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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 10| October 2011| Page o2772
https://doi.org/10.1107/S1600536811037093

Bupropion hydro­bromide propanol hemisolvate

Min Liu,a Xiu-Rong Hu,a* Jian-Ming Gub and Gu-Ping Tanga

aChemistry Department, Zhejiang University, Hangzhou, Zhejiang 310028, People's Republic of China, and bCenter of Analysis and Measurement, Zhejiang University, Hangzhou, Zhejiang 310028, People's Republic of China
*Correspondence e-mail: huxiurong@yahoo.com.cn

(Received 8 September 2011; accepted 13 September 2011; online 30 September 2011)

The title compound {systematic name: N-[1-(3-chloro­phen­yl)-1-oxopropan-2-yl]-tert-butanaminium bromide propanol hemisolvate}, C13H19ClNO+·Br−·0.5C3H8O, crystallizes with two independent bupropion hydro­bromide ion pairs and a solvent 1-propanol mol­ecule in the asymmetric unit. In both mol­ecules, the expected proton transfer from HBr to the amino group of the bupropion mol­ecule is observed, and intra- and inter­molecular N—H⋯Br hydrogen-bond inter­actions are formed. These inter­actions link the mol­ecules into hydrogen-bond dimers. The side chains of the two cations have slightly different orientations. The 1-propanol solvent mol­ecule is linked to a bromide ion by an O—H⋯Br hydrogen bond.

Related literature

For applications of bupropion in the medicine field, see: Fryer et al. (1999[Fryer, J. D. & Lukas, R. J. (1999). J. Pharmacol. Exp. Ther. 288, 88-92.]); Stewart et al. (2001[Stewart, J. J., Berkel, H. J., Parish, R. C., Simar, M. R., Syed, A., Bocchini, J. A. Jr, Wilson, J. T. & Manno, J. E. (2001). J. Clin. Pharmacol. 41, 770-778.]); Fang et al. (2000[Fang, Q. K., Han, Z., Grover, P., Kessler, D., Senanayake, C. H. & Wald, S. (2000). Tetrahedron Asymmetry, 11, 3659-3663.]). For the related structures of an ethanol hemi-solvate bupropion derivative and bupropion hydro­chloride, see: Froimowitz et al. (1998[Froimowitz, M. & George, C. (1998). J. Chem. Inf. Comput. Sci. 38, 506-510.]); Maccaroni et al. (2009[Maccaroni, E., Malpezzi, L. & Masciocchi, N. (2009). J. Pharm. Biomed. Anal. 50, 257-261.]).

[Scheme 1]

Experimental

Crystal data

  • C13H19ClNO+·Br−·0.5C3H8O

  • Mr = 350.70

  • Triclinic, P 1

  • a = 7.8614 (4) Å

  • b = 9.4100 (6) Å

  • c = 11.8477 (7) Å

  • α = 85.783 (2)°

  • β = 78.159 (2)°

  • γ = 89.450 (2)°

  • V = 855.46 (9) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 2.56 mm−1

  • T = 296 K

  • 0.46 × 0.28 × 0.14 mm
Data collection

  • Rigaku R-AXIS RAPID diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.361, Tmax = 0.647

  • 8456 measured reflections

  • 6355 independent reflections

  • 4179 reflections with I > 2σ(I)

  • Rint = 0.031
Refinement

  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.138

  • S = 1.00

  • 6355 reflections

  • 354 parameters

  • 77 restraints

  • H-atom parameters constrained

  • Δρmax = 0.74 e Å−3

  • Δρmin = −0.97 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 2490 Friedel pairs

  • Flack parameter: 0.34 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1A—H1A1⋯Br1A 0.90 2.46 3.353 (9) 174
N1A—H1A2⋯Br1Bi 0.90 2.60 3.410 (9) 150
N1B—H1B1⋯Br1Bii 0.90 2.46 3.362 (9) 175
N1B—H1B2⋯Br1Aiii 0.90 2.58 3.383 (9) 149
O21—H21⋯Br1A 0.82 2.73 3.487 (10) 153
Symmetry codes: (i) x-1, y, z; (ii) x, y+1, z; (iii) x+1, y+1, z.

