A versatile synthesis of cyclic dipeptides using the stepwise construction of the piperazine-2,5-dione ring from simple precursors: synthetic sequence and the structure of a representative product, (3RS)-4-(2-allyl-3,5-di­methyl­phen­yl)-1-benzyl-3-phenyl­piperazine-2,5-dione

A versatile synthesis of multiply substituted cyclic dipeptides has been designed, based on the stepwise construction of the piperazine-2,5-dione ring using mol­ecular fragments from four different precursor mol­ecules. Starting from substituted 2-allyl­anilines, reaction with methyl 2-bromo-2-phenyl­acetate yields the corresponding methyl 2-(2-allyl­anilino)-2-phenyl­acetates, which react with haloacetyl chlorides to give methyl 2-[N-(2-allyl­phen­yl)-2-haloacetamido]-2-phenyl­acetates, which then undergo ring closure with benzyl­amine to yield the corresponding cyclic dipeptides of type 4-(2-allyl­phen­yl)-1-benzyl-3-phenyl­piperazine-2,5-dione. (3RS)-4-(2-Allyl-3,5-di­methyl­phen­yl)-1-benzyl-3-phenyl­piperazine-2,5-dione, C₂₈H₂₈N₂O₂, (IIId), crystallizes with Z′ = 2 in the space group P2₁/c; the allyl groups in the two independent mol­ecules adopt different conformations and, in one of them, the allyl group is disordered over two sets of atomic sites having occupancies of 0.534 (4) and 0.466 (4). In both mol­ecules, the piperazine-2,5-dione ring adopts a boat conformation, with the 3-phenyl ring in a quasi-axial site. The mol­ecules of (IIId) are linked into a three-dimensional framework structure by a combination of three C—H...O hydrogen bonds and three C—H...π(arene) hydrogen bonds. Comparisons are made with some related structures.

Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(3RS)-4-(2-Allyl-3,5-dimethylphenyl)-1-benzyl-3-phenylpiperazine-2,5-dione

Crystal data

C28H28N2O2	F(000) = 1808
Mr = 424.52	Dx = 1.240 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.3641 (8) Å	Cell parameters from 10436 reflections
b = 10.0825 (3) Å	θ = 2.2–27.6°
c = 21.4524 (7) Å	µ = 0.08 mm^−1
β = 115.885 (1)°	T = 100 K
V = 4546.5 (3) Å^3	Block, colourless
Z = 8	0.15 × 0.15 × 0.12 mm

Data collection

Bruker D8 Venture diffractometer	10435 independent reflections
Radiation source: INCOATEC high brilliance microfocus sealed tube	7625 reflections with I > 2σ(I)
Multilayer mirror monochromator	Rint = 0.050
φ and ω scans	θmax = 27.6°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −30→30
Tmin = 0.967, Tmax = 0.991	k = −13→11
35190 measured reflections	l = −27→24

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.049	H-atom parameters constrained
wR(F^2) = 0.117	w = 1/[σ^2(Fo^2) + (0.0485P)^2 + 1.7906P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
10435 reflections	Δρmax = 0.30 e Å^−3
588 parameters	Δρmin = −0.29 e Å^−3

Special details

Experimental. Spectroscopic characterization for compounds (Ia–d), (IIa–d) and (IIIa–d).

(Ia), IR (ATR, cm^-1) 3421 (N—H), 1741 [C=O (ester)], 1635 [C=C (allyl)], 918 [=C—H (allyl)]; NMR (CDCl₃) δ(¹H) 3.43 (d, J = 6.2 Hz, 2H, –CH₂–), 3.73 (s, 3H, OCH₃), 5.12 (s, 1H, N—CH), 5.16 (s, 1H, N—H), 5.23 (dq, J = 10.0, 1.6 Hz, 1H, =CH₂ (H-cis)), 5.26 (dq, J = 17.2, 1.6 Hz, 1H, =CH₂ (H-trans)), 6.01 (ddt, J = 17.2, 10.0, 6.2 Hz, 1H, =CH–), 6.35 (d, J = 7.6 Hz, 1H, 6'-H), 6.69 (td, J = 7.4, 0.8 Hz, 1H, 4'-H), 7.01 (td, J = 7.6, 1.2 Hz, 1H, 5'-H), 7.08 (dd, J = 7.2, 1.2 Hz, 1H, 3'-H), 7.28–7.32 (m, 1H, 4-H), 7.33–7.37 (m, 2H, 3-H, 5-H), 7.46–7.49 (m, 2H, 2-H, 6-H), δ(¹³C) 36.8 (–CH₂–), 52.9 (OCH₃), 60.5 (N—CH–), 111.3 (6'-C), 116.7 (=CH₂), 117.8 (4'-C), 124.1 (2'-C), 127.2 (2-C, 6-C), 127.6 (5'-C), 128.3 (4-C), 128.9 (3-C, 5-C), 130.0 (3'-C), 135.7 (=CH–), 137.6 (1-C), 144.0 (1'-C), 172.4 (C=O); GC—MS (70 eV) m/z (%) 281 (M⁺, 20), 223 (24), 222 (100), 130 (21), 91 (27).

(Ib), IR (ATR, cm^-1) 3382 (N—H), 1739 [C=O (ester)], 1635 [C=C (allyl)], 925 [=C—H (allyl)]; NMR (CDCl₃) δ(¹H) 2.20 (s, 3H, 4'-CH₃), 3.40 (dt, J = 6.4, 1.6 Hz, 2H, –CH₂–), 3.73 (s, 3H, OCH₃), 5.01 (d, J = 6.0 Hz, 1H, N—H), 5.09 (d, J = 6.0 Hz, 1H, N—CH), 5.22 (dq, J = 10.0, 1.6 Hz, 1H, =CH₂ (H-cis)), 5.25 (dq, J = 16.8, 1.6 Hz, 1H, =CH₂ (H-trans)), 6.00 (ddt, J = 16.8, 10.0, 6.4 Hz, 1H, =CH–), 6.27 (d, J = 8.0 Hz, 1H, 6'-H), 6.81 (dd, J = 8.0, 1.8 Hz, 1H, 5'-H), 6.90 (d, J = 1.8 Hz, 1H, 3'-H), 7.28–7.30 (m, 1H, 4-H), 7.31–7.37 (m, 2H, 3-H, 5-H), 7.46–7.49 (m, 2H, 2-H, 6-H), δ(¹³C) 20.4 (4'-CH₃), 36.8 (–CH₂–), 52.8 (OCH₃), 60.8 (N—CH–), 111.4 (6'-C), 116.6 (=CH₂), 124.2 (2'-C), 127.0 (4'-C), 127.2 (2-C, 6-C), 127.9 (5'-C), 128.2 (4-C), 128.8 (3-C, 5-C), 130.9 (3'-C), 135.9 (=CH–), 137.8 (1-C), 141.7 (1'-C), 172.6 (C=O); GC—MS (70 eV) m/z (%) 295 (M⁺, 27), 237 (26), 236 (100), 144 (25), 91 (18).

(Ic), IR (ATR, cm^-1) 3406 (NH), 1733 [C=O (ester)], 1634 [C=C (allyl)], 929 [=CH (allyl)]; NMR (CDCl₃) δ(¹H) 3.38 (dt, J = 6.4, 1.6 Hz, 2H, –CH₂–), 3.73 (s, 3H, OCH₃) 5.06 (d, J = 6.0 Hz, 1H, N—CH), 5.15 (d, J = 5.8 Hz, 1H, N—H), 5.24–5.29 (m, 2H, =CH₂), 5.92–6.02 (m, 1H, =CH–), 6.24 (d, J = 8.4 Hz, 1H, 6'-H), 6.94 (dd, J = 8.4, 2.4 Hz, 1H, 5'-H), 7.05 (d, J = 2.4 Hz, 1H, 3'-H), 7.29–7.38 (m, 3H, 3-H, 4-H, 5-H), 7.43–7.46 (m, 2H, 2-H, 6-H), δ(¹³C) 36.5 (–CH₂–), 52.9 (OCH₃), 60.5 (N—CH–), 112.3 (6'-C), 117.4 (=CH₂), 122.4 (4'-C), 125.8 (2'-C), 127.2 (5'-C, 2-C, 6-C), 128.5 (4-C), 129.0 (3-C, 5-C), 129.7 (3'-C), 134.8 (=CH–), 137.2 (1-C), 142.4 (1'-C), 172.1 (C=O); GC– MS (70 eV) m/z (%) 315 (M⁺, 35Cl, 20), 258 (33), 257 (22), 256 (100), 164 (13), 91 (24).

