The Reaction of Molybdenum with 2,3‐Dihydroxynaphthalene

[H 2 N(CH 2 ) 3 NH 3 ] 2 [MoO 2 (C 10 H 6 O 2 ) 2 ] ( 1 ) was synthesized by the reaction of ( n ‐Bu 4 N) 4 [Mo 8 O 26 ] with 2,3‐dihydroxynaphthalene in the mixed solvent of CH 3 OH, CH 3 CN and 1,3‐propanediamine. (C 5 H 11 N 2 ) 2 ‐ [H 2 N(CH 2 ) 3 NH 2 ][MoO 2 (C 10 H 6 O 2 ) 2 ] ( 2 ) was obtained by the reaction of Na 2 MoO 4 ·2H 2 O with 2,3‐dihydroxy‐ naphthalene in the same solvent above. Both of the complexes possess complex anion [Mo(VI)O 2 (OC 10 H 6 O) 2 ] 2− which shows pseudo‐octahedrally coordinated fashion, while the counterions are two protonated 1,3‐propanedia‐ mine in complex 1 and (C 5 H 11 N 2 ) + in complex 2 . (C 5 H 11 N 2 ) + is the byproduct of reaction 2, which results from combination of acetonitrile with 1,3‐propanediamine. Packing diagrams of the two complexes are also different. There is anti‐parallel‐aligned‐double‐meso‐bilayer unit in complex 1 . However there are four chiral anions arranged in anticlockwise orientation in complex 2 .