1,1′:4′,1′′-Terphenyl-2′,5′-dicarb­oxy­lic acid dimethyl sulfoxide-d6 disolvate

Pop, L.C.; Preite, M.; Manriquez, J.M.; Vega, A.; Chavez, I.

doi:10.1107/S1600536812012056

organic compounds

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Volume 68| Part 4| April 2012| Page o1192

doi:10.1107/S1600536812012056

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1,1′:4′,1′′-Terphenyl-2′,5′-dicarboxylic acid dimethyl sulfoxide-d₆ disolvate

Lucian C. Pop,^a Marcelo Preite,^b Juan Manuel Manriquez,^c Andrés Vega ^d,^e ^* and Ivonne Chavez ^c ^*

^aUniversité Paul Sabatier, Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/CNRS 5069, France, ^bDepartamento de Química Orgánica, Facultad de Química, Pontificia Universidad Católica, Santiago, Chile, ^cDepartamento de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica, Santiago, Chile, Casilla 306 Correo 22, Santiago, Chile, ^dUniversidad Andres Bello, Departamento de Ciencias Químicas, Facultad de Ciencias Exactas, Av. República 275 3^er Piso, Santiago, Chile, and ^eCentro para el Desarrollo de la Nanociencia y la Nanotecnología, CEDENNA, Chile
^*Correspondence e-mail: andresvega@unab.cl, ichavez@uc.cl

(Received 30 January 2012; accepted 20 March 2012; online 28 March 2012)

The asymmetric unit of the title solvate, C₂₀H₁₄O₄·2C₂D₆OS, contains half of the substituted terephthalic acid molecule and one solvent molecule. The centroid of the central benzene ring in the acid molecule is coincident with a crystallographic inversion center. Neither the carboxyl nor the phenyl substituents are coplanar with the central aromatic ring, showing dihedral angles of 53.18 (11) and 47.83 (11)°, respectively. The dimethyl sulfoxide solvent molecules are hydrogen bonded to the carboxylic acid groups.

Related literature

For the synthesis of the title compound, see: Deuschel (1951 ); Ebel & Deuschel (1956 ). For similar molecules, see: Tanaka et al. (2009 ).

Experimental

Crystal data

C₂₀H₁₄O₄·2C₂D₆OS
M_r = 486.61
Triclinic, $[P \overline 1]$
a = 6.5184 (9) Å
b = 8.8273 (12) Å
c = 10.6017 (14) Å
α = 97.076 (2)°
β = 97.074 (2)°
γ = 93.127 (2)°
V = 599.26 (14) Å³
Z = 1
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 150 K
0.29 × 0.22 × 0.10 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.929, T_max = 0.975
3730 measured reflections
2101 independent reflections
1707 reflections with I > 2σ(I)
R_int = 0.012

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.145
S = 1.04
2101 reflections
148 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H10⋯O3ⁱ	0.926	1.659	2.581 (2)	174
Symmetry code: (i) x+1, y, z.

Data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 1999 ); data reduction: SAINT-NT; program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-NT; molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812012056/fy2045sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812012056/fy2045Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812012056/fy2045Isup3.cml

checkCIF report

Comment top

2,5-Diphenyl-1,4-benzenedicarboxylic acid (2,5-Diphenylterephthalic acid) has been described previously as a precursor towards trans-fluorenacenedione, prepared by its dehydration with sulfuric acid (Ebel & Deuschel, 1956).

The compound has a central terephtalic acid core, substituted at positions 2 and 5 with phenyl groups. The molecule has been previoulsy described by Tanaka et al. (Tanaka et al., 2009) in the form of an ethanol solvate. Tanaka et al. also described a related compound where the phenyl groups were replaced by p-fluorophenyl groups, which crystallized as a dimethylformamide solvate.

The carboxylic acid and the phenyl groups are highly planar. They define dihedral angles of 53.18 (11)° and 47.83 (11)°, respectively, with the central aromatic ring. The corresponding values are 28.2 (2)° and 57.2 (1)°, and 115.3 (1)° and 46.3 (1)°, for both dihedral angles in the ethanol solvate, and in the p-fluoro compound, respectively.

The molecule has an inversion center (crystallographic) coincident with the centroid of the central ring, so the point group symmetry of the isolated molecule is C_i. The same happens for the ethanol solvate and the p-fluoro compounds respectively.

