Crystal structures of two thia-zolidinone derivatives bearing a tri-chloro-methyl substituent at the 2-position.

The title compounds 2-tri-chloro-methyl-3-phenyl-1,3-thia-zolidin-4-one (C10H8Cl3NOS), 1 and 3-(4-chloro-phen-yl)-2-tri-chloro-methyl-1,3-thia-zolidin-4-one (C10H7Cl4NOS) 2, are structurally related with one atom substitution difference in the para position of the benzene ring. In both structures, the thia-zolidinone ring adopts an envelope conformation with the S atom as the flap. The dihedral angles between the rings [48.72 (11) in 1 and 48.42 (9)° in 2] are very similar and the mol-ecules are almost superimposable. In both crystal structures, C-H⋯O 'head-to-tail' inter-actions between the chiral carbon atoms and the thia-zolidinone oxygen atoms result in infinite monochiral chains along the direction of the shortest unit-cell parameter, namely a in 1 and b in 2. C-H⋯π inter-actions between the thia-zolidinone carbon atom at the 4-position and the phenyl ring of the neighboring enanti-omer also help to stabilize the packing in each case, although the crystals are not isostructural.

Chemical context

The title compounds 1 and 2 are unique structures containing a tri­chloro­methyl substituent at the 2-position of the thia­zolidinone ring. Their synthesis was first reported as two of only three known 2-alkyl thia­zolidin-4-one compounds (Tierney, 1989 ▸; Issac et al., 1996 ▸). Substituted thia­zolidin-4-one compounds are synthesized by reacting an in situ generated imine (Schiff base) with thio­glycolic acid and with a mechanism to remove the water byproduct (Surrey, 1947 ▸; Erlenmeyer & Oberlin, 1947 ▸). Therefore, when chloral is reacted with aryl­amines, the corresponding imine is formed, which, upon reacting with thio­glycolic acid, produces the desired 2-tri­chloro­methyl-3-aryl-thia­zolidin-4-one (Issac et al., 1996 ▸). It is inter­esting to note, however, that the reaction of chloral with some alkyl amines results in an N-alkyl­formamide product when the initially formed aminol loses chloro­form instead of water (Mascavage et al., 2010 ▸). The loss of chloro­form appears to be more facile in electron-rich N-alkyl­amines that can stabilize the transition state and lower the energy of activation of the elimination step better than the less electron-rich N-aryl­amines. On the other hand, imine formation is favored with aryl­amines because of the lower pK of the proton on the nitro­gen in the aminol, which facilitates the removal of water to give an imine. As part of our ongoing studies in this area, we now describe the crystal structures of 1 and 2.

Structural commentary

Compounds 1 and 2 are structurally related with one atom substitution difference in the para position of the benzene ring; a hydrogen atom is substituted for a chlorine atom (Figs. 1 ▸ and 2 ▸). Both contain a stereogenic centre at C1, which is arbitrarily assigned as having an R configuration in the asymmetric units of the centrosymmetric unit cells. In both structures, the thia­zolidinone ring adopts an envelope conformation with the S atom as the flap. The sulfur atom is displaced from the thia­zolidinone ring plane by 0.35 (2) Å in both structures. The dihedral angles between the thia­zolidinone and phenyl rings are 48.72 (11) in 1 and 48.42 (9)° in 2. The C1—N1 and C1—S1 bond lengths are 1.445 (2) Å and 1.816 (2) Å, respectively, for structure 1 and 1.4471 (18) Å and 1.8181 (16) Å, respectively, for structure 2. The N—C—S bond angle is found to be 106.52 (12)° in structure 1 and 106.23 (10)° in structure 2. Overall, the molecular structures of both are almost exactly superimposable (Fig. 3 ▸). Bond length and angle values in the thia­zolidinone ring in both structures appear to be typical and match currently available data (Yennawar et al., 2015 ▸).

Figure 1

The mol­ecular structure of compound 1 with displacement ellipsoids drawn at the 50% probability level.

