Data collection. Refinement. R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 315 parameters

Transcription

1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN N-(2,4,5-Trichlorophenyl)maleamic acid B. Thimme Gowda, a * Miroslav Tokarčík, b Jozef Kožíšek, b K. Shakuntala a and Hartmut Fuess c a Department of Chemistry, Mangalore University, Mangalagangotri , Mangalore, India, b Faculty of Chemical and Food Technology, Slovak Technical University, Radlinského 9, SK Bratislava, Slovak Republic, and c Institute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D Darmstadt, Germany Correspondence gowdabt@yahoo.com Data collection Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector Absorption correction: analytical (CrysAlis PRO; Oxford Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 315 parameters Table 1 Hydrogen-bond geometry (Å, ). Diffraction, 2009) T min = 0.794, T max = measured reflections 4424 independent reflections 3825 reflections with I > 2(I) R int = H atoms treated by a mixture of independent and constrained refinement max = 0.28 e Å 3 min = 0.32 e Å 3 Received 26 November 2009; accepted 7 December 2009 Key indicators: single-crystal X-ray study; T = 295 K; mean (C C) = Å; R factor = 0.028; wr factor = 0.079; data-to-parameter ratio = The title compound, C 10 H 6 Cl 3 NO 3, crystallizes with two independent molecules in the asymmetric unit. The molecular structure is stabilized by a short intramolecular O HO hydrogen bond within the maleamic unit. In the crystal, each molecule self-associates via N HO hydrogen bonds into chains, each running along the b axis. Two short intermolecular ClO contacts [ (15) and (12) Å] and C HO interactions interconnect these chains into a threedimensional network. Related literature For studies on the effect of ring- and side-chain substitutions on the crystal structures of amides, see: Gowda et al. (2009, 2010); Lo & Ng (2009); Prasad et al. (2002); Shakuntala et al. (2009). For the concept of orthogonality of halogen and hydrogen bonds, see: Voth et al. (2009). For a review on short halogen oxygen contacts, see: Fourmigué (2009); Kubicki (2004). D HA D H HA DA D HA O2 H2AO (15) 175 O5 H5AO (17) 175 N1 H1NO3 i 0.77 (2) 2.30 (2) (18) (19) N2 H2NO6 ii 0.81 (2) (19) (19) (16) N1 H1NCl (2) 2.56 (2) (14) (17) N2 H2NCl (2) (18) (14) (15) C2 H2O3 i (2) 149 C12 H12O (2) 154 Symmetry codes: (i) x þ 1; y þ 1 2 ; z þ 3 2 ; (ii) x; y þ 1 2 ; z þ 3 2. Table 2 Halogen-bond geometry (Å, ). C ClO ClO C ClO C9 Cl3O6 iii (15) (6) C16 Cl4O (12) (7) Symmetry code: (iii) x; y þ 1 2 ; z 1 2 : Data collection: CrysAlis PRO (Oxford Diffraction, 2009); 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 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009) and WinGX (Farrugia, 1999). Experimental Crystal data C 10 H 6 Cl 3 NO 3 M r = Monoclinic, P2 1 =c a = (2) Å b = (2) Å c = (3) Å = (9) V = (7) Å 3 Z =8 Mo K radiation = 0.78 mm 1 T = 295 K mm MT and JK thank the Grant Agency of the Slovak Republic (VEGA 1/0817/08) and Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer. KS thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship under its faculty improvement programme Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: TK2591). o182 Gowda et al. doi: /s

2 organic compounds References Brandenburg, K. (2002). DIAMOND. Crystal Impact GbR, Bonn, Germany. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, Fourmigué, M. (2009). Curr. Opin. Solid State Mater. Sci. 13, Gowda, B. T., Tokarčík, M., Kožíšek, J., Shakunthala, K. & Fuess, H. (2009). Acta Cryst. E65, o2945. Gowda, B. T., Tokarčík, M., Kožíšek, J., Shakunthala, K. & Fuess, H. (2010). Acta Cryst. E66, o51. Kubicki, M. (2004). J. Mol. Struct. 698, Lo, K. M. & Ng, S. W. (2009). Acta Cryst. E65, o1101. Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Prasad, S. M., Sinha, R. B. P., Mandal, D. K. & Rani, A. (2002). Acta Cryst. E58, o1296 o1297. Shakuntala, K., Gowda, B. T., Tokarčík, M. & Kožíšek, J. (2009). Acta Cryst. E65, o3119. Sheldrick, G. M. (2008). Acta Cryst. A64, Spek, A. L. (2009). Acta Cryst. D65, Voth, A. R., Khuu, P., Oishi, K. & Ho, P. S. (2009). Nat. Chem. 1, Gowda et al. C 10 H 6 Cl 3 NO 3 o183

