[Co(dmg)2Cl2]3·[Co(dmg)2Cl(OH)]·[Co(dmg)(phen)]·(H2O)4的合成和晶体结构

本文合成了一个复杂的单核配合物 [Co(H2dmg)2Cl2]3·[Co(H2dmg)2Cl(OH)]·[Co(Hdmg)(phen)]·(H2O)4 (H2dmg＝dimethylglyoxime, phen＝1,10-Phenanthroline).通过X射线衍射技术获得其单晶结构.在单晶结构中,每五个单核钴(II)的配位结构形成一个重复单元,是一个较为复杂的单晶.其空间群为P-1,晶胞参数为a＝1.3738nm;b＝1.4396nm;c＝1.8656nm.本文中我们将讨论该化合物的分子结构及相关光谱性质.     

Molecular structure of [trans-FeCl2(imidazole)4]Cl·THF·H2O

The structure of [trans-FeCl₂(imidazole)₄]Cl has been determined as the THF/H₂O solvate. The Fe-Cl and Fe-N distances in the cation are shorter than analogous trans-FeCl₂(L)₄ compounds, concomitant with the decreased ionic radius of Fe³⁺ versus Fe²⁺. Crystal data: orthorhombic, Pnma, a = 8.456(2), b = 20.991(4), c = 13.288(3) Å, V = 2358.6(8), andZ = 4.     

Synthesis and structural characterization of [VS4(CuPPh3)4Br]·CH2Cl2

Heating a solid mixture of (NH₄)₃VS₄, CuCl, PPh₃, and NEt₄Br at 100°C for 10 h and extraction with CH₂Cl₂ yielded [VS₄(CuPPh₃)₄Br]·CH₂Cl₂. Crystallographic data: Triclinic, P1¯, a = 15.189(3), b = 20.093(6), c = 12.031(3) Å, = 102.39(2), = 100.05(2), = 82.86(2)°, V = 3517(3) ų, and Z = 2. The configuration of the VS₄Cu₄Br core can be described as a distorted cubane with an additional face. The V atom has retained the tetrahedral geometry of the free [VS₄]^3– moiety. The four Cu atoms have three different coordination environments, strongly distorted tetrahedral, nearly trigonal planar, and strictly trigonal planar. The infrared, electronic, and ⁵¹V NMR spectra have also been reported.     

The synthesis and crystal structure of [La(OH2)5(phen)2]Cl3·4H2O·phen

[La(OH₂)₅(phen)₂]Cl₃·4H₂O·phen is centric, Pnna, witha=19.946(7),b=16.458(5),c=12.207(4)Å andD _calc=1.57 g cm^–3 forZ=4. The La(III) ion resides on a crystallographic twofold axis and is coordinated to four nitrogen atoms (from two phen molecules) and five water molecules resulting in a distorted tricapped trigonal prismatic geometry. An uncoordinated phen molecule, two chloride anions, and four uncoordinated water molecules are hydrogen bonded to the coordinated water molecules. The coordinated and uncoordinated phen molecules -stack diagonally through the unit cell.     

Crystal structure ofcis-[Ru(bpy)2(PPh3)Cl+][ClO 4 − ]·(toluene)·∼0.5(CH2Cl2), a species with two different disordered solvent molecules of crystallization

The complexcis-[Ru(bpy)₂(PPh₃)Cl⁺][ClO ₄ ^– ] (where bpy=2,2-bipyridyl) crystallizes from a solution in toluene/dichloromethane as the toluene-hemi(dichloromethane) solvate in the centrosymmetric space group witha=10.343(2)Å,b=11.823(3)Å,c=18.469(4)Å, =98.90(2)^o, =93.32(2)^o, =101.46(2)^o,V=2177.8(8)ų andZ=2. The structure was refined toR(F)=4.6% for those 4248 reflections above 6(F _o ). The octahedral Ru(II) cation is associated with the bond lengths Ru–Cl=2.424(2)Å, Ru–PPh₃=2.328(1) Å and Ru–N=2.045(5)–2.109(4)Å. Both the cation and the perchlorate anion are ordered. However, the unit cell also contains two disordered toluene molecules (centered about inversion centers at 1, 1/2, 0 and 1/2, 0, 1/2), and a disordered dichloromethane molecule of a partial occupancy (centered about 1/2, 0, 1).     

