Crystal structures of three (trichloromethyl)(carbamoyl)disulfanes.

The present paper reports crystallographic studies on three related compounds that were of inter-est as precursors for synthetic and mechanistic work in organosulfur chemistry, as well as to model nitro-gen-protecting groups: (N-methyl-carbamo-yl)(tri-chloro-meth-yl)disulfane, C3H4Cl3NOS2, (1), (N-benzyl-carbamo-yl)(tri-chloro-meth-yl)disulfane, C9H8Cl3NOS2, (2), and (N-methyl-N-phenyl-carbamo-yl)(tri-chloro-meth-yl)disulfane, C9H8Cl3NOS2, (3). Their mol-ecular structures, with similar bond lengths and angles for the CCl3SS(C=O)N moieties, are confirmed. Compounds (1) and (3) both crystallized with two independent mol-ecules in the asymmetric unit. Classical hydrogen bonding, as well as chlorine-dense regions, are evident in the crystal packing for (1) and (2). In the crystal of (1), mol-ecules are linked via N-H⋯O hydrogen bonds forming chains along [110], which are linked by short Cl⋯Cl and S⋯O contacts forming sheets parallel to (001). In the crystal of (2), mol-ecules are linked via N-H⋯O hydrogen bonds forming chains along [001], which in turn are linked by pairs of short O⋯Cl contacts forming ribbons along the c-axis direction. In the crystal of (3), there are no classical hydrogen bonds present and the chlorine-dense regions observed in (1) and (2) are lacking.

Chemical context

Carbamoyl disulfanes were first reported by Harris (1960 ▸). This family of compounds has served as useful model compounds for synthetic and mechanistic work in organosulfur chemistry and nitro­gen-protecting-group development (Barany & Merrifield, 1977 ▸; Barany et al., 1983 ▸; Schroll & Barany, 1986 ▸; Barany et al., 2005 ▸; Schrader et al., 2011 ▸). The tri­chloro­methyl derivatives reported here, (tri­chloro­meth­yl)(N-methyl­carbamo­yl)disulfane, (1) (Fig. 1 ▸), (tri­chloro­meth­yl)(N-benz­yl­carbamo­yl)disulfane, (2) (Fig. 2 ▸), and (tri­chloro­meth­yl)(N-methyl-N-phenyl­carbamo­yl)disulfane, (3) (Fig. 3 ▸), are partic­ularly stable. All three compounds have been stored under ambient conditions for periods in the range of two to four decades, with no evidence of decomposition based on unchanged 1H NMR spectra and melting points.

Figure 1

The mol­ecular structure of compound (1) showing the atom-labelling scheme, with two mol­ecules (Z′ = 2) per asymmetric unit. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2

The mol­ecular structure of compound (2) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 3

The mol­ecular structure of compound (3) showing the atom-labelling scheme, with two mol­ecules (Z′ = 2) per asymmetric unit. Displacement ellipsoids are drawn at the 50% probability level.

Structural commentary

The three (tri­chloro­meth­yl)(carbamo­yl)disulfanes differ in the substituents on the carbamoyl nitro­gen, but the bond lengths and angles of the common CCl3SS(C=O)N moieties of each are markedly similar for the two mol­ecules in the asymmetric units of (1) and (3), as well as for the single conformation of (2) (Tables 1 ▸ and 2 ▸). The corresponding structural features of (3) are also similar to the bond lengths and torsion angles of other carbamoyl disulfanes that include an SS(C=O)N(Me)Ph chain, including, for example, bis­(N-methyl-N-phenyl­carbamo­yl)disulfane (ZAQWUL, formula [Ph(Me)N(C=O)S]2) (Schroll et al., 2012 ▸) and (N-methyl-N-phenyl­carbamo­yl)(N-methyl-N-phenyl­amino)­disulfane [formula Ph(Me)N(C=O)SSN(Me)Ph] (Henley et al., 2015 ▸).

Table 1

Selected bond lengths (Å) and angles (°) for CCl3SS(C=O)N moieties

	(1a)	(1b)	(2)	(3a)	(3b)
S1—C1	1.8242 (18)	1.8261 (18)	1.826 (3)	1.824 (2)	1.822 (2)
S1—S2	2.0100 (7)	2.0126 (6)	2.0099 (11)	2.0202 (7)	2.0160 (7)
S2—C2	1.8367 (17)	1.8426 (17)	1.842 (3)	1.856 (2)	1.842 (2)
O1—C2	1.214 (2)	1.212 (2)	1.213 (4)	1.208 (2)	1.211 (2)
N1—C2	1.322 (2)	1.324 (2)	1.319 (4)	1.345 (3)	1.346 (3)
N1—C3	1.458 (2)	1.460 (2)	1.475 (4)	1.467 (3)	1.460 (3)
N1—C4	–	–	–	1.440 (3)	1.447 (3)
C1—S1—S2	103.09 (6)	103.10 (6)	103.68 (11)	102.38 (7)	104.40 (7)
C2—S2—S1	102.20 (6)	101.43 (6)	101.40 (10)	99.96 (7)	101.59 (7)
C2—N1—C3	121.71 (15)	120.35 (14)	121.8 (3)	118.95 (18)	119.49 (18)
O1—C2—N1	126.31 (16)	126.23 (16)	126.4 (3)	125.9 (2)	126.4 (2)
O1—C2—S2	123.02 (13)	122.17 (13)	122.4 (2)	122.09 (16)	122.96 (16)
N1—C2—S2	110.67 (12)	111.58 (12)	111.2 (2)	111.99 (15)	110.65 (14)

Table 2

Comparison of selected torsion angles (°)

	(1a)	(1b)	(2)	(3a)	(3b)
C1—S1—S2—C2	93.63 (8)	93.49 (8)	96.54 (14)	92.91 (10)	−95.23 (10)
C3—N1—C2—O1	3.3 (3)	1.6 (3)	−1.3 (5)	0.3 (3)	−0.8 (3)
C3—N1—C2—S2	−176.22 (14)	−176.67 (12)	−178.2 (3)	−179.98 (15)	179.73 (16)
S1—S2—C2—O1	2.87 (16)	−0.66 (15)	−2.5 (3)	10.32 (19)	6.32 (19)
S1—S2—C2—N1	−177.64 (11)	177.64 (11)	174.6 (2)	−169.40 (14)	−174.23 (13)
C2—N1—C4—C9	–	–	–	−72.9 (3)	93.8 (2)
C2—N1—C4—C5	–	–	–	109.7 (2)	−86.4 (3)
C3—N1—C4—C9	–	–	–	104.1 (2)	−78.0 (3)
C3—N1—C4—C5	–	–	–	−73.3 (3)	101.8 (2)

