S-Ethyl N-benzoyl­di­thio­carbamate: two independent hydrogen-bonded R_{\bf 2}^{\bf 2}(8) dimers of different symmetry linked into chains by a C—H⋯π(arene) interaction

Low, J.N.; Cobo, J.; Insuasty, H.; Estrada, M.; Cortés, E.; Glidewell, C.

doi:10.1107/S0108270104012090

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 7| July 2004| Pages o483-o485

doi:10.1107/S0108270104012090

S-Ethyl N-benzoyldithiocarbamate: two independent hydrogen-bonded R $[_{\bf 2}^{\bf 2}]$ (8) dimers of different symmetry linked into chains by a C—H⋯π(arene) interaction

John N. Low,^a Justo Cobo,^b Henry Insuasty,^c Martin Estrada,^c Edward Cortés ^c and Christopher Glidewell ^d ^*

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, ^bDepartamento de Química Inorgánica y Orgánica, Universidad de Jaén, 23071 Jaén, Spain, ^cDepartamento de Química, Universidad de Nariño, Cuidad Universitaria, Torobajo, AA1175 Pasto, Colombia, and ^dSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 17 May 2004; accepted 18 May 2004; online 22 June 2004)

The title compound, C₁₀H₁₁NOS₂, crystallizes with Z′ = 2 in space group C2/c. The molecules are linked by two N—H⋯S hydrogen bonds [H⋯S = 2.60 and 2.62 Å, N⋯S = 3.350 (2) and 3.490 (2) Å, and N—H⋯S = 143 and 172°] into two distinct types of [R_2^2] (8) dimer, viz. one generated by inversion and the other by a twofold rotation axis. A single C—H⋯π(arene) hydrogen bond links the two types of dimer into chains.

Comment

It has been shown (Elmore et al., 1956 ; Nash et al., 1969 ) that alkanethiols, RSH, react smoothly with aroylisothiocyanates, ArCONCS, to give S-alkyl N-aroyldithiocarbamates, (ArCO)NHC(=S)SR, in good yields. We report here the molecular and supramolecular structures of the title compound, (PhCO)NHC(=S)SEt, (I), which is an important intermediate in the preparation of S,S-dialkyl N-aroyliminodithiocarbonates used in the synthesis of many organic compounds (Augustín et al., 1980 ). We have modified the reported method for the synthesis of S-methyl N-benzoyldithiocarbamate (Elmore et al., 1956), so enhancing the yield from 49 to 87%.

The title compound crystallizes in space group C2/c, with Z′ = 2 (Fig. 1). The bond lengths (Table 1), which are normal for their types (Allen et al., 1987 ), are, in general, almost identical in the two independent molecules, as are the overall molecular conformations. However, the two torsion angles defining the orientation of the benzene rings relative to the rest of the nearly planar molecular skeletons differ by 22°. This fact alone suffices to preclude the possibility of any additional symmetry.

Such a possibility is also ruled out by the observation that each type of molecule forms a hydrogen-bonded dimer but that these have different symmetries. For molecules of type 1 (Fig. 1a), atom N12 in the molecule at (x, y, z) acts as a hydrogen-bond donor to thione atom S13 in the molecule at (1 − x, 1 − y, 1 − z), so generating a centrosymmetric [R_2^2] (8) dimer (Bernstein et al., 1995 ) centred at ( $[1 \over 2]$ , $[1 \over 2]$ , $[1 \over 2]$ ) (Fig. 2a). However, for molecules of type 2 (Fig. 1b), atom N22 at (x, y, z) acts as a donor to thione atom S23 at (1 − x, y, $[3 \over 2]$ − z), so that this [R_2^2] (8) dimer (Fig. 2b) lies across the twofold rotation axis along ( $[1 \over 2]$ , y, $[3 \over 4]$ ). The dimensions of the two independent N—H⋯S hydrogen bonds (Table 2) are markedly different.

Although the N⋯S distance is above the sum of the conventional van der Waals radii (3.3 Å; Bondi, 1964 ), an analysis (Allen et al., 1997 ) of hydrogen bonds having a secondary amine donor and a thione-type S atom as the acceptor, using data retrieved from the Cambridge Structural Database (Allen, 2002 ), indicated mean H⋯S, N⋯S and N—H⋯S parameters of 2.46 (1) Å, 3.40 (1) Å and 158 (1)°, respectively, in such bonds involving the neutral species R¹R²C=S as an acceptor, and 2.51 (1) Å, 3.44 (1) Å and 158 (1)°, respectively, in such bonds involving neutral thioureas as an acceptor. Accordingly, the N—H⋯S interactions in (I) appear to be fairly typical of such hydrogen bonds.

