3 Nitro­cinnamic acid

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Structure Reports Online

ISSN 1600-5368

3-Nitrocinnamic acid

K. Udaya Lakshmi,a*

S. Thamotharan,bM. Srinivasan,c K. Ramamurthiaand

B. Varghesec

a_{School of Physics, Bharathidasan University,} Tiruchirappalli 620 024, India,b_Molecular Biophysics Unit, Indian Institute of Science, Bangalore 560 012, India, andc_{Sophisticated} Analytical Instrument Facility, Indian Institute of Technology Madras, Chennai 600 036, India

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 293 K

Mean(C–C) = 0.003 A˚ Rfactor = 0.046 wRfactor = 0.146

Data-to-parameter ratio = 11.5

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

The title compound, C9H7NO4, forms centrosymmetric dimers

through intermolecular O—H O hydrogen bonds in the crystal structure. The nitro group deviates slightly from coplanarity with the benzene ring. The benzene ring and the carboxylic acid group are in an E configuration about the ethylenic double bond.

Comment

Various cinnamic acid derivatives form substrate inter-mediates with the enzyme papain (Huber, 1985). m -Nitro-cinnamic acid crystallizes in two modifications and the unit-cell dimensions of these polymorphs have been reported previously (Schmidt, 1964). In this paper, we report the crystal structure of thepolymorph ofm-nitrocinnamic acid, (I).

A perspective view of (I), with the atomic numbering scheme, is shown in Fig. 1. The bond lengths and angles agree well with literature values (Allenet al., 1987). The C1—C7— C8—C9 torsion angle of 179.5 (2)_{indicates that the benzene}

ring and the carboxylic acid group are in an Econfiguration about the C7 C8 bond and the propenoic acid moiety exists in an extended conformation. The alkenecarbonyl

conforma-Received 30 September 2005 Accepted 6 October 2005 Online 12 October 2005

Figure 1

tion [C7—C8—C9—O9 =2.5 (4)_{] is synperiplanar, which is}

the most common conformation for trans-cinnamic acids (Leiserowitz, 1976).

The dihedral angle between the 3-nitro group and the benzene ring is 8.9 (9)_{. In a related structure, viz. p}

-nitro-cinnamic acid (Kageyama et al., 1993), the nitro group is coplanar (2.2) with the benzene ring. With respect to the plane of the benzene ring, the 3-nitro group is oriented at an angle of 45.3 _{in 4-dimethylamino-3-nitrocinnamic acid}

(Huber, 1985), 3.6_{in 3,5-dinitrocinnamic acid and 2.3in the}

3,5-dinitrocinnamic acid 2,5-dimethoxycinnamic acid complex (Desiraju & Sharma, 1991), 3.0 _{in the 3,5-dinitrocinnamic}

acid 4-(N,N-dimethylamino)benzoic acid complex and 6.1_in

the 3,5-dinitrocinnamic acid 4-(N,N-dimethylamino)cinnamic acid complex (Sharmaet al., 1993).

The angle between the mean plane of the benzene ring and the mean plane of the propenoic acid moiety is 3.5 (7)_{in (I)}

and 2.6 _{in 4-dimethylamino-3-nitrocinnamic acid (Huber,}

1985). The corresponding angles in 4-chlorocinnamic acid (Gluskeret al., 1975), 4-iodocinnamic acid (Goudet al., 1993),

p-nitrocinnamic acid (Kageyama et al., 1993), 3,5-dinitro-cinnamic acid and the 3,5-dinitrocinnamic acid 2,5-dimethoxycinnamic acid complex (Desiraju & Sharma, 1991) are 14.1, 13.8, 4.7, 28.7 and 6.4_{, respectively. In the}

3,5-dinitrocinnamic acid 4-(N,N-dimethylamino)cinnamic acid complex, the propenoic acid group is twisted by 7.6_{out of the}

mean plane of the benzene ring (Sharmaet al., 1993). In the crystalline state, the molecules form O—H O hydrogen-bonded dimers across an inversion centre (Table 1). These dimers are stacked along the shortest cell axis and lead to anR2

2(8) motif (Fig. 2) (Bernsteinet al., 1995).

Experimental

The title compound, (I), was prepared by dissolving m -nitro-benzaldehyde (6 g, 0.04 mol) and malonic acid (8.3 g, 0.08 mol) in a mixture of 5 ml of pyridine and 0.25 ml of piperidine. The solution was allowed to reflux for 1 h, with rapid evolution of CO2. The

resulting title compound was recrystallized from ethanol.

