Inclusion complexes of the natural product gossypol. Crystal structures of gossypol complexes with benzene and chloroform as guests

The crystal structures of the lattice inclusion complexes of gossypol with benzene and chloroform have been determined by X-ray structure analysis. The crystals of (C₃₀H₃₀O₈)₂ · C₆H₆ (GPBNZ) are triclinic, space groupPI,a = 11.241(3),b = 14.986(4),c = 17.380(4) Å, = 98.89(2), = 99.86(2), = 98.91(2)°,V = 2800(2) ų,Z = 2,D _x = 1.32 g cm^–3, (CuK ) = 7.35 cm^–1. The structure has been refined to a finalR value of 0.050 for 6146 observed reflections. The crystals of C₃₀H₃₀O₈·CHCl₃ (GPCLF) are monoclinic, space groupC2/c,a = 28.464(4),b = 8.948(1),c = 26.480(4) Å, = 108.93(2)°,V = 6380(2) ų,Z = 8,D _x = 1.33 g cm^–3, (CuK) = 30.42 cm^–1. The structure has been refined to a finalR value of 0.100 for 1980 observed reflections.GPCLF forms an intercalate-type structure and GPBNZ a clathrate-type structure. There are, however, some similarities in the packing mode of the host molecules in these two structures. On a basis of comparison of the crystal packing of GPCLF and GPBNZ one can postulate that in the desorption process of the intercalate-type GPCLF complex an intermediate clathrate structure of the GPBNZ-type should be formed.     

Heterometallic two-dimensional polymer containing cyanide-bridged praseodymium(III) and transition metals

A heterometallic cyanide-bridged 3d–4f heterometallic coordination polymer [Pr(DMF)₄(H₂O)_3.5Fe(CN)₆]·H₂O (DMF = N,N-dimethylformamide) has been synthesized and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic space group P2(1)/n with cell parameters: a = 17.669(5) ų, b = 8.927(3) ų, c = 19.967(6) ų, = 95.807(5)°, V = 3133.2(16) ų, Z = 4. Multiple hydrogen bonds extend the dinuclear units into a novel 2-D topological architecture of an irregular triangular lattice of iron and praseodymium ions. The magnetic properties have been investigated.     

Synthesis and characterization of two-dimensional fluorinated metal phosphates incorporating 2,2′-bipyridine ligands: M2F2(2,2′-bpy)(HPO4)2(H2O) (M=Fe, Ga)

Two fluorinated metal phosphates, M₂F₂(2,2′-bpy)(HPO₄)₂(H₂O) (M=Fe, Ga), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility. The two compounds are isostructural and crystallize in the triclinic space group , a=7.6595(8)Å, b=10.101(1)Å, c=11.260(1)Å, α=107.555(2)°, β=105.174(2)°, γ=98.975(2)°, V=775.1(2)ų and Z=2 for the Fe compound, and a=7.5816(6)Å, b=9.9943(7)Å, c=11.1742(8)Å, α=107.333(1)°, β=105.014(1)°, γ=99.261(1)° and V=754.2(2)ų for the Ga compound. They are the first fluorinated metal phosphates which incorporate 2,2′-bipyridine ligands. The structure consists of edge-sharing octahedral dimers with the composition Fe₂F₄(H₂O)₂O₄ and discrete FeN₂O₄ octahedra, which are linked into two-dimensional sheets through corner-sharing phosphate tetrahedra. The 2,2′-bpy ligands bind in a bidentate fashion to the metal atoms and project into interlamellar region. The layers are extended into a three-dimensional supramolecular array via π-π stacking interactions of the 2,2′-bpy ligands. Magnetic susceptibility of the iron compound confirms the presence of Fe^III.     

