Presented herein are detailed optical, thermal, spectroscopic and structural analyses of the phase transformation occurring in tapentadol hydrochloride (C
14H
24NO
+·Cl
−), a phenomenon already reported [Fischer
et al. (2006); Patent: WO 2006000441 A2]. The thermal behaviour of the compound was studied using single-crystal X-ray diffraction, differential scanning calorimetry and Raman scattering measurements. The compound undergoes a first-order reversible phase transition at
Theat = 318.0 (1) K,
Tcool = 300.0 (1) K, as assessed by the coexistence of both phases in the vicinity of the transition and the abrupt changes observed in the unit-cell parameters with temperature. The process is accompanied by clear thermosalient behaviour, with a conspicuous movement of the samples. On cooling, the transformation leads from a
P2
12
12
1 symmetry (
Z′ = 1) to
P2
1, with an abrupt change in β [90 ↔ 94.78 (1)°] and duplication of the asymmetric unit contents (
Z′ = 2). The main structural differences observed across the transition are extremely small, with almost no changes in the stronger, non-covalent interaction scheme involving the `conventional' (N—H
Cl, O—H
Cl) hydrogen bonds.
Supporting information
CCDC references: 1892585; 1892586; 1892587
For all structures, data collection: Bruker APEX2; cell refinement: Bruker SAINT; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2018); molecular graphics: Bruker SHELXTL; software used to prepare material for publication: Bruker SHELXTL.
(2R,3R)-3-(3-Hydroxyphenyl)-N,N,2-trimethylpentan-1-aminium (150K)
top
Crystal data top
C14H24NO·Cl | F(000) = 560 |
Mr = 257.79 | Dx = 1.201 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1062 (2) Å | Cell parameters from 9942 reflections |
b = 11.5821 (3) Å | θ = 2.4–35.1° |
c = 17.3894 (5) Å | µ = 0.25 mm−1 |
β = 94.9978 (11)° | T = 150 K |
V = 1425.79 (7) Å3 | Fragment, colourless |
Z = 4 | 0.22 × 0.18 × 0.12 mm |
Data collection top
Bruker APEX-II CCD diffractometer | 10087 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.034 |
Absorption correction: multi-scan Bruker SAINT | θmax = 35.3°, θmin = 2.4° |
Tmin = 0.94, Tmax = 0.98 | h = −11→11 |
21367 measured reflections | k = −18→18 |
11698 independent reflections | l = −27→27 |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(Fo2) + (0.0545P)2 + 0.4317P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.113 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.40 e Å−3 |
11698 reflections | Δρmin = −0.32 e Å−3 |
319 parameters | Absolute structure: Flack x determined using 4082 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
5 restraints | Absolute structure parameter: 0.009 (15) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.2252 (3) | 0.53153 (17) | 0.77549 (11) | 0.0156 (3) | |
C2A | 0.1684 (3) | 0.42233 (18) | 0.79950 (13) | 0.0178 (4) | |
H2AA | 0.210582 | 0.394694 | 0.849495 | 0.021* | |
C3A | 0.0503 (3) | 0.35451 (18) | 0.75007 (13) | 0.0195 (4) | |
H3AA | 0.012454 | 0.280753 | 0.766999 | 0.023* | |
C4A | −0.0135 (3) | 0.3920 (2) | 0.67674 (13) | 0.0204 (4) | |
H4AA | −0.093582 | 0.344529 | 0.643504 | 0.025* | |
C5A | 0.0423 (3) | 0.5008 (2) | 0.65262 (12) | 0.0187 (4) | |
C6A | 0.1605 (3) | 0.56937 (19) | 0.70149 (12) | 0.0178 (4) | |
H6AA | 0.197804 | 0.643105 | 0.684339 | 0.021* | |
C7A | 0.3537 (3) | 0.60877 (18) | 0.82701 (12) | 0.0159 (3) | |
H7AA | 0.408626 | 0.665765 | 0.791995 | 0.019* | |
C8A | 0.5232 (3) | 0.5431 (2) | 0.86810 (14) | 0.0211 (4) | |
H8AA | 0.595464 | 0.596167 | 0.904241 | 0.025* | |
H8AB | 0.475547 | 0.479021 | 0.898701 | 0.025* | |
C9A | 0.6538 (3) | 0.4946 (2) | 0.81147 (17) | 0.0281 (5) | |
H9AA | 0.758904 | 0.453862 | 0.839871 | 0.042* | |
H9AB | 0.583497 | 0.440843 | 0.776223 | 0.042* | |
H9AC | 0.703391 | 0.557967 | 0.781762 | 0.042* | |
C10A | 0.2490 (3) | 0.68103 (17) | 0.88543 (12) | 0.0158 (3) | |
H10A | 0.346249 | 0.727594 | 0.916780 | 0.019* | |
C11A | 0.1091 (4) | 0.7656 (2) | 0.84449 (14) | 0.0233 (4) | |
H11A | 0.174884 | 0.814373 | 0.809356 | 0.035* | |
H11B | 0.008353 | 0.722558 | 0.814989 | 0.035* | |
H11C | 0.054142 | 0.814303 | 0.882860 | 0.035* | |
C12A | 0.1540 (3) | 0.60324 (18) | 0.94073 (13) | 0.0188 (4) | |
H12A | 0.051606 | 0.559870 | 0.911228 | 0.023* | |
H12B | 0.247650 | 0.546357 | 0.962847 | 0.023* | |
C13A | −0.0110 (4) | 0.5812 (2) | 1.05751 (16) | 0.0317 (5) | |
H13A | −0.101212 | 0.531788 | 1.026991 | 0.048* | |
H13B | 0.089691 | 0.533422 | 1.083066 | 0.048* | |
H13C | −0.076381 | 0.622540 | 1.096531 | 0.048* | |
C14A | 0.2100 (4) | 0.7425 (3) | 1.05007 (16) | 0.0339 (6) | |
H14A | 0.262701 | 0.797453 | 1.014822 | 0.051* | |
H14B | 0.146001 | 0.784909 | 1.089042 | 0.051* | |
H14C | 0.312072 | 0.695792 | 1.075577 | 0.051* | |
N1A | 0.0723 (3) | 0.66600 (17) | 1.00575 (11) | 0.0192 (3) | |
H1NA | −0.019 (3) | 0.709 (2) | 0.9870 (17) | 0.023* | |
