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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): o2565.
Published online 2010 September 15. doi:  10.1107/S1600536810035877
PMCID: PMC2983141

1,4,5,8-Tetra-n-butyl­anthracene

Abstract

The mol­ecule of the title compound, C30H42, occupies a special position on an inversion center. The four butyl side chains have all-trans planar conformations, and the alkyl planes are nearly orthogonal to the anthracene plane [C—C—C—C torsion angles of 79.6 (2) and 78.2 (2)°]. The overall mol­ecule has a stair-like shape with the n-butyl groups at the 1 and 8 positions extending towards the same side of the anthracene plane. In the crystal structure, mol­ecules adopt a slipped–parallel arrangement without π–π stacking.

Related literature

For background to solid-state packing effects in electronic and photonic materials, see: Curtis et al. (2004 [triangle]). For the correlation between π–π stacking and fluorescence quantum yields, see: Yoshida et al. (2002 [triangle]). For related structures and their solid-state fluorescence, see: Kitamura, Abe et al. (2007 [triangle]); Kitamura, Ohara et al. (2007 [triangle]); Kitamura et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2565-scheme1.jpg

Experimental

Crystal data

  • C30H42
  • M r = 402.64
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2565-efi1.jpg
  • a = 4.793 (2) Å
  • b = 11.497 (6) Å
  • c = 11.753 (6) Å
  • α = 83.052 (14)°
  • β = 82.205 (15)°
  • γ = 83.202 (15)°
  • V = 633.5 (5) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.06 mm−1
  • T = 223 K
  • 0.50 × 0.05 × 0.02 mm

Data collection

  • Rigaku/MSC Mercury CCD area-detector diffractometer
  • Absorption correction: numerical (NUMABS; Higashi, 2000 [triangle]) T min = 0.988, T max = 0.999
  • 5371 measured reflections
  • 3103 independent reflections
  • 1361 reflections with I > 2σ(I)
  • R int = 0.033

Refinement

  • R[F 2 > 2σ(F 2)] = 0.073
  • wR(F 2) = 0.246
  • S = 0.98
  • 3103 reflections
  • 138 parameters
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.17 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2006 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR2004 (Burla et al., 2005 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810035877/ya2127sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035877/ya2127Isup2.hkl

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

Acknowledgments

We thank the Instrument Center of the Institute for Mol­ecular Science in Okazaki, Japan, for assistance in obtaining the X-ray data. This work was supported by a Grant-in-Aid (No. 20550128) for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

supplementary crystallographic information

Comment

Solid-state packing effects play an important role in the performance of electronic and photonic materials (Curtis et al., 2004). However, there has been relatively little research on the correlation between solid-state packing patterns and fluorescence properties. Therefore, molecular design principles which could allow to control solid-state fluorescence are not fully understood.

We have recently found that the introduction of different alkyl side chains onto anthracene nucleus at the 1, 4, 5, and 8 positions brought about considerable variety in alkyl conformations, packing patterns, and solid-state fluorescence properties. As a part of systematic investigation of this phenomena, we report herein the structure of the title compound, namely, the anthracene tetra-n-butyl derivative (Fig.1).

The molecule occupies a special position in the inversion center. The bond lengths and bond angles are comparable to those of other 1,4,5,8-tetraalkylanthracenes (Kitamura, Abe et al., 2007). Four butyl side chains adopt all-trans planar conformations, and the alkyl planes are nearly orthogonal to the anthracene plane; the torsion angles of C6—C1—C8—C9 and C5—C4—C12—C13 are 79.6 (2) and 78.2 (2)°, respectively. Thus, the molecule of the title compound has a stair-like shape, and two butyl groups at the 1 and 8 positions extend towards the same side of the anthracene plane. This molecular structure is similar to that of 1,4,7,10-tetra-n-butyltetracene (Kitamura, Ohara et al., 2007; Kitamura et al., 2010).

In crystal the molecules show a slipped-parallel arrangement without π-π stacking (Fig. 2). Such packing, as has been shown (Yoshida et al., 2002), can enhance fluorescence quantum yields because of the same directions of transition dipole moments for all molecules as well as no concentration quenching (Kitamura, Abe et al., 2007).

