Crystal structure of form 1, magnetic properties and polymorphism of bis (NN-di-(n-propyl)dithiocarbamato iron (III) iodide

The crystal structure of bis (NN-di(n-propyl)dithiocarbamato iron(III) iodide, Fe^III(S₂CN₆H₁₄)₂I, has been determined by the heavy-atom method and refined toR=0.055 for 3487 reflections withI(hkl)>3I(hkl). The crystals are triclinic,C¯1,Z=8,a=27.644(6),b=19.186(4),c=8.694(2) Å,=87.79(1),=88.72(1), =101.87(2)°. The I-Fe bond lengths are different in the two moleculesA andB in the asymmetric unit, having values of 2.642 Å (2.655) and 2.612 Å (2.634) respectively (libration-corrected values given in parentheses). The measured effective magnetic moment _eff3.89 BM, independent of temperature (93-353K), suggests a spinS of 3/2 with three unpaired electrons for Fe^III.     

On the organoaluminum chemistry of multidentate phosphine ligands. Reaction of trimethylaluminum with bis(diphenylphosphino)methane: Synthesis and molecular structure of [Al(CH3)3]2[(C6H5)2PCH2P(C6H5)2]

Reaction of an excess of trimethylaluminum with bis(diphenylphosphino)-methane in heptane affords the crystalline complex [A1(CH₃)₃]₂[(C₆H₅)₂PCH₂P(C₆H₅)₂]. The title compound crystallizes in the triclinic space group P¯1 with unit cell parametersa=10.053(6),b=11.017(6),c=15.908(8) Å,=85.58(4),=71.80(4), =77.49(4)°,V=1634(1) ų, andD _c=1.07 g cm^–3 forZ=2. Least-squares refinement based on 2924 observed reflection with intensitiesI3I) in the range 2.00245.0° converged atR=0.050 (R _w=0.067). The Al-P distances are 2.585(2) and 2.521(2) Å, and the P-C-P angle is 121.4(2)°.     

Structure of (Z)-1-p-methoxyphenyltelluro-1,4-diphenyl but-1-en-3-yne

C₂₃H₁₈TeO,M _r=437.97, ,a=9.940(2),b=13.664(3),c=7.895(2) Å, =80.60(1), =69.71(2), =75.95(1)°,V=972.0(4) ų,Z=2,R=0.041 for 2668 observed reflections. The Te–C bond distances are 2.109(5)Å and the C–Te–C angle is 96.0(2)°. The phenyl rings are planar to within experimental accuracy, making dihedral angles of 64.6(2), 65.3(2) and 31.1(3)°.     

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.     

Crystal and molecular structure of (exo)-2-methoxycarbonyl-5-ethoxycarbonyl-4,5,6,11b-tetrahydroisoxazolidino-[2,3-a]-β-carboline,C18H20N2O5

The structure of the title compound, C₁₈H₂₀N₂O₅, was determined by X-rays atT=290 K.M _r =344.366, monoclinic, space groupP2₁/c,a=13.7850(8),b=8.8951(7),c=15.1603(11) Å, =111.410(6)°,V _c =1730.7 ų,Z=4,D _x =1.322 Mgm^–3. Cu K radiation (graphite crystal monochromator, =1.54178 Å),(Cu K)=7.69 cm^–1. Final conventionalR-factor=0.057,R _w =0.076 for 2160 observed reflections and 271 variables. The structure was solved usingMultan.     

