4a-Hydroxy-9-(4-hydroxyphenyl)-4,4a,5,6,9,9a-hexahydro-3H-xanthene-1,8(2H,7H)-dione

Liying Wang; Weicheng Lu; Yan Yang; Yulin Zhu

doi:10.1107/S1600536811038335

. 2011 Sep 30;67(Pt 10):o2751. doi: 10.1107/S1600536811038335

4a-Hydroxy-9-(4-hydroxyphenyl)-4,4a,5,6,9,9a-hexahydro-3H-xanthene-1,8(2H,7H)-dione

Liying Wang ^a, Weicheng Lu ^a, Yan Yang ^a, Yulin Zhu ^a,^*

PMCID: PMC3201323 PMID: 22058809

Abstract

The title compound, C₁₉H₂₀O₅, was synthesized by the reaction of 1,3-cyclohexanedione and 4-hydroxybenzaldehyde in the presence of PdCl₂ and thiourea. The tetrahydropyran ring and the six-membered cyclohexene ring adopt envelope conformations, and the six-membered cyclohexane ring is in a chair conformation. The crystal packing is stabilized by classical intermolecular O—H⋯O hydrogen bonds and weak C—H⋯O interactions.

Related literature

For applications of related compounds, see: Menchen et al. (2003 ▶); Saint-Ruf et al. (1972 ▶); Reddy et al. (2009 ▶); Mehdi et al. (2011 ▶). For the synthesis of related compounds, see: Karade et al. (2007 ▶); Luna et al. (2009 ▶). For related structures, see: Loh et al. (2011 ▶); Yang et al. (2011 ▶).

Experimental

Crystal data

C₁₉H₂₀O₅
M _r = 328.35
Monoclinic,
a = 9.014 (4) Å
b = 10.242 (4) Å
c = 9.289 (4) Å
β = 108.194 (4)°
V = 814.7 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.35 × 0.30 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.967, T _max = 0.981
4840 measured reflections
1876 independent reflections
1652 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.113
S = 1.04
1863 reflections
219 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811038335/rk2296sup1.cif

e-67-o2751-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038335/rk2296Isup2.hkl

e-67-o2751-Isup2.hkl^{(91.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811038335/rk2296Isup3.cml

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
O4—H4⋯O5ⁱ	0.82	2.07	2.852 (3)	160
O5—H5⋯O2ⁱⁱ	0.82	1.94	2.758 (4)	175
C4—H4B⋯O4ⁱⁱⁱ	0.97	2.50	3.274 (5)	137
C8A—H13⋯O3^iv	0.98	2.59	3.535 (4)	161
C12—H18⋯O2ⁱⁱ	0.93	2.55	3.251 (4)	132

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

Acknowledgments

The authors thank South China Normal University for financial support (grants SCNU G21096).

supplementary crystallographic information

Comment

Xanthenes are an important class of heterocyclic compounds which attract researchers by their spectroscopic and biological properties. Their derivatives had been widely used as dyes, fluorescent materials for visualization and in laser technologies (Menchen et al., 2003; Saint-Ruf et al., 1972; Reddy et al., 2009; Mehdi et al., 2011). Due to their wide range of applications, a well established method used for the construction of xanthene unit was set up, which was a Tandem Michael reaction between 1,3-cyclohexanedione and benzaldehyde (Luna et al., 2009; Karade et al., 2007). The reaction between 1,3-cyclohexanedione and 4-hydroxybenzaldehyde in the presence of thiourea and PdCl₂ proceeded to give the title compound in isolated yield 86% (Fig. 1).

The molecular structure of the title compound is illustrated in Fig. 2. There are no unusual bond lengths and angles in the molecule. The tricyclo system is connected with a phenly ring at the C9 position. The tetrahydropyran ring (O1/C4B/C8A/C9/C9A/C4A) and the six-membered cyclohexene ring (C1–C4/C4A/C9A) adopt envelope conformations, the other six-membered cyclohexane ring (C4B/C5–C8/C8A) is in a chair conformation. Other than the published structure 4a-hydroxy-9-(2-methoxyphenyl)-4,4a,5,6,7,8,9,9a-octahydro-3H-xanthene-1,8(2H)-dione or 3,4,4a,5,6,7,9,9a-octahydro-4a-hydroxyl-9-(4-chlorophenyl)-1H-xanthene-1,8(2H)-dione (Loh et al., 2011; Yang et al., 2011), the main structure of this compound is a derivated xanthene–dione fused tricyclo system with a hydroxyl group at its C4b position. The hydroxy group in phenly ring, tetrahydropyran ring with a hydroxyl group and carbonyl O atom allow the formation of two intermolecular O4—H4···O5ⁱ and O5—H5···O2ⁱⁱ hydrogen bonds. There are weak intermolecular C4—H4B···O4ⁱⁱⁱ, C8A—H13···O3^iv and C12—H18···O2ⁱⁱ interactions which link molecules into chains. Symmetyry codes: (i) x+1, y, z+1; (ii) -x, y+1/2, -z+1; (iii) -x+1, y+1/2, -z+2; (iv) -x, y+1/2, -z+2.

Experimental

A mixture of 1,3-cyclohexanedione (1.12 g, 10 mmol), 4-hydroxybenzaldehyde (0.61 g, 5 mmol), thiourea (0.76 g,10 mmol) and PdCl₂ (0.0020 mg) was refluxed in anhydrous acetonitrile (12 ml) at 373 K for 4 h. After being cooled to room temperature, the reaction mixture was poured into water. The white precipitate was filtered off with a silica pad, washed twice with anhydrous ethanol, and the filtrate was then dried under vacuum to yield the product in yield of 86%. Single crystals of the title compound were obtained by slow evaporation from anhydrous ethanol at room temperature to yield colourless, block-shaped crystal.