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Acta Cryst. (2007). E63, o3715    [ doi:10.1107/S1600536807036331 ]

2-(1H-1,2,3-Benzotriazol-1-yl)-1-benzoylethyl 4-methylbenzoate

W.-L. Zeng, Y.-C. Zhang and Y.-M. Hong

Abstract top

In the crystal structure of the title compound, C23H19N3O3, molecules are linked into chains parallel to the c axis by C-H...O hydrogen bonds. Adjacent chains are assembled into two-dimensional layers via C-H...N hydrogen bonds. The packing is further stabilized by [pi]-[pi] interactions between triazole and phenyl rings.

Comment top

1H-Benzotriazole and its derivatives are an important class of compounds because they exhibit a broad spectrum of pharmacological activities such as antifungal, antitumor and antineoplastic activities (Chen & Wu, 2005). We report here the synthesis and crystal structure of the title compound as part of our ongoing studies on new benzotriazole compounds with higher bioactivity.

In the title compound (Fig. 1), all bond lengths and angles are within normal ranges (Allen et al., 1987). The benzotriazole ring system is essentially planar, with a dihedral angle of 2.67 (1)° between the triazole ring (atoms N1—N3/C1/C6) and the benzene ring (C1—C6). The dihedral angles between the mean planes of the benzotriazole system and the six-membered aromatic rings C10—C15 and C17—C22 are 6.85 (1) and 66.06 (1)°, respectively. The dihedral angle between these two latter rings is 61.7 (2)°. In the crystal structure, intermolecular C—H···O hydrogen bonds (Table1) link the molecules into chains running parallel to the c axis. Adjacent chains are assembled into two-dimensional layers via C—H···N hydrogen bonds (Fig. 2). The packing is further stabilized by π···π interactions occurring between symmetry-related triazole and phenyl rings [Cg1···Cg2i = 3.578 (3) Å; perpendicular interplanar distance = 3.568 (3) Å; Cg1 and Cg2 are the centroids of the N1—N3/C1/C6 triazole ring and C10—C15 phenyl ring, respectively; symmetry code: (i) 1/2 − x, 1/2 − y, 2 − z].

Related literature top

For a general background on the pharmacological activities of benzotriazoles, see: Chen & Wu (2005). For related literature, see: Allen et al. (1987).

Experimental top

Bromine (3.2 g, 0.02 mol) was added dropwise to a solution of 3-(1H-benzo[d][1,2,3]triazol-1-yl)-1-phenylpropan-1-one (5.0 g, 0.02 mol) and sodium acetate (1.6 g, 0.02 mol) in acetic acid (50 ml). The reaction proceeded for 7 h. Water (50 ml) and chloroform (20 ml) were then added. The organic layer was washed successively with a saturated sodium bicarbonate solution and brine, dried over anhydrous magnesium sulfate and the chloroform solution filtered. This fraction was cooled with ice-water, then a solution of 4-methylbenzoic acid (2.7 g, 0.02 mol) in acetone (10 ml) and triethylamine (2.8 ml) was added. The mixture was stirred with ice-water for about 6 h. The solution was then filtered and concentrated. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an acetone-ethylacetate (1:1 v/v) solution at room temperature over a period of one week.

