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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110005032/fa3214sup1.cif
Contains datablocks global, I, II, III, IV

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110005032/fa3214Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110005032/fa3214IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110005032/fa3214IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110005032/fa3214IVsup5.hkl
Contains datablock IV

CCDC references: 774090; 774091; 774092; 774093

Comment top

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 CO and CS 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 CS 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 N2C3. 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 ππ 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 ππ 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, ππ 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 ππ 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.

Experimental top

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.

Refinement top

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 Uiso(H) = kUeq(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 top

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 top
[Figure 1] 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.
[Figure 2] Fig. 2. Part of the crystal structure of (I), showing the formation of a ribbon along [100] containing R21(6) and R12(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 ($) or an ampersand (&) are at the symmetry positions (-1/2 + x, 3/2 - y, z) (-1 + x, y, z), (1/2 + x, 3/2 - y, z) and (1 + x, y, z), respectively.
[Figure 3] Fig. 3. Part of the crystal structure of (I), showing the formation of a C(7) chain along [011]. For the sake of clarity, H atoms not involved in the motifs shown have been omitted. Atoms marked with an asterisk (*), a hash symbol (#) or a dollar sign ($) 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.
[Figure 4] Fig. 4. Part of the crystal structure of (II), showing the formation of a chain of R12(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.
[Figure 5] 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.
[Figure 6] 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).
[Figure 7] 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 top
Crystal data top
C10H11NO2SF(000) = 440
Mr = 209.27Dx = 1.366 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 1889 reflections
a = 9.9418 (8) Åθ = 2.9–25.5°
b = 9.3619 (5) ŵ = 0.29 mm1
c = 10.9337 (13) ÅT = 120 K
V = 1017.65 (16) Å3Block, green
Z = 40.50 × 0.42 × 0.41 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
1889 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1284 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.074
Detector resolution: 9.091 pixels mm-1θmax = 25.5°, θmin = 2.9°
ϕ and ω scansh = 1211
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1111
Tmin = 0.868, Tmax = 0.890l = 1313
13852 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.130 w = 1/[σ2(Fo2) + (0.0546P)2 + 0.655P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max = 0.001
1889 reflectionsΔρmax = 0.45 e Å3
128 parametersΔρmin = 0.29 e Å3
1 restraintAbsolute structure: Flack (1983), with 890 Bijvoet pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.08 (17)
Crystal data top
C10H11NO2SV = 1017.65 (16) Å3
Mr = 209.27Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 9.9418 (8) ŵ = 0.29 mm1
b = 9.3619 (5) ÅT = 120 K
c = 10.9337 (13) Å0.50 × 0.42 × 0.41 mm
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
1889 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1284 reflections with I > 2σ(I)
Tmin = 0.868, Tmax = 0.890Rint = 0.074
13852 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.130Δρmax = 0.45 e Å3
