Influence of hydrogen bonding on the assembly of six-membered vanadium borophosphate cluster anions: synthesis and structures of (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12](6)10H2O, (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12](6)17H2O, and (NH4)3(C4H14N2)4 5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O

Three new strontium vanadium borophosphate compounds, (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O (Sr-VBPO1) (1), (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O (Sr-VBPO2) (2), and (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O (Sr-VBPO3) (3) have been synthesized by interdiffusion methods in the presence of diprotonated ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane. Compound 1 has a chain structure, whereas 2 and 3 have layered structures with different arrangements of [(NH4) [symbol: see text] [V2P2BO12]6] cluster anions within the layers. Crystal data: (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 21.552(1) A, b = 27.694(2) A, c = 20.552(1) A, beta = 113.650(1) degrees, Z = 4; (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O, monoclinic, space group I2/m (no. 12), a = 15.7618(9) A, b = 16.4821(9) A, c = 21.112(1) A, beta = 107.473(1) degrees, Z = 2; (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4] [V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 39.364(2) A, b = 14.0924(7) A, c = 25.342(1) A, beta = 121.259(1) degrees, Z = 4. The differences in the three structures arise from the different steric requirements of the amines that lead to different amine-cluster hydrogen bonds.     

Inclusion Compounds of Thiourea and Peralkylated Ammonium Salts. Part IV. Hydrogen-Bonded Host Lattices Built of Thiourea and Formate Ions

New inclusion complexes(C2H5)4N+HCO2-·(NH2)2CS·H2O (1),[(C2H5)4N]2+[(HCO2)2H]-(HCO2-)·2(NH2)2CS(2), (n-C3H7)4N+HCO2-·3(NH2)2CS·H2O (3)and (n-C4H9)4N+[(HCO2)2H]-·2(NH2)2CS(4) have been prepared and characterized by X-ray crystallography. Crystal data, MoK radiation: 1, space group P21/c, a = 7.199(2), b = 16.851(2),c = 13.044(2) Å, = 100.13(2)°, Z = 4, and RF = 0.065 for 1011 observed data; 2, space group Pca21, a = 25.803(5), b = 7.190(2), c = 17.394(2) Å, Z = 4, and RF= 0.073 for 1515 observed data; 3, space group P21/n, a = 8.533(2), b = 9.423(5), c = 33.517(7) Å, = 90.44(2)°, Z = 4, and RF = 0.052 for 2521 observed data; 4, space group Pbca, a = 17.389(3), b = 16.622(2),c = 20.199(3) Å, Z = 8, and RF = 0.056for 1910 observed data. In both 1 and 2 the tetraethylammonium ions are sandwiched between puckered layers, which are constructed by the cross-linkage of a parallel arrangement of infinite chains. In 1 each chain is composed of twisted(thiourea–formate)2 tetramers bridged by water molecules, whereas in 2 it comprises an alternate arrangement of thiourea dimers and protonated formate trimers each formed by the linkage of a hydrogen diformate ion, [(HCO2)2H]-, to a formate ion via} a C–-H·sO hydrogen bond. In compound 3 two independent thiourea molecules are used to construct a hydrogen-bonded puckered layer normal to thec axis, whereas the remaining thiourea molecule, together with the formate ion and water molecule, generate another puckered layer that is parallel to the first one. Hydrogen bonding between these two types of layers gives rise to a network containing channels running parallel to the [100] direction, and the cations are stacked regularly within each column. In the crystal structure of 4, the thiourea molecules form hydrogen-bonded zigzag ribbons running parallel to the b axis, which are cross-linked by the dimeric formate moieties [(HCO2)2H]- to form a puckered layer, and the(n-C4H9)N+ cations occupy the space between adjacent layers.     

