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

Ezhilarasi, K.S.; Selvarani, S.; Rajakumar, P.; Revathi, B.K.; Usha, G.

doi:10.1107/S2056989015009846

organic compounds

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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 and G. Usha ^a ^*

^aPG and Research Department of Physics, Queen Mary's College, Chennai-4, Tamilnadu, India, and ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai-25, India
^*Correspondence e-mail: guqmc@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 12 May 2015; accepted 21 May 2015; online 30 May 2015)

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 R₂²(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.

CCDC reference: 1402145

1. 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 ).

2. Experimental

2.1. Crystal data

C₁₄H₉NO₆
M_r = 287.22
Orthorhombic, P c c n
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

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O1ⁱ	0.97	2.46	3.334 (2)	150
C6—H6B⋯O1ⁱⁱ	0.97	2.57	3.313 (2)	134
C8—H8⋯O3ⁱⁱ	0.93	2.50	3.251 (2)	138
Symmetry codes: (i) -x+2, -y+1, -z; (ii) $[-x+{\script{5\over 2}}, y, z-{\script{1\over 2}}]$ .

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 ).

Supporting information

CCDC reference: 1402145

Crystal structure: contains datablocks I, Global. DOI: 10.1107/S2056989015009846/su5137sup1.cif

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

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

checkCIF report

Comments top

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.

Synthesis and crystallization top

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.

Refinement top

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.

Related literature top

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).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. 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 + 3/2, -y + 1/2, z].
	Fig. 2. 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).

Bis(prop-2-yn-1-yl) 5-nitrobenzene-1,3-dicarboxylate top

Crystal data top

C₁₄H₉NO₆	F(000) = 592
M_r = 287.22	D_x = 1.482 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	θ = 2.5–28.4°
a = 6.679 (5) Å	µ = 0.12 mm⁻¹
b = 11.679 (5) Å	T = 293 K
c = 16.503 (5) Å	Block, colourless
V = 1287.3 (12) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	1613 independent reflections
Radiation source: fine-focus sealed tube	1316 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω and ϕ scan	θ_max = 28.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
T_min = 0.965, T_max = 0.977	k = −15→7
6369 measured reflections	l = −12→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.136	w = 1/[σ²(F_o²) + (0.1246P)² + 0.5331P] where P = (F_o² + 2F_c²)/3
S = 0.73	(Δ/σ)_max < 0.001
1523 reflections	Δρ_max = 0.26 e Å⁻³
98 parameters	Δρ_min = −0.21 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.030 (5)

Crystal data top

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

Data collection top

Bruker Kappa APEXII CCD diffractometer	1613 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1316 reflections with I > 2σ(I)
T_min = 0.965, T_max = 0.977	R_int = 0.021
6369 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 0.73	Δρ_max = 0.26 e Å⁻³
1523 reflections	Δρ_min = −0.21 e Å⁻³
98 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.7500	0.2500	0.05352 (9)	0.0336 (4)
C2	0.90289 (17)	0.30592 (10)	0.01386 (7)	0.0351 (3)
H2	1.0033	0.3433	0.0426	0.042*
C3	0.90264 (16)	0.30486 (10)	−0.07063 (7)	0.0329 (3)
C4	0.7500	0.2500	−0.11315 (9)	0.0328 (4)
H4	0.7500	0.2500	−0.1695	0.039*
C5	1.07371 (18)	0.36348 (11)	−0.11169 (7)	0.0377 (3)
C6	1.2259 (2)	0.41344 (12)	−0.23491 (7)	0.0431 (3)
H6A	1.2527	0.4888	−0.2127	0.052*
H6B	1.3450	0.3669	−0.2284	0.052*
C7	1.17465 (19)	0.42270 (11)	−0.32014 (8)	0.0412 (3)
C8	1.1422 (2)	0.43439 (16)	−0.38961 (9)	0.0565 (4)
H8	1.1166	0.4436	−0.4446	0.068*
N1	0.7500	0.2500	0.14284 (8)	0.0377 (4)
O1	0.86053 (16)	0.31731 (9)	0.17767 (6)	0.0525 (3)
O3	1.21118 (18)	0.40639 (12)	−0.07644 (6)	0.0700 (4)
O2	1.05835 (13)	0.36103 (8)	−0.19240 (5)	0.0404 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0357 (8)	0.0445 (8)	0.0205 (8)	0.0030 (6)	0.000	0.000
C2	0.0344 (6)	0.0445 (6)	0.0263 (6)	−0.0024 (4)	−0.0023 (4)	−0.0013 (4)
C3	0.0328 (6)	0.0407 (6)	0.0254 (6)	−0.0011 (4)	0.0013 (4)	0.0007 (4)
C4	0.0355 (8)	0.0411 (8)	0.0218 (7)	−0.0010 (6)	0.000	0.000
C5	0.0378 (6)	0.0483 (7)	0.0270 (6)	−0.0062 (5)	0.0000 (5)	0.0015 (5)
C6	0.0392 (7)	0.0559 (7)	0.0342 (7)	−0.0110 (5)	0.0065 (5)	0.0047 (5)
C7	0.0401 (6)	0.0463 (6)	0.0370 (7)	−0.0021 (5)	0.0090 (5)	0.0045 (5)
C8	0.0549 (8)	0.0771 (10)	0.0376 (7)	−0.0064 (7)	0.0045 (6)	0.0094 (7)
N1	0.0369 (7)	0.0529 (8)	0.0234 (7)	0.0042 (6)	0.000	0.000
O1	0.0568 (6)	0.0728 (7)	0.0278 (5)	−0.0089 (5)	−0.0065 (4)	−0.0078 (4)
O3	0.0606 (7)	0.1147 (11)	0.0345 (5)	−0.0461 (7)	−0.0069 (5)	0.0068 (6)
O2	0.0393 (5)	0.0563 (6)	0.0256 (5)	−0.0124 (4)	0.0048 (3)	−0.0012 (3)

