Hybrid Inorganic-Organic Host-Guest Compounds: Open-Framework Cadmium Oxalates Incorporating Novel Extended Structures of Alkali Halides
详细信息 查看全文
- 作者：R. Vaidhyanathan ; Srinivasan Natarajan ; and C. N. R. Rao
- 刊名：Chemistry of Materials
- 出版年：2001
- 出版时间：October 2001
- 年：2001
- 卷：13
- 期：10
- 页码：3524 - 3533
- 全文大小：1391K
- 年卷期：v.13,no.10(October 2001)
- ISSN：1520-5002
文摘
Four unusual inorganic-organic nanocomposites containing extended alkali halidestructures, present as layers or as three-dimensional units, have been synthesized by ametathetic reaction carried out under hydrothermal conditions. These compounds, withcadmium oxalate host lattices and the alkali halide structures as guests, have thecompositions [RbCl][Cd6(C2O4)6]·2H2O, I; 2[CsBr][Cd(C2O4)]·H2O, II; 2[CsBr][Cd2(C2O4)(Br)2]·2H2O, III; and 3[RbCl][Cd2(C2O4)(Cl2)]·H2O, IV. Crystal data for I, rhombohedral, spacegroup = R-3 (no. 148), a = 9.3859(3), c = 23.9086(8) Å; V = 1824.05(1) Å3, Z = 18, M =1359.51, 
calcd = 3.702 g cm-3, 
(Mo K
) = 7.375 mm-1, R1 = 0.04, wR2 = 0.0904 [537 observedreflections with I > 2
(I)]; for II, orthorhombic, space group = Pbcm (no. 57), a = 6.0854(6),b = 11.0793(11), c = 16.889(2) Å; V = 1138.7(2) Å3, Z = 8, M = 644.06, calcd = 3.745 g cm-3,(Mo K) = 15.219 mm-1, R1 = 0.04, wR2 = 0.08 [408 observed reflections with I > 2(I)];for III, orthorhombic, space group = Cmcm (no.63), a = 23.6151(14), b = 10.2528(6), c =7.8199(6) Å; V = 1894.2(2) Å3, Z = 16, M = 970.33, calcd = 3.374 g cm-3, (Mo K) = 14.487mm-1, R1 = 0.03, wR2 = 0.0744 [651 observed reflections with I > 2(I)]; for IV, monoclinic,space group = P21/c (no. 14), a = 8.0648(2)(3), b = 22.9026(4), c = 9.3967(3) Å; V = 1681.10(7)Å3, Z = 4, M = 782.53, calcd = 3.076 g cm-3, (Mo K) = 11.961 mm-1, R1 = 0.04, wR2 =0.093 [2071 observed reflections with I > 2(I)]. Compounds I-IV possess many unusualstructural features. While I has interpenetrating lattices of the three-dimensional cadmiumoxalate and RbCl with an expanded lattice, giving rise to a super rock-salt cell, II possessesalternating cadmium oxalate and CsBr layers, the latter comprising six-membered CsBrrings. Compounds III and IV have isolated cadmium oxalate units (zero-dimensional) linkedand stabilized by the alkali halides.
calcd = 3.702 g cm-3, (Mo K) = 7.375 mm-1, R1 = 0.04, wR2 = 0.0904 [537 observedreflections with I > 2(I)]; for II, orthorhombic, space group = Pbcm (no. 57), a = 6.0854(6),b = 11.0793(11), c = 16.889(2) Å; V = 1138.7(2) Å3, Z = 8, M = 644.06, calcd = 3.745 g cm-3,(Mo K) = 15.219 mm-1, R1 = 0.04, wR2 = 0.08 [408 observed reflections with I > 2(I)];for III, orthorhombic, space group = Cmcm (no.63), a = 23.6151(14), b = 10.2528(6), c =7.8199(6) Å; V = 1894.2(2) Å3, Z = 16, M = 970.33, calcd = 3.374 g cm-3, (Mo K) = 14.487mm-1, R1 = 0.03, wR2 = 0.0744 [651 observed reflections with I > 2(I)]; for IV, monoclinic,space group = P21/c (no. 14), a = 8.0648(2)(3), b = 22.9026(4), c = 9.3967(3) Å; V = 1681.10(7)Å3, Z = 4, M = 782.53, calcd = 3.076 g cm-3, (Mo K) = 11.961 mm-1, R1 = 0.04, wR2 =0.093 [2071 observed reflections with I > 2(I)]. Compounds I-IV possess many unusualstructural features. While I has interpenetrating lattices of the three-dimensional cadmiumoxalate and RbCl with an expanded lattice, giving rise to a super rock-salt cell, II possessesalternating cadmium oxalate and CsBr layers, the latter comprising six-membered CsBrrings. Compounds III and IV have isolated cadmium oxalate units (zero-dimensional) linkedand stabilized by the alkali halides.