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

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

doi:10.1107/S1600536813033795

organic compounds

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

Akira Uchida,^a ^* Masatoshi Hasegawa,^b Shinya Yamaguchi,^c Eiichiro Takezawa,^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 11 December 2013; accepted 13 December 2013; online 21 December 2013)

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.

CCDC reference: 976953

Related literature

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

Crystal data

C₁₀H₁₂O₈
M_r = 260.20
Trigonal, $[R \overline 3]$
a = 17.6970 (6) Å
c = 9.5455 (6) Å
V = 2589.0 (2) Å³
Z = 9
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.33 × 0.26 × 0.26 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.891, T_max = 0.966
6439 measured reflections
1653 independent reflections
1388 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.119
S = 1.06
1653 reflections
90 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H4⋯O1ⁱ	0.81 (3)	1.93 (3)	2.705 (2)	160 (3)
O4—H5⋯O3ⁱⁱ	0.94 (3)	1.70 (3)	2.632 (1)	176 (3)
Symmetry codes: (i) -x+y+1, -x+1, z; (ii) -x+1, -y, -z+1.

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

Supporting information

CCDC reference: 976953

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813033795/is5327sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813033795/is5327Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813033795/is5327Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S1600536813033795/is5327Isup4.cml

checkCIF report

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 (T_g), 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 T_gs (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.

Structure description 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).

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

	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.
	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

C₁₀H₁₂O₈	D_x = 1.502 Mg m⁻³
M_r = 260.20	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 2340 reflections
a = 17.6970 (6) Å	θ = 2.3–30.0°
c = 9.5455 (6) Å	µ = 0.13 mm⁻¹
V = 2589.0 (2) Å³	T = 298 K
Z = 9	Block, colourless
F(000) = 1224	0.33 × 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 tube	R_int = 0.019
φ and ω scans	θ_max = 30.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −24→21
T_min = 0.891, T_max = 0.966	k = −20→24
6439 measured reflections	l = −13→11
1653 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0607P)² + 1.9122P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1653 reflections	Δρ_max = 0.38 e Å⁻³
90 parameters	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₀H₁₂O₈	Z = 9
M_r = 260.20	Mo Kα radiation
Trigonal, R3	µ = 0.13 mm⁻¹
a = 17.6970 (6) Å	T = 298 K
c = 9.5455 (6) Å	0.33 × 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)
T_min = 0.891, T_max = 0.966	R_int = 0.019
6439 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.38 e Å⁻³
1653 reflections	Δρ_min = −0.21 e Å⁻³
90 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.

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

	x	y	z	U_iso*/U_eq
C1	0.51496 (8)	0.07671 (7)	−0.08154 (11)	0.0279 (3)
H1A	0.4929	0.1116	−0.1242	0.034*
H1B	0.5770	0.1045	−0.1011	0.034*
C2	0.50063 (7)	0.07293 (7)	0.07787 (11)	0.0233 (2)
H2	0.4383	0.0484	0.0969	0.028*
C3	0.53165 (7)	0.01523 (7)	0.14585 (11)	0.0242 (2)
H3	0.5944	0.0414	0.1285	0.029*
C4	0.55013 (8)	0.16503 (7)	0.13456 (12)	0.0283 (3)
C5	0.51702 (8)	0.00882 (8)	0.30236 (12)	0.0267 (3)
O1	0.62253 (6)	0.19739 (7)	0.18327 (13)	0.0471 (3)
H4	0.5352 (17)	0.2558 (18)	0.151 (3)	0.083 (8)*
O2	0.50596 (8)	0.20615 (8)	0.12244 (15)	0.0543 (3)
O3	0.46919 (7)	0.03210 (7)	0.35746 (9)	0.0380 (3)
O4	0.55716 (7)	−0.02417 (7)	0.37025 (10)	0.0400 (3)
H5	0.5485 (19)	−0.0245 (19)	0.467 (3)	0.110 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0389 (6)	0.0247 (5)	0.0218 (5)	0.0171 (5)	0.0021 (4)	0.0033 (4)
C2	0.0259 (5)	0.0227 (5)	0.0214 (5)	0.0123 (4)	0.0009 (4)	0.0002 (4)
C3	0.0274 (5)	0.0268 (5)	0.0198 (5)	0.0147 (4)	0.0014 (4)	0.0015 (4)
C4	0.0309 (6)	0.0246 (5)	0.0267 (5)	0.0119 (5)	0.0041 (4)	0.0008 (4)
C5	0.0310 (6)	0.0282 (5)	0.0214 (5)	0.0153 (5)	−0.0010 (4)	0.0009 (4)
O1	0.0302 (5)	0.0342 (5)	0.0672 (8)	0.0088 (4)	−0.0056 (5)	−0.0095 (5)
O2	0.0559 (7)	0.0333 (5)	0.0820 (9)	0.0285 (5)	−0.0212 (6)	−0.0187 (5)
O3	0.0517 (6)	0.0540 (6)	0.0237 (4)	0.0380 (5)	0.0042 (4)	0.0031 (4)
O4	0.0531 (6)	0.0611 (7)	0.0238 (4)	0.0420 (6)	0.0015 (4)	0.0059 (4)

