N (p Chloro­phenyl)­maleamic acid

organic papers

o1296

Structure Reports Online

ISSN 1600-5368

N

-(

p

-Chlorophenyl)maleamic acid

Satya Murti Prasad,* R. B. P. Sinha, Deo Kumar Mandal and Asha Rani

Department of Physics, Ranchi University, Ranchi 834 008, India

Correspondence e-mail: prasadsm50@hotmail.com

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.003 AÊ

Rfactor = 0.054

wRfactor = 0.140

Data-to-parameter ratio = 12.5

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

#2002 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title molecule, C10H8ClNO3, is nearly planar, with the

mean planes through the p-chlorophenyl and maleamic acid groups inclined at an angle of 4.45 (1) _{to each other.}

Symmetry-related molecules are linked by NÐH O, CÐ H O and CÐH Cl intermolecular hydrogen bonds, to form molecular layers parallel to thebcplane.

Comment

The structure ofN-(p-chlorophenyl)-maleamic acid, (I), was brie¯y reported by Prasad & Mandal (1978), with anRvalue of 0.16, using photographic X-ray diffraction data. The struc-ture has now been re®ned using diffractometer X-ray data and the results are presented here. We have previously reported the structure of a related compound,N-(p-tolyl)maleamic acid (Prasadet al., 2002). The two structures are similar but not exactly isostructural. The substitution of CH3by a Cl atom has

reduced the unit-cell volume by 37.8 AÊ3_.

A displacement ellipsoid plot of (I) is shown in Fig. 1. The bond lengths and angles of the maleamic acid group agree with those in N-(p-tolyl)maleamic acid and also with those in maleic acid (James & Williams, 1974). The molecule is nearly planar, with atom O3 deviating by a maximum by 0.116 (2) AÊ. The dihedral angle between the mean planes through thep -chlorophenyl and maleamic acid groups is 4.45 (1)_{. The}

carboxyl H atom is involved in an intramolecular OÐH O hydrogen bond with carbonyl atom O3. In the crystal, symmetry-related molecules are linked by NÐH O, CÐ H O and CÐH Cl intermolecular hydrogen bonds (Table 2 and Fig. 2), to form molecular layers parallel to thebc

plane, approximately atx=1

4and34. These layers are stacked

alternately at distances of 3.405 and 3.341 AÊ, indicating signi®cant interactions between the phenyl and maleamic acid groups, as observed inN-(p-tolyl)maleamic acid (Prasadet al., 2002). A list of some short intermolecular contacts is given in Table 3.

Experimental

The title compound was prepared by a solid-state reaction between

p-chloroaniline and maleic anhydride, by Professor R. P. Rastogi (Ghorakhpur University) and his co-workers (private communica-tion). It was recrystallized from methanol at room temperature.

Crystal data

C10H8ClNO3

Mr= 225.62 Monoclinic,P21=c

a= 7.306 (3) AÊ

b= 11.765 (4) AÊ

c= 12.828 (4) AÊ

= 116.09 (4)

V= 990.3 (6) AÊ3

Z= 4

Dx= 1.513 Mg mÿ3 MoKradiation Cell parameters from 25

re¯ections

= 8.2±18.9

= 0.37 mmÿ1

T= 293 (2) K Needle, light yellow 0.250.230.10 mm

Data collection

Enraf±Nonius CAD-4 diffractometer

!±2scans

Absorption correction: none 1707 measured re¯ections 1707 independent re¯ections 1224 re¯ections withI> 2(I)

max= 25.0

h= 0!8

k= 0!13

l=ÿ15!13 3 standard re¯ections

every 50 re¯ections intensity decay: none

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.054}

wR(F2_{) = 0.140}

S= 0.92 1707 re¯ections 137 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.102P)2] whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001

max= 0.51 e AÊÿ3

min=ÿ0.31 e AÊÿ3

Extinction correction:SHELXL97 Extinction coef®cient: 0.006 (2)

Table 1

Selected geometric parameters (AÊ,_).

