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

Xiao, L.; Zhang, Y.-H.; Cui, Y.; Jin, X.-H.; Wang, W.

doi:10.1107/S1600536807067633

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o350

doi:10.1107/S1600536807067633

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

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

^aCollege of Pharmaceuticals and Biotechnology, Tianjin University, Tianjin 300072, People's Republic of China, and ^bSchool of Chemical Engineering, University of Science and Technology, Liaoning, Anshan 114051, People's Republic of China
^*Correspondence e-mail: tju_chemistry@yahoo.com.cn

(Received 12 December 2007; accepted 19 December 2007; online 4 January 2008)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.040
wR(F²) = 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

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

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Bruker, 1997).

Figures top

Fig. 1. The content of asymmetric unit of (I) with the atomic numbering and 35% probability displacement ellipsoids.

4-Hydroxy-2,2,6,6-tetramethylpiperidinium hydrogensulfate monohydrat top

Crystal data top

C₉H₂₀NO⁺·HO₄S⁻·H₂O	Z = 2
M_r = 273.34	F(000) = 296
Triclinic, P1	D_x = 1.346 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.334 (3) Å	Cell parameters from 1816 reflections
b = 8.518 (3) Å	θ = 2.6–26.2°
c = 10.245 (3) Å	µ = 0.26 mm⁻¹
α = 78.465 (5)°	T = 294 K
β = 82.546 (5)°	Plate, colourless
γ = 71.586 (4)°	0.26 × 0.24 × 0.20 mm
V = 674.3 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2374 independent reflections
Radiation source: fine-focus sealed tube	1929 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −9→6
T_min = 0.936, T_max = 0.951	k = −10→9
3506 measured reflections	l = −11→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.045P)² + 0.4673P] where P = (F_o² + 2F_c²)/3
2374 reflections	(Δ/σ)_max < 0.001
176 parameters	Δρ_max = 0.41 e Å⁻³
5 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₉H₂₀NO⁺·HO₄S⁻·H₂O	γ = 71.586 (4)°
M_r = 273.34	V = 674.3 (3) Å³
Triclinic, P1	Z = 2
a = 8.334 (3) Å	Mo Kα radiation
b = 8.518 (3) Å	µ = 0.26 mm⁻¹
c = 10.245 (3) Å	T = 294 K
α = 78.465 (5)°	0.26 × 0.24 × 0.20 mm
β = 82.546 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2374 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1929 reflections with I > 2σ(I)
T_min = 0.936, T_max = 0.951	R_int = 0.016
3506 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	5 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.41 e Å⁻³
2374 reflections	Δρ_min = −0.33 e Å⁻³
176 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