Data collection: PROCESS-AUTO (Rigaku, 2006[Rigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007[Rigaku (2007). CrystalStructure. Rigaku, Tokyo, Japan.]); 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: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811037093/bx2372sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811037093/bx2372Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811037093/bx2372Isup3.cml

checkCIF report


Comment top

The title compound, bupropion hydrobromide, 1-(3-chlorophenyl)-2-[(1,1- dimethylethyl)amino]-1-propanone hydrobromide, belongs to the class of antidepressants known as aminoketones and it is known also with the drug name Aplenzin. It is a second generation antidepressant approved in US and in some European countries, its mechanism of action, both as an antidepressant and as an aids to smoking cessation, is thought to involve nicotinic acetylcholine receptors that are linked to dopamine and norepinephrine release (Fryer et al. 1999 & Stewart et al., 2001). Pure bupropion enantiomers were successfully synthesized but they give rise to a rapid racemization (Fang et al., 2000). In literature, crystal structure of an ethanol hemi-solvate bupropion derivative and bupropion hydrochloride, obtained from single-crystal X-ray analysis and powder diffraction, were reported (Froimowitz et al., 1998 & Maccaroni et al., 2009). Here, we reported crystal structure of bupropion hydrobromide propanol solvate. The asymmetric unit consists of two bupropion cations, two bromide anions and one 1-propanol molecule (Fig.1). Expected proton transfer from HBr to amino group of bupropion is observed, intramolecular and intermolecular hydrogen bond interactions are formed (Table 1).These interactions result in hydrogen-bond dimers in the two polymorphic forms, in which two Br- ions bridge the NH2—NH2 contact (above 4.2 Å), similar to that of BUP hydrochloride (Maccaroni et al., 2009). Solvent molecule 1-propanol is linked to bupropion hydrobromide by intramolecular hydrogen bond O21—H21···Br1A. The side chains of the two molecules have slightly different orientations, as seen by the torsion angles of C6—C5—C7—C8, C5—C7—C8—N1, C7—C8—N1—C10 and O1—C7—C5—C6. Carbonyl groups in the two molecules are not coplanar with phenyl ring plane, atom O1A and O1B deviated from the least-squares plane of phenyl ring (C1A/C6A and C1B/C6B) 0.238Å and 0.139 Å, respectively.

Related literature top

For applications of bupropion in the medicine field, see: Fryer et al. (1999); Stewart et al. (2001); Fang et al. (2000). For the related structures of an ethanol

hemi-solvate bupropion derivative and bupropion hydrochloride, see: Froimowitz et al. (1998); Maccaroni et al. (2009).

Experimental top

The crude product is supplied by Zhejiang Apeloa Pharmaceutical Co.,LTD. It was recrystallized from 1-propanol solution, giving colorless crystals of (1) suitable for X-ray diffraction.

Refinement top

The residual electron density to indicate the presence of a possible H atom on the atoms N1A and N1B, showing that a proton transfer from HBr to amino group of bupropion molecule. These H atoms were placed in calculated positions with N—H = 0.90Å and refined as riding with Uiso(H) = 1.2Ueq(N). All other H atoms were placed in calculated positions with C—H = 0.93–0.99Å and included in the refinement in riding model, with Uiso(H) = 1.2Ueq or 1.5Ueq(carrier atom). Temperature factor of atom O21, C21, C22 and C23 from solvent molecule were restrained with effective standard deviations so that their Uij components approximate to isotropic behavior; however the corresponding isotropic U is free to vary.

Structure description top

The title compound, bupropion hydrobromide, 1-(3-chlorophenyl)-2-[(1,1- dimethylethyl)amino]-1-propanone hydrobromide, belongs to the class of antidepressants known as aminoketones and it is known also with the drug name Aplenzin. It is a second generation antidepressant approved in US and in some European countries, its mechanism of action, both as an antidepressant and as an aids to smoking cessation, is thought to involve nicotinic acetylcholine receptors that are linked to dopamine and norepinephrine release (Fryer et al. 1999 & Stewart et al., 2001). Pure bupropion enantiomers were successfully synthesized but they give rise to a rapid racemization (Fang et al., 2000). In literature, crystal structure of an ethanol hemi-solvate bupropion derivative and bupropion hydrochloride, obtained from single-crystal X-ray analysis and powder diffraction, were reported (Froimowitz et al., 1998 & Maccaroni et al., 2009). Here, we reported crystal structure of bupropion hydrobromide propanol solvate. The asymmetric unit consists of two bupropion cations, two bromide anions and one 1-propanol molecule (Fig.1). Expected proton transfer from HBr to amino group of bupropion is observed, intramolecular and intermolecular hydrogen bond interactions are formed (Table 1).These interactions result in hydrogen-bond dimers in the two polymorphic forms, in which two Br- ions bridge the NH2—NH2 contact (above 4.2 Å), similar to that of BUP hydrochloride (Maccaroni et al., 2009). Solvent molecule 1-propanol is linked to bupropion hydrobromide by intramolecular hydrogen bond O21—H21···Br1A. The side chains of the two molecules have slightly different orientations, as seen by the torsion angles of C6—C5—C7—C8, C5—C7—C8—N1, C7—C8—N1—C10 and O1—C7—C5—C6. Carbonyl groups in the two molecules are not coplanar with phenyl ring plane, atom O1A and O1B deviated from the least-squares plane of phenyl ring (C1A/C6A and C1B/C6B) 0.238Å and 0.139 Å, respectively.

