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.     

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.     

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.     

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.     

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.     

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.     

Crystal structures of acid ethylenediaminetetraacetates [Cd(H2 Edta)(H2O)] · 2H2O and [Mn(H2O)4][Mn(HEdta)(H2O)]2 · 4H2O

The crystal structures of [Cd(H₂ Edta)(H₂O)] · 2H₂O (I) and [Mn(H₂O)₄][Mn(HEdta)(H₂O)]₂ · 4H₂O (II) are studied by X-ray diffraction [R ₁ = 0.0209 (0.0272), wR ₂ = 0.0571 (0.0730) for 2551 (4025) reflections with I > 2σ(I) in I (II), respectively]. Structure I contains mononuclear [Cd(H₂ Edta)(H₂O)] complexes with the C ₂ symmetry, and structure II contains centrosymmetric trinuclear [Mn(H₂O)₄][Mn(HEdta)(H₂O)]₂ complexes. In I and II, the protonated ligands are hexadentate (2N + 4O), and the water molecule increases the coordination number of the metal atom to seven. The acid protons participate in short intermolecular hydrogen bonds, which are symmetric in II and asymmetric in I.     

一维镉(Ⅱ)配合物[Cd(H2ASA)2(H2O)2]n的合成、晶体结构及光致变色性质

以5-偶氮四唑水杨酸(H3ASA)和CdCl2·2.5H2O为原料,通过常规溶液法合成了一个镉配合物[Cd(H2ASA)2(H2O)2]n(1).通过X-射线单晶衍射、X-射线粉末衍射、元素分析、红外光谱、热重分析、紫外光谱进行结构解析和性质表征.结果 表明配合物1属于三斜晶系,Pi空间群,晶胞参数为a =0.702 39(5) nm,b=0.735 15(6) nm,c=1.229 41(7)nm,α =82.557(5)°,β=75.453(6)°,γ =61.882(8)°,V=0.541 90(8) nm3,Z=1,μ=1.083 mm-1,Dc=1.884g/cm3.配合物1中具有H2ASA-,作为μ2-桥联配体连接两个不同的Cd(Ⅱ)离子形成无限一维链结构,相邻直链通过O…O、O…N氢键和π-π堆积作用形成三维超分子框架.紫外光谱测试表明配合物1在365 nm紫外光照射下具有光致异构性质.     

{[La(phen-dione)2(H2dhtp)0.5(H2O)]·H2O}n配合物的合成、晶体结构及荧光性质

采用低温水热法合成了一个新的镧(Ⅲ)配位聚合物{[La(phen-dione)2(H2dhtp)0.5(H2O)]·H2O}n(phen-dione＝1,10-邻菲啰啉-5,6-二酮,H2dhtp＝2,5-二羟基对苯二甲酸酯).单晶衍射分析结果表明,该配合物属三斜晶系,P-1空间群,晶胞参数为a＝9.4600(19)nm,b ＝11.810(2)nm,c ＝12.280(3)nm,α＝93.34(3)°,β＝106.74(3)°,γ＝103.21(3)°,V＝1267.7(5)nm3,Dc ＝1.806 g/cm3,Z＝2,μ＝1.752mm-1,F(000)＝678.用X-射线单晶衍射、元素分析、IR、TG和荧光光谱对配合物进行了表征.测量晶体的荧光光谱特性发现,该配合物在488 nm 和532nm有较强的荧光发射峰.     

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.     

[Mn(H2O)6][Bi(edta)2.2H2O的合成与晶体结构

以MnCO3与多胺羧酸铋反应,合成了含铋多金属配合物[Mn(H2O)6][Bi(edta)]2.2H2O,通过元素分析和红外光谱对配合物的组成和结构进行了表征.用热重-差热手段研究了配合物的热分解过程,用x射线单晶衍射法测定了其晶体结构.[Mn(H2O)6][Bi(edta)]2·2H2O属单斜晶系,C2/c空间群,晶胞参数:a=2.37013(4)nm,b=0.87111(2)nm,c=1.61082(3)nm,β=97.273(1).,Z=4,Mr=1193.46,V=3.299.01(11)nm3,Dc=2.403g.cm-3,μ=11.123mm-1,F(000)=2284,R1=:0.0210,wR2=0.0567.大量分子间氢键将整个连接起来形成无限3-D结构.     

Crystal structure of triethanolammonium bis(1-hydroxyethane-1,1-diphosphonato)diaquazincate pentahydrate, [(OHCH2CH2)3NH][Zn(H2O)2(H2.5 L)2] ⋅ 5H2O

The crystal structure of [(HOCH₂CH₂)₃NH][Zn(H₂O)₂(H_2.5 L)₂] ? 5H₂O, where H₄ L is 1-hydroxyethane-1,1-diphosphonic acid, was determined by X-ray diffraction. The anionic complex has a cis-octahedral structure. The zinc atom is coordinated by four O atoms of two bidentate chelate H_2.5 L ^1.5? ligands and two O atoms of water molecules. The Zn-O(L) bond lengths range between 2.050 and 2.175 Å, and the Zn-O(H₂O) bond lengths are 2.105 and 2.133 Å. The anionic complexes, triethanolammonium cations, and molecules of crystallization water are interlinked by an extensive network of hydrogen bonds. The crystallographic data for isostructural complexes of cobalt and nickel are given.     

BaBPO5和(H3O)Zn(H2O)2BP2O8·H2O的低温溶剂热合成及表征

以乙醇为溶剂,在低温条件下合成出了两种手性硼磷酸盐化合物BaBPO5(1)(T=120℃,t=5d)和(H3O)Zn(H2O)2BP2O8·H2O (2)(T=80℃,t=5d).XRD单晶衍射仪测定了化合物的结构,结果表明:(1)属三方晶系,P3221空间群,a=b=7.1162(3)(A),c=6.9979(6),(A)=3,该晶体含有一维线性链状阴离子结构;(2)属六方晶系,P6122空间群,a=b =9.513(2)(A),c=15.906(8),(A)=6.该晶体具有三维骨架结构.实验结果表明使用乙醇作溶剂可以极大降低硼磷酸盐的合成温度,进而有助于获得手性硼磷酸盐化合物,这为手性硼磷酸盐的合成提供了一种新思路.     

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.     

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.     

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.     

Structure of a Cu(II)-containing peptide,diaquo-gly-l-tyr Cu(II) dihydrate, [Cu(C11N2O4H13)(H2O)2·2H2O

The structure of the Cu(II) complex of gly-l-tyr [Cu(C₁₁N₂O₄H₁₃) (H₂O)₂]·2H₂O has been solved by X-ray diffraction methods. The compound crystallizes in the orthorhombic space groupP2₁2₁2₁ witha=11.970(2) Å,b=12.485(2) Å andc=10.418(3) Å, respectively, (MoK)=0.710 Å,D _c =1.59 Mgm^–3,D _m =1.59 Mgm^–3, finalR=0.04. The structure was solved by heavy atom (Cu) phased Fourier and refined by full-matrix least squares methods. The coordination geometry of the ligand around the Cu(II) ion has been established as a distorted tetragonal pyramid. The peptide molecule behaves as a tridentate ligand via its amino (N2), amido (N1) nitrogens and carboxyl (O2) oxygens. The peptide nitrogen is found to be deprotonated.     

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).