Each unit cell contains four dimers of each type, and the two types are linked into chains by a single C—H⋯π(arene) hydrogen bond. Atoms C46 in the type 2 molecules at (x, y, z) and (1 − x, y, $[3 \over 2]$ − z) lie in the dimer across the twofold axis along ( $[1\over 2]$ , y, $[3 \over 4]$ ). These atoms act as hydrogen-bond donors, respectively, to the C31–C36 rings in the type 1 molecules at (− $[1 \over 2 ]$ + x, $[1 \over 2 ]$ + y, z) and ( $[3 \over 2]$ − x, $[1 \over 2]$ + y, $[3 \over 2]$ − z), which are themselves components of the type 1 dimers centred at (0, 1, $[1 \over 2]$ ) and (1, 1, 1), respectively. Within these type 1 dimers, the molecules at ( $[1 \over 2]$ − x, $[3 \over 2]$ − y, 1 − z) and ( $[1 \over 2]$ + x, $[3 \over 2]$ − y, $[1 \over 2]$ + z) similarly accept hydrogen bonds from atoms C46 in the type 2 molecules at (1 − x, 2 − y, 1 − z) and (1 + x, 2 − y, $[1 \over 2]$ + z), respectively, which themselves lie in the type 2 dimers across the rotation axes along ( $[1 \over 2]$ , −y, $[1 \over 4]$ ) and ( $[3 \over 2]$ , −y, $[5 \over 4]$ ). Propagation of this single C—H⋯π(arene) hydrogen bond by inversion and rotation thus links dimers of the two types into a chain of rings running parallel to the [201] direction (Fig. 3). Four chains pass through each unit cell, but there are no direction-specific interactions between adjacent chains.

Figure 1
The two independent molecules in (I

), showing the atom-labelling scheme in (a) the type 1 molecule and (b) the type 2 molecule. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2
The two independent hydrogen-bonded dimers in the structure of (I

), showing (a) that generated by inversion, where atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z), and (b) that generated by rotation, where atoms marked with an asterisk (*) are at the symmetry position (1 − x, y, $[3 \over 2]$ − z).

Figure 3
A stereoview of part of the crystal structure of (I

), showing the formation of the [201] chain of rings linking the two types of [R_2^2]

(8) dimer.

Experimental

Benzoyl chloride (5 ml, 0.043 mol) was added to a solution of potassium thiocyanate (4.1 g, 0.043 mol) in acetonitrile (75 ml) and this mixture was heated under reflux for 15 min to afford benzoyl isothiocyanate. The mixture was cooled to 273 K under an inert atmosphere; ethanethiol (35 ml, 0.47 mol) was added, and this mixture was then stirred at room temperature for 27 h. Ice-water was added and the title compound was extracted with ethyl acetate (3 × 25 ml). The combined organic extracts were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The resulting yellow solid was recrystallized from ethanol to give crystals of (I) suitable for single-crystal X-ray diffraction [yield 87%, m.p. 348 K; literature (Nash et al., 1969) m.p. 352–353 K, yield 49%].

Crystal data

C₁₀H₁₁NOS₂
M_r = 225.34
Monoclinic, C2/c
a = 21.8190 (5) Å
b = 8.4596 (2) Å
c = 23.1792 (5) Å
β = 94.5140 (14)°
V = 4265.15 (17) Å³
Z = 16
D_x = 1.404 Mg m⁻³
Mo Kα radiation
Cell parameters from 4840 reflections
θ = 3.1–27.5°
μ = 0.46 mm⁻¹
T = 120 (2) K
Block, colourless
0.20 × 0.20 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer
φ scans, and ω scans with κ offsets
Absorption correction: multi-scan (SORTAV; Blessing, 1995 , 1997 ) T_min = 0.902, T_max = 0.929
33 304 measured reflections
4840 independent reflections
3569 reflections with I > 2σ(I)
R_int = 0.067
θ_max = 27.5°
h = −28 → 28
k = −10 → 10
l = −30 → 29

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.089
S = 1.01
4840 reflections
255 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0447P)² + 0.8703P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C11—O11	1.214 (2)
C11—N12	1.394 (2)
N12—C13	1.376 (2)
C13—S13	1.6586 (18)
C13—S14	1.7414 (19)
S14—C15	1.8103 (18)
C21—O21	1.214 (2)
C21—N22	1.394 (2)
N22—C23	1.379 (2)
C23—S23	1.6552 (18)
C23—S24	1.7333 (19)
S24—C25	1.8116 (18)

