3-Ethyl-6-[3-(4-fluoro-phen-yl)-1H-pyrazol-4-yl]-1,2,4-triazolo[3,4-b][1,3,4]thia-diazole.

In the title compound, C(14)H(11)FN(6)S, the 1,2,4-triazolo[3,4-b][1,3,4]thia-diazole ring system is essentially planar [maximum deviation = 0.022 (3) Å] and is inclined at dihedral angles of 15.00 (18) and 52.82 (16)° with respect to the pyrazole and phenyl rings. In the crystal, mol-ecules are linked into two-dimensional networks parallel to (100) via inter-molecular N-H⋯N and weak C-H⋯N hydrogen bonds. The crystal packing is further consolidated by weak π-π stacking inter-actions, with a centroid-centroid distance of 3.590 (2) Å. The crystal studied was an inversion twin with a 0.37 (13):0.63 (13) domain ratio.

Related literature

For general background to and the biological activity of heterocycles bearing a triazole or 1,3,4-thia­diazole group, see: Farghaly (2004 ▶); Czarnocka et al. (1991 ▶); Unangst et al. (1992 ▶); Dhanya et al. (2009 ▶); Farghaly et al. (2006 ▶); Omar & Aboulwafa (1986 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C14H11FN6S

M = 314.35

Orthorhombic,

a = 35.053 (2) Å

b = 3.8463 (2) Å

c = 9.9482 (6) Å

V = 1341.26 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 100 K

0.64 × 0.27 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.852, T max = 0.978

6132 measured reflections

2884 independent reflections

2814 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.123

S = 1.21

2884 reflections

205 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.45 e Å−3

Δρmin = −0.43 e Å−3

Absolute structure: Flack (1983 ▶), 1283 Friedel pairs

Flack parameter: 0.37 (13)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810040067/lh5142sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040067/lh5142Isup2.hkl

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

C14H11FN6S	F(000) = 648
Mr = 314.35	Dx = 1.557 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 4113 reflections
a = 35.053 (2) Å	θ = 2.3–30.0°
b = 3.8463 (2) Å	µ = 0.26 mm−1
c = 9.9482 (6) Å	T = 100 K
V = 1341.26 (13) Å3	Plate, colourless
Z = 4	0.64 × 0.27 × 0.09 mm

Bruker SMART APEXII CCD area-detector diffractometer	2884 independent reflections
Radiation source: fine-focus sealed tube	2814 reflections with I > 2σ(I)
graphite	Rint = 0.030
φ and ω scans	θmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −45→38
Tmin = 0.852, Tmax = 0.978	k = −4→4
6132 measured reflections	l = −12→12

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.123	w = 1/[σ2(Fo2) + (0.0155P)2 + 3.5431P] where P = (Fo2 + 2Fc2)/3
S = 1.21	(Δ/σ)max < 0.001
2884 reflections	Δρmax = 0.45 e Å−3
205 parameters	Δρmin = −0.43 e Å−3
1 restraint	Absolute structure: Flack (1983), 1283 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.37 (13)

