Acta Cryst. (2008). E64, o2100 [ doi:10.1107/S1600536808032340 ]
The title compound, C8H20N+·Cl-·H2O, has been prepared by a simple one-pot synthesis route followed by anion exchange using resin. In the crystal structure, the cations are packed in such a way that channels exist parallel to the b axis. These channels are filled by the anions and water molecules, which interact via O-H
Cl hydrogen bonds [OCl = 3.285 (3) and 3.239 (3) Å] to form helical chains. The cations are involved in weak intermolecular C-HCl and C-HO hydrogen bonds. The title compound is not isomorphous with the bromo or iodo analogues.
The mixture of 1-bromopropane (95.2 mmol) and dimethylformamide (0.47 mol) in the presence of potassiumcarbonate (95.2 mmol) was stirred at 70°C for 72 h. The reaction mixture was cooled and filtered and the filtrate was evaporated. The product (white powder) was washed with diethyl ether and recrystallized from dichloromethane and dried in vacuo. The anion exhange was performed in a suitable resin, resulting in a light yellow, hygroscopic final product.
The water H atoms were located from the difference Fourier map and refined isotropically. Other H atoms were positioned geometrically and refined using a riding model with C—H = 0.98–0.99 Å and with Uĩso~(H) = 1.2 (1.5 for methyl groups) times U~eq~(C).
Data collection: COLLECT (Nonius, 2002); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997; Otwinowski et al., 2003); data reduction: DENZO-SMN (Otwinowski & Minor, 1997; Otwinowski et al., 2003); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./cv2460fig1thm.gif)
| Fig. 1. The molecular structure of (1) showing the atomic numbering and 50% probability displacement ellipsoids. |
![[Figure 2]](./cv2460fig2thm.gif)
| Fig. 2. The packing of (1) viewed along the crystallographic b-axis. Dashed lines indicate hydrogen bonds. The helical structure of the network between the anions and the water molecules can be seen. The H atoms not involved in the network have been omitted for clarity, as well as some of the cations. |
| C8H20N+·Cl−·H2O | F(000) = 408 |
| Mr = 183.72 | Dx = 1.108 Mg m−3 |
| Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
| a = 7.9870 (16) Å | Cell parameters from 1705 reflections |
| b = 9.4210 (19) Å | θ = 0.9–63.7° |
| c = 14.875 (3) Å | µ = 2.71 mm−1 |
| β = 100.23 (3)° | T = 173 K |
| V = 1101.5 (4) Å3 | Rod, colourless |
| Z = 4 | 0.40 × 0.12 × 0.12 mm |
| Nonius Kappa APEXII diffractometer | 1784 independent reflections |
| Radiation source: fine-focus sealed tube | 1474 reflections with I > 2σ(I) |
| graphite | Rint = 0.056 |
| φ and ω scans | θmax = 63.4°, θmin = 5.6° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −7→9 |
| Tmin = 0.534, Tmax = 0.737 | k = −10→10 |
| 6471 measured reflections | l = −17→16 |
