5-(2-Pyridyl)-1,3-dithiane-2-thione

Article abstract of DOI:10.1107/S0108270101008198

The title compound, C₉H₉NS₃, crystallizes with two molecules in the asymmetric unit. In both molecules, the dithiane-2-thione rings adopt a symmetric half-boat conformation with the C atom opposite the C - S_thione

Full text of DOI:10.1107/S0108270101008198

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
of copper complexes (Bellito et al., 1994). The bond distances
2
(Table 1) found here [S C 1.658 (1) and 1.662 (1) A, Csp ÐS
Ê
3
Ê
Ê
1.714 (1)±1.719 (1) A and SÐCsp 1.810 (1)Ð1.815 (1) A] are
very similar to those in the copper complexes, although there
the ligand is mono-, di- or tridentate. For both molecules, the
pyridine ring is in an equatorial position and is twisted by
82.7 (2) and 84.5 (2)ꢀ out of the plane of the half-boat. In both
molecules, the N atom is trans to the axial CÐH bond so that
the molecules have approximate mirror symmetry. The two
ISSN 0108-2701
5-(2-Pyridyl)-1,3-dithiane-2-thione
Alan Hazell,a* Christine J. McKenzieb and Jimmi Nielsenb
aDepartment of Chemistry, Aarhus University, Langelandsgade 140, DK-8000
Arhus C, Denmark, and bDepartment of Chemistry, University of Southern Denmark,
Ê
Odense Campus, DK-5230 Odense M, Denmark
Correspondence e-mail: ach@chem.au.dk
Received 9 February 2001
Accepted 15 May 2001
The title compound, C9H9NS3, crystallizes with two molecules
in the asymmetric unit. In both molecules, the dithiane-2-
thione rings adopt a symmetric half-boat conformation with
the C atom opposite the CÐSthione bond out of the plane. The
pyridine ring is in an equatorial position and is twisted out of
the plane of the half-boat by 82.7 (2) and 84.5 (2)ꢀ in the two
molecules, so that the N atom is trans to the axial CÐH bond
in both cases.
Figure 1
Comment
View of the two molecules of the title compound showing the labelling of
the non-H atoms. Displacement ellipsoids are shown at the 50%
probability level and H atoms are drawn as small circles of arbitrary
radii. The short SÁ Á ÁS interaction is shown by a dashed line.
We were unsuccessful in reproducing the synthesis of S,S0-
[2-(2-pyridyl)trimethylene]bis(O-ethyl dithiocarbonate), (I)
(Uneme et al., 1992). Instead, the previously unknown ring-
closed product 5-(2-pyridyl)-1,3-dithiane-2-thione, (II), was
recovered. The only important difference in the procedures
was that we heated the heterogeneous reaction mixture for a
short time.
molecules are not exactly identical; superimposing the non-H
Ê 2
atoms gives a mean-square deviation of 0.42 A . The differ-
ence is mainly in the angle between the C2/C3/C4 and S1/S2/
S3/C1/C2/C4 planes, which is 124.8 (2)ꢀ for molecule 1 and
120.4 (2)ꢀ for molecule 2 (the molecule with suf®x A on the
labels). This, together with a difference in the angle between
C5ÐC3 and the C2/C3/C4 plane [55.5 (1)ꢀ for molecule 1 and
54.0 (1)ꢀ for molecule 2] means that the angles between C5Ð
C3 and the S1/S2/S3/C1/C2/C4 plane differ by 6.0 (2)ꢀ, so that
in molecule 2, the pyridine ring is bent out of plane.
Ê
The shortest intermolecular SÁ Á ÁS contact is 3.570 (1) A
1
2
between S2 and S3A(x,
y, 12 + z). The x and y coordinates
of the two independent molecules are related approximately
by 32 x and y, but there is no simple relation between the z
coordinates.
The crystal structure of (II) has two almost identical mol-
ecules in the asymmetric unit (Fig. 1). Both the dithiane-2-
thione rings adopt a symmetric half-boat conformation, with
the C atom opposite the CÐSthione bond out of the plane
de®ned by the other atoms; the largest deviations from the
Experimental
Triethylamine (3.95 g, 39 mmol) was added dropwise to a solution of
2-(2-pyridyl)-1,3-propanediol (2.40 g, 16 mmol) (Guanti et al., 1997)
and p-toluenesulfonyl chloride (6.55 g, 34 mmol) in acetonitrile
(32 ml) at 273 K over a period of ca 30 min. The mixture was kept at
279 K for 24 h and then poured into water (120 ml). An oil precipi-
tated which crystallized after removal of the water and the addition of
a little ethanol. The crude product was recrystallized from ethanol,
giving 3.10 g (43%) of 2-(pyridyl)trimethylene bis(p-toluene-
sulfonate). 1H NMR (CDCl3): ꢀ 2.40 (6H, s), 3.46 (1H, quintet),
Ê
Ê
plane are 0.05 (4) A for S3 and 0.04 (2) A for S2A. This
symmetric half-boat conformation is one of the intermediates
postulated for the preferential mode of inversion for the chair
form of cyclohexanone (Bucourt & Hainaut, 1967). This
conformation is also found for 1,3-dithiane-2-thione in a series
ꢁ
Acta Cryst. (2001). C57, 859±860
# 2001 International Union of Crystallography
Printed in Great Britain ± all rights reserved 859

