A second monoclinic polymorph of N-(2,4-dinitro­phen­yl)-2,4-dinitro­aniline

Yui Tokutome; Tsunehisa Okuno

doi:10.1107/S1600536812051288

. 2013 Jan 4;69(Pt 2):o152. doi: 10.1107/S1600536812051288

A second monoclinic polymorph of N-(2,4-dinitrophenyl)-2,4-dinitroaniline

Yui Tokutome ^a, Tsunehisa Okuno ^a,^*

PMCID: PMC3569221 PMID: 23424444

Abstract

The title compound, C₁₂H₇N₅O₈, was previously described in space group P2₁/n with Z = 4 [Wu et al. (2007 ▶). Acta Cryst. E63, o4194]. The current monoclinic P2₁/c polymorph was obtained from a mixed solution of dichloromethane and hexane. The dihedral angle between the benzene rings is 44.16 (5)°, smaller than in the previously reported polymorph [56.3 (2)°]. As a result of the steric hinderance of the nitro groups, hydrogen bonding is limited intramolecularly. The dihedral angles between the phenyl rings and their attached nitro groups are 18.97 (6) and 17.71 (5)° at the 2-position, and 18.52 (6) and 32.41 (6)° at the 4-position.

Related literature

For the preparation of the title compound, see: Elliot & Smith (2000 ▶). For general background, see Espinoza & Thornton (1994 ▶); Farrell et al. (1985 ▶); Chattanathan & Kalidas (1971 ▶); Southgate & Hall (1971 ▶); Stewart & O’Donnell (1964 ▶). For the first monoclinic polymorph, see: Wu et al. (2007 ▶). graphic file with name e-69-0o152-scheme1.jpg

Experimental

Crystal data

C₁₂H₇N₅O₈
M _r = 349.22
Monoclinic,
a = 12.827 (4) Å
b = 7.4997 (18) Å
c = 15.486 (4) Å
β = 113.906 (4)°
V = 1362.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 93 K
0.10 × 0.10 × 0.06 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: numerical (NUMABS; Rigaku, 1999 ▶) T _min = 0.980, T _max = 0.991
10755 measured reflections
3119 independent reflections
2767 reflections with F ² > 2σ(F ²)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.105
S = 1.06
3119 reflections
230 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXD (Schneider, et al., 2002 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2010 ▶).

Supplementary Material

Click here for additional data file.^{(25KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812051288/ff2093sup1.cif

e-69-0o152-sup1.cif^{(25KB, cif)}

Click here for additional data file.^{(153.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051288/ff2093Isup2.hkl

e-69-0o152-Isup2.hkl^{(153.1KB, hkl)}

Click here for additional data file.^{(5.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812051288/ff2093Isup3.cml

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

Acknowledgments

This work was supported by Research for Promoting Technological Seeds from the Japan Science and Technology Agency (JST).

supplementary crystallographic information

Comment

The title compound, (I), is a derivative of nitrodiphenylamines which were used in nonlinear optical materials (Southgate & Hall, 1971). And the title compound was also used in smokeless gunpowder as a stabilizer (Espinoza & Thornton, 1994). Previously, (I) was isolated in a monoclinic P2₁/n polymorph with Z = 4 (Wu et al., 2007). A new monoclinic P2₁/c polymorph was obtained by recrystallization from a mixed solution of dichloromethane and hexane.

The bond lengths and angles of the current molecule were almost similar to those of the reported one. However the significant difference was recognized at the dihedral angle between the two benzene rings. Although the angle of the reported molecule was 56.3 (2)°, that of the current molecule was 44.16 (5)°. Owing to the relatively small dihedral angle, the intramolecular distances between the N-bound H atom and the O atoms of the nitro groups at 2-position became close (Table 1). Because of the steric hinderance of the nitro groups, hydrogen-bondings are limited within the molecule.

The intermolecular contact was recognized between the oxygen atoms of the nitro groups, where the distances were 2.8032 (14) Å for O4···O4ⁱ and 2.8859 (17) Å for O7···O7ⁱⁱ [Symmetry codes: (i) -x, -y + 1, -z + 1; (ii) -x + 1, -y + 1, -z] (Figure 2).

Experimental

Preparation of the title compound was carried out according to the reported procedure (Elliot & Smith, 2000). Single crystals with sufficient quality for X-ray crystallographical analysis were prepared by recrystallization from a mixed solution of dichloromethane and hexane.