Abstract: | The reaction of CuBr2 with 1,10‐phen‐H2O (1,10‐phen = 1,10‐phenanthroline) gave two compounds: CuBr2(C12H8N2) and Cu3Br3(C12H8N2)2. Their structures have been characterized by single‐crystal X‐ray diffraction analysis, elemental analyses, thermogravimetric analyses (TGA) and measurement of variable temperature magnetic susceptibility. Crystal data for CuBr2(C12‐H8N2): monoclinic, space group P21/n, a = 0.9977(3) nm, b = 0.65138(14) nm, c = 1.8207(4) nm, β = 91.624(18)°, V = 1.1828(5) nm3, Z = 2. Crystal data for Cu3Br3(C12H8N2)2: monoclinic, space group C2/c, a = 1.00167(11) nm, b = 1.4523(4) nm, c = 1.6295(3) nm, β = 94.386(14)°, V = 2.3635(8) nm3, Z = 3. |