Structural Characterization of Some Coinage Metal(I) Thiosulfate Complexes, $\rm M^{1}_{a}M\rm ^{2}_{b}(X_{c}) (S_{2}O_{3})_{d}(\cdot eS)$ (M1 = Group 1 Cation, X = Univalent Anion, M2 = CuI, AgI, S = Solvent)
Authors: Chan Eric J. , Skelton Brian W. , White Allan H. 
Published: November 2008

Building on previous single crystal X‐ray structure determinations for the group 1 salts of complex thiosulfate/univalent coinage metal anions previously defined for (NH4)9AgCl2(S2O3)4, NaAgS2O3·H2O and Na4[Cu(NH3)4][Cu(S2O3)2]·NH3, a wide variety of similar salts, of the form $\rm M^{1}_{a}M\rm ^{2}_{b}(X_{c}) (S_{2}O_{3})_{d}$, M1 = group 1 metal cation, M2 = univalent coinage metal cation (Cu, Ag), (X = univalent anion), most previously known, but some not, have been isolated and subjected to similar determinations. These have defined further members of the isotypic, tetragonal $I{\bar 4} {\rm 2}d \textrm{ }{\rm M^{1}_{9}M^{2}X_{2}(S_{2}O_{3})_{4}({\equiv}M^{1}_{9}X_{2}[M^{2}}(S{\rm SO_{3})_{4}]{\equiv}2M^{1}X}.\textrm{ } {\rm M^{1}_{7}[M^{2}}(S{\rm SO_{3})_{4}]}$ series, for M1 = NH4, M2 = Cu, Ag, X = NO3, Cl, Br, I, together with the K/Cu/NO3 complex, all containing the complex anion [M2(SSO3)4]7− with M2 in an environment of $\rm {\bar 4}$ symmetry, Cu, Ag‐S typically ca. 2.37, 2.58Å, with quasi‐tetrahedral S‐M‐S angular environments. Further salts of the form $\rm M^{1}_{2n-1}M^{2}(S_{2}O_{3})_{n}(\cdot xH_{2}O)$, n = 1‐3, have also been defined: For n = 3, M2 = Cu, M1/x = K/2.25 or 1 5/6, NH4/6, (and also for the (NH4)4Na/4H2O·MeOH adduct) the arrays take the form ${\rm M^{1}_{5}[Cu}(S{\rm SO_{3})_{3}]{\cdot}xS}$ with distorted trigonal planar CuS3 coordination environments, Cu‐S distances being typically 2.21Å, S‐Cu‐S ranging between 105.31(4)–129.77(4)°; the silver counterparts take the form ${\rm M^{1}_{10}[(O_{3}S}S){\rm_{2}Ag(\mu-}S{\rm SO_{3}})_{2}{\rm Ag}(S{\rm SO_{3}})_{2}]$ for M1 = K, NH4. For n = 2, adducts have only been defined for M2 = Ag, the anions of the M1 = Na, K adducts being dimeric and polymeric respectively: Na6[(O3SS)2Ag(μ‐SSO3)2Ag(SSO3)]·3H2O, K3[Ag(μ‐SSO3)2](∞|∞)·H2O; a polymeric copper(I) counterpart of the latter is found in Na5Cu(NO3)2(S2O3)2 ≡ 2NaNO3·Na3[Cu(μ‐SSO3)2](∞|∞). For n = 1, NaAgS2O3, the an‐ and mono‐ hydrates, exhibit a two‐dimensional polymeric complex anion in both forms but with different contributing motifs. (NH4)13Ag3(S2O3)8·2H2O takes the form (NH4)13[{(O3SS)3Ag(μ‐SSO3)}2Ag], a linearly coordinated central silver atom linking a pair of peripheral [Ag(SSO3)4]7− entities. In Na6[(O3SS)Ag(μ‐SSO3)2Ag(SSO3)]·3H2O, the binuclear anions present as Ag2S4 sheets, the associated oxygen atoms being disposed to one side, thus sandwiching layers of sodium ions; the remarkable complex Na5[Ag3(S2O3)4](∞|∞)·H2O is a variant, in which one sodium atom is transformed into silver, linking the binuclear species into a one‐dimensional polymer. In (NH4)8[Cu2(S2O3)5]·2H2O a binuclear anion of the form [(O3SS)2Cu(μ‐S.SO3)Cu(SSO3)2]8− is found; the complex (NH4)11Cu(S2O3)6 is 2(NH4)2(S2O3)·(NH4)7[Cu(SSO3)4]. A novel new hydrate of sodium thiosulfate is described, 4Na4S2O3·5H2O, largely describable as sheets of the salt, shrouded in water molecules to either side, together with a redetermination of the structure of 3K2S2O3·H2O.