Bromido(dodecafluorosubphthalo-cyaninato)boron(III).

The title compound, C(24)BBrF(12)N(6) or Br-F(12)BsubPc (BsubPc is boronsubphtalocyanine), has a bowl-shaped structure with an approximate mol-ecular C(3v) symmetry characteristic of boronsubphthalocyanine compounds. In the crystal, mol-ecules are arranged in one-dimensional columns and the boron-subphthalocyanine units within each column are offset and angled in a bowl-to-ligand packing arrangement such that the axial Br atom rests in the aromatic concaved bowl of the neighboring subphthalocyanine with an inter-molecular Br⋯B distance of 3.721 (3) Å.

Related literature

For general background to boronsubphthalocyanines, see: Claessens et al. (2002 ▶). For examples of related halogenated boronsubphthalocyanines, see: Morse et al. (2010 ▶); Paton et al. (2010 ▶); Rodriguez-Morgade et al. (2008 ▶); Sharman & van Lier (2005 ▶); Ros-Lis et al. (2005 ▶); Fuduka et al. (2002 ▶); Claessens & Torres (2002 ▶). For applications of boronsubphthalocyanines in organic electronics, see: Mutolo et al. (2006 ▶); Gommans et al. (2007 ▶, 2009 ▶); Kumar et al. (2009 ▶); Ma et al. (2009a ▶,b ▶); Klaus et al. (2009 ▶); Chen et al. (2009 ▶, 2010 ▶); Díaz et al. (2007 ▶); Yasuda & Tsutsui (2007 ▶); Renshaw et al. (2010 ▶). For van der Waals radii, see: Bondi (1964 ▶).

Experimental

Crystal data

C24BBrF12N6

M = 691.02

Monoclinic,

a = 11.1681 (5) Å

b = 10.8858 (2) Å

c = 19.0664 (7) Å

β = 95.2270 (15)°

V = 2308.33 (14) Å3

Z = 4

Mo Kα radiation

μ = 1.91 mm−1

T = 150 K

0.14 × 0.14 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T min = 0.775, T max = 0.835

15166 measured reflections

5263 independent reflections

3728 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.109

S = 1.04

5263 reflections

397 parameters

Δρmax = 0.95 e Å−3

Δρmin = −0.41 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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810041863/nc2200sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041863/nc2200Isup2.hkl

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

C24BBrF12N6	F(000) = 1336
Mr = 691.02	Dx = 1.988 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 15166 reflections
a = 11.1681 (5) Å	θ = 2.6–27.5°
b = 10.8858 (2) Å	µ = 1.91 mm−1
c = 19.0664 (7) Å	T = 150 K
β = 95.2270 (15)°	Block, purple
V = 2308.33 (14) Å3	0.14 × 0.14 × 0.10 mm
Z = 4

Nonius KappaCCD diffractometer	5263 independent reflections
Radiation source: fine-focus sealed tube	3728 reflections with I > 2σ(I)
graphite	Rint = 0.046
Detector resolution: 9 pixels mm-1	θmax = 27.5°, θmin = 2.6°
φ scans and ω scans with κ offsets	h = −14→14
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −12→14
Tmin = 0.775, Tmax = 0.835	l = −21→24
15166 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.045	Secondary atom site location: difference Fourier map
wR(F2) = 0.109	w = 1/[σ2(Fo2) + (0.0553P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
5263 reflections	Δρmax = 0.95 e Å−3
397 parameters	Δρmin = −0.41 e Å−3

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 > 2σ(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.

	x	y	z	Uiso*/Ueq
Br1	0.54911 (3)	0.40086 (2)	0.211746 (16)	0.02854 (12)
F1	0.52166 (15)	0.13977 (15)	0.52612 (9)	0.0308 (4)
F2	0.31173 (16)	0.13286 (16)	0.58691 (9)	0.0335 (4)
F3	0.09951 (16)	0.16152 (16)	0.51060 (10)	0.0364 (5)
F4	0.08838 (15)	0.18422 (15)	0.36791 (9)	0.0302 (4)
F5	0.05945 (15)	0.06664 (17)	0.12934 (10)	0.0365 (4)
F6	0.04016 (16)	−0.11128 (16)	0.02786 (11)	0.0411 (5)
F7	0.23599 (17)	−0.19317 (16)	−0.02953 (10)	0.0401 (5)
F8	0.45774 (15)	−0.11084 (14)	0.01579 (9)	0.0282 (4)
F9	0.85617 (15)	−0.07367 (15)	0.13742 (10)	0.0326 (4)
F10	1.04672 (16)	−0.14952 (18)	0.22740 (11)	0.0444 (5)
F11	1.06140 (16)	−0.08814 (17)	0.36440 (11)	0.0442 (5)
F12	0.88979 (15)	0.05387 (16)	0.41661 (9)	0.0352 (4)
N1	0.4472 (2)	0.2141 (2)	0.30191 (12)	0.0218 (5)
N2	0.2545 (2)	0.1752 (2)	0.24173 (12)	0.0231 (5)
N3	0.4328 (2)	0.1592 (2)	0.18160 (13)	0.0217 (5)
N4	0.5946 (2)	0.0451 (2)	0.13988 (13)	0.0231 (5)
N5	0.6199 (2)	0.1505 (2)	0.24953 (12)	0.0213 (5)
N6	0.6238 (2)	0.1572 (2)	0.37443 (13)	0.0239 (6)
C1	0.5068 (3)	0.1882 (2)	0.36615 (16)	0.0235 (6)
C2	0.4140 (3)	0.1777 (2)	0.41463 (15)	0.0221 (6)
C3	0.4175 (3)	0.1550 (3)	0.48641 (16)	0.0243 (7)
C4	0.3113 (3)	0.1491 (3)	0.51729 (16)	0.0273 (7)
C5	0.2002 (3)	0.1616 (3)	0.47737 (17)	0.0271 (7)
C6	0.1951 (3)	0.1764 (2)	0.40552 (16)	0.0244 (7)
C7	0.3015 (3)	0.1865 (2)	0.37388 (16)	0.0235 (6)
C8	0.3254 (3)	0.1999 (2)	0.30061 (16)	0.0228 (6)
C9	0.3109 (3)	0.1472 (2)	0.18449 (15)	0.0220 (6)
C10	0.2697 (3)	0.0688 (3)	0.12508 (16)	0.0235 (6)
C11	0.1577 (3)	0.0248 (3)	0.10206 (16)	0.0283 (7)
C12	0.1472 (3)	−0.0642 (3)	0.05019 (17)	0.0313 (7)
C13	0.2494 (3)	−0.1071 (3)	0.02084 (16)	0.0278 (7)
C14	0.3619 (3)	−0.0637 (3)	0.04319 (15)	0.0249 (7)
C15	0.3744 (3)	0.0259 (2)	0.09517 (15)	0.0226 (6)
C16	0.4785 (3)	0.0802 (2)	0.13529 (15)	0.0222 (6)
C17	0.6618 (3)	0.0783 (2)	0.19883 (16)	0.0220 (6)
C18	0.7745 (3)	0.0277 (3)	0.23143 (16)	0.0247 (7)
C19	0.8630 (3)	−0.0444 (3)	0.20584 (17)	0.0276 (7)
C20	0.9576 (3)	−0.0830 (3)	0.25135 (19)	0.0326 (8)
C21	0.9660 (3)	−0.0509 (3)	0.32254 (19)	0.0324 (8)
C22	0.8793 (3)	0.0217 (3)	0.34902 (17)	0.0289 (7)
C23	0.7829 (3)	0.0615 (3)	0.30424 (16)	0.0238 (6)
C24	0.6767 (3)	0.1334 (2)	0.31523 (15)	0.0217 (6)
B1	0.5091 (3)	0.2236 (3)	0.23690 (17)	0.0218 (7)

