5-(2-Chloro­phenyl­diazenyl)­salicyl­aldehyde and 4-(2-chloro­phenyl­diazenyl)-2-{[tris­(hydroxy­methyl)­methyl]­amino­methyl­ene}cyclo­hexa-3,5-dien-1(2H)-one

The mol­ecule of the former title compound, C₁₃H₉ClN₂O₂, (I), is nearly planar, with an intramolecular O...O hydrogen bond of 2.692 (2) Å. The latter title compound, C₁₇H₁₈ClN₃O₄, (II), exists in the keto–amine tautomeric form, with a strong intramolecular hydrogen bond of 2.640 (2) Å between the O and N atoms, the H atom being bonded to the N atom. The azo­benzene moieties of both mol­ecules have trans configurations, and the dihedral angle between the planes of the two aromatic rings is 4.1 (1)° in (I) and 9.9 (1)° in (II). The N—H...O hydrogen-bonded rings are almost planar and coupled with the cyclo­hexa­diene rings in (II).

S1. Comment

Azo compounds are the most widely used class of dyes, due to their versatile application in various fields, such as the dyeing of textiles and fibres, the colouring of different materials, and high-technology areas, such as electro-optical devices and ink-jet printers (Peters & Freeman, 1991). Schiff bases have been used extensively as ligands in the field of coordination chemistry (Garnovskii et al., 1993). There is considerable interest in Schiff base complexes due to their striking antitumour activities (Zhou et al., 2000). Schiff base compounds show photochromism and thermochromism in the solid state by proton transfer from the hydroxyl O atom to the imine N atom (Hadjoudis et al., 1987). Photochromic compounds are of great interest for the control and measurement of radiation intensity, optical computers and display systems (Dürr & Bouas-Laurent, 1990). Azo-azomethine compounds are also widely used in the textile industry as synthetic colouring materials (Kamel et al., 1971).

2-Hydroxy Schiff base ligands are of interest mainly due to the existence of O—H···N and N—H···O hydrogen bonds and tautomerism between enol and keto forms. In the aldimine compounds made from 2-hydroxy-1-naphthaldehyde, both types of hydrogen bonds were found (Fernández et al., 2001). The structures of Schiff bases derived from salicylaldehyde generally exist in the phenol-imine form (Elmalı et al., 1999; Filarowski et al., 1999). In contrast, the structures of Schiff bases derived from the condensation of salicylaldehyde and substituted salicylaldehyde with tris(hydroxymethyl)aminomethane only exist in the keto-amine form (Odabaşoǧlu, Albayrak, Büyükgüngör & Lönnecke, 2003).

As part of a general study of the crystal chemistry of dyes, and to provide templates for molecular-modelling studies, the crystal structures of the title compounds, (I) and (II), have been determined. The molecular structures of (I) and (II), with the atom-labelling schemes, are shown in Figs. 1 and 2, respectively, and selected bond lengths and angles are shown in Tables 1 and 3, respectively. \sch

In (I), the aromatic rings, which adopt a trans configuration about the N═N double bond, are nearly coplanar, with a dihedral angle of 4.1 (1)°. A significant intramolecular interaction is noted, involving the phenolic atom H1 and carbonyl atom O2, such that a six-membered ring is formed (Table 2). The C—Cl bond distance in (I) is consistent with that in 4-[(3-chlorophenyl)diazenyl]-2- {[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one (Odabaşoǧlu, Albayrak, Büyükgüngör & Goesmann, 2003). The C13—O2 bond distance in (I) is also consistent with the value of a C═O double bond for carbonyl compounds (Loudon, 2002).

In compound (II), the azobenzene moieties of the molecules have the trans configuration, and the dihedral angle between the planes of the two aromatic rings is 9.9 (1)°. In our previous work, the same dihedral angle was 20.47 (10)° in 4-(3-chlorophenyldiazenyl)-2-{[tris (hydroxymethyl)methyl]aminomethylene} cyclohexa-3,5-dien-1(2H)-one (Odabaşoǧlu, Albayrak, Büyükgüngör & Goesmann, 2003). The present X-ray structure determination reveals that, in the solid state, the keto-amine tautomer exists in the molecule of (II). This is evident from the observed contraction of the C10—O1, C9—C13, C7—C8 and C11—C12 distances and the elongation of C8—C9, C9—C10 and C10—C11, relative to the starting material, (I) (Tables 1 and 3). Furthermore, the C13—N3 bond in (II) is elongated relative to the C═N bond [1.275 (2) Å] in 2-[2-(hydroxymethyl)phenyliminokethyl]phenol, which exists in the phenol-imine form (Ersanlı et al., 2004). The N1═N2, N1—C1 and N2—C7 bond lengths are approximately the same in both (I) and (II). That is to say, transforming to the keto-amine form of the salicylidene ring does not affect bond distances but slightly changes the torsion angle (C1—N1—N2—C7) in the azo moiety.

The intra- and intermolecular hydrogen-bonding for (II) is shown in Fig.3 and the geometric values are given in Table 4. Atom H33 bonded to N3 forms a strong intramolecular hydrogen bond with atom O1 [2.640 (2) Å], as in our previous work (Odabaşoğlu, Albayrak, Büyükgüngör & Goesmann, 2003; Odabaşoğlu, Albayrak, Büyükgüngör & Lönnecke, 2003).

