Crystal structure of 1-(4-meth­oxy­phen­yl)-4-(4-nitro­phen­yl)-3-phen­oxy­azetidin-2-one

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

doi:10.1107/S2056989014025833

. 2015 Jan 1;71(Pt 1):o12–o13. doi: 10.1107/S2056989014025833

Crystal structure of 1-(4-methoxyphenyl)-4-(4-nitrophenyl)-3-phenoxyazetidin-2-one

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

PMCID: PMC4331848 PMID: 25705479

Abstract

In the title compound, C₂₂H₁₈N₂O₅, the central β-lactam ring (r.m.s. deviation = 0.002 Å) makes dihedral angles of 64.21 (14), 82.35 (12) and 20.66 (13)° with the phenyl ring and the nitro- and methoxybenzene rings, respectively. The molecular structure is stabilized by an intramolecular C—H⋯O hydrogen bond. In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming slabs lying parallel to (111). The slabs are linked via C—H⋯π interactions, forming a three-dimensional network.

Keywords: crystal structure, phenoxyazetidin-2-one, β-lactam ring, four-membered monocyclic aza-heterocycles, antibiotics, C—H⋯O hydrogen bonds, C—H⋯π interactions

Related literature

For general properties and applications in medicinal chemistry of four-membered monocyclic aza-heterocycles, see: Bode et al. (1989 ▸); Gerona-Navarro et al. (2004 ▸); Grafe (1992 ▸); Gérard et al. (2004 ▸); Mehta et al. (2010 ▸); Setti et al. (2005 ▸); Singh et al. (2008 ▸); Southgate (1994 ▸); Sutton et al. (2004 ▸); Sperka et al. (2005 ▸). For related structures, see: Akkurt et al. (2011 ▸); Butcher et al. (2011 ▸). graphic file with name e-71-00o12-scheme1.jpg

Experimental

Crystal data

C₂₂H₁₈N₂O₅
M _r = 390.38
Triclinic,
a = 9.8044 (3) Å
b = 10.6483 (3) Å
c = 11.1573 (3) Å
α = 66.957 (1)°
β = 70.105 (1)°
γ = 65.973 (1)°
V = 956.06 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
16870 measured reflections
3586 independent reflections
2860 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.125
S = 1.09
3586 reflections
257 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.17 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/S2056989014025833/su5026sup1.cif

e-71-00o12-sup1.cif^{(29KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989014025833/su5026Isup2.hkl

e-71-00o12-Isup2.hkl^{(196.8KB, hkl)}

Click here for additional data file.^{(7.3KB, cml)}

Supporting information file. DOI: 10.1107/S2056989014025833/su5026Isup3.cml

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

. DOI: 10.1107/S2056989014025833/su5026fig1.tif

Perspective view of the molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

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

a . DOI: 10.1107/S2056989014025833/su5026fig2.tif

View of the hydrogen bonding and molecular packing of the title compound along a axis (only H atoms involved in hydrogen bonding are shown; see Table 1 for details).

CCDC reference: 1036033

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

Table 1. Hydrogen-bond geometry (, ).

Cg4 is the centroid of the methoxyphenyl ring (C16C21).

DHA	DH	HA	D A	DHA
C17H17O1	0.93	2.60	3.172(3)	120
C12H12O1ⁱ	0.93	2.37	3.103(2)	135
C21H21O4ⁱⁱ	0.93	2.43	3.127(3)	132
C15H15Cg4ⁱⁱⁱ	0.93	2.75	3.674(2)	173

Open in a new tab

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

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

Four-membered monocyclic aza-heterocycles (Singh, et al., 2008), even more than 70 years after the discovery of penicillin, β-lactam antibiotics remain as one of the most important contributions of science to humanity (Southgate, 1994). β-Lactam antibiotics have been successfully used in the treatment of infectious diseases for many years (Grafe, 1992). Literature survey reveals that 2-azetidinones show to possess other relevant biological activities (Gerona-Navarro et al., 2004). which include human cytomegalovirus (HCMV) inhibitor, (Mehta et al., 2010), human leukocyte elastase (HLE) inhibitor, (Gérard et al., 2004), thrombin inhibitor, (Sutton et al., 2004), porcine pancreatic elastase (PPE) inhibitor, (Bode et al., 1989), HIV-1 protease inhibitor (Sperka et al., 2005), cysteine protease inhibitor (Setti et al., 2005).

In the title compound (Fig. 1), the β-lactam ring (N1/C1–C3) is nearly planar [r.m.s. deviation = 0.002 Å]. It makes dihedral angles of 64.21 (14), 82.35 (12) and 20.66 (13)° with the phenyl ring (C4–C9) and the nitro- and methoxybenzene rings (C10–C15 and C16–C21), respectively.

The bond lengths and bond angles are normal and are similar to the corresponding bond distances and angles reported for similar compound, viz. 1-(4-methoxyphenyl)-4-(4-methylphenyl)-3-phenoxyazetidin-2-one (Akkurt et al., 2011) and 3-(4-chlorophenoxy)-1-(4-methoxyphenyl)-4-(4-nitrophenyl)azetidin-2-one (Butcher et al., 2011).

A weak intramolecular C—H···O hydrogen bond stabilizes the molecular conformation (Table 1).

In the crystal, molecules are linked by C—H···O hydrogen bonds forming slabs lying parallel to (111). The slabs are linked via C—H···π interactions forming a three dimensional network (Table 1 and Fig. 2).

S2. Experimental

A solution of (E)-4-methoxy-N-(4-nitrobenzylidene)aniline (1.00 mmol) was stirred with the phenoxy acetic acid (1.50 mmol), p-toluenesulfonyl chloride (1.50 mmol) and triethylamine (5.0 mmol) in dry CH₂Cl₂ at room temperature overnight. Then it was washed with HCl 1 N (20 ml), saturated NaHCO₃ (20 ml), brine (20 ml), dried over Na₂SO₄ and the solvent was evaporated under reduced pressure to give the crude product. It was then recrystallized from hexan/EtOAc (2:6) to give colourless prisms (yield 75%; m.p: 413–415 K). IR (KBr, cm^-1): 1744 (CO, β-lactam). ¹H-NMR (250 MHz CDCl₃), δ (p.p.m.): 3.69 (OMe, s, 3H), 5.01 (H-4, d, 1H, J = 4.7 HZ), 5.40 (H-3, d, 1H, J = 4.7 HZ), 6.69–8.10 (ArH, m, 13H). ¹³C-NMR (62.9 MHz, CDCl₃), δ (p.p.m.): 54.3 (OMe), 63.7 (C-4), 83.1 (C-3), 114.5–157.2 (aromatic carbons), 162.8 (CO, β-lactam). GC—MS m/z = 391 [M+]. Analysis calculated for C₂₂H₁₈N₂O₅: C, 67.69; H, 4.65; N, 7.18%. Found: C, 67.65; H, 4.70; N, 7.20%.