Ergometrinine.

The absolute configuration of ergometrinine, C(19)H(23)N(3)O(2) {systematic name: (6aR,9S)-N-[(S)-1-hy-droxy-propan-2-yl]-7-methyl-4,6,6a,7,8,9-hexa-hydro-indolo[4,3-fg]quinoline-9-carb-ox-amide}, was established based on epimerization reaction of ergometrine, which was followed by preparative HPLC. The non-aromatic ring (ring C of the ergoline skeleton) directly fused to the aromatic rings is nearly planar [maximum deviation = 0.271 (3) Å] and shows an envelope conformation, whereas ring D, involved in an intra-molecular N-H⋯N hydrogen bond, exibits a slightly distorted chair conformation. The structure displays undulating layers in the ac plane formed by O-H⋯O and N-H⋯O hydrogen bonds.

Related literature

Ergometrinine is one of the main ergot alkaloids produced by the fungus Claviceps purpurea on cereal grains in the field, see: Crews et al. (2009 ▶); Müller et al. (2009 ▶). For investigations of the biologically inactive C8-(S)-isomer of ergometrinine, see: Pierri et al. (1982 ▶); Komarova & Tolkachev (2001 ▶). For the crystal structure of ergometrine maleate, see: Cejka et al. (1996 ▶).

Experimental

Crystal data

C19H23N3O2

M = 325.40

Orthorhombic,

a = 7.4097 (5) Å

b = 12.7313 (7) Å

c = 18.2648 (9) Å

V = 1723.01 (17) Å3

Z = 4

Cu Kα radiation

μ = 0.66 mm−1

T = 298 K

0.20 × 0.05 × 0.02 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971 ▶) T min = 0.879, T max = 0.986

4023 measured reflections

1889 independent reflections

1269 reflections with I > 2σ(I)

R int = 0.056

3 standard reflections every 60 min intensity decay: 2%

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.112

S = 1.00

1889 reflections

219 parameters

H-atom parameters constrained

Δρmax = 0.14 e Å−3

Δρmin = −0.16 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: CORINC (Dräger & Gattow, 1971 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810030825/sj5027sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030825/sj5027Isup2.hkl

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

C19H23N3O2	F(000) = 696
Mr = 325.40	Dx = 1.254 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 7.4097 (5) Å	θ = 15–23°
b = 12.7313 (7) Å	µ = 0.66 mm−1
c = 18.2648 (9) Å	T = 298 K
V = 1723.01 (17) Å3	Needle, yellow
Z = 4	0.20 × 0.05 × 0.02 mm

Enraf–Nonius CAD-4 diffractometer	1269 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.056
graphite	θmax = 70.0°, θmin = 4.2°
ω/2θ scans	h = −8→9
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971)	k = −15→15
Tmin = 0.879, Tmax = 0.986	l = −22→22
4023 measured reflections	3 standard reflections every 60 min
1889 independent reflections	intensity decay: 2%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0561P)2 + 0.0234P] where P = (Fo2 + 2Fc2)/3
1889 reflections	(Δ/σ)max < 0.001
219 parameters	Δρmax = 0.14 e Å−3
0 restraints	Δρmin = −0.16 e Å−3