For applications of bupropion in the medicine field, see: Fryer et al. (1999); Stewart et al. (2001); Fang et al. (2000). For the related structures of an ethanol

hemi-solvate bupropion derivative and bupropion hydrochloride, see: Froimowitz et al. (1998); Maccaroni et al. (2009).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound (1) showing atom-labelling scheme and displacement ellipsoids at 40% probability level. H atoms are shown as small circles of arbitrary radii.
N-[1-(3-Chlorophenyl)-1-oxopropan-2-yl]-tert-butanaminium bromide propanol hemisolvate top
Crystal data top
C13H19ClNO+·Br−·0.5C3H8OZ = 2
Mr = 350.70F(000) = 362
Triclinic, P1Dx = 1.361 Mg m−3
Hall symbol: P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.8614 (4) ÅCell parameters from 5965 reflections
b = 9.4100 (6) Åθ = 3.4–27.4°
c = 11.8477 (7) ŵ = 2.56 mm−1
α = 85.783 (2)°T = 296 K
β = 78.159 (2)°Chunk, colorless
γ = 89.450 (2)°0.46 × 0.28 × 0.14 mm
V = 855.46 (9) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer		6355 independent reflections
Radiation source: rolling anode4179 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
Detector resolution: 10.00 pixels mm-1θmax = 27.5°, θmin = 3.4°
ω scansh = −10→8
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		k = −12→12
Tmin = 0.361, Tmax = 0.647l = −15→15
8456 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.043 w = 1/[σ2(Fo2) + (0.0295P)2 + 2.750P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.138(Δ/σ)max = 0.002
S = 1.00Δρmax = 0.74 e Å−3
6355 reflectionsΔρmin = −0.97 e Å−3
354 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
77 restraintsExtinction coefficient: 0.038 (2)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 2490 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.34 (3)
Crystal data top
C13H19ClNO+·Br−·0.5C3H8Oγ = 89.450 (2)°
Mr = 350.70V = 855.46 (9) Å3
Triclinic, P1Z = 2
a = 7.8614 (4) ÅMo Kα radiation
b = 9.4100 (6) ŵ = 2.56 mm−1
c = 11.8477 (7) ÅT = 296 K
α = 85.783 (2)°0.46 × 0.28 × 0.14 mm
β = 78.159 (2)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer		6355 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		4179 reflections with I > 2σ(I)
Tmin = 0.361, Tmax = 0.647Rint = 0.031
8456 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.138Δρmax = 0.74 e Å−3
S = 1.00Δρmin = −0.97 e Å−3
6355 reflectionsAbsolute structure: Flack (1983), 2490 Friedel pairs
354 parametersAbsolute structure parameter: 0.34 (3)
77 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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Br1A0.2817 (5)0.0940 (4)0.4424 (3)0.0574 (4)
