Crystal structure of bis­(prop-2-yn-1-yl) 5-nitro­isophthalate

K S Ezhilarasi; Sivasamy Selvarani; Perumal Rajakumar; B K Revathi; G Usha

doi:10.1107/S2056989015009846

. 2015 May 30;71(Pt 6):o435. doi: 10.1107/S2056989015009846

Crystal structure of bis(prop-2-yn-1-yl) 5-nitroisophthalate

K S Ezhilarasi ^a, Sivasamy Selvarani ^b, Perumal Rajakumar ^b, B K Revathi ^a, G Usha ^a,^*

PMCID: PMC4459362 PMID: 26090213

Abstract

The whole molecule of the title compound, C₁₄H₉NO₆, is generated by twofold rotation symmetry; the twofold axis bisects the nitro group and the benzene ring. The nitro group is inclined to the benzene ring by 14.42 (9)°. The prop-2-yn-1-yl groups are inclined to the benzene ring by 13 (2)° and to each other by 24 (3)°; one directed above the plane of the benzene ring and the other below. In the crystal, molecules are linked via pairs of C—H⋯O hydrogen bonds, forming inversion dimers with an R ₂ ²(18) ring motif. The dimers are linked by further C—H⋯O hydrogen bonds, forming sheets lying parallel to (100).

Keywords: crystal structure, 5-nitroisophthalate, prop-2-yn-1-yl, twofold rotation symmetry, C—H⋯O hydrogen bonding

Related literature

For the biological activities of carboxylates, see: Choudhary et al. (2002 ▸). For the uses and properties of nitroaromatics, see: Lee et al. (2013 ▸); Somerville et al. (1995 ▸). graphic file with name e-71-0o435-scheme1.jpg

Experimental

Crystal data

C₁₄H₉NO₆
M _r = 287.22
Orthorhombic,
a = 6.679 (5) Å
b = 11.679 (5) Å
c = 16.503 (5) Å
V = 1287.3 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.965, T _max = 0.977
6369 measured reflections
1613 independent reflections
1316 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.136
S = 0.73
1523 reflections
98 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; 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 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989015009846/su5137sup1.cif

e-71-0o435-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015009846/su5137Isup2.hkl

e-71-0o435-Isup2.hkl^{(73.7KB, hkl)}

Click here for additional data file.^{(4.9KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015009846/su5137Isup3.cml

Click here for additional data file.^{(1.6MB, tif)}

x y z . DOI: 10.1107/S2056989015009846/su5137fig1.tif

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. The unlabelled atoms are related to the labelled atoms by twofold rotation symmetry [symmetry code: (i) −x + Inline graphic , −y + , z].

Click here for additional data file.^{(2.6MB, tif)}

a . DOI: 10.1107/S2056989015009846/su5137fig2.tif

A view along the a axis of the crystal packing of the title compound. The dashed lines indicate hydrogen bonds (see Table 1 for details).

CCDC reference: 1402145

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C6H6AO1ⁱ	0.97	2.46	3.334(2)	150
C6H6BO1ⁱⁱ	0.97	2.57	3.313(2)	134
C8H8O3ⁱⁱ	0.93	2.50	3.251(2)	138

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

Acknowledgments

The authors thank the SAIF, IIT Madras, for providing the X-ray data-collection facility.

supplementary crystallographic information

S1. Comments

Carboxylates have promising activity against various antitumor cells (Choudharyl et al., 2002). Nitroaromatic compounds are used in the production of dyes, plastics, high explosives, pharmaceuticals, and pesticides (Somerville et al., 1995). Nitrobenzene is mostly used in the synthesis of aniline and in the production of benzidine, quinolone and azobenzene (Lee et al., 2013).

In the title compound, Fig. 1, the two-fold rotation bisects the benzene ring and the nitro group; atoms C1, C4, H4 and N1 lie on the two-fold rotation axis. The nitro group is inclined to the benzene ring by 14.42 (9) °. The prop-2-yn-1-yl groups are inclined to the benzene ring by 13 (2) ° and to each other by 24 (3) °; one directed above the plane of the benzene ring and the other below.

In the crystal, molecules are linked via pairs of C—H···O hydrogen bonds forming inversion dimers with an R₂²(18) ring motif (Table 1). The dimers are linked by further C—H···O hydrogen bonds forming sheets lying parallel to (100); see Table 1 and Fig. 2.

S2. Synthesis and crystallization

The title compound was synthesized by Steglich esterification of 5-nitro isophthalic acid (1 equiv) which together with propargyl alcohol (2.2 equiv) was added at 273 K to DMAP (2.5 equiv) and DCC (2.2 equiv) in dichloromethane (100 ml). The mixture was stirred under nitrogen at room temperature for 24 h. The white precipitate that formed was filtered off and washed with DCM (150 ml) and brine (150 ml), then dried over Na₂SO₄, filtered and evaporated to afforded the title compound. It was purified by column chromatography using CHCl₃:hexane (9:1) as a eluent. Crystals were obtained by slow evaporation of the solvent.

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned geometrically and treated as riding atoms: C—H = 0.93-0.97 Å with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for other H atoms.