1-(Aceton­yl)-3-(2-thienylmeth­yl)-4-(4H-1,2,4-triazol-4-yl)-1H-1,2,4-triazol-5(4H)-one

In the title compound, C₁₂H₁₂N₆O₂S, the thio­phene ring is disordered equally over two positions, corresponding to rotation of approximately 180° about the C—C single bond. The central triazole ring has substituents at the 1-, 3-, 4- and 5-positions. Inter­molecular C—H...N and C—H...O inter­actions help to stabilize the structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.047
• wR factor = 0.089
• Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.685     0.969
            Tmin(prime) and Tmax expected:      0.911     0.969
            RR(prime) =      0.751
            Please check that your absorption correction is appropriate.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.75
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C22
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for       C22'
PLAT301_ALERT_3_C Main Residue  Disorder .........................      19.00 Perc.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O41    ..  C5      ..       2.94 Ang.

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
   7 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

In a continuing search for pharmacologically active, 1,2,4-triazol and 1,2,4 triazol-5-one compounds it was found that most azole fungicides have been developed for diseases of cereal crops; examples include fluconazole (Ichikawa et al., 2001), ravuconazole (Ueda, 2003) and posaconazole (Kim et al., 2003). The properties of 1,2,4-triazole derivatives have broad-spectrum biological effects, such as insecticidal (Tsuda et al., 2004), herbicidal (Chai et al., 2003), anticonvulsant (Er-Rahimini & Mornet, 1992), antitumour (Nakip et al., 1994) and plant growth regulatory activities (Jenkins et al., 1989). Di- or tri-substituted 1,2,4-triazole derivatives have also been reported to show antituberculotic and antimicrobial activities (Demirbaş et al., 2004). Additionally, thermally stable polymers containing the 1, 2, 4-triazole moiety have been prepared (Shaikh et al., 2002).

The title compound (I)(Fig.1) consists of a triazole ring with an acetonyl group substituted at N4, a disordered (2,5-thienyl methyl) group substituted at C2, a 1,2,4-triazole ring substituted at N1 and an oxo O atom at C5. The N1—C5 bond length, 1.396 (3) Å, agrees with reported values [1.390 (3)Å in C₁₃H₁₃ClN₄O₂ (Çoruh, Kahveci, Şaşmaz, Aǧar, Kim & Erdönmez, 2003), 1.387 (3)Å in C₁₂H₁₁ClN₄O₂ (Çoruh, Kahveci, Şaşmaz, Aǧar & Kim, 2003)]. In the 1,2,4-triazole ring the N12—N13 bond length, 1.404 (4) Å, agrees with reported values [1.403 (8)Å in C₁₉H₁₈N₆O₂S (Sancak et al., 2005)].

The presence of a substituent on N4 causes a lengthening of the N—N bond length [N3—N4= 1.390 (3) Å] with respect to the corresponding bonds in 5-(2-chlorophenyl)-4-phenyl-3,4-dihydro-2H-1,2,4-triazole-3-thione [N—N= 1.374 (2) Å; Puviarasan et al., 1999] and in 4-methyl-1,2,4- triazole and 1-methyltetrazole [N—N= 1.344 (2) Å; Palmer & Parsons, 1996]. The S—C bond lengths [S21—C22= 1.681 (4)Å and S21—C25= 1.6807 Å] agree with values reported in the literature [S41—C44=1.676 (4)Å and S41—C41=1.689 (3)Å (Vrabel et al., 2005), C14—S1=1.692Å and C11—S1=1.708Å (Yılmaz et al., 2006)].

The thiophene ring is disordered over two positions, corresponding to rotation of approximately 180° about the single C21—C22 bond, with a major-minor ratio of about 50:50. Intermolecular hydrogen bonds are effective in stabilizing the crystal structure.

Related literature

For related literature, see: Chai et al. (2003); Demirbaş et al. (2004); Er-Rahimini & Mornet (1992); Ichikawa et al. (2001); Jenkins et al. (1989); Kim et al. (2003); Nakib et al. (1994); Palmer & Parsons (1996); Puviarason et al. (1999); Sancak et al. (2005); Shaikh et al. (2002); Sheldrick (1997a, 1997b); Tsuda et al. (2004); Ueda (2003); Vrábel et al. (2005); Yılmaz, Arslan, Kazak, Sancak & Er (2006); Çoruh, Kahveci, Şaşmaz, Aǧar & Kim (2003); Çoruh, Kahveci, Şaşmaz, Aǧar, Kim & Erdönmez (2003).

