9-O-Butyl-berberrubinium bromide.

In the title compound, C(23)H(24)NO(4) (+)·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 inter-actions into stacks propagating in the [010] direction. Weak inter-molecular 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 = 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

Δρmax = 0.58 e Å−3

Δρmin = −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.

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

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

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

C23H24NO4+·Br−	F(000) = 944
Mr = 458.34	Dx = 1.500 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1163 reflections
a = 9.716 (4) Å	θ = 2.8–19.6°
b = 7.623 (3) Å	µ = 2.06 mm−1
c = 27.443 (11) Å	T = 295 K
β = 92.983 (8)°	Block, yellow
V = 2029.9 (14) Å3	0.12 × 0.10 × 0.06 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	3592 independent reflections
Radiation source: fine-focus sealed tube	1965 reflections with I > 2σ(I)
graphite	Rint = 0.069
φ and ω scans	θmax = 25.1°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker 2005)	h = −11→11
Tmin = 0.791, Tmax = 0.887	k = −7→9
10394 measured reflections	l = −32→32

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.060	H-atom parameters constrained
wR(F2) = 0.161	w = 1/[σ2(Fo2) + (0.0623P)2 + 1.1441P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
3592 reflections	Δρmax = 0.58 e Å−3
276 parameters	Δρmin = −0.55 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0020 (7)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.19113 (6)	0.34507 (10)	0.58534 (2)	0.0683 (3)
O1	0.4605 (4)	0.4269 (6)	0.31978 (15)	0.0691 (13)
O2	0.8340 (4)	−0.0249 (7)	0.66220 (16)	0.0802 (14)
O3	0.5968 (4)	0.0055 (6)	0.66073 (16)	0.0708 (12)
O4	0.1935 (4)	0.5291 (6)	0.31514 (15)	0.0741 (13)
N1	0.6413 (4)	0.2391 (6)	0.44906 (17)	0.0469 (12)
C1'	0.5253 (10)	0.5997 (11)	0.3125 (3)	0.073 (2)	0.735 (7)
H1'1	0.5814	0.6382	0.3407	0.088*	0.735 (7)
H1'2	0.4589	0.6897	0.3027	0.088*	0.735 (7)
C1	0.4509 (12)	0.5865 (18)	0.2933 (5)	0.073 (2)	0.265 (7)
H1A	0.4497	0.6807	0.3170	0.088*	0.265 (7)
H1B	0.3617	0.5872	0.2757	0.088*	0.265 (7)
C2	0.5550 (11)	0.6342 (14)	0.2577 (4)	0.107 (3)	0.735 (7)
H2A	0.5042	0.6720	0.2282	0.128*	0.735 (7)
H2B	0.6033	0.7367	0.2708	0.128*	0.735 (7)
C3	0.6599 (11)	0.5126 (15)	0.2427 (4)	0.117 (3)	0.735 (7)
H3A	0.6196	0.3962	0.2410	0.140*	0.735 (7)
H3B	0.7335	0.5103	0.2679	0.140*	0.735 (7)
C4	0.7234 (15)	0.5492 (18)	0.1943 (4)	0.120 (4)	0.735 (7)
H4A	0.7620	0.4430	0.1822	0.180*	0.735 (7)
H4B	0.7948	0.6357	0.1990	0.180*	0.735 (7)
H4C	0.6537	0.5922	0.1713	0.180*	0.735 (7)
C2'	0.611 (3)	0.540 (3)	0.2709 (9)	0.107 (3)	0.265 (7)
H2'1	0.6905	0.4764	0.2843	0.128*	0.265 (7)
H2'2	0.5562	0.4586	0.2506	0.128*	0.265 (7)
C3'	0.659 (3)	0.687 (3)	0.2392 (8)	0.117 (3)	0.265 (7)
H3'1	0.7435	0.7352	0.2543	0.140*	0.265 (7)
H3'2	0.5904	0.7792	0.2382	0.140*	0.265 (7)
C4'	0.686 (5)	0.633 (5)	0.1874 (8)	0.120 (4)	0.265 (7)
H4'1	0.7240	0.7304	0.1705	0.180*	0.265 (7)
H4'2	0.6009	0.5976	0.1709	0.180*	0.265 (7)
H4'3	0.7498	0.5369	0.1880	0.180*	0.265 (7)
C5	0.3838 (6)	0.4217 (8)	0.3608 (2)	0.0544 (14)
C6	0.2479 (6)	0.4712 (8)	0.3590 (2)	0.0570 (15)
C7	0.1715 (6)	0.4554 (8)	0.4011 (2)	0.0592 (16)
H7	0.0792	0.4880	0.3995	0.071*
C8	0.2291 (6)	0.3941 (8)	0.4439 (2)	0.0533 (15)
H8	0.1758	0.3835	0.4710	0.064*
C9	0.3696 (5)	0.3464 (8)	0.4475 (2)	0.0482 (13)
C10	0.4459 (5)	0.3590 (8)	0.4044 (2)	0.0479 (13)
C11	0.0506 (6)	0.5753 (10)	0.3118 (2)	0.080 (2)
H11A	−0.0039	0.4744	0.3190	0.121*
H11B	0.0260	0.6157	0.2794	0.121*
H11C	0.0339	0.6668	0.3348	0.121*
C12	0.4368 (5)	0.2854 (7)	0.4901 (2)	0.0482 (14)
H12	0.3883	0.2809	0.5184	0.058*
C13	0.5723 (5)	0.2312 (7)	0.4923 (2)	0.0460 (13)
C14	0.5833 (5)	0.3019 (7)	0.4082 (2)	0.0488 (14)
H14	0.6356	0.3086	0.3808	0.059*
C15	0.6459 (5)	0.1642 (7)	0.5359 (2)	0.0476 (13)
C16	0.7894 (5)	0.1470 (8)	0.5374 (2)	0.0507 (14)
C17	0.8631 (6)	0.2081 (8)	0.4940 (2)	0.0573 (16)
H17A	0.8781	0.3337	0.4964	0.069*
H17B	0.9524	0.1514	0.4938	0.069*
C18	0.7835 (5)	0.1681 (8)	0.4478 (2)	0.0567 (15)
H18A	0.7797	0.0421	0.4429	0.068*
H18B	0.8292	0.2195	0.4206	0.068*
C19	0.5729 (6)	0.1186 (7)	0.5774 (2)	0.0508 (14)
H19	0.4775	0.1284	0.5772	0.061*
C20	0.6445 (6)	0.0617 (8)	0.6165 (2)	0.0532 (15)
C21	0.7863 (6)	0.0423 (8)	0.6182 (2)	0.0597 (15)
C22	0.8615 (6)	0.0853 (8)	0.5790 (2)	0.0580 (15)
H22	0.9569	0.0738	0.5803	0.070*
C23	0.7160 (7)	−0.0309 (10)	0.6915 (2)	0.0759 (19)
H23A	0.7082	−0.1461	0.7061	0.091*
H23B	0.7252	0.0554	0.7174	0.091*

	U11	U22	U33	U12	U13	U23
Br1	0.0502 (4)	0.0849 (6)	0.0714 (5)	−0.0009 (4)	0.0186 (3)	0.0016 (4)
O1	0.066 (3)	0.088 (3)	0.055 (3)	0.020 (2)	0.017 (2)	−0.005 (2)
O2	0.069 (3)	0.111 (4)	0.060 (3)	0.010 (3)	−0.007 (3)	0.011 (3)
O3	0.067 (3)	0.088 (3)	0.058 (3)	0.000 (3)	0.006 (2)	0.010 (2)
O4	0.051 (3)	0.116 (4)	0.056 (3)	0.018 (3)	0.003 (2)	−0.001 (3)
N1	0.039 (2)	0.056 (3)	0.047 (3)	0.002 (2)	0.010 (2)	0.000 (2)
C1'	0.077 (4)	0.080 (4)	0.064 (4)	0.002 (4)	0.020 (4)	0.015 (4)
C1	0.077 (4)	0.080 (4)	0.064 (4)	0.002 (4)	0.020 (4)	0.015 (4)
C2	0.117 (6)	0.108 (6)	0.098 (5)	0.002 (5)	0.034 (5)	0.020 (5)
C3	0.133 (6)	0.114 (6)	0.107 (6)	0.002 (6)	0.039 (5)	0.015 (5)
C4	0.140 (9)	0.132 (10)	0.092 (7)	−0.003 (8)	0.061 (6)	0.002 (7)
C2'	0.117 (6)	0.108 (6)	0.098 (5)	0.002 (5)	0.034 (5)	0.020 (5)
C3'	0.133 (6)	0.114 (6)	0.107 (6)	0.002 (6)	0.039 (5)	0.015 (5)
C4'	0.140 (9)	0.132 (10)	0.092 (7)	−0.003 (8)	0.061 (6)	0.002 (7)
C5	0.052 (3)	0.059 (3)	0.054 (3)	0.005 (3)	0.016 (3)	−0.002 (3)
C6	0.051 (3)	0.071 (4)	0.049 (3)	0.004 (3)	0.004 (3)	−0.002 (3)
C7	0.044 (3)	0.074 (4)	0.060 (4)	0.007 (3)	0.005 (3)	−0.005 (3)
C8	0.041 (3)	0.066 (4)	0.054 (3)	0.003 (3)	0.010 (3)	−0.003 (3)
C9	0.044 (3)	0.052 (3)	0.049 (3)	−0.001 (3)	0.011 (3)	−0.008 (3)
C10	0.043 (3)	0.051 (3)	0.050 (3)	0.005 (3)	0.008 (3)	−0.002 (3)
C11	0.061 (4)	0.114 (6)	0.065 (5)	0.016 (4)	−0.003 (4)	0.005 (4)
C12	0.044 (3)	0.055 (3)	0.047 (3)	0.001 (3)	0.012 (3)	0.000 (3)
C13	0.040 (3)	0.049 (3)	0.049 (3)	−0.004 (2)	0.010 (3)	−0.005 (3)
C14	0.043 (3)	0.058 (3)	0.047 (3)	−0.001 (3)	0.014 (3)	−0.004 (3)
C15	0.043 (3)	0.046 (3)	0.055 (3)	−0.003 (3)	0.006 (3)	0.001 (3)
C16	0.044 (3)	0.053 (3)	0.056 (3)	0.001 (3)	0.007 (3)	−0.004 (3)
C17	0.041 (3)	0.064 (4)	0.068 (4)	0.007 (3)	0.011 (3)	−0.001 (3)
C18	0.043 (3)	0.066 (4)	0.062 (4)	0.011 (3)	0.014 (3)	−0.001 (3)
C19	0.041 (3)	0.055 (3)	0.057 (3)	−0.005 (3)	0.007 (3)	−0.006 (3)
C20	0.048 (3)	0.058 (4)	0.053 (4)	−0.003 (3)	0.004 (3)	−0.010 (3)
C21	0.053 (3)	0.066 (4)	0.059 (4)	0.001 (3)	−0.006 (3)	0.001 (3)
C22	0.044 (3)	0.068 (4)	0.063 (4)	0.003 (3)	0.003 (3)	−0.004 (3)
C23	0.074 (4)	0.094 (5)	0.060 (4)	0.005 (4)	0.005 (4)	−0.001 (4)