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.47232 (2)	0.8682 (2)	0.07220 (9)	0.01492 (19)
F1	0.23063 (7)	0.4421 (7)	0.0128 (3)	0.0271 (6)
N1	0.38932 (9)	0.3394 (9)	−0.2794 (3)	0.0178 (7)
N2	0.42751 (9)	0.3714 (10)	−0.2988 (3)	0.0180 (7)
N3	0.40306 (9)	0.6762 (8)	0.1424 (3)	0.0143 (7)
N4	0.42034 (9)	0.8422 (8)	0.2497 (3)	0.0136 (6)
N5	0.46852 (9)	1.1284 (9)	0.3395 (3)	0.0178 (7)
N6	0.43819 (9)	1.1004 (9)	0.4319 (3)	0.0162 (7)
C1	0.33272 (11)	0.3145 (10)	0.0202 (4)	0.0157 (7)
H1A	0.3513	0.2268	0.0775	0.019*
C2	0.29475 (10)	0.3088 (9)	0.0598 (4)	0.0160 (7)
H2A	0.2876	0.2148	0.1421	0.019*
C3	0.26802 (11)	0.4463 (11)	−0.0264 (4)	0.0185 (8)
C4	0.27725 (12)	0.5778 (11)	−0.1507 (4)	0.0207 (9)
H4A	0.2584	0.6626	−0.2079	0.025*
C5	0.31518 (12)	0.5807 (12)	−0.1884 (4)	0.0204 (9)
H5A	0.3220	0.6721	−0.2716	0.024*
C6	0.34334 (10)	0.4494 (10)	−0.1041 (4)	0.0133 (7)
C7	0.38318 (11)	0.4419 (10)	−0.1510 (4)	0.0136 (7)
C8	0.41873 (10)	0.5305 (9)	−0.0900 (4)	0.0111 (7)
C9	0.44590 (11)	0.4807 (10)	−0.1900 (4)	0.0146 (8)
H9A	0.4720	0.5171	−0.1821	0.017*
C10	0.42692 (10)	0.6731 (10)	0.0422 (3)	0.0147 (8)
C11	0.45625 (11)	0.9692 (10)	0.2316 (3)	0.0118 (7)
C12	0.40957 (10)	0.9339 (9)	0.3769 (4)	0.0123 (7)
C13	0.37264 (10)	0.8435 (11)	0.4415 (4)	0.0153 (7)
H13A	0.3710	0.9620	0.5273	0.018*
H13B	0.3722	0.5954	0.4589	0.018*
C14	0.33739 (11)	0.9399 (10)	0.3566 (4)	0.0166 (8)
H14A	0.3147	0.8962	0.4077	0.025*
H14B	0.3370	0.8017	0.2763	0.025*
H14C	0.3385	1.1817	0.3331	0.025*
H1N2	0.4397 (12)	0.306 (13)	−0.389 (4)	0.024 (13)*

	U11	U22	U33	U12	U13	U23
S1	0.0157 (4)	0.0175 (4)	0.0115 (4)	−0.0014 (4)	0.0014 (4)	−0.0018 (4)
F1	0.0180 (12)	0.0346 (15)	0.0287 (13)	0.0023 (11)	0.0020 (10)	0.0012 (12)
N1	0.0195 (17)	0.0204 (17)	0.0136 (16)	0.0036 (14)	−0.0003 (12)	−0.0017 (14)
N2	0.0194 (16)	0.0230 (18)	0.0117 (14)	0.0023 (15)	0.0022 (13)	−0.0031 (14)
N3	0.0209 (16)	0.0097 (16)	0.0123 (15)	0.0002 (13)	−0.0036 (13)	−0.0057 (13)
N4	0.0165 (15)	0.0151 (15)	0.0093 (13)	0.0011 (13)	−0.0026 (12)	−0.0019 (14)
N5	0.0173 (16)	0.0198 (18)	0.0163 (16)	0.0012 (14)	0.0005 (13)	−0.0056 (14)
N6	0.0165 (15)	0.0197 (18)	0.0124 (14)	−0.0003 (14)	−0.0001 (12)	−0.0019 (14)
C1	0.0189 (18)	0.0148 (18)	0.0133 (16)	0.0005 (15)	−0.0039 (14)	−0.0022 (15)
C2	0.0217 (17)	0.0153 (18)	0.0108 (17)	−0.0031 (14)	0.0016 (16)	−0.0029 (17)
C3	0.0142 (18)	0.021 (2)	0.0204 (19)	0.0006 (16)	−0.0016 (16)	−0.0025 (17)
C4	0.023 (2)	0.024 (2)	0.0146 (19)	0.0035 (18)	−0.0070 (15)	−0.0009 (17)
C5	0.025 (2)	0.021 (2)	0.0151 (18)	−0.0004 (18)	0.0005 (16)	−0.0035 (16)
C6	0.0158 (17)	0.0099 (17)	0.0142 (18)	−0.0005 (14)	0.0006 (14)	−0.0048 (14)
C7	0.0198 (18)	0.0101 (18)	0.0108 (17)	0.0018 (14)	−0.0018 (14)	0.0002 (15)
C8	0.0152 (17)	0.0080 (17)	0.0102 (16)	0.0012 (13)	−0.0007 (13)	−0.0005 (14)
C9	0.0199 (19)	0.013 (2)	0.0105 (16)	−0.0015 (15)	−0.0011 (15)	−0.0013 (14)
C10	0.0151 (17)	0.0125 (17)	0.017 (2)	0.0032 (14)	−0.0025 (13)	−0.0007 (15)
C11	0.0173 (17)	0.0112 (17)	0.0069 (16)	0.0003 (14)	−0.0004 (13)	−0.0031 (14)
C12	0.0177 (17)	0.0082 (17)	0.0109 (16)	0.0005 (14)	−0.0037 (13)	−0.0009 (14)
C13	0.0194 (18)	0.0132 (18)	0.0132 (17)	−0.0046 (15)	0.0008 (14)	0.0001 (15)
C14	0.0169 (18)	0.0162 (19)	0.0166 (18)	−0.0017 (15)	0.0017 (15)	−0.0019 (16)

