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

Article abstract of DOI:10.1107/S0108270104029361

Molecules of the title compound, C₁₀H₁₀ClNOS ₂, are linked into C(4) chains by an N-H...O hydrogen bond [H...O = 2.16 A, N...O = 3.013 (3) A and N-H...O = 176°], and the chains are linked into sheets by a centrosymmetric π

Full text of DOI:10.1107/S0108270104029361

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
but this is probably just an adventitious consequence of the
NÐHÁ Á ÁO hydrogen bond. A second [001] chain, related to
the ®rst by inversion, is generated by the c-glide plane at y = 34.
The [001] chains in (I) are weakly linked into sheets by an
aromatic ꢀ±ꢀ stacking interaction. The aryl rings of the mol-
ecules at (x, y, z) and (1 x, 1 y, 1 z), which form parts of
ISSN 0108-2701
1
3
S-Ethyl N-(4-chlorobenzoyl)dithio-
carbamate: sheets built from p-stacked
hydrogen-bonded chains
the chains along y = and y = , respectively, are strictly
4
4
Ê
parallel; the interplanar spacing is 3.464 (2) A and the ring-
Ê
centroid separation is 3.865 (2) A, corresponding to a ring-
Ê
centroid offset of 1.714 (2) A. Propagation of this interaction
then links the [001] chains into a (100) sheet (Fig. 3); there are
no direction-speci®c interactions between adjacent sheets.
John N. Low,a*³ Justo Cobo,b Henry Insuasty,c Edward
c
d
e
Â
Cortes, Braulio Insuasty and Christopher Glidewell
aDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen
b
Â
Â
Â
AB24 3UE, Scotland, Departamento de Quõmica Inorganica y Organica, Univer-
c
Â
Â
Â
sidad de Jaen, 23071 Jaen, Spain, Departamento de Quõmica, Universidad de
Narino, Cuidad Universitaria, Torobajo, AA1175 Pasto, Colombia, dGrupo de
Ä
Â
Â
Â
Investigacion de Compuestos Heterociclõcos, Departamento de Quõmica, Univer-
sidad de Valle, AA 25360 Cali, Colombia, and eSchool of Chemistry, University of St
Andrews, Fife KY16 9ST, Scotland
Correspondence e-mail: che562@abdn.ac.uk
Received 8 November 2004
Accepted 11 November 2004
Online 11 December 2004
Molecules of the title compound, C10H10ClNOS2, are linked
into C(4) chains by an NÐHÁ Á ÁO hydrogen bond [HÁ Á ÁO =
ꢀ
Ê
Ê
2.16 A, NÁ Á ÁO = 3.013 (3) A and NÐHÁ Á ÁO = 176 ], and the
chains are linked into sheets by a centrosymmetric ꢀ±ꢀ
stacking interaction.
There is a ClÁ Á ÁCl contact involving molecules at (x, y, z)
and (1 x, 2 y, 1 z), with a ClÁ Á ÁCl distance of
ꢀ
Ê
3.135 (2) A and a CÐClÁ Á ÁCl angle of 165.5 (2) ; however,
these two molecules lie in the same (100) sheet. The ClÁ Á ÁCl
distance is certainly shorter than the sum of the van der Waals
Comment
Ê
radii (3.52 A) given by Bondi (1964); however, the sum of the
S-Alkyl N-aroyldithiocarbamates are utilized in the prepara-
tion of S,S-dialkyl N-aroyliminodithiocarbonates, which are
themselves useful intermediates for organic synthesis
Â
(Augustõn 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 unsub-
stituted analogue (II) (Low et al., 2004). Compound (I) crys-
tallizes in space group P21/c with Z0 = 1, whereas (II)
crystallizes in C2/c with Z0 = 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 CÐ
SÐCÐC torsion angles are both close to 180ꢀ, 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 NÐHÁ Á ÁO 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 = 14 (Fig. 2). There is also a short intermolecular CÐ
HÁ Á ÁO contact involving the same two molecules (Table 1),
Figure 1
The molecule of (I), showing the atom-labelling scheme. Displacement
ellipsoids are drawn at the 30% probability level.
³ Correspondence address: Department of Electrical Engineering and Physics,
School of Engineering and Physical Science, University of Dundee, Dundee
DD1 4HN, Scotland.
Acta Cryst. (2005). C61, o7±o9
DOI: 10.1107/S0108270104029361
# 2005 International Union of Crystallography o7

