Crystal structure of dicesium thorium trisulfate dihydrate,Cs2Th(SO4)3·2H2O

Dicesium Di--sulfatosulphatobisaquothorate(IV), H₄O₁₄S₃Cs₂Th, (M _r =821.8) crystallized from water in the monoclinic space groupP2₁/c (No. 14), witha=6.415(2),b=15.95(1),c=13.078(8) Å,=90.88(4)°,V=1338(14) ų,Z=4,D _x =4.08 g cm^–3, MoK (=0.71069 Å),=195.8 cm^–1,F(000)=1407.3, room temperature, finalR=0.086 for 1699 unique observed reflexions. Two of the sulfate groups are tridentate (chelating and bridging) and the other is bidentate chelating. As the waters are both coordinated the thorium is 10-coordinate. It shows an unusual 2/4/2/2 geometry.     

Reaction of trimethylaluminum and trimethylgallium with bifunctional amines: Syntheses and molecular structures of [Me2Al−N(CH2CH2)2−C−(OCH2)2]2 and [Me2Ga−N(Si(H)Me2)2]2

The crystalline products [Me₂Al–N(CH₂CH₂)₂–C–(OCH₂)₂]₂ (I) and [Me₂Ga–N(Si(H)Me₂)₂]₂ (II) were prepared from reactions of trimethylaluminum and trimethylgallium with 1,4-dioxa-8-azaspiro[4.5]-decane and 1,1,3,3-tetramethyldisilazane, respectively, in toluene. The organoaluminum dimer crystallizes in the monoclinic space groupP2₁/c with unit cell parametersa=8.970(2) ,b=9.683(2) ,c=12.833(3) , =103.18(2)°,V=1085.3(3) ³, andD _calcd=1.22 g cm^–3 forZ=2. Least-squares refinement based on 935 observed reflectionsI>3(I) in the range 3.5°<2<45.0° led to a finalR factor of 0.033 (R _w =0.041). The dimeric organosilazagallium crystallizes in the triclinic space group with unit cell parametersa=7.636(2) ,b=9.168(2) ,c=9.466(3), =72.81(2)°, =87.94(2)°, =69.90(2)°,V=593.0(3) ³, andD _calcd=1.30 g cm^–3 forZ=1. Least-squares refinement based on 1661 observed reflectionsI>3(I) in the range 3.5°<2<48.0° led to a finalR factor of 0.055 (R _w =0.070). Both compoundsI andII reside about a crystallographic center of symmetry and contain a planar M₂N₂ (M=Al forI, Ga forII) four-membered ring withI having an Al...Al contact of 2.801 .     

Structural characterization and photophysical properties of a luminescent trinuclear zinc(II) complex exhibiting multiple coordination geometries

A luminescent trinuclear zinc(II) complex, tris(-2,3-toluenedithiolato)-1:2²S¹;1:2²S¹, 2:3²S²;3S², 1:3²S³;3S³-bis(2,2-bypyridine)-1²N,N,2²N,N-trizinc, containing 3,4-dimercaptotoluene (tdt) and 2,2-bipyridine (bpy) has been synthesized and found to have the trinuclear formulation Zn₃(tdt)₃(bpy)₂ (I). The complex crystallizes in the monoclinic space group P2₁/n with a = 11.7247(12), b = 20.134(2), c = 17.7376(18) Å and = 103.743(2). The complex has two heteroleptic zinc(II) centers exhibiting similar distorted trigonal bipyramidal geometries with the third homoleptic zinc(II) center displaying a flattened tetrahedral geometry. Present in the solid state are both intra- and intermolecular – interactions. The complex is emissive at 77 K in the solid state with an emission maximum at 574± 2 nm with a luminescence lifetime of 7.4± 0.4 ns. The unstructured emission is assigned as a metal-mediated ligand-to-ligand –^* charge transfer transition.     

