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

Wang, J.; Bai, J.; Pan, Y.

doi:10.1107/S1600536807062988

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o106

https://doi.org/10.1107/S1600536807062988

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

Junke Wang,^a Junfeng Bai ^a and Yi Pan ^a ^*

^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 ); Aoi & Okada (1996 ); Decken et al. (2006 ); Eisnor et al. (2006 ); Meyers (2005 ).

Experimental

Crystal data

C₁₀H₉BrN₂O₂
M_r = 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 ) T_min = 0.32, T_max = 0.38
5489 measured reflections
2016 independent reflections
1523 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807062988/tk2220sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062988/tk2220Isup2.hkl

checkCIF report

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.

Structure description top

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

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

C₁₀H₉BrN₂O₂	F(000) = 536
M_r = 269.10	D_x = 1.743 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2276 reflections
a = 8.3877 (9) Å	θ = 2.6–27.0°
b = 12.5593 (14) Å	µ = 3.99 mm⁻¹
c = 10.1907 (12) Å	T = 291 K
β = 107.222 (2)°	Block, colourless
V = 1025.4 (2) Å³	0.30 × 0.26 × 0.24 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	2016 independent reflections
Radiation source: sealed tube	1523 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
φ and ω scans	θ_max = 26.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.32, T_max = 0.38	k = −15→12
5489 measured reflections	l = −8→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0638P)²] where P = (F_o² + 2F_c²)/3
2016 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

C₁₀H₉BrN₂O₂	V = 1025.4 (2) Å³
M_r = 269.10	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.3877 (9) Å	µ = 3.99 mm⁻¹
b = 12.5593 (14) Å	T = 291 K
c = 10.1907 (12) Å	0.30 × 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)
T_min = 0.32, T_max = 0.38	R_int = 0.043
5489 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.35 e Å⁻³
2016 reflections	Δρ_min = −0.68 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Br1	0.04206 (6)	1.43302 (3)	0.32211 (5)	0.04284 (18)
C1	0.0393 (6)	1.1042 (4)	0.3277 (5)	0.0444 (10)
C2	0.0857 (6)	1.2085 (4)	0.3458 (5)	0.0490 (11)
H2	0.1950	1.2257	0.3946	0.059*
C3	−0.0281 (6)	1.2896 (4)	0.2923 (5)	0.0404 (10)
C4	−0.1893 (6)	1.2665 (4)	0.2181 (5)	0.0455 (11)
H4	−0.2645	1.3206	0.1801	0.055*
C5	−0.2374 (5)	1.1618 (4)	0.2011 (5)	0.0502 (11)
H5	−0.3472	1.1450	0.1532	0.060*
C6	−0.1254 (5)	1.0807 (4)	0.2540 (5)	0.0436 (10)
H6	−0.1600	1.0101	0.2404	0.052*
C7	0.1639 (6)	1.0192 (4)	0.3880 (5)	0.0444 (10)
C8	0.2087 (5)	0.8408 (3)	0.4213 (4)	0.0371 (9)
C9	0.4320 (5)	0.7332 (4)	0.5310 (5)	0.0456 (11)
H9A	0.4701	0.7237	0.6299	0.055*
H9B	0.5225	0.7167	0.4931	0.055*
C10	0.2784 (5)	0.6662 (4)	0.4651 (5)	0.0476 (11)
H10A	0.2988	0.6185	0.3969	0.057*
H10B	0.2479	0.6242	0.5339	0.057*
N1	0.1044 (5)	0.9177 (3)	0.3686 (5)	0.0496 (10)
N2	0.3674 (5)	0.8409 (3)	0.4935 (4)	0.0446 (9)
H2A	0.372 (6)	0.884 (5)	0.566 (5)	0.053*
O1	0.3084 (4)	1.0460 (3)	0.4488 (5)	0.0657 (12)
O2	0.1470 (4)	0.7416 (2)	0.4011 (3)	0.0413 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0564 (3)	0.0335 (3)	0.0415 (3)	−0.0033 (2)	0.01904 (19)	−0.00697 (19)
C1	0.044 (2)	0.037 (2)	0.050 (3)	0.000 (2)	0.012 (2)	−0.003 (2)
C2	0.046 (3)	0.046 (3)	0.052 (3)	−0.006 (2)	0.011 (2)	−0.008 (2)
C3	0.039 (2)	0.033 (2)	0.050 (3)	−0.0011 (18)	0.0145 (19)	−0.0056 (18)
C4	0.042 (2)	0.039 (2)	0.054 (3)	0.0062 (19)	0.012 (2)	−0.003 (2)
C5	0.028 (2)	0.048 (3)	0.068 (3)	0.0001 (19)	0.004 (2)	0.000 (2)
C6	0.032 (2)	0.037 (2)	0.058 (3)	−0.0041 (18)	0.0079 (19)	−0.002 (2)
C7	0.045 (2)	0.034 (2)	0.049 (3)	−0.0020 (19)	0.006 (2)	−0.0057 (19)
C8	0.027 (2)	0.038 (2)	0.044 (2)	−0.0029 (16)	0.0072 (16)	−0.0023 (18)
C9	0.030 (2)	0.045 (2)	0.061 (3)	−0.0017 (18)	0.011 (2)	0.006 (2)
C10	0.038 (2)	0.035 (2)	0.073 (3)	0.0006 (19)	0.020 (2)	0.006 (2)
N1	0.046 (2)	0.036 (2)	0.059 (2)	−0.0029 (18)	0.0049 (18)	0.0021 (18)
N2	0.0314 (19)	0.038 (2)	0.056 (2)	−0.0071 (15)	−0.0002 (17)	0.0013 (18)
O1	0.0422 (19)	0.0362 (19)	0.101 (3)	−0.0062 (15)	−0.0059 (19)	−0.0101 (19)
O2	0.0309 (14)	0.0372 (16)	0.0486 (17)	−0.0080 (12)	0.0005 (12)	0.0050 (13)

