Bis(tetra­methyl­ammonium) oxalate monohydrate

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

doi:10.1107/S1600536809039099

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2602

https://doi.org/10.1107/S1600536809039099

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Bis(tetramethylammonium) oxalate monohydrate

Yun-Xia Yang,^a Qi Li ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry, Beijing Normal University, Beijing 100875, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 25 September 2009; accepted 26 September 2009; online 3 October 2009)

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

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

Experimental

Crystal data

2C₄H₁₂N⁺·C₂O₄²⁻·H₂O
M_r = 254.33
Orthorhombic, P n m a
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[F² > 2σ(F²)] = 0.053
wR(F²) = 0.164
S = 1.01
1367 reflections
99 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1⋯O3	0.95 (3)	1.82 (3)	2.764 (2)	171 (3)

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039099/xu2618Isup2.hkl

checkCIF report

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.

Structure description top

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

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

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⁻·H₂O	F(000) = 560
M_r = 254.33	D_x = 1.180 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1201 reflections
a = 24.614 (4) Å	θ = 2.5–25.0°
b = 6.738 (1) Å	µ = 0.09 mm⁻¹
c = 8.633 (2) Å	T = 293 K
V = 1431.8 (4) Å³	Block, colorless
Z = 4	0.50 × 0.10 × 0.10 mm

Data collection top

Bruker APEX2 diffractometer	1043 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 25.0°, θ_min = 2.5°
φ and ω scans	h = −29→11
3915 measured reflections	k = −8→8
1367 independent reflections	l = −10→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.164	w = 1/[σ²(F_o²) + (0.0847P)² + 0.5757P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
1367 reflections	Δρ_max = 0.25 e Å⁻³
99 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (5)

Crystal data top

2C₄H₁₂N⁺·C₂O₄²⁻·H₂O	V = 1431.8 (4) Å³
M_r = 254.33	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 24.614 (4) Å	µ = 0.09 mm⁻¹
b = 6.738 (1) Å	T = 293 K
c = 8.633 (2) Å	0.50 × 0.10 × 0.10 mm

Data collection top

Bruker APEX2 diffractometer	1043 reflections with I > 2σ(I)
3915 measured reflections	R_int = 0.024
1367 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.25 e Å⁻³
1367 reflections	Δρ_min = −0.25 e Å⁻³
99 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.29989 (10)	0.7500	0.4672 (3)	0.0944 (10)
O2	0.38001 (14)	0.7500	0.3510 (3)	0.1103 (12)
O3	0.38835 (9)	0.5888 (4)	0.6773 (3)	0.1216 (10)
O1W	0.40771 (12)	0.2500	0.8491 (3)	0.0790 (8)
H1	0.3983 (11)	0.358 (4)	0.784 (3)	0.098 (9)*
N1	0.04672 (8)	0.7500	0.7763 (3)	0.0442 (6)
N2	0.27226 (8)	0.7500	1.0044 (2)	0.0372 (6)
C1	0.02478 (11)	0.5681 (4)	0.7022 (3)	0.0864 (9)
H1A	−0.0141	0.5665	0.7121	0.130*
H1B	0.0397	0.4531	0.7522	0.130*
H1C	0.0345	0.5669	0.5945	0.130*
C2	0.10673 (11)	0.7500	0.7595 (5)	0.0679 (10)
H2A	0.1218	0.8579	0.8181	0.102*	0.50
H2B	0.1161	0.7654	0.6522	0.102*	0.50
H2C	0.1211	0.6267	0.7974	0.102*	0.50
C3	0.03268 (14)	0.7500	0.9431 (3)	0.0652 (9)
H3A	−0.0060	0.7379	0.9548	0.098*	0.50
H3B	0.0447	0.8719	0.9894	0.098*	0.50
H3C	0.0502	0.6402	0.9932	0.098*	0.50
C4	0.30685 (10)	0.5697 (3)	1.0196 (3)	0.0620 (7)
H4A	0.3247	0.5708	1.1185	0.093*
H4B	0.3336	0.5689	0.9387	0.093*
H4C	0.2846	0.4533	1.0113	0.093*
C5	0.22984 (12)	0.7500	1.1282 (3)	0.0522 (8)
H5A	0.2459	0.7116	1.2249	0.078*	0.50
H5B	0.2016	0.6577	1.1014	0.078*	0.50
H5C	0.2147	0.8807	1.1377	0.078*	0.50
C6	0.24524 (12)	0.7500	0.8504 (3)	0.0548 (8)
H6A	0.2219	0.8636	0.8423	0.082*	0.50
H6B	0.2241	0.6311	0.8391	0.082*	0.50
H6C	0.2723	0.7554	0.7704	0.082*	0.5
C7	0.35047 (12)	0.7500	0.4666 (3)	0.0486 (7)
C8	0.37795 (10)	0.7500	0.6197 (3)	0.0479 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0651 (17)	0.124 (3)	0.0938 (19)	0.000	−0.0318 (14)	0.000
O2	0.134 (3)	0.146 (3)	0.0503 (15)	0.000	0.0259 (16)	0.000
O3	0.1149 (17)	0.126 (2)	0.1237 (18)	0.0185 (14)	−0.0231 (13)	0.0734 (15)
O1W	0.113 (2)	0.0643 (16)	0.0591 (15)	0.000	−0.0145 (14)	0.000
N1	0.0386 (12)	0.0467 (13)	0.0473 (13)	0.000	0.0020 (9)	0.000
N2	0.0416 (11)	0.0366 (11)	0.0334 (11)	0.000	−0.0011 (9)	0.000
C1	0.0809 (17)	0.093 (2)	0.0849 (17)	−0.0298 (16)	0.0007 (14)	−0.0317 (15)
C2	0.0404 (15)	0.060 (2)	0.103 (3)	0.000	0.0112 (16)	0.000
C3	0.069 (2)	0.078 (2)	0.0486 (17)	0.000	0.0046 (15)	0.000
C4	0.0677 (13)	0.0551 (14)	0.0631 (13)	0.0215 (11)	−0.0031 (10)	0.0016 (11)
C5	0.0562 (17)	0.0583 (18)	0.0419 (15)	0.000	0.0097 (12)	0.000
C6	0.0586 (17)	0.071 (2)	0.0352 (14)	0.000	−0.0093 (12)	0.000
C7	0.0614 (18)	0.0383 (15)	0.0461 (15)	0.000	−0.0003 (13)	0.000
C8	0.0356 (14)	0.0592 (18)	0.0489 (15)	0.000	0.0053 (11)	0.000

