Structural analysis of conformational flexibility in (aqua)(propanediamine- N,N ′-diacetato- N -propionato)chromium(III) dihydrate. Crystal structure of cis -polar,trans (H2O,O5)-[Cr(1,3-pddap)(H2O)]·2H2O

The quinquedentate complex trans(H₂O,O⁵)-[Cr(1,3-pddap)(H₂O)]?·?2H₂O (where 1,3-pddap is the 1,3-propanediamine-N,N?′-diacetate-N-3-propionate ion) was prepared and its structure established by X-ray diffraction method. It crystallizes in the orthorhombic space group Pna2₁, a?=?17.290(2), b?=?10.821(2), c?=?7.872(1)?Å, Z?=?4. The metal atom is surrounded octahedrally with two nitrogen and three oxygen donors of (1,3-pddap)^3?, forming two six-membered and two five-membered metal chelate rings, and with one water molecule occupying the trans position with respect to the oxygen of the axial glycinate ring. Conformational analysis of the five geometrical isomers of [Cr(1,3-pddap)(H₂O)], performed with the Consistent Force Field (CFF) program and recently developed edta force field, revealed that the global minimum is indeed the trans(H₂O,O⁵) isomer with the geometry in a very good agreement with the crystallographic structure. General patterns for the conformational preferences of edta-type complexes of trivalent first-row transition metals are exposed and discussed.     

Synthesis, crystal structure, and thermal stability of [Mo2O4(μ2-O)(C6H4O2)2(H2O)] · (C8H9N2)2 · 2H2O

From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO₃ in acetic acid solution, a new compound, [Mo₂(μ₂-O)₂(C₆H₄O₂)₂(H₂O)] · (C₈H₉N₂)₂ · 2H₂O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P2₁/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) β = 97.929(4), V = 3225.6(5), Z = 4, M = 808.46, ρ_c = 1.665 g/cm³, μ(MoK _α) = 0.84 mm^?1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with R _int = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N-H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O-H...O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N-H...O to form a quasi-two dimensional structure.     

Syntheses and crystal structures of two Cd(II) coordination polymers: one-dimensional chain [Cd(C4H6N2)2(C4H2O4)(H2O)2] n and two-dimensional sheet [Cd(C4H6N2)(H2O)(C4H4O4)] n · n H2O

Two new Cd(II) coordination polymers, [Cd(C₄H₆N₂)₂(C₄H₂O₄)(H₂O)₂] _n (1) (where C₄H₆N₂?=?2-methylimidazole, C₄H₂O₄?=?fumarate), and [Cd(C₄H₆N₂)(H₂O)(C₄H₄O₄)] _n ?·?nH₂O (2), (where C₄H₄O₄?=?succinates), have been prepared and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 in a one-dimensional chain structure, in which carboxy is monodentate; a three-dimensional supermolecular network structure was formed through hydrogen bonding. In complex 2, the coordination geometry of the Cd atoms is a pentagonal bipyramid, and a two-dimensional sheet is formed though carboxyl group bridging. In 1 and 2, IR spectra indicate the presence of bridging carboxyl groups, confirmed by structure analyses.     

Synthesis and Crystal Structure of Diaqua(2,2"-Dipyridyl)isothiocyanatoneptunoyl Monohydrate [NpO2(C10H8N2)(NCS)(H2O)2] · H2O

The crystal structure of the complex [NpO₂(C₁₀H₈N₂)(NCS)(H₂O)₂] · H₂O is determined. The unit cell parameters are a= 7.406, b= 9.517, c= 11.518 Å, = 103.65°, = 92.68°, = 96.53°, V= 781.6 ų, space group , Z= 2, (calcd) = 2.257 g/cm³, R= 0.046, R _w= 0.122. The coordination polyhedron of the Np atom is a pentagonal bipyramid with two nitrogen atoms of dipyridyl, a nitrogen atom of isothiocyanate ion, two oxygen atoms of water molecules lying in the equatorial plane, and oxygen atoms of the neptunoyl group lying in the axial positions.     

