Pyridyl-substituted [1,3]dithiolo-[4,5-b][1,4]dithiine-2-thiones

Article abstract of DOI:10.1007/s10593-005-0157-9

We have obtained 5-(2-pyridyl)[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione for the first time by cycloaddition of 2-ethynylpyridine to 4,5-dihydro-1,3- dithioltrithione (isotrithionedithiol). We have studied this thione, 5-(2-pyridyl)- and 5-(4-pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2- thiones by mass spectroscopy and also IR, UV, ¹H and ¹³C NMR spectra. We have determined the crystal and molecular structure of 5-(2-pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione.

Full text of DOI:10.1007/s10593-005-0157-9

Chemistry of Heterocyclic Compounds, Vol. 41, No. 3, 2005
PYRIDYL-SUBSTITUTED [1,3]DITHIOLO-
[
4,5-b][1,4]DITHIINE-2-THIONES
1
1
2
A. Yu. Koshevaya , V. A. Starodub , and D. Fenske
We have obtained 5-(2-pyridyl)[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione for the first time by
cycloaddition of 2-ethynylpyridine to 4,5-dihydro-1,3-dithioltrithione (isotrithionedithiol). We have
studied this thione, 5-(2-pyridyl)- and 5-(4-pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-
1
13
thiones by mass spectroscopy and also IR, UV, H and C NMR spectra. We have determined the crystal
and molecular structure of 5-(2-pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione.
Keywords: 4,5-dihydro-1,3-dithioltrithione (isotrithionedithiol), 5-(2-pyridyl)[1,3]dithiolo[4,5-b][1,4]-
dithiine-2-thione, 5-(2-pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione, 5-(4-pyridyl)-5,6-
1
13
dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione, IR, H and C NMR spectra, X-ray diffraction
analysis.
4
,5-Dihydro-1,3-dithioltrithione, or isotrithionedithiol (dmit), is widely used to obtain derivatives of
tetrathiafulvalene: components of synthetic metals and superconductors [1-3] and also many mononuclear and
polynuclear metal complexes [4, 5] which can be used to obtain synthetic metals and superconductors. In recent
years, interest has also grown in the chemistry of complexes based on 4,5-ethylenedithio-1,3-dithiol-2-thione
(
C H S ) [6-8]. In this connection, the work of J. Becher et al. [9] on functionalization of dmit with alkylpyridyl
5 4 5
groups is of interest. The Becher method makes it possible to obtain derivatives of dmit that contain two
alkylpyridyl substituents at the 4 and 5 positions. Thus in reaction of the complex [(H C ) N] [Zn(dmit) ] with 2-
5
2 4
2
2
vinylpyridine, the compound 4,5-bis(2-pyridylethylsulfanyl)-1,3-dithiol-2-thione (1) is obtained.
Another reaction route is also possible. In [10], 4,5-(2-pyridylethylenedithio)-1,3-dithiol-2-thione (2)
and 4,5-(4-pyridylethylenedithio)-1,3-dithiol-2-thione (3) are described, the products of cycloaddition of
respectively 2- and 4-vinylpyridine to isotrithionedithiol. Such compounds are of significant interest as ligands
in polynuclear complexes and clusters.
A method has been described for obtaining substituted 4,5-ethylenedithio-1,3-dithiol-2-thiones, based on
the reaction observed by the authors of [10,11] between alkenes and isotrithionedithiol, a compound to which
they assigned a polymeric structure (C S ) . As we established in [12], isotrithionedithiol, synthesized by
3
5 x
oxidation of a solution of sodium isotrithionedithiolate Na C S in DMF by a methanol solution of iodine at 0°C,
2
3 5
has a dimer structure: C S , which is consistent with X-ray diffraction data [13] and allows us to hypothesize the
6
10
possibility of a Diels–Alder type reaction between isotrithionedithiol and alkenes (Scheme 1).
Accordingly, the aim of this work was to study the products of condensation of isotrithionedithiol with
2
- and 4-vinylpyridines, obtained by the method of O. Neiland and J. Becher, and also with 2-ethynylpyridine.
In the latter case, a bicyclic conjugated system is formed.
_
________________________________________________________________________________________
1
V. N. Karazin Kharkov National University, Kharkov 61077, Ukraine; e-mail:
2
vladimir.a.starodub@univer.kharkov.ua. Institute of Inorganic Chemistry, Technical University of Karlsruhe,
Karlsruhe, Germany. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 429-434, March,
2
005. Original article submitted February 11, 2003; revised November 22, 2004.
3
74 0009-3122/05/4103-0374©2005 Springer Science+Business Media, Inc.

