S-Ethyl N-(4-chloro­benzoyl)­di­thio­carbamate: sheets built from π-stacked hydrogen-bonded chains

Molecules of the title compound, C₁₀H₁₀ClNOS₂, are linked into C(4) chains by an N—H⋯O hydrogen bond [H⋯O = 2.16 Å, N⋯O = 3.013 (3) Å and N—H⋯O = 176°], and the chains are linked into sheets by a centrosymmetric π–π stacking interaction.

Comment

S-Alkyl N-aroyldi­thio­carbamates are utilized in the preparation of S,S-di­alkyl N-aroyl­imino­di­thio­carbonates, which are themselves useful intermediates for organic synthesis (Augustín et al., 1980). We report here the molecular and supramolecular structures of the title compound, (I) (Fig. 1), which differ in several respects from those of the unsubstituted analogue (II) (Low et al., 2004). Compound (I) crystallizes in space group P2₁/c with Z′ = 1, whereas (II) crystallizes in C2/c with Z′ = 2. While the corresponding bond distances and angles in (I) and (II) are very similar, the molecular conformations adopted by the S-ethyl substituent are different. For the independent mol­ecules in (II), the C—S—C—C torsion angles are both close to 180°, but in (I) this angle is only 82.5 (3)° (Fig. 1).

The most striking difference between (I) and (II) lies in their supramolecular aggregations. In (I), this is dominated by a nearly linear N—H⋯O hydrogen bond (Table 1), which gives rise to a C(4) chain (Bernstein et al., 1995) running parallel to the [001] direction and generated by the c-glide plane at y = (Fig. 2). There is also a short intermolecular C—H⋯O contact involving the same two mol­ecules (Table 1), but this is probably just an adventitious consequence of the N—H⋯O hydrogen bond. A second [001] chain, related to the first by inversion, is generated by the c-glide plane at y = .

The [001] chains in (I) are weakly linked into sheets by an aromatic π–π stacking interaction. The aryl rings of the mol­ecules at (x, y, z) and (1 − x, 1 − y, 1 − z), which form parts of the chains along y = and y = , respectively, are strictly parallel; the interplanar spacing is 3.464 (2) Å and the ring-centroid separation is 3.865 (2) Å, corresponding to a ring-centroid offset of 1.714 (2) Å. Propagation of this interaction then links the [001] chains into a (100) sheet (Fig. 3); there are no direction-specific interactions between adjacent sheets.

There is a Cl⋯Cl contact involving mol­ecules at (x, y, z) and (1 − x, 2 − y, 1 − z), with a Cl⋯Cl distance of 3.135 (2) Å and a C—Cl⋯Cl angle of 165.5 (2)°; however, these two mol­ecules lie in the same (100) sheet. The Cl⋯Cl distance is certainly shorter than the sum of the van der Waals radii (3.52 Å) given by Bondi (1964); however, the sum of the minor radii in the polar flattening model (Nyburg & Faerman, 1985) is only 3.16 Å, so this contact may be of limited significance. Nonetheless, the C—Cl⋯Cl angle is consistent with the results of a database analysis (Ramasubbu et al., 1986), which showed that such angles fall into two clusters, one around 90° and the other around 180°.

By contrast, the hydrogen bonding in (II) does not involve the O atom at all; instead, the primary aggregation is dominated by the formation, by means of pairs of N—H⋯S hydrogen bonds, of two independent R₂²(8) dimers, one generated by inversion and the other generated by a twofold screw axis. These two independent dimers are then linked into chains by a single C—H⋯π(arene) hydrogen bond. Thus, the types of intermolecular interaction manifested in the supramolecular aggregation in (I) and (II) are entirely different; it is striking that the introduction of a remote substituent is associated with such a difference in the nature of the hydrogen bonding.

Figure 1 The mol­ecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

Figure 2 Part of the crystal structure of (I), showing the formation of a hydrogen-bonded C(4) chain along [001]. For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, 1 − y, − + z) and (x, 1 − y,  + z), respectively.

Figure 3 A stereoview of part of the crystal structure of (I), showing the formation of a (100) sheet of π-stacked [001] chains. For clarity, H atoms bonded to C atoms have been omitted.