Crystal structures of 1-(2-hydroxyphenyl)-3-phenyl-1,3-propanedione and 1-(1,3-benzodioxol-5-yl)-3-(2,4-dimethoxyphenyl)-1,3-propanedione

1-(2-Hydroxyphenyl)-3-phenyl-1,3-propanedione crystallizes in the triclinic space group (a=5.4233(5),b=13.910(1),c=17.036(1) Å, =68.311(6), =80.854(7), =78.760(8)°) as two independent enolic tautomers in which the hydroxyl and phenolic protons are hydrogen bonded to the ketonic oxygen atom. The structure was refined toR=0.039 for 2085I3(I) reflections. 1-(1,3-Benzodioxol-5-yl)-3-(2,4-dimethoxyphenyl)-1,3-propanedione, which belongs to the triclinic space group (a=7.3990(7),b=8.1239(5),c=14.004(1) Å, =86.673(6). =88.574(7), =64.885(7)°) also exists in the enolic form. The structure was refined toR=0.040 for 1564I3(I) reflections.     

Synthesis,characterization and crystal structure of oxovanadium(IV) complex with tridentate o-van-gly and bidentate phenanthroline

A novel oxovanadium(IV) complex with tridentate schiff base and bidentate phenanthroline ligands, VO(o-van)(phen) 2H₂O[o-van-gly: o-vanillin-glycine; phen: phenanthroline], was synthesized and characterized by elemental analysis, IR and UV-vis spectra. The crystal structure was determined by X-ray single crystal diffraction analysis. The crystal of title complex (C₂₂H₂₁N₃O₇V, M_w = 490.36) belongs to triclinic, space group P-1 with the following crystallographic parameters: a = 9.247(3) Å, b = 10.125(4) Å, c = 13.100(5) Å, = 106.343(6), = 96.042(7), = 101.726(7), V = 1135.0(7) ų, Z = 2, D_c = 1.435 Mg m^–3, (MoK = 0.485 mm^–1, F(000) = 506, and final R₁ = 0.0779, wR₂ = 0.1598 for observed reflections 1606 (I > 2(I)). V(IV) is six-coordinate with three oxygen atoms and three nitrogen atoms in a distorted octahedral geometry. The complex forms a 3-D network via – stacking and hydrogen bonds.     

X-ray structures of two methoxybenzo[b]thiophenes

The crystal and molecular structures of two methoxybenzo[b]thiophenes have been determined by three-dimensional, single-crystal X-ray diffractometry. Both 3-(4-hydroxy-3, 5-dimethoxybenzoyl)-2-(4-methoxyphenyl)-6-methoxybenzo[b]thiophene and 3-(2,6-dimethoxybenzoyl)-2-(4-methoxyphenyl)-6-methoxybenzo[b]thiophene (hereafter referred to asI andII, respectively) crystallize in the monoclinic centrosymmetric space groupP2₁/n (No. 14, C _2h ⁵ ) with four formula units-per cell witha=6.866(1),b=28.638(2),c=11.830(2) Å, and =105.52(1)° anda=9.328(1),b=7.977(1),c=29.650(4) Å, and =97.87(1)°, respectively. The phase problems were solved by direct methods and the respective final full-matrix least-squares refinements converged toR=0.046 and 0.031. The structures differ in the positioning of the dimethoxy groups of the benzoyl ligands and the addition of a hydroxyl group inI. The molecules in the crystal lattice are held together by van der Waals forces plus the addition of hydrogen bonding in compoundI. Selected bond distances and angles and torsion angles are tabularized.     

Crystal structure of 5α-bromo-8β,9α-dimethyl-hydrindane-1,4-dione

The molecular structure of 5-bromo-8,9-dimethylhydrindane-1,4-dione (C₁₁H₁₅BrO₂) has been confirmed using three-dimensional X-ray data collected by means of a Picker FACS-1 four-circle diffractometer. The compound crystallized in the space groupC2/c with unit cell constantsa = 26.56(5),b = 6.68(1),c = 12.32(2) Å and = 90.6(1) °; the density was 1.55 g cm^–3 andZ = 8. Least-squares refinement of the positional and anistropic thermal parameters gave a finalR ₁ value of 0.083 for 793 significant reflections.     