Synthesis and Crystal Structure of a New Copper–PMIDA Compound (H4PMIDA=H2O3PCH2N(CH2CO2H)2)

A new Cu(II)PMIDA compound [Cu(H₂PMIDA)(phen)] 3H₂O (1) (H₄PMIDA = H₂O₃PCH₂N (CH₂CO₂H)₂,phen = 1,10-phenanthroline) has been successfully synthesized and structurally characterized. In complex 1, Cu (II) is six coordinated by chelation in a tetradentate fashion by a PMIDA ligand and by two N atoms of a phen ligand. Every phen–Cu(II)–PMIDA group connects with each other via a hydrogen bond and the edge-to-face -stacking interaction. Complex 1 crystallized in triclinic P-1 with cell dimensions of a = 7.5817(6) Å, b = 10.6980(8) Å, c = 13.1852(10) Å, =82.350(2)°, = 84.151(2)°, =78.4250(2), V= 1035.25(14) ų, Z = 2, Dc = 1.677 Mg/m³.     

Synthesis,crystal structure and reaction of differentially ring-substituted titanocene dichlorides

Summary A new class of differentially ring-substituted titanocene dichlorides of the type CpCpTiCl₂ has been prepared by reacting CpM (M=Li, K; Cp=RC₅H₄) with CpTiCl₃ (Cp=MeOCH₂CH₂C₅H₄). The crystal structure of Cp(PhCEt₂C₅H₄)TiCl₂, the first example, has been determined by x-ray diffraction and refined to a final R factor of 0.0532 for 2304 reflections. The crystal belongs to the monoclinic space group C _2h ⁵ –P2₁/c with unit cell parameters:a 10.205(6),b 13.003(5),c 17.591(9) Å, 101.91(4)°, V=2284 ų, Z=4 and Dc=1.32 g/cm^–3. Replacement of one neomenthyl in bis(neomenthyl-cyclopentadienyl)titanium dichloride by one MeOCH₂CH₂ — raises the e.e. value from 5.8% to 11.2% in the catalytic asymmetric hydrogenation of 2-phenyl-1-butene.     

Structural study of the 1:1 clathrate of an asymmetric calix[4]arene and acetone

The crystal and molecular structure of the 1:1 clathrate of the asymmetric calix[4]arene,1, and acetone has been determined by X-ray analysis. The crystal data are: tetragonal, space groupP4/n,a=b=12.574(6),c=12.572(6) Å,V=1988(2) ų,Z=2,D _x =1.111 g cm^–3,D _m =1.108 g cm^–3. Least-squares refinement based on 1131 observed reflections withF ₀>3(F ₀) and anisotropic temperature factors led toR=0.096. In spite of the molecular asymmetric calixarene1 the crystal structure has high symmetry, because a part of the host and guest molecules are in disordered states.     

Cation and anion coordination chemistry of palladium(II) with polyazacycloalkanes. Thermodynamic and structural studies

The interaction of PdCl ₄ ^2– with the macrocyclic ligands of the series [3k]aneN _k has been studied both in solution and in the solid state. [18]aneN₆ and [21]aneN₇ form both mono- and binuclear Pd²⁺ complexes, whose stability constants have been determined in 0.5 mol dm^–3 NaCl at 298.15 K. [21]aneN₇ also forms, in solution, a trinuclear species in which an amino group deprotonates to bridge two Pd²⁺ ions, as observed in the solid state. The crystal structure of the complexes [Pd₂([18]aneN₆)Cl₂][ClO₄]₂ and [Pd₃([21]aneN₇)Cl₃][ClO₄]₂ · H₂O have been solved by single crystal X-ray analysis. C₁₂H₃₀N₆Cl₄O₈Pd₂: monoclinic, space group C2/m,a = 10.876(2),b = 18.117(2),c = 7.043(2) Å, = 113.78(2)°,V = 1270(12) ų,Z = 2,D _calc = 1.92 g cm^-3, = 16.94 cm^–1.R = 0.063,R _w = 0.059. C₁₄H₃₆N₇CI₅O₉Pd₃: orthorhombic, space groupPcab,a = 13.125(7),b = 13.213(3),c = 33.570(5) Å,V = 5822(3) ų,Z = 8,D _calc = 2.15 g cm^–3, = 21.20 cm^–1.R = 0.074,R _w = 0.061. In very acidic solutions the polyammonium cations (H _k [3k]aneN _k ) ^k+ interact with PdCl ₄ ^2– forming second sphere coordinated species. These reactions have been followed by a microcalorimetric technique in 2 mol dm^–3 HCl solutions. The slowness of the reactions of (H₁₀[30]aneN₁₀)¹⁰⁺ with PdCl ₄ ^2– has been interpreted in terms of inclusion of the anion into the receptor's cavity as shown by the crystal structure of [(PdCl₄)(H₁₀[30]aneN₁₀)][PdCl₄]₂Cl₄: triclinic, space group PT,a = 7.760(3),b = 11.448(4),c = 13.399(11) Å, = 96.31(8)°, = 104.50(6)°, = 92.30(3)°,Z = 1.R = 0.046 andR _w = 0.039.This paper is dedicated to the memory of the late Dr C. J. Pedersen.     

