Ergotaminine.

The title compound {systematic name: (6aR,9S)-N-[(2R,5S,10aS,10bS)-5-benzyl-10b-hy-droxy-2-methyl-3,6-dioxoocta-hydro-8H-oxazolo[3,2-a]pyrrolo-[2,1-c]pyrazin-2-yl]-7-methyl-4,6,6a,7,8,9-hexa-hydro-indolo[4,3-fg]quinoline-9-carboxamide}, C(33)H(35)N(5)O(5), was formed by an epimerization reaction of ergotamine. The non-aromatic ring (ring C of the ergoline skeleton) directly fused to the aromatic rings is nearly planar [maximum deviation = 0.317 (4) Å] and shows an envelope conformation, whereas ring D, involved in an intra-molecular N-H⋯N hydrogen bond exhibits a slightly distorted chair conformation. The structure displays chains running approximately parallel to the diagonal of bc plane that are formed through N-H⋯O hydrogen bonds.

Related literature

Ergotaminine is an ergot alkaloid formed by, among others, the fungus Claviceps purpurea on cereal grains and grasses during the growth process; see: Crews et al. (2009 ▶); Müller et al. (2009 ▶). For investigations of the biologically inactive C8-(S)-isomer ergotaminine, see: Pierri et al. (1982 ▶); Komarova & Tolkachev (2001 ▶). For the crystal structure of ergotamine tartrate ethanol solvate, see: Pakhomova et al. (1995 ▶). For the crystal structure of ergometrinine, another C8-(S)-configured ergotalkaloid, see: Merkel et al. (2010 ▶). For the solubility of ergotaminine, see: Stoll (1945 ▶).

Experimental

Crystal data

C33H35N5O5

M = 581.66

Monoclinic,

a = 10.974 (3) Å

b = 9.662 (2) Å

c = 14.450 (4) Å

β = 105.059 (15)°

V = 1479.5 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.2 × 0.1 × 0.06 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.879, T max = 0.986

20196 measured reflections

2781 independent reflections

2240 reflections with I > 2σ(I)

R int = 0.087

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.093

S = 1.12

2781 reflections

390 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.15 e Å−3

Δρmin = −0.19 e Å−3

Absolute structure: determined from the synthesis

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812003674/ds2173sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003674/ds2173Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812003674/ds2173Isup3.mol

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

C33H35N5O5	F(000) = 616
Mr = 581.66	Dx = 1.306 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 86 reflections
a = 10.974 (3) Å	θ = 4–29°
b = 9.662 (2) Å	µ = 0.09 mm−1
c = 14.450 (4) Å	T = 296 K
β = 105.059 (15)°	Plate, colourless
V = 1479.5 (7) Å3	0.2 × 0.1 × 0.06 mm
Z = 2

Bruker APEX CCD area-detector diffractometer	2781 independent reflections
Radiation source: fine-focus sealed tube	2240 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
ω/2θ scans	θmax = 25.1°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→12
Tmin = 0.879, Tmax = 0.986	k = −11→11
20196 measured reflections	l = −14→17

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)] = 0.047	H-atom parameters constrained
wR(F2) = 0.093	w = 1/[σ2(Fo2) + (0.0345P)2] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max < 0.001
2781 reflections	Δρmax = 0.15 e Å−3
390 parameters	Δρmin = −0.19 e Å−3
1 restraint	Absolute structure: syn
Primary atom site location: structure-invariant direct methods

