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ISSN: 2056-9890

(4-Acetyl­phenolato)(subphthalo­cyaninato)boron(III)

aDepartment of Chemical Engineering & Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario, Canada M5S 3E5, and bDepartment of Chemistry, University of Toronto, 80 St George Street, Toronto, Ontario, Canada M5S 3H6
*Correspondence e-mail: tim.bender@utoronto.ca

(Received 29 October 2010; accepted 8 November 2010; online 20 November 2010)

In the title compound, C32H19BN6O2, the B atom adopts a BON3 tetra­hedral coordination geometry. In the crystal, pairs of mol­ecules are associated through aromatic ππ stacking inter­actions between the concave faces of the boronsubphthalocyanine fragments at a centroid–centroid distance of 3.4951 (19) Å and a weaker inter­action of the same type between the convex faces of the same group [centroid–centroid separation = 3.5669 (18) Å] also occurs.

Related literature

For related structures and discussion of electronic effects, see: Paton et al. (2010[Paton, A. S., Morse, G. E., Lough, A. J. & Bender, T. P. (2010). CrystEngComm, doi:10.1039/C0CE00599A.]). For further synthetic details, see: Claessens et al. (2002)[Claessens, C. G., González-Rodríguez, D., del Rey, B. & Torres, T. (2002). Chem. Rev. 102, 835-853.]; Zyskowski & Kennedy (2000[Zyskowski, C. D. & Kennedy, V. O. (2000). J. Porphyrins Phthalocyanins, pp. 707-712.]).

[Scheme 1]

Experimental

Crystal data
  • C32H19BN6O2

  • Mr = 530.34

  • Triclinic, [P \overline 1]

  • a = 10.5471 (8) Å

  • b = 10.5786 (5) Å

  • c = 11.5375 (9) Å

  • α = 77.446 (4)°

  • β = 88.817 (3)°

  • γ = 83.966 (4)°

  • V = 1249.54 (15) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.09 mm−1

  • T = 150 K

  • 0.08 × 0.08 × 0.05 mm

Data collection
  • Nonius KappaCCD diffractometer

  • Absorption correction: multi-scan (SORTAV; Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.858, Tmax = 1.002

  • 8602 measured reflections

  • 4273 independent reflections

  • 2393 reflections with I > 2σ(I)

  • Rint = 0.078

Refinement
  • R[F2 > 2σ(F2)] = 0.055

  • wR(F2) = 0.146

  • S = 0.98

  • 4273 reflections

  • 372 parameters

  • H-atom parameters constrained

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.22 e Å−3

Table 1
Selected bond lengths (Å)

B1—O1 1.457 (4)
B1—N1 1.487 (4)
B1—N3 1.494 (4)
B1—N5 1.487 (4)

Data collection: COLLECT (Nonius, 2002[Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

We report the crystal structure of 4-acetylphenoxy-boronsubphthalocyanine (AcPhO-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-BsubPcs in which most of the substituents were alkyl (electron donating) (Paton et al., 2010). Contained within the 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. Our goal is to study the effect of the placement of strong electron withdrawing groups on the phenoxy molecular fragment and to determine any effect on the crystal structure of the resulting phenoxy-BsubPc. The structure of the current report is described and compared to FPhO-BsubPc, which typifies the phenoxy-BsubPc packing motif. The title compound was prepared by a method described previously (Paton et al., 2010, Claessens et al., 2002), in which chloro-boronsubphthalocyanine (Cl-BsubPc) is reacted with an excess of 4-hydroxy-acetophenone (4-acetylphenol) until substitution is complete. After purification, single crystals suitable for diffraction were grown using vapour diffusion of heptane into a solution of the product in benzene. The molecular structure of the title compound is shown in Fig. 1. The compound shows the expected bowl shape of the BsubPc ligand. The boron-oxygen-carbon (B—O—C) angle in the molecule is 130.3 (2)°; this value differs from both the experimental and computational gas-phase values of B—O—C angle for the typical FPhO-BsubPc, which are significantly smaller, at 115.2 (2)° and around 115°, respectively (Paton et al., 2010). Looking at the torsion angle between the boron, oxygen, and the first two carbon atoms on the phenoxy substituent (B—O—C—C) gives a value of -22.0 (5). In contrast, the angle associated with typical phenoxy-BsubPc is -91.0 (2)° relative to the plane of the BsubPc fragment (Paton et al., 2010). The extended crystal structure of AcPhO-BsubPc (Fig. 2), is typical to that which we have seen for para-alkylphenoxy-BsubPc when the alkyl group was sufficiently large (Paton et al. 2010). Each BsubPc molecular fragment associates with its nearest neighbour through a π-interaction [C18/C19/C20/C21/C22/C23 and C17/C18/C23/C24/N5, (-x, -y, -z)] between concave faces, with a centroid-to-centroid distance of 3.4951 (19) Å. The arrangement of the nearest neighbours is one-dimensional through the crystal parallel to the b axis of the unit cell and resembles something between the dimer arrangement seen for p-H, p-methyl and p-t-butylphenoxy-BsubPc and the ribbon arrangement seen for p-t-octylphenoxy-BsubPc. (Paton et al. 2010) Finally, there is a π-interaction linking adjacent rows between the BsubPc convex faces [C10/C11/C12/C13/C14/C15 and C9/C10/C15/C16/N3, (-x, -y, -z)] at a distance of 3.5669 (18) Å (Fig. 2).