Experimental

4-Chloro­benzoyl chloride (5.5 ml, 0.043 mol) was added to a solution of potassium thio­cyanate (4.1 g, 0.043 mol) in aceto­nitrile (75 ml); this mixture was heated under reflux for 15 min to afford 4-chloro­benzoyl iso­thio­cyanate, which was not isolated. After cooling the intermediate solution 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 then 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 89%, m.p. 398 K).

Crystal data

• C₁₀H₁₀ClNOS₂

• M_r = 259.76

• Monoclinic, P2₁/c

• a = 14.4020 (7) Å

• b = 9.1110 (14) Å

• c = 9.7040 (13) Å

• β = 108.484 (8)°

• V = 1207.6 (3) ų

• Z = 4

• D_x = 1.429 Mg m⁻³

• Mo Kα radiation

• Cell parameters from 2756 reflections

• θ = 5.0–27.5°

• μ = 0.63 mm⁻¹

• T = 120 (2) K

• Block, colourless

• 0.41 × 0.28 × 0.23 mm

Data collection

• Nonius KappaCCD area-detector diffractometer

• φ and ω scans

• Absorption correction: multi-scan (EvalCCD; Duisenberg et al., 2003) T_min = 0.781, T_max = 0.868

• 22 106 measured reflections

• 2756 independent reflections

• 1334 reflections with I > 2σ(I)

• R_int = 0.136

• θ_max = 27.5°

• h = −18 → 18

• k = −11 → 11

• l = −12 → 12

Refinement

• Refinement on F²

• R[F² > 2σ(F²)] = 0.055

• wR(F²) = 0.139

• S = 1.00

• 2756 reflections

• 137 parameters

• H-atom parameters constrained

• w = 1/[σ²(F_o²) + (0.0655P)² + 0.0228P] where P = (F_o² + 2F_c²)/3

• (Δ/σ)_max < 0.001

• Δρ_max = 0.35 e Å⁻³

• Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1^i	0.86	2.16	3.013 (3)	176
C12—H12⋯O1^i	0.93	2.50	3.070 (3)	120
Symmetry code: (i) .

The space group P2₁/c was uniquely assigned from the systematic absences. All H atoms were located from difference maps and then treated as riding atoms, with C—H distances of 0.93 (aromatic), 0.96 (CH₃) and 0.97 Å (CH₂), and N—H distances of 0.86 Å, and with U_iso(H) values of 1.2U_eq(C,N) or 1.5U_eq(C_methyl).

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EvalCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Supporting information

S1. Comment

S-Alkyl N-aroyldithiocarbamates are utilized in the preparation of S,S-dialkyl N-aroyliminodithiocarbonates, which are themselves useful intermediates for organic synthesis (Augustín et al., 1980). We report here the molecular and supramolecular structures of the title compound, (I) (Fig. 1), which differ in several respects from those of the unsubstituted analogue, (II) (Low et al., 2004). Compound (I) crystallizes in space group P2₁/c with Z' = 1, whereas (II) crystallizes in C2/c with Z' = 2. While the corresponding bond distances and angles in (I) and (II) are very similar, the molecular conformations adopted by the S-ethyl substituent are different. For the independent molecules in (II), the C—S—C—C torsion angles are both close to 180°, but in (I) this angle is only 82.5 (3)° (Fig. 1).

The most striking difference between (I) and (II) lies in their supramolecular aggregation. In (I), this is dominated by a nearly linear N—H···O hydrogen bond (Table 1), which gives rise to a C(4) chain (Bernstein et al., 1995) running parallel to the [001] direction and generated by the c-glide plane at y = 0.25 (Fig. 2). There is also a short intermolecular C—H···O contact involving the same two molecules (Table 1), but this is probably just an adventitious consequence of the N—H···O hydrogen bond. A second [001] chain, related to the first by inversion, is generated by the c-glide plane at y = 0.75.

