5,7-Diacetyl-13-benzyl-7,8-dihydro-5H,8aH,13H-di­indolo[2,3-c;2,3-d]pyrimidin-8-yl acetate, the result of an intra­molecular cyclo­addition between an N-benzyl­indole and a 1,2,4,5-tetra­zine

An intra­molecular Diels–Alder-type cyclo­addition between an indole and a 1,2,4,5-tetra­zine produced the title compound, C₂₉H₂₆N₄O₄, the first example of a penta­heterocyclic structure obtained via loss of nitro­gen and addition of the elements of acetic anhydride. Of the four N atoms in the mol­ecule, one is in a dihydro­indole, while the other three are in an N,N′-diacyl­amidrazone unit, of which there are no previous examples. The N,N′-diacyl­amidrazone is almost planar and is involved in π–π stacking with the N-benzyl phenyl ring. There are inter­molecular C—H...O hydrogen bonds, linking the mol­ecules into chains.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.045
• wR factor = 0.115
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Datablock: 3


Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000)         200 Deg.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART [PLEASE PROVIDE YEAR/VERSION NUMBER/REFERENCE]; cell refinement: SMART; data reduction: SAINT [PLEASE PROVIDE YEAR/VERSION NUMBER/REFERENCE]; program(s) used to solve structure: SHELXTL [PLEASE PROVIDE YEAR/VERSION NUMBER/REFERENCE]; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

5,7-diacetyl-13-benzyl-7,8-dihydro-5H,8aH,13H-diindolo[2,3 - c;2,3 - d]pyrimidin- 8-yl acetate

Crystal data

C29H26N4O4	Z = 2
Mr = 494.54	F(000) = 520
Triclinic, P1	Dx = 1.377 Mg m^−3
a = 9.8170 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.2404 (14) Å	Cell parameters from 2177 reflections
c = 11.5762 (14) Å	θ = 2.2–28.0°
α = 109.371 (2)°	µ = 0.09 mm^−1
β = 95.624 (2)°	T = 100 K
γ = 93.782 (2)°	Plate, yellow
V = 1192.7 (3) Å^3	0.60 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	5269 independent reflections
Radiation source: fine-focus sealed tube	4159 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
φ and ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→13
Tmin = 0.946, Tmax = 0.991	k = −14→14
7514 measured reflections	l = −14→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0523P)^2 + 0.4497P] where P = (Fo^2 + 2Fc^2)/3
5269 reflections	(Δ/σ)max < 0.001
337 parameters	Δρmax = 0.42 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Special details

Experimental. Preparation of 1-benzyl-2-(2-nitrophenyl)indole: to an ice-cooled stirred solution of hexane-washed sodium hydride (177 mg, 4.6 mmol) in DMF (10 ml, anhydrous) under N₂, a solution of 2-(o-nitrophenyl)indole (Dalton et al., 1983) (1 g, 4.2 mmol) in DMF (5 ml, anhydrous) was added over a period of 15 min. The mixture was left for a further 15 min, then benzyl bromide (1.1 ml, 9.2 mmol) was added dropwise, and the mixture left for 1 h at 273 K. The reaction was quenched with saturated aqueous NH₄Cl, CH₂Cl₂ (10 ml) added, the organic layer separated, washed with brine, dried with Na₂SO₄, filtered, and the solvent removed by distillation under vacuum to afford the benzylated indole as an essentially pure red solid (1.3 g, 94%; m.p. 382–385 K). δ_H (CDCl₃): 5.26 (2H, s, benzyl-CH₂), 6.61 (1H, s, indol-3-yl), 6.96–7.00 (2H, m, ArH), 7.17–7.31 (5H, m, ArH), 7.38–7.43 (2H, m, ArH), 7.56–7.60 (2H, m, ArH), 7.69–7.74 (1H, dd, J = 7.3, 1.2 Hz, ArH), 8.00–8.06 (1H, m, ArH). δ_C (CDCl₃): 47.88, 103.22, 110.41, 120.11, 120.84, 122.36, 124.06, 126.18, 127.23, 127.26, 127.94, 128.54, 29.58, 132.14, 133.40, 135.27, 137.37, 137.46, 149.86, m/z [CI]: 330 (M + 2, 8%), 329 (M + 1, 28%), 299 (100%), 288 (42%), 209 (22%), 108 (32%), 105 (30%), 91 (49%), [EI] 239 (M + 1, 3%), 328 (M⁺, 15%), 204 (10%), 105 (12%), 91 (100%), 49 (48%). C₂₁H₁₆N₂O₂ requires C 76.81, H 4.91, N 8.53%; found C 76.65, H 4.80, N 8.35%.

