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Acta Cryst. (2009). E65, o2602    [ doi:10.1107/S1600536809039099 ]

Bis(tetramethylammonium) oxalate monohydrate

Y.-X. Yang, Q. Li and S. W. Ng

Abstract top

In the crystal structure of the title hydrated salt, 2C4H12N+·C2O42-·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 top

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

Experimental top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] 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.
Bis(tetramethylammonium) oxalate monohydrate top
Crystal data top
2C4H12N+·C2O42−·H2OF(000) = 560
Mr = 254.33Dx = 1.180 Mg m−3
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 mm−1
c = 8.633 (2) ÅT = 293 K
V = 1431.8 (4) Å3Block, colorless
Z = 40.50 × 0.10 × 0.10 mm
Data collection top
Bruker APEX2
diffractometer		1043 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.024
graphiteθmax = 25.0°, θmin = 2.5°
φ and ω scansh = −29→11
3915 measured reflectionsk = −8→8
1367 independent reflectionsl = −10→8
Refinement top
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) = 0.164 w = 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 Å−3
99 parametersΔρmin = −0.25 e Å−3
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)
Crystal data top
2C4H12N+·C2O42−·H2OV = 1431.8 (4) Å3
Mr = 254.33Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 24.614 (4) ŵ = 0.09 mm−1
b = 6.738 (1) ÅT = 293 K
c = 8.633 (2) Å0.50 × 0.10 × 0.10 mm
Data collection top
Bruker APEX2
diffractometer		Rint = 0.024
3915 measured reflectionsθmax = 25.0°
1367 independent reflectionsStandard reflections: 0
1043 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.164Δρmax = 0.25 e Å−3
S = 1.01Δρmin = −0.25 e Å−3
1367 reflectionsAbsolute structure: ?
99 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
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) top
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, °) top
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, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···O30.95 (3)1.82 (3)2.764 (2)171 (3)
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1···O30.95 (3)1.82 (3)2.764 (2)171 (3)
Acknowledgements top

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

references
References top

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.

Westrip, S. P. (2009). publCIF. In preparation.