2,4-Dinitro-1-naphthol

Abdul Rauf Raza; Aeysha Sultan; M Nawaz Tahir; Amra Rubab

doi:10.1107/S1600536810045034

. 2010 Nov 6;66(Pt 12):o3101. doi: 10.1107/S1600536810045034

2,4-Dinitro-1-naphthol

Abdul Rauf Raza ^a, Aeysha Sultan ^a, M Nawaz Tahir ^b,^*, Amra Rubab ^a

PMCID: PMC3011602 PMID: 21589407

Abstract

In the title compound, C₁₀H₆N₂O₅, the two fused rings are almost co-planar, with an r.m.s. deviation of 0.0163 Å. The nitro groups are oriented at dihedral angles of 2.62 (11) and 44.69 (11)° with respect to the plane of the parent fused rings. Intramolecular O—H⋯O and C—H⋯O hydrogen bonds complete S(6) ring motifs. In the crystal, molecules are linked into chains along [101] by intermolecular O—H⋯O hydrogen bonds. π–π interactions [centroid–centroid distances = 3.6296 (15), 3.8104 (15) and 3.6513 (14) Å] might play a role in stabilizing the structure.

Related literature

For background to estrogens, see: Schwartz et al. (1995 ▶); O’Donnell et al. (2001) ▶. For related structures, see: Filipenko et al. (2001 ▶); Rozycka-Sokolowska et al. (2004 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶). For π–π interactions, see: Janiak (2000 ▶).

Experimental

Crystal data

C₁₀H₆N₂O₅
M _r = 234.17
Monoclinic,
a = 7.0512 (10) Å
b = 16.3541 (19) Å
c = 8.7988 (10) Å
β = 111.452 (6)°
V = 944.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 296 K
0.32 × 0.14 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.978, T _max = 0.982
6868 measured reflections
1684 independent reflections
1058 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.119
S = 1.00
1684 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810045034/dn2615sup1.cif

e-66-o3101-sup1.cif^{(15.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810045034/dn2615Isup2.hkl

e-66-o3101-Isup2.hkl^{(81.3KB, 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
O5—H5A⋯O1ⁱ	0.82	2.53	3.006 (3)	118
O5—H5A⋯O4	0.82	1.87	2.573 (2)	142
O5—H5A⋯N2	0.82	2.47	2.892 (3)	113
C5—H5⋯O1	0.93	2.35	2.902 (3)	118

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. ARR also acknowledges the Higher Education Commission, Government of Pakistan, for generous support of the research project (20–819).

supplementary crystallographic information

Comment

Estrogens have been found to have maintenance effects on bone, brain, skin, cardiovascular system (Schwartz et al., 1995). In spite of their beneficial biological effects, estrogens are suspected to have relationship with the risk of cancer and thromboemetic diseases (O'Donnell et al., 2001). The title compound was obtained as an interesting side product while synthesizing substituted 1-tetralone as AB ring of the estrogen skeleton which will bear substituent at positions not found in nature.

The title compound (I) is related to the published crystal structures of 1-naphthalenol (Rozycka-Sokolowska et al., 2004) and hydroxonium 2,4-dinitro-1-hydroxy-7-sulfonatonaphthalene monohydrate (Filipenko et al., 2001).

In (I), the two fused rings (C1—C10) are neraly planar with the largest deviation being 0.033 (2)Å at C10 (Fig. 1). The hydroxyl O5 atom is only deviating by 0.129 (2)Å from the mean plane. Owing to the intramolecular O5–H···O4 hydrogen bond (Table 1), the O3 and O4 atoms are only slightly displaced from the mean plane of the fused rings by -0.074 (2)Å and 0.023 (2) Å, respectively. The other nitro group is twisted by 44.72 (12)° with respect to the fused rings.

Strong intramolecular H-bondings of O—H···O and C—H···O types (Table 1, Fig. 1) complete S(6) ring motifs (Bernstein et al., 1995). The molecules are stabilized in the form of polymeric chains due to intermolecular O—H···O hydrogen bonds (Table 1, Fig. 2). Slippest weak π–π interactions (Table 2) might play a role in stabilizing the packing.

Experimental

The 1-tetralone (1 ml, 1.1 g, 1 eq) was added to a chilled and well stirred nitrating mixture containing H₂SO₄ (2 ml, 0.57 g, 2 eq) and HNO₃ (0.5 ml, 0.7 g, 1.5 eq). The reaction mixture was then neutralized and extracted with EtOAc (3 × 25 ml) and the combined organic extract was dried over anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography and the title compound (I) was obtained as dull brown crystalline solid in 61–79^th fraction (20 ml each) using 2.5% CHCl₃ (3 × 500 ml) as mobile phase. Yield: 15%.