C31—C11—N12—C13	175.14 (16)
C11—N12—C13—S14	−1.6 (2)
N12—C13—S14—C15	−173.39 (13)
C13—S14—C15—C16	−174.12 (13)
N12—C11—C31—C32	−45.0 (2)
C41—C21—N22—C23	−177.70 (16)
C21—N22—C23—S24	−4.1 (2)
N22—C23—S24—C25	176.92 (14)
C23—S24—C25—C26	−173.31 (13)
N22—C21—C41—C42	−22.7 (3)

Table 2
Hydrogen-bonding geometry (Å, °)

Cg1 is the centroid of the C31–C36 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N12—H12⋯S13ⁱ	0.88	2.62	3.490 (2)	172
N22—H22⋯S23ⁱⁱ	0.88	2.60	3.350 (2)	143
C46—H46⋯Cg1ⁱⁱⁱ	0.95	2.85	3.678 (2)	146
Symmetry codes: (i) 1-x,1-y,1-z; (ii) $[1-x,y,{\script{3\over 2}}-z]$ ; (iii) $[x-{\script{1\over 2}},{\script{1\over 2}}+y,z]$ .

The systematic absences permitted C2/c and Cc as possible space groups; C2/c was selected and confirmed by the structure analysis. All H atoms were located from difference maps and subsequently treated as riding atoms, with C—H distances of 0.95 (aromatic), 0.98 (CH₃) or 0.99 Å (CH₂), an N—H distance of 0.88 Å, and U_iso(H) values of 1.2U_eq(C,N) or 1.5U_eq(C_methyl).

Data collection: KappaCCD Server Software (Nonius, 1997 ); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO–SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003 ) and SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270104012090/sk1733sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104012090/sk1733Isup2.hkl

Comment top

It has been shown (Elmore et al., 1956; Nash et al., 1969) that alkanethiols, RSH, react smoothly with aroylisothiocyanates, ArCONCS, to give S-alkyl N-aroyldithiocarbamates, (ArCO)NHC(=S)SR, in good yields. We report here the molecular and supramolecular structures of the title compound, (PhCO)NHC(=S)SEt, which is an important intermediate for the preparation of S,S-dialkyl N-aroyliminodithiocarbonates used in the synthesis of many organic compounds (Augustín et al., 1980). We have modified the reported method for the synthesis of S-methyl N-benzoyldithiocarbamate (Elmore et al., 1956), so enhancing the yield from 49 to 87%.

The title compound crystallizes in space group C2/c, with Z' = 2 (Fig. 1). The bond lengths (Table 1), which are normal for their types (Allen et al., 1987), are, in general, almost identical in the two independent molecules, as are the overall molecular conformations. However, the two torsion angles defining the orientation of the phenyl rings relative to the rest of the nearly planar molecular skeletons differ by 22°. This fact alone suffices to preclude the possibility of any additional symmetry.

Such a possibility is also ruled out by the observation that each type of molecule forms a hydrogen-bonded dimer but that these have different symmetries. For molecules of type 1 (Fig. 1a), atom N12 in the molecule at (x, y, z) acts as a hydrogen-bond donor to thione atom S13 in the molecule at (1 − x, 1 − y, 1 − z), so generating a centrosymmetric R²₂(8) dimer (Bernstein et al., 1995) centred at (1/2, 1/2, 1/2) (Fig. 2a). However, for molecules of type 2 (Fig. 1 b), atom N22 at (x, y, z) acts as a donor to thione atom S23 at (1 − x, y, 1.5 − z), so that this R²₂(8) dimer (Fig. 2 b) lies across the twofold rotation axis along (1/2,y, 3/4). The dimensions of the two independent N—H···S hydrogen bonds (Table 2) are markedly different.

Although the N···S distance is above the sum, 3.3 Å, of the conventional van der Waals radii (Bondi, 1964), an analysis (Allen et al., 1997) of hydrogen bonds having a secondary amine donor and a thione-type S atom as the acceptor, using data retrieved from the Cambridge Structural Database (Allen, 2002), indicated mean H···S, N···S and N—H···S parameters of 2.46 (1) Å, 3.40 (1) Å and 158 (1)° in such bonds involving the neutral species R¹R²C=S as an acceptor, and 2.51 (1) Å, 3.44 (1) Å and 158 (1)° in such bonds involving neutral thioureas as an acceptor. Accordingly, the N—H···S interactions in (I) appear to be fairly typical of such hydrogen bonds.