Preparation of 1-benzyl-2-(2-aminophenyl)indole: to 1-benzyl-2-(2-nitrophenyl)indole (1 g, 3 mmol) dissolved with a minimum amount of CH₂Cl₂ in EtOH (100 ml) palladium on carbon (120 mg, 10%) was added and the mixture treated with hydrogen at room pressure with stirring overnight. The mixture was filtered through Celite and the solvent removed by distillation under vacuum, to afford the amine as an essentially pure clear oil which solidified as a wax (0.89 g, 98%; m.p. 373–377 K). δ_H (CDCl₃): 3.59 (2H, bs, NH₂), 5.19 (2H, s, benzyl-CH₂), 6.48 (1H, s, indol-3-yl-H), 6.69–6.72 (2H, d, J = 7.0 Hz, ArH), 6.82–6.91 (2H, m, ArH), 7.09–7.18 (8H, m, ArH), 7.64 (1H, m, ArH). δ_C (CDCl₃): 47.47, 102.61, 110.59, 115.28, 117.99, 119.94, 120.49, 121.75, 126.38, 127.07, 127.78, 128.16, 128.47, 129.85, 131.54, 137.22, 137.83, 138.03, 145.59. m/z [CI]: 301 (M + 3, 3%), 300 (M + 2, 20%), 299 (M + 1, 100%), 209 (7%), [EI] 299 (M + 1, 10%), 298 (M⁺, 63%), 221 (25%), 207 (41%), 206 (100%), 91 (50%), 49 (55%). C₂₀H₁₈N₂ requires [M] 298.1470; found [M⁺] 298.1468.

Preparation of 1-benzyl-2-(2-(1,2,4,5-tetrazin-3-ylamino)phenyl)indole: n-nutyllithium (0.18 ml, 1.6 M in hexanes) was added slowly to a solution of 1-benzyl-2-(2-aminophenyl)indole (100 mg, 0.3 mmol) in tetrahydrofuran (1 ml, anhydrous), at 233 K and the mixture stirred for 20 min. 3-(Methylsulfanyl)-1,2,4,5-tetrazine (Grasa et al., 2001) (40 mg, 0.3 mmol) in tetrahydrofuran (1 ml, anhydrous) was added dropwise and the temperature maintained at 233 K for 1 h, then allowed to warm to room temperature. The reaction was quenched with saturated aqueous NH₄Cl, and CH₂Cl₂ (5 ml) added, the organic layer separated, dried with Na₂SO₄, filtered, and solvent removed by distillation under vacuum to give a red oil (185 mg). The oil was purified by flash chromatography to afford the title compound as a bright-red oil (72 mg, 63%). δ_H (CDCl₃): 5.21 (2H, bs, benzyl-CH₂), 6.76 (1H, s, indol-3-yl-H), 6.81–6.86 (2H, d, J 8.7, ArH), 6.95–7.09 (3H, m, ArH), 7.23–7.36 (4H, m, ArH), 7.38–7.45 (1H, m, ArH), 7.52–7.58 (1H, m, ArH), 7.69 (1H, bs, NH), 7.76–7.79 (1H, d, J = 7.6 Hz, ArH), 8.39–8.44 (1H, d, J = 8.1 Hz, ArH), 9.74 (1H, s, tetrazin-3-yl-H). δ_C (CDCl₃): 47.41, 104.16, 110.37, 120.02, 120.43, 120.97, 122.70, 122.88, 123.82, 126.69, 127.95, 128.50, 130.02, 131.45, 134.95, 135.96, 137.35, 137.86, 153.88, 161.39. m/z (CI): 382 (M + 3, 10%), 381 (M + 2, 100%), 379 (M + 1, 72%), 299 (10%), 205 (22%), 108 (12%). (EI) 378 (M⁺, 3%), 322 (7%), 83 (3%), 49 (100%). C₂₃H₁₂N₆ requires [M] 378.1592; found [M⁺] 378.1595.