Figure 2

The mol­ecular structure of compound 2 with displacement ellipsoids drawn at the 50% probability level.

Figure 3

Superposition image for structures 1 and 2 showing similarity of conformation.

Supra­molecular features

Both extended structures exhibit C—H⋯O ‘head-to-tail’ inter­molecular inter­actions between the chiral carbon atom C1 and the thia­zolidinone oxygen atom (Tables 1 ▸ and 2 ▸; Figs. 4 ▸ and 5 ▸) that result in infinite monochiral chains propagating along the shortest unit-cell dimension, namely a in 1 and b in 2; in both cases adjacent mol­ecules are related only by translational symmetry. The short H⋯O distances of 2.30 Å suggest that these inter­actions are relatively strong. Weak C—H⋯π inter­actions between the tetra­hedral, non-chiral carbon atom (C3) of the thia­zolidinone ring and the phenyl ring of the symmetry-related enanti­omer are also observed in both structures (Tables 1 ▸ and 2 ▸). Despite the similar mol­ecular conformations and inter­molecular inter­actions, the crystals are not isostructural (1 is triclinic and 2 is monoclinic).

Table 1

Hydrogen-bond geometry (Å, °) for 1

Cg2 is the centroid of the C5–C10 ring

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1i	0.98	2.30	3.251 (2)	164
C3—H3A⋯Cg2ii	0.97	2.79	3.748 (2)	170

Symmetry codes: (i) ; (ii) .

Table 2

Hydrogen-bond geometry (Å, °) for 2

Cg2 is the centroid of the C5–C10 ring

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O1i	0.98	2.30	3.2643 (19)	168
C3—H3A⋯Cg2ii	0.97	2.85	3.797 (2)	166

Symmetry codes: (i) ; (ii) .

Figure 4

Crystal packing diagram for 1 with red dotted lines for C—H⋯O contacts.

Figure 5

Crystal packing diagram for 2 with red dotted lines for C—H⋯O contacts.

Database survey

To date, there have been no reported X-ray structures of substituted 2-tri­chloro­methyl-3-phenyl-1,3-thia­zolidin-4-ones or the unsubstituted parent compound. However, there are a number of studies for structures containing aromatic moieties at the 2- and 3-positions of the thia­zolidin-4-one ring (Kumar et al., 2016 ▸; Yennawar et al., 2014 ▸). In addition, there is a structural and conformational study of 3-cyclo­hexyl-2-phenyl-1,3-thia­zolidin-4-one (Cannon et al., 2013 ▸).

Synthesis and crystallization

The two compounds were synthesized using previously reported procedures (Tierney, 1989 ▸; Issac et al., 1996 ▸).

2-Tri­chloro­methyl-3-phenyl-1,3-thia­zolidin-4-one (1): Yield 43%; m.p. 447–448 K; IR: 1687 cm−1; 1H NMR: δ 7.1–7.5 (m, 5H, aromatics), 5.72 (s, J = 1.6 Hz, 1H), 3.77–3.96 (dd, J = 1.6, 14.1 Hz, 2H); 13C NMR: δ 171.65 (C=O), 138.45 (N—Ar), 129.17, 127.98, 126.98, 103.18 (CC13), 77.69 (C2), 33.08 (C5). Analysis calculated for C10H8NOSC13: C, 40.40; H, 2.72; N, 4.72; Cl, 35.86. Found: C, 40.60, H, 2.74; N, 4.60; Cl, 35.44.

2-Tri­chloro­methyl-3-(4-chloro­phen­yl)-1,3-thia­zolidin-4-one (2): Yield 20%; mp 456–458 K; IR: 1685 cm−1; 1H NMR: δ 7.11–7.50 (m, 4H, aromatics), 6.04 (s, J = 1.2 Hz, 1H), 3.80–3.92 (dd, J = 1.2, 15.9 Hz, 2H); 13C NMR: δ 171.61 (C=O), 136.96 (N—Ar), 133.78 (C—CI), 129.46, 127.92, 103.06 (CCI3), 77.51 (C2), 32.65 (C5). Analysis calculated for C10H7NOSC14: C, 36.47; H, 2.13; N, 4.25. Found: C, 36.65; H, 2.12; N, 4.04.

