1-(4-Phenyl-3-thioxo-1,2,4-triazolidin-1-yl)-2-(1H-1,2,4-triazol-1-yl)ethanone

In the title compound, C₁₂H₁₂N₆OS, the dihedral angles made by the plane of the thione-substituted triazolidine ring with the planes of the triazole ring and the benzene ring are 87.77 (2) and 52.07 (3)°, respectively. In the crystal structure, weak inter­molecular N—H...N, C—H...N and C—H...O hydrogen bonds stabilize the packing.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.045
• wR factor = 0.116
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C7
PLAT432_ALERT_2_C Short Inter X...Y Contact  O1     ..  C11     ..       2.98 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

Research findings indicate that the 1,2,4-triazole ring is associated with diverse pharmacological activities, such as analgesic, anti-asthmatic, diuretic, antifungal, antibacterial, pesticidal and anti-inflammatory activities (Bennur et al., 1976; Heubach et al., 1980; Sharma & Babel, 1982; Mohamed et al., 1993). In view of this, the crystal structure determination of the title compound, (I), has been carried out in order to elucidate the stereochemistry and the molecular conformation.

Bond lengths and angles of the the triazole ring (Table 1) are in agreement with the values in our previous report of a similar structure (Xu et al., 2005). The C═S distance is essentially the same as the mean value of 1.660 Å reported by Allen et al. (1987). The dihedral angles made by the plane of the thione-substituted triazolidine ring (C1/C2/N1–N3/S1) with the planes of the triazole ring (C11/C12/N4–N6) and the benzene ring (C3–C8) are 87.77 (2) and 52.07 (3)°, respectively. In the crystal structure weak C—H···O, C—H···N and N—H···N intermolecular hydrogen-bond interactions stabilize the packing (Table 2).

S2. Experimental

A mixture of 5-[(1H-1,2,4-triazol-1-yl)methyl]-1,3,4-oxadiazole-2-thiol (0.02 mol), aniline (0.02 mol) and formaldehyde (0.02 mol) was stirred in ethanol (30 ml) for 15 h at 278 K to afford the title compound (2.62 g, yield 91%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

S3. Refinement

All H atoms were placed in calculated positions. H atoms bonded to C atoms were constrained to ride on their parent atom (C—H=0.93–0.97 Å), with U_iso values of 1.2U_eq(C). The position and isotropic displacement parameter of the N-bound H atom were refined freely.

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 drawn at the 40% probability level.
	Fig. 2. A packing diagram of the molecule of the title compound, viewed along the a axis. Weak hydrogen bonds are shown as dashed lines.

1-(4-phenyl-3-thioxo-1,2,4-triazolidin-1-yl)-2-(1H-1,2,4-triazol-1-yl)ethanone

Crystal data

C12H12N6OS	F(000) = 600
Mr = 288.34	Dx = 1.420 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb c	Cell parameters from 1493 reflections
a = 9.7112 (19) Å	θ = 2.5–22.4°
b = 13.589 (3) Å	µ = 0.25 mm^−1
c = 10.711 (2) Å	T = 294 K
β = 107.362 (4)°	Block, yellow
V = 1349.0 (5) Å^3	0.22 × 0.18 × 0.14 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2748 independent reflections
Radiation source: fine-focus sealed tube	1557 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
ϕ and ω scans	θmax = 26.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→10
Tmin = 0.942, Tmax = 0.966	k = −16→16
7473 measured reflections	l = −6→13

