4-[(E)-(3-Methyl-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-4-yl)imino­meth­yl]benzonitrile

In the title compound, C₁₁H₉N₅S, the dihedral angle between the mean planes of the thione-substituted triazole ring and benzonitrile ring is 4.28 (3)°. Inter­molecular N—H...S hydrogen bonds link the mol­ecules together into characteristic dimers.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.043
• wR factor = 0.116
• Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.07
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C8     -   C11    ...       1.44 Ang.
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT063_ALERT_4_C Crystal Probably too Large for Beam Size .......       0.70 mm
PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ...     589.50 Ang-3
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        200 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         13
            C7  -C8  -C11 -N5     18.00  0.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         14
            C9  -C8  -C11 -N5      4.00 17.00   1.555   1.555   1.555   1.555

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   4 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
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

It has been found that 1,2,4-thiadiazoles possess a broad spectrum of biological activities and can be widely used as fungicides (Sharma & Bahel, 1982) and insecticides (Grasso, 1988). In addition, amine- and thione-substituted triazoles have been studied as anti-inflammatory and antimicrobial agents (Eweiss et al., 1986; Awad et al., 1991). Benzotriazole and its derivatives comprise an important class of corrosion inhibitors, typically used as trace additives in industrial chemical mixtures, such as coolants, cutting fluids and hydraulic fluids (Pillard et al., 2001). We present its crystal structure here. The molecule exists in the thione tautomeric form, with an S···C distance of 1.6752 (3) A °, which indicates substantial double-bond character for this bond [1.671 (24) A °, Allen et al., 1987]. The dihedral angle between thione-substituted triazole ring and benzonitrile ring is 4.28 (3) °. N-H···N hydrogen bonds are observed in the crystal structure which link the molecules into dimers.

Related literature

For the application of benzotriazole compounds in industry, see: Sharma & Bahel (1982); Grasso (1988); Eweiss et al. (1986); Awad et al. (1991); Pillard et al. (2001). For bond-length data, see: Allen et al. (1987).

S2. Experimental

A mixture of 4-amino-3-methanyl-1H-1,2,4-triazole-5(4H)- thione (0.02 mol) and 4-formylbenzonitrile (0.02 mol) was refluxed at 391 K for 20 min in methanol. The mixture was then filtered and crystallized from ethanol to afford the target material (yield 89%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

H atoms were calculated geometrically, with C—H distances in the range 0.93 to 0.97Å and an N—H distance of 0.86 Å, and refined using a riding model, with U_iso(H) =1.5Ueq(C) for methyl H atoms and 1.2Ueq(C,N) for the other H atoms.

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
	Fig. 2. A packing diagram of the title compound, viewed down the a axis.

4-[(E)-(3-Methyl-5-thioxo-4,5-dihydro-1H-1,2,4-triazol-4- yl)iminomethyl]benzonitrile

Crystal data

C11H9N5S	Z = 2
Mr = 243.29	F(000) = 252
Triclinic, P1	Dx = 1.371 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.975 (2) Å	Cell parameters from 1492 reflections
b = 7.682 (2) Å	θ = 3.0–27.4°
c = 11.412 (2) Å	µ = 0.26 mm^−1
α = 90.262 (7)°	T = 293 K
β = 94.328 (14)°	Block, colorless
γ = 104.713 (17)°	0.70 × 0.50 × 0.50 mm
V = 589.5 (3) Å^3

