organic papers Acta Crystallographica Section E Structure Reports Online 3-[(2,4-Dinitrophenyl)hydrazono]butan-2-one oxime ISSN 1600-5368 Hanife SaracËogÆlu,a* Ceyda È mer Davran,b Serkan Soylu,a O b b AndacË, Hu Èmeyra Batõ and Nezihe C Ë alõsËkana a Ondokuz Mayõs University Art and Sciences Faculty, Department of Physics, 55139 Samsun, Turkey, and bOndokuz Mayõs University Art and Sciences Faculty, Department of Chemistry, 55139 Samsun, Turkey Correspondence e-mail: hanifesa@omu.edu.tr Key indicators Single-crystal X-ray study T = 293 K Ê Mean (C±C) = 0.004 A R factor = 0.050 wR factor = 0.132 Data-to-parameter ratio = 11.6 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e. # 2004 International Union of Crystallography Printed in Great Britain ± all rights reserved Acta Cryst. (2004). E60, o1307±o1309 The title compound, C10H11N5O5, contains of dinitrophenyl, monooxime and hydrazone groups. The molecules are linked through OÐH


N and CÐH


O hydrogen bonds. There are also ± interactions and intramolecular hydrogen bonds. All these hydrogen bonds are highly effective in forming dimeric chains, thereby stabilizing the crystal structure. The monooxime and hydrazone groups both have an E con®guration. Received 6 May 2004 Accepted 22 June 2004 Online 9 July 2004 Comment Various hydrazone compounds possess strong bactericidal, herbicidal, insecticidal and fungicidal properties (Sahni et al., 1977). Some phenylhydrazone derivatives have been shown to be potentially DNA-damaging and are mutagenic agents (Okabe et al., 1993). In addition, hydrazones have analytical applications (Heit & Ryan, 1966; Jensen & P¯aum, 1967; Dey et al., 1985). Hydrazones have interesting ligational properties due to the presence of several potential coordination sites (Dutta & Hossain, 1985), and both transition and non-transition metal complexes of these ligands have been synthesized previously (Dey et al., 1992). Oximes and their derivatives are very important compounds for the chemical industry, and in medicine as a result of their biological activity. The oxime group possesses stronger hydrogen-bonding capabilities than alcohol, phenol and carboxylic acid groups (Marsman et al., 1999). Hydrogen bonding plays a key role in molecular recognition in crystal engineering (Bertolasi et al., 1982; Gilli et al., 1983). The crystal structure determination of the title compound, (I), was carried out to determine the strength of the hydrogenbonding capabilities of the oxime (C NÐOH) and hydrazone (HNÐN C) groups, as well as to establish the molecular arrangement; the aim also was to compare the geometry of oxime and hydrazone moieties with those found in 4methyl-2-[N-(3,4-methylenedioxybenzylidene)hydrazino]thiazole and its reduction product 4-methyl-2-[N-(3,4-methylenedioxybenzylidene)hydrazono]-4,5-dihydrothiazole, (II) (Wouters et al., 2002), propiophenone 2,4-dinitrophenylhydrazone, (III) (Shan et al., 2002a), and acetophenone (2,4dinitrophenyl)hydrazone, (IV) (Shan et al., 2002b). DOI: 10.1107/S1600536804015235 Hanife Sarac ËogÆlu et al.  C10H11N5O5 o1307 organic papers Ê [symmetry code: (i) 1 ÿx, ÿy, 1 ÿ z] and C8i ring is 3.292 A Ê . An the distance between the ring centroids is 3.538 (3) A uneven distribution of -electron density in the aromatic ring is probably responsible for the mutual orientation of these rings (Bogdanovic et al., 2002). Experimental Figure 1 A view of the molecular structure of (I), with the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. 2,4-Dinitrophenylhydrazine (1 mmol, 0.198 g) was dissolved by heating in ethanol (5 ml). H2SO4 (98%, 1 ml) solution was added to this, giving a clear orange solution at 373 K. Butane-2,3-dione monooxime (1 mmol, 0.101 g) in ethanol (4 ml) was added dropwise with stirring and the mixture re¯uxed for 2 h. The product was ®ltered off and dried before being dissolved in ethanol and left at room temperature to yield orange crystals. Crystal data Dx = 1.503 Mg mÿ3 Mo K radiation Cell parameters from 8500 re¯ections  = 2.0±26.8  = 0.12 mmÿ1 T = 293 (2) K Prism, orange 0.35  0.23  0.12 mm C10H11N5O5 Mr = 281.24 Monoclinic, P21 =c Ê a = 10.1400 (16) A Ê b = 12.3079 (19) A Ê c = 10.6624 (18) A = 110.950 (12) Ê3 V = 1242.7 (3) A Z=4 Data collection Figure 2 Diagram showing the hydrogen-bonding and ± interactions in (I). Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 1 ÿ x, ÿy, 1 ÿ z; (ii) ÿx, 1 ÿ y, ÿz; (iii) 1 ÿ x, 1 3 2 + y, 2 ÿ z.] Rint = 0.103 max = 25.0 h = ÿ12 ! 11 k = ÿ14 ! 14 l = ÿ12 ! 12 Stoe IPDS-2 diffractometer ! and ' scans Absorption correction: none 12 323 measured re¯ections 2180 independent re¯ections 1207 re¯ections with I > 2(I) Re®nement Compound (I) contains three moieties: dinitrophenyl, monooxime and hydrazone (Fig. 1). The dihedral angles between oxime plane A (O1/N1/C1), hydrazone plane B (C2/ N2/N3) and benzene plane C (C3±C8) are A/B = 1.91 (26) , A/C = 4.49 (17) and B/C = 4.74 (17) . The molecule has an approximately planar structure. Oxime and dinitrophenyl groups are linked through a hydrazone moiety. The bond lengths and angles of the oxime and hydrazone moieties are given in Table 1 and a comparison of bond lengths and angles of (I) with those in the related compounds (II), (III) and (IV) is given in Table 3. Both the oxime and hydrazone moieties in (I) have an E con®guration [O1ÐN1ÐC1ÐC2 = ÿ179.4 (3) and N3ÐN2ÐC2ÐC1 = ÿ178.5 (3) ]. In these groups, atom O1 of the oxime group behaves as a donor, resulting in the formation of OÐH


