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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o2036.
Published online 2009 July 29. doi:  10.1107/S1600536809029481
PMCID: PMC2977322

2-(1H-Benzotriazol-1-yl)-1-(2-fluoro­benzo­yl)ethyl 4-methyl­benzoate

Abstract

In the crystal structure of the title compound, C23H18FN3O3, inter­molecular C—H(...)N hydrogen bonds link the mol­ecules into chains extended along the c axis. The packing is further stabilized by weak C—H(...)O and C—H(...)F inter­actions. The F atom is disordered over two equally occupied 1- and 5-positions of the benzene ring.

Related literature

For the pharmacological activity of 1H-benzotriazole and its derivatives, see: Chen & Wu (2005 [triangle]). For bond-length data, see: Allen et al. (1987 [triangle]).

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Object name is e-65-o2036-scheme1.jpg

Experimental

Crystal data

  • C23H18FN3O3
  • M r = 403.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2036-efi1.jpg
  • a = 20.478 (4) Å
  • b = 19.570 (4) Å
  • c = 9.969 (2) Å
  • β = 107.12 (3)°
  • V = 3818.0 (13) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 293 K
  • 0.10 × 0.06 × 0.02 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1997 [triangle]) T min = 0.990, T max = 0.998
  • 19476 measured reflections
  • 3368 independent reflections
  • 2698 reflections with I > 2σ(I)
  • R int = 0.058

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.177
  • S = 1.08
  • 3368 reflections
  • 282 parameters
  • 2 restraints
  • H-atom parameters constrained
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 1997 [triangle]); cell refinement: SAINT (Bruker, 1997 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809029481/at2823sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809029481/at2823Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This research has been supported by the Foundation of Weifang University.

supplementary crystallographic information

Comment

1H-Benzotriazoles 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 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 (Allen et al., 1987) and angles in (I) are within their normal ranges. The dihedral angle between the triazole ring (N1–N3/C10/C15) and the benzene ring (C10–C15) is 2.86 (12)°. The dihedral angles between the triazole ring and the C1–C6 and C17–C22 aromatic rings are 4.78 (13)° and 65.34 (13)°, respectively. The dihedral angle between the C1—C6 and C17–C22 rings is 62.04 (14)°. Molecule (I) is chiral. In the crystal structure, intermolecular C—H···N hydrogen bonds (Table1) link the molecules into chains extended along the c axis. The packing (Fig. 2) is further stabilized by weak C—H···O and C—H···F interactions (Table 1).

Experimental

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-(2-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 4-methylbenzoic acid (2.72 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. Single crystals of (I) were obtained by slow evaporation of an acetone-ethylacetate (3:1 v/v) solution at room temperature over a period of one week.

Refinement

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) and 1.5 Ueq(methyl C) H atoms. The F atom is disordered over two equally occupied positions on the 1 and 5-positions of the benzene ring.

Figures

Fig. 1.
The molecular structure of (I), drawn with 30% probability ellipsoids.

Crystal data

C23H18FN3O3F(000) = 1680
Mr = 403.40Dx = 1.404 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3992 reflections
a = 20.478 (4) Åθ = 2.1–25.0°
b = 19.570 (4) ŵ = 0.10 mm1
c = 9.969 (2) ÅT = 293 K
β = 107.12 (3)°Block, colourless
V = 3818.0 (13) Å30.10 × 0.06 × 0.02 mm
Z = 8

Data collection

Bruker SMART CCD diffractometer3368 independent reflections
Radiation source: fine-focus sealed tube2698 reflections with I > 2σ(I)
graphiteRint = 0.058
ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1997)h = −24→24
Tmin = 0.990, Tmax = 0.998k = −23→23
19476 measured reflectionsl = −11→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.177w = 1/[σ2(Fo2) + (0.0959P)2 + 1.3136P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.031
3368 reflectionsΔρmax = 0.38 e Å3
282 parametersΔρmin = −0.26 e Å3
2 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0028 (6)

Special details

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)

xyzUiso*/UeqOcc. (<1)
F10.46661 (19)0.21126 (19)0.3054 (4)0.0709 (10)0.50
F1'0.24580 (17)0.2535 (2)0.3171 (4)0.0717 (12)0.50
O10.29447 (10)0.12509 (10)0.30001 (18)0.0462 (5)
O20.35449 (9)0.05690 (8)0.13268 (16)0.0371 (5)
O30.43939 (11)0.06667 (10)0.3332 (2)0.0622 (7)
N10.23322 (11)0.12861 (10)−0.02778 (19)0.0326 (5)
N20.19010 (12)0.17037 (10)0.0132 (2)0.0378 (5)
N30.13058 (12)0.14092 (11)−0.0135 (2)0.0401 (6)
C10.41929 (16)0.25100 (14)0.3243 (3)0.0452 (7)
H1A0.45180.22100.30240.054*0.50
C20.44099 (19)0.31500 (17)0.3776 (3)0.0602 (9)
H20.48620.32860.39360.072*
C30.3935 (2)0.35812 (16)0.4063 (3)0.0649 (10)
H30.40640.40180.44050.078*
C40.3281 (2)0.33705 (15)0.3850 (3)0.0603 (9)
H40.29640.36620.40530.072*
C50.30868 (16)0.27283 (14)0.3337 (3)0.0487 (8)
H5A0.26240.25850.32040.058*0.50
C60.35371 (14)0.22830 (13)0.3012 (2)0.0367 (6)
C70.33146 (13)0.15790 (13)0.2505 (2)0.0349 (6)
C80.35328 (14)0.12962 (12)0.1289 (2)0.0358 (6)
H80.39890.14690.13390.043*
C90.30282 (13)0.15017 (12)−0.0110 (2)0.0365 (6)
H9A0.30360.1995−0.01990.044*
H9B0.31780.1307−0.08640.044*
C100.20015 (13)0.07007 (12)−0.0843 (2)0.0312 (6)
C110.21918 (14)0.01290 (12)−0.1472 (2)0.0361 (6)
H110.26320.0075−0.15380.043*
C120.16911 (14)−0.03490 (13)−0.1989 (3)0.0397 (7)
H120.1795−0.0740−0.24170.048*
C130.10262 (14)−0.02655 (14)−0.1889 (3)0.0435 (7)
H130.0701−0.0600−0.22610.052*
C140.08430 (14)0.02928 (14)−0.1262 (3)0.0418 (7)
H140.04030.0342−0.11870.050*
C150.13458 (13)0.07866 (12)−0.0740 (2)0.0341 (6)
C160.40188 (14)0.03020 (14)0.2459 (3)0.0439 (7)
C170.40226 (13)−0.04463 (13)0.2469 (2)0.0382 (6)
C180.36063 (14)−0.08304 (13)0.1382 (3)0.0391 (6)
H180.3305−0.06130.06180.047*
C190.36382 (15)−0.15284 (13)0.1430 (3)0.0397 (6)
H190.3358−0.17810.06920.048*
C200.40830 (14)−0.18695 (14)0.2562 (3)0.0418 (7)
C210.44946 (15)−0.14802 (15)0.3646 (3)0.0448 (7)
H210.4795−0.16970.44120.054*
C220.44658 (14)−0.07813 (14)0.3607 (3)0.0449 (7)
H220.4745−0.05290.43460.054*
C230.41090 (17)−0.26339 (14)0.2594 (3)0.0553 (8)
H23A0.4499−0.27810.33380.083*
H23B0.4145−0.28010.17140.083*
H23C0.3700−0.28090.27510.083*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
