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The mol­ecules of the title compound, C12H11ClN4O2, are arranged as layers, stacking approximately along the b axis through C—H...O intermolecular hydrogen bonds. Some of these hydrogen-bond interactions which link two centrosymetric­ally related mol­ecules generate π–π-stacking interactions between triazole rings.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005129/dn6057sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005129/dn6057Isup2.hkl
Contains datablock I

CCDC reference: 209975

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.041
  • wR factor = 0.121
  • Data-to-parameter ratio = 14.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The 1,2,4-triazole ring systems are typically planar 6p-electron partially aromatic systems. They possess an extensive chemistry (Temple, 1981; Benson, 1967). 1,2,4-Triazole and its derivatives are starting materials for the synthesis of many heterocycles (Desenko, 1995). In addition to its extensive chemical significance, the 1,2,4-triazole nucleus is also found to be associated with diverse pharmacological properties, such as analgesic, anti-asthmatic, diuretic, anti-inflammantory, fungicidal, bactericidal and pesticidal activities (Mohamed et al., 1993; Sharma & Bahel, 1982; Heubach et al., 1980; Bennur et al., 1976; Webb & Parsons, 1977). Knowledge of the molecular structure of these compounds is important for understanding their reactivity under condensation reaction conditions. Therefore, the crystal structure analysis of the title compound, (I), has been carried out.

The structure of (I) (Fig. 1) consist of one 1,2,4-triazole ring (ring A: N2/C8/N3/N4/C11) with an acetyl group substituted at N3, and a methyl group and O atom substituted at C11 and C8, respectively. It also has a benzene ring (ring B: C1–C6). NC bond lengths [N4C11 = 1.278 (3) Å and N1C7 = 1.269 (3) Å] agree with literature values (Puviarasan et al., 1999; Liu et al., 1999). The triazole ring is planar and the maximum deviation observed is −0.0026 (3) Å for atom C11. Atom O1 is also located in the plane. The bond lengths and angles in the acetyl group are comparable with reported values (Singh & Izydore, 1996). The dihedral angle between rings A and B is 7.29 (1)°. indicating that the whole molecule is nearly planar.

Atom H12B of the methyl group (C12) forms an intermolecular hydrogen bond with the acetyl group O atom (O2) of a symetry-related molecule [C12···O2ii = 3.41 Å; symmetry code: (ii) 1 − x, −y, 2 − z]. Atom H10C of the cordinated acetyl group C10 is also involved in intermolecular hydrogen bonding with atom O1 [C10···O1iii = 3.500 (1) Å; symmetry code: (iii) x − 1, y, z]. Furthermore, the sum of the van der Waals radii of H and O [1.20 + 1.52 = 2.72 Å; calculated using PLATON (Spek, 2000)] is somewhat longer than the distances found for C7—H7···O1 [2.34 (1) Å] and C2—H2···O2i (2.52 Å), with C—H···O angles of 123.7 (11) and 126°, respectively. Therefore, these contacts might be considered as weak interactions.

The crystal structure is stabilized not only by intermolecular hydrogen-bond interactions but also by ππ-stacking interactions occurring between the 1,2,4-triazole rings which are in hydrogen-bond interactions through an inversion center. The distance between the centroids of these rings is 3.4570 (8) Å.

Experimental top

3-Methyl-4-(p-chlorobenzylideneamino)-4,5-dihydro-1H-1,2,4-triazol-5-one (0.01 mol) was treated with 10 ml of acetic anhydride and the mixture was refluxed for 30 min. After addition of 30 ml of absolute ethanol to the solution, the mixture was refluxed for one hour. The formed product was filtered and dried in vacuo. Several recrystallizations of this product from ethanol gave the pure compound. Yield: 82%, m.p: 454–455 K. IR data (KBr/cm−1): νC=O: 1769, 1697; νC=N: 1623, 1593; νbenzoid ring: 820. 1H NMR (δ/p.p.m. in DMSO-d6): 2.40 (s, 3H), 2.50 (s, acetyl 3H), 7.36 (d, 2H, Ar—H), 7.60 (d, 2H, Ar—H), 9.36 (s, CH). 13C NMR (in DMSO-d6): 166.24 (acetyl CO), 155.79 (NCH), 151.18 (triazole CO), 148.14, 133.68, 132.95, 132.13 (2 C), 131.80 (2 C), 23.61, 12.18.

