Acta Cryst. (2008). E64, o1763 [ doi:10.1107/S1600536808025300 ]
In the title compound, C13H28N22+·SO42-·H2O, extensive hydrogen-bonding interactions between the protonated 4,4'-(propane-1,3-diyl)dipiperidinium ions, the sulfate anions and the water molecules lead to a three-dimensional pillared and layered structure with the 4,4'-(propane-1,3-diyl)dipiperidinium ions acting as the pillars.
A solution of 4,4-trimethylenedipiperidine (1 mmol), sulfuric acid (1 mmol) and H2O (10 ml) was slowly evaporated at room temperature, giving colorless single crystals suitable for X-ray analysis.
The H atoms bonded to C and O atoms were placed at calculated positions, and refined with isotropic displacement parameters, using a riding model [C—H 0.93Å and Uiso(H) = 1.2Ueq(C); O—H 0.85Å and Uiso(H) = 1.5Ueq(C)]. The H atoms bonded to N atoms were refined freely.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Bergerhoff et al., 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./fj2138fig1thm.gif)
| Fig. 1. A view of the title compound, showing 30% probability displacement ellipsoids. |
![[Figure 2]](./fj2138fig2thm.gif)
| Fig. 2. The three-dimensional structure of the title compound, showing the hydrogen bonding interactions (dashed lines). |
| C13H28N22+·S1O42–·H2O | F000 = 712 |
| Mr = 326.45 | Dx = 1.315 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 99 reflections |
| a = 6.2019 (2) Å | θ = 2.0–25.1º |
| b = 22.5110 (5) Å | µ = 0.22 mm−1 |
| c = 12.0052 (3) Å | T = 293 (2) K |
| β = 100.439 (2)º | Prism, colorless |
| V = 1648.32 (8) Å3 | 0.22 × 0.14 × 0.09 mm |
| Z = 4 |
| Siemens SMART 1K CCD area-detector diffractometer | 2932 independent reflections |
| Radiation source: fine-focus sealed tube | 2011 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.066 |
| T = 293(2) K | θmax = 25.1º |
| φ and ω scans | θmin = 2.0º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→7 |
| Tmin = 0.927, Tmax = 0.98 | k = −26→26 |
| 13022 measured reflections | l = −13→14 |
| 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)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.131 | w = 1/[σ2(Fo2) + (0.0635P)2 + 0.5599P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.03 | (Δ/σ)max < 0.001 |
| 2932 reflections | Δρmax = 0.34 e Å−3 |
| 202 parameters | Δρmin = −0.39 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C13H28N22+·S1O42–·H2O | V = 1648.32 (8) Å3 |
| Mr = 326.45 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 6.2019 (2) Å | µ = 0.22 mm−1 |
| b = 22.5110 (5) Å | T = 293 (2) K |
| c = 12.0052 (3) Å | 0.22 × 0.14 × 0.09 mm |
| β = 100.439 (2)º |
