4-Benzyl-1-p-tolyl-1H-1,2,4-triazol-5(4H)-one

Zhu, Y.-J.; Duan, H.-Q.

doi:10.1107/S1600536809002487

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o384

doi:10.1107/S1600536809002487

Open

access

4-Benzyl-1-p-tolyl-1H-1,2,4-triazol-5(4H)-one

Yu-Jin Zhu ^a,^b and Hong-Quan Duan ^a ^*

^aSchool of Pharmacy, Tianjin Medical University, Tianjin 300070, People's Republic of China, and ^bSchool of Chinese Armed Police Force Medical College, Tianjin 300162, People's Republic of China
^*Correspondence e-mail: duanhongquan2009@yahoo.cn

(Received 20 January 2009; accepted 20 January 2009; online 23 January 2009)

In the title compound, C₁₆H₁₅N₃O, the triazole ring makes dihedral angles of 7.08 (2) and 74.53 (3)° with the two outer aromatic rings. The crystal packing is stabilized by very short intermolecular C—H⋯O hydrogen bonds and weak π–π stacking interactions [centroid-to-centroid distance 3.632 (3) Å], resulting in the formation of zigzag chains parallel to the b axis.

Related literature

For details of the biological activity of trisubstituted triazolinones, see: Chang et al. (1993 , 1994 ). For bond-length data, see: Allen et al. (1987 ). For details of synthesis, see: Theodoridis (1998 ).

Experimental

Crystal data

C₁₆H₁₅N₃O
M_r = 265.31
Monoclinic, P 2₁ /n
a = 4.6130 (9) Å
b = 25.488 (5) Å
c = 11.460 (2) Å
β = 96.18 (3)°
V = 1339.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 113 (2) K
0.18 × 0.04 × 0.04 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.985, T_max = 0.997
9828 measured reflections
2333 independent reflections
1998 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.150
S = 1.10
2333 reflections
183 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1ⁱ	0.93	2.19	3.114 (2)	174
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809002487/hg2470sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809002487/hg2470Isup2.hkl

checkCIF report

Comment top

4-Benzyl-1-p-tolyl-1H-1,2,4-triazol-5(4H)-one is a N-substituted triazolinone. It was reported that trisubstituted triazolinones were employed as nonpeptide angiotensin II receptor antagonists (Chang et al., 1993, 1994). In our effort to further study triazolinone derivatives as novel AII antagonists, the title compound was prepared. Here, we report the crystal structure of it.

In title compound, all bond lengths in the molecule are normal (Allen et al., 1987). The triazole ring N1–N3/C8–C9 makes dihedral angles of 7.08 (2) and 74.53 (3)° with the two phenyl rings (C1–C6, C11–C16). The relatively short distance of 3.632 (3) Å between the centroids of triazole ring N1–N3/C8–C9 and benzene ring C1–C6 [at -1 + x, y, z] indicates the presence of weak π–π interactions, The crystal packing is stabilized by intermolecular C—H···O hydrogen bonds, linking the molecules into zigzag chains parallel to the b axis.

Related literature top

For details of the biological activity of trisubstituted triazolinones, see: Chang et al. (1993, 1994). For bond-length data, see: Allen et al. (1987). For details of synthesis, see: Theodoridis (1998).

Experimental top

1-p-Tolyl-1H-1,2,4-triazol-5(4H)one (1.75 g, 0.01 mol) was dissolved in 30 ml of acetic anhydride, 1.38 g (0.01 mol) potassium carbonate and 0.75 ml (0.01 mol) phenylmethanol were added. The solution was heated to reflux and stirred for 2 h and then cooled to room temperature. 100 ml of water was added and the deposited precipitate filtered. The precipitate was recrystallized with aetone and dried to give 4-benzyl-1-p-tolyl-1H-1,2,4-triazol-5(4H)one as a colorless power (2.40 g, yield 90.5%) (Theodoridis, 1998). Crystals suitable for X-ray diffraction were obtained through slow evaporation of the solution of the title compound in dichloromethane and ethyl acetate (v/v 1:1).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.