Synthesis and crystal structure of [Y(NO3)3(OH2)3]·(Me2-16-crown-5)·H2O

The complex [Y(NO₃)₃(OH₂)₃]·(Me₂-16-crown-5)·H₂O has been prepared and its crystal and molecular structure determined using single crystal X-ray diffraction. The colorless crystals belong to the monoclinic space group P2₁/n with Z = 4. Lattice parameters are a = 10.420(1), b = 17.257(3), c = 14.646(2) Å, = 96.79(1)°, V = 2615.1(6) ų. The yttrium(III) ion is nine-coordinate, bonded to three bidentate nitrate groups and three water molecules. The average Y–O(nitrate) and Y–O(water) distances are 2.42(3) and 2.33(1) Å, respectively. The average HO–H···O hydrogen bonded separation is 2.767Å.     

[Co（amghCl2]3·[Co（amg）2Cl（OH）]·[Co（amg）（phen）]·（R2O）4的合成和晶体结构

本文合成了一个复杂的单核配合物 [Co(H2dmg)2Cl2]3·[Co(H2dmg)2Cl(OH)]·[Co(Hdmg)(phen)]·(H2O)4 (H2dmg＝dimethylglyoxime, phen＝1,10-Phenanthroline).通过X射线衍射技术获得其单晶结构.在单晶结构中,每五个单核钴(II)的配位结构形成一个重复单元,是一个较为复杂的单晶.其空间群为P-1,晶胞参数为a＝1.3738nm;b＝1.4396nm;c＝1.8656nm.本文中我们将讨论该化合物的分子结构及相关光谱性质.     

Crystal structure of chloro[1-hydroxyethane-1,1-diphosphonato(3−)]ditin(II) monohydrate Sn2(HL)Cl · H2O

The synthesis and X-ray structure analysis of Sn₂(HL)Cl · H₂O, where HL ^3? is the anion of 1-hydroxyethane-1,1-diphosphonic acid, are reported. The coordination polyhedra of two independent tin(II) atoms are the Sn(1)O₂Cl and Sn(2)O₃ trigonal pyramids, in which one of the vertices is occupied by a lone electron pair (Sn-O, 2.144–2.218 Å and Sn-Cl, 2.573 Å). The pyramids are complemented by weaker Sn?O and Sn?Cl contacts to form severely distorted (3 + 3) octahedra. The SnO₂Cl and SnO₃ pyramids are linked by the HL ^3? bridging ligands into the [Sn₂(HL)Cl]₆ cyclic molecules, which, in turn, are joined by additional Sn?O, Sn?Cl, O(H₂O)?O(L), and O(H₂O)?Cl contacts with each other and with crystallization water molecules into a three-dimensional framework.     

Structure of (meso-5,10,15,20-tetraphenylporphyrinato) dichlorophosphorus(V) chloride, [P(tpp)Cl2]+Cl−

The title compound [P(tpp)Cl₂]⁺Cl^– crystallizes in the space group P2₁/n witha=10.701(2),b=24.860(2),c=14.799(2), =94.24(2)°,Z=4. The phosphorus atom has an octahedral coordination geometry formed by the four nitrogen atoms (Np) of the porphyrinato group and the two chloride ions. The average phosphorus-chloride distance is 2.150(1) Å, with phosphorus situated 0.006 Å below the porphyrin ring.     

配合物[Cu2(C6H2Cl2OC=N-C3H6COO)2(H2O)2]·3H2O合成与晶体结构

本文以苏氨酸,3,5-二溴水杨醛以及醋酸铜为原料合成了新型配合物[Cu2(C6H2Cl2OC=N-C3H6COO)2(H2O)2]·3H2O,并对其晶体结构经元素分析,红外光谱及X射线单晶衍射表征.结果表明:该晶体属单斜晶体结构,晶胞参数分别为:a=0.6985(2) nm, b=1.0789(2) nm, c=1.9639(3) nm, β=92.182(3) °, Mr=797.34, V=1.4789(6) nm3 , Z=2, Dc=1.790 g/cm3, μ(MoKa) =1.867 mm-1, F(000)=808, R=0.0321, wR= 0.0566.Cu(II)与一个N原子,两个O原子以及一个水分子构成三齿链状席夫碱.不对称单元结构包含两个配合物分子及三个由氢键链接的水分子.     

