The reaction of anhydrous CuCl 2 with HCl and 2-amino-5-iodopyridine in 1-propanol resulted in two polymorphs of (5-IAP) 2 [CuCl 4 ] [5-IAP ¼ 2-amino-5-iodopyridinium], one as red rods (1) and one as orange prisms (2). The two polymorphs have been characterized by single crystal x-ray diffraction and variable temperature magnetic susceptibility. Crystal data: triclinic, P-1, F(000) ¼ 606, MoK ( ¼ 0.71073 Å ): for (1): a ¼ 9.248 (6), b ¼ 10.202(7), c ¼ 10.368(7) Å , ¼ 102.451(9), ¼ 96.662(8), ¼ 96.725(8) , V ¼ 938.4(11) Å 3 , Z ¼ 2, D calc ¼ 2.291 Mg/m 3 , ¼ 5.020 mm À1 , R ¼ 0.0392 for [|I| ! 2 (I)]. For (2): a ¼ 8.966(2), b ¼ 10.755(2), c ¼ 11.359(2) Å , ¼ 89.63(3), ¼ 68.04(3), ¼ 69.07(3) , V ¼ 938.6(3) Å 3 , Z ¼ 2, D calc ¼ 2.291 Mg/m 3 , ¼ 5.019 mm À1 , R ¼ 0.0217 for [|I| ! 2 (I)]. The crystal packing for both polymorphs suggests that their magnetic behavior should be that of weakly interacting alternating linear chains. Temperature dependent susceptibility measurements yield: for 1, C ¼ 0.43, g ¼ 2.14, ¼ À 1.98; for 2, C ¼ 0.45, g ¼ 2.19, ¼ À 4.15.