supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

hb2525 scheme

Acta Cryst. (2007). E63, o3978    [ doi:10.1107/S1600536807041876 ]

3-(1H-Benzotriazol-1-yl)-1-(4-fluorobenzoyl)ethyl benzoate

W.-L. Zeng

Abstract top

In the crystal structure of the title compound, C22H16FN3O3, weak intermolecular C-H...O hydrogen bonds link the molecules into chains extending along the C axis. The packing is further stabilized by weak C-H...[pi] interactions.

Comment top

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

All the bond lengths and angles in (I) are within their normal ranges (Allen et al., 1987). The benzotriazole ring system is essentially planar, with a dihedral angle of 0.83 (1)° between the triazole ring (atoms N1–N3/C10/C15) and the C10–C15 benzene ring. The dihedral angles between the mean planes of the benzotriazole system and the C1–C6 and C17–C22 aromatic rings are 6.52 (1)° and 82.67 (1)°, respectively. The dihedral angle between rings C1–C6 and C17–C22 is 78.04 (2)°. In the arbitrarily chosen asymmetric molecule, atom C8 has R configuration, but crystal symmetry generates a racemic mixture.

In the crystal structure of (I), weak intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into chains extended along the c axis. The packing is further stabilized by weak C—H···π interactions.

Related literature top

For background, see Chen & Wu (2005). For reference structural data, 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-(4-fluorophenyl)propan-1-one (5.38 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 saturated sodium bicarbonate solution and brine, dried over anhydrous magnesium sulfate and the chloroform solution filtered. It was cooled with ice–water, and then an acetone solution (10 ml) of benzoic acid (2.44 g, 0.02 mol) and triethylamine (2.8 ml) was added. The mixture was stirred with ice–water for 6 h. The solution was then filtered and concentrated. Colourless blocks of (I) were obtained by slow evaporation of an acetone–ethyl acetate (1:1 v/v) solution at room temperature over a period of one week.