(Id), IR (ATR, cm^-1) 3420 (N—H), 1735 [C=O (ester)], 1636 [C=C (allyl)], 927 [=C—H (allyl)]; NMR (CDCl₃) δ¹H) 2.14 (s, 3H, 5_-CH3), 2.25 (s, 3H, 3'-CH₃), 3.43 (br d, J = 5.8 Hz, 2H, –CH₂–), 3.73 (s, 3H, OCH₃), 5.10 (s, 1H, N—CH), 5.16 (dq, J = 10.0, 1.6 Hz, 1H, =CH₂ (H-cis)), 5.17 (dq, J = 17.0, 1.6 Hz, 1H, =CH₂ (H-trans)), 5.96 (ddt, J = 17.0, 10.0, 5.8 Hz, 1H, =CH–), 6.09 (s, 1H, 6'-H), 6.44 (s, 1H, 4'-H), 7.28–7.32 (m, 1H, 4-H), 7.33–7.37 (m, 2H, 3-H, 5-H), 7.46–7.49 (m, 2H, 2-H, 6-H), δ(¹³C) 20.1 (3'-CH₃), 21.5 (5'-CH₃), 31.6 (–CH₂–), 52.8 (OCH₃), 60.7 (N—CH–), 110.3 (6'-C), 115.7 (=CH₂), 119.4 (2'-C), 121.1 (4'-C), 127.2 (2-C, 6-C), 128.2 (4-C), 128.8 (3-C, 5-C), 134.9 (=CH–), 136.4 (5'-C), 136.9 (3'-C), 137.9 (1-C), 144.1 (1'-C), 172.6 (C=O); GC—MS (70 eV): m/z (%) 309 (M⁺, 26), 251 (26), 250 (100), 158 (30).

(IIa), IR (ATR, cm^-1) 1744 [C=O (ester)], 1664 [C=O (amide)], 1600 [C=C (allyl)], 920 [=C—H (allyl)]; NMR (CDCl₃) δ¹H) 2.78 (ddt, J = 15.6, 5.7, 1.5 Hz, 1H, –CH_AH_B–), 3.07 (dd, J = 15.6, 7.8 Hz, 1H, –CH_AH_B–), 3.72 (d, J = 14.0 Hz, 1H, –CH_AH_B—Cl), 3.76 (s, 3H, OCH₃), 3.81 (d, J = 14.0 Hz, 1H, –CH_AH_B—Cl), 4.98 (dq, J = 17.0, 1.6 Hz, 1H, =CH₂ (H-trans)), 5.03 (dq, J = 10.1, 1.6 Hz, 1H, =CH₂ (H-cis)), 5.44 (dddd, J = 17.0, 10.1, 7.8, 5.8 Hz, 1H, =CH–), 6.01 (s, 1H, N—CH), 7.01–7.04 (m, 3H, 3'-H, 2''-H, 6''-H), 7.10–7.15 (m, 2H, 3''-H, 5''-H), 7.18–7.24 (m, 3H, 4'-H, 5'-H, 4''-H), 7.64–7.74 (m, 1H, 6'-H), δ(¹³C) 35.1 (–CH₂–), 42.6 (CH₂Cl), 52.7 (OCH₃), 65.0 (N—CH–), 117.3 (=CH₂), 127.4 (5'-C), 128.2 (3''-C, 5''-C), 128.8 (4''-C), 129.6 (4'-C), 130.2 (3'-C), 130.6 (2''-C, 6''-C), 131.2 (6'-C), 131.8 (1''-C), 135.3 (=CH–), 136.2 (1'-C), 139.0 (2'-C), 167.1 (N—C=O), 170.6 (C=O); GC—MS (70 eV) m/z (%) 357 (M⁺, ³⁵Cl, 4), 298 (61), 222 (100), 208 (64), 149 (35), 132 (20), 130 (44), 121 (69), 91 (62), 77 (40).

(IIb), IR (ATR, cm^-1) 1746 [C=O (ester)], 1673 [C=O (amide)], 1598 [C=C (allyl)], 919 [=C—H (allyl)]; NMR (CDCl₃) δ(¹H) 2.26 (s, 3H, 4'-CH₃), 2.70 (dd, J = 15.6, 5.6 Hz, 1H, –CH_AH_B–), 3.00 (dd, J = 15.6, 8.0 Hz, 1H, –CH_AH_B–), 3.71 (d, J = 14.1 Hz, 1H, –CH_AH_B—Br), 3.74 (s, 3H, OCH₃), 3.82 (d, J = 14.1 Hz, 1H, –CH_AH_B—Br), 4.95–5.02 (m, 2H, =CH₂), 5.35–5.45 (m, 1H, =CH–), 5.98 (s, 1H, N—CH), 6.81 (s, 1H, 3'-H), 7.01–7.03 (m, 3H, 5'-H, 2''-H, 6''-H), 7.11–7.15 (m, 2H, 3''-H, 5''-H), 7.19–7.23 (m, 1H, 4''-H), 7.53 (d, J = 8.0 Hz, 1H, 6'-H), δ(¹³C) 21.2 (4'-CH₃), 35.1 (–CH₂–), 42.8 (–CH₂Br), 52.7 (OCH₃), 65.0 (N—CH–), 117.2 (=CH₂), 128.2 (5'-C, 3''-C, 5''-C), 128.8 (4''-C), 130.7 (2''-C, 6''-C), 130.8 (3'-C, 6'-C), 131.9 (1''-C), 133.5 (1'-C), 135.6 (=CH–), 138.4 (2'-C), 139.7 (4'-C), 167.4 (N—CO–), 170.7 (C=O); GC—MS (70 eV) m/z (%) 415 (M+⁺, ⁷⁹Br, 13), 356 (35), 266 (35), 236 (100), 149 (31), 146 (22), 144 (39), 121 (46), 91 (38), 77 (22).

(IIc), IR (ATR, cm^-1) 1739 [C=O (ester)], 1674 [C=O (amide)], 1643 [C=C (allyl)], 920 [=C—H (allyl)]; NMR (CDCl₃) δ(¹H) 2.71 (dd, J = 15.7, 5.8 Hz, 1H, –CH_AH_B–), 3.02 (dd, J = 15.7, 7.7 Hz, 1H, –CH_AH_B–), 3.70 (d, J = 13.8 Hz, 1H, –CH_AH_B—Cl), 3.75 (s, 3H, OCH₃), 3.78 (d, J = 13.8 Hz, 1H, –CH_AH_B—Cl), 5.00 (dq, J = 17.0, 1.6 Hz, 1H, =CH₂ (H-trans)), 5.07 (dq, J = 10.0, 1.5 Hz, 1H, =CH₂ (H-cis)), 5.37 (dddd, J = 17.0, 10.0, 7.7, 5.8 Hz, 1 H, =CH–), 6.04 (s, 1H, N—CH), 7.01 (s, 1H, 3'-H), 6.99–7.02 (m, 2H, 2''-H, 6''-H), 7.14–7.18 (m, 2H, 3''-H, 5''-H), 7.23 (dd, J = 8.5, 1.8 Hz, 1H, 5'-H), 7.23–7.26 (m, 1H, 4''-H), 7.71 (d, J = 8.5 Hz, 1H, 6'-H), δ(¹³C) 35.0 (–CH₂–), 42.3 (–CH₂Cl), 52.7 (OCH₃), 64.8 (N—CH–), 118.2 (=CH₂), 127.6 (5'-C), 128.4 (3''-C, 5''-C), 129.1 (4''- C), 130.1 (3'-C), 130.6 (2''-C, 6''-C), 131.5 (1''-C), 132.6 (6'-C), 134.4 (=CH–), 134.7 (1'-C), 135.5 (4'-C), 141.1 (2'-C), 167.1 (N—CO–), 170.6 (C=O); GC—MS (70 eV), m/z (%) 391 (M⁺, ³⁵Cl, 12), 332 (62), 256 (100), 242 (50), 166 (22), 164 (28), 149 (55), 121 (78), 91 (52), 77 (45); HR—MS (EI—MS, 70 eV) m/z found 391.0737, C₂₀H₁₉³⁵Cl₂NO₃ requires 391.0742.