Synthesis and Crystal Structure of o-Methylisourea Hydrosulfate

l INTRODUCTION As an important and capital intermediate of chemi- cal engineering, medicine and pesticide, o-methyli- sourea today is mainly used to synthesize fluoracil antitumor drugs, pesticides and polyantibacterials. According to the applications and syntheses, o- methylisourea is usually prepared as its salts and es- ters, such as o-methylisourea hydrosulfate, o-me- thylisourea sulfate, o-methylisourea acetate, o-methy- lisourea formate, and so on, since o-methylisourea is unstable.…     

Structure of Metal Aluminophosphates:Al9-xMxP12O48(TREN)4·yNH4·zH2O[TREN=N(CH2CH2NH3)Hm, M=Mn, Co]

Two large-pore metal-doped aluminophosphates, Mn4Al5(PO4)12[N(C2H4NH3)3]3[N(C2H4NH3)2·(C2H4NH2)](NH4)2·14H2O(Mn4-NJU) and Co4Al5(PO4)12[N(C2H4NH3)3][N(C2H4NH3)2(C2H4NH2)]3·(NH4)4·13H2O(Co4-NJU), which have the same open framework structures, were hydrothermally synthesized. The structures of these compounds consist of TO4 tetrahedra, which are linked together by corner-sharing to form an open framework with unique intersecting twelve-membered ring channels in three dimensions. The compounds crystallize in cubic space group I(-4)3m with a=1.6795(2) nm and V=4.7374(9) nm3 for Mn4-NJU, and a=1.67372(19) nm and V=4.6887(9) nm3 for Co4-NJU, respectively. Single crystal structure analyses show that the protruding O atoms of the frameworks of the compounds are linked to protonated 4-(2-aminoethyl)diethylenetriamine(TREN, C6H18N4) ions in the windows by means of hydrogen-bonding under the hydrothermal condition. It is also found that the components inside the super cages of the compounds are changeable, and the metal ions M2 (M=Mn, Co) and Al3 disorderedly occupy the same crystallographic positions.     

Carbonate and oxalate dianions as prolific hydrogen-bond acceptors in supramolecular assembly

In the new inclusion compound [(C2H5)4N+]2 x CO3(2-) x 7(NH2)2CS, the carbonate ion is surrounded by twelve convergent NH donor groups from six thiourea molecules to form a hydrogen-bonded aggregate shaped like two concave three-leaved propellers sharing a common core, whereas in [(n-C3H7)4N+]2 x C2O4(2-) x 4(NH2)2CS the oxalate ion serves as a hub for binding four thiourea molecules to generate a cross-shaped structural motif.     

CS2N3(-)-containing pseudohalide species: an experimental and theoretical study

The first structural reports of anhydrous salts containing the CS2N3 moiety are presented. The new M(+)CS2N3- species (M = NH4 (1), (CH3)4N (2), Cs (3), K (4)) were characterized by vibrational spectroscopy (IR, Raman), as well as multinuclear NMR spectroscopy (1H, 13C, 14N NMR). Moreover, the solid-state structures of NH4CS2N3 (1) [orthorhombic, Pbca, a = 10.6787(1) A, b = 6.8762(1) A, c = 15.2174(2) A, V = 1117.40(2) A3, Z = 8] and (H4C)4NCS2N3 (2) [monoclinic, P2(1)/m, a = 5.9011(1) A, b = 7.3565(2) A, c = 10.9474(3) A, beta = 91.428(1) degrees, V = 475.09(2) A3, Z = 2] were determined using X-ray diffraction techniques. The covalent compound CH3CS2N3 (5) was prepared by the reaction of methyl iodide with sodium azidodithiocarbonate and was characterized by vibrational spectroscopy (IR, Raman), multinuclear NMR spectroscopy (1H, 13C, 14N), and X-ray diffraction techniques [monoclinic, P2(1)/m, a = 5.544(1) A, b = 6.4792(7) A, c = 7.629(1) A, beta = 105.53(2) degrees, V = 264.06(7) A3, Z = 2]. Furthermore, the gas-phase structure of 5 was calculated (MPW1PW91/cc-pVTZ) and found to be in very good agreement with the experimentally determined structure. Improved synthetic routes for the recently reported dipseudohalogen (CS2N3)2 and interpseudohalogen CS2N3CN (6) are described, and the calculated gas-phase structure of 6 was compared with the experimentally determined structure (X-ray). The vibrational spectra of 6 and HCS2N3 (7) are also reported. Furthermore, several plausible isomers for 7 were calculated in an attempt to rationalize the experimentally observed structure which has N-H and not S-H connectivity. The lowest energy isomer for 7 is in agreement with the experimentally observed structure, and the Br?nsted acidity was calculated at the MPW1PW91/cc-pVTZ level of theory. The unknown CSe2N3- anion (8) was also investigated both theoretically and experimentally, and the structure and vibrational data for the unknown CTe2N3- anion (9) were investigated by quantum-chemical calculations using a quasi-relativistic pseudopotential for Te (ECP46MWB) and a cc-pVTZ basis set for C and N. The gas-phase structure of 9 is predicted to be that of a five-membered ring in analogy to the sulfur and selenium analogues.     

