Crystal structure of trans-W2(CO)6(PPh2H)2(μ2-PPh2)2

The molecular structure of trans-W²(CO)₆(PPh²H)²(₂-PPh²)² was determined by X-ray diffraction analysis. The two tungsten centers, bridged by two diphenylphosphido ligands, are separated by 3.0667(6) Å with W–P–W angles of 77.10(5) and 77.08(5). Average tungsten–phosphorus bond distances are 2.461(17) and 2.4576(21) Å for bridging and terminal phosphorus groups, respectively, with a range of 0.037 Å for the former and 0.001 Å for the latter. The complex crystallizes in the monoclinic space group P2₁/c with a = 19.282(4) Å, b = 12.158(2) Å, c = 21.294(9) Å, = 92.821(4), and Z = 4.     

Crystal structure of triethylentetraammonium bis monohydrogen-monophosphate dihydrate β-NH3(CH2)2NH2(CH2)2NH2(CH2)2NH3(HPO4)2·2H2O

The salt triethylentetraammonium bis monohydrogen-monophosphate dihydrate is orthorhombic Pbca with unit cell dimensions a = 8.963(2), b = 10.326(2), c = 17.381(4)Å; Z = 4; D_m = 1.540 g cm^–3; D _x = 1.562 g cm^–3. The examination of the structure shows a layer arrangement parallel to the axis: planes of [HPO₄]^2– tetrahedra alternate with planes of [(NH₃(CH₂)₂NH₂CH₂)₂]⁴⁺. The [HPO₄]^2– tetrahedra are connected through O(W)s--H···O hydrogen bonds, so that infinite chains of the composition [HPO₄(H₂O)]_n ^2n– are formed in the structure parallel to the axis. The structure of this compound is built from [HPO₄]^2– anions, [(NH₃(CH₂)₂NH₂CH₂)₂]⁴⁺ cations and zeolitic water molecules connected by hydrogen bonds.     

Crystal structure of triethylentetraammonium bis monohydrogenmonophosphate dihydrate, [NH3(CH2)2NH2(CH2)2NH2(CH2)2NH3](HPO4)2 · 2H2O

The salt triethylentetraammonium bis monohydrogenmonophosphate dihydrate is monoclinic with the following unit cell dimensions: a = 8.462(1), b = 10.500(1), c = 9.520 Å, = 99.297(1)°, space group P2₁/n with Z = 2. The structure was solved by the Patterson method and refined to final R value of 0.043 for 1590 independent reflections. The structure consists of infinite parallel two-dimensional [ 01] planes built of mutually connected ions and water molecules by strong O—H···O and N—H···O hydrogen bonding.     

Structure of the adduct of bis(O,O′-diisopropyldithiophosphato) metal with pyridine: Ni[(iPrO)2PS2]2(py)2 and Cd[(iPrO)2PS2]2 (py)2(py = pyridine)

The crystal and molecular structures of the complex of [Ni{(iPrO)₂dtp}₂(py)₂] and [Cd{(iPrO)₂dtp}₂(py)₂] (dtp = dithiophosphate, py = pyridine) have been determined by X-ray crystallography. They are isomorphous. The crystal structures are very similar and consist of discrete molecules of [Ni{(iPrO)₂dtp}₂(py)₂] and [Cd{(iPrO)₂dtp}₂(py)₂], respectively. They both crystallize in the monoclinic system, space group P2₁/c, the former with lattice parameters a = 6.489(1) Å, b = 14.830(3) Å, c = 16.386(3) Å, = 99.74(3), and Z = 2; the latter with a = 6.461(3) Å, b = 14.583(4) Å, c = 17.433(4) Å, = 99.55(3)°, and Z = 2. They all display distorted octahedral geometry around the central metal atom. In the complexes, two O,O-diisopropyl dithiophosphate ions act as bidentate ligands with their S atoms coordinated to metal. Each forms a four-membered chelate ring in the equatorial plane. The N atoms from two pyridine ligands are axially coordinated to the metal atom. The Ni–S bond distances are 2.5137(10) and 2.5386(9) Å, and the Ni–N bond distances are 2.127(3) Å. The Cd–S(1) and Cd–S(2) bond distance are 2.694(1) and 2.704(1) Å, respectively, and the Cd–N bond distances are 2.399(3) Å. The IR spectra data is in agreement with the structural data.     

