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The title salt, [K(C(12)H(24)O(6))][Fe(C(8)H(12))(C(10)H(8))], is the only known naphthalene complex containing iron in a formally negative oxidation state. Each (naphthalene)(1,5-cod)ferrate(-I) anion is in contact with one (18-crown-6)potassium cation via K⋯C contacts to the outer four carbon atoms of the naphthalene ligand (cod = 1,5-cyclo-octa-diene, 18-crown-6 = 1,4,7,10,13,16-hexa-oxacyclo-octa-deca-ne). When using the midpoints of the coordinating olefin bonds, the overall geometry of the coordination sphere around iron can be best described as distorted tetra-hedral. The naphthalene fold angle between the plane of the iron-coordinating butadiene unit and the plane containing the exo-benzene moiety is 19.2 (1)°.

(18-Crown-6)potassium [(1,2,5,6-η)-cycloocta-1,5-diene][(1,2,3,4-η)-naphthalene]ferrate(−I)