(IId), IR (ATR, cm^-1) 1742 [C=O (ester)], 1672 [C=O (amide)], 1610 [C=C (allyl)], 922 [=C—H (allyl)]; NMR (CDCl₃) δ(¹H) 2.09 (s, 3H, 3'-CH₃), 2.25 (s, 3H, 5'-CH₃), 2.89–2.95 (m, 1H, –CH_AH_B–), 3.13 (dd, J = 15.9, 7.0 Hz, 1H, –CH_AH_B–), 3.76 (s, 3H, OCH₃), 3.77 (d, J = 14.1 Hz, 1H, –CH_AH_B—Cl), 3.80 (d, J = 14.1 Hz, 1H, –CH_AH_B—Cl), 4.85 (dq, J = 17.1, 1.6 Hz, 1H, =CH₂ (H-trans)), 4.99 (dq, J = 10.1, 1.6 Hz, 1H, =CH₂ (H-cis)), 5.59 (dddd, J = 17.1, 10.1, 7.0, 4.8 Hz, 1H, =CH–), 5.74 (s, 1H, N—CH), 6.93 (s, 1H, 4'-H), 7.05–7.08 (m, 2H, 2''-H, 6''-H), 7.15 (s, 1H, 6'-H), 7.12–7.16 (m, 2H, 3''-H, 5''-H), 7.18–7.21 (m, 1H, 4''-H), δ(¹³C) 19.6 (3'-CH₃), 20.7 (5'-CH₃), 32.5 (–CH₂–), 43.0 (–CH₂Cl), 52.6 (OCH₃), 65.6 (N—CH–), 116.1 (=CH₂), 128.0 (3''-C, 5''-C), 128.7 (4''-C), 129.1 (6'-C), 130.3 (1''-C), 130.6 (2''-C, 6''-C), 132.3 (5'-C), 132.4 (4'-C), 133.4 (2'-C), 134.6 (=CH–), 136.9 (1'-C), 138.6 (3'-C), 167.2 (N—CO–), 170.3 (C=O); GC—MS (70 eV) m/z (%) 385 (M⁺, ³⁵Cl, 13), 326 (36), 250 (83), 236 (92), 160 (72), 158 (100), 149 (83), 121 (88), 91 (58), 77 (58); HR—MS (EI—MS, 70 eV) m/z found 385.1440, C₂₂H₂₄³⁵ClNO₃ requires 385.1445.

(IIIa), IR (ATR, cm^-1) 1686/1676 [C=O (lactam)], 1599 [C=C (allyl)], 930 [=C—H (allyl)]; NMR (CDCl₃) δ(¹H) 3.36 (d, J = 6.5 Hz, 2H, –CH₂–), 4.00 (d, J = 17.7 Hz, 1H, 6-H_AH_B), 4.21 (d, J = 17.7 Hz, 1H, 6-H_AH_B), 4.62 (s, 2H, N—CH₂–), 5.04 (dd, J = 17.1, 1.4 Hz, 1H, =CH₂ (H-trans)), 5.11 (dd, J = 10.0, 1.4 Hz, 1H, =CH₂ (H-cis)), 5.15 (s, 1H, 3-H), 6.78 (d, J = 7.9 Hz, 1H, 6'-H), 5.92 (ddt, J = 17.1, 10.0, 6.5 Hz, 1H, =CH–), 7.07 (td, J = 7.9, 1.5 Hz, 1H, 5'-H), 7.15–7.18 (m, 2H, 2'''-H, 6'''-H), 7.24–7.28 (m, 1H, 4'-H), 7.29–7.32 (m, 4H, 3'-H, 3'''-H, 5'''-H, 4'''-H), 7.36–7.40 (m, 5H, 2''-H, 6''-H, 3''-H, 5''-H, 4''-H), δ(¹³C) 36.0 (–CH₂–), 49.5 (N—CH₂–), 49.6 (6-C), 68.1 (3-C), 116.8 (=CH₂), 126.8 (2''-C, 6''-C), 127.3 (5'-C), 128.2 (2'''-C, 6'''-C, 4'''-C, 6'-C), 128.9 (4'-C, 4''-C, 3'''-C, 5'''-C), 129.2 (3''-C, 5''-C), 130.9 (3'-C), 135.1 (1'''-C), 135.8 (=CH–), 136.0 (1''-C), 136.6 (2'-C), 137.8 (1'-C), 164.6 (5-C=O), 165.2 (2-C=O); GC—MS (70 eV) m/z (%) 396 (M⁺, 23), 248 (12), 220 (37), 172 (6), 118 (46), 91 (100), 77 (11); HR—MS (EI—MS, 70 eV) m/z found 396.1838, C₂₆H₂₄N₂O₂ requires 396.1836.

(IIIb), IR (ATR, cm^-1) 1665 [C=O (lactam)], 1608 [C=C (ally)], 916 [=C—H (allyl)]; NMR (CDCl₃) δ(¹H) 2.28 (s, 3H, 4'-CH₃), 3.32 (br d, J = 6.8 Hz, 2H, –CH₂–), 4.01 (d, J = 18.0 Hz, 1H, 6-H_AH_B), 4.22 (d, J = 18.0 Hz, 1H, 6-H_AH_B), 4.59 (d, J = 14.6 Hz, 1H, N—CH_AH_B–), 4.64 (d, J = 14.6 Hz, 1H, N—CH_AH_B–), 5.04 (dq, J = 17.2, 1.6 Hz, 1H, =CH₂ (H-trans)), 5.10 (dq, J = 10.0, 1.6 Hz, 1H, =CH₂ (H-cis)), 5.13 (s, 1H, 3-H), 5.91 (ddt, J = 17.2, 10.0, 6.8 Hz, 1H, =CH–), 6.64 (d, J = 8.0 Hz, 1H, 6'-H), 6.87 (dd, J = 8.0, 1.6 Hz, 1H, 5'-H), 7.11 (d, J = 1.6 Hz, 1H, 3'-H), 7.16–7.18 (m, 2H, 2'''-H, 6'''-H), 7.29- 7.32 (m, 3H, 3'''-H, 5'''-H, 4'''-H), 7.38–7.41 (m, 5H, 2''-H, 6''-H, 3''-H, 5''-H, 4''-H), δ(¹³) 21.1 (4'-CH₃), 36.1 (–CH₂–), 49.5 (N—CH₂–), 49.6 (6-C), 68.1 (3-C), 116.7 (=CH₂), 126.9 (2''-C, 6''-C), 128.0 (4'''-C), 128.1 (6'-C), 128.2 (4'''-C), 128.3 (2'''-C, 6'''-C), 128.5 (5'-C), 128.9 (4''-C), 129.0 (3'''-C, 5'''-C), 129.2 (3''-C, 5''-C), 131.7 (3'-C), 135.1 (1'-C), 135.2 (1'''-C), 136.0 (=CH–), 136.1 (1''-C), 136.3 (2'-C), 139.0 (4'-C), 164.7 (5-C=O), 165.3 (2-C=O); GC—MS (70 eV) m/z (%) 410 (M⁺, 91), 262 (16), 234 (50), 186 (6), 118 (44), 91 (100), 77 (7).

(IIIc), IR (ATR, cm^-1) 1661 [C=O (lactam)], 1597 [C=C (allyl)], 919 [=C—H (allyl)]; NMR (CDCl₃) δ(¹H) 3.32 (br d, J = 6.5 Hz, 2H, –CH₂–), 4.00 (d, J = 17.8 Hz, 1H, 6-H_AH_B), 4.21 (d, J = 17.8 Hz, 1H, 6-H_AH_B), 4.59 (d, J = 14.6 Hz, 1H, N—CH_AH_B–), 4.64 (d, J = 14.6 Hz, 1H, N—CH_AH_B–), 5.07 (dq, J = 17.1, 1.5 Hz, 1H, =CH₂ (H-trans)), 5.10 (s, 1H, 3-H), 5.15 (dq, J = 10.1, 1.5 Hz, 1H, =CH₂ (H-cis)), 5.88 (ddt, J = 17.1, 10.1, 6.5 Hz, 1H, =CH–), 6.68 (d, J = 8.5 Hz, 1H, 6'-H), 7.03 (dd, J = 8.5, 2.4 Hz, 1H, 5'-H), 7.15–7.18 (m, 2H, 2'''-H, 6'''-H), 7.30 (d, J = 2.4 Hz, 1H, 3'-H), 7.28–7.31 (m, 2H, 3'''-H, 5'''-H), 7.34–7.37 (m, 3H, 2''-H, 6''-H, 4''-H), 7.39–7.42 (m, 3H, 3''-H, 5''-H, 4'''-H), δ(¹³C) 35.8 (–CH₂–), 49.5 (N—CH₂–), 49.6 (6-C), 68.0 (3-C), 117.6 (=CH₂), 126.8 (2''-C, 6''-C), 127.5 (5'-C), 128.2 (2'''-C, 6'''-C, 4'''-C), 129.0 (3'''-C, 5'''-C), 129.1 (4''-C), 129.3 (3''-C, 5''-C), 129.5 (6'-C), 130.9 (3'-C), 134.7 (4'-C), 134.8 (=CH–), 135.0 (1'''-C), 135.8 (1''-C), 136.2 (1'-C), 138.8 (2'-C), 164.5 (5-C=O), 164.9 (2-C=O); GC—MS (70 eV) m/z (%) 430 (M⁺, ³⁵Cl, 20), 282 (8), 254 (25), 218 (5), 118 (42), 91 (100), 77 (4).

