4-Hydr­oxy-2,2,6,6-tetra­methyl­piperidinium trichloro­acetate

Zhang, P.-W.; Zhang, T.-Y.; Zhang, L.; Deng, Y.

doi:10.1107/S1600536808005369

organic compounds

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ISSN: 2056-9890

Volume 64| Part 3| March 2008| Page o641

doi:10.1107/S1600536808005369

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4-Hydroxy-2,2,6,6-tetramethylpiperidinium trichloroacetate

Peng-Wei Zhang,^a,^b ^* Tong-Yun Zhang,^c Li Zhang ^b and Yi Deng ^a

^aSchool of Pharmaceutical Science & Technology, Tianjin University, Tianjin 300072, People's Republic of China, ^bDepartment of Pharmaceutics, Medical College of Chinese People's Armed Police Force, Tianjin 300162, People's Republic of China, and ^cDarentang Pharmaceutical Factory, Tianjin Zhongxin Pharmaceutical Group Co. Ltd, Tianjin 300457, People's Republic of China
^*Correspondence e-mail: zpw0803@gmail.com

(Received 19 February 2008; accepted 26 February 2008; online 29 February 2008)

In the crystal structure of the title compound, C₉H₂₀NO⁺·Cl₃CCOO⁻, the cations and anions are connected via O—H⋯O, N—H⋯O, O—H⋯Cl and N—H⋯Cl hydrogen bonding. The six-membered ring adopts a chair conformation with the hydroxyl group in an equatorial position.

Related literature

For related literature, see: Borzatta & Carrozza (1991 ).

Experimental

Crystal data

C₉H₂₀NO⁺·C₂Cl₃O₂⁻
M_r = 320.63
Monoclinic, P 2₁
a = 6.3468 (13) Å
b = 14.450 (3) Å
c = 8.2175 (16) Å
β = 95.19 (3)°
V = 750.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.61 mm⁻¹
T = 113 (2) K
0.12 × 0.10 × 0.08 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.930, T_max = 0.953
5459 measured reflections
2858 independent reflections
2636 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.060
S = 1.06
2858 reflections
179 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.23 e Å⁻³
Absolute structure: Flack (1983 ), 996 Friedel pairs
Flack parameter: 0.04 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.89 (3)	1.99 (3)	2.8095 (18)	152 (3)
O1—H1⋯Cl1ⁱ	0.89 (3)	2.92 (3)	3.6201 (16)	136 (2)
N1—H1A⋯O3ⁱⁱ	0.95 (3)	1.87 (3)	2.8085 (19)	170 (2)
N1—H1B⋯O2ⁱⁱⁱ	0.94 (2)	1.87 (2)	2.796 (2)	165.1 (19)
N1—H1B⋯Cl2ⁱⁱⁱ	0.94 (2)	2.94 (2)	3.5647 (16)	124.5 (16)
Symmetry codes: (i) x+1, y, z; (ii) $[-x, y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+1]$ .

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/S1600536808005369/hg2380sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808005369/hg2380Isup2.hkl

checkCIF report

Comment top

The title compound was obtained as a byproduct in the synthesis of hindered amine light stabilizers preventing the degradation of polyolefins in sunlight, in which 2,2,6,6-tetramethylpiperidin-4-ol is a very important intermediate (Borzatta & Carrozza,1991). We report here the crystal structure 4-hydroxy-2,2,6,6-tetramethylpiperidinium trichloroacetate (Fig. 1). Intermolecular O—H···O, N—H···O, O—H···Cl, N—H···Cl hydrogen bonds are observed which help to establish the crystal packing. The piperidine ring adopts a chair conformation.

Related literature top

For related literature, see: Borzatta & Carrozza (1991).

Experimental top

0.25 g (1.6 mmol) of 2,2,6,6-tetramethylpiperidin-4-ol was dissolved in 3.2 ml of trichloroacetate acid solution (1.6 mmol, 0.26 g). 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 atom labeling and displacement ellipsoids drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radii.

