S-ethyl N-benzoyldithiocarbamate: Two independent hydrogen-bonded R 22(8) dimers of different symmetry linked into chains by a C-H...π(arene) interaction

Article abstract of DOI:10.1107/S0108270104012090

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 A, N...S = 3.350 (2) and 3.490 (2) A, and N-H...S = 143 and 172°] into two distinct types of R₂²(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.

Full text of DOI:10.1107/S0108270104012090

organic compounds
Acta Crystallographica Section C
Crystal Structure
This fact alone suf®ces to preclude the possibility of any
additional symmetry.
Communications
ISSN 0108-2701
S-Ethyl N-benzoyldithiocarbamate:
two independent hydrogen-bonded
2
2
R (8) dimers of different
symmetry linked into chains by a
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
CÐHÁ Á Áp(arene) interaction
a
b
c
John N. Low, Justo Cobo, Henry Insuasty, Martin
c
c
d
Estrada, Edward Cort e s and Christopher Glidewell *
2
(
1 � x, 1 � y, 1 � z), so generating a centrosymmetric R (8)
2
a
1
1
1
Department of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen
dimer (Bernstein et al., 1995) centred at ( , , ) (Fig. 2a).
2 2 2
b
AB24 3UE, Scotland, Departamento de Qu Âõ mica Inorg a nica y Org a nica,
However, for molecules of type 2 (Fig. 1b), atom N22 at (x, y,
3
c
Universidad de Ja e n, 23071 Ja e n, Spain, Departamento de Qu Âõ mica, Universidad de
z) acts as a donor to thione atom S23 at (1 � x, y, � z), so
d
2
Nari Än o, Cuidad Universitaria, Torobajo, AA1175 Pasto, Colombia, and School
2
2
that this R (8) dimer (Fig. 2b) lies across the twofold rotation
1
of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
Correspondence e-mail: cg@st-andrews.ac.uk
3
4
axis along ( , y, ). The dimensions of the two independent
NÐHÁ Á ÁS hydrogen bonds (Table 2) are markedly different.
Although the NÁ Á ÁS distance is above the sum of the
2
Received 17 May 2004
Accepted 18 May 2004
Online 22 June 2004
Ê
conventional van der Waals radii (3.3 A; 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 HÁ Á ÁS, NÁ Á ÁS and NÐ
0
The title compound, C H NOS , crystallizes with Z = 2 in
2
1
0
11
space group C2/c. The molecules are linked by two NÐHÁ Á ÁS
Ê
hydrogen bonds [HÁ Á ÁS = 2.60 and 2.62 A, NÁ Á ÁS = 3.350 (2)
Ê
Ê
ꢀ
HÁ Á ÁS parameters of 2.46 (1) A, 3.40 (1) A and 158 (1) ,
Ê
ꢀ
and 3.490 (2) A, and NÐHÁ Á ÁS = 143 and 172 ] into two
respectively, in such bonds involving the neutral species
2
2
distinct types of R (8) dimer, viz. one generated by inversion
and the other by a twofold rotation axis. A single CÐ
1
R R C S as an acceptor, and 2.51 (1) A, 3.44 (1) A and
2
Ê
Ê
cH hÁaÁiÁ nꢀs .( arene) hydrogen bond links the two types of dimer into
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-aroylimino-
dithiocarbonates used in the synthesis of many organic
compounds (August õÂ n et al., 1980). We have modi®ed the
reported method for the synthesis of S-methyl N-benzoyldi-
thiocarbamate (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
0
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
de®ning the orientation of the benzene rings relative to the
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.
ꢀ
rest of the nearly planar molecular skeletons differ by 22 .
Acta Cryst. (2004). C60, o483±o485
DOI: 10.1107/S0108270104012090
# 2004 International Union of Crystallography o483

