1,3-Bis[2-(2-hydroxybenzylideneamino)phenoxy]propane

The title compound {systematic name: 2,2'-[1,3-propanediyldioxydi-o-phenylenebis(nitrilomethylidyne)]diphenol}, C₂₉H₂₆N₂O₄, exists as the phenol-imine form in the crystal, and there are strong intramolecular O-H...N hydrogen bonds, with O...N distances of 2.545 (2) and 2.579 (2) Å. The C=N imine bond distances are in the range 1.276 (2)-1.279 (2) Å and the C=N-C bond angles are in the range 123.05 (16)-124.64 (17)°. The configurations about the C=N bonds are anti (1E).

S1. Comment

Tautomerism and intramolecular hydrogen bonds in 2-hydroxy Schiff bases in solution and the solid state have been investigated using IR and UV spectroscopies (Hayvalı et al., 2003), ¹H, ¹³C and ¹⁵N NMR spectroscopies (Salman et al., 1991; Pizzala et al., 2000; Gilli et al., 2000), and X-ray crystallography techniques (Kaitner & Pavlovic, 1996). A good review of hydrogen bonds has been published by Steiner (2002). Tautomerism in Schiff bases plays an important role in distinguishing their photochromic (Hadjoudis, 1981; Dürr, 1989) and thermochromic (Moustakali-Mavridis et al., 1980) characteristics.

In solution, the existence of tautomeric equilibria [phenol-imine (O—H···N) and keto-amine (O···H—N) forms] in polar and non-polar solvents, depending on the formation of intermolecular hydrogen bonding, is observed (Costamagna et al., 1992). This tautomerism strongly depends on the solvent polarity and the ability of the solvents to form hydrogen bonds, as reported by Hayvalı et al. (2003). It is claimed that the phenol-imine form is dominant in salicylaldimine, with the keto-amine form dominant in naphthaldimine derivatives, depending on the solvent polarities (Salman et al., 1993). However, in the solid state, it is generally specified by X-ray analysis that the keto-amine form is observed in naphthaldimine, while the phenol-imine form is observed in salicylaldimine Schiff bases (Gavranic et al., 1996; Kaitner & Pavlovic, 1996), although it is claimed that both keto-amine and phenol-imine forms are present in the crystalline state, based on NMR study (Pizzala et al., 2000).

The structures of naphthaldimine and salicylaldimine Schiff base derivatives with different substituents have been the subject of much interest in our laboratory. Examples include compounds (II) (Hökelek Kılıç et al., 2000), (III) (Hökelek Işıklan & Kılıç, 2000), (IV) (Hökelek Kılıç Işıklan Dal & Nazır, 2002), (V) (Hökelek Kılıç Işıklan & Hayvalı, 2002), (VI) (Hökelek, Akduran et al., 2000), (VII) (Hökelek et al., 2001) and (VIII) (Yıldız et al., 1998). Our crystallographic studies have shown a phenol-imine form in (V) and (VII), which are naphthaldimine and salicylaldimine Schiff bases, respectively. Compound (IV) is also a salicylaldimine Schiff base, having nitro groups at the 3- and 5-positions of the phenyl ring. The molecular structure observed in (IV) corresponds to the situation where symmetric hydrogen bonds occur between the two forms (Scheme 2), which might be an artifact due to the disorder caused by H-atom transfer. The N-substituents in (IV), (V) and (VII) are the same, but in (IV) and (V), the aldehyde parts are different. It was once claimed that the hydrogen-bond type depends neither on the stereochemistry of the molecule nor on the type of substituent bonded to the imino N atom, but on the type of aldehyde used (Gavranic et al., 1996), with only an intramolecular O—H···N (phenol-imine form) type of hydrogen bond being observed in salicylaldimines, and an O···H—N (keto-amine form) type of hydrogen bond in naphthaldimines (Kaitner & Pavlovic, 1996; Elerman et al., 1998). However, compound (V) indicates that the naphthaldimine could also exist in the phenol-imine form. These crystallographic results clearly reflect the importance of the stereochemistry of the molecule and the kind of N-substituents in salicylaldimine and naphthaldimine Schiff bases. In this paper, the structure of the title compound, (I), has been determined and is compared with those reported previously. \sch

The molecule of (I) is in the phenol-imine form (Fig. 1). In CDCl₃ solution, ¹H NMR data for (I) also show the existence of only the phenol-imine form (δ = 13.97 p.p.m., singlet for OH; δ = 8.67 p.p.m., singlet for HC═N). The C═N imine bond distances and C—N—C bond angles (Table 1) are comparable with the corresponding values of 1.270 (3) Å and 123.5 (2)° in (VIII), and those of 1.288 (4) Å and 121.3 (3)°, and 1.277 (4) Å and 124.3 (3)° in (VI).

