(3R*,4R*)-1-(4-Chloro­phen­yl)-4-[2-hy­droxy-3-(morpholinomethyl)­phen­yl]-3-phen­oxy­azetidin-2-one

Mehmet Akkurt; Aliasghar Jarrahpour; Hashem Sharghi; Seid Ali Torabi Badrabady; Orhan Büyükgüngör

doi:10.1107/S1600536811000675

. 2011 Jan 12;67(Pt 2):o325. doi: 10.1107/S1600536811000675

(3R,4R)-1-(4-Chlorophenyl)-4-[2-hydroxy-3-(morpholinomethyl)phenyl]-3-phenoxyazetidin-2-one

Mehmet Akkurt ^a,^*, Aliasghar Jarrahpour ^b, Hashem Sharghi ^b, Seid Ali Torabi Badrabady ^b, Orhan Büyükgüngör ^c

PMCID: PMC3051698 PMID: 21523011

Abstract

The β-lactam ring of the title compound, C₂₆H₂₅ClN₂O₄, is nearly planar (r.m.s. deviation = 0.025 Å) and the morpholine ring adopts a chair conformation. The mean plane of the β-lactam ring makes dihedral angles of 21.6 (4), 84.4 (4) and 33.7 (4)° with the two benzene rings and the phenyl ring, respectively. The conformation of the title compound is stabilized by intramolecular C—H⋯O and O—H⋯N interactions. The crystal structure features C—H⋯π and aromatic π–π stacking interactions [centroid–centroid distances = 3.684 (4) and 3.883 (4) Å].

Related literature

For a related structure, see: Akkurt et al. (2011 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₆H₂₅ClN₂O₄
M _r = 464.93
Monoclinic,
a = 29.6418 (18) Å
b = 6.7166 (3) Å
c = 28.5708 (15) Å
β = 123.043 (4)°
V = 4768.2 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 296 K
0.53 × 0.23 × 0.04 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.904, T _max = 0.992
16824 measured reflections
4707 independent reflections
1712 reflections with I > 2σ(I)
R _int = 0.159

Refinement

R[F ² > 2σ(F ²)] = 0.087
wR(F ²) = 0.130
S = 1.00
4707 reflections
302 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000675/hb5782sup1.cif

e-67-0o325-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000675/hb5782Isup2.hkl

e-67-0o325-Isup2.hkl^{(230.7KB, hkl)}

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

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

Cg5 is a centroid of the C16–C21 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯N2	0.85 (6)	1.87 (6)	2.642 (8)	150 (5)
C2—H2⋯O2	0.93	2.50	3.304 (6)	144
C15—H15⋯O2	0.93	2.54	3.148 (7)	123
C20—H20⋯Cg5ⁱ	0.93	2.88	3.596 (5)	134

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund). AJ, HS, SATB and MA thank the Shiraz University Research Council for financial support (grant No. 89-GR—SC-23).

supplementary crystallographic information

Comment

As part of our ongoing structural studies of β-lactams (Akkurt et al., 2011), we now report the structure of the title compound, (I).

In the title compound, (I), (Fig. 1), the β-lactam ring (N1/C7–C9) is almost planar, with long C—C distances [C7–C9 = 1.518 (7) Å and C7–C8 = 1.553 (6) Å]. The morpholine ring (N2/O4/C23—C26) adopts a chair conformation, with the puckering parameters of Q_T = 0.594 (8) Å, θ = 177.1 (8)° and φ = 305 (17)° (Cremer & Pople, 1975). The dihedral angles between the mean planes of the rings in (I) are given in Table 2.

The molecular conformation of (I) is stabilized by intra-molecular C— H···O and O— H···N interactions (Table 1). The crystal structure is stabilized by C—H&ctdot;π interactions (Table 1) and two π-π stacking interactions [Cg1···Cg5(x, y, z) = 3.684 (4) Å and Cg4···Cg4(1 - x, -y, -z) = 3.883 (4) Å, where Cg1, Cg4 and Cg5 are the centroids of the N1/C7–C9 β-lactam, the C10–C15 and C16–C21 benzene rings, respectively]. Fig. 2 shows the packing of (I), down the b axis.

Experimental

To a solution of (E)-2-((4-chlorophenylimino)methyl)-6-(morpholinomethyl)phenol (1.0 mmol) and triethylamine (2.6 mmol) in dry CH₂Cl₂ was slowly added phenoxyacetyl chloride (1.3 mmol) in dry CH₂Cl₂ (10 ml) at 195 K. The reaction mixture was then allowed to warm to room temperature, stirred over night and then it was washed with saturated sodium bicarbonate solution (20 ml), brine (20 ml), dried (Na₂SO₄). The solvent was evaporated under reduced pressure to give the crude product which was then purified by column chromatography over silica gel. Colourless needles were recrystallised from ethyl acetate (yield 65%). [mp: 463–465 K]. IR (KBr, cm^-1): 1758.5 (CO β-Lactam), 3311–3497 (OH). ¹H-NMR (250 MHz, CDCl₃) δ (p.p.m): 3.43 (CH₂—N, t, 4H, J = 13.5 Hz), 3.70 (CH₂, s, 2H), 3.88 (CH₂—O, t, 4H, J = 13.9 Hz), 5.59 (H-8, d, 1H, J = 1.6 Hz), 5.91 (H-7, d, 1H, J = 1.6 Hz), 6.67–7.35 (ArH, m, 12H); ¹³C-NMR (62.9 MHz, CDCl₃) δ (p.p.m): 52.6 (CH₂—N), 55.9 (C-22), 50.2 (O—CH₂), 66.5 (C-8), 80.9 (C-7), 115.2–157.0 (aromatic carbons), 163.1 (CO β-Lactam). Analysis calculated for C₂₆H₂₅ClN₂O₄: C 67.17, H 5.42, N 6.03%. found: C 67.05, H 5.47, N 6.08%.