Ethyl 23-benzyl-8,11,14-trioxa-23,28,29-triaza-penta-cyclo-[19.7.1.0(2,7).0(15,20).0(22,27)]nona-cosa-2,4,6,15(20),16,18,21,26-octa-ene-26-carboxyl-ate.

The title compound, C33H35N3O5, is the product of the multicomponent condensation of 1-benzyl-4-eth-oxy-carbonyl-piperidin-3-one with 1,5-bis-(2-formyl-phen-oxy)-3-oxapentane and ammonium acetate. The mol-ecule comprises a penta-cyclic system containing the aza-14-crown-4-ether macrocycle, tetra-hydro-pyrimidine, tetra-hydro-pyridine and two benzene rings. The aza-14-crown-4-ether ring adopts a bowl conformation with a dihedral angle of 62.37 (5)° between the benzene rings. The tetra-hydro-pyrimidine ring has an envelope conformation with the chiral C atom as the flap, whereas the tetra-hydro-pyridine ring adopts a distorted chair conformation. Two amino groups are involved in intra-molecular N-H⋯O hydrogen bonds. In the crystal, weak C-H⋯O hydrogen bonds link the mol-ecules into layers parallel to the ab plane.

Related literature

For general background to the design, synthesis, chemical properties and applications of macrocyclic ligands for coordination chemistry, see: Hiraoka (1982 ▶); Pedersen (1988 ▶); Gokel & Murillo (1996 ▶); Bradshaw & Izatt (1997 ▶). For the crystal structures of related compounds, see: Levov et al. (2006 ▶, 2008 ▶); Komarova et al. (2008 ▶); Anh et al. (2008 ▶, 2012a ▶,b ▶,c ▶); Hieu et al. (2009 ▶, 2011 ▶, 2012a ▶,b ▶); Khieu et al. (2011 ▶); Sokol et al. (2011 ▶).

Experimental

Crystal data

C33H35N3O5

M = 553.64

Monoclinic,

a = 10.5304 (5) Å

b = 12.6363 (5) Å

c = 10.7246 (5) Å

β = 92.865 (1)°

V = 1425.29 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.30 × 0.24 × 0.21 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.974, T max = 0.982

18837 measured reflections

8289 independent reflections

6878 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.094

S = 1.00

8289 reflections

377 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAIn class="Chemical">NT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813007241/cv5393sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007241/cv5393Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813007241/cv5393Isup3.cml

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

C33H35N3O5	F(000) = 588
Mr = 553.64	Dx = 1.290 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5715 reflections
a = 10.5304 (5) Å	θ = 2.5–31.8°
b = 12.6363 (5) Å	µ = 0.09 mm−1
c = 10.7246 (5) Å	T = 100 K
β = 92.865 (1)°	Prism, yellow
V = 1425.29 (11) Å3	0.30 × 0.24 × 0.21 mm
Z = 2

Bruker APEXII CCD diffractometer	8289 independent reflections
Radiation source: fine-focus sealed tube	6878 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
φ and ω scans	θmax = 30.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −14→14
Tmin = 0.974, Tmax = 0.982	k = −17→17
18837 measured reflections	l = −15→15

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)] = 0.040	Hydrogen site location: difference Fourier map
wR(F2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0431P)2 + 0.123P] where P = (Fo2 + 2Fc2)/3
8289 reflections	(Δ/σ)max < 0.001
377 parameters	Δρmax = 0.23 e Å−3
1 restraint	Δρmin = −0.18 e Å−3

