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Acta Crystallogr Sect E Struct Rep Online. 2008 September 1; 64(Pt 9): o1763.
Published online 2008 August 16. doi:  10.1107/S1600536808025300
PMCID: PMC2960564

4,4′-(Propane-1,3-di­yl)dipiperidinium sulfate monohydrate

Abstract

In the title compound, C13H28N2 2+·SO4 2−·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.

An external file that holds a picture, illustration, etc.
Object name is e-64-o1763-scheme1.jpg

Experimental

Crystal data

  • C13H28N2 2+·SO4 2−·H2O
  • M r = 326.45
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1763-efi1.jpg
  • a = 6.2019 (2) Å
  • b = 22.5110 (5) Å
  • c = 12.0052 (3) Å
  • β = 100.439 (2)°
  • V = 1648.32 (8) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.22 mm−1
  • T = 293 (2) K
  • 0.22 × 0.14 × 0.09 mm

Data collection

  • Siemens SMART 1K CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.927, T max = 0.98
  • 13022 measured reflections
  • 2932 independent reflections
  • 2011 reflections with I > 2σ(I)
  • R int = 0.066

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.131
  • S = 1.03
  • 2932 reflections
  • 202 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.34 e Å−3
  • Δρmin = −0.40 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Bergerhoff et al., 1999 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808025300/fj2138sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025300/fj2138Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge financial support from the Natural Science Foundation of Fujian Province (2006 F3042).

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

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.

Figures

Fig. 1.
A view of the title compound, showing 30% probability displacement ellipsoids.
Fig. 2.
The three-dimensional structure of the title compound, showing the hydrogen bonding interactions (dashed lines).

Crystal data

C13H28N22+·S1O42–·H2OF000 = 712
Mr = 326.45Dx = 1.315 Mg m3
Monoclinic, P21/nMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 99 reflections
a = 6.2019 (2) Åθ = 2.0–25.1º
b = 22.5110 (5) ŵ = 0.22 mm1
c = 12.0052 (3) ÅT = 293 (2) K
β = 100.439 (2)ºPrism, colorless
V = 1648.32 (8) Å30.22 × 0.14 × 0.09 mm
Z = 4

Data collection

Siemens SMART 1K CCD area-detector diffractometer2932 independent reflections
Radiation source: fine-focus sealed tube2011 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.066
T = 293(2) Kθmax = 25.1º
[var phi] and ω scansθmin = 2.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −7→7
Tmin = 0.927, Tmax = 0.98k = −26→26
13022 measured reflectionsl = −13→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.048H 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 reflectionsΔρmax = 0.34 e Å3
202 parametersΔρmin = −0.39 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

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)