S = 1.14Δρmin = 0.29 e Å3
1889 reflectionsAbsolute structure: Flack (1983), with 890 Bijvoet pairs
128 parametersAbsolute structure parameter: 0.08 (17)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.5732 (4)0.7797 (5)0.2183 (4)0.0260 (10)
O10.6860 (3)0.7329 (3)0.2110 (3)0.0307 (7)
N20.4670 (3)0.6998 (4)0.2635 (3)0.0270 (9)
H20.38570.73100.24610.032*
C30.4743 (4)0.5764 (5)0.3329 (4)0.0279 (10)
S30.60817 (10)0.49807 (13)0.38277 (14)0.0356 (3)
O40.3488 (3)0.5368 (3)0.3554 (3)0.0362 (9)
C50.3277 (5)0.4172 (5)0.4363 (5)0.0337 (11)
H5A0.35270.44290.52120.040*
H5B0.38280.33450.41030.040*
C60.1807 (4)0.3815 (5)0.4290 (5)0.0365 (12)
H6A0.12740.46670.44790.055*
H6B0.15960.30590.48800.055*
H6C0.15900.34850.34620.055*
C110.5382 (4)0.9261 (5)0.1803 (4)0.0300 (11)
C120.4230 (4)0.9969 (4)0.2190 (4)0.0262 (10)
H120.35960.94910.26950.031*
C130.4006 (4)1.1359 (5)0.1842 (5)0.0342 (12)
H130.32211.18430.21120.041*
C140.4913 (5)1.2049 (5)0.1106 (5)0.0387 (12)
H140.47531.30120.08740.046*
C150.6053 (4)1.1359 (5)0.0700 (4)0.0328 (12)
H150.66711.18370.01780.039*
C160.6287 (5)0.9976 (4)0.1058 (5)0.0269 (10)
H160.70790.95020.07910.032*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.021 (2)0.031 (3)0.027 (2)0.0004 (19)0.0034 (19)0.006 (2)
O10.0219 (15)0.0322 (17)0.0380 (18)0.0010 (13)0.0002 (14)0.0041 (15)
N20.0190 (18)0.029 (2)0.033 (2)0.0024 (16)0.0011 (16)0.0025 (18)
C30.033 (3)0.021 (2)0.029 (3)0.002 (2)0.002 (2)0.007 (2)
S30.0267 (5)0.0359 (6)0.0441 (6)0.0034 (5)0.0018 (7)0.0087 (5)
O40.0270 (17)0.0363 (17)0.045 (2)0.0023 (13)0.0020 (15)0.0123 (16)
C50.033 (3)0.029 (2)0.039 (3)0.000 (2)0.004 (2)0.011 (2)
C60.035 (3)0.034 (3)0.040 (3)0.004 (2)0.003 (2)0.007 (2)
C110.027 (3)0.031 (2)0.032 (3)0.005 (2)0.002 (2)0.005 (2)
C120.024 (2)0.028 (2)0.026 (2)0.0015 (18)0.0010 (19)0.000 (2)
C130.029 (3)0.031 (3)0.042 (3)0.003 (2)0.001 (2)0.000 (2)
C140.040 (3)0.029 (2)0.047 (3)0.005 (2)0.004 (2)0.003 (2)
C150.029 (3)0.034 (3)0.035 (3)0.010 (2)0.006 (2)0.008 (2)
C160.024 (2)0.027 (2)0.030 (2)0.001 (2)0.0035 (18)0.005 (2)
Geometric parameters (Å, º) top
C1—O11.206 (5)C6—H6C0.9800
C1—N21.385 (5)C11—C161.386 (6)
C1—C111.473 (6)C11—C121.389 (6)
N2—C31.384 (6)C12—C131.374 (6)
N2—H20.8800C12—H120.9500
C3—O41.325 (5)C13—C141.369 (7)
C3—S31.615 (4)C13—H130.9500
O4—C51.443 (5)C14—C151.378 (6)
C5—C61.501 (6)C14—H140.9500
C5—H5A0.9900C15—C161.373 (6)
C5—H5B0.9900C15—H150.9500
C6—H6A0.9800C16—H160.9500
C6—H6B0.9800
O1—C1—N2122.4 (4)H6A—C6—H6C109.5
O1—C1—C11122.6 (4)H6B—C6—H6C109.5
N2—C1—C11115.0 (4)C16—C11—C12118.9 (4)
C3—N2—C1127.3 (4)C16—C11—C1117.5 (4)
C3—N2—H2116.3C12—C11—C1123.6 (4)
C1—N2—H2116.3C13—C12—C11120.1 (4)
O4—C3—N2106.6 (3)C13—C12—H12120.0
O4—C3—S3125.9 (3)C11—C12—H12120.0
N2—C3—S3127.4 (3)C14—C13—C12120.2 (4)
C3—O4—C5117.9 (4)C14—C13—H13119.9
O4—C5—C6106.3 (4)C12—C13—H13119.9
O4—C5—H5A110.5C13—C14—C15120.7 (4)
C6—C5—H5A110.5C13—C14—H14119.7
O4—C5—H5B110.5C15—C14—H14119.7
C6—C5—H5B110.5C16—C15—C14119.3 (4)
H5A—C5—H5B108.7C16—C15—H15120.4
C5—C6—H6A109.5C14—C15—H15120.4
C5—C6—H6B109.5C15—C16—C11120.9 (4)
H6A—C6—H6B109.5C15—C16—H16119.6
C5—C6—H6C109.5C11—C16—H16119.6
O1—C1—N2—C317.4 (6)N2—C1—C11—C1219.3 (6)
C11—C1—N2—C3162.4 (4)C16—C11—C12—C130.5 (6)
C1—N2—C3—O4179.9 (4)C1—C11—C12—C13176.8 (5)
C1—N2—C3—S32.5 (6)C11—C12—C13—C140.4 (7)
N2—C3—O4—C5174.4 (4)C12—C13—C14—C150.4 (8)
S3—C3—O4—C53.2 (6)C13—C14—C15—C161.1 (8)
C3—O4—C5—C6171.0 (4)C14—C15—C16—C111.0 (7)
O1—C1—C11—C1616.9 (7)C12—C11—C16—C150.2 (7)
N2—C1—C11—C16163.3 (4)C1—C11—C16—C15177.7 (4)
O1—C1—C11—C12160.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.882.052.921 (4)170
C12—H12···S3i0.952.833.606 (4)139
C12—H12···O1i0.952.513.192 (5)129
C16—H16···S3ii0.952.863.576 (5)134
Symmetry codes: (i) x1/2, y+3/2, z; (ii) x+3/2, y+1/2, z1/2.
