NH2SO3H and H6P2W18O62 · 18H2O-Catalyzed,Three-Component,One-Pot Synthesis of Benzo[c]acridine Derivatives

We report here two simple methods for the synthesis of benzo[c]acridine derivatives from three-component, one-pot condensation of 1-naphthylamine, dimedone, and a variety of substituted aldehydes in the presence of a catalytic amount of NH₂SO₃H or H₆P₂W₁₈O₆₂ · 18H₂O under solvent-free conditions at 120 °C or in refluxing ethanol.     

Theoretical study of [Ni (H2O)n]2+(H2O)m (n ≤ 6, m ≤ 18)

The [Ni-(H(2)O)(n)](2+)(H(2)O)(m) (n ≤ 6, m ≤ 18) complexes were studied by means of first-principles all-electron calculations performed with the BPW91 gradient corrected functional and the 6-311+G(d,p) basis sets for the H, O, and Ni atoms. Triplet states were found as low-lying states for each (n, m) combination. The estimated Ni(2+)-(H(2)O)(n) binding energies (112.8-57.4 kcal/mol for the first layer and 52.0-23.0 kcal/mol for the second one) decreases and the Ni(2+)-OH(2) bond lengths lengthen as n + m increases. With six H(2)O moieties the Ni(2+) ion furnishes its first coordination sphere of octahedral geometry. Further water addition renders the formation of the second layer. The effect of Ni(2+) on the (H(2)O)(n)···(H(2)O)(m) hydrogen bond formation for several "n" and "m" combinations was studied, revealing an enhancement of this kind of bonding, which is of key importance for the stabilization and growth of the clusters. For some n + m isomers the second layer appears before the first octahedral layer is fully formed. For example, the square planar Ni(2+)-(H(2)O)(4) core originates two-dimensional 4 + 2 and 4 + 4 isomers, where each outer water molecule accepts two H-bonds, lying 2.0 kcal/mol above the 6 and 6 + 2 ground states. The clusters were also studied by IR spectra; the OH stretching vibrational frequencies allowed us to identify the outer solvation shells by the presence of red-shifted hydrogen bond regions.     

三缺位杂多化合物K8[P2W18Mo2CO2（H2O）2O68].MoO6.15H2O…

合成了杂多化合物Ｋ８［Ｐ２Ｗ１８Ｍｏ２Ｃｏ２（Ｈ２Ｏ）Ｏ６８］．ＭｏＯ６．１５Ｈ２Ｏ，依据ＸＲＤ、ＩＲ、ＵＶ－Ｖｉｓ及ＸＰＳ确定了其晶体结构的晶位原子价态，考察了该化合物催化Ｈ２Ｏ２分解动力学行为。     

Synthesis, crystal structure, and thermal stability of [Mo2O4(μ2-O)(C6H4O2)2(H2O)] · (C8H9N2)2 · 2H2O

From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO₃ in acetic acid solution, a new compound, [Mo₂(μ₂-O)₂(C₆H₄O₂)₂(H₂O)] · (C₈H₉N₂)₂ · 2H₂O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P2₁/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) β = 97.929(4), V = 3225.6(5), Z = 4, M = 808.46, ρ_c = 1.665 g/cm³, μ(MoK _α) = 0.84 mm^?1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with R _int = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N-H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O-H...O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N-H...O to form a quasi-two dimensional structure.     

Structure of the complex [trans-SnF4(H2O)2· (18-crown-6)· 2H2O]

The molecular and crystal structure of the title complex (I) obtained by addition of tin fluoride in a hydrofluoric acid solution to 18-crown-6 in methanol was investigated by X-ray structure analysis. The crystals are monoclinic, space group P2₁/n, a = 13.497(3), b = 7.806(2), c = 9.892(2) Å, β = 95.57(3)°, Z = 2 for C₁₂H₃₂F₄O₁₀Sn. In the polymer chain, the crown ether molecules alternate with the inorganic complexes [trans-SnF₄(H₂O)₂] and are linked to them by O-H...O type hydrogen bonds involving the intermediate water molecules. The weak C-H...F interactions bind the chains into the layers which are parallel to the xz plane.     