	U11	U22	U33	U12	U13	U23
Br1	0.0370 (2)	0.02078 (17)	0.02777 (19)	−0.00196 (12)	0.00258 (14)	0.00042 (12)
F1	0.0324 (10)	0.0365 (9)	0.0229 (10)	−0.0030 (8)	−0.0018 (8)	0.0011 (7)
F2	0.0411 (11)	0.0404 (10)	0.0193 (10)	−0.0054 (8)	0.0048 (8)	0.0015 (8)
F3	0.0329 (11)	0.0457 (11)	0.0321 (11)	0.0009 (8)	0.0110 (9)	0.0040 (8)
F4	0.0243 (9)	0.0354 (9)	0.0303 (11)	−0.0009 (7)	0.0001 (8)	0.0015 (8)
F5	0.0243 (10)	0.0496 (11)	0.0353 (12)	−0.0035 (8)	0.0017 (8)	−0.0064 (8)
F6	0.0304 (11)	0.0470 (11)	0.0444 (13)	−0.0118 (8)	−0.0053 (9)	−0.0094 (9)
F7	0.0447 (12)	0.0381 (10)	0.0365 (12)	−0.0062 (9)	−0.0024 (9)	−0.0156 (8)
F8	0.0346 (10)	0.0264 (9)	0.0236 (10)	0.0017 (7)	0.0036 (8)	−0.0040 (7)
F9	0.0291 (10)	0.0351 (10)	0.0338 (11)	0.0012 (8)	0.0037 (8)	−0.0094 (8)
F10	0.0286 (11)	0.0462 (11)	0.0576 (14)	0.0126 (9)	−0.0004 (10)	−0.0105 (10)
F11	0.0279 (11)	0.0512 (12)	0.0510 (14)	0.0107 (8)	−0.0102 (9)	0.0040 (9)
F12	0.0326 (10)	0.0442 (10)	0.0273 (11)	−0.0021 (8)	−0.0053 (8)	0.0045 (8)
N1	0.0225 (13)	0.0217 (12)	0.0210 (14)	0.0004 (10)	0.0008 (11)	−0.0024 (10)
N2	0.0247 (13)	0.0254 (12)	0.0188 (14)	0.0037 (10)	−0.0004 (11)	−0.0002 (10)
N3	0.0232 (13)	0.0215 (12)	0.0202 (14)	0.0014 (10)	0.0006 (10)	0.0022 (10)
N4	0.0248 (14)	0.0243 (12)	0.0203 (14)	−0.0022 (10)	0.0023 (11)	0.0015 (10)
N5	0.0246 (13)	0.0202 (12)	0.0189 (14)	−0.0022 (10)	0.0012 (11)	−0.0009 (10)
N6	0.0256 (14)	0.0233 (12)	0.0222 (14)	−0.0037 (11)	−0.0020 (11)	−0.0007 (10)
C1	0.0260 (16)	0.0182 (14)	0.0255 (17)	−0.0012 (12)	−0.0028 (13)	−0.0034 (12)
C2	0.0242 (16)	0.0216 (14)	0.0199 (16)	−0.0020 (12)	−0.0012 (13)	−0.0027 (11)
C3	0.0282 (17)	0.0226 (15)	0.0214 (17)	−0.0018 (13)	−0.0015 (13)	−0.0011 (12)
