1,14-Dioxa-5,10-di­aza-2,3:12,13-dibenzo­cyclo­octadeca-2,12-diene monohydrate

The title compound, C₂₂H₃₀N₂O₂·H₂O, is an 18-membered di­aza-crown ether ligand containing two ether O and two aza N atoms. In the macrocyclic ring, the mean N...O distance is 4.526 (4) Å. The macrocyclic inner-hole size, estimated as twice the mean distance of the donor atoms from their centroid, is ~2.29 Å.

S1. Comment

Macrocyclic multidentate ligands, such as the 16-, 17-, 18- and 19-membered ring containing the –O_xN_y-donor type (where x = 2 and 3, and y = 2 and 3), have been the subject of structural studies as potential metal-ion selective reagents for transition metal-ion recognition (Goodwin et al., 1982; Adam, Leong et al., 1983; Lindoy, 1987; Lindoy et al., 1993; Esteban et al., 2000). Particular metal-ion binding applications (e.g. selective extraction of heavy and precious metals) are of great interest in environmental, inorganic, organic, bio- and coordination chemistry (Esteban et al., 2000; Hökelek, Kaya & Kılıç, 2001; Lindoy, 1997; Hayvalı et al., 1999; Vicente et al., 2000).

Some of the macrocyclic ligands may act as capping ligands, favouring both the blocking of transition metal coordination sites and the formation of discrete metal complexes in inorganic chemistry (Blake & Schröder, 1990; Blake et al., 2000; Nunes et al., 2003). On the other hand, the azamacrocycles, crown ethers and cryptates also play a part in forming host–guest-type inclusion complexes with neutral polar molecules and onium salts (Byriel et al., 2003; Lehn, 1985; Newcomb et al., 1977).

Many investigations have been devoted to the synthetic, thermodynamic and/or structural properties of selective complex formation of a range of transition metal ions and neutral molecules (Adam, Lindoy et al., 1979; Adam, Clarkson et al., 1994; Fenton et al., 1987). However, there are only a limited number of reports concerning the structures of the free macrocyclic multidentate N₂O₂ and N₂O₃ donor-type ligands and neutral molecular complexes (Hökelek et al., 1999a,b, 2000; Hökelek, Akduran et al., 2001a,b; Hökelek, Bilge et al., 2001; Hökelek, Kaya & Kılıç, 2001; Hökelek, Bilge & Kılıç, 2002, 2003). The title compound, (I), may be a potential cation selective reagent for transition metal ions. Its dionium salt may also be a potential anion selective reagent. The structure determination of (I) was carried out in order to estimate the macrocyclic ring hole size.

Fig. 1 shows the molecular structure of (I), with the atomic numbering scheme. The macrocyclic ring comprises two ether O and two N atoms and crystallizes with one water molecule. The ligand cavity plays an important role in metal-ion selectivity. The intramolecular O2···N15 [6.877 (3) Å], O7···N20 [5.113 (4) Å], O2···C14 [6.988 (3) Å], O7···C21 [6.118 (4) Å], C3···C16 [7.611 (4) Å] C5···C18 [4.109 (3) Å] and C13···C22 [8.711 (4) Å] distances may indicate the hole size of the macrocyclic ring. When only the N and O atoms are taken into account, the average value of the four N···O distances in the ring is 4.526 (4) Å [O2···N20 = 2.985 (4) Å and O7···N15 = 3.130 (4) Å]. The deviations from the least-squares plane defined by atoms O2, O7, N15 andN 20 are −0.009 (2) Å (O2), 0.012 (2) Å (O7), −0.021 (2) Å (N15) and 0.017 (2) Å (N20).

The macrocyclic inner-hole size, estimated as twice the mean distance of the donor atoms from their centroid, is approximately 2.29 Å, using the 'modified covalent radii' of the Nsp² (0.66 Å) and Osp³ (0.76 Å) atoms as in the literature method (Goodwin et al., 1982; Adam, Leong et al., 1983; Drummond et al., 1982). The inner hole size of (I) (2.29 Å), which is an 18-membered macrocycle, can be compared with the 16- (1.57 Å; Hökelek et al., 2000), 17- [1.29 (Hökelek et al., 2003) and 2.08 Å (Hökelek, Kaya & Kılıç, 2001)], 18- [1.63 and 1.87 Å (Hökelek, Akduran et al., 2001a), 2.15 Å (Hökelek, Akduran et al., 2001b), and 2.28 Å (Hökelek, Bilge et al., 2001)] and 19-membered (2.53 Å: Hökelek et al., 1999b) multidentate ligand hole sizes. The 15- and 17-membered rings containing the N₂O₂ and N₃O₂-donor type ligands afford the Ni^II and Pd^II complexes (Bilge et al., 2004). The title ligand, (I), may also give similar complexes with Ni^II, Pd^II and other transition metal cations.

