Ž . Inorganic Chemistry Communications 3 2000 345–349 www.elsevier.nlrlocaterinoche Unexpected guest-controlled formation of two-layered structure in w ž / x 4q supramolecular adduct of W S H O and cucurbituril 3 4 2 9 Danil N. Dybtsev, Olga A. Gerasko, Alexander V. Virovets, Maxim N. Sokolov, Vladimir P. Fedin ) Institute of Inorganic Chemistry, Russian Academy of Sciences, pr. LaÕrentyeÕa 3, NoÕosibirsk 630090, Russia Received 2 May 2000 Abstract w Ž . xwŽ .x4 Ž . A new supramolecular adduct WS HO Cl PyH ; C H N O Cl P 15.5H O 1 P 15.5H O was obtained when pyridine 3 4 2 8 36 36 24 12 4 2 2 w Ž . x 4q was added to the reaction mixture of cucurbituril and WS HO in 3 M HCl. X-ray crystal structure analysis of 1 P 15.5H O 3 4 2 9 2 revealed layered motive of the structure with two different types of cucurbituril molecules. A PyH q molecule is encapsulated in the w Ž . xwŽ cavity of each of the cucurbituril molecule. Under vacuum it loses 13.5 H O molecules and gives WS HO Cl PyH ; 2 3 4 2 8 .x4 Ž . C H N O Cl P 2H O 1 P 2H O . q 2000 Elsevier Science S.A. All rights reserved. 36 36 24 12 4 2 2 Keywords: Sulfide clusters; Tungsten; Cucurbituril; Supramolecular adducts; Inclusion compounds; Crystal structures 1. Introduction Ž . Cucurbituril C H N O is a macrocyclic cavitand 36 36 24 12 with D symmetry, having two identical carbonyl-fringed 6 h w x portals 1,2 . Kim and coworkers explored and structurally character- ized a number of adducts of cucurbituril and alkali metals ) Corresponding author. Tel.: q7-3832-344253; fax: q 7-3832-344489. Ž . E-mail address: cluster@che.nsk.su V.P. Fedin . w x with their quite unique structures and reactivities 3–6 . Recently rational design of supramolecular assemblies based on cucurbituril adducts of hydrogen-bonded molyb- denum and tungsten incomplete cuboidal and heterometal double cube aqua cluster complexes has been reported w x 7,8 . These results show a wide diversity of crystal struc- tures, affected by cluster metal, chalcogen and guest molecule accommodated in the cucurbituril cavity. In the most cases one-dimensional motives of these supramolec- ular assemblies were achieved due to shape and symmetry of the building blocks. The chains are formed via comple- mentary H-bond system between the carbonyl groups of cucurbituril and the six coordinated H O molecules which 2 are cis to the core m -Q atom of the cluster cation 3 w Ž .Ž .Ž . x 4q Ž M m -Q m -Q HO M s Mo, W; Q s S, 3 3 2 3 2 9 . Se as well as specific Van-der-Waals Q PPP Q interactions w x between the cluster molecules 7,8 . Understanding the factors that control the self-assembly process is still urgent. We have already described one-di- w Ž . x mensional supramolecular compound WS HO Cl - 3 4 2 7 2 Ž .4 C H N O Cl P 10H O obtained by reaction of cu- 36 36 24 12 2 2 w Ž . x 4q curbituril with WS HO in 3 M HCl aqueous 3 4 2 9 wx solution 7 . Here we report unexpected guest-controlled formation of two-layered structure in a supramolecular adduct obtained under similar experimental conditions but in the presence of pyridine. 1387-7003r00r$ - see front matter q 2000 Elsevier Science S.A. All rights reserved. Ž . PII: S1387-7003 00 00096-4