A novel tetranuclear μ 3 ,η 3 -HPO42- Cu(II) complex with a new coordination mode of a hydrogenphosphato bridge, [Cu 4 (di-2-pyridylamine) 4 (μ 3 ,η 3 -HPO 4 ) 2 (H 2 O) 2 (NO 3 ) 2 ](NO 3 ) 2 (H 2 O) 2 has been synthesised and characterised structurally, spectroscopically and magnetically. The geometry around the Cu(II) ions is distorted square pyramidal for Cu(1) and an intermediate between square pyramidal and trigonal pyramidal. The magnetic susceptibility measurements have been fit for a weak antiferromagnetic interaction of J=−10.3(1) cm −1 between outer Cu ions and J=−5.3(2) cm −1 between inner Cu atoms.