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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): o2602.
Published online 2009 October 3. doi:  10.1107/S1600536809039099
PMCID: PMC2971246

Bis(tetra­methyl­ammonium) oxalate monohydrate

Abstract

In the crystal structure of the title hydrated salt, 2C4H12N+·C2O4 2−·H2O, the two independent cations, the anion and the water mol­ecule all lie on special positions of m site symmetry. In both cations, the mirror plane passes through the nitrogen atom and two methyl groups; in the anion, the mirror plane passes through two carbon and two oxygen atoms. The anions and water mol­ecules inter­act by O—H(...)O hydrogen bonding, forming a chain running along the b axis.

Related literature

For the crystal structure of tetra­methyl­ammonium hydrogen oxalate, see: Mascal et al. (2000 [triangle]).

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Object name is e-65-o2602-scheme1.jpg

Experimental

Crystal data

  • 2C4H12N+·C2O4 2−·H2O
  • M r = 254.33
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2602-efi1.jpg
  • a = 24.614 (4) Å
  • b = 6.738 (1) Å
  • c = 8.633 (2) Å
  • V = 1431.8 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 293 K
  • 0.50 × 0.10 × 0.10 mm

Data collection

  • Bruker APEX2 diffractometer
  • Absorption correction: none
  • 3915 measured reflections
  • 1367 independent reflections
  • 1043 reflections with I > 2σ(I)
  • R int = 0.024

Refinement

  • R[F 2 > 2σ(F 2)] = 0.053
  • wR(F 2) = 0.164
  • S = 1.01
  • 1367 reflections
  • 99 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.25 e Å−3
  • Δρmin = −0.25 e Å−3

Data collection: APEX2 (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: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809039099/xu2618sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039099/xu2618Isup2.hkl

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

Acknowledgments

We thank Beijing Normal University and the University of Malaya for supporting this study.

supplementary crystallographic information

Experimental

Oxalic acid (0.126 g, 1 mmol) was dissolved in a water-ethanol (1:2 v/v) mixture and a 25% solution of tetramethylammonium hydroxide was added to neutralize the acid. Colorless block crystals were separated after several weeks.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.5U(C). The water H-atom was freely refined.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of 2[(CH3)4N](C2O4).H2O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

2C4H12N+·C2O42·H2OF(000) = 560
Mr = 254.33Dx = 1.180 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2nCell parameters from 1201 reflections
a = 24.614 (4) Åθ = 2.5–25.0°
b = 6.738 (1) ŵ = 0.09 mm1
c = 8.633 (2) ÅT = 293 K
V = 1431.8 (4) Å3Block, colorless
Z = 40.50 × 0.10 × 0.10 mm

Data collection

Bruker APEX2 diffractometer1043 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
graphiteθmax = 25.0°, θmin = 2.5°
[var phi] and ω scansh = −29→11
3915 measured reflectionsk = −8→8
1367 independent reflectionsl = −10→8

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.164w = 1/[σ2(Fo2) + (0.0847P)2 + 0.5757P] where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.001
1367 reflectionsΔρmax = 0.25 e Å3
99 parametersΔρmin = −0.25 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.022 (5)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
O10.29989 (10)0.75000.4672 (3)0.0944 (10)
O20.38001 (14)0.75000.3510 (3)0.1103 (12)
O30.38835 (9)0.5888 (4)0.6773 (3)0.1216 (10)
O1W0.40771 (12)0.25000.8491 (3)0.0790 (8)
H10.3983 (11)0.358 (4)0.784 (3)0.098 (9)*
N10.04672 (8)0.75000.7763 (3)0.0442 (6)
N20.27226 (8)0.75001.0044 (2)0.0372 (6)
C10.02478 (11)0.5681 (4)0.7022 (3)0.0864 (9)
H1A−0.01410.56650.71210.130*
H1B0.03970.45310.75220.130*
H1C0.03450.56690.59450.130*
C20.10673 (11)0.75000.7595 (5)0.0679 (10)
H2A0.12180.85790.81810.102*0.50
H2B0.11610.76540.65220.102*0.50
H2C0.12110.62670.79740.102*0.50
C30.03268 (14)0.75000.9431 (3)0.0652 (9)
H3A−0.00600.73790.95480.098*0.50
H3B0.04470.87190.98940.098*0.50
H3C0.05020.64020.99320.098*0.50
C40.30685 (10)0.5697 (3)1.0196 (3)0.0620 (7)
H4A0.32470.57081.11850.093*
H4B0.33360.56890.93870.093*
H4C0.28460.45331.01130.093*
C50.22984 (12)0.75001.1282 (3)0.0522 (8)
H5A0.24590.71161.22490.078*0.50
H5B0.20160.65771.10140.078*0.50
H5C0.21470.88071.13770.078*0.50
C60.24524 (12)0.75000.8504 (3)0.0548 (8)
H6A0.22190.86360.84230.082*0.50
H6B0.22410.63110.83910.082*0.50
H6C0.27230.75540.77040.082*0.5
C70.35047 (12)0.75000.4666 (3)0.0486 (7)
C80.37795 (10)0.75000.6197 (3)0.0479 (7)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0651 (17)0.124 (3)0.0938 (19)0.000−0.0318 (14)0.000
O20.134 (3)0.146 (3)0.0503 (15)0.0000.0259 (16)0.000
O30.1149 (17)0.126 (2)0.1237 (18)0.0185 (14)−0.0231 (13)0.0734 (15)
O1W0.113 (2)0.0643 (16)0.0591 (15)0.000−0.0145 (14)0.000
N10.0386 (12)0.0467 (13)0.0473 (13)0.0000.0020 (9)0.000
N20.0416 (11)0.0366 (11)0.0334 (11)0.000−0.0011 (9)0.000
C10.0809 (17)0.093 (2)0.0849 (17)−0.0298 (16)0.0007 (14)−0.0317 (15)
C20.0404 (15)0.060 (2)0.103 (3)0.0000.0112 (16)0.000
C30.069 (2)0.078 (2)0.0486 (17)0.0000.0046 (15)0.000
C40.0677 (13)0.0551 (14)0.0631 (13)0.0215 (11)−0.0031 (10)0.0016 (11)
C50.0562 (17)0.0583 (18)0.0419 (15)0.0000.0097 (12)0.000
C60.0586 (17)0.071 (2)0.0352 (14)0.000−0.0093 (12)0.000
C70.0614 (18)0.0383 (15)0.0461 (15)0.000−0.0003 (13)0.000
C80.0356 (14)0.0592 (18)0.0489 (15)0.0000.0053 (11)0.000

