7-(2,4-Dichloro-phen-yl)-2-methyl-sulfanyl-pyrazolo[1,5-a]pyrimidine-3-carbonitrile.

In the mol-ecule of the title compound, C(14)H(8)Cl(2)N(4)S, all the ring atoms in the pyrazolopyrimidine system are almost coplanar, the largest deviation from the mean plane being 0.027 (2) Å for a C atom. The conformation of the methyl-sulfanyl group is anti-periplanar, with a torsion angle of -176.7 (2)°. A weak inter-molecular C-H⋯N hydrogen bond and a Cl⋯N halogen bond [Cl⋯N = 3.196 (5) Å] with a nearly linear N⋯Cl-C angle [174.2 (1)°] link the mol-ecules into a two-dimensional assembly. Face-to-face π-π stacking, with a centroid-centroid separation of 3.557 (2) Å and an angle of 7.1 (1)° between the two planes, completes the inter-molecular inter-actions in the solid state.

Related literature

For the biological activity of pyrazolo[1,5-a]pyrimidine derivatives, see: Li et al. (1995 ▶). For applications of enamino­nes, see: El-Taweei et al. (2001 ▶); Hernandez et al. (2003 ▶); Olivera et al. (2000 ▶). For bond-length data, see: Allen et al. (1987 ▶). For Cl⋯N halogen bonds, see: Chu, et al. (2001 ▶); Lommerse et al. (1996 ▶); Ramasubbu et al. (1986 ▶).

Experimental

Crystal data

C14H8Cl2N4S

M = 335.20

Monoclinic,

a = 8.230 (2) Å

b = 14.656 (4) Å

c = 12.667 (4) Å

β = 108.460 (5)°

V = 1449.3 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.59 mm−1

T = 293 K

0.32 × 0.26 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.814, T max = 0.879

8252 measured reflections

2965 independent reflections

2181 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.095

S = 1.04

2965 reflections

191 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014792/zl2192sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809014792/zl2192Isup2.hkl

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

C14H8Cl2N4S	F(000) = 680
Mr = 335.20	Dx = 1.536 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 970 reflections
a = 8.230 (2) Å	θ = 2.8–26.3°
b = 14.656 (4) Å	µ = 0.59 mm−1
c = 12.667 (4) Å	T = 293 K
β = 108.460 (5)°	Prism, colorless
V = 1449.3 (7) Å3	0.32 × 0.26 × 0.22 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2965 independent reflections
Radiation source: fine-focus sealed tube	2181 reflections with I > 2σ(I)
graphite	Rint = 0.032
φ and ω scans	θmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→10
Tmin = 0.814, Tmax = 0.879	k = −16→18
8252 measured reflections	l = −15→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0395P)2 + 0.5056P] where P = (Fo2 + 2Fc2)/3
2965 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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 matrix. 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, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating 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.

	x	y	z	Uiso*/Ueq
S1	0.07522 (9)	1.04589 (4)	0.33961 (6)	0.0515 (2)
Cl1	0.27654 (9)	0.56767 (4)	0.47097 (6)	0.0587 (2)
Cl2	0.81796 (7)	0.72025 (5)	0.77238 (6)	0.0570 (2)
N1	0.1176 (2)	0.88388 (12)	0.44665 (15)	0.0337 (4)
N2	0.0148 (2)	0.81205 (12)	0.45471 (14)	0.0304 (4)
N4	−0.4254 (3)	0.99138 (17)	0.2170 (2)	0.0694 (8)
C1	0.3585 (3)	0.65420 (15)	0.56647 (18)	0.0351 (5)
C2	0.5304 (3)	0.65097 (16)	0.62770 (19)	0.0399 (6)
H2	0.5982	0.6025	0.6193	0.048*
C3	0.6000 (3)	0.72040 (16)	0.70121 (19)	0.0373 (5)
C4	0.4996 (3)	0.79158 (16)	0.71666 (19)	0.0385 (5)
H4	0.5468	0.8373	0.7681	0.046*
C5	0.3289 (3)	0.79383 (16)	0.65490 (19)	0.0383 (5)
H5	0.2616	0.8420	0.6648	0.046*
C6	0.2541 (3)	0.72596 (14)	0.57789 (18)	0.0317 (5)
C7	0.0708 (3)	0.73292 (15)	0.51216 (18)	0.0335 (5)
C8	−0.0531 (3)	0.66876 (16)	0.5045 (2)	0.0437 (6)
H8	−0.0243	0.6132	0.5411	0.052*
C9	−0.2230 (3)	0.68669 (18)	0.4416 (2)	0.0479 (6)
H9	−0.3036	0.6412	0.4376	0.057*
N3	−0.2771 (2)	0.76324 (14)	0.38782 (17)	0.0427 (5)
C10	−0.1555 (3)	0.82588 (15)	0.39444 (18)	0.0336 (5)
C11	−0.1611 (3)	0.91130 (15)	0.34518 (18)	0.0352 (5)
C12	0.0087 (3)	0.94280 (15)	0.38006 (18)	0.0342 (5)
C13	0.3024 (4)	1.0381 (2)	0.4068 (3)	0.0697 (9)
H13A	0.3249	1.0229	0.4838	0.105*
H13B	0.3547	1.0957	0.4012	0.105*
H13C	0.3489	0.9916	0.3714	0.105*
C14	−0.3084 (3)	0.95536 (16)	0.2741 (2)	0.0429 (6)

