Hydrogen-bonding patterns in two aroylthio­carbamates and two aroylimidothio­carbonates

In O-ethyl N-benzoyl­thio­carbamate, C₁₀H₁₁NO₂S, the mol­ecules are linked into sheets by a combination of two-centre N—H...O and C—H...S hydrogen bonds and a three-centre C—H...(O,S) hydrogen bond. A combination of two-centre N—H...O and C—H...O hydrogen bonds links the mol­ecules of O-ethyl N-(4-methyl­benzoyl)thio­carbamate, C₁₁H₁₃NO₂S, into chains of rings, which are linked into sheets by an aromatic π–π stacking inter­action. In O,S-diethyl N-(4-methyl­benzoyl)imidothio­carbonate, C₁₃H₁₇NO₂S, pairs of mol­ecules are linked into centrosymmetric dimers by pairs of symmetry-related C—H...π(arene) hydrogen bonds, while the mol­ecules of O,S-diethyl N-(4-chloro­benzoyl)imidothio­carbonate, C₁₂H₁₄ClNO₂S, are linked by a single C—H...O hydrogen bond into simple chains, pairs of which are linked by an aromatic π–π stacking inter­action to form a ladder-type structure.

S1. Comment

O,S-Dialkyl aroyliminothiocarbonates are structural analogues of S,S-dialkyl aroyliminothiocarbonates, which have been widely used as synthetic starting materials (Augustín et al., 1980; Sato et al., 1981; Fukada et al., 1985, 1986, 1990; Insuasty et al., 2006, 2008). We report here the structures of two O-ethyl aroylthiocarbamates, (I) and (II) (Fig. 1a and b), and two O,S-diethyl aroylimidothiocarbonates, (III) and (IV) (Fig. 1c and d), and we compare these structures with those of the closely related S-ethyl aroyldithiocarbamates, (V) and (VI) (see scheme) (Low et al., 2004, 2005). The structure of (I) has been briefly reported previously [Cambridge Strutural Database (Allen, 2002) refcode GIFSUK; Arslan et al., 2007)], but the authors' primary concern was the comparison of the experimental geometry and vibrational frequencies with those calculated from first principles at various levels of theory. The hydrogen bonding was described extremely briefly, in terms of only an N—H···O interaction, and no structure factors were deposited. Accordingly, we have thought it worthwhile to report here a more complete description of the hydrogen bonding in (I).

Compounds (I) and (II) were prepared by the addition of ethanol to the corresponding intermediate aroylisothiocyanate, (B) (see scheme), itself prepared by reaction of potassium thiocyanate with the aroyl chloride, (A). Deprotonation of the O-ethyl aroylthiocarbamates yields the ionic intermediate, (C), reaction of which with bromoethane gives (III) and (IV). The corresponding reactions of the appropriate aroylisothiocyanate, (B), with ethanethiol rather than with ethanol produces the dithiocarbamate esters (V) and (VI) (Low et al., 2004, 2005). It is interesting to note that in the conversion of (A) to (B), the thiocyanate anion reacts with the aroyl chloride exclusively via the harder N-terminus, while in the formation of (III) and (IV) from (C), this anionic component of (C) reacts with bromoethane exclusively at the softer S centre.

Despite the close pairwise similarities between the molecular constitutions within the pairs of compounds (I) and (II), (III) and (IV), and (V) and (VI), and the overall similarities within the group (I), (II), (V) and (VI), no two of these compounds are isomorphous. Thus, for example, while compounds (I) and (II) crystallize in the space groups Pna2₁ and P2₁/c, respectively, both with Z' = 1, their close analogues (V) and (VI) crystallize in, respectively, C2/c with Z' = 2, and P2₁/c with Z' = 1. The unit-cell dimensions of (II) and (VI), which could well have been isomorphous and isostructural are, in fact, significantly different, particularly for the cell repeat distance a and the cell angle β. In addition, (III) and (IV), which might plausibly have been expected to be isomorphous, crystallize with triclinic cells in which the real and reduced cell angles are very different: the cell angles in (III) are all significantly greater than 90°, while those in (IV) are all well below 90°. Hence the unit cell for (III) can be assigned as belonging to type II, designation 4R (Buerger, 1956), while that of (IV) can be assigned as type I, designation 1R.

In the thiocarbamate esters, (I) and (II), the molecular skeletons adopt chain-extended conformations which, apart from the aryl substituents, are close to planarity, as shown by the leading torsion angles (Table 1). The most striking feature of the conformations of the thiocarbonates, (III) and (IV), is the orientation of the S-ethyl groups (Figs. 1c and d). Whereas in (III) this ethyl group is almost coplanar with the rest of the skeleton, in (IV) this unit is almost orthogonal to the rest of the molecule (Table 1). In addition, whereas in the thiocarbamate esters, (I) and (II), the formal double bonds C═O and C═S are mutually cisoid, in the dithiocarbamate esters, (V) and (VI) (Low et al., 2004, 2005), these units adopt a transoid arrangement (cf. scheme).

In each of compounds (I)–(IV), the C—O bond distances involving atom O3, namely C3—O4 in (I) and (II), and C3—O41 in (III) and (IV), are all the same within experimental uncertainty. In addition, the N2—C3 bonds in (I) and (II) are long for their type (Allen et al., 1997a). These observations, taken together, indicate that in (I) and (II) there is very little electronic delocalization from atoms N2 and O4 onto atom S3. By contrast, in (V) and (VI), the C═S bond distances are 1.6586 (18) and 1.6552 (18) Å in (V), where Z' = 2 (Low et al., 2004), and 1.631 (3) Å in (VI) (Low et al., 2005), typical of such distances in compounds containing >N—C(═S)—S– fragments (Allen et al., 1997a) and consistent with the occurrence of conjugative delocalization. In (III) and (IV) the C—N distances provide a clear distinction between the formal single bonds C1—N2 and the formal double bonds N2═C3. Despite the apparent lack of any significant polarization of the electronic structures in (I) and (II), the bond angles at atoms C1, N2 and C3 are certainly consistent with a strongly repulsive non-bonded interaction between atom O1 and S3. A similar pattern of bond angles is apparent in (III) and (IV).

The supramolecular aggregation in (I) and (II) is dominated by a combination of N—H···O and C—H···O hydrogen bonds, utilizing the same acceptor atom O1 in each compound (Table 2). These interactions are augmented, in the case of (I) only, by two C—H···S interactions. In (I), molecules related by the a-glide plane at y = 3/4 are linked by a combination of a two-centre N—H···O hydrogen bond and a weaker three-centre C—H···(O,S) hydrogen bond to form a ribbon containing alternating R²₁(6) (Bernstein et al., 1995) and R¹₂(7) rings and running parallel to the [100] direction (Fig. 2). A second C—H···S interaction links molecules related by the n-glide plane at x = 3/4 into a simple C(7) chain running parallel to the [011] direction (Fig. 3). The combination of the ribbon along [100] and the chain along [011] generates a hydrogen-bonded sheet parallel to (011), but there are no direction-specific interactions between adjacent sheets. In particular, both C—H···π(arene) hydrogen bonds and aromatic π–π stacking interactions are absent from the crystal structure of (I).

