2 [(2 Phenyl 1,3 oxazol 4 yl)­methyl] 2H 1,2,3 benzotriazole

Acta Cryst.(2001). E57, o35±o36 DOI: 101107/S1600536800018808 Swaleh and Ziemer C₁₆H₁₂N₄O

o35

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Acta Crystallographica Section E

Structure Reports

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ISSN 1600-5368

2-[(2-Phenyl-1,3-oxazol-4-yl)methyl]-2H-1,2,3-benzo-triazole

Sauda Swaleh and Burkhard Ziemer*

Institut fuÈr Chemie, Humboldt-UniversitaÈt zu Berlin, Hessische Straûe 1-2, 10115 Berlin, Germany

Correspondence e-mail:

[email protected]

Key indicators

Single-crystal X-ray study

T= 180 K

Mean(C±C) = 0.003 AÊ

Rfactor = 0.040

wRfactor = 0.082 Data-to-parameter ratio = 8.3

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, C16H12N4O, was obtained through a two-step process. There are two molecules in the asymmetric unit with essentially equal bond lengths. The phenyl and oxazole rings are essentially coplanar. Steric interactions between the two halves of the molecule produce a wide angle at the central C atom.

Comment

The title compound, (I), was obtained through a two-step process. By reaction of 5-bromo-4-(bromomethyl)-2-phenyl-1,3-oxazole and a mixture of N -(1-cyanoethyl)benzene-sulfonamide and benzotriazole in the presence of a base and small traces of DMSO, the N-alkylation took place with the more reactive benzotriazole. A halogen±lithium exchange reaction was conducted on the obtained product resulting in the formation of (I).

There are two molecules in the asymmetric unit. All corresponding bond lengths are equal within 2 and in accordance with the chemical diagram. In both molecules, the dihedral angle between the phenyl and oxazole rings (less than 5_{) indicates communicatingsystems. The steric demand of}

the ring systems on the two sides of the molecule seems to have the effects (i) that the tetrahedral angle at the centre of the molecule formed by the non-H atoms is signi®cantly enlarged to 112.0 (3) and 111.0 (3) _{in the two molecules,}

respectively, and (ii) that the halves of the molecule are inclined to each other by about 43 and 33 _{in the two}

mol-ecules.

Experimental

Following the method of Lesbosquain & Decruix (1993), 5-bromo-4-(bromomethyl)-2-phenyl-1,3-oxazole, K2CO3and a mixture ofN

-(1-cyanoethyl)benzenesulfonamide and benzotriazole in the presence of traces of DMSO were re¯uxed in acetonitrile for 1 h. The resulting suspension was cooled, ®ltered and concentrated under reduced pressure, and the obtained compound was puri®ed by column

matography. Br±Li exchange reaction was further carried out on the puri®ed compound at 173 K for 2 h, as already described by Swaleh & Liebscher (1999). The compound isolated by subsequent column chromatography was recrystallized from absolute ethanol, affording (I).

Crystal data C16H12N4O Mr= 276.30

Monoclinic,P21 a= 14.880 (2) AÊ b= 4.6251 (5) AÊ c= 20.043 (3) AÊ = 100.963 (19) V= 1354.2 (3) AÊ3 Z= 4

Dx= 1.355 Mg mÿ3

MoKradiation Cell parameters from 4003

re¯ections = 3.1±24.3 = 0.09 mmÿ1 T= 180 (2) K Prism, colorless 0.520.240.12 mm Data collection

Stoe IPDS diffractometer Scans:'-rotation,'-incr. = 1.2_{, 183}

exposures

9269 measured re¯ections 2943 independent re¯ections 2202 re¯ections withI> 2(I)

Rint= 0.068

max= 25.9 h=ÿ18!18 k=ÿ5!5 l=ÿ24!24

Re®nement Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.040} wR(F2_{) = 0.082} S= 0.95 2943 re¯ections 356 parameters

H-atom parameters not re®ned

w= 1/[2_(F

o2) + (0.0401P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.17 e AÊÿ3

min=ÿ0.16 e AÊÿ3

Extinction correction:SHELXL97 Extinction coef®cient: 0.009 (2)

To save variable parameters, both monosubstituted benzene rings were re®ned as rigid ideal hexagons. This seems to be justi®ed, because every ring is bonded to a C atom; and in such a case, according to Domenicanoet al.(1975), the ideal symmetry of the C6

-hexagon is maintained. 2235 Friedel pairs were measured,i.e.75.2% of those possible, and they were merged in the data set.