organic compounds
4.32 (4H, d), 7.0±7.4 (6H, m), 7.5±7.8 (5H, m), 8.3±8.4 (1H, m).
13C NMR (CDCl3): ꢀ 22 (CH3), 46 (CH), 68 (CH2), 122.5 (py-C3), 124
(py-C5), 128 (Ar-C3,C5), 130 (Ar-C2,C6), 132 (Ar-C4), 137 (py-C4),
134 (Ar-C1), 149.5 (py-C6), 155.5 (py-C2). A suspension of
2-(pyridyl)trimethylene bis(p-toluenesulfonate) (3.1 g, 6.9 mmol) and
potassium O-ethyldithiocarbonate (3.18 g, 20 mmol) in acetonitrile
(50 ml) was heated under re¯ux for 20 min and then poured into
water (250 ml). The reaction product was extracted with CHCl3 (3 Â
100 ml) and puri®ed by column chromatography (CH2Cl2) to afford a
crude product (ca 300 mg) and a yellow oil. The crude product was
crystallized from ethanol; yield: 200 mg (14%) of (II) as yellow
crystals. The crystals used for the structure analysis were deposited
from CDCl3 (m.p. 393±394 K). Analysis calculated for C9H9NS3:
C 47.54, H 3.99, N 6.16, S 42.31%; found: C 47.59, H 4.10, N 6.17,
Table 1
Selected bond lengths (A).
Ê
S1ÐC1
S2ÐC1
S2ÐC2
S3ÐC1
S3ÐC4
1.658 (1)
S1AÐC1A
S2AÐC1A
S2AÐC2A
S3AÐC1A
S3AÐC4A
1.662 (1)
1.717 (1)
1.810 (1)
1.714 (1)
1.815 (1)
1.719 (1)
1.815 (1)
1.719 (1)
1.812 (1)
The H atoms were included using a riding model and were
Ê
constrained to have CÐH = 0.95 A and Uiso = 1.2Ueq of their parent
atom.
Data collection: SMART (Siemens, 1995); cell re®nement: SAINT
(Siemens, 1995); data reduction: SAINT; program(s) used to solve
structure: SIR97 (Altomare et al., 1997) and KRYSTAL (Hazell,
1995); program(s) used to re®ne structure: modi®ed ORFLS (Busing
et al., 1962) and KRYSTAL; molecular graphics: ORTEPIII (Burnett
& Johnson, 1996) and KRYSTAL; software used to prepare material
for publication: KRYSTAL.
1
S 32.30%. H NMR (CDCl3): ꢀ 3.2±3.8 (5H, m), 7.2±7.4 (3H, m),
7.6±7.8 (1H, m), 8.5±8.6 (1H, m); 13C NMR (CDCl3): ꢀ 39.1 (CH2),
39.2 (CH), 122.2 (py-C3), 122.7 (py-C5), 137 (py-C4), 150 (py-C6),
160 (py-C2), 220 (CÐS); IR: 1010 cm 1, ꢁ(C S); EIMS: m/z 227
(M+, 58), 194 (23), 180 (17), 162 (11), 150 (10), 136 (26), 118 (32),
106 (100), 79 (25).
AH is indebted to the Carslberg Foundation for the
