1-(4-Chloro­phen­yl)-1H-1,2,4-triazol-5(4H)-one

Kattimani, P.P.; Kamble, R.R.; Kumbar, M.N.; Arunkashi, H.K.; Devarajegowda, H.C.

doi:10.1107/S1600536814006412

organic compounds

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ISSN: 2056-9890

Volume 70| Part 4| April 2014| Page o499

doi:10.1107/S1600536814006412

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1-(4-Chlorophenyl)-1H-1,2,4-triazol-5(4H)-one

Pramod P. Kattimani,^a Ravindra R. Kamble,^a ^* Mahadev N. Kumbar,^a H. K. Arunkashi ^b and H. C. Devarajegowda ^c ^*

^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

(Received 18 March 2014; accepted 23 March 2014; online 29 March 2014)

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

C₈H₆ClN₃O
M_r = 195.61
Triclinic, $[P \overline 1]$
a = 6.5791 (4) Å
b = 7.2663 (4) Å
c = 9.3342 (5) Å
α = 80.121 (4)°
β = 85.042 (4)°
γ = 70.235 (4)°
V = 413.52 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 296 K
0.24 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: ψ scan (SADABS; Sheldrick, 2007 ) T_min = 0.770, T_max = 1.000
5938 measured reflections
1438 independent reflections
1270 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.094
S = 1.06
1438 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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.

Data collection: SMART (Bruker, 2001 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814006412/hb7211sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814006412/hb7211Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814006412/hb7211Isup3.cml

checkCIF report

Comment top

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. C_g(1)π–πC_g(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.

Related literature top

For a related structure and background to 1,2,4-triazoles, see: Devarajegowda et al.(2012).

Experimental top

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).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: 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).

Figures top

	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.

1-(4-Chlorophenyl)-1H-1,2,4-triazol-5(4H)-one top

Crystal data top

C₈H₆ClN₃O	Z = 2
M_r = 195.61	F(000) = 200
Triclinic, P1	D_x = 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

Data collection top

Bruker SMART CCD diffractometer	1438 independent reflections
Radiation source: fine-focus sealed tube	1270 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω and ϕ scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: ψ scan (SADABS; Sheldrick, 2007)	h = −7→7
T_min = 0.770, T_max = 1.000	k = −8→8
5938 measured reflections	l = −11→11

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0473P)² + 0.1038P] where P = (F_o² + 2F_c²)/3
1438 reflections	(Δ/σ)_max = 0.001
118 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₈H₆ClN₃O	γ = 70.235 (4)°
M_r = 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)°

Data collection top

Bruker SMART CCD diffractometer	1438 independent reflections
Absorption correction: ψ scan (SADABS; Sheldrick, 2007)	1270 reflections with I > 2σ(I)
T_min = 0.770, T_max = 1.000	R_int = 0.025
5938 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.06	Δρ_max = 0.17 e Å⁻³
1438 reflections	Δρ_min = −0.15 e Å⁻³
118 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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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