Supra­molecular features

The three compounds arrange in three distinct packing configurations. The two nearly superimposable mol­ecular structures of (1) are alternately hydrogen-bonded (NH⋯O=C) in chains along [110] (Table 3 ▸). Successive mol­ecules of each of two chains are linked by 3.162 (1) Å S1A⋯O1B contacts, 0.157 Å less than their van der Waals radii sum (Fig. 4 ▸). Additional packing features result in a Z = 16 unit cell. A chlorine from each of four mol­ecules – in separate hydrogen-bonded chains – form a short-contact skew quadrilateral with inter­molecular contact distances of 3.4304 (8) Å (−0.070 Å less than their van der Waals radii sum) and 3.3463 (8) Å (−0.154 Å less than their van der Waals radii sum), Cl3B⋯Cl1A⋯Cl3B and Cl1A⋯Cl3B⋯Cl1A angles 73.40 (2) and 82.01 (2)°, and Cl3B⋯Cl1A⋯Cl3B⋯Cl1A and Cl1A⋯Cl3B⋯Cl1A⋯Cl3B torsion angles −50.45 (2) and 48.78 (2)°. These result in chlorine-dense regions of the crystal structure (Fig. 5 ▸), and the formation of sheets parallel to (001). Halogen bonding involving tri­chloro­methyl groups in supra­molecular structures was described by Rybarczyk-Pirek et al. (2013 ▸).

Table 3

Hydrogen-bond geometry (Å, °) for (1)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1AA⋯O1B i	0.86 (1)	1.94 (1)	2.7825 (18)	164 (2)
N1B—H1BA⋯O1A ii	0.86 (1)	1.97 (1)	2.8231 (18)	175 (2)

Symmetry codes: (i) ; (ii) .

Figure 4

Hydrogen-bonded chains of (1) are linked by S1A⋯O1B contacts. Only H atoms involved in N—H⋯O=C bonds are shown.

Figure 5

A chlorine from each of four mol­ecules of (1), in separate chains, form a short-contact skew quadrilateral. Only H atoms involved in N—H⋯O=C bonds are shown.

The unit cell of (2) consists of pairs of hydrogen-bonded dimers about an inversion center. The mol­ecules in each dimer are linked by NH⋯O=C hydrogen bonds (Table 4 ▸), which extend into hydrogen-bonded mol­ecular chains along [001]. A network of linked chains is formed by O1⋯Cl3 contacts. Two O1⋯Cl3 contacts [3.028 (2) Å, 0.242 Å less than their van der Waals radii sum] form between each pair of mol­ecules in separate hydrogen-bonded chains, and the links extend throughout the chains in alternate mol­ecules. In this way, each hydrogen-bonded chain has extensive links to two other chains. The resulting structure features alternating layers of tri­chloro­methyl and benzyl groups (Fig. 6 ▸).

Table 4

Hydrogen-bond geometry (Å, °) for (2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.87 (1)	2.02 (1)	2.887 (3)	174 (3)

Symmetry code: (i) .

Figure 6

Packing structure of (2). Hydrogen-bonded chains are linked by pairs of O1⋯Cl3 contacts. H atoms are not shown unless they participate in hydrogen bonding.

Compound (3) has no available classical hydrogen bonding and lacks the chlorine-dense regions of (1) and (2). Of the two conformations available for (3), it is noteworthy that the four sulfurs of two adjacent mol­ecules of (3 ) are positioned in a parallelogram [angles 80.65 (2) and 99.35 (2)°, torsion angle 0.00 (2)°] with inter­molecular contact distances of 3.5969 (8) Å, slightly less than the sum of their van der Waals radii; no such configuration is evident for mol­ecules of (3 ). Fig. 7 ▸ shows a schematic view of the inter­molecular inter­actions. A pair of non-classical hydrogen bonds [C9A—H9AA⋯O1B and C9B—H9BA⋯O1A, with H⋯C contact distances 2.55 and 2.54 Å, C⋯O distances of 3.360 (3) and 3.432 (3) Å, and C—H⋯O angles of 143 and 157°] connect (3 ) and (3 ) mol­ecules. Two additional non-classical hydrogen bonds [C5A—H5AA⋯Cl1B and C3B—H3BA⋯Cl3A, with H⋯Cl contact distances 2.82 and 2.81 Å, C⋯Cl distances of 3.732 (2) and 3.649 (2) Å, and C—H⋯Cl angles of 161 and 144°] are shown.

Figure 7

Packing diagram for (3). H atoms are not shown unless they participate in hydrogen bonding. [Symmetry codes: (i) −x + 1, −y, −z; (ii) x, y + 1, z.]

Database survey

Crystal structures for two additional carbamoyl disulfanes have been reported: bis­(indolylcarbamo­yl)disulfane (BOWGAV, formula [C8H6N(C=O)S]2) (Bereman et al., 1983 ▸) and bis­(N,N-di­cyclo­hexyl­carbamo­yl)disulfane (UDALER, [cHex2N(C=O)S]2) (Li et al., 2006 ▸). Their mol­ecular structures are consistent with those of the three compounds reported here. Neither of these comparison structures contains halogen atoms or supra­molecular hydrogen bonds. The crystal structure of 1,7-bis­(tri­chloro­meth­yl)hepta­sulfane contains both short Cl⋯Cl contacts and a parallelogram (four sulfurs) formed from the tri­chloro­methyl-adjacent S–S bonds of two mol­ecules (REHKUK; Steudel et al., 1995 ▸).

Synthesis and crystallization

Compounds (1) (Harris, 1960 ▸; Barany et al., 2005 ▸), (2) (Barany et al., 2005 ▸), and (3) (Barany et al., 1983 ▸; Schroll & Barany, 1986 ▸) were synthesized and crystallized as outlined in Fig. 8 ▸ and described in the referenced publications. The reaction of (4) plus (5), shown in the top pathway of Fig. 8 ▸, is termed the Harris reaction (Harris, 1960 ▸). For the alternative Harris pathway shown in the middle of Fig. 8 ▸, compound (6), a thio­carbamate salt, is typically made by reaction of carbonyl sulfide (COS) with a primary or secondary amine HNR 1 R 2. Therefore B+ is usually the appropriate ammonium counter-ion H2N+ R 1 R 2. Finally, several variations of acyl­ation chemistry are summarized in the bottom pathway of Fig. 8 ▸, as originally worked out by Barany et al. (2005 ▸). When R 3 = H, starting amine HNR 1 R 2 is present in sufficient excess so that a second equivalent of amine can absorb the HCl co-product. When R 1 and/or R 3 = TMS, stoichiometric ratios can be used, since co-product TMS-Cl is neutral. Note that for some reactions, a TMS group attached to N becomes an H after aqueous workup.

Figure 8

Synthetic routes to (tri­chloro­meth­yl)(carbamo­yl)disulfanes, (1), (2) and (3). See text for further details.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 5 ▸. N—H hydrogen atoms were refined positionally, with restrained d(N—H) = 0.85 (1)Å. H atoms attached to C were idealized (C—H: 0.95 Å, C—H2: 0.99 Å, C—H3: 0.98 Å). In all cases, U iso(H) = x × U eq(Host), x = 1.2 except for methyl groups, where x = 1.5.

