N-Ethylazatribenzo-21-crown-7

The structure of the title compound, 25-ethyl-2,5,12,15,22,28-hexa­oxa-25-aza­tetra­cyclo­[27.4.0.0^6,11.0^16,21]­tri­tria­conta-1(29),6(11),7,9,16(21),17,19,30,32-nona­ene, C₂₈H₃₃NO₆, does not exhibit a binding cavity for cations, but is collapsed in on itself. The conformation is unique among known tri­benzo-21-crown-7 structures, and may be a result of intermolecular (C—H...π) and intramolecular (C—H...O) hydrogen bonding.

S1. Comment

We recently reported that tribenzo-21-crown-7 exhibits modest selectivity for large alkali metal cations over smaller ions (Sachleben et al., 1996). This selectivity was subsequently illuminated by a crystallographic and molecular-mechanics study of six different conformations of the free and complexed crown ether ligand (Bryan et al., 1998). Further examination of the Cs(tribenzo-21-crown-7)NO₃ structure reported as part of that study showed that one of the seven crown ether O donor atoms is significantly further from Cs⁺ and its dipole is roughly orthogonal to the Cs—O bond, suggesting that it binds the cation relatively weakly (Hay & Rustad, 1994). Replacement of this O atom with an NR group may result in orientation of the amine dipole more directly towards Cs⁺, allowing enhanced binding and selectivity towards Cs⁺. In this paper, we describe the structure and synthesis of such an NR-containing crown ether, (I).

The structure of (I) is depicted in Fig. 1, which clearly demonstrates that it is not preorganized for cation binding as the ring has collapsed in on itself, which is commonly observed in large uncomplexed crown ether structures (Bryan et al., 1999, 1998, and references therein). In doing so, the crown fills its cavity with methylene groups, which allows for intramolecular hydrogen bonding between methylene H and ether O atoms (Table 2 and Fig. 2). Only those interactions with C—H···O angles greater than 100° and C···O separations less than 3.72 Å are listed in Table 2 (Steiner, 1996).

No π stacking of arene rings is observed in the structure. However, close C—H···π contacts, some of which may represent hydrogen bonds (Steiner et al., 1996; Bryan et al., 1999) or edge-face arene interactions, are clearly present (Fig. 2). These weak intermolecular bonds may also play a role in determining the observed crown conformation. The metrical parameters for these potential hydrogen bonds, as calculated by PLATON (Spek, 1999), are presented in Table 2, with ring centroids represented as Cg2 (C9–C14) and Cg3 (C17–C22).

The crown conformation observed here differs slightly from that of the closely related compound 4,4'-bis-tert-butyl-benzo-benzo-21-crown-7 (Bryan et al., 1998). For instance, the O—C—C—O torsion angles follow the patterns 0 g^-0 g^-0ag^- and 0 g⁺0 g⁺0ag⁺ in the two conformations of the previously reported crown, while the analogous angles in (I) follow the pattern 0 g^-0 g⁺0ag^-. All bond lengths and angles are in good agreement with standard values (Allen, et al., 1987). For example, the C(sp³)—C(sp³) bond lengths range from 1.493 (3) to 1.513 (3) Å, while the C(sp²)—C(sp²) lengths range from 1.377 (3) to 1.410 (2) Å.

S2. Experimental

The title compound was synthesized in 63% yield by heating 1,2-bis[2'(2''-hydroxyphenoxy)ethoxy]benzene (1.3 mmol), N,N-bis(2-chloroethyl)ethylamine (1.3 mmol) and caesium carbonate (13 mmol) in acetonitrile (10 ml) at reflux under argon for 1 h. Aqueous workup was followed by chromatographic purification on silica gel (ether/methanol gradient elution). Crystals were grown by slow evaporation of a diethyl ether solution.

S3. Refinement

Each H atom was placed in a calculated position, refined using a riding model, and given an isotropic displacement parameter equal to 1.2 (CH₂) or 1.5 (CH₃) times the equivalent isotropic displacement parameter of the atom to which it was attached. The C—H distances used depend on the type of C atom: C_aromatic—H = 0.95, C_primary—H = 0.98, C_secondary—H = 0.99 Å. Methyl H atoms were allowed to rotate about C—C.

Computing details

Data collection: CAD-4-PC (Nonius, 1993); cell refinement: CAD-4-PC; data reduction: XCAD4 (Harms, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1995); software used to prepare material for publication: PLATON (Spek, 1999).