Data collection: IPDS-2.87 (Stoe & Cie, 1997); cell re®nement:

IPDS-2.87; data reduction: IPDS-2.87; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

OPTEP-3 (Farrugia, 1997); software used to prepare material for publication:SHELXL97.

References

Domenicano, A., Vaciago, A. & Coulson, C. A. (1975).Acta Cryst.B31, 221± 233.

Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.

Lesbosquain, D. & Decruix, B. (1993).Heterocycles,36, 2303±2314. Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Stoe & Cie (1997).IPDS-2.87. Stoe & Cie, Darmstadt, Germany. Swaleh, S. M. & Liebscher, J. (1999).Tetrahedron Lett.40, 2099±2100. Figure 1

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Acta Cryst. (2001). E57, o35–o36 [doi:10.1107/S1600536800018808]

2-[(2-Phenyl-1,3-oxazol-4-yl)methyl]-2

H

-1,2,3-benzotriazole

Sauda Swaleh and Burkhard Ziemer

S1. Comment

The title compound, (I), was obtained through a two-step process. By reaction of 5-bromo-4-(bromomethyl)-2-phenyl-1,3-oxazole and a mixture of N-(1-cyanoethyl)benzenesulfonamide and benzotriazole in the presence of a base and small traces of DMSO, the N-alkylation took place with the more reactive benzotriazole. A halogen–lithium exchange reaction was conducted on the obtained product resulting in the formation of (I).

There are two molecules in the asymmetric unit. All corresponding bond lengths are equal within 2σ and in accordance with the chemical diagram. In both molecules, the dihedral angle between the phenyl and oxazole rings (less than 5°) indicates communicating π systems. The steric demand of the ring systems on the two sides of the molecule seems to have the effects (i) that the tetrahedral angle at the centre of the molecule formed by the non-H atoms is significantly enlarged to 112.0 (3) and 111.0 (3)° in the two molecules, respectively, and (ii) that the halves of the molecule are inclined to each other by about 43 and 33° in the two molecules.

S2. Experimental

Following the method of Lesbosquain & Decruix (1993), 5-bromo-4(bromomethyl)-2-phenyl-1,3-oxazole, K2CO3 and a

mixture of N-(1-cyanoethyl)benzenesulfonamide and benzotriazole in the presence of traces of DMSO were refluxed in acetonitrile for 1 h. The resulting suspension was cooled, filtered and concentrated under reduced pressure, and the obtained compound was purified by column chromatography. Br–Li exchange reaction was further carried out on the purified compound at 173 K for 2 h, as already described by Swaleh & Liebscher (1999). The compound isolated by subsequent column chromatography was recrystallized from absolute ethanol, affording (I).

S3. Refinement

To save variable parameters, both monosubstituted benzene rings were refined as rigid ideal hexagons. This seems to be justified, because every ring is bonded to a C atom; and in such a case, according to Domenicano et al. (1975), the ideal symmetry of the C6-hexagon is maintained. 2235 Friedel pairs were measured, i.e. 75.2% of those possible, and they were

Figure 1

The structure of one molecule OF (I) showing 50% probability ellipsoids.

