TY - JOUR
T1 - Polyoxo Alkoxide Clusters of Vanadium
T2 - Structural Characterization of the Decavanadate Core in the “Fully Reduced” Vanadium(IV) Species [V10O16{(OCH2)3CCH2CH3}4]4− and [V10O16(OH)2{(OCH)2)3CCH2OH}4]2− and in the Mixed-Valence Clusters [VIV8VV2O16{(OCH2)3CR}4]2− (R = -CH2CH3, -CH3)
AU - Khan, M. Ishaque
AU - Chen, Qin
AU - Goshorn, D. P.
AU - Zubieta, Jon
PY - 1993
Y1 - 1993
N2 - The hydrothermal reaction of a mixture of vanadium oxides with (HOCH2)3CCH2OH in the presence of Me3NHCl yields the reduced species (Me3NH)2[VIV10O14(OH)2{(OCH2)CCH2OH}4]·2H2O (1). In contrast, the reactions of vanadium oxides with (HOCH2)3CR3, using NaCl, KCl, or (C4H9)4NCl as mineralizers, yield the mixed-valence species M2[VIV8VV2O16{(OCH2)3CR}4]·nH2O (M = Na, n = 0, R = -CH2CH3 (2); ? = ?, n = 2, R = -CH2CH3 (3); M = (C4H9)4N, n = 0, R = -CH3 (4)). These compounds exhibit structures based on the decavanadate core {V10O28}, with ten doubly-bridging and two triply-bridging oxo groups of this parent structure replaced by the alkoxy donors of the ligands. The structural consequences of protonation of the core in 1 and of oxidation of two vanadium centers in 2-4 are presented. The crystal packing patterns of anion clusters and cations in these species reveal the common structural motif of anion stacking to produce polar and nonpolar channels. The influence of the cation on the details of the extended structure is apparent in the crystal packing descriptions. Crystal data are as follows. (Me3NH)2[V10O14(OH)2){(OCH2)3CCH2OH}4]-2H2O (1): monoclinic space group P21/c, a = 10.243(2) Å, b = 18.237(4) Å, c = 13.055(2) Å, β = 103.48(2)o, V = 2371.5(9) Å3, ? = 2, Dcalc = 1.95 g cm-3; structure solution and refinement based on 3505 reflections converged at R = 0.038. Na2[V10O16{(OCH2)3CCH2CH3}4] (2): monoclinic space group P21/c, a = 12.861(2) Å, b = 10.536(2) Å, c = 15.909(4) Å, β = 109.21(2)o, V= 2035.7(8) Å3, ? = 2, Dcalc = 2.18 g cm-3; 3006 reflections, R = 0.042. K2[V10O16{(OCH2)3CCH2CH3}4]-2H2O (3): triclinic space group P1̄, a = 10.249(2) Å, b = 12.438(2) Å, c = 9.903(2) Å, a = 97.51(1)o, β = 109.30(1)o, γ = 68.41(1)o, V = 1107.8(6) Å3, Dcalc = 2.10 g cm-3; 4441 reflections, R = 0.030. [(C4H9)4N]2[V10O16{(OCH2)3CCH3}4] (4): monoclinic space group, ?21/n, a = 13.523(4) Å, b= 18.453(3) Å, c = 14.375(6) Å, β= 104.87(2)o, V = 3466.9(15) Å3, ? = 2, Dcalc = 1.65 g cm-3; 2964 reflections, R = 0.047.
AB - The hydrothermal reaction of a mixture of vanadium oxides with (HOCH2)3CCH2OH in the presence of Me3NHCl yields the reduced species (Me3NH)2[VIV10O14(OH)2{(OCH2)CCH2OH}4]·2H2O (1). In contrast, the reactions of vanadium oxides with (HOCH2)3CR3, using NaCl, KCl, or (C4H9)4NCl as mineralizers, yield the mixed-valence species M2[VIV8VV2O16{(OCH2)3CR}4]·nH2O (M = Na, n = 0, R = -CH2CH3 (2); ? = ?, n = 2, R = -CH2CH3 (3); M = (C4H9)4N, n = 0, R = -CH3 (4)). These compounds exhibit structures based on the decavanadate core {V10O28}, with ten doubly-bridging and two triply-bridging oxo groups of this parent structure replaced by the alkoxy donors of the ligands. The structural consequences of protonation of the core in 1 and of oxidation of two vanadium centers in 2-4 are presented. The crystal packing patterns of anion clusters and cations in these species reveal the common structural motif of anion stacking to produce polar and nonpolar channels. The influence of the cation on the details of the extended structure is apparent in the crystal packing descriptions. Crystal data are as follows. (Me3NH)2[V10O14(OH)2){(OCH2)3CCH2OH}4]-2H2O (1): monoclinic space group P21/c, a = 10.243(2) Å, b = 18.237(4) Å, c = 13.055(2) Å, β = 103.48(2)o, V = 2371.5(9) Å3, ? = 2, Dcalc = 1.95 g cm-3; structure solution and refinement based on 3505 reflections converged at R = 0.038. Na2[V10O16{(OCH2)3CCH2CH3}4] (2): monoclinic space group P21/c, a = 12.861(2) Å, b = 10.536(2) Å, c = 15.909(4) Å, β = 109.21(2)o, V= 2035.7(8) Å3, ? = 2, Dcalc = 2.18 g cm-3; 3006 reflections, R = 0.042. K2[V10O16{(OCH2)3CCH2CH3}4]-2H2O (3): triclinic space group P1̄, a = 10.249(2) Å, b = 12.438(2) Å, c = 9.903(2) Å, a = 97.51(1)o, β = 109.30(1)o, γ = 68.41(1)o, V = 1107.8(6) Å3, Dcalc = 2.10 g cm-3; 4441 reflections, R = 0.030. [(C4H9)4N]2[V10O16{(OCH2)3CCH3}4] (4): monoclinic space group, ?21/n, a = 13.523(4) Å, b= 18.453(3) Å, c = 14.375(6) Å, β= 104.87(2)o, V = 3466.9(15) Å3, ? = 2, Dcalc = 1.65 g cm-3; 2964 reflections, R = 0.047.
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U2 - 10.1021/ic00057a030
DO - 10.1021/ic00057a030
M3 - Article
AN - SCOPUS:0001298819
SN - 0020-1669
VL - 32
SP - 672
EP - 680
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -