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Acta Cryst. (2008). E64, o1085    [ doi:10.1107/S1600536808014256 ]

Piperidinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate

Z. Li, B. Cheng and S. Kunmei

Abstract top

The asymmetric unit of the title compound, C5H12N+·C7H5O6S-·H2O, contains a piperidinium cation, one 3-carboxy-4-hydroxybenzenesulfonate anion and one water molecule. Intermolecular O-H...O, O-H...S and N-H...O hydrogen bonds generate a three-dimensional hydrogen-bonded framework.

Comment top

5-Sulfosalicylic acid (SSA) has six potential donor sites in the three substituent groups (the sulfonic acid, the carboxylic acid and the phenolic groups), and it gives mono-, di- and trianionic ligand species through deprotonation. The presence of numerous oxygen atoms in the substituent groups usually results in hydrogen-bonding associations, and the self-assembly process of crystallization often requires the incorporation of water molecules in the structures (Smith et al. 2007). We report here the crystal structure of the title compound.

The asymmetric unit of the title compound contains one piperidium cation cation, one 3-carboxyl-4-hydroxyl-benzenesulfonate anion and one water molecule (Fig. 1). The bond distances and angles in the cationic and anionic species are normal. An intramolecular O6—H6···O5 hydrogen bond is observed. The molecular packing (Fig. 2) is stabilized by intermolecular O—H···O, O—H···S and N—H···O hydrogen bonds (Table 1), These interactions generate a three-dimensional hydrogen-bonded framework structure.

Related literature top

For related literature, see: Smith et al. (2007).

Experimental top

2-Hydroxy-5-sulfobenzoic acid (2.18 g, 10 mmol), piperidine (0.85 g, 10 mmol) and H2O (20 ml) were loaded into a 50 ml roundbottom flask, and heated to dissolve the solid. Crystals of the title compound were obtained by slow evaporation of deionic H2O solution.