[Ni(bpy)(mal)(H2O)3]·H2O and [Ni(4,4′-dmbpy)(mal)(H2O)3]·1.5H2O: syntheses,crystal structures,magnetic properties,and computational study of stacking interactions

[Ni(bpy)(mal)(H₂O)₃]·H₂O and [Ni(4,4′-dmbpy)(mal)(H₂O)₃]·1.5H₂O (mal = maleato; bpy = 2,2′-bipyridine; 4,4′-dmbpy = 4,4′-dimethyl-2,2′-bipyridine) exhibit molecular crystal structures. The Ni(II) central ions in both complexes are six-coordinate by one chelate bonded L–L ligand, three aqua ligands, and one position is occupied by a maleato oxygen donor atom. Hydrogen bonded ribbon-like supramolecular structural motifs are present in both studied complexes; these are linked by weaker C–H?O hydrogen bonds in [Ni(bpy)(mal)(H₂O)₃]·H₂O, whereas in [Ni(4,4′-dmbpy)(mal)(H₂O)₃]·1,5H₂O the hydrogen bonded ribbons are linked by O?H-O-H?O hydrogen bonds with the participation of the additional water solvate molecule positioned on the twofold axis. In both structures, π–π stacking interactions with different patterns in respective structures were found. The role of dispersion energy and many-body effects in the stabilization of bpy and 4,4′-dmbpy stacking interactions were investigated using methods of computational chemistry. Those confirm the dispersion-dominated stabilization of the 4,4′-dmbpy supramolecular chain-like structure, with only marginal impact of cooperativity effects. Thermal decompositions of both complexes start with dehydration. Magnetic susceptibility studies performed from 2 to 300 K revealed a dominant effect of the zero-field splitting of the Ni(II) ion, governing the low-temperature magnetic properties of both compounds.     

Synthesis,structure, and Mössbauer study of [Fe(H2O)(2)(C(9)O(6)H4)].H2O: a two-dimensional iron(II) trimellitate (MIL-67)

The two-dimensional (2D) iron trimellitate [Fe(H(2)O)(2)(C(9)O(6)H(4))].H(2)O, labeled MIL-67, has been obtained under hydrothermal conditions (473 K, 48 h). In the 2D structure of MIL-67, the Fe(2+) ions display two different octahedral environments: [FeO(4)(H(2)O)(2)] and [FeO(2)(H(2)O)(4)]. These octahedra share an apical water molecule to form infinite chains. The chains are linked by partly deprotonated C(9)O(6)H(4)(2-) anions to give hybrid organic-inorganic layers; the remaining acidic-CO(2)H group is dangling in the interlayer space. Below 8(1) K, MIL-67 displays a canted antiferromagnetic behavior, according to analyses via magnetic measurements and M?ssbauer spectroscopy. Crystal data for MIL-67 are as follows: triclinic; space group P1 (No. 2), with a = 6.9671(2) A, b = 7.3089(3) A, c = 12.5097(3) A, alpha = 78.758(1) degrees, beta = 89.542(2) degrees, and gamma = 65.197(1) degrees; volume V = 565.21(3) A(3); and Z = 2.     

Synthesis,crystal structure and properties of a manganese(III) Schiff-base complex: [{Mn(vanen)(Him)(H2O)}{Mn(vanen)(Him)2}](ClO4)2 · 4H2O(H2vanen = N,N′-bis(methoxysalicylidene)-1,2-diaminoethane)

A novel manganese(III) complex, [{Mn(vanen)(Him)(H₂O)}(Mn(vanen)(Him)}](ClO₄)₂ · 4H2O [H₂vanen = N,N-bis(methoxysalicylidene)-1,2-diaminoethane], has been synthesized and characterized by elemental analysis, i.r. spectroscopy, t.g.a. and by an X-ray single crystal study. The complex consists of two sets of cations: [Mn(vanen)(Him)(H₂O)]⁺ (A) and [Mn(vanen)(Him)₂]⁺ (B), each of which has six-coordinate geometry, significantly elongated due to the Jahn-Teller distortion at the d⁴ manganese(III) center. The presence of lattice and coordinate water molecules are also confirmed by the t.g. study and the i.r. spectra.     

混合配体的铜(Ⅱ)配合［Cu(C2H4O2N)(C12H8N2)(H2O)］.ClO4.2.5H2O的合成、性质及晶体结构

本文对甘氨酸、1,10 -邻菲咯啉铜 ( )固体配合物进行了合成和表征 ,并利用 X射线分析研究了其晶体结构     

Manganese(II) complexes with edta-type ligands. The molecular structure of aquo-dihydrogen(1,2-propanediamine-N,N,N′,N′-tetraacetate)manganese(II) trihydrate, [Mn(H21,2-pdta)(H2O)] · 3H2O

