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Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

Four stereoisomers of the novel μ-opioid receptor agonist ta­penta­dol hydro­chloride

aLaboratory of X-ray Crystallography, Indian Institute of Chemical Technology, Hyderabad 500 007, India, and bResearch and Development Centre, Actavis Pharmaceutical Development Centre Pvt. Ltd, Bangalore 560 034, India
*Correspondence e-mail: sshiya@yahoo.com

(Received 26 October 2010; accepted 12 January 2011; online 20 January 2011)

The crystal and mol­ecular structures of four stereoisomers of tapenta­dol hydro­chloride [systematic name: 3-(3-hy­droxy­phenyl)-N,N,2-trimethyl­pentan-1-aminium chloride], C14H24NO+·Cl, a novel analgesic agent, have been determined by X-ray crystal structure analysis. Resolution of the isomers was carried out by reverse-phase and chiral high-performance liquid chromatographic (HPLC) methods. Stereoisomers (I)[link] and (II)[link] crystallize in the monoclinic space group P21, each with two tapenta­dol cations and two chloride anions in the asymmetric unit, while stereoisomers (III)[link] and (IV)[link] crystallize in the ortho­rhom­bic space group P212121, with one tapenta­dol cation and one chloride anion in the asymmetric unit. The absolute configurations of the four enantio­mers were determined unambiguously by X-ray crystallography. The crystal structures reveal the stereochemistries at the 3-ethyl and 2-methyl groups to be R,R, S,S, S,R and R,S in stereoisomers (I)[link]–(IV)[link], respectively. The ethyl and amino­propyl groups adopt different orientations with respect to the phenol ring for (I)[link] and (IV)[link]. In all four structures, the chloride ions take part in N—H⋯Cl and O—H⋯Cl hydrogen bonds with the tapenta­dol mol­ecules, resulting in one-dimensional helical chains in the crystal packing in each case.

Comment

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[Tzschentke, T. M., Christoph, T., Kögel, B., Schiene, K., Hennies, H. H., Englberger, W., Haurand, M., Jahnel, U., Cremers, T. I., Friderichs, E. & De Vry, J. (2007). J. Pharmacol. Exp. Ther. 323, 265-276.]). It acts in two ways, viz. 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 re-uptake 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[Etropolski, M. S., Okamoto, A., Shapiro, D. Y. & Rauschkolb, C. (2010). Pain Physician, 13, 61-70.]).

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, both 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)[link]–(IV)[link], as part of our ongoing study of the structural characterization of drug mol­ecules (Ravikumar & Sridhar, 2009[Ravikumar, K. & Sridhar, B. (2009). Acta Cryst. C65, o502-o505.], 2010[Ravikumar, K. & Sridhar, B. (2010). Acta Cryst. C66, o97-o100.]).

[Scheme 1]

Resolution of the four isomers was carried out using reverse-phase and chiral high-performance liquid chromatography (HPLC) methods; compounds (I)[link]–(IV)[link] 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)[link], (II)[link], (III)[link] and (IV)[link] eluted at retention times of 19.21, 24.56, 17.81 and 16.61 min, respectively (Fig. 1[link]), 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)[link] and (II)[link] are one pair of enantio­mers, and isomers (III)[link] and (IV)[link] are a second pair, having similar retention times 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 (I)–(IV)[link] show sharp endothermic peaks, corresponding to melting points, at 482, 480, 477 and 478 K for isomers (I)–(IV)[link], respectively (Fig. 2[link]).

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[Franklin, R., Golding, T. & Tyson, R. G. (2010). US Patent No. 2010/0227921A1.]). Tapenta­dol is structurally the closest chemical relative of tramadol[link] in clinical use. Both tramadol[link] and venlafaxine[link] are racemic mixtures (Reeves & Cox, 2008[Reeves, R. R. & Cox, S. K. (2008). South. Med. J. 101, 193-195.]), whereas tapenta­dol represents only one stereo­isomer, viz. (1R,2R). Structurally, tapenta­dol differs from tramadol[link] in being a phenol and not an ether. Also, both tramadol[link] and venlafaxine[link] incorporate a cyclo­hexyl group attached directly to the aromatic ring, while tapenta­dol lacks this feature.

The crystal structures of isomers (I)[link] and (II)[link] are enantio­morphs, crystallizing in the space group P21. Similarly, the crystal structures of isomers (III)[link] and (IV)[link] are also enantio­morphs, but crystallizing in the space group P212121. Thus, (I)[link]/(III)[link] and (II)[link]/(IV)[link] are pairs of diastereomers. Unambiguous determination of the absolute configurations of all four structures was carried out by means of refinement of the Flack parameter (Flack & Bernardinelli, 2000[Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143-1148.]). It was therefore assigned that (I)[link] is the R,R enantio­mer and (II)[link] is the S,S enantio­mer, with melting points of 482–483 and 480–481 K, respectively. It was also found that (III)[link] is the S,R isomer and (IV)[link] is the R,S isomer, with melting points of 477–478 and 478–479 K, respectively, from the above-mentioned DSC studies. Each asymmetric unit in (I)[link] and (II)[link] comprises two tapenta­dol cations and two chloride anions (Fig. 3[link]). In the case of (III)[link] and (IV)[link], the asymmetric unit consists of one tapenta­dol cation and one chloride anion (Fig. 4[link]).

The geometric parameters of (I)[link]–(IV)[link] are similar. However, there are significant angular variations observed between the two independent mol­ecules of (I)[link] and (II)[link] involving the chiral atom C7, the differences being C7—C8—C9 = 2.5 (2) [in (I)[link]] and 2.7 (2)° [in (II)[link]], and C8—C7—C10 = 2.1 (1) [in (I)[link]] and 2.3 (2)° [in (II)[link]] (Table 1[link]). This may perhaps be attributed to the syn/anti conformers found around the C8—C9 bond.

The amino­propyl and ethyl groups are located on opposite sides of the plane defined by the aromatic ring. The two cations in asymmetric unit of (I)[link], although constructed from mol­ecules with the same chirality, are paired around a pseudo­centre of symmetry at ([{1 \over 4}], 0.65, [{3 \over 4}]) 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 molecule A of (I)[link] and trans in molecule B, while in (III)[link] it adopts a cis orientation. The conformation of the amino­propyl group can be defined from the C—C—C—C and C—C—C—N torsion angles, and the conformation is cistrans for both mol­ecules of (I)[link], while it is transtrans for (III)[link] (Table 1[link]). An overlay of the tapenta­dol mol­ecules, superimposing atoms C1–C7 of the phenol ring system, reveals the differences in orientation of both the ethyl and amino­propyl groups with respect to the phenol ring (Fig. 5[link]). It is inter­esting to note that the ethyl group of (III)[link] adopts a similar conformation to mol­ecule (IA)[link], while the conformation of the amino­propyl group is entirely different from (I)[link]. This difference might influence the participation of the amino­propyl group in C—H⋯Cl inter­actions in (III)[link], which are absent in (I)[link].

The crystal structures of the four stereoisomers, (I)[link]–(IV)[link], feature N—H⋯Cl and O—H⋯Cl hydrogen bonds (Tables 2[link]–5[link][link][link]) between the chloride ions and the amino and hydroxy groups of the tapenta­dol mol­ecules. Each chloride ion accepts two hydrogen bonds from the amino and hydroxy groups of the tapenta­dol mol­ecules and forms a one-dimensional helical chain. In (I)[link] and (II)[link], the helical chain is along the a axis (Fig. 6[link]), while in (III)[link] and (IV)[link] it is along the b axis (Fig. 7[link]). Furthermore, in (III)[link] and (IV)[link] C—H⋯Cl inter­actions link the helical chains to adjacent chains.

[Figure 1]
Figure 1
Chiral HPLC profiles of the four stereoisomers of tapenta­dol hydro­chloride, using a CHIRALPAK AD-3 (250 × 4.6 mm × 5 µm) column and an 85:15 (v/v) hexane–tetra­hydro­furan solvent system.
[Figure 2]
Figure 2
Comparative differential scanning calorimetric (DSC) thermographs for the four stereoisomers of tapenta­dol hydro­chloride.
[Figure 3]
Figure 3
Views of (a) (I)[link] and (b) (II)[link], showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 4]
Figure 4
Views of (a) (III)[link] and (b) (IV)[link], showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 5]
Figure 5
Superposition of the mol­ecular conformations of the tapenta­dol mol­ecules of (I)[link] and (IV)[link], showing the orientations of the ethyl and amino­propyl groups with respect to the phenol ring. The overlay was made by making a least-squares fit through the planar phenol ring (atoms C1–C7) of tapenta­dol [mol­ecules (IA)[link] and (IB)[link]] and (IV)[link].
[Figure 6]
Figure 6
Part of the crystal packing for (I)[link], showing the involvement of the chloride ions in N—H⋯Cl and O—H⋯Cl hydrogen bonds with the tapenta­dol mol­ecules, resulting in a one-dimensional helical chain along the a axis. Hydrogen bonds are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity. Only atoms involved in hydrogen bonding have been labelled. [Symmetry code: (i) x − 1, y, z.]
[Figure 7]
Figure 7
Part of the crystal packing for (III)[link], showing the helical chains of tapenta­dol mol­ecules linked by the chloride ions via N—H⋯Cl and O—H⋯Cl hydrogen bonds. Also shown are the helical chains inter­linked by C—H⋯Cl hydrogen bonds. Hydrogen bonds are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity. Only atoms involved in hydrogen bonding have been labelled. [Symmetry codes: (i) −x + 2, y + [{1\over 2}], −z + [{1\over 2}]; (ii) x + [{1\over 2}], −y − [{1\over 2}], −z.]

Experimental

(2R,3R)-3-(3-Hy­droxy­phenyl)-N,N,2-trimethyl­pentan-1-aminium chloride, (I)[link], was prepared as follows. (2R,3S)-1-Dimethyl­amino-3-(3-hy­droxy­phenyl)-2-methyl­pentan-3-ol tartaric acid salt (35 g, 1 mol) 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 into dichloro­methane (150 ml) at 293–298 K. The organic layer was separated, dried over anhydrous sodium sulfate and concentrated under reduced pressure to afford 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 cm−2; 1 kg cm−2 = 98066.5 Pa) was applied. The reaction mixture was heated to 318–323 K for 5 h. After cooling, the reaction mass was filtered through Celite Hyflo Super Cel 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 separated, dried over anhydrous sodium sulfate and concentrated 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 filtered 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 butanone to yield a white solid. Purity by HPLC: 99.53%; m.p. 482–483 K; 1H NMR (D2O): δ 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)[link], was prepared as follows. Using (2S,3R)-1-dimethyl­amino-3-(3-hy­droxy­phenyl)-2-methyl­pentan-3-ol tartaric acid salt, (25 g, 1 mol), the above process was followed to obtain (II)[link]. It was recrystallized from butanone to yield a white solid. Purity by HPLC: 99.85%; m.p. 480–481 K; 1H NMR (D2O): δ 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)[link], 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, 1 mol) 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), dried over anhydrous sodium sulfate and concentrated 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 butanone to yield a white solid (m.p. 477–478 K). 1H NMR (D2O): δ 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)[link], was prepared as follows. (2S,3R)-1-Dimethyl­amino-3-(3-meth­oxy­phenyl)-2-methyl­pentane (12 g, 1 mol) 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 separated, dried over anhydrous sodium sulfate and concentrated 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 butanone to yield a white solid (m.p. 478–479 K). 1H NMR (D2O): δ 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 × 5 µm) 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)[link]–(IV)[link], suitable for X-ray crystallography studies were obtained by cooling hot methanol solutions.

