Synthesis and structures of Cs4[(UO2)2(C2O4)(SO4)2(NCS)2] · 4H2O and (NH4)4[(UO2)2(C2O4)(SO4)2(NCS)2] · 6H2O

Single crystals of Cs₄[(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂] · 4H₂O (I) and (NH₄)₄[(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂] · 6H₂O (II) have been synthesized and studied by X-ray diffraction. The crystals of both compounds are orthorhombic with the space group Pbam, Z = 2, and unit cell parameters a = 12.0177(3) ?, b = 18.6182(5) ?, c = 6.7573(10) ?, R = 0.0376 (I); a = 11.6539(9) ?, b = 18.3791(13) ?, c = 6.7216(5) ?, R = 0.0179 (II). The main structural units of crystals I and II are [(UO₂)₂(C₂O₄)(SO₄)₂(NCS)₂]⁴⁻ chains belonging to the crystal-chemical group A₂K⁰²B₂²M₂¹ (A = UO₂²⁺, K⁰² = C₂O₄²⁻, B² = SO₄²⁻, M¹ = NCS⁻) of the uranyl complexes. The uranium-containing chains are joined into a three-dimensional framework due to a system of electrostatic interactions with the cesium or ammonium ions in the structure of I. In the structure of II, this framework is additionally stabilized by hydrogen bonds involving the outer-sphere water molecules and ammonium ions. Original Russian Text ? I.V. Medrish, A.V. Virovets, E.V. Peresypkina, L.B. Serezhkina, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 7, pp. 1115–1120.     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

Hydrothermal synthesis and crystal structures of new uranyl oxalate hydroxides: α- and β-[(UO2)2(C2O4)(OH)2(H2O)2] and [(UO2)2(C2O4)(OH)2(H2O)2]·H2O

Two modifications of the new uranyl oxalate hydroxide dihydrate [UO₂)₂(C₂O₄)(OH)₂(H₂O)₂] (1 and 2) and one form of the new uranyl oxalate hydroxide trihydrate [(UO₂)₂(C₂O₄)(OH)₂(H₂O)₂]·H₂O (3) were synthesized by hydrothermal methods and their structures determined from single-crystal X-ray diffraction data. The crystal structures were refined by full-matrix least-squares methods to agreement indices R(wR)=0.0372(0.0842) and 0.0267(0.0671) calculated for 1096 and 1167 unique observed reflections (I>2σ(I)), for α (1) and β (2) forms, respectively and to R(wR)=0.0301(0.0737) calculated for 2471 unique observed reflections (I>2σ(I)), for 3. The α-form of the dihydrate is triclinic, space group , Z=1, a=6.097(2), b=5.548(2), , α=89.353(5), β=94.387(5), γ=97.646(5)°, , β-form is monoclinic, space group C2/c, Z=4, a=12.180(3), b=8.223(2), , β=95.817(4), . The trihydrate is monoclinic, space group P2₁/c, Z=4, a=5.5095(12), b=15.195(3), , β=93.927(3), . In the three structures, the coordination of uranium atom is a pentagonal bipyramid composed of dioxo UO₂²⁺ cation perpendicular to five equatorial oxygen atoms belonging to one bidentate oxalate ion, one water molecule and two hydroxyl ions in trans configuration in 2 and in cis configuration in 1 and 3. The UO₇ polyhedra are linked through hydroxyl oxygen atoms to form different structural building units, dimers [U₂O₁₀] obtained by edge-sharing in 1, chains [UO₆]_∞ and tetramers [U₄O₂₆] built by corner-sharing in 2 and 3, respectively. These units are further connected by oxalate entities that act as bis-bidentate to form one-dimensional chains in 1 and bi-dimensional network in 2 and 3. These chains or layers are connected in frameworks by hydrogen-bond arrays.     