Crystal data

C9H7NO4

Mr= 193.16

Monoclinic,P2₁=n a= 3.7756 (2) A˚

b= 9.4584 (13) A˚

c= 24.295 (4) A˚

= 90.875 (8)

V= 867.52 (18) A˚3

Z= 4

Dx= 1.479 Mg m

3

CuKradiation Cell parameters from 25

reflections

= 20–30

= 1.02 mm1

T= 293 (2) K Block, colourless 0.300.200.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

!–2scans

Absorption correction: scan (Northet al., 1968)

Tmin= 0.751,Tmax= 0.823

1733 measured reflections 1478 independent reflections 1068 reflections withI> 2(I)

Rint= 0.043

max= 67.9

h= 0!4

k= 0!11

l=29!29 3 standard reflections

frequency: 120 min intensity decay: none

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.046

wR(F2_{) = 0.146}

S= 1.03 1478 reflections 129 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0726P)2

+ 0.3649P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.30 e A˚ 3

min=0.17 e A˚ 3

Extinction correction:SHELXL97

Extinction coefficient: 0.0054 (11)

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

O10—H10 O9i

0.82 1.83 2.636 (3) 169

Symmetry code: (i)xþ1;y1;z.

All the H atoms were placed in idealized positions (C—H = 0.93 A˚ and O—H = 0.82 A˚ ) and constrained to ride on their parent atoms, withUiso(H) = 1.2Ueq(parent atom).

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement:CAD-4 EXPRESS; data reduction:MolEN(Fair, 1990); program(s) used to solve structure:SIR92 (Altomare et al., 1994); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:ORTEP3 for Windows(Farrugia, 1997); software used to prepare material for publication:SHELXL97andPLATON

(Spek, 2003).

KU and KR thank Professor R. Jeyaraman and Dr K. Sarkunam, School of Chemistry, Bharathidasan University, Tiruchirappalli, India, for providing the chemicals.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987).J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994).J. Appl. Cryst.27, 435.

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995).Angew. Chem. Int. Ed. Engl.34, 1555–1573.

Desiraju, G. R. & Sharma, C. V. K. (1991).J. Chem. Soc. Chem. Commun.pp. 1239–1241.

Enraf–Nonius (1994). CAD-4 EXPRESS. Version 5.1/1.2. Enraf–Nonius, Delft, The Netherlands.

Fair, C. K. (1990).MolEN. Enraf–Nonius, Delft, The Netherlands. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.

Glusker, J. P., Zacharias, D. E. & Carrell, H. L. (1975).J. Chem. Soc. Perkin Trans. 2, pp. 68–74.

Goud, B. S., Pathaneni, S. S. & Desiraju, G. R. (1993).Acta Cryst.C49, 1107– 1111.

Huber, C. P. (1985).Acta Cryst.C41, 1076–1079.

organic papers

Acta Cryst.(2005). E61, o3636–o3638 Udaya lakshmiet al. _C9H7NO4

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Figure 2

Kageyama, Y., Iwamoto, T., Haisa, M. & Kashino, S. (1993).Acta Cryst.C49, 833–834.

Leiserowitz, L. (1976).Acta Cryst.B32, 775–802.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351– 359.

Schmidt, G. M. J. (1964).J. Chem. Soc.pp. 2014–2021.

Sharma, C. V. K., Panneerselvam, K., Pilati, T. & Desiraju, G. R. (1993).J. Chem. Soc. Perkin Trans. 2, pp. 2209–2216.

Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany. Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

organic papers

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sup-1 Acta Cryst. (2005). E61, o3636–o3638

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Acta Cryst. (2005). E61, o3636–o3638 [https://doi.org/10.1107/S1600536805031879]

3-Nitrocinnamic acid

K. Udaya Lakshmi, S. Thamotharan, M. Srinivasan, K. Ramamurthi and B. Varghese

3-Nitrocinnamic acid

Crystal data

C9H7NO4

Mr = 193.16 Monoclinic, P21/n

Hall symbol: -P 2yn a = 3.7756 (2) Å b = 9.4584 (13) Å c = 24.295 (4) Å β = 90.875 (8)° V = 867.52 (18) Å3

Z = 4

F(000) = 400 Dx = 1.479 Mg m−3

Cu Kα radiation, λ = 1.54180 Å Cell parameters from 25 reflections θ = 20–30°

µ = 1.02 mm−1

T = 293 K Block, colourless 0.30 × 0.20 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω–2θ scans

Absorption correction: ψ scan (North et al., 1968)

Tmin = 0.751, Tmax = 0.823

1733 measured reflections

1478 independent reflections 1068 reflections with I > 2σ(I) Rint = 0.043

θmax = 67.9°, θmin = 3.6°

h = 0→4 k = 0→11 l = −29→29

3 standard reflections every 120 min intensity decay: none

Refinement

Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.046}

wR(F2_{) = 0.146}

S = 1.03 1478 reflections 129 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.0726P)2 + 0.3649P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.30 e Å−3

Δρmin = −0.17 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3/sin(2θ)]_-1/4

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sup-2 Acta Cryst. (2005). E61, o3636–o3638

Special details

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 weightedR-factorwRand goodness of fitSare 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 calculatingR-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₎

x y z Uiso*/Ueq

C1 0.3333 (6) 0.0198 (2) 0.11430 (10) 0.0508 (6) C2 0.4539 (6) 0.0178 (2) 0.16858 (9) 0.0465 (6) H2 0.5548 −0.0636 0.1835 0.056* C3 0.4216 (6) 0.1376 (2) 0.19963 (9) 0.0458 (6) C4 0.2784 (7) 0.2620 (2) 0.17952 (12) 0.0592 (7) H4 0.2600 0.3417 0.2017 0.071* C5 0.1638 (7) 0.2640 (3) 0.12542 (13) 0.0647 (7) H5 0.0688 0.3464 0.1105 0.078* C6 0.1888 (7) 0.1455 (3) 0.09359 (11) 0.0590 (7) H6 0.1078 0.1485 0.0573 0.071* N1 0.5488 (6) 0.1356 (2) 0.25715 (9) 0.0559 (6) C7 0.3562 (7) −0.1043 (3) 0.07858 (10) 0.0592 (7) H7 0.2666 −0.0932 0.0430 0.071* C8 0.4884 (7) −0.2302 (3) 0.09062 (10) 0.0617 (7) H8 0.5826 −0.2459 0.1257 0.074* C9 0.4915 (7) −0.3454 (3) 0.05071 (10) 0.0565 (6) O1 0.4837 (7) 0.2370 (2) 0.28617 (9) 0.0890 (7) O2 0.7153 (6) 0.0337 (2) 0.27319 (8) 0.0752 (6) O9 0.3566 (5) −0.3298 (2) 0.00408 (7) 0.0708 (6) O10 0.6367 (6) −0.4602 (2) 0.06723 (8) 0.0758 (6) H10 0.6165 −0.5206 0.0432 0.091*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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sup-3 Acta Cryst. (2005). E61, o3636–o3638

O2 0.0967 (16) 0.0674 (12) 0.0611 (12) 0.0120 (11) −0.0161 (10) 0.0039 (9) O9 0.0944 (15) 0.0670 (12) 0.0504 (10) 0.0113 (10) −0.0157 (9) 0.0000 (8) O10 0.1078 (16) 0.0607 (11) 0.0582 (11) 0.0143 (11) −0.0221 (10) −0.0038 (8)

Geometric parameters (Å, º)

C1—C2 1.389 (3) C6—H6 0.9300 C1—C6 1.398 (3) N1—O2 1.211 (3) C1—C7 1.463 (3) N1—O1 1.218 (3) C2—C3 1.368 (3) C7—C8 1.323 (3) C2—H2 0.9300 C7—H7 0.9300 C3—C4 1.381 (3) C8—C9 1.459 (3) C3—N1 1.471 (3) C8—H8 0.9300 C4—C5 1.378 (4) C9—O9 1.244 (3) C4—H4 0.9300 C9—O10 1.278 (3) C5—C6 1.366 (4) O10—H10 0.8200 C5—H5 0.9300

C2—C1—C6 118.3 (2) C5—C6—H6 119.2 C2—C1—C7 122.1 (2) C1—C6—H6 119.2 C6—C1—C7 119.7 (2) O2—N1—O1 123.3 (2) C3—C2—C1 118.8 (2) O2—N1—C3 118.4 (2) C3—C2—H2 120.6 O1—N1—C3 118.3 (2) C1—C2—H2 120.6 C8—C7—C1 128.1 (2) C2—C3—C4 123.3 (2) C8—C7—H7 116.0 C2—C3—N1 118.86 (19) C1—C7—H7 116.0 C4—C3—N1 117.9 (2) C7—C8—C9 122.2 (2) C5—C4—C3 117.7 (2) C7—C8—H8 118.9 C5—C4—H4 121.2 C9—C8—H8 118.9 C3—C4—H4 121.2 O9—C9—O10 123.7 (2) C6—C5—C4 120.4 (2) O9—C9—C8 120.6 (2) C6—C5—H5 119.8 O10—C9—C8 115.7 (2) C4—C5—H5 119.8 C9—O10—H10 109.5 C5—C6—C1 121.6 (2)

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sup-4 Acta Cryst. (2005). E61, o3636–o3638

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

O10—H10···O9i _{0.82 1.83 2.636 (3) 169}