In (I), the intermolecular O—H···N hydrogen bonds (Table 2) between the water molecule and atoms N15 and N20 of the macrocycle, and the intramolecular N—H···O close contacts, seem to affect? the macrocyclic ring conformation and, therefore, the macrocyclic inner-hole size. The conformation of the macrocyclic ring is given by the torsion angles. The optimum values of the torsion angles in the macrocyclic ring must be 180° (anti) or 60° (gauche), and in (I), eleven are anti and five are gauche (Table 1). As can be seen from the packing diagram (Fig. 2), the macrocyclic ligands are elongated approximately parallel to the c axis and are stacked along the a axis. The intermolecular hydrogen bonds between the water molecules and the N atoms of the macrocycles result in the formation of zigzag polymeric chains (supramolecules; Lindoy & Atkinson, 2000) parallel to the c axis.

S2. Experimental

The title compound, (I), was obtained from the reaction of 1,4-bis(salicyloxy)butane (0.5 g, 1.65 mmol; Hökelek, Kaya & Kılıç, 2001) in methanol (100 ml) and 1,4-diaminobutane (0.26 ml, 2.47 mmol) in methanol (50 ml). Argon was passed over the reaction mixture, and the mixture was refluxed for 1 h, after which excess amounts of borax (2.51 g, 6.60 mmol) and sodium borohydride (0.25 g, 6.60 mmol) were partially added. The reduction was completed after 2 h. The solvent was then evaporated under reduced pressure. The residue was dissolved in chloroform and extracted with water, and the chloroform layers were collected and evaporated under reduced pressure. The oily residue was crystallized from n-heptane (yield 0.58 g, 56%; m.p. 352 K).

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The broken lines show hydrogen bonds.
	Fig. 2. Packing diagram of (I). The broken lines show hydrogen bonds.