Table 5

Experimental details

	(1)	(2)	(3)
Crystal data
Chemical formula	C3H4Cl3NOS2	C9H8Cl3NOS2	C9H8Cl3NOS2
M r	240.54	316.63	316.63
Crystal system, space group	Monoclinic, C2/c	Monoclinic, P21/c	Triclinic, P
Temperature (K)	123	173	123
a, b, c (Å)	13.1141 (16), 13.9234 (17), 20.172 (3)	11.4247 (17), 13.548 (2), 8.5675 (12)	8.9231 (12), 10.1724 (13), 15.364 (2)
α, β, γ (°)	90, 98.969 (2), 90	90, 103.176 (2), 90	81.964 (2), 81.806 (2), 68.851 (2)
V (Å3)	3638.3 (8)	1291.2 (3)	1281.5 (3)
Z	16	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm−1)	1.40	1.01	1.02
Crystal size (mm)	0.40 × 0.30 × 0.11	0.30 × 0.15 × 0.10	0.25 × 0.20 × 0.09
Data collection
Diffractometer	Bruker SMART CCD area detector	Bruker SMART CCD area detector	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008 ▸)	Multi-scan SADABS, (Sheldrick, 2008 ▸)	Multi-scan (SADABS; Sheldrick, 2008 ▸)
T min, T max	0.646, 0.746	0.752, 0.906	0.676, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	21324, 4168, 3556	12180, 2284, 2056	15282, 5790, 4557
R int	0.030	0.041	0.034
(sin θ/λ)max (Å−1)	0.650	0.596	0.649
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.025, 0.061, 1.03	0.042, 0.080, 1.00	0.030, 0.073, 0.97
No. of reflections	4168	2284	5790
No. of parameters	189	148	291
No. of restraints	2	1	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.80, −0.63	0.33, −0.27	0.39, −0.27

Computer programs: SMART and SAINT (Bruker, 2007 ▸), SHELXL2014 (Sheldrick, 2015 ▸), SHELXTL (Sheldrick, 2008 ▸), Mercury (Macrae et al., 2008 ▸), PLATON (Spek, 2009 ▸) and ACD/ChemBioDraw (ACD/Labs, 2014 ▸).

Crystal structure: contains datablock(s) 1, 2, 3. DOI: 10.1107/S2056989015015893/bg2565sup1.cif

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015015893/bg25651sup2.cdx

Structure factors: contains datablock(s) 1. DOI: 10.1107/S2056989015015893/bg25651sup8.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015015893/bg25652sup3.cdx

Structure factors: contains datablock(s) 2. DOI: 10.1107/S2056989015015893/bg25652sup9.hkl

Structure factors: contains datablock(s) 3. DOI: 10.1107/S2056989015015893/bg25653sup10.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015015893/bg25653sup4.cdx

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015015893/bg25651sup8.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015015893/bg25652sup9.cml

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015015893/bg25653sup10.cml

CCDC references: 1420526, 1420527, 1420528

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

C3H4Cl3NOS2	Dx = 1.757 Mg m−3
Mr = 240.54	Melting point = 352–353 K
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.1141 (16) Å	Cell parameters from 2920 reflections
b = 13.9234 (17) Å	θ = 2.5–27.5°
c = 20.172 (3) Å	µ = 1.40 mm−1
β = 98.969 (2)°	T = 123 K
V = 3638.3 (8) Å3	Plate, colorless
Z = 16	0.40 × 0.30 × 0.11 mm
F(000) = 1920

Bruker SMART CCD area detector diffractometer	3556 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.030
phi and ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −16→17
Tmin = 0.646, Tmax = 0.746	k = −18→17
21324 measured reflections	l = −26→26
4168 independent reflections

Refinement on F2	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.061	w = 1/[σ2(Fo2) + (0.0241P)2 + 4.8271P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.002
4168 reflections	Δρmax = 0.80 e Å−3
189 parameters	Δρmin = −0.63 e Å−3

Experimental. Compound (1) (Harris, 1960; Barany et al., 2005) was synthesized and crystallized as outlined in the Scheme and described in the referenced publications.

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.

	x	y	z	Uiso*/Ueq
Cl1A	−0.00541 (4)	0.37732 (4)	0.35962 (3)	0.04712 (15)
Cl2A	0.19373 (3)	0.28755 (4)	0.39682 (2)	0.03390 (11)
Cl3A	0.08631 (4)	0.35934 (3)	0.49989 (3)	0.03684 (12)
S1A	−0.00492 (3)	0.19396 (3)	0.41765 (2)	0.02805 (11)
S2A	0.08261 (4)	0.10871 (3)	0.48401 (2)	0.02537 (10)
O1A	−0.04393 (10)	0.18404 (9)	0.56382 (7)	0.0302 (3)
N1A	0.08133 (11)	0.08323 (10)	0.61229 (7)	0.0239 (3)
H1AA	0.1296 (12)	0.0437 (12)	0.6058 (10)	0.029*
C1A	0.07085 (13)	0.30414 (13)	0.42009 (9)	0.0255 (4)
C2A	0.02947 (13)	0.13163 (11)	0.56154 (9)	0.0211 (3)
C3A	0.05085 (16)	0.08425 (15)	0.67878 (9)	0.0334 (4)
H3AA	0.0441	0.0181	0.6942	0.050*
H3AB	−0.0155	0.1174	0.6767	0.050*
H3AC	0.1034	0.1179	0.7102	0.050*
Cl1B	0.27558 (4)	0.53778 (4)	0.16143 (2)	0.03787 (12)
Cl2B	0.08921 (4)	0.64264 (4)	0.17392 (3)	0.04065 (13)
Cl3B	0.15634 (4)	0.48946 (4)	0.26583 (2)	0.03589 (12)
S1B	0.28444 (4)	0.66744 (3)	0.27052 (2)	0.02689 (10)
S2B	0.19567 (4)	0.71821 (3)	0.33553 (2)	0.02639 (10)
O1B	0.29056 (10)	0.57063 (9)	0.40606 (6)	0.0273 (3)
N1B	0.18133 (11)	0.65897 (10)	0.45778 (7)	0.0222 (3)
H1BA	0.1388 (12)	0.7061 (11)	0.4536 (10)	0.027*
C1B	0.19848 (14)	0.58421 (13)	0.21883 (8)	0.0254 (4)
C2B	0.22943 (12)	0.63574 (11)	0.40702 (8)	0.0195 (3)
C3B	0.20171 (14)	0.60575 (13)	0.52084 (9)	0.0262 (4)
H3BA	0.1735	0.6412	0.5558	0.039*
H3BB	0.2764	0.5979	0.5341	0.039*
H3BC	0.1690	0.5424	0.5149	0.039*

