organic compounds
1-(4-Chlorophenyl)-1H-1,2,4-triazol-5(4H)-one
aDepartment of Studies in Chemistry, Karnataka University, Dharwad 580 003, Karnataka, India, bDepartment of Physics, Moodlakatte Institute of Technology, Kundapura 576 217, Karnataka, India, and cDepartment of Physics, Yuvaraja's College (Constituent College), University of Mysore, Mysore 570 005, Karnataka, India
*Correspondence e-mail: ravichem@kud.ac.in, devarajegowda@yahoo.com
In the title compound, C8H6ClN3O, the dihedral angle between the 1,2,4-triazole and benzene rings is 4.60 (9)° and an intramolecular C—H⋯O interaction closes an S(6) ring. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R22(8) loops and C—H⋯O interactions link the dimers into [100] chains. Weak π–π stacking interactions [centroid–centroid distance = 3.644 (1) Å] are also observed.
CCDC reference: 993126
Related literature
For a related structure and background to 1,2,4-triazoles, see: Devarajegowda et al.(2012).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 993126
10.1107/S1600536814006412/hb7211sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814006412/hb7211Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814006412/hb7211Isup3.cml
2-(4-Chlorophenyl)-2,4-dihydro-3H-1,2,4-triazol-3-one was refluxed with formamide at 453 K. After completion of the reaction, the reaction mixture was poured into ice cold water to recover the title compound, which was recrystallized from ethanol solution as colourless plates (m.p. 528 K).
All H atoms were positioned geometrically, with N—H = 0.86 Å, and C—H = 0.93 Å for aromatic H and refined using a riding model with Uiso(H) = 1.2Ueq(C, N) for aromatic and amide H.
Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. The packing of the title compound. |
C8H6ClN3O | Z = 2 |
Mr = 195.61 | F(000) = 200 |
Triclinic, P1 | Dx = 1.571 Mg m−3 |
Hall symbol: -P 1 | Melting point: 528 K |
a = 6.5791 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.2663 (4) Å | Cell parameters from 1438 reflections |
c = 9.3342 (5) Å | θ = 2.2–25.0° |
α = 80.121 (4)° | µ = 0.42 mm−1 |
β = 85.042 (4)° | T = 296 K |
γ = 70.235 (4)° | Plate, colourless |
V = 413.52 (4) Å3 | 0.24 × 0.20 × 0.12 mm |
Bruker SMART CCD diffractometer | 1438 independent reflections |
Radiation source: fine-focus sealed tube | 1270 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω and ϕ scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: ψ scan (SADABS; Sheldrick, 2007) | h = −7→7 |
Tmin = 0.770, Tmax = 1.000 | k = −8→8 |
5938 measured reflections | l = −11→11 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0473P)2 + 0.1038P] where P = (Fo2 + 2Fc2)/3 |
1438 reflections | (Δ/σ)max = 0.001 |
118 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
C8H6ClN3O | γ = 70.235 (4)° |
Mr = 195.61 | V = 413.52 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.5791 (4) Å | Mo Kα radiation |
b = 7.2663 (4) Å | µ = 0.42 mm−1 |
c = 9.3342 (5) Å | T = 296 K |
α = 80.121 (4)° | 0.24 × 0.20 × 0.12 mm |
β = 85.042 (4)° |
Bruker SMART CCD diffractometer | 1438 independent reflections |
Absorption correction: ψ scan (SADABS; Sheldrick, 2007) | 1270 reflections with I > 2σ(I) |
