1,8-Bis(tos­yloxy)-9,10-anthraquinone

Paweł Niedziałkowski; Damian Trzybiński; Artur Sikorski; Tadeusz Ossowski

doi:10.1107/S1600536809051009

. 2009 Dec 4;66(Pt 1):o33–o34. doi: 10.1107/S1600536809051009

1,8-Bis(tosyloxy)-9,10-anthraquinone

Paweł Niedziałkowski ^a, Damian Trzybiński ^a, Artur Sikorski ^a,^*, Tadeusz Ossowski ^a

PMCID: PMC2980119 PMID: 21580139

Abstract

In the crystal structure of the title compound, C₂₈H₂₀O₈S₂, adjacent anthracene skeletons are parallel or inclined at an angle of 20.6 (1)°. In the molecular structure, the mean plane of the anthracene skeleton makes dihedral angles of 49.6 (1) and 76.8 (1)° with the tosyl rings, and the two terminal benzene rings are oriented at an angle of 74.5 (1)° with respect to each other. The crystal structure is stabilized by intermolecular C—H⋯O and C—O⋯π interactions.

Related literature

For general background to anthraquinones, see: Cheng & Zee-Cheng (1983 ▶); Dzierzbicka et al. (2006 ▶); Gatto et al. (1996 ▶); Hunger (2003 ▶); Krapcho et al. (1991 ▶); Nakanishi et al. (2005 ▶); Zielske (1987 ▶); Zon et al. (2003 ▶). For related structures, see: Sereda & Akhvlediani (2003 ▶); Slouf (2002 ▶); Zain & Ng (2005 ▶). For molecular interactions, see: Bianchi et al. (2004 ▶); Santos-Contreras et al. (2007 ▶); Spek (2009 ▶); Steiner (1999 ▶). For the synthesis, see: Ossowski et al. (2000 ▶).

Experimental

Crystal data

C₂₈H₂₀O₈S₂
M _r = 548.58
Monoclinic,
a = 8.263 (2) Å
b = 27.473 (5) Å
c = 11.162 (2) Å
β = 100.36 (3)°
V = 2492.6 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 295 K
0.4 × 0.3 × 0.15 mm

Data collection

Oxford Diffraction Gemini R ULTRA Ruby CCD diffractometer
18048 measured reflections
4371 independent reflections
3374 reflections with I > 2σ(I)
R _int = 0.050

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.163
S = 1.15
4371 reflections
345 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; 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: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809051009/xu2694sup1.cif

e-66-00o33-sup1.cif^{(23.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809051009/xu2694Isup2.hkl

e-66-00o33-Isup2.hkl^{(214.2KB, 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
C24—H24⋯O18ⁱ	0.93	2.54	3.332 (4)	143
C33—H33⋯O30ⁱⁱ	0.93	2.56	3.241 (4)	130
C36—H36⋯O31ⁱⁱⁱ	0.93	2.58	3.458 (4)	156

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

Table 2. C–O⋯π interactions (Å,°).

C	O	J	O⋯J	C⋯J	C–O⋯J
C10	O27	Cg1^iv	3.688 (3)	3.481 (3)	70.71 (17)
C10	O27	Cg2^v	3.452 (3)	3.528 (3)	83.41 (18)

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Symmetry codes: (iv) −x, −y + 1, −z + 1; (v) −x + 1, −y + 1, −z + 1. Cg1 and Cg2 are the centroids of the C1—C4/C11/C12 and C5—C8/C13/C14 rings respectively.

Acknowledgments

This work was supported by the Polish State Committee for Scientific Research (grant Nos. R02 0010 06 and DS 8210–4-0177–9).

supplementary crystallographic information

Comment

Anthraquinones, its amino and hydroxy derivatives as the largest group of naturally occurring quinines are of great practical significance in pharmacology, biochemistry and dye chemistry (Hunger, 2003). Anthraquinones are widely widespread in nature, they are occur in bark, or roots of different plants, and display various pharmacological activities such as anti-oxidant, anti-microbial, anti-fungal and anti-viral (Nakanishi et al., 2005). The anthraquinone ring system is often found in antitumor drugs, such as anthracyclines, mitoxantrone, ametantrone and anthrapyrazoles (Cheng & Zee-Cheng, 1983). Its planarity allows an intercalation between base pairs of DNA in the β conformation, while its redox properties are linked to the production of radical species in biological systems. The chemical and biological activity of anthraquinone compounds depends on the different substituents of the planar ring system (Krapcho et al., 1991, Gatto et al., 1996). Anthraquinones are also interesting compounds for the investigations in analytical and electroanalytical chemistry due to the fact that they contain several π electrons, the reducible p-quinone system and are electroactive (Zon et al., 2003). The tosyl group is a very good leaving group, commonly used in organic synthesis in nucleophilic substitution reaction. This phenomenon is applicable to prepare the various aminoanthraquinone from (tosy1oxy)anthraquinone precursors (Zielske, 1987). The 1,8-Bis(tosyloxy)-9,10-anthraquinone is a very convenient and often used precursor to obtain the 1,8-diaminoanthraquinones derivatives (Dzierzbicka et al., 2006).

In the molecule of the title compound (Fig. 1) the bond lengths and angles characterizing the geometry of the anthraquinone skeleton are typical for this group of compounds (Sereda & Akhvlediani, 2003; Slouf, 2002; Zain & Ng, 2005).

In the packing of molecules of the title compound, the anthracene skeletons, with an average deviations from planarity of 0.044 (1) Å, are parallel or inclined at an angle of 20.1 (1)°. The mean plane of the anthracene skeleton makes dihedral angles of 49.6 (1)° and 76.8 (1)°, with the tosyl phenyl rings. Those phenyl rings are oriented at the angle of 74.5 (1)° to each other.

The crystal structure is stabilized by C–H···O (Table 1, Fig. 2) and C–O···π (Table 1, Fig. 3) intermolecular interactions. The C–H···O interactions are the hydrogen bond type (Steiner, 1999, Bianchi et al., 2004). All interactions demonstrated were found by PLATON (Spek, 2009).

Experimental

1,8-Bis(tosyloxy)-9,10-anthraquinone was synthesized according to the method reported in the literature (Ossowski et al., 2000). To the stirring mixture of 5.0 g (20.8 mmol) 1,8-dihydroxy-9,10-anthraquinone and 5.22 g (27.4 mmol) of p-toluenesulfonyl chloride in 200 ml dichloromethane was dropwise added over 5 h 15 ml triethylamine in 100 ml dichloromethane. The progress of the reaction was monitored by TLC (SiO₂, dichloromethane-petroleum ether 1:1 v/v) until the completion of reaction. The reaction mixture was stirred 6 h at room temperature. The solution was washed with water (3 x 100 ml), the organic phase was dried over MgSO₄ and concentrated. The residue was purified by column chromatography on silica gel (dichloromethane-petroleum ether, 1:0.8 v/v) to afford the title compound as a yellow solid. (3.64 g, 28%). Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in methanol at room temperature (m.p. = 448–450 K; elemental analysis (% found/calculated: C 61.41/61.30, H 3.65/3.67, S 11.69/11.69)).