The syntheses and characterization of several complexes of Mn(II) with cyclen derivatives having variable numbers of pendant N-acetic acid or N-acetamide arms are reported. X-ray crystallographic results are presented for Mn(DOTAM)Cl2·2H2O (monoclinic C2/c, a=18.5798(15), b=13.6006(11), c=10.5800(8) Å, β=110.490(1)°, Z=4), [Mn(DO3AM)][MnCl4]·EtOH (monoclinic P21/n, a=8.366(8), b=19.483(2), c=16.3627(16) Å, β=99.254(2)°, Z=4), and Mn(H2DOTA) (monoclinic C2/c, a=16.374(3), b=6.6559(13), c=16.750(3) Å, β=98.381(3)°, Z=4), which exhibit 8-, 7-, and 6-coordinate Mn(II), respectively. 1H relaxivity data in water at 20 MHz and 37°C is presented and interpreted in terms of a mechanism involving transient binding of water in an associative intermediate. Relaxivity studies in mixed water/methanol solvents are consistent with this interpretation.