diffrn_reflns_theta_max         28.26
_reflns_number_total             1391
_reflns_number_gt                1314
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.1207P)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    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.0(2)
_refine_ls_number_reflns         1391
_refine_ls_number_parameters     146
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0628
_refine_ls_R_factor_gt           0.0602
_refine_ls_wR_factor_ref         0.1595
_refine_ls_wR_factor_gt          0.1572
_refine_ls_goodness_of_fit_ref   1.119
_refine_ls_restrained_S_all      1.118
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.001

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
C7 C 0.659(3) 1.036(4) 0.1715(6) 0.030(3) Uani 1 1 d . . .
I1 I 0.72096(12) 0.1290(2) -0.14820(4) 0.0343(3) Uani 1 1 d . . .
Se3 Se 0.5803(3) 0.8526(5) 0.09683(8) 0.0347(5) Uani 1 1 d . . .
Se2 Se 1.0492(3) 0.8208(4) 0.14980(9) 0.0338(4) Uani 1 1 d . . .
Cl1 Cl 1.2300(7) 0.1186(12) -0.0860(2) 0.0398(11) Uani 1 1 d . . .
N1 N 0.932(3) 1.137(4) 0.2475(6) 0.037(4) Uani 1 1 d . . .
C1 C 0.845(3) 0.724(5) 0.0863(6) 0.030(4) Uani 1 1 d . . .
C4 C 0.590(4) 1.295(5) 0.2527(9) 0.053(6) Uani 1 1 d . . .
H4 H 0.4994 1.4029 0.2733 0.064 Uiso 1 1 calc R . .
C5 C 0.887(2) 0.572(4) 0.0369(6) 0.024(3) Uani 1 1 d . . .
C3 C 0.786(4) 1.277(5) 0.2777(9) 0.051(6) Uani 1 1 d . . .
H3 H 0.8211 1.3585 0.3154 0.061 Uiso 1 1 calc R . .
C6 C 0.852(3) 0.295(4) -0.0663(7) 0.026(3) Uani 1 1 d . . .
N2 N 0.522(3) 1.166(4) 0.1999(8) 0.045(4) Uani 1 1 d . . .
C2 C 0.866(2) 1.016(4) 0.1948(6) 0.024(3) Uani 1 1 d . . .
S1 S 1.1243(8) 0.4370(13) 0.0244(2) 0.0369(10) Uani 1 1 d . . .
S2 S 0.6925(6) 0.4735(13) -0.01998(18) 0.0342(10) Uani 1 1 d . . .
C8 C 1.048(3) 0.294(4) -0.0463(7) 0.034(4) Uani 1 1 d . . .

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
C7 0.033(9) 0.034(8) 0.024(7) 0.001(6) 0.013(7) -0.013(7)
I1 0.0438(7) 0.0351(5) 0.0252(5) -0.0043(4) 0.0090(4) -0.0022(5)
Se3 0.0291(10) 0.0472(11) 0.0279(8) -0.0084(6) 0.0035(7) 0.0010(8)
Se2 0.0297(9) 0.0437(9) 0.0278(8) -0.0107(6) 0.0034(7) -0.0004(8)
Cl1 0.030(2) 0.055(3) 0.037(2) -0.0082(17) 0.015(2) 0.005(2)
N1 0.046(10) 0.045(10) 0.021(6) -0.006(5) 0.010(7) -0.003(7)
C1 0.027(9) 0.050(10) 0.014(6) -0.002(6) 0.004(6) 0.000(8)
C4 0.082(18) 0.045(11) 0.043(10) -0.006(8) 0.050(12) -0.004(11)
C5 0.020(7) 0.031(8) 0.020(6) -0.005(5) 0.003(6) -0.006(6)
C3 0.09(2) 0.028(9) 0.038(9) -0.006(7) 0.022(11) 0.002(11)
C6 0.030(9) 0.028(8) 0.023(6) -0.004(5) 0.011(7) 0.006(7)
N2 0.060(12) 0.037(9) 0.043(8) 0.001(6) 0.024(9) 0.010(8)
C2 0.032(9) 0.027(8) 0.015(6) 0.001(5) 0.007(6) -0.007(7)
S1 0.028(2) 0.053(3) 0.0301(19) -0.0130(17) 0.0028(17) -0.001(2)
S2 0.025(2) 0.053(3) 0.0237(17) -0.0098(16) 0.0027(17) 0.001(2)
C8 0.044(11) 0.037(9) 0.024(7) -0.001(6) 0.021(8) 0.002(8)

_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
C7 N2 1.31(2) . ?
C7 C2 1.43(2) . ?
C7 Se3 1.886(16) . ?
I1 C6 2.090(16) . ?
Se3 C1 1.911(18) . ?
Se2 C2 1.886(15) . ?
Se2 C1 1.919(17) . ?
Cl1 C8 1.773(16) . ?
N1 C2 1.33(2) . ?
N1 C3 1.40(3) . ?
C1 C5 1.353(19) . ?
C4 N2 1.35(3) . ?
C4 C3 1.38(4) . ?
C5 S1 1.752(16) . ?
C5 S2 1.782(16) . ?
C6 C8 1.34(3) . ?
C6 S2 1.765(14) . ?
S1 C8 1.741(18) . ?

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
N2 C7 C2 123.6(16) . . ?
N2 C7 Se3 118.4(16) . . ?
C2 C7 Se3 118.0(11) . . ?
C7 Se3 C1 93.4(7) . . ?
C2 Se2 C1 92.6(7) . . ?
C2 N1 C3 115.0(18) . . ?
C5 C1 Se3 121.9(13) . . ?
C5 C1 Se2 121.7(13) . . ?
Se3 C1 Se2 116.3(8) . . ?
N2 C4 C3 123.7(17) . . ?
C1 C5 S1 124.9(13) . . ?
C1 C5 S2 120.4(13) . . ?
S1 C5 S2 114.6(8) . . ?
C4 C3 N1 121.1(18) . . ?
C8 C6 S2 116.4(12) . . ?
C8 C6 I1 126.7(10) . . ?
S2 C6 I1 116.9(9) . . ?
C7 N2 C4 115(2) . . ?
N1 C2 C7 121.4(13) . . ?
N1 C2 Se2 118.9(12) . . ?
C7 C2 Se2 119.6(10) . . ?
C8 S1 C5 94.9(8) . . ?
C6 S2 C5 94.8(8) . . ?
C6 C8 S1 119.0(11) . . ?
C6 C8 Cl1 122.8(12) . . ?
S1 C8 Cl1 117.9(12) . . ?

_diffrn_measured_fraction_theta_max 0.814
_diffrn_reflns_theta_full        28.26
_diffrn_measured_fraction_theta_full 0.814
_refine_diff_density_max         2.025
_refine_diff_density_min         -1.372
_refine_diff_density_rms         0.352



