Synthesis, structure, and thermal properties of soluble hydrazinium germanium(IV) and tin(IV) selenide salts

The crystal structures of two hydrazinium-based germanium(IV) and tin(IV) selenide salts are determined. (N(2)H(5))(4)Ge(2)Se(6) (1) [I4(1)cd, a = 12.708(1) Angstroms, c = 21.955(2) Angstroms, Z = 8] and (N(2)H(4))(3)(N(2)H(5))(4)Sn(2)Se(6) (2) [P, a = 6.6475(6) Angstroms, b = 9.5474(9) Angstroms, c = 9.8830(10) Angstroms, alpha = 94.110(2) degrees, beta = 99.429(2) degrees, gamma = 104.141(2) degrees, Z = 1] each consist of anionic dimers of edge-sharing metal selenide tetrahedra, M(2)Se(6)(4-) (M = Ge or Sn), separated by hydrazinium cations and, for 2, additional neutral hydrazine molecules. Substantial hydrogen bonding exists among the hydrazine/hydrazinium molecules as well as between the hydrazinium cations and the selenide anions. Whereas the previously reported tin(IV) sulfide system, (N(2)H(5))(4)Sn(2)S(6), decomposes cleanly to microcrystalline SnS(2) when heated to 200 degrees C in an inert atmosphere, higher temperatures (>300 degrees C) are required to dissociate selenium from 1 and 2 for the analogous preparations of single-phase metal selenides. The metal chalcogenide salts are highly soluble in hydrazine, as well as in a variety of amines and DMSO, highlighting the potential usefulness of these compounds as precursors for the solution deposition of the corresponding metal chalcogenide films.     

From 1D chain to 3D network: tuning hybrid II-VI nanostructures and their optical properties

In an effort to make semiconductor nanomaterials with tunable properties, we have deliberately designed and synthesized a family of novel organic-inorganic hybrid nanocomposites based on II-VI semiconductors with structures ranging from one-dimensional (1-D) chain to two-dimensional layer (2-D) to three-dimensional (3-D) framework. All nanostructures exhibit strong quantum confinement effect (QCE), while possessing a perfectly periodic arrangement. The optical absorption experiments show that all compounds generate a very large blue shift in the absorption edge (1.0-2.0 eV) due to the strong QCE. More significantly, their band edge shift and optical properties can be tuned by changing the dimensionality of inorganic motifs as well as overall crystal structures. Raman studies reveal that not only do these structures have distinctly different vibrational signatures from those of the II-VI host semiconductors, but they also differ significantly from each other as a result of changes in dimensionality. The crystal structures of these nanocomposite materials have been characterized by single crystal and/or powder X-ray diffraction methods. [ZnTe(pda)] (1; pda = propanediamine) is composed of 1-D chains of [ZnTe] with pda chelating to Zn atoms. [ZnTe(N(2)H(4))] (2; N(2)H(4) = hydrazine) and [ZnTe(ma)] (3; ma = MeNH(2) = methylamine) are two-dimensional (2-D) layered structures containing [ZnTe] slabs and terminal hydrazine (2) or methylamine (3) molecules. The crystal structures of [CdSe(en)(0.5)] (4; en = ethylenediamine) and [CdSe(pda)(0.5)] (5) are 3-D networks containing [CdSe] slabs bridged by bidentate organic diamine molecules. Crystal data for 1: Orthorhombic, space group Pbcm, a = 9.997(2), b = 6.997(1), c = 10.332(2) A, Z = 4. For 2: Monoclinic, space group P2(1), a = 4.2222(6), b = 6.9057(9), c = 7.3031(10) A, beta = 98.92(8) degrees, Z = 2. For 3: Orthorhombic, Pbca, a = 7.179(1), b = 6.946(1), c = 18.913(4) A, Z = 8. For 4: Orthorhombic, Pbca, a = 7.0949(3), b = 6.795(3), c = 16.7212(8) A, Z = 8. For 5: Orthorhombic, Cmc2(1), a = 20.6660(12), b = 6.8900(4), c = 6.7513(4) A, Z = 8.     

The reaction between ZnO and molten Na2S2O7 or K2S2O7 forming Na2Zn(SO4)2 orK2Zn(SO4)2, studied by Raman spectroscopy and x-ray diffraction