O1A | −0.0218 (3) | 0.53470 (18) | 0.57942 (10) | 0.0295 (4) | |
H1OA | 0.043 (5) | 0.589 (2) | 0.562 (2) | 0.035* | |
C1B | 0.6929 (3) | 1.01289 (18) | 0.73270 (12) | 0.0163 (4) | |
C2B | 0.6185 (3) | 1.11833 (18) | 0.70472 (13) | 0.0188 (4) | |
H2BA | 0.659113 | 1.150519 | 0.658706 | 0.023* | |
C3B | 0.4850 (3) | 1.17575 (19) | 0.74453 (14) | 0.0215 (4) | |
H3BA | 0.434264 | 1.246867 | 0.724995 | 0.026* | |
C4B | 0.4246 (3) | 1.1311 (2) | 0.81221 (14) | 0.0216 (4) | |
H4BA | 0.334360 | 1.171676 | 0.839101 | 0.026* | |
C5B | 0.4974 (3) | 1.0265 (2) | 0.84024 (12) | 0.0199 (4) | |
C6B | 0.6301 (3) | 0.96767 (19) | 0.80023 (12) | 0.0185 (4) | |
H6BA | 0.678344 | 0.895711 | 0.819351 | 0.022* | |
C7B | 0.8437 (3) | 0.94833 (18) | 0.69268 (12) | 0.0162 (3) | |
H7BA | 0.911188 | 0.899058 | 0.733480 | 0.019* | |
C8B | 0.9932 (3) | 1.0311 (2) | 0.66602 (14) | 0.0203 (4) | |
H8BA | 0.932721 | 1.082243 | 0.625459 | 0.024* | |
H8BB | 1.039913 | 1.080350 | 0.710139 | 0.024* | |
C9B | 1.1606 (4) | 0.9715 (2) | 0.63458 (17) | 0.0303 (5) | |
H9BA | 1.249613 | 1.029665 | 0.618793 | 0.045* | |
H9BB | 1.223761 | 0.922169 | 0.674728 | 0.045* | |
H9BC | 1.116412 | 0.924066 | 0.589925 | 0.045* | |
C10B | 0.7626 (3) | 0.86337 (17) | 0.62906 (12) | 0.0151 (3) | |
H10B | 0.872150 | 0.823534 | 0.608217 | 0.018* | |
C11B | 0.6390 (4) | 0.7704 (2) | 0.66121 (14) | 0.0232 (4) | |
H11D | 0.711083 | 0.730052 | 0.703706 | 0.035* | |
H11E | 0.527204 | 0.806312 | 0.680251 | 0.035* | |
H11F | 0.599535 | 0.715050 | 0.620316 | 0.035* | |
C12B | 0.6588 (3) | 0.92956 (17) | 0.56259 (12) | 0.0169 (3) | |
H12C | 0.552640 | 0.972315 | 0.582568 | 0.020* | |
H12D | 0.746269 | 0.987159 | 0.543343 | 0.020* | |
C13B | 0.4928 (3) | 0.9309 (2) | 0.43327 (14) | 0.0247 (4) | |
H13D | 0.398239 | 0.980746 | 0.454223 | 0.037* | |
H13E | 0.589924 | 0.978735 | 0.412280 | 0.037* | |
H13F | 0.431640 | 0.882520 | 0.392132 | 0.037* | |
C14B | 0.7267 (4) | 0.7787 (2) | 0.46636 (15) | 0.0268 (5) | |
H14D | 0.783064 | 0.730426 | 0.508534 | 0.040* | |
H14E | 0.666980 | 0.729407 | 0.425435 | 0.040* | |
H14F | 0.825264 | 0.825621 | 0.445583 | 0.040* | |
N1B | 0.5821 (3) | 0.85576 (16) | 0.49599 (10) | 0.0162 (3) | |
H1NB | 0.493 (3) | 0.811 (2) | 0.5087 (17) | 0.019* | |
O1B | 0.4395 (3) | 0.98642 (17) | 0.90817 (11) | 0.0291 (4) | |
H1OB | 0.503 (5) | 0.927 (2) | 0.922 (2) | 0.035* | |
Cl1A | 0.22719 (7) | 0.71302 (4) | 0.50862 (3) | 0.02152 (11) | |
Cl1B | 0.71455 (7) | 0.81187 (4) | 0.98817 (3) | 0.02193 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.0153 (8) | 0.0161 (8) | 0.0156 (8) | 0.0010 (6) | 0.0026 (6) | −0.0015 (7) |
C2A | 0.0185 (9) | 0.0163 (8) | 0.0187 (9) | 0.0017 (7) | 0.0024 (7) | −0.0011 (7) |
C3A | 0.0197 (9) | 0.0159 (8) | 0.0237 (10) | −0.0007 (7) | 0.0063 (7) | −0.0027 (7) |
C4A | 0.0178 (9) | 0.0232 (10) | 0.0206 (10) | −0.0033 (7) | 0.0032 (7) | −0.0054 (7) |
C5A | 0.0164 (9) | 0.0250 (10) | 0.0147 (8) | −0.0025 (7) | 0.0014 (7) | −0.0010 (7) |
C6A | 0.0171 (9) | 0.0206 (9) | 0.0159 (8) | −0.0031 (7) | 0.0021 (7) | 0.0000 (7) |
C7A | 0.0152 (8) | 0.0170 (8) | 0.0155 (8) | 0.0001 (6) | 0.0011 (6) | −0.0008 (6) |
C8A | 0.0158 (9) | 0.0230 (10) | 0.0241 (10) | 0.0037 (7) | −0.0004 (7) | −0.0015 (8) |
C9A | 0.0191 (10) | 0.0279 (11) | 0.0382 (14) | 0.0054 (9) | 0.0071 (9) | −0.0013 (10) |
C10A | 0.0169 (8) | 0.0142 (8) | 0.0162 (8) | 0.0020 (6) | 0.0006 (7) | −0.0011 (6) |
C11A | 0.0257 (11) | 0.0206 (9) | 0.0231 (10) | 0.0087 (8) | −0.0003 (8) | 0.0021 (8) |
C12A | 0.0217 (9) | 0.0158 (8) | 0.0197 (9) | 0.0035 (7) | 0.0063 (7) | −0.0010 (7) |
C13A | 0.0327 (13) | 0.0345 (13) | 0.0302 (12) | 0.0080 (10) | 0.0164 (10) | 0.0090 (10) |
C14A | 0.0356 (14) | 0.0428 (15) | 0.0223 (11) | −0.0028 (11) | −0.0026 (10) | −0.0112 (10) |
N1A | 0.0182 (8) | 0.0214 (8) | 0.0180 (8) | 0.0055 (6) | 0.0024 (6) | −0.0007 (6) |
O1A | 0.0285 (9) | 0.0409 (10) | 0.0177 (7) | −0.0134 (8) | −0.0055 (6) | 0.0053 (7) |
C1B | 0.0143 (8) | 0.0179 (8) | 0.0161 (9) | 0.0026 (7) | −0.0013 (7) | −0.0031 (7) |
C2B | 0.0181 (9) | 0.0183 (9) | 0.0198 (9) | 0.0029 (7) | 0.0002 (7) | 0.0001 (7) |
C3B | 0.0209 (10) | 0.0191 (9) | 0.0242 (10) | 0.0059 (7) | −0.0006 (8) | −0.0019 (8) |
C4B | 0.0180 (9) | 0.0231 (10) | 0.0237 (10) | 0.0074 (8) | 0.0012 (8) | −0.0030 (8) |
C5B | 0.0175 (9) | 0.0240 (10) | 0.0179 (9) | 0.0037 (7) | −0.0001 (7) | −0.0007 (7) |
C6B | 0.0189 (9) | 0.0194 (9) | 0.0169 (9) | 0.0048 (7) | −0.0006 (7) | −0.0006 (7) |
C7B | 0.0139 (8) | 0.0183 (8) | 0.0158 (8) | 0.0034 (6) | −0.0024 (6) | −0.0019 (7) |
C8B | 0.0130 (8) | 0.0208 (9) | 0.0268 (10) | −0.0010 (7) | 0.0001 (7) | −0.0066 (8) |
C9B | 0.0198 (10) | 0.0313 (12) | 0.0408 (14) | −0.0015 (9) | 0.0084 (10) | −0.0097 (11) |
C10B | 0.0145 (8) | 0.0143 (8) | 0.0160 (8) | 0.0005 (6) | −0.0009 (6) | −0.0003 (6) |
C11B | 0.0278 (11) | 0.0194 (9) | 0.0220 (10) | −0.0053 (8) | −0.0009 (8) | 0.0039 (8) |
