2-Amino-4-nitro­phenol–1-(2,4,6-trihy­droxy­phen­yl)ethanone (1/1)

Can Kocabıyık; Hümeyra Paşaoğlu; Taşkın Basılı; Erbil Ağar

doi:10.1107/S1600536812017497

. 2012 Apr 25;68(Pt 5):o1527–o1528. doi: 10.1107/S1600536812017497

2-Amino-4-nitrophenol–1-(2,4,6-trihydroxyphenyl)ethanone (1/1)

Can Kocabıyık ^a,^*, Hümeyra Paşaoğlu ^a, Taşkın Basılı ^b, Erbil Ağar ^b

PMCID: PMC3344630 PMID: 22590392

Abstract

In the title compound, C₆H₆N₂O₃·C₈H₈O₄, the 2-amino-4-nitrophenol (ANP) and 1-(2,4,6-trihydroxyphenyl)ethanone (THA) molecules are both nearly planar, with r.m.s. deviations of 0.0630 and 0.0313 Å, respectively. The angle between the least-squares planes of THA and ANP is 48.99 (2)°. In THA, an intramolecular O—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds lead to the formation of a three-dimensional network. There are also intermolecular π–π interactions between the benzene rings of ANP–ANP and of THA–THA molecules, with centroid–centroid distances of 3.5313 (14) and 3.8440 (16) Å, respectively. Weak C—O⋯π and N—O⋯π interactions also occur.

Related literature

For the use of nitroaromatics as intermediates in explosives, dyestuffs, pesticides and organic synthesis, see: Yan et al. (2006 ▶). For the occurrence of nitroaromatics in industrial wastes and as direct pollutants in the environment, see: Yan et al. (2006 ▶); Soojhawon et al. (2005 ▶). For graph-set motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Tanak et al. (2009 ▶, 2010 ▶); Ali et al. (2008 ▶); Bi et al. (2009 ▶); Garden et al. (2004 ▶); Serdiuk et al. (2011 ▶).

Experimental

Crystal data

C₆H₆N₂O₃·C₈H₈O₄
M _r = 322.27
Monoclinic,
a = 7.7255 (6) Å
b = 13.2184 (11) Å
c = 15.8335 (12) Å
β = 118.148 (5)°
V = 1425.67 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.80 × 0.35 × 0.09 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED; Stoe & Cie, 2002 ▶) T _min = 0.942, T _max = 0.992
15333 measured reflections
2961 independent reflections
1841 reflections with I > 2σ(I)
R _int = 0.065

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.098
S = 0.97
2961 reflections
252 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); 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 Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812017497/kj2199sup1.cif

e-68-o1527-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017497/kj2199Isup2.hkl

e-68-o1527-Isup2.hkl^{(142.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812017497/kj2199Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C7–C12 and C1–C6 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O6ⁱ	0.93 (3)	2.28 (3)	3.067 (2)	141.5 (19)
N2—H2B⋯O6ⁱⁱ	0.93 (3)	2.36 (3)	3.241 (3)	157 (2)
O3—H3A⋯N1ⁱⁱⁱ	0.84 (3)	2.59 (3)	3.358 (3)	153 (3)
O3—H3A⋯O1ⁱⁱⁱ	0.84 (3)	2.39 (3)	2.953 (3)	125 (3)
O3—H3A⋯O2ⁱⁱⁱ	0.84 (3)	2.13 (3)	2.975 (3)	178 (3)
O4—H4⋯N2	0.86 (3)	1.94 (3)	2.784 (2)	166 (2)
O5—H5A⋯O7ⁱ	0.88 (3)	1.87 (3)	2.748 (2)	175 (3)
O6—H6⋯O7	0.92 (3)	1.64 (3)	2.478 (2)	150 (2)
N1—O2⋯Cg2^iv	1.22 (1)	3.82 (1)	3.599 (3)	70 (1)
C13—O7⋯Cg1^v	1.25 (1)	3.52 (1)	3.722 (3)	89 (1)

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

Acknowledgments

The authors sincerely thank Professor Dr Orhan Büyükgüngör and Dr Gökhan Kaştaş for their contributions.

supplementary crystallographic information

Comment

Nitroaromatics are widely used either as materials or as intermediates in explosives, dyestuffs, pesticides and organic synthesis (Yan et al., 2006). Nitroaromatics occur as industrial wastes and direct pollutants in the environment, and are relatively soluble in water and detectable in rivers, ponds and soil (Yan et al., 2006; Soojhawon et al., 2005).