Stereoisomer (I)[link]

Crystal data
  • C14H24NO+·Cl

  • Mr = 257.79

  • Monoclinic, P 21

  • a = 7.1600 (15) Å

  • b = 11.688 (3) Å

  • c = 17.514 (4) Å

  • β = 94.535 (3)°

  • V = 1461.1 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.25 mm−1

  • T = 294 K

  • 0.18 × 0.15 × 0.09 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SAINT (Version 6.28A), SMART (Version 5.625) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.955, Tmax = 0.976

  • 14096 measured reflections

  • 5135 independent reflections

  • 4972 reflections with I > 2σ(I)

  • Rint = 0.022

Refinement
  • R[F2 > 2σ(F2)] = 0.027

  • wR(F2) = 0.072

  • S = 1.06

  • 5135 reflections

  • 331 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.14 e Å−3

  • Δρmin = −0.12 e Å−3

  • Absolute structure: Flack & Bernardinelli (2000[Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143-1148.]), with 2430 Friedel pairs

  • Flack parameter: 0.03 (4)

Table 1
Selected valence and torsion angles (°) for stereoisomers (I)[link]–(IV)[link]

Parameter (I)[link], molecule A (I)[link], molecule B (II)[link], molecule A (II)[link], molecule B (III)[link] (IV)[link]
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)

Table 2
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A DA 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.

Stereoisomer (II)[link]

Crystal data
  • C14H24NO+·Cl

  • Mr = 257.79

  • Monoclinic, P 21

  • a = 7.160 (3) Å

  • b = 11.688 (5) Å

  • c = 17.526 (8) Å

  • β = 94.570 (7)°

  • V = 1462.0 (11) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.25 mm−1

  • T = 294 K

  • 0.15 × 0.12 × 0.06 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SAINT (Version 6.28A), SMART (Version 5.625) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.963, Tmax = 0.986

  • 13998 measured reflections

  • 5139 independent reflections

  • 4883 reflections with I > 2σ(I)

  • Rint = 0.021

Refinement
  • R[F2 > 2σ(F2)] = 0.031

  • wR(F2) = 0.075

  • S = 1.06

  • 5139 reflections

  • 331 parameters

  • 1 restraint

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.14 e Å−3

  • Δρmin = −0.10 e Å−3

  • Absolute structure: Flack & Bernardinelli (2000[Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143-1148.]), with 2431 Friedel pairs

  • Flack parameter: −0.02 (4)

Table 3
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A DA 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.

Stereoisomer (III)[link]

Crystal data
  • C14H24NO+·Cl

  • Mr = 257.79

  • Orthorhombic, P 21 21 21

  • a = 8.8218 (6) Å

  • b = 12.1304 (8) Å

  • c = 14.0031 (9) Å

  • V = 1498.50 (17) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.24 mm−1

  • T = 294 K

  • 0.17 × 0.14 × 0.09 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SAINT (Version 6.28A), SMART (Version 5.625) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.958, Tmax = 0.975

  • 14552 measured reflections

  • 2653 independent reflections

  • 2540 reflections with I > 2σ(I)

  • Rint = 0.022

Refinement
  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.081

  • S = 1.03

  • 2653 reflections

  • 166 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.13 e Å−3

  • Absolute structure: Flack & Bernardinelli (2000[Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143-1148.]), with 1113 Friedel pairs

  • Flack parameter: −0.02 (7)

Table 4
Hydrogen-bond geometry (Å, °) for (III)[link]

D—H⋯A D—H H⋯A DA 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+{\script{1\over 2}}, -z-{\script{1\over 2}}]; (ii) [x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z].

Stereoisomer (IV)[link]

Crystal data
  • C14H24NO+·Cl

  • Mr = 257.79

  • Orthorhombic, P 21 21 21

  • a = 8.8101 (6) Å

  • b = 12.1094 (8) Å

  • c = 13.9784 (9) Å

  • V = 1491.29 (17) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.24 mm−1

  • T = 294 K

  • 0.21 × 0.17 × 0.12 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2001[Bruker (2001). SAINT (Version 6.28A), SMART (Version 5.625) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.948, Tmax = 0.969

  • 14415 measured reflections

  • 2630 independent reflections

  • 2548 reflections with I > 2σ(I)

  • Rint = 0.019

Refinement
  • R[F2 > 2σ(F2)] = 0.030

  • wR(F2) = 0.083

  • S = 1.05

  • 2630 reflections

  • 166 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.13 e Å−3

  • Absolute structure: Flack & Bernardinelli (2000[Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143-1148.]), with 1104 Friedel pairs

  • Flack parameter: 0.00 (6)

Table 5
Hydrogen-bond geometry (Å, °) for (IV)[link]

D—H⋯A D—H H⋯A DA 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-{\script{1\over 2}}, -z+{\script{5\over 2}}]; (ii) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2].

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 or 1.2Ueq(C) for other H atoms. The methyl groups were allowed to rotate but not to tip.

For all compounds, data collection: SMART (Bruker, 2001[Bruker (2001). SAINT (Version 6.28A), SMART (Version 5.625) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SAINT (Version 6.28A), SMART (Version 5.625) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg & Putz, 2005[Brandenburg, K. & Putz, H. (2005). DIAMOND. Release 3.0c. Crystal Impact GbR, Bonn, Germany.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

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 cistrans 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 cistrans for both molecules of (I), while it is transtrans 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.

Related literature top

For related literature, see: Etropolski et al. (2010); Flack & Bernardinelli (2000); Franklin et al. (2010); Ravikumar & Sridhar (2009, 2010); Tzschentke et al. (2007).