To examine the influence of crystal packing on the solid-state fluorescence properties, the fluorescence spectrum and the absolute quantum yield of the title compound were measured with a Hamamatsu Photonics PMA11 calibrated optical multichannel analyzer with a solid-state blue laser (λex = 377 nm) and a Labsphere IS-040-SF integrating sphere. The crystals exhibited a broad fluorescence spectrum with a fluorescence maximum at 450 nm, a shoulder peak around 467 nm and very high quantum yield (Φ = 0.78). Among 1,4,5,8-tetraalkylanthracenes, only the propyl derivative had higher quantum yield of 0.85 (Kitamura, Abe et al., 2007), which is of course still quite comparable to that of the title compound.

Experimental

1,4,5,8-Tetra-n-butylanthracene was prepared according to the method described by Kitamura, Abe et al. (2007). A mixture of 2,5-dibutylfuran (2.99 g, 16.3 mmol) and 1,2,4,5-tetrabromobenzene (3.10 g, 7.88 mmol) in dry toluene (50 ml) was cooled to 243 K. To the mixture, 1.6 M n-BuLi in hexane (14.8 ml, 23.7 mmol) was added dropwise over 15 min. Then the mixture was warmed up to room temperature over 2 h and stirred at room temperature for additional 18 h. After quenching with water, the aqueous layer was extracted with CHCl3. The combined organic layer was washed with brine and dried over Na2SO4. After evaporation, the residue was subjected to slica-gel chromatography with (2:1)-hexane/CHCl3 to afford bis(furan)adduct as an orange solid (602 mg, 18°). The bis(furan)adduct (602 mg, 1.38 mmol) in EtOH (60 ml) was hydrogenated over 10° Pd/C (125 mg) under atmospheric pressure at room temperature for 3 h. The catalyst was removed by filtration, and the filtrate was evaporated under reduced pressure. To the residue, an ice-cooled solution of (1:5)-conc. HCl/Ac2O (6 ml) was added. The mixture was stirred at room temperature for 3 h. After cooling with ice, water was added into the mixture. The resultant mixture was extracted with CHCl3, and the extract was washed with aqueous Na2CO3 and brine, and dried over Na2SO4. After evaporation of the solvent, column chromatography on silica gel with (2:1)-hexane/CHCl3 gave the title compound as a pale yellow solid (412 mg, 45°). Recrystallization was performed with hexane to obtain colorless single crystals of the title compound. 1H-NMR: δ 1.00 (t, J = 7.2 Hz, 12H), 1.48–1.55 (m, 8H), 1.80–1.86 (m, 8H), 3.18 (t, J = 7.6 Hz, 8H), 7.22 (s, 4H), 8.80 (s, 2H); 13C-NMR: δ 14.06, 23.05, 33.03, 33.30, 120.04, 124.66, 130.03, 137.03; EIMS: m/z (°) 402 (100); Elemental analysis for C30H42: C, 89.49; H, 10.51. Found: C, 89.41; H, 10.60.

Refinement

All the H atoms were positioned geometrically and refined using a riding model with C—H bonds of 0.94 \%A, 0.98\%A, and 0.97\%A for aromatic, methylene, and methyl groups, respectively, and Uiso(H) = 1.2Ueq(C) [Uiso(H) = 1.5Ueq(C) for methyl H atoms].

Figures

Fig. 1.
Molecular structure of the title compound; displacement ellipsoids are drawn at the 30° probability level; the unlabelled atoms are derived by the symmetry transformation -x + 2, -y + 1, -z + 1.
Fig. 2.
The packing diagram of the title compound viewed down the long molecular axis of anthracene ring; hydrogen atoms are omitted for clarity.

Crystal data

C30H42Z = 1
Mr = 402.64F(000) = 222
Triclinic, P1Dx = 1.055 Mg m3
Hall symbol: -P 1Melting point: 368 K
a = 4.793 (2) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.497 (6) ÅCell parameters from 1148 reflections
c = 11.753 (6) Åθ = 2.4–30.0°
α = 83.052 (14)°µ = 0.06 mm1
β = 82.205 (15)°T = 223 K
γ = 83.202 (15)°Needle, colorless
V = 633.5 (5) Å30.50 × 0.05 × 0.02 mm

Data collection

Rigaku/MSC Mercury CCD area-detector diffractometer3103 independent reflections
Radiation source: rotating-anode X-ray tube1361 reflections with I > 2σ(I)
graphiteRint = 0.033
Detector resolution: 14.7059 pixels mm-1θmax = 28.3°, θmin = 2.6°
[var phi] and ω scansh = −6→5
Absorption correction: numerical (NUMABS; Higashi, 2000)k = −12→15
Tmin = 0.988, Tmax = 0.999l = −10→15
5371 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.073H-atom parameters constrained
wR(F2) = 0.246w = 1/[σ2(Fo2) + (0.1174P)2] where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
3103 reflectionsΔρmax = 0.31 e Å3
138 parametersΔρmin = −0.17 e Å3
0 restraints

