organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

(E)-3-Bromo-N-(1,3-oxazolidin-2-yl­­idene)benzamide

aSchool of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China
*Correspondence e-mail: njupanyi@yahoo.com.cn

(Received 16 November 2007; accepted 24 November 2007; online 6 December 2007)

The five- and six-membered rings in the title compound, C10H9BrN2O2, are essentially coplanar. This is consistent with a highly conjugated system, as seen in the short N—C bond distances of 1.308 (6) and 1.317 (5) Å.

Related literature

For related literature, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]); Aoi & Okada (1996[Aoi, K. & Okada, M. (1996). Prog. Polym. Sci. 21, 151-208.]); Decken et al. (2006[Decken, A., Eisnor, C. R., Gossage, R. A. & Jackson, S. M. (2006). Inorg. Chim. Acta, 359, 1743-1753.]); Eisnor et al. (2006[Eisnor, C. R., Gossage, R. A. & Yadav, P. N. (2006). Tetrahedron, 62, 3395-3401.]); Meyers (2005[Meyers, A. I. (2005). J. Org. Chem. 70, 6137-6151.]).

[Scheme 1]

Experimental

Crystal data
  • C10H9BrN2O2

  • Mr = 269.10

  • Monoclinic, P 21 /n

  • a = 8.3877 (9) Å

  • b = 12.5593 (14) Å

  • c = 10.1907 (12) Å

  • β = 107.222 (2)°

  • V = 1025.4 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 3.99 mm−1

  • T = 291 (2) K

  • 0.30 × 0.26 × 0.24 mm

Data collection
  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2000[Bruker (2000). SMART (Version 5.618), SAINT (Version 6.02), SADABS (Version 2.03) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.32, Tmax = 0.38

  • 5489 measured reflections

  • 2016 independent reflections

  • 1523 reflections with I > 2σ(I)

  • Rint = 0.043

Refinement
  • R[F2 > 2σ(F2)] = 0.046

  • wR(F2) = 0.109

  • S = 0.99

  • 2016 reflections

  • 139 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.35 e Å−3

  • Δρmin = −0.68 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C6—H6⋯N1 0.93 2.50 2.817 (6) 100

Data collection: SMART (Bruker, 2000[Bruker (2000). SMART (Version 5.618), SAINT (Version 6.02), SADABS (Version 2.03) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SMART (Version 5.618), SAINT (Version 6.02), SADABS (Version 2.03) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000[Bruker (2000). SMART (Version 5.618), SAINT (Version 6.02), SADABS (Version 2.03) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

2-Oxazolines are an important class of heterocyclic compounds which have been applied to a number of areas of chemical endeavour. For example, asymmetric organic synthesis (Meyers, 2005), polymerization chemistry (Aoi & Okada, 1996), Lewis acid catalysis (Eisnor et al., 2006), and coordination chemistry (Decken et al., 2006). Although their coordination complexes are widespread used, few metal-free species have been characterized crystallographically (Allen, 2002). Herein, the molecular structure of the title compound (I) is described.

The bond lengths and angles determined for (I) have the usual values found for structurally similar molecules (Allen, 2002). The existence of a conjugated system is found in the values of the N1—C8 [1.308 (6) Å] and N2—C8 [1.317 (5) Å] bond distances. The dihedral angle between the aryl rings and the oxazolidine ring is 1.82 (2)° and the C4—C7—N2—C8 torsion angle is 179.10 (4)°, indicating planarity of the model.

Related literature top

For related literature, see: Allen (2002); Aoi & Okada (1996); Decken et al. (2006); Eisnor et al. (2006); Meyers (2005).

Experimental top

To a solution of 4-chlorobenzoyl chloride (1 mmol) in CH2Cl2 (5 ml) was added ammonium thiocyanate (1.3 mmol) and PEG-400 (0.1 mmol). The mixture was then stirred at room temperature for 1 h. A solution of 2-aminoethanol (0.9 mmol) in CH2Cl2 (2 ml) was added. The mixture was continuously stirred for 30 min. After the reaction was completed, water (10 ml) was added and the organic phase was dried over anhydrous sodium sulfate. The solvent was removed under vacuum and the residue was purified by flash chromatography to give 1-(3-bromobenzoyl)-3-(2-hydroxyethyl)thiourea in 95% yield. This compound was reacted with dicyclohexylcarbodiimide under weakly basic conditions in acetonitrile to give (I) in 93% yield. Single crystals suitable for the X-ray diffraction study were obtained by slow evaporation of an acetone/water solution of (I); m. p. 374–375 K.

Refinement top

The positional parameters of the N—H atom were refined freely with Uiso(H) = 1.2Ueq(N); N—H = 0.91 (6) Å. The C-bound H atoms were included in the riding model approximation with C—H = 0.93 Å, and with Uiso(H) = 1.2Ueq(C).