Crystal Structure of Cesium-Sodium Molybdate Dihydrate

Structure of CsNaMoO₄ · 2H₂O crystals formed in Cs₂MoO₄–Na₂MoO₄–H₂O system is determined by X-ray diffraction study. The unit cell parameters a = 6.379(2) Å, b = 8.631(2) Å, c = 13.670(2) Å, V = 752.6(3) ų, Z = 4, M = 351.87, (calcd) = 3.105 g/cm³, space group P2₁2₁2₁. The isle crystal structure is built of MoO₄ ^2-, Cs⁺, and Na⁺ ions. The Mo–O bond lengths lie within 1.756(2)–1.769(3) Å range. The OMoO bond angle is 109.45° on average. Three oxygen atoms of MoO₄ ^2- anion are involved in hydrogen bonds with water molecules., while the fourth O atom participates in the formation of Na polyhedra only. The octahedral environment of Cs⁺ ions is formed by oxygen atoms of MoO₄ ^2- anions, without participation of water molecules. The structure contains two crystallographically independent water molecules, whose tetrahedral coordination consists of two Na⁺ ions and two MoO₄ ^2- anions.     

Synthesis,Crystal and Molecular Structures of [Co(MH)2(Thio)2][BF4] · H2O and [Co(DH)2(NH3)2][BF4]

Crystal structures of [Co(MH)₂(Thio)₂][BF₄] · H₂O (I) and [Co(DH)₂(NH₃)₂][BF₄] (II), where MH^– is H₃C–C(NOH)–C(NO^–)–H and DH^– is H₃C–C(NOH)–C(NO^–)–CH₃, were determined by X-ray diffraction. The crystals are monoclinic, space group C2/c, unit cell parameters (for I and II, respectively): a = 22.018(2) Å, b = 7.943(1) Å, c = 11.681(1) Å, = 92.68(1)° and a = 21.436(2) Å, b = 6.400(2) Å, c = 12.389(2) Å, = 113.13(1)°. In both cases, the Co(III) coordination polyhedron is a centrosymmetrical trans-octahedron, N₄S₂ for I and N₆ for II. In the crystals of I and II, the complex cations and the outer-sphere [BF₄]^– anions (and the crystal water molecules in I) form elaborate hydrogen bonding system.     

Crystalline complexes of N,N'-ditritylurea (DTU) and N-tritylurea (NTU) hosts with molecular guests

This paper reports crystalline complexes of the new hosts N,N'-ditritylurea (DTU) and N-tritylurea (NTU) with various uncharged molecular guests. The crystal structures of the following complexes were elucidated by single crystal X-ray diffraction analysis at 115^oK: (I) 1:1 DTU-propanamide — space group C2/c, a=15.839Å, b=9.088Å, c=24.584Å, =111.05^o, Z=4; (II) 1:1 DTU-ethyl N-acetylglycinate — space group P1, a=9.010Å, b=10.800Å, c=19.810 Å, =105.29^o =94.33^o, =93.03^o, Z=2; (III) 2:1 NTU-N, N-dimethylformamide — space group Cc, a=29.614Å, b=8.906Å, c=16.127Å, =121.04^o, Z=4. The three crystal structures are stabilized mainly by a cooperative effect of hydrogen bonding between amide fragments displaced along the shortest axis of each crystal. This interaction occurs between host and guest in complexes I and II, and between host and host in complex III. The latter also represents a cage-type clathrate in which the guest molecules are accommodated in voids between the hydrophobic fragments of four neighboring NTU hosts. On the other hand, complexes of DTU are characterized by a more specific interaction between the two components, each guest molecule being inserted between two adjacent hosts (related by translation) and strongly bound to them via hydrogen bridges. These results illustrate a useful concept in the design of molecular species which can be potential hosts upon crystallization with neutral molecular guests. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82022 (7 pages).     

Two clathrates of bis(isothiocyanato)tetrakis(4-methylpyridine)magnesium(II) as a host with 4-methylpyridine as a guest

Two clathrate modifications of the title host with 4-methylpyridine (4-CH₃C₅H₄N) as a guest have been determined at –50°C. [Mg(4-CH₃C₅H₄N)₄(NCS)₂] · 2/3(4-CH₃C₅H₄N) · 1/3H₂O is trigonal, space group , witha=27.630(7),c=11.219(3) ÅV=7417(4) ų,Z=9,D _calc=1.171 g cm^–3,(CuK )=18.506 cm^–1, finalR=0.064. [Mg(4-CH₃C₅H₄N)₄(NCS)₂] · (4-CH₃C₅H₄N) is tetragonal, space group I4_l/a, witha=16.944(7),c=23.552(9)Å,V=6762(5) Å,Z=8,D _calc=1.191 g cm^–3, (CuK )=18.200 cm^–1, finalR=0.071.The structures consist of molecular packings of the same host complex units and the guest species. The Mg(II) cation is octahedrally coordinated to theN-atoms of four 4-methylpyridine and twotrans-coordinated isothiocyanato ligands in the host molecule. The conformations of the molecule are considerably different both in symmetry and in geometry in these two structures. The guest 4-methylpyridine molecules are disordered into channels which have different topology in these two clathrates resulting in different thermal stability.     

Inclusion Compounds of Thiourea and Paralkylated Ammonium Salts. Part VII. Hydrogen-Bonded Host Lattices Constructed from Thiourea and Anionic Species Derived from Benzoic Acid

New inclusion complexes (n-C₃H₇)₄N⁺C₆H₅CO ₂ ^– · 3(NH₂)₂CS (1), (n-C₄H₉)₄N⁺[(C₆H₅CO₂)₂H]^–·6(NH₂)₂CS (2) and (C₂H₅)₄N⁺C₆H₅CO ₂ ^– ·(NH₂)₂CS (3) have been prepared and characterized by X-ray crystallography. Crystal data, MoK radiation: 1, space group P2₁2₁2₁, Z = 4, a = 8.544(3), b = 14.588(4), c = 24.448(4) Å, and R1 = 0.062 for 1536 observed data; 2, space group Pbcn, Z = 4, a = 24.938(3), b = 8.911(1), c = 23.733(9) Å, and R1 = 0.055 for 2132 observed data; 3, space group P2₁2₁2₁, Z = 4, a = 9.996(2), b = 10.122(4), c = 18.350(2) Å, and R1 = 0.049 for 1180 observed data. In the crystal structure of 1, the (n-C₃H₇)₄N⁺ cations are stacked in a single column and accommodated within each channel built up by wide thiourea ribbons and benzoate ions via N—H···O hydrogen bonds. In the crystal structure of 2, the tetrabutylammonium cations are arranged in a zigzag column within each channel built of parallel corrugated thiourea layers that are inter-linked by dimeric [(C₆H₅CO₂)₂H]^– groups through N—H·O hydrogen bonds. In compound 3 the (C₂H₅)₄N⁺ cations are accommodated in pseudo-channels generated from infinitely extended thiourea-benzoate composite ribbons.     