F10.056 (2)0.074 (2)0.086 (3)−0.018 (2)0.027 (2)−0.013 (2)
F1'0.034 (2)0.099 (3)0.070 (2)0.0195 (19)−0.0037 (17)−0.037 (2)
O10.0466 (12)0.0547 (12)0.0385 (10)−0.0151 (9)0.0143 (9)−0.0042 (9)
O20.0374 (10)0.0336 (9)0.0341 (9)0.0032 (8)0.0012 (8)−0.0012 (7)
O30.0624 (15)0.0522 (12)0.0512 (13)0.0025 (11)−0.0156 (11)−0.0096 (10)
N10.0364 (12)0.0303 (11)0.0287 (11)0.0038 (9)0.0059 (9)0.0007 (8)
N20.0453 (14)0.0351 (11)0.0301 (11)0.0105 (10)0.0065 (10)−0.0004 (9)
N30.0426 (14)0.0419 (13)0.0333 (12)0.0087 (10)0.0069 (10)−0.0014 (9)
C10.0571 (19)0.0436 (16)0.0391 (15)−0.0061 (14)0.0209 (14)0.0011 (12)
C20.078 (2)0.060 (2)0.0430 (17)−0.0303 (18)0.0181 (16)0.0019 (14)
C30.113 (3)0.0395 (17)0.0376 (17)−0.0130 (19)0.0156 (19)0.0022 (13)
C40.089 (3)0.0447 (17)0.0426 (17)0.0191 (18)0.0129 (17)−0.0022 (14)
C50.057 (2)0.0470 (17)0.0339 (14)0.0092 (14)0.0009 (13)−0.0034 (12)
C60.0462 (17)0.0371 (14)0.0244 (12)−0.0004 (12)0.0069 (11)0.0021 (10)
C70.0308 (14)0.0422 (14)0.0285 (12)−0.0025 (11)0.0039 (11)0.0057 (11)
C80.0369 (15)0.0328 (13)0.0361 (14)−0.0027 (11)0.0082 (12)−0.0007 (11)
C90.0429 (16)0.0329 (13)0.0321 (13)−0.0008 (11)0.0082 (12)0.0018 (10)
C100.0348 (14)0.0309 (13)0.0245 (12)0.0034 (10)0.0034 (10)0.0022 (10)
C110.0377 (15)0.0378 (14)0.0314 (13)0.0071 (11)0.0079 (11)−0.0006 (11)
C120.0440 (17)0.0340 (14)0.0365 (14)0.0032 (11)0.0046 (12)−0.0061 (11)
C130.0387 (16)0.0416 (15)0.0413 (15)−0.0038 (12)−0.0020 (12)−0.0023 (12)
C140.0334 (15)0.0512 (17)0.0378 (14)0.0042 (12)0.0058 (12)0.0023 (12)
C150.0370 (15)0.0344 (13)0.0268 (12)0.0075 (11)0.0029 (11)0.0016 (10)
C160.0405 (16)0.0475 (16)0.0356 (15)0.0056 (13)−0.0012 (13)−0.0016 (12)
C170.0388 (15)0.0419 (15)0.0310 (13)0.0085 (12)0.0058 (11)−0.0004 (11)
C180.0425 (16)0.0430 (15)0.0285 (13)0.0082 (12)0.0055 (12)0.0028 (11)
C190.0514 (17)0.0407 (15)0.0268 (13)0.0093 (12)0.0110 (12)−0.0001 (11)
C200.0509 (18)0.0456 (16)0.0364 (14)0.0138 (13)0.0244 (13)0.0071 (12)
C210.0438 (17)0.0564 (18)0.0339 (14)0.0192 (14)0.0109 (13)0.0098 (13)
C220.0388 (16)0.0559 (18)0.0347 (14)0.0100 (13)0.0025 (12)0.0005 (12)
C230.072 (2)0.0493 (17)0.0518 (17)0.0197 (15)0.0292 (16)0.0130 (14)

