PhPMe2 ligand substitution in the tetracobalt cluster Co4(CO)10(μ4-PPh)2: X-ray diffraction structure of Co4(CO)8(PPhMe2)2(μ4-PPh)2

The thermal substitution chemistry of the tetracobalt cluster Co₄(CO)₁₀(₄-PPh)₂ with the phosphine ligand PhPMe₂ (2.5 equiv) has been explored and found to afford the bis(phosphine)-substituted cluster Co₄(CO)₈(PPhMe₂)₂(₄-PPh)₂ as the major reaction product. The regiochemistry and stereoselectivity exhibited by the two phosphine ligands in Co₄(CO)₈(PPhMe₂)₂(₄-PPh)₂ have been unambiguously established by X-diffraction analysis as having a 1,3-cis orientation. Co₄(CO)₈(PPhMe₂)₂(₄-PPh)₂ crystallizes in the monoclinic space group P2₁/n,a=10.314(1) Å,b=18.051(3) Å,c=21.313(2) Å, =90.10(1)°,V=3968.0(8) ų,Z=4,d _calc=1.590 g cm^–3;R=0.051,R _w=0.042 for 4987 observed reflections withI>3(I). Generalizations concerning the stereochemical disposition of two P-ligands about the Co₄(CO)₈P₂(₄-PPh)₂ (where P=phosphine or phosphite) polyhedron are discussed with respect to the cone angle of the P-ligand and its steric interactions with the capping phenylphosphinidene group.     

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.     

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.     

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.     

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.     

孔道结构铁磷酸盐(C4H12N2)2[Fe6(HPO4)2(PO4)6(H2O)2]·H2O的水热合成及热变化过程研究

在与前人不同的条件下水热合成了孔道结构铁磷酸盐(C4H12N2)2[Fe6(HPO4)2(PO4)6(H2O)2]·H2O.用ICP、有机元素分析仪、TG-DTA、变温XRD、变温FT-IR等分析技术对其成份、物相和热变化过程进行了系统研究.结果表明,室温-330℃,化合物失去吸附水,有机模板哌嗪开始氧化脱氢;330-380℃,哌嗪环破坏,大部分有机模板和结晶水脱除,化合物结构骨架明显破坏;470℃化合物完全非晶化;650℃形成FePO4和Fe4(P2O7)3新物相.哌嗪起到平衡电荷和支撑结构的作用.哌嗪环破坏并脱除是导致结构破坏的根本原因.     

Synthesis and structure of (NH4)3[UO2(C3H2O4)2(NCS)] · 2H2O

Malonate-thiocyanate complex (NH₄)₃[UO₂(C₃H₂O₄)₂(NCS)] · 2H₂O is synthesized and studied by X-ray diffraction. The compound crystallizes in the monoclinic system: a = 13.9983(4) Å, b = 8.1947(2) Å, c = 16.4678(4) Å, β = 100.846(1)°, space group Cc, Z = 4, and R = 0.0158. The main structural units of the crystal are mononuclear [UO₂(C₃H₂O₄)₂(NCS)]^3? groups belonging to the AB ₂ ⁰¹ M ₁ crystal chemical group of uranyl complexes (A = UO ₂ ²⁺ , B ⁰¹ = C₃H₂O ₄ ^2? , M ¹ = NCS^?). Discrete uranium-containing groups are connected by electrostatic interactions with ammonium ions and by hydrogen bonds. Some specific structural features of crystals containing [UO₂(L)₂(NCS)]^3? complexes, where L is the oxalate or malonate ion, are discussed.     

新型磷酸钒孔道结构化合物(H3NCH2CH2NH3)3[(VO)4(PO4)2(HPO4)4]的表征及热性能研究

利用五氧化二钒、磷酸作前驱物,乙二胺作模板,水热法合成了新型孔道结构磷酸盐化合物(H3NCH2CH2NH3)3[(VO)4(PO4)2(HPO4)4].借助红外光谱(FT-IR)、热分析(TG-DTA)、粉晶X 射线衍射(XRD)及扫描电镜(SEM)等手段,对该化合物晶体在受热条件下的孔容脱除、结构变化及热相变特征等进行了系统研究.从晶体化学角度对其成分、结构及热稳定性之间的关系进行了探讨.指出应通过优化模板、元素替代等方法减弱模板分子与无机骨架间的键联强度及改善基本结构骨架的牢固性,进一步提高其热稳定性.     

