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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o2074.
Published online 2010 July 21. doi:  10.1107/S1600536810027868
PMCID: PMC3007286

Bis[dieth­yl(hy­droxy)ammonium] benzene-1,4-dicarboxyl­ate

Abstract

In the centrosymmetric title compound, 2C4H12NO+·C8H4O4 2−, two N,N-dieth­yl(hy­droxy)ammonium cations are linked to a benzene-1,4-dicarboxyl­ate dianion by a combination of O—H(...)O and N—H(...)O hydrogen bonds, which can be described in graph-set terminology as R 2 2(7). The crystal structure is further stabilized by C—H(...)O hydrogen bonds, leading to the fomation of a ribbon-like network.

Related literature

For similar supamolecular structures involving benzene­dicarb­oxy­lic acids, see: Chatterjee et al. (2000 [triangle]); Herbstein & Kapon (1978 [triangle]); Karpova et al. (2004 [triangle]); Mak & Xue (2000 [triangle]); Yuge et al. (2006 [triangle]); Zhao et al. (2007 [triangle]). For graph-set theory, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2074-scheme1.jpg

Experimental

Crystal data

  • 2C4H12NO+·C8H4O4 2−
  • M r = 344.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2074-efi1.jpg
  • a = 6.507 (2) Å
  • b = 11.478 (4) Å
  • c = 12.649 (5) Å
  • β = 97.380 (7)°
  • V = 936.9 (6) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 273 K
  • 0.37 × 0.31 × 0.27 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2007 [triangle]) T min = 0.954, T max = 0.969
  • 4737 measured reflections
  • 1653 independent reflections
  • 1460 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.087
  • wR(F 2) = 0.220
  • S = 1.13
  • 1653 reflections
  • 112 parameters
  • H-atom parameters constrained
  • Δρmax = 0.66 e Å−3
  • Δρmin = −0.27 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; 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: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810027868/su2169sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810027868/su2169Isup2.hkl

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

supplementary crystallographic information

Comment

Supramolecular aggregate design is an active field of research and in a series of papers various supramolecular structures comprising benzene-dicarboxylic acids have been elucidated (Herbstein et al., 1978; Chatterjee et al., 2000; Karpova et al., 2004; Zhao et al., 2007). Some cases have been reported where the use of terephthalic acid has lead to the fomation of supramolecular architectures through hydrogen bonding (Mak et al., 2000; Yuge et al., 2006). The title compound was synthesized by the reaction of terephthalic acid with N,N-diethylhydroxylammine.

As shown in Fig. 1 two N,N-diethylhydroxylammonium (DTHA) cations are linked to the benzene-1,4-dicarboxylate anion (BDL), which is situated about an inversion center, by a special combination of O—H···O and N—H···O hydrogen bonds (Table 1), N1—H1···O1 and O3—H3···O2, which can be described by graph-set R22(7) [Bernstein, et al., 1995].

In the BDL anion the dihedral angle between phenyl ring and carboxylate group is 11.3 (3)/%. In general the BDLanion is almost coplanar with the mean plane through the C and N-atoms in the DTHA cations. The carboxylate groups are nearly perpendicular with the mean plane through the C and N-atoms of DTHA [dihedral angle of 81.0 (3)/%].

In the crystal structure a ribbon-like structure (Fig. 2 and Table 1), is fomed via C7—H7···O2i interactions [symmetry code (i) = 1 + x, y, z] .

Experimental

N,N-diethylhydroxylammine and terephthalic acid, in a molar ratio of 2:1, were mixed and dissolved in sufficient ethanol that by heating to 353 K a clear solution was obtained. The reaction system was then cooled slowly to RT, and crystals of the title compound were formed. They were collected and washed with ethanol.

Refinement

The H-atoms were included in calculated positions and treated as riding atoms: O-H = 0.82 Å, N-H = 0.91 Å, C-H = 0.93, 0.96, and 0.97 Å for aromatic, methyl and methylene H-atoms, respectively, with Uiso(H) = k × Ueq(parent O, N or C atom), where k = 1.5 for hydroxyl and methyl H-atoms and = 1.2 for all others.

Figures

Fig. 1.
A view of the molecular structure of the title compound [The O—H···O and N—H···O hydrogen bonds are illustrated by dotted lines].
Fig. 2.
A perspective view, along the c-axis, of the crystal packing of the title compound [The O—H···O and N—H···O hydrogen bonds nd the C-H···O interactions are illustrated ...

Crystal data

2C4H12NO+·C8H4O42F(000) = 372.0
Mr = 344.40Dx = 1.221 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2185 reflections
a = 6.507 (2) Åθ = 2.1–25.0°
b = 11.478 (4) ŵ = 0.09 mm1
c = 12.649 (5) ÅT = 273 K
β = 97.380 (7)°Block, colorless
V = 936.9 (6) Å30.37 × 0.31 × 0.27 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer1653 independent reflections
Radiation source: fine-focus sealed tube1460 reflections with I > 2σ(I)
graphiteRint = 0.023
phi and ω scansθmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)h = −7→7
Tmin = 0.954, Tmax = 0.969k = −10→13
4737 measured reflectionsl = −14→15

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)] = 0.087Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.220H-atom parameters constrained
S = 1.13w = 1/[σ2(Fo2) + (0.0871P)2 + 0.9891P] where P = (Fo2 + 2Fc2)/3
1653 reflections(Δ/σ)max < 0.001
112 parametersΔρmax = 0.66 e Å3
0 restraintsΔρmin = −0.27 e Å3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
O10.4427 (3)0.3065 (2)0.0657 (2)0.0636 (8)
O20.1752 (4)0.2241 (2)0.1261 (2)0.0682 (8)
C10.2564 (5)0.3044 (3)0.0788 (3)0.0482 (8)
C20.1228 (4)0.4052 (3)0.0370 (2)0.0423 (8)
C3−0.0744 (5)0.4198 (3)0.0657 (3)0.0476 (8)
H3A−0.12580.36530.11000.057*
C40.1945 (5)0.4869 (3)−0.0298 (3)0.0469 (8)
H40.32570.4784−0.05050.056*
O30.4471 (5)0.0641 (2)0.1778 (3)0.0851 (10)
H30.34440.10520.16290.128*
N10.6262 (5)0.1284 (3)0.1645 (2)0.0573 (8)
H10.58470.19670.13200.069*
C50.6600 (11)0.2447 (5)0.3266 (4)0.110 (2)
H5A0.63820.31430.28460.164*
H5B0.74860.26170.39140.164*
H5C0.52920.21620.34330.164*
C60.7561 (8)0.1574 (4)0.2672 (3)0.0784 (13)
H6A0.77860.08740.31010.094*
H6B0.89010.18550.25250.094*
C70.7465 (6)0.0633 (4)0.0917 (3)0.0660 (11)
H7A0.65990.05200.02410.079*
H7B0.86440.11020.07830.079*
C80.8225 (8)−0.0519 (4)0.1328 (4)0.0938 (16)
H8A0.9352−0.04110.18880.141*
H8B0.8694−0.09610.07610.141*
H8C0.7121−0.09300.16010.141*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0377 (13)0.0655 (17)0.0879 (19)0.0015 (11)0.0087 (12)0.0270 (14)
O20.0510 (15)0.0536 (15)0.103 (2)−0.0012 (12)0.0227 (14)0.0214 (15)
C10.0434 (19)0.0489 (19)0.0519 (19)−0.0079 (15)0.0049 (14)−0.0012 (15)
C20.0377 (16)0.0466 (18)0.0418 (16)−0.0111 (13)0.0013 (13)−0.0047 (14)
C30.0415 (17)0.053 (2)0.0490 (18)−0.0096 (15)0.0093 (14)0.0067 (15)
C40.0342 (16)0.058 (2)0.0500 (18)−0.0045 (14)0.0094 (13)0.0012 (16)
O30.0704 (18)0.0558 (17)0.137 (3)0.0022 (14)0.0415 (19)0.0251 (18)
N10.0621 (18)0.0444 (16)0.0636 (19)−0.0028 (14)0.0010 (15)0.0095 (14)
C50.167 (6)0.094 (4)0.070 (3)0.034 (4)0.024 (3)−0.002 (3)
C60.100 (3)0.071 (3)0.062 (2)0.019 (2)0.004 (2)0.010 (2)
C70.058 (2)0.072 (3)0.066 (2)−0.0090 (19)0.0050 (18)0.002 (2)
C80.100 (4)0.073 (3)0.111 (4)0.015 (3)0.020 (3)−0.006 (3)

Geometric parameters (Å, °)

O1—C11.245 (4)N1—H10.9100
O2—C11.252 (4)C5—C61.442 (6)
C1—C21.502 (5)C5—H5A0.9600
C2—C41.384 (4)C5—H5B0.9600
C2—C31.388 (4)C5—H5C0.9600
C3—C4i1.368 (5)C6—H6A0.9700
C3—H3A0.9300C6—H6B0.9700
C4—C3i1.368 (5)C7—C81.481 (6)
C4—H40.9300C7—H7A0.9700
O3—N11.408 (4)C7—H7B0.9700
O3—H30.8200C8—H8A0.9600
N1—C71.484 (5)C8—H8B0.9600
N1—C61.494 (5)C8—H8C0.9600
O1—C1—O2123.8 (3)C6—C5—H5C109.5
O1—C1—C2117.9 (3)H5A—C5—H5C109.5
O2—C1—C2118.3 (3)H5B—C5—H5C109.5
C4—C2—C3118.3 (3)C5—C6—N1111.9 (4)
C4—C2—C1120.8 (3)C5—C6—H6A109.2
C3—C2—C1120.9 (3)N1—C6—H6A109.2
C4i—C3—C2121.0 (3)C5—C6—H6B109.2
C4i—C3—H3A119.5N1—C6—H6B109.2
C2—C3—H3A119.5H6A—C6—H6B107.9
C3i—C4—C2120.7 (3)C8—C7—N1114.3 (4)
C3i—C4—H4119.7C8—C7—H7A108.7
C2—C4—H4119.7N1—C7—H7A108.7
N1—O3—H3109.5C8—C7—H7B108.7
O3—N1—C7108.7 (3)N1—C7—H7B108.7
O3—N1—C6113.4 (3)H7A—C7—H7B107.6
C7—N1—C6111.6 (3)C7—C8—H8A109.5
O3—N1—H1107.7C7—C8—H8B109.5
C7—N1—H1107.7H8A—C8—H8B109.5
C6—N1—H1107.7C7—C8—H8C109.5
C6—C5—H5A109.5H8A—C8—H8C109.5
C6—C5—H5B109.5H8B—C8—H8C109.5
H5A—C5—H5B109.5
O1—C1—C2—C411.2 (5)C3—C2—C4—C3i0.6 (5)
O2—C1—C2—C4−169.9 (3)C1—C2—C4—C3i−178.4 (3)
O1—C1—C2—C3−167.8 (3)O3—N1—C6—C5−71.7 (5)
O2—C1—C2—C311.1 (5)C7—N1—C6—C5165.2 (4)
C4—C2—C3—C4i−0.6 (5)O3—N1—C7—C8−62.6 (4)
C1—C2—C3—C4i178.4 (3)C6—N1—C7—C863.1 (5)

Symmetry codes: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···O20.821.782.576 (5)164
N1—H1···O10.911.722.605 (5)164
C7—H7b···O2ii0.972.423.327 (5)156

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SU2169).

References

  • Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Bruker (2007). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Chatterjee, S., Pedireddi, V. R., Ranganathan, A. & Rao, C. N. R. (2000). J. Mol. Struct.520, 107–115.
  • Herbstein, F. H. & Kapon, M. (1978). Acta Cryst. B34, 1608–1612.
  • Karpova, E. V., Zakharov, M. A., Gutnikov, S. I. & Alekseyev, R. S. (2004). Acta Cryst. E60, o2491–o2492.
  • Mak, T. C. W. & Xue, F. (2000). J. Am. Chem. Soc.122, 9860–9861.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Yuge, T., Miyata, M. & Tohnai, N. (2006). Cryst. Growth Des.6, 1272–1273.
  • Zhao, W.-X., Gao, Y.-X., Dong, S.-F., Li, Y. & Zhang, W.-P. (2007). Acta Cryst. E63, o2728.

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