C12B | 0.0190 (9) | 0.0155 (8) | 0.0157 (8) | −0.0006 (7) | −0.0025 (7) | −0.0003 (6) |
C13B | 0.0222 (10) | 0.0302 (11) | 0.0204 (10) | −0.0028 (8) | −0.0056 (8) | 0.0061 (8) |
C14B | 0.0253 (11) | 0.0337 (12) | 0.0218 (10) | 0.0050 (9) | 0.0032 (9) | −0.0081 (9) |
N1B | 0.0138 (7) | 0.0197 (8) | 0.0151 (7) | −0.0021 (6) | 0.0003 (6) | 0.0001 (6) |
O1B | 0.0291 (9) | 0.0356 (10) | 0.0239 (9) | 0.0126 (8) | 0.0096 (7) | 0.0051 (7) |
Cl1A | 0.0191 (2) | 0.0181 (2) | 0.0271 (2) | −0.00398 (18) | 0.00062 (17) | −0.00143 (19) |
Cl1B | 0.0196 (2) | 0.0190 (2) | 0.0271 (2) | 0.00380 (18) | 0.00135 (17) | −0.00214 (19) |
Geometric parameters (Å, º) top
C1A—C6A | 1.399 (3) | C1B—C6B | 1.394 (3) |
C1A—C2A | 1.402 (3) | C1B—C2B | 1.401 (3) |
C1A—C7A | 1.515 (3) | C1B—C7B | 1.523 (3) |
C2A—C3A | 1.391 (3) | C2B—C3B | 1.392 (3) |
C2A—H2AA | 0.9500 | C2B—H2BA | 0.9500 |
C3A—C4A | 1.385 (3) | C3B—C4B | 1.387 (3) |
C3A—H3AA | 0.9500 | C3B—H3BA | 0.9500 |
C4A—C5A | 1.397 (3) | C4B—C5B | 1.389 (3) |
C4A—H4AA | 0.9500 | C4B—H4BA | 0.9500 |
C5A—O1A | 1.371 (3) | C5B—O1B | 1.366 (3) |
C5A—C6A | 1.391 (3) | C5B—C6B | 1.397 (3) |
C6A—H6AA | 0.9500 | C6B—H6BA | 0.9500 |
C7A—C8A | 1.546 (3) | C7B—C8B | 1.532 (3) |
C7A—C10A | 1.555 (3) | C7B—C10B | 1.553 (3) |
C7A—H7AA | 1.0000 | C7B—H7BA | 1.0000 |
C8A—C9A | 1.519 (3) | C8B—C9B | 1.518 (3) |
C8A—H8AA | 0.9900 | C8B—H8BA | 0.9900 |
C8A—H8AB | 0.9900 | C8B—H8BB | 0.9900 |
C9A—H9AA | 0.9800 | C9B—H9BA | 0.9800 |
C9A—H9AB | 0.9800 | C9B—H9BB | 0.9800 |
C9A—H9AC | 0.9800 | C9B—H9BC | 0.9800 |
C10A—C12A | 1.518 (3) | C10B—C12B | 1.523 (3) |
C10A—C11A | 1.527 (3) | C10B—C11B | 1.526 (3) |
C10A—H10A | 1.0000 | C10B—H10B | 1.0000 |
C11A—H11A | 0.9800 | C11B—H11D | 0.9800 |
C11A—H11B | 0.9800 | C11B—H11E | 0.9800 |
C11A—H11C | 0.9800 | C11B—H11F | 0.9800 |
C12A—N1A | 1.503 (3) | C12B—N1B | 1.503 (3) |
C12A—H12A | 0.9900 | C12B—H12C | 0.9900 |
C12A—H12B | 0.9900 | C12B—H12D | 0.9900 |
C13A—N1A | 1.489 (3) | C13B—N1B | 1.493 (3) |
C13A—H13A | 0.9800 | C13B—H13D | 0.9800 |
C13A—H13B | 0.9800 | C13B—H13E | 0.9800 |
C13A—H13C | 0.9800 | C13B—H13F | 0.9800 |
C14A—N1A | 1.485 (3) | C14B—N1B | 1.486 (3) |
C14A—H14A | 0.9800 | C14B—H14D | 0.9800 |
C14A—H14B | 0.9800 | C14B—H14E | 0.9800 |
C14A—H14C | 0.9800 | C14B—H14F | 0.9800 |
N1A—H1NA | 0.857 (13) | N1B—H1NB | 0.864 (13) |
O1A—H1OA | 0.843 (13) | O1B—H1OB | 0.846 (13) |
| | | |
C6A—C1A—C2A | 118.45 (19) | C6B—C1B—C2B | 118.77 (19) |
C6A—C1A—C7A | 119.48 (18) | C6B—C1B—C7B | 119.32 (18) |
C2A—C1A—C7A | 122.07 (18) | C2B—C1B—C7B | 121.89 (19) |
C3A—C2A—C1A | 119.9 (2) | C3B—C2B—C1B | 119.8 (2) |
C3A—C2A—H2AA | 120.0 | C3B—C2B—H2BA | 120.1 |
C1A—C2A—H2AA | 120.0 | C1B—C2B—H2BA | 120.1 |
C4A—C3A—C2A | 121.6 (2) | C4B—C3B—C2B | 121.3 (2) |
C4A—C3A—H3AA | 119.2 | C4B—C3B—H3BA | 119.4 |
C2A—C3A—H3AA | 119.2 | C2B—C3B—H3BA | 119.4 |
C3A—C4A—C5A | 118.7 (2) | C3B—C4B—C5B | 119.3 (2) |
C3A—C4A—H4AA | 120.6 | C3B—C4B—H4BA | 120.4 |
C5A—C4A—H4AA | 120.6 | C5B—C4B—H4BA | 120.4 |
O1A—C5A—C6A | 122.5 (2) | O1B—C5B—C4B | 118.0 (2) |
O1A—C5A—C4A | 117.2 (2) | O1B—C5B—C6B | 122.1 (2) |
C6A—C5A—C4A | 120.3 (2) | C4B—C5B—C6B | 119.9 (2) |
C5A—C6A—C1A | 121.06 (19) | C1B—C6B—C5B | 121.02 (19) |
C5A—C6A—H6AA | 119.5 | C1B—C6B—H6BA | 119.5 |
C1A—C6A—H6AA | 119.5 | C5B—C6B—H6BA | 119.5 |
C1A—C7A—C8A | 112.83 (17) | C1B—C7B—C8B | 111.39 (17) |
C1A—C7A—C10A | 113.96 (17) | C1B—C7B—C10B | 113.84 (16) |
C8A—C7A—C10A | 111.14 (17) | C8B—C7B—C10B | 113.87 (17) |
C1A—C7A—H7AA | 106.1 | C1B—C7B—H7BA | 105.6 |
C8A—C7A—H7AA | 106.1 | C8B—C7B—H7BA | 105.6 |
C10A—C7A—H7AA | 106.1 | C10B—C7B—H7BA | 105.6 |
C9A—C8A—C7A | 112.19 (19) | C9B—C8B—C7B | 114.21 (19) |
C9A—C8A—H8AA | 109.2 | C9B—C8B—H8BA | 108.7 |
C7A—C8A—H8AA | 109.2 | C7B—C8B—H8BA | 108.7 |
C9A—C8A—H8AB | 109.2 | C9B—C8B—H8BB | 108.7 |
C7A—C8A—H8AB | 109.2 | C7B—C8B—H8BB | 108.7 |
H8AA—C8A—H8AB | 107.9 | H8BA—C8B—H8BB | 107.6 |
C8A—C9A—H9AA | 109.5 | C8B—C9B—H9BA | 109.5 |
C8A—C9A—H9AB | 109.5 | C8B—C9B—H9BB | 109.5 |
H9AA—C9A—H9AB | 109.5 | H9BA—C9B—H9BB | 109.5 |
C8A—C9A—H9AC | 109.5 | C8B—C9B—H9BC | 109.5 |
H9AA—C9A—H9AC | 109.5 | H9BA—C9B—H9BC | 109.5 |
H9AB—C9A—H9AC | 109.5 | H9BB—C9B—H9BC | 109.5 |
C12A—C10A—C11A | 111.64 (19) | C12B—C10B—C11B | 112.17 (17) |
C12A—C10A—C7A | 111.03 (16) | C12B—C10B—C7B | 110.29 (16) |
C11A—C10A—C7A | 111.72 (18) | C11B—C10B—C7B | 112.07 (18) |
C12A—C10A—H10A | 107.4 | C12B—C10B—H10B | 107.3 |
C11A—C10A—H10A | 107.4 | C11B—C10B—H10B | 107.3 |
C7A—C10A—H10A | 107.4 | C7B—C10B—H10B | 107.3 |
C10A—C11A—H11A | 109.5 | C10B—C11B—H11D | 109.5 |
C10A—C11A—H11B | 109.5 | C10B—C11B—H11E | 109.5 |
H11A—C11A—H11B | 109.5 | H11D—C11B—H11E | 109.5 |
C10A—C11A—H11C | 109.5 | C10B—C11B—H11F | 109.5 |
H11A—C11A—H11C | 109.5 | H11D—C11B—H11F | 109.5 |
H11B—C11A—H11C | 109.5 | H11E—C11B—H11F | 109.5 |
N1A—C12A—C10A | 114.32 (17) | N1B—C12B—C10B | 114.69 (16) |
N1A—C12A—H12A | 108.7 | N1B—C12B—H12C | 108.6 |