Figures

	Fig. 1. Molecular structure of (I) showing 50% probability displacement ellipsoids.
	Fig. 2. Hydrogen-bond interactions of (I). For clarity, only fragments of symmetry-equivalent molecules are shown, all atoms are represented as circles, and only H atoms functioning as hydrogen-bond donors are drawn. Symmetry codes: (i) 1 - x, 1 - y, -z; (ii) x, y, z - 1; (iii) -x, 1 - y, -z; (iv) x, 3/2 - y, z - 1/2; (v) x, 3/2 - y, 1/2 + z.

(I)

Crystal data

C28H33NO6	F(000) = 1024
Mr = 479.6	Dx = 1.28 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 11.0160 (12) Å	θ = 10.1–12.7°
b = 23.084 (3) Å	µ = 0.09 mm^−1
c = 9.9323 (12) Å	T = 173 K
β = 98.977 (9)°	Block, colourless
V = 2494.8 (5) Å^3	0.57 × 0.48 × 0.43 mm
Z = 4

Data collection

Nonius CAD-4 with cryostat diffractometer	Rint = 0.037
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.0°
Graphite monochromator	h = −13→8
ω scans	k = −16→27
6915 measured reflections	l = −11→11
4373 independent reflections	3 standard reflections every 120 min
3312 reflections with I > 2σ(I)	intensity decay: 9%

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.040	Riding
wR(F^2) = 0.110	w = 1/[σ^2(Fo^2) + (0.0631P)^2 + 0.2606P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
4373 reflections	Δρmax = 0.23 e Å^−3
317 parameters	Δρmin = −0.26 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

