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Acta Cryst. (2008). E64, o654    [ doi:10.1107/S1600536808002997 ]

4-Hydroxy-2,2,6,6-tetramethylpiperidinium perchlorate

Y. Cui, Y.-H. Zhang and P.-W. Zhang

Abstract top

In the title salt, C9H20NO+·ClO4-, intermolecular hydrogen bonds are observed, which determine the crystal packing.

Comment top

2,2,6,6-Tetramethyl-4-hydroxy-piperidin-4-ol is a very important intermediate in the synthesis of hindered light stabilizers (Borzatta & Carrozza, 1991). We report here the crystal structure (2,2,6,6-tetramethyl-4-hydroxypiperidinium perchlorate) (Fig. 1).

Intermolecular N—H···O, O—H···O, O—H···Cl hydrogen bonds are observed which help to establish the crystal packing. The piperidine ring adopts chair conformation.

Related literature top

For general background, see Borzatta & Carrozza (1991).

Experimental top

2,2,6,6-tetramethylpiperidin-4-ol (3.2 mmol,0.5 g) was dissolved in perchloric acid solution(2.5 mol/l, 3 ml). Block shaped colorless crystals grew with slow evaporation of solvent.

Refinement top

All H atoms were constrained; positioned geometrically (C—H = 0.99–1.00 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier) or 1.5eq(methyl groups).