Related literature top

For related structures and discussion of electronic effects, see: Paton et al. (2010). For further synthetic details, see: Claessens et al. (2002); Zyskowski & Kennedy (2000).

Experimental top

Cl-BsubPc, synthesized by a procedure adapted from Zyskowski and Kennedy (2000). The title compound was synthesized using a method adapted from Claessens et al. (2002) and Paton et al. (2010): 4-Acetylphenoxy-boronsubphthalocyanine. Cl-BsubPc (0.510 g, 0.0012 mol) was mixed with 4-hydroxy-acetophenone (4-acetyl-phenol, 0.860 g, 0.0063 mol) in 1,2-dichlorobenzene (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 purified on a Kauffman column using standard basic alumina (300 mesh) as the adsorbent and dichloromethane as the eluent. The product elutes from the Kauffman column while the excess phenol remains adsorbed. The dichloromethane was then removed under reduced pressure yielding a dark pink/magenta powder of the title compound (0.215 g, 34%). For further details of the Kauffman apparatus, see: Paton et al. (2010).

Structure description top

We report the crystal structure of 4-acetylphenoxy-boronsubphthalocyanine (AcPhO-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-BsubPcs in which most of the substituents were alkyl (electron donating) (Paton et al., 2010). Contained within the 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. Our goal is to study the effect of the placement of strong electron withdrawing groups on the phenoxy molecular fragment and to determine any effect on the crystal structure of the resulting phenoxy-BsubPc. The structure of the current report is described and compared to FPhO-BsubPc, which typifies the phenoxy-BsubPc packing motif. The title compound was prepared by a method described previously (Paton et al., 2010, Claessens et al., 2002), in which chloro-boronsubphthalocyanine (Cl-BsubPc) is reacted with an excess of 4-hydroxy-acetophenone (4-acetylphenol) until substitution is complete. After purification, single crystals suitable for diffraction were grown using vapour diffusion of heptane into a solution of the product in benzene. The molecular structure of the title compound is shown in Fig. 1. The compound shows the expected bowl shape of the BsubPc ligand. The boron-oxygen-carbon (B—O—C) angle in the molecule is 130.3 (2)°; this value differs from both the experimental and computational gas-phase values of B—O—C angle for the typical FPhO-BsubPc, which are significantly smaller, at 115.2 (2)° and around 115°, respectively (Paton et al., 2010). Looking at the torsion angle between the boron, oxygen, and the first two carbon atoms on the phenoxy substituent (B—O—C—C) gives a value of -22.0 (5). In contrast, the angle associated with typical phenoxy-BsubPc is -91.0 (2)° relative to the plane of the BsubPc fragment (Paton et al., 2010). The extended crystal structure of AcPhO-BsubPc (Fig. 2), is typical to that which we have seen for para-alkylphenoxy-BsubPc when the alkyl group was sufficiently large (Paton et al. 2010). Each BsubPc molecular fragment associates with its nearest neighbour through a π-interaction [C18/C19/C20/C21/C22/C23 and C17/C18/C23/C24/N5, (-x, -y, -z)] between concave faces, with a centroid-to-centroid distance of 3.4951 (19) Å. The arrangement of the nearest neighbours is one-dimensional through the crystal parallel to the b axis of the unit cell and resembles something between the dimer arrangement seen for p-H, p-methyl and p-t-butylphenoxy-BsubPc and the ribbon arrangement seen for p-t-octylphenoxy-BsubPc. (Paton et al. 2010) Finally, there is a π-interaction linking adjacent rows between the BsubPc convex faces [C10/C11/C12/C13/C14/C15 and C9/C10/C15/C16/N3, (-x, -y, -z)] at a distance of 3.5669 (18) Å (Fig. 2).

