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

Sayed Hasan Mehdi; Rokiah Hashim; Raza Murad Ghalib; Chin Sing Yeap; Hoong-Kun Fun

doi:10.1107/S1600536811017867

. 2011 May 20;67(Pt 6):o1449. doi: 10.1107/S1600536811017867

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

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

PMCID: PMC3120437 PMID: 21754824

Abstract

In the title compound, C₂₁H₂₂O₅, the mean planes of the pyran and dimethoxyphenyl rings are nearly perpendicular to one another, with the dihedral angle between them being 88.21 (8)°. The pyran ring adopts a boat conformation whereas the two fused cyclohexane rings adopt envelope conformations. In the crystal, molecules are linked into a three-dimensional network by intermolecular C—H⋯O hydrogen bonds.

Related literature

For condensation reactions between carbonyl compounds with active methylene compounds, see: Chalais et al. (1985 ▶); Prajapati & Sanduh (1993 ▶); Texier-Boullet & Foucaud (1982 ▶); Jone (1967 ▶). 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

C₂₁H₂₂O₅
M _r = 354.39
Monoclinic,
a = 8.7733 (3) Å
b = 15.2246 (5) Å
c = 14.6646 (4) Å
β = 116.891 (2)°
V = 1746.95 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.58 × 0.30 × 0.18 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.947, T _max = 0.983
19254 measured reflections
5118 independent reflections
4066 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.130
S = 1.05
5118 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.35 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 datablocks global, I. DOI: 10.1107/S1600536811017867/bq2301sup1.cif

e-67-o1449-sup1.cif^{(22KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017867/bq2301Isup2.hkl

e-67-o1449-Isup2.hkl^{(250.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811017867/bq2301Isup3.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
C3—H3A⋯O4ⁱ	0.99	2.41	3.3647 (18)	161
C5—H5A⋯O5ⁱⁱ	0.99	2.56	3.2366 (17)	126
C9—H9A⋯O2ⁱⁱ	0.99	2.55	3.3210 (17)	135
C10—H10B⋯O5ⁱⁱⁱ	0.99	2.50	3.4822 (19)	173
C21—H21C⋯O2^iv	0.98	2.57	3.1069 (18)	114

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

Acknowledgments

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

supplementary crystallographic information

Comment

The most important synthetic method for the preparation of substituted alkenes is the condensation reaction between carbonyl compounds with active methylene compounds. Xonotlite, cadmium iodide aluminium oxide and other Lewis acids and bases have been previously used for such type of reactions (Chalais et al., 1985; Prajapati & Sanduh, 1993; Texier-Boullet & Foucaud, 1982; Jone, 1967). In this paper we are reporting the synthesis of title compound (Fig. 1) by simple heating of 1,3-cyclohexanedione with veratraldehyde in acetic acid without the use of any catalyst. The structure is supported by spectral analysis like IR, ¹H NMR, ¹³C NMR and finally confirmed by x-ray crystallography.

In the title compound, the mean plane of pyran ring and the dimethoxyphenyl ring are nearly perpendicular to each other with the dihedral angle between them being 88.21 (8)°. The dimethoxyphenyl ring is planar with the torsion angle of C20–O4–C18–C19 = -5.34 (18)° and C21–O5–C17–C16 = -5.67 (18)°. The two cyclohexane rings adopt envelope conformations [puckering amplitude Q = 0.4284 (16) Å, θ = 124.3 (2)°, φ = 359.0 (3)°; Q = 0.4899 (15) Å, θ = 57.91 (18)°, φ = 132.8 (2)°, whereas the pyran ring adopt a boat conformation [Q = 0.2125 (13) Å, θ = 77.9 (4)°, φ = 187.0 (4)°] (Cremer & Pople, 1975). In the crystal structure, the molecules are linked into a three-dimensional network (Fig. 2) by intermolecular C3—H3A···O4, C5—H5A···O5, C9—H9A···O2, C10—H10B···O5 and C21—H21C···O2 hydrogen bonds (Table 1).

Experimental

A mixture of 1,3-cyclohexanedione (1.12 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 chloroform and ethanol. The ethanol fraction on crystallization furnished cream colored crystals of title compound (yield 90%, m. pt. 216°C). IR (KBr) ν_max: 2966, 2933, 2868, 2833, 1664, 1620, 1513, 1441, 1358, 1261, 1240, 1171, 1132, 1025, 956, 906, 859, 807, 726 cm^{-1. 1}H NMR (300 MHz, DMSO-d₆): δ1.75–1.88 (m, 2H), 1.94–2.06 (m, 2H), 2.20–2.38 (m, 42H), 2.48–2.68 (m, 4H), 4.21 (s, 1H), 6.78–6.96 (3H, m). ¹³C NMR (75 MHz, DMSO-d₆): δ 21.6, 26.9, 30.2, 36.6, 56.8, 112.6, 114.4, 115.8, 123.2, 136.4, 146.2, 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.