Crystal structure of 2-[(3S,4S)-4-(anthracen-9-yl)-1-(4-meth­oxy­phen­yl)-2-oxoazetidin-3-yl]-2-aza-2H-phenalene-1,3-dione unknown solvate

Ísmail Çelik; Mehmet Akkurt; Aliasghar Jarrahpour; Javad Ameri Rad; Ömer Çelik

doi:10.1107/S2056989015002959

. 2015 Feb 13;71(Pt 3):o184–o185. doi: 10.1107/S2056989015002959

Crystal structure of 2-[(3S,4S)-4-(anthracen-9-yl)-1-(4-methoxyphenyl)-2-oxoazetidin-3-yl]-2-aza-2H-phenalene-1,3-dione unknown solvate

Ísmail Çelik ^a, Mehmet Akkurt ^b,^*, Aliasghar Jarrahpour ^c, Javad Ameri Rad ^c, Ömer Çelik ^d,^e

PMCID: PMC4350708 PMID: 25844239

Abstract

The central β-lactam ring of the title compound, C₃₆H₂₄N₂O₄, is almost planar (r.m.s. deviation = 0.003 Å) and makes dihedral angles of 17.17 (19), 89.76 (17) and 78.44 (17)° with the benzene ring, the anthracene ring (r.m.s. deviation = 0.003 Å) and the 1H-benzo[de]isoquinoline-1,3(2H)-dione moiety, which is nearly planar [maximum deviation = 0.098 (2) Å], respectively. The molecular structure is stabilized by an intramolecular C—H⋯N hydrogen bond. In the crystal, molecules are linked via C—H⋯π and π–π stacking interactions [centroid–centroid distances = 3.5270 (19) and 3.779 (2) Å], forming a three-dimensional structure. A region of disordered electron density, probably disordered solvent molecules, was treated with the SQUEEZE procedure in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9–18], which indicated a solvent cavity of 322 Å³ containing approximately 91 electrons. Their formula mass and unit-cell characteristics were not taken into account during the refinement.

Keywords: crystal structure, β-lactam ring, 2-azetidinone, anthracene, intramolecular C—H⋯N hydrogen bond, C—H⋯π interactions, π–π stacking interactions

Related literature

For general background to β-lactams and their biological properties, see: Fischbach & Walsh (2009 ▸); Georg (1992 ▸); Kim et al. (2014 ▸); Ocampo & Dolbier (2004 ▸); Palomo et al. (2004 ▸); Smith et al. (2014 ▸); Soengas et al. (2011 ▸); von Nussbaum et al. (2006 ▸); Walsh & Wencewicz (2014 ▸). For related structures, see: Çelik et al. (2015 ▸); Atioğlu et al. (2014 ▸); Butcher et al. (2011 ▸); Jarrahpour et al. (2012 ▸); Jarrahpoor & Khalili (2007 ▸); Jarrahpour & Ebrahimi (2010 ▸). For details of the SQUEEZE procedure in PLATON, see: Spek (2015 ▸).

Experimental

Crystal data

C₃₆H₂₄N₂O₄
M _r = 548.57
Monoclinic,
a = 9.9880 (1) Å
b = 29.1281 (4) Å
c = 11.0751 (2) Å
β = 101.367 (1)°
V = 3158.89 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.35 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
33697 measured reflections
6431 independent reflections
3502 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.072
wR(F ²) = 0.242
S = 1.10
6431 reflections
349 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.30 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, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL2014 and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015002959/su5084sup1.cif

e-71-0o184-sup1.cif^{(475.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002959/su5084Isup2.hkl

e-71-0o184-Isup2.hkl^{(352.4KB, hkl)}

Click here for additional data file.^{(10.5KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015002959/su5084Isup3.cml

Click here for additional data file.^{(1.9MB, tif)}

. DOI: 10.1107/S2056989015002959/su5084fig1.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.^{(1.6MB, tif)}

a . DOI: 10.1107/S2056989015002959/su5084fig2.tif

View along a-axis of the crystal packing of the title compound.

CCDC reference: 1048898

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

Table 1. Hydrogen-bond geometry (, ).

Cg5 is the centroid of the C16/C17/C22C24/C29 benzene ring.

DHA	DH	HA	D A	DHA
C28H28N1	0.93	2.35	3.022(4)	129
C13H13Cg5ⁱ	0.93	2.84	3.713(4)	158

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Symmetry code: (i) Inline graphic .

