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

Abstract

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,

• a = 6.3468 (13) Å

• b = 14.450 (3) Å

• c = 8.2175 (16) Å

• β = 95.19 (3)°

• V = 750.5 (3) ų

• 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[F ² > 2σ(F ²)] = 0.024

• wR(F ²) = 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)

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.

Supplementary Material

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
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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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.

Experimental

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

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

Figures

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.

Crystal data

C9H20NO+·C2Cl3O2–	F000 = 336
Mr = 320.63	Dx = 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 = 1.4–27.9º
b = 14.450 (3) Å	µ = 0.61 mm−1
c = 8.2175 (16) Å	T = 113 (2) K
β = 95.19 (3)º	Block, colorless
V = 750.5 (3) Å3	0.12 × 0.10 × 0.08 mm
Z = 2

Data collection

Rigaku Saturn diffractometer	2858 independent reflections
Radiation source: rotating anode	2636 reflections with I > 2σ(I)
Monochromator: confocal	Rint = 0.028
T = 113(2) K	θmax = 27.9º
ω and φ scans	θmin = 2.5º
Absorption correction: multi-scan(CrystalClear; Rigaku/MSC, 2005)	h = −8→8
Tmin = 0.930, Tmax = 0.953	k = −15→19
5459 measured reflections	l = −10→10

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H 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 = 1.06	Δρmax = 0.21 e Å−3
2858 reflections	Δρmin = −0.23 e Å−3
179 parameters	Extinction correction: none
1 restraint	Absolute structure: Flack (1983), 996 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.04 (4)
Secondary atom site location: difference Fourier map

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.