4-Hydroxy-2,2,6,6-tetramethylpiperidinium trichloroacetate top

Crystal data top

C₉H₂₀NO⁺·C₂Cl₃O₂⁻	F(000) = 336
M_r = 320.63	D_x = 1.419 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2559 reflections
a = 6.3468 (13) Å	θ = 1.4–27.9°
b = 14.450 (3) Å	µ = 0.61 mm⁻¹
c = 8.2175 (16) Å	T = 113 K
β = 95.19 (3)°	Block, colorless
V = 750.5 (3) Å³	0.12 × 0.10 × 0.08 mm
Z = 2

Data collection top

Rigaku Saturn diffractometer	2858 independent reflections
Radiation source: rotating anode	2636 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.028
ω and ϕ scans	θ_max = 27.9°, θ_min = 2.5°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −8→8
T_min = 0.930, T_max = 0.953	k = −15→19
5459 measured reflections	l = −10→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.0324P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
2858 reflections	Δρ_max = 0.21 e Å⁻³
179 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 996 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (4)

Crystal data top

C₉H₂₀NO⁺·C₂Cl₃O₂⁻	V = 750.5 (3) Å³
M_r = 320.63	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.3468 (13) Å	µ = 0.61 mm⁻¹
b = 14.450 (3) Å	T = 113 K
c = 8.2175 (16) Å	0.12 × 0.10 × 0.08 mm
β = 95.19 (3)°

Data collection top

Rigaku Saturn diffractometer	2858 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2636 reflections with I > 2σ(I)
T_min = 0.930, T_max = 0.953	R_int = 0.028
5459 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.060	Δρ_max = 0.21 e Å⁻³
S = 1.06	Δρ_min = −0.23 e Å⁻³
2858 reflections	Absolute structure: Flack (1983), 996 Friedel pairs
179 parameters	Absolute structure parameter: 0.04 (4)
1 restraint

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
Cl1	−0.04464 (7)	0.51471 (3)	0.10942 (5)	0.01980 (10)
Cl2	0.34863 (6)	0.41431 (3)	0.12885 (6)	0.02203 (11)
Cl3	−0.00077 (8)	0.35637 (3)	−0.09864 (5)	0.02572 (11)
O1	0.7973 (2)	0.47566 (9)	0.51619 (17)	0.0227 (3)
H1	0.798 (4)	0.453 (2)	0.415 (4)	0.063 (10)*
O2	0.1032 (2)	0.27147 (9)	0.27469 (18)	0.0247 (3)
O3	−0.20242 (18)	0.34925 (9)	0.25644 (15)	0.0169 (3)
N1	0.4803 (2)	0.71305 (9)	0.64562 (18)	0.0111 (3)
C1	0.4608 (3)	0.62855 (12)	0.75507 (19)	0.0129 (3)
C2	0.6286 (3)	0.55858 (11)	0.7135 (2)	0.0139 (3)
H2A	0.7701	0.5832	0.7515	0.017*
H2B	0.6080	0.5005	0.7739	0.017*
C3	0.6235 (3)	0.53661 (11)	0.5324 (2)	0.0159 (4)
H3	0.4876	0.5051	0.4945	0.019*
C4	0.6475 (3)	0.62493 (13)	0.4346 (2)	0.0164 (3)
H4A	0.6371	0.6090	0.3170	0.020*
H4B	0.7905	0.6506	0.4638	0.020*
C5	0.4836 (3)	0.69993 (12)	0.46158 (19)	0.0135 (3)
C6	0.2366 (3)	0.58770 (13)	0.7353 (2)	0.0198 (4)
H6A	0.1327	0.6377	0.7379	0.030*
H6B	0.2191	0.5443	0.8248	0.030*
H6C	0.2149	0.5550	0.6306	0.030*
C7	0.5076 (3)	0.66393 (13)	0.9293 (2)	0.0189 (4)
H7A	0.6495	0.6912	0.9419	0.028*
H7B	0.5003	0.6124	1.0061	0.028*
H7C	0.4029	0.7110	0.9519	0.028*
C8	0.2629 (3)	0.67658 (13)	0.3825 (2)	0.0198 (4)
H8A	0.1595	0.7193	0.4228	0.030*
H8B	0.2266	0.6130	0.4104	0.030*
H8C	0.2609	0.6825	0.2636	0.030*
C9	0.5521 (3)	0.79290 (13)	0.3950 (2)	0.0213 (4)
H9A	0.4450	0.8399	0.4123	0.032*
H9B	0.5676	0.7871	0.2779	0.032*
H9C	0.6878	0.8113	0.4523	0.032*
C10	0.0700 (3)	0.40324 (12)	0.09850 (19)	0.0130 (3)
C11	−0.0172 (3)	0.33454 (11)	0.2249 (2)	0.0133 (3)
H1A	0.373 (4)	0.7546 (18)	0.674 (3)	0.037 (7)*
H1B	0.610 (4)	0.7410 (15)	0.683 (3)	0.025 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0227 (2)	0.01408 (19)	0.0232 (2)	0.00440 (16)	0.00505 (17)	0.00388 (16)
Cl2	0.01100 (19)	0.0235 (2)	0.0318 (3)	−0.00221 (15)	0.00291 (17)	0.00920 (19)
Cl3	0.0321 (3)	0.0304 (3)	0.0149 (2)	−0.0025 (2)	0.00289 (18)	−0.00596 (17)
O1	0.0249 (7)	0.0194 (7)	0.0241 (7)	0.0108 (5)	0.0033 (6)	−0.0052 (6)
O2	0.0147 (6)	0.0220 (7)	0.0377 (8)	0.0023 (5)	0.0044 (6)	0.0151 (6)
O3	0.0125 (6)	0.0160 (6)	0.0230 (7)	−0.0007 (5)	0.0056 (5)	−0.0007 (5)
N1	0.0114 (7)	0.0098 (7)	0.0124 (7)	0.0007 (5)	0.0033 (6)	−0.0002 (5)
C1	0.0127 (8)	0.0130 (8)	0.0133 (8)	0.0010 (6)	0.0032 (6)	0.0029 (6)
C2	0.0137 (8)	0.0124 (8)	0.0156 (9)	0.0027 (6)	0.0014 (7)	0.0001 (6)
C3	0.0152 (8)	0.0131 (8)	0.0193 (9)	0.0035 (6)	0.0010 (7)	−0.0028 (6)
C4	0.0164 (9)	0.0187 (8)	0.0149 (8)	0.0020 (6)	0.0049 (7)	−0.0023 (7)
C5	0.0167 (8)	0.0153 (8)	0.0089 (7)	0.0010 (6)	0.0031 (6)	0.0010 (6)
C6	0.0152 (9)	0.0174 (9)	0.0276 (10)	−0.0007 (7)	0.0059 (8)	0.0059 (7)
C7	0.0228 (9)	0.0215 (10)	0.0127 (8)	0.0047 (7)	0.0028 (7)	0.0000 (7)
C8	0.0196 (9)	0.0215 (9)	0.0176 (9)	−0.0002 (7)	−0.0023 (7)	0.0013 (7)
C9	0.0272 (11)	0.0164 (9)	0.0214 (10)	−0.0001 (7)	0.0090 (8)	0.0043 (7)
C10	0.0118 (8)	0.0134 (8)	0.0141 (8)	0.0009 (6)	0.0021 (6)	0.0010 (6)
C11	0.0124 (8)	0.0145 (8)	0.0130 (8)	−0.0019 (6)	0.0010 (6)	−0.0006 (6)

