4-Hydr­oxy-2,2,6,6-tetra­methyl­piperidinium chloride–hydroxonium chloride (3/1)

Zhang, L.; Zhang, P.-W.; Wang, X.-H.; Chen, L.; Shen, Q.-F.

doi:10.1107/S1600536808002158

organic compounds

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doi:10.1107/S1600536808002158

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4-Hydroxy-2,2,6,6-tetramethylpiperidinium chloride–hydroxonium chloride (3/1)

Li Zhang,^a ^* Peng-Wei Zhang,^a,^b Xiao-Hui Wang,^a Li Chen ^a and Qu-Fei Shen ^a

^aDepartment of Pharmaceutics, Medical College of the Chinese People's Armed Police Force, Tianjin 300162, People's Republic of China, and ^bSchool of Pharmaceutical Science & Technology, Tianjin University, Tianjin 300072, People's Republic of China
^*Correspondence e-mail: zpw0803@gmail.com

(Received 9 January 2008; accepted 21 January 2008; online 25 January 2008)

The crystal structure of the title compound, C₉H₂₀NO⁺·Cl⁻·0.33(H₃O⁺·Cl⁻), is composed of 4-hydroxy-2,2,6,6-tetramethylpiperidinium cations, hydroxonium cations and chloride anions, which are connected via O—H⋯O, O—H⋯Cl and N—H⋯Cl hydrogen bonding. The 4-hydroxy-2,2,6,6-tetramethylpiperidinium cation and one of the two crystallographically independent chloride anions are located on a mirror plane. The hydroxonium cation is located on a threefold axis and the second crystallographically independent chloride anion is located on a sixfold rotoinversion axis. Due to symmetry, the hydroxonium cation is disordered over two positions.

Experimental

Crystal data

C₉H₂₀NO⁺·Cl⁻·0.33(H₃O⁺·Cl⁻)
M_r = 211.87
Hexagonal, P 6₃ /m
a = 13.4460 (19) Å
c = 11.528 (2) Å
V = 1804.9 (5) Å³
Z = 6
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 113 (2) K
0.10 × 0.10 × 0.04 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.968, T_max = 0.989
14051 measured reflections
1513 independent reflections
1424 reflections with I > 2σ(I)
R_int = 0.075

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.130
S = 1.08
1513 reflections
68 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl2ⁱ	0.85	2.15	2.991 (2)	172
N1—H1B⋯Cl2ⁱⁱ	0.92	2.22	3.139 (2)	175
N1—H1C⋯Cl1ⁱⁱⁱ	0.92	2.25	3.166 (2)	176
O2—H2⋯O1^iv	0.85	1.63	2.475 (2)	175
Symmetry codes: (i) -y, x-y, z; (ii) -x+y+1, -x+1, z; (iii) -x+1, -y+1, -z+1; (iv) x+1, y, z.

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536808002158/nc2088sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808002158/nc2088Isup2.hkl

checkCIF report

Comment top

The title compound was obtained as a byproduct in the synthesis of hindered light stabilizer. For the characterization of this compound a crystal structure analysis was performed. The crystal structure of this compound consists of 4-hydroxy-2,2,6,6-tetramethylpiperidinium cations, hydroxonium cations and chloride anions, all of them located in special positions (Fig. 1). The cations and the anions are connected via O—H···O, O—H···Cl and N—H···Cl hydrogen bonding (Table 1). The isolated water oxygen atom, which is located on a 3-fold axis is disordered in two positions because of symmetry. For charge balance it must be protonated. However, the corresponding H atom was clearly located in difference map.

Experimental top

0.25 g(1.6 mmol) of 2,2,6,6-tetramethylpiperidin-4-ol was dissolved in 3.2 ml of hydrochloric acid (3.2 mmol. Colorless crystals of the title compound were obtained by slow evaporation of the solvent.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); 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. Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radii. Symmetry codes: A = x,y,0.5 - z.

