2,4,6-Tri­nitro­phenyl 3-chloro­benzoate

Rodolfo Moreno-Fuquen; Fabricio Mosquera; Javier Ellena; C A De Simone; Juan C Tenorio

doi:10.1107/S1600536813013792

. 2013 May 25;69(Pt 6):o966. doi: 10.1107/S1600536813013792

2,4,6-Trinitrophenyl 3-chlorobenzoate

Rodolfo Moreno-Fuquen ^a,^*, Fabricio Mosquera ^a, Javier Ellena ^b, C A De Simone ^b, Juan C Tenorio ^b

PMCID: PMC3685104 PMID: 23795123

Abstract

In the title benzoate derivative, C₁₃H₆ClN₃O₈, the planes of the benzene rings form a dihedral angle of 73.59 (7)°. The central ester unit forms an angle of 20.38 (12)° with the chloro-substituted benzene ring. In the crystal, molecules are linked by weak C—H⋯O interactions, forming helical chains along [101] and [100].

Related literature

For investigations on reaction kinetics, see: Kirkien-Konasiewicz & Maccoll (1964 ▶); Belousova et al. (2000 ▶). For spectroscopic and theoretical studies, see: Ibrahim et al. (2011 ▶). For bond-length data, see: Allen et al. (1987 ▶). For similar structures, see: Moreno-Fuquen et al. (2012a ▶,b ▶,c ▶, 2013 ▶). For hydrogen bonding, see: Nardelli (1995 ▶) and for hydrogen-bond motifs, see: Etter et al. (1990 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). graphic file with name e-69-0o966-scheme1.jpg

Experimental

Crystal data

C₁₃H₆ClN₃O₈
M _r = 367.66
Monoclinic,
a = 11.0633 (4) Å
b = 9.6560 (4) Å
c = 14.0251 (6) Å
β = 94.009 (2)°
V = 1494.60 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 295 K
0.24 × 0.24 × 0.17 mm

Data collection

Nonius KappaCCD diffractometer
16939 measured reflections
3383 independent reflections
2015 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.162
S = 1.00
3383 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: 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, 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.^{(18.4KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813013792/hg5316sup1.cif

e-69-0o966-sup1.cif^{(18.4KB, cif)}

Click here for additional data file.^{(165.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813013792/hg5316Isup2.hkl

e-69-0o966-Isup2.hkl^{(165.9KB, hkl)}

Click here for additional data file.^{(5.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813013792/hg5316Isup3.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⋯O3ⁱ	0.93	2.50	3.167 (3)	128
C11—H11⋯O1ⁱⁱ	0.93	2.46	3.263 (3)	145
C13—H13⋯O4ⁱⁱⁱ	0.93	2.41	3.312 (3)	165
C10—H10⋯O2^iv	0.93	2.60	3.278 (3)	131
C5—H5⋯O8^v	0.93	2.48	3.404 (3)	174

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

Acknowledgments

RMF is grateful to the Universidad del Valle, Colombia, for partial financial support.

supplementary crystallographic information

Comment

The title compound, C₁₃H₆ClN₃O₈[2,4,6-trinitrophenyl 3-chlorobenzoate] (I), belongs to a group of molecules known as picryl substituted-benzoates (or 2,4,6-trinitrofenil substituted-benzoates). Our research group has been lately investigating about this type of compound, in order to complete the crystallographic information around picryl substituted-benzoates. Also, the structural information can be linked or be useful to explain the results found at investigations of reaction kinetics (Kirkien-Konasiewicz & Maccoll, 1964; Belousova et al., 2000), spectroscopic behavior and theoretical studies (Ibrahim et al., 2011) underwent over this same group of compounds. The molecular structure of (I) is shown in Fig. 1, with a numbering scheme similar to that for TNP4ClBA (Moreno-Fuquen et al., 2013), TNP3MeBA (Moreno-Fuquen et al., 2012a), TNP4MeBA(Moreno-Fuquen et al., 2012b) and TNPBA (Moreno-Fuquen et al., 2012c) in order to simplify structural comparisons. As a general fact, described deeply in previous papers (Moreno-Fuquen et al., 2012c and 2013), the structural parameters of substituted picryl benzoates, including (I), show significant differences in the bond distances C1—O7 and C7—O7 if they are compared with analogous distances in other phenyl benzoates reported in the literature (Allen, 2002, Version 5.33). The benzene rings of (I) form a dihedral angle of 73.59 (7)°. The central ester moiety forms an angle of 20.38 (12)° with the chloro-substituted benzene ring to which it is attached and an angle of 86.03 (7)° with the picryl ring. The nitro groups form dihedral angles with the adjacent benzene ring of 59.14 (9)°, 3.6 (2)° and 21.48 (14)° for O1—N1—O2, O3—N2—O4 and O5—N3—O6, respectively. The molecules are packed in a three dimensional network, through weak interactions C—H···O (see Table 1; Nardelli, 1995). Weak C3-H3···O3 and C11-H11···O1 contacts which reinforced each other, allow the molecules to propagate, forming one-dimensional helical chains, along [101]. Both weak contacts form dimers within the structure, as is shown in Fig. 2, and allow the formation of R₂²(10) and R₂²(22) rings respectively (Etter, 1990). In addition to the mentioned interactions other weak C-H···O interactions are observed. Indeed, the C13-H13···O4 and C10-H10···O2 weak contacts, form C(9) and C(12) chains of molecules allowing the crystal to grow also along [100] (see Fig. 3).

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 3-chlorobenzoic acid (0.20g, 0.554 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 3-chorobenzoyl chloride obtained as a pale yellow traslucent liquid. The same reaction flask was rearranged and a solution of picric acid (0.12 g, 0.554 mmol) in acetonitrile was added dropwise with constant stirring. The reaction mixture was left 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 65%; m.p 408 (1)K. IR (KBr) 3092.32 cm^-1 (aromatic C—H); 1763.27 cm^-1 (ester C=O); 1615.65 cm^-1 (C=C); 1546.61 cm^-1, 1340.90 cm^-1 (–NO₂); 1216.82 cm^-1 (C(=O)—O).