Methyl-ergometrine maleate from synchrotron powder diffraction data.

The title compound {systematic name: 9,10-didehydro-N-[1-(hydroxy-meth-yl)prop-yl]-d-lysergamide maleate}, C(20)H(26)N(3)O(2) (+)·C(4)H(3)O(4) (-), contains a large rigid ergolene group. This group consists of an indole plane connected to a six-membered carbon ring adopting an envelope conformation and N-methyl-tetra-hydro-pyridine where the methyl group is in an equatorial position. In the crystal, inter-molecular N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds form an extensive three-dimensional hydrogen-bonding network, which holds the cations and anions together.

Related literature

For background to ergometrine, see: Dudley & Moir (1935 ▶); Kharasch & Legault (1935 ▶). Formethyl­ergometrine, see Stoll & Hofmann (1943 ▶). For crystal structure determinations of ergometrine, see: Čejka et al. (1996 ▶); Hušák et al. (1998 ▶).

Experimental

Crystal data

C20H26N3O2 +·C4H3O4 −

M = 455.51

Orthorhombic,

a = 5.71027 (5) Å

b = 12.76978 (17) Å

c = 33.1455 (4) Å

V = 2416.93 (5) Å3

Z = 4

Synchrotron radiation

λ = 0.6996 Å

T = 293 K

Specimen shape: cylinder

40 × 1 × 1 mm

Specimen prepared at 101 kPa

Specimen prepared at 293 K

Particle morphology: needle, white

Data collection

BM01B, ESRF, Grenoble

Specimen mounting: 1.0 mm borosilicate glass capillary

Specimen mounted in transmission mode

Scan method: step

Absorption correction: none

2θmin = 0.5, 2θmax = 29.5°

Increment in 2θ = 0.003°

Refinement

R p = 0.060

R wp = 0.080

R exp = 0.021

R B = 0.088

S = 3.76

Wavelength of incident radiation: 0.6996 Å

Excluded region(s): none

Profile function: pseudo-Voigt profile coefficients as parameterized in Thompson et al. (1987 ▶), asymmetry correction according to Finger et al. (1994 ▶)

617 reflections

100 parameters

96 restraints

H-atom parameters not refined

Preferred orientation correction: March–Dollase (Dollase, 1986 ▶); direction of preferred orientation - 011, MD = 1.26

Data collection: ESRF SPEC package (Certified Scientific Software, 2003 ▶); cell refinement: GSAS (Larson & Von Dreele, 1994 ▶); data reduction: CRYSFIRE (Shirley, 2000 ▶); program(s) used to solve structure: FOX (Favre-Nicolin & Černý, 2002 ▶); program(s) used to refine structure: GSAS; molecular graphics: Mercury (Macrae et al., 2006 ▶) and PLATON (Spek, 2003 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809050351/cv2630sup1.cif

Rietveld powder data: contains datablocks I. DOI: 10.1107/S1600536809050351/cv2630Isup2.rtv

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

C20H26N3O2+·C4H3O4−	F(000) = 960.0
Mr = 455.51	Dx = 1.246 Mg m−3
Orthorhombic, P212121	Synchrotron radiation, λ = 0.6996 Å
a = 5.71027 (5) Å	T = 293 K
b = 12.76978 (17) Å	Particle morphology: needle
c = 33.1455 (4) Å	white
V = 2416.93 (5) Å3	cylinder, 40 × 1 mm
Z = 4	Specimen preparation: Prepared at 293 K and 101 kPa

ID31 diffractometer	Data collection mode: transmission
Radiation source: X-Ray	Scan method: step
Si(111)	2θmin = 0.52°, 2θmax = 29.49°, 2θstep = 0.003°
Specimen mounting: 1.0 mm borosilicate glass capillary

Least-squares matrix: full	Profile function: Pseudo-Voigt profile coefficients as parameterized in Thompson et al. (1987), asymmetry correction according to Finger et al. (1994)
Rp = 0.060	100 parameters
Rwp = 0.080	96 restraints
Rexp = 0.021	0 constraints
RBragg = 0.088	H-atom parameters not refined
R(F2) = 0.08232	Weighting scheme based on measured s.u.'s w = 1/σ(Yobs)2
χ2 = 14.138	(Δ/σ)max = 0.03
11591 data points	Background function: Shifted Chebyschev
Excluded region(s): no	Preferred orientation correction: March–Dollase (Dollase, 1986); direction of preferred orientation - 011, MD = 1.26