Refinement top

All H atoms were located in difference Fourier maps and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.97 Å, and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C) for the methyl group.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound with 30% probability ellipsoids.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed along the c axis. Intermolecular hydrogen bonds are shown as dashed lines.
2-(1H-1,2,3-Benzotriazol-1-yl)-1-benzoylethyl 4-methylbenzoate top
Crystal data top
C23H19N3O3F000 = 1616
Mr = 385.41Dx = 1.314 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1885 reflections
a = 20.376 (4) Åθ = 2.3–22.6º
b = 19.648 (4) ŵ = 0.09 mm−1
c = 10.213 (2) ÅT = 294 (2) K
β = 107.605 (4)ºBlock, colourless
V = 3897.3 (13) Å30.22 × 0.18 × 0.12 mm
Z = 8
Data collection top
Siemens SMART CCD area-detector
diffractometer		3994 independent reflections
Radiation source: fine-focus sealed tube2014 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.046
T = 294(2) Kθmax = 26.4º
φ and ω scansθmin = 1.5º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→25
Tmin = 0.981, Tmax = 0.989k = −24→20
11106 measured reflectionsl = −12→9
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.140  w = 1/[σ2(Fo2) + (0.063P)2 + 0.064P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.004
3994 reflectionsΔρmax = 0.26 e Å−3
263 parametersΔρmin = −0.17 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C23H19N3O3V = 3897.3 (13) Å3
Mr = 385.41Z = 8
Monoclinic, C2/cMo Kα
a = 20.376 (4) ŵ = 0.09 mm−1
b = 19.648 (4) ÅT = 294 (2) K
c = 10.213 (2) Å0.22 × 0.18 × 0.12 mm
β = 107.605 (4)º
Data collection top
Siemens SMART CCD area-detector
diffractometer		3994 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2014 reflections with I > 2σ(I)
Tmin = 0.981, Tmax = 0.989Rint = 0.046
11106 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.049263 parameters
wR(F2) = 0.140H-atom parameters constrained
S = 1.00Δρmax = 0.26 e Å−3
3994 reflectionsΔρmin = −0.17 e Å−3
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 > 2sigma(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
xyzUiso*/Ueq
O10.20658 (8)0.12677 (8)0.70219 (18)0.0703 (5)
O20.14502 (7)0.05617 (7)0.86281 (16)0.0550 (4)
O30.05904 (9)0.06461 (9)0.6674 (2)0.0879 (6)
N10.36982 (10)0.14012 (10)1.0086 (2)0.0598 (5)
N20.30975 (10)0.16959 (9)0.9822 (2)0.0581 (5)
N30.26645 (9)0.12819 (9)1.02305 (18)0.0471 (5)
C10.36587 (11)0.07846 (11)1.0694 (2)0.0475 (6)
C20.41650 (11)0.02937 (13)1.1214 (3)0.0624 (7)
H20.46080.03421.11460.075*
C30.39807 (13)−0.02585 (13)1.1825 (3)0.0703 (8)