Refinement top

The H atoms were positioned geometrically and refined using a riding model, fixing the aromatic C—H distance at 0.93 Å and the methyl C—H distance at 0.96 Å, with Uiso(H) = 1.2Ueq(C) or 1.5eq(C) for the methyl group.

Computing details top

Data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: CAD-4-PC Software; data reduction: XCAD4 (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL7 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of (I) and its centrosymetrically related molecule with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The hydrogen-bonding network observed in (I), viewed approximately along the [100] axis of the triclinic cell.
1-Acetyl-3-methyl-4-(P-chlorobenzylidenamino)-4,5-dihydro- 1H-1,2,4-triazol-5-one top
Crystal data top
C12H11ClN4O2Z = 2
Mr = 278.70F(000) = 288
Triclinic, P1Dx = 1.456 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.910 (3) ÅCell parameters from 25 reflections
b = 7.5682 (10) Åθ = 8.2–13.4°
c = 12.380 (3) ŵ = 0.30 mm1
α = 93.13 (2)°T = 293 K
β = 98.20 (2)°Needle, colorless
γ = 95.86 (2)°0.25 × 0.15 × 0.1 mm
V = 635.9 (3) Å3
Data collection top
Enraf-Nonius CAD-4 MACH3
diffractometer
Rint = 0.015
Radiation source: fine-focus sealed tubeθmax = 26.0°, θmin = 2.7°
Graphite monochromatorh = 08
ω–2θ scansk = 99
2723 measured reflectionsl = 1515
2503 independent reflections3 standard reflections every 60 min
1527 reflections with I > 2σ(I) intensity decay: 0.1%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0593P)2 + 0.0855P]
where P = (Fo2 + 2Fc2)/3
2503 reflections(Δ/σ)max = 0.004
174 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C12H11ClN4O2γ = 95.86 (2)°
Mr = 278.70V = 635.9 (3) Å3
Triclinic, P1Z = 2
a = 6.910 (3) ÅMo Kα radiation
b = 7.5682 (10) ŵ = 0.30 mm1
c = 12.380 (3) ÅT = 293 K
α = 93.13 (2)°0.25 × 0.15 × 0.1 mm
β = 98.20 (2)°
Data collection top
Enraf-Nonius CAD-4 MACH3
diffractometer
Rint = 0.015
2723 measured reflections3 standard reflections every 60 min
2503 independent reflections intensity decay: 0.1%
1527 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 1.02Δρmax = 0.19 e Å3
2503 reflectionsΔρmin = 0.24 e Å3
174 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Cl11.30518 (13)0.31259 (12)0.43443 (6)0.0939 (3)
C11.1650 (4)0.3165 (3)0.53956 (19)0.0599 (6)
C21.2396 (4)0.4034 (3)0.63867 (19)0.0586 (6)
H21.36530.46460.64980.070*
C31.1281 (3)0.3998 (3)0.72144 (18)0.0520 (6)
H31.17870.45940.78880.062*
C40.9406 (3)0.3085 (3)0.70658 (18)0.0483 (5)
C50.8667 (4)0.2255 (3)0.6043 (2)0.0653 (7)
H50.74000.16620.59200.078*
C60.9769 (4)0.2298 (4)0.5216 (2)0.0703 (8)
H60.92540.17440.45320.084*
C70.8276 (3)0.2997 (3)0.79634 (18)0.0503 (6)
H70.87380.36440.86270.060*
N10.6640 (3)0.2020 (2)0.78283 (15)0.0507 (5)
N20.5517 (3)0.1937 (2)0.86630 (14)0.0474 (5)
C80.5795 (3)0.2824 (3)0.96927 (17)0.0452 (5)
O10.7185 (2)0.3842 (2)1.01258 (12)0.0548 (4)
N30.4083 (3)0.2233 (2)1.00901 (14)0.0461 (4)
N40.2821 (3)0.1039 (2)0.93391 (15)0.0511 (5)
C90.3485 (3)0.2796 (3)1.10770 (18)0.0488 (5)
O20.4589 (2)0.3780 (2)1.17304 (14)0.0636 (5)
C100.1472 (4)0.2092 (3)1.1229 (2)0.0641 (7)
H10A0.12730.24001.19650.096*