1,14-Dioxa-5,10-diaza-2,3:12,13-dibenzocyclooctadeca-2,12-diene monohydrate

Crystal data

C22H30N2O2·H2O	F(000) = 808
Mr = 372.50	Dx = 1.183 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.6247 (12) Å	θ = 10–18°
b = 14.7854 (10) Å	µ = 0.08 mm^−1
c = 16.6181 (14) Å	T = 293 K
β = 99.352 (12)°	Block, colourless
V = 2091.0 (4) Å^3	0.40 × 0.25 × 0.25 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	Rint = 0.024
Radiation source: fine-focus sealed tube	θmax = 26.3°, θmin = 2.4°
Graphite monochromator	h = 0→10
non–profiled ω scans	k = −18→0
4475 measured reflections	l = −20→20
4190 independent reflections	3 standard reflections every 120 min
2237 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0633P)^2 + 0.5446P] where P = (Fo^2 + 2Fc^2)/3
4190 reflections	(Δ/σ)max < 0.001
356 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.19 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
O	0.3867 (3)	0.31760 (17)	0.14114 (17)	0.0969 (7)
C1	0.2804 (3)	0.61633 (15)	0.14932 (14)	0.0553 (6)
O2	0.24524 (18)	0.63035 (10)	0.22599 (9)	0.0602 (4)
C3	0.3435 (4)	0.69184 (19)	0.27798 (17)	0.0669 (7)
C4	0.2975 (4)	0.68882 (18)	0.36109 (17)	0.0675 (7)
C5	0.2965 (4)	0.59452 (18)	0.39728 (16)	0.0638 (7)
C6	0.3203 (3)	0.59607 (18)	0.48886 (16)	0.0630 (7)
O7	0.2752 (2)	0.51010 (11)	0.51630 (10)	0.0708 (5)
C8	0.2822 (3)	0.49612 (16)	0.59858 (15)	0.0576 (6)
C9	0.3633 (3)	0.5513 (2)	0.65858 (17)	0.0668 (7)
C10	0.3682 (3)	0.5292 (2)	0.73964 (18)	0.0724 (8)
C11	0.2921 (4)	0.4537 (2)	0.76098 (19)	0.0761 (8)
C12	0.2099 (3)	0.4007 (2)	0.70109 (18)	0.0720 (7)
C13	0.2023 (3)	0.41994 (16)	0.61892 (15)	0.0596 (6)
C14	0.1114 (3)	0.3611 (2)	0.55346 (19)	0.0713 (7)
N15	0.2147 (3)	0.30138 (15)	0.51556 (13)	0.0683 (6)
C16	0.1311 (4)	0.2409 (2)	0.45236 (17)	0.0866 (9)
C17	0.0518 (4)	0.2830 (2)	0.37635 (17)	0.0840 (9)
C18	0.1595 (4)	0.3358 (2)	0.32873 (18)	0.0706 (7)
C19	0.0730 (3)	0.3814 (2)	0.25617 (18)	0.0693 (7)
N20	0.1778 (2)	0.43240 (14)	0.21247 (13)	0.0594 (5)
C21	0.0927 (3)	0.48672 (19)	0.14543 (17)	0.0668 (7)
C22	0.2024 (3)	0.54426 (16)	0.10655 (14)	0.0592 (6)
C23	0.2339 (4)	0.5267 (2)	0.02881 (17)	0.0775 (9)
C24	0.3384 (4)	0.5790 (2)	−0.0057 (2)	0.0875 (10)
C25	0.4126 (4)	0.6486 (2)	0.03730 (18)	0.0779 (8)
C26	0.3862 (3)	0.66828 (19)	0.11481 (16)	0.0659 (7)
H1	0.332 (3)	0.279 (2)	0.0999 (18)	0.089 (10)*
H2	0.328 (5)	0.351 (3)	0.169 (2)	0.145 (16)*
H15	0.286 (4)	0.338 (2)	0.4960 (17)	0.092 (10)*
H16A	0.2061	0.1972	0.4382	0.104*
H16B	0.0529	0.2076	0.4762	0.104*
H17A	−0.0287	0.3237	0.3896	0.101*
H17B	−0.0005	0.2360	0.3413	0.101*
H20	0.236 (3)	0.4676 (16)	0.2468 (14)	0.064 (8)*
H31	0.455 (3)	0.6725 (17)	0.2787 (14)	0.071 (8)*
H32	0.325 (3)	0.7528 (19)	0.2511 (15)	0.082 (8)*
H41	0.375 (3)	0.729 (2)	0.3962 (17)	0.096 (9)*
H42	0.200 (4)	0.719 (2)	0.3577 (18)	0.111 (12)*
H51	0.383 (3)	0.5566 (18)	0.3796 (16)	0.086 (8)*
H52	0.195 (3)	0.5659 (18)	0.3783 (15)	0.078 (8)*
H61	0.261 (3)	0.6439 (16)	0.5101 (13)	0.060 (7)*