S1—C11	1.727 (3)	C2—H2A	0.9300
S1—C10	1.784 (4)	C3—C4	1.374 (6)
F1—C3	1.367 (4)	C4—C5	1.382 (6)
N1—C7	1.354 (5)	C4—H4A	0.9300
N1—N2	1.358 (4)	C5—C6	1.390 (5)
N2—C9	1.328 (5)	C5—H5A	0.9300
N2—H1N2	1.02 (5)	C6—C7	1.473 (5)
N3—C10	1.301 (5)	C7—C8	1.427 (5)
N3—N4	1.383 (4)	C8—C9	1.390 (5)
N4—C11	1.362 (5)	C8—C10	1.453 (5)
N4—C12	1.367 (5)	C9—H9A	0.9300
N5—C11	1.309 (5)	C12—C13	1.486 (5)
N5—N6	1.409 (4)	C13—C14	1.542 (5)
N6—C12	1.310 (5)	C13—H13A	0.9700
C1—C2	1.388 (5)	C13—H13B	0.9700
C1—C6	1.391 (5)	C14—H14A	0.9600
C1—H1A	0.9300	C14—H14B	0.9600
C2—C3	1.376 (5)	C14—H14C	0.9600
C11—S1—C10	87.55 (17)	N1—C7—C6	117.1 (3)
C7—N1—N2	105.3 (3)	C8—C7—C6	133.5 (3)
C9—N2—N1	113.0 (3)	C9—C8—C7	105.1 (3)
C9—N2—H1N2	126 (2)	C9—C8—C10	124.3 (3)
N1—N2—H1N2	121 (2)	C7—C8—C10	130.3 (3)
C10—N3—N4	108.3 (3)	N2—C9—C8	107.1 (3)
C11—N4—C12	106.6 (3)	N2—C9—H9A	126.4
C11—N4—N3	117.9 (3)	C8—C9—H9A	126.4
C12—N4—N3	135.4 (3)	N3—C10—C8	124.7 (3)
C11—N5—N6	104.5 (3)	N3—C10—S1	116.2 (3)
C12—N6—N5	110.0 (3)	C8—C10—S1	119.1 (3)
C2—C1—C6	121.0 (4)	N5—C11—N4	111.3 (3)
C2—C1—H1A	119.5	N5—C11—S1	138.7 (3)
C6—C1—H1A	119.5	N4—C11—S1	110.0 (3)
C3—C2—C1	118.0 (4)	N6—C12—N4	107.5 (3)
C3—C2—H2A	121.0	N6—C12—C13	127.0 (3)
C1—C2—H2A	121.0	N4—C12—C13	125.5 (3)
F1—C3—C4	119.1 (4)	C12—C13—C14	113.9 (3)
F1—C3—C2	118.1 (4)	C12—C13—H13A	108.8
C4—C3—C2	122.8 (4)	C14—C13—H13A	108.8
C3—C4—C5	118.3 (4)	C12—C13—H13B	108.8
C3—C4—H4A	120.9	C14—C13—H13B	108.8
C5—C4—H4A	120.9	H13A—C13—H13B	107.7
C4—C5—C6	121.1 (4)	C13—C14—H14A	109.5
C4—C5—H5A	119.5	C13—C14—H14B	109.5
C6—C5—H5A	119.5	H14A—C14—H14B	109.5
C5—C6—C1	118.8 (3)	C13—C14—H14C	109.5
