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• W2014295477 abstract "Reaction of aqueous AgNO3 with aqueous M3[Cr(ox)3] in ≥3:1 molar ratio causes the rapid growth of large, cherry-black, light-stable crystals which are not Ag3[Cr(ox)3], but [M0.5(H2O)3]@[Ag2.5Cr(ox)3] (ox2- = oxalate, C2O42-; M = Na, K, Cs, Ag, or mixtures of Ag and a group 1 element). The structure of these crystals contains an invariant channeled framework, with composition {[Ag2.5Cr(ox)3]-0.5}∞, constructed with [Cr(ox)3] coordination units linked by Ag atoms through centrosymmetric {Cr−O2C2O2−Ag}2 double bridges. The framework composition [Ag2.5Cr(ox)3]-0.5 occurs because one Ag is located on a 2-fold axis. Within the channels there is a well-defined and ordered set of six water molecules, strongly hydrogen bonded to each other and some of the oxalate O atoms. This invariant channel plus water structure accommodates group 1 cations, and/or Ag cations, in different locations and in variable proportions, but always coordinated by channel water and some oxalate O atoms. The general formulation of these crystals is therefore [MxAg0.5-x(H2O)3]@[Ag2.5Cr(ox)3]. Five different crystals with this structure are reported, with compositions 1 Ag0.5[Ag2.5Cr(ox)3](H2O)3, 2 Cs0.19Ag0.31[Ag2.5Cr(ox)3](H2O)3, 3 K0.28Ag0.22[Ag2.5Cr(ox)3](H2O)3, 4 Cs0.41Ag0.09[Ag2.5Cr(ox)3](H2O)3, and 5 Cs0.43Ag0.07 [Ag2.5Cr(ox)3](H2O)3. All crystallize in space group C2/c, with a ≈ 18.4, b ≈ 14.6, c ≈ 12.3 Å, β ≈ 113°. Pure Ag3[Cr(ox)3](H2O)3, which has the same crystal structure (1), was obtained from water by treating Li3[Cr(ox)3] with excess AgNO3. Complete dehydration of all of these compounds occurs between 30 and 100 °C, with loss of diffraction, but rehydration by exposure to H2O(g) at ambient temperature leads to recovery of the original diffraction pattern. In single crystals, this reversible dehydration−hydration occurs without visually evident crystal change, but with loss of mechanical strength. We postulate a general mechanism for transport of water molecules along the channels, associated with local partial collapses of the channel framework, with concomitant bending but little breaking of the host Ag−O and Cr−O bonds, which is readily reversed." @default.
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• W2014295477 title "A Variable Ag−Cr−Oxalate Channel Lattice: [M_<i>x</i>Ag_0.5_-<i>_x</i>(H₂O)₃]@[Ag_2.5Cr(C₂O₄)₃], M = K, Cs, Ag" @default.
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• W2014295477 doi "https://doi.org/10.1021/ic034988k" @default.
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