(II) O-ethyl (4-methylbenzoyl)thiocarbamate top
Crystal data top
C11H13NO2SF(000) = 472
Mr = 223.29Dx = 1.349 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2026 reflections
a = 12.2845 (14) Åθ = 3.1–25.5°
b = 9.1431 (17) ŵ = 0.27 mm1
c = 9.7897 (4) ÅT = 120 K
β = 90.182 (7)°Block, green
V = 1099.6 (2) Å30.34 × 0.30 × 0.24 mm
Z = 4
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2026 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1334 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
Detector resolution: 9.091 pixels mm-1θmax = 25.5°, θmin = 3.1°
ϕ and ω scansh = 1414
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1111
Tmin = 0.918, Tmax = 0.937l = 1111
11469 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0646P)2 + 0.4813P]
where P = (Fo2 + 2Fc2)/3
2026 reflections(Δ/σ)max = 0.001
138 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.29 e Å3
Crystal data top
C11H13NO2SV = 1099.6 (2) Å3
Mr = 223.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.2845 (14) ŵ = 0.27 mm1
b = 9.1431 (17) ÅT = 120 K
c = 9.7897 (4) Å0.34 × 0.30 × 0.24 mm
β = 90.182 (7)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2026 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1334 reflections with I > 2σ(I)
Tmin = 0.918, Tmax = 0.937Rint = 0.051
11469 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.134H-atom parameters constrained
S = 1.07Δρmax = 0.31 e Å3
2026 reflectionsΔρmin = 0.29 e Å3
138 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2612 (2)0.7412 (3)0.5728 (3)0.0330 (7)
O10.25886 (19)0.7948 (2)0.68555 (18)0.0497 (6)
N20.22197 (17)0.8125 (2)0.4599 (2)0.0300 (5)
H20.22880.76680.38130.036*
C30.1730 (2)0.9479 (3)0.4559 (3)0.0313 (7)
S30.16384 (6)1.06818 (8)0.57612 (7)0.0422 (3)
O40.13528 (15)0.96362 (19)0.32994 (18)0.0358 (5)
C50.0823 (2)1.1002 (3)0.2940 (3)0.0422 (8)
H5A0.13581.18110.29190.051*
H5B0.02501.12440.36120.051*
C60.0340 (2)1.0774 (3)0.1566 (3)0.0464 (8)
H6A0.09161.05300.09150.070*
H6B0.00291.16710.12710.070*
H6C0.01870.99700.16050.070*
C110.3084 (2)0.5953 (3)0.5491 (2)0.0293 (6)
C120.2867 (2)0.5081 (3)0.4378 (3)0.0292 (6)
H120.24080.54360.36690.035*
C130.3304 (2)0.3710 (3)0.4279 (3)0.0310 (6)
H130.31310.31220.35080.037*
C140.3990 (2)0.3160 (3)0.5272 (3)0.0319 (7)
C150.4228 (2)0.4060 (3)0.6366 (3)0.0354 (7)
H150.47160.37260.70530.042*
C160.3781 (2)0.5411 (3)0.6481 (3)0.0364 (7)
H160.39490.59950.72560.044*
C170.4463 (2)0.1660 (3)0.5182 (3)0.0417 (8)
H17A0.40910.11100.44600.062*
H17B0.43690.11570.60570.062*
H17C0.52410.17290.49690.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0435 (17)0.0310 (15)0.0245 (14)0.0072 (13)0.0004 (12)0.0018 (12)
O10.0930 (18)0.0335 (12)0.0226 (10)0.0052 (11)0.0007 (10)0.0019 (9)
N20.0395 (13)0.0276 (12)0.0229 (11)0.0011 (11)0.0005 (10)0.0007 (9)
C30.0279 (14)0.0346 (17)0.0314 (15)0.0086 (13)0.0027 (12)0.0038 (12)
S30.0533 (5)0.0322 (4)0.0413 (5)0.0006 (4)0.0001 (4)0.0063 (3)
O40.0407 (11)0.0346 (11)0.0322 (11)0.0023 (9)0.0023 (9)0.0048 (8)
C50.0384 (17)0.0328 (17)0.055 (2)0.0019 (14)0.0029 (15)0.0118 (14)
C60.0385 (17)0.056 (2)0.0446 (18)0.0059 (15)0.0024 (14)0.0141 (15)
C110.0349 (15)0.0313 (15)0.0216 (14)0.0024 (12)0.0025 (12)0.0036 (11)
C120.0324 (15)0.0313 (15)0.0238 (14)0.0038 (13)0.0008 (11)0.0034 (12)
C130.0378 (16)0.0294 (15)0.0259 (14)0.0021 (13)0.0003 (12)0.0014 (12)
C140.0328 (16)0.0325 (15)0.0303 (15)0.0015 (12)0.0035 (12)0.0063 (12)
C150.0391 (16)0.0379 (17)0.0291 (15)0.0032 (13)0.0041 (13)0.0074 (13)
C160.0470 (18)0.0399 (18)0.0222 (14)0.0051 (14)0.0028 (13)0.0002 (12)
