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.     

Polymeric copper(II)-orotato complexes, [(C5H2N2O4)Cu(H2O)2]n

The compound [(C₅H₂N₂O₄)Cu(H₂O)₂]_n has been synthesized and its structure determined at room temperature. The primary coordination sphere at the Cu ion is square planar with the orotate dianion coordinating at the metal through heterocyclic nitrogen atom and adjacent oxygen of the carboxylate group, the remaining coordination sites are occupied by two water molecules. The orotate dianion is tricoordinated to one copper via N₁ and one oxygen of the carboxylato group and to another copper atom via the other oxygen of the carboxylato group. The coordination at copper is extended to five by the other oxygen of the carboxylate group of another orotate molecule. Thus, the molecules are associated to form chains, the carboxylato group acting as a bridge between the metal ions, the orotato-group being tridentate. The title compound crystallizes in the monoclinic space group. P2₁/n₁ with a = 9.515(5), b = 6.925(2), c = 11.861(6) Å, = 95.285(9)°, D _calc = 2.17 g cm^–3, and z = 4.     

{[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.     

Vacuum-ultraviolet absorption of interstitial O2 and H2O molecules in SiO2 glass

Vacuum-ultraviolet (VUV) absorption of O₂ and H₂O molecules incorporated in interstitial voids in SiO₂ glass by thermal annealings was examined. Interactions of the interstitial molecules with the surrounding SiO₂ glass network lead to a redshift of the VUV absorption band of interstitial O₂, while a blueshift of that of interstitial H₂O, both accompanied by an increase in the intensity of the absorption bands. The Coulomb repulsion, London dispersion, and hydrogen bonding are the main interactions responsible for the modification of the VUV absorption bands.     

Structure of 18-cyanoprogesterone,C22H29O2N

The crystal structure of 18-cyanoprogesterone was determined by X-ray diffraction methods:P2₁2₁2₁ a=7.436(2),b=11.322(2),c=22.642(2) Å. The structure was solved usingShelx-86. Final conventionalR=0.054.R _w =0.051 for 1841 reflections. TheA ring has an intermediate sofa-half-chair conformation with asymmetry parameters C _s ^/1 =11.0, C ₂ ^3,4 =14.9. The steroid skeleton exhibits a flattening of theA ring relative to the rest of the molecule. The progesterone side chain has a typical conformation, and the C16-C17-C20-O20 torsion angle is –19.0(6)°.     

(C2N2H10)2Mg(HP2O7)2·2H2O synthesis and crystal structure

(C₂N₂H₁₀)₂Mg(HP₂O₇)₂·2H₂O, is a new inorganic organic hybrid structure. It has been synthetized using wet chemistry. Its crystal structure consists of cis- and trans-edge sharing [MgO₄(H₂O)₂] octahedra resulting in chains, which are linked via [HP₂O₇] units to form [Mg(HP₂O₇)₂(H₂O)₂]⁴⁻ layers. The Mg²⁺ cations and the ethylendiammonium cations are located on centers of inversion. The ethylendiammonium cations are alternately located in the interlayer space. The cohesion of the crystal is well ensured by coulombic interactions between anions and cations and by several hydrogen bonds. The diphosphate anion shows an eclipsed conformation.     

Seven-coordinated chelate [Cd(SCZ)3·H2O](HTNR)2(H2O)2: Synthesis,crystal structure and energetic properties

To deepen the study on heptacoordinate transition metal coordination complexes, a novel seven-coordinated coordination compound [Cd(SCZ)₃·H₂O](HTNR)₂(H₂O)₂ (1, SCZ = semicarbazide, H₂TNR = styphnic acid) was synthesized and characterized by elemental analysis and FTIR spectroscopy. Single-crystal X-ray diffraction analysis revealed that 1 crystallizes in the triclinic space group P-1. The thermal decomposition mechanism of 1 was studied by differential scanning calorimetry (DSC). The non-isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa-Doyle's method, respectively. Sensitivity tests revealed that 1 is insensitive to mechanical stimuli. The heat of combustion was measured by oxygen bomb calorimetry and the enthalpy of formation was calculated.     

Thermal expansion,pyroelectricity and linear optical properties of Li2SeO4·H2O and Li2SO4·H2O

Large single crystals of polar Li₂SeO₄·H₂O were grown at 343 K from aqueous solution. Temperature dependent thermal expansion coefficients of Li₂SeO₄·H₂O and Li₂SO₄·H₂O were determined within the temperature range 133 K–313 K and coefficients of the pyroelectric effect within the temperature range 183–343 K. Refractive indices between 365 nm and 1530 nm as well as unpolarized absorption spectra of Li₂SeO₄·H₂O and Li₂SO₄·H₂O were measured and phase‐matching curves for second harmonic generation were calculated. Both compounds allow type I and type II phase‐matching at wavelengths from about 650 nm to the near infrared region. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal and molecular structure of pyridinium di-μ-oxo-bis(oxodichloroaquomolybdate(V)) monohydrate, (pyh)2[Mo2O4Cl4(H2O)2] · H2O

