Description:
<jats:title>Abstract</jats:title>
<jats:p>Colorless powders of orthorhombic Ag[N(CN)<jats:sub>2</jats:sub>] were synthesized by blending aqueous solutions Ag[NO<jats:sub>3</jats:sub>] with stoichiometric amounts of Na[N(CN)<jats:sub>2</jats:sub>] equally dissolved in water. Single crystals of both modifications of Ag[N(CN)<jats:sub>2</jats:sub>] could be obtained by recrystallizing the powder with aqueous ammonia. Non-isothermal evaporation of the solvent at room temperature within a few hours yielded the orthorhombic modification as the main product crystallizing in the space group <jats:italic>Pnma</jats:italic> (no. 62) with the unit-cell parameters <jats:italic>a</jats:italic> = 1612.45(12), <jats:italic>b</jats:italic> = 361.58(3) and <jats:italic>c</jats:italic> = 599.02(4) pm (<jats:italic>Z</jats:italic> = 4). Upon evaporating the solvent much more slowly, isothermally within a few days, mainly thin hexagonal platelets of the trigonal modification of Ag[N(CN)<jats:sub>2</jats:sub>] were obtained, crystallizing in the space group <jats:italic>P</jats:italic>3<jats:sub>1</jats:sub>21 (no. 152) with the lattice constants <jats:italic>a</jats:italic> = 359.86(3) and <jats:italic>c</jats:italic> = 2285.91(17) pm (<jats:italic>Z</jats:italic> = 3). Both results corroborate earlier structure determinations, but show higher precision. The vibrational spectra confirm the presence of the dicyanamide anion [N(CN)<jats:sub>2</jats:sub>]<jats:sup>−</jats:sup>, but exhibit slight differences to literature data. Differential scanning calorimetry/thermogravimetry (DSC/TG) analyses were performed to further characterize the two modifications.</jats:p>