PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1794.
Published online 2009 July 8. doi:  10.1107/S1600536809025793
PMCID: PMC2977459

Benzene-1,4-dicarboxylic acid–N,N-dimethyl­acetamide (1/2)

Abstract

The asymmetric unit of title compound, C8H6O4·2C4H9NO, contains one half-mol­ecule (an inversion centre in P21/n generates the other half of the molecule) of terephthalic acid (TA) and one mol­ecule of N,N-dimethyl­acetamide (DMAC). The DMAC mol­ecules are linked to TA by strong O—H(...)O hydrogen bonds.

Related literature

For the crystal structure of terephthalic acid-bis­(N,N-dimethyl­formamide), see: Dale & Elsegood (2004 [triangle]). For the polymorphism of terephthalic acid, see: Bailey & Brown (1967 [triangle]); Sledz et al. (2001 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1794-scheme1.jpg

Experimental

Crystal data

  • C8H6O4·2C4H9NO
  • M r = 340.37
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1794-efi1.jpg
  • a = 10.191 (2) Å
  • b = 8.5228 (17) Å
  • c = 10.719 (2) Å
  • β = 110.67 (3)°
  • V = 871.0 (3) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 113 K
  • 0.60 × 0.51 × 0.38 mm

Data collection

  • Rigaku R-AXIS RAPID diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.940, T max = 0.961
  • 6605 measured reflections
  • 1522 independent reflections
  • 1395 reflections with I > 2σ(I)
  • R int = 0.014

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.118
  • S = 1.08
  • 1522 reflections
  • 116 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.58 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 [triangle]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025793/gk2216sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025793/gk2216Isup2.hkl

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

Acknowledgments

The authors thank Dr Xu Wei for the X-ray data collection and would like to express sincere thanks to Professor Li Xi for providing the study environment and helpful comments.

supplementary crystallographic information

Comment

Terephthalic acid (TA) is an important intermediate in the production of polyesters for plastics and fiber applications. According to Bailey & Brown (1967), TA exists in two polymorphic modifications (forms 1 and 2), both triclinic. Recently Sledz et al. (2001) reported a new crystalline form of TA which is monoclinic and designated as form 3.

N,N-Dimethylformamide (DMF) and N,N-dimethylacetamide (DMAC) are the two of a few organic solvents capable of dissolving TA. The crystal structure of the 2:1 DMF solvate of terephthalic acid was reported recently (Dale & Elsegood, 2004). The solvent molecules and TA form a centrosymmetric descrete planar assembly with both carboxylic acid groups hydrogen bonded to DMF molecules via R22(7) motif (O—H···O/C—H···O interactions). Recently we have obtained single crystals of the DMAC solvate of TA and here we report its crystal structure.

The asymmetric unit of title compound contains one half-molecule of TA and one N, N-dimethyl acetamide (DMAC) molecule (Fig. 2). The DMAC molecules are linked to TA by strong O—H···O hydrogen bonds (Fig.3 and Table 1), which may be effective in stablilizing the crystal structure. The carboxylic group is roughly coplanar with the benzene ring forming dihedral angle of 0.6 (3)° . The dihedral angle between TA and the dimethylacetamide molecule is 21.7 (1)°.

Experimental

Single crystals were obtained by dissolving TA (1.0 g) in DMAC (20 ml) at 80°C and then allowing the solvent to cool to room temperature. The sample proved unstable in the air.

Refinement

The H atom of the carboxylic group was located from a difference Fourier map and fully refined. The remaining H atoms were placed in geometrically calculated positions and refined using a riding model, with Uiso(H) = 1.2 Ueq(C).

Figures

Fig. 1.
View of the title compound showing 50% probability displacement ellipsoids. Symmetry operation for atoms with '#': -x,-y,-z + 1.
Fig. 2.
The packing diagram for the title compound; dashed lines indicate hydrogen bonds.

Crystal data

C8H6O4·2C4H9NOF(000) = 364
Mr = 340.37Dx = 1.298 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 6873 reflections
a = 10.191 (2) Åθ = 3.1–27.5°
b = 8.5228 (17) ŵ = 0.10 mm1
c = 10.719 (2) ÅT = 113 K
β = 110.67 (3)°Block, colorless
V = 871.0 (3) Å30.60 × 0.51 × 0.38 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer1522 independent reflections
Radiation source: fine-focus sealed tube1395 reflections with I > 2σ(I)
graphiteRint = 0.014
Detector resolution: 0 pixels mm-1θmax = 25.0°, θmin = 3.1°
ω scansh = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)k = −9→10
Tmin = 0.940, Tmax = 0.961l = −12→12
6605 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.08w = 1/[σ2(Fo2) + (0.0571P)2 + 0.6867P] where P = (Fo2 + 2Fc2)/3
1522 reflections(Δ/σ)max < 0.001
116 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = −0.26 e Å3

