2-Meth­oxy­anilinium 3-hy­droxy-2,4,6-trinitro­phenolate

Doraisamyraja Kalaivani; Rangasamy Malarvizhi; Kaliyaperumal Thanigaimani; Packianathan Thomas Muthiah

doi:10.1107/S1600536811005708

. 2011 Feb 23;67(Pt 3):o686. doi: 10.1107/S1600536811005708

2-Methoxyanilinium 3-hydroxy-2,4,6-trinitrophenolate

Doraisamyraja Kalaivani ^a,^*, Rangasamy Malarvizhi ^a, Kaliyaperumal Thanigaimani ^b, Packianathan Thomas Muthiah ^c

PMCID: PMC3052155 PMID: 21522431

Abstract

The cation and anion of the title molecular salt, C₇H₁₀NO⁺·C₆H₂N₃O₈ ⁻, are linked via an N—H⋯O hydrogen bond. An intramolecular O—H⋯O hydrogen bond is also found in the anion. In the crystal, the anions self-assemble via O—H⋯O hydrogen bonds, forming a C(9) supramolecular chain the b axis. Further intermolecular N—H⋯O interactions also occur.

Related literature

For crystalline metal complexes of styphnic acid, see: Cui et al. (2008a ▶,b ▶); Orbovic & Codoceo (2008 ▶); Zheng et al. (2006a ▶,b ▶); Zhu & Xiao (2009 ▶). For crystalline adducts of styphnic acid with organic bases, see: Abashev et al. (2001 ▶); Liu et al. (2008 ▶); Tenishev et al. (2002 ▶); For related molecular salts, see: Kalaivani & Malarvizhi (2010 ▶); Vogel (1978 ▶).

Experimental

Crystal data

C₇H₁₀NO⁺·C₆H₂N₃O₈ ⁻
M _r = 368.27
Monoclinic,
a = 10.6957 (4) Å
b = 17.8368 (5) Å
c = 8.0527 (3) Å
β = 91.991 (2)°
V = 1535.34 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 293 K
0.22 × 0.18 × 0.12 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.978, T _max = 0.988
19208 measured reflections
4930 independent reflections
3539 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.142
S = 1.04
4930 reflections
238 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.40 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: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005708/bv2174sup1.cif

e-67-0o686-sup1.cif^{(23.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005708/bv2174Isup2.hkl

e-67-0o686-Isup2.hkl^{(236.6KB, 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
N1—H1A⋯O2	0.89	1.89	2.7408 (16)	158
N1—H1C⋯O2ⁱ	0.89	1.87	2.7569 (16)	177
O5—H5⋯O6	0.82	1.95	2.6311 (18)	140
O5—H5⋯O9ⁱⁱ	0.82	2.29	2.9263 (17)	135

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

Acknowledgments

The authors thank the DST-India (FIST programme) for the use of the Bruker SMART APEXII diffractometer at the School of Chemistry, Bharathidasan University.

supplementary crystallographic information

Comment

In spite of the fact that many crystalline complexes have been derived from styphnic acid and metals in recent years [(Cui et al., 2008a, 2008b), (Orbovic et al., 2008), (Zheng et al., 2006a, 2006b), (Zhu & Xiao, 2009)], only a few crystalline complexes are known from styphnic acid and organic molecules [(Abashev et al., 2001), (Liu et al., 2008), (Tenishev et al., 2002)]. It has also been pointed out that aromatic hydrocarbons (and also some amines) form 1:1 adducts with styphnic acid and these derivatives do not crystallize as well as the corresponding picrates (Vogel, 1978). In the present work an elegant method has been proposed to prepare a crystalline molecular salt from 2-methoxyaniline and styphnic acid.

The title compound (I), is shown in Fig 1. The adduct formation between styphnic acid and 2-methoxyaniline may involve two important types of charge-transfer interactions (i) π-π^* transition and (ii) proton transfer. A view of the crystal packing is shown in Fig 2. The proton transfer from phenolic OH to amino group is the main contributing factor which stabilizes the title molecular salt. The same observation has been reported by us in a related molecular salt (Kalaivani & Malarvizhi, 2010). The 3-hydroxy-2,4,6-trinitrophenolate ions self-assemble via O—H···O hydrogen bonds to from a supramolecular chain the b axis, with the graph-set notation C(9); this is shown in Fig. 3.

Experimental

2,4,6-Trinitro-1,3-benzenediol (styphnic acid: 2.45 g, 0.01 mol) was dissolved in the minimum quantity of dimethyl sulphoxide. 2-Methoxyaniline (1.23 g, 0.01 mol) dissolved in the minimum amount of dimethyl sulphoxide was added to styphnic acid solution. The mixture was stirred well for 3 h and kept as such for another 12 h. The mixture was then poured into ice cold water with stirring. The molecular salt (adduct) formed was filtered and washed first with water and then with alcohol and dried. The dried adduct was washed several times with ether and recrystallized from ethanol (yield 70–75%, mp.455 K). Good pale yellow crystals of the molecular salt were obtained by slow evaporation of ethanol at room temperature. The same molecular salt was obtained when styphnic acid (0.01 mol) was mixed with excess of 2-methoxyaniline (0.03 mol).