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.     

[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.     

Crystal structure of aqua[S-prolinato-N-monoacetato)copper(II) dihydrate [Cu(Proma)H2O] ⋅ 2H2O

The crystal structure of [Cu(C₇H₉NO₄)H₂O] ? 2H₂O is determined by X-ray diffraction (λMo, R = 0.0316 for 857 reflections). The crystals are tetragonal, a = 8.219(1) Å, c = 17.449(3) Å, Z = 4, ρ_calcd = 1.627 g cm^?3, and space group P4₃. The coordination polyhedron of the Cu atom is a tetragonal pyramid with the O atom of the acetate arm of the prolinatomonoacetate ion (Proma) in the apical position [Cu-O 2.312(6) Å]. The O atom of the water molecule and the N and O atoms of the prolinate group of the Proma ligand lie in the basal plane. The Cu-N bond length is 2.044(6) Å, and the Cu-O bond lengths are 1.932(7) and 1.927(6) Å. The O atom of the acetate arm of the neighboring Proma ion completes the basal plane [Cu-O 1.951(6) Å], thus linking the copper complexes into infinite chains.     

Reactions of [Mn2(μ-pyS)2(CO)6] with bidentate phosphines: X-ray structure of [Mn(η2-pyS) (η2-dppp)(CO)2] [dppp = Ph2P(CH2)3PPh2, pySH = pyridine-2-thiol]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 molar equivalents of Ph₂P(CH₂)₃PPh₂ (dppp) and Ph₂P(CH₂)₂PPh₂ (dppe) to give the respective monomeric chelate complexes [Mn(²-pyS)(²-dppp)(CO)₂] (2) and [Mn(²-pyS)(²-dppe)(CO)₂] (3). In contrast, with 2 molar equivalents of Ph₂P(CH₂)₅PPh₂ (dpppe), 1 gave the highly insoluble polymeric complex [Mn(²-pyS)(-dpppe)(CO)₂]n (4). An X-ray structure determination shows that 2 crystallizes in the monoclinic space group P2₁/n with a = 10.721(2) Å, b = 19.712(5) Å, c = 14.846(4) Å, = 109.06(2)°, V = 2965.5(14) ų, and Z = 4. The complex has a distorted octahedral geometry with the dppp ligand, one CO group and the N atom of the chelating pyS ligand occupying equatorial sites, and one CO group and the S atom of the pyS ligand lying in the axial positions.     

配合物[Co(SCN)2(HSCN)2(dabco)2]的合成、晶体结构与表征

以SCN-和三乙撑二胺(dabco)为配体,以钴为中心离子采用自组装的方法合成了配合物[Co(SCN)2(HSCN)2(dabco)2],采用单晶X射线衍射、红外光谱、热重分析和元素分析等方法对其进行了晶体结构的解析和表征.它属于单斜晶系,P21/n空间群,晶胞参数分别为a＝0.71964(11)nm,b＝1.12716(17)nm,c＝1.4454(2)nm,β＝96.629(2)°,V＝1.1646(3)nm3,Dc＝1.470 g/cm3,Z＝2,F(000)＝534,μ＝1.115mm-1.热重分析表明,该配合物在530 K以下稳定.     

钴(Ⅱ)三元配合物[Co(pht)2(MeOH)2(H2O)2]的合成与晶体结构

利用溶剂热法合成了一个新的钴(Ⅱ)配合物[Co(pht)2(MeOH)2(H2O)2](Hpht:苯妥英,即5,5-二苯基-2,2咪唑烷酮),通过元素分析、红外光谱、热重差热分析、X射线单晶衍射等技术对其结构进行了表征.单晶结构分析表明,该晶体属单斜晶系,P21/C空间群,晶胞参数:a=1.2124(2)nm,b=1.09996(19)nm,c=1.1574(2)nm,β=92.555(2)°,V=1.5419(5)nm3,Dc=1.425 mg/m3,Z=2,F(000)=690,μ=0.615 nm-1,R1=0.0467,wR2=0.1116[I>2σ(I)],GOF=1.026.Co(Ⅱ)离子位于八面体的中心,与六个配位原子配位(40+2N).     

