(1R*,2S*,4S*,5R*)-Cyclo­hexane-1,2:4,5-tetra­carb­oxy­lic dianhydride

Uchida, A.; Hasegawa, M.; Takezawa, E.; Yamaguchi, S.; Ishikawa, A.; Kagayama, T.

doi:10.1107/S1600536812003571

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o579

doi:10.1107/S1600536812003571

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(1R,2S,4S,5R)-Cyclohexane-1,2:4,5-tetracarboxylic dianhydride

Akira Uchida,^a ^* Masatoshi Hasegawa,^b Eiichiro Takezawa,^c Shinya Yamaguchi,^c Atsushi Ishikawa ^c and Takashi Kagayama ^c

^aDepartment of Biomolecular Science, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan, ^bDepartment of Chemistry, Faculty of Science, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan, and ^cDepartment of Research and Development, Gas Chemical Division, Iwatani Industrial Gases Corporation Ltd, 10 Otakasu-cho, Amagasaki, Hyogo 660-0842, Japan
^*Correspondence e-mail: auchida@biomol.sci.toho-u.ac.jp

(Received 28 December 2011; accepted 26 January 2012; online 4 February 2012)

The title compound, C₁₀H₈O₆, a promising raw material to obtain colorless polyimides which are applied to microelectronic and optoelectronic devices, adopts a folded conformation in which the dihedral angle between the two anhydro rings is 55.15 (8)°. The central six-membered ring assumes a conformation intermediate between boat and twist-boat. In the crystal, molecules are linked by weak C—H⋯O interactions, forming a layer parallel to the bc plane.

Related literature

For microelectronic applications of the present compound, see: Ando et al. (2010 ). For background to polyimides, see: Hasegawa et al. (2007 , 2008 ); Hasegawa & Horie (2001 ). For a related structure, see: Uchida et al. (2003 ).

Experimental

Crystal data

C₁₀H₈O₆
M_r = 224.16
Monoclinic, P 2₁ /c
a = 12.167 (2) Å
b = 7.1380 (14) Å
c = 10.626 (2) Å
β = 90.12 (3)°
V = 922.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 296 K
0.51 × 0.42 × 0.42 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.934, T_max = 0.945
6648 measured reflections
2285 independent reflections
2015 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.140
S = 1.00
2285 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O3ⁱ	0.98	2.40	3.3384 (19)	159
C3—H3B⋯O6ⁱⁱ	0.97	2.58	3.429 (2)	146
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ) and ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXL97 and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812003571/is5043sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812003571/is5043Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812003571/is5043Isup3.mol

Supporting information file. DOI: 10.1107/S1600536812003571/is5043Isup4.cml

checkCIF report

Comment top

Aromatic polyimides (PI) have been widely applied to microelectronic and optoelectronic devices for their reliable combined properties: considerably high glass transition temperatures (T_g), non-flammability, and good dielectric and mechanical properties (Ando et al., 2010). Conventional aromatic PI films are intensively colored on the basis of charge-transfer (CT) interactions (Hasegawa & Horie, 2001). However, the coloration often disturbs optical applications of PIs. Recently, there is a strong demand that further lightens the total weights of flat panel displays by replacing fragile inorganic glass substrates (~400 µm thick) by plastic substrates (~100 µm thick). However, it is not easy to develop the practically useful plastic substrates simultaneously possessing excellent optical transparency and sufficient heat resistance (T_g's > 250 °C) for the device fabrication processes such as inorganic transparent electrode deposition. The most effective strategy for completely erasing the significant PI film coloration is to use non-aromatic (cycloaliphatic) monomers either in tetracarboxylic dianhydride or diamine, thereby the CT interactions are inhibited. Our previous work illustrated that the equimolar polyaddition of cis, cis, cis-1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), synthesized by hydrogenation of pyromellitic dianhydride (PMDA), and some diamines indeed led to colorless PIs with very high T_g's (Hasegawa et al., 2007). However, the obtained PI films were very brittle in some cases owing to poor chain entanglement caused by insufficient molecular weights of the resultant PIs, which come from the insufficient reactivity of H-PMDA with diamines. The low reactivity of H-PMDA can be explained in terms of its steric structure (Uchida et al., 2003). In order to solve this crucial problem, we developed another H-PMDA isomer, i.e., 1R*, 2S*, 4S*, 5R*-cyclohexanetetracarboxylic dianhydride (H"-PMDA) (Hasegawa et al., 2008). The present work reports the crystal structure of this compound.

