N,N′-Bis(1-acetyl­cyclo­hexyl)-1,8:4,5-naphthalene­tetra­carboximide

Abstract

The title compound, C₃₀H₃₀N₂O₆, has crystallographic inversion symmetry with the nitro­gen atom and the two oxygen atoms of the naphthalene diimide system deviating by −0.243 (2), 0.109 (3) and 0.247 (2) Å, respectively, from the plane defined by the carbon atoms.

Related literature

For the structure of a related benzene diimide derivative with terminal acetyl­ene groups, see: Gondo et al. (2009 ▶). For preparative procedures for compounds of this type and for the title compound, see Hamilton et al. (1998 ▶, 1999 ▶); Raehm et al. (2002 ▶); Ahn et al. (1997 ▶).

Experimental

Crystal data

• C₃₀H₃₀N₂O₆

• M _r = 514.56

• Monoclinic,

• a = 5.8553 (2) Å

• b = 13.6603 (6) Å

• c = 15.2820 (6) Å

• β = 94.001 (2)°

• V = 1219.35 (8) ų

• Z = 2

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 120 K

• 0.20 × 0.18 × 0.06 mm

Data collection

• Bruker–Nonius 95 mm CCD camera on κ-goniostat diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.981, T _max = 0.994

• 11932 measured reflections

• 2397 independent reflections

• 1949 reflections with I > 2σ(I)

• R _int = 0.049

Refinement

• R[F ² > 2σ(F ²)] = 0.063

• wR(F ²) = 0.150

• S = 1.17

• 2397 reflections

• 174 parameters

• H-atom parameters constrained

• Δρ_max = 0.60 e Å⁻³

• Δρ_min = −0.59 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

supplementary crystallographic information

Comment

In a previous paper we presented the structure of a benzene diimide derivative having terminal acetylene groups and solubilizing cyclohexyl substituents (Gondo et al., 2009). This material was prepared for use in oxidative coupling reactions, thereby forming macrocycles as either isolated entities (Hamilton et al., 1999), or as components of molecularly interlocked systems (Hamilton et al., 1998; Raehm et al., 2002). As the corresponding naphthalene diimide analogues of benzene diimide derivatives are known to be generally more powerful electron acceptors, and have therefore been deployed in a variety of supramolecular and materials chemistry contexts, we attempted the preparation of the corresponding naphthalene diimide. However, under all of the standard conditions generally employed in the synthesis of benzene and naphthalene diimides we failed to obtain the desired compound. Only under rather forcing conditions was evidence of ring closure to the imide obtained, but under these conditions adventitious water was also found to have added to the acetylene groups (Ahn et al., 1997). Thus, a low yield of the diketone was the only isolable material obtained from this process and the structure of this compound (I) is reported here.

The title compound has crystallographic inversion symmetry (Fig. 1), (symmetry code: a -x + 1, -y + 1, -z + 1). The nitrogen and the two oxygen atoms of the naphthalene diimide systems deviate by -0.243 (2), 0.109 (3) and 0.247 (2) Å respectively from the plane defined by the carbon atoms.

Experimental

Under standard conditions for aromatic diimide formation (Hamilton et al., 1998; Hamilton et al., 1999) no evidence for the production of the desired acetylenic diimide could be found. Ring closure accompanied by unwanted addition of water across the acetylene bonds was observed using an alternative protocol (Ahn et al., 1997), giving a very low yield (<5%) of diketone (I) after chromatographic isolation. Single crystals of suitable quality for structure determination were grown by vapor diffusion of water into a DMF solution of the title compound.

Refinement

All H atoms were included in the refinement at calculated positions, in the riding-model approximation, with C–H distances of 0.95 (ArH), 0.98 (CH₃) and 0.99Å (CH₂). The isotropic displacement parameters for all H atoms were set equal to 1.25U_eq of the carrier atom. A large residual electron density (0.60 eÅ^-3) is located 0.57Å from H4.

Figures

Fig. 1.

Molecular configuration and atom-numbering scheme for (I) which has inversion symetry (symmetry code: a -x + 1, -y + 1, -z + 1). Displacement ellipsoids are drawn at the 50% probability level.

