organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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4,4-Di­fluoro-1,3,5,7-tetra­methyl-8-penta­fluoro­phenyl-4-bora-3a,4a-di­aza-s-indacene

aCollege of Transportation, Southeast University, Nanjing 210096, People's Republic of China
*Correspondence e-mail: xfzhouphy@263.net

(Received 4 January 2010; accepted 29 January 2010; online 6 March 2010)

In the title dye compound, C19H14BF7N2, the boron–dipyrromethene core lies on a crystallographic mirror plane which bis­ects the BF2 and penta­fluoro­phenyl groups. The dihedral angle between the penta­fluoro­phenyl ring and the tricyclic system is thus 90° by symmetry. The sp3-hybridized B atom has a slightly distorted tetra­hedral coordination.

Related literature

For boron–dipyrromethene (BODIPY) dyes, see: Bergström et al. (2002[Bergström, F., Mikhalyov, I., Hägglöf, P., Wortmann, R., Ny, T. & Johansson, L. B.-Å. (2002). J. Am. Chem. Soc. 124, 196-204.]); Trieflinger et al. (2005[Trieflinger, C., Rurack, K. & Daub, J. (2005). Angew. Chem. Int. Ed. 44, 2288-2291.]). For geometrical parameters in other BODIPY-based compounds, see: Picou et al.(1990[Picou, C. L., Stevens, E. D., Shah, M. & Boyer, J. H. (1990). Acta Cryst. C46, 1148-1150.]); Wang et al.(2007[Wang, D.-C., He, C., Fan, J.-L., Huang, W.-W. & Peng, X.-J. (2007). Acta Cryst. E63, o2900.]); Kuhn et al. (1990[Kuhn, N., Kuhn, A., Speis, M., Bläser, D. & Böse, R. (1990). Chem. Ber. 123, 1301-1306.]).

[Scheme 1]

Experimental

Crystal data
  • C19H14BF7N2

  • Mr = 414.13

  • Monoclinic, C 2/m

  • a = 12.4060 (5) Å

  • b = 7.5490 (9) Å

  • c = 19.720 (3) Å

  • β = 97.12 (2)°

  • V = 1832.6 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.14 mm−1

  • T = 293 K

  • 0.2 × 0.2 × 0.2 mm

Data collection
  • Rigaku SCXmini diffractometer

  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.973, Tmax = 0.979

  • 8232 measured reflections

  • 1936 independent reflections

  • 1585 reflections with I > 2σ(I)

  • Rint = 0.032

Refinement
  • R[F2 > 2σ(F2)] = 0.056

  • wR(F2) = 0.162

  • S = 1.06

  • 1936 reflections

  • 170 parameters

  • H-atom parameters constrained

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.23 e Å−3

Data collection: CrystalClear (Rigaku, 2005[Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Boron-dipyrromethene (BODIPY) dyes are excellent and famous fluorophores, with a high molar extinction coefficient and high fluorescence quantum yield, which have recently received considerable attention with regard to the design of fluorescence labels and biomolecular sensors (Bergström et al., 2002; Trieflinger et al., 2005). Here, the synthesis and the crystal structure of the title compound are reported. The observed geometric parameters are generally comparable with the reported values for other BODIPY-based compounds (Picou et al., 1990; Wang et al., 2007).

As shown in Fig. 1, the BODIPY skeleton of the molecule, which is formed from three fused heterocyclic rings, is planar, as this system lies on a mirror plane. The sp3-hybridized B centre appears as a slightly distorted tetrahedron, with N—B—N and F—B—F angles of 107.5 (2) and 109.8 (3)°. The two B—N distances are almost identical, implying the usual delocalization of the positive charge. The average bond lengths for B—N and B—F and the average N—B—N, F—B—F and F—B—N bond angles indicate a tetrahedral BF2N2 configuration and are in good agreement with previous published data (Kuhn, et al., 1990; Picou et al., 1990; Wang et al., 2007). No unusual values are observed in the molecular structure. Perhaps due to the steric repulsion from the C11 and C13 methyl groups, the pentafluorophenyl ring is perpendicular to the BODIPY ring plane, with a dihedral angle constrained by symmetry to be 90°.

Related literature top

For boron–dipyrromethene (BODIPY) dyes, see: Bergström et al. (2002); Trieflinger et al. (2005). For geometrical parameters in other BODIPY-based compounds, see: Picou et al.(1990); Wang et al.(2007); Kuhn et al. (1990).

