The structure of Cu 2(OH) 2(C 8H 4O 4) has been determined by ab initio XRPD methods from synchrotron data. The compound crystallizes in P-1 space group, a = 10.1423 ( 4 ) Å , b = 6.3388 ( 2 ) Å , c = 3.4841 ( 1 ) Å , α = 99.170 ( 2 ) ° , β = 96.567 ( 2 ) ° , γ = 98.760 ( 3 ) ° , D x = 2.497 g cm −3 . The structure has been fully refined by the Rietveld method down to R p = 0.077 for 9651 observed data points (513 reflections of which 193 are independent). The structure consists of layered hydroxides Cu(OH) 2 intercalated by terephthalate anions, at the interlayer space forming a 3D framework similar to Co(II)-based compound. The apticity of the tp anion and the octahedral coordination of the metal ions are similar in both compounds and can be formulated as M 2( μ 3-OH) 2( μ 6- η 1, η 2, η 1, η 2-tp) with M = Cu and Co. Although Cu(II)-based structure is very similar to the monoclinic ( C 2 / m ) Co(II)-based analogue, the former is completely ordered in contrast with the later which is disordered. The lower symmetry in Cu(II)-based compound due to the Jahn–Teller effects inducing an elongation of the octahedrons CuO 6 with four short distances of about 2.0 Å and two long distances Cu O up to 2.8 Å is also observed to be different from Co(II)-based compound. Whereas the Co(II) derivative exhibits noncollinear antiferromagnetic coupling between the ferrimagnetic hydroxide layers, the magnetic behavior of the copper(II) analogue indicate a ferromagnetic coupling through the terephthalate bridge between ferromagnetic sheets with in-plane interaction J = + 5.5 K .