Reactions between solid zinc oxide and molten sodium or potassium pyrosulfates at 500 degrees C are shown by Raman spectroscopy to be 1:1 reactions leading to solutions. By lowering the temperature of the solution melts, colorless crystals form. Raman spectra of the crystals are given and tentatively assigned. Crystal structures of the monoclinic salts at room temperature are given. Na(2)Zn(SO(4))(2): space group = P2/n (No. 13), Z = 8, a = 8.648(3) Angstroms, b = 10.323(3) Angstroms, c = 15.103(5) Angstroms, beta = 90.879(6) degrees, and wR(2) = 0.0945 for 2748 independent reflections. K(2)Zn(SO(4))(2): space group = P2(1)/n (No.14), Z = 4, a = 5.3582(11) Angstroms, b = 8.7653(18) Angstroms, c = 16.152(3) Angstroms, beta = 91.78(3) degrees , and wR(2) = 0.0758 for 1930 independent reflections. In both compounds, zinc is nearly perfectly trigonally bipyramidal, coordinated to five oxygen atoms, with Zn-O bond lengths ranging from 1.99 to 2.15 Angstroms, equatorial bonds being slightly shorter on the average. The O-Zn-O angles are approximately 90 degrees and 120 degrees . The sulfate groups connect adjacent Zn(2+) ions, forming complicated three-dimensional networks. All oxygen atoms belong to nearly perfect tetrahedral SO(4)(2-) groups, bound to zinc. No oxygen atom is terminally bound to zinc; all zinc oxygens are further connected to sulfur atoms (Zn-O-S bridging). In both structures, some oxygen atoms are uniquely bound to certain S atoms. The sulfate group tetrahedra have quite short (1.42-1.45 Angstroms) terminal S-O bonds in comparison to the longer (1.46-1.50 Angstroms) Zn-bridging S-O bonds. The Na(+) or K(+) ions adopt positions between the ZnO(5) hexahedra and the SO(4) tetrahedra, completing the three-dimensional network of the M(2)Zn(SO(4))(2) structures. Bond distances and angles compare well with literature values. Empirical correlations between S-O bond distances and average O-S-O bond angles follow a previously found trend.     

Synthesis and structural characterization of symmetrical closo-4,7-I2-1,2-C2B10H10 and [(CH3)3NH][nido-2,4-I2-7,8-C2B9H10

The boron-atom insertion reaction of nido-9,11-I(2)-7,8-C(2)B(9)H(9)(2-), with the HBCl(2):SMe(2) complex yields closo-4,7-I(2)-1,2-C(2)B(10)H(10), 1, in excellent yield. Although the two boron atoms (B3 and B6) nearest to the carbon atoms in 1 are equally available for attack by nucleophiles, the boron-degradation reaction of 1 with alkoxide ion occurs only at the B6 vertex, yielding regioselectively [(CH(3))(3)NH][nido-2,4-I(2)-7,8-C(2)B(9)H(10)], 2. The molecular structures of 1 and 2 have been determined by X-ray diffraction studies. Crystallographic data are as follows. For 1, monoclinic, space group P2(1)/n, a = 6.9199(19) Angstroms, b = 23.9560(7) Angstroms, c = 7.2870(2) Angstroms, beta = 94.081(4) degrees, V = 1204.9(6) Angstroms(3), Z = 4, rho(calcd) = 2.18 g cm(-3), R = 0.020, R(w) = 0.0610; for 2, orthorhombic, space group Pca2(1), a = 14.1141(7) Angstroms, b = 7.0276(4) Angstroms, c = 16.4602(9) Angstroms, V = 1632.7(15) Angstroms(3), Z = 4, rho(calcd) = 1.81 gcm(-3), R = 0.022, R(w) = 0.0623.     

New hydrothermal synthesis and structure of Th2(PO4)2(HPO4).H2O: the first structurally characterized thorium Hydrogenphosphate

Th(2)(PO(4))(2)(HPO(4)).H(2)O was synthesized under wet hydrothermal conditions starting from a mixture of H(3)PO(3) and Th(NO(3))(4).5H(2)O. The crystal structure was solved by powder X-ray diffraction data. The unit cell parameters are a = 6.7023(8) Angstroms, b = 7.0150(8) Angstroms, c = 11.184(1) Angstroms, beta = 107.242(4) degrees, space group P2(1), and Z = 2. The structure consists of layers of both thorium atoms and PO(4) groups, alternating with a layer formed by HPO(4) entities and water molecules. By thermal treatment, this compound turns into Th(4)(PO(4))(4)P(2)O(7), a ceramic already described in the field of the immobilization of tetravalent actinides.     

Crystal structures of two polymorphs of Ca3[Al2N4

Green transparent single crystals of alpha-Ca3[Al2N4] (monoclinic, P2(1)/c, No. 14, a = 957.2(3) pm, b = 580.2(3) pm, c = 956.3(5) pm, beta = 111.62(3) degrees; Z = 4) were obtained from reactions of mixtures of the representative metals with nitrogen above temperatures of 1000 degrees C. beta-Ca3[Al2N4] (monoclinic, C2/c, No. 15, a = 1060.6(2) pm, b = 826.0(2) pm, c = 551.7(1) pm, beta = 92.1(1) degrees; Z = 4) was formed as a byproduct of a reaction of calcium with alumina under nitrogen at T = 930 degrees C in form of colorless crystals. The crystal structures of the two polymorphs contain edge- and corner-sharing AlN4 tetrahedra, leading to different layered anionic partial structures: infinity 2[AlN2/2N2/3)2(AlNN2/2N1/3)6/3(12-)] in the alpha-phase and infinity 2[Al2N2N4/2(6-)] in the beta-polymorph.     