H10B0.13070.08201.10970.096*
H10C0.05310.25991.07250.096*
C110.3725 (3)0.0897 (3)0.85118 (19)0.0475 (5)
C120.2981 (4)0.0240 (3)0.7496 (2)0.0619 (7)
H12A0.16200.06570.74900.093*
H12B0.37270.12400.74670.093*
H12C0.31150.04390.68730.093*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0981 (6)0.1181 (7)0.0628 (5)0.0192 (5)0.0326 (4)0.0141 (4)
C10.0640 (17)0.0648 (15)0.0493 (14)0.0035 (13)0.0119 (12)0.0008 (11)
C20.0539 (15)0.0656 (15)0.0510 (14)0.0108 (12)0.0060 (12)0.0043 (11)
C30.0528 (14)0.0520 (13)0.0454 (12)0.0058 (11)0.0007 (11)0.0058 (10)
C40.0473 (13)0.0479 (12)0.0466 (12)0.0014 (10)0.0014 (10)0.0035 (10)
C50.0515 (15)0.0809 (18)0.0556 (15)0.0116 (13)0.0017 (12)0.0141 (13)
C60.0697 (18)0.0851 (18)0.0472 (14)0.0096 (15)0.0011 (13)0.0150 (13)
C70.0474 (13)0.0503 (12)0.0493 (13)0.0015 (11)0.0001 (11)0.0049 (10)
N10.0453 (11)0.0538 (11)0.0504 (11)0.0013 (9)0.0041 (9)0.0037 (9)
N20.0422 (10)0.0468 (10)0.0492 (10)0.0028 (8)0.0020 (9)0.0048 (8)
C80.0413 (12)0.0438 (11)0.0468 (12)0.0010 (10)0.0020 (10)0.0010 (10)
O10.0427 (9)0.0611 (9)0.0529 (9)0.0113 (7)0.0020 (7)0.0092 (7)
N30.0376 (10)0.0469 (10)0.0486 (10)0.0049 (8)0.0014 (8)0.0043 (8)
N40.0428 (10)0.0493 (10)0.0550 (11)0.0073 (9)0.0015 (9)0.0053 (9)
C90.0425 (12)0.0526 (12)0.0486 (13)0.0005 (10)0.0008 (10)0.0037 (11)
O20.0515 (10)0.0793 (11)0.0530 (9)0.0066 (9)0.0004 (8)0.0120 (8)
C100.0482 (14)0.0764 (16)0.0654 (16)0.0052 (12)0.0117 (12)0.0030 (13)
C110.0408 (12)0.0430 (11)0.0533 (13)0.0024 (10)0.0040 (10)0.0022 (10)
C120.0555 (15)0.0582 (14)0.0635 (15)0.0084 (12)0.0023 (12)0.0154 (12)
Geometric parameters (Å, º) top
Cl1—C11.730 (3)N2—C81.387 (3)
C1—C21.366 (3)C8—O11.209 (2)
C1—C61.377 (4)C8—N31.387 (3)
C2—C31.367 (3)N3—N41.399 (2)
C2—H20.9300N3—C91.403 (3)
C3—C41.387 (3)N4—C111.279 (3)
C3—H30.9300C9—O21.197 (3)
C4—C51.387 (3)C9—C101.479 (3)
C4—C71.447 (3)C10—H10A0.9600
C5—C61.360 (4)C10—H10B0.9600
C5—H50.9300C10—H10C0.9600
C6—H60.9300C11—C121.481 (3)
C7—N11.271 (3)C12—H12A0.9600
C7—H70.9300C12—H12B0.9600
N1—N21.378 (2)C12—H12C0.9600
N2—C111.381 (3)
C2—C1—C6120.6 (2)O1—C8—N2128.4 (2)
C2—C1—Cl1120.7 (2)O1—C8—N3129.4 (2)
C6—C1—Cl1118.77 (19)N2—C8—N3102.13 (17)
C1—C2—C3119.5 (2)C8—N3—N4112.27 (18)
C1—C2—H2120.3C8—N3—C9127.54 (17)
C3—C2—H2120.3N4—N3—C9120.01 (18)
C2—C3—C4121.1 (2)C11—N4—N3104.64 (17)
C2—C3—H3119.5O2—C9—N3119.8 (2)
C4—C3—H3119.5O2—C9—C10124.5 (2)
C5—C4—C3118.2 (2)N3—C9—C10115.73 (19)
C5—C4—C7121.5 (2)C9—C10—H10A109.5
C3—C4—C7120.38 (19)C9—C10—H10B109.5
C6—C5—C4120.9 (2)H10A—C10—H10B109.5
C6—C5—H5119.6C9—C10—H10C109.5
C4—C5—H5119.6H10A—C10—H10C109.5
C5—C6—C1119.8 (2)H10B—C10—H10C109.5
C5—C6—H6120.1N4—C11—N2112.30 (18)
C1—C6—H6120.1N4—C11—C12125.2 (2)
N1—C7—C4118.7 (2)N2—C11—C12122.5 (2)
N1—C7—H7120.6C11—C12—H12A109.5
C4—C7—H7120.6C11—C12—H12B109.5
C7—N1—N2119.93 (18)H12A—C12—H12B109.5
N1—N2—C11120.01 (17)C11—C12—H12C109.5
N1—N2—C8131.24 (17)H12A—C12—H12C109.5
C11—N2—C8108.66 (19)H12B—C12—H12C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O10.932.282.938 (3)127
C2—H2···O2i0.932.523.162 (3)126
C12—H12B···O2ii0.962.523.414 (3)154
C10—H10C···O1iii0.962.613.499 (3)154
Symmetry codes: (i) x+2, y+1, z+2; (ii) x+1, y, z+2; (iii) x1, y, z.