C10A—C12A—H12A | 108.7 | C10B—C12B—H12C | 108.6 |
N1A—C12A—H12B | 108.7 | N1B—C12B—H12D | 108.6 |
C10A—C12A—H12B | 108.7 | C10B—C12B—H12D | 108.6 |
H12A—C12A—H12B | 107.6 | H12C—C12B—H12D | 107.6 |
N1A—C13A—H13A | 109.5 | N1B—C13B—H13D | 109.5 |
N1A—C13A—H13B | 109.5 | N1B—C13B—H13E | 109.5 |
H13A—C13A—H13B | 109.5 | H13D—C13B—H13E | 109.5 |
N1A—C13A—H13C | 109.5 | N1B—C13B—H13F | 109.5 |
H13A—C13A—H13C | 109.5 | H13D—C13B—H13F | 109.5 |
H13B—C13A—H13C | 109.5 | H13E—C13B—H13F | 109.5 |
N1A—C14A—H14A | 109.5 | N1B—C14B—H14D | 109.5 |
N1A—C14A—H14B | 109.5 | N1B—C14B—H14E | 109.5 |
H14A—C14A—H14B | 109.5 | H14D—C14B—H14E | 109.5 |
N1A—C14A—H14C | 109.5 | N1B—C14B—H14F | 109.5 |
H14A—C14A—H14C | 109.5 | H14D—C14B—H14F | 109.5 |
H14B—C14A—H14C | 109.5 | H14E—C14B—H14F | 109.5 |
C14A—N1A—C13A | 111.0 (2) | C14B—N1B—C13B | 111.05 (19) |
C14A—N1A—C12A | 113.49 (19) | C14B—N1B—C12B | 113.17 (17) |
C13A—N1A—C12A | 109.61 (18) | C13B—N1B—C12B | 109.51 (17) |
C14A—N1A—H1NA | 107 (2) | C14B—N1B—H1NB | 106 (2) |
C13A—N1A—H1NA | 107 (2) | C13B—N1B—H1NB | 105 (2) |
C12A—N1A—H1NA | 109 (2) | C12B—N1B—H1NB | 112 (2) |
C5A—O1A—H1OA | 113 (3) | C5B—O1B—H1OB | 109 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1NA···Cl1Bi | 0.86 (1) | 2.24 (2) | 3.0453 (19) | 156 (3) |
O1A—H1OA···Cl1A | 0.84 (1) | 2.21 (1) | 3.0481 (19) | 173 (4) |
N1B—H1NB···Cl1A | 0.86 (1) | 2.20 (2) | 3.0396 (19) | 163 (3) |
O1B—H1OB···Cl1B | 0.85 (1) | 2.25 (2) | 3.0609 (19) | 161 (3) |
Symmetry code: (i) x−1, y, z. |
(2R,3R)-3-(3-Hydroxyphenyl)-N,N,2-trimethylpentan-1-aminium (250K)
top
Crystal data top
C14H24NO·Cl | F(000) = 560 |
Mr = 257.79 | Dx = 1.185 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1350 (2) Å | Cell parameters from 7469 reflections |
b = 11.6402 (4) Å | θ = 2.9–30.7° |
c = 17.4546 (5) Å | µ = 0.25 mm−1 |
β = 94.7791 (14)° | T = 250 K |
V = 1444.61 (8) Å3 | Fragment, colourless |
Z = 4 | 0.22 × 0.18 × 0.12 mm |
Data collection top
Bruker APEX-II CCD diffractometer | 9197 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.057 |
Absorption correction: multi-scan Bruker SAINT | θmax = 35.2°, θmin = 2.3° |
Tmin = 0.94, Tmax = 0.98 | h = −11→11 |
21544 measured reflections | k = −18→18 |
11785 independent reflections | l = −27→27 |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.054 | w = 1/[σ2(Fo2) + (0.0667P)2 + 0.3037P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.136 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.34 e Å−3 |
11785 reflections | Δρmin = −0.33 e Å−3 |
319 parameters | Absolute structure: Flack x determined using 3504 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
5 restraints | Absolute structure parameter: −0.01 (5) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.2246 (3) | 0.5313 (2) | 0.77568 (14) | 0.0199 (4) | |
C2A | 0.1680 (4) | 0.4228 (2) | 0.79943 (16) | 0.0236 (5) | |
H2AA | 0.209481 | 0.395502 | 0.848621 | 0.028* | |
C3A | 0.0502 (4) | 0.3552 (2) | 0.75029 (16) | 0.0257 (5) | |
H3AA | 0.012189 | 0.282808 | 0.767085 | 0.031* | |
C4A | −0.0121 (4) | 0.3926 (2) | 0.67710 (16) | 0.0265 (5) | |
H4AA | −0.090348 | 0.345795 | 0.644248 | 0.032* | |
C5A | 0.0433 (4) | 0.5006 (2) | 0.65312 (15) | 0.0241 (5) | |
C6A | 0.1609 (4) | 0.5691 (2) | 0.70177 (14) | 0.0228 (5) | |
H6AA | 0.197938 | 0.641618 | 0.684815 | 0.027* | |
C7A | 0.3529 (3) | 0.6085 (2) | 0.82707 (14) | 0.0205 (4) | |
H7AA | 0.407132 | 0.664594 | 0.792432 | 0.025* | |
C8A | 0.5219 (4) | 0.5432 (2) | 0.86785 (16) | 0.0268 (5) | |
H8AA | 0.592714 | 0.595461 | 0.903510 | 0.032* | |
H8AB | 0.474928 | 0.479951 | 0.897987 | 0.032* | |
C9A | 0.6527 (4) | 0.4952 (3) | 0.8115 (2) | 0.0370 (7) | |
H9AA | 0.756111 | 0.455155 | 0.839528 | 0.055* | |
H9AB | 0.583912 | 0.442175 | 0.776741 | 0.055* | |
H9AC | 0.701679 | 0.557665 | 0.782263 | 0.055* | |
C10A | 0.2480 (4) | 0.6808 (2) | 0.88533 (14) | 0.0206 (4) | |
H10A | 0.343752 | 0.726836 | 0.916014 | 0.025* | |
C11A | 0.1085 (4) | 0.7650 (2) | 0.84452 (17) | 0.0302 (6) | |
H11A | 0.173380 | 0.812845 | 0.809691 | 0.045* | |
H11B | 0.009199 | 0.722513 | 0.815659 | 0.045* | |
H11C | 0.054370 | 0.813128 | 0.882353 | 0.045* | |
C12A | 0.1541 (4) | 0.6035 (2) | 0.94075 (15) | 0.0240 (5) | |
H12A | 0.053545 | 0.560281 | 0.911912 | 0.029* | |
H12B | 0.246805 | 0.547864 | 0.962595 | 0.029* | |
C13A | −0.0119 (5) | 0.5816 (3) | 1.0573 (2) | 0.0416 (8) | |
H13A | −0.100472 | 0.532877 | 1.027297 | 0.062* | |
H13B | 0.087106 | 0.534655 | 1.082630 | 0.062* | |
H13C | −0.076761 | 0.622494 | 1.095710 | 0.062* | |
C14A | 0.2090 (6) | 0.7426 (3) | 1.0496 (2) | 0.0447 (8) | |
H14A | 0.261246 | 0.796530 | 1.014752 | 0.067* | |
H14B | 0.145543 | 0.784554 | 1.087949 | 0.067* | |
H14C | 0.309410 | 0.696714 | 1.074869 | 0.067* | |
N1A | 0.0719 (3) | 0.6660 (2) | 1.00554 (13) | 0.0250 (4) | |
H1NA | −0.020 (4) | 0.708 (3) | 0.9880 (19) | 0.030* | |
O1A | −0.0203 (3) | 0.5346 (2) | 0.58002 (12) | 0.0381 (5) | |