Each unit cell contains four dimers of each type and the two types are linked into chains by a single C—H···π(arene) hydrogen bond. Atoms C46 in the type 2 molecules at (x, y, z) and (1 − x, y, 1.5 − z) lie in the dimer across the twofold axis along (1/2, y, 3/4). These atoms act as hydrogen-bond donors, respectively, to the C31—C36 rings in the type 1 molecules at (−0.5 + x, 0.5 + y, z) and (1.5 − x, 0.5 + y, 1.5 − z), which are themselves components of the type 1 dimers centred at (0, 1, 1/2) and (1, 1, 1), respectively. Within these type 1 dimers, the molecules at (0.5 − x, 1.5 − y, 1 − z) and (0.5 + x, 1.5 − y, 0.5 + z) similarly accept hydrogen bonds from atoms C46 in the type 2 molecules at (1 − x, 2 − y, 1 − z) and (1 + x, 2 − y, 0.5 + z), respectively, which themselves lie in the type 2 dimers acoss the rotation axes along (−0.5, −y, 1/4) and (1.5, −y, 1.25). Propagation of this single C—H..π(arene) hydrogen bond by inversion and rotation thus links dimers of the two types into a chain of rings running parallel to the [201] direction (Fig. 3). Four chains pass through each unit cell, but there are no direction-specific interactions betweeen adjacent chains.

Experimental top

Benzoyl chloride (5 ml, 0.043 mol) was added to a solution of potassium thiocyanate (4.1 g, 0.043 mol) in acetonitrile (75 ml) and this mixture was heated under reflux for 15 min to afford benzoyl isothiocyanate. The mixture was cooled to 273 K under an inert atmosphere; ethanethiol (35 ml, 0.47 mol) was added, and this mixture was then stirred at room temperature for 27 h. Ice-water was added and the title compound was extracted with ethyl acetate (3 x 25 ml). The combined organic extracts were dried over anhydrous sodium sulfate and the solvent was removed under reduced pressure. The resulting yellow solid was recrystallized from ethanol to give crystals of (I) suitable for single-crystal X-ray diffraction. Yield 87%, m.p. 348 K. Literature (Nash et al., 1969) m.p. 352–353 K, yield 49%.

Computing details top

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: OSCAIL and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures top

	Fig. 1. The two independent molecules in (I), showing the atom-labelling scheme: (a) the type 1 molecule and (b) the type 2 molecule. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The two independent hydrogen-bonded dimers in the structure of (I): (a) that generated by inversion, where atoms marked with an asterisk () are at the symmetry position (1 − x, 1 − y, 1 − z), and (b) that generated by rotation, where atoms marked with an asterisk () are at the symmetry position (1 − x, y, 1.5 − z).
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of the [201] chain of rings linking the two types of R²₂(8) dimer.

S-Ethyl N-benzoyldithiocarbamate top

Crystal data top

C₁₀H₁₁NOS₂	F(000) = 1888
M_r = 225.34	D_x = 1.404 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4840 reflections
a = 21.8190 (5) Å	θ = 3.1–27.5°
b = 8.4596 (2) Å	µ = 0.46 mm⁻¹
c = 23.1792 (5) Å	T = 120 K
β = 94.5140 (14)°	Block, colourless
V = 4265.15 (17) Å³	0.20 × 0.20 × 0.16 mm
Z = 16

Data collection top

Nonius KappaCCD diffractometer	4840 independent reflections
Radiation source: rotating anode	3569 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
ϕ scans, and ω scans with κ offsets	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	h = −28→28
T_min = 0.902, T_max = 0.929	k = −10→10
33304 measured reflections	l = −30→29

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0447P)² + 0.8703P] where P = (F_o² + 2F_c²)/3
4840 reflections	(Δ/σ)_max = 0.001
255 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₁₀H₁₁NOS₂	V = 4265.15 (17) Å³
M_r = 225.34	Z = 16
Monoclinic, C2/c	Mo Kα radiation
a = 21.8190 (5) Å	µ = 0.46 mm⁻¹
b = 8.4596 (2) Å	T = 120 K
c = 23.1792 (5) Å	0.20 × 0.20 × 0.16 mm
β = 94.5140 (14)°

Data collection top

Nonius KappaCCD diffractometer	4840 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	3569 reflections with I > 2σ(I)
T_min = 0.902, T_max = 0.929	R_int = 0.067
33304 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.01	Δρ_max = 0.29 e Å⁻³
4840 reflections	Δρ_min = −0.38 e Å⁻³
255 parameters

