N,N′-Bis(1-ethynylcyclo­hexyl)­pyro­mellitic diimide

Gondo, C.A.; Lynch, D.E.; Hamilton, D.G.

doi:10.1107/S1600536809030979

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2122

doi:10.1107/S1600536809030979

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N,N′-Bis(1-ethynylcyclohexyl)pyromellitic diimide

Chenaimwoyo A. Gondo,^a Daniel E. Lynch ^b and Darren G. Hamilton ^a ^*

^aDepartment of Chemistry, Mount Holyoke College, South Hadley, Masssachusetts 01075, USA, and ^bExilica Limited, The Technocentre, Puma Way, Coventry CV1 2TT, England
^*Correspondence e-mail: hamilton@mtholyoke.edu

(Received 14 July 2009; accepted 4 August 2009; online 8 August 2009)

The title compound, C₂₆H₂₄N₂O₄, consists of a symmetrical molecule that lies across a crystallographic inversion centre. The C—C distance in the triple bond is 1.188 (2) Å and there is also an intermolecular C—H⋯O contact from a terminal acetylene C—H to one of the dimiide O atoms [3.4349 (19) Å].

Related literature

For literature relating to the oxidative coupling of terminal acetylenes, see: Anderson, Anderson & Sanders (1995 ); Anderson, Walter et al. (1995 ); Hamilton et al. (1998 ); Raehm et al. (2002 ).

Experimental

Crystal data

C₂₆H₂₄N₂O₄
M_r = 428.47
Monoclinic, P 2₁ /c
a = 13.1774 (3) Å
b = 7.1519 (1) Å
c = 11.8104 (3) Å
β = 112.495 (1)°
V = 1028.36 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 120 K
0.40 × 0.35 × 0.20 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.963, T_max = 0.982
12939 measured reflections
2022 independent reflections
1898 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.158
S = 1.29
2022 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.80 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H12⋯O2ⁱ	0.95	2.52	3.4349 (19)	161
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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: PLATON97 (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809030979/zs2003sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030979/zs2003Isup2.hkl

checkCIF report

Comment top

The oxidative coupling of terminal acetylenes has proven to be a valuable architectural tool in the preparation of large macrocycles, especially when coupled to a templating mechanism to organize the premacrocycle components (Anderson, Anderson & Sanders, 1995). In this manner some remarkable structures have been assembled with admirable efficiency, given the entropic handicap imposed on the synthesis of large ring macrocycles (Anderson, Walter et al., 1995). One area in which a template greatly favors cyclization, and subsequently forms an integral part of the product structure, is in the synthesis of interlocked molecular compounds (catenanes and rotaxanes, Hamilton et al., 1998). Numerous systems have been reported that rely on the attractive interaction between π-electron deficient aromatic diimides and π-electron rich aromatic diethers to establish the desired templating effect (Raehm et al., 2002). In many of these instances the diimide component was equipped with terminal acetylenes, susbsequent oxidative coupling of which afforded the desired interlocked molecular systems. The title compound was prepared to address a key shortcoming of many acetylenic diimides of this type, namely their relatively low solubility in most organic solvents, in particular those in which the templating effects, so crucial to macrocycle synthesis, would be most effectively deployed. The presence of cyclohexyl substituents at the junctures of the diimide core with the acetylene substituents engendered high organic solvent solubility while retaining the key structural features required of the diimide unit. Reported here is the structure of the title compound (I), which is a symmetrical molecule that lies across a crystallographic inversion centre (Fig. 1), the asymmetric unit comprising half of the molecule. With such a simple molecule there are very few distinct features to report although it is worth mentioning that the C—C distance in the triple bond is 1.188 (2) Å. There is also an intermolecular C—H···O contact between the terminal acetylene C—H and one of the dimiide O atoms (Table 1).

Related literature top

For literature relating to the oxidative coupling of terminal acetylenes, see: Anderson, Anderson & Sanders (1995); Anderson, Walter et al. (1995); Hamilton et al. (1998); Raehm et al. (2002).

