Crystal structures of three (trichloromethyl)(carbamoyl)disulfanes

Goldenberg, B.L.; Young Jr, V.G.; Barany, G.

doi:10.1107/S2056989015015893

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Volume 71| Part 10| October 2015| Pages 1169-1173

doi:10.1107/S2056989015015893

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Crystal structures of three (trichloromethyl)(carbamoyl)disulfanes

Barbara L. Goldenberg,^a Victor G. Young Jr ^a and George Barany ^a ^*

^aDepartment of Chemistry, University of Minnesota, Minneapolis, MN 55455, USA
^*Correspondence e-mail: barany@umn.edu

Edited by R. F. Baggio, Comisión Nacional de Energía Atómica, Argentina (Received 8 August 2015; accepted 25 August 2015; online 12 September 2015)

The present paper reports crystallographic studies on three related compounds that were of interest as precursors for synthetic and mechanistic work in organosulfur chemistry, as well as to model nitrogen-protecting groups: (N-methylcarbamoyl)(trichloromethyl)disulfane, C₃H₄Cl₃NOS₂, (1), (N-benzylcarbamoyl)(trichloromethyl)disulfane, C₉H₈Cl₃NOS₂, (2), and (N-methyl-N-phenylcarbamoyl)(trichloromethyl)disulfane, C₉H₈Cl₃NOS₂, (3). Their molecular 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 molecules 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), molecules 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), molecules 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.

Keywords: crystal structures; carbamoyl disulfanes; hydrogen bonding; Z = 16; Z′ = 2; halogen bonding.

CCDC references: 1420526; 1420527; 1420528

1. 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.

2. 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)

3. 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⋯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)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x, -y+1, -z+1.

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) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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 (3b) 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 (3a). 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 (3a) and (3b) 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.]

4. 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 ).

5. 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 HNR¹R². Therefore B⁺ is usually the appropriate ammonium counter-ion H₂N⁺R¹R². 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 R³ = H, starting amine HNR¹R² is present in sufficient excess so that a second equivalent of amine can absorb the HCl co-product. When R¹ and/or R³ = 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.

6. 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—H_3: 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 $[\overline{1}]$
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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (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 ).

Supporting information

CCDC references: 1420526; 1420527; 1420528

Crystal structure: contains datablocks 1, 2, 3. DOI: 10.1107/S2056989015015893/bg2565sup1.cif

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

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

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

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

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

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

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

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

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

checkCIF report

Chemical context top

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, 2005; Schroll & Barany, 1986; Schrader et al., 2011). The trichloromethyl derivatives reported here, (N-methylcarbamoyl)(trichloromethyl)disulfane, (1) (Fig. 1), (N-benzylcarbamoyl)(trichloromethyl)disulfane, (2) (Fig. 2), and (N-methyl-N-phenylcarbamoyl)(trichloromethyl)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 as evidenced by unchanged ¹H NMR spectra and melting points.

Structural commentary top

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).

Supramolecular features top

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 (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). Halogen bonding involving trichloromethyl groups in supramolecular structures was described by Rybarczyk-Pirek et al. (2013).

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. 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).

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 (3b) 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 (3a). Fig 8 shows a schematic view of the intermolecular interactions. A pair of non-classical hydrogen bonds [C9A—H9AA···O1Bⁱⁱ and C9Bⁱⁱ—H9BAⁱⁱ···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 (3a) and (3b) molecules. Two additional non-classical hydrogen bonds [C5A—H5AA···Cl1B and C3Bⁱ—H3BAⁱ···Cl3A, with H···C 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.

Database survey top

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-dicyclohexylthiocarbamoyl)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 top

Refinement top

Related literature top

For related literature, see: Barany & Merrifield (1977); Barany et al. (1983, 2005); Bereman et al. (1983); Harris (1960); Henley et al. (2015); Li et al. (2006); Rybarczyk-Pirek, Chęcińska, Malecka & Wojtulewski (2013); Schrader et al. (2011); Schroll & Barany (1986); Schroll et al. (2012); Steudel et al. (1995).

Computing details top

For all compounds, data collection: SMART (Bruker, 2007); cell refinement: SMART (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009), ACD/ChemBioDraw (ACD/Labs, 2014).

Figures top

	Fig. 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.
	Fig. 2. The molecular structure of compound (2) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 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.
	Fig. 4. Hydrogen-bonded chains of (1) are linked by S1A···O1B contacts. Only H atoms involved in N—H···O=C bonds are shown.
	Fig. 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.
	Fig. 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.
	Fig. 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]
	Fig. 8. Synthetic routes to (trichloromethyl)(carbamoyl)disulfanes, (1), (2) and (3).

(1) (N-Methylcarbamoyl)(trichloromethyl)disulfane top

Crystal data top

C₃H₄Cl₃NOS₂	D_x = 1.757 Mg m⁻³
M_r = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0241P)² + 4.8271P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.002
4168 reflections	Δρ_max = 0.80 e Å⁻³
189 parameters	Δρ_min = −0.63 e Å⁻³

Crystal data top

C₃H₄Cl₃NOS₂	V = 3638.3 (8) Å³
M_r = 240.54	Z = 16
Monoclinic, C2/c	Mo Kα radiation
a = 13.1141 (16) Å	µ = 1.40 mm⁻¹
b = 13.9234 (17) Å	T = 123 K
c = 20.172 (3) Å	0.40 × 0.30 × 0.11 mm
β = 98.969 (2)°

Data collection top

Bruker SMART CCD area detector diffractometer	4168 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	3556 reflections with I > 2σ(I)
T_min = 0.646, T_max = 0.746	R_int = 0.030
21324 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	2 restraints
wR(F²) = 0.061	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.80 e Å⁻³
4168 reflections	Δρ_min = −0.63 e Å⁻³
189 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, −y+1, −z+1.

(2) (N-Benzylcarbamoyl)(trichloromethyl)disulfane top

Crystal data top

C₉H₈Cl₃NOS₂	D_x = 1.629 Mg m⁻³
M_r = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0157P)² + 3.520P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2284 reflections	Δρ_max = 0.33 e Å⁻³
148 parameters	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₉H₈Cl₃NOS₂	V = 1291.2 (3) Å³
M_r = 316.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.4247 (17) Å	µ = 1.01 mm⁻¹
b = 13.548 (2) Å	T = 173 K
c = 8.5675 (12) Å	0.30 × 0.15 × 0.10 mm
β = 103.176 (2)°

Data collection top

Bruker SMART CCD area detector diffractometer	2284 independent reflections
Absorption correction: multi-scan SADABS, (Sheldrick, 2008)	2056 reflections with I > 2σ(I)
T_min = 0.752, T_max = 0.906	R_int = 0.041
12180 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	1 restraint
wR(F²) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.33 e Å⁻³
2284 reflections	Δρ_min = −0.27 e Å⁻³
148 parameters

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) x, −y+3/2, z+1/2.

(3) (N-Methyl-N-phenylcarbamoyl)(trichloromethyl)disulfane top

Crystal data top

C₉H₈Cl₃NOS₂	F(000) = 640
M_r = 316.63	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0294P)² + 0.677P] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max = 0.001
5790 reflections	Δρ_max = 0.39 e Å⁻³
291 parameters	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₉H₈Cl₃NOS₂	γ = 68.851 (2)°
M_r = 316.63	V = 1281.5 (3) Å³
Triclinic, P1	Z = 4
a = 8.9231 (12) Å	Mo Kα radiation
b = 10.1724 (13) Å	µ = 1.02 mm⁻¹
c = 15.364 (2) Å	T = 123 K
α = 81.964 (2)°	0.25 × 0.20 × 0.09 mm
β = 81.806 (2)°

Data collection top

Bruker SMART CCD area detector diffractometer	5790 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	4557 reflections with I > 2σ(I)
T_min = 0.676, T_max = 0.746	R_int = 0.034
15282 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.073	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.39 e Å⁻³
5790 reflections	Δρ_min = −0.27 e Å⁻³
291 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

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

	(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)

Comparison of selected torsion angles (°) top

	(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)

Hydrogen-bond geometry (Å, º) for (1) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1AA···O1Bⁱ	0.864 (9)	1.941 (11)	2.7825 (18)	164.4 (19)
N1B—H1BA···O1Aⁱⁱ	0.857 (9)	1.968 (10)	2.8231 (18)	175.1 (19)

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) for (2) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.870 (10)	2.020 (11)	2.887 (3)	174 (3)

Symmetry code: (i) x, −y+3/2, z+1/2.

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, P1
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 diffractometer	Bruker SMART CCD area detector diffractometer	Bruker SMART CCD area detector diffractometer
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[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.63	0.33, −0.27	0.39, −0.27

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

Acknowledgements

We thank Al-Mutassim Abu-Khdeir, Michael J. Barany, Charles S. Barrett, Megan M. Corey, Courtney Elm, David A. Halsrud, Michael C. Hanson, Matthew J. Henley, Isaac D. Mitchell, Ross A. Moretti, Alex M. Schrader, Matthew J. Turcotte and Xiaolu Zheng for preparing compounds used in this work, as well as studies on their chemistry, and Alayne L. Schroll for helpful discussions during the preparation of this manuscript.

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Volume 71| Part 10| October 2015| Pages 1169-1173

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