三维孔道结构(H_3NCH_2CH_2NH_3)_2(H_3NCH_2CH_2NH_2)[V~Ⅲ(H_2O)_2(V~ⅣO)_8(OH)_4(H(P,B)O_4)_4(P,B)O_4)_4(H_2O)_2]·3H_2O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 0. 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。     

Crystal structure of (4α,4aα,8aα)-(±)-octahydro-2-(phenylmethyl)-2H-1,2-benzoxazin-4-ol, 4-methylbenzenesulfonate(ester)

The title compound, a bicyclic tetrahydro-1,2-oxazine, crystallizes in a monoclinic lattice, space group P2₁/c, with a = 12.9809(18)Å, b = 12.920(2)Å, c = 13.631(2)Å, = 110.713(12)°, and Z = 4. The structure found in the solid state for this conformationally mobile molecule shows the tosyl group in an axial position and a benzyl group in an equatorial position of the bicyclic system.     

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.     

A comparison of the crystal structures of (dabcoH2)CuCl4 and (dabcoH2)CuCl4⋅H2O

The crystal structures of the anhydrous and monohydrated (dabcoH₂)CuCl₄nH₂O salts (n = 0,1) have been determined and a comparison of their crystal structures has been reported. The anhydrous salt is monoclinic P2₁/c with a = 9.045(2) Å, b = 6.9270(10) Å, c = 18.767(4) Å and = 90.07(3)° with V = 1175.8(4) ų. The hydrated salt is also monoclinic P2₁/c with a = 9.266(2) Å, b = 9.395(2) Å, c = 14.386(3) Å and = 93.32(3)° with V = 1250.3(5) ų. The structures of the two salts are closely related. Both compounds contain isolated distorted (compressed) tetrahedral CuCl₄ ^2– anions, diprotonated dabco cations, and in the case of the hydrated salt, lattice H₂O molecules. In the anhydrous salt, each of the two N–H⁺ groups of the dabcoH₂ ²⁺ dications form bifurcated hydrogen bonds to chloride ions on adjacent CuCl₄ ^2– anions along the c axis, thus forming chains running parallel to the c axis. In the hydrated salt, a water molecule is inserted into one of the pair of bifurcated hydrogen bonds, forming instead N–H O–H CuCl₄ ^2– linkages. The chains thus formed are cross-linked by O–H Cl hydrogen bonds between the chains. Because of this additional hydrogen bonding, the CuCl₄ ^2– anions in the hydrated salt are distorted further from tetrahedral geometry.     

Synthesis,crystal structure and spectral studies of the complex [Ni(C3H4N2)4(H2O)2]·(C6H4COSO2N)2

The title compound has been synthesized and its crystal structure determined at room temperature.M _r =731.39, triclinic, space groupP¯1,a=9.020(3),b=11.280(7),c=7.784(2)Å,=97.05(4),=97.08(2), =105.32(4)°, U=748(1)ų,Z=1,D _calc.=1.624 g/cm³. The finalR is 0.030 for 3095 independent observed reflections withI3(I). The crystal structure consists of repeated [Ni(im)₄(H₂O)₂]²⁺ cations and noncoordinated saccharin anions. In the complex cation [Ni(im)₄(H₂O)₂]²⁺, Ni² is bonded to four N atoms from four imidazole molecules and two O atoms from two water molecules forming an approximately square octahedral stereochemistry. The d-d transition spectrum of the title compound is also reported and is explained perfectly with the scaling radial theory which was proposed by us.     

