Crystal structure of 3-(4-chloro­phen­oxy)-4-(2-nitro­phen­yl)azetidin-2-one with an unknown solvate

Sevim Türktekin Çelikesir; Mehmet Akkurt; Aliasghar Jarrahpour; Habib Allah Shafie; Ömer Çelik

doi:10.1107/S2056989014025845

. 2015 Jan 1;71(Pt 1):o8–o9. doi: 10.1107/S2056989014025845

Crystal structure of 3-(4-chlorophenoxy)-4-(2-nitrophenyl)azetidin-2-one with an unknown solvate

Sevim Türktekin Çelikesir ^a, Mehmet Akkurt ^a,^*, Aliasghar Jarrahpour ^b, Habib Allah Shafie ^b, Ömer Çelik ^c

PMCID: PMC4331907 PMID: 25705514

Abstract

In the title compound, C₁₅H₁₁ClN₂O₄, the central β-lactam ring is approximately planar [maximum deviation = 0.044 (2) Å for the N atom from the mean plane] and subtends dihedral angles of 61.17 (11) and 40.21 (12) °, respectively, with the nitro and chlorobenzene rings. Both substituents lie to the same side of the β-lactam core. In the crystal, N—H⋯O hydrogen bonds link the molecules into C(4) chains propagating in [010]. The chains are cross-linked by C—H⋯O and weak C—H⋯π interactions, generating a three-dimensional network. The solvent molecules were found to be highly disordered and their contribution to the scattering was removed with the SQUEEZE procedure in PLATON [Spek (2009 ▸). Acta Cryst. D65, 148–155], which indicated a solvent cavity of volume 318 Å³ containing approximately 114 electrons. These solvent molecules are not considered in the given chemical formula and other crystal data.

Keywords: crystal structure, β-lactam ring, C(4) chain, hydrogen bonding, N-unsubstituted 2-azetidinone, hydrogen bonds, C—H⋯π interactions

Related literature

For the application of N-unsubstituted 2-azetidinones in the synthesis of β-lactam antibiotics, see: Cossio et al. (1987 ▸); Jarrahpour & Zarei (2007 ▸, 2008 ▸). For a related structure with a β-lactam ring, see: Butcher et al. (2011 ▸). graphic file with name e-71-000o8-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₁ClN₂O₄
M _r = 318.71
Monoclinic,
a = 16.9505 (4) Å
b = 4.6517 (1) Å
c = 21.7167 (6) Å
β = 99.757 (1)°
V = 1687.56 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
16293 measured reflections
4358 independent reflections
3158 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.135
S = 1.04
4358 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989014025845/hb7322sup1.cif

e-71-000o8-sup1.cif^{(187.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014025845/hb7322Isup2.hkl

e-71-000o8-Isup2.hkl^{(239.1KB, hkl)}

Click here for additional data file.^{(5.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014025845/hb7322Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989014025845/hb7322fig1.tif

View of the title compound with displacement ellipsoids for non-H atoms drawn at the 30% probability level.

Click here for additional data file.^{(2.2MB, tif)}

b . DOI: 10.1107/S2056989014025845/hb7322fig2.tif

View of the hydrogen bonding of the title compound along b axis. Only H atoms involved in H bonding are shown.

CCDC reference: 1036035

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg2 is the centroid of the nitrobenzene ring (C4C9).

DHA	DH	HA	D A	DHA
N1H1O1ⁱ	0.86	2.09	2.936(2)	166
C8H8O3ⁱⁱ	0.93	2.53	3.307(2)	142
C15H15O2ⁱⁱⁱ	0.93	2.51	3.338(2)	149
C3H3Cg2^iv	0.98	2.70	3.5118(19)	141

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

Acknowledgments

The authors are indebted to the X-ray laboratory of Dicle University Scientific and Technological Applied and Research Center, Diyarbakir, Turkey, for use of the X-ray diffractometer. AJ and HAS thank the Shiraz University Research Council for financial support.

supplementary crystallographic information

S1. Comment

N-Unsubstituted 2-azetidinones offer major synthetic opportunities in the synthesis of β-lactam antibiotics such as the carbapenems, penams, monobactams, nocardicins, and the glutamine synthetase inhibitor, tabtoxin (Cossio, et al., 1987) The application of N-unsubstituted 2-azetidinones in the semi-synthesis of the anticancer agents, Taxol and Taxotere has also been reported (Jarrahpour, et al., 2007). N-Unsubstituted 2-azetidinones have been prepared by several methods. Among these methods, oxidative cleavage by ceric ammonium nitrate (CAN) of p-alkoxyphenyl moiety attached to the nitrogen of the β-lactam ring offers the most direct synthesis of N-unsubstituted β-lactams (Jarrahpour, et al., 2008).

In the title compound (Fig. 1), the β-lactam ring is nearly planar with a maximum deviation of 0.044 (2) Å for N1 from the mean plane. The carboxyl O atom O1 attached to the β-lactam ring deviates by -0.137 (1) Å from the mean plane of the ring. The β-lactam ring makes dihedral angles of 61.17 (11) and 40.21 (12) ° with the nitro and choloro-benzene rings, respectively.

All bond lengths and angles are comparable with those reported in a related structure (Butcher et al., 2011).

In the crystal, molecules are linked into [010] C(4) chains by N—H···O hydrogen bonds. C—H···O hydrogen bonds (Fig. 2) and weak C—H···π interactions link the chains into a three-dimensional network (Table 1).

S2. Experimental

A solution of (NH₄)₂Ce(NO₃)₆ (CAN) (3.00 mmol) in water (15.00 ml) was added dropwise to a solution of β-lactam (1.00 mmol) in CH₃CN (30.00 ml) at room temperature and stirred for 45 min. Then water (30.00 ml) was added and the mixture was extracted with EtOAc (3 × 20 ml) and washed with 10% of NaHCO₃ (40 ml). The aqueous layer of NaHCO₃ was extracted again with EtOAc (15 ml), and all organic extracts were combined and washed successively with 10% NaHSO₃ (2×30 ml), 10% NaHCO₃ (20 ml), brine (20 ml) and then dried over sodium sulfate. After filtration and evaporation of the solvent in vacuo, the crude product was purified by column chromatography or recrystallization from hexane/EtOAc (4:6) solution to give colourless prisms (Yield 75%). Mp 350–352 K IR (KBr, cm^-1): 1774 (CO β-lactam), 3217 (NH). ¹H NMR (250 MHz, DMSO-d₆) δ(p.p.m.): 5.74 (H-3, d, 1H, J=5.5 Hz), 6.23 (H-4, d, 1H, J=5.5 Hz), 7.27–8.15 (aromatic H, m, 8H), 9.13 (NH, brs, 1H). ¹³C NMR (62.9 MHz, DMSO-d₆) δ(p.p.m.): 54.60 (C-4), 83.18 (C-3), 117.5, 124.7, 125.9, 128.7, 128.9, 129.1, 132.8, 134.4, 147.4, 155.8 (aromatic carbons), 165.90 (CO, β- lactam). Analysis calculated for C₁₅H₁₁ClN₂O₄: C, 51.01; H, 2.85; N, 7.93%. Found: C, 51.03; H, 2.87; N, 7.91%.