In (II), a combination of N—H···O and C—H···O hydrogen bonds, similar to the corresponding combination in (I), links molecules related by the c-glide plane at y = 3/4 into a chain of R¹₂(7) rings running parallel to the [001] direction (Fig. 4). The closest intermolecular contacts between atom S3 and the H atoms in (II) corresponding to the C—H···S interactions in (I) all have H···S distances well in excess of 3 Å, and hence they cannot be regarded as structurally significant. Although significant C—H···S interactions are absent from the crystal structure of (II), the hydrogen-bonded chains are linked by an aromatic π–π stacking interaction. The aryl rings in the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) are parallel by symmetry, with an interplanar spacing of 3.479 (2) Å. The corresponding ring-centroid separation is 3.746 (2) Å and the ring-centroid offset (slippage) is 1.389 (2) Å. The effect of this stacking interaction is to link the hydrogen-bonded chains into a sheet parallel to (100) (Fig. 5).

Since no N—H bonds are present in (III) and (IV), the modes of supramolecular aggregation in these compounds necessarily differ substantially from those observed in (I) and (II). In (III), a single C—H···π(arene) hydrogen bond links pairs of molecules into centrosymmetric dimers (Fig. 6). However, π–π stacking interactions are absent and there are no direction-specific interactions between the dimeric units. By contrast, the crystal structure of (IV) contains no C—H···π(arene) hydrogen bonds, but instead chains built from C—H···O hydrogen bonds are linked in pairs to form a ladder-type structure, in which molecules related by translation form C(6) chains running parallel to the [100] direction. The aryl rings of the molecules at (x, y, z) and (1 - x, 1 - y, 1 - z) are strictly parallel, with an interplanar spacing of 3.428 (2) Å. The ring-centroid separation and offset are 3.787 (2) and 1.609 (2) Å, respectively, so that pairs of antiparallel C(6) chains are weakly linked (Fig. 7).

It is of interest briefly to compare the supramolecular aggregation in (V) and (VI) (Low et al., 2004, 2005) with that in (I)–(IV). Compound (V) crystallizes with Z' = 2 in space group C2/c (Low et al., 2004) and each type of molecule independently forms a cyclic R²₂(8) dimer. These dimers are built using two symmetry-related N—H···S hydrogen bonds, with the thione-type S atoms as the acceptors in both types of dimer. One type of dimer contains molecules related by inversion and the other contains molecules related by a twofold rotation axis, and the two independent types of dimer are linked into chains by a single C—H···π(arene) hydrogen bond. It is striking that there is no participation by the amidic O atom in the hydrogen bonding in (V). In compound (VI), on the other hand, where Z' = 1 (Low et al., 2005), a combination of N—H···O and C—H···O hydrogen bonds generates a chain of R¹₂(7) rings along [001], and chains of this type are linked into a sheet by a single aromatic π–π stacking interaction. Thus, while (II) and (VI) are not isomorphous, and while their molecules adopt different conformations, nonetheless their crystal structures exhibit very similar patterns of intermolecular interaction.

The only hydrogen bonds in this series of compounds, (I)–(VI), which involve S atoms as the acceptors utilize the thione-type S atoms in (I) and (V), but the two-coordinate S atoms in compounds (III)–(VI) do not participate in any hydrogen-bond formation. This observation is certainly consistent with the deductions drawn from database analyses (Allen et al., 1997a,b) that, while thione-type S atoms can in some circumstances act as effective hydrogen-bond acceptors, two-coordinate S atoms are, in general, very poor acceptors.

S2. Experimental

For the synthesis of (I) and (II), the appropriate aroyl chloride (0.043 mol) was added to a solution of potassium thiocyanate (0.043 mol) in acetonitrile (75 ml). This mixture was heated under reflux for 15 min to afford the corresponding aroyl isothiocyanate, which was not isolated. After cooling the intermediate solution to 273 K under an inert atmosphere, dry ethanol (0.47 mol) was added, and this mixture was then stirred at ambient temperature for 24 h. Ice–water was added to the reaction mixture and the resulting light-green solid was collected by filtration, washed with water, dried under reduced pressure and finally crystallized by slow evaporation, at ambient temperature and in air, of a solution in n-hexane, to give crystals suitable for single-crystal X-ray diffraction. For (I), yield 95%, m.p. 345 K. For (II), yield 92%, m.p. 331 K.

For the synthesis of (III) and (IV), a slight excess of sodium hydride (60% suspension in oil, 0.020 mol) was added under an inert atmosphere to an ice-cold solution of the corresponding O-ethyl aroyliminothiocarbonate (0.010 mol) in N,N-dimethylformamide (6 ml). This mixture was stirred for 45 min at ambient temperature, and then bromoethane (0.012 mol) was slowly added and the stirring was continued for a further 30 min. Ice–water was added to the reaction mixture and the resulting colourless solid was collected by filtration, washed with water, dried under reduced pressure and finally crystallized by slow evaporation, at ambient temperature and in air, of a solution in dry ethanol, to give crystals suitable for single-crystal X-ray diffraction. For (III), yield 94%, m.p. 333 K. For (IV), yield 95%, m.p. 373 K.

S3. Refinement

All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H = 0.95 (aromatic), 0.98 (CH₃) or 0.99 Å (CH₂) and N—H = 0.88 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms. For (I), the correct orientation of the structure with respect to the polar axis direction was established by means of the Flack x parameter (Flack, 1983), x = 0.08 (17), and the Hooft y parameter (Hooft et al., 2008), y = 0.03 (5), for 99.6% coverage of the Bijvoet pairs. Compound (III) was handled as a non-merohedral twin, in which the two twin components are related by the matrix (1.000, 0.557, 0.320/0.000, -1.000, 0.000/0.000, 0.000, -1.000). Using the original HKLF file [15150 reflections, R(int) = 0.0581], a modified file [2460 reflections, R(int) = 0.0000] was prepared using the TwinRotMat option in PLATON (Spek, 2009) and then used in conjunction with the HKLF 5 option in SHELXL97 (Sheldrick, 2008), giving twin fractions of 0.268 (5) and 0.732 (5).