	x	y	z	Uiso*/Ueq
N1	−0.2972 (5)	0.6888 (3)	0.29856 (7)	0.07305*
C2	−0.1311 (5)	0.6344 (2)	0.27627 (8)	0.04511*
C3	−0.0706 (4)	0.6910 (2)	0.24331 (7)	0.03699*
C4	−0.2019 (3)	0.7843 (2)	0.24509 (6)	0.03942*
C5	−0.3442 (4)	0.7819 (3)	0.27994 (6)	0.05116*
C6	−0.4884 (4)	0.8647 (3)	0.28782 (7)	0.04053*
C7	−0.4901 (4)	0.9470 (3)	0.26187 (8)	0.03292*
C8	−0.3485 (4)	0.9500 (2)	0.22692 (7)	0.02676*
C9	−0.2006 (3)	0.86750 (18)	0.21789 (6)	0.04409*
C10	−0.0383 (3)	0.85683 (16)	0.18355 (6)	0.05585*
C11	0.0703 (5)	0.66917 (18)	0.20642 (8)	0.01406*
C12	0.1520 (3)	0.77235 (18)	0.18765 (6)	0.02621*
N13	0.2572 (4)	0.7525 (2)	0.14658 (7)	0.02834*
C14	0.4543 (6)	0.6780 (3)	0.14769 (10)	0.04728*
C15	0.3333 (4)	0.8518 (2)	0.12743 (7)	0.0149*
C16	−0.0506 (3)	0.9178 (3)	0.15108 (8)	0.01827*
C17	0.1276 (3)	0.9217 (2)	0.11776 (6)	0.05457*
C18	0.2054 (3)	1.0353 (2)	0.11406 (5)	0.01555*
O19	0.3842 (5)	1.0675 (3)	0.13078 (10)	0.03564*
N20	0.0695 (5)	1.0956 (2)	0.09146 (10)	0.0567*
C21	0.0846 (6)	1.2096 (2)	0.08735 (7)	0.12048*
C22	−0.1555 (8)	1.2575 (4)	0.09008 (13)	0.13815*
O23	−0.2828 (7)	1.2409 (7)	0.12481 (15)	0.18992*
C24	0.1859 (9)	1.2439 (4)	0.04775 (12)	0.16384*
C25	0.254 (2)	1.3598 (5)	0.0502 (2)	0.24862*
O1s	0.1598 (8)	0.5073 (3)	−0.05735 (10)	0.05346*
O2s	0.3200 (5)	0.6095 (3)	−0.01229 (11)	0.09409*
O3s	−0.0518 (7)	0.6674 (3)	0.09751 (9)	0.05776*
O4s	0.2452 (6)	0.6788 (3)	0.05636 (10)	0.06078*
C5s	0.1379 (6)	0.56141 (17)	−0.02617 (8)	0.06152*
C6s	−0.0894 (5)	0.57248 (19)	−0.00445 (9)	0.0169*
C7s	−0.1334 (5)	0.61043 (19)	0.03209 (9)	0.05644*
C8s	0.0294 (5)	0.65414 (14)	0.06283 (8)	0.01622*
H21	−0.0702	0.5649	0.2836	0.0541*
H61	−0.5833	0.8631	0.3116	0.0486*
H71	−0.5868	1.0027	0.268	0.0395*
H81	−0.3514	1.0068	0.2101	0.0324*
H111	0.2034	0.6252	0.2141	0.0169*
H112	−0.0222	0.629	0.1881	0.0169*
H121	0.273	0.7969	0.2049	0.0315*
H141	0.5132	0.6649	0.1216	0.0567*
H142	0.5746	0.7014	0.165	0.0567*
H143	0.4012	0.6094	0.1585	0.0567*
H151	0.4358	0.8844	0.1458	0.0179*
H152	0.4147	0.8326	0.1036	0.0179*
H161	−0.1831	0.9588	0.1491	0.0219*
H171	0.0579	0.8964	0.0936	0.0655*
H211	0.1864	1.2337	0.1082	0.1804*
H221	−0.1257	1.3314	0.0901	0.2258*
H222	−0.2393	1.2362	0.0685	0.2258*
H241	0.0678	1.2255	0.0272	0.1966*
H242	0.3175	1.1955	0.0415	0.1966*
H251	0.3132	1.3721	0.0222	0.4183*
H252	0.118	1.3943	0.0536	0.4183*
H253	0.3677	1.3643	0.068	0.4183*
H601	−0.223	0.549	−0.019	0.0203*
H701	−0.292	0.61	0.04	0.0677*
H11	−0.3603	0.6651	0.3211	0.0877*
H201	−0.0502	1.0631	0.0811	0.068*
H131	0.148	0.725	0.132	0.0411*
H202	0.285	0.643	0.021	0.1129*
H232	−0.3996	1.2015	0.1235	0.27*