There are short intramolecular O—H···N hydrogen bonds in the structure of (I) (Table 2). The dihedral angles between the best planes of the salicylidenes and the N-substituted benzene rings are 6.09 (6) and 9.30 (5)°. The C6—C7—N1—C8 and C22—N2—C23—C24 torsion angles (Table 1) show that the configurations about the C7—N1 and N2—C23 bonds are anti (1E), while the O1—C14—C15—C16 and C14—C15—C16—O2 torsion angles correspond to the gauche conformation (Hilgenfeld & Saenger, 1982). The dihedral angle between the two N-substituted benzene rings is 86.72 (6)°. Scheme 2 here.

For all compounds (I)-(VIII), the salicylidene and naphthalidene groups are characterized by short N···O distances (Table 3). On the basis of studies of intramolecular hydrogen bonds (Gilli et al., 1989), a short hydrogen bond associated with a charge flow through the system of conjugated double bonds (Scheme 2) is denoted `resonance-assisted hydrogen bonding' and a delocalization parameter, Q = (d₁-d₄) + (d₃-d₂), is defined (distances d₁ to d₄ are as defined in Scheme 2). In general, the Q values (Table 3) have negative and positive signs in the naphthaldimine and salicylaldimine derivatives, respectively, and there is no clear relationship between the corresponding Q and N···O values. In the extreme case of a symmetric position of the H atom, Q is nearly zero, as in the salicylaldimine derivative (IV). In contrast, the Q value is positive in the naphthaldimine derivative (V), due to the strongly electron-withdrawing N-substituent group.

S2. Experimental

A solution of 1,3-propanedioxybis(2-aminophenyl ether) (0.50 g, 1.94 mmol) in dry MeOH (25 ml) was added dropwise to a stirred solution of salicylaldehyde (0.47 g, 3.88 mmol) in dry MeOH (75 ml) over the period of 1 h. The mixture was refluxed for 4 h and then cooled. The precipitated orange solid of (I) was filtered off and crystallized from ethanol (yield 0.73 g, 81%; m.p. 406 K).

S3. Refinement

H atoms were located from difference syntheses and refined isotropically [C—H = 0.93 (2)–1.04 (2) Å and O—H = 0.96 (3)–0.985 (18) Å].

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 (Farrugia, 1999).

Figures

Fig. 1. A drawing of the molecule of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The broken lines show the intramolecular hydrogen bonds.