| 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: inferred from neighbouring sites |
| wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0535P)2 + 0.2799P] where P = (Fo2 + 2Fc2)/3 |
| 1784 reflections | (Δ/σ)max < 0.001 |
| 112 parameters | Δρmax = 0.20 e Å−3 |
| 0 restraints | Δρmin = −0.21 e Å−3 |
| C8H20N+·Cl−·H2O | V = 1101.5 (4) Å3 |
| Mr = 183.72 | Z = 4 |
| Monoclinic, P21/n | Cu Kα radiation |
| a = 7.9870 (16) Å | µ = 2.71 mm−1 |
| b = 9.4210 (19) Å | T = 173 K |
| c = 14.875 (3) Å | 0.40 × 0.12 × 0.12 mm |
| β = 100.23 (3)° |
| Nonius Kappa APEXII diffractometer | 1474 reflections with I > 2σ(I) |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | Rint = 0.056 |
| Tmin = 0.534, Tmax = 0.737 | θmax = 63.4° |
| 6471 measured reflections | Standard reflections: 0 |
| 1784 independent reflections |
| R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.108 | Δρmax = 0.20 e Å−3 |
| S = 1.04 | Δρmin = −0.21 e Å−3 |
| 1784 reflections | Absolute structure: ? |
| 112 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 | ||
| Cl1 | 0.33660 (7) | −0.05079 (6) | 0.66252 (4) | 0.0363 (2) | |
| N1 | 0.7874 (2) | 0.10789 (19) | 0.61585 (11) | 0.0244 (4) | |
| O1W | 0.0649 (3) | −0.2974 (3) | 0.68554 (19) | 0.0673 (7) | |
| C21 | 0.9430 (2) | 0.1617 (2) | 0.58112 (14) | 0.0272 (5) | |
| H4A | 1.0416 | 0.1023 | 0.6077 | 0.033* | |
| H4B | 0.9243 | 0.1489 | 0.5140 | 0.033* | |
| C31 | 0.7647 (3) | −0.0457 (2) | 0.59034 (16) | 0.0311 (5) | |
| H5A | 0.6659 | −0.0836 | 0.6131 | 0.047* | |
| H5B | 0.8668 | −0.0987 | 0.6175 | 0.047* | |
| H5C | 0.7466 | −0.0551 | 0.5237 | 0.047* | |
| C13 | 0.9427 (3) | 0.0851 (3) | 0.87601 (15) | 0.0366 (6) | |
| H6A | 0.9657 | 0.1866 | 0.8863 | 0.055* | |
| H6B | 1.0303 | 0.0295 | 0.9153 | 0.055* | |
| H6C | 0.8308 | 0.0622 | 0.8905 | 0.055* | |
| C41 | 0.6317 (3) | 0.1857 (3) | 0.56898 (16) | 0.0333 (5) | |
| H7A | 0.6236 | 0.1783 | 0.5026 | 0.050* | |
| H7B | 0.6399 | 0.2859 | 0.5870 | 0.050* | |
| H7C | 0.5302 | 0.1437 | 0.5868 | 0.050* | |
| C11 | 0.7990 (2) | 0.1267 (2) | 0.71770 (13) | 0.0269 (5) | |
| H8A | 0.6911 | 0.0936 | 0.7346 | 0.032* | |
| H8B | 0.8097 | 0.2294 | 0.7319 | 0.032* | |
| C12 | 0.9448 (3) | 0.0497 (3) | 0.77691 (15) | 0.0319 (5) | |
| H9A | 0.9323 | −0.0540 | 0.7672 | 0.038* | |
| H9B | 1.0542 | 0.0796 | 0.7604 | 0.038* | |
| C22 | 0.9876 (3) | 0.3154 (2) | 0.60251 (17) | 0.0360 (6) | |
| H10A | 1.0077 | 0.3301 | 0.6695 | 0.043* | |
| H10B | 0.8915 | 0.3768 | 0.5749 | 0.043* | |
| C23 | 1.1457 (3) | 0.3563 (3) | 0.5653 (2) | 0.0497 (7) | |
| H11A | 1.2408 | 0.2956 | 0.5929 | 0.074* | |
| H11B | 1.1739 | 0.4558 | 0.5802 | 0.074* | |
| H11C | 1.1247 | 0.3438 | 0.4989 | 0.074* | |
| H1W | 0.141 (4) | −0.250 (4) | 0.675 (2) | 0.065 (11)* | |
| H2W | 0.100 (4) | −0.360 (4) | 0.724 (3) | 0.084 (12)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0368 (3) | 0.0399 (4) | 0.0335 (3) | 0.0034 (2) | 0.0099 (2) | 0.0041 (2) |
