Steviamine, a new class of indolizidine alkaloid [(1R,2S,3R,5R,8aR)-3-hydroxy-meth-yl-5-methyl-octa-hydro-indolizine-1,2-diol hydro-bromide].

X-ray crystallographic analysis of the title hydro-bromide salt, C(10)H(20)N(+)·Br(-), of (1R,2S,3R,5R,8aR)-3-hydroxy-meth-yl-5-methyl-octa-hydro-indolizine-1,2-diol defines the absolute and relative stereochemistry at the five chiral centres in steviamine, a new class of polyhydroxy-lated indolizidine alkaloid isolated from Stevia rebaudiana (Asteraceae) leaves. In the crystal structure, mol-ecules are linked by inter-molecular O-H⋯Br and N-H⋯Br hydrogen bonds, forming double chains around the twofold screw axes along the b-axis direction. Intra-molecular O-H⋯O inter-actions occur.

Related literature

For background to the biological activity of indolizidines, see: Asano et al. (2000a ▶,2000b ▶); Colegate et al. (1979 ▶); Davis et al. (1996 ▶); Donohoe et al. (2008 ▶); Durantel (2009 ▶); Hakansson et al. (2008 ▶); Hohenschutz et al. (1981 ▶); Kato et al. (1999 ▶, 2007 ▶); Klein et al. (1999 ▶); Lagana et al. (2006 ▶); Sengoku et al. (2009 ▶); Watson et al. (2001 ▶); Whitby et al. (2005 ▶); Yamashita et al. (2002 ▶). For the Hooft parameter, see: Hooft et al. (2008 ▶). For the extinction correction, see: Larson (1970 ▶).

Experimental

Crystal data

C10H20N+·Br−

M = 282.18

Orthorhombic,

a = 8.4616 (1) Å

b = 8.8762 (1) Å

c = 15.8270 (2) Å

V = 1188.72 (2) Å3

Z = 4

Mo Kα radiation

μ = 3.45 mm−1

T = 150 K

0.46 × 0.46 × 0.26 mm

Data collection

Nonius KappaCCD area-detector diffractometer

Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.20, T max = 0.41

2675 measured reflections

2658 independent reflections

2484 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.052

S = 1.00

2658 reflections

138 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.52 e Å−3

Absolute structure: Flack (1983 ▶), 1102 Friedel pairs

Flack parameter: 0.002 (10)

Data collection: COLLECT (Nonius, 2001 ▶).; cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: CRYSTALS.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809043827/lh2918sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043827/lh2918Isup2.hkl

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

C10H20N+·Br−	Dx = 1.577 Mg m−3
Mr = 282.18	Melting point: not measured K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1544 reflections
a = 8.4616 (1) Å	θ = 5–27°
b = 8.8762 (1) Å	µ = 3.45 mm−1
c = 15.8270 (2) Å	T = 150 K
V = 1188.72 (2) Å3	Plate, colourless
Z = 4	0.46 × 0.46 × 0.26 mm
F(000) = 584

Nonius KappaCCD area-detector diffractometer	2484 reflections with I > 2σ(I)
graphite	Rint = 0.042
ω scans	θmax = 27.5°, θmin = 5.1°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997)	h = −10→10
Tmin = 0.20, Tmax = 0.41	k = −11→11
2675 measured reflections	l = −20→20
2658 independent reflections

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	Method = Modified Sheldrick w = 1/[σ2(F2) + ( 0.01P)2 + 0.86P], where P = [max(Fo2,0) + 2Fc2]/3
R[F2 > 2σ(F2)] = 0.025	(Δ/σ)max = 0.001
wR(F2) = 0.052	Δρmax = 0.37 e Å−3
S = 1.00	Δρmin = −0.52 e Å−3
2658 reflections	Extinction correction: Larson (1970), Equation 22
138 parameters	Extinction coefficient: 75 (8)
0 restraints	Absolute structure: Flack (1983), 1102 Friedel-pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.002 (10)
Hydrogen site location: inferred from neighbouring sites