Experimental top

Pentafluorobenzaldehyde (2 mmol) and 2,4-dimethyl-1H-pyrrole (4 mmol) were dissolved in 50 ml of dry CH2Cl2 under an Ar atmosphere. One drop of trifluoroacetic acid (TFA) was added, and the solution was stirred at room temperature overnight. Thin layer chromatography (TLC) monitoring (silica; CH2Cl2) showed complete consumption of the aldehyde. At this point, a solution of dichlorodicyanobenzoquinone (DDQ, 2 mmol) in dry CH2Cl2 (20 ml) was added, and the mixture was stirred for additional 15 min. The reaction mixture was then treated with N,N-diisopropylethylamine (DIEA, 3 ml) and boron trifluoride etherate (3 ml). After stirring for another 30 min, the dark brown solution was washed with water (3×50 ml) and brine (50 ml), dried over Na2SO4, and concentrated under reduced pressure. The crude product was purified by silica-gel flash column chromatography and recrystallization from CHCl3/hexane. Single crystals suitable for X-ray analysis were obtained from an acetonitrile solution by slow evaporation.

Refinement top

Positional parameters of all the H atoms were calculated geometrically and were allowed to ride on the C atoms to which they are bonded. Isotropic displacement parameters for H atoms were refined.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level. 'A' labeled atoms are generated by symmetry code x, 1-y, z.
4,4-Difluoro-1,3,5,7-tetramethyl-8-pentafluorophenyl-4-bora-3a,4a-diaza- s-indacene top
Crystal data top
C19H14BF7N2F(000) = 840
Mr = 414.13Dx = 1.501 Mg m3
Monoclinic, C2/mMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 2191 reflections
a = 12.4060 (5) Åθ = 3.1–27.5°
b = 7.5490 (9) ŵ = 0.14 mm1
c = 19.720 (3) ÅT = 293 K
β = 97.12 (2)°Prism, red
V = 1832.6 (4) Å30.2 × 0.2 × 0.2 mm
Z = 4
Data collection top
Rigaku SCXmini
diffractometer
1936 independent reflections
Radiation source: fine-focus sealed tube1585 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 13.6612 pixels mm-1θmax = 26.0°, θmin = 3.1°
ω scansh = 1515
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
k = 99
Tmin = 0.973, Tmax = 0.979l = 2424
8232 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.091P)2 + 0.8854P]
where P = (Fo2 + 2Fc2)/3
1936 reflections(Δ/σ)max < 0.001
170 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.23 e Å3
0 constraints
Crystal data top
C19H14BF7N2V = 1832.6 (4) Å3
Mr = 414.13Z = 4
Monoclinic, C2/mMo Kα radiation
a = 12.4060 (5) ŵ = 0.14 mm1
b = 7.5490 (9) ÅT = 293 K
c = 19.720 (3) Å0.2 × 0.2 × 0.2 mm
β = 97.12 (2)°
Data collection top
Rigaku SCXmini
diffractometer
1936 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
1585 reflections with I > 2σ(I)
Tmin = 0.973, Tmax = 0.979Rint = 0.032
8232 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.162H-atom parameters constrained
S = 1.06Δρmax = 0.24 e Å3
1936 reflectionsΔρmin = 0.23 e Å3
170 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
F10.12945 (15)0.3502 (3)0.07469 (8)0.1040 (7)
F30.28302 (13)0.18847 (16)0.34101 (7)0.0721 (5)
F40.35839 (14)0.1888 (2)0.47541 (8)0.0928 (6)
F50.39356 (18)0.50000.54333 (9)0.0988 (9)
N10.08602 (19)0.50000.17499 (11)0.0486 (6)
N20.2747 (2)0.50000.14360 (11)0.0523 (6)
C10.0234 (2)0.50000.17144 (15)0.0564 (7)
C20.0523 (2)0.50000.23784 (16)0.0597 (8)
H2A0.12290.50000.24900.104 (14)*
C30.0406 (2)0.50000.28399 (14)0.0489 (7)
C40.1291 (2)0.50000.24405 (12)0.0446 (6)
C50.2418 (2)0.50000.26194 (12)0.0422 (6)
C60.3151 (2)0.50000.21363 (13)0.0475 (6)
C70.4316 (2)0.50000.21939 (16)0.0563 (7)
C80.4565 (3)0.50000.15330 (17)0.0682 (9)
H8A0.52630.50000.14080.080 (11)*
C90.3606 (3)0.50000.10769 (15)0.0627 (8)
C100.0981 (3)0.50000.10532 (18)0.0783 (11)
H10A0.05590.50000.06770.16 (2)*
H10B0.14300.60380.10310.23 (3)*
C110.0428 (3)0.50000.36050 (15)0.0629 (9)
H11A0.03020.50000.37190.079 (11)*
H11B0.08010.60380.37920.093 (9)*
C120.3492 (4)0.50000.03121 (18)0.0875 (13)
H12A0.27350.50000.01350.25 (4)*
H12B0.38330.39620.01560.172 (19)*
C130.5127 (3)0.50000.28225 (19)0.0693 (9)
H13A0.58470.50000.26930.126 (17)*
H13B0.50270.39620.30890.129 (13)*
C140.2846 (2)0.50000.33641 (13)0.0425 (6)
