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Acta Cryst. (2008). E64, o1735    [ doi:10.1107/S1600536808025221 ]

N,N'-Dicyclohexylnaphthalene-1,8;4:5-dicarboximide

D. Shukla and M. Rajeswaran

Abstract top

The title compound, C26H26N2O4, synthesized by the reaction of naphthalene-1,4,5,8-tetracarboxylic acid anhydride and cyclohexylamine, exhibits good n-type semiconducting properties. Accordingly, thin-film transistor devices comprising this compound show n-type behavior with high field-effect electron moblity ca 6 cm2/Vs [Shukla, Nelson, Freeman, Rajeswaran, Ahearn, Meyer & Carey(2008). Chem. Mater. Submitted]. The asymmetric unit comprises one-quarter of the centrosymmetric molecule in which all but two methylene C atoms of the cyclohexane ring lie on a mirror plane; the point-group symmetry is 2/m. The naphthalenediimide unit is strictly planar, and the cyclohexane rings adopt chair conformations with the diimide unit in an equatorial position on each ring.

Comment top

Amongst n-type semiconductors, naphthalene diimide (NDI) and perylene diimide (PDI) based systems have been studied extensively (Chesterfield, et al., 2004a; Chesterfield et al., 2004b; Facceti et al., 2008; Jones, et al., 2004; Katz, et al., 2000a; Katz, et al., 2000b). We report here the structure of the title diimide molecule, I, (Fig. 1).

Related literature top

For general background on the semi-conducting properties and use of this class of material in organic thin-film transistor applications, see: Chesterfield et al. (2004a,b); Facceti et al. (2008); Jones et al. (2004); Katz et al. (2000a,b); Shukla et al. (2008).

Experimental top

The diimide 1 was prepared by direct condensation of 1,4,5,8-naphthalenetetracarboxylic acid anhydride (1.34 g, 5.00 mmol) and cyclohexylamine (30 mmol) in the presence of zinc acetate (50 mg) in 15 mL quinoline. The mixture was heated at 140-150°C for four hours, cooled and diluted with several volumes of methanol. The resulting slurry was filtered, the collected solid washed with methanol and dried in air. The crude product was then purified by train sublimation at 10-4 to 10-6 torr. 1H NMR (CD2Cl2,500.05 MHz): δ (ppm) = 8.76 (s, 4H), 5.10 (t,2H, J = 12 Hz), 2.64 (dt, 2H, J = 12 and 11.7 Hzs), 1.57 (dt, 2H, J = 12 and11.7 Hz), 2.03 (d, 2H, J = 12 Hz), 1.87 (d, 2H, J = 12 Hz), 1.47 (m, 2H); 13C(CD2Cl2, 500.05 MHz): d = 163.23, 130.74, 127.13, 126.70,54.85, 29.38, 26.66, 25.52; MS (MALDI-TOF) m/z cald. for [C26H26N2O4]430.5 found: 430.2.

Refinement top

All H-atoms were positioned geometrically using a riding model with d(C-H) = 0.93Å, Uiso=1.2Ueq (C) for aromatic 0.97Å, Uiso = 1.2Ueq (C) for CH2 atoms.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Structure of the title compound (I), with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are omitted for clarity.
N,N'-dicyclohexylnaphthalene-1,8;4:5-dicarboximide top
Crystal data top
C26H26N2O4F000 = 456
Mr = 430.49Dx = 1.393 Mg m−3
Monoclinic, C2/mMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2yCell parameters from 21067 reflections
a = 8.5410 (2) Åθ = 1.0–27.5º
b = 6.6780 (2) ŵ = 0.09 mm−1
c = 18.4270 (9) ÅT = 293 (2) K
β = 102.4790 (18)ºBlock, orange
V = 1026.19 (6) Å30.35 × 0.25 × 0.17 mm
Z = 2
Data collection top
Nonius KappaCCD
diffractometer		1227 independent reflections
Radiation source: fine-focus sealed tube787 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.087
Detector resolution: 9 pixels mm-1θmax = 27.4º
T = 293(2) Kθmin = 4.3º
φ and ω scansh = −10→10
Absorption correction: nonek = −8→8
3354 measured reflectionsl = −23→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.067H-atom parameters constrained
wR(F2) = 0.182  w = 1/[σ2(Fo2) + (0.0638P)2 + 1.0546P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1227 reflectionsΔρmax = 0.39 e Å−3
91 parametersΔρmin = −0.29 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C26H26N2O4V = 1026.19 (6) Å3
Mr = 430.49Z = 2
Monoclinic, C2/mMo Kα
a = 8.5410 (2) ŵ = 0.09 mm−1
b = 6.6780 (2) ÅT = 293 (2) K
c = 18.4270 (9) Å0.35 × 0.25 × 0.17 mm
β = 102.4790 (18)º
Data collection top
Nonius KappaCCD
diffractometer		1227 independent reflections
Absorption correction: none787 reflections with I > 2σ(I)
3354 measured reflectionsRint = 0.087
Refinement top
R[F2 > 2σ(F2)] = 0.06791 parameters
wR(F2) = 0.182H-atom parameters constrained
S = 1.06Δρmax = 0.39 e Å−3
1227 reflectionsΔρmin = −0.29 e Å−3
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
xyzUiso*/Ueq
O10.2160 (3)0.00000.28476 (12)0.0594 (8)
O20.7630 (3)0.00000.33332 (13)0.0647 (8)
N10.4894 (3)0.00000.30625 (13)0.0431 (7)
C10.6391 (4)0.00000.35566 (18)0.0457 (8)
C20.6418 (3)0.00000.43622 (17)0.0422 (8)
C30.7854 (4)0.00000.48703 (18)0.0510 (9)
H30.88060.00000.47030.061*
C40.4979 (3)0.00000.46157 (16)0.0384 (7)
C50.2086 (4)0.00000.43639 (18)0.0494 (9)
H50.11000.00000.40300.059*
C60.3486 (3)0.00000.41020 (17)0.0410 (7)
C70.3427 (4)0.00000.32968 (18)0.0446 (8)
C80.4868 (4)0.00000.22507 (16)0.0460 (8)
H80.59910.00000.22070.055*
C90.4125 (3)0.1896 (4)0.18665 (13)0.0591 (7)
H9A0.46840.30600.21100.071*
H9B0.30100.19860.19010.071*
C100.4238 (3)0.1862 (5)0.10529 (14)0.0708 (9)
H10A0.36990.30310.08030.085*
H10B0.53560.19260.10220.085*
C110.3488 (5)0.00000.0665 (2)0.0664 (11)
H11A0.36240.00000.01560.080*
H11B0.23480.00000.06540.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0365 (12)0.088 (2)0.0494 (14)0.0000.0005 (9)0.000
