The crystal structure of adenosinium 3,5-dinitrosalicylicate, C10H14N5O4+烷H3N2O7-, 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 - interactions giving a three-dimensional hydrogen-bonded polymer structure.Full Tex

Healy, Peter

Smith, Graham

Wermuth, Urs

Acta Crystallographica Section E

English

D. Wermuth, Urs

Griffith Research Online

organic papersActa Cryst. (2004). E60, o1573±o1576 DOI: 10.1107/S1600536804019920 Graham Smith et al.  C10H14N5O4+C7H3N2O7ÿ o1573Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368Adenosinium 3,5-dinitrosalicylateGraham Smith,a* Urs D.Wermutha and Peter C. HealybaSchool of Physical and Chemical Sciences,Queensland University of Technology, GPOBox 2434, Brisbane 4001, Australia, andbSchool of Science, Griffith University, Nathan4111, AustraliaCorrespondence e-mail: g.smith@qut.edu.auKey indicatorsSingle-crystal X-ray studyT = 298 KMean (C±C) = 0.005 AÊR factor = 0.036wR factor = 0.122Data-to-parameter ratio = 7.6For details of how these key indicators wereautomatically derived from the article, seehttp://journals.iucr.org/e.# 2004 International Union of CrystallographyPrinted in Great Britain ± all rights reservedThe crystal structure of adenosinium 3,5-dinitrosalicylicate,C10H14N5O4+C7H3N2O7ÿ, shows the presence of a primarychain structure formed through homomeric head-to-tail cyclicR22(10) hydrogen-bonding interactions between hydroxy O-and both purine and amine N-donor and acceptor groups ofthe furanose and purine moieties of the adenosinium species.These chain structures are related by crystallographic 21symmetry. Secondary hetero-ionic hydrogen bonding, invol-ving the 3,5-dinitrosalicylate anion, including a cyclic R22(8)interaction between the carboxylate group and the protonatedpurine and amine groups of the adenosinium cation are alsopresent, together with heteromolecular ± interactionsgiving a three-dimensional hydrogen-bonded polymer struc-ture.CommentThe nucleoside adenosine (6-amino-9-d-ribofuranosyl-9H-purine) is an essential biological molecule, which in its 50-di-and triphosphorolated forms (ADP, ATP) is associated withenergy-transfer processes in muscle tissue (Wilson et al., 1991),where the ATP levels in mammals are commonly 350±400 mgper 100 g (Stecher, 1968). Also as its 30,50-cyclic monopho-sphate ester (cAMP) it is associated with G proteins in secondmessenger systems for a number of hormones (Wilson et al.,1991). Adenosine is also involved in a number of otherbiological processes involving RNA where it is present withhigh frequency among the structural motifs (Portmann et al.,1996; Ortoleva-Donnelly et al., 1998), while it has also been atargeted molecule for derivatization for enzyme pro-drugtherapy (Vogt et al., 2000; Bressi et al., 2000; Qiu et al., 2002;Costanzi et al., 2003). The structures of many simple neutraladenosine analogues have been reported, including the parent[Lai & Marsh, 1972 (X-ray); Klooster et al., 1991 (neutron,123 K)], adenosine-50-phosphate (Kraut & Jensen, 1963),adenosine-30-phosphate dihydrate (adenylic acid b) (Brown etal., 1953; Sundaralingam, 1966), deoxyadenosine monohydrate(Watson et al., 1965), adenosine-50-O-methylphosphate(Hoogendorp et al., 1978), 30-O-acetyladenosine (Rao &Sundaralingam, 1970), and -d-20-deoxyadenosine mono-hydrate (Rohrer & Sundaralingam, 1970). The stereo-chemistry of 30-N-substituted 30-deoxyadenosines has alsobeen reviewed (Sheldrick & Morr, 1980) and the structure ofthe Na salt of deoxyadenosine-50-phosphate hexahydrate hasbeen determined (Reddy & Viswamitra, 1975). The di- andtrinucleoside phosphate esters -adenosine-20--uridine-50-phosphate (Shefter et al., 1969) and adenylyl-(30,50)-adenylyl-(30,50)-adenosine (Suck et al., 1976) are also known. Thestructures of neutral adducts of adenosine with 5-bromo-uridine (Haschemeyer & Sobell, 1965), 5-bromouracil (Aiba etReceived 2 August 2004Accepted 11 August 2004Online 21 August 2004al., 1978) and pro¯avine (Swaminathan et al., 1982) have beenreported, and in this 1:2 pro¯avine structure, stability isenhanced by the presence of heteromolecular ± ringinteractions, as well as the expected conventional hydrogen-bonding interactions.As a base, adenosine will react with the stronger carboxylicacids, resulting in protonation at the N1 position of the purinering, giving salts with enhanced crystallinity due to hydrogen-bonding