	U11	U22	U33	U12	U13	U23
S1	0.0594 (4)	0.0374 (4)	0.0588 (4)	0.0004 (3)	0.0206 (3)	0.0114 (3)
Cl1	0.0602 (4)	0.0408 (4)	0.0615 (4)	0.0086 (3)	−0.0002 (3)	−0.0164 (3)
Cl2	0.0290 (3)	0.0678 (5)	0.0654 (5)	0.0002 (3)	0.0025 (3)	0.0056 (4)
N1	0.0313 (10)	0.0320 (10)	0.0379 (11)	0.0008 (8)	0.0110 (8)	0.0017 (8)
N2	0.0266 (9)	0.0312 (10)	0.0319 (10)	0.0020 (7)	0.0069 (7)	0.0012 (8)
N4	0.0641 (15)	0.0544 (15)	0.0648 (16)	0.0238 (12)	−0.0150 (13)	−0.0040 (12)
C1	0.0396 (13)	0.0294 (11)	0.0335 (12)	0.0021 (10)	0.0075 (10)	0.0003 (10)
C2	0.0361 (13)	0.0379 (13)	0.0445 (14)	0.0101 (10)	0.0113 (11)	0.0052 (11)
C3	0.0276 (11)	0.0421 (13)	0.0400 (13)	−0.0003 (10)	0.0075 (10)	0.0083 (11)
C4	0.0385 (13)	0.0377 (13)	0.0347 (12)	−0.0040 (10)	0.0049 (10)	−0.0013 (10)
C5	0.0391 (13)	0.0346 (13)	0.0388 (13)	0.0072 (10)	0.0089 (10)	−0.0002 (10)
C6	0.0309 (11)	0.0302 (11)	0.0312 (11)	0.0028 (9)	0.0056 (9)	0.0034 (9)
C7	0.0338 (12)	0.0325 (12)	0.0323 (12)	0.0048 (9)	0.0079 (10)	0.0029 (9)
C8	0.0417 (14)	0.0374 (14)	0.0475 (15)	−0.0015 (11)	0.0075 (11)	0.0110 (11)
C9	0.0385 (14)	0.0461 (15)	0.0550 (16)	−0.0102 (11)	0.0089 (12)	0.0053 (12)
N3	0.0289 (10)	0.0456 (12)	0.0497 (12)	−0.0016 (9)	0.0070 (9)	0.0027 (10)
C10	0.0280 (11)	0.0383 (13)	0.0327 (12)	0.0045 (10)	0.0069 (9)	−0.0005 (10)
C11	0.0353 (12)	0.0347 (12)	0.0319 (12)	0.0072 (10)	0.0054 (9)	0.0002 (10)
C12	0.0391 (12)	0.0320 (12)	0.0319 (12)	0.0021 (10)	0.0117 (10)	0.0001 (10)
C13	0.0535 (17)	0.0595 (19)	0.104 (3)	−0.0107 (14)	0.0367 (17)	0.0076 (18)
C14	0.0450 (14)	0.0362 (13)	0.0393 (13)	0.0077 (11)	0.0016 (11)	−0.0040 (11)