The title compound (Fig. 1) crystallizes in the monoclinic space group P2/c with Z = 4 in the unit cell. The asymmetric unit in the crystal structure therefore contains only one formula unit. The bond lengths and angles of the ANP and THA moieties have normal values. The C4—N1 [1.448 (3) Å] and C13—C14 [1.486 (3) Å] bond distances are comparable to those observed in related structures (Ali et al., 2008; Tanak et al., 2009; Tanak et al., 2010; Bi et al., 2009; Garden et al., 2004; Serdiuk et al. 2011). The ANP and THA molecules are almost planar with the maximum deviations, -0.0694 (18) Å for atom O1 in the ANP and -0.152 (2) Å for atom C14 in the THA molecules. The dihedral angle between these rings is 48.99 (2)°.

The crystal packing of the title compound is stabilized by non-covalent hydrogen bond, π-π and X—Y···π-ring interactions. It can be seen from Fig. 2 that neighbouring ANP moieties are linked by O3—H3A···O1ⁱⁱⁱ and O3—H3A···O2ⁱⁱⁱ (iii: x - 1, -y + 1, z - 1/2) hydrogen bonds to form C(8) chains in direction [201], producing R¹₂(4) rings (Bernstein et al., 1995). In addition, THA moieties are mutually connected to each other by O5—H5A···O7ⁱ hydrogen bonds (i: x, -y, z + 1/2), forming a C(8) chain running in direction [001] (Fig. 3). These two chains are further connected by N2—H2A···O6ⁱ, N2—H2B···O6ⁱⁱ (ii: -x + 1, -y, -z + 1) and O4—H4···N2 hydrogen bonds between ANP and THA moieties. The arrangement of ANP and THA gives rise to R²₂(8) and R³₄(12) rings. The N2 (in ANP) and O6 (in THA) atoms act as both donor and acceptor. Finally, the intra-molecular O6—H6···O7 hydrogen bond of THA generates an S(6) ring motif (Fig. 4).

In the extended structure of the compound, there are weak π-π and X—Y···π-ring interactions. The intermolecular π-π contact occurs between the two symmetry-related ANP (ring A) rings of neighboring molecules. Ring A is oriented in such a way that the distance between the ring centroids is 3.8440 (16) Å. The other π-π interaction is between THA (ring B) rings, with a distance of 3.5313 (14) Å between the ring centroids. Rings A and B are also involved in intermolecular N—O···π and C—O···π interactions through N atom of ANP and C atom of THA. With regard to the N—O···π contact, for two neighboring B rings,the distance between atom O2 and the center of ring B (CgB) is 3.822 (2) Å and the N1—O2···CgB angle is 70.29 (15)°. In addition, there are also C—O···π interactions between C13—O7 and A rings, which can be characterized by the O7···CgA distance of 3.521 (3) Å and the C13—O7···CgA angle of 89.33 (15)°.

Experimental

1-(2,4,6-trihydroxyphenyl)ethanone-2-amino-4-nitrophenol (1/1) was prepared by refluxing a mixture of a solution containing 2,4,6-trihydroxyacetephenone (18,6 mg, 0,1 mmol) in ethanol (25 ml) and a solution containing 2-amino-4-nitrophenol (15,4 mg, 0,1 mmol) in ethanol (20 ml). The reaction mixture was stirred for 4 h under reflux. Single crystals of the title compound for X-ray analysis were obtained by slow evaporation of an ethanol solution (Yield 74%; m.p 442.-446 K).