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.052P)^2] where P = (Fo^2 + 2Fc^2)/3
2748 reflections	(Δ/σ)max < 0.001
185 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.19 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	0.48455 (8)	0.68174 (5)	0.45003 (8)	0.0515 (3)
N1	0.7120 (2)	0.56074 (15)	0.5107 (2)	0.0385 (5)
N2	0.7714 (2)	0.48294 (13)	0.45398 (19)	0.0373 (5)
N3	0.5567 (2)	0.52994 (13)	0.3165 (2)	0.0369 (5)
N4	1.0114 (2)	0.35454 (14)	0.7346 (2)	0.0401 (5)
N5	1.1473 (2)	0.35944 (16)	0.7252 (3)	0.0594 (7)
N6	1.1158 (3)	0.21997 (15)	0.8267 (3)	0.0590 (7)
O1	0.8705 (2)	0.33348 (13)	0.47776 (19)	0.0574 (6)
C1	0.5844 (3)	0.58960 (16)	0.4231 (3)	0.0363 (6)
C2	0.6739 (3)	0.46062 (17)	0.3252 (3)	0.0409 (6)
H2A	0.6404	0.3931	0.3199	0.049*
H2B	0.7191	0.4724	0.2572	0.049*
C3	0.4306 (3)	0.52904 (17)	0.2071 (2)	0.0376 (6)
C4	0.3803 (3)	0.6128 (2)	0.1361 (3)	0.0542 (8)
H4	0.4289	0.6721	0.1596	0.065*
C5	0.2584 (3)	0.6090 (2)	0.0305 (3)	0.0638 (9)
H5	0.2251	0.6659	−0.0172	0.077*
C6	0.1857 (3)	0.5229 (3)	−0.0051 (3)	0.0707 (10)
H6	0.1025	0.5211	−0.0760	0.085*
C7	0.2361 (4)	0.4389 (2)	0.0644 (4)	0.0838 (11)
H7	0.1872	0.3798	0.0399	0.101*
C8	0.3591 (3)	0.4414 (2)	0.1705 (3)	0.0635 (9)
H8	0.3933	0.3842	0.2170	0.076*
C9	0.8478 (3)	0.40966 (18)	0.5286 (3)	0.0381 (6)
C10	0.9068 (3)	0.42941 (17)	0.6733 (2)	0.0426 (7)
H10A	0.9522	0.4937	0.6874	0.051*
H10B	0.8286	0.4293	0.7123	0.051*
C11	0.9964 (3)	0.27200 (18)	0.7938 (3)	0.0497 (7)
H11	0.9115	0.2529	0.8103	0.060*
C12	1.2040 (3)	0.2771 (2)	0.7814 (3)	0.0657 (9)
H12	1.2987	0.2592	0.7895	0.079*
H1	0.770 (3)	0.606 (2)	0.541 (3)	0.065 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0518 (4)	0.0422 (4)	0.0562 (5)	0.0099 (3)	0.0097 (4)	−0.0101 (3)
N1	0.0431 (13)	0.0272 (11)	0.0400 (14)	0.0018 (10)	0.0043 (11)	−0.0065 (10)
N2	0.0438 (12)	0.0308 (10)	0.0352 (13)	0.0028 (10)	0.0084 (11)	−0.0040 (10)
N3	0.0396 (12)	0.0308 (11)	0.0376 (13)	0.0006 (9)	0.0074 (11)	−0.0023 (9)
N4	0.0385 (12)	0.0389 (12)	0.0440 (14)	0.0073 (10)	0.0139 (11)	0.0102 (10)
N5	0.0422 (14)	0.0572 (15)	0.081 (2)	0.0061 (12)	0.0212 (14)	0.0225 (14)
N6	0.0613 (16)	0.0441 (13)	0.073 (2)	0.0152 (13)	0.0215 (15)	0.0210 (13)
O1	0.0702 (13)	0.0474 (11)	0.0511 (13)	0.0222 (10)	0.0128 (11)	−0.0107 (9)
C1	0.0396 (15)	0.0296 (13)	0.0394 (16)	−0.0052 (11)	0.0112 (13)	0.0007 (12)
C2	0.0429 (15)	0.0387 (14)	0.0395 (17)	0.0030 (12)	0.0096 (13)	−0.0046 (12)
C3	0.0412 (15)	0.0397 (14)	0.0305 (15)	−0.0011 (12)	0.0085 (12)	−0.0016 (12)
C4	0.0613 (18)	0.0448 (16)	0.0475 (19)	−0.0024 (14)	0.0025 (16)	0.0034 (14)
C5	0.073 (2)	0.0617 (19)	0.047 (2)	0.0127 (18)	0.0030 (18)	0.0093 (16)
C6	0.063 (2)	0.086 (2)	0.046 (2)	0.010 (2)	−0.0091 (17)	−0.0065 (19)
C7	0.083 (2)	0.070 (2)	0.072 (3)	−0.021 (2)	−0.018 (2)	−0.017 (2)
C8	0.070 (2)	0.0433 (16)	0.059 (2)	−0.0058 (15)	−0.0082 (17)	−0.0030 (15)
C9	0.0359 (14)	0.0357 (14)	0.0431 (17)	0.0040 (11)	0.0122 (13)	0.0023 (12)
C10	0.0433 (16)	0.0393 (14)	0.0423 (17)	0.0108 (12)	0.0082 (14)	0.0023 (12)
C11	0.0516 (17)	0.0445 (15)	0.057 (2)	−0.0002 (14)	0.0227 (16)	0.0141 (14)
C12	0.0515 (19)	0.0639 (19)	0.084 (3)	0.0226 (16)	0.0239 (19)	0.0246 (18)

Geometric parameters (Å, º)

