1,3-Di-1-adamantylimidazolium (phthalocyaninato)lithium(I) acetone hemisolvate monohydrate

The asymmetric unit of the title compound, (C23H33N2)[Li(C32H16N8)]·0.5C3H6O·H2O, consists of two symmetry-unrelated lithium phthalocyanine (LiPc−) half-anions, centered at (1,0,0) and (0,,0), respectively, the bis(adamantyl)imidazolium cation (BAI+), occupying a general site, an acetone molecule, disordered about the inversion centre at (0, , ) and a water molecule at a general site. The LiPc− anions pack in a stepped pattern enclosing the bis(adamantyl)imidazolium cation. Attractions between the anion and cation are mediated by a water molecule which forms O—H⋯N hydrogen bonds. In addition, two C—H⋯O interactions are seen.


Experimental
Crystal data (C 23 Table 1 Hydrogen-bond geometry (Å , ).  The asymmetric unit of the title compound consists of two symmetry-unrelated halves of lithium phthalocyanine anions (LiPc -), centered at 1,0,0 and 0, 1/2,0, respectively; the bis(adamantyl)imidazolium cation (BAI + ), occupying a general site, an acetone molecule, at 0, 1/2,0.5, and a water molecule at a general site, Fig 1. In addition, the unit cell packing provides interesting detail of the arrangement of molecules within the crystal structure, as seen in Figure 2. Similar compounds utilizing nitrogen-based cations have been reported by Homborg & Kalz (1978a, 1978b. Although they may appear to be in Figure 2, the symmetry-related LiPcanions are not parallel, as seen in the angle (2.39°) between their mean planes. Additionally, their intermolecular distances are quite large (10.10 Å as measured between mesonitrogens) in comparison to those seen in Li 2 PC (3.06-3.38 Å) (Grossie, et al., 2006) The large spacing between LiPcmolecules is easily attributed to the bulky adamantyl substituents of the BAI + molecules, in which one cation appears to be enclosed within four LiPcanions forming ionic pockets. This is shown in Fig. 2, which presents the organized but unique packing of molecules. Rows of symmetry-related anions along the b axis are offset from each other, stacking in a stair-step manner. These molecules appear to be nearly orthogonal to the columnar anions, in which alternating columns have slightly different orientations. It is necessary, though, to view the packing from all angles to get a true understanding of ion arrangements.
Probably the most intriguing information obtained was the role of solvent molecules within the crystal structure. It was seen in the crystal structure of Li 2 PC that acetone and water ligated to lithium, forming dimers that were found in between LiPcpairs. In the current structure it can be seen that water molecules are crucial to the crystallization of the complex ions. Here, it is noticed that water forms O-H···N and C-H···O hydrogen bonds, Table 1, with the two symmetry-unrelated LiPcanions and one BAI + cation, acting as an intermediate to the three ions. Interatomic distances between hydrogen atoms and isoindoline and meso nitrogen of individual LiPcions were found to be 2.405 (17) Å and 2.025 (19) Å, respectively. The distance between the oxygen atom of water and the hydrogen on the 2-position of the BAI + cation was calculated to be about 2.18 Å.

S2. Experimental
The 1,3-bis(1-adamantyl)imidazolium tetrafluoroborate (0.884 g) was purified by dissolving it in 70 ml of acetone and filtering the insoluble impurities. The solution was evaporated to dryness to give 0.843 g (1.98 mmol) of the pure salt, which was redissolved in 10 ml of acetone and added to a solution of 0.   .76;N,16.34. Found: C,76.89;H,5.90;N,15.94.

S3. Refinement
Hydrogen atoms of the water molecule and of the methyl group of the acetone molecule were located in a difference Fourier map and refined with appropriate distance restraints. All other H-atoms were positioned geometrically and refined using a riding model with d(C-H) = 0.95Å, U iso =1.2U eq (C) for aromatic 1.00Å, U iso = 1.2U eq (C) for CH and 0.99Å, U iso = 1.2U eq (C) for CH 2 atoms

Figure 1
The asymmetric unit of I. Labelled atoms are related to unlabelled atoms by the symmetry codes -x+2, -y, -z for the Li1 anion and -x, -y+1, -z for the Li2 anion. Hydrogen atoms are not shown.  Unit cell packing diagram, viewed along the b axis. Acetone molecules have been omitted for clarity.

1,3-Bis(1-adamantyl)imidazolium lithium phthalocyanine monohydrate acetone hemisolvate.
Crystal data (C 23   Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.