organic compounds
ꢀ
1
58 (1) , respectively, in such bonds involving neutral thio-
ureas as an acceptor. Accordingly, the NÐHÁ Á ÁS 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 CÐHÁ Á Áꢀ(arene)
hydrogen bond. Atoms C46 in the type 2 molecules at (x, y, z)
3
2
and (1 � x, y, � z) lie in the dimer across the twofold axis
Figure 3
A stereoview of part of the crystal structure of (I), showing the formation
2
2
of the [201] chain of rings linking the two types of R (8) dimer.
1
3
along ( , y, ). These atoms act as hydrogen-bond donors,
respectively, to the C31±C36 rings in the type 1 molecules at
2
4
1
2
1
2
3
2
1
2
3
2
(
components of the type 1 dimers centred at (0, 1, ) and (1, 1,
� + x, + y, z) and ( � x, + y, � z), which are themselves
1
2
1
(
), respectively. Within these type 1 dimers, the molecules at
1
3
1
3
1
� x, 2 � y, 1 � z) and ( + x, � y, 2 + z) similarly accept
2
2
2
hydrogen bonds from atoms C46 in the type 2 molecules at
1
(
1 � x, 2 � y, 1 � z) and (1 + x, 2 � y, 2 + z), respectively,
which themselves lie in the type 2 dimers across the rotation
1
1
3
5
axes along ( , � y, ) and ( , � y, ). Propagation of this single
2
4
2
4
CÐHÁ Á Áꢀ(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-speci®c
interactions between adjacent chains.
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 re¯ux 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 Â 25 ml). The combined organic extracts were dried over an-
hydrous 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
8
4
7%, m.p. 348 K; literature (Nash et al., 1969) m.p. 352±353 K, yield
9%].
Crystal data
�
3
C
10
H11NOS
2
D
x
= 1.404 Mg m
M
r
= 225.34
Mo Kꢂ radiation
Monoclinic, C2=c
Cell parameters from 4840
re¯ections
Figure 2
Ê
a = 21.8190 (5) A
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, 2 � z).
Ê
b = 8.4596 (2) A
ꢀ
ꢃ = 3.1±27.5
ꢄ = 0.46 mm
T = 120 (2) K
Ê
� 1
c = 23.1792 (5) A
ꢁ = 94.5140 (14)
ꢀ
Ê
3
V = 4265.15 (17) A
Z = 16
Block, colourless
0.20 Â 0.20 Â 0.16 mm
3
ꢁ
o484 John N. Low et al.
C
10
H
11NOS
2
Acta Cryst. (2004). C60, o483±o485