(IIId), IR (ATR, cm^-1) 1665 [C=O (lactam)], 1613 [C=C (allyl)], 900 [=C—H (allyl)]; NMR (CDCl₃) δ(¹H) 2.08 (s, 3H, 5'-CH₃), 2.29 (s, 3H, 3'-CH₃), 3.26–3.37 (m, 2H, –CH₂–), 4.00 (d, J = 17.7 Hz, 1H, 6-H_AH_B), 4.22 (d, J = 17.7 Hz, 1H, 6-H_AH_B), 4.57 (d, J = 14.6 Hz, 1H, N—CH_AH_B–), 4.66 (d, J = 14.6 Hz, 1H, N—CH_AH_B–), 4.89 (dq, J = 17.1, 1.6 Hz, 1H, =CH₂ (H-trans)), 5.15 (s, 1H, 3-H), 5.07 (dq, J = 10.2, 1.6 Hz, 1H, =CH₂ (H-cis)), 5.83–5.93 (m, 1H, =CH–), 6.42 (s, 1H, 6'-H), 6.96 (s, 1H, 4'-H), 7.16–7.19 (m, 2H, 2'''-H, 6'''-H), 7.28–7.32 (m, 3H, 3'''-H, 5'''-H, 4'''-H), 7.35–7.40 m, 5H, 2''-H, 6''-H, 3''-H, 5''-H, 4''-H), δ(¹³C) 19.8 (3'-CH₃), 20.7 (5'-CH₃), 32.3 (–CH₂–), 49.5 (N—CH₂–), 49.6 (6-C), 68.2 (3-C), 115.9 (=CH₂), 126.9 (6'-C), 127.0 (2''-C, 6''-C), 128.1 (4'''-C), 128.2 (2'''-C, 6'''-C), 128.8 (4''-C), 128.9 (5'''-C, 3'''-C), 129.1 (3''-C, 5''-C), 131.4 (2'-C), 131.9 (4'-C), 135.1 (=CH–), 135.2 (1'''-C), 136.1 (1''-C), 136.6 (5'-C), 137.9 (1'-C), 138.7 (3'-C), 164.7 (5-C=O), 165.3 (2-C=O); GC—MS (70 eV) m/z (%) 424 (M⁺, 24), 276 (12), 248 (35), 200 (6), 118 (43), 91 (100), 77 (9); HR—MS (EI—MS, 70 eV) m/z found 424.2145, C₂₈H₂₈N₂O₂ requires 424.2151.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N11	0.49184 (6)	0.79569 (12)	0.63445 (7)	0.0160 (3)
C12	0.43177 (7)	0.81150 (15)	0.58557 (8)	0.0158 (3)
O12	0.41013 (5)	0.75649 (11)	0.52881 (6)	0.0217 (3)
C13	0.38860 (7)	0.90236 (14)	0.60278 (8)	0.0151 (3)
H13	0.3619	0.9523	0.5595	0.018*
N14	0.42363 (6)	1.00168 (12)	0.65606 (6)	0.0143 (3)
C15	0.48274 (7)	0.98184 (14)	0.70731 (8)	0.0145 (3)
O15	0.50869 (5)	1.05941 (10)	0.75554 (6)	0.0207 (3)
C16	0.51692 (7)	0.85789 (15)	0.70279 (8)	0.0159 (3)
H16B	0.5622	0.8801	0.7172	0.019*
H16A	0.5152	0.7923	0.7363	0.019*
C117	0.53437 (7)	0.70366 (15)	0.62255 (9)	0.0192 (3)
H11A	0.5088	0.6461	0.5826	0.023*
H11B	0.5552	0.6460	0.6638	0.023*
C111	0.58541 (7)	0.77210 (16)	0.60834 (8)	0.0196 (3)
C112	0.63616 (8)	0.6971 (2)	0.61018 (10)	0.0324 (4)
H112	0.6385	0.6053	0.6211	0.039*
C113	0.68315 (9)	0.7544 (2)	0.59640 (12)	0.0437 (5)
H113	0.7175	0.7021	0.5978	0.052*
C114	0.68015 (9)	0.8876 (2)	0.58055 (11)	0.0429 (5)
H114	0.7124	0.9269	0.5709	0.051*
C115	0.63028 (9)	0.9640 (2)	0.57873 (10)	0.0344 (5)
H115	0.6285	1.0559	0.5683	0.041*
C116	0.58286 (8)	0.90604 (17)	0.59213 (9)	0.0237 (4)
H116	0.5483	0.9585	0.5902	0.028*
C131	0.34310 (7)	0.82154 (14)	0.62156 (8)	0.0161 (3)
C132	0.36518 (8)	0.75635 (16)	0.68476 (9)	0.0212 (4)
H132	0.4090	0.7613	0.7163	0.025*
C133	0.32378 (8)	0.68403 (16)	0.70228 (9)	0.0246 (4)
H133	0.3393	0.6398	0.7457	0.029*
C134	0.26005 (8)	0.67634 (16)	0.65668 (10)	0.0264 (4)
H134	0.2316	0.6278	0.6689	0.032*
C135	0.23773 (8)	0.73922 (16)	0.59335 (10)	0.0274 (4)
H135	0.1940	0.7331	0.5618	0.033*
C136	0.27918 (7)	0.81169 (16)	0.57552 (9)	0.0224 (4)
H136	0.2637	0.8545	0.5317	0.027*
C141	0.38972 (7)	1.12302 (14)	0.65377 (8)	0.0155 (3)
C142	0.39739 (7)	1.23103 (15)	0.61735 (8)	0.0191 (3)
C143	0.36172 (8)	1.34625 (15)	0.61338 (9)	0.0232 (4)
C144	0.32063 (8)	1.34677 (16)	0.64436 (9)	0.0247 (4)
H144	0.2963	1.4245	0.6406	0.030*
C145	0.31321 (7)	1.23918 (16)	0.68074 (9)	0.0217 (4)
C146	0.34888 (7)	1.12590 (15)	0.68533 (8)	0.0178 (3)
H146	0.3453	1.0506	0.7100	0.021*
C147	0.36800 (10)	1.46881 (17)	0.57627 (10)	0.0371 (5)
H17A	0.3349	1.5328	0.5720	0.056*
H17B	0.3632	1.4444	0.5300	0.056*
H17C	0.4100	1.5087	0.6028	0.056*
C148	0.26633 (9)	1.24471 (19)	0.71168 (11)	0.0348 (5)
H18A	0.2682	1.1616	0.7362	0.052*
H18B	0.2233	1.2570	0.6747	0.052*
H18C	0.2771	1.3191	0.7443	0.052*
C151	0.44283 (8)	1.22442 (18)	0.58450 (10)	0.0307 (4)	0.534 (4)
H15A	0.4605	1.1337	0.5896	0.037*	0.534 (4)
H15B	0.4196	1.2441	0.5344	0.037*	0.534 (4)
C152	0.49575 (17)	1.3211 (4)	0.6175 (2)	0.0235 (7)	0.534 (4)
H152	0.4935	1.3842	0.6493	0.028*	0.534 (4)
C153	0.5461 (7)	1.322 (3)	0.6037 (7)	0.057 (3)	0.534 (4)
H15C	0.5490	1.2593	0.5721	0.068*	0.534 (4)
H15D	0.5792	1.3847	0.6256	0.068*	0.534 (4)
