Heterometallic Trinuclear Ni2Zn and Ni2Mn Complexes of Macrocyclic Oxamide: Synthesis and Crystal Structures

Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn(NiL)2(HBTC)H2O] (1) and [Zn(NiL)2(HBTC)H2O] (2) (NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid) have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595(5), b = 23.1498(11), c = 17.2558(8) and =101.2530(10)°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214(8), b = 20.6566(14), c = 18.4126(13)  and = 92.6770(10)°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O-H…O intermolecular hydrogen bonds.     

Crystal structures of two polymorphs of Ca3[Al2N4

Green transparent single crystals of alpha-Ca3[Al2N4] (monoclinic, P2(1)/c, No. 14, a = 957.2(3) pm, b = 580.2(3) pm, c = 956.3(5) pm, beta = 111.62(3) degrees; Z = 4) were obtained from reactions of mixtures of the representative metals with nitrogen above temperatures of 1000 degrees C. beta-Ca3[Al2N4] (monoclinic, C2/c, No. 15, a = 1060.6(2) pm, b = 826.0(2) pm, c = 551.7(1) pm, beta = 92.1(1) degrees; Z = 4) was formed as a byproduct of a reaction of calcium with alumina under nitrogen at T = 930 degrees C in form of colorless crystals. The crystal structures of the two polymorphs contain edge- and corner-sharing AlN4 tetrahedra, leading to different layered anionic partial structures: infinity 2[AlN2/2N2/3)2(AlNN2/2N1/3)6/3(12-)] in the alpha-phase and infinity 2[Al2N2N4/2(6-)] in the beta-polymorph.     

Crystals from concentrated glyme mixtures. The single-crystal structure of LiClO4

A procedure for the preparation of high-quality single crystals from concentrated glyme mixtures is presented. Anhydrous single crystals of LiNO(3) and LiClO(4) were prepared in this manner, and the single-crystal structure of LiClO(4) (orthorhombic, Pnma, a = 8.6447(12) A, b = 6.8512(10) A, c = 4.8254(7) A, Z = 4) was determined as an example. This procedure is expected to be widely applicable for not only salts but also a wide range of other materials solvated by glymes.     

Crystal and Molecular Structure of 6,7,9,10,12,13-Hexahydrodibenzo[d, p][1,3,6,9,12,15,2]hexaoxathiacycloheptadecine-20-oxide

An X-ray diffraction (XRD) analysis of the title crystals has been carried out: space group P2_1/c, a=12.834(2), b=13.342(3), c=11.462(2) Å, β=111.15(1)°, Z=4; 3983 unique reflections collected; R=0.040. The molecular structure of this new crown compound has been determined.     

Co[(C2H5O)2PS2]2·2Py的合成及其晶体结构

用光谱法研究了Co[(C2H5O)2PS2]3与吡啶的取代还原反应, 测定了反应的平衡常数K=0.66±0.05(mol·dm^-^3)^-^3。用X射线单晶衍射方法测定了Co[(C2H5O)2PS2]2·2Py的晶体结构。晶体空间群为P21/c, 晶胞参数a=8.117(7), b=17.813(4),c=9.901(3)埃; β=104.19(5)°; Z=2; 晶体密度计算值Dc=1.406g.cm^-^3。差热分析印证了标题化合物含二分子吡啶, 提出了可能的取代还反应的机理。     

[Co(N-(3-Aminopropyl)-1,3-propanediamine)(2-(Aminomethyl)pyridine) Cl][ZnCl_4]的一对差向异构体的合成及晶体结构

用过氧化物法合成了 [Co(3,3-tri)(amp)Cl][ZnCl4]的两个经式异构体,晶体结构解析表明两者互为差向异构体。其中反式异构体 (仲氢相对于 Cl)晶体属单斜晶系,空间群 C2/c, a=2.7663(7)nm, b=0.9505(1)nm, c=1.8288(4)nm,β =105.57(2)°, V=4.632(1)nm3, Dc=1.706g· cm-3, Z=8, F000=2432.00,μ (MoKα )=23.51cm-1, R=0.033, Rw=0.041;顺式异构体 (仲氢相对于 Cl)晶体属三斜晶系,空间群, a=1.0790(2)nm, b=1.1749(1)nm, c=0.8920(1)nm,α =90.73(1)°,β =109.573(9)°,γ =80.60(1)°, V=1.0500(2)nm3, Dc=1.71g· cm-3, Z=2, F000=548.00,μ (MoKα )=25.73cm-1, R=0.022, Rw=0.030。两异构体中 Co3＋为六配位,其差异仅表现在 3,3-tri仲胺上氢的取向不同。     