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
O1	0.2918 (3)	−0.17372 (18)	0.36716 (13)	0.0586 (7)
O2	0.7137 (5)	−0.32052 (18)	0.48938 (13)	0.0815 (10)
H2O	0.7329	−0.3191	0.5439	0.122*
N1	0.5819 (4)	−0.1255 (2)	0.35374 (16)	0.0550 (8)
H1N	0.6603	−0.0793	0.3259	0.066*
N2	0.6383 (4)	0.06231 (19)	0.26795 (14)	0.0519 (8)
N3	0.7306 (5)	0.4652 (2)	0.43312 (17)	0.0666 (9)
H3N	0.7302	0.5372	0.4476	0.080*
C1	0.4047 (6)	−0.1103 (2)	0.34594 (17)	0.0464 (9)
C2	0.6592 (5)	−0.2226 (3)	0.38200 (17)	0.0520 (9)
H2	0.5736	−0.2793	0.3715	0.062*
C3	0.6825 (6)	−0.2176 (2)	0.46383 (19)	0.0602 (11)
H2A	0.7839	−0.1727	0.4761	0.072*
H2B	0.5749	−0.1889	0.4864	0.072*
C4	0.8315 (6)	−0.2470 (4)	0.3419 (2)	0.0890 (15)
H4A	0.8070	−0.2530	0.2904	0.133*
H4B	0.8802	−0.3121	0.3596	0.133*
H4C	0.9170	−0.1916	0.3500	0.133*
C5	0.3492 (5)	−0.0110 (2)	0.30590 (17)	0.0493 (9)
H5	0.2276	−0.0228	0.2865	0.059*
C6	0.4692 (6)	0.0159 (3)	0.24169 (19)	0.0584 (11)
H6A	0.4950	−0.0471	0.2137	0.070*
H6B	0.4077	0.0653	0.2098	0.070*
C7	0.6047 (5)	0.1676 (2)	0.29911 (16)	0.0440 (8)
H7	0.5654	0.2129	0.2588	0.053*
C8	0.7810 (5)	0.2148 (3)	0.32985 (19)	0.0527 (9)
H8A	0.8389	0.1644	0.3620	0.063*
H8B	0.8631	0.2303	0.2899	0.063*
C9	0.7408 (5)	0.3130 (2)	0.37121 (18)	0.0491 (9)
C10	0.8341 (6)	0.4010 (3)	0.3898 (2)	0.0622 (10)
H10	0.9516	0.4157	0.3752	0.075*
C11	0.5652 (6)	0.4189 (3)	0.44279 (19)	0.0543 (10)
C12	0.5701 (5)	0.3240 (2)	0.40378 (16)	0.0435 (8)
C13	0.4242 (5)	0.2560 (2)	0.40020 (16)	0.0436 (8)
C14	0.4491 (5)	0.1623 (2)	0.35402 (16)	0.0417 (8)
C15	0.3382 (5)	0.0807 (2)	0.35753 (18)	0.0459 (8)
H15	0.2495	0.0802	0.3936	0.055*
C16	0.2697 (5)	0.2850 (3)	0.43839 (18)	0.0545 (9)
H16	0.1681	0.2421	0.4373	0.065*
C17	0.2672 (7)	0.3792 (3)	0.4786 (2)	0.0685 (12)
H17	0.1631	0.3962	0.5045	0.082*
C18	0.4104 (7)	0.4473 (3)	0.4817 (2)	0.0656 (11)
H18	0.4047	0.5094	0.5083	0.079*
C19	0.7721 (7)	0.0655 (3)	0.2083 (2)	0.0793 (14)
H19A	0.7780	−0.0020	0.1850	0.119*
H19B	0.8884	0.0830	0.2279	0.119*
H19C	0.7371	0.1175	0.1730	0.119*

	U11	U22	U33	U12	U13	U23
O1	0.0606 (17)	0.0495 (13)	0.0658 (15)	−0.0125 (13)	0.0060 (14)	0.0047 (12)
O2	0.129 (3)	0.0458 (13)	0.0695 (17)	0.0021 (17)	−0.0340 (18)	0.0006 (12)
N1	0.048 (2)	0.0480 (16)	0.0684 (19)	−0.0048 (15)	−0.0015 (17)	0.0171 (14)
N2	0.067 (2)	0.0411 (14)	0.0477 (15)	0.0007 (15)	0.0157 (16)	−0.0004 (12)
N3	0.090 (3)	0.0410 (15)	0.0693 (19)	−0.0083 (18)	−0.017 (2)	−0.0049 (15)
C1	0.054 (3)	0.0427 (17)	0.0426 (17)	−0.0070 (19)	0.0016 (18)	−0.0021 (14)
C2	0.054 (2)	0.0444 (18)	0.058 (2)	−0.0008 (18)	−0.0048 (19)	0.0014 (16)
C3	0.071 (3)	0.0408 (18)	0.069 (2)	−0.0040 (19)	−0.017 (2)	0.0001 (16)
C4	0.069 (3)	0.094 (3)	0.104 (4)	0.013 (3)	0.018 (3)	0.011 (3)
C5	0.051 (2)	0.0449 (17)	0.0523 (19)	−0.0076 (18)	−0.0095 (18)	0.0020 (15)
C6	0.084 (3)	0.0473 (19)	0.0442 (18)	0.000 (2)	−0.005 (2)	−0.0034 (16)
C7	0.050 (2)	0.0414 (15)	0.0408 (16)	0.0026 (17)	0.0039 (17)	0.0042 (14)
C8	0.046 (2)	0.0538 (19)	0.058 (2)	−0.0014 (18)	0.0112 (18)	0.0019 (16)
C9	0.051 (2)	0.0431 (18)	0.0531 (19)	−0.0019 (17)	−0.0028 (19)	0.0044 (15)
C10	0.059 (3)	0.054 (2)	0.074 (2)	−0.007 (2)	−0.008 (2)	0.0077 (19)
C11	0.072 (3)	0.0394 (17)	0.0520 (19)	0.0029 (19)	−0.010 (2)	0.0001 (16)
C12	0.052 (2)	0.0381 (16)	0.0408 (17)	0.0039 (18)	−0.0029 (17)	0.0020 (14)
C13	0.049 (2)	0.0412 (16)	0.0409 (16)	0.0084 (18)	0.0016 (17)	0.0048 (13)
C14	0.048 (2)	0.0368 (15)	0.0406 (16)	0.0042 (16)	−0.0001 (16)	0.0035 (13)
C15	0.046 (2)	0.0443 (16)	0.0476 (17)	0.0042 (17)	0.0016 (17)	0.0024 (14)
C16	0.058 (3)	0.0512 (18)	0.0541 (19)	0.0053 (19)	0.010 (2)	0.0019 (17)
C17	0.087 (3)	0.060 (2)	0.059 (2)	0.021 (3)	0.018 (2)	−0.0003 (19)
C18	0.098 (3)	0.0418 (18)	0.057 (2)	0.018 (2)	0.004 (2)	−0.0066 (16)
C19	0.104 (4)	0.061 (2)	0.073 (2)	0.004 (3)	0.042 (3)	−0.0040 (19)

