2-{Hy­droxy[1-(4-meth­oxy­phen­yl)-4-oxo-3-phenyl­azetidin-2-yl]meth­yl}acrylonitrile

C M Sai Prasanna; K Sethusankar; R Rajesh; R Raghunathan

doi:10.1107/S1600536811032247

. 2011 Aug 17;67(Pt 9):o2340. doi: 10.1107/S1600536811032247

2-{Hydroxy[1-(4-methoxyphenyl)-4-oxo-3-phenylazetidin-2-yl]methyl}acrylonitrile

C M Sai Prasanna ^a, K Sethusankar ^b,^*, R Rajesh ^c, R Raghunathan ^c

PMCID: PMC3200613 PMID: 22058961

Abstract

In the title compound, C₂₀H₁₈N₂O₃, the β-lactam ring is essentially planar, having a maximum deviation of 0.0291 (15) Å for the N atom, and perpendicular to the phenyl ring [dihedral angle = 85.55 (11)°]. The carbonitrile side chain is almost linear, the C—C—N angle being 176.8 (2)°. The crystal packing is stabilized by intermolecular O—H⋯O and C—H⋯O interactions.

Related literature

For uses of acrylonitrile derivatives, see: Ambrosi et al. (1994 ▶). For the pharmacological properties of β-lactam derivatives, see: Brakhage (1998 ▶). For related structures, see: Sundaresan et al. (2008 ▶); Kamala et al. (2008 ▶). For related geometrical parameters, see: Nizam Mohideen et al. (2007 ▶).

Experimental

Crystal data

C₂₀H₁₈N₂O₃
M _r = 334.36
Monoclinic,
a = 9.9694 (3) Å
b = 19.8196 (6) Å
c = 9.6013 (3) Å
β = 112.718 (1)°
V = 1749.93 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
10596 measured reflections
4368 independent reflections
3621 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.100
S = 1.01
4368 reflections
228 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811032247/rk2289sup1.cif

e-67-o2340-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032247/rk2289Isup2.hkl

e-67-o2340-Isup2.hkl^{(209.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811032247/rk2289Isup3.cml

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
O3—H3⋯O1ⁱ	0.82	1.90	2.716 (2)	172
C9—H9⋯O2ⁱⁱ	0.98	2.50	3.467 (2)	169

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

Acknowledgments

CMS and KS thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the X-ray intensity data collection and Dr V. Murugan, Head of the Department of Physics, for providing facilities in the department to carry out this work.

supplementary crystallographic information

Comment

Acrylonitriles are useful intermediates in organic synthesis and are capable of undergoing many useful organic transformations (Ambrosi et al., 1994), for example, into pyrazole, isoxazole and pyrimidine derivatives. β-Lactams are one of the best known and most extensively studied class of compounds due to their biological activities. The most commonly used β-lactam antibiotics for the therapy of infectious diseases are penicillin and cephalosporin (Brakhage, 1998). X-ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1.

In the title compound C₂₀H₁₈N₂O₃, due to conjugation in the C19═C18–C20≡N2 moiety, the bond length between C18 and C20 (1.429 (3)Å) shows a significant shortening (Nizam Mohideen et al., 2007). The β-lactam ring is essentially planar and the keto O1 atom deviates from this mean plane by -0.1095 (13)°. The methoxy phenyl (C11-C15) and the phenyl rings (C1-C6) form dihedral angles of 15.66 (10)° and 85.55 (11)°, respectively, with the β-lactam ring. The sum of the angles around N1 atom of the β-lactam ring system accounts for 359.5 (3)° which is in accordance with sp² hybridization. The phenyl ring and methoxy phenyl ring are cis related with respect to the β-lactam ring.

The bond angles at C18 deviate significantly from regular trigonal geometry. The bond angle around C20, in the chains of atoms C18/C20/N2, is 176.8 (2)° and thus the carbonitrile side chain is almost linear. The torsion angle of -112.87 (19)° for C7–C17–C18═C19 indicates a deviation of the β-lactam ring from the plane of the olefinic double bond. The methoxy group is slightly twisted from the plane of the phenyl ring (C10-C15) to which it is attached as evidenced by the torsion angle C14-C13-O2-C16 of 7.8 (2)°. The interplanar angle between the phenyl (C1-C6) and methoxy phenyl group (C10-C15) is 81.04 (9)°. The title compound exhibits structural similarities with the already reported related structures (Sundaresan et al., 2008, Kamala et al., 2008).

The crystal packing is stabilized by O–H···O and C–H···O hydrogen bonds via O3–H3···O1ⁱ and C9–H9···O2ⁱⁱ intermolecular interactions, viewed down the a axis. Symmetry codes: (i) x, -y, z+1/2; (ii) x+1, y, z. The packing view of the title compound is shown in Fig. 2.

Experimental

To the reaction mixture of 1-(4-methoxyphenyl)-4-oxo-3-phenylazetidine-2-carbaldehyde (1 mmol) with acrylonitrile (2 mmol), a catalytic quantity of 1,4-diazabicyclo[2.2.2]octane (10-15 mol %) was added. The reaction mixture was left standing at room temperature in a stoppered sample flask. The progress of the reaction was monitored by TLC over a period of several days. After a period of 10 days, the TLC revealed the presence of a product. The reaction mixture was dissolved in ethyl acetate and washed with aqueous HCl solution (0.25 M) and water followed by brine solution. The organic layer was separated and dried over sodium sulfate. Filtering and evaporation of the organic solvent was done under reduced pressure. The product was separated by flash column chromatography using hexane and ethyl acetate as an eluent (1:9) to give colourless solid. The product was dissolved in chloroform and heated for two minutes. The resulting solution was subjected to crystallization by slow evaporation of the solvent resulting in single crystals suitable for XRD studies.