C1ÐCl 1.729 (3) C4ÐN1 1.407 (4) C7ÐO3 1.239 (3)

C7ÐN1 1.340 (3) C10ÐO2 1.201 (3) C10ÐO1 1.302 (3)

C2ÐC1ÐCl 120.7 (2) C6ÐC1ÐCl 119.2 (2) C3ÐC4ÐN1 124.1 (2) C5ÐC4ÐN1 116.8 (2)

O3ÐC7ÐN1 122.2 (3) O3ÐC7ÐC8 123.3 (2) N1ÐC7ÐC8 114.4 (2) C7ÐN1ÐC4 128.9 (2)

O3ÐC7ÐC8ÐC9 3.5 (5) O3ÐC7ÐN1ÐC4 0.7 (4) C8ÐC7ÐN1ÐC4 ÿ179.1 (3)

C3ÐC4ÐN1ÐC7 ÿ8.4 (4) C5ÐC4ÐN1ÐC7 172.0 (3)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N1ÐH1N O2i _{0.86 2.02 2.870 (3) 169} O1ÐH1O O3 0.82 1.68 2.496 (3) 174 C3ÐH3 O3 0.93 2.26 2.847 (4) 121 C5ÐH5 O2i _{0.93 2.58 3.315 (3) 137} C8ÐH8 O1i _{0.93 2.65 3.567 (4) 168} C9ÐH9 Clii _{0.93 2.86 3.720 (3) 154}

Symmetry codes: (i)x;3

2ÿy;zÿ12; (ii)x;1‡y;z.

Table 3

Short contact distances (AÊ).

Cl O1iii _{3.121 (3)} Cl O3iii _{3.458 (3)} C2 C8iv _{3.494 (5)} C3 C8iv _{3.454 (5)}

C4 O2i _{3.576 (3)} C6 C8v _{3.588 (4)} C7 O3vi _{3.538 (4)} O3 O3vi _{3.440 (3)}

Symmetry codes: (i) x;3

2ÿy;zÿ12; (iii) x;12ÿy;zÿ12; (iv) 1ÿx;1ÿy;1ÿz; (v)

ÿx;yÿ1

2;12ÿz; (vi)ÿx;1ÿy;1ÿz.

After location in a difference map, all the H atoms were ®xed geometrically and were treated as riding on their parent atoms, with CÐH = 0.93 AÊ, NÐH = 0.86 AÊ and OÐH = 0.82 AÊ. The initial coordinates were taken from the related previous work (Prasad & Mandal, 1978).

Data collection: CAD-4 EXPRESS (Enraf±Nonius, 1994); cell re®nement:CAD-4EXPRESS; data reduction:MolEN(Fair, 1990); program(s) used to solve structure: see above; program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:

ORTEP-3 (Farrugia, 1997); software used to prepare material for publication:SHELXL97.

The authors acknowledge Professor R. P. Rastogi, Depart-ment of Chemistry, Gorakhpur University, for the gift of the crystals and the Regional Sophisticated Instrumentation Centre, Bose Institute, Kolkata, for the collection of the X-ray diffraction data.

References

Enraf±Nonius (1994).CAD-4EXPRESS. Enraf±Nonius, Delft, The Nether-lands.

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

James, M. N. G. & Williams, G. J. B. (1974).Acta Cryst.B30, 1249±1257. Prasad, S. M. & Mandal, D. K. (1978).Indian J. Phys. Sect. A,52, 585±587. Prasad, S. M., Sinha, R. B. P., Mandal, D. K. & Rani, A. (2002).Acta Cryst.E58,

o891±o892.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany.