Metal-organic framework H-bonded like a polycatenane: coexistence of acyclic water trimer and nonamer

Pyridine-2,6-dicarboxylic acid and 1,2-di-4-pyridylethylene react hydrothermally with nickel(II) nitrate, forming a metal-organic framework that forms a polycatenane-like structure through H-bonding interactions between water molecules and carboxylate O atoms with void spaces. Discrete acyclic trimeric and nonameric water clusters occupy the voids in the structures. X-ray powder diffraction and X-ray structure analysis have been used to characterize this compound. Crystal data for 1 {(3dpeH(2))[Ni(pdc)(2)](3).15H(2)O}: monoclinic space group P2(1)/c, a = 24.730(5) Angstroms, b = 19.895(2) Angstroms, c = 17.257(4) Angstroms, beta = 104.832(5) degrees, V = 8208(4) Angstroms(3), Z = 4, R1 = 0.0429, wR2 = 0.1072, and S = 1.051.     

The dianion of 5-cyanoiminotetrazoline: C2N62-

Several salts (alkali, Pd(NH(3))(3), and (i)PrNH(2)) of 5-cyanoiminotetrazoline (C(2)N(6)(2-), 5-cyanoiminotetrazolinediide, CIT) were investigated. A full characterization by means of X-ray, Raman, NMR techniques, mass spectrometry, and elemental analysis is presented for the (i)()PrNH(2) (4), Cs (5), and Pd(NH(3))(3) (6) salts. The CIT dianion represents a nitrogen-rich binary CN dianion, and 5 forms monoclinic crystals (a = 7.345(2) Angstroms, b = 9.505(2) Angstroms, c = 10.198(2) Angstroms, beta = 92.12(3) degrees, space group P2(1)/n, Z = 4). DSC and in situ temperature-dependent X-ray diffraction measurements of the cesium salt 5 revealed an astonishing thermal stability accompanied by a reversible phase transition from the low-temperature alpha modification to the metastable beta modification at 253 degrees C. Above the melting point (334 degrees C), the cesium salt decomposes yielding cesium azide and cesium dicyanamide, which decomposes under further heating under release of nitrogen. The reaction of Cs(2)CIT with SO(2) resulted in the surprising formation of a new cesium salt with the 5-cyaniminotetrazoline-1-sulfonate dianion (Cs(2)CITSO(3).SO(2) (7)). 7 crystallizes in the monoclinic space group P2(1) with one SO(2) solvent molecule (a = 8.0080(2) Angstroms, b = 8.0183(2) Angstroms, c = 9.8986(3) Angstroms, beta = 108.619(1) degrees, Z = 2). The structure and bonding of the 10pi dianion are discussed on the basis B3LYP/aug-cc-pvTZ computations (MO, NBO), and the three-dimensional array of the cesium salts with respect to the Cs(delta) (+)-N(delta)(-) in 5 compared to the Cs(delta)(+)-N(delta)(-) and Cs(delta)(+)-O(delta)(-) in 7 is discussed. Due to the expected rich bonding modes of the CIT anions, the coordination chemistry with palladium was also studied, yielding monoclinic crystals of [Pd(CIT)(NH(3))(3)].H(2)O (6, a = 7.988(2) Angstroms, b = 8.375(2) Angstroms, c = 13.541(3) Angstroms, beta = 104.56 degrees, space group P2(1)/n, Z = 4). In the solid state, the complex is composed of dimers, showing two agostic interactions and an unusual close interplanar pi-pi stacking of the tetrazole moiety of the CIT ligand.     

A new type of single-helix coordination polymer with mixed ligands [M2(phen)2(e,a-cis-1,4-chdc)2(H2O)2]n (M=Co and Ni; phen=1,10-phenanthroline; chdc=cyclohexanedicarboxylate)

A new family of single-stranded helices coordination polymers with mixed ligands, [M2(phen)2(e,a-cis-1,4-chdc)2(H2O)2]n (1, M=Co; 2, M=Ni; chdc=cyclohexanedicarboxylic acid; phen=1,10-phenanthroline), were prepared under hydrothermal conditions and characterized by elemental analyses, IR spectra, TG analysis, and single-crystal X-ray diffraction analysis. X-ray crystal structural analyses reveal that 1 and 2 are isomorphic and belong to the monoclinic system. C40H36Co2N4O10, P2(1)/c, a=10.0566(5) A, b=8.8843(5) A, c=20.2912(14) A, beta=100.052(3) degrees, Z=2 for 1; and C40H36Ni2N4O10, P2(1)/c, a=9.8921(6) A, b=9.0151(4) A, c=20.1628(17) A, beta=100.31(2) degrees, Z=2 for 2. In the structures of 1 and 2, the 1,4-chdc ligand possesses only one kind of e,a-cis-conformation although there are both cis- and trans-conformations in the raw material. Two oxygen atoms of one carboxyl in 1,4-chdc ligand and another oxygen atom of contraposition carboxyl link adjacent Co or Ni atoms into an infinite 1-D zigzag chain. The most attractive structural feature of 1 and 2 is that they both exhibit an infinite chiral chainlike structure with 2(1) helices along the b axis. In addition, the right-handed and the left-handed chains are alternate. Meanwhile, the adjacent chains of 1 and 2 are linked via hydrogen bonds into 2-D network structures, which further form 3-D frameworks via pi-pi interactions of 1,10-phen.     