Geometric parameters (Å, °)

F1—C11.298 (4)C9—H9A0.9700
F1—H1A0.3515C9—H9B0.9700
F1'—C51.305 (4)C10—C151.387 (3)
F1'—H5A0.3449C10—C111.393 (3)
O1—C71.204 (3)C11—C121.371 (4)
O2—C161.358 (3)C11—H110.9300
O2—C81.424 (3)C12—C131.403 (4)
O3—C161.209 (3)C12—H120.9300
N1—N21.352 (3)C13—C141.365 (4)
N1—C101.365 (3)C13—H130.9300
N1—C91.448 (3)C14—C151.396 (4)
N2—N31.303 (3)C14—H140.9300
N3—C151.373 (3)C16—C171.465 (4)
C1—C61.368 (4)C17—C181.387 (4)
C1—C21.382 (4)C17—C221.390 (4)
C1—H1A0.9599C18—C191.368 (3)
C2—C31.379 (5)C18—H180.9300
C2—H20.9300C19—C201.394 (4)
C3—C41.357 (5)C19—H190.9300
C3—H30.9300C20—C211.386 (4)
C4—C51.371 (4)C20—C231.497 (4)
C4—H40.9300C21—C221.369 (4)
C5—C61.375 (4)C21—H210.9300
C5—H5A0.9601C22—H220.9300
C6—C71.492 (4)C23—H23A0.9600
C7—C81.515 (3)C23—H23B0.9600
C8—C91.525 (3)C23—H23C0.9600
C8—H80.9800
C1—F1—H1A13.4H9A—C9—H9B107.6
C5—F1'—H5A1.9N1—C10—C15104.0 (2)
C16—O2—C8114.16 (19)N1—C10—C11133.5 (2)
N2—N1—C10110.1 (2)C15—C10—C11122.4 (2)
N2—N1—C9119.8 (2)C12—C11—C10116.1 (2)
C10—N1—C9130.1 (2)C12—C11—H11122.0
N3—N2—N1109.03 (19)C10—C11—H11122.0
N2—N3—C15108.0 (2)C11—C12—C13121.9 (2)
F1—C1—C6121.2 (3)C11—C12—H12119.1
F1—C1—C2115.4 (3)C13—C12—H12119.1
C6—C1—C2123.2 (3)C14—C13—C12121.9 (3)
F1—C1—H1A4.9C14—C13—H13119.0
C6—C1—H1A118.4C12—C13—H13119.0
C2—C1—H1A118.4C13—C14—C15116.9 (3)
C3—C2—C1117.9 (3)C13—C14—H14121.5
C3—C2—H2121.1C15—C14—H14121.5
C1—C2—H2121.1N3—C15—C10108.9 (2)
C4—C3—C2120.3 (3)N3—C15—C14130.2 (2)
C4—C3—H3119.8C10—C15—C14120.8 (2)
C2—C3—H3119.8O3—C16—O2121.2 (2)
C3—C4—C5120.1 (3)O3—C16—C17125.7 (2)
C3—C4—H4119.9O2—C16—C17113.1 (2)
C5—C4—H4119.9C18—C17—C22119.0 (2)
F1'—C5—C4118.7 (3)C18—C17—C16122.4 (2)
F1'—C5—C6119.5 (3)C22—C17—C16118.6 (2)
C4—C5—C6121.8 (3)C19—C18—C17120.1 (2)
F1'—C5—H5A0.7C19—C18—H18119.9
C4—C5—H5A119.1C17—C18—H18119.9
C6—C5—H5A119.1C18—C19—C20121.3 (2)
C1—C6—C5116.6 (3)C18—C19—H19119.3
C1—C6—C7122.9 (2)C20—C19—H19119.4
C5—C6—C7120.4 (3)C21—C20—C19118.0 (2)
O1—C7—C6121.3 (2)C21—C20—C23121.5 (3)
O1—C7—C8120.2 (2)C19—C20—C23120.4 (3)
C6—C7—C8118.4 (2)C22—C21—C20121.0 (2)
O2—C8—C7110.6 (2)C22—C21—H21119.5
O2—C8—C9106.83 (19)C20—C21—H21119.5
C7—C8—C9110.8 (2)C21—C22—C17120.4 (3)
O2—C8—H8109.5C21—C22—H22119.8
C7—C8—H8109.5C17—C22—H22119.8
C9—C8—H8109.5C20—C23—H23A109.5