New manganese(II) complexes with ethylenediamine-N,N,N,N-tetra-3-propionate (edtp) and 1,2-propanediamine-N,N,N,N-tetraacetate (1,2-pdta) were prepared and characterized by elemental analysis, i.r. spectroscopy and magnetic measurements. The structure of [Mn(H₂1,2-pdta)(H₂O] · 3H₂O was determined by the single crystal X-ray diffraction technique. The complex crystallizes in the space group P2₁/n(#14) of the monoclinic crystal system with unit cell parameters a = 10.993(2) Å, b = 14.092(2) Å, c = 11.753(1) Å, = 96.302(9)⁰, V = 1809.7(3) ų, Z = 4 and R = 0.051. The complex contains seven-coordinated Mn^II ion with H₂1,2-pdta ion acting as hexadentate ligand and one water molecule.     

Keggin polyoxoanion supported organic-inorganic trinuclear lutetium cluster, {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}[SiW(12)O(40)]·26.5H(2)O

A novel strawberry-like organic-inorganic hybrid, {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}[SiW(12)O(40)]·26.5H(2)O (H(2)pydc = pyridine-2,6-dicarboxylate) containing an intriguing trinuclear lutetium cluster {Na(H(2)O)(3)[Lu(pydc)(H(2)O)(3)](3)}(4+) has been synthesized and its luminescent properties, IR, UV, TG, PXRD analyses and single crystal X-ray diffraction were investigated.     

N,N''''-(2-苯并咪唑基甲基)亚氨基甲基膦酸的双核镍化合物Ni2(bbimp)2(4,4''''-bipy)(H2O)2·2H2O和Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O的晶体结构和磁学性质

该文报道了N,N′-(2-苯并咪唑基甲基)亚氨基甲基膦酸{bbimpH_2,[(C7H5N2)CH2]2NCH2PO3H2}的2个镍化合物Ni2(bbimp)2(4,4′-bipy)(H2O)2·2H2O(1)和[Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O(2)。化合物1是4,4′-联吡啶作为桥连配体的中性双核结构。化合物2含有1个中性的[Ni2(bbimp)2(H2O)2]双核分子与2个中性的[Ni(bbimp)(H2O)2]单核分子。双核分子单元中的2个Ni!离子被2个膦酸氧桥连。在化合物2中,膦酸氧桥连的2个Ni!离子之间存在铁磁性相互作用。     

Syntheses and structures of seven-coordinate K3[Cd(Dtpa)], K2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O, and Na2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O complexes

The title complexes, K₃[Cd(Dtpa)] (H₅Dtpa = diethylenetriamine-N,N,N,N′,N′-pentaacetic acid, (I)), K₂[Cd(H₂O)₄][Cd(Edta)(H₂O)]₂ · 2H₂O (H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid, (II)), and Na₂[Cd(H₂O)₄][Cd(Edta)(H₂O)]₂ · 2H₂O (III), were prepared, and their compositions and structures were determined by elemental analyses, IR spectra, and single-crystal X-ray diffraction techniques, respectively. In complex I, the Cd is seven-coordinated by one Dtpa ligand yielding a pseudo-monocapped trigonal prism conformation, and the complex crystallizes in the triclinic crystal system with the Pi space group. The crystal data are as follows: a = 8.7300(17), b = 9.1200(18), c = 15.110(3) Å, α = 95.52(3)°, β = 96.59(3)°, γ = 99.63(3)°, V = 1170.0(4) ų, Z = 2, ρ = 1.754 g/cm³, μ = 1.519 mm^?1, F(000) = 616, R = 0.0644 and wR = 0.1712 for 3842 observed reflections with I ≥ 2σ(I). For complex II, in the [Cd(Edta)(H₂O)]^2? complex anion the Cd²⁺ ion is seven-coordinated by one Edta ligand and one water molecule, yielding a pseudo-pentagonal bipyramid conformation. In the [Cd(H₂O)₄]²⁺ cation, the bridged Cd is six-coordinated, yielding an almost standard octahedral conformation. The complex crystallizes in the monoclinic system with P2₁/n space group. The crystal data are as follows: a = 9.098(3), b = 16.442(6), c = 12.023(4) Å, β = 91.053(6)°, V = 1798.3(12) ų, Z = 2, ρ = 2.098 g/cm³, μ = 2.086 mm^?1, F(000) =1124, R = 0.0406 and wR = 0.1152 for 3680 observed reflections with I ≥ 2σ(I). In complex III, the conformations of Cd²⁺ ions are similar to those of the potassium salt complex, and the complex also crystallizes in the monoclinic crystal system with the P2₁/n space group. The crystal data are as follows: a = 9.134(7), b = 16.500(13), c = 12.075(10) Å, β = 91.054(12)°, V = 1820(2) ų, Z = 2, ρ = 2.015 g/cm³, μ = 1.856 mm^?1, F(000) = 1092, R = 0.0363 and wR = 0.0879 for 3707 observed reflections with I ≥ 2σ(I).     