1,3-[Bis(N-2-oxyphenylsalicylydene)]propane

Crystal data

C29H26N2O4	F(000) = 1968
Mr = 466.52	Dx = 1.272 Mg m^−3
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 14.3665 (10) Å	θ = 10–22°
b = 17.1608 (18) Å	µ = 0.69 mm^−1
c = 19.762 (3) Å	T = 293 K
V = 4872.1 (10) Å^3	Block, orange
Z = 8	0.35 × 0.25 × 0.15 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	3296 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.051
Graphite monochromator	θmax = 74.2°, θmin = 4.5°
non–profiled ω scans	h = 0→17
Absorption correction: ψ scan (North et al., 1968)	k = 0→21
Tmin = 0.814, Tmax = 0.902	l = −24→0
4900 measured reflections	3 standard reflections every 120 min
4893 independent reflections	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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.136	All H-atom parameters refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0646P)^2 + 0.4634P] where P = (Fo^2 + 2Fc^2)/3
4893 reflections	(Δ/σ)max < 0.001
420 parameters	Δρmax = 0.13 e Å^−3
1 restraint	Δρmin = −0.21 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
O1	0.39443 (9)	0.15739 (8)	0.49362 (6)	0.0632 (3)
O2	0.19042 (10)	0.10168 (7)	0.56907 (6)	0.0658 (4)
O3	0.13643 (14)	0.02279 (10)	0.41059 (9)	0.0924 (5)
O4	0.48972 (11)	0.25102 (10)	0.62570 (9)	0.0896 (5)
N1	0.55973 (11)	0.15060 (9)	0.54573 (8)	0.0596 (4)
N2	0.12482 (11)	−0.03363 (9)	0.53125 (7)	0.0586 (4)
C1	0.57325 (14)	0.25106 (12)	0.65768 (11)	0.0669 (5)
C2	0.58790 (18)	0.30317 (14)	0.71031 (13)	0.0808 (6)
C3	0.67162 (19)	0.30428 (14)	0.74397 (12)	0.0808 (6)
C4	0.74173 (17)	0.25370 (14)	0.72651 (12)	0.0768 (6)
C5	0.72802 (15)	0.20155 (13)	0.67469 (11)	0.0678 (5)
C6	0.64396 (13)	0.19897 (10)	0.63918 (9)	0.0573 (4)
C7	0.63287 (14)	0.14699 (12)	0.58221 (10)	0.0600 (5)
C8	0.54506 (13)	0.10691 (11)	0.48615 (9)	0.0589 (4)
C9	0.61174 (16)	0.06279 (15)	0.45290 (12)	0.0799 (6)
C10	0.59024 (18)	0.02503 (16)	0.39317 (13)	0.0893 (8)
C11	0.50244 (18)	0.03097 (15)	0.36639 (12)	0.0839 (7)
C12	0.43484 (16)	0.07465 (13)	0.39844 (10)	0.0700 (5)
C13	0.45561 (13)	0.11259 (11)	0.45813 (9)	0.0570 (4)
C14	0.30310 (13)	0.16830 (14)	0.46600 (11)	0.0644 (5)
C15	0.24838 (16)	0.21440 (13)	0.51704 (12)	0.0685 (5)
C16	0.23688 (16)	0.17299 (11)	0.58384 (11)	0.0642 (5)
C17	0.17664 (12)	0.04948 (10)	0.62027 (8)	0.0541 (4)