C161	0.44283 (8)	1.22442 (18)	0.58450 (10)	0.0307 (4)	0.466 (4)
H16C	0.4426	1.1319	0.5690	0.037*	0.466 (4)
H16D	0.4249	1.2803	0.5423	0.037*	0.466 (4)
C162	0.51010 (16)	1.2639 (5)	0.6247 (2)	0.0235 (7)	0.466 (4)
H162	0.5327	1.2305	0.6704	0.028*	0.466 (4)
C163	0.5404 (8)	1.344 (3)	0.5997 (9)	0.057 (3)	0.466 (4)
H16E	0.5188	1.3790	0.5542	0.068*	0.466 (4)
H16F	0.5837	1.3668	0.6275	0.068*	0.466 (4)
N21	0.04212 (6)	0.63560 (12)	0.16810 (6)	0.0132 (3)
C22	0.09475 (7)	0.59764 (14)	0.16241 (8)	0.0136 (3)
O22	0.11420 (5)	0.64804 (10)	0.12304 (6)	0.0194 (2)
C23	0.13169 (7)	0.48355 (14)	0.21050 (8)	0.0128 (3)
H23	0.1555	0.4372	0.1878	0.015*
N24	0.08851 (6)	0.38576 (11)	0.21790 (6)	0.0125 (3)
C25	0.03629 (7)	0.42531 (14)	0.22520 (7)	0.0129 (3)
O25	0.00104 (5)	0.34973 (10)	0.23653 (6)	0.0181 (2)
C26	0.02417 (7)	0.57354 (14)	0.21879 (8)	0.0152 (3)
H26A	−0.0216	0.5900	0.2049	0.018*
H26B	0.0486	0.6154	0.2646	0.018*
C217	0.00332 (7)	0.74618 (14)	0.12708 (8)	0.0143 (3)
H21B	0.0243	0.7860	0.1002	0.017*
H21A	0.0011	0.8150	0.1589	0.017*
C211	−0.06361 (7)	0.70544 (15)	0.07761 (8)	0.0148 (3)
C212	−0.11271 (7)	0.79748 (16)	0.05874 (8)	0.0195 (3)
H212	−0.1043	0.8833	0.0790	0.023*
C213	−0.17388 (8)	0.76513 (18)	0.01053 (9)	0.0266 (4)
H213	−0.2071	0.8287	−0.0021	0.032*
C214	−0.18647 (8)	0.64005 (18)	−0.01923 (9)	0.0283 (4)
H214	−0.2283	0.6177	−0.0522	0.034*
C215	−0.13801 (8)	0.54777 (17)	−0.00089 (9)	0.0251 (4)
H215	−0.1465	0.4623	−0.0216	0.030*
C216	−0.07709 (8)	0.57976 (15)	0.04761 (8)	0.0191 (3)
H216	−0.0442	0.5154	0.0606	0.023*
C231	0.18120 (7)	0.53956 (14)	0.27904 (8)	0.0163 (3)
C232	0.17819 (8)	0.52047 (16)	0.34157 (8)	0.0213 (4)
H232	0.1445	0.4698	0.3429	0.026*
C233	0.22437 (9)	0.57528 (17)	0.40248 (9)	0.0293 (4)
H233	0.2218	0.5621	0.4450	0.035*
C234	0.27385 (8)	0.64874 (17)	0.40124 (10)	0.0308 (4)
H234	0.3056	0.6851	0.4428	0.037*
C235	0.27673 (8)	0.66881 (17)	0.33891 (10)	0.0283 (4)
H235	0.3103	0.7203	0.3377	0.034*
C236	0.23097 (7)	0.61432 (16)	0.27800 (9)	0.0222 (4)
H236	0.2336	0.6281	0.2355	0.027*
C241	0.10316 (7)	0.24620 (14)	0.21712 (8)	0.0126 (3)
C242	0.09176 (7)	0.18795 (14)	0.15371 (8)	0.0133 (3)
C243	0.10867 (7)	0.05387 (14)	0.15368 (8)	0.0138 (3)
C244	0.13213 (7)	−0.01712 (14)	0.21546 (8)	0.0143 (3)
H244	0.1428	−0.1079	0.2149	0.017*
C245	0.14059 (7)	0.03980 (14)	0.27801 (8)	0.0148 (3)
C246	0.12735 (7)	0.17423 (14)	0.27844 (8)	0.0136 (3)
H246	0.1349	0.2169	0.3208	0.016*
C247	0.10033 (8)	−0.01281 (15)	0.08729 (8)	0.0193 (3)
H27A	0.1123	−0.1065	0.0964	0.029*
H27B	0.1275	0.0309	0.0693	0.029*
H27C	0.0558	−0.0061	0.0531	0.029*
C248	0.16066 (8)	−0.04413 (16)	0.34240 (8)	0.0215 (4)
H28A	0.1723	0.0136	0.3829	0.032*
H28B	0.1974	−0.0986	0.3481	0.032*
H28C	0.1254	−0.1019	0.3380	0.032*
C251	0.05832 (8)	0.26180 (15)	0.08601 (8)	0.0177 (3)
H25A	0.0688	0.3573	0.0943	0.021*
H25B	0.0747	0.2296	0.0533	0.021*
C252	−0.01264 (8)	0.24622 (16)	0.05317 (8)	0.0228 (4)
H252	−0.0357	0.2842	0.0086	0.027*
C253	−0.04598 (8)	0.18456 (19)	0.08062 (9)	0.0298 (4)
H25C	−0.0250	0.1451	0.1251	0.036*
H25D	−0.0910	0.1796	0.0559	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0155 (6)	0.0158 (6)	0.0174 (7)	0.0011 (5)	0.0077 (5)	−0.0020 (5)
C12	0.0176 (8)	0.0134 (7)	0.0179 (8)	−0.0034 (6)	0.0092 (6)	0.0008 (6)
O12	0.0240 (6)	0.0223 (6)	0.0179 (6)	−0.0037 (5)	0.0083 (5)	−0.0058 (5)
C13	0.0149 (7)	0.0134 (7)	0.0135 (7)	−0.0010 (6)	0.0030 (6)	−0.0013 (6)
N14	0.0127 (6)	0.0103 (6)	0.0162 (6)	−0.0002 (5)	0.0029 (5)	−0.0006 (5)
C15	0.0141 (7)	0.0145 (7)	0.0144 (7)	−0.0010 (6)	0.0057 (6)	0.0027 (6)
O15	0.0200 (6)	0.0168 (5)	0.0187 (6)	−0.0002 (5)	0.0024 (5)	−0.0039 (5)
C16	0.0139 (7)	0.0161 (7)	0.0154 (8)	0.0015 (6)	0.0043 (6)	−0.0002 (6)
C117	0.0212 (8)	0.0137 (7)	0.0247 (9)	0.0032 (6)	0.0119 (7)	0.0005 (6)
C111	0.0178 (8)	0.0228 (8)	0.0183 (8)	0.0025 (7)	0.0080 (6)	−0.0001 (7)
C112	0.0278 (9)	0.0375 (10)	0.0354 (11)	0.0086 (8)	0.0170 (8)	0.0039 (9)
C113	0.0237 (10)	0.0682 (15)	0.0465 (13)	0.0092 (10)	0.0221 (9)	0.0063 (11)
