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

Deepak Shukla; Manju Rajeswaran

doi:10.1107/S1600536808025221

. 2008 Aug 9;64(Pt 9):o1735. doi: 10.1107/S1600536808025221

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

Deepak Shukla ^a, Manju Rajeswaran ^a,^*

PMCID: PMC2960487 PMID: 21201718

Abstract

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.

Related literature

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 ▶). graphic file with name e-64-o1735-scheme1.jpg

Experimental

Crystal data

C₂₆H₂₆N₂O₄
M _r = 430.49
Monoclinic,
a = 8.5410 (2) Å
b = 6.6780 (2) Å
c = 18.4270 (9) Å
β = 102.4790 (18)°
V = 1026.19 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.35 × 0.25 × 0.17 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
3354 measured reflections
1227 independent reflections
787 reflections with I > 2σ(I)
R _int = 0.087

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.182
S = 1.06
1227 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.29 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808025221/sj2528sup1.cif

e-64-o1735-sup1.cif^{(15.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025221/sj2528Isup2.hkl

e-64-o1735-Isup2.hkl^{(60.7KB, hkl)}

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

Acknowledgments

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

supplementary crystallographic information

Comment

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).

Experimental

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.

Figures

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.

Crystal data

C₂₆H₂₆N₂O₄	F₀₀₀ = 456
M_r = 430.49	D_x = 1.393 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 21067 reflections
a = 8.5410 (2) Å	θ = 1.0–27.5º
b = 6.6780 (2) Å	µ = 0.09 mm⁻¹
c = 18.4270 (9) Å	T = 293 (2) K
β = 102.4790 (18)º	Block, orange
V = 1026.19 (6) Å³	0.35 × 0.25 × 0.17 mm
Z = 2

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Data collection

Nonius KappaCCD diffractometer	1227 independent reflections
Radiation source: fine-focus sealed tube	787 reflections with I > 2σ(I)
Monochromator: graphite	R_int = 0.087
Detector resolution: 9 pixels mm^-1	θ_max = 27.4º
T = 293(2) K	θ_min = 4.3º
φ and ω scans	h = −10→10
Absorption correction: none	k = −8→8
3354 measured reflections	l = −23→20

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Refinement

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)] = 0.067	H-atom parameters constrained
wR(F²) = 0.182	w = 1/[σ²(F_o²) + (0.0638P)² + 1.0546P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1227 reflections	Δρ_max = 0.39 e Å⁻³
91 parameters	Δρ_min = −0.29 e Å⁻³
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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Special details

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.

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

	x	y	z	U_iso*/U_eq
O1	0.2160 (3)	0.0000	0.28476 (12)	0.0594 (8)
O2	0.7630 (3)	0.0000	0.33332 (13)	0.0647 (8)
N1	0.4894 (3)	0.0000	0.30625 (13)	0.0431 (7)
C1	0.6391 (4)	0.0000	0.35566 (18)	0.0457 (8)
C2	0.6418 (3)	0.0000	0.43622 (17)	0.0422 (8)
C3	0.7854 (4)	0.0000	0.48703 (18)	0.0510 (9)
H3	0.8806	0.0000	0.4703	0.061*
C4	0.4979 (3)	0.0000	0.46157 (16)	0.0384 (7)
C5	0.2086 (4)	0.0000	0.43639 (18)	0.0494 (9)
H5	0.1100	0.0000	0.4030	0.059*
C6	0.3486 (3)	0.0000	0.41020 (17)	0.0410 (7)
C7	0.3427 (4)	0.0000	0.32968 (18)	0.0446 (8)
C8	0.4868 (4)	0.0000	0.22507 (16)	0.0460 (8)
H8	0.5991	0.0000	0.2207	0.055*
C9	0.4125 (3)	0.1896 (4)	0.18665 (13)	0.0591 (7)
H9A	0.4684	0.3060	0.2110	0.071*
H9B	0.3010	0.1986	0.1901	0.071*
C10	0.4238 (3)	0.1862 (5)	0.10529 (14)	0.0708 (9)
H10A	0.3699	0.3031	0.0803	0.085*
H10B	0.5356	0.1926	0.1022	0.085*
C11	0.3488 (5)	0.0000	0.0665 (2)	0.0664 (11)
H11A	0.3624	0.0000	0.0156	0.080*
H11B	0.2348	0.0000	0.0654	0.080*

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Atomic displacement parameters (Å²)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0365 (12)	0.088 (2)	0.0494 (14)	0.000	0.0005 (9)	0.000
O2	0.0363 (12)	0.105 (2)	0.0535 (14)	0.000	0.0113 (10)	0.000
N1	0.0330 (12)	0.0522 (17)	0.0428 (14)	0.000	0.0052 (10)	0.000
C1	0.0323 (15)	0.051 (2)	0.0514 (19)	0.000	0.0047 (12)	0.000
C2	0.0322 (15)	0.0478 (19)	0.0456 (18)	0.000	0.0066 (12)	0.000
C3	0.0296 (15)	0.071 (2)	0.0513 (19)	0.000	0.0072 (12)	0.000
C4	0.0309 (14)	0.0364 (16)	0.0459 (16)	0.000	0.0040 (11)	0.000
C5	0.0292 (14)	0.065 (2)	0.0503 (19)	0.000	0.0012 (12)	0.000
C6	0.0303 (15)	0.0445 (18)	0.0460 (17)	0.000	0.0033 (12)	0.000
C7	0.0357 (15)	0.0466 (19)	0.0491 (18)	0.000	0.0038 (13)	0.000
C8	0.0379 (15)	0.059 (2)	0.0403 (17)	0.000	0.0059 (12)	0.000
C9	0.0643 (15)	0.0483 (15)	0.0601 (16)	−0.0050 (13)	0.0033 (11)	0.0031 (12)
C10	0.0716 (17)	0.080 (2)	0.0561 (16)	−0.0103 (17)	0.0045 (12)	0.0170 (15)
C11	0.056 (2)	0.094 (3)	0.047 (2)	0.000	0.0059 (16)	0.000

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Geometric parameters (Å, °)

O1—C7	1.212 (3)	C5—H5	0.9300
O2—C1	1.216 (4)	C6—C7	1.474 (4)
N1—C1	1.401 (4)	C8—C9ⁱⁱ	1.521 (3)
N1—C7	1.411 (4)	C8—C9	1.521 (3)
N1—C8	1.491 (4)	C8—H8	0.9800
C1—C2	1.480 (4)	C9—C10	1.523 (3)
C2—C3	1.373 (4)	C9—H9A	0.9700
C2—C4	1.406 (4)	C9—H9B	0.9700
C3—C5ⁱ	1.401 (4)	C10—C11	1.506 (4)
C3—H3	0.9300	C10—H10A	0.9700
C4—C4ⁱ	1.409 (6)	C10—H10B	0.9700
C4—C6	1.415 (4)	C11—C10ⁱⁱ	1.506 (4)
C5—C6	1.382 (4)	C11—H11A	0.9700
C5—C3ⁱ	1.401 (4)	C11—H11B	0.9700

C1—N1—C7	123.2 (3)	N1—C8—C9ⁱⁱ	112.42 (17)
C1—N1—C8	117.8 (3)	N1—C8—C9	112.42 (17)
C7—N1—C8	119.0 (2)	C9ⁱⁱ—C8—C9	112.7 (3)
O2—C1—N1	121.3 (3)	N1—C8—H8	106.2
O2—C1—C2	120.9 (3)	C9ⁱⁱ—C8—H8	106.2
N1—C1—C2	117.8 (3)	C9—C8—H8	106.2
C3—C2—C4	119.3 (3)	C8—C9—C10	109.7 (2)
C3—C2—C1	120.1 (3)	C8—C9—H9A	109.7
C4—C2—C1	120.5 (3)	C10—C9—H9A	109.7
C2—C3—C5ⁱ	121.3 (3)	C8—C9—H9B	109.7
C2—C3—H3	119.3	C10—C9—H9B	109.7
C5ⁱ—C3—H3	119.3	H9A—C9—H9B	108.2
C2—C4—C4ⁱ	120.0 (3)	C11—C10—C9	111.6 (3)
C2—C4—C6	120.3 (3)	C11—C10—H10A	109.3
C4ⁱ—C4—C6	119.7 (3)	C9—C10—H10A	109.3
C6—C5—C3ⁱ	120.4 (3)	C11—C10—H10B	109.3
C6—C5—H5	119.8	C9—C10—H10B	109.3
C3ⁱ—C5—H5	119.8	H10A—C10—H10B	108.0
C5—C6—C4	119.3 (3)	C10—C11—C10ⁱⁱ	111.3 (3)
C5—C6—C7	120.5 (3)	C10—C11—H11A	109.4
C4—C6—C7	120.2 (3)	C10ⁱⁱ—C11—H11A	109.4
O1—C7—N1	120.8 (3)	C10—C11—H11B	109.4
O1—C7—C6	121.2 (3)	C10ⁱⁱ—C11—H11B	109.4
N1—C7—C6	118.0 (2)	H11A—C11—H11B	108.0

C7—N1—C1—O2	180.0	C2—C4—C6—C7	0.0
C8—N1—C1—O2	0.0	C4ⁱ—C4—C6—C7	180.0
C7—N1—C1—C2	0.0	C1—N1—C7—O1	180.0
C8—N1—C1—C2	180.0	C8—N1—C7—O1	0.0
O2—C1—C2—C3	0.0	C1—N1—C7—C6	0.0
N1—C1—C2—C3	180.0	C8—N1—C7—C6	180.0
O2—C1—C2—C4	180.0	C5—C6—C7—O1	0.0
N1—C1—C2—C4	0.0	C4—C6—C7—O1	180.0
C4—C2—C3—C5ⁱ	0.000 (1)	C5—C6—C7—N1	180.0
C1—C2—C3—C5ⁱ	180.0	C4—C6—C7—N1	0.0
C3—C2—C4—C4ⁱ	0.0	C1—N1—C8—C9ⁱⁱ	115.76 (19)
C1—C2—C4—C4ⁱ	180.0	C7—N1—C8—C9ⁱⁱ	−64.24 (19)
C3—C2—C4—C6	180.0	C1—N1—C8—C9	−115.76 (19)
C1—C2—C4—C6	0.0	C7—N1—C8—C9	64.24 (19)
C3ⁱ—C5—C6—C4	0.000 (1)	N1—C8—C9—C10	176.2 (2)
C3ⁱ—C5—C6—C7	180.0	C9ⁱⁱ—C8—C9—C10	−55.5 (4)
C2—C4—C6—C5	180.0	C8—C9—C10—C11	55.2 (3)
C4ⁱ—C4—C6—C5	0.000 (1)	C9—C10—C11—C10ⁱⁱ	−56.5 (4)

