STUDY OF THE STRUCTURE OF (CARBAMIMIDOYLSULFANYL)ACETIC
677
Leco CHNS(O) 942.
stirring a solution of 1.89 g (20 mmol) of monochloro-
acetic acid in 10 ml of water, and the mixture was stirred
for 3 h. After 24 h the separated precipitate was filtered
off and several times was thoroughly washed with hot
water. The product was dried in a vacuum desiccator
over CaCl2. Yield 1.12 g (42%), mp 255°C (234°C [3]).
IR spectrum (thin film), ν, cm–1: 1119, 1150, 1230, 1366,
1406, 1434, 1439, 1585 (C–N, bending NH), 1682, 1686
(С=О), 2782 (CH2), 2948 (NH), 3082 sh, 3182, 3279,
3356 sh, 3544 sh. Found, %: C 26.56; H 4.58; N 20.23;
S 23.79. C3H6N2O2S. Calculated, %: С 26.86; Н 4.51;
N 20.88; S 23.90.
A polycrystalline sample of compound I was investi-
gated at room temperature on a diffractometer Shimadzu
A7000 (CuKα radiation, Ni-filter, 30 kV, 35 mA). The
registering was carried out in a step mode in the angles
range 2θ 5–120° with a step 0.02° and exposure of 10 s
in the point. The peaks were approximated by the func-
tion Pearson VII. The indexing and the evaluation of
the unit cell parameters was performed using a program
N-TREOR09 from the program package EXPO 2009
[12]. Compound I crystallizes in the monoclinic crystal
system, space group P21/n. Parameters of the unit cell
are as follows: a 9.7425(2), b 8.0864(1), c 6.9950(1) Å,
β 106.913(1)°, V 527.914(2) Å3, ρcalc 1.615 g cm–3, Z 4.
The structure was solved by the direct method and refined
by Rietveld method till Rp 5.203, Rwp 7.131, Re 1.527,
GOF 4.670. (Experimental and theoretical diffractograms
of acid I are available from the authors).
REFERENCES
1. Maly, R. Lieb. Ann. 1877, vol. 189, p. 380.
2. Ray, P.C. and Fernandes, F.V. J. Chem. Soc., 1914, vol. 105,
p. 2159.
3. Desai, R.D., Hunter, R.F., and Koppar, L.G., Rec. Trav.
Chim., 1935, vol. 54, p. 118.
All calculations were performed using EXPO 2009
software. The images of crystal structure are obtained
applying Mercury 2.3 program [13].
4. Lazarev, D.B., Ramsh, S.M., and Ivanenko, A.G., Zh. Org.
Khim., 2000, vol. 70, p. 475.
5. Allen, F.H., Kennard, O., Watson, D.G., Brammer, L.,
Orpen, A. G., and Taylor, R., J. Chem. Soc., Perkin Trans.
II, 1987, S1.
6. Brand, H., Hubrich, C., Polborn, K., Schulz, A., and
Villinger, A., Acta Cryst., Sect. E: Struct. Rep. Online.,
2007, 63, no. 12, o4733.
7. Kushakova, P.M., Ramsh, S.M., and Garabadzhiu, A.V.,
Khim. Geterotsikl. Soedin., 2006, p. 250.
8. Roothaan, C.C., J. Rev. Mod. Phys., 1951, vol. 23, no. 2,
p. 69.
9. Stewart, J.J.P., J. Mol. Model., 2007, vol. 13, p. 1173.
10. Mulliken, R.S., J. Chem. Phys., 1955, vol. 23, p. 1833.
11. Pal’m, V.A., Vvedenie v teoreticheskuyu organicheskuyu
khimiyu (Introduction on Theoretical Organic Chemistry),
Moscow: Vysshaya Shkola, 1974, p. 168.
Semiempirical quantum-chemical calculations were
performed by PM6 method [9] using MOPAC2009 (ver-
sion 9.069W) software [14]. The solid-state calculations
were performed for a cluster model containing (2 × 2 × 2)
unit cells of the crystal of acid I [key word of the program
MERS=(2,2,2)]. The translation vectors were set by the
positions of three auxiliary atoms having in the list of
the initial data symbol marking “Tv” The optimization
process of the system was terminated at reaching the
threshold value of gradient norm (GNORM) equal 1.0.
The calculated unit cell parameters4 of compound I
in the crystal and its density are as follows: a 9.815, b
7.971, c 6.308 Å, β85.11°, V 491.69 Å3, ρ1.812 g cm–3.
The ab initio quantum-chemical calculations were
carried out by Hartree-Fock method [8] using a mini-
mum basis. The use of an extended but unbalanced basis
(employing d-functions only for sulfur atom) resulted in
unnatural overestimation of the negative charge on the
sulfur atom. The atomic functions were represented as the
sum of Gaussians (basis 3-21G* was applied). The cal-
culations were performed using GAMESS program [15].
12. Altomare, A., Camalli, M., Cuocci, C., Giacovazzo, C.,
Moliterni, A., and Rizzi, R., J. Appl. Cryst., 2009, vol. 42,
p. 1197.
13. Macrae, C.F., Bruno, I.J., Chisholm, J.A., Edgington, P.A.,
McCabe, P., Pidcock, E., Rodrigues-Monge, L., Taylor, R.,
van de Streek, J., and Wood, P.A., J. Appl. Cryst., 2008,
vol. 41, p. 466.
14. Stewart, J.J.P., Program package MOPAC2009. http://
OpenMOPAC.net
(Carbamimidoylsulfanyl)acetic acid (I) was ob-
tained by modified procedure [3]. To a solution of 1.52 g
(20 mmol) of thiourea in 10 ml of water was added at
15. Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T.,
Gordon, M.S., Jensen, J.H., Koseki, S., Matsunaga, N.,
Nguyen, K.A., Su, S., Windus, T.L., Dupuis, M., and Mont-
gomery, J.A., J. Comput. Chem., 1993, vol. 14, p. 1347;
gamess.
____________
4 The difference in the parameters of the a and с axes and consequently
of angle β from the parameters determined by XRD analysis was
due by slightly another choice of the cell.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 5 2013