Synthesis and structural analysis of (μ-SCH2CH2CH2S-μ)Fe2(CO)5(2-C5H4NPPh2)

Treatment of (μ-SCH₂CH₂CH₂S-μ)Fe₂(CO)₆ with equimolar 2-C₅H₄NPPh₂ in the presence of Me₃NO·2H₂O in CH₂Cl₂/MeCN solutions gave the title complex (μ-SCH₂CH₂CH₂S-μ)Fe₂(CO)₅(2-C₅H₄NPPh₂) in 76% yield. The title complex was characterized by spectroscopy as well as by single crystal X-ray diffraction analysis. The molecular structure consists of a butterfly [Fe₂S₂] cluster with propane, five carbonyls, and 2-C₅H₄NPPh₂. In the crystal packing diagram, intermolecular C–H···O hydrogen bonds between phenyl and carbonyl groups stabilize the solid state.     

三维孔道结构(H3 NCH2 CH2 NH3)2(H3 NCH2 CH2 NH2)[VⅢ(H2O)2(VⅣ O)8(OH)4(H(P,B)O4)4((P,B)O4)4(H2O)2]·3H2O的水热合成及晶体化学研究 --(2)晶体结构与晶体化学

在单晶X射线衍射实验的基础上,对孔道结构化合物V9P8-en的类质同象物V9(P,B)8-en的晶体结构和晶体化学进行了深入研究.结果表明,该化合物的晶体学数据为:P2(1)/n,a=1.43134(9)nm,b=1.01256(6)nm,c=1.83156(12)nm,β=90.280(2)°,V=2.6545(3)nm3,Z=2,R=0.0540,wR2=0.1551.结构中,沿着三个结晶轴方向发育复杂而规整的三维孔道,最大孔径达1.83nm(∥b轴),质子化乙二胺和水分子居于孔道中.硼部分替代四面体配位的磷,替代率为B8:P8=0.1838:7.8162;其中B与{P-OH}位P的替代量大于与[P-O]位P的替代量.相对于V9P8-en来说,V9(P,B)8-en的晶胞参数发生了变化,导致b轴增长(1.0150→1.0256nm)和c轴缩短(1.8374→1.8316nm),同时β角变小(90.39→90.278(2)°).二者的化学计量比也不同,体现在结构与孔容的关系、电荷平衡、满足亲水-疏水作用的结晶水的数量及有机模板分子的赋存状态等方面都有差异.     

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).     

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 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.     

层状结构钒磷酸盐(pipzH2)2[(VO)3(HPO4)2(PO4)2]·H2O的水热合成及热稳定性研究

水热合成了钒磷酸盐体系中少有的结构中具有多面体共棱连接的层状孔道结构化合物(pipzH2)2[(VO)3(HPO4)2(PO4)2]·H2O的纯相.用ICP、单晶XRD、TG-DTA、粉晶XRD和SEM对产物进行了表征.结果表明,化合物在空气中开始失重的温度为274 ℃,随着温度的升高,化合物中有机分子分解,同时伴随着重结晶过程,但晶体的外观形貌保持不变直至有机部分分解殆尽.相变过程分析和与模板相同的(pipzH2)0.5[(VO)(PO4)]的热稳定性对比研究表明,有机模板的稳定性及分解过程不但影响化合物的热稳定性和热变化过程,还影响原晶体微形貌的保持;无机骨架结合的牢固程度在很大程度上影响化合物的热稳定性.     

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 cyanocadmate clathrate with 2-methylimidazole (2-Meim): [Cd3(CN)6(2-Meim)2] ⋅ 2Me2SO

The cyanocadmate clathrate with 2-methylimidazole, [Cd₃(CN)₆(2-Meim)₂] 2Me₂SO, has been prepared and its crystal structure analyzed by X-ray diffraction method. This clathrate crystallizes in the orthorhombic system, space group Pbcn, with a = 13.237(3), b = 14.870(3), c = 14.698(3) Å, V = 2893.1(10) ų, Z = 4. The three-dimensional (3D) host framework is built of the cyanide bridges among two kinds of Cd ions, octahedral and tetrahedral in a ratio of 1:2. The octahedral Cd(1) center is linked to six tetrahedral Cd atoms; the tetrahedral Cd(2) center is linked to three octahedral Cd atoms and ligated by one 2-methylimidazole ligand. The novel host structure provides two types of channel, vacant distorted-diamond channel and rectangular channel which is occupied by dimethylsulfoxide guest molecule and 2-methylimidazole ligand coordinated to the tetrahedral Cd site.     

Reaction of trimethylaluminum and trimethylgallium with bifunctional amines: Syntheses and molecular structures of [Me2Al−N(CH2CH2)2−C−(OCH2)2]2 and [Me2Ga−N(Si(H)Me2)2]2

The crystalline products [Me₂Al–N(CH₂CH₂)₂–C–(OCH₂)₂]₂ (I) and [Me₂Ga–N(Si(H)Me₂)₂]₂ (II) were prepared from reactions of trimethylaluminum and trimethylgallium with 1,4-dioxa-8-azaspiro[4.5]-decane and 1,1,3,3-tetramethyldisilazane, respectively, in toluene. The organoaluminum dimer crystallizes in the monoclinic space groupP2₁/c with unit cell parametersa=8.970(2) ,b=9.683(2) ,c=12.833(3) , =103.18(2)°,V=1085.3(3) ³, andD _calcd=1.22 g cm^–3 forZ=2. Least-squares refinement based on 935 observed reflectionsI>3(I) in the range 3.5°<2<45.0° led to a finalR factor of 0.033 (R _w =0.041). The dimeric organosilazagallium crystallizes in the triclinic space group with unit cell parametersa=7.636(2) ,b=9.168(2) ,c=9.466(3), =72.81(2)°, =87.94(2)°, =69.90(2)°,V=593.0(3) ³, andD _calcd=1.30 g cm^–3 forZ=1. Least-squares refinement based on 1661 observed reflectionsI>3(I) in the range 3.5°<2<48.0° led to a finalR factor of 0.055 (R _w =0.070). Both compoundsI andII reside about a crystallographic center of symmetry and contain a planar M₂N₂ (M=Al forI, Ga forII) four-membered ring withI having an Al...Al contact of 2.801 .     

Site-selective ligand substitution in CoRu(CO)7(μ-PPh2) using (Z)-Ph2PCH=CHPPh2 and reactivity of DMAD with CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](μ-PPh2). X-ray structures of CoRu(CO)5[(Z)-Ph2PCH=CHPPh2](μ-PPh2) and CoRu(CO)3(μ-CO)[(Z)-Ph2PCH=CHPPh2] [μ, η3-Ph2PC(CO2Me)C(CO2Me)]

The heterometallic complex CoRu(CO)₇(μ-PPh₂) (1) reacts with the diphosphine ligand (Z)-Ph₂PCH=CHPPh₂ under both thermolysis and Me₃NO activation to furnish CoRu(CO)₅[(Z)-Ph₂PCH=CHPPh₂](μ-PPh₂) (2) in good yield. Treatment of 2 with dimethyl acetylenedicarboxylate (DMAD) at elevated temperature leads to the formal insertion of the DMAD ligand into the Co–phosphido bond and formation of the metallocyclic compound CoRu(CO)₃(μ-CO)[(Z)-Ph₂PCH=CHPPh₂][μ,η³-Ph₂PC(CO₂Me)C(CO₂Me)] (3) that contains a 5e^? alkenylphosphine moiety. These new CoRu compounds have been isolated by chromatography and fully characterized in solution by IR and NMR (¹H and ³¹P) spectroscopies, and the solid-state structures of both 2 and 3 have been determined by X-ray diffraction analysis. CoRu(CO)₅[(Z)-Ph₂PCH=CHPPh₂](μ-PPh₂) crystallizes in the monoclinic space group P2 ₁/n, a = 11.493(8), b = 20.24(1), c = 17.04(1) Å, β = 91.03(1)°, V = 3964(5) ų, Z = 4, D _calc = 1.477 Mg/m³; R = 0.0475, R _w = 0.1054 for 5120 observed reflections with I > 2σ (I). CoRu(CO)₃(μ-CO)(Z)-Ph₂PCH=CHPPh₂][μ,η³-Ph₂PC(CO₂Me)C(CO₂Me)], as the CH₂Cl₂ solvate, crystallizes in monoclinic space group P2 ₁/c, a = 17.0307(9) Å, b = 11.2124(6) Å, c = 24.083(1) Å, β = 97.755(1)°, V = 4556.8(4) ų, Z = 4, D _calc = 1.579 Mg/m³; R = 0.0379, R _w = 0.0609 for 10774 observed reflections with I > 2σ(I). The regioselective coordination of the (Z)-Ph₂PCH=CHPPh₂ ligand to the two equatorial sites of the ruthenium center in 2 and the presence of the metallocyclic alkenylphosphine ligand in 3 are confirmed by the structural studies. The regiochemistry found in the coordination of (Z)-Ph₂PCH=CHPPh₂ to 1 is contrasted with the related diphosphine ligands bma and bpcd, while the DMAD insertion reactivity with 2 is discussed relative to alkyne reactions reported for the parent compound CoRu(CO)₇(μ-PPh₂).     

三维孔道结构(H3NCH2CH2NH3)2(H3NCH2CH2NH2)[VⅢ(H2O)2(VⅣO)8(OH)4(H(P,B)O4)4(P,B)O4)4(H2O)2]·3H2O的水热合成及晶体化学研究——(1)水热合成与产物表征

为了探讨化学成份对VPO体系孔道结构化合物结构稳定性的影响,根据酸碱平衡原理进行了合成实验设计;利用V2O5、H3PO4、H3BO3等简单的无机前驱物、乙二胺作结构导向剂,水热法合成了孔道结构钒硼磷酸盐化合物(H3NCH2CH2NH3)2(H3NCH2CH2NH2)[VⅢ(H2O)2(VⅣO)8(OH)4(H(P,B)O4)4((P,B)O4)4(H2O)2]·3H2O(简称V9(P,B)8-en).典型的反应起始物摩尔比为n(V2O5):n(H3BO3):n(H3PO4):n(en):n(H2O)=0.89:3.50:3.50:3.60:265(pH值为6.5),在175℃、自生压力条件下恒温晶化6.5d(最终pH值为5.9).通过电子探针、粉末X射线衍射、红外吸收光谱、原子占位度修正等方法,对产物的化学成份、物相及其结构等进行了实验研究.证实V9(P,B)8-en为V9P8-en的类质同象化合物,不同晶粒中B与P的含量有差别,B与P之比为O.1:7.9～2.54:5.46(原子比),但恒有V:(P+B)≈9:8.表明通过合理设计和控制合成条件,可在保持V9P8-en基本结构不变的前提下通过同晶取代引入新的化学成份,并由此探讨成份与结构稳定性的关系.     

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.     

Synthesis of [Mn(O2CCH2CH2CO2)(2,2′-bipyridyl) (H2O)2]n·H2O

The title compound exists as a 1D coordination polymer consisting of succinate anions, manganese cations and 2,2-bipyridyl molecules. Twelve water molecules are present in the unit cell and are part of a hydrogen bonding system. Some of these waters are binding to manganese cations while others are only participating in hydrogen bonding. The structure has a monoclinic space group P2₁/c with a = 8.2750(3) Å, b = 11.5104(3) Å and c = 16.9113(6) Å, = 95.2727(16); V = 1603.96(9) ų and Z = 4.     

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.     

Crystal structure of [WBr2(CO)(PPh2Cy)2(η2-MeC2Me)]·CH2Cl2 (Cy = cyclohexyl)

[WBr₂(Co)(PPh₂Cy)₂(²-MeC₂Me)]·CH₂Cl₂ (Cy = cyclohexyl) crystallizes in the monoclinic space group, P2₁/n, with a = 10.606(12), b = 23.11(3), c = 18.19(2) Å, = 106.070(10) D_calc = 1.610g cm^–3 for Z = 4. The tungsten coordination geometry can best be considered as a distorted octahedron, with the but-2-yne ligand occupying one coordination site, which has a trans-Br(2) group. The equatorial plane is made up of trans-PPh₂Cy groups, with the bromo and carbonyl ligands occupying the other two sites.