organic compounds
Data collection
Data collection: KappaCCD Server Software (Nonius, 1997); cell
re®nement: 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 re®ne structure: OSCAIL and SHELXL97
Nonius KappaCCD diffractometer
3569 re¯ections with I > 2ꢆ(I)
int = 0.067
'
scans, and ! scans with ꢅ offsets
Absorption correction: multi-scan
SORTAV; Blessing, 1995, 1997)
min = 0.902, Tmax = 0.929
R
ꢀ
ꢃ
max = 27.5
(
T
h = � 28 ! 28
k = � 10 ! 10
l = � 30 ! 29
(Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); soft-
3
4
3 304 measured re¯ections
840 independent re¯ections
ware used to prepare material for publication: SHELXL97 and
PRPKAPPA (Ferguson, 1999).
Re®nement
2
2
2
2
Re®nement on F
2
w = 1/[ꢆ (F ) + (0.0447P)
o
2
X-ray data were collected at the EPSRC X-ray Crystal-
lographic 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
Consejer õ a de Educaci o n y Ciencia (Junta de Andaluc õ a,
Spain) and the Universidad de Ja e n for ®nancial support. HI,
ME and EC thank COLCIENCIAS and UDENAR (Univer-
sidad de Nari nÄ o) for ®nancial support.
R[F > 2ꢆ(F )] = 0.037
wR(F ) = 0.089
S = 1.01
+ 0.8703P]
where P = (Fo + 2F )/3
2
2
2
c
(Á/ꢆ)max = 0.001
Ê
� 3
Áꢇmax = 0.29 e A
4
2
840 re¯ections
55 parameters
Áꢇmin = � 0.38 e AÊ
� 3
H-atom parameters constrained
Table 1
Selected geometric parameters (A, ).
Ê
ꢀ
C11ÐO11
C11ÐN12
N12ÐC13
C13ÐS13
C13ÐS14
S14ÐC15
1.214 (2)
1.394 (2)
1.376 (2)
1.6586 (18)
1.7414 (19)
1.8103 (18)
C21ÐO21
C21ÐN22
N22ÐC23
C23ÐS23
C23ÐS24
S24ÐC25
1.214 (2)
1.394 (2)
1.379 (2)
1.6552 (18)
1.7333 (19)
1.8116 (18)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1733). Services for accessing these data are
described at the back of the journal.
C31ÐC11ÐN12ÐC13
C11ÐN12ÐC13ÐS14
175.14 (16)
� 1.6 (2)
C41ÐC21ÐN22ÐC23 � 177.70 (16)
C21ÐN22ÐC23ÐS24
N22ÐC23ÐS24ÐC25
C23ÐS24ÐC25ÐC26
N22ÐC21ÐC41ÐC42
� 4.1 (2)
176.92 (14)
� 173.31 (13)
� 22.7 (3)
References
N12ÐC13ÐS14ÐC15 � 173.39 (13)
C13ÐS14ÐC15ÐC16
N12ÐC11ÐC31ÐC32
� 174.12 (13)
� 45.0 (2)
Allen, F. H. (2002). Acta Cryst. B58, 380±388.
Allen, F. H., Bird, C. M., Rowland, R. S. & Raithby, P. R. (1997). Acta Cryst.
B53, 680±695.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1±19.
August Âõ n, M., Richter, M. & Salas, S. (1980). J. Prakt. Chem. 322, 55±68.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Table 2
Hydrogen-bonding geometry (A, ).
Ê
ꢀ
Cg1 is the centroid of the C31±C36 ring.
Blessing, R. H. (1995). Acta Cryst. A51, 33±37.
Blessing, R. H. (1997). J. Appl. Cryst. 30, 421±426.
Bondi, A. (1964). J. Phys. Chem. 68, 441±451.
Elmore, D. T., Ogle, J. R., Fletcher, W. & Toseland, P. A. (1956). J. Chem. Soc.
pp. 4458±4463.
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada.
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography
Centre, Chemistry Department, NUI Galway, Ireland.
Nash, B. W., Newberry, R. A., Pickles, R. & Warburton, W. K. (1969). J. Chem.
Soc. C, pp. 2794±2799.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
i
N12ÐH12Á Á ÁS13
N22ÐH22Á Á ÁS23
0.88
0.88
0.95
2.62
2.60
2.85
3.490 (2)
3.350 (2)
3.678 (2)
172
143
146
ii
iii
C46ÐH46Á Á ÁCg1
3
1 1
2
Symmetry codes: (i) 1 � x; 1 � y; 1 � z; (ii) 1 � x; y; 2 � z; (iii) x � 2
;
‡ y; z.
Nonius (1997). KappaCCD Server Software. Windows 3.11 Version. Nonius
BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M.
Sweet, pp. 307±326. New York: Academic Press.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
G oÈ ttingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
The systematic absences permitted C2/c and Cc as possible space
groups; C2/c was selected and con®rmed by the structure analysis. All
H atoms were located from difference maps and subsequently treated
as riding atoms, with CÐH distances of 0.95 (aromatic), 0.98 (CH
3
) or
), an NÐH distance of 0.88 A, and Uiso(H) values of
.2Ueq(C,N) or 1.5Ueq(Cmethyl).
Ê
Ê
0
1
.99 A (CH
2
ꢁ
Acta Cryst. (2004). C60, o483±o485
John N. Low et al.
C
10
H
11NOS
2
o485