Structure description top

2-Oxazolines are an important class of heterocyclic compounds which have been applied to a number of areas of chemical endeavour. For example, asymmetric organic synthesis (Meyers, 2005), polymerization chemistry (Aoi & Okada, 1996), Lewis acid catalysis (Eisnor et al., 2006), and coordination chemistry (Decken et al., 2006). Although their coordination complexes are widespread used, few metal-free species have been characterized crystallographically (Allen, 2002). Herein, the molecular structure of the title compound (I) is described.

The bond lengths and angles determined for (I) have the usual values found for structurally similar molecules (Allen, 2002). The existence of a conjugated system is found in the values of the N1—C8 [1.308 (6) Å] and N2—C8 [1.317 (5) Å] bond distances. The dihedral angle between the aryl rings and the oxazolidine ring is 1.82 (2)° and the C4—C7—N2—C8 torsion angle is 179.10 (4)°, indicating planarity of the model.

For related literature, see: Allen (2002); Aoi & Okada (1996); Decken et al. (2006); Eisnor et al. (2006); Meyers (2005).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and 30% probability displacement ellipsoids.
(E)-3-Bromo-N-(1,3-oxazolidin-2-ylidene)benzamide top
Crystal data top
C10H9BrN2O2F(000) = 536
Mr = 269.10Dx = 1.743 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2276 reflections
a = 8.3877 (9) Åθ = 2.6–27.0°
b = 12.5593 (14) ŵ = 3.99 mm1
c = 10.1907 (12) ÅT = 291 K
β = 107.222 (2)°Block, colourless
V = 1025.4 (2) Å30.30 × 0.26 × 0.24 mm
Z = 4
Data collection top
Bruker SMART APEX CCD
diffractometer
2016 independent reflections
Radiation source: sealed tube1523 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
φ and ω scansθmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1010
Tmin = 0.32, Tmax = 0.38k = 1512
5489 measured reflectionsl = 812
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.0638P)2]
where P = (Fo2 + 2Fc2)/3
2016 reflections(Δ/σ)max < 0.001
139 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.68 e Å3
Crystal data top
C10H9BrN2O2V = 1025.4 (2) Å3
Mr = 269.10Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.3877 (9) ŵ = 3.99 mm1
b = 12.5593 (14) ÅT = 291 K
c = 10.1907 (12) Å0.30 × 0.26 × 0.24 mm
β = 107.222 (2)°
Data collection top
Bruker SMART APEX CCD
diffractometer
2016 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1523 reflections with I > 2σ(I)
Tmin = 0.32, Tmax = 0.38Rint = 0.043
5489 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.109H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.35 e Å3
2016 reflectionsΔρmin = 0.68 e Å3
139 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
xyzUiso*/Ueq
Br10.04206 (6)1.43302 (3)0.32211 (5)0.04284 (18)
C10.0393 (6)1.1042 (4)0.3277 (5)0.0444 (10)
C20.0857 (6)1.2085 (4)0.3458 (5)0.0490 (11)
H20.19501.22570.39460.059*
C30.0281 (6)1.2896 (4)0.2923 (5)0.0404 (10)
C40.1893 (6)1.2665 (4)0.2181 (5)0.0455 (11)
H40.26451.32060.18010.055*
C50.2374 (5)1.1618 (4)0.2011 (5)0.0502 (11)
H50.34721.14500.15320.060*
C60.1254 (5)1.0807 (4)0.2540 (5)0.0436 (10)
H60.16001.01010.24040.052*
C70.1639 (6)1.0192 (4)0.3880 (5)0.0444 (10)
C80.2087 (5)0.8408 (3)0.4213 (4)0.0371 (9)
C90.4320 (5)0.7332 (4)0.5310 (5)0.0456 (11)
H9A0.47010.72370.62990.055*
H9B0.52250.71670.49310.055*
C100.2784 (5)0.6662 (4)0.4651 (5)0.0476 (11)
H10A0.29880.61850.39690.057*
H10B0.24790.62420.53390.057*
N10.1044 (5)0.9177 (3)0.3686 (5)0.0496 (10)
N20.3674 (5)0.8409 (3)0.4935 (4)0.0446 (9)
H2A0.372 (6)0.884 (5)0.566 (5)0.053*
O10.3084 (4)1.0460 (3)0.4488 (5)0.0657 (12)
O20.1470 (4)0.7416 (2)0.4011 (3)0.0413 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0564 (3)0.0335 (3)0.0415 (3)0.0033 (2)0.01904 (19)0.00697 (19)
C10.044 (2)0.037 (2)0.050 (3)0.000 (2)0.012 (2)0.003 (2)
C20.046 (3)0.046 (3)0.052 (3)0.006 (2)0.011 (2)0.008 (2)
C30.039 (2)0.033 (2)0.050 (3)0.0011 (18)0.0145 (19)0.0056 (18)
C40.042 (2)0.039 (2)0.054 (3)0.0062 (19)0.012 (2)0.003 (2)
C50.028 (2)0.048 (3)0.068 (3)0.0001 (19)0.004 (2)0.000 (2)
C60.032 (2)0.037 (2)0.058 (3)0.0041 (18)0.0079 (19)0.002 (2)
C70.045 (2)0.034 (2)0.049 (3)0.0020 (19)0.006 (2)0.0057 (19)
C80.027 (2)0.038 (2)0.044 (2)0.0029 (16)0.0072 (16)0.0023 (18)
C90.030 (2)0.045 (2)0.061 (3)0.0017 (18)0.011 (2)0.006 (2)
C100.038 (2)0.035 (2)0.073 (3)0.0006 (19)0.020 (2)0.006 (2)
N10.046 (2)0.036 (2)0.059 (2)0.0029 (18)0.0049 (18)0.0021 (18)
N20.0314 (19)0.038 (2)0.056 (2)0.0071 (15)0.0002 (17)0.0013 (18)
O10.0422 (19)0.0362 (19)0.101 (3)0.0062 (15)0.0059 (19)0.0101 (19)
O20.0309 (14)0.0372 (16)0.0486 (17)0.0080 (12)0.0005 (12)0.0050 (13)
Geometric parameters (Å, º) top
Br1—C31.891 (4)C7—N11.362 (6)
C1—C21.364 (7)C8—N11.308 (6)
C1—C61.395 (6)C8—N21.317 (5)
C1—C71.494 (7)C8—O21.340 (5)
C2—C31.392 (7)C9—N21.466 (6)
C2—H20.9300C9—C101.519 (6)
C3—C41.371 (6)C9—H9A0.9700
C4—C51.371 (7)C9—H9B0.9700
C4—H40.9300C10—O21.453 (5)
C5—C61.383 (6)C10—H10A0.9700
C5—H50.9300C10—H10B0.9700
C6—H60.9300N2—H2A0.91 (6)
C7—O11.233 (5)
C2—C1—C6118.3 (4)N1—C8—N2132.1 (4)
C2—C1—C7119.6 (4)N1—C8—O2116.3 (4)
C6—C1—C7122.1 (4)N2—C8—O2111.6 (4)
C1—C2—C3121.0 (4)N2—C9—C10101.3 (3)
C1—C2—H2119.5N2—C9—H9A111.5
C3—C2—H2119.5C10—C9—H9A111.5
C4—C3—C2120.7 (4)N2—C9—H9B111.5
C4—C3—Br1120.0 (3)C10—C9—H9B111.5
C2—C3—Br1119.3 (3)H9A—C9—H9B109.3
C3—C4—C5118.6 (4)O2—C10—C9105.6 (3)
C3—C4—H4120.7O2—C10—H10A110.6
C5—C4—H4120.7C9—C10—H10A110.6
C4—C5—C6121.1 (4)O2—C10—H10B110.6
C4—C5—H5119.4C9—C10—H10B110.6
C6—C5—H5119.4H10A—C10—H10B108.8
C5—C6—C1120.3 (4)C8—N1—C7117.4 (4)
C5—C6—H6119.9C8—N2—C9112.3 (4)
C1—C6—H6119.9C8—N2—H2A104 (3)
O1—C7—N1126.4 (4)C9—N2—H2A115 (4)
O1—C7—C1118.4 (4)C8—O2—C10109.2 (3)
N1—C7—C1115.3 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N10.932.502.817 (6)100

