Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111001727/sf3144sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111001727/sf3144Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111001727/sf3144IIsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111001727/sf3144IIIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111001727/sf3144IVsup5.hkl |
CCDC references: 817046; 817047; 817048; 817049
(2R,3R)-3-(3-Hydroxyphenyl)-N,N,2-trimethylpentan-1-aminium chloride, (I), was prepared as follows. [(2R,3S)-1-(Dimethylamino)-3-(3-hydroxyphenyl)-2-methylpentan-3-ol tartaric acid salt (35 g) and water (150 ml) were placed in a round-bottomed flask and an aqueous ammonia solution (30 ml) was added to obtain a basic pH, followed by extraction in dichloromethane (150 ml) at 293–298 K. The organic layer was separated and distilled completely to obtain an oil. 2-Methyltetrahydrofuran (300 ml) and trifluoroacetic anhydride (50 ml) were added to this oil at 293–298 K. The mixture was transferred to an autoclave, Pd/C (9 g, 10% Pd, 50% wet) was added and a hydrogen pressure (5 to 7 kg) was applied. The reaction mixture was heated to 318–323 K for 5 h. After cooling, the reaction mass was filtered through Hyflo (Manufacturer?) and the filtrate was distilled under vacuum at 318–323 K to obtain an oil, to which water (150 ml) and aqueous ammonia (30 ml) were added. The aqueous layer was extracted using dichloromethane (150 ml) and the organic layer was distilled off under vacuum at 308–313 K to obtain an oil. Propan-2-ol (100 ml) and propan-2-ol–HCl (30 ml, pH 1–2) were added to this oil and the mixture stirred for 1 h at 293–298 K. The resulting slurry was cooled to 273–278 K for 1 h. The solid was fltered off and washed with propan-2-ol (30 ml), and then dried in an air oven at 328 K for 10–12 h. The solid was then recrystallized from a solution in butanone to yield a white solid. Purity by HPLC: 99.53%; m.p. 482–483 K; 1H NMR (D2O, δ, p.p.m.): 0.54 (t, 3H, –CH2—CH3), 0.96 (d, 3H, –CH—CH3), 1.42, 1.73 (m, 2H, –CH2—CH3), 2.04 (m, 1H, –CH–Ethyl), 2.20 (m, 1H, –CH—CH3), 2.61 [s, 6H, –N(Me)2], 2.70, 2.74 (m, 2H, –CH2), 6.62 (d, 1H, Ar—H), 6.69 (dd, 2H, Ar—H), 7.13 (t, 1H, Ar—H); MS: m/z 221 (M+).
(2S,3S)-3-(3-Hydroxyphenyl)-N,N,2-trimethylpentan-1-aminium chloride, (II), was prepared as follows. Using [(2S,3R)-1-(dimethylamino)-3-(3-hydroxyphenyl)-2-methylpentan-3-ol tartaric acid salt, the above process was followed to obtain (II). It was recrystallized from a solution in butanone to yield a white solid. Purity by HPLC: 99.85%; m.p. 480–481 K; 1H NMR (D2O, δ, p.p.m.): 0.55 (t, 3H, –CH2—CH3), 0.97 (d, 3H, –CH—CH3), 1.45, 1.74 (m, 2H, –CH2—CH3), 2.06 (m, 1H, –CH-Ethyl), 2.23 (m, 1H, –CH—CH3), 2.65 [s, 6H, –N(Me)2], 2.70, 2.78 (m, 2H, –CH2), 6.64 (d, 1H, Ar—H), 6.69 (dd, 2H, Ar—H), 7.15 (t, 1H, Ar—H); MS: m/z 221 (M+).
(2R,3S)-3-(3-Hydroxyphenyl)-N,N,2-trimethylpentan-1-aminium chloride, (III), was prepared as follows. Toluene (160 ml), aluminium chloride (45.3 g) and thiourea (20 g) were placed in a round-bottomed flask and stirred at 293–298 K for 30 min. [(2R,3S)-1-(Dimethylamino)-3-(3-methoxyphenyl)-2-methylpentane (20 g) was dissolved in toluene (40 ml). This solution was added to the above mixture at 293–298 K and the combined mixture heated at 383–388 K for 6 h. After cooling, water (50 ml) and aqueous ammonia (100 ml) were added, and the mixture was filtered through Hyflo and the organic layer separated. The aqueous layer was extracted with toluene (100 ml). The combined organic layers were washed with water (100 ml) and then distilled off under vacuum at 323–328 K to obtain an oil. Propan-2-ol (50 ml) and propan-2-ol–HCl (30 ml, pH 1–2) were added to this oil and the mixture was stirred for 2 h at 273–278 K. The solid was then filtered off, washed with propan-2-ol (10 ml), dried under vacuum at 313–318 K for 2 h and recrystallized from a solution in butanone to yield a white solid (m.p. 477–478 K). 1H NMR (D2O, δ, p.p.m.): 0.60 (t, 3H, –CH2—CH3), 0.75 (d, 3H, –CH—CH3), 1.57 (m, 2H, –CH2—CH3), 2.10 (m, 1H, –CH-Ethyl), 2.35 (p, 1H, –CH—CH3), 2.72 [s, 6H, –N(Me)2], 3.09 (dd, 2H, –CH2), 6.62 (d, 1H, Ar—H), 6.69 (dd, 2H, Ar—H), 7.13 (t, 1H, Ar—H); MS: m/z 221 (M+).
(2S,3R)-3-(3-Hydroxyphenyl)- N,N,2-trimethylpentan-1-aminium chloride, (IV), was prepared as follows. [(2S,3R)-1-(Dimethylamino)-3-(3-methoxyphenyl)-2-methylpentane (12 g) and aqueous HBr (80 ml) were placed in a round-bottomed flask at 293–298 K. The reaction mass was heated to 373 K for 15–16 h. After cooling, water (200 ml), ice (200 g) and aqueous ammonia (200 ml) were added to the reaction mass at 278–283 K. The product was extracted with dichloromethane (400 ml) and the organic layer was distilled off under vacuum at 308–313 K to obtain an oil. Propan-2-ol (100 ml) and propan-2-ol–HCl (20 ml, pH 1–2) were added to this oil and the mixture stirred for 2 h at 273–278 K. The solid was then filtered off, washed with propan-2-ol (25 ml), dried in an air oven at 323–328 K and recrystallized from a solution in butanone to yield a white solid (m.p. 478–479 K). 1H NMR (D2O, δ, p.p.m.): 0.61 (t, 3H, –CH2—CH3), 0.75 (d, 3H, –CH—CH3), 1.59 (m, 2H, –CH2—CH3), 2.10 (m, 1H, –CH-Ethyl), 2.36 (p, 1H, –CH—CH3), 2.73 [s, 6H, –N(Me)2], 3.09 (dd, 2H, –CH2), 6.63 (d, 1H, Ar—H), 6.69 (dd, 2H, Ar—H), 7.15 (t, 1H, Ar—H); MS: m/z 221 (M+).
HPLC analysis was performed with a Shimadzu LC 2010 series HPLC system (EMPOWER software) equipped with a quaternary pump and UV detector monitoring the range 200–400 nm. Isomers were analysed on a CHIRALPAK AD-3 (250 × 4.6 mm × 5µm) column using the normal-phase method, while a reverse-phase HPLC analysis was carried out using INERTSIL ODS-3 V (4.6 × 250 mm × 5 µm). The mobile phase was an 85:15 (v/v) mixture of hexane and tetrahydrofuran, respectively.
Single crystals of all four isomers, (I)–(IV), suitable for X-ray crystallography studies were obtained by cooling hot methanol solutions.
All N and O-bound H atoms were located in a difference Fourier density map and refined isotropically. All other H atoms were positioned geometrically and treated as riding on their parent C atoms, with C—H = 0.93–0.98 Å, and with Uiso(H) = 1.5Ueq(C) for methyl H or 1.2Ueq(C) for other H atoms. The methyl groups were allowed to rotate but not to tip. The absolute configuration was determined from the anomalous X-ray scattering from the Cl atoms. The Flack absolute configuration parameters were 0.03 (4) for (I), -0.02 (4) for (II), -0.02 (7) for (III) and 0.00 (6) for (IV) (Flack & Bernardinelli, 2000). A value of zero represents the correct structure and a value of one represents the inverted structure. The parameters were determined from the refinement of 2430 Friedel pairs for (I), 2431 pairs for (II), 1113 pairs for (III) and 1104 pairs for (IV).
For all compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C14H24NO+·Cl− | F(000) = 560 |
Mr = 257.79 | Dx = 1.172 Mg m−3 |
Monoclinic, P21 | Melting point: 482 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1600 (15) Å | Cell parameters from 5112 reflections |
b = 11.688 (3) Å | θ = 2.3–28.0° |
c = 17.514 (4) Å | µ = 0.25 mm−1 |
β = 94.535 (3)° | T = 294 K |
V = 1461.1 (5) Å3 | Block, colourless |
Z = 4 | 0.18 × 0.15 × 0.09 mm |
Bruker SMART APEX CCD area-detector diffractometer | 5135 independent reflections |
Radiation source: fine-focus sealed tube | 4972 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 25.0°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −8→8 |
Tmin = 0.955, Tmax = 0.976 | k = −13→13 |
14096 measured reflections | l = −20→20 |
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)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.072 | w = 1/[σ2(Fo2) + (0.0389P)2 + 0.130P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
5135 reflections | Δρmax = 0.14 e Å−3 |
331 parameters | Δρmin = −0.12 e Å−3 |
1 restraint | Absolute structure: Flack & Bernardinelli (2000), with 2430 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (4) |
C14H24NO+·Cl− | V = 1461.1 (5) Å3 |
Mr = 257.79 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.1600 (15) Å | µ = 0.25 mm−1 |
b = 11.688 (3) Å | T = 294 K |
c = 17.514 (4) Å | 0.18 × 0.15 × 0.09 mm |
β = 94.535 (3)° |