	x	y	z	U_iso*/U_eq
S1	0.14016 (7)	0.73866 (7)	0.24152 (5)	0.03302 (19)
O1	0.4452 (2)	0.7411 (3)	0.46414 (17)	0.0535 (5)
H1	0.547 (2)	0.720 (4)	0.457 (4)	0.080*
O2	0.3063 (3)	0.7840 (3)	0.24406 (19)	0.0642 (6)
H2	0.344 (5)	0.760 (5)	0.319 (2)	0.096*
O3	0.0141 (2)	0.8333 (2)	0.33050 (17)	0.0468 (5)
O4	0.1771 (3)	0.5626 (3)	0.2834 (2)	0.0752 (7)
O5	0.0982 (3)	0.7967 (3)	0.10455 (17)	0.0676 (6)
N1	0.1898 (2)	0.8477 (2)	0.83066 (18)	0.0273 (4)
H1A	0.164 (3)	0.832 (3)	0.9156 (11)	0.033*
H1B	0.124 (2)	0.9428 (18)	0.795 (2)	0.033*
C1	0.3968 (3)	0.7257 (3)	0.6054 (2)	0.0361 (5)
H1C	0.4668	0.6187	0.6519	0.043*
C2	0.4211 (3)	0.8696 (3)	0.6595 (2)	0.0349 (5)
H2A	0.3553	0.9749	0.6101	0.042*
H2B	0.5396	0.8656	0.6444	0.042*
C3	0.3682 (3)	0.8660 (3)	0.8082 (2)	0.0302 (5)
C4	0.1464 (3)	0.7153 (3)	0.7725 (2)	0.0325 (5)
C5	0.2122 (3)	0.7299 (3)	0.6255 (2)	0.0368 (5)
H5A	0.1989	0.6383	0.5891	0.044*
H5B	0.1442	0.8343	0.5763	0.044*
C6	0.4904 (3)	0.7243 (3)	0.8968 (2)	0.0427 (6)
H6A	0.4410	0.7137	0.9870	0.064*
H6B	0.5952	0.7495	0.8946	0.064*
H6C	0.5116	0.6208	0.8645	0.064*
C7	0.3528 (3)	1.0332 (3)	0.8499 (3)	0.0435 (6)
H7A	0.2729	1.1223	0.7972	0.065*
H7B	0.4614	1.0530	0.8359	0.065*
H7C	0.3145	1.0291	0.9427	0.065*
C8	−0.0472 (3)	0.7621 (3)	0.7869 (3)	0.0463 (6)
H8A	−0.0831	0.6808	0.7552	0.069*
H8B	−0.0942	0.8711	0.7354	0.069*
H8C	−0.0859	0.7639	0.8792	0.069*
C9	0.2196 (4)	0.5397 (3)	0.8522 (3)	0.0497 (7)
H9A	0.1695	0.4635	0.8278	0.075*
H9B	0.1950	0.5431	0.9459	0.075*
H9C	0.3401	0.5023	0.8328	0.075*
O6	0.7835 (3)	0.6591 (3)	0.4742 (2)	0.0653 (6)
H6D	0.858 (4)	0.702 (5)	0.442 (4)	0.098*
H6E	0.814 (5)	0.591 (4)	0.540 (3)	0.098*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0324 (3)	0.0395 (3)	0.0236 (3)	−0.0090 (2)	0.0009 (2)	−0.0016 (2)
O1	0.0404 (10)	0.0952 (15)	0.0292 (9)	−0.0222 (11)	0.0056 (8)	−0.0224 (9)
O2	0.0442 (11)	0.1171 (19)	0.0365 (11)	−0.0394 (12)	0.0015 (8)	−0.0028 (11)
O3	0.0428 (10)	0.0516 (11)	0.0402 (10)	−0.0059 (8)	0.0048 (8)	−0.0131 (8)
O4	0.0928 (17)	0.0381 (11)	0.0867 (17)	−0.0123 (11)	−0.0044 (13)	−0.0057 (11)
O5	0.0535 (12)	0.1205 (19)	0.0234 (9)	−0.0260 (12)	−0.0040 (8)	0.0006 (10)
N1	0.0263 (10)	0.0300 (10)	0.0244 (9)	−0.0080 (8)	0.0000 (7)	−0.0038 (8)
C1	0.0352 (13)	0.0462 (14)	0.0251 (12)	−0.0095 (11)	0.0008 (9)	−0.0083 (10)
C2	0.0320 (12)	0.0450 (14)	0.0287 (12)	−0.0159 (10)	0.0019 (9)	−0.0040 (10)
C3	0.0272 (11)	0.0382 (12)	0.0264 (11)	−0.0122 (9)	−0.0018 (9)	−0.0043 (9)
C4	0.0349 (12)	0.0315 (12)	0.0345 (13)	−0.0155 (10)	−0.0001 (10)	−0.0055 (9)
C5	0.0376 (13)	0.0440 (14)	0.0328 (12)	−0.0144 (11)	−0.0019 (10)	−0.0123 (10)
C6	0.0321 (13)	0.0579 (16)	0.0334 (13)	−0.0081 (11)	−0.0067 (10)	−0.0030 (11)
C7	0.0448 (15)	0.0486 (15)	0.0456 (15)	−0.0221 (12)	−0.0031 (11)	−0.0139 (12)
C8	0.0398 (14)	0.0552 (16)	0.0521 (16)	−0.0243 (12)	0.0039 (12)	−0.0158 (13)
C9	0.0630 (18)	0.0324 (13)	0.0528 (16)	−0.0184 (12)	−0.0020 (13)	0.0003 (11)
O6	0.0456 (12)	0.0785 (16)	0.0653 (15)	−0.0238 (11)	0.0011 (10)	0.0083 (11)

Geometric parameters (Å, º) top

S1—O4	1.419 (2)	C4—C8	1.529 (3)
S1—O5	1.4411 (18)	C4—C9	1.530 (3)
S1—O3	1.4476 (18)	C4—C5	1.530 (3)
S1—O2	1.555 (2)	C5—H5A	0.9700
O1—C1	1.443 (3)	C5—H5B	0.9700
O1—H1	0.81 (2)	C6—H6A	0.9600
O2—H2	0.83 (2)	C6—H6B	0.9600
N1—C3	1.528 (3)	C6—H6C	0.9600
N1—C4	1.529 (3)	C7—H7A	0.9600
N1—H1A	0.86 (2)	C7—H7B	0.9600
N1—H1B	0.86 (2)	C7—H7C	0.9600
C1—C5	1.515 (3)	C8—H8A	0.9600
C1—C2	1.519 (3)	C8—H8B	0.9600
C1—H1C	0.9800	C8—H8C	0.9600
C2—C3	1.528 (3)	C9—H9A	0.9600
C2—H2A	0.9700	C9—H9B	0.9600
C2—H2B	0.9700	C9—H9C	0.9600
C3—C7	1.529 (3)	O6—H6D	0.82 (2)
C3—C6	1.531 (3)	O6—H6E	0.81 (2)