草酸根桥联的双核铜(Ⅱ)配合物[Cu2(phen)2(H2O)2(μ2-C2O4)](NO3)2的合成及晶体结构

A new binuclear copper(Ⅱ) complex, [Cu₂(phen)₂(H₂O)₂(μ₂-C₂O₄)](NO₃)₂, has been synthesized and characterized by elemental analysis, IR and UV-Vis spectrum. Its crystal structure was determined by single crystal X-ray diffraction techniques. Crystal data: monoclinic, space group P2₁/c, a=0.712 21(8) nm, b=1.170 93(14) nm, c=1.783 7(2) nm, β=111.828(2)°, and V=1.380 8(3) nm³, D_c=1.769 Mg·m^-3, Z=2, F(000)=744, R₁=0.025 4, wR₂=0.069 5, Gof=1.077, Δρ=328～-455 e·nm^-3. The complex is packed by one centrosymmetry binuclear copper(Ⅱ) unit, oxalate dianion and NO₃^- anion. In the molecule structure of the title complex, two Cu(Ⅱ) ions are bridged by oxalate dianion and each Cu(Ⅱ) ions coordinates with two nitrogen atoms from 1,10-phenanthroline ligand and one oxygen atom from water to form a five-coordinate distorted square-pyramidal configuration. The hydrogen bonds are observed between coordinated water molecules and NO₃^- anions. The analysis of the crystal structure indicates that the complex has a two-dimensional stacking network structure, which is formed by intramolecular hydrogen bonds, intermolecular hydrogen bonds and stacking effect of aromatic ring. CCDC: 255345.     

2D层状焦磷酸锰(Ⅱ)[NH4]2[Mn3(P2O7)2(H2O)2]的结构和磁性研究

A two-dimensional layered manganese(Ⅱ) pyrophosphate, [NH₄]₂[Mn₃(P₂O₇)₂(H₂O)₂] (1), has been synthesized hydrothermally. Its structure is determined by single-crystal X-ray diffraction analysis. Its structure is built up by MnO₆ octahedra and P₂O₇ units, with ammonium NH₄⁺ cations residing in the interlayer regions. The manganese pyrophosphate layer consists of infinite chains of cis and trans edge sharing MnO₆ octahedra linked by P₂O₇ units. Magnetic susceptibility measurements show that this compound exhibits ferrimagnetic-like ordering below 3.2 K. Further study shows that there are two possible superexchange pathways via the oxygen anions in Mn²⁺ ions. Owing to the different bridging modes of O^2-, the competition between ferromagnetic interactions and antiferromagnetic interactions in Mn²⁺ ions results in the ferrimagnetic behavior of 1.     

(ZrO2)0.86(Sm2O3)0.14纳米粉体的水热法合成及其烧结体的电性能

以湿化学法制得Zr(OH)₄和Sm(OH)₃的共沉淀为前驱体, 在碱性介质中用水热法合成了(ZrO₂)_0.86(Sm₂O₃)_0.14及(ZrO₂)_0.88(Sm₂O₃)_0.12纳米粉体. 将纳米粉体在较低温度(1450 ℃)下烧结制得了致密的固体电解质陶瓷样品, 比通常高温固相反应法采用的烧结温度(＞1600 ℃)降低了150 ℃以上. XRD测定结果表明, (ZrO₂)_0.86(Sm₂O₃)_0.14纳米粉体及其烧结体均为立方相, 但(ZrO₂)_0.88(Sm₂O₃)_0.12纳米粉体为立方相, 它的烧结体为立方相和单斜相的混合相. 用交流阻抗谱法、氧浓差电池法及氧泵(氧的电化学透过)法研究了(ZrO₂)_0.86(Sm₂O₃)_0.14陶瓷样品在600～1000 ℃下的离子导电特性. 结果表明, 该陶瓷样品在600～1000 ℃下氧离子迁移数为1, 氧离子电导率的最大值为3.2×10^－2 S•cm^－1, 是一个优良的氧离子导体; 它的氧泵性能明显地优于YSZ.     

Synthesis and Crystal Structure of (H)2[Y(H2O)8]2(NO3)8(C36H36N24O12)?13H2O

The compound of (H)₂[Y(H₂O)₈]₂(NO₃)₈(C₃₆H₃₆N₂₄O₁₂)13H₂O composition was obtained from a nitric acid solution of yttrium nitrate and a macrocyclic cavitand cucurbituryl. According to X-ray diffraction data, the crystal structure of the compound involves alternating layers of cucurbituryl molecules and eight-coordinate yttrium aqua complexes. The structure has a complex system of hydrogen bonds involving the oxygen atoms of cucurbituryl and water molecules and the nitrate anions and linking all structural elements of the crystal.     

Synthesis and crystal structure of new one-dimensional copper(II) complex [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2]n

A new polymer azido-bridged copper(II) complex [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂] _n (I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂], in which the azido ions display three different bridging modes.     

Sandwich-type Uranium-Substituted of Bismuthotungstate: Synthesis and Structure Determination of [Na(UO2)2(H2O)4(BiW9O33)2]13?

