5-[(1H-1,2,4-Yriazol-1-yl)meth­yl]-4-(4-fluoro­benzylidene­amino)-2H-1,2,4-triazole-3(4H)-thione

In the title compound, C₁₂H₁₀FN₇S, the dihedral angles made by the plane of the thione-substituted triazole ring with the planes of the other triazole ring and the benzene ring are 71.94 (3) and 40.10 (2)°, respectively. Inter- and intra­mol­ecular hydrogen-bond and π–π stacking inter­actions stabilize the structure.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.044
• wR factor = 0.111
• Data-to-parameter ratio = 14.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C5      ..       5.30 su
PLAT432_ALERT_2_C Short Inter X...Y Contact  F1     ..  C2      ..       2.92 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Compounds containing the 1,2,4-triazole ring possess a broad pharmacological activity spectrum encompassing anti-inflammatory (Prasad et al., 1989), sedative, smooth-muscle relaxation (Gall et al., 1976), anticonvulsant (Kane et al., 1990), antituberculosis (Mir et al., 1970) and platelet-aggregation inhibitory activities (Lagorce et al., 1992). In search of better biological activity, the title compound, (I), was synthesized. We report here the crystal structure of (I).

The bond lengths and angles of the thione-substituted triazole ring and the other triazole ring (Table 1) are in agreement with the values quotes in previous reports (Li et al., 2005; Xu et al., 2005). The molecule exists in the thione tautomeric form, with an S═ C distance of 1.668 (2) Å, which indicates substantial double-bond character (Allen et al., 1987). The planes C1–C3/N1–N3 and C6–C12/N7/F1 make angles of 71.94 (3) and 40.10 (2)°, respectively, with the thione-substituted triazole plane C4/C5/N4–N6/S1. The crystal structure of (I) is stabilized by weak intra- and intermolecular hydrogen bonds and double π–π stacking interactions. The π–π stacking interactions invole the thione-substituted triazole ring (C4/C5/N4–N6/S1) R1 and the benzene ring (C7–C12) R2. The distance between the centroids of rings R1 and R2 are 3.589 (8) Å at (−1/2 + x, 1/2 − y, −z) and 3.857 (4) Å at (1/2 + x, 1/2 − y, −z).

S2. Experimental

A mixture of 4-amino-3-(1,2,4-triazol-1-yl)-1H-1,2,4-triazole-5(4H)-thione (0.02 mol) and 4-fluorobenzaldehyde (0.02 mol) were refluxed at 391 K for 15–20 min in glacial acetic acid to yield a yellow crystalline precitate which was re-crystallized from ethanol to afford yellow crystals of the title compound (5.45 g, yield 90%; m.p. 497–498 K). ¹H NMR (DMSO, 600 MHz): δ 14.16 (s, 1H), 10.00 (s, 1H), 8.70 (s, 1H), 7.41–7.99 (m, 4H), 5.70 (s, 2H). IR (KBr, cm⁻¹): 3437, 3109, 2889, 1600, 1509, 1273. Analysis calculated for C₁₂H₁₀FN₇S (Mr = 303.3): C 47.52, H 3.32, N 32.32%; found C 47.53, H 3.30, N 32.33%. Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

All C-bound H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å, and included in the final cycles of refinement using a riding model, with U_iso(H) = 1.2U_eq(C). NH H atom treatment?

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of the title compound, (I), with displacement ellipsoids for non-H atoms drawn at the 40% probability level. H atoms are represented as spheres of arbitrary radii.
	Fig. 2. A packing diagram of the molecule of the title compound, viewed down the a axis. Hydrogen bonds are shown as dashed lines.

