(Z)-6-{[1,3-Dihydroxy-2-(hydroxy­methyl)propan-2-ylamino]methyl­ene}-2-methoxy-4-[(E)-o-tolyl­diazenyl]­cyclo­hexa-2,4-dienone

The title compound, C₁₉H₂₃N₃O₅, adopts the keto–amine tautomeric form with the hydr­oxy H atom located on the N atom, where it is involved in a strong intra­molecular N—H...O hydrogen bond. The compound exhibits trans geometry with respect to the azo N=N double bond, with a dihedral angle between the two benzene rings of 38.03 (6)°. The packing of the mol­ecules in the crystal structure is determined by O—H...O and C—H...O hydrogen bonds. A comparison with closely related compounds is given.

S1. Comment

Schiff base compounds can be classified by their photochromic and thermochromic characteristics (Cohen et al., 1964). Optically active azobenzene polymers are very important because of their photo-responsive properties. Such photochromic compounds have been increasing in number ever since their potential applications were realised in areas such as the control and measurement of radiation intensity, optical computers and display systems (Dürr, 1989; Dürr & Bouas-Laurent, 1990).

In this paper, we report the synthesis and crystal structure of the title compound, (I), and compare it with those of other diazenes (see scheme), namely (Z)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxy-4-{(E)-[3-(trifluoromethyl)phenyl]diazenyl}cyclohexa-2,4-dienone, (II) (Ersanlı, Albayrak, Odabaşoğlu & Kazak, 2005), (Z)-4-[(E)-(4-butylphenyl)diazenyl]-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxycyclohexa-2,4-dienone, (III) (Ersanlı, Albayrak, Odabaşoğlu & Büyükgüngör et al., 2005), (Z)-4-(2,6-dichlorophenyldiazenyl)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxycyclohexa-2,4-dienone and the 3-methoxyphenyldiazenyl and 4-methoxyphenyldiazenyl analogues, (IV) (Özek et al., 2006), 4-[(3-chlorophenyl)diazenyl]-6-methoxy-2-{[tris(hydroxymethyl)methyl]-aminomethylene}cyclohexa-3,5-dien-1(2H)-one, (V) (Koşar et al., 2004a), 4-[(4-methylphenyl)diazenyl]-6-methoxy-2-{[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one, (VI) (Koşar et al., 2004b), and (Z)-6-[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene-4-[(E)-(4-ethylphenyl)diazenyl]cyclohexa-2,4-dienone, (VII) (Şahin et al., 2005).

The structure of (I) (Fig. 1, Table 1) is very similar to those of diazene(azo) compounds reported previously (Table 3). The molecule consists of two aromatic groups linked through a diazene bridge; we designate the aromatic rings and azo group A, B and C, corresponding to the C1–C6 ring, the C8–C13 ring and the C1—N═N2—C8 group, respectively. The dihedral angles between these groups are A/C = 27.54 (7), B/C = 10.49 (16) and A/B = 38.03 (6)°. Ring A is essentially planar, with an r.m.s. deviation of 0.010 (2) Å and a maximum deviation from this plane of 0.016 (2) Å for atom C1. Ring B is almost planar [r.m.s. deviaton 0.016 (1) Å], with a maximum deviation from this plane of 0.025 (1) Å for atom C11. The aromatic rings are in a trans configuration with respect to the azo double bond. The N1—C1 and N2—C8 bond lengths indicate single-bond character, and the N═N bond length is indicative of significant double-bond character as has been observed in other trans-azo compounds (Ersanlı, Odabaşoğlu et al., 2004a; Ersanlı, Albayrak, Odabaşoğlu, Kazak & Erdönmez, 2004).

There is a strong intramolecular N3—H3N···O2 hydrogen bond, with the N3···O2 distance shorter than the sum of the van der Waals radii of O and N (3.07 Å; Bondi, 1964) and comparable with the distances observed in (II) [2.585 (2) Å] and (IV) [2.587 (2) Å].

