Abstract: | The ammoniates K(18‐crown‐6)(NH3)2]3Sb11 · 5.5NH3 ( 1 ) and Cs(18‐crown‐6)]2CsAs11 · 8NH3 ( 2 ) (18‐crown‐6 = 18C6: 1,4,7,10,13,16‐Hexaoxacyclooctadecan) were synthesized by either the reaction of K3Sb7 with SbPh3 in liquid ammonia or by extraction of Cs3As11 with liquid ammonia. Single crystals were isolated and characterized by low temperature X‐ray structure analysis. K(18‐crown‐6)(NH3)2]3Sb11 · 5.5NH3 crystallizes in the space group with a = 13.31(2) Å, b = 15.161(2) Å, c = 22.521(3) Å, α = 99.23(1)°, β = 100.99(1)° and γ = 105.03(1)°. Cs(18‐crown‐6)]2CsAs11 · 8NH3 crystallizes in the monoclinic space group C2/c with a = 20.009(3) Å, b = 17.024(1) Å, c = 19.838(2) Å and β = 119.732(9)°. While 1 contains isolated Sb11]3? anions and K(18‐crown‐6)(NH3)2]+ complexes, cesium–arsenic contacts lead to one–dimensionally infinite chains in 2 . |