Crystal and molecular structure of 1,N6-ethenoadenosine hydrochloride

The X-ray structure of 1,N ⁶-ethenoadenosine hydrochloride, C₁₂H₁₄N₅O₄Cl, has been determined from three-dimensional diffractometer data and refined by full-matrix least-squares techniques. The crystals are monoclinic:P2₁ No. 14,a=6.1540(5),b=18.511(1),c=6.7412(4) Å,=112.602(5)°,andZ=2; finalR=0.045 for 2662 observed reflections. The crystal and molecular structure of Ado·HC1 is very similar to that of Ado·HC1. On the other hand, the dimensions and conformation of the Ado·H⁺ cation are drastically different from those of Et Ado·H⁺. The adenosine·H⁺ moiety is not planar but has an S shape. The ribose is 2-endo-3-exo puckered, with ag ⁺ side chain; the glycosidic torsion angle is in theanti region. The structure contains a three-dimensional network of H bonds in which also C-HA interactions seem to play an important role. There is no base stacking in the structure.     

Synthesis,structural, and spectroscopic study of rhenium(III) and rhenium(V) 4,6-dimethylpyrimidine-2-thiolate/triphenylphosphine mixed complexes: Crystal and molecular structure of ∥ReCl2(pymS)(PPh3)2∥·C3H6O and ∥ReOCl2(pymS)(PPh3)∥

4,6-dimethylpyrimidine-2(1H)-thione reacts with rhenium(V) precursorstrans-ReOX₃(PPh₃)₂ (X=Cl, Br) in acetone, to afford two classes of crystalline pyrimidinethiolate/triphenylphosphine mixed complexes:trans-Re^IIIX₂(C₆H₇N₂S)(PPh₃)₂·C₃H₆O and Re^vOX₂(C₆H₇N₂S)(PPh₃) (X=Cl, Br). The crystal structures oftrans-ReCl₂(C₆H₇N₂S)(PPh₃)₂·C₃H₆O (I) and ReOCl₂(C₆H₇N₂S)(PPh₃) (II) have been determined from single-crystal diffractometer data and refined toR factors of 0.0496 and 0.0365, respectively. (I) crystallizes in the triclinic space group P¯1 witha=16.875(4),b=13.969(7),c=9.510(2) Å;=81.78(2)°,=85.15(12)°, =107.97(8)° andZ=2. The coordination geometry around the rhenium center exhibit mutuallytrans phosphine groups and chloride ligands disposedtrans to the nitrogen and sulfur donors of the pyrimidinethiolate ligand which form a four-membered chelate ring with the metal. (II) crystallizes in the monoclinic space group P2₁/c witha=12.554(3),b=10.501(1),c=19.200(5) Å;=106.54(2)° andZ=4. The rhenium atom presents a very distorted octahedral configuration with a chlorine atomtrans to phosphine ligand in the axial position and the N,S-chelate ligand in the equatorial plane with the sulfur donor atomtrans the Re=O_oxo group. The compounds were characterized also by means of ir and nmr spectroscopic measurements; reaction pathways are discussed on the basis of structural data.     

Crystal and molecular structure of powerine: Methyl 10,17-dihydroxy-(16β,17β,20α)-yohimban-16-carboxylate

The methanol adduct of powerine [methyl 10,17-dihydroxy-(16,17,20)-yohimban-16-carboxylate], C₂₁H₂₆N₂O₄. CH₃ OH, crystallizes in the orthorhombic space groupP2₁2₁2₁ (no. 19) with cell dimensionsa = 8.558(3),b = 14.162(7),c = 16.993(7) Å. The crystal and molecular structure has been determined by X-ray diffraction analysis and refined using full-matrix least squares methods to a reliability index,R, of 0.090 with 1139 observed (F 2.5 _F ) intensities. With the configuration at C15 arbitrarily assigned those at the chiral centers C3-H, C16-CO₂Me, C17-OH and C20-H are respectively ,,,: theC-D ring junction istrans and that ofD-E iscis. All bond lengths and bond angles are normal.     

Crystal structure of 14, α-hydroxy,sandarocopimar-7, 15-diene-19-oic acid

C₂₀H₃₀O₃, M _r =318.46, Monoclinic,P2₁,a=12.232(2) ,b=11.491(2) ,c=14.160(3) , =115.2°(3),V=1800.3(7) ³,Z=4,D _x =1.18 Mg m^–3, (CuK)=1.5418 , =5.3 cm^–1,F(000)=696,T=298 K. FinalR=0.044 for 2645 reflections withI>2. The two crystallographically independent molecules in the unit cell adopt essentially similar conformations. The structure reveals atrans relationship between the hydrogen at C(9) and the methyl group at C(20). The stereochemistry at C(13) is S. Apart from van der Waals forces the structure is stabilized by hydrogen bonds.     