A comparison of bond lengths and angles associated with the azo group is given in Table 3 for structures (I)–(VII). The steric effect of the ortho-methyl group has caused an enlargement in (I) of the dihedral angle between the ring planes [38.03 (6)°] similar to that found in the o-chloro derivative, (IV), but it has no significant affect on the C1—N1, N2—C8 and N1—N2 bonds. However, the A/B dihedral angles of most of the compounds which do not have ortho-substituents on ring A [(II), (III), (V) and (VII)] range from 7.81 (4) to 13.99 (18)°, in contrast with the value of 34.88 (21)° for compound (VI). Accordingly, it can be said that the dihedral angles A/B may be affected by both the positions of the substituents and by the crystal packing.

The structural data clearly show that (I) adopts the keto–amine form, as indicated by the C11—O2, N3—C15, C12—C15 and C11—C12 bond lengths (Fig. 1 and Table 1). There are significant elongations of the N3—C15 bonds and contractions of the C11—O2 bonds. Similar o-hydroxy Schiff bases have been found to adopt the keto (Ersanlı et al., 2003; Ersanlı, Albayrak, Odabaşoğlu, Thöne & Erdönmez, 2004), enol (Ersanlı, Albayrak, Odabaşoğlu & Erdönmez, 2004; Ersanlı, Odabaşoğlu et al., 2004b) or enol/keto mixtures (Nazır et al., 2000). The N3—C15 and O2—C11 bond distances (Table 1) are reasonably similar, a characteristic of systems in the keto–amine form, comparable with those found in (II) [1.291 (2) and 1.281 (2) Å] and (III) [1.289 (5) and 1.276 (5) Å]. In contrast, the same bonds can be compared with the corresponding distances in 2-[2-(hydroxymethyl)phenyliminomethyl]phenol [1.275 (2) and 1.354 (2) Å; Ersanlı, Odabaşoğlu et al., 2004b] and 4-(2-hydroxyphenyliminomethylene)phenol [1.278 (2) and 1.355 (2) Å; Ersanlı, Albayrak, Odabaşoğlu & Erdönmez, 2004], which exist in the enol–imine tautomeric form.

In the crystal structure of (I), O—H···O and C—H···O hydrogen bonds (Fig. 2, Table 2) generate edge-fused R₂²(8) and R₂²(9) rings (Etter, 1990), forming a three-dimensional network.

S2. Experimental

The title compound, (I), was prepared as previously described by Ersanlı, Albayrak, Odabaşoğlu, Thöne & Erdönmez, 2004). The product was recrystallized from ethanol and well shaped crystals were obtained by slow evaporation of a methanol solution (yield 88%; m.p. 490–492 K).

S3. Refinement

H atoms attached to N and O atoms were refined with isotropic displacement parameters. All H atoms bound to C atoms were refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic C atoms, C—H = 0.97 Å and U_iso(H) = 1.2U_eq(C) for methylene C atoms, and C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl C atoms.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); 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 view 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 dashed line indicates the intramolecular hydrogen bond.
	Fig. 2. A packing diagram for (I), with hydrogen bonds drawn as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. The symmetry codes are as given in Table 2.

(Z)-6-{[1,3-Dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxy- 4-[(E)-o-tolyldiazenyl]cyclohexa-2,4-dienone