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. A view of the molecule (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
4-Hydroxy-2,2,6,6-tetramethylpiperidinium perchlorate top
Crystal data top
C9H20NO+·ClO4–F000 = 552
Mr = 257.71Dx = 1.376 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2824 reflections
a = 7.5712 (15) Åθ = 2.3–28.1º
b = 13.927 (3) ŵ = 0.31 mm−1
c = 12.007 (2) ÅT = 113 (2) K
β = 100.71 (3)ºBlock, colorless
V = 1244.0 (4) Å30.12 × 0.04 × 0.04 mm
Z = 4
Data collection top
Rigaku Saturn
diffractometer		2183 independent reflections
Radiation source: rotating anode1797 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.046
Detector resolution: 7.31 pixels mm-1θmax = 25.0º
T = 113(2) Kθmin = 2.3º
ω and φ scansh = −9→7
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		k = −11→16
Tmin = 0.963, Tmax = 0.988l = −13→14
7480 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.127  w = 1/[σ2(Fo2) + (0.0763P)2 + 0.0376P]
where P = (Fo2 + 2Fc2)/3
S = 1.10(Δ/σ)max = 0.001
2183 reflectionsΔρmax = 0.60 e Å−3
157 parametersΔρmin = −0.48 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C9H20NO+·ClO4–V = 1244.0 (4) Å3
Mr = 257.71Z = 4
Monoclinic, P21/nMo Kα
a = 7.5712 (15) ŵ = 0.31 mm−1
b = 13.927 (3) ÅT = 113 (2) K
c = 12.007 (2) Å0.12 × 0.04 × 0.04 mm
β = 100.71 (3)º
Data collection top
Rigaku Saturn
diffractometer		2183 independent reflections
Absorption correction: multi-scan
(CrystalClear; Rigaku/MSC, 2005)		1797 reflections with I > 2σ(I)
Tmin = 0.963, Tmax = 0.988Rint = 0.046
7480 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045157 parameters
wR(F2) = 0.127H atoms treated by a mixture of
independent and constrained refinement
S = 1.10Δρmax = 0.60 e Å−3
2183 reflectionsΔρmin = −0.48 e Å−3
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
O10.8859 (2)0.66280 (10)0.28774 (12)0.0224 (4)
H10.91650.61180.26310.034*
N10.6419 (2)0.74364 (13)−0.04347 (15)0.0172 (4)
H1A0.694 (4)0.6951 (17)−0.078 (2)0.027 (6)*
H1B0.570 (4)0.7733 (17)−0.099 (2)0.029 (7)*
C10.7957 (3)0.80834 (14)0.01410 (18)0.0200 (5)
C20.8982 (3)0.75325 (14)0.11605 (18)0.0216 (5)
H2A0.96520.70010.08820.026*
H2B0.98740.79690.16090.026*
C30.7796 (3)0.71199 (14)0.19322 (16)0.0184 (5)
H30.71500.76610.22300.022*
C40.6403 (3)0.64456 (14)0.12660 (17)0.0187 (5)
H4A0.56460.61810.17820.022*
H4B0.70300.59020.09770.022*
C50.5198 (3)0.69386 (14)0.02718 (17)0.0188 (5)
C60.3909 (3)0.76627 (15)0.06528 (19)0.0240 (5)
H6A0.33640.80600.00060.036*
H6B0.45740.80730.12500.036*
H6C0.29630.73180.09460.036*
C70.4117 (3)0.62072 (15)−0.05253 (19)0.0248 (5)
H7A0.49400.5759−0.07970.037*
H7B0.33970.6542−0.11720.037*
H7C0.33190.5851−0.01180.037*
C80.9141 (3)0.82429 (17)−0.0744 (2)0.0292 (6)
H8A1.01640.8651−0.04220.044*
H8B0.84370.8557−0.14120.044*
H8C0.95820.7623−0.09650.044*
C90.7249 (3)0.90544 (15)0.0458 (2)0.0277 (5)
H9A0.66070.89700.10880.042*
H9B0.64270.9320−0.01970.042*
H9C0.82590.94960.06850.042*
Cl10.15810 (8)0.46849 (3)0.19458 (5)0.0256 (2)
O2−0.0091 (3)0.47048 (12)0.23547 (17)0.0431 (5)
O30.2067 (3)0.56462 (12)0.17449 (16)0.0423 (5)
O40.1359 (3)0.41692 (15)0.08989 (19)0.0627 (7)
O50.2955 (3)0.42562 (16)0.2770 (2)0.0603 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0226 (9)0.0236 (8)0.0180 (7)0.0044 (6)−0.0039 (7)−0.0023 (6)
N10.0133 (10)0.0196 (9)0.0184 (9)0.0023 (7)0.0026 (8)0.0006 (7)
C10.0124 (11)0.0205 (11)0.0266 (12)−0.0036 (8)0.0023 (10)−0.0006 (8)
C20.0135 (11)0.0233 (11)0.0262 (11)−0.0014 (8)−0.0012 (10)−0.0017 (8)