5-((1H-1,2,4-triazol-1-yl)methyl)-4-(4-fluorobenzylideneamino)-2H- 1,2,4-triazole-3(4H)-thione

Crystal data

C12H10FN7S	F(000) = 1248
Mr = 303.33	Dx = 1.452 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2822 reflections
a = 7.146 (4) Å	θ = 2.3–25.1°
b = 17.906 (9) Å	µ = 0.25 mm^−1
c = 21.697 (11) Å	T = 294 K
V = 2776 (3) Å^3	Block, yellow
Z = 8	0.32 × 0.22 × 0.10 mm

Data collection

Bruker SMART CCD area detector diffractometer	2855 independent reflections
Radiation source: fine-focus sealed tube	1673 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ϕ and ω scans	θmax = 26.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→6
Tmin = 0.910, Tmax = 0.971	k = −17→22
14610 measured reflections	l = −27→27

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0423P)^2 + 0.939P] where P = (Fo^2 + 2Fc^2)/3
2855 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.23628 (11)	0.09151 (4)	0.48858 (3)	0.0593 (2)
F1	0.1853 (3)	0.47698 (12)	0.28040 (8)	0.1076 (8)
N1	0.3211 (4)	0.45649 (12)	0.64024 (10)	0.0556 (6)
N2	0.2937 (3)	0.34949 (12)	0.69400 (10)	0.0535 (6)
N3	0.1566 (3)	0.35474 (11)	0.65073 (8)	0.0408 (5)
N4	0.0901 (3)	0.16373 (11)	0.65095 (8)	0.0425 (5)
N5	0.1469 (3)	0.11142 (12)	0.60851 (9)	0.0434 (5)
N6	0.1253 (3)	0.21347 (10)	0.55896 (8)	0.0367 (5)
N7	0.1476 (3)	0.27395 (11)	0.51807 (8)	0.0412 (5)
C1	0.1769 (4)	0.41843 (15)	0.61978 (11)	0.0513 (7)
H1	0.0991	0.4339	0.5879	0.062*
C2	0.3876 (4)	0.41172 (15)	0.68522 (13)	0.0574 (7)
H2	0.4926	0.4240	0.7084	0.069*
C3	0.0112 (4)	0.29788 (13)	0.64484 (11)	0.0430 (6)
H3A	−0.0865	0.3167	0.6179	0.052*
H3B	−0.0441	0.2892	0.6850	0.052*
C4	0.0808 (3)	0.22546 (13)	0.61986 (10)	0.0359 (6)
C5	0.1705 (3)	0.13854 (13)	0.55131 (11)	0.0401 (6)
C6	0.1001 (3)	0.26136 (14)	0.46212 (11)	0.0423 (6)
H6	0.0508	0.2151	0.4512	0.051*
C7	0.1228 (3)	0.31919 (14)	0.41548 (10)	0.0390 (6)
C8	0.0703 (4)	0.30365 (16)	0.35493 (11)	0.0515 (7)
H8	0.0220	0.2569	0.3453	0.062*