H30.4306−0.05961.21800.084*
C40.33142 (12)−0.03349 (12)1.1938 (3)0.0648 (7)
H40.3213−0.07181.23770.078*
C50.28111 (11)0.01386 (11)1.1421 (2)0.0538 (6)
H50.23680.00861.14820.065*
C60.30000 (10)0.07063 (10)1.0794 (2)0.0431 (5)
C70.19630 (11)0.14953 (11)1.0045 (2)0.0542 (6)
H7A0.19530.19871.01300.065*
H7B0.18080.13001.07730.065*
C80.14636 (11)0.12887 (11)0.8666 (2)0.0519 (6)
H80.10030.14570.86090.062*
C90.16798 (11)0.15841 (12)0.7499 (2)0.0524 (6)
C100.14402 (11)0.22827 (11)0.7005 (2)0.0500 (6)
C110.18920 (13)0.27258 (14)0.6695 (3)0.0662 (7)
H110.23450.25930.68240.079*
C120.16787 (18)0.33635 (15)0.6197 (3)0.0817 (9)
H120.19900.36650.60080.098*
C130.1012 (2)0.35565 (15)0.5977 (3)0.0873 (10)
H130.08680.39880.56320.105*
C140.05536 (15)0.31160 (16)0.6266 (3)0.0809 (9)
H140.00970.32450.61060.097*
C150.07713 (12)0.24794 (13)0.6795 (3)0.0642 (7)
H150.04630.21830.70090.077*
C160.09767 (11)0.02871 (13)0.7527 (3)0.0605 (7)
C170.09855 (10)−0.04588 (12)0.7526 (2)0.0522 (6)
C180.05402 (11)−0.08051 (14)0.6424 (2)0.0627 (7)
H180.0250−0.05630.56940.075*
C190.05285 (12)−0.15056 (14)0.6412 (3)0.0636 (7)
H190.0227−0.17300.56700.076*
C200.09510 (12)−0.18837 (13)0.7469 (3)0.0597 (7)
C210.13932 (12)−0.15321 (13)0.8558 (3)0.0611 (6)
H210.1684−0.17760.92840.073*
C220.14135 (12)−0.08347 (12)0.8595 (2)0.0597 (7)
H220.1716−0.06130.93400.072*
C230.09377 (14)−0.26485 (13)0.7461 (3)0.0859 (9)
H23A0.1385−0.28190.75070.129*
H23B0.0607−0.28060.66320.129*
H23C0.0812−0.28090.82410.129*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0719 (11)0.0785 (12)0.0655 (12)0.0248 (9)0.0282 (10)0.0047 (9)
O20.0508 (9)0.0517 (10)0.0530 (11)−0.0020 (7)0.0011 (8)0.0017 (8)
O30.0787 (13)0.0800 (13)0.0767 (14)−0.0005 (10)−0.0187 (10)0.0139 (11)
N10.0540 (12)0.0652 (14)0.0566 (14)−0.0139 (10)0.0112 (10)0.0065 (10)
N20.0613 (13)0.0522 (12)0.0573 (14)−0.0143 (10)0.0124 (10)0.0042 (10)
N30.0496 (11)0.0458 (11)0.0425 (12)−0.0046 (9)0.0087 (9)−0.0003 (9)
C10.0451 (13)0.0523 (14)0.0410 (14)−0.0127 (11)0.0065 (10)−0.0011 (11)
C20.0433 (13)0.0721 (18)0.0647 (18)−0.0037 (13)0.0059 (12)0.0003 (14)
C30.0598 (17)0.0604 (17)0.077 (2)0.0031 (13)0.0007 (14)0.0091 (14)
C40.0644 (17)0.0558 (16)0.0639 (18)−0.0124 (13)0.0040 (13)0.0122 (13)
C50.0488 (13)0.0560 (15)0.0517 (16)−0.0076 (12)0.0079 (11)0.0042 (12)
C60.0437 (12)0.0437 (13)0.0363 (13)−0.0070 (10)0.0037 (10)−0.0021 (10)
C70.0607 (15)0.0494 (14)0.0532 (16)0.0033 (11)0.0182 (12)0.0002 (11)
C80.0467 (13)0.0529 (15)0.0520 (16)0.0078 (11)0.0087 (11)0.0023 (12)
C90.0439 (13)0.0620 (16)0.0468 (15)0.0083 (12)0.0072 (11)−0.0041 (12)
