Quanming Wang

Microporous networks co-assembled by both rigid and flexible building blocks

Abstract The porous networks of [Cu2(malonato)2(bipy)(H2O)2]·H2O (I) and [Cd(malonato)(py)(H2O)] (II) were co-assembled by rigid 4,4′-bipyridine or pyridine and the flexible malonate ion. In the network of compound I, 4,4′-bipy acts as a bone, separating and supporting the flexible malonate–Cu units to form a nearly strain-free square framework and a chiral square cavity in the solid state. In compound II, the rigid pyridine rings sustain the network by saturating the coordination sphere of Cd(II) ion to avoid a high coordination number and self-inclusion, and to prevent the two-dimensional network from forming a non-porous phase.

Three New Structural Types of Mo/Ag/S Polymeric Complexes

Wavelike, zigzag, and helical polymers are formed by the reaction of [MoS4 ]2- , Ag2 S, and a complementary cation. The framework of the polymeric anions depends on the valence state of the latter. For example, the butterfly-type anionic chain shown in the picture is formed upon use of a divalent cation. There is a general tendency that a higher valence state of the cation will induce a more compact chain structure.

Two novel polymeric bismuth(III) complexes with dmit: syntheses and structures of {[Et4N][Bi(dmit)2]}n and {[Et4N]2[Bi2(dmit)4]·Et2O}n (dmit=1,3-dithiole-2-thione-4,5-dithiolate)

Abstract Two novel polymeric bismuth(III) complexes with dmit, {[Et4N][Bi(dmit)2]}n (1) and {[Et4N]2[Bi2(dmit)4]·Et2O}n (2), have been synthesized and structurally characterized. Complex 1 is a one-dimensional polymer consisting of repeating Bi(dmit)2 units in which each Bi atom is six-coordinated by six sulfur atoms from dmit ligands to form a distorted octahedron. Whereas the anions of complex 2 can be described as polymeric chains being composed of the repeating dimeric Bi2(dmit)4 units, in which the environment of the Bi atoms are similar to that in complex 1. In contrast to 1, there exists S⋯S contacts less than 3.7 A between two neighboring independent polymeric anions in complex 2, through which complex 2 forms a quasi two-dimensional structure.

Synthesis and crystal structure of the cryptate complex [Gd(L) (DMF)] · KSCN · CH3CN · 3H20 (L is a deprotonated phenol-based N803 cryptand)

The cryptate complex [Gd(L)(DMF)]. KSCN . CH3CN . 3H(2)O has been synthesized by the reaction of gadolinium isothiocyanate and potassium thiocyanate with cryptate [Na(H(2)L)], which was prepared by a (2+3) Schiff-base condensation of tris(2-aminoethyl)amine and 2,6-diformyl-4-methoxyphenol in the presence of NaOH. The Gd atom is encapsulated in the cryptand with an unsymmetric eight-coordinate environment. Copyright (C) 1996 Elsevier Science Ltd

SYNTHESES AND STRUCTURES OF [Et4N]2[Sn(DMIT)3] AND [Pb(DMIT)(DMF)]n (DMIT = 2-THIOXO-1,3-DITHIOLE-4,5-DITHIOLATO)

Abstract Two complexes, [Et4N]2[Sn(dmit)3], 1, and [Pb(dmit)(DMF)]n L, have been obtained and their structures crystallographically determined. In complex 1, the Sn atom is six-coordinated to ax sulfur atoms from three dmit ligands; the anions form a one-dimensional network through S S contacts shorter than 3.7 A. Complex 2 forms a two-dimensional polymer, achieved through Pb atom coordinating not only to the chelating sulfur atoms of the dithiolate fragment of dmit, but also to the sulfur atom of the thiocarbonyl group of a dmit ligand. In complex 2, the central Pb atom is six-coordinated by four sulfur atoms from dmit ligands and two oxygen atoms of N,N,-dimethyIformamide ligands, exhibiting a distorted octahedral structure.

Syntheses, characterizations and structures of a novel double-chain polymeric cluster complex [WS4Ag · NH3C(CH20H)3 · H20]n and its precursory single-chain complex [WS4Ag · NH3C(CH20H)3 · 2DMF]n

Abstract The title single chain complex 1 was obtained from reaction of ammonium tetrathiotungstate, silver nitrate and tris(hydroxy-methyl)-amino-methane in DMF, and the title double-chain complex 2 from the recrystallization of 1 in ethanol and a little amount of water. The anionic structure of 1 is a [WAgS 4 ] n linear chain, and that of 2 is a [WAgS 4 ] n double chain which can be viewed as two zigzag — SWSAg — chains bridged by μ in 2-S atoms. In 2 , H 2 O molecules and NH 3 C(CH 2 OH) 3 + cations interact with each other through hydrogen bonding and form a two-dimensional network supramolecular structure. The inversion of configurations from 1 to 2 by re-self-assembly of [WAgS 4 ] fragments, as well as IR spectra of both complexes, is described.

Crystal structure of a flexible self-assembled two-dimensionalsquare network complex[Cu2(C3H2O4)2(H2O)2(4,4′-bpy)]·H2O

The structure of a self-assembled two-dimensional square network complex, [Cu 2 (C 3 H 2 O 4 ) 2 (H 2 O) 2 (4,4′-bpy)]·H 2 O, comprising both flexible and rigid ligands and having a large inner cavity of 15.776(3) × 15.786(2) A, is reported.

The first metal–dmit polymer with 3D supramolecular networks. Synthesis and crystal structure of [(Et4N)2{Ag4(dmit)3} · DMF]∞ (dmit=1,3-dithiole-2-thione-4,5-dithiolate)

Abstract The first metal–dmit polymeric complex, [(Et4N)2{Ag4(dmit)3} · DMF]∞, has been synthesized and structurally characterized. The crystal of the complex is monoclinic with space group C2/c, a=32.078(4), b=11.791(2), c=29.409(4) A, β=124.14(1)°, V=9206.8, Z=8, R=0.053, Rw=0.061. In the complex, the S · · · S contacts exist both intra- and inter-molecularly, through the intermolecular S · · · S contacts shorter than 3.7 A the two-dimensional polymeric anions form a three-dimensional unique supramolecular networks.

Drei neuartige Strukturtypen von polymeren Mo/Ag/S-Komplexen

Wellenformige, zickzackformige und helicale Polymere entstehen bei der Reaktion von [MoS4]2−, Ag2S und einem Gegenkation. Die Struktur des polymeren Anions hangt dabei von der Ladung des Kations ab: Mit einem zweifach geladenen Kation entsteht z. B. eine schmetterlingsartige Anionenkette (siehe Bild). Eine hohere Ladungszahl des Kations fuhrt hierbei tendenziell zu einer kompakteren Kettenstruktur.

Syntheses and crystal structures of two heterometallic incomplete cubane-like clusters: [-MoAg2S3C5H5NS-(PPh3)2(S)]·CH2Cl2 and [-WAg2Se3C5H5NS-(PPh3)2(Se)]·CH2Cl2

Abstract Two incomplete cubane-like clusters, [{MoAg2S3C5H5NS}(PPh3)2(S)]·CH2Cl2 (I) and [{WAg2Se3C5H5NS}(PPh3)2(Se)]·CH2Cl2 (II), were obtained from the reaction of MoS4Ag2(PPh3)3 and WSe4 Ag2(PPh3)3 with excess C5H5NS in CH2Cl2 solvent. The X-ray crystallography analysis shows that I and II have incomplete cubane-like structures, in which the Mo(W) and Ag atoms are tetrahedrally coordinated.