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The title compound, C20H18ClNOS2, is a thia­zole-derived thio­hydroxamic acid O-ester. The value of Z' is 3 and the asymmetric unit comprises three mol­ecules of identical helicity along the N-O bond. Two of these show an anti and the third a syn arrangement of substituents attached in positions 3 and 4 to the 1,3-thia­zole nucleus.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106004677/hj1090sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106004677/hj1090Isup2.hkl
Contains datablock I

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Portable Document Format (PDF) file https://doi.org/10.1107/S0108270106004677/hj1090Isup3.pdf
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108270106004677/hj1090Isup4.pdf
Supplementary material

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108270106004677/hj1090Isup5.pdf
Supplementary material

CCDC reference: 616134

Comment top

The title compound, (I), furnishes 3-phenyltetrahydropyran as the major non-thiazole-derived product if photolyzed in the presence of reactive H-atom donors. The 4-methyl derivative of (I), i.e. 4-(4-chlorophenyl)-3-(4-methylpent-4-enyloxy)thiazole-2(3H)-thione, affords 2,2-dimethyltetrahydrofuran as the major cyclic ether under identical conditions (Hartung et al., 1999, 2004). This unexpected complementary selectivity initiated a series of experimental and theoretical studies directed toward elucidating polar and steric substituent effects in the underlying ring closure, i.e. the 4-penten-1-oxyl radical cyclization, (Gottwald et al., 2004; Hartung et al. 2004). In order to correlate regioselectivities with conformational preferences, NOE experiments were conducted in CDCl3 solution, however, without leading to decisive results. In view of these difficulties, the crystal structure of 4-(4-chlorophenyl)-3-(4-phenylpent-4-enoxy)thiazole-2(3H)-thione, (I), was investigated. The results of the study are outlined below.

Compound (I) forms colorless hexagonal rods (Fig. 1) and crystallizes in the trigonal space group P31c. The trigonal symmetry of the racemic crystal structure is evident from a projection of the unit cell (Z = 18) along [001] (Figs. 2 and 3). The asymmetric unit comprises three molecules, denoted (Ia), (Ib) and (Ic), of identical helicity with respect to the stereogenic N—O axis (Table 1 and Fig. 2). Its orientation unit with respect to the polar axis, which coincides with the trigonal axis, i.e. the c axis, is given by the Flack (1983) parameter [χ = 0.11 (7)]. Geometrical details of the 1,3-thiazolidinethione substructure of molecules (Ia)–(Ic) are similar to those reported for 3-acetoxy-4-(4-chlorophenyl)-1,3-thiazole-2(3H)-thione, 4-(4-chlorophenyl)-3-hydroxy-1,3-thiazole-2(3H)-thione, and two secondary 3-(alkyloxy)-4-(4-chlorophenyl)-1,3-thiazole-2(3H)-thiones (Hartung et al., 1999). Marked differences, however, were noted for bond angles at On1 (n = 1–3), which are smaller than the reference data for secondary derivatives and 3-acetoxy-4-(4-chlorophenyl)-1,3-thiazole-2(3H)-thione. The values determined for molecules (Ia)–(Ic), on the other hand, are larger than the N—O—H angle found in the crystal structure of 4-(4-chlorophenyl)-3-hydroxy-1,3-thiazole-2(3H)-thione (Hartung et al., 1999). It is therefore tempting to interprete this sequencing of angles in terms of differences in steric congestion caused by substituents at oxygen in cyclic thiohydroxmates of this type. The dihedral angle associated with the offset of Cn12 is slightly larger than the tilt of the 1,3-thiazolidinethione plane from the 4-chlorophenyl plane (Table 1). The relative orientation of the two substituents is anti in molecules (Ia) and (Ic), and syn in (Ib) (Fig. 5). A survey of the literature indicated that a syn arrangement has hitherto not been reported for solid state geometries of O-acyl or O-alkyl derivatives of 4-(4-chlorophenyl)-3-hydroxy-1,3-thiazole-2(3H)-thione (Hartung et al., 1999, 2006). The situation is different in isotropic media. In solution, both conformers exist. This argumentation originates from a topomerization of substituents due to rotation about the N—O bond (Hartung et al., 2001). Data from a computational study on the N-methoxy derivative of (I) predict that the anti arrangement is lower in conformational free energy than the syn rotamer, at least in the applied model that refers to the gas phase (Hartung et al., 2006). The alkenoxy chain, i.e. the reactive part of the molecule upon UV–Vis excitation, shows a +synclinal positioning of atoms On1—Cn12—Cn13—Cn14, antiperiplanar for Cn12—Cn13—Cn14—Cn15, and synperiplanar for Cn13—Cn14—Cn15—Cn16 in M-configured thiones (Ia)–(Ic) (Table 1). This orientation gives rise to a notable distance between atoms that –undergo C—O bond formation upon N—O homolysis [O11···C116 = 5.028 (8) Å for (Ia), O21···C216 = 4.986 (8) Å for (Ib) and O31···C316 = 5.013 (8) Å for (Ic)]. The only conformational change that is, however, necessary in order to convert the side-chain arrangement seen in the crystal structure of (I) into a geometry that closely resembles the calculated lowest energy transition structure of the 6-endo-trig 4-phenyl-4-pentenyl-1-oxyl radical ring closure, is a rotation about the Cn13—Cn14 (n = 1–3) bond. Torsional movements like this are readily feasible at 298 K in solution. In view of the planar solid-state geometry of α-methylstyrene (Bond & Davies, 2002), it was surprising to note that the planes of the olefinic π-bond and the phenyl group are tilted by 20.1 (1)° in (Ia), −31.9 (9)° in (Ib) and −31.9 (9)° in (Ic), as measured by appropriate torsion angles (Table 1). This finding, however, correlates with the calculated dihedral angle in the equilibrium structure of the 4-phenylpent-4-enyl-1-oxyl radical in the gas phase (40.3°; Hartung et al., 2004). This feature is an important aspect in the model that was established for interpreting the origin of the 6-endo selectivity in cyclizations of 4-substituted pent-4-en-1-oxyl radicals on the basis of relative orbital energies (Hartung et al. 2004).