Compound 1 was crystallized by vapor diffusion where the sample was dissolved in acetone and placed in a chamber containing hexa­nes. Compound 2 was crystallized by the same method using methyl­ene chloride as the solvent and a chamber containing hexa­nes.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. The hydrogen atoms were placed in calculated positions with C—H = 0.93–0.98 Å and refined using a riding model with fixed isotropic displacement parameters: U iso(H) = 1.5U eq(C) for the methyl group and U iso(H) = 1.2U eq(C) for the remaining H atoms.

Table 3

Experimental details

	1	2
Crystal data
Chemical formula	C10H8Cl3NOS	C10H7Cl4NOS
M r	296.58	331.03
Crystal system, space group	Triclinic, P	Monoclinic, P21/n
Temperature (K)	298	298
a, b, c (Å)	6.1968 (13), 9.578 (2), 10.854 (2)	10.907 (2), 6.1686 (12), 19.885 (4)
α, β, γ (°)	103.135 (4), 91.319 (3), 99.239 (3)	90, 96.02 (3), 90
V (Å3)	618.0 (2)	1330.5 (5)
Z	2	4
Radiation type	Mo Kα	Mo Kα
μ (mm−1)	0.89	1.03
Crystal size (mm)	0.3 × 0.05 × 0.03	0.25 × 0.13 × 0.1
Data collection
Diffractometer	Bruker SMART CCD area detector	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001 ▸)	Multi-scan (SADABS; BRUKER, 2001 ▸)
T min, T max	0.769, 0.9	0.868, 0.9
No. of measured, independent and observed [I > 2σ(I)] reflections	5921, 2977, 2634	12273, 3302, 2883
R int	0.016	0.018
(sin θ/λ)max (Å−1)	0.667	0.668
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.038, 0.118, 1.01	0.036, 0.107, 1.00
No. of reflections	2977	3302
No. of parameters	145	154
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.53, −0.47	0.47, −0.25

Computer programs: SMART and SAINT (Bruker, 2001 ▸), olex2.solve (Bourhis et al., 2015 ▸), SHELXS and SHELXL (Sheldrick, 2008 ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

Crystal structure: contains datablock(s) I, 2, 1. DOI: 10.1107/S2056989018013257/hb7769sup1.cif

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018013257/hb77691sup2.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989018013257/hb77692sup3.cml

CCDC references: 1868299, 1868298

Additional supporting information: crystallographic information; 3D view; checkCIF report

C10H8Cl3NOS	Z = 2
Mr = 296.58	F(000) = 300
Triclinic, P1	Dx = 1.594 Mg m−3
a = 6.1968 (13) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.578 (2) Å	Cell parameters from 3362 reflections
c = 10.854 (2) Å	θ = 2.2–28.3°
α = 103.135 (4)°	µ = 0.89 mm−1
β = 91.319 (3)°	T = 298 K
γ = 99.239 (3)°	Needle, colorless
V = 618.0 (2) Å3	0.3 × 0.05 × 0.03 mm

Bruker SMART CCD area detector diffractometer	2977 independent reflections
Radiation source: fine-focus sealed tube	2634 reflections with I > 2σ(I)
Parallel,graphite monochromator	Rint = 0.016
phi and ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −8→8
Tmin = 0.769, Tmax = 0.9	k = −12→12
5921 measured reflections	l = −14→13

Refinement on F2	Primary atom site location: iterative
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0658P)2 + 0.2774P] where P = (Fo2 + 2Fc2)/3
2977 reflections	(Δ/σ)max < 0.001
145 parameters	Δρmax = 0.53 e Å−3
0 restraints	Δρmin = −0.47 e Å−3

Experimental. The data collection nominally covered a full sphere of reciprocal space by a combination of 4 sets of ω scans each set at different φ and/or 2θ angles and each scan (20 s exposure) covering -0.300° degrees in ω. The crystal to detector distance was 5.82 cm.(SADABS; Bruker, 2001) was used for absorption correction. R(int) was 0.0816 before and 0.0197 after correction. The Ratio of minimum to maximum transmission is 0.7686. The λ/2 correction factor is 0.0015.