C18	0.19653 (14)	0.06512 (13)	0.68779 (9)	0.0631 (5)
C19	0.18124 (15)	0.00822 (13)	0.73612 (10)	0.0674 (5)
C20	0.14651 (16)	−0.06302 (13)	0.71770 (10)	0.0700 (5)
C21	0.12609 (15)	−0.07883 (12)	0.65078 (10)	0.0659 (5)
C22	0.14087 (12)	−0.02241 (10)	0.60134 (9)	0.0536 (4)
C23	0.08074 (13)	−0.09234 (12)	0.50756 (10)	0.0590 (4)
C24	0.06788 (13)	−0.10155 (11)	0.43550 (10)	0.0603 (5)
C25	0.02694 (16)	−0.16956 (14)	0.41017 (12)	0.0746 (6)
C26	0.01388 (17)	−0.17936 (18)	0.34162 (14)	0.0880 (8)
C27	0.04015 (18)	−0.1213 (2)	0.29744 (14)	0.0915 (8)
C28	0.08053 (18)	−0.05406 (18)	0.32064 (12)	0.0827 (7)
C29	0.09587 (15)	−0.04370 (13)	0.38965 (10)	0.0674 (5)
H2	0.5409 (15)	0.3376 (13)	0.7231 (10)	0.076 (6)*
H3	0.6833 (15)	0.3434 (12)	0.7776 (11)	0.081 (7)*
H3A	0.140 (2)	0.0161 (17)	0.4585 (17)	0.136 (11)*
H4	0.7994 (19)	0.2527 (14)	0.7497 (12)	0.098 (8)*
H4A	0.502 (2)	0.2132 (15)	0.5893 (12)	0.137 (11)*
H5	0.7765 (17)	0.1656 (13)	0.6614 (11)	0.092 (8)*
H7	0.6861 (17)	0.1130 (13)	0.5735 (10)	0.086 (7)*
H9	0.6756 (18)	0.0593 (13)	0.4745 (12)	0.099 (7)*
H10	0.6359 (19)	−0.0062 (14)	0.3683 (13)	0.107 (8)*
H11	0.4872 (16)	0.0011 (13)	0.3237 (12)	0.089 (7)*
H12	0.3730 (15)	0.0814 (11)	0.3788 (10)	0.069 (6)*
H18	0.2180 (14)	0.1178 (12)	0.7003 (9)	0.068 (6)*
H19	0.1944 (16)	0.0211 (12)	0.7854 (12)	0.088 (7)*
H20	0.1333 (16)	−0.1041 (14)	0.7520 (12)	0.098 (7)*
H21	0.0996 (16)	−0.1330 (13)	0.6384 (11)	0.092 (7)*
H23	0.0533 (13)	−0.1341 (11)	0.5355 (9)	0.066 (6)*
H25	0.0060 (15)	−0.2072 (13)	0.4437 (10)	0.079 (7)*
H26	−0.0137 (18)	−0.2255 (15)	0.3256 (12)	0.100 (8)*
H27	0.0319 (17)	−0.1270 (14)	0.2472 (13)	0.104 (8)*
H28	0.102 (2)	−0.0132 (15)	0.2913 (14)	0.112 (9)*
H141	0.3080 (14)	0.1977 (12)	0.4213 (10)	0.076 (6)*
H142	0.2738 (14)	0.1184 (12)	0.4564 (10)	0.069 (6)*
H151	0.2782 (14)	0.2648 (12)	0.5247 (10)	0.073 (6)*
H152	0.1895 (18)	0.2243 (12)	0.4974 (11)	0.086 (7)*
H161	0.1990 (14)	0.2040 (11)	0.6148 (10)	0.069 (6)*
H162	0.3008 (15)	0.1624 (11)	0.6070 (10)	0.070 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0508 (7)	0.0763 (8)	0.0626 (7)	0.0090 (6)	−0.0015 (6)	−0.0022 (6)
O2	0.0758 (9)	0.0651 (8)	0.0566 (7)	−0.0122 (7)	0.0026 (6)	0.0034 (6)
O3	0.1181 (14)	0.0853 (11)	0.0739 (10)	−0.0262 (10)	−0.0077 (9)	0.0116 (8)
O4	0.0648 (9)	0.0945 (11)	0.1094 (12)	0.0190 (8)	−0.0174 (9)	−0.0233 (10)
