A new 3D-layered inorganic-organic hybrid [D/L-C6H13O2N-H](3)[(PO4)W12O36]center dot 4.5H(2)O (1), as racemic material in the solid phase, has been synthesized and fully characterized by elemental microanalysis, single crystal X-ray diffraction, and infrared, Raman, and proton nuclear magnetic resonance spectroscopes. The most unique structural feature of I is its three-dimensional inorganic infinite tunnel-like framework that results in weak van der Waals interactions along the a-axis. A weak interlayer interaction between the titled layers provides a desirable condition to explore its potential as a host in a host-guest complex. The racemization has been observed in the crystal structure with the centric space group (P2(1)/c). The latter consists of alpha-[(PO4)W12O36](3-) and [D/L-C6H13O2N-H](+) moieties with water molecules linked together by a complex network of hydrogen bond interactions. (c) 2009 Published by Elsevier Ltd.