H62	0.433 (3)	0.6059 (17)	0.5135 (14)	0.075 (8)*
H91	0.418 (3)	0.6011 (19)	0.6423 (15)	0.081 (9)*
H101	0.426 (3)	0.5683 (18)	0.7837 (16)	0.085 (8)*
H111	0.296 (3)	0.4386 (17)	0.8163 (16)	0.072 (8)*
H121	0.156 (3)	0.3486 (17)	0.7137 (15)	0.076 (8)*
H141	0.038 (3)	0.3211 (18)	0.5780 (15)	0.083 (8)*
H142	0.048 (3)	0.4016 (19)	0.5102 (17)	0.094 (9)*
H181	0.248 (2)	0.2955 (13)	0.3217 (10)	0.031 (5)*
H182	0.213 (3)	0.3833 (18)	0.3664 (15)	0.079 (8)*
H191	−0.008 (4)	0.423 (2)	0.2754 (18)	0.103 (10)*
H192	0.018 (3)	0.3336 (19)	0.2150 (16)	0.089 (8)*
H211	0.040 (3)	0.4423 (17)	0.1045 (15)	0.078 (8)*
H212	0.007 (3)	0.5243 (16)	0.1653 (14)	0.068 (7)*
H231	0.186 (4)	0.477 (2)	0.0036 (18)	0.094 (10)*
H241	0.360 (3)	0.566 (2)	−0.0599 (19)	0.102 (10)*
H251	0.483 (4)	0.683 (2)	0.0150 (18)	0.100 (11)*
H261	0.443 (3)	0.7167 (16)	0.1457 (14)	0.065 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O	0.0697 (14)	0.0952 (16)	0.1222 (19)	0.0128 (13)	0.0053 (14)	−0.0249 (15)
C1	0.0541 (13)	0.0553 (14)	0.0554 (14)	0.0112 (12)	0.0057 (11)	0.0064 (11)
O2	0.0618 (10)	0.0579 (9)	0.0614 (10)	−0.0066 (8)	0.0113 (8)	−0.0065 (8)
C3	0.080 (2)	0.0562 (15)	0.0659 (17)	−0.0142 (15)	0.0170 (14)	−0.0059 (13)
C4	0.080 (2)	0.0538 (15)	0.0720 (18)	−0.0115 (15)	0.0221 (15)	−0.0084 (13)
C5	0.0676 (17)	0.0560 (15)	0.0700 (17)	−0.0017 (14)	0.0177 (14)	−0.0048 (12)
C6	0.0601 (16)	0.0580 (15)	0.0710 (17)	−0.0070 (14)	0.0113 (14)	−0.0023 (13)
O7	0.0838 (13)	0.0605 (10)	0.0671 (11)	−0.0139 (9)	0.0096 (9)	0.0006 (8)
C8	0.0518 (14)	0.0614 (15)	0.0593 (15)	0.0056 (12)	0.0081 (11)	0.0012 (12)
C9	0.0609 (16)	0.0659 (17)	0.0731 (19)	0.0007 (14)	0.0095 (13)	−0.0053 (14)
C10	0.0660 (18)	0.081 (2)	0.0662 (18)	0.0136 (15)	0.0003 (14)	−0.0124 (16)
C11	0.085 (2)	0.082 (2)	0.0623 (19)	0.0187 (17)	0.0124 (15)	0.0041 (16)
C12	0.0736 (18)	0.0679 (17)	0.076 (2)	0.0059 (16)	0.0173 (15)	0.0087 (16)
C13	0.0517 (14)	0.0587 (14)	0.0683 (16)	0.0067 (12)	0.0094 (12)	0.0043 (12)
C14	0.0565 (16)	0.0691 (17)	0.086 (2)	−0.0116 (14)	0.0047 (15)	0.0068 (16)
N15	0.0714 (15)	0.0669 (14)	0.0667 (14)	−0.0137 (12)	0.0116 (12)	−0.0034 (11)
C16	0.104 (2)	0.0714 (18)	0.082 (2)	−0.0320 (17)	0.0081 (17)	0.0023 (15)
C17	0.086 (2)	0.0807 (19)	0.083 (2)	−0.0352 (16)	0.0059 (16)	0.0011 (16)
C18	0.0724 (19)	0.0649 (17)	0.0731 (18)	−0.0212 (16)	0.0074 (15)	−0.0017 (14)
C19	0.0672 (17)	0.0681 (17)	0.0729 (18)	−0.0138 (15)	0.0123 (14)	−0.0030 (15)
N20	0.0591 (13)	0.0573 (12)	0.0600 (12)	−0.0072 (10)	0.0046 (10)	−0.0037 (10)
C21	0.0633 (17)	0.0633 (16)	0.0688 (17)	0.0003 (14)	−0.0040 (14)	−0.0057 (14)
C22	0.0596 (15)	0.0571 (14)	0.0575 (15)	0.0112 (12)	−0.0011 (12)	0.0041 (12)
C23	0.098 (2)	0.0717 (19)	0.0588 (18)	0.0161 (17)	−0.0004 (16)	−0.0011 (15)
C24	0.108 (3)	0.096 (2)	0.0608 (19)	0.023 (2)	0.0191 (18)	0.0117 (18)
C25	0.082 (2)	0.085 (2)	0.068 (2)	0.0112 (18)	0.0170 (16)	0.0241 (17)
C26	0.0686 (17)	0.0646 (16)	0.0639 (17)	0.0019 (14)	0.0086 (14)	0.0114 (14)