Computing details

For all compounds, data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I); SIR2004 (Burla et al., 2005) for (II), (III), (IV). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structures of (a) (I), (b) (II), (c) (III) and (d) (IV), showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a ribbon along [100] containing R^21(6) and R^12(7) rings. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. Atoms marked with an asterisk (*), a hash symbol (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (-1/2 + x, 3/2 - y, z) (-1 + x, y, z), (1/2 + x, 3/2 - y, z) and (1 + x, y, z), respectively.
	Fig. 3. Part of the crystal structure of (I), showing the formation of a C(7) chain along [011]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. Atoms marked with an asterisk (*), a hash symbol (#) or a dollar sign ($) are at the symmetry positions (3/2 - x, 1/2 + y, -1/2 + z), (3/2 - x, - 1/2 + y, 1/2 + z) and (x, -1 + y, 1 + z), respectively.
	Fig. 4. Part of the crystal structure of (II), showing the formation of a chain of R^12(7) rings along [001]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. Atoms marked with an asterisk (*), a hash symbol (#), a dollar sign ($) or an ampersand (&) are at the symmetry positions (x, 3/2 - y, -1/2 + z), (x, y, -1 + z), (x, 3/2 - y, 1/2 + z) and (x, y, 1 + z), respectively.
	Fig. 5. A stereoview of part of the crystal structure of (II), showing the π-stacking of hydrogen-bonded chains along [001] to form a sheet parallel to (100). For the sake of clarity, H atoms not involved in the motifs shown have been omitted.
	Fig. 6. Part of the crystal structure of (III), showing the formation of a centrosymmetric dimer by means of symmetry-related C—H···π(arene) hydrogen bonds. For the sake of clarity, H atoms bonded to C atoms which are not involved in the motif shown have been omitted. The atom marked with an asterisk (*) is at the symmetry position (1 - x, 1 - y, 1 - z).
	Fig. 7. A stereoview of part of the crystal structure of (IV), showing a π-stacked pair of antiparallel hydrogen-bonded chains along [100]. For the sake of clarity, H atoms not involved in the motif shown have been omitted.

(I) O-ethyl benzoylthiocarbamate

Crystal data

C10H11NO2S	F(000) = 440
Mr = 209.27	Dx = 1.366 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 1889 reflections
a = 9.9418 (8) Å	θ = 2.9–25.5°
b = 9.3619 (5) Å	µ = 0.29 mm^−1
c = 10.9337 (13) Å	T = 120 K
V = 1017.65 (16) Å^3	Block, green
Z = 4	0.50 × 0.42 × 0.41 mm

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	1889 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1284 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
Detector resolution: 9.091 pixels mm^-1	θmax = 25.5°, θmin = 2.9°
ϕ and ω scans	h = −12→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
Tmin = 0.868, Tmax = 0.890	l = −13→13
13852 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0546P)^2 + 0.655P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max = 0.001
1889 reflections	Δρmax = 0.45 e Å^−3
128 parameters	Δρmin = −0.29 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 890 Bijvoet pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.08 (17)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5732 (4)	0.7797 (5)	0.2183 (4)	0.0260 (10)
O1	0.6860 (3)	0.7329 (3)	0.2110 (3)	0.0307 (7)
N2	0.4670 (3)	0.6998 (4)	0.2635 (3)	0.0270 (9)
H2	0.3857	0.7310	0.2461	0.032*
C3	0.4743 (4)	0.5764 (5)	0.3329 (4)	0.0279 (10)
S3	0.60817 (10)	0.49807 (13)	0.38277 (14)	0.0356 (3)
O4	0.3488 (3)	0.5368 (3)	0.3554 (3)	0.0362 (9)
C5	0.3277 (5)	0.4172 (5)	0.4363 (5)	0.0337 (11)
H5A	0.3527	0.4429	0.5212	0.040*
H5B	0.3828	0.3345	0.4103	0.040*
C6	0.1807 (4)	0.3815 (5)	0.4290 (5)	0.0365 (12)
H6A	0.1274	0.4667	0.4479	0.055*
H6B	0.1596	0.3059	0.4880	0.055*
H6C	0.1590	0.3485	0.3462	0.055*
C11	0.5382 (4)	0.9261 (5)	0.1803 (4)	0.0300 (11)
C12	0.4230 (4)	0.9969 (4)	0.2190 (4)	0.0262 (10)
H12	0.3596	0.9491	0.2695	0.031*
C13	0.4006 (4)	1.1359 (5)	0.1842 (5)	0.0342 (12)
H13	0.3221	1.1843	0.2112	0.041*
C14	0.4913 (5)	1.2049 (5)	0.1106 (5)	0.0387 (12)
H14	0.4753	1.3012	0.0874	0.046*
C15	0.6053 (4)	1.1359 (5)	0.0700 (4)	0.0328 (12)
H15	0.6671	1.1837	0.0178	0.039*
C16	0.6287 (5)	0.9976 (4)	0.1058 (5)	0.0269 (10)
H16	0.7079	0.9502	0.0791	0.032*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.021 (2)	0.031 (3)	0.027 (2)	−0.0004 (19)	−0.0034 (19)	−0.006 (2)
O1	0.0219 (15)	0.0322 (17)	0.0380 (18)	0.0010 (13)	−0.0002 (14)	0.0041 (15)
N2	0.0190 (18)	0.029 (2)	0.033 (2)	−0.0024 (16)	0.0011 (16)	0.0025 (18)
C3	0.033 (3)	0.021 (2)	0.029 (3)	0.002 (2)	−0.002 (2)	−0.007 (2)
S3	0.0267 (5)	0.0359 (6)	0.0441 (6)	0.0034 (5)	−0.0018 (7)	0.0087 (5)
O4	0.0270 (17)	0.0363 (17)	0.045 (2)	−0.0023 (13)	0.0020 (15)	0.0123 (16)
C5	0.033 (3)	0.029 (2)	0.039 (3)	0.000 (2)	−0.004 (2)	0.011 (2)
C6	0.035 (3)	0.034 (3)	0.040 (3)	−0.004 (2)	0.003 (2)	0.007 (2)
C11	0.027 (3)	0.031 (2)	0.032 (3)	−0.005 (2)	−0.002 (2)	0.005 (2)
C12	0.024 (2)	0.028 (2)	0.026 (2)	−0.0015 (18)	−0.0010 (19)	0.000 (2)
C13	0.029 (3)	0.031 (3)	0.042 (3)	0.003 (2)	−0.001 (2)	0.000 (2)
C14	0.040 (3)	0.029 (2)	0.047 (3)	−0.005 (2)	−0.004 (2)	0.003 (2)
C15	0.029 (3)	0.034 (3)	0.035 (3)	−0.010 (2)	0.006 (2)	0.008 (2)
C16	0.024 (2)	0.027 (2)	0.030 (2)	−0.001 (2)	0.0035 (18)	−0.005 (2)

Geometric parameters (Å, º)