C170.0433 (18)0.0409 (18)0.0408 (17)0.0098 (15)0.0007 (14)0.0057 (14)
Geometric parameters (Å, º) top
C1—O11.208 (3)C11—C121.376 (4)
C1—N21.370 (3)C11—C161.383 (4)
C1—C111.473 (4)C12—C131.367 (4)
N2—C31.377 (3)C12—H120.9500
N2—H20.8800C13—C141.379 (4)
C3—O41.324 (3)C13—H130.9500
C3—S31.615 (3)C14—C151.381 (4)
O4—C51.451 (3)C14—C171.492 (4)
C5—C61.483 (4)C15—C161.357 (4)
C5—H5A0.9900C15—H150.9500
C5—H5B0.9900C16—H160.9500
C6—H6A0.9800C17—H17A0.9800
C6—H6B0.9800C17—H17B0.9800
C6—H6C0.9800C17—H17C0.9800
O1—C1—N2122.3 (3)C12—C11—C1125.0 (2)
O1—C1—C11121.5 (2)C16—C11—C1117.2 (2)
N2—C1—C11116.2 (2)C13—C12—C11120.8 (2)
C1—N2—C3127.1 (2)C13—C12—H12119.6
C1—N2—H2116.4C11—C12—H12119.6
C3—N2—H2116.4C12—C13—C14121.6 (2)
O4—C3—N2106.0 (2)C12—C13—H13119.2
O4—C3—S3125.5 (2)C14—C13—H13119.2
N2—C3—S3128.5 (2)C13—C14—C15117.2 (2)
C3—O4—C5118.3 (2)C13—C14—C17122.1 (3)
O4—C5—C6106.1 (2)C15—C14—C17120.8 (2)
O4—C5—H5A110.5C16—C15—C14121.5 (2)
C6—C5—H5A110.5C16—C15—H15119.3
O4—C5—H5B110.5C14—C15—H15119.3
C6—C5—H5B110.5C15—C16—C11121.2 (3)
H5A—C5—H5B108.7C15—C16—H16119.4
C5—C6—H6A109.5C11—C16—H16119.4
C5—C6—H6B109.5C14—C17—H17A109.5
H6A—C6—H6B109.5C14—C17—H17B109.5
C5—C6—H6C109.5H17A—C17—H17B109.5
H6A—C6—H6C109.5C14—C17—H17C109.5
H6B—C6—H6C109.5H17A—C17—H17C109.5
C12—C11—C16117.7 (3)H17B—C17—H17C109.5
O1—C1—N2—C32.0 (4)C16—C11—C12—C131.8 (4)
C11—C1—N2—C3179.0 (2)C1—C11—C12—C13176.8 (2)
C1—N2—C3—O4171.7 (2)C11—C12—C13—C141.2 (4)
C1—N2—C3—S39.7 (4)C12—C13—C14—C150.7 (4)
N2—C3—O4—C5177.8 (2)C12—C13—C14—C17179.4 (3)
S3—C3—O4—C50.9 (3)C13—C14—C15—C161.9 (4)
C3—O4—C5—C6171.3 (2)C17—C14—C15—C16178.2 (3)
O1—C1—C11—C12159.5 (3)C14—C15—C16—C111.3 (4)
N2—C1—C11—C1221.4 (4)C12—C11—C16—C150.6 (4)
O1—C1—C11—C1619.1 (4)C1—C11—C16—C15178.1 (3)
N2—C1—C11—C16160.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.882.032.896 (3)167
C12—H12···O1i0.952.323.075 (3)136
Symmetry code: (i) x, y+3/2, z1/2.
(III) O,S-diethyl (4-methylbenzoyl)imidothiocarbonate top
Crystal data top
C13H17NO2SZ = 2
Mr = 251.35F(000) = 268
Triclinic, P1Dx = 1.327 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.2470 (16) ÅCell parameters from 2460 reflections
b = 8.8870 (7) Åθ = 3.2–26.0°
c = 10.737 (1) ŵ = 0.25 mm1
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) Å3
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2460 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode2064 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.000
Detector resolution: 9.091 pixels mm-1θmax = 26.0°, θmin = 3.2°
ϕ and ω scansh = 88
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1010
Tmin = 0.889, Tmax = 0.938l = 1313
2460 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.167H-atom parameters constrained
S = 1.18 w = 1/[σ2(Fo2) + (0.0398P)2 + 1.4311P]
where P = (Fo2 + 2Fc2)/3
2460 reflections(Δ/σ)max = 0.001
158 parametersΔρmax = 0.71 e Å3
0 restraintsΔρmin = 0.46 e Å3
Crystal data top
C13H17NO2Sγ = 107.307 (11)°
Mr = 251.35V = 629.19 (17) Å3
Triclinic, P1Z = 2
a = 7.2470 (16) ÅMo Kα radiation
b = 8.8870 (7) ŵ = 0.25 mm1
c = 10.737 (1) ÅT = 120 K
α = 100.691 (7)°0.42 × 0.33 × 0.26 mm
β = 99.984 (13)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2460 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
2064 reflections with I > 2σ(I)
Tmin = 0.889, Tmax = 0.938Rint = 0.000
2460 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.167H-atom parameters constrained
S = 1.18Δρmax = 0.71 e Å3
2460 reflectionsΔρmin = 0.46 e Å3
