AbstractAt 150 K [Ba(TDFND)2, tetraglyme] crystallises in theP1/cspace group witha= 17.15(2) Åb= 10.735(5) Å,c= 22.830(7) A, β = 97.56 (7)°,V= 4165 (5) Å3,Z=4.R1= 0.0435,wR2= 0.1079. The barium atom is nine‐co‐ordinate, with binding to all the O atoms. The two BaTDFND rings are planar but tilted by 26° from being co‐planar. The five O atoms of the tetraglyme ligand are also essentially co‐planar, but this plane subtends angles of 88.8(1)° and 67.4(1)° to the two BaTDFND planes. The BaO (TDFND) bond lengths are longer than for other related compounds, but the BaO (tetraglyme) bond lengths are similar to those in [Ba(HFA)2.tetraglyme] (HFA  CF3C(O)CHC(O)CF3). The low melting point and the fact that [Ba(TDFND)2.tetraglyme], alone of barium complexes of this kind, can be evaporated without decomposition at 1 atm are attributed to lower intermolecular forces for this compound and to its grea