Laser-induced fluorescence (LIF), resonant two-photon ionization (R2PI), ultraviolet hole-burning (UVHB), resonant ion-dip infrared (RIDIR), and infrared-infrared ultraviolet hole-burning (IR-IR-UV) spectroscopies were carried out on benzo-15-crown-5 ether-(H2O)(n) (B15C-(H2O)(n)) and 4'-amino-benzo-15-crown-5 ether-(H2O)(n) (ABC-(H2O)(n)) clusters with n = 1,2 formed in a supersonic expansion. Two isomers of B15C-(H2O)(1) with S-0-S-1 origins at 35 628 and 35 685 cm(-1) (B15C-(H2O)(1)(A) and B15C-(H2O)(1)(B), respectively) were identified and, oil the basis of the combined evidence from the single-isomer UV and IR spectra, assigned to structures in which the H2O molecule donates both its OH groups to H-bonds to the crown oxygens. Both isomers share the same open, chairlike C-s, symmetry structure for the crown ether that exposes the crown oxygen lone pairs to binding to H2O on the interior of the crown. This crown conformation is not among those represented in the observed conformers in the absence of the H2O molecule, indicating that even a single water molecule is capable of reshaping the crown binding pocket in binding to it. In B15C-(H2O)(1)(A), the water molecule takes up a position parallel to the crown plane of symmetry, using one OH group to bind to the two benzo oxygens, while the other OH binds to a single crown oxygen on the opposite side of the crown. The H2O molecule in B15C-(H2O)(1)(B) binds to the other two crown oxygens, in an orientation perpendicular to the crown's symmetry plane. B15C-(H2O)(2) also has two isomers. The first, B15C-(H2O)(2)(A) with S-0-S-1 origin at 35 813 cm(-1), is assigned to a structure in which the two water molecules take up the two Positions Occupied by individual water molecules in B15C-(H2O)(1) A and B. The second isomer, with S-0-S-1 origin at 35 665 cm(-1), has ail OH stretch RIDIR spectrum that reflects a water-water H-bond, with the second water molecule binding to the crown-bound water in the parallel binding site. The combined data from B15C-(H2O)(1), ABC-(H2O)(1), and ABC-(HOD) complexes is used to deduce the uncoupled OH stretch wavenumber shifts associated with each of the unique binding sites for H2O to the crown. Arguments are presented that the binding pocket present in benzo-15-crown-5 ether is of a near ideal size to accommodate strong bidentate binding of individual water molecules to its most open crown conformation.