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	0.2567 (2)	0.1765 (2)	0.57682 (16)	0.0564 (7)
O2	0.3529 (2)	0.2000 (2)	0.45142 (16)	0.0526 (6)
H1	0.3525	0.2846	0.4559	0.079*
O3	−0.0202 (3)	0.3535 (3)	0.45451 (19)	0.0753 (8)
O4	0.2943 (3)	0.4688 (3)	0.52044 (19)	0.0787 (9)
O5	0.0781 (3)	−0.0063 (3)	0.21039 (18)	0.0726 (8)
N1	0.1306 (2)	0.2059 (3)	0.42571 (18)	0.0458 (7)
N2	0.2054 (3)	0.3898 (3)	0.6360 (2)	0.0589 (8)
H2	0.1851	0.4118	0.6877	0.071*
N3	0.3774 (3)	0.4339 (3)	0.8282 (2)	0.0594 (8)
N4	0.1372 (4)	0.7970 (5)	1.0691 (3)	0.0918 (13)
H3	0.1068	0.8344	1.1123	0.110*
N5	0.2018 (2)	−0.0396 (3)	0.36023 (19)	0.0478 (7)
C1	0.2503 (3)	0.1457 (3)	0.4785 (2)	0.0438 (8)
C2	0.0775 (3)	0.2859 (4)	0.4814 (3)	0.0529 (9)
C3	0.1537 (3)	0.2655 (4)	0.5853 (2)	0.0513 (9)
C4	0.2866 (4)	0.4728 (4)	0.6038 (3)	0.0606 (10)
C5	0.3716 (4)	0.5658 (4)	0.6793 (3)	0.0626 (11)
H4	0.4299	0.6130	0.6487	0.075*
C6	0.4514 (4)	0.4756 (4)	0.7608 (3)	0.0710 (12)
H5	0.4799	0.3936	0.7338	0.085*
H6	0.5253	0.5270	0.7951	0.085*
C7	0.3456 (3)	0.5530 (4)	0.8811 (3)	0.0563 (10)
H7	0.4227	0.5813	0.9287	0.068*
C8	0.2471 (4)	0.5103 (4)	0.9358 (3)	0.0649 (11)
H8	0.1736	0.4707	0.8913	0.078*
H9	0.2830	0.4407	0.9834	0.078*
C9	0.2085 (4)	0.6349 (5)	0.9840 (3)	0.0637 (11)
C10	0.1623 (4)	0.6591 (6)	1.0624 (3)	0.0858 (14)
H10	0.1499	0.5914	1.1048	0.103*
C11	0.1678 (4)	0.8663 (5)	0.9949 (3)	0.0732 (12)
C12	0.2133 (3)	0.7655 (4)	0.9420 (3)	0.0573 (10)
C13	0.2523 (3)	0.7954 (4)	0.8593 (3)	0.0532 (9)
C14	0.3004 (3)	0.6764 (4)	0.8136 (2)	0.0487 (9)
C15	0.3054 (3)	0.6754 (4)	0.7218 (3)	0.0548 (9)
H11	0.2654	0.7467	0.6822	0.066*
C16	0.2457 (4)	0.9325 (4)	0.8304 (3)	0.0661 (11)
H12	0.2718	0.9580	0.7765	0.079*
C17	0.1988 (4)	1.0347 (4)	0.8837 (3)	0.0831 (14)
H13	0.1944	1.1262	0.8631	0.100*
C18	0.1594 (4)	1.0026 (6)	0.9656 (3)	0.0841 (15)
H14	0.1286	1.0705	0.9991	0.101*
C19	0.4491 (5)	0.3282 (5)	0.8935 (3)	0.0904 (14)
H15	0.4720	0.2545	0.8567	0.136*
H16	0.3980	0.2920	0.9326	0.136*
H17	0.5240	0.3690	0.9336	0.136*
C20	0.0706 (4)	0.1934 (5)	0.6393 (3)	0.0718 (11)
H18	0.0020	0.2532	0.6426	0.108*
H19	0.1195	0.1718	0.7030	0.108*
H20	0.0378	0.1095	0.6066	0.108*
C21	0.0681 (3)	0.1685 (4)	0.3258 (2)	0.0502 (9)
H21	−0.0208	0.1523	0.3235	0.060*
C22	0.1174 (3)	0.0328 (4)	0.2951 (3)	0.0507 (9)
C23	0.2471 (3)	−0.0094 (4)	0.4643 (2)	0.0470 (8)
H22	0.1881	−0.0499	0.4973	0.056*
C24	0.3714 (4)	−0.0875 (4)	0.4936 (3)	0.0651 (11)
H23	0.4400	−0.0325	0.4822	0.078*
H24	0.3914	−0.1134	0.5607	0.078*
C25	0.3467 (4)	−0.2143 (4)	0.4293 (3)	0.0805 (13)
H25	0.3059	−0.2862	0.4573	0.097*
H26	0.4252	−0.2505	0.4202	0.097*
C26	0.2613 (4)	−0.1660 (4)	0.3349 (3)	0.0577 (10)
H27	0.3097	−0.1456	0.2891	0.069*
H28	0.1984	−0.2355	0.3080	0.069*
C27	0.0694 (4)	0.2867 (4)	0.2538 (3)	0.0658 (11)
H29	0.0173	0.2584	0.1917	0.079*
H30	0.0296	0.3669	0.2737	0.079*
C28	0.1947 (4)	0.3310 (4)	0.2411 (2)	0.0551 (10)
C29	0.2512 (5)	0.2625 (5)	0.1781 (3)	0.0706 (12)
H31	0.2115	0.1859	0.1443	0.085*
C30	0.3658 (5)	0.3069 (5)	0.1651 (3)	0.0863 (15)
H32	0.4021	0.2597	0.1229	0.104*
C31	0.4258 (5)	0.4192 (6)	0.2138 (4)	0.0921 (15)
H33	0.5020	0.4494	0.2041	0.110*
C32	0.3729 (5)	0.4871 (5)	0.2769 (3)	0.0867 (13)
H34	0.4143	0.5624	0.3113	0.104*
C33	0.2586 (4)	0.4445 (4)	0.2899 (3)	0.0667 (11)
H35	0.2234	0.4927	0.3323	0.080*