Tmin = 0.770, Tmax = 1.000 | Rint = 0.025 |
5938 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.17 e Å−3 |
1438 reflections | Δρmin = −0.15 e Å−3 |
118 parameters |
Experimental. IR (KBr): 1686 (C=O), 3433 (NH); 1H-NMR (400 MHz, DMSO-D6, δ p.p.m.): 7.46–7.50 (d, 2H, ArH, J = 16 Hz), 7.90–7.94 (d, 2H, ArH, J = 16 Hz), 8.12 (s, 1H, C5H), 12.00 (s, 1H, NH); 13C-NMR (100 MHz, DMSO-D6, δ p.p.m.): 119.26, 128.77, 128.84, 136.66, 136.72, 152.17; MS (m/z, 70 eV): 197 (M2+), 195 (M+), 127, 125, 113, 111. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | −0.31296 (10) | 0.62029 (8) | 1.39673 (5) | 0.0705 (2) | |
O2 | −0.1420 (2) | 0.9297 (2) | 0.66886 (13) | 0.0595 (4) | |
N3 | 0.1322 (2) | 0.79679 (19) | 0.83947 (14) | 0.0385 (3) | |
N4 | 0.3528 (2) | 0.7607 (2) | 0.83651 (15) | 0.0488 (4) | |
N5 | 0.2213 (2) | 0.8940 (2) | 0.62018 (15) | 0.0457 (4) | |
H5 | 0.2196 | 0.9413 | 0.5291 | 0.055* | |
C11 | −0.1807 (3) | 0.6731 (2) | 1.23269 (18) | 0.0462 (4) | |
C10 | −0.2983 (3) | 0.7604 (3) | 1.1128 (2) | 0.0600 (5) | |
H10 | −0.4479 | 0.7927 | 1.1186 | 0.072* | |
C9 | −0.1960 (3) | 0.8017 (3) | 0.9812 (2) | 0.0557 (5) | |
H9 | −0.2767 | 0.8615 | 0.8986 | 0.067* | |
C8 | 0.0241 (2) | 0.7544 (2) | 0.97287 (16) | 0.0369 (3) | |
C7 | 0.0477 (3) | 0.8791 (2) | 0.70550 (17) | 0.0414 (4) | |
C12 | 0.0388 (3) | 0.6240 (3) | 1.2260 (2) | 0.0600 (5) | |
H12 | 0.1183 | 0.5645 | 1.3092 | 0.072* | |
C13 | 0.1426 (3) | 0.6632 (3) | 1.0949 (2) | 0.0563 (5) | |
H13 | 0.2924 | 0.6278 | 1.0894 | 0.068* | |
C6 | 0.3967 (3) | 0.8216 (3) | 0.70340 (19) | 0.0500 (4) | |
H6 | 0.5350 | 0.8162 | 0.6684 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0853 (4) | 0.0835 (4) | 0.0407 (3) | −0.0336 (3) | 0.0192 (2) | −0.0029 (2) |
O2 | 0.0439 (7) | 0.0937 (10) | 0.0378 (6) | −0.0286 (7) | −0.0083 (5) | 0.0143 (6) |
N3 | 0.0342 (7) | 0.0481 (7) | 0.0320 (7) | −0.0137 (5) | −0.0030 (5) | −0.0012 (5) |
N4 | 0.0351 (8) | 0.0675 (9) | 0.0393 (8) | −0.0140 (6) | −0.0019 (6) | −0.0020 (6) |
N5 | 0.0429 (8) | 0.0615 (8) | 0.0319 (7) | −0.0210 (6) | 0.0008 (6) | 0.0018 (6) |
C11 | 0.0586 (11) | 0.0470 (9) | 0.0333 (8) | −0.0202 (8) | 0.0072 (7) | −0.0046 (7) |
C10 | 0.0396 (9) | 0.0893 (14) | 0.0466 (10) | −0.0202 (9) | 0.0037 (8) | −0.0030 (9) |
C9 | 0.0403 (9) | 0.0861 (13) | 0.0344 (9) | −0.0181 (9) | −0.0046 (7) | 0.0041 (8) |
C8 | 0.0399 (8) | 0.0389 (8) | 0.0313 (8) | −0.0132 (6) | −0.0013 (6) | −0.0029 (6) |
C7 | 0.0411 (9) | 0.0499 (9) | 0.0337 (8) | −0.0187 (7) | −0.0030 (7) | 0.0011 (6) |
C12 | 0.0579 (12) | 0.0775 (13) | 0.0346 (9) | −0.0167 (10) | −0.0070 (8) | 0.0096 (8) |
C13 | 0.0399 (9) | 0.0786 (12) | 0.0412 (10) | −0.0149 (8) | −0.0072 (8) | 0.0087 (8) |
C6 | 0.0377 (9) | 0.0696 (11) | 0.0405 (9) | −0.0180 (8) | 0.0025 (7) | −0.0041 (8) |
Cl1—C11 | 1.7444 (16) | C11—C12 | 1.364 (3) |
O2—C7 | 1.237 (2) | C10—C9 | 1.385 (3) |
N3—C7 | 1.367 (2) | C10—H10 | 0.9300 |
N3—N4 | 1.3833 (19) | C9—C8 | 1.369 (2) |
N3—C8 | 1.419 (2) | C9—H9 | 0.9300 |
N4—C6 | 1.288 (2) | C8—C13 | 1.375 (2) |
N5—C6 | 1.348 (2) | C12—C13 | 1.383 (3) |
N5—C7 | 1.359 (2) | C12—H12 | 0.9300 |
N5—H5 | 0.8600 | C13—H13 | 0.9300 |