O20.0363 (12)0.105 (2)0.0535 (14)0.0000.0113 (10)0.000
N10.0330 (12)0.0522 (17)0.0428 (14)0.0000.0052 (10)0.000
C10.0323 (15)0.051 (2)0.0514 (19)0.0000.0047 (12)0.000
C20.0322 (15)0.0478 (19)0.0456 (18)0.0000.0066 (12)0.000
C30.0296 (15)0.071 (2)0.0513 (19)0.0000.0072 (12)0.000
C40.0309 (14)0.0364 (16)0.0459 (16)0.0000.0040 (11)0.000
C50.0292 (14)0.065 (2)0.0503 (19)0.0000.0012 (12)0.000
C60.0303 (15)0.0445 (18)0.0460 (17)0.0000.0033 (12)0.000
C70.0357 (15)0.0466 (19)0.0491 (18)0.0000.0038 (13)0.000
C80.0379 (15)0.059 (2)0.0403 (17)0.0000.0059 (12)0.000
C90.0643 (15)0.0483 (15)0.0601 (16)−0.0050 (13)0.0033 (11)0.0031 (12)
C100.0716 (17)0.080 (2)0.0561 (16)−0.0103 (17)0.0045 (12)0.0170 (15)
C110.056 (2)0.094 (3)0.047 (2)0.0000.0059 (16)0.000
Geometric parameters (Å, °) top
O1—C71.212 (3)C5—H50.9300
O2—C11.216 (4)C6—C71.474 (4)
N1—C11.401 (4)C8—C9ii1.521 (3)
N1—C71.411 (4)C8—C91.521 (3)
N1—C81.491 (4)C8—H80.9800
C1—C21.480 (4)C9—C101.523 (3)
C2—C31.373 (4)C9—H9A0.9700
C2—C41.406 (4)C9—H9B0.9700
C3—C5i1.401 (4)C10—C111.506 (4)
C3—H30.9300C10—H10A0.9700
C4—C4i1.409 (6)C10—H10B0.9700
C4—C61.415 (4)C11—C10ii1.506 (4)
C5—C61.382 (4)C11—H11A0.9700
C5—C3i1.401 (4)C11—H11B0.9700
C1—N1—C7123.2 (3)N1—C8—C9ii112.42 (17)
C1—N1—C8117.8 (3)N1—C8—C9112.42 (17)
C7—N1—C8119.0 (2)C9ii—C8—C9112.7 (3)
O2—C1—N1121.3 (3)N1—C8—H8106.2
O2—C1—C2120.9 (3)C9ii—C8—H8106.2
N1—C1—C2117.8 (3)C9—C8—H8106.2
C3—C2—C4119.3 (3)C8—C9—C10109.7 (2)
C3—C2—C1120.1 (3)C8—C9—H9A109.7
C4—C2—C1120.5 (3)C10—C9—H9A109.7
C2—C3—C5i121.3 (3)C8—C9—H9B109.7
C2—C3—H3119.3C10—C9—H9B109.7
C5i—C3—H3119.3H9A—C9—H9B108.2
C2—C4—C4i120.0 (3)C11—C10—C9111.6 (3)
C2—C4—C6120.3 (3)C11—C10—H10A109.3
C4i—C4—C6119.7 (3)C9—C10—H10A109.3
C6—C5—C3i120.4 (3)C11—C10—H10B109.3
C6—C5—H5119.8C9—C10—H10B109.3
C3i—C5—H5119.8H10A—C10—H10B108.0
C5—C6—C4119.3 (3)C10—C11—C10ii111.3 (3)
C5—C6—C7120.5 (3)C10—C11—H11A109.4
C4—C6—C7120.2 (3)C10ii—C11—H11A109.4
O1—C7—N1120.8 (3)C10—C11—H11B109.4
O1—C7—C6121.2 (3)C10ii—C11—H11B109.4
N1—C7—C6118.0 (2)H11A—C11—H11B108.0
C7—N1—C1—O2180.0C2—C4—C6—C70.0
C8—N1—C1—O20.0C4i—C4—C6—C7180.0
C7—N1—C1—C20.0C1—N1—C7—O1180.0
C8—N1—C1—C2180.0C8—N1—C7—O10.0
O2—C1—C2—C30.0C1—N1—C7—C60.0
N1—C1—C2—C3180.0C8—N1—C7—C6180.0
O2—C1—C2—C4180.0C5—C6—C7—O10.0
N1—C1—C2—C40.0C4—C6—C7—O1180.0
C4—C2—C3—C5i0.000 (1)C5—C6—C7—N1180.0
C1—C2—C3—C5i180.0C4—C6—C7—N10.0
C3—C2—C4—C4i0.0C1—N1—C8—C9ii115.76 (19)
C1—C2—C4—C4i180.0C7—N1—C8—C9ii−64.24 (19)
C3—C2—C4—C6180.0C1—N1—C8—C9−115.76 (19)
C1—C2—C4—C60.0C7—N1—C8—C964.24 (19)
C3i—C5—C6—C40.000 (1)N1—C8—C9—C10176.2 (2)
C3i—C5—C6—C7180.0C9ii—C8—C9—C10−55.5 (4)
C2—C4—C6—C5180.0C8—C9—C10—C1155.2 (3)
C4i—C4—C6—C50.000 (1)C9—C10—C11—C10ii−56.5 (4)
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y, z.
Acknowledgements top

We thank Ms Wendy Ahearn and Ms Dianne Meyer of Eastman Kodak Company for material purification and crystal growth via sublimation.

references
References top

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