S2. Experimental

5-(Thien-2-ylmethyl)4, 4'-bi-1, 2, 4-triazol-3(2H)-one (0.001 mol) was refluxed with sodium metal (0.001 mol) in absolute ethanol (50 ml) for 1 h. Chloro acetone (0.001 mol) was added and the solution refluxed for 8 h. The resulting solution was filtered and then evaporated under reduced pressure. The solid residue was crystallized from absolute ethanol-diethylether (1:4). (Yield: 52%; m.p. 438–439 K).

S3. Refinement

H atoms were placed in idealized positions and were constrained using riding models at distances ranging between 0.93–0.97Å with isotropic displacement parameters derived from their carrier atoms (U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_Me).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. An ORTEP drawing of (I), with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

1-(Acetonyl)-3-(2-thienylmethyl)-4-(4H-1,2,4-triazol-4-yl)-1H- 1,2,4-triazol-5(4H)-one

Crystal data

C12H12N6O2S	F(000) = 632
Mr = 304.34	Dx = 1.446 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1214 reflections
a = 5.8357 (8) Å	θ = 2.5–25.3°
b = 32.084 (4) Å	µ = 0.25 mm^−1
c = 7.4958 (10) Å	T = 293 K
β = 95.087 (3)°	Irregular, colorless
V = 1397.9 (3) Å^3	0.37 × 0.30 × 0.13 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2412 independent reflections
Radiation source: fine-focus sealed tube	1214 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.086
φ and ω scans	θmax = 25.3°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −6→7
Tmin = 0.685, Tmax = 0.969	k = −38→38
6559 measured reflections	l = −8→5

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.089	w = 1/[σ^2(Fo^2) + (0.028P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.82	(Δ/σ)max < 0.001
2412 reflections	Δρmax = 0.17 e Å^−3
201 parameters	Δρmin = −0.17 e Å^−3
183 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0045 (8)

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	Occ. (<1)
C21	−0.1123 (5)	0.62882 (8)	0.4109 (4)	0.0508 (8)
H21A	−0.2652	0.6397	0.4233	0.061*
H21B	−0.1177	0.6134	0.2992	0.061*
C22	0.0521 (5)	0.66449 (9)	0.4029 (4)	0.0505 (7)	0.50
C23	0.238 (2)	0.6635 (5)	0.313 (2)	0.0758 (7)	0.50
H23	0.2751	0.6408	0.2430	0.091*	0.50
C24	0.379 (3)	0.7009 (3)	0.332 (2)	0.0774 (13)	0.50
H24	0.5122	0.7057	0.2763	0.093*	0.50
C25	0.2859 (7)	0.72750 (11)	0.4445 (5)	0.0764 (12)	0.50
H25	0.3509	0.7531	0.4787	0.092*	0.50
S21	0.0395 (7)	0.70954 (11)	0.5162 (5)	0.0742 (7)	0.50
C22'	0.0521 (5)	0.66449 (9)	0.4029 (4)	0.0505 (7)	0.50
C23'	0.021 (3)	0.7032 (4)	0.4704 (18)	0.0742 (7)	0.50
H23'	−0.1058	0.7117	0.5278	0.089*	0.50
C24'	0.2230 (14)	0.7298 (3)	0.4377 (10)	0.0764 (12)	0.50
H24'	0.2445	0.7570	0.4781	0.092*	0.50
C25'	0.366 (3)	0.7094 (3)	0.344 (2)	0.0774 (13)	0.50
H25'	0.5009	0.7210	0.3092	0.093*	0.50
S21'	0.2842 (6)	0.66048 (14)	0.2919 (6)	0.0758 (7)	0.50
N1	−0.0889 (3)	0.60701 (6)	0.7383 (3)	0.0403 (6)
C2	−0.0471 (4)	0.59995 (8)	0.5620 (4)	0.0399 (7)
N3	0.0634 (4)	0.56527 (7)	0.5507 (3)	0.0457 (6)
N4	0.0926 (3)	0.54966 (6)	0.7243 (3)	0.0419 (6)
C5	−0.0098 (4)	0.57328 (8)	0.8443 (4)	0.0421 (7)
O51	−0.0271 (3)	0.56817 (5)	1.0029 (3)	0.0559 (6)
N11	−0.2326 (4)	0.63674 (6)	0.7998 (3)	0.0439 (6)
O41	0.5537 (3)	0.53282 (6)	0.7185 (3)	0.0744 (7)
C41	0.1784 (4)	0.50814 (7)	0.7550 (4)	0.0456 (7)
H41A	0.0980	0.4897	0.6682	0.055*
H41B	0.1426	0.4993	0.8730	0.055*
C42	0.4318 (5)	0.50339 (9)	0.7430 (3)	0.0440 (7)
C43	0.5203 (5)	0.45964 (8)	0.7612 (4)	0.0584 (8)
H43A	0.6821	0.4601	0.7981	0.088*
H43B	0.4949	0.4456	0.6481	0.088*
H43C	0.4407	0.4451	0.8492	0.088*
N12	−0.3510 (6)	0.68921 (9)	0.9474 (4)	0.0846 (9)
N13	−0.5427 (5)	0.66589 (10)	0.8810 (4)	0.0817 (9)
C12	−0.4651 (5)	0.63472 (10)	0.7955 (4)	0.0630 (9)
H12	−0.5556	0.6139	0.7391	0.076*
C11	−0.1712 (6)	0.67082 (9)	0.8970 (4)	0.0649 (9)
H11	−0.0206	0.6798	0.9241	0.078*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C21	0.0548 (19)	0.0479 (18)	0.049 (2)	0.0007 (15)	0.0017 (16)	0.0037 (15)
C22	0.0550 (17)	0.0433 (15)	0.0531 (18)	0.0029 (13)	0.0045 (15)	0.0094 (14)
C23	0.0557 (16)	0.0810 (11)	0.0934 (14)	0.0008 (12)	0.0219 (11)	0.0207 (10)
C24	0.066 (2)	0.074 (3)	0.092 (3)	−0.010 (2)	0.0082 (18)	0.024 (2)
C25	0.085 (3)	0.059 (2)	0.085 (2)	−0.016 (2)	0.002 (2)	0.0139 (18)
S21	0.0963 (14)	0.0515 (13)	0.078 (2)	−0.0098 (11)	0.0229 (14)	−0.0079 (11)
C22'	0.0550 (17)	0.0433 (15)	0.0531 (18)	0.0029 (13)	0.0045 (15)	0.0094 (14)
C23'	0.0963 (14)	0.0515 (13)	0.078 (2)	−0.0098 (11)	0.0229 (14)	−0.0079 (11)
C24'	0.085 (3)	0.059 (2)	0.085 (2)	−0.016 (2)	0.002 (2)	0.0139 (18)
C25'	0.066 (2)	0.074 (3)	0.092 (3)	−0.010 (2)	0.0082 (18)	0.024 (2)
S21'	0.0557 (16)	0.0810 (11)	0.0934 (14)	0.0008 (12)	0.0219 (11)	0.0207 (10)
N1	0.0394 (14)	0.0349 (13)	0.0476 (16)	0.0072 (11)	0.0093 (12)	0.0006 (12)
C2	0.0347 (17)	0.0408 (18)	0.0445 (19)	−0.0041 (14)	0.0048 (14)	−0.0011 (15)
N3	0.0496 (16)	0.0409 (14)	0.0481 (16)	0.0039 (11)	0.0119 (12)	0.0005 (12)
N4	0.0441 (15)	0.0343 (13)	0.0481 (16)	0.0058 (11)	0.0087 (12)	0.0043 (12)
C5	0.0342 (18)	0.0373 (17)	0.055 (2)	−0.0024 (13)	0.0060 (16)	0.0045 (17)
O51	0.0665 (15)	0.0568 (13)	0.0458 (13)	0.0074 (10)	0.0124 (11)	0.0097 (11)
N11	0.0423 (15)	0.0369 (13)	0.0535 (16)	0.0049 (12)	0.0103 (12)	−0.0045 (12)
O41	0.0484 (14)	0.0548 (13)	0.121 (2)	−0.0130 (11)	0.0126 (13)	−0.0001 (13)
C41	0.0428 (18)	0.0358 (16)	0.059 (2)	0.0027 (13)	0.0107 (15)	0.0047 (14)
C42	0.0396 (17)	0.0449 (18)	0.0478 (19)	0.0000 (15)	0.0052 (15)	−0.0050 (15)
C43	0.0533 (19)	0.0534 (18)	0.069 (2)	0.0144 (15)	0.0101 (16)	0.0003 (16)
N12	0.093 (3)	0.075 (2)	0.088 (2)	0.0220 (19)	0.018 (2)	−0.0249 (17)
N13	0.072 (2)	0.086 (2)	0.092 (2)	0.0272 (19)	0.0309 (19)	−0.0095 (18)
C12	0.047 (2)	0.065 (2)	0.078 (3)	0.0035 (17)	0.0101 (18)	−0.0026 (19)
C11	0.067 (2)	0.055 (2)	0.074 (2)	0.0001 (18)	0.0108 (19)	−0.0189 (19)