	U11	U22	U33	U12	U13	U23
Cl1A	0.0370 (3)	0.0591 (3)	0.0472 (3)	0.0132 (2)	0.0127 (2)	0.0337 (3)
Cl2A	0.0227 (2)	0.0413 (3)	0.0390 (3)	−0.00235 (18)	0.00915 (18)	0.0030 (2)
Cl3A	0.0477 (3)	0.0276 (2)	0.0371 (3)	−0.0091 (2)	0.0123 (2)	−0.00656 (19)
S1A	0.0242 (2)	0.0362 (3)	0.0220 (2)	−0.00899 (18)	−0.00211 (17)	0.00193 (18)
S2A	0.0311 (2)	0.0216 (2)	0.0251 (2)	0.00138 (17)	0.00954 (17)	−0.00147 (16)
O1A	0.0276 (7)	0.0306 (7)	0.0346 (7)	0.0138 (5)	0.0115 (5)	0.0094 (6)
N1A	0.0233 (7)	0.0235 (7)	0.0258 (7)	0.0083 (6)	0.0063 (6)	0.0027 (6)
C1A	0.0236 (8)	0.0281 (9)	0.0250 (9)	−0.0008 (7)	0.0044 (7)	0.0071 (7)
C2A	0.0216 (8)	0.0180 (8)	0.0250 (8)	−0.0005 (6)	0.0072 (7)	0.0001 (6)
C3A	0.0377 (11)	0.0366 (10)	0.0276 (10)	0.0080 (9)	0.0101 (8)	0.0080 (8)
Cl1B	0.0494 (3)	0.0412 (3)	0.0250 (2)	0.0009 (2)	0.0121 (2)	−0.00839 (19)
Cl2B	0.0380 (3)	0.0494 (3)	0.0303 (2)	0.0055 (2)	−0.0078 (2)	−0.0003 (2)
Cl3B	0.0457 (3)	0.0362 (3)	0.0246 (2)	−0.0184 (2)	0.00170 (19)	0.00053 (18)
S1B	0.0291 (2)	0.0312 (2)	0.0211 (2)	−0.00846 (18)	0.00602 (17)	−0.00414 (17)
S2B	0.0358 (2)	0.0232 (2)	0.0198 (2)	0.00546 (18)	0.00314 (17)	−0.00014 (16)
O1B	0.0289 (6)	0.0262 (6)	0.0270 (6)	0.0102 (5)	0.0051 (5)	−0.0037 (5)
N1B	0.0237 (7)	0.0207 (7)	0.0227 (7)	0.0074 (6)	0.0047 (6)	−0.0002 (6)
C1B	0.0307 (9)	0.0288 (9)	0.0163 (8)	−0.0028 (7)	0.0023 (7)	−0.0016 (7)
C2B	0.0197 (8)	0.0184 (8)	0.0193 (8)	0.0001 (6)	−0.0003 (6)	−0.0023 (6)
C3B	0.0308 (9)	0.0258 (9)	0.0228 (9)	0.0012 (7)	0.0065 (7)	0.0021 (7)

Cl1A—C1A	1.7736 (18)	Cl1B—C1B	1.7736 (18)
Cl2A—C1A	1.7625 (18)	Cl2B—C1B	1.7696 (19)
Cl3A—C1A	1.7667 (19)	Cl3B—C1B	1.7629 (18)
S1A—C1A	1.8242 (18)	S1B—C1B	1.8261 (18)
S1A—S2A	2.0100 (7)	S1B—S2B	2.0126 (6)
S2A—C2A	1.8367 (17)	S2B—C2B	1.8426 (17)
O1A—C2A	1.214 (2)	O1B—C2B	1.212 (2)
N1A—C2A	1.322 (2)	N1B—C2B	1.324 (2)
N1A—C3A	1.458 (2)	N1B—C3B	1.460 (2)
N1A—H1AA	0.864 (9)	N1B—H1BA	0.857 (9)
C3A—H3AA	0.9800	C3B—H3BA	0.9800
C3A—H3AB	0.9800	C3B—H3BB	0.9800
C3A—H3AC	0.9800	C3B—H3BC	0.9800
C1A—S1A—S2A	103.09 (6)	C1B—S1B—S2B	103.10 (6)
C2A—S2A—S1A	102.20 (6)	C2B—S2B—S1B	101.43 (6)
C2A—N1A—C3A	121.71 (15)	C2B—N1B—C3B	120.35 (14)
C2A—N1A—H1AA	120.5 (14)	C2B—N1B—H1BA	119.5 (14)
C3A—N1A—H1AA	117.3 (14)	C3B—N1B—H1BA	120.2 (14)
Cl2A—C1A—Cl3A	108.65 (10)	Cl3B—C1B—Cl2B	108.82 (10)
Cl2A—C1A—Cl1A	109.45 (9)	Cl3B—C1B—Cl1B	109.68 (10)
Cl3A—C1A—Cl1A	110.43 (10)	Cl2B—C1B—Cl1B	109.38 (9)
Cl2A—C1A—S1A	113.54 (10)	Cl3B—C1B—S1B	112.65 (9)
Cl3A—C1A—S1A	112.03 (9)	Cl2B—C1B—S1B	112.28 (10)
Cl1A—C1A—S1A	102.60 (9)	Cl1B—C1B—S1B	103.90 (9)
O1A—C2A—N1A	126.31 (16)	O1B—C2B—N1B	126.23 (16)
O1A—C2A—S2A	123.02 (13)	O1B—C2B—S2B	122.17 (13)
N1A—C2A—S2A	110.67 (12)	N1B—C2B—S2B	111.58 (12)
N1A—C3A—H3AA	109.5	N1B—C3B—H3BA	109.5
N1A—C3A—H3AB	109.5	N1B—C3B—H3BB	109.5
H3AA—C3A—H3AB	109.5	H3BA—C3B—H3BB	109.5
N1A—C3A—H3AC	109.5	N1B—C3B—H3BC	109.5
H3AA—C3A—H3AC	109.5	H3BA—C3B—H3BC	109.5
H3AB—C3A—H3AC	109.5	H3BB—C3B—H3BC	109.5
C1A—S1A—S2A—C2A	93.63 (8)	C1B—S1B—S2B—C2B	93.49 (8)
S2A—S1A—C1A—Cl2A	60.37 (10)	S2B—S1B—C1B—Cl3B	−60.94 (10)
S2A—S1A—C1A—Cl3A	−63.18 (10)	S2B—S1B—C1B—Cl2B	62.34 (9)
S2A—S1A—C1A—Cl1A	178.38 (6)	S2B—S1B—C1B—Cl1B	−179.58 (6)
C3A—N1A—C2A—O1A	3.3 (3)	C3B—N1B—C2B—O1B	1.6 (3)
C3A—N1A—C2A—S2A	−176.22 (14)	C3B—N1B—C2B—S2B	−176.67 (12)
S1A—S2A—C2A—O1A	2.87 (16)	S1B—S2B—C2B—O1B	−0.66 (15)
S1A—S2A—C2A—N1A	−177.64 (11)	S1B—S2B—C2B—N1B	177.64 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O1Bi	0.86 (1)	1.94 (1)	2.7825 (18)	164 (2)
N1B—H1BA···O1Aii	0.86 (1)	1.97 (1)	2.8231 (18)	175 (2)