158 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2399 (5)0.3732 (4)0.3110 (3)0.0209 (8)
O10.2428 (4)0.4849 (3)0.2609 (2)0.0273 (6)
N20.2465 (4)0.3780 (4)0.4408 (3)0.0209 (6)
C30.2579 (5)0.5096 (4)0.5199 (3)0.0192 (7)
S310.26244 (14)0.69351 (11)0.48636 (9)0.0220 (3)
C320.2713 (6)0.8125 (4)0.6447 (3)0.0233 (8)
H32A0.15340.75940.67560.028*
H32B0.39270.82270.70920.028*
C330.2735 (7)0.9786 (5)0.6291 (4)0.0295 (9)
H33A0.39151.03020.59930.044*
H33B0.27721.04640.71330.044*
H33C0.15310.96680.56460.044*
O410.2677 (4)0.5126 (3)0.6444 (2)0.0214 (6)
C420.2605 (6)0.3634 (4)0.6821 (3)0.0232 (8)
H42A0.37540.33140.66520.028*
H42B0.13610.27410.63200.028*
C430.2679 (8)0.3969 (5)0.8243 (4)0.0361 (10)
H43A0.39180.48540.87250.054*
H43B0.26300.29860.85450.054*
H43C0.15370.42880.83950.054*
C110.2342 (5)0.2128 (4)0.2367 (3)0.0213 (7)
C120.2106 (5)0.0801 (4)0.2895 (3)0.0237 (8)
H120.19630.09050.37670.028*
C130.2074 (6)0.0675 (4)0.2185 (4)0.0250 (8)
H130.18920.15750.25660.030*
C140.2305 (6)0.0847 (4)0.0919 (4)0.0251 (8)
C150.2545 (6)0.0478 (5)0.0396 (4)0.0292 (9)
H150.27180.03790.04690.035*
C160.2542 (6)0.1947 (5)0.1091 (3)0.0249 (8)
H160.26760.28340.06970.030*
C170.2257 (7)0.2452 (5)0.0150 (4)0.0344 (10)
H17A0.09100.30600.03990.052*
H17B0.26290.30790.07500.052*
H17C0.32010.22680.04050.052*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0179 (17)0.0253 (19)0.0148 (17)0.0019 (15)0.0029 (13)0.0039 (14)
O10.0408 (16)0.0279 (14)0.0176 (13)0.0150 (13)0.0100 (11)0.0083 (11)
N20.0207 (15)0.0246 (16)0.0170 (14)0.0071 (13)0.0058 (12)0.0044 (12)
C30.0188 (17)0.0214 (17)0.0180 (17)0.0075 (14)0.0051 (13)0.0049 (14)
S310.0273 (5)0.0226 (5)0.0189 (4)0.0105 (4)0.0069 (4)0.0073 (3)
C320.0282 (19)0.0202 (18)0.0230 (18)0.0106 (16)0.0076 (15)0.0035 (14)
C330.041 (2)0.0215 (19)0.027 (2)0.0134 (17)0.0081 (17)0.0053 (16)
O410.0317 (14)0.0183 (13)0.0139 (12)0.0071 (11)0.0068 (10)0.0048 (9)
C420.035 (2)0.0159 (17)0.0205 (18)0.0099 (16)0.0074 (15)0.0056 (14)
C430.066 (3)0.021 (2)0.023 (2)0.013 (2)0.013 (2)0.0086 (16)
C110.0181 (17)0.0235 (18)0.0221 (18)0.0058 (15)0.0052 (14)0.0070 (15)
C120.0252 (19)0.0255 (19)0.0152 (17)0.0041 (15)0.0041 (14)0.0011 (14)
C130.028 (2)0.0211 (19)0.0244 (19)0.0062 (16)0.0050 (15)0.0076 (15)
C140.0259 (19)0.0243 (19)0.0212 (18)0.0067 (16)0.0054 (15)0.0002 (15)
C150.036 (2)0.034 (2)0.0180 (18)0.0126 (18)0.0088 (16)0.0041 (15)
C160.031 (2)0.028 (2)0.0168 (17)0.0100 (17)0.0072 (15)0.0067 (15)
C170.043 (2)0.029 (2)0.029 (2)0.0140 (19)0.0082 (18)0.0004 (17)
Geometric parameters (Å, º) top
C1—O11.210 (4)C43—H43A0.9800
C1—N21.379 (4)C43—H43B0.9800
C1—C111.484 (5)C43—H43C0.9800
N2—C31.283 (4)C11—C121.380 (5)
C3—O411.321 (4)C11—C161.386 (5)
C3—S311.730 (4)C12—C131.381 (5)
S31—C321.807 (4)C12—H120.9500
C32—C331.512 (5)C13—C141.384 (5)
C32—H32A0.9900C13—H130.9500
C32—H32B0.9900C14—C151.375 (5)
C33—H33A0.9800C14—C171.497 (5)
C33—H33B0.9800C15—C161.380 (5)
C33—H33C0.9800C15—H150.9500
O41—C421.445 (4)C16—H160.9500
C42—C431.489 (5)C17—H17A0.9800
C42—H42A0.9900C17—H17B0.9800
C42—H42B0.9900C17—H17C0.9800
O1—C1—N2125.7 (3)H43A—C43—H43B109.5
O1—C1—C11122.4 (3)C42—C43—H43C109.5
N2—C1—C11111.9 (3)H43A—C43—H43C109.5
C3—N2—C1120.0 (3)H43B—C43—H43C109.5
N2—C3—O41119.1 (3)C12—C11—C16118.3 (3)
N2—C3—S31128.3 (3)C12—C11—C1122.6 (3)
O41—C3—S31112.6 (2)C16—C11—C1119.1 (3)
C3—S31—C32101.54 (16)C11—C12—C13121.4 (3)
C33—C32—S31107.2 (2)C11—C12—H12119.3
C33—C32—H32A110.3C13—C12—H12119.3
S31—C32—H32A110.3C12—C13—C14120.2 (4)
C33—C32—H32B110.3C12—C13—H13119.9
S31—C32—H32B110.3C14—C13—H13119.9