Coordination chemistry of alkali and alkaline earth cations. Barium-crown encapsulation studies: The synthesis and crystal structure of barium(picrate)2(benzo-15-crown-5) monohydrate

The interaction of barium with benzo-15-crown-5 (B15C5) has been followed under the competitive effect of various chelating organic anions (L), nitrophenolates and nitrobenzoates, in ethanol and ethanol-water (9:1). The rather heavily hydrated BaL₂ salts yield novel 1:1 stoichiometric products in monohydrated or anhydrous states. Use of excess crown does not under any condition lead to the formation of 1:2 charge separated complexes, expected in view of the cavity and the cation sizes. The 1:1 Ba–B15C5 interaction is counteracted by L in accordance with its nucleophilicity, i.e., the pK _a value of its parent acid, HL. The complex Ba(picrate)₂(B15C5)·H₂O (BaC₂₆H₂₆N₆O₂₀, FW=879.0), is monoclinic,P2₁/c,a=11.43(1),b=16.31(3),c=17.38(2) Å, =92.265(3)°,Z=4,D _c=1.77 g/cm³,D ₀=1.73 g/cm³, MoK, =0.71069 Å, 2 (4.0–50°), =13.5 cm^–1,F(000)=1752,T=–32°C. FinalR for the 5926 reflections was 0.049. The structure reveals barium to be 10-coordinated through all the five crown oxygens (Ba–O, 2.800 to 3.002 Å), the two bidentate picrates (Ba–O, 2.642 and 2.666 Å; Ba–ONO, 2.825 and 2.994 Å), and the water molecule (2.711 Å) so that the cation constitutes a pseudo-sandwich of the crown on one side and the anionic species on the other. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82007 (50 pages). To obtain copies, see page ii of this issue.     

Molecular Structure of an Isocytosine Analog: Combined X-ray Structural and Computational Study of 2-Diethylamino-6-methyl-5-n-propyl-4(3H)-pyrimidinone

The structure of 2-diethylamino-6-methyl-5-n-propyl-4(3H)-pyrimidinone has been studied by X-ray crystallography and quantum-chemical calculations. X-ray analysis established that 2-diethylamino-6-methyl-5-n-propyl-4(3H)-pyrimidinone exists exclusively as the lactam tautomer protonated at the N3 ring nitrogen in the solid state. Crystals of 2-diethylamino-6-methyl-5-n-propyl-4(3H)-pyrimidinone are monoclinic (space group P2₁/n); the unit-cell dimensions are: a = 11.0460(8) Å, b = 5.0064(4) Å, c = 22.8358(17) Å, = = 90°, = 90.521(1)°. In the crystal, molecules of 2-diethylamino-6-methyl-5-n-propyl-4(3H)-pyrimidinone are assembled in planar centrosymmetric dimers by strong resonance-assisted N—H···O intermolecular hydrogen bonds from the NH group of one molecule to the C=O of the adjacent molecule (N—H···O distance 2.804 Å). Bond distances and angles are generally similar to those reported for the corresponding tautomer of isocytosine and derivatives. Quantum-chemical calculations on 2-diethylamino-6-methyl-5-n-propyl-4(3H)-pyrimidinone are also reported in order to estimate the relative energies of the possible tautomeric forms; ab initio and DFT results predict the coexistence of the N3 and AH tautomers in the gas phase. There is excellent correspondence between the crystal and the HF/6-311G** or B3LYP/6-31G* calculated structures of the N3 lactam form; the largest deviations between the experimental and computed structures are mostly the effects of strong intermolecular H bonds in the crystal.     