Crystal data

C30H30N2O6	F(000) = 544
Mr = 514.56	Dx = 1.401 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2881 reflections
a = 5.8553 (2) Å	θ = 2.9–27.5°
b = 13.6603 (6) Å	µ = 0.10 mm−1
c = 15.2820 (6) Å	T = 120 K
β = 94.001 (2)°	Plate, orange
V = 1219.35 (8) Å3	0.20 × 0.18 × 0.06 mm
Z = 2

Data collection

Bruker–Nonius 95 mm CCD camera on κ-goniostat diffractometer	2397 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1949 reflections with I > 2σ(I)
10 cm confocal mirrors	Rint = 0.049
Detector resolution: 9.091 pixels mm-1	θmax = 26.0°, θmin = 3.1°
φ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −16→16
Tmin = 0.981, Tmax = 0.994	l = −18→16
11932 measured reflections

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)] = 0.063	H-atom parameters constrained
wR(F2) = 0.150	w = 1/[σ2(Fo2) + (0.0786P)2 + 0.2672P] where P = (Fo2 + 2Fc2)/3
S = 1.17	(Δ/σ)max < 0.001
2397 reflections	Δρmax = 0.60 e Å−3
174 parameters	Δρmin = −0.59 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.094 (8)

Special details

Experimental. The minimum and maximum absorption values stated above are those calculated in SHELXL97 from the given crystal dimensions. The ratio of minimum to maximum apparent transmission was determined experimentally as 0.770335.

Geometry. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 3.5634 (0.0035) x - 0.8935 (0.0092) y + 11.4066 (0.0079) z = 7.0465 (0.0048) * -0.0167 (0.0010) C2 * 0.0088 (0.0016) C3 * -0.0098 (0.0013) C4 * -0.0071 (0.0012) C5 * 0.0161 (0.0011) C6 * 0.0087 (0.0011) C7 - 0.0027 (0.0028) C8 - 0.2429 (0.0022) N1 0.1089 (0.0026) O1 0.2471 (0.0023) O2 Rms deviation of fitted atoms = 0.0118

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

	x	y	z	Uiso*/Ueq
O1	0.9857 (2)	0.37034 (9)	0.34838 (9)	0.0236 (4)
O2	0.4959 (2)	0.19444 (9)	0.49973 (9)	0.0223 (4)
O3	1.0165 (2)	0.19678 (10)	0.23338 (9)	0.0266 (4)
N1	0.6940 (3)	0.28341 (11)	0.40186 (10)	0.0170 (4)
C2	0.8167 (3)	0.37028 (13)	0.39014 (12)	0.0181 (4)
C3	0.7265 (3)	0.46151 (13)	0.42772 (11)	0.0173 (4)
C4	0.5438 (3)	0.45653 (13)	0.48277 (11)	0.0164 (4)
C5	0.4497 (3)	0.36554 (13)	0.50527 (12)	0.0171 (4)
C6	0.5449 (3)	0.27368 (13)	0.47037 (12)	0.0177 (4)
C7	0.8165 (3)	0.55098 (13)	0.40659 (12)	0.0190 (4)
H1	0.9401	0.5540	0.3695	0.024*
C8	0.2735 (3)	0.36217 (13)	0.56043 (12)	0.0190 (4)