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
C1	0.22606 (12)	0.22945 (12)	0.85547 (12)	0.0266 (3)
H1	0.1992	0.2950	0.8090	0.032*
C2	0.16248 (12)	0.22544 (12)	0.97887 (12)	0.0271 (3)
C3	0.13663 (14)	0.13054 (13)	1.03713 (13)	0.0310 (3)
H3	0.1570	0.0660	0.9974	0.037*
C4	0.08137 (14)	0.12737 (14)	1.15267 (14)	0.0347 (3)
H4	0.0644	0.0615	1.1912	0.042*
C5	0.05172 (14)	0.22147 (15)	1.21021 (14)	0.0376 (3)
H5	0.0148	0.2200	1.2892	0.045*
C6	0.07508 (15)	0.31771 (14)	1.15432 (14)	0.0365 (3)
H6	0.0533	0.3819	1.1942	0.044*
C7	0.13097 (13)	0.31993 (13)	1.03861 (13)	0.0312 (3)
O8	0.15789 (13)	0.41119 (10)	0.97691 (11)	0.0441 (3)
C9	0.16598 (16)	0.50775 (12)	1.04698 (14)	0.0360 (3)
H9A	0.2106	0.4957	1.1292	0.043*
H9B	0.0799	0.5356	1.0607	0.043*
C10	0.23872 (16)	0.58408 (13)	0.97119 (14)	0.0367 (3)
H10A	0.2017	0.5874	0.8846	0.044*
H10B	0.2362	0.6558	1.0081	0.044*
O11	0.36498 (10)	0.54650 (9)	0.97231 (10)	0.0380 (3)
C12	0.43821 (16)	0.59053 (13)	0.87902 (14)	0.0372 (3)
H12A	0.4594	0.6651	0.8995	0.045*
H12B	0.3899	0.5889	0.7975	0.045*
C13	0.55719 (15)	0.52654 (12)	0.87280 (14)	0.0338 (3)
H13A	0.6134	0.5571	0.8108	0.041*
H13B	0.6039	0.5252	0.9552	0.041*
O14	0.51863 (10)	0.42183 (9)	0.83650 (11)	0.0372 (2)
C15	0.61093 (14)	0.35024 (12)	0.81031 (13)	0.0298 (3)
C16	0.74063 (14)	0.37340 (13)	0.81731 (15)	0.0361 (3)
H16	0.7694	0.4404	0.8472	0.043*
C17	0.82748 (14)	0.29860 (14)	0.78062 (15)	0.0388 (4)
H17	0.9156	0.3150	0.7847	0.047*
C18	0.78697 (14)	0.20051 (13)	0.73815 (15)	0.0367 (4)
H18	0.8465	0.1499	0.7114	0.044*
C19	0.65764 (14)	0.17656 (13)	0.73505 (14)	0.0325 (3)
H19	0.6300	0.1085	0.7075	0.039*
C20	0.56790 (13)	0.25002 (12)	0.77133 (12)	0.0273 (3)
C21	0.43077 (12)	0.22008 (12)	0.76601 (12)	0.0269 (3)
