(Dodecafluorosubphthalocyaninato)(4-methylphenolato)boron(III)

Andrew S Paton; Graham E Morse; Jozef F Maka; Alan J Lough; Timothy P Bender

doi:10.1107/S1600536810042716

. 2010 Nov 6;66(Pt 12):o3059. doi: 10.1107/S1600536810042716

(Dodecafluorosubphthalocyaninato)(4-methylphenolato)boron(III)

Andrew S Paton ^a, Graham E Morse ^a, Jozef F Maka ^a, Alan J Lough ^b, Timothy P Bender ^a,^*

PMCID: PMC3011663 PMID: 21589369

Abstract

In the title compound, C₃₁H₇BF₁₂N₆O, molecules are arranged into one-dimensional columns with an intermolecular B⋯B distance of 5.3176 (8) Å. Bowl-shaped molecules are arranged within the columns in a concave bowl-to-ligand arrangement separated by a ring centroid distance of 3.532 (2) Å between the benzene ring of the 4-methylphenoxy ligand and one of the three five-membered rings of a symmetry-related molecule.

Related literature

For a general review of boronsubphthalocyanine compounds (BsubPcs), see: Claessens et al. (2002 ▶). For the application of BsubPcs in organic light-emitting diodes, see: Morse et al. (2010a ▶) and references cited therein. For applications of BsubPcs in organic solar cells, see: Gommans et al. (2009 ▶). For the first reported synthesis, characterization and crystal structure of PhO-F₁₂BsubPc, see: Claessens & Torres (2002 ▶). For a synthetic process to obtain the precursor compound, Br-F₁₂BsubPc, see: Sharman & van Lier (2005 ▶); Morse et al. (2010b ▶).

Experimental

Crystal data

C₃₁H₇BF₁₂N₆O
M _r = 718.24
Monoclinic,
a = 14.6522 (5) Å
b = 10.5510 (6) Å
c = 18.0010 (7) Å
β = 96.663 (3)°
V = 2764.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 150 K
0.46 × 0.42 × 0.34 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.764, T _max = 0.959
16887 measured reflections
6256 independent reflections
3481 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.172
S = 1.03
6256 reflections
460 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXTL (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810042716/jj2067sup1.cif

e-66-o3059-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810042716/jj2067Isup2.hkl

e-66-o3059-Isup2.hkl^{(306.2KB, hkl)}

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

Acknowledgments

The authors acknowledge the Natural Sciences and Engineering Research Council (NSERC) of Canada for funding this research in the form of a Discovery Grant (TPB), a Canada Graduate Scholarship (GEM) and a Post Graduate Scholarship (ASP).

supplementary crystallographic information

Comment

Boronsubphthalocyanine (BsubPc) is unique amongst all phthalocyanines (Pcs) as only boron templates the formation of its cone-shaped macrocyclic aromatic ligand (Claessens et al., 2002). Recently, BsubPcs have been shown to be useful as functional solid state materials in organic solar cells (Gommans et al., 2009) and organic light emitting diodes (Morse et al., 2010a). Two subclasses of BsubPcs are commonly used – dodecahydrogenated and dodecafluorinated – and they are generally applied as either their halo or phenoxy derivatives. However, little is known about their arrangement in the solid state, which is of interest to those who want to engineer functional devices containing BsubPcs.

We have synthesized 4-methylphenoxydodecafluoroboronsubphthalocyanine (4-MePhO-F₁₂BsubPc) and obtained single crystals using a solvent diffusion method. The molecular structure of the title compound is shown in Fig. 1. In the crystal structure molecules are arranged into one-dimensional columns aligned approximately with the B—O bonds. (Fig. 2 b) with an intermolecular B···B distance of 5.3176 (8) Å (-x + 3/2, y + 1/2, -z + 1/2). Bowl-shaped molecules are arranged within the columns in a concave bowl to ligand arrangement separated by a ring centroid distance of 3.532 (2)Å between the benzene ring of the 4-methylphenoxy ligand (C25—C30) and one of the three five membered rings (N1/C1/C2/C7/C8) of a molecule at 3/2 - x,1/2 + y,1/2 - z (see Fig. 2).

A closely related compound, phenoxydodecafluoroboronsubphthalocyanine (PhO-F₁₂BsubPc) has been previously synthesized (Claessens & Torres et al., 2002; Morse et al. 2010a) and its crystal structures reported. In each case, with crystals grown under different conditions. As in the title compound, in the crystal structure of PhO-F₁₂BsubPc, molecules arrange into one-dimensional columns again approximately aligned with the B—O bond regardless of the method of growth. The crystal structure of PhO-F₁₂BsubPc (Morse et al., 2010a) is re-illustrated for reference (Fig. 3). The intermolecular B···B distance in PhO-F₁₂BsubPc is 5.3379 (7) Å (-x + 2, y + 1/2, -z + 3/2). a

The crystal structure of the title compound in addition to those of PhO-F₁₂BsubPc suggest the arrangement of phenoxy-F₁₂BsubPcs in the solid state may be predominant. In an effort to confirm or refute this, and to test the dependence on the nature of the alkyl substituent on the phenoxy group, we attempted to grow single crystals of 4 - t-butylphenoxydodecafluoroboronsubphthalocyanine. Unfortunately we found this derivative very soluble in organic solvents and were not able obtain single crystals as of yet.

Experimental

Br-F₁₂BsubPc was synthesized according to Morse et al. (2010a) which is an adaptation of the method of Sharman et al. (2005). For its crystal structure see Morse et al. (2010b).

4-MePhO-F₁₂BsubPc. A solution of 1.00 g of (Br-F₁₂BsubPc) in 5 ml of toluene was mixed with 0.78 g of 4-methylphenol. The mixture was stirred and heated to reflux under argon for 8 h. Reaction was determined complete via HPLC (RP-18 column, acetonitrile mobile phase 1.2 ml/min). The crude product was purified first by dissolving the product in toluene (300 ml) and extracting with 3.0 M KOH solution in distilled water (3 x 300 ml). The solvent was evaporated under vacuum and the product purified on a Kauffman column of alumina (absorbent) and dichloromethane (eluent). The Kauffman column was run overnight and subsequently the dichloromethane was removed under reduced pressure leaving a dark pink powder (0.52 g, 0.00072 mol, 44% yield). Crystals of the title compound were grown by slow diffusion of heptane into a solution of the title compound in benzene.