2,4,6-Trinitro­phenyl 4-chloro­benzoate

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

doi:10.1107/S1600536813007332

. 2013 Mar 23;69(Pt 4):o570. doi: 10.1107/S1600536813007332

2,4,6-Trinitrophenyl 4-chlorobenzoate

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

PMCID: PMC3629618 PMID: 23634105

Abstract

In the title benzoate derivative, C₁₃H₆ClN₃O₈, the planes of the benzene rings form a dihedral angle of 63.46 (5)°. The dihedral angles between the benzene ring and its nitro groups are 12.78 (16)° for the first ortho, 28.4 (4) and 17.4 (4)° for the second (disordered) ortho and 3.58 (16)° for the para nitro group. The central ester moiety, –C—(C=O)—O–, is essentially planar (r.m.s. deviation for all non-H atoms = 0.0229 Å) and forms dihedral angles of 7.37 (14)° with the chloro-substituted benzene ring and 69.85 (6)° with the trinitro-substituted benzene ring. One of the nitro groups was refined as disordered over two sets of sites with fixed site occupancies of 0.61 and 0.39. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For the industrial and synthetic applications of nitroaryl compounds, see: Moreno-Fuquen et al. (2012a ▶) and references therein. For similar structures, see: Moreno-Fuquen et al. (2012b ▶,c ▶). For hydrogen bonding, see: Nardelli (1995 ▶). For hydrogen-bond motifs, see: Etter et al. (1990 ▶). For a description of the Cambridge Structural Database (CSD), see: Allen (2002 ▶). graphic file with name e-69-0o570-scheme1.jpg

Experimental

Crystal data

C₁₃H₆ClN₃O₈
M _r = 367.66
Monoclinic,
a = 9.3526 (3) Å
b = 11.4793 (3) Å
c = 13.6089 (4) Å
β = 93.612 (2)°
V = 1458.17 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 295 K
0.35 × 0.31 × 0.24 mm

Data collection

Nonius KappaCCD diffractometer
15908 measured reflections
3288 independent reflections
2424 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.151
S = 1.02
3288 reflections
246 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.24 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.^{(24.5KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813007332/lh5591sup1.cif

e-69-0o570-sup1.cif^{(24.5KB, cif)}

Click here for additional data file.^{(158KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007332/lh5591Isup2.hkl

e-69-0o570-Isup2.hkl^{(158KB, hkl)}

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

Supplementary material file. DOI: 10.1107/S1600536813007332/lh5591Isup3.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
C13—H13⋯O4ⁱ	0.93	2.55	3.472 (3)	174
C5—H5⋯O8ⁱⁱ	0.93	2.53	3.457 (2)	174
C3—H3⋯O6B ⁱⁱⁱ	0.93	2.36	3.188 (5)	147
C12—H12⋯O1^iv	0.93	2.51	3.377 (2)	156

Open in a new tab

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

Acknowledgments

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

supplementary crystallographic information

Comment

The title compound (I) belongs to a group of molecules known as nitro aryl benzoates. The vast applications at the industrial and synthetic level of nitro aryl compounds have been described in an earlier paper (Moreno-Fuquen et al., 2012a). Compound (I) is part of a series of studies on substituted 2,4,6-trinitrophenyl benzoates, also called picryl benzoates, undergone by our research group concerning the synthesis, properties and main features of the group of compounds. The molecular structure of (I) is shown in Fig. 1, with a numbering scheme similar to that for 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. The substituted picryl benzoates, including (I), show noticeable differences only in C1—O7 and C7—O7 bond distances, if they are compared with bond and angles parameters in other phenyl benzoates reported in the Cambridge Structural Database (Version 5.33, Allen, 2002). This fact has been highlighted in previous papers (Moreno-Fuquen et al., 2012b,c) and it suggests a generalized effect over the ester moiety caused by the nitro substituents on the picryl fragment. The benzene rings of (I) form a dihedral angle of 63.46 (5)°. The central ester moiety forms an angle of 7.37 (14)° with the benzene ring to which it is attached. One of the nitro groups on the picryl fragment is disordered over two positions. The occupancies were initially refined but were fixed at 0.61 and 0.39 in the final cycles of refinement for O5A/O6A and O5B/O6B, respectively.

In the crystal, in a first substructure, the molecules are linked by weak C—H···O interactions, forming helical chains along [010]. The C5 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 + 3/2). Growth in this direction is reinforced by the weak C13—H13···O4 interaction, in which the C13 atom of the chloro substituted benzene ring at (x,y,z) acts as hydrogen-bond donor to atom O4 from one of the nitro groups at (-x, y-1/2, -z+3/2). The combination of these two contacts generate R²₂(10) rings (Etter et al., 1990), along [010] (See Fig. 2). This type of crystal growth for (I), was also observed for TNP3MeBA (Moreno-Fuquen et al., 2012a). Additionally to those interactions, other weak C—H···O contacts were observed in (I) and they complement the main growth previously described. In a second substructure shown in Fig. 3, it can be observed the formation of dimers through the weak C12—-H12···O1 interactions. Indeed, the C12 atom at (x,y,z) acts as hydrogen-bond donor to O1 atom of the nitro group at (-x+1,-y+1,-z+2) forming R²₂(20) rings (Etter et al., 1990). These dimers are clearly connected to each other, through the weak C3—H3···O6B contact, allowing them to grow along [001]. The C3 atom at (x,y,z) acts as a hydrogen-bond donor to O6B atom of the nitro group at (x,-y+3/2,+z-1/2). Hence, in the crystal, the formation of an overall three-dimensional structure is observed, via weak C—H···O hydrogen bonds (see Table 1, Nardelli, 1995).

Experimental

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 model. First the 4-chlorobenzoic acid (0.270 g, 0.734 mmol) was refluxed in an excess amount of thionyl chloride (10 ml) during an hour. Then thionyl chloride was distilled under reduce pressure to purify the 4-chlorobenzoyl chloride obtained as a pale yellow traslucent liquid. The same reaction flask was rearranged and a solution of picric acid (0.170 g, 0.734 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 72%; m.p 433 (1) K. IR (KBr) 3096.55 cm^-1 (aromatic C—H); 1752.53 cm^-1 (ester C=O); 1615.98, 1590.04 cm^-1 (C=C); 1543.34 cm^-1, 1340.73 cm^-1 (–NO₂); 1218.96 cm^-1 (C(=O)—O).