Preparation, crystal structures, EHT band calculations and physical properties of κ-(EDS-EDT-TTF)2[Ag2(CN)3] and α-(BETS)2Ag(CN)2

Preparation, crystal structures, EHT band calculations and physical properties of a semi-conducting κ-(EDS-EDT-TTF) 2 [Ag 2 (CN) 3 ] (1) and a new metallic-like species α-(BETS) 2 Ag(CN) 2 (2) are reported. κ-(EDS-EDT-TTF) 2 [Ag 2 (CN) 3 ] 1: M r =625.3, monoclinic space group P2 1 /c, a=15.157(9), b=8.732(2), c=13.51(2) A,β=90.94(3)°, V=1788 A 3 , Z=2, D c =2.324 g cm –3 , R=0.055 for 2572 reflections with F 2 ≥2σ(F 2 ). In this compound the organic molecules adopt the so-called κ type of packing. In the inorganic sublattice the [Ag 2 (CN) 3 ] – units form an infinite two-dimensional polymeric sheet. This compound shows a semi conducting behaviour, withσ 300 K =3.0×10 –4 S cm –1 and E a =120 meV. α-(BETS) 2 Ag(CN) 2 2: M r =1304.4, orthorhombic space group P2 1 2 1 2, a=9.5839(8), b=4.983(3), c=34.645(6), V=1654 A 3 , Z=2, D c =2.618 g cm –3 , R=0.057 for 1136 reflections with F 2 ≥2 σ(F 2 ). Its crystal structure consists of two-dimensional organic sheets separated by linear Ag(CN) 2 – anions. The organic molecules adopt the so-called α type of packing with a dihedral angle between two molecules belonging to two adjacent chains of ca. 78°. This compound shows metallic behaviour in the range 300-2 K, with σ 300 K =100 S cm –1 .