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

	x	y	z	U_iso*/U_eq
S13	0.43471 (2)	0.36946 (6)	0.54420 (2)	0.02042 (12)
S14	0.49163 (2)	0.24080 (5)	0.65662 (2)	0.01954 (12)
O11	0.60744 (6)	0.34703 (16)	0.66461 (6)	0.0243 (3)
N12	0.55035 (6)	0.40915 (17)	0.58096 (6)	0.0175 (3)
C11	0.60505 (8)	0.4030 (2)	0.61624 (8)	0.0188 (4)
C13	0.49451 (8)	0.3452 (2)	0.59213 (8)	0.0163 (4)
C15	0.41451 (8)	0.1605 (2)	0.64882 (8)	0.0208 (4)
C16	0.40314 (9)	0.0795 (2)	0.70572 (9)	0.0276 (5)
C31	0.65977 (8)	0.4715 (2)	0.59075 (8)	0.0180 (4)
C32	0.67309 (8)	0.4399 (2)	0.53411 (8)	0.0212 (4)
C33	0.72637 (8)	0.5011 (2)	0.51352 (8)	0.0252 (4)
C34	0.76538 (9)	0.5960 (2)	0.54910 (9)	0.0266 (4)
C35	0.75195 (8)	0.6278 (2)	0.60514 (9)	0.0260 (5)
C36	0.69969 (8)	0.5635 (2)	0.62660 (8)	0.0219 (4)
S23	0.56865 (2)	0.73412 (6)	0.69753 (2)	0.02289 (13)
S24	0.51204 (2)	0.84877 (6)	0.58307 (2)	0.02053 (12)
O21	0.39103 (6)	0.77129 (15)	0.58351 (6)	0.0244 (3)
N22	0.45330 (6)	0.69264 (18)	0.66186 (6)	0.0184 (3)
C21	0.39665 (8)	0.7034 (2)	0.62979 (8)	0.0188 (4)
C23	0.50920 (8)	0.7543 (2)	0.64916 (8)	0.0174 (4)
C25	0.59095 (8)	0.9172 (2)	0.58779 (9)	0.0253 (4)
C26	0.59880 (9)	1.0212 (2)	0.53514 (8)	0.0253 (4)
C41	0.34413 (8)	0.6283 (2)	0.65692 (8)	0.0185 (4)
C42	0.35075 (8)	0.5093 (2)	0.69847 (8)	0.0206 (4)
C43	0.29949 (8)	0.4416 (2)	0.71982 (8)	0.0232 (4)
C44	0.24097 (8)	0.4920 (2)	0.70002 (9)	0.0254 (4)
C45	0.23416 (9)	0.6117 (2)	0.65953 (9)	0.0274 (5)
C46	0.28515 (9)	0.6793 (2)	0.63742 (9)	0.0239 (4)
H12	0.5507	0.4606	0.5480	0.021*
H15A	0.3842	0.2462	0.6405	0.025*
H15B	0.4106	0.0835	0.6166	0.025*
H16A	0.4356	0.0015	0.7152	0.041*
H16B	0.3631	0.0262	0.7019	0.041*
H16C	0.4034	0.1586	0.7366	0.041*
H32	0.6459	0.3769	0.5097	0.025*
H33	0.7362	0.4781	0.4752	0.030*
H34	0.8014	0.6391	0.5347	0.032*
H35	0.7785	0.6937	0.6291	0.031*
H36	0.6912	0.5822	0.6656	0.026*
H22	0.4525	0.6558	0.6973	0.022*
H25A	0.6001	0.9785	0.6238	0.030*
H25B	0.6195	0.8261	0.5881	0.030*
H26A	0.5904	0.9588	0.4998	0.038*
H26B	0.6410	1.0615	0.5368	0.038*
H26C	0.5700	1.1102	0.5350	0.038*
H42	0.3907	0.4745	0.7122	0.025*
H43	0.3043	0.3604	0.7481	0.028*
H44	0.2058	0.4442	0.7143	0.031*
