3-Hy­droxy-2-[(2-hy­droxy-4,4-dimethyl-6-oxocyclo­hex-1-en-1-yl)(3-nitro­phen­yl)meth­yl]-5,5-dimethyl­cyclo­hex-2-en-1-one

B Palakshi Reddy; V Vijayakumar; S Sarveswari; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536810040079

. 2010 Oct 13;66(Pt 11):o2806–o2807. doi: 10.1107/S1600536810040079

3-Hydroxy-2-[(2-hydroxy-4,4-dimethyl-6-oxocyclohex-1-en-1-yl)(3-nitrophenyl)methyl]-5,5-dimethylcyclohex-2-en-1-one

B Palakshi Reddy ^a, V Vijayakumar ^a,^‡, S Sarveswari ^a, Seik Weng Ng ^b, Edward R T Tiekink ^b,^*

PMCID: PMC3009059 PMID: 21589000

Abstract

Each of the cyclohexenone rings in the title compound, C₂₃H₂₇NO₆, adopts a half-chair (envelope) conformation with the C atom carrying the methyl groups lying out of the plane defined by the five remaining C atoms; the O atoms lie to the same side of the molecule as the respective >C(CH₃)₂ atoms. The hydroxy and carbonyl O atoms face each other and are orientated to allow for the formation of two intramolecular O—H⋯O hydrogen bonds. In the crystal, the presence of C—H⋯O contacts leads to the formation of supramolecular chains along the b axis. These aggregate into layers that stack along c.

Related literature

For the biological activity and uses of xanthenes, see: Jonathan et al. (1988 ▶); Pohlers & Scaiano (1997 ▶); Hilderbrand & Weissleder (2007 ▶). For background to xanthenedione derivatives, see: Hatakeyama et al. (1988 ▶); Shchekotikhin & Nikolaeva (2006 ▶).

Experimental

Crystal data

C₂₃H₂₇NO₆
M _r = 413.46
Monoclinic,
a = 14.2326 (10) Å
b = 8.6505 (6) Å
c = 16.8410 (12) Å
β = 97.796 (1)°
V = 2054.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.792, T _max = 0.862
18883 measured reflections
4717 independent reflections
3928 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.112
S = 1.03
4717 reflections
279 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810040079/hb5662sup1.cif

e-66-o2806-sup1.cif^{(23.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810040079/hb5662Isup2.hkl

e-66-o2806-Isup2.hkl^{(231.1KB, 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
O1—H1o⋯O4	0.85 (1)	1.80 (1)	2.6392 (13)	167 (2)
O3—H3o⋯O2	0.86 (1)	1.75 (1)	2.5985 (13)	170 (2)
C5—H5a⋯O4ⁱ	0.99	2.34	3.2781 (16)	158
C9—H9⋯O6ⁱⁱ	1.00	2.56	3.3431 (16)	135
C21—H21⋯O2ⁱⁱⁱ	0.95	2.44	3.3121 (16)	152

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

Acknowledgments

VV is grateful to the DST, India, for funding through the Young Scientist Scheme (Fast Track Proposal). The authors are also grateful to the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

Xanthenes are known for to possess various biological properties including anti-bacterial, anti-viral and anti-inflammatory activities (Jonathan et al., 1988). In particular, xanthenedione derivatives constitute a structural unit in several natural products (Hatakeyama et al., 1988), and they are valuable synthons because of the inherent reactivity of the in-built pyran ring (Shchekotikhin & Nikolaeva, 2006). Xanthene derivatives are also very useful and important organic compounds widely used as dyes (Hilderbrand & Weissleder, 2007), in laser technologies, and as fluorescent materials for visualization of biomolecules (Pohlers & Scaiano, 1997).

The molecular structure of the title compound, Fig. 1, features two cyclohexene rings, each with a half-chair conformation as, in each case, the C4 and C13 atoms, i.e. carrying two methyl groups, lie above the respective least-squares plane through the remaining five carbon atoms. For each ring, the O atoms lie to the same side of the molecule as the C4 or C13 atoms. The hydroxyl- and carbonyl-O atoms of one cyclohexene ring face the carbonyl- and hydroxyl-O atoms of the other to allow for the formation of intramolecular O—H···O hydrogen bonds, Table 1. The nitro group is co-planar with the benzene ring to which it is attached as seen in the O5—N1—C22—C21 torsion angle of -176.02 (11) °. The nitro-substituted benzene ring occupies a position almost side-on to both cyclohexene rings.

The most prominent intermolecular interactions in the crystal packing are of the type C—H···O, Table 1. These serve to link molecules into a supramolecular chain along the b axis, Fig. 2. The chains pack into layers in the ab plane which stack along the c axis, Fig. 3.

Experimental

A mixture of 3-nitrobenaldehyde (0.377 g, 0.0025 mol), dimedone (0.7 g, 0.005 mol) was refluxed in acetonitrile (20 ml) for 3 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the solution was left for 2 days to precipitate the solid product. The product was recrystallized by slow evaporation of its acetonitrile solution which yielded colourless blocks of (I). Yield: 72%. M.pt. 443–445 K.