Geometry. 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.

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 > 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.

	x	y	z	Uiso*/Ueq
Cl1	0.06476 (9)	0.12635 (6)	0.75819 (5)	0.05390 (17)
Cl3	0.50432 (10)	0.09734 (7)	0.68826 (7)	0.0654 (2)
Cl2	0.42957 (13)	0.34274 (7)	0.87998 (6)	0.0692 (2)
S1	0.22368 (9)	0.18205 (6)	0.47724 (5)	0.04902 (16)
O1	−0.1907 (2)	0.43408 (17)	0.58501 (16)	0.0491 (4)
N1	0.1467 (2)	0.40320 (17)	0.65276 (15)	0.0367 (3)
C3	−0.0461 (3)	0.2263 (2)	0.4763 (2)	0.0469 (5)
H3A	−0.0878	0.2397	0.3937	0.056*
H3B	−0.1511	0.1483	0.4950	0.056*
C2	−0.0430 (3)	0.3648 (2)	0.57597 (18)	0.0377 (4)
C1	0.3059 (3)	0.3068 (2)	0.62984 (18)	0.0369 (4)
H1	0.4498	0.3643	0.6244	0.044*
C5	0.1956 (3)	0.5430 (2)	0.73953 (18)	0.0399 (4)
C10	0.0444 (4)	0.5876 (3)	0.8246 (2)	0.0599 (6)
H10	−0.0856	0.5257	0.8292	0.072*
C9	0.0893 (6)	0.7262 (4)	0.9031 (3)	0.0798 (9)
H9	−0.0133	0.7584	0.9592	0.096*
C8	0.2836 (6)	0.8162 (3)	0.8989 (3)	0.0743 (8)
H8	0.3127	0.9086	0.9526	0.089*
C7	0.4339 (5)	0.7705 (3)	0.8162 (3)	0.0609 (6)
H7	0.5660	0.8316	0.8145	0.073*
C6	0.3914 (4)	0.6338 (2)	0.7347 (2)	0.0467 (4)
H6	0.4932	0.6033	0.6774	0.056*
C4	0.3226 (3)	0.2231 (2)	0.7350 (2)	0.0420 (4)

	U11	U22	U33	U12	U13	U23
Cl1	0.0461 (3)	0.0603 (3)	0.0560 (3)	−0.0005 (2)	0.0048 (2)	0.0215 (2)
Cl3	0.0508 (3)	0.0625 (4)	0.0953 (5)	0.0280 (3)	0.0029 (3)	0.0312 (3)
Cl2	0.0806 (4)	0.0620 (4)	0.0589 (4)	0.0015 (3)	−0.0314 (3)	0.0126 (3)
S1	0.0514 (3)	0.0515 (3)	0.0447 (3)	0.0196 (2)	0.0057 (2)	0.0045 (2)
O1	0.0336 (7)	0.0512 (8)	0.0644 (9)	0.0133 (6)	−0.0008 (6)	0.0138 (7)
N1	0.0307 (7)	0.0353 (8)	0.0443 (8)	0.0086 (6)	0.0001 (6)	0.0076 (6)
C3	0.0442 (10)	0.0450 (11)	0.0498 (11)	0.0091 (8)	−0.0080 (8)	0.0072 (9)
C2	0.0317 (8)	0.0383 (9)	0.0448 (10)	0.0058 (7)	0.0017 (7)	0.0133 (7)
C1	0.0302 (8)	0.0369 (9)	0.0450 (9)	0.0079 (7)	0.0021 (7)	0.0108 (7)
C5	0.0437 (9)	0.0370 (9)	0.0399 (9)	0.0102 (8)	−0.0011 (7)	0.0091 (7)
C10	0.0561 (13)	0.0633 (14)	0.0547 (13)	0.0111 (11)	0.0109 (10)	0.0010 (11)
C9	0.090 (2)	0.080 (2)	0.0598 (16)	0.0294 (17)	0.0101 (15)	−0.0135 (14)
C8	0.098 (2)	0.0517 (14)	0.0621 (16)	0.0133 (15)	−0.0183 (15)	−0.0089 (12)
C7	0.0715 (15)	0.0427 (12)	0.0623 (14)	−0.0014 (11)	−0.0179 (12)	0.0095 (10)
C6	0.0486 (11)	0.0407 (10)	0.0512 (11)	0.0051 (8)	−0.0028 (9)	0.0136 (9)
C4	0.0339 (8)	0.0432 (10)	0.0502 (11)	0.0063 (7)	−0.0044 (7)	0.0143 (8)