C1—O1	1.206 (5)	C6—H6C	0.9800
C1—N2	1.385 (5)	C11—C16	1.386 (6)
C1—C11	1.473 (6)	C11—C12	1.389 (6)
N2—C3	1.384 (6)	C12—C13	1.374 (6)
N2—H2	0.8800	C12—H12	0.9500
C3—O4	1.325 (5)	C13—C14	1.369 (7)
C3—S3	1.615 (4)	C13—H13	0.9500
O4—C5	1.443 (5)	C14—C15	1.378 (6)
C5—C6	1.501 (6)	C14—H14	0.9500
C5—H5A	0.9900	C15—C16	1.373 (6)
C5—H5B	0.9900	C15—H15	0.9500
C6—H6A	0.9800	C16—H16	0.9500
C6—H6B	0.9800
O1—C1—N2	122.4 (4)	H6A—C6—H6C	109.5
O1—C1—C11	122.6 (4)	H6B—C6—H6C	109.5
N2—C1—C11	115.0 (4)	C16—C11—C12	118.9 (4)
C3—N2—C1	127.3 (4)	C16—C11—C1	117.5 (4)
C3—N2—H2	116.3	C12—C11—C1	123.6 (4)
C1—N2—H2	116.3	C13—C12—C11	120.1 (4)
O4—C3—N2	106.6 (3)	C13—C12—H12	120.0
O4—C3—S3	125.9 (3)	C11—C12—H12	120.0
N2—C3—S3	127.4 (3)	C14—C13—C12	120.2 (4)
C3—O4—C5	117.9 (4)	C14—C13—H13	119.9
O4—C5—C6	106.3 (4)	C12—C13—H13	119.9
O4—C5—H5A	110.5	C13—C14—C15	120.7 (4)
C6—C5—H5A	110.5	C13—C14—H14	119.7
O4—C5—H5B	110.5	C15—C14—H14	119.7
C6—C5—H5B	110.5	C16—C15—C14	119.3 (4)
H5A—C5—H5B	108.7	C16—C15—H15	120.4
C5—C6—H6A	109.5	C14—C15—H15	120.4
C5—C6—H6B	109.5	C15—C16—C11	120.9 (4)
H6A—C6—H6B	109.5	C15—C16—H16	119.6
C5—C6—H6C	109.5	C11—C16—H16	119.6
O1—C1—N2—C3	17.4 (6)	N2—C1—C11—C12	19.3 (6)
C11—C1—N2—C3	−162.4 (4)	C16—C11—C12—C13	−0.5 (6)
C1—N2—C3—O4	−179.9 (4)	C1—C11—C12—C13	176.8 (5)
C1—N2—C3—S3	2.5 (6)	C11—C12—C13—C14	0.4 (7)
N2—C3—O4—C5	−174.4 (4)	C12—C13—C14—C15	0.4 (8)
S3—C3—O4—C5	3.2 (6)	C13—C14—C15—C16	−1.1 (8)
C3—O4—C5—C6	−171.0 (4)	C14—C15—C16—C11	1.0 (7)
O1—C1—C11—C16	16.9 (7)	C12—C11—C16—C15	−0.2 (7)
N2—C1—C11—C16	−163.3 (4)	C1—C11—C16—C15	−177.7 (4)
O1—C1—C11—C12	−160.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.88	2.05	2.921 (4)	170
C12—H12···S3^i	0.95	2.83	3.606 (4)	139
C12—H12···O1^i	0.95	2.51	3.192 (5)	129
C16—H16···S3^ii	0.95	2.86	3.576 (5)	134

Symmetry codes: (i) x−1/2, −y+3/2, z; (ii) −x+3/2, y+1/2, z−1/2.

(II) O-ethyl (4-methylbenzoyl)thiocarbamate

Crystal data

C11H13NO2S	F(000) = 472
Mr = 223.29	Dx = 1.349 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2026 reflections
a = 12.2845 (14) Å	θ = 3.1–25.5°
b = 9.1431 (17) Å	µ = 0.27 mm^−1
c = 9.7897 (4) Å	T = 120 K
β = 90.182 (7)°	Block, green
V = 1099.6 (2) Å^3	0.34 × 0.30 × 0.24 mm
Z = 4

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2026 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1334 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 9.091 pixels mm^-1	θmax = 25.5°, θmin = 3.1°
ϕ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
Tmin = 0.918, Tmax = 0.937	l = −11→11
11469 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.134	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0646P)^2 + 0.4813P] where P = (Fo^2 + 2Fc^2)/3
2026 reflections	(Δ/σ)max = 0.001
138 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.29 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2612 (2)	0.7412 (3)	0.5728 (3)	0.0330 (7)
O1	0.25886 (19)	0.7948 (2)	0.68555 (18)	0.0497 (6)
N2	0.22197 (17)	0.8125 (2)	0.4599 (2)	0.0300 (5)
H2	0.2288	0.7668	0.3813	0.036*
C3	0.1730 (2)	0.9479 (3)	0.4559 (3)	0.0313 (7)
S3	0.16384 (6)	1.06818 (8)	0.57612 (7)	0.0422 (3)
O4	0.13528 (15)	0.96362 (19)	0.32994 (18)	0.0358 (5)
C5	0.0823 (2)	1.1002 (3)	0.2940 (3)	0.0422 (8)
H5A	0.1358	1.1811	0.2919	0.051*
H5B	0.0250	1.1244	0.3612	0.051*
C6	0.0340 (2)	1.0774 (3)	0.1566 (3)	0.0464 (8)
H6A	0.0916	1.0530	0.0915	0.070*
H6B	−0.0029	1.1671	0.1271	0.070*
H6C	−0.0187	0.9970	0.1605	0.070*
C11	0.3084 (2)	0.5953 (3)	0.5491 (2)	0.0293 (6)
C12	0.2867 (2)	0.5081 (3)	0.4378 (3)	0.0292 (6)
H12	0.2408	0.5436	0.3669	0.035*
C13	0.3304 (2)	0.3710 (3)	0.4279 (3)	0.0310 (6)
H13	0.3131	0.3122	0.3508	0.037*
C14	0.3990 (2)	0.3160 (3)	0.5272 (3)	0.0319 (7)
C15	0.4228 (2)	0.4060 (3)	0.6366 (3)	0.0354 (7)
H15	0.4716	0.3726	0.7053	0.042*
C16	0.3781 (2)	0.5411 (3)	0.6481 (3)	0.0364 (7)
H16	0.3949	0.5995	0.7256	0.044*
C17	0.4463 (2)	0.1660 (3)	0.5182 (3)	0.0417 (8)
H17A	0.4091	0.1110	0.4460	0.062*
H17B	0.4369	0.1157	0.6057	0.062*
H17C	0.5241	0.1729	0.4969	0.062*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0435 (17)	0.0310 (15)	0.0245 (14)	−0.0072 (13)	0.0004 (12)	0.0018 (12)
O1	0.0930 (18)	0.0335 (12)	0.0226 (10)	0.0052 (11)	0.0007 (10)	−0.0019 (9)
N2	0.0395 (13)	0.0276 (12)	0.0229 (11)	0.0011 (11)	0.0005 (10)	−0.0007 (9)
C3	0.0279 (14)	0.0346 (17)	0.0314 (15)	−0.0086 (13)	0.0027 (12)	0.0038 (12)
S3	0.0533 (5)	0.0322 (4)	0.0413 (5)	−0.0006 (4)	−0.0001 (4)	−0.0063 (3)
O4	0.0407 (11)	0.0346 (11)	0.0322 (11)	0.0023 (9)	−0.0023 (9)	0.0048 (8)
C5	0.0384 (17)	0.0328 (17)	0.055 (2)	0.0019 (14)	−0.0029 (15)	0.0118 (14)
C6	0.0385 (17)	0.056 (2)	0.0446 (18)	0.0059 (15)	−0.0024 (14)	0.0141 (15)
C11	0.0349 (15)	0.0313 (15)	0.0216 (14)	−0.0024 (12)	0.0025 (12)	0.0036 (11)
C12	0.0324 (15)	0.0313 (15)	0.0238 (14)	−0.0038 (13)	−0.0008 (11)	0.0034 (12)
C13	0.0378 (16)	0.0294 (15)	0.0259 (14)	−0.0021 (13)	0.0003 (12)	−0.0014 (12)
C14	0.0328 (16)	0.0325 (15)	0.0303 (15)	0.0015 (12)	0.0035 (12)	0.0063 (12)
C15	0.0391 (16)	0.0379 (17)	0.0291 (15)	0.0032 (13)	−0.0041 (13)	0.0074 (13)
C16	0.0470 (18)	0.0399 (18)	0.0222 (14)	−0.0051 (14)	−0.0028 (13)	−0.0002 (12)
C17	0.0433 (18)	0.0409 (18)	0.0408 (17)	0.0098 (15)	0.0007 (14)	0.0057 (14)