The Crystal Structures of Rubidium and 4-Amino-1,2,4-Triazolium Tetrafluoroantimonates(III)

The crystal structures of complex antimony(III) fluorides RbSbF₄ (I) and (C₂N₄H₅)SbF₄ (II) were determined. The crystals of I and II are monoclinic; for I: a = 4.628(1) Å, b = 6.167(1) Å, c = 7.922(1) Å, = 100.582(3)°, V = 222.24(7) ų, Z = 2, (calcd.) = 4.23 g/cm³, (exp.) = 4.25 g/cm³, F(000) = 248, space group P2₁/m, R = 0.0395; for II: a = 4.678(1) Å, b = 7.339(4) Å, c = 10.185(1) Å, = 90.88(2)°, V = 349.6(2) ų, Z = 2, (calcd.) = 2.69 g/cm³, (exp.) = 2.70 g/cm³, F(000) = 264, space group P2₁. The structure of I is formed by Rb⁺ cations and [SbF₄] ^n– _n anionic chains composed of SbF₅E octahedra with two bridging fluorine atoms. The structure of IIis formed by (C₂N₄H₅)⁺ cations and isolated [SbF₄]^– anions in which the antimony polyhedra are SbF₄E trigonal bipyramids. The relationship between the crystal structures and electrophysical and biological properties of single-charged cation tetrafluoroantimonates(III) was studied.     

Single Crystal Growth,Crystal Structure and Thermal Behaviour of Mercury(II) Pyrophosphate Dihydrate

Summary. Colourless single crystals of Hg₂P₂O₇(H₂O)₂ up to 0.4 mm in length were grown by a diffusion technique starting from aqueous solutions of Na₄P₂O₇ and Hg(NO₃)₂. The crystal structure is isotypic with that of Ca₂P₂O₇(H₂O)₂ and was determined from a four-circle diffractometer data set (space group , Z=2, a=6.9374(7), b=7.4396(8), c=7.9863(7)Å, =84.685(8), =75.158(8), =72.818(8)°, 2413 structure factors, 132 parameters, R[F ²>2(F ²)]=0.0181, wR(F ² all)= 0.0384). Hg₂P₂O₇(H₂O)₂ is composed of approximately eclipsed P₂O₇ ^4– anions and distorted [HgO₆] octahedra and [HgO₇] pentagonal bipyramids as the main building units. The structure is stabilized by inter-water hydrogen bonding and by hydrogen bonding between terminal pyrophosphate oxygen atoms and the water molecules. The P–O distances to the terminal oxygen atoms range from 1.501(4) to 1.536(3)Å, with an average of 1.522Å; the mean distance of 1.615Å to the bridging O atom is considerably longer with an (O–P–O) bridging angle of 123.44(19)°. Both Hg atoms have two short Hg–O bonds around 2.17Å and additional bonds ranging from 2.381(3) to 2.708(4)Å. Upon heating above 160°C, both crystal water molecules are released simultaneously and anhydrous Hg₂P₂O₇ is formed which is stable up to ca. 660°C. Above this temperature the material decomposes completely.     

Analysis of atomic displacement parameters and molecular motion in crystals. Part 2. X-ray crystal structure of K2Ru(SO4)2 * 6H2O at 160 K and 295 K

Atomic displacement parameters determined from a single-crystal X-ray-diffraction study on K₂Ru(SO₄)₂ * 6H₂O are analyzed in the molecular mean field approximation. The motion of SO₂ ^2– can be described with a rigid-body model, whereas for [Ru(H₂O)₆]²⁺ internal stretching motion and coupling between stretching motion and overall translation are found to be necessary for explaining the observed atomic displacement parameters. Frequencies and force constants of internal motion are not significantly affected by such couplings. K₂Ru(SO₄)₂ * 6H₂O crystallizes in the monoclinic space groupP2₁/c (No. 14), witha = 6.1211(7)Å,b = 12.226(2) Å,c = 8.916(2)Å, = 105.11(1)°,Z = 2 at 160 K anda = 6.1402(7)Å,b = 12.274(2)Å,c = 8.957(1)Å, = 105.25(1)°,Z = 2 at 295 K. The structure was refined to a finalR(F) of 0.017 at 160 K and of 0.019 at 295 K for 1438 and 1299 observed reflections withF ₀ > 6(F₀) and sin / > 0.617 Å^1–.     