Geometric parameters (Å, º)

O—H2	0.89 (4)	C3—H32	1.01 (3)
O—H1	0.96 (3)	C5—C4	1.519 (4)
O2—C1	1.373 (3)	C5—H51	1.02 (3)
O2—C3	1.433 (3)	C5—H52	0.98 (3)
O7—C8	1.375 (3)	C26—C25	1.375 (4)
O7—C6	1.426 (3)	C26—H261	0.97 (2)
C13—C12	1.386 (4)	C9—C10	1.380 (4)
C13—C8	1.390 (3)	C9—H91	0.94 (3)
C13—C14	1.509 (4)	C18—C17	1.529 (4)
C8—C9	1.386 (4)	C18—H181	0.991 (19)
N15—C14	1.467 (3)	C18—H182	1.00 (3)
N15—C16	1.475 (3)	C25—C24	1.354 (4)
N15—H15	0.92 (3)	C25—H251	0.92 (3)
C1—C26	1.386 (3)	C10—C11	1.370 (4)
C1—C22	1.392 (3)	C10—H101	1.00 (3)
C22—C23	1.387 (4)	C23—C24	1.382 (5)
C22—C21	1.495 (4)	C23—H231	0.91 (3)
N20—C19	1.458 (3)	C11—C12	1.371 (4)
N20—C21	1.470 (3)	C11—H111	0.94 (2)
N20—H20	0.87 (2)	C17—C16	1.473 (4)
C6—C5	1.502 (4)	C17—H17A	0.9700
C6—H62	1.00 (3)	C17—H17B	0.9700
C6—H61	0.97 (2)	C12—H121	0.94 (3)
C21—H212	1.02 (2)	C16—H16A	0.9700
C21—H211	1.00 (3)	C16—H16B	0.9700
C19—C18	1.474 (4)	C4—H42	0.95 (3)
C19—H192	1.04 (3)	C4—H41	1.00 (3)
C19—H191	1.02 (3)	C24—H241	0.97 (3)
C3—C4	1.498 (4)	C14—H142	1.02 (3)
C3—H31	1.00 (3)	C14—H141	1.00 (3)
H2—O—H1	117 (3)	C1—C26—H261	120.0 (14)
C1—O2—C3	117.21 (19)	C10—C9—C8	119.7 (3)
C8—O7—C6	118.83 (19)	C10—C9—H91	122.0 (16)
C12—C13—C8	117.4 (2)	C8—C9—H91	118.2 (16)
C12—C13—C14	121.8 (3)	C19—C18—C17	112.8 (2)
C8—C13—C14	120.8 (2)	C19—C18—H181	118.4 (11)
O7—C8—C9	124.2 (2)	C17—C18—H181	107.4 (11)
O7—C8—C13	114.9 (2)	C19—C18—H182	108.1 (14)
C9—C8—C13	120.9 (2)	C17—C18—H182	106.9 (15)
C14—N15—C16	114.2 (2)	H181—C18—H182	102.1 (18)
C14—N15—H15	106.4 (18)	C24—C25—C26	121.3 (3)
C16—N15—H15	112.7 (18)	C24—C25—H251	119.8 (19)
O2—C1—C26	124.1 (2)	C26—C25—H251	119 (2)
O2—C1—C22	115.3 (2)	C11—C10—C9	120.3 (3)
C26—C1—C22	120.6 (2)	C11—C10—H101	118.8 (15)
C23—C22—C1	117.9 (3)	C9—C10—H101	120.8 (16)
C23—C22—C21	122.0 (3)	C24—C23—C22	121.5 (3)
C1—C22—C21	120.2 (2)	C24—C23—H231	122.3 (19)
C19—N20—C21	112.7 (2)	C22—C23—H231	116.1 (19)
C19—N20—H20	108.9 (16)	C10—C11—C12	119.4 (3)
C21—N20—H20	109.6 (16)	C10—C11—H111	120.2 (16)
O7—C6—C5	108.1 (2)	C12—C11—H111	120.3 (16)
O7—C6—H62	107.2 (15)	C16—C17—C18	115.0 (3)
C5—C6—H62	112.4 (14)	C16—C17—H17A	108.5
O7—C6—H61	110.3 (13)	C18—C17—H17A	108.5
C5—C6—H61	112.7 (13)	C16—C17—H17B	108.5
H62—C6—H61	106.1 (19)	C18—C17—H17B	108.5
N20—C21—C22	111.4 (2)	H17A—C17—H17B	107.5
N20—C21—H212	110.5 (14)	C11—C12—C13	122.3 (3)