| Siemens SMART 1K CCD area-detector diffractometer | 2932 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2011 reflections with I > 2σ(I) |
| Tmin = 0.927, Tmax = 0.98 | Rint = 0.066 |
| 13022 measured reflections |
| R[F2 > 2σ(F2)] = 0.048 | 202 parameters |
| wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.03 | Δρmax = 0.34 e Å−3 |
| 2932 reflections | Δρmin = −0.39 e Å−3 |
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 | ||
| S1 | 0.28582 (11) | 0.18642 (3) | 0.35885 (6) | 0.0255 (2) | |
| O1W | 0.7186 (3) | −0.20465 (10) | 0.15532 (19) | 0.0458 (6) | |
| H1WA | 0.6074 | −0.2274 | 0.1421 | 0.069* | |
| H1WB | 0.8181 | −0.2279 | 0.1410 | 0.069* | |
| O1 | 0.2335 (3) | 0.19986 (9) | 0.23718 (16) | 0.0346 (5) | |
| O2 | 0.2510 (4) | 0.12374 (10) | 0.38116 (19) | 0.0489 (6) | |
| O3 | 0.5164 (3) | 0.20349 (10) | 0.40084 (18) | 0.0431 (6) | |
| O4 | 0.1467 (3) | 0.22203 (10) | 0.42124 (19) | 0.0493 (7) | |
| N1 | 0.1395 (4) | −0.13893 (12) | 0.4911 (2) | 0.0310 (6) | |
| H1NA | 0.026 (5) | −0.1498 (14) | 0.529 (3) | 0.046* | |
| H1NB | 0.258 (6) | −0.1500 (14) | 0.533 (3) | 0.046* | |
| N2 | 0.8705 (4) | 0.19250 (11) | 0.0746 (2) | 0.0279 (6) | |
| H2NA | 0.986 (5) | 0.1962 (14) | 0.128 (3) | 0.042* | |
| H2NB | 0.851 (5) | 0.2258 (14) | 0.029 (3) | 0.042* | |
| C1 | 0.1335 (5) | −0.07379 (13) | 0.4752 (3) | 0.0328 (7) | |
| H1A | 0.1482 | −0.0545 | 0.5484 | 0.039* | |
| H1B | −0.0068 | −0.0624 | 0.4306 | 0.039* | |
| C2 | 0.3159 (5) | −0.05304 (13) | 0.4160 (2) | 0.0279 (7) | |
| H2A | 0.4555 | −0.0589 | 0.4661 | 0.033* | |
| H2B | 0.2987 | −0.0108 | 0.4007 | 0.033* | |
| C3 | 0.3192 (4) | −0.08591 (12) | 0.3044 (2) | 0.0249 (6) | |
| H3A | 0.1859 | −0.0756 | 0.2507 | 0.030* | |
| C4 | 0.3183 (5) | −0.15306 (12) | 0.3261 (2) | 0.0300 (7) | |
| H4A | 0.3080 | −0.1739 | 0.2546 | 0.036* | |
| H4B | 0.4554 | −0.1643 | 0.3739 | 0.036* | |
| C5 | 0.1292 (5) | −0.17174 (14) | 0.3825 (2) | 0.0351 (8) | |
| H5A | −0.0087 | −0.1634 | 0.3326 | 0.042* | |
| H5B | 0.1369 | −0.2141 | 0.3972 | 0.042* | |
| C6 | 0.5170 (5) | −0.06873 (12) | 0.2525 (2) | 0.0297 (7) | |
| H6A | 0.5259 | −0.0957 | 0.1905 | 0.036* | |
| H6B | 0.6483 | −0.0743 | 0.3092 | 0.036* | |
| C7 | 0.5158 (4) | −0.00503 (12) | 0.2080 (3) | 0.0296 (7) | |
| H7A | 0.3918 | −0.0001 | 0.1466 | 0.036* | |
| H7B | 0.4964 | 0.0222 | 0.2681 | 0.036* | |
| C8 | 0.7255 (5) | 0.01124 (13) | 0.1655 (3) | 0.0315 (7) | |
| H8A | 0.8465 | 0.0112 | 0.2293 | 0.038* | |
| H8B | 0.7549 | −0.0191 | 0.1129 | 0.038* | |
| C9 | 0.6696 (5) | 0.18163 (13) | 0.1245 (3) | 0.0298 (7) | |