H32A—C32—H32B108.5C15—C14—C13118.2 (3)
C32—C33—H33A109.5C15—C14—C17121.7 (3)
C32—C33—H33B109.5C13—C14—C17120.0 (4)
H33A—C33—H33B109.5C14—C15—C16121.8 (3)
C32—C33—H33C109.5C14—C15—H15119.1
H33A—C33—H33C109.5C16—C15—H15119.1
H33B—C33—H33C109.5C15—C16—C11119.9 (4)
C3—O41—C42116.9 (3)C15—C16—H16120.0
O41—C42—C43106.4 (3)C11—C16—H16120.0
O41—C42—H42A110.4C14—C17—H17A109.5
C43—C42—H42A110.4C14—C17—H17B109.5
O41—C42—H42B110.4H17A—C17—H17B109.5
C43—C42—H42B110.4C14—C17—H17C109.5
H42A—C42—H42B108.6H17A—C17—H17C109.5
C42—C43—H43A109.5H17B—C17—H17C109.5
C42—C43—H43B109.5
O1—C1—N2—C30.4 (6)O1—C1—C11—C167.0 (5)
C11—C1—N2—C3177.9 (3)N2—C1—C11—C16171.4 (3)
C1—N2—C3—O41178.8 (3)C16—C11—C12—C130.2 (5)
C1—N2—C3—S311.3 (5)C1—C11—C12—C13179.5 (3)
N2—C3—S31—C32178.1 (3)C11—C12—C13—C140.8 (6)
O41—C3—S31—C321.8 (3)C12—C13—C14—C150.6 (6)
C3—S31—C32—C33179.4 (3)C12—C13—C14—C17179.6 (4)
N2—C3—O41—C421.3 (5)C13—C14—C15—C160.6 (6)
S31—C3—O41—C42178.7 (3)C17—C14—C15—C16178.4 (4)
C3—O41—C42—C43178.4 (3)C14—C15—C16—C111.6 (6)
O1—C1—C11—C12173.3 (4)C12—C11—C16—C151.4 (6)
N2—C1—C11—C128.3 (5)C1—C11—C16—C15178.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C32—H32B···Cg1i0.992.623.554 (5)158
Symmetry code: (i) x+1, y+1, z+1.
(IV) O,S-diethyl (4-chlorobenzoyl)imidothiocarbonate top
Crystal data top
C12H14ClNO2SZ = 2
Mr = 271.75F(000) = 284
Triclinic, P1Dx = 1.424 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8028 (14) ÅCell parameters from 2363 reflections
b = 9.480 (2) Åθ = 3.1–25.5°
c = 9.860 (2) ŵ = 0.46 mm1
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) Å3
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2363 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode1707 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
Detector resolution: 9.091 pixels mm-1θmax = 25.5°, θmin = 3.1°
ϕ and ω scansh = 99
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
k = 1111
Tmin = 0.778, Tmax = 0.879l = 1111
14986 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H-atom parameters constrained
S = 1.12 w = 1/[σ2(Fo2) + (0.0506P)2 + 0.5461P]
where P = (Fo2 + 2Fc2)/3
2363 reflections(Δ/σ)max = 0.001
156 parametersΔρmax = 0.49 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C12H14ClNO2Sγ = 69.548 (15)°
Mr = 271.75V = 633.7 (2) Å3
Triclinic, P1Z = 2
a = 7.8028 (14) ÅMo Kα radiation
b = 9.480 (2) ŵ = 0.46 mm1
c = 9.860 (2) ÅT = 120 K
α = 69.545 (13)°0.52 × 0.45 × 0.29 mm
β = 75.683 (14)°
Data collection top
Bruker Nonius KappaCCD area-detector
diffractometer
2363 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1707 reflections with I > 2σ(I)
Tmin = 0.778, Tmax = 0.879Rint = 0.051
14986 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.119H-atom parameters constrained
S = 1.12Δρmax = 0.49 e Å3
2363 reflectionsΔρmin = 0.34 e Å3
156 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.6593 (4)0.7556 (3)0.4431 (3)0.0240 (6)
O10.8135 (3)0.7656 (2)0.3846 (2)0.0325 (5)
N20.5661 (3)0.7985 (3)0.5679 (2)0.0226 (5)
C30.6490 (4)0.8421 (3)0.6362 (3)0.0223 (6)
S310.87215 (10)0.85769 (9)0.59107 (8)0.0268 (2)
C320.9012 (4)0.8995 (3)0.7480 (3)0.0273 (7)
H32A1.00370.94740.72030.033*
H32B0.78710.97710.77720.033*
C330.9421 (4)0.7544 (4)0.8772 (3)0.0328 (7)
H33A0.83400.71460.91380.049*
H33B0.97050.78120.95490.049*
H33C1.04820.67330.84670.049*
O410.5607 (2)0.8827 (2)0.7565 (2)0.0251 (5)
C420.3756 (4)0.8675 (4)0.8099 (3)0.0292 (7)
H42A0.37860.75530.84560.035*
H42B0.29690.92240.73120.035*
C430.3037 (4)0.9407 (3)0.9311 (3)0.0304 (7)
H43A0.38760.88941.00490.046*