Synthesis, characterization, and electrochemical studies on [1.1]ferrocenophanes containing aluminum, gallium, and indium

The synthesis, characterization, structure, and electrochemistry of [1.1]ferrocenophanes, bridged by the heavier group 13 elements aluminum (1a), gallium (1b), and indium (1c), are described and discussed. Compounds 1a-c have been synthesized from dilithioferrocene and intramolecularly coordinated group 13 element dihalides Ar'EX(2) (Ar' = 2-(Me(2)NCH(2))C(6)H(4); EX(2) = AlCl(2), GaCl(2), InI(2)). Although the synthesis and characterization of 1a by single-crystal X-ray analysis has been described recently (Braunschweig, H.; Burschka, C.; Clentsmith, G. K. B.; Kupfer, T.; Radacki, K. Inorg. Chem. 2005, 44, 4906), compounds 1b and 1c are described for the first time. The galla (1b) and the inda (1c) [1.1]ferrocenophane have been characterized by single-crystal X-ray determination [1b: C(38)H(40)Fe(2)Ga(2)N(2), monoclinic, P2(1)/c, a = 10.3467(5) Angstroms, b = 11.6311(4) Angstroms, c = 14.0747(7) Angstroms, beta = 105.931(2) degrees, Z = 2; 1c: C(38)H(40)Fe(2)In(2)N(2), monoclinic, P2(1)/c, a = 10.5522(7) Angstroms, b = 11.8476(8) Angstroms, c = 13.9855(9) Angstroms, beta = 104.990(3) degrees, Z = 2]. All three compounds 1a-c are anti conformers with trans orientations of the two donating NMe(2) groups. For the [1.1]ferrocenophane 1a, an unprecedented fully reversible two-electron redox process was observed by cyclic voltammetry, whereas the corresponding Ga and In species exhibit a more conventional stepwise redox chemistry. According to the Robin-Day classification, 1a is a class I and 1b and 1c are class II species. In addition to the reversible processes, compound 1a shows an irreversible oxidation at higher voltages accompanied by adsorption processes. The irreversible adsorption process was investigated with an electrochemical quartz crystal microbalance (EQCM).     

Di- and tetranuclear metal complexes with phenoxo bridges: synthesis, structures, and photoluminescent and electroluminescent properties

Dinuclear and tetranuclear copper 2,6-bis(2-hydroxyphenyl)pyridine (H(2)L) complexes Cu2(L)2(py)2 (1) and Cu4(L)4(DMF) (2) were synthesized. The complexes 1 and 2 were characterized by elemental analyses, mass spectrometry, and single-crystal X-ray diffraction analyses. 1 crystallizes in the monoclinic space group P2(1)/n with a = 13.330(2) Angstroms, b = 9.361(1) Angstroms, c = 14.676(1) Angstroms, beta = 100.94(1) degrees, V = 1798.1(3) Angstroms(3), and Z = 2. 2 crystallizes in the monoclinic space group P2(1)/n with a = 13.360(1) Angstroms, b = 14.884(1) Angstroms, c = 15.462(2) Angstroms, beta = 97.50(4) degrees, V = 3048.4(1) Angstroms(3), and Z = 2. Tetranuclear zinc complex Zn4(L)4(py)4 (3) was prepared and characterized by X-ray diffraction. 3 crystallizes in the triclinic space group P with a = 13.770(1) Angstroms, b = 15.465(1) A, c = 16.409(2) Angstroms, alpha = 88.877(9) degrees, beta = 88.035(4) degrees, gamma = 82.956(3) degrees, V = 3465.6(5) Angstroms(3), and Z = 2. The di- and tetranuclear complexes 1-3contain phenoxo bridges. 1 is a dinuclear complex with two Cu(II) centers, two py ligands, and two L ligands, and each L ligand donates its pyridyl ring and one of the phenolate groups to one metal and shares the other phenolate group between both metals, affording a Cu(2)(mu-O)(2) core. 2, in contrast, is a tetranuclear complex with four Cu(II) centers and four L ligands. Two of the L ligands have the same coordination mode as 1, and the other two L ligands donate their pyridyl rings to one metal and share both phenolate groups between four metals, resulting in three four-membered Cu2(mu-O)2 rings, which joined each other and showed great distortion from planarity. 3 is a tetranuclear complex with four Zn(II) centers, four pyridine ligands, and four L ligands, and the L ligands have the same coordination modes as those of 2. Single-crystal X-ray analysis showed that hydrogen-bonding and pi-pi stacking interactions exist in complexes 1 and 2 resulting in two- and three-dimensional molecular arrangements, and the parallel arrangement of the ligand in the crystal of complex 3 resulted in a close inter- and intramolecular pi-pi interactions. Investigation of the crystals, as well as an amorphous thin film and powder of 3, by photoluminescence (PL) allowed the effect of the molecular packing on the emission properties to be elucidated. Furthermore, the electroluminescent (EL) properties of 3 were examined by fabricating a multilayer device with structure of [ITO/NPB/(ZnL)(n)/Alq3/LiF/Al] (NPB = N,N'-bis(alpha-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine, Alq3 = tris(8-hydroxyquinolinato)aluminum).     

