25,27:26,28-Bis(3,9-dioxa-6-aza­undecane-1,11-dioxy)­calix­[4]­arene tetrahydrate

The title compound, C₄₄H₅₄N₂O₈·4H₂O, has twofold crystallographic symmetry and consists of a calix­[4]­arene moiety with four phenyl rings arranged alternately in anti-orientation fashion and two aza­crown units attached on the lower rims of calix­[4]­arene. This seems to offer a big cavity inside the mol­ecule which might possess a potential for forming host-guest complexes.

S1. Comment

Calix[4]arenes have been of particular interest as organic hosts and selective ionophores in inclusion complexation (Gutsche, 1989) and it is known that the calix[4]arenes are able to exist in the following four different conformations: cone (Guelzim et al., 1997; Harkema et al., 1998), partial cone (Kim et al., 1993), 1,2-alternate and 1,3-alternate (Ungaro & Pochini, 1991). In order to investigate the characteristics of the calix[4]arene compounds, a series of calix[4]arene derivatives has been synthesized and their structures elucidated (Kim et al., 1997; Kim, Pang et al., 1998; Kim, Yu et al., 1998; Kim, Suh et al., 1998; Kim, Kim, Lee et al., 1999; Kim, Kim, Choo et al., 1999).

In the title compound, (I), a half molecule belongs to an asymmetric unit and a molecule is completed by another half primed molecule translated by twofold symmetry along the b axis [symmetry code: (i) 1 - x, y, 1/2 - z] (Fig. 1). \sch

(I) consists of the calix[4]arene molecule adopting the 1,3-alternate conformation: two phenyl groups A and B' lie above and the other two phenyl groups A' and B below the least-squares plane defined by the four bridging methylene groups as clearly illustrated in Figure 1, two azacrown units: one of them bonded to phenyl rings A and B' and another one to phenyl rings A' and B, respectively, and four water molecules not represented in the Figure.

The aromatic Csp²– Csp² distances in the molecule vary from 1.367 (5) to 1.397 (5) Å with an average value of 1.385 (1) Å, Csp²—Csp³ distances from 1.511 (4) to 1.522 (4) Å with a mean value of 1.516 (2) Å, Csp³—Csp³ distances from 1.480 (5) to 1.490 (5) Å with a mean value of 1.485 (3) Å, O-Csp³ distances from 1.377 (4) to 1.438 (4) Å with a mean value of 1.414 (2) Å, and a mean value of two O-Csp² bonds is 1.383 (3) Å. All of these are very close to those in 25,27-bis(1-propyloxy)calix[4]arene- 26,28-[(5',6')(14',15')-dibenzo]crown-7 (Kim, Pang et al., 1999) and in 1,3-alternate calix[4]arenebiscrown-7 (Khrifi et al., 1997).

Bond angles involving the bridging methylenes C2—C3—C2' = 113.7 (4), C7—C8—C9 = 114.4 (3) and C13—C14—C13' = 114.6 (4)° are quite larger than the tetrahedral angle due to repulsions among the four phenyl groups.

Two adjacent phenyl rings in the calix[4]arene are perpendicular to each other with dihedral angle of A—B = 89.76 (8)° so that the calix[4]arene has a fairly perfect square cavity. However, two facing rings A and B' are slightly splayed out upwards from the central axis with a dihedral angle of 11.6 (2)° leading to C1···C15' 5.337 (4) and C5···C11' 5.870 (5) Å, and the same for the pair facing rings A' and B because of symmetry.

In the azacrown unit, O···O and N···O distances are O1···O2' 5.135 (3), O3···O4' 5.311 (4), N···O1' 4.742 (4) and N···O2 4.800 (4) Å, so that the somewhat flexible cavity lined with four oxygen atoms and a nitrogen atom might enable the molecule to introduce a guest atom. Additionally the torsion angles of O2—C16—C17—O3 and O4—C22—C23—O1 in the azacrown unit are both gauche being -58.5 (5) and 59.9 (4)°, respectively.