CRYSTAL AND MOLECULAR STRUCTURE OF 1.3-DI-ISO-PROPYL-2-PHENYL-4-METHOXY-4,5-DIOXO-2-THIO-1,3,2,4-DIAZADTPHOSPHOLANE

<正> The structure of the title compound has been determined by X-ray analysis. The crystals of this coiapound are monoclinic, space group P21/c with a=8.432(1),b=11.735(3),c=18.254(4)A,β=93.25(2)°,Z=4, and Dx=1.33 g/cm3. The final refinement converged with R=0.031 and Rw=0.031 for 1788 observed independent reflections.     

Crystal and molecular structures of ionophore-siderophore host-guest supramolecular assemblies relevant to molecular recognition

Ionophore-siderophore host-guest assemblies composed of 18-crown-6 and ferrioxamine B, benzo-18-crown-6 and ferrioxamine B, and cis-syn-cis-dicyclohexano-18-crown-6 and ferrioxamine B were successfully crystallized, and their structures were determined by single-crystal X-ray diffraction. All three crystal lattices also include solvated Mg(II) and perchlorate ions. The ionophore-siderophore host-guest assembly is noncovalently held together by a hydrogen bonding interaction between the pendant protonated amine in the second coordination sphere of ferrioxamine B and the hydrogen bond acceptor oxygen atoms in the crown ether. The crystals of 18-crown-6:ferrioxamine B host-guest assembly are monoclinic, with space group P2(1)/c, and four molecules per unit cell with dimensions a = 19.8327(11) A, b = 20.4111(11) A, c = 15.1698(8) A, and beta = 96.435(1) degrees. The crystals of benzo-18-crown-6:ferrioxamine B host-guest assembly are triclinic, with space group P(-)1, and two molecules per unit cell with dimensions a = 11.1747(10) A, b = 16.0580(15) A, c = 18.4175(17) A, alpha = 80.469(3) degrees, beta = 81.481(3) degrees and gamma = 70.212(2) degrees. The crystals of cis-syn-cis-dicyclohexano-18-crown-6:ferrioxamine B host-guest assembly are monoclinic, with space group P2(1)/c, and four molecules per unit cell with dimensions a = 20.1473(13) A, b = 21.5778(15) A, c = 14.8013(10) A, and beta = 94.586(2) degrees. The crystal structures of all three host-guest assemblies contain a racemic mixture of Lambda-N-cis, cis and Delta-N-cis, cis coordination isomers of ferrioxamine B. The crystal structures indicate that the steric rigidity of the benzo-18-crown-6 and cis-syn-cis-dicyclohexano-18-crown-6 cavity has a pronounced effect on the conformation of the crown ring and ultimately on the hydrogen bonding interactions between the crown ethers and ferrioxamine B. The structural parameters and the conformational features of the ferrioxamine B guests compare very well with each other and with those of the ferrioxamine B structure obtained in the absence of a host. Structural features relevant to siderophore molecular recognition are discussed.     

Deformation-induced phosphorescence shift in a 2D elastically flexible organic single crystal: role of chalcogen-centered weak interactions

Mechanically responsive organic luminescent crystals are one of the promising choices of materials for flexible photonic devices. However, the change in phosphorescence emission as a function of the flexibility of a crystal has never been reported. Our current findings demonstrate two-dimensional (2D) and one-dimensional (1D) macroscopic elastic deformability, under mechanical stress, in elastically flexible single crystals of dibenzothiophene, and its brominated derivative, respectively. Unlike the presence of dual fluorescence (FL) and room temperature phosphorescence (RTP) in dibenzothiophene single crystals, the derivative was found to show only RTP. Interestingly, upon elastic deformation, single crystals of the dual emissive dibenzothiophene show a noticeable blue shift (∼20 nm) of RTP emission when compared to their pristine crystals (straight and naturally bent). However, their FL peaks remain nearly unchanged irrespective of the crystal deformation. A hierarchy of structure-elastic functionality to RTP modulation has been quantitatively mapped by rationalizing the role of chalcogen-involved weak interactions.