O1—C1	1.226 (4)	C6—H6B	0.9700
O2—C3	1.410 (4)	C7—C14	1.530 (4)
O2—H2O	1.0068	C7—C8	1.544 (5)
N1—C1	1.334 (5)	C7—H7	0.9800
N1—C2	1.457 (4)	C8—C9	1.490 (5)
N1—H1N	0.9707	C8—H8A	0.9700
N2—C6	1.466 (5)	C8—H8B	0.9700
N2—C19	1.474 (5)	C9—C10	1.360 (5)
N2—C7	1.477 (4)	C9—C12	1.405 (5)
N3—C11	1.371 (5)	C10—H10	0.9300
N3—C10	1.372 (5)	C11—C18	1.397 (6)
N3—H3N	0.9537	C11—C12	1.403 (4)
C1—C5	1.517 (4)	C12—C13	1.386 (5)
C2—C4	1.505 (5)	C13—C16	1.391 (5)
C2—C3	1.506 (5)	C13—C14	1.473 (4)
C2—H2	0.9800	C14—C15	1.325 (4)
C3—H2A	0.9700	C15—H15	0.9300
C3—H2B	0.9700	C16—C17	1.407 (5)
C4—H4A	0.9600	C16—H16	0.9300
C4—H4B	0.9600	C17—C18	1.371 (6)
C4—H4C	0.9600	C17—H17	0.9300
C5—C15	1.503 (4)	C18—H18	0.9300
C5—C6	1.511 (5)	C19—H19A	0.9600
C5—H5	0.9800	C19—H19B	0.9600
C6—H6A	0.9700	C19—H19C	0.9600
C3—O2—H2O	109.5	N2—C7—H7	107.2
C1—N1—C2	123.2 (3)	C14—C7—H7	107.2
C1—N1—H1N	116.4	C8—C7—H7	107.2
C2—N1—H1N	117.7	C9—C8—C7	110.0 (3)
C6—N2—C19	110.1 (3)	C9—C8—H8A	109.7
C6—N2—C7	110.3 (3)	C7—C8—H8A	109.7
C19—N2—C7	111.9 (3)	C9—C8—H8B	109.7
C11—N3—C10	108.5 (3)	C7—C8—H8B	109.7
C11—N3—H3N	112.1	H8A—C8—H8B	108.2
C10—N3—H3N	137.2	C10—C9—C12	105.6 (3)
O1—C1—N1	122.8 (3)	C10—C9—C8	135.7 (4)
O1—C1—C5	121.1 (3)	C12—C9—C8	118.6 (3)
N1—C1—C5	116.1 (3)	C9—C10—N3	110.5 (4)
N1—C2—C4	109.6 (3)	C9—C10—H10	124.7
N1—C2—C3	111.1 (3)	N3—C10—H10	124.7
C4—C2—C3	113.3 (4)	N3—C11—C18	133.5 (3)
N1—C2—H2	107.5	N3—C11—C12	106.4 (3)
C4—C2—H2	107.5	C18—C11—C12	120.1 (4)
C3—C2—H2	107.5	C13—C12—C11	122.8 (3)
O2—C3—C2	107.9 (3)	C13—C12—C9	128.3 (3)
O2—C3—H2A	110.1	C11—C12—C9	108.9 (3)
C2—C3—H2A	110.1	C12—C13—C16	116.9 (3)
O2—C3—H2B	110.1	C12—C13—C14	115.8 (3)
C2—C3—H2B	110.1	C16—C13—C14	127.2 (3)
H2A—C3—H2B	108.4	C15—C14—C13	122.0 (3)
C2—C4—H4A	109.5	C15—C14—C7	122.3 (3)
C2—C4—H4B	109.5	C13—C14—C7	115.7 (3)
H4A—C4—H4B	109.5	C14—C15—C5	123.0 (3)
C2—C4—H4C	109.5	C14—C15—H15	118.5
H4A—C4—H4C	109.5	C5—C15—H15	118.5
H4B—C4—H4C	109.5	C13—C16—C17	119.9 (4)
C15—C5—C6	110.0 (3)	C13—C16—H16	120.0
C15—C5—C1	111.1 (2)	C17—C16—H16	120.0
C6—C5—C1	113.8 (3)	C18—C17—C16	123.4 (4)
C15—C5—H5	107.2	C18—C17—H17	118.3