C22	0.37341 (13)	0.17558 (12)	0.66288 (13)	0.0272 (3)
C23	0.24979 (13)	0.12495 (11)	0.66886 (12)	0.0255 (3)
N24	0.19281 (12)	0.13681 (10)	0.78031 (11)	0.0289 (3)
H24	0.1137 (17)	0.1140 (14)	0.7817 (16)	0.035*
N25	0.36503 (11)	0.22816 (11)	0.87544 (11)	0.0278 (2)
H25	0.3951 (16)	0.2792 (14)	0.9247 (16)	0.033*
N1'	0.43614 (11)	0.17458 (10)	0.54726 (10)	0.0272 (2)
C4'	0.20023 (13)	0.06475 (12)	0.57082 (12)	0.0280 (3)
C5'	0.27720 (14)	0.04519 (14)	0.45751 (13)	0.0353 (3)
H5A	0.2425	0.0885	0.3869	0.042*
H5B	0.2699	−0.0302	0.4331	0.042*
C6'	0.41709 (14)	0.07292 (12)	0.48401 (13)	0.0306 (3)
H6A	0.4575	0.0165	0.5364	0.037*
H6B	0.4602	0.0747	0.4041	0.037*
C7'	0.39864 (15)	0.26627 (13)	0.46972 (15)	0.0357 (3)
H7A	0.3881	0.3282	0.5248	0.043*
H7B	0.3151	0.2514	0.4269	0.043*
C8'	0.49217 (14)	0.29427 (11)	0.37288 (13)	0.0301 (3)
C9'	0.44865 (17)	0.34402 (13)	0.26331 (15)	0.0399 (4)
H9	0.3599	0.3525	0.2462	0.048*
C10'	0.5333 (2)	0.38131 (15)	0.17872 (17)	0.0510 (5)
H10	0.5024	0.4164	0.1049	0.061*
C11'	0.6611 (2)	0.36766 (15)	0.20134 (18)	0.0542 (5)
H11	0.7189	0.3930	0.1431	0.065*
C12'	0.70637 (18)	0.31703 (15)	0.30879 (18)	0.0474 (4)
H12	0.7952	0.3070	0.3239	0.057*
C13'	0.62174 (15)	0.28063 (13)	0.39512 (15)	0.0366 (3)
H13	0.6531	0.2464	0.4693	0.044*
C14'	0.07571 (14)	0.01805 (12)	0.57658 (13)	0.0298 (3)
O1'	0.00688 (10)	0.02090 (9)	0.66562 (9)	0.0342 (2)
O2'	0.03869 (11)	−0.03237 (11)	0.46902 (11)	0.0452 (3)
C15'	−0.08813 (17)	−0.07689 (17)	0.46202 (18)	0.0507 (5)
H15A	−0.1111	−0.1000	0.5462	0.061*
H15B	−0.0901	−0.1397	0.4068	0.061*
C16'	−0.1818 (2)	0.0022 (2)	0.4129 (3)	0.0858 (9)
H16A	−0.2654	−0.0313	0.4006	0.129*
H16B	−0.1548	0.0298	0.3330	0.129*
H16C	−0.1871	0.0605	0.4727	0.129*

