The reactions of UO2SO4.3H2O with 12-crown-4, 15-crown-5, benzo-15-crown-5, 18-crown-6, and dibenzo-18-crown-6 were investigated in nitric, acetic, hydrochloric, and sulfuric acids. Impurities in the nitric acid resulted in the isolation of the complexes [(H5O2)((NO2)2benzo-15-crown-5)2]2[(UO2(NO3)2)2C2O4] (benzo-15-crown-5 was nitrated during the reaction) and [(H3O)-(18-crown-6)]2[(UO2(NO3)2)2C2O4], which were crystallographically characterized. [Mg(OH2)6][(H3O)(15-crown-5)]2[(UO2-(SO4))2C2O4]2 was also isolated from nitric acid and partially characterized crystallographically. Reactions in acetic acid produced uranyl sulfate polymers with layers of hydrogen-bonded crown ethers in the lattice: [UO2(SO4)(OH2)2].0.5(12-crown-4).H2O, [UO2(SO4)(OH2)2].0.5(benzo-15-crown-5).1.5H2O, and [UO2(SO4)(OH2)3].0.5(18-crown-6). Hydronium ion complexes of crown ethers stabilized by [UO2Cl4]2- anions were isolated from hydrochloric acid. The complexes [(H5O2)(H9O4)(benzo-15-crown-5)2][UO2Cl4] and [(H5O2)2(18-crown-6)][UO2Cl4] were isolated and crystallographically characterized. Reactions in sulfuric acid for the most part produced decomposition products. [(H3O)(dibenzo-18-crown-6)][HSO4].CH3CN was isolated by recrystallization of a purple precipitate from CH3CN/CH3OH (3:1). [(H5O2)((NO2)2benzo-15-crown-5)2]2[(UO2(NO3)2)2C2O4] crystallizes in the monoclinic space group P2(1)/n with (at 22-degrees-C) a = 8.995 (4) angstrom, b = 19.684 (5) angstrom, c = 24.739 (4) angstrom, beta = 90.42 (2)-degrees, and D(calcd) = 1.81 g cm-3 for Z = 2 formula units. A final conventional R value of 0.038 was obtained by least-squares refinement with 4790 independent observed reflections [F(o) greater-than-or-equal-to 5-sigma(F(o))]. [(H3O)(18-crown-6)]2[(UO2(NO3)2)2C2O4] is monoclinic, P2(1)/n, with (at 22-degrees-C) a = 9.804 (1) angstrom, b = 21.037 (7) angstrom, c = 11.827 (3) angstrom, beta = 94.70 (2)-degrees, D(calcd) = 1.97 g cm-3 for Z = 2, and R = 0.040 for 2587 observed reflections. [UO2(SO4)(OH2)2].0.5(12-crown-4).H2O is triclinic, P1BAR, with (at 22-degrees-C) a = 7.007 (1) angstrom, b = 8.0408 (6) angstrom, c = 10.776 (2) angstrom, alpha = 91.31 (1)-degrees, beta = 93.60 (2)-degrees, gamma = 100.18 (1)-degrees, D(calcd) = 2.83 g cm-3, Z = 2, and R = 0.032 for 1883 observed reflections. [UO2(SO4)(OH2)2].0.5(benzo-15-crown-5).1.5H2O is triclinic, P1BAR with (at 22-degrees-C) a = 6.908 (2) angstrom, b = 8.717 (4) angstrom, c = 13.578 (2) angstrom, alpha = 79.46 (2)-degrees, beta = 75.28 (2)-degrees, gamma = 89.98 (3)-degrees, D(calcd) = 2.41 g cm-3, Z = 2, and R = 0.056 for 2261 observed reflections. [UO2(SO4)(OH2)3].0.5(18-crown-6) is monoclinic, P2(1)/n, with (at 20-degrees-C) a = 9.314 (5) angstrom, b = 9.339 (3) angstrom, c = 16.734 (3) angstrom, beta = 103.62 (3)-degrees, D(calcd) = 2.59 g cm-3 for Z = 4, and R = 0.071 for 1649 observed reflections. [(H5O2)(H9O4)(benzo-15-crown-5)2][UO2Cl4] is triclinic, P1BAR, with (at 20-degrees-C) a = 8.889 (3) angstrom, b = 10.149 (3) angstrom, c = 11.626 (3) angstrom, alpha = 94.54 (2)-degrees, beta = 91.04 (2)-degrees, gamma = 104.29 (3)-degrees, D(calcd) = 1.74 g cm-3, Z = 1, and R = 0.034 for 3455 observed reflections. [(H5O2)2(18-crown-6)][UO2Cl4] is triclinic, P1BAR, with (at - 150-degrees-C) a = 6.9265 (8) angstrom, b = 9.239 (1) angstrom, c = 10.429 (2) angstrom, alpha = 93.34 (1)-degrees, beta = 103.50 (1)-degrees, gamma = 106.15 (1)-degrees, D(calcd) = 2.02 g cm-3, Z = 1, and R = 0.025 for 2153 observed reflections. [(H3O)(dibenzo-18-crown-6)][HSO4].CH3CN is triclinic, P1BAR, with (at 18-degrees-C), a = 9.118 (2) angstrom, b = 9.348 (5) angstrom, c = 15.879 (4) angstrom, alpha = 77.60 (3)-degrees, beta = 80.99 (2)-degrees, gamma = 78.22 (3)-degrees, D(calcd) = 1.34 g cm-3, Z = 2, and R = 0.073 for 1070 observed reflections.