N1	0.0517 (8)	0.0627 (9)	0.0645 (9)	−0.0003 (7)	−0.0015 (7)	0.0032 (7)
N2	0.0586 (9)	0.0613 (9)	0.0557 (8)	−0.0005 (7)	−0.0023 (7)	−0.0004 (7)
C1	0.0615 (11)	0.0620 (11)	0.0771 (13)	−0.0014 (10)	−0.0065 (10)	0.0042 (10)
C2	0.0781 (15)	0.0764 (15)	0.0878 (16)	0.0015 (12)	−0.0017 (13)	−0.0084 (13)
C3	0.0936 (17)	0.0756 (14)	0.0733 (14)	−0.0152 (13)	−0.0079 (13)	−0.0020 (12)
C4	0.0705 (14)	0.0847 (15)	0.0751 (13)	−0.0115 (12)	−0.0145 (12)	0.0132 (12)
C5	0.0634 (12)	0.0729 (13)	0.0672 (12)	−0.0024 (11)	−0.0067 (10)	0.0116 (11)
C6	0.0566 (10)	0.0555 (10)	0.0599 (10)	−0.0036 (8)	−0.0019 (8)	0.0129 (8)
C7	0.0542 (11)	0.0631 (11)	0.0626 (11)	0.0028 (9)	−0.0010 (9)	0.0105 (9)
C8	0.0541 (10)	0.0642 (11)	0.0585 (10)	0.0026 (9)	0.0013 (8)	0.0053 (8)
C9	0.0596 (12)	0.1024 (17)	0.0777 (14)	0.0157 (12)	−0.0016 (11)	−0.0082 (13)
C10	0.0763 (15)	0.113 (2)	0.0789 (15)	0.0301 (14)	0.0045 (12)	−0.0183 (14)
C11	0.0828 (16)	0.1029 (18)	0.0659 (13)	0.0128 (14)	0.0012 (12)	−0.0157 (13)
C12	0.0626 (12)	0.0893 (15)	0.0580 (11)	0.0055 (11)	−0.0042 (10)	−0.0015 (10)
C13	0.0535 (10)	0.0611 (10)	0.0564 (10)	0.0049 (8)	0.0045 (8)	0.0089 (8)
C14	0.0495 (10)	0.0784 (14)	0.0653 (11)	0.0041 (10)	−0.0010 (9)	0.0167 (11)
C15	0.0586 (12)	0.0612 (12)	0.0857 (14)	0.0089 (10)	0.0069 (11)	0.0152 (11)
C16	0.0645 (12)	0.0575 (11)	0.0706 (12)	−0.0017 (9)	0.0082 (10)	−0.0027 (9)
C17	0.0481 (9)	0.0613 (10)	0.0530 (9)	0.0026 (8)	0.0040 (7)	0.0037 (8)
C18	0.0634 (12)	0.0685 (12)	0.0576 (11)	−0.0011 (10)	0.0028 (9)	−0.0068 (9)
C19	0.0680 (12)	0.0833 (14)	0.0509 (10)	0.0054 (11)	0.0000 (9)	0.0000 (10)
C20	0.0777 (14)	0.0739 (13)	0.0583 (11)	0.0089 (11)	0.0010 (10)	0.0103 (10)
C21	0.0718 (13)	0.0619 (11)	0.0641 (11)	−0.0003 (10)	0.0006 (10)	0.0050 (9)
C22	0.0502 (9)	0.0582 (10)	0.0525 (9)	0.0063 (8)	0.0008 (8)	0.0003 (8)
C23	0.0539 (10)	0.0605 (11)	0.0627 (11)	0.0023 (9)	−0.0009 (8)	0.0008 (9)
C24	0.0523 (10)	0.0645 (11)	0.0643 (11)	0.0077 (9)	−0.0075 (8)	−0.0048 (9)
C25	0.0637 (13)	0.0768 (14)	0.0832 (15)	0.0051 (11)	−0.0104 (11)	−0.0139 (12)
C26	0.0713 (15)	0.0992 (18)	0.0935 (18)	0.0116 (14)	−0.0253 (13)	−0.0328 (16)
C27	0.0764 (16)	0.128 (2)	0.0704 (15)	0.0280 (16)	−0.0201 (12)	−0.0213 (16)
C28	0.0774 (15)	0.1066 (19)	0.0641 (13)	0.0158 (14)	−0.0078 (11)	0.0016 (14)
C29	0.0632 (12)	0.0775 (13)	0.0614 (11)	0.0049 (11)	−0.0060 (9)	0.0010 (10)