H2	0.2125	0.3007	0.5763	0.024*
C9	0.7659 (3)	0.19434 (13)	0.35194 (12)	0.0173 (4)
C10	0.8453 (3)	0.22945 (13)	0.26254 (12)	0.0204 (5)
C11	0.6832 (4)	0.29318 (15)	0.20654 (13)	0.0273 (5)
H3	0.7698	0.3451	0.1795	0.034*
H4	0.5707	0.3226	0.2432	0.034*
H5	0.6039	0.2533	0.1606	0.034*
C12	0.9518 (3)	0.13813 (13)	0.40723 (13)	0.0210 (5)
H6	0.9015	0.1301	0.4673	0.026*
H7	1.0936	0.1778	0.4115	0.026*
C13	1.0070 (3)	0.03672 (14)	0.37068 (14)	0.0245 (5)
H8	1.0946	0.0450	0.3180	0.031*
H9	1.1052	0.0007	0.4151	0.031*
C14	0.7927 (3)	−0.02394 (15)	0.34620 (15)	0.0278 (5)
H10	0.8365	−0.0859	0.3182	0.035*
H11	0.7153	−0.0404	0.3999	0.035*
C15	0.6295 (3)	0.03341 (14)	0.28330 (13)	0.0234 (5)
H12	0.4928	−0.0069	0.2668	0.029*
H13	0.7062	0.0489	0.2292	0.029*
C16	0.5565 (3)	0.12816 (13)	0.32632 (13)	0.0202 (5)
H14	0.4763	0.1124	0.3795	0.025*
H15	0.4483	0.1640	0.2852	0.025*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0219 (7)	0.0232 (7)	0.0269 (8)	−0.0025 (5)	0.0105 (6)	−0.0044 (6)
O2	0.0292 (8)	0.0171 (7)	0.0213 (7)	−0.0026 (6)	0.0057 (6)	0.0012 (5)
O3	0.0294 (8)	0.0235 (7)	0.0284 (8)	0.0017 (6)	0.0124 (6)	−0.0047 (6)
N1	0.0176 (8)	0.0171 (8)	0.0166 (8)	0.0003 (6)	0.0036 (6)	−0.0009 (6)
C2	0.0186 (9)	0.0210 (10)	0.0146 (9)	−0.0016 (7)	0.0007 (7)	−0.0005 (7)
C3	0.0182 (9)	0.0209 (10)	0.0125 (9)	−0.0015 (7)	−0.0003 (7)	−0.0020 (7)
C4	0.0149 (9)	0.0206 (10)	0.0132 (9)	−0.0001 (7)	−0.0016 (7)	−0.0001 (7)
C5	0.0184 (9)	0.0185 (10)	0.0140 (9)	−0.0003 (7)	−0.0013 (7)	−0.0001 (7)
C6	0.0178 (9)	0.0204 (10)	0.0147 (9)	−0.0015 (8)	−0.0003 (7)	−0.0010 (7)
C7	0.0197 (9)	0.0223 (10)	0.0153 (9)	−0.0015 (8)	0.0042 (7)	0.0004 (7)
C8	0.0218 (10)	0.0194 (9)	0.0160 (10)	−0.0039 (8)	0.0024 (7)	0.0016 (7)
C9	0.0163 (9)	0.0167 (9)	0.0192 (10)	0.0011 (7)	0.0032 (7)	−0.0016 (7)
C10	0.0240 (10)	0.0152 (9)	0.0223 (10)	−0.0024 (8)	0.0032 (8)	−0.0051 (7)
C11	0.0334 (12)	0.0279 (11)	0.0202 (10)	−0.0019 (9)	−0.0006 (9)	0.0019 (8)
C12	0.0189 (10)	0.0208 (10)	0.0232 (10)	0.0003 (8)	0.0007 (8)	0.0005 (8)
C13	0.0209 (10)	0.0213 (10)	0.0312 (11)	0.0041 (8)	0.0017 (8)	0.0028 (8)
C14	0.0257 (11)	0.0188 (10)	0.0397 (12)	0.0005 (8)	0.0074 (9)	−0.0013 (9)
C15	0.0212 (10)	0.0214 (10)	0.0280 (11)	−0.0043 (8)	0.0042 (8)	−0.0057 (8)
C16	0.0174 (9)	0.0210 (10)	0.0221 (10)	−0.0008 (8)	0.0013 (7)	−0.0020 (8)