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Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, −y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ2528).

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.
Chesterfield, R. J., McKeen, J. C., Newman, C. R., Ewbank, P. C., da SilvaFilho, D. A., Brédas, J. L., Miller, L. L., Mann, K. R. & Frisbie, C. D. (2004a). J. Phys. Chem. B, 108, 19281–19292.
Chesterfield, R. J., McKeen, J. C., Newman, C. R., Frisbie, C. D., Ewbank, P. C., Mann, K. R. & Miller, L. L. (2004b). Appl. Phys. Lett.95, 6396–6405.
Facceti, A., Yoon, M.-H. & Marks, T. J. (2008). Adv. Mater.17, 1705–1725.
Jones, B. A., Ahrens, M. J., Yoon, M.–H., Facchetti, A., Marks, T. J. & Wasielewski, M. R. (2004). Angew. Chem. Int. Ed 43, 6363–6366. [DOI] [PubMed]
Katz, H. E., Johnson, J., Lovinger, A. J. & Li, W. (2000a). J. Am. Chem. Soc.122, 7787–7792.
Katz, H. E., Lovinger, A. J., Johnson, J., Kloc, C., Siegrist, T., Li, W., Lin, Y.-Y. & Dodabalapur, A. (2000b). Nature (London), 404, 478–481. [DOI] [PubMed]
Nonius (2000). COLLECT Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
Shukla, D., Nelson, S. F., Freeman, D. C., Rajeswaran, M., Ahearn, W. G., Meyer, D. M. & Carey, J. T. (2008). Chem. Mater. Submitted.
Westrip, S. P. (2007). publCIF In preparation.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808025221/sj2528sup1.cif

e-64-o1735-sup1.cif^{(15.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025221/sj2528Isup2.hkl

e-64-o1735-Isup2.hkl^{(60.7KB, hkl)}

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

[bb1] Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst.32, 115–119.

[bb2] Chesterfield, R. J., McKeen, J. C., Newman, C. R., Ewbank, P. C., da SilvaFilho, D. A., Brédas, J. L., Miller, L. L., Mann, K. R. & Frisbie, C. D. (2004a). J. Phys. Chem. B, 108, 19281–19292.

[bb3] Chesterfield, R. J., McKeen, J. C., Newman, C. R., Frisbie, C. D., Ewbank, P. C., Mann, K. R. & Miller, L. L. (2004b). Appl. Phys. Lett.95, 6396–6405.

[bb4] Facceti, A., Yoon, M.-H. & Marks, T. J. (2008). Adv. Mater.17, 1705–1725.

[bb5] Jones, B. A., Ahrens, M. J., Yoon, M.–H., Facchetti, A., Marks, T. J. & Wasielewski, M. R. (2004). Angew. Chem. Int. Ed 43, 6363–6366. [DOI] [PubMed]

[bb6] Katz, H. E., Johnson, J., Lovinger, A. J. & Li, W. (2000a). J. Am. Chem. Soc.122, 7787–7792.

[bb7] Katz, H. E., Lovinger, A. J., Johnson, J., Kloc, C., Siegrist, T., Li, W., Lin, Y.-Y. & Dodabalapur, A. (2000b). Nature (London), 404, 478–481. [DOI] [PubMed]

[bb8] Nonius (2000). COLLECT Nonius BV, Delft, The Netherlands.

[bb9] Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

[bb10] Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]

[bb11] Shukla, D., Nelson, S. F., Freeman, D. C., Rajeswaran, M., Ahearn, W. G., Meyer, D. M. & Carey, J. T. (2008). Chem. Mater. Submitted.

[bb12] Westrip, S. P. (2007). publCIF In preparation.

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

Deepak Shukla

Manju Rajeswaran

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

Special details

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

Atomic displacement parameters (Å²)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

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RESOURCES

Cite

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PERMALINK

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

Deepak Shukla

Manju Rajeswaran

Abstract

Related literature

Experimental

Crystal data

Data collection

Refinement

Supplementary Material

Acknowledgments

supplementary crystallographic information

Comment

Experimental

Refinement

Figures

Fig. 1.

Crystal data

Data collection

Refinement

Special details

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

Atomic displacement parameters (Å2)

Geometric parameters (Å, °)

Footnotes

References

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

Similar articles

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

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

Atomic displacement parameters (Å²)