H1OA | 0.040 (6) | 0.589 (3) | 0.561 (2) | 0.046* | |
C1B | 0.6938 (3) | 1.0129 (2) | 0.73271 (14) | 0.0209 (4) | |
C2B | 0.6191 (4) | 1.1178 (2) | 0.70489 (16) | 0.0244 (5) | |
H2BA | 0.658889 | 1.149367 | 0.659396 | 0.029* | |
C3B | 0.4864 (4) | 1.1752 (2) | 0.74447 (17) | 0.0281 (5) | |
H3BA | 0.436251 | 1.245079 | 0.725093 | 0.034* | |
C4B | 0.4265 (4) | 1.1310 (2) | 0.81220 (17) | 0.0277 (5) | |
H4BA | 0.337817 | 1.171187 | 0.838811 | 0.033* | |
C5B | 0.4988 (4) | 1.0270 (2) | 0.84028 (15) | 0.0254 (5) | |
C6B | 0.6310 (4) | 0.9681 (2) | 0.80002 (15) | 0.0233 (5) | |
H6BA | 0.678040 | 0.897123 | 0.818742 | 0.028* | |
C7B | 0.8434 (3) | 0.9486 (2) | 0.69249 (14) | 0.0207 (4) | |
H7BA | 0.909990 | 0.900103 | 0.732638 | 0.025* | |
C8B | 0.9925 (4) | 1.0305 (2) | 0.66564 (17) | 0.0263 (5) | |
H8BA | 0.933291 | 1.080410 | 0.625355 | 0.032* | |
H8BB | 1.037684 | 1.079637 | 0.708913 | 0.032* | |
C9B | 1.1599 (5) | 0.9716 (3) | 0.6348 (2) | 0.0392 (7) | |
H9BA | 1.247443 | 1.029033 | 0.619116 | 0.059* | |
H9BB | 1.222064 | 0.923593 | 0.674682 | 0.059* | |
H9BC | 1.117503 | 0.924367 | 0.590989 | 0.059* | |
C10B | 0.7625 (3) | 0.86362 (19) | 0.62917 (14) | 0.0189 (4) | |
H10B | 0.870575 | 0.824539 | 0.608334 | 0.023* | |
C11B | 0.6396 (5) | 0.7708 (2) | 0.66139 (17) | 0.0297 (6) | |
H11D | 0.710699 | 0.731034 | 0.703136 | 0.045* | |
H11E | 0.529329 | 0.806049 | 0.680394 | 0.045* | |
H11F | 0.600691 | 0.716342 | 0.621086 | 0.045* | |
C12B | 0.6583 (4) | 0.9294 (2) | 0.56308 (14) | 0.0218 (4) | |
H12C | 0.553490 | 0.971223 | 0.583064 | 0.026* | |
H12D | 0.744023 | 0.986462 | 0.543964 | 0.026* | |
C13B | 0.4920 (4) | 0.9305 (3) | 0.43400 (17) | 0.0326 (6) | |
H13D | 0.399031 | 0.979647 | 0.454906 | 0.049* | |
H13E | 0.587368 | 0.977471 | 0.412869 | 0.049* | |
H13F | 0.431243 | 0.882636 | 0.393730 | 0.049* | |
C14B | 0.7250 (5) | 0.7792 (3) | 0.46666 (18) | 0.0348 (6) | |
H14D | 0.781081 | 0.731788 | 0.508156 | 0.052* | |
H14E | 0.665756 | 0.730436 | 0.426590 | 0.052* | |
H14F | 0.821880 | 0.825272 | 0.445728 | 0.052* | |
N1B | 0.5818 (3) | 0.85580 (18) | 0.49649 (12) | 0.0209 (4) | |
H1NB | 0.495 (4) | 0.810 (3) | 0.5106 (18) | 0.025* | |
O1B | 0.4410 (3) | 0.9866 (2) | 0.90800 (13) | 0.0380 (5) | |
H1OB | 0.506 (6) | 0.929 (2) | 0.923 (2) | 0.046* | |
Cl1A | 0.22801 (9) | 0.71266 (5) | 0.50908 (4) | 0.02838 (14) | |
Cl1B | 0.71506 (9) | 0.81214 (5) | 0.98762 (4) | 0.02909 (14) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.0191 (10) | 0.0201 (10) | 0.0207 (10) | 0.0020 (8) | 0.0029 (8) | −0.0017 (8) |
C2A | 0.0251 (12) | 0.0205 (10) | 0.0254 (11) | 0.0022 (9) | 0.0038 (9) | −0.0008 (9) |
C3A | 0.0255 (12) | 0.0200 (10) | 0.0325 (13) | −0.0014 (9) | 0.0076 (10) | −0.0028 (9) |
C4A | 0.0232 (12) | 0.0289 (12) | 0.0278 (13) | −0.0047 (9) | 0.0050 (10) | −0.0079 (10) |
C5A | 0.0210 (11) | 0.0309 (12) | 0.0205 (11) | −0.0035 (9) | 0.0020 (9) | −0.0010 (9) |
C6A | 0.0224 (11) | 0.0246 (11) | 0.0218 (11) | −0.0038 (9) | 0.0038 (9) | 0.0001 (8) |
C7A | 0.0192 (10) | 0.0214 (10) | 0.0209 (10) | −0.0002 (8) | 0.0017 (8) | −0.0005 (8) |
C8A | 0.0191 (11) | 0.0292 (12) | 0.0317 (13) | 0.0048 (9) | 0.0002 (9) | −0.0018 (10) |
C9A | 0.0242 (14) | 0.0363 (15) | 0.0514 (19) | 0.0071 (11) | 0.0090 (13) | −0.0007 (13) |
C10A | 0.0224 (11) | 0.0176 (9) | 0.0216 (11) | 0.0024 (8) | 0.0007 (8) | −0.0007 (8) |
C11A | 0.0343 (15) | 0.0263 (12) | 0.0297 (14) | 0.0112 (11) | 0.0003 (11) | 0.0033 (10) |
C12A | 0.0274 (12) | 0.0190 (10) | 0.0265 (12) | 0.0049 (9) | 0.0075 (9) | −0.0011 (8) |
C13A | 0.0433 (19) | 0.0449 (17) | 0.0399 (17) | 0.0118 (14) | 0.0222 (14) | 0.0129 (14) |
C14A | 0.0447 (19) | 0.057 (2) | 0.0318 (16) | −0.0019 (15) | −0.0023 (14) | −0.0163 (14) |
N1A | 0.0235 (11) | 0.0279 (10) | 0.0236 (10) | 0.0078 (8) | 0.0027 (8) | −0.0013 (8) |
O1A | 0.0382 (12) | 0.0510 (13) | 0.0239 (10) | −0.0175 (10) | −0.0055 (8) | 0.0069 (9) |
C1B | 0.0181 (10) | 0.0231 (10) | 0.0212 (11) | 0.0035 (8) | −0.0007 (8) | −0.0042 (8) |
C2B | 0.0231 (11) | 0.0234 (11) | 0.0266 (12) | 0.0036 (9) | 0.0003 (9) | 0.0000 (9) |
C3B | 0.0280 (13) | 0.0223 (11) | 0.0335 (14) | 0.0077 (9) | −0.0005 (10) | −0.0017 (10) |
C4B | 0.0229 (12) | 0.0282 (12) | 0.0320 (13) | 0.0090 (9) | 0.0018 (10) | −0.0047 (10) |
C5B | 0.0233 (12) | 0.0304 (12) | 0.0223 (11) | 0.0052 (10) | 0.0006 (9) | −0.0022 (9) |
C6B | 0.0231 (11) | 0.0246 (11) | 0.0218 (11) | 0.0068 (9) | −0.0009 (9) | −0.0018 (9) |
C7B | 0.0168 (10) | 0.0236 (10) | 0.0212 (11) | 0.0044 (8) | −0.0023 (8) | −0.0021 (8) |
C8B | 0.0161 (11) | 0.0267 (12) | 0.0359 (14) | −0.0016 (9) | 0.0002 (9) | −0.0086 (10) |
C9B | 0.0262 (14) | 0.0399 (16) | 0.0532 (19) | −0.0039 (12) | 0.0124 (13) | −0.0136 (14) |
C10B | 0.0186 (10) | 0.0173 (9) | 0.0205 (10) | 0.0011 (8) | −0.0006 (8) | 0.0000 (8) |
C11B | 0.0351 (15) | 0.0245 (11) | 0.0290 (13) | −0.0080 (10) | 0.0002 (11) | 0.0051 (10) |