Experimental top

To a stirred solution of 1,2,4,5-benzenetetracarboxylic dianhydride (2.18 g, 10 mmol) in dry THF (20 mL) was added a solution of 1-ethynylcyclohexylamine (2.50 g, 2.74 ml, 20 mmol) in dry THF (10 ml). After 6 h the reaction was evaporated to give a white foam to which was added acetic anhydride (30 ml). After heating at 130° C for 2 h the reaction was cooled to room temperature and poured into vigorously stirred icecold water. The precipitated solids were collected at the pump, washed with cold water, and recrystallized from aqueous DMF to afford pale yellow crystals of the title compound (0.71 g, 17%): m.p. 219–220° C; ¹³C NMR (100 MHz, CDCl₃) δ 166.5, 138.0, 119.0, 83.0, 75.0, 60.0, 36.0, 25.0, 23.0; ¹H NMR (400 MHz, CDCl₃) δ 8.21 (s, 2H), 2.65 (s, 2H), 2.56–2.45, 2.44–2.29, 1.90–1.60, 1.40–1.20 (4 x multiplet, 20H). Single crystals of suitable quality for structure determination were grown by vapor diffusion of water into a DMF solution of the title compound.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON97 (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

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

N,N'-Bis(1-ethynylcyclohexyl)pyromellitic diimide top

Crystal data top

C₂₆H₂₄N₂O₄	F(000) = 452
M_r = 428.47	D_x = 1.384 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 492–493 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 13.1774 (3) Å	Cell parameters from 2528 reflections
b = 7.1519 (1) Å	θ = 2.9–27.5°
c = 11.8104 (3) Å	µ = 0.09 mm⁻¹
β = 112.495 (1)°	T = 120 K
V = 1028.36 (4) Å³	Prism, colourless
Z = 2	0.40 × 0.35 × 0.20 mm

Data collection top

Bruker–Nonius KappaCCD diffractometer	2022 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	1898 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.033
Detector resolution: 9.091 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ϕ & ω scans	h = −16→16
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −8→8
T_min = 0.963, T_max = 0.982	l = −13→14
12939 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)] = 0.065	H-atom parameters constrained
wR(F²) = 0.158	w = 1/[σ²(F_o²) + (0.091P)² + 0.2895P] where P = (F_o² + 2F_c²)/3
S = 1.29	(Δ/σ)_max = 0.001
2022 reflections	Δρ_max = 0.60 e Å⁻³
146 parameters	Δρ_min = −0.80 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.38 (3)

Crystal data top

C₂₆H₂₄N₂O₄	V = 1028.36 (4) Å³
M_r = 428.47	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.1774 (3) Å	µ = 0.09 mm⁻¹
b = 7.1519 (1) Å	T = 120 K
c = 11.8104 (3) Å	0.40 × 0.35 × 0.20 mm
β = 112.495 (1)°

Data collection top

Bruker–Nonius KappaCCD diffractometer	2022 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1898 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.982	R_int = 0.033
12939 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.29	Δρ_max = 0.60 e Å⁻³
2022 reflections	Δρ_min = −0.80 e Å⁻³
146 parameters

Special details top

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 0.798007.

