2,4,6-Trinitro­phenyl benzoate

Rodolfo Moreno-Fuquen; Fabricio Mosquera; Alan R Kennedy; Catriona A Morrison; Regina H De Almeida Santos

doi:10.1107/S1600536812048362

. 2012 Nov 30;68(Pt 12):o3493. doi: 10.1107/S1600536812048362

2,4,6-Trinitrophenyl benzoate

Rodolfo Moreno-Fuquen ^a,^*, Fabricio Mosquera ^a, Alan R Kennedy ^b, Catriona A Morrison ^b, Regina H De Almeida Santos ^c

PMCID: PMC3589064 PMID: 23476300

Abstract

In the title molecule, C₁₃H₇N₃O₈, the phenyl and benzene rings are rotated from the mean plane of the central ester group by 18.41 (9) and 81.80 (5)°, respectively. The dihedral angle between the rings is 80.12 (14)°. In the crystal, molecules are linked by weak C—H⋯O interactions, forming helical chains along [010].

Related literature

For theoretical and spectroscopic properties of nitrophenyl esters, see: Ibrahim et al. (2011 ▶); Kirkien-Konasievicz & Maccoll (1964 ▶). For the structures of similar esters, see: Moreno-Fuquen et al. (2012a ▶,b ▶); Shibakami & Sekiya (1995 ▶); Gowda et al. (2007 ▶). For structural properties of nitrophenyl compounds, see: Domenicano et al. (1990 ▶); Glidewell et al. (2005 ▶). For hydrogen-bonding information, see: Nardelli (1995 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). graphic file with name e-68-o3493-scheme1.jpg

Experimental

Crystal data

C₁₃H₇N₃O₈
M _r = 333.22
Orthorhombic,
a = 7.5818 (3) Å
b = 8.3714 (2) Å
c = 21.0625 (10) Å
V = 1336.84 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 123 K
0.31 × 0.21 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur E diffractometer
5179 measured reflections
2758 independent reflections
2563 reflections with I > 2σ(I)’
R _int = 0.019
Standard reflections: 0

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.073
S = 1.05
2758 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Supplementary Material

Click here for additional data file.^{(18KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812048362/lh5562sup1.cif

e-68-o3493-sup1.cif^{(18KB, cif)}

Click here for additional data file.^{(132.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812048362/lh5562Isup2.hkl

e-68-o3493-Isup2.hkl^{(132.7KB, hkl)}

Click here for additional data file.^{(5.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812048362/lh5562Isup3.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	0.95	2.44	3.388 (2)	177

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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 and also thanks the Universidad del Valle, Colombia, for partial financial support.

supplementary crystallographic information

Comment

In our research group, we have recently investigated the synthesis, crystalline properties and main structural features of nitro aryl benzoates, in particular, the derivatives of picric acid (trinitrophenol - TNP). These types of compounds have been synthetically obtained and studied at a spectroscopic and theoretical level (Ibrahim et al., 2011) but there are no prior entries in Cambridge Structural Database (Version 5.33, Allen, 2002) of such related esters. Consequently, there is an absence of structural information about these esters. In order to fulfill this absence, we present the structure determination of the title compound, as part of a group of nitro aryl benzoates such as 2,4,6-trinitrophenyl-3-methylbenzoate (TNP3MeBA) and 2,4,6-trinitrophenyl-4-methylbenzoate (TNP4MeBA), the structures of which are already published (Moreno-Fuquen et al., 2012a,b).

The molecular structure of (I) is shown in Fig. 1, with a numbering scheme similar to that for TNP3MeBA and TNP4MeBA in order to simplify structural comparisons. In (I) the bond lengths and bond angles agree closely with those for its homologous esters TNP3MeBA (Moreno-Fuquen et al., 2012a) and TNP4MeBA (Moreno-Fuquen et al., 2012b). However, if these structural parameters are strictly checked in other phenyl benzoates having no nitro substituent over the structure (Shibakami & Sekiya, 1995, Gowda et al., 2007), it should be noticed that the phenolic C1—O7 bond length is significantly shortened [1.3695 (19) Å] and the benzoic C7—O7 bond length is significantly elongated [1.3876 (17) Å]. These changes in the bond parameters in (I) seem to be a feature of this kind of nitro phenyl benzoates , as they were found also in TNP3MeBA and TNP4MeBA, and are probably related with the presence of nitro substituents in the structure. Such effects have been well described by other authors (Kirkien-Konasievicz & Maccoll, 1964; Domenicano et al., 1990; Ibrahim et al., 2011) in a large varied number of other organic structures and can be rationalized in terms of inductive, resonance, reactivity and steric effects produced by nitro groups over aromatic rings. The benzene rings of (I) form a dihedral angle of 80.12 (14)°, compared with values of 87.48 (5)° and 69.02 (5)°, in TNP3MeBA and TNP4MeBA respectively. The central ester moiety forms an angle of 18.41 (9)° with the phenyl ring to which it is attached. This value is similar to the corresponding angle in the homologous ester TNP3MeBA 19.42 (7)°. The nitro groups form dihedral angles with the adjacent benzene ring of 29.55 (8)°, 13.94 (9)° and 8.84 (7)° for O1—N1—O2, O3—N2—O4 and O5—N3—O6, respectively. It was noted that for TNP4MeBA those same dihedral angles present almost identical values 30.57 (11)°, 14.75 (16)° and 7.37 (17)° and for TNP3MeBA the differences appear to increase 43.15 (10)°, 7.72 (14)° and 13.56 (18)°. The molecules are packed forming weak interactions C—H···O in one-dimensional helical chains which propagate 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,+y-1/2,-z+1/2) (see Table 1; Nardelli, 1995). This molecular interaction, involving the same atoms and given akin supramolecular behavior, is also found in TNP3MeBA and TNP4MeBA. For (I), the interaction is defined by distance D..A [3.388 (2) Å] and the angle D-H..A [176°], shown in Table 1, which compared with its analogous values in TNP4MeBA [3.4286 (19) Å, 175°] and TNP3MeBA [3.4276 (19) Å, 176°] reveal an extraordinary similarity at structural level among these group of compounds; very uncommon if it is taken into account that small changes in the molecular structures of a group of molecules 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 synthesized using equimolar quantities of benzoyl chloride (0.235 g, 1.673 mmol) and picric acid (0.383g). The reagents were dissolved in acetonitrile and the solution was taken 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 72%; m.p 435 K. IR (KBr) 3082.38 cm^-1, 3025.48 cm^-1 (aromatic C—H); 1759.15 cm^-1 (ester C=O); 1618.34 cm^-1, 1611.59 cm^-1 (C=C); 1544.08 cm^-1, 1342.51 cm^-1 (–NO2); 1224.85 cm^-1 (C(=O)—O).