The crystal and molecular structure of pyridinium di--oxo-bis(oxodichloroaquomolybdate(V)) monohydrate has been determined from MoK diffractometer data. The compound crystallizes in the monoclinic space groupP2 ₁/m witha = 7.544(1),b= 17.046(3),c = 7.894(1) Å, = 106.00(1) ° andZ = 2. The structure was solved by the heavy-atom technique and refined by full-matrix least-squares method toR = 0.046, using 1800 reflections for whichF> 4(F). Molybdenum atoms are linked by the double oxygen bridge with an Mo—O distance of 1.943(4) Å and an Mo—O—Mo angle of 83.4(2) °. The Mo—Mo distance is 2.584(1) Å, indicating direct Mo—Mo bonding. The pyridinium and [Mo₂O₄C1₄(H₂O)₂]^2- ions are hydrogen bonded through N—H ... O bonds. The N ... O contact is 2.656(8) Å.     

Synthesis and crystal structure of [Tb4(H2O)2](C2O4)2(C5H6O4)4

A terbium complex associating two ligands, oxalate and glutarate, was prepared under hydrothermal conditions at 200°C by treating an aqueous suspension of terbium oxalate decahydrate with glutaric acid and guanidinium carbonate. Its structure was solved by X-ray diffraction on a single crystal. It crystallizes in the monoclinic space group P2₁ with lattice constants, a = 9.514(1) Å, b = 9.0681(8) Å, c = 19.702(2) Å, and = 97.90(1)°. The terbium atoms and the oxalate ligands build dense chains which are connected by one side of the carboxylic group of some glutarate ligands, thus forming a sheet at the c level 0 and 1/2. These sheets are bridged by glutarate groups. The terbium atoms are ninefold coordinate with nine oxygen atoms of the ligands or with one water molecule and eight oxygen atoms of the ligands. Each polyhedron of the terbium atoms share one edge and one face of oxygen atoms with the two neighboring ones. The oxalate ligands are bischelating and bismonodentate. The coordination scheme of glutarate differs: either they are bismonodentate from one side and chelating and monodentate from the other side or they are chelating and monodentate from both sides.     

Crystal and molecular structures of two polymeric organotin carboxylates,C5H12O2Sn and C5H9F3O2Sn

The crystal and molecular structures of trimethyltin(IV) acetate and trimethyltin(IV) trifluoroacetate have been determined from three-dimensional X-ray data collected by counter methods using MoK radiation. Both compounds crystallize in the orthorhombic space groupPnma withZ = 4. The acetate hasa = 10·516,b = 8·013,c = 9·706 Å and the trifluoroacetate hasa = 10·567,b = 9·237,c = 9·985 Å. ConventionalR-factors for the two compounds following least squares refinement are, for the acetate, 0·018 (for 731 reflexions) and, for the trifluoroacetate, 0·055 (for 460 reflexions) respectively. The compounds are isostructural and are polymeric with tin atoms linked by carboxylate bridges which are exactly planar. The tin atoms are in five-fold trigonal bipyramidal coordination with the methyl groups in the basal plane and oxygen atoms at the apices. Sn-O interatomic distances are, for the acetate, 2·205(3) and 2·391(4) Å, and for the trifluoroacetate, 2·18(1) and 2·46(2) Å.     

Synthesis, structure and characterization of a new inorganic-organic hybrid complex (C3H5N2)2[Cd(C3H4N2)2Nb2O3F8]·2H2O

(C₃H₅N₂)₂[Cd(C₃H₄N₂)₂Nb₂O₃F₈]·2H₂O (C₃H₄N₂=imidazole) (1) was prepared from the hydrothermal reaction of Nb₂O₅, 3CdSO₄·8H₂O, C₃H₄N₂, HF and H₂O at 403 K, and characterized by single crystal X-ray diffraction and IR spectra. 1 crystallizes in the orthorhombic system, space group Pba2, with a=11.0192(9), b=16.8012(14), c=6.8717(6) ?, and Z=2. The crystal is made up of [Cd(C₃H₄N₂)₂Nb₂O₃F₈]²⁻ anions, [C₃H₅N₂]⁺ complex cations and H₂O molecules of crystallization. And the backbone of the compound is a one dimension coordination polymeric chain containing the anions. The complex cations and anions are linked through hydrogen bonding interactions. Co-crystallized water molecules fill in the pores and hydrogen bond to the host. Bond valence sums show that O1, O3 and F3 have much more negative charge, which are in agreement with the crystal structure that they act as bridging atoms.Supplementary material CCDC-606794 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at http://www.ccdc.cam.ac.uk/ const/retrieving.html or from the Cambridge Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033 or e-mail: deposit@ccdc.cam.ac.uk.     

Crystal and molecular structure of 1,4,10-trioxa-7,13-diaza-cyclopentadecane-7,13-diacetatocopper (II) dihydrate,C114H24N2O7Cu · 2H2O

l,4,10-Trioxa-7,13-diazacyclopentadecane-7,13-diacetatocopper(II) dihydrate: space groupP4₃, witha=b=7.217(1),c=34.553(7) Å, andZ=4. The structure was solved by direct methods, and refined by full-matrix least-squares toR=0.039 andR _w=0.043. The Cu(II) atom is seven-coordinated (deformed pentagonal bipyramidal coordination) by the two nitrogens and three oxygens of the 15-membered ring and by two oxygens from acetato groups. These groups form 5-membered chelate rings positioned on opposite sides of the macrocycle.     

