Tetra­methyl­ammonium dihydrogen phosphate hemihydrate

Fujita, K.; MacFarlane, D.R.; Noguchi, K.; Ohno, H.

doi:10.1107/S1600536809009179

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o797

doi:10.1107/S1600536809009179

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Tetramethylammonium dihydrogen phosphate hemihydrate

Kyoko Fujita,^a Douglas R. MacFarlane,^b Keiichi Noguchi ^c and Hiroyuki Ohno ^a ^*

^aDepartment of Biotechnology, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan, ^bSchool of Chemistry, Monash University, Wellington Road, Clayton, Victoria 3800, Australia, and ^cInstrumentation Analysis Center, Tokyo University of Agriculture and Technology, 2-24-16 Naka-cho, Koganei, Tokyo 184-8588, Japan
^*Correspondence e-mail: ohnoh@cc.tuat.ac.jp

(Received 24 February 2009; accepted 12 March 2009; online 19 March 2009)

In the crystal structure of the title compound, C₄H₁₂N⁺·H₂PO₄⁻·0.5H₂O, the anions form an infinite hydrogen-bonded chain along the [1 $[\overline{1}]$ 0] direction. The anion chains are connected by water molecules, which lie on crystallographic twofold rotation axes, through O—H⋯O hydrogen bonds. These hydrogen bonds are almost perpendicular to the other hydrogen bonds which create an assembled structure of anions. In addition, C—H⋯O hydrogen bonds between anions and cations are observed.

Related literature

For the structure of tetramethylammonium dihydrogen phosphate monohydrate, see: Ohama et al. (1987 ).

Experimental

Crystal data

C₄H₁₂N⁺·H₂PO₄⁻·0.5H₂O
M_r = 180.14
Monoclinic, C 2/c
a = 14.3213 (3) Å
b = 9.2607 (2) Å
c = 13.1990 (2) Å
β = 103.614 (1)°
V = 1701.34 (6) Å³
Z = 8
Cu Kα radiation
μ = 2.72 mm⁻¹
T = 193 K
0.40 × 0.35 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ) T_min = 0.390, T_max = 0.580
14805 measured reflections
1565 independent reflections
1505 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.084
S = 1.05
1565 reflections
113 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O2ⁱ	0.96 (4)	1.57 (4)	2.5196 (18)	169 (4)
O4—H4O⋯O1ⁱⁱ	0.75 (3)	1.83 (3)	2.5644 (19)	169 (3)
O5—H5O⋯O1	0.83 (3)	2.06 (3)	2.8883 (15)	173 (3)
C1—H1B⋯O1ⁱⁱⁱ	0.98	2.62	3.405 (2)	137
C2—H2B⋯O4^iv	0.98	2.39	3.291 (3)	153
C2—H2C⋯O2	0.98	2.59	3.506 (3)	156
C2—H2C⋯O1	0.98	2.62	3.473 (3)	145
C3—H3A⋯O3^v	0.98	2.57	3.495 (3)	157
C4—H4C⋯O3^vi	0.98	2.62	3.465 (3)	144
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) -x+1, -y, -z+1; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y, z-{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku/MSC, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009179/is2395sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809009179/is2395Isup2.hkl

checkCIF report

Comment top

The title compound, (I), forms two hydrate states, hemihydrate and monohydrate. Basic structure about monohydrate had been published (Ohama et al., 1987). We report herein the crystal structure of the hemihydrate compound.

The molecular structures of (I) are shown in Fig. 1. There are eight anions and cations, and four water molecules in a unit cell. The water molecules are located on twofold rotation axes. The anions create infinite chains by using two hydrogen bonds of O4—H···O1 and O3—H···O2 (Fig. 2). These chains run two different directions mutually along the c axis. One is [110] direction, the other is [110] direction. Water molecules connect the anion chains by hydrogen bonds of O5—H···O1, so as to create three dimensional networks. The cations are arranged along with the anion chains (Fig. 3). Molecular packing is additionally stabilized by C—H···O hydrogen bonds between anions and cations (Table 1).

Related literature top

For the structure of tetramethylammonium dihydrogen phosphate monohydrate, see: Ohama et al. (1987).

Experimental top

Tetramethylammonium hydrated solution was mixed with phosphoric acid. The solvent was evaporated and product was dried in vacuo. Final purification was achieved by recrystallization from a methanol solution. The compound was identified using ¹H NMR, DSC and Electrospray mass spectrometry.

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC, 1998); cell refinement: PROCESS-AUTO (Rigaku/MSC, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Displacement ellipsoid plot and atomic numbering scheme of (I). Ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Symmetry code: (vii) -x + 1, y, -z + 1/2.]
	Fig. 2. The molecular packing of (I), viewed along the b axis. Dashed lines indicate intermolecular O—H···O hydrogen bonds. For clarity, only H atoms involved in O—H···O hydrogen bonding have been included. [Symmetry codes: (i) -x + 1/2,-y + 1/2, -z + 1; (ii) -x + 1, -y, -z + 1.]
	Fig. 3. The molecular packing of (I), viewed along the c axis. Dashed lines indicate intermolecular O—H···O hydrogen bonds. For clarity, only H atoms involved in O—H···O hydrogen bonding have been included. [Symmetry codes: (i) -x + 1/2,-y + 1/2, -z + 1; (ii) -x + 1, -y, -z + 1; (iii) -x + 1/2, y + 1/2, -z + 1/2.]

Tetramethylammonium dihydrogen phosphate hemihydrate top

Crystal data top

C₄H₁₂N⁺·H₂O₄P⁻·0.5H₂O	F(000) = 776
M_r = 180.14	D_x = 1.407 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -C 2yc	Cell parameters from 13463 reflections
a = 14.3213 (3) Å	θ = 3.4–68.2°
b = 9.2607 (2) Å	µ = 2.72 mm⁻¹
c = 13.1990 (2) Å	T = 193 K
β = 103.614 (1)°	Block, colorless
V = 1701.34 (6) Å³	0.40 × 0.35 × 0.20 mm
Z = 8

Data collection top

Rigaku R-AXIS RAPID diffractometer	1565 independent reflections
Radiation source: rotating anode	1505 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 10.00 pixels mm^-1	θ_max = 68.2°, θ_min = 5.7°
ω scans	h = −17→17
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −11→11
T_min = 0.390, T_max = 0.580	l = −15→15
14805 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0404P)² + 2.3234P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1565 reflections	Δρ_max = 0.23 e Å⁻³
113 parameters	Δρ_min = −0.31 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: 0.0039 (3)

