Table of Contents

Abstract: A reaction of YI₃, dibenzo-24-crown-8 and iodine in ethanol yielded, as a by-product, red single crystals of (I₂)@(db24c8). In the triclinic crystal, P-1, a = 485.0(1), b = 1203.7(3), c = 1280.4(2) pm, α = 64.56(2)°, β = 86.82(2)°, γ = 83.89(2)°, V = 671.1(2) × 10^6.pm³, Z = 1, R₁= 0.0301 for 1965 reflections with I₀ > 2σ(I₀), iodine molecules with an I–I distance of 268.39(7) pm, slightly longer than in the gas phase, are included in a matrix of db24c8 molecules.

Abstract: The reaction of bismuth triiodide with iodine and benzo-15-crown-5 in ethanol/dichloromethane yielded red single crystals of (b15c5)BiI₃(I₂) (monoclinic, P2₁/c (no. 14), a = 1376.9(1), b = 1172.7(1), c = 1700.2(2) pm, b = 115.197(6), V = 2484.1(4)·10⁶ pm³, Z = 4). Neutral pseudo-octahedral complexes (b15c5)BiI₃ are connected by secondary bonding interactions via iodine molecules to chains. Electronic structure calculations of the neutral complex (b15c5)BiI₃ reveal that the compound can indeed be described as b15c5 interacting with a molecular BiI₃ unit. However, bonding has to be mainly electrostatic as the interactions of the bismuth 6s lone pair with the 2p orbitals of the oxygen atoms of the crown ether are clearly antibonding.

Abstract: The crystal and molecular structure of the title compound, viz., (2Z)-2-[3-(4-methoxybenzoyl)-4,4-dimethyl-1,2,-oxazolidin-2-ylidene]-1-(4-methoxyphenyl)ethanone (4), is reported. Compound 4 crystallises from toluene/hexanes mixtures in the P2₁/c space group with eight molecules in the unit cell. The unit cell parameters are: a = 20.9410(11) Å, b = 8.7523(5) Å, c = 21.2291(9) Å; β = 93.529(3)° and V = 3883.5(3) ų. There are two structurally distinct molecules of 4 found in the solid-state which differ primarily in terms of the observed torsion angles and the overall intramolecular spacing between the aromatic groups. Bond lengths and angles of this tertiary amide are otherwise typical. This is the first crystallographically characterised example of this class of oxazoline precursors, which have previously found application in the syntheses of other heterocycles. Density functional theory (b3lyp 6-311++G** level of sophistication) has likewise been applied to estimate the gas-phase structure of the title compound.

Abstract: The crystal structures of C₅H₁₄N₂·HPO₃·H₂O (1) and C₅H₁₄N₂·HPO₃·2.23H₂O (2) are described and compared. Compound 1 contains homochiral (S)-2-methyl piperizinium cations, hydrogen phosphite ions and water molecules. The components are linked by N–H⋯O and O–H⋯O hydrogen bonds into a three-dimensional network. In compound 2, racemic (R,S)-2-methyl piperizinium cations combine with the same anions and water molecules to generate a far more complex, high symmetry “supramolecular” structure, which features distinctive R⁶₆(12) loops and helical C(2) chain hydrogen-bonding motifs involving the water molecules. Crystal data: 1 (C₅H₁₇N₂O₄P), M_r = 200.18, orthorhombic, P2₁2₁2₁ (No. 19), Z = 4, a = 8.564 (5) Å, b = 9.593 (6) Å, c = 11.607 (6) Å, V = 953.6 (9) ų, R(F) = 0.066, wR(F²) = 0.081. 2 (C₅H_19.47N₂O_5.24P), M_r = 222.49, trigonal, (No. 148), Z = 18, a = 31.075 (2) Å, c = 6.1875 (4) Å, V = 5174.5 (6) ų, R(F) = 0.044, wR(F²) = 0.107.

Abstract: The rare-earth metal(III) ortho-oxomolybdates with the formula Ln_0.667[MoO₄] (Ln = Ce, Pr, Nd, and Sm) and defect scheelite-type structure crystallize in the tetragonal space group I4₁/a (a = 533–525, c = 1183–1158 pm) with four formula units per unit cell. The Ln³⁺ cations at Wyckoff position 4b exhibit a coordination sphere of eight oxygen atoms in the shape of a trigonal dodecahedron. The same site symmetry (..) is observed for the tetrahedral oxomolybdate(VI) entities [MoO₄]^2–, since their central Mo⁶⁺ cation is situated at the 4a position. Due to this equal site multiplicity, the lanthanoid(III) cations have to be statistically under-occupied to maintain electroneutrality, thus a defect scheelite structure emerges. The partial structure of both the Ln³⁺ cations and the [MoO₄]^2– anions (if shrunk to their centers of gravity) can be best described as distorted diamond-like arrangements. Therefore, these two interpenetrating partial structures exhibit a similar setup as found in the zircon-type as well as in the NaTl-type structure.

Abstract: The base catalyzed intramolecular nucleophilic cyclization of 1-(2-bromobenzoyl)-3-(2-fluorophenyl)thiourea (1) in the presence of N,N-dimethyl formamide (DMF) afforded the 1-(3-fluorophenyl)-2-thioxo-2,3-dihydroquinazolin-4(1H)-one (2) by an intramolecular nucleophilic substitution S_NAr mechanism. The structure was supported by the spectroscopic data and unambiguously confirmed by the single crystal X-ray diffraction data. It crystallizes in the orthorhombic space group P na2₁ with unit cell dimensions a = 22.430(4), b = 8.1478(16), c = 13.522(3) Å, V = 2471.2(9) ų. There are two independent molecules per asymmetric unit that are linked to centrosymmetric AB-dimers via intermolecular N-H…S bonds.