Experimental top

Crystals suitable for X-ray diffraction were obtained from a saturated solution of 4-(4-chlorophenyl)-3-(4-phenyl-4-penten-1-oxy)thiazole-2(3H)-thione (Hartung et al., 1999) in diethyl ether, which was stored at 293 K under an atmosphere saturated with n-pentane vapour.

Refinement top

All H atoms were positioned geometrically and treated as riding atoms (C—H = 0.93–0.98 Å), with Uiso(H) set at 1.2Ueq of the parent atom.

Computing details top

Data collection: AXS-software; cell refinement: AXS-software; data reduction: AXS-software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and ORTEP-3 (Farrugia, 1997, 2005); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1]
[Figure 2]
Fig. 1. Photograph showing the crystal selected for structure determination of (I).

Fig. 2. Molecular structure of crystallographically independent molecules Ia—Ic in the solid state. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small cirles of an arbitrary radius

Fig. 3. Packing of (I), viewed along [001]. Chlorine atoms are depicted in green, nitrogen atoms in blue, oxygen atoms in red, and sulfur atoms in orange.

Fig. 4. A ssignment of absolute configurations at the N—O bond (R = 4-phenyl-4-penten-1-oxy).

Fig. 5. Visualization of anti and syn arrangements of substituents attached to the thiazole-2(3H)-thione entity in I (CP = p-chlorophenyl, R = 4-phenyl-4-penten-1-oxy).
4-(4-Chlorophenyl)-3-(4-phenylpent-4-enyloxy)thiazole-2(3H)-thione top
Crystal data top
C20H18ClNOS2Dx = 1.331 Mg m3
Mr = 387.92Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31cCell parameters from 10106 reflections
a = 36.2171 (1) Åθ = 1.1–25.7°
c = 7.6695 (1) ŵ = 0.42 mm1
V = 8712.14 (12) Å3T = 293 K
Z = 18Hexagonal rod, colourless
F(000) = 36360.48 × 0.20 × 0.20 mm
Data collection top
Bruker four-circle CCD area-detector
diffractometer
8858 reflections with I > 2σ(I)
Radiation source: rotating anode,focus:0.5 x 5mm,50 kV,120 mARint = 0.036
Graphite monochromatorθmax = 25.7°, θmin = 1.3°
ω and ϕ scansh = 4241
49608 measured reflectionsk = 4443
10106 independent reflectionsl = 99
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.096 w = 1/[σ2(Fo2) + (0.0132P)2 + 4.1632P]
where P = (Fo2 + 2Fc2)/3
S = 1.30(Δ/σ)max = 0.001
10106 reflectionsΔρmax = 0.14 e Å3
677 parametersΔρmin = 0.16 e Å3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.11 (7)
Crystal data top
C20H18ClNOS2Z = 18
Mr = 387.92Mo Kα radiation
Trigonal, P31cµ = 0.42 mm1
a = 36.2171 (1) ÅT = 293 K
c = 7.6695 (1) Å0.48 × 0.20 × 0.20 mm
V = 8712.14 (12) Å3
Data collection top
Bruker four-circle CCD area-detector
diffractometer
8858 reflections with I > 2σ(I)
49608 measured reflectionsRint = 0.036
10106 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.096Δρmax = 0.14 e Å3
S = 1.30Δρmin = 0.16 e Å3
10106 reflectionsAbsolute structure: Flack (1983)
677 parametersAbsolute structure parameter: 0.11 (7)
1 restraint
Special details top

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

Refinement. 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 > σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O110.27828 (10)0.48772 (8)0.1173 (4)0.0551 (8)
C1020.31916 (19)0.56186 (14)0.0614 (8)0.0761 (16)
N130.28050 (12)0.52631 (11)0.0815 (6)0.0615 (10)
C1040.24403 (17)0.52983 (16)0.0679 (8)0.0688 (14)
C1050.2548 (2)0.57056 (19)0.0332 (10)0.093 (2)
H1050.23520.57980.01800.140*
C1060.20030 (17)0.49291 (16)0.0833 (7)0.0638 (13)
C1070.1681 (2)0.4907 (2)0.0230 (8)0.0832 (17)
H1070.17460.51180.10620.125*
C1080.1270 (2)0.4582 (2)0.0069 (9)0.093 (2)
H1080.10570.45790.07580.139*
C1090.11706 (18)0.4261 (2)0.1095 (9)0.0812 (17)
C1100.14750 (18)0.42635 (17)0.2179 (8)0.0726 (15)
H1100.14050.40450.29760.109*
C1110.18944 (17)0.46060 (16)0.2043 (7)0.0641 (13)
H1110.21030.46160.27800.096*
C1120.28060 (16)0.46836 (13)0.0469 (7)0.0603 (13)
H110.30760.48640.10460.090*
H120.25770.46440.12450.090*
C1130.27633 (15)0.42587 (14)0.0005 (7)0.0639 (13)
H130.28410.41510.10120.096*
H140.29630.43020.09220.096*
C1140.23302 (16)0.39344 (14)0.0564 (7)0.0648 (13)
H150.21290.39190.03100.097*
H160.22670.40340.16350.097*
C1150.22496 (16)0.34864 (15)0.0875 (8)0.0681 (14)
C1160.2545 (2)0.33901 (19)0.0636 (14)0.128 (3)
H170.24860.31110.07940.192*
H180.28180.36000.03060.192*
C1170.18099 (17)0.31590 (14)0.1404 (7)0.0644 (13)
C1180.14614 (16)0.32236 (16)0.1206 (8)0.0727 (15)
H1180.15050.34780.07260.109*
C1190.10576 (18)0.29202 (18)0.1704 (8)0.0850 (18)
H1190.08320.29710.15410.128*
C1200.0982 (2)0.25426 (19)0.2442 (9)0.0899 (19)
H1200.07080.23380.27820.135*
C1210.1315 (2)0.24736 (17)0.2663 (8)0.0849 (17)
H1210.12670.22180.31510.127*
C1220.17240 (18)0.27757 (15)0.2176 (8)0.0740 (15)
H1220.19470.27220.23680.111*
Cl10.06499 (6)0.38341 (7)0.1270 (3)0.1278 (7)
S110.30874 (6)0.60296 (5)0.0208 (3)0.1043 (6)
S120.36709 (4)0.56718 (4)0.0708 (3)0.0807 (4)
O210.17492 (9)0.03906 (9)0.1929 (4)0.0543 (8)
C2020.10099 (15)0.00329 (18)0.2575 (9)0.0712 (15)
N230.13806 (11)0.03959 (11)0.2392 (6)0.0616 (11)
C2040.13751 (15)0.07788 (15)0.2394 (8)0.0643 (13)
C2050.09797 (15)0.07055 (17)0.2667 (9)0.0810 (18)
H2050.09070.09180.27170.121*
C2060.17553 (14)0.11999 (14)0.2057 (7)0.0545 (12)
C2070.17110 (17)0.14783 (16)0.0922 (8)0.0754 (15)
H2070.14510.13910.03760.113*
C2080.20520 (19)0.18819 (18)0.0609 (9)0.0856 (17)
H2080.20220.20700.01210.128*
C2090.24329 (17)0.19978 (15)0.1393 (8)0.0700 (15)
C2100.24897 (15)0.17351 (15)0.2498 (8)0.0656 (14)
H2100.27540.18220.30080.098*
C2110.21426 (15)0.13353 (14)0.2840 (7)0.0605 (13)
H2110.21730.11550.36170.091*
C2120.19260 (14)0.02767 (16)0.3404 (7)0.0609 (13)
H220.17240.00060.38270.091*
H210.19960.04790.43490.091*
C2130.23238 (14)0.02887 (15)0.2722 (7)0.0639 (13)
H240.22480.00970.17330.096*
H230.24380.01860.36230.096*
C2140.26671 (14)0.07332 (16)0.2164 (7)0.0647 (13)
H250.25600.08200.11820.097*
H260.27150.09290.31140.097*
C2150.30922 (15)0.07799 (18)0.1652 (8)0.0688 (15)
C2160.31574 (19)0.0465 (2)0.1418 (11)0.117 (3)
H270.34260.05150.10870.175*
H280.29360.01870.15800.175*
C2170.34425 (15)0.12313 (18)0.1402 (7)0.0673 (14)
C2180.33627 (15)0.15501 (17)0.0854 (8)0.0703 (14)
H2180.30820.14820.06630.106*
C2190.36856 (17)0.19663 (19)0.0581 (8)0.0792 (16)
H2190.36230.21710.01760.119*
C2200.40976 (18)0.2071 (2)0.0918 (8)0.0837 (17)
H2200.43170.23500.07540.126*
C2210.41892 (16)0.1772 (2)0.1488 (8)0.0804 (18)
H2210.44710.18480.17020.121*
C2220.38689 (16)0.1353 (2)0.1757 (7)0.0798 (17)
H2220.39370.11540.21740.120*
Cl20.28707 (6)0.25040 (5)0.0946 (3)0.1127 (6)
S210.06202 (4)0.01696 (5)0.2915 (3)0.0990 (6)
S220.09101 (4)0.04685 (4)0.2431 (3)0.0856 (5)
O310.16453 (9)0.48097 (8)0.1152 (4)0.0525 (7)
C3020.23863 (15)0.43639 (14)0.0580 (8)0.0695 (15)
N330.19908 (11)0.44128 (10)0.0762 (6)0.0564 (9)
C3040.19395 (16)0.40566 (14)0.0569 (8)0.0663 (13)
C3050.23231 (19)0.37109 (16)0.0240 (9)0.089 (2)
H3050.23630.34390.00780.133*
C3060.15241 (15)0.40760 (13)0.0706 (7)0.0624 (13)
C3070.1427 (2)0.38534 (18)0.0510 (9)0.0870 (18)
H3070.16140.37080.14170.131*
C3080.1048 (2)0.3850 (2)0.0356 (10)0.104 (2)
H3080.09770.37070.11810.156*