Bruker SMART APEX CCD area-detector diffractometer | 5135 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 4972 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.976 | Rint = 0.022 |
14096 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.072 | Δρmax = 0.14 e Å−3 |
S = 1.06 | Δρmin = −0.12 e Å−3 |
5135 reflections | Absolute structure: Flack & Bernardinelli (2000), with 2430 Friedel pairs |
331 parameters | Absolute structure parameter: 0.03 (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. |
x | y | z | Uiso*/Ueq | ||
C1A | 0.2230 (2) | 0.53067 (13) | 0.77595 (8) | 0.0411 (3) | |
C2A | 0.1655 (2) | 0.42334 (14) | 0.79941 (10) | 0.0468 (4) | |
H2A | 0.2051 | 0.3966 | 0.8480 | 0.056* | |
C3A | 0.0501 (2) | 0.35644 (14) | 0.75092 (10) | 0.0506 (4) | |
H3A | 0.0129 | 0.2850 | 0.7675 | 0.061* | |
C4A | −0.0113 (2) | 0.39336 (15) | 0.67811 (10) | 0.0511 (4) | |
H4A | −0.0884 | 0.3473 | 0.6458 | 0.061* | |
C5A | 0.0441 (2) | 0.50000 (15) | 0.65445 (9) | 0.0484 (4) | |
C6A | 0.1607 (2) | 0.56758 (15) | 0.70285 (9) | 0.0451 (3) | |
H6A | 0.1979 | 0.6389 | 0.6861 | 0.054* | |
C7A | 0.3508 (2) | 0.60749 (14) | 0.82733 (9) | 0.0434 (3) | |
H7A | 0.4042 | 0.6628 | 0.7931 | 0.052* | |
C8A | 0.5179 (2) | 0.54344 (17) | 0.86704 (11) | 0.0548 (4) | |
H8A | 0.5873 | 0.5950 | 0.9022 | 0.066* | |
H8B | 0.4721 | 0.4809 | 0.8968 | 0.066* | |
C9A | 0.6488 (3) | 0.4961 (2) | 0.81056 (13) | 0.0711 (6) | |
H9A | 0.5840 | 0.4395 | 0.7788 | 0.107* | |
H9B | 0.7557 | 0.4618 | 0.8381 | 0.107* | |
H9C | 0.6894 | 0.5571 | 0.7791 | 0.107* | |
C10A | 0.2460 (2) | 0.67956 (13) | 0.88482 (9) | 0.0433 (3) | |
H10A | 0.3407 | 0.7250 | 0.9147 | 0.052* | |
C11A | 0.1098 (3) | 0.76350 (16) | 0.84416 (10) | 0.0593 (4) | |
H11A | 0.0079 | 0.7222 | 0.8181 | 0.089* | |
H11B | 0.1735 | 0.8071 | 0.8077 | 0.089* | |
H11C | 0.0619 | 0.8142 | 0.8811 | 0.089* | |
C12A | 0.1527 (2) | 0.60464 (14) | 0.94078 (9) | 0.0474 (4) | |
H12A | 0.0535 | 0.5616 | 0.9129 | 0.057* | |
H12B | 0.2440 | 0.5500 | 0.9626 | 0.057* | |
C13A | −0.0158 (3) | 0.5842 (2) | 1.05630 (13) | 0.0767 (6) | |
H13A | 0.0765 | 0.5293 | 1.0751 | 0.115* | |
H13B | −0.1173 | 0.5453 | 1.0281 | 0.115* | |
H13C | −0.0624 | 0.6243 | 1.0987 | 0.115* | |
C14A | 0.2065 (3) | 0.7431 (2) | 1.04853 (12) | 0.0782 (7) | |
H14A | 0.3152 | 0.6997 | 1.0663 | 0.117* | |
H14B | 0.1493 | 0.7746 | 1.0916 | 0.117* | |
H14C | 0.2427 | 0.8040 | 1.0160 | 0.117* | |
N1A | 0.0712 (2) | 0.66755 (13) | 1.00491 (8) | 0.0498 (3) | |
H1N | −0.021 (3) | 0.7102 (16) | 0.9856 (9) | 0.042 (4)* | |
O1A | −0.0167 (2) | 0.53353 (14) | 0.58189 (7) | 0.0686 (4) | |
H1O | 0.044 (3) | 0.589 (2) | 0.5671 (13) | 0.075 (7)* | |
C1B | 0.6956 (2) | 1.01275 (14) | 0.73214 (8) | 0.0428 (3) | |
C2B | 0.6216 (2) | 1.11695 (15) | 0.70488 (10) | 0.0500 (4) | |
H2B | 0.6607 | 1.1481 | 0.6599 | 0.060* | |
C3B | 0.4905 (3) | 1.17376 (15) | 0.74463 (10) | 0.0558 (4) | |
H3B | 0.4406 | 1.2424 | 0.7255 | 0.067* | |
C4B | 0.4319 (2) | 1.13059 (16) | 0.81210 (10) | 0.0555 (4) | |
H4B | 0.3450 | 1.1704 | 0.8386 | 0.067* | |
C5B | 0.5039 (2) | 1.02764 (16) | 0.83984 (9) | 0.0508 (4) | |
C6B | 0.6346 (2) | 0.96934 (15) | 0.79978 (9) | 0.0472 (4) | |
H6B | 0.6821 | 0.8999 | 0.8186 | 0.057* | |
C7B | 0.8437 (2) | 0.94794 (14) | 0.69167 (9) | 0.0437 (3) | |
H7B | 0.9092 | 0.9000 | 0.7311 | 0.052* | |
C8B | 0.9929 (2) | 1.02946 (16) | 0.66432 (11) | 0.0536 (4) | |
H8C | 0.9351 | 1.0771 | 0.6237 | 0.064* | |
H8D | 1.0350 | 1.0794 | 0.7065 | 0.064* | |
C9B | 1.1617 (3) | 0.9715 (2) | 0.63533 (14) | 0.0744 (6) | |
H9D | 1.2096 | 0.9157 | 0.6720 | 0.112* | |
H9E | 1.2566 | 1.0275 | 0.6280 | 0.112* | |
H9F | 1.1262 | 0.9344 | 0.5875 | 0.112* | |
C10B | 0.7620 (2) | 0.86367 (14) | 0.62899 (9) | 0.0418 (3) | |
H10B | 0.8681 | 0.8250 | 0.6080 | 0.050* | |
C11B | 0.6406 (3) | 0.77170 (16) | 0.66174 (10) | 0.0582 (4) | |
H11D | 0.5319 | 0.8065 | 0.6806 | 0.087* | |
H11E | 0.7111 | 0.7330 | 0.7029 | 0.087* | |
H11F | 0.6024 | 0.7176 | 0.6223 | 0.087* | |
C12B | 0.6575 (2) | 0.92858 (13) | 0.56351 (9) | 0.0443 (4) | |
H12C | 0.5545 | 0.9698 | 0.5836 | 0.053* | |
H12D | 0.7417 | 0.9848 | 0.5443 | 0.053* | |
C13B | 0.4897 (3) | 0.93067 (18) | 0.43623 (11) | 0.0628 (5) | |
H13D | 0.5796 | 0.9845 | 0.4198 | 0.094* | |
H13E | 0.3870 | 0.9712 | 0.4558 | 0.094* | |
H13F | 0.4440 | 0.8842 | 0.3936 | 0.094* | |
C14B | 0.7238 (3) | 0.7802 (2) | 0.46717 (11) | 0.0663 (5) | |
H14D | 0.6710 | 0.7429 | 0.4217 | 0.099* | |
H14E | 0.7630 | 0.7238 | 0.5049 | 0.099* | |
H14F | 0.8300 | 0.8251 | 0.4552 | 0.099* | |
N1B | 0.58074 (19) | 0.85609 (12) | 0.49780 (7) | 0.0445 (3) | |
H2N | 0.492 (3) | 0.8086 (19) | 0.5141 (11) | 0.062 (5)* | |
O1B | 0.4466 (2) | 0.98863 (15) | 0.90748 (8) | 0.0696 (4) | |
H2O | 0.505 (4) | 0.934 (2) | 0.9218 (14) | 0.079 (8)* | |
Cl1A | 0.22980 (6) | 0.71158 (4) | 0.51060 (3) | 0.05598 (11) | |
Cl1B | 0.71615 (6) | 0.81338 (4) | 0.98631 (3) | 0.05652 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0380 (8) | 0.0436 (8) | 0.0424 (8) | 0.0047 (6) | 0.0079 (6) | −0.0020 (6) |
C2A | 0.0496 (9) | 0.0450 (8) | 0.0460 (8) | 0.0077 (7) | 0.0054 (7) | −0.0008 (7) |
C3A | 0.0537 (9) | 0.0411 (8) | 0.0585 (10) | −0.0016 (7) | 0.0137 (8) | −0.0037 (7) |
C4A | 0.0427 (9) | 0.0564 (10) | 0.0549 (9) | −0.0083 (7) | 0.0088 (7) | −0.0127 (8) |
C5A | 0.0428 (8) | 0.0612 (10) | 0.0416 (8) | −0.0021 (8) | 0.0059 (6) | −0.0030 (7) |
C6A | 0.0434 (8) | 0.0487 (9) | 0.0436 (8) | −0.0048 (7) | 0.0066 (6) | −0.0008 (7) |
C7A | 0.0399 (8) | 0.0480 (8) | 0.0422 (8) | −0.0013 (7) | 0.0028 (6) | −0.0006 (7) |
C8A | 0.0421 (9) | 0.0611 (11) | 0.0606 (10) | 0.0066 (8) | −0.0011 (7) | −0.0033 (8) |
C9A | 0.0482 (10) | 0.0724 (13) | 0.0943 (15) | 0.0117 (10) | 0.0158 (10) | −0.0027 (11) |
C10A | 0.0428 (8) | 0.0421 (8) | 0.0442 (8) | 0.0016 (6) | −0.0012 (6) | −0.0023 (6) |
C11A | 0.0692 (12) | 0.0533 (10) | 0.0550 (10) | 0.0170 (9) | 0.0030 (9) | 0.0046 (8) |
C12A | 0.0526 (9) | 0.0403 (8) | 0.0502 (9) | 0.0081 (7) | 0.0102 (7) | −0.0014 (7) |
C13A | 0.0839 (14) | 0.0799 (14) | 0.0709 (13) | 0.0194 (12) | 0.0357 (11) | 0.0217 (11) |
C14A | 0.0765 (14) | 0.0992 (18) | 0.0577 (11) | 0.0006 (12) | −0.0027 (10) | −0.0235 (12) |
N1A | 0.0493 (8) | 0.0534 (8) | 0.0472 (7) | 0.0120 (7) | 0.0066 (6) | 0.0003 (6) |
O1A | 0.0699 (9) | 0.0868 (10) | 0.0470 (7) | −0.0242 (8) | −0.0089 (6) | 0.0078 (7) |
C1B | 0.0369 (8) | 0.0467 (8) | 0.0436 (8) | 0.0019 (7) | −0.0041 (6) | −0.0069 (7) |
C2B | 0.0482 (9) | 0.0499 (9) | 0.0512 (9) | 0.0038 (7) | −0.0006 (7) | 0.0020 (7) |
C3B | 0.0547 (10) | 0.0488 (9) | 0.0628 (11) | 0.0132 (8) | −0.0011 (8) | −0.0005 (8) |
C4B | 0.0499 (9) | 0.0582 (10) | 0.0584 (10) | 0.0136 (8) | 0.0049 (8) | −0.0078 (8) |
C5B | 0.0462 (9) | 0.0605 (10) | 0.0455 (9) | 0.0046 (8) | 0.0021 (7) | −0.0034 (8) |
C6B | 0.0453 (9) | 0.0483 (9) | 0.0468 (8) | 0.0074 (7) | −0.0047 (7) | −0.0020 (7) |
C7B | 0.0371 (8) | 0.0488 (9) | 0.0444 (8) | 0.0079 (7) | −0.0024 (6) | 0.0008 (7) |
C8B | 0.0364 (8) | 0.0576 (10) | 0.0662 (11) | −0.0026 (7) | 0.0000 (7) | −0.0107 (8) |
C9B | 0.0495 (10) | 0.0774 (14) | 0.0984 (15) | −0.0036 (10) | 0.0182 (10) | −0.0195 (12) |
C10B | 0.0394 (8) | 0.0405 (8) | 0.0453 (8) | 0.0038 (6) | 0.0028 (6) | 0.0009 (7) |
C11B | 0.0718 (12) | 0.0490 (9) | 0.0531 (10) | −0.0090 (8) | 0.0005 (8) | 0.0066 (8) |
C12B | 0.0444 (8) | 0.0414 (8) | 0.0464 (8) | −0.0024 (7) | −0.0004 (7) | 0.0012 (6) |
C13B | 0.0617 (11) | 0.0703 (12) | 0.0538 (10) | −0.0102 (9) | −0.0129 (8) | 0.0125 (9) |
C14B | 0.0650 (12) | 0.0815 (14) | 0.0528 (10) | 0.0079 (10) | 0.0076 (9) | −0.0157 (9) |
N1B | 0.0407 (7) | 0.0490 (8) | 0.0437 (7) | −0.0059 (6) | 0.0015 (5) | 0.0030 (6) |
O1B | 0.0704 (9) | 0.0804 (10) | 0.0606 (8) | 0.0256 (8) | 0.0207 (7) | 0.0100 (7) |
Cl1A | 0.0526 (2) | 0.0472 (2) | 0.0679 (3) | −0.00960 (19) | 0.00320 (17) | −0.00328 (19) |
Cl1B | 0.0522 (2) | 0.0498 (2) | 0.0675 (3) | 0.00818 (19) | 0.00444 (17) | −0.0043 (2) |
C1A—C6A | 1.391 (2) | C1B—C6B | 1.390 (2) |
C1A—C2A | 1.392 (2) | C1B—C2B | 1.397 (2) |
C1A—C7A | 1.524 (2) | C1B—C7B | 1.523 (2) |
C2A—C3A | 1.380 (2) | C2B—C3B | 1.382 (3) |
C2A—H2A | 0.9300 | C2B—H2B | 0.9300 |
C3A—C4A | 1.385 (3) | C3B—C4B | 1.380 (3) |
C3A—H3A | 0.9300 | C3B—H3B | 0.9300 |
C4A—C5A | 1.382 (3) | C4B—C5B | 1.382 (3) |
C4A—H4A | 0.9300 | C4B—H4B | 0.9300 |