Preparation of pentacycle (3): 1-benzyl-2-[2-(1,2,4,5-tetrazin-3-ylamino)phenyl]indole (80 mg, 0.21 mmol) dissolved in acetic anhydride (1 ml) was heated at reflux for 3 h. The Ac₂O was removed by distillation under vacuum and the resulting oil was purified by flash chromatography to afford the pentacycle as a white solid (46 mg, 63%). The spectroscopic solution data showed the presence of two amide rotamers. Data for the major rotamer are reported here. δ_H (CDCl₃): 1.93 (3H, s, NAc), 1.96 (3H, s, NAc), 2.08 (3H, s, OAc), 3.26–4.18 (2H, m, benzyl-CH₂), 4.10 (1H, s, CH), 6.32–6.36 (1H, d, J = 7.8 Hz, ArH), 6.77 (1H, s, CH), 6.78–6.84 (1H, t, J = 7.4 Hz, ArH), 6.94–7.04 (3H, m, ArH), 7.04–7.17 (4H, m, ArH), 7.30–7.43 (2H, m, ArH), 7.56–7.60 (1H, d, J = 7.4 Hz, ArH), 8.28–8.34 (1H, d, J = 8.2 Hz, ArH). m/z (EI) 393 (M-OAc) (32%), 341 (15%), 332 (25%), 208 (68%), 119 (100%), 108 (70%), 77 (95%).

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.11134 (12)	0.33701 (10)	0.07327 (10)	0.0217 (3)
O2	−0.15831 (14)	0.95401 (11)	0.44132 (12)	0.0293 (3)
O3	−0.16566 (11)	0.86451 (10)	0.16542 (10)	0.0185 (3)
O4	−0.15330 (13)	1.05788 (12)	0.14730 (12)	0.0290 (3)
N1	0.12035 (13)	0.55021 (11)	0.13084 (11)	0.0136 (3)
N2	−0.00939 (13)	0.69152 (12)	0.26750 (11)	0.0143 (3)
N3	−0.02978 (13)	0.82048 (12)	0.31650 (12)	0.0157 (3)
N4	0.27975 (13)	0.84166 (12)	0.27116 (12)	0.0143 (3)
C1	0.20606 (15)	0.56391 (14)	0.04140 (13)	0.0138 (3)
C2	0.26322 (16)	0.47064 (15)	−0.04707 (14)	0.0169 (3)
H2	0.2471	0.3835	−0.0562	0.020*
C3	0.34489 (17)	0.51082 (16)	−0.12148 (15)	0.0198 (3)
H3	0.3862	0.4495	−0.1820	0.024*
C4	0.36819 (17)	0.63795 (16)	−0.11029 (15)	0.0199 (3)
H4	0.4235	0.6620	−0.1634	0.024*
C5	0.31032 (16)	0.72991 (15)	−0.02101 (14)	0.0168 (3)
H5	0.3253	0.8169	−0.0126	0.020*
C6	0.23082 (15)	0.69195 (14)	0.05496 (13)	0.0138 (3)
C7	0.17114 (15)	0.77162 (14)	0.16750 (13)	0.0133 (3)
C8	0.08526 (15)	0.67217 (14)	0.19810 (13)	0.0132 (3)
C9	−0.03043 (16)	0.89815 (14)	0.23869 (14)	0.0154 (3)
H9	−0.0223	0.9894	0.2921	0.018*
C10	0.08520 (15)	0.87819 (14)	0.15452 (14)	0.0139 (3)
H10	0.0467	0.8603	0.0665	0.017*