Crystal and molecular structure of: 5-(1-oxoethyl)-1-methyl-2-(5-bromo-6-methoxy-2-naphthyl)-6-oxabicyclo[3.2.1]octan-7-one and 5-(1-oxoethyl)-1-methyl-2-(5-bromo-6-methoxy-2-naphthyl)-6-oxabicyclo[3.2.1]octane

X-ray crystallographic studies of the two title compounds have shown that the molecules crystallize in the same triclinic space group, , with very similar cell dimensions. For C₂₁H₂₁BrO₄,a=12.056(5),b=13.206(5),c=7.595(3)Å, =90.38(3), =106.07(3) and =124.42(3)° and for C₂₁H₂₃BrO₃,a=12.076(6),b=13.090(5),c=7.490(3)Å, =92.65(5), =104.90(5) and =124.55(5)°. Both compounds possess the oxabicyclo[3.2.1]octane bridged ring system and differ only at the carbon to the ring oxygen where the Csp³ in the ether is replaced by Csp²=O in the lactone. Both cyclohexane rings adopt distorted chair conformations and the lactone and ether rings approximate closely to the envelope conformation. The bromine substituent at C(4) results in distortion of the naphthalene ring. Both molecules pack with the naphthalene rings parallel to each other with interplanar spacings of 3.71 Å in the ether and 3.66Å in the lactone.     

Crystal structure of di(N-benzyl piperidinium) pentachloroantimonate(III) dihydrate

The salt di(N-benzyl piperidinium) pentachloroantimonate(III) dihydrate crystallizes in the orthorhombic system with space group Cmc2₁, the unit cell dimensions are: a = 29.383(1), b = 10.509(2), c = 9.941(1) Å, with Z = 8. The structure shows a layer arrangement perpendicular to the a axis: planes of SbCl₆ octahedra alternate with planes of [C₁₂H₁₇N]⁺ cations. The SbCl₆ octahedra are connected through a O(W)–HCl hydrogen bonds and a chlorine bridge, so that infinite unidimensional chains of composition [SbCl₅(H₂O)₂]^2n– _n are formed in the structure along the c direction. These chains are connected to [C₁₂H₁₇N]⁺ entities by N–HCl and N–HO(W) hydrogen bonds, forming a three-dimensional network. It was found that lengths of Sb–Cl bonds may differ from each other. The differences shown as a distortion of the SbCl₆ octahedra were attributed to the Sb(III) lone electron pair stereoactivity.     

Hydrogen-bonded coordination network in crystal structures of [Cu(3-PM)4Cl2] and [Cu(4-PM)4Cl]Cl, (PM = pyridylmethanol)

The crystal and molecular structures of [Cu(3-PM)₄Cl₂] (1) and [Cu(4-PM)₄Cl]Cl (2) have been determinated by X-ray crystallography. Complex 1 crystallizes in the triclinic system, space group P–1, with lattice parameters a = 7.972(2) Å, b = 8.293(2) Å, c = 10.707(2) Å, = 105.73(3)°, = 90.04(3)°, = 110.38(3)°, and Z = 1 at 100 K. The coordination geometry of each Cu atom is approximately octahedral formed by four nitrogen atoms of pyridine rings of 3-pyridylmethanol molecules in the equatorial plane and two chlorine atoms occupying the axial positions. The O—HsO, C—HsCl, and O—HsCl intermolecular hydrogen bonds and s stacking link the molecules in 3-D hydrogen-bonded coordination network. Complex 2 crystallizes in the tetragonal system, space group P4/n, with lattice parameters a = 10.464(1) Å, c = 11.339(2) Å, and Z = 2 at 217 K and a = 10.352(1) Å, c = 11.201(2) Å, and Z = 2 at 293 K. The coordination geometry of Cu atom in the [Cu(4-PM)₄Cl]⁺ ion is approximately square pyramidal formed by four nitrogen atoms of pyridine rings of 4-pyridylmethanol molecules in equatorial plane and one chlorine atom in axial position. The O—HsCl and C—HsCl intermolecular hydrogen bonds link the molecules in 2-D hydrogen-bonded coordination network.     