	x	y	z	Uiso*/Ueq
O1	0.22952 (11)	0.42669 (5)	−0.01095 (12)	0.0299 (4)
O2	0.21392 (11)	0.48253 (5)	0.22514 (12)	0.0293 (4)
O3	0.29218 (11)	0.59750 (5)	0.35069 (12)	0.0312 (4)
O4	0.28088 (10)	0.70145 (5)	0.21709 (11)	0.0263 (3)
O5	0.38584 (10)	0.71160 (5)	−0.02061 (11)	0.0255 (3)
O6	0.42470 (10)	0.61440 (5)	−0.14273 (11)	0.0267 (4)
N	0.37255 (13)	0.46256 (6)	−0.24132 (13)	0.0255 (4)
C1	0.1308 (2)	0.41372 (7)	0.0519 (2)	0.0274 (5)
C2	0.1226 (2)	0.44409 (7)	0.1723 (2)	0.0273 (5)
C3	0.0261 (2)	0.43395 (8)	0.2424 (2)	0.0349 (6)
C4	−0.0640 (2)	0.39354 (8)	0.1945 (2)	0.0386 (6)
C5	−0.0563 (2)	0.36372 (8)	0.0757 (2)	0.0370 (6)
C6	0.0407 (2)	0.37333 (7)	0.0050 (2)	0.0323 (6)
C7	0.2063 (2)	0.53738 (7)	0.1546 (2)	0.0301 (5)
C8	0.3091 (2)	0.57575 (7)	0.2178 (2)	0.0322 (6)
C9	0.19314 (15)	0.63401 (7)	0.3511 (2)	0.0265 (5)
C10	0.18538 (15)	0.68787 (7)	0.2838 (2)	0.0245 (5)
C11	0.08602 (15)	0.72370 (8)	0.2922 (2)	0.0299 (5)
C12	−0.0029 (2)	0.70772 (8)	0.3702 (2)	0.0352 (6)
C13	0.0058 (2)	0.65528 (9)	0.4384 (2)	0.0399 (6)
C14	0.1035 (2)	0.61854 (8)	0.4271 (2)	0.0356 (6)
C15	0.2706 (2)	0.75388 (7)	0.1388 (2)	0.0252 (5)
C16	0.38233 (15)	0.75920 (7)	0.0718 (2)	0.0246 (5)
C17	0.48809 (14)	0.70980 (7)	−0.0838 (2)	0.0227 (5)
C18	0.50761 (14)	0.65777 (7)	−0.1516 (2)	0.0229 (5)
C19	0.6075 (2)	0.65343 (7)	−0.2199 (2)	0.0279 (5)
C20	0.6881 (2)	0.69952 (8)	−0.2223 (2)	0.0307 (6)
C21	0.6685 (2)	0.75034 (8)	−0.1564 (2)	0.0318 (6)
C22	0.5692 (2)	0.75541 (7)	−0.0869 (2)	0.0283 (5)
C23	0.4473 (2)	0.56049 (7)	−0.2071 (2)	0.0293 (6)
C24	0.3623 (2)	0.51541 (7)	−0.1624 (2)	0.0278 (5)
C25	0.3723 (2)	0.40851 (7)	−0.1641 (2)	0.0280 (5)
C26	0.2535 (2)	0.38928 (7)	−0.1194 (2)	0.0313 (6)
C27	0.2905 (2)	0.46296 (7)	−0.3718 (2)	0.0314 (5)
C28	0.3245 (2)	0.41845 (9)	−0.4704 (2)	0.0485 (7)
H3	0.0212	0.4547	0.3240	0.042*
H4	−0.1303	0.3865	0.2432	0.046*
H5	−0.1182	0.3364	0.0421	0.044*
H6	0.0455	0.3522	−0.0761	0.039*
H7A	0.1264	0.5561	0.1606	0.036*
H7B	0.2118	0.5311	0.0572	0.036*
H8A	0.3871	0.5538	0.2270	0.039*
H8B	0.3159	0.6090	0.1563	0.039*
H11	0.0786	0.7594	0.2442	0.036*
H12	−0.0698	0.7329	0.3767	0.042*
H13	−0.0545	0.6445	0.4924	0.048*
H14	0.1087	0.5822	0.4725	0.043*
H15A	0.2644	0.7876	0.1990	0.030*
H15B	0.1959	0.7527	0.0691	0.030*
H16A	0.3801	0.7963	0.0213	0.029*
H16B	0.4570	0.7589	0.1416	0.029*
H19	0.6212	0.6185	−0.2656	0.033*
H20	0.7565	0.6960	−0.2693	0.037*
H21	0.7232	0.7820	−0.1585	0.038*
H22	0.5568	0.7905	−0.0409	0.034*
H23A	0.5340	0.5486	−0.1798	0.035*
H23B	0.4313	0.5648	−0.3075	0.035*
H24A	0.3856	0.5073	−0.0638	0.033*
H24B	0.2765	0.5297	−0.1784	0.033*
H25A	0.4349	0.4121	−0.0815	0.034*
H25B	0.3997	0.3771	−0.2202	0.034*
H26A	0.1852	0.3916	−0.1968	0.038*
H26B	0.2607	0.3486	−0.0873	0.038*