C6—C5—H5	107.2	C16—C17—H17	118.3
C1—C5—H5	107.2	C17—C18—C11	116.8 (3)
N2—C6—C5	109.9 (3)	C17—C18—H18	121.6
N2—C6—H6A	109.7	C11—C18—H18	121.6
C5—C6—H6A	109.7	N2—C19—H19A	109.5
N2—C6—H6B	109.7	N2—C19—H19B	109.5
C5—C6—H6B	109.7	H19A—C19—H19B	109.5
H6A—C6—H6B	108.2	N2—C19—H19C	109.5
N2—C7—C14	109.8 (2)	H19A—C19—H19C	109.5
N2—C7—C8	110.5 (3)	H19B—C19—H19C	109.5
C14—C7—C8	114.6 (2)
C2—N1—C1—O1	5.7 (5)	N3—C11—C12—C9	0.7 (4)
C2—N1—C1—C5	−171.7 (3)	C18—C11—C12—C9	−178.6 (3)
C1—N1—C2—C4	142.9 (4)	C10—C9—C12—C13	178.9 (3)
C1—N1—C2—C3	−91.1 (4)	C8—C9—C12—C13	−3.3 (5)
N1—C2—C3—O2	165.5 (3)	C10—C9—C12—C11	−1.0 (4)
C4—C2—C3—O2	−70.6 (4)	C8—C9—C12—C11	176.9 (3)
O1—C1—C5—C15	96.5 (4)	C11—C12—C13—C16	−0.9 (5)
N1—C1—C5—C15	−86.0 (4)	C9—C12—C13—C16	179.3 (3)
O1—C1—C5—C6	−138.6 (3)	C11—C12—C13—C14	177.2 (3)
N1—C1—C5—C6	38.8 (4)	C9—C12—C13—C14	−2.6 (5)
C19—N2—C6—C5	166.6 (3)	C12—C13—C14—C15	165.5 (3)
C7—N2—C6—C5	−69.4 (3)	C16—C13—C14—C15	−16.6 (5)
C15—C5—C6—N2	48.3 (4)	C12—C13—C14—C7	−17.5 (4)
C1—C5—C6—N2	−77.1 (3)	C16—C13—C14—C7	160.3 (3)
C6—N2—C7—C14	50.1 (3)	N2—C7—C14—C15	−14.9 (4)
C19—N2—C7—C14	173.1 (3)	C8—C7—C14—C15	−140.1 (3)
C6—N2—C7—C8	177.6 (3)	N2—C7—C14—C13	168.2 (3)
C19—N2—C7—C8	−59.4 (4)	C8—C7—C14—C13	43.0 (4)
N2—C7—C8—C9	−171.3 (2)	C13—C14—C15—C5	173.7 (3)
C14—C7—C8—C9	−46.5 (4)	C7—C14—C15—C5	−3.1 (5)
C7—C8—C9—C10	−155.5 (4)	C6—C5—C15—C14	−13.5 (5)
C7—C8—C9—C12	27.4 (4)	C1—C5—C15—C14	113.5 (4)
C12—C9—C10—N3	0.9 (4)	C12—C13—C16—C17	−0.5 (5)
C8—C9—C10—N3	−176.4 (4)	C14—C13—C16—C17	−178.3 (3)
C11—N3—C10—C9	−0.5 (4)	C13—C16—C17—C18	1.2 (5)
C10—N3—C11—C18	179.1 (4)	C16—C17—C18—C11	−0.6 (6)
C10—N3—C11—C12	−0.2 (4)	N3—C11—C18—C17	−179.9 (4)
N3—C11—C12—C13	−179.1 (3)	C12—C11—C18—C17	−0.7 (5)
C18—C11—C12—C13	1.5 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2	0.97	2.10	2.890 (4)	138.
O2—H2O···O1i	1.01	1.68	2.684 (3)	172.
N3—H3N···O2ii	0.95	1.97	2.918 (4)	173.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N2	0.97	2.10	2.890 (4)	138
O2—H2O⋯O1i	1.01	1.68	2.684 (3)	172
N3—H3N⋯O2ii	0.95	1.97	2.918 (4)	173

Symmetry codes: (i) ; (ii) .