Hydrothermal synthesis and structure of a novel terbium coordination polymer with packing cavities, {[Tb(TCB)1/2(H2TCB)1/2(H2O)](H2O)2}n (H2TCB = 1, 2, 4, 5‐benzenetetracarboxylic acid)

A novel terbium coordination polymer {[Tb(TCB)_1/2(H₂TCB)_1/2(H₂O)](H₂O)₂}_n (H₂TCB = 1, 2, 4, 5‐benzenetetracarboxylic acid) ( 1 ) has been hydrothermally synthesized and determined by single crystal X‐ray diffraction method, which features a very interesting three‐dimensional framework with large packing cavities. It crystallizes in the monoclinic space group P2₁/n with a = 1.0723(4) nm, b = 0.7168(3) nm, c = 1.7155(6) nm, β = 97.079(4)°, V = 1.3086(8) nm³, Z = 4, and final R₁ = 0.0203, wR₂ = 0.0404. In 1, the protonated carboxylate groups are free, the other carboxylate groups are bonded to Tb³⁺ ion in three modes: the chelating bidentate, the bridging bidentate and bridging tridentate. Moreover each Tb³⁺ ion is coordinated by nine oxygen atoms from six carboxylate groups and one water molecule respectively to complete a deformed tricapped trigonal prismatic geometry. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure analyses of menthone- and isomenthone-tosylhydrazones,C17H26N2O2S

The crystal and molecular structures of two configurational isomers of the title compound have been determined by three-dimensional, single-crystal X-ray diffractometry. Both (2S,5R)- and (2R,5R)-4-methylbenzenesulfonic acid-[5-methyl-2-(1-methylethyl)cyclohexylidene] hydrazide (hereafter referred to as menthone- and isomenthone-tosylhydrazone, orI andII, respectively) crystallize in the orthorhombic space groupP2₁2₁2₁ (No. 19, D ₂ ⁴ ) with four formula units per cell anda=5.209(1),b=17.501(1),c=20.154(1)Å anda=5.281(1),b=17.300(1),c=20.422(1)Å, respectively. The phase problems were solved by direct methods and the respective final full-matrix least-squares refinements of 1767 and 3010 unique reflections converged toR=0.046 and 0.052. In both structures, the toluenesulfonamide group occupies a positionanti to the more substituted side of the cyclohexyl ring, the C(16)-C(11)-N(2) angles are significantly wider than 120°, and each sulfonamide nitrogen (1) atom appears to exhibit a distorted trigonal pyramidal geometry. The structures differ in the positioning of the isopropyl and methyl substituents on the cyclohexane ring, with thetrans isomerI having both groups equatorial, while thecis isomerII exhibits an axial isopropyl group. The molecules in the crystal lattice are held together by van der Waals forces. X-ray powder diffraction, conoscopic, infrared, and¹H and¹³C NMR analyses have been performed.(2S,5R)- and (2R,5R)-4-Methylbenzenesulfonic acid-[5-methyl-2-(1-methylethyl)cyclohexylidene]hydrazide.     

Structure of a potent neuromuscular blocking agent: Caracurine-II dimethochloride octahydrate, [C40H44N4O2]2+·2CI−·8H2O

Crystals of this calabash curare alkaloid, space groupP2₁; havea=12.695(4), Å,b=7.424(2) Å,c=21.762(6) Å,=98.03(5)°,Z=2,F(000)=884. The structure was solved by direct methods and refined by least squares toR=0.10. The alkaloid cation, with two-fold molecular symmetry, has a highly fused ring system and is structurally rigid. This determination provides accurate stereochemical parameters for those atoms and groups (N⁺ centers, aromatic rings, and hydrogen bond acceptors) postulated by various theories as involved in binding to the acetylcholine receptor. In the crystal, layers of alkaloid cations parallel to thebc plane alternate with layers containing two Cl^– ions and eight water molecules distributed almost randomly over ten sites. Electrostatic attractions between N⁺ and Cl^– bind the alternating layers together. Each one of the ten sites is, on average, 4.60 Å from one or two N⁺, allowing the two Cl_– ions to be disordered. Binding interactions within the alkaloid layers are solely van der Waals attractions. Within each H²O/C1^– layer there is a complex hydrogen bond system, including four infinite spirals parallel to theb axis, with an average bonding distance of 2.94 Å. There are no hydrogen bonds between layers. The possible relevance to the activity of the alkaloid of its ability to organize large amounts of water is discussed.     

Growth,Properties, and Structure of Cadmium Sulfamate Cd(NH2SO3)2 · 2H2O

Crystallography Reports - The temperature dependence of the solubility of Cd(NH2SO3)2 compound in the range from 25 to 80°C has been determined. It is found that Cd(NH2SO3)2 · 2H2O and...