Acta Cryst. (2009). E65, o709 [ doi:10.1107/S1600536809007259 ]
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-HO hydrogen bond with the hydroxyl groups of the cations, constructing a columner structure along the a axis. A number of C-HO interactions are also present.
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.
The H atoms of the OH groups were found in difference maps and refined freely. The other C-bound H atoms were subsequently refined as riding atoms, with C—H = 0.98 and 0.99Å and Uiso(H) = 1.2 or 1.5Ueq(C).
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).
![[Figure 1]](./at2730fig1thm.gif)
| 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. |
![[Figure 2]](./at2730fig2thm.gif)
| 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.] |
| C5H14NO+·H2PO4− | Z = 2 |
| Mr = 201.16 | F(000) = 216 |
| Triclinic, P1 | Dx = 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 |
| Rigaku RAXIS-RAPID diffractometer | 1714 independent reflections |
| Radiation source: rotating anode | 1344 reflections with I > 2σ(I) |
| graphite | Rint = 0.053 |
| Detector resolution: 10.00 pixels mm-1 | θmax = 68.3°, θmin = 5.1° |
| ω scans | h = −8→8 |
| Absorption correction: numerical (NUMABS; Higashi, 1999) | k = −9→9 |
| Tmin = 0.429, Tmax = 0.950 | l = −11→11 |
| 8717 measured reflections |
| 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(Fo2) + (0.0626P)2 + 0.050P] where P = (Fo2 + 2Fc2)/3 |
| 1714 reflections | (Δ/σ)max < 0.001 |
| 124 parameters | Δρmax = 0.21 e Å−3 |
| 0 restraints | Δρmin = −0.38 e Å−3 |
| C5H14NO+·H2PO4− | γ = 70.758 (3)° |
| Mr = 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)° |
| Rigaku RAXIS-RAPID diffractometer | 1714 independent reflections |
| Absorption correction: numerical (NUMABS; Higashi, 1999) | 1344 reflections with I > 2σ(I) |
| Tmin = 0.429, Tmax = 0.950 | Rint = 0.053 |
| 8717 measured reflections | θmax = 68.3° |
| R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.121 | Δρmax = 0.21 e Å−3 |
| S = 1.12 | Δρmin = −0.38 e Å−3 |
| 1714 reflections | Absolute structure: ? |
| 124 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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. |
| x | y | z | Uiso*/Ueq | ||
| 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)* |
| 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) |
| 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) |
| 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···O1iv | 0.98 | 2.49 | 3.457 (3) | 168 |
| C5—H5A···O3iv | 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. |
| 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···O1iv | 0.98 | 2.49 | 3.457 (3) | 168 |
| C5—H5A···O3iv | 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. |
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.
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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).