4-Hydroxy-2,2,6,6-tetramethylpiperidinium chloride–hydroxonium chloride (3/1) top

Crystal data top

C₉H₂₀NO⁺·Cl⁻·0.33(H₃O⁺·Cl⁻)	D_x = 1.170 Mg m⁻³
M_r = 211.87	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6₃/m	Cell parameters from 4368 reflections
a = 13.4460 (19) Å	θ = 1.8–27.9°
c = 11.528 (2) Å	µ = 0.36 mm⁻¹
V = 1804.9 (5) Å³	T = 113 K
Z = 6	Block, colorless
F(000) = 692	0.10 × 0.10 × 0.04 mm

Data collection top

Rigaku Saturn diffractometer	1513 independent reflections
Radiation source: rotating anode	1424 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.075
Detector resolution: 7.31 pixels mm^-1	θ_max = 27.9°, θ_min = 2.5°
ω scans	h = −13→17
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −17→16
T_min = 0.968, T_max = 0.989	l = −14→15
14051 measured reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0699P)² + 0.5807P] where P = (F_o² + 2F_c²)/3
1513 reflections	(Δ/σ)_max < 0.001
68 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₉H₂₀NO⁺·Cl⁻·0.33(H₃O⁺·Cl⁻)	Z = 6
M_r = 211.87	Mo Kα radiation
Hexagonal, P6₃/m	µ = 0.36 mm⁻¹
a = 13.4460 (19) Å	T = 113 K
c = 11.528 (2) Å	0.10 × 0.10 × 0.04 mm
V = 1804.9 (5) Å³

Data collection top

Rigaku Saturn diffractometer	1513 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1424 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.989	R_int = 0.075
14051 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.08	Δρ_max = 0.33 e Å⁻³
1513 reflections	Δρ_min = −0.26 e Å⁻³
68 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	Occ. (<1)
O1	−0.13431 (15)	0.43006 (16)	0.2500	0.0420 (6)
H1	−0.0986	0.5031	0.2500	0.050*
N1	0.16134 (16)	0.39830 (16)	0.2500	0.0174 (4)
H1B	0.2019	0.3598	0.2500	0.021*
H1C	0.2145	0.4755	0.2500	0.021*
C1	−0.0587 (2)	0.3833 (2)	0.2500	0.0283 (6)
H1A	−0.1063	0.2976	0.2500	0.034*
C2	0.01605 (15)	0.42088 (15)	0.35766 (18)	0.0260 (4)
H2A	−0.0339	0.3965	0.4271	0.031*
H2B	0.0625	0.5058	0.3587	0.031*
C3	0.09668 (15)	0.37155 (15)	0.36468 (16)	0.0213 (4)
C4	0.03335 (16)	0.24188 (16)	0.38919 (18)	0.0279 (4)
H4A	−0.0362	0.2037	0.3415	0.042*
H4B	0.0123	0.2284	0.4714	0.042*
H4C	0.0836	0.2108	0.3702	0.042*
C5	0.18849 (18)	0.43315 (17)	0.45708 (17)	0.0302 (4)
H5A	0.2438	0.4060	0.4542	0.045*
H5B	0.1523	0.4170	0.5338	0.045*
H5C	0.2283	0.5161	0.4426	0.045*
Cl1	0.6667	0.3333	0.7500	0.0219 (3)
Cl2	0.71701 (5)	0.03169 (5)	0.2500	0.0244 (2)
O2	0.6667	0.3333	0.3252 (4)	0.0276 (10)	0.50
H2	0.7352	0.3704	0.2999	0.041*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0168 (9)	0.0200 (9)	0.091 (2)	0.0103 (8)	0.000	0.000
N1	0.0169 (9)	0.0186 (9)	0.0159 (11)	0.0083 (8)	0.000	0.000
C1	0.0176 (12)	0.0170 (11)	0.052 (2)	0.0096 (9)	0.000	0.000
C2	0.0239 (9)	0.0212 (8)	0.0318 (11)	0.0105 (7)	0.0114 (8)	0.0049 (7)
C3	0.0232 (8)	0.0232 (8)	0.0173 (9)	0.0114 (7)	0.0050 (7)	0.0036 (6)
C4	0.0278 (9)	0.0248 (9)	0.0313 (11)	0.0133 (8)	0.0075 (8)	0.0092 (8)
C5	0.0376 (10)	0.0329 (10)	0.0162 (10)	0.0146 (9)	−0.0007 (8)	0.0022 (8)
Cl1	0.0202 (3)	0.0202 (3)	0.0254 (6)	0.01012 (16)	0.000	0.000
Cl2	0.0251 (3)	0.0203 (3)	0.0295 (4)	0.0125 (2)	0.000	0.000
O2	0.0243 (14)	0.0243 (14)	0.034 (3)	0.0121 (7)	0.000	0.000