	x	y	z	Uiso*/Ueq
Br1	0.29652 (3)	0.79140 (2)	0.693045 (16)	0.0373
O2	−0.0613 (2)	0.2681 (2)	0.63610 (12)	0.0470
C3	0.0377 (3)	0.3939 (3)	0.65007 (17)	0.0381
C4	0.1564 (4)	0.3703 (3)	0.72343 (15)	0.0436
O5	0.1230 (3)	0.2427 (2)	0.77338 (12)	0.0682
C6	0.3207 (4)	0.3611 (2)	0.68353 (14)	0.0362
N7	0.2994 (3)	0.45785 (19)	0.60566 (10)	0.0248
C8	0.1381 (3)	0.4183 (3)	0.57125 (14)	0.0267
C9	0.0873 (3)	0.5356 (3)	0.50829 (16)	0.0349
C10	0.2069 (4)	0.5435 (3)	0.43633 (14)	0.0389
C11	0.3726 (3)	0.5724 (3)	0.47093 (16)	0.0394
C12	0.4244 (3)	0.4594 (3)	0.53787 (15)	0.0330
C13	0.5841 (3)	0.4996 (4)	0.5756 (2)	0.0490
C14	0.3784 (4)	0.2019 (3)	0.66419 (17)	0.0517
O15	0.2695 (3)	0.12282 (19)	0.61308 (12)	0.0522
H31	−0.0258	0.4840	0.6613	0.0459*
H41	0.1545	0.4576	0.7609	0.0522*
H61	0.4003	0.4116	0.7186	0.0435*
H81	0.1481	0.3216	0.5435	0.0325*
H92	0.0822	0.6334	0.5366	0.0421*
H91	−0.0170	0.5096	0.4861	0.0419*
H102	0.1762	0.6219	0.3973	0.0473*
H101	0.2044	0.4458	0.4063	0.0468*
H111	0.3741	0.6720	0.4958	0.0478*
H112	0.4450	0.5700	0.4237	0.0485*
H121	0.4243	0.3580	0.5138	0.0384*
H132	0.6602	0.5024	0.5310	0.0746*
H131	0.5781	0.5970	0.6021	0.0735*
H133	0.6131	0.4254	0.6167	0.0738*
H141	0.3923	0.1509	0.7163	0.0614*
H142	0.4798	0.2080	0.6355	0.0607*
H151	0.2850	0.0336	0.6278	0.0778*
H21	−0.1216	0.2726	0.6762	0.0723*
H51	0.0999	0.1687	0.7424	0.1018*
H71	0.2900	0.5607	0.6279	0.0500*

	U11	U22	U33	U12	U13	U23
Br1	0.04557 (13)	0.02142 (11)	0.04505 (13)	−0.00181 (11)	0.00573 (13)	−0.00477 (10)
O2	0.0451 (11)	0.0463 (11)	0.0495 (11)	−0.0168 (9)	0.0134 (8)	0.0013 (9)
C3	0.0472 (16)	0.0264 (12)	0.0406 (14)	−0.0030 (11)	0.0188 (12)	−0.0031 (10)
C4	0.078 (2)	0.0311 (12)	0.0220 (11)	−0.0217 (13)	0.0128 (12)	−0.0036 (9)
O5	0.1153 (19)	0.0591 (14)	0.0301 (9)	−0.0488 (13)	−0.0052 (11)	0.0145 (9)
C6	0.0647 (17)	0.0209 (10)	0.0230 (11)	−0.0009 (11)	−0.0096 (13)	0.0022 (9)
N7	0.0324 (9)	0.0199 (8)	0.0220 (8)	−0.0004 (9)	0.0005 (9)	−0.0002 (6)
C8	0.0307 (12)	0.0229 (10)	0.0266 (11)	−0.0031 (9)	0.0027 (10)	−0.0016 (8)
C9	0.0349 (13)	0.0358 (13)	0.0339 (13)	0.0056 (11)	−0.0047 (11)	−0.0005 (11)
C10	0.0489 (14)	0.0414 (13)	0.0263 (11)	0.0028 (14)	−0.0021 (13)	0.0093 (10)
C11	0.0466 (15)	0.0391 (14)	0.0326 (13)	−0.0071 (12)	0.0113 (12)	0.0065 (11)
C12	0.0317 (13)	0.0356 (13)	0.0316 (12)	0.0015 (10)	0.0044 (10)	−0.0048 (10)
C13	0.0316 (14)	0.0627 (19)	0.0526 (17)	0.0008 (13)	0.0022 (13)	−0.0101 (14)
C14	0.091 (2)	0.0238 (12)	0.0401 (13)	0.0082 (16)	−0.0209 (14)	−0.0002 (12)
O15	0.0927 (18)	0.0219 (8)	0.0419 (10)	0.0030 (10)	−0.0184 (11)	−0.0038 (7)