Eight- and 16-membered cyanuric-sulfanuric ring systems: C2N4S2-->C2N3S ring contraction

Eight- and 16-membered cyanuric-sulfanuric ring systems of the type Ar2C2N4S2(O)2Ar'2 (3a, Ar = 4-BrC6H4, Ar' = Ph; 3b, Ar = 4-CF3C6H4, Ar' = Ph; 3c, Ar = 4-CF3C6H4, Ar' = 4-CH3C6H4) and Ar4C4N8S4(O)4Ar'4 (4b, Ar = 4-CF3C6H4, Ar' = Ph; 4c, Ar = 4-CH3C6H4, Ar' = Ph; 4d, Ar = 4-CF3C6H4, Ar' = 4-CH3C6H4), respectively, were prepared in good yields by the reaction of the corresponding sulfur(IV) systems with m-chloroperbenzoic acid. The X-ray structures of 3b, 3c.C7H14, 4b.CH2Cl2, 4c, and the S(IV) system Ar4C4N8S4Ar'4 (2c, Ar = 4-CH3C6H4, Ar' = Ph) were determined. Upon oxidation the two oxygen atoms in 3b and 3c.C7H14 adopt endo positions leading to a twist boat conformation for the C2N4S2 ring. The 16-membered C4N8S4 rings in 4b and 4c retain a cradle conformation upon oxidation. The S-N bond distances are ca. 0.06 A shorter in all the S(VI) systems compared to those in the corresponding S(IV) rings. The thermolysis of 3b at ca. 220 degrees C occurs primarily via loss of a sulfanuric group, NS(O)Ph, to give the six-membered ring (4-CF3C6H4)2C2N3S(O)Ph (6). The structure of 6 was confirmed by X-ray crystallography. Crystal data: 2c, triclinic, space group P1 with a = 13.917(2) A, b = 15.610(4) A, c = 13.491(3) A, alpha = 95.77(2) degrees, beta = 114.82(1) degrees, gamma = 76.21(2) degrees, V = 2583(1) A3, and Z = 2; 3b, monoclinic, space group P2(1)/a with a = 7.316(2) A, b = 29.508(5) A, c = 12.910(2) A, beta = 101.30(2) degrees, V = 2733(1) A3, and Z = 4; 3c.C7H14, triclinic, space group P1 with a = 12.849(4) A, b = 12.863(4) A, c = 12.610(7) A, alpha = 110.61(3) degrees, beta = 105.77(3) degrees, gamma = 62.77(2) degrees, V = 1719(1) A3, and Z = 2; 4b.CH2Cl2, triclinic, space group P1 with a = 12.647(3) A, b = 19.137(3) A, c = 12.550(2) A, alpha = 105.765(11) degrees, beta = 93.610(15) degrees, gamma = 88.877(16) degrees, V = 2917.2(9) A3, and Z = 2; 4c, orthorhombic, space group Pba2 with a = 22.657(2) A, b = 10.570(2) A, c = 10.664(3) A, alpha = beta = gamma = 90 degrees, V = 2554(1) A3, and Z = 2; 6, triclinic, space group P1 with a = 7.4667(8) A, b = 11.3406(12) A, c = 13.5470(14) A, alpha = 108.000(2) degrees, beta = 105.796(2) degrees, gamma = 94.300(2) degrees, V = 1033.8(2) A3, and Z = 2.     

Nickel(II) and zinc(II) dibenzoylmethanates: molecular and crystal structure, polymorphism, and guest- or temperature-induced oligomerization

Four forms of nickel(II) and two of zinc(II) dibenzoylmethanates have been isolated and characterized with powder and single-crystal X-ray diffraction analyses, differential scanning calorimetry, magnetic susceptibility measurements, and solid-state 13C cross-polarization/magic angle spinning NMR. Nickel dibenzoylmethanate, Ni(DBM)2 (DBM = PhCOCHCOPh-), forms three polymorphic forms (light-green, brown, and green) and a fourth clathrate form with guest benzene included. The light-green polymorph is metastable. Substituted benzenes induce recrystallization of the polymorph into a stable brown form (C30H22NiO4; a = 26.502(3) A, b = 5.774(1) A, c = 16.456(2) A, beta = 116.03(1) degrees; monoclinic, C2/c; Z = 4). Unlike the other forms, the brown form is diamagnetic and is comprised of monomers of the low-spin [Ni(DBM)2] complex. The Ni(II) is chelated by two DBM ligands in a square planar environment by four donor oxygen atoms. When heated, the brown form transforms to a green form which is stable above 202 degrees C (C90H66Ni3O12; a = 13.819(2) A, b = 16.252(2) A, c = 17.358(2) A, beta = 108.28(1) degrees; monoclinic, P2(1)/n; Z = 2). This polymorph is formed by van der Waals packing of trimers [Ni3(DBM)6] containing linear Ni3 clusters with an Ni-Ni distance of 2.81 A. The cluster is surrounded by six DBM ligands, providing a distorted octahedral environment about each Ni by six oxygen atoms. Benzene stabilizes the trimeric structure at room temperature, forming a [Ni3(DBM)6].2(benzene) inclusion compound (Ni-Ni distance of 2.83 A) with guest benzene molecules located in channels (C90H66Ni3O12 + 2(C6H6); a = 17.670(2) A, b = 20.945(3) A, c=11.209(2) A, beta = 102.57(1) degrees; monoclinic, P2(1)/c; Z = 2). Zinc dibenzoylmethanate has been prepared in two polymorphic forms. The monomeric form contains [Zn(DBM)2] molecules with the zinc center in a distorted tetrahedral environment of four oxygens from the two chelated DBMs (C30H22O4Zn; a = 10.288(2) A, b = 10.716(2) A, c = 12.243(2) A, alpha = 89.19(1) degrees, beta = 75.39(1) degrees, gamma = 64.18(1) degrees; triclinic, P1; Z = 2). Another, dimeric form contains [Zn2(DBM)4] species, with two zinc atoms separated by a distance of 3.14 A and each zinc coordinated by five oxygen atoms (C60H44O8Zn2; a = 25.792(3) A, b = 7.274(1) A, c = 24.307(2) A, beta = 90.58(1) degrees; monoclinic, C2/c; Z = 4). The polymorphic variety of the title complexes and the peculiarities of the Ni(II) and Zn(II) coordination environments are discussed in the context of using the complexes as precursors for new metal complex hosts.     

