12-Di­methyl­amino-2,2-di­fluoro-8-phenyl-1λ5,3-di­aza-2λ4-boratri­cyclo­[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaen-1-ylium

Zhao-Yun Wang

doi:10.1107/S1600536813010404

. 2013 Apr 24;69(Pt 5):o781. doi: 10.1107/S1600536813010404

12-Dimethylamino-2,2-difluoro-8-phenyl-1λ⁵,3-diaza-2λ⁴-boratricyclo[7.3.0.0^3,7]dodeca-1(12),4,6,8,10-pentaen-1-ylium

Zhao-Yun Wang ^a,^*

PMCID: PMC3648305 PMID: 23723925

Abstract

In the title boron–dipyrromethene derivative, C₁₇H₁₆BF₂N₃, the benzene ring and the boron–dipyrromethene mean plane form a dihedral angle of 55.82 (8)°. In the crystal, pairs of C—H⋯F interactions link the molecules, forming inversion dimers. Further C—H⋯F interactions link the dimers into a three-dimensional network.

Related literature

For the synthesis and applications of related 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene derivatives, see: Trieflinger et al. (2005 ▶). For related structures, see: Jiao et al. (2011 ▶). graphic file with name e-69-0o781-scheme1.jpg

Experimental

Crystal data

C₁₇H₁₆BF₂N₃
M _r = 311.14
Monoclinic,
a = 7.8033 (6) Å
b = 25.524 (2) Å
c = 9.9776 (5) Å
β = 128.671 (4)°
V = 1551.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.972, T _max = 0.981
11054 measured reflections
2736 independent reflections
2025 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.119
S = 1.03
2736 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; 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: SHELXTL.

Supplementary Material

Click here for additional data file.^{(19.4KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813010404/rk2400sup1.cif

e-69-0o781-sup1.cif^{(19.4KB, cif)}

Click here for additional data file.^{(134.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813010404/rk2400Isup2.hkl

e-69-0o781-Isup2.hkl^{(134.4KB, hkl)}

Click here for additional data file.^{(6.3KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813010404/rk2400Isup3.cml

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯F2ⁱ	0.93	2.51	3.291 (3)	142
C17—H17C⋯F2ⁱⁱ	0.96	2.49	3.282 (3)	140

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

Acknowledgments

This work was supported by the Research Culture Funds of Anhui Normal University (160–721137).

supplementary crystallographic information

Comment

Fluorescent dyes, especially 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY), have been led to the increased research interest in these molecules lately, BODIPYs have found wide applications in fluorescence labels and biomolecular sensors (Trieflinger et al., 2005), due to their remarkable properties, including large molar absorption coefficient, sharp fluorescence emissions, high fluorescence quantum yields, and high photophysical stability. As part of our ongoing studies (Jiao et al., 2011), we have obtained the title compound, and report its molecular structure here (Fig. 1). The bond lengths and angles are within normal ranges. By short contact C1—H1···F2ⁱ = 2.512Å, molecule forms 10-members centrosymmetrical dimers. Next short contact C17—H17···F2ⁱⁱ = 2.491Å form a three-dimensional network, which seem to be very effective in the stabilization of the crystal structure (Fig. 2). Symmetry codes: (i) -x, 2-y, 1-z; (ii) -x, 2-y, 2-z.

Experimental

To 4,4-difluoro-8-phenyl-4-bora-3a,4a-diaza-s-indacene (134 mg, 0.5 mmol) in 3 ml of DMF. was added Potassium tert-butoxide (561 mg, 5 mmol). After stirring at 323 k for 3 h, the reaction was monitored by TLC, then the mixture was poured into water (50 ml), adjusted pH value to 7 with hydrochloric acid and extracted with CH₂Cl₂ (3×30 ml). Organic layers were combined, dried over Mg₂SO₄, and evaporated to dryness under vacuum. Purification was performed by column chromatography on silica gel using hexane / CH₂Cl₂ (v/v, 2:1) as eluent, from which the desired product was obtained in 51% yield (80 mg).