C9	0.0889 (4)	0.35663 (19)	0.30910 (12)	0.0630 (8)
H9	0.0530	0.3465	0.2688	0.076*
C10	0.1620 (4)	0.42445 (18)	0.32505 (12)	0.0623 (8)
C11	0.2145 (4)	0.44279 (16)	0.38383 (11)	0.0547 (7)
H11	0.2622	0.4899	0.3929	0.066*
C12	0.1948 (3)	0.38969 (14)	0.42907 (11)	0.0443 (6)
H12	0.2299	0.4009	0.4693	0.053*
H5	0.156 (4)	0.0618 (18)	0.6218 (13)	0.081 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0780 (5)	0.0430 (4)	0.0570 (4)	0.0004 (4)	0.0135 (4)	−0.0167 (3)
F1	0.170 (2)	0.0931 (16)	0.0593 (10)	−0.0086 (14)	−0.0064 (12)	0.0396 (11)
N1	0.0808 (17)	0.0315 (13)	0.0544 (13)	−0.0061 (11)	−0.0022 (12)	−0.0023 (11)
N2	0.0733 (17)	0.0336 (13)	0.0535 (13)	0.0017 (11)	−0.0156 (11)	−0.0009 (11)
N3	0.0594 (13)	0.0255 (11)	0.0376 (10)	0.0034 (9)	−0.0032 (10)	−0.0030 (9)
N4	0.0587 (14)	0.0295 (12)	0.0393 (11)	−0.0026 (9)	0.0014 (10)	0.0001 (10)
N5	0.0585 (14)	0.0253 (12)	0.0465 (13)	−0.0007 (10)	0.0032 (10)	0.0005 (10)
N6	0.0500 (12)	0.0250 (10)	0.0350 (10)	−0.0007 (9)	0.0024 (9)	0.0019 (9)
N7	0.0551 (13)	0.0300 (12)	0.0386 (11)	0.0008 (9)	0.0031 (10)	0.0042 (9)
C1	0.077 (2)	0.0329 (15)	0.0441 (14)	0.0028 (14)	−0.0074 (14)	0.0035 (12)
C2	0.071 (2)	0.0352 (16)	0.0659 (18)	0.0003 (14)	−0.0135 (15)	−0.0106 (15)
C3	0.0528 (15)	0.0333 (15)	0.0430 (13)	0.0011 (11)	0.0018 (12)	−0.0060 (12)
C4	0.0453 (14)	0.0277 (14)	0.0348 (12)	−0.0035 (10)	0.0016 (11)	0.0000 (11)
C5	0.0452 (15)	0.0278 (14)	0.0474 (14)	−0.0032 (11)	0.0002 (12)	−0.0001 (11)
C6	0.0458 (16)	0.0389 (15)	0.0422 (14)	−0.0007 (12)	0.0000 (11)	−0.0029 (12)
C7	0.0417 (14)	0.0409 (15)	0.0344 (13)	0.0043 (11)	0.0014 (11)	−0.0002 (11)
C8	0.0596 (17)	0.0527 (18)	0.0424 (14)	−0.0029 (14)	−0.0034 (13)	−0.0055 (14)
C9	0.080 (2)	0.077 (2)	0.0320 (14)	0.0017 (18)	−0.0095 (13)	−0.0004 (15)
C10	0.086 (2)	0.062 (2)	0.0387 (15)	0.0091 (17)	0.0040 (15)	0.0166 (15)
C11	0.079 (2)	0.0398 (16)	0.0456 (15)	0.0036 (14)	0.0063 (14)	0.0034 (13)
C12	0.0590 (17)	0.0412 (16)	0.0328 (12)	0.0002 (12)	0.0010 (11)	−0.0019 (11)

