supplementary materials


is5327 scheme

Acta Cryst. (2014). E70, o75    [ doi:10.1107/S1600536813033795 ]

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

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

Abstract top

The title compound, C10H12O8, a prospective raw material for colourless polyimides which are applied to electronic and microelectronic devices, lies about an inversion centre and the cyclo­hexane ring adopts a chair conformation. Two crystallographycally independent carb­oxy­lic acid groups on adjacent C atoms are in equatorial positions, resulting in a mutually trans conformation. In the crystal, O-H...O hydrogen bonds around an inversion centre and a threefold rotoinversion axis, respectively, form an inversion dimer with an R22(8) motif and a trimer with an R33(12) motif.

Comment top

Aromatic polyimides (PI) are one of the most important heat-resistant polymeric materials in various electronic applications for their reliable combined properties: considerably high glass transition temperatures (Tg), non-flammability, and good dielectric and mechanical properties (Ando et al., 2010). However, intensive coloration of conventional PI films, which arises from charge-transfer (CT) interactions (Hasegawa & Horie, 2001), often disturbs their applications as optical materials. A recent strong demand is to replace inorganic glass substrates in flat panel displays (300–700 µm thick) by plastic substrates (< 100 µm thick), thereby the displays become drastically light and flexible. However, it is difficult to obtain the substrate materials simultaneously possessing excellent combined properties, i.e., optical transparency, heat resistance, dimensional stability against thermal cycles undergoing in the device fabrication process, flexibility, and processability. The most effective strategy for completely erasing the coloration is to inhibit the CT interactions by using non-aromatic (cycloaliphatic) monomers either in tetracarboxylic dianhydride or diamine components. For this purpose, we previously investigated the steric structures of hydrogenated pyromellitic dianhydride isomers, i.e., 1S,2R,4S,5R-cyclohexanetetracarboxylic dianhydride (H-PMDA) (Uchida et al., 2003) and 1R,2S,4S,5R-cyclohexanetetracarboxylic dianhydride (H"-PMDA) (Uchida et al., 2012). H"-PMDA showed much higher reactivity with diamines than H-PMDA and provided highly flexible colourless PI films with significantly improved solution-processability while keeping very high Tgs (Hasegawa et al., 2007, 2013). The results are based on a peculiar steric structure of H"-PMDA. Unfortunately, neither H-PMDA nor H"-PMDA led to PI films with low coefficients of thermal expansion (CTE) required for the excellent dimensional stability, probably owing to their non-linear/non-planar steric structures. An additional H-PMDA isomer, i.e., 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride (H'-PMDA) can be expected to derive a novel low-CTE colourless PI system. The present work reports a crystal structure of a hydrolyzed compound of H'-PMDA.

Related literature top

For background to polyimides, see: Ando et al. (2010); Hasegawa et al. (2007, 2013); Hasegawa & Horie (2001). For related structures, see: Uchida et al. (2003, 2012).

Experimental top

The title compound, (I), was synthesized as follows. Pyromellitic dianhydride was first hydrolyzed with a NaOH aqueous solution. The pyromellitic acid tetrasodium salt formed was hydrogenated in a high-pressure hydrogen atmosphere at 160 °C in the presence of a ruthenium catalyst. After hydrogenation was completed, the solution was additionally heated at a precisely controlled temperature for several hours, and cooled to room temperature. The solution was neutralized by slowly adding conc. HCl. The white precipitate formed was collected by filtration, recrystallized from water, and dried in vacuum at 80 °C for 5 h to obtain crystals of (I) suitable for X-ray analysis.

Refinement top

All H atoms were observable in a difference Fourier map. H atoms on O atoms were refined freely [O—H = 0.81 (3) and 0.94 (3) Å]. Other H atoms were placed in calculated positions with C—H = 0.97–0.98 Å, and allowed to ride on their carrier atoms, with Uiso(H) = 1.2Ueq(C).