Related literature top

For microelectronic application of the present compound, see: Ando et al. (2010). For background to polyimides, see: Hasegawa et al. (2007, 2008); Hasegawa & Horie (2001). For a related structure, see: Uchida et al. (2003).

Experimental top

H"-PMDA was synthesized as follows (Hasegawa et al., 2008); PMDA was hydrolyzed with a NaOH aqueous solution. The pyromellitic acid tetrasodium salt formed was hydrogenated in a high-pressure hydrogen atmosphere in the presence of a ruthenium catalyst, and neutralized with conc. HCl. The tetracarboxylic acid obtained was isomerized by dehydrating with acetic anhydride at a precisely controlled temperature. Crystals of the title compound suitable for X-ray analysis were obtained from an acetic anhydride solution.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level.
	Fig. 2. The crystal packing of the title compound viewed along the b axis. The dashed lines indicate C—H···O intermolecular interactions.

(1R*,3R*,7S*,9S*)- 5,11-dioxatricyclo[7.3.0.0^3,7]dodecane-4,6,10,12-tetrone top

Crystal data top

C₁₀H₈O₆	F(000) = 464
M_r = 224.16	D_x = 1.613 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3549 reflections
a = 12.167 (2) Å	θ = 2.5–28.3°
b = 7.1380 (14) Å	µ = 0.14 mm⁻¹
c = 10.626 (2) Å	T = 296 K
β = 90.12 (3)°	Block, colorless
V = 922.8 (3) Å³	0.51 × 0.42 × 0.42 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2285 independent reflections
Radiation source: fine-focus sealed tube	2015 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 28.3°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→16
T_min = 0.934, T_max = 0.945	k = −9→9
6648 measured reflections	l = −7→14

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.140	w = 1/[σ²(F_o²) + (0.0954P)² + 0.121P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2285 reflections	Δρ_max = 0.30 e Å⁻³
146 parameters	Δρ_min = −0.18 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: 0.057 (8)

Crystal data top

C₁₀H₈O₆	V = 922.8 (3) Å³
M_r = 224.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.167 (2) Å	µ = 0.14 mm⁻¹
b = 7.1380 (14) Å	T = 296 K
c = 10.626 (2) Å	0.51 × 0.42 × 0.42 mm
β = 90.12 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2285 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2015 reflections with I > 2σ(I)
T_min = 0.934, T_max = 0.945	R_int = 0.026
6648 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.140	H-atom parameters constrained
S = 1.00	Δρ_max = 0.30 e Å⁻³
2285 reflections	Δρ_min = −0.18 e Å⁻³
146 parameters