interactions, such as in the adenosinium chloridestructure (Shikata et al., 1973) and the structural aspects ofprotonated and complexed adenosine have also beenreviewed (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).We report here the crystal structure of a proton-transfercompound formed from the reaction of adenosine with an acidsimilar to picric acid, 3,5-dinitrosalicylic acid (DNSA)±adenosinium 3,5-dinitrosalicylate, (I). We have previouslycompleted the structures of more than 40 charge-transfercompounds of DNSA with both aliphatic and aromatic Lewisbases (Smith et al., 2002; Smith et al., 2003, 2004). In these,conventional hydrogen bonding is the most signi®cant inter-molecular interaction in determining the crystal packing, withinter-species ± interactions limited to those examples withthe polycyclic heteroaromatic bases quinoline, 2,20-bipyridineand 1,10-phenanthroline (Smith et al., 2004).In the structure of (I) (Fig. 1), proton transfer to N12 of thepurine ring occurs with subsequent formation of both homo-and heteromolecular hydrogen-bonding associations (Table 1),resulting in a three-dimensional polymer structure. Theprimary structure involves the adenosinium cations in homo-meric cyclic R22(10) head-to-tail associations involving two ofthe nitrogen groups of the purine residue and two hydroxygroups of the ribose residue [O31ÐH31A  N72iii:2.785 (4) AÊ ; N62ÐH62A  O21v: 2.886 (4) AÊ ; symmetrycodes: (iii) x, y + 1, z; (v) x, y ÿ 1, z]. These 21 screw-relatedchains extend along the b-cell direction (Fig. 2). The DNSAanions are primarily associated with the adenosinium cationsperipherally through R22(8) cyclic hydrogen-bonded dimersinvolving the two carboxylate O-atom acceptors and twopurine donors, the protonated hetero N atom and the substi-tuent amine N atom [N12ÐH12  O7Ai: 2.763 (4) AÊ ; N62ÐH62B  O7Bi: 2.785 (5) AÊ ; symmetry code: (i) 1 ÿ x, y ÿ 12,1 ÿ z] (Fig. 3). This type of association is similar to thecommon symmetric carboxylate 2-aminopyrimidine interac-tion found in the DNSA-2-aminopyrimidine structure (Smithet al., 2003) and in other similar structures (Lynch et al., 1994,1997; Smith et al., 1995). The O21 ribose hydroxy group is alsostrongly linked to a DNSA carboxyl O atom (O7Aii) down thec-cell direction [2.782 (4) AÊ : symmetry code: (ii) x, y, 1 + z].Other weaker ribose-O  DNSA 5-nitro-O associations alsolink the polymer strands while the 3-nitro group is unasso-ciated, as are O41 of the ribose and N32 of the purine residuesof the adenosinium cation. There are also signi®cant hetero-molecular ± stacking interactions between the six-organic paperso1574 Graham Smith et al.  C10H14N5O4+C7H3N2O7ÿ Acta Cryst. (2004). E60, o1573±o1576Figure 1The molecular con®guration and atom-numbering scheme for theadeninium cation and the DNSA anion in (I), with displacementellipsoids drawn at the 30% probability level and H atoms representedby spheres of arbitrary radius. The intramolecular hydrogen bond isshown as a dashed line.Figure 2Head-to-tail homomeric adenosinium cation±chain associations along theb-cell direction, with A and B chains related by a 21 screw operation.Hydrogen bonds are shown as dashed lines.membered DNSA anion benzene rings with the ®ve-membered (N72±C82) portions of the adenosinium cationrings down the c axis [minimum ring centroid separation =3.61 (1) AÊ ]. The overall result is a three-dimensional polymerstructure.The conformation of the adenosinium cation appears to bein¯uenced in (I) by the presence of an intramolecular CÐH  O interaction between H82 of the purine ring and theO51 hydroxy group [3.278 (5) AÊ ]. However, the resultanttorsion angle C82ÐN92ÐC11ÐC21 [ÿ71.4 (4)] is a valuewhich is extremely variable among the adenosine analogues.Within the DNSA anion, the structural features vary fromthose of the majority of the proton-transfer compounds(Smith et al., 2002, 2003) mainly in the conformation of thenitro substituent groups. The proximal nitro group at C3 ismore commonly involved in hydrogen bonding and thereforeshows a greater rotation out of the plane of the ring than theC5 group. However, in (I), where both O5A and O5B areassociated, C5 rotation is greater than usual but C3 rotation isalso signi®cant, despite being unassociated [torsion angles:C4ÐC5ÐN5ÐO5B = 152.6 (4) AÊ and C2ÐC3ÐN3ÐO5B =146.8 (4)]. By comparison, the torsion angle C2ÐC1ÐC7ÐO7A, associated