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

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

doi:10.1107/S1600536808002997

organic compounds

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Volume 64| Part 4| April 2008| Page o654

doi:10.1107/S1600536808002997

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

Ying Cui,^a ^* Yun-Hui Zhang ^a and Peng-Wei Zhang ^a

^aSchool of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, People's Republic of China
^*Correspondence e-mail: flyingyting@yahoo.com.cn

(Received 15 January 2008; accepted 28 January 2008; online 5 March 2008)

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

Related literature

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

Experimental

Crystal data

C₉H₂₀NO⁺·ClO₄⁻
M_r = 257.71
Monoclinic, P 2₁ /n
a = 7.5712 (15) Å
b = 13.927 (3) Å
c = 12.007 (2) Å
β = 100.71 (3)°
V = 1244.0 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 113 (2) K
0.12 × 0.04 × 0.04 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ) T_min = 0.963, T_max = 0.988
7480 measured reflections
2183 independent reflections
1797 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.127
S = 1.10
2183 reflections
157 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4ⁱ	0.92 (3)	2.05 (3)	2.914 (3)	157 (2)
N1—H1B⋯O1ⁱⁱ	0.88 (3)	1.97 (3)	2.847 (3)	173 (2)
O1—H1⋯O2ⁱⁱⁱ	0.82	2.09	2.896 (2)	167
O1—H1⋯Cl1ⁱⁱⁱ	0.82	2.93	3.6985 (16)	158
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (iii) 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/S1600536808002997/hg2373sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808002997/hg2373Isup2.hkl

checkCIF report

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.

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. 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⁻	F(000) = 552
M_r = 257.71	D_x = 1.376 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2824 reflections
a = 7.5712 (15) Å	θ = 2.3–28.1°
b = 13.927 (3) Å	µ = 0.31 mm⁻¹
c = 12.007 (2) Å	T = 113 K
β = 100.71 (3)°	Block, colorless
V = 1244.0 (4) Å³	0.12 × 0.04 × 0.04 mm
Z = 4

Data collection top

Rigaku Saturn diffractometer	2183 independent reflections
Radiation source: rotating anode	1797 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.046
Detector resolution: 7.31 pixels mm^-1	θ_max = 25.0°, θ_min = 2.3°
ω and ϕ scans	h = −9→7
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −11→16
T_min = 0.963, T_max = 0.988	l = −13→14
7480 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.0763P)² + 0.0376P] where P = (F_o² + 2F_c²)/3
2183 reflections	(Δ/σ)_max = 0.001
157 parameters	Δρ_max = 0.60 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

C₉H₂₀NO⁺·ClO₄⁻	V = 1244.0 (4) Å³
M_r = 257.71	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.5712 (15) Å	µ = 0.31 mm⁻¹
b = 13.927 (3) Å	T = 113 K
c = 12.007 (2) Å	0.12 × 0.04 × 0.04 mm
β = 100.71 (3)°

