9-(3,4-Dimeth­oxy­phen­yl)-3,3,6,6-tetra­methyl-4,5,6,9-tetra­hydro-3H-xanthene-1,8(2H,7H)-dione

Sayed Hasan Mehdi; Othman Sulaiman; Raza Murad Ghalib; Chin Sing Yeap; Hoong-Kun Fun

doi:10.1107/S1600536811023014

. 2011 Jun 18;67(Pt 7):o1719–o1720. doi: 10.1107/S1600536811023014

9-(3,4-Dimethoxyphenyl)-3,3,6,6-tetramethyl-4,5,6,9-tetrahydro-3H-xanthene-1,8(2H,7H)-dione

Sayed Hasan Mehdi ^a, Othman Sulaiman ^a, Raza Murad Ghalib ^a, Chin Sing Yeap ^b,^‡, Hoong-Kun Fun ^b,^*,^§

PMCID: PMC3152024 PMID: 21837111

Abstract

The asymmetric unit of the title xanthene compound, C₂₅H₃₀O₅, contains two molecules in which the pyran ring and the dimethoxyphenyl ring are nearly perpendicular to one another [dihedral angles = 86.81 (8) and 84.45 (9)°]. One of the methoxy groups in one molecule is twisted away from the phenyl ring [C—O—C—C torsion angle = −103.40 (16)°]. The pyran ring adopts a boat conformation whereas the two fused cyclohexane rings adopt envelope conformations in both molecules. In the crystal, molecules are linked into a three-dimensional network by C—H⋯O hydrogen bonds.

Related literature

For applications of xanthene derivatives, see: Lambert et al. (1997 ▶); Hideo (1981 ▶); Poupelin et al. (1978 ▶); Menchen et al. (2003 ▶); Banerjee & Mukherjee (1981 ▶); Ravindranath & Seshadri (1973) ▶. For the synthesis of xanthene and 1,8-dioxooctahydroxanthene derivatives with or without the use of a catalyst, see: Fan et al. (2005 ▶); Jin et al. (2005 ▶); Srihari et al. (2008 ▶). For a related structure, see: Mehdi et al. (2011 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For ring conformations, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₅H₃₀O₅
M _r = 410.49
Triclinic,
a = 9.4895 (7) Å
b = 10.2283 (7) Å
c = 23.3218 (16) Å
α = 85.872 (4)°
β = 86.537 (4)°
γ = 74.425 (3)°
V = 2172.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.42 × 0.39 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.965, T _max = 0.983
44431 measured reflections
11497 independent reflections
8871 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.127
S = 1.01
11497 reflections
553 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811023014/hb5885sup1.cif

e-67-o1719-sup1.cif^{(39.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811023014/hb5885Isup2.hkl

e-67-o1719-Isup2.hkl^{(562.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811023014/hb5885Isup3.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
C10A—H10A⋯O4Aⁱ	0.99	2.38	3.2817 (19)	152
C18A—H18A⋯O2Aⁱⁱ	0.95	2.35	3.2943 (19)	176
C18B—H18B⋯O2Bⁱⁱⁱ	0.95	2.45	3.4000 (19)	175
C20A—H20A⋯O3A^iv	0.98	2.59	3.4144 (19)	142
C24B—H24D⋯O4A^v	0.98	2.48	3.453 (2)	171

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

Acknowledgments

SHM, OS and RMG would like to acknowledge Universiti Sains Malaysia (USM) for the University Grant 1001/PTEKIND/8140152. HKF and CSY also thank USM for the Research University Grant 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Synthesis of xanthene derivatives is currently of great interest and has attracted considerable attention by chemists because of their biological and pharmaceutical properties as antiviral (Lambert et al., 1997), antibacterial (Hideo, 1981), and anti-inflammatory (Poupelin et al., 1978). Xanthenes derivatives also find use as dyes, fluorescent material for visualization of biomolecules and in laser technologies (Menchen et al., 2003; Banerjee & Mukherjee, 1981). Several natural occurring polycyclic compounds containing xanthene nucleus are also reported (Ravindranath & Seshadri, 1973). Synthesis of xanthene and 1,8-dioxooctahydroxanthene derivatives have been reported in literature under the different reaction conditions with or without the use of catalyst (Fan et al., 2005; Jin et al., 2005; Srihari et al., 2008). Here we are reporting the synthesis of title compound, (I). The structure of the title compound was established on the basis of its IR, ¹H NMR, ¹³C NMR spectra and finally confirmed by X-ray analysis.

The asymmetric unit of (I) consists of two crystallographically independent molecules, A and B (Fig. 1). The geometric parameters and the conformations are very similar to the previously reported structure (Mehdi et al., 2011). However, only the dimethoxyphenyl of molecule B is different from others. The dimethoxyphenyl grouping in molecule A is almost planar [C20A–O4A–C17A–C18A = -1.9 (2)° and C21A–O5A–C16A–C17A = 4.6 (2)°] whereas for molecule B is not planar [C20B–O4B–C17B–C18B = -6.1 (2)° and C21B–O5B–C16B–C15B = -103.40 (16)°]. Similarly, the mean plane of pyran ring and the dimethoxyphenyl ring for both A and B molecules are nearly perpendicular to one another with the dihedral angles between them being 86.81 (8) and 84.45 (9)°, respectively. For both molecules, the two cyclohexane rings adopt envelope conformations whereas the pyran ring adopts a boat conformation (Cremer & Pople, 1975).

In the crystal, the molecules are linked into a three-dimensional network (Fig. 2) by C—H···O hydrogen bonds (Table 1).

Experimental

A mixture of dimedone (1.40 g m, 10 mmol) and veratraldehyde (1.66 g m, 10 mmol) was heated in 25 ml of glacial acetic acid for three hours. Completion of the reaction was monitored by TLC. The reaction mixture was dried on rotary evaporator under reduced pressure. The crude mixture thus obtained was successively treated with di ethyl ether chloroform and ethanol. The ethanol fraction on crystallization furnished yellow blocks of (I) (m pt. 208 °C, Yield 90%). IR (KBr) ν_max: 3085, 3005, 2956, 2929, 2870, 2822, 1667, 1624, 1515, 1467, 1419, 1358, 1227, 1141, 1105, 1023, 851, 830, 751 cm^{-1. 1}H NMR (300 MHz, DMSO-d₆): δ 6.75–6.92 (3H, m, Aromatic protons), 4.72 (1H, s), 3.83 (3H, s), 3.78 (3H, s), 2.40 (4H, s), 2.17 (4H, s), 1.05 (6H, s), 1.02 (6H, s). ¹³C NMR (75 MHz, DMSO-d₆): δ 27.2, 36.8, 42.4, 52.2, 56.4, 112.2, 114.6, 115.2, 123.4, 136.8, 146.6, 148.4, 198.2. IR spectrum was taken on Shimadzu IR-408 Perkin Elmer 1800 (FTIR). ¹H NMR was recorded on Bruker Avance 300 MHz with TMS as an internal standard and 75 MHz for ¹³C NMR. Spectrum was recorded in DMSO-d₆. The melting point was taken on Thermo Fisher digital melting point apparatus of IA9000 series and is uncorrected.