Geometric parameters (Å, º)

O1—C13	1.362 (2)	C19—C20	1.370 (3)
O1—C14	1.433 (2)	C19—C18	1.383 (3)
O2—C16	1.424 (2)	C21—C20	1.382 (3)
O2—C17	1.366 (2)	C25—C26	1.378 (3)
O3—C29	1.346 (3)	C27—C26	1.377 (4)
O4—C1	1.356 (2)	C5—C4	1.374 (3)
N1—C7	1.276 (2)	C7—H7	0.98 (2)
N1—C8	1.412 (2)	C23—H23	0.99 (2)
N2—C22	1.417 (2)	C19—H19	1.02 (2)
N2—C23	1.279 (2)	C18—H18	0.99 (2)
C1—C2	1.388 (3)	C16—H162	1.04 (2)
C1—C6	1.402 (3)	C16—H161	0.98 (2)
C2—C3	1.375 (3)	O3—H3A	0.96 (3)
C3—C4	1.374 (3)	O4—H4A	0.985 (18)
C5—C6	1.397 (3)	C14—H142	0.97 (2)
C6—C7	1.445 (3)	C14—H141	1.02 (2)
C8—C9	1.387 (3)	C21—H21	1.03 (2)
C8—C13	1.403 (2)	C15—H151	0.98 (2)
C9—C10	1.382 (3)	C15—H152	0.95 (2)
C10—C11	1.372 (3)	C20—H20	1.00 (2)
C11—C12	1.381 (3)	C25—H25	0.97 (2)
C14—C15	1.504 (3)	C27—H27	1.01 (3)
C15—C16	1.508 (3)	C5—H5	0.97 (2)
C17—C22	1.388 (2)	C12—H12	0.98 (2)
C23—C24	1.445 (3)	C28—H28	0.96 (3)
C24—C25	1.399 (3)	C9—H9	1.01 (3)
C24—C29	1.403 (3)	C4—H4	0.95 (3)
C27—C28	1.371 (4)	C11—H11	1.01 (2)
C28—C29	1.393 (3)	C2—H2	0.93 (2)
C22—C21	1.392 (2)	C10—H10	0.98 (3)
C13—C12	1.380 (3)	C3—H3	0.96 (2)
C17—C18	1.391 (2)	C26—H26	0.94 (3)
C13—O1—C14	117.93 (15)	O1—C14—H141	109.4 (12)
C17—O2—C16	118.66 (15)	C15—C14—H141	110.9 (11)
C7—N1—C8	124.64 (17)	H142—C14—H141	107.2 (16)
C23—N2—C22	123.05 (16)	C20—C21—C22	120.2 (2)
O4—C1—C2	118.9 (2)	C20—C21—H21	118.7 (12)
O4—C1—C6	121.30 (18)	C22—C21—H21	121.1 (12)
C2—C1—C6	119.8 (2)	C14—C15—C16	113.36 (17)
C5—C6—C1	118.37 (19)	C14—C15—H151	110.0 (12)
C5—C6—C7	120.40 (18)	C16—C15—H151	109.2 (12)
C1—C6—C7	121.12 (17)	C14—C15—H152	106.6 (13)
N1—C7—C6	120.06 (18)	C16—C15—H152	110.2 (14)
C9—C8—N1	125.60 (18)	H151—C15—H152	107.3 (18)
C13—C8—N1	115.41 (16)	C19—C20—C21	120.5 (2)
C17—C22—N2	116.39 (15)	C19—C20—H20	121.3 (13)
C21—C22—N2	124.52 (17)	C21—C20—H20	118.2 (13)
O3—C29—C28	118.5 (2)	C26—C25—C24	120.7 (3)
O3—C29—C24	121.68 (18)	C26—C25—H25	123.2 (13)
C28—C29—C24	119.8 (2)	C24—C25—H25	116.1 (13)
C17—C22—C21	119.06 (17)	C28—C27—C26	120.9 (2)
O1—C13—C12	124.53 (17)	C28—C27—H27	117.5 (15)
O1—C13—C8	115.28 (16)	C26—C27—H27	121.6 (15)
C12—C13—C8	120.18 (18)	C4—C5—C6	121.2 (2)
C9—C8—C13	118.93 (19)	C4—C5—H5	121.0 (14)
O2—C17—C22	115.91 (15)	C6—C5—H5	117.8 (14)
O2—C17—C18	123.67 (17)	C13—C12—C11	119.7 (2)
C22—C17—C18	120.42 (17)	C13—C12—H12	118.7 (12)
N1—C7—H7	125.1 (13)	C11—C12—H12	121.5 (12)
C6—C7—H7	114.8 (13)	C27—C28—C29	120.1 (3)
C25—C24—C29	118.66 (19)	C27—C28—H28	123.3 (16)
C25—C24—C23	119.8 (2)	C29—C28—H28	116.6 (17)
C29—C24—C23	121.51 (18)	C10—C9—C8	120.4 (2)
N2—C23—C24	120.69 (19)	C10—C9—H9	122.3 (14)
N2—C23—H23	124.4 (11)	C8—C9—H9	117.2 (14)
C24—C23—H23	114.9 (11)	C3—C4—C5	119.6 (2)
C20—C19—C18	120.30 (19)	C3—C4—H4	122.1 (15)
C20—C19—H19	121.1 (12)	C5—C4—H4	118.3 (15)
C18—C19—H19	118.6 (12)	C10—C11—C12	120.7 (2)
C19—C18—C17	119.57 (19)	C10—C11—H11	118.9 (13)
C19—C18—H18	121.6 (11)	C12—C11—H11	120.4 (14)
C17—C18—H18	118.7 (11)	C3—C2—C1	120.3 (2)
O2—C16—C15	106.07 (17)	C3—C2—H2	119.6 (14)
O2—C16—H162	110.7 (11)	C1—C2—H2	120.1 (14)
C15—C16—H162	111.8 (11)	C11—C10—C9	120.0 (2)
O2—C16—H161	109.6 (12)	C11—C10—H10	117.6 (15)
C15—C16—H161	110.6 (11)	C9—C10—H10	122.4 (15)
H162—C16—H161	108.2 (16)	C4—C3—C2	120.7 (2)
C29—O3—H3A	103.2 (18)	C4—C3—H3	119.2 (14)
C1—O4—H4A	100.3 (19)	C2—C3—H3	119.9 (14)
O1—C14—C15	106.97 (18)	C27—C26—C25	119.8 (3)
O1—C14—H142	110.8 (12)	C27—C26—H26	120.8 (15)
C15—C14—H142	111.6 (12)	C25—C26—H26	119.4 (15)
C23—N2—C22—C17	−170.27 (17)	C13—O1—C14—C15	175.91 (16)
C23—N2—C22—C21	11.9 (3)	C17—C22—C21—C20	0.3 (3)
C14—O1—C13—C12	−2.3 (3)	N2—C22—C21—C20	178.04 (18)
C14—O1—C13—C8	177.28 (16)	C25—C24—C29—O3	−179.40 (19)
O1—C13—C8—C9	−179.58 (18)	C25—C24—C29—C28	1.5 (3)
C12—C13—C8—C9	0.1 (3)	C23—C24—C29—C28	−178.7 (2)
O1—C13—C8—N1	−2.1 (2)	C18—C19—C20—C21	−0.2 (3)
C12—C13—C8—N1	177.49 (17)	C22—C21—C20—C19	0.1 (3)
C7—N1—C8—C9	−10.1 (3)	C5—C6—C1—O4	−179.33 (18)
C7—N1—C8—C13	172.69 (17)	C5—C6—C1—C2	−0.2 (3)
C16—O2—C17—C22	−172.81 (17)	C29—C24—C25—C26	−0.4 (3)
C16—O2—C17—C18	7.1 (3)	C23—C24—C25—C26	179.8 (2)
C21—C22—C17—O2	179.23 (16)	C1—C6—C5—C4	−0.1 (3)
N2—C22—C17—O2	1.3 (2)	C7—C6—C5—C4	176.23 (18)
C21—C22—C17—C18	−0.6 (3)	O1—C13—C12—C11	179.7 (2)
N2—C22—C17—C18	−178.58 (16)	C8—C13—C12—C11	0.1 (3)
O1—C14—C15—C16	−62.1 (2)	C26—C27—C28—C29	0.2 (4)
O2—C16—C15—C14	−59.0 (2)	O3—C29—C28—C27	179.4 (2)
C1—C6—C7—N1	3.5 (3)	C24—C29—C28—C27	−1.5 (3)
C5—C6—C7—N1	−172.73 (18)	C13—C8—C9—C10	−0.1 (3)
C7—C6—C1—O4	4.4 (3)	N1—C8—C9—C10	−177.2 (2)
C7—C6—C1—C2	−176.50 (19)	C6—C5—C4—C3	0.1 (3)
C8—N1—C7—C6	174.92 (16)	C13—C12—C11—C10	−0.2 (4)
C22—N2—C23—C24	−178.86 (16)	O4—C1—C2—C3	179.6 (2)
C23—C24—C29—O3	0.4 (3)	C6—C1—C2—C3	0.5 (3)
C25—C24—C23—N2	174.22 (18)	C12—C11—C10—C9	0.2 (4)
C29—C24—C23—N2	−5.6 (3)	C8—C9—C10—C11	−0.1 (4)
C20—C19—C18—C17	−0.2 (3)	C5—C4—C3—C2	0.2 (4)
O2—C17—C18—C19	−179.27 (17)	C1—C2—C3—C4	−0.4 (4)
C22—C17—C18—C19	0.6 (3)	C28—C27—C26—C25	0.9 (4)
C17—O2—C16—C15	175.45 (16)	C24—C25—C26—C27	−0.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···N2	0.96 (3)	1.69 (3)	2.579 (2)	154 (3)
O4—H4A···N1	0.98 (2)	1.61 (3)	2.545 (2)	158 (3)