Cl1—C4	1.767 (2)	C1—C4	1.547 (3)
Cl3—C4	1.778 (2)	C5—C10	1.379 (3)
Cl2—C4	1.766 (2)	C5—C6	1.384 (3)
S1—C3	1.790 (2)	C10—H10	0.9300
S1—C1	1.816 (2)	C10—C9	1.386 (4)
O1—C2	1.208 (2)	C9—H9	0.9300
N1—C2	1.374 (2)	C9—C8	1.372 (5)
N1—C1	1.445 (2)	C8—H8	0.9300
N1—C5	1.434 (2)	C8—C7	1.362 (4)
C3—H3A	0.9700	C7—H7	0.9300
C3—H3B	0.9700	C7—C6	1.386 (3)
C3—C2	1.506 (3)	C6—H6	0.9300
C1—H1	0.9800
C3—S1—C1	92.98 (9)	C5—C10—H10	120.5
C2—N1—C1	117.34 (16)	C5—C10—C9	119.0 (3)
C2—N1—C5	120.50 (15)	C9—C10—H10	120.5
C5—N1—C1	121.60 (15)	C10—C9—H9	119.7
S1—C3—H3A	110.2	C8—C9—C10	120.6 (3)
S1—C3—H3B	110.2	C8—C9—H9	119.7
H3A—C3—H3B	108.5	C9—C8—H8	119.9
C2—C3—S1	107.58 (14)	C7—C8—C9	120.1 (2)
C2—C3—H3A	110.2	C7—C8—H8	119.9
C2—C3—H3B	110.2	C8—C7—H7	119.8
O1—C2—N1	124.51 (18)	C8—C7—C6	120.5 (3)
O1—C2—C3	123.05 (18)	C6—C7—H7	119.8
N1—C2—C3	112.43 (16)	C5—C6—C7	119.2 (2)
S1—C1—H1	108.8	C5—C6—H6	120.4
N1—C1—S1	106.52 (12)	C7—C6—H6	120.4
N1—C1—H1	108.8	Cl1—C4—Cl3	108.87 (11)
N1—C1—C4	112.89 (16)	Cl2—C4—Cl1	108.94 (12)
C4—C1—S1	110.96 (14)	Cl2—C4—Cl3	108.22 (10)
C4—C1—H1	108.8	C1—C4—Cl1	111.51 (13)
C10—C5—N1	119.72 (19)	C1—C4—Cl3	108.20 (14)
C10—C5—C6	120.6 (2)	C1—C4—Cl2	111.02 (14)
C6—C5—N1	119.70 (18)
S1—C3—C2—O1	168.28 (16)	C1—S1—C3—C2	15.36 (16)
S1—C3—C2—N1	−10.8 (2)	C1—N1—C2—O1	179.29 (18)
S1—C1—C4—Cl1	−64.40 (16)	C1—N1—C2—C3	−1.7 (2)
S1—C1—C4—Cl3	55.31 (15)	C1—N1—C5—C10	−135.2 (2)
S1—C1—C4—Cl2	173.93 (9)	C1—N1—C5—C6	46.7 (3)
N1—C1—C4—Cl1	55.1 (2)	C5—N1—C2—O1	−9.2 (3)
N1—C1—C4—Cl3	174.80 (12)	C5—N1—C2—C3	169.87 (17)
N1—C1—C4—Cl2	−66.58 (18)	C5—N1—C1—S1	−158.41 (14)
N1—C5—C10—C9	−176.5 (2)	C5—N1—C1—C4	79.6 (2)
N1—C5—C6—C7	177.9 (2)	C5—C10—C9—C8	−1.8 (5)
C3—S1—C1—N1	−16.08 (14)	C10—C5—C6—C7	−0.2 (3)
C3—S1—C1—C4	107.16 (14)	C10—C9—C8—C7	0.7 (5)
C2—N1—C1—S1	13.0 (2)	C9—C8—C7—C6	0.7 (4)
C2—N1—C1—C4	−108.99 (19)	C8—C7—C6—C5	−1.0 (4)
C2—N1—C5—C10	53.6 (3)	C6—C5—C10—C9	1.5 (4)
C2—N1—C5—C6	−124.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1i	0.98	2.30	3.251 (2)	164
C3—H3A···Cg2ii	0.97	2.79	3.748 (2)	170