Polymorphism of Inclusion Complexes and Unsolvated Hosts. IV. Dimorphism of the Acetone Host–Guest Complex of Dianilinegossypol. Structures of the α- and β-Phase Complexes

Crystal structures of the - and -phase inclusion complexes of dianilinegossypol with acetone obtained at 20° and 30 °C, respectively, have been determined by X-ray structure analysis. Crystal data of the -phase complex are: C₄₂H₄₀O₆N₂2C₃H₆O, orthorhombic, space group Pccn, a = 29.501(9), b = 10.866(2), c = 13.756(3) Å, V = 4409(1) ų, Z = 4, D _x = 1.18 g cm^-3. The structure has been refined to a final R value of 0.117 for 1401 observed reflections. The host–guest ratio for the -phase complex is the same (1 : 2) and the crystals are monoclinic, space group C2/c, a = 28.352(6), b = 11.836(2), c = 13.196(1) Å, = 93.05(1)°, V = 4422(2) Å3, Z = 4, D _x =1.18 g cm^-3. The structure has been refined to a final R value of 0.077 for 1414 observed reflections.In both phases molecules of dianilinegossypol form hydrogen-bondedribbons by O(4)–-HO(3) H-bonds. Phases are determined by the same structural motif. In the -phase complex the cages are in the form of prisms but in the -phase clathrate they undergo a modification by shrinking in two directions and widening in one. Molecules of acetone are hydrogen bonded to the host molecules via aO(1)–-HO(G) bond and are accommodated in cavities for both complexes, i.e. both phases are cryptate-type inclusion complexes.Supplementary data relevant to this publicationhave been deposited with the British Library,No. SUP 82227 (24 pages).     

Crystal Structure of Thallium Tridecafluorotetraantimonate(III) TlSb4F13

The crystal structure of thallium fluoroantimonate(III) complex TlSb₄F₁₃ (I), which is isostructural to KSb₄F₁₃ (II), is determined. Crystals I are tetragonal: a = 9.634(2) Å, c = 6.590(2) Å, V = 611.7(2) ų, Z = 2, (calcd) = 5.094 g/cm³, F(000) = 804.0, space group I4¯. The structure consists of tetrameric [Sb₄F₁₃]^– anions formed by SbF₃ groups connected by the fluoride ion and the l⁺ cations.     

Nickel complexes of 1-methylimidazoline-2(3H)-thione: crystal structures of trans-dichlorotetrakis(1-methylimidazoline-2(3H)-thione)nickel(II) and tetrakis[1-methylimidazoline-2(3H)-thione]nickel(II) tetrafluoroborate

Summary Crystal structures have been determined for two nickel complexes of the monodentate S-donating ligand 1-methyl imidazoline-2(3H)-thione (mimtH). The parainagnetic trans-octahedral complex, [Ni(mimtH)₄Cl₂], crystallises in an orthorhombic unit cell (a=12.459(1),b=13.078(1),c=15.406(1)Å, V=2510.24ų,Z=4, space group Pbca). Final conventional R from 1848 observed data [F>4(F)] is 0.0273. The Ni–Cl distance is. 2.537(1) Å and the mean Ni–S distance is 2.479 Å.The diamagnetic complex, [Ni(mimtH)₄](BF₄)₂, contains a distorted square-planar cation which is H-bonded. to [BF₄]^– anions. The complex crystallises in an orthorhombic unit cell [a=9.810(1),b=14.585(1),c=20.120(2)Å, V=2878.8ų,Z=4, space group Pbcn]. Final conventional R from 1756 observed data [F>4(F)] is 0.0629. The average Ni–S distance is 2.216Å.