Crystal structure of an AgClO4 π complex with 2-amino-5-allylthio-1,3,4-thiadiazole of the composition [Ag(C5H7N3S2)(ClO4)]

Article abstract of DOI:10.1134/S0022476617020184

By interaction of AgClO₄ with 2-amino-5-allylthio-1,3,4-thiadiazole (Aаtd) in the ethanol solution, a new [Ag(Aаtd)(ClO₄)] π complex is obtained. It is studied by single crystal X-ray diffraction.

Full text of DOI:10.1134/S0022476617020184

Journal of Structural Chemistry. Vol. 58, No. 2, pp. 356-357, 2017.
Original Russian Text © 2017 Yu. I. Slyvka.
CRYSTAL STRUCTURE OF AN AgClO
4
π COMPLEX
WITH 2-AMINO-5-ALLYLTHIO-1,3,4-THIADIAZOLE
5 7 3 2 4
OF THE COMPOSITION [Ag(C H N S )(ClO )]
Yu. I. Slyvka
UDC 548.736:661
By interaction of AgClO
4
with 2-amino-5-allylthio-1,3,4-thiadiazole (Aаtd) in the ethanol solution,
4
a new [Ag(Aаtd)(ClO )] π complex is obtained. It is studied by single crystal X-ray diffraction.
DOI: 10.1134/S0022476617020184
Keywords: synthesis, silver(I), π complex, 1,3,4-thiadiazole, crystal structure.
The 1,3,4-thiadiazole derivatives have a wide spectrum of properties promoting their use as biologically active
substrates, phytohormones, optically active materials, and effective tools in crystal engineering of metal complexes [1-3].
Among the olefinic π complexes with transition metal ions containing a 1,3,4-thiadiazole core, about a dozen compounds
have been structurally studied; five of them are Cu(I) π complexes with allyl derivatives of thiadiazole [4, 5]. With the aim to
+
investigate the coordination capacities and behavior of allyl derivatives of 1,3,4-thiadiazole with respect to Ag , this
communication reports the results of the synthesis and single crystal X-ray diffraction analysis of new π complex
[Ag(Aаtd)(ClO )] (1) with 2-amino-5-allylthio-1,3,4-thiadiazole (Aаtd).
4
Experimental. Synthesis. 5-Amino-1,3,4-thiadiazole-2-thiol was obtained by the known procedure [6] and its allyl
derivative Aаtd was obtained from 5-amino-1,3,4-thiadiazole-2-thiol and allyl chloride in the presence of NaHCO in the
3
ethanol solution. Yield was 92%.
The crystals of [Ag(Aаtd)(ClO )] compound (1) were synthesized by direct interaction of silver(I) perchlorate
4
(formed in situ from Ag CO and HClO ) with Aаtd in ethanol. To Aаtd solution in ethanol at room temperature an equimolar
2 3 4
amount of freshly prepared Ag
2
CO
3
4
was added; the resulting suspension was acidified with concentrated HClO to pH ∼ 3. In
two days, colorless crystals of compound 1 formed.
Single crystal X-ray diffraction. Integrated reflection intensities for the crystal of compound 1 were measured on
a Kuma KM-4-CCD single crystal diffractometer (MoK radiation, graphite monochromator). The structure was solved and
α
2
refined with the ShelXT and ShelXL software using the OLEX interface [7, 8]. The details of the single crystal X-ray
diffraction study and the main crystallographic data for 1 are as follows: composition C H AgClN O S , M = 380.58 g/mol,
5 7 3 4 2
3
1
monoclinic crystals, space group P2 /c, a = 9.517(3) Å, b = 7.900(3) Å, c = 14.752(4) Å, β = 102.79(3)°, V = 1081.6(6) Å ,
3 –1
Z = 4, ρcalc = 2.337 g/cm , μ(MoK ) = 2.497 mm , S = 1.053, R(F) = 0.0557 for 2014 reflections with I ≥ 2σ(I), R = 0.1514
α
w
for all 2526 independent reflections. Atomic coordinates and other parameters of compound 1 have been deposited with the
Cambridge Structural Database (No. CCDC 1495708) at www.ccdc.cam.ac.uk/data_request/cif.
Franko National University of Lviv, Lviv, Ukraine; y_slyvka@franko.lviv.ua. Translated from Zhurnal Strukturnoi
Khimii, Vol. 58, No. 2, pp. 373/374, February-March, 2017. Original article submitted July 28, 2016.
356
0022-4766/17/5802-0356 © 2017 by Pleiades Publishing, Ltd.

i
Fig. 1. Fragment of the structure of [Ag(Aаtd)(ClO )] (1). Symmetry codes: 1–x,
4
ii
–y, 1–z; 1–x, 2–y, 1–z.
1
Results and discussion. In the structure of 1, the organic Aаtd ligand molecule acts as a bridging chelate π,σ ligand
and is coordinated to the Ag(I) atom by the olefinic C=C bond of the S-allyl group and by two (N3 and N4) atoms of the
1
,3,4-thiadiazole core (Fig. 1). The silver(I) atom is disordered over two positions with the respective site occupancies of
.76(3) (Ag1a) and 0.24(3) (Ag1b). An almost trigonal environment of Ag1a consists of the above mentioned active centers
0
i
of the two neighboring Aаtd molecules: the Ag1a–m (where m is the middle of the C=C bond, 1–x, 1–y, 1–z), Ag1a–N4,
i
i
and Ag1a–N3 distances are, respectively, 2.337(5) Å, 2.267(5) Å, and 2.188(5) Å. Therefore, two nearest Ag1a atoms join
2+
two Aаtd molecules into a centrosymmetric {[Ag(Aаtd)]
2
} dimer.
The coordination environment of the Ag1b atom increases to five due to the formation of two additional bonds:
ii ii
Ag1b–O1 (2.956(5) Å) with an oxygen atom of the perchlorate anion and Ag1b–S2 (3.002(5) Å, 1– x, 2–y, 1–z) with the
2+
2
sulfur atom of the allylthiol group of the neighboring {[Ag(Aаtd)] } dimer. Both Ag1b–O1 and Ag1b–S2 distances are far
i
i
less than the sum of the van der Waals radii of the respective atoms [9]. The Ag1b–m , Ag1b–N4, and Ag1b–N3 distances
are, respectively, 2.35(1) Å, 2.344(9) Å, and 2.36(1) Å.
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