H43B0.18090.92810.97570.046*
H43C0.29501.05290.89280.046*
C110.5539 (4)0.6970 (3)0.3790 (3)0.0211 (6)
C120.3699 (4)0.7069 (3)0.4287 (3)0.0236 (6)
H120.30880.74860.50840.028*
C130.2736 (4)0.6566 (3)0.3632 (3)0.0242 (6)
H130.14660.66400.39680.029*
C140.3655 (4)0.5958 (3)0.2486 (3)0.0250 (6)
Cl140.24405 (10)0.53734 (8)0.16335 (8)0.0315 (2)
C150.5495 (4)0.5827 (3)0.1988 (3)0.0263 (6)
H150.61090.53910.12030.032*
C160.6435 (4)0.6338 (3)0.2646 (3)0.0271 (6)
H160.77070.62550.23110.033*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0224 (15)0.0244 (15)0.0243 (15)0.0039 (12)0.0070 (12)0.0063 (12)
O10.0244 (11)0.0500 (13)0.0283 (11)0.0146 (10)0.0005 (9)0.0167 (10)
N20.0184 (12)0.0261 (13)0.0247 (12)0.0057 (10)0.0039 (10)0.0094 (10)
C30.0234 (15)0.0206 (14)0.0207 (14)0.0043 (11)0.0050 (11)0.0041 (11)
S310.0216 (4)0.0374 (4)0.0246 (4)0.0120 (3)0.0027 (3)0.0100 (3)
C320.0236 (15)0.0363 (17)0.0279 (16)0.0130 (13)0.0067 (12)0.0096 (13)
C330.0324 (17)0.0354 (17)0.0326 (17)0.0061 (14)0.0099 (14)0.0124 (14)
O410.0182 (10)0.0317 (11)0.0281 (11)0.0085 (8)0.0015 (8)0.0118 (9)
C420.0195 (15)0.0390 (18)0.0338 (17)0.0119 (13)0.0012 (12)0.0161 (14)
C430.0308 (17)0.0314 (17)0.0304 (16)0.0111 (14)0.0012 (13)0.0106 (13)
C110.0220 (14)0.0191 (13)0.0192 (13)0.0038 (11)0.0055 (11)0.0022 (11)
C120.0218 (14)0.0223 (14)0.0261 (15)0.0045 (12)0.0051 (11)0.0072 (12)
C130.0210 (15)0.0256 (15)0.0251 (15)0.0052 (12)0.0039 (12)0.0075 (12)
C140.0319 (16)0.0220 (14)0.0220 (15)0.0074 (12)0.0092 (12)0.0045 (12)
Cl140.0374 (5)0.0333 (4)0.0305 (4)0.0114 (3)0.0119 (3)0.0112 (3)
C150.0278 (16)0.0285 (16)0.0217 (15)0.0048 (13)0.0024 (12)0.0103 (12)
C160.0247 (15)0.0279 (15)0.0260 (15)0.0059 (12)0.0021 (12)0.0076 (12)
Geometric parameters (Å, º) top
C1—O11.220 (3)C42—H42B0.9900
C1—N21.382 (3)C43—H43A0.9800
C1—C111.485 (4)C43—H43B0.9800
N2—C31.281 (3)C43—H43C0.9800
C3—O411.326 (3)C11—C121.379 (4)
C3—S311.733 (3)C11—C161.382 (4)
S31—C321.808 (3)C12—C131.384 (4)
C32—C331.512 (4)C12—H120.9500
C32—H32A0.9900C13—C141.375 (4)
C32—H32B0.9900C13—H130.9500
C33—H33A0.9800C14—C151.373 (4)
C33—H33B0.9800C14—Cl141.731 (3)
C33—H33C0.9800C15—C161.377 (4)
O41—C421.449 (3)C15—H150.9500
C42—C431.484 (4)C16—H160.9500
C42—H42A0.9900
O1—C1—N2125.1 (3)H42A—C42—H42B108.7
O1—C1—C11120.5 (2)C42—C43—H43A109.5
N2—C1—C11114.4 (2)C42—C43—H43B109.5
C3—N2—C1119.2 (2)H43A—C43—H43B109.5
N2—C3—O41119.5 (2)C42—C43—H43C109.5
N2—C3—S31127.9 (2)H43A—C43—H43C109.5
O41—C3—S31112.63 (19)H43B—C43—H43C109.5
C3—S31—C32102.47 (13)C12—C11—C16119.7 (3)
C33—C32—S31112.8 (2)C12—C11—C1121.8 (2)
C33—C32—H32A109.0C16—C11—C1118.5 (3)
S31—C32—H32A109.0C11—C12—C13120.5 (3)
C33—C32—H32B109.0C11—C12—H12119.8
S31—C32—H32B109.0C13—C12—H12119.8
H32A—C32—H32B107.8C14—C13—C12118.6 (3)
C32—C33—H33A109.5C14—C13—H13120.7
C32—C33—H33B109.5C12—C13—H13120.7
H33A—C33—H33B109.5C15—C14—C13121.8 (3)
C32—C33—H33C109.5C15—C14—Cl14119.4 (2)
H33A—C33—H33C109.5C13—C14—Cl14118.8 (2)
H33B—C33—H33C109.5C14—C15—C16119.0 (3)
C3—O41—C42118.0 (2)C14—C15—H15120.5
O41—C42—C43105.8 (2)C16—C15—H15120.5
O41—C42—H42A110.6C15—C16—C11120.4 (3)
C43—C42—H42A110.6C15—C16—H16119.8
O41—C42—H42B110.6C11—C16—H16119.8
C43—C42—H42B110.6
O1—C1—N2—C35.3 (4)O1—C1—C11—C169.0 (4)
C11—C1—N2—C3176.1 (2)N2—C1—C11—C16172.4 (2)
C1—N2—C3—O41179.6 (2)C16—C11—C12—C131.1 (4)
C1—N2—C3—S310.7 (4)C1—C11—C12—C13177.6 (2)
N2—C3—S31—C32172.7 (3)C11—C12—C13—C140.4 (4)
O41—C3—S31—C327.7 (2)C12—C13—C14—C150.5 (4)
C3—S31—C32—C3378.7 (2)C12—C13—C14—Cl14178.4 (2)
N2—C3—O41—C423.2 (4)C13—C14—C15—C160.8 (4)
