(1E,3E)-4-(tetra-O-acetyl-D-arabino-tetritol-1-yl)-1-(4-tolyl)-1,2-diaza-1, 3-butadiene

organic papers Acta Cryst. (2006). E62, o2811–o2812 doi:10.1107/S1600536806021428 Dia ´nez et al. C 21 H 26 N 2 O 8 o2811 Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 (1E,3E)-4-(Tetra-O-acetyl-D-arabino-tetritol-1-yl)- 1-(4-tolyl)-1,2-diaza-1,3-butadiene Marı ´a Jesu ´sDia ´nez, Marı ´a Dolores Estrada and Simeo ´nPe ´rez-Garrido* Instituto de Ciencias de Materiales de Sevilla and Departamento de Fı ´sica de la Materia Condensada, CSIC-Universidad de Sevilla, Apartado 1065, 41080 Sevilla, Spain Correspondence e-mail: [email protected] Key indicators Single-crystal X-ray study T= 293 K Mean (C–C) = 0.009 A ˚ Rfactor = 0.046 wR factor = 0.166 Data-to-parameter ratio = 8.8 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e. Received 23 May 2006 Accepted 6 June 2006 #2006 International Union of Crystallography All rights reserved In the title compound, C 21 H 26 N 2 O 8 , the configurations of the three chiral centres are known from the synthesis, corresponding to a d-arabino configuration. Both double bonds show the Econfiguration in the solid state. Packing of the molecules is governed by normal van der Waals contacts. Comment Following current work on asymmetric synthesis from carbohydrates, Avalos et al. (1995) developed a general synthesis of sugar 1,2-diaza-1,3-butadienes. The title compound, (I), was prepared by treatment of d-mannose with aryl hydrazines, and the corresponding aryl hydrazones were readily obtained. Further conventional acetylation and thermal 1,4-elimination gave 1-aryl-1,2-diaza-1,3-butadienes. In all cases, aryl diazabutadienes were coloured crystalline compounds and could be stored for long periods without appreciable decomposition. An X-ray investigation of compound (I) was carried out in order to elucidate unequivocally the molecular conformation of (I) in the solid state. A perspective view of (I) with the atom-numbering scheme is shown in Fig. 1. Prinicpal geometric parameters are given in Table 1. Both double bonds exist in the Econfiguration in the solid state. The arabino chain (C4/C41/C42/C43) is planar, with the terminal atom C44 having a maximum deviation from the least-squares plane of 0.017 (5) A ˚. The configurations of the chiral centres C41, C42 and C43 are R,Sand R, respectively. The packing of the molecules is governed by normal van der Waals contacts. Experimental The title compound was synthesized from d-mannose (4-methyl- phenyl) hydrazone, according to the procedure of Avalos et al. (1995). Compound (I) was recrystallized from ethanol–water. Crystal data C 21 H 26 N 2 O 8 M r = 434.44 Orthorhombic, P212121 a= 14.065 (1) A ˚ b= 30.189 (2) A ˚ c= 5.6414 (3) A ˚ V= 2395.4 (3) A ˚ 3 Z=4 D x = 1.205 Mg m 3 Mo Kradiation = 0.09 mm 1 T= 293 (2) K Prism, light brown 0.32 0.28 0.16 mm Data collection Enraf–Nonius CAD-4 diffractometer !/2scans Absorption correction: none 5210 measured reflections 2458 independent reflections 1196 reflections with I>2(I) R int = 0.027  max =25  3 standard reflections frequency: 60 min intensity decay: 6% Refinement Refinement on F 2 R[F 2 >2(F 2 )] = 0.046 wR(F 2 ) = 0.166 S= 0.97 2458 reflections 280 parameters . w= 1/[ 2 (F o2 ) + (0.0855P) 2 + 0.3134P] where P=(F o 2 +2F c 2 )/3 (/) max = 0.009  max = 0.22 e A ˚ 3  min =0.17 e A ˚ 3 Table 1 Selected geometric parameters (A ˚,). N2—N1 1.254 (6) N2—C3 1.404 (7) N1—C11 1.427 (7) C41—C4 1.493 (7) C4—C3 1.318 (8) N1—N2—C3 112.2 (5) N2—N1—C11 113.1 (5) C3—C4—C41 123.8 (5) C4—C3—N2 119.3 (5) H atoms were refined using a riding model, with C—H distances in the range 0.93–0.98 A ˚and with U iso (H)=1.2U eq (C) or 1.5U eq (C methyl ). In the absence of significant anomalous scatterers, Friedel pairs were merged. The absolute configuration was assigned by reference to the known chirality of the starting material used in the synthesis. Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995). The authors thank Dr Palacios, Universidad de Extremadura, Badajoz, Spain, for supplying the crystal, and the Junta de Andalucı ´a for financial support. References Avalos, M., Babiano, R., Cintas, P., Jimenez, J. L., Palacios, J. C. & Sanchez, J. B. (1995). Tetrahedron Asymmetry,6, 954–956. Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103. Enraf–Nonius (1994). CAD-4 EXPRESS. Version 5.1/1.2. Enraf–Nonius, Delft, The Netherlands. Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Nardelli, M. (1995). J. Appl. Cryst. 28, 659. Sheldrick, G. M. (1997). SHELXL97. Release 97-2. University of Go ¨ttingen, Germany. organic papers o2812 Dia ´nez et al. C 21 H 26 N 2 O 8 Acta Cryst. (2006). E62, o2811–o2812 Figure 1 A view of the molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. For clarity, only the most important H atoms are shown.