Data collection top

Rigaku Saturn diffractometer	2183 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	1797 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.988	R_int = 0.046
7480 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.60 e Å⁻³
2183 reflections	Δρ_min = −0.48 e Å⁻³
157 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
O1	0.8859 (2)	0.66280 (10)	0.28774 (12)	0.0224 (4)
H1	0.9165	0.6118	0.2631	0.034*
N1	0.6419 (2)	0.74364 (13)	−0.04347 (15)	0.0172 (4)
H1A	0.694 (4)	0.6951 (17)	−0.078 (2)	0.027 (6)*
H1B	0.570 (4)	0.7733 (17)	−0.099 (2)	0.029 (7)*
C1	0.7957 (3)	0.80834 (14)	0.01410 (18)	0.0200 (5)
C2	0.8982 (3)	0.75325 (14)	0.11605 (18)	0.0216 (5)
H2A	0.9652	0.7001	0.0882	0.026*
H2B	0.9874	0.7969	0.1609	0.026*
C3	0.7796 (3)	0.71199 (14)	0.19322 (16)	0.0184 (5)
H3	0.7150	0.7661	0.2230	0.022*
C4	0.6403 (3)	0.64456 (14)	0.12660 (17)	0.0187 (5)
H4A	0.5646	0.6181	0.1782	0.022*
H4B	0.7030	0.5902	0.0977	0.022*
C5	0.5198 (3)	0.69386 (14)	0.02718 (17)	0.0188 (5)
C6	0.3909 (3)	0.76627 (15)	0.06528 (19)	0.0240 (5)
H6A	0.3364	0.8060	0.0006	0.036*
H6B	0.4574	0.8073	0.1250	0.036*
H6C	0.2963	0.7318	0.0946	0.036*
C7	0.4117 (3)	0.62072 (15)	−0.05253 (19)	0.0248 (5)
H7A	0.4940	0.5759	−0.0797	0.037*
H7B	0.3397	0.6542	−0.1172	0.037*
H7C	0.3319	0.5851	−0.0118	0.037*
C8	0.9141 (3)	0.82429 (17)	−0.0744 (2)	0.0292 (6)
H8A	1.0164	0.8651	−0.0422	0.044*
H8B	0.8437	0.8557	−0.1412	0.044*
H8C	0.9582	0.7623	−0.0965	0.044*
C9	0.7249 (3)	0.90544 (15)	0.0458 (2)	0.0277 (5)
H9A	0.6607	0.8970	0.1088	0.042*
H9B	0.6427	0.9320	−0.0197	0.042*
H9C	0.8259	0.9496	0.0685	0.042*
Cl1	0.15810 (8)	0.46849 (3)	0.19458 (5)	0.0256 (2)
O2	−0.0091 (3)	0.47048 (12)	0.23547 (17)	0.0431 (5)
O3	0.2067 (3)	0.56462 (12)	0.17449 (16)	0.0423 (5)
O4	0.1359 (3)	0.41692 (15)	0.08989 (19)	0.0627 (7)
O5	0.2955 (3)	0.42562 (16)	0.2770 (2)	0.0603 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0226 (9)	0.0236 (8)	0.0180 (7)	0.0044 (6)	−0.0039 (7)	−0.0023 (6)
N1	0.0133 (10)	0.0196 (9)	0.0184 (9)	0.0023 (7)	0.0026 (8)	0.0006 (7)
C1	0.0124 (11)	0.0205 (11)	0.0266 (12)	−0.0036 (8)	0.0023 (10)	−0.0006 (8)
C2	0.0135 (11)	0.0233 (11)	0.0262 (11)	−0.0014 (8)	−0.0012 (10)	−0.0017 (8)
C3	0.0153 (12)	0.0205 (10)	0.0173 (10)	0.0024 (8)	−0.0021 (9)	−0.0012 (8)
C4	0.0159 (11)	0.0203 (10)	0.0191 (11)	−0.0012 (8)	0.0009 (9)	0.0001 (8)
C5	0.0146 (12)	0.0202 (10)	0.0218 (11)	−0.0040 (8)	0.0040 (10)	0.0013 (8)
C6	0.0141 (12)	0.0292 (12)	0.0300 (12)	0.0026 (9)	0.0075 (10)	0.0034 (9)
C7	0.0222 (13)	0.0248 (11)	0.0240 (12)	−0.0065 (9)	−0.0043 (10)	0.0025 (9)
C8	0.0194 (13)	0.0350 (13)	0.0344 (13)	0.0002 (10)	0.0081 (11)	0.0099 (10)
C9	0.0241 (13)	0.0215 (12)	0.0365 (13)	−0.0024 (9)	0.0030 (11)	−0.0001 (9)
Cl1	0.0215 (4)	0.0218 (3)	0.0361 (4)	0.0047 (2)	0.0119 (3)	0.0035 (2)
O2	0.0254 (11)	0.0522 (12)	0.0575 (13)	0.0051 (8)	0.0223 (10)	0.0141 (8)
O3	0.0465 (13)	0.0299 (10)	0.0501 (11)	−0.0063 (8)	0.0079 (10)	0.0074 (8)
O4	0.0644 (16)	0.0566 (13)	0.0694 (15)	0.0081 (11)	0.0189 (13)	−0.0359 (11)
O5	0.0340 (12)	0.0705 (15)	0.0760 (15)	0.0229 (10)	0.0091 (12)	0.0437 (12)

Geometric parameters (Å, º) top

O1—C3	1.437 (2)	C5—C6	1.532 (3)
O1—H1	0.8199	C6—H6A	0.9800
N1—C1	1.532 (3)	C6—H6B	0.9800
N1—C5	1.532 (3)	C6—H6C	0.9800
N1—H1A	0.92 (3)	C7—H7A	0.9800
N1—H1B	0.88 (3)	C7—H7B	0.9800
C1—C9	1.528 (3)	C7—H7C	0.9800
C1—C2	1.529 (3)	C8—H8A	0.9800
C1—C8	1.529 (3)	C8—H8B	0.9800
C2—C3	1.518 (3)	C8—H8C	0.9800
C2—H2A	0.9900	C9—H9A	0.9800
C2—H2B	0.9900	C9—H9B	0.9800
C3—C4	1.523 (3)	C9—H9C	0.9800
C3—H3	1.0000	Cl1—O3	1.4210 (18)
C4—C5	1.524 (3)	Cl1—O5	1.427 (2)
C4—H4A	0.9900	Cl1—O4	1.430 (2)
C4—H4B	0.9900	Cl1—O2	1.4408 (18)
C5—C7	1.527 (3)