H45	0.1942	0.6479	0.6467	0.033*
H46	0.2801	0.7602	0.6090	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S13	0.0160 (2)	0.0259 (3)	0.0189 (3)	−0.00182 (18)	−0.00175 (18)	0.00254 (19)
S14	0.0168 (2)	0.0220 (3)	0.0197 (3)	−0.00085 (18)	0.00062 (18)	0.00365 (19)
O11	0.0206 (7)	0.0314 (8)	0.0203 (7)	−0.0020 (6)	−0.0019 (5)	0.0058 (6)
N12	0.0163 (7)	0.0184 (8)	0.0176 (8)	−0.0008 (6)	0.0004 (6)	0.0032 (6)
C11	0.0172 (9)	0.0181 (9)	0.0208 (10)	0.0030 (7)	−0.0005 (7)	−0.0022 (8)
C13	0.0175 (8)	0.0131 (9)	0.0187 (9)	0.0004 (7)	0.0033 (7)	−0.0030 (7)
C15	0.0188 (9)	0.0233 (10)	0.0206 (10)	−0.0025 (8)	0.0033 (8)	0.0001 (8)
C16	0.0284 (10)	0.0289 (12)	0.0263 (11)	−0.0041 (9)	0.0073 (9)	0.0049 (9)
C31	0.0149 (8)	0.0173 (9)	0.0215 (10)	0.0023 (7)	0.0000 (7)	0.0032 (8)
C32	0.0184 (9)	0.0239 (10)	0.0206 (10)	−0.0004 (8)	−0.0016 (7)	0.0009 (8)
C33	0.0237 (10)	0.0326 (12)	0.0199 (11)	0.0022 (8)	0.0052 (8)	0.0011 (8)
C34	0.0185 (9)	0.0287 (11)	0.0330 (12)	−0.0014 (8)	0.0050 (8)	0.0043 (9)
C35	0.0168 (9)	0.0268 (11)	0.0339 (12)	−0.0033 (8)	−0.0007 (8)	−0.0044 (9)
C36	0.0173 (9)	0.0264 (11)	0.0221 (10)	0.0020 (8)	0.0011 (8)	−0.0029 (8)
S23	0.0169 (2)	0.0346 (3)	0.0169 (3)	0.00119 (19)	0.00015 (18)	0.0016 (2)
S24	0.0201 (2)	0.0246 (3)	0.0168 (2)	−0.00065 (18)	0.00092 (18)	0.00270 (19)
O21	0.0258 (7)	0.0264 (7)	0.0202 (7)	−0.0023 (6)	−0.0023 (6)	0.0047 (6)
N22	0.0176 (7)	0.0219 (8)	0.0156 (8)	−0.0004 (6)	0.0008 (6)	0.0008 (6)
C21	0.0203 (9)	0.0167 (9)	0.0188 (10)	0.0017 (7)	−0.0026 (7)	−0.0049 (8)
C23	0.0204 (9)	0.0159 (9)	0.0159 (9)	0.0018 (7)	0.0011 (7)	−0.0032 (7)
C25	0.0190 (9)	0.0292 (11)	0.0276 (11)	−0.0015 (8)	0.0013 (8)	0.0031 (9)
C26	0.0272 (10)	0.0235 (11)	0.0258 (11)	−0.0014 (8)	0.0060 (8)	0.0018 (8)
C41	0.0193 (9)	0.0181 (10)	0.0178 (10)	−0.0002 (7)	−0.0012 (7)	−0.0042 (7)
C42	0.0201 (9)	0.0208 (10)	0.0200 (10)	0.0007 (8)	−0.0043 (8)	−0.0039 (8)
C43	0.0268 (10)	0.0222 (10)	0.0201 (10)	−0.0018 (8)	0.0002 (8)	−0.0005 (8)
C44	0.0201 (9)	0.0289 (11)	0.0281 (11)	−0.0033 (8)	0.0065 (8)	−0.0062 (9)
C45	0.0196 (10)	0.0282 (11)	0.0339 (12)	0.0043 (8)	−0.0006 (8)	−0.0019 (9)
C46	0.0236 (10)	0.0226 (10)	0.0247 (11)	0.0011 (8)	−0.0034 (8)	0.0001 (8)