	U11	U22	U33	U12	U13	U23
C1	0.0254 (6)	0.0334 (7)	0.0211 (6)	0.0014 (6)	0.0027 (5)	−0.0038 (5)
C2	0.0213 (6)	0.0390 (7)	0.0210 (6)	0.0017 (6)	0.0012 (5)	−0.0044 (6)
C3	0.0274 (7)	0.0388 (8)	0.0271 (7)	0.0060 (6)	0.0032 (5)	−0.0015 (6)
C4	0.0281 (7)	0.0466 (9)	0.0299 (7)	0.0044 (6)	0.0053 (6)	0.0039 (6)
C5	0.0307 (7)	0.0566 (10)	0.0262 (7)	0.0022 (7)	0.0087 (5)	−0.0027 (7)
C6	0.0354 (8)	0.0456 (9)	0.0295 (7)	0.0015 (7)	0.0089 (6)	−0.0103 (7)
C7	0.0298 (7)	0.0385 (8)	0.0257 (7)	−0.0007 (6)	0.0045 (5)	−0.0063 (6)
O8	0.0656 (8)	0.0368 (6)	0.0311 (6)	−0.0050 (6)	0.0139 (5)	−0.0102 (5)
C9	0.0405 (8)	0.0359 (8)	0.0317 (7)	0.0062 (6)	0.0044 (6)	−0.0091 (6)
C10	0.0431 (9)	0.0337 (8)	0.0329 (8)	0.0110 (7)	−0.0015 (6)	−0.0025 (6)
O11	0.0395 (6)	0.0419 (6)	0.0330 (5)	0.0087 (5)	0.0049 (5)	0.0092 (5)
C12	0.0484 (9)	0.0305 (7)	0.0327 (8)	0.0005 (7)	0.0014 (7)	0.0052 (6)
C13	0.0386 (8)	0.0323 (8)	0.0306 (7)	−0.0076 (6)	0.0026 (6)	0.0011 (6)
O14	0.0305 (5)	0.0331 (6)	0.0484 (7)	−0.0034 (4)	0.0060 (5)	−0.0088 (5)
C15	0.0286 (7)	0.0345 (7)	0.0267 (7)	−0.0018 (6)	0.0049 (5)	0.0024 (5)
C16	0.0315 (8)	0.0398 (9)	0.0370 (8)	−0.0073 (6)	0.0027 (6)	0.0032 (7)
C17	0.0251 (7)	0.0517 (10)	0.0399 (8)	−0.0032 (7)	0.0043 (6)	0.0146 (7)
C18	0.0283 (7)	0.0469 (10)	0.0353 (8)	0.0096 (6)	0.0059 (6)	0.0089 (7)
C19	0.0322 (7)	0.0368 (8)	0.0288 (7)	0.0029 (6)	0.0035 (6)	0.0033 (6)
C20	0.0252 (6)	0.0358 (8)	0.0211 (6)	−0.0013 (5)	0.0034 (5)	0.0027 (5)
C21	0.0244 (6)	0.0309 (7)	0.0257 (6)	−0.0001 (6)	0.0046 (5)	−0.0027 (6)
C22	0.0266 (7)	0.0336 (7)	0.0220 (6)	−0.0012 (6)	0.0070 (5)	−0.0004 (5)
C23	0.0260 (6)	0.0287 (7)	0.0220 (6)	0.0024 (5)	0.0026 (5)	−0.0005 (5)
N24	0.0261 (6)	0.0375 (7)	0.0237 (5)	−0.0049 (5)	0.0061 (5)	−0.0066 (5)
N25	0.0242 (5)	0.0367 (6)	0.0229 (5)	−0.0029 (5)	0.0039 (4)	−0.0067 (5)
N1'	0.0292 (6)	0.0331 (6)	0.0197 (5)	0.0018 (5)	0.0057 (4)	0.0014 (4)
C4'	0.0285 (7)	0.0341 (8)	0.0216 (6)	0.0000 (6)	0.0020 (5)	−0.0031 (5)
C5'	0.0343 (8)	0.0487 (9)	0.0230 (6)	−0.0027 (7)	0.0043 (6)	−0.0086 (6)
C6'	0.0305 (7)	0.0380 (8)	0.0236 (6)	0.0027 (6)	0.0058 (5)	−0.0037 (6)
C7'	0.0349 (8)	0.0405 (8)	0.0323 (7)	0.0109 (6)	0.0092 (6)	0.0078 (6)
C8'	0.0372 (8)	0.0272 (7)	0.0265 (7)	0.0017 (6)	0.0064 (6)	0.0013 (5)
C9'	0.0499 (9)	0.0385 (9)	0.0311 (7)	0.0039 (7)	0.0001 (7)	0.0061 (6)
C10'	0.0774 (14)	0.0410 (10)	0.0352 (9)	−0.0028 (9)	0.0092 (9)	0.0128 (7)
C11'	0.0757 (14)	0.0426 (10)	0.0466 (10)	−0.0157 (9)	0.0262 (10)	0.0039 (8)
C12'	0.0409 (9)	0.0468 (10)	0.0555 (10)	−0.0095 (8)	0.0138 (8)	−0.0014 (9)
C13'	0.0377 (8)	0.0378 (8)	0.0346 (8)	0.0006 (6)	0.0047 (6)	0.0034 (6)
C14'	0.0307 (7)	0.0312 (7)	0.0273 (7)	−0.0001 (6)	−0.0015 (5)	−0.0019 (6)
O1'	0.0327 (5)	0.0388 (6)	0.0314 (5)	−0.0058 (4)	0.0052 (4)	−0.0018 (4)
O2'	0.0381 (6)	0.0640 (8)	0.0335 (6)	−0.0157 (6)	0.0017 (5)	−0.0158 (5)
C15'	0.0457 (10)	0.0629 (12)	0.0430 (10)	−0.0233 (9)	−0.0026 (8)	−0.0109 (9)
C16'	0.0484 (12)	0.113 (2)	0.0931 (19)	−0.0321 (13)	−0.0237 (12)	0.0484 (17)