The [001] chains in (I) are weakly linked into sheets by an aromatic π–π stacking interaction. The aryl rings of the molecules at (x, y, z) and (1 − x, 1 − y, 1 − z), which form parts of the chains along y = 0.25 and y = 0.75 respectively, are strictly parallel; the interplanar spacing is 3.464 (2) Å and the ring-centroid separation is 3.865 (2) Å, corresponding to a ring-centroid offset of 1.714 (2) Å. Propagation of this interaction then links the [001] chains into a (100) sheet (Fig. 3); there are no direction-specific interactions between adjacent sheets.

There is a Cl···Cl contact involving molecules at (x, y, z) and (1 − x, 2 − y, 1 − z), with a Cl···Clⁱ distance of 3.135 (2) Å and a C—Cl···Clⁱ angle of 165.5 (2)° [symmetry code: (i) 1 − x, 2 − y, 1 − z]; however, these two molecules lie in the same (100) sheet. The Cl···Cl distance is certainly shorter than the sum of the van der Waals radii (3.52 Å) given by Bondi (1964); however, the sum of the minor radii in the polar flattening model (Nyburg & Faerman, 1985) is only 3.16 Å, so this contact may be of limited significance. Nonetheless, the C—Cl···Cl angle is consistent with the results of a database analysis (Ramasubbu et al., 1986), which showed that such angles fall into two clusters, one around 90° and the other around 180°.

By contrast, the hydrogen bonding in (II) does not involve the O atom at all; instead, the primary aggregation is dominated by the formation, by means of pairs of N—H···S hydrogen bonds, of two independent R²₂(8) dimers, one generated by inversion and the other generated by a twofold screw axis. These two independent dimers are then linked into chains by a single C—H···π(arene) hydrogen bond. Thus the types of intermolecular interaction manifested in the supramolecular aggregation in (I) and (II) are entirely different; it is striking that the introduction of a remote substituent is associated with such a difference in the nature of the hydrogen bonding.

S2. Experimental

4-Chlorobenzoyl chloride (5.5 ml, 0.043 mol) was added to a solution of potassium thiocyanate (4.1 g, 0.043 mol) in acetonitrile (75 ml); this mixture was heated under reflux for 15 min to afford 4-chlorobenzoyl isothiocyanate, which was not isolated. After cooling the intermediate solution 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 then 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 89%, m.p. 398 K).

S3. Refinement

The space group P2₁/c was uniquely assigned from the systematic absences. All H atoms were located from difference maps, and then treated as riding atoms with C—H distances of 0.93 (aromatic), 0.96 (CH₃) and 0.97 Å (CH₂), and N—H distances of 0.86 Å, with U_iso(H) values of 1.2U_eq(C,N) or 1.5U_eq(C_methyl).

Computing details

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: OSCAIL (McArdle, 2003)? and SIR97 (Altomare et al., 1999); 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

	Fig. 1. The molecule of (I), showing the atom-labelling scheme. Displacememt ellipsoids are drawn at the 30% probability level.
	Fig. 2. Part of the crystal structure of (I), showing the formation of a hydrogen-bonded C(4) chain along [001]. For clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (x, 1 − y, −0.5 + z) and (x, 1 − y, 0.5 + z), respectively.
	Fig. 3. A stereoview of part of the crystal structure of (I), showing the formation of a (100) sheet of π-stacked [001] chains. For clarity, H atoms bonded to C atoms have been omitted.

S-Ethyl N-(4-chlorobenzoyl)dithiocarbamate

Crystal data

C10H10ClNOS2	F(000) = 536
Mr = 259.76	Dx = 1.429 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2756 reflections
a = 14.4020 (7) Å	θ = 5.0–27.5°
b = 9.1110 (14) Å	µ = 0.63 mm^−1
c = 9.7040 (13) Å	T = 120 K
β = 108.484 (8)°	Block, colourless
V = 1207.6 (3) Å^3	0.41 × 0.28 × 0.23 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	2756 independent reflections
Radiation source: fine-focus sealed X-ray tube	1334 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.136
ϕ and ω scans	θmax = 27.5°, θmin = 5.0°
Absorption correction: multi-scan (EVALCCD; Duisenberg et al., 2003)	h = −18→18
Tmin = 0.781, Tmax = 0.868	k = −11→11
22106 measured reflections	l = −12→12