Experimental details

Crystal data
Chemical formulaC12H11ClN4O2
Mr278.70
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)6.910 (3), 7.5682 (10), 12.380 (3)
α, β, γ (°)93.13 (2), 98.20 (2), 95.86 (2)
V3)635.9 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.30
Crystal size (mm)0.25 × 0.15 × 0.1
Data collection
DiffractometerEnraf-Nonius CAD-4 MACH3
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2723, 2503, 1527
Rint0.015
(sin θ/λ)max1)0.616
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.121, 1.02
No. of reflections2503
No. of parameters174
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.24

Computer programs: CAD-4-PC Software (Enraf-Nonius, 1992), CAD-4-PC Software, XCAD4 (Harms, 1997), SHELXS97 (Sheldrick, 1990), SHELXL7 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
Cl1—C11.730 (3)C8—N31.387 (3)
C4—C71.447 (3)N3—N41.399 (2)
C7—N11.271 (3)N3—C91.403 (3)
N1—N21.378 (2)N4—C111.279 (3)
N2—C111.381 (3)C9—O21.197 (3)
N2—C81.387 (3)C9—C101.479 (3)
C8—O11.209 (2)C11—C121.481 (3)
O2—C9—N3119.8 (2)N4—C11—N2112.30 (18)
O2—C9—C10124.5 (2)N4—C11—C12125.2 (2)
N3—C9—C10115.73 (19)N2—C11—C12122.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C7—H7···O10.932.282.938 (3)127
C2—H2···O2i0.932.523.162 (3)126
C12—H12B···O2ii0.962.523.414 (3)154
C10—H10C···O1iii0.962.613.499 (3)154
Symmetry codes: (i) x+2, y+1, z+2; (ii) x+1, y, z+2; (iii) x1, y, z.
 

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