9,10-Dioxoanthracene-1,4-diyl bis­(4-methyl­benzene­sulfonate)

Thapong Teerawatananond; Chiaranan Kerdsamut; Sirirat Kokpol; Nongnuj Muangsin

doi:10.1107/S1600536812015814

. 2012 Apr 18;68(Pt 5):o1423–o1424. doi: 10.1107/S1600536812015814

9,10-Dioxoanthracene-1,4-diyl bis(4-methylbenzenesulfonate)

Thapong Teerawatananond ^a, Chiaranan Kerdsamut ^b, Sirirat Kokpol ^c, Nongnuj Muangsin ^d,^*

PMCID: PMC3344545 PMID: 22590307

Abstract

The title molecule, C₂₈H₂₀O₈S₂, has a T-shaped conformation. The central 9,10-anthraquinone moiety is bow-shaped with the two outer aromatic rings being inclined to one another by 13.99 (11)°. The benzenesulfonate rings are inclined to one another by 47.35 (12)°, and by 34.51 (11) and 17.88 (11)° to the bridging aromatic ring of the 9,10-anthraquinone moiety. In the crystal, C—H⋯O interactions link the molecules into ribbons in [100].

Related literature

For background to the structures of anthraquinones and their biological activity, see: Zielske (1987 ▶); Yatsenko et al. (2000 ▶); Huang et al. (2004 ▶); Meng et al. (2005 ▶); García-Sosa et al. (2006 ▶); Cho et al. (2006 ▶); Carland et al. (2010 ▶). For related structures, see: Swaminathan & Nigam (1967 ▶); Cao et al. (2007 ▶).

Experimental

Crystal data

C₂₈H₂₀O₈S₂
M _r = 548.56
Triclinic,
a = 9.6796 (2) Å
b = 10.9426 (3) Å
c = 13.1833 (4) Å
α = 111.122 (1)°
β = 90.961 (1)°
γ = 107.190 (1)°
V = 1232.41 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 296 K
0.35 × 0.20 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.912, T _max = 0.948
12983 measured reflections
5616 independent reflections
3997 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.127
S = 1.02
5616 reflections
343 parameters
346 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.30 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 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812015814/cv5268sup1.cif

e-68-o1423-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015814/cv5268Isup2.hkl

e-68-o1423-Isup2.hkl^{(269.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812015814/cv5268Isup3.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
C7—H7⋯O4ⁱ	0.93	2.48	3.333 (3)	153
C3—H3⋯O8ⁱⁱ	0.93	2.49	3.245 (3)	139

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

Acknowledgments

We thank the Organizing Commitee for a bursary to attend the XXII IUCr 2011 Congress, the American Crystallographic Association (ACA) for a scholarship to attend the 2009 ACA Summer Course in Small Molecule Crystallography, the 90th Anniversary of Chulalongkorn University Fund (Ratchadaphisek Somphot Endowment Fund), the Thai Government Stimulus Package 2 (TKK2555) project, the Center for Petroleum Petrochemicals and Advanced Materials, and the Research Centre for Bioorganic Chemistry (RCBC), Chulalongkorn University, for financial support.

supplementary crystallographic information

Comment

Anthraquinone and its derivatives have been studies in the many fields, for example, antimicrobial and antibiotic activity (García-Sosa et al., 2006), anticancer agents (Huang, et al., 2004; Carland et al., 2010). Additionally, both of unsubstituted and substituted anthraquinone play an important role in various photochemical and colorimetric sensor systems (Cho et al., 2006). The natural extracts or synthetic anthraquinones have been used in the field of dyes and pigments (Meng et al., 2005; Yatsenko et al., 2000; Cao et al., 2007).

1,4-Bis(hydroxy)anthraquinone is one of an important anthraquinone starting materials for preparation the various anthraquinone dyes and pigments (Zielske, 1987). In this work, we report the intermediate of an anthraquinone dye with the two symmetric tosylate substituents.

The molecular structure of 1,4-bis(tosyloxy)anthraquinone consisting of the two tosylate groups substituted at 1,4-positions of anthraquinone core, has a dragonfly-like conformation with the stranded 9,10-anthraquinone fragment. The anthraquinone plane is distorted by 0.1814 Å from the mean plane defined by 16 atoms becuase of the steric effect of two substitued tosyl groups. The O1 and O2 atoms were deviatated from the anthraquinone mean plane with the distances of -0.2736 (16) Å and -0.1467 (15) Å, respectively, which are respectively in the normal range for the distortion of oxyquinone reported for 1,4-bis(hydroxy)anthraquinone (Swaminathan et al., 1967). Additionally, the moderate intermolecular hydrogen bonds of sp²C—H···O have been investigated between the hydrogen atom bound the aromatic carbon inside quinone ring, and the oxygen atom at the sulfonate group in the p-toluenesulfonate moiety as Figure 2. The distance of C(7)—H(7)···O(4) is 3.333 (3) Å and C(3)—H(3)···O(8) is 3.245 (3) Å that showed in the Table 1. In the crystal structure, non-classical intermolecular C—H···O hydrogen bonds link molecules into ribbons in [100].

Experimental

1,4-Bis(tosyloxy)anthraquinone was prepared by a stirred solution of 1,4-bis(hydroxyl)anthraquinone or quinizarin (0.241 g, 1.00 mmol) in 25 mL of dry dichloromethane was added triethylamine (0.205 g, 2.03 mmol) and p-toluenesulfonyl chloride (0.383 g, 2.01 mmol). The solution was stirred at room temperature for 24 hours. The precipitate was filtered off and then washed with water and dried over magnesium sulfate. Filtration of slurry gave a bright yellow-green solid. The final product was recrystallized in hexane:dichloromethane using slow evaporation which was suitable for X-ray diffraction analysis. Additionally, ¹H of 1,4-bis(tosyloxy)anthraquinone were recorded in CDCl₃ solution on a Varian Mercury Plus 400 spectrometer. ¹H NMR spectrum (δ, ppm): 7.94-8.02 (2H,m); 7.69-7.91 (6H,m); 7.45 (2H,s); 7.24-7.33 (4H,m); 2.35 (6H,s) (Zielske et al., 1987).