C150.30342 (16)0.3443 (3)0.37278 (10)0.0490 (5)
C160.34105 (17)0.3429 (3)0.44160 (11)0.0602 (6)
C170.3592 (2)0.50000.47584 (15)0.0638 (9)
B10.1532 (3)0.50000.11399 (17)0.0612 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0923 (11)0.1505 (17)0.0710 (10)0.0214 (11)0.0177 (8)0.0597 (10)
F30.0976 (11)0.0457 (7)0.0730 (9)0.0076 (7)0.0110 (7)0.0018 (6)
F40.1028 (12)0.1033 (12)0.0732 (10)0.0309 (10)0.0147 (8)0.0448 (9)
F50.0785 (14)0.177 (3)0.0379 (10)0.0000.0059 (9)0.000
N10.0560 (13)0.0546 (13)0.0346 (11)0.0000.0027 (9)0.000
N20.0601 (14)0.0615 (14)0.0377 (12)0.0000.0155 (10)0.000
C10.0547 (17)0.0633 (18)0.0491 (16)0.0000.0017 (12)0.000
C20.0491 (16)0.079 (2)0.0516 (16)0.0000.0085 (13)0.000
C30.0495 (15)0.0576 (16)0.0405 (14)0.0000.0086 (11)0.000
C40.0520 (15)0.0477 (14)0.0337 (12)0.0000.0041 (10)0.000
C50.0507 (14)0.0386 (13)0.0380 (13)0.0000.0081 (11)0.000
C60.0535 (15)0.0490 (15)0.0408 (14)0.0000.0089 (11)0.000
C70.0541 (16)0.0601 (17)0.0570 (17)0.0000.0157 (13)0.000
C80.0590 (19)0.087 (2)0.064 (2)0.0000.0271 (16)0.000
C90.075 (2)0.071 (2)0.0468 (16)0.0000.0246 (15)0.000
C100.069 (2)0.108 (3)0.0514 (19)0.0000.0157 (16)0.000
C110.0517 (16)0.095 (3)0.0437 (15)0.0000.0130 (13)0.000
C120.099 (3)0.121 (4)0.0486 (19)0.0000.033 (2)0.000
C130.0507 (17)0.088 (3)0.069 (2)0.0000.0068 (15)0.000
C140.0428 (13)0.0479 (14)0.0375 (13)0.0000.0077 (10)0.000
C150.0507 (10)0.0498 (11)0.0474 (10)0.0060 (9)0.0099 (8)0.0030 (8)
C160.0533 (11)0.0795 (16)0.0488 (11)0.0128 (11)0.0104 (9)0.0208 (11)
C170.0490 (16)0.104 (3)0.0380 (14)0.0000.0051 (12)0.000
B10.068 (2)0.082 (2)0.0346 (15)0.0000.0083 (14)0.000
Geometric parameters (Å, º) top
B1—F11.382 (3)C7—C81.376 (4)
B1—N11.546 (4)C7—C131.497 (5)
B1—N21.548 (5)C8—C91.400 (5)
F3—C151.342 (3)C8—H8A0.9301
F4—C161.345 (3)C9—C121.497 (4)
F5—C171.346 (3)C10—H10A0.9598
N1—C11.350 (4)C10—H10B0.9600
N1—C41.400 (3)C11—H11A0.9601
N2—C91.350 (4)C11—H11B0.9600
N2—C61.409 (4)C12—H12A0.9600
C1—C21.400 (4)C12—H12B0.9601
C1—C101.503 (4)C13—H13A0.9600
C2—C31.377 (4)C13—H13B0.9600
C2—H2A0.9298C14—C151.382 (2)
C3—C41.428 (4)C14—C15i1.382 (2)
C3—C111.506 (4)C15—C161.379 (3)
C4—C51.398 (4)C16—C171.370 (3)
C5—C61.397 (4)C17—C16i1.370 (3)
C5—C141.498 (3)B1—F1i1.382 (3)
C6—C71.435 (4)
C1—N1—C4108.1 (2)C8—C9—C12127.9 (3)
C1—N1—B1126.5 (2)C1—C10—H10A109.6
C4—N1—B1125.4 (2)C1—C10—H10B109.4
C9—N2—C6107.8 (3)H10A—C10—H10B109.5
C9—N2—B1126.6 (3)C3—C11—H11A109.5
C6—N2—B1125.5 (2)C3—C11—H11B109.5
N1—C1—C2108.9 (3)H11A—C11—H11B109.5
N1—C1—C10123.6 (3)C9—C12—H12A109.5
C2—C1—C10127.6 (3)C9—C12—H12B109.5
C3—C2—C1109.2 (3)H12A—C12—H12B109.5
C3—C2—H2A125.5C7—C13—H13A109.4
C1—C2—H2A125.4C7—C13—H13B109.5
C2—C3—C4105.8 (2)H13A—C13—H13B109.5
C2—C3—C11124.9 (3)C15—C14—C15i116.6 (2)
C4—C3—C11129.2 (3)C15—C14—C5121.69 (13)
N1—C4—C5119.6 (2)C15i—C14—C5121.69 (13)
N1—C4—C3108.0 (2)F3—C15—C14119.56 (18)
C5—C4—C3132.3 (2)F3—C15—C16118.27 (19)
C6—C5—C4122.9 (2)C14—C15—C16122.2 (2)
C6—C5—C14119.1 (2)F4—C16—C17119.9 (2)
C4—C5—C14118.0 (2)F4—C16—C15120.6 (2)
C5—C6—N2119.1 (2)C17—C16—C15119.5 (2)
C5—C6—C7132.9 (3)F5—C17—C16119.99 (14)
N2—C6—C7108.0 (2)F5—C17—C16i119.99 (14)
C8—C7—C6105.5 (3)C16—C17—C16i120.0 (3)
C8—C7—C13125.3 (3)F1—B1—F1i109.8 (3)
C6—C7—C13129.2 (3)N1—B1—N2107.5 (2)
C7—C8—C9109.6 (3)F1—B1—N1109.8 (2)
C7—C8—H8A125.2F1i—B1—N1109.8 (2)
C9—C8—H8A125.1F1—B1—N2110.0 (2)
N2—C9—C8109.0 (3)F1i—B1—N2110.0 (2)
N2—C9—C12123.1 (3)
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC19H14BF7N2
Mr414.13
Crystal system, space groupMonoclinic, C2/m
Temperature (K)293
a, b, c (Å)12.4060 (5), 7.5490 (9), 19.720 (3)
β (°) 97.12 (2)
V3)1832.6 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.14
Crystal size (mm)0.2 × 0.2 × 0.2
Data collection
DiffractometerRigaku SCXmini
diffractometer
Absorption correctionMulti-scan
(CrystalClear; Rigaku, 2005)
Tmin, Tmax0.973, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
8232, 1936, 1585
Rint0.032
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.162, 1.06
No. of reflections1936
No. of parameters170
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.24, 0.23