There are four hydrogen bonds involving the N atom in the amine group and the two water molecules in an asymmetric unit and it is especially worth mentioning that two water oxygen atoms donate and accept their hydrogen atoms with each other as shown in Table 1, where the distances between H2W1····H1W2 and H2W2····H2W2 (2 - x, -y, 1 - z) are 1.76 and 1.74 Å, respectively. This hydrogen-bond scheme makes an infinite molecular chain running in the [201] direction and the closest contact between the molecular chains is OW1···HC3 (1/2 + x, -1/2 + y, 1/2 - z) = 2.51 Å.

S2. Experimental

Under nitrogen, into a three-neck round-bottom flask, K₂CO₃ (0.96 g, 6.95 mmol), pre-dried N,N-dimethylformamide (DMF) (60 ml), 25,26,27,28-tetra(5-chloro-3-oxapentyloxy)calix[4]arene (5.00 g, 5.88 mmol), and p-toluenesulfonamide (2.11 g, 12.3 mmol) were placed and refluxed for 24 h. DMF was completely removed in vacuo and 10% NaHCO₃ aqueous solution (100 ml) and CH₂Cl₂ (100 ml) were added and then the organic layer was separated. The organic layer was washed with water (2 x 50 ml) and dried over anhydrous MgSO₄ and filtered. Evaporation of the CH₂Cl₂ in vacuo gave a yellowish oil which was purified by column chromatography (R_f 0.3) using ethyl acetate: hexane (1:8) to provide 4.00 g (65%) of N-tosyl calix[4]arene bis(azacrown-5) as a white solid (m.p. 421–424 K). To a solution of 1,4-dioxane (100 ml) and methanol (20 ml) were carefully added N-tosyl calix[4]arene bisazacrown-5 (3.00 g, 2.86 mmol) and 6% Na(Hg) amalgam (0.853 g). The reaction mixture refluxed for 2 d at 353 K. After cooling to room temperature the solvent was evaporated in vacuo. CH₂Cl₂ (50 ml) and water (50 ml) were added and the organic layer was separated. The CH₂Cl₂ layer was washed twice with 10% Na₂HPO₄ aqueous solution followed by drying over anhydrous MgSO₄. After filtration of magnesium sulfate, removal of the solvent in vacuo gave calix[4]arene bis(azacrown-5) as a white solid which can be recrystallized with diethyl ether (30 ml) (m.p. 458–461 K, 52% yield). IR (KBr pellet, cm^-1): 2926, 1456, 1359, 1176, 1094, 928, 767, 664. ¹H NMR (CDCl₃, p.p.m.): delta 7.18–6.64 (m, 12 H, Ar—H), 3.88 (s, 8 H, ArCH₂Ar), 3.67–3.46 (m, 24 H, –CH₂–), 2.81(s, 8 H, –OCH₂CH₂NCH₂–): p.p.m. 157.3,134.6, 131.8, 122.7, 71.7, 71.4, 70.9, 49.6, 38.5. FAB MS m/z (M⁺) calculated 738.9, found 739.1.

S3. Refinement

An H atom of the amine group and those of C3 and C14 sat on a twofold axis could be located from a difference Fourier map and the positions of the four hydrogen atoms of two water molecules were calculated by the program HYDROGEN (Nardelli, 1999), and their positions were fixed with U_iso (H) = 1.2U_eq (N, C, O), while all other H atoms were placed in calculated positions and allowed to ride upon the carbon atoms with U_iso (H) = 1.2U_eq (C).

Computing details

Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Johnson, 1976); software used to prepare material for publication: WinGX publication routines (Farrugia, 1998).

Figures

Fig. 1. ORTEP (Johnson, 1976) drawing of (I) with atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level. The unprimed atoms belong to an asymmetric unit and a molecule is completed by another primed asymmetric unit translated by a symmetry code, 1 - x, y, 0.5 - z. Phenyl rings A and B' are slightly splayed out upwards. The oxygen and nitrogen atoms are expressed with ellipsoids with octant shading, and water molecules and H atoms are omitted for clarity.

(I)

Crystal data

C44H54N2O8·4H2O	Dx = 1.225 Mg m^−3
Mr = 810.96	Mo Kα radiation, λ = 0.71069 Å
Orthorhombic, Pbcn	Cell parameters from 25 reflections
a = 15.922 (2) Å	θ = 11.0–12.5°
b = 16.7908 (16) Å	µ = 0.09 mm^−1
c = 16.453 (4) Å	T = 288 K
V = 4398.6 (13) Å^3	Block, colorless
Z = 4	0.73 × 0.59 × 0.59 mm
F(000) = 1744

Data collection

Enraf Nonius CAD4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 2.2°
Graphite monochromator	h = 0→18
non–profiled ω/2θ scans	k = 0→19
4330 measured reflections	l = −19→0
3861 independent reflections	3 standard reflections every 300 min
2185 reflections with I > 2σ(I)	intensity decay: 2%

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.205	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Calculated w = 1/[σ^2(Fo^2) + (0.0944P)^2 + 2.5719P] where P = (Fo^2 + 2Fc^2)/3
3861 reflections	(Δ/σ)max < 0.001
263 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

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
N	0.83325 (17)	0.19262 (18)	0.21232 (18)	0.0564 (8)
HN	0.7724	0.1956	0.2139	0.068*
O1	0.40432 (14)	0.29323 (13)	0.14743 (13)	0.0477 (6)
O2	0.57001 (14)	0.07666 (13)	0.13362 (14)	0.0506 (6)
O3	0.73809 (15)	0.09153 (15)	0.09413 (15)	0.0638 (7)
O4	0.23551 (15)	0.32006 (17)	0.18414 (16)	0.0710 (8)
C1	0.4904 (2)	0.29852 (18)	0.13584 (19)	0.0436 (8)
C2	0.5380 (2)	0.35139 (19)	0.1824 (2)	0.0486 (8)
C3	0.5000	0.4006 (3)	0.2500	0.0540 (13)
HC3	0.4531	0.4423	0.2264	0.065*
C4	0.6235 (2)	0.3552 (2)	0.1657 (2)	0.0610 (10)
HC4	0.6569	0.3908	0.1946	0.073*
C5	0.6599 (2)	0.3078 (3)	0.1075 (3)	0.0682 (11)
HC5	0.7170	0.3126	0.0964	0.082*
C6	0.6124 (2)	0.2537 (2)	0.0658 (2)	0.0630 (11)
HC6	0.6380	0.2204	0.0280	0.076*
C7	0.5266 (2)	0.2476 (2)	0.0788 (2)	0.0494 (9)
C8	0.4745 (2)	0.1864 (2)	0.0340 (2)	0.0593 (10)
HC8A	0.5099	0.1601	−0.0058	0.071*
HC8B	0.4302	0.2137	0.0047	0.071*
C9	0.4351 (2)	0.1235 (2)	0.0880 (2)	0.0497 (9)
C10	0.3484 (2)	0.1151 (2)	0.0914 (2)	0.0605 (10)
HC10	0.3150	0.1471	0.0586	0.073*
C11	0.3108 (2)	0.0607 (2)	0.1418 (3)	0.0655 (11)
HC11	0.2527	0.0549	0.1419	0.079*
C12	0.3599 (2)	0.0146 (2)	0.1924 (2)	0.0601 (10)
HC12	0.3343	−0.0215	0.2274	0.072*
C13	0.4464 (2)	0.02107 (19)	0.1919 (2)	0.0501 (9)
C14	0.5000	−0.0279 (3)	0.2500	0.0599 (14)
HC14	0.4603	−0.0675	0.2801	0.072*
C15	0.4835 (2)	0.07318 (18)	0.1368 (2)	0.0444 (8)
C16	0.6072 (2)	0.0311 (3)	0.0689 (3)	0.0702 (12)
H16A	0.6007	0.0593	0.0178	0.084*
H16B	0.5790	−0.0199	0.0643	0.084*
C17	0.6975 (2)	0.0186 (2)	0.0861 (3)	0.0696 (12)
H17A	0.7037	−0.0119	0.1359	0.084*
H17B	0.7228	−0.0116	0.0422	0.084*
C18	0.8247 (2)	0.0836 (2)	0.1134 (2)	0.0622 (11)
H18A	0.8547	0.0602	0.0680	0.075*
H18B	0.8316	0.0492	0.1603	0.075*
C19	0.8584 (2)	0.1642 (2)	0.1314 (2)	0.0630 (10)
H19A	0.9193	0.1628	0.1282	0.076*
H19B	0.8384	0.2013	0.0906	0.076*