organic compounds
room temperature for 27 h. Ice-water was added and the title
compound was extracted with ethyl acetate (3 Â 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
3
C10H10ClNOS2
Mr = 259.76
Monoclinic, P21=c
Dx = 1.429 Mg m
Mo Kꢂ radiation
Cell parameters from 2756
re¯ections
Ê
Ê
a = 14.4020 (7) A
Figure 2
b = 9.1110 (14) A
ꢃ = 5.0±27.5ꢀ
ꢄ = 0.63 mm
T = 120 (2) K
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, 12 + z) and (x, 1 y, 21 + z),
respectively.
1
Ê
c = 9.7040 (13) A
ꢁ = 108.484 (8)ꢀ
3
Ê
V = 1207.6 (3) A
Z = 4
Block, colourless
0.41 Â 0.28 Â 0.23 mm
Data collection
Nonius KappaCCD area-detector
diffractometer
' and ! scans
Absorption correction: multi-scan
(EvalCCD; Duisenberg et al.,
2003)
Tmin = 0.781, Tmax = 0.868
22 106 measured re¯ections
2756 independent re¯ections
1334 re¯ections with I > 2ꢅ(I)
Rint = 0.136
ꢃmax = 27.5ꢀ
h = 18 ! 18
k = 11 ! 11
l = 12 ! 12
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.055
wR(F2) = 0.139
S = 1.00
2756 re¯ections
w = 1/[ꢅ2(F2o) + (0.0655P)2
+ 0.0228P]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max < 0.001
Figure 3
A stereoview of part of the crystal structure of (I), showing the formation
of a (100) sheet of ꢀ-stacked [001] chains. For clarity, H atoms bonded to
C atoms have been omitted.
3
Ê
Áꢆmax = 0.35 e A
3
Ê
0.33 e A
137 parameters
H-atom parameters constrained
Áꢆmin
=
minor radii in the polar ¯attening model (Nyburg & Faerman,
Ê
1985) is only 3.16 A, so this contact may be of limited signif-
Table 1
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
icance. Nonetheless, the CÐClÁ Á ÁCl 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 90ꢀ and the other around 180ꢀ.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N2ÐH2Á Á ÁO1i
0.86
0.93
2.16
2.50
3.013 (3)
3.070 (3)
176
120
C12ÐH12Á Á ÁO1i
Symmetry code: (i) x; 12 y; z
.
1
2
By contrast, the hydrogen bonding in (II) does not involve
the O atom at all; instead, the primary aggregation is domi-
nated by the formation, by means of pairs of NÐHÁ Á ÁS
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 CÐHÁ Á Áꢀ(arene) hydrogen bond. Thus, the
types of intermolecular interaction manifested in the supra-
molecular aggregation in (I) and (II) are entirely different; it is
striking that the introduction of a remote substituent is asso-
ciated with such a difference in the nature of the hydrogen
bonding.
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 CÐH distances of 0.93 (aromatic), 0.96
Ê
Ê
(CH3) and 0.97 A (CH2), and NÐH distances of 0.86 A, and with
Uiso(H) values of 1.2Ueq(C,N) or 1.5Ueq(Cmethyl).
Data collection: COLLECT (Hooft, 1999); cell re®nement:
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 re®ne 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).
Experimental
Â
X-ray data were collected at the `Servicios Tecnicos de
Investigacion', University of Jaen. JC thanks the Consejerõa de
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 re¯ux for 15 min to afford 4-chloro-
benzoyl isothiocyanate, which was not isolated. After cooling the
intermediate solution to 273 K under an inert atmosphere, ethane-
thiol (35 ml, 0.47 mol) was added, and this mixture was then stirred at
Â
Â
Â
Â
Educacion y Ciencia (Junta de Andalucõa, Spain) and the
Universidad de Jaen for ®nancial support. HI, ME and EC
Â
Â
thank COLCIENCIAS and UDENAR (Universidad de
NarinÄo) for ®nancial support. BI thanks COLCIENCIAS and
ꢁ
o8 John N. Low et al.
C10H10ClNOS2
Acta Cryst. (2005). C61, o7±o9

organic compounds
Bondi, A. (1964). J. Phys. Chem. 68, 441±451.
Duisenberg, A. J. M., Hooft, R. W. W., Schreurs, A. M. M. & Kroon, J. (2000).
J. Appl. Cryst. 33, 893±898.
Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003).
J. Appl. Cryst. 36, 220±229.
UNIVALLE (Universidad del Valle) for ®nancial support.
JNL thanks NCR Self-Service, Dundee, for grants which have
provided computing facilities for this work.
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Nether-
lands.
Â
Low, J. N., Cobo, J., Insuasty, H., Estrada, M., Cortes, E. & Glidewell, C. (2004).
Acta Cryst. C60, o483±o485.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1793). Services for accessing these data are
described at the back of the journal.
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography
Centre, Chemistry Department, NUI Galway, Ireland.
Nyburg, S. C. & Faerman, C. H. (1985). Acta Cryst. B41, 274±279.
Ramasubbu, N., Parthasarathy, R. & Murray-Rust, P. (1986). J. Am. Chem.
Soc. 108, 4308±4314.
References
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C.,
Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J.
Appl. Cryst. 32, 115±119.
Â
Augustõn, M., Richter, M. & Salas, S. (1980). J. Prakt. Chem. 322, 55±68.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
GoÈttingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
ꢁ
Acta Cryst. (2005). C61, o7±o9
John N. Low et al. C10H10ClNOS2 o9