C114	0.0262 (10)	0.0703 (15)	0.0367 (12)	−0.0155 (10)	0.0180 (9)	−0.0022 (11)
C115	0.0380 (11)	0.0381 (11)	0.0280 (10)	−0.0160 (9)	0.0153 (8)	−0.0022 (8)
C116	0.0261 (9)	0.0235 (8)	0.0224 (9)	−0.0014 (7)	0.0114 (7)	−0.0003 (7)
C131	0.0145 (7)	0.0127 (7)	0.0216 (8)	−0.0003 (6)	0.0083 (6)	−0.0044 (6)
C132	0.0169 (8)	0.0208 (8)	0.0239 (9)	−0.0027 (7)	0.0070 (7)	−0.0020 (7)
C133	0.0296 (9)	0.0194 (8)	0.0296 (10)	−0.0014 (7)	0.0175 (8)	−0.0010 (7)
C134	0.0256 (9)	0.0174 (8)	0.0464 (12)	−0.0024 (7)	0.0252 (9)	−0.0048 (8)
C135	0.0147 (8)	0.0220 (8)	0.0438 (11)	−0.0017 (7)	0.0113 (8)	−0.0036 (8)
C136	0.0176 (8)	0.0183 (8)	0.0272 (9)	0.0014 (7)	0.0060 (7)	−0.0014 (7)
C141	0.0116 (7)	0.0121 (7)	0.0166 (8)	0.0002 (6)	0.0004 (6)	−0.0014 (6)
C142	0.0162 (8)	0.0155 (7)	0.0193 (8)	−0.0028 (6)	0.0021 (6)	0.0017 (6)
C143	0.0239 (9)	0.0124 (7)	0.0203 (9)	−0.0011 (6)	−0.0024 (7)	0.0012 (6)
C144	0.0219 (8)	0.0137 (7)	0.0266 (9)	0.0054 (7)	−0.0004 (7)	−0.0050 (7)
C145	0.0146 (7)	0.0208 (8)	0.0222 (9)	0.0014 (6)	0.0012 (6)	−0.0068 (7)
C146	0.0158 (7)	0.0143 (7)	0.0206 (8)	−0.0017 (6)	0.0053 (6)	−0.0008 (6)
C147	0.0527 (12)	0.0169 (8)	0.0282 (10)	−0.0022 (8)	0.0050 (9)	0.0059 (7)
C148	0.0270 (9)	0.0347 (10)	0.0453 (12)	0.0043 (8)	0.0182 (9)	−0.0076 (9)
C151	0.0262 (9)	0.0298 (9)	0.0349 (11)	−0.0012 (8)	0.0122 (8)	0.0126 (8)
C152	0.0241 (16)	0.0234 (19)	0.0252 (13)	0.0036 (14)	0.0129 (12)	0.0007 (16)
C153	0.036 (3)	0.046 (7)	0.097 (2)	−0.010 (4)	0.037 (2)	−0.013 (3)
C161	0.0262 (9)	0.0298 (9)	0.0349 (11)	−0.0012 (8)	0.0122 (8)	0.0126 (8)
C162	0.0241 (16)	0.0234 (19)	0.0252 (13)	0.0036 (14)	0.0129 (12)	0.0007 (16)
C163	0.036 (3)	0.046 (7)	0.097 (2)	−0.010 (4)	0.037 (2)	−0.013 (3)
N21	0.0156 (6)	0.0118 (6)	0.0139 (6)	0.0015 (5)	0.0080 (5)	0.0029 (5)
C22	0.0155 (7)	0.0108 (7)	0.0140 (7)	−0.0030 (6)	0.0059 (6)	−0.0018 (6)
O22	0.0228 (6)	0.0175 (5)	0.0232 (6)	0.0010 (5)	0.0150 (5)	0.0053 (5)
C23	0.0125 (7)	0.0106 (6)	0.0163 (8)	−0.0004 (6)	0.0072 (6)	0.0006 (6)
N24	0.0148 (6)	0.0098 (6)	0.0146 (6)	−0.0011 (5)	0.0078 (5)	−0.0003 (5)
C25	0.0158 (7)	0.0139 (7)	0.0091 (7)	0.0003 (6)	0.0054 (6)	−0.0002 (6)
O25	0.0203 (5)	0.0162 (5)	0.0228 (6)	−0.0008 (4)	0.0142 (5)	0.0030 (4)
C26	0.0196 (7)	0.0134 (7)	0.0166 (8)	0.0029 (6)	0.0116 (6)	0.0026 (6)
C217	0.0190 (7)	0.0106 (7)	0.0146 (7)	0.0022 (6)	0.0085 (6)	0.0027 (6)
C211	0.0190 (8)	0.0161 (7)	0.0121 (7)	−0.0003 (6)	0.0095 (6)	0.0034 (6)
C212	0.0227 (8)	0.0198 (8)	0.0179 (8)	0.0046 (7)	0.0107 (7)	0.0034 (6)
C213	0.0202 (8)	0.0333 (9)	0.0239 (9)	0.0077 (7)	0.0073 (7)	0.0088 (8)
C214	0.0200 (8)	0.0371 (10)	0.0208 (9)	−0.0064 (8)	0.0024 (7)	0.0056 (8)
C215	0.0292 (9)	0.0235 (8)	0.0212 (9)	−0.0079 (7)	0.0096 (7)	−0.0007 (7)
C216	0.0217 (8)	0.0168 (7)	0.0191 (8)	0.0001 (6)	0.0093 (7)	0.0017 (6)
C231	0.0146 (7)	0.0107 (7)	0.0192 (8)	0.0025 (6)	0.0033 (6)	0.0016 (6)
C232	0.0229 (8)	0.0174 (8)	0.0182 (8)	−0.0034 (7)	0.0041 (7)	0.0013 (6)
C233	0.0356 (10)	0.0241 (9)	0.0183 (9)	−0.0020 (8)	0.0026 (8)	0.0005 (7)
C234	0.0236 (9)	0.0198 (8)	0.0294 (10)	−0.0001 (7)	−0.0065 (7)	−0.0029 (7)
C235	0.0155 (8)	0.0207 (8)	0.0398 (11)	−0.0027 (7)	0.0039 (8)	−0.0006 (8)
C236	0.0187 (8)	0.0179 (8)	0.0292 (9)	0.0005 (7)	0.0099 (7)	0.0018 (7)
C241	0.0111 (7)	0.0098 (6)	0.0174 (8)	−0.0011 (6)	0.0067 (6)	−0.0013 (6)
C242	0.0144 (7)	0.0115 (7)	0.0154 (8)	−0.0016 (6)	0.0078 (6)	0.0001 (6)
C243	0.0121 (7)	0.0123 (7)	0.0179 (8)	−0.0030 (6)	0.0074 (6)	−0.0023 (6)
C244	0.0127 (7)	0.0094 (6)	0.0215 (8)	−0.0008 (6)	0.0080 (6)	−0.0004 (6)
C245	0.0115 (7)	0.0148 (7)	0.0175 (8)	0.0000 (6)	0.0057 (6)	0.0023 (6)
C246	0.0132 (7)	0.0152 (7)	0.0132 (7)	−0.0024 (6)	0.0066 (6)	−0.0019 (6)
C247	0.0273 (8)	0.0141 (7)	0.0204 (8)	−0.0004 (7)	0.0139 (7)	−0.0024 (6)
C248	0.0238 (8)	0.0190 (8)	0.0201 (9)	0.0033 (7)	0.0080 (7)	0.0046 (6)
C251	0.0287 (8)	0.0124 (7)	0.0138 (8)	−0.0001 (6)	0.0109 (7)	−0.0017 (6)
C252	0.0302 (9)	0.0183 (8)	0.0143 (8)	0.0051 (7)	0.0044 (7)	−0.0018 (6)
C253	0.0205 (9)	0.0392 (10)	0.0224 (9)	0.0004 (8)	0.0025 (7)	−0.0022 (8)

