4-Hydr­oxy-2,2,6,6-tetra­methyl­piperidinium hydrogensulfate monohydrate

Li Xiao; Yun-Hui Zhang; Ying Cui; Xing-Hua Jin; Wei Wang

doi:10.1107/S1600536807067633

. 2008 Jan 4;64(Pt 2):o350. doi: 10.1107/S1600536807067633

4-Hydroxy-2,2,6,6-tetramethylpiperidinium hydrogensulfate monohydrate

Li Xiao ^a, Yun-Hui Zhang ^a, Ying Cui ^a, Xing-Hua Jin ^a, Wei Wang ^b,^*

PMCID: PMC2960323 PMID: 21201382

Abstract

In the title compound, C₉H₂₀NO⁺·HO₄S⁻·H₂O, the piperidinium ring adopts a chair conformation. Intermolecular O—H⋯O and N—H⋯O hydrogen bonds form an extensive three-dimensional network, which consolidates the crystal structure.

Related literature

For useful applications of tetramethylpiperidinol, see: Gray (1991 ▶); Liu et al. (2006 ▶).

Experimental

Crystal data

C₉H₂₀NO⁺·HO₄S⁻·H₂O
M _r = 273.34
Triclinic,
a = 8.334 (3) Å
b = 8.518 (3) Å
c = 10.245 (3) Å
α = 78.465 (5)°
β = 82.546 (5)°
γ = 71.586 (4)°
V = 674.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 294 (2) K
0.26 × 0.24 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.936, T _max = 0.951
3506 measured reflections
2374 independent reflections
1929 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.108
S = 1.06
2374 reflections
176 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 1997 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807067633/cv2376sup1.cif

e-64-0o350-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067633/cv2376Isup2.hkl

e-64-0o350-Isup2.hkl^{(116.6KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1	0.83 (2)	1.76 (2)	2.576 (3)	168 (4)
N1—H1A⋯O5ⁱ	0.86 (2)	1.933 (17)	2.795 (3)	178 (2)
N1—H1B⋯O3ⁱⁱ	0.86 (2)	2.154 (19)	3.002 (3)	168 (2)
O6—H6D⋯O3ⁱⁱⁱ	0.82 (2)	2.06 (2)	2.874 (3)	169 (4)
O6—H6E⋯O4^iv	0.81 (2)	2.00 (2)	2.790 (3)	165 (4)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

Tetramethylpiperidinol is an important intermediate used in the synthesis of hindered amine light stabilizer (HALS) (Gray, 1991; Liu et al., 2006). The title compound, (I), is a new derivative of tetramethylpiperidinol. Herein we report its crystal structure.

In (I) (Fig. 1), the piperidinium ring adopts a chair conformation. The hydroxy group attached at C1 is in equatorial position. In the crystal, the intermolecular O—H···O and N—H···O hydrogen bonds (Table 1) form an extensive three-dimensional network, which consolidates the packing.

Experimental

2,2,6,6-Tetramethylpiperidin-4-ol (40.0 g, 254 mmol) was dissolved in 98% H₂SO₄ (24.5 g) and then cooled to 278 K. With stirring, water (100 ml) was then added dropwise to the mixture over a period of 0.5 h. The mixture was stirred at 273–278 K for a further 3 h. The title compound (54.50 g) was obtained in powder form in a yield of 75.6%. Crystals of (I) were obtained by slow evaporation of a solution of water.