C3—O1—H1	106.4	C4—C5—N1	107.61 (17)
C1—N1—C5	120.17 (16)	C7—C5—N1	105.26 (16)
C1—N1—H1A	106.5 (16)	C6—C5—N1	110.57 (16)
C5—N1—H1A	105.7 (15)	C5—C6—H6A	109.5
C1—N1—H1B	112.1 (16)	C5—C6—H6B	109.5
C5—N1—H1B	106.2 (16)	H6A—C6—H6B	109.5
H1A—N1—H1B	105 (2)	C5—C6—H6C	109.5
C9—C1—C2	113.22 (18)	H6A—C6—H6C	109.5
C9—C1—C8	108.82 (17)	H6B—C6—H6C	109.5
C2—C1—C8	110.68 (18)	C5—C7—H7A	109.5
C9—C1—N1	111.14 (18)	C5—C7—H7B	109.5
C2—C1—N1	107.24 (16)	H7A—C7—H7B	109.5
C8—C1—N1	105.46 (17)	C5—C7—H7C	109.5
C3—C2—C1	114.12 (18)	H7A—C7—H7C	109.5
C3—C2—H2A	108.7	H7B—C7—H7C	109.5
C1—C2—H2A	108.7	C1—C8—H8A	109.5
C3—C2—H2B	108.7	C1—C8—H8B	109.5
C1—C2—H2B	108.7	H8A—C8—H8B	109.5
H2A—C2—H2B	107.6	C1—C8—H8C	109.5
O1—C3—C2	110.75 (17)	H8A—C8—H8C	109.5
O1—C3—C4	110.62 (16)	H8B—C8—H8C	109.5
C2—C3—C4	110.06 (16)	C1—C9—H9A	109.5
O1—C3—H3	108.4	C1—C9—H9B	109.5
C2—C3—H3	108.4	H9A—C9—H9B	109.5
C4—C3—H3	108.4	C1—C9—H9C	109.5
C3—C4—C5	112.87 (16)	H9A—C9—H9C	109.5
C3—C4—H4A	109.0	H9B—C9—H9C	109.5
C5—C4—H4A	109.0	O3—Cl1—O5	109.47 (13)
C3—C4—H4B	109.0	O3—Cl1—O4	108.40 (13)
C5—C4—H4B	109.0	O5—Cl1—O4	110.53 (14)
H4A—C4—H4B	107.8	O3—Cl1—O2	108.16 (11)
C4—C5—C7	111.31 (16)	O5—Cl1—O2	110.23 (11)
C4—C5—C6	112.63 (16)	O4—Cl1—O2	110.00 (13)
C7—C5—C6	109.21 (18)

C5—N1—C1—C9	−76.1 (2)	O1—C3—C4—C5	178.28 (15)
C5—N1—C1—C2	48.2 (2)	C2—C3—C4—C5	−59.0 (2)
C5—N1—C1—C8	166.19 (18)	C3—C4—C5—C7	167.26 (17)
C9—C1—C2—C3	72.5 (2)	C3—C4—C5—C6	−69.7 (2)
C8—C1—C2—C3	−165.05 (17)	C3—C4—C5—N1	52.4 (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—C4	58.3 (2)	C1—N1—C5—C6	73.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.92 (3)	2.05 (3)	2.914 (3)	157 (2)
N1—H1B···O1ⁱⁱ	0.88 (3)	1.97 (3)	2.847 (3)	173 (2)
O1—H1···O2ⁱⁱⁱ	0.82	2.09	2.896 (2)	167
O1—H1···Cl1ⁱⁱⁱ	0.82	2.93	3.6985 (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.

Experimental details

Crystal data
Chemical formula	C₉H₂₀NO⁺·ClO₄⁻
M_r	257.71
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	113
a, b, c (Å)	7.5712 (15), 13.927 (3), 12.007 (2)
β (°)	100.71 (3)
V (Å³)	1244.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.12 × 0.04 × 0.04

Data collection
Diffractometer	Rigaku Saturn diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.963, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	7480, 2183, 1797
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.127, 1.10
No. of reflections	2183
No. of parameters	157
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.60, −0.48

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
N1—H1A···O4ⁱ	0.92 (3)	2.05 (3)	2.914 (3)	157 (2)
N1—H1B···O1ⁱⁱ	0.88 (3)	1.97 (3)	2.847 (3)	173 (2)
O1—H1···O2ⁱⁱⁱ	0.82	2.09	2.896 (2)	167.4
O1—H1···Cl1ⁱⁱⁱ	0.82	2.93	3.6985 (16)	157.9

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1/2, −y+3/2, z−1/2; (iii) x+1, y, z.

References

Borzatta, V. & Carrozza, P. (1991). Eur. Patent No. EP 0 462 069. Google Scholar
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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doi:10.1107/S1600536808002997

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