Geometric parameters (Å, º) top

C1—C2ⁱ	1.3775 (15)	C5—O2	1.3363 (15)
C1—C2	1.3775 (15)	C6—C7	1.4517 (18)
C1—N1	1.474 (2)	C6—O2	1.4555 (15)
C2—C3	1.3944 (16)	C6—H6A	0.9700
C2—H2	0.9300	C6—H6B	0.9700
C3—C4	1.3937 (15)	C7—C8	1.175 (2)
C3—C5	1.4944 (17)	C8—H8	0.9300
C4—C3ⁱ	1.3937 (15)	N1—O1	1.2220 (12)
C4—H4	0.9300	N1—O1ⁱ	1.2220 (12)
C5—O3	1.1970 (17)

C2ⁱ—C1—C2	123.27 (14)	O2—C5—C3	112.55 (10)
C2ⁱ—C1—N1	118.36 (7)	C7—C6—O2	108.50 (11)
C2—C1—N1	118.36 (7)	C7—C6—H6A	110.0
C1—C2—C3	118.03 (11)	O2—C6—H6A	110.0
C1—C2—H2	121.0	C7—C6—H6B	110.0
C3—C2—H2	121.0	O2—C6—H6B	110.0
C4—C3—C2	120.56 (11)	H6A—C6—H6B	108.4
C4—C3—C5	122.79 (11)	C8—C7—C6	176.19 (14)
C2—C3—C5	116.64 (10)	C7—C8—H8	180.0
C3—C4—C3ⁱ	119.53 (14)	O1—N1—O1ⁱ	123.89 (15)
C3—C4—H4	120.2	O1—N1—C1	118.06 (7)
C3ⁱ—C4—H4	120.2	O1ⁱ—N1—C1	118.06 (7)
O3—C5—O2	123.52 (11)	C5—O2—C6	114.36 (9)
O3—C5—C3	123.92 (12)

C2ⁱ—C1—C2—C3	−0.45 (8)	C2—C3—C5—O2	−178.24 (10)
N1—C1—C2—C3	179.55 (8)	O2—C6—C7—C8	166 (2)
C1—C2—C3—C4	0.91 (15)	C2ⁱ—C1—N1—O1	−165.80 (8)
C1—C2—C3—C5	−178.32 (9)	C2—C1—N1—O1	14.20 (8)
C2—C3—C4—C3ⁱ	−0.46 (8)	C2ⁱ—C1—N1—O1ⁱ	14.20 (8)
C5—C3—C4—C3ⁱ	178.71 (12)	C2—C1—N1—O1ⁱ	−165.80 (8)
C4—C3—C5—O3	−176.32 (13)	O3—C5—O2—C6	1.09 (19)
C2—C3—C5—O3	2.9 (2)	C3—C5—O2—C6	−177.80 (10)
C4—C3—C5—O2	2.56 (15)	C7—C6—O2—C5	−170.29 (11)

Symmetry code: (i) −x+3/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O1ⁱⁱ	0.97	2.46	3.334 (2)	150
C6—H6B···O1ⁱⁱⁱ	0.97	2.57	3.313 (2)	134
C8—H8···O3ⁱⁱⁱ	0.93	2.50	3.251 (2)	138

Symmetry codes: (ii) −x+2, −y+1, −z; (iii) −x+5/2, y, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O1ⁱ	0.97	2.46	3.334 (2)	150
C6—H6B···O1ⁱⁱ	0.97	2.57	3.313 (2)	134
C8—H8···O3ⁱⁱ	0.93	2.50	3.251 (2)	138

Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+5/2, y, z−1/2.

Acknowledgements

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

References

Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Choudhary, M. A., Mazhar, M., Ali, S., Song, X. & Eng, G. (2002). Met.-Based Drugs, 8, 275–281. CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Lee, C. H., Kim, S. H., Kwon, D. H., Jang, K. H., Chung, Y. H. & Moon, J. D. (2013). Ann. Occup. Environ. Med. 25, 31. PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Somerville, C. C., Nishino, F. S. & Spain, C. J. (1995). J. Bacteriol. 177, 3837–3842. CAS PubMed Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 6| June 2015| Page o435

doi:10.1107/S2056989015009846

Open

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