C100.0558 (14)0.0502 (14)0.0396 (14)0.0047 (12)0.0079 (11)−0.0036 (11)
C110.0646 (16)0.0695 (18)0.0588 (17)−0.0023 (14)0.0101 (13)−0.0005 (14)
C120.111 (3)0.065 (2)0.068 (2)−0.0196 (18)0.0262 (18)−0.0009 (16)
C130.136 (3)0.0563 (18)0.062 (2)0.024 (2)0.019 (2)0.0025 (15)
C140.084 (2)0.084 (2)0.070 (2)0.0360 (18)0.0181 (16)0.0020 (17)
C150.0630 (16)0.0662 (17)0.0630 (18)0.0133 (13)0.0183 (13)0.0049 (14)
C160.0463 (14)0.0723 (19)0.0525 (17)−0.0045 (13)−0.0007 (12)0.0066 (14)
C170.0469 (13)0.0599 (16)0.0456 (15)−0.0069 (11)0.0074 (11)0.0016 (12)
C180.0523 (15)0.079 (2)0.0481 (16)−0.0104 (13)0.0026 (12)0.0011 (13)
C190.0606 (16)0.079 (2)0.0513 (17)−0.0233 (14)0.0168 (13)−0.0140 (14)
C200.0667 (16)0.0667 (17)0.0547 (17)−0.0143 (13)0.0319 (14)−0.0076 (14)
C210.0711 (17)0.0628 (17)0.0472 (16)−0.0055 (13)0.0145 (13)−0.0017 (13)
C220.0612 (15)0.0623 (17)0.0468 (16)−0.0076 (12)0.0033 (12)−0.0037 (13)
C230.106 (2)0.071 (2)0.090 (2)−0.0212 (16)0.0433 (18)−0.0181 (16)
Geometric parameters (Å, °) top
O1—C91.214 (2)C10—C111.372 (3)
O2—C161.353 (3)C11—C121.373 (4)
O2—C81.429 (2)C11—H110.9300
O3—C161.209 (3)C12—C131.362 (4)
N1—N21.306 (2)C12—H120.9300
N1—C11.375 (3)C13—C141.369 (4)
N2—N31.356 (2)C13—H130.9300
N3—C61.356 (3)C14—C151.381 (4)
N3—C71.446 (3)C14—H140.9300
C1—C61.385 (3)C15—H150.9300
C1—C21.395 (3)C16—C171.466 (3)
C2—C31.360 (3)C17—C221.386 (3)
C2—H20.9300C17—C181.391 (3)
C3—C41.405 (3)C18—C191.377 (3)
C3—H30.9300C18—H180.9300
C4—C51.367 (3)C19—C201.377 (3)
C4—H40.9300C19—H190.9300
C5—C61.397 (3)C20—C211.386 (3)
C5—H50.9300C20—C231.503 (3)
C7—C81.522 (3)C21—C221.371 (3)
C7—H7A0.9700C21—H210.9300
C7—H7B0.9700C22—H220.9300
C8—C91.507 (3)C23—H23A0.9600
C8—H80.9800C23—H23B0.9600
C9—C101.493 (3)C23—H23C0.9600
C10—C151.370 (3)
C16—O2—C8115.11 (18)C10—C11—C12120.4 (2)
N2—N1—C1107.75 (18)C10—C11—H11119.8
N1—N2—N3109.08 (18)C12—C11—H11119.8
N2—N3—C6109.84 (17)C13—C12—C11120.2 (3)
N2—N3—C7119.70 (18)C13—C12—H12119.9
C6—N3—C7130.46 (18)C11—C12—H12119.9
N1—C1—C6108.76 (19)C12—C13—C14120.0 (3)
N1—C1—C2130.1 (2)C12—C13—H13120.0
C6—C1—C2121.1 (2)C14—C13—H13120.0
C3—C2—C1116.8 (2)C13—C14—C15119.8 (3)
C3—C2—H2121.6C13—C14—H14120.1
C1—C2—H2121.6C15—C14—H14120.1
C2—C3—C4122.1 (2)C10—C15—C14120.2 (3)
C2—C3—H3119.0C10—C15—H15119.9
C4—C3—H3119.0C14—C15—H15119.9
C5—C4—C3121.7 (2)O3—C16—O2120.8 (2)
C5—C4—H4119.1O3—C16—C17126.0 (2)
C3—C4—H4119.1O2—C16—C17113.2 (2)
C4—C5—C6116.3 (2)C22—C17—C18118.5 (2)
C4—C5—H5121.9C22—C17—C16122.5 (2)
C6—C5—H5121.9C18—C17—C16119.0 (2)
N3—C6—C1104.56 (18)C19—C18—C17120.1 (2)
N3—C6—C5133.4 (2)C19—C18—H18120.0
C1—C6—C5122.0 (2)C17—C18—H18120.0