	U11	U22	U33	U12	U13	U23
O1	0.0583 (15)	0.0628 (17)	0.0461 (14)	0.0085 (13)	0.0098 (12)	−0.0074 (12)
O2	0.0457 (13)	0.0436 (13)	0.0695 (15)	−0.0059 (11)	0.0167 (12)	0.0008 (12)
O3	0.0698 (18)	0.077 (2)	0.0795 (18)	0.0295 (17)	0.0199 (15)	−0.0057 (16)
O4	0.127 (3)	0.0594 (17)	0.0620 (17)	−0.0228 (17)	0.0460 (17)	−0.0118 (14)
O5	0.0844 (19)	0.0737 (18)	0.0501 (15)	0.0090 (16)	0.0004 (14)	−0.0174 (14)
N1	0.0429 (15)	0.0467 (16)	0.0466 (16)	0.0038 (14)	0.0095 (13)	−0.0067 (14)
N2	0.078 (2)	0.0510 (18)	0.0569 (19)	−0.0101 (16)	0.0347 (17)	−0.0146 (15)
N3	0.0624 (19)	0.0521 (19)	0.0624 (19)	0.0094 (16)	0.0140 (16)	−0.0056 (16)
N4	0.107 (3)	0.116 (4)	0.056 (2)	0.025 (3)	0.027 (2)	−0.015 (2)
N5	0.0486 (16)	0.0409 (16)	0.0509 (16)	0.0013 (13)	0.0077 (13)	−0.0074 (13)
C1	0.0418 (19)	0.0470 (19)	0.0424 (19)	−0.0020 (16)	0.0107 (16)	−0.0030 (15)
C2	0.053 (2)	0.046 (2)	0.062 (2)	0.0042 (19)	0.0190 (19)	−0.0042 (18)
C3	0.057 (2)	0.047 (2)	0.053 (2)	0.0019 (18)	0.0218 (18)	−0.0087 (17)
C4	0.080 (3)	0.051 (2)	0.058 (2)	−0.008 (2)	0.031 (2)	−0.013 (2)
C5	0.071 (3)	0.056 (2)	0.071 (3)	−0.014 (2)	0.037 (2)	−0.018 (2)
C6	0.059 (2)	0.065 (3)	0.093 (3)	0.000 (2)	0.026 (2)	−0.021 (3)
C7	0.054 (2)	0.056 (2)	0.054 (2)	0.0060 (19)	0.0054 (18)	−0.0090 (18)
C8	0.069 (3)	0.064 (3)	0.061 (2)	0.001 (2)	0.016 (2)	0.004 (2)
C9	0.061 (2)	0.082 (3)	0.047 (2)	0.008 (2)	0.012 (2)	−0.001 (2)
C10	0.095 (3)	0.109 (4)	0.054 (3)	0.013 (3)	0.022 (3)	0.004 (3)
C11	0.073 (3)	0.093 (4)	0.047 (2)	0.014 (3)	0.005 (2)	−0.017 (2)
C12	0.053 (2)	0.070 (3)	0.044 (2)	0.005 (2)	0.0044 (18)	−0.014 (2)
C13	0.051 (2)	0.053 (2)	0.051 (2)	0.0027 (18)	0.0046 (17)	−0.0153 (18)
C14	0.0437 (19)	0.052 (2)	0.049 (2)	−0.0028 (17)	0.0092 (16)	−0.0082 (17)
C15	0.060 (2)	0.048 (2)	0.058 (2)	−0.0043 (18)	0.0192 (19)	−0.0085 (18)
C16	0.071 (3)	0.064 (3)	0.060 (2)	0.005 (2)	0.013 (2)	−0.012 (2)
C17	0.100 (3)	0.059 (3)	0.081 (3)	0.017 (2)	0.007 (3)	−0.021 (2)
C18	0.094 (3)	0.094 (4)	0.056 (3)	0.025 (3)	0.005 (2)	−0.033 (3)
C19	0.091 (3)	0.070 (3)	0.100 (3)	0.023 (3)	0.006 (3)	0.006 (3)
C20	0.083 (3)	0.067 (3)	0.074 (3)	−0.011 (2)	0.036 (2)	−0.003 (2)
C21	0.0438 (19)	0.050 (2)	0.053 (2)	0.0042 (17)	0.0063 (16)	−0.0035 (17)
C22	0.047 (2)	0.051 (2)	0.052 (2)	0.0033 (17)	0.0077 (17)	−0.0039 (17)
C23	0.0468 (19)	0.0442 (18)	0.050 (2)	0.0003 (16)	0.0123 (16)	−0.0009 (16)
C24	0.068 (3)	0.049 (2)	0.070 (2)	0.009 (2)	0.003 (2)	0.001 (2)
C25	0.085 (3)	0.056 (2)	0.089 (3)	0.018 (2)	0.003 (2)	−0.012 (2)
C26	0.059 (2)	0.047 (2)	0.070 (2)	0.0059 (19)	0.021 (2)	−0.0106 (19)
C27	0.072 (3)	0.068 (3)	0.053 (2)	0.023 (2)	0.007 (2)	0.002 (2)
C28	0.067 (3)	0.050 (2)	0.046 (2)	0.0169 (19)	0.0103 (19)	0.0089 (18)
C29	0.093 (3)	0.065 (3)	0.058 (2)	0.014 (3)	0.028 (2)	−0.003 (2)
C30	0.116 (4)	0.075 (3)	0.081 (3)	0.034 (3)	0.049 (3)	0.013 (3)
C31	0.085 (3)	0.084 (4)	0.117 (4)	0.019 (3)	0.044 (3)	0.031 (3)
C32	0.091 (4)	0.070 (3)	0.094 (3)	0.001 (3)	0.015 (3)	0.003 (3)
C33	0.086 (3)	0.055 (3)	0.060 (2)	0.010 (2)	0.022 (2)	−0.001 (2)