Geometric parameters (Å, º) top

C11—O11	1.214 (2)	C21—O21	1.214 (2)
C11—N12	1.394 (2)	C21—N22	1.394 (2)
C11—C31	1.491 (3)	C21—C41	1.492 (3)
N12—C13	1.376 (2)	N22—C23	1.379 (2)
N12—H12	0.88	N22—H22	0.88
C13—S13	1.6586 (18)	C23—S23	1.6552 (18)
C13—S14	1.7414 (19)	C23—S24	1.7333 (19)
S14—C15	1.8103 (18)	S24—C25	1.8116 (18)
C15—C16	1.524 (3)	C25—C26	1.525 (3)
C15—H15A	0.99	C25—H25A	0.99
C15—H15B	0.99	C25—H25B	0.99
C16—H16A	0.98	C26—H26A	0.98
C16—H16B	0.98	C26—H26B	0.98
C16—H16C	0.98	C26—H26C	0.98
C31—C32	1.393 (3)	C41—C42	1.393 (3)
C31—C36	1.393 (3)	C41—C46	1.398 (3)
C32—C33	1.391 (3)	C42—C43	1.383 (3)
C32—H32	0.95	C42—H42	0.95
C33—C34	1.393 (3)	C43—C44	1.389 (3)
C33—H33	0.95	C43—H43	0.95
C34—C35	1.380 (3)	C44—C45	1.381 (3)
C34—H34	0.95	C44—H44	0.95
C35—C36	1.390 (3)	C45—C46	1.385 (3)
C35—H35	0.95	C45—H45	0.95
C36—H36	0.95	C46—H46	0.95

O11—C11—N12	121.93 (17)	O21—C21—N22	121.70 (17)
O11—C11—C31	122.69 (16)	O21—C21—C41	123.10 (16)
N12—C11—C31	115.37 (16)	N22—C21—C41	115.19 (16)
C13—N12—C11	127.21 (15)	C23—N22—C21	128.55 (16)
C13—N12—H12	115.2	C23—N22—H22	114.6
C11—N12—H12	117.6	C21—N22—H22	116.0
N12—C13—S13	119.11 (13)	N22—C23—S23	118.39 (13)
N12—C13—S14	116.96 (13)	N22—C23—S24	117.17 (13)
S13—C13—S14	123.93 (10)	S23—C23—S24	124.44 (11)
C13—S14—C15	101.57 (8)	C23—S24—C25	101.18 (9)
C16—C15—S14	107.20 (13)	C26—C25—S24	107.59 (13)
C16—C15—H15A	110.3	C26—C25—H25A	110.2
S14—C15—H15A	110.3	S24—C25—H25A	110.2
C16—C15—H15B	110.3	C26—C25—H25B	110.2
S14—C15—H15B	110.3	S24—C25—H25B	110.2
H15A—C15—H15B	108.5	H25A—C25—H25B	108.5
C15—C16—H16A	109.5	C25—C26—H26A	109.5
C15—C16—H16B	109.5	C25—C26—H26B	109.5
H16A—C16—H16B	109.5	H26A—C26—H26B	109.5
C15—C16—H16C	109.5	C25—C26—H26C	109.5
H16A—C16—H16C	109.5	H26A—C26—H26C	109.5
H16B—C16—H16C	109.5	H26B—C26—H26C	109.5
C32—C31—C36	120.16 (17)	C42—C41—C46	119.29 (17)
C32—C31—C11	122.14 (16)	C42—C41—C21	123.90 (16)
C36—C31—C11	117.62 (17)	C46—C41—C21	116.77 (17)
C33—C32—C31	119.60 (17)	C43—C42—C41	120.27 (17)
C33—C32—H32	120.2	C43—C42—H42	119.9
C31—C32—H32	120.2	C41—C42—H42	119.9
C32—C33—C34	120.00 (18)	C42—C43—C44	120.19 (18)
C32—C33—H33	120.0	C42—C43—H43	119.9
C34—C33—H33	120.0	C44—C43—H43	119.9
C35—C34—C33	120.29 (18)	C45—C44—C43	119.78 (18)
C35—C34—H34	119.9	C45—C44—H44	120.1
C33—C34—H34	119.9	C43—C44—H44	120.1
C34—C35—C36	120.08 (18)	C44—C45—C46	120.52 (18)
C34—C35—H35	120.0	C44—C45—H45	119.7
C36—C35—H35	120.0	C46—C45—H45	119.7
C35—C36—C31	119.82 (18)	C45—C46—C41	119.93 (18)
C35—C36—H36	120.1	C45—C46—H46	120.0
C31—C36—H36	120.1	C41—C46—H46	120.0