Crystal structures of mixed ligand complexes containing saccharinate and nicotinamide: [Cu(saccharinato)2 (nicotinamide) (H2O)]⋅(H2O) and [M(nicotinamide)2 (H2O)4]⋅(saccharinate)2 (M = Ni2+, Co2+)

[M(saccharinato)₂(H₂O)₄] (M = Cu²⁺, Ni²⁺, Co²⁺) react with nicotinamide to form mixed ligand complexes, [Cu(saccharinato)₂(nicotinamide)(H₂O)](H₂O) (1) and [M(nicotinamide)₂(H₂O)₄](saccharinate)₂ (2: M = Ni²⁺; 3: M = Co²⁺), and their crystal structures have been determined by X-ray diffraction. In 1, the Cu²⁺ atom in an octahedral configuration is coordinated by two monodentate saccharinato ligands in the trans arrangement through the deprotonated ring nitrogens, by two bidentate nicotinamide ligands, one through the pyridyl ring nitrogen and the other through the amide oxygen, and by a water molecule, thus forming a nicotinamide-bridged one-dimensional extended structure. In the isomorphous complexes 2 and 3, the octahedral metal atom, which rides on a crystallographic center of symmetry, is coordinated by two monodentate nicotinamide ligands through the ring nitrogens and four water molecules to form a discrete [M(nicotinamide)₂(H₂O)₄]^{2 +} structural unit, which captures up and down two saccharinate ions, each through three hydrogen bonds: two hydrogen bonds between two water ligands and the ring N and the carbonyl O atoms and one between the amide N of the nicotinamide ligand and the carbonyl O.     

Structure of bis[α-(1,2,4-triazole-1-yl)-acetophenone] dichorozinc(II) complex [ZnCl2(C2H2N3CH2COPh)2]

The crystal and molecular structure of [ZnCl₂(N⁴-trzCH₂COPh)₂] (trz = 1,2,4-triazole) has been determined by X-ray crystallography. It crystallizes in the monoclinic system, space group C2/c, with lattice parameters a = 26.7892(4) Å, b = 4.9392(2) Å, c = 20.7872(1) Å, = 127.517 (1), and z = 4. The complex has C ₂ symmetry. The coordination geometry of each Zn atom is distorted tetrahedral formed by two Cl atoms and two tertiary N atoms of the -(1,2,4-triazole-1-yl)-acetophenone ligands. The two equivalent Zn–Cl and Zn–N bonds form bond angles around the Zn(II) atom in the range 101.4(1)–120.8(1). C–H O intermolecular interactions link the molecules in infinite chains in the [101] direction.     

Reactions of [Mn2(μ-pyS)2(CO)6] (pySH=pyridine-2-thiol) with triphenylphosphine (PPh3), diphenylphosphine (PHPh2) and bis(diphenylphosphino)methane (dppm): X-ray crystal structure of [Mn(pyS)(η1-dppm)2(CO)2]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 M equivalents of both PPh₃ and PHPh₂ to give the respective monomeric phosphine complexes [Mn(pyS)(L)(CO)₃][L = PPh₃ (2) and PHPh₂ (3)]; with 4 M equivalents of dppm, it yielded the complex [Mn(pyS)(¹-dppm)₂(CO)₂](4). An X-ray structure determination of 4 shows that it crystallizes in the monoclinic space group P2₁/n with a = 11.027(3), b = 24.984(7), c = 18.379(5) Å, = 99.870(8)°, V = 4988(2) ų, and Z = 4. The complex has an octahedral geometry with the chelating pyS ligand and two CO groups occupying the equatorial sites and the two monodentate dppm ligands lying in the trans positions.     