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C10.7400 (4)0.4153 (2)0.3252 (2)0.0481 (6)
C20.8025 (5)0.2989 (2)0.3077 (2)0.0584 (7)
H20.72140.26950.250.07*
C30.9869 (5)0.2214 (2)0.3745 (2)0.0583 (7)
H31.02590.14240.35880.07*
C41.1078 (4)0.2577 (2)0.4598 (2)0.0481 (6)
C51.0540 (4)0.37919 (19)0.48075 (18)0.0423 (6)
C60.8697 (4)0.45829 (19)0.41302 (18)0.0430 (6)
C70.8223 (4)0.5758 (2)0.43552 (18)0.0461 (6)
H70.70030.62740.39180.055*
C80.5481 (4)0.4958 (2)0.2522 (2)0.0544 (7)
H8A0.4240.54820.30160.065*
H8B0.4280.44820.21980.065*
C90.7059 (4)0.5708 (2)0.1533 (2)0.0560 (7)
H9A0.82830.61730.18580.067*
H9B0.82810.51820.10350.067*
C100.5175 (5)0.6530 (2)0.0806 (2)0.0684 (8)
H10A0.39910.70720.12980.082*
H10B0.39160.60690.04950.082*
C110.6765 (7)0.7242 (3)−0.0187 (3)0.0873 (10)
H11A0.80210.77010.01110.131*
H11B0.54270.7767−0.06060.131*
H11C0.78670.6714−0.07030.131*
C121.2822 (5)0.1713 (2)0.5349 (2)0.0563 (7)
H12A1.44720.20770.54930.068*
H12B1.35140.10220.49390.068*
C131.1155 (5)0.1314 (2)0.6507 (2)0.0563 (7)
H13A1.02870.20140.68720.068*
H13B0.96220.08810.6360.068*
C141.2883 (5)0.0551 (2)0.7335 (2)0.0708 (8)
H14A1.43680.09950.7510.085*
H14B1.3813−0.01350.69610.085*
C151.1173 (6)0.0126 (3)0.8457 (2)0.0865 (10)
H15A1.02220.07980.88280.13*
H15B1.2427−0.03350.89630.13*
H15C0.9777−0.03590.82970.13*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0437 (10)0.0523 (15)0.0476 (13)−0.0138 (10)−0.0001 (9)0.0003 (11)
C20.0682 (14)0.0565 (17)0.0521 (15)−0.0177 (12)−0.0026 (12)−0.0069 (13)
C30.0745 (14)0.0430 (14)0.0546 (15)−0.0093 (11)0.0047 (12)−0.0055 (12)
C40.0515 (11)0.0456 (14)0.0438 (13)−0.0073 (10)0.0046 (10)−0.0005 (11)
C50.0422 (10)0.0419 (13)0.0403 (12)−0.0073 (9)0.0048 (9)−0.0025 (10)
C60.0393 (10)0.0465 (14)0.0409 (12)−0.0092 (9)0.0042 (9)−0.0014 (11)
C70.0430 (10)0.0493 (15)0.0426 (12)−0.0051 (9)0.0012 (9)0.0022 (10)
C80.0469 (11)0.0663 (17)0.0508 (14)−0.0147 (11)−0.0041 (10)−0.0035 (12)
C90.0501 (11)0.0670 (17)0.0487 (14)−0.0074 (11)−0.0058 (10)0.0034 (12)
C100.0667 (14)0.073 (2)0.0632 (17)−0.0037 (13)−0.0133 (13)0.0043 (15)
C110.105 (2)0.085 (2)0.070 (2)−0.0111 (17)−0.0247 (17)0.0186 (17)
C120.0641 (13)0.0464 (15)0.0532 (15)−0.0004 (11)0.0033 (11)−0.0006 (12)
C130.0617 (12)0.0459 (15)0.0572 (15)−0.0038 (10)−0.0026 (11)0.0041 (12)
C140.0745 (15)0.070 (2)0.0613 (17)0.0007 (13)−0.0017 (13)0.0026 (15)
C150.108 (2)0.085 (2)0.0570 (18)0.0006 (17)−0.0018 (16)0.0125 (16)

Geometric parameters (Å, °)