Crystal data

C19H23N3O5	F(000) = 792
Mr = 373.40	Dx = 1.355 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25953 reflections
a = 15.6582 (7) Å	θ = 1.9–27.9°
b = 10.6380 (6) Å	µ = 0.10 mm^−1
c = 11.1041 (5) Å	T = 296 K
β = 98.238 (4)°	Plate, orange
V = 1830.55 (16) Å^3	0.50 × 0.28 × 0.06 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	4371 independent reflections
Radiation source: fine-focus sealed tube	2882 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.074
Detector resolution: 6.67 pixels mm^-1	θmax = 28.0°, θmin = 2.3°
ω scans	h = −20→20
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→14
Tmin = 0.964, Tmax = 0.994	l = −14→14
30866 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 0.87	w = 1/[σ^2(Fo^2) + (0.0535P)^2] where P = (Fo^2 + 2Fc^2)/3
4371 reflections	(Δ/σ)max = 0.001
262 parameters	Δρmax = 0.13 e Å^−3
0 restraints	Δρmin = −0.16 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
C1	0.57389 (8)	0.43789 (11)	0.28916 (12)	0.0422 (3)
C2	0.50039 (9)	0.37646 (14)	0.31564 (14)	0.0542 (4)
H2	0.4867	0.3778	0.3944	0.065*
C3	0.44793 (10)	0.31384 (16)	0.22520 (16)	0.0676 (4)
H3	0.3988	0.2726	0.2428	0.081*
C4	0.46799 (11)	0.31221 (17)	0.10941 (16)	0.0704 (5)
H4	0.4332	0.2683	0.0486	0.084*
C5	0.53937 (11)	0.37520 (17)	0.08277 (15)	0.0665 (4)
H5	0.5519	0.3741	0.0034	0.080*
C6	0.59357 (9)	0.44077 (14)	0.17139 (12)	0.0510 (3)
C7	0.67206 (11)	0.5080 (2)	0.14022 (16)	0.0758 (5)
H7A	0.6814	0.5831	0.1881	0.114*
H7B	0.6633	0.5295	0.0554	0.114*
H7C	0.7215	0.4541	0.1573	0.114*
C8	0.68950 (8)	0.50216 (12)	0.58083 (11)	0.0388 (3)
C9	0.69767 (8)	0.43071 (11)	0.68875 (11)	0.0413 (3)
H9	0.6655	0.3575	0.6911	0.050*
C10	0.75190 (8)	0.46721 (11)	0.78953 (11)	0.0388 (3)
C11	0.79919 (7)	0.58280 (10)	0.79157 (10)	0.0343 (3)
C12	0.79172 (7)	0.65136 (10)	0.68003 (10)	0.0342 (3)
C13	0.73666 (8)	0.61009 (11)	0.57597 (11)	0.0379 (3)
H13	0.7323	0.6560	0.5041	0.046*
C14	0.73332 (13)	0.28018 (14)	0.90043 (16)	0.0702 (5)
H14A	0.6715	0.2851	0.8882	0.105*
H14B	0.7528	0.2431	0.9784	0.105*
H14C	0.7520	0.2294	0.8376	0.105*
C15	0.84358 (7)	0.75925 (10)	0.67074 (11)	0.0354 (3)
H15	0.8385	0.8023	0.5972	0.042*
C16	0.95832 (7)	0.90525 (10)	0.76611 (10)	0.0333 (3)
C17	1.04734 (8)	0.85515 (11)	0.82079 (11)	0.0394 (3)
H17A	1.0710	0.8054	0.7603	0.047*
H17B	1.0860	0.9253	0.8429	0.047*
C18	0.92421 (8)	1.00232 (11)	0.84861 (11)	0.0383 (3)
H18A	0.8667	1.0288	0.8136	0.046*
H18B	0.9210	0.9657	0.9279	0.046*
C19	0.96696 (8)	0.95921 (11)	0.64179 (11)	0.0382 (3)
H19A	1.0203	1.0067	0.6476	0.046*
H19B	0.9706	0.8905	0.5853	0.046*