Self-assemblies of Ni(II) with phenanthroline and maleate anions: [Ni(H2O)3(phen)L] ⋅ H2O (1) and [Ni(H2O)2(phen)L] ⋅ 2H2O (2) with H2L = maleic acid

The complex [Ni(H₂O)₃(phen)(C₄H₂O₄)] H₂O (1), which was obtained by reaction of phenanthroline, Ni(NO₃)₂ 6H₂O, and maleic acid in CH₃OH/H₂O at pH = 7.05, crystallized in the monoclinic space group P2₁ (no. 4) with cell dimensions: a = 9.350(1) Å, b = 7.631(1) Å, c = 12.821(1) Å, = 106.25(1), and D _calc = 1.607 g/cm³ for Z = 2. The Ni atoms are each octahe drally coordinated by one chelating phen ligand, three H₂O molecules and one monodentate maleato ligand to form [Ni(H₂O)₃(phen)(C₄H₂O₄)] complex molecules with d(Ni–O) = 2.038–2.090 Å, d(Ni–N) = 2.066, 2.089 Å. The formed complex molecules are, via the intermolecular hydrogen bonds, assembled into columnar 1D chains. Interdigitation of the chelating phen ligands of the neighboring chains leads to 2D layers and the crystal H₂O molecules are hydrogen bonded to the oxygen atoms of the maleate not coordinated to the Ni atom. However, reaction of NiCO₃, phen, and maleic acid in CH₃OH/H₂O at pH = 6.33 afforded [Ni(H₂O)₂(phen)(C₄H₂O₄)] 2H₂O (2), which crystallized in the triclinic space group (no. 2) with cell dimensions: a = 7.971(1) Å, b = 8.237(1) Å, c = 13.304(1) Å, = 81.005(6)°, = 87.877(8)°, = 78.322(8)°, and D _calc = 1.671 g/cm³ for Z = 2. The Ni atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of two H₂O molecules and two bis–monodentate maleato ligands with d(Ni–O) = 2.041–2.120 Å and d(Ni–N) = 2.095 Å. The Ni atoms are bridged by the maleato ligands to generate 1D ¹ [Ni(H₂O)₂(phen)(C₄H₂O₄)_2/2] chains along [100]. The supramolecular assemblies of the 1D chains via – stacking inter- actions result in thick 2D layers parallel to (001), between which the noncoordinating H₂O molecules are sandwiched. The paramagnetic [Ni(H₂O)₂(phen)(C₄H₂O₄)_2/2] 2H₂O (2) obeys the Curie–Weiss law _m(T-) = 1.139cm³ mol^–1 K with the Weiss constant = –0.95 K.     

Synthesis and crystal structure of (CN3H6)2[UO2(OH)2(NCS)]NO3 and β-Cs3[UO2(NCS)5]

Compounds (CN₃H₆)₂[UO₂(OH)₂(NCS)]NO₃ (I) and β-Cs₃[UO₂(NCS)₅] (II) are synthesized and studied by IR spectroscopy and single-crystal X-ray diffraction. I and II crystallize in the orthorhombic system. For I, a = 12.2015(13) Å, b = 7.3295(8) Å, c = 16.310(2) Å, space group Pnma, Z = 4, and R = 0.0327; for II, a = 21.7891(6) Å, b = 13.5120(3) Å, c = 6.8522(2) Å, space group Pnma, Z = 4, and R = 0.0268. In structure I, complex groups form infinite chains [UO₂(OH)₂(NCS)] _n ^n? belonging to the AM ₂ ² M ¹ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , M ² = OH^?, and M ¹ = NCS^?). The main structural elements of crystals II are mononuclear [UO₂(NCS)₅]^3? groups belonging to the AM ₅ ¹ group of uranyl complexes (A = UO ₂ ²⁺ and M ¹ = NCS^?). In I and II, uranium-containing complexes are connected with outer-sphere cations by electrostatic interactions, and in I a system of hydrogen bonds also contributes to their binding. Specific features of the packing of complex [UO₂(NCS)₅]^3? groups in the structures of two modifications of Cs₃[UO₂(NCS)₅] are discussed.     

