N,N′,N″,N‴-Tetraisopropylpyrophosphoramide 1 is a pyrophosphoramide with documented butyrylcholinesterase inhibition, a property shared with the more widely studied octamethylphosphoramide (Schradan). Unlike Schradan, 1 is a solid at room temperature making it one of a few known pyrophosphoramide solids. The crystal structure of 1 was determined by single-crystal X-ray diffraction and compared with that of other previously described solid pyrophosphoramides. The pyrophosphoramide discussed in this study was synthesised by reacting iso-propyl amine with pyrophosphoryl tetrachloride under anhydrous conditions. A unique supramolecular motif was observed when compared with previously published pyrophosphoramide structures having two different intermolecular hydrogen bonding synthons. Furthermore, the potential of a wider variety of supramolecular structures in which similar pyrophosphoramides can crystallise was recognised. Proton (1H) and Phosphorus 31 (31P) Nuclear Magnetic Resonance (NMR) spectroscopy, infrared (IR) spectroscopy, mass spectrometry (MS) were carried out to complete the analysis of the compound.

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Most inorganic pigments generally consist of the colouring agents such as hematite (red) or glauconite (green) together with white pigments, including alumosilicates and calcium compounds. This usually leads to a wide colour range dependent on the exact percentage of the colouring agent in the solid mixture. Some inorganic pigments have been in use for thousands of years due to their easy availability and desirable attributes: ochres have been in use since prehistoric times to produce cave and rock paintings, and are still used to this day; terra verde (green earth) first made its appearance in decorations and frescos in the first century B.C. Whether these pigments are used in frescos, cave ornaments or paintings, shortcomings in their particular hue, transparency or fading character very often inspire research towards a better understanding of these physical characteristics. We present a study in which crystal engineering was applied in an attempt to tackle such problems. The solubility of Venetian red ochre and its solid state behaviour at higher temperatures were investigated and compared with similar studies on terra verde. Hot stage microscopy showed that, although the pigment retained its red colour upon heating, some crystallites lost transparency, indicating a phase change. The actual colouring agents hematite and goethite in Venetian red ochre are insoluble in most solvents and solvent mixtures. However, the solvent was found to have a significant effect on the undissolved pigment and other components. The pigment examined in this study was a mixture of microcrystalline powders with smaller quantities of larger crystallites thought to be gypsum. Multi-elemental analysis by X-ray fluorescence spectroscopy showed the most abundant elements to be sulphur, calcium, iron, magnesium, silicon and aluminium. Fourier-Transform Infrared (FTIR) spectroscopy indicated the presence of metal oxides, metal carbonates and alumosilicates. Powder X-ray diffraction experiments helped to identify and quantify the proportions of hematite and goethite in four different pigments.

The title compound, di-μ-nitrato-κ3 O,O′:O;O:O,O′-bis(μ-octaethyl pyrophosphoramide-κ2 O:O′)bis[aquabis(nitrato-κ2 O,O′)calcium(II)], [Ca2(NO3)4(C16H40N4O3P2)2(H2O)2] was obtained as a side product during the work up of the synthesis of octaethyl pyrophosphoramide and represents the first structurally characterized complex of this ligand. The compound crystallizes in the monoclinic space group P21/n and the asymmetric unit contains one pyrophosphoramide molecule and one Ca2+ ion coordinated to two nitrate ions and one water molecule. The complex exists as a dimer with a centre of inversion located between two eight-coordinate calcium(II) centres, which are bridged by two nitrate ions and two octaethyl pyrophosphoramide ligands. Each Ca2+ cation is also coordinated to a further nitrate anion, acting as a bidentate ligand, and a water molecule. The complexes stack parallel to the a axis and are held in place by a network of intermolecular O—H...O hydrogen bonds also running parallel to a.