Experimental top

(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.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. Chiral HPLC profiles of the four stereoisomers of tapentadol hydrochloride, using a CHIRALPAK AD-3 (250 × 4.6 mm × 5 µm) column and an 85:15 (v/v) hexane–tetrahydrofuran solvent system.
[Figure 2] Fig. 2. Comparative DSC monographs for the four stereoisomers of tapentadol hydrochloride.
[Figure 3] Fig. 3. Views of (a) (I) and (b) (II), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 4] Fig. 4. Views of (a) (III) and (b) (IV), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines indicate hydrogen bonds.
[Figure 5] Fig. 5. Superposition of the molecular conformations of the tapentadol molecules of (I) and (IV), showing the orientational differences of the ethyl and aminopropyl groups with respect to the phenol ring. The overlay was made by making a least-squares fit through the planar phenol ring (atoms C1–C7) of tapentadol [molecule 1 of (I), labelled 1]. Molecule 2 of (I) is labelled 2 [r.m.s. deviation 0.011 Å] and the molecule of (IV) is labelled 3 [r.m.s. deviation 0.022 Å].
[Figure 6] Fig. 6. Part of the crystal packing for (I), showing the involvement of the chloride ions in N—H···Cl and O—H···Cl hydrogen bonds with the tapentadol molecules, resulting in an infinite one-dimensional helical chain along the a axis. Hydrogen bonds are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity. Only atoms involved in hydrogen bonding have been labelled. [Symmetry code: (i) x - 1, y, z.]
[Figure 7] Fig. 7. Part of the crystal packing for (III), showing the helical chains of tapentadol molecules linked by the chloride ions via N—H···Cl and O—H···Cl hydrogen bonds. Also shown are the helical chains interlinked by C—H···Cl hydrogen bonds. Hydrogen bonds are shown as dashed lines and H atoms not involved in hydrogen bonding have been omitted for clarity. Only atoms involved in hydrogen bonding have been labelled. [Symmetry codes: (i) -x + 2, y + 1/2, -z + 1/2; (ii) x + 1/2, -y - 1/2, -z.]
(I) (2R,3R)-3-(3-hydroxyphenyl)- N,N,2-trimethylpentan-1-aminium chloride top
Crystal data top
C14H24NO+·ClF(000) = 560
Mr = 257.79Dx = 1.172 Mg m3
Monoclinic, P21Melting point: 482 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 7.1600 (15) ÅCell parameters from 5112 reflections
b = 11.688 (3) Åθ = 2.3–28.0°
c = 17.514 (4) ŵ = 0.25 mm1
β = 94.535 (3)°T = 294 K
V = 1461.1 (5) Å3Block, colourless
Z = 40.18 × 0.15 × 0.09 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
5135 independent reflections
Radiation source: fine-focus sealed tube4972 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 25.0°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 88
Tmin = 0.955, Tmax = 0.976k = 1313
14096 measured reflectionsl = 2020
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H 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 reflectionsΔρmax = 0.14 e Å3
331 parametersΔρmin = 0.12 e Å3
1 restraintAbsolute structure: Flack & Bernardinelli (2000), with 2430 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.03 (4)
Crystal data top
C14H24NO+·ClV = 1461.1 (5) Å3
Mr = 257.79Z = 4
Monoclinic, P21Mo Kα radiation
a = 7.1600 (15) ŵ = 0.25 mm1
b = 11.688 (3) ÅT = 294 K
c = 17.514 (4) Å0.18 × 0.15 × 0.09 mm
β = 94.535 (3)°
Data collection top
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 = 0.976Rint = 0.022
14096 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.072Δρmax = 0.14 e Å3
S = 1.06Δρmin = 0.12 e Å3
5135 reflectionsAbsolute structure: Flack & Bernardinelli (2000), with 2430 Friedel pairs
331 parametersAbsolute structure parameter: 0.03 (4)
1 restraint
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1A0.2230 (2)0.53067 (13)0.77595 (8)0.0411 (3)
C2A0.1655 (2)0.42334 (14)0.79941 (10)0.0468 (4)
H2A0.20510.39660.84800.056*
C3A0.0501 (2)0.35644 (14)0.75092 (10)0.0506 (4)
H3A0.01290.28500.76750.061*
C4A0.0113 (2)0.39336 (15)0.67811 (10)0.0511 (4)
H4A0.08840.34730.64580.061*
C5A0.0441 (2)0.50000 (15)0.65445 (9)0.0484 (4)
C6A0.1607 (2)0.56758 (15)0.70285 (9)0.0451 (3)
H6A0.19790.63890.68610.054*
C7A0.3508 (2)0.60749 (14)0.82733 (9)0.0434 (3)
H7A0.40420.66280.79310.052*
C8A0.5179 (2)0.54344 (17)0.86704 (11)0.0548 (4)
H8A0.58730.59500.90220.066*
H8B0.47210.48090.89680.066*
C9A0.6488 (3)0.4961 (2)0.81056 (13)0.0711 (6)
H9A0.58400.43950.77880.107*
H9B0.75570.46180.83810.107*
H9C0.68940.55710.77910.107*
C10A0.2460 (2)0.67956 (13)0.88482 (9)0.0433 (3)
H10A0.34070.72500.91470.052*
C11A0.1098 (3)0.76350 (16)0.84416 (10)0.0593 (4)
H11A0.00790.72220.81810.089*
H11B0.17350.80710.80770.089*
H11C0.06190.81420.88110.089*
C12A0.1527 (2)0.60464 (14)0.94078 (9)0.0474 (4)
H12A0.05350.56160.91290.057*
H12B0.24400.55000.96260.057*
C13A0.0158 (3)0.5842 (2)1.05630 (13)0.0767 (6)
H13A0.07650.52931.07510.115*
H13B0.11730.54531.02810.115*
H13C0.06240.62431.09870.115*
C14A0.2065 (3)0.7431 (2)1.04853 (12)0.0782 (7)
H14A0.31520.69971.06630.117*
H14B0.14930.77461.09160.117*
H14C0.24270.80401.01600.117*
N1A0.0712 (2)0.66755 (13)1.00491 (8)0.0498 (3)
H1N0.021 (3)0.7102 (16)0.9856 (9)0.042 (4)*
O1A0.0167 (2)0.53353 (14)0.58189 (7)0.0686 (4)
H1O0.044 (3)0.589 (2)0.5671 (13)0.075 (7)*
C1B0.6956 (2)1.01275 (14)0.73214 (8)0.0428 (3)
C2B0.6216 (2)1.11695 (15)0.70488 (10)0.0500 (4)
H2B0.66071.14810.65990.060*
C3B0.4905 (3)1.17376 (15)0.74463 (10)0.0558 (4)
H3B0.44061.24240.72550.067*
C4B0.4319 (2)1.13059 (16)0.81210 (10)0.0555 (4)
H4B0.34501.17040.83860.067*
C5B0.5039 (2)1.02764 (16)0.83984 (9)0.0508 (4)
C6B0.6346 (2)0.96934 (15)0.79978 (9)0.0472 (4)
H6B0.68210.89990.81860.057*
C7B0.8437 (2)0.94794 (14)0.69167 (9)0.0437 (3)
H7B0.90920.90000.73110.052*
C8B0.9929 (2)1.02946 (16)0.66432 (11)0.0536 (4)
H8C0.93511.07710.62370.064*
H8D1.03501.07940.70650.064*
C9B1.1617 (3)0.9715 (2)0.63533 (14)0.0744 (6)
H9D1.20960.91570.67200.112*
H9E1.25661.02750.62800.112*
H9F1.12620.93440.58750.112*
C10B0.7620 (2)0.86367 (14)0.62899 (9)0.0418 (3)
H10B0.86810.82500.60800.050*
C11B0.6406 (3)0.77170 (16)0.66174 (10)0.0582 (4)
H11D0.53190.80650.68060.087*
H11E0.71110.73300.70290.087*
H11F0.60240.71760.62230.087*
C12B0.6575 (2)0.92858 (13)0.56351 (9)0.0443 (4)
H12C0.55450.96980.58360.053*
H12D0.74170.98480.54430.053*
C13B0.4897 (3)0.93067 (18)0.43623 (11)0.0628 (5)
H13D0.57960.98450.41980.094*
H13E0.38700.97120.45580.094*
H13F0.44400.88420.39360.094*
C14B0.7238 (3)0.7802 (2)0.46717 (11)0.0663 (5)
H14D0.67100.74290.42170.099*
H14E0.76300.72380.50490.099*
H14F0.83000.82510.45520.099*
N1B0.58074 (19)0.85609 (12)0.49780 (7)0.0445 (3)
H2N0.492 (3)0.8086 (19)0.5141 (11)0.062 (5)*
O1B0.4466 (2)0.98863 (15)0.90748 (8)0.0696 (4)
H2O0.505 (4)0.934 (2)0.9218 (14)0.079 (8)*
Cl1A0.22980 (6)0.71158 (4)0.51060 (3)0.05598 (11)
Cl1B0.71615 (6)0.81338 (4)0.98631 (3)0.05652 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0380 (8)0.0436 (8)0.0424 (8)0.0047 (6)0.0079 (6)0.0020 (6)
C2A0.0496 (9)0.0450 (8)0.0460 (8)0.0077 (7)0.0054 (7)0.0008 (7)
C3A0.0537 (9)0.0411 (8)0.0585 (10)0.0016 (7)0.0137 (8)0.0037 (7)
C4A0.0427 (9)0.0564 (10)0.0549 (9)0.0083 (7)0.0088 (7)0.0127 (8)
C5A0.0428 (8)0.0612 (10)0.0416 (8)0.0021 (8)0.0059 (6)0.0030 (7)
C6A0.0434 (8)0.0487 (9)0.0436 (8)0.0048 (7)0.0066 (6)0.0008 (7)
C7A0.0399 (8)0.0480 (8)0.0422 (8)0.0013 (7)0.0028 (6)0.0006 (7)
C8A0.0421 (9)0.0611 (11)0.0606 (10)0.0066 (8)0.0011 (7)0.0033 (8)
C9A0.0482 (10)0.0724 (13)0.0943 (15)0.0117 (10)0.0158 (10)0.0027 (11)
C10A0.0428 (8)0.0421 (8)0.0442 (8)0.0016 (6)0.0012 (6)0.0023 (6)
C11A0.0692 (12)0.0533 (10)0.0550 (10)0.0170 (9)0.0030 (9)0.0046 (8)
C12A0.0526 (9)0.0403 (8)0.0502 (9)0.0081 (7)0.0102 (7)0.0014 (7)
C13A0.0839 (14)0.0799 (14)0.0709 (13)0.0194 (12)0.0357 (11)0.0217 (11)
C14A0.0765 (14)0.0992 (18)0.0577 (11)0.0006 (12)0.0027 (10)0.0235 (12)
N1A0.0493 (8)0.0534 (8)0.0472 (7)0.0120 (7)0.0066 (6)0.0003 (6)
O1A0.0699 (9)0.0868 (10)0.0470 (7)0.0242 (8)0.0089 (6)0.0078 (7)
C1B0.0369 (8)0.0467 (8)0.0436 (8)0.0019 (7)0.0041 (6)0.0069 (7)
C2B0.0482 (9)0.0499 (9)0.0512 (9)0.0038 (7)0.0006 (7)0.0020 (7)
C3B0.0547 (10)0.0488 (9)0.0628 (11)0.0132 (8)0.0011 (8)0.0005 (8)
C4B0.0499 (9)0.0582 (10)0.0584 (10)0.0136 (8)0.0049 (8)0.0078 (8)
C5B0.0462 (9)0.0605 (10)0.0455 (9)0.0046 (8)0.0021 (7)0.0034 (8)
C6B0.0453 (9)0.0483 (9)0.0468 (8)0.0074 (7)0.0047 (7)0.0020 (7)
