# Supplementary Material (ESI) for Organic & Biomolecular Chemistry
# This journal is © The Royal Society of Chemistry 2004

data_sad
_database_code_depnum_ccdc_archive 'CCDC 233572'

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
?
;
_chemical_name_common            
;(2Z)-2-(3-[(Methoxycarbonyl)methyl]benzylidene)-3-oxo-2,3-dihydro-
1-benzothiophene-7-carboxylic acid methyl ester (Z-23)
;

_chemical_melting_point          200-202°C
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H16 O6 S'
_chemical_formula_weight         384.39

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           ?
_symmetry_space_group_name_H-M   ?

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                   11.2062(2)
_cell_length_b                   9.5158(2)
_cell_length_c                   17.31690(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 107.0850(10)
_cell_angle_gamma                90.00
_cell_volume                     1765.11(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       ?
_exptl_crystal_colour            'light orange'
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.446
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             800
_exptl_absorpt_coefficient_mu    0.219
_exptl_absorpt_correction_type   ?
_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  ?
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            13132
_diffrn_reflns_av_R_equivalents  0.1168
_diffrn_reflns_av_sigmaI/netI    0.1017
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         1.90
_diffrn_reflns_theta_max         27.50
_reflns_number_total             4060
_reflns_number_gt                2534
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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)+(0.0601P)²+1.6982P] 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     SHELXL
_refine_ls_extinction_coef       0.0021(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         4060
_refine_ls_number_parameters     245
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0854
_refine_ls_R_factor_gt           0.0445
_refine_ls_wR_factor_ref         0.1202
_refine_ls_wR_factor_gt          0.1003
_refine_ls_goodness_of_fit_ref   0.689
_refine_ls_restrained_S_all      0.689
_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
S1 S 0.82608(5) 0.57363(5) 0.04030(3) 0.03655(16) Uani 1 1 d . . .
C5 C 0.81803(19) 0.4268(2) -0.09142(14) 0.0377(5) Uani 1 1 d . . .
O4 O 0.63851(17) 1.21936(15) 0.13489(10) 0.0523(4) Uani 1 1 d . . .
C10 C 0.70206(19) 0.9003(2) -0.01352(13) 0.0355(5) Uani 1 1 d . . .
C7 C 0.76325(19) 0.6583(2) -0.05320(13) 0.0352(5) Uani 1 1 d . . .
C6 C 0.85634(18) 0.4196(2) -0.00727(13) 0.0338(5) Uani 1 1 d . . .
C8 C 0.7637(2) 0.5639(2) -0.12213(14) 0.0403(5) Uani 1 1 d . . .
C11 C 0.6437(2) 1.0242(2) -0.04757(14) 0.0399(5) Uani 1 1 d . . .
H11A H 0.6193 1.0341 -0.1035 0.048 Uiso 1 1 calc R . .
C13 C 0.6574(2) 1.1195(2) 0.08236(14) 0.0395(5) Uani 1 1 d . . .
O6 O 0.52145(17) 1.56116(16) 0.13960(10) 0.0533(4) Uani 1 1 d . . .
C9 C 0.71866(19) 0.7900(2) -0.06730(14) 0.0379(5) Uani 1 1 d . . .
H9A H 0.6939 0.8150 -0.1216 0.045 Uiso 1 1 calc R . .
O3 O 0.72400(18) 0.59645(18) -0.19315(11) 0.0622(5) Uani 1 1 d . . .
O1 O 1.02250(17) 0.17574(16) 0.14860(11) 0.0542(4) Uani 1 1 d . . .
O5 O 0.63281(19) 1.42540(18) 0.24034(11) 0.0659(5) Uani 1 1 d . . .
C16 C 0.5880(2) 1.3495(2) 0.10146(15) 0.0409(5) Uani 1 1 d . . .
H16A H 0.5043 1.3361 0.0655 0.049 Uiso 1 1 calc R . .
H16B H 0.6392 1.3900 0.0707 0.049 Uiso 1 1 calc R . .
C15 C 0.7374(2) 0.8903(2) 0.07095(15) 0.0493(6) Uani 1 1 d . . .
H15A H 0.7769 0.8090 0.0957 0.059 Uiso 1 1 calc R . .
C14 C 0.7153(2) 0.9974(2) 0.11821(15) 0.0516(6) Uani 1 1 d . . .
H14A H 0.7391 0.9880 0.1741 0.062 Uiso 1 1 calc R . .
C12 C 0.6209(2) 1.1332(2) -0.00096(14) 0.0409(5) Uani 1 1 d . . .
H12A H 0.5814 1.2148 -0.0253 0.049 Uiso 1 1 calc R . .
C17 C 0.5850(2) 1.4460(2) 0.17001(15) 0.0407(5) Uani 1 1 d . . .
C1 C 0.91383(19) 0.2977(2) 0.03168(14) 0.0377(5) Uani 1 1 d . . .
C4 C 0.8330(2) 0.3128(2) -0.13774(15) 0.0465(6) Uani 1 1 d . . .
H4A H 0.8053 0.3175 -0.1938 0.056 Uiso 1 1 calc R . .
O2 O 0.9319(2) 0.3784(2) 0.16356(12) 0.0742(6) Uani 1 1 d . . .
C19 C 0.9555(2) 0.2903(2) 0.12072(15) 0.0444(6) Uani 1 1 d . . .
C2 C 0.9298(2) 0.1863(2) -0.01667(16) 0.0479(6) Uani 1 1 d . . .
H2A H 0.9692 0.1050 0.0080 0.058 Uiso 1 1 calc R . .
C3 C 0.8893(2) 0.1928(2) -0.09964(16) 0.0515(6) Uani 1 1 d . . .
H3A H 0.9000 0.1159 -0.1301 0.062 Uiso 1 1 calc R . .
C18 C 0.5109(3) 1.6658(3) 0.19828(17) 0.0652(8) Uani 1 1 d . . .
H18A H 0.4634 1.7444 0.1707 0.098 Uiso 1 1 calc R . .
H18B H 0.5927 1.6969 0.2287 0.098 Uiso 1 1 calc R . .
H18C H 0.4695 1.6253 0.2343 0.098 Uiso 1 1 calc R . .
C20 C 1.0710(3) 0.1619(3) 0.23542(18) 0.0753(9) Uani 1 1 d . . .
H20A H 1.1178 0.0762 0.2484 0.113 Uiso 1 1 calc R . .
H20B H 1.0029 0.1601 0.2586 0.113 Uiso 1 1 calc R . .
H20C H 1.1244 0.2402 0.2569 0.113 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
S1 C7 1.760(2) . ?
S1 C6 1.762(2) . ?
C5 C4 1.388(3) . ?
C5 C6 1.395(3) . ?
C5 C8 1.471(3) . ?
O4 C13 1.375(3) . ?
O4 C16 1.413(2) . ?
C10 C11 1.393(3) . ?
C10 C15 1.402(3) . ?
C10 C9 1.451(3) . ?
C7 C9 1.345(3) . ?
C7 C8 1.495(3) . ?
C6 C1 1.400(3) . ?
C8 O3 1.219(3) . ?
C11 C12 1.384(3) . ?
C13 C14 1.385(3) . ?
C13 C12 1.385(3) . ?
O6 C17 1.329(3) . ?
O6 C18 1.452(3) . ?
O1 C19 1.331(3) . ?
O1 C20 1.447(3) . ?
O5 C17 1.194(3) . ?
C16 C17 1.509(3) . ?
C15 C14 1.375(3) . ?
C1 C2 1.395(3) . ?
C1 C19 1.476(3) . ?
C4 C3 1.375(3) . ?
O2 C19 1.199(3) . ?
C2 C3 1.375(3) . ?