O4—S1—O5	114.56 (15)	N1—C4—C5	107.47 (17)
O4—S1—O3	112.68 (13)	C8—C4—C5	111.10 (19)
O5—S1—O3	111.13 (12)	C9—C4—C5	112.8 (2)
O4—S1—O2	107.34 (14)	C1—C5—C4	112.66 (18)
O5—S1—O2	103.30 (11)	C1—C5—H5A	109.1
O3—S1—O2	107.04 (12)	C4—C5—H5A	109.1
C1—O1—H1	106 (3)	C1—C5—H5B	109.1
S1—O2—H2	114 (3)	C4—C5—H5B	109.1
C3—N1—C4	120.80 (17)	H5A—C5—H5B	107.8
C3—N1—H1A	107.9 (16)	C3—C6—H6A	109.5
C4—N1—H1A	107.7 (16)	C3—C6—H6B	109.5
C3—N1—H1B	105.5 (16)	H6A—C6—H6B	109.5
C4—N1—H1B	105.6 (16)	C3—C6—H6C	109.5
H1A—N1—H1B	109 (2)	H6A—C6—H6C	109.5
O1—C1—C5	108.04 (18)	H6B—C6—H6C	109.5
O1—C1—C2	109.83 (19)	C3—C7—H7A	109.5
C5—C1—C2	110.27 (19)	C3—C7—H7B	109.5
O1—C1—H1C	109.6	H7A—C7—H7B	109.5
C5—C1—H1C	109.6	C3—C7—H7C	109.5
C2—C1—H1C	109.6	H7A—C7—H7C	109.5
C1—C2—C3	113.44 (18)	H7B—C7—H7C	109.5
C1—C2—H2A	108.9	C4—C8—H8A	109.5
C3—C2—H2A	108.9	C4—C8—H8B	109.5
C1—C2—H2B	108.9	H8A—C8—H8B	109.5
C3—C2—H2B	108.9	C4—C8—H8C	109.5
H2A—C2—H2B	107.7	H8A—C8—H8C	109.5
N1—C3—C2	107.19 (16)	H8B—C8—H8C	109.5
N1—C3—C7	105.65 (18)	C4—C9—H9A	109.5
C2—C3—C7	111.28 (19)	C4—C9—H9B	109.5
N1—C3—C6	110.75 (18)	H9A—C9—H9B	109.5
C2—C3—C6	112.80 (19)	C4—C9—H9C	109.5
C7—C3—C6	108.92 (19)	H9A—C9—H9C	109.5
N1—C4—C8	105.19 (18)	H9B—C9—H9C	109.5
N1—C4—C9	111.11 (19)	H6D—O6—H6E	111 (4)
C8—C4—C9	108.9 (2)

O1—C1—C2—C3	178.44 (18)	C3—N1—C4—C8	−167.05 (19)
C5—C1—C2—C3	59.5 (2)	C3—N1—C4—C9	75.2 (2)
C4—N1—C3—C2	47.9 (2)	C3—N1—C4—C5	−48.6 (2)
C4—N1—C3—C7	166.70 (19)	O1—C1—C5—C4	−179.71 (19)
C4—N1—C3—C6	−75.5 (2)	C2—C1—C5—C4	−59.7 (3)
C1—C2—C3—N1	−50.8 (2)	N1—C4—C5—C1	51.7 (3)
C1—C2—C3—C7	−165.8 (2)	C8—C4—C5—C1	166.3 (2)
C1—C2—C3—C6	71.4 (2)	C9—C4—C5—C1	−71.1 (3)

Hydrogen-bond geometry (Å, º) top

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)	1.93 (2)	2.795 (3)	178 (2)
N1—H1B···O3ⁱⁱ	0.86 (2)	2.15 (2)	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)

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

Experimental details

Crystal data
Chemical formula	C₉H₂₀NO⁺·HO₄S⁻·H₂O
M_r	273.34
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	8.334 (3), 8.518 (3), 10.245 (3)
α, β, γ (°)	78.465 (5), 82.546 (5), 71.586 (4)
V (Å³)	674.3 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.26 × 0.24 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.936, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	3506, 2374, 1929
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.108, 1.06
No. of reflections	2374
No. of parameters	176
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.33

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top

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)

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

References

Bruker (1997). SMART (Version 5.611), SAINT (Version 6.0), SADABS (Version 2.03) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gray, R. L. (1991). Plast. Eng. 47, 21–23. CAS Google Scholar
Liu, X., Ju, C. X., Hu, R. S. & Gu, D. P. (2006). J. Heibei Normal Univ. (Nat. Sci. Ed.), 30, 326–328. CAS Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

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Volume 64| Part 2| February 2008| Page o350

doi:10.1107/S1600536807067633

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