C1—N24	1.4542 (18)	C21—C22	1.3556 (19)
C1—N25	1.4685 (17)	C21—N25	1.3957 (16)
C1—C2	1.5135 (17)	C22—N1'	1.4338 (17)
C1—H1	1.0000	C22—C23	1.4548 (19)
C2—C3	1.386 (2)	C23—N24	1.3721 (17)
C2—C7	1.403 (2)	C23—C4'	1.3790 (19)
C3—C4	1.396 (2)	N24—H24	0.882 (18)
C3—H3	0.9500	N25—H25	0.883 (18)
C4—C5	1.383 (2)	N1'—C6'	1.4620 (19)
C4—H4	0.9500	N1'—C7'	1.4687 (19)
C5—C6	1.383 (3)	C4'—C14'	1.442 (2)
C5—H5	0.9500	C4'—C5'	1.5144 (19)
C6—C7	1.400 (2)	C5'—C6'	1.527 (2)
C6—H6	0.9500	C5'—H5A	0.9900
C7—O8	1.366 (2)	C5'—H5B	0.9900
O8—C9	1.4334 (18)	C6'—H6A	0.9900
C9—C10	1.497 (2)	C6'—H6B	0.9900
C9—H9A	0.9900	C7'—C8'	1.509 (2)
C9—H9B	0.9900	C7'—H7A	0.9900
C10—O11	1.4114 (19)	C7'—H7B	0.9900
C10—H10A	0.9900	C8'—C13'	1.384 (2)
C10—H10B	0.9900	C8'—C9'	1.390 (2)
O11—C12	1.4079 (18)	C9'—C10'	1.386 (2)
C12—C13	1.495 (2)	C9'—H9	0.9500
C12—H12A	0.9900	C10'—C11'	1.367 (3)
C12—H12B	0.9900	C10'—H10	0.9500
C13—O14	1.4322 (18)	C11'—C12'	1.382 (3)
C13—H13A	0.9900	C11'—H11	0.9500
C13—H13B	0.9900	C12'—C13'	1.395 (2)
O14—C15	1.3672 (18)	C12'—H12	0.9500
C15—C16	1.395 (2)	C13'—H13	0.9500
C15—C20	1.402 (2)	C14'—O1'	1.2279 (17)
C16—C17	1.386 (2)	C14'—O2'	1.3578 (17)
C16—H16	0.9500	O2'—C15'	1.448 (2)
C17—C18	1.381 (2)	C15'—C16'	1.482 (3)
C17—H17	0.9500	C15'—H15A	0.9900
C18—C19	1.394 (2)	C15'—H15B	0.9900
C18—H18	0.9500	C16'—H16A	0.9800
C19—C20	1.394 (2)	C16'—H16B	0.9800
C19—H19	0.9500	C16'—H16C	0.9800
C20—C21	1.4912 (18)
N24—C1—N25	106.41 (11)	N25—C21—C20	117.99 (11)
N24—C1—C2	110.67 (12)	C21—C22—N1'	120.23 (12)
N25—C1—C2	110.68 (11)	C21—C22—C23	120.64 (12)
N24—C1—H1	109.7	N1'—C22—C23	119.09 (12)
N25—C1—H1	109.7	N24—C23—C4'	123.99 (12)
C2—C1—H1	109.7	N24—C23—C22	114.94 (12)
C3—C2—C7	118.32 (12)	C4'—C23—C22	120.95 (12)
C3—C2—C1	121.92 (13)	C23—N24—C1	117.85 (12)
C7—C2—C1	119.74 (13)	C23—N24—H24	115.7 (11)
C2—C3—C4	121.69 (14)	C1—N24—H24	117.0 (11)
C2—C3—H3	119.2	C21—N25—C1	114.25 (11)
C4—C3—H3	119.2	C21—N25—H25	112.2 (11)
C5—C4—C3	119.02 (15)	C1—N25—H25	113.9 (11)
C5—C4—H4	120.5	C22—N1'—C6'	110.52 (11)
C3—C4—H4	120.5	C22—N1'—C7'	111.12 (11)
C4—C5—C6	120.91 (13)	C6'—N1'—C7'	113.80 (11)
C4—C5—H5	119.5	C23—C4'—C14'	120.22 (12)
C6—C5—H5	119.5	C23—C4'—C5'	120.30 (12)
C5—C6—C7	119.57 (14)	C14'—C4'—C5'	119.46 (12)
C5—C6—H6	120.2	C4'—C5'—C6'	111.30 (11)
C7—C6—H6	120.2	C4'—C5'—H5A	109.4
O8—C7—C6	123.56 (14)	C6'—C5'—H5A	109.4
O8—C7—C2	115.95 (12)	C4'—C5'—H5B	109.4
C6—C7—C2	120.49 (14)	C6'—C5'—H5B	109.4