O1—C5	1.382 (6)	C4'—H4'3	0.9600
O1—C1	1.418 (12)	C5—C6	1.372 (8)
O1—C1'	1.477 (8)	C5—C10	1.397 (8)
O2—C21	1.370 (7)	C6—C7	1.412 (8)
O2—C23	1.434 (7)	C7—C8	1.358 (8)
O3—C20	1.389 (7)	C7—H7	0.9300
O3—C23	1.424 (7)	C8—C9	1.412 (7)
O4—C6	1.361 (7)	C8—H8	0.9300
O4—C11	1.430 (7)	C9—C12	1.389 (7)
N1—C14	1.319 (7)	C9—C10	1.431 (7)
N1—C13	1.393 (6)	C10—C14	1.403 (7)
N1—C18	1.486 (6)	C11—H11A	0.9600
C1'—C2'	1.517 (8)	C11—H11B	0.9600
C1'—H1'1	0.9700	C11—H11C	0.9600
C1'—H1'2	0.9700	C12—C13	1.378 (7)
C1—C2	1.487 (7)	C12—H12	0.9300
C1—H1A	0.9700	C13—C15	1.456 (8)
C1—H1B	0.9700	C14—H14	0.9300
C2—C3	1.454 (7)	C15—C16	1.399 (7)
C2—H2A	0.9700	C15—C19	1.416 (7)
C2—H2B	0.9700	C16—C22	1.391 (8)
C3—C4	1.517 (7)	C16—C17	1.497 (7)
C3—H3A	0.9700	C17—C18	1.483 (8)
C3—H3B	0.9700	C17—H17A	0.9700
C4—H4A	0.9600	C17—H17B	0.9700
C4—H4B	0.9600	C18—H18A	0.9700
C4—H4C	0.9600	C18—H18B	0.9700
C2'—C3'	1.510 (8)	C19—C20	1.321 (8)
C2'—H2'1	0.9700	C19—H19	0.9300
C2'—H2'2	0.9700	C20—C21	1.384 (8)
C3'—C4'	1.516 (8)	C21—C22	1.370 (8)
C3'—H3'1	0.9700	C22—H22	0.9300
C3'—H3'2	0.9700	C23—H23A	0.9700
C4'—H4'1	0.9600	C23—H23B	0.9700
C4'—H4'2	0.9600
Cg1···Cg3i	3.780 (4)	Cg2···Cg3ii	3.775 (4)
C5—O1—C1	114.8 (6)	C8—C7—H7	119.0
C5—O1—C1'	112.8 (5)	C6—C7—H7	119.0
C21—O2—C23	105.2 (5)	C7—C8—C9	120.1 (5)
C20—O3—C23	106.2 (5)	C7—C8—H8	119.9
C6—O4—C11	117.9 (5)	C9—C8—H8	119.9
C14—N1—C13	122.5 (5)	C12—C9—C8	123.7 (5)
C14—N1—C18	117.9 (4)	C12—C9—C10	118.5 (5)
C13—N1—C18	119.6 (5)	C8—C9—C10	117.8 (5)
O1—C1'—C2'	95.0 (10)	C5—C10—C14	122.4 (5)
O1—C1'—H1'1	112.7	C5—C10—C9	120.8 (5)
C2'—C1'—H1'1	112.7	C14—C10—C9	116.7 (5)
O1—C1'—H1'2	112.7	O4—C11—H11A	109.5
C2'—C1'—H1'2	112.7	O4—C11—H11B	109.5
H1'1—C1'—H1'2	110.2	H11A—C11—H11B	109.5
O1—C1—C2	121.2 (9)	O4—C11—H11C	109.5
O1—C1—H1A	107.0	H11A—C11—H11C	109.5
C2—C1—H1A	107.0	H11B—C11—H11C	109.5
O1—C1—H1B	107.0	C13—C12—C9	122.8 (5)
C2—C1—H1B	107.0	C13—C12—H12	118.6
H1A—C1—H1B	106.8	C9—C12—H12	118.6