S1—C1	1.661 (2)	C2—H2B	0.9700
N1—C1	1.369 (3)	C3—C4	1.375 (3)
N1—N2	1.425 (3)	C3—C8	1.375 (3)
N1—H1	0.83 (3)	C4—C5	1.372 (4)
N2—C9	1.352 (3)	C4—H4	0.9300
N2—C2	1.453 (3)	C5—C6	1.361 (4)
N3—C1	1.360 (3)	C5—H5	0.9300
N3—C3	1.420 (3)	C6—C7	1.371 (4)
N3—C2	1.459 (3)	C6—H6	0.9300
N4—C11	1.318 (3)	C7—C8	1.382 (4)
N4—N5	1.355 (3)	C7—H7	0.9300
N4—C10	1.449 (3)	C8—H8	0.9300
N5—C12	1.312 (3)	C9—C10	1.507 (3)
N6—C11	1.313 (3)	C10—H10A	0.9700
N6—C12	1.349 (3)	C10—H10B	0.9700
O1—C9	1.220 (3)	C11—H11	0.9300
C2—H2A	0.9700	C12—H12	0.9300
C1—N1—N2	108.6 (2)	C3—C4—H4	119.9
C1—N1—H1	115.0 (19)	C6—C5—C4	120.7 (3)
N2—N1—H1	114 (2)	C6—C5—H5	119.7
C9—N2—N1	121.0 (2)	C4—C5—H5	119.7
C9—N2—C2	119.65 (19)	C5—C6—C7	119.5 (3)
N1—N2—C2	109.12 (18)	C5—C6—H6	120.2
C1—N3—C3	127.2 (2)	C7—C6—H6	120.2
C1—N3—C2	112.1 (2)	C6—C7—C8	120.4 (3)
C3—N3—C2	120.74 (19)	C6—C7—H7	119.8
C11—N4—N5	109.1 (2)	C8—C7—H7	119.8
C11—N4—C10	130.7 (2)	C3—C8—C7	119.7 (3)
N5—N4—C10	119.9 (2)	C3—C8—H8	120.2
C12—N5—N4	102.1 (2)	C7—C8—H8	120.2
C11—N6—C12	101.5 (2)	O1—C9—N2	120.1 (2)
N3—C1—N1	108.5 (2)	O1—C9—C10	123.1 (2)
N3—C1—S1	128.0 (2)	N2—C9—C10	116.7 (2)
N1—C1—S1	123.55 (19)	N4—C10—C9	109.9 (2)
N2—C2—N3	101.59 (18)	N4—C10—H10A	109.7
N2—C2—H2A	111.5	C9—C10—H10A	109.7
N3—C2—H2A	111.5	N4—C10—H10B	109.7
N2—C2—H2B	111.5	C9—C10—H10B	109.7
N3—C2—H2B	111.5	H10A—C10—H10B	108.2
H2A—C2—H2B	109.3	N6—C11—N4	111.8 (2)
C4—C3—C8	119.6 (3)	N6—C11—H11	124.1
C4—C3—N3	121.7 (2)	N4—C11—H11	124.1
C8—C3—N3	118.7 (2)	N5—C12—N6	115.5 (2)
C5—C4—C3	120.1 (3)	N5—C12—H12	122.2
C5—C4—H4	119.9	N6—C12—H12	122.2
C1—N1—N2—C9	−146.4 (2)	C3—C4—C5—C6	0.2 (5)
C1—N1—N2—C2	−1.4 (3)	C4—C5—C6—C7	−0.9 (5)
C11—N4—N5—C12	−0.1 (3)	C5—C6—C7—C8	0.5 (6)
C10—N4—N5—C12	−174.9 (2)	C4—C3—C8—C7	−1.2 (5)
C3—N3—C1—N1	174.7 (2)	N3—C3—C8—C7	180.0 (3)
C2—N3—C1—N1	−4.1 (3)	C6—C7—C8—C3	0.5 (6)
C3—N3—C1—S1	−4.4 (4)	N1—N2—C9—O1	163.8 (2)
C2—N3—C1—S1	176.81 (18)	C2—N2—C9—O1	22.4 (3)
N2—N1—C1—N3	3.3 (3)	N1—N2—C9—C10	−18.8 (3)
N2—N1—C1—S1	−177.53 (16)	C2—N2—C9—C10	−160.3 (2)
C9—N2—C2—N3	144.6 (2)	C11—N4—C10—C9	−94.7 (3)
N1—N2—C2—N3	−0.9 (2)	N5—N4—C10—C9	78.9 (3)
C1—N3—C2—N2	3.1 (2)	O1—C9—C10—N4	10.1 (3)
C3—N3—C2—N2	−175.8 (2)	N2—C9—C10—N4	−167.2 (2)
C1—N3—C3—C4	54.0 (4)	C12—N6—C11—N4	−0.6 (3)
C2—N3—C3—C4	−127.3 (3)	N5—N4—C11—N6	0.5 (3)
C1—N3—C3—C8	−127.1 (3)	C10—N4—C11—N6	174.5 (3)
C2—N3—C3—C8	51.6 (3)	N4—N5—C12—N6	−0.3 (4)
C8—C3—C4—C5	0.9 (4)	C11—N6—C12—N5	0.6 (4)
N3—C3—C4—C5	179.7 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N6^i	0.83 (3)	2.16 (3)	2.962 (3)	160 (3)
C2—H2B···N5^ii	0.97	2.61	3.138 (3)	115
C5—H5···O1^iii	0.93	2.54	3.288 (4)	138
C11—H11···O1^iv	0.93	2.28	2.978 (3)	132

Symmetry codes: (i) −x+2, y+1/2, −z+3/2; (ii) −x+2, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+1/2, z+1/2.