C20	0.8704 (2)	0.2694 (2)	0.2325 (3)	0.0668 (11)
H20A	0.8500	0.3093	0.1947	0.080*
H20B	0.9309	0.2661	0.2265	0.080*
C21	0.1500 (2)	0.2947 (2)	0.1834 (3)	0.0702 (12)
H21A	0.1426	0.2506	0.1460	0.084*
H21B	0.1136	0.3380	0.1667	0.084*
C22	0.2670 (2)	0.3332 (3)	0.1074 (2)	0.0701 (12)
H22A	0.2352	0.3754	0.0814	0.084*
H22B	0.2605	0.2853	0.0751	0.084*
C23	0.3575 (2)	0.3559 (2)	0.1102 (2)	0.0630 (11)
H23A	0.3781	0.3652	0.0556	0.076*
H23B	0.3642	0.4046	0.1412	0.076*
OW1	0.9337 (2)	0.08721 (18)	0.30622 (19)	0.0895 (10)
H1W1	0.9003	0.1133	0.2746	0.107*
H2W1	0.9028	0.0496	0.3270	0.107*
OW2	0.9462 (3)	0.0594 (2)	0.47177 (19)	0.1154 (13)
H1W2	0.9501	0.0715	0.4210	0.138*
H2W2	0.9531	0.0083	0.4738	0.138*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N	0.0451 (16)	0.0609 (19)	0.0630 (19)	−0.0039 (14)	−0.0002 (14)	0.0018 (16)
O1	0.0504 (14)	0.0452 (13)	0.0475 (13)	0.0034 (11)	−0.0032 (11)	0.0050 (11)
O2	0.0478 (14)	0.0540 (14)	0.0501 (14)	0.0019 (11)	−0.0031 (11)	−0.0147 (11)
O3	0.0529 (16)	0.0665 (17)	0.0721 (18)	0.0063 (13)	−0.0026 (13)	−0.0025 (14)
O4	0.0557 (17)	0.087 (2)	0.0707 (18)	0.0031 (14)	−0.0090 (14)	0.0063 (15)
C1	0.0469 (19)	0.0437 (18)	0.0402 (17)	0.0018 (16)	−0.0009 (15)	0.0148 (16)
C2	0.055 (2)	0.0423 (19)	0.049 (2)	−0.0025 (17)	−0.0049 (17)	0.0150 (16)
C3	0.068 (3)	0.039 (3)	0.055 (3)	0.000	−0.009 (3)	0.000
C4	0.062 (2)	0.059 (2)	0.061 (2)	−0.013 (2)	−0.008 (2)	0.018 (2)
C5	0.054 (2)	0.082 (3)	0.069 (3)	−0.001 (2)	0.009 (2)	0.022 (2)
C6	0.064 (3)	0.073 (3)	0.052 (2)	0.010 (2)	0.011 (2)	0.011 (2)
C7	0.060 (2)	0.050 (2)	0.0381 (18)	0.0057 (17)	0.0015 (17)	0.0091 (16)
C8	0.071 (2)	0.066 (2)	0.0411 (19)	0.013 (2)	−0.0044 (18)	−0.0031 (18)
C9	0.058 (2)	0.049 (2)	0.0428 (19)	0.0076 (17)	−0.0097 (17)	−0.0126 (16)
C10	0.057 (2)	0.060 (2)	0.065 (3)	0.012 (2)	−0.018 (2)	−0.017 (2)
C11	0.049 (2)	0.069 (3)	0.079 (3)	−0.001 (2)	−0.009 (2)	−0.016 (2)
C12	0.059 (2)	0.052 (2)	0.069 (3)	−0.0110 (19)	−0.002 (2)	−0.009 (2)
C13	0.057 (2)	0.0392 (19)	0.055 (2)	−0.0028 (16)	−0.0065 (18)	−0.0099 (16)
C14	0.066 (3)	0.041 (3)	0.073 (4)	0.000	−0.006 (3)	0.000
C15	0.044 (2)	0.0414 (18)	0.0472 (19)	0.0009 (15)	−0.0066 (16)	−0.0174 (16)
C16	0.061 (2)	0.076 (3)	0.074 (3)	0.009 (2)	0.003 (2)	−0.034 (2)
C17	0.063 (3)	0.073 (3)	0.073 (3)	0.013 (2)	0.004 (2)	−0.025 (2)
C18	0.054 (2)	0.069 (3)	0.063 (2)	0.0112 (19)	0.0025 (19)	−0.002 (2)
C19	0.056 (2)	0.076 (3)	0.057 (2)	0.002 (2)	0.0065 (19)	0.008 (2)
C20	0.051 (2)	0.067 (2)	0.083 (3)	−0.009 (2)	−0.005 (2)	0.005 (2)
C21	0.053 (2)	0.066 (3)	0.092 (3)	0.004 (2)	−0.014 (2)	0.009 (2)
C22	0.069 (3)	0.084 (3)	0.058 (2)	0.018 (2)	−0.010 (2)	0.009 (2)
C23	0.061 (2)	0.069 (2)	0.059 (2)	0.011 (2)	−0.0058 (19)	0.021 (2)
OW1	0.101 (2)	0.088 (2)	0.079 (2)	0.0274 (18)	−0.0023 (17)	0.0165 (17)
OW2	0.179 (4)	0.103 (3)	0.065 (2)	0.027 (3)	0.009 (2)	−0.0020 (19)

Geometric parameters (Å, º)

N—C20	1.457 (4)	C6—C7	1.386 (5)
N—C19	1.471 (5)	C7—C8	1.513 (5)
O1—C1	1.386 (4)	C8—C9	1.516 (5)
O1—C23	1.428 (4)	C9—C10	1.389 (5)
O2—C15	1.380 (4)	C9—C15	1.397 (5)
O2—C16	1.438 (4)	C10—C11	1.371 (5)
O3—C17	1.392 (4)	C11—C12	1.379 (5)
O3—C18	1.421 (4)	C12—C13	1.382 (5)
O4—C22	1.377 (4)	C13—C15	1.392 (5)
O4—C21	1.427 (4)	C13—C14^i	1.522 (4)
C1—C2	1.397 (4)	C13—C14	1.522 (4)
C1—C7	1.395 (4)	C14—C13^i	1.522 (4)
C2—C4	1.392 (5)	C16—C17	1.480 (5)
C2—C3	1.511 (4)	C18—C19	1.486 (5)
C3—C2^i	1.511 (4)	C20—C21^i	1.482 (6)
C4—C5	1.374 (5)	C21—C20^i	1.482 (6)
C5—C6	1.367 (5)	C22—C23	1.490 (5)
C20—N—C19	112.5 (3)	C15—C9—C8	122.0 (3)
C1—O1—C23	114.2 (2)	C11—C10—C9	121.8 (4)
C15—O2—C16	114.6 (3)	C10—C11—C12	119.4 (4)
C17—O3—C18	112.9 (3)	C11—C12—C13	121.2 (4)
C22—O4—C21	112.8 (3)	C12—C13—C15	118.4 (3)
O1—C1—C2	120.1 (3)	C12—C13—C14^i	120.9 (3)
O1—C1—C7	117.5 (3)	C15—C13—C14^i	120.7 (3)
C2—C1—C7	122.3 (3)	C12—C13—C14	120.9 (3)
C4—C2—C1	116.9 (3)	C15—C13—C14	120.7 (3)
C4—C2—C3	120.8 (3)	C13^i—C14—C13	114.6 (4)
C1—C2—C3	122.3 (3)	O2—C15—C13	118.3 (3)
C2—C3—C2^i	113.7 (4)	O2—C15—C9	120.2 (3)
C5—C4—C2	121.6 (4)	C13—C15—C9	121.4 (3)
C6—C5—C4	120.1 (4)	O2—C16—C17	109.5 (3)
C5—C6—C7	121.1 (4)	O3—C17—C16	110.1 (3)
C6—C7—C1	117.8 (3)	O3—C18—C19	108.1 (3)
C6—C7—C8	121.0 (3)	N—C19—C18	112.2 (3)
C1—C7—C8	121.2 (3)	N—C20—C21^i	112.2 (3)
C7—C8—C9	114.4 (3)	O4—C21—C20^i	106.7 (3)
C10—C9—C15	117.6 (3)	O4—C22—C23	111.3 (3)
C10—C9—C8	120.4 (3)	O1—C23—C22	109.3 (3)
C23—O1—C1—C2	78.6 (4)	C12—C13—C14—C14^i	0 (68)
C23—O1—C1—C7	−103.6 (3)	C15—C13—C14—C14^i	0 (67)
O1—C1—C2—C4	−178.0 (3)	C12—C13—C14—C13^i	−119.5 (3)
C7—C1—C2—C4	4.3 (5)	C15—C13—C14—C13^i	60.8 (2)
O1—C1—C2—C3	3.9 (4)	C14^i—C13—C14—C13^i	0 (100)
C7—C1—C2—C3	−173.7 (3)	C16—O2—C15—C13	99.0 (4)
C4—C2—C3—C2^i	−117.0 (3)	C16—O2—C15—C9	−83.8 (4)
C1—C2—C3—C2^i	61.0 (3)	C12—C13—C15—O2	−176.8 (3)
C1—C2—C4—C5	−1.6 (5)	C14^i—C13—C15—O2	2.8 (4)
C3—C2—C4—C5	176.5 (3)	C14—C13—C15—O2	2.8 (4)
C2—C4—C5—C6	−1.8 (6)	C12—C13—C15—C9	6.0 (5)
C4—C5—C6—C7	2.6 (6)	C14^i—C13—C15—C9	−174.4 (3)
C5—C6—C7—C1	0.1 (5)	C14—C13—C15—C9	−174.4 (3)
C5—C6—C7—C8	−178.6 (3)	C10—C9—C15—O2	177.4 (3)
O1—C1—C7—C6	178.7 (3)	C8—C9—C15—O2	−3.5 (5)
C2—C1—C7—C6	−3.6 (5)	C10—C9—C15—C13	−5.4 (5)
O1—C1—C7—C8	−2.6 (4)	C8—C9—C15—C13	173.7 (3)
C2—C1—C7—C8	175.1 (3)	C15—O2—C16—C17	−162.5 (3)
C6—C7—C8—C9	115.6 (4)	C18—O3—C17—C16	178.0 (3)
C1—C7—C8—C9	−63.0 (4)	O2—C16—C17—O3	−58.5 (5)
C7—C8—C9—C10	119.4 (4)	C17—O3—C18—C19	−172.5 (3)
C7—C8—C9—C15	−59.6 (4)	C20—N—C19—C18	176.4 (3)
C15—C9—C10—C11	1.4 (5)	O3—C18—C19—N	76.2 (4)
C8—C9—C10—C11	−177.7 (3)	C19—N—C20—C21^i	−175.6 (3)
C9—C10—C11—C12	1.9 (6)	C22—O4—C21—C20^i	170.2 (3)
C10—C11—C12—C13	−1.3 (6)	C21—O4—C22—C23	−177.3 (3)
C11—C12—C13—C15	−2.5 (5)	C1—O1—C23—C22	165.1 (3)
C11—C12—C13—C14^i	177.8 (3)	O4—C22—C23—O1	59.9 (4)
C11—C12—C13—C14	177.8 (3)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
OW1—H1W1···N	0.86	1.99	2.842 (4)	168
OW1—H2W1···OW2	0.87	2.49	2.771 (4)	100
OW2—H1W2···OW1	0.86	1.92	2.771 (4)	167
OW2—H2W2···OW2^ii	0.87	2.16	2.788 (7)	129

Symmetry code: (ii) −x+2, −y, −z+1.