C4	0.0376 (19)	0.0230 (15)	0.0214 (17)	−0.0028 (14)	0.0037 (14)	−0.0005 (12)
C5	0.0289 (18)	0.0252 (16)	0.0283 (19)	0.0019 (13)	0.0099 (14)	0.0014 (13)
C6	0.0230 (16)	0.0222 (14)	0.0278 (18)	−0.0021 (12)	0.0016 (13)	−0.0003 (12)
C7	0.0285 (17)	0.0196 (14)	0.0222 (17)	−0.0010 (12)	0.0018 (13)	−0.0006 (12)
C8	0.0242 (16)	0.0209 (14)	0.0233 (17)	0.0034 (12)	0.0014 (13)	−0.0001 (12)
C9	0.0238 (16)	0.0194 (14)	0.0219 (17)	0.0013 (12)	−0.0032 (13)	0.0036 (12)
C10	0.0266 (16)	0.0231 (14)	0.0203 (16)	−0.0016 (13)	−0.0008 (13)	0.0003 (12)
C11	0.0257 (17)	0.0353 (17)	0.0236 (17)	−0.0001 (14)	0.0013 (14)	0.0004 (13)
C12	0.0256 (17)	0.0362 (17)	0.0303 (19)	−0.0081 (14)	−0.0071 (14)	0.0009 (14)
C13	0.0371 (19)	0.0246 (15)	0.0205 (17)	−0.0043 (13)	−0.0031 (14)	−0.0041 (12)
C14	0.0323 (18)	0.0235 (15)	0.0191 (16)	0.0017 (13)	0.0029 (14)	0.0008 (12)
C15	0.0273 (16)	0.0220 (14)	0.0181 (16)	0.0010 (12)	0.0002 (13)	0.0045 (11)
C16	0.0266 (16)	0.0218 (14)	0.0178 (16)	−0.0029 (12)	0.0005 (12)	0.0016 (11)
C17	0.0235 (16)	0.0219 (14)	0.0212 (16)	−0.0039 (12)	0.0047 (13)	0.0008 (12)
C18	0.0221 (16)	0.0219 (14)	0.0297 (18)	−0.0029 (12)	0.0003 (13)	0.0009 (12)
C19	0.0267 (17)	0.0234 (15)	0.033 (2)	−0.0043 (13)	0.0036 (14)	−0.0020 (13)
C20	0.0219 (17)	0.0312 (17)	0.045 (2)	0.0007 (14)	0.0031 (15)	−0.0010 (15)
C21	0.0225 (17)	0.0321 (17)	0.040 (2)	0.0007 (14)	−0.0077 (15)	0.0032 (15)
C22	0.0286 (18)	0.0299 (16)	0.0277 (19)	−0.0057 (14)	−0.0012 (14)	0.0029 (13)
C23	0.0212 (16)	0.0244 (14)	0.0257 (17)	−0.0030 (12)	0.0023 (13)	0.0040 (12)
C24	0.0237 (16)	0.0203 (14)	0.0205 (17)	−0.0050 (12)	−0.0012 (13)	0.0004 (12)
B1	0.0264 (18)	0.0197 (16)	0.0189 (18)	−0.0035 (14)	−0.0007 (15)	0.0001 (13)