Copper(I) halide complexation to norbornene: (CuCl)5(norbornene)4: A complex of novel structure

Cu(I) bromide and chloride form complexes with norbornene which differ in stoichiometry and copper-halide motif. (CuCl)₅(norbornene)₄: [triclinic space group P¯1,a=12.138(6),b=22.849(6),c=5.953(1)Å,=90.012(3),=75.792(3), =87.776(4)°,Z=2,R=10.8%, 1365 obs. refl.] displays a structure of new motif in which an eight-membered ring of alternating copper and chloride atoms is bridged by a fifth copper atom which binds to ring chloride atoms in the 1,5 positions and is further bound to a terminal chlorine atom. The four copper atoms of the ring are each bound to a norbornene molecule. [CuBr(norbornene)]₄ crystallizes with an eight membered tub shaped ring of alternating copper and bromine atoms having each copper atom bound to a norbornene molecule via donation of the electrons of the double bond.     

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 of 5-ethoxy-4-methylene-exo-10-oxatricyclo[5.2.1.02,6]-deca-8-ene-3-ol,C12H16O3

The structure of the title compound, C₁₂H₁₆O₃, was determined by X-rays.M _r =208.26, triclinic, space groupP¯1,a=7.802(2),b=8.449(2),c=9.069(1) Å,=90.79(1)°,=105.57(1)°, =106.07(1)°,Z=2,D _x =1.26 Mg m^–3; MoK radiation (graphite crystal monochromator, =0.71069 Å),(MoK)=0.96 cm^–1,T=290 K. Final conventionalR-factor=0.046,R _w =0.067 for 3009 observed reflections and 184 variables. The structure was solved using Patterson methods andDirdif, and the resulting all cis-endo configuration of the alcohol group on C(3) and the ethoxy group on C(5) shows that the stereochemistry of the metal-mediated addition reaction involved is solely determined by steric factors.     

Molecular structure and some reactivity aspects of 2,6-diamino-4(3H)-pyrimidinone monohydrate

Crystals of C₄H₆N₄O·H₂O are orthorhombic:Pbca,a=16.721(2),b=4.242(1),c=18.293(2)Å,Z=8. The structure has been solved by direct methods and refined by full-matrix least-squares techniques toR=0.046 for 1252 unique reflections. The structure consists of approximately planar molecules of the 3(H)4-one tautomer. Delocalization of the ring and the C=O-electrons, and conjugation of the lone-pair electrons of the amine groups with the pyrimidinone nucleus are observed. The molecules are connected by O-HO, N-HN, and N-HO hydrogen bonds. The molecular structure clarifies the chemical properties of the compound.     

Crystal and molecular structure of palladium(II), copper(II) and zinc(II) complexes of 1-methyl-3-(4-methyl)phenyltriazen-1-oxide

The structures of palladium(II), copper(II) and zinc(II) bis(chelates) of 1-methyl-3-(4-methyl)phenyltriazen-1-oxide have been determined by single-crystal X-ray methods. The crystals of [Pd(OMeN₃C₆H₄Me-4)₂] (I) are triclinic witha=7.410(3),b=7.806(3),c=8.371(2) Å, =65.80(2), =88.73(3), =81.04(3)°,Z=1, space group . The crystals of [Cu(OMeN₃C₆H₄Me-4)₂] (II) are monoclinic,a=14.934(5),b=10.111(4),c=11.762(3) Å, =96.00(2)°,Z=4, space group P2₁/c. The crystals of [Zn(OMeN₃C₆H₄Me-4)₂] (III) are triclinic witha=7.912(2),b=10.056(2),c=11.600(2) Å, =87.31(3), =74.96(3), =74.02(3)°,Z=2, space group . The structures of (I), (II), and (III) were solved to final values ofR=0.029, 0.043 and 0.034, respectively. A planar structure has been found for (I), (II) exhibits a tetrahedrally distorted square planar structure, whereas (III) is tetrahedral. The crystals of all three complexes are held by networks of stacking interactions.     