3 supporting information [doi: /s ] N-(2,4,5-Trichlorophenyl)maleamic acid B. Thimme Gowda, Miroslav Tokarčík, Jozef Kožíšek, K. Shakuntala and Hartmut Fuess S1. Comment In the present work, as a part of studying the effect of ring- and side-chain substitutions on the crystal structures of biologically significant amides (Gowda et al., 2009, 2010; Shakuntala et al., 2009; Prasad et al., 2002), the crystal structure of N-(2,4,5-trichlorophenyl)-maleamic acid (I) has been determined. The asymmetric unit of (I) contains two independent molecules (Fig. 1). The conformations of the N H and C=O bonds in the amide segment of the structure are anti to each other, and the amide-o atom and the carbonyl-o atom of the acid segment are also anti to each other. Further, the amide-o atom is anti to the H atom attached to the adjacent C atom, while the carbonyl-o atom is syn to the H atom attached to its adjacent C atom (Fig.1). In the structure, a rare anti conformation of the C=O and O H bonds of the acid group has been observed, similar to that observed in N-phenylmaleamic acid (Lo & Ng, 2009), N-(2,5-dichlorophenyl)maleamic acid (Shakuntala et al., 2009), N-(3,5-dichlorophenyl)maleamic acid (Gowda et al., 2010) and N-(2,4,6-dimethylphenyl)maleamic acid (Gowda et al., 2009). Further, the conformation of the N H bond is syn to the 2-Cl in the phenyl ring, while it is anti to the 5-Cl in the ring. Each maleamic unit includes a short intramolecular hydrogen O H O bond (Table 1). The bond lengths of C2 C3 and C12 C13 (i.e (2) and (2) Å) clearly indicate double bond character. In both the molecules, the dihedral angle between the amido group NHCO and the tri-substituted phenyl ring is 6.1 (3). The two N H O hydrogen bonds have quite different geometry, as seen in the N H O angles (Table 1). Remarkably small N2 H2N O6 ii angle of (16) can be attributed to the competing effect of the neighbouring C9 Cl3 O6 iii halogen bond. The angle Cl3 O6 iii H2N =78.24 (6) is close to 90 and can be interpreted within the concept of orthogonality of halogen and hydrogen bonds (Voth et al., 2009). The N1 H1N O3 i hydrogen bond with the angle of (19) is much less influenced by the near C6 Cl1 O3 i halogen bond, which is weaker as indicated by the Cl1 O3 i contact of (13) A. [Symmetry codes: (i) -x + 1, y + 1/2, -z + 3/2; (ii) -x, y + 1/2, -z + 3/2; (iii) x, -y + 1/2, z - 1/2.] In the crystal of (I), the intermolecular N H O hydrogen bonds link the molecules, which self-associate, into infinite chains running along the b axis. These chains are connected through relatively short Cl O contacts: Cl4 O1 = (12), Cl3 O6(iii) = (15) Å. [Symmetry codes: (iii) x, -y + 1/2, z - 1/2].(iii) x, -y + 1/2, z - 1/2] as well as C H O contacts to consolidate the crystal packing. Fig. 2 outlines part of the crystal structure of (I) with the N H O hydrogen bonding and Cl O contacts highlighted. The data for the C Cl O halogen bonds are in agreement with others (Kubicki, 2004; Fourmigué, 2009). S2. Experimental The solution of maleic anhydride (0.025 mol) in toluene (25 ml) was treated drop-wise with the solution of 2,4,5-trichloroaniline (0.025 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was warmed with stirring for over 30 min and set aside for an additional 30 min at room temperature for completion of the reaction. The mixture sup-1

4 was then treated with dilute hydrochloric acid to remove the unreacted 2,4,5-trichloroaniline. The resultant solid N-(2,4,5-trichlorophenyl)maleamic acid was filtered under suction and washed thoroughly with water to remove the unreacted maleic anhydride and maleic acid. It was recrystallized to constant melting point from ethanol. The purity of the compound was checked by elemental analysis and characterized by its infrared spectra. Colourless single crystals used in X-ray diffraction studies were grown in an ethanol solution by slow evaporation at room temperature. S3. Refinement H atoms were visible in difference maps. In the final cycles of refinement, the amido-h atoms were refined freely, while the C,O-bound H atoms were placed in calculated positions and refined using the riding model with C H = 0.93Å and O H = 0.82 Å. The U iso (H) values were set at 1.2U eq (C,O). Figure 1 Molecular structure of the two independent molecules comprising the asymmetric unit in (I) showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. sup-2