O1—C1	1.435 (4)	C13—C16	1.385 (5)
O1—C3	1.451 (4)	C13—C14	1.490 (5)
O2—C1	1.388 (4)	C14—C15	1.340 (5)
O2—H1	0.8201	C15—H11	0.9300
O3—C2	1.229 (4)	C16—C17	1.428 (6)
O4—C4	1.230 (4)	C16—H12	0.9300
O5—C22	1.246 (4)	C17—C18	1.396 (6)
N1—C2	1.353 (4)	C17—H13	0.9300
N1—C1	1.458 (4)	C18—H14	0.9300
N1—C21	1.474 (4)	C19—H15	0.9600
N2—C4	1.367 (5)	C19—H16	0.9600
N2—C3	1.444 (4)	C19—H17	0.9600
N2—H2	0.8600	C20—H18	0.9600
N3—C19	1.472 (5)	C20—H19	0.9600
N3—C7	1.472 (4)	C20—H20	0.9600
N3—C6	1.477 (5)	C21—C22	1.527 (5)
N4—C10	1.369 (6)	C21—C27	1.547 (5)
N4—C11	1.378 (6)	C21—H21	0.9800
N4—H3	0.8600	C23—C24	1.519 (5)
N5—C22	1.334 (4)	C23—H22	0.9800
N5—C26	1.475 (4)	C24—C25	1.519 (6)
N5—C23	1.485 (4)	C24—H23	0.9700
C1—C23	1.512 (5)	C24—H24	0.9700
C2—C3	1.529 (5)	C25—C26	1.514 (5)
C3—C20	1.515 (5)	C25—H25	0.9700
C4—C5	1.530 (5)	C25—H26	0.9700
C5—C15	1.503 (5)	C26—H27	0.9700
C5—C6	1.542 (6)	C26—H28	0.9700
C5—H4	0.9800	C27—C28	1.495 (5)
C6—H5	0.9700	C27—H29	0.9700
C6—H6	0.9700	C27—H30	0.9700
C7—C14	1.539 (5)	C28—C33	1.391 (5)
C7—C8	1.552 (5)	C28—C29	1.395 (5)
C7—H7	0.9800	C29—C30	1.387 (6)
C8—C9	1.506 (5)	C29—H31	0.9300
C8—H8	0.9700	C30—C31	1.366 (7)
C8—H9	0.9700	C30—H32	0.9300
C9—C10	1.376 (5)	C31—C32	1.370 (6)
C9—C12	1.407 (6)	C31—H33	0.9300
C10—H10	0.9300	C32—C33	1.378 (6)
C11—C18	1.379 (7)	C32—H34	0.9300
C11—C12	1.406 (5)	C33—H35	0.9300
C12—C13	1.400 (5)
C1—O1—C3	111.6 (2)	C5—C15—H11	118.1
C1—O2—H1	109.5	C13—C16—C17	119.8 (4)
C2—N1—C1	112.7 (3)	C13—C16—H12	120.1
C2—N1—C21	124.1 (3)	C17—C16—H12	120.1
C1—N1—C21	122.8 (3)	C18—C17—C16	122.5 (4)
C4—N2—C3	121.4 (3)	C18—C17—H13	118.7
C4—N2—H2	119.3	C16—C17—H13	118.7
C3—N2—H2	119.4	C11—C18—C17	117.5 (4)
C19—N3—C7	111.6 (3)	C11—C18—H14	121.3
C19—N3—C6	108.5 (3)	C17—C18—H14	121.3
C7—N3—C6	112.0 (3)	N3—C19—H15	109.5
C10—N4—C11	108.9 (4)	N3—C19—H16	109.5
C10—N4—H3	125.7	H15—C19—H16	109.5
C11—N4—H3	125.5	N3—C19—H17	109.5
C22—N5—C26	122.0 (3)	H15—C19—H17	109.5
C22—N5—C23	126.8 (3)	H16—C19—H17	109.5
C26—N5—C23	111.1 (3)	C3—C20—H18	109.5
O2—C1—O1	111.5 (3)	C3—C20—H19	109.5
O2—C1—N1	112.8 (3)	H18—C20—H19	109.5
O1—C1—N1	104.0 (2)	C3—C20—H20	109.5
O2—C1—C23	109.2 (3)	H18—C20—H20	109.5
O1—C1—C23	109.5 (3)	H19—C20—H20	109.5
N1—C1—C23	109.8 (3)	N1—C21—C22	112.7 (3)
O3—C2—N1	126.2 (3)	N1—C21—C27	113.2 (3)
O3—C2—C3	126.1 (3)	C22—C21—C27	111.9 (3)
N1—C2—C3	107.5 (3)	N1—C21—H21	106.1
N2—C3—O1	108.9 (3)	C22—C21—H21	106.1
N2—C3—C20	109.3 (3)	C27—C21—H21	106.1
O1—C3—C20	110.9 (3)	O5—C22—N5	122.3 (3)
N2—C3—C2	115.7 (3)	O5—C22—C21	119.1 (3)
O1—C3—C2	103.4 (3)	N5—C22—C21	118.6 (3)
C20—C3—C2	108.5 (3)	N5—C23—C1	108.8 (3)
O4—C4—N2	122.1 (3)	N5—C23—C24	103.0 (3)
O4—C4—C5	122.2 (4)	C1—C23—C24	117.8 (3)
N2—C4—C5	115.7 (3)	N5—C23—H22	108.9
C15—C5—C4	115.8 (3)	C1—C23—H22	108.9
C15—C5—C6	109.0 (3)	C24—C23—H22	108.9
C4—C5—C6	109.4 (3)	C25—C24—C23	103.0 (3)
C15—C5—H4	107.4	C25—C24—H23	111.2
C4—C5—H4	107.4	C23—C24—H23	111.2
C6—C5—H4	107.4	C25—C24—H24	111.2
N3—C6—C5	110.9 (3)	C23—C24—H24	111.2
N3—C6—H5	109.5	H23—C24—H24	109.1
C5—C6—H5	109.5	C24—C25—C26	105.8 (3)
N3—C6—H6	109.5	C24—C25—H25	110.6
C5—C6—H6	109.5	C26—C25—H25	110.6
H5—C6—H6	108.0	C24—C25—H26	110.6
N3—C7—C14	110.9 (3)	C26—C25—H26	110.6
N3—C7—C8	110.3 (3)	H25—C25—H26	108.7
C14—C7—C8	112.1 (3)	N5—C26—C25	104.0 (3)
N3—C7—H7	107.8	N5—C26—H27	111.0
C14—C7—H7	107.8	C25—C26—H27	111.0
C8—C7—H7	107.8	N5—C26—H28	111.0
C9—C8—C7	109.9 (3)	C25—C26—H28	111.0
C9—C8—H8	109.7	H27—C26—H28	109.0
C7—C8—H8	109.7	C28—C27—C21	117.6 (3)
C9—C8—H9	109.7	C28—C27—H29	107.9
C7—C8—H9	109.7	C21—C27—H29	107.9
H8—C8—H9	108.2	C28—C27—H30	107.9
C10—C9—C12	105.4 (4)	C21—C27—H30	107.9
C10—C9—C8	136.4 (4)	H29—C27—H30	107.2
C12—C9—C8	118.1 (3)	C33—C28—C29	117.0 (4)
N4—C10—C9	110.3 (4)	C33—C28—C27	121.5 (4)
N4—C10—H10	124.8	C29—C28—C27	121.5 (4)
C9—C10—H10	124.8	C30—C29—C28	121.0 (4)
N4—C11—C18	133.8 (4)	C30—C29—H31	119.5
N4—C11—C12	106.2 (4)	C28—C29—H31	119.5
C18—C11—C12	120.0 (4)	C31—C30—C29	120.6 (5)
C13—C12—C11	123.4 (4)	C31—C30—H32	119.7
C13—C12—C9	127.4 (3)	C29—C30—H32	119.7
C11—C12—C9	109.2 (4)	C30—C31—C32	119.5 (5)
C16—C13—C12	116.8 (3)	C30—C31—H33	120.3
C16—C13—C14	127.0 (3)	C32—C31—H33	120.3
C12—C13—C14	116.2 (3)	C31—C32—C33	120.4 (5)
C15—C14—C13	123.6 (3)	C31—C32—H34	119.8
C15—C14—C7	122.2 (3)	C33—C32—H34	119.8
C13—C14—C7	114.2 (3)	C32—C33—C28	121.6 (4)
C14—C15—C5	123.9 (4)	C32—C33—H35	119.2
C14—C15—H11	118.1	C28—C33—H35	119.2
C3—O1—C1—O2	115.5 (3)	C9—C12—C13—C14	−3.5 (5)
C3—O1—C1—N1	−6.4 (3)	C16—C13—C14—C15	−23.1 (6)
C3—O1—C1—C23	−123.6 (3)	C12—C13—C14—C15	159.1 (3)
C2—N1—C1—O2	−111.3 (3)	C16—C13—C14—C7	156.5 (4)
C21—N1—C1—O2	75.9 (4)	C12—C13—C14—C7	−21.3 (4)
C2—N1—C1—O1	9.6 (4)	N3—C7—C14—C15	−7.1 (5)
C21—N1—C1—O1	−163.2 (3)	C8—C7—C14—C15	−130.9 (4)
C2—N1—C1—C23	126.7 (3)	N3—C7—C14—C13	173.2 (3)
C21—N1—C1—C23	−46.1 (4)	C8—C7—C14—C13	49.5 (4)
C1—N1—C2—O3	176.7 (4)	C13—C14—C15—C5	170.2 (3)
C21—N1—C2—O3	−10.6 (6)	C7—C14—C15—C5	−9.4 (5)
C1—N1—C2—C3	−8.9 (4)	C4—C5—C15—C14	113.1 (4)
C21—N1—C2—C3	163.8 (3)	C6—C5—C15—C14	−10.7 (5)
C4—N2—C3—O1	56.9 (4)	C12—C13—C16—C17	−1.0 (5)
C4—N2—C3—C20	178.3 (3)	C14—C13—C16—C17	−178.8 (4)
C4—N2—C3—C2	−59.0 (5)	C13—C16—C17—C18	0.5 (6)
C1—O1—C3—N2	−122.1 (3)	N4—C11—C18—C17	−178.9 (4)
C1—O1—C3—C20	117.6 (3)	C12—C11—C18—C17	−0.8 (7)
C1—O1—C3—C2	1.5 (4)	C16—C17—C18—C11	0.5 (7)
O3—C2—C3—N2	−62.1 (5)	C2—N1—C21—C22	−154.1 (3)
N1—C2—C3—N2	123.5 (3)	C1—N1—C21—C22	17.9 (4)
O3—C2—C3—O1	178.9 (4)	C2—N1—C21—C27	77.7 (4)
N1—C2—C3—O1	4.5 (4)	C1—N1—C21—C27	−110.3 (3)
O3—C2—C3—C20	61.1 (5)	C26—N5—C22—O5	4.5 (5)
N1—C2—C3—C20	−113.3 (3)	C23—N5—C22—O5	−174.5 (3)
C3—N2—C4—O4	19.6 (6)	C26—N5—C22—C21	−175.2 (3)
