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The crystal structure of Cs 3 Sr[Ag 2 (SCN) 7 ] was determined from single crystal X-ray diffraction data (tetragonal,  I [unk]2 m ,  a  = 11.083(2) Å,  c  = 20.117(3) Å,  Z  = 4,  D x   = 2.98 Mgm −3 ,  μ (Mo K α  ) = 8.55 mm −1 ,  T  = 293 K,  R  = 0.040 for 1183 unique reflections). The main structural feature is the binuclear  μ -thiocyanato(S)-bis[trithiocyanato(S)-argentate(I)]-complex [Ag 2 (SCN) 7 ] 5− , where the silver atoms are tetrahedral coordinated by the sulphur atoms of the linear SCN groups. Cs 3 Ba[Ag 2 (SCN) 7 ] [ a  = 11.210(9) Å,  c  = 20.30(1) Å] is isotypic with the strontium compound. Large single crystals of optical quality of Cs 3 Sr[Ag 2 (SCN) 7 ] and Cs 3 Ba[Ag 2 (SCN) 7 ] were grown from stoichiometric aqueous solutions at 28°C. The tensor of linear electrostriction [ d ijk  ] and the unclamped electro-optic tensor [ r ijk  σ  ] were determined for both compounds at room temperature and  λ  = 633 nm. The value of the electro-optic constants is only one third of the corresponding constants of KH 2 PO 4 (KDP). The maximum value of the electrostrictive coefficients is six times that of  α -quartz. A comparison with the isotypic copper compound Cs 3 Sr[Cu 2 (SCN) 7 ] shows that the exchange of Ag for Cu within the binuclear complex causes a strong increase in both effects.

zeitschrift für kristallographie

Crystal growth, crystal structure, optical, electro-optic and electrostrictive properties of the complex silver thiocyanates Cs 3 Sr[Ag 2 (SCN) 7 ] and Cs 3 Ba[Ag 2 (SCN) 7 ]