Data collection

Rigaku Mercury2 diffractometer	2659 independent reflections
Radiation source: fine-focus sealed tube	2178 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 13.6612 pixels mm^-1	θmax = 27.5°, θmin = 3.2°
CCD_Profile_fitting scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.854, Tmax = 0.901	l = −14→14
5954 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0532P)^2 + 0.1343P] where P = (Fo^2 + 2Fc^2)/3
2659 reflections	(Δ/σ)max = 0.002
155 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.21 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
C1	0.2635 (2)	1.3033 (2)	0.27180 (13)	0.0379 (3)
C2	0.1665 (3)	1.0264 (2)	0.18636 (14)	0.0439 (4)
C3	0.1029 (4)	0.8280 (3)	0.17603 (17)	0.0617 (5)
H3A	0.0629	0.7922	0.0953	0.093*
H3B	−0.0070	0.7840	0.2230	0.093*
H3C	0.2115	0.7789	0.2030	0.093*
C4	0.2745 (2)	1.1001 (2)	0.49268 (13)	0.0400 (4)
H4	0.3196	1.2248	0.4992	0.048*
C5	0.2738 (2)	0.9871 (2)	0.59672 (13)	0.0371 (3)
C6	0.3299 (3)	1.0685 (2)	0.70682 (14)	0.0487 (4)
H6	0.3678	1.1934	0.7142	0.058*
C7	0.3300 (3)	0.9654 (3)	0.80588 (15)	0.0539 (5)
H7	0.3652	1.0206	0.8798	0.065*
C8	0.2773 (3)	0.7799 (2)	0.79417 (15)	0.0476 (4)
C9	0.2227 (3)	0.6970 (2)	0.68453 (16)	0.0514 (4)
H9	0.1879	0.5721	0.6772	0.062*
C10	0.2200 (3)	0.8001 (2)	0.58632 (15)	0.0461 (4)
H10	0.1821	0.7445	0.5127	0.055*
C11	0.2800 (3)	0.6704 (3)	0.89609 (17)	0.0601 (5)
N1	0.21505 (19)	1.11995 (17)	0.29285 (10)	0.0362 (3)
N2	0.1847 (2)	1.1369 (2)	0.10000 (12)	0.0524 (4)
N3	0.2429 (2)	1.3038 (2)	0.15394 (12)	0.0485 (4)
H3D	0.2647	1.4017	0.1151	0.058*
N4	0.2117 (2)	1.02188 (17)	0.39419 (11)	0.0385 (3)
N5	0.2817 (3)	0.5822 (3)	0.97577 (16)	0.0811 (6)
S1	0.32744 (8)	1.48037 (6)	0.36283 (4)	0.05691 (18)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0412 (8)	0.0381 (8)	0.0336 (8)	0.0090 (6)	0.0012 (6)	0.0115 (6)
C2	0.0541 (10)	0.0461 (9)	0.0328 (8)	0.0162 (7)	−0.0013 (7)	0.0027 (6)
C3	0.0905 (15)	0.0456 (10)	0.0494 (11)	0.0217 (10)	−0.0072 (10)	−0.0044 (8)
C4	0.0457 (9)	0.0390 (8)	0.0350 (8)	0.0100 (7)	0.0031 (6)	0.0111 (6)
C5	0.0366 (8)	0.0433 (8)	0.0325 (7)	0.0115 (6)	0.0048 (6)	0.0131 (6)
C6	0.0612 (11)	0.0433 (9)	0.0377 (8)	0.0070 (8)	0.0003 (7)	0.0109 (7)
C7	0.0647 (11)	0.0623 (11)	0.0325 (8)	0.0130 (9)	0.0007 (7)	0.0134 (8)
C8	0.0463 (9)	0.0592 (11)	0.0412 (9)	0.0186 (8)	0.0096 (7)	0.0259 (8)
C9	0.0628 (11)	0.0426 (9)	0.0525 (10)	0.0180 (8)	0.0112 (8)	0.0191 (8)
C10	0.0576 (10)	0.0443 (9)	0.0382 (9)	0.0160 (8)	0.0048 (7)	0.0102 (7)
C11	0.0646 (12)	0.0709 (13)	0.0517 (11)	0.0264 (10)	0.0144 (9)	0.0305 (10)
N1	0.0438 (7)	0.0370 (7)	0.0279 (6)	0.0105 (5)	0.0016 (5)	0.0089 (5)
N2	0.0719 (10)	0.0542 (9)	0.0308 (7)	0.0172 (8)	−0.0013 (6)	0.0065 (6)
N3	0.0652 (9)	0.0451 (8)	0.0328 (7)	0.0103 (7)	0.0016 (6)	0.0154 (6)
N4	0.0465 (7)	0.0389 (7)	0.0312 (6)	0.0125 (6)	0.0041 (5)	0.0136 (5)
N5	0.1056 (16)	0.0881 (14)	0.0603 (11)	0.0394 (12)	0.0213 (10)	0.0456 (10)
S1	0.0794 (4)	0.0363 (2)	0.0488 (3)	0.0070 (2)	−0.0080 (2)	0.00552 (19)