Refinement top

The H atoms of the water molecule, and the N-bound H atom H atom were located in a difference Fourier map, and refined with the O—H and N—H distance restraints of 0.86 (1) and 0.90 (1) Å, respectively. All other H atoms were positioned geometrically [O—H = 0.82 Å (hydroxyl), C—H = 0.93 Å (aromatic) and 0.96 Å (methyl)] and refined using a riding model, with Uiso(H) = 1.5Ueq(carrier) for hydroxyl and methyl H atoms and 1.2Ueq(C) for other H atoms.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The asymmteric unit of title compound. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. Part of the crystal packing of the title compound. O—H···O and N—H···O hydrogen bonds are shown as dashed lines.
Piperidinium 3-carboxy-4-hydroxybenzenesulfonate monohydrate top
Crystal data top
C5H12N+·C7H5O6S–·H2OF000 = 680
Mr = 321.34Dx = 1.447 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2608 reflections
a = 6.8895 (14) Åθ = 3.0–25.1º
b = 13.202 (3) ŵ = 0.25 mm−1
c = 16.255 (3) ÅT = 294 (2) K
β = 93.739 (3)ºStick, colourless
V = 1475.3 (5) Å30.24 × 0.20 × 0.16 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		2602 independent reflections
Radiation source: fine-focus sealed tube1966 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.031
T = 294(2) Kθmax = 25.0º
φ and ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.942, Tmax = 0.961k = −15→15
7480 measured reflectionsl = −19→10
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.091  w = 1/[σ2(Fo2) + (0.0392P)2 + 0.5098P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2602 reflectionsΔρmax = 0.26 e Å−3
209 parametersΔρmin = −0.28 e Å−3
3 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0191 (15)
Crystal data top
C5H12N+·C7H5O6S–·H2OV = 1475.3 (5) Å3
Mr = 321.34Z = 4
Monoclinic, P21/nMo Kα
a = 6.8895 (14) ŵ = 0.25 mm−1
b = 13.202 (3) ÅT = 294 (2) K
c = 16.255 (3) Å0.24 × 0.20 × 0.16 mm
β = 93.739 (3)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2602 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1966 reflections with I > 2σ(I)
Tmin = 0.942, Tmax = 0.961Rint = 0.031
7480 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0353 restraints
wR(F2) = 0.091H atoms treated by a mixture of
independent and constrained refinement
S = 1.04Δρmax = 0.26 e Å−3
2602 reflectionsΔρmin = −0.28 e Å−3
209 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
xyzUiso*/Ueq
S10.16322 (7)0.89594 (4)0.24082 (3)0.03289 (18)
O10.3120 (2)0.93486 (13)0.19039 (9)0.0516 (4)
O2−0.0297 (2)0.93311 (11)0.21241 (10)0.0483 (4)
O30.1658 (2)0.78755 (11)0.25065 (9)0.0479 (4)
O40.1660 (2)0.78250 (12)0.55005 (9)0.0464 (4)
H40.160 (4)0.752 (2)0.5956 (17)0.070*
O50.2197 (2)0.91602 (11)0.63192 (9)0.0462 (4)
O60.2977 (2)1.08950 (12)0.56636 (10)0.0487 (4)
H60.279 (4)1.044 (2)0.6018 (17)0.073*
N10.1423 (3)0.86332 (17)0.80518 (12)0.0481 (5)
H1A0.100 (3)0.928 (2)0.7936 (15)0.058*
H1B0.124 (4)0.8238 (18)0.7615 (16)0.058*
C10.2116 (3)0.95050 (14)0.33929 (12)0.0294 (4)
C20.1907 (3)0.89450 (15)0.40946 (12)0.0296 (4)
H20.15650.82650.40500.036*