Br1B0.8907 (5)0.3667 (4)0.2779 (3)0.0577 (4)
Cl1A0.5787 (10)1.0426 (6)−0.1054 (6)0.096 (2)
Cl1B0.5901 (10)0.4189 (6)0.8270 (6)0.099 (2)
N1A0.2948 (10)0.4307 (9)0.3266 (6)0.044 (3)
H1A10.29160.33810.35200.053*
H1A20.19450.44980.30320.053*
O1A0.2393 (18)0.6111 (14)0.1487 (11)0.073 (4)
C5B0.6396 (10)0.7943 (10)0.6451 (12)0.049 (3)
N1B0.8848 (10)1.0271 (9)0.3887 (6)0.041 (3)
H1B10.88911.11970.36320.049*
H1B20.98701.00660.40910.049*
C7A0.398 (2)0.5823 (16)0.1472 (13)0.055 (4)
C8A0.4388 (13)0.4504 (9)0.2238 (8)0.045 (3)
H8A0.55180.45930.24550.054*
O1B0.9229 (17)0.8444 (14)0.5699 (13)0.080 (4)
C10B0.8749 (8)0.9430 (6)0.2890 (6)0.050 (4)
C6B0.670 (2)0.6656 (11)0.7018 (12)0.053 (4)
H6B0.78410.63440.69580.063*
C13A0.4498 (12)0.4659 (13)0.4839 (11)0.062 (4)
H13A0.55480.46330.42600.092*
H13B0.42460.37230.52140.092*
H13C0.46450.53080.54010.092*
C1A0.6250 (10)0.8758 (9)−0.0469 (12)0.064 (5)
C10A0.2985 (8)0.5161 (6)0.4266 (6)0.051 (4)
C8B0.7476 (14)1.0115 (9)0.4957 (8)0.049 (3)
H8B0.63710.99650.47210.059*
C6A0.500 (2)0.7921 (12)0.0245 (13)0.059 (4)
H6A0.38460.82090.03860.071*
C4B0.4675 (9)0.8365 (11)0.6632 (12)0.069 (4)
H4B0.44100.92250.62680.083*
C4A0.7179 (8)0.6209 (11)0.0595 (12)0.058 (4)
H4A0.74820.53650.09630.070*
C11B0.846 (2)0.7831 (7)0.3252 (16)0.071 (5)
H11A0.84940.73170.25770.106*
H11B0.73540.76900.37660.106*
H11C0.93650.74890.36380.106*
C5A0.5463 (9)0.6643 (11)0.0754 (12)0.048 (3)
C11A0.321 (2)0.6762 (8)0.3895 (15)0.070 (5)
H11D0.43550.69370.34360.105*
H11E0.30540.72950.45690.105*
H11F0.23610.70540.34480.105*
C12B1.0499 (12)0.9757 (14)0.2054 (10)0.061 (4)
H12A1.06841.07690.19480.091*
H12B1.04820.93880.13220.091*
H12C1.14220.93170.23700.091*
C12A0.1247 (13)0.4992 (16)0.5144 (11)0.074 (5)
H12D0.12560.55830.57700.112*
H12E0.10890.40150.54400.112*
H12F0.03100.52740.47700.112*
C13B0.7260 (13)1.0021 (17)0.2329 (11)0.071 (5)
H13D0.74011.10320.21680.107*
H13E0.61680.98200.28490.107*
H13F0.72840.95780.16220.107*
C2B0.3677 (10)0.6293 (11)0.7882 (13)0.070 (5)
H2B0.28030.57650.83810.084*
C7B0.7805 (18)0.8790 (15)0.5713 (13)0.049 (4)
C9A0.433 (2)0.3227 (11)0.1505 (11)0.057 (4)
H9A10.45100.23620.19460.085*
H9A20.52220.33330.08180.085*
H9A30.32140.31890.12950.085*
C1B0.5383 (12)0.5830 (9)0.7665 (12)0.067 (5)
C2A0.7974 (10)0.8344 (13)−0.0634 (13)0.082 (6)
H2A0.88300.8932−0.10900.098*
C3B0.3327 (15)0.7575 (12)0.7325 (11)0.074 (5)
H3B0.21910.79040.74150.088*
C9B0.728 (3)1.1461 (12)0.5637 (12)0.072 (5)
H9B10.63181.13370.62830.108*
H9B20.70721.22690.51400.108*
H9B30.83251.16150.59110.108*
C3A0.8433 (17)0.7064 (12)−0.0127 (14)0.089 (6)
H3A0.95880.6777−0.02710.106*
O210.0850 (16)0.0562 (11)0.7350 (9)0.140 (3)
H210.09560.05840.66460.211*
C230.016 (3)0.3261 (16)0.9379 (14)0.167 (5)
H23A0.09300.36660.98070.250*
H23B−0.09730.31390.98610.250*
H23C0.00980.38880.87130.250*
C210.142 (3)0.1909 (14)0.7667 (10)0.152 (4)
H21A0.08640.27030.73230.183*
H21B0.26730.20190.74260.183*
C220.086 (3)0.1810 (15)0.8990 (10)0.158 (4)
H22A0.18500.15460.93360.190*
H22B−0.00300.10860.92400.190*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br1A0.0472 (9)0.0500 (9)0.0750 (11)−0.0012 (7)−0.0172 (8)0.0093 (8)
Br1B0.0486 (9)0.0505 (9)0.0743 (11)−0.0007 (7)−0.0185 (8)0.0109 (8)
Cl1A0.138 (6)0.060 (3)0.082 (4)−0.010 (3)−0.018 (4)0.024 (3)
Cl1B0.150 (7)0.058 (3)0.088 (4)−0.022 (3)−0.031 (4)0.027 (3)
N1A0.039 (6)0.041 (6)0.053 (7)0.006 (5)−0.013 (5)0.003 (5)
O1A0.058 (8)0.069 (7)0.084 (8)−0.004 (6)−0.011 (6)0.031 (6)
C5B0.047 (7)0.047 (8)0.051 (8)0.005 (6)−0.010 (6)−0.002 (6)
N1B0.033 (6)0.042 (6)0.046 (6)−0.004 (5)−0.006 (5)0.006 (5)
C7A0.059 (9)0.060 (9)0.053 (8)0.017 (7)−0.031 (7)0.000 (7)
C8A0.039 (6)0.044 (7)0.046 (7)0.002 (5)0.001 (5)0.012 (6)
O1B0.041 (7)0.075 (8)0.120 (10)−0.003 (6)−0.021 (7)0.038 (8)
C10B0.050 (9)0.051 (8)0.052 (8)0.010 (7)−0.017 (7)−0.011 (7)
C6B0.073 (11)0.039 (7)0.046 (7)−0.007 (7)−0.017 (7)0.013 (6)
C13A0.077 (11)0.046 (7)0.073 (10)0.017 (7)−0.039 (9)−0.014 (7)
C1A0.080 (13)0.056 (9)0.052 (9)−0.006 (9)−0.004 (9)−0.003 (8)
C10A0.043 (9)0.047 (8)0.059 (8)−0.008 (7)−0.005 (7)−0.002 (7)
C8B0.035 (6)0.048 (7)0.066 (9)0.004 (5)−0.018 (6)0.002 (6)
C6A0.056 (10)0.060 (9)0.057 (8)−0.005 (8)−0.003 (7)−0.005 (7)
C4B0.096 (11)0.045 (7)0.066 (9)−0.025 (7)−0.016 (8)0.010 (6)
C4A0.029 (5)0.070 (8)0.066 (8)0.016 (5)0.007 (5)0.000 (7)
C11B0.078 (12)0.046 (8)0.095 (12)0.025 (7)−0.029 (9)−0.014 (8)
C5A0.050 (7)0.047 (7)0.049 (8)−0.004 (6)−0.021 (6)0.003 (6)
C11A0.066 (10)0.047 (8)0.091 (11)−0.021 (7)−0.002 (9)−0.006 (8)
C12B0.059 (8)0.067 (7)0.045 (6)0.034 (6)0.017 (6)−0.011 (6)
C12A0.070 (9)0.066 (8)0.093 (10)−0.024 (7)−0.034 (8)0.008 (7)
C13B0.048 (9)0.112 (13)0.058 (9)0.005 (8)−0.019 (7)−0.015 (9)
C2B0.089 (13)0.061 (10)0.059 (9)−0.024 (9)−0.011 (8)−0.001 (8)
C7B0.032 (7)0.046 (7)0.061 (8)−0.018 (6)0.004 (6)0.014 (6)
C9A0.064 (9)0.040 (6)0.059 (8)−0.002 (6)0.000 (7)0.011 (6)
C1B0.109 (16)0.043 (8)0.045 (8)−0.021 (9)−0.011 (9)0.013 (7)
C2A0.090 (15)0.069 (11)0.067 (10)−0.020 (10)0.030 (9)0.001 (9)
C3B0.049 (9)0.091 (13)0.074 (11)−0.011 (9)0.008 (8)−0.019 (9)
C9B0.097 (14)0.066 (9)0.048 (7)0.014 (9)−0.004 (8)−0.007 (7)
C3A0.075 (13)0.062 (10)0.107 (14)−0.004 (9)0.028 (10)0.010 (10)
O210.176 (9)0.144 (8)0.092 (6)0.003 (7)−0.009 (6)−0.006 (5)