C11	0.19288 (16)	0.99178 (14)	0.19872 (13)	0.0139 (3)
C12	0.19083 (16)	1.10831 (14)	0.18364 (14)	0.0161 (3)
H12	0.1148	1.1261	0.1368	0.019*
C13	0.30314 (17)	1.19974 (15)	0.23884 (14)	0.0180 (3)
H13	0.3046	1.2802	0.2285	0.022*
C14	0.41228 (17)	1.17327 (15)	0.30860 (14)	0.0184 (3)
H14	0.4873	1.2367	0.3462	0.022*
C15	0.41490 (16)	1.05566 (14)	0.32505 (14)	0.0168 (3)
H15	0.4900	1.0385	0.3733	0.020*
C16	0.30380 (16)	0.96465 (14)	0.26845 (13)	0.0140 (3)
C17	0.08150 (16)	0.43470 (14)	0.14608 (14)	0.0152 (3)
C18	0.00639 (17)	0.43655 (15)	0.25245 (15)	0.0193 (3)
H18A	−0.0870	0.4589	0.2381	0.029*
H18B	0.0551	0.4994	0.3283	0.029*
H18C	0.0017	0.3525	0.2609	0.029*
C19	−0.11128 (17)	0.85215 (15)	0.41157 (15)	0.0193 (3)
C20	−0.13559 (19)	0.75664 (17)	0.47392 (16)	0.0255 (4)
H20A	−0.1773	0.7956	0.5493	0.038*
H20B	−0.0477	0.7276	0.4952	0.038*
H20C	−0.1977	0.6842	0.4181	0.038*
C21	−0.21793 (17)	0.95751 (16)	0.13152 (15)	0.0204 (3)
C22	−0.36440 (18)	0.91917 (19)	0.07458 (17)	0.0294 (4)
H22A	−0.4253	0.9601	0.1348	0.044*
H22B	−0.3839	0.8269	0.0495	0.044*
H22C	−0.3801	0.9454	0.0021	0.044*
C23	0.38708 (16)	0.77433 (15)	0.30949 (14)	0.0162 (3)
H23A	0.4684	0.8355	0.3524	0.019*
H23B	0.4152	0.7116	0.2354	0.019*
C24	0.34071 (15)	0.70640 (14)	0.39457 (14)	0.0147 (3)
C25	0.37201 (16)	0.58401 (15)	0.37962 (14)	0.0172 (3)
H25	0.4200	0.5406	0.3133	0.021*
C26	0.33333 (17)	0.52432 (15)	0.46144 (15)	0.0197 (3)
H26	0.3550	0.4405	0.4507	0.024*
C27	0.26344 (17)	0.58741 (15)	0.55809 (14)	0.0195 (3)
H27	0.2376	0.5471	0.6141	0.023*
C28	0.23110 (17)	0.70966 (16)	0.57334 (15)	0.0197 (3)
H28	0.1831	0.7529	0.6397	0.024*
C29	0.26891 (16)	0.76862 (15)	0.49149 (14)	0.0173 (3)
H29	0.2457	0.8519	0.5016	0.021*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0339 (7)	0.0101 (6)	0.0220 (6)	0.0046 (5)	0.0084 (5)	0.0050 (5)
O2	0.0378 (7)	0.0174 (6)	0.0355 (7)	0.0114 (5)	0.0184 (6)	0.0071 (5)
O3	0.0161 (6)	0.0151 (6)	0.0225 (6)	0.0028 (4)	−0.0002 (4)	0.0044 (5)
O4	0.0303 (7)	0.0241 (7)	0.0377 (7)	0.0045 (5)	−0.0007 (6)	0.0182 (6)
N1	0.0176 (6)	0.0088 (6)	0.0143 (6)	0.0023 (5)	0.0030 (5)	0.0034 (5)