Rearrangement of molybdocene tetraoxotetrasulfide Cp2MoS4O4 to Give [(Cp2MoS2H)2](HSO4)2: a novel proton-stabilized molybdocene disulfide dimer

Cp(2)MoS(4), 1, in CH(2)Cl(2) undergoes extensive oxidation by m-CPBA at -78 degrees C to give a 1,1,4,4-tetroxide, 2 (59%). Tetraoxide 2 rearranges at room temperature to give an unusual sulfur-atom protonated molybdocene disulfide dimer [(Cp(2)MoS(2)H)(2)](HSO(4))(2), 3. Crystal data for 3 are P, a = 6.751(2) Angstroms, b = 9.865(4) Angstroms, c = 11.549(5) Angstroms, alpha = 109.95(3) degrees, beta = 96.11(3) degrees, gamma = 108.22(3) degrees, V = 666.9(4) Angstroms(3), and Z = 1. The dimer was also obtained directly when the oxidation was conducted at 0 degree C in DMF. Under basic conditions, the dimer is cleaved to give molybdocene disulfide Cp(2)MoS(2), while treatment of the latter with acid converts it to the dimer 3.     

New framework connectivity patterns in templated networks: the creatinine zinc phosphites C4N3OH7.ZnHPO3, C4N3OH7.Zn(H2O)HPO3, and (C4N3OH7)2.ZnHPO3.H2O

The syntheses, crystal structures, and properties of C(4)N(3)OH(7).ZnHPO(3), C(4)N(3)OH(7).Zn(H(2)O)HPO(3), and (C(4)N(3)OH(7))(2).ZnHPO(3).H(2)O are reported. These new creatinine zinc phosphites are built up from networks of vertex-sharing HPO(3) pseudopyramids and various types of ZnO(2)N(2), ZnO(3)N, and ZnO(2)N(H(2)O) tetrahedra, resulting in extended structures of different dimensionalities (as sheets, clusters, and chains, respectively). They demonstrate the structural effect of incorporating "terminal" (nonnetworking) Zn-N and Zn-OH(2) moieties into zinc centers. Crystal data: C(4)N(3)OH(7).ZnHPO(3), triclinic, P1 (No. 2), a = 8.9351(4) A, b = 9.5011(4) A, c = 9.9806(4) A, alpha = 87.451(1) degrees, beta = 85.686(1) degrees, gamma = 89.551(1) degrees, Z = 4; C(4)N(3)OH(7).Zn(H(2)O)HPO(3), monoclinic, P2(1)/c (No. 14), a = 10.1198(7) A, b = 7.2996(5) A, c = 13.7421(9) A, beta = 107.522(1) degrees, Z = 4; (C(4)N(3)OH(7))(2).ZnHPO(3).H(2)O, triclinic, P1 (No. 2), a = 10.7289(6) A, b = 10.9051(6)A, c = 13.9881(8) A, alpha = 89.508(1) degrees, beta = 74.995(1) degrees, gamma = 74.932(1) degrees, Z = 4.     

