# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_ax81
_database_code_depnum_ccdc_archive 'CCDC 1402849'
_audit_update_record             
;
2015-05-26 deposited with the CCDC.
2015-07-23 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 '4-(4-chlorobenzoyl)-5-(methylthio)-thiophen-2(2H)-one' 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H9 Cl O2 S2'
_chemical_formula_sum            'C12 H9 Cl O2 S2'
_chemical_formula_weight         284.76

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'
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'
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   'P 21/c  '
_symmetry_space_group_name_Hall  '-P 2ybc '
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                   12.2624(8)
_cell_length_b                   13.4433(9)
_cell_length_c                   7.9968(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 106.1680(10)
_cell_angle_gamma                90.00
_cell_volume                     1266.11(14)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    9189
_cell_measurement_theta_min      2.30
_cell_measurement_theta_max      28.20

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.30
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.494
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             584
_exptl_absorpt_coefficient_mu    0.616
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7689
_exptl_absorpt_correction_T_max  0.8367
_exptl_absorpt_process_details   'Bruker AXS SADABS program'

_exptl_special_details           
; 
  Sheldrick,G.M.,(2003),University of gottingen,Germany 
;

_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 ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            11867
_diffrn_reflns_av_R_equivalents  0.0203
_diffrn_reflns_av_sigmaI/netI    0.0137
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         2.30
_diffrn_reflns_theta_max         24.99
_reflns_number_total             2225
_reflns_number_gt                2099
_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)+(0.0530P)²+0.4969P] 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         2225
_refine_ls_number_parameters     155
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0368
_refine_ls_R_factor_gt           0.0354
_refine_ls_wR_factor_ref         0.0955
_refine_ls_wR_factor_gt          0.0940
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_restrained_S_all      1.054
_refine_ls_shift/su_max          0.001
_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
C1 C 0.51848(19) 0.8491(2) 0.1490(4) 0.0723(7) Uani 1 1 d . . .
C2 C 0.5407(2) 0.9423(2) 0.2186(4) 0.0794(8) Uani 1 1 d . . .