with the intramolecularly hydrogen-bondedcarboxylate group, is ÿ177.7 (4). This hydrogen bond[O2  O7B = 2.438 (5) AÊ ] has the proton located on thephenol O atom rather than the carboxyl group, such as isfound in ca 70% of the proton-transfer compounds of DNSA(Smith et al., 2002, 2003).ExperimentalThe title compound was synthesized by heating under re¯ux for10 min, 1 mmol quantities of adenosine and 3,5-dinitrosalicylic acid(DNSA) in 50 ml of 50% ethanol/water. After concentration to ca30 ml, partial room temperature evaporation of the hot-®lteredsolution gave thin pale-yellow crystal plates (m.p. 487.2±488.5 K).Crystal dataC10H14N5O4+C7H3N2O7ÿMr = 495.38Monoclinic, P21a = 15.297 (2) AÊb = 8.8543 (14) AÊc = 7.2805 (8) AÊ = 92.32 (1)V = 985.3 (2) AÊ 3Z = 2Dx = 1.670 Mg mÿ3Mo K radiationCell parameters from 25re¯ections = 12.5±16.9 = 0.14 mmÿ1T = 298 (2) KPlate, pale yellow0.40  0.35  0.03 mmData collectionRigaku AFC-7R diffractometer!±2 scansAbsorption correction:  scan(TEXSAN for Windows;Molecular StructureCorporation, 1999)Tmin = 0.945, Tmax = 0.9952690 measured re¯ections2406 independent re¯ections1873 re¯ections with I > 2(I)Rint = 0.018max = 27.5h = ÿ8! 19k = 0! 11l = ÿ9! 93 standard re¯ectionsfrequency: 150 minintensity decay: noneRe®nementRe®nement on F 2R[F 2 > 2(F 2)] = 0.037wR(F 2) = 0.122S = 0.882406 re¯ections317 parametersH-atom parameters not re®nedw = 1/[2(Fo2) + (0.1P)2+ 2.5029P]where P = (Fo2 + 2Fc2)/3(/)max = 0.003max = 0.20 e AÊÿ3min = ÿ0.24 e AÊ ÿ3Extinction correction: SHELXL97Extinction coef®cient: 0.013 (3)Table 1Hydrogen-bonding geometry (AÊ , ).DÐH  A DÐH H  A D  A DÐH  AO2ÐH2  O7B 0.92 1.61 2.438 (5) 147N12ÐH12  O7Ai 0.90 1.87 2.763 (4) 170N62ÐH62B  O7Bi 0.88 1.92 2.785 (5) 167O21ÐH21A  O7Aii 0.91 1.90 2.782 (4) 163O51ÐH51C  O5Bii 0.80 2.42 2.955 (5) 125O31ÐH31A  N72iii 0.93 1.93 2.785 (4) 152O51ÐH51C  O5Aiv 0.80 2.45 3.164 (5) 149N62ÐH62A  O21v 0.84 2.12 2.886 (4) 152C22ÐH22  O2vi 0.96 2.22 3.041 (5) 142C82ÐH82  O51 0.97 2.42 3.278 (5) 148Symmetry codes: (i) 1ÿ x; yÿ 12; 1ÿ z; (ii) x; y; 1 z; (iii) x; 1 y; z; (iv)2 ÿ x; 12 y; 2ÿ z; (v) x; y ÿ 1; z; (vi) 1ÿ x; 12 y; 1ÿ z.H atoms potentially involved in hydrogen-bonding interactionswere located by difference methods, while others were included in there®nement at calculated positions (CÐH = 0.96 AÊ ). All were treatedas riding, with Uiso(H) ®xed at 1.2Ueq(attached atom). The absolutecon®guration was not determined but was assumed from that knownfor the parent adenosine [C10(R), C20(R), C30(S) and C40(R)]. Friedelpairs were merged before re®nement.Data collection: MSC/AFC Diffractometer Control Software(Molecular Structure Corporation, 1999); cell re®nement: MSC/AFCorganic papersActa Cryst. (2004). E60, o1573±o1576 Graham Smith et al.  C10H14N5O4+C7H3N2O7ÿ o1575Figure 3The crystal packing of (I), viewed down the c axis, showing cation±anionhydrogen-bonding associations and partial inter-species ring super-imposition with ± stacking.Diffractometer Control Software; data reduction: TEXSAN forWindows (Molecular Structure Corporation, 1999); program(s) usedto solve structure: SIR92 (Altomare et al., 1994); program(s) used tore®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:PLATON for Windows (Spek, 1999); software used to preparematerial for publication: PLATON for Windows.The authors acknowledge ®nancial support from the Schoolof Physical and Chemical Sciences (Queensland University ofTechnology) and the School of Science, Grif®th University.ReferencesAiba, K., Hata, T., Sato, S. & Tamura, C. (1978). Acta Cryst. B34, 1259±1263.Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C.,Polidori, G. & Camalli, M. (1994). J. Appl. 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Adenosinium 3,5-dinitrosalicylate

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Wermuth, UD

Healy, PC

Acta Crystallographica Section E Crystallographic Communications

Acta Cryst. 19, 111–124.supplementary materialssupplementary materials sup-1 publCIF adenosinium 3,5-dinitrosalicylate

In the structure of (I), proton transfer to N1 of the purine ring occurs with subsequent formation of an R2 2(8) cyclic hydrogen-bonded dimer, similar to that formed in the common symmetric carboxylate–pyrimidine interaction

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Adenosinium 3,5-dinitrosalicylate

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