Crystal structure of a 1:1 molecular adduct of hexamethylenetetramine with phenylacetic acid

A 11 crystalline adduct of hexamethylenetetramine with phenylacetic acid, (CH₂)₆N₄·C₆H₅CH₂COOH, has been isolated and characterized by X-ray analysis. The compound crystallizes in space groupI¯4 (No. 82), witha=20.576(3),c=6.907(1) Å, andZ=8. The crystal structure is composed of a packing of discrete molecular aggregates corresponding to the stoichiometric formula, each being consolidated by a NH-O hydrogen bond of length 2.643(8) Å, which has no significant effect on the regular geometry of the (CH₂)₆N₄ cage system. The C-CO₂ and phenyl groups in the C₆H₅CH₂COOH moiety make a dihedral angle of 74(1)°. The structure has been refined toR=0.071 for 1350 observed (F _o >2F _o ) MoK data.     

Structural investigation of compounds related to α,β-dehydroaminoacids: (E)-methyl-α-cyanocinnamate

The crystal and molecular structure of the methyl ester of-cyanocinnamic acid [(E)-methyl--cyanocinnamate] has been determined from three-dimensional X-ray data. C₁₁H₉NO₂ is monoclinic, space groupC2/c,Z=8,a=12.386(2),b=8.237(1),c=19.320(2) Å,=98.49(5)°. The He(I) and He(II) photoelectron (PE) spectra of (E)-methyl--cyanocinnamate are presented and discussed in comparison with those of previously investigated molecules, within a comprehensive investigation of the electronic structure of,-dehydroamino acid derivatives and related compounds.     

Molecular structure of N-(2-phenylethyl)amide of α-(1,1-ethylenedioxy)-ethyl γ-hydroxybutyric acid (I) and1H NMR spectra of (I) and N-(p-methoxybenzyl)derivative (III)

The spectroscopic and X-ray investigation of the N-(2-phenylethyl) amide of -(1,1-ethylenedioxy)-ethyl--hydroxybutyric acid are reported. The¹H NMR spectra for the title structure and for the N-(p-methoxybenzyl) amide of -(1,1-ethylenedioxy)-ethyl--hydroxybutyric acid are given. The N-(2-phenylethyl)amide of -(1,1-ethylenedioxy)-ethyl--hydroxybutyric acid, C₁₆H₂₃O₄N, crustallizes in the monoclinic space groupP2 ₁/c witha=21.547(5),b=6.333(2),c=11.822(3) Å and =101.01(2)°. The dioxolane ring has a half-chair conformation with C₂(O3)=2.4° and ||_av=18.2°. The inconsiderable deviations from planarity of the six atoms of the amide group are caused mainly by twist around the C4–N1 bond and out-of-plane bending at the N1 atom ((C4–N1)=4°, X_N =7°, X_c =0.4° ). The amide group plane is nearly coplanar with the phenyl ring. The molecules are connected by two intermolecular hydrogen bonds.     

Bis(2,6-(2′,6′-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II)

Bis(2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II) was prepared by the reaction of 2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenol with nickel chloride. The title complex crystallized in P2₁/c, with cell dimensions a = 9.962(2) Å, b = 12.087(3) Å, c = 24.445(6) Å, and = 97.032(5), giving a volume of 2921.4(13) ų. The bis(2,6-(2,6-diisoproylanil)diformyl-4-chloro-phenolate) nickel(II) adapts an ideal parallelogram, in which the Ni atom is coordinated with two phenolic oxygen atoms [O(1), O(1A)] and two imino nitrogen atoms [N(1), N(1A)].     

