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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1622.
Published online 2008 July 31. doi:  10.1107/S1600536808022460
PMCID: PMC2962183

5-Hydr­oxy-1-methyl-3,4-dihydro-2H-pyrrolium hydrogensulfate

Abstract

The title compound, C5H10NO+·HSO4 , has been synthesized by reaction of 1-methyl­pyrrolidin-2-one with H2SO4 in a 1:1 molar ratio. The substituted pyrrolium ring adopts an envelope conformation. The hydrogensulfate anions form infinite helical chains parallel to the a axis via strong O—H(...)O hydrogen bonds. The pyrrolium cations are pendant from the chains. These cations are the hydrogen donors in the strong O—H(...)O hydrogen bonds to the hydrogensulfates. In addition, there are weak C—H(...)O hydrogen bonds in the structure.

Related literature

For related literature, see: Forbes & Weaver (2004 [triangle]); Zhu et al. (2003 [triangle]); Desiraju & Steiner (1999 [triangle]).

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Object name is e-64-o1622-scheme1.jpg

Experimental

Crystal data

  • C5H10NO+·HSO4
  • M r = 197.21
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1622-efi3.jpg
  • a = 6.5418 (14) Å
  • b = 10.964 (2) Å
  • c = 11.614 (2) Å
  • V = 833.0 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.37 mm−1
  • T = 173 (2) K
  • 0.48 × 0.25 × 0.22 mm

Data collection

  • Bruker SMART 1K area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.841, T max = 0.922
  • 4132 measured reflections
  • 1578 independent reflections
  • 1519 reflections with I > 2σ(I)
  • R int = 0.023

Refinement

  • R[F 2 > 2σ(F 2)] = 0.027
  • wR(F 2) = 0.089
  • S = 1.20
  • 1578 reflections
  • 113 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.36 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 609 Friedel pairs
  • Flack parameter: 0.01 (9)

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808022460/fb2100sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022460/fb2100Isup2.hkl

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

Acknowledgments

This work was supported by Guangdong Provincial Science Foundation.

supplementary crystallographic information

Comment

1-methyl-2-hydroxyl-pyrrolium hydrogensulfate is applied in the green chemical engineering field as a replacement of volatile organic solvents (Forbes et al., 2004) or as a catalyst for esterification (Zhu et al., 2003).

In the title structure, the bond distances and angles are normal. The most important structural feature is presence of strong intermolecular O—H···O hydrogen bonds (Desiraju & Steiner, 1999) that interconnect the hydrogensulfate anions (Tab. 1). The hydrogensulfates form infinite left-handed helical chains along the axis a. The hydrogensulfates are acceptors of another short hydrogen O—H···O bond donated by the 1-methyl-2-hydroxyl-pyrrolium cations (Tab. 1). In addition, there are also C—H···O weak hydrogen bonds present in the structure (Tab. 1).

The unconstrained refinement of the hydroxyl hydrogens resulted in the less probable distances: 0.92 (4) and 0.72 (4)Å for O1-H1 and O3-H3, respectively.

Experimental

The title compound was prepared by the reaction of 1-methylpyrrolidin-2-one and H2SO4 in 1:1 mole ratio. 3.675 g (0.0375 mol) H2SO4 was added dropwise under stirring at room temperature to a boiling flask containing 3.712 g (0.0375 mol) of 1-methylpyrrolidin-2-one. Then the mixture was heated to 373 K. After 2 h, the mixture was cooled to room temperature and the title compound was obtained. Its crystals of were obtained from petroleum/ethyl acetate (v/v = 1/1) by solvent evaporation at 4° C. The longest dimension of the crystals was about 10 mm. The compound's identity was confirmed by IR and NMR spectra. 1H NMR in CD3CN (500 MHz): 5.4–6.3(H),3.59 (t, 7 Hz, 2H), 2.94 (s, 3H), 2.74(t, 8 Hz, 2H), 2.10 (m, 8 Hz, 2H).

