14-Bromo-12-chloro-2,16-dioxa­penta­cyclo­[7.7.5.01,21.03,8.010,15]henicosa-3(8),10,12,14-tetra­ene-7,20-dione

Alan R Kennedy; Mehmet Akkurt; Shaaban K Mohamed; Antar A Abdelhamid; Adel A E Marzouk

doi:10.1107/S1600536813010374

. 2013 Apr 20;69(Pt 5):o769–o770. doi: 10.1107/S1600536813010374

14-Bromo-12-chloro-2,16-dioxapentacyclo[7.7.5.0^1,21.0^3,8.0^10,15]henicosa-3(8),10,12,14-tetraene-7,20-dione

Alan R Kennedy ^a, Mehmet Akkurt ^b, Shaaban K Mohamed ^c,^d,^*, Antar A Abdelhamid ^c, Adel A E Marzouk ^e

PMCID: PMC3648294 PMID: 23723914

Abstract

In the title compound, C₁₉H₁₆BrClO₄, both the fused xanthene rings and one of the cyclohexane rings adopt envelope conformations, while the other cyclohexane ring is in a chair conformation. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming infinite chains running along [10-1] incorporating R ₂ ²(16) ring motifs. In addition, C—H⋯π interactions and weak π–π stacking interactions [centroid–centroid distance = 3.768 (3) Å] help to consolidate the packing.

Related literature

For similar structures, see: Mohamed et al. (2012b ▶); Lu et al. (2011 ▶); Abdelhamid et al. (2011 ▶). For the bioactiviy of xanthenones, see: Mohamed et al. (2012a ▶); Gobbi et al. (2006 ▶); Na (2009 ▶). For ring conformations, see: Cremer and Pople (1975 ▶). graphic file with name e-69-0o769-scheme1.jpg

Experimental

Crystal data

C₁₉H₁₆BrClO₄
M _r = 423.67
Monoclinic,
a = 10.2741 (6) Å
b = 10.2800 (6) Å
c = 15.8581 (8) Å
β = 102.073 (5)°
V = 1637.85 (16) Å³
Z = 4
Mo Kα radiation
μ = 2.70 mm⁻¹
T = 123 K
0.25 × 0.20 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.529, T _max = 0.616
7243 measured reflections
3516 independent reflections
2547 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.134
S = 1.04
3516 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(27.8KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813010374/hb7072sup1.cif

e-69-0o769-sup1.cif^{(27.8KB, cif)}

Click here for additional data file.^{(172.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813010374/hb7072Isup2.hkl

e-69-0o769-Isup2.hkl^{(172.4KB, hkl)}

Click here for additional data file.^{(6.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813010374/hb7072Isup3.cml

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

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

Cg3 is the centroid of the C1–C6 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O3ⁱ	0.99	2.53	3.407 (6)	147
C9—H9B⋯Cg3ⁱⁱ	0.99	2.89	3.731 (5)	143

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

Acknowledgments

This work was supported financially by the Higher Education Ministry of Egypt. The authors gratefully acknowledge Manchester Metropolitan University, the University of Strathclyde and Erciyes University for supporting this study.

supplementary crystallographic information

Comment

Xanthenones have very diverse biological profiles, including antihypertensive, anti-oxidative, antithrombotic and anticancer activity, depending on their diverse structures, which are modified by substituents on the ring system (Gobbi et al., 2006; Na, 2009). Following to our earlier study on synthesis of series of the bioactive oxanthenediones (Abdelhamid et al., 2011), acridinediones (Mohamed et al., 2012a) and benzopyranes (Mohamed et al., 2012b) we became interested in synthesizing the title compound to investigate the relationship between antibacterial activity and structure.

In the title compound, (Fig. 1), the two fused xanthene rings (O2/C7/C12–C14/C19 and O4/C5–C7/C12/C13) adopt envelope conformations [the puckering parameters (Cremer & Pople, 1975) are Q_T = 0.522 (5) Å, θ = 127.4 (5) °, φ = 299.1 (6) ° and Q_T = 0.539 (5) Å, θ = 125.9 (5) °, φ = 51.2 (6) °, respectively], one (C14–C19) of the cyclohexane rings is also in an envelope conformation with puckering parameters of Q_T = 0.440 (5) Å, θ = 129.9 (7) °, φ = 344.4 (9) °, and the other (C7–C12) is in a chair conformation with puckering parameters of Q_T = 0.518 (5) Å, θ = 8.0 (6) °, φ = 84 (4). All the bond lengths and bond angles of the title compound are within the expected values and are comparable with those reported for similar structures (Mohamed et al., 2012b; Lu et al., 2011; Abdelhamid et al., 2011).

In the crystal structure, long-range C—H···O hydrogen bonds (Table 1, Fig. 2) connect the adjacent molecules into infinite chains running along [101] with R²₂(16) ring motifs. C–H···π interactions and weak π-π stacking interactions [Cg3···Cg3ⁱ= 3.768 (3) Å; Cg3 is a centroid of the C1–C6 benzene ring and symmetry code: (i) = 1 - x, 1 - y, 1 - z] also contribute to the consolidation of the crystal packing.

Experimental

A mixture of 1 mmol (236 mg) 3-bromo-5-chloro-2-hydroxybenzaldehyde, 1 mmol (112 mg) cyclohexane-1,3-dione and 1 mmol (123 mg) (4-aminophenyl)methanol in 50 ml e thanol was refluxed at 350 K. The reaction progress was monitored by TLC till completion after 5 h. Excess solvent was evaporated under vacuum and the resulted solid was filtered, washed with cold ethanol and recrystallized from ethanol to afford 61% of the title compound. Colourless blocks were obtained by slow evaporation of ethanol solution of (I) at room temperature for two days. M.P. 504 K.