C5A—O1A | 1.368 (2) | C5B—O1B | 1.362 (2) |
C5A—C6A | 1.389 (2) | C5B—C6B | 1.392 (2) |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C7A—C8A | 1.531 (2) | C7B—C8B | 1.536 (2) |
C7A—C10A | 1.551 (2) | C7B—C10B | 1.554 (2) |
C7A—H7A | 0.9800 | C7B—H7B | 0.9800 |
C8A—C9A | 1.520 (3) | C8B—C9B | 1.508 (3) |
C8A—H8A | 0.9700 | C8B—H8C | 0.9700 |
C8A—H8B | 0.9700 | C8B—H8D | 0.9700 |
C9A—H9A | 0.9600 | C9B—H9D | 0.9600 |
C9A—H9B | 0.9600 | C9B—H9E | 0.9600 |
C9A—H9C | 0.9600 | C9B—H9F | 0.9600 |
C10A—C12A | 1.509 (2) | C10B—C12B | 1.522 (2) |
C10A—C11A | 1.520 (2) | C10B—C11B | 1.523 (2) |
C10A—H10A | 0.9800 | C10B—H10B | 0.9800 |
C11A—H11A | 0.9600 | C11B—H11D | 0.9600 |
C11A—H11B | 0.9600 | C11B—H11E | 0.9600 |
C11A—H11C | 0.9600 | C11B—H11F | 0.9600 |
C12A—N1A | 1.499 (2) | C12B—N1B | 1.498 (2) |
C12A—H12A | 0.9700 | C12B—H12C | 0.9700 |
C12A—H12B | 0.9700 | C12B—H12D | 0.9700 |
C13A—N1A | 1.496 (3) | C13B—N1B | 1.495 (2) |
C13A—H13A | 0.9600 | C13B—H13D | 0.9600 |
C13A—H13B | 0.9600 | C13B—H13E | 0.9600 |
C13A—H13C | 0.9600 | C13B—H13F | 0.9600 |
C14A—N1A | 1.478 (3) | C14B—N1B | 1.487 (2) |
C14A—H14A | 0.9600 | C14B—H14D | 0.9600 |
C14A—H14B | 0.9600 | C14B—H14E | 0.9600 |
C14A—H14C | 0.9600 | C14B—H14F | 0.9600 |
N1A—H1N | 0.875 (19) | N1B—H2N | 0.90 (2) |
O1A—H1O | 0.83 (3) | O1B—H2O | 0.79 (3) |
C6A—C1A—C2A | 118.07 (15) | C6B—C1B—C2B | 118.24 (15) |
C6A—C1A—C7A | 119.64 (14) | C6B—C1B—C7B | 119.49 (14) |
C2A—C1A—C7A | 122.28 (14) | C2B—C1B—C7B | 122.25 (15) |
C3A—C2A—C1A | 120.36 (15) | C3B—C2B—C1B | 120.06 (16) |
C3A—C2A—H2A | 119.8 | C3B—C2B—H2B | 120.0 |
C1A—C2A—H2A | 119.8 | C1B—C2B—H2B | 120.0 |
C2A—C3A—C4A | 121.43 (16) | C4B—C3B—C2B | 121.33 (16) |
C2A—C3A—H3A | 119.3 | C4B—C3B—H3B | 119.3 |
C4A—C3A—H3A | 119.3 | C2B—C3B—H3B | 119.3 |
C5A—C4A—C3A | 118.65 (16) | C3B—C4B—C5B | 119.29 (16) |
C5A—C4A—H4A | 120.7 | C3B—C4B—H4B | 120.4 |
C3A—C4A—H4A | 120.7 | C5B—C4B—H4B | 120.4 |
O1A—C5A—C4A | 117.34 (16) | O1B—C5B—C4B | 117.89 (16) |
O1A—C5A—C6A | 122.42 (16) | O1B—C5B—C6B | 122.35 (16) |
C4A—C5A—C6A | 120.22 (15) | C4B—C5B—C6B | 119.73 (16) |
C5A—C6A—C1A | 121.27 (15) | C1B—C6B—C5B | 121.34 (15) |
C5A—C6A—H6A | 119.4 | C1B—C6B—H6B | 119.3 |
C1A—C6A—H6A | 119.4 | C5B—C6B—H6B | 119.3 |
C1A—C7A—C8A | 113.03 (14) | C1B—C7B—C8B | 111.32 (14) |
C1A—C7A—C10A | 113.87 (13) | C1B—C7B—C10B | 114.01 (12) |
C8A—C7A—C10A | 111.80 (13) | C8B—C7B—C10B | 113.89 (13) |
C1A—C7A—H7A | 105.8 | C1B—C7B—H7B | 105.6 |
C8A—C7A—H7A | 105.8 | C8B—C7B—H7B | 105.6 |
C10A—C7A—H7A | 105.8 | C10B—C7B—H7B | 105.6 |
C9A—C8A—C7A | 112.48 (16) | C9B—C8B—C7B | 114.95 (16) |
C9A—C8A—H8A | 109.1 | C9B—C8B—H8C | 108.5 |
C7A—C8A—H8A | 109.1 | C7B—C8B—H8C | 108.5 |
C9A—C8A—H8B | 109.1 | C9B—C8B—H8D | 108.5 |
C7A—C8A—H8B | 109.1 | C7B—C8B—H8D | 108.5 |
H8A—C8A—H8B | 107.8 | H8C—C8B—H8D | 107.5 |
C8A—C9A—H9A | 109.5 | C8B—C9B—H9D | 109.5 |
C8A—C9A—H9B | 109.5 | C8B—C9B—H9E | 109.5 |
H9A—C9A—H9B | 109.5 | H9D—C9B—H9E | 109.5 |
C8A—C9A—H9C | 109.5 | C8B—C9B—H9F | 109.5 |
H9A—C9A—H9C | 109.5 | H9D—C9B—H9F | 109.5 |
H9B—C9A—H9C | 109.5 | H9E—C9B—H9F | 109.5 |
C12A—C10A—C11A | 112.23 (14) | C12B—C10B—C11B | 112.00 (13) |
C12A—C10A—C7A | 111.60 (13) | C12B—C10B—C7B | 110.58 (13) |
C11A—C10A—C7A | 111.82 (13) | C11B—C10B—C7B | 112.05 (13) |
C12A—C10A—H10A | 106.9 | C12B—C10B—H10B | 107.3 |
C11A—C10A—H10A | 106.9 | C11B—C10B—H10B | 107.3 |
C7A—C10A—H10A | 106.9 | 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 | 114.86 (13) | N1B—C12B—C10B | 115.19 (12) |
N1A—C12A—H12A | 108.6 | N1B—C12B—H12C | 108.5 |
C10A—C12A—H12A | 108.6 | C10B—C12B—H12C | 108.5 |
N1A—C12A—H12B | 108.6 | N1B—C12B—H12D | 108.5 |
C10A—C12A—H12B | 108.6 | C10B—C12B—H12D | 108.5 |
H12A—C12A—H12B | 107.5 | 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 | 111.43 (17) | C14B—N1B—C13B | 111.16 (14) |
C14A—N1A—C12A | 113.74 (15) | C14B—N1B—C12B | 113.15 (13) |
C13A—N1A—C12A | 109.67 (15) | C13B—N1B—C12B | 109.68 (13) |
C14A—N1A—H1N | 107.7 (12) | C14B—N1B—H2N | 105.5 (13) |
C13A—N1A—H1N | 105.4 (11) | C13B—N1B—H2N | 108.0 (13) |
C12A—N1A—H1N | 108.5 (11) | C12B—N1B—H2N | 109.1 (12) |
C5A—O1A—H1O | 112.0 (17) | C5B—O1B—H2O | 111.0 (19) |
C6A—C1A—C2A—C3A | 0.0 (2) | C6B—C1B—C2B—C3B | −0.4 (2) |
C7A—C1A—C2A—C3A | −179.81 (14) | C7B—C1B—C2B—C3B | −178.55 (15) |
C1A—C2A—C3A—C4A | 0.1 (2) | C1B—C2B—C3B—C4B | 1.0 (3) |
C2A—C3A—C4A—C5A | −0.5 (2) | C2B—C3B—C4B—C5B | −1.0 (3) |
C3A—C4A—C5A—O1A | 179.14 (15) | C3B—C4B—C5B—O1B | 178.50 (17) |
C3A—C4A—C5A—C6A | 0.7 (2) | C3B—C4B—C5B—C6B | 0.3 (3) |
O1A—C5A—C6A—C1A | −178.96 (15) | C2B—C1B—C6B—C5B | −0.2 (2) |
C4A—C5A—C6A—C1A | −0.6 (2) | C7B—C1B—C6B—C5B | 177.96 (14) |
C2A—C1A—C6A—C5A | 0.2 (2) | O1B—C5B—C6B—C1B | −177.82 (16) |
C7A—C1A—C6A—C5A | −179.95 (14) | C4B—C5B—C6B—C1B | 0.3 (2) |
C6A—C1A—C7A—C8A | −134.29 (15) | C6B—C1B—C7B—C8B | −136.29 (15) |
C2A—C1A—C7A—C8A | 45.5 (2) | C2B—C1B—C7B—C8B | 41.82 (19) |
C6A—C1A—C7A—C10A | 96.70 (17) | C6B—C1B—C7B—C10B | 93.19 (17) |
C2A—C1A—C7A—C10A | −83.48 (18) | C2B—C1B—C7B—C10B | −88.71 (19) |
C1A—C7A—C8A—C9A | 63.8 (2) | C1B—C7B—C8B—C9B | 170.38 (16) |
C10A—C7A—C8A—C9A | −166.17 (16) | C10B—C7B—C8B—C9B | −59.0 (2) |
C1A—C7A—C10A—C12A | 63.21 (17) | C1B—C7B—C10B—C12B | 65.15 (17) |
C8A—C7A—C10A—C12A | −66.42 (18) | C8B—C7B—C10B—C12B | −64.09 (17) |
C1A—C7A—C10A—C11A | −63.43 (19) | C1B—C7B—C10B—C11B | −60.57 (18) |
C8A—C7A—C10A—C11A | 166.94 (15) | C8B—C7B—C10B—C11B | 170.19 (14) |
C11A—C10A—C12A—N1A | −61.72 (19) | C11B—C10B—C12B—N1B | −57.16 (19) |
C7A—C10A—C12A—N1A | 171.87 (13) | C7B—C10B—C12B—N1B | 177.09 (13) |
C10A—C12A—N1A—C14A | −54.2 (2) | C10B—C12B—N1B—C14B | −52.66 (19) |
C10A—C12A—N1A—C13A | −179.73 (16) | C10B—C12B—N1B—C13B | −177.40 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1N···Cl1Bi | 0.875 (19) | 2.23 (2) | 3.0569 (17) | 157 (2) |
O1A—H1O···Cl1A | 0.83 (3) | 2.24 (3) | 3.0584 (17) | 168 (2) |
N1B—H2N···Cl1A | 0.90 (2) | 2.19 (2) | 3.0506 (15) | 158 (2) |
O1B—H2O···Cl1B | 0.79 (3) | 2.30 (3) | 3.0667 (17) | 164 (2) |
Symmetry code: (i) x−1, y, z. |
C14H24NO+·Cl− | F(000) = 560 |
Mr = 257.79 | Dx = 1.171 Mg m−3 |
Monoclinic, P21 | Melting point: 480 K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 7.160 (3) Å | Cell parameters from 6730 reflections |
b = 11.688 (5) Å | θ = 2.3–26.0° |
c = 17.526 (8) Å | µ = 0.25 mm−1 |
β = 94.570 (7)° | T = 294 K |
V = 1462.0 (11) Å3 | Needle, colourless |
Z = 4 | 0.15 × 0.12 × 0.06 mm |
Bruker SMART APEX CCD area-detector diffractometer | 5139 independent reflections |
Radiation source: fine-focus sealed tube | 4883 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω scans | θmax = 25.0°, θmin = 1.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −8→8 |
Tmin = 0.963, Tmax = 0.986 | k = −13→13 |
13998 measured reflections | l = −20→20 |
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)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.0334P)2 + 0.1722P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max < 0.001 |
5139 reflections | Δρmax = 0.14 e Å−3 |
331 parameters | Δρmin = −0.10 e Å−3 |
1 restraint | Absolute structure: Flack & Bernardinelli (2000), with 2431 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (4) |
C14H24NO+·Cl− | V = 1462.0 (11) Å3 |
Mr = 257.79 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.160 (3) Å | µ = 0.25 mm−1 |
b = 11.688 (5) Å | T = 294 K |
c = 17.526 (8) Å | 0.15 × 0.12 × 0.06 mm |
β = 94.570 (7)° |
Bruker SMART APEX CCD area-detector diffractometer | 5139 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 4883 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.986 | Rint = 0.021 |
13998 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.075 | Δρmax = 0.14 e Å−3 |
S = 1.06 | Δρmin = −0.10 e Å−3 |
5139 reflections | Absolute structure: Flack & Bernardinelli (2000), with 2431 Friedel pairs |
331 parameters | Absolute structure parameter: −0.02 (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. |
x | y | z | Uiso*/Ueq | ||
C1A | 0.7769 (2) | 0.46893 (15) | 0.22428 (10) | 0.0395 (4) | |
C2A | 0.8344 (3) | 0.57641 (16) | 0.20069 (11) | 0.0449 (4) | |
H2A | 0.7951 | 0.6031 | 0.1521 | 0.054* | |
C3A | 0.9493 (3) | 0.64304 (16) | 0.24915 (11) | 0.0489 (5) | |
H3A | 0.9864 | 0.7145 | 0.2326 | 0.059* | |
C4A | 1.0108 (3) | 0.60649 (18) | 0.32172 (12) | 0.0501 (5) | |
