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

David A Grossie; William A Feld; John Kelley

doi:10.1107/S1600536808041135

. 2008 Dec 17;65(Pt 1):m72. doi: 10.1107/S1600536808041135

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

David A Grossie ^a,^*, William A Feld ^a, John Kelley ^a

PMCID: PMC2967910 PMID: 21581539

Abstract

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, Inline graphic ,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.

Related literature

Similar compounds utilizing nitrogen-based cations have been reported by Homborg & Kalz (1978a ▶,b ▶). For related structures see: Grossie et al. (2006 ▶).

Experimental

Crystal data

(C₂₃H₃₃N₂)[Li(C₃₂H₁₆N₈)]·0.5C₃H₆O·H₂O
M _r = 904.04
Monoclinic,
a = 15.799 (3) Å
b = 17.165 (4) Å
c = 17.831 (4) Å
β = 108.374 (3)°
V = 4588.9 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 173 (2) K
0.44 × 0.39 × 0.20 mm

Data collection

Bruker Smart APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.901, T _max = 0.985
54676 measured reflections
14917 independent reflections
11038 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.129
S = 1.03
14917 reflections
649 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶), ORTEP-3 for Windows, (Farrugia, 1997 ▶), OSCAIL, (McArdle, 1995 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶) and publCIF (Westrip, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536808041135/sj2558sup1.cif

e-65-00m72-sup1.cif^{(44.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041135/sj2558Isup2.hkl

e-65-00m72-Isup2.hkl^{(729.1KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N6	0.861 (18)	2.405 (17)	3.1618 (17)	147.1 (18)
O1—H1B⋯N3ⁱ	0.889 (18)	2.025 (19)	2.8911 (17)	164.3 (16)
C33—H33⋯O1	0.95	2.18	3.127 (2)	171
C37—H37A⋯O1	0.99	2.52	3.493 (2)	166

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the diffractometer time granted by A. Hunter, Youngstown State University.

supplementary crystallographic information

Comment

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 LiPc^- anions 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 Li₂PC (3.06–3.38 Å)(Grossie, et al., 2006) The large spacing between LiPc^- molecules is easily attributed to the bulky adamantyl substituents of the BAI⁺ molecules, in which one cation appears to be enclosed within four LiPc^- anions 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 Li₂PC that acetone and water ligated to lithium, forming dimers that were found in between LiPc^- pairs. 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 LiPc^- anions and one BAI⁺ cation, acting as an intermediate to the three ions. Interatomic distances between hydrogen atoms and isoindoline and meso nitrogen of individual LiPc^- ions 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.

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 0.991 g (1.98 mmol) of dilithium phthalocyanine in 100 ml of acetone. The solution was evaporated to approximately 20–30 ml under reduced pressure to the point of crystallization, sealed and crystallized at 5°C for 72 h. The resulting solid was redissolved in 125 ml of hot acetone with stirring (some undissolved solid remained). The volume was reduced and crystallized at 5°C. The dry product isolated by filtration gave 0.893 g (55.3%) of purple crystals. m.p. 349–351°C. Anal. Calc. for C55H49LiN10 (856.99): C, 77.08; H, 5.76; N, 16.34. Found: C, 76.89; H, 5.90; N, 15.94.