Geometric parameters (Å, º)

C1—O1	1.208 (3)	C11—C12	1.376 (4)
C1—N2	1.370 (3)	C11—C16	1.383 (4)
C1—C11	1.473 (4)	C12—C13	1.367 (4)
N2—C3	1.377 (3)	C12—H12	0.9500
N2—H2	0.8800	C13—C14	1.379 (4)
C3—O4	1.324 (3)	C13—H13	0.9500
C3—S3	1.615 (3)	C14—C15	1.381 (4)
O4—C5	1.451 (3)	C14—C17	1.492 (4)
C5—C6	1.483 (4)	C15—C16	1.357 (4)
C5—H5A	0.9900	C15—H15	0.9500
C5—H5B	0.9900	C16—H16	0.9500
C6—H6A	0.9800	C17—H17A	0.9800
C6—H6B	0.9800	C17—H17B	0.9800
C6—H6C	0.9800	C17—H17C	0.9800
O1—C1—N2	122.3 (3)	C12—C11—C1	125.0 (2)
O1—C1—C11	121.5 (2)	C16—C11—C1	117.2 (2)
N2—C1—C11	116.2 (2)	C13—C12—C11	120.8 (2)
C1—N2—C3	127.1 (2)	C13—C12—H12	119.6
C1—N2—H2	116.4	C11—C12—H12	119.6
C3—N2—H2	116.4	C12—C13—C14	121.6 (2)
O4—C3—N2	106.0 (2)	C12—C13—H13	119.2
O4—C3—S3	125.5 (2)	C14—C13—H13	119.2
N2—C3—S3	128.5 (2)	C13—C14—C15	117.2 (2)
C3—O4—C5	118.3 (2)	C13—C14—C17	122.1 (3)
O4—C5—C6	106.1 (2)	C15—C14—C17	120.8 (2)
O4—C5—H5A	110.5	C16—C15—C14	121.5 (2)
C6—C5—H5A	110.5	C16—C15—H15	119.3
O4—C5—H5B	110.5	C14—C15—H15	119.3
C6—C5—H5B	110.5	C15—C16—C11	121.2 (3)
H5A—C5—H5B	108.7	C15—C16—H16	119.4
C5—C6—H6A	109.5	C11—C16—H16	119.4
C5—C6—H6B	109.5	C14—C17—H17A	109.5
H6A—C6—H6B	109.5	C14—C17—H17B	109.5
C5—C6—H6C	109.5	H17A—C17—H17B	109.5
H6A—C6—H6C	109.5	C14—C17—H17C	109.5
H6B—C6—H6C	109.5	H17A—C17—H17C	109.5
C12—C11—C16	117.7 (3)	H17B—C17—H17C	109.5
O1—C1—N2—C3	−2.0 (4)	C16—C11—C12—C13	1.8 (4)
C11—C1—N2—C3	179.0 (2)	C1—C11—C12—C13	−176.8 (2)
C1—N2—C3—O4	−171.7 (2)	C11—C12—C13—C14	−1.2 (4)
C1—N2—C3—S3	9.7 (4)	C12—C13—C14—C15	−0.7 (4)
N2—C3—O4—C5	−177.8 (2)	C12—C13—C14—C17	179.4 (3)
S3—C3—O4—C5	0.9 (3)	C13—C14—C15—C16	1.9 (4)
C3—O4—C5—C6	−171.3 (2)	C17—C14—C15—C16	−178.2 (3)
O1—C1—C11—C12	159.5 (3)	C14—C15—C16—C11	−1.3 (4)
N2—C1—C11—C12	−21.4 (4)	C12—C11—C16—C15	−0.6 (4)
O1—C1—C11—C16	−19.1 (4)	C1—C11—C16—C15	178.1 (3)
N2—C1—C11—C16	160.0 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.88	2.03	2.896 (3)	167
C12—H12···O1^i	0.95	2.32	3.075 (3)	136

Symmetry code: (i) x, −y+3/2, z−1/2.

