5-Hydr­oxy-8-nitro-1,4-naphthoquinone

Daniel Teoh-Chuan Tan; Hasnah Osman; Azlina Harun Kamaruddin; Reza Kia; Hoong-Kun Fun

doi:10.1107/S1600536808021594

. 2008 Jul 19;64(Pt 8):o1523–o1524. doi: 10.1107/S1600536808021594

5-Hydroxy-8-nitro-1,4-naphthoquinone

Daniel Teoh-Chuan Tan ^a, Hasnah Osman ^a,^‡, Azlina Harun Kamaruddin ^b, Reza Kia ^c, Hoong-Kun Fun ^c,^*

PMCID: PMC2962149 PMID: 21203231

Abstract

The title compound, C₁₀H₅NO₅, features an intramolecular O—H⋯O hydrogen bond, forming a six-membered ring with an S(6) ring motif. The nitro group makes a dihedral angle of 71.66 (5)° with the plane of the benzene ring to which it is bound. The two rings are almost coplanar, with a dihedral angle of 4.44 (5)°. Short intermolecular distances between the centroids of the six-membered rings [3.7188 (6)–3.8299 (6) Å] indicate the existence of π–π interactions. The interesting features of the crystal structure are the short intermolecular O⋯O and O⋯N interactions. The crystal packing is stabilized by intramolecular O—H⋯O and intermolecular C—H⋯O (×3) hydrogen bonds, and C—H⋯π interactions.

Related literature

For related literature on hydrogen-bond motifs, see Bernstein et al. (1995 ▶). For values of bond lengths, see Allen et al. (1987 ▶). For related literature, see, for example: Guingant & Barreto (1987 ▶); Larsen et al. (1996 ▶); Krohn et al. (2004 ▶); Krohn et al. (2004 ▶); Cui et al. (2006 ▶); Anuradha et al. (2006 ▶).

Experimental

Crystal data

C₁₀H₅NO₅
M _r = 219.15
Monoclinic,
a = 8.6809 (2) Å
b = 8.4250 (2) Å
c = 12.1845 (3) Å
β = 93.946 (1)°
V = 889.02 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 100.0 (1) K
0.35 × 0.14 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.900, T _max = 0.982
22792 measured reflections
3028 independent reflections
2493 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.119
S = 1.11
3028 reflections
165 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); 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, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021594/at2591sup1.cif

e-64-o1523-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021594/at2591Isup2.hkl

e-64-o1523-Isup2.hkl^{(148.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected interatomic and centroid–centroid distances (Å).

Cg1 and Cg2 are the centroids of the C1–C5/C10 and C5–C10 rings, respectively.

Cg1⋯Cg2ⁱ	3.7188 (6)
Cg1⋯Cg2ⁱ	3.8299 (6)
O2⋯O5ⁱ	2.9940 (11)
O5⋯O5ⁱⁱ	3.0367 (11)
O5⋯N1ⁱⁱ	3.0608 (11)

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

Table 2. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C1–C5/C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O2	0.889 (18)	1.769 (19)	2.5695 (10)	148.5 (16)
C2—H2⋯O3ⁱⁱⁱ	0.969 (15)	2.547 (16)	3.1853 (12)	123.4 (12)
C3—H3⋯O5ⁱⁱ	0.970 (15)	2.577 (15)	3.3827 (13)	140.6 (11)
C7—H7⋯O1^iv	0.982 (16)	2.561 (16)	3.1851 (13)	121.4 (12)
C8—H8⋯Cg1^v	0.950 (15)	2.976 (14)	3.6548 (11)	129.5 (11)

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

Acknowledgments

HO thanks the Malaysian government for the FRGS fund (grant No. 203/PKIMIA/671026). DTCT thanks Universiti Sains Malaysia for financial support. HKF and RK thank the Malaysian government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. RK thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

5-Hydroxy-1,4-naphthoquinone (juglone) and its 5-acetoxy-2-bromo analogue is the essential dienophile in the highly convergent and regiospecific Diels-Alder synthesis of ochromycinone (Guingant & Barreto, 1987; Larsen et al., 1996; Krohn et al., 2004) a type of natural anthraquinone which exhibits remarkable antibiotic and antitumour activities (Krohn et al., 2004; Cui et al., 2006). Our aim is to prepare aromatic ring substituted juglone analogues for the purpose of synthesizing new ochromycinone analogues. The title compound was prepared by the direct nitration of juglone with nickel(II) nitrate. The method outlined previously (Anuradha et al., 2006) predicted a ortho-nitro product. However the product that we obtained is a para-nitro product.

Compound (I), ( Fig. 1), features an intramolecular O—H···O hydrogen bond to form a six-membered ring, producing a S(6) ring motif (Bernstein et al., 1995). The bond lenghts and angles are within the normal ranges (Allen et al., 1987). The two phenyl rings are almost coplanar with the dihedral angle of 4.44 (5)°. The nitro group is not coplanar with the benzene ring and its orientation is indicated by the dihedral angle of 71.66 (5)° with the plane of the benzene ring to which it is bound. The short intermolecular distances between the centroids of six-membered rings [3.7188 (6) - 3.8299 (6) Å] prove existence of π–π interactions (Table 1). The interesting feature of the crystal structure is the short intermolecular O···O and O···N interactions (Table 1). The crystal packing,(Fig. 2), of the compound shows one-dimensional infinite chains along the b axis.The crystal packing is stabilized by the intramolecular O—H···O, intermolecular C—H···O hydrogen bonds, π–π, and C—H···π interactions.

Experimental

8-Nitro-5-hydroxy-1,4-naphthoquinone was prepared from 5-hydroxy-1,4-naphthoquinone by the protocol outlined by (Anuradha et al., 2006). Single crystals of 8-nitro-5-hydroxy-1,4-naphthoquinone was obtained by slow evaporation of a chloroform solution at 286 K° C.