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
C7 S1 C6 91.75(10) . . ?
C4 C5 C6 120.9(2) . . ?
C4 C5 C8 126.2(2) . . ?
C6 C5 C8 112.89(18) . . ?
C13 O4 C16 117.13(18) . . ?
C11 C10 C15 116.94(19) . . ?
C11 C10 C9 118.3(2) . . ?
C15 C10 C9 124.78(19) . . ?
C9 C7 C8 120.2(2) . . ?
C9 C7 S1 128.36(18) . . ?
C8 C7 S1 111.43(15) . . ?
C5 C6 C1 120.04(19) . . ?
C5 C6 S1 113.91(15) . . ?
C1 C6 S1 126.04(17) . . ?
O3 C8 C5 125.5(2) . . ?
O3 C8 C7 124.5(2) . . ?
C5 C8 C7 110.00(19) . . ?
C12 C11 C10 122.1(2) . . ?
O4 C13 C14 115.2(2) . . ?
O4 C13 C12 124.60(19) . . ?
C14 C13 C12 120.2(2) . . ?
C17 O6 C18 115.64(19) . . ?
C7 C9 C10 131.9(2) . . ?
C19 O1 C20 116.8(2) . . ?
O4 C16 C17 108.05(19) . . ?
C14 C15 C10 121.7(2) . . ?
C15 C14 C13 119.8(2) . . ?
C11 C12 C13 119.2(2) . . ?
O5 C17 O6 124.6(2) . . ?
O5 C17 C16 126.6(2) . . ?
O6 C17 C16 108.9(2) . . ?
C2 C1 C6 117.6(2) . . ?
C2 C1 C19 122.3(2) . . ?
C6 C1 C19 120.16(19) . . ?
C3 C4 C5 119.2(2) . . ?
O2 C19 O1 123.5(2) . . ?
O2 C19 C1 123.6(2) . . ?
O1 C19 C1 112.9(2) . . ?
C3 C2 C1 122.1(2) . . ?
C2 C3 C4 120.2(2) . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        27.50
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.362
_refine_diff_density_min         -0.444
_refine_diff_density_rms         0.124


