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

Fang, Y.-X.; Huang, H.-R.; Du, Z.-Y.; Huang, B.-H.; Zhang, K.

doi:10.1107/S1600536808022460

organic compounds

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ISSN: 2056-9890

Volume 64| Part 8| August 2008| Page o1622

doi:10.1107/S1600536808022460

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

Yan-Xiong Fang,^a ^* Hua-Rong Huang,^a Zhi-Yun Du,^a Bao-Hua Huang ^a and Kun Zhang ^a

^aFaculty of Light Industrial and Chemical Engineering, Guangdong University of Technology, Guangzhou 510090, People's Republic of China
^*Correspondence e-mail: corihr@yahoo.com.cn

(Received 17 June 2008; accepted 17 July 2008; online 31 July 2008)

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 ); Zhu et al. (2003 ); Desiraju & Steiner (1999 ).

Experimental

Crystal data

C₅H₁₀NO⁺·HSO₄⁻
M_r = 197.21
Orthorhombic, P 2₁ 2₁ 2₁
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 ) 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[F² > 2σ(F²)] = 0.027
wR(F²) = 0.089
S = 1.20
1578 reflections
113 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ), 609 Friedel pairs
Flack parameter: 0.01 (9)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O5ⁱ	0.84	1.75	2.569 (3)	164
O1—H1⋯O2	0.84	1.70	2.540 (2)	177
C2—H2A⋯O5ⁱⁱ	0.99	2.45	3.250 (3)	137
C5—H5C⋯O2ⁱⁱⁱ	0.98	2.59	3.488 (3)	152
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; 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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART (Bruker, 1999); data reduction: SAINT [or SAINT-Plus?] (Bruker, 1999); 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

	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 are oriented parallel to the crystallographic axis a. Symmetry codes: (I) x - 1/2,0.5 - y,-z; (II) x + 1/2,0.5 - y,-z.

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

Crystal data top

C₅H₁₀NO⁺·HSO₄⁻	F(000) = 416
M_r = 197.21	D_x = 1.573 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3942 reflections
a = 6.5418 (14) Å	θ = 2.6–27.0°
b = 10.964 (2) Å	µ = 0.37 mm⁻¹
c = 11.614 (2) Å	T = 173 K
V = 833.0 (3) Å³	Prism, colourless
Z = 4	0.48 × 0.25 × 0.22 mm

Data collection top

Bruker SMART 1K area-detector diffractometer	1578 independent reflections
Radiation source: medium-focus sealed tube	1519 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→8
T_min = 0.841, T_max = 0.922	k = −13→12
4132 measured reflections	l = −10→14

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.027	w = 1/[σ²(F_o²) + (0.047P)² + 0.264P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.089	(Δ/σ)_max < 0.001
S = 1.20	Δρ_max = 0.28 e Å⁻³
1578 reflections	Δρ_min = −0.36 e Å⁻³
113 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.020 (4)
41 constraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (9)
Secondary atom site location: difference Fourier map

Crystal data top

C₅H₁₀NO⁺·HSO₄⁻	V = 833.0 (3) Å³
M_r = 197.21	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.5418 (14) Å	µ = 0.37 mm⁻¹
b = 10.964 (2) Å	T = 173 K
c = 11.614 (2) Å	0.48 × 0.25 × 0.22 mm

Data collection top

Bruker SMART 1K area-detector diffractometer	1578 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1519 reflections with I > 2σ(I)
T_min = 0.841, T_max = 0.922	R_int = 0.023
4132 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.089	Δρ_max = 0.28 e Å⁻³
S = 1.20	Δρ_min = −0.36 e Å⁻³
1578 reflections	Absolute structure: Flack (1983)
113 parameters	Absolute structure parameter: 0.01 (9)
0 restraints

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

	x	y	z	U_iso*/U_eq
C1	0.6096 (4)	0.42511 (19)	0.26605 (17)	0.0238 (5)
C2	0.5508 (4)	0.3055 (2)	0.31637 (19)	0.0275 (5)
H2A	0.5667	0.2389	0.2596	0.033*
H2B	0.4078	0.3068	0.3443	0.033*
C3	0.7017 (4)	0.2912 (2)	0.4163 (2)	0.0346 (6)
H3A	0.6369	0.3142	0.4902	0.042*
H3B	0.7507	0.2060	0.4219	0.042*
C4	0.8773 (4)	0.3774 (2)	0.38749 (19)	0.0296 (5)
H4A	0.9259	0.4207	0.4571	0.035*
H4B	0.9932	0.3326	0.3526	0.035*
C5	0.8878 (4)	0.5749 (2)	0.2701 (2)	0.0309 (5)
H5A	0.8521	0.5941	0.1902	0.046*
H5B	1.0361	0.5644	0.2766	0.046*
H5C	0.8438	0.6418	0.3203	0.046*
N1	0.7857 (3)	0.46269 (17)	0.30466 (16)	0.0242 (4)
O1	0.5090 (3)	0.48791 (14)	0.19136 (14)	0.0299 (4)
H1	0.4010	0.4508	0.1739	0.045*
O5	0.1546 (3)	0.27995 (19)	−0.05492 (17)	0.0434 (5)
O3	−0.1165 (2)	0.40674 (14)	0.01936 (15)	0.0318 (4)
H3	−0.1724	0.3407	0.0382	0.048*
O4	0.1944 (3)	0.49886 (18)	−0.03734 (17)	0.0418 (5)
O2	0.1898 (3)	0.37202 (16)	0.13185 (14)	0.0308 (4)
S1	0.11940 (8)	0.38873 (5)	0.01336 (4)	0.02365 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0289 (12)	0.0234 (10)	0.0192 (9)	0.0026 (10)	−0.0002 (9)	−0.0042 (7)
C2	0.0325 (12)	0.0242 (10)	0.0257 (10)	−0.0049 (10)	0.0011 (9)	−0.0005 (9)
C3	0.0380 (14)	0.0303 (12)	0.0355 (13)	0.0013 (12)	−0.0029 (11)	0.0070 (10)
C4	0.0296 (12)	0.0289 (11)	0.0302 (10)	0.0052 (12)	−0.0059 (10)	0.0043 (9)
C5	0.0342 (14)	0.0237 (11)	0.0346 (11)	−0.0064 (11)	0.0021 (11)	−0.0001 (8)
N1	0.0266 (9)	0.0213 (9)	0.0246 (9)	0.0022 (9)	−0.0012 (7)	−0.0014 (7)
O1	0.0322 (9)	0.0284 (8)	0.0290 (8)	−0.0007 (7)	−0.0092 (7)	0.0032 (6)
O5	0.0456 (12)	0.0447 (11)	0.0398 (9)	0.0131 (9)	−0.0127 (8)	−0.0166 (8)
O3	0.0246 (9)	0.0263 (8)	0.0445 (9)	0.0001 (7)	−0.0038 (8)	0.0019 (7)
O4	0.0416 (10)	0.0427 (11)	0.0411 (11)	−0.0084 (9)	−0.0052 (8)	0.0160 (8)
O2	0.0332 (9)	0.0338 (9)	0.0253 (8)	−0.0011 (8)	−0.0057 (6)	0.0015 (7)
S1	0.0244 (3)	0.0233 (3)	0.0232 (3)	0.0004 (2)	−0.0032 (2)	0.00028 (19)

Geometric parameters (Å, º) top

C1—O1	1.288 (3)	C4—H4B	0.9900
C1—N1	1.303 (3)	C5—N1	1.457 (3)
C1—C2	1.486 (3)	C5—H5A	0.9800
C2—C3	1.532 (3)	C5—H5B	0.9800
C2—H2A	0.9900	C5—H5C	0.9800
C2—H2B	0.9900	O1—H1	0.8400
C3—C4	1.525 (4)	O5—S1	1.4507 (19)
C3—H3A	0.9900	O3—S1	1.5576 (17)
C3—H3B	0.9900	O3—H3	0.8400
C4—N1	1.469 (3)	O4—S1	1.4302 (19)
C4—H4A	0.9900	O2—S1	1.4626 (17)

O1—C1—N1	121.0 (2)	C3—C4—H4B	111.1
O1—C1—C2	127.2 (2)	H4A—C4—H4B	109.1
N1—C1—C2	111.9 (2)	N1—C5—H5A	109.5
C1—C2—C3	102.82 (19)	N1—C5—H5B	109.5
C1—C2—H2A	111.2	H5A—C5—H5B	109.5
C3—C2—H2A	111.2	N1—C5—H5C	109.5
C1—C2—H2B	111.2	H5A—C5—H5C	109.5
C3—C2—H2B	111.2	H5B—C5—H5C	109.5
H2A—C2—H2B	109.1	C1—N1—C5	125.3 (2)
C4—C3—C2	104.78 (19)	C1—N1—C4	112.62 (19)
C4—C3—H3A	110.8	C5—N1—C4	122.1 (2)
C2—C3—H3A	110.8	C1—O1—H1	109.5
C4—C3—H3B	110.8	S1—O3—H3	109.5
C2—C3—H3B	110.8	O4—S1—O5	114.49 (13)
H3A—C3—H3B	108.9	O4—S1—O2	112.65 (11)
N1—C4—C3	103.36 (19)	O5—S1—O2	111.19 (11)
N1—C4—H4A	111.1	O4—S1—O3	104.56 (11)
C3—C4—H4A	111.1	O5—S1—O3	106.63 (11)
N1—C4—H4B	111.1	O2—S1—O3	106.60 (10)

O1—C1—C2—C3	−168.1 (2)	C2—C1—N1—C5	178.53 (19)
N1—C1—C2—C3	13.3 (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—N1	20.1 (2)	C3—C4—N1—C1	−13.0 (3)
O1—C1—N1—C5	−0.2 (4)	C3—C4—N1—C5	168.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5ⁱ	0.84	1.75	2.569 (3)	164
O1—H1···O2	0.84	1.70	2.540 (2)	177
C2—H2A···O5ⁱⁱ	0.99	2.45	3.250 (3)	137
C5—H5C···O2ⁱⁱⁱ	0.98	2.59	3.488 (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.

Experimental details

Crystal data
Chemical formula	C₅H₁₀NO⁺·HSO₄⁻
M_r	197.21
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	173
a, b, c (Å)	6.5418 (14), 10.964 (2), 11.614 (2)
V (Å³)	833.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.48 × 0.25 × 0.22

Data collection
Diffractometer	Bruker SMART 1K area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.841, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	4132, 1578, 1519
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.089, 1.20
No. of reflections	1578
No. of parameters	113
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.36
Absolute structure	Flack (1983)
Absolute structure parameter	0.01 (9)

Computer programs: SMART (Bruker, 1999), SAINT [or SAINT-Plus?] (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O5ⁱ	0.84	1.75	2.569 (3)	163.9
O1—H1···O2	0.84	1.70	2.540 (2)	176.6
C2—H2A···O5ⁱⁱ	0.99	2.45	3.250 (3)	137
C5—H5C···O2ⁱⁱⁱ	0.98	2.59	3.488 (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.

Acknowledgements

This work was supported by Guangdong Provincial Science Foundation.

References

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