4-Benzyl-1-p-tolyl-1H-1,2,4-triazol-5(4H)-one top

Crystal data top

C₁₆H₁₅N₃O	F(000) = 560
M_r = 265.31	D_x = 1.315 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2910 reflections
a = 4.6130 (9) Å	θ = 1.6–27.9°
b = 25.488 (5) Å	µ = 0.09 mm⁻¹
c = 11.460 (2) Å	T = 113 K
β = 96.18 (3)°	Block, colourless
V = 1339.6 (5) Å³	0.18 × 0.04 × 0.04 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	2333 independent reflections
Radiation source: rotating anode	1998 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.052
ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −5→5
T_min = 0.985, T_max = 0.997	k = −30→30
9828 measured reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.150	w = 1/[σ²(F_o²) + (0.0922P)²] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max < 0.001
2333 reflections	Δρ_max = 0.23 e Å⁻³
183 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.030 (5)

Crystal data top

C₁₆H₁₅N₃O	V = 1339.6 (5) Å³
M_r = 265.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.6130 (9) Å	µ = 0.09 mm⁻¹
b = 25.488 (5) Å	T = 113 K
c = 11.460 (2) Å	0.18 × 0.04 × 0.04 mm
β = 96.18 (3)°

Data collection top

Rigaku Saturn diffractometer	2333 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1998 reflections with I > 2σ(I)
T_min = 0.985, T_max = 0.997	R_int = 0.052
9828 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.150	H-atom parameters constrained
S = 1.10	Δρ_max = 0.23 e Å⁻³
2333 reflections	Δρ_min = −0.26 e Å⁻³
183 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
O1	0.4812 (3)	0.20822 (5)	0.27648 (11)	0.0298 (4)
N1	0.5904 (3)	0.17809 (5)	0.09066 (12)	0.0250 (4)
N2	0.5011 (4)	0.19124 (6)	−0.02578 (13)	0.0328 (4)
N3	0.2711 (3)	0.24033 (5)	0.09506 (13)	0.0267 (4)
C1	0.7986 (4)	0.13699 (6)	0.11575 (15)	0.0247 (4)
C2	0.8840 (4)	0.10765 (7)	0.02333 (16)	0.0295 (5)
H2	0.8061	0.1147	−0.0533	0.035*
C3	1.0867 (4)	0.06763 (7)	0.04622 (16)	0.0310 (5)
H3	1.1441	0.0483	−0.0162	0.037*
C4	1.2065 (4)	0.05553 (7)	0.15959 (17)	0.0281 (5)
C5	1.1164 (4)	0.08567 (7)	0.25051 (17)	0.0305 (5)
H5	1.1928	0.0784	0.3272	0.037*
C6	0.9155 (4)	0.12638 (7)	0.23019 (16)	0.0284 (5)
H6	0.8605	0.1462	0.2923	0.034*
C7	1.4263 (4)	0.01155 (7)	0.18258 (18)	0.0337 (5)
H7A	1.6175	0.0243	0.1720	0.051*
H7B	1.3764	−0.0167	0.1287	0.051*
H7C	1.4243	−0.0009	0.2616	0.051*
C8	0.4527 (4)	0.20823 (6)	0.16844 (16)	0.0242 (4)
C9	0.3125 (4)	0.22863 (7)	−0.01808 (17)	0.0328 (5)
H9	0.2161	0.2456	−0.0828	0.039*
C10	0.0864 (4)	0.28203 (7)	0.13604 (18)	0.0306 (5)
H10A	0.0539	0.2752	0.2169	0.037*
H10B	−0.1016	0.2817	0.0891	0.037*
C11	0.2243 (4)	0.33566 (7)	0.12782 (15)	0.0265 (5)
C12	0.4397 (4)	0.35251 (7)	0.21405 (16)	0.0326 (5)
H12	0.4966	0.3310	0.2779	0.039*
C13	0.5705 (5)	0.40130 (8)	0.20553 (18)	0.0370 (5)
H13	0.7158	0.4121	0.2631	0.044*
C14	0.4840 (5)	0.43383 (7)	0.11114 (17)	0.0374 (5)
H14	0.5691	0.4667	0.1057	0.045*
C15	0.2713 (5)	0.41719 (8)	0.02540 (18)	0.0388 (5)
H15	0.2142	0.4389	−0.0381	0.047*
C16	0.1420 (4)	0.36866 (7)	0.03274 (17)	0.0328 (5)
H16	−0.0006	0.3579	−0.0259	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0334 (8)	0.0304 (7)	0.0250 (7)	0.0016 (5)	0.0005 (6)	−0.0033 (5)
N1	0.0277 (9)	0.0245 (8)	0.0224 (8)	0.0005 (6)	0.0004 (6)	0.0006 (6)
N2	0.0443 (10)	0.0300 (9)	0.0235 (9)	0.0029 (8)	0.0013 (7)	0.0019 (7)
N3	0.0273 (9)	0.0239 (8)	0.0284 (9)	0.0020 (6)	0.0012 (7)	0.0001 (6)
C1	0.0235 (10)	0.0226 (9)	0.0282 (10)	−0.0032 (7)	0.0032 (8)	0.0008 (7)
C2	0.0331 (11)	0.0297 (10)	0.0266 (10)	−0.0023 (8)	0.0066 (8)	0.0018 (7)
C3	0.0328 (11)	0.0295 (10)	0.0326 (11)	−0.0003 (8)	0.0125 (9)	−0.0039 (8)
C4	0.0217 (10)	0.0250 (9)	0.0384 (11)	−0.0046 (7)	0.0063 (8)	0.0005 (8)
C5	0.0273 (11)	0.0337 (11)	0.0295 (10)	−0.0012 (8)	−0.0012 (8)	0.0006 (8)
C6	0.0288 (11)	0.0274 (10)	0.0285 (11)	0.0000 (8)	0.0013 (8)	−0.0038 (7)
C7	0.0286 (11)	0.0288 (10)	0.0440 (12)	0.0015 (8)	0.0053 (9)	0.0009 (9)
C8	0.0244 (10)	0.0217 (9)	0.0258 (10)	−0.0045 (7)	0.0002 (7)	−0.0009 (7)
C9	0.0377 (12)	0.0308 (10)	0.0287 (11)	0.0021 (8)	−0.0019 (9)	0.0032 (8)
C10	0.0258 (11)	0.0271 (10)	0.0395 (11)	0.0012 (8)	0.0056 (9)	0.0002 (8)
C11	0.0265 (10)	0.0251 (9)	0.0292 (10)	0.0033 (7)	0.0088 (8)	−0.0008 (7)
C12	0.0383 (12)	0.0303 (10)	0.0292 (10)	0.0032 (8)	0.0035 (9)	−0.0023 (8)
C13	0.0376 (12)	0.0362 (11)	0.0365 (12)	−0.0032 (9)	0.0013 (9)	−0.0107 (9)
C14	0.0443 (13)	0.0280 (10)	0.0421 (13)	−0.0082 (9)	0.0151 (10)	−0.0037 (9)
C15	0.0486 (14)	0.0325 (11)	0.0360 (12)	−0.0005 (9)	0.0075 (10)	0.0066 (9)
C16	0.0332 (12)	0.0321 (10)	0.0319 (11)	0.0009 (8)	−0.0008 (9)	0.0002 (8)

