Choline dihydrogen phosphate

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

doi:10.1107/S1600536809007259

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o709

doi:10.1107/S1600536809007259

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Choline dihydrogen phosphate

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

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

(Received 24 February 2009; accepted 27 February 2009; online 6 March 2009)

In the cystal structure of the title compound, (2-hydroxyethyl)trimethylammonium dihydrogen phosphate, C₅H₁₄NO⁺·H₂PO₄⁻, two anions create dimeric structures via two O—H⋯O hydrogen bonds. The hydrogen-bonded dimers are connected by another O—H⋯O hydrogen bond with the hydroxyl groups of the cations, constructing a columner structure along the a axis. A number of C—H⋯O interactions are also present.

Related literature

For background to ionic liquids, see: Byrne et al. (2007 ); Fujita et al. (2005 ); Ohno (2005 ); van Rantwijk et al. (2003 ); Seddon (1997 ); Wasserscheid & Welton (2002 ); Welton (1999 ); Zhao et al. (2008 ).

Experimental

Crystal data

C₅H₁₄NO⁺·H₂PO₄⁻
M_r = 201.16
Triclinic, $[P \overline 1]$
a = 6.9232 (3) Å
b = 8.2807 (4) Å
c = 9.2333 (3) Å
α = 84.458 (3)°
β = 71.414 (3)°
γ = 70.758 (3)°
V = 473.68 (4) Å³
Z = 2
Cu Kα radiation
μ = 2.55 mm⁻¹
T = 193 K
0.60 × 0.10 × 0.02 mm

Data collection

Rigaku RAXIS-RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ) T_min = 0.429, T_max = 0.950
8717 measured reflections
1714 independent reflections
1344 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.121
S = 1.12
1714 reflections
124 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O5ⁱ	0.80 (4)	1.79 (4)	2.586 (3)	178 (3)
O4—H4O⋯O2ⁱ	0.93 (4)	1.60 (4)	2.526 (2)	173 (3)
O5—H5O⋯O1ⁱⁱ	0.93 (4)	1.63 (4)	2.556 (3)	176 (4)
C3—H3B⋯O1	0.98	2.48	3.439 (3)	166
C4—H4B⋯O3ⁱⁱⁱ	0.98	2.54	3.504 (3)	170
C4—H4C⋯O1^iv	0.98	2.49	3.457 (3)	168
C5—H5A⋯O3^iv	0.98	2.46	3.430 (3)	172
C5—H5B⋯O1ⁱⁱⁱ	0.98	2.42	3.382 (3)	169
C5—H5C⋯O2	0.98	2.60	3.549 (3)	164
Symmetry codes: (i) -x+2, -y+1, -z; (ii) -x+1, -y+1, -z; (iii) -x+1, -y+1, -z+1; (iv) x, y-1, z.

Data collection: PROCESS-AUTO (Rigaku, 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/S1600536809007259/at2730sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007259/at2730Isup2.hkl

checkCIF report

Comment top

Some ionic liquids (ILs) possess negligible vapor pressure as well as fascinating features such as high thermal, chemical and electrochemical stability. ILs have gained increasing attention as green, multi-use reaction media as well as solvents for a electrochemistry and chemistry (Welton, 1999; Seddon, 1997; Wasserscheid & Welton, 2002). ILs are also currently being investigated for a variety of bio-applications including media for biocatalytic reactions (van Rantwijk et al., 2003; Zhao et al., 2008), biosensors (Ohno, 2005) and protein stabilization (Fujita et al., 2005; Byrne et al., 2007). We have been studying hydrated IL as solvents for proteins. We have already reported that some proteins are soluble, stable, and remain active in some hydrated ILs. For example, the title compounds, acts as an excellent preserver of proteins such as cytochrome c.

The title compound (I) consists of cations and anions. The molecular structures of (I) are shown in Fig. 1. Two hydrogen bonds of O4—H···O2 connect anions and construct dimer along the b axis (Fig. 2). The dimers are connected with each other by the two hydrogen bonds of O5—H···O1 and O3—H···O5, through the hydroxyl group (Table 1). These hydrogen bonds create a columnar structure of anions and cations along the a axis. The columnar structures interact with each other by C—H···O hydrogen bond and van der Waals forces (Table 1).