(III) O,S-diethyl (4-methylbenzoyl)imidothiocarbonate

Crystal data

C13H17NO2S	Z = 2
Mr = 251.35	F(000) = 268
Triclinic, P1	Dx = 1.327 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2470 (16) Å	Cell parameters from 2460 reflections
b = 8.8870 (7) Å	θ = 3.2–26.0°
c = 10.737 (1) Å	µ = 0.25 mm^−1
α = 100.691 (7)°	T = 120 K
β = 99.984 (13)°	Block, colourless
γ = 107.307 (11)°	0.42 × 0.33 × 0.26 mm
V = 629.19 (17) Å^3

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2460 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2064 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
Detector resolution: 9.091 pixels mm^-1	θmax = 26.0°, θmin = 3.2°
ϕ and ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −10→10
Tmin = 0.889, Tmax = 0.938	l = −13→13
2460 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.167	H-atom parameters constrained
S = 1.18	w = 1/[σ^2(Fo^2) + (0.0398P)^2 + 1.4311P] where P = (Fo^2 + 2Fc^2)/3
2460 reflections	(Δ/σ)max = 0.001
158 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2399 (5)	0.3732 (4)	0.3110 (3)	0.0209 (8)
O1	0.2428 (4)	0.4849 (3)	0.2609 (2)	0.0273 (6)
N2	0.2465 (4)	0.3780 (4)	0.4408 (3)	0.0209 (6)
C3	0.2579 (5)	0.5096 (4)	0.5199 (3)	0.0192 (7)
S31	0.26244 (14)	0.69351 (11)	0.48636 (9)	0.0220 (3)
C32	0.2713 (6)	0.8125 (4)	0.6447 (3)	0.0233 (8)
H32A	0.1534	0.7594	0.6756	0.028*
H32B	0.3927	0.8227	0.7092	0.028*
C33	0.2735 (7)	0.9786 (5)	0.6291 (4)	0.0295 (9)
H33A	0.3915	1.0302	0.5993	0.044*
H33B	0.2772	1.0464	0.7133	0.044*
H33C	0.1531	0.9668	0.5646	0.044*
O41	0.2677 (4)	0.5126 (3)	0.6444 (2)	0.0214 (6)
C42	0.2605 (6)	0.3634 (4)	0.6821 (3)	0.0232 (8)
H42A	0.3754	0.3314	0.6652	0.028*
H42B	0.1361	0.2741	0.6320	0.028*
C43	0.2679 (8)	0.3969 (5)	0.8243 (4)	0.0361 (10)
H43A	0.3918	0.4854	0.8725	0.054*
H43B	0.2630	0.2986	0.8545	0.054*
H43C	0.1537	0.4288	0.8395	0.054*
C11	0.2342 (5)	0.2128 (4)	0.2367 (3)	0.0213 (7)
C12	0.2106 (5)	0.0801 (4)	0.2895 (3)	0.0237 (8)
H12	0.1963	0.0905	0.3767	0.028*
C13	0.2074 (6)	−0.0675 (4)	0.2185 (4)	0.0250 (8)
H13	0.1892	−0.1575	0.2566	0.030*
C14	0.2305 (6)	−0.0847 (4)	0.0919 (4)	0.0251 (8)
C15	0.2545 (6)	0.0478 (5)	0.0396 (4)	0.0292 (9)
H15	0.2718	0.0379	−0.0469	0.035*
C16	0.2542 (6)	0.1947 (5)	0.1091 (3)	0.0249 (8)
H16	0.2676	0.2834	0.0697	0.030*
C17	0.2257 (7)	−0.2452 (5)	0.0150 (4)	0.0344 (10)
H17A	0.0910	−0.3060	−0.0399	0.052*
H17B	0.2629	−0.3079	0.0750	0.052*
H17C	0.3201	−0.2268	−0.0405	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0179 (17)	0.0253 (19)	0.0148 (17)	0.0019 (15)	0.0029 (13)	0.0039 (14)
O1	0.0408 (16)	0.0279 (14)	0.0176 (13)	0.0150 (13)	0.0100 (11)	0.0083 (11)
N2	0.0207 (15)	0.0246 (16)	0.0170 (14)	0.0071 (13)	0.0058 (12)	0.0044 (12)
C3	0.0188 (17)	0.0214 (17)	0.0180 (17)	0.0075 (14)	0.0051 (13)	0.0049 (14)
S31	0.0273 (5)	0.0226 (5)	0.0189 (4)	0.0105 (4)	0.0069 (4)	0.0073 (3)
C32	0.0282 (19)	0.0202 (18)	0.0230 (18)	0.0106 (16)	0.0076 (15)	0.0035 (14)
C33	0.041 (2)	0.0215 (19)	0.027 (2)	0.0134 (17)	0.0081 (17)	0.0053 (16)
O41	0.0317 (14)	0.0183 (13)	0.0139 (12)	0.0071 (11)	0.0068 (10)	0.0048 (9)
C42	0.035 (2)	0.0159 (17)	0.0205 (18)	0.0099 (16)	0.0074 (15)	0.0056 (14)
C43	0.066 (3)	0.021 (2)	0.023 (2)	0.013 (2)	0.013 (2)	0.0086 (16)
C11	0.0181 (17)	0.0235 (18)	0.0221 (18)	0.0058 (15)	0.0052 (14)	0.0070 (15)
C12	0.0252 (19)	0.0255 (19)	0.0152 (17)	0.0041 (15)	0.0041 (14)	0.0011 (14)
C13	0.028 (2)	0.0211 (19)	0.0244 (19)	0.0062 (16)	0.0050 (15)	0.0076 (15)
C14	0.0259 (19)	0.0243 (19)	0.0212 (18)	0.0067 (16)	0.0054 (15)	−0.0002 (15)
C15	0.036 (2)	0.034 (2)	0.0180 (18)	0.0126 (18)	0.0088 (16)	0.0041 (15)
C16	0.031 (2)	0.028 (2)	0.0168 (17)	0.0100 (17)	0.0072 (15)	0.0067 (15)
C17	0.043 (2)	0.029 (2)	0.029 (2)	0.0140 (19)	0.0082 (18)	−0.0004 (17)

Geometric parameters (Å, º)