Refinement

All the H atoms were discernible in the difference Fourier maps. However, the H atoms were constrained in a riding-motion approximation. C—Hmethyl 0.98, C—Hmethylene0.99, O—H 0.84 Å. Uiso(Hmethylene)=1.2Ueq(Cmethylene); Uiso(Hmethyl)=1.5Ueq(Cmethyl); Uiso(HO)=1.5(O).

Figures

Fig. 1.
The molecules in the asymmetric unit of the title compound, with anisotropic displacement parameters drawn at the 50% probability level.
Fig. 2.
A view of the O—H···O hydrogen-bond pattern. The H atoms that are not involved in the O—H···O hydrogen bonds have been omitted for the sake of clarity. The chains of the hydrogensulfates ...

Crystal data

C5H10NO+·HSO4F000 = 416
Mr = 197.21Dx = 1.573 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3942 reflections
a = 6.5418 (14) Åθ = 2.6–27.0º
b = 10.964 (2) ŵ = 0.37 mm1
c = 11.614 (2) ÅT = 173 (2) K
V = 833.0 (3) Å3Prism, colourless
Z = 40.48 × 0.25 × 0.22 mm

Data collection

Bruker SMART 1K area-detector diffractometer1578 independent reflections
Radiation source: medium-focus sealed tube1519 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.023
T = 173(2) Kθmax = 26.0º
[var phi] and ω scansθmin = 2.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −7→8
Tmin = 0.841, Tmax = 0.922k = −13→12
4132 measured reflectionsl = −10→14

Refinement

Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.027  w = 1/[σ2(Fo2) + (0.047P)2 + 0.264P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.089(Δ/σ)max < 0.001
S = 1.20Δρmax = 0.28 e Å3
1578 reflectionsΔρmin = −0.36 e Å3
113 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
41 constraintsExtinction coefficient: 0.020 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapFlack parameter: 0.01 (9)

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
C10.6096 (4)0.42511 (19)0.26605 (17)0.0238 (5)
C20.5508 (4)0.3055 (2)0.31637 (19)0.0275 (5)
H2A0.56670.23890.25960.033*
H2B0.40780.30680.34430.033*
C30.7017 (4)0.2912 (2)0.4163 (2)0.0346 (6)
H3A0.63690.31420.49020.042*
H3B0.75070.20600.42190.042*
C40.8773 (4)0.3774 (2)0.38749 (19)0.0296 (5)
H4A0.92590.42070.45710.035*
H4B0.99320.33260.35260.035*
C50.8878 (4)0.5749 (2)0.2701 (2)0.0309 (5)
H5A0.85210.59410.19020.046*
H5B1.03610.56440.27660.046*
H5C0.84380.64180.32030.046*
N10.7857 (3)0.46269 (17)0.30466 (16)0.0242 (4)
O10.5090 (3)0.48791 (14)0.19136 (14)0.0299 (4)
H10.40100.45080.17390.045*
O50.1546 (3)0.27995 (19)−0.05492 (17)0.0434 (5)
O3−0.1165 (2)0.40674 (14)0.01936 (15)0.0318 (4)
H3−0.17240.34070.03820.048*
O40.1944 (3)0.49886 (18)−0.03734 (17)0.0418 (5)
O20.1898 (3)0.37202 (16)0.13185 (14)0.0308 (4)
S10.11940 (8)0.38873 (5)0.01336 (4)0.02365 (18)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0289 (12)0.0234 (10)0.0192 (9)0.0026 (10)−0.0002 (9)−0.0042 (7)
C20.0325 (12)0.0242 (10)0.0257 (10)−0.0049 (10)0.0011 (9)−0.0005 (9)
C30.0380 (14)0.0303 (12)0.0355 (13)0.0013 (12)−0.0029 (11)0.0070 (10)
C40.0296 (12)0.0289 (11)0.0302 (10)0.0052 (12)−0.0059 (10)0.0043 (9)
C50.0342 (14)0.0237 (11)0.0346 (11)−0.0064 (11)0.0021 (11)−0.0001 (8)
N10.0266 (9)0.0213 (9)0.0246 (9)0.0022 (9)−0.0012 (7)−0.0014 (7)
O10.0322 (9)0.0284 (8)0.0290 (8)−0.0007 (7)−0.0092 (7)0.0032 (6)
O50.0456 (12)0.0447 (11)0.0398 (9)0.0131 (9)−0.0127 (8)−0.0166 (8)
O30.0246 (9)0.0263 (8)0.0445 (9)0.0001 (7)−0.0038 (8)0.0019 (7)
O40.0416 (10)0.0427 (11)0.0411 (11)−0.0084 (9)−0.0052 (8)0.0160 (8)
O20.0332 (9)0.0338 (9)0.0253 (8)−0.0011 (8)−0.0057 (6)0.0015 (7)
S10.0244 (3)0.0233 (3)0.0232 (3)0.0004 (2)−0.0032 (2)0.00028 (19)