Scheme 1
S
S
S
S
S
S
S
S
∆
S
S
S
S
S
2
S
S
R
H
H
S
S
S
S
H
S
S
S
S
S
R
R
S
+
2, 3
S
R C
C
H
S
S
S
S
4
R = 2-pyridyl (2, 4), 4-pyridyl (3)
In the mass spectrum of compound 1, we observe a molecular ion peak m/z 408 (I , 16%) with a
rel
3
2
33
34
corresponding isotope distribution for S, S, and S; the molecular ion peak for compound 2, formed as a
+
result of fragmentation (Scheme 2); and also the peaks for pyridine derivatives with m/z: 107 [C H N] (14), 106
7
9
+
+
[
C H N] (98.7), and 105 [C H N] (100). In the mass spectra of compounds 2 and 3, we observe molecular ion
7 8 7 7
+
+
+
peaks 301.1 (100); the major fragmentary ions are [Sn] , n = 1-8 (12-18); [CS ] (100), and [CS] (20). The mass
2
spectrum of the conjugated compound 4 contains the molecular ion peak 299 (100).
Scheme 2
+
Me
N
S
N
N
S
S
S
+
S
S
S
S
S
S
N
In the IR spectra of compounds 2-4, we observe bands for stretching vibrations ν(C=S) respectively at
-
1
-1
-1
-1
1
059 cm (2), 1065 cm (3), and 1075 cm (4). The band at 1259 cm in the spectrum of compound 4, which is
missing in the spectra of compounds 2 and 3, may be assigned to vibrations of the HC=CPy bond. According to
-
1
[
14], the ν(C=C) vibration band is observed in dithiolate compounds in the 1250-1550 cm region. Other intense
-
bands in the spectra of compounds 2-4 are assigned to stretching vibrations of the pyridine ring (1420-1600 cm
1
)
and to bending vibrations of the C–H bonds [15].
In the electronic spectra, we observe two absorption maxima in the ranges 392-408 nm and 255-270 nm,
which may be assigned to the C S moiety (their position and intensity in compounds 2-4 are practically
3
5
identical) and the pyridyl substituent respectively [16]. Thus the pyridyl and isotrithionedithiol moieties are
weakly coupled even in the conjugated system 4. The reason for this is obvious in the case of compounds 2 and
3
; in compound 4, this is possibly explained by the appreciable dihedral angle between the planes of these
1
13
moieties. The H and C NMR spectra unambiguously confirm the correctness of the hypothesized structures for
compounds 2-4 (see Experimental).
3
75

Fig. 1. Numbering of atoms and thermal vibration ellipsoids
50% probability level) in the structure of compound 2.
(
The conclusions drawn are confirmed by the X-ray diffraction analysis carried out for crystals of
compound 2 (Fig. 1, Tables 1 and 2). As we see from Fig. 1, the C S moiety is practically flat; the pyridyl
3
5
radical is rotated by a 69.12(8)° angle with respect to the C(4)–C(6) bond. The C–C and C–S bond lengths of the
C S moiety (Table 1) are found within ranges typical of isotrithionedithiols [17, 18]. The molecule consists of
3
5
two planar moieties: the isotrithionedithiol moiety (the atoms S(1)–S(5), C(1)–C(3), mean-square deviation 0.04
Å) and the pyridine moiety (C(6)–C(10), N(1), mean-square deviation 0.008 Å). The bond lengths, bond angles,
and orientation of the thermal vibration ellipsoids in the ethylene group suggest disordering of the C(4) and C(5)
atoms. In the packing of the molecules in the crystal, shortened intermolecular contacts
-
x,3-y,1-z
x,y+1,z
S(2)···S(2)
3.44 Å and S(4)···H(7)
2.92 Å are formed (the van der Waals radii of S and H are equal to
1
.84 and 1.16 Å respectively [19]).
TABLE 1. Bond Lengths (d) in the Structure of Compound 2
Bond
S(1)−C(1)
d, Å
Bond
S(2)−C(1)
d, Å
1.653(3)
1.736(3)
1.747(2)
1.780(4)
1.796(3)
1.376(6)
1.340(4)
1.356(4)
1.370(4)
1.708(3)
1.722(3)
1.745(3)
1.739(3)
1.336(4)
1.518(4)
1.370(4)
1.362(4)
1.332(4)
S(2)−C(2)
S(3)−C(3)
S(4)−C(4)
S(5)−C(5)
C(4)−C(5)
C(6)−N(1)
C(7)−C(8)
C(9)−C(10)
S(3)−C(1)
S(4)−C(2)
S(5)−C(3)
C(2)−C(3)
C(4)−C(6)
C(6)−C(7)
C(8)−C(9)
C(10)−N(1)
EXPERIMENTAL
-
1
The IR spectra were recorded on a Specord IR-75 spectrometer in the range 400-4000 cm . The samples
were prepared by pressing in the form of KBr disks. The mass spectra were obtained on a MAT 8200 with
1
13
ionizing electron energy 70 eV. The H and C NMR spectra were obtained on a Bruker AC 250 and Avance
4
00 spectrometer (operating frequencies 400 MHz and 100 MHz). Internal standard TMS. Elemental analysis
76
3

