4-n-Butyl-3-(3-methyl­phen­yl)-1H-1,2,4-triazol-5(4H)-one

Akhtar, T.; Hameed, S.; Zia-ur-Rehman, M.; Hussain Bukhari, T.; Khan, I.

doi:10.1107/S1600536808019661

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1388

doi:10.1107/S1600536808019661

Open

access

4-n-Butyl-3-(3-methylphenyl)-1H-1,2,4-triazol-5(4H)-one

Tashfeen Akhtar,^a Shahid Hameed,^a Muhammad Zia-ur-Rehman,^b Tanveer Hussain Bukhari ^c ^* and Islamullah Khan ^c

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, ^bApplied Chemistry Research Centre, PCSIR Laboratories Complex, Lahore 54600, Pakistan, and ^cChemistry Department, Government College University, Lahore, Pakistan
^*Correspondence e-mail: tanveerhusari@yahoo.com

(Received 23 June 2008; accepted 27 June 2008; online 5 July 2008)

In the molecule of the title compound, C₁₃H₁₇N₃O, the two rings make a dihedral angle of 56.63 (13)°. Molecules are linked by strong N—H⋯O intermolecular hydrogen bonds into chains running along the c axis.

Related literature

For related literature, see: Akhtar et al. (2006 , 2007 , 2008 ); Aoyama et al. (1984 ); Al-Masoudi et al. (2006 ); Demirbas et al. (2002 ); Lin et al. (2005 ); Torres et al. (2005 ); Witkowski et al. (1972 ).

Experimental

Crystal data

C₁₃H₁₇N₃O
M_r = 231.30
Orthorhombic, C c c 2
a = 16.905 (5) Å
b = 18.139 (5) Å
c = 8.145 (2) Å
V = 2497.5 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 (2) K
0.26 × 0.19 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: none
8129 measured reflections
1791 independent reflections
1118 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.106
S = 1.07
1791 reflections
160 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H22⋯O1ⁱ	0.94 (3)	1.84 (3)	2.775 (3)	170 (3)
Symmetry code: (i) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2007); 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, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808019661/bt2734sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808019661/bt2734Isup2.hkl

checkCIF report

Comment top

1,2,4-Triazoles are known to possess a broad range of biological activities, finding applications as antifungal (Al-Masoudi et al., 2006; Torres et al., 2005), anticancer (Lin et al., 2005; Demirbas et al., 2002) and antiviral (Witkowski et al., 1972; Aoyama et al.,1984) activities. Besides, these derivatives have shown herbicidal, anticonvulsant and hypocholesteramic activities.

As part of our on going research on the synthesis of biologically active heterocyclic compounds (Akhtar et al., 2006, 2007, 2008), the title compound (I) was synthesized by cyclodehydration of 4-n-butyl-1-(3-methylbenzoyl) semicarbazide under basic conditions (Akhtar et al., 2006) to evaluate its biological activities.

The two rings enclose a dihedral angle of 56.63 (13)°. There is an intermolecular N—H···O=C hydrogen bond between the amino hydrogen and the carbonyl oxygen giving rise to a zigzag chain of molecules parallel to the c axis (Fig. 2).

Related literature top

For related literature, see: Akhtar et al. (2006, 2007, 2008); Aoyama et al. (1984); Al-Masoudi et al. (2006); Demirbas et al. (2002); Lin et al. (2005); Torres et al. (2005); Witkowski et al. (1972).

Experimental top

A solution of 4-n-butyl-1-(3-methylbenzoyl) semicarbazide (0.30 g) and aqueous sodium hydroxide (5%, 30 ml) was refluxed for a period of five hours till the complete consumption of semicarbazide. The reaction mixture was cooled to room temperature and neutralized with 6M HCl. The precipitated solid was filtered, washed with excess water, dried and recrystallized from aqueous ethanol to afford pure crystalline 4-n-butyl-5-(3-methyl phenyl)-2H-1,2,4-triazol-3(4H)-one.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The asymmetric unit of the title compound showing the intramolecular hydrogen bond. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Perspective view of the three-dimensional crystal packing showing hydrogen-bonds and other intermolecular interactions (dashed lines). H atoms not involved in hydrogen bonding have been omitted for clarity.