三维孔道结构钒磷酸盐[H3N(CH2)3NH3]2[H3N(CH2)3NH2][H2N(CH2)3NH2]-[V(H2O)2(VO)8(OH)4(PO4)4(HPO4)4]·4H2O的水热合成和结构表征

以1,3-丙二胺为模板,水热合成了三维孔道结构钒磷酸盐[H3N(CH2)3NH3]2[H3N(CH2)3NH2][H2N(CH2)3NH2][V(H2O)2(VO)8(OH)4(PO4)4(HPO4)4]·4H2O(DAP-V9P8).用单晶X射线衍射、红外光谱和热重法对该化合物的晶体结构进行了表征.DAP-V9P8的无机骨架由[VO5]、[VO6]、[PO4]和[HPO4]通过共顶点连接而成.孔道中充填的丙二胺分子随所处结晶学位置不同,有三种完全不同的分子构象.其中,位于//b轴直径达1.82nm椭圆形孔道中心的丙二胺分子碳链呈独特的直线状分布.晶体学参数:a=1.4820(9)nm,b=1.0255(4)nm,c=1.8181(9)nm,β=90.391(8)°;P21/n(No.14);R1=0.0772,wR2=0.2004(I＞(2σI)).与等结构的其它化合物进行了系统的结构比较.     

f-Element/crown ether complexes. 20. Synthesis and structure of [Y(NO3)3(OH2)3]·1.5(15-crown-5)·Me2O

The title complex was prepared by the addition of 15-crown-5, dissolved in acetone, to a solution of Y(NO₃)₃·nH₂O in the same solvent. The crystal structure of this complex, determined by single-crystal X-ray diffraction using counter methods, was carried out on a crystal grown by slow evaporation of the reaction mixture at room temperature. [Y(NO₃)₃(OH₂)₃]·1.5(15-crown-5) Me₂CO crystallizes in the acentric space group, P2₁, with unit cell dataa=15.900(5),b=16.530(6),c=11.821(5) Å,=92.12(3)°,D _calc=1.53 g cm^–3 forZ=4. Each unit cell consists of two dimers of the formula unit. One crown molecule bridges two [Y(NO₃)₃(OH₂)₃] units via hydrogen bonding with one water molecule of each. The two remaining water molecules per metal moiety form three hydrogen bonds to another 15-crown-5 molecule and one to an acetone molecule. The average bonding parameters in the nine-coordinate metal complexes are Y-O(NO₃)=2.43(4) Å and Y-O(OH₂)=2.34(5) Å.For Part 19 see Rogers, 1987.     

The synthesis and X-ray structure of [Sr2(OSiPh3)4(NH3)5]·0.5C7H8

The title complex [Sr₂(OSiPh₃)₄(NH₃)₅]·0.5C₇H₈ was prepared by the reaction of strontium metal granules with triphenylsilanol in an ammoniacal-toluene solution at –40°C. It crystallizes in monoclinic space group P2₁/n with a = 14.465(3), b = 20.715 (6), c = 25.199(6) Å, = 95.98(2)°, and Z = 4. The complex has a dimeric structure with one terminal and three bridging triphenylsiloxy ligands, the remaining coordination sites being occupied by five ammonia molecules. The central Sr₂O₄N₅ moiety adopts a distorted M₂X₉ face-sharing bioctahedral arrangement.     

Primary to secondary sphere coordination of 15-crown-5 to lanthanide(III) chlorides: structural analysis of [MCl3(15-crown-5)] (M=La,Ce) and [Er(OH2)8]Cl3·15-crown-5

Complexes of LaCl₃·7H₂O and CeCl₃·7H₂O directly coordinated to 15-crown-5 were prepared by placing the reactants in 31 CH₃CNCH₃OH on opposite sides of a fine porosity glass frit in a U-shaped cell and passing a 10 A current through the cell. The crystal structures of the two anhydrous 8-coordinate complexes, [MCl₃(15-crown-5)] (M=La, Ce) have been determined. Each contains the lanthanide in a bicapped trigonal prismatic geometry. The two complexes are isostructural crystallizing in the monoclinic space groupP2₁/c with (at 20°C) for M=La:a=8.217(8),b=14.298(2),c=14.341(9) Å, =104.79(8)°, andD _calc=1.90 g cm^–3 forZ=4; for M=Ce:a=8.208(9),b=14.263(6),c=14.270(8) Å, =104.74(7)°, andD _calc=1.92 g cm^–3 forZ=4. Direct reaction of ErCl₃·6H₂O with 15-crown-5 in 31 CH₃CNCH₃OH resulted in the crystallization of the second sphere hydrogen bonded complex [Er(OH₂)₈]Cl₃·15-crown-5. This complex is monoclinic,P2₁/n with (at 18°C)a=9.193(3),b=17.235(9),c=15.216(5) Å, =92.48(3)°, andD _calc=1.76 g cm^–3 forZ=4. The Er³⁺ ion is dodecahedral.     