Synthesis and Structural Characterization of a New Polyoxovanadium Borate: (H3NCH2CH2NH3)4[(VO)6(B10O22)2]·(H3O)7

The title compound (H3NCH2CH2NH3)4[(VO)6(B10O22)2](H3O)7 1 has been synthe- sized by the hydrothermal method and determined by X-ray crystallography.Crystallographic data: monoclinic, space group C2/c, a = 20.250(4), b = 13.448(3), c = 21.655(4) (A), β = 97.05(3)°, Mr = 851.74 (C4H30.5B10N4O28.5V3), V = 5852(2) (A)3, Z = 8, Dc = 1.933 g/cm3, μ = 1.057 mm-1, F(000) = 3436, R = 0.0500 and wR = 0.1442 for 4511 observed reflections with I > 2δ(I).The structure con- sists of [(VO)6(B10O22)2]15- cluster anions that have a central band of six trans-edge-sharing VO5 square pyramids capped by two [B10O22]14- polyborate ligands.Other characterizations are also describ- ed by elemental analysis, IR spectrum and thermal analysis.     

Synthesis and Structural Characterization of a New Polyoxovanadium Borate: (H_3NCH_2CH_2NH_3)_4[(VO)_6(B_(10)O_(22))_2]·(H_3O)_7

1 INTRODUCTION Transition metal oxide clusters and their deriva- tives offer an unmatched variety of structural motifs and wide ranging applications in several areas, such as analytical chemistry, materials science and cataly- sis, nanotechnology, chemical sensing, environmental decontamination, biochemical and geochemical pro- cesses, and medicine[1～3]. Polyoxovanadates or vana- dium oxide clusters constitute an important subclass of polyoxometalates and have been studied exten- sively.…     

A hydrothermal investigation of the 1/2V2O5-H2C2O4/H3PO4/NH4OH system: synthesis and structures of (NH4)VOPO(4).1.5H2O, (NH4)0.5VOPO(4).1.5H2O, (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2](2).3H2O, and (NH4)2[VO(HPO4)]2(C2O4).5H2O

The 1/2V2O5-H2C2O4/H3PO4/NH4OH system was investigated using hydrothermal techniques. Four new phases, (NH4)VOPO(4).1.5H2O (1), (NH4)0.5VOPO(4).1.5H2O (2), (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O (3), and (NH4)2[VO(HPO4)]2(C2O4).H2O (4), have been prepared and structurally characterized. Compounds 1 and 2 have layered structures closely related to VOPO(4).2H2O and A0.5VOPO4.yH2O (A = mono- or divalent metals), whereas 3 has a 3D open-framework structure. Compound 4 has a layered structure and contains both oxalate and phosphate anions coordinated to vanadium cations. Crystal data: (NH4)VOPO(4).1.5H2O, tetragonal (I), space group I4/mmm (No. 139), a = 6.3160(5) A, c = 13.540(2) A, Z = 4; (NH4)0.5VOPO(4).1.5H2O, monoclinic, space group P2(1)/m (No. 11), a = 6.9669(6) A, b = 17.663(2) A, c = 8.9304(8) A, beta = 105.347(1) degrees, Z = 8; (NH4)2[VO(H2O)3]2[VO(H2O)][VO(PO4)2]2.3H2O, triclinic, space group P1 (No. 2), a = 10.2523(9) A, b = 12.263(1) A, c = 12.362(1) A, alpha = 69.041(2) degrees, beta = 65.653(2) degrees, gamma = 87.789(2) degrees, Z = 2; (NH4)2[VO(HPO4)]2(C2O4).5H2O, monoclinic (C), space group C2/m (No. 12), a = 17.735(2) A, b = 6.4180(6) A, c = 22.839(2) A, beta = 102.017(2) degrees, Z = 6.     