4-n-Butyl-3-(3-methylphenyl)-1H-1,2,4-triazol-5(4H)-one top

Crystal data top

C₁₃H₁₇N₃O	F(000) = 992
M_r = 231.30	D_x = 1.230 Mg m⁻³
Orthorhombic, Ccc2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2 -2c	Cell parameters from 1751 reflections
a = 16.905 (5) Å	θ = 3.0–22.2°
b = 18.139 (5) Å	µ = 0.08 mm⁻¹
c = 8.145 (2) Å	T = 296 K
V = 2497.5 (11) Å³	Orthorhombic, white
Z = 8	0.26 × 0.19 × 0.12 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1118 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.066
Graphite monochromator	θ_max = 29.2°, θ_min = 2.4°
Detector resolution: 7.40 pixels mm^-1	h = −20→23
ϕ and ω scans	k = −23→24
8129 measured reflections	l = −11→7
1791 independent reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0435P)²] where P = (F_o² + 2F_c²)/3
1791 reflections	(Δ/σ)_max < 0.001
160 parameters	Δρ_max = 0.15 e Å⁻³
1 restraint	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₁₃H₁₇N₃O	V = 2497.5 (11) Å³
M_r = 231.30	Z = 8
Orthorhombic, Ccc2	Mo Kα radiation
a = 16.905 (5) Å	µ = 0.08 mm⁻¹
b = 18.139 (5) Å	T = 296 K
c = 8.145 (2) Å	0.26 × 0.19 × 0.12 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1118 reflections with I > 2σ(I)
8129 measured reflections	R_int = 0.066
1791 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	1 restraint
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.15 e Å⁻³
1791 reflections	Δρ_min = −0.25 e Å⁻³
160 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	U_iso*/U_eq
N1	0.09066 (14)	0.37056 (10)	0.2364 (3)	0.0349 (5)
N2	0.08503 (15)	0.41720 (12)	−0.0051 (3)	0.0407 (6)
N3	0.08408 (14)	0.34149 (11)	−0.0273 (3)	0.0412 (6)
O1	0.09681 (11)	0.49894 (11)	0.2110 (2)	0.0500 (6)
C1	0.08634 (17)	0.23582 (14)	0.1565 (3)	0.0350 (6)
C2	0.02844 (17)	0.20574 (14)	0.2574 (4)	0.0449 (8)
H2	−0.0090	0.2359	0.3072	0.054*
C3	0.0272 (2)	0.13041 (15)	0.2829 (4)	0.0531 (9)
H3	−0.0111	0.1100	0.3510	0.064*
C4	0.08179 (19)	0.08554 (16)	0.2092 (4)	0.0501 (8)
H4	0.0791	0.0349	0.2257	0.060*
C5	0.14059 (18)	0.11403 (14)	0.1111 (4)	0.0423 (7)
C6	0.14204 (17)	0.18975 (14)	0.0851 (3)	0.0389 (7)
H6	0.1811	0.2099	0.0185	0.047*
C7	0.08757 (16)	0.31523 (14)	0.1205 (3)	0.0355 (6)
C8	0.09113 (17)	0.43677 (14)	0.1525 (3)	0.0360 (6)
C9	0.11284 (18)	0.36397 (14)	0.4094 (3)	0.0385 (7)
H9A	0.0902	0.3192	0.4546	0.046*
H9B	0.0916	0.4055	0.4701	0.046*
C10	0.20182 (18)	0.36205 (16)	0.4290 (4)	0.0475 (7)
H10A	0.2223	0.3202	0.3683	0.057*
H10B	0.2239	0.4063	0.3803	0.057*
C11	0.22993 (18)	0.35668 (17)	0.6045 (4)	0.0499 (8)
H11A	0.2064	0.3137	0.6557	0.060*
H11B	0.2125	0.3999	0.6646	0.060*
C12	0.2024 (2)	0.06501 (17)	0.0313 (5)	0.0615 (10)
H13A	0.2245	0.0325	0.1123	0.092*
H13B	0.2436	0.0951	−0.0145	0.092*
H13C	0.1782	0.0364	−0.0543	0.092*
H22	0.0837 (17)	0.4487 (16)	−0.097 (4)	0.060 (10)*
C13	0.31893 (19)	0.35095 (19)	0.6144 (5)	0.0622 (9)
H13D	0.3366	0.3098	0.5500	0.093*
H13E	0.3345	0.3440	0.7267	0.093*
H13F	0.3423	0.3955	0.5730	0.093*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0461 (15)	0.0309 (11)	0.0277 (12)	−0.0011 (10)	−0.0020 (12)	−0.0027 (9)
N2	0.0577 (17)	0.0319 (12)	0.0325 (14)	−0.0033 (11)	−0.0061 (12)	0.0009 (10)
N3	0.0553 (15)	0.0328 (12)	0.0356 (14)	−0.0028 (10)	−0.0050 (12)	−0.0019 (11)
O1	0.0770 (15)	0.0307 (9)	0.0422 (12)	−0.0055 (11)	−0.0009 (11)	−0.0052 (9)
C1	0.0398 (16)	0.0312 (13)	0.0341 (15)	−0.0004 (12)	−0.0074 (13)	−0.0035 (12)
C2	0.047 (2)	0.0412 (15)	0.0464 (18)	−0.0008 (12)	0.0070 (15)	−0.0014 (14)
C3	0.056 (2)	0.0449 (16)	0.058 (2)	−0.0091 (15)	0.0099 (16)	0.0072 (15)
C4	0.063 (2)	0.0333 (14)	0.054 (2)	−0.0028 (14)	−0.0098 (18)	0.0041 (15)
C5	0.0478 (18)	0.0347 (14)	0.0444 (17)	0.0043 (13)	−0.0105 (16)	−0.0025 (14)
C6	0.0432 (17)	0.0385 (15)	0.0350 (16)	−0.0024 (12)	−0.0011 (13)	−0.0017 (13)
C7	0.0373 (16)	0.0332 (13)	0.0361 (16)	−0.0021 (11)	−0.0073 (14)	−0.0013 (11)
C8	0.0434 (17)	0.0343 (14)	0.0303 (15)	−0.0015 (12)	−0.0013 (13)	−0.0029 (12)
C9	0.0486 (19)	0.0365 (14)	0.0303 (15)	−0.0052 (12)	0.0002 (13)	−0.0013 (12)
C10	0.052 (2)	0.0548 (17)	0.0358 (16)	−0.0006 (14)	−0.0003 (15)	−0.0009 (13)
C11	0.057 (2)	0.0537 (18)	0.0393 (17)	0.0043 (15)	−0.0044 (16)	0.0027 (14)
C12	0.068 (3)	0.0503 (18)	0.066 (2)	0.0181 (17)	−0.0004 (19)	−0.0076 (17)
C13	0.059 (2)	0.069 (2)	0.059 (2)	0.0085 (17)	−0.012 (2)	−0.0021 (18)