H4A | 1.0877 | 0.6527 | 0.3540 | 0.060* | |
C5A | 0.9557 (3) | 0.49968 (18) | 0.34556 (10) | 0.0477 (5) | |
C6A | 0.8395 (3) | 0.43246 (17) | 0.29711 (10) | 0.0439 (4) | |
H6A | 0.8025 | 0.3611 | 0.3139 | 0.053* | |
C7A | 0.6493 (2) | 0.39218 (16) | 0.17290 (10) | 0.0417 (4) | |
H7A | 0.5957 | 0.3369 | 0.2071 | 0.050* | |
C8A | 0.4820 (3) | 0.45647 (19) | 0.13298 (12) | 0.0536 (5) | |
H8A | 0.5282 | 0.5189 | 0.1032 | 0.064* | |
H8B | 0.4125 | 0.4049 | 0.0979 | 0.064* | |
C9A | 0.3511 (3) | 0.5042 (2) | 0.18914 (15) | 0.0697 (7) | |
H9A | 0.4175 | 0.5583 | 0.2224 | 0.105* | |
H9B | 0.3057 | 0.4429 | 0.2191 | 0.105* | |
H9C | 0.2472 | 0.5416 | 0.1615 | 0.105* | |
C10A | 0.7538 (3) | 0.32029 (16) | 0.11544 (10) | 0.0417 (4) | |
H10A | 0.6590 | 0.2747 | 0.0857 | 0.050* | |
C11A | 0.8907 (3) | 0.23620 (19) | 0.15597 (12) | 0.0587 (5) | |
H11A | 0.9912 | 0.2776 | 0.1830 | 0.088* | |
H11B | 0.9405 | 0.1867 | 0.1189 | 0.088* | |
H11C | 0.8267 | 0.1913 | 0.1916 | 0.088* | |
C12A | 0.8466 (3) | 0.39528 (16) | 0.05926 (11) | 0.0464 (4) | |
H12A | 0.7549 | 0.4496 | 0.0374 | 0.056* | |
H12B | 0.9456 | 0.4386 | 0.0870 | 0.056* | |
C13A | 1.0150 (4) | 0.4161 (2) | −0.05637 (15) | 0.0765 (7) | |
H13A | 0.9222 | 0.4705 | −0.0754 | 0.115* | |
H13B | 1.0624 | 0.3760 | −0.0985 | 0.115* | |
H13C | 1.1159 | 0.4555 | −0.0282 | 0.115* | |
C14A | 0.7936 (4) | 0.2570 (3) | −0.04862 (14) | 0.0787 (8) | |
H14A | 0.6866 | 0.3009 | −0.0678 | 0.118* | |
H14B | 0.7542 | 0.1974 | −0.0158 | 0.118* | |
H14C | 0.8522 | 0.2236 | −0.0907 | 0.118* | |
N1A | 0.9286 (2) | 0.33246 (15) | −0.00489 (10) | 0.0485 (4) | |
H1N | 1.020 (3) | 0.287 (2) | 0.0139 (11) | 0.049 (5)* | |
O1A | 1.0170 (2) | 0.46626 (17) | 0.41803 (9) | 0.0685 (5) | |
H1O | 0.960 (4) | 0.412 (3) | 0.4334 (15) | 0.080 (9)* | |
C1B | 0.3051 (2) | −0.01273 (16) | 0.26777 (10) | 0.0419 (4) | |
C2B | 0.3791 (3) | −0.11668 (18) | 0.29481 (12) | 0.0493 (5) | |
H2B | 0.3404 | −0.1479 | 0.3398 | 0.059* | |
C3B | 0.5099 (3) | −0.17357 (17) | 0.25496 (12) | 0.0549 (5) | |
H3B | 0.5595 | −0.2424 | 0.2739 | 0.066* | |
C4B | 0.5684 (3) | −0.13031 (19) | 0.18768 (12) | 0.0551 (5) | |
H4B | 0.6557 | −0.1699 | 0.1613 | 0.066* | |
C5B | 0.4962 (3) | −0.02755 (18) | 0.15989 (11) | 0.0493 (5) | |
C6B | 0.3660 (3) | 0.03083 (17) | 0.20013 (11) | 0.0459 (4) | |
H6B | 0.3188 | 0.1004 | 0.1815 | 0.055* | |
C7B | 0.1570 (2) | 0.05200 (16) | 0.30845 (10) | 0.0425 (4) | |
H7B | 0.0915 | 0.1000 | 0.2690 | 0.051* | |
C8B | 0.0075 (3) | −0.02905 (18) | 0.33563 (12) | 0.0523 (5) | |
H8C | −0.0349 | −0.0788 | 0.2934 | 0.063* | |
H8D | 0.0652 | −0.0770 | 0.3761 | 0.063* | |
C9B | −0.1609 (3) | 0.0287 (2) | 0.36476 (16) | 0.0746 (7) | |
H9D | −0.2105 | 0.0835 | 0.3277 | 0.112* | |
H9E | −0.1247 | 0.0669 | 0.4121 | 0.112* | |
H9F | −0.2548 | −0.0276 | 0.3730 | 0.112* | |
C10B | 0.2388 (2) | 0.13632 (16) | 0.37091 (10) | 0.0408 (4) | |
H10B | 0.1326 | 0.1750 | 0.3918 | 0.049* | |
C11B | 0.3599 (3) | 0.22841 (18) | 0.33827 (12) | 0.0573 (5) | |
H11D | 0.4679 | 0.1937 | 0.3188 | 0.086* | |
H11E | 0.3994 | 0.2820 | 0.3778 | 0.086* | |
H11F | 0.2887 | 0.2677 | 0.2976 | 0.086* | |
C12B | 0.3427 (3) | 0.07153 (16) | 0.43648 (10) | 0.0438 (4) | |
H12C | 0.2582 | 0.0154 | 0.4556 | 0.053* | |
H12D | 0.4457 | 0.0302 | 0.4165 | 0.053* | |
C13B | 0.5104 (3) | 0.0693 (2) | 0.56374 (13) | 0.0627 (6) | |
H13D | 0.4208 | 0.0151 | 0.5799 | 0.094* | |
H13E | 0.5554 | 0.1158 | 0.6065 | 0.094* | |
H13F | 0.6136 | 0.0292 | 0.5443 | 0.094* | |
C14B | 0.2762 (3) | 0.2194 (2) | 0.53298 (13) | 0.0652 (6) | |
H14D | 0.3297 | 0.2579 | 0.5779 | 0.098* | |
H14E | 0.1713 | 0.1741 | 0.5459 | 0.098* | |
H14F | 0.2349 | 0.2749 | 0.4949 | 0.098* | |
N1B | 0.4194 (2) | 0.14384 (15) | 0.50231 (9) | 0.0440 (4) | |
H2N | 0.510 (3) | 0.190 (2) | 0.4860 (12) | 0.063 (6)* | |
O1B | 0.5535 (2) | 0.01155 (17) | 0.09237 (9) | 0.0694 (5) | |
H2O | 0.494 (4) | 0.065 (3) | 0.0774 (15) | 0.077 (9)* | |
Cl1A | 0.77045 (7) | 0.28837 (4) | 0.48961 (3) | 0.05532 (14) | |
Cl1B | 0.28374 (7) | 0.18675 (4) | 0.01351 (3) | 0.05592 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0361 (9) | 0.0411 (10) | 0.0422 (10) | 0.0050 (8) | 0.0090 (7) | −0.0017 (8) |
C2A | 0.0477 (11) | 0.0426 (10) | 0.0451 (10) | 0.0060 (8) | 0.0070 (8) | −0.0004 (8) |
C3A | 0.0498 (11) | 0.0400 (10) | 0.0583 (12) | −0.0014 (9) | 0.0136 (9) | −0.0042 (9) |
C4A | 0.0420 (10) | 0.0552 (13) | 0.0539 (12) | −0.0090 (9) | 0.0094 (9) | −0.0137 (9) |
C5A | 0.0426 (10) | 0.0613 (13) | 0.0395 (10) | −0.0037 (9) | 0.0054 (8) | −0.0021 (9) |
C6A | 0.0423 (10) | 0.0477 (11) | 0.0421 (10) | −0.0051 (8) | 0.0063 (8) | −0.0002 (8) |
C7A | 0.0406 (9) | 0.0442 (10) | 0.0403 (9) | 0.0000 (8) | 0.0036 (7) | 0.0018 (8) |
C8A | 0.0418 (10) | 0.0585 (13) | 0.0598 (12) | 0.0054 (9) | −0.0003 (9) | −0.0047 (10) |
C9A | 0.0487 (12) | 0.0709 (15) | 0.0912 (18) | 0.0131 (11) | 0.0154 (12) | −0.0015 (13) |
C10A | 0.0406 (9) | 0.0391 (10) | 0.0446 (10) | 0.0027 (7) | −0.0019 (8) | −0.0027 (8) |
C11A | 0.0681 (14) | 0.0516 (12) | 0.0561 (12) | 0.0165 (10) | 0.0034 (10) | 0.0044 (10) |
C12A | 0.0498 (11) | 0.0401 (10) | 0.0503 (11) | 0.0075 (8) | 0.0100 (9) | −0.0010 (9) |
C13A | 0.0830 (17) | 0.0794 (17) | 0.0721 (15) | 0.0202 (14) | 0.0371 (13) | 0.0211 (13) |
C14A | 0.0773 (16) | 0.101 (2) | 0.0568 (14) | 0.0000 (15) | −0.0019 (12) | −0.0231 (14) |
N1A | 0.0488 (9) | 0.0515 (10) | 0.0457 (9) | 0.0125 (8) | 0.0061 (8) | 0.0006 (8) |
O1A | 0.0684 (10) | 0.0877 (13) | 0.0470 (9) | −0.0250 (10) | −0.0093 (7) | 0.0089 (8) |
C1B | 0.0368 (9) | 0.0460 (10) | 0.0417 (10) | 0.0014 (8) | −0.0042 (8) | −0.0064 (8) |
C2B | 0.0464 (10) | 0.0507 (11) | 0.0497 (11) | 0.0031 (9) | −0.0020 (8) | 0.0030 (9) |
C3B | 0.0535 (12) | 0.0480 (12) | 0.0625 (13) | 0.0127 (9) | −0.0004 (10) | −0.0020 (10) |
C4B | 0.0491 (11) | 0.0586 (13) | 0.0577 (12) | 0.0153 (10) | 0.0055 (9) | −0.0082 (10) |
C5B | 0.0447 (10) | 0.0589 (13) | 0.0440 (11) | 0.0052 (9) | 0.0023 (8) | −0.0026 (9) |
C6B | 0.0437 (10) | 0.0465 (11) | 0.0461 (10) | 0.0075 (9) | −0.0047 (8) | −0.0013 (9) |
C7B | 0.0372 (9) | 0.0473 (11) | 0.0419 (10) | 0.0080 (8) | −0.0039 (8) | 0.0036 (8) |
C8B | 0.0369 (10) | 0.0562 (12) | 0.0630 (13) | −0.0024 (9) | −0.0011 (9) | −0.0100 (10) |
C9B | 0.0519 (13) | 0.0749 (16) | 0.0990 (19) | −0.0044 (12) | 0.0187 (12) | −0.0179 (14) |
C10B | 0.0373 (9) | 0.0405 (10) | 0.0446 (10) | 0.0046 (8) | 0.0030 (7) | 0.0012 (8) |
C11B | 0.0698 (14) | 0.0474 (11) | 0.0537 (12) | −0.0082 (10) | −0.0009 (10) | 0.0073 (9) |
C12B | 0.0444 (10) | 0.0408 (10) | 0.0457 (10) | −0.0027 (8) | 0.0012 (8) | 0.0007 (8) |
C13B | 0.0614 (13) | 0.0710 (15) | 0.0529 (12) | −0.0112 (11) | −0.0127 (10) | 0.0125 (11) |
C14B | 0.0617 (13) | 0.0812 (17) | 0.0532 (12) | 0.0083 (12) | 0.0080 (11) | −0.0157 (11) |
N1B | 0.0393 (8) | 0.0494 (10) | 0.0431 (9) | −0.0058 (7) | 0.0013 (7) | 0.0034 (7) |
O1B | 0.0693 (11) | 0.0804 (12) | 0.0608 (10) | 0.0267 (10) | 0.0200 (8) | 0.0105 (9) |
Cl1A | 0.0519 (3) | 0.0465 (3) | 0.0673 (3) | −0.0098 (2) | 0.0030 (2) | −0.0033 (2) |
Cl1B | 0.0513 (3) | 0.0491 (3) | 0.0674 (3) | 0.0085 (2) | 0.0047 (2) | −0.0039 (2) |
C1A—C6A | 1.386 (3) | C1B—C6B | 1.392 (3) |
C1A—C2A | 1.395 (3) | C1B—C2B | 1.393 (3) |
C1A—C7A | 1.523 (3) | C1B—C7B | 1.525 (2) |
C2A—C3A | 1.376 (3) | C2B—C3B | 1.382 (3) |
C2A—H2A | 0.9300 | C2B—H2B | 0.9300 |
C3A—C4A | 1.380 (3) | C3B—C4B | 1.379 (3) |
C3A—H3A | 0.9300 | C3B—H3B | 0.9300 |
C4A—C5A | 1.384 (3) | C4B—C5B | 1.381 (3) |
C4A—H4A | 0.9300 | C4B—H4B | 0.9300 |
C5A—O1A | 1.367 (2) | C5B—O1B | 1.362 (3) |
C5A—C6A | 1.385 (3) | C5B—C6B | 1.391 (3) |
C6A—H6A | 0.9300 | C6B—H6B | 0.9300 |
C7A—C8A | 1.534 (3) | C7B—C8B | 1.533 (3) |
C7A—C10A | 1.549 (3) | C7B—C10B | 1.553 (3) |
C7A—H7A | 0.9800 | C7B—H7B | 0.9800 |
C8A—C9A | 1.519 (3) | C8B—C9B | 1.506 (3) |
C8A—H8A | 0.9700 | C8B—H8C | 0.9700 |
C8A—H8B | 0.9700 | C8B—H8D | 0.9700 |
C9A—H9A | 0.9600 | C9B—H9D | 0.9600 |
C9A—H9B | 0.9600 | C9B—H9E | 0.9600 |
C9A—H9C | 0.9600 | C9B—H9F | 0.9600 |
C10A—C12A | 1.511 (3) | C10B—C12B | 1.520 (3) |
C10A—C11A | 1.523 (3) | C10B—C11B | 1.522 (3) |
C10A—H10A | 0.9800 | C10B—H10B | 0.9800 |
C11A—H11A | 0.9600 | C11B—H11D | 0.9600 |
C11A—H11B | 0.9600 | C11B—H11E | 0.9600 |
C11A—H11C | 0.9600 | C11B—H11F | 0.9600 |
C12A—N1A | 1.501 (2) | C12B—N1B | 1.499 (2) |
