Spectroscopic study of interaction of 1H-1,2,4-triazoline-3-thione with molecular iodine

Article abstract of DOI:10.1134/S1070363213050186

The formation by 1H-1,2,4-triazoline-3-thiones in dilute chloroform solution of n-σ*-complex with molecular iodine of the composition C₂H₂N₃S·I₂ was studied by electronic spectroscopy in the UV and visible regio

Full text of DOI:10.1134/S1070363213050186

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 5, pp. 986–988. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © M.S. Chernovyants, N.V. Aleshina, I.N. Shcherbakov, Z.A. Starikova, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83,
No. 5, pp. 852–854.
Spectroscopic Study of Interaction
of 1H-1,2,4-Triazoline-3-thione with Molecular Iodine
M. S. Chernovyantsa, N. V. Aleshinaa, I. N. Shcherbakova, and Z. A. Starikovab
a Southern Federal University, ul. Zorge 7, Rostov-on-Don, 344090 Russia
e-mail: chernov@sfedu.ru
b Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
Received March 5, 2012
Abstract―The formation by 1H-1,2,4-triazoline-3-thiones in dilute chloroform solution of n–σ*-complex with
molecular iodine of the composition C2H2N3S·I2 was studied by electronic spectroscopy in the UV and visible
regions (log β = 2.14±0.05). By the XRD method the crystal and molecular structure of the product of chemical
interaction of the thione with molecular iodine in ethanol, 1,2-di(1H-1,2,4-triazol-3-yl) disulfide, was determined.
DOI: 10.1134/S1070363213050186
Derivatives of 1,2,4-triazoline-5-thione have a broad
spectrum of biological activity, including analgesic [1],
anti-inflammatory [2], bacteriostatic [3, 4], and
antifungal [5] action. In [6] a synthesis was described
of a series of new derivatives of 1,2,4-triazoline-5-
thione with a potential pharmacological activity.
Biological activity of 1,2,4-triazoline-5-thione is
correlated with their ability to form complexes with
transition metal ions [7]. In [8] the synthesis conditions
were described and the results of research on
chemosensory properties of 5-amino-3,4-dihydro-2H-
1,2,4-triazolyl-3-thiones. The 3(5)-sulfhydryl-1,2,4-
triazoles unsubstituted at the S and N atoms have been
used successfully in organic synthesis of bicyclic
1,2,4-triazoles [9–11]. Besides these compounds have
antithyroid action and interact with molecular iodine
like N-methylimidazoline-2-thione (methimazole) and
3-methyl-2-thioxo-4-imidazoline-1-carboxylate
molecular adduct of the thione (L) with elemental
iodine was evaluated by the spectroscopic method of
shifting the reaction equilibrium:
L·nI2
[L][I2]n
β = –——— .
(1)
Electronic spectra of solutions with constant con-
centration of 1H-1,2,4-triazoline-3-thione and the con-
centration of iodine varied from 4×10–5 to 1.2×10–3 M,
are shown in Fig. 1.
The stability constant was calculated by the method
of least squares using the Eq. (2), the linearized form
of Eq. (1):
A
(carbimazole) [12, 13].
The aim of our work was to study the interaction of
1H-1,2,4-triazoline-3-thione with elemental iodine in
chloroform and ethanol solutions.
In chloroform solutions reversible complexation of
1H-1,2,4-triazoline-3-thione with elemental iodine was
observed, which we studied by UV/vis spectroscopy:
λ, nm
L + nI2 ⇄ L·nI2
Fig. 1. Electron absorption spectra of solutions of thione
(4.0×10–5 M) with molecular iodine at concentrations of the
latter 4.0×10–5 (1), 8.0×10–5 (2), 1.6×10–4 (3) 3.2×10–4 (4),
4.8×10–4 (5), 8.0×10–4 (6), 1.2×10–3 (7).
The number of I2 molecules coordinated by the
thione (L) in solution and the stability constant of the
986

