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Acta Cryst. (2008). E64, o641    [ doi:10.1107/S1600536808005369 ]

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

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

Abstract top

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.

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.

Refinement top

All H atoms bound to C atoms were constrained; positioned geometrically (C—H = 0.96–0.98 Å) and refined as riding with Uiso(H)=1.2Ueq(carrier) or 1.5eq(methyl groups). H atoms of O—H and N—H were located from difference maps and then refined freely.

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
[Figure 1] 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–F000 = 336
Mr = 320.63Dx = 1.419 Mg m−3
Monoclinic, P21Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 2559 reflections
a = 6.3468 (13) Åθ = 1.4–27.9º
b = 14.450 (3) ŵ = 0.61 mm−1
c = 8.2175 (16) ÅT = 113 (2) K
β = 95.19 (3)ºBlock, colorless
V = 750.5 (3) Å30.12 × 0.10 × 0.08 mm
Z = 2
Data collection top
Rigaku Saturn
diffractometer		2858 independent reflections
Radiation source: rotating anode2636 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.028
T = 113(2) Kθmax = 27.9º
ω and φ scansθmin = 2.5º
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		h = −8→8
Tmin = 0.930, Tmax = 0.953k = −15→19
5459 measured reflectionsl = −10→10
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.024  w = 1/[σ2(Fo2) + (0.0324P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.060(Δ/σ)max = 0.001
S = 1.06Δρmax = 0.21 e Å−3
2858 reflectionsΔρmin = −0.23 e Å−3
179 parametersExtinction correction: none
1 restraintAbsolute structure: Flack (1983), 996 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.04 (4)
Secondary atom site location: difference Fourier map
Crystal data top
C9H20NO+·C2Cl3O2–V = 750.5 (3) Å3
Mr = 320.63Z = 2
Monoclinic, P21Mo Kα
a = 6.3468 (13) ŵ = 0.61 mm−1
b = 14.450 (3) ÅT = 113 (2) K
c = 8.2175 (16) Å0.12 × 0.10 × 0.08 mm
β = 95.19 (3)º
Data collection top
Rigaku Saturn
diffractometer		2858 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		2636 reflections with I > 2σ(I)
Tmin = 0.930, Tmax = 0.953Rint = 0.028
5459 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.060Δρmax = 0.21 e Å−3
S = 1.06Δρmin = −0.23 e Å−3
2858 reflectionsAbsolute structure: Flack (1983), 996 Friedel pairs
179 parametersFlack 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
xyzUiso*/Ueq
Cl1−0.04464 (7)0.51471 (3)0.10942 (5)0.01980 (10)
Cl20.34863 (6)0.41431 (3)0.12885 (6)0.02203 (11)
Cl3−0.00077 (8)0.35637 (3)−0.09864 (5)0.02572 (11)
O10.7973 (2)0.47566 (9)0.51619 (17)0.0227 (3)
H10.798 (4)0.453 (2)0.415 (4)0.063 (10)*