Geometric parameters (Å, °)

O1—C2	1.214 (2)	C9—C16	1.552 (3)
O2—C6	1.214 (2)	C10—C11	1.509 (3)
O3—C10	1.210 (2)	C11—H3	0.98
N1—C2	1.405 (2)	C11—H4	0.98
N1—C6	1.415 (2)	C11—H5	0.98
N1—C9	1.512 (2)	C12—C13	1.537 (3)
C2—C3	1.485 (3)	C12—H6	0.99
C3—C7	1.378 (3)	C12—H7	0.99
C3—C4	1.408 (3)	C13—C14	1.528 (3)
C4—C4i	1.410 (3)	C13—H8	0.99
C4—C5	1.412 (3)	C13—H9	0.99
C5—C8	1.378 (3)	C14—C15	1.524 (3)
C5—C6	1.487 (3)	C14—H10	0.99
C7—C8i	1.406 (3)	C14—H11	0.99
C7—H1	0.95	C15—C16	1.526 (3)
C8—C7i	1.406 (3)	C15—H12	0.99
C8—H2	0.95	C15—H13	0.99
C9—C12	1.536 (3)	C16—H14	0.99
C9—C10	1.550 (3)	C16—H15	0.99
C2—N1—C6	121.39 (15)	H3—C11—H4	109.5
C2—N1—C9	116.90 (14)	C10—C11—H5	109.5
C6—N1—C9	120.37 (14)	H3—C11—H5	109.5
O1—C2—N1	120.69 (16)	H4—C11—H5	109.5
O1—C2—C3	121.85 (16)	C9—C12—C13	114.19 (16)
N1—C2—C3	117.42 (16)	C9—C12—H6	108.7
C7—C3—C4	120.12 (16)	C13—C12—H6	108.7
C7—C3—C2	120.09 (16)	C9—C12—H7	108.7
C4—C3—C2	119.76 (16)	C13—C12—H7	108.7
C3—C4—C4i	119.6 (2)	H6—C12—H7	107.6
C3—C4—C5	120.91 (16)	C14—C13—C12	112.81 (16)
C4i—C4—C5	119.5 (2)	C14—C13—H8	109.0
C8—C5—C4	120.00 (16)	C12—C13—H8	109.0
C8—C5—C6	120.44 (16)	C14—C13—H9	109.0
C4—C5—C6	119.55 (16)	C12—C13—H9	109.0
O2—C6—N1	122.08 (16)	H8—C13—H9	107.8
O2—C6—C5	121.05 (16)	C15—C14—C13	110.10 (16)
N1—C6—C5	116.87 (15)	C15—C14—H10	109.6
C3—C7—C8i	120.33 (17)	C13—C14—H10	109.6
C3—C7—H1	119.8	C15—C14—H11	109.6
C8i—C7—H1	119.8	C13—C14—H11	109.6
C5—C8—C7i	120.45 (17)	H10—C14—H11	108.2
C5—C8—H2	119.8	C14—C15—C16	110.27 (16)
C7i—C8—H2	119.8	C14—C15—H12	109.6
N1—C9—C12	109.66 (14)	C16—C15—H12	109.6
N1—C9—C10	107.88 (14)	C14—C15—H13	109.6
C12—C9—C10	113.28 (15)	C16—C15—H13	109.6
N1—C9—C16	110.69 (14)	H12—C15—H13	108.1
C12—C9—C16	111.39 (15)	C15—C16—C9	111.25 (15)
C10—C9—C16	103.78 (15)	C15—C16—H14	109.4
O3—C10—C11	120.53 (17)	C9—C16—H14	109.4
O3—C10—C9	121.16 (17)	C15—C16—H15	109.4
C11—C10—C9	117.60 (16)	C9—C16—H15	109.4
C10—C11—H3	109.5	H14—C16—H15	108.0
C10—C11—H4	109.5
C6—N1—C2—O1	160.09 (17)	C2—C3—C7—C8i	177.80 (17)
C9—N1—C2—O1	−6.8 (2)	C4—C5—C8—C7i	1.1 (3)
C6—N1—C2—C3	−22.2 (2)	C6—C5—C8—C7i	−179.98 (17)
C9—N1—C2—C3	170.95 (15)	C2—N1—C9—C12	89.38 (18)
O1—C2—C3—C7	8.2 (3)	C6—N1—C9—C12	−77.62 (19)
N1—C2—C3—C7	−169.49 (17)	C2—N1—C9—C10	−34.4 (2)
O1—C2—C3—C4	−173.83 (17)	C6—N1—C9—C10	158.59 (15)
N1—C2—C3—C4	8.5 (2)	C2—N1—C9—C16	−147.33 (16)
C7—C3—C4—C4i	−1.0 (3)	C6—N1—C9—C16	45.7 (2)
C2—C3—C4—C4i	−179.01 (19)	N1—C9—C10—O3	136.51 (17)
C7—C3—C4—C5	−179.86 (17)	C12—C9—C10—O3	14.9 (2)
C2—C3—C4—C5	2.2 (3)	C16—C9—C10—O3	−106.01 (19)
C3—C4—C5—C8	178.90 (16)	N1—C9—C10—C11	−53.1 (2)
C4i—C4—C5—C8	0.1 (3)	C12—C9—C10—C11	−174.65 (15)
C3—C4—C5—C6	0.0 (3)	C16—C9—C10—C11	64.39 (19)
C4i—C4—C5—C6	−178.82 (19)	N1—C9—C12—C13	169.46 (15)
C2—N1—C6—O2	−155.80 (17)	C10—C9—C12—C13	−70.0 (2)
C9—N1—C6—O2	10.6 (3)	C16—C9—C12—C13	46.6 (2)
C2—N1—C6—C5	24.2 (2)	C9—C12—C13—C14	−48.2 (2)
C9—N1—C6—C5	−169.37 (15)	C12—C13—C14—C15	54.2 (2)
C8—C5—C6—O2	−11.5 (3)	C13—C14—C15—C16	−60.5 (2)
C4—C5—C6—O2	167.34 (17)	C14—C15—C16—C9	60.2 (2)
C8—C5—C6—N1	168.43 (16)	N1—C9—C16—C15	−174.79 (15)
C4—C5—C6—N1	−12.7 (2)	C12—C9—C16—C15	−52.5 (2)
C4—C3—C7—C8i	−0.2 (3)	C10—C9—C16—C15	69.71 (18)

Symmetry codes: (i) −x+1, −y+1, −z+1.