For related structures and discussion of electronic effects, see: Paton et al. (2010). For further synthetic details, see: Claessens et al. (2002); Zyskowski & Kennedy (2000).

Computing details top

Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); 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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of AcPhO-BsubPc with displacement ellipsoids drawn at the 30% probability level.
[Figure 2] Fig. 2. Extended crystal structure of AcPhO-BsubPc shown from two perspectives (side and end).
(4-Acetylphenolato)(1,2,3,4,8,9,10,11,15,16,17,18-dodecafluoro-7,12:14,19- diimino-21,5-nitrilo-5H- tribenzo[c,h,m][1,6,11]triazacyclopentadecinato)boron(III) top
Crystal data top
C32H19BN6O2Z = 2
Mr = 530.34F(000) = 548
Triclinic, P1Dx = 1.410 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.5471 (8) ÅCell parameters from 8602 reflections
b = 10.5786 (5) Åθ = 2.6–25.0°
c = 11.5375 (9) ŵ = 0.09 mm1
α = 77.446 (4)°T = 150 K
β = 88.817 (3)°Block, magenta
γ = 83.966 (4)°0.08 × 0.08 × 0.05 mm
V = 1249.54 (15) Å3
Data collection top
Nonius KappaCCD
diffractometer
4273 independent reflections
Radiation source: fine-focus sealed tube2393 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.078
Detector resolution: 9 pixels mm-1θmax = 25.0°, θmin = 2.6°
φ scans and ω scans with κ offsetsh = 1212
Absorption correction: multi-scan
from symmetry-related measurements (SORTAV; Blessing, 1995)
k = 1112
Tmin = 0.858, Tmax = 1.002l = 1213
8602 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.146 w = 1/[σ2(Fo2) + (0.0559P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
4273 reflectionsΔρmax = 0.23 e Å3
372 parametersΔρmin = 0.22 e Å3
0 restraintsExtinction correction: SHELXTL (Version 6.1; Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0102 (19)
Crystal data top
C32H19BN6O2γ = 83.966 (4)°
Mr = 530.34V = 1249.54 (15) Å3
Triclinic, P1Z = 2
a = 10.5471 (8) ÅMo Kα radiation
b = 10.5786 (5) ŵ = 0.09 mm1
c = 11.5375 (9) ÅT = 150 K
α = 77.446 (4)°0.08 × 0.08 × 0.05 mm
β = 88.817 (3)°
Data collection top
Nonius KappaCCD
diffractometer
4273 independent reflections
Absorption correction: multi-scan
from symmetry-related measurements (SORTAV; Blessing, 1995)
2393 reflections with I > 2σ(I)
Tmin = 0.858, Tmax = 1.002Rint = 0.078
8602 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.146H-atom parameters constrained
S = 0.98Δρmax = 0.23 e Å3
4273 reflectionsΔρmin = 0.22 e Å3
372 parameters
Special details top