N2	0.0179 (6)	0.0087 (6)	0.0162 (6)	0.0030 (5)	0.0019 (5)	0.0037 (5)
N3	0.0209 (7)	0.0091 (6)	0.0182 (6)	0.0039 (5)	0.0056 (5)	0.0046 (5)
N4	0.0168 (6)	0.0092 (6)	0.0164 (6)	0.0007 (5)	−0.0015 (5)	0.0052 (5)
C1	0.0139 (7)	0.0134 (7)	0.0142 (7)	0.0004 (6)	−0.0003 (6)	0.0057 (6)
C2	0.0196 (8)	0.0125 (8)	0.0185 (8)	0.0038 (6)	0.0031 (6)	0.0044 (6)
C3	0.0201 (8)	0.0201 (8)	0.0175 (8)	0.0058 (6)	0.0050 (6)	0.0028 (6)
C4	0.0196 (8)	0.0236 (9)	0.0183 (8)	0.0007 (6)	0.0049 (6)	0.0089 (7)
C5	0.0171 (8)	0.0160 (8)	0.0186 (8)	0.0003 (6)	0.0022 (6)	0.0079 (6)
C6	0.0146 (7)	0.0118 (7)	0.0146 (7)	0.0030 (6)	0.0002 (6)	0.0042 (6)
C7	0.0151 (7)	0.0117 (7)	0.0137 (7)	0.0019 (6)	0.0023 (6)	0.0047 (6)
C8	0.0169 (7)	0.0095 (7)	0.0129 (7)	0.0016 (6)	−0.0015 (6)	0.0041 (6)
C9	0.0171 (7)	0.0107 (7)	0.0171 (7)	0.0027 (6)	−0.0008 (6)	0.0036 (6)
C10	0.0178 (7)	0.0099 (7)	0.0142 (7)	0.0029 (6)	0.0009 (6)	0.0045 (6)
C11	0.0173 (7)	0.0116 (7)	0.0132 (7)	0.0008 (6)	0.0029 (6)	0.0044 (6)
C12	0.0212 (8)	0.0129 (7)	0.0154 (7)	0.0042 (6)	0.0027 (6)	0.0060 (6)
C13	0.0268 (9)	0.0099 (7)	0.0188 (8)	0.0019 (6)	0.0053 (7)	0.0062 (6)
C14	0.0219 (8)	0.0129 (8)	0.0183 (8)	−0.0023 (6)	0.0034 (6)	0.0030 (6)
C15	0.0191 (8)	0.0146 (8)	0.0160 (7)	0.0012 (6)	0.0004 (6)	0.0048 (6)
C16	0.0194 (8)	0.0106 (7)	0.0129 (7)	0.0026 (6)	0.0043 (6)	0.0043 (6)
C17	0.0177 (8)	0.0118 (7)	0.0165 (7)	0.0018 (6)	−0.0007 (6)	0.0062 (6)
C18	0.0236 (8)	0.0145 (8)	0.0228 (8)	0.0032 (6)	0.0057 (7)	0.0094 (6)
C19	0.0203 (8)	0.0159 (8)	0.0201 (8)	0.0028 (6)	0.0061 (6)	0.0027 (6)
C20	0.0331 (10)	0.0227 (9)	0.0245 (9)	0.0078 (7)	0.0151 (8)	0.0089 (7)
C21	0.0215 (8)	0.0230 (9)	0.0188 (8)	0.0067 (7)	0.0045 (6)	0.0084 (7)
C22	0.0209 (9)	0.0410 (11)	0.0294 (9)	0.0072 (8)	0.0009 (7)	0.0162 (8)
C23	0.0168 (8)	0.0151 (8)	0.0186 (8)	0.0031 (6)	0.0010 (6)	0.0082 (6)
C24	0.0153 (7)	0.0131 (7)	0.0154 (7)	0.0013 (6)	−0.0026 (6)	0.0055 (6)
C25	0.0190 (8)	0.0153 (8)	0.0170 (7)	0.0038 (6)	0.0020 (6)	0.0046 (6)
C26	0.0244 (8)	0.0132 (8)	0.0225 (8)	0.0026 (6)	0.0001 (7)	0.0082 (6)
C27	0.0227 (8)	0.0202 (8)	0.0172 (8)	−0.0022 (6)	−0.0005 (6)	0.0104 (7)
