[K₃₆(<i>μ</i>₆‐Cl)₂(H₂O)₁₁(MeOH)₃₂][SnSe₄][Co₄(<i>μ</i>₄‐Se)(SnSe₄)₄]₃: Synthesis and Crystal Structure of a Novel Compound Containing Ternary [Co₄(<i>μ</i>₄‐Se)(SnSe₄)₄]^10— Anions and a Novel [(<i>μ</i>₆‐Cl)₂K₉]⁷⁺ Coordination Aggregate

Abstract

Abstract Formation of the novel compound [K 36 ( μ 6 ‐Cl) 2 (H 2 O) 11 (MeOH) 32 ][SnSe 4 ][Co 4 ( μ 4 ‐Se)(SnSe 4 ) 4 ] 3 ( 2 ) was achieved by variation of the crystallization conditions that recently enabled synthesis of the quaternary compound [K 22 (H 2 O) 17 (MeOH) 8 ][SnSe 4 ] 3 [Co 4 ( μ 4 ‐Se)(SnSe 4 ) 4 ] ( 1 ) by reaction of K 4 [SnSe 4 ] with [Co( en ) 3 ]Cl 3 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)Å 3 ; R 1 [ I &gt; 2 σ ( I )] = 0.0674; wR 2 = 0.1271) differs from 1 in that the [Co 4 ( μ 4 ‐Se)(SnSe) 4 ] 10— anions are embedded in an even more complex counterion aggregation; the latter contains solvated K + cations, additional [SnSe 4 ] 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 [( μ 6 ‐Cl) 2 K 9 ] 7+ coordination aggregate, formed by two face‐sharing [( μ 6 ‐Cl)K 6 ] octahedra.