Abstract: | Crystal Structure of BeCl2(15‐Crown‐5)] Single crystals of BeCl2(15‐crown‐5)] ( 1 ) were obtained from dichloromethane solutions of BeCl2 in the presence of the equivalent amount of 15‐crown‐5 and characterized by IR spectroscopy and X‐ray diffraction. Space group P21/c, Z = 4, lattice dimensions at 100 K: a = 1036.2(1), b = 1071.1(1), c = 1360.1(1) pm, β = 109.86(1)°, R1 = 0.0225. The structure determination shows no disorder, all hydrogen positions were refined isotropically. The results are in contrast to the previously reported crystal structure determination in the space group P21nb. The beryllium atom of 1 forms a BeO2C2 five‐membered heterocycle with terminal chlorine atoms to give a distorted tetrahedral coordination with distances Be–O 166.5(2), 169.9(2) pm, and Be–Cl 195.8(2), 197.8(2) pm. The structural results are in good agreement with DFT calculations on B3LYP/6‐311+G** level. |