In response to macroscopic elastical bending, single crystals of dual emissive dibenzothiophene depict a significant blue shift (∼20 nm) of RTP emission when compared to their pristine crystals (straight and naturally bent).     

Solvent isotope effects on interfacial protein electron transfer in crystals and electrode films

D(2)O-grown crystals of yeast zinc porphyrin substituted cytochrome c peroxidase (ZnCcP) in complex with yeast iso-1-cytochrome c (yCc) diffract to higher resolution (1.7 A) and pack differently than H(2)O-grown crystals (2.4-3.0 A). Two ZnCcP's bind the same yCc (porphyrin-to-porphyrin separations of 19 and 29 A), with one ZnCcP interacting through the same interface found in the H(2)O crystals. The triplet excited-state of at least one of the two unique ZnCcP's is quenched by electron transfer (ET) to Fe(III)yCc (k(e) = 220 s(-1)). Measurement of thermal recombination ET between Fe(II)yCc and ZnCcP+ in the D(2)O-treated crystals has both slow and fast components that differ by 2 orders of magnitude (k(eb)(1) = 2200 s(-1), k(eb)(2) = 30 s(-1)). Back ET in H(2)O-grown crystals is too fast for observation, but soaking H(2)O-grown crystals in D(2)O for hours generates slower back ET, with kinetics similar to those of the D(2)O-grown crystals (k(eb)(1) = 7000 s(-1), k(eb)(2) = 100 s(-1)). Protein-film voltammetry of yCc adsorbed to mixed alkanethiol monolayers on gold electrodes shows slower ET for D(2)O-grown yCc films than for H(2)O-grown films (k(H) = 800 s(-1); k(D) = 540 s(-1) at 20 degrees C). Soaking H(2)O- or D(2)O-grown films in the counter solvent produces an immediate inverse isotope effect that diminishes over hours until the ET rate reaches that found in the counter solvent. Thus, D(2)O substitution perturbs interactions and ET between yCc and either CcP or electrode films. The effects derive from slow exchanging protons or solvent molecules that in the crystal produce only small structural changes.     

MORPHOLOGY OF HEAD-TO-TAIL POLY（3-HEXYLTHIOPHENE） SINGLE CRYSTALS FROM SOLUTION CRYSTALLIZATION

Single crystals of head-to-tail poly(3-hexylthiophene)s have been grown through the method of isothermal solution crystallization. Electron diffraction in combination with powder X-ray diffraction revealed the crystal structure, a = 1.52 nm, b = 3.36 nm, c= 1.56 nm andα=β=γ= 90°.     

Homoleptic tris(dithiolene) and tetrakis(dithiolene) complexes of uranium(IV)

Reaction of UCl4 with 3 or 4 mol equiv of Na2dddt (dddt = 5,6-dihydro-1,4-dithiine-2,3-dithiolate) in THF afforded the first example of a tetrakis(dithiolene) metal compound, [Na4(THF)8U(dddt)4](infinity) (1). The red crystals of 1 are composed of infinite zigzag chains in which Na2(micro-THF)3 fragments ensure the linking of Na2(THF)5U(dddt)4 moieties; the uranium atom is in a dodecahedral environment of eight sulfur atoms. Treatment of UCl4 with 3 mol equiv of Na2dddt in pyridine gave a mixture of tris- and tetrakis(dithiolene) compounds. After addition of 18c6 (18-crown-6), only the tris(dithiolene) complex was obtained and crystallized as orange crystals of [Na(18c6)(py)2]2[U(dddt)3].2py (2.2py) in which the isolated [U(dddt)3]2- anion adopts a slightly distorted trigonal prismatic configuration. A few red crystals of the unsolvated complex 2 and the trinuclear anionic compound [Na(18c6)(py)2]3[Na{U(dddt)3}2] (3) were also obtained along with orange crystals of 2.2py. All the tris(dithiolene) compounds exhibit large folding of the dddt ligand and significant interaction between the C=C double bond and the metal center.     

