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

Guo, X.; Cheng, Y.; Li, X.

doi:10.1107/S1600536809025793

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1794

doi:10.1107/S1600536809025793

Open

access

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

Xia Guo,^a Youwei Cheng ^a and Xi Li ^a ^*

^aCollege of Materials Science and Chemical Engineering, Zhejiang University, Zhejiang 310027, People's Republic of China
^*Correspondence e-mail: guoxia0502@gmail.com

(Received 8 June 2009; accepted 3 July 2009; online 8 July 2009)

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 ). For the polymorphism of terephthalic acid, see: Bailey & Brown (1967 ); Sledz et al. (2001 ).

Experimental

Crystal data

C₈H₆O₄·2C₄H₉NO
M_r = 340.37
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.043
wR(F²) = 0.118
S = 1.08
1522 reflections
116 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.91 (3)	1.65 (3)	2.551 (2)	173 (2)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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)°.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

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

Crystal data top

C₈H₆O₄·2C₄H₉NO	F(000) = 364
M_r = 340.37	D_x = 1.298 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6873 reflections
a = 10.191 (2) Å	θ = 3.1–27.5°
b = 8.5228 (17) Å	µ = 0.10 mm⁻¹
c = 10.719 (2) Å	T = 113 K
β = 110.67 (3)°	Block, colorless
V = 871.0 (3) Å³	0.60 × 0.51 × 0.38 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	1522 independent reflections
Radiation source: fine-focus sealed tube	1395 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.014
Detector resolution: 0 pixels mm^-1	θ_max = 25.0°, θ_min = 3.1°
ω scans	h = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −9→10
T_min = 0.940, T_max = 0.961	l = −12→12
6605 measured reflections

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0571P)² + 0.6867P] where P = (F_o² + 2F_c²)/3
1522 reflections	(Δ/σ)_max < 0.001
116 parameters	Δρ_max = 0.58 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₈H₆O₄·2C₄H₉NO	V = 871.0 (3) Å³
M_r = 340.37	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.191 (2) Å	µ = 0.10 mm⁻¹
b = 8.5228 (17) Å	T = 113 K
c = 10.719 (2) Å	0.60 × 0.51 × 0.38 mm
β = 110.67 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1522 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1395 reflections with I > 2σ(I)
T_min = 0.940, T_max = 0.961	R_int = 0.014
6605 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.58 e Å⁻³
1522 reflections	Δρ_min = −0.26 e Å⁻³
116 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
N1	0.74204 (15)	0.07465 (18)	0.88639 (15)	0.0233 (4)
O1	0.95506 (11)	0.13078 (14)	0.88125 (11)	0.0207 (3)
O2	0.30574 (13)	−0.23616 (15)	0.52621 (12)	0.0248 (3)
O3	0.35578 (12)	−0.10972 (15)	0.72025 (11)	0.0237 (3)
C1	0.89721 (19)	0.2372 (2)	1.06449 (18)	0.0266 (4)
H1A	0.9097	0.1670	1.1378	0.040*
H1B	0.8203	0.3067	1.0557	0.040*
H1C	0.9813	0.2973	1.0806	0.040*
C2	0.86637 (18)	0.1442 (2)	0.93832 (17)	0.0224 (4)
C3	0.71443 (18)	−0.0191 (2)	0.76458 (17)	0.0241 (4)
H3A	0.7248	0.0458	0.6954	0.036*
H3B	0.6206	−0.0598	0.7363	0.036*
H3C	0.7799	−0.1046	0.7824	0.036*
C4	0.63337 (19)	0.0830 (3)	0.9455 (2)	0.0304 (5)
H4A	0.6764	0.0888	1.0408	0.046*
H4B	0.5755	−0.0090	0.9216	0.046*
H4C	0.5768	0.1746	0.9131	0.046*
C5	−0.08828 (17)	−0.03522 (19)	0.37140 (16)	0.0171 (4)
H5	−0.1477	−0.0586	0.2852	0.020*
C6	0.04270 (17)	−0.10394 (19)	0.42154 (16)	0.0175 (4)
H6A	0.0712	−0.1734	0.3692	0.021*
C7	0.13228 (16)	−0.06918 (18)	0.55081 (15)	0.0152 (4)
C8	0.27579 (16)	−0.13973 (18)	0.60876 (15)	0.0163 (4)
H2	0.394 (3)	−0.276 (3)	0.563 (2)	0.052 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0191 (8)	0.0254 (8)	0.0268 (8)	−0.0007 (6)	0.0097 (6)	0.0006 (6)
O1	0.0166 (6)	0.0255 (7)	0.0209 (6)	−0.0043 (5)	0.0080 (5)	0.0014 (5)
O2	0.0174 (7)	0.0324 (7)	0.0224 (7)	0.0083 (5)	0.0044 (5)	−0.0055 (5)
O3	0.0182 (6)	0.0282 (7)	0.0200 (6)	0.0047 (5)	0.0012 (5)	−0.0035 (5)
C1	0.0258 (9)	0.0256 (10)	0.0299 (10)	−0.0037 (7)	0.0117 (8)	−0.0079 (7)
C2	0.0227 (9)	0.0179 (9)	0.0248 (9)	0.0013 (7)	0.0060 (7)	0.0051 (7)
C3	0.0227 (9)	0.0265 (10)	0.0205 (9)	−0.0061 (7)	0.0047 (7)	−0.0023 (7)
C4	0.0192 (9)	0.0407 (11)	0.0344 (11)	−0.0024 (8)	0.0133 (8)	−0.0086 (8)
C5	0.0168 (8)	0.0189 (8)	0.0145 (8)	−0.0012 (6)	0.0043 (6)	−0.0011 (6)
C6	0.0187 (8)	0.0176 (8)	0.0171 (8)	0.0005 (6)	0.0076 (6)	−0.0018 (6)
C7	0.0140 (8)	0.0156 (8)	0.0170 (8)	−0.0014 (6)	0.0066 (6)	0.0022 (6)
C8	0.0164 (8)	0.0159 (8)	0.0175 (8)	−0.0009 (6)	0.0072 (6)	0.0017 (6)