TABLE 2. Bond Angles (ω) in the Structure of Compound 2
Angle
ω, deg.
Angle
ω, deg.
97.40(12)
C(1)−S(2)−C(2)
C(2)−S(4)−C(4)
S(1)−C(1)−S(2)
S(2)−C(1)−S(3)
C(3)−C(2)−S(4)
C(2)−C(3)−S(5)
S(5)−C(3)−S(3)
C(5)−C(4)−S(4)
C(4)−C(5)−S(5)
N(1)−C(6)−C(4)
C(8)−C(7)−C(6)
C(8)−C(9)−C(10)
C(10)−N(1)−C(6)
97.33(13)
101.32(15)
123.49(18)
113.16(15)
128.7(2)
C(1)−S(3)−C(3)
C(3)−S(5)−C(5)
S(1)−C(1)−S(3)
C(3)−C(2)−S(2)
S(2)−C(2)−S(4)
C(2)−C(3)−S(3)
C(5)−C(4)−C(6)
C(6)−C(4)−S(4)
N(1)−C(6)−C(7)
C(7)−C(6)−C(4)
C(7)−C(8)−C(9)
N(1)−C(10)−C(9)
100.28(16)
123.35(16)
116.78(19)
114.50(15)
115.2(2)
128.96(19)
115.84(14)
119.2(3)
116.2(4)
107.1(2)
122.1(3)
122.8(3)
117.2(3)
120.0(3)
119.2(3)
119.4(3)
118.1(2)
124.0(3)
116.4(3)
was carried out on an automatic Elementar Vario EL. The electronic absorption spectra were recorded on a
Hitachi U 3210 in the range 200-750 nm in acetonitrile.
The X-ray Diffraction Study of the crystals was carried out on a Bruker P4 automatic four-circle
diffractometer (MoKα, graphite monochromator). The intensities were measured by the ω-scanning method in
the angle range 4° ≤ 2θ ≤ 64°. A total of 8800 reflections were measured, of which 2769 were independent
(
R = 0.078) and 2053 were observed with I > 2σ(I). Crystallographic data: C H NS ; M = 301.47; T = 293 K;
int
10
7
5
r
3
monoclinic; P2 /c; a = 11.600(2), b = 6.0010(12), c = 17.964(4) Å; β = 108.27(3)°; V = 1187.5(4) Å ; Z = 4; d
=
1
calc
3
-1
1.686 g/cm ; F(000) = 616; µ(MoKα) = 0.943 mm ·Å.
The structure was solved by the direct method and refined by full-matrix least-squares on F in the
2
anisotropic approximation. The hydrogen atoms were introduced geometrically and refined using a horse and
rider model with Uiso = 1.2 U of the corresponding carbon atom. The final reliability indices were R = 0.080,
eq
wR = 0.243 with respect to the observed reflections and R = 0.102, wR = 0.276 with respect to all the
independent reflections, S = 1.00.
The bond lengths and bond angles are given in Tables 1 and 2. Figure 1 shows the numbering of the
atoms used in discussion of the X-ray diffraction data and the thermal vibration ellipsoids in the molecule. We
used the programs SHELX-97 and Ortep-3 to do the calculations and prepare the illustrations [20, 21].
1
4
,5-Bis(2-pyridylethylsulfanyl)-1,3-dithiol-2-thione (1) was obtained as in [9]; the IR and H and
1
3
C NMR spectra were consistent with the data in [9].
-(2-Pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione (4,5-(2-Pyridylethylenedithio)-
,3-dithiolo-2-thione) (2). Obtained according to the method described in [10], but the yield was 32% instead of
5
1
1
3
2
0%; mp 126°C. UV spectrum (MeCN), λmax, nm (log ε): 408 (3.65), shoulder 327, 308 (3.61), 257 (3.69). C
NMR spectrum (CD Cl ), δ, ppm: 35.30 (SCH ); 49.74 (CHPy); 123.03 (C(3)pyrid); 123.75 (C(5)pyrid); 124.24
2
2
2
(
C=C); 137.50 (C(4)pyrid); 150.25 (C(6)pyrid); 156.91 (C(2)pyrid); 208.88 (C=S).
-(4-Pyridyl)-5,6-dihydro[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione (4,5-(4-Pyridylethylenedithio)-
,3-dithiol-2-thiol) (3). Obtained by the method described in [10], but the yield was 41% instead of 15%;
5
1
1
3
mp 138°C. UV spectrum (MeCN), λmax, nm (log ε): 406 (3.56), 268 (3.42). C NMR spectrum (benzene-d ),
6
δ, ppm: 34.98 (SCH ); 47.16 (CHPy); 122.54 (C=C); 122.83 (C(3)pyrid, C(5)pyrid); 124.00 (C=C); 146.69 (C(4)pyrid);
2
1
51.92 (C(2)pyrid, C(6)pyrid); 207.87 (C=S).
5
-(2-Pyridyl)[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione (4,5-(2-Pyridylvinylenedithio)-1,3-dithiol-2-
thione) (4). 2-Ethynylpyridine (0.5 ml, 5.14 mmol) was added to isotrithionedithiol (0.5 g, 1.27 mmol) in
benzene (25 ml). The reaction mixture was boiled under reflux for 17 h. After cooling, the solution was filtered,
3
77

and the solvent was evaporated on a rotary evaporator. The powdery precipitate was washed with acetone.
-
1
Yield 0.57 g (75%). IR spectrum, ν, cm : 1075 (C=S), 1427-1581 (the pyridyl moiety). UV spectrum (MeCN),
1
λmax, nm (log ε): 392 (2.94), 288 (2.98), 256 (3.12). H NMR spectrum (benzene-d ), δ, ppm (J, Hz): 6.84 (1H, s,
6
HCS); 7.28 (1H, ddd, J = 7.5, J = 4.8, J = 1, H(5)pyrid); 7.30 (1H, dd, J = 7.5, J = 1, H(3)pyrid); 7.60 (1H, dt, J = 8
1
3
and J = 1, H(4)pyrid); 8.60 (1H, dd, J = 4.8 and J = 1, H(6)pyrid). C NMR spectrum (benzene-d ), δ, ppm (J, Hz):
6
1
20.05 (C(3)pyrid); 121.5 (C ); 122.67 (C(5)pyrid); 123.89 (C(3a) or C(7a)); 137.18 (C(4)pyrid); 142.2 (C ); 149.84
(
6
)
(
5
)
(
C(6)pyrid); 156.6 (C(2)pyrid); we could not identify C(7a) or C(3a) due to the low signal-to-noise ratio of the C=S
signal. Found, %: C 39.42; H 1.92; N 4.57. C H NS . Calculated, %: C 40.13; H 1.67; N 4.68.
1
0
5
5
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