Unusual template center dot center dot center dot template interactions in organically templated zincophosphate networks: {apyH[Zn(HPO4)(H2PO4)]center dot H2O }(n) and [meenH(2) [Zn-5 (PO4)(4)]}(n) (apyH=2-aminopyridinium and meenH(2) = monoethanol-ethylenediammonium)

Abstract

The solution-mediated syntheses, single crystal structures and some physical data for [apyH[Zn(HPO4)(H2PO4)]center dot H2O}(n) (I) and {meenH(2)[Zn-5(PO4)(4)]}(n) (II) are reported. Compound (1), templated by mono-protonated 2-aminopyridine, apyH, contains infinite 4-ring chains of vertex-sharing ZnO4 and H2PO4/HPO4 groups with the protonated organic moiety acting as a template and interacting with the chains by way of N-H center dot center dot center dot O hydrogen bonds. Intra-chain and inter-chain P-OH center dot center dot center dot O hydrogen bonds and a distinctive template center dot center dot center dot template interaction in the form of pi center dot center dot center dot pi stacking help to establish the crystal packing. In (II), the polyhedral ZnO4 and PO4 building units link together to form a distinctive three-dimensional framework containing squares of four ZnO4 units and intersecting 8 ring channels. The anionic framework encapsulates the doubly-protonated monoethanol-ethylenediamine templating meenH(2) cations which interact with each other by way of N-H center dot center dot center dot O hydrogen bonds as well as forming N-H center dot center dot center dot O links to framework O atoms. Similarities and differences to other zinc phosphates are briefly discussed for the title compounds. Compound (1): C5H12N2O9P2Zn, M-r = 371.48, monoclinic, P2(1)/n (No. 14), a = 11.5161(7) angstrom, b = 8.0218(3) angstrom, c = 13.2213(9) angstrom, 6 = 99.649(5)degrees, V = 1204.10(12) angstrom(3), Z = 4, R(F) = 0.031, w R(F-2) = 0.072. Compound (II): C4H14N2O17P5Zn5, M-r = 812.90, orthorhombic, P2(1)2(1)2(1) (No. 19), a = 7.497(4) angstrom, b = 13.154(2) angstrom, c = 18.206(4) angstrom, V = 1795.4(11) angstrom(3), Z = 4, R(F) = 0.033, w R(F-2) = 0.069. (c) 2005 Elsevier SAS. All rights reserved.