Protonation and methylation of an Anderson-type polyoxoanion [IMo6O24]5-

A series of protonated and methylated Anderson-type molybdoperiodates as well as the unprotonated [IMo6O24]5- have been synthesized and structurally characterized as tetra-n-butylammonium salts: [(n-C4H9)4N]5[IMo6O24] [monoclinic, space group C2/c, a = 33.6101(3) A, b = 15.2575(1) A, c = 24.0294(2) A, beta = 126.9569(3) degrees , Z = 4], [(n-C4H9)4N]4[IMo6O23(OH)] [monoclinic, space group P21/c, a = 9.5587(1) A, b = 24.1364(2) A, c = 18.2788(2) A, beta = 90.1562(5) degrees , Z = 2], [(n-C4H9)4N]3[IMo6O22(OH)2].2DMF [monoclinic, space group P21/a, a = 17.6105(4) A, b = 15.5432(5) A, c = 29.3316(9) A, beta = 91.475(3) degrees , Z = 4], [(n-C4H9)4N]4[IMo6O23(OMe)].3H2O [orthorhombic, space group Pbca, a = 17.0679(4) A, b = 25.6998(6) A, c = 20.7428(4) A, Z = 4], [(n-C4H9)4N]3[IMo6O22(OMe)2] [monoclinic, space group P21/n, a = 10.4009(1) A, b = 14.6658(3) A, c = 23.5395(4) A, beta = 100.324(1) degrees , Z = 2]. In all of these compounds, the [IMo6O24]5- anion is protonated or methylated selectively at O atoms shared by two Mo atoms. The results have also revealed that the protonated Anderson-type molybdoperiodates readily react with methanol in a very selective manner, while the unprotonated [IMo6O24]5- anion does not react with methanol under similar conditions.     

Three-, two-, and one-dimensional metal phosphonates based on [hydroxy(4-pyridyl)methyl]phosphonate: M{(4-C5H4N)CH(OH)PO3}(H2O) (M = Ni, Cd) and Gd{(4-C5H4N)CH(OH)P(OH)O2}3.6H2O

Based on the [hydroxy(4-pyridyl)methyl]phosphonate ligand, three compounds with formula Ni{(4-C(5)H(4)N)CH(OH)PO(3)}(H(2)O) (1), Cd{(4-C(5)H(4)N)CH(OH)PO(3)}(H(2)O) (2), and Gd{(4-C(5)H(4)N)CH(OH)P(OH)O(2)}(3).6H(2)O (3) have been synthesized under hydrothermal conditions. The crystal data for 1 are as follows: orthorhombic, space group Pbca, a = 8.7980(13) A, b = 10.1982(15) A, and c = 17.945(3) A. For 2 the crystal data are as follows: monoclinic, space group C2/c, a = 23.344(6) Angstroms, b = 5.2745(14) Angstroms, c = 16.571(4) Angstroms, and beta = 121.576(4) degrees. The crystal data for 3 are as follows: rhombohedral, space group R, a = 22.2714(16) Angstroms, b = 22.2714(16) Angstroms, and c = 9.8838(11) Angstroms. Compound 1 adopts a three-dimensional pillared layered structure in which the inorganic layers made up of corner-sharing {NiO(5)N} octahedra and {CPO(3)} tetrahedra are connected by pyridyl groups. A two-dimensional layer structure is found in compound 2, which contains alternating inorganic double chains and pyridyl rings. Compound 3 has a one-dimensional chain structure where the Gd atoms are triply bridged by O-P-O linkages. The pyridyl nitrogen atom in 3 remains uncoordinated and is involved in the interchain hydrogen bonds. Magnetic susceptibility studies of 1 and 3 reveal that weak ferromagnetic interactions are mediated between Ni(II) centers in compound 1. For compound 3, the behavior is principally paramagnetic.     

GeO2 natrolite-type infinite four and eight R-containing layers in a 2D pure-Ge framework: Ge3O5(OH)4[C2N2H10

A new two-dimensional framework germanate, Ge3O5(OH)4[C2N2H10] (denoted ICMM-8), with a 3:9 Ge:O ratio has been synthesized, using a mixture of pyridine, water, and ethanol as the solvent and 1,4-diazabicyclo[2.2.2]octane and ethylenediamine as the structure-directing agents, under solvothermal conditions. The structure was determined by single-crystal X-ray diffraction. In this new compound, the GeO2 natrolite-type infinite four and eight R-containing layers appears for the first time in a pure GeO2 framework. The total 2D structure is built up from SBU-6, four tetrahedra, and two octahedra. The hydroxyl groups occupy four positions of each octahedral germanium atom. The compound is characterized by IR spectra and TGA-DTA. Crystal data: Ge3O5(OH)4[C2N2H10], monoclinic space group P2(1)/c; a = 11.3570(9) Angstroms, b = 8.8819(7) Angstroms, c = 9.9200(8) Angstroms, beta = 90.710(1), V = 1000.6(1) Angstroms(3), Z = 4, R(1) = 0.044 (I > 2(I)), and wR(2) = 0.1051 (all data).     

Syntheses,structures, and properties of the bis(cyclopentadienyl) rare-earth imidodiphosphinochalocogenido compounds Cp2Ln[N(QPPh2)2] (Ln = La,Gd, Er,or Yb for Q = Se; Ln = Yb for Q = S)

