2,4,6-Trinitro­phenyl 4-methyl­benzoate

Rodolfo Moreno-Fuquen; Fabricio Mosquera; Javier Ellena; Juan C Tenorio; Rodrigo S Corrêa

doi:10.1107/S1600536812041773

. 2012 Oct 13;68(Pt 11):o3107. doi: 10.1107/S1600536812041773

2,4,6-Trinitrophenyl 4-methylbenzoate

Rodolfo Moreno-Fuquen ^a,^*, Fabricio Mosquera ^a, Javier Ellena ^b, Juan C Tenorio ^b, Rodrigo S Corrêa ^c

PMCID: PMC3515213 PMID: 23284433

Abstract

In the title compound, C₁₄H₉N₃O₈, the benzene rings form a dihedral angle of 69.02 (5)°. The central ester group is rotated by 25.86 (9)° relative to the p-tolyl group. In the crystal, the molecules are linked by C—H⋯O interactions into helical chains along [010].

Related literature

For optical, pharmacological and crystalline properties of picric acid, see: Khan et al. (2010 ▶); Zaderenko et al. (1997 ▶). For picric acid derivatives, see: Bertolasi et al. (2011 ▶). For bond-length data, see: Allen et al. (1987 ▶). For similar structures, see: Moreno-Fuquen et al. (2012 ▶); Bibi et al. (2009 ▶); Shibakami et al. (1994 ▶); Shibakami & Sekiya (1995 ▶); For hydrogen bonding, see: Nardelli (1995 ▶) and for supramolecular aggregation behaviour of isomers, see: Glidewell et al. (2005 ▶).

Experimental

Crystal data

C₁₄H₉N₃O₈
M _r = 347.24
Monoclinic,
a = 7.6126 (2) Å
b = 8.2124 (2) Å
c = 23.9893 (7) Å
β = 94.448 (1)°
V = 1495.24 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 295 K
0.27 × 0.22 × 0.18 mm

Data collection

Nonius KappaCCD diffractometer
5494 measured reflections
3044 independent reflections
2296 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.123
S = 1.02
3044 reflections
227 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: HKL DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; 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

Click here for additional data file.^{(18.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812041773/ld2074sup1.cif

e-68-o3107-sup1.cif^{(18.7KB, cif)}

Click here for additional data file.^{(149.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812041773/ld2074Isup2.hkl

e-68-o3107-Isup2.hkl^{(149.4KB, hkl)}

Click here for additional data file.^{(5.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812041773/ld2074Isup3.cml

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
C3—H3⋯O8ⁱ	0.93	2.50	3.4286 (19)	175

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Symmetry code: (i) Inline graphic .

Acknowledgments

RMF is grateful to the Spanish Research Council (CSIC) for the use of a free-of-charge licence to the Cambridge Structural Database. RMF also thanks the Universidad del Valle, Colombia, for partial financial support.

supplementary crystallographic information

Comment

The title compound, C₁₄H₉O₈N₃ [2,4,6-trinitrophenyl 4-methylbenzoate] (I), belongs to a group of molecules known as nitro aryl benzoates. Recently, we have been investigating the synthesis, properties and main features of these nitroaromatic compounds, in particular - the derivatives of picric acid (trinitrophenol - TNP) (Bertolasi et al., 2011). These compounds have never been synthesized before and there is no any prior entries in CCSD related to such esters, except 2,4,6-trinitrophenyl 3-methylbenzoate (TNP3MeBA), an isomer of the title compound, that we recently published (Moreno-Fuquen et al., 2012). Our special interest in TNP is attributable to the optical, pharmacological and solid-state properties of its molecular adducts (Khan et al., 2010); Zaderenko et al., 1997) and the absence of any information of the picric acid as a part of aryl esters that probably can show similar or more interesting properties. In order to find out the molecular conformation of (I) and its supramolecular behavior, the title compound was synthesized. The molecular structure of (I) is presented on Fig. 1 with the numbering scheme similar to that for TNP-3MeBA in order to simplify structural comparisons. In the title structure, the phenolic C1—O7 bond length is significantly shortened [1.3715 (17) Å] and the benzoic C7—O7 bond length is significantly elongated [1.3898 (17) Å] as compared to other phenylbenzoates systems [1.422 (5) Å and 1.354 (5) Å respectively (Shibakami et al., 1994) and 1.415 (2) Å and 1.351 (2) Å respectively (Shibakami & Sekiya, 1995)]. However, these parameters are pretty close to the values presented in other crystal systems which contain similar substituents with respect to this structure, more specifically when there is nitro substituent in any of the benzene rings at the benzoate [for C1—O7= 1.395 (2) Å and for C7—O7= 1.376 (3) Å (Bibi et al., 2009) and 1.3676 (17) Å and 1.3820 (18) Å respectively (Moreno-Fuquen et al., 2012)]. Other bond lengths and bond angles of (I) agree with the literature values (Allen et al., 1987). The benzene rings of (I) form a dihedral angle of 69.02 (5)°, compared with values of 87.48 (5)° in TNP3MeBA. The central ester moiety forms an angle of 25.86 (9)° with the methylbenzene ring to which it is attached. This value is similar to the corresponding angle in its structural isomer TNP3MeBA - 19.42 (7)°. The nitro groups form dihedral angles with the adjacent benzene ring of 30.57 (11)°, 14.75 (16)° and 7.37 (17)° for O1—N1—O2, O3—N2—O4 and O5—N3—O6, respectively. The molecules are packed forming weak interactions C—H···O in one-dimensional helical chains which grow along [010] (see Fig. 2). The C3 atom of the phenyl ring at (x,y,z) acts as a hydrogen-bond donor to carbonyl atom O8 at (-x + 1,+y + 1/2,-z + 1/2) (see Table 1; Nardelli, 1995). We have found that (I) and its isomer TNP3MeBA show a marked similarity in terms of spatial group, unit-cell parameters and finally the intermolecular interactions given the supramolecular aggregation of these isomers. This behavior is very uncommon in compounds showing constitutional isomerism, since small changes in the molecular structures of the isomers usually lead to large changes in molecular aggregation of the structures (Glidewell et al., 2005).

Experimental

The reagents and solvents for the synthesis were obtained from the Aldrich Chemical Co., and were used without additional purification. The title molecule was obtained through a two-step reaction. First the 4-methylbenzoic acid (0.25 g, 1.836 mmol) was refluxed in an excess of thionyl chloride (10 ml) during an hour. Then thionyl chloride was distilled off under reduced pressure to purify the 4-methylbenzoyl chloride obtained as a pale yellow traslucent liquid. The same reaction flask was rearranged and a solution of picric acid (0.42 g, 1.835 mmol) in acetonitrile was added dropwise with constant stirring. The reaction mixture was let to reflux for about an hour. A pale yellow solid was obtained after leaving the solvent to evaporate. The solid was washed with distilled water and cold methanol to eliminate impurities. Crystals of good quality and suitable for single-crystal X-ray diffraction were grown from acetonitrile. IR spectra were recorded on a FT—IR SHIMADZU IR-Affinity-1 spectrophotometer. Pale Yellow crystals; yield 38%; m.p 417 (1) K. IR (KBr) 3112.86 cm^-1, 3086.07 cm^-1 (aromatic C—H); 2962.07 cm^-1, 2915.70 cm^-1 (methyl C—H); 1754.68 cm^-1 (ester C=O); 1609.43 cm^-1 (C=C); 1549.55 cm^-1, 1341.69 cm^-1 (–NO2); 1224.07 cm^-1 (C(=O)—O).