Synthesis and Crystal Structure of the Heteropolymate Compound Na3H2[Ce3(H2O)18Bi2W22O76]·23H2O

A Bi(Ⅲ) contained heteropolymate compound Na3H2[Ce3(H2O)18Bi2W22O76] (23H2O 1 has been synthesized. It crystallizes in the triclinic system, space group P with a = 14.370(3), b = 17.113(3), c = 24.764(5) A, α = 74.33(3), β = 77.20(3), γ = 65.29(3)o, V = 5285.3(18) A3, Z = 2, Mr = 6908.66, Dc = 4.341 g/cm3, F(000) = 6042, μ(MoKσ) = 28.543 mm-1, R = 0.0604 and wR = 0.1659 for 15788 reflections with I > 2σ(I). The structure analysis revealed that in the anionic framework of the title compound the [Bi2W22O76]14- anions are connected by Ce3+ and Na+ cations into a three dimensional network.     

Syntheses and Crystal Structures of (H3O)(C3H5N2)[Mn(OH)6 Mo6O18]·3.5H2O and (H3O)3[Co(OH)6Mo6O18]·7H2O

The crystals of the title compounds (H3O)(C3H5N2)[Mn(OH)6Mo6O18]·3.5H2O 1 and (H3O)3[Co(OH)6Mo6O18]·7H2O 2 have been prepared and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 21.5018(9), b = 10.9331(5), c = 11.8667(5)A,β = 95.3570(10)o, V = 2777.5(2)A3, Z = 4, Dc = 2.802 g/cm3, Mr = 1171.80,μ(MoKα) = 3.173 mm-1, F(000) = 223, the final R = 0.0458 and wR = 0.1041 for 2093 observed reflections (I>2σ(I)); Compound 2 crystallizes in monoclinic, space group P21/c with a = 11.4042(12), b = 10.9481(11), c = 11.6722(12)A, β= 99.948(2)o, V = 1435.4(3)A3, Z = 2, Dc = 2.794 g/cm3, Mr = 1207.80,μ(MoKα) = 3.223 mm-1, F(000) = 1160, the final R = 0.0544 and wR = 0.1066 for 1906 observed reflections (I > 2σ(I)). Both compounds 1 and 2 adopt the Anderson structure, in which the anion is of centrosymmetry and formed by six octahedral edge-sharing MoO6 units surrounding the central MO6 (M = Mn or Co) octahedron.     

LaX3-C18H16N3O2Cl-H2O三元体系的相平衡

测定了ＬａＸ３－Ｃ１８Ｈ１６Ｎ３Ｏ２Ｃｌ－Ｈ２Ｏ（Ｘ＝ＮＯ＾３,Ｃｌ＾－）三元体系在３０℃时的溶度和饱和溶液的折光率。发现Ｌａ（ＮＯ３）３＝Ｃ１８Ｈ１６Ｎ３Ｏ２Ｃｌ－Ｈ２Ｏ体系有不一致溶化合物Ｌａ（Ｃ１８Ｈ１６Ｎ３Ｏ２Ｃｌ）３（ＮＯ３）３生成,而ＬａＣｌ３－Ｃ１８Ｈ１６Ｎ３Ｏ２Ｃｌ－Ｈ２Ｏ体系为简单共饱体系。     

Syntheses and structures of seven-coordinate K3[Cd(Dtpa)], K2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O, and Na2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O complexes