Synthesis and crystallographic characterization of [Cd(OH2)2 (μ-Br)4 (Cd(2-hydroxyethyl sulfide) (μ-Br))2]n

The reaction of equal millimolar quantities of CdBr₂ and 2-hydroxyethyl sulfide in 31 CH₃CNCH₃OH produced [Cd(OH₂)₂(Br)₄ (Cd(2-hydroxy ethyl sulfide) (-Br))₂]_n. The compound crystallizes as a bromide-bridged polymer with hydrogen bonding interactions between the polymeric chains. Each of the two unique metal centers has a distorted octahedral geometry. The thioether ligand is bidentate to one cadmium position with one alcoholic terminus uncoordinated. The uncoordinated portion of the molecule is disordered with each conformation participating in slightly different hydrogen bonding environments. The other unique cadmium center is coordinated to four bridging bromides and twotrans water molecules.     

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.     

配合物[Cu(pht)2(fa)2](H2O)2的合成、晶体结构及性质研究

用醋酸铜、苯妥英(即5,5-二苯基-2,2咪唑烷酮,简称Hpht)与糠胺(2-furfurylamine,简称fa)反应,得到一种新的配合物[Cu(pht)2 (fa)2] (H2O)2,通过红外光谱、元素分析以及Ⅹ-射线单晶衍射的方法,对配合物的结构进行了表征.该晶体属三斜晶系,Pt空间群,晶胞参数:a =0.9878(2) nm,b=1.0068(2) nm,c=1.0640(3) nm,α=78.664(3)°,β=75.490(2)°,γ=72.050(3)°,Z=1,Dc=1.368 mg·m-3,R1=0.0986,ωR2 =0.2191.每个标题配合物分子中Cu(Ⅱ)离子与2个Hphi配体、2个fa配体的4个氮原子形成四方形构型,同时利用琼脂扩散法测试了配合物、苯妥英和铜盐对大肠杆菌(Escherichia Coli),金黄色葡萄球菌(Staphylococcus Aureus),枯草芽孢杆菌(Bacillus Subtilis)的抑菌活性,结果表明,它们对3种致病细菌均有一定的抑制作用.     

Crystal structure of [WI2(CO)2{P(OiPr)3}(η2-EtC2Et)]

[WI₂(CO)₂{P(OⁱPr)₃}(²-EtC₂Et)] crystallizes in the monoclinic space group P2₁/n, with a = 11.101(12), b = 16.272(18), c = 14.892(17) Å, = 93.27(1), Z = 4. The geometry can be considered to be pseudo-octahedral, with the 3-hexyne ligand occupying one site, with two iodo-groups, and the P(OⁱPr)₃ ligand completing the equational plane of ligands, with two trans-carbonyl groups occupying the axial sites.     

Molecular and crystal structure of [NO2Py]2[Ni(mnt)2](NO2Py=1-(4-nitrobenzyl)pyridinium, mnt2−=maleonitriledithiolate)

The structure of [NO₂Py]₂[Ni(mnt)₂], as determined by x-ray single crystal analysis, consists of two 1-(4-nitrobenzyl)pyridinium cations and one [Ni(mnt)₂]^2– anion. The crystallographic data for the complex:monoclinic P2₁/n, a = 9.913(2) Å, b = 11.968(2) Å, c = 14.566(3) Å, = 100.36(3)°, V = 1699.9(6) ų, Z = 2. The [Ni(mnt)₂]^2– anion has a crystallographically imposed center of symmetry and exhibits a relatively planar structure. The cation, [NO₂Py]⁺, adopts a conformation where both the aromatic rings are twisted to the C11-C10-N3 reference plane. The anions (A) and the cations (C) consist of alternating layers (i.e., of type ···C₁A₁C₂A₂C₁A₁C₂···) along the c axis of the crystallographic unit cell.     