Refinement top

The H atoms were geometrically placed (C—H = 0.93–0.97 Å), and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Bruker, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids (arbitrary spheres for the H atoms).
3-(1H-Benzotriazol-1-yl)-1-(4-fluorobenzoyl)ethyl benzoate top
Crystal data top
C22H16FN3O3F000 = 808
Mr = 389.38Dx = 1.375 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1779 reflections
a = 10.302 (10) Åθ = 2.6–22.7º
b = 9.089 (9) ŵ = 0.10 mm−1
c = 20.38 (2) ÅT = 294 (2) K
β = 99.687 (18)ºBlock, colourless
V = 1881 (3) Å30.22 × 0.20 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		3322 independent reflections
Radiation source: fine-focus sealed tube1791 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.056
T = 294(2) Kθmax = 25.0º
ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −12→12
Tmin = 0.978, Tmax = 0.990k = −10→8
9421 measured reflectionsl = −24→24
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)] = 0.047H-atom parameters constrained
wR(F2) = 0.130  w = 1/[σ2(Fo2) + (0.0593P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
3322 reflectionsΔρmax = 0.16 e Å−3
262 parametersΔρmin = −0.23 e Å−3
6 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
C22H16FN3O3V = 1881 (3) Å3
Mr = 389.38Z = 4
Monoclinic, P21/cMo Kα
a = 10.302 (10) ŵ = 0.10 mm−1
b = 9.089 (9) ÅT = 294 (2) K
c = 20.38 (2) Å0.22 × 0.20 × 0.10 mm
β = 99.687 (18)º
Data collection top
Bruker SMART CCD
diffractometer		3322 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		1791 reflections with I > 2σ(I)
Tmin = 0.978, Tmax = 0.990Rint = 0.056
9421 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0476 restraints
wR(F2) = 0.130H-atom parameters constrained
S = 1.01Δρmax = 0.16 e Å−3
3322 reflectionsΔρmin = −0.23 e Å−3
262 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 > 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
F10.94092 (17)0.1533 (3)0.44908 (9)0.1242 (8)
O10.39664 (16)−0.0227 (2)0.28432 (8)0.0588 (5)
O20.31492 (14)0.16117 (18)0.18101 (7)0.0469 (5)
O30.32855 (15)0.30853 (19)0.26935 (8)0.0532 (5)
N10.48331 (19)0.1106 (2)0.08562 (9)0.0496 (6)
N20.5827 (2)0.1996 (3)0.07466 (11)0.0709 (7)
N30.5485 (3)0.2671 (3)0.01856 (12)0.0819 (8)
C10.6228 (3)0.0203 (3)0.37736 (11)0.0581 (8)
H10.5576−0.04110.38850.070*
C20.7357 (3)0.0418 (4)0.42226 (13)0.0745 (9)
H20.7476−0.00340.46380.089*
C30.8298 (3)0.1305 (4)0.40478 (14)0.0739 (9)
C40.8165 (3)0.1986 (4)0.34496 (14)0.0747 (9)
H40.88300.25900.33460.090*
C50.7027 (2)0.1770 (3)0.29968 (13)0.0574 (7)
H50.69240.22240.25820.069*
C60.6038 (2)0.0881 (3)0.31566 (11)0.0430 (6)
C70.4792 (2)0.0597 (3)0.26952 (11)0.0436 (6)
C80.4535 (2)0.1342 (3)0.20131 (10)0.0431 (6)
H80.50190.22740.20320.052*
C90.4947 (2)0.0355 (3)0.14860 (11)0.0526 (7)
H9A0.58510.00440.16270.063*
H9B0.4396−0.05170.14340.063*
C100.3811 (2)0.1219 (3)0.03451 (11)0.0517 (7)
C110.2580 (3)0.0561 (3)0.02138 (14)0.0711 (9)
H110.2302−0.01280.04980.085*
C120.1798 (3)0.1005 (5)−0.03694 (17)0.0938 (12)
H120.09550.0615−0.04820.113*
C130.2236 (4)0.2020 (5)−0.07940 (15)0.1014 (13)
H130.16740.2280−0.11830.122*
C140.3428 (4)0.2638 (4)−0.06664 (14)0.0909 (11)
H140.37020.3315−0.09570.109*
C150.4241 (3)0.2226 (3)−0.00807 (12)0.0633 (8)
C160.2639 (2)0.2577 (3)0.22011 (11)0.0420 (6)