N1	0.63276 (7)	0.49804 (10)	0.38150 (10)	0.0439 (3)
N2	0.63182 (7)	0.44984 (10)	0.48393 (10)	0.0427 (3)
N3	0.89766 (6)	0.79952 (9)	0.76118 (9)	0.0342 (2)
O1	0.76840 (7)	0.40273 (9)	0.89619 (8)	0.0564 (3)
O2	0.84738 (5)	0.61801 (8)	0.88933 (7)	0.0407 (2)
O3	1.04227 (6)	0.77999 (8)	0.92556 (8)	0.0433 (2)
O4	0.98033 (7)	1.10667 (8)	0.86088 (9)	0.0520 (3)
O5	0.89716 (6)	1.03864 (8)	0.59485 (8)	0.0445 (2)
H3N	0.8966 (10)	0.7507 (15)	0.8313 (15)	0.061 (4)*
H5O	0.8735 (12)	1.0063 (18)	0.5246 (18)	0.082 (6)*
H4O	0.9698 (11)	1.1473 (17)	0.9306 (17)	0.075 (5)*
H3O	1.0616 (11)	0.7024 (16)	0.9191 (15)	0.068 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0395 (6)	0.0406 (6)	0.0437 (7)	0.0022 (5)	−0.0036 (5)	−0.0047 (5)
C2	0.0452 (7)	0.0635 (9)	0.0520 (8)	−0.0059 (7)	−0.0002 (6)	−0.0062 (7)
C3	0.0504 (8)	0.0761 (11)	0.0723 (11)	−0.0171 (8)	−0.0045 (8)	−0.0114 (9)
C4	0.0594 (10)	0.0791 (11)	0.0662 (11)	−0.0073 (8)	−0.0128 (8)	−0.0244 (9)
C5	0.0656 (10)	0.0846 (11)	0.0459 (8)	0.0018 (9)	−0.0037 (7)	−0.0165 (8)
C6	0.0484 (7)	0.0582 (8)	0.0437 (8)	0.0016 (6)	−0.0025 (6)	−0.0047 (6)
C7	0.0678 (10)	0.1060 (14)	0.0543 (9)	−0.0170 (10)	0.0111 (8)	−0.0010 (9)
C8	0.0378 (6)	0.0376 (6)	0.0394 (7)	−0.0023 (5)	−0.0007 (5)	−0.0056 (5)
C9	0.0423 (7)	0.0376 (6)	0.0429 (7)	−0.0086 (5)	0.0018 (5)	−0.0016 (5)
C10	0.0433 (7)	0.0371 (6)	0.0355 (6)	−0.0056 (5)	0.0039 (5)	0.0025 (5)
C11	0.0347 (6)	0.0339 (6)	0.0336 (6)	−0.0010 (5)	0.0027 (5)	−0.0029 (5)
C12	0.0355 (6)	0.0303 (5)	0.0360 (6)	−0.0014 (5)	0.0023 (5)	−0.0011 (5)
C13	0.0410 (6)	0.0358 (6)	0.0354 (6)	−0.0005 (5)	0.0000 (5)	0.0003 (5)
C14	0.0916 (12)	0.0502 (8)	0.0640 (10)	−0.0286 (8)	−0.0048 (9)	0.0168 (7)
C15	0.0408 (6)	0.0321 (6)	0.0323 (6)	−0.0019 (5)	0.0021 (5)	0.0002 (5)
C16	0.0386 (6)	0.0276 (5)	0.0330 (6)	−0.0046 (5)	0.0031 (5)	−0.0011 (4)
C17	0.0418 (6)	0.0354 (6)	0.0404 (7)	−0.0017 (5)	0.0036 (5)	−0.0020 (5)
C18	0.0480 (7)	0.0316 (6)	0.0349 (6)	−0.0014 (5)	0.0043 (5)	−0.0018 (5)
C19	0.0444 (7)	0.0348 (6)	0.0353 (6)	−0.0054 (5)	0.0053 (5)	0.0001 (5)
N1	0.0428 (6)	0.0446 (6)	0.0417 (6)	−0.0026 (5)	−0.0031 (5)	−0.0035 (5)
N2	0.0437 (6)	0.0407 (5)	0.0414 (6)	−0.0030 (5)	−0.0022 (5)	−0.0054 (5)
N3	0.0409 (5)	0.0294 (5)	0.0316 (5)	−0.0039 (4)	0.0028 (4)	0.0005 (4)
O1	0.0734 (7)	0.0492 (5)	0.0426 (5)	−0.0256 (5)	−0.0052 (5)	0.0119 (4)
O2	0.0463 (5)	0.0405 (5)	0.0332 (4)	−0.0096 (4)	−0.0013 (4)	0.0008 (4)
O3	0.0563 (5)	0.0332 (4)	0.0381 (5)	0.0067 (4)	−0.0007 (4)	−0.0015 (4)
O4	0.0760 (7)	0.0336 (5)	0.0470 (5)	−0.0129 (4)	0.0113 (5)	−0.0085 (4)
O5	0.0583 (6)	0.0373 (4)	0.0350 (5)	−0.0022 (4)	−0.0033 (4)	0.0019 (4)