C12B | 0.0239 (11) | 0.0184 (10) | 0.0225 (11) | −0.0015 (8) | −0.0021 (9) | −0.0002 (8) |
C13B | 0.0302 (14) | 0.0387 (15) | 0.0272 (13) | −0.0053 (11) | −0.0084 (11) | 0.0091 (11) |
C14B | 0.0343 (16) | 0.0425 (16) | 0.0277 (14) | 0.0053 (12) | 0.0039 (12) | −0.0114 (11) |
N1B | 0.0187 (9) | 0.0237 (9) | 0.0199 (9) | −0.0038 (7) | −0.0007 (7) | 0.0002 (7) |
O1B | 0.0384 (12) | 0.0455 (13) | 0.0319 (11) | 0.0159 (10) | 0.0133 (9) | 0.0062 (9) |
Cl1A | 0.0251 (3) | 0.0230 (3) | 0.0369 (3) | −0.0057 (2) | 0.0016 (2) | −0.0021 (2) |
Cl1B | 0.0254 (3) | 0.0245 (3) | 0.0373 (3) | 0.0051 (2) | 0.0024 (2) | −0.0030 (2) |
Geometric parameters (Å, º) top
C1A—C2A | 1.400 (3) | C1B—C6B | 1.393 (4) |
C1A—C6A | 1.402 (3) | C1B—C2B | 1.404 (3) |
C1A—C7A | 1.521 (3) | C1B—C7B | 1.522 (3) |
C2A—C3A | 1.393 (4) | C2B—C3B | 1.389 (4) |
C2A—H2AA | 0.9400 | C2B—H2BA | 0.9400 |
C3A—C4A | 1.387 (4) | C3B—C4B | 1.389 (4) |
C3A—H3AA | 0.9400 | C3B—H3BA | 0.9400 |
C4A—C5A | 1.393 (4) | C4B—C5B | 1.389 (4) |
C4A—H4AA | 0.9400 | C4B—H4BA | 0.9400 |
C5A—O1A | 1.376 (3) | C5B—O1B | 1.368 (3) |
C5A—C6A | 1.393 (4) | C5B—C6B | 1.402 (4) |
C6A—H6AA | 0.9400 | C6B—H6BA | 0.9400 |
C7A—C8A | 1.548 (4) | C7B—C8B | 1.531 (4) |
C7A—C10A | 1.559 (4) | C7B—C10B | 1.558 (3) |
C7A—H7AA | 0.9900 | C7B—H7BA | 0.9900 |
C8A—C9A | 1.517 (4) | C8B—C9B | 1.514 (4) |
C8A—H8AA | 0.9800 | C8B—H8BA | 0.9800 |
C8A—H8AB | 0.9800 | C8B—H8BB | 0.9800 |
C9A—H9AA | 0.9700 | C9B—H9BA | 0.9700 |
C9A—H9AB | 0.9700 | C9B—H9BB | 0.9700 |
C9A—H9AC | 0.9700 | C9B—H9BC | 0.9700 |
C10A—C12A | 1.517 (4) | C10B—C11B | 1.528 (4) |
C10A—C11A | 1.530 (4) | C10B—C12B | 1.526 (3) |
C10A—H10A | 0.9900 | C10B—H10B | 0.9900 |
C11A—H11A | 0.9700 | C11B—H11D | 0.9700 |
C11A—H11B | 0.9700 | C11B—H11E | 0.9700 |
C11A—H11C | 0.9700 | C11B—H11F | 0.9700 |
C12A—N1A | 1.505 (3) | C12B—N1B | 1.509 (3) |
C12A—H12A | 0.9800 | C12B—H12C | 0.9800 |
C12A—H12B | 0.9800 | C12B—H12D | 0.9800 |
C13A—N1A | 1.493 (4) | C13B—N1B | 1.496 (3) |
C13A—H13A | 0.9700 | C13B—H13D | 0.9700 |
C13A—H13B | 0.9700 | C13B—H13E | 0.9700 |
C13A—H13C | 0.9700 | C13B—H13F | 0.9700 |
C14A—N1A | 1.489 (4) | C14B—N1B | 1.483 (4) |
C14A—H14A | 0.9700 | C14B—H14D | 0.9700 |
C14A—H14B | 0.9700 | C14B—H14E | 0.9700 |
C14A—H14C | 0.9700 | C14B—H14F | 0.9700 |
N1A—H1NA | 0.853 (13) | N1B—H1NB | 0.867 (13) |
O1A—H1OA | 0.844 (14) | O1B—H1OB | 0.845 (13) |
| | | |
C2A—C1A—C6A | 118.4 (2) | C6B—C1B—C2B | 118.5 (2) |
C2A—C1A—C7A | 122.2 (2) | C6B—C1B—C7B | 119.5 (2) |
C6A—C1A—C7A | 119.4 (2) | C2B—C1B—C7B | 121.9 (2) |
C3A—C2A—C1A | 120.1 (2) | C3B—C2B—C1B | 120.1 (3) |
C3A—C2A—H2AA | 119.9 | C3B—C2B—H2BA | 119.9 |
C1A—C2A—H2AA | 119.9 | C1B—C2B—H2BA | 119.9 |
C4A—C3A—C2A | 121.4 (2) | C4B—C3B—C2B | 121.1 (2) |
C4A—C3A—H3AA | 119.3 | C4B—C3B—H3BA | 119.5 |
C2A—C3A—H3AA | 119.3 | C2B—C3B—H3BA | 119.5 |
C3A—C4A—C5A | 118.8 (2) | C3B—C4B—C5B | 119.4 (2) |
C3A—C4A—H4AA | 120.6 | C3B—C4B—H4BA | 120.3 |
C5A—C4A—H4AA | 120.6 | C5B—C4B—H4BA | 120.3 |
O1A—C5A—C6A | 122.4 (2) | O1B—C5B—C4B | 118.4 (2) |
O1A—C5A—C4A | 117.3 (2) | O1B—C5B—C6B | 121.9 (2) |
C6A—C5A—C4A | 120.3 (2) | C4B—C5B—C6B | 119.7 (3) |
C5A—C6A—C1A | 121.0 (2) | C1B—C6B—C5B | 121.1 (2) |
C5A—C6A—H6AA | 119.5 | C1B—C6B—H6BA | 119.4 |
C1A—C6A—H6AA | 119.5 | C5B—C6B—H6BA | 119.4 |
C1A—C7A—C8A | 112.9 (2) | C1B—C7B—C8B | 111.5 (2) |
C1A—C7A—C10A | 113.9 (2) | C1B—C7B—C10B | 114.0 (2) |
C8A—C7A—C10A | 111.3 (2) | C8B—C7B—C10B | 113.8 (2) |
C1A—C7A—H7AA | 106.0 | C1B—C7B—H7BA | 105.5 |
C8A—C7A—H7AA | 106.0 | C8B—C7B—H7BA | 105.5 |
C10A—C7A—H7AA | 106.0 | C10B—C7B—H7BA | 105.5 |
C9A—C8A—C7A | 112.4 (2) | C9B—C8B—C7B | 114.5 (2) |
C9A—C8A—H8AA | 109.1 | C9B—C8B—H8BA | 108.6 |
C7A—C8A—H8AA | 109.1 | C7B—C8B—H8BA | 108.6 |
C9A—C8A—H8AB | 109.1 | C9B—C8B—H8BB | 108.6 |
C7A—C8A—H8AB | 109.1 | C7B—C8B—H8BB | 108.6 |
H8AA—C8A—H8AB | 107.9 | H8BA—C8B—H8BB | 107.6 |
C8A—C9A—H9AA | 109.5 | C8B—C9B—H9BA | 109.5 |
C8A—C9A—H9AB | 109.5 | C8B—C9B—H9BB | 109.5 |
H9AA—C9A—H9AB | 109.5 | H9BA—C9B—H9BB | 109.5 |
C8A—C9A—H9AC | 109.5 | C8B—C9B—H9BC | 109.5 |
H9AA—C9A—H9AC | 109.5 | H9BA—C9B—H9BC | 109.5 |
H9AB—C9A—H9AC | 109.5 | H9BB—C9B—H9BC | 109.5 |
C12A—C10A—C11A | 111.8 (2) | C11B—C10B—C12B | 112.0 (2) |
C12A—C10A—C7A | 110.95 (19) | C11B—C10B—C7B | 112.2 (2) |
C11A—C10A—C7A | 111.8 (2) | C12B—C10B—C7B | 110.24 (18) |
C12A—C10A—H10A | 107.3 | C11B—C10B—H10B | 107.4 |
C11A—C10A—H10A | 107.3 | C12B—C10B—H10B | 107.4 |
C7A—C10A—H10A | 107.3 | C7B—C10B—H10B | 107.4 |
C10A—C11A—H11A | 109.5 | C10B—C11B—H11D | 109.5 |
C10A—C11A—H11B | 109.5 | C10B—C11B—H11E | 109.5 |
H11A—C11A—H11B | 109.5 | H11D—C11B—H11E | 109.5 |
C10A—C11A—H11C | 109.5 | C10B—C11B—H11F | 109.5 |
H11A—C11A—H11C | 109.5 | H11D—C11B—H11F | 109.5 |
H11B—C11A—H11C | 109.5 | H11E—C11B—H11F | 109.5 |
N1A—C12A—C10A | 114.4 (2) | N1B—C12B—C10B | 114.79 (18) |
N1A—C12A—H12A | 108.7 | N1B—C12B—H12C | 108.6 |
