Difluoro­[2-(quinolin-2-yl)phenolato]borane

Yang, X.; Xia, M.

doi:10.1107/S1600536811011895

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1049

doi:10.1107/S1600536811011895

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Difluoro[2-(quinolin-2-yl)phenolato]borane

Xi Yang ^a and Min Xia ^a ^*

^aDepartment of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China
^*Correspondence e-mail: xiamin@hzcnc.com

(Received 17 March 2011; accepted 30 March 2011; online 7 April 2011)

The title compound, C₁₅H₁₀BF₂NO, was synthesized by the reaction of 2-(quinolin-2-yl)phenol and boron trifluoride etherate. The quinoline ring system and the benzene ring are twisted, making a dihedral angle of 8.3 (2)°. In the crystal, π–π interactions between the aromatic rings [centroid–centroid distance = 3.638 (9) Å] link the molecules into chains propagating in [100].

Related literature

For the properties and the preparation of difluoroboron complexes, see: Loudet et al. (2007 ); Ulrich et al. (2008 ); Ono et al. (2009 ); Zhou et al. (2008 ); Xia et al. (2008 ).

Experimental

Crystal data

C₁₅H₁₀BF₂NO
M_r = 269.05
Triclinic, $[P \overline 1]$
a = 7.4660 (15) Å
b = 8.6300 (17) Å
c = 9.3420 (19) Å
α = 97.71 (3)°
β = 95.63 (3)°
γ = 92.61 (3)°
V = 592.5 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 295 K
0.46 × 0.22 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.949, T_max = 0.984
4885 measured reflections
2169 independent reflections
1329 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.127
S = 1.13
2169 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011895/si2346sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011895/si2346Isup2.hkl

checkCIF report

Comment top

Recently, the interest in synthesis and property research on novel difluoroboron complexes has been becoming increasingly intensive, due to their distinguishing fluorescence and important applications in chemical and biological fields [Loudet et al., 2007]. Among them, the two types with N, N– and O, O-double dentate ligands are dominantly focused, like boradipyrromethene [Ulrich et al., 2008] and 1, 3, 2- dioxaborine [Ono et al., 2009] as the corresponding representatives. However, the isosteric analogues with N, O-double dentate ligands are limitedly reported, especially those having strong fluorescence intensity and high quantum yields [Zhou et al., 2008]. We reported our example of N, O-double dentate difluoroborane complexes with outstandingly intensive green fluorescence based on 1,3-enamino-ketone structures [Xia et al., 2008]. In connection with our study, herein we describe another complex exhibiting strong cyan fluorescence.

The bond lengths and angles of the title molecule (Fig. 1) are within normal ranges. The aromatic quinoline [C1–C9/N1] and benzene [C10–C15] rings are twisted at a dihedral angle of 8.3 (2)°. In the crystal structure, π-π interactions between the aromatic rings [Cg1···Cg2¹ = 3.638 (9) Å, symm. code i = -x, -y, 1 - z] link molecules into chains propagated in direction [1 0 0], the two aromatic planes are partial overlap. The van der Waals forces stabilize further the crystal packing.

Related literature top

For the properties and the preparation of difluoroboron complexes, see: Loudet et al. (2007); Ulrich et al. (2008); Ono et al. (2009); Zhou et al. (2008); Xia et al. (2008).

Experimental top

At room temperature, triethylamine (21 mmol, 2.9 mL) is added to the solution of 2-quinolin-2-yl- phenol (10 mmol, 2.21 g) in benzene(15 mL), the resulted mixture is stirred for 20 min and boron trifluoride etherate (30 mmol, 2.8 mL) is dropped into it. The large amount of yellow solid is precipitated after stirring for about 40 min, the solid is collected by filtration and washed by ether for several times. After dried in air, the corresponding difluoroboron complex is obtained in 92% yield as bright yellow powder(m.p. 537–538 K). At room temperature, ether is carefully and slowly dropped into the solution of the complex in dichoromethane and the resulted mixture is kept without any disturb under the airproof condition until the crystal is formed.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. View of the title molecule. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by circles of arbitrary size.

Difluoro[2-(quinolin-2-yl)phenolato]borane top

Crystal data top

C₁₅H₁₀BF₂NO	Z = 2
M_r = 269.05	F(000) = 276
Triclinic, P1	D_x = 1.508 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4660 (15) Å	Cell parameters from 3364 reflections
b = 8.6300 (17) Å	θ = 3.0–27.4°
c = 9.3420 (19) Å	µ = 0.12 mm⁻¹
α = 97.71 (3)°	T = 295 K
β = 95.63 (3)°	Prism, yellow
γ = 92.61 (3)°	0.46 × 0.22 × 0.14 mm
V = 592.5 (2) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	2169 independent reflections
Radiation source: fine-focus sealed tube	1329 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.4°, θ_min = 3.0°
ω scans	h = −8→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
T_min = 0.949, T_max = 0.984	l = −11→11
4885 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.127	w = 1/[σ²(F_o²) + (0.0631P)²] where P = (F_o² + 2F_c²)/3
S = 1.13	(Δ/σ)_max < 0.001
2169 reflections	Δρ_max = 0.29 e Å⁻³
182 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.033 (7)