C230.241 (12)0.138 (11)0.104 (8)0.023 (11)0.000 (9)0.007 (8)
C210.218 (10)0.127 (9)0.100 (7)0.019 (9)−0.009 (7)0.006 (6)
C220.234 (10)0.133 (10)0.097 (7)0.018 (9)−0.013 (8)−0.005 (6)
Geometric parameters (Å, º) top
Cl1A—C1A1.735 (11)C4A—H4A0.9300
Cl1B—C1B1.735 (11)C11B—H11A0.9601
N1A—C8A1.485 (12)C11B—H11B0.9601
N1A—C10A1.485 (10)C11B—H11C0.9601
N1A—H1A10.9000C11A—H11D0.9601
N1A—H1A20.9000C11A—H11E0.9601
O1A—C7A1.271 (19)C11A—H11F0.9601
C5B—C4B1.385 (12)C12B—H12A0.9600
C5B—C6B1.384 (16)C12B—H12B0.9600
C5B—C7B1.464 (15)C12B—H12C0.9600
N1B—C10B1.485 (10)C12A—H12D0.9600
N1B—C8B1.485 (12)C12A—H12E0.9600
N1B—H1B10.9000C12A—H12F0.9600
N1B—H1B20.9000C13B—H13D0.9600
C7A—C5A1.481 (19)C13B—H13E0.9600
C7A—C8A1.553 (17)C13B—H13F0.9600
C8A—C9A1.540 (14)C2B—C3B1.385 (16)
C8A—H8A0.9800C2B—C1B1.385 (13)
O1B—C7B1.160 (18)C2B—H2B0.9300
C10B—C13B1.541 (13)C9A—H9A10.9600
C10B—C11B1.540 (10)C9A—H9A20.9600
C10B—C12B1.540 (12)C9A—H9A30.9600
C6B—C1B1.367 (17)C2A—C3A1.385 (17)
C6B—H6B0.9300C2A—H2A0.9300
C13A—C10A1.540 (12)C3B—H3B0.9300
C13A—H13A0.9600C9B—H9B10.9600
C13A—H13B0.9600C9B—H9B20.9600
C13A—H13C0.9600C9B—H9B30.9600
C1A—C6A1.370 (16)C3A—H3A0.9300
C1A—C2A1.385 (12)O21—C211.449 (18)
C10A—C11A1.540 (11)O21—H210.8200
C10A—C12A1.540 (12)C23—C221.530 (19)
C8B—C7B1.532 (17)C23—H23A0.9600
C8B—C9B1.540 (15)C23—H23B0.9600
C8B—H8B0.9800C23—H23C0.9600
C6A—C5A1.385 (17)C21—C221.535 (17)
C6A—H6A0.9300C21—H21A0.9700
C4B—C3B1.385 (16)C21—H21B0.9700
C4B—H4B0.9300C22—H22A0.9700
C4A—C3A1.385 (17)C22—H22B0.9700
C4A—C5A1.385 (11)
C8A—N1A—C10A118.2 (8)C10A—C11A—H11E109.5
C8A—N1A—H1A1107.8H11D—C11A—H11E109.5
C10A—N1A—H1A1107.8C10A—C11A—H11F109.5
C8A—N1A—H1A2107.8H11D—C11A—H11F109.5
C10A—N1A—H1A2107.8H11E—C11A—H11F109.5
H1A1—N1A—H1A2107.1C10B—C12B—H12A109.5
C4B—C5B—C6B115.4 (11)C10B—C12B—H12B109.5
C4B—C5B—C7B122.8 (10)H12A—C12B—H12B109.5
C6B—C5B—C7B121.9 (10)C10B—C12B—H12C109.5
C10B—N1B—C8B120.2 (8)H12A—C12B—H12C109.5
C10B—N1B—H1B1107.3H12B—C12B—H12C109.5
C8B—N1B—H1B1107.3C10A—C12A—H12D109.5
C10B—N1B—H1B2107.3C10A—C12A—H12E109.5
C8B—N1B—H1B2107.3H12D—C12A—H12E109.5
H1B1—N1B—H1B2106.9C10A—C12A—H12F109.5
O1A—C7A—C5A124.3 (12)H12D—C12A—H12F109.5
O1A—C7A—C8A117.8 (13)H12E—C12A—H12F109.5
C5A—C7A—C8A117.9 (11)C10B—C13B—H13D109.5
N1A—C8A—C9A107.1 (9)C10B—C13B—H13E109.5
N1A—C8A—C7A108.5 (10)H13D—C13B—H13E109.5
C9A—C8A—C7A105.0 (10)C10B—C13B—H13F109.4
N1A—C8A—H8A112.0H13D—C13B—H13F109.5
C9A—C8A—H8A111.9H13E—C13B—H13F109.5
C7A—C8A—H8A112.0C3B—C2B—C1B117.2 (10)
N1B—C10B—C13B108.6 (8)C3B—C2B—H2B121.4
N1B—C10B—C11B112.0 (9)C1B—C2B—H2B121.4
C13B—C10B—C11B110.3 (10)O1B—C7B—C5B118.7 (13)