Figure 1

An ORTEP-3 plot (Farrugia, 1997) of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Figure 2

supporting information

sup-1

Acta Cryst. (2002). E58, o1296–o1297

supporting information

Acta Cryst. (2002). E58, o1296–o1297 [https://doi.org/10.1107/S1600536802019293]

N

-(

p

-Chlorophenyl)maleamic acid

Satya Murti Prasad, R. B. P. Sinha, Deo Kumar Mandal and Asha Rani

N-(p-chlorophenyl)maleamic acid

Crystal data

C10H8ClNO3 Mr = 225.62

Monoclinic, P21/c

Hall symbol: -P 2ybc

a = 7.306 (3) Å

b = 11.765 (4) Å

c = 12.828 (4) Å

β = 116.09 (4)°

V = 990.3 (6) Å3 Z = 4

F(000) = 464

Dx = 1.513 Mg m−3

Mo Kα radiation, λ = 0.71069 Å Cell parameters from 25 reflections

θ = 8.2–18.9°

µ = 0.37 mm−1 T = 293 K

Needle, light yellow 0.25 × 0.23 × 0.10 mm

Data collection

Enraf-Nonius CAD-4 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω–2θ scans

1707 measured reflections 1707 independent reflections 1224 reflections with I > 2σ(I)

Rint = 0.000

θmax = 25.0°, θmin = 2.5°

h = 0→8

k = 0→13

l = −15→13

3 standard reflections every 50 reflections intensity decay: nil

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.054} wR(F2_{) = 0.140} S = 0.92 1707 reflections 137 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_(Fo2_{) + (0.102P)}2_]

where P = (Fo2 _{+ 2Fc}2_)/3

(Δ/σ)max < 0.001

Δρmax = 0.51 e Å−3

Δρmin = −0.31 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

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 weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

Cl 0.26209 (14) 0.02180 (7) 0.35580 (7) 0.0632 (3) C1 0.2566 (4) 0.1669 (3) 0.3758 (2) 0.0430 (7) C2 0.2834 (5) 0.2104 (2) 0.4811 (2) 0.0475 (7) H2 0.3028 0.1614 0.5420 0.057* C3 0.2815 (4) 0.3263 (2) 0.4968 (2) 0.0436 (7) H3 0.3009 0.3553 0.5684 0.052* C4 0.2505 (4) 0.3999 (2) 0.4057 (2) 0.0375 (6) C5 0.2257 (4) 0.3548 (2) 0.2996 (2) 0.0420 (7) H5 0.2056 0.4030 0.2381 0.050* C6 0.2310 (4) 0.2389 (2) 0.2861 (2) 0.0445 (7) H6 0.2171 0.2092 0.2159 0.053* C7 0.2406 (4) 0.5830 (2) 0.4987 (2) 0.0382 (6) C8 0.2300 (4) 0.7058 (2) 0.4767 (2) 0.0391 (6) H8 0.2189 0.7272 0.4044 0.047* C9 0.2340 (4) 0.7909 (2) 0.5464 (2) 0.0426 (7) H9 0.2231 0.8625 0.5134 0.051* C10 0.2525 (4) 0.7936 (2) 0.6668 (2) 0.0421 (7) N1 0.2435 (3) 0.51903 (19) 0.41304 (17) 0.0390 (6) H1N 0.2408 0.5559 0.3545 0.047* O1 0.2716 (3) 0.69932 (17) 0.72392 (16) 0.0566 (6) H1O 0.2711 0.6453 0.6834 0.068* O2 0.2541 (4) 0.88419 (17) 0.71042 (17) 0.0599 (6) O3 0.2460 (3) 0.54096 (17) 0.58852 (16) 0.0551 (6)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

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Acta Cryst. (2002). E58, o1296–o1297

C9 0.0633 (18) 0.0300 (15) 0.0379 (14) 0.0003 (12) 0.0254 (13) 0.0005 (11) C10 0.0543 (17) 0.0336 (16) 0.0399 (14) −0.0051 (12) 0.0223 (12) −0.0091 (12) N1 0.0561 (14) 0.0300 (12) 0.0322 (11) −0.0029 (10) 0.0206 (10) −0.0010 (9) O1 0.1026 (17) 0.0362 (12) 0.0407 (10) −0.0001 (10) 0.0404 (11) −0.0030 (8) O2 0.0986 (17) 0.0371 (12) 0.0528 (12) −0.0055 (11) 0.0414 (12) −0.0119 (10) O3 0.0970 (17) 0.0362 (12) 0.0414 (11) −0.0043 (10) 0.0391 (11) −0.0025 (9)