Geometric parameters (Å, º) top

C1—C3ⁱ	1.5370 (16)	C3—H3	0.9800
C1—C2	1.5386 (15)	C4—O1	1.2049 (16)
C1—H1A	0.9700	C4—O2	1.3126 (16)
C1—H1B	0.9700	C5—O3	1.2295 (15)
C2—C4	1.5130 (15)	C5—O4	1.2961 (14)
C2—C3	1.5251 (15)	O2—H4	0.81 (3)
C2—H2	0.9800	O4—H5	0.94 (3)
C3—C5	1.5108 (15)

C3ⁱ—C1—C2	111.06 (9)	C5—C3—C1ⁱ	109.53 (9)
C3ⁱ—C1—H1A	109.4	C2—C3—C1ⁱ	110.89 (9)
C2—C1—H1A	109.4	C5—C3—H3	108.3
C3ⁱ—C1—H1B	109.4	C2—C3—H3	108.3
C2—C1—H1B	109.4	C1ⁱ—C3—H3	108.3
H1A—C1—H1B	108.0	O1—C4—O2	123.84 (12)
C4—C2—C3	111.15 (9)	O1—C4—C2	123.74 (11)
C4—C2—C1	108.23 (9)	O2—C4—C2	112.41 (11)
C3—C2—C1	110.07 (9)	O3—C5—O4	124.14 (11)
C4—C2—H2	109.1	O3—C5—C3	121.25 (10)
C3—C2—H2	109.1	O4—C5—C3	114.60 (10)
C1—C2—H2	109.1	C4—O2—H4	109.5 (18)
C5—C3—C2	111.43 (9)	C5—O4—H5	111.8 (17)

C3ⁱ—C1—C2—C4	178.45 (9)	C1—C2—C4—O1	−95.39 (14)
C3ⁱ—C1—C2—C3	56.81 (13)	C3—C2—C4—O2	−155.53 (11)
C4—C2—C3—C5	61.11 (12)	C1—C2—C4—O2	83.49 (13)
C1—C2—C3—C5	−179.00 (9)	C2—C3—C5—O3	14.47 (16)
C4—C2—C3—C1ⁱ	−176.60 (9)	C1ⁱ—C3—C5—O3	−108.61 (13)
C1—C2—C3—C1ⁱ	−56.70 (13)	C2—C3—C5—O4	−166.81 (10)
C3—C2—C4—O1	25.59 (16)	C1ⁱ—C3—C5—O4	70.12 (13)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H4···O1ⁱⁱ	0.81 (3)	1.93 (3)	2.705 (2)	160 (3)
O4—H5···O3ⁱⁱⁱ	0.94 (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···A	D—H	H···A	D···A	D—H···A
O2—H4···O1ⁱ	0.81 (3)	1.93 (3)	2.705 (2)	160 (3)
O4—H5···O3ⁱⁱ	0.94 (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

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 1| January 2014| Page o75

https://doi.org/10.1107/S1600536813033795

Open

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