N1B—C10B—C12B103.2 (7)O1B—C7B—C8B118.6 (11)
C13B—C10B—C12B109.3 (9)C5B—C7B—C8B122.7 (11)
C11B—C10B—C12B113.1 (10)C8A—C9A—H9A1109.5
C1B—C6B—C5B122.1 (12)C8A—C9A—H9A2109.5
C1B—C6B—H6B119.0H9A1—C9A—H9A2109.5
C5B—C6B—H6B119.0C8A—C9A—H9A3109.5
C10A—C13A—H13A109.5H9A1—C9A—H9A3109.5
C10A—C13A—H13B109.5H9A2—C9A—H9A3109.5
H13A—C13A—H13B109.5C6B—C1B—C2B121.9 (8)
C10A—C13A—H13C109.5C6B—C1B—Cl1B118.3 (8)
H13A—C13A—H13C109.5C2B—C1B—Cl1B119.8 (8)
H13B—C13A—H13C109.5C1A—C2A—C3A120.6 (11)
C6A—C1A—C2A119.5 (8)C1A—C2A—H2A119.7
C6A—C1A—Cl1A122.1 (7)C3A—C2A—H2A119.7
C2A—C1A—Cl1A118.0 (8)C2B—C3B—C4B119.7 (12)
N1A—C10A—C11A111.6 (9)C2B—C3B—H3B120.1
N1A—C10A—C12A109.8 (7)C4B—C3B—H3B120.1
C11A—C10A—C12A106.6 (9)C8B—C9B—H9B1109.5
N1A—C10A—C13A109.4 (8)C8B—C9B—H9B2109.5
C11A—C10A—C13A109.1 (10)H9B1—C9B—H9B2109.5
C12A—C10A—C13A110.3 (9)C8B—C9B—H9B3109.5
N1B—C8B—C7B110.4 (9)H9B1—C9B—H9B3109.5
N1B—C8B—C9B112.6 (9)H9B2—C9B—H9B3109.5
C7B—C8B—C9B111.6 (11)C4A—C3A—C2A120.3 (13)
N1B—C8B—H8B107.3C4A—C3A—H3A119.9
C7B—C8B—H8B107.3C2A—C3A—H3A119.9
C9B—C8B—H8B107.3C21—O21—H21109.5
C1A—C6A—C5A119.7 (12)C22—C23—H23A109.5
C1A—C6A—H6A120.1C22—C23—H23B109.5
C5A—C6A—H6A120.1H23A—C23—H23B109.5
C5B—C4B—C3B123.5 (11)C22—C23—H23C109.5
C5B—C4B—H4B118.3H23A—C23—H23C109.5
C3B—C4B—H4B118.3H23B—C23—H23C109.5
C3A—C4A—C5A118.3 (12)O21—C21—C22103.6 (11)
C3A—C4A—H4A120.9O21—C21—H21A111.1
C5A—C4A—H4A120.9C22—C21—H21A111.0
C10B—C11B—H11A109.5O21—C21—H21B111.0
C10B—C11B—H11B109.5C22—C21—H21B111.0
H11A—C11B—H11B109.5H21A—C21—H21B109.0
C10B—C11B—H11C109.5C21—C22—C23109.0 (11)
H11A—C11B—H11C109.5C21—C22—H22A109.9
H11B—C11B—H11C109.5C23—C22—H22A109.9
C6A—C5A—C4A121.5 (11)C21—C22—H22B109.9
C6A—C5A—C7A114.1 (10)C23—C22—H22B109.9
C4A—C5A—C7A124.4 (10)H22A—C22—H22B108.3
C10A—C11A—H11D109.5
C10A—N1A—C8A—C9A163.9 (10)O1A—C7A—C5A—C6A11 (2)
C10A—N1A—C8A—C7A−83.3 (12)C8A—C7A—C5A—C6A−170.2 (13)
O1A—C7A—C8A—N1A−30.1 (17)O1A—C7A—C5A—C4A−169.4 (16)
C5A—C7A—C8A—N1A151.2 (12)C8A—C7A—C5A—C4A9 (2)
O1A—C7A—C8A—C9A84.1 (16)C4B—C5B—C7B—O1B172.1 (16)
C5A—C7A—C8A—C9A−94.6 (14)C6B—C5B—C7B—O1B−8 (2)
C8B—N1B—C10B—C13B71.2 (11)C4B—C5B—C7B—C8B−8 (2)
C8B—N1B—C10B—C11B−50.9 (13)C6B—C5B—C7B—C8B171.9 (13)
C8B—N1B—C10B—C12B−172.9 (10)N1B—C8B—C7B—O1B31.9 (19)
C4B—C5B—C6B—C1B3 (2)C9B—C8B—C7B—O1B−94.2 (18)
C7B—C5B—C6B—C1B−176.9 (16)N1B—C8B—C7B—C5B−148.0 (13)
C8A—N1A—C10A—C11A52.4 (12)C9B—C8B—C7B—C5B85.9 (17)
C8A—N1A—C10A—C12A170.4 (10)C5B—C6B—C1B—C2B−6 (3)
C8A—N1A—C10A—C13A−68.4 (11)C5B—C6B—C1B—Cl1B176.3 (12)
C10B—N1B—C8B—C7B81.1 (13)C3B—C2B—C1B—C6B6 (3)
C10B—N1B—C8B—C9B−153.4 (11)C3B—C2B—C1B—Cl1B−176.5 (12)