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

	x	y	z	U_iso*/U_eq
O1	0.06501 (9)	0.08401 (16)	0.34794 (11)	0.0222 (4)
O2	0.22629 (9)	0.66713 (15)	0.40367 (11)	0.0202 (4)
N1	0.16857 (10)	0.35785 (17)	0.36123 (11)	0.0156 (4)
C2	0.08812 (12)	0.2440 (2)	0.37881 (13)	0.0158 (4)
C3	0.03482 (12)	0.3636 (2)	0.44392 (13)	0.0151 (4)
C4	0.07781 (12)	0.5432 (2)	0.45479 (13)	0.0152 (4)
C5	0.16567 (12)	0.5404 (2)	0.40426 (13)	0.0158 (4)
C6	−0.04412 (12)	0.3126 (2)	0.48923 (13)	0.0162 (4)
H1	−0.0726	0.1893	0.4825	0.020*
C7	0.25590 (11)	0.3002 (2)	0.31631 (13)	0.0150 (4)
C8	0.36865 (12)	0.3129 (2)	0.42496 (14)	0.0169 (4)
H2	0.3812	0.4431	0.4557	0.021*
H3	0.3680	0.2316	0.4925	0.021*
C9	0.46204 (12)	0.2530 (2)	0.38642 (15)	0.0208 (4)
H4	0.4676	0.3424	0.3251	0.026*
H5	0.5323	0.2563	0.4586	0.026*
C10	0.44355 (13)	0.0570 (2)	0.33209 (16)	0.0250 (4)
H6	0.4485	−0.0345	0.3969	0.031*
H7	0.5020	0.0272	0.3017	0.031*
C11	0.33156 (13)	0.0392 (2)	0.22690 (15)	0.0210 (4)
H8	0.3201	−0.0920	0.1979	0.026*
H9	0.3298	0.1191	0.1578	0.026*
C12	0.23911 (12)	0.0975 (2)	0.26781 (13)	0.0169 (4)
H10	0.2376	0.0120	0.3331	0.021*
H11	0.1677	0.0875	0.1977	0.021*
C13	0.25281 (12)	0.4268 (2)	0.21565 (14)	0.0178 (4)
C14	0.25817 (13)	0.5152 (2)	0.13290 (15)	0.0211 (4)
H12	0.2625	0.5858	0.0668	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0244 (6)	0.0177 (6)	0.0284 (7)	−0.0040 (4)	0.0144 (5)	−0.0057 (5)
O2	0.0223 (6)	0.0163 (6)	0.0262 (6)	−0.0021 (4)	0.0141 (5)	−0.0008 (4)
N1	0.0160 (6)	0.0157 (7)	0.0173 (7)	0.0003 (5)	0.0089 (5)	−0.0002 (5)
C2	0.0153 (7)	0.0177 (8)	0.0150 (7)	0.0000 (5)	0.0065 (6)	0.0006 (6)
C3	0.0151 (7)	0.0160 (8)	0.0138 (7)	0.0004 (5)	0.0051 (6)	0.0002 (5)
C4	0.0144 (7)	0.0165 (8)	0.0144 (7)	0.0004 (5)	0.0053 (6)	0.0019 (5)
C5	0.0167 (7)	0.0158 (8)	0.0153 (8)	0.0011 (5)	0.0068 (6)	0.0014 (5)
C6	0.0164 (7)	0.0147 (7)	0.0173 (8)	−0.0008 (5)	0.0064 (6)	−0.0003 (6)
C7	0.0150 (7)	0.0165 (8)	0.0159 (7)	0.0017 (5)	0.0085 (6)	0.0004 (6)
C8	0.0175 (8)	0.0182 (8)	0.0154 (8)	0.0004 (5)	0.0069 (6)	−0.0006 (6)
C9	0.0161 (8)	0.0257 (9)	0.0211 (8)	0.0010 (6)	0.0078 (6)	0.0001 (6)
C10	0.0205 (8)	0.0294 (9)	0.0251 (9)	0.0066 (6)	0.0086 (7)	−0.0039 (7)
C11	0.0227 (8)	0.0228 (9)	0.0185 (8)	0.0032 (6)	0.0091 (6)	−0.0038 (6)
C12	0.0181 (8)	0.0174 (8)	0.0159 (8)	−0.0001 (6)	0.0071 (6)	−0.0010 (6)
C13	0.0159 (7)	0.0189 (8)	0.0196 (8)	0.0027 (5)	0.0081 (6)	0.0001 (6)
C14	0.0219 (8)	0.0224 (8)	0.0217 (8)	0.0040 (6)	0.0111 (6)	0.0048 (7)

Geometric parameters (Å, º) top

O1—C2	1.2042 (19)	C8—H2	0.99
O2—C5	1.2100 (18)	C8—H3	0.99
N1—C5	1.4066 (19)	C9—C10	1.522 (2)
N1—C2	1.4136 (19)	C9—H4	0.99
N1—C7	1.4976 (18)	C9—H5	0.99
C2—C3	1.493 (2)	C10—C11	1.528 (2)
C3—C6	1.388 (2)	C10—H6	0.99
C3—C4	1.389 (2)	C10—H7	0.99
C4—C6ⁱ	1.387 (2)	C11—C12	1.530 (2)
C4—C5	1.492 (2)	C11—H8	0.99
C6—C4ⁱ	1.387 (2)	C11—H9	0.99
C6—H1	0.95	C12—H10	0.99
C7—C13	1.482 (2)	C12—H11	0.99
C7—C12	1.543 (2)	C13—C14	1.188 (2)
C7—C8	1.550 (2)	C14—H12	0.95
C8—C9	1.528 (2)