Crystal structure of an intermediate in the synthesis of artemisinin

C₁₄H₂₂O₃,M _r =238.33, P2₁2₁2₁,Z=4,a=6.892(2),b=11.453(1),c=17.159(5) Å. [1R–[1(R^*), 4, 4a, 8a]]–,4-Dimethyl-decahydro-7-oxo-1-naphtaleneacetic acid. The cyclohexane ring adopts a chair conformation and thecis-fused cyclohexanone ring is in a slightly distorted chair conformation. The molecular packing involves an hydrogen bond and C–H...O contacts.     

Structure of bis(2-pyridine-N-oxide) diselenide and its formation from tetraphenylantimony(V)selenopyridine-N-oxide

The structure of bis(2-pyridine-N-oxide) diselenide was determined by single crystal X-ray diffraction. The compound crystallized in the triclinic system and the structure was solved in the space group . The lattice constants were determined to bea=7.174(2),b=7.176(2),c=11.070(2) , =87.67(2)°, =73.68(2)°, and =89.57(2)°;Z=2,D _x=1.906 Mg m^–3. The final least squares refinement based on 1942 independent observed reflections yieldedR=0.033,wR=0.044. The Se–Se bond length is 2.326(1) and each Se is coordinated to the O atom of the corresponding N-oxide moiety at a distance of about 2.6 .     

Crystallographic and spectroscopic studies on ethylenediaminetetraacetic acid (edta) III. Crystal and molecular structure of α-edta and infrared studies on α- and β-edta

-Edta is monoclinic:C2/c,a= 11.812,b = 9.647,c = 12.970 Å, = 113.23 ° andZ = 4. The structure has been determined by direct methods with CuK diffractometer data, and refined by full-matrix least squares toR = 7.2% for 737 observed reflexions. The molecule exists as a zwitter ion in acis conformation, and possesses crystallographic two-fold symmetry. The nitrogen atom is protonated and takes part in hydrogen bonding. -Edta is hydrated, in this specimen, refinement indicated a value of 0.39 H₂O per molecule of edta. A short (2.47 Å) hydrogen bond links oxygen atoms in adjacent molecules. Infrared spectra are reported for both -edta and -edta; the results are discussed in terms of the crystal structures. The formulation of -edta with 0.39 mole H₂O is explained.     

A comparison of the coordination preferences of Zn, Co, and Cd(II) with the heteroscorpionate ligand (2-hydroxy-3-t-butyl-methylphenyl)bis (3,5-dimethylpyrazolyl)methane

Reaction of the Zn, Cd, or Co nitrate salts with the deprotonated ligand (2-hydroxy-3-t-butyl-methylphenyl)bis(3,5-dimethylpyrazolyl)methane (L1O^–) in methanol produced the following complexes: [(L1OH)Zn(NO₃)₂] in two isomorphs, a = 40.983(8) Å, b = 9.571(2) Å, c = 15.667(8) Å, = 90, = 106.38(1), = 90, C2/c, and a = 13.027(3) Å, b = 14.781(4) Å, c = 16.107(3) Å, = 90, = 105.30(1), = 90, P2₁/n; [(L1OH)Cd(pz)(NO₃)₂] a = 14.7476(2) Å, b = 13.5411(2) Å, c = 16.7223(2) Å, = 90, = 110.3840(10), = 90, P2₁/c; and [(L1O)Co(pz)(NO₃)] a = 11.4240(2) Å, b = 13.4498(2) Å, c = 13.8056(2) Å, = 105.2080(10), = 105.8130(10), = 112.7470(10), P . The Zn adopts a pseudotetrahedral four-coordinate geometry where the potentially tridentate ligand is actually bidentate with a protonated and uncoordinated phenoxy arm. The Co complex is pseudooctahedral six-coordinate where the phenoxy arm is deprotonated and coordinated. Finally the Cd complex is seven-coordinate but the metal is not coordinated through the phenoxy group that is again protonated.     

Crystal and molecular structure oftrans-1-benzylidene-1,2,3,4-tetrahydronaphthalene

The compound C₁₇H₁₆ crystallizes in the triclinic space groupP¯1 witha=6.719(1),b=11.598(2),c=8.757(2) Å, =108.54(2),=97.58(1), =97.40(1)°,Z=2. The structure was determined by direct methods and refined by full-matrix least squares toR=0.045 for 1012 reflections. The molecule adopts thetrans configuration. The cyclohexenylidene ring has the half-chair conformation.