Geometric parameters (Å, º)

N11—C12	1.3452 (19)	C163—H16E	0.9500
N11—C117	1.4612 (19)	C163—H16F	0.9500
N11—C16	1.4615 (19)	N21—C22	1.3433 (19)
C12—O12	1.2281 (18)	N21—C217	1.4639 (18)
C12—C13	1.523 (2)	N21—C26	1.4657 (19)
C13—N14	1.4706 (18)	C22—O22	1.2300 (18)
C13—C131	1.527 (2)	C22—C23	1.535 (2)
C13—H13	1.0000	C23—N24	1.4678 (18)
N14—C15	1.3529 (18)	C23—C231	1.528 (2)
N14—C141	1.4468 (19)	C23—H23	1.0000
C15—O15	1.2256 (18)	N24—C25	1.3562 (19)
C15—C16	1.509 (2)	N24—C241	1.4499 (18)
C16—H16B	0.9900	C25—O25	1.2218 (18)
C16—H16A	0.9900	C25—C26	1.516 (2)
C117—C111	1.520 (2)	C26—H26A	0.9900
C117—H11A	0.9900	C26—H26B	0.9900
C117—H11B	0.9900	C217—C211	1.514 (2)
C111—C116	1.389 (2)	C217—H21B	0.9900
C111—C112	1.392 (2)	C217—H21A	0.9900
C112—C113	1.382 (3)	C211—C212	1.391 (2)
C112—H112	0.9500	C211—C216	1.394 (2)
C113—C114	1.379 (3)	C212—C213	1.389 (2)
C113—H113	0.9500	C212—H212	0.9500
C114—C115	1.383 (3)	C213—C214	1.386 (3)
C114—H114	0.9500	C213—H213	0.9500
C115—C116	1.389 (2)	C214—C215	1.383 (3)
C115—H115	0.9500	C214—H214	0.9500
C116—H116	0.9500	C215—C216	1.385 (2)
C131—C132	1.388 (2)	C215—H215	0.9500
C131—C136	1.388 (2)	C216—H216	0.9500
C132—C133	1.388 (2)	C231—C232	1.387 (2)
C132—H132	0.9500	C231—C236	1.394 (2)
C133—C134	1.381 (2)	C232—C233	1.395 (2)
C133—H133	0.9500	C232—H232	0.9500
C134—C135	1.379 (3)	C233—C234	1.383 (3)
C134—H134	0.9500	C233—H233	0.9500
C135—C136	1.393 (2)	C234—C235	1.383 (3)
C135—H135	0.9500	C234—H234	0.9500
C136—H136	0.9500	C235—C236	1.390 (2)
C141—C146	1.391 (2)	C235—H235	0.9500
C141—C142	1.397 (2)	C236—H236	0.9500
C142—C143	1.411 (2)	C241—C246	1.388 (2)
C142—C151	1.510 (3)	C241—C242	1.396 (2)
C143—C144	1.386 (3)	C242—C243	1.408 (2)
C143—C147	1.511 (2)	C242—C251	1.511 (2)
C144—C145	1.391 (2)	C243—C244	1.391 (2)
C144—H144	0.9500	C243—C247	1.509 (2)
C145—C146	1.392 (2)	C244—C245	1.392 (2)
C145—C148	1.509 (3)	C244—H244	0.9500
C146—H146	0.9500	C245—C246	1.391 (2)
C147—H17A	0.9800	C245—C248	1.509 (2)
C147—H17B	0.9800	C246—H246	0.9500
C147—H17C	0.9800	C247—H27A	0.9800
C148—H18A	0.9800	C247—H27B	0.9800
C148—H18B	0.9800	C247—H27C	0.9800
C148—H18C	0.9800	C248—H28A	0.9800
C151—C152	1.488 (3)	C248—H28B	0.9800
C151—H15A	0.9900	C248—H28C	0.9800
C151—H15B	0.9900	C251—C252	1.500 (2)
C152—C153	1.333 (11)	C251—H25A	0.9900
C152—H152	0.9500	C251—H25B	0.9900
C153—H15C	0.9500	C252—C253	1.319 (3)
C153—H15D	0.9500	C252—H252	0.9500
C162—C163	1.333 (12)	C253—H25C	0.9500
C162—H162	0.9500	C253—H25D	0.9500
C12—N11—C117	119.78 (13)	C162—C163—H16F	120.0
C12—N11—C16	123.79 (13)	H16E—C163—H16F	120.0
C117—N11—C16	116.25 (12)	C22—N21—C217	120.91 (12)
O12—C12—N11	123.86 (14)	C22—N21—C26	121.04 (12)
O12—C12—C13	118.85 (13)	C217—N21—C26	117.94 (12)
N11—C12—C13	117.29 (13)	O22—C22—N21	124.88 (13)
N14—C13—C12	113.29 (12)	O22—C22—C23	120.22 (13)
N14—C13—C131	111.95 (13)	N21—C22—C23	114.89 (13)
C12—C13—C131	110.75 (12)	N24—C23—C231	114.31 (12)
N14—C13—H13	106.8	N24—C23—C22	111.40 (11)
C12—C13—H13	106.8	C231—C23—C22	109.71 (11)
C131—C13—H13	106.8	N24—C23—H23	107.0
C15—N14—C141	120.15 (12)	C231—C23—H23	107.0
C15—N14—C13	123.73 (12)	C22—C23—H23	107.0
C141—N14—C13	116.02 (11)	C25—N24—C241	121.03 (12)
O15—C15—N14	123.02 (14)	C25—N24—C23	120.69 (12)
O15—C15—C16	120.14 (13)	C241—N24—C23	118.29 (11)
N14—C15—C16	116.83 (13)	O25—C25—N24	123.93 (13)
N11—C16—C15	115.35 (12)	O25—C25—C26	121.16 (13)
N11—C16—H16B	108.4	N24—C25—C26	114.91 (12)
C15—C16—H16B	108.4	N21—C26—C25	112.68 (12)
N11—C16—H16A	108.4	N21—C26—H26A	109.1
C15—C16—H16A	108.4	C25—C26—H26A	109.1
H16B—C16—H16A	107.5	N21—C26—H26B	109.1
N11—C117—C111	113.56 (13)	C25—C26—H26B	109.1
N11—C117—H11A	108.9	H26A—C26—H26B	107.8
C111—C117—H11A	108.9	N21—C217—C211	113.20 (12)
N11—C117—H11B	108.9	N21—C217—H21B	108.9
C111—C117—H11B	108.9	C211—C217—H21B	108.9
H11A—C117—H11B	107.7	N21—C217—H21A	108.9
C116—C111—C112	118.56 (16)	C211—C217—H21A	108.9
C116—C111—C117	122.69 (14)	H21B—C217—H21A	107.8
C112—C111—C117	118.74 (15)	C212—C211—C216	118.74 (14)
C113—C112—C111	120.85 (19)	C212—C211—C217	119.42 (13)
C113—C112—H112	119.6	C216—C211—C217	121.77 (14)
C111—C112—H112	119.6	C213—C212—C211	120.65 (15)
C114—C113—C112	120.02 (19)	C213—C212—H212	119.7
C114—C113—H113	120.0	C211—C212—H212	119.7
C112—C113—H113	120.0	C214—C213—C212	119.96 (16)
C113—C114—C115	120.03 (18)	C214—C213—H213	120.0
C113—C114—H114	120.0	C212—C213—H213	120.0
C115—C114—H114	120.0	C215—C214—C213	119.88 (15)
C114—C115—C116	119.88 (19)	C215—C214—H214	120.1
C114—C115—H115	120.1	C213—C214—H214	120.1
C116—C115—H115	120.1	C214—C215—C216	120.13 (16)
C115—C116—C111	120.65 (17)	C214—C215—H215	119.9
C115—C116—H116	119.7	C216—C215—H215	119.9
C111—C116—H116	119.7	C215—C216—C211	120.63 (15)
C132—C131—C136	119.12 (15)	C215—C216—H216	119.7
C132—C131—C13	120.41 (13)	C211—C216—H216	119.7
C136—C131—C13	120.47 (14)	C232—C231—C236	119.04 (14)
C133—C132—C131	120.52 (15)	C232—C231—C23	122.87 (14)
C133—C132—H132	119.7	C236—C231—C23	118.09 (14)
C131—C132—H132	119.7	C231—C232—C233	120.39 (16)
C134—C133—C132	120.07 (16)	C231—C232—H232	119.8
C134—C133—H133	120.0	C233—C232—H232	119.8
C132—C133—H133	120.0	C234—C233—C232	120.34 (18)
C135—C134—C133	119.93 (16)	C234—C233—H233	119.8
C135—C134—H134	120.0	C232—C233—H233	119.8
C133—C134—H134	120.0	C235—C234—C233	119.41 (16)
C134—C135—C136	120.16 (15)	C235—C234—H234	120.3
C134—C135—H135	119.9	C233—C234—H234	120.3
C136—C135—H135	119.9	C234—C235—C236	120.59 (16)
C131—C136—C135	120.19 (16)	C234—C235—H235	119.7
C131—C136—H136	119.9	C236—C235—H235	119.7
C135—C136—H136	119.9	C235—C236—C231	120.21 (17)
C146—C141—C142	122.62 (14)	C235—C236—H236	119.9
C146—C141—N14	118.89 (14)	C231—C236—H236	119.9
C142—C141—N14	118.43 (14)	C246—C241—C242	121.92 (13)
C141—C142—C143	117.33 (16)	C246—C241—N24	119.79 (13)
C141—C142—C151	120.97 (14)	C242—C241—N24	118.28 (13)
C143—C142—C151	121.69 (15)	C241—C242—C243	118.03 (13)
C144—C143—C142	119.27 (15)	C241—C242—C251	121.84 (13)
C144—C143—C147	119.77 (16)	C243—C242—C251	120.00 (13)
C142—C143—C147	120.96 (17)	C244—C243—C242	119.16 (14)