Geometric parameters (Å, º)

C1—C6	1.386 (2)	C13—H13	0.9300
C1—C2	1.3912 (19)	C14—O1	1.4181 (16)
C1—N1	1.428 (2)	C14—H14A	0.9600
C2—C3	1.375 (2)	C14—H14B	0.9600
C2—H2	0.9300	C14—H14C	0.9600
C3—C4	1.367 (2)	C15—N3	1.291 (1)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.371 (2)	C16—N3	1.468 (1)
C4—H4	0.9300	C16—C19	1.5189 (16)
C5—C6	1.391 (2)	C16—C18	1.5268 (16)
C5—H5	0.9300	C16—C17	1.5339 (16)
C6—C7	1.504 (2)	C17—O3	1.4231 (15)
C7—H7A	0.9600	C17—H17A	0.9700
C7—H7B	0.9600	C17—H17B	0.9700
C7—H7C	0.9600	C18—O4	1.4102 (14)
C8—C13	1.3703 (17)	C18—H18A	0.9700
C8—C9	1.4093 (17)	C18—H18B	0.9700
C8—N2	1.416 (2)	C19—O5	1.4202 (15)
C9—C10	1.3608 (16)	C19—H19A	0.9700
C9—H9	0.9300	C19—H19B	0.9700
C10—O1	1.361 (1)	N1—N2	1.250 (2)
C10—C11	1.4338 (16)	N3—H3N	0.939 (17)
C11—O2	1.286 (1)	O3—H3O	0.885 (17)
C11—C12	1.428 (2)	O4—H4O	0.922 (19)
C12—C13	1.4092 (16)	O5—H5O	0.88 (2)
C12—C15	1.418 (2)
C6—C1—C2	120.81 (12)	O1—C14—H14A	109.5
C6—C1—N1	117.37 (12)	O1—C14—H14B	109.5
C2—C1—N1	121.81 (12)	H14A—C14—H14B	109.5
C3—C2—C1	119.93 (15)	O1—C14—H14C	109.5
C3—C2—H2	120.0	H14A—C14—H14C	109.5
C1—C2—H2	120.0	H14B—C14—H14C	109.5
C4—C3—C2	119.97 (16)	N3—C15—C12	122.06 (11)
C4—C3—H3	120.0	N3—C15—H15	119.0
C2—C3—H3	120.0	C12—C15—H15	119.0
C3—C4—C5	120.07 (14)	N3—C16—C19	113.39 (9)
C3—C4—H4	120.0	N3—C16—C18	105.10 (9)
C5—C4—H4	120.0	C19—C16—C18	111.97 (9)
C4—C5—C6	121.72 (16)	N3—C16—C17	107.15 (9)
C4—C5—H5	119.1	C19—C16—C17	107.27 (10)
C6—C5—H5	119.1	C18—C16—C17	111.94 (9)
C1—C6—C5	117.43 (14)	O3—C17—C16	111.40 (10)
C1—C6—C7	121.79 (12)	O3—C17—H17A	109.3
C5—C6—C7	120.74 (14)	C16—C17—H17A	109.3
C6—C7—H7A	109.5	O3—C17—H17B	109.3
C6—C7—H7B	109.5	C16—C17—H17B	109.3
H7A—C7—H7B	109.5	H17A—C17—H17B	108.0
C6—C7—H7C	109.5	O4—C18—C16	108.88 (10)
H7A—C7—H7C	109.5	O4—C18—H18A	109.9
H7B—C7—H7C	109.5	C16—C18—H18A	109.9
C13—C8—C9	120.10 (11)	O4—C18—H18B	109.9
C13—C8—N2	126.02 (12)	C16—C18—H18B	109.9
C9—C8—N2	113.86 (11)	H18A—C18—H18B	108.3
C10—C9—C8	121.02 (11)	O5—C19—C16	113.23 (10)
C10—C9—H9	119.5	O5—C19—H19A	108.9
C8—C9—H9	119.5	C16—C19—H19A	108.9
C9—C10—O1	126.1 (1)	O5—C19—H19B	108.9
C9—C10—C11	121.17 (11)	C16—C19—H19B	108.9
