[K36(μ6‐Cl)2(H2O)11(MeOH)32][SnSe4][Co4(μ4‐Se)(SnSe4)4]3: Synthesis and Crystal Structure of a Novel Compound Containing Ternary [Co4(μ4‐Se)(SnSe4)4]10— Anions and a Novel [(μ6‐Cl)2K9]7+ Coordination Aggregate

Formation of the novel compound [K36(μ6‐Cl)2(H2O)11(MeOH)32][SnSe4][Co4(μ4‐Se)(SnSe4)4]3 (2) was achieved by variation of the crystallization conditions that recently enabled synthesis of the quaternary compound [K22(H2O)17(MeOH)8][SnSe4]3[Co4(μ4‐Se)(SnSe4)4] (1) by reaction of K4[SnSe4] with [Co(en)3]Cl3 in a methanol/water mixture (19:1). The crystal structure of 2, which was determined by means of single crystal X‐ray diffraction (orthorhombic space group Pbcm; lattice dimensions at 200 K: a = 18.7122(8), b = 20.9653(9), c = 57.340(3)Å, V = 22494.9(17)Å3; R1 [I > 2σ(I)] = 0.0674; wR2 = 0.1271) differs from 1 in that the [Co4(μ4‐Se)(SnSe)4]10— anions are embedded in an even more complex counterion aggregation; the latter contains solvated K+ cations, additional [SnSe4]4— groups and, in contrast to 1, Cl— anions. As a part of the counterion assembly, the Cl— and some of the K+ ions are arranged in a previously unknown [(μ6‐Cl)2K9]7+ coordination aggregate, formed by two face‐sharing [(μ6‐Cl)K6] octahedra.