C3—N2—C4—C5	−157.6 (3)	C23—N5—C22—C21	5.7 (5)
O4—C4—C5—C15	117.7 (4)	N1—C21—C22—O5	−175.5 (3)
N2—C4—C5—C15	−65.1 (5)	C27—C21—C22—O5	−46.7 (4)
O4—C4—C5—C6	−118.7 (4)	N1—C21—C22—N5	4.2 (4)
N2—C4—C5—C6	58.5 (4)	C27—C21—C22—N5	133.1 (3)
C19—N3—C6—C5	169.6 (3)	C22—N5—C23—C1	−33.7 (4)
C7—N3—C6—C5	−66.7 (4)	C26—N5—C23—C1	147.2 (3)
C15—C5—C6—N3	47.1 (4)	C22—N5—C23—C24	−159.5 (3)
C4—C5—C6—N3	−80.4 (4)	C26—N5—C23—C24	21.4 (4)
C19—N3—C7—C14	166.1 (3)	O2—C1—C23—N5	−74.8 (3)
C6—N3—C7—C14	44.2 (4)	O1—C1—C23—N5	162.9 (2)
C19—N3—C7—C8	−69.1 (4)	N1—C1—C23—N5	49.3 (3)
C6—N3—C7—C8	169.0 (3)	O2—C1—C23—C24	41.9 (4)
N3—C7—C8—C9	−176.1 (3)	O1—C1—C23—C24	−80.4 (4)
C14—C7—C8—C9	−52.0 (4)	N1—C1—C23—C24	166.0 (3)
C7—C8—C9—C10	−154.0 (5)	N5—C23—C24—C25	−33.9 (4)
C7—C8—C9—C12	28.8 (5)	C1—C23—C24—C25	−153.6 (3)
C11—N4—C10—C9	−0.5 (6)	C23—C24—C25—C26	35.2 (4)
C12—C9—C10—N4	0.9 (5)	C22—N5—C26—C25	−178.9 (3)
C8—C9—C10—N4	−176.5 (4)	C23—N5—C26—C25	0.2 (4)
C10—N4—C11—C18	178.1 (5)	C24—C25—C26—N5	−22.0 (4)
C10—N4—C11—C12	−0.1 (5)	N1—C21—C27—C28	65.2 (4)
N4—C11—C12—C13	178.8 (3)	C22—C21—C27—C28	−63.3 (4)
C18—C11—C12—C13	0.2 (6)	C21—C27—C28—C33	−96.9 (4)
N4—C11—C12—C9	0.7 (5)	C21—C27—C28—C29	84.6 (4)
C18—C11—C12—C9	−177.8 (4)	C33—C28—C29—C30	−0.2 (5)
C10—C9—C12—C13	−179.0 (4)	C27—C28—C29—C30	178.3 (4)
C8—C9—C12—C13	−1.0 (6)	C28—C29—C30—C31	−0.1 (6)
C10—C9—C12—C11	−1.0 (4)	C29—C30—C31—C32	1.0 (7)
C8—C9—C12—C11	177.0 (3)	C30—C31—C32—C33	−1.4 (7)
C11—C12—C13—C16	0.7 (5)	C31—C32—C33—C28	1.1 (6)
C9—C12—C13—C16	178.4 (4)	C29—C28—C33—C32	−0.2 (5)
C11—C12—C13—C14	178.7 (3)	C27—C28—C33—C32	−178.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N3	0.86	2.53	2.955 (4)	112
N4—H3···O5i	0.86	2.17	2.981 (5)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N3	0.86	2.53	2.955 (4)	112
N4—H3⋯O5i	0.86	2.17	2.981 (5)	157

Symmetry code: (i) .