C5—C6—C7	119.3 (3)	H14A—C14—H14C	109.5
C1—C6—C7	121.8 (3)	H14B—C14—H14C	109.5
N1—C7—C8	109.4 (3)
C7—N1—N2—C9	1.3 (5)	C10—C8—C9—N2	−175.5 (4)
C10—N3—N4—C11	1.2 (4)	N4—N3—C10—C8	−178.0 (3)
C10—N3—N4—C12	177.3 (4)	N4—N3—C10—S1	0.7 (4)
C11—N5—N6—C12	−0.7 (4)	C9—C8—C10—N3	−169.9 (4)
C6—C1—C2—C3	−1.2 (6)	C7—C8—C10—N3	16.1 (6)
C1—C2—C3—F1	−179.7 (3)	C9—C8—C10—S1	11.4 (5)
C1—C2—C3—C4	2.1 (6)	C7—C8—C10—S1	−162.5 (3)
F1—C3—C4—C5	179.8 (4)	C11—S1—C10—N3	−1.7 (3)
C2—C3—C4—C5	−2.0 (6)	C11—S1—C10—C8	177.0 (3)
C3—C4—C5—C6	1.0 (6)	N6—N5—C11—N4	−0.1 (4)
C4—C5—C6—C1	−0.2 (6)	N6—N5—C11—S1	−179.4 (4)
C4—C5—C6—C7	177.0 (4)	C12—N4—C11—N5	0.9 (4)
C2—C1—C6—C5	0.3 (6)	N3—N4—C11—N5	178.0 (3)
C2—C1—C6—C7	−176.9 (4)	C12—N4—C11—S1	−179.6 (2)
N2—N1—C7—C8	−1.4 (4)	N3—N4—C11—S1	−2.5 (4)
N2—N1—C7—C6	177.2 (3)	C10—S1—C11—N5	−178.5 (5)
C5—C6—C7—N1	−42.4 (5)	C10—S1—C11—N4	2.2 (3)
C1—C6—C7—N1	134.7 (4)	N5—N6—C12—N4	1.3 (4)
C5—C6—C7—C8	135.7 (4)	N5—N6—C12—C13	178.5 (4)
C1—C6—C7—C8	−47.2 (6)	C11—N4—C12—N6	−1.3 (4)
N1—C7—C8—C9	1.1 (4)	N3—N4—C12—N6	−177.7 (4)
C6—C7—C8—C9	−177.2 (4)	C11—N4—C12—C13	−178.6 (3)
N1—C7—C8—C10	175.9 (4)	N3—N4—C12—C13	5.0 (6)
C6—C7—C8—C10	−2.4 (7)	N6—C12—C13—C14	131.2 (4)
N1—N2—C9—C8	−0.6 (5)	N4—C12—C13—C14	−52.0 (5)
C7—C8—C9—N2	−0.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···N6i	1.03 (4)	1.95 (4)	2.899 (4)	153 (4)
C9—H9A···N5ii	0.93	2.50	3.368 (5)	156
C13—H13A···N1iii	0.97	2.49	3.419 (5)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯N6i	1.03 (4)	1.95 (4)	2.899 (4)	153 (4)
C9—H9A⋯N5ii	0.93	2.50	3.368 (5)	156
C13—H13A⋯N1iii	0.97	2.49	3.419 (5)	160

Symmetry codes: (i) ; (ii) ; (iii) .