N1—C9—C8114.0 (2)C20—C23—H23B109.5
N1—C9—H9A108.7H23A—C23—H23B109.5
C8—C9—H9A108.7C20—C23—H23C109.5
N1—C9—H9B108.7H23A—C23—H23C109.5
C8—C9—H9B108.7H23B—C23—H23C109.5
C10—N1—N2—N30.5 (2)C9—N1—C10—C15−178.9 (2)
C9—N1—N2—N3179.16 (19)N2—N1—C10—C11176.5 (2)
N1—N2—N3—C15−0.3 (2)C9—N1—C10—C11−2.0 (4)
F1—C1—C2—C3−176.8 (3)N1—C10—C11—C12−176.5 (2)
C6—C1—C2—C3−1.2 (4)C15—C10—C11—C12−0.1 (3)
C1—C2—C3—C41.3 (4)C10—C11—C12—C130.1 (4)
C2—C3—C4—C5−0.5 (4)C11—C12—C13—C14−0.6 (4)
C3—C4—C5—F1'178.6 (3)C12—C13—C14—C151.0 (4)
C3—C4—C5—C6−0.6 (4)N2—N3—C15—C100.0 (3)
F1—C1—C6—C5175.6 (3)N2—N3—C15—C14−177.3 (2)
C2—C1—C6—C50.1 (4)N1—C10—C15—N30.2 (2)
F1—C1—C6—C7−1.4 (4)C11—C10—C15—N3−177.1 (2)
C2—C1—C6—C7−176.8 (2)N1—C10—C15—C14177.9 (2)
F1'—C5—C6—C1−178.4 (3)C11—C10—C15—C140.5 (4)
C4—C5—C6—C10.8 (4)C13—C14—C15—N3176.1 (2)
F1'—C5—C6—C7−1.4 (4)C13—C14—C15—C10−1.0 (4)
C4—C5—C6—C7177.8 (2)C8—O2—C16—O3−0.7 (4)
C1—C6—C7—O1137.2 (3)C8—O2—C16—C17−179.7 (2)
C5—C6—C7—O1−39.6 (4)O3—C16—C17—C18−175.6 (3)
C1—C6—C7—C8−46.1 (3)O2—C16—C17—C183.4 (4)
C5—C6—C7—C8137.1 (2)O3—C16—C17—C223.7 (4)
C16—O2—C8—C7−65.0 (3)O2—C16—C17—C22−177.3 (2)
C16—O2—C8—C9174.4 (2)C22—C17—C18—C19−0.5 (4)
O1—C7—C8—O2−28.4 (3)C16—C17—C18—C19178.8 (2)
C6—C7—C8—O2154.9 (2)C17—C18—C19—C200.2 (4)
O1—C7—C8—C989.9 (3)C18—C19—C20—C210.0 (4)
C6—C7—C8—C9−86.8 (3)C18—C19—C20—C23179.9 (3)
N2—N1—C9—C890.5 (3)C19—C20—C21—C220.0 (4)
C10—N1—C9—C8−91.1 (3)C23—C20—C21—C22−179.9 (3)
O2—C8—C9—N163.0 (3)C20—C21—C22—C17−0.3 (4)
C7—C8—C9—N1−57.5 (3)C18—C17—C22—C210.5 (4)
N2—N1—C10—C15−0.4 (2)C16—C17—C22—C21−178.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C8—H8···F10.982.242.938 (5)127
C9—H9A···N2i0.972.553.515 (3)174
C12—H12···O1ii0.932.483.118 (4)126
C18—H18···O20.932.432.741 (3)100
C22—H22···O3iii0.932.483.259 (4)142
C23—H23C···F1'iv0.962.373.090 (5)131

Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x, −y, z−1/2; (iii) −x+1, −y, −z+1; (iv) −x+1/2, y−1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2823).

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.
  • Bruker (1997). SADABS, SMART and SAINT . Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chen, Z.-Y. & Wu, M.-J. (2005). Org. Lett.7, 475–477. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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