(Ph 4 P) 2 [Be 3 (μ‐OH) 3 (H 2 O) 6 ]Cl 5 : Crystal Structure and DFT Calculations

Bis(tetraphenylphosphonium)‐tris(μ‐hydroxo)hexaaquatriberylliumpentachloride, (Ph 4 P) 2 [Be 3 (μ‐OH) 3 (H 2 O) 6 ]Cl 5 ( 1 ), was surprisingly obtained by reaction of (Ph 4 P)N 3 · n H 2 O with BeCl 2 in dichloromethane suspension and subsequent crystallization from acetonitrile to give single crystals of composition 1· 5.25CH 3 CN. According to the crystal structure determination space group P $\bar{1}$ , Z = 2, lattice dimensions at 100 K: a = 1354.8(2), b = 1708.7(2), c = 1753.2(2) pm, α = 114.28(1)°, β = 94.80(1)°, γ = 104.51(1)°, R 1 = 0.0586] the [Be 3 (μ‐OH) 3 (H 2 O) 6 ] 3+ cations form six‐mem‐bered Be 3 O 3 rings with boat conformation and distorted tetrahedrally coordinated beryllium atoms with the terminally coordinated H 2 O molecules. The structure ist characterized by a complicated three dimensional hydrogen‐bridging network including O–H ··· O, O–H ··· Cl, and O–H ··· NCCH 3 contacts. DFT calculations result in nearly planar [Be 3 (OH) 3 ] six‐membered ring conformations.