N hydrogen bonds which link two molecules related by an inversion centre. Atom C7 of the benzene ring also behaves as a donor, resulting in the formation of CÐH


O hydrogen bonds which link another two molecules to form the supramolecular layered structure (Fig. 2). There is also an intramolecular N3ÐH


O2 hydrogen bond, as found in many other studies (Vickery et al., 1985) In addition, there is an intermolecular ± interaction between the benzene rings. The rings are oriented in such a way that the perpendicular distance from C3ÐC8 to the C3i± o1308 Hanife Sarac ËogÆlu et al.  C10H11N5O5 Re®nement on F 2 R[F 2 > 2(F 2)] = 0.050 wR(F 2) = 0.132 S = 0.87 2180 re¯ections 188 parameters H atoms treated by a mixture of independent and constrained re®nement w = 1/[ 2(Fo2) + (0.0738P)2] where P = (Fo2 + 2Fc2)/3 (
/)max < 0.001 Ê ÿ3
max = 0.20 e A Ê ÿ3
min = ÿ0.17 e A Extinction correction: SHELXL97 Extinction coef®cient: 0.018 (4) Table 1 Ê ,  ). Selected geometric parameters (A N1ÐC1 N1ÐO1 N2ÐC2 N2ÐN3 N3ÐC3 1.292 (3) 1.396 (3) 1.290 (3) 1.373 (3) 1.358 (3) N4ÐC4 N5ÐC6 C1ÐC2 C1ÐC9 C2ÐC10 1.454 (3) 1.467 (3) 1.473 (4) 1.477 (4) 1.492 (4) C1ÐN1ÐO1 C2ÐN2ÐN3 C3ÐN3ÐN2 N1ÐC1ÐC2 111.6 (2) 114.2 (2) 122.5 (2) 113.9 (3) N1ÐC1ÐC9 N2ÐC2ÐC1 N3ÐC3ÐC4 N3ÐC3ÐC8 124.7 (2) 115.9 (2) 121.9 (2) 120.9 (2) C2ÐN2ÐN3ÐC3 O1ÐN1ÐC1ÐC2 O1ÐN1ÐC1ÐC9 N3ÐN2ÐC2ÐC1 N1ÐC1ÐC2ÐN2 ÿ175.4 (2) ÿ179.47 (19) ÿ0.6 (4) ÿ178.4 (2) 179.3 (2) N1ÐC1ÐC2ÐC10 C9ÐC1ÐC2ÐC10 N2ÐN3ÐC3ÐC4 N2ÐN3ÐC3ÐC8 N3ÐC3ÐC4ÐN4 ÿ0.9 (4) ÿ179.8 (3) 178.0 (2) ÿ1.4 (4) 1.1 (4) Acta Cryst. (2004). E60, o1307±o1309 organic papers Table 2 Ê ,  ). Hydrogen-bonding geometry (A DÐH