H2 H 0.4834 0.9799 0.2432 0.095 Uiso 1 1 calc R . .
C3 C 0.64958(18) 0.97989(19) 0.2517(3) 0.0649(6) Uani 1 1 d . . .
H3 H 0.6651 1.0440 0.2955 0.078 Uiso 1 1 calc R . .
C4 C 0.73588(16) 0.92282(15) 0.2201(3) 0.0494(4) Uani 1 1 d . . .
C5 C 0.71092(17) 0.82895(16) 0.1484(3) 0.0544(5) Uani 1 1 d . . .
H5 H 0.7681 0.7903 0.1257 0.065 Uiso 1 1 calc R . .
C6 C 0.6011(2) 0.79243(18) 0.1103(3) 0.0650(6) Uani 1 1 d . . .
H6 H 0.5836 0.7302 0.0590 0.078 Uiso 1 1 calc R . .
C7 C 0.85101(16) 0.96853(14) 0.2526(3) 0.0482(4) Uani 1 1 d . . .
C8 C 0.95402(15) 0.90899(13) 0.3132(2) 0.0424(4) Uani 1 1 d . . .
C9 C 1.05727(15) 0.94340(12) 0.2994(2) 0.0397(4) Uani 1 1 d . . .
C10 C 1.08509(18) 0.77543(15) 0.4509(3) 0.0567(5) Uani 1 1 d . . .
H10A H 1.0872 0.7111 0.3968 0.068 Uiso 1 1 calc R . .
H10B H 1.1141 0.7676 0.5760 0.068 Uiso 1 1 calc R . .
C11 C 0.96444(17) 0.81415(14) 0.4045(2) 0.0473(4) Uani 1 1 d . . .
C12 C 1.22739(19) 1.05112(17) 0.2251(3) 0.0642(6) Uani 1 1 d . . .
H12A H 1.2719 1.0444 0.3440 0.096 Uiso 1 1 calc R . .
H12B H 1.2487 1.1111 0.1770 0.096 Uiso 1 1 calc R . .
H12C H 1.2406 0.9950 0.1591 0.096 Uiso 1 1 calc R . .
Cl1 Cl 0.38168(6) 0.80153(8) 0.10900(16) 0.1256(4) Uani 1 1 d . . .
O1 O 0.85773(13) 1.05771(10) 0.2242(3) 0.0691(5) Uani 1 1 d . . .
O2 O 0.89125(14) 0.76873(11) 0.4483(2) 0.0634(4) Uani 1 1 d . . .
S1 S 1.17060(4) 0.86294(4) 0.37443(7) 0.05026(17) Uani 1 1 d . . .
S2 S 1.07969(4) 1.05662(3) 0.21590(7) 0.04840(17) 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
C1 0.0433(12) 0.0886(18) 0.0843(16) -0.0127(13) 0.0167(11) -0.0121(11)
C2 0.0419(12) 0.094(2) 0.1049(19) -0.0293(15) 0.0241(12) 0.0021(11)
C3 0.0471(11) 0.0633(13) 0.0845(15) -0.0213(11) 0.0184(11) 0.0017(10)
C4 0.0419(10) 0.0512(10) 0.0574(11) -0.0051(9) 0.0178(8) -0.0007(8)
C5 0.0488(11) 0.0538(11) 0.0646(12) -0.0078(9) 0.0224(9) -0.0017(9)
C6 0.0576(13) 0.0601(13) 0.0757(14) -0.0128(11) 0.0160(11) -0.0120(10)
C7 0.0454(10) 0.0420(10) 0.0612(11) -0.0048(8) 0.0214(9) -0.0003(8)
C8 0.0438(10) 0.0369(9) 0.0484(9) -0.0054(7) 0.0159(7) -0.0024(7)
C9 0.0428(9) 0.0367(9) 0.0397(8) -0.0051(7) 0.0116(7) -0.0015(7)
C10 0.0576(12) 0.0435(10) 0.0654(12) 0.0094(9) 0.0114(10) -0.0017(9)
C11 0.0556(11) 0.0407(10) 0.0480(10) -0.0049(8) 0.0184(8) -0.0061(8)
C12 0.0535(12) 0.0609(13) 0.0841(15) 0.0097(11) 0.0286(11) -0.0072(10)
Cl1 0.0498(4) 0.1458(8) 0.1812(10) -0.0453(7) 0.0321(5) -0.0333(4)
O1 0.0525(9) 0.0418(8) 0.1154(13) 0.0060(8) 0.0274(9) 0.0032(6)
O2 0.0702(10) 0.0522(8) 0.0771(10) 0.0065(7) 0.0359(8) -0.0098(7)
S1 0.0411(3) 0.0446(3) 0.0614(3) 0.0023(2) 0.0083(2) 0.00090(18)
S2 0.0473(3) 0.0382(3) 0.0619(3) 0.00321(19) 0.0189(2) -0.00302(18)