O11—C11—N12—C13	−5.6 (3)	O21—C21—N22—C23	1.4 (3)
C31—C11—N12—C13	175.14 (16)	C41—C21—N22—C23	−177.70 (16)
C11—N12—C13—S13	178.96 (14)	C21—N22—C23—S23	175.75 (14)
C11—N12—C13—S14	−1.6 (2)	C21—N22—C23—S24	−4.1 (2)
N12—C13—S14—C15	−173.39 (13)	N22—C23—S24—C25	176.92 (14)
S13—C13—S14—C15	6.04 (14)	S23—C23—S24—C25	−2.88 (15)
C13—S14—C15—C16	−174.12 (13)	C23—S24—C25—C26	−173.31 (13)
O11—C11—C31—C32	135.8 (2)	O21—C21—C41—C42	158.22 (18)
N12—C11—C31—C32	−45.0 (2)	N22—C21—C41—C42	−22.7 (3)
O11—C11—C31—C36	−41.0 (3)	O21—C21—C41—C46	−19.8 (3)
N12—C11—C31—C36	138.22 (17)	N22—C21—C41—C46	159.28 (16)
C36—C31—C32—C33	−0.2 (3)	C46—C41—C42—C43	0.5 (3)
C11—C31—C32—C33	−176.96 (17)	C21—C41—C42—C43	−177.46 (17)
C31—C32—C33—C34	−1.3 (3)	C41—C42—C43—C44	−0.1 (3)
C32—C33—C34—C35	1.1 (3)	C42—C43—C44—C45	−1.0 (3)
C33—C34—C35—C36	0.8 (3)	C43—C44—C45—C46	1.6 (3)
C34—C35—C36—C31	−2.3 (3)	C44—C45—C46—C41	−1.2 (3)
C32—C31—C36—C35	2.0 (3)	C42—C41—C46—C45	0.1 (3)
C11—C31—C36—C35	178.91 (17)	C21—C41—C46—C45	178.24 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12···S13ⁱ	0.88	2.62	3.490 (2)	172
N22—H22···S23ⁱⁱ	0.88	2.60	3.350 (2)	143
C46—H46···Cg1ⁱⁱⁱ	0.95	2.85	3.678 (2)	146

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁NOS₂
M_r	225.34
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	120
a, b, c (Å)	21.8190 (5), 8.4596 (2), 23.1792 (5)
β (°)	94.5140 (14)
V (Å³)	4265.15 (17)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.20 × 0.20 × 0.16

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995, 1997)
T_min, T_max	0.902, 0.929
No. of measured, independent and observed [I > 2σ(I)] reflections	33304, 4840, 3569
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.089, 1.01
No. of reflections	4840
No. of parameters	255
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.38

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, OSCAIL (McArdle, 2003) and SHELXS97 (Sheldrick, 1997), OSCAIL and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97 and PRPKAPPA (Ferguson, 1999).

Selected geometric parameters (Å, º) top

C11—O11	1.214 (2)	C21—O21	1.214 (2)
C11—N12	1.394 (2)	C21—N22	1.394 (2)
N12—C13	1.376 (2)	N22—C23	1.379 (2)
C13—S13	1.6586 (18)	C23—S23	1.6552 (18)
C13—S14	1.7414 (19)	C23—S24	1.7333 (19)
S14—C15	1.8103 (18)	S24—C25	1.8116 (18)

C31—C11—N12—C13	175.14 (16)	C41—C21—N22—C23	−177.70 (16)
C11—N12—C13—S14	−1.6 (2)	C21—N22—C23—S24	−4.1 (2)
N12—C13—S14—C15	−173.39 (13)	N22—C23—S24—C25	176.92 (14)
C13—S14—C15—C16	−174.12 (13)	C23—S24—C25—C26	−173.31 (13)
N12—C11—C31—C32	−45.0 (2)	N22—C21—C41—C42	−22.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N12—H12···S13ⁱ	0.88	2.62	3.490 (2)	172
N22—H22···S23ⁱⁱ	0.88	2.60	3.350 (2)	143
C46—H46···Cg1ⁱⁱⁱ	0.95	2.85	3.678 (2)	146

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

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JNL thanks NCR Self-Service, Dundee, for grants that have provided computing facilities for this work. JC thanks the Consejería de Educación y Ciencia (Junta de Andalucía, Spain) and the Universidad de Jaén for financial support. HI, ME and EC thank COLCIENCIAS and UDENAR (Universidad de Nariño) for financial support.

References

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Volume 60| Part 7| July 2004| Pages o483-o485

doi:10.1107/S0108270104012090

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

S-Ethyl N-benzoyl­di­thio­carbamate: two independent hydrogen-bonded R(8) dimers of different symmetry linked into chains by a C—H⋯π(arene) interaction

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

S-Ethyl N-benzoyldithiocarbamate: two independent hydrogen-bonded R $[_{\bf 2}^{\bf 2}]$ (8) dimers of different symmetry linked into chains by a C—H⋯π(arene) interaction