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

	x	y	z	U_iso*/U_eq
O1	1.05049 (8)	−0.0274 (2)	0.67601 (13)	0.0712 (4)
O2	0.97350 (9)	0.22073 (16)	0.58580 (11)	0.0583 (3)
O3	0.85376 (13)	0.43198 (17)	0.50962 (13)	0.0773 (4)
O4	0.54696 (9)	0.16073 (17)	0.83493 (12)	0.0642 (3)
O5	0.61479 (8)	−0.12795 (16)	0.85526 (9)	0.0504 (3)
O6	0.68964 (10)	−0.40914 (17)	0.82316 (12)	0.0662 (4)
C1	0.85268 (9)	0.02100 (17)	0.69704 (11)	0.0371 (3)
H1	0.8492	0.0003	0.7881	0.045*
C2	0.79051 (10)	0.20009 (16)	0.66127 (11)	0.0382 (3)
H2	0.7781	0.2748	0.7373	0.046*
C3	0.68030 (11)	0.16836 (17)	0.59459 (13)	0.0439 (3)
H3A	0.6350	0.2794	0.6032	0.053*
H3B	0.6930	0.1473	0.5056	0.053*
C4	0.62021 (9)	0.00055 (17)	0.65005 (11)	0.0374 (3)
H4	0.5530	−0.0204	0.6010	0.045*
C5	0.68715 (10)	−0.18238 (16)	0.65113 (11)	0.0363 (3)
H5	0.6573	−0.2689	0.5881	0.044*
C6	0.80993 (10)	−0.15105 (16)	0.62629 (12)	0.0401 (3)
H6A	0.8509	−0.2608	0.6528	0.048*
H6B	0.8216	−0.1342	0.5367	0.048*
C7	0.96943 (10)	0.0603 (2)	0.65718 (13)	0.0479 (3)
C8	0.86994 (13)	0.3023 (2)	0.57707 (14)	0.0508 (4)
C9	0.58864 (9)	0.0285 (2)	0.78582 (13)	0.0431 (3)
C10	0.66715 (10)	−0.2597 (2)	0.78074 (13)	0.0434 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0325 (5)	0.0985 (10)	0.0825 (9)	0.0007 (5)	−0.0011 (5)	0.0044 (7)
O2	0.0524 (6)	0.0621 (7)	0.0605 (7)	−0.0161 (5)	0.0189 (5)	−0.0008 (5)
O3	0.1034 (10)	0.0551 (7)	0.0736 (8)	−0.0151 (7)	0.0130 (7)	0.0214 (6)
O4	0.0493 (6)	0.0756 (8)	0.0679 (7)	0.0162 (5)	0.0054 (5)	−0.0189 (6)
O5	0.0465 (5)	0.0679 (7)	0.0369 (5)	0.0015 (4)	0.0045 (4)	0.0062 (4)
O6	0.0716 (7)	0.0576 (7)	0.0694 (7)	0.0034 (5)	0.0005 (6)	0.0278 (6)
C1	0.0332 (5)	0.0456 (6)	0.0326 (5)	−0.0024 (4)	0.0015 (4)	0.0029 (5)
C2	0.0437 (6)	0.0349 (6)	0.0359 (6)	−0.0044 (4)	0.0042 (5)	−0.0022 (4)
C3	0.0494 (7)	0.0388 (6)	0.0436 (7)	0.0024 (5)	−0.0066 (5)	0.0077 (5)
C4	0.0318 (5)	0.0427 (6)	0.0377 (6)	0.0014 (4)	−0.0066 (4)	0.0019 (5)
C5	0.0359 (6)	0.0361 (6)	0.0368 (6)	−0.0030 (4)	0.0003 (4)	0.0013 (4)
C6	0.0365 (6)	0.0379 (6)	0.0461 (7)	0.0009 (4)	0.0073 (5)	−0.0005 (5)
C7	0.0383 (6)	0.0595 (8)	0.0460 (7)	−0.0094 (6)	0.0031 (5)	−0.0051 (6)
C8	0.0627 (9)	0.0427 (7)	0.0471 (7)	−0.0126 (6)	0.0090 (6)	0.0006 (6)
C9	0.0282 (5)	0.0548 (7)	0.0464 (7)	0.0024 (5)	−0.0005 (5)	−0.0042 (5)
C10	0.0368 (6)	0.0487 (7)	0.0447 (7)	−0.0040 (5)	−0.0011 (5)	0.0091 (5)

Geometric parameters (Å, º) top

O1—C7	1.1850 (19)	C2—C3	1.5322 (18)
O2—C7	1.3745 (19)	C2—H2	0.9800
O2—C8	1.391 (2)	C3—C4	1.5226 (17)
O3—C8	1.1869 (19)	C3—H3A	0.9700
O4—C9	1.1923 (17)	C3—H3B	0.9700
O5—C9	1.3754 (18)	C4—C9	1.5070 (18)
O5—C10	1.3853 (18)	C4—C5	1.5390 (16)
O6—C10	1.1898 (18)	C4—H4	0.9800
C1—C7	1.5095 (17)	C5—C10	1.5039 (17)
C1—C6	1.5304 (17)	C5—C6	1.5341 (17)
C1—C2	1.5328 (17)	C5—H5	0.9800
C1—H1	0.9800	C6—H6A	0.9700
C2—C8	1.5068 (18)	C6—H6B	0.9700