Geometric parameters (Å, º) top

N1—C7	1.379 (3)	C5—C12	1.518 (4)
N1—C8	1.382 (3)	C6—H6	0.9300
N1—C9	1.463 (3)	C9—C10	1.513 (4)
N2—C8	1.336 (4)	C9—H9A	0.9700
N2—N3	1.385 (3)	C9—H9B	0.9700
N2—H22	0.94 (3)	C10—C11	1.509 (4)
N3—C7	1.296 (3)	C10—H10A	0.9700
O1—C8	1.228 (3)	C10—H10B	0.9700
C1—C6	1.387 (4)	C11—C13	1.510 (4)
C1—C2	1.390 (4)	C11—H11A	0.9700
C1—C7	1.470 (4)	C11—H11B	0.9700
C2—C3	1.382 (3)	C12—H13A	0.9600
C2—H2	0.9300	C12—H13B	0.9600
C3—C4	1.369 (4)	C12—H13C	0.9600
C3—H3	0.9300	C13—H13D	0.9600
C4—C5	1.376 (4)	C13—H13E	0.9600
C4—H4	0.9300	C13—H13F	0.9600
C5—C6	1.390 (4)

C7—N1—C8	107.1 (2)	N1—C9—C10	111.0 (2)
C7—N1—C9	127.6 (2)	N1—C9—H9A	109.4
C8—N1—C9	123.1 (2)	C10—C9—H9A	109.4
C8—N2—N3	113.0 (2)	N1—C9—H9B	109.4
C8—N2—H22	127.2 (19)	C10—C9—H9B	109.4
N3—N2—H22	119.8 (19)	H9A—C9—H9B	108.0
C7—N3—N2	104.0 (2)	C11—C10—C9	114.5 (3)
C6—C1—C2	119.3 (2)	C11—C10—H10A	108.6
C6—C1—C7	119.8 (3)	C9—C10—H10A	108.6
C2—C1—C7	120.8 (3)	C11—C10—H10B	108.6
C3—C2—C1	119.2 (3)	C9—C10—H10B	108.6
C3—C2—H2	120.4	H10A—C10—H10B	107.6
C1—C2—H2	120.4	C10—C11—C13	111.7 (3)
C4—C3—C2	120.8 (3)	C10—C11—H11A	109.3
C4—C3—H3	119.6	C13—C11—H11A	109.3
C2—C3—H3	119.6	C10—C11—H11B	109.3
C3—C4—C5	121.2 (3)	C13—C11—H11B	109.3
C3—C4—H4	119.4	H11A—C11—H11B	108.0
C5—C4—H4	119.4	C5—C12—H13A	109.5
C4—C5—C6	118.2 (3)	C5—C12—H13B	109.5
C4—C5—C12	121.7 (3)	H13A—C12—H13B	109.5
C6—C5—C12	120.1 (3)	C5—C12—H13C	109.5
C5—C6—C1	121.3 (3)	H13A—C12—H13C	109.5
C5—C6—H6	119.3	H13B—C12—H13C	109.5
C1—C6—H6	119.3	C11—C13—H13D	109.5
N3—C7—N1	111.7 (2)	C11—C13—H13E	109.5
N3—C7—C1	123.0 (2)	H13D—C13—H13E	109.5
N1—C7—C1	125.2 (2)	C11—C13—H13F	109.5
O1—C8—N2	128.5 (3)	H13D—C13—H13F	109.5
O1—C8—N1	127.4 (2)	H13E—C13—H13F	109.5
N2—C8—N1	104.1 (2)