Hydrothermal Synthesis and Crystal Structure of a Novel Polymolybdate with Two Kinds of Organonitrogen Ligands

A novel inorganic-organic compound (C4N2H12)(C2N2H10)2[Mo5P2O23] (1) has been synthesized by the reaction of (NH4)2MoO4, H3PO4, C2N2H8 (ethylenediaminium), C4N2H10·6H2O (piperazine hexahydrate) and water in aqueous solution under mild hydrothermal conditions. Single-crystal X-ray analysis reveals that the title compound is crystallized in the triclinic system, space group P1 with a = 9.258(19), b = 9.382(19), c = 17.681(4), α = 76.28(3), β = 84.48(3), γ = 70.82(3)o, V = 1408.9(6)3, Mr = 1122.04, Z = 2, Dc = 2.645 g/cm3, μ = 2.384 mm-1, F(000) = 1092.0, the final R = 0.0391, wR = 0.1185 and S = 1.006 for 6169 observed reflections with I > 2σ(I). The crystal packing is stabilized by intra- and intermolecular N-H···O hydrogen bonds to form an infinite 3D network.     

12-钼磷酸四丁基铵杂多蓝的光化学合成表征与晶体结构

用450W高压汞灯照射H3PMo12O40·5H2O和（Bu4N）Br（TBA）的DMF（N,N-二甲基甲酰胺）溶液,合成了12-钼磷酸四丁基铵杂多蓝（Bu4N）4[PMo12O40]·2DMF·H2O,用元素分析,IR,固体漫反射电子光谱,ESR,XPS和CV等进行了表征。晶体结构分析表明,标题化合物属单斜晶系,空间群P21/c,晶胞参数a=14.124（3）,b=17.481（4）,c=22.744（5）A,β=101.66（3）°,V=5500（2）A3,C70H160Mo12N6O43P,Mr=2956.29,Z=2,Dc=1.785g/cm3,F（000）=2970,μ（MoKα）=1.412mm-1,R=0.0638,wR=0.1975。标题化合物是由4个四丁基铵阳离子、1个12-钼磷混合价杂多阴离子[PMo12O40]4-、2个DMF分子和1个水分子构成。     

The First Example of a Supramolecular Structure Containing [2-（1H-Pyrazol-3-yl）-pyridine] Complex and both α- and β-Octamolybdates

The title compound, [Ni（C8N3H7）3]4[Mo8O26]2·6H2O 1, has been synthesized from the reaction of 2-（1H-pyrazol-3-yl）-pyridine （L） with （NH4）2MoO4·2H2O and NiCl2·6H2O. Elemental analysis, IR, UV spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the compound. Crystal data： C96H96Mo16N36Ni4O58, Mr = 4451.97, monoclinic system, space group P21/n, a = 20.846（5）, b = 14.825（5）, c = 23.122（5） A ,β= 91.594（5）°, V = 7143（3）A^3, Z = 2, F（000） = 4344, Dc = 2.070 g/cm^3,μ = 1.968 mm^-1, R = 0.0452 and wR = 0.1056 for 17102 independent reflections （Rint = 0.0442） and 11074 observed reflections （I 〉 2σ（I））. Structural analysis indicates that two kinds of octamolybdates （[α-Mo8026]^4- and [β-Mo8026]^4-） co-exist in the compound. This is the first example of a supramolecular structure containing L complex as well as both α- and β-octamolybdate clusters.     