5 Figure 2 Part of crystal structure of (I) showing the main intermolecular interactions: N H O hydrogen bonds and short Cl O contacts (all represented by dashed lines). Symmetry codes: (i) -x + 1, y + 1/2, -z + 3/2; (ii) -x, y + 1/2, -z + 3/2; (iii) x, -y + 1/2, z - 1/2. N-(2,4,5-Trichlorophenyl)maleamic acid Crystal data C 10 H 6 Cl 3 NO 3 M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (2) Å b = (2) Å c = (3) Å β = (9) V = (7) Å 3 Z = 8 F(000) = 1184 D x = 1.68 Mg m 3 Mo Kα radiation, λ = Å Cell parameters from reflections sup-3

6 θ = µ = 0.78 mm 1 T = 295 K Data collection Oxford Diffraction Xcalibur diffractometer with a Ruby Gemini detector Graphite monochromator Detector resolution: pixels mm -1 ω scans Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2009) T min = 0.794, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 315 parameters 0 restraints Primary atom site location: structure-invariant direct methods Block, colourless mm measured reflections 4424 independent reflections 3825 reflections with I > 2σ(I) R int = θ max = 25.7, θ min = 1.9 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.0464P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.28 e Å 3 Δρ min = 0.32 e Å 3 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 F 2 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 F 2. 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 F 2 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 (Å 2 ) x y z U iso */U eq C (14) (14) (8) (3) C (16) (15) (8) (4) H * C (16) (16) (8) (4) H * C (14) (14) (8) (3) C (14) (13) (8) (3) C (15) (14) (8) (4) C (17) (15) (9) (4) H * C (16) (15) (8) (4) C (15) (15) (8) (4) sup-4

7 C (15) (14) (8) (3) H * N (13) (12) (7) (3) H1N (19) (18) (10) (6)* O (12) (11) (6) (3) O (10) (10) (6) (3) H2A * O (11) (10) (6) (3) Cl (5) (5) (2) (15) Cl (5) (4) (3) (15) Cl (4) (5) (2) (14) C (14) (14) (8) (3) C (15) (15) (8) (4) H * C (15) (16) (8) (4) H * C (16) (17) (9) (4) C (14) (14) (7) (3) C (16) (15) (8) (4) C (17) (16) (8) (4) H * C (16) (15) (8) (4) C (15) (15) (8) (3) C (15) (14) (8) (4) H * N (14) (13) (7) (3) H2N (18) (17) (9) (5)* O (13) (12) (6) (4) O (16) (15) (7) (5) H5A * O (14) (13) (7) (4) Cl (5) (4) (2) (14) Cl (5) (5) (2) (15) Cl (4) (4) (2) (14) Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 C (8) (8) (8) (6) (6) (6) C (10) (9) (8) (7) (7) (7) C (10) (9) (8) (8) (7) (7) C (8) (8) (8) (6) (6) (7) C (8) (8) (7) (6) (6) (6) C (9) (8) (8) (7) (7) (7) C (10) (9) (9) (7) (8) (7) C (10) (9) (8) (7) (7) (7) C (8) (9) (8) (7) (7) (7) C (8) (8) (8) (7) (7) (7) sup-5

8 N (7) (7) (7) (6) (6) (6) O (8) (7) (6) (6) (6) (5) O (7) (6) (6) (5) (5) (5) O (7) (6) (6) (5) (5) (5) Cl (3) (3) (3) (2) (2) (2) Cl (3) (3) (3) (2) (2) (2) Cl (3) (3) (2) (2) (19) (2) C (8) (8) (8) (7) (6) (6) C (8) (9) (8) (7) (7) (7) C (9) (10) (8) (7) (7) (7) C (10) (10) (9) (8) (8) (8) C (8) (8) (7) (6) (6) (6) C (9) (9) (8) (7) (7) (7) C (10) (9) (8) (8) (7) (7) C (9) (9) (7) (7) (7) (7) C (8) (9) (8) (7) (6) (6) C (9) (8) (8) (7) (7) (6) N (8) (8) (7) (6) (6) (6) O (8) (8) (6) (7) (6) (6) O (12) (12) (8) (10) (8) (8) O (9) (9) (7) (7) (6) (6) Cl (3) (3) (2) (2) (2) (2) Cl (3) (3) (2) (3) (2) (2) Cl (3) (3) (2) (2) (2) (2) Geometric parameters (Å, º) C1 O (18) C11 O (19) C1 N (2) C11 N (2) C1 C (2) C11 C (2) C2 C (2) C12 C (2) C2 H C12 H C3 C (2) C13 C (2) C3 H C13 H C4 O (18) C14 O (2) C4 O (18) C14 O (2) C5 C (2) C15 C (2) C5 C (2) C15 C (2) C5 N (2) C15 N (2) C6 C (2) C16 C (2) C6 Cl (16) C16 Cl (16) C7 C (3) C17 C (2) C7 H C17 H C8 C (2) C18 C (2) C8 Cl (16) C18 Cl (16) C9 C (2) C19 C (2) C9 Cl (16) C19 Cl (16) C10 H C20 H sup-6