C28	0.0220 (8)	0.0208 (8)	0.0155 (7)	0.0033 (6)	0.0029 (6)	0.0048 (6)
C29	0.0205 (8)	0.0120 (7)	0.0179 (8)	0.0041 (6)	0.0000 (6)	0.0033 (6)

Geometric parameters (Å, º)

O1—C17	1.2162 (18)	C12—C13	1.399 (2)
O2—C19	1.217 (2)	C12—H12	0.9500
O3—C21	1.347 (2)	C13—C14	1.386 (2)
O3—C9	1.4577 (18)	C13—H13	0.9500
O4—C21	1.206 (2)	C14—C15	1.398 (2)
N1—C17	1.4008 (19)	C14—H14	0.9500
N1—C8	1.4181 (18)	C15—C16	1.391 (2)
N1—C1	1.4364 (19)	C15—H15	0.9500
N2—C8	1.270 (2)	C17—C18	1.491 (2)
N2—N3	1.4065 (17)	C18—H18A	0.9800
N3—C19	1.389 (2)	C18—H18B	0.9800
N3—C9	1.447 (2)	C18—H18C	0.9800
N4—C16	1.3981 (19)	C19—C20	1.498 (2)
N4—C23	1.4548 (19)	C20—H20A	0.9800
N4—C7	1.4861 (19)	C20—H20B	0.9800
C1—C2	1.393 (2)	C20—H20C	0.9800
C1—C6	1.397 (2)	C21—C22	1.494 (2)
C2—C3	1.391 (2)	C22—H22A	0.9800
C2—H2	0.9500	C22—H22B	0.9800
C3—C4	1.393 (2)	C22—H22C	0.9800
C3—H3	0.9500	C23—C24	1.517 (2)
C4—C5	1.394 (2)	C23—H23A	0.9900
C4—H4	0.9500	C23—H23B	0.9900
C5—C6	1.380 (2)	C24—C25	1.387 (2)
C5—H5	0.9500	C24—C29	1.394 (2)
C6—C7	1.512 (2)	C25—C26	1.396 (2)
C7—C8	1.511 (2)	C25—H25	0.9500
C7—C10	1.548 (2)	C26—C27	1.383 (2)
C9—C10	1.547 (2)	C26—H26	0.9500
C9—H9	1.0000	C27—C28	1.389 (2)
C10—C11	1.514 (2)	C27—H27	0.9500
C10—H10	1.0000	C28—C29	1.388 (2)
C11—C12	1.379 (2)	C28—H28	0.9500
C11—C16	1.402 (2)	C29—H29	0.9500
C21—O3—C9	115.61 (12)	C13—C14—H14	119.1
C17—N1—C8	127.75 (13)	C15—C14—H14	119.1
C17—N1—C1	124.37 (12)	C16—C15—C14	117.76 (14)
C8—N1—C1	107.89 (12)	C16—C15—H15	121.1
C8—N2—N3	112.69 (12)	C14—C15—H15	121.1
C19—N3—N2	115.85 (12)	C15—C16—N4	129.41 (14)
C19—N3—C9	116.97 (13)	C15—C16—C11	120.49 (14)
N2—N3—C9	120.06 (12)	N4—C16—C11	110.08 (13)
C16—N4—C23	123.21 (12)	O1—C17—N1	119.06 (14)
C16—N4—C7	107.55 (12)	O1—C17—C18	122.43 (14)
C23—N4—C7	119.78 (12)	N1—C17—C18	118.50 (13)
C2—C1—C6	121.28 (14)	C17—C18—H18A	109.5
C2—C1—N1	128.92 (14)	C17—C18—H18B	109.5
C6—C1—N1	109.79 (13)	H18A—C18—H18B	109.5
C3—C2—C1	116.97 (15)	C17—C18—H18C	109.5
C3—C2—H2	121.5	H18A—C18—H18C	109.5
C1—C2—H2	121.5	H18B—C18—H18C	109.5
C2—C3—C4	122.22 (15)	O2—C19—N3	120.01 (15)
C2—C3—H3	118.9	O2—C19—C20	123.10 (15)
C4—C3—H3	118.9	N3—C19—C20	116.89 (14)