Geometric parameters (Å, º) top

O1—C7	1.245 (4)	C2—H2B	0.9600
O2—C7	1.235 (4)	C2—H2C	0.9600
O3—C8	1.222 (2)	C3—H3A	0.9600
O1W—H1	0.95 (3)	C3—H3B	0.9600
N1—C3	1.481 (3)	C3—H3C	0.9600
N1—C2	1.484 (3)	C4—H4A	0.9600
N1—C1	1.484 (3)	C4—H4B	0.9600
N1—C1ⁱ	1.484 (3)	C4—H4C	0.9600
N2—C6	1.487 (3)	C5—H5A	0.9600
N2—C4	1.489 (2)	C5—H5B	0.9600
N2—C4ⁱ	1.489 (2)	C5—H5C	0.9600
N2—C5	1.494 (3)	C6—H6A	0.9600
C1—H1A	0.9600	C6—H6B	0.9600
C1—H1B	0.9600	C6—H6C	0.9600
C1—H1C	0.9600	C7—C8	1.484 (4)
C2—H2A	0.9600	C8—O3ⁱ	1.222 (2)

C3—N1—C2	109.1 (3)	N1—C3—H3C	109.5
C3—N1—C1	109.52 (16)	H3A—C3—H3C	109.5
C2—N1—C1	108.66 (17)	H3B—C3—H3C	109.5
C3—N1—C1ⁱ	109.52 (16)	N2—C4—H4A	109.5
C2—N1—C1ⁱ	108.66 (17)	N2—C4—H4B	109.5
C1—N1—C1ⁱ	111.3 (3)	H4A—C4—H4B	109.5
C6—N2—C4	109.54 (13)	N2—C4—H4C	109.5
C6—N2—C4ⁱ	109.54 (13)	H4A—C4—H4C	109.5
C4—N2—C4ⁱ	109.3 (2)	H4B—C4—H4C	109.5
C6—N2—C5	109.1 (2)	N2—C5—H5A	109.5
C4—N2—C5	109.68 (14)	N2—C5—H5B	109.5
C4ⁱ—N2—C5	109.68 (14)	H5A—C5—H5B	109.5
N1—C1—H1A	109.5	N2—C5—H5C	109.5
N1—C1—H1B	109.5	H5A—C5—H5C	109.5
H1A—C1—H1B	109.5	H5B—C5—H5C	109.5
N1—C1—H1C	109.5	N2—C6—H6A	109.5
H1A—C1—H1C	109.5	N2—C6—H6B	109.5
H1B—C1—H1C	109.5	H6A—C6—H6B	109.5
N1—C2—H2A	109.5	N2—C6—H6C	109.5
N1—C2—H2B	109.5	H6A—C6—H6C	109.5
H2A—C2—H2B	109.5	H6B—C6—H6C	109.5
N1—C2—H2C	109.5	O2—C7—O1	126.3 (3)
H2A—C2—H2C	109.5	O2—C7—C8	116.8 (3)
H2B—C2—H2C	109.5	O1—C7—C8	116.9 (3)
N1—C3—H3A	109.5	O3ⁱ—C8—O3	125.5 (3)
N1—C3—H3B	109.5	O3ⁱ—C8—C7	117.26 (17)
H3A—C3—H3B	109.5	O3—C8—C7	117.26 (17)

O2—C7—C8—O3ⁱ	89.9 (2)	O2—C7—C8—O3	−89.9 (2)
O1—C7—C8—O3ⁱ	−90.1 (2)	O1—C7—C8—O3	90.1 (2)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1···O3	0.95 (3)	1.82 (3)	2.764 (2)	171 (3)

Experimental details

Crystal data
Chemical formula	2C₄H₁₂N⁺·C₂O₄²⁻·H₂O
M_r	254.33
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	293
a, b, c (Å)	24.614 (4), 6.738 (1), 8.633 (2)
V (Å³)	1431.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEX2
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	3915, 1367, 1043
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.164, 1.01
No. of reflections	1367
No. of parameters	99
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.25

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1···O3	0.95 (3)	1.82 (3)	2.764 (2)	171 (3)

Acknowledgements

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

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mascal, M., Marjo, C. E. & Blake, A. J. (2000). Chem. Commun. pp. 1591–1592. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar