




Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808002158/nc2088sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808002158/nc2088Isup2.hkl |
CCDC reference: 677644
Key indicators
- Single-crystal X-ray study
- T = 113 K
- Mean
(C-C) = 0.003 Å
- Disorder in main residue
- R factor = 0.051
- wR factor = 0.130
- Data-to-parameter ratio = 22.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.17 Ratio PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT301_ALERT_3_C Main Residue Disorder ......................... 7.00 Perc. PLAT417_ALERT_2_C Short Inter D-H..H-D H1 .. H2 .. 2.13 Ang. PLAT417_ALERT_2_C Short Inter D-H..H-D H1 .. H2 .. 2.13 Ang. PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 92.00 A 3 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.12 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
0.25 g(1.6 mmol) of 2,2,6,6-tetramethylpiperidin-4-ol was dissolved in 3.2 ml of hydrochloric acid (3.2 mmol. Colorless crystals of the title compound were obtained by slow evaporation of the solvent.
The C—H and N—H H atoms were positioned with idealized geometry (methyl allowed to rotate but not to tip) and refined isotropic with Uiso(H)=1.2 Ueq(carrier atom; 1.5 for methyl H atoms) using a riding model with C—H = 0.98 - 1.00Å and N—H = 1.00 Å. The O—H H atoms were located in different map, their bond length were set to 0.85Å and afterwards they were refined isotropic (Uiso(H)=1.2Ueq(carrier atom)) using a riding model.
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).
C9H20NO+·Cl−·0.33(H3O+·Cl−) | Dx = 1.170 Mg m−3 |
Mr = 211.87 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P63/m | Cell parameters from 4368 reflections |
a = 13.4460 (19) Å | θ = 1.8–27.9° |
c = 11.528 (2) Å | µ = 0.36 mm−1 |
V = 1804.9 (5) Å3 | T = 113 K |
Z = 6 | Block, colorless |
F(000) = 692 | 0.10 × 0.10 × 0.04 mm |
Rigaku Saturn diffractometer | 1513 independent reflections |
Radiation source: rotating anode | 1424 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.075 |
Detector resolution: 7.31 pixels mm-1 | θmax = 27.9°, θmin = 2.5° |
ω scans | h = −13→17 |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | k = −17→16 |
Tmin = 0.968, Tmax = 0.989 | l = −14→15 |
14051 measured reflections |
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0699P)2 + 0.5807P] where P = (Fo2 + 2Fc2)/3 |
1513 reflections | (Δ/σ)max < 0.001 |
68 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C9H20NO+·Cl−·0.33(H3O+·Cl−) | Z = 6 |
Mr = 211.87 | Mo Kα radiation |
Hexagonal, P63/m | µ = 0.36 mm−1 |
a = 13.4460 (19) Å | T = 113 K |
c = 11.528 (2) Å | 0.10 × 0.10 × 0.04 mm |
V = 1804.9 (5) Å3 |
Rigaku Saturn diffractometer | 1513 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 1424 reflections with I > 2σ(I) |
Tmin = 0.968, Tmax = 0.989 | Rint = 0.075 |
14051 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.33 e Å−3 |
1513 reflections | Δρmin = −0.26 e Å−3 |
68 parameters |
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 | Occ. (<1) | |
O1 | −0.13431 (15) | 0.43006 (16) | 0.2500 | 0.0420 (6) | |
H1 | −0.0986 | 0.5031 | 0.2500 | 0.050* | |
N1 | 0.16134 (16) | 0.39830 (16) | 0.2500 | 0.0174 (4) | |
H1B | 0.2019 | 0.3598 | 0.2500 | 0.021* | |
H1C | 0.2145 | 0.4755 | 0.2500 | 0.021* | |
C1 | −0.0587 (2) | 0.3833 (2) | 0.2500 | 0.0283 (6) | |
H1A | −0.1063 | 0.2976 | 0.2500 | 0.034* | |
C2 | 0.01605 (15) | 0.42088 (15) | 0.35766 (18) | 0.0260 (4) | |
H2A | −0.0339 | 0.3965 | 0.4271 | 0.031* | |
H2B | 0.0625 | 0.5058 | 0.3587 | 0.031* | |
C3 | 0.09668 (15) | 0.37155 (15) | 0.36468 (16) | 0.0213 (4) | |
C4 | 0.03335 (16) | 0.24188 (16) | 0.38919 (18) | 0.0279 (4) | |
H4A | −0.0362 | 0.2037 | 0.3415 | 0.042* | |
H4B | 0.0123 | 0.2284 | 0.4714 | 0.042* | |
H4C | 0.0836 | 0.2108 | 0.3702 | 0.042* | |
C5 | 0.18849 (18) | 0.43315 (17) | 0.45708 (17) | 0.0302 (4) | |
H5A | 0.2438 | 0.4060 | 0.4542 | 0.045* | |
H5B | 0.1523 | 0.4170 | 0.5338 | 0.045* | |
H5C | 0.2283 | 0.5161 | 0.4426 | 0.045* | |
Cl1 | 0.6667 | 0.3333 | 0.7500 | 0.0219 (3) | |
Cl2 | 0.71701 (5) | 0.03169 (5) | 0.2500 | 0.0244 (2) | |
O2 | 0.6667 | 0.3333 | 0.3252 (4) | 0.0276 (10) | 0.50 |
H2 | 0.7352 | 0.3704 | 0.2999 | 0.041* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0168 (9) | 0.0200 (9) | 0.091 (2) | 0.0103 (8) | 0.000 | 0.000 |
N1 | 0.0169 (9) | 0.0186 (9) | 0.0159 (11) | 0.0083 (8) | 0.000 | 0.000 |
C1 | 0.0176 (12) | 0.0170 (11) | 0.052 (2) | 0.0096 (9) | 0.000 | 0.000 |
C2 | 0.0239 (9) | 0.0212 (8) | 0.0318 (11) | 0.0105 (7) | 0.0114 (8) | 0.0049 (7) |
C3 | 0.0232 (8) | 0.0232 (8) | 0.0173 (9) | 0.0114 (7) | 0.0050 (7) | 0.0036 (6) |
C4 | 0.0278 (9) | 0.0248 (9) | 0.0313 (11) | 0.0133 (8) | 0.0075 (8) | 0.0092 (8) |
C5 | 0.0376 (10) | 0.0329 (10) | 0.0162 (10) | 0.0146 (9) | −0.0007 (8) | 0.0022 (8) |
Cl1 | 0.0202 (3) | 0.0202 (3) | 0.0254 (6) | 0.01012 (16) | 0.000 | 0.000 |
Cl2 | 0.0251 (3) | 0.0203 (3) | 0.0295 (4) | 0.0125 (2) | 0.000 | 0.000 |
O2 | 0.0243 (14) | 0.0243 (14) | 0.034 (3) | 0.0121 (7) | 0.000 | 0.000 |
O1—C1 | 1.438 (3) | C2—H2B | 0.9900 |
O1—H1 | 0.8500 | C3—C5 | 1.524 (3) |
N1—C3 | 1.523 (2) | C3—C4 | 1.536 (2) |
N1—C3i | 1.523 (2) | C4—H4A | 0.9800 |
N1—H1B | 0.9200 | C4—H4B | 0.9800 |
N1—H1C | 0.9200 | C4—H4C | 0.9800 |
C1—C2 | 1.516 (2) | C5—H5A | 0.9800 |
C1—C2i | 1.516 (2) | C5—H5B | 0.9800 |
C1—H1A | 1.0000 | C5—H5C | 0.9800 |
C2—C3 | 1.530 (2) | O2—O2i | 1.733 (10) |
C2—H2A | 0.9900 | O2—H2 | 0.8501 |
C1—O1—H1 | 113.0 | N1—C3—C5 | 105.47 (14) |
C3—N1—C3i | 120.43 (18) | N1—C3—C2 | 107.23 (15) |
C3—N1—H1B | 107.2 | C5—C3—C2 | 111.00 (16) |
C3i—N1—H1B | 107.2 | N1—C3—C4 | 110.77 (15) |
C3—N1—H1C | 107.2 | C5—C3—C4 | 109.09 (15) |
C3i—N1—H1C | 107.2 | C2—C3—C4 | 113.01 (14) |
H1B—N1—H1C | 106.9 | C3—C4—H4A | 109.5 |
