Journal of Solid State Chemistry 177 (2004) 1896–1904 A family of three-dimensional porous coordination polymers with general formula (Kat) 2 [{M(H 2 O) n } 3 {Re 6 Q 8 (CN) 6 } 2 ]  xH 2 O (Q=S, Se; n=1.5, 2) $ N.G. Naumov, a, * A.V. Virovets, a S.B. Artemkina, a D.Yu. Naumov, a J.A.K. Howard, b and V.E. Fedorov a a Laboratory of Chemistry of Superconductors, Russian Academy of Sciences, Nikolaev Institute of Inorganic Chemistry, SB RAS, Siberian Branch 3, Ak. Lavrentiev Avenue, Novosibirsk 630090, Russia b Department of Chemistry, University of Duhram, Duhram, UK Received 3 September 2003; received in revised form 24 December 2003; accepted 14 January 2004 Abstract The X-ray crystal structures of a series of new compounds (H 3 O) 2 [{Mn(H 2 O) 1.5 } 3 {Re 6 Se 8 (CN) 6 } 2 ]  19H 2 O(1), (Me 4 N) 2 [{Co (H 2 O) 1.5 } 3 {Re 6 S 8 (CN) 6 } 2 ]  13H 2 O(2), (Me 4 N) 2 [{Co(H 2 O) 1.5 } 3 {Re 6 Se 8 (CN) 6 } 2 ]  3H 2 O(3), ðEt 4 NÞ 2 ½fMnðH 2 OÞ 2 g 3 fRe 6 Se 8 ðCNÞ 6 g 2  6:5H 2 O(4), (Et 4 N) 2 [{Ni(H 2 O) 2 } 3 {Re 6 S 8 (CN) 6 } 2 ]  6.5H 2 O(5), and (Et 4 N) 2 [{Co(H 2 O) 2 } 3 {Re 6 S 8 (CN) 6 } 2 ]  10H 2 O(6) are reported. All six compounds are isostructural crystallizing in cubic Im % 3m space group with four formulae per unit cell. For compounds 1, 3–5 the following parameters were found: (1) a ¼ 19:857ð2Þ A ˚ , R1 ¼ 0:0283; (3 at 150K) a ¼ 19:634ð1Þ A ˚ , R1 ¼ 0:0572; (4) a ¼ 20:060ð2Þ A ˚ , R1=0.0288; (5) a=19.697(2)A ˚ , R1 ¼ 0:0224: The structures consist three-dimensional cyano-bridged framework formed by cyano cluster anions [Re 6 Q 8 (CN) 6 ] 4 , Q ¼ S; Se and transition metal cations, M 2+ =Mn 2+ , Co 2+ , Ni 2+ . Water molecules and large organic cations Me 4 N + and Et 4 N + are included in cavities of this framework. Porosity of the framework, its ability to accommodate different cations and water molecules by little changes in the structure, as well as distortion of coordination framework under loss of water of crystallization is discussed. r 2004 Elsevier Inc. All rights reserved. Keywords: Rhenium; Octahedral cluster; Cyanide; Coordination framework; Transition metals 1. Introduction In recent years there has been a great deal of interest in the use of molecular species as precursors for the formation of organic and organic–inorganic materials [1–4]. Transition metal cyanides were widely used for these purposes. Ambidentate nature of CN  and stability of cyanometallate complexes make transition metal cyanides convenient building blocks, while wide variety of coordination numbers (from two in [Ag(CN) 2 ]  to eight in [Mo(CN) 8 ] 4 ) and of arrange- ment of metal centers favor to formation a diversity of coordination arrays (see e.g., reviews [5–7]). The most famous examples of these compounds are Prussian Blue and their analogues [8–10], and Hoffman clathrates [11– 14]. 3D framework of Prussian Blue type compounds contains large cavities enough for including water molecules, large inorganic cations (up to Cs + ) and small neutral organic molecules. Zeolitic and ion exchange properties [15–17] as well as magnetic proper- ties [18–20] of above compounds are well known. Discovery of octahedral rhenium chalcocyanide com- plexes [Re 6 Q 8 (CN) 6 ] 4 (Q=S, Se, Te) (Fig. 1) 5–8 years ago [21–24] have excited interest to them as to potential building blocks which are able to coordinate to metal cations forming extended cyano-bridged fragments ?2NC2Re 6 Q 8 2CN2M2? [25]. Since that time a numerous contributions from Long’s group [26–28], Kim’s [29–31] and ours [32–36], devoted to synthesis, structural studies and some properties of such com- pounds have appeared. Topological similarity of the ARTICLE IN PRESS $ Supplementary data associated with this article can be found, in the online version, at doi:10.1016/j.jssc.2004.01.001 *Corresponding author. Fax: +7-3832-344489. E-mail address: naumov@che.nsk.su (N.G. Naumov). 0022-4596/$-see front matter r 2004 Elsevier Inc. All rights reserved. doi:10.1016/j.jssc.2004.01.001