Geometric parameters (Å, º) top

N1—C2	1.330 (2)	C3—H3B	0.9600
N1—C4	1.459 (2)	C3—H3C	0.9600
N1—C3	1.471 (2)	C4—H4A	0.9600
O1—C2	1.263 (2)	C4—H4B	0.9600
O2—C8	1.320 (2)	C4—H4C	0.9600
O2—H2	0.91 (3)	C5—C6	1.381 (2)
O3—C8	1.213 (2)	C5—C7ⁱ	1.397 (2)
C1—C2	1.502 (2)	C5—H5	0.9300
C1—H1A	0.9600	C6—C7	1.396 (2)
C1—H1B	0.9600	C6—H6A	0.9300
C1—H1C	0.9600	C7—C5ⁱ	1.397 (2)
C3—H3A	0.9600	C7—C8	1.498 (2)

C2—N1—C4	123.61 (16)	N1—C4—H4A	109.5
C2—N1—C3	117.98 (15)	N1—C4—H4B	109.5
C4—N1—C3	118.39 (14)	H4A—C4—H4B	109.5
C8—O2—H2	111.4 (16)	N1—C4—H4C	109.5
C2—C1—H1A	109.5	H4A—C4—H4C	109.5
C2—C1—H1B	109.5	H4B—C4—H4C	109.5
H1A—C1—H1B	109.5	C6—C5—C7ⁱ	120.51 (15)
C2—C1—H1C	109.5	C6—C5—H5	119.7
H1A—C1—H1C	109.5	C7ⁱ—C5—H5	119.7
H1B—C1—H1C	109.5	C5—C6—C7	119.99 (15)
O1—C2—N1	119.73 (16)	C5—C6—H6A	120.0
O1—C2—C1	121.74 (15)	C7—C6—H6A	120.0
N1—C2—C1	118.53 (16)	C6—C7—C5ⁱ	119.50 (15)
N1—C3—H3A	109.5	C6—C7—C8	121.80 (15)
N1—C3—H3B	109.5	C5ⁱ—C7—C8	118.70 (14)
H3A—C3—H3B	109.5	O3—C8—O2	123.91 (15)
N1—C3—H3C	109.5	O3—C8—C7	122.83 (15)
H3A—C3—H3C	109.5	O2—C8—C7	113.26 (14)
H3B—C3—H3C	109.5

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱⁱ	0.91 (3)	1.65 (3)	2.551 (2)	173 (2)

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

Experimental details

Crystal data
Chemical formula	C₈H₆O₄·2C₄H₉NO
M_r	340.37
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	10.191 (2), 8.5228 (17), 10.719 (2)
β (°)	110.67 (3)
V (Å³)	871.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.60 × 0.51 × 0.38

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.940, 0.961
No. of measured, independent and observed [I > 2σ(I)] reflections	6605, 1522, 1395
R_int	0.014
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.118, 1.08
No. of reflections	1522
No. of parameters	116
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.26

Computer programs: RAPID-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.91 (3)	1.65 (3)	2.551 (2)	173 (2)

Symmetry code: (i) −x+3/2, y−1/2, −z+3/2.

Acknowledgements

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.

References

Bailey, M. & Brown, C. J. (1967). Acta Cryst. 22, 387–391. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Dale, S. H. & Elsegood, M. R. J. (2004). Acta Cryst. C60, o444–o448. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Crtyst. A64, 112-122. CrossRef CAS Google Scholar
Sledz, M., Janczak, J. & Kubiak, R. (2001). J. Mol. Struct. 595, 77–82. Web of Science CSD CrossRef CAS Google Scholar