4-(9-Anthr­yl)-1-(2,4-dimethoxy­phen­yl)spiro­[azetidine-3,9′-xanthen]-2-one

Zeliha Baktır; Mehmet Akkurt; Aliasghar Jarrahpour; Edris Ebrahimi; Orhan Büyükgüngör

doi:10.1107/S1600536809022739

. 2009 Jun 20;65(Pt 7):o1623–o1624. doi: 10.1107/S1600536809022739

4-(9-Anthryl)-1-(2,4-dimethoxyphenyl)spiro[azetidine-3,9′-xanthen]-2-one

Zeliha Baktır ^a, Mehmet Akkurt ^a,^*, Aliasghar Jarrahpour ^b, Edris Ebrahimi ^b, Orhan Büyükgüngör ^c

PMCID: PMC2969353 PMID: 21582891

Abstract

The title compound, C₃₇H₂₇NO₄, crystallizes with two molecules in the asymmetric unit. The β-lactam ring of each molecule is very nearly planar, with maximum deviations of 0.001 (2) and 0.017 (2) Å in the two molecules. The crystal structure is stabilized by intermolecular C—H⋯O and C—H⋯N contacts, as well as by weak C—H⋯π interactions.

Related literature

For the biological properties of spiro-β-lactams, see: Kobayashi et al. (1991 ▶); Sheehan et al. (1978 ▶); Skiles & McNeil (1990 ▶); Waldmann (1995 ▶). For polycyclic aromatic β-lactams with anti-cancer activity, see: Banik et al. (2003 ▶, 2004 ▶); Becker & Banik (1998 ▶). For several syntheses of spiro-β-lactams, see: Jarrahpoor & Khalili (2007 ▶). For the structural characterizations of some β-lactam compounds, see: Akkurt et al. (2008a ▶,b ▶); Yalçın et al. (2009 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₃₇H₂₇NO₄
M _r = 549.60
Triclinic,
a = 12.3164 (6) Å
b = 13.1277 (7) Å
c = 18.4838 (11) Å
α = 92.434 (5)°
β = 109.236 (4)°
γ = 91.357 (4)°
V = 2816.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 295 K
0.35 × 0.32 × 0.28 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.971, T _max = 0.977
30264 measured reflections
11851 independent reflections
6076 reflections with I > 2σ(I)
R _int = 0.100

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.131
S = 0.88
11851 reflections
762 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 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: 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: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022739/tk2470sup1.cif

e-65-o1623-sup1.cif^{(57.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022739/tk2470Isup2.hkl

e-65-o1623-Isup2.hkl^{(567.7KB, hkl)}

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
C2—H2⋯N1	0.93	2.33	2.964 (3)	125
C2′—H2′⋯N1′	0.93	2.31	2.957 (3)	126
C3—H3⋯O4′ⁱ	0.93	2.59	3.484 (4)	163
C9—H9⋯O1ⁱⁱ	0.93	2.56	3.458 (4)	164
C35—H35⋯O2	0.93	2.58	3.132 (3)	119
C35—H35⋯O2ⁱⁱⁱ	0.93	2.52	3.212 (3)	131
C35′—H35′⋯O2′	0.93	2.52	3.106 (3)	121
C2—H2⋯Cg1	0.93	2.59	3.188 (3)	122
C2′—H2′⋯Cg15	0.93	2.62	3.196 (3)	121

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 and Cg15 are the centroids of the N1/C15/C16/C29 and N1′/C15′/C16′/C29′ rings, respectively.

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).

supplementary crystallographic information

Comment

Spiro compounds represent an important class of naturally occurring compounds characterized by pronounced biological properties (Kobayashi et al., 1991; Waldmann, 1995). Spiro-β-lactams are also interesting due to their anti-viral (Skiles & McNeil, 1990) and anti-bacterial properties (Sheehan et al., 1978). Several syntheses of spiro-β-lactams are available in the literature (Jarrahpoor & Khalili, 2007). Some polycyclic aromatic β-lactams with anti-cancer effects have also been reported (Banik et al., 2003 & 2004; Becker & Banik, 1998). As an extension of our work (Yalçın et al., 2009; Akkurt et al., 2008a,b) on structural characterization of the β-lactam compounds, the title compound, (I), is reported herein.

The asymmetric unit of (I) contains two enantiomorphic molecules IA and IB (Fig. 1 for molecule IA and Fig. 2 for molecule IB) and there is one chiral centre in each molecule, i.e. at C15, which have S and R configurations. In (I), the bond lengths and angles are comparable with the values found in related structures (Yalçın et al., 2009; Akkurt et al., 2008a,b). The β-lactam units of molecules IA and IB are very nearly planar, with maximum deviations of 0.001 (2) Å and -0.017 (2) Å, respectively, from the respective least-squares plane. The dihedral angles between the planes in molecules IA and IB are given in Table 2, and those between the similar planes of the molecules IA and IB are given in Table 3.

In the xanthene ring systems, the central ring, [O1/C16/C17/C22/C23/C28 for molecule IA, and O1'/C16'/C17'/C22'/C23'/C28' for molecule IB] is not planar, with puckering parameters: Q_T= 0.417 (3) Å, θ = 98.2 (4)° and φ = 4.8 (4)° for molecule IA and Q_T= 0.357 (2) Å, θ = 81.1 (3)° and φ = 185.9 (4)° for molecule IB (Cremer & Pople, 1975).

The anthracene ring systems, attached at C15 for molecule IA and C15' for molecule IB, are almost planar, with significant deviations of -0.068 (4) Å for C3, 0.050 (3) Å for C6, and -0.052 (3) Å for C10 in molecule IA, and with significant deviations of -0.040 (3) Å for C6', 0.043 (3) Å for C11', and -0.075 (2) Å for C14' in molecule IB.

The molecular conformation is stabilized by intramolecular C—H···O and C—H···N contacts. Molecules are linked to each other by intermolecular C—H···O and C—H···N contacts and by weak C—H···π interactions (Table 1).

Experimental

A mixture of the Schiff base (E)—N-(anthracen-9-ylmethylene)-2,4-dimethoxybenzamine (0.30 g, 0.87 mmol) and triethylamine (0.44 g, 4.39 mmol), 9H-xanthen-9-carboxylic acid (0.30 g,1.31 mmol) and tosyl chloride (0.25 g, 1.31 mmol) in CH₂Cl₂ (15 ml) was stirred at room temperature for 24 h. The solution was washed with HCl (1 N, 20 ml), a saturated sodium bicarbonate solution (20 ml), and then brine (20 ml). It was then dried over Na₂SO₄. The solvent was evaporated to give the crude product as a light-green crystalline material which was then purified by recrystallization from ethylacetate [yield 69%, m.p. 453–455 K]. IR (KBr, cm^-1): 1739 (CO β-lactam). ¹H-NMR δ (p.p.m.): 2.91, 3.58 (s, 6H, 2OMe) 6.16 (s, 1H, 4), 6.17–8.18 (m, ArH, 20H). ¹³C-NMR δ (p.p.m.): 55.4, 55.5(2OMe), 65.9 (C-3), 78.1 (C-4), 100.2–158.2 (aromatic carbon), 167.7 (CO β-lactam). Analysis calculated for C₃₇H₂₇NO₄: C 80.86, H 4.95, N 2.55%. Found: C 80.03, H 4.98, N 2.83%