C170.1242 (2)0.2922 (3)0.19600 (11)0.0451 (6)
C180.0535 (3)0.2316 (3)0.13901 (13)0.0731 (9)
H180.09370.16520.11400.088*
C19−0.0769 (3)0.2694 (4)0.11903 (15)0.0917 (11)
H19−0.12430.22840.08050.110*
C20−0.1362 (3)0.3655 (4)0.15498 (16)0.0776 (9)
H20−0.22430.38970.14140.093*
C21−0.0677 (3)0.4266 (4)0.21063 (15)0.0718 (9)
H21−0.10880.49350.23490.086*
C220.0624 (2)0.3907 (3)0.23167 (12)0.0582 (7)
H220.10870.43320.27010.070*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0861 (13)0.177 (2)0.0929 (12)−0.0360 (14)−0.0312 (11)0.0036 (13)
O10.0515 (10)0.0589 (13)0.0657 (11)−0.0106 (10)0.0090 (9)0.0108 (10)
O20.0415 (9)0.0508 (12)0.0469 (9)0.0075 (8)0.0031 (7)−0.0072 (8)
O30.0537 (10)0.0575 (13)0.0471 (10)−0.0039 (9)0.0049 (8)−0.0114 (9)
N10.0454 (12)0.0618 (16)0.0429 (11)0.0074 (11)0.0108 (10)0.0017 (11)
N20.0561 (14)0.097 (2)0.0633 (15)−0.0029 (14)0.0204 (12)0.0056 (15)
N30.0809 (19)0.106 (2)0.0638 (15)−0.0046 (16)0.0251 (14)0.0170 (16)
C10.0610 (17)0.068 (2)0.0448 (14)−0.0075 (14)0.0080 (13)0.0028 (14)
C20.077 (2)0.099 (3)0.0440 (15)−0.0052 (19)−0.0001 (15)0.0075 (17)
C30.0587 (18)0.096 (3)0.0601 (18)−0.0087 (18)−0.0102 (15)−0.0058 (18)
C40.0537 (17)0.084 (2)0.083 (2)−0.0153 (16)−0.0003 (15)0.0078 (19)
C50.0504 (16)0.063 (2)0.0584 (15)0.0008 (15)0.0073 (13)0.0114 (15)
C60.0423 (14)0.0426 (16)0.0450 (14)0.0004 (12)0.0099 (11)−0.0013 (13)
C70.0405 (14)0.0415 (16)0.0501 (14)0.0037 (12)0.0110 (11)−0.0040 (13)
C80.0391 (13)0.0444 (16)0.0453 (13)0.0061 (12)0.0057 (11)0.0004 (12)
C90.0535 (15)0.0586 (19)0.0461 (14)0.0164 (13)0.0093 (12)0.0050 (14)
C100.0538 (16)0.0589 (19)0.0429 (14)0.0141 (14)0.0094 (13)−0.0100 (14)
C110.0649 (19)0.083 (2)0.0644 (18)0.0010 (17)0.0082 (15)−0.0143 (17)
C120.070 (2)0.135 (4)0.071 (2)0.006 (2)−0.0037 (19)−0.031 (2)
C130.099 (3)0.157 (4)0.0454 (18)0.038 (3)0.0023 (19)−0.001 (2)
C140.102 (3)0.118 (3)0.0538 (19)0.029 (2)0.0181 (18)0.016 (2)
C150.072 (2)0.079 (2)0.0414 (15)0.0200 (17)0.0172 (14)0.0067 (16)
C160.0469 (14)0.0382 (16)0.0423 (13)0.0013 (12)0.0114 (12)0.0013 (13)
C170.0451 (14)0.0451 (16)0.0458 (13)0.0008 (12)0.0098 (11)0.0001 (13)
C180.0512 (17)0.091 (2)0.0729 (18)0.0159 (16)−0.0013 (14)−0.0283 (18)
C190.0537 (18)0.126 (3)0.087 (2)0.021 (2)−0.0109 (16)−0.036 (2)
C200.0441 (16)0.093 (3)0.094 (2)0.0149 (17)0.0089 (16)−0.004 (2)
C210.0556 (18)0.072 (2)0.092 (2)0.0141 (16)0.0238 (16)−0.0106 (18)
C220.0573 (17)0.061 (2)0.0580 (15)0.0033 (15)0.0148 (13)−0.0084 (15)
Geometric parameters (Å, °) top
F1—C31.349 (3)C9—H9A0.9700
O1—C71.209 (3)C9—H9B0.9700
O2—C161.350 (3)C10—C151.384 (4)
O2—C81.439 (3)C10—C111.387 (4)
O3—C161.200 (3)C11—C121.379 (4)
N1—N21.353 (3)C11—H110.9300
N1—C101.355 (3)C12—C131.391 (5)
N1—C91.441 (3)C12—H120.9300
N2—N31.293 (3)C13—C141.336 (5)
N3—C151.366 (4)C13—H130.9300
C1—C21.368 (4)C14—C151.389 (4)
C1—C61.384 (3)C14—H140.9300
C1—H10.9300C16—C171.474 (3)
C2—C31.354 (4)C17—C221.375 (3)
C2—H20.9300C17—C181.378 (3)
C3—C41.353 (4)C18—C191.380 (4)
C4—C51.379 (3)C18—H180.9300
C4—H40.9300C19—C201.351 (4)
C5—C61.381 (3)C19—H190.9300
C5—H50.9300C20—C211.350 (4)
C6—C71.481 (3)C20—H200.9300
C7—C81.529 (3)C21—C221.377 (4)
C8—C91.514 (3)C21—H210.9300
C8—H80.9800C22—H220.9300
C16—O2—C8114.01 (17)N1—C10—C15104.0 (2)
N2—N1—C10109.9 (2)N1—C10—C11133.1 (3)
