Effect of outer sphere anions on the structure and color of nitrosylpentaamminechromium complex

Three kinds of crystalline compounds containing the nitrosylpentaamminechromium complexes [Cr(NO)(NH3)5]2+(A) were obtained: chloride ACl2 (red–orange), chloride perchlorate ACl(ClO4) (brown), and perchlorate A(ClO4)2 (green). The cause of the color change of the complex A with the change of outer sphere anions was sought using X-ray structural data of ACl2, ACl(ClO4), and A(ClO4)2. Crystal data: ACl2, orthorhombic, space group Cmcm, a=10.0236 (9) Å, b=9.098 (3) Å, c=10.357(1) Å, V=944.5 (5) Å3, Z=4; ACl(ClO4), tetragonal, space group P4/nmm, a=7.6986 (8) Å, c=9.9566(8) Å, V=590.1 (1) Å3,Z=2; A(ClO4)2, orthorhombic, space group Pnma, a=15.760 (2) Å, b=11.480(2) Å, c=7.920 (2) Å, V=1432.9 (4) Å3, Z=4. The complex cation in ACl2 has a distorted octahedral structure with a linear CrNO moiety. The short CrN (nitrosyl) distance of 1.692 (7) Å indicates the presence of multiple bonding between the chromium atom and the nitrogen atom in the nitrosyl group. The interatomic distances and angles within the complex cations hardly change with the change of the counter anions, while the distances between the complex cations in each crystal increase in the order ACl2