H27A	0.2924	0.5019	−0.4133	0.038*
H27B	0.2055	0.4556	−0.3557	0.038*
H28A	0.2750	0.4246	−0.5602	0.073*
H28B	0.3088	0.3796	−0.4376	0.073*
H28C	0.4119	0.4223	−0.4777	0.073*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0348 (7)	0.0233 (6)	0.0321 (7)	−0.0042 (5)	0.0066 (5)	−0.0037 (5)
O2	0.0352 (7)	0.0194 (6)	0.0321 (6)	−0.0015 (5)	0.0018 (5)	0.0041 (5)
O3	0.0329 (7)	0.0247 (7)	0.0355 (7)	0.0030 (5)	0.0039 (5)	−0.0007 (5)
O4	0.0283 (6)	0.0193 (6)	0.0326 (6)	0.0015 (5)	0.0089 (5)	0.0017 (5)
O5	0.0289 (6)	0.0199 (6)	0.0289 (6)	−0.0031 (5)	0.0083 (5)	−0.0063 (5)
O6	0.0328 (7)	0.0166 (6)	0.0322 (6)	−0.0023 (5)	0.0096 (5)	−0.0040 (5)
N	0.0338 (8)	0.0164 (7)	0.0257 (7)	0.0024 (6)	0.0030 (6)	−0.0012 (6)
C1	0.0278 (9)	0.0206 (9)	0.0329 (10)	0.0017 (7)	0.0016 (7)	0.0065 (7)
C2	0.0281 (9)	0.0191 (8)	0.0332 (9)	0.0007 (7)	0.0004 (7)	0.0063 (7)
C3	0.0392 (11)	0.0283 (10)	0.0382 (10)	0.0024 (8)	0.0095 (9)	0.0041 (8)
C4	0.0324 (10)	0.0348 (11)	0.0494 (12)	−0.0017 (8)	0.0089 (9)	0.0121 (9)
C5	0.0335 (10)	0.0278 (10)	0.0467 (12)	−0.0063 (8)	−0.0033 (9)	0.0105 (9)
C6	0.0370 (10)	0.0234 (9)	0.0341 (10)	−0.0030 (8)	−0.0016 (8)	0.0031 (8)
C7	0.0426 (10)	0.0182 (9)	0.0305 (9)	0.0051 (8)	0.0088 (8)	0.0037 (7)
C8	0.0369 (10)	0.0207 (9)	0.0420 (10)	0.0025 (8)	0.0158 (8)	−0.0005 (8)
C9	0.0275 (9)	0.0239 (9)	0.0276 (9)	−0.0021 (7)	0.0026 (7)	−0.0052 (7)
C10	0.0251 (9)	0.0237 (9)	0.0250 (8)	−0.0033 (7)	0.0045 (7)	−0.0056 (7)
C11	0.0272 (9)	0.0271 (9)	0.0348 (10)	−0.0008 (7)	0.0028 (7)	−0.0061 (8)
C12	0.0241 (9)	0.0379 (11)	0.0441 (11)	0.0008 (8)	0.0066 (8)	−0.0113 (9)
C13	0.0330 (10)	0.0458 (12)	0.0440 (11)	−0.0091 (9)	0.0157 (9)	−0.0068 (9)
C14	0.0385 (11)	0.0321 (10)	0.0372 (10)	−0.0088 (8)	0.0092 (8)	−0.0006 (8)
C15	0.0308 (9)	0.0168 (8)	0.0273 (9)	0.0027 (7)	0.0025 (7)	−0.0010 (7)
C16	0.0307 (9)	0.0161 (8)	0.0264 (9)	−0.0003 (7)	0.0030 (7)	−0.0042 (7)
C17	0.0245 (8)	0.0204 (8)	0.0224 (8)	0.0022 (7)	0.0009 (7)	0.0006 (7)
C18	0.0265 (8)	0.0178 (8)	0.0237 (8)	0.0002 (7)	0.0014 (7)	0.0023 (7)
C19	0.0329 (9)	0.0233 (9)	0.0275 (9)	0.0046 (7)	0.0051 (7)	0.0006 (7)
C20	0.0248 (9)	0.0326 (10)	0.0358 (10)	0.0033 (8)	0.0082 (7)	0.0042 (8)
C21	0.0272 (9)	0.0256 (9)	0.0424 (11)	−0.0041 (8)	0.0051 (8)	0.0013 (8)
C22	0.0306 (9)	0.0201 (9)	0.0334 (9)	−0.0007 (7)	0.0026 (7)	−0.0032 (7)
C23	0.0368 (10)	0.0186 (9)	0.0338 (10)	0.0004 (7)	0.0094 (8)	−0.0058 (7)
C24	0.0345 (10)	0.0207 (9)	0.0291 (9)	0.0008 (7)	0.0076 (8)	−0.0037 (7)
C25	0.0359 (10)	0.0198 (9)	0.0276 (9)	0.0019 (7)	0.0030 (7)	−0.0004 (7)
C26	0.0425 (11)	0.0211 (9)	0.0295 (9)	−0.0039 (8)	0.0031 (8)	−0.0026 (7)
C27	0.0407 (10)	0.0223 (9)	0.0297 (9)	0.0029 (8)	0.0006 (8)	0.0020 (8)
C28	0.0694 (15)	0.0453 (12)	0.0281 (10)	0.0131 (11)	−0.0008 (10)	−0.0054 (9)