xyzUiso*/Ueq
S10.28582 (11)0.18642 (3)0.35885 (6)0.0255 (2)
O1W0.7186 (3)−0.20465 (10)0.15532 (19)0.0458 (6)
H1WA0.6074−0.22740.14210.069*
H1WB0.8181−0.22790.14100.069*
O10.2335 (3)0.19986 (9)0.23718 (16)0.0346 (5)
O20.2510 (4)0.12374 (10)0.38116 (19)0.0489 (6)
O30.5164 (3)0.20349 (10)0.40084 (18)0.0431 (6)
O40.1467 (3)0.22203 (10)0.42124 (19)0.0493 (7)
N10.1395 (4)−0.13893 (12)0.4911 (2)0.0310 (6)
H1NA0.026 (5)−0.1498 (14)0.529 (3)0.046*
H1NB0.258 (6)−0.1500 (14)0.533 (3)0.046*
N20.8705 (4)0.19250 (11)0.0746 (2)0.0279 (6)
H2NA0.986 (5)0.1962 (14)0.128 (3)0.042*
H2NB0.851 (5)0.2258 (14)0.029 (3)0.042*
C10.1335 (5)−0.07379 (13)0.4752 (3)0.0328 (7)
H1A0.1482−0.05450.54840.039*
H1B−0.0068−0.06240.43060.039*
C20.3159 (5)−0.05304 (13)0.4160 (2)0.0279 (7)
H2A0.4555−0.05890.46610.033*
H2B0.2987−0.01080.40070.033*
C30.3192 (4)−0.08591 (12)0.3044 (2)0.0249 (6)
H3A0.1859−0.07560.25070.030*
C40.3183 (5)−0.15306 (12)0.3261 (2)0.0300 (7)
H4A0.3080−0.17390.25460.036*
H4B0.4554−0.16430.37390.036*
C50.1292 (5)−0.17174 (14)0.3825 (2)0.0351 (8)
H5A−0.0087−0.16340.33260.042*
H5B0.1369−0.21410.39720.042*
C60.5170 (5)−0.06873 (12)0.2525 (2)0.0297 (7)
H6A0.5259−0.09570.19050.036*
H6B0.6483−0.07430.30920.036*
C70.5158 (4)−0.00503 (12)0.2080 (3)0.0296 (7)
H7A0.3918−0.00010.14660.036*
H7B0.49640.02220.26810.036*
C80.7255 (5)0.01124 (13)0.1655 (3)0.0315 (7)
H8A0.84650.01120.22930.038*
H8B0.7549−0.01910.11290.038*
C90.6696 (5)0.18163 (13)0.1245 (3)0.0298 (7)
H9A0.54130.18200.06470.036*
H9B0.65360.21320.17740.036*
C100.6836 (4)0.12266 (12)0.1851 (2)0.0269 (7)
H10A0.54940.11600.21410.032*
H10B0.80420.12360.24910.032*
C110.7181 (4)0.07147 (12)0.1069 (2)0.0264 (7)
H11A0.59430.07120.04330.032*
C120.9259 (5)0.08438 (13)0.0598 (3)0.0332 (7)
H12A1.05080.08440.12150.040*
H12B0.94790.05300.00760.040*
C130.9149 (5)0.14331 (13)−0.0008 (3)0.0346 (8)
H13A1.05280.1506−0.02580.042*
H13B0.79970.1420−0.06730.042*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0231 (4)0.0290 (4)0.0237 (4)−0.0011 (3)0.0024 (3)−0.0009 (3)
O1W0.0439 (13)0.0327 (13)0.0623 (16)0.0011 (10)0.0131 (12)−0.0080 (11)
O10.0342 (11)0.0457 (14)0.0209 (12)0.0003 (9)−0.0027 (9)0.0051 (9)
O20.0630 (16)0.0310 (14)0.0508 (16)−0.0044 (11)0.0049 (12)0.0120 (11)
O30.0239 (11)0.0606 (15)0.0401 (14)−0.0115 (10)−0.0070 (10)0.0122 (11)
O40.0416 (13)0.0637 (17)0.0469 (15)0.0067 (12)0.0196 (11)−0.0167 (12)
N10.0267 (13)0.0376 (16)0.0275 (16)−0.0033 (11)0.0019 (12)0.0095 (12)
N20.0327 (14)0.0249 (15)0.0230 (14)−0.0041 (11)−0.0036 (11)0.0046 (11)
C10.0350 (16)0.0349 (19)0.0274 (17)0.0063 (14)0.0028 (13)−0.0008 (14)
C20.0298 (15)0.0218 (16)0.0298 (17)−0.0013 (12)−0.0008 (13)−0.0008 (13)
C30.0267 (14)0.0203 (15)0.0258 (16)−0.0005 (12)−0.0008 (12)0.0047 (12)
C40.0401 (17)0.0219 (17)0.0266 (17)−0.0035 (13)0.0022 (14)−0.0004 (13)
C50.0396 (18)0.0320 (18)0.0291 (18)−0.0142 (14)−0.0058 (14)0.0019 (14)
C60.0318 (16)0.0244 (17)0.0326 (18)0.0010 (12)0.0047 (13)0.0020 (13)
C70.0324 (15)0.0227 (16)0.0357 (18)0.0010 (12)0.0110 (13)0.0020 (13)
C80.0347 (16)0.0229 (17)0.0379 (19)0.0002 (13)0.0094 (14)−0.0012 (13)
C90.0325 (16)0.0251 (17)0.0317 (18)0.0027 (12)0.0051 (13)0.0021 (13)
C100.0300 (15)0.0235 (17)0.0286 (17)0.0016 (12)0.0093 (13)0.0005 (13)
C110.0272 (15)0.0248 (17)0.0275 (17)0.0003 (12)0.0058 (13)0.0011 (12)
C120.0407 (17)0.0243 (17)0.0398 (19)−0.0020 (13)0.0206 (15)−0.0047 (14)
C130.0391 (17)0.0342 (19)0.0324 (19)−0.0038 (14)0.0114 (15)−0.0033 (14)

Geometric parameters (Å, °)