Br1—B1	2.047 (3)	N6—C1	1.345 (4)
F1—C3	1.339 (3)	N6—C24	1.346 (4)
F2—C4	1.339 (3)	C1—C2	1.454 (4)
F3—C5	1.340 (3)	C2—C3	1.388 (4)
F4—C6	1.336 (3)	C2—C7	1.419 (4)
F5—C11	1.337 (3)	C3—C4	1.373 (4)
F6—C12	1.334 (3)	C4—C5	1.402 (4)
F7—C13	1.340 (3)	C5—C6	1.376 (4)
F8—C14	1.336 (3)	C6—C7	1.385 (4)
F9—C19	1.338 (4)	C7—C8	1.454 (4)
F10—C20	1.344 (4)	C9—C10	1.459 (4)
F11—C21	1.335 (4)	C10—C11	1.373 (4)
F12—C22	1.330 (3)	C10—C15	1.425 (4)
N1—C8	1.366 (4)	C11—C12	1.381 (4)
N1—C1	1.369 (4)	C12—C13	1.397 (4)
N1—B1	1.477 (4)	C13—C14	1.373 (4)
N2—C8	1.341 (4)	C14—C15	1.388 (4)
N2—C9	1.344 (4)	C15—C16	1.458 (4)
N3—C16	1.365 (4)	C17—C18	1.460 (4)
N3—C9	1.373 (4)	C18—C19	1.385 (4)
N3—B1	1.472 (4)	C18—C23	1.431 (4)
N4—C17	1.343 (4)	C19—C20	1.371 (4)
N4—C16	1.347 (4)	C20—C21	1.396 (5)
N5—C17	1.361 (4)	C21—C22	1.381 (4)
N5—C24	1.364 (4)	C22—C23	1.382 (4)
N5—B1	1.472 (4)	C23—C24	1.451 (4)
C8—N1—C1	113.3 (2)	F6—C12—C11	120.9 (3)
C8—N1—B1	122.3 (3)	F6—C12—C13	119.0 (3)
C1—N1—B1	122.6 (2)	C11—C12—C13	120.1 (3)
C8—N2—C9	116.1 (2)	F7—C13—C14	120.1 (3)
C16—N3—C9	113.4 (2)	F7—C13—C12	118.6 (3)
C16—N3—B1	122.5 (2)	C14—C13—C12	121.2 (3)
C9—N3—B1	121.9 (2)	F8—C14—C13	119.3 (3)
C17—N4—C16	116.0 (2)	F8—C14—C15	121.1 (3)
C17—N5—C24	114.3 (2)	C13—C14—C15	119.5 (3)
C17—N5—B1	122.3 (2)	C14—C15—C10	118.9 (3)
C24—N5—B1	122.5 (2)	C14—C15—C16	133.1 (3)
C1—N6—C24	116.5 (2)	C10—C15—C16	107.5 (2)
N6—C1—N1	123.0 (3)	N4—C16—N3	123.5 (3)
N6—C1—C2	130.3 (3)	N4—C16—C15	129.5 (3)
N1—C1—C2	105.6 (2)	N3—C16—C15	105.5 (2)
C3—C2—C7	119.7 (3)	N4—C17—N5	123.2 (3)
C3—C2—C1	133.1 (3)	N4—C17—C18	130.5 (3)
C7—C2—C1	107.1 (3)	N5—C17—C18	104.7 (2)
F1—C3—C4	119.4 (3)	C19—C18—C23	120.1 (3)
F1—C3—C2	121.6 (3)	C19—C18—C17	132.8 (3)
C4—C3—C2	118.9 (3)	C23—C18—C17	107.1 (2)
F2—C4—C3	120.4 (3)	F9—C19—C20	121.0 (3)
F2—C4—C5	118.3 (3)	F9—C19—C18	120.0 (3)
C3—C4—C5	121.3 (3)	C20—C19—C18	119.0 (3)
F3—C5—C6	120.7 (3)	F10—C20—C19	120.2 (3)
F3—C5—C4	118.9 (3)	F10—C20—C21	118.6 (3)
C6—C5—C4	120.5 (3)	C19—C20—C21	121.2 (3)
F4—C6—C5	119.8 (3)	F11—C21—C22	120.2 (3)
F4—C6—C7	121.3 (3)	F11—C21—C20	119.0 (3)
C5—C6—C7	118.9 (3)	C22—C21—C20	120.8 (3)
C6—C7—C2	120.6 (3)	F12—C22—C21	120.1 (3)
C6—C7—C8	131.8 (3)	F12—C22—C23	120.7 (3)
C2—C7—C8	107.5 (2)	C21—C22—C23	119.1 (3)
N2—C8—N1	123.3 (3)	C22—C23—C18	119.8 (3)
N2—C8—C7	129.6 (3)	C22—C23—C24	132.9 (3)
N1—C8—C7	105.3 (3)	C18—C23—C24	107.3 (3)
N2—C9—N3	123.4 (3)	N6—C24—N5	122.7 (3)
N2—C9—C10	128.6 (3)	N6—C24—C23	130.7 (3)
N3—C9—C10	105.6 (2)	N5—C24—C23	105.0 (2)
C11—C10—C15	120.9 (3)	N3—B1—N5	106.4 (2)
C11—C10—C9	131.8 (3)	N3—B1—N1	106.4 (2)
C15—C10—C9	106.9 (2)	N5—B1—N1	106.0 (2)
F5—C11—C10	120.9 (3)	N3—B1—Br1	113.9 (2)
F5—C11—C12	119.9 (3)	N5—B1—Br1	110.5 (2)
C10—C11—C12	119.3 (3)	N1—B1—Br1	113.1 (2)