C10A—C12A—H12A | 108.7 | C10B—C12B—H12C | 108.6 |
N1A—C12A—H12B | 108.7 | N1B—C12B—H12D | 108.6 |
C10A—C12A—H12B | 108.7 | C10B—C12B—H12D | 108.6 |
H12A—C12A—H12B | 107.6 | H12C—C12B—H12D | 107.5 |
N1A—C13A—H13A | 109.5 | N1B—C13B—H13D | 109.5 |
N1A—C13A—H13B | 109.5 | N1B—C13B—H13E | 109.5 |
H13A—C13A—H13B | 109.5 | H13D—C13B—H13E | 109.5 |
N1A—C13A—H13C | 109.5 | N1B—C13B—H13F | 109.5 |
H13A—C13A—H13C | 109.5 | H13D—C13B—H13F | 109.5 |
H13B—C13A—H13C | 109.5 | H13E—C13B—H13F | 109.5 |
N1A—C14A—H14A | 109.5 | N1B—C14B—H14D | 109.5 |
N1A—C14A—H14B | 109.5 | N1B—C14B—H14E | 109.5 |
H14A—C14A—H14B | 109.5 | H14D—C14B—H14E | 109.5 |
N1A—C14A—H14C | 109.5 | N1B—C14B—H14F | 109.5 |
H14A—C14A—H14C | 109.5 | H14D—C14B—H14F | 109.5 |
H14B—C14A—H14C | 109.5 | H14E—C14B—H14F | 109.5 |
C14A—N1A—C13A | 111.1 (3) | C14B—N1B—C13B | 111.0 (2) |
C14A—N1A—C12A | 113.4 (2) | C14B—N1B—C12B | 113.4 (2) |
C13A—N1A—C12A | 109.7 (2) | C13B—N1B—C12B | 109.7 (2) |
C14A—N1A—H1NA | 107 (3) | C14B—N1B—H1NB | 105 (2) |
C13A—N1A—H1NA | 105 (3) | C13B—N1B—H1NB | 107 (2) |
C12A—N1A—H1NA | 110 (2) | C12B—N1B—H1NB | 110 (2) |
C5A—O1A—H1OA | 116 (3) | C5B—O1B—H1OB | 110 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1NA···Cl1Bi | 0.85 (1) | 2.25 (2) | 3.056 (2) | 159 (3) |
O1A—H1OA···Cl1A | 0.84 (1) | 2.22 (2) | 3.055 (2) | 172 (4) |
N1B—H1NB···Cl1A | 0.87 (1) | 2.22 (2) | 3.048 (2) | 161 (3) |
O1B—H1OB···Cl1B | 0.85 (1) | 2.25 (2) | 3.070 (2) | 163 (4) |
Symmetry code: (i) x−1, y, z. |
(2R,3R)-3-(3-Hydroxyphenyl)-N,N,2-trimethylpentan-1-aminium (325K)
top
Crystal data top
C14H24NO·Cl | Dx = 1.160 Mg m−3 |
Mr = 257.79 | Melting point: 477 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0653 (2) Å | Cell parameters from 4830 reflections |
b = 11.8351 (3) Å | θ = 2.9–24.9° |
c = 17.6593 (5) Å | µ = 0.25 mm−1 |
V = 1476.64 (7) Å3 | T = 325 K |
Z = 4 | Fragment, colourless |
F(000) = 560 | 0.28 × 0.16 × 0.14 mm |
Data collection top
Bruker APEX-II CCD diffractometer | 2216 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.057 |
Absorption correction: multi-scan Bruker SAINT | θmax = 26.4°, θmin = 2.1° |
Tmin = 0.93, Tmax = 0.97 | h = −8→8 |
9587 measured reflections | k = −14→14 |
3015 independent reflections | l = −18→22 |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.045 | w = 1/[σ2(Fo2) + (0.0512P)2 + 0.4533P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.103 | (Δ/σ)max < 0.001 |
S = 0.90 | Δρmax = 0.22 e Å−3 |
3015 reflections | Δρmin = −0.19 e Å−3 |
164 parameters | Absolute structure: Flack x determined using 731 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). |
2 restraints | Absolute structure parameter: 0.01 (3) |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.2309 (4) | 0.4870 (3) | 0.47040 (17) | 0.0397 (8) | |
C2 | 0.1820 (5) | 0.5952 (3) | 0.44499 (19) | 0.0472 (8) | |
H2 | 0.222886 | 0.619824 | 0.397736 | 0.057* | |
C3 | 0.0741 (6) | 0.6649 (3) | 0.4894 (2) | 0.0544 (10) | |
H3 | 0.044201 | 0.736826 | 0.471942 | 0.065* | |
C4 | 0.0089 (5) | 0.6310 (3) | 0.5593 (2) | 0.0532 (10) | |
H4A | −0.064912 | 0.679181 | 0.588667 | 0.064* | |
C5 | 0.0550 (5) | 0.5243 (3) | 0.58520 (18) | 0.0493 (9) | |
C6 | 0.1663 (5) | 0.4537 (3) | 0.54110 (17) | 0.0439 (8) | |
H6 | 0.198201 | 0.382433 | 0.559321 | 0.053* | |
C7 | 0.3525 (4) | 0.4071 (3) | 0.42299 (17) | 0.0418 (8) | |
H7 | 0.408176 | 0.353758 | 0.459134 | 0.050* | |
C8 | 0.5211 (5) | 0.4656 (3) | 0.3845 (2) | 0.0558 (10) | |
H8A | 0.586853 | 0.410857 | 0.353154 | 0.067* | |
H8B | 0.473702 | 0.524662 | 0.351479 | 0.067* | |
C9 | 0.6590 (6) | 0.5162 (4) | 0.4391 (3) | 0.0773 (13) | |
H9A | 0.766851 | 0.544333 | 0.411973 | 0.116* | |
H9B | 0.699139 | 0.459588 | 0.474591 | 0.116* | |
H9C | 0.599425 | 0.577206 | 0.465901 | 0.116* | |
C10 | 0.2393 (4) | 0.3341 (3) | 0.36671 (17) | 0.0419 (8) | |
H10 | 0.330783 | 0.287265 | 0.339252 | 0.050* | |
C11 | 0.1024 (6) | 0.2541 (3) | 0.4064 (2) | 0.0624 (11) | |
H11A | 0.050139 | 0.202451 | 0.370062 | 0.094* | |
H11B | 0.002215 | 0.296962 | 0.429232 | 0.094* | |
H11C | 0.168765 | 0.212570 | 0.444776 | 0.094* | |
C12 | 0.1396 (5) | 0.4073 (3) | 0.30852 (18) | 0.0462 (8) | |
H12A | 0.042488 | 0.451078 | 0.333947 | 0.055* | |
H12B | 0.230471 | 0.460002 | 0.287405 | 0.055* | |
C13 | −0.0424 (7) | 0.4225 (4) | 0.1913 (2) | 0.0735 (13) | |
H13A | −0.099830 | 0.380542 | 0.150822 | 0.110* | |
H13B | 0.050716 | 0.473133 | 0.170876 | 0.110* | |
H13C | −0.137764 | 0.465161 | 0.217412 | 0.110* | |
C14 | 0.1824 (7) | 0.2654 (4) | 0.2052 (2) | 0.0742 (12) | |
H14A | 0.121221 | 0.234784 | 0.161235 | 0.111* | |
H14B | 0.217908 | 0.204965 | 0.238598 | 0.111* | |
H14C | 0.293390 | 0.306368 | 0.190119 | 0.111* | |
N1 | 0.0501 (4) | 0.3429 (2) | 0.24513 (15) | 0.0463 (7) | |
H1N | −0.039 (4) | 0.302 (2) | 0.2630 (19) | 0.056* | |
O1 | −0.0106 (5) | 0.4938 (3) | 0.65487 (15) | 0.0740 (9) | |
H1O | 0.045 (6) | 0.439 (3) | 0.676 (2) | 0.089* | |