The title complexes, K₃[Cd(Dtpa)] (H₅Dtpa = diethylenetriamine-N,N,N,N′,N′-pentaacetic acid, (I)), K₂[Cd(H₂O)₄][Cd(Edta)(H₂O)]₂ · 2H₂O (H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid, (II)), and Na₂[Cd(H₂O)₄][Cd(Edta)(H₂O)]₂ · 2H₂O (III), were prepared, and their compositions and structures were determined by elemental analyses, IR spectra, and single-crystal X-ray diffraction techniques, respectively. In complex I, the Cd is seven-coordinated by one Dtpa ligand yielding a pseudo-monocapped trigonal prism conformation, and the complex crystallizes in the triclinic crystal system with the Pi space group. The crystal data are as follows: a = 8.7300(17), b = 9.1200(18), c = 15.110(3) Å, α = 95.52(3)°, β = 96.59(3)°, γ = 99.63(3)°, V = 1170.0(4) ų, Z = 2, ρ = 1.754 g/cm³, μ = 1.519 mm^?1, F(000) = 616, R = 0.0644 and wR = 0.1712 for 3842 observed reflections with I ≥ 2σ(I). For complex II, in the [Cd(Edta)(H₂O)]^2? complex anion the Cd²⁺ ion is seven-coordinated by one Edta ligand and one water molecule, yielding a pseudo-pentagonal bipyramid conformation. In the [Cd(H₂O)₄]²⁺ cation, the bridged Cd is six-coordinated, yielding an almost standard octahedral conformation. The complex crystallizes in the monoclinic system with P2₁/n space group. The crystal data are as follows: a = 9.098(3), b = 16.442(6), c = 12.023(4) Å, β = 91.053(6)°, V = 1798.3(12) ų, Z = 2, ρ = 2.098 g/cm³, μ = 2.086 mm^?1, F(000) =1124, R = 0.0406 and wR = 0.1152 for 3680 observed reflections with I ≥ 2σ(I). In complex III, the conformations of Cd²⁺ ions are similar to those of the potassium salt complex, and the complex also crystallizes in the monoclinic crystal system with the P2₁/n space group. The crystal data are as follows: a = 9.134(7), b = 16.500(13), c = 12.075(10) Å, β = 91.054(12)°, V = 1820(2) ų, Z = 2, ρ = 2.015 g/cm³, μ = 1.856 mm^?1, F(000) = 1092, R = 0.0363 and wR = 0.0879 for 3707 observed reflections with I ≥ 2σ(I).     

X-ray powder structure determination of Li6P6O18·3H2O

Preparation, characterization by X-ray diffraction, IR absorption, DTA-GTA analysis and ab-initio crystal structure determination are reported for a new lithium cyclohexaphosphate hydrate Li₆P₆O₁₈·3H₂O. It crystallizes in a trigonal (rhomboedral) cell (space group R 3¯m No 166, Z = 6) with a = 15.7442(2) Å, c = 12.5486(2) Å. X-ray powder diffraction pattern data was refined by Rietveld profile technique and lead to R_Bragg = 0.09. The crystal structure of Li₆P₆O₁₈·3H₂O is built up from [P₆O₁₈]^6- ring anions, having the 3m symmetry, alternating along the 3¯ axis with rings made of six LiO₄ tetrahedra and six LiO₅ pseudo square pyramids sharing common edges.     

Syntheses, Crystal Structures and Characterization of Two Zeotype Crystals of K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62] ·9.5H2O and K4[Cr3O(H2O)3(OOCH)6[H3P2W17Co(H2O)O61]·20H2O

Two novel zeotype crystals, K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62]·9.5H2O(1) and K4 [Cr3O(H2O)3·X-ray single crystal diffraction. Crystal data: C12H43O103.5K4Cr6P2W18(1), hexagonal P6(3)/m, a=1.5895(2)nm, b=1.5895(2) nm, c=2.1620(4) nm, α=90°, β=90°, γ =120°, V=4.7305(13) nm3, Z=2,R1 =0. 0726, wR2=0. 1542; C6H57O98K4Cr3CoP2W17(2), hexagonal P6(3)/mmc, a=1. 61328 (3) nm, b=1.61328(3) nm, c=2. 06613 (9) nm, α=90°,β=90°, γ=120°, V=4. 6570(2) nm3, Z=2, R1=0. 0377,wR2 =0.1070. These crystals were characterized using elemental analysis, IR, TG-DTA, and XRD. It was found that the polyoxometalate anions maintained Wells-Dawson structure for crystal 1 and lacunary Wells-Dawson structure for crystal 2. Thermal analysis showed that crystal 1 lost the water of crystallization at 132 ℃, whereas crystal 2 lost the water of crystallization at 100 ℃. Crystal 1 could reversibly desorb and adsorb water molecules and its crystal structure could be restored after re-adsorbing the water molecules. It was also found from the XRD patterns that the void size of crystal 2 is smaller compared with that of crystal 1, which is attributed to the higher anion charges.     