SPECTROSCOPIC STUDY OF INTERACTION OF 1H-1,2,4-TRIAZOLINE-3-THIONE
987
Fig. 2. The molecular structure of 1,2-di(1H-1,2,4-triazole-
3-yl) disulfide.
Fig. 3. The crystal packing the layers of 1,2-di(1H-1,2,4-
triazole-3-yl) disulfide parallel to the 0yz plane.
EXPERIMENTAL
Ai
log –———– = logβ + nlog cI2 – n –—— cL ,
max – Ai Amax
Ai
(2)
1,2,4-Triazoline-3-thione (98%, Aldrich) was used
without further purification. 1,2-Di(1H-1,2,4-triazol-3-
yl) disulfide was synthesized by mixing 1,2,4-tria-
zoline-3-thione) (1 mmol, 0.1011 g) with I2 (2 mmol,
0.5076 g) in ethanol (15 ml). Solvents were purified by
known methods [15].
A
where Amax is the optical density of the solution in
which the thione L is fully bound in the adduct (λmax
=
303 nm); Ai is the optical density of solutions con-
taining L and the molecular adduct; β is the stability
constant; n is the number of iodine molecules coor-
dinated by the thione, cI2, cL are analytical concentra-
tions of molecular iodine and the thione, respectively.
Electronic spectra of chloroform solutions with
different ratios of thione and molecular iodine were
obtained on a Cary 100 spectrophotometer in the
region of 250–650 nm using the cells with a thickness
of the absorbing layer 1.0 cm,. As the initial solutions
From the equation of strait line (2) y = 1.04x + 2.14
(ρ = 0.992), it follows that in the chloroform solution
the thione is coordinated with one molecule of iodine,
and the stability constant is log β = 2.14 ± 0.05.
Selected geometric parameters of the crystal structure of
1,2-di(1H-1,2,4-triazole-3-yl) disulfide obtained by oxidation
with I2 and by autoxidation
The interaction of 1H-1,2,4-triazoline-3-thione with
elemental iodine in ethanol leads to irreversible
oxidation of thione to form 1,2-di(1H-1,2,4-triazol-3-
yl) disulfide, whose molecular and crystal structure we
studied using X-ray diffraction method (Figs. 2 and 3).
Hydrogen bonds NH···N and weak dipole–dipole S···N
interactions stabilize the crystal structure of 1,2-di(1H-
1,2,4-triazole-3-yl) disulfide.
Geometrical
The oxidation with
molecular iodine
Autoxidation [14]
parameters (Å, deg)
S1–S1A
S1–C1
2.0718(6)
1.7587(13)
1.3268(15)
1.3600(15)
0.88(2)
2.0693(11)
1.7541(15)
1.3225(19)
1.3549(18)
0.89(2)
N1–C1
Previously [14] a similar product of autoxidation of
1H-1,2,4-triazoline-3-thione was obtained in the
presence of sodium hydroxide in boiling ethanol. In
the table comparative geometric parameters (bond
lengths, bond and torsion angles) of the crystal
structure of 1,2-di(1H-1,2,4-triazole-3-yl) disulfide are
presented synthesized by us and described in [14].
N1–N2
N2–H(2N)
C1–N3
1.3677(16)
1.3335(16)
1.3303(16)
101.64(4)
123.1(1)
1.3653(19)
1.324(2)
C2–N2
C2–N3
1.322(2)
It should be noted that we have achieved a high
degree of refinement of molecular and crystal structure
of 1,2-di(1H-1,2,4-triazole-3-yl) disulfide (R1
0.0237, wR2 = 0.0573, S = 1.008). The refinement
parameters in [14] are as follows: R1 = 0.029, wR2 =
0.081, S = 1.09).
C1S1S1A
N1C1S1
N3C1S1
C1S1S2C3
101.72(5)
123.30(12)
122.40(11)
83.69 (8)
=
122.24(9)
83.70(4)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 5 2013

988
CHERNOVYANTS et al.
isomolar chloroform solutions of the thione and iodine
(2.0×10–3 M) were used. Prior to the measurements the
exact value of molar absorption coefficient ε510 of
iodine was determined. In the reaction series the
concentration of molecular iodine was changed from
the deficit up to 30-fold excess at a constant
concentration of thione (4.0×10–5 M).
wR2 = 0.0553, number of refined parameters 59. The
values of maximum and minimum residual peaks are
0.532 and –0.227 e Å–3, respectively.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 5 2013