C10H7Cl4NOS	F(000) = 664
Mr = 331.03	Dx = 1.653 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.907 (2) Å	Cell parameters from 5450 reflections
b = 6.1686 (12) Å	θ = 2.2–28.3°
c = 19.885 (4) Å	µ = 1.03 mm−1
β = 96.02 (3)°	T = 298 K
V = 1330.5 (5) Å3	Block, colorless
Z = 4	0.25 × 0.13 × 0.1 mm

Bruker SMART CCD area detector diffractometer	3302 independent reflections
Radiation source: fine-focus sealed tube	2883 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; BRUKER, 2001)	h = −12→14
Tmin = 0.868, Tmax = 0.9	k = −8→8
12273 measured reflections	l = −26→23

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.069P)2 + 0.2954P] where P = (Fo2 + 2Fc2)/3
3302 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Experimental. The data collection nominally covered a full sphere of reciprocal space by a combination of 4 sets of ω scans each set at different φ and/or 2θ angles and each scan (10 s exposure) covering -0.300° degrees in ω. The crystal to detector distance was 5.82 cm.SADABS V2.05 (BRUKER, 2001) was used for absorption correction. R(int) was 0.0443 before and 0.0167 after correction. The Ratio of minimum to maximum transmission is 0.8678. The λ/2 correction factor is 0.0015.

Geometry. 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.

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 > 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.

	x	y	z	Uiso*/Ueq
S1	0.57569 (4)	0.69974 (7)	0.15220 (2)	0.04596 (13)
Cl1	0.87252 (5)	0.86052 (9)	0.16992 (3)	0.05996 (16)
Cl3	0.81425 (5)	0.41241 (9)	0.19023 (3)	0.06369 (16)
Cl2	0.92398 (5)	0.53959 (10)	0.07182 (3)	0.06652 (18)
Cl4	0.85656 (7)	0.75038 (16)	−0.22386 (3)	0.0903 (2)
N1	0.67812 (13)	0.8295 (2)	0.04570 (6)	0.0375 (3)
C5	0.72089 (15)	0.8111 (3)	−0.01992 (8)	0.0379 (3)
C4	0.81846 (16)	0.6202 (3)	0.12933 (8)	0.0407 (3)
C1	0.68725 (15)	0.6485 (2)	0.09226 (7)	0.0356 (3)
H1	0.6640	0.5154	0.0672	0.043*
C2	0.61543 (16)	1.0100 (3)	0.06349 (8)	0.0412 (3)
O1	0.60428 (13)	1.17453 (19)	0.03021 (7)	0.0531 (3)
C8	0.80220 (18)	0.7763 (4)	−0.14533 (9)	0.0555 (5)
C6	0.68763 (17)	0.6339 (3)	−0.05979 (8)	0.0446 (4)
H6	0.6373	0.5273	−0.0443	0.053*
C3	0.56058 (19)	0.9806 (3)	0.12923 (10)	0.0507 (4)
H3A	0.4743	1.0222	0.1240	0.061*
H3B	0.6037	1.0704	0.1641	0.061*
C10	0.79363 (19)	0.9722 (3)	−0.04301 (10)	0.0555 (5)
H10	0.8158	1.0918	−0.0160	0.067*
C9	0.8334 (2)	0.9550 (4)	−0.10653 (11)	0.0657 (6)
H9	0.8811	1.0642	−0.1228	0.079*
C7	0.72899 (18)	0.6145 (3)	−0.12273 (9)	0.0518 (4)
H7	0.7079	0.4941	−0.1496	0.062*

	U11	U22	U33	U12	U13	U23
S1	0.0473 (3)	0.0496 (2)	0.0431 (2)	−0.00669 (17)	0.01474 (18)	−0.00091 (17)
Cl1	0.0493 (3)	0.0606 (3)	0.0695 (3)	−0.0120 (2)	0.0035 (2)	−0.0186 (2)
Cl3	0.0798 (4)	0.0595 (3)	0.0508 (3)	0.0090 (2)	0.0024 (2)	0.0189 (2)
Cl2	0.0631 (3)	0.0876 (4)	0.0511 (3)	0.0291 (3)	0.0168 (2)	−0.0008 (2)
Cl4	0.0881 (5)	0.1389 (6)	0.0497 (3)	0.0127 (4)	0.0347 (3)	0.0164 (3)
N1	0.0477 (7)	0.0317 (6)	0.0336 (6)	−0.0006 (5)	0.0070 (5)	0.0000 (5)
C5	0.0417 (8)	0.0386 (7)	0.0338 (7)	−0.0018 (6)	0.0058 (6)	0.0037 (6)
C4	0.0480 (9)	0.0404 (8)	0.0346 (8)	0.0026 (6)	0.0082 (6)	0.0001 (6)
C1	0.0449 (8)	0.0315 (6)	0.0307 (7)	−0.0035 (6)	0.0063 (6)	−0.0016 (5)
C2	0.0457 (8)	0.0349 (7)	0.0419 (8)	−0.0017 (6)	−0.0005 (6)	−0.0047 (6)
O1	0.0675 (9)	0.0331 (6)	0.0581 (8)	0.0029 (5)	0.0030 (6)	0.0019 (5)
C8	0.0502 (10)	0.0796 (13)	0.0390 (9)	0.0082 (9)	0.0155 (8)	0.0131 (9)
C6	0.0533 (10)	0.0455 (8)	0.0360 (8)	−0.0065 (7)	0.0098 (7)	0.0006 (6)
C3	0.0551 (10)	0.0501 (9)	0.0477 (10)	0.0101 (8)	0.0087 (8)	−0.0055 (8)
C10	0.0612 (11)	0.0503 (10)	0.0567 (11)	−0.0161 (8)	0.0139 (9)	0.0015 (8)
C9	0.0635 (13)	0.0725 (13)	0.0650 (13)	−0.0143 (10)	0.0256 (10)	0.0165 (11)
C7	0.0578 (11)	0.0627 (11)	0.0359 (8)	−0.0008 (9)	0.0090 (7)	−0.0040 (8)

S1—C1	1.8181 (16)	C2—O1	1.211 (2)
S1—C3	1.795 (2)	C2—C3	1.505 (3)
Cl1—C4	1.7595 (17)	C8—C9	1.368 (3)
Cl3—C4	1.7674 (17)	C8—C7	1.382 (3)
Cl2—C4	1.7766 (17)	C6—H6	0.9300
Cl4—C8	1.7349 (19)	C6—C7	1.379 (2)
N1—C5	1.436 (2)	C3—H3A	0.9700
N1—C1	1.4471 (18)	C3—H3B	0.9700
N1—C2	1.372 (2)	C10—H10	0.9300
C5—C6	1.377 (2)	C10—C9	1.382 (3)
C5—C10	1.380 (2)	C9—H9	0.9300
C4—C1	1.549 (2)	C7—H7	0.9300
C1—H1	0.9800
C3—S1—C1	92.91 (8)	C9—C8—Cl4	119.59 (16)
C5—N1—C1	120.90 (12)	C9—C8—C7	121.07 (17)
C2—N1—C5	121.10 (13)	C7—C8—Cl4	119.33 (18)
C2—N1—C1	117.64 (13)	C5—C6—H6	120.0
C6—C5—N1	119.66 (14)	C5—C6—C7	119.99 (17)
C6—C5—C10	120.42 (16)	C7—C6—H6	120.0
C10—C5—N1	119.91 (15)	S1—C3—H3A	110.2
Cl1—C4—Cl3	109.17 (9)	S1—C3—H3B	110.2
Cl1—C4—Cl2	108.82 (10)	C2—C3—S1	107.67 (12)
Cl3—C4—Cl2	107.64 (9)	C2—C3—H3A	110.2
C1—C4—Cl1	111.83 (11)	C2—C3—H3B	110.2
C1—C4—Cl3	108.57 (11)	H3A—C3—H3B	108.5
C1—C4—Cl2	110.71 (11)	C5—C10—H10	120.2
S1—C1—H1	108.9	C5—C10—C9	119.67 (19)
N1—C1—S1	106.23 (10)	C9—C10—H10	120.2
N1—C1—C4	112.92 (13)	C8—C9—C10	119.64 (18)
N1—C1—H1	108.9	C8—C9—H9	120.2
C4—C1—S1	110.85 (10)	C10—C9—H9	120.2
C4—C1—H1	108.9	C8—C7—H7	120.4
N1—C2—C3	112.34 (14)	C6—C7—C8	119.18 (19)
O1—C2—N1	124.29 (16)	C6—C7—H7	120.4
O1—C2—C3	123.36 (16)
Cl1—C4—C1—S1	−65.17 (12)	C1—S1—C3—C2	15.17 (13)
Cl1—C4—C1—N1	53.89 (15)	C1—N1—C5—C6	47.7 (2)
Cl3—C4—C1—S1	55.34 (12)	C1—N1—C5—C10	−133.18 (17)
Cl3—C4—C1—N1	174.40 (10)	C1—N1—C2—O1	177.64 (15)
Cl2—C4—C1—S1	173.30 (8)	C1—N1—C2—C3	−2.8 (2)
Cl2—C4—C1—N1	−67.64 (14)	C2—N1—C5—C6	−125.20 (17)
Cl4—C8—C9—C10	−177.79 (18)	C2—N1—C5—C10	54.0 (2)
Cl4—C8—C7—C6	178.93 (15)	C2—N1—C1—S1	13.99 (17)
N1—C5—C6—C7	−179.61 (16)	C2—N1—C1—C4	−107.72 (16)
N1—C5—C10—C9	−179.26 (18)	O1—C2—C3—S1	169.53 (14)
N1—C2—C3—S1	−10.00 (18)	C6—C5—C10—C9	−0.1 (3)
C5—N1—C1—S1	−159.12 (12)	C3—S1—C1—N1	−16.38 (12)
C5—N1—C1—C4	79.18 (17)	C3—S1—C1—C4	106.63 (12)
C5—N1—C2—O1	−9.3 (3)	C10—C5—C6—C7	1.2 (3)
C5—N1—C2—C3	170.25 (14)	C9—C8—C7—C6	−0.4 (3)
C5—C6—C7—C8	−1.0 (3)	C7—C8—C9—C10	1.5 (3)
C5—C10—C9—C8	−1.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1i	0.98	2.30	3.2643 (19)	168
C3—H3A···Cg2ii	0.97	2.85	3.797 (2)	166