


Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810041863/nc2200sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536810041863/nc2200Isup2.hkl |
CCDC reference: 803080
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean
(C-C) = 0.005 Å
- R factor = 0.045
- wR factor = 0.109
- Data-to-parameter ratio = 13.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.30 PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 3 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 2 PLAT040_ALERT_1_C No H-atoms in this Carbon Containing Compound .. ? PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 39
Alert level G PLAT431_ALERT_2_G Short Inter HL..A Contact F3 .. F12 .. 2.72 Ang. PLAT431_ALERT_2_G Short Inter HL..A Contact F4 .. F9 .. 2.71 Ang. PLAT431_ALERT_2_G Short Inter HL..A Contact F5 .. F9 .. 2.75 Ang. PLAT431_ALERT_2_G Short Inter HL..A Contact F6 .. F6 .. 2.76 Ang. PLAT431_ALERT_2_G Short Inter HL..A Contact F8 .. F8 .. 2.68 Ang. PLAT432_ALERT_2_G Short Inter X...Y Contact F4 .. C22 .. 2.93 Ang. PLAT432_ALERT_2_G Short Inter X...Y Contact F8 .. C3 .. 2.91 Ang. PLAT432_ALERT_2_G Short Inter X...Y Contact F8 .. C2 .. 2.96 Ang. PLAT432_ALERT_2_G Short Inter X...Y Contact F9 .. C6 .. 2.88 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 9 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 10 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Br-F12BsubPc was synthesized as previously reported (Morse et al. 2010). Single crystals suitable for X-ray diffraction were prepared by slow vapour diffusion of heptane into a solution of Br-F12BsubPc in benzene.
Boronsubphthalocyanine (BsubPc), a lower analogue of phthalocyanine, is of interest to researchers in the field of organic electronics (Morse et al., 2010; Mutolo et al. 2006; Gommans et al. 2007; Gommans et al. 2009; Kumar et al. 2009; Ma et al. 2009a; Klaus et al. 2009; Ma et al. 2009b; Chen et al. 2010; Chen et al. 2009; Díaz et al. 2007; Yasuda et al. 2007; and Renshaw et al. 2010). We have synthesized the title compound as it is a precursor to fluorinated phenoxy-BsubPcs (Morse et al. 2010; Paton et al. 2010). The molecular structure of the title compound is shown in Fig. 1. In the crystal structure the molecules are arranged in a concave bowl to ligand motif similar to those of F-F12BsubPc (Rodriguez-Morgade et al. 2008) and Cl-F12BsubPc (Fuduka et al. 2002) whereby the axial halogen atom lies within the concaved face of the BsubPc molecular fragment in close proximately to the boron atom. The net effect is the formation of distinctive columns throughout the crystal structure (Fig. 2). In this arrangment the intermolecular bromine to nitrogen distances are 3.420 (2), 3.466 (2), and 3.427 (2) Å which are close to the sum of the van der Waals radii at 3.40 Å (1.85 Å[Br]+1.55 Å[N]). The distance between Br1 and B1(1 - x, y + 1/2, -z + 1/2) is 3.721 (3) Å which is less the sum of the van der Waals radii at 3.85 Å (1.85 Å[Br]+2.0 Å[B]). The axial boron-bromine bond is oriented towards the inner 5-membered ring of the nieghboring BsubPc unit. This interaction occurs at a distance of 3.471 Å, less than the sum of the van der Waals raddi at 3.55Å (1.85 Å[Br]+1.70 Å[C]). The other two 5-membered rings are seperated from the bromine atom by a distance of 3.572 Å and 3.518 Å, near the sum of the respective van der Waals radii. Neighboring BsubPc units are separated by a B···B distance of 5.471 (5) Å. All van der Waals radii were calculated using the values determined by Bondi (1964).
For general background to boronsubphthalocyanines, see Claessens et al. (2002a). For examples of related halogenated boronsubphthalocyanines, see: Morse et al. (2010); Paton et al. (2010); Rodriguez-Morgade et al. (2008); Sharman et al. (2005); Ros-Lis et al. (2005); Fuduka et al. (2002); Claessens et al. (2002b). 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 et al. (2007); Renshaw et al. (2010). For van der Waals radii, see: Bondi (1964).
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) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![]() | Fig. 1. The molecular structure of the title compound with 30% probability ellipsoids. |
![]() | Fig. 2. Part of the crystal structure of the title compound. |
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 monochromator | 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 |
C24BBrF12N6 | V = 2308.33 (14) Å3 |
Mr = 691.02 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.1681 (5) Å | µ = 1.91 mm−1 |
b = 10.8858 (2) Å | T = 150 K |
c = 19.0664 (7) Å | 0.14 × 0.14 × 0.10 mm |
β = 95.2270 (15)° |
Nonius KappaCCD diffractometer | 5263 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 3728 reflections with I > 2σ(I) |
Tmin = 0.775, Tmax = 0.835 | Rint = 0.046 |
15166 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 397 parameters |
wR(F2) = 0.109 | 0 restraints |
S = 1.04 | Δρmax = 0.95 e Å−3 |
5263 reflections | 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) |
Experimental details
Crystal data | |
Chemical formula | C24BBrF12N6 |
Mr | 691.02 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 11.1681 (5), 10.8858 (2), 19.0664 (7) |
β (°) | 95.2270 (15) |
V (Å3) | 2308.33 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.91 |
Crystal size (mm) | 0.14 × 0.14 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.775, 0.835 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15166, 5263, 3728 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.109, 1.04 |
No. of reflections | 5263 |
No. of parameters | 397 |
Δρmax, Δρmin (e Å−3) | 0.95, −0.41 |
Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).
Boronsubphthalocyanine (BsubPc), a lower analogue of phthalocyanine, is of interest to researchers in the field of organic electronics (Morse et al., 2010; Mutolo et al. 2006; Gommans et al. 2007; Gommans et al. 2009; Kumar et al. 2009; Ma et al. 2009a; Klaus et al. 2009; Ma et al. 2009b; Chen et al. 2010; Chen et al. 2009; Díaz et al. 2007; Yasuda et al. 2007; and Renshaw et al. 2010). We have synthesized the title compound as it is a precursor to fluorinated phenoxy-BsubPcs (Morse et al. 2010; Paton et al. 2010). The molecular structure of the title compound is shown in Fig. 1. In the crystal structure the molecules are arranged in a concave bowl to ligand motif similar to those of F-F12BsubPc (Rodriguez-Morgade et al. 2008) and Cl-F12BsubPc (Fuduka et al. 2002) whereby the axial halogen atom lies within the concaved face of the BsubPc molecular fragment in close proximately to the boron atom. The net effect is the formation of distinctive columns throughout the crystal structure (Fig. 2). In this arrangment the intermolecular bromine to nitrogen distances are 3.420 (2), 3.466 (2), and 3.427 (2) Å which are close to the sum of the van der Waals radii at 3.40 Å (1.85 Å[Br]+1.55 Å[N]). The distance between Br1 and B1(1 - x, y + 1/2, -z + 1/2) is 3.721 (3) Å which is less the sum of the van der Waals radii at 3.85 Å (1.85 Å[Br]+2.0 Å[B]). The axial boron-bromine bond is oriented towards the inner 5-membered ring of the nieghboring BsubPc unit. This interaction occurs at a distance of 3.471 Å, less than the sum of the van der Waals raddi at 3.55Å (1.85 Å[Br]+1.70 Å[C]). The other two 5-membered rings are seperated from the bromine atom by a distance of 3.572 Å and 3.518 Å, near the sum of the respective van der Waals radii. Neighboring BsubPc units are separated by a B···B distance of 5.471 (5) Å. All van der Waals radii were calculated using the values determined by Bondi (1964).