Experimental. (SORTAV; Blessing, 1995)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.84545 (19)0.21044 (17)0.32764 (17)0.0390 (6)
O21.2585 (2)0.5988 (2)0.3568 (2)0.0493 (6)
N10.7983 (2)0.1720 (2)0.1263 (2)0.0334 (6)
N20.7054 (2)0.0271 (2)0.1944 (2)0.0373 (6)
N30.6430 (2)0.1576 (2)0.2758 (2)0.0342 (6)
N40.5094 (2)0.3473 (2)0.2935 (2)0.0360 (6)
N50.6990 (2)0.3625 (2)0.1770 (2)0.0338 (6)
N60.8102 (2)0.3770 (2)0.0067 (2)0.0356 (6)
C10.8329 (3)0.2456 (3)0.0194 (3)0.0348 (8)
C20.8656 (3)0.1542 (3)0.0569 (3)0.0351 (8)
C30.9125 (3)0.1700 (3)0.1722 (3)0.0416 (8)
H3A0.93290.25240.21550.050*
C40.9285 (3)0.0610 (3)0.2218 (3)0.0448 (9)
H4A0.96390.06850.29900.054*
C50.8939 (3)0.0592 (3)0.1609 (3)0.0429 (8)
H5A0.90390.13130.19830.052*
C60.8452 (3)0.0755 (3)0.0474 (3)0.0385 (8)
H6A0.82110.15740.00640.046*
C70.8325 (3)0.0317 (3)0.0055 (3)0.0343 (8)
C80.7819 (3)0.0472 (3)0.1197 (3)0.0348 (8)
C90.6314 (3)0.0325 (3)0.2668 (3)0.0335 (7)
C100.5121 (3)0.0000 (3)0.3263 (2)0.0332 (8)
C110.4524 (3)0.1143 (3)0.3485 (3)0.0366 (8)
H11A0.49090.19050.32560.044*
C120.3356 (3)0.1134 (3)0.4047 (3)0.0396 (8)
H12A0.29460.19110.42350.048*
C130.2768 (3)0.0006 (3)0.4345 (3)0.0389 (8)
H13A0.19660.00300.47350.047*
C140.3323 (3)0.1145 (3)0.4087 (3)0.0368 (8)
H14A0.29010.19170.42680.044*
C150.4514 (3)0.1145 (3)0.3557 (2)0.0320 (7)
C160.5348 (3)0.2169 (3)0.3156 (3)0.0331 (7)
C170.5876 (3)0.4175 (3)0.2165 (3)0.0340 (8)
C180.5647 (3)0.5469 (3)0.1419 (3)0.0341 (8)
C190.4719 (3)0.6503 (3)0.1443 (3)0.0396 (8)
H19A0.40820.64390.20410.048*
C200.4753 (3)0.7628 (3)0.0569 (3)0.0406 (8)
H20A0.41580.83610.05940.049*
C210.5650 (3)0.7704 (3)0.0351 (3)0.0404 (8)
H21A0.56480.84880.09380.048*
C220.6538 (3)0.6665 (3)0.0425 (3)0.0367 (8)
H22A0.71120.67030.10740.044*
C230.6558 (3)0.5557 (3)0.0492 (3)0.0329 (7)
C240.7357 (3)0.4319 (3)0.0686 (3)0.0338 (7)
C250.9382 (3)0.2846 (3)0.3453 (3)0.0343 (8)
C260.9781 (3)0.2682 (3)0.4620 (3)0.0372 (8)
H26A0.93950.20930.52320.045*
C271.0731 (3)0.3366 (3)0.4899 (3)0.0398 (8)
H27A1.10050.32320.57000.048*
C281.1292 (3)0.4251 (3)0.4021 (3)0.0338 (7)
C291.0886 (3)0.4412 (3)0.2854 (3)0.0361 (8)
H29A1.12620.50140.22450.043*
C300.9946 (3)0.3714 (3)0.2561 (3)0.0366 (8)
H30A0.96890.38280.17580.044*
C311.2310 (3)0.5024 (3)0.4297 (3)0.0406 (8)
C321.2969 (4)0.4619 (3)0.5468 (3)0.0601 (10)
H32A1.36360.51900.55000.090*
H32B1.33550.37180.55720.090*
H32C1.23510.46840.61040.090*
B10.7555 (3)0.2280 (3)0.2299 (3)0.0362 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0413 (13)0.0386 (12)0.0360 (13)0.0134 (10)0.0056 (10)0.0005 (10)
O20.0517 (15)0.0442 (13)0.0549 (16)0.0146 (11)0.0061 (12)0.0127 (12)
N10.0343 (15)0.0325 (14)0.0330 (16)0.0058 (11)0.0030 (12)0.0054 (12)
N20.0372 (16)0.0352 (14)0.0393 (16)0.0060 (12)0.0015 (13)0.0068 (12)
N30.0364 (16)0.0334 (14)0.0334 (15)0.0067 (12)0.0020 (12)0.0071 (12)