| N1 | 0.0251 (9) | 0.0244 (10) | 0.0234 (9) | 0.0008 (7) | 0.0037 (7) | 0.0005 (7) |
| O1W | 0.0431 (12) | 0.0528 (15) | 0.1006 (19) | −0.0032 (11) | −0.0020 (12) | 0.0265 (13) |
| C21 | 0.0270 (11) | 0.0327 (13) | 0.0226 (11) | 0.0014 (9) | 0.0067 (8) | 0.0011 (9) |
| C31 | 0.0359 (12) | 0.0241 (12) | 0.0326 (12) | −0.0012 (9) | 0.0038 (9) | −0.0041 (9) |
| C13 | 0.0479 (14) | 0.0344 (14) | 0.0265 (12) | 0.0043 (11) | 0.0038 (10) | −0.0001 (10) |
| C41 | 0.0264 (11) | 0.0375 (14) | 0.0333 (13) | 0.0071 (10) | −0.0020 (9) | 0.0037 (10) |
| C11 | 0.0281 (11) | 0.0305 (13) | 0.0232 (11) | 0.0028 (9) | 0.0074 (8) | 0.0002 (9) |
| C12 | 0.0321 (11) | 0.0384 (14) | 0.0251 (12) | 0.0046 (10) | 0.0047 (9) | 0.0023 (10) |
| C22 | 0.0391 (12) | 0.0319 (14) | 0.0390 (14) | −0.0060 (10) | 0.0122 (10) | −0.0033 (10) |
| C23 | 0.0465 (14) | 0.0420 (16) | 0.0639 (18) | −0.0122 (12) | 0.0192 (13) | 0.0043 (13) |
| N1—C31 | 1.499 (3) | C13—H6C | 0.9800 |
| N1—C41 | 1.504 (3) | C41—H7A | 0.9800 |
| N1—C11 | 1.512 (3) | C41—H7B | 0.9800 |
| N1—C21 | 1.515 (3) | C41—H7C | 0.9800 |
| O1W—H1W | 0.79 (4) | C11—C12 | 1.514 (3) |
| O1W—H2W | 0.84 (4) | C11—H8A | 0.9900 |
| C21—C22 | 1.512 (3) | C11—H8B | 0.9900 |
| C21—H4A | 0.9900 | C12—H9A | 0.9900 |
| C21—H4B | 0.9900 | C12—H9B | 0.9900 |
| C31—H5A | 0.9800 | C22—C23 | 1.516 (3) |
| C31—H5B | 0.9800 | C22—H10A | 0.9900 |
| C31—H5C | 0.9800 | C22—H10B | 0.9900 |
| C13—C12 | 1.514 (3) | C23—H11A | 0.9800 |
| C13—H6A | 0.9800 | C23—H11B | 0.9800 |
| C13—H6B | 0.9800 | C23—H11C | 0.9800 |
| C31—N1—C41 | 107.48 (16) | N1—C41—H7C | 109.5 |
| C31—N1—C11 | 110.50 (16) | H7A—C41—H7C | 109.5 |
| C41—N1—C11 | 107.79 (16) | H7B—C41—H7C | 109.5 |
| C31—N1—C21 | 107.86 (15) | N1—C11—C12 | 115.50 (16) |
| C41—N1—C21 | 109.83 (16) | N1—C11—H8A | 108.4 |
| C11—N1—C21 | 113.22 (15) | C12—C11—H8A | 108.4 |
| H1W—O1W—H2W | 110 (3) | N1—C11—H8B | 108.4 |
| C22—C21—N1 | 115.22 (17) | C12—C11—H8B | 108.4 |
| C22—C21—H4A | 108.5 | H8A—C11—H8B | 107.5 |
| N1—C21—H4A | 108.5 | C13—C12—C11 | 108.70 (18) |
| C22—C21—H4B | 108.5 | C13—C12—H9A | 109.9 |
| N1—C21—H4B | 108.5 | C11—C12—H9A | 109.9 |
| H4A—C21—H4B | 107.5 | C13—C12—H9B | 109.9 |
| N1—C31—H5A | 109.5 | C11—C12—H9B | 109.9 |
| N1—C31—H5B | 109.5 | H9A—C12—H9B | 108.3 |
| H5A—C31—H5B | 109.5 | C21—C22—C23 | 110.3 (2) |
| N1—C31—H5C | 109.5 | C21—C22—H10A | 109.6 |
| H5A—C31—H5C | 109.5 | C23—C22—H10A | 109.6 |
| H5B—C31—H5C | 109.5 | C21—C22—H10B | 109.6 |
| C12—C13—H6A | 109.5 | C23—C22—H10B | 109.6 |
| C12—C13—H6B | 109.5 | H10A—C22—H10B | 108.1 |
| H6A—C13—H6B | 109.5 | C22—C23—H11A | 109.5 |
| C12—C13—H6C | 109.5 | C22—C23—H11B | 109.5 |
| H6A—C13—H6C | 109.5 | H11A—C23—H11B | 109.5 |
| H6B—C13—H6C | 109.5 | C22—C23—H11C | 109.5 |