C1—C21.370 (3)C9—H9B0.98
C1—C61.438 (3)C10—C111.513 (4)
C1—C81.503 (3)C10—H10A0.98
C2—C31.422 (3)C10—H10B0.98
C2—H20.94C11—H11A0.97
C3—C41.353 (3)C11—H11B0.97
C3—H30.94C11—H11C0.97
C4—C51.435 (3)C12—C131.530 (3)
C4—C121.502 (3)C12—H12A0.98
C5—C7i1.394 (3)C12—H12B0.98
C5—C61.438 (3)C13—C141.498 (3)
C6—C71.394 (3)C13—H13A0.98
C7—C5i1.394 (3)C13—H13B0.98
C7—H70.94C14—C151.515 (3)
C8—C91.530 (3)C14—H14A0.98
C8—H8A0.98C14—H14B0.98
C8—H8B0.98C15—H15A0.97
C9—C101.500 (3)C15—H15B0.97
C9—H9A0.98C15—H15C0.97
C2—C1—C6117.9 (2)C11—C10—H10A108.8
C2—C1—C8120.7 (2)C9—C10—H10B108.8
C6—C1—C8121.3 (2)C11—C10—H10B108.8
C1—C2—C3121.8 (2)H10A—C10—H10B107.7
C1—C2—H2119.1C10—C11—H11A109.5
C3—C2—H2119.1C10—C11—H11B109.5
C4—C3—C2122.1 (2)H11A—C11—H11B109.5
C4—C3—H3118.9C10—C11—H11C109.5
C2—C3—H3118.9H11A—C11—H11C109.5
C3—C4—C5118.6 (2)H11B—C11—H11C109.5
C3—C4—C12120.7 (2)C4—C12—C13112.63 (17)
C5—C4—C12120.7 (2)C4—C12—H12A109.1
C7i—C5—C4122.1 (2)C13—C12—H12A109.1
C7i—C5—C6118.3 (2)C4—C12—H12B109.1
C4—C5—C6119.6 (2)C13—C12—H12B109.1
C7—C6—C5118.1 (2)H12A—C12—H12B107.8
C7—C6—C1122.0 (2)C14—C13—C12114.55 (19)
C5—C6—C1119.9 (2)C14—C13—H13A108.6
C6—C7—C5i123.6 (2)C12—C13—H13A108.6
C6—C7—H7118.2C14—C13—H13B108.6
C5i—C7—H7118.2C12—C13—H13B108.6
C1—C8—C9113.77 (16)H13A—C13—H13B107.6
C1—C8—H8A108.8C13—C14—C15113.7 (2)
C9—C8—H8A108.8C13—C14—H14A108.8
C1—C8—H8B108.8C15—C14—H14A108.8
C9—C8—H8B108.8C13—C14—H14B108.8
H8A—C8—H8B107.7C15—C14—H14B108.8
C10—C9—C8114.48 (17)H14A—C14—H14B107.7
C10—C9—H9A108.6C14—C15—H15A109.5
C8—C9—H9A108.6C14—C15—H15B109.5
C10—C9—H9B108.6H15A—C15—H15B109.5
C8—C9—H9B108.6C14—C15—H15C109.5
H9A—C9—H9B107.6H15A—C15—H15C109.5
C9—C10—C11113.8 (2)H15B—C15—H15C109.5
C9—C10—H10A108.8
C6—C1—C2—C30.7 (3)C8—C1—C6—C70.6 (3)
C8—C1—C2—C3179.03 (17)C2—C1—C6—C5−1.2 (3)
C1—C2—C3—C40.9 (3)C8—C1—C6—C5−179.49 (16)
C2—C3—C4—C5−1.9 (3)C5—C6—C7—C5i0.6 (3)
C2—C3—C4—C12174.95 (18)C1—C6—C7—C5i−179.46 (16)
C3—C4—C5—C7i−177.93 (17)C2—C1—C8—C9−98.6 (2)
C12—C4—C5—C7i5.2 (3)C6—C1—C8—C979.6 (2)
C3—C4—C5—C61.3 (3)C1—C8—C9—C10−179.2 (2)
C12—C4—C5—C6−175.48 (16)C8—C9—C10—C11−178.5 (2)
C7i—C5—C6—C7−0.6 (3)C3—C4—C12—C13−98.5 (2)
C4—C5—C6—C7−179.91 (16)C5—C4—C12—C1378.2 (3)
C7i—C5—C6—C1179.49 (16)C4—C12—C13—C14−173.9 (2)
C4—C5—C6—C10.2 (3)C12—C13—C14—C15−177.7 (2)
C2—C1—C6—C7178.90 (17)

Symmetry codes: (i) −x+2, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: YA2127).

References

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