(4-Cyano­phenolato)(subphthalocyaninato)boron

Andrew S Paton; Alan J Lough; Timothy P Bender

doi:10.1107/S1600536811000869

. 2011 Jan 29;67(Pt 2):o505–o506. doi: 10.1107/S1600536811000869

(4-Cyanophenolato)(subphthalocyaninato)boron¹

Andrew S Paton ^a, Alan J Lough ^b, Timothy P Bender ^a,^*

PMCID: PMC3051429 PMID: 21523157

Abstract

The crystal structure of the title compound, C₃₁H₁₆BN₇O, (CNPhO-BsubPc) is characterized by pairs of π–π stacking interactions between the concave faces of inversion-related BsubPc fragments with a centroid–centroid distance of 3.600 (1) Å. In addition, these pairs of molecules are linked into chains along [101] through further weak π–π stacking interactions with a centroid–centroid distance of 3.8587 (9) Å. There are also weak C—H⋯π(arene) interactions within the chains.

Related literature

For a general review of boronsubphthalocyanine compounds (BsubPcs), see: Claessens et al. (2002 ▶). For the synthesis of boronsubphthalocyanine and its derivatives, see: Zyskowski & Kennedy (2000 ▶); Claessens et al. (2003 ▶); Paton et al. (2011b ▶). For the application of BsubPcs in organic electronic devices, see: Morse et al. (2010 ▶) and references cited therein; Gommans et al. (2009) ▶. For related crystal structures of non-halogenated boronsubphthalocyanine derivatives, see: Potz et al. (2000 ▶); Paton et al. (2010 ▶, 2011a ▶,b ▶). For the treatment of disordered solvent molecules, see: Athimoolam et al. (2005 ▶); Cox et al. (2003 ▶); Mohamed et al. (2003 ▶); Stähler et al. (2001 ▶).

Experimental

Crystal data

C₃₁H₁₆BN₇O
M _r = 513.32
Monoclinic,
a = 16.2310 (3) Å
b = 27.5129 (7) Å
c = 13.4385 (2) Å
β = 119.4050 (12)°
V = 5228.00 (18) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 150 K
0.40 × 0.30 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.711, T _max = 0.994
21404 measured reflections
5914 independent reflections
4290 reflections with I > 2σ(I)
R _int = 0.087

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.141
S = 1.06
5914 reflections
361 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.26 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 global, I. DOI: 10.1107/S1600536811000869/zl2323sup1.cif

e-67-0o505-sup1.cif^{(22.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000869/zl2323Isup2.hkl

e-67-0o505-Isup2.hkl^{(289.6KB, hkl)}

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

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

Cg1, Cg2 and Cg3 are the centroids of the C25–C30, N1/C1/C2/C7/C8 and N3/C9/C10/C15/C19 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯Cg1ⁱ	0.95	2.70	3.499 (3)	143
C20—H20A⋯Cg2ⁱⁱ	0.95	2.59	3.254 (4)	127
C21—H21A⋯Cg3ⁱⁱ	0.95	2.70	3.238 (4)	116

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We wish to acknowledge funding for this research from the Natural Sciences and Engineering Research Council (NSERC) of Canada.

supplementary crystallographic information

Comment

We report the crystal structure of 4-cyanophenoxy-boronsubphthalocyanine (CNPhO-BsubPc), which possesses an electron withdrawing group in the para position of the phenoxy molecular fragment. We have recently reported a study of the crystal structures of a series of para-substituted phenoxy-BsubPc wherein most of the substituents were electron-donating alkyl groups (Paton et al., 2011b). Contained within that study was 4-fluorophenoxy-BsubPc (FPhO-BsubPc). While fluorine is moderately electron withdrawing we did not observe any difference in its crystal structure compared to the baseline phenoxy-BsubPc structure which contains pairs of molecules associated through π-stacking via the concave faces of two BsubPc molecules related by inversion centers. We have also have reported two BsubPc derivatives with electron-withdrawing groups in the para position, 4-acetylphenoxy-BsubPc (Paton et al., 2010) and 4-nitrophenoxy-BsubPc (Paton et al., 2011a). Both of these compounds are similar in structure to the FPhO-BsubPc, which typifies the substituted phenoxy-BsubPc packing motif.

The molecular structure of the title compound is shown in Fig. 1. The molecule shows the expected bowl shape of the BsubPc ligand. The B—O—C angle is 128.89 (11)°; however, both experimental and computational gas-phase values of B—O—C angles for phenoxy-derivatized BsubPc compounds have been shown to be significantly smaller, at 115.2 (2)° for the typical FPhO-BsubPc, and around 115° for the computationally determined gas-phase value (Paton et al., 2011b). The torsion angle between the boron, oxygen, and the first two carbon atoms on the phenoxy substituent (B—O—C—C) is -1.9 (3)° while in FPhO-BsubPc it is -91.0 (2)°.

In the crystal structure, there are π···π interactions between the concave faces of pairs of molecules at a distance of 3.6002 (10) Å across an inversion centre (for rings N5/C17/C18/C23/C24 and C18—C23 related by 1/2-x, 1/2-y, 1-z). These types of π···π stacking interactions are common to other BsubPc derivatives mentioned above. In the crystal structure the title compound, additional weaker π···π-stacking interactions between inversion related pairs at a distance of 3.8587 (9) Å involving rings C18—C23 and C18—C23 related by 1-x, y, 3/2-z, form one-dimensional chains along [101].

Solvent voids are present in the structure (see experimental). The channel-like voids in which the solvent resides extend along the c axis (see Fig. 3) and are bordered by the convex-faces of the BsubPc fragment and the cyanophenoxy units. Diffusing heptane into a solution of the title compound in acetone, instead of heptane into a benzene solution as in the current experiment, gave the same crystal structure in terms of unit-cell parameters, cell volume, and solvent cavity volume.

Experimental

Cl-BsubPc was synthesized by a procedure adapted from Zyskowski and Kennedy (2000). The title compound was synthesized using a method adapted from Claessens et al. (2003) and Paton et al. (2011b): 4-Cyanophenoxyboronsubphthalocyanine. Cl-BsubPc (0.510 g, 0.0012 mol) was mixed with 4-cyanophenol (0.714 g, 0.0060 mol) in toluene (10 ml) in a cylindrical vessel fitted with a reflux condenser and argon inlet. The mixture was stirred and heated at reflux under a constant pressure of argon for 17 h. Reaction was determined complete via HPLC by the absence of Cl-BsubPc. The solvent was evaporated under rotary evaporation. The crude product was purified on a Kauffman column using standard basic alumina (300 mesh) as the adsorbent and dichloromethane as the eluent. The product eluted from the Kauffman column while the excess phenol remained adsorbed. The dichloromethane was then removed under reduced pressure yielding a dark pink/magenta powder of the title compound (0.236 g, 40%).