Adenosinium 3,5-dinitrosalicylate

Graham Smith,Urs D Wermuth,Peter C Healy

doi:10.1107/s1600536804019920

Abstract

The crystal structure of adenosinium 3,5-dinitrosalicylicate, C10H14N5O4+·C7H3N2O7−, shows the presence of a primary chain structure formed through homomeric head-to-tail cyclic R22(10) hydrogen-bonding interactions between hydroxy O- and both purine and amine N-donor and acceptor groups of the furanose and purine moieties of the adenosinium species. These chain structures are related by crystallographic 21 symmetry. Secondary hetero-ionic hydrogen bonding, involving the 3,5-dinitrosalicylate anion, including a cyclic R22(8) interaction between the carboxylate group and the protonated purine and amine groups of the adenosinium cation are also present, together with heteromolecular π–π interactions giving a three-dimensional hydrogen-bonded polymer structure.

Highlights

Adenosinium picrate has been known for some time (Stecher, 1968), but its crystal structure has only recently been reported (Goto et al, 2004)
We report here the crystal structure of a proton-transfer compound formed from the reaction of adenosine with an acid similar to picric acid, 3,5-dinitrosalicylic acid (DNSA)± adenosinium 3,5-dinitrosalicylate, (I)
The DNSA anions are primarily associated with the adenosinium cations peripherally through R22(8) cyclic hydrogen-bonded dimers involving the two carboxylate O-atom acceptors and two purine donors, the protonated hetero N atom and the substituent amine N atom [N12ÐH12Á Á ÁO7Ai: 2.763 (4) AÊ ; N62Ð H62BÁ Á ÁO7Bi: 2.785 (5) AÊ ; symmetry code: (i) 1 À x, y À 12, 1 À z] (Fig. 3)

Summary

Structure Reports Online

Adenosine will react with the stronger carboxylic acids, resulting in protonation at the N1 position of the purine ring, giving salts with enhanced crystallinity due to hydrogenbonding interactions, such as in the adenosinium chloride structure (Shikata et al, 1973) and the structural aspects of protonated and complexed adenosine have been reviewed (Hauser & Keese, 2002) One such compound, adenosinium picrate has been known for some time (Stecher, 1968), but its crystal structure has only recently been reported (Goto et al, 2004). The DNSA anions are primarily associated with the adenosinium cations peripherally through R22(8) cyclic hydrogen-bonded dimers involving the two carboxylate O-atom acceptors and two purine donors, the protonated hetero N atom and the substituent amine N atom [N12ÐH12Á Á ÁO7Ai: 2.763 (4) AÊ ; N62Ð H62BÁ Á ÁO7Bi: 2.785 (5) AÊ ; symmetry code: (i) 1 À x, y À 12, 1 À z] (Fig. 3). After concentration to ca 30 ml, partial room temperature evaporation of the hot-®ltered solution gave thin pale-yellow crystal plates (m.p. 487.2±488.5 K)

Data collection

Findings

DÁ Á ÁA