C3—C2—C1	122.8 (8)	C12—C13—N1	116.9 (5)
C3—C2—H2A	106.6	C12—C13—C15	124.6 (5)
C1—C2—H2A	106.6	N1—C13—C15	118.6 (5)
C3—C2—H2B	106.6	N1—C14—C10	122.5 (5)
C1—C2—H2B	106.6	N1—C14—H14	118.7
H2A—C2—H2B	106.6	C10—C14—H14	118.7
C2—C3—C4	117.0 (8)	C16—C15—C19	119.6 (5)
C2—C3—H3A	108.0	C16—C15—C13	120.2 (5)
C4—C3—H3A	108.0	C19—C15—C13	120.2 (5)
C2—C3—H3B	108.0	C22—C16—C15	121.0 (5)
C4—C3—H3B	108.0	C22—C16—C17	121.2 (5)
H3A—C3—H3B	107.3	C15—C16—C17	117.7 (5)
C3—C4—H4A	109.5	C18—C17—C16	111.6 (5)
C3—C4—H4B	109.5	C18—C17—H17A	109.3
H4A—C4—H4B	109.5	C16—C17—H17A	109.3
C3—C4—H4C	109.5	C18—C17—H17B	109.3
H4A—C4—H4C	109.5	C16—C17—H17B	109.3
H4B—C4—H4C	109.5	H17A—C17—H17B	108.0
C3'—C2'—C1'	114.1 (9)	C17—C18—N1	110.4 (5)
C3'—C2'—H2'1	108.7	C17—C18—H18A	109.6
C1'—C2'—H2'1	108.7	N1—C18—H18A	109.6
C3'—C2'—H2'2	108.7	C17—C18—H18B	109.6
C1'—C2'—H2'2	108.7	N1—C18—H18B	109.6
H2'1—C2'—H2'2	107.6	H18A—C18—H18B	108.1
C2'—C3'—C4'	114.3 (10)	C20—C19—C15	118.0 (5)
C2'—C3'—H3'1	108.7	C20—C19—H19	121.0
C4'—C3'—H3'1	108.7	C15—C19—H19	121.0
C2'—C3'—H3'2	108.7	C19—C20—C21	123.0 (6)
C4'—C3'—H3'2	108.7	C19—C20—O3	128.7 (5)
H3'1—C3'—H3'2	107.6	C21—C20—O3	108.3 (6)
C3'—C4'—H4'1	109.5	O2—C21—C22	127.7 (6)
C3'—C4'—H4'2	109.5	O2—C21—C20	111.1 (6)
H4'1—C4'—H4'2	109.5	C22—C21—C20	121.2 (6)
C3'—C4'—H4'3	109.5	C21—C22—C16	117.3 (5)
H4'1—C4'—H4'3	109.5	C21—C22—H22	121.3
H4'2—C4'—H4'3	109.5	C16—C22—H22	121.3
C6—C5—O1	121.4 (6)	O3—C23—O2	108.1 (5)
C6—C5—C10	119.8 (5)	O3—C23—H23A	110.1
O1—C5—C10	118.8 (5)	O2—C23—H23A	110.1
O4—C6—C5	116.8 (5)	O3—C23—H23B	110.1
O4—C6—C7	123.7 (5)	O2—C23—H23B	110.1
C5—C6—C7	119.5 (6)	H23A—C23—H23B	108.4
C8—C7—C6	121.9 (5)

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

Table 1

Centroid-to-centroid distances (Å)

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

Symmetry codes: (i) ; (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

Symmetry code: (iii) .