C9H8Cl3NOS2	Dx = 1.629 Mg m−3
Mr = 316.63	Melting point = 357–359 K
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.4247 (17) Å	Cell parameters from 2312 reflections
b = 13.548 (2) Å	θ = 2.4–24.9°
c = 8.5675 (12) Å	µ = 1.01 mm−1
β = 103.176 (2)°	T = 173 K
V = 1291.2 (3) Å3	Rod, white
Z = 4	0.30 × 0.15 × 0.10 mm
F(000) = 640

Bruker SMART CCD area detector diffractometer	2056 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.041
phi and ω scans	θmax = 25.1°, θmin = 1.8°
Absorption correction: multi-scan SADABS, (Sheldrick, 2008)	h = −13→13
Tmin = 0.752, Tmax = 0.906	k = −16→16
12180 measured reflections	l = −10→10
2284 independent reflections

Refinement on F2	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.080	w = 1/[σ2(Fo2) + (0.0157P)2 + 3.520P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max < 0.001
2284 reflections	Δρmax = 0.33 e Å−3
148 parameters	Δρmin = −0.27 e Å−3

Experimental. Compound (2) (Barany et al., 2005) was synthesized and crystallized as outlined in the Scheme and described in the referenced publication.

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.

	x	y	z	Uiso*/Ueq
Cl1	0.57223 (8)	0.68834 (7)	0.12990 (11)	0.0399 (2)
Cl2	0.69283 (7)	0.60896 (7)	0.43579 (10)	0.0320 (2)
Cl3	0.64826 (8)	0.48462 (7)	0.15317 (11)	0.0385 (2)
S1	0.44925 (7)	0.53104 (6)	0.27940 (9)	0.02193 (18)
S2	0.37502 (7)	0.64387 (6)	0.37478 (9)	0.0249 (2)
O1	0.26774 (19)	0.66377 (16)	0.0620 (2)	0.0250 (5)
N1	0.2069 (2)	0.7676 (2)	0.2344 (3)	0.0247 (6)
H1A	0.222 (3)	0.785 (2)	0.3348 (16)	0.030*
C1	0.5911 (3)	0.5817 (2)	0.2514 (4)	0.0249 (7)
C2	0.2734 (3)	0.6962 (2)	0.1955 (3)	0.0207 (7)
C3	0.1156 (3)	0.8196 (3)	0.1127 (4)	0.0327 (8)
H2A	0.0778	0.7728	0.0272	0.039*
H2B	0.1544	0.8728	0.0632	0.039*
C4	0.0210 (3)	0.8631 (2)	0.1889 (4)	0.0258 (7)
C5	0.0178 (3)	0.9637 (3)	0.2167 (4)	0.0319 (8)
H5A	0.0737	1.0060	0.1833	0.038*
C6	−0.0662 (3)	1.0032 (3)	0.2928 (5)	0.0374 (9)
H6A	−0.0681	1.0724	0.3102	0.045*
C7	−0.1466 (3)	0.9429 (3)	0.3430 (4)	0.0347 (9)
H7A	−0.2029	0.9701	0.3974	0.042*
C8	−0.1457 (3)	0.8434 (3)	0.3145 (4)	0.0377 (9)
H8A	−0.2023	0.8019	0.3481	0.045*
C9	−0.0627 (3)	0.8028 (3)	0.2371 (4)	0.0333 (8)
H9A	−0.0632	0.7338	0.2171	0.040*

	U11	U22	U33	U12	U13	U23
Cl1	0.0348 (5)	0.0426 (5)	0.0407 (5)	−0.0039 (4)	0.0055 (4)	0.0208 (4)
Cl2	0.0283 (4)	0.0376 (5)	0.0262 (4)	−0.0033 (4)	−0.0021 (3)	−0.0023 (4)
Cl3	0.0296 (5)	0.0506 (6)	0.0360 (5)	0.0088 (4)	0.0088 (4)	−0.0132 (4)
S1	0.0225 (4)	0.0209 (4)	0.0225 (4)	0.0011 (3)	0.0054 (3)	0.0005 (3)
S2	0.0263 (4)	0.0321 (5)	0.0159 (4)	0.0072 (4)	0.0036 (3)	−0.0006 (3)
O1	0.0283 (12)	0.0321 (13)	0.0143 (11)	0.0036 (10)	0.0043 (9)	−0.0007 (9)
N1	0.0275 (15)	0.0317 (15)	0.0137 (13)	0.0101 (12)	0.0020 (11)	−0.0024 (11)
C1	0.0216 (16)	0.0311 (18)	0.0216 (16)	0.0023 (14)	0.0038 (13)	0.0012 (14)
C2	0.0210 (16)	0.0242 (17)	0.0176 (16)	−0.0015 (13)	0.0059 (12)	0.0018 (13)
C3	0.0319 (19)	0.041 (2)	0.0228 (17)	0.0146 (17)	0.0023 (14)	0.0023 (16)
C4	0.0239 (17)	0.0323 (19)	0.0188 (16)	0.0067 (14)	−0.0004 (13)	0.0013 (14)
C5	0.0242 (18)	0.0318 (19)	0.038 (2)	0.0007 (15)	0.0032 (15)	0.0032 (16)
C6	0.030 (2)	0.0291 (19)	0.052 (2)	0.0074 (16)	0.0059 (17)	−0.0070 (17)
C7	0.0199 (17)	0.048 (2)	0.035 (2)	0.0112 (16)	0.0039 (15)	−0.0053 (17)
C8	0.0246 (18)	0.051 (2)	0.037 (2)	−0.0034 (17)	0.0051 (16)	0.0099 (18)
C9	0.0334 (19)	0.0282 (19)	0.0344 (19)	0.0018 (16)	−0.0006 (16)	−0.0005 (15)