N2—N1—C9118.7 (2)C15—C10—C11122.9 (3)
C10—N1—C9131.1 (2)C12—C11—C10115.0 (3)
N3—N2—N1109.2 (2)C12—C11—H11122.5
N2—N3—C15108.0 (2)C10—C11—H11122.5
C2—C1—C6121.2 (3)C11—C12—C13121.8 (3)
C2—C1—H1119.4C11—C12—H12119.1
C6—C1—H1119.4C13—C12—H12119.1
C3—C2—C1118.4 (3)C14—C13—C12122.8 (3)
C3—C2—H2120.8C14—C13—H13118.6
C1—C2—H2120.8C12—C13—H13118.6
F1—C3—C4118.6 (3)C13—C14—C15117.1 (3)
F1—C3—C2118.7 (3)C13—C14—H14121.5
C4—C3—C2122.7 (3)C15—C14—H14121.5
C3—C4—C5118.9 (3)N3—C15—C10108.9 (2)
C3—C4—H4120.5N3—C15—C14130.6 (3)
C5—C4—H4120.5C10—C15—C14120.4 (3)
C4—C5—C6120.2 (2)O3—C16—O2121.8 (2)
C4—C5—H5119.9O3—C16—C17124.8 (2)
C6—C5—H5119.9O2—C16—C17113.4 (2)
C5—C6—C1118.5 (2)C22—C17—C18118.7 (2)
C5—C6—C7123.2 (2)C22—C17—C16118.4 (2)
C1—C6—C7118.3 (2)C18—C17—C16122.9 (2)
O1—C7—C6121.4 (2)C17—C18—C19119.9 (3)
O1—C7—C8118.6 (2)C17—C18—H18120.0
C6—C7—C8120.0 (2)C19—C18—H18120.0
O2—C8—C9106.25 (17)C20—C19—C18120.5 (3)
O2—C8—C7110.42 (18)C20—C19—H19119.7
C9—C8—C7110.9 (2)C18—C19—H19119.7
O2—C8—H8109.8C21—C20—C19120.1 (3)
C9—C8—H8109.8C21—C20—H20119.9
C7—C8—H8109.7C19—C20—H20119.9
N1—C9—C8111.1 (2)C20—C21—C22120.5 (3)
N1—C9—H9A109.4C20—C21—H21119.7
C8—C9—H9A109.4C22—C21—H21119.7
N1—C9—H9B109.4C17—C22—C21120.2 (3)
C8—C9—H9B109.4C17—C22—H22119.9
H9A—C9—H9B108.0C21—C22—H22119.9
C10—N1—N2—N3−0.2 (3)N2—N1—C10—C11−179.8 (3)
C9—N1—N2—N3−173.8 (2)C9—N1—C10—C11−7.2 (4)
N1—N2—N3—C150.2 (3)N1—C10—C11—C12178.7 (3)
C6—C1—C2—C3−0.6 (4)C15—C10—C11—C12−1.2 (4)
C1—C2—C3—F1179.4 (3)C10—C11—C12—C131.0 (5)
C1—C2—C3—C40.1 (5)C11—C12—C13—C14−0.5 (6)
F1—C3—C4—C5−179.4 (3)C12—C13—C14—C150.0 (5)
C2—C3—C4—C5−0.1 (5)N2—N3—C15—C10−0.2 (3)
C3—C4—C5—C60.5 (4)N2—N3—C15—C14178.9 (3)
C4—C5—C6—C1−0.9 (4)N1—C10—C15—N30.1 (3)
C4—C5—C6—C7−179.9 (2)C11—C10—C15—N3180.0 (2)
C2—C1—C6—C51.0 (4)N1—C10—C15—C14−179.1 (3)
C2—C1—C6—C7180.0 (2)C11—C10—C15—C140.8 (4)
C5—C6—C7—O1177.5 (2)C13—C14—C15—N3−179.2 (3)
C1—C6—C7—O1−1.5 (4)C13—C14—C15—C10−0.2 (5)
C5—C6—C7—C8−2.0 (4)C8—O2—C16—O3−4.1 (3)
C1—C6—C7—C8179.1 (2)C8—O2—C16—C17175.90 (19)
C16—O2—C8—C9−175.00 (19)O3—C16—C17—C220.6 (4)
C16—O2—C8—C764.7 (3)O2—C16—C17—C22−179.3 (2)
O1—C7—C8—O232.2 (3)O3—C16—C17—C18179.9 (3)
C6—C7—C8—O2−148.3 (2)O2—C16—C17—C18−0.1 (3)
O1—C7—C8—C9−85.2 (3)C22—C17—C18—C19−0.4 (4)
C6—C7—C8—C994.2 (3)C16—C17—C18—C19−179.6 (3)
N2—N1—C9—C883.0 (3)C17—C18—C19—C20−0.1 (5)
C10—N1—C9—C8−89.1 (3)C18—C19—C20—C210.6 (6)
O2—C8—C9—N165.9 (2)C19—C20—C21—C22−0.6 (5)
C7—C8—C9—N1−174.1 (2)C18—C17—C22—C210.3 (4)
N2—N1—C10—C150.0 (3)C16—C17—C22—C21179.6 (2)
C9—N1—C10—C15172.7 (2)C20—C21—C22—C170.2 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O1i0.932.593.292 (5)133
C8—H8···O1i0.982.503.470 (5)173
C9—H9A···O3ii0.972.343.057 (4)130
C1—H1···Cgii0.932.953.730 (5)143
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O1i0.932.593.292 (5)133
C8—H8···O1i0.982.503.470 (5)173
C9—H9A···O3ii0.972.343.057 (4)130
C1—H1···Cgii0.932.953.730 (5)143
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2.
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). SMART, SAINT, SADABS and SHELXTL. Bruker AXS, Inc., Madison, Wisconsin, USA.

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

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. [Reference not cited - may it be removed?]