Macrocyclic copper(II) and zinc(II) complexes incorporating phosphate esters

Slow evaporation of solutions prepared by adding either Cu(ClO(4))(2).6H(2)O or Zn(ClO(4))(2).6H(2)O to solutions containing appropriate proportions of Me(3)tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) and sodium phenyl phosphate (Na(2)PhOPO(3)) gave dark blue crystals of [Cu(3)(Me(3)tacn)(3)(PhOPO(3))(2)](ClO(4))(2).(1)/(2)H(2)O (1) and colorless crystals of [Zn(2)(Me(3)tacn)(2)(H(2)O)(4)(PhOPO(3))](ClO(4))(2).H(2)O (2), respectively. Blue crystals of [Cu(tacn)(2)](BNPP)(2) (3) formed in an aqueous solution of [Cu(tacn)Cl(2)], bis(p-nitrophenyl phosphate) (BNPP), and HEPES buffer (pH 7.4). Compound 1 crystallizes in the triclinic space group P1 (No. 2) with a = 9.8053(2) A, b = 12.9068(2) A, c = 22.1132(2) A, alpha = 98.636(1) degrees, beta = 99.546(1) degrees, gamma = 101.1733(8) degrees, and Z = 2 and exhibits trinuclear Cu(II) clusters in which square pyramidal metal centers are capped by two phosphate esters located above and below the plane of the metal centers. The trinuclear cluster is asymmetric having Cu...Cu distances of 4.14, 4.55, and 5.04 A. Compound 2 crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 13.6248(2) A, b = 11.6002(2) A, c = 25.9681(4) A, beta = 102.0072(9) degrees, and Z = 4 and contains a dinuclear Zn(II) complex formed by linking two units of [Zn(Me(3)tacn)(OH(2))(2)](2+) by a single phosphate ester. Compound 3 crystallizes in the monoclinic space group C2/c (No. 15) with a = 24.7105(5) A, b = 12.8627(3) A, c = 14.0079(3) A, beta = 106.600(1) degrees, and Z = 4 and consists of mononuclear [Cu(tacn)(2)](2+) cations whose charge is balanced by the BNPP(-) anions.     

La9RbIr4O24: a rubidium-containing oxide with a new structure type

Single crystals of La9RbIr4O24, grown from a molten rubidium hydroxide flux, crystallize in the space group I4/m with lattice parameters a = 7.7422(3) A and c = 17.7979(11) A. The oxide forms in a new complex structure type.     

Structural studies of metabolic products of dopamine. III. Crystal and molecular structure of (--)-adrenaline.

The crystal structure of (--)-adrenaline has been determined by X-ray methods, using 831 observed reflections collected by counter methods. The crystals are monoclinic, space group P2-1 with a=7.873(2), b=6.790(2), c=8.638(2) A and beta=98.01(2) degrees. Least-squares refinements yielded a conventional R-factor of 0.053. Standard deviations in bond lengths are 0.005-0.006 A and in bond lengths aree 0.005-0.006 A and in bond angles 0.4 degrees. The adrenaline molecules were found to exist as zwitterions in the crystals. The conformation of the adrenaline molecule corresponds closely to that usually encountered among the salts of the sympathomimetic amines. The crystals consist of molecular double layers parallel to (100). The molecules within a layer are linked through hydrogen bonds of the types N--H...O and O--H...O, whereas the layers are connected by van der Waals interactions.     