C12A—H12A | 0.9700 | C12B—H12C | 0.9700 |
C12A—H12B | 0.9700 | C12B—H12D | 0.9700 |
C13A—N1A | 1.497 (3) | C13B—N1B | 1.493 (3) |
C13A—H13A | 0.9600 | C13B—H13D | 0.9600 |
C13A—H13B | 0.9600 | C13B—H13E | 0.9600 |
C13A—H13C | 0.9600 | C13B—H13F | 0.9600 |
C14A—N1A | 1.477 (3) | C14B—N1B | 1.486 (3) |
C14A—H14A | 0.9600 | C14B—H14D | 0.9600 |
C14A—H14B | 0.9600 | C14B—H14E | 0.9600 |
C14A—H14C | 0.9600 | C14B—H14F | 0.9600 |
N1A—H1N | 0.88 (2) | N1B—H2N | 0.91 (3) |
O1A—H1O | 0.81 (3) | O1B—H2O | 0.79 (3) |
C6A—C1A—C2A | 117.94 (17) | C6B—C1B—C2B | 118.16 (17) |
C6A—C1A—C7A | 119.87 (16) | C6B—C1B—C7B | 119.58 (16) |
C2A—C1A—C7A | 122.19 (16) | C2B—C1B—C7B | 122.24 (17) |
C3A—C2A—C1A | 120.19 (18) | C3B—C2B—C1B | 120.15 (19) |
C3A—C2A—H2A | 119.9 | C3B—C2B—H2B | 119.9 |
C1A—C2A—H2A | 119.9 | C1B—C2B—H2B | 119.9 |
C2A—C3A—C4A | 121.66 (19) | C4B—C3B—C2B | 121.33 (19) |
C2A—C3A—H3A | 119.2 | C4B—C3B—H3B | 119.3 |
C4A—C3A—H3A | 119.2 | C2B—C3B—H3B | 119.3 |
C3A—C4A—C5A | 118.67 (18) | C3B—C4B—C5B | 119.33 (19) |
C3A—C4A—H4A | 120.7 | C3B—C4B—H4B | 120.3 |
C5A—C4A—H4A | 120.7 | C5B—C4B—H4B | 120.3 |
O1A—C5A—C4A | 117.39 (18) | O1B—C5B—C4B | 117.91 (19) |
O1A—C5A—C6A | 122.69 (19) | O1B—C5B—C6B | 122.42 (19) |
C4A—C5A—C6A | 119.90 (18) | C4B—C5B—C6B | 119.66 (19) |
C5A—C6A—C1A | 121.63 (18) | C5B—C6B—C1B | 121.36 (18) |
C5A—C6A—H6A | 119.2 | C5B—C6B—H6B | 119.3 |
C1A—C6A—H6A | 119.2 | C1B—C6B—H6B | 119.3 |
C1A—C7A—C8A | 113.00 (16) | C1B—C7B—C8B | 111.54 (16) |
C1A—C7A—C10A | 113.93 (15) | C1B—C7B—C10B | 114.05 (14) |
C8A—C7A—C10A | 111.66 (15) | C8B—C7B—C10B | 113.99 (15) |
C1A—C7A—H7A | 105.8 | C1B—C7B—H7B | 105.4 |
C8A—C7A—H7A | 105.8 | C8B—C7B—H7B | 105.4 |
C10A—C7A—H7A | 105.8 | C10B—C7B—H7B | 105.4 |
C9A—C8A—C7A | 112.59 (18) | C9B—C8B—C7B | 115.22 (19) |
C9A—C8A—H8A | 109.1 | C9B—C8B—H8C | 108.5 |
C7A—C8A—H8A | 109.1 | C7B—C8B—H8C | 108.5 |
C9A—C8A—H8B | 109.1 | C9B—C8B—H8D | 108.5 |
C7A—C8A—H8B | 109.1 | C7B—C8B—H8D | 108.5 |
H8A—C8A—H8B | 107.8 | H8C—C8B—H8D | 107.5 |
C8A—C9A—H9A | 109.5 | C8B—C9B—H9D | 109.5 |
C8A—C9A—H9B | 109.5 | C8B—C9B—H9E | 109.5 |
H9A—C9A—H9B | 109.5 | H9D—C9B—H9E | 109.5 |
C8A—C9A—H9C | 109.5 | C8B—C9B—H9F | 109.5 |
H9A—C9A—H9C | 109.5 | H9D—C9B—H9F | 109.5 |
H9B—C9A—H9C | 109.5 | H9E—C9B—H9F | 109.5 |
C12A—C10A—C11A | 112.21 (16) | C12B—C10B—C11B | 112.17 (16) |
C12A—C10A—C7A | 111.66 (15) | C12B—C10B—C7B | 110.56 (15) |
C11A—C10A—C7A | 111.90 (16) | C11B—C10B—C7B | 112.21 (16) |
C12A—C10A—H10A | 106.9 | C12B—C10B—H10B | 107.2 |
C11A—C10A—H10A | 106.9 | C11B—C10B—H10B | 107.2 |
C7A—C10A—H10A | 106.9 | C7B—C10B—H10B | 107.2 |
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 | 115.01 (15) | N1B—C12B—C10B | 115.35 (15) |
N1A—C12A—H12A | 108.5 | N1B—C12B—H12C | 108.4 |
C10A—C12A—H12A | 108.5 | C10B—C12B—H12C | 108.4 |
N1A—C12A—H12B | 108.5 | N1B—C12B—H12D | 108.4 |
C10A—C12A—H12B | 108.5 | C10B—C12B—H12D | 108.4 |
H12A—C12A—H12B | 107.5 | 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 | 111.2 (2) | C14B—N1B—C13B | 111.10 (17) |
C14A—N1A—C12A | 113.71 (17) | C14B—N1B—C12B | 113.12 (16) |
C13A—N1A—C12A | 109.69 (17) | C13B—N1B—C12B | 109.77 (16) |
C14A—N1A—H1N | 105.6 (14) | C14B—N1B—H2N | 107.2 (15) |
C13A—N1A—H1N | 106.7 (14) | C13B—N1B—H2N | 106.8 (14) |
C12A—N1A—H1N | 109.6 (13) | C12B—N1B—H2N | 108.5 (14) |
C5A—O1A—H1O | 113 (2) | C5B—O1B—H2O | 111 (2) |
C6A—C1A—C2A—C3A | −0.2 (3) | C6B—C1B—C2B—C3B | 0.2 (3) |
C7A—C1A—C2A—C3A | 179.75 (16) | C7B—C1B—C2B—C3B | 178.48 (18) |
C1A—C2A—C3A—C4A | 0.0 (3) | C1B—C2B—C3B—C4B | −0.8 (3) |
C2A—C3A—C4A—C5A | 0.4 (3) | C2B—C3B—C4B—C5B | 0.6 (3) |
C3A—C4A—C5A—O1A | −179.26 (18) | C3B—C4B—C5B—O1B | −178.5 (2) |
C3A—C4A—C5A—C6A | −0.7 (3) | C3B—C4B—C5B—C6B | 0.1 (3) |
O1A—C5A—C6A—C1A | 179.01 (17) | O1B—C5B—C6B—C1B | 177.87 (19) |
C4A—C5A—C6A—C1A | 0.5 (3) | C4B—C5B—C6B—C1B | −0.7 (3) |
C2A—C1A—C6A—C5A | −0.1 (3) | C2B—C1B—C6B—C5B | 0.5 (3) |
C7A—C1A—C6A—C5A | 179.97 (17) | C7B—C1B—C6B—C5B | −177.79 (17) |
C6A—C1A—C7A—C8A | 134.47 (18) | C6B—C1B—C7B—C8B | 136.15 (18) |
C2A—C1A—C7A—C8A | −45.5 (2) | C2B—C1B—C7B—C8B | −42.1 (2) |
C6A—C1A—C7A—C10A | −96.69 (19) | C6B—C1B—C7B—C10B | −92.95 (19) |
C2A—C1A—C7A—C10A | 83.3 (2) | C2B—C1B—C7B—C10B | 88.8 (2) |
C1A—C7A—C8A—C9A | −63.6 (2) | C1B—C7B—C8B—C9B | −170.38 (18) |
C10A—C7A—C8A—C9A | 166.36 (18) | C10B—C7B—C8B—C9B | 58.7 (2) |
C1A—C7A—C10A—C12A | −63.4 (2) | C1B—C7B—C10B—C12B | −65.6 (2) |
C8A—C7A—C10A—C12A | 66.1 (2) | C8B—C7B—C10B—C12B | 64.1 (2) |
C1A—C7A—C10A—C11A | 63.3 (2) | C1B—C7B—C10B—C11B | 60.5 (2) |
C8A—C7A—C10A—C11A | −167.15 (17) | C8B—C7B—C10B—C11B | −169.85 (16) |
C11A—C10A—C12A—N1A | 61.4 (2) | C11B—C10B—C12B—N1B | 57.0 (2) |
C7A—C10A—C12A—N1A | −172.03 (15) | C7B—C10B—C12B—N1B | −176.92 (15) |
C10A—C12A—N1A—C14A | 54.5 (2) | C10B—C12B—N1B—C14B | 52.9 (2) |
C10A—C12A—N1A—C13A | 179.75 (18) | C10B—C12B—N1B—C13B | 177.63 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1O···Cl1A | 0.81 (3) | 2.26 (3) | 3.060 (2) | 169 (3) |
N1A—H1N···Cl1Bi | 0.88 (2) | 2.23 (2) | 3.056 (2) | 156.5 (18) |
N1B—H2N···Cl1A | 0.91 (3) | 2.19 (3) | 3.051 (2) | 158.9 (19) |
O1B—H2O···Cl1B | 0.79 (3) | 2.30 (3) | 3.067 (2) | 166 (3) |
Symmetry code: (i) x+1, y, z. |
C14H24NO+·Cl− | Dx = 1.143 Mg m−3 |
Mr = 257.79 | Melting point: 477 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 7888 reflections |
a = 8.8218 (6) Å | θ = 2.2–27.3° |
b = 12.1304 (8) Å | µ = 0.24 mm−1 |
c = 14.0031 (9) Å | T = 294 K |
V = 1498.50 (17) Å3 | Block, colourless |
Z = 4 | 0.17 × 0.14 × 0.09 mm |
F(000) = 560 |
Bruker SMART APEX CCD area-detector diffractometer | 2653 independent reflections |
Radiation source: fine-focus sealed tube | 2540 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −10→10 |
Tmin = 0.958, Tmax = 0.975 | k = −14→14 |
14552 measured reflections | l = −16→16 |
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)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0443P)2 + 0.2546P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2653 reflections | Δρmax = 0.20 e Å−3 |
166 parameters | Δρmin = −0.13 e Å−3 |
0 restraints | Absolute structure: Flack & Bernardinelli (2000), with 1113 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (7) |
C14H24NO+·Cl− | V = 1498.50 (17) Å3 |
Mr = 257.79 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.8218 (6) Å | µ = 0.24 mm−1 |
b = 12.1304 (8) Å | T = 294 K |
c = 14.0031 (9) Å | 0.17 × 0.14 × 0.09 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2653 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2540 reflections with I > 2σ(I) |
Tmin = 0.958, Tmax = 0.975 | Rint = 0.022 |
14552 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.081 | Δρmax = 0.20 e Å−3 |
S = 1.03 | Δρmin = −0.13 e Å−3 |
2653 reflections | Absolute structure: Flack & Bernardinelli (2000), with 1113 Friedel pairs |
166 parameters | Absolute structure parameter: −0.02 (7) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | −0.06780 (19) | 0.59630 (13) | −0.05664 (12) | 0.0434 (4) | |
C2 | −0.1656 (2) | 0.50805 (15) | −0.06853 (14) | 0.0499 (4) | |
H2 | −0.1540 | 0.4452 | −0.0312 | 0.060* | |
C3 | −0.2810 (2) | 0.51297 (17) | −0.13582 (14) | 0.0556 (5) | |
H3 | −0.3466 | 0.4535 | −0.1429 | 0.067* | |
C4 | −0.2992 (2) | 0.60582 (16) | −0.19258 (13) | 0.0511 (4) | |
H4 | −0.3780 | 0.6095 | −0.2366 | 0.061* | |
C5 | −0.1994 (2) | 0.69241 (14) | −0.18304 (12) | 0.0463 (4) | |
C6 | −0.0850 (2) | 0.68787 (13) | −0.11503 (12) | 0.0444 (4) | |
H6 | −0.0189 | 0.7471 | −0.1085 | 0.053* | |
C7 | 0.0534 (2) | 0.59329 (13) | 0.01990 (12) | 0.0450 (4) | |
H7 | 0.1066 | 0.6642 | 0.0187 | 0.054* | |
C8 | −0.0207 (2) | 0.58101 (17) | 0.11877 (14) | 0.0579 (5) | |
H8A | −0.0758 | 0.5119 | 0.1211 | 0.069* | |
H8B | 0.0581 | 0.5783 | 0.1671 | 0.069* | |
C9 | −0.1284 (3) | 0.6746 (2) | 0.14176 (17) | 0.0780 (7) | |
H9A | −0.2121 | 0.6731 | 0.0980 | 0.117* | |
H9B | −0.0759 | 0.7436 | 0.1360 | 0.117* | |
H9C | −0.1653 | 0.6663 | 0.2058 | 0.117* | |
C10 | 0.1712 (2) | 0.50158 (15) | −0.00155 (12) | 0.0449 (4) | |
H10 | 0.1233 | 0.4296 | 0.0085 | 0.054* | |
C11 | 0.2266 (3) | 0.50847 (19) | −0.10535 (16) | 0.0701 (6) | |
H11A | 0.3081 | 0.4572 | −0.1148 | 0.105* | |
H11B | 0.2618 | 0.5818 | −0.1184 | 0.105* | |
H11C | 0.1447 | 0.4907 | −0.1477 | 0.105* | |
