Crystal structure of carbohydrazidium(1+) p-toluenesulfonate, (NH2NHCONHNH3)[CH3C6H4SO3]

Abstract

Source of materialCarbohydrazide (CHZ) was prepared according to [1]. 0.05 mol CHZ was dissolved in water (20 mL), then the aqueous of toluene-p-sulfonate (TPS) was added until pH = 6. Single crystals of (NH 3 NHCONHNH 2 )(CH 3 C 6 H 4 SO 3 ) (CHZTPS) suitable for Xray diffraction were obtained by slow evaporation at room temperature. Experimental detailsThe H atoms were positioned geometrically and refined by riding rigid body approximation, with exception of the H1A, H1B, H2N and H3N atoms which were refined under using of restraints for the NH bond lengths (0.86(1) Å). Additionally, the H atoms of the methyl group are found to be disordered uniformly by a rotation about 60°, whereupon their site occupancies were fixed to 0.5. DiscussionCarbohydrazide (CHZ) is a ramification of hydrazine, which has more functional groups [1]. So, it has been used in the field of intermediate of the organic synthesis for the fine chemicals and medicine. Because CHZ possesses relatively strong reduction ability, it has been used to design a variety of energetic coordination compounds with explosive properties, our group has done a lot of work in this field [2][3][4][5][6][7]. The title compound is a water-soluble derivative of CHZ, which is composed of one NH 3NHCONHNH2 + cation and one toluenep-sulfonate anion (figure, top). In the cation the bond lengths and bond angles of NH 3 NHCONHNH 2 + are similar to those of carbohydrazide [1], picric carbohydrazide (CHZPA) [2] and 3-nitro-1,2,4-triazol-5-one carbohydrazide (CHZNTO) [3]. Owing to the partial protonation of CHZ, the bond lengths of C1N3 and N3N4 are a little longer than those of C1N2 and N1N2 because of the electrostatic interaction between the cation and anion, which is in agreement with CHZPA and CHZNTO. Comparing the bond angles of CHZTPS, CHZPA, CHZNTO with CHZ, we can find that the bond angles of CNN of the formers are larger than those of the latter, and for CHZTPS, CHZPA and CHZNTO the bond angles of NH 3NHC are smaller than those of NH 2 NHC. NH 3 NHCONHNH 2 + cation and toluene-p-sulfonate anion are linked together by electrostatic interaction and hydrogen bonds, and there are seven kinds of hydrogen bonds in the crystal, among which five kinds of hydrogen bonds are between NH 3 NHCONHNH 2 + cations and toluene-p-sulfonate anions (N1H1B···O2(x,y, The hydrogen bonds link the molecules to form an infinite two-dimensional network structure, which make an important contribution to the stability of the title compound (figure, bottom).Acknowledgment. We are grateful to the Excellent Young Scholars Research Fund of the Beijing Institute of Technology (grant no. 000Y02-8).