The packing shows a deuterated dimethyl sulfoxide solvent molecule hydrogen bonded with each carboxylic acid group, with O1···O3ⁱⁱ distance of 2.581 (2) Å (ii: x + 1, y, z). There are two molecules of solvent for a single diacid molecule, each one defining one of the aforementioned hydrogen bond with each carboxylic acid group. A closely related pattern occurs for the ethanol solvate of the title molecule and the dimethylformamide solvate of the p-fluoro derivative (Tanaka et al., 2009): two molecules of solvent, ethanol or dimethylformamide, are bonded by hydrogen bonds to both carboxylic acid groups.

Related literature top

For the synthesis of the title compound, see: Deuschel (1951); Ebel & Deuschel (1956). For similar molecules, see: Tanaka et al. (2009).

Experimental top

The compound was prepared by a method described in the literature (Deuschel, 1951; Ebel & Deuschel, 1956), slighty modified by using d₆-DMSO for crystallization instead of C₆H₅CN, giving the DMSO-clathrate. The title compound was prepared in a 93% yield, mp. = 280°C (dec).

Structure description top

For the synthesis of the title compound, see: Deuschel (1951); Ebel & Deuschel (1956). For similar molecules, see: Tanaka et al. (2009).

Computing details top

Data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 1999); data reduction: SAINT-NT (Bruker, 1999); program(s) used to solve structure: SHELXTL-NT (Sheldrick, 2008); program(s) used to refine structure: SHELXTL-NT (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure diagram for I, showing the numbering scheme. Displacement ellipsoids are drawn at the 25% probability level and H atoms are shown as spheres of arbitrary radii. Symmetry codes (i): –x+1, –y+1, –z+1; (ii) x + 1, y, z; (iii): –x, –y+1, –z+1.

1,1':4',1''-Terphenyl-2',5'-dicarboxylic acid dimethyl sulfoxide-d₆ disolvate top

Crystal data top

C₂₀H₁₄O₄·2C₂D₆OS	Z = 1
M_r = 486.61	F(000) = 250
Triclinic, P1	D_x = 1.348 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5184 (9) Å	Cell parameters from 1643 reflections
b = 8.8273 (12) Å	θ = 2.3–24.2°
c = 10.6017 (14) Å	µ = 0.26 mm⁻¹
α = 97.076 (2)°	T = 150 K
β = 97.074 (2)°	Block, colorless
γ = 93.127 (2)°	0.29 × 0.22 × 0.10 mm
V = 599.26 (14) Å³