C22—C21—H212	111.8 (13)	C11—C12—H121	121.5 (16)
N20—C21—H211	105.8 (14)	C13—C12—H121	116.3 (16)
C22—C21—H211	109.1 (14)	C17—C16—N15	117.4 (2)
H212—C21—H211	108 (2)	C17—C16—H16A	108.0
N20—C19—C18	111.8 (2)	N15—C16—H16A	108.0
N20—C19—H192	105.9 (15)	C17—C16—H16B	108.0
C18—C19—H192	109.9 (15)	N15—C16—H16B	108.0
N20—C19—H191	111.2 (17)	H16A—C16—H16B	107.2
C18—C19—H191	107.5 (17)	C3—C4—C5	114.3 (2)
H192—C19—H191	111 (2)	C3—C4—H42	107.4 (19)
O2—C3—C4	108.5 (2)	C5—C4—H42	113 (2)
O2—C3—H31	107.4 (14)	C3—C4—H41	105.4 (16)
C4—C3—H31	112.1 (14)	C5—C4—H41	110.8 (16)
O2—C3—H32	105.3 (15)	H42—C4—H41	105 (2)
C4—C3—H32	112.8 (15)	C25—C24—C23	119.4 (3)
H31—C3—H32	110 (2)	C25—C24—H241	119.7 (18)
C6—C5—C4	112.2 (2)	C23—C24—H241	120.9 (18)
C6—C5—H51	108.4 (15)	N15—C14—C13	112.1 (2)
C4—C5—H51	109.9 (15)	N15—C14—H142	110.1 (16)
C6—C5—H52	107.6 (15)	C13—C14—H142	108.9 (16)
C4—C5—H52	109.4 (15)	N15—C14—H141	106.8 (15)
H51—C5—H52	109 (2)	C13—C14—H141	109.6 (15)
C25—C26—C1	119.4 (3)	H142—C14—H141	109 (2)
C25—C26—H261	120.6 (14)
C6—O7—C8—C9	−15.6 (4)	O7—C8—C9—C10	−177.4 (2)
C6—O7—C8—C13	165.3 (2)	C13—C8—C9—C10	1.6 (4)
C12—C13—C8—O7	177.8 (2)	N20—C19—C18—C17	179.2 (2)
C14—C13—C8—O7	−2.2 (3)	C1—C26—C25—C24	−0.6 (4)
C12—C13—C8—C9	−1.3 (3)	C8—C9—C10—C11	−0.6 (4)
C14—C13—C8—C9	178.7 (2)	C1—C22—C23—C24	−0.3 (4)
C3—O2—C1—C26	−11.2 (3)	C21—C22—C23—C24	−178.4 (3)
C3—O2—C1—C22	168.4 (2)	C9—C10—C11—C12	−0.6 (4)
O2—C1—C22—C23	−179.8 (2)	C19—C18—C17—C16	−176.2 (3)
C26—C1—C22—C23	−0.1 (3)	C10—C11—C12—C13	0.9 (4)
O2—C1—C22—C21	−1.7 (3)	C8—C13—C12—C11	0.1 (4)
C26—C1—C22—C21	177.9 (2)	C14—C13—C12—C11	−180.0 (3)
C8—O7—C6—C5	−178.0 (2)	C18—C17—C16—N15	59.9 (4)
C19—N20—C21—C22	175.0 (2)	C14—N15—C16—C17	67.9 (4)
C23—C22—C21—N20	109.3 (3)	O2—C3—C4—C5	53.4 (4)
C1—C22—C21—N20	−68.7 (3)	C6—C5—C4—C3	155.0 (3)
C21—N20—C19—C18	−173.5 (2)	C26—C25—C24—C23	0.1 (5)
C1—O2—C3—C4	−173.3 (2)	C22—C23—C24—C25	0.4 (4)
O7—C6—C5—C4	164.3 (2)	C16—N15—C14—C13	178.7 (2)
O2—C1—C26—C25	−179.8 (2)	C12—C13—C14—N15	−102.2 (3)
C22—C1—C26—C25	0.6 (4)	C8—C13—C14—N15	77.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O—H1···N15^i	0.96 (3)	1.98 (3)	2.940 (3)	179 (3)
O—H2···N20	0.89 (4)	1.99 (4)	2.868 (3)	170 (4)
N15—H15···O7	0.92 (3)	2.57 (3)	3.130 (3)	120 (2)
N20—H20···O2	0.87 (2)	2.43 (2)	2.985 (3)	122 (2)

Symmetry code: (i) x, −y+1/2, z−1/2.