Related literature top

For background to ionic liquids, see: Byrne et al. (2007); Fujita et al. (2005); Ohno (2005); van Rantwijk et al. (2003); Seddon (1997); Wasserscheid & Welton (2002); Welton (1999); Zhao et al. (2008).

Experimental top

Choline bromide solution was treated on an ion exchange resin (Amberlite IRN77), then mixed with phosphoric acid solution. The solvent evaporated and the product was dried in vacuo. White powder was dissolved in methanol, then reprecipited by dropping in acetone. This reprecipitation was repeated four times. Final purification was achieved by drowning-out crystallization from methanol solution. Aceton was used as antisolvent. This drowning-out crystallization was repeated twice at room temperature for X-ray measurements. The compound was identified using ¹H NMR, DSC and Electrospray mass spectrometry.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 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); 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 arbitary radii.
	Fig. 2. The molecular packing of (I) viewed along 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 + 2, -y + 1, -z; (ii) -x + 1, -y + 1, -z.]

(2-hydroxyethyl)trimethylammonium dihydrogen phosphate top

Crystal data top

C₅H₁₄NO⁺·H₂PO₄⁻	Z = 2
M_r = 201.16	F(000) = 216
Triclinic, P1	D_x = 1.410 Mg m⁻³
Hall symbol: -P 1	Melting point: 392 K
a = 6.9232 (3) Å	Cu Kα radiation, λ = 1.54187 Å
b = 8.2807 (4) Å	Cell parameters from 6930 reflections
c = 9.2333 (3) Å	θ = 5.1–68.3°
α = 84.458 (3)°	µ = 2.55 mm⁻¹
β = 71.414 (3)°	T = 193 K
γ = 70.758 (3)°	Platelet, colourless
V = 473.68 (4) Å³	0.60 × 0.10 × 0.02 mm

Data collection top

Rigaku RAXIS-RAPID diffractometer	1714 independent reflections
Radiation source: rotating anode	1344 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 10.00 pixels mm^-1	θ_max = 68.3°, θ_min = 5.1°
ω scans	h = −8→8
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −9→9
T_min = 0.429, T_max = 0.950	l = −11→11
8717 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: difference Fourier map
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0626P)² + 0.050P] where P = (F_o² + 2F_c²)/3
1714 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₅H₁₄NO⁺·H₂PO₄⁻	γ = 70.758 (3)°
M_r = 201.16	V = 473.68 (4) Å³
Triclinic, P1	Z = 2
a = 6.9232 (3) Å	Cu Kα radiation
b = 8.2807 (4) Å	µ = 2.55 mm⁻¹
c = 9.2333 (3) Å	T = 193 K
α = 84.458 (3)°	0.60 × 0.10 × 0.02 mm
β = 71.414 (3)°

Data collection top

Rigaku RAXIS-RAPID diffractometer	1714 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	1344 reflections with I > 2σ(I)
T_min = 0.429, T_max = 0.950	R_int = 0.053
8717 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.21 e Å⁻³
1714 reflections	Δρ_min = −0.38 e Å⁻³
124 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	0.81645 (9)	0.68990 (7)	0.17447 (6)	0.0335 (2)
O1	0.5777 (2)	0.7534 (2)	0.24514 (18)	0.0430 (5)
O2	0.9220 (3)	0.50241 (19)	0.19693 (17)	0.0439 (5)
O3	0.9039 (3)	0.8007 (2)	0.25187 (19)	0.0390 (4)
O4	0.8798 (3)	0.7343 (2)	0.00080 (18)	0.0406 (4)
O5	0.7017 (3)	0.2172 (2)	−0.10979 (19)	0.0452 (5)
N1	0.4405 (3)	0.2917 (2)	0.3125 (2)	0.0340 (5)
C1	0.5122 (4)	0.3227 (3)	0.1424 (2)	0.0342 (5)
H1A	0.5978	0.4020	0.1227	0.041*
H1B	0.3832	0.3801	0.1096	0.041*
C2	0.6444 (4)	0.1635 (3)	0.0453 (2)	0.0391 (6)
H2A	0.7750	0.1035	0.0755	0.047*
H2B	0.5596	0.0844	0.0584	0.047*
C3	0.3093 (4)	0.4616 (3)	0.3894 (3)	0.0417 (6)
H3A	0.1821	0.5104	0.3547	0.050*
H3B	0.3958	0.5391	0.3633	0.050*
H3C	0.2640	0.4464	0.5003	0.050*
C4	0.3029 (4)	0.1774 (3)	0.3487 (3)	0.0458 (7)
H4A	0.1836	0.2257	0.3057	0.055*
H4B	0.2458	0.1681	0.4597	0.055*
H4C	0.3893	0.0636	0.3042	0.055*
C5	0.6299 (4)	0.2169 (3)	0.3699 (3)	0.0435 (6)
H5A	0.7117	0.1024	0.3255	0.052*
H5B	0.5805	0.2089	0.4815	0.052*
H5C	0.7219	0.2902	0.3403	0.052*
H3O	1.025 (5)	0.793 (4)	0.209 (3)	0.058 (9)*
H4O	0.959 (6)	0.643 (5)	−0.067 (4)	0.096 (12)*
H5O	0.597 (5)	0.232 (4)	−0.158 (4)	0.090 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0331 (4)	0.0388 (4)	0.0280 (4)	−0.0104 (3)	−0.0088 (3)	−0.0016 (2)
O1	0.0311 (9)	0.0607 (12)	0.0372 (9)	−0.0139 (8)	−0.0102 (7)	−0.0032 (8)
O2	0.0622 (11)	0.0359 (10)	0.0292 (9)	−0.0108 (8)	−0.0130 (8)	0.0003 (7)
O3	0.0323 (9)	0.0490 (10)	0.0363 (9)	−0.0148 (8)	−0.0066 (7)	−0.0093 (7)
O4	0.0474 (10)	0.0392 (10)	0.0298 (9)	−0.0082 (8)	−0.0099 (7)	−0.0009 (7)
O5	0.0372 (9)	0.0728 (13)	0.0290 (9)	−0.0221 (9)	−0.0102 (7)	0.0022 (8)
N1	0.0408 (11)	0.0326 (10)	0.0299 (10)	−0.0123 (8)	−0.0125 (8)	0.0028 (8)
C1	0.0372 (12)	0.0396 (13)	0.0284 (12)	−0.0143 (10)	−0.0124 (10)	0.0042 (9)
C2	0.0421 (13)	0.0476 (14)	0.0282 (12)	−0.0154 (11)	−0.0103 (10)	0.0001 (10)
C3	0.0476 (14)	0.0366 (13)	0.0340 (12)	−0.0063 (11)	−0.0097 (11)	−0.0028 (10)
C4	0.0574 (16)	0.0469 (15)	0.0356 (13)	−0.0284 (13)	−0.0064 (11)	0.0038 (11)
C5	0.0506 (15)	0.0435 (14)	0.0352 (13)	−0.0045 (12)	−0.0223 (11)	0.0006 (11)

Geometric parameters (Å, º) top

P1—O1	1.4969 (16)	C1—H1A	0.9900
P1—O2	1.5080 (16)	C1—H1B	0.9900
P1—O4	1.5629 (16)	C2—H2A	0.9900
P1—O3	1.5771 (17)	C2—H2B	0.9900
O3—H3O	0.79 (3)	C3—H3A	0.9800
O4—H4O	0.93 (4)	C3—H3B	0.9800
O5—C2	1.427 (3)	C3—H3C	0.9800
O5—H5O	0.93 (4)	C4—H4A	0.9800
N1—C5	1.493 (3)	C4—H4B	0.9800
N1—C4	1.499 (3)	C4—H4C	0.9800
N1—C3	1.499 (3)	C5—H5A	0.9800
N1—C1	1.513 (3)	C5—H5B	0.9800
C1—C2	1.513 (3)	C5—H5C	0.9800

O1—P1—O2	115.19 (10)	C1—C2—H2A	110.3
O1—P1—O4	110.63 (9)	O5—C2—H2B	110.3
O2—P1—O4	110.24 (9)	C1—C2—H2B	110.3
O1—P1—O3	104.81 (9)	H2A—C2—H2B	108.6
O2—P1—O3	109.78 (10)	N1—C3—H3A	109.5
O4—P1—O3	105.63 (10)	N1—C3—H3B	109.5
P1—O3—H3O	113 (2)	H3A—C3—H3B	109.5
P1—O4—H4O	117 (2)	N1—C3—H3C	109.5
C2—O5—H5O	114 (2)	H3A—C3—H3C	109.5
C5—N1—C4	110.68 (19)	H3B—C3—H3C	109.5
C5—N1—C3	108.80 (19)	N1—C4—H4A	109.5
C4—N1—C3	108.66 (19)	N1—C4—H4B	109.5
C5—N1—C1	110.65 (17)	H4A—C4—H4B	109.5
C4—N1—C1	110.51 (18)	N1—C4—H4C	109.5
C3—N1—C1	107.44 (16)	H4A—C4—H4C	109.5
N1—C1—C2	114.88 (18)	H4B—C4—H4C	109.5
N1—C1—H1A	108.5	N1—C5—H5A	109.5
C2—C1—H1A	108.5	N1—C5—H5B	109.5
N1—C1—H1B	108.5	H5A—C5—H5B	109.5
C2—C1—H1B	108.5	N1—C5—H5C	109.5
H1A—C1—H1B	107.5	H5A—C5—H5C	109.5
O5—C2—C1	107.09 (19)	H5B—C5—H5C	109.5
O5—C2—H2A	110.3

C5—N1—C1—C2	62.5 (3)	C3—N1—C1—C2	−178.9 (2)
C4—N1—C1—C2	−60.5 (3)	N1—C1—C2—O5	−178.51 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O5ⁱ	0.80 (4)	1.79 (4)	2.586 (3)	178 (3)
O4—H4O···O2ⁱ	0.93 (4)	1.60 (4)	2.526 (2)	173 (3)
O5—H5O···O1ⁱⁱ	0.93 (4)	1.63 (4)	2.556 (3)	176 (4)
C3—H3B···O1	0.98	2.48	3.439 (3)	166
C4—H4B···O3ⁱⁱⁱ	0.98	2.54	3.504 (3)	170
C4—H4C···O1^iv	0.98	2.49	3.457 (3)	168
C5—H5A···O3^iv	0.98	2.46	3.430 (3)	172
C5—H5B···O1ⁱⁱⁱ	0.98	2.42	3.382 (3)	169
C5—H5C···O2	0.98	2.60	3.549 (3)	164

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

Experimental details

Crystal data
Chemical formula	C₅H₁₄NO⁺·H₂PO₄⁻
M_r	201.16
Crystal system, space group	Triclinic, P1
Temperature (K)	193
a, b, c (Å)	6.9232 (3), 8.2807 (4), 9.2333 (3)
α, β, γ (°)	84.458 (3), 71.414 (3), 70.758 (3)
V (Å³)	473.68 (4)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	2.55
Crystal size (mm)	0.60 × 0.10 × 0.02

Data collection
Diffractometer	Rigaku RAXIS-RAPID diffractometer
Absorption correction	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.429, 0.950
No. of measured, independent and observed [I > 2σ(I)] reflections	8717, 1714, 1344
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.121, 1.12
No. of reflections	1714
No. of parameters	124
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.38

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O5ⁱ	0.80 (4)	1.79 (4)	2.586 (3)	178 (3)
O4—H4O···O2ⁱ	0.93 (4)	1.60 (4)	2.526 (2)	173 (3)
O5—H5O···O1ⁱⁱ	0.93 (4)	1.63 (4)	2.556 (3)	176 (4)
C3—H3B···O1	0.98	2.48	3.439 (3)	166
C4—H4B···O3ⁱⁱⁱ	0.98	2.54	3.504 (3)	170
C4—H4C···O1^iv	0.98	2.49	3.457 (3)	168
C5—H5A···O3^iv	0.98	2.46	3.430 (3)	172
C5—H5B···O1ⁱⁱⁱ	0.98	2.42	3.382 (3)	169
C5—H5C···O2	0.98	2.60	3.549 (3)	164

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

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 the Promotion of Science (Research Fellowship for Young Scientists) for support.

References

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