C3090.07788 (18)0.40542 (18)0.1000 (10)0.0794 (16)
C3100.08697 (18)0.42726 (15)0.2214 (8)0.0704 (15)
H3100.06830.44100.31330.106*
C3110.12427 (16)0.42859 (14)0.2060 (7)0.0645 (13)
H3110.13060.44370.28720.097*
C3120.14780 (14)0.50642 (14)0.0449 (6)0.0572 (12)
H310.16900.51200.09640.086*
H320.14020.49140.12950.086*
C3130.10886 (13)0.54758 (14)0.0085 (7)0.0586 (12)
H340.11620.55990.10570.088*
H330.10000.56760.08790.088*
C3140.07197 (13)0.54130 (13)0.0608 (7)0.0556 (12)
H350.06770.52540.03080.083*
H360.08010.52390.16530.083*
C3150.02942 (14)0.58185 (14)0.0955 (8)0.0631 (12)
C3160.02578 (17)0.61901 (16)0.1074 (10)0.094 (2)
H380.00090.64290.12580.140*
H370.04980.62190.09760.140*
C3170.00791 (13)0.57527 (13)0.1102 (7)0.0538 (11)
C3180.00397 (17)0.53796 (17)0.1770 (8)0.0698 (14)
H3180.02260.51670.21610.105*
C3190.03825 (18)0.53138 (19)0.1873 (8)0.0831 (17)
H3190.03470.50590.23160.125*
C3200.07765 (17)0.56258 (19)0.1319 (7)0.0740 (16)
H3200.10090.55830.13950.111*
C3210.08295 (15)0.59997 (18)0.0656 (7)0.0712 (15)
H3210.10970.62110.02850.107*
C3220.04824 (14)0.60632 (16)0.0537 (7)0.0645 (13)
H3220.05200.63170.00730.097*
Cl30.03108 (6)0.40294 (7)0.1203 (3)0.1279 (7)
S310.27244 (5)0.38239 (4)0.0154 (3)0.0995 (6)
S320.25399 (4)0.47203 (4)0.0733 (2)0.0758 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O110.0710 (19)0.0394 (15)0.062 (2)0.0332 (15)0.0045 (17)0.0071 (15)
C1020.105 (4)0.043 (3)0.092 (4)0.045 (3)0.003 (4)0.002 (3)
N130.075 (3)0.043 (2)0.074 (3)0.036 (2)0.006 (2)0.012 (2)
C1040.083 (3)0.061 (3)0.080 (4)0.050 (3)0.012 (3)0.011 (3)
C1050.119 (5)0.077 (4)0.119 (6)0.076 (4)0.011 (4)0.006 (4)
C1060.089 (4)0.075 (3)0.057 (3)0.064 (3)0.000 (3)0.003 (3)
C1070.097 (5)0.091 (4)0.091 (4)0.069 (4)0.001 (4)0.004 (4)
C1080.103 (5)0.114 (5)0.095 (5)0.080 (5)0.019 (4)0.009 (4)
C1090.068 (3)0.095 (4)0.090 (5)0.048 (3)0.002 (3)0.017 (4)
C1100.081 (4)0.084 (4)0.071 (4)0.055 (3)0.004 (3)0.004 (3)
C1110.071 (3)0.069 (3)0.066 (3)0.046 (3)0.001 (3)0.004 (3)
C1120.073 (3)0.046 (3)0.070 (3)0.036 (2)0.004 (3)0.002 (2)
C1130.065 (3)0.049 (3)0.081 (4)0.030 (2)0.008 (3)0.007 (3)
C1140.075 (3)0.055 (3)0.075 (4)0.041 (3)0.003 (3)0.011 (3)
C1150.069 (3)0.050 (3)0.088 (4)0.032 (2)0.009 (3)0.012 (3)
C1160.089 (4)0.062 (3)0.242 (10)0.044 (3)0.047 (6)0.039 (5)
C1170.074 (3)0.040 (2)0.071 (3)0.022 (2)0.003 (3)0.000 (2)
C1180.071 (3)0.057 (3)0.088 (4)0.030 (3)0.008 (3)0.006 (3)
C1190.063 (3)0.070 (4)0.101 (5)0.018 (3)0.007 (3)0.008 (3)
C1200.076 (4)0.067 (4)0.091 (5)0.010 (3)0.004 (4)0.005 (3)
C1210.081 (4)0.051 (3)0.092 (4)0.010 (3)0.005 (4)0.000 (3)
C1220.086 (4)0.052 (3)0.079 (4)0.031 (3)0.005 (3)0.000 (3)
Cl10.0748 (10)0.1357 (16)0.161 (2)0.0437 (11)0.0126 (13)0.0102 (15)
S110.1137 (13)0.0494 (8)0.1605 (18)0.0488 (9)0.0099 (13)0.0142 (10)
S120.0744 (8)0.0475 (7)0.1132 (12)0.0252 (6)0.0060 (9)0.0076 (8)
O210.0408 (15)0.0561 (17)0.072 (2)0.0291 (14)0.0021 (15)0.0004 (16)
C2020.046 (3)0.064 (3)0.107 (5)0.029 (2)0.003 (3)0.005 (3)
N230.042 (2)0.050 (2)0.097 (3)0.0263 (18)0.006 (2)0.003 (2)
C2040.053 (3)0.050 (3)0.095 (4)0.030 (2)0.005 (3)0.009 (3)
C2050.050 (3)0.067 (3)0.138 (6)0.038 (3)0.003 (3)0.010 (4)
C2060.058 (3)0.053 (2)0.067 (3)0.039 (2)0.005 (2)0.005 (2)
C2070.072 (3)0.069 (3)0.095 (4)0.043 (3)0.013 (3)0.002 (3)
C2080.097 (4)0.074 (4)0.102 (5)0.054 (3)0.006 (4)0.018 (4)
C2090.072 (3)0.051 (3)0.087 (4)0.031 (3)0.017 (3)0.012 (3)
C2100.059 (3)0.052 (3)0.090 (4)0.031 (2)0.003 (3)0.004 (3)
C2110.058 (3)0.051 (3)0.082 (4)0.034 (2)0.008 (3)0.004 (2)
C2120.052 (3)0.066 (3)0.073 (3)0.036 (2)0.000 (2)0.006 (3)
C2130.052 (3)0.068 (3)0.080 (4)0.036 (2)0.003 (3)0.008 (3)
C2140.048 (3)0.071 (3)0.078 (4)0.032 (2)0.005 (3)0.008 (3)
C2150.045 (3)0.078 (3)0.089 (4)0.035 (3)0.002 (3)0.000 (3)
C2160.064 (4)0.106 (5)0.191 (9)0.051 (4)0.023 (4)0.000 (5)
C2170.048 (3)0.093 (4)0.058 (3)0.033 (3)0.002 (2)0.006 (3)
C2180.047 (3)0.081 (4)0.076 (4)0.027 (3)0.004 (3)0.001 (3)
C2190.071 (3)0.089 (4)0.066 (4)0.031 (3)0.003 (3)0.001 (3)
C2200.066 (4)0.096 (4)0.066 (4)0.023 (3)0.000 (3)0.009 (4)
C2210.036 (3)0.111 (5)0.073 (4)0.021 (3)0.004 (3)0.011 (4)
C2220.050 (3)0.111 (5)0.076 (4)0.039 (3)0.005 (3)0.000 (3)