O1—C10—C11	112.66 (10)	H19A—C19—H19B	107.7
O2—C11—C12	123.28 (10)	N2—N1—C1	112.28 (11)
O2—C11—C10	120.16 (10)	N1—N2—C8	116.17 (11)
C12—C11—C10	116.52 (10)	C15—N3—C16	129.22 (10)
C13—C12—C15	118.81 (11)	C15—N3—H3N	112.0 (9)
C13—C12—C11	121.11 (10)	C16—N3—H3N	118.8 (9)
C15—C12—C11	120.00 (10)	C10—O1—C14	117.78 (11)
C8—C13—C12	119.91 (11)	C17—O3—H3O	113.4 (11)
C8—C13—H13	120.0	C18—O4—H4O	105.4 (11)
C12—C13—H13	120.0	C19—O5—H5O	107.2 (12)
C6—C1—C2—C3	2.3 (2)	C15—C12—C13—C8	176.39 (11)
N1—C1—C2—C3	−176.41 (13)	C11—C12—C13—C8	−0.29 (18)
C1—C2—C3—C4	−0.1 (2)	C13—C12—C15—N3	−177.46 (11)
C2—C3—C4—C5	−1.4 (3)	C11—C12—C15—N3	−0.75 (18)
C3—C4—C5—C6	0.7 (3)	N3—C16—C17—O3	−45.91 (12)
C2—C1—C6—C5	−2.9 (2)	C19—C16—C17—O3	−167.99 (9)
N1—C1—C6—C5	175.87 (13)	C18—C16—C17—O3	68.82 (12)
C2—C1—C6—C7	179.21 (15)	N3—C16—C18—O4	178.57 (9)
N1—C1—C6—C7	−2.0 (2)	C19—C16—C18—O4	−57.91 (12)
C4—C5—C6—C1	1.4 (2)	C17—C16—C18—O4	62.59 (12)
C4—C5—C6—C7	179.31 (16)	N3—C16—C19—O5	78.08 (12)
C13—C8—C9—C10	0.2 (2)	C18—C16—C19—O5	−40.63 (13)
N2—C8—C9—C10	178.78 (12)	C17—C16—C19—O5	−163.82 (9)
C8—C9—C10—O1	−176.33 (12)	C6—C1—N1—N2	−152.16 (12)
C8—C9—C10—C11	3.3 (2)	C2—C1—N1—N2	26.63 (17)
C9—C10—C11—O2	177.17 (12)	C1—N1—N2—C8	178.87 (10)
O1—C10—C11—O2	−3.17 (17)	C13—C8—N2—N1	9.66 (19)
C9—C10—C11—C12	−4.97 (18)	C9—C8—N2—N1	−168.87 (11)
O1—C10—C11—C12	174.68 (11)	C12—C15—N3—C16	177.20 (11)
O2—C11—C12—C13	−178.74 (11)	C19—C16—N3—C15	−10.64 (17)
C10—C11—C12—C13	3.48 (17)	C18—C16—N3—C15	111.96 (13)
O2—C11—C12—C15	4.63 (18)	C17—C16—N3—C15	−128.81 (12)
C10—C11—C12—C15	−173.15 (11)	C9—C10—O1—C14	6.9 (2)
C9—C8—C13—C12	−1.64 (19)	C11—C10—O1—C14	−172.75 (13)
N2—C8—C13—C12	179.92 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O3^i	0.92 (2)	1.81 (2)	2.7282 (13)	174.8 (16)
O5—H5O···O2^ii	0.88 (2)	2.00 (2)	2.8430 (12)	159.3 (17)
O3—H3O···O5^iii	0.89 (2)	1.872 (18)	2.7576 (13)	179.7 (18)
C15—H15···O2^ii	0.93	2.48	3.3951 (14)	167
C17—H17A···O4^iii	0.97	2.57	3.3157 (15)	134
C19—H19A···O2^iv	0.97	2.47	3.4223 (15)	167
N3—H3N···O2	0.94 (2)	1.772 (17)	2.5873 (13)	143.4 (15)

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