S1—O21.459 (2)C4—H4B0.9700
S1—O11.469 (2)C5—H5A0.9700
S1—O41.477 (2)C5—H5B0.9700
S1—O31.478 (2)C6—C71.530 (4)
O1W—H1WA0.8501C6—H6A0.9700
O1W—H1WB0.8500C6—H6B0.9700
N1—C11.478 (4)C7—C81.525 (4)
N1—C51.489 (4)C7—H7A0.9700
N1—H1NA0.94 (3)C7—H7B0.9700
N1—H1NB0.85 (3)C8—C111.524 (4)
N2—C131.488 (4)C8—H8A0.9700
N2—C91.497 (4)C8—H8B0.9700
N2—H2NA0.88 (3)C9—C101.509 (4)
N2—H2NB0.92 (3)C9—H9A0.9700
C1—C21.515 (4)C9—H9B0.9700
C1—H1A0.9700C10—C111.526 (4)
C1—H1B0.9700C10—H10A0.9700
C2—C31.534 (4)C10—H10B0.9700
C2—H2A0.9700C11—C121.527 (4)
C2—H2B0.9700C11—H11A0.9800
C3—C61.523 (4)C12—C131.509 (4)
C3—C41.534 (4)C12—H12A0.9700
C3—H3A0.9800C12—H12B0.9700
C4—C51.516 (4)C13—H13A0.9700
C4—H4A0.9700C13—H13B0.9700
O2—S1—O1111.60 (13)C3—C6—C7115.3 (2)
O2—S1—O4108.18 (14)C3—C6—H6A108.4
O1—S1—O4110.38 (13)C7—C6—H6A108.4
O2—S1—O3110.79 (13)C3—C6—H6B108.4
O1—S1—O3108.13 (12)C7—C6—H6B108.4
O4—S1—O3107.69 (14)H6A—C6—H6B107.5
H1WA—O1W—H1WB100.7C8—C7—C6113.0 (2)
C1—N1—C5112.5 (2)C8—C7—H7A109.0
C1—N1—H1NA108.6 (19)C6—C7—H7A109.0
C5—N1—H1NA112.1 (19)C8—C7—H7B109.0
C1—N1—H1NB111 (2)C6—C7—H7B109.0
C5—N1—H1NB106 (2)H7A—C7—H7B107.8
H1NA—N1—H1NB107 (3)C11—C8—C7114.3 (2)
C13—N2—C9112.4 (2)C11—C8—H8A108.7
C13—N2—H2NA108 (2)C7—C8—H8A108.7
C9—N2—H2NA110 (2)C11—C8—H8B108.7
C13—N2—H2NB105.2 (19)C7—C8—H8B108.7
C9—N2—H2NB109.9 (19)H8A—C8—H8B107.6
H2NA—N2—H2NB111 (3)N2—C9—C10110.9 (2)
N1—C1—C2111.3 (2)N2—C9—H9A109.4
N1—C1—H1A109.4C10—C9—H9A109.4
C2—C1—H1A109.4N2—C9—H9B109.4
N1—C1—H1B109.4C10—C9—H9B109.4
C2—C1—H1B109.4H9A—C9—H9B108.0
H1A—C1—H1B108.0C9—C10—C11111.7 (2)
C1—C2—C3113.0 (2)C9—C10—H10A109.3
C1—C2—H2A109.0C11—C10—H10A109.3
C3—C2—H2A109.0C9—C10—H10B109.3
C1—C2—H2B109.0C11—C10—H10B109.3
C3—C2—H2B109.0H10A—C10—H10B107.9
H2A—C2—H2B107.8C8—C11—C10112.6 (2)
C6—C3—C2112.0 (2)C8—C11—C12112.5 (2)
C6—C3—C4110.4 (2)C10—C11—C12107.8 (2)
C2—C3—C4109.0 (2)C8—C11—H11A107.9
C6—C3—H3A108.5C10—C11—H11A107.9
C2—C3—H3A108.5C12—C11—H11A107.9
C4—C3—H3A108.5C13—C12—C11112.3 (2)
C5—C4—C3112.1 (2)C13—C12—H12A109.2
C5—C4—H4A109.2C11—C12—H12A109.2
C3—C4—H4A109.2C13—C12—H12B109.2
C5—C4—H4B109.2C11—C12—H12B109.2
C3—C4—H4B109.2H12A—C12—H12B107.9
H4A—C4—H4B107.9N2—C13—C12111.0 (2)
N1—C5—C4109.9 (2)N2—C13—H13A109.4
N1—C5—H5A109.7C12—C13—H13A109.4
C4—C5—H5A109.7N2—C13—H13B109.4
N1—C5—H5B109.7C12—C13—H13B109.4
C4—C5—H5B109.7H13A—C13—H13B108.0
H5A—C5—H5B108.2

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O4i0.851.982.819 (3)168
O1W—H1WB···O3ii0.851.972.799 (3)165
N1—H1NA···O4iii0.94 (3)2.09 (3)2.904 (3)144 (3)
N1—H1NB···O3iv0.85 (3)1.91 (3)2.711 (3)157 (3)
N2—H2NA···O1v0.88 (3)1.83 (3)2.704 (3)177 (3)
N2—H2NB···O4vi0.92 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2138).

References

  • 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. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

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