Geometric parameters (Å, º)

Cl—C1 1.729 (3) C7—O3 1.239 (3) C1—C6 1.374 (4) C7—N1 1.340 (3) C1—C2 1.375 (4) C7—C8 1.468 (4) C2—C3 1.380 (4) C8—C9 1.333 (4)

C2—H2 0.93 C8—H8 0.93

C3—C4 1.391 (4) C9—C10 1.491 (4)

C3—H3 0.93 C9—H9 0.93

C4—C5 1.396 (4) C10—O2 1.201 (3) C4—N1 1.407 (4) C10—O1 1.302 (3) C5—C6 1.377 (4) N1—H1N 0.86

C5—H5 0.93 O1—H1O 0.82

C6—H6 0.93

Cl···O1i _{3.121 (3) C4···O2}iii _{3.576 (3)}

Cl···O3i _{3.458 (3) C6···C8}iv _{3.588 (4)}

C2···C8ii _{3.494 (5) C7···O3}v _{3.538 (4)}

C3···C8ii _{3.454 (5) O3···O3}v _{3.440 (3)}

C6—C1—C2 120.1 (3) C5—C6—H6 119.8 C6—C1—Cl 119.2 (2) O3—C7—N1 122.2 (3) C2—C1—Cl 120.7 (2) O3—C7—C8 123.3 (2) C1—C2—C3 120.3 (3) N1—C7—C8 114.4 (2) C1—C2—H2 119.8 C9—C8—C7 128.8 (2) C3—C2—H2 119.8 C9—C8—H8 115.6 C2—C3—C4 120.1 (2) C7—C8—H8 115.6 C2—C3—H3 120.0 C8—C9—C10 132.5 (2) C4—C3—H3 120.0 C8—C9—H9 113.7 C3—C4—C5 119.1 (3) C10—C9—H9 113.7 C3—C4—N1 124.1 (2) O2—C10—O1 121.1 (2) C5—C4—N1 116.8 (2) O2—C10—C9 118.7 (2) C6—C5—C4 120.0 (2) O1—C10—C9 120.2 (2) C6—C5—H5 120.0 C7—N1—C4 128.9 (2) C4—C5—H5 120.0 C7—N1—H1N 115.5 C1—C6—C5 120.4 (2) C4—N1—H1N 115.5 C1—C6—H6 119.8 C10—O1—H1O 109.5

C2—C3—C4—C5 −1.3 (4) C8—C9—C10—O2 179.2 (3) C2—C3—C4—N1 179.2 (3) C8—C9—C10—O1 1.0 (5) C3—C4—C5—C6 0.3 (4) O3—C7—N1—C4 0.7 (4) N1—C4—C5—C6 179.9 (3) C8—C7—N1—C4 −179.1 (3) C2—C1—C6—C5 −2.0 (4) C3—C4—N1—C7 −8.4 (4) Cl—C1—C6—C5 179.9 (2) C5—C4—N1—C7 172.0 (3) C4—C5—C6—C1 1.3 (4)

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+3/2, z−1/2; (iv) −x, y−1/2, −z+1/2; (v) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1—H1N···O2iii _{0.86 2.02 2.870 (3) 169}

O1—H1O···O3 0.82 1.68 2.496 (3) 174 C3—H3···O3 0.93 2.26 2.847 (4) 121 C5—H5···O2iii _{0.93 2.58 3.315 (3) 137}

C8—H8···O1iii _{0.93 2.65 3.567 (4) 168}

C9—H9···Clvi _{0.93 2.86 3.720 (3) 154}