Geometric parameters (Å, º) top

Cl1—C10	1.7729 (17)	C4—C5	1.532 (2)
Cl2—C10	1.7710 (17)	C4—H4A	0.9900
Cl3—C10	1.7756 (17)	C4—H4B	0.9900
O1—C3	1.427 (2)	C5—C8	1.528 (2)
O1—H1	0.89 (3)	C5—C9	1.529 (3)
O2—C11	1.235 (2)	C6—H6A	0.9800
O3—C11	1.245 (2)	C6—H6B	0.9800
N1—C5	1.526 (2)	C6—H6C	0.9800
N1—C1	1.528 (2)	C7—H7A	0.9800
N1—H1A	0.95 (3)	C7—H7B	0.9800
N1—H1B	0.94 (2)	C7—H7C	0.9800
C1—C7	1.524 (2)	C8—H8A	0.9800
C1—C2	1.529 (2)	C8—H8B	0.9800
C1—C6	1.535 (2)	C8—H8C	0.9800
C2—C3	1.519 (2)	C9—H9A	0.9800
C2—H2A	0.9900	C9—H9B	0.9800
C2—H2B	0.9900	C9—H9C	0.9800
C3—C4	1.523 (2)	C10—C11	1.573 (2)
C3—H3	1.0000

C3—O1—H1	112.3 (19)	C8—C5—C4	113.00 (15)
C5—N1—C1	119.53 (13)	C9—C5—C4	110.55 (15)
C5—N1—H1A	113.1 (15)	C1—C6—H6A	109.5
C1—N1—H1A	105.4 (15)	C1—C6—H6B	109.5
C5—N1—H1B	106.5 (14)	H6A—C6—H6B	109.5
C1—N1—H1B	105.4 (13)	C1—C6—H6C	109.5
H1A—N1—H1B	106 (2)	H6A—C6—H6C	109.5
C7—C1—N1	105.40 (13)	H6B—C6—H6C	109.5
C7—C1—C2	110.56 (14)	C1—C7—H7A	109.5
N1—C1—C2	107.56 (13)	C1—C7—H7B	109.5
C7—C1—C6	109.16 (14)	H7A—C7—H7B	109.5
N1—C1—C6	111.62 (14)	C1—C7—H7C	109.5
C2—C1—C6	112.31 (14)	H7A—C7—H7C	109.5
C3—C2—C1	113.80 (14)	H7B—C7—H7C	109.5
C3—C2—H2A	108.8	C5—C8—H8A	109.5
C1—C2—H2A	108.8	C5—C8—H8B	109.5
C3—C2—H2B	108.8	H8A—C8—H8B	109.5
C1—C2—H2B	108.8	C5—C8—H8C	109.5
H2A—C2—H2B	107.7	H8A—C8—H8C	109.5
O1—C3—C2	105.80 (14)	H8B—C8—H8C	109.5
O1—C3—C4	110.67 (14)	C5—C9—H9A	109.5
C2—C3—C4	110.33 (14)	C5—C9—H9B	109.5
O1—C3—H3	110.0	H9A—C9—H9B	109.5
C2—C3—H3	110.0	C5—C9—H9C	109.5
C4—C3—H3	110.0	H9A—C9—H9C	109.5
C3—C4—C5	114.51 (14)	H9B—C9—H9C	109.5
C3—C4—H4A	108.6	C11—C10—Cl2	111.74 (11)
C5—C4—H4A	108.6	C11—C10—Cl1	111.69 (11)
C3—C4—H4B	108.6	Cl2—C10—Cl1	108.65 (9)
C5—C4—H4B	108.6	C11—C10—Cl3	106.67 (11)
H4A—C4—H4B	107.6	Cl2—C10—Cl3	109.25 (9)
N1—C5—C8	110.77 (14)	Cl1—C10—Cl3	108.77 (9)
N1—C5—C9	105.97 (14)	O2—C11—O3	128.65 (16)
C8—C5—C9	108.77 (14)	O2—C11—C10	116.15 (14)
N1—C5—C4	107.55 (13)	O3—C11—C10	115.14 (14)

C5—N1—C1—C7	168.77 (14)	C1—N1—C5—C9	−167.95 (14)
C5—N1—C1—C2	50.78 (19)	C1—N1—C5—C4	−49.69 (19)
C5—N1—C1—C6	−72.85 (19)	C3—C4—C5—N1	50.25 (19)
C7—C1—C2—C3	−166.72 (14)	C3—C4—C5—C8	−72.32 (19)
N1—C1—C2—C3	−52.12 (18)	C3—C4—C5—C9	165.51 (16)
C6—C1—C2—C3	71.08 (18)	Cl2—C10—C11—O2	−29.86 (19)
C1—C2—C3—O1	176.40 (14)	Cl1—C10—C11—O2	−151.81 (14)
C1—C2—C3—C4	56.67 (19)	Cl3—C10—C11—O2	89.47 (17)
O1—C3—C4—C5	−172.59 (14)	Cl2—C10—C11—O3	152.80 (13)
C2—C3—C4—C5	−55.84 (19)	Cl1—C10—C11—O3	30.85 (18)
C1—N1—C5—C8	74.25 (18)	Cl3—C10—C11—O3	−87.87 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.89 (3)	1.99 (3)	2.8095 (18)	152 (3)
O1—H1···Cl1ⁱ	0.89 (3)	2.92 (3)	3.6201 (16)	136 (2)
N1—H1A···O3ⁱⁱ	0.95 (3)	1.87 (3)	2.8085 (19)	170 (2)
N1—H1B···O2ⁱⁱⁱ	0.94 (2)	1.87 (2)	2.796 (2)	165.1 (19)
N1—H1B···Cl2ⁱⁱⁱ	0.94 (2)	2.94 (2)	3.5647 (16)	124.5 (16)

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

Experimental details

Crystal data
Chemical formula	C₉H₂₀NO⁺·C₂Cl₃O₂⁻
M_r	320.63
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	113
a, b, c (Å)	6.3468 (13), 14.450 (3), 8.2175 (16)
β (°)	95.19 (3)
V (Å³)	750.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.930, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	5459, 2858, 2636
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.060, 1.06
No. of reflections	2858
No. of parameters	179
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.23
Absolute structure	Flack (1983), 996 Friedel pairs
Absolute structure parameter	0.04 (4)

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···O3ⁱ	0.89 (3)	1.99 (3)	2.8095 (18)	152 (3)
O1—H1···Cl1ⁱ	0.89 (3)	2.92 (3)	3.6201 (16)	136 (2)
N1—H1A···O3ⁱⁱ	0.95 (3)	1.87 (3)	2.8085 (19)	170 (2)
N1—H1B···O2ⁱⁱⁱ	0.94 (2)	1.87 (2)	2.796 (2)	165.1 (19)
N1—H1B···Cl2ⁱⁱⁱ	0.94 (2)	2.94 (2)	3.5647 (16)	124.5 (16)

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

References

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Volume 64| Part 3| March 2008| Page o641

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