_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 1.367(4) . ?
C1 C6 1.370(4) . ?
C1 Cl1 1.740(2) . ?
C2 C3 1.383(3) . ?
C2 H2 0.9300 . ?
C3 C4 1.386(3) . ?
C3 H3 0.9300 . ?
C4 C5 1.385(3) . ?
C4 C7 1.495(3) . ?
C5 C6 1.385(3) . ?
C5 H5 0.9300 . ?
C6 H6 0.9300 . ?
C7 O1 1.227(2) . ?
C7 C8 1.459(3) . ?
C8 C9 1.381(2) . ?
C8 C11 1.457(3) . ?
C9 S2 1.7146(17) . ?
C9 S1 1.7311(18) . ?
C10 C11 1.514(3) . ?
C10 S1 1.793(2) . ?
C10 H10A 0.9700 . ?
C10 H10B 0.9700 . ?
C11 O2 1.215(2) . ?
C12 S2 1.794(2) . ?
C12 H12A 0.9600 . ?
C12 H12B 0.9600 . ?
C12 H12C 0.9600 . ?

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 C6 121.7(2) . . ?
C2 C1 Cl1 119.0(2) . . ?
C6 C1 Cl1 119.3(2) . . ?
C1 C2 C3 119.0(2) . . ?
C1 C2 H2 120.5 . . ?
C3 C2 H2 120.5 . . ?
C2 C3 C4 120.6(2) . . ?
C2 C3 H3 119.7 . . ?
C4 C3 H3 119.7 . . ?
C5 C4 C3 119.21(19) . . ?
C5 C4 C7 122.40(17) . . ?
C3 C4 C7 118.22(18) . . ?
C4 C5 C6 120.2(2) . . ?
C4 C5 H5 119.9 . . ?
C6 C5 H5 119.9 . . ?
C1 C6 C5 119.2(2) . . ?
C1 C6 H6 120.4 . . ?
C5 C6 H6 120.4 . . ?
O1 C7 C8 120.05(17) . . ?
O1 C7 C4 118.57(18) . . ?
C8 C7 C4 121.37(17) . . ?
C9 C8 C11 112.26(16) . . ?
C9 C8 C7 121.18(17) . . ?
C11 C8 C7 126.39(16) . . ?
C8 C9 S2 125.34(14) . . ?
C8 C9 S1 115.36(13) . . ?
S2 C9 S1 119.30(10) . . ?
C11 C10 S1 108.39(13) . . ?
C11 C10 H10A 110.0 . . ?
S1 C10 H10A 110.0 . . ?
C11 C10 H10B 110.0 . . ?
S1 C10 H10B 110.0 . . ?
H10A C10 H10B 108.4 . . ?
O2 C11 C8 127.99(19) . . ?
O2 C11 C10 120.44(18) . . ?
C8 C11 C10 111.52(16) . . ?
S2 C12 H12A 109.5 . . ?
S2 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
S2 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C9 S1 C10 92.23(9) . . ?
C9 S2 C12 102.53(10) . . ?

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
C6 C1 C2 C3 -0.5(5) . . . . ?
Cl1 C1 C2 C3 179.5(2) . . . . ?
C1 C2 C3 C4 -2.0(4) . . . . ?
C2 C3 C4 C5 2.5(4) . . . . ?
C2 C3 C4 C7 177.9(2) . . . . ?
C3 C4 C5 C6 -0.6(3) . . . . ?
C7 C4 C5 C6 -175.8(2) . . . . ?
C2 C1 C6 C5 2.4(4) . . . . ?
Cl1 C1 C6 C5 -177.58(19) . . . . ?
C4 C5 C6 C1 -1.8(4) . . . . ?
C5 C4 C7 O1 140.9(2) . . . . ?
C3 C4 C7 O1 -34.3(3) . . . . ?
C5 C4 C7 C8 -37.7(3) . . . . ?
C3 C4 C7 C8 147.0(2) . . . . ?
O1 C7 C8 C9 -16.1(3) . . . . ?
C4 C7 C8 C9 162.56(17) . . . . ?
O1 C7 C8 C11 158.7(2) . . . . ?
C4 C7 C8 C11 -22.6(3) . . . . ?
C11 C8 C9 S2 -174.54(13) . . . . ?
C7 C8 C9 S2 1.0(3) . . . . ?
C11 C8 C9 S1 5.4(2) . . . . ?
C7 C8 C9 S1 -179.11(14) . . . . ?
C9 C8 C11 O2 174.14(19) . . . . ?
C7 C8 C11 O2 -1.1(3) . . . . ?
C9 C8 C11 C10 -3.3(2) . . . . ?
C7 C8 C11 C10 -178.59(18) . . . . ?
S1 C10 C11 O2 -177.61(15) . . . . ?
S1 C10 C11 C8 0.1(2) . . . . ?
C8 C9 S1 C10 -4.56(15) . . . . ?
S2 C9 S1 C10 175.36(12) . . . . ?
C11 C10 S1 C9 2.34(15) . . . . ?
C8 C9 S2 C12 -177.04(16) . . . . ?
S1 C9 S2 C12 3.05(14) . . . . ?

_diffrn_measured_fraction_theta_max 1.000
_diffrn_reflns_theta_full        24.99
_diffrn_measured_fraction_theta_full 1.000
_refine_diff_density_max         0.311
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.063
####################################################################### 
# 
# 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_ay58m
_database_code_depnum_ccdc_archive 'CCDC 1402850'
_audit_update_record             
;
2015-05-26 deposited with the CCDC.
2015-07-23 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 '4-(4-ethylbenzoyl)-5-(methylthio)thiophen-2,3-dione' 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H12 O3 S2'
_chemical_formula_sum            'C14 H12 O3 S2'
_chemical_formula_weight         292.36

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'
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'

_symmetry_cell_setting           Triclinic
_symmetry_space_group_name_H-M   'P-1   '
_symmetry_space_group_name_Hall  '-P 1'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   5.7321(15)
_cell_length_b                   8.788(2)
_cell_length_c                   13.769(4)
_cell_angle_alpha                99.381(5)
_cell_angle_beta                 101.216(4)
_cell_angle_gamma                90.696(4)
_cell_volume                     670.6(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2233
_cell_measurement_theta_min      2.35
_cell_measurement_theta_max      25.69

_exptl_crystal_description       needle
_exptl_crystal_colour            ?
_exptl_crystal_size_max          0.48
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.08
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             304
_exptl_absorpt_coefficient_mu    0.397
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8324
_exptl_absorpt_correction_T_max  0.9690
_exptl_absorpt_process_details   'Bruker AXS SADABS program'

_exptl_special_details           
; 
  Sheldrick,G.M.,(2003),University of gottingen,Germany 
;

_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 ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6310
_diffrn_reflns_av_R_equivalents  0.0395
_diffrn_reflns_av_sigmaI/netI    0.0462
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         1.53
_diffrn_reflns_theta_max         25.00
_reflns_number_total             2349
_reflns_number_gt                2070
_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)+(0.0892P)²+1.5175P] 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         2349
_refine_ls_number_parameters     194
_refine_ls_number_restraints     45
_refine_ls_R_factor_all          0.0812
_refine_ls_R_factor_gt           0.0726
_refine_ls_wR_factor_ref         0.2122
_refine_ls_wR_factor_gt          0.2068
_refine_ls_goodness_of_fit_ref   1.177
_refine_ls_restrained_S_all      1.196
_refine_ls_shift/su_max          0.012
_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
C1 C 1.052(3) 0.6455(17) 0.6858(9) 0.106(4) Uani 0.771(18) 1 d PDU A 1
H1A H 0.9903 0.5455 0.6505 0.159 Uiso 0.771(18) 1 calc PR A 1
H1B H 1.0479 0.6526 0.7558 0.159 Uiso 0.771(18) 1 calc PR A 1
H1C H 1.2137 0.6604 0.6784 0.159 Uiso 0.771(18) 1 calc PR A 1
C2 C 0.900(3) 0.7707(18) 0.6423(6) 0.108(4) Uani 0.771(18) 1 d PDU A 1
H2A H 0.7379 0.7568 0.6512 0.130 Uiso 0.771(18) 1 calc PR A 1
H2B H 0.9617 0.8715 0.6788 0.130 Uiso 0.771(18) 1 calc PR A 1
C3 C 0.9004(14) 0.7640(10) 0.5326(4) 0.082(2) Uani 1 1 d D . .
C4 C 1.0927(13) 0.8162(10) 0.4986(5) 0.082(2) Uani 1 1 d . A .
H4 H 1.2321 0.8509 0.5444 0.099 Uiso 1 1 calc R . .
C5 C 1.0822(11) 0.8178(8) 0.3986(4) 0.0616(17) Uani 1 1 d . . .
H5 H 1.2159 0.8496 0.3770 0.074 Uiso 1 1 calc R A .
C6 C 0.8729(10) 0.7722(7) 0.3291(4) 0.0473(13) Uani 1 1 d . A .
C7 C 0.6766(11) 0.7221(8) 0.3618(5) 0.0572(15) Uani 1 1 d . . .
H7 H 0.5348 0.6929 0.3162 0.069 Uiso 1 1 calc R A .
C8 C 0.6918(13) 0.7156(9) 0.4626(5) 0.071(2) Uani 1 1 d . A .
H8 H 0.5612 0.6785 0.4839 0.086 Uiso 1 1 calc R . .
C9 C 0.8692(9) 0.7647(6) 0.2197(4) 0.0419(12) Uani 1 1 d . . .
C10 C 0.6558(8) 0.8093(6) 0.1544(4) 0.0369(11) Uani 1 1 d . A .
C11 C 0.5980(8) 0.7570(5) 0.0546(4) 0.0357(11) Uani 1 1 d . . .
C12 C 0.2906(9) 0.9427(6) 0.1001(4) 0.0418(12) Uani 1 1 d . . .
C13 C 0.4936(9) 0.9235(6) 0.1881(4) 0.0405(12) Uani 1 1 d . A .
C14 C 0.5968(11) 0.5926(7) -0.1365(4) 0.0545(15) Uani 1 1 d . . .
H14A H 0.4367 0.5599 -0.1359 0.082 Uiso 1 1 calc R A .
H14B H 0.6689 0.5125 -0.1752 0.082 Uiso 1 1 calc R . .
H14C H 0.5946 0.6845 -0.1659 0.082 Uiso 1 1 calc R . .
C1D C 0.882(9) 0.605(4) 0.646(3) 0.109(4) Uani 0.229(18) 1 d PDU A 2
H1D H 0.7115 0.5945 0.6259 0.163 Uiso 0.229(18) 1 calc PR A 2
H1E H 0.9295 0.5810 0.7121 0.163 Uiso 0.229(18) 1 calc PR A 2
H1F H 0.9517 0.5344 0.5995 0.163 Uiso 0.229(18) 1 calc PR A 2
C2D C 0.967(7) 0.772(5) 0.6446(8) 0.106(4) Uani 0.229(18) 1 d PDU A 2
H2C H 0.8791 0.8482 0.6805 0.127 Uiso 0.229(18) 1 calc PR A 2
H2D H 1.1362 0.7905 0.6701 0.127 Uiso 0.229(18) 1 calc PR A 2
O1 O 1.0404(7) 0.7181(5) 0.1848(3) 0.0546(10) Uani 1 1 d . A .
O2 O 0.5019(7) 1.0029(5) 0.2689(3) 0.0607(12) Uani 1 1 d . . .
O3 O 0.1333(7) 1.0306(5) 0.1053(3) 0.0557(11) Uani 1 1 d . A .
S1 S 0.3321(2) 0.81915(15) -0.01252(9) 0.0392(4) Uani 1 1 d . A .
S2 S 0.7659(2) 0.63192(16) -0.00978(10) 0.0437(4) Uani 1 1 d . A .