The sandwich-type [Na(UO₂)₂(H₂O)₄(BiW₉O₃₃)₂]¹³⁻ uranium (VI) has been synthesized by reacting the trivacant species of B-α-[BiW₉O₃₃]⁹⁻ with and investigated by IR and UV–Vis spectroscopy, and elemental analysis. The X-ray single crystal analysis was carried out on Na₁₃[Na(UO₂)₂(H₂O)₄(BiW₉O₃₃)₂] · 33H₂O (I) which crystallizes in the orthorhombic system, space group Pna2₁ with a = 33.8454(19) ?, b = 21.1484(12) ?, c = 13.2403(7) ?, α = 90°, β = 90°, γ = 90°, and Z = 4. The polyanion consists of two lacunary B-α-[BiW₉O₃₃]⁹⁻ groups which sandwich two uranyl cations and one sodium cation. The uranium atoms adopt distorted pentagonal–bipyramidal coordination, achieved by two equatorial bonds to each BiW₉O₃₃ unit and one external water ligand. The coordination of each uranium atom is evident by the shift of ν_as(W–O_b–W) and ν_as(Bi–O) stretching vibrational bonds. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Stepwise addition of CuBr at [(dtc)2Mo2(S)2(μ-S)2] (dtc=diethyldithiocarbamate): syntheses and crystal structures of two Mo/Cu/S clusters [(dtc)2Mo2(μ3-S)(μ-S)3(CuBr)] and [(dtc)2Mo2(μ3-S)4(CuBr)2]

Reactions of [(dtc)₂Mo₂(S)₂(μ-S)₂] with one or two equivalents of CuBr in CH₂Cl₂ afforded two new heterobimetallic sulfide clusters, [(dtc)₂Mo₂(μ₃-S)(μ-S)₃(CuBr)] (1) and [(dtc)₂Mo₂(μ₃-S)₄(CuBr)₂] (2). Both compounds were characterized by elemental analysis, IR, UV-vis and X-ray analysis. Compound 1 contains a butterfly-shaped Mo₂S₄Cu core in which one CuBr unit is coordinated by one bridging S and two terminal S atoms of the [(dtc)₂Mo₂(S)₂(μ-S)₂] moiety. In the structure of 2, one [(dtc)₂Mo₂(S)₂(μ-S)₂] moiety and two CuBr units are held together by six Cu-μ₃-S bonds, forming a cubane-like Mo₂S₄Cu₂ core.     

(ZrO2)0.92(Gd2O3)0.08纳米晶的水热合成及其烧结体的电性能

用新制备的(Gd，Zr)(OH)_x·yH₂O共沉淀作前驱体，在强碱性介质中用水热法合成了(ZrO₂)_0.92(Gd₂O₃)_0.08纳米立方晶，考察了反应温度、pH值等水热反应条件对纳米晶粒大小的影响。将(ZrO₂)_0.92(Gd₂O₃)_0.08     

Two novel Mo(V) and Mo(V)/Mo(VI) barium phosphates with a tunnel structure: β-Ba(MoO)2(P2O7)2, and Ba(MoO)2O(P2O7)PO4

Two new Mo(V) and Mo(V)/Mo(VI) phosphates, β-Ba(MoO)₂(P₂O₇)₂ and Ba(MoO)₂O(P₂O₇)PO₄, with original tunnel structures have been synthesized. The first one crystallizes in the space group P2₁/n with , , , β=91.67°, and the second one in the space group Cc with , , , β=99.50°. β-Ba(MoO)₂(P₂O₇)₂ shows close relationships with the α-form, i.e., it consists of similar MoP₂O₁₁ units sharing their apices and forming [MoP₂O₁₀]_∞ chains. It differs from the latter by the configuration of the chains, so that one chain is linked to four other identical chains, instead of six chains in the α-form. Like the α-form, the β-form exhibits intersecting tunnels running along [010] and [011] direction where the Ba²⁺ cations sit. The 3D-framework of the second phosphate Ba(MoO)₂O(P₂O₇)PO₄, is built up of MoO₆ octahedra, P₂O₇ groups, and PO₄ tetrahedra, can be described by the assemblage of zig-zag [Mo₂P₂O₁₄]_∞ chains through PO₄ tetrahedra, forming large tunnels running along , occupied by Ba²⁺ cations. In this framework one observes that adjacent tunnels communicate through large six-sided windows, showing the opened character of this structure. The magnetic behaviour of these phosphates is discussed with respect to the results previously obtained by Canadell et al. [Chem. Mater. 9 (1997) 68].     