C12 | 0.3057 (2) | 0.51131 (17) | 0.06455 (18) | 0.0672 (6) | |
H12A | 0.3729 | 0.5681 | 0.0403 | 0.081* | |
H12B | 0.2703 | 0.5348 | 0.1269 | 0.081* | |
C13 | 0.3254 (3) | 0.3263 (2) | 0.14156 (17) | 0.0790 (7) | |
H13A | 0.3164 | 0.3586 | 0.2039 | 0.118* | |
H13B | 0.3883 | 0.2618 | 0.1451 | 0.118* | |
H13C | 0.2267 | 0.3061 | 0.1186 | 0.118* | |
C14 | 0.5508 (2) | 0.4316 (2) | 0.10597 (17) | 0.0696 (6) | |
H14A | 0.6096 | 0.3650 | 0.1065 | 0.104* | |
H14B | 0.5496 | 0.4630 | 0.1689 | 0.104* | |
H14C | 0.5951 | 0.4832 | 0.0621 | 0.104* | |
N1 | 0.39406 (16) | 0.40635 (12) | 0.07588 (11) | 0.0471 (3) | |
H1N | 0.397 (2) | 0.3717 (16) | 0.0139 (14) | 0.050 (5)* | |
O1 | −0.20577 (19) | 0.78479 (11) | −0.23829 (10) | 0.0637 (4) | |
H1O | −0.268 (3) | 0.778 (2) | −0.2782 (19) | 0.076 (8)* | |
Cl1 | 0.43172 (5) | 0.25035 (4) | −0.09402 (3) | 0.05870 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0447 (9) | 0.0427 (8) | 0.0428 (8) | 0.0053 (8) | −0.0013 (7) | −0.0018 (7) |
C2 | 0.0532 (10) | 0.0457 (9) | 0.0509 (10) | −0.0035 (8) | −0.0037 (8) | 0.0077 (8) |
C3 | 0.0545 (11) | 0.0576 (11) | 0.0547 (10) | −0.0134 (9) | −0.0056 (9) | −0.0008 (9) |
C4 | 0.0508 (10) | 0.0608 (10) | 0.0416 (9) | 0.0027 (9) | −0.0091 (8) | −0.0037 (8) |
C5 | 0.0555 (10) | 0.0453 (9) | 0.0380 (8) | 0.0101 (8) | −0.0019 (8) | −0.0029 (7) |
C6 | 0.0481 (9) | 0.0386 (8) | 0.0465 (9) | 0.0015 (7) | −0.0027 (8) | −0.0025 (7) |
C7 | 0.0481 (9) | 0.0376 (8) | 0.0495 (9) | 0.0031 (8) | −0.0072 (8) | −0.0022 (7) |
C8 | 0.0630 (11) | 0.0636 (11) | 0.0471 (10) | 0.0108 (9) | −0.0089 (9) | −0.0019 (9) |
C9 | 0.0831 (16) | 0.0864 (16) | 0.0647 (13) | 0.0253 (13) | 0.0025 (12) | −0.0131 (12) |
C10 | 0.0477 (9) | 0.0381 (8) | 0.0489 (10) | 0.0019 (7) | −0.0077 (8) | −0.0029 (7) |
C11 | 0.0783 (14) | 0.0633 (12) | 0.0688 (13) | 0.0220 (11) | 0.0097 (12) | 0.0071 (11) |
C12 | 0.0608 (12) | 0.0555 (11) | 0.0854 (15) | 0.0125 (10) | −0.0265 (12) | −0.0209 (11) |
C13 | 0.0827 (16) | 0.0922 (17) | 0.0619 (13) | −0.0181 (14) | 0.0008 (12) | 0.0073 (12) |
C14 | 0.0492 (11) | 0.0878 (14) | 0.0718 (14) | 0.0030 (10) | −0.0124 (11) | 0.0050 (12) |
N1 | 0.0457 (7) | 0.0538 (8) | 0.0419 (8) | 0.0072 (6) | −0.0086 (6) | −0.0065 (6) |
O1 | 0.0855 (11) | 0.0500 (7) | 0.0556 (8) | 0.0057 (7) | −0.0228 (8) | 0.0064 (6) |
Cl1 | 0.0700 (3) | 0.0532 (2) | 0.0529 (2) | 0.0116 (2) | −0.0140 (2) | −0.0109 (2) |
C1—C2 | 1.385 (2) | C9—H9C | 0.9600 |
C1—C6 | 1.388 (2) | C10—C12 | 1.509 (3) |
C1—C7 | 1.514 (2) | C10—C11 | 1.536 (3) |
C2—C3 | 1.388 (3) | C10—H10 | 0.9800 |
C2—H2 | 0.9300 | C11—H11A | 0.9600 |
C3—C4 | 1.388 (3) | C11—H11B | 0.9600 |
C3—H3 | 0.9300 | C11—H11C | 0.9600 |
C4—C5 | 1.377 (3) | C12—N1 | 1.501 (2) |
C4—H4 | 0.9300 | C12—H12A | 0.9700 |
C5—O1 | 1.363 (2) | C12—H12B | 0.9700 |
C5—C6 | 1.389 (2) | C13—N1 | 1.468 (3) |
C6—H6 | 0.9300 | C13—H13A | 0.9600 |
C7—C8 | 1.538 (3) | C13—H13B | 0.9600 |
C7—C10 | 1.552 (2) | C13—H13C | 0.9600 |
C7—H7 | 0.9800 | C14—N1 | 1.478 (2) |
C8—C9 | 1.515 (3) | 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 | 0.97 (2) |
C9—H9B | 0.9600 | O1—H1O | 0.79 (3) |
C2—C1—C6 | 118.67 (15) | C12—C10—C7 | 110.60 (14) |
C2—C1—C7 | 120.42 (15) | C11—C10—C7 | 110.94 (15) |
C6—C1—C7 | 120.90 (15) | C12—C10—H10 | 108.7 |
C1—C2—C3 | 120.34 (17) | C11—C10—H10 | 108.7 |
C1—C2—H2 | 119.8 | C7—C10—H10 | 108.7 |
C3—C2—H2 | 119.8 | C10—C11—H11A | 109.5 |
C4—C3—C2 | 120.57 (17) | C10—C11—H11B | 109.5 |
C4—C3—H3 | 119.7 | H11A—C11—H11B | 109.5 |
C2—C3—H3 | 119.7 | C10—C11—H11C | 109.5 |
C5—C4—C3 | 119.30 (16) | H11A—C11—H11C | 109.5 |
C5—C4—H4 | 120.4 | H11B—C11—H11C | 109.5 |
C3—C4—H4 | 120.4 | N1—C12—C10 | 113.99 (15) |
O1—C5—C4 | 123.07 (16) | N1—C12—H12A | 108.8 |
O1—C5—C6 | 116.86 (16) | C10—C12—H12A | 108.8 |
C4—C5—C6 | 120.07 (16) | N1—C12—H12B | 108.8 |
C1—C6—C5 | 121.01 (15) | C10—C12—H12B | 108.8 |
C1—C6—H6 | 119.5 | H12A—C12—H12B | 107.6 |
C5—C6—H6 | 119.5 | N1—C13—H13A | 109.5 |
C1—C7—C8 | 109.87 (15) | N1—C13—H13B | 109.5 |
C1—C7—C10 | 110.68 (13) | H13A—C13—H13B | 109.5 |
C8—C7—C10 | 112.91 (14) | N1—C13—H13C | 109.5 |
C1—C7—H7 | 107.7 | H13A—C13—H13C | 109.5 |
C8—C7—H7 | 107.7 | H13B—C13—H13C | 109.5 |
C10—C7—H7 | 107.7 | N1—C14—H14A | 109.5 |
C9—C8—C7 | 112.65 (17) | N1—C14—H14B | 109.5 |
C9—C8—H8A | 109.1 | H14A—C14—H14B | 109.5 |
C7—C8—H8A | 109.1 | N1—C14—H14C | 109.5 |
C9—C8—H8B | 109.1 | H14A—C14—H14C | 109.5 |
C7—C8—H8B | 109.1 | H14B—C14—H14C | 109.5 |
H8A—C8—H8B | 107.8 | C13—N1—C14 | 110.14 (17) |
C8—C9—H9A | 109.5 | C13—N1—C12 | 114.40 (18) |
C8—C9—H9B | 109.5 | C14—N1—C12 | 109.89 (16) |
H9A—C9—H9B | 109.5 | C13—N1—H1N | 106.7 (11) |
C8—C9—H9C | 109.5 | C14—N1—H1N | 108.7 (11) |
H9A—C9—H9C | 109.5 | C12—N1—H1N | 106.8 (11) |
H9B—C9—H9C | 109.5 | C5—O1—H1O | 109.9 (18) |
C12—C10—C11 | 109.03 (18) | ||
C6—C1—C2—C3 | −1.8 (3) | C2—C1—C7—C10 | 65.2 (2) |
C7—C1—C2—C3 | 177.07 (16) | C6—C1—C7—C10 | −115.97 (17) |
C1—C2—C3—C4 | 0.5 (3) | C1—C7—C8—C9 | −59.4 (2) |
C2—C3—C4—C5 | 1.4 (3) | C10—C7—C8—C9 | 176.47 (17) |
C3—C4—C5—O1 | 177.52 (18) | C1—C7—C10—C12 | 170.15 (16) |
C3—C4—C5—C6 | −2.1 (3) | C8—C7—C10—C12 | −66.2 (2) |
C2—C1—C6—C5 | 1.1 (3) | C1—C7—C10—C11 | 49.0 (2) |
C7—C1—C6—C5 | −177.72 (15) | C8—C7—C10—C11 | 172.66 (16) |
O1—C5—C6—C1 | −178.83 (16) | C11—C10—C12—N1 | −79.9 (2) |
C4—C5—C6—C1 | 0.8 (3) | C7—C10—C12—N1 | 157.87 (17) |
C2—C1—C7—C8 | −60.2 (2) | C10—C12—N1—C13 | −78.9 (2) |
C6—C1—C7—C8 | 118.66 (18) | C10—C12—N1—C14 | 156.57 (19) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1 | 0.97 (2) | 2.13 (2) | 3.0580 (15) | 160.5 (16) |
O1—H1O···Cl1i | 0.79 (3) | 2.32 (3) | 3.1083 (16) | 174 (2) |
C11—H11A···Cl1 | 0.96 | 2.75 | 3.620 (2) | 151 |
C13—H13C···Cl1ii | 0.96 | 2.71 | 3.657 (3) | 168 |
Symmetry codes: (i) −x, y+1/2, −z−1/2; (ii) x−1/2, −y+1/2, −z. |
C14H24NO+·Cl− | Dx = 1.148 Mg m−3 |
Mr = 257.79 | Melting point: 478 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 9741 reflections |
a = 8.8101 (6) Å | θ = 2.2–27.7° |
b = 12.1094 (8) Å | µ = 0.24 mm−1 |
c = 13.9784 (9) Å | T = 294 K |
V = 1491.29 (17) Å3 | Block, colourless |
Z = 4 | 0.21 × 0.17 × 0.12 mm |
F(000) = 560 |
Bruker SMART APEX CCD area-detector diffractometer | 2630 independent reflections |
Radiation source: fine-focus sealed tube | 2548 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −10→10 |
Tmin = 0.948, Tmax = 0.969 | k = −14→14 |
14415 measured reflections | l = −16→16 |
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)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.083 | w = 1/[σ2(Fo2) + (0.048P)2 + 0.2289P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2630 reflections | Δρmax = 0.22 e Å−3 |
166 parameters | Δρmin = −0.13 e Å−3 |
0 restraints | Absolute structure: Flack & Bernardinelli (2000), with 1104 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (6) |
C14H24NO+·Cl− | V = 1491.29 (17) Å3 |
Mr = 257.79 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.8101 (6) Å | µ = 0.24 mm−1 |
b = 12.1094 (8) Å | T = 294 K |
c = 13.9784 (9) Å | 0.21 × 0.17 × 0.12 mm |
Bruker SMART APEX CCD area-detector diffractometer | 2630 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2548 reflections with I > 2σ(I) |
Tmin = 0.948, Tmax = 0.969 | Rint = 0.019 |
14415 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.083 | Δρmax = 0.22 e Å−3 |
S = 1.05 | Δρmin = −0.13 e Å−3 |
2630 reflections | Absolute structure: Flack & Bernardinelli (2000), with 1104 Friedel pairs |
166 parameters | Absolute structure parameter: 0.00 (6) |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 1.06779 (18) | 0.40372 (13) | 1.05655 (11) | 0.0436 (3) | |
C2 | 1.1658 (2) | 0.49194 (15) | 1.06865 (13) | 0.0506 (4) | |
H2 | 1.1543 | 0.5550 | 1.0314 | 0.061* | |
C3 | 1.2809 (2) | 0.48691 (16) | 1.13582 (13) | 0.0560 (4) | |
H3 | 1.3466 | 0.5464 | 1.1429 | 0.067* | |
C4 | 1.2992 (2) | 0.39420 (15) | 1.19260 (12) | 0.0517 (4) | |
H4 | 1.3781 | 0.3905 | 1.2367 | 0.062* | |
C5 | 1.1993 (2) | 0.30752 (13) | 1.18298 (12) | 0.0465 (4) | |
C6 | 1.08491 (19) | 0.31209 (12) | 1.11502 (12) | 0.0445 (4) | |
H6 | 1.0186 | 0.2528 | 1.1085 | 0.053* | |
C7 | 0.9467 (2) | 0.40666 (13) | 0.98005 (12) | 0.0455 (4) | |
H7 | 0.8934 | 0.3356 | 0.9814 | 0.055* | |
C8 | 1.0205 (2) | 0.41879 (17) | 0.88136 (13) | 0.0584 (5) | |
H8A | 0.9416 | 0.4215 | 0.8330 | 0.070* | |