C1—O1	1.210 (4)	C43—H43A	0.9800
C1—N2	1.379 (4)	C43—H43B	0.9800
C1—C11	1.484 (5)	C43—H43C	0.9800
N2—C3	1.283 (4)	C11—C12	1.380 (5)
C3—O41	1.321 (4)	C11—C16	1.386 (5)
C3—S31	1.730 (4)	C12—C13	1.381 (5)
S31—C32	1.807 (4)	C12—H12	0.9500
C32—C33	1.512 (5)	C13—C14	1.384 (5)
C32—H32A	0.9900	C13—H13	0.9500
C32—H32B	0.9900	C14—C15	1.375 (5)
C33—H33A	0.9800	C14—C17	1.497 (5)
C33—H33B	0.9800	C15—C16	1.380 (5)
C33—H33C	0.9800	C15—H15	0.9500
O41—C42	1.445 (4)	C16—H16	0.9500
C42—C43	1.489 (5)	C17—H17A	0.9800
C42—H42A	0.9900	C17—H17B	0.9800
C42—H42B	0.9900	C17—H17C	0.9800
O1—C1—N2	125.7 (3)	H43A—C43—H43B	109.5
O1—C1—C11	122.4 (3)	C42—C43—H43C	109.5
N2—C1—C11	111.9 (3)	H43A—C43—H43C	109.5
C3—N2—C1	120.0 (3)	H43B—C43—H43C	109.5
N2—C3—O41	119.1 (3)	C12—C11—C16	118.3 (3)
N2—C3—S31	128.3 (3)	C12—C11—C1	122.6 (3)
O41—C3—S31	112.6 (2)	C16—C11—C1	119.1 (3)
C3—S31—C32	101.54 (16)	C11—C12—C13	121.4 (3)
C33—C32—S31	107.2 (2)	C11—C12—H12	119.3
C33—C32—H32A	110.3	C13—C12—H12	119.3
S31—C32—H32A	110.3	C12—C13—C14	120.2 (4)
C33—C32—H32B	110.3	C12—C13—H13	119.9
S31—C32—H32B	110.3	C14—C13—H13	119.9
H32A—C32—H32B	108.5	C15—C14—C13	118.2 (3)
C32—C33—H33A	109.5	C15—C14—C17	121.7 (3)
C32—C33—H33B	109.5	C13—C14—C17	120.0 (4)
H33A—C33—H33B	109.5	C14—C15—C16	121.8 (3)
C32—C33—H33C	109.5	C14—C15—H15	119.1
H33A—C33—H33C	109.5	C16—C15—H15	119.1
H33B—C33—H33C	109.5	C15—C16—C11	119.9 (4)
C3—O41—C42	116.9 (3)	C15—C16—H16	120.0
O41—C42—C43	106.4 (3)	C11—C16—H16	120.0
O41—C42—H42A	110.4	C14—C17—H17A	109.5
C43—C42—H42A	110.4	C14—C17—H17B	109.5
O41—C42—H42B	110.4	H17A—C17—H17B	109.5
C43—C42—H42B	110.4	C14—C17—H17C	109.5
H42A—C42—H42B	108.6	H17A—C17—H17C	109.5
C42—C43—H43A	109.5	H17B—C17—H17C	109.5
C42—C43—H43B	109.5
O1—C1—N2—C3	−0.4 (6)	O1—C1—C11—C16	7.0 (5)
C11—C1—N2—C3	177.9 (3)	N2—C1—C11—C16	−171.4 (3)
C1—N2—C3—O41	−178.8 (3)	C16—C11—C12—C13	0.2 (5)
C1—N2—C3—S31	1.3 (5)	C1—C11—C12—C13	−179.5 (3)
N2—C3—S31—C32	178.1 (3)	C11—C12—C13—C14	0.8 (6)
O41—C3—S31—C32	−1.8 (3)	C12—C13—C14—C15	−0.6 (6)
C3—S31—C32—C33	−179.4 (3)	C12—C13—C14—C17	−179.6 (4)
N2—C3—O41—C42	−1.3 (5)	C13—C14—C15—C16	−0.6 (6)
S31—C3—O41—C42	178.7 (3)	C17—C14—C15—C16	178.4 (4)
C3—O41—C42—C43	−178.4 (3)	C14—C15—C16—C11	1.6 (6)
O1—C1—C11—C12	−173.3 (4)	C12—C11—C16—C15	−1.4 (6)
N2—C1—C11—C12	8.3 (5)	C1—C11—C16—C15	178.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C32—H32B···Cg1^i	0.99	2.62	3.554 (5)	158

Symmetry code: (i) −x+1, −y+1, −z+1.

(IV) O,S-diethyl (4-chlorobenzoyl)imidothiocarbonate

Crystal data

C12H14ClNO2S	Z = 2
Mr = 271.75	F(000) = 284
Triclinic, P1	Dx = 1.424 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8028 (14) Å	Cell parameters from 2363 reflections
b = 9.480 (2) Å	θ = 3.1–25.5°
c = 9.860 (2) Å	µ = 0.46 mm^−1
α = 69.545 (13)°	T = 120 K
β = 75.683 (14)°	Block, colourless
γ = 69.548 (15)°	0.52 × 0.45 × 0.29 mm
V = 633.7 (2) Å^3

Data collection

Bruker Nonius KappaCCD area-detector diffractometer	2363 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1707 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 9.091 pixels mm^-1	θmax = 25.5°, θmin = 3.1°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −11→11
Tmin = 0.778, Tmax = 0.879	l = −11→11
14986 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0506P)^2 + 0.5461P] where P = (Fo^2 + 2Fc^2)/3
2363 reflections	(Δ/σ)max = 0.001
156 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.34 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.6593 (4)	0.7556 (3)	0.4431 (3)	0.0240 (6)
O1	0.8135 (3)	0.7656 (2)	0.3846 (2)	0.0325 (5)
N2	0.5661 (3)	0.7985 (3)	0.5679 (2)	0.0226 (5)
C3	0.6490 (4)	0.8421 (3)	0.6362 (3)	0.0223 (6)
S31	0.87215 (10)	0.85769 (9)	0.59107 (8)	0.0268 (2)
C32	0.9012 (4)	0.8995 (3)	0.7480 (3)	0.0273 (7)
H32A	1.0037	0.9474	0.7203	0.033*
H32B	0.7871	0.9771	0.7772	0.033*
C33	0.9421 (4)	0.7544 (4)	0.8772 (3)	0.0328 (7)
H33A	0.8340	0.7146	0.9138	0.049*
H33B	0.9705	0.7812	0.9549	0.049*
H33C	1.0482	0.6733	0.8467	0.049*
O41	0.5607 (2)	0.8827 (2)	0.7565 (2)	0.0251 (5)
C42	0.3756 (4)	0.8675 (4)	0.8099 (3)	0.0292 (7)
H42A	0.3786	0.7553	0.8456	0.035*
H42B	0.2969	0.9224	0.7312	0.035*
C43	0.3037 (4)	0.9407 (3)	0.9311 (3)	0.0304 (7)
H43A	0.3876	0.8894	1.0049	0.046*
H43B	0.1809	0.9281	0.9757	0.046*
H43C	0.2950	1.0529	0.8928	0.046*
C11	0.5539 (4)	0.6970 (3)	0.3790 (3)	0.0211 (6)
C12	0.3699 (4)	0.7069 (3)	0.4287 (3)	0.0236 (6)
H12	0.3088	0.7486	0.5084	0.028*
C13	0.2736 (4)	0.6566 (3)	0.3632 (3)	0.0242 (6)
H13	0.1466	0.6640	0.3968	0.029*
C14	0.3655 (4)	0.5958 (3)	0.2486 (3)	0.0250 (6)
Cl14	0.24405 (10)	0.53734 (8)	0.16335 (8)	0.0315 (2)
C15	0.5495 (4)	0.5827 (3)	0.1988 (3)	0.0263 (6)
H15	0.6109	0.5391	0.1203	0.032*
C16	0.6435 (4)	0.6338 (3)	0.2646 (3)	0.0271 (6)
H16	0.7707	0.6255	0.2311	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0224 (15)	0.0244 (15)	0.0243 (15)	−0.0039 (12)	−0.0070 (12)	−0.0063 (12)
O1	0.0244 (11)	0.0500 (13)	0.0283 (11)	−0.0146 (10)	0.0005 (9)	−0.0167 (10)
N2	0.0184 (12)	0.0261 (13)	0.0247 (12)	−0.0057 (10)	−0.0039 (10)	−0.0094 (10)
C3	0.0234 (15)	0.0206 (14)	0.0207 (14)	−0.0043 (11)	−0.0050 (11)	−0.0041 (11)
S31	0.0216 (4)	0.0374 (4)	0.0246 (4)	−0.0120 (3)	−0.0027 (3)	−0.0100 (3)
C32	0.0236 (15)	0.0363 (17)	0.0279 (16)	−0.0130 (13)	−0.0067 (12)	−0.0096 (13)
C33	0.0324 (17)	0.0354 (17)	0.0326 (17)	−0.0061 (14)	−0.0099 (14)	−0.0124 (14)
O41	0.0182 (10)	0.0317 (11)	0.0281 (11)	−0.0085 (8)	−0.0015 (8)	−0.0118 (9)
C42	0.0195 (15)	0.0390 (18)	0.0338 (17)	−0.0119 (13)	0.0012 (12)	−0.0161 (14)
C43	0.0308 (17)	0.0314 (17)	0.0304 (16)	−0.0111 (14)	−0.0012 (13)	−0.0106 (13)
C11	0.0220 (14)	0.0191 (13)	0.0192 (13)	−0.0038 (11)	−0.0055 (11)	−0.0022 (11)
C12	0.0218 (14)	0.0223 (14)	0.0261 (15)	−0.0045 (12)	−0.0051 (11)	−0.0072 (12)
C13	0.0210 (15)	0.0256 (15)	0.0251 (15)	−0.0052 (12)	−0.0039 (12)	−0.0075 (12)
C14	0.0319 (16)	0.0220 (14)	0.0220 (15)	−0.0074 (12)	−0.0092 (12)	−0.0045 (12)
Cl14	0.0374 (5)	0.0333 (4)	0.0305 (4)	−0.0114 (3)	−0.0119 (3)	−0.0112 (3)
C15	0.0278 (16)	0.0285 (16)	0.0217 (15)	−0.0048 (13)	−0.0024 (12)	−0.0103 (12)
C16	0.0247 (15)	0.0279 (15)	0.0260 (15)	−0.0059 (12)	−0.0021 (12)	−0.0076 (12)