Cl1—C1	1.764 (3)	C3—H2B	0.9900
Cl2—C1	1.773 (3)	C4—C5	1.386 (5)
Cl3—C1	1.766 (3)	C4—C9	1.391 (5)
S1—C1	1.826 (3)	C5—C6	1.385 (5)
S1—S2	2.0099 (11)	C5—H5A	0.9500
S2—C2	1.842 (3)	C6—C7	1.369 (5)
O1—C2	1.213 (4)	C6—H6A	0.9500
N1—C2	1.319 (4)	C7—C8	1.370 (5)
N1—C3	1.475 (4)	C7—H7A	0.9500
N1—H1A	0.870 (10)	C8—C9	1.389 (5)
C3—C4	1.504 (4)	C8—H8A	0.9500
C3—H2A	0.9900	C9—H9A	0.9500
C1—S1—S2	103.68 (11)	H2A—C3—H2B	108.2
C2—S2—S1	101.40 (10)	C5—C4—C9	118.7 (3)
C2—N1—C3	121.8 (3)	C5—C4—C3	120.7 (3)
C2—N1—H1A	117 (2)	C9—C4—C3	120.6 (3)
C3—N1—H1A	121 (2)	C6—C5—C4	120.6 (3)
Cl1—C1—Cl3	109.72 (17)	C6—C5—H5A	119.7
Cl1—C1—Cl2	108.81 (18)	C4—C5—H5A	119.7
Cl3—C1—Cl2	109.94 (17)	C7—C6—C5	120.3 (3)
Cl1—C1—S1	113.13 (17)	C7—C6—H6A	119.9
Cl3—C1—S1	102.59 (17)	C5—C6—H6A	119.9
Cl2—C1—S1	112.48 (17)	C6—C7—C8	119.9 (3)
O1—C2—N1	126.4 (3)	C6—C7—H7A	120.1
O1—C2—S2	122.4 (2)	C8—C7—H7A	120.1
N1—C2—S2	111.2 (2)	C7—C8—C9	120.6 (3)
N1—C3—C4	110.0 (3)	C7—C8—H8A	119.7
N1—C3—H2A	109.7	C9—C8—H8A	119.7
C4—C3—H2A	109.7	C8—C9—C4	119.9 (3)
N1—C3—H2B	109.7	C8—C9—H9A	120.0
C4—C3—H2B	109.7	C4—C9—H9A	120.0
C1—S1—S2—C2	96.54 (14)	N1—C3—C4—C9	−72.6 (4)
S2—S1—C1—Cl1	−57.38 (18)	C9—C4—C5—C6	0.8 (5)
S2—S1—C1—Cl3	−175.51 (11)	C3—C4—C5—C6	−177.4 (3)
S2—S1—C1—Cl2	66.42 (17)	C4—C5—C6—C7	0.7 (5)
C3—N1—C2—O1	−1.3 (5)	C5—C6—C7—C8	−1.5 (5)
C3—N1—C2—S2	−178.2 (3)	C6—C7—C8—C9	0.9 (5)
S1—S2—C2—O1	−2.5 (3)	C7—C8—C9—C4	0.5 (5)
S1—S2—C2—N1	174.6 (2)	C5—C4—C9—C8	−1.4 (5)
C2—N1—C3—C4	155.8 (3)	C3—C4—C9—C8	176.8 (3)
N1—C3—C4—C5	105.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.87 (1)	2.02 (1)	2.887 (3)	174 (3)

C9H8Cl3NOS2	F(000) = 640
Mr = 316.63	Dx = 1.641 Mg m−3
Triclinic, P1	Melting point = 327–328 K
a = 8.9231 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1724 (13) Å	Cell parameters from 2932 reflections
c = 15.364 (2) Å	θ = 2.5–27.4°
α = 81.964 (2)°	µ = 1.02 mm−1
β = 81.806 (2)°	T = 123 K
γ = 68.851 (2)°	Plate, colourless
V = 1281.5 (3) Å3	0.25 × 0.20 × 0.09 mm
Z = 4

Bruker SMART CCD area detector diffractometer	4557 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.034
phi and ω scans	θmax = 27.5°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −11→11
Tmin = 0.676, Tmax = 0.746	k = −13→12
15282 measured reflections	l = −19→19
5790 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.073	w = 1/[σ2(Fo2) + (0.0294P)2 + 0.677P] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max = 0.001
5790 reflections	Δρmax = 0.39 e Å−3
291 parameters	Δρmin = −0.27 e Å−3

Experimental. Compound (3) (Barany et al., 1983; Schroll & Barany, 1986) was synthesized and crystallized as outlined in the Scheme and described in the reference publications.

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.

	x	y	z	Uiso*/Ueq
Cl1A	0.39735 (6)	0.18646 (6)	0.21843 (4)	0.02947 (13)
Cl2A	0.74662 (6)	0.06953 (6)	0.18508 (4)	0.02861 (13)
Cl3A	0.54721 (7)	0.15353 (7)	0.04057 (4)	0.03453 (14)
S1A	0.59372 (6)	0.36579 (6)	0.14069 (4)	0.02254 (12)
S2A	0.37780 (6)	0.50367 (6)	0.10688 (3)	0.02229 (12)
O1A	0.34261 (18)	0.50799 (16)	0.28397 (10)	0.0278 (3)
N1A	0.1137 (2)	0.61782 (18)	0.21527 (11)	0.0216 (4)
C1A	0.5668 (2)	0.1953 (2)	0.14591 (14)	0.0222 (4)
C2A	0.2724 (3)	0.5449 (2)	0.21823 (14)	0.0216 (4)
C3A	0.0124 (3)	0.6590 (3)	0.29789 (15)	0.0330 (5)
H3AA	0.0804	0.6312	0.3468	0.050*
H3AB	−0.0674	0.6115	0.3089	0.050*
H3AC	−0.0433	0.7618	0.2931	0.050*
C4A	0.0386 (2)	0.6638 (2)	0.13409 (13)	0.0202 (4)
C5A	−0.0647 (3)	0.6002 (2)	0.11406 (15)	0.0264 (5)
H5AA	−0.0818	0.5242	0.1525	0.032*
C6A	−0.1425 (3)	0.6478 (3)	0.03785 (16)	0.0300 (5)
H6AA	−0.2142	0.6052	0.0244	0.036*
C7A	−0.1160 (3)	0.7568 (3)	−0.01833 (15)	0.0307 (5)
H7AA	−0.1693	0.7889	−0.0707	0.037*
C8A	−0.0124 (3)	0.8198 (2)	0.00094 (15)	0.0301 (5)
H8AA	0.0066	0.8940	−0.0386	0.036*
C9A	0.0643 (3)	0.7748 (2)	0.07821 (14)	0.0255 (5)
H9AA	0.1332	0.8195	0.0924	0.031*
Cl1B	−0.02011 (7)	0.26039 (6)	0.25446 (4)	0.03331 (14)
Cl2B	−0.30856 (6)	0.26958 (5)	0.37202 (4)	0.02562 (12)
Cl3B	−0.02396 (7)	0.27511 (6)	0.43942 (4)	0.03100 (14)
S1B	−0.04426 (6)	0.01403 (5)	0.38013 (3)	0.02037 (12)
S2B	0.19477 (6)	−0.06161 (6)	0.39221 (3)	0.02144 (12)
O1B	0.19752 (18)	−0.07526 (17)	0.21777 (10)	0.0290 (4)
N1B	0.4406 (2)	−0.17006 (18)	0.27509 (11)	0.0220 (4)
C1B	−0.0950 (2)	0.2053 (2)	0.36108 (14)	0.0213 (4)
C2B	0.2795 (3)	−0.1046 (2)	0.27890 (13)	0.0205 (4)
C3B	0.5317 (3)	−0.2140 (3)	0.19095 (15)	0.0352 (6)
H3BA	0.4622	−0.1715	0.1431	0.053*
H3BB	0.5691	−0.3174	0.1926	0.053*
H3BC	0.6250	−0.1826	0.1807	0.053*
C4B	0.5250 (2)	−0.2155 (2)	0.35376 (13)	0.0191 (4)
C5B	0.5752 (2)	−0.1230 (2)	0.39013 (14)	0.0213 (4)
H5BA	0.5574	−0.0298	0.3626	0.026*
C6B	0.6515 (3)	−0.1679 (2)	0.46693 (14)	0.0241 (5)
H6BA	0.6852	−0.1048	0.4926	0.029*
C7B	0.6789 (2)	−0.3044 (2)	0.50636 (15)	0.0243 (5)
H7BA	0.7295	−0.3344	0.5596	0.029*
C8B	0.6322 (3)	−0.3973 (2)	0.46799 (15)	0.0269 (5)
H8BA	0.6535	−0.4917	0.4943	0.032*
C9B	0.5547 (2)	−0.3531 (2)	0.39146 (15)	0.0245 (5)
H9BA	0.5223	−0.4166	0.3652	0.029*