Geometric parameters (Å, º)

C1—N3	1.3420 (19)	C6—C7	1.383 (2)
C1—N1	1.3887 (19)	C6—H6	0.9300
C1—S1	1.6546 (17)	C7—C8	1.382 (3)
C2—N2	1.296 (2)	C7—H7	0.9300
C2—N1	1.384 (2)	C8—C9	1.383 (3)
C2—C3	1.477 (2)	C8—C11	1.440 (2)
C3—H3A	0.9600	C9—C10	1.377 (2)
C3—H3B	0.9600	C9—H9	0.9300
C3—H3C	0.9600	C10—H10	0.9300
C4—N4	1.266 (2)	C11—N5	1.137 (2)
C4—C5	1.4735 (19)	N1—N4	1.3815 (16)
C4—H4	0.9300	N2—N3	1.371 (2)
C5—C6	1.384 (2)	N3—H3D	0.8600
C5—C10	1.391 (2)
N3—C1—N1	101.52 (13)	C8—C7—C6	119.51 (17)
N3—C1—S1	127.16 (12)	C8—C7—H7	120.2
N1—C1—S1	131.32 (11)	C6—C7—H7	120.2
N2—C2—N1	110.55 (15)	C7—C8—C9	120.50 (15)
N2—C2—C3	126.08 (16)	C7—C8—C11	120.31 (18)
N1—C2—C3	123.37 (15)	C9—C8—C11	119.20 (18)
C2—C3—H3A	109.5	C10—C9—C8	119.79 (17)
C2—C3—H3B	109.5	C10—C9—H9	120.1
H3A—C3—H3B	109.5	C8—C9—H9	120.1
C2—C3—H3C	109.5	C9—C10—C5	120.33 (16)
H3A—C3—H3C	109.5	C9—C10—H10	119.8
H3B—C3—H3C	109.5	C5—C10—H10	119.8
N4—C4—C5	117.83 (15)	N5—C11—C8	179.2 (2)
N4—C4—H4	121.1	N4—N1—C2	118.04 (13)
C5—C4—H4	121.1	N4—N1—C1	133.14 (13)
C6—C5—C10	119.33 (14)	C2—N1—C1	108.80 (13)
C6—C5—C4	119.41 (15)	C2—N2—N3	104.07 (13)
C10—C5—C4	121.26 (14)	C1—N3—N2	115.04 (13)
C7—C6—C5	120.52 (17)	C1—N3—H3D	122.5
C7—C6—H6	119.7	N2—N3—H3D	122.5
C5—C6—H6	119.7	C4—N4—N1	120.55 (13)
N4—C4—C5—C6	−176.05 (15)	C3—C2—N1—N4	2.8 (2)
N4—C4—C5—C10	4.7 (2)	N2—C2—N1—C1	1.31 (19)
C10—C5—C6—C7	−0.9 (3)	C3—C2—N1—C1	−178.55 (17)
C4—C5—C6—C7	179.80 (16)	N3—C1—N1—N4	177.34 (15)
C5—C6—C7—C8	1.3 (3)	S1—C1—N1—N4	−3.4 (3)
C6—C7—C8—C9	−0.7 (3)	N3—C1—N1—C2	−0.99 (17)
C6—C7—C8—C11	178.86 (17)	S1—C1—N1—C2	178.25 (13)
C7—C8—C9—C10	−0.3 (3)	N1—C2—N2—N3	−0.99 (19)
C11—C8—C9—C10	−179.81 (17)	C3—C2—N2—N3	178.87 (18)
C8—C9—C10—C5	0.6 (3)	N1—C1—N3—N2	0.42 (19)
C6—C5—C10—C9	−0.1 (3)	S1—C1—N3—N2	−178.87 (13)
C4—C5—C10—C9	179.22 (16)	C2—N2—N3—C1	0.3 (2)
C7—C8—C11—N5	−176 (100)	C5—C4—N4—N1	−177.73 (12)
C9—C8—C11—N5	4 (17)	C2—N1—N4—C4	172.61 (15)
N2—C2—N1—N4	−177.30 (14)	C1—N1—N4—C4	−5.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3D···N5^i	0.86	2.11	2.934 (2)	162

Symmetry code: (i) x, y+1, z−1.