Geometric parameters (Å, º) top

O1—C8	1.231 (2)	C7—H7A	0.9600
N1—C8	1.382 (2)	C7—H7B	0.9600
N1—N2	1.394 (2)	C7—H7C	0.9600
N1—C1	1.429 (2)	C9—H9	0.9300
N2—C9	1.299 (2)	C10—C11	1.515 (2)
N3—C9	1.364 (2)	C10—H10A	0.9700
N3—C8	1.388 (2)	C10—H10B	0.9700
N3—C10	1.471 (2)	C11—C12	1.392 (3)
C1—C2	1.388 (2)	C11—C16	1.397 (3)
C1—C6	1.390 (2)	C12—C13	1.390 (3)
C2—C3	1.390 (3)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.387 (3)
C3—C4	1.391 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.379 (3)
C4—C5	1.394 (3)	C14—H14	0.9300
C4—C7	1.516 (2)	C15—C16	1.379 (3)
C5—C6	1.394 (3)	C15—H15	0.9300
C5—H5	0.9300	C16—H16	0.9300
C6—H6	0.9300

C8—N1—N2	112.01 (14)	O1—C8—N1	129.94 (16)
C8—N1—C1	128.55 (15)	O1—C8—N3	126.98 (16)
N2—N1—C1	119.43 (14)	N1—C8—N3	103.07 (15)
C9—N2—N1	104.01 (15)	N2—C9—N3	112.84 (16)
C9—N3—C8	108.06 (15)	N2—C9—H9	123.6
C9—N3—C10	127.37 (16)	N3—C9—H9	123.6
C8—N3—C10	124.41 (15)	N3—C10—C11	111.73 (14)
C2—C1—C6	120.14 (16)	N3—C10—H10A	109.3
C2—C1—N1	118.77 (16)	C11—C10—H10A	109.3
C6—C1—N1	121.10 (15)	N3—C10—H10B	109.3
C1—C2—C3	119.47 (17)	C11—C10—H10B	109.3
C1—C2—H2	120.3	H10A—C10—H10B	107.9
C3—C2—H2	120.3	C12—C11—C16	118.79 (17)
C2—C3—C4	122.05 (17)	C12—C11—C10	120.45 (16)
C2—C3—H3	119.0	C16—C11—C10	120.75 (17)
C4—C3—H3	119.0	C13—C12—C11	120.55 (18)
C3—C4—C5	117.13 (17)	C13—C12—H12	119.7
C3—C4—C7	121.17 (17)	C11—C12—H12	119.7
C5—C4—C7	121.71 (17)	C14—C13—C12	119.93 (19)
C4—C5—C6	122.13 (18)	C14—C13—H13	120.0
C4—C5—H5	118.9	C12—C13—H13	120.0
C6—C5—H5	118.9	C15—C14—C13	119.65 (18)
C1—C6—C5	119.08 (17)	C15—C14—H14	120.2
C1—C6—H6	120.5	C13—C14—H14	120.2
C5—C6—H6	120.5	C14—C15—C16	120.78 (19)
C4—C7—H7A	109.5	C14—C15—H15	119.6
C4—C7—H7B	109.5	C16—C15—H15	119.6
H7A—C7—H7B	109.5	C15—C16—C11	120.30 (18)
C4—C7—H7C	109.5	C15—C16—H16	119.8
H7A—C7—H7C	109.5	C11—C16—H16	119.8
H7B—C7—H7C	109.5

C8—N1—N2—C9	−0.07 (19)	C9—N3—C8—O1	178.18 (18)
C1—N1—N2—C9	179.13 (15)	C10—N3—C8—O1	2.4 (3)
C8—N1—C1—C2	172.54 (16)	C9—N3—C8—N1	−0.95 (18)
N2—N1—C1—C2	−6.5 (2)	C10—N3—C8—N1	−176.71 (14)
C8—N1—C1—C6	−7.7 (3)	N1—N2—C9—N3	−0.6 (2)
N2—N1—C1—C6	173.26 (15)	C8—N3—C9—N2	1.0 (2)
C6—C1—C2—C3	0.1 (3)	C10—N3—C9—N2	176.61 (16)
N1—C1—C2—C3	179.85 (15)	C9—N3—C10—C11	−75.1 (2)
C1—C2—C3—C4	0.5 (3)	C8—N3—C10—C11	99.78 (19)
C2—C3—C4—C5	−0.5 (3)	N3—C10—C11—C12	−80.5 (2)
C2—C3—C4—C7	179.72 (15)	N3—C10—C11—C16	98.3 (2)
C3—C4—C5—C6	−0.1 (3)	C16—C11—C12—C13	−0.1 (3)
C7—C4—C5—C6	179.67 (16)	C10—C11—C12—C13	178.78 (17)
C2—C1—C6—C5	−0.7 (3)	C11—C12—C13—C14	0.7 (3)
N1—C1—C6—C5	179.57 (15)	C12—C13—C14—C15	−0.9 (3)
C4—C5—C6—C1	0.7 (3)	C13—C14—C15—C16	0.4 (3)
N2—N1—C8—O1	−178.45 (17)	C14—C15—C16—C11	0.3 (3)
C1—N1—C8—O1	2.4 (3)	C12—C11—C16—C15	−0.4 (3)
N2—N1—C8—N3	0.64 (18)	C10—C11—C16—C15	−179.28 (17)
C1—N1—C8—N3	−178.46 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.93	2.19	3.114 (2)	174

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅N₃O
M_r	265.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	4.6130 (9), 25.488 (5), 11.460 (2)
β (°)	96.18 (3)
V (Å³)	1339.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.18 × 0.04 × 0.04

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.985, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	9828, 2333, 1998
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.150, 1.10
No. of reflections	2333
No. of parameters	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.26

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.93	2.19	3.114 (2)	174.4

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Chang, L. L., Ashton, W. T., Flanagan, K. L., Chen, T.-B., O'Malley, S. S., Zingaro, G. J., Siegl, P. K. S., Kivlighn, S. D., Lotti, V. J. & Greenlee, W. J. (1994). J. Med. Chem. 37, 4464–4478. CrossRef CAS PubMed Web of Science Google Scholar
Chang, L. L., Ashton, W. T., Flanagan, K. L., Strelitz, R. A., MacCoss, M., Greenlee, W. J., Chang, R. S. L., Lotti, V. J., Faust, K. A., Chen, T.-B., Bunting, P., Zingaro, G. J., Kivlighn, S. D. & Siegl, P. K. S. (1993). J. Med. Chem. 36, 2558–2568. CrossRef CAS PubMed Web of Science Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Theodoridis, G. (1998). Tetrahedron Lett. 39, 9365–9368. Web of Science CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o384

doi:10.1107/S1600536809002487

Open

access