Data collection top

Siemens SMART CCD area-detector diffractometer	2101 independent reflections
Radiation source: fine-focus sealed tube	1707 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.012
φ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −7→7
T_min = 0.929, T_max = 0.975	k = −10→10
3730 measured reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0891P)² + 0.1414P] where P = (F_o² + 2F_c²)/3
2101 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₀H₁₄O₄·2C₂D₆OS	γ = 93.127 (2)°
M_r = 486.61	V = 599.26 (14) Å³
Triclinic, P1	Z = 1
a = 6.5184 (9) Å	Mo Kα radiation
b = 8.8273 (12) Å	µ = 0.26 mm⁻¹
c = 10.6017 (14) Å	T = 150 K
α = 97.076 (2)°	0.29 × 0.22 × 0.10 mm
β = 97.074 (2)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2101 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1707 reflections with I > 2σ(I)
T_min = 0.929, T_max = 0.975	R_int = 0.012
3730 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.04	Δρ_max = 0.53 e Å⁻³
2101 reflections	Δρ_min = −0.17 e Å⁻³
148 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
C1	0.6023 (3)	0.3696 (2)	0.48626 (19)	0.0397 (5)
H1	0.6737	0.2814	0.4770	0.048*
C2	0.6546 (3)	0.4883 (2)	0.41945 (19)	0.0371 (5)
C10	0.8077 (3)	0.4593 (2)	0.3263 (2)	0.0408 (5)
O1	0.9582 (2)	0.37837 (18)	0.36916 (14)	0.0503 (4)
O2	0.7903 (3)	0.5003 (2)	0.22114 (16)	0.0603 (5)
H10	1.0348	0.3461	0.3042	0.073 (8)*
C3	0.5515 (3)	0.6244 (2)	0.43352 (19)	0.0385 (5)
C4	0.6018 (3)	0.7627 (2)	0.3727 (2)	0.0413 (5)
C5	0.4423 (4)	0.8397 (3)	0.3156 (2)	0.0532 (6)
H5	0.3059	0.8007	0.3118	0.064*
C6	0.4828 (5)	0.9733 (3)	0.2644 (3)	0.0637 (7)
H6	0.3746	1.0236	0.2265	0.076*
C7	0.6846 (5)	1.0312 (3)	0.2699 (3)	0.0640 (7)
H7	0.7132	1.1199	0.2343	0.077*
C8	0.8446 (4)	0.9578 (3)	0.3283 (2)	0.0607 (7)
H8	0.9807	0.9980	0.3329	0.073*
C9	0.8033 (4)	0.8244 (3)	0.3801 (2)	0.0500 (6)
H9	0.9118	0.7760	0.4200	0.060*
S1	0.18071 (11)	0.35077 (8)	0.07652 (6)	0.0630 (3)
O3	0.1731 (3)	0.2709 (3)	0.19405 (18)	0.0834 (7)
C11	0.4021 (4)	0.2871 (4)	0.0103 (3)	0.0744 (8)
D11A	0.5249	0.3310	0.0647	0.112*
D11B	0.4020	0.3183	−0.0733	0.112*
D11C	0.3993	0.1776	0.0035	0.112*
C12	−0.0093 (5)	0.2526 (4)	−0.0412 (3)	0.0850 (10)
D12A	0.0088	0.1449	−0.0479	0.127*
D12B	0.0036	0.2878	−0.1222	0.127*
D12C	−0.1442	0.2715	−0.0180	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0418 (11)	0.0386 (11)	0.0396 (11)	0.0091 (8)	0.0070 (9)	0.0044 (9)
C2	0.0362 (10)	0.0422 (11)	0.0333 (10)	0.0052 (8)	0.0054 (8)	0.0045 (8)
C10	0.0433 (11)	0.0400 (11)	0.0397 (12)	0.0049 (9)	0.0094 (9)	0.0030 (9)
O1	0.0478 (9)	0.0628 (10)	0.0453 (9)	0.0194 (7)	0.0156 (7)	0.0105 (7)
O2	0.0705 (11)	0.0738 (12)	0.0461 (10)	0.0263 (9)	0.0230 (8)	0.0208 (8)
C3	0.0386 (11)	0.0411 (11)	0.0359 (11)	0.0049 (8)	0.0046 (8)	0.0050 (8)
C4	0.0470 (12)	0.0416 (12)	0.0377 (11)	0.0087 (9)	0.0115 (9)	0.0065 (9)
C5	0.0520 (13)	0.0555 (15)	0.0569 (14)	0.0134 (11)	0.0118 (11)	0.0177 (11)
C6	0.0789 (18)	0.0539 (15)	0.0655 (17)	0.0245 (13)	0.0157 (14)	0.0211 (12)
C7	0.098 (2)	0.0383 (13)	0.0591 (16)	0.0018 (13)	0.0223 (14)	0.0104 (11)
C8	0.0687 (16)	0.0521 (15)	0.0605 (16)	−0.0109 (12)	0.0133 (13)	0.0055 (12)
C9	0.0497 (13)	0.0495 (13)	0.0519 (14)	0.0036 (10)	0.0091 (10)	0.0090 (10)
S1	0.0719 (5)	0.0675 (5)	0.0573 (5)	0.0266 (3)	0.0223 (3)	0.0148 (3)
O3	0.1020 (16)	0.1079 (16)	0.0601 (12)	0.0620 (13)	0.0431 (11)	0.0331 (11)
C11	0.0644 (17)	0.102 (2)	0.0625 (17)	0.0194 (16)	0.0214 (14)	0.0155 (16)
C12	0.0634 (18)	0.104 (2)	0.091 (2)	0.0067 (17)	0.0121 (16)	0.0226 (19)

Geometric parameters (Å, º) top

C1—C2	1.385 (3)	C6—H6	0.9300
C1—C3ⁱ	1.391 (3)	C7—C8	1.380 (4)
C1—H1	0.9300	C7—H7	0.9300
C2—C3	1.410 (3)	C8—C9	1.386 (3)
C2—C10	1.498 (3)	C8—H8	0.9300
C10—O2	1.209 (3)	C9—H9	0.9300
C10—O1	1.314 (3)	S1—O3	1.5101 (19)
O1—H10	0.926	S1—C12	1.754 (3)
C3—C1ⁱ	1.391 (3)	S1—C11	1.769 (3)
C3—C4	1.489 (3)	C11—D11A	0.9600
C4—C9	1.384 (3)	C11—D11B	0.9600
C4—C5	1.390 (3)	C11—D11C	0.9600
C5—C6	1.384 (3)	C12—D12A	0.9600
C5—H5	0.9300	C12—D12B	0.9600
C6—C7	1.377 (4)	C12—D12C	0.9600