C2A—C1A—C6A—C5A−3 (3)C6A—C1A—C2A—C3A3 (3)
Cl1A—C1A—C6A—C5A−175.4 (12)Cl1A—C1A—C2A—C3A176.0 (14)
C6B—C5B—C4B—C3B0 (2)C1B—C2B—C3B—C4B−3 (2)
C7B—C5B—C4B—C3B179.8 (15)C5B—C4B—C3B—C2B0 (2)
C1A—C6A—C5A—C4A2 (2)C5A—C4A—C3A—C2A3 (3)
C1A—C6A—C5A—C7A−178.1 (15)C1A—C2A—C3A—C4A−3 (3)
C3A—C4A—C5A—C6A−2 (2)O21—C21—C22—C23−140.0 (16)
C3A—C4A—C5A—C7A178.3 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A1···Br1A0.902.463.353 (9)174
N1A—H1A2···Br1Bi0.902.603.410 (9)150
N1B—H1B1···Br1Bii0.902.463.362 (9)175
N1B—H1B2···Br1Aiii0.902.583.383 (9)149
O21—H21···Br1A0.822.733.487 (10)153
Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z; (iii) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC13H19ClNO+·Br−·0.5C3H8O
Mr350.70
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)7.8614 (4), 9.4100 (6), 11.8477 (7)
α, β, γ (°)85.783 (2), 78.159 (2), 89.450 (2)
V (Å3)855.46 (9)
Z2
Radiation typeMo Kα
µ (mm−1)2.56
Crystal size (mm)0.46 × 0.28 × 0.14
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.361, 0.647
No. of measured, independent and
observed [I > 2σ(I)] reflections		8456, 6355, 4179
Rint0.031
(sin θ/λ)max (Å−1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.138, 1.00
No. of reflections6355
No. of parameters354
No. of restraints77
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.74, −0.97
Absolute structureFlack (1983), 2490 Friedel pairs
Absolute structure parameter0.34 (3)

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1A—H1A1···Br1A0.902.463.353 (9)173.7
N1A—H1A2···Br1Bi0.902.603.410 (9)149.8
N1B—H1B1···Br1Bii0.902.463.362 (9)174.7
N1B—H1B2···Br1Aiii0.902.583.383 (9)148.9
O21—H21···Br1A0.822.733.487 (10)153.4
Symmetry codes: (i) x−1, y, z; (ii) x, y+1, z; (iii) x+1, y+1, z.
 

Acknowledgements

The project was supported by the Zhejiang Provincial Natural Science Foundation of China (J200801).

References

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 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
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 First citationRigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationRigaku (2007). CrystalStructure. Rigaku, Tokyo, Japan.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationStewart, J. J., Berkel, H. J., Parish, R. C., Simar, M. R., Syed, A., Bocchini, J. A. Jr, Wilson, J. T. & Manno, J. E. (2001). J. Clin. Pharmacol. 41, 770–778.  CrossRef PubMed CAS Google Scholar

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ISSN: 2056-9890
Volume 67| Part 10| October 2011| Page o2772
https://doi.org/10.1107/S1600536811037093
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