9-O-Butyl­berberrubinium bromide

Zhu Chen; Xue-Gang Li; Yong-Sheng Xie; Xiao-Li Ye

doi:10.1107/S1600536809018388

. 2009 May 23;65(Pt 6):o1370. doi: 10.1107/S1600536809018388

9-O-Butylberberrubinium bromide

Zhu Chen ^a, Xue-Gang Li ^a, Yong-Sheng Xie ^b, Xiao-Li Ye ^c,^*

PMCID: PMC2969731 PMID: 21583219

Abstract

In the title compound, C₂₃H₂₄NO₄ ⁺·Br⁻, the butyl chain is disordered between two conformations; the occupancies refined to 0.735 (7) and 0.265 (7). The dihedral angle between the naphthalene ring system and the phenyl ring is 11.6 (2)°. In the crystal structure, the cations are packed via π–π interactions into stacks propagating in the [010] direction. Weak intermolecular C—H⋯O and C—H⋯Br hydrogen bonds contribute further to the crystal packing stability.

Related literature

For the bioactivity of berberine, see: Jiang et al. (1998 ▶); Kupeli et al.. (2002 ▶). For the bioactivity of 9-O-butyl-berberrubine bromide, see Ye & Li (2007 ▶).

Experimental

Crystal data

C₂₃H₂₄NO₄ ⁺·Br⁻
M _r = 458.34
Monoclinic,
a = 9.716 (4) Å
b = 7.623 (3) Å
c = 27.443 (11) Å
β = 92.983 (8)°
V = 2029.9 (14) Å³
Z = 4
Mo Kα radiation
μ = 2.06 mm⁻¹
T = 295 K
0.12 × 0.10 × 0.06 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2005 ▶) T _min = 0.791, T _max = 0.887
10394 measured reflections
3592 independent reflections
1965 reflections with I > 2σ(I)
R _int = 0.069

Refinement

R[F ² > 2σ(F ²)] = 0.060
wR(F ²) = 0.161
S = 1.08
3592 reflections
276 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: SMART (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018388/cv2550sup1.cif

e-65-o1370-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018388/cv2550Isup2.hkl

e-65-o1370-Isup2.hkl^{(176.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Centroid-to-centroid distances (Å).

Cg1⋯Cg3ⁱ	3.780 (4)
Cg2⋯Cg3ⁱⁱ	3.775 (4)

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1, Cg2 and Cg3 are the centroids of the N1/C13/C12/C9/C10/C14, C5–C10 and C15/C19–C22/C16 rings, respectively.

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯Br1	0.93	2.77	3.658 (5)	161
C2—H2A⋯O2ⁱⁱⁱ	0.97	2.64	3.404 (14)	136

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Symmetry code: (iii) Inline graphic .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 20673084), the Natural Science Foundation Project of CQ CSTC (grant No. 2008BB5257) and the Major Technologies R & D Program of CQ CSTC (grant No. 2008AA5021).

supplementary crystallographic information

Comment

Berberine is a main compound presented in the rhizome of Coptis chinensis Franch. Berberine and its derivatives are used for treating diarrhoea (Kupeli et al., 2002) and anti-inflammatory (Jiang et al., 1998). Herewith we report the crystal structure of the title compound (I), which exhibits an excellent antibacterial activity (Ye & Li, 2007).

In (I) (Fig. 1), the dihedral angles formed by the benzene rings C5–C10 and C15/C19/C20/C21/C22/C16 with the pyridine ring are 2.2 (3) and 12.8 (3)°, respectively. The six-membered heterocyclic ring (C13/C15/C16/C17/C18/N1) adopts screw-boat conformation. In the crystal structure, weak intermolecular C—H···O and C—H···Br hydrogen bonds (Table 2) link the molecules. The aromatic rings in the cations are involved in π–π interactions (Table 1). The cations are packed viaπ–π interactions into stacks propagated in direction [010].

Experimental

Berberrubine was obtained from berberine by pyrolysis at 180 °C for 1 h. Then dried berberrubine (10 mmol) was dissolved in DMF (200 ml) and incubated with n-butyl bromide (11 mmol) for 5 h at 100 °C to give the corresponding crude 9-O-butyl-berberrubine bromide. The product was purified by recrystallization from methanol at -18 °C. Crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution of the solid dissolved in methanol at room temperature for 15 d.