The compounds Cp2Ln[N(QPPh2)2] (Ln = La (1), Gd (2), Er (3), or Yb (4) for Q = Se, Ln = Yb (5) for Q = S) have been synthesized from the corresponding rare-earth tris(cyclopentadienyl) compound and H[N(QPPh2)2]. The structures of compounds 1, 2, 3, and 5, as determined by X-ray crystallography, consist of a Cp2Ln fragment, coordinated eta 3 through two chalcogen atoms and an N atom of the imidodiphosphinochalcogenido ligand [N(QPPh2)2]-. In compound 4, the Cp2Yb moiety is coordinated eta 2 through the two Se atoms of the [N(SePPh2)2]-ligand. 31P and 77Se (for 1) NMR spectroscopies lend insight into the solution nature of these species. Crystal data: 1, C34H30LaNP2Se2, triclinic, P1, a = 9.7959(10) A, b = 12.4134(13) A, c = 13.9077(14) A, alpha = 88.106(2) degrees, beta = 88.327(2) degrees, gamma = 68.481(2) degrees, V = 1572.2(3) A3, T = 153 K, Z = 2, and R1(F) = 0.0257 for the 5947 reflections with I > .2 sigma(I); 2, C34H30GdNP2Se2, triclinic, P1, a = 9.7130(14) A, b = 12.2659(17) A, c = 13.953(2) A, alpha = 88.062(2) degrees, beta = 87.613(2) degrees, gamma = 69.041(2) degrees, V = 1550.7(4) A3, T = 153 K, Z = 2, and R1(F) = 0.0323 for the 5064 reflections with I > 2 sigma(I); 3, C34H30ErNP2Se2, triclinic, P1, a = 9.704(2) A, b = 12.222(3) A, c = 13.980(4) A, alpha = 88.230(4) degrees, beta = 87.487(4) degees, gamma = 69.107(4) degrees, V = 1547.4(7) A3, T = 153 K, Z = 2, and R1(F) = 0.0278 for the 6377 reflections with I > 2 sigma(I); 4, C34H30NP2Se2Yb.C4H8O, triclinic, P1, a = 12.087(4) A, b = 12.429(4) A, c = 23.990(7) A, alpha = 89.406(5) degrees, beta = 86.368(5) degrees, gamma = 81.664(5) degrees, V = 3558.8(18) A3, T = 153 K, Z = 4, and R1(F) = 0.0321 for the 11,883 reflections with I > 2 sigma(I); and 5, C34H30NP2S2Yb, monoclinic, P21/n, a = 13.8799(18) A, b = 12.6747(16) A, c = 17.180(2) A, beta = 91.102(3) degrees, V = 3021.8(7) A3, T = 153 K, Z = 4, and R1(F) = 0.0218 for the 6698 reflections with I > 2 sigma(I).     

Zinc diphosphonates templated by organic amines: syntheses and characterizations of [NH3(CH2)2NH3]Zn(hedpH2)2*2H2O and [NH3(CH2)nNH3(CH2)nNH3]Zn2(hedpH)2*2H2O (n=4,5,6) (hedp=1-hydroxyethylidenediphophonate)

Four new zinc diphosphonate compounds with formulas [NH(3)(CH(2))(2)NH(3)]Zn(hedpH(2))(2).2H(2)O, 1, [NH(3)(CH(2))(n)()NH(3)]Zn(2)(hedpH)(2).2H(2)O, (n = 4, 2; n = 5, 3; n = 6, 4) (hedp = 1-hydroxyethylidenediphosphonate) have been synthesized under hydrothermal conditions at 110 degrees C and in the presence of alkylenediamines NH(2)(CH(2))(n)()NH(2) (n = 2, 4, 5, 6). Crystallographic data for 1: monoclinic, space group C2/c, a = 24.7422(15), b = 5.2889(2), c = 16.0338(2) A, beta = 117.903(1) degrees, V = 1856.17(18) A(3), Z = 4; 2: monoclinic, space group P2(1)/n, a = 5.4970(3), b = 12.1041(6), c = 16.2814(12) A, beta = 98.619(5) degrees, V = 1071.07(11) A(3), Z = 2; 3: monoclinic, space group P2(1)/n, a = 5.5251(2), b = 12.5968(3), c = 16.1705(5) A, beta = 99.182(1) degrees, V = 1111.02(6) A(3), Z = 2; 4: triclinic, space group P-1, a = 5.4785(2), b = 14.1940(5), c = 16.0682(6) A, alpha = 81.982(2) degrees, beta = 89.435(2) degrees, gamma = 79.679(2) degrees, V = 1217.11(8) A(3), Z = 2. In compound 1, two of the phosphonate oxygens are protonated. The metal ions are bridged by the hedpH(2)(2-) groups through three of the remaining four phosphonate oxygens, forming a one-dimensional infinite chain. The protonated ethylenediamines locate between the chains in the lattice. In compounds 2-4, only one phosphonate oxygen is protonated. Compounds 2 and 3 have a similar three-dimensional open-network structure composed of [Zn(2)(hedpH)(2)](n) double chains with strong hydrogen bonding interactions between them, thus generating channels along the [100] direction. The protonated diamines and water molecules reside in the channels. Compound 4 contains two types of [Zn(2)(hedpH)(2)](n) double chains which are held together by strong hydrogen bonds, forming a two-dimensional network. The interlayer spaces are occupied by the [NH(3)(CH(2))(6)NH(3)](2+) cations and water molecules. The significant difference between structures 2-4 is also featured by the coordination geometries of the zinc atoms. The geometries of those in 2 can be described as distorted octahedral, and those in 3 as distorted square pyramidal. In 4, two independent zinc atoms are found, each with a distorted octahedral and a tetrahedral geometry, respectively.