Cl20.1006 (11)0.0594 (8)0.1562 (18)0.0236 (8)0.0191 (13)0.0216 (10)
S210.0431 (7)0.0681 (9)0.191 (2)0.0315 (6)0.0046 (10)0.0141 (11)
S220.0489 (7)0.0522 (7)0.1550 (16)0.0247 (6)0.0022 (9)0.0074 (9)
O310.0439 (15)0.0396 (15)0.0590 (19)0.0097 (13)0.0053 (15)0.0045 (14)
C3020.050 (3)0.043 (2)0.086 (4)0.001 (2)0.001 (3)0.009 (3)
N330.047 (2)0.0349 (18)0.073 (3)0.0092 (15)0.005 (2)0.0073 (19)
C3040.064 (3)0.045 (2)0.076 (4)0.017 (2)0.010 (3)0.012 (3)
C3050.084 (4)0.044 (3)0.121 (6)0.019 (3)0.013 (4)0.003 (3)
C3060.072 (3)0.037 (2)0.073 (3)0.023 (2)0.005 (3)0.003 (3)
C3070.107 (5)0.076 (4)0.091 (4)0.055 (4)0.017 (4)0.031 (3)
C3080.128 (6)0.093 (5)0.112 (6)0.071 (5)0.003 (5)0.036 (4)
C3090.081 (4)0.072 (3)0.099 (5)0.049 (3)0.006 (4)0.000 (4)
C3100.082 (4)0.050 (3)0.083 (4)0.036 (3)0.008 (3)0.006 (3)
C3110.071 (3)0.045 (3)0.074 (3)0.026 (2)0.002 (3)0.000 (2)
C3120.049 (3)0.049 (2)0.062 (3)0.016 (2)0.000 (2)0.005 (2)
C3130.046 (2)0.044 (2)0.072 (3)0.012 (2)0.002 (2)0.001 (2)
C3140.043 (2)0.047 (2)0.065 (3)0.014 (2)0.003 (2)0.008 (2)
C3150.050 (2)0.053 (3)0.071 (3)0.015 (2)0.002 (3)0.008 (3)
C3160.054 (3)0.045 (3)0.173 (7)0.017 (2)0.004 (4)0.006 (4)
C3170.043 (2)0.048 (2)0.059 (3)0.014 (2)0.001 (2)0.007 (2)
C3180.052 (3)0.062 (3)0.086 (4)0.021 (2)0.006 (3)0.005 (3)
C3190.072 (4)0.076 (4)0.096 (5)0.033 (3)0.005 (3)0.002 (3)
C3200.061 (3)0.092 (4)0.069 (4)0.038 (3)0.014 (3)0.020 (3)
C3210.050 (3)0.079 (4)0.071 (4)0.022 (3)0.003 (3)0.003 (3)
C3220.049 (2)0.063 (3)0.068 (3)0.018 (2)0.004 (2)0.007 (3)
Cl30.1161 (14)0.1380 (16)0.169 (2)0.0926 (13)0.0055 (15)0.0110 (16)
S310.0562 (8)0.0485 (7)0.1604 (18)0.0012 (6)0.0114 (10)0.0126 (10)
S320.0472 (6)0.0584 (7)0.1102 (12)0.0176 (6)0.0038 (8)0.0075 (8)
Geometric parameters (Å, º) top
O11—N131.387 (4)C212—H210.9700
O11—C1121.464 (6)C213—C2141.523 (6)
C102—N131.356 (6)C213—H240.9700
C102—S121.650 (6)C213—H230.9700
C102—S111.737 (5)C214—C2151.514 (6)
N13—C1041.393 (6)C214—H250.9700
C104—C1051.350 (7)C214—H260.9700
C104—C1061.481 (7)C215—C2161.289 (8)
C105—S111.706 (7)C215—C2171.498 (7)
C105—H1050.9300C216—H270.9300
C106—C1111.388 (7)C216—H280.9300
C106—C1071.393 (7)C217—C2181.388 (7)
C107—C1081.365 (9)C217—C2221.404 (7)
C107—H1070.9300C218—C2191.386 (7)
C108—C1091.362 (8)C218—H2180.9300
C108—H1080.9300C219—C2201.368 (7)
C109—C1101.377 (8)C219—H2190.9300
C109—Cl11.747 (6)C220—C2211.352 (8)
C110—C1111.405 (7)C220—H2200.9300
C110—H1100.9300C221—C2221.389 (8)
C111—H1110.9300C221—H2210.9300
C112—C1131.511 (6)C222—H2220.9300
C112—H110.9700O31—N331.387 (4)
C112—H120.9700O31—C3121.472 (6)
C113—C1141.479 (6)C302—N331.360 (6)
C113—H130.9700C302—S321.646 (5)
C113—H140.9700C302—S311.742 (4)
C114—C1151.517 (6)N33—C3041.400 (6)
C114—H150.9700C304—C3051.350 (7)
C114—H160.9700C304—C3061.474 (7)
C115—C1161.295 (7)C305—S311.697 (7)
C115—C1171.489 (7)C305—H3050.9300
C116—H170.9300C306—C3111.385 (7)
C116—H180.9300C306—C3071.389 (7)
C117—C1221.394 (7)C307—C3081.382 (9)
C117—C1181.402 (7)C307—H3070.9300
C118—C1191.373 (7)C308—C3091.364 (9)
C118—H1180.9300C308—H3080.9300
C119—C1201.375 (8)C309—C3101.365 (8)
C119—H1190.9300C309—Cl31.749 (5)
C120—C1211.360 (8)C310—C3111.381 (7)
C120—H1200.9300C310—H3100.9300
C121—C1221.382 (7)C311—H3110.9300
C121—H1210.9300C312—C3131.509 (6)
C122—H1220.9300C312—H310.9700
O21—N231.391 (4)C312—H320.9700
O21—C2121.457 (6)C313—C3141.517 (6)
C202—N231.336 (6)C313—H340.9700
C202—S221.669 (6)C313—H330.9700
C202—S211.733 (5)C314—C3151.529 (6)
N23—C2041.397 (6)C314—H350.9700
C204—C2051.336 (6)C314—H360.9700
C204—C2061.479 (6)C315—C3161.288 (7)
C205—S211.724 (6)C315—C3171.490 (6)
C205—H2050.9300C316—H380.9300
C206—C2111.372 (6)C316—H370.9300
C206—C2071.401 (7)C317—C3181.384 (7)
C207—C2081.384 (7)C317—C3221.394 (6)
C207—H2070.9300C318—C3191.378 (8)
C208—C2091.365 (8)C318—H3180.9300
C208—H2080.9300C319—C3201.372 (8)
C209—C2101.365 (7)C319—H3190.9300
C209—Cl21.757 (5)C320—C3211.367 (7)
C210—C2111.387 (6)C320—H3200.9300
C210—H2100.9300C321—C3221.389 (7)
C211—H2110.9300C321—H3210.9300
C212—C2131.513 (6)C322—H3220.9300
C212—H220.9700
N13—O11—C112108.9 (3)C212—C213—C214112.9 (4)
N13—C102—S12129.2 (3)C212—C213—H24109.0
N13—C102—S11105.7 (4)C214—C213—H24109.0
S12—C102—S11125.1 (3)C212—C213—H23109.0
C102—N13—O11119.4 (4)C214—C213—H23109.0
C102—N13—C104118.7 (4)H24—C213—H23107.8
O11—N13—C104121.8 (4)C215—C214—C213116.0 (4)
C105—C104—N13110.2 (5)C215—C214—H25108.3
C105—C104—C106126.6 (5)C213—C214—H25108.3
N13—C104—C106123.1 (4)C215—C214—H26108.3
C104—C105—S11111.6 (4)C213—C214—H26108.3
C104—C105—H105124.2H25—C214—H26107.4
S11—C105—H105124.2C216—C215—C217121.2 (5)
C111—C106—C107117.9 (5)C216—C215—C214124.3 (5)
C111—C106—C104122.6 (5)C217—C215—C214114.5 (4)
C107—C106—C104119.5 (5)C215—C216—H27120.0
C108—C107—C106121.1 (6)C215—C216—H28120.0
C108—C107—H107119.5H27—C216—H28120.0
C106—C107—H107119.5C218—C217—C222116.8 (5)
C109—C108—C107120.4 (6)C218—C217—C215122.1 (4)
C109—C108—H108119.8C222—C217—C215121.1 (5)
C107—C108—H108119.8C219—C218—C217122.5 (5)
C108—C109—C110121.4 (6)C219—C218—H218118.8
C108—C109—Cl1120.9 (5)C217—C218—H218118.8
C110—C109—Cl1117.7 (5)C220—C219—C218118.8 (6)
C109—C110—C111118.0 (5)C220—C219—H219120.6
C109—C110—H110121.0C218—C219—H219120.6
C111—C110—H110121.0C221—C220—C219120.7 (6)
C106—C111—C110121.3 (5)C221—C220—H220119.7
C106—C111—H111119.4C219—C220—H220119.7
C110—C111—H111119.4C220—C221—C222121.1 (5)
O11—C112—C113106.5 (4)C220—C221—H221119.5
O11—C112—H11110.4C222—C221—H221119.5
C113—C112—H11110.4C221—C222—C217120.1 (6)
O11—C112—H12110.4C221—C222—H222119.9
C113—C112—H12110.4C217—C222—H222119.9
H11—C112—H12108.6C205—S21—C20292.3 (2)
C114—C113—C112114.0 (4)N33—O31—C312110.1 (3)
C114—C113—H13108.8N33—C302—S32129.6 (3)
C112—C113—H13108.8N33—C302—S31105.6 (3)
C114—C113—H14108.8S32—C302—S31124.8 (3)
C112—C113—H14108.8C302—N33—O31120.2 (3)
H13—C113—H14107.7C302—N33—C304119.1 (4)
C113—C114—C115117.2 (4)O31—N33—C304120.7 (4)
C113—C114—H15108.0C305—C304—N33109.0 (5)
C115—C114—H15108.0C305—C304—C306127.6 (5)
C113—C114—H16108.0N33—C304—C306123.4 (4)
C115—C114—H16108.0C304—C305—S31113.1 (4)
H15—C114—H16107.3C304—C305—H305123.5
C116—C115—C117121.6 (5)S31—C305—H305123.5
C116—C115—C114121.5 (5)C311—C306—C307119.4 (5)
C117—C115—C114116.9 (4)C311—C306—C304122.2 (5)
C115—C116—H17120.0C307—C306—C304118.3 (5)
C115—C116—H18120.0C308—C307—C306119.3 (6)
H17—C116—H18120.0C308—C307—H307120.3
C122—C117—C118116.1 (5)C306—C307—H307120.3
C122—C117—C115121.7 (5)C309—C308—C307120.2 (6)
C118—C117—C115122.1 (4)C309—C308—H308119.9
C119—C118—C117121.6 (5)C307—C308—H308119.9
C119—C118—H118119.2C308—C309—C310121.4 (5)
C117—C118—H118119.2C308—C309—Cl3119.3 (5)
C118—C119—C120120.9 (6)C310—C309—Cl3119.3 (5)
C118—C119—H119119.6C309—C310—C311119.0 (5)
C120—C119—H119119.6C309—C310—H310120.5
C121—C120—C119118.7 (6)C311—C310—H310120.5
C121—C120—H120120.6C310—C311—C306120.6 (5)
C119—C120—H120120.6C310—C311—H311119.7
C120—C121—C122121.3 (6)C306—C311—H311119.7
C120—C121—H121119.4O31—C312—C313106.3 (4)
C122—C121—H121119.4O31—C312—H31110.5
C121—C122—C117121.4 (6)C313—C312—H31110.5
C121—C122—H122119.3O31—C312—H32110.5
C117—C122—H122119.3C313—C312—H32110.5
C105—S11—C10293.7 (3)H31—C312—H32108.7
N23—O21—C212111.5 (3)C312—C313—C314112.4 (4)
N23—C202—S22128.9 (4)C312—C313—H34109.1
N23—C202—S21107.2 (4)C314—C313—H34109.1
S22—C202—S21123.8 (3)C312—C313—H33109.1
C202—N23—O21120.8 (3)C314—C313—H33109.1
C202—N23—C204118.1 (4)H34—C313—H33107.8
O21—N23—C204120.3 (3)C313—C314—C315116.2 (4)
C205—C204—N23110.4 (4)C313—C314—H35108.2
C205—C204—C206125.8 (5)C315—C314—H35108.2
N23—C204—C206123.7 (4)C313—C314—H36108.2
C204—C205—S21111.8 (4)C315—C314—H36108.2
C204—C205—H205124.1H35—C314—H36107.4
S21—C205—H205124.1C316—C315—C317122.3 (4)
C211—C206—C207118.7 (4)C316—C315—C314122.9 (5)
C211—C206—C204123.4 (4)C317—C315—C314114.7 (4)
C207—C206—C204117.9 (4)C315—C316—H38120.0
C208—C207—C206120.4 (5)C315—C316—H37120.0
C208—C207—H207119.8H38—C316—H37120.0
C206—C207—H207119.8C318—C317—C322117.2 (5)
C209—C208—C207118.7 (5)C318—C317—C315121.7 (4)
C209—C208—H208120.7C322—C317—C315121.1 (4)
C207—C208—H208120.7C319—C318—C317121.8 (5)
C208—C209—C210122.8 (5)C319—C318—H318119.1
C208—C209—Cl2118.8 (4)C317—C318—H318119.1
C210—C209—Cl2118.5 (4)C320—C319—C318119.7 (6)
C209—C210—C211118.1 (5)C320—C319—H319120.1
C209—C210—H210120.9C318—C319—H319120.1
C211—C210—H210120.9C321—C320—C319120.3 (5)
C206—C211—C210121.4 (5)C321—C320—H320119.9
C206—C211—H211119.3C319—C320—H320119.9
C210—C211—H211119.3C320—C321—C322119.9 (5)
O21—C212—C213105.7 (4)C320—C321—H321120.1
O21—C212—H22110.6C322—C321—H321120.1
C213—C212—H22110.6C321—C322—C317121.1 (5)
O21—C212—H21110.6C321—C322—H322119.5
C213—C212—H21110.6C317—C322—H322119.5
H22—C212—H21108.7C305—S31—C30293.3 (3)
S12—C102—N13—O110.8 (8)C207—C206—C211—C2101.5 (8)
S11—C102—N13—O11179.5 (3)C204—C206—C211—C210179.3 (5)
S12—C102—N13—C104179.9 (5)C209—C210—C211—C2061.9 (8)
S11—C102—N13—C1040.4 (7)N23—O21—C212—C213179.3 (3)
C112—O11—N13—C10284.3 (5)O21—C212—C213—C21464.6 (5)
C112—O11—N13—C10496.6 (5)C212—C213—C214—C215173.6 (5)
C102—N13—C104—C1050.7 (8)C213—C214—C215—C21610.7 (9)
O11—N13—C104—C105179.8 (5)C213—C214—C215—C217170.3 (5)
C102—N13—C104—C106178.4 (5)C216—C215—C217—C218149.7 (7)
O11—N13—C104—C1062.5 (8)C214—C215—C217—C21829.4 (8)
N13—C104—C105—S110.6 (7)C216—C215—C217—C22231.9 (9)
C106—C104—C105—S11178.3 (5)C214—C215—C217—C222149.0 (5)
C105—C104—C106—C111142.5 (6)C222—C217—C218—C2193.1 (9)
N13—C104—C106—C11140.1 (8)C215—C217—C218—C219178.5 (5)
C105—C104—C106—C10735.2 (9)C217—C218—C219—C2202.2 (9)
N13—C104—C106—C107142.2 (6)C218—C219—C220—C2210.8 (9)
C111—C106—C107—C1080.8 (8)C219—C220—C221—C2220.4 (9)
C104—C106—C107—C108177.0 (5)C220—C221—C222—C2171.4 (9)
C106—C107—C108—C1092.5 (9)C218—C217—C222—C2212.6 (8)
C107—C108—C109—C1102.2 (9)C215—C217—C222—C221178.9 (5)
C107—C108—C109—Cl1178.0 (5)C204—C205—S21—C2021.8 (6)
C108—C109—C110—C1110.3 (9)N23—C202—S21—C2053.1 (5)
Cl1—C109—C110—C111179.9 (4)S22—C202—S21—C205174.5 (5)
C107—C106—C111—C1101.1 (8)S32—C302—N33—O310.7 (8)
C104—C106—C111—C110178.9 (5)S31—C302—N33—O31178.6 (4)
C109—C110—C111—C1061.3 (8)S32—C302—N33—C304180.0 (5)
N13—O11—C112—C113177.9 (4)S31—C302—N33—C3040.7 (6)
O11—C112—C113—C11471.3 (6)C312—O31—N33—C30282.9 (5)
C112—C113—C114—C115173.9 (5)C312—O31—N33—C30497.8 (5)
C113—C114—C115—C1160.8 (10)C302—N33—C304—C3050.9 (8)
C113—C114—C115—C117178.5 (5)O31—N33—C304—C305178.4 (5)
C116—C115—C117—C12220.1 (10)C302—N33—C304—C306178.8 (5)
C114—C115—C117—C122162.2 (5)O31—N33—C304—C3061.9 (8)
C116—C115—C117—C118162.0 (8)N33—C304—C305—S310.6 (7)
C114—C115—C117—C11815.8 (8)C306—C304—C305—S31179.0 (5)
C122—C117—C118—C1191.7 (9)C305—C304—C306—C311133.0 (6)
C115—C117—C118—C119179.7 (6)N33—C304—C306—C31147.4 (8)
C117—C118—C119—C1200.9 (10)C305—C304—C306—C30743.0 (9)
C118—C119—C120—C1210.3 (10)N33—C304—C306—C307136.6 (6)
C119—C120—C121—C1220.6 (10)C311—C306—C307—C3080.7 (9)
C120—C121—C122—C1171.5 (10)C304—C306—C307—C308176.8 (6)
C118—C117—C122—C1212.0 (9)C306—C307—C308—C3091.6 (11)
C115—C117—C122—C121180.0 (6)C307—C308—C309—C3101.2 (11)
C104—C105—S11—C1020.4 (6)C307—C308—C309—Cl3177.9 (6)
N13—C102—S11—C1050.0 (5)C308—C309—C310—C3110.0 (9)
S12—C102—S11—C105179.7 (5)Cl3—C309—C310—C311179.1 (4)
S22—C202—N23—O213.8 (9)C309—C310—C311—C3060.9 (8)
S21—C202—N23—O21173.6 (4)C307—C306—C311—C3100.5 (8)
S22—C202—N23—C204173.5 (5)C304—C306—C311—C310175.4 (5)
S21—C202—N23—C2043.9 (7)N33—O31—C312—C313176.4 (3)
C212—O21—N23—C20277.0 (6)O31—C312—C313—C31469.9 (5)
C212—O21—N23—C204113.6 (5)C312—C313—C314—C315172.8 (4)
C202—N23—C204—C2052.7 (8)C313—C314—C315—C31610.6 (9)
O21—N23—C204—C205172.4 (5)C313—C314—C315—C317167.9 (5)
C202—N23—C204—C206174.7 (5)C316—C315—C317—C318149.5 (7)
O21—N23—C204—C2065.0 (8)C314—C315—C317—C31832.0 (7)
N23—C204—C205—S210.1 (7)C316—C315—C317—C32231.7 (9)
C206—C204—C205—S21177.3 (5)C314—C315—C317—C322146.8 (5)
C205—C204—C206—C211135.6 (7)C322—C317—C318—C3190.3 (8)
N23—C204—C206—C21147.4 (8)C315—C317—C318—C319178.6 (5)
C205—C204—C206—C20742.2 (9)C317—C318—C319—C3200.7 (9)
N23—C204—C206—C207134.8 (6)C318—C319—C320—C3210.5 (9)
C211—C206—C207—C2080.2 (8)C319—C320—C321—C3220.2 (8)
C204—C206—C207—C208177.7 (5)C320—C321—C322—C3170.7 (8)
C206—C207—C208—C2091.6 (10)C318—C317—C322—C3210.4 (8)
C207—C208—C209—C2101.2 (9)C315—C317—C322—C321179.3 (5)
C207—C208—C209—Cl2178.1 (5)C304—C305—S31—C3020.2 (6)
C208—C209—C210—C2110.5 (8)N33—C302—S31—C3050.2 (5)
Cl2—C209—C210—C211179.8 (4)S32—C302—S31—C305179.6 (5)