Formation of the silylene-bridged complex Fe2(CO)6(μ2-SiCl2)3 from cis-Fe(CO)4(SiCl3)2: an experimental and computational study

Abstract  

Thermolysis of cis-Fe(CO)₄(SiCl₃)₂ results in the formation of the novel compound Fe₂(CO)₆(μ₂-SiCl₂)₃, which was characterized by single crystal X-ray diffraction. Density functional theory calculations were carried out to elucidate possible reaction steps leading to the formation of Fe₂(CO)₆(SiCl₂)₃, including CO dissociation and chlorine abstraction by a SiCl₃ radical generated from homolytic Fe–Si bond cleavage involving a singlet–triplet intersystem crossing.     

Synthesis,structure characterization and thermal properties of [Zr6(μ3-O)4(μ3-OH)4(OOCCH2Bu)9(μ2-OH)3]2

Oxo/hydoxo zirconium(IV) complex of the general formula [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ has been isolated, when Zr(OⁱPr)₄ reacted with a 2-fold excess of 3,3-dimethylbutyric acid. Single crystal X-ray diffraction data, collected at 103 and 153 K, showed that the studied compound crystallizes in hexagonal system (P6₃/m (no. 176)). Structure consists of dimers composed of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉] sub-units, linked by six μ₂-OH bridges. Infrared spectroscopic studies proved the presence of hydroxo groups in the structure of studied clusters and formation of different types of oxo/hydroxo bridges. The application of variable temperature infrared spectroscopy and differential scanning calorimetry revealed that the structure of this complex undergoes the phase transitions at 143–183 and 203–293 K. Comparison of spectral and crystallographic data suggests that these phase transitions might be related to changes in the strength of Zr–O bonds of μ₂-OH bridges linking complex sub-units, and change in symmetry of the crystal lattice (from hexagonal to trigonal). Analysis of thermogravimetric data showed that decomposition of [Zr₆(μ₃-O)₄(μ₃-OH)₄(OOCCH₂^tBu)₉(μ₂-OH)₃]₂ proceeds with complete conversion to ZrO₂ (monoclinic form) between 603 and 803 K.     

[Cu(TO)2(H2O)4](PA)2的合成和晶体结构

[Cu(TO)₂(H₂O)₄](PA)₂ was prepared by mixing the aqueous solution of 1,2,4-triazol-5-one(TO) and Cu(PA)₂. The molecular structure and crystal structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm³,Z=1. The Cu²⁺ coordinated with two TO molecule through its 2-nitrogen atom and four water molecules and showed an octahedral configuration.     

Synthesis and characterization of a new octamolybdate (NH4)4[Mo8O24(C3H2O2)2] · 4H2O

A new complex with the formula (NH₄)₄[Mo₈O₂₄(C₃H₂O₂)₂] · 4H₂O (1) has been synthesized and characterized by single crystal X-ray diffraction and infrared spectrum. The complex is small yellow crystal and space group P ₁ with a = 9.9869(18) ?, b = 10.030(19) ?, c = 10.366(19) ?, α = 91.68(3)°, β = 98.94(3)°, γ = 119.37(2)°, V = 887(3) ?³, and Z = 1. The complex contains two malonic acid ligands bonded to the γ-Mo_{8 26}⁴⁻ ions which consist of eight MoO₆ edge-sharing octahedral. In this crystal structure, the octamolybdate anion is mutually hydrogen bonded by ammonium ions and water molecules.     

Mixed-ligand complexes [Cd(DMSO)5(NCS)][Cr(NH3)2(NCS)4] · 3DMSO and [Mn(DMSO)4(H2O)2][Cr(NH3)2(NCS)4]2 · 6DMSO · 2H2O: Syntheses and crystal structures

New mixed-ligand coordination compounds[Cd(DMSO)₅(NCS)][Cr(NH₃)₂(NCS)₄] · 3DMSO (I) and [Mn(DMSO)₄(H₂O)₂][Cr(NH₃)₂(NCS)₄]₂ · 6DMSO · 2H₂O (II) have been synthesized and studied by IR spectroscopy and X-ray diffraction analysis. The crystals of compound I are monoclinic, a = 14.5275(7), b = 23.1692(11), c = 14.6969(6) ?, β = 97.057(2)°, V = 4909.4(4) ?³, space group P2₁/c, Z = 4, ρ_calcd = 1.507 g/cm³, R = 0.0556. The crystals of compound II are triclinic, a = 11.7784(3), b = 12.1760(3), c = 13.1922(2) ?, α = 85.5420(10)°, β = 87.9000(10)°, γ = 70.3680(10)°, V = 1776.46(7) ?³, space group P , Z = 1, ρ_calcd = 1.444 g/cm³, R = 0.0350. Original Russian Text ? E.A. Gerasimova, T.V. Utkina, E.V. Peresypkina, A.V. Virovets, T.G. Cherkasova, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 5, pp. 751–755.     