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 0.112(8) 0.159(8) 0.063(5) 0.055(5) 0.025(5) 0.060(7)
C2 0.112(8) 0.164(8) 0.061(5) 0.043(5) 0.026(5) 0.069(6)
C3 0.083(5) 0.126(7) 0.044(4) 0.017(4) 0.019(4) 0.065(5)
C4 0.064(4) 0.121(7) 0.047(4) -0.008(4) -0.006(3) 0.040(4)
C5 0.048(3) 0.086(5) 0.044(3) -0.002(3) 0.003(3) 0.020(3)
C6 0.045(3) 0.056(3) 0.040(3) 0.006(2) 0.006(2) 0.020(2)
C7 0.052(3) 0.072(4) 0.048(3) 0.013(3) 0.010(3) 0.019(3)
C8 0.070(4) 0.100(5) 0.056(4) 0.027(4) 0.029(3) 0.041(4)
C9 0.041(3) 0.045(3) 0.041(3) 0.008(2) 0.012(2) 0.010(2)
C10 0.034(2) 0.041(3) 0.034(3) 0.004(2) 0.007(2) 0.006(2)
C11 0.035(2) 0.034(2) 0.040(3) 0.009(2) 0.011(2) 0.001(2)
C12 0.041(3) 0.044(3) 0.042(3) 0.007(2) 0.011(2) 0.007(2)
C13 0.040(3) 0.042(3) 0.040(3) 0.004(2) 0.012(2) 0.010(2)
C14 0.070(4) 0.055(3) 0.041(3) 0.002(3) 0.020(3) 0.011(3)
C1D 0.113(9) 0.165(9) 0.064(7) 0.045(7) 0.030(7) 0.063(9)
C2D 0.110(9) 0.162(8) 0.061(6) 0.045(6) 0.027(6) 0.068(7)
O1 0.043(2) 0.077(3) 0.048(2) 0.015(2) 0.0157(18) 0.0226(19)
O2 0.063(3) 0.070(3) 0.040(2) -0.014(2) 0.0068(19) 0.027(2)
O3 0.052(2) 0.060(2) 0.055(2) 0.0093(19) 0.0125(19) 0.028(2)
S1 0.0345(7) 0.0461(8) 0.0362(7) 0.0057(5) 0.0055(5) 0.0067(5)
S2 0.0416(7) 0.0483(8) 0.0433(8) 0.0040(6) 0.0158(6) 0.0102(6)