Experimental details

Crystal data
Chemical formulaC20H18ClNOS2
Mr387.92
Crystal system, space groupTrigonal, P31c
Temperature (K)293
a, c (Å)36.2171 (1), 7.6695 (1)
V3)8712.14 (12)
Z18
Radiation typeMo Kα
µ (mm1)0.42
Crystal size (mm)0.48 × 0.20 × 0.20
Data collection
DiffractometerBruker four-circle CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
49608, 10106, 8858
Rint0.036
(sin θ/λ)max1)0.611
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.096, 1.30
No. of reflections10106
No. of parameters677
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.16
Absolute structureFlack (1983)
Absolute structure parameter0.11 (7)

Computer programs: AXS-software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and ORTEP-3 (Farrugia, 1997, 2005), SHELXL97.

Selected geometric parameters (Å, º) top
O11—N131.387 (4)N23—C2041.397 (6)
C102—N131.356 (6)C204—C2051.336 (6)
C102—S121.650 (6)C205—S211.724 (6)
C102—S111.737 (5)O31—N331.387 (4)
N13—C1041.393 (6)C302—N331.360 (6)
C104—C1051.350 (7)C302—S321.646 (5)
C105—S111.706 (7)C302—S311.742 (4)
O21—N231.391 (4)N33—C3041.400 (6)
C202—N231.336 (6)C304—C3051.350 (7)
C202—S221.669 (6)C305—S311.697 (7)
C202—S211.733 (5)
N13—C102—S11105.7 (4)C205—C204—N23110.4 (4)
C102—N13—C104118.7 (4)C204—C205—S21111.8 (4)
C105—C104—N13110.2 (5)C205—S21—C20292.3 (2)
C104—C105—S11111.6 (4)N33—C302—S31105.6 (3)
C105—S11—C10293.7 (3)C302—N33—C304119.1 (4)
N23—C202—S21107.2 (4)C305—C304—N33109.0 (5)
C202—N23—C204118.1 (4)C304—C305—S31113.1 (4)
C112—O11—N13—C10284.3 (5)C212—C213—C214—C215173.6 (5)
N13—C104—C106—C11140.1 (8)C213—C214—C215—C21610.7 (9)
O11—C112—C113—C11471.3 (6)C216—C215—C217—C22231.9 (9)
C112—C113—C114—C115173.9 (5)C312—O31—N33—C30282.9 (5)
C113—C114—C115—C1160.8 (10)N33—C304—C306—C31147.4 (8)
C116—C115—C117—C12220.1 (10)O31—C312—C313—C31469.9 (5)
C212—O21—N23—C20277.0 (6)C312—C313—C314—C315172.8 (4)
N23—C204—C206—C21147.4 (8)C313—C314—C315—C31610.6 (9)
O21—C212—C213—C21464.6 (5)C316—C315—C317—C32231.7 (9)
 

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