Crystal data top

C₁₅H₁₀BF₂NO	γ = 92.61 (3)°
M_r = 269.05	V = 592.5 (2) Å³
Triclinic, P1	Z = 2
a = 7.4660 (15) Å	Mo Kα radiation
b = 8.6300 (17) Å	µ = 0.12 mm⁻¹
c = 9.3420 (19) Å	T = 295 K
α = 97.71 (3)°	0.46 × 0.22 × 0.14 mm
β = 95.63 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2169 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1329 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.984	R_int = 0.025
4885 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.13	Δρ_max = 0.29 e Å⁻³
2169 reflections	Δρ_min = −0.20 e Å⁻³
182 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
F1	0.38077 (17)	0.27217 (11)	0.25453 (14)	0.0696 (4)
F2	0.07658 (16)	0.22181 (12)	0.23344 (13)	0.0700 (4)
O1	0.2311 (2)	0.34773 (14)	0.44802 (16)	0.0710 (5)
N1	0.26036 (19)	0.06102 (14)	0.37319 (17)	0.0427 (4)
C1	0.3005 (2)	−0.06216 (19)	0.2687 (2)	0.0441 (5)
C2	0.3067 (3)	−0.0422 (2)	0.1235 (2)	0.0579 (6)
H2	0.2826	0.0541	0.0939	0.069*
C3	0.3479 (3)	−0.1635 (2)	0.0245 (2)	0.0640 (6)
H3	0.3524	−0.1481	−0.0718	0.077*
C4	0.3833 (3)	−0.3099 (2)	0.0649 (3)	0.0624 (6)
H4	0.4125	−0.3905	−0.0037	0.075*
C5	0.3750 (3)	−0.3344 (2)	0.2044 (3)	0.0563 (6)
H5	0.3972	−0.4322	0.2313	0.068*
C6	0.3324 (2)	−0.21077 (19)	0.3095 (2)	0.0465 (5)
C7	0.3186 (3)	−0.2317 (2)	0.4545 (2)	0.0554 (5)
H7	0.3407	−0.3284	0.4840	0.066*
C8	0.2735 (3)	−0.1123 (2)	0.5524 (2)	0.0511 (5)
H8	0.2625	−0.1285	0.6476	0.061*
C9	0.2435 (2)	0.03633 (18)	0.5099 (2)	0.0425 (4)
C10	0.1944 (2)	0.16571 (19)	0.6148 (2)	0.0441 (5)
C11	0.1542 (3)	0.1444 (2)	0.7542 (2)	0.0556 (5)
H11	0.1573	0.0449	0.7817	0.067*
C12	0.1102 (3)	0.2672 (3)	0.8516 (2)	0.0629 (6)
H12	0.0857	0.2506	0.9442	0.075*
C13	0.1024 (3)	0.4155 (2)	0.8112 (2)	0.0602 (6)
H13	0.0710	0.4983	0.8766	0.072*
C14	0.1407 (3)	0.4412 (2)	0.6757 (2)	0.0591 (6)
H14	0.1355	0.5411	0.6493	0.071*
C15	0.1874 (3)	0.3172 (2)	0.5773 (2)	0.0498 (5)
B1	0.2359 (3)	0.2321 (2)	0.3236 (3)	0.0502 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0908 (10)	0.0476 (6)	0.0785 (9)	0.0031 (5)	0.0333 (7)	0.0210 (6)
F2	0.0803 (9)	0.0602 (7)	0.0707 (9)	0.0220 (6)	−0.0066 (7)	0.0181 (6)
O1	0.1229 (14)	0.0395 (7)	0.0548 (10)	0.0104 (7)	0.0259 (9)	0.0080 (6)
N1	0.0465 (9)	0.0372 (8)	0.0449 (10)	0.0025 (6)	0.0032 (7)	0.0089 (7)
C1	0.0420 (10)	0.0382 (9)	0.0508 (13)	0.0034 (7)	0.0027 (9)	0.0031 (8)
C2	0.0719 (14)	0.0489 (10)	0.0536 (14)	0.0113 (9)	0.0089 (11)	0.0057 (9)
C3	0.0769 (16)	0.0611 (12)	0.0542 (14)	0.0151 (10)	0.0107 (11)	0.0019 (10)
C4	0.0588 (13)	0.0511 (11)	0.0718 (17)	0.0090 (9)	0.0043 (11)	−0.0112 (11)
C5	0.0515 (12)	0.0393 (10)	0.0760 (16)	0.0048 (8)	0.0003 (11)	0.0044 (10)
C6	0.0384 (10)	0.0430 (10)	0.0567 (13)	−0.0010 (7)	−0.0011 (9)	0.0072 (8)
C7	0.0554 (12)	0.0402 (10)	0.0724 (15)	0.0034 (8)	0.0011 (11)	0.0179 (9)
C8	0.0569 (12)	0.0468 (10)	0.0516 (12)	0.0029 (8)	0.0018 (9)	0.0175 (9)
C9	0.0390 (10)	0.0449 (9)	0.0442 (12)	−0.0019 (7)	0.0006 (8)	0.0132 (8)
C10	0.0379 (10)	0.0442 (9)	0.0481 (12)	−0.0002 (7)	0.0004 (8)	0.0030 (8)
C11	0.0510 (12)	0.0656 (12)	0.0522 (13)	0.0037 (9)	0.0050 (10)	0.0158 (10)
C12	0.0570 (13)	0.0839 (15)	0.0485 (13)	0.0044 (10)	0.0110 (10)	0.0080 (11)
C13	0.0529 (13)	0.0657 (13)	0.0570 (15)	−0.0005 (9)	0.0095 (10)	−0.0106 (11)
C14	0.0676 (14)	0.0479 (10)	0.0603 (15)	0.0033 (9)	0.0124 (11)	−0.0023 (10)
C15	0.0556 (12)	0.0499 (11)	0.0440 (12)	−0.0009 (8)	0.0077 (10)	0.0065 (9)
B1	0.0666 (15)	0.0391 (11)	0.0489 (14)	0.0099 (9)	0.0138 (12)	0.0133 (9)

Geometric parameters (Å, º) top

F1—B1	1.367 (3)	C6—C7	1.403 (3)
F2—B1	1.381 (3)	C7—C8	1.360 (3)
O1—C15	1.338 (2)	C7—H7	0.9300
O1—B1	1.431 (3)	C8—C9	1.414 (2)
N1—C9	1.339 (2)	C8—H8	0.9300
N1—C1	1.408 (2)	C9—C10	1.468 (3)
N1—B1	1.619 (2)	C10—C11	1.398 (3)
C1—C2	1.395 (3)	C10—C15	1.400 (3)
C1—C6	1.410 (2)	C11—C12	1.374 (3)
C2—C3	1.368 (2)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.384 (3)
C3—C4	1.396 (3)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.369 (3)
C4—C5	1.354 (3)	C13—H13	0.9300
C4—H4	0.9300	C14—C15	1.394 (3)
C5—C6	1.420 (3)	C14—H14	0.9300
C5—H5	0.9300

Cg1···Cg2ⁱ	3.638 (9)

C15—O1—B1	124.65 (15)	N1—C9—C8	120.27 (16)
C9—N1—C1	120.50 (15)	N1—C9—C10	119.15 (16)
C9—N1—B1	121.28 (15)	C8—C9—C10	120.58 (18)
C1—N1—B1	118.22 (15)	C11—C10—C15	117.48 (17)
C2—C1—N1	121.58 (16)	C11—C10—C9	122.35 (17)
C2—C1—C6	118.53 (16)	C15—C10—C9	120.17 (18)
N1—C1—C6	119.88 (18)	C12—C11—C10	121.6 (2)
C3—C2—C1	120.35 (18)	C12—C11—H11	119.2
C3—C2—H2	119.8	C10—C11—H11	119.2
C1—C2—H2	119.8	C11—C12—C13	119.7 (2)
C2—C3—C4	121.3 (2)	C11—C12—H12	120.1
C2—C3—H3	119.3	C13—C12—H12	120.1
C4—C3—H3	119.3	C14—C13—C12	120.48 (18)
C5—C4—C3	119.90 (18)	C14—C13—H13	119.8
C5—C4—H4	120.1	C12—C13—H13	119.8
C3—C4—H4	120.1	C13—C14—C15	119.88 (19)
C4—C5—C6	120.01 (18)	C13—C14—H14	120.1
C4—C5—H5	120.0	C15—C14—H14	120.1
C6—C5—H5	120.0	O1—C15—C14	118.28 (17)
C7—C6—C1	118.21 (17)	O1—C15—C10	120.85 (16)
C7—C6—C5	121.96 (18)	C14—C15—C10	120.83 (19)
C1—C6—C5	119.83 (19)	F1—B1—F2	111.96 (18)
C8—C7—C6	120.81 (17)	F1—B1—O1	107.42 (17)
C8—C7—H7	119.6	F2—B1—O1	111.11 (16)
C6—C7—H7	119.6	F1—B1—N1	109.25 (15)
C7—C8—C9	120.25 (19)	F2—B1—N1	106.83 (15)
C7—C8—H8	119.9	O1—B1—N1	110.27 (17)
C9—C8—H8	119.9

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₀BF₂NO
M_r	269.05
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	7.4660 (15), 8.6300 (17), 9.3420 (19)
α, β, γ (°)	97.71 (3), 95.63 (3), 92.61 (3)
V (Å³)	592.5 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.46 × 0.22 × 0.14

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.949, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	4885, 2169, 1329
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.127, 1.13
No. of reflections	2169
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.20

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

We are grateful for financial support by the Natural Science Foundation of Zhejiang Province (Y4100034) and the Innovation Fund Program for Graduate Students of Zhejiang Sci-Tech University (YCX–S10015).

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