C7B0.0371 (8)0.0488 (9)0.0444 (8)0.0079 (7)0.0024 (6)0.0008 (7)
C8B0.0364 (8)0.0576 (10)0.0662 (11)0.0026 (7)0.0000 (7)0.0107 (8)
C9B0.0495 (10)0.0774 (14)0.0984 (15)0.0036 (10)0.0182 (10)0.0195 (12)
C10B0.0394 (8)0.0405 (8)0.0453 (8)0.0038 (6)0.0028 (6)0.0009 (7)
C11B0.0718 (12)0.0490 (9)0.0531 (10)0.0090 (8)0.0005 (8)0.0066 (8)
C12B0.0444 (8)0.0414 (8)0.0464 (8)0.0024 (7)0.0004 (7)0.0012 (6)
C13B0.0617 (11)0.0703 (12)0.0538 (10)0.0102 (9)0.0129 (8)0.0125 (9)
C14B0.0650 (12)0.0815 (14)0.0528 (10)0.0079 (10)0.0076 (9)0.0157 (9)
N1B0.0407 (7)0.0490 (8)0.0437 (7)0.0059 (6)0.0015 (5)0.0030 (6)
O1B0.0704 (9)0.0804 (10)0.0606 (8)0.0256 (8)0.0207 (7)0.0100 (7)
Cl1A0.0526 (2)0.0472 (2)0.0679 (3)0.00960 (19)0.00320 (17)0.00328 (19)
Cl1B0.0522 (2)0.0498 (2)0.0675 (3)0.00818 (19)0.00444 (17)0.0043 (2)
Geometric parameters (Å, º) top
C1A—C6A1.391 (2)C1B—C6B1.390 (2)
C1A—C2A1.392 (2)C1B—C2B1.397 (2)
C1A—C7A1.524 (2)C1B—C7B1.523 (2)
C2A—C3A1.380 (2)C2B—C3B1.382 (3)
C2A—H2A0.9300C2B—H2B0.9300
C3A—C4A1.385 (3)C3B—C4B1.380 (3)
C3A—H3A0.9300C3B—H3B0.9300
C4A—C5A1.382 (3)C4B—C5B1.382 (3)
C4A—H4A0.9300C4B—H4B0.9300
C5A—O1A1.368 (2)C5B—O1B1.362 (2)
C5A—C6A1.389 (2)C5B—C6B1.392 (2)
C6A—H6A0.9300C6B—H6B0.9300
C7A—C8A1.531 (2)C7B—C8B1.536 (2)
C7A—C10A1.551 (2)C7B—C10B1.554 (2)
C7A—H7A0.9800C7B—H7B0.9800
C8A—C9A1.520 (3)C8B—C9B1.508 (3)
C8A—H8A0.9700C8B—H8C0.9700
C8A—H8B0.9700C8B—H8D0.9700
C9A—H9A0.9600C9B—H9D0.9600
C9A—H9B0.9600C9B—H9E0.9600
C9A—H9C0.9600C9B—H9F0.9600
C10A—C12A1.509 (2)C10B—C12B1.522 (2)
C10A—C11A1.520 (2)C10B—C11B1.523 (2)
C10A—H10A0.9800C10B—H10B0.9800
C11A—H11A0.9600C11B—H11D0.9600
C11A—H11B0.9600C11B—H11E0.9600
C11A—H11C0.9600C11B—H11F0.9600
C12A—N1A1.499 (2)C12B—N1B1.498 (2)
C12A—H12A0.9700C12B—H12C0.9700
C12A—H12B0.9700C12B—H12D0.9700
C13A—N1A1.496 (3)C13B—N1B1.495 (2)
C13A—H13A0.9600C13B—H13D0.9600
C13A—H13B0.9600C13B—H13E0.9600
C13A—H13C0.9600C13B—H13F0.9600
C14A—N1A1.478 (3)C14B—N1B1.487 (2)
C14A—H14A0.9600C14B—H14D0.9600
C14A—H14B0.9600C14B—H14E0.9600
C14A—H14C0.9600C14B—H14F0.9600
N1A—H1N0.875 (19)N1B—H2N0.90 (2)
O1A—H1O0.83 (3)O1B—H2O0.79 (3)
C6A—C1A—C2A118.07 (15)C6B—C1B—C2B118.24 (15)
C6A—C1A—C7A119.64 (14)C6B—C1B—C7B119.49 (14)
C2A—C1A—C7A122.28 (14)C2B—C1B—C7B122.25 (15)
C3A—C2A—C1A120.36 (15)C3B—C2B—C1B120.06 (16)
C3A—C2A—H2A119.8C3B—C2B—H2B120.0
C1A—C2A—H2A119.8C1B—C2B—H2B120.0
C2A—C3A—C4A121.43 (16)C4B—C3B—C2B121.33 (16)
C2A—C3A—H3A119.3C4B—C3B—H3B119.3
C4A—C3A—H3A119.3C2B—C3B—H3B119.3
C5A—C4A—C3A118.65 (16)C3B—C4B—C5B119.29 (16)
C5A—C4A—H4A120.7C3B—C4B—H4B120.4
C3A—C4A—H4A120.7C5B—C4B—H4B120.4
O1A—C5A—C4A117.34 (16)O1B—C5B—C4B117.89 (16)
O1A—C5A—C6A122.42 (16)O1B—C5B—C6B122.35 (16)
C4A—C5A—C6A120.22 (15)C4B—C5B—C6B119.73 (16)
C5A—C6A—C1A121.27 (15)C1B—C6B—C5B121.34 (15)
C5A—C6A—H6A119.4C1B—C6B—H6B119.3
C1A—C6A—H6A119.4C5B—C6B—H6B119.3
C1A—C7A—C8A113.03 (14)C1B—C7B—C8B111.32 (14)
C1A—C7A—C10A113.87 (13)C1B—C7B—C10B114.01 (12)
C8A—C7A—C10A111.80 (13)C8B—C7B—C10B113.89 (13)
C1A—C7A—H7A105.8C1B—C7B—H7B105.6
C8A—C7A—H7A105.8C8B—C7B—H7B105.6
C10A—C7A—H7A105.8C10B—C7B—H7B105.6
C9A—C8A—C7A112.48 (16)C9B—C8B—C7B114.95 (16)
C9A—C8A—H8A109.1C9B—C8B—H8C108.5
C7A—C8A—H8A109.1C7B—C8B—H8C108.5
C9A—C8A—H8B109.1C9B—C8B—H8D108.5
C7A—C8A—H8B109.1C7B—C8B—H8D108.5
H8A—C8A—H8B107.8H8C—C8B—H8D107.5
C8A—C9A—H9A109.5C8B—C9B—H9D109.5
C8A—C9A—H9B109.5C8B—C9B—H9E109.5
H9A—C9A—H9B109.5H9D—C9B—H9E109.5
C8A—C9A—H9C109.5C8B—C9B—H9F109.5
H9A—C9A—H9C109.5H9D—C9B—H9F109.5
H9B—C9A—H9C109.5H9E—C9B—H9F109.5
C12A—C10A—C11A112.23 (14)C12B—C10B—C11B112.00 (13)
C12A—C10A—C7A111.60 (13)C12B—C10B—C7B110.58 (13)
C11A—C10A—C7A111.82 (13)C11B—C10B—C7B112.05 (13)
C12A—C10A—H10A106.9C12B—C10B—H10B107.3
C11A—C10A—H10A106.9C11B—C10B—H10B107.3
C7A—C10A—H10A106.9C7B—C10B—H10B107.3
C10A—C11A—H11A109.5C10B—C11B—H11D109.5
C10A—C11A—H11B109.5C10B—C11B—H11E109.5
H11A—C11A—H11B109.5H11D—C11B—H11E109.5
C10A—C11A—H11C109.5C10B—C11B—H11F109.5
H11A—C11A—H11C109.5H11D—C11B—H11F109.5
H11B—C11A—H11C109.5H11E—C11B—H11F109.5
N1A—C12A—C10A114.86 (13)N1B—C12B—C10B115.19 (12)
N1A—C12A—H12A108.6N1B—C12B—H12C108.5
C10A—C12A—H12A108.6C10B—C12B—H12C108.5
N1A—C12A—H12B108.6N1B—C12B—H12D108.5
C10A—C12A—H12B108.6C10B—C12B—H12D108.5
H12A—C12A—H12B107.5H12C—C12B—H12D107.5
N1A—C13A—H13A109.5N1B—C13B—H13D109.5
N1A—C13A—H13B109.5N1B—C13B—H13E109.5
H13A—C13A—H13B109.5H13D—C13B—H13E109.5
N1A—C13A—H13C109.5N1B—C13B—H13F109.5
H13A—C13A—H13C109.5H13D—C13B—H13F109.5
H13B—C13A—H13C109.5H13E—C13B—H13F109.5
N1A—C14A—H14A109.5N1B—C14B—H14D109.5
N1A—C14A—H14B109.5N1B—C14B—H14E109.5
H14A—C14A—H14B109.5H14D—C14B—H14E109.5
N1A—C14A—H14C109.5N1B—C14B—H14F109.5
H14A—C14A—H14C109.5H14D—C14B—H14F109.5
H14B—C14A—H14C109.5H14E—C14B—H14F109.5
C14A—N1A—C13A111.43 (17)C14B—N1B—C13B111.16 (14)
C14A—N1A—C12A113.74 (15)C14B—N1B—C12B113.15 (13)
C13A—N1A—C12A109.67 (15)C13B—N1B—C12B109.68 (13)
C14A—N1A—H1N107.7 (12)C14B—N1B—H2N105.5 (13)
C13A—N1A—H1N105.4 (11)C13B—N1B—H2N108.0 (13)
C12A—N1A—H1N108.5 (11)C12B—N1B—H2N109.1 (12)
C5A—O1A—H1O112.0 (17)C5B—O1B—H2O111.0 (19)
C6A—C1A—C2A—C3A0.0 (2)C6B—C1B—C2B—C3B0.4 (2)
C7A—C1A—C2A—C3A179.81 (14)C7B—C1B—C2B—C3B178.55 (15)
C1A—C2A—C3A—C4A0.1 (2)C1B—C2B—C3B—C4B1.0 (3)
C2A—C3A—C4A—C5A0.5 (2)C2B—C3B—C4B—C5B1.0 (3)
C3A—C4A—C5A—O1A179.14 (15)C3B—C4B—C5B—O1B178.50 (17)
C3A—C4A—C5A—C6A0.7 (2)C3B—C4B—C5B—C6B0.3 (3)
O1A—C5A—C6A—C1A178.96 (15)C2B—C1B—C6B—C5B0.2 (2)
C4A—C5A—C6A—C1A0.6 (2)C7B—C1B—C6B—C5B177.96 (14)
C2A—C1A—C6A—C5A0.2 (2)O1B—C5B—C6B—C1B177.82 (16)
C7A—C1A—C6A—C5A179.95 (14)C4B—C5B—C6B—C1B0.3 (2)
C6A—C1A—C7A—C8A134.29 (15)C6B—C1B—C7B—C8B136.29 (15)
C2A—C1A—C7A—C8A45.5 (2)C2B—C1B—C7B—C8B41.82 (19)
C6A—C1A—C7A—C10A96.70 (17)C6B—C1B—C7B—C10B93.19 (17)
C2A—C1A—C7A—C10A83.48 (18)C2B—C1B—C7B—C10B88.71 (19)
C1A—C7A—C8A—C9A63.8 (2)C1B—C7B—C8B—C9B170.38 (16)
C10A—C7A—C8A—C9A166.17 (16)C10B—C7B—C8B—C9B59.0 (2)
C1A—C7A—C10A—C12A63.21 (17)C1B—C7B—C10B—C12B65.15 (17)
C8A—C7A—C10A—C12A66.42 (18)C8B—C7B—C10B—C12B64.09 (17)
C1A—C7A—C10A—C11A63.43 (19)C1B—C7B—C10B—C11B60.57 (18)
C8A—C7A—C10A—C11A166.94 (15)C8B—C7B—C10B—C11B170.19 (14)
C11A—C10A—C12A—N1A61.72 (19)C11B—C10B—C12B—N1B57.16 (19)
C7A—C10A—C12A—N1A171.87 (13)C7B—C10B—C12B—N1B177.09 (13)
C10A—C12A—N1A—C14A54.2 (2)C10B—C12B—N1B—C14B52.66 (19)
C10A—C12A—N1A—C13A179.73 (16)C10B—C12B—N1B—C13B177.40 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1N···Cl1Bi0.875 (19)2.23 (2)3.0569 (17)157 (2)
O1A—H1O···Cl1A0.83 (3)2.24 (3)3.0584 (17)168 (2)
N1B—H2N···Cl1A0.90 (2)2.19 (2)3.0506 (15)158 (2)
O1B—H2O···Cl1B0.79 (3)2.30 (3)3.0667 (17)164 (2)
Symmetry code: (i) x1, y, z.
(II) (2S,3S)-3-(3-hydroxyphenyl)- N,N,2-trimethylpentan-1-aminium chloride top
Crystal data top
C14H24NO+·ClF(000) = 560
Mr = 257.79Dx = 1.171 Mg m3
Monoclinic, P21Melting point: 480 K
Hall symbol: P 2ybMo Kα radiation, λ = 0.71073 Å
a = 7.160 (3) ÅCell parameters from 6730 reflections
b = 11.688 (5) Åθ = 2.3–26.0°
c = 17.526 (8) ŵ = 0.25 mm1
β = 94.570 (7)°T = 294 K
V = 1462.0 (11) Å3Needle, colourless
Z = 40.15 × 0.12 × 0.06 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
5139 independent reflections
Radiation source: fine-focus sealed tube4883 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.021
ω scansθmax = 25.0°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 88
Tmin = 0.963, Tmax = 0.986k = 1313
13998 measured reflectionsl = 2020
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H 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 reflectionsΔρmax = 0.14 e Å3
331 parametersΔρmin = 0.10 e Å3
1 restraintAbsolute structure: Flack & Bernardinelli (2000), with 2431 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (4)
Crystal data top
C14H24NO+·ClV = 1462.0 (11) Å3
Mr = 257.79Z = 4
Monoclinic, P21Mo Kα radiation
a = 7.160 (3) ŵ = 0.25 mm1
b = 11.688 (5) ÅT = 294 K
c = 17.526 (8) Å0.15 × 0.12 × 0.06 mm
β = 94.570 (7)°
Data collection top
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 = 0.986Rint = 0.021
13998 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.075Δρmax = 0.14 e Å3
S = 1.06Δρmin = 0.10 e Å3
5139 reflectionsAbsolute structure: Flack & Bernardinelli (2000), with 2431 Friedel pairs
331 parametersAbsolute structure parameter: 0.02 (4)
1 restraint
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1A0.7769 (2)0.46893 (15)0.22428 (10)0.0395 (4)
C2A0.8344 (3)0.57641 (16)0.20069 (11)0.0449 (4)
H2A0.79510.60310.15210.054*
C3A0.9493 (3)0.64304 (16)0.24915 (11)0.0489 (5)
H3A0.98640.71450.23260.059*
C4A1.0108 (3)0.60649 (18)0.32172 (12)0.0501 (5)
H4A1.08770.65270.35400.060*
C5A0.9557 (3)0.49968 (18)0.34556 (10)0.0477 (5)
C6A0.8395 (3)0.43246 (17)0.29711 (10)0.0439 (4)
H6A0.80250.36110.31390.053*
C7A0.6493 (2)0.39218 (16)0.17290 (10)0.0417 (4)
H7A0.59570.33690.20710.050*
C8A0.4820 (3)0.45647 (19)0.13298 (12)0.0536 (5)
H8A0.52820.51890.10320.064*
H8B0.41250.40490.09790.064*
C9A0.3511 (3)0.5042 (2)0.18914 (15)0.0697 (7)
H9A0.41750.55830.22240.105*
H9B0.30570.44290.21910.105*
H9C0.24720.54160.16150.105*
C10A0.7538 (3)0.32029 (16)0.11544 (10)0.0417 (4)
H10A0.65900.27470.08570.050*
C11A0.8907 (3)0.23620 (19)0.15597 (12)0.0587 (5)
H11A0.99120.27760.18300.088*
H11B0.94050.18670.11890.088*
H11C0.82670.19130.19160.088*
C12A0.8466 (3)0.39528 (16)0.05926 (11)0.0464 (4)
H12A0.75490.44960.03740.056*
H12B0.94560.43860.08700.056*
C13A1.0150 (4)0.4161 (2)0.05637 (15)0.0765 (7)
H13A0.92220.47050.07540.115*
H13B1.06240.37600.09850.115*
H13C1.11590.45550.02820.115*
C14A0.7936 (4)0.2570 (3)0.04862 (14)0.0787 (8)
H14A0.68660.30090.06780.118*
H14B0.75420.19740.01580.118*
H14C0.85220.22360.09070.118*
N1A0.9286 (2)0.33246 (15)0.00489 (10)0.0485 (4)
H1N1.020 (3)0.287 (2)0.0139 (11)0.049 (5)*
O1A1.0170 (2)0.46626 (17)0.41803 (9)0.0685 (5)
H1O0.960 (4)0.412 (3)0.4334 (15)0.080 (9)*
C1B0.3051 (2)0.01273 (16)0.26777 (10)0.0419 (4)
C2B0.3791 (3)0.11668 (18)0.29481 (12)0.0493 (5)
H2B0.34040.14790.33980.059*
C3B0.5099 (3)0.17357 (17)0.25496 (12)0.0549 (5)
H3B0.55950.24240.27390.066*
C4B0.5684 (3)0.13031 (19)0.18768 (12)0.0551 (5)
H4B0.65570.16990.16130.066*
C5B0.4962 (3)0.02755 (18)0.15989 (11)0.0493 (5)
C6B0.3660 (3)0.03083 (17)0.20013 (11)0.0459 (4)
H6B0.31880.10040.18150.055*
C7B0.1570 (2)0.05200 (16)0.30845 (10)0.0425 (4)
H7B0.09150.10000.26900.051*
C8B0.0075 (3)0.02905 (18)0.33563 (12)0.0523 (5)
H8C0.03490.07880.29340.063*
H8D0.06520.07700.37610.063*
C9B0.1609 (3)0.0287 (2)0.36476 (16)0.0746 (7)
H9D0.21050.08350.32770.112*
H9E0.12470.06690.41210.112*
H9F0.25480.02760.37300.112*
C10B0.2388 (2)0.13632 (16)0.37091 (10)0.0408 (4)
H10B0.13260.17500.39180.049*
C11B0.3599 (3)0.22841 (18)0.33827 (12)0.0573 (5)
H11D0.46790.19370.31880.086*
H11E0.39940.28200.37780.086*
H11F0.28870.26770.29760.086*
C12B0.3427 (3)0.07153 (16)0.43648 (10)0.0438 (4)
H12C0.25820.01540.45560.053*
H12D0.44570.03020.41650.053*
C13B0.5104 (3)0.0693 (2)0.56374 (13)0.0627 (6)
H13D0.42080.01510.57990.094*
H13E0.55540.11580.60650.094*
H13F0.61360.02920.54430.094*
C14B0.2762 (3)0.2194 (2)0.53298 (13)0.0652 (6)
H14D0.32970.25790.57790.098*
H14E0.17130.17410.54590.098*
H14F0.23490.27490.49490.098*
N1B0.4194 (2)0.14384 (15)0.50231 (9)0.0440 (4)
H2N0.510 (3)0.190 (2)0.4860 (12)0.063 (6)*
O1B0.5535 (2)0.01155 (17)0.09237 (9)0.0694 (5)
H2O0.494 (4)0.065 (3)0.0774 (15)0.077 (9)*
Cl1A0.77045 (7)0.28837 (4)0.48961 (3)0.05532 (14)
Cl1B0.28374 (7)0.18675 (4)0.01351 (3)0.05592 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.0361 (9)0.0411 (10)0.0422 (10)0.0050 (8)0.0090 (7)0.0017 (8)
C2A0.0477 (11)0.0426 (10)0.0451 (10)0.0060 (8)0.0070 (8)0.0004 (8)
C3A0.0498 (11)0.0400 (10)0.0583 (12)0.0014 (9)0.0136 (9)0.0042 (9)
C4A0.0420 (10)0.0552 (13)0.0539 (12)0.0090 (9)0.0094 (9)0.0137 (9)
C5A0.0426 (10)0.0613 (13)0.0395 (10)0.0037 (9)0.0054 (8)0.0021 (9)
C6A0.0423 (10)0.0477 (11)0.0421 (10)0.0051 (8)0.0063 (8)0.0002 (8)
C7A0.0406 (9)0.0442 (10)0.0403 (9)0.0000 (8)0.0036 (7)0.0018 (8)
C8A0.0418 (10)0.0585 (13)0.0598 (12)0.0054 (9)0.0003 (9)0.0047 (10)
C9A0.0487 (12)0.0709 (15)0.0912 (18)0.0131 (11)0.0154 (12)0.0015 (13)
C10A0.0406 (9)0.0391 (10)0.0446 (10)0.0027 (7)0.0019 (8)0.0027 (8)
C11A0.0681 (14)0.0516 (12)0.0561 (12)0.0165 (10)0.0034 (10)0.0044 (10)
C12A0.0498 (11)0.0401 (10)0.0503 (11)0.0075 (8)0.0100 (9)0.0010 (9)
C13A0.0830 (17)0.0794 (17)0.0721 (15)0.0202 (14)0.0371 (13)0.0211 (13)
C14A0.0773 (16)0.101 (2)0.0568 (14)0.0000 (15)0.0019 (12)0.0231 (14)
N1A0.0488 (9)0.0515 (10)0.0457 (9)0.0125 (8)0.0061 (8)0.0006 (8)
O1A0.0684 (10)0.0877 (13)0.0470 (9)0.0250 (10)0.0093 (7)0.0089 (8)
C1B0.0368 (9)0.0460 (10)0.0417 (10)0.0014 (8)0.0042 (8)0.0064 (8)
C2B0.0464 (10)0.0507 (11)0.0497 (11)0.0031 (9)0.0020 (8)0.0030 (9)
C3B0.0535 (12)0.0480 (12)0.0625 (13)0.0127 (9)0.0004 (10)0.0020 (10)
C4B0.0491 (11)0.0586 (13)0.0577 (12)0.0153 (10)0.0055 (9)0.0082 (10)
C5B0.0447 (10)0.0589 (13)0.0440 (11)0.0052 (9)0.0023 (8)0.0026 (9)
C6B0.0437 (10)0.0465 (11)0.0461 (10)0.0075 (9)0.0047 (8)0.0013 (9)
C7B0.0372 (9)0.0473 (11)0.0419 (10)0.0080 (8)0.0039 (8)0.0036 (8)
C8B0.0369 (10)0.0562 (12)0.0630 (13)0.0024 (9)0.0011 (9)0.0100 (10)
C9B0.0519 (13)0.0749 (16)0.0990 (19)0.0044 (12)0.0187 (12)0.0179 (14)
C10B0.0373 (9)0.0405 (10)0.0446 (10)0.0046 (8)0.0030 (7)0.0012 (8)
C11B0.0698 (14)0.0474 (11)0.0537 (12)0.0082 (10)0.0009 (10)0.0073 (9)
C12B0.0444 (10)0.0408 (10)0.0457 (10)0.0027 (8)0.0012 (8)0.0007 (8)
C13B0.0614 (13)0.0710 (15)0.0529 (12)0.0112 (11)0.0127 (10)0.0125 (11)
C14B0.0617 (13)0.0812 (17)0.0532 (12)0.0083 (12)0.0080 (11)0.0157 (11)
N1B0.0393 (8)0.0494 (10)0.0431 (9)0.0058 (7)0.0013 (7)0.0034 (7)
O1B0.0693 (11)0.0804 (12)0.0608 (10)0.0267 (10)0.0200 (8)0.0105 (9)
Cl1A0.0519 (3)0.0465 (3)0.0673 (3)0.0098 (2)0.0030 (2)0.0033 (2)
Cl1B0.0513 (3)0.0491 (3)0.0674 (3)0.0085 (2)0.0047 (2)0.0039 (2)
Geometric parameters (Å, º) top
C1A—C6A1.386 (3)C1B—C6B1.392 (3)
C1A—C2A1.395 (3)C1B—C2B1.393 (3)
C1A—C7A1.523 (3)C1B—C7B1.525 (2)
C2A—C3A1.376 (3)C2B—C3B1.382 (3)
C2A—H2A0.9300C2B—H2B0.9300
C3A—C4A1.380 (3)C3B—C4B1.379 (3)
C3A—H3A0.9300C3B—H3B0.9300
C4A—C5A1.384 (3)C4B—C5B1.381 (3)
C4A—H4A0.9300C4B—H4B0.9300
C5A—O1A1.367 (2)C5B—O1B1.362 (3)
C5A—C6A1.385 (3)C5B—C6B1.391 (3)
C6A—H6A0.9300C6B—H6B0.9300
C7A—C8A1.534 (3)C7B—C8B1.533 (3)
C7A—C10A1.549 (3)C7B—C10B1.553 (3)
C7A—H7A0.9800C7B—H7B0.9800
C8A—C9A1.519 (3)C8B—C9B1.506 (3)
C8A—H8A0.9700C8B—H8C0.9700
C8A—H8B0.9700C8B—H8D0.9700
C9A—H9A0.9600C9B—H9D0.9600
C9A—H9B0.9600C9B—H9E0.9600
C9A—H9C0.9600C9B—H9F0.9600
C10A—C12A1.511 (3)C10B—C12B1.520 (3)
C10A—C11A1.523 (3)C10B—C11B1.522 (3)
C10A—H10A0.9800C10B—H10B0.9800
C11A—H11A0.9600C11B—H11D0.9600
C11A—H11B0.9600C11B—H11E0.9600
C11A—H11C0.9600C11B—H11F0.9600
C12A—N1A1.501 (2)C12B—N1B1.499 (2)
C12A—H12A0.9700C12B—H12C0.9700
C12A—H12B0.9700C12B—H12D0.9700
C13A—N1A1.497 (3)C13B—N1B1.493 (3)
C13A—H13A0.9600C13B—H13D0.9600
C13A—H13B0.9600C13B—H13E0.9600
C13A—H13C0.9600C13B—H13F0.9600
C14A—N1A1.477 (3)C14B—N1B1.486 (3)
C14A—H14A0.9600C14B—H14D0.9600
C14A—H14B0.9600C14B—H14E0.9600
C14A—H14C0.9600C14B—H14F0.9600
N1A—H1N0.88 (2)N1B—H2N0.91 (3)
O1A—H1O0.81 (3)O1B—H2O0.79 (3)
C6A—C1A—C2A117.94 (17)C6B—C1B—C2B118.16 (17)
C6A—C1A—C7A119.87 (16)C6B—C1B—C7B119.58 (16)
C2A—C1A—C7A122.19 (16)C2B—C1B—C7B122.24 (17)
C3A—C2A—C1A120.19 (18)C3B—C2B—C1B120.15 (19)
C3A—C2A—H2A119.9C3B—C2B—H2B119.9
C1A—C2A—H2A119.9C1B—C2B—H2B119.9
C2A—C3A—C4A121.66 (19)C4B—C3B—C2B121.33 (19)
C2A—C3A—H3A119.2C4B—C3B—H3B119.3
C4A—C3A—H3A119.2C2B—C3B—H3B119.3
C3A—C4A—C5A118.67 (18)C3B—C4B—C5B119.33 (19)
C3A—C4A—H4A120.7C3B—C4B—H4B120.3
C5A—C4A—H4A120.7C5B—C4B—H4B120.3
O1A—C5A—C4A117.39 (18)O1B—C5B—C4B117.91 (19)
O1A—C5A—C6A122.69 (19)O1B—C5B—C6B122.42 (19)
C4A—C5A—C6A119.90 (18)C4B—C5B—C6B119.66 (19)
C5A—C6A—C1A121.63 (18)C5B—C6B—C1B121.36 (18)
C5A—C6A—H6A119.2C5B—C6B—H6B119.3
C1A—C6A—H6A119.2C1B—C6B—H6B119.3
C1A—C7A—C8A113.00 (16)C1B—C7B—C8B111.54 (16)
C1A—C7A—C10A113.93 (15)C1B—C7B—C10B114.05 (14)
C8A—C7A—C10A111.66 (15)C8B—C7B—C10B113.99 (15)
C1A—C7A—H7A105.8C1B—C7B—H7B105.4
C8A—C7A—H7A105.8C8B—C7B—H7B105.4
C10A—C7A—H7A105.8C10B—C7B—H7B105.4
C9A—C8A—C7A112.59 (18)C9B—C8B—C7B115.22 (19)
C9A—C8A—H8A109.1C9B—C8B—H8C108.5
C7A—C8A—H8A109.1C7B—C8B—H8C108.5
C9A—C8A—H8B109.1C9B—C8B—H8D108.5
C7A—C8A—H8B109.1C7B—C8B—H8D108.5
H8A—C8A—H8B107.8H8C—C8B—H8D107.5
C8A—C9A—H9A109.5C8B—C9B—H9D109.5
C8A—C9A—H9B109.5C8B—C9B—H9E109.5
H9A—C9A—H9B109.5H9D—C9B—H9E109.5
C8A—C9A—H9C109.5C8B—C9B—H9F109.5
H9A—C9A—H9C109.5H9D—C9B—H9F109.5
H9B—C9A—H9C109.5H9E—C9B—H9F109.5
C12A—C10A—C11A112.21 (16)C12B—C10B—C11B112.17 (16)
C12A—C10A—C7A111.66 (15)C12B—C10B—C7B110.56 (15)
C11A—C10A—C7A111.90 (16)C11B—C10B—C7B112.21 (16)
C12A—C10A—H10A106.9C12B—C10B—H10B107.2
C11A—C10A—H10A106.9C11B—C10B—H10B107.2
C7A—C10A—H10A106.9C7B—C10B—H10B107.2
C10A—C11A—H11A109.5C10B—C11B—H11D109.5
C10A—C11A—H11B109.5C10B—C11B—H11E109.5