N40.0418 (16)0.0333 (15)0.0335 (16)0.0085 (12)0.0027 (13)0.0067 (12)
N50.0368 (16)0.0335 (14)0.0318 (16)0.0063 (12)0.0009 (12)0.0074 (12)
N60.0357 (16)0.0345 (14)0.0376 (16)0.0065 (12)0.0006 (13)0.0083 (12)
C10.0325 (18)0.0363 (18)0.0355 (19)0.0065 (14)0.0010 (15)0.0062 (15)
C20.0315 (18)0.0375 (18)0.035 (2)0.0002 (14)0.0030 (15)0.0053 (15)
C30.040 (2)0.0448 (19)0.036 (2)0.0013 (15)0.0007 (16)0.0017 (16)
C40.045 (2)0.052 (2)0.035 (2)0.0063 (17)0.0049 (16)0.0100 (17)
C50.041 (2)0.045 (2)0.044 (2)0.0033 (15)0.0056 (17)0.0135 (17)
C60.0305 (19)0.0419 (19)0.042 (2)0.0021 (14)0.0051 (16)0.0079 (16)
C70.0276 (18)0.0376 (18)0.038 (2)0.0025 (14)0.0015 (15)0.0087 (15)
C80.0322 (19)0.0325 (17)0.038 (2)0.0014 (14)0.0022 (15)0.0047 (15)
C90.0347 (19)0.0286 (16)0.0363 (19)0.0027 (14)0.0040 (15)0.0049 (14)
C100.0366 (19)0.0342 (17)0.0281 (18)0.0083 (14)0.0014 (14)0.0025 (14)
C110.041 (2)0.0368 (18)0.0319 (19)0.0070 (15)0.0025 (16)0.0067 (14)
C120.046 (2)0.0345 (18)0.039 (2)0.0126 (15)0.0011 (16)0.0058 (15)
C130.0367 (19)0.0419 (19)0.0368 (19)0.0120 (15)0.0001 (15)0.0018 (15)
C140.041 (2)0.0347 (17)0.0348 (19)0.0082 (14)0.0050 (16)0.0060 (14)
C150.0349 (19)0.0332 (17)0.0281 (18)0.0083 (14)0.0031 (14)0.0045 (14)
C160.038 (2)0.0363 (18)0.0263 (17)0.0087 (15)0.0010 (15)0.0074 (14)
C170.039 (2)0.0368 (18)0.0291 (18)0.0076 (15)0.0006 (15)0.0113 (15)
C180.040 (2)0.0302 (17)0.0332 (19)0.0080 (14)0.0021 (15)0.0083 (14)
C190.041 (2)0.0389 (19)0.042 (2)0.0123 (15)0.0013 (16)0.0111 (16)
C200.037 (2)0.0354 (18)0.051 (2)0.0053 (14)0.0063 (17)0.0103 (16)
C210.044 (2)0.0346 (18)0.041 (2)0.0085 (16)0.0061 (17)0.0025 (15)
C220.0381 (19)0.0377 (18)0.0358 (19)0.0131 (15)0.0027 (15)0.0064 (15)
C230.0374 (19)0.0281 (16)0.0355 (19)0.0109 (14)0.0002 (15)0.0083 (14)
C240.0335 (19)0.0382 (18)0.0300 (19)0.0081 (14)0.0013 (15)0.0058 (15)
C250.0315 (18)0.0347 (17)0.037 (2)0.0046 (14)0.0003 (15)0.0091 (15)
C260.040 (2)0.0438 (18)0.0281 (19)0.0090 (15)0.0039 (15)0.0059 (14)
C270.037 (2)0.0471 (19)0.034 (2)0.0037 (15)0.0004 (16)0.0081 (16)
C280.0323 (18)0.0350 (17)0.036 (2)0.0040 (14)0.0002 (15)0.0113 (15)
C290.040 (2)0.0316 (17)0.036 (2)0.0057 (14)0.0064 (15)0.0053 (14)
C300.044 (2)0.0359 (17)0.0294 (18)0.0081 (15)0.0008 (15)0.0042 (15)
C310.040 (2)0.0415 (19)0.043 (2)0.0057 (15)0.0073 (17)0.0145 (16)
C320.063 (3)0.066 (2)0.058 (3)0.0208 (19)0.015 (2)0.019 (2)
B10.033 (2)0.037 (2)0.037 (2)0.0075 (17)0.0000 (18)0.0036 (17)
Geometric parameters (Å, º) top
O1—C251.361 (3)C12—C131.394 (4)
O2—C311.229 (3)C12—H12A0.9500
N1—C81.367 (3)C13—C141.377 (4)
N1—C11.373 (3)C13—H13A0.9500
B1—O11.457 (4)C14—C151.386 (4)
B1—N11.487 (4)C14—H14A0.9500
B1—N31.494 (4)C15—C161.458 (4)
B1—N51.487 (4)C17—C181.449 (4)
N2—C91.342 (4)C18—C191.393 (4)
N2—C81.351 (3)C18—C231.418 (4)
N3—C161.364 (4)C19—C201.385 (4)
N3—C91.368 (3)C19—H19A0.9500
N4—C161.346 (3)C20—C211.402 (4)
N4—C171.354 (3)C20—H20A0.9500
N5—C171.371 (4)C21—C221.383 (4)
N5—C241.376 (3)C21—H21A0.9500
N6—C241.343 (4)C22—C231.396 (4)
N6—C11.353 (3)C22—H22A0.9500
C1—C21.454 (4)C23—C241.457 (4)
C2—C31.392 (4)C25—C261.388 (4)
C2—C71.413 (4)C25—C301.391 (4)
C3—C41.388 (4)C26—C271.378 (4)
C3—H3A0.9500C26—H26A0.9500
C4—C51.393 (4)C27—C281.390 (4)
C4—H4A0.9500C27—H27A0.9500
C5—C61.379 (4)C28—C291.390 (4)
C5—H5A0.9500C28—C311.495 (4)
C6—C71.393 (4)C29—C301.386 (4)
C6—H6A0.9500C29—H29A0.9500
C7—C81.447 (4)C30—H30A0.9500
C9—C101.458 (4)C31—C321.490 (5)
C10—C111.395 (4)C32—H32A0.9800
C10—C151.412 (4)C32—H32B0.9800
C11—C121.381 (4)C32—H32C0.9800
C11—H11A0.9500
C25—O1—B1130.3 (2)N4—C16—C15130.5 (3)
C8—N1—C1112.4 (2)N3—C16—C15105.9 (2)
C8—N1—B1122.7 (2)N4—C17—N5122.4 (2)
C1—N1—B1123.5 (2)N4—C17—C18130.3 (3)
C9—N2—C8116.7 (2)N5—C17—C18106.1 (2)
C16—N3—C9113.1 (2)C19—C18—C23120.4 (3)
C16—N3—B1123.2 (2)C19—C18—C17132.4 (3)
C9—N3—B1123.1 (3)C23—C18—C17107.1 (3)
C16—N4—C17116.8 (3)C20—C19—C18118.1 (3)
C17—N5—C24112.3 (2)C20—C19—H19A121.0
C17—N5—B1123.0 (2)C18—C19—H19A121.0
C24—N5—B1123.1 (3)C19—C20—C21121.2 (3)
C24—N6—C1117.2 (2)C19—C20—H20A119.4
N6—C1—N1121.8 (3)C21—C20—H20A119.4
N6—C1—C2130.9 (3)C22—C21—C20121.6 (3)
N1—C1—C2105.8 (2)C22—C21—H21A119.2
C3—C2—C7120.6 (3)C20—C21—H21A119.2
C3—C2—C1132.4 (3)C21—C22—C23117.4 (3)
C7—C2—C1106.9 (3)C21—C22—H22A121.3
C4—C3—C2117.7 (3)C23—C22—H22A121.3
C4—C3—H3A121.2C22—C23—C18121.1 (3)
C2—C3—H3A121.2C22—C23—C24131.3 (3)
C3—C4—C5121.6 (3)C18—C23—C24107.4 (2)
C3—C4—H4A119.2N6—C24—N5122.5 (3)
C5—C4—H4A119.2N6—C24—C23130.7 (3)
C6—C5—C4121.2 (3)N5—C24—C23105.4 (3)
C6—C5—H5A119.4O1—C25—C26115.6 (3)
C4—C5—H5A119.4O1—C25—C30124.9 (3)
C5—C6—C7118.0 (3)C26—C25—C30119.4 (3)
C5—C6—H6A121.0C27—C26—C25120.6 (3)
C7—C6—H6A121.0C27—C26—H26A119.7
C6—C7—C2120.8 (3)C25—C26—H26A119.7
C6—C7—C8131.3 (3)C26—C27—C28120.6 (3)
C2—C7—C8107.8 (3)C26—C27—H27A119.7
N2—C8—N1122.8 (3)C28—C27—H27A119.7
N2—C8—C7129.5 (3)C27—C28—C29118.5 (3)
N1—C8—C7105.8 (2)C27—C28—C31122.0 (3)
N2—C9—N3122.2 (3)C29—C28—C31119.5 (3)
N2—C9—C10131.0 (3)C30—C29—C28121.4 (3)
N3—C9—C10105.3 (3)C30—C29—H29A119.3
C11—C10—C15120.6 (3)C28—C29—H29A119.3
C11—C10—C9131.6 (3)C29—C30—C25119.5 (3)
C15—C10—C9107.6 (2)C29—C30—H30A120.3
C12—C11—C10117.9 (3)C25—C30—H30A120.3
C12—C11—H11A121.1O2—C31—C32120.7 (3)
C10—C11—H11A121.1O2—C31—C28120.2 (3)
C11—C12—C13121.2 (3)C32—C31—C28119.1 (3)
C11—C12—H12A119.4C31—C32—H32A109.5
C13—C12—H12A119.4C31—C32—H32B109.5
C14—C13—C12121.5 (3)H32A—C32—H32B109.5
C14—C13—H13A119.2C31—C32—H32C109.5
C12—C13—H13A119.2H32A—C32—H32C109.5
C13—C14—C15118.1 (3)H32B—C32—H32C109.5
C13—C14—H14A120.9O1—B1—N5118.0 (3)
C15—C14—H14A120.9O1—B1—N1117.1 (3)
C14—C15—C10120.6 (2)N5—B1—N1104.7 (3)
C14—C15—C16132.4 (3)O1—B1—N3107.7 (2)
C10—C15—C16107.0 (3)N5—B1—N3104.0 (3)
N4—C16—N3122.2 (2)N1—B1—N3103.8 (2)