| H9A | 0.5413 | 0.1820 | 0.0647 | 0.036* | |
| H9B | 0.6536 | 0.2132 | 0.1774 | 0.036* | |
| C10 | 0.6836 (4) | 0.12266 (12) | 0.1851 (2) | 0.0269 (7) | |
| H10A | 0.5494 | 0.1160 | 0.2141 | 0.032* | |
| H10B | 0.8042 | 0.1236 | 0.2491 | 0.032* | |
| C11 | 0.7181 (4) | 0.07147 (12) | 0.1069 (2) | 0.0264 (7) | |
| H11A | 0.5943 | 0.0712 | 0.0433 | 0.032* | |
| C12 | 0.9259 (5) | 0.08438 (13) | 0.0598 (3) | 0.0332 (7) | |
| H12A | 1.0508 | 0.0844 | 0.1215 | 0.040* | |
| H12B | 0.9479 | 0.0530 | 0.0076 | 0.040* | |
| C13 | 0.9149 (5) | 0.14331 (13) | −0.0008 (3) | 0.0346 (8) | |
| H13A | 1.0528 | 0.1506 | −0.0258 | 0.042* | |
| H13B | 0.7997 | 0.1420 | −0.0673 | 0.042* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0231 (4) | 0.0290 (4) | 0.0237 (4) | −0.0011 (3) | 0.0024 (3) | −0.0009 (3) |
| O1W | 0.0439 (13) | 0.0327 (13) | 0.0623 (16) | 0.0011 (10) | 0.0131 (12) | −0.0080 (11) |
| O1 | 0.0342 (11) | 0.0457 (14) | 0.0209 (12) | 0.0003 (9) | −0.0027 (9) | 0.0051 (9) |
| O2 | 0.0630 (16) | 0.0310 (14) | 0.0508 (16) | −0.0044 (11) | 0.0049 (12) | 0.0120 (11) |
| O3 | 0.0239 (11) | 0.0606 (15) | 0.0401 (14) | −0.0115 (10) | −0.0070 (10) | 0.0122 (11) |
| O4 | 0.0416 (13) | 0.0637 (17) | 0.0469 (15) | 0.0067 (12) | 0.0196 (11) | −0.0167 (12) |
| N1 | 0.0267 (13) | 0.0376 (16) | 0.0275 (16) | −0.0033 (11) | 0.0019 (12) | 0.0095 (12) |
| N2 | 0.0327 (14) | 0.0249 (15) | 0.0230 (14) | −0.0041 (11) | −0.0036 (11) | 0.0046 (11) |
| C1 | 0.0350 (16) | 0.0349 (19) | 0.0274 (17) | 0.0063 (14) | 0.0028 (13) | −0.0008 (14) |
| C2 | 0.0298 (15) | 0.0218 (16) | 0.0298 (17) | −0.0013 (12) | −0.0008 (13) | −0.0008 (13) |
| C3 | 0.0267 (14) | 0.0203 (15) | 0.0258 (16) | −0.0005 (12) | −0.0008 (12) | 0.0047 (12) |
| C4 | 0.0401 (17) | 0.0219 (17) | 0.0266 (17) | −0.0035 (13) | 0.0022 (14) | −0.0004 (13) |
| C5 | 0.0396 (18) | 0.0320 (18) | 0.0291 (18) | −0.0142 (14) | −0.0058 (14) | 0.0019 (14) |
| C6 | 0.0318 (16) | 0.0244 (17) | 0.0326 (18) | 0.0010 (12) | 0.0047 (13) | 0.0020 (13) |
| C7 | 0.0324 (15) | 0.0227 (16) | 0.0357 (18) | 0.0010 (12) | 0.0110 (13) | 0.0020 (13) |
| C8 | 0.0347 (16) | 0.0229 (17) | 0.0379 (19) | 0.0002 (13) | 0.0094 (14) | −0.0012 (13) |
| C9 | 0.0325 (16) | 0.0251 (17) | 0.0317 (18) | 0.0027 (12) | 0.0051 (13) | 0.0021 (13) |
| C10 | 0.0300 (15) | 0.0235 (17) | 0.0286 (17) | 0.0016 (12) | 0.0093 (13) | 0.0005 (13) |
| C11 | 0.0272 (15) | 0.0248 (17) | 0.0275 (17) | 0.0003 (12) | 0.0058 (13) | 0.0011 (12) |
| C12 | 0.0407 (17) | 0.0243 (17) | 0.0398 (19) | −0.0020 (13) | 0.0206 (15) | −0.0047 (14) |
| C13 | 0.0391 (17) | 0.0342 (19) | 0.0324 (19) | −0.0038 (14) | 0.0114 (15) | −0.0033 (14) |