	U11	U22	U33	U12	U13	U23
Cl1A	0.0243 (3)	0.0276 (3)	0.0345 (3)	−0.0101 (2)	0.0015 (2)	0.0022 (2)
Cl2A	0.0235 (3)	0.0256 (3)	0.0300 (3)	0.0005 (2)	−0.0074 (2)	−0.0007 (2)
Cl3A	0.0382 (3)	0.0403 (3)	0.0264 (3)	−0.0111 (3)	−0.0104 (2)	−0.0075 (2)
S1A	0.0169 (3)	0.0241 (3)	0.0257 (3)	−0.0062 (2)	−0.0052 (2)	0.0014 (2)
S2A	0.0195 (3)	0.0243 (3)	0.0189 (3)	−0.0028 (2)	−0.0042 (2)	0.0009 (2)
O1A	0.0284 (8)	0.0337 (9)	0.0205 (8)	−0.0074 (7)	−0.0086 (7)	−0.0031 (7)
N1A	0.0222 (9)	0.0225 (9)	0.0173 (9)	−0.0035 (7)	−0.0029 (7)	−0.0030 (7)
C1A	0.0182 (10)	0.0252 (11)	0.0205 (11)	−0.0041 (9)	−0.0028 (8)	−0.0019 (9)
C2A	0.0244 (11)	0.0194 (10)	0.0215 (11)	−0.0072 (9)	−0.0038 (9)	−0.0026 (8)
C3A	0.0304 (13)	0.0390 (14)	0.0248 (12)	−0.0056 (11)	0.0022 (10)	−0.0100 (10)
C4A	0.0167 (10)	0.0203 (10)	0.0189 (10)	0.0003 (8)	−0.0013 (8)	−0.0054 (8)
C5A	0.0239 (11)	0.0248 (11)	0.0301 (12)	−0.0082 (9)	−0.0023 (9)	−0.0028 (9)
C6A	0.0214 (11)	0.0370 (13)	0.0329 (13)	−0.0081 (10)	−0.0035 (10)	−0.0122 (11)
C7A	0.0214 (11)	0.0432 (14)	0.0200 (11)	0.0001 (10)	−0.0034 (9)	−0.0080 (10)
C8A	0.0284 (12)	0.0304 (12)	0.0255 (12)	−0.0044 (10)	−0.0024 (10)	0.0014 (10)
C9A	0.0238 (11)	0.0241 (11)	0.0273 (12)	−0.0062 (9)	−0.0035 (9)	−0.0028 (9)
Cl1B	0.0299 (3)	0.0319 (3)	0.0323 (3)	−0.0101 (2)	0.0021 (2)	0.0089 (2)
Cl2B	0.0155 (2)	0.0262 (3)	0.0328 (3)	−0.0023 (2)	−0.0045 (2)	−0.0064 (2)
Cl3B	0.0288 (3)	0.0259 (3)	0.0428 (3)	−0.0104 (2)	−0.0143 (2)	−0.0046 (2)
S1B	0.0169 (2)	0.0196 (3)	0.0239 (3)	−0.0055 (2)	−0.0045 (2)	0.0002 (2)
S2B	0.0169 (2)	0.0262 (3)	0.0181 (3)	−0.0022 (2)	−0.0042 (2)	−0.0037 (2)
O1B	0.0285 (8)	0.0374 (9)	0.0212 (8)	−0.0080 (7)	−0.0092 (7)	−0.0065 (7)
N1B	0.0224 (9)	0.0251 (9)	0.0180 (9)	−0.0060 (7)	−0.0013 (7)	−0.0071 (7)
C1B	0.0169 (10)	0.0212 (11)	0.0251 (11)	−0.0058 (8)	−0.0046 (8)	0.0005 (9)
C2B	0.0253 (11)	0.0185 (10)	0.0185 (10)	−0.0073 (9)	−0.0020 (9)	−0.0052 (8)
C3B	0.0332 (13)	0.0463 (15)	0.0239 (12)	−0.0089 (11)	0.0030 (10)	−0.0158 (11)
C4B	0.0149 (10)	0.0209 (10)	0.0196 (10)	−0.0028 (8)	−0.0010 (8)	−0.0053 (8)
C5B	0.0205 (10)	0.0187 (10)	0.0242 (11)	−0.0057 (8)	−0.0015 (8)	−0.0045 (8)
C6B	0.0221 (11)	0.0272 (11)	0.0268 (12)	−0.0113 (9)	−0.0042 (9)	−0.0061 (9)
C7B	0.0163 (10)	0.0279 (11)	0.0270 (12)	−0.0056 (9)	−0.0045 (9)	−0.0005 (9)
C8B	0.0213 (11)	0.0202 (11)	0.0370 (13)	−0.0057 (9)	−0.0047 (10)	0.0017 (10)
C9B	0.0207 (11)	0.0217 (11)	0.0322 (12)	−0.0072 (9)	−0.0018 (9)	−0.0074 (9)