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 JAR thank the Shiraz University Research Council for financial support (grant No. 93-GR–SC-23).

supplementary crystallographic information

S1. Comment

β-Lactams are a very important class of heterocyclic compounds due to their obvious biological activity (Von Nussbaum, et al., 2006). Because the β-lactam ring forms the main part of the penicillin structure, the β-lactam antibiotics have been the subject of much discussion and investigation (Soengas, et al., 2011). However, due to their extensive use common infections are once again becoming deadly (Fischbach & Walsh, 2009) and there is still a significant need for new research on β-lactams (Walsh & Wencewicz, 2014). Furthermore, β-lactams have been used in the synthesis of a wide variety of compounds which contain a nitrogen atom in their structures (Kim et al., 2014). In the past decades, a growing interest has been shown in the development of the various methods for the synthesis of β-lactams (Georg, 1992; Palomo et al., 2004; Ocampo & Dolbier, 2004). It has been observed that the most direct synthetic way to access β-lactam rings remains the formal [2 + 2] cycloaddition of ketenes and imines (Staudinger reaction) [Smith et al., 2014].

The β-lactam ring (N1/C1–C3) of the title compound, Fig. 1, is nearly planar [maximum deviation for atom N1 = 0.051 (2) Å]. It makes dihedral angles of 17.17 (19), 89.76 (17) and 78.44 (17)° with the benzene ring (C30–C35), the anthracene ring system (C16–C29) and the 1H-benzo[de]isoquinoline-1,3(2H)-dione (N2/O2/O3/C4–C15) moiety, respectively. The maximum deviations in the latter two ring systems are 0.050 (2) and 0.098 (2) Å, respectively.

All bond lengths and bond angles are normal and comparable with those reported for related compounds (Çelik et al., 2015; Butcher et al., 2011; Atioğlu et al., 2014; Jarrahpour et al., 2012; Jarrahpoor & Khalili, 2007; Jarrahpour & Ebrahimi, 2010). An intramolecular C—H···N hydrogen bond (Table 1) stabilizes the molecular conformation.

In the crystal, molecules are connected by C—H···π and π-π stacking interactions forming a three-dimensional structure; see Table 1 and Fig. 2 [Cg2···Cg3ⁱ = 3.5270 (19) and Cg6···Cg7ⁱⁱ = 3.779 (2) Å; where Cg2, Cg3, Cg6 and Cg7 are centroids of the N2/C4/C5/C10/C11/C15, C5–C10, C17–C22 and C24–C29 rings, respectively; symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, -y +1/2, z+1/2].

S2. Experimental

1-(anthracen-9-yl)-N-(4-methoxyphenyl) methanimine (1 mmol), triethylamine (5 mmol), 2-(1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl) acetic acid (1.50 mmol) and tosyl chloride (1.50 mmol) were added to anhydrous CH₂Cl₂ (5 ml) and the mixture was stirred at room temperature for 24 h. The mixture was then washed with HCl 1N (2 × 20 ml), saturated aqueous NaHCO₃ solution (50 ml) and brine (20 ml). The organic layer was dried (Na₂SO₄) and the solvent was removed in vacuo to give the product as a yellow solid. It was then purified by recrystallization from DMSO to afford yellow crystals (yield: 80%; m.p.: 458–460 K; IR (KBr, cm^-1): 1751 (CO β-lactam),1704 (CO Naph), 1666 (CO Naph); ¹H-NMR (250 MHz, DMSO-d₆) δ: 3.57 (CH₃ s, 3H), 6.73–6.79 (m, 4H), 6.97 (d, 2H, J = 2.5), 7.09 (aromatic d, 2H, J = 8.75), 7.49–7.57 (aromatic, m, 4H), 7.81–7.90 (aromatic, m, 2H), 8.16 (aromatic d, 2H, J = 7.75), 8.42–8.51 (aromatic, m, 6H), 8.51(aromatic s, 1H); ¹³C-NMR (62 MHz, DMSO-d₆) δ 163.81 (CO β-lactam), 162.18 (CO Naph), 155.77, 134.93, 131.30, 131.18, 131.07, 130.96, 130.01, 129.84, 129.78, 127.52, 127.44, 127.25, 125.17, 124.14, 122.57, 121.41, 117.75, 114.55(aromatic carbons), 62.10 (C β-lactam), 55.58 (C β-lactam), 55.05 (CH₃—O); GC—MS m/z = 548 [M+]; Analysis calculated for C₃₆H₂₄N₂O₄: C, 78.82; H, 4.41; N, 5.11%. Found: C, 76.53; H, 4.45; N, 5.81%.