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
B1—F11.382 (3)B1—N21.548 (5)
B1—N11.546 (4)
F1—B1—F1i109.8 (3)F1i—B1—N1109.8 (2)
N1—B1—N2107.5 (2)F1—B1—N2110.0 (2)
F1—B1—N1109.8 (2)F1i—B1—N2110.0 (2)
Symmetry code: (i) x, y+1, z.
 

Footnotes

Other affiliations: Department of Physics, Southeast University, Nanjing 210096, People's Republic of China, and Department of Fundamental Sciences, Yancheng Institute of Technology, Yancheng 224003, People's Republic of China.

Acknowledgements

This work is supported by Jiangsu Province Innovation (project No. CX07B-032z) and the Scientific Research Foundation of the Graduate School of Southeast University.

References

First citationBergström, F., Mikhalyov, I., Hägglöf, P., Wortmann, R., Ny, T. & Johansson, L. B.-Å. (2002). J. Am. Chem. Soc. 124, 196–204.  Web of Science PubMed Google Scholar
First citationKuhn, N., Kuhn, A., Speis, M., Bläser, D. & Böse, R. (1990). Chem. Ber. 123, 1301–1306.  CrossRef CAS Web of Science Google Scholar
First citationPicou, C. L., Stevens, E. D., Shah, M. & Boyer, J. H. (1990). Acta Cryst. C46, 1148–1150.  CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationRigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationTrieflinger, C., Rurack, K. & Daub, J. (2005). Angew. Chem. Int. Ed. 44, 2288–2291.  Web of Science CrossRef CAS Google Scholar
First citationWang, D.-C., He, C., Fan, J.-L., Huang, W.-W. & Peng, X.-J. (2007). Acta Cryst. E63, o2900.  Web of Science CSD CrossRef IUCr Journals Google Scholar

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