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The molecules of the title compound, C
12H
11ClN
4O
2, 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
CCDC reference: 209975
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (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
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 C═O), 155.79 (N═CH), 151.18 (triazole C═O), 148.14, 133.68, 132.95, 132.13 (2 C), 131.80 (2 C), 23.61, 12.18.
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.
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.
1-Acetyl-3-methyl-4-(
P-chlorobenzylidenamino)-4,5-dihydro- 1
H-1,2,4-triazol-5-one
top
Crystal data top
C12H11ClN4O2 | Z = 2 |
Mr = 278.70 | F(000) = 288 |
Triclinic, P1 | Dx = 1.456 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.910 (3) Å | Cell parameters from 25 reflections |
b = 7.5682 (10) Å | θ = 8.2–13.4° |
c = 12.380 (3) Å | µ = 0.30 mm−1 |
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 tube | θmax = 26.0°, θmin = 2.7° |
Graphite monochromator | h = 0→8 |
ω–2θ scans | k = −9→9 |
2723 measured reflections | l = −15→15 |
2503 independent reflections | 3 standard reflections every 60 min |
1527 reflections with I > 2σ(I) | intensity decay: 0.1% |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-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 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
Crystal data top
C12H11ClN4O2 | γ = 95.86 (2)° |
Mr = 278.70 | V = 635.9 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.910 (3) Å | Mo Kα radiation |
b = 7.5682 (10) Å | µ = 0.30 mm−1 |
c = 12.380 (3) Å | T = 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 reflections | 3 standard reflections every 60 min |
2503 independent reflections | intensity decay: 0.1% |
1527 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.19 e Å−3 |
2503 reflections | Δρmin = −0.24 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Cl1 | 1.30518 (13) | 0.31259 (12) | 0.43443 (6) | 0.0939 (3) | |
C1 | 1.1650 (4) | 0.3165 (3) | 0.53956 (19) | 0.0599 (6) | |
C2 | 1.2396 (4) | 0.4034 (3) | 0.63867 (19) | 0.0586 (6) | |
H2 | 1.3653 | 0.4646 | 0.6498 | 0.070* | |
C3 | 1.1281 (3) | 0.3998 (3) | 0.72144 (18) | 0.0520 (6) | |
H3 | 1.1787 | 0.4594 | 0.7888 | 0.062* | |
C4 | 0.9406 (3) | 0.3085 (3) | 0.70658 (18) | 0.0483 (5) | |
C5 | 0.8667 (4) | 0.2255 (3) | 0.6043 (2) | 0.0653 (7) | |
H5 | 0.7400 | 0.1662 | 0.5920 | 0.078* | |
C6 | 0.9769 (4) | 0.2298 (4) | 0.5216 (2) | 0.0703 (8) | |
H6 | 0.9254 | 0.1744 | 0.4532 | 0.084* | |
C7 | 0.8276 (3) | 0.2997 (3) | 0.79634 (18) | 0.0503 (6) | |
H7 | 0.8738 | 0.3644 | 0.8627 | 0.060* | |
N1 | 0.6640 (3) | 0.2020 (2) | 0.78283 (15) | 0.0507 (5) | |
N2 | 0.5517 (3) | 0.1937 (2) | 0.86630 (14) | 0.0474 (5) | |
C8 | 0.5795 (3) | 0.2824 (3) | 0.96927 (17) | 0.0452 (5) | |
O1 | 0.7185 (2) | 0.3842 (2) | 1.01258 (12) | 0.0548 (4) | |
N3 | 0.4083 (3) | 0.2233 (2) | 1.00901 (14) | 0.0461 (4) | |
N4 | 0.2821 (3) | 0.1039 (2) | 0.93391 (15) | 0.0511 (5) | |
C9 | 0.3485 (3) | 0.2796 (3) | 1.10770 (18) | 0.0488 (5) | |
O2 | 0.4589 (2) | 0.3780 (2) | 1.17304 (14) | 0.0636 (5) | |
C10 | 0.1472 (4) | 0.2092 (3) | 1.1229 (2) | 0.0641 (7) | |
H10A | 0.1273 | 0.2400 | 1.1965 | 0.096* | |
H10B | 0.1307 | 0.0820 | 1.1097 | 0.096* | |
H10C | 0.0531 | 0.2599 | 1.0725 | 0.096* | |
C11 | 0.3725 (3) | 0.0897 (3) | 0.85118 (19) | 0.0475 (5) | |
C12 | 0.2981 (4) | −0.0240 (3) | 0.7496 (2) | 0.0619 (7) | |
H12A | 0.1620 | −0.0657 | 0.7490 | 0.093* | |
H12B | 0.3727 | −0.1240 | 0.7467 | 0.093* | |
H12C | 0.3115 | 0.0439 | 0.6873 | 0.093* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0981 (6) | 0.1181 (7) | 0.0628 (5) | −0.0192 (5) | 0.0326 (4) | −0.0141 (4) |
C1 | 0.0640 (17) | 0.0648 (15) | 0.0493 (14) | −0.0035 (13) | 0.0119 (12) | −0.0008 (11) |
C2 | 0.0539 (15) | 0.0656 (15) | 0.0510 (14) | −0.0108 (12) | 0.0060 (12) | −0.0043 (11) |
C3 | 0.0528 (14) | 0.0520 (13) | 0.0454 (12) | −0.0058 (11) | −0.0007 (11) | −0.0058 (10) |
C4 | 0.0473 (13) | 0.0479 (12) | 0.0466 (12) | 0.0014 (10) | 0.0014 (10) | −0.0035 (10) |
C5 | 0.0515 (15) | 0.0809 (18) | 0.0556 (15) | −0.0116 (13) | 0.0017 (12) | −0.0141 (13) |
C6 | 0.0697 (18) | 0.0851 (18) | 0.0472 (14) | −0.0096 (15) | −0.0011 (13) | −0.0150 (13) |
C7 | 0.0474 (13) | 0.0503 (12) | 0.0493 (13) | 0.0015 (11) | −0.0001 (11) | −0.0049 (10) |
N1 | 0.0453 (11) | 0.0538 (11) | 0.0504 (11) | 0.0013 (9) | 0.0041 (9) | −0.0037 (9) |
N2 | 0.0422 (10) | 0.0468 (10) | 0.0492 (10) | −0.0028 (8) | 0.0020 (9) | −0.0048 (8) |
C8 | 0.0413 (12) | 0.0438 (11) | 0.0468 (12) | 0.0010 (10) | −0.0020 (10) | −0.0010 (10) |
O1 | 0.0427 (9) | 0.0611 (9) | 0.0529 (9) | −0.0113 (7) | −0.0020 (7) | −0.0092 (7) |
N3 | 0.0376 (10) | 0.0469 (10) | 0.0486 (10) | −0.0049 (8) | −0.0014 (8) | −0.0043 (8) |
N4 | 0.0428 (10) | 0.0493 (10) | 0.0550 (11) | −0.0073 (9) | −0.0015 (9) | −0.0053 (9) |
C9 | 0.0425 (12) | 0.0526 (12) | 0.0486 (13) | 0.0005 (10) | 0.0008 (10) | 0.0037 (11) |
O2 | 0.0515 (10) | 0.0793 (11) | 0.0530 (9) | −0.0066 (9) | 0.0004 (8) | −0.0120 (8) |
C10 | 0.0482 (14) | 0.0764 (16) | 0.0654 (16) | −0.0052 (12) | 0.0117 (12) | −0.0030 (13) |
C11 | 0.0408 (12) | 0.0430 (11) | 0.0533 (13) | −0.0024 (10) | −0.0040 (10) | −0.0022 (10) |
C12 | 0.0555 (15) | 0.0582 (14) | 0.0635 (15) | −0.0084 (12) | −0.0023 (12) | −0.0154 (12) |
Geometric parameters (Å, º) top
Cl1—C1 | 1.730 (3) | N2—C8 | 1.387 (3) |
C1—C2 | 1.366 (3) | C8—O1 | 1.209 (2) |
C1—C6 | 1.377 (4) | C8—N3 | 1.387 (3) |
C2—C3 | 1.367 (3) | N3—N4 | 1.399 (2) |
C2—H2 | 0.9300 | N3—C9 | 1.403 (3) |
C3—C4 | 1.387 (3) | N4—C11 | 1.279 (3) |
C3—H3 | 0.9300 | C9—O2 | 1.197 (3) |
C4—C5 | 1.387 (3) | C9—C10 | 1.479 (3) |
C4—C7 | 1.447 (3) | C10—H10A | 0.9600 |
C5—C6 | 1.360 (4) | C10—H10B | 0.9600 |
C5—H5 | 0.9300 | C10—H10C | 0.9600 |
C6—H6 | 0.9300 | C11—C12 | 1.481 (3) |
C7—N1 | 1.271 (3) | C12—H12A | 0.9600 |
C7—H7 | 0.9300 | C12—H12B | 0.9600 |
N1—N2 | 1.378 (2) | C12—H12C | 0.9600 |
N2—C11 | 1.381 (3) | | |
| | | |
C2—C1—C6 | 120.6 (2) | O1—C8—N2 | 128.4 (2) |