C7—O2—C8	110.60 (10)	C5—C4—H4	108.4
C9—O5—C10	110.53 (10)	C10—C5—C6	111.75 (10)
C7—C1—C6	109.29 (10)	C10—C5—C4	103.39 (10)
C7—C1—C2	103.86 (10)	C6—C5—C4	112.99 (9)
C6—C1—C2	112.36 (10)	C10—C5—H5	109.5
C7—C1—H1	110.4	C6—C5—H5	109.5
C6—C1—H1	110.4	C4—C5—H5	109.5
C2—C1—H1	110.4	C1—C6—C5	111.25 (10)
C8—C2—C3	111.02 (11)	C1—C6—H6A	109.4
C8—C2—C1	103.55 (10)	C5—C6—H6A	109.4
C3—C2—C1	114.98 (10)	C1—C6—H6B	109.4
C8—C2—H2	109.0	C5—C6—H6B	109.4
C3—C2—H2	109.0	H6A—C6—H6B	108.0
C1—C2—H2	109.0	O1—C7—O2	120.18 (13)
C4—C3—C2	110.96 (9)	O1—C7—C1	129.62 (14)
C4—C3—H3A	109.4	O2—C7—C1	110.16 (12)
C2—C3—H3A	109.4	O3—C8—O2	121.05 (14)
C4—C3—H3B	109.4	O3—C8—C2	129.08 (16)
C2—C3—H3B	109.4	O2—C8—C2	109.86 (12)
H3A—C3—H3B	108.0	O4—C9—O5	120.41 (13)
C9—C4—C3	112.95 (11)	O4—C9—C4	129.29 (13)
C9—C4—C5	103.95 (10)	O5—C9—C4	110.30 (10)
C3—C4—C5	114.57 (10)	O6—C10—O5	119.85 (13)
C9—C4—H4	108.4	O6—C10—C5	129.67 (14)
C3—C4—H4	108.4	O5—C10—C5	110.48 (11)

C7—C1—C2—C8	13.48 (13)	C6—C1—C7—O2	109.53 (12)
C6—C1—C2—C8	−104.52 (11)	C2—C1—C7—O2	−10.57 (13)
C7—C1—C2—C3	134.77 (11)	C7—O2—C8—O3	−172.68 (15)
C6—C1—C2—C3	16.77 (14)	C7—O2—C8—C2	6.61 (15)
C8—C2—C3—C4	155.23 (11)	C3—C2—C8—O3	42.5 (2)
C1—C2—C3—C4	38.11 (15)	C1—C2—C8—O3	166.44 (16)
C2—C3—C4—C9	63.98 (13)	C3—C2—C8—O2	−136.70 (12)
C2—C3—C4—C5	−54.81 (14)	C1—C2—C8—O2	−12.78 (14)
C9—C4—C5—C10	11.25 (11)	C10—O5—C9—O4	−176.99 (12)
C3—C4—C5—C10	134.99 (11)	C10—O5—C9—C4	3.01 (13)
C9—C4—C5—C6	−109.73 (11)	C3—C4—C9—O4	45.97 (18)
C3—C4—C5—C6	14.02 (14)	C5—C4—C9—O4	170.76 (14)
C7—C1—C6—C5	−172.96 (10)	C3—C4—C9—O5	−134.04 (11)
C2—C1—C6—C5	−58.22 (13)	C5—C4—C9—O5	−9.25 (12)
C10—C5—C6—C1	−74.30 (13)	C9—O5—C10—O6	−175.24 (13)
C4—C5—C6—C1	41.81 (13)	C9—O5—C10—C5	4.90 (14)
C8—O2—C7—O1	−179.25 (14)	C6—C5—C10—O6	−68.34 (18)
C8—O2—C7—C1	2.77 (15)	C4—C5—C10—O6	169.85 (14)
C6—C1—C7—O1	−68.20 (19)	C6—C5—C10—O5	111.50 (11)
C2—C1—C7—O1	171.70 (15)	C4—C5—C10—O5	−10.31 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱ	0.98	2.40	3.3384 (19)	159
C3—H3B···O6ⁱⁱ	0.97	2.58	3.429 (2)	146

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₈O₆
M_r	224.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.167 (2), 7.1380 (14), 10.626 (2)
β (°)	90.12 (3)
V (Å³)	922.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.51 × 0.42 × 0.42

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.934, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	6648, 2285, 2015
R_int	0.026

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.140, 1.00
No. of reflections	2285
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.18

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXS97 (Sheldrick, 2008), PLATON (Spek, 2009) and ORTEPIII (Burnett & Johnson, 1996), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱ	0.98	2.40	3.3384 (19)	159
C3—H3B···O6ⁱⁱ	0.97	2.58	3.429 (2)	146

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y−1/2, z−1/2.

References

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o579

doi:10.1107/S1600536812003571

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