C11—C10 | 1.352 (3) | C6—H6 | 0.9300 |
C7—N3—N4 | 111.34 (13) | C9—C8—C13 | 119.67 (15) |
C7—N3—C8 | 128.99 (13) | C9—C8—N3 | 120.90 (14) |
N4—N3—C8 | 119.63 (12) | C13—C8—N3 | 119.43 (15) |
C6—N4—N3 | 103.86 (13) | O2—C7—N5 | 127.42 (15) |
C6—N5—C7 | 107.98 (14) | O2—C7—N3 | 128.69 (15) |
C6—N5—H5 | 126.0 | N5—C7—N3 | 103.89 (13) |
C7—N5—H5 | 126.0 | C11—C12—C13 | 119.63 (17) |
C10—C11—C12 | 120.83 (16) | C11—C12—H12 | 120.2 |
C10—C11—Cl1 | 119.12 (14) | C13—C12—H12 | 120.2 |
C12—C11—Cl1 | 120.04 (14) | C8—C13—C12 | 119.95 (17) |
C11—C10—C9 | 119.95 (17) | C8—C13—H13 | 120.0 |
C11—C10—H10 | 120.0 | C12—C13—H13 | 120.0 |
C9—C10—H10 | 120.0 | N4—C6—N5 | 112.93 (15) |
C8—C9—C10 | 119.94 (17) | N4—C6—H6 | 123.5 |
C8—C9—H9 | 120.0 | N5—C6—H6 | 123.5 |
C10—C9—H9 | 120.0 | ||
C7—N3—N4—C6 | 0.28 (18) | C6—N5—C7—N3 | 0.31 (18) |
C8—N3—N4—C6 | −177.50 (14) | N4—N3—C7—O2 | 179.93 (18) |
C12—C11—C10—C9 | −0.3 (3) | C8—N3—C7—O2 | −2.6 (3) |
Cl1—C11—C10—C9 | −179.35 (16) | N4—N3—C7—N5 | −0.37 (18) |
C11—C10—C9—C8 | −0.1 (3) | C8—N3—C7—N5 | 177.14 (14) |
C10—C9—C8—C13 | 1.1 (3) | C10—C11—C12—C13 | −0.3 (3) |
C10—C9—C8—N3 | −179.50 (17) | Cl1—C11—C12—C13 | 178.82 (16) |
C7—N3—C8—C9 | −2.1 (3) | C9—C8—C13—C12 | −1.6 (3) |
N4—N3—C8—C9 | 175.26 (15) | N3—C8—C13—C12 | 178.97 (17) |
C7—N3—C8—C13 | 177.37 (16) | C11—C12—C13—C8 | 1.2 (3) |
N4—N3—C8—C13 | −5.3 (2) | N3—N4—C6—N5 | −0.1 (2) |
C6—N5—C7—O2 | −179.98 (18) | C7—N5—C6—N4 | −0.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O2i | 0.86 | 1.95 | 2.7924 (18) | 166 |
C6—H6···O2ii | 0.93 | 2.53 | 3.360 (3) | 149 |
C9—H9···O2 | 0.93 | 2.29 | 2.933 (2) | 126 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N5—H5···O2i | 0.86 | 1.95 | 2.7924 (18) | 166 |
C6—H6···O2ii | 0.93 | 2.53 | 3.360 (3) | 149 |
C9—H9···O2 | 0.93 | 2.29 | 2.933 (2) | 126 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x+1, y, z. |
Acknowledgements
The authors acknowledge the University Scientific Instrumentation Centre (USIC), Karnatak University, Dharwad, for providing the XRD data. PPK thanks the University Grants Commission (UGC), New Delhi, for financial assistance under the RFSMS scheme. The authors are grateful to the University Grants Commission, New Delhi [F. No. 14–3/2012 (NS/PE) Dated: 14–03-2012] for providing financial support under Antitumor activity an integrated approach, a focused area of the UPE programme.
References
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As part of our onging studies of 1,2,4-triazoles (Devarajegowda et al., 2012), we now describe the synthesis and structure of the title compound.
The asymmetric unit of 2-(4-chlorophenyl)-2,4-dihydro-3H-1,2,4-triazol- 3-one is shown in Fig. 1. The dihedral angle between the 1,2,4-triazol ring (N3/N4/N5/C6/C7) and the benzene ring (C8–C13) is 4.60 (9)°. In the crystal, inversion related N5—H5···O2 interactions generate an R22(8) ring pattern and link pairs of independent molecules into dimers and C6—H6···O interactions generate R22(10) ring motifs. Cg(1)π–πCg(2) interactions [centroid–centroid distance = 3.644 (1) Å] between 1,2,4 triazole (N3/N4/N5/C6/C7) and benzene (C8–C13) rings are also observed.