Geometric parameters (Å, º)

C1—O1	1.220 (3)	C42—H42B	0.9900
C1—N2	1.382 (3)	C43—H43A	0.9800
C1—C11	1.485 (4)	C43—H43B	0.9800
N2—C3	1.281 (3)	C43—H43C	0.9800
C3—O41	1.326 (3)	C11—C12	1.379 (4)
C3—S31	1.733 (3)	C11—C16	1.382 (4)
S31—C32	1.808 (3)	C12—C13	1.384 (4)
C32—C33	1.512 (4)	C12—H12	0.9500
C32—H32A	0.9900	C13—C14	1.375 (4)
C32—H32B	0.9900	C13—H13	0.9500
C33—H33A	0.9800	C14—C15	1.373 (4)
C33—H33B	0.9800	C14—Cl14	1.731 (3)
C33—H33C	0.9800	C15—C16	1.377 (4)
O41—C42	1.449 (3)	C15—H15	0.9500
C42—C43	1.484 (4)	C16—H16	0.9500
C42—H42A	0.9900
O1—C1—N2	125.1 (3)	H42A—C42—H42B	108.7
O1—C1—C11	120.5 (2)	C42—C43—H43A	109.5
N2—C1—C11	114.4 (2)	C42—C43—H43B	109.5
C3—N2—C1	119.2 (2)	H43A—C43—H43B	109.5
N2—C3—O41	119.5 (2)	C42—C43—H43C	109.5
N2—C3—S31	127.9 (2)	H43A—C43—H43C	109.5
O41—C3—S31	112.63 (19)	H43B—C43—H43C	109.5
C3—S31—C32	102.47 (13)	C12—C11—C16	119.7 (3)
C33—C32—S31	112.8 (2)	C12—C11—C1	121.8 (2)
C33—C32—H32A	109.0	C16—C11—C1	118.5 (3)
S31—C32—H32A	109.0	C11—C12—C13	120.5 (3)
C33—C32—H32B	109.0	C11—C12—H12	119.8
S31—C32—H32B	109.0	C13—C12—H12	119.8
H32A—C32—H32B	107.8	C14—C13—C12	118.6 (3)
C32—C33—H33A	109.5	C14—C13—H13	120.7
C32—C33—H33B	109.5	C12—C13—H13	120.7
H33A—C33—H33B	109.5	C15—C14—C13	121.8 (3)
C32—C33—H33C	109.5	C15—C14—Cl14	119.4 (2)
H33A—C33—H33C	109.5	C13—C14—Cl14	118.8 (2)
H33B—C33—H33C	109.5	C14—C15—C16	119.0 (3)
C3—O41—C42	118.0 (2)	C14—C15—H15	120.5
O41—C42—C43	105.8 (2)	C16—C15—H15	120.5
O41—C42—H42A	110.6	C15—C16—C11	120.4 (3)
C43—C42—H42A	110.6	C15—C16—H16	119.8
O41—C42—H42B	110.6	C11—C16—H16	119.8
C43—C42—H42B	110.6
O1—C1—N2—C3	−5.3 (4)	O1—C1—C11—C16	9.0 (4)
C11—C1—N2—C3	176.1 (2)	N2—C1—C11—C16	−172.4 (2)
C1—N2—C3—O41	−179.6 (2)	C16—C11—C12—C13	−1.1 (4)
C1—N2—C3—S31	0.7 (4)	C1—C11—C12—C13	177.6 (2)
N2—C3—S31—C32	−172.7 (3)	C11—C12—C13—C14	0.4 (4)
O41—C3—S31—C32	7.7 (2)	C12—C13—C14—C15	0.5 (4)
C3—S31—C32—C33	78.7 (2)	C12—C13—C14—Cl14	−178.4 (2)
N2—C3—O41—C42	3.2 (4)	C13—C14—C15—C16	−0.8 (4)
S31—C3—O41—C42	−177.08 (19)	Cl14—C14—C15—C16	178.1 (2)
C3—O41—C42—C43	−172.5 (2)	C14—C15—C16—C11	0.1 (4)
O1—C1—C11—C12	−169.8 (3)	C12—C11—C16—C15	0.9 (4)
N2—C1—C11—C12	8.9 (4)	C1—C11—C16—C15	−177.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1^i	0.95	2.45	3.345 (4)	156

Symmetry code: (i) x−1, y, z.