Crystal Structure and Interaction with DNA of [Ni(phen)(mal)(H2O)2]·3H2O

A new complex [Ni(phen)(mal)(H2O)2]·3H2O (phen = 1,10-phenanthroline,mal2-= malonic acid) has been synthesized by the reaction of nickel nitrate,phen and malonic acid.EA,IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the title complex.Crystal data:monoclinic system,space group P2/c,a =8.937(3),b = 12.163(5),c = 9.725(3)(A),β = 119.36°,C15H19N2O9Ni,Mr= 430.03,Z = 2,F(000) =446,V = 921.3 (A)3,Dc = 1.550 g/cm3,μ = 1.104 mm-1,-10≤h≤ 10,-12≤k≤ 14,-11 ≤l≤7,R =0.0261 and wR = 0.0609 for 4376 (Rint = 0.0203) independent reflections and 1631 observed ones (I＞ 2σ(I)).Ni(Ⅱ) exhibits an octahedral coordination geometry,with hydrogen bonds and π-π interactions stabilizing the whole structure.UV spectrum of the complex interacting with protamine DNA indicates that the title compound interacts with DNA via insertion mode with bonding constant Kb of 1.11 × 104.     

Syntheses and Structures of Two New Coordination Polymers:[Cu(C14H9O4)(C14H10O4)(C12H12N2)2] and [Ag(C14H9O4)(C13H14N2)]·0.5 H2O

Under hydrothermal conditions, two new ribbon-like structures, [Cu(C14H9O4)-analysis revealed that these structures were constructed by mixed ligands. The coordination polymer forms the basic architecture while the weak interactions extend the framework into a secondary structure. The whole structures of them are governed by collaboration of the strong and weak interactions. Compound 1 crystallizes in monoclinic, space group C2/c with a = 17.0485(3), b =1 1.0558(3), c = 22.7623(4) A, β = 102.465(1)°, V = 4189.2(2) A3, Z = 4, Mr = 915.44, Dc = 1.451g/mL, F(000) = 1900 andμ(MoKα) = 0.587 cm-1. The final R and wR are 0.0030 and 0.1022,respectively for 3037 observed reflections with I ＞ 2σ(I). Compound 2 crystallizes in monoclinic,space group P21/c with a = 11.5963(4), b = 11.7004(5), c = 17.1254(5) A,β = 95.620(1)°, V =2312.4(1) A3, Z = 4, Mr = 556.35, Dc = 1.598 g/mL, F(000) = 1132 andμ(MoKα) = 0.912 cm-1The final R and wR are 0.0431 and 0.1050, respectively for 2629 observed reflections with I ＞ 2σ(I).     

X-ray crystal structure of [VO(DPA)(H2O)2]·2H2O (DPA=Dipicolinate dianion)

The X-ray crystal structure of the trans-diaqua complex [VO(DPA)(H2O2)]·2H2O (1) (DPA=dipicolinate dianion) has been determined. Comparison with the known structure of [VO(DPA)(o-phen)]·3H2O (2), obtained from (1) by displacement of the two coordinated aqua molecules, shows that the coordination sphere around vanadium is reorganised during this reaction.     

Solvothermal Synthesis, Crystal Structure and Electrochemical Property of Complex [Co(p-MBA)2(2,2'-bipy)(H2O)]·(H2O)

One novel complex [Co(p-MBA)2(2,2'-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2'-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic, space group P-1 with a=0.70479(14), b=1.1211(2), c=1.6718(3) nm, α=103.806(3), β=90.795(3), γ=104.207(3)°, V=1.2399(4) nm3, Mr=512.41, Dc=1.373 g/cm3, Z=2, F(000)=532, μ=0.733 mm-1, R=0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2'-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported.     