O1—C1—C2 | 110.50 (13) | C3—C4—H4B | 109.5 |
O1—C1—C2i | 110.51 (13) | H4A—C4—H4B | 109.5 |
C2—C1—C2i | 109.9 (2) | C3—C4—H4C | 109.5 |
O1—C1—H1A | 108.6 | H4A—C4—H4C | 109.5 |
C2—C1—H1A | 108.6 | H4B—C4—H4C | 109.5 |
C2i—C1—H1A | 108.6 | C3—C5—H5A | 109.5 |
C1—C2—C3 | 113.23 (16) | C3—C5—H5B | 109.5 |
C1—C2—H2A | 108.9 | H5A—C5—H5B | 109.5 |
C3—C2—H2A | 108.9 | C3—C5—H5C | 109.5 |
C1—C2—H2B | 108.9 | H5A—C5—H5C | 109.5 |
C3—C2—H2B | 108.9 | H5B—C5—H5C | 109.5 |
H2A—C2—H2B | 107.7 | O2i—O2—H2 | 69.9 |
O1—C1—C2—C3 | 178.55 (15) | C3i—N1—C3—C4 | 74.5 (2) |
C2i—C1—C2—C3 | −59.2 (2) | C1—C2—C3—N1 | 51.7 (2) |
C3i—N1—C3—C5 | −167.57 (14) | C1—C2—C3—C5 | 166.46 (16) |
C3i—N1—C3—C2 | −49.2 (2) | C1—C2—C3—C4 | −70.6 (2) |
Symmetry code: (i) x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cl2ii | 0.85 | 2.15 | 2.991 (2) | 172 |
N1—H1B···Cl2iii | 0.92 | 2.22 | 3.139 (2) | 175 |
N1—H1C···Cl1iv | 0.92 | 2.25 | 3.166 (2) | 176 |
O2—H2···O1v | 0.85 | 1.63 | 2.475 (2) | 175 |
Symmetry codes: (ii) −y, x−y, z; (iii) −x+y+1, −x+1, z; (iv) −x+1, −y+1, −z+1; (v) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C9H20NO+·Cl−·0.33(H3O+·Cl−) |
Mr | 211.87 |
Crystal system, space group | Hexagonal, P63/m |
Temperature (K) | 113 |
a, c (Å) | 13.4460 (19), 11.528 (2) |
V (Å3) | 1804.9 (5) |
Z | 6 |
Radiation type | Mo Kα |
µ (mm−1) | 0.36 |
Crystal size (mm) | 0.10 × 0.10 × 0.04 |
Data collection | |
Diffractometer | Rigaku Saturn diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku/MSC, 2005) |
Tmin, Tmax | 0.968, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14051, 1513, 1424 |
Rint | 0.075 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.130, 1.08 |
No. of reflections | 1513 |
No. of parameters | 68 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.26 |
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···Cl2i | 0.85 | 2.15 | 2.991 (2) | 172.0 |
N1—H1B···Cl2ii | 0.92 | 2.22 | 3.139 (2) | 174.6 |
N1—H1C···Cl1iii | 0.92 | 2.25 | 3.166 (2) | 175.7 |
O2—H2···O1iv | 0.85 | 1.63 | 2.475 (2) | 174.8 |
Symmetry codes: (i) −y, x−y, z; (ii) −x+y+1, −x+1, z; (iii) −x+1, −y+1, −z+1; (iv) x+1, y, z. |
The title compound was obtained as a byproduct in the synthesis of hindered light stabilizer. For the characterization of this compound a crystal structure analysis was performed. The crystal structure of this compound consists of 4-hydroxy-2,2,6,6-tetramethylpiperidinium cations, hydroxonium cations and chloride anions, all of them located in special positions (Fig. 1). The cations and the anions are connected via O—H···O, O—H···Cl and N—H···Cl hydrogen bonding (Table 1). The isolated water oxygen atom, which is located on a 3-fold axis is disordered in two positions because of symmetry. For charge balance it must be protonated. However, the corresponding H atom was clearly located in difference map.