Cl1A—C1A	1.768 (2)	Cl1B—C1B	1.774 (2)
Cl2A—C1A	1.776 (2)	Cl2B—C1B	1.768 (2)
Cl3A—C1A	1.777 (2)	Cl3B—C1B	1.771 (2)
S1A—C1A	1.824 (2)	S1B—C1B	1.822 (2)
S1A—S2A	2.0202 (7)	S1B—S2B	2.0160 (7)
S2A—C2A	1.856 (2)	S2B—C2B	1.842 (2)
O1A—C2A	1.208 (2)	O1B—C2B	1.211 (2)
N1A—C2A	1.345 (3)	N1B—C2B	1.346 (3)
N1A—C4A	1.440 (3)	N1B—C4B	1.447 (3)
N1A—C3A	1.467 (3)	N1B—C3B	1.460 (3)
C3A—H3AA	0.9800	C3B—H3BA	0.9800
C3A—H3AB	0.9800	C3B—H3BB	0.9800
C3A—H3AC	0.9800	C3B—H3BC	0.9800
C4A—C9A	1.387 (3)	C4B—C9B	1.384 (3)
C4A—C5A	1.389 (3)	C4B—C5B	1.386 (3)
C5A—C6A	1.385 (3)	C5B—C6B	1.385 (3)
C5A—H5AA	0.9500	C5B—H5BA	0.9500
C6A—C7A	1.376 (3)	C6B—C7B	1.385 (3)
C6A—H6AA	0.9500	C6B—H6BA	0.9500
C7A—C8A	1.383 (3)	C7B—C8B	1.387 (3)
C7A—H7AA	0.9500	C7B—H7BA	0.9500
C8A—C9A	1.393 (3)	C8B—C9B	1.387 (3)
C8A—H8AA	0.9500	C8B—H8BA	0.9500
C9A—H9AA	0.9500	C9B—H9BA	0.9500
C1A—S1A—S2A	102.38 (7)	C1B—S1B—S2B	104.40 (7)
C2A—S2A—S1A	99.96 (7)	C2B—S2B—S1B	101.59 (7)
C2A—N1A—C4A	123.13 (17)	C2B—N1B—C4B	122.00 (17)
C2A—N1A—C3A	118.95 (18)	C2B—N1B—C3B	119.49 (18)
C4A—N1A—C3A	117.85 (17)	C4B—N1B—C3B	118.00 (17)
Cl1A—C1A—Cl2A	110.05 (11)	Cl2B—C1B—Cl3B	109.89 (11)
Cl1A—C1A—Cl3A	108.33 (11)	Cl2B—C1B—Cl1B	110.25 (11)
Cl2A—C1A—Cl3A	108.62 (11)	Cl3B—C1B—Cl1B	107.66 (11)
Cl1A—C1A—S1A	112.54 (11)	Cl2B—C1B—S1B	103.07 (10)
Cl2A—C1A—S1A	104.78 (11)	Cl3B—C1B—S1B	113.09 (11)
Cl3A—C1A—S1A	112.43 (11)	Cl1B—C1B—S1B	112.83 (11)
O1A—C2A—N1A	125.9 (2)	O1B—C2B—N1B	126.4 (2)
O1A—C2A—S2A	122.09 (16)	O1B—C2B—S2B	122.96 (16)
N1A—C2A—S2A	111.99 (15)	N1B—C2B—S2B	110.65 (14)
N1A—C3A—H3AA	109.5	N1B—C3B—H3BA	109.5
N1A—C3A—H3AB	109.5	N1B—C3B—H3BB	109.5
H3AA—C3A—H3AB	109.5	H3BA—C3B—H3BB	109.5
N1A—C3A—H3AC	109.5	N1B—C3B—H3BC	109.5
H3AA—C3A—H3AC	109.5	H3BA—C3B—H3BC	109.5
H3AB—C3A—H3AC	109.5	H3BB—C3B—H3BC	109.5
C9A—C4A—C5A	120.4 (2)	C9B—C4B—C5B	120.95 (19)
C9A—C4A—N1A	120.05 (19)	C9B—C4B—N1B	118.54 (18)
C5A—C4A—N1A	119.51 (19)	C5B—C4B—N1B	120.51 (18)
C6A—C5A—C4A	119.8 (2)	C6B—C5B—C4B	119.38 (19)
C6A—C5A—H5AA	120.1	C6B—C5B—H5BA	120.3
C4A—C5A—H5AA	120.1	C4B—C5B—H5BA	120.3
C7A—C6A—C5A	120.0 (2)	C7B—C6B—C5B	120.23 (19)
C7A—C6A—H6AA	120.0	C7B—C6B—H6BA	119.9
C5A—C6A—H6AA	120.0	C5B—C6B—H6BA	119.9
C6A—C7A—C8A	120.4 (2)	C6B—C7B—C8B	119.9 (2)
C6A—C7A—H7AA	119.8	C6B—C7B—H7BA	120.1
C8A—C7A—H7AA	119.8	C8B—C7B—H7BA	120.1
C7A—C8A—C9A	120.2 (2)	C9B—C8B—C7B	120.3 (2)
C7A—C8A—H8AA	119.9	C9B—C8B—H8BA	119.8
C9A—C8A—H8AA	119.9	C7B—C8B—H8BA	119.8
C4A—C9A—C8A	119.2 (2)	C4B—C9B—C8B	119.2 (2)
C4A—C9A—H9AA	120.4	C4B—C9B—H9BA	120.4
C8A—C9A—H9AA	120.4	C8B—C9B—H9BA	120.4
C1A—S1A—S2A—C2A	92.91 (10)	C1B—S1B—S2B—C2B	−95.23 (10)
S2A—S1A—C1A—Cl1A	−55.40 (11)	S2B—S1B—C1B—Cl2B	−169.19 (7)
S2A—S1A—C1A—Cl2A	−174.96 (8)	S2B—S1B—C1B—Cl3B	−50.59 (12)
S2A—S1A—C1A—Cl3A	67.26 (11)	S2B—S1B—C1B—Cl1B	71.90 (11)
C4A—N1A—C2A—O1A	177.3 (2)	C4B—N1B—C2B—O1B	−172.5 (2)
C3A—N1A—C2A—O1A	0.3 (3)	C3B—N1B—C2B—O1B	−0.8 (3)
C4A—N1A—C2A—S2A	−3.0 (2)	C4B—N1B—C2B—S2B	8.1 (2)
C3A—N1A—C2A—S2A	−179.98 (15)	C3B—N1B—C2B—S2B	179.73 (16)
S1A—S2A—C2A—O1A	10.32 (19)	S1B—S2B—C2B—O1B	6.32 (19)
S1A—S2A—C2A—N1A	−169.40 (14)	S1B—S2B—C2B—N1B	−174.23 (13)
C2A—N1A—C4A—C9A	−72.9 (3)	C2B—N1B—C4B—C9B	93.8 (2)
C3A—N1A—C4A—C9A	104.1 (2)	C3B—N1B—C4B—C9B	−78.0 (3)
C2A—N1A—C4A—C5A	109.7 (2)	C2B—N1B—C4B—C5B	−86.4 (3)
C3A—N1A—C4A—C5A	−73.3 (3)	C3B—N1B—C4B—C5B	101.8 (2)
C9A—C4A—C5A—C6A	0.0 (3)	C9B—C4B—C5B—C6B	−2.1 (3)
N1A—C4A—C5A—C6A	177.36 (19)	N1B—C4B—C5B—C6B	178.12 (19)
C4A—C5A—C6A—C7A	0.8 (3)	C4B—C5B—C6B—C7B	0.7 (3)
C5A—C6A—C7A—C8A	−0.3 (3)	C5B—C6B—C7B—C8B	1.1 (3)
C6A—C7A—C8A—C9A	−1.0 (3)	C6B—C7B—C8B—C9B	−1.6 (3)
C5A—C4A—C9A—C8A	−1.2 (3)	C5B—C4B—C9B—C8B	1.6 (3)
N1A—C4A—C9A—C8A	−178.58 (19)	N1B—C4B—C9B—C8B	−178.57 (19)
C7A—C8A—C9A—C4A	1.7 (3)	C7B—C8B—C9B—C4B	0.2 (3)