Analysis of the powder X-ray diffraction (PXRD) data confirmed that we were able to produce the desired phase up to x t ≤ 0.75 [Fig. ESI Fig. ], however, we found that the the pure bod phase did not form. Consequently, we synthesised a series through the reaction of ethanolic solutions of nickel chloride and ligands over the same target range of x t , analogous to CoCl 2 (btd). We found by analysis of PXRD data that this again produced powders isostructural to NiCl 2 (btd) up to x t ≤ 0.75, but at x t = 1 we obtained a phase mixture for which primary phase was unknown. The purity of all other compounds was assessed using Pawley refinement of the PXRD data, which showed that the samples synthesised through direct reaction contained very small quantities of starting material, but that the solution-synthesised samples had broader diffraction peaks, likely due to small particle sizes [Fig. The phase mixture formed during solution synthesis with x t = 1 included a number of small single crystals (further details of the single crystal diffraction characterisation can be found in the ESI Sections S2.3, S2.4). We isolated a larger crystal (63 × 14 × 10 µm 3 ) which we found using single crystal X-ray diffraction to be a new 1D coordination polymer NiCl ], though we also were also able to find crystals of NiCl 2 • 2 H 2 O. Re-analysis of our PXRD data in the light of this new structure showed that it was primarily NiCl 2 (bod) 2 and a small quantity of nickel chloride hydrates. Further examination using single crystal electron diffraction of the remainder of the reaction mixture, which was dispersed as powder after being ]. Comparison of refinements with only bod, only btd and mixed ligand showed that the sample included nanocrystals of a monoclinic twinned NiCl 2 (bod) and an orthorhombic polymorph of NiCl 2 (btd), although we cannot exclude that this orthorhombic phase includes a low proportion of bod (<5%). We note these phases are not seen in the bulk PXRD and hence, we ascribe the formation of a small number of nanocrystals of NiCl 2 (btd) to the presence of adventitious btd, likely facilitated by its high vapour pressure. This highlights the capability of electron diffraction to find and solve the structures of even minor crystalline phases. To determine the btd:bod ratio, and hence x, we dissolved a portion of each sample in d 6 -DMSO and carried out solution state 1 H NMR [Fig. (a), Fig. ]. This revealed that the bod content determined by NMR, x NMR , was uniformly bod-poor compared to the target composition. This, together with the formation of NiCl 2 (bod) 2 in preference to NiCl 2 (bod), suggests that the more electron deficient bod ligand does not coordinate as readily as the btd ligand. This is further borne out by the lack of reported metal complexes containing bod as a ligand in the CSD. We found that the x NMR = 0.31 (x t = 0.75) sample synthesised through direct reaction was poorly crystalline and contained significant impurities, so has not been further analysed. We thus focussed on samples with x t ≤ 0.75 for solution state reaction and x t ≤ 0.50 for solid state samples.