2,4,6-Tri­nitro­phenyl furan-2-carboxyl­ate

Rodolfo Moreno-Fuquen; Fabricio Mosquera; Alan R Kennedy

doi:10.1107/S1600536813028274

. 2013 Oct 23;69(Pt 11):o1682. doi: 10.1107/S1600536813028274

2,4,6-Trinitrophenyl furan-2-carboxylate

Rodolfo Moreno-Fuquen ^a,^*, Fabricio Mosquera ^a, Alan R Kennedy ^b

PMCID: PMC3884337 PMID: 24454113

Abstract

In the title carboxylate derivative, C₁₁H₅N₃O₉, the picryl ring forms an angle of 75.79 (7)° with the ester fragment, indicating a near perpendicular disposition. The nitro substituents are variously oriented with respect to the picryl ring [dihedral angles = 3.22 (10), 16.03 (12) and 36.63 (10)°]. In the crystal, molecules form helical chains sustained by C—H⋯O interactions along [010]. The furanyl residue is disordered, having two coplanar slightly displaced orientations [major component = 0.730 (9)].

Related literature

For similar esters, see: Moreno-Fuquen et al. (2012 ▶, 2013 ▶). For hydrogen bonding, see: Nardelli (1995 ▶). graphic file with name e-69-o1682-scheme1.jpg

Experimental

Crystal data

C₁₁H₅N₃O₉
M _r = 323.18
Orthorhombic,
a = 7.0982 (3) Å
b = 8.4931 (4) Å
c = 20.4970 (9) Å
V = 1235.68 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 123 K
0.35 × 0.22 × 0.11 mm

Data collection

Oxford Diffraction Xcalibur E diffractometer
4861 measured reflections
2669 independent reflections
2395 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.095
S = 1.06
2669 reflections
224 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.27 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

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813028274/tk5263sup1.cif

e-69-o1682-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813028274/tk5263Isup2.hkl

e-69-o1682-Isup2.hkl^{(128.4KB, hkl)}

Click here for additional data file.^{(5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813028274/tk5263Isup3.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
C5—H5⋯O8ⁱ	0.95	2.32	3.270 (2)	180

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

1. Comment

In the present work, the structure of the 2,4,6-trinitrophenyl furan 2-carboxylate (I) has been determined as a part of an in-depth study of picryl substituted-esters carried out in our research group. Descriptions of similar structures have been published recently: 2,4,6-trinitrophenyl 3-chlorobenzoate (Moreno-Fuquen et al., 2013), and 2,4,6-trinitrophenyl benzoate (Moreno-Fuquen et al., 2012). The molecular structure of (I) is shown in Fig. 1. Bond distances and angles agree with the molecular features exhibited by other picryl substituted-esters, as described in detail in previous work (Moreno-Fuquen et al., 2012 and 2013). The picryl ring forms an angle of 75.79 (7)° with the ester fragment. The nitro groups form dihedral angles with the adjacent benzene ring of 3.22 (10), 16.03 (12) and 36.63 (10)° for O1—N1—O2, O3—N2—O4 and O5—N3—O6, respectively. The atoms at the furanyl ring are disordered over two positions with occupancies refined to 0.730 (9) and 0.270 (9) for C8A–C11A/O9A and C8B–C11B/O9B, respectively. Appropriate restraints were required (see experimental section) to give chemically acceptable geometries for these fragments. In the crystal the molecules are linked by weak C—H···O interactions, forming one-dimensional helical chains running along [010], as shown in Fig. 2 & Table 1. The C5 atom of the benzene 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 Nardelli, 1995).

2. 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 2-furoyl chloride (0.252 g, 1.931 mmol) and picric acid (0.442 g). 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 its acetonitrile solution. IR spectra were recorded on a FT—IR SHIMADZU IR-Affinity-1 spectrophotometer. Pale Yellow crystals; yield 52%; m.p 383 (1) K. IR (KBr) 3088.17 cm^-1 (aromatic C—H); 1764.94 cm^-1 (ester C=O); 1544.08 cm^-1, 1343.48 cm^-1 (–NO2); 1234.50 cm^-1 (C(=O)—O).