C2—C1—Cl1 | 120.7 (2) | O1—C8—N3 | 129.4 (2) |
C6—C1—Cl1 | 118.77 (19) | N2—C8—N3 | 102.13 (17) |
C1—C2—C3 | 119.5 (2) | C8—N3—N4 | 112.27 (18) |
C1—C2—H2 | 120.3 | C8—N3—C9 | 127.54 (17) |
C3—C2—H2 | 120.3 | N4—N3—C9 | 120.01 (18) |
C2—C3—C4 | 121.1 (2) | C11—N4—N3 | 104.64 (17) |
C2—C3—H3 | 119.5 | O2—C9—N3 | 119.8 (2) |
C4—C3—H3 | 119.5 | O2—C9—C10 | 124.5 (2) |
C5—C4—C3 | 118.2 (2) | N3—C9—C10 | 115.73 (19) |
C5—C4—C7 | 121.5 (2) | C9—C10—H10A | 109.5 |
C3—C4—C7 | 120.38 (19) | C9—C10—H10B | 109.5 |
C6—C5—C4 | 120.9 (2) | H10A—C10—H10B | 109.5 |
C6—C5—H5 | 119.6 | C9—C10—H10C | 109.5 |
C4—C5—H5 | 119.6 | H10A—C10—H10C | 109.5 |
C5—C6—C1 | 119.8 (2) | H10B—C10—H10C | 109.5 |
C5—C6—H6 | 120.1 | N4—C11—N2 | 112.30 (18) |
C1—C6—H6 | 120.1 | N4—C11—C12 | 125.2 (2) |
N1—C7—C4 | 118.7 (2) | N2—C11—C12 | 122.5 (2) |
N1—C7—H7 | 120.6 | C11—C12—H12A | 109.5 |
C4—C7—H7 | 120.6 | C11—C12—H12B | 109.5 |
C7—N1—N2 | 119.93 (18) | H12A—C12—H12B | 109.5 |
N1—N2—C11 | 120.01 (17) | C11—C12—H12C | 109.5 |
N1—N2—C8 | 131.24 (17) | H12A—C12—H12C | 109.5 |
C11—N2—C8 | 108.66 (19) | H12B—C12—H12C | 109.5 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O1 | 0.93 | 2.28 | 2.938 (3) | 127 |
C2—H2···O2i | 0.93 | 2.52 | 3.162 (3) | 126 |
C12—H12B···O2ii | 0.96 | 2.52 | 3.414 (3) | 154 |
C10—H10C···O1iii | 0.96 | 2.61 | 3.499 (3) | 154 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y, −z+2; (iii) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | C12H11ClN4O2 |
Mr | 278.70 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 635.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.25 × 0.15 × 0.1 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 MACH3 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2723, 2503, 1527 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.616 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.121, 1.02 |
No. of reflections | 2503 |
No. of parameters | 174 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.24 |
Selected geometric parameters (Å, º) topCl1—C1 | 1.730 (3) | C8—N3 | 1.387 (3) |
C4—C7 | 1.447 (3) | N3—N4 | 1.399 (2) |
C7—N1 | 1.271 (3) | N3—C9 | 1.403 (3) |
N1—N2 | 1.378 (2) | N4—C11 | 1.279 (3) |
N2—C11 | 1.381 (3) | C9—O2 | 1.197 (3) |
N2—C8 | 1.387 (3) | C9—C10 | 1.479 (3) |
C8—O1 | 1.209 (2) | C11—C12 | 1.481 (3) |
| | | |
O2—C9—N3 | 119.8 (2) | N4—C11—N2 | 112.30 (18) |
O2—C9—C10 | 124.5 (2) | N4—C11—C12 | 125.2 (2) |
N3—C9—C10 | 115.73 (19) | N2—C11—C12 | 122.5 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O1 | 0.93 | 2.28 | 2.938 (3) | 127 |
C2—H2···O2i | 0.93 | 2.52 | 3.162 (3) | 126 |
C12—H12B···O2ii | 0.96 | 2.52 | 3.414 (3) | 154 |
C10—H10C···O1iii | 0.96 | 2.61 | 3.499 (3) | 154 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y, −z+2; (iii) x−1, y, z. |
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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). N═C bond lengths [N4═C11 = 1.278 (3) Å and N1═C7 = 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 π–π-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.