C5—N1—C2	110.85 (12)	C7—C8—H3	109.4
C5—N1—C7	120.94 (12)	H2—C8—H3	108.0
C2—N1—C7	127.92 (12)	C10—C9—C8	111.50 (13)
O1—C2—N1	128.31 (14)	C10—C9—H4	109.3
O1—C2—C3	125.88 (13)	C8—C9—H4	109.3
N1—C2—C3	105.81 (12)	C10—C9—H5	109.3
C6—C3—C4	123.13 (14)	C8—C9—H5	109.3
C6—C3—C2	128.11 (14)	H4—C9—H5	108.0
C4—C3—C2	108.76 (13)	C9—C10—C11	111.64 (13)
C3—C4—C6ⁱ	122.54 (14)	C9—C10—H6	109.3
C3—C4—C5	107.58 (13)	C11—C10—H6	109.3
C6ⁱ—C4—C5	129.77 (14)	C9—C10—H7	109.3
O2—C5—N1	125.73 (14)	C11—C10—H7	109.3
O2—C5—C4	127.39 (14)	H6—C10—H7	108.0
N1—C5—C4	106.83 (12)	C10—C11—C12	111.00 (12)
C3—C6—C4ⁱ	114.32 (14)	C10—C11—H8	109.4
C3—C6—H1	122.8	C12—C11—H8	109.4
C4ⁱ—C6—H1	122.8	C10—C11—H9	109.4
C13—C7—N1	109.08 (12)	C12—C11—H9	109.4
C13—C7—C12	108.67 (12)	H8—C11—H9	108.0
N1—C7—C12	111.69 (12)	C11—C12—C7	110.79 (12)
C13—C7—C8	110.59 (12)	C11—C12—H10	109.5
N1—C7—C8	108.28 (11)	C7—C12—H10	109.5
C12—C7—C8	108.54 (12)	C11—C12—H11	109.5
C9—C8—C7	111.30 (12)	C7—C12—H11	109.5
C9—C8—H2	109.4	H10—C12—H11	108.1
C7—C8—H2	109.4	C14—C13—C7	172.85 (16)
C9—C8—H3	109.4	C13—C14—H12	180.0

C5—N1—C2—O1	176.47 (15)	C6ⁱ—C4—C5—N1	178.17 (14)
C7—N1—C2—O1	−9.7 (2)	C4—C3—C6—C4ⁱ	0.8 (2)
C5—N1—C2—C3	−3.03 (16)	C2—C3—C6—C4ⁱ	−179.81 (14)
C7—N1—C2—C3	170.78 (13)	C5—N1—C7—C13	−57.01 (17)
O1—C2—C3—C6	5.3 (3)	C2—N1—C7—C13	129.74 (15)
N1—C2—C3—C6	−175.23 (14)	C5—N1—C7—C12	−177.14 (12)
O1—C2—C3—C4	−175.27 (14)	C2—N1—C7—C12	9.6 (2)
N1—C2—C3—C4	4.25 (16)	C5—N1—C7—C8	63.40 (17)
C6—C3—C4—C6ⁱ	−0.8 (3)	C2—N1—C7—C8	−109.86 (16)
C2—C3—C4—C6ⁱ	179.65 (13)	C13—C7—C8—C9	−61.41 (16)
C6—C3—C4—C5	175.74 (13)	N1—C7—C8—C9	179.13 (12)
C2—C3—C4—C5	−3.77 (16)	C12—C7—C8—C9	57.70 (16)
C2—N1—C5—O2	178.38 (14)	C7—C8—C9—C10	−56.05 (17)
C7—N1—C5—O2	4.1 (2)	C8—C9—C10—C11	54.10 (18)
C2—N1—C5—C4	0.82 (16)	C9—C10—C11—C12	−54.98 (18)
C7—N1—C5—C4	−173.49 (12)	C10—C11—C12—C7	57.87 (17)
C3—C4—C5—O2	−175.58 (15)	C13—C7—C12—C11	61.74 (15)
C6ⁱ—C4—C5—O2	0.7 (3)	N1—C7—C12—C11	−177.88 (11)
C3—C4—C5—N1	1.92 (16)	C8—C7—C12—C11	−58.57 (15)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H12···O2ⁱⁱ	0.95	2.52	3.4349 (19)	161

Symmetry code: (ii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₂₆H₂₄N₂O₄
M_r	428.47
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	13.1774 (3), 7.1519 (1), 11.8104 (3)
β (°)	112.495 (1)
V (Å³)	1028.36 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.35 × 0.20

Data collection
Diffractometer	Bruker–Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.963, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	12939, 2022, 1898
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.158, 1.29
No. of reflections	2022
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.80

Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON97 (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H12···O2ⁱ	0.95	2.52	3.4349 (19)	161.4

Symmetry code: (i) x, −y+3/2, z−1/2.

Acknowledgements

We thank the National Science Foundation (award No. 0314514), the Camille and Henry Dreyfus Foundation (Henry Dreyfus Teacher Scholar Award to DGH, 2005–2010), and the EPSRC National Crystallography Service (University of Southampton, England) for their support of this work.

References

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