Structures and crystallization behavior of cis-α-[Co(trien)(NO2)2]·ClO4 (I), cis-β-[Co(trien)(NO2)2]Br·2H2O (II), and cis-β-[Co(trien)(NO2)2]·ClO3 (III)

Structures, conformations, and crystallization behavior of compounds cis--[Co(trien)(NO₂)₂]·ClO₄ (I), cis--[Co(trien)(NO₂)₂]Br·2H₂O (II), and cis--[Co(trien)(NO₂)₂]·ClO₃ (III) are reported. Compound (I) crystallized in space group Pbca, with a = 12.3323(9), b = 13.0265(9) and c = 18.1597(13) Å; compound (II) crystallized in space group Pca2₁, with a = 8.1844(7), b = 14.7011(14) and c = 12.4875(12) Å, while compound (III) also crystallized in space group Pca2₁, with a = 12.4897(8), b = 8.8499(6) and c = 12.6500(8) Å. In all three cases, the Co(III) ions were six-coordinated with nitrogens from trien and two nitrates. Inter- and intramolecular hydrogen bonding interactions are discussed to explain the conglomerate versus racemate crystallization behavior adopted by these three compounds, with comparison of their known analogue compounds of cis-/-[Co(trien)(NO₂)₂]X, where X = halide and NO^– ₃. For the cis--[Co(trien)(NO₂)₂]⁺ cation, the conformation of the cation itself determines the intramolecular hydrogen bonding pattern, and the interaction of counteranions can be ignored, while in cis--[Co(trien)(NO₂)₂]·ClO₄, the perchlorate interrupts the intramolecular hydrogen bonding pattern observed in the halide analog.     

X-ray crystal structures of [HB(3,4,5-Me3pz)3[2Zn, [H2B(3,4,5-Me3pz)2]Zn(μ-3,4,5-Me3pz)2Zn[H2B(3,4,5-Me3pz)2], and [H2B(pz)2]2Zn (pz = pyrazolyl ring)

[HB(3,4,5-Me₃pz)₃]₂Zn (1) and [H₂B(3,4,5-Me₃pz)₂]Zn(-3,4,5-Me₃pz)₂Zn[H₂B(3,4,5-Me₃pz)₂] (2) are present in equal amounts in a crystal in the triclinic space group, P-1 with a = 11.5924(11) Å, b = 12.7799(12) Å, c = 15.7317(14) Å = 107.905(2)° = 96.796(2)°, = 105.786(2)°, and Z = 1. The structure of 1 is a trigonally distorted octahedron and is very similar to the structure of [HB(3,5-Me₂pz)₃]₂Zn showing that the introduction of the third methyl group on the pyrazolyl ring does not impact on structure. [H₂B(pz)₂]₂Zn (3) is orthorhombic, Pca2(1) with a = 10.1473(3) Å, b = 11.1117(2) Å, c = 14.1831(5) Å, = = = 90° and Z = 4. The zinc(II) centers in both 2 and 3 are similar and have pseudotetrahedral structures.     

Crystal structure of cesium sodium hexathiocyanatobismuthate Cs2Na[Bi(SCN)6] and characterization of Cs2Na[Bi(SCN)6−x Cl x ] and Cs2Na[Bi2(SCN)9−x Cl x ] complexes by X-ray powder diffraction

Cs₂Na[Bi(SCN)₆] crystallizes in the trigonal space group with one formal molecule per unit cell.M=846.25,a=7.189(1),c=10.580(2) ,V=473.5(1) ,D _x =2.967 g cm^–3, (MoK)=13.70 mm^–1,F(000)=378. FinalR=0.029 for 917 absorption-corrected reflections. The structure consists of infinite[Bi(SCN)₆Na] ^2– anionic chains along thec axis with slightly distorted octahedral Bi–6S and Na–6N coordination and Cs⁺ ions surrounded by three anionic chains with irregular coordination by six N and three S atoms. X-ray powder diffractograms of three complexes, Cs₂Na[Bi(SCN)_6–x Cl _x ] withx=2, 3 and 4, indicate that the mixed complexes are not isostructural and can be indexed in different orthorombic unit cells witha=14.617(8),b=12.32(1),c=10.769(6) forx=2;a=15.37(1),b=10.81(1),c=10.287(6) forx=3 anda=14.662(7),b=14.366(7),c=7.932(4) forx=4. The two dinuclear complexes Cs₂Na[Bi₂(SCN)_9–x Cl _x ] withx=2 and 3, despite the large similarity of their diffractograms, are not isostructural and can be indexed in different orthorombic unit cells witha=14.79(1),b=13.72(1),c=10.591(5) forx=2 anda=18.423(8),b=15.657(7),c=7.410(7) forx=3.     

Molecular structure of [CpRu(PPh3)2(C6H11SH)]BF4·CH2Cl2

The structure of the [CpRu(PPh₃)₂(C₆H₁₁SH)]BF₄·CH₂Cl₂ complex was determined by X-ray diffraction techniques; triclinic space group ,a=12.567(1),b=13.409(1),c=14.733(1) Å, =95.380(7), =111.041(7), =96.454(8)°,V=2278.5(4) ų,Z=2,R=0.056,R _w=0.088. The Ru is attached to two triphenylphosphine ligands, a cyclopentadienyl and the S atom of the cyclohexylthiol. The Ru–S distance is 2.389(2) Å and the S–H distance is 1.23 Å.     

Reaction of 1,2-bis(diphenylphosphino)cyclobutenedione (bpcbd) with fac-BrRe(CO)3(THF)2: X-ray diffraction structure of the dimeric complex [BrRe(CO)3]2(bpcbd) ⋅ CH2Cl2

Treatment of the diphosphine ligand 1,2-bis(diphenylphosphino)cyclobutenedione (bpcbd) with the THF adduct fac-BrRe(CO)₃(THF)₂ at room temperature furnishes the new dirhenium compound [BrRe(CO)₃]₂(bpcbd) instead of the expected mononuclear compound fac-BrRe(CO)₃(bpcbd). [BrRe(CO)₃]₂(bpcbd) was characterized in solution by IR spectroscopy, and the solid-state structure was solved by X-ray crystallography. [BrRe(CO)₃]₂(bpcbd), as the CH₂Cl₂ solvate, crystallizes in the space group P , a = 11.173(1), b = 13.362(1), c = 15.250(1) Å, = 108.973(7)°, = 99.477(8)°, = 110.466(7)°, V = 1915.0(3) ų, Z = 2, and d _calc = 2.143 g-cm^–3. The structure of [BrRe(CO)₃]₂(bpcbd) consists of two rhenium centers that are six-coordinate and possess nearly ideal octahedral geometry. The two Re(CO)₃ units are linked together by the bridging diphosphine ligand and two bridging bromide groups.     

Hydrothermal crystallization and X-ray structure determination of a new decavanadate with mixed cations [Mn(H2O)6]2[N(CH3)4]2[V10O28]·2H2O

A new decavanadate with mixed cations, [Mn(H₂O)₆]₂[N(CH₃)₄]₂[V₁₀O₂₈]·2H₂O (1), was crystallized from a hydrothermal reaction between MnCO₃ and V₂O₅ in the presence of N(CH₃)₄Br at 100°C. The structure of 1, as determined by x-ray single crystal analysis, consists of cations and anions of hexa-aqua manganese [Mn(H₂O)₆]²⁺, tetramethyl ammonium [N(CH₃)₄]⁺ and decavanadate [V₁₀O₂₈]^6–. The extended H-bonding between the [Mn(H₂O)₆]²⁺ and [V₁₀O₂₈]^6– ions gives rise to a pseudo- two-dimensional network in the crystal lattice x-ray crystallographic data for 1: monoclinic P2₁/n, a = 9.1499(5), b = 12.8725(7), c = 18.625(1) Å, = 92.252(1)°, V = 2192.0(2) ų, MZ = 2, and D _calcd = 2.22 g cm^–3.