Poly[[tri-μ-cyanido-cyanido(1,4,10,13-tetra­oxa-7,16-diaza­cyclo­octa­deca­ne)barium(II)platinum(II)] hemihydrate]

The title compound, {[BaPt(CN)4(C12H26N2O4)]·0.5H2O}n, is a two-dimensional coordination polymer in which the sheets are oriented approximately parallel to the (01) set of crystal planes. In the crystal structure, disordered water mol­ecules (half occupancy) connect the sheets into a three-dimensional network via inter­molecular O—H⋯O hydrogen bonds. An N—H⋯N inter­action is also present. The shortest Pt⋯Pt contacts are 7.5969 (4) Å by an inversion relationship and 7.6781 (4) Å by translation along the a axis

Monomers, dimers, and trimers of [Au(CN)2]− in a Ba(diaza-18-crown-6)2+ coordination polymer

The structure of the title compound, poly[triaquatetra-μ-cyanido-tetracyanidobis­(1,4,10,13-tetra­oxa-7,16-diaza­cyclo­octa­deca­ne)di­barium(II)tetra­gold(I)], [Au4Ba2(CN)8(C12H26N2O4)2(H2O)3]n, displays O—H⋯N hydrogen bonding between water molecules and cyano ligands and an unusual pattern of aurophilic inter­actions that yields a monomer, dimer, and trimer of [Au(CN)2]− within the same crystal structure. In two of the five Au positions, the atom resides on a center of inversion. The overall arrangement is that of a coordination polymer assisted by aurophilic and hydrogen-bonded inter­actions

Synthesis, structure, magnetism, and high temperature thermoelectric properties of Ge doped Yb_(14)MnSb_(11)

The Zintl phase Yb_(14)MnSb_(11) was successfully doped with Ge utilizing a tin flux technique. The stoichiometry was determined by microprobe analysis to be Yb_(13.99(14))Mn_(1.05(5))Sb_(10.89(16))Ge_(0.06(3)). This was the maximum amount of Ge that could be incorporated into the structure via flux synthesis regardless of the amount included in the reaction. Single crystal X-ray diffraction could not unambiguously determine the site occupancy for Ge. Bond lengths varied by about 1% or less, compared with the undoped structure, suggesting that the small amount of Ge dopant does not significantly perturb the structure. Differential scanning calorimetry/thermogravimetry (DSC/TG) show that the doped compound's melting point is greater than 1200 K. The electrical resistivity and magnetism are virtually unchanged from the parent material, suggesting that Yb is present as Yb^(2+) and that the Ge dopant has little effect on the magnetic structure. At 900 K the resistivity and Seebeck coefficient decrease resulting in a zT of 0.45 at 1100 K, significantly lower than the undoped compound

Pressure-induced inclusion of neon in the crystal structure of a molecular Cu2(pacman) complex at 4.67 GPa

Crystals of a Cu complex of the macrocyclic Schiff-base calixpyrrole or 'Pacman' ligand, Cu2(L), do not contain any solvent-accessible void space at ambient pressure, but adsorb neon at 4.67 GPa, forming Cu2(L)·3.5Ne

The Effect of Pressure on Halogen Bonding in 4-Iodobenzonitrile

The crystal structure of 4-iodobenzonitrile, which is monoclinic (space group I2/a) under ambient conditions, contains chains of molecules linked through C≡N···I halogen-bonds. The chains interact through CH···I, CH···N and π-stacking contacts. The crystal structure remains in the same phase up to 5.0 GPa, the b axis compressing by 3.3%, and the a and c axes by 12.3 and 10.9 %. Since the chains are exactly aligned with the crystallographic b axis these data characterise the compressibility of the I···N interaction relative to the inter-chain interactions, and indicate that the halogen bond is the most robust intermolecular interaction in the structure, shortening from 3.168(4) at ambient pressure to 2.840(1) Å at 5.0 GPa. The π∙∙∙π contacts are most sensitive to pressure, and in one case the perpendicular stacking distance shortens from 3.6420(8) to 3.139(4) Å. Packing energy calculations (PIXEL) indicate that the π∙∙∙π interactions have been distorted into a destabilising region of their potentials at 5.0 GPa. The structure undergoes a transition to a triclinic ( P 1 ¯ ) phase at 5.5 GPa. Over the course of the transition, the initially colourless and transparent crystal darkens on account of formation of microscopic cracks. The resistance drops by 10% and the optical transmittance drops by almost two orders of magnitude. The I···N bond increases in length to 2.928(10) Å and become less linear [<C−I∙∙∙N = 166.2(5)°]; the energy stabilises by 2.5 kJ mol−1 and the mixed C-I/I..N stretching frequency observed by Raman spectroscopy increases from 249 to 252 cm−1. The driving force of the transition is shown to be relief of strain built-up in the π∙∙∙π interactions rather than minimisation of the molar volume. The triclinic phase persists up to 8.1 GPa

High-pressure polymorphism in pyridine

Single crystals of the high-pressure phases II and III of pyridine have been obtained by in situ crystallization at 1.09 and 1.69 GPa, revealing the crystal structure of phase III for the first time using X-ray diffraction. Phase II crystallizes in P212121 with Z' = 1 and phase III in P41212 with Z' = ½. Neutron powder diffraction experiments using pyridine-d5 establish approximate equations of state of both phases. The space group and unit-cell dimensions of phase III are similar to the structures of other simple compounds with C 2v molecular symmetry, and the phase becomes stable at high pressure because it is topologically close-packed, resulting in a lower molar volume than the topologically body-centred cubic phase II. Phases II and III have been observed previously by Raman spectroscopy, but have been mis-identified or inconsistently named. Raman spectra collected on the same samples as used in the X-ray experiments establish the vibrational characteristics of both phases unambiguously. The pyridine molecules interact in both phases through CH⋯π and CH⋯N interactions. The nature of individual contacts is preserved through the phase transition between phases III and II, which occurs on decompression. A combination of rigid-body symmetry mode analysis and density functional theory calculations enables the soft vibrational lattice mode which governs the transformation to be identified