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0655P)^2 + 0.0228P] where P = (Fo^2 + 2Fc^2)/3
2756 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.33 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cl14	0.55581 (8)	0.85530 (10)	0.56450 (11)	0.0789 (4)
S3	0.84470 (9)	−0.00157 (13)	0.47246 (11)	0.0873 (4)
S4	0.82619 (7)	−0.03878 (10)	0.76842 (10)	0.0642 (3)
O1	0.70464 (16)	0.1825 (2)	0.7886 (2)	0.0560 (6)
N2	0.74835 (16)	0.1775 (3)	0.5837 (2)	0.0425 (6)
C1	0.7079 (2)	0.2449 (3)	0.6787 (3)	0.0409 (7)
C3	0.8033 (2)	0.0508 (3)	0.6028 (3)	0.0465 (8)
C5	0.9118 (3)	−0.1788 (4)	0.7599 (5)	0.0806 (12)
C6	1.0153 (3)	−0.1250 (6)	0.8008 (6)	0.127 (2)
C11	0.66898 (19)	0.3941 (3)	0.6409 (3)	0.0374 (7)
C12	0.7049 (2)	0.4906 (3)	0.5601 (3)	0.0417 (7)
C13	0.6706 (2)	0.6326 (3)	0.5368 (3)	0.0484 (8)
C14	0.5995 (2)	0.6772 (3)	0.5940 (3)	0.0488 (8)
C15	0.5618 (2)	0.5839 (4)	0.6744 (3)	0.0529 (8)
C16	0.5975 (2)	0.4425 (4)	0.6981 (3)	0.0495 (8)
H2	0.7379	0.2207	0.5014	0.051*
H5A	0.9084	−0.2583	0.8246	0.097*
H5B	0.8931	−0.2179	0.6619	0.097*
H6A	1.0561	−0.2004	0.7816	0.191*
H6B	1.0380	−0.1008	0.9023	0.191*
H6C	1.0182	−0.0393	0.7447	0.191*
H12	0.7527	0.4593	0.5211	0.050*
H13	0.6953	0.6973	0.4830	0.058*
H15	0.5132	0.6154	0.7119	0.064*
H16	0.5734	0.3786	0.7533	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl14	0.1020 (7)	0.0495 (6)	0.0965 (7)	0.0314 (5)	0.0472 (6)	0.0161 (5)
S3	0.1175 (9)	0.0928 (9)	0.0616 (6)	0.0554 (7)	0.0424 (6)	0.0056 (5)
S4	0.0758 (6)	0.0578 (6)	0.0646 (6)	0.0219 (5)	0.0301 (5)	0.0194 (4)
O1	0.0875 (16)	0.0429 (13)	0.0467 (13)	0.0105 (11)	0.0343 (12)	0.0067 (10)
N2	0.0560 (15)	0.0378 (15)	0.0353 (13)	0.0097 (12)	0.0167 (12)	0.0035 (11)
C1	0.0497 (17)	0.0372 (18)	0.0364 (16)	0.0010 (14)	0.0143 (14)	−0.0019 (14)
C3	0.0488 (17)	0.0433 (19)	0.0478 (18)	0.0062 (15)	0.0157 (15)	−0.0002 (14)
C5	0.090 (3)	0.065 (3)	0.094 (3)	0.034 (2)	0.041 (2)	0.027 (2)
C6	0.077 (3)	0.147 (6)	0.147 (5)	0.039 (3)	0.022 (3)	0.014 (4)
C11	0.0421 (16)	0.0376 (17)	0.0339 (15)	0.0032 (13)	0.0139 (14)	0.0003 (12)
C12	0.0482 (17)	0.0394 (18)	0.0434 (16)	0.0046 (14)	0.0230 (14)	−0.0028 (14)
C13	0.0559 (19)	0.040 (2)	0.0551 (19)	0.0024 (15)	0.0259 (16)	0.0060 (15)
C14	0.0585 (19)	0.0383 (19)	0.0489 (18)	0.0130 (15)	0.0161 (16)	0.0013 (15)
C15	0.0588 (19)	0.052 (2)	0.058 (2)	0.0190 (17)	0.0325 (17)	0.0046 (17)
C16	0.0559 (19)	0.049 (2)	0.0509 (19)	0.0049 (16)	0.0274 (16)	0.0065 (15)

