Ethyl 5-chloro-methyl-2-methyl-sulfanyl-7-phenyl-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine-6-carboxyl-ate.

Abstract

In the title compound, C(16)H(17)ClN(4)O(2)S, the bicyclic triazolopyrimidine ring system is nearly planar and oriented with respect to the benzene ring at a dihedral angle of 87.24 (3)°. In the crystal structure, inter-molecular N-H⋯N hydrogen bonds link the mol-ecules into centrosymmetric dimers; an intra-molecular C-H⋯O hydrogen bond is also present.

Full text

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Ethyl 5-chloromethyl-2-methylsulfanyl-7-
phenyl-4,7-dihydro-1,2,4-triazolo[1,5-a]-
pyrimidine-6-carboxylate
Dan-Dan Songaand Qiong Chenb*
aCollege of Chemistry, Central China Normal University, Wuhan 430079, People’s
Republic of China, andbKey Laboratory of Pesticides and Chemical Biology of the
Ministry of Education, College of Chemistry, Central China Normal University,
Wuhan 430079, People’s Republic of China
Correspondence e-mail: qchen@mail.ccnu.edu.cn
Received 23 November 2007; accepted 23 November 2007
Key indicators: single-crystal X-ray study; T = 292 K; mean ?(C–C) = 0.005 A ˚;
R factor = 0.055; wR factor = 0.155; data-to-parameter ratio = 14.8.
In the title compound, C16H17ClN4O2S, the bicyclic triazolo-
pyrimidine ring system is nearly planar and oriented with
respect to the benzene ring at a dihedral angle of 87.24 (3)?. In
the crystal structure, intermolecular N—H???N hydrogen
bonds link the molecules into centrosymmetric dimers; an
intramolecular C—H???O hydrogen bond is also present.
Related literature
For related literature, see: Fedorova et al. (2003). For bond-
length data, see: Allen et al. (1987).
Experimental
Crystal data
C16H17ClN4O2S
Mr= 364.85
Triclinic, P1
a = 8.9280 (8) A˚
b = 9.8217 (9) A˚
c = 11.3775 (10) A˚
? = 106.022 (2)?
? = 102.631 (2)?
? = 109.919 (2)?
V = 845.85 (13) A˚3
Z = 2
Mo K? radiation
? = 0.37 mm?1
T = 292 (2) K
0.20 ? 0.10 ? 0.02 mm
Data collection
Bruker SMART 4K CCD area-
detector diffractometer
Absorption correction: none
6662 measured reflections
3281 independent reflections
2295 reflections with I > 2?(I)
Rint= 0.030
Refinement
R[F2> 2?(F2)] = 0.055
wR(F2) = 0.156
S = 1.02
3281 reflections
222 parameters
H atoms treated by a mixture of
independent and constrained
refinement
??max= 0.40 e A˚?3
??min= ?0.42 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
N4—H4???N2i
C7—H7B???O2
Symmetry code: (i) ?x þ 1;?y;?z þ 1.
D—HH???AD???AD—H???A
0.85 (3)
0.97
2.11 (3)
2.15
2.939 (3)
2.888 (4)
164 (3)
132
Data collection: SMART (Bruker, 2001); cell refinement: SAINT
(Bruker, 2001); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine
structure:SHELXL97(Sheldrick,
PLATON (Spek, 2003); software used to prepare material for
publication: SHELXTL (Bruker, 2001).
1997);moleculargraphics:
The present work was supported by the National NSFC
(grant Nos. 20572030,20432010 and 20528201), the Cultivation
Fund of the Key Scientific and Technical Innovation Project,
Ministry of Education of China (grant No. 705039), and the
Program for Excellent Research Groups of Hubei Province
(grant No. 2004ABC002).
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: HK2399).
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Bruker (2001). SHELXTL (Version 6.12), SMART (Version 5.628) and
SAINT (Version 6.45). Bruker AXS Inc., Madison, Wisconsin, USA.
Fedorova, O. V., Zhidovinova, M. S., Rusinov, G. L. & Ovchinnikova, I. G.
(2003). Russ. Chem. Bull. Int. Ed. 52, 1768–1769.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of
Go ¨ttingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
organic compounds
Acta Cryst. (2008). E64, o45doi:10.1107/S1600536807062629Song and Chen
o45
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials

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supplementary materials
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Acta Cryst. (2008). E64, o45 [ doi:10.1107/S1600536807062629 ]
Ethyl
carboxylate
5-chloromethyl-2-methylsulfanyl-7-phenyl-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine-6-
D.-D. Song and Q. Chen
Comment
In recent years, growing attention has been paid to analogues of purines and nucleosides, including azolopyrimidines
containing the bridge head nitrogen atom and their dihydro derivatives, among which promising biologically active com-
pounds were found (Fedorova et al., 2003). We synthesized a novel class of ethyl 7-alkylthio-4,7-dihydro-1,2,4-triazolo[1,5-
a]pyrimidine-6-carboxylate derivatives by three component condensation of 3-amino-5-alkylthio-1,2,4 -triazoles with aro-
matic aldehydes and β-keto ester. We report herein the crystal structure of one such analogue, a triazolopyrimidine derivat-
ive, the title compound, (I).
In the molecule of (I), (Fig. 1) the bond lengths and angles are within normal ranges (Allen et al., 1987). Rings A
(N1—N3/C2/C3), B (N3/N4/C3—C6) and C (C11—C16) are, of course, planar. The bicyclic triazolopyrimidine ring system
(N1—N4/C2—C6) is nearly planar with a maximum deviation of 0.152 (3) Å (for atom C6), and it is oriented with respect
to ring C at a dihedral angle of 87.24 (3)°.
In the crystal structure, intermolecular N—H···N hydrogen bonds (Table 1, Fig 2) link the molecules into centrosymmetric
dimers; an intramolecular C—H···O hydrogen bond (Table 1) is also present.
Experimental
For the preparation of the title compound, a mixture of 4-chloro acetylacetic ester (1 mmol), benzaldehyde (1 mmol), and
3-amino-5-methylthio-1,2,4-triazole (1 mmol) in EtOH (3 ml) was added into a microwave tube. The sealed tube was placed
in a Smith synthesizer and irradiated at 333 K for 30 min. The reaction mixture was cooled to room temperature, and the
precipitate was filtered and recrystallized from ethanol to give the title compound, (I). Single crystals of (I) suitable for
X-ray analysis were grown from an acetone solution at 293 K. 1H NMR (CDCl3, 400 MHz): σ 10.56(s, 1 H), 7.28–7.33(m,
5 H), 6.40(s, 1H), 5.14(d, 1H), 4.95(d, 1H), 4.11(q,2 H), 2.51(s, 3H),1.15(t, 3H).
Refinement
H atom (for NH) was located in a difference sythesis and refined [N—H = 0.85 (3) Å and Uiso(H) = 1.2Ueq(N)]. The
remaining H atoms were positioned geometrically, with C—H = 0.93, 0.98, 0.97 and 0.96 Å for aromatic, methine, methylene
and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl
H, and x = 1.2 for all other H atoms.

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Figures
Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Dis-
placement ellipsoids are drawn at the 50% probability level.
Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.
Ethyl 5-chloromethyl-2-methylsulfanyl-7-phenyl-4,7-dihydro- 1,2,4-triazolo[1,5-a]pyrimidine-6-carboxylate
Crystal data
C16H17ClN4O2S
Mr = 364.85
Z = 2
F000 = 380
Dx = 1.433 Mg m−3
Mo Kα radiation
λ = 0.71073 Å
Cell parameters from 1660 reflections
θ = 2.4–22.5º
µ = 0.37 mm−1
T = 292 (2) K
Block, colorless
0.20 × 0.10 × 0.02 mm
Triclinic, P1
Hall symbol: -P 1
a = 8.9280 (8) Å
b = 9.8217 (9) Å
c = 11.3775 (10) Å
α = 106.022 (2)º
β = 102.631 (2)º
γ = 109.919 (2)º
V = 845.85 (13) Å3
Data collection
Bruker SMART 4K CCD area-detector
diffractometer
Radiation source: fine-focus sealed tube
Monochromator: graphite
T = 292(2) K
φ and ω scans
Absorption correction: none
6662 measured reflections
3281 independent reflections
2295 reflections with I > 2σ(I)
Rint = 0.030
θmax = 26.0º
θmin = 2.4º
h = −10→11
k = −12→12
l = −14→13
Refinement
Refinement on F2
Secondary atom site location: difference Fourier map

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Least-squares matrix: full
Hydrogen site location: inferred from neighbouring
sites
H atoms treated by a mixture of
independent and constrained refinement
w = 1/[σ2(Fo2) + (0.0839P)2P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.40 e Å−3
Δρmin = −0.42 e Å−3
R[F2 > 2σ(F2)] = 0.055
wR(F2) = 0.156
S = 1.02
3281 reflections
222 parameters
Primary atom site location: structure-invariant direct
methods
Extinction correction: none
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance mat-
rix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations
between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of
cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculat-
ing R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice
as large as those based on F, and R– factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
0.52275 (12)
0.33719 (10)
0.7924 (2)
0.8859 (3)
0.5299 (3)
0.4832 (3)
0.6027 (3)
0.6300 (3)
0.603 (4)
0.3128 (5)
0.4175
0.2245
0.2831
0.4589 (3)
0.5739 (3)
0.6994 (3)
0.7350 (3)
0.7104 (3)
0.6505
0.7226 (4)
0.7719
y
0.20019 (13)
0.12878 (9)
0.7426 (2)
0.6249 (3)
0.3688 (3)
0.1259 (2)
0.3760 (2)
0.2107 (3)
0.119 (4)
0.2917 (4)
0.3619
0.2552
0.3456
0.2173 (3)
0.2331 (3)
0.3357 (3)
0.4840 (3)
0.5239 (3)
0.5913
0.2871 (3)
0.2125
z
0.21023 (8)
0.82617 (8)
0.57614 (18)
0.4314 (2)
0.7737 (2)
0.6417 (2)
0.6786 (2)
0.5023 (2)
0.448 (3)
0.9220 (4)
0.9926
0.9564
0.8687
0.7451 (3)
0.6044 (2)
0.4670 (3)
0.5433 (3)
0.6746 (3)
0.6795
0.3381 (3)
0.3329
Uiso*/Ueq
0.0802 (4)
0.0506 (3)
0.0458 (5)
0.0745 (8)
0.0399 (6)
0.0394 (6)
0.0378 (5)
0.0423 (6)
0.051*
0.0875 (14)
0.131*
0.131*
0.131*
0.0372 (6)
0.0355 (6)
0.0396 (7)
0.0373 (6)
0.0371 (6)
0.045*
0.0480 (8)
0.058*
Cl1
S1
O1
O2
N1
N2
N3
N4
H4
C1
H1A
H1B
H1C
C2
C3
C4
C5
C6
H6
C7
H7A