Geometric parameters (Å, º)

C21—C2	1.487 (3)	C2—N3	1.292 (3)
C21—C22	1.498 (3)	N3—N4	1.390 (3)
C21—H21A	0.9700	N4—C5	1.355 (3)
C21—H21B	0.9700	N4—C41	1.434 (3)
C22—C23	1.330 (13)	C5—O51	1.213 (3)
C22—S21	1.681 (4)	N11—C11	1.345 (3)
C23—C24	1.456 (17)	N11—C12	1.356 (3)
C23—H23	0.9300	O41—C42	1.206 (3)
C24—C25	1.345 (10)	C41—C42	1.497 (3)
C24—H24	0.9300	C41—H41A	0.9700
C25—S21	1.6807	C41—H41B	0.9700
C25—H25	0.9300	C42—C43	1.498 (3)
C23'—C24'	1.493 (13)	C43—H43A	0.9600
C23'—H23'	0.9300	C43—H43B	0.9600
C24'—C25'	1.313 (10)	C43—H43C	0.9600
C24'—H24'	0.9300	N12—C11	1.289 (3)
C25'—S21'	1.675 (11)	N12—N13	1.400 (4)
C25'—H25'	0.9300	N13—C12	1.291 (3)
N1—N11	1.376 (3)	C12—H12	0.9300
N1—C2	1.383 (3)	C11—H11	0.9300
N1—C5	1.396 (3)
C2—C21—C22	112.6 (2)	C5—N4—N3	113.2 (2)
C2—C21—H21A	109.1	C5—N4—C41	125.5 (2)
C22—C21—H21A	109.1	N3—N4—C41	119.8 (2)
C2—C21—H21B	109.1	O51—C5—N4	130.9 (3)
C22—C21—H21B	109.1	O51—C5—N1	127.6 (3)
H21A—C21—H21B	107.8	N4—C5—N1	101.5 (2)
C23—C22—C21	123.8 (8)	C11—N11—C12	105.7 (3)
C23—C22—S21	110.7 (8)	C11—N11—N1	127.1 (3)
C21—C22—S21	125.4 (2)	C12—N11—N1	126.7 (2)
C22—C23—C24	113.9 (13)	N4—C41—C42	114.7 (2)
C22—C23—H23	123.0	N4—C41—H41A	108.6
C24—C23—H23	123.0	C42—C41—H41A	108.6
C25—C24—C23	109.4 (11)	N4—C41—H41B	108.6
C25—C24—H24	125.3	C42—C41—H41B	108.6
C23—C24—H24	125.3	H41A—C41—H41B	107.6
C24—C25—S21	112.7 (6)	O41—C42—C41	121.9 (2)
C24—C25—H25	123.6	O41—C42—C43	123.0 (3)
S21—C25—H25	123.6	C41—C42—C43	115.1 (2)
C25—S21—C22	93.23 (16)	C42—C43—H43A	109.5
C24'—C23'—H23'	125.4	C42—C43—H43B	109.5
C25'—C24'—C23'	110.5 (9)	H43A—C43—H43B	109.5
C25'—C24'—H24'	124.8	C42—C43—H43C	109.5
C23'—C24'—H24'	124.8	H43A—C43—H43C	109.5
C24'—C25'—S21'	114.3 (11)	H43B—C43—H43C	109.5
C24'—C25'—H25'	122.9	C11—N12—N13	107.3 (3)
S21'—C25'—H25'	122.9	C12—N13—N12	106.6 (3)
N11—N1—C2	126.7 (2)	N13—C12—N11	110.2 (3)
N11—N1—C5	121.8 (2)	N13—C12—H12	124.9
C2—N1—C5	109.8 (2)	N11—C12—H12	124.9
N3—C2—N1	109.6 (2)	N12—C11—N11	110.2 (3)
N3—C2—C21	125.6 (3)	N12—C11—H11	124.9
N1—C2—C21	124.8 (2)	N11—C11—H11	124.9
C2—N3—N4	105.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C24^'—H25···N12^i	1.08	2.57	3.593 (9)	158
C25—H25···N12^i	0.93	2.57	3.409 (5)	151
C41—H41A···N3^ii	0.97	2.53	3.495 (3)	172
C41—H41B···O51^iii	0.97	2.47	3.217 (3)	134
C43—H43A···O51^iv	0.96	2.56	3.426 (3)	150

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