C30.0153 (12)0.0205 (10)0.0173 (10)0.0024 (8)−0.0021 (9)−0.0012 (8)
C40.0159 (11)0.0203 (10)0.0191 (11)−0.0012 (8)0.0009 (9)0.0001 (8)
C50.0146 (12)0.0202 (10)0.0218 (11)−0.0040 (8)0.0040 (10)0.0013 (8)
C60.0141 (12)0.0292 (12)0.0300 (12)0.0026 (9)0.0075 (10)0.0034 (9)
C70.0222 (13)0.0248 (11)0.0240 (12)−0.0065 (9)−0.0043 (10)0.0025 (9)
C80.0194 (13)0.0350 (13)0.0344 (13)0.0002 (10)0.0081 (11)0.0099 (10)
C90.0241 (13)0.0215 (12)0.0365 (13)−0.0024 (9)0.0030 (11)−0.0001 (9)
Cl10.0215 (4)0.0218 (3)0.0361 (4)0.0047 (2)0.0119 (3)0.0035 (2)
O20.0254 (11)0.0522 (12)0.0575 (13)0.0051 (8)0.0223 (10)0.0141 (8)
O30.0465 (13)0.0299 (10)0.0501 (11)−0.0063 (8)0.0079 (10)0.0074 (8)
O40.0644 (16)0.0566 (13)0.0694 (15)0.0081 (11)0.0189 (13)−0.0359 (11)
O50.0340 (12)0.0705 (15)0.0760 (15)0.0229 (10)0.0091 (12)0.0437 (12)
Geometric parameters (Å, °) top
O1—C31.437 (2)C5—C61.532 (3)
O1—H10.8199C6—H6A0.9800
N1—C11.532 (3)C6—H6B0.9800
N1—C51.532 (3)C6—H6C0.9800
N1—H1A0.92 (3)C7—H7A0.9800
N1—H1B0.88 (3)C7—H7B0.9800
C1—C91.528 (3)C7—H7C0.9800
C1—C21.529 (3)C8—H8A0.9800
C1—C81.529 (3)C8—H8B0.9800
C2—C31.518 (3)C8—H8C0.9800
C2—H2A0.9900C9—H9A0.9800
C2—H2B0.9900C9—H9B0.9800
C3—C41.523 (3)C9—H9C0.9800
C3—H31.0000Cl1—O31.4210 (18)
C4—C51.524 (3)Cl1—O51.427 (2)
C4—H4A0.9900Cl1—O41.430 (2)
C4—H4B0.9900Cl1—O21.4408 (18)
C5—C71.527 (3)
C3—O1—H1106.4C4—C5—N1107.61 (17)
C1—N1—C5120.17 (16)C7—C5—N1105.26 (16)
C1—N1—H1A106.5 (16)C6—C5—N1110.57 (16)
C5—N1—H1A105.7 (15)C5—C6—H6A109.5
C1—N1—H1B112.1 (16)C5—C6—H6B109.5
C5—N1—H1B106.2 (16)H6A—C6—H6B109.5
H1A—N1—H1B105 (2)C5—C6—H6C109.5
C9—C1—C2113.22 (18)H6A—C6—H6C109.5
C9—C1—C8108.82 (17)H6B—C6—H6C109.5
C2—C1—C8110.68 (18)C5—C7—H7A109.5
C9—C1—N1111.14 (18)C5—C7—H7B109.5
C2—C1—N1107.24 (16)H7A—C7—H7B109.5
C8—C1—N1105.46 (17)C5—C7—H7C109.5
C3—C2—C1114.12 (18)H7A—C7—H7C109.5
C3—C2—H2A108.7H7B—C7—H7C109.5
C1—C2—H2A108.7C1—C8—H8A109.5
C3—C2—H2B108.7C1—C8—H8B109.5
C1—C2—H2B108.7H8A—C8—H8B109.5
H2A—C2—H2B107.6C1—C8—H8C109.5
O1—C3—C2110.75 (17)H8A—C8—H8C109.5
O1—C3—C4110.62 (16)H8B—C8—H8C109.5
C2—C3—C4110.06 (16)C1—C9—H9A109.5
O1—C3—H3108.4C1—C9—H9B109.5
C2—C3—H3108.4H9A—C9—H9B109.5
C4—C3—H3108.4C1—C9—H9C109.5
C3—C4—C5112.87 (16)H9A—C9—H9C109.5
C3—C4—H4A109.0H9B—C9—H9C109.5
C5—C4—H4A109.0O3—Cl1—O5109.47 (13)
C3—C4—H4B109.0O3—Cl1—O4108.40 (13)
C5—C4—H4B109.0O5—Cl1—O4110.53 (14)
H4A—C4—H4B107.8O3—Cl1—O2108.16 (11)
C4—C5—C7111.31 (16)O5—Cl1—O2110.23 (11)
C4—C5—C6112.63 (16)O4—Cl1—O2110.00 (13)
C7—C5—C6109.21 (18)
C5—N1—C1—C9−76.1 (2)O1—C3—C4—C5178.28 (15)
C5—N1—C1—C248.2 (2)C2—C3—C4—C5−59.0 (2)
C5—N1—C1—C8166.19 (18)C3—C4—C5—C7167.26 (17)
C9—C1—C2—C372.5 (2)C3—C4—C5—C6−69.7 (2)
C8—C1—C2—C3−165.05 (17)C3—C4—C5—N152.4 (2)
N1—C1—C2—C3−50.5 (2)C1—N1—C5—C4−49.6 (2)
C1—C2—C3—O1−179.04 (15)C1—N1—C5—C7−168.37 (17)
C1—C2—C3—C458.3 (2)C1—N1—C5—C673.8 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4i0.92 (3)2.05 (3)2.914 (3)157 (2)
N1—H1B···O1ii0.88 (3)1.97 (3)2.847 (3)173 (2)
O1—H1···O2iii0.822.092.896 (2)167
O1—H1···Cl1iii0.822.933.6985 (16)158
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x+1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O4i0.92 (3)2.05 (3)2.914 (3)157 (2)
N1—H1B···O1ii0.88 (3)1.97 (3)2.847 (3)173 (2)
O1—H1···O2iii0.822.092.896 (2)167
O1—H1···Cl1iii0.822.933.6985 (16)158
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x+1, y, z.
references
References top

Borzatta, V. & Carrozza, P. (1991). Eur. Patent No. EP 0 462 069.

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

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