_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 1.538(5) . ?
C1 H1A 0.9600 . ?
C1 H1B 0.9600 . ?
C1 H1C 0.9600 . ?
C2 C3 1.503(5) . ?
C2 H2A 0.9700 . ?
C2 H2B 0.9700 . ?
C3 C4 1.380(12) . ?
C3 C8 1.395(11) . ?
C3 C2D 1.504(5) . ?
C4 C5 1.368(9) . ?
C4 H4 0.9300 . ?
C5 C6 1.390(8) . ?
C5 H5 0.9300 . ?
C6 C7 1.383(8) . ?
C6 C9 1.492(7) . ?
C7 C8 1.384(8) . ?
C7 H7 0.9300 . ?
C8 H8 0.9300 . ?
C9 O1 1.221(6) . ?
C9 C10 1.469(7) . ?
C10 C11 1.350(7) . ?
C10 C13 1.457(7) . ?
C11 S2 1.720(5) . ?
C11 S1 1.764(5) . ?
C12 O3 1.199(6) . ?
C12 C13 1.540(7) . ?
C12 S1 1.800(5) . ?
C13 O2 1.205(6) . ?
C14 S2 1.800(6) . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C1D C2D 1.547(5) . ?
C1D H1D 0.9600 . ?
C1D H1E 0.9600 . ?
C1D H1F 0.9600 . ?
C2D H2C 0.9700 . ?
C2D H2D 0.9700 . ?

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
C3 C2 C1 111.5(8) . . ?
C3 C2 H2A 109.3 . . ?
C1 C2 H2A 109.3 . . ?
C3 C2 H2B 109.3 . . ?
C1 C2 H2B 109.3 . . ?
H2A C2 H2B 108.0 . . ?
C4 C3 C8 118.3(6) . . ?
C4 C3 C2D 109.2(15) . . ?
C8 C3 C2D 132.5(16) . . ?
C4 C3 C2 122.6(10) . . ?
C8 C3 C2 118.9(9) . . ?
C2D C3 C2 14.4(19) . . ?
C3 C4 C5 121.2(7) . . ?
C3 C4 H4 119.4 . . ?
C5 C4 H4 119.4 . . ?
C4 C5 C6 120.5(7) . . ?
C4 C5 H5 119.8 . . ?
C6 C5 H5 119.8 . . ?
C7 C6 C5 119.2(6) . . ?
C7 C6 C9 120.8(5) . . ?
C5 C6 C9 119.7(5) . . ?
C6 C7 C8 119.8(6) . . ?
C6 C7 H7 120.1 . . ?
C8 C7 H7 120.1 . . ?
C7 C8 C3 120.9(7) . . ?
C7 C8 H8 119.5 . . ?
C3 C8 H8 119.5 . . ?
O1 C9 C10 120.5(5) . . ?
O1 C9 C6 120.0(5) . . ?
C10 C9 C6 119.4(4) . . ?
C11 C10 C13 112.4(4) . . ?
C11 C10 C9 123.4(5) . . ?
C13 C10 C9 124.1(4) . . ?
C10 C11 S2 123.8(4) . . ?
C10 C11 S1 117.6(4) . . ?
S2 C11 S1 118.6(3) . . ?
O3 C12 C13 125.0(5) . . ?
O3 C12 S1 125.2(4) . . ?
C13 C12 S1 109.7(3) . . ?
O2 C13 C10 130.5(5) . . ?
O2 C13 C12 119.2(5) . . ?
C10 C13 C12 110.3(4) . . ?
S2 C14 H14A 109.5 . . ?
S2 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
S2 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C2D C1D H1D 109.5 . . ?
C2D C1D H1E 109.5 . . ?
H1D C1D H1E 109.5 . . ?
C2D C1D H1F 109.5 . . ?
H1D C1D H1F 109.5 . . ?
H1E C1D H1F 109.5 . . ?
C3 C2D C1D 96(2) . . ?
C3 C2D H2C 112.5 . . ?
C1D C2D H2C 112.5 . . ?
C3 C2D H2D 112.5 . . ?
C1D C2D H2D 112.5 . . ?
H2C C2D H2D 110.0 . . ?
C11 S1 C12 89.7(2) . . ?
C11 S2 C14 104.6(3) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C1 C2 C3 C4 -75.1(18) . . . . ?
C1 C2 C3 C8 110.5(14) . . . . ?
C1 C2 C3 C2D -53(8) . . . . ?
C8 C3 C4 C5 -1.3(12) . . . . ?
C2D C3 C4 C5 179(2) . . . . ?
C2 C3 C4 C5 -175.8(8) . . . . ?
C3 C4 C5 C6 2.5(12) . . . . ?
C4 C5 C6 C7 -1.3(10) . . . . ?
C4 C5 C6 C9 -176.0(6) . . . . ?
C5 C6 C7 C8 -1.0(9) . . . . ?
C9 C6 C7 C8 173.5(6) . . . . ?
C6 C7 C8 C3 2.2(10) . . . . ?
C4 C3 C8 C7 -1.1(11) . . . . ?
C2D C3 C8 C7 179(3) . . . . ?
C2 C3 C8 C7 173.6(8) . . . . ?
C7 C6 C9 O1 -136.1(6) . . . . ?
C5 C6 C9 O1 38.5(8) . . . . ?
C7 C6 C9 C10 42.2(8) . . . . ?
C5 C6 C9 C10 -143.3(5) . . . . ?
O1 C9 C10 C11 22.9(8) . . . . ?
C6 C9 C10 C11 -155.3(5) . . . . ?
O1 C9 C10 C13 -152.0(5) . . . . ?
C6 C9 C10 C13 29.7(8) . . . . ?
C13 C10 C11 S2 175.3(4) . . . . ?
C9 C10 C11 S2 -0.2(7) . . . . ?
C13 C10 C11 S1 -5.8(6) . . . . ?
C9 C10 C11 S1 178.8(4) . . . . ?
C11 C10 C13 O2 -173.0(6) . . . . ?
C9 C10 C13 O2 2.4(9) . . . . ?
C11 C10 C13 C12 4.1(6) . . . . ?
C9 C10 C13 C12 179.6(5) . . . . ?
O3 C12 C13 O2 -1.2(9) . . . . ?
S1 C12 C13 O2 176.5(4) . . . . ?
O3 C12 C13 C10 -178.7(5) . . . . ?
S1 C12 C13 C10 -1.1(5) . . . . ?
C4 C3 C2D C1D -130(3) . . . . ?
C8 C3 C2D C1D 50(5) . . . . ?
C2 C3 C2D C1D 70(7) . . . . ?
C10 C11 S1 C12 4.3(4) . . . . ?
S2 C11 S1 C12 -176.7(3) . . . . ?
O3 C12 S1 C11 176.1(5) . . . . ?
C13 C12 S1 C11 -1.6(4) . . . . ?
C10 C11 S2 C14 176.3(4) . . . . ?
S1 C11 S2 C14 -2.6(4) . . . . ?

_diffrn_measured_fraction_theta_max 0.995
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.995
_refine_diff_density_max         0.541
_refine_diff_density_min         -0.375
_refine_diff_density_rms         0.085