O2—C3	1.414 (3)	C9—H92	0.978
O2—H21	0.815	C9—H91	0.977
C3—C4	1.549 (4)	C10—C11	1.527 (4)
C3—C8	1.525 (3)	C10—H102	0.965
C3—H31	0.980	C10—H101	0.989
C4—O5	1.409 (3)	C11—C12	1.523 (4)
C4—C6	1.529 (4)	C11—H111	0.968
C4—H41	0.976	C11—H112	0.967
O5—H51	0.843	C12—C13	1.519 (4)
C6—N7	1.513 (3)	C12—H121	0.977
C6—C14	1.526 (3)	C13—H132	0.955
C6—H61	0.981	C13—H131	0.963
N7—C8	1.511 (3)	C13—H133	0.958
N7—C12	1.507 (3)	C14—O15	1.412 (3)
N7—H71	0.982	C14—H141	0.949
C8—C9	1.504 (3)	C14—H142	0.972
C8—H81	0.967	O15—H151	0.836
C9—C10	1.525 (4)
C3—O2—H21	102.1	C8—C9—H91	109.4
O2—C3—C4	113.2 (2)	C10—C9—H91	110.0
O2—C3—C8	108.3 (2)	H92—C9—H91	109.5
C4—C3—C8	105.7 (2)	C9—C10—C11	110.44 (19)
O2—C3—H31	110.4	C9—C10—H102	109.4
C4—C3—H31	109.3	C11—C10—H102	110.8
C8—C3—H31	109.8	C9—C10—H101	107.7
C3—C4—O5	113.5 (2)	C11—C10—H101	109.8
C3—C4—C6	106.69 (19)	H102—C10—H101	108.6
O5—C4—C6	111.8 (2)	C10—C11—C12	113.8 (2)
C3—C4—H41	109.7	C10—C11—H111	108.1
O5—C4—H41	107.1	C12—C11—H111	108.4
C6—C4—H41	107.9	C10—C11—H112	107.5
C4—O5—H51	110.3	C12—C11—H112	109.9
C4—C6—N7	101.4 (2)	H111—C11—H112	109.0
C4—C6—C14	115.0 (2)	C11—C12—N7	107.4 (2)
N7—C6—C14	113.58 (19)	C11—C12—C13	112.0 (2)
C4—C6—H61	111.5	N7—C12—C13	110.3 (2)
N7—C6—H61	106.4	C11—C12—H121	109.6
C14—C6—H61	108.5	N7—C12—H121	105.6
C6—N7—C8	105.63 (18)	C13—C12—H121	111.7
C6—N7—C12	120.1 (2)	C12—C13—H132	108.4
C8—N7—C12	112.30 (16)	C12—C13—H131	109.6
C6—N7—H71	104.2	H132—C13—H131	109.5
C8—N7—H71	105.8	C12—C13—H133	109.5
C12—N7—H71	107.6	H132—C13—H133	110.3
C3—C8—N7	103.98 (19)	H131—C13—H133	109.6
C3—C8—C9	118.7 (2)	C6—C14—O15	111.5 (2)
N7—C8—C9	109.66 (19)	C6—C14—H141	107.9
C3—C8—H81	107.1	O15—C14—H141	110.0
N7—C8—H81	106.9	C6—C14—H142	108.9
C9—C8—H81	109.8	O15—C14—H142	109.6
C8—C9—C10	109.7 (2)	H141—C14—H142	108.8
C8—C9—H92	108.9	C14—O15—H151	102.1
C10—C9—H92	109.3

D—H···A	D—H	H···A	D···A	D—H···A
O5—H51···O2	0.84	2.34	2.684 (3)	105
O5—H51···O15	0.84	2.53	3.018 (3)	118
N7—H71···Br1	0.98	2.29	3.268 (2)	172
O2—H21···Br1i	0.82	2.55	3.364 (2)	177
O15—H151···Br1ii	0.84	2.39	3.211 (2)	169

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H51⋯O2	0.84	2.34	2.684 (3)	105
O5—H51⋯O15	0.84	2.53	3.018 (3)	118
N7—H71⋯Br1	0.98	2.29	3.268 (2)	172
O2—H21⋯Br1i	0.82	2.55	3.364 (2)	177
O15—H151⋯Br1ii	0.84	2.39	3.211 (2)	169

Symmetry codes: (i) ; (ii) .