S31—C3—O41—C42177.08 (19)Cl14—C14—C15—C16178.1 (2)
C3—O41—C42—C43172.5 (2)C14—C15—C16—C110.1 (4)
O1—C1—C11—C12169.8 (3)C12—C11—C16—C150.9 (4)
N2—C1—C11—C128.9 (4)C1—C11—C16—C15177.9 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O1i0.952.453.345 (4)156
Symmetry code: (i) x1, y, z.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC10H11NO2SC11H13NO2SC13H17NO2SC12H14ClNO2S
Mr209.27223.29251.35271.75
Crystal system, space groupOrthorhombic, Pna21Monoclinic, P21/cTriclinic, P1Triclinic, P1
Temperature (K)120120120120
a, b, c (Å)9.9418 (8), 9.3619 (5), 10.9337 (13)12.2845 (14), 9.1431 (17), 9.7897 (4)7.2470 (16), 8.8870 (7), 10.737 (1)7.8028 (14), 9.480 (2), 9.860 (2)
α, β, γ (°)90, 90, 9090, 90.182 (7), 90100.691 (7), 99.984 (13), 107.307 (11)69.545 (13), 75.683 (14), 69.548 (15)
V3)1017.65 (16)1099.6 (2)629.19 (17)633.7 (2)
Z4422
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.290.270.250.46
Crystal size (mm)0.50 × 0.42 × 0.410.34 × 0.30 × 0.240.42 × 0.33 × 0.260.52 × 0.45 × 0.29
Data collection
DiffractometerBruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Bruker Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Multi-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.868, 0.8900.918, 0.9370.889, 0.9380.778, 0.879
No. of measured, independent and
observed [I > 2σ(I)] reflections
13852, 1889, 1284 11469, 2026, 1334 2460, 2460, 2064 14986, 2363, 1707
Rint0.0740.0510.0000.051
(sin θ/λ)max1)0.6060.6060.6170.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.130, 1.14 0.049, 0.134, 1.07 0.060, 0.167, 1.18 0.045, 0.119, 1.12
No. of reflections1889202624602363
No. of parameters128138158156
No. of restraints1000
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.45, 0.290.31, 0.290.71, 0.460.49, 0.34
Absolute structureFlack (1983), with 890 Bijvoet pairs???
Absolute structure parameter0.08 (17)???

Computer programs: COLLECT (Nonius, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected geometric parameters (Å, °) for (I)–(IV) top
Parameter(I)(II)(III)(IV)
(a) Bond distances
C1-O11.206 (5)1.208 (3)1.210 (4)1.220 (3)
C1-N21.385 (5)1.370 (3)1.379 (4)1.382 (3)
N2-C31.384 (6)1.377 (3)1.283 (4)1.281 (3)
C3-S31.615 (4)1.615 (3)
C3-O41.325 (5)1.324 (3)
C3-S311.730 (4)1.733 (3)
C3-O411.321 (4)1.326 (3)
(b) Inter-bond angles
O1-C1-N2122.4 (4)122.3 (3)125.7 (3)125.1 (3)
C1-N2-C3127.3 (4)127.1 (2)120.0 (3)119.2 (2)
N2-C3-S3127.4 (3)128.5 (2)
N2-C3-S31128.3 (3)127.9 (2)
(c) Torsion angles
C12-C11-C1-N219.3 (6)-21.4 (4)8.3 (5)8.9 (4)
C11-C1-N2-C3-162.4 (4)179.0 (2)177.9 (3)176.1 (2)
C1-N2-C3-O4-179.9 (4)-171.7 (2)
N2-C3-O4-C5-174.4 (4)-177.8 (2)
C3-O4-C5-C6-171.0 (4)-171.3 (2)
C1-N2-C3-S311.3 (5)0.7 (4)
C1-N2-C3-O41-178.8 (3)-179.6 (2)
N2-C3-C31-C32178.1 (3)-172.7 (3)
C3-S31-C32-C33-179.4 (3)78.7 (2)
N2-C3-O41-C42-1.3 (5)3.2 (4)
C3-O41-C42-C43-178.4 (3)-172.5 (2)
Hydrogen bonds and short intermolecular contacts (Å, °) for (I)–(IV) top
CompoundD—H···AD—HH···AD···AD—H···A
(I)N2-H2···O1i0.882.052.921 (4)170
C12-H12···S3i0.952.833.606 (4)139
C12-H12···O1i0.952.513.192 (5)129
C16-H16···S3ii0.952.863.576 (5)134
(II)N2-H2···O1iii0.882.032.896 (3)167
C12-H12···O1iii0.952.323.075 (3)136
(III)C32-H32B···Cg1iv0.992.623.554 (5)158
(IV)C13-H13···O1v0.952.453.345 (4)156
Cg1 represents the centroid of the ring C11–C16. Symmetry codes: (i) -1/2 + x, 3/2 - y, z; (ii) 3/2 - x, 1/2 + y, -1/2 + z; (iii) x, 3/2 - y, -1/2 + z; (iv) 1 - x, 1 - y, 1 - z; (v) -1 + x, y, z.
 

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