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 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 structure of trans-C2SnO5 pentagonal bipyramidal dibutylbis(phenylacetato)tin(IV) hydrate

The Lewis acidity of tin in a diorganotin dicarboxylate is demonstrated in this first example of a 1/1 adduct of the ester with a neutral ligand. The structure of dibutyltin bisphenylacetate hydrate [(C₄H₉)₂Sn(O₂CCH₂C₆H₅)₂·H₂O] has been determined from 1211 F ₀6F _c MoK reflections and refined to anR _F of 0.061 [space groupP2/a witha=8.416(2),b=10.391(5),c=14.28(1) Å,=98.42(4)° andZ=2]. TheC atoms [Sn-C 2.101(8) Å; C-Sn-C 169.9(5)°] make up the apices and the O_carboxylate [Sn-O 2.234(5), 2.439(7) Å; O-Sn-O 55.7(2)°] and O_water [Sn-O 2.342(8) Å] atoms the equatorial points of thetrans-C₂SnO₅ pentagonal bipyramid around the Sn atom. The molecular symmetry isC ₂, and the Sn and O_water atoms lie along a crystallographic twofold axis. The aqua ligand forms donor H-bonds with neighboring carboxylato groups to link the molecules into a double zigzag chain running parallel toa.     

Crystal and molecular structures of three modifications of the androgen dehydroepiandrosterone (DHEA)

The crystal and molecular structures of three forms of the androgen DHEA (dehydroepiandrosterone) have been determined by single crystal X-ray diffraction. They are: Form I, a polymorph crystallizing in space group P2₁ withZ=4; Form S1, a hydrate with composition DHEA. (1/4)H₂O, space group C2,Z=8; and Form S4, a methanol half-solvate, DHEA. (1/2)CH₃OH, space group C222₁,Z=8. The A, B, and C steroid ring conformations adopted in the five crystallographically independent DHEA molecules are invariably: chair, 8, 9-half-chair, and chair, respectively, while the D ring conformation ranges from a 14-envelope to a 13, 14-half-chair. In Forms I and S1, intermolecular hydrogen bonding is of the head-to-tail type with water molecules participating as donors in Form S1. In Form S4, DHEA molecules pack in head-to-head fashion, their hydroxyl groups being linked by hydrogen bonding to the solvent hydroxyl group. The hydroxyl H atoms of both DHEA and the included methanol are disordered, giving rise to an unusual linearly-propagating flip-flop hydrogen bonding scheme.     

Molecular structure of 3-(3-oxo-bicyclo[2.2.1]hept-5-en-2-yl)-oxirane-2-carboxylic acid methyl ester

The crystal and molecular structure of an epoxy ester is described. The structure has been solved by vector search methods and refined by least squares methods toR ₁=0.0372 [I>2(I)]. The structure consists of two independent molecules in the asymmetric unit. These molecules are chemically the same. Crystal data: C₁₁H₁₂O₄, triclinic, space group ,a=10.324(3),b=10.553(7),c=10.869(5)Å, =61.77(4), =88.64(4), =88.16(6)°,V=1042.7(9)ų,Z=4.     

Structure of fruticuline B: A new natural anthracene quinodimethide of abietanoid origin

The title compound is C₁₉H₁₈O₄·1/2 CH₃OH, triclinic,P¯1,a=9.891(2),b=13.273(4),c=13.860(4) Å,a=66.47(2),=86.91(2), and =85.59(2)°. The structure was solved by direct methods and refined by least-squares techniques to anR factor of 0.082 for 2282 observed reflections. The X-ray structure uniquely resolves the one remaining ambiguity, namely the assignment of the correct structure4. There are two crystallographically independent molecules (A and B) and one disordered methanol molecule. Both molecular skeletons show small distortions from planarity with inclinations of 1.7 and 4.0° between the outermost rings A/C in molecules A and B, respectively. Intramolecular hydrogen bonds of the form O(3A)-HO(2A) and O(3B)-HO(2B) are observed in molecules A and B, respectively. The molecules are linked by pairs of O(3A)-HO(2B) and O(3B)-HO(2A) hydrogen bonds. The dimerlike structures are stabilized by intermolecular C-HO interactions and van der Waals forces.