C8—N2—N3—C7	1.7 (3)	C9—N1—C7—C1	16.6 (4)
C6—C1—C2—C3	−0.6 (4)	C6—C1—C7—N3	55.9 (4)
C7—C1—C2—C3	177.3 (3)	C2—C1—C7—N3	−122.1 (3)
C1—C2—C3—C4	−0.5 (5)	C6—C1—C7—N1	−125.7 (3)
C2—C3—C4—C5	1.7 (5)	C2—C1—C7—N1	56.4 (4)
C3—C4—C5—C6	−1.6 (5)	N3—N2—C8—O1	176.6 (3)
C3—C4—C5—C12	178.8 (3)	N3—N2—C8—N1	−2.6 (3)
C4—C5—C6—C1	0.5 (4)	C7—N1—C8—O1	−176.8 (3)
C12—C5—C6—C1	−179.9 (3)	C9—N1—C8—O1	−12.7 (5)
C2—C1—C6—C5	0.7 (4)	C7—N1—C8—N2	2.5 (3)
C7—C1—C6—C5	−177.3 (3)	C9—N1—C8—N2	166.6 (3)
N2—N3—C7—N1	0.0 (3)	C7—N1—C9—C10	80.2 (3)
N2—N3—C7—C1	178.7 (3)	C8—N1—C9—C10	−80.5 (3)
C8—N1—C7—N3	−1.6 (3)	N1—C9—C10—C11	178.9 (2)
C9—N1—C7—N3	−164.8 (3)	C9—C10—C11—C13	177.0 (2)
C8—N1—C7—C1	179.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H22···O1ⁱ	0.94 (3)	1.84 (3)	2.775 (3)	170 (3)

Symmetry code: (i) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₇N₃O
M_r	231.30
Crystal system, space group	Orthorhombic, Ccc2
Temperature (K)	296
a, b, c (Å)	16.905 (5), 18.139 (5), 8.145 (2)
V (Å³)	2497.5 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.26 × 0.19 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8129, 1791, 1118
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.106, 1.07
No. of reflections	1791
No. of parameters	160
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.25

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H22···O1ⁱ	0.94 (3)	1.84 (3)	2.775 (3)	170 (3)

Symmetry code: (i) x, −y+1, z−1/2.

Acknowledgements

The authors are grateful to the Higher Education Commission of Pakistan for a grant to purchase the diffractometer.

References

Akhtar, T., Hameed, S., Al-Masoudi, N. A. & Khan, K. M. (2007). Heteroatom. Chem. 18, 316–322. Web of Science CrossRef CAS Google Scholar
Akhtar, T., Hameed, S., Al-Masoudi, N. A., Loddo, R. & La Colla, P. (2008). Acta Pharm. 58, 135–149. Web of Science CrossRef PubMed CAS Google Scholar
Akhtar, T., Hameed, S., Lu, X., Yasin, K. A. & &Khan, M. H. (2006). Anal. Sci. X-ray Struct. Anal. Online, 22, x307–308. CSD CrossRef CAS Google Scholar
Al-Masoudi, I. A., Al-Soud, Y. A., Al-Salihi, N. J. & Al-Masoudi, N. A. (2006). Chem. Heterocycl. Compd, 42, 1377–1403. CrossRef CAS Google Scholar
Aoyama, Y., Yoshida, Y. & Sato, R. (1984). J. Biol. Chem. 259, 1661–1666. CAS PubMed Web of Science Google Scholar
Bruker (2007). APEX2, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Demirbas, N., Ugurluoglu, R. & Demirbas, A. (2002). Bioorg. Med. Chem. 10, 3717–3723. Web of Science CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Lin, R., Connolly, P. J., Huang, S., Wetter, S. K., Lu, Y., Murray, W. V., Emanuel, S. L., Gruninger, R. H., Fuentes-Pesquera, A. R., Rugg, C. A., Middleton, S. A. & Jolliffe, L. K. (2005). J. Med. Chem. 48, 4208-4211. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Torres, H. A., Hachem, R. Y., Chemaly, R. F., Kontoyiannis, D. P. & Raad, I. I. (2005). Lancet Infect. Dis. 5, 775–85. Web of Science CrossRef PubMed CAS Google Scholar
Witkowski, J. J., Robin, R. K., Sidwell, R. W. & Simon, L. N. (1972). J. Med. Chem. 15, 1150–1154. CrossRef CAS PubMed Web of Science Google Scholar