Experimental details

Crystal data
Chemical formulaC10H9BrN2O2
Mr269.10
Crystal system, space groupMonoclinic, P21/n
Temperature (K)291
a, b, c (Å)8.3877 (9), 12.5593 (14), 10.1907 (12)
β (°) 107.222 (2)
V3)1025.4 (2)
Z4
Radiation typeMo Kα
µ (mm1)3.99
Crystal size (mm)0.30 × 0.26 × 0.24
Data collection
DiffractometerBruker SMART APEX CCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.32, 0.38
No. of measured, independent and
observed [I > 2σ(I)] reflections
5489, 2016, 1523
Rint0.043
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.109, 0.99
No. of reflections2016
No. of parameters139
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.35, 0.68

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C6—H6···N10.932.502.817 (6)100
 

Acknowledgements

Financial support from the 863 High Technology Programme, the Qing-Lan Programme of Jiangsu Province, the Kua-Shi-Ji Programme of the Education Ministry of China, the Talent Foundation of Jiangsu Province (grant No. BK2006513), the Major State Basic Research Development Programme (grant No. 2006CB806104) and the Twenty-one Century Talent Foundation of the Ministry of Education is acknowledged.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationAoi, K. & Okada, M. (1996). Prog. Polym. Sci. 21, 151–208.  CrossRef CAS Web of Science Google Scholar
First citationBruker (2000). SMART (Version 5.618), SAINT (Version 6.02), SADABS (Version 2.03) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDecken, A., Eisnor, C. R., Gossage, R. A. & Jackson, S. M. (2006). Inorg. Chim. Acta, 359, 1743–1753.  Web of Science CSD CrossRef CAS Google Scholar
First citationEisnor, C. R., Gossage, R. A. & Yadav, P. N. (2006). Tetrahedron, 62, 3395–3401.  Web of Science CrossRef CAS Google Scholar
First citationMeyers, A. I. (2005). J. Org. Chem. 70, 6137–6151.  Web of Science CrossRef PubMed CAS Google Scholar

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