Geometric parameters (Å, °)

C1—O11.288 (3)C4—H4B0.9900
C1—N11.303 (3)C5—N11.457 (3)
C1—C21.486 (3)C5—H5A0.9800
C2—C31.532 (3)C5—H5B0.9800
C2—H2A0.9900C5—H5C0.9800
C2—H2B0.9900O1—H10.8400
C3—C41.525 (4)O5—S11.4507 (19)
C3—H3A0.9900O3—S11.5576 (17)
C3—H3B0.9900O3—H30.8400
C4—N11.469 (3)O4—S11.4302 (19)
C4—H4A0.9900O2—S11.4626 (17)
O1—C1—N1121.0 (2)C3—C4—H4B111.1
O1—C1—C2127.2 (2)H4A—C4—H4B109.1
N1—C1—C2111.9 (2)N1—C5—H5A109.5
C1—C2—C3102.82 (19)N1—C5—H5B109.5
C1—C2—H2A111.2H5A—C5—H5B109.5
C3—C2—H2A111.2N1—C5—H5C109.5
C1—C2—H2B111.2H5A—C5—H5C109.5
C3—C2—H2B111.2H5B—C5—H5C109.5
H2A—C2—H2B109.1C1—N1—C5125.3 (2)
C4—C3—C2104.78 (19)C1—N1—C4112.62 (19)
C4—C3—H3A110.8C5—N1—C4122.1 (2)
C2—C3—H3A110.8C1—O1—H1109.5
C4—C3—H3B110.8S1—O3—H3109.5
C2—C3—H3B110.8O4—S1—O5114.49 (13)
H3A—C3—H3B108.9O4—S1—O2112.65 (11)
N1—C4—C3103.36 (19)O5—S1—O2111.19 (11)
N1—C4—H4A111.1O4—S1—O3104.56 (11)
C3—C4—H4A111.1O5—S1—O3106.63 (11)
N1—C4—H4B111.1O2—S1—O3106.60 (10)
O1—C1—C2—C3−168.1 (2)C2—C1—N1—C5178.53 (19)
N1—C1—C2—C313.3 (3)O1—C1—N1—C4−179.01 (19)
C1—C2—C3—C4−20.2 (2)C2—C1—N1—C4−0.3 (3)
C2—C3—C4—N120.1 (2)C3—C4—N1—C1−13.0 (3)
O1—C1—N1—C5−0.2 (4)C3—C4—N1—C5168.2 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···O5i0.841.752.569 (3)164
O1—H1···O20.841.702.540 (2)177
C2—H2A···O5ii0.992.453.250 (3)137
C5—H5C···O2iii0.982.593.488 (3)152

Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) x+1/2, −y+1/2, −z; (iii) −x+1, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FB2100).

References

  • Bruker (1999). SMART and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology, p. 13. International Union of Crystallography, Monographs on Crystallography. Oxford University Press.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Forbes, D. C. & Weaver, K. J. (2004). J. Mol. Catal. A Chem.214, 129–132.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhu, H. P., Yang, F., Tang, J. & He, M. Y. (2003). Green Chem.5, 38–39.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography