Ergometrinine

Merkel, S.; Köppen, R.; Koch, M.; Emmerling, F.; Nehls, I.

doi:10.1107/S1600536810030825

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2275

https://doi.org/10.1107/S1600536810030825

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Ergometrinine

Stefan Merkel,^a Robert Köppen,^a Matthias Koch,^a Franziska Emmerling ^a ^* and Irene Nehls ^a

^aBAM Federal Institute for Materials Research and Testing, Department Analytical Chemistry, Reference Materials, Richard-Willstätter-Strasse 11, D-12489 Berlin-Adlershof, Germany
^*Correspondence e-mail: franziska.emmerling@bam.de

(Received 21 June 2010; accepted 2 August 2010; online 11 August 2010)

The absolute configuration of ergometrinine, C₁₉H₂₃N₃O₂ {systematic name: (6aR,9S)-N-[(S)-1-hydroxypropan-2-yl]-7-methyl-4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide}, 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 intramolecular 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_r = 325.40
Orthorhombic, P 2₁ 2₁ 2₁
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[F² > 2σ(F²)] = 0.044
wR(F²) = 0.112
S = 1.00
1889 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.16 e Å⁻³

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) $[x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+1]$ ; (ii) x, y+1, z.

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 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030825/sj5027Isup2.hkl

checkCIF report

Comment top

Ergometrinine is one of the main ergot alkaloids produced by the fungus Claviceps purpurea on cereal grains in the field. Contamination of flour and cereal based foods with ergot alkaloids including ergometrinine has previously been reported (Crews et al., 2009, Müller et al., 2009). The biologically inactive C8-(S)-isomer ergometrinine (Pierri et al., 1982) can be converted to the biologically active C8-(R)-isomer ergometrine and vice versa (Komarova & Tolkachev, 2001). The molecule crystallizes in the orthorhombic space group P2₁2₁2₁. The molecular structure of the compound and the atom labeling scheme are shown in Fig 1. The absolute configuration could not be defined confidently based on the single crystal diffraction data. It was however established based on epimerization reaction of ergometrine, whose absolute configuration was determined previously (Cejka et al., 1996). Besides the intramolecular hydrogen bonds between N1-H1N and N2 (not shown in Fig. 2), each molecule is connected to four adjacent molecules via intermolecular hydrogen bonds (see dashed green bonds in Fig. 2). As a result undulating layers are formed in the the ac plane.

Related literature top

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 top

Ergometrine maleate salt was purchased from Sigma-Aldrich (Taufkirchen, Germany). The isomeric purity (> 99%) of ergometrine was proved by HPLC-FLD. The stereoselective conversion of ergometrine to ergometrinine was carried out as follows: 40 mg of ergometrine maleate were placed in a 250 ml round-bottom flask, dissolved in 100 ml methanol and 4 ml 28% ammonium hydroxide solution was added. The resulting mixture was stored at 40 °C in a drying cabinet in darkness for epimerization reaction. After 4 days liquid chromatography showed two different compounds, the reactant ergometrine and the product ergometrinine. Afterwards the solvent was removed in vacuo and the residue of compounds was redissolved in a mixture of water and acetonitrile (70:30, v:v) and subjected to preparative HPLC for separation and purification of the two epimers. Colourless crystals of ergometrinine were grown by slow solvent evaporation from acetonitrile:water (80:20, v:v) in the absence of light at ambient temperature.

Structure description top

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).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); 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).

Figures top

	Fig. 1. : ORTEP representation of the title compound with atomic labeling shown with 30% probability displacement ellipsoids.
	Fig. 2. : View of the unit cell of the title compound along [100], showing the hydrogen-bonded layers stacked along the [001] direction. Hydrogen bonds are drawn as dashed lines.

(6aR,9S)-N-[(S)-1-hydroxypropan-2-yl]-7-methyl- 4,6,6a,7,8,9-hexahydroindolo[4,3-fg]quinoline-9-carboxamide top

Crystal data top

C₁₉H₂₃N₃O₂	F(000) = 696
M_r = 325.40	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0561P)² + 0.0234P] where P = (F_o² + 2F_c²)/3
1889 reflections	(Δ/σ)_max < 0.001
219 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₉H₂₃N₃O₂	V = 1723.01 (17) Å³
M_r = 325.40	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 7.4097 (5) Å	µ = 0.66 mm⁻¹
b = 12.7313 (7) Å	T = 298 K
c = 18.2648 (9) Å	0.20 × 0.05 × 0.02 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1269 reflections with I > 2σ(I)
Absorption correction: ψ scan (CORINC; Dräger & Gattow, 1971)	R_int = 0.056
T_min = 0.879, T_max = 0.986	3 standard reflections every 60 min
4023 measured reflections	intensity decay: 2%
1889 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.00	Δρ_max = 0.14 e Å⁻³
1889 reflections	Δρ_min = −0.16 e Å⁻³
219 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) x+1/2, −y−1/2, −z+1; (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₉H₂₃N₃O₂
M_r	325.40
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	298
a, b, c (Å)	7.4097 (5), 12.7313 (7), 18.2648 (9)
V (Å³)	1723.01 (17)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.66
Crystal size (mm)	0.20 × 0.05 × 0.02

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (CORINC; Dräger & Gattow, 1971)
T_min, T_max	0.879, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	4023, 1889, 1269
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.112, 1.00
No. of reflections	1889
No. of parameters	219
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.16

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), CORINC (Dräger & Gattow, 1971), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N2	0.97	2.10	2.890 (4)	137.6
O2—H2O···O1ⁱ	1.01	1.68	2.684 (3)	172.0
N3—H3N···O2ⁱⁱ	0.95	1.97	2.918 (4)	172.5

Symmetry codes: (i) x+1/2, −y−1/2, −z+1; (ii) x, y+1, z.

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
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