The organotin(IV) coordination polymer [(Me3Sn)4Fe(CN)6.2H2O.C4H8O2].infin.: a three-dimensional host-guest network involving "cascade type" guests

Abstract

The Organotin(IV) Coordination Polymer (( ß38 )4 ß(€ )6•2 2 •€4 802)": A Three-Dimensional Host-Guest Network Involving "Cascade-Type" Guests Macroor polycyclic Lewis base receptors1 require an appropriate disposition of Lewis acidic centers over the respective organic rings. Frequently, after the anchoring of at least two metal ions to selected N and/or 0 atoms of the ring as "primary guests",

Unprecedented N-E Bond Cleavage (E=Sn, Pb) by R4N+ Ions (R=nBu, nPr): Formation, Architecture, and Multinuclear Magnetic Resonance Spectroscopy of Novel Supramolecular [(R4N)(Me3E)2M(CN)6⋅H2O] Assemblies (M=Fe, Co)

“…The corresponding O´´´N distances (Table 4) are considerably shorter than the shortest O´´´N contacts which have been observed, for example in 4 (312.2 pm [10] ) and in 5 (305.2 and 297.2 pm [11] ). The OÀH´´´N cyanide bridges with O´´´N distances ranging between 280 and 295 pm are, however, wellknown for numerous salt hydrates, for example the dihydrated cyanoelpasolites [(NMe 4 ) 2 LiM(CN) 6´2 H 2 O] (M Fe,Co [13] ).…”

Spontaneously Organizing Metal Connectors as Supramolecular Structure Directors of Two‐ and Three‐Dimensional Organometallic Assemblies

“…Most unexpectedly, excellent single crystals of 11 were also obtained in low yields during attempts to grow crystals of the coordination polymer [(Me 3 Sn) 6 {Fe II 2 (m-bpy)(CN) 10 }] [9] from very slowly warmed stacks of initially frozen solutions of Me 3 SnCl and K 6 [Fe 2 (mbpy)(CN) 10 ], respectively, separated by layers of pure ice (route 2). Single crystals of 9 and 10 resulted after one to three days when samples of 1 a or 1 (which are sparingly soluble in pure H 2 O) had been completely dissolved in mixtures of H 2 O (excess), L, and (traces of) MeCN (route 3).…”

“…The five-atom metal connectors, or spacers, -CN 3 Sn 2 NC-(type I) usually result by rapid self-assembly when dissolved [M(CN) m ] nÀ ions meet hydrated Me 3 Sn ions. The somewhat modified host ± guest system [(Ph 3 Sn) 3 Fe III (CN) 6 [5] is, on the other hand, a heteroleptic congener of 1 and 1 a (M Fe), [2b] in that its six-connected net contains, in the ratio 2:1, both spacer I and the seven-atom spacer II: -CN ¥¥ HO(H) 3 Sn 2 NC-. Another long known [6] assembly with a related heteroleptic framework structure is the guest-free system [(Me 3 Sn) 4 Fe II (CN) 6 3 )NC}] (diox dioxane) (5) wherein both spacer I and the notably more expanded spacer III: -CNSnO(H)H ¥¥ L ¥¥ HO(H)SnNC-(with L diox) span a strongly elongated six-connected framework.…”

“…The somewhat modified host ± guest system [(Ph 3 Sn) 3 Fe III (CN) 6 [5] is, on the other hand, a heteroleptic congener of 1 and 1 a (M Fe), [2b] in that its six-connected net contains, in the ratio 2:1, both spacer I and the seven-atom spacer II: -CN ¥¥ HO(H) 3 Sn 2 NC-. Another long known [6] assembly with a related heteroleptic framework structure is the guest-free system [(Me 3 Sn) 4 Fe II (CN) 6 3 )NC}] (diox dioxane) (5) wherein both spacer I and the notably more expanded spacer III: -CNSnO(H)H ¥¥ L ¥¥ HO(H)SnNC-(with L diox) span a strongly elongated six-connected framework. [7] In view of the spontaneous formation of 4 and 5 from dissolved R 3 Sn and [Fe(CN) 6 ] 3À /[Fe(CN) 6 ] 4À ions in the presence of acetonitrile and dioxane, respectively, the spacers II and III obviously owe their existence to self-assembly, too.…”

“…[(Me 3 Sn) 4 Mo IV (CN) 8 4 Mo IV (C-N) 8 4 Fe II (CN) 6 ¥ H 2 O ¥ 3/2 bpy] (11), and [(Me 3 Sn) 4 Ru II (CN) 6 ¥ 2 H 2 O ¥ 3/ 2 cpy] (12) are presented. H 2 O molecules are usually coordinated to tin atoms and involved in two significant O À H ¥¥¥ N hydrogen bonds, wherein the nitrogen atoms belong either to bpy (bpe, cpy) molecules or to M-coordinated cyanide ligands.…”