C3—C4—C5	119.94 (15)	C19—C20—H20A	109.5
C3—C4—H4	120.0	C19—C20—H20B	109.5
C5—C4—H4	120.0	H20A—C20—H20B	109.5
C6—C5—C4	118.61 (15)	C19—C20—H20C	109.5
C6—C5—H5	120.7	H20A—C20—H20C	109.5
C4—C5—H5	120.7	H20B—C20—H20C	109.5
C5—C6—C1	120.95 (14)	O4—C21—O3	123.38 (15)
C5—C6—C7	129.36 (14)	O4—C21—C22	125.81 (16)
C1—C6—C7	109.40 (13)	O3—C21—C22	110.80 (15)
N4—C7—C8	111.34 (12)	C21—C22—H22A	109.5
N4—C7—C6	112.14 (12)	C21—C22—H22B	109.5
C8—C7—C6	101.78 (12)	H22A—C22—H22B	109.5
N4—C7—C10	102.54 (11)	C21—C22—H22C	109.5
C8—C7—C10	111.47 (12)	H22A—C22—H22C	109.5
C6—C7—C10	117.84 (12)	H22B—C22—H22C	109.5
N2—C8—N1	124.08 (13)	N4—C23—C24	112.47 (13)
N2—C8—C7	126.42 (13)	N4—C23—H23A	109.1
N1—C8—C7	109.40 (12)	C24—C23—H23A	109.1
N3—C9—O3	104.65 (12)	N4—C23—H23B	109.1
N3—C9—C10	114.36 (12)	C24—C23—H23B	109.1
O3—C9—C10	110.91 (12)	H23A—C23—H23B	107.8
N3—C9—H9	108.9	C25—C24—C29	119.23 (14)
O3—C9—H9	108.9	C25—C24—C23	120.95 (14)
C10—C9—H9	108.9	C29—C24—C23	119.79 (14)
C11—C10—C9	110.75 (12)	C24—C25—C26	120.39 (15)
C11—C10—C7	101.48 (12)	C24—C25—H25	119.8
C9—C10—C7	111.30 (12)	C26—C25—H25	119.8
C11—C10—H10	111.0	C27—C26—C25	119.91 (15)
C9—C10—H10	111.0	C27—C26—H26	120.0
C7—C10—H10	111.0	C25—C26—H26	120.0
C12—C11—C16	121.32 (14)	C26—C27—C28	120.06 (15)
C12—C11—C10	130.05 (14)	C26—C27—H27	120.0
C16—C11—C10	108.57 (13)	C28—C27—H27	120.0
C11—C12—C13	118.51 (14)	C29—C28—C27	119.97 (15)
C11—C12—H12	120.7	C29—C28—H28	120.0
C13—C12—H12	120.7	C27—C28—H28	120.0
C14—C13—C12	120.16 (14)	C28—C29—C24	120.43 (15)
C14—C13—H13	119.9	C28—C29—H29	119.8
C12—C13—H13	119.9	C24—C29—H29	119.8
C13—C14—C15	121.75 (14)
C8—N2—N3—C19	−167.67 (13)	N3—C9—C10—C7	3.56 (17)
C8—N2—N3—C9	42.72 (18)	O3—C9—C10—C7	−114.48 (13)
C17—N1—C1—C2	1.8 (2)	N4—C7—C10—C11	29.17 (14)
C8—N1—C1—C2	−178.50 (14)	C8—C7—C10—C11	148.38 (12)
C17—N1—C1—C6	−176.86 (13)	C6—C7—C10—C11	−94.49 (14)
C8—N1—C1—C6	2.81 (16)	N4—C7—C10—C9	−88.69 (14)
C6—C1—C2—C3	−0.5 (2)	C8—C7—C10—C9	30.53 (16)
N1—C1—C2—C3	−179.01 (14)	C6—C7—C10—C9	147.66 (13)
C1—C2—C3—C4	−0.7 (2)	C9—C10—C11—C12	−78.53 (19)
C2—C3—C4—C5	0.9 (2)	C7—C10—C11—C12	163.21 (15)
C3—C4—C5—C6	0.2 (2)	C9—C10—C11—C16	98.62 (14)