C30.2204 (3)0.93869 (15)0.48727 (12)0.0310 (5)
C40.2711 (3)1.04151 (15)0.49318 (13)0.0349 (5)
C50.2947 (3)1.09718 (16)0.42200 (14)0.0387 (5)
H50.33021.16510.42580.046*
C60.2656 (3)1.05223 (15)0.34626 (13)0.0365 (5)
H6A0.28191.08990.29890.044*
C70.2020 (3)0.87879 (16)0.56285 (13)0.0345 (5)
C80.0182 (4)0.81764 (19)0.86596 (17)0.0630 (8)
H8A0.05100.74660.87320.076*
H8B−0.11720.82210.84580.076*
C90.0467 (4)0.8713 (2)0.94665 (16)0.0691 (8)
H9A−0.02990.83810.98680.083*
H9B0.00080.94050.94030.083*
C100.2573 (4)0.8719 (2)0.97778 (15)0.0629 (7)
H10A0.27220.91051.02860.075*
H10B0.30020.80310.98950.075*
C110.3795 (4)0.9178 (2)0.91490 (17)0.0648 (8)
H11A0.34610.98880.90810.078*
H11B0.51540.91360.93430.078*
C120.3510 (4)0.8657 (3)0.83399 (17)0.0726 (9)
H12A0.42420.90080.79370.087*
H12B0.40020.79700.83900.087*
O70.6418 (2)0.81286 (11)0.18899 (10)0.0456 (4)
H7A0.7460 (19)0.8483 (15)0.1972 (16)0.068*
H7B0.5375 (18)0.8480 (15)0.1880 (17)0.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0357 (3)0.0317 (3)0.0308 (3)0.0030 (2)−0.0010 (2)0.0020 (2)
O10.0537 (10)0.0640 (11)0.0382 (9)−0.0077 (8)0.0121 (7)0.0017 (8)
O20.0434 (9)0.0428 (9)0.0561 (10)0.0062 (7)−0.0162 (7)−0.0029 (7)
O30.0720 (11)0.0301 (8)0.0405 (9)0.0082 (7)−0.0032 (8)−0.0010 (7)
O40.0677 (11)0.0385 (9)0.0334 (9)−0.0039 (8)0.0054 (8)0.0020 (7)
O50.0549 (10)0.0521 (10)0.0317 (9)−0.0034 (8)0.0037 (7)−0.0078 (7)
O60.0595 (10)0.0418 (10)0.0445 (10)−0.0072 (8)0.0004 (8)−0.0151 (7)
N10.0664 (14)0.0453 (12)0.0314 (10)0.0145 (10)−0.0064 (9)−0.0087 (9)
C10.0253 (10)0.0302 (11)0.0327 (11)0.0025 (8)0.0022 (8)−0.0003 (8)
C20.0268 (10)0.0274 (10)0.0347 (11)0.0009 (8)0.0017 (8)−0.0035 (9)
C30.0243 (10)0.0347 (11)0.0340 (11)0.0017 (8)0.0014 (8)−0.0026 (9)
C40.0263 (10)0.0359 (12)0.0422 (13)0.0010 (9)−0.0001 (9)−0.0102 (10)
C50.0363 (12)0.0291 (11)0.0507 (14)−0.0026 (9)0.0032 (10)−0.0027 (10)
C60.0332 (11)0.0333 (12)0.0430 (13)0.0007 (9)0.0034 (9)0.0043 (10)
C70.0276 (11)0.0398 (13)0.0361 (12)0.0019 (9)0.0030 (9)−0.0046 (10)
C80.0621 (17)0.0474 (15)0.0756 (19)−0.0215 (13)−0.0251 (14)0.0167 (13)
C90.0687 (19)0.092 (2)0.0485 (16)−0.0086 (16)0.0178 (14)0.0167 (15)
C100.082 (2)0.0681 (18)0.0357 (14)−0.0133 (15)−0.0139 (13)0.0039 (12)
C110.0533 (16)0.0748 (19)0.0635 (18)−0.0191 (14)−0.0169 (13)0.0147 (14)
C120.0524 (17)0.107 (2)0.0592 (18)0.0259 (16)0.0114 (13)0.0104 (16)
O70.0447 (9)0.0437 (9)0.0486 (10)−0.0015 (7)0.0040 (8)−0.0046 (7)
Geometric parameters (Å, °) top
S1—O31.4398 (15)C5—C61.370 (3)
S1—O11.4478 (16)C5—H50.9300
S1—O21.4628 (15)C6—H6A0.9300
S1—C11.767 (2)C8—C91.492 (4)
O4—C71.309 (3)C8—H8A0.9700
O4—H40.85 (3)C8—H8B0.9700
O5—C71.224 (2)C9—C101.505 (4)
O6—C41.350 (2)C9—H9A0.9700
O6—H60.84 (3)C9—H9B0.9700
N1—C81.477 (3)C10—C111.494 (4)
N1—C121.483 (3)C10—H10A0.9700
N1—H1A0.92 (3)C10—H10B0.9700
N1—H1B0.88 (3)C11—C121.485 (4)
C1—C21.375 (3)C11—H11A0.9700
C1—C61.396 (3)C11—H11B0.9700
C2—C31.396 (3)C12—H12A0.9700
C2—H20.9300C12—H12B0.9700
C3—C41.403 (3)O7—H7A0.859 (9)
C3—C71.473 (3)O7—H7B0.855 (9)
C4—C51.389 (3)
O3—S1—O1114.30 (10)O5—C7—C3122.69 (19)