Molecular Replacement Studies of Cucurmosin from Cucurbita Moschata:Structure Homology with Trichosanthin

1 INTRODUCTION Many plants contain proteins that are capable of inactivating ribosomes and therefore are called ribosome-inactivating proteins or RIPs[1]. RIPs are RNA N-glycosidases that inactivate ribosomes through a site-specific deadenylation of the large ribosomal RNA[2, 3]. RIPs are also capable of inactivating many nonribosomal nucleic acid substrates and can be considered as polynucleotide: adenosine glycosidases[4～6]. There are two types of RIPs: type I, single chain pr…     

Molecular Replacement Studies of Cucurmosin from Cucurbita oschata：Structure Homology with Trichosanthin

High diffraction quality crystals of cucurmosin,a type I ribosome inactivating protein isolated from the sarcocarp of Cucurbita moschata(pumpkin),have been grown under newly optimised conditions.With in-house rotating anode X-ray source,these crystals diffract to 1.65A resolution which is moch higher than that of the previously reported crystals that diffracted only to 3A resolution.The crystals belong to space group P212121with cell parameters a=41.5,b=58.4 and c=99.3A.Molecular replacement studies indicate that the cucurmosin structure is homologous to trichosanthin.The initial structural model has been obtained and the model fitting/refinement is in progress.     

两类稀土钒酸盐的合成与结构

通过（１）ＬｎＯＣｌ／Ｖ＿２Ｏ＿５，（２）ＬｎＣｌ３／Ｖ及（３）ＬｎＯＣｌ／ＬｎＣｌ／Ｖ＿２Ｏ＿５／Ｖ的高温固态化学反应，得到两种稀土钒酸盐：Ｌｎ＿６Ｖ＿３Ｃｌ＿（１０）Ｏ＿（１２）（Ｌｎ＝Ｌａ）及Ｌｎ＿４Ｖ＿５Ｓｉ＿４Ｏ＿（２２）（Ｌｎ＝Ｌａ～Ｎｄ）。Ｌａ＿６Ｖ＿３Ｏ＿（１０）Ｏ＿（１２）晶体呈浅色透明片状，其结构可认为是由［Ｌａ＿３（ＶＯ＿４）＿３Ｃｌ］单元插入到ＬａＣｌ３结构单元中而形成的，在结构中沿ｃ轴方向存在一系列截面积为１９．１的空洞。Ｌｎ＿４Ｖ＿５Ｓｉ＿４Ｏ＿（２２）（Ｌｎ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ）晶体呈，黑色针状，其结构可认为是由交替的稀土钒硅酸盐薄层及钒氧金红石层沿ｃ轴堆叠而表现为准二维Ｃｈｅｖｋｉｎｉｔｅ型结构。     

Einkristallzüchtung und Verfeinerung der Kristallstruktur von BaPb(1-x)BixO3 (x = 0, 15)

Crystal Growth and Structure Determination of BaPb_(1–x)Bi_xO₃ (x = 0.15) Single crystals (0.15X0.20X0.20 mm) of BaPb_(1–x)Bi_xO₃ (x = 0.15) have been grown from a lead (II)-oxide melt. The refinement of the crystal structure (I4/mcm; a = 6.047(5), c = 8.603(8) Å; Z = 4; 281 diffractometer data, R = 0.03) resulted in Pb(Bi)? O? Pb(Bi) bonding angles of 180° (2X), and 165° (4X) within the a/b plane. The identity of single crystals and powder material was ensured by an Rietveld profile fit of the X-ray powder diagram. The compositions of the single crystals have been determined applying electron microprobe techniques. T_c of the single crystals was found to be 13.2 K (onset, S QUID-magnetometer).     

Das Dreistoffsystem Kaliumazid-Strontiumazid-Wasser bei 268 K

Ternary System Potassium Azide – Strontium Azide – Water at 268 K The 268 K isotherm of the ternary system KN₃? Sr(N₃)₂? H₂O has been investigated by means of solubility measurements and x-ray methods. The following compounds were identified: KN₃; K₂Sr(N₃)₄ · 4 H₂O (orthorhombic, a = 1898, b = 1101, c = 624 pm, space group Cmmm); stable mixed crystals K_xSr_y(N₃)_4.69(H₂O)_6.62 with x = 2.08 to 1.34 and y = 1.30 to 1.67 (orthorhombic, a = 638 to 644, b = 1092 to 1082 and c = 627 to 623 pm, space group C222); metastable mixed crystals in the areas between stable mixed crystals and stoichiometric compounds; Sr(N₃)₂ · 5 H₂O (orthorhombic, a = 669, b = 1058, c = 611 pm, space group C222); Sr(N₃)₂ · 4 H₂O (orthorhombic, a = 643, b = 1096, c = 4396 pm).