Geometric parameters (Å, °)

O1—C71.245 (4)C2—H2B0.9600
O2—C71.235 (4)C2—H2C0.9600
O3—C81.222 (2)C3—H3A0.9600
O1W—H10.95 (3)C3—H3B0.9600
N1—C31.481 (3)C3—H3C0.9600
N1—C21.484 (3)C4—H4A0.9600
N1—C11.484 (3)C4—H4B0.9600
N1—C1i1.484 (3)C4—H4C0.9600
N2—C61.487 (3)C5—H5A0.9600
N2—C41.489 (2)C5—H5B0.9600
N2—C4i1.489 (2)C5—H5C0.9600
N2—C51.494 (3)C6—H6A0.9600
C1—H1A0.9600C6—H6B0.9600
C1—H1B0.9600C6—H6C0.9600
C1—H1C0.9600C7—C81.484 (4)
C2—H2A0.9600C8—O3i1.222 (2)
C3—N1—C2109.1 (3)N1—C3—H3C109.5
C3—N1—C1109.52 (16)H3A—C3—H3C109.5
C2—N1—C1108.66 (17)H3B—C3—H3C109.5
C3—N1—C1i109.52 (16)N2—C4—H4A109.5
C2—N1—C1i108.66 (17)N2—C4—H4B109.5
C1—N1—C1i111.3 (3)H4A—C4—H4B109.5
C6—N2—C4109.54 (13)N2—C4—H4C109.5
C6—N2—C4i109.54 (13)H4A—C4—H4C109.5
C4—N2—C4i109.3 (2)H4B—C4—H4C109.5
C6—N2—C5109.1 (2)N2—C5—H5A109.5
C4—N2—C5109.68 (14)N2—C5—H5B109.5
C4i—N2—C5109.68 (14)H5A—C5—H5B109.5
N1—C1—H1A109.5N2—C5—H5C109.5
N1—C1—H1B109.5H5A—C5—H5C109.5
H1A—C1—H1B109.5H5B—C5—H5C109.5
N1—C1—H1C109.5N2—C6—H6A109.5
H1A—C1—H1C109.5N2—C6—H6B109.5
H1B—C1—H1C109.5H6A—C6—H6B109.5
N1—C2—H2A109.5N2—C6—H6C109.5
N1—C2—H2B109.5H6A—C6—H6C109.5
H2A—C2—H2B109.5H6B—C6—H6C109.5
N1—C2—H2C109.5O2—C7—O1126.3 (3)
H2A—C2—H2C109.5O2—C7—C8116.8 (3)
H2B—C2—H2C109.5O1—C7—C8116.9 (3)
N1—C3—H3A109.5O3i—C8—O3125.5 (3)
N1—C3—H3B109.5O3i—C8—C7117.26 (17)
H3A—C3—H3B109.5O3—C8—C7117.26 (17)
O2—C7—C8—O3i89.9 (2)O2—C7—C8—O3−89.9 (2)
O1—C7—C8—O3i−90.1 (2)O1—C7—C8—O390.1 (2)

Symmetry codes: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1···O30.95 (3)1.82 (3)2.764 (2)171 (3)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2618).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Mascal, M., Marjo, C. E. & Blake, A. J. (2000). Chem. Commun. pp. 1591–1592.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF In preparation.

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