The Layered Coordination Polymer Bi(SCN) 3 ·1/2H 2 O

Yellow crystals of Bi(SCN) 3 ·1/2H 2 O are obtained by reacting (BiO) 2 CO 3 and HSCN in aqueous solution. X‐ray diffraction on a single‐crystal revealed a triclinic lattice (space group P $\rm \overline1$ ) with a = 843.6(2) pm, b = 920.4 (2) pm, c = 1210.7(2) pm, α = 109.16(3) °, β = 109.06(3) °, γ = 90.22(3) °, V = 832.8(3)·10 6  pm 3 , and Z = 4. All thiocyanate anions bind with both ends to different cations. The coordination network expands in plane layers parallel (1 $\rm\overline1$ 0). The water molecule coordinates one of the two independent Bi 3+ cations. Dehydration sets in at 100 °C, followed by stepwise thermal decomposition to Bi 2 S 3 .