H11A—C11A—H11B109.5H11D—C11B—H11E109.5
C10A—C11A—H11C109.5C10B—C11B—H11F109.5
H11A—C11A—H11C109.5H11D—C11B—H11F109.5
H11B—C11A—H11C109.5H11E—C11B—H11F109.5
N1A—C12A—C10A115.01 (15)N1B—C12B—C10B115.35 (15)
N1A—C12A—H12A108.5N1B—C12B—H12C108.4
C10A—C12A—H12A108.5C10B—C12B—H12C108.4
N1A—C12A—H12B108.5N1B—C12B—H12D108.4
C10A—C12A—H12B108.5C10B—C12B—H12D108.4
H12A—C12A—H12B107.5H12C—C12B—H12D107.5
N1A—C13A—H13A109.5N1B—C13B—H13D109.5
N1A—C13A—H13B109.5N1B—C13B—H13E109.5
H13A—C13A—H13B109.5H13D—C13B—H13E109.5
N1A—C13A—H13C109.5N1B—C13B—H13F109.5
H13A—C13A—H13C109.5H13D—C13B—H13F109.5
H13B—C13A—H13C109.5H13E—C13B—H13F109.5
N1A—C14A—H14A109.5N1B—C14B—H14D109.5
N1A—C14A—H14B109.5N1B—C14B—H14E109.5
H14A—C14A—H14B109.5H14D—C14B—H14E109.5
N1A—C14A—H14C109.5N1B—C14B—H14F109.5
H14A—C14A—H14C109.5H14D—C14B—H14F109.5
H14B—C14A—H14C109.5H14E—C14B—H14F109.5
C14A—N1A—C13A111.2 (2)C14B—N1B—C13B111.10 (17)
C14A—N1A—C12A113.71 (17)C14B—N1B—C12B113.12 (16)
C13A—N1A—C12A109.69 (17)C13B—N1B—C12B109.77 (16)
C14A—N1A—H1N105.6 (14)C14B—N1B—H2N107.2 (15)
C13A—N1A—H1N106.7 (14)C13B—N1B—H2N106.8 (14)
C12A—N1A—H1N109.6 (13)C12B—N1B—H2N108.5 (14)
C5A—O1A—H1O113 (2)C5B—O1B—H2O111 (2)
C6A—C1A—C2A—C3A0.2 (3)C6B—C1B—C2B—C3B0.2 (3)
C7A—C1A—C2A—C3A179.75 (16)C7B—C1B—C2B—C3B178.48 (18)
C1A—C2A—C3A—C4A0.0 (3)C1B—C2B—C3B—C4B0.8 (3)
C2A—C3A—C4A—C5A0.4 (3)C2B—C3B—C4B—C5B0.6 (3)
C3A—C4A—C5A—O1A179.26 (18)C3B—C4B—C5B—O1B178.5 (2)
C3A—C4A—C5A—C6A0.7 (3)C3B—C4B—C5B—C6B0.1 (3)
O1A—C5A—C6A—C1A179.01 (17)O1B—C5B—C6B—C1B177.87 (19)
C4A—C5A—C6A—C1A0.5 (3)C4B—C5B—C6B—C1B0.7 (3)
C2A—C1A—C6A—C5A0.1 (3)C2B—C1B—C6B—C5B0.5 (3)
C7A—C1A—C6A—C5A179.97 (17)C7B—C1B—C6B—C5B177.79 (17)
C6A—C1A—C7A—C8A134.47 (18)C6B—C1B—C7B—C8B136.15 (18)
C2A—C1A—C7A—C8A45.5 (2)C2B—C1B—C7B—C8B42.1 (2)
C6A—C1A—C7A—C10A96.69 (19)C6B—C1B—C7B—C10B92.95 (19)
C2A—C1A—C7A—C10A83.3 (2)C2B—C1B—C7B—C10B88.8 (2)
C1A—C7A—C8A—C9A63.6 (2)C1B—C7B—C8B—C9B170.38 (18)
C10A—C7A—C8A—C9A166.36 (18)C10B—C7B—C8B—C9B58.7 (2)
C1A—C7A—C10A—C12A63.4 (2)C1B—C7B—C10B—C12B65.6 (2)
C8A—C7A—C10A—C12A66.1 (2)C8B—C7B—C10B—C12B64.1 (2)
C1A—C7A—C10A—C11A63.3 (2)C1B—C7B—C10B—C11B60.5 (2)
C8A—C7A—C10A—C11A167.15 (17)C8B—C7B—C10B—C11B169.85 (16)
C11A—C10A—C12A—N1A61.4 (2)C11B—C10B—C12B—N1B57.0 (2)
C7A—C10A—C12A—N1A172.03 (15)C7B—C10B—C12B—N1B176.92 (15)
C10A—C12A—N1A—C14A54.5 (2)C10B—C12B—N1B—C14B52.9 (2)
C10A—C12A—N1A—C13A179.75 (18)C10B—C12B—N1B—C13B177.63 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1A—H1O···Cl1A0.81 (3)2.26 (3)3.060 (2)169 (3)
N1A—H1N···Cl1Bi0.88 (2)2.23 (2)3.056 (2)156.5 (18)
N1B—H2N···Cl1A0.91 (3)2.19 (3)3.051 (2)158.9 (19)
O1B—H2O···Cl1B0.79 (3)2.30 (3)3.067 (2)166 (3)
Symmetry code: (i) x+1, y, z.
(III) (2R,3S)-3-(3-hydroxyphenyl)- N,N,2-trimethylpentan-1-aminium chloride top
Crystal data top
C14H24NO+·ClDx = 1.143 Mg m3
Mr = 257.79Melting point: 477 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 7888 reflections
a = 8.8218 (6) Åθ = 2.2–27.3°
b = 12.1304 (8) ŵ = 0.24 mm1
c = 14.0031 (9) ÅT = 294 K
V = 1498.50 (17) Å3Block, colourless
Z = 40.17 × 0.14 × 0.09 mm
F(000) = 560
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2653 independent reflections
Radiation source: fine-focus sealed tube2540 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.022
ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1010
Tmin = 0.958, Tmax = 0.975k = 1414
14552 measured reflectionsl = 1616
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H 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 reflectionsΔρmax = 0.20 e Å3
166 parametersΔρmin = 0.13 e Å3
0 restraintsAbsolute structure: Flack & Bernardinelli (2000), with 1113 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.02 (7)
Crystal data top
C14H24NO+·ClV = 1498.50 (17) Å3
Mr = 257.79Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.8218 (6) ŵ = 0.24 mm1
b = 12.1304 (8) ÅT = 294 K
c = 14.0031 (9) Å0.17 × 0.14 × 0.09 mm
Data collection top
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 = 0.975Rint = 0.022
14552 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.081Δρmax = 0.20 e Å3
S = 1.03Δρmin = 0.13 e Å3
2653 reflectionsAbsolute structure: Flack & Bernardinelli (2000), with 1113 Friedel pairs
166 parametersAbsolute structure parameter: 0.02 (7)
0 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.06780 (19)0.59630 (13)0.05664 (12)0.0434 (4)
C20.1656 (2)0.50805 (15)0.06853 (14)0.0499 (4)
H20.15400.44520.03120.060*
C30.2810 (2)0.51297 (17)0.13582 (14)0.0556 (5)
H30.34660.45350.14290.067*
C40.2992 (2)0.60582 (16)0.19258 (13)0.0511 (4)
H40.37800.60950.23660.061*
C50.1994 (2)0.69241 (14)0.18304 (12)0.0463 (4)
C60.0850 (2)0.68787 (13)0.11503 (12)0.0444 (4)
H60.01890.74710.10850.053*
C70.0534 (2)0.59329 (13)0.01990 (12)0.0450 (4)
H70.10660.66420.01870.054*
C80.0207 (2)0.58101 (17)0.11877 (14)0.0579 (5)
H8A0.07580.51190.12110.069*
H8B0.05810.57830.16710.069*
C90.1284 (3)0.6746 (2)0.14176 (17)0.0780 (7)
H9A0.21210.67310.09800.117*
H9B0.07590.74360.13600.117*
H9C0.16530.66630.20580.117*
C100.1712 (2)0.50158 (15)0.00155 (12)0.0449 (4)
H100.12330.42960.00850.054*
C110.2266 (3)0.50847 (19)0.10535 (16)0.0701 (6)
H11A0.30810.45720.11480.105*
H11B0.26180.58180.11840.105*
H11C0.14470.49070.14770.105*
C120.3057 (2)0.51131 (17)0.06455 (18)0.0672 (6)
H12A0.37290.56810.04030.081*
H12B0.27030.53480.12690.081*
C130.3254 (3)0.3263 (2)0.14156 (17)0.0790 (7)
H13A0.31640.35860.20390.118*
H13B0.38830.26180.14510.118*
H13C0.22670.30610.11860.118*
C140.5508 (2)0.4316 (2)0.10597 (17)0.0696 (6)
H14A0.60960.36500.10650.104*
H14B0.54960.46300.16890.104*
H14C0.59510.48320.06210.104*
N10.39406 (16)0.40635 (12)0.07588 (11)0.0471 (3)
H1N0.397 (2)0.3717 (16)0.0139 (14)0.050 (5)*
O10.20577 (19)0.78479 (11)0.23829 (10)0.0637 (4)
H1O0.268 (3)0.778 (2)0.2782 (19)0.076 (8)*
Cl10.43172 (5)0.25035 (4)0.09402 (3)0.05870 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0447 (9)0.0427 (8)0.0428 (8)0.0053 (8)0.0013 (7)0.0018 (7)
C20.0532 (10)0.0457 (9)0.0509 (10)0.0035 (8)0.0037 (8)0.0077 (8)
C30.0545 (11)0.0576 (11)0.0547 (10)0.0134 (9)0.0056 (9)0.0008 (9)
C40.0508 (10)0.0608 (10)0.0416 (9)0.0027 (9)0.0091 (8)0.0037 (8)
C50.0555 (10)0.0453 (9)0.0380 (8)0.0101 (8)0.0019 (8)0.0029 (7)
C60.0481 (9)0.0386 (8)0.0465 (9)0.0015 (7)0.0027 (8)0.0025 (7)
C70.0481 (9)0.0376 (8)0.0495 (9)0.0031 (8)0.0072 (8)0.0022 (7)
C80.0630 (11)0.0636 (11)0.0471 (10)0.0108 (9)0.0089 (9)0.0019 (9)
C90.0831 (16)0.0864 (16)0.0647 (13)0.0253 (13)0.0025 (12)0.0131 (12)
C100.0477 (9)0.0381 (8)0.0489 (10)0.0019 (7)0.0077 (8)0.0029 (7)
C110.0783 (14)0.0633 (12)0.0688 (13)0.0220 (11)0.0097 (12)0.0071 (11)
C120.0608 (12)0.0555 (11)0.0854 (15)0.0125 (10)0.0265 (12)0.0209 (11)
C130.0827 (16)0.0922 (17)0.0619 (13)0.0181 (14)0.0008 (12)0.0073 (12)
C140.0492 (11)0.0878 (14)0.0718 (14)0.0030 (10)0.0124 (11)0.0050 (12)
N10.0457 (7)0.0538 (8)0.0419 (8)0.0072 (6)0.0086 (6)0.0065 (6)
O10.0855 (11)0.0500 (7)0.0556 (8)0.0057 (7)0.0228 (8)0.0064 (6)
Cl10.0700 (3)0.0532 (2)0.0529 (2)0.0116 (2)0.0140 (2)0.0109 (2)
Geometric parameters (Å, º) top
C1—C21.385 (2)C9—H9C0.9600
C1—C61.388 (2)C10—C121.509 (3)
C1—C71.514 (2)C10—C111.536 (3)
C2—C31.388 (3)C10—H100.9800
C2—H20.9300C11—H11A0.9600
C3—C41.388 (3)C11—H11B0.9600
C3—H30.9300C11—H11C0.9600
C4—C51.377 (3)C12—N11.501 (2)
C4—H40.9300C12—H12A0.9700
C5—O11.363 (2)C12—H12B0.9700
C5—C61.389 (2)C13—N11.468 (3)
C6—H60.9300C13—H13A0.9600
C7—C81.538 (3)C13—H13B0.9600
C7—C101.552 (2)C13—H13C0.9600
C7—H70.9800C14—N11.478 (2)
C8—C91.515 (3)C14—H14A0.9600
C8—H8A0.9700C14—H14B0.9600
C8—H8B0.9700C14—H14C0.9600
C9—H9A0.9600N1—H1N0.97 (2)
C9—H9B0.9600O1—H1O0.79 (3)
C2—C1—C6118.67 (15)C12—C10—C7110.60 (14)
C2—C1—C7120.42 (15)C11—C10—C7110.94 (15)
C6—C1—C7120.90 (15)C12—C10—H10108.7
C1—C2—C3120.34 (17)C11—C10—H10108.7
C1—C2—H2119.8C7—C10—H10108.7
C3—C2—H2119.8C10—C11—H11A109.5
C4—C3—C2120.57 (17)C10—C11—H11B109.5
C4—C3—H3119.7H11A—C11—H11B109.5
C2—C3—H3119.7C10—C11—H11C109.5
C5—C4—C3119.30 (16)H11A—C11—H11C109.5
C5—C4—H4120.4H11B—C11—H11C109.5
C3—C4—H4120.4N1—C12—C10113.99 (15)
O1—C5—C4123.07 (16)N1—C12—H12A108.8
O1—C5—C6116.86 (16)C10—C12—H12A108.8
C4—C5—C6120.07 (16)N1—C12—H12B108.8
C1—C6—C5121.01 (15)C10—C12—H12B108.8
C1—C6—H6119.5H12A—C12—H12B107.6
C5—C6—H6119.5N1—C13—H13A109.5
C1—C7—C8109.87 (15)N1—C13—H13B109.5
C1—C7—C10110.68 (13)H13A—C13—H13B109.5