O20.1032 (2)0.27147 (9)0.27469 (18)0.0247 (3)
O3−0.20242 (18)0.34925 (9)0.25644 (15)0.0169 (3)
N10.4803 (2)0.71305 (9)0.64562 (18)0.0111 (3)
C10.4608 (3)0.62855 (12)0.75507 (19)0.0129 (3)
C20.6286 (3)0.55858 (11)0.7135 (2)0.0139 (3)
H2A0.77010.58320.75150.017*
H2B0.60800.50050.77390.017*
C30.6235 (3)0.53661 (11)0.5324 (2)0.0159 (4)
H30.48760.50510.49450.019*
C40.6475 (3)0.62493 (13)0.4346 (2)0.0164 (3)
H4A0.63710.60900.31700.020*
H4B0.79050.65060.46380.020*
C50.4836 (3)0.69993 (12)0.46158 (19)0.0135 (3)
C60.2366 (3)0.58770 (13)0.7353 (2)0.0198 (4)
H6A0.13270.63770.73790.030*
H6B0.21910.54430.82480.030*
H6C0.21490.55500.63060.030*
C70.5076 (3)0.66393 (13)0.9293 (2)0.0189 (4)
H7A0.64950.69120.94190.028*
H7B0.50030.61241.00610.028*
H7C0.40290.71100.95190.028*
C80.2629 (3)0.67658 (13)0.3825 (2)0.0198 (4)
H8A0.15950.71930.42280.030*
H8B0.22660.61300.41040.030*
H8C0.26090.68250.26360.030*
C90.5521 (3)0.79290 (13)0.3950 (2)0.0213 (4)
H9A0.44500.83990.41230.032*
H9B0.56760.78710.27790.032*
H9C0.68780.81130.45230.032*
C100.0700 (3)0.40324 (12)0.09850 (19)0.0130 (3)
C11−0.0172 (3)0.33454 (11)0.2249 (2)0.0133 (3)
H1A0.373 (4)0.7546 (18)0.674 (3)0.037 (7)*
H1B0.610 (4)0.7410 (15)0.683 (3)0.025 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0227 (2)0.01408 (19)0.0232 (2)0.00440 (16)0.00505 (17)0.00388 (16)
Cl20.01100 (19)0.0235 (2)0.0318 (3)−0.00221 (15)0.00291 (17)0.00920 (19)
Cl30.0321 (3)0.0304 (3)0.0149 (2)−0.0025 (2)0.00289 (18)−0.00596 (17)
O10.0249 (7)0.0194 (7)0.0241 (7)0.0108 (5)0.0033 (6)−0.0052 (6)
O20.0147 (6)0.0220 (7)0.0377 (8)0.0023 (5)0.0044 (6)0.0151 (6)
O30.0125 (6)0.0160 (6)0.0230 (7)−0.0007 (5)0.0056 (5)−0.0007 (5)
N10.0114 (7)0.0098 (7)0.0124 (7)0.0007 (5)0.0033 (6)−0.0002 (5)
C10.0127 (8)0.0130 (8)0.0133 (8)0.0010 (6)0.0032 (6)0.0029 (6)
C20.0137 (8)0.0124 (8)0.0156 (9)0.0027 (6)0.0014 (7)0.0001 (6)
C30.0152 (8)0.0131 (8)0.0193 (9)0.0035 (6)0.0010 (7)−0.0028 (6)
C40.0164 (9)0.0187 (8)0.0149 (8)0.0020 (6)0.0049 (7)−0.0023 (7)
C50.0167 (8)0.0153 (8)0.0089 (7)0.0010 (6)0.0031 (6)0.0010 (6)
C60.0152 (9)0.0174 (9)0.0276 (10)−0.0007 (7)0.0059 (8)0.0059 (7)
C70.0228 (9)0.0215 (10)0.0127 (8)0.0047 (7)0.0028 (7)0.0000 (7)
C80.0196 (9)0.0215 (9)0.0176 (9)−0.0002 (7)−0.0023 (7)0.0013 (7)
C90.0272 (11)0.0164 (9)0.0214 (10)−0.0001 (7)0.0090 (8)0.0043 (7)
C100.0118 (8)0.0134 (8)0.0141 (8)0.0009 (6)0.0021 (6)0.0010 (6)
C110.0124 (8)0.0145 (8)0.0130 (8)−0.0019 (6)0.0010 (6)−0.0006 (6)
Geometric parameters (Å, °) top
Cl1—C101.7729 (17)C4—C51.532 (2)
Cl2—C101.7710 (17)C4—H4A0.9900
Cl3—C101.7756 (17)C4—H4B0.9900
O1—C31.427 (2)C5—C81.528 (2)
O1—H10.89 (3)C5—C91.529 (3)
O2—C111.235 (2)C6—H6A0.9800
O3—C111.245 (2)C6—H6B0.9800
N1—C51.526 (2)C6—H6C0.9800
N1—C11.528 (2)C7—H7A0.9800