9 N1 H1N 0.77 (2) N2 H2N 0.81 (2) O2 H2A O5 H5A O1 C1 N (14) O4 C11 N (14) O1 C1 C (14) O4 C11 C (14) N1 C1 C (13) N2 C11 C (14) C3 C2 C (15) C13 C12 C (15) C3 C2 H C13 C12 H C1 C2 H C11 C12 H C2 C3 C (15) C12 C13 C (15) C2 C3 H C12 C13 H C4 C3 H C14 C13 H O3 C4 O (14) O6 C14 O (16) O3 C4 C (14) O6 C14 C (16) O2 C4 C (13) O5 C14 C (15) C10 C5 C (14) C20 C15 C (14) C10 C5 N (14) C20 C15 N (14) C6 C5 N (14) C16 C15 N (14) C7 C6 C (15) C17 C16 C (15) C7 C6 Cl (13) C17 C16 Cl (13) C5 C6 Cl (12) C15 C16 Cl (12) C6 C7 C (15) C16 C17 C (15) C6 C7 H C16 C17 H C8 C7 H C18 C17 H C7 C8 C (15) C17 C18 C (14) C7 C8 Cl (13) C17 C18 Cl (13) C9 C8 Cl (13) C19 C18 Cl (13) C8 C9 C (15) C20 C19 C (15) C8 C9 Cl (13) C20 C19 Cl (12) C10 C9 Cl (13) C18 C19 Cl (12) C9 C10 C (14) C19 C20 C (15) C9 C10 H C19 C20 H C5 C10 H C15 C20 H C1 N1 C (14) C11 N2 C (14) C1 N1 H1N (15) C11 N2 H2N (13) C5 N1 H1N (15) C15 N2 H2N (13) C4 O2 H2A C14 O5 H5A O1 C1 C2 C3 0.1 (3) O4 C11 C12 C (3) N1 C1 C2 C (18) N2 C11 C12 C (18) C1 C2 C3 C4 1.6 (3) C11 C12 C13 C (3) C2 C3 C4 O (19) C12 C13 C14 O (2) C2 C3 C4 O2 0.8 (3) C12 C13 C14 O5 6.7 (3) C10 C5 C6 C7 2.3 (2) C20 C15 C16 C (2) N1 C5 C6 C (15) N2 C15 C16 C (16) C10 C5 C6 Cl (12) C20 C15 C16 Cl (13) N1 C5 C6 Cl1 2.4 (2) N2 C15 C16 Cl4 1.9 (2) C5 C6 C7 C8 1.3 (3) C15 C16 C17 C (3) sup-7

10 Cl1 C6 C7 C (13) Cl4 C16 C17 C (14) C6 C7 C8 C9 0.9 (3) C16 C17 C18 C (3) C6 C7 C8 Cl (13) C16 C17 C18 Cl (14) C7 C8 C9 C (2) C17 C18 C19 C (3) Cl2 C8 C9 C (13) Cl5 C18 C19 C (13) C7 C8 C9 Cl (13) C17 C18 C19 Cl (14) Cl2 C8 C9 Cl3 0.9 (2) Cl5 C18 C19 Cl6 0.3 (2) C8 C9 C10 C5 1.0 (2) C18 C19 C20 C (3) Cl3 C9 C10 C (12) Cl6 C19 C20 C (12) C6 C5 C10 C9 1.1 (2) C16 C15 C20 C (2) N1 C5 C10 C (15) N2 C15 C20 C (15) O1 C1 N1 C5 1.4 (3) O4 C11 N2 C (3) C2 C1 N1 C (15) C12 C11 N2 C (16) C10 C5 N1 C1 5.1 (3) C20 C15 N2 C (3) C6 C5 N1 C (15) C16 C15 N2 C (16) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O2 H2A O (15) 175 O5 H5A O (17) 175 N1 H1N O3 i 0.77 (2) 2.30 (2) (18) (19) N2 H2N O6 ii 0.81 (2) (19) (19) (16) N1 H1N Cl (2) 2.56 (2) (14) (17) N2 H2N Cl (2) (18) (14) (15) C2 H2 O3 i (2) 149 C12 H12 O (2) 154 Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y+1/2, z+3/2. sup-8