C2—C1—C3ⁱ	123.41 (19)	C6—C7—H7	120.0
C2—C1—H1	118.3	C8—C7—H7	120.0
C3ⁱ—C1—H1	118.3	C7—C8—C9	120.2 (2)
C1—C2—C3	119.46 (18)	C7—C8—H8	119.9
C1—C2—C10	117.34 (18)	C9—C8—H8	119.9
C3—C2—C10	122.99 (19)	C4—C9—C8	120.4 (2)
O2—C10—O1	123.55 (19)	C4—C9—H9	119.8
O2—C10—C2	123.75 (19)	C8—C9—H9	119.8
O1—C10—C2	112.63 (18)	O3—S1—C12	105.90 (15)
C10—O1—H10	110.50	O3—S1—C11	105.11 (13)
C1ⁱ—C3—C2	117.12 (19)	C12—S1—C11	98.15 (16)
C1ⁱ—C3—C4	118.39 (18)	S1—C11—D11A	109.5
C2—C3—C4	124.45 (18)	S1—C11—D11B	109.5
C9—C4—C5	118.6 (2)	D11A—C11—D11B	109.5
C9—C4—C3	121.63 (19)	S1—C11—D11C	109.5
C5—C4—C3	119.6 (2)	D11A—C11—D11C	109.5
C6—C5—C4	121.2 (2)	D11B—C11—D11C	109.5
C6—C5—H5	119.4	S1—C12—D12A	109.5
C4—C5—H5	119.4	S1—C12—D12B	109.5
C7—C6—C5	119.5 (2)	D12A—C12—D12B	109.5
C7—C6—H6	120.2	S1—C12—D12C	109.5
C5—C6—H6	120.2	D12A—C12—D12C	109.5
C6—C7—C8	120.1 (2)	D12B—C12—D12C	109.5

C3ⁱ—C1—C2—C3	1.1 (3)	C2—C3—C4—C9	−48.8 (3)
C3ⁱ—C1—C2—C10	−173.80 (19)	C1ⁱ—C3—C4—C5	−46.1 (3)
C1—C2—C10—O2	137.8 (2)	C2—C3—C4—C5	136.4 (2)
C3—C2—C10—O2	−37.0 (3)	C9—C4—C5—C6	1.4 (4)
C1—C2—C10—O1	−39.3 (3)	C3—C4—C5—C6	176.4 (2)
C3—C2—C10—O1	145.9 (2)	C4—C5—C6—C7	0.0 (4)
C1—C2—C3—C1ⁱ	−1.1 (3)	C5—C6—C7—C8	−1.2 (4)
C10—C2—C3—C1ⁱ	173.57 (18)	C6—C7—C8—C9	0.9 (4)
C1—C2—C3—C4	176.46 (19)	C5—C4—C9—C8	−1.8 (3)
C10—C2—C3—C4	−8.9 (3)	C3—C4—C9—C8	−176.6 (2)
C1ⁱ—C3—C4—C9	128.7 (2)	C7—C8—C9—C4	0.6 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H10···O3ⁱⁱ	0.926	1.659	2.581 (2)	174

Symmetry code: (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₄O₄·2C₂D₆OS
M_r	486.61
Crystal system, space group	Triclinic, P1
Temperature (K)	150
a, b, c (Å)	6.5184 (9), 8.8273 (12), 10.6017 (14)
α, β, γ (°)	97.076 (2), 97.074 (2), 93.127 (2)
V (Å³)	599.26 (14)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.29 × 0.22 × 0.10

Data collection
Diffractometer	Siemens SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.929, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	3730, 2101, 1707
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.145, 1.04
No. of reflections	2101
No. of parameters	148
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.17

Computer programs: SMART-NT (Bruker, 2001), SAINT-NT (Bruker, 1999), SHELXTL-NT (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H10···O3ⁱ	0.926	1.659	2.581 (2)	174

Symmetry code: (i) x+1, y, z.

Acknowledgements

The authors acknowledge financial support from FONDECYT 1110902 and Proyecto P07-006-F de la Iniciativa Científica Milenio del Ministerio de Economía, Fomento y Turismo. AV is a member of Financiamiento Basal para Centros Científicos y Tecnológicos de Excelencia FB0807.

References

Bruker (1999). SAINT-NT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SMART-NT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Deuschel, W. (1951). Helv. Chim. Acta, 34, 168–185. CrossRef CAS Web of Science Google Scholar
Ebel, F. & Deuschel, W. (1956). Chem. Ber. 69, 2794–2799. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tanaka, K., Akiyoshi, T., Itoh, H., Takahashi, H. & Urbanczyk-Lipkowska, Z. (2009). Tetrahedron, 65, 2318–2321. Web of Science CSD CrossRef CAS Google Scholar

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