N1—H1A0.95 (3)C7—H7B0.9800
N1—H1B0.94 (2)C7—H7C0.9800
C1—C71.524 (2)C8—H8A0.9800
C1—C21.529 (2)C8—H8B0.9800
C1—C61.535 (2)C8—H8C0.9800
C2—C31.519 (2)C9—H9A0.9800
C2—H2A0.9900C9—H9B0.9800
C2—H2B0.9900C9—H9C0.9800
C3—C41.523 (2)C10—C111.573 (2)
C3—H31.0000
C3—O1—H1112.3 (19)C8—C5—C4113.00 (15)
C5—N1—C1119.53 (13)C9—C5—C4110.55 (15)
C5—N1—H1A113.1 (15)C1—C6—H6A109.5
C1—N1—H1A105.4 (15)C1—C6—H6B109.5
C5—N1—H1B106.5 (14)H6A—C6—H6B109.5
C1—N1—H1B105.4 (13)C1—C6—H6C109.5
H1A—N1—H1B106 (2)H6A—C6—H6C109.5
C7—C1—N1105.40 (13)H6B—C6—H6C109.5
C7—C1—C2110.56 (14)C1—C7—H7A109.5
N1—C1—C2107.56 (13)C1—C7—H7B109.5
C7—C1—C6109.16 (14)H7A—C7—H7B109.5
N1—C1—C6111.62 (14)C1—C7—H7C109.5
C2—C1—C6112.31 (14)H7A—C7—H7C109.5
C3—C2—C1113.80 (14)H7B—C7—H7C109.5
C3—C2—H2A108.8C5—C8—H8A109.5
C1—C2—H2A108.8C5—C8—H8B109.5
C3—C2—H2B108.8H8A—C8—H8B109.5
C1—C2—H2B108.8C5—C8—H8C109.5
H2A—C2—H2B107.7H8A—C8—H8C109.5
O1—C3—C2105.80 (14)H8B—C8—H8C109.5
O1—C3—C4110.67 (14)C5—C9—H9A109.5
C2—C3—C4110.33 (14)C5—C9—H9B109.5
O1—C3—H3110.0H9A—C9—H9B109.5
C2—C3—H3110.0C5—C9—H9C109.5
C4—C3—H3110.0H9A—C9—H9C109.5
C3—C4—C5114.51 (14)H9B—C9—H9C109.5
C3—C4—H4A108.6C11—C10—Cl2111.74 (11)
C5—C4—H4A108.6C11—C10—Cl1111.69 (11)
C3—C4—H4B108.6Cl2—C10—Cl1108.65 (9)
C5—C4—H4B108.6C11—C10—Cl3106.67 (11)
H4A—C4—H4B107.6Cl2—C10—Cl3109.25 (9)
N1—C5—C8110.77 (14)Cl1—C10—Cl3108.77 (9)
N1—C5—C9105.97 (14)O2—C11—O3128.65 (16)
C8—C5—C9108.77 (14)O2—C11—C10116.15 (14)
N1—C5—C4107.55 (13)O3—C11—C10115.14 (14)
C5—N1—C1—C7168.77 (14)C1—N1—C5—C9−167.95 (14)
C5—N1—C1—C250.78 (19)C1—N1—C5—C4−49.69 (19)
C5—N1—C1—C6−72.85 (19)C3—C4—C5—N150.25 (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—C9165.51 (16)
C6—C1—C2—C371.08 (18)Cl2—C10—C11—O2−29.86 (19)
C1—C2—C3—O1176.40 (14)Cl1—C10—C11—O2−151.81 (14)
C1—C2—C3—C456.67 (19)Cl3—C10—C11—O289.47 (17)
O1—C3—C4—C5−172.59 (14)Cl2—C10—C11—O3152.80 (13)
C2—C3—C4—C5−55.84 (19)Cl1—C10—C11—O330.85 (18)
C1—N1—C5—C874.25 (18)Cl3—C10—C11—O3−87.87 (15)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.89 (3)1.99 (3)2.8095 (18)152 (3)
O1—H1···Cl1i0.89 (3)2.92 (3)3.6201 (16)136 (2)
N1—H1A···O3ii0.95 (3)1.87 (3)2.8085 (19)170 (2)
N1—H1B···O2iii0.94 (2)1.87 (2)2.796 (2)165.1 (19)
N1—H1B···Cl2iii0.94 (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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O3i0.89 (3)1.99 (3)2.8095 (18)152 (3)
O1—H1···Cl1i0.89 (3)2.92 (3)3.6201 (16)136 (2)
N1—H1A···O3ii0.95 (3)1.87 (3)2.8085 (19)170 (2)
N1—H1B···O2iii0.94 (2)1.87 (2)2.796 (2)165.1 (19)
N1—H1B···Cl2iii0.94 (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
References top

Borzatta, V. & Carrozza, P. (1991). European Patent EP 0 462 069.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.