Ethyl 7-chloro­methyl-5-(2-chloro­phen­yl)-7-hydr­oxy-2-methyl­sulfanyl-4,5,6,7-tetra­hydro-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxyl­ate

Shao-wei Huang

doi:10.1107/S1600536809039373

. 2009 Oct 10;65(Pt 11):o2671. doi: 10.1107/S1600536809039373

Ethyl 7-chloromethyl-5-(2-chlorophenyl)-7-hydroxy-2-methylsulfanyl-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylate

Shao-wei Huang ^a,^*

PMCID: PMC2971018 PMID: 21578280

Abstract

In the title compound, C₁₆H₁₈Cl₂N₄O₃S, the five-membered ring is almost planar [maximum deviation = 0.011 (3) Å] and the six-membered ring adopts an envelope conformation. In the crystal structure, N—H⋯N, O—H⋯N and C—H⋯O interactions link molecules into a three-dimensional network.

Related literature

For general background to tetrahydro triazolo[1,5-a]pyrimidine derivatives as potential biologically active compounds, see: Pryadeina et al. (2004 ▶). For related structures, see: Chen et al. (2005 ▶); Hu et al. (2005 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₆H₁₈Cl₂N₄O₃S
M _r = 417.30
Triclinic,
a = 8.4534 (14) Å
b = 10.5082 (17) Å
c = 12.0846 (19) Å
α = 66.660 (3)°
β = 79.519 (3)°
γ = 84.795 (3)°
V = 969.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.47 mm⁻¹
T = 292 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART 4K CCD diffractometer
Absorption correction: none
6772 measured reflections
3759 independent reflections
2661 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.141
S = 1.08
3759 reflections
249 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809039373/hb5113sup1.cif

e-65-o2671-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039373/hb5113Isup2.hkl

e-65-o2671-Isup2.hkl^{(184.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N4ⁱ	0.93 (3)	2.04 (3)	2.969 (3)	172 (2)
O3—H3A⋯N3ⁱⁱ	0.77 (3)	2.05 (3)	2.806 (3)	170 (3)
C16—H16A⋯O3ⁱⁱ	0.96	2.47	3.290 (4)	143

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors acknowledge financial support from the National Natural Science Foundation of China (grant No. 20702018).

supplementary crystallographic information

Comment

In recent years, tetrahydro triazolo1,5-a]pyrimidine derivatives nave attracted interest as potential biologically active compounds (Pryadeina et al., 2004). In this paper, we present the structure of one such analogue, the title compound, (I) (Fig. 1), in which the bond lengths (Allen et al., 1987) and angles are within normal ranges.

The bicyclic triazolopyrimidine system is not on the same plane because they can not form a conjugated system. Ring A (N2-4/C14-15) is close to planarity with a maximum deviation of 0.011Å for C15. Rng B (N1-2/C7-8/C12/C14) dopt envelope conformations with atom C8 displaced by 0.333 (3) Å from the plane of the other ring atoms. The dihedral angle between the Ring (C1-C6) and the ring A is 51.86°.

In the crystal structure, weak N-H···N, O-H···N and C-H···O interactions link the molecules into a three-dimensional network (Fig. 2).

Experimental

A solution of 4-chloro acetylacetic ester (1 mmol), 2-chloro benzaldehyde (1 mmol), and 3-amino-5-methylthio-1,2,4-triazole (1mmol) in water (3 ml) containing a catalytic amount of TSA was heated under 353 K for 10 h. The resulting mixture was extracted with CH₂Cl₂ and the extra was dried over sodium sulfate, filtered, the filtrate was condensed under reduced pressure and the residue was purified by chromatography on SiO₂ to afford the title compound. Colourless blocks of (I) were grown from an acetone solution at 293K. ¹H NMR (CDCl₃, 400 MHz): σ 7.03-7.40(m, 4 H), 6.42(s, 1H), 4.99(d, 1H), 4.35(d, 1H), 4.00(q,2 H), 3.91(d, 1H), 3.05(d, 1H), 2.35(s, 3H), 1.03(t,3H).