Geometric parameters (Å, º)

C1—O1	1.222 (3)	C16—H16	0.93
C1—N2	1.381 (3)	N2—C3	1.379 (4)
C1—C11	1.471 (4)	N2—H2	0.86
C11—C12	1.383 (4)	C3—S3	1.631 (3)
C11—C16	1.387 (4)	C3—S4	1.738 (3)
C12—C13	1.377 (4)	S4—C5	1.794 (4)
C12—H12	0.93	C5—C6	1.498 (6)
C13—C14	1.373 (4)	C5—H5A	0.97
C13—H13	0.93	C5—H5B	0.97
C14—C15	1.377 (4)	C6—H6A	0.96
C14—Cl14	1.731 (3)	C6—H6B	0.96
C15—C16	1.379 (4)	C6—H6C	0.96
C15—H15	0.93
O1—C1—N2	121.1 (3)	C11—C16—H16	119.5
O1—C1—C11	122.0 (2)	C3—N2—C1	129.0 (2)
N2—C1—C11	116.9 (2)	C3—N2—H2	115.6
C12—C11—C16	118.9 (3)	C1—N2—H2	115.5
C12—C11—C1	123.2 (2)	N2—C3—S3	118.4 (2)
C16—C11—C1	117.8 (2)	N2—C3—S4	116.7 (2)
C13—C12—C11	120.8 (3)	S3—C3—S4	124.84 (18)
C13—C12—H12	119.6	C3—S4—C5	102.85 (17)
C11—C12—H12	119.6	C6—C5—S4	113.3 (3)
C14—C13—C12	119.1 (3)	C6—C5—H5A	108.9
C14—C13—H13	120.4	S4—C5—H5A	108.9
C12—C13—H13	120.4	C6—C5—H5B	108.9
C13—C14—C15	121.7 (3)	S4—C5—H5B	108.9
C13—C14—Cl14	119.3 (2)	H5A—C5—H5B	107.7
C15—C14—Cl14	119.0 (2)	C5—C6—H6A	109.5
C14—C15—C16	118.6 (3)	C5—C6—H6B	109.5
C14—C15—H15	120.7	H6A—C6—H6B	109.5
C16—C15—H15	120.7	C5—C6—H6C	109.5
C15—C16—C11	121.0 (3)	H6A—C6—H6C	109.5
C15—C16—H16	119.5	H6B—C6—H6C	109.5
O1—C1—C11—C12	151.7 (3)	C14—C15—C16—C11	−0.9 (5)
N2—C1—C11—C12	−28.5 (4)	C12—C11—C16—C15	0.6 (4)
O1—C1—C11—C16	−23.7 (4)	C1—C11—C16—C15	176.2 (3)
N2—C1—C11—C16	156.1 (3)	O1—C1—N2—C3	−11.8 (5)
C16—C11—C12—C13	0.1 (4)	C11—C1—N2—C3	168.4 (3)
C1—C11—C12—C13	−175.3 (3)	C1—N2—C3—S3	−178.3 (2)
C11—C12—C13—C14	−0.5 (4)	C1—N2—C3—S4	−0.1 (4)
C12—C13—C14—C15	0.2 (5)	N2—C3—S4—C5	−172.2 (2)
C12—C13—C14—Cl14	−179.8 (2)	S3—C3—S4—C5	5.9 (3)
C13—C14—C15—C16	0.5 (5)	C3—S4—C5—C6	82.5 (3)
Cl14—C14—C15—C16	−179.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1^i	0.86	2.16	3.013 (3)	176
C12—H12···O1^i	0.93	2.50	3.070 (3)	120

Symmetry code: (i) x, −y+1/2, z−1/2.

 

Footnotes

‡Correspondence address: Department of Electrical Engineering and Physics, School of Engineering and Physical Science, University of Dundee, Dundee DD1 4HN, Scotland.