Geometric parameters (Å, º)

S1—C5	1.668 (2)	C2—H2	0.9300
F1—C10	1.361 (3)	C3—C4	1.491 (3)
N1—C1	1.313 (3)	C3—H3A	0.9700
N1—C2	1.350 (3)	C3—H3B	0.9700
N2—C2	1.315 (3)	C6—C7	1.457 (3)
N2—N3	1.360 (3)	C6—H6	0.9300
N3—C1	1.331 (3)	C7—C8	1.394 (3)
N3—C3	1.460 (3)	C7—C12	1.395 (3)
N4—C4	1.297 (3)	C8—C9	1.381 (4)
N4—N5	1.375 (3)	C8—H8	0.9300
N5—C5	1.343 (3)	C9—C10	1.366 (4)
N5—H5	0.94 (3)	C9—H9	0.9300
N6—C4	1.376 (3)	C10—C11	1.369 (4)
N6—C5	1.390 (3)	C11—C12	1.374 (3)
N6—N7	1.409 (3)	C11—H11	0.9300
N7—C6	1.280 (3)	C12—H12	0.9300
C1—H1	0.9300
C1—N1—C2	102.3 (2)	N4—C4—C3	124.7 (2)
C2—N2—N3	102.1 (2)	N6—C4—C3	124.2 (2)
C1—N3—N2	109.2 (2)	N5—C5—N6	102.07 (19)
C1—N3—C3	129.1 (2)	N5—C5—S1	127.36 (19)
N2—N3—C3	121.7 (2)	N6—C5—S1	130.57 (18)
C4—N4—N5	104.34 (19)	N7—C6—C7	120.3 (2)
C5—N5—N4	114.2 (2)	N7—C6—H6	119.9
C5—N5—H5	128.2 (18)	C7—C6—H6	119.9
N4—N5—H5	117.4 (18)	C8—C7—C12	118.6 (2)
C4—N6—C5	108.61 (18)	C8—C7—C6	118.9 (2)
C4—N6—N7	120.73 (18)	C12—C7—C6	122.5 (2)
C5—N6—N7	129.80 (18)	C9—C8—C7	121.0 (3)
C6—N7—N6	115.6 (2)	C9—C8—H8	119.5
N1—C1—N3	111.1 (2)	C7—C8—H8	119.5
N1—C1—H1	124.5	C10—C9—C8	117.7 (2)
N3—C1—H1	124.5	C10—C9—H9	121.1
N2—C2—N1	115.4 (2)	C8—C9—H9	121.1
N2—C2—H2	122.3	F1—C10—C9	118.7 (3)
N1—C2—H2	122.3	F1—C10—C11	117.6 (3)
N3—C3—C4	113.6 (2)	C9—C10—C11	123.6 (3)
N3—C3—H3A	108.8	C10—C11—C12	118.1 (3)
C4—C3—H3A	108.8	C10—C11—H11	120.9
N3—C3—H3B	108.8	C12—C11—H11	120.9
C4—C3—H3B	108.8	C11—C12—C7	120.9 (2)
H3A—C3—H3B	107.7	C11—C12—H12	119.6
N4—C4—N6	110.8 (2)	C7—C12—H12	119.6
C2—N2—N3—C1	−0.2 (3)	N4—N5—C5—N6	0.2 (3)
C2—N2—N3—C3	−177.7 (2)	N4—N5—C5—S1	−179.46 (18)
C4—N4—N5—C5	−1.1 (3)	C4—N6—C5—N5	0.8 (2)
C4—N6—N7—C6	−147.8 (2)	N7—N6—C5—N5	170.0 (2)
C5—N6—N7—C6	44.1 (3)	C4—N6—C5—S1	−179.6 (2)
C2—N1—C1—N3	0.4 (3)	N7—N6—C5—S1	−10.4 (4)
N2—N3—C1—N1	−0.1 (3)	N6—N7—C6—C7	−178.08 (19)
C3—N3—C1—N1	177.1 (2)	N7—C6—C7—C8	179.8 (2)
N3—N2—C2—N1	0.4 (3)	N7—C6—C7—C12	−0.4 (4)
C1—N1—C2—N2	−0.5 (3)	C12—C7—C8—C9	0.1 (4)
C1—N3—C3—C4	112.5 (3)	C6—C7—C8—C9	179.9 (2)
N2—N3—C3—C4	−70.5 (3)	C7—C8—C9—C10	0.6 (4)
N5—N4—C4—N6	1.5 (3)	C8—C9—C10—F1	178.6 (3)
N5—N4—C4—C3	175.2 (2)	C8—C9—C10—C11	−1.0 (5)
C5—N6—C4—N4	−1.5 (3)	F1—C10—C11—C12	−178.8 (2)
N7—N6—C4—N4	−171.89 (19)	C9—C10—C11—C12	0.9 (5)
C5—N6—C4—C3	−175.3 (2)	C10—C11—C12—C7	−0.2 (4)
N7—N6—C4—C3	14.3 (3)	C8—C7—C12—C11	−0.3 (4)
N3—C3—C4—N4	112.2 (3)	C6—C7—C12—C11	179.9 (2)
N3—C3—C4—N6	−74.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···N1^i	0.94 (3)	1.94 (3)	2.867 (3)	174 (3)
C6—H6···S1	0.93	2.70	3.244 (3)	118
C9—H9···N4^ii	0.93	2.58	3.451 (4)	157
C11—H11···S1^iii	0.93	2.76	3.519 (3)	139

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x, −y+1/2, z−1/2; (iii) −x+1/2, y+1/2, z.