Komplexe einwertiger Dibenzo‐18‐Krone‐6‐Kationen mit Triiodid als Anionen

Abstract

Abstract Complexes of Monovalent Dibenzo‐18‐crown‐6 Cations with Triiodide as Anions The new polyiodides [NH 4 (db18c6)] 2 (I 3 ) 2 ( 1 ), [NH 4 (db18c6)](db18c6)I 3 ( 2 ), [Na 1/2 (db18c6)H 2 O] 2 I 3 ( 3 ), [Rb(db18c6)]I 3 ( 4 ), [Rb(db18c6)] 2 (I 3 ) 2 ( 5 ), [Cs(db18c6)]I 3 ( 6 ), and [Cs 2 (db18c6) 3 ][Cs(db18c6) 3/2 ](I 3 ) 3 ( 7 ) were obtained from reactions of dibenzo‐18‐crown‐6 (db18c6) and iodine with NH 4 I, NaI, RbI, and CsI. Their crystal structures were determined by single‐crystal X‐ray diffraction. ( 1 ) M = NH 4 , ( 5 ) M = Rb: monoclinic, P2 1 /n, a = 1409,67(8), b = 2211,63(14), c = 1627,16(10) pm, β = 101,030(5)°, Z = 4 (crystal data for M = NH 4 ); ( 2 ): monoclinic, Pn, a = 1345,26(14), b = 773,82(4), c = 2095,10(20) pm, β = 94,439(8)°, Z = 2; ( 3 ): orthorhombic, Pnaa, a = 931,59(13), b = 2213,3(5), c = 2223,9(4) pm, Z = 4; ( 4 ): monoclinic, P2 1 /n, a = 999,50(6), b = 1711,33(10), c = 1517,45(9) pm, β = 99,021(5)°, Z = 4; ( 6 ): triclinic, $\rm P{\bar 1}$ , a = 705,16(9), b = 1137,93(14), c = 1678,90(20) pm, α = 73,719(10), β = 79,782(10), γ = 83,669(10)°, Z = 2; ( 7 ): triclinic, $\rm P{\bar 1}$ , a = 1519,25(6), b = 1702,49(7), c = 2136,41(9) pm, α = 102,641(3), β = 101,989(3), γ = 91,911(3)°, Z = 2. 1 : 1 cations centered by M, [M(db18c6)] + , are found in the structures of ( 1 – 6 ). In contrast, the triple decker cation found in ( 7 ) is less common. The crystal structures are completed by mostly asymmetrically linear I 3 − anions.