S1—C12	1.739 (2)	C5—C6	1.393 (3)
S1—C13	1.796 (3)	C5—H5	0.9300
Cl1—C1	1.735 (2)	C6—C7	1.478 (3)
Cl2—C3	1.734 (2)	C7—C8	1.368 (3)
N1—C12	1.335 (3)	C8—C9	1.398 (3)
N1—N2	1.375 (2)	C8—H8	0.9300
N2—C7	1.369 (3)	C9—N3	1.315 (3)
N2—C10	1.383 (3)	C9—H9	0.9300
N4—C14	1.135 (3)	N3—C10	1.341 (3)
C1—C2	1.382 (3)	C10—C11	1.393 (3)
C1—C6	1.394 (3)	C11—C12	1.404 (3)
C2—C3	1.376 (3)	C11—C14	1.416 (3)
C2—H2	0.9300	C13—H13A	0.9600
C3—C4	1.383 (3)	C13—H13B	0.9600
C4—C5	1.375 (3)	C13—H13C	0.9600
C4—H4	0.9300
C12—S1—C13	100.53 (12)	N2—C7—C6	118.02 (18)
C12—N1—N2	103.65 (17)	C7—C8—C9	120.0 (2)
C7—N2—N1	125.20 (17)	C7—C8—H8	120.0
C7—N2—C10	121.97 (18)	C9—C8—H8	120.0
N1—N2—C10	112.79 (17)	N3—C9—C8	124.7 (2)
C2—C1—C6	121.5 (2)	N3—C9—H9	117.6
C2—C1—Cl1	117.98 (17)	C8—C9—H9	117.6
C6—C1—Cl1	120.48 (17)	C9—N3—C10	115.34 (19)
C3—C2—C1	119.2 (2)	N3—C10—N2	122.7 (2)
C3—C2—H2	120.4	N3—C10—C11	132.0 (2)
C1—C2—H2	120.4	N2—C10—C11	105.25 (18)
C2—C3—C4	120.9 (2)	C10—C11—C12	105.43 (18)
C2—C3—Cl2	119.44 (18)	C10—C11—C14	126.5 (2)
C4—C3—Cl2	119.59 (18)	C12—C11—C14	128.1 (2)
C5—C4—C3	119.1 (2)	N1—C12—C11	112.9 (2)
C5—C4—H4	120.4	N1—C12—S1	122.49 (17)
C3—C4—H4	120.4	C11—C12—S1	124.61 (17)
C4—C5—C6	121.8 (2)	S1—C13—H13A	109.5
C4—C5—H5	119.1	S1—C13—H13B	109.5
C6—C5—H5	119.1	H13A—C13—H13B	109.5
C5—C6—C1	117.5 (2)	S1—C13—H13C	109.5
C5—C6—C7	119.43 (19)	H13A—C13—H13C	109.5
C1—C6—C7	123.12 (19)	H13B—C13—H13C	109.5
C8—C7—N2	115.24 (19)	N4—C14—C11	179.3 (3)
C8—C7—C6	126.7 (2)
C12—N1—N2—C7	177.7 (2)	N2—C7—C8—C9	−0.3 (3)
C12—N1—N2—C10	−0.1 (2)	C6—C7—C8—C9	177.8 (2)
C6—C1—C2—C3	−0.3 (3)	C7—C8—C9—N3	−0.8 (4)
Cl1—C1—C2—C3	177.75 (18)	C8—C9—N3—C10	1.3 (4)
C1—C2—C3—C4	1.8 (4)	C9—N3—C10—N2	−0.9 (3)
C1—C2—C3—Cl2	−176.31 (18)	C9—N3—C10—C11	176.2 (2)
C2—C3—C4—C5	−1.9 (4)	C7—N2—C10—N3	−0.1 (3)
Cl2—C3—C4—C5	176.16 (18)	N1—N2—C10—N3	177.8 (2)
C3—C4—C5—C6	0.6 (4)	C7—N2—C10—C11	−177.85 (19)
C4—C5—C6—C1	0.9 (3)	N1—N2—C10—C11	0.1 (2)
C4—C5—C6—C7	−178.7 (2)	N3—C10—C11—C12	−177.4 (2)
C2—C1—C6—C5	−1.0 (3)	N2—C10—C11—C12	0.0 (2)
Cl1—C1—C6—C5	−179.02 (18)	N3—C10—C11—C14	1.9 (4)
C2—C1—C6—C7	178.6 (2)	N2—C10—C11—C14	179.4 (2)
Cl1—C1—C6—C7	0.6 (3)	N2—N1—C12—C11	0.1 (2)
N1—N2—C7—C8	−177.0 (2)	N2—N1—C12—S1	−178.37 (15)
C10—N2—C7—C8	0.7 (3)	C10—C11—C12—N1	−0.1 (3)
N1—N2—C7—C6	4.8 (3)	C14—C11—C12—N1	−179.5 (2)
C10—N2—C7—C6	−177.55 (19)	C10—C11—C12—S1	178.38 (17)
C5—C6—C7—C8	−125.1 (3)	C14—C11—C12—S1	−1.0 (3)
C1—C6—C7—C8	55.3 (3)	C13—S1—C12—N1	1.7 (2)
C5—C6—C7—N2	52.9 (3)	C13—S1—C12—C11	−176.7 (2)
C1—C6—C7—N2	−126.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···N4i	0.93	2.61	3.474 (3)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯N4i	0.93	2.61	3.474 (3)	154

Symmetry code: (i) .