1-[(2-phenyl-1,3-oxazol-4-yl)methyl]-1H-1,2,3-benzotriazole

Crystal data

C16H12N4O

Mr = 276.30 Monoclinic, P21

a = 14.880 (2) Å

b = 4.6251 (5) Å

c = 20.043 (3) Å

β = 100.963 (19)°

V = 1354.2 (3) Å3

Z = 4

F(000) = 576

Dx = 1.355 Mg m−3

Melting point: 376(1) K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4003 reflections

θ = 3.1–24.3°

µ = 0.09 mm−1

T = 180 K Prism, colorless 0.52 × 0.24 × 0.12 mm

Data collection

Stoe IPDS diffractometer

Radiation source: fine-focus sealed X-ray tube Planar graphite monochromator

Detector resolution: 6.667 pixels mm-1

φ–rotation, φ–incr. = 1.2°, 183 exposures scans 9269 measured reflections

2943 independent reflections 2202 reflections with I > 2σ(I)

Rint = 0.068

θmax = 25.9°, θmin = 2.3°

h = −18→18

k = −5→5

l = −24→24

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.040}

wR(F2_{) = 0.082}

S = 0.95 2943 reflections 356 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters not refined

w = 1/[σ2_(F

o2) + (0.0401P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.17 e Å−3

Δρmin = −0.16 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

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Special details

Experimental. Recrystallized from ethanol. During data collection the crystal was in cold N2 gas of the Cryostream

Cooler (Oxford Cryosystems, 1992) mounted on a φ-axis diffractometer supplied with an area detector.

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

H35 0.1963 −0.4027 0.6703 0.060* C36 0.11415 (14) −0.4811 (5) 0.57853 (10) 0.0525 (10) H36 0.0748 −0.6145 0.5948 0.063* C37 0.09956 (12) −0.4118 (5) 0.50984 (9) 0.0493 (9) H37 0.0502 −0.4978 0.4792 0.059* C38 0.15710 (13) −0.2166 (5) 0.48599 (7) 0.0402 (8) H38 0.1471 −0.1692 0.4390 0.048* C40 0.35437 (17) 0.4084 (8) 0.44633 (13) 0.0301 (7) C41 0.39498 (19) 0.4419 (8) 0.51185 (13) 0.0365 (8) H41 0.4438 0.5709 0.5284 0.044* C42 0.37294 (19) 0.5678 (8) 0.38533 (12) 0.0339 (7) H42A 0.3168 0.6707 0.3631 0.041* H42B 0.4214 0.7136 0.3998 0.041* C45 0.39843 (17) 0.1057 (7) 0.25065 (13) 0.0289 (7) C46 0.37797 (18) −0.0470 (8) 0.18831 (13) 0.0347 (8) H46 0.3214 −0.0214 0.1577 0.042* C47 0.44326 (19) −0.2325 (8) 0.17417 (13) 0.0371 (8) H47 0.4317 −0.3381 0.1328 0.045* C48 0.5284 (2) −0.2719 (8) 0.21994 (13) 0.0390 (8) H48 0.5717 −0.4050 0.2084 0.047* C49 0.54947 (19) −0.1230 (8) 0.28005 (13) 0.0359 (8) H49 0.6067 −0.1478 0.3099 0.043* C50 0.48256 (18) 0.0686 (7) 0.29570 (12) 0.0289 (7) O1 −0.00585 (11) 0.1743 (5) 0.12147 (8) 0.0339 (5) O31 0.35385 (12) 0.2580 (5) 0.55065 (8) 0.0370 (5) N9 0.14449 (14) 0.0937 (6) 0.13455 (10) 0.0312 (6) N13 0.23177 (14) 0.2829 (6) 0.01091 (10) 0.0297 (6) N14 0.32274 (14) 0.2526 (6) 0.02065 (10) 0.0324 (6) N21 0.18141 (15) 0.1361 (6) −0.04007 (11) 0.0353 (7) N39 0.28587 (15) 0.1994 (6) 0.44192 (10) 0.0316 (6) N43 0.40198 (14) 0.3690 (6) 0.33659 (10) 0.0295 (6) N44 0.34733 (14) 0.3007 (6) 0.27797 (10) 0.0323 (6) N51 0.48369 (14) 0.2369 (6) 0.35103 (10) 0.0316 (6)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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C16 0.0268 (14) 0.046 (2) 0.0372 (15) −0.0009 (15) 0.0063 (11) 0.0022 (15) C17 0.0365 (16) 0.040 (2) 0.0407 (15) 0.0038 (16) 0.0182 (12) 0.0041 (16) C18 0.0443 (18) 0.051 (3) 0.0368 (15) −0.0085 (17) 0.0171 (13) −0.0099 (15) C19 0.0341 (16) 0.053 (3) 0.0375 (15) −0.0121 (16) 0.0112 (12) −0.0099 (16) C20 0.0278 (14) 0.034 (2) 0.0287 (13) −0.0053 (13) 0.0120 (11) 0.0008 (13) C32 0.0321 (15) 0.028 (2) 0.0340 (14) 0.0076 (14) 0.0084 (12) −0.0020 (13) C33 0.0370 (16) 0.032 (2) 0.0370 (14) 0.0093 (15) 0.0179 (12) 0.0029 (14) C34 0.0557 (19) 0.042 (3) 0.0400 (16) 0.0029 (18) 0.0196 (14) 0.0038 (16) C35 0.066 (2) 0.047 (3) 0.0452 (17) 0.009 (2) 0.0301 (17) 0.0077 (17) C36 0.058 (2) 0.039 (3) 0.073 (2) 0.0071 (18) 0.0421 (18) 0.0106 (19) C37 0.0434 (18) 0.044 (3) 0.065 (2) 0.0016 (17) 0.0224 (16) 0.0014 (19) C38 0.0408 (16) 0.038 (2) 0.0456 (16) 0.0040 (16) 0.0184 (13) 0.0029 (16) C40 0.0254 (14) 0.031 (2) 0.0345 (15) 0.0036 (13) 0.0064 (11) −0.0049 (13) C41 0.0332 (15) 0.039 (2) 0.0384 (16) −0.0007 (15) 0.0101 (12) −0.0038 (15) C42 0.0373 (16) 0.031 (2) 0.0346 (14) 0.0017 (15) 0.0099 (12) 0.0015 (14) C45 0.0262 (14) 0.033 (2) 0.0297 (13) 0.0001 (14) 0.0111 (11) 0.0062 (13) C46 0.0331 (15) 0.041 (2) 0.0313 (14) −0.0033 (15) 0.0087 (12) 0.0036 (14) C47 0.0421 (16) 0.043 (2) 0.0301 (13) −0.0053 (17) 0.0154 (12) −0.0013 (15) C48 0.0434 (17) 0.040 (2) 0.0388 (15) 0.0059 (16) 0.0213 (13) 0.0069 (16) C49 0.0341 (15) 0.042 (2) 0.0330 (14) 0.0048 (15) 0.0098 (12) 0.0063 (15) C50 0.0292 (14) 0.0314 (19) 0.0276 (13) −0.0003 (14) 0.0096 (11) 0.0071 (13) O1 0.0243 (10) 0.0412 (16) 0.0376 (10) 0.0033 (9) 0.0099 (8) 0.0029 (10) O31 0.0407 (11) 0.0414 (15) 0.0288 (9) 0.0010 (11) 0.0067 (8) −0.0010 (10) N9 0.0256 (11) 0.0378 (18) 0.0312 (12) 0.0016 (12) 0.0079 (9) −0.0030 (12) N13 0.0305 (12) 0.0317 (17) 0.0291 (11) −0.0044 (12) 0.0117 (9) −0.0013 (11) N14 0.0279 (12) 0.0392 (18) 0.0309 (11) −0.0016 (12) 0.0074 (9) 0.0018 (12) N21 0.0292 (12) 0.042 (2) 0.0362 (12) −0.0055 (12) 0.0107 (10) −0.0055 (12) N39 0.0330 (13) 0.0344 (18) 0.0283 (11) 0.0033 (12) 0.0079 (9) −0.0016 (11) N43 0.0293 (12) 0.0318 (17) 0.0288 (11) 0.0019 (11) 0.0090 (9) 0.0036 (11) N44 0.0273 (12) 0.0398 (19) 0.0297 (11) −0.0029 (12) 0.0049 (9) 0.0046 (11) N51 0.0316 (12) 0.0348 (17) 0.0289 (11) 0.0045 (12) 0.0072 (9) 0.0039 (12)

Geometric parameters (Å, º)

C10—C11 1.343 (4) C40—C42 1.498 (4) C10—N9 1.397 (4) C41—O31 1.372 (4) C10—C12 1.504 (4) C41—H41 0.950 C11—O1 1.382 (3) C42—N43 1.465 (4) C11—H11 0.950 C42—H42A 0.990 C12—N13 1.470 (4) C42—H42B 0.990 C12—H12A 0.990 C45—N44 1.360 (4) C12—H12B 0.990 C45—C50 1.408 (4) C15—N14 1.364 (4) C45—C46 1.417 (4) C15—C20 1.410 (4) C46—C47 1.366 (4) C15—C16 1.422 (4) C46—H46 0.950 C16—C17 1.358 (4) C47—C48 1.428 (4) C16—H16 0.950 C47—H47 0.950 C17—C18 1.423 (4) C48—C49 1.371 (4) C17—H17 0.950 C48—H48 0.950 C18—C19 1.379 (4) C49—C50 1.412 (4) C18—H18 0.950 C49—H49 0.950 C19—C20 1.413 (4) C50—N51 1.352 (4) C19—H19 0.950 N13—N21 1.332 (3) C20—N21 1.356 (4) N13—N14 1.338 (3) C32—N39 1.308 (3) N43—N44 1.333 (3) C32—O31 1.373 (3) N43—N51 1.342 (3)

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C10—C11—H11 126.1 H42A—C42—H42B 108.0 O1—C11—H11 126.1 N44—C45—C50 108.6 (2) N13—C12—C10 112.0 (3) N44—C45—C46 130.0 (2) N13—C12—H12A 109.2 C50—C45—C46 121.4 (3) C10—C12—H12A 109.2 C47—C46—C45 117.0 (2) N13—C12—H12B 109.2 C47—C46—H46 121.5 C10—C12—H12B 109.2 C45—C46—H46 121.5 H12A—C12—H12B 107.9 C46—C47—C48 121.8 (3) N14—C15—C20 108.4 (2) C46—C47—H47 119.1 N14—C15—C16 130.6 (2) C48—C47—H47 119.1 C20—C15—C16 121.0 (3) C49—C48—C47 121.8 (3) C17—C16—C15 117.0 (3) C49—C48—H48 119.1 C17—C16—H16 121.5 C47—C48—H48 119.1 C15—C16—H16 121.5 C48—C49—C50 117.2 (3) C16—C17—C18 122.4 (3) C48—C49—H49 121.4 C16—C17—H17 118.8 C50—C49—H49 121.4 C18—C17—H17 118.8 N51—C50—C45 109.1 (2) C19—C18—C17 121.5 (3) N51—C50—C49 130.1 (2) C19—C18—H18 119.3 C45—C50—C49 120.8 (3) C17—C18—H18 119.3 C2—O1—C11 104.5 (2) C18—C19—C20 117.0 (3) C41—O31—C32 104.5 (2) C18—C19—H19 121.5 C2—N9—C10 104.5 (2) C20—C19—H19 121.5 N21—N13—N14 117.7 (2) N21—C20—C15 109.1 (2) N21—N13—C12 120.8 (2) N21—C20—C19 129.9 (2) N14—N13—C12 121.5 (2) C15—C20—C19 121.1 (2) N13—N14—C15 102.3 (2) N39—C32—O31 113.1 (3) N13—N21—C20 102.5 (2) N39—C32—C33 128.9 (2) C32—N39—C40 104.8 (2) O31—C32—C33 118.0 (2) N44—N43—N51 117.3 (2) C34—C33—C38 120.0 N44—N43—C42 121.9 (2) C34—C33—C32 121.02 (16) N51—N43—C42 120.8 (2) C38—C33—C32 118.97 (15) N43—N44—C45 102.6 (2) C35—C34—C33 120.0 N43—N51—C50 102.5 (2)