C7—O8—C9	118.22 (11)	H5A—C5'—H5B	108.0
O8—C9—C10	106.41 (12)	N1'—C6'—C5'	113.37 (12)
O8—C9—H9A	110.4	N1'—C6'—H6A	108.9
C10—C9—H9A	110.4	C5'—C6'—H6A	108.9
O8—C9—H9B	110.4	N1'—C6'—H6B	108.9
C10—C9—H9B	110.4	C5'—C6'—H6B	108.9
H9A—C9—H9B	108.6	H6A—C6'—H6B	107.7
O11—C10—C9	106.62 (12)	N1'—C7'—C8'	114.11 (12)
O11—C10—H10A	110.4	N1'—C7'—H7A	108.7
C9—C10—H10A	110.4	C8'—C7'—H7A	108.7
O11—C10—H10B	110.4	N1'—C7'—H7B	108.7
C9—C10—H10B	110.4	C8'—C7'—H7B	108.7
H10A—C10—H10B	108.6	H7A—C7'—H7B	107.6
C12—O11—C10	114.21 (12)	C13'—C8'—C9'	118.85 (14)
O11—C12—C13	107.93 (12)	C13'—C8'—C7'	121.60 (13)
O11—C12—H12A	110.1	C9'—C8'—C7'	119.27 (14)
C13—C12—H12A	110.1	C10'—C9'—C8'	120.77 (16)
O11—C12—H12B	110.1	C10'—C9'—H9	119.6
C13—C12—H12B	110.1	C8'—C9'—H9	119.6
H12A—C12—H12B	108.4	C11'—C10'—C9'	120.05 (17)
O14—C13—C12	106.55 (12)	C11'—C10'—H10	120.0
O14—C13—H13A	110.4	C9'—C10'—H10	120.0
C12—C13—H13A	110.4	C10'—C11'—C12'	120.14 (16)
O14—C13—H13B	110.4	C10'—C11'—H11	119.9
C12—C13—H13B	110.4	C12'—C11'—H11	119.9
H13A—C13—H13B	108.6	C11'—C12'—C13'	120.06 (17)
C15—O14—C13	118.19 (12)	C11'—C12'—H12	120.0
O14—C15—C16	123.66 (14)	C13'—C12'—H12	120.0
O14—C15—C20	115.89 (12)	C8'—C13'—C12'	120.10 (15)
C16—C15—C20	120.43 (14)	C8'—C13'—H13	119.9
C17—C16—C15	119.99 (15)	C12'—C13'—H13	119.9
C17—C16—H16	120.0	O1'—C14'—O2'	121.26 (13)
C15—C16—H16	120.0	O1'—C14'—C4'	126.49 (13)
C18—C17—C16	120.57 (14)	O2'—C14'—C4'	112.25 (12)
C18—C17—H17	119.7	C14'—O2'—C15'	116.83 (12)
C16—C17—H17	119.7	O2'—C15'—C16'	110.61 (17)
C17—C18—C19	119.21 (14)	O2'—C15'—H15A	109.5
C17—C18—H18	120.4	C16'—C15'—H15A	109.5
C19—C18—H18	120.4	O2'—C15'—H15B	109.5
C20—C19—C18	121.60 (15)	C16'—C15'—H15B	109.5
C20—C19—H19	119.2	H15A—C15'—H15B	108.1
C18—C19—H19	119.2	C15'—C16'—H16A	109.5
C19—C20—C15	118.12 (13)	C15'—C16'—H16B	109.5
C19—C20—C21	119.28 (13)	H16A—C16'—H16B	109.5
C15—C20—C21	122.59 (12)	C15'—C16'—H16C	109.5
C22—C21—N25	119.80 (12)	H16A—C16'—H16C	109.5
C22—C21—C20	121.84 (12)	H16B—C16'—H16C	109.5
N24—C1—C2—C3	30.99 (17)	C21—C22—C23—N24	6.9 (2)
N25—C1—C2—C3	−86.73 (16)	N1'—C22—C23—N24	−175.27 (12)
N24—C1—C2—C7	−150.56 (13)	C21—C22—C23—C4'	−169.29 (14)
N25—C1—C2—C7	91.72 (15)	N1'—C22—C23—C4'	8.5 (2)
C7—C2—C3—C4	−0.4 (2)	C4'—C23—N24—C1	−157.44 (13)
C1—C2—C3—C4	178.09 (13)	C22—C23—N24—C1	26.47 (18)
C2—C3—C4—C5	0.0 (2)	N25—C1—N24—C23	−55.37 (16)
C3—C4—C5—C6	0.6 (2)	C2—C1—N24—C23	−175.67 (12)
C4—C5—C6—C7	−0.8 (2)	C22—C21—N25—C1	−24.73 (19)
C5—C6—C7—O8	−179.74 (15)	C20—C21—N25—C1	162.10 (13)
C5—C6—C7—C2	0.4 (2)	N24—C1—N25—C21	53.10 (16)
C3—C2—C7—O8	−179.70 (13)	C2—C1—N25—C21	173.39 (12)
C1—C2—C7—O8	1.80 (18)	C21—C22—N1'—C6'	139.13 (14)
C3—C2—C7—C6	0.1 (2)	C23—C22—N1'—C6'	−38.69 (17)
C1—C2—C7—C6	−178.37 (13)	C21—C22—N1'—C7'	−93.54 (16)
C6—C7—O8—C9	19.4 (2)	C23—C22—N1'—C7'	88.65 (16)
C2—C7—O8—C9	−160.75 (13)	N24—C23—C4'—C14'	6.2 (2)
C7—O8—C9—C10	160.67 (13)	C22—C23—C4'—C14'	−177.91 (13)
O8—C9—C10—O11	−68.86 (15)	N24—C23—C4'—C5'	−172.46 (14)
C9—C10—O11—C12	163.21 (13)	C22—C23—C4'—C5'	3.4 (2)
C10—O11—C12—C13	−167.25 (13)	C23—C4'—C5'—C6'	15.1 (2)
O11—C12—C13—O14	62.76 (15)	C14'—C4'—C5'—C6'	−163.57 (13)
C12—C13—O14—C15	172.76 (12)	C22—N1'—C6'—C5'	57.81 (15)
C13—O14—C15—C16	0.2 (2)	C7'—N1'—C6'—C5'	−68.03 (15)
C13—O14—C15—C20	−177.99 (12)	C4'—C5'—C6'—N1'	−46.07 (17)
O14—C15—C16—C17	−175.38 (15)	C22—N1'—C7'—C8'	158.26 (13)
C20—C15—C16—C17	2.7 (2)	C6'—N1'—C7'—C8'	−76.22 (16)
C15—C16—C17—C18	−0.7 (2)	N1'—C7'—C8'—C13'	−34.0 (2)
C16—C17—C18—C19	−1.4 (2)	N1'—C7'—C8'—C9'	152.10 (14)
C17—C18—C19—C20	1.4 (2)	C13'—C8'—C9'—C10'	−1.3 (2)
C18—C19—C20—C15	0.7 (2)	C7'—C8'—C9'—C10'	172.83 (16)
C18—C19—C20—C21	179.96 (13)	C8'—C9'—C10'—C11'	1.2 (3)
O14—C15—C20—C19	175.56 (13)	C9'—C10'—C11'—C12'	−0.3 (3)
C16—C15—C20—C19	−2.7 (2)	C10'—C11'—C12'—C13'	−0.6 (3)
O14—C15—C20—C21	−3.7 (2)	C9'—C8'—C13'—C12'	0.4 (2)
C16—C15—C20—C21	178.04 (13)	C7'—C8'—C13'—C12'	−173.59 (16)
C19—C20—C21—C22	−49.5 (2)	C11'—C12'—C13'—C8'	0.6 (3)
C15—C20—C21—C22	129.79 (16)	C23—C4'—C14'—O1'	−4.2 (2)
C19—C20—C21—N25	123.54 (15)	C5'—C4'—C14'—O1'	174.51 (14)
C15—C20—C21—N25	−57.19 (19)	C23—C4'—C14'—O2'	175.85 (13)
N25—C21—C22—N1'	174.95 (13)	C5'—C4'—C14'—O2'	−5.5 (2)
C20—C21—C22—N1'	−12.2 (2)	O1'—C14'—O2'—C15'	3.5 (2)
N25—C21—C22—C23	−7.3 (2)	C4'—C14'—O2'—C15'	−176.51 (15)
C20—C21—C22—C23	165.62 (13)	C14'—O2'—C15'—C16'	88.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N24—H24···O1′	0.882 (18)	2.015 (18)	2.6928 (16)	132.8 (15)
N25—H25···O14	0.882 (18)	2.441 (17)	2.9744 (17)	119.3 (13)
C6—H6···O1′i	0.95	2.42	3.3516 (19)	168
C18—H18···O1′ii	0.95	2.42	3.3613 (19)	174

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N24—H24⋯O1′	0.882 (18)	2.015 (18)	2.6928 (16)	132.8 (15)
N25—H25⋯O14	0.882 (18)	2.441 (17)	2.9744 (17)	119.3 (13)
C6—H6⋯O1′i	0.95	2.42	3.3516 (19)	168
C18—H18⋯O1′ii	0.95	2.42	3.3613 (19)	174

Symmetry codes: (i) ; (ii) .