A DÐH H


A D


A DÐH


A O1ÐH1


N1ii C7ÐH7


O4iii N3ÐH3


O2 0.82 0.93 0.85 (3) 2.22 2.54 1.92 (3) 2.932 (3) 3.230 (4) 2.587 (3) 146 131 135 (2) Symmetry codes: (i) ÿx; 1 ÿ y; ÿz; (iii) 1 ÿ x; 12 ‡ y; 32 ÿ z. Table 3 Ê ,  ) in the hydrazone moiety of (I) compared Geometrical parameters (A with those in the related compounds (II), (III) and (IV). Bonds (I) (II) (III) (IV) N3ÐC3 N2ÐN3 N2ÐC2 1.358 (3) 1.373 (3) 1.290 (3) 1.356 (2) 1.3714 (18) 1.276 (2) 1.343 (3) 1.379 (3) 1.289 (3) 1.351 (3) 1.367 (3) 1.286 (3) C3ÐN3ÐN2 C2ÐN2ÐN3 122.5 (2) 114.2 (2) 116.11 (13) 116.83 (14) 119.1 (2) 117.0 (2) 120.39 (19) 116.7 (2) The H atom bound to N3 was found in a difference map and re®ned freely; the other H atoms were placed in calculated positions and constrained to an idealized geometry, with an OÐH distance of Ê , and CÐH distances of 0.93 and 0.96 A Ê . The Uiso(H) values 0.82 A were constrained to be 1.2 (1.5 for hydroxy and methyl groups) times Ueq of the carrier atom. Acta Cryst. (2004). E60, o1307±o1309 Data collection: X-AREA (Stoe & Cie, 2002); cell re®nement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999). References Bertolasi, V., Gilli, G. & Veronese, A. C. (1982). Acta Cryst. B38, 502±511. BogdanovicÂ, G. A., Miadragovic, D. U. & Malinar, M. J. (2002). Acta Cryst. C58, m338±m340. Dey, K., Mandal, K. & Bandyopadhyay, D. (1992). Indian J. Chem. Sect. A, 31, 937±942. Dey, K., Ray, S. B., Bhattacharya, P. K., Gangopadhyay, A., Bhasin, K. K. & Verma, R. D. (1985). J. Indian Chem. Soc. 62, 809±814. Dutta, R. L. & Hossain, M. (1985). J. Sci. Ind. Res. 44, 635±674. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838. Gilli, G., Bertolasi, V. & Veronese, A. C. (1983). Acta Cryst. B39, 450±456. Heit, M. L. & Ryan, D. E. (1966). Anal. Chim. Acta, 34, 407±411. Jensen, R. E. & P¯aum, R. T. (1967). Anal. Chim. Acta, 37, 397±400. Marsman, A. W., Leussink, E. D., Zwikker, J. W. & Jenneskens, L. W. (1999). Chem. Mater. 11, 1484±1491. Okabe, N., Nakamura, T. & Fukuda, H. (1993). Acta Cryst. C49, 1678±1680. Sahni, S. K., Sangal, S. K., Gupta, S. P. & Rana, V. B. (1977). J. Inorg. Nucl. Chem. 39, 1098±1100. Shan, S., Xu, D., Wu, J. & Chiang, M. (2002a). Acta Cryst. E58, o1444±o1445. Shan, S., Xu, D., Wu, J. & Chiang, M. (2002b). Acta Cryst. E58, o1333±o1335. Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473. Sheldrick, G. M. (1997). SHELXL97. University of GoÈttingen, Germany. Stoe & Cie (2002). X-AREA (Version 1.18) and X-RED32 (Version 1.04). Stoe & Cie, Darmstadt, Germany. Vickery, B., Willey, G. R. & Drew, M. G. B. (1985). Acta Cryst. C41, 1072±1075. Wouters, J., Norberg, B. & Guccione, S. (2002). Acta Cryst. C58, o69±o71. Hanife Sarac ËogÆlu et al.  C10H11N5O5 o1309