11-Hy­droxy-9-[1-(4-methyl­phen­yl)-4-oxo-3-phenyl­azetidin-2-yl]-18-oxo-10-oxa-2-aza­penta­cyclo­[9.7.0.01,8.02,6.012,17]octa­deca-12,14,16-triene-8-carbonitrile

Sivasubramanian Suhitha; Thothadri Srinivasan; Raju Rajesh; Raghavachary Raghunathan; Devadasan Velmurugan

doi:10.1107/S1600536812044479

. 2012 Nov 7;68(Pt 12):o3290–o3291. doi: 10.1107/S1600536812044479

11-Hydroxy-9-[1-(4-methylphenyl)-4-oxo-3-phenylazetidin-2-yl]-18-oxo-10-oxa-2-azapentacyclo[9.7.0.0^1,8.0^2,6.0^12,17]octadeca-12,14,16-triene-8-carbonitrile

Sivasubramanian Suhitha ^a, Thothadri Srinivasan ^a, Raju Rajesh ^b, Raghavachary Raghunathan ^b, Devadasan Velmurugan ^a,^*

PMCID: PMC3588836 PMID: 23468801

Abstract

In the title compound, C₃₃H₂₉N₃O₅, the four-membered ring of the β-lactam fragment is essentially planar (r.m.s. deviation = 0.0122 Å), with the carbonyl O atom displaced from this ring by 0.856 (9) Å. The mean planes of the methoxyphenyl and phenyl rings are inclined at dihedral angles 85.10 (7) and 21.56 (14)°, respectively, with respect to the mean plane of the four-membered ring. The pyrrolidine rings adopt envelope conformations with C atoms lying 0.535 (4) and 0.519 (4) Å out of the planes formed by the remaining ring atoms. The furan ring also adopts an envelope conformation with a C atom 0.560 (3) Å out of the plane formed by the remaining ring atoms. The nine-membered indene ring is almost planar (r.m.s. deviation = 0.0240 Å), with the carbonyl O atom displaced by 0.145 (3) Å from this ring. The molecular structure is stabilized by a strong intramolecular O—H⋯N hydrogen bond and the crystal structure is consolidated by C—H⋯O hydrogen bonds.

Related literature

For general background to β-lactams, see: Brakhage (1998 ▶). For a related structure, see: Sundaramoorthy et al. (2012 ▶).

Experimental

Crystal data

C₃₃H₂₉N₃O₅
M _r = 547.59
Orthorhombic,
a = 10.2874 (16) Å
b = 14.138 (3) Å
c = 18.866 (3) Å
V = 2743.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.973, T _max = 0.982
14810 measured reflections
6406 independent reflections
4551 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.123
S = 1.00
6406 reflections
375 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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

Click here for additional data file.^{(38.4KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812044479/pv2596sup1.cif

e-68-o3290-sup1.cif^{(38.4KB, cif)}

Click here for additional data file.^{(307.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044479/pv2596Isup2.hkl

e-68-o3290-Isup2.hkl^{(307.2KB, hkl)}

Click here for additional data file.^{(10.7KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812044479/pv2596Isup3.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
C10—H10⋯O2ⁱ	0.98	2.43	3.337 (3)	154
C13—H13A⋯O2ⁱ	0.97	2.41	3.321 (3)	156
C29—H29⋯O4ⁱ	0.93	2.55	3.228 (3)	130
O4—H4A⋯N2	0.93 (3)	1.84 (3)	2.602 (3)	137 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection and TS thanks the DST for an Inspire fellowship.

supplementary crystallographic information

Comment

The most commonly used β-lactam antibiotics for the therapy of infectious diseases are penicillin and cephalosporin (Brakhage, 1998). In view of potential applications, the crystal structure determination of the titled β-lactam derivative was carried out that is reported in this artiucle.

In the title compound (Fig. 1), the four membered ring of the β-lactam fragment (N1/C8–C10) is essentially planar (rmsd = 0.0122 Å) with O1 displaced from this ring by 0.856 (9) Å. The mean-planes of the benzene rings C2–C7 and C27–C32 are inclined at dihedral angles 85.10 (7) and 21.56 (14)°, respectively, with respect to the mean-plane of the four membered ring (N1/C8–C10).

The pyrrolidine rings (N1/C14–C17) and (N2/C12–C14/C18) adopt C16- and C13-envelope conformations with C16 and C13 atoms lying 0.535 (4) and 0.519 (4) Å, respectively, out of the planes formed by the remaining ring atoms. The furan ring (O3/C11/C12/C18/C19) also adopts a C11-envelope conformation with C11 atom 0.560 (3) Å out of the plane formed by the remaining ring atoms. The nine membered indene ring (C18–C26) is almost planar (rmsd = 0.0240 Å) with O5 displaced by 0.145 (3)Å from this ring.

The molecular structure of the title compound is stabilized by a strong intramolecular hydrogen bond O4—H4A···N2 (Table 1). The crystal structure is consolidated by intermolecular C—H···O hydrogen bonds (Tab. 1 & Fig. 2).

Experimental

A reaction mixture of 2-(hydroxy(1-(4-methoxyphenyl)-4-oxo-3-phenylazetidin -2-yl)methyl)acrylonitrile (1.0 mmol), ninhydrine (1.1 mmol) and proline (1.1 mmol) was refluxed in methanol (20 ml) until completion of the reaction was evidenced by TLC analysis. After completion of the reaction the solvent was evaporated under reduced pressure. The crude reaction mixture was dissolved in dichloromethane (2 x 50 ml) and washed with water followed by brine solution. The organic layer was separated and dried over sodium sulfate. After filteration and evaporation of the organic solvent was carried out under reduced pressure. The product was separated by column chromatography using hexane and ethyl acetate (4:6) as an eluent to give a colorless solid. The product was dissolved in chloroform (3 ml) and heated for two minutes. The resulting solution was subjected to crystallization by slow evaporation of the solvent resulting in single crystals suitable for X-ray crystallographic studies.