C8—C7—C10112.91 (14)N1—C13—H13C109.5
C1—C7—H7107.7H13A—C13—H13C109.5
C8—C7—H7107.7H13B—C13—H13C109.5
C10—C7—H7107.7N1—C14—H14A109.5
C9—C8—C7112.65 (17)N1—C14—H14B109.5
C9—C8—H8A109.1H14A—C14—H14B109.5
C7—C8—H8A109.1N1—C14—H14C109.5
C9—C8—H8B109.1H14A—C14—H14C109.5
C7—C8—H8B109.1H14B—C14—H14C109.5
H8A—C8—H8B107.8C13—N1—C14110.14 (17)
C8—C9—H9A109.5C13—N1—C12114.40 (18)
C8—C9—H9B109.5C14—N1—C12109.89 (16)
H9A—C9—H9B109.5C13—N1—H1N106.7 (11)
C8—C9—H9C109.5C14—N1—H1N108.7 (11)
H9A—C9—H9C109.5C12—N1—H1N106.8 (11)
H9B—C9—H9C109.5C5—O1—H1O109.9 (18)
C12—C10—C11109.03 (18)
C6—C1—C2—C31.8 (3)C2—C1—C7—C1065.2 (2)
C7—C1—C2—C3177.07 (16)C6—C1—C7—C10115.97 (17)
C1—C2—C3—C40.5 (3)C1—C7—C8—C959.4 (2)
C2—C3—C4—C51.4 (3)C10—C7—C8—C9176.47 (17)
C3—C4—C5—O1177.52 (18)C1—C7—C10—C12170.15 (16)
C3—C4—C5—C62.1 (3)C8—C7—C10—C1266.2 (2)
C2—C1—C6—C51.1 (3)C1—C7—C10—C1149.0 (2)
C7—C1—C6—C5177.72 (15)C8—C7—C10—C11172.66 (16)
O1—C5—C6—C1178.83 (16)C11—C10—C12—N179.9 (2)
C4—C5—C6—C10.8 (3)C7—C10—C12—N1157.87 (17)
C2—C1—C7—C860.2 (2)C10—C12—N1—C1378.9 (2)
C6—C1—C7—C8118.66 (18)C10—C12—N1—C14156.57 (19)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl10.97 (2)2.13 (2)3.0580 (15)160.5 (16)
O1—H1O···Cl1i0.79 (3)2.32 (3)3.1083 (16)174 (2)
C11—H11A···Cl10.962.753.620 (2)151
C13—H13C···Cl1ii0.962.713.657 (3)168
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x1/2, y+1/2, z.
(IV) (2S,3R)-3-(3-hydroxyphenyl)- N,N,2-trimethylpentan-1-aminium chloride top
Crystal data top
C14H24NO+·ClDx = 1.148 Mg m3
Mr = 257.79Melting point: 478 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 9741 reflections
a = 8.8101 (6) Åθ = 2.2–27.7°
b = 12.1094 (8) ŵ = 0.24 mm1
c = 13.9784 (9) ÅT = 294 K
V = 1491.29 (17) Å3Block, colourless
Z = 40.21 × 0.17 × 0.12 mm
F(000) = 560
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
2630 independent reflections
Radiation source: fine-focus sealed tube2548 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 1010
Tmin = 0.948, Tmax = 0.969k = 1414
14415 measured reflectionsl = 1616
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H 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 reflectionsΔρmax = 0.22 e Å3
166 parametersΔρmin = 0.13 e Å3
0 restraintsAbsolute structure: Flack & Bernardinelli (2000), with 1104 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.00 (6)
Crystal data top
C14H24NO+·ClV = 1491.29 (17) Å3
Mr = 257.79Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 8.8101 (6) ŵ = 0.24 mm1
b = 12.1094 (8) ÅT = 294 K
c = 13.9784 (9) Å0.21 × 0.17 × 0.12 mm
Data collection top
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 = 0.969Rint = 0.019
14415 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.083Δρmax = 0.22 e Å3
S = 1.05Δρmin = 0.13 e Å3
2630 reflectionsAbsolute structure: Flack & Bernardinelli (2000), with 1104 Friedel pairs
166 parametersAbsolute structure parameter: 0.00 (6)
0 restraints
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C11.06779 (18)0.40372 (13)1.05655 (11)0.0436 (3)
C21.1658 (2)0.49194 (15)1.06865 (13)0.0506 (4)
H21.15430.55501.03140.061*
C31.2809 (2)0.48691 (16)1.13582 (13)0.0560 (4)
H31.34660.54641.14290.067*
C41.2992 (2)0.39420 (15)1.19260 (12)0.0517 (4)
H41.37810.39051.23670.062*
C51.1993 (2)0.30752 (13)1.18298 (12)0.0465 (4)
C61.08491 (19)0.31209 (12)1.11502 (12)0.0445 (4)
H61.01860.25281.10850.053*
C70.9467 (2)0.40666 (13)0.98005 (12)0.0455 (4)
H70.89340.33560.98140.055*
C81.0205 (2)0.41879 (17)0.88136 (13)0.0584 (5)
H8A0.94160.42150.83300.070*
H8B1.07560.48810.87900.070*
C91.1281 (3)0.3254 (2)0.85824 (17)0.0785 (7)
H9A1.21200.32680.90210.118*
H9B1.16520.33380.79410.118*
H9C1.07570.25620.86390.118*
C100.82882 (19)0.49841 (14)1.00152 (11)0.0455 (4)
H100.87670.57050.99140.055*
C110.7734 (3)0.49147 (18)1.10529 (16)0.0706 (6)
H11A0.69130.54251.11460.106*
H11B0.85530.50981.14780.106*
H11C0.73900.41781.11850.106*
C120.6942 (2)0.48848 (17)0.93555 (17)0.0674 (6)
H12A0.72940.46460.87310.081*
H12B0.62670.43190.96010.081*
C130.6747 (3)0.6738 (2)0.85849 (16)0.0796 (7)
H13A0.68470.64120.79620.119*
H13B0.77310.69460.88180.119*
H13C0.61120.73800.85440.119*
C140.4496 (2)0.5685 (2)0.89392 (17)0.0701 (5)
H14A0.39050.63510.89380.105*
H14B0.40550.51640.93760.105*
H14C0.45090.53750.83070.105*
N10.60614 (16)0.59374 (12)0.92404 (10)0.0474 (3)
H1N0.602 (2)0.6281 (15)0.9853 (14)0.049 (5)*
O11.20575 (19)0.21526 (11)1.23837 (10)0.0636 (4)
H1O1.269 (3)0.224 (2)1.280 (2)0.084 (8)*
Cl10.56842 (5)0.74966 (4)1.09407 (3)0.05924 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0450 (8)0.0426 (7)0.0431 (8)0.0049 (7)0.0017 (7)0.0016 (6)
C20.0540 (9)0.0461 (9)0.0518 (10)0.0045 (8)0.0043 (8)0.0070 (8)
C30.0555 (10)0.0581 (10)0.0543 (10)0.0127 (9)0.0047 (8)0.0006 (8)
C40.0508 (9)0.0614 (10)0.0430 (9)0.0030 (8)0.0090 (7)0.0043 (8)
C50.0562 (10)0.0447 (8)0.0384 (8)0.0101 (7)0.0024 (7)0.0030 (7)
C60.0486 (8)0.0383 (7)0.0467 (8)0.0020 (6)0.0022 (7)0.0027 (7)
C70.0489 (8)0.0381 (8)0.0495 (9)0.0027 (7)0.0074 (7)0.0018 (7)
C80.0637 (11)0.0639 (11)0.0475 (9)0.0114 (9)0.0085 (8)0.0010 (8)
C90.0854 (15)0.0859 (15)0.0643 (13)0.0259 (13)0.0024 (12)0.0125 (11)
C100.0487 (9)0.0381 (8)0.0498 (9)0.0024 (7)0.0080 (7)0.0031 (7)
C110.0790 (13)0.0631 (11)0.0698 (13)0.0229 (10)0.0107 (11)0.0070 (10)
C120.0622 (11)0.0559 (10)0.0841 (14)0.0121 (10)0.0268 (11)0.0209 (10)
C130.0838 (15)0.0923 (17)0.0628 (13)0.0168 (14)0.0013 (12)0.0073 (12)
C140.0492 (10)0.0886 (14)0.0724 (13)0.0031 (10)0.0124 (10)0.0043 (12)
N10.0463 (7)0.0545 (8)0.0414 (7)0.0072 (6)0.0082 (6)0.0066 (6)
O10.0851 (10)0.0498 (7)0.0560 (8)0.0052 (7)0.0223 (8)0.0062 (6)
Cl10.0709 (3)0.0537 (2)0.0531 (2)0.0116 (2)0.01407 (19)0.0110 (2)
Geometric parameters (Å, º) top
C1—C21.384 (2)C9—H9C0.9600
C1—C61.386 (2)C10—C121.507 (2)
C1—C71.511 (2)C10—C111.533 (3)
C2—C31.383 (3)C10—H100.9800
C2—H20.9300C11—H11A0.9600
C3—C41.384 (3)C11—H11B0.9600
C3—H30.9300C11—H11C0.9600
C4—C51.377 (3)C12—N11.501 (2)
C4—H40.9300C12—H12A0.9700
C5—O11.360 (2)C12—H12B0.9700
C5—C61.386 (2)C13—N11.464 (3)
C6—H60.9300C13—H13A0.9600
C7—C81.532 (3)C13—H13B0.9600
C7—C101.550 (2)C13—H13C0.9600
C7—H70.9800C14—N11.474 (2)
C8—C91.511 (3)C14—H14A0.9600
C8—H8A0.9700C14—H14B0.9600
C8—H8B0.9700C14—H14C0.9600
C9—H9A0.9600N1—H1N0.95 (2)
C9—H9B0.9600O1—H1O0.81 (3)
C2—C1—C6118.54 (15)C12—C10—C7110.59 (14)
C2—C1—C7120.59 (14)C11—C10—C7110.93 (14)
C6—C1—C7120.86 (15)C12—C10—H10108.8
C3—C2—C1120.42 (16)C11—C10—H10108.8
C3—C2—H2119.8C7—C10—H10108.8
C1—C2—H2119.8C10—C11—H11A109.5
C2—C3—C4120.70 (17)C10—C11—H11B109.5
C2—C3—H3119.6H11A—C11—H11B109.5
C4—C3—H3119.6C10—C11—H11C109.5
C5—C4—C3119.18 (16)H11A—C11—H11C109.5
C5—C4—H4120.4H11B—C11—H11C109.5
C3—C4—H4120.4N1—C12—C10113.87 (14)
O1—C5—C4122.93 (15)N1—C12—H12A108.8
O1—C5—C6116.97 (16)C10—C12—H12A108.8
C4—C5—C6120.10 (15)N1—C12—H12B108.8
C5—C6—C1121.01 (15)C10—C12—H12B108.8
C5—C6—H6119.5H12A—C12—H12B107.7
C1—C6—H6119.5N1—C13—H13A109.5
C1—C7—C8109.85 (14)N1—C13—H13B109.5
C1—C7—C10110.67 (13)H13A—C13—H13B109.5
C8—C7—C10112.95 (14)N1—C13—H13C109.5
C1—C7—H7107.7H13A—C13—H13C109.5
C8—C7—H7107.7H13B—C13—H13C109.5
C10—C7—H7107.7N1—C14—H14A109.5
C9—C8—C7112.78 (16)N1—C14—H14B109.5
C9—C8—H8A109.0H14A—C14—H14B109.5
C7—C8—H8A109.0N1—C14—H14C109.5
C9—C8—H8B109.0H14A—C14—H14C109.5
C7—C8—H8B109.0H14B—C14—H14C109.5
H8A—C8—H8B107.8C13—N1—C14110.15 (17)
C8—C9—H9A109.5C13—N1—C12114.60 (18)
C8—C9—H9B109.5C14—N1—C12109.75 (16)
H9A—C9—H9B109.5C13—N1—H1N106.7 (11)
C8—C9—H9C109.5C14—N1—H1N108.3 (11)
H9A—C9—H9C109.5C12—N1—H1N107.0 (11)
H9B—C9—H9C109.5C5—O1—H1O109.4 (19)
C12—C10—C11108.90 (17)
C6—C1—C2—C31.9 (3)C2—C1—C7—C1065.1 (2)
C7—C1—C2—C3177.07 (16)C6—C1—C7—C10115.94 (17)
C1—C2—C3—C40.6 (3)C1—C7—C8—C959.4 (2)
C2—C3—C4—C51.4 (3)C10—C7—C8—C9176.48 (17)
C3—C4—C5—O1177.47 (17)C1—C7—C10—C12170.03 (15)
C3—C4—C5—C62.1 (3)C8—C7—C10—C1266.3 (2)
O1—C5—C6—C1178.81 (15)C1—C7—C10—C1149.1 (2)
C4—C5—C6—C10.8 (2)C8—C7—C10—C11172.73 (16)
C2—C1—C6—C51.2 (2)C11—C10—C12—N180.2 (2)
C7—C1—C6—C5177.71 (15)C7—C10—C12—N1157.68 (17)
C2—C1—C7—C860.3 (2)C10—C12—N1—C1378.7 (2)
C6—C1—C7—C8118.65 (17)C10—C12—N1—C14156.77 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl10.95 (2)2.14 (2)3.0536 (15)161.0 (16)
O1—H1O···Cl1i0.81 (3)2.29 (3)3.1013 (15)175 (2)
C11—H11A···Cl10.962.753.614 (2)151
C13—H13B···Cl1ii0.962.713.651 (3)167
Symmetry codes: (i) x+2, y1/2, z+5/2; (ii) x+1/2, y+3/2, z+2.