Synthesis and characterization of uranyl compounds with iminodiacetate and oxydiacetate displaying variable denticity

Eight uranyl compounds containing the dicarboxylate ligands iminodiacetate (IDA) or oxydiacetate (ODA) have been characterized in the solid state. The published polymeric structures for [UO(2)(C(4)H(6)NO(4))(2)] and [UO(2)(C(4)H(4)O(5))](n) have been confirmed, while Ba[UO(2)(C(4)H(5)NO(4))(2)] x 3H(2)O, [(CH(3))(2)NH(CH(2))(2)NH(CH(3))(2)][UO(2)(C(4)H(4)O(5))(2)] [orthorhombic space group Pnma, a = 10.996(5) A, b = 21.42(1) A, c = 8.700(3) A, Z = 4], and [C(2)H(5)NH(2)(CH(2))(2)NH(2)C(2)H(5)][UO(2)(C(4)H(4)O(5))(2)] [monoclinic space group P2(1)/n, a = 6.857(3) A, b = 9.209(5) A, c = 16.410(7) A, beta = 91.69(3), Z = 2] contain monomeric anions. The distance from the uranium atom to the central heteroatom (O or N) in the ligand varies. Crystallographic study shows that U-heteroatom (O/N) distances fall into two groups, one 2.6-2.7 A in length and one 3.1-3.2 A, the latter implying no bonding interaction. By contrast, EXAFS analysis of bulk samples suggests that either a long U-heteroatom (O/N) distance (2.9 A) or a range of distances may be present. Three possible structural types, two symmetric and one asymmetric, are identified on the basis of these results and on solid-state (13)C NMR spectroscopy. The two ligands in the complex can be 1,4,7-tridentate, giving five-membered rings, or 1,7-bidentate, to form an eight-membered ring. (C(4)H(12)N(2))[(UO(2))(2)(C(4)H(5)NO(4))(2)(OH)(2)] x 8H(2)O [monoclinic space group P2(1)/a, a = 7.955(9) A, b = 24.050(8) A, c = 8.223(6) A, beta = 112.24(6), Z = 2], (C(2)H(10)N(2))[(UO(2))(2)(C(4)H(5)NO(4))(2)(OH)(2)] x 4H(2)O, and (C(6)H(13)N(4))(2)[(UO(2))(2)(C(4)H(4)O(5))(2)(OH)(2)] x 2H(2)O [monoclinic space group C2/m, a = 19.024(9) A, b = 7.462(4) A, c = 2.467(6) A, beta = 107.75(4), Z = 4] have a dimeric structure with two capping tridentate ligands and two mu(2)-hydroxo bridges, giving edge-sharing pentagonal bipyramids.     

Building unit and topological evolution in the hydrothermal DABCO-U-F system

Compounds NDUF-1 ([C(6)H(14)N(2)](UO(2))(2)F(6); P2(1)/c, a = 6.9797(15) A, b = 8.3767(15) A, c = 23.760(5) A, beta = 91.068(4) degrees, V = 1388.9(5) A(3), Z = 4), NDUF-2 ([C(6)H(14)N(2)](2)(UO(2))(2)F(5)UF(7).H(2)O), NDUF-3 ((NH(4))(7)U(6)F(31); R3, a = 15.4106(8) A, c = 10.8142(8) A, V = 2224.1(2) A(3), Z = 3), and NDUF-4 ([NH(4)]U(3)F(13)) have been synthesized hydrothermally from fixed composition reactant mixtures over variable time periods [DABCO (C(6)H(12)N(2)), UO(2)(NO(3))(2).6H(2)O, HF, and H(2)O; 2-14 days]. Observed is a systematic evolution of the structural building units within these materials from the UO(2)F(5) pentagonal bipyramid in NDUF-1 and -2 to the UF(8) trigonal prism in NDUF-2 and finally to the UF(9) polyhedron in NDUF-3 and -4 as a function of reaction time. Coupled to this coordination change is a reduction of U(VI) to U(IV) as well as a breakdown of the organic structure-directing agent from DABCO to NH(4)(+). These processes contribute to a structural transition from layered topologies (NDUF-1) to chain (NDUF-2), back to layered (NDUF-3), and ultimately to framework (NDUF-4) connectivities. The synthesis conditions, crystal structures, and possible transformation mechanisms within this system are presented.     

Hydrothermal Syntheses and Structural Characterization of Layered Vanadium Oxides Incorporating Organic Cations: alpha-, beta-(H(3)N(CH(2))(2)NH(3))[V(4)O(10)] and alpha-, beta-(H(2)N(C(2)H(4))(2)NH(2))[V(4)O(10)

Four new layered mixed-valence vanadium oxides, which contain interlamellar organic cations, alpha-(H(3)N(CH(2))(2)NH(3))[V(4)O(10)] (1a), beta-(H(3)N(CH(2))(2)NH(3))[V(4)O(10)] (1b), alpha-(H(2)N(C(2)H(4))(2)NH(2))[V(4)O(10)] (2a), and beta-(H(2)N(C(2)H(4))(2)NH(2))[V(4)O(10)] (2b), have been prepared under hydrothermal conditions and their single-crystal structures determined: 1a, triclinic, space group P&onemacr;, a = 6.602(2) ?, b = 7.638(2) ?, c = 5.984(2) ?, alpha = 109.55(3) degrees, beta = 104.749(2) degrees, gamma = 82.31(3) degrees, Z = 1; 1b, triclinic, P&onemacr;, a = 6.387(1) ?, b = 7.456(2) ?, c = 6.244(2) ?, alpha = 99.89(2) degrees, beta = 102.91(2) degrees, gamma = 78.74(2) degrees, Z = 1; 2a, triclinic, P&onemacr;, a = 6.3958(5) ?, b = 8.182(1) ?, c = 6.3715(7) ?, alpha = 105.913(9) degrees, beta = 104.030(8) degrees, gamma = 94.495(8) degrees, Z = 1; 2b, monoclinic, space group P2(1)/n, a = 9.360(2) ?, b = 6.425(3) ?, c = 10.391(2) ?, beta = 105.83(1) degrees, Z = 2. All four of the compounds contain mixed-valence V(5+)/V(4+) vanadium oxide layers constructed from V(5+)O(4) tetrahedra and pairs of edge-sharing V(4+)O(5) square pyramids with protonated organic amines occupying the interlayer space.     

含有十二元环交叉孔道的新颖亚磷酸铟[In4(HPO3)7(H2O)3](NH3CH2CH2NH3)·(H2O)的水热合成与表征

在含有HF的体系中, 用乙二胺作模板剂, 通过水热方法合成了一个新的三维亚磷酸铟[In4(HPO3)7(H2O)3](NH3CH2CH2NH3)·(H2O), 并对其进行了红外光谱、热重、ICP和CHN元素分析等表征. 单晶X射线衍射分析结果表明, 该化合物属于三方晶系, P3空间群, 晶胞参数a=1.37883(7) nm, c=0.93450(9) nm, V=1.53862(2) nm3, Z=2, Dc=2.489 Mg/m3, 最终一致性因子R1[I >2σ(I)]=0.0526, wR2[I>2σ(I)]=0.1328, GOF=1.082. 其结构中的InO6八面体、InO5(H2O)八面体和HPO3假四面体通过O原子共顶点连接, 分别沿a, b轴方向形成含有十二元环的交叉孔道, 客体水分子和双质子化的乙二胺分子存在于孔道中.     

New light on an old story: formation of melam during thermal condensation of melamine

We report on the existence and formation of the carbon nitride precursor melam (H(2)N)(2)(C(3)N(3))NH(C(3)N(3))(NH(2))(2), thereby clarifying one of the last unresolved issues posed by the complex thermal condensation of melamine C(3)N(3)(NH(2))(3). Experimental proof is put forward that melam is a direct condensation product of melamine, but can be detected only in small amounts under special reaction conditions owing to its rapid transformation into melem. The coexistence of melamine and melem during thermal condensation yields two adduct phases with distinct compositions [C(3)N(3)(NH(2))(3)](2)[C(6)N(7)(NH(2))(3)] and [C(3)N(3)(NH(2))(3)][C(6)N(7)(NH(2))(3)](2). They may be considered as co-crystallizates of melamine and melem and can be isolated as intermediates between 590 and 650 K prior to the formation of single-phase melem C(6)N(7)(NH(2))(3). Melam (C2/c, a=1811.0(4), b=1086.7(2), c=1398.4(3) pm, beta=96.31(3) degrees, V=2735.3(9)x10(6) pm(3), T=130 K) adopts a ditriazinylamine-type structure with a twisted conformation about the bridging NH moiety and transforms into melem around 640 K. Two compounds deriving from melam have been synthesized by solution and solid-state reactions. The salt melamium diperchlorate C(6)N(11)H(11)(ClO(4))(2).2H(2)O (C2/c, a=1747.8(4), b=1148.2(2), c=993.6(2) pm, beta=118.79(3) degrees, V=1747.4(6)x10(6) pm(3), T=130 K) crystallizes as a dihydrate and exhibits a doubly protonated, planar melam core. In the neutral complex Zn[C(6)N(11)H(9)]Cl(2) (P2(1)/c, a=743.00(15), b=2233.2(5), c=762.5(2) pm, beta=99.86(3) degrees, V=1246.5(4)x10(6) pm(3), T=200 K), melam acts as a symmetrically bent bidentate ligand, which is coordinated to the Lewis acid Zn-site through two ring nitrogen atoms.     

Tautomerization of methyldiazene to formaldehyde-hydrazone in ruthenium and osmium complexes

Mixed-ligand hydrazine complexes [M(CO)(RNHNH2)P4](BPh4)2 (1, 2) [M = Ru, Os; R = H, CH3, C6H5; P = P(OEt)3] with carbonyl and triethyl phosphite were prepared by allowing hydride [MH(CO)P4]BPh4 species to react first with HBF4.Et2O and then with hydrazines. Depending on the nature of the hydrazine ligand, the oxidation of [M(CO)(RNHNH2)P4](BPh4)2 derivatives with Pb(OAc)4 at -30 C gives acetate [M(kappa1-OCOCH3)(CO)P4]BPh4 (3a), phenyldiazene [M(CO)(C6H5N=NH)P4](BPh4)2 (3c, 4c), and methyldiazene [M(CO)(CH3N=NH)P4](BPh4)2 (3b, 4b) derivatives. Methyldiazene complexes 3b and 4b undergo base-catalyzed tautomerization of the CH3N=NH ligand to formaldehyde-hydrazone NH2N=CH2, giving the [M(CO)(NH2N=CH2)P4](BPh4)2 (5, 6) derivatives. Complexes 5 and 6 were characterized spectroscopically and by the X-ray crystal structure determination of the [Ru(CO)(NH2N=CH2)[P(OEt)3]4](BPh4)2 (5) derivative. Acetone-hydrazone [M(CO)[NH2N=C(CH3)2]P4](BPh4)2 (7, 8) complexes were also prepared by allowing hydrazine [M(CO)(NH2NH2)P4](BPh4)2 derivatives to react with acetone.     

New molecular perovskites: cubic C(4)N(2)H(12).NH(4)Cl(3).H(2)O and 2-H hexagonal C(6)N(2)H(14).NH(4)Cl(3)

The room-temperature syntheses and single-crystal structures of C(4)N(2)H(12).NH(4)Cl(3).H(2)O and C(6)N(2)H(14).NH(4)Cl(3) are reported. These novel molecular perovskites contain vertex-sharing octahedral (NH(4))Cl(6) arrays which replicate the octahedral packing in the cubic (SrTiO(3)) and 2-H hexagonal (BaNiO(3)) perovskite structures, respectively. The structures are completed by doubly protonated organic cations and, for the cubic phase, water molecules. Crystal data: C(4)N(2)H(12).NH(4)Cl(3).H(2)O, M(r) = 230.56, orthorhombic, Pbcm (No. 57), a = 6.5279(13) A, b = 12.935(3) A, c = 12.849(3) A, V = 1085.0(4) A(3), Z = 4; C(6)N(2)H(14).NH(4)Cl(3), M(r) = 238.59, trigonal, Pthremacr;c1 (No. 165), a = 16.1616(2) A, c = 22.3496(4) A, V = 5055.5(2) A(3), Z = 18.     

Synthesis and Crystal Structure of Bis(nitrate)bis(dipiperidin-1-yl-methanone)uranyl(II)

1 INTRODUCTION The extraction chemistry of uranium is a veryimportant research field, and the new high extrac-tants of uranium have being studied for several deca-des[1, . Our interest is studying the behaviors of new 2]extractants and their st…