N13—C14	1.474 (4)	N13—H131	0.86
N13—C15	1.483 (4)	N20—H201	0.87
N20—C18	1.325 (4)	C2—H21	0.98
N20—C21	1.465 (4)	C6—H61	0.96
C2—C3	1.355 (4)	C7—H71	0.92
C3—C4	1.409 (3)	C8—H81	0.91
C3—C11	1.490 (4)	C11—H111	0.98
C4—C5	1.413 (3)	C11—H112	0.95
C4—C9	1.393 (3)	C12—H121	0.95
C5—C6	1.365 (5)	C14—H141	0.94
C6—C7	1.358 (5)	C14—H142	0.94
C7—C8	1.413 (3)	C14—H143	0.99
C8—C9	1.383 (3)	C15—H151	0.94
C9—C10	1.474 (3)	C15—H152	0.95
C10—C12	1.538 (3)	C16—H161	0.92
C10—C16	1.330 (4)	C17—H171	0.95
C11—C12	1.530 (3)	C21—H211	0.95
C15—C17	1.510 (3)	C22—H221	0.96
C16—C17	1.503 (3)	C22—H222	0.90
C17—C18	1.522 (4)	C24—H241	0.99
C21—C22	1.504 (6)	C24—H242	0.99
C21—C24	1.500 (5)	C25—H251	1.00
C24—C25	1.532 (9)	C25—H252	0.90
O23—H232	0.84	C25—H253	0.88
N1—H11	0.88
C2—N1—C5	109.2 (2)	C3—C2—H21	126
C12—N13—C14	112.9 (2)	C5—C6—H61	119
C12—N13—C15	111.0 (2)	C7—C6—H61	122
C14—N13—C15	109.8 (2)	C6—C7—H71	117
C18—N20—C21	126.6 (3)	C8—C7—H71	120
N1—C2—C3	109.7 (2)	C7—C8—H81	121
C2—C3—C4	106.4 (2)	C9—C8—H81	119
C2—C3—C11	134.4 (2)	C3—C11—H111	108
C4—C3—C11	118.7 (2)	C3—C11—H112	109
C3—C4—C5	108.8 (2)	C12—C11—H111	111
C3—C4—C9	127.96 (19)	C12—C11—H112	112
C5—C4—C9	123.3 (2)	H111—C11—H112	107
N1—C5—C4	106.0 (3)	N13—C12—H121	108
N1—C5—C6	134.9 (2)	C10—C12—H121	110
C4—C5—C6	119.1 (3)	C11—C12—H121	105
C5—C6—C7	118.8 (2)	N13—C14—H141	111
C6—C7—C8	122.4 (3)	N13—C14—H142	112
C7—C8—C9	120.4 (2)	N13—C14—H143	110
C4—C9—C8	115.97 (19)	H141—C14—H142	111
C4—C9—C10	115.61 (18)	H141—C14—H143	106
C8—C9—C10	128.4 (2)	H142—C14—H143	106
C9—C10—C12	116.18 (17)	N13—C15—H151	106
C9—C10—C16	122.53 (19)	N13—C15—H152	106
C12—C10—C16	121.28 (18)	C17—C15—H151	111
C3—C11—C12	109.71 (19)	C17—C15—H152	111
N13—C12—C10	108.63 (17)	H151—C15—H152	110
N13—C12—C11	110.09 (19)	C10—C16—H161	116
C10—C12—C11	115.12 (17)	C17—C16—H161	119
N13—C15—C17	111.62 (19)	C15—C17—H171	108
C10—C16—C17	125.4 (2)	C16—C17—H171	109
C15—C17—C16	110.6 (2)	C18—C17—H171	112
C15—C17—C18	110.70 (16)	N20—C21—H211	107
C16—C17—C18	106.8 (2)	C22—C21—H211	112
O19—C18—N20	123.1 (3)	C24—C21—H211	108
O19—C18—C17	121.6 (2)	O23—C22—H221	104
N20—C18—C17	115.37 (19)	O23—C22—H222	110
N20—C21—C22	110.2 (3)	C21—C22—H221	104
N20—C21—C24	113.2 (3)	C21—C22—H222	108
C22—C21—C24	106.6 (3)	H221—C22—H222	113
O23—C22—C21	117.9 (4)	C21—C24—H241	106
C21—C24—C25	109.5 (4)	C21—C24—H242	107
C22—O23—H232	118	C25—C24—H241	116
C2—N1—H11	124	C25—C24—H242	115
C5—N1—H11	127	H241—C24—H242	103
C12—N13—H131	107	C24—C25—H251	101
C14—N13—H131	108	C24—C25—H252	105
C15—N13—H131	109	C24—C25—H253	107
C18—N20—H201	114	H251—C25—H252	109
C21—N20—H201	119	H251—C25—H253	111
N1—C2—H21	124	H252—C25—H253	121

D—H···A	D—H	H···A	D···A	D—H···A
O2s—H202···O4s	1.20	1.28	2.479 (5)	179
N13—H131···O3s	0.86	1.77	2.634 (4)	173
O23—H232···O19i	0.83	2.12	2.925 (8)	160
N20—H201···O1sii	0.87	2.04	2.912 (5)	177
N1—H11···O19iii	0.88	2.03	2.852 (4)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2s—H202⋯O4s	1.20	1.28	2.479 (5)	179
N13—H131⋯O3s	0.86	1.77	2.634 (4)	173
O23—H232⋯O19i	0.83	2.12	2.925 (8)	160
N20—H201⋯O1s ii	0.87	2.04	2.912 (5)	177
N1—H11⋯O19iii	0.88	2.03	2.852 (4)	154

Symmetry codes: (i) ; (ii) ; (iii) .