I. The crystal structure of potassium bis(tricyanovinyl)amine. II. Nuclear magnetic resonance studies of alkali halide solutions. III. Elucidation of the intramolecular hydrogen bond in acetylacetone by the deuterium isotope effect on the chemical shift of the bridge hydrogen

Part I

Potassium bis-(tricyanovinyl) amine, K⁺N[C(CN)=C(CN)₂]₂^-, crystallizes in the monoclinic system with the space group Cc and lattice constants, a = 13.346 ± 0.003 Å, c = 8.992 ± 0.003 Å, B = 114.42 ± 0.02°, and Z = 4. Three dimensional intensity data were collected by layers perpendicular to b* and c* axes. The crystal structure was refined by the least squares method with anisotropic temperature factor to an R value of 0.064.

The average carbon-carbon and carbon-nitrogen bond distances in –C-CΞN are 1.441 ± 0.016 Å and 1.146 ± 0.014 Å respectively. The bis-(tricyanovinyl) amine anion is approximately planar. The coordination number of the potassium ion is eight with bond distances from 2.890 Å to 3.408 Å. The bond angle C-N-C of the amine nitrogen is 132.4 ± 1.9°. Among six cyano groups in the molecule, two of them are bent by what appear to be significant amounts (5.0° and 7.2°). The remaining four are linear within the experimental error. The bending can probably be explained by molecular packing forces in the crystals.

Part II

The nuclear magnetic resonance of ⁸¹Br and ¹²⁷I in aqueous solutions were studied. The cation-halide ion interactions were studied by studying the effect of the Li⁺, Na⁺, K⁺, Mg⁺⁺, Cs⁺ upon the line width of the halide ions. The solvent-halide ion interactions were studied by studying the effects of methanol, acetonitrile, and acetone upon the line width of ⁸¹Br and ¹²⁷I in the aqueous solutions. It was found that the viscosity plays a very important role upon the halide ions line width. There is no specific cation-halide ion interaction for those ions such as Mg⁺⁺, Di⁺, Na⁺, and K⁺, whereas the Cs⁺ - halide ion interaction is strong. The effect of organic solvents upon the halide ion line width in aqueous solutions is in the order acetone ˃ acetonitrile ˃ methanol. It is suggested that halide ions do form some stable complex with the solvent molecules and the reason Cs⁺ can replace one of the ligands in the solvent-halide ion complex.

Part III

An unusually large isotope effect on the bridge hydrogen chemical shift of the enol form of pentanedione-2, 4(acetylacetone) and 3-methylpentanedione-2, 4 has been observed. An attempt has been made to interpret this effect. It is suggested from the deuterium isotope effect studies, temperature dependence of the bridge hydrogen chemical shift studies, IR studies in the OH, OD, and C=O stretch regions, and the HMO calculations, that there may probably be two structures for the enol form of acetylacetone. The difference between these two structures arises mainly from the electronic structure of the π-system. The relative population of these two structures at various temperatures for normal acetylacetone and at room temperature for the deuterated acetylacetone were calculated.

An assessment of the efficiency of three active fish capture methods and a study of roach / bream hybrids on the Crossens drainage system near Southport.

An assessment of three methods of fish capture, to establish the best fishing method which reflects the best range of sizes and species of fish in a given area. The methods used were trawl netting, electrofishing, and seine netting which were assessed on the Crossens drainage system near Southport. The report also includes a study of roach / bream hybrids that were found at the site, which focuses on their distinguishing features and compared with the features of roach and bream.

The vulnerability of reproductively active squaretail coralgrouper (Plectropomus areolatus) to fishing

Squaretail coralgrouper (Plectropomus areolatus) were captured and tagged at a fish spawning aggregation (FSA) site with conventional and acoustic tags to assess their vulnerability to fishing and spatial dynamics during reproductive periods. Males outnumbered females in catch and, on average, were larger than females. Findings revealed a high vulnerability to fishing, particularly during reproductive periods, and most fish were recaptured within the 5-month spawning season and within 10−12 km of the aggregation site. Individual and sex-specific variability in movement to, and residency times at, the FSA site indicates that individual monthly spawning aggregations represent subsets of the total reproductive population. Some individuals appeared to move along a common migratory corridor to reach the FSA site. Sex-specific behavioral differences, particularly longer residency times, appear to increase the vulnerability of reproductively active males to fishing, particularly within a FSA, which could reduce reproductive output. Both fishery-dependent and fishery-independent data indicate that only males were present within the first month of aggregation. The combined results indicate that reproductively active P. areolatus are highly vulnerable to fishing and that FSAs and migratory corridors of reproductively active fish should be incorporated into marine protected areas. The capture of P. areolatus during reproductive periods should be restricted as part of a comprehensive management strateg