H8B | 1.0756 | 0.4881 | 0.8790 | 0.070* | |
C9 | 1.1281 (3) | 0.3254 (2) | 0.85824 (17) | 0.0785 (7) | |
H9A | 1.2120 | 0.3268 | 0.9021 | 0.118* | |
H9B | 1.1652 | 0.3338 | 0.7941 | 0.118* | |
H9C | 1.0757 | 0.2562 | 0.8639 | 0.118* | |
C10 | 0.82882 (19) | 0.49841 (14) | 1.00152 (11) | 0.0455 (4) | |
H10 | 0.8767 | 0.5705 | 0.9914 | 0.055* | |
C11 | 0.7734 (3) | 0.49147 (18) | 1.10529 (16) | 0.0706 (6) | |
H11A | 0.6913 | 0.5425 | 1.1146 | 0.106* | |
H11B | 0.8553 | 0.5098 | 1.1478 | 0.106* | |
H11C | 0.7390 | 0.4178 | 1.1185 | 0.106* | |
C12 | 0.6942 (2) | 0.48848 (17) | 0.93555 (17) | 0.0674 (6) | |
H12A | 0.7294 | 0.4646 | 0.8731 | 0.081* | |
H12B | 0.6267 | 0.4319 | 0.9601 | 0.081* | |
C13 | 0.6747 (3) | 0.6738 (2) | 0.85849 (16) | 0.0796 (7) | |
H13A | 0.6847 | 0.6412 | 0.7962 | 0.119* | |
H13B | 0.7731 | 0.6946 | 0.8818 | 0.119* | |
H13C | 0.6112 | 0.7380 | 0.8544 | 0.119* | |
C14 | 0.4496 (2) | 0.5685 (2) | 0.89392 (17) | 0.0701 (5) | |
H14A | 0.3905 | 0.6351 | 0.8938 | 0.105* | |
H14B | 0.4055 | 0.5164 | 0.9376 | 0.105* | |
H14C | 0.4509 | 0.5375 | 0.8307 | 0.105* | |
N1 | 0.60614 (16) | 0.59374 (12) | 0.92404 (10) | 0.0474 (3) | |
H1N | 0.602 (2) | 0.6281 (15) | 0.9853 (14) | 0.049 (5)* | |
O1 | 1.20575 (19) | 0.21526 (11) | 1.23837 (10) | 0.0636 (4) | |
H1O | 1.269 (3) | 0.224 (2) | 1.280 (2) | 0.084 (8)* | |
Cl1 | 0.56842 (5) | 0.74966 (4) | 1.09407 (3) | 0.05924 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0450 (8) | 0.0426 (7) | 0.0431 (8) | 0.0049 (7) | −0.0017 (7) | −0.0016 (6) |
C2 | 0.0540 (9) | 0.0461 (9) | 0.0518 (10) | −0.0045 (8) | −0.0043 (8) | 0.0070 (8) |
C3 | 0.0555 (10) | 0.0581 (10) | 0.0543 (10) | −0.0127 (9) | −0.0047 (8) | −0.0006 (8) |
C4 | 0.0508 (9) | 0.0614 (10) | 0.0430 (9) | 0.0030 (8) | −0.0090 (7) | −0.0043 (8) |
C5 | 0.0562 (10) | 0.0447 (8) | 0.0384 (8) | 0.0101 (7) | −0.0024 (7) | −0.0030 (7) |
C6 | 0.0486 (8) | 0.0383 (7) | 0.0467 (8) | 0.0020 (6) | −0.0022 (7) | −0.0027 (7) |
C7 | 0.0489 (8) | 0.0381 (8) | 0.0495 (9) | 0.0027 (7) | −0.0074 (7) | −0.0018 (7) |
C8 | 0.0637 (11) | 0.0639 (11) | 0.0475 (9) | 0.0114 (9) | −0.0085 (8) | −0.0010 (8) |
C9 | 0.0854 (15) | 0.0859 (15) | 0.0643 (13) | 0.0259 (13) | 0.0024 (12) | −0.0125 (11) |
C10 | 0.0487 (9) | 0.0381 (8) | 0.0498 (9) | 0.0024 (7) | −0.0080 (7) | −0.0031 (7) |
C11 | 0.0790 (13) | 0.0631 (11) | 0.0698 (13) | 0.0229 (10) | 0.0107 (11) | 0.0070 (10) |
C12 | 0.0622 (11) | 0.0559 (10) | 0.0841 (14) | 0.0121 (10) | −0.0268 (11) | −0.0209 (10) |
C13 | 0.0838 (15) | 0.0923 (17) | 0.0628 (13) | −0.0168 (14) | 0.0013 (12) | 0.0073 (12) |
C14 | 0.0492 (10) | 0.0886 (14) | 0.0724 (13) | 0.0031 (10) | −0.0124 (10) | 0.0043 (12) |
N1 | 0.0463 (7) | 0.0545 (8) | 0.0414 (7) | 0.0072 (6) | −0.0082 (6) | −0.0066 (6) |
O1 | 0.0851 (10) | 0.0498 (7) | 0.0560 (8) | 0.0052 (7) | −0.0223 (8) | 0.0062 (6) |
Cl1 | 0.0709 (3) | 0.0537 (2) | 0.0531 (2) | 0.0116 (2) | −0.01407 (19) | −0.0110 (2) |
C1—C2 | 1.384 (2) | C9—H9C | 0.9600 |
C1—C6 | 1.386 (2) | C10—C12 | 1.507 (2) |
C1—C7 | 1.511 (2) | C10—C11 | 1.533 (3) |
C2—C3 | 1.383 (3) | C10—H10 | 0.9800 |
C2—H2 | 0.9300 | C11—H11A | 0.9600 |
C3—C4 | 1.384 (3) | C11—H11B | 0.9600 |
C3—H3 | 0.9300 | C11—H11C | 0.9600 |
C4—C5 | 1.377 (3) | C12—N1 | 1.501 (2) |
C4—H4 | 0.9300 | C12—H12A | 0.9700 |
C5—O1 | 1.360 (2) | C12—H12B | 0.9700 |
C5—C6 | 1.386 (2) | C13—N1 | 1.464 (3) |
C6—H6 | 0.9300 | C13—H13A | 0.9600 |
C7—C8 | 1.532 (3) | C13—H13B | 0.9600 |
C7—C10 | 1.550 (2) | C13—H13C | 0.9600 |
C7—H7 | 0.9800 | C14—N1 | 1.474 (2) |
C8—C9 | 1.511 (3) | 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 | 0.95 (2) |
C9—H9B | 0.9600 | O1—H1O | 0.81 (3) |
C2—C1—C6 | 118.54 (15) | C12—C10—C7 | 110.59 (14) |
C2—C1—C7 | 120.59 (14) | C11—C10—C7 | 110.93 (14) |
C6—C1—C7 | 120.86 (15) | C12—C10—H10 | 108.8 |
C3—C2—C1 | 120.42 (16) | C11—C10—H10 | 108.8 |
C3—C2—H2 | 119.8 | C7—C10—H10 | 108.8 |
C1—C2—H2 | 119.8 | C10—C11—H11A | 109.5 |
C2—C3—C4 | 120.70 (17) | C10—C11—H11B | 109.5 |
C2—C3—H3 | 119.6 | H11A—C11—H11B | 109.5 |
C4—C3—H3 | 119.6 | C10—C11—H11C | 109.5 |
C5—C4—C3 | 119.18 (16) | H11A—C11—H11C | 109.5 |
C5—C4—H4 | 120.4 | H11B—C11—H11C | 109.5 |
C3—C4—H4 | 120.4 | N1—C12—C10 | 113.87 (14) |
O1—C5—C4 | 122.93 (15) | N1—C12—H12A | 108.8 |
O1—C5—C6 | 116.97 (16) | C10—C12—H12A | 108.8 |
C4—C5—C6 | 120.10 (15) | N1—C12—H12B | 108.8 |
C5—C6—C1 | 121.01 (15) | C10—C12—H12B | 108.8 |
C5—C6—H6 | 119.5 | H12A—C12—H12B | 107.7 |
C1—C6—H6 | 119.5 | N1—C13—H13A | 109.5 |
C1—C7—C8 | 109.85 (14) | N1—C13—H13B | 109.5 |
C1—C7—C10 | 110.67 (13) | H13A—C13—H13B | 109.5 |
C8—C7—C10 | 112.95 (14) | N1—C13—H13C | 109.5 |
C1—C7—H7 | 107.7 | H13A—C13—H13C | 109.5 |
C8—C7—H7 | 107.7 | H13B—C13—H13C | 109.5 |
C10—C7—H7 | 107.7 | N1—C14—H14A | 109.5 |
C9—C8—C7 | 112.78 (16) | N1—C14—H14B | 109.5 |
C9—C8—H8A | 109.0 | H14A—C14—H14B | 109.5 |
C7—C8—H8A | 109.0 | N1—C14—H14C | 109.5 |
C9—C8—H8B | 109.0 | H14A—C14—H14C | 109.5 |
C7—C8—H8B | 109.0 | H14B—C14—H14C | 109.5 |
H8A—C8—H8B | 107.8 | C13—N1—C14 | 110.15 (17) |
C8—C9—H9A | 109.5 | C13—N1—C12 | 114.60 (18) |
C8—C9—H9B | 109.5 | C14—N1—C12 | 109.75 (16) |
H9A—C9—H9B | 109.5 | C13—N1—H1N | 106.7 (11) |
C8—C9—H9C | 109.5 | C14—N1—H1N | 108.3 (11) |
H9A—C9—H9C | 109.5 | C12—N1—H1N | 107.0 (11) |
H9B—C9—H9C | 109.5 | C5—O1—H1O | 109.4 (19) |
C12—C10—C11 | 108.90 (17) | ||
C6—C1—C2—C3 | 1.9 (3) | C2—C1—C7—C10 | −65.1 (2) |
C7—C1—C2—C3 | −177.07 (16) | C6—C1—C7—C10 | 115.94 (17) |
C1—C2—C3—C4 | −0.6 (3) | C1—C7—C8—C9 | 59.4 (2) |
C2—C3—C4—C5 | −1.4 (3) | C10—C7—C8—C9 | −176.48 (17) |
C3—C4—C5—O1 | −177.47 (17) | C1—C7—C10—C12 | −170.03 (15) |
C3—C4—C5—C6 | 2.1 (3) | C8—C7—C10—C12 | 66.3 (2) |
O1—C5—C6—C1 | 178.81 (15) | C1—C7—C10—C11 | −49.1 (2) |
C4—C5—C6—C1 | −0.8 (2) | C8—C7—C10—C11 | −172.73 (16) |
C2—C1—C6—C5 | −1.2 (2) | C11—C10—C12—N1 | 80.2 (2) |
C7—C1—C6—C5 | 177.71 (15) | C7—C10—C12—N1 | −157.68 (17) |
C2—C1—C7—C8 | 60.3 (2) | C10—C12—N1—C13 | 78.7 (2) |
C6—C1—C7—C8 | −118.65 (17) | C10—C12—N1—C14 | −156.77 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1 | 0.95 (2) | 2.14 (2) | 3.0536 (15) | 161.0 (16) |
O1—H1O···Cl1i | 0.81 (3) | 2.29 (3) | 3.1013 (15) | 175 (2) |
C11—H11A···Cl1 | 0.96 | 2.75 | 3.614 (2) | 151 |
C13—H13B···Cl1ii | 0.96 | 2.71 | 3.651 (3) | 167 |
Symmetry codes: (i) −x+2, y−1/2, −z+5/2; (ii) x+1/2, −y+3/2, −z+2. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C14H24NO+·Cl− | C14H24NO+·Cl− | C14H24NO+·Cl− | C14H24NO+·Cl− |
Mr | 257.79 | 257.79 | 257.79 | 257.79 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 | Orthorhombic, P212121 | Orthorhombic, P212121 |
Temperature (K) | 294 | 294 | 294 | 294 |
a, b, c (Å) | 7.1600 (15), 11.688 (3), 17.514 (4) | 7.160 (3), 11.688 (5), 17.526 (8) | 8.8218 (6), 12.1304 (8), 14.0031 (9) | 8.8101 (6), 12.1094 (8), 13.9784 (9) |
α, β, γ (°) | 90, 94.535 (3), 90 | 90, 94.570 (7), 90 | 90, 90, 90 | 90, 90, 90 |
V (Å3) | 1461.1 (5) | 1462.0 (11) | 1498.50 (17) | 1491.29 (17) |
Z | 4 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.25 | 0.25 | 0.24 | 0.24 |
Crystal size (mm) | 0.18 × 0.15 × 0.09 | 0.15 × 0.12 × 0.06 | 0.17 × 0.14 × 0.09 | 0.21 × 0.17 × 0.12 |
Data collection | ||||
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) | Multi-scan (SADABS; Bruker, 2001) | Multi-scan (SADABS; Bruker, 2001) | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.955, 0.976 | 0.963, 0.986 | 0.958, 0.975 | 0.948, 0.969 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14096, 5135, 4972 | 13998, 5139, 4883 | 14552, 2653, 2540 | 14415, 2630, 2548 |
Rint | 0.022 | 0.021 | 0.022 | 0.019 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.595 | 0.595 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.072, 1.06 | 0.031, 0.075, 1.06 | 0.030, 0.081, 1.03 | 0.030, 0.083, 1.05 |
No. of reflections | 5135 | 5139 | 2653 | 2630 |
No. of parameters | 331 | 331 | 166 | 166 |
No. of restraints | 1 | 1 | 0 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.14, −0.12 | 0.14, −0.10 | 0.20, −0.13 | 0.22, −0.13 |
Absolute structure | Flack & Bernardinelli (2000), with 2430 Friedel pairs | Flack & Bernardinelli (2000), with 2431 Friedel pairs | Flack & Bernardinelli (2000), with 1113 Friedel pairs | Flack & Bernardinelli (2000), with 1104 Friedel pairs |