N3—C7—C8113.69 (18)C18—C19—C20121.8 (2)
N3—C7—H7A108.8C18—C19—H19119.1
C8—C7—H7A108.8C20—C19—H19119.1
N3—C7—H7B108.8C19—C20—C21117.4 (2)
C8—C7—H7B108.8C19—C20—C23122.0 (2)
H7A—C7—H7B107.7C21—C20—C23120.6 (3)
O2—C8—C9111.77 (18)C22—C21—C20121.8 (2)
O2—C8—C7107.09 (18)C22—C21—H21119.1
C9—C8—C7110.83 (19)C20—C21—H21119.1
O2—C8—H8109.0C21—C22—C17120.3 (2)
C9—C8—H8109.0C21—C22—H22119.8
C7—C8—H8109.0C17—C22—H22119.8
O1—C9—C10121.4 (2)C20—C23—H23A109.5
O1—C9—C8120.0 (2)C20—C23—H23B109.5
C10—C9—C8118.51 (19)H23A—C23—H23B109.5
C15—C10—C11119.3 (2)C20—C23—H23C109.5
C15—C10—C9121.4 (2)H23A—C23—H23C109.5
C11—C10—C9119.2 (2)H23B—C23—H23C109.5
C1—N1—N2—N3−0.6 (2)C7—C8—C9—C10−87.0 (2)
N1—N2—N3—C60.9 (2)O1—C9—C10—C15138.4 (2)
N1—N2—N3—C7−179.93 (18)C8—C9—C10—C15−44.9 (3)
N2—N1—C1—C60.2 (2)O1—C9—C10—C11−38.5 (3)
N2—N1—C1—C2−177.3 (2)C8—C9—C10—C11138.1 (2)
N1—C1—C2—C3176.8 (2)C15—C10—C11—C120.9 (4)
C6—C1—C2—C3−0.4 (3)C9—C10—C11—C12177.9 (2)
C1—C2—C3—C4−0.2 (4)C10—C11—C12—C13−1.4 (4)
C2—C3—C4—C50.9 (4)C11—C12—C13—C140.6 (4)
C3—C4—C5—C6−1.0 (3)C12—C13—C14—C150.8 (4)
N2—N3—C6—C1−0.7 (2)C11—C10—C15—C140.5 (4)
C7—N3—C6—C1−179.8 (2)C9—C10—C15—C14−176.4 (2)
N2—N3—C6—C5176.6 (2)C13—C14—C15—C10−1.3 (4)
C7—N3—C6—C5−2.4 (4)C8—O2—C16—O3−1.6 (3)
N1—C1—C6—N30.3 (2)C8—O2—C16—C17179.55 (18)
C2—C1—C6—N3178.1 (2)O3—C16—C17—C22−175.4 (3)
N1—C1—C6—C5−177.4 (2)O2—C16—C17—C223.4 (3)
C2—C1—C6—C50.3 (3)O3—C16—C17—C183.5 (4)
C4—C5—C6—N3−176.6 (2)O2—C16—C17—C18−177.7 (2)
C4—C5—C6—C10.4 (3)C22—C17—C18—C190.3 (3)
N2—N3—C7—C889.4 (2)C16—C17—C18—C19−178.6 (2)
C6—N3—C7—C8−91.6 (3)C17—C18—C19—C20−0.2 (4)
C16—O2—C8—C9−65.0 (2)C18—C19—C20—C210.1 (3)
C16—O2—C8—C7173.46 (19)C18—C19—C20—C23179.8 (2)
N3—C7—C8—O263.2 (2)C19—C20—C21—C220.1 (4)
N3—C7—C8—C9−58.9 (2)C23—C20—C21—C22−179.7 (2)
O2—C8—C9—O1−29.6 (3)C20—C21—C22—C170.0 (4)
C7—C8—C9—O189.8 (3)C18—C17—C22—C21−0.2 (4)
O2—C8—C9—C10153.67 (18)C16—C17—C22—C21178.7 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O1i0.932.503.157 (3)128
C7—H7A···N2ii0.972.593.560 (3)176
C18—H18···O3iii0.932.513.317 (3)145
Symmetry codes: (i) x, −y, z+1/2; (ii) −x+1/2, −y+1/2, −z+2; (iii) −x, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O1i0.932.503.157 (3)128
C7—H7A···N2ii0.972.593.560 (3)176
C18—H18···O3iii0.932.513.317 (3)145
Symmetry codes: (i) x, −y, z+1/2; (ii) −x+1/2, −y+1/2, −z+2; (iii) −x, −y, −z+1.
references
References top

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.

Bruker (1997). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Chen, Z.-Y. & Wu, M.-J. (2005). Org. Lett. 7, 475–477.

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