4-[(Dimethyl­amino)methyl­idene]-2-(4-nitro­phen­yl)-1,3-oxazol-5(4H)-one

Gilberto A Romeiro; Carlos M R Ribeiro; Solange M S V Wardell; James L Wardell; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536810018635

. 2010 May 26;66(Pt 6):o1450–o1451. doi: 10.1107/S1600536810018635

4-[(Dimethylamino)methylidene]-2-(4-nitrophenyl)-1,3-oxazol-5(4H)-one

Gilberto A Romeiro ^a, Carlos M R Ribeiro ^a, Solange M S V Wardell ^b, James L Wardell ^c,^‡, Seik Weng Ng ^d, Edward R T Tiekink ^d,^*

PMCID: PMC2979566 PMID: 21579521

Abstract

The title molecule, C₁₂H₁₁N₃O₄, is essentially planar, the r.m.s. deviation for all non-H atoms being 0.068 Å. An intramolecular C—H⋯N hydrogen bond occurs. The crystal packing is dominated by π–π interactions [shortest centroid–centroid distance = 3.6312 (16) Å], which lead to supramolecular chains that are linked into a three-dimensional network via C—H⋯O contacts. The crystal was found to be a non-merohedral twin (twin law −1 0 0/0 −1 0/ 0.784 0 1), the fractional contribution of the minor component being approximately 22%.

Related literature

For the synthesis, synthetic uses and properties of 4-(N,N-dimethylaminomethylene)-2-aryl-2-oxazolin-5-one derivatives, see: Singh & Singh (1994 ▶, 2008 ▶); Takahashi & Izawa (2005 ▶); Singh et al. (1994 ▶); Kmetic & Stanovnik (1995 ▶). For the Vilsmeier–Haack reaction, see: Meth-Cohn & Stanforth (1991 ▶). For related structures, see Vasuki et al. (2002 ▶); Vijayalakshmi et al. (1998 ▶). For the treatment of twinned diffraction data, see: Spek (2009 ▶).

Experimental

Crystal data

C₁₂H₁₁N₃O₄
M _r = 261.24
Monoclinic,
a = 9.5313 (2) Å
b = 9.5204 (3) Å
c = 13.0349 (4) Å
β = 106.661 (2)°
V = 1133.15 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 120 K
0.42 × 0.38 × 0.22 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.661, T _max = 1.000
14210 measured reflections
2581 independent reflections
2030 reflections with I > 2σ(I)
R _int = 0.071

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.220
S = 1.19
2581 reflections
176 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018635/ez2209sup1.cif

e-66-o1450-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018635/ez2209Isup2.hkl

e-66-o1450-Isup2.hkl^{(126.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5c⋯N1	0.98	2.28	3.074 (5)	137
C5—H5a⋯O2ⁱ	0.98	2.53	3.504 (4)	177
C5—H5c⋯O4ⁱⁱ	0.98	2.57	3.259 (5)	127
C9—H9⋯O1ⁱⁱⁱ	0.95	2.56	3.304 (4)	135
C11—H11⋯O2^iv	0.95	2.45	3.144 (4)	130

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CAPES (Brazil).

supplementary crystallographic information

Comment

The preparations of 4-(N,N-dimethylaminomethylene)-2-aryl-2-oxazolin-5-one derivatives have been reported using the Vilsmeier-Haack reactions (Meth-Cohn & Stanforth, 1991) of acylaminoacetanilides with POCl₃ and DMF (Singh & Singh, 1994; Takahashi & Izawa, 2005; Singh et al., 1994; Kmetic & Stanovnik, 1995). The compounds have been used as precursors of 4-hydroxymethylene-2-aryl-2-oxazolin-5-one, which have been tested for anti-bacterial activities (Singh & Singh, 2008). The crystal structures of 4-(N,N-dimethylaminomethylene)-2-phenyl-2-oxazolin-5-one (Vasuki et al., 2002) and 4-(N,N-dimethylaminomethylene)-2-(2-nitrophenyl)-2-oxazolin-5-one (Vijayalakshmi et al., 1998) have been reported. We now report the crystal structure of 4-(N,N-dimethylaminomethylene)-2-(4-nitrophenyl)-2-oxazolin-5-one, (I).

The molecule of (I), Fig. 1, is essentially planar with the maximum deviations from the least-squares plane through all non-hydrogen atoms being 0.157 (4) Å for atom C5 and -0.158 (3) for atom O4; the r.m.s. = 0.068 Å. The sequence of C1–N1, N1–C2, C2–C4, and C4–N2 bond distances of 1.289 (4), 1.398 (4), 1.382 (5), and 1.317 (4) Å, respectively, indicate substantial delocalisation of π-electron density over these atoms. The geometric parameters in (I) match closely those found in the parent compound, namely 4-(N,N-dimethylaminomethylene)-2-phenyl-2-oxazolin-5-one (Vasuki et al., 2002) and in the 2-nitro derivative (Vijayalakshmi et al., 1998).

The crystal packing is dominated by C–H···O and π–π interactions; the N1 atom of the oxazolin-5-one is involved in an intramolecular C–H···N contact that shields this atom from forming intermolecular interactions, Table 1. Columns of molecules orientated along the b axis are stabilised by π–π contacts with the shortest of these occurring between centrosymmetrically related benzene rings [ring centroid(C7–C12)···ring centroid(C7–C12)ⁱ = 3.6312 (16) Å for i: 1-x, 1-y, 2-z]. The benzene rings also form π–π interactions with the oxazolin-5-one rings [ring centroid(C7–C12)···ring centroid(O1,N1,C1–C3)ⁱⁱ = 3.7645 (17) Å for ii: 1-x, -y, 2-z] to form a supramolecular chain, Fig. 2. The chains are connected by a series of C–H···O contacts, Table 1, to form a 3-D network, Fig. 3.

Experimental

The title compound was prepared as per published procedures (Singh & Singh, 1994; Singh et al., 1994). Physical properties were in agreement with published data. The crystal used in the structure determination was grown from EtOH solution.