Addition of t-butylcyclohexano-15-crown-5 (tBC-15C5) induces a synergistic effect in the extraction of Mn2+ion with didodecylnaphthalenesulfonic acid (HDDNS). This synergism is the result of the inner-sphere complexation of the crown ether to the manganese(II) ion. The formation of this complex, first suggested by distribution studies, has been confirmed by FTIR experiments. The C-O-C stretching bands for the crown ether ligand shift to lower frequency when Mn2+ion is extracted into a CC14 solution of HDDNS and tBC15C5. A similar C-O-C Btretching band is observed for the crystalline complex [Mn(15C5 ) (Bu3CS03)2] (where 15C5 = 15-crown-5 and Bu = n-butyl).Formation of analogous complexes is not observed for Fe3+, co2+,N2+,cu2+, or zn2+under similar conditions.