Crystal structure of K2[Mo3(PdPPh3)S4(C2O4)3(H2O)3]·0.5H2O

By the reaction of [Mo₃S₄(C₂O₄)₃(H₂O)₃]²⁻ with PdCl₂ and NH₄H₂PO₂ as a reducing agent, followed by the addition of PPh₃, a new oxalate cuboidal cluster complex [Mo₃(PdPPh₃)S₄(C₂O₄)₃(H₂O)₃]²⁻ is obtained. It was isolated and structurally characterized as K₂[Mo₃(PdPPh₃)S₄(C₂O₄)₃(H₂O)₃]·0.5H₂O. Original Russian Text Copyright ? 2008 by A. L. Gushchin, M. N. Sokolov, D. Yu. Naumov, and V. P. Fedin __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 49, No. 4, pp. 775–778, May–June, 2008.     

Diverse coordination of two ligands in ferromagnetic [Cu(μ-HCO2)2(3-pyOH)]n and [Cu2(μ-HCO2)2(μ-3-pyOH)2(3-pyOH)2(HCO2)2]n

Two novel polynuclear complexes with methanoate anions and 3-hydroxypyridine ligands [Cu(μ-HCO₂)₂(3-pyOH)]_n (1) and [Cu₂(μ-HCO₂)₂(μ-3-pyOH)₂(3-pyOH)₂(HCO₂)₂]_n (2), respectively, were synthesized and characterized. The central copper atom in 1 is surrounded by four methanoates and a 3-pyOH molecule, forming a square-pyramidal CuO₃NO chromophore. All the methanoates are bidentate and serve as bridges between the adjacent copper ions via syn-anti and anti–anti coordination. The basal square coordination axes are formed by O(syn), N(3-pyOH) (1.974(2), 2.016(2) Å) and O(anti), O(anti) (1.945(2), 1.960(2) Å), while the third O(anti) (2.247(2) Å) is on the top of the pyramid. A ferromagnetic transition with an exchange constant 2J/k_B = 9.2 cm⁻¹ is found for 1 below 20 K. This interaction probably takes place through two syn-anti methanoates extended in a chain through the 2D structure. On the other hand, two monoatomic Cu–O–Cu intra-dinuclear asymmetric (1.986(2), 2.415(2) Å) bridges of two methanoates in [Cu₂(HCO₂)₄(3-pyOH)₄] (2) are present. An elongated distorted octahedral coordination sphere around each copper(II) atom is completed by an additional monodentate terminal methanoate (1.975(2) Å), two N-coordinated 3-pyOH (2.005(2), 2.002(2) Å) and the third weakly O-coordinated 3-pyOH (2.732(2) Å). Although a shorter Cu?Cu distance is noticed in 2 than in 1 (4.690(1) Å 1, 3.442(1) Å 2), much weaker ferromagnetism is found in 2.     

Crystal structures of barium bis(iminodiacetato)cobaltates(III): [Ba(H2O)6][Co(Ida)2]2 · H2O and Ba4(H2O)14][Co(Ida)2]5(ClO4)3 · 5.46H2O · 2CH3OH

The structures of the crystals of Ba₄[trans(N)-Co(Ida)₂]₃[cis-(N)-Co(Ida)₂]₂(ClO₄)₃ · 19.46H₂O · 2CH₃OH (I) and Ba[trans-(N)-Co(Ida)₂]₂ · 7H₂O (II) (H₂Ida is iminodiacetic acid) were determin by X-ray diffraction. The crystals of I containing two geometric isomers of the complex anions [Co(Ida)₂]⁻ were obtained by a slow cooling of a hot solution, which contained initially only the cis-isomer. One Ba atom in I interacts with the trans-complex and with two cis-complexes to give a three-dimensional framework in crystal I. The positive charge of the last framework is compensated by one more trans-complex and by the perchlorate ions, one of which acts as a bidentate ligand with respect to the Ba atom. The crystals of II are built of the chains with the alternating Ba atoms and the trans-(N)-[Co(Ida)₂]⁻ anions. The other anions of the same structure are each “suspended” to the Ba atoms of the chain. Original Russian Text ? M. Zabel, A.I. Poznyak, V.I. Pawlowskii, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 11, pp. 831–836.