Infrared photodissociation spectroscopy of H(+)(H2O)6·M(m) (M = Ne, Ar, Kr, Xe, H2, N2, and CH4): messenger-dependent balance between H3O(+) and H5O2(+) core isomers

Although messenger mediated spectroscopy is a widely-used technique to study gas phase ionic species, effects of messengers themselves are not necessarily clear. In this study, we report infrared photodissociation spectroscopy of H(+)(H(2)O)(6)·M(m) (M = Ne, Ar, Kr, Xe, H(2), N(2), and CH(4)) in the OH stretch region to investigate messenger(M)-dependent cluster structures of the H(+)(H(2)O)(6) moiety. The H(+)(H(2)O)(6), the protonated water hexamer, is the smallest system in which both the H(3)O(+) (Eigen) and H(5)O(2)(+) (Zundel) hydrated proton motifs coexist. All the spectra show narrower band widths reflecting reduced internal energy (lower vibrational temperature) in comparison with bare H(+)(H(2)O)(6). The Xe-, CH(4)-, and N(2)-mediated spectra show additional band features due to the relatively strong perturbation of the messenger. The observed band patterns in the Ar-, Kr-, Xe-, N(2)-, and CH(4)-mediated spectra are attributed mainly to the "Zundel" type isomer, which is more stable. On the other hand, the Ne- and H(2)-mediated spectra are accounted for by a mixture of the "Eigen" and "Zundel" types, like that of bare H(+)(H(2)O)(6). These results suggest that a messenger sometimes imposes unexpected isomer-selectivity even though it has been thought to be inert. Plausible origins of the isomer-selectivity are also discussed.     

[4,4'-bpyH2]5H2[α-P2W18O62]2·4H2O的合成与结构表征

利用水热方法合成了一种基于双Dawson多阴离子和质子化的4,4'-联吡啶阳离子构筑的化合物[4,4'-bpyH2]5H2[α-P2W18O62]2·4H2O,并经IR光谱、元素分析、热重分析和X射线单晶衍射等测试技术进行了表征.标题化合物属于三斜品系,Pi空间群,品胞参数:a=1.353 73(5),b=2.242 56(13),c=2.732 82(11)nm,α=79.890(13),β=77.568(8),γ=80.349(11)°,V=7.902 9(6)nm3,Z=2,Dc=4.031 g/cm3,GOOF=1.049,R1=0.067 4,wR2=0.143 4.结构分析结果表明,标题化合物分子由5个质子化的4,4'-联吡啶阳离子、2个H+离子、2个饱和Dawson结构多阴离子[P2W18O62]6-和4个结晶水分子组成.     

Syntheses,structures, and properties of two new hybrid Dawson-based polyoxotungstates [Mn(2,2′-bipy)3]H2 [Mn(2,2′-bipy)2][P2W18O62] and [Co(H2biim)3)]2H2[P2W18O62] · 8H2O

Two new hybrid Dawson-based polyoxotungstates, [Mn(2,2′-bipy)₃]H₂[Mn(2,2′-bipy)₂][P₂W₁₈O₆₂] (1) and [Co(H₂biim)₃)]₂H₂[P₂W₁₈O₆₂] · 8H₂O (2) (2,2′-bipy = 2,2′-bipyridine, H₂biim = 2,2′-biimdazole), have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric analyses (TGA), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectra. Compound 1 is a 1-D zigzag chain constructed from alternate Dawson-type heteropolyanions [α-P₂W₁₈O₆₂]^6? and metal coordination cations [Mn(2,2′-bipy)₂]²⁺, in which the 1-D chains are extended into a 3-D framework through C–H ··· π and π–π stacking interactions. Compound 2 is a discrete structure consisting of [α-P₂W₁₈O₆₂]^6? and two [Co(H₂biim)₃)]²⁺ cations, forming a 3-D supramolecular framework via N–H ··· O hydrogen bonds and C–H ··· π interactions. Photoluminescence properties of 1 and 2 have been investigated at room temperature.