C143—C144—C145	123.26 (15)	C244—C243—C247	120.33 (13)
C143—C144—H144	118.4	C242—C243—C247	120.50 (13)
C145—C144—H144	118.4	C243—C244—C245	122.51 (13)
C144—C145—C146	117.53 (16)	C243—C244—H244	118.7
C144—C145—C148	120.68 (15)	C245—C244—H244	118.7
C146—C145—C148	121.75 (16)	C246—C245—C244	118.01 (14)
C141—C146—C145	119.98 (15)	C246—C245—C248	121.42 (14)
C141—C146—H146	120.0	C244—C245—C248	120.51 (13)
C145—C146—H146	120.0	C241—C246—C245	120.18 (14)
C143—C147—H17A	109.5	C241—C246—H246	119.9
C143—C147—H17B	109.5	C245—C246—H246	119.9
H17A—C147—H17B	109.5	C243—C247—H27A	109.5
C143—C147—H17C	109.5	C243—C247—H27B	109.5
H17A—C147—H17C	109.5	H27A—C247—H27B	109.5
H17B—C147—H17C	109.5	C243—C247—H27C	109.5
C145—C148—H18A	109.5	H27A—C247—H27C	109.5
C145—C148—H18B	109.5	H27B—C247—H27C	109.5
H18A—C148—H18B	109.5	C245—C248—H28A	109.5
C145—C148—H18C	109.5	C245—C248—H28B	109.5
H18A—C148—H18C	109.5	H28A—C248—H28B	109.5
H18B—C148—H18C	109.5	C245—C248—H28C	109.5
C152—C151—C142	110.9 (2)	H28A—C248—H28C	109.5
C152—C151—H15A	109.5	H28B—C248—H28C	109.5
C142—C151—H15A	109.5	C252—C251—C242	113.68 (13)
C152—C151—H15B	109.5	C252—C251—H25A	108.8
C142—C151—H15B	109.5	C242—C251—H25A	108.8
H15A—C151—H15B	108.0	C252—C251—H25B	108.8
C153—C152—C151	121.9 (8)	C242—C251—H25B	108.8
C153—C152—H152	119.0	H25A—C251—H25B	107.7
C151—C152—H152	119.0	C253—C252—C251	125.92 (15)
C152—C153—H15C	120.0	C253—C252—H252	117.0
C152—C153—H15D	120.0	C251—C252—H252	117.0
H15C—C153—H15D	120.0	C252—C253—H25C	120.0
C163—C162—H162	118.5	C252—C253—H25D	120.0
C162—C163—H16E	120.0	H25C—C253—H25D	120.0
C117—N11—C12—O12	−3.1 (2)	C217—N21—C22—O22	−1.3 (2)
C16—N11—C12—O12	−177.96 (14)	C26—N21—C22—O22	−177.22 (14)
C117—N11—C12—C13	176.37 (13)	C217—N21—C22—C23	177.97 (12)
C16—N11—C12—C13	1.5 (2)	C26—N21—C22—C23	2.07 (19)
O12—C12—C13—N14	−156.18 (13)	O22—C22—C23—N24	−143.34 (14)
N11—C12—C13—N14	24.34 (19)	N21—C22—C23—N24	37.34 (17)
O12—C12—C13—C131	77.08 (17)	O22—C22—C23—C231	89.07 (17)
N11—C12—C13—C131	−102.39 (15)	N21—C22—C23—C231	−90.25 (15)
C12—C13—N14—C15	−30.1 (2)	C231—C23—N24—C25	83.51 (16)
C131—C13—N14—C15	95.98 (17)	C22—C23—N24—C25	−41.55 (18)
C12—C13—N14—C141	153.42 (13)	C231—C23—N24—C241	−96.54 (15)
C131—C13—N14—C141	−80.48 (16)	C22—C23—N24—C241	138.40 (13)
C141—N14—C15—O15	4.3 (2)	C241—N24—C25—O25	5.5 (2)
C13—N14—C15—O15	−171.99 (14)	C23—N24—C25—O25	−174.54 (13)
C141—N14—C15—C16	−175.23 (13)	C241—N24—C25—C26	−174.92 (13)
C13—N14—C15—C16	8.4 (2)	C23—N24—C25—C26	5.03 (19)
C12—N11—C16—C15	−23.7 (2)	C22—N21—C26—C25	−39.10 (19)
C117—N11—C16—C15	161.20 (13)	C217—N21—C26—C25	144.88 (13)
O15—C15—C16—N11	−161.15 (14)	O25—C25—C26—N21	−145.46 (14)
N14—C15—C16—N11	18.4 (2)	N24—C25—C26—N21	34.96 (18)
C12—N11—C117—C111	107.13 (16)	C22—N21—C217—C211	117.40 (15)
C16—N11—C117—C111	−77.60 (17)	C26—N21—C217—C211	−66.57 (17)
N11—C117—C111—C116	−14.3 (2)	N21—C217—C211—C212	151.72 (14)
N11—C117—C111—C112	167.11 (15)	N21—C217—C211—C216	−31.5 (2)
C116—C111—C112—C113	0.2 (3)	C216—C211—C212—C213	−0.5 (2)
C117—C111—C112—C113	178.85 (18)	C217—C211—C212—C213	176.41 (15)
C111—C112—C113—C114	0.0 (3)	C211—C212—C213—C214	0.1 (3)
C112—C113—C114—C115	0.3 (3)	C212—C213—C214—C215	−0.1 (3)
C113—C114—C115—C116	−0.7 (3)	C213—C214—C215—C216	0.6 (3)
C114—C115—C116—C111	0.9 (3)	C214—C215—C216—C211	−1.1 (3)
C112—C111—C116—C115	−0.6 (3)	C212—C211—C216—C215	1.0 (2)
C117—C111—C116—C115	−179.24 (16)	C217—C211—C216—C215	−175.84 (15)
N14—C13—C131—C132	−54.07 (18)	N24—C23—C231—C232	−12.1 (2)
C12—C13—C131—C132	73.40 (17)	C22—C23—C231—C232	113.88 (16)
N14—C13—C131—C136	126.28 (15)	N24—C23—C231—C236	168.72 (13)
C12—C13—C131—C136	−106.25 (16)	C22—C23—C231—C236	−65.33 (17)
C136—C131—C132—C133	−1.1 (2)	C236—C231—C232—C233	−0.1 (2)
C13—C131—C132—C133	179.29 (14)	C23—C231—C232—C233	−179.26 (15)
C131—C132—C133—C134	0.1 (2)	C231—C232—C233—C234	−0.3 (3)
C132—C133—C134—C135	0.8 (2)	C232—C233—C234—C235	0.8 (3)
C133—C134—C135—C136	−0.7 (2)	C233—C234—C235—C236	−0.9 (3)
C132—C131—C136—C135	1.2 (2)	C234—C235—C236—C231	0.6 (2)
C13—C131—C136—C135	−179.15 (15)	C232—C231—C236—C235	−0.1 (2)
C134—C135—C136—C131	−0.3 (2)	C23—C231—C236—C235	179.17 (14)
C15—N14—C141—C146	−92.93 (17)	C25—N24—C241—C246	−74.62 (18)
C13—N14—C141—C146	83.67 (17)	C23—N24—C241—C246	105.43 (16)
C15—N14—C141—C142	89.70 (18)	C25—N24—C241—C242	104.86 (16)
C13—N14—C141—C142	−93.70 (16)	C23—N24—C241—C242	−75.09 (17)
C146—C141—C142—C143	0.1 (2)	C246—C241—C242—C243	−3.3 (2)
N14—C141—C142—C143	177.34 (13)	N24—C241—C242—C243	177.27 (12)
C146—C141—C142—C151	179.29 (15)	C246—C241—C242—C251	172.64 (14)
N14—C141—C142—C151	−3.4 (2)	N24—C241—C242—C251	−6.8 (2)
C141—C142—C143—C144	−0.9 (2)	C241—C242—C243—C244	3.9 (2)
C151—C142—C143—C144	179.89 (15)	C251—C242—C243—C244	−172.04 (13)
C141—C142—C143—C147	178.75 (15)	C241—C242—C243—C247	−177.18 (13)
C151—C142—C143—C147	−0.5 (2)	C251—C242—C243—C247	6.8 (2)
C142—C143—C144—C145	1.1 (2)	C242—C243—C244—C245	−1.0 (2)
C147—C143—C144—C145	−178.53 (15)	C247—C243—C244—C245	−179.90 (14)
C143—C144—C145—C146	−0.4 (2)	C243—C244—C245—C246	−2.7 (2)
C143—C144—C145—C148	−178.35 (16)	C243—C244—C245—C248	174.56 (14)
C142—C141—C146—C145	0.6 (2)	C242—C241—C246—C245	−0.5 (2)
N14—C141—C146—C145	−176.65 (13)	N24—C241—C246—C245	178.98 (13)
C144—C145—C146—C141	−0.4 (2)	C244—C245—C246—C241	3.4 (2)
C148—C145—C146—C141	177.46 (15)	C248—C245—C246—C241	−173.81 (14)
C141—C142—C151—C152	−115.4 (2)	C241—C242—C251—C252	−89.37 (17)
C143—C142—C151—C152	63.7 (3)	C243—C242—C251—C252	86.46 (17)
C142—C151—C152—C153	171.0 (12)	C242—C251—C252—C253	5.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C234—H234···O12	0.95	2.44	3.347 (2)	160
C16—H16A···O15^i	0.99	2.44	3.2682 (19)	141
C217—H21A···O25^ii	0.99	2.29	3.150 (2)	144
C151—H15B···Cg1^iii	0.99	2.60	3.498 (2)	151
C161—H16D···Cg1^iii	0.99	2.86	3.598 (2)	122
C251—H25B···Cg2^iv	0.99	2.70	3.515 (2)	139

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x, y+1/2, −z+1/2; (iii) −x+1, −y+2, −z+1; (iv) −x, −y+1, −z.