Hydrothermal synthesis and X-ray structure: A reduced titanic molybdenum(V) phosphate (NH3CH2CH2NH2)5Na [Ti2Mo12O30(PO4)(HPO4)4(H2PO4)3]⋅6H2O

A novel titanic molybdenum(V) phosphate (NH₃CH₂CH₂NH₂)₅Na [Ti₂Mo₁₂O₃₀(PO₄) (HPO₄)₄(H₂PO₄)₃]6H₂O crystallizes in the triclinic space group P1 with a = 12.057(3) Å, b = 14.668(2) Å, c = 21.2680(10) Å, = 80.840(10)°, = 82.960(10)°, = 76.65(2)°, and D _c = 2.707 g cm^–3 for Z = 2, Refinement based on 12,037 observed reflections led to R = 0.0609. The result of single crystal x-ray diffraction revealed the presence of a tunnel and two crystallographically independent clusters in the solid state structure. The plane layers in its solid-state structure are interconnected in-sheet (axial) through multipoint hydrogen bonding between the ethylenediamine nitrogen atoms and the cluster oxygen atoms.     

共生晶体Mn2Hg4(SCN)12和MnHg(SCN)4的形成

采用恒温蒸发法从水溶液中生长Hg2+、Mn2+为双配位中心的SCN- 的配合物晶体.生长液中Hg2+含量较SCN-适当过量的条件下,出现Mn2Hg4(SCN)12晶体和MnHg(SCN)4晶体共生现象.MnHg (SCN)4晶体中Hg2+只与SCN-配位,Mn2+只与NCS-配位,而Mn2Hg4(SCN)12晶体中部分Hg2+可以同时与SCN-和NCS-配位体结合,并且部分SCN-同时和2个Hg2+结合成桥式结构.Mn2Hg4(SCN)12晶体中Mn2+的配位数由MnHg(SCN)4晶体中的4配位增大为5配位和6配位.Mn(NCS)4-6 和Mn(NCS)3-5 配位多面体的存在使Mn2Hg4(SCN)12晶体的颜色比MnHg(SCN)4晶体的颜色浅.     

Nd:KY(WO4)2、Nd:KG(WO4)2晶体光谱性能研究比较

在室温下测试了Nd:KYW(Nd:KY(WO4)2)、Nd:KGW(Nd:KG(WO4)2)晶体的吸收光谱,有相似性,这是由于结构相似.吸收峰位置稍有偏移,因为Nd3+离子进入晶体取代离子的半径不同,晶格对Nd3+跃迁影响大小不同.根据J-O理论计算的晶场强度参数反映了它们性质的炯异.同时测试的偏振吸收光谱,表明了明显的偏振性,不同的偏振有不同性质,同一偏振两晶体的性质存有差异.     

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.     

Synthesis and crystal structure of [Co(phen)(H2O)4](SO4)⋅2(H2O)

The title complex, [Co(phen)(H₂O)₄](SO₄)2(H₂O) (phen = 1,10-phenanthroline) was prepared in aqua tert-butylperoxohydrogen solution. X-ray single crystal structure determination reveals that the complex consists of a phenanthrolinatocobalt(II)tetrahydrate dication, two uncoordinated water molecules and a sulfate anion. It crystallizes in the orthorhombic space group Pbca with a = 8.856(1), b = 18.318(3), c =21.918(5) Å, V = 3555.6(11) ų. The coordination geometry at each cobalt(II) atom is a slightly distorted octahedron.     

晶体(NH_4)_2C_4H_4O_6∶VO~(2 )的EPR参量及局域结构的研究

采用叠加模型和双旋-轨耦合参量模型,建立了结构参数与EPR参量之间的定量关系;较好地解释了[VO(H2O)5]2 络离子的局域结构和EPR参量;研究结果发现,(NH4)2C4H4O6:VO2 晶体中络离子[VO(H2O)5]2 的键长为R//≈0.130nm,R⊥≈0.195nm;在(NH4)2C4H4O6:VO2 晶体中,局域结构沿C4轴方向呈压缩的八面体结构;所得EPR参量的理论计算与实验测量数据符合很好。     

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.