Crystal data top

C₄H₁₂N⁺·H₂O₄P⁻·0.5H₂O	V = 1701.34 (6) Å³
M_r = 180.14	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 14.3213 (3) Å	µ = 2.72 mm⁻¹
b = 9.2607 (2) Å	T = 193 K
c = 13.1990 (2) Å	0.40 × 0.35 × 0.20 mm
β = 103.614 (1)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1565 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	1505 reflections with I > 2σ(I)
T_min = 0.390, T_max = 0.580	R_int = 0.040
14805 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.23 e Å⁻³
1565 reflections	Δρ_min = −0.31 e Å⁻³
113 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
P1	0.37195 (3)	0.13092 (4)	0.48223 (3)	0.02350 (19)
O1	0.43439 (8)	0.11276 (14)	0.40616 (9)	0.0306 (3)
O2	0.26771 (8)	0.08626 (14)	0.43819 (10)	0.0355 (3)
O3	0.37576 (9)	0.28806 (13)	0.52247 (11)	0.0355 (3)
O4	0.41159 (10)	0.03446 (16)	0.58089 (10)	0.0375 (4)
N1	0.15455 (10)	0.15807 (15)	0.14754 (10)	0.0264 (3)
C1	0.11725 (17)	0.2789 (2)	0.20042 (16)	0.0456 (5)
H1A	0.0469	0.2784	0.1808	0.055*
H1B	0.1410	0.3707	0.1793	0.055*
H1C	0.1393	0.2675	0.2761	0.055*
C2	0.26055 (16)	0.1614 (4)	0.17612 (19)	0.0726 (9)
H2A	0.2831	0.2550	0.1566	0.087*
H2B	0.2856	0.0841	0.1392	0.087*
H2C	0.2833	0.1472	0.2515	0.087*
C3	0.12037 (14)	0.1727 (2)	0.03190 (14)	0.0384 (5)
H3A	0.0502	0.1653	0.0122	0.046*
H3B	0.1484	0.0956	−0.0023	0.046*
H3C	0.1401	0.2667	0.0100	0.046*
C4	0.1185 (3)	0.0209 (3)	0.1815 (2)	0.0816 (10)
H4A	0.0481	0.0194	0.1602	0.098*
H4B	0.1390	0.0128	0.2576	0.098*
H4C	0.1444	−0.0605	0.1493	0.098*
O5	0.5000	0.2765 (2)	0.2500	0.0533 (6)
H3O	0.318 (3)	0.325 (5)	0.537 (3)	0.130 (14)*
H4O	0.4569 (19)	−0.003 (3)	0.5780 (19)	0.048 (7)*
H5O	0.4803 (19)	0.223 (3)	0.291 (2)	0.059 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0201 (3)	0.0248 (3)	0.0272 (3)	0.00388 (15)	0.00872 (17)	−0.00004 (15)
O1	0.0281 (6)	0.0381 (7)	0.0282 (6)	0.0099 (5)	0.0117 (5)	0.0056 (5)
O2	0.0240 (6)	0.0379 (7)	0.0445 (7)	−0.0021 (5)	0.0074 (5)	−0.0135 (6)
O3	0.0291 (6)	0.0264 (7)	0.0538 (8)	−0.0022 (5)	0.0155 (6)	−0.0083 (6)
O4	0.0340 (7)	0.0466 (8)	0.0380 (7)	0.0179 (6)	0.0206 (6)	0.0146 (6)
N1	0.0293 (7)	0.0262 (7)	0.0246 (7)	0.0037 (6)	0.0081 (6)	0.0018 (5)
C1	0.0584 (13)	0.0441 (12)	0.0370 (10)	0.0183 (10)	0.0169 (9)	−0.0020 (9)
C2	0.0317 (11)	0.145 (3)	0.0396 (12)	0.0238 (14)	0.0061 (9)	−0.0052 (15)
C3	0.0414 (10)	0.0471 (11)	0.0260 (9)	0.0102 (9)	0.0064 (8)	0.0030 (8)
C4	0.162 (3)	0.0378 (13)	0.0494 (14)	−0.0344 (17)	0.0325 (17)	−0.0002 (11)
O5	0.0807 (17)	0.0291 (11)	0.0653 (15)	0.000	0.0476 (13)	0.000

Geometric parameters (Å, º) top

P1—O1	1.5029 (12)	C1—H1C	0.9800
P1—O2	1.5261 (12)	C2—H2A	0.9800
P1—O3	1.5456 (12)	C2—H2B	0.9800
P1—O4	1.5710 (13)	C2—H2C	0.9800
O3—H3O	0.96 (5)	C3—H3A	0.9800
O4—H4O	0.75 (3)	C3—H3B	0.9800
N1—C2	1.476 (3)	C3—H3C	0.9800
N1—C4	1.480 (3)	C4—H4A	0.9800
N1—C1	1.483 (2)	C4—H4B	0.9800
N1—C3	1.495 (2)	C4—H4C	0.9800
C1—H1A	0.9800	O5—H5O	0.83 (3)
C1—H1B	0.9800

O1—P1—O2	113.43 (7)	H1B—C1—H1C	109.5
O1—P1—O3	110.89 (7)	N1—C2—H2A	109.5
O2—P1—O3	109.77 (7)	N1—C2—H2B	109.5
O1—P1—O4	109.53 (7)	H2A—C2—H2B	109.5
O2—P1—O4	106.97 (8)	N1—C2—H2C	109.5
O3—P1—O4	105.89 (8)	H2A—C2—H2C	109.5
P1—O3—H3O	116 (3)	H2B—C2—H2C	109.5
P1—O4—H4O	111.8 (19)	N1—C3—H3A	109.5
C2—N1—C4	110.6 (2)	N1—C3—H3B	109.5
C2—N1—C1	109.08 (18)	H3A—C3—H3B	109.5
C4—N1—C1	108.36 (18)	N1—C3—H3C	109.5
C2—N1—C3	109.20 (15)	H3A—C3—H3C	109.5
C4—N1—C3	109.46 (17)	H3B—C3—H3C	109.5
C1—N1—C3	110.14 (14)	N1—C4—H4A	109.5
N1—C1—H1A	109.5	N1—C4—H4B	109.5
N1—C1—H1B	109.5	H4A—C4—H4B	109.5
H1A—C1—H1B	109.5	N1—C4—H4C	109.5
N1—C1—H1C	109.5	H4A—C4—H4C	109.5
H1A—C1—H1C	109.5	H4B—C4—H4C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2ⁱ	0.96 (4)	1.57 (4)	2.5196 (18)	169 (4)
O4—H4O···O1ⁱⁱ	0.75 (3)	1.83 (3)	2.5644 (19)	169 (3)
O5—H5O···O1	0.83 (3)	2.06 (3)	2.8883 (15)	173 (3)
C1—H1B···O1ⁱⁱⁱ	0.98	2.62	3.405 (2)	137
C2—H2B···O4^iv	0.98	2.39	3.291 (3)	153
C2—H2C···O2	0.98	2.59	3.506 (3)	156
C2—H2C···O1	0.98	2.62	3.473 (3)	145
C3—H3A···O3^v	0.98	2.57	3.495 (3)	157
C4—H4C···O3^vi	0.98	2.62	3.465 (3)	144

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, −y, z−1/2; (v) x−1/2, −y+1/2, z−1/2; (vi) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₄H₁₂N⁺·H₂O₄P⁻·0.5H₂O
M_r	180.14
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	193
a, b, c (Å)	14.3213 (3), 9.2607 (2), 13.1990 (2)
β (°)	103.614 (1)
V (Å³)	1701.34 (6)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	2.72
Crystal size (mm)	0.40 × 0.35 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.390, 0.580
No. of measured, independent and observed [I > 2σ(I)] reflections	14805, 1565, 1505
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.084, 1.05
No. of reflections	1565
No. of parameters	113
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.31

Computer programs: PROCESS-AUTO (Rigaku/MSC, 1998), CrystalStructure (Rigaku/MSC, 2004), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2ⁱ	0.96 (4)	1.57 (4)	2.5196 (18)	169 (4)
O4—H4O···O1ⁱⁱ	0.75 (3)	1.83 (3)	2.5644 (19)	169 (3)
O5—H5O···O1	0.83 (3)	2.06 (3)	2.8883 (15)	173 (3)
C1—H1B···O1ⁱⁱⁱ	0.98	2.62	3.405 (2)	137
C2—H2B···O4^iv	0.98	2.39	3.291 (3)	153
C2—H2C···O2	0.98	2.59	3.506 (3)	156
C2—H2C···O1	0.98	2.62	3.473 (3)	145
C3—H3A···O3^v	0.98	2.57	3.495 (3)	157
C4—H4C···O3^vi	0.98	2.62	3.465 (3)	144

Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x, −y, z−1/2; (v) x−1/2, −y+1/2, z−1/2; (vi) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

This study was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology of Japan. KF thanks the Japan Society for Promotion of Science (Research Fellowship for Young Scientists) for support.

References

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