| S1—O2 | 1.459 (2) | C4—H4B | 0.9700 |
| S1—O1 | 1.469 (2) | C5—H5A | 0.9700 |
| S1—O4 | 1.477 (2) | C5—H5B | 0.9700 |
| S1—O3 | 1.478 (2) | C6—C7 | 1.530 (4) |
| O1W—H1WA | 0.8501 | C6—H6A | 0.9700 |
| O1W—H1WB | 0.8500 | C6—H6B | 0.9700 |
| N1—C1 | 1.478 (4) | C7—C8 | 1.525 (4) |
| N1—C5 | 1.489 (4) | C7—H7A | 0.9700 |
| N1—H1NA | 0.94 (3) | C7—H7B | 0.9700 |
| N1—H1NB | 0.85 (3) | C8—C11 | 1.524 (4) |
| N2—C13 | 1.488 (4) | C8—H8A | 0.9700 |
| N2—C9 | 1.497 (4) | C8—H8B | 0.9700 |
| N2—H2NA | 0.88 (3) | C9—C10 | 1.509 (4) |
| N2—H2NB | 0.92 (3) | C9—H9A | 0.9700 |
| C1—C2 | 1.515 (4) | C9—H9B | 0.9700 |
| C1—H1A | 0.9700 | C10—C11 | 1.526 (4) |
| C1—H1B | 0.9700 | C10—H10A | 0.9700 |
| C2—C3 | 1.534 (4) | C10—H10B | 0.9700 |
| C2—H2A | 0.9700 | C11—C12 | 1.527 (4) |
| C2—H2B | 0.9700 | C11—H11A | 0.9800 |
| C3—C6 | 1.523 (4) | C12—C13 | 1.509 (4) |
| C3—C4 | 1.534 (4) | C12—H12A | 0.9700 |
| C3—H3A | 0.9800 | C12—H12B | 0.9700 |
| C4—C5 | 1.516 (4) | C13—H13A | 0.9700 |
| C4—H4A | 0.9700 | C13—H13B | 0.9700 |
| O2—S1—O1 | 111.60 (13) | C3—C6—C7 | 115.3 (2) |
| O2—S1—O4 | 108.18 (14) | C3—C6—H6A | 108.4 |
| O1—S1—O4 | 110.38 (13) | C7—C6—H6A | 108.4 |
| O2—S1—O3 | 110.79 (13) | C3—C6—H6B | 108.4 |
| O1—S1—O3 | 108.13 (12) | C7—C6—H6B | 108.4 |
| O4—S1—O3 | 107.69 (14) | H6A—C6—H6B | 107.5 |
| H1WA—O1W—H1WB | 100.7 | C8—C7—C6 | 113.0 (2) |
| C1—N1—C5 | 112.5 (2) | C8—C7—H7A | 109.0 |
| C1—N1—H1NA | 108.6 (19) | C6—C7—H7A | 109.0 |
| C5—N1—H1NA | 112.1 (19) | C8—C7—H7B | 109.0 |
| C1—N1—H1NB | 111 (2) | C6—C7—H7B | 109.0 |
| C5—N1—H1NB | 106 (2) | H7A—C7—H7B | 107.8 |
| H1NA—N1—H1NB | 107 (3) | C11—C8—C7 | 114.3 (2) |
| C13—N2—C9 | 112.4 (2) | C11—C8—H8A | 108.7 |
| C13—N2—H2NA | 108 (2) | C7—C8—H8A | 108.7 |
| C9—N2—H2NA | 110 (2) | C11—C8—H8B | 108.7 |
| C13—N2—H2NB | 105.2 (19) | C7—C8—H8B | 108.7 |
| C9—N2—H2NB | 109.9 (19) | H8A—C8—H8B | 107.6 |
| H2NA—N2—H2NB | 111 (3) | N2—C9—C10 | 110.9 (2) |
| N1—C1—C2 | 111.3 (2) | N2—C9—H9A | 109.4 |
| N1—C1—H1A | 109.4 | C10—C9—H9A | 109.4 |
| C2—C1—H1A | 109.4 | N2—C9—H9B | 109.4 |
| N1—C1—H1B | 109.4 | C10—C9—H9B | 109.4 |
| C2—C1—H1B | 109.4 | H9A—C9—H9B | 108.0 |
| H1A—C1—H1B | 108.0 | C9—C10—C11 | 111.7 (2) |
| C1—C2—C3 | 113.0 (2) | C9—C10—H10A | 109.3 |
| C1—C2—H2A | 109.0 | C11—C10—H10A | 109.3 |
| C3—C2—H2A | 109.0 | C9—C10—H10B | 109.3 |
| C1—C2—H2B | 109.0 | C11—C10—H10B | 109.3 |
| C3—C2—H2B | 109.0 | H10A—C10—H10B | 107.9 |
| H2A—C2—H2B | 107.8 | C8—C11—C10 | 112.6 (2) |
| C6—C3—C2 | 112.0 (2) | C8—C11—C12 | 112.5 (2) |
| C6—C3—C4 | 110.4 (2) | C10—C11—C12 | 107.8 (2) |
| C2—C3—C4 | 109.0 (2) | C8—C11—H11A | 107.9 |
| C6—C3—H3A | 108.5 | C10—C11—H11A | 107.9 |
| C2—C3—H3A | 108.5 | C12—C11—H11A | 107.9 |
| C4—C3—H3A | 108.5 | C13—C12—C11 | 112.3 (2) |
| C5—C4—C3 | 112.1 (2) | C13—C12—H12A | 109.2 |
| C5—C4—H4A | 109.2 | C11—C12—H12A | 109.2 |
| C3—C4—H4A | 109.2 | C13—C12—H12B | 109.2 |
| C5—C4—H4B | 109.2 | C11—C12—H12B | 109.2 |
| C3—C4—H4B | 109.2 | H12A—C12—H12B | 107.9 |
| H4A—C4—H4B | 107.9 | N2—C13—C12 | 111.0 (2) |
| N1—C5—C4 | 109.9 (2) | N2—C13—H13A | 109.4 |
| N1—C5—H5A | 109.7 | C12—C13—H13A | 109.4 |
| C4—C5—H5A | 109.7 | N2—C13—H13B | 109.4 |
| N1—C5—H5B | 109.7 | C12—C13—H13B | 109.4 |
| C4—C5—H5B | 109.7 | H13A—C13—H13B | 108.0 |
| H5A—C5—H5B | 108.2 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1WA···O4i | 0.85 | 1.98 | 2.819 (3) | 168 |
| O1W—H1WB···O3ii | 0.85 | 1.97 | 2.799 (3) | 165 |
| N1—H1NA···O4iii | 0.94 (3) | 2.09 (3) | 2.904 (3) | 144 (3) |
| N1—H1NB···O3iv | 0.85 (3) | 1.91 (3) | 2.711 (3) | 157 (3) |
| N2—H2NA···O1v | 0.88 (3) | 1.83 (3) | 2.704 (3) | 177 (3) |
| N2—H2NB···O4vi | 0.92 (3) | 2.02 (3) | 2.845 (4) | 149 (3) |
| Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x, −y, −z+1; (iv) −x+1, −y, −z+1; (v) x+1, y, z; (vi) x+1/2, −y+1/2, z−1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H1WA···O4i | 0.85 | 1.98 | 2.819 (3) | 168 |
| O1W—H1WB···O3ii | 0.85 | 1.97 | 2.799 (3) | 165 |
| N1—H1NA···O4iii | 0.94 (3) | 2.09 (3) | 2.904 (3) | 144 (3) |
| N1—H1NB···O3iv | 0.85 (3) | 1.91 (3) | 2.711 (3) | 157 (3) |
| N2—H2NA···O1v | 0.88 (3) | 1.83 (3) | 2.704 (3) | 177 (3) |
| N2—H2NB···O4vi | 0.92 (3) | 2.02 (3) | 2.845 (4) | 149 (3) |
| Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x, −y, −z+1; (iv) −x+1, −y, −z+1; (v) x+1, y, z; (vi) x+1/2, −y+1/2, z−1/2. |
The authors acknowledge the financial support from Natural Science Foundation of Fujian Province (2006 F3042).
Bergerhoff, G., Berndt, M. & Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
The asymmetric unit of the title compound, (I), consists of one protonated 4,4'-(propane-1,3-diyl)dipiperidinium ion, one deprotonated sulfate anion and one water molecule (Figure 1). Both protonated N ends of the 4,4'-(propane-1,3-diyl)dipiperidinium ion form N—H···O hydrogen bonds with the sulfate anion, as well as the water molecules form O—H···O hydrogen bonds with the sulfate anion, which leads to the formation of two-dimensional hydrogen-bonding layer parallel to the ac plane (Table 1 & Figure 2). The resulting layers are further pillared by the 4,4'-(propane-1,3-diyl)dipiperidinium ions to complete the three-dimensional structure.