Geometric parameters (Å, º)

O1—C1	1.369 (2)	C25—C26	1.513 (3)
O1—C26	1.437 (2)	C27—C28	1.506 (3)
O2—C2	1.382 (2)	C3—H3	0.95
O2—C7	1.443 (2)	C4—H4	0.95
O3—C8	1.451 (2)	C5—H5	0.95
O3—C9	1.379 (2)	C6—H6	0.95
O4—C10	1.364 (2)	C7—H7A	0.99
O4—C15	1.433 (2)	C7—H7B	0.99
O5—C16	1.436 (2)	C8—H8A	0.99
O5—C17	1.373 (2)	C8—H8B	0.99
O6—C18	1.367 (2)	C11—H11	0.95
O6—C23	1.438 (2)	C12—H12	0.95
N—C24	1.464 (2)	C13—H13	0.95
N—C25	1.465 (2)	C14—H14	0.95
N—C27	1.460 (2)	C15—H15A	0.99
C1—C2	1.401 (3)	C15—H15B	0.99
C1—C6	1.388 (3)	C16—H16A	0.99
C2—C3	1.379 (3)	C16—H16B	0.99
C3—C4	1.391 (3)	C19—H19	0.95
C4—C5	1.380 (3)	C20—H20	0.95
C5—C6	1.385 (3)	C21—H21	0.95
C7—C8	1.496 (3)	C22—H22	0.95
C9—C10	1.408 (2)	C23—H23A	0.99
C9—C14	1.380 (3)	C23—H23B	0.99
C10—C11	1.385 (2)	C24—H24A	0.99
C11—C12	1.390 (3)	C24—H24B	0.99
C12—C13	1.383 (3)	C25—H25A	0.99
C13—C14	1.388 (3)	C25—H25B	0.99
C15—C16	1.493 (3)	C26—H26A	0.99
C17—C18	1.410 (2)	C26—H26B	0.99
C17—C22	1.384 (2)	C27—H27A	0.99
C18—C19	1.383 (3)	C27—H27B	0.99
C19—C20	1.388 (3)	C28—H28A	0.98
C20—C21	1.377 (3)	C28—H28B	0.98
C21—C22	1.387 (3)	C28—H28C	0.98
C23—C24	1.512 (3)
C1—O1—C26	117.6 (1)	O3—C8—H8B	109
C2—O2—C7	113.3 (1)	C7—C8—H8A	109
C8—O3—C9	115.4 (1)	C7—C8—H8B	109
C10—O4—C15	117.1 (1)	H8A—C8—H8B	108
C16—O5—C17	114.9 (1)	C10—C11—H11	120
C18—O6—C23	116.2 (1)	C12—C11—H11	120
C24—N—C25	115.0 (1)	C11—C12—H12	120
C24—N—C27	112.4 (1)	C13—C12—H12	120
C25—N—C27	114.8 (1)	C12—C13—H13	120
O1—C1—C2	116.2 (2)	C14—C13—H13	120
O1—C1—C6	124.8 (2)	C9—C14—H14	120
C2—C1—C6	119.0 (2)	C13—C14—H14	119
O2—C2—C1	120.4 (2)	O4—C15—H15A	110
O2—C2—C3	119.4 (2)	O4—C15—H15B	110
C1—C2—C3	120.2 (2)	C16—C15—H15A	110
C2—C3—C4	120.4 (2)	C16—C15—H15B	110
C3—C4—C5	119.4 (2)	H15A—C15—H15B	108
C4—C5—C6	120.6 (2)	O5—C16—H16A	110
C1—C6—C5	120.4 (2)	O5—C16—H16B	110
O2—C7—C8	109.4 (2)	C15—C16—H16A	110
O3—C8—C7	113.0 (2)	C15—C16—H16B	110
O3—C9—C10	121.9 (2)	H16A—C16—H16B	108
O3—C9—C14	118.5 (2)	C18—C19—H19	120
C10—C9—C14	119.5 (2)	C20—C19—H19	120
O4—C10—C9	116.1 (1)	C19—C20—H20	120
O4—C10—C11	124.7 (2)	C21—C20—H20	120
C9—C10—C11	119.3 (2)	C20—C21—H21	120
C10—C11—C12	120.5 (2)	C22—C21—H21	120
C11—C12—C13	120.3 (2)	C17—C22—H22	120
C12—C13—C14	119.4 (2)	C21—C22—H22	120
C9—C14—C13	121.1 (2)	O6—C23—H23A	110
O4—C15—C16	108.1 (2)	O6—C23—H23B	110
O5—C16—C15	109.2 (1)	C24—C23—H23A	110
O5—C17—C18	116.2 (1)	C24—C23—H23B	110
O5—C17—C22	124.4 (2)	H23A—C23—H23B	108
C18—C17—C22	119.4 (2)	N—C24—H24A	110
O6—C18—C17	116.1 (1)	N—C24—H24B	110
O6—C18—C19	124.7 (2)	C23—C24—H24A	110
C17—C18—C19	119.2 (2)	C23—C24—H24B	110
