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1,1':4',1''-Terphenyl-2',5'-dicarb-oxy-lic acid dimethyl sulfoxide-d(6) disolvate.
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PMID:  22606132     Owner:  NLM     Status:  In-Data-Review    
Abstract/OtherAbstract:
The asymmetric unit of the title solvate, C(20)H(14)O(4)·2C(2)D(6)OS, contains half of the substituted terephthalic acid mol-ecule and one solvent mol-ecule. The centroid of the central benzene ring in the acid mol-ecule 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 mol-ecules are hydrogen bonded to the carb-oxy-lic acid groups.
Authors:
Lucian C Pop; Marcelo Preite; Juan Manuel Manriquez; Andrés Vega; Ivonne Chavez
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Type:  Journal Article     Date:  2012-03-28
Journal Detail:
Title:  Acta crystallographica. Section E, Structure reports online     Volume:  68     ISSN:  1600-5368     ISO Abbreviation:  Acta Crystallogr Sect E Struct Rep Online     Publication Date:  2012 Apr 
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Created Date:  2012-05-18     Completed Date:  -     Revised Date:  -    
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Nlm Unique ID:  101089178     Medline TA:  Acta Crystallogr Sect E Struct Rep Online     Country:  United States    
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Languages:  eng     Pagination:  o1192     Citation Subset:  -    
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Journal ID (nlm-ta): Acta Crystallogr Sect E Struct Rep Online
Journal ID (iso-abbrev): Acta Crystallogr Sect E Struct Rep Online
Journal ID (publisher-id): Acta Cryst. E
ISSN: 1600-5368
Publisher: International Union of Crystallography
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A full version of this article is available from Crystallography Journals Online.© Pop et al. 2012
open-access:
Received Day: 30 Month: 1 Year: 2012
Accepted Day: 20 Month: 3 Year: 2012
collection publication date: Day: 01 Month: 4 Year: 2012
Electronic publication date: Day: 28 Month: 3 Year: 2012
pmc-release publication date: Day: 28 Month: 3 Year: 2012
Volume: 68 Issue: Pt 4
First Page: o1192 Last Page: o1192
ID: 3344129
PubMed Id: 22606132
Publisher Id: fy2045
DOI: 10.1107/S1600536812012056
Coden: ACSEBH
Publisher Item Identifier: S1600536812012056

1,1′:4′,1′′-Terphenyl-2′,5′-dicarb­oxy­lic acid dimethyl sulfoxide-d6 disolvate Alternate Title:C20H14O4·2C2D6OS
Lucian C. Popa
Marcelo Preiteb
Juan Manuel Manriquezc
Andrés Vegade*
Ivonne Chavezc*
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 3er Piso, Santiago, Chile
eCentro para el Desarrollo de la Nanociencia y la Nanotecnología, CEDENNA, Chile
Correspondence: Correspondence e-mail: andresvega@unab.cl, ichavez@uc.cl

Related literature  

For the synthesis of the title compound, see: Deuschel (1951); Ebel & Deuschel (1956). For similar mol­ecules, see: Tanaka et al. (2009).[Chemical Structure ID: scheme1]


Experimental  
Crystal data  

  • C20H14O4·2C2D6OS
  • Mr = 486.61
  • Triclinic,
  • 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) Tmin = 0.929, Tmax = 0.975
  • 3730 measured reflections
  • 2101 independent reflections
  • 1707 reflections with I > 2σ(I)
  • Rint = 0.012

Refinement  

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

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.


Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812012056/fy2045sup1.cif

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

Supplementary material file. DOI: 10.1107/S1600536812012056/fy2045Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report


Notes

fnu1Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FY2045).

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.

supplementary crystallographic information
Comment

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 Ci. 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.

Experimental

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).

Refinement

The hydrogen atoms positions were calculated after each cycle of refinement with SHELXL (Bruker,1999) using a riding model, with C—H distances in the range of 0.93 to 0.96 Å. Uiso(H) values were set equal to 1.5Ueq of the parent carbon atom for methyl groups, and 1.2Ueq for the others. The carboxylic acid hydrogen atom was located in the difference Fourier map, and its coordinates were subsequentely kept fixed (by adding 10 to the coordinates in SHELXL), while Uiso(H) was left free to refine.

Figures
Crystal data
Data collection
Refinement
Special details
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
Atomic displacement parameters (Å2)
Geometric parameters (Å, º)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

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


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

Figures

[Figure ID: Fap1]
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.



Tables
[TableWrap ID: d1e206]
C20H14O4·2C2D6OS Z = 1
Mr = 486.61 F(000) = 250
Triclinic, P1 Dx = 1.348 Mg m3
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 mm1
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

[TableWrap ID: d1e346]
Siemens SMART CCD area-detector diffractometer 2101 independent reflections
Radiation source: fine-focus sealed tube 1707 reflections with I > 2σ(I)
Graphite monochromator Rint = 0.012
φ and ω scans θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001) h = −7→7
Tmin = 0.929, Tmax = 0.975 k = −10→10
3730 measured reflections l = −12→12

[TableWrap ID: d1e463]
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(Fo2) + (0.0891P)2 + 0.1414P] where P = (Fo2 + 2Fc2)/3
2101 reflections (Δ/σ)max < 0.001
148 parameters Δρmax = 0.53 e Å3
0 restraints Δρmin = −0.17 e Å3

[TableWrap ID: d1e620]
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.

[TableWrap ID: d1e719]
x y z Uiso*/Ueq
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*

[TableWrap ID: d1e1119]
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)

[TableWrap ID: d1e1407]
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)

[TableWrap ID: d1e1948]
D—H···A D—H H···A D···A D—H···A
O1—H10···O3ii 0.926 1.659 2.581 (2) 174


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