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

Ísmail Çelik; Mehmet Akkurt; Aliasghar Jarrahpour; Edris Ebrahimi; Orhan Büyükgüngör

doi:10.1107/S1600536809037830

. 2009 Sep 26;65(Pt 10):o2522–o2523. doi: 10.1107/S1600536809037830

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

Ísmail Çelik ^a, Mehmet Akkurt ^b,^*, Aliasghar Jarrahpour ^c, Edris Ebrahimi ^c, Orhan Büyükgüngör ^d

PMCID: PMC2970342 PMID: 21577969

Abstract

In the title molecule, C₃₅H₂₂BrNO₂, the four-membered ring of the β-lactam unit is nearly planar [maximum deviation = 0.003 (3) Å] and makes dihedral angles of 87.07 (15), 59.80 (16) and 20.81 (19)°, respectively, with the xanthene system, the anthracene system and the bromo-substituted benzene ring. The molecular conformation is stabilized by weak intramolecular C—H⋯O and C—H⋯N hydrogen bonds. The crystal structure features weak C—H⋯π interactions.

Related literature

For general background to β-lactam antibiotics, see: Jarrahpour & Khalili (2007 ▶); Landis-Piwowar et al. (2006 ▶); Palomo et al. (2003 ▶); Skiles & McNeil (1990 ▶); Wu & Tormos (1997 ▶). For related structures, see: Akkurt et al. (2006 ▶, 2007 ▶); Akkurt, Jarrahpour et al. (2008 ▶); Akkurt, Karaca et al. (2008 ▶); Pınar et al. (2006 ▶). For geometric analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₃₅H₂₂BrNO₂
M _r = 568.44
Monoclinic,
a = 11.1143 (4) Å
b = 19.9412 (5) Å
c = 14.0317 (5) Å
β = 122.106 (2)°
V = 2634.28 (16) Å³
Z = 4
Mo Kα radiation
μ = 1.59 mm⁻¹
T = 295 K
0.71 × 0.59 × 0.39 mm

Data collection

Stoe IPDS2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.397, T _max = 0.575
39287 measured reflections
5424 independent reflections
4308 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.122
S = 1.08
5424 reflections
352 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.74 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/S1600536809037830/is2462sup1.cif

e-65-o2522-sup1.cif^{(31.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809037830/is2462Isup2.hkl

e-65-o2522-Isup2.hkl^{(260.2KB, 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	2.30	2.968 (4)	128
C31—H31⋯O2	0.93	2.46	3.073 (4)	123
C11—H11⋯Cg2ⁱ	0.93	2.75	3.653 (5)	164
C26—H26⋯Cg1ⁱ	0.93	2.96	3.616 (4)	129

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Symmetry code: (i) Inline graphic . Cg1 and Cg2 are the centroids of the C8–C13 C30–C35 rings, respectively].

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS2 diffractometer (purchased under grant F.279 of the University Research Fund). The authors thank the Cumhuriyet University Research Foundation (CUBAP grant No 2009/F-266) for financial support.

supplementary crystallographic information

Comment

The application of spiro-β-lactams in peptidomimetic chemistry is well documented, and relevant examples include the development of constrained β-turn mimetics (Palomo et al., 2003). Also, spiro-β-lactams have received attention in medicinal chemistry owing to their antiviral and antibacterial properties, (Skiles et al., 1990) as well as recognized activity as cholesterol absorption inhibitors (Wu & Tormos, 1997). Syntheses of new spiro-β-lactams have been reported in the literature (Jarrahpour & Khalili, 2007). Persistent but relatively limited research has been devoted to the use of compounds related to polycyclic aromatic hydrocarbons (PAH) asanticancer agents. Banik and co-workers have described the cytotoxicity of a number of new and novel PAH against human cancer cell lines (Landis-Piwowar et al., 2006).

In the title compound (I) (Fig. 1), the β-lactam ring (N1/C15/C16/C29) is essentially planar with a maximum deviation of 0.003 (3) Å for C29 from the mean plane and its bond lengths and angles are comparable with the values in our previously papers (Akkurt, Jarrahpour et al., 2008; Akkurt, Karaca et al., 2008; Akkurt et al., 2006,2007; Pınar et al., 2006). Atom O2 lies almost in the β-lactam plane, with a deviation of -0.032 (2) Å. The dihedral angle between the benzene ring (C30—C35) attached at N1 and the β-lactam ring is 20.81 (19)°.

In the xanthene ring system (O1/C17–C28), attached at C16, the benzene rings (C17–C22) and (C23–C28) are almost planar, forming a dihedral angle of 12.84 (16)° with each other. Its central ring, O1/C16/C17/C22/C23/C28, is not planar, with puckering parameters: Q_T= 0.198 (3) Å, θ = 99.3 (9)° and φ = 6.5 (9)° (Cremer & Pople, 1975). The mean plane of the xanthene ring system forms the dihedral angles of 87.07 (15)°, and 84.80 (13)°, with the β-lactam ring and the benzene ring (C30–C35), respectively.

The anthracene ring system, attached at C15, is almost planar, with maximum deviations of -0.034 (3) Å for C14, 0.032 (3) Å for C13 and 0.031 (4) Å for C1, makes dihedral angle of 59.80 (16)°, 78.58 (13)° and 62.40 (8)°, with the β-lactam, benzene and the mean plane of the xanthene ring system, respectively.

Molecular conformation is stabilized by weak intramolecular C—H···O and C—H···N hydrogen bonds. The crystal packing is stabilized by two weak C—H···π interactions [Table 1; Cg1 and Cg2 refer to the ring centroids of the rings (C8–C13) and (C30–C35), respectively]. Fig. 2 shows a view down the a axis of the crystal packing of compound (I).

Experimental

A mixture of (E)-N-(anthracen-10-ylmethylene)-3-bromobenzenamine (0.30 g, 0.83 mmol) and triethylamine (0.42 g, 4.15 mmol), 9H-xanthen-9-carboxylic acid (0.28 g, 1.24 mmol) and tosyl chloride (0.24 g, 1.24 mmol) in CH₂Cl₂(15 ml) was stirred at room temperature for 24 h. Then it was washed with HCl 1 N (20 ml) and saturated sodiumbicarbonate solution (20 ml), brine (20 ml), dried (Na₂SO₄) and the solvent was evaporated to give the crude product as an orange crystal which was then purified by recrystallization from ethyl acetate (yield: 55%, m.p.: 495–497 K). IR (KBr, cm^-1): 1755 (CO β-lactam). ¹H-NMR δ (p.p.m.): 6.18 (s, 1H, H-4), 6.23–8.65 (m, ArH, 21H).¹³C-NMR δ (p.p.m.): 66.0 (C-3), 75.6 (C-4), 115.7–151.9 (aromatic carbon), 167.7 (CO β-lactam). Analysis calculated for C₃₅H₂₂BrNO₂: C 73.95, H 3.90, N 2.46%. Found: C 73.90, H 3.93, N 2.51%.