New organic-inorganic frameworks incorporating iso- and heteropolymolybdate units and a 3,3 ',5,5 '-tetramethyl-4,4 '-bi-1H-pyrazole-2,2 '-diium multiple hydrogen-bond donor

作者：Lukashuk Liliana V; Lysenko Andrey B; Krautscheid Harald; Domasevitch Konstantin V^*

来源：Acta Crystallographica Section C-Crystal Structure Communications, 2011, 67: M378-M383.

DOI：10.1107/S0108270111047159

Poly[bis(3,3',5,5'-tetramethyl-4,4'-bi-1H-pyrazole-2,2'-diium) gamma-octamolybdate(VI) dihydrate], {(C10H16N4)(2)[Mo8O26]center dot-2H(2)O}(n), (I), and bis(3,3',5,5'-tetramethyl-4,4'-bi-1H-pyrazole-2,2'-diium) alpha-dodecamolybdo(VI) silicate tetrahydrate, (C10H16N4)(2)[SiMo12O40]center dot 4H(2)O, (II), display intense hydrogen bonding between the cationic pyrazolium species and the metal oxide anions. In (I), the asymmetric unit contains half a centrosymmetric gamma-type [Mo8O26](4-) anion, which produces a one-dimensional polymeric chain by corner-sharing, one cation and one water molecule. Three-centre bonding with 3,3',5,5'-tetramethyl-4,4'-bi-1H-pyrazole-2,2'-diium, denoted [H(2)Me(4)bpz](2+) [N center dot center dot center dot O = 2.770 (4)-3.146 (4) angstrom], generates two-dimensional layers that are further linked by hydrogen bonds involving water molecules [O center dot center dot center dot O = 2.902 (4) and 3.010 (4) angstrom]. In (II), each of the four independent [H(2)Me(4)bpz](2+) cations lies across a twofold axis. They link layers of [SiMo12O40](4-) anions into a three-dimensional framework, and the preferred sites for pyrazolium/anion hydrogen bonding are the terminal oxide atoms [N center dot center dot center dot O = 2.866 (6)-2.999 (6) angstrom], while anion/aqua interactions occur preferentially via mu(2)-O sites [O center dot center dot center dot O = 2.910 (6)-3.151 (6) angstrom].

• 出版日期2011-12