Synthesis and structure of [UO2(SeO4)(C2H4N4)2] · 0.5H2O

The single-crystal X-ray diffraction analysis of [UO₂(SeO₄)(C₂H₄N₄)₂] · 0.5H₂O (I) is performed. The crystals are monoclinic: space group C2/c, Z = 8, a = 19.035(2), b = 7.1326(8), c = 21.477(2) Å, β = 109.683(4)°. The main structural units of the crystal are chains of [UO₂(SeO₄)(C₂H₄N₄)₂]. Compound I belongs to the crystal-chemical group AT³M ₂ ¹ (A = UO ₂ ²⁺ , T³ = SeO ₄ ^2? , M¹ is a cyanoguanidine molecule) of the uranyl complexes. The chains are united into three-dimensional framework through hydrogen bonds involving the oxygen atoms of the selenate and uranyl groups, the nitrogen atoms of cyanoguanidine, and the hydrogen atoms of the cyanoguanidine or water molecules.     

Synthesis and Structure of a Novel Compound [Cu2(EDTA)(Py)2(H2O)2]·2H2O

A novel compound [Cu2(EDTA)(Py)2(H2O)2]·2H2O was synthesized by the reaction of CuSO4(5H2O with H4EDTA in pyridine/water (V/V = 1/4) solvent, and characterized by elemental analysis, IR spectrum and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 1.26974(6), b = 0.67949(3), c = 1.48548(3) nm, β = 91.454(2)o, V = 1.28122(9) nm3, Z = 2, Dc = 1.673 g/cm3, Mr = 645.56, F(000) = 664, μ(MoKα) = 1.729 mm-1, the final R = 0.0353 and wR = 0.0832 for 1920 observed reflections (I > 2((I)). The compound is a centrosymmetric binuclear molecule with bridged EDTA group. Each Cu(II) atom is linked to two oxygen atoms and one nitrogen atom of EDTA, one oxygen atom of water and one nitrogen atom of pyridine to form a distorted square pyramidal environment. There exist face-to-face π-π stacking interactions between pyridine rings from neighboring molecule with the interplanar distance of 0.3670 nm and hydrogen bonding between EDTA and water molecules.     

Synthesis,Spectroscopic Properties and Crystal Structure of (C4N2H12)2Zr(C2O4)4·H2O

The title compound (C4N2H12)2Zr(C2O4)4·H2O 1 was synthesized by the reaction of ZrOCl2·8H2O, H2C2O4·2H2O and piperazinium in aqueous solution. Single-crystal X-ray analysis has revealed that compound 1 (C16H26N4O17Zr, Mr = 637.63) crystallizes in the monoclinic system, space group P21/c with a = 9.0425(3), b = 13.3844(3), c = 19.1191(5)A, β = 98.365(1)o, V = 2289.34(11) A3, Z = 4, Dc = 1.850 g/cm3, F(000) = 1304, μ = 0.577 mm-1, the final R = 0.0240 and wR = 0.0628 for 4386 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Zr(C2O4)4]4- anion and two protonated piperazinium cations. The anions are linked through hydrogen bonds of piperazinium. FT-IR and Raman spectra clearly show the existence of oxalate groups in the crystal lattice.     

[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O超分子化合物的晶体结构、荧光性质及热稳定性

在水-乙醇混合体系中,以2-羰基丙酸水杨酰腙(C10H10N2O4,简作H3L)、1,10-菲啰啉C12H8N2,简作phen)与Eu(NO3)3·4H2O反应,首次培养出黄色单晶[Eu(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O.该晶体属三斜晶系,P1空间群,晶胞参数a=1.378 6(12) nm,b=1.398 8(12) nm,c=1.759 7(16) nm,α=73.977(11)°,β=68.598(12)°,γ=71.224(12)°,V=29.42(4) nm3,Z=2,μ=2.208 mm-1,Dc=1.746 Mg/m3,F(000)=1 556,R=0.037 7,ωR=0.074 4,GOF=0.916.每个配合物晶体中均有两个相似的结构单元,每个结构单元中铕(Ⅲ)配位数为9,分别与两个2-羰基丙酸水杨酰腙和3个水分子配位; 每个2-羰基丙酸水杨酰腙中的羧基氧、酰胺基中的羰基氧和CN中的氮与Eu3+配位,形成两个共边的稳定的五元环,另3个配位原子则分别来自3个水分子中的氧原子,该结构单元在空间呈扭曲的单帽四方反棱柱,而在每两个铕的九配位单元周围还有一个游离的1,10-菲啰啉分子和4个水分子.IR,1H NMR及热分解结果佐证了配合物的组成.该配合物具有很好的荧光特性.