Absolute structure parameter | 0.03 (4) | −0.02 (4) | −0.02 (7) | 0.00 (6) |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1N···Cl1Bi | 0.875 (19) | 2.23 (2) | 3.0569 (17) | 157 (2) |
O1A—H1O···Cl1A | 0.83 (3) | 2.24 (3) | 3.0584 (17) | 168 (2) |
N1B—H2N···Cl1A | 0.90 (2) | 2.19 (2) | 3.0506 (15) | 158 (2) |
O1B—H2O···Cl1B | 0.79 (3) | 2.30 (3) | 3.0667 (17) | 164 (2) |
Symmetry code: (i) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1O···Cl1A | 0.81 (3) | 2.26 (3) | 3.060 (2) | 169 (3) |
N1A—H1N···Cl1Bi | 0.88 (2) | 2.23 (2) | 3.056 (2) | 156.5 (18) |
N1B—H2N···Cl1A | 0.91 (3) | 2.19 (3) | 3.051 (2) | 158.9 (19) |
O1B—H2O···Cl1B | 0.79 (3) | 2.30 (3) | 3.067 (2) | 166 (3) |
Symmetry code: (i) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1 | 0.97 (2) | 2.13 (2) | 3.0580 (15) | 160.5 (16) |
O1—H1O···Cl1i | 0.79 (3) | 2.32 (3) | 3.1083 (16) | 174 (2) |
C11—H11A···Cl1 | 0.96 | 2.75 | 3.620 (2) | 150.9 |
C13—H13C···Cl1ii | 0.96 | 2.71 | 3.657 (3) | 167.7 |
Symmetry codes: (i) −x, y+1/2, −z−1/2; (ii) x−1/2, −y+1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1 | 0.95 (2) | 2.14 (2) | 3.0536 (15) | 161.0 (16) |
O1—H1O···Cl1i | 0.81 (3) | 2.29 (3) | 3.1013 (15) | 175 (2) |
C11—H11A···Cl1 | 0.96 | 2.75 | 3.614 (2) | 151 |
C13—H13B···Cl1ii | 0.96 | 2.71 | 3.651 (3) | 167 |
Symmetry codes: (i) −x+2, y−1/2, −z+5/2; (ii) x+1/2, −y+3/2, −z+2. |
Parameter | (I), cation A | (I), cation B | (II), cation A | (II), cation B | (III) | (IV) |
C7—C8—C9 | 112.48 (16) | 114.95 (16) | 112.59 (18) | 115.22 (19) | 112.65 (17) | 112.78 (16) |
C8—C7—C10 | 118.80 (13) | 113.89 (13) | 111.66 (15) | 113.99 (15) | 112.91 (13) | 112.95 (14) |
C1—C7—C8—C9 | 63.8 (2) | 170.38 (16) | -63.6 (2) | -170.38 (18) | -59.4 (2) | 59.4 (2) |
C1—C7—C10—C12 | 63.21 (17) | 65.15 (17) | -63.4 (2) | -65.6 (2) | 170.15 (16) | -170.03 (15) |
C7—C10—C12—N1 | 171.87 (13) | 177.09 (13) | -172.03 (15) | -176.92 (15) | 157.87 (17) | -157.68 (17) |
Tapentadol is a novel centrally acting synthetic analgesic with a unique profile of action for the treatment of moderate to severe pain (Tzschentke et al., 2007). It acts in two ways, opioid (narcotic) and non-opioid. Tapentadol affects the brain and body primarily by activating opioid receptors in the brain, spinal cord and gastrointestinal tract. In addition, it inhibits the reuptake of the brain chemical norepinephrine which possibly has an analgesic effect. Tapentadol is being developed in immediate-release and extended-release formulations (Etropolski et al., 2010).
The United States Food and Drug Administration (US FDA) approved tapentadol hydrochloride in 2008 as an immediate-release oral tablet for the relief of moderate to severe acute pain, cancer-related and other. Tapentadol is manufactured by Janssen Ortho LLC, Gurabo, Puerto Rico, USA, and was initially developed by Grunenthal GmbH, Aachen, Germany, in conjunction with Johnson & Johnson Pharmaceutical Research and Development. We report here the crystal structures of four stereoisomers of tapentadol hydrochloride, (I)–(IV), as part of our ongoing study of the structural characterization of drug molecules (Ravikumar & Sridhar, 2009, 2010).
Resolution of the four isomers was carried out using reverse-phase and chiral high-performance liquid chromatography (HPLC) methods; compounds (I)–(IV) showed good resolution in HPLC analysis and diastereomeric isomer separation in reverse-phase HPLC analysis. The purities of all individual isomers were confirmed by both chiral and reverse-phase HPLC. In the chiral method, isomers (I), (II), (III) and (IV) eluted at retention times of 19.21, 24.56, 17.81 and 16.61 min, respectively (Fig. 1), whereas in the reverse-phase method, the retention times were 17.00, 17.21, 15.58 and 15.48 min, respectively. It can be seen that isomers (I) and (II) are one pair of enantiomers, and isomers (III) and (IV) are a second pair, as both pairs elute at the same retention time in reverse-phase HPLC analysis.
Differential scanning calorimetric (DSC) measurements were carried out using a Perkin–Elmer Diamond DSC apparatus. Experiments were performed at a heating rate of 10.0 K min-1 over a temperature range of 303–533 K under a nitrogen flow of 50 ml min-1. The DSC curves for all four isomers show sharp endothermic peaks at 482, 480, 477 and 478 K for isomers (I)–(IV), respectively (Fig. 2).
Tapentadol consists of a meta-substituted phenol ring possessing an ethyl and an aminopropyl residue at C7. It has two stereogenic centres at C7 and C10, which results in four possible diastereomers; the (R,R) isomer is currently the clinically used form (Franklin et al., 2010). Structurally, tapentadol is the closest chemical relative of tramadol in clinical use. Both tramdol and venlafaxine are racemic mixtures, whereas tapentadol represents only one stereoisomer, (1R,2R). Structurally, tapentadol differs from tramadol in being a phenol and not an ether. Also, both tramadol and venlafaxine incorporate a cyclohexyl moiety attached directly to the aromatic ring, while tapentadol lacks this feature.
The crystal structures of isomers (I) and (II) are enantiomorphs, crystallizing in the space group P21. Similarly, the crystal structures of isomers (III) and (IV) are also enantiomorphs, but crystallizing in the space group P212121. Thus, (I) and (III), and (II) and (IV), are pairs of diastereomers. Unambiguous determination of the absolute configurations of all four structures was confirmed by means of refinement of the Flack parameter (Flack & Bernardinelli, 2000). It was therefore confirmed that (I) is the R,R enantiomer and (II) is the S,S enantiomer, with melting points of 482–483 and 480–481 K, respectively. It was also found that (III) is the S,R isomer and (IV) is the R,S isomer, with melting points of 477–478 and 478–479 K, respectively. Each asymmetric unit in (I) and (II) includes two tapentadol cations and two chloride anions (Fig. 3). In the case of (III) and (IV), the asymmetric unit consists of one tapentadol cation and one chloride anion (Fig. 4).
The geometric parameters of (I)–(IV) are unremarkable. However, there are significant angular variations observed between the two independent molecules of (I) and (II) involving the chiral atom C7, the differences being C7—C8—C9 = 2.5 [(I)] and 2.6° [(II)], and C8—C7—C10 = 2.1 [(I)] and 2.3° [(II)] (Table 1). This may perhaps be attributed to the cis–trans orientation of the ethyl group.
The aminopropyl and ethyl groups are located on each side of the plane defined by the aromatic ring. The two molecules constituting the asymmetric unit of (I), although constructed from molecules with the same chirality, pair around a pseudo-centrosymmetry at (1/4, 0.65, 0.75) and differ significantly in the orientation of atom C9 of the ethyl group. The orientation of the ethyl group with respect to the phenol ring can be seen from the torsion angle C1—C7—C8—C9, which is cis in (IA) and trans in (1B), while in (III) it adopts a cis orientation. The conformation of the aminopropyl group can be defined from the torsion angles C—C—C—C and C—C—C—N, and the conformation is cis–trans for both molecules of (I), while it is trans–trans for (III) (Table 1). An overlay of the tapentadol molecules, superimposing atoms C1–C7 of the phenol ring system, reveals the orientational differences of both the ethyl and aminopropyl groups with respect to the phenol ring (Fig. 5). It is interesting to note that the ethyl group of (III) adopts a similar conformation to molecule A of the (I), while the conformation of the aminopropyl group is entirely different from (I). This difference might influence the participation of the aminopropyl group in C—H···Cl interactions in (III), which are absent in (I).
The crystal structures of the four stereoisomers, (I)–(IV), are stabilized by N—H···Cl and O—H···Cl hydrogen bonds (Tables 2–5) between the chloride ions and the amino and hydroxyl groups of the tapentadol molecules. Each chloride ion accepts two hydrogen bonds from the amino and hydroxyl groups of the tapentadol molecules and forms an infinite one-dimensional helical chain. In (I) and (II), the helical chain is along the a axis (Fig. 6), while in (III) and (IV) it is along the b axis (Fig. 7). Furthermore, in (III) and (IV) C—H···Cl interactions link the helical chains to adjacent chains.