C18—C19—C20	120.8 (2)	H24A—C24—H24B	108
C19—C20—C21	119.8 (2)	N—C25—H25A	108
C20—C21—C22	120.2 (2)	N—C25—H25B	108
C17—C22—C21	120.6 (2)	C26—C25—H25A	108
O6—C23—C24	107.9 (2)	C26—C25—H25B	108
N—C24—C23	108.3 (2)	H25A—C25—H25B	107
N—C25—C26	118.4 (2)	O1—C26—H26A	110
O1—C26—C25	108.2 (1)	O1—C26—H26B	110
N—C27—C28	113.0 (2)	C25—C26—H26A	110
C2—C3—H3	120	C25—C26—H26B	110
C4—C3—H3	120	H26A—C26—H26B	108
C3—C4—H4	120	N—C27—H27A	109
C5—C4—H4	120	N—C27—H27B	109
C4—C5—H5	120	C28—C27—H27A	109
C6—C5—H5	120	C28—C27—H27B	109
C1—C6—H6	120	H27A—C27—H27B	108
C5—C6—H6	120	C27—C28—H28A	110
O2—C7—H7A	110	C27—C28—H28B	110
O2—C7—H7B	110	C27—C28—H28C	109
C8—C7—H7A	110	H28A—C28—H28B	110
C8—C7—H7B	110	H28A—C28—H28C	109
H7A—C7—H7B	108	H28B—C28—H28C	110
O3—C8—H8A	109
C1—C2—C3—C4	0.0 (3)	C26—O1—C1—C2	168.7 (2)
C1—O1—C26—C25	−174.8 (2)	C26—O1—C1—C6	−11.2 (3)
C10—C11—C12—C13	−1.2 (3)	C27—N—C24—C23	−86.2 (2)
C10—C9—C14—C13	−0.1 (3)	C27—N—C25—C26	−61.5 (2)
C10—O4—C15—C16	−178.3 (1)	C3—C4—C5—C6	0.6 (3)
C11—C12—C13—C14	−0.6 (3)	C4—C5—C6—C1	−0.8 (3)
C12—C13—C14—C9	1.2 (3)	C6—C1—C2—O2	176.9 (2)
C14—C9—C10—O4	176.5 (2)	C6—C1—C2—C3	−0.2 (3)
C14—C9—C10—C11	−1.7 (3)	C7—O2—C2—C3	−105.2 (2)
C15—O4—C10—C9	175.2 (2)	C7—O2—C2—C1	77.7 (2)
C15—O4—C10—C11	−6.8 (3)	C8—O3—C9—C14	120.9 (2)
C16—O5—C17—C18	166.9 (2)	C8—O3—C9—C10	−63.3 (2)
C16—O5—C17—C22	−14.5 (2)	C9—C10—C11—C12	2.3 (3)
C17—C18—C19—C20	0.0 (3)	C9—O3—C8—C7	−65.0 (2)
C17—O5—C16—C15	−176.8 (1)	N—C25—C26—O1	−72.4 (2)
C18—C17—C22—C21	0.3 (3)	O1—C1—C2—C3	179.9 (2)
C18—C19—C20—C21	−0.2 (3)	O1—C1—C2—O2	−3.1 (3)
C18—O6—C23—C24	168.8 (2)	O1—C1—C6—C5	−179.5 (2)
C19—C20—C21—C22	0.5 (3)	O2—C2—C3—C4	−177.1 (2)
C2—C1—C6—C5	0.6 (3)	O2—C7—C8—O3	−72.5 (2)
C2—C3—C4—C5	−0.2 (3)	O3—C9—C10—C11	−177.5 (2)
C2—O2—C7—C8	−179.5 (2)	O3—C9—C10—O4	0.7 (3)
C20—C21—C22—C17	−0.6 (3)	O3—C9—C14—C13	175.9 (2)
C22—C17—C18—O6	179.2 (2)	O4—C10—C11—C12	−175.7 (2)
C22—C17—C18—C19	0.0 (3)	O4—C15—C16—O5	62.9 (2)
C23—O6—C18—C17	−177.5 (2)	O5—C17—C18—C19	178.6 (2)
C23—O6—C18—C19	1.7 (3)	O5—C17—C18—O6	−2.1 (2)
C24—N—C25—C26	71.2 (2)	O5—C17—C22—C21	−178.2 (2)
C24—N—C27—C28	163.3 (2)	O6—C18—C19—C20	−179.2 (2)
C25—N—C24—C23	140.0 (2)	O6—C23—C24—N	172.4 (1)
C25—N—C27—C28	−62.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···O1	0.99	2.52	3.071 (2)	115
C8—H8B···O4	0.99	2.27	2.918 (2)	122
C25—H25A···O6^i	0.99	2.58	3.527 (2)	160
C28—H28A···O2^ii	0.98	2.52	3.416 (2)	152
C6—H6···Cg2^iii	0.95	3.05	3.84	142
C15—H15B···Cg2^iv	0.99	2.81	3.56	134
C16—H16B···Cg3^v	0.99	2.46	3.37	154

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