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.     

Synthesis and crystal structure of bis(carbamide)chromatoneptunyl NpO2CrO4 · 2[OC(NH2)2]

The crystal structure of the hexavalent neptunium complex NpO₂CrO₄ · 2[OC(NH₂)₂] is determined. The crystal data are a = 7.192(2) Å, b = 12.902(4) Å, c = 11.226(3) Å, β = 92.19(2)°, V = 1040.9(4) ų, space group P2₁/n, Z = 4, d _calcd = 3.223 g/cm³, R = 0.045, and R _w = 0.130. The coordination polyhedron of the Np atom is the pentagonal bipyramid whose equatorial plane is formed by the oxygen atoms of the chromate ions and carbamide molecules.     

新型配位聚合物[Co(pda)2(H2O)2]n的水热合成和晶体结构

以CoCl2·6H2O和3-(3-吡啶基)丙烯酸(pda)为原料,在中温水热反应条件下,合成了一种新型配位聚合物[Co(pda)2(H2O)2]n单晶体,并对其进行了元素分析、红外光谱表征、TGA-GTA分析和X射线单晶衍射测定.该配位聚合物属单斜晶系,P2(1)/c空间群,晶胞参数为a=1.6958(8)nm;b=0.5466(3)nm;c=1.8034(8)nm;α=90°;β=106.209(7)°;γ=90°;Mr=391.24;V=1.6051(13)nm3;Z=4;dc=1.619g/cm3;μ=1.106mm-1;F(000)=804;R1=0.0367;wR2=0.0711.该晶体通过配位键的连接形成二维结构,又通过分子间氢键和π-π相互作用形成三维的网状结构.     

2-pyridylbis(diphenylphosphino)methane chemistry. Synthesis and structures of [Cu(μ−η2:η1(Ph2P)2−CHC5H4N)(THF)]2(BF4)2 and [Ni(Ph2PCH2C5H4N)2]-[NiCl4]·0.85CH2Cl2and [Ni(Ph2PCH2C5H4N)2]-[NiCl4]·0.85CH2Cl2

Reaction of 2-pyridylbis(diphenylphosphino)methane (NPP) with [Cu(NCMe)₄]BF₄ and with [Ni(H₂O)₆]Cl₂ forms [Cu(NPP)(THF)]₂(BF₄)₂ (after recrystallization in the presence of THF) (1) and NiCl₂(NPP) (2) respectively Attempts to recrystallize2 led ultimately to the ligand cleavage product [Ni(Ph₂PCH₂C₅H₄N)₂][NiCl₄]·0.85CH₂Cl₂ (3). Complex1 crystallizes in the monoclinic space groupP2₁/n witha=13.148(2),b=19.221(2),c=13.458(2) ų, β=108.61(1)^o,V=3222.6(8) ÅZ=2. The structure was refined onF ² toR1=0.11,wR2=0.14 (R1=0.044 forI≥2σ(I)) for 5661 observed reflections. Complex3 crystallizes in the triclinic space groupP1 witha=12.795(2),b=17.535(1),c=10.203(1) Å, α=107.564(6), β=114.260(8), γ=78.435(8)^o,V=1982.1(8) ų;Z=2. The structure was refined onF toR1=0.044,R _w=0.059 for 3534 observed reflections. Dinuclear complex1 has crystallographically imposed centrosymmetry with the NPP ligands arranged in a head-to-tail fashion. The Cu...Cu separation of 3.372(1) Å is too long to support significant metal-metal interaction. Complex3 results from the cleavage of a {PPh₂} unit from the NPP ligand and contains an approximately square nickel atom surrounded by two Ph₂PCH₂C₅H₄N ligands coordinated in a head-to-head fashion.