Experimental details

Crystal data
Chemical formulaC32H19BN6O2
Mr530.34
Crystal system, space groupTriclinic, P1
Temperature (K)150
a, b, c (Å)10.5471 (8), 10.5786 (5), 11.5375 (9)
α, β, γ (°)77.446 (4), 88.817 (3), 83.966 (4)
V3)1249.54 (15)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.08 × 0.08 × 0.05
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
from symmetry-related measurements (SORTAV; Blessing, 1995)
Tmin, Tmax0.858, 1.002
No. of measured, independent and
observed [I > 2σ(I)] reflections
8602, 4273, 2393
Rint0.078
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.146, 0.98
No. of reflections4273
No. of parameters372
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.22

Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).

Selected bond lengths (Å) top
B1—O11.457 (4)B1—N31.494 (4)
B1—N11.487 (4)B1—N51.487 (4)
 

Acknowledgements

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

References

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First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationClaessens, C. G., González-Rodríguez, D., del Rey, B. & Torres, T. (2002). Chem. Rev. 102, 835–853.  Web of Science CrossRef PubMed CAS Google Scholar
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First citationPaton, A. S., Morse, G. E., Lough, A. J. & Bender, T. P. (2010). CrystEngComm, doi:10.1039/C0CE00599A.  Google Scholar
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First citationZyskowski, C. D. & Kennedy, V. O. (2000). J. Porphyrins Phthalocyanins, pp. 707–712.  Google Scholar

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