Synthesis and structure of Cu 3 PO 4 [1,2,4-triazole] 2 OH with a hybrid layered structure: A new organically templated copper (II) hydroxyphosphate Bernard Malaman a, * , Radia Bagtache b, c , Kaîssa Abdmeziem c a Institut Jean Lamour, CNRS (UMR 7198) e Nancy Université, B.P. 70239, 54506 Vandoeuvre-les-Nancy Cedex, France b Centre de Recherches et Analyses Physicochimiques BP n  248, 16004 RP Alger, Algeria c Laboratoire d’Electrochimie-Corrosion, Métallurgie et Chimie Minérale, Faculté de Chimie, U S T Houari Boumediène, BP 32 El Alia, Bab-Ezzouar,16111 Alger, Algeria article info Article history: Received 22 January 2010 Received in revised form 23 March 2010 Accepted 31 March 2010 Available online 8 April 2010 Keywords: Copper hydroxyphosphate Hydrothermal synthesis Hybrid lamellar Layered material 1,2,4-Triazole Crystal structure abstract A new layered copper hydroxyphosphate Cu 3 PO 4 (1,2,4-triazole) 2 OH was synthesized by the mild hydrothermal route and the crystal structure was solved by the single crystal X-ray diffraction method. This compound crystallizes in the monoclinic space group P2 1 /a with: a ¼ 10.1456(5)  A, b ¼ 7.8756(4)  A, c ¼ 12.9008(6)  A, b ¼ 111.64(2)  ,V ¼ 960.86(8)  A 3 , Z ¼ 4, D x ¼ 3.033 g cm 3 . The Cu(II) atoms are embedded in deformed square-pyramidal (Cu1 and Cu3) or octahedral (Cu2) sites made of N and O (or OH) atoms. Both Cu1 and Cu2 polyhedra form dimers connected one to each other, via OH groups, in ribbons which built a bidimensional (001) layer through PO 4 connections. The Cu3 polyhedra built a (001) double-sheet layer through triazol connections. These layers are bridged by triazole and PO 4 groups along the c-direction yielding a lamellar arrangement. Its structural analysis evidences a two- dimensional character for this copper hybrid material which could begin a new series of MOF compounds. Ó 2010 Elsevier Masson SAS. All rights reserved. 1. Introduction Following the first discovery of microporous alumi- nophosphates in 1982 [1], a large number of open framework metal phosphates have been hydrothermally synthesized, in the presence of an organic template. The elimination of the organic molecule moieties in these compounds may lead to new inorganic micro- porous materials which could not be obtained otherwise. The rational design and synthesis of these metal oxide based organ- iceinorganic hybrid materials with two or three-dimensional structure are receiving increasing interest in solid-state chemistry owing to their fascinating properties and great potential applica- tions in many fields such as catalysis, material science, electrical conductivity, magnetism, photochemistry, biology and medicine. Amongst the many structures known to-date, those incorpo- rating d-block transition metal constitute an important group. In recent years, a variety of new compounds with fascinating struc- tural architectures ranging from clusters, chains, layers and open frameworks have been prepared in the presence of organic ‘templates’. Such examples include: zinc [2], nickel [3], iron [4], manganese [5], titanium [6], vanadium [7], copper [8], molybdenum [9], cobalt [10] and tin [11]. A lot of bimetallic phases were also reported: cobaltemolybdenum [12], cobaltetungsten [13], cobaltemanganese [14], molybdenumemanganese [15], molybdenumezinc [16]. 1,2,4-Triazole and its derivatives are interesting bridging ligands. Various coordination compounds with this group of ligands coordinated to transition metal ions have been described [8,17e19]. In this paper, we report on the hydrothermal synthesis and crystal structure determination of a novel copper (II) hydroxy- phosphate with the following formula: Cu 3 PO 4 [C 2 N 3 H 2 ] 2 OH for which single crystals have been obtained. 2. Experimental 2.1. Hydrothermal synthesis and chemical analysis All chemicals purchased were of reagent grade and used without further purification. The title compound was prepared hydrothermally, under autogenous pressure. In a typical synthesis, 0.51 g (2.98 mmol) of CuCl 2 $2H 2 O was first dissolved in 20 mL of H 2 O. 0.2 g (4.76 mmol) of NaF was then added, followed by 0.27 g (3.91 mmol) of 1,2,4-triazole and 0.72 g of phosphoric acid (H 3 PO 4 85 wt%) under constant stirring. Finally, a KOH solution (0.98 g (17.5 mmol) in 2.75 mL H 2 O) was poured to the above and the * Corresponding author. Tel.: þ33 (0) 383684671; fax: þ33 (0) 383684171. E-mail address: Bernard.Malaman@lcsm.uhp-nancy.fr (B. Malaman). Contents lists available at ScienceDirect Solid State Sciences journal homepage: www.elsevier.com/locate/ssscie 1293-2558/$ e see front matter Ó 2010 Elsevier Masson SAS. All rights reserved. doi:10.1016/j.solidstatesciences.2010.03.020 Solid State Sciences 12 (2010) 1178e1182