Special details

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)

xyzUiso*/Ueq
N10.74204 (15)0.07465 (18)0.88639 (15)0.0233 (4)
O10.95506 (11)0.13078 (14)0.88125 (11)0.0207 (3)
O20.30574 (13)−0.23616 (15)0.52621 (12)0.0248 (3)
O30.35578 (12)−0.10972 (15)0.72025 (11)0.0237 (3)
C10.89721 (19)0.2372 (2)1.06449 (18)0.0266 (4)
H1A0.90970.16701.13780.040*
H1B0.82030.30671.05570.040*
H1C0.98130.29731.08060.040*
C20.86637 (18)0.1442 (2)0.93832 (17)0.0224 (4)
C30.71443 (18)−0.0191 (2)0.76458 (17)0.0241 (4)
H3A0.72480.04580.69540.036*
H3B0.6206−0.05980.73630.036*
H3C0.7799−0.10460.78240.036*
C40.63337 (19)0.0830 (3)0.9455 (2)0.0304 (5)
H4A0.67640.08881.04080.046*
H4B0.5755−0.00900.92160.046*
H4C0.57680.17460.91310.046*
C5−0.08828 (17)−0.03522 (19)0.37140 (16)0.0171 (4)
H5−0.1477−0.05860.28520.020*
C60.04270 (17)−0.10394 (19)0.42154 (16)0.0175 (4)
H6A0.0712−0.17340.36920.021*
C70.13228 (16)−0.06918 (18)0.55081 (15)0.0152 (4)
C80.27579 (16)−0.13973 (18)0.60876 (15)0.0163 (4)
H20.394 (3)−0.276 (3)0.563 (2)0.052 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0191 (8)0.0254 (8)0.0268 (8)−0.0007 (6)0.0097 (6)0.0006 (6)
O10.0166 (6)0.0255 (7)0.0209 (6)−0.0043 (5)0.0080 (5)0.0014 (5)
O20.0174 (7)0.0324 (7)0.0224 (7)0.0083 (5)0.0044 (5)−0.0055 (5)
O30.0182 (6)0.0282 (7)0.0200 (6)0.0047 (5)0.0012 (5)−0.0035 (5)
C10.0258 (9)0.0256 (10)0.0299 (10)−0.0037 (7)0.0117 (8)−0.0079 (7)
C20.0227 (9)0.0179 (9)0.0248 (9)0.0013 (7)0.0060 (7)0.0051 (7)
C30.0227 (9)0.0265 (10)0.0205 (9)−0.0061 (7)0.0047 (7)−0.0023 (7)
C40.0192 (9)0.0407 (11)0.0344 (11)−0.0024 (8)0.0133 (8)−0.0086 (8)
C50.0168 (8)0.0189 (8)0.0145 (8)−0.0012 (6)0.0043 (6)−0.0011 (6)
C60.0187 (8)0.0176 (8)0.0171 (8)0.0005 (6)0.0076 (6)−0.0018 (6)
C70.0140 (8)0.0156 (8)0.0170 (8)−0.0014 (6)0.0066 (6)0.0022 (6)
C80.0164 (8)0.0159 (8)0.0175 (8)−0.0009 (6)0.0072 (6)0.0017 (6)

Geometric parameters (Å, °)

N1—C21.330 (2)C3—H3B0.9600
N1—C41.459 (2)C3—H3C0.9600
N1—C31.471 (2)C4—H4A0.9600
O1—C21.263 (2)C4—H4B0.9600
O2—C81.320 (2)C4—H4C0.9600
O2—H20.91 (3)C5—C61.381 (2)
O3—C81.213 (2)C5—C7i1.397 (2)
C1—C21.502 (2)C5—H50.9300
C1—H1A0.9600C6—C71.396 (2)
C1—H1B0.9600C6—H6A0.9300
C1—H1C0.9600C7—C5i1.397 (2)
C3—H3A0.9600C7—C81.498 (2)
C2—N1—C4123.61 (16)N1—C4—H4A109.5
C2—N1—C3117.98 (15)N1—C4—H4B109.5
C4—N1—C3118.39 (14)H4A—C4—H4B109.5
C8—O2—H2111.4 (16)N1—C4—H4C109.5
C2—C1—H1A109.5H4A—C4—H4C109.5
C2—C1—H1B109.5H4B—C4—H4C109.5
H1A—C1—H1B109.5C6—C5—C7i120.51 (15)
C2—C1—H1C109.5C6—C5—H5119.7
H1A—C1—H1C109.5C7i—C5—H5119.7
H1B—C1—H1C109.5C5—C6—C7119.99 (15)
O1—C2—N1119.73 (16)C5—C6—H6A120.0
O1—C2—C1121.74 (15)C7—C6—H6A120.0
N1—C2—C1118.53 (16)C6—C7—C5i119.50 (15)
N1—C3—H3A109.5C6—C7—C8121.80 (15)
N1—C3—H3B109.5C5i—C7—C8118.70 (14)
H3A—C3—H3B109.5O3—C8—O2123.91 (15)
N1—C3—H3C109.5O3—C8—C7122.83 (15)
H3A—C3—H3C109.5O2—C8—C7113.26 (14)
H3B—C3—H3C109.5

Symmetry codes: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O1ii0.91 (3)1.65 (3)2.551 (2)173 (2)

Symmetry codes: (ii) −x+3/2, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2216).

References

  • Bailey, M. & Brown, C. J. (1967). Acta Cryst.22, 387–391.
  • Dale, S. H. & Elsegood, M. R. J. (2004). Acta Cryst. C60, o444–o448. [PubMed]
  • Higashi, T. (1995). ABSCOR Rigaku Corporation, Tokyo, Japan.
  • Rigaku (1998). RAPID-AUTO Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Crtyst. A64, 112-122. [PubMed]
  • Sledz, M., Janczak, J. & Kubiak, R. (2001). J. Mol. Struct. 595, 77–82.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography