Polyhedron 18 (1999) 2061–2067 Synthesis and characterization of binuclear and polymeric five-coordinate copper(II) complexes derived from 3,39,30-triaminotripropylamine (trpn) Crystal structure of [Cu(trpn)(N )]ClO ( I ) and 3 4 [Cu (trpn)(tren)(NO )(H O)](ClO ) ( II ) 2 2 2 4 3 a, b b ,1 c * Salah S. Massoud , Franz A. Mautner , Morsy A.M. Abu-Youssef , Nadia M. Shuaib a Department of Chemistry, Faculty of Science, Alexandria University, P .O. Box 426, Ibrahimia, Alexandria 21321, Egypt b ¨ ¨ Institut f ur Physikalische und Theoretische Chemie, Technische Universitat Graz, A-8010 Graz, Austria c Department of Chemistry, Faculty of Science, Kuwait University, P .O. Box 5969, Safat 13060, Kuwait Received 5 January 1999; accepted 29 March 1999 Abstract The synthesis and characterization of five-coordinate copper(II) complexes derived from 3,39,30-triaminotripropylamine (trpn) are described. The X-ray diffraction studies have established the structures [Cu(trpn)(N )]ClO (I) and [Cu (trpn)(tren)(NO )(H O)](ClO ) 3 4 2 2 2 4 3 2 ( II). Compound (I) consists of a polymeric cation chain and ClO counter ions. The coordination geometry of the Cu(II) centers may be 4 described as distorted square pyramidal (SP) with the azido group at the apical site and three nitrogen donors of the trpn molecule occupy the basal sites. The CuN5 chromophore is completed by a bridging aminopropyl group of neighboring trpn ligand. Compound (II) is a dinuclear complex cation with two different cation geometries in the unit cell. The geometry of the Cu(II) binding tren ligand is close to trigonal bipyramidal (TBP), with the basal and apical sites are occupied by the four nitrogen atoms of the tren ligand. The fifth coordination site is bridged to one of the aminopropyl arms of the trpn ligand. The geometry of the second Cu(II) center may be described as close to distorted SP, where the trpn ligand is binding the Cu(II) ion via the two primary aminopropyl groups and the tertiary nitrogen. The remaining two sites are occupied by oxygen atoms of a water molecule and nitrite ion. The intramolecular Cu . . . Cu distance in I and ˚ ˚ II ranges from 7.55 A to 7.94 A. The visible spectra of the complexes in DMSO are consistent with the X-ray results found for I and II and show a greater tendency toward SP geometry.  1999 Elsevier Science Ltd. All rights reserved. Keywords: Copper(II)-(3,39,30-triaminotripropylamine) complexes; Copper(II)-(2,29,20-triaminotriethylamine) complexes; Azido complexes; Nitrito complexes; Dinuclear copper(II) complexes; Polymeric copper(II) complexes; Crystal structure; Tripod amines 1. Introduction meric copper(II) complexes bridged by aliphatic chain amines are quite rare [15,16,22,23], and even very few Numerous five- and six-coordinate dinuclear copper(II) examples with the same coordination mode were found for complexes derived from macrocyclic ligands linked by other metal complexes such as Na [(VO) (TTHA)]– 2 2 alkyl chains and from polydentate ligands with pendant 10H O [24,25], [Mn (tren) (O) ](CF SO ) [26], 2 2 2 2 3 3 3 coordinating arms have been recently described [1–4]. [Ni (tren) (trien)](ClO ) [22], [Cr (OH) (ac)(trpn)]- 2 2 4 4 2 2 Bridging through oxo, hydroxo, carboxylato and acetato (ClO ) [27] and [Cr (tren) (OH) ]Br –2H O [28]. Thus, 4 2 2 2 2 4 2 groups has also been reported [5–10], and some of these it came to our attention that most of the binuclear metal compounds have served as models for a variety of bio- complexes bridged with aliphatic amines were obtained logical reactions [11–14]. The bridge formation between with tripodal amines [22,23,25–28] and it seemed possible the Cu(II) centers was promoted by the presence of to have the same coordination mode by using 3,39,30- potential donor atoms such as oxygen [5–10,15–17] and triaminotripropylamine (trpn5N(CH CH CH NH ) ) 2 2 2 2 3 nitrogen [18–21]. On the other hand, binuclear and poly- with Cu(II) salts. The tripodal nature of the amine ligand enforces the formation of metal complexes of cis-geometry [29,30]. *Corresponding author. Present address: Department of Chemistry and The stereochemistry of five-coordinate copper(II) com- Biochemistry, Ohio University, Athens, OH 45701-2979, USA. 1 On leave from Alexandria University. plexes ranges between square pyramidal (SP) and trigonal 0277-5387 / 99 / $ – see front matter  1999 Elsevier Science Ltd. All rights reserved. PII: S0277-5387(99)00080-7