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: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids at the 50% probability level. H atoms are represented by circles of arbitrary size.
[Figure 2] Fig. 2. The packing of the title compound, viewed down the c axis,
(1S*,2S*,4R*,5R*)-Cyclohexane-1,2,4,5-tetracarboxylic acid top
Crystal data top
C10H12O8Dx = 1.502 Mg m3
Mr = 260.20Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 2340 reflections
a = 17.6970 (6) Åθ = 2.3–30.0°
c = 9.5455 (6) ŵ = 0.13 mm1
V = 2589.0 (2) Å3T = 298 K
Z = 9Block, colourless
F(000) = 12240.33 × 0.26 × 0.26 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1388 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.019
φ and ω scansθmax = 30.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2421
Tmin = 0.891, Tmax = 0.966k = 2024
6439 measured reflectionsl = 1311
1653 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.119 w = 1/[σ2(Fo2) + (0.0607P)2 + 1.9122P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1653 reflectionsΔρmax = 0.38 e Å3
90 parametersΔρmin = 0.21 e Å3
Crystal data top
C10H12O8Z = 9
Mr = 260.20Mo Kα radiation
Trigonal, R3µ = 0.13 mm1
a = 17.6970 (6) ÅT = 298 K
c = 9.5455 (6) Å0.33 × 0.26 × 0.26 mm
V = 2589.0 (2) Å3
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1653 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1388 reflections with I > 2σ(I)
Tmin = 0.891, Tmax = 0.966Rint = 0.019
6439 measured reflectionsθmax = 30.0°
Refinement top
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.119Δρmax = 0.38 e Å3
S = 1.06Δρmin = 0.21 e Å3
1653 reflectionsAbsolute structure: ?
90 parametersAbsolute structure parameter: ?
0 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.51496 (8)0.07671 (7)0.08154 (11)0.0279 (3)
H1A0.49290.11160.12420.034*
H1B0.57700.10450.10110.034*
C20.50063 (7)0.07293 (7)0.07787 (11)0.0233 (2)
H20.43830.04840.09690.028*
C30.53165 (7)0.01523 (7)0.14585 (11)0.0242 (2)
H30.59440.04140.12850.029*
C40.55013 (8)0.16503 (7)0.13456 (12)0.0283 (3)
C50.51702 (8)0.00882 (8)0.30236 (12)0.0267 (3)
O10.62253 (6)0.19739 (7)0.18327 (13)0.0471 (3)
H40.5352 (17)0.2558 (18)0.151 (3)0.083 (8)*
O20.50596 (8)0.20615 (8)0.12244 (15)0.0543 (3)
O30.46919 (7)0.03210 (7)0.35746 (9)0.0380 (3)
O40.55716 (7)0.02417 (7)0.37025 (10)0.0400 (3)
H50.5485 (19)0.0245 (19)0.467 (3)0.110 (10)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0389 (6)0.0247 (5)0.0218 (5)0.0171 (5)0.0021 (4)0.0033 (4)
C20.0259 (5)0.0227 (5)0.0214 (5)0.0123 (4)0.0009 (4)0.0002 (4)
C30.0274 (5)0.0268 (5)0.0198 (5)0.0147 (4)0.0014 (4)0.0015 (4)
C40.0309 (6)0.0246 (5)0.0267 (5)0.0119 (5)0.0041 (4)0.0008 (4)
C50.0310 (6)0.0282 (5)0.0214 (5)0.0153 (5)0.0010 (4)0.0009 (4)
O10.0302 (5)0.0342 (5)0.0672 (8)0.0088 (4)0.0056 (5)0.0095 (5)
O20.0559 (7)0.0333 (5)0.0820 (9)0.0285 (5)0.0212 (6)0.0187 (5)
O30.0517 (6)0.0540 (6)0.0237 (4)0.0380 (5)0.0042 (4)0.0031 (4)
O40.0531 (6)0.0611 (7)0.0238 (4)0.0420 (6)0.0015 (4)0.0059 (4)
Geometric parameters (Å, º) top
C1—C3i1.5370 (16)C3—H30.9800
C1—C21.5386 (15)C4—O11.2049 (16)
C1—H1A0.9700C4—O21.3126 (16)
C1—H1B0.9700C5—O31.2295 (15)
C2—C41.5130 (15)C5—O41.2961 (14)
C2—C31.5251 (15)O2—H40.81 (3)
C2—H20.9800O4—H50.94 (3)
C3—C51.5108 (15)
C3i—C1—C2111.06 (9)C5—C3—C1i109.53 (9)
C3i—C1—H1A109.4C2—C3—C1i110.89 (9)
C2—C1—H1A109.4C5—C3—H3108.3
C3i—C1—H1B109.4C2—C3—H3108.3
C2—C1—H1B109.4C1i—C3—H3108.3
H1A—C1—H1B108.0O1—C4—O2123.84 (12)
C4—C2—C3111.15 (9)O1—C4—C2123.74 (11)
C4—C2—C1108.23 (9)O2—C4—C2112.41 (11)
C3—C2—C1110.07 (9)O3—C5—O4124.14 (11)
C4—C2—H2109.1O3—C5—C3121.25 (10)
C3—C2—H2109.1O4—C5—C3114.60 (10)
C1—C2—H2109.1C4—O2—H4109.5 (18)
C5—C3—C2111.43 (9)C5—O4—H5111.8 (17)
C3i—C1—C2—C4178.45 (9)C1—C2—C4—O195.39 (14)
C3i—C1—C2—C356.81 (13)C3—C2—C4—O2155.53 (11)
C4—C2—C3—C561.11 (12)C1—C2—C4—O283.49 (13)
C1—C2—C3—C5179.00 (9)C2—C3—C5—O314.47 (16)
C4—C2—C3—C1i176.60 (9)C1i—C3—C5—O3108.61 (13)
C1—C2—C3—C1i56.70 (13)C2—C3—C5—O4166.81 (10)
C3—C2—C4—O125.59 (16)C1i—C3—C5—O470.12 (13)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H4···O1ii0.81 (3)1.93 (3)2.705 (2)160 (3)
O4—H5···O3iii0.94 (3)1.70 (3)2.632 (1)176 (3)
Symmetry codes: (ii) x+y+1, x+1, z; (iii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H4···O1i0.81 (3)1.93 (3)2.705 (2)160 (3)
O4—H5···O3ii0.94 (3)1.70 (3)2.632 (1)176 (3)
Symmetry codes: (i) x+y+1, x+1, z; (ii) x+1, y, z+1.
references
References top

Ando, S., Ueda, M., Kakimoto, M., Kochi, M., Takeichi, T., Hasegawa, M. & Yokota, R. (2010). The Latest Polyimides: Fundamentals and Applications, 2nd ed. Tokyo: NTS.

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Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.

Hasegawa, M., Hirano, D., Fujii, M., Haga, M., Takezawa, E., Yamaguchi, S., Ishikawa, A. & Kagayama, T. (2013). J. Polym. Sci. Part A, 51, 575–592.

Hasegawa, M. & Horie, K. (2001). Prog. Polym. Sci. 26, 259–335.

Hasegawa, M., Horiuchi, M. & Wada, Y. (2007). High Perform. Polym. 19, 175–193.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Uchida, A., Hasegawa, M. & Manami, H. (2003). Acta Cryst. C59, o435–o438.

Uchida, A., Hasegawa, M., Takezawa, E., Yamaguchi, S., Ishikawa, A. & Kagayama, T. (2012). Acta Cryst. E68, o579.