Geometric parameters (Å, º) top

O1—C1	1.438 (3)	C2—H2B	0.9900
O1—H1	0.8500	C3—C5	1.524 (3)
N1—C3	1.523 (2)	C3—C4	1.536 (2)
N1—C3ⁱ	1.523 (2)	C4—H4A	0.9800
N1—H1B	0.9200	C4—H4B	0.9800
N1—H1C	0.9200	C4—H4C	0.9800
C1—C2	1.516 (2)	C5—H5A	0.9800
C1—C2ⁱ	1.516 (2)	C5—H5B	0.9800
C1—H1A	1.0000	C5—H5C	0.9800
C2—C3	1.530 (2)	O2—O2ⁱ	1.733 (10)
C2—H2A	0.9900	O2—H2	0.8501

C1—O1—H1	113.0	N1—C3—C5	105.47 (14)
C3—N1—C3ⁱ	120.43 (18)	N1—C3—C2	107.23 (15)
C3—N1—H1B	107.2	C5—C3—C2	111.00 (16)
C3ⁱ—N1—H1B	107.2	N1—C3—C4	110.77 (15)
C3—N1—H1C	107.2	C5—C3—C4	109.09 (15)
C3ⁱ—N1—H1C	107.2	C2—C3—C4	113.01 (14)
H1B—N1—H1C	106.9	C3—C4—H4A	109.5
O1—C1—C2	110.50 (13)	C3—C4—H4B	109.5
O1—C1—C2ⁱ	110.51 (13)	H4A—C4—H4B	109.5
C2—C1—C2ⁱ	109.9 (2)	C3—C4—H4C	109.5
O1—C1—H1A	108.6	H4A—C4—H4C	109.5
C2—C1—H1A	108.6	H4B—C4—H4C	109.5
C2ⁱ—C1—H1A	108.6	C3—C5—H5A	109.5
C1—C2—C3	113.23 (16)	C3—C5—H5B	109.5
C1—C2—H2A	108.9	H5A—C5—H5B	109.5
C3—C2—H2A	108.9	C3—C5—H5C	109.5
C1—C2—H2B	108.9	H5A—C5—H5C	109.5
C3—C2—H2B	108.9	H5B—C5—H5C	109.5
H2A—C2—H2B	107.7	O2ⁱ—O2—H2	69.9

O1—C1—C2—C3	178.55 (15)	C3ⁱ—N1—C3—C4	74.5 (2)
C2ⁱ—C1—C2—C3	−59.2 (2)	C1—C2—C3—N1	51.7 (2)
C3ⁱ—N1—C3—C5	−167.57 (14)	C1—C2—C3—C5	166.46 (16)
C3ⁱ—N1—C3—C2	−49.2 (2)	C1—C2—C3—C4	−70.6 (2)

Symmetry code: (i) x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl2ⁱⁱ	0.85	2.15	2.991 (2)	172
N1—H1B···Cl2ⁱⁱⁱ	0.92	2.22	3.139 (2)	175
N1—H1C···Cl1^iv	0.92	2.25	3.166 (2)	176
O2—H2···O1^v	0.85	1.63	2.475 (2)	175

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

Experimental details

Crystal data
Chemical formula	C₉H₂₀NO⁺·Cl⁻·0.33(H₃O⁺·Cl⁻)
M_r	211.87
Crystal system, space group	Hexagonal, P6₃/m
Temperature (K)	113
a, c (Å)	13.4460 (19), 11.528 (2)
V (Å³)	1804.9 (5)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.10 × 0.10 × 0.04

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.968, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	14051, 1513, 1424
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.130, 1.08
No. of reflections	1513
No. of parameters	68
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.26

Computer programs: CrystalClear (Rigaku/MSC, 2005), 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
O1—H1···Cl2ⁱ	0.85	2.15	2.991 (2)	172.0
N1—H1B···Cl2ⁱⁱ	0.92	2.22	3.139 (2)	174.6
N1—H1C···Cl1ⁱⁱⁱ	0.92	2.25	3.166 (2)	175.7
O2—H2···O1^iv	0.85	1.63	2.475 (2)	174.8

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

References

Rigaku/MSC (2005). CrystalClear and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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doi:10.1107/S1600536808002158

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-Hydr­­oxy-2,2,6,6-tetra­methyl­piperidinium chloride–hydroxonium chloride (3/1)

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

4-Hydroxy-2,2,6,6-tetramethylpiperidinium chloride–hydroxonium chloride (3/1)