Geometric parameters (Å, º) top

Br1—C3	1.891 (4)	C7—N1	1.362 (6)
C1—C2	1.364 (7)	C8—N1	1.308 (6)
C1—C6	1.395 (6)	C8—N2	1.317 (5)
C1—C7	1.494 (7)	C8—O2	1.340 (5)
C2—C3	1.392 (7)	C9—N2	1.466 (6)
C2—H2	0.9300	C9—C10	1.519 (6)
C3—C4	1.371 (6)	C9—H9A	0.9700
C4—C5	1.371 (7)	C9—H9B	0.9700
C4—H4	0.9300	C10—O2	1.453 (5)
C5—C6	1.383 (6)	C10—H10A	0.9700
C5—H5	0.9300	C10—H10B	0.9700
C6—H6	0.9300	N2—H2A	0.91 (6)
C7—O1	1.233 (5)

C2—C1—C6	118.3 (4)	N1—C8—N2	132.1 (4)
C2—C1—C7	119.6 (4)	N1—C8—O2	116.3 (4)
C6—C1—C7	122.1 (4)	N2—C8—O2	111.6 (4)
C1—C2—C3	121.0 (4)	N2—C9—C10	101.3 (3)
C1—C2—H2	119.5	N2—C9—H9A	111.5
C3—C2—H2	119.5	C10—C9—H9A	111.5
C4—C3—C2	120.7 (4)	N2—C9—H9B	111.5
C4—C3—Br1	120.0 (3)	C10—C9—H9B	111.5
C2—C3—Br1	119.3 (3)	H9A—C9—H9B	109.3
C3—C4—C5	118.6 (4)	O2—C10—C9	105.6 (3)
C3—C4—H4	120.7	O2—C10—H10A	110.6
C5—C4—H4	120.7	C9—C10—H10A	110.6
C4—C5—C6	121.1 (4)	O2—C10—H10B	110.6
C4—C5—H5	119.4	C9—C10—H10B	110.6
C6—C5—H5	119.4	H10A—C10—H10B	108.8
C5—C6—C1	120.3 (4)	C8—N1—C7	117.4 (4)
C5—C6—H6	119.9	C8—N2—C9	112.3 (4)
C1—C6—H6	119.9	C8—N2—H2A	104 (3)
O1—C7—N1	126.4 (4)	C9—N2—H2A	115 (4)
O1—C7—C1	118.4 (4)	C8—O2—C10	109.2 (3)
N1—C7—C1	115.3 (4)

Hydrogen-bond geometry (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₁₀H₉BrN₂O₂
M_r	269.10
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	8.3877 (9), 12.5593 (14), 10.1907 (12)
β (°)	107.222 (2)
V (Å³)	1025.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.99
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.32, 0.38
No. of measured, independent and observed [I > 2σ(I)] reflections	5489, 2016, 1523
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.109, 0.99
No. of reflections	2016
No. of parameters	139
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.68

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1	0.93	2.50	2.817 (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

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