O3—S1—O2111.89 (9)O4—C7—C3114.48 (18)
O1—S1—O2111.36 (10)N1—C8—C9110.2 (2)
O3—S1—C1107.72 (9)N1—C8—H8A109.6
O1—S1—C1105.64 (9)C9—C8—H8A109.6
O2—S1—C1105.25 (9)N1—C8—H8B109.6
C7—O4—H4109.9 (19)C9—C8—H8B109.6
C4—O6—H6105 (2)H8A—C8—H8B108.1
C8—N1—C12112.9 (2)C8—C9—C10111.5 (2)
C8—N1—H1A109.1 (15)C8—C9—H9A109.3
C12—N1—H1A109.4 (16)C10—C9—H9A109.3
C8—N1—H1B103.9 (16)C8—C9—H9B109.3
C12—N1—H1B110.4 (16)C10—C9—H9B109.3
H1A—N1—H1B111 (2)H9A—C9—H9B108.0
C2—C1—C6119.45 (18)C11—C10—C9110.2 (2)
C2—C1—S1120.57 (15)C11—C10—H10A109.6
C6—C1—S1119.95 (15)C9—C10—H10A109.6
C1—C2—C3120.67 (18)C11—C10—H10B109.6
C1—C2—H2119.7C9—C10—H10B109.6
C3—C2—H2119.7H10A—C10—H10B108.1
C2—C3—C4119.16 (18)C12—C11—C10111.7 (2)
C2—C3—C7121.05 (18)C12—C11—H11A109.3
C4—C3—C7119.78 (18)C10—C11—H11A109.3
O6—C4—C5117.99 (18)C12—C11—H11B109.3
O6—C4—C3122.22 (19)C10—C11—H11B109.3
C5—C4—C3119.79 (19)H11A—C11—H11B107.9
C6—C5—C4120.09 (19)N1—C12—C11111.0 (2)
C6—C5—H5120.0N1—C12—H12A109.4
C4—C5—H5120.0C11—C12—H12A109.4
C5—C6—C1120.8 (2)N1—C12—H12B109.4
C5—C6—H6A119.6C11—C12—H12B109.4
C1—C6—H6A119.6H12A—C12—H12B108.0
O5—C7—O4122.83 (19)H7A—O7—H7B113.6 (15)
O3—S1—C1—C2−17.95 (18)C3—C4—C5—C61.0 (3)
O1—S1—C1—C2−140.49 (16)C4—C5—C6—C10.2 (3)
O2—S1—C1—C2101.57 (16)C2—C1—C6—C5−1.1 (3)
O3—S1—C1—C6164.09 (15)S1—C1—C6—C5176.88 (15)
O1—S1—C1—C641.55 (18)C2—C3—C7—O5−177.13 (18)
O2—S1—C1—C6−76.39 (17)C4—C3—C7—O53.7 (3)
C6—C1—C2—C30.9 (3)C2—C3—C7—O43.2 (3)
S1—C1—C2—C3−177.12 (14)C4—C3—C7—O4−175.97 (18)
C1—C2—C3—C40.3 (3)C12—N1—C8—C955.3 (3)
C1—C2—C3—C7−178.85 (17)N1—C8—C9—C10−55.7 (3)
C2—C3—C4—O6178.52 (17)C8—C9—C10—C1156.0 (3)
C7—C3—C4—O6−2.3 (3)C9—C10—C11—C12−55.3 (3)
C2—C3—C4—C5−1.2 (3)C8—N1—C12—C11−54.9 (3)
C7—C3—C4—C5177.93 (17)C10—C11—C12—N154.5 (3)
O6—C4—C5—C6−178.76 (18)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O7—H7B···O10.855 (9)1.933 (10)2.786 (2)176 (2)
O7—H7A···O2i0.859 (9)1.912 (10)2.770 (2)177 (2)
N1—H1B···O50.88 (3)2.55 (2)2.983 (3)110.6 (18)
N1—H1B···O7ii0.88 (3)2.16 (3)2.996 (3)157 (2)
N1—H1A···O2iii0.92 (3)1.90 (3)2.807 (3)170 (2)
O6—H6···O50.84 (3)1.82 (3)2.597 (2)153 (3)
O4—H4···O7ii0.85 (3)1.75 (3)2.601 (2)179 (3)
Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y+3/2, z+1/2; (iii) −x, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O7—H7B···O10.855 (9)1.933 (10)2.786 (2)176 (2)
O7—H7A···O2i0.859 (9)1.912 (10)2.770 (2)177 (2)
N1—H1B···O50.88 (3)2.55 (2)2.983 (3)110.6 (18)
N1—H1B···O7ii0.88 (3)2.16 (3)2.996 (3)157 (2)
N1—H1A···O2iii0.92 (3)1.90 (3)2.807 (3)170 (2)
O6—H6···O50.84 (3)1.82 (3)2.597 (2)153 (3)
O4—H4···O7ii0.85 (3)1.75 (3)2.601 (2)179 (3)
Symmetry codes: (i) x+1, y, z; (ii) x−1/2, −y+3/2, z+1/2; (iii) −x, −y+2, −z+1.
Acknowledgements top

The authors are grateful for the financial support of Tianjin Polytechnic University (029623 and 029817) and the Natural Science Foundation of Tianjin Education Committee (20070607).

references
References top

Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Smith, G., Wermuth, U. D., Young, D. J. & White, J. M. (2007). Polyhedron, 26, 3645–3652.