C4—C5—C6—C1	−1.4 (2)	C7—C10—C11—C16	−19.64 (15)
C4—C5—C6—C7	171.82 (14)	C16—C11—C12—C13	0.6 (2)
C2—C1—C6—C5	1.5 (2)	C10—C11—C12—C13	177.40 (15)
N1—C1—C6—C5	−179.66 (13)	C11—C12—C13—C14	−1.1 (2)
C2—C1—C6—C7	−172.88 (13)	C12—C13—C14—C15	0.7 (2)
N1—C1—C6—C7	5.93 (16)	C13—C14—C15—C16	0.2 (2)
C16—N4—C7—C8	−149.37 (13)	C14—C15—C16—N4	−179.06 (15)
C23—N4—C7—C8	63.19 (17)	C14—C15—C16—C11	−0.7 (2)
C16—N4—C7—C6	97.32 (14)	C23—N4—C16—C15	−16.9 (2)
C23—N4—C7—C6	−50.12 (18)	C7—N4—C16—C15	−162.96 (15)
C16—N4—C7—C10	−30.06 (15)	C23—N4—C16—C11	164.64 (13)
C23—N4—C7—C10	−177.50 (12)	C7—N4—C16—C11	18.58 (16)
C5—C6—C7—N4	−66.2 (2)	C12—C11—C16—C15	0.4 (2)
C1—C6—C7—N4	107.59 (14)	C10—C11—C16—C15	−177.09 (13)
C5—C6—C7—C8	174.70 (15)	C12—C11—C16—N4	178.98 (13)
C1—C6—C7—C8	−11.50 (15)	C10—C11—C16—N4	1.53 (17)
C5—C6—C7—C10	52.5 (2)	C8—N1—C17—O1	173.86 (14)
C1—C6—C7—C10	−133.71 (14)	C1—N1—C17—O1	−6.5 (2)
N3—N2—C8—N1	−175.74 (13)	C8—N1—C17—C18	−6.9 (2)
N3—N2—C8—C7	0.2 (2)	C1—N1—C17—C18	172.69 (13)
C17—N1—C8—N2	−14.3 (2)	N2—N3—C19—O2	−164.34 (15)
C1—N1—C8—N2	166.07 (14)	C9—N3—C19—O2	−13.8 (2)
C17—N1—C8—C7	169.22 (14)	N2—N3—C19—C20	16.2 (2)
C1—N1—C8—C7	−10.45 (15)	C9—N3—C19—C20	166.82 (14)
N4—C7—C8—N2	77.17 (18)	C9—O3—C21—O4	8.2 (2)
C6—C7—C8—N2	−163.17 (14)	C9—O3—C21—C22	−171.12 (13)
C10—C7—C8—N2	−36.7 (2)	C16—N4—C23—C24	136.03 (14)
N4—C7—C8—N1	−106.42 (13)	C7—N4—C23—C24	−81.80 (16)
C6—C7—C8—N1	13.24 (15)	N4—C23—C24—C25	136.79 (14)
C10—C7—C8—N1	139.74 (12)	N4—C23—C24—C29	−45.03 (19)
C19—N3—C9—O3	−71.56 (15)	C29—C24—C25—C26	−0.7 (2)
N2—N3—C9—O3	77.72 (15)	C23—C24—C25—C26	177.52 (14)
C19—N3—C9—C10	166.90 (13)	C24—C25—C26—C27	0.0 (2)
N2—N3—C9—C10	−43.83 (18)	C25—C26—C27—C28	0.4 (2)
C21—O3—C9—N3	149.60 (13)	C26—C27—C28—C29	0.0 (2)
C21—O3—C9—C10	−86.60 (15)	C27—C28—C29—C24	−0.7 (2)
N3—C9—C10—C11	−108.54 (14)	C25—C24—C29—C28	1.1 (2)
O3—C9—C10—C11	133.42 (13)	C23—C24—C29—C28	−177.16 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1	0.95	2.26	2.814 (2)	116
C10—H10···O1^i	1.00	2.57	3.2685 (19)	127
C29—H29···O2^ii	0.95	2.31	3.242 (2)	167

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