A new software system called PHENIX (Python-based Hierarchical ENvironment for Integrated Xtallography) is being developed for the automation of crystallographic structure solution. This will provide the necessary algorithms to proceed from reduced intensity data to a refined molecular model, and facilitate structure solution for both the novice and expert crystallographer. Here we review the features of PHENIX and briefly describe the recent advances in infrastructure and algorithms.

A series of diorganotin complexes of dithiocarbamates [Sn(C4H9)2(S2CN(RR′)2)2] (R, R′ = ethyl (1); R = methyl, R′ = butyl (2); R, R′ = butyl (3); R = methyl, R′ = hexyl (4); and [Sn(C6H5)2(S2CN(RR′)2)2] (R, R′ = ethyl (5); R = methyl, R′ = butyl (6); R, R′ = butyl (7); R = methyl, R′ = hexyl (8) were synthesized. Single-crystal X-ray structures of 2, 3, and 8 were determined. Thermogravimetric analysis (TGA) showed single-step decomposition for the complexes 1, 3, and 5–8, and double-step decomposition for the complexes 2 and 4 between 195 °C and 325 °C. Complexes 1–4 were used as single-source precursors for the deposition of SnS thin films by aerosol-assisted chemical vapor deposition (AACVD) at temperatures from 400 °C to 530 °C. Orthorhombic SnS thin films were deposited from all four complexes at all deposition temperatures. The films were characterized by UV–vis spectroscopy, powder X-ray diffraction (p-XRD), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and also electrical resistivity measurements.

Three new Cu-Ln cage complexes bridged by phosphonates and acetates are reported; one--a Cu(24)Dy(8) cage--is a new single molecule magnet (SMM).

Organooxotin cages, clusters, and coordination polymers containing [Sn 2(mu-O)], [Sn 2(mu-OH)], [Sn 2(mu-O) 2], [Sn 2(mu-OH) 2], and [Sn 3(mu 3-O)(mu-OR) 3] building blocks have been assembled by the reactions of organotin precursors with phosphonic, phosphinic, carboxylic, or sulfonic acids. Various synthetic methodologies including Sn-C bond cleavage reactions and solventless procedures have been utilized to generate several nanodimensional organostannoxane assemblies. The synthesis, structure, and structural interrelationship of these diverse organostannoxane compounds are discussed. The synthetic knowledge gained to prepare specific organostannoxane structural forms in high yields has been utilized for the construction of dendrimer-like molecules. These contain a central stannoxane core and a functional periphery. The functional periphery can be readily modulated to assemble photoactive, electroactive, or multisite coordinating molecules. The synthesis, structure, and potential uses of these compounds are discussed.

Organostannoxane-based multiredox assemblies containing ferrocenyl peripheries have been readily synthesized by a simple one-pot synthesis, either by a solution method or by room-temperature solid-state synthesis, in nearly quantitative yields. The number of ferrocenyl units in the multiredox assembly is readily varied by stoichiometric control as well as by the choice of the organotin precursors. Thus, the reaction of the diorganotin oxides, R2SnO (R = Ph, nBu and tBu) with ferrocene carboxylic acid affords tetra-, di-, and mononuclear derivatives [{Ph2Sn[OC(O)Fc]2}2] (1), [{[nBu2SnOC(O)Fc]2O}2] (2), [nBu2Sn{OC(O)Fc}2] (3), [{tBu2Sn(OH)OC(O)Fc}2] (4), and [tBu2Sn{OC(O)Fc}2] (5) (Fc = eta(5)C5H4-Fe-eta(5)C5H5). The reaction of triorganotin oxides, R3SnOSnR3 (R = nBu and Ph) with ferrocene carboxylic acid leads to the formation of the mono-nuclear derivatives [Ph3SnOC(O)Fc] (6) and [{nBu3SnOC(O)Fc}(n)] (7). Molecular structures of the compounds 1-4 and 6 have been determined by single-crystal X-ray analysis. The molecular structure of compound 1 is new among organotin carboxylates. In this compound, ferrocenyl carboxylates are involved in both chelating and bridging coordination modes to the tin atoms to form an eight-membered cyclic structure. In all of these compounds, the acidic protons of the cyclopentadienyl groups are hydrogen bonded to the carboxylate oxygens (C-HO) to form rich supramolecular assemblies. In addition to this, pi-pi, T-shaped, L-shaped, and side-to-face stacking interactions involving ferrocenyl groups also occur. Compound 6 shows an interesting and novel intermolecular CO2-pi stacking interaction. Electrochemical analysis of the compounds 1-4, 6, and 7 shows a single, quasi-reversible oxidation peak corresponding to the simultaneous oxidation of four, two, and one ferrocenyl substituents, respectively. Compound 5 shows two quasi-reversible oxidation peaks. This is attributed to the positional difference among the ferrocenyl substituents on the tin atom. Additionally, while compounds 2 and 4 are electrochemically quite robust and do not decompose even after ten continuous CV cycles, compounds 1, and 3, 5-7 start to show decomposition after five cycles.