diffractometer and cooling device.
Crystal data
3
C9H9NS3
Mr = 227.38
Dx = 1.511 Mg m
Mo Kꢃ radiation
Cell parameters from 7124
re¯ections
Monoclinic, P21/c
Ê
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: JZ1452). Services for accessing these data are
described at the back of the journal.
a = 17.444 (2) A
Ê
b = 9.6329 (9) A
Ê
ꢄ = 2.5±30.5ꢀ
ꢅ = 0.69 mm
T = 120 K
1
c = 12.680 (1) A
ꢂ = 110.245 (2)ꢀ
3
Ê
V = 1999.1 (3) A
Z = 8
Plate, yellow
0.58 Â 0.40 Â 0.16 mm
References
Data collection
Altomare, A., Cascarano, C., Giacovazzo, C., Guagliardi, A., Moliterni, A. G.
G., Burla, M. C., Polidori, G., Camalli, M. & Spagna, R. (1997). SIR97.
University of Bari, Italy.
Bellito, C., Bigoli, F., Deplano, P., Mercuri, M. L., Pellinghelli, M. A., Staulo, H.
& Trogu, E. F. (1994). Inorg. Chem. 33, 3005±3009.
Bucourt, A. & Hainaut, D. (1967). Bull. Soc. Chim. Fr. pp. 4562±4567.
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak
Ridge National Laboratory, Tennessee, USA.
Busing, W. R., Martin, K. O. & Levy, H. A. (1962). ORFLS. Report ORNL-
TM-305. Oak Ridge National Laboratory, Tennessee, USA.
Guanti, G., Narisano, E. & Riva, R. (1997). Tetrahedron Asymmetry, 13, 2175±
2188.
Hazell, A. (1995). KRYSTAL. Aarhus University, Denmark.
Siemens (1995). SMART, SAINT and XPREP. Siemens Analytical X-ray
Instruments Inc., Madison, Wisconsin, USA.
Uneme, H., Mitsudera, H., Kamikado, T., Kono, Y., Manabe, Y. & Numata, M.
(1992). Biosci. Biotechnol. Biochem. 12, 2023±2033.
Siemens SMART CCD diffrac-
tometer
4802 re¯ections with I > 3ꢆ(I)
Rint = 0.047
! rotation scans with narrow frames
Absorption correction: by integra-
tion (XPREP; Siemens, 1995)
Tmin = 0.687, Tmax = 0.894
25 069 measured re¯ections
6191 independent re¯ections
ꢄ
max = 30.5ꢀ
h = 24 ! 24
k = 13 ! 13
l = 17 ! 17
Intensity decay: none
Re®nement
Re®nement on F
R = 0.024
wR = 0.034
S = 1.27
4802 re¯ections
235 parameters
H-atom parameters constrained
w = 1/{[ꢆcs(F2) + 1.03F2]1/2 |F|}2
(Á/ꢆ)max = 0.001
3
Ê
Áꢇmax = 0.48 (5) e A
3
Ê
0.39 (5) e A
Áꢇmin
=
ꢁ
860 Alan Hazell et al.
C9H9NS3
Acta Cryst. (2001). C57, 859±860