| N1—C41—H7A | 109.5 | H11A—C23—H11C | 109.5 |
| N1—C41—H7B | 109.5 | H11B—C23—H11C | 109.5 |
| H7A—C41—H7B | 109.5 | ||
| C31—N1—C21—C22 | −178.85 (18) | C41—N1—C11—C12 | 177.38 (18) |
| C41—N1—C21—C22 | 64.3 (2) | C21—N1—C11—C12 | −60.9 (2) |
| C11—N1—C21—C22 | −56.3 (2) | N1—C11—C12—C13 | 177.40 (18) |
| C31—N1—C11—C12 | 60.2 (2) | N1—C21—C22—C23 | 179.42 (19) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W···Cl1 | 0.79 (4) | 2.47 (4) | 3.239 (3) | 164 (3) |
| O1Wi—H2Wi···Cl1 | 0.84 (4) | 2.46 (4) | 3.285 (3) | 172 (4) |
| C31ii—H5Bii···O1W | 0.98 | 2.54 | 3.489 (4) | 162 |
| C21ii—H4Aii···Cl1 | 0.99 | 2.76 | 3.742 (2) | 172 |
| C41iii—H7Aiii···Cl1 | 0.98 | 2.80 | 3.721 (3) | 156 |
| C41—H7C···Cl1 | 0.98 | 2.76 | 3.691 (3) | 158 |
| Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x−1, y, z; (iii) −x+1, −y, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1W···Cl1 | 0.79 (4) | 2.47 (4) | 3.239 (3) | 164 (3) |
| O1Wi—H2Wi···Cl1 | 0.84 (4) | 2.46 (4) | 3.285 (3) | 172 (4) |
| C31ii—H5Bii···O1W | 0.98 | 2.54 | 3.489 (4) | 162 |
| C21ii—H4Aii···Cl1 | 0.99 | 2.76 | 3.742 (2) | 172 |
| C41iii—H7Aiii···Cl1 | 0.98 | 2.80 | 3.721 (3) | 156 |
| C41—H7C···Cl1 | 0.98 | 2.76 | 3.691 (3) | 158 |
| Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) x−1, y, z; (iii) −x+1, −y, −z+1. |
The authors thank the Inorganic Materials Chemistry Graduate Program for financial support.
Brandenburg, K. (2008). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Burla, M. C., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Polidori, G. & Spagna, R. (2003). J. Appl. Cryst. 36, 1103.
Busi, S., Lahtinen, M., Mansikkamäki, H., Valkonen, J. & Rissanen, K. (2005). J. Solid State Chem. 178, 1722–1737.
Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z., Borek, D., Majewski, W. & Minor, W. (2003). Acta Cryst. A59, 228–234.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
Ropponen, J., Lahtinen, M., Busi, S., Nissinen, M., Kolehmainen, E. & Rissanen, K. (2004). New J. Chem. 28, 1426–1430.
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
As a part of our ongoing study of small R2R'2N+ X--type quaternary ammonium halides (Ropponen et al., 2004; Busi et al., 2005) the title compound (Fig. 1) has been synthesized and its crystal structure is reported here.
The asymmetric unit consists of one cation and one anion with one water molecule. The intermolecular (O)H···Cl distances vary from 2.456 (41) to 2.477 (40) Å. The shortest intermolecular (C)H···Cl distance is 2.779 (1) Å and the shortest (C)H···O distance is 2.561 (3) Å. The packing is affected by these weak intermolecular bonds (Table 1) causing the cations to arrange in layers which are separated by anions and the water molecules. The anions and the water molecules form a hydrogen-bonded chain along the crystallographic b-axis.