2,5-Bis[(3-hy­droxy­prop­yl)amino]-1,4-benzoquinone monohydrate

Jian Wang; Weiwei Liu; Tongwei Guan; Fujun Yin; Yuxi Sun

doi:10.1107/S1600536811021635

. 2011 Jun 11;67(Pt 7):o1632. doi: 10.1107/S1600536811021635

2,5-Bis[(3-hydroxypropyl)amino]-1,4-benzoquinone monohydrate

Jian Wang ^a,^*, Weiwei Liu ^a, Tongwei Guan ^a, Fujun Yin ^a, Yuxi Sun ^b

PMCID: PMC3152041 PMID: 21837038

Abstract

The title compound, C₁₂H₁₈N₂O₄·H₂O, was obtained as a product of the reaction of hydroquinone with n-propanol amine. The compound crystallizes as a monohydrate, integrating water into its hydrogen-bonded network. Each diaminoquinone moiety forms two centrosymmetric 10-membered rings through C=O⋯H—N bonds. The resulting bands along [102] are interlinked through hydroxy groups and water molecules into three-dimensional network. The chemically equivalent bond lengths in the diaminoquinone moiety exhibit a perceptible discrepancy [e.g. C=O bond lengths differ by 0.016 (2) Å], apparently as a result of asymmetric hydrogen bonding: one O atom serves as an acceptor of one hydrogen bond, whereas the other is an acceptor of two.

Related literature

For the synthesis of the title compound see: Jian et al. (2009 ▶). For related literature on aminoquinones, see: Der (2010 ▶), Nisha et al. (2010 ▶).

Experimental

Crystal data

C₁₂H₁₈N₂O₄·H₂O
M _r = 272.30
Triclinic,
a = 4.9272 (8) Å
b = 11.673 (2) Å
c = 11.933 (2) Å
α = 82.104 (2)°
β = 87.994 (2)°
γ = 80.849 (2)°
V = 671.13 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.25 × 0.18 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008 ▶) T _min = 0.974, T _max = 0.989
5966 measured reflections
2895 independent reflections
1963 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.116
S = 1.03
2895 reflections
196 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021635/ld2011sup1.cif

e-67-o1632-sup1.cif^{(18KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021635/ld2011Isup2.hkl

e-67-o1632-Isup2.hkl^{(142.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811021635/ld2011Isup3.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
O5—H5B⋯O4ⁱ	0.85 (1)	1.98 (1)	2.818 (2)	168 (2)
O5—H5A⋯O3ⁱⁱ	0.85 (1)	1.90 (1)	2.736 (2)	169 (2)
O3—H3⋯O2ⁱⁱ	0.84 (2)	1.90 (2)	2.7398 (19)	173 (3)
N1—H1⋯O2ⁱⁱ	0.89 (1)	2.20 (1)	2.9865 (18)	146 (2)
N2—H2⋯O1ⁱⁱⁱ	0.89 (1)	2.17 (1)	2.9508 (17)	146 (2)
O4—H4⋯O5^iv	0.85 (2)	1.88 (2)	2.727 (2)	173 (2)

Open in a new tab

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

Acknowledgments

We acknowledge the financial support of the foundation of Jiangsu Key Laboratory of Marine Biotechnology (2010HS07), the Jiangsu Marine Resources Development Research Institute (JSIMR10E02), the Major Program of the Natural Science Foundation of Jiangsu Education Committee (10 K J A170003), the Natural Science Foundation of Jiangsu Education Committee (08KJB150002), the Six Kinds of Professional Elite Foundation of Jiangsu Province (No. 07-A-024), the Science and Technology Critical Project Foundation of Lianyungang (CG0803–2), the Doctoral Scientific Research Project (KQ09006) and the partnership of Huaihai Institute of Technology.

supplementary crystallographic information

Comment

Aminoquinones are used as medicines and herbicides and have interesting redox switching properties. They are formed in the reactions of different amines with quinones or hydroquinone. For example, 1,4-benzoquinone reacts with primary amines to give 2,5-diamino-1,4-benzoquinones. Recently, by reacting hydroquinone with n-propanol amine, 2,5-di[(3-hydroxypropyl)amino]-1,4-benzoquinone has been synthesized. The product was characterized with IR, UV and mass spectrometry, as well as NMR. This and related compounds are of considerable interest since they exhibit potent antitumor and antimalarial activities. However, the single-crystal structure of 2,5-di[(3-hydroxypropyl)amino]-1,4-benzoquinone has not been reported.

Experimental

Methanol solution (10 ml) of n-propanol amine(2.3 mmol) was added to methanol solution (10 ml) of hydroquinone (0.05 g=0.46 mmol), and was stirred for 0.5 h at room temperature. Then the reaction was refluxed at 50°C for 4 h. A deep-red ropiness crude product was formed. The product was purified by recrystallization from methanol. Long red flat prisms were obtained from methanol solution after vaporizing at room temperature for two weeks.