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC14H24NO+·ClC14H24NO+·ClC14H24NO+·ClC14H24NO+·Cl
Mr257.79257.79257.79257.79
Crystal system, space groupMonoclinic, P21Monoclinic, P21Orthorhombic, P212121Orthorhombic, P212121
Temperature (K)294294294294
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), 9090, 94.570 (7), 9090, 90, 9090, 90, 90
V3)1461.1 (5)1462.0 (11)1498.50 (17)1491.29 (17)
Z4444
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.250.250.240.24
Crystal size (mm)0.18 × 0.15 × 0.090.15 × 0.12 × 0.060.17 × 0.14 × 0.090.21 × 0.17 × 0.12
Data collection
DiffractometerBruker 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 correctionMulti-scan
(SADABS; Bruker, 2001)
Multi-scan
(SADABS; Bruker, 2001)
Multi-scan
(SADABS; Bruker, 2001)
Multi-scan
(SADABS; Bruker, 2001)
Tmin, Tmax0.955, 0.9760.963, 0.9860.958, 0.9750.948, 0.969
No. of measured, independent and
observed [I > 2σ(I)] reflections
14096, 5135, 4972 13998, 5139, 4883 14552, 2653, 2540 14415, 2630, 2548
Rint0.0220.0210.0220.019
(sin θ/λ)max1)0.5950.5950.5950.595
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 reflections5135513926532630
No. of parameters331331166166
No. of restraints1100
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.14, 0.120.14, 0.100.20, 0.130.22, 0.13
Absolute structureFlack & Bernardinelli (2000), with 2430 Friedel pairsFlack & Bernardinelli (2000), with 2431 Friedel pairsFlack & Bernardinelli (2000), with 1113 Friedel pairsFlack & Bernardinelli (2000), with 1104 Friedel pairs
Absolute structure parameter0.03 (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).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1A—H1N···Cl1Bi0.875 (19)2.23 (2)3.0569 (17)157 (2)
O1A—H1O···Cl1A0.83 (3)2.24 (3)3.0584 (17)168 (2)
N1B—H2N···Cl1A0.90 (2)2.19 (2)3.0506 (15)158 (2)
O1B—H2O···Cl1B0.79 (3)2.30 (3)3.0667 (17)164 (2)
Symmetry code: (i) x1, y, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1A—H1O···Cl1A0.81 (3)2.26 (3)3.060 (2)169 (3)
N1A—H1N···Cl1Bi0.88 (2)2.23 (2)3.056 (2)156.5 (18)
N1B—H2N···Cl1A0.91 (3)2.19 (3)3.051 (2)158.9 (19)
O1B—H2O···Cl1B0.79 (3)2.30 (3)3.067 (2)166 (3)
Symmetry code: (i) x+1, y, z.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl10.97 (2)2.13 (2)3.0580 (15)160.5 (16)
O1—H1O···Cl1i0.79 (3)2.32 (3)3.1083 (16)174 (2)
C11—H11A···Cl10.962.753.620 (2)150.9
C13—H13C···Cl1ii0.962.713.657 (3)167.7
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x1/2, y+1/2, z.
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Cl10.95 (2)2.14 (2)3.0536 (15)161.0 (16)
O1—H1O···Cl1i0.81 (3)2.29 (3)3.1013 (15)175 (2)
C11—H11A···Cl10.962.753.614 (2)151
C13—H13B···Cl1ii0.962.713.651 (3)167
Symmetry codes: (i) x+2, y1/2, z+5/2; (ii) x+1/2, y+3/2, z+2.
Table 1. Selected geometric parameters (°) for stereoisomers (I)–(IV) top
Parameter(I), cation A(I), cation B(II), cation A(II), cation B(III)(IV)
C7—C8—C9112.48 (16)114.95 (16)112.59 (18)115.22 (19)112.65 (17)112.78 (16)
C8—C7—C10118.80 (13)113.89 (13)111.66 (15)113.99 (15)112.91 (13)112.95 (14)
C1—C7—C8—C963.8 (2)170.38 (16)-63.6 (2)-170.38 (18)-59.4 (2)59.4 (2)
C1—C7—C10—C1263.21 (17)65.15 (17)-63.4 (2)-65.6 (2)170.15 (16)-170.03 (15)
C7—C10—C12—N1171.87 (13)177.09 (13)-172.03 (15)-176.92 (15)157.87 (17)-157.68 (17)
 

Acknowledgements

The authors thank Dr J. S. Yadav, Director, IICT, Hyderabad, for his kind encouragement.

References

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