organic compounds
4-Hydroxy-2,2,6,6-tetramethylpiperidinium trichloroacetate
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
In the 9H20NO+·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.
of the title compound, CExperimental
Crystal data
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Data collection: CrystalClear (Rigaku/MSC, 2005); cell 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
10.1107/S1600536808005369/hg2380sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808005369/hg2380Isup2.hkl
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.
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.
Data collection: CrystalClear (Rigaku/MSC, 2005); cell
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).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. |
C9H20NO+·C2Cl3O2− | F(000) = 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 = 1.4–27.9° |
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 |
Rigaku Saturn diffractometer | 2858 independent reflections |
Radiation source: rotating anode | 2636 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.028 |
ω and ϕ scans | θmax = 27.9°, θmin = 2.5° |
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 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(Fo2) + (0.0324P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
2858 reflections | Δρmax = 0.21 e Å−3 |
179 parameters | Δρmin = −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) |
C9H20NO+·C2Cl3O2− | V = 750.5 (3) Å3 |
Mr = 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)° |
Rigaku Saturn diffractometer | 2858 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 2636 reflections with I > 2σ(I) |
Tmin = 0.930, Tmax = 0.953 | Rint = 0.028 |
5459 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.060 | Δρmax = 0.21 e Å−3 |
S = 1.06 | Δρmin = −0.23 e Å−3 |
2858 reflections | Absolute structure: Flack (1983), 996 Friedel pairs |
179 parameters | Absolute structure parameter: 0.04 (4) |
1 restraint |
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. |
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)* |
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) |
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) |
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− |
Mr | 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) |
Tmin, Tmax | 0.930, 0.953 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5459, 2858, 2636 |
Rint | 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 |
Δρmax, Δρmin (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).
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
Borzatta, V. & Carrozza, P. (1991). European Patent EP 0 462 069. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Rigaku/MSC (2005). CrystalClear. 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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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.