Cl1 | 0.19886 (13) | 0.30455 (7) | 0.73521 (5) | 0.0562 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0350 (17) | 0.0446 (18) | 0.0395 (18) | −0.0037 (14) | −0.0138 (14) | 0.0007 (14) |
C2 | 0.053 (2) | 0.0425 (18) | 0.0456 (17) | −0.0059 (18) | −0.0105 (18) | 0.0031 (15) |
C3 | 0.062 (2) | 0.043 (2) | 0.058 (2) | 0.0019 (18) | −0.0182 (19) | −0.0006 (17) |
C4 | 0.050 (2) | 0.052 (2) | 0.058 (2) | 0.0143 (18) | −0.0135 (18) | −0.0125 (18) |
C5 | 0.048 (2) | 0.063 (2) | 0.0367 (18) | 0.0113 (19) | −0.0087 (16) | −0.0024 (16) |
C6 | 0.042 (2) | 0.0469 (18) | 0.0424 (18) | 0.0084 (16) | −0.0074 (16) | −0.0012 (15) |
C7 | 0.0379 (19) | 0.0473 (18) | 0.0404 (17) | 0.0019 (15) | −0.0053 (14) | 0.0055 (15) |
C8 | 0.039 (2) | 0.065 (2) | 0.064 (2) | −0.0082 (18) | 0.0008 (18) | −0.0028 (19) |
C9 | 0.050 (3) | 0.085 (3) | 0.097 (3) | −0.016 (2) | −0.011 (2) | −0.006 (3) |
C10 | 0.044 (2) | 0.0404 (18) | 0.0415 (17) | −0.0010 (14) | 0.0013 (14) | 0.0017 (13) |
C11 | 0.078 (3) | 0.056 (2) | 0.053 (2) | −0.021 (2) | −0.006 (2) | 0.0121 (18) |
C12 | 0.050 (2) | 0.0425 (18) | 0.0461 (18) | −0.0092 (16) | −0.0080 (16) | 0.0042 (16) |
C13 | 0.079 (3) | 0.076 (3) | 0.065 (2) | −0.012 (3) | −0.030 (2) | 0.023 (2) |
C14 | 0.070 (3) | 0.099 (3) | 0.054 (2) | −0.002 (3) | 0.009 (2) | −0.021 (2) |
N1 | 0.0445 (16) | 0.0524 (16) | 0.0420 (16) | −0.0125 (13) | −0.0025 (13) | 0.0044 (12) |
O1 | 0.080 (2) | 0.086 (2) | 0.0556 (17) | 0.0391 (16) | 0.0127 (15) | 0.0104 (15) |
Cl1 | 0.0527 (5) | 0.0503 (5) | 0.0657 (5) | 0.0112 (4) | −0.0019 (5) | −0.0051 (4) |
Geometric parameters (Å, º) top
C1—C6 | 1.387 (4) | C9—H9C | 0.9600 |
C1—C2 | 1.400 (5) | C10—C12 | 1.517 (4) |
C1—C7 | 1.528 (5) | C10—C11 | 1.524 (5) |
C2—C3 | 1.370 (5) | C10—H10 | 0.9800 |
C2—H2 | 0.9300 | C11—H11A | 0.9600 |
C3—C4 | 1.378 (5) | C11—H11B | 0.9600 |
C3—H3 | 0.9300 | C11—H11C | 0.9600 |
C4—C5 | 1.382 (5) | C12—N1 | 1.494 (4) |
C4—H4A | 0.9300 | C12—H12A | 0.9700 |
C5—C6 | 1.387 (5) | C12—H12B | 0.9700 |
C5—O1 | 1.363 (4) | C13—N1 | 1.489 (5) |
C6—H6 | 0.9300 | C13—H13A | 0.9600 |
C7—C10 | 1.541 (4) | C13—H13B | 0.9600 |
C7—C8 | 1.536 (5) | C13—H13C | 0.9600 |
C7—H7 | 0.9800 | C14—N1 | 1.487 (5) |
C8—C9 | 1.497 (5) | C14—H14A | 0.9600 |
C8—H8A | 0.9700 | C14—H14B | 0.9600 |
C8—H8B | 0.9700 | C14—H14C | 0.9600 |
C9—H9A | 0.9600 | N1—H1N | 0.856 (13) |
C9—H9B | 0.9600 | O1—H1O | 0.846 (13) |
| | | |
C6—C1—C2 | 117.9 (3) | C7—C10—C11 | 112.4 (3) |
C6—C1—C7 | 120.2 (3) | C12—C10—C11 | 111.8 (3) |
C2—C1—C7 | 122.0 (3) | C7—C10—H10 | 107.1 |
C3—C2—C1 | 120.3 (3) | C12—C10—H10 | 107.1 |
C3—C2—H2 | 119.9 | C11—C10—H10 | 107.1 |
C1—C2—H2 | 119.9 | C10—C11—H11A | 109.5 |
C4—C3—C2 | 121.6 (3) | C10—C11—H11B | 109.5 |
C4—C3—H3 | 119.2 | H11A—C11—H11B | 109.5 |
C2—C3—H3 | 119.2 | C10—C11—H11C | 109.5 |
C3—C4—C5 | 118.9 (3) | H11A—C11—H11C | 109.5 |
C3—C4—H4A | 120.6 | H11B—C11—H11C | 109.5 |
C5—C4—H4A | 120.6 | N1—C12—C10 | 114.4 (3) |
C6—C5—O1 | 122.7 (3) | N1—C12—H12A | 108.7 |
C6—C5—C4 | 119.9 (3) | C10—C12—H12A | 108.7 |
O1—C5—C4 | 117.4 (3) | N1—C12—H12B | 108.7 |
C5—C6—C1 | 121.4 (3) | C10—C12—H12B | 108.7 |
C5—C6—H6 | 119.3 | H12A—C12—H12B | 107.6 |
C1—C6—H6 | 119.3 | N1—C13—H13A | 109.5 |
C10—C7—C1 | 114.1 (3) | N1—C13—H13B | 109.5 |
C10—C7—C8 | 111.7 (3) | H13A—C13—H13B | 109.5 |
C1—C7—C8 | 113.6 (3) | N1—C13—H13C | 109.5 |
C10—C7—H7 | 105.5 | H13A—C13—H13C | 109.5 |
C1—C7—H7 | 105.5 | H13B—C13—H13C | 109.5 |
C8—C7—H7 | 105.5 | N1—C14—H14A | 109.5 |
C9—C8—C7 | 113.5 (3) | N1—C14—H14B | 109.5 |
C9—C8—H8A | 108.9 | H14A—C14—H14B | 109.5 |
C7—C8—H8A | 108.9 | N1—C14—H14C | 109.5 |
C9—C8—H8B | 108.9 | H14A—C14—H14C | 109.5 |
C7—C8—H8B | 108.9 | H14B—C14—H14C | 109.5 |
H8A—C8—H8B | 107.7 | C14—N1—C12 | 113.8 (3) |
C8—C9—H9A | 109.5 | C14—N1—C13 | 111.3 (3) |
C8—C9—H9B | 109.5 | C12—N1—C13 | 110.0 (3) |
H9A—C9—H9B | 109.5 | C14—N1—H1N | 107 (2) |
C8—C9—H9C | 109.5 | C12—N1—H1N | 109 (2) |
H9A—C9—H9C | 109.5 | C13—N1—H1N | 106 (2) |
H9B—C9—H9C | 109.5 | C5—O1—H1O | 117 (3) |
C7—C10—C12 | 111.0 (3) | | |
| | | |
C6—C1—C2—C3 | 0.2 (5) | C6—C1—C7—C8 | −137.2 (3) |
C7—C1—C2—C3 | −179.4 (3) | C2—C1—C7—C8 | 42.4 (4) |
C1—C2—C3—C4 | −0.8 (5) | C10—C7—C8—C9 | −167.3 (3) |
C2—C3—C4—C5 | 0.5 (5) | C1—C7—C8—C9 | 62.0 (4) |
C3—C4—C5—C6 | 0.4 (5) | C1—C7—C10—C12 | 62.8 (3) |
C3—C4—C5—O1 | 179.5 (3) | C8—C7—C10—C12 | −67.7 (4) |
O1—C5—C6—C1 | 180.0 (3) | C1—C7—C10—C11 | −63.2 (4) |
C4—C5—C6—C1 | −1.0 (5) | C8—C7—C10—C11 | 166.3 (3) |
C2—C1—C6—C5 | 0.7 (5) | C7—C10—C12—N1 | 171.4 (3) |
C7—C1—C6—C5 | −179.7 (3) | C11—C10—C12—N1 | −62.2 (4) |
C6—C1—C7—C10 | 93.3 (3) | C10—C12—N1—C14 | −54.0 (4) |
C2—C1—C7—C10 | −87.2 (4) | C10—C12—N1—C13 | −179.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1i | 0.86 (1) | 2.24 (2) | 3.054 (3) | 159 (3) |
O1—H1O···Cl1 | 0.85 (1) | 2.19 (1) | 3.037 (3) | 177 (5) |
Symmetry code: (i) x−1/2, −y+1/2, −z+1. |