S2. Experimental

The title compounds were obtained as described in our previous work (Odabaşoǧlu, Albayrak, Büyükgüngör & Goesmann, 2003) using 2-chloroaniline, salicylaldehyde and tris(hydroxymethyl)aminomethane as starting materials. Suitable single crystals of (I) were obtained by slow evaporation from ethyl alcohol (yield 85%; m.p. 424–426 K) and of (II) from acetonitrile (yield 72%; m.p. 479–481 K).

S3. Refinement

All H atoms were refined freely. For (I), the refined C—H distances are in the range 0.87 (2)–1.00 (2) Å and U_iso(H) values are in the range 0.031 (5)–0.052 (6) Ų. For (II), the refined C—H distances are in the range 0.92 (2)–1.02 (2) Å and U_iso(H) values are in the range 0.024 (4)–0.054 (6) Ų.

Computing details

For both compounds, data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); 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 and 50% probability displacement ellipsoids.
	Fig. 2. A view of(II), with the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 3. A packing diagram for (II), viewed along the b axis.

(I) 5-(2-chlorophenyldiazenyl)salicylaldehyde

Crystal data

C13H9ClN2O2	F(000) = 536
Mr = 260.67	Dx = 1.490 Mg m^−3
Monoclinic, P21/n	Melting point = 424–426 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 6.9938 (11) Å	Cell parameters from 2275 reflections
b = 21.636 (3) Å	θ = 1.9–26.0°
c = 8.1078 (13) Å	µ = 0.32 mm^−1
β = 108.724 (3)°	T = 213 K
V = 1161.9 (3) Å^3	Prism, dark red
Z = 4	0.40 × 0.40 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2275 independent reflections
Radiation source: fine-focus sealed tube	1783 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
ω scans	θmax = 26.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −8→8
Tmin = 0.882, Tmax = 0.909	k = −19→26
6246 measured reflections	l = −9→9

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)] = 0.044	Hydrogen site location: difference Fourier map
wR(F^2) = 0.108	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0571P)^2 + 0.066P] where P = (Fo^2 + 2Fc^2)/3
2275 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.23 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
Cl1	0.45370 (9)	0.73574 (3)	0.37535 (7)	0.0478 (2)
O2	0.6761 (3)	0.49762 (7)	1.42581 (19)	0.0538 (5)
O1	0.3429 (3)	0.56209 (8)	1.2524 (2)	0.0497 (4)
N1	0.6563 (2)	0.64782 (7)	0.65391 (19)	0.0322 (4)
N2	0.7496 (3)	0.61509 (7)	0.7823 (2)	0.0339 (4)
C1	0.7677 (3)	0.65952 (8)	0.5374 (2)	0.0288 (4)
C2	0.6824 (3)	0.69980 (8)	0.3986 (2)	0.0307 (4)
C3	0.7794 (3)	0.71250 (10)	0.2781 (3)	0.0376 (5)
C4	0.9624 (4)	0.68577 (11)	0.2960 (3)	0.0423 (5)
C5	1.0512 (3)	0.64630 (11)	0.4339 (3)	0.0422 (5)
C6	0.9541 (3)	0.63332 (10)	0.5525 (3)	0.0357 (5)
C7	0.6397 (3)	0.60346 (8)	0.8993 (2)	0.0305 (4)
C8	0.7354 (3)	0.56687 (9)	1.0417 (2)	0.0338 (5)
C9	0.6395 (3)	0.55229 (9)	1.1644 (2)	0.0332 (5)
C10	0.4460 (3)	0.57486 (9)	1.1418 (2)	0.0360 (5)
C11	0.3513 (4)	0.61266 (10)	0.9987 (3)	0.0396 (5)
C12	0.4476 (3)	0.62651 (10)	0.8804 (3)	0.0354 (5)
C13	0.7464 (4)	0.51422 (10)	1.3144 (3)	0.0413 (5)
H1	0.430 (5)	0.5356 (14)	1.338 (4)	0.085 (10)*
H3	0.715 (4)	0.7389 (10)	0.183 (3)	0.046 (6)*
H4	1.024 (3)	0.6941 (10)	0.220 (3)	0.047 (6)*
H5	1.174 (4)	0.6275 (10)	0.440 (3)	0.047 (6)*
H6	1.005 (3)	0.6082 (10)	0.639 (3)	0.045 (6)*
H8	0.873 (3)	0.5501 (9)	1.058 (2)	0.031 (5)*
H11	0.223 (4)	0.6258 (10)	0.985 (3)	0.042 (6)*
H12	0.383 (3)	0.6545 (11)	0.788 (3)	0.052 (6)*
H13	0.887 (4)	0.5055 (10)	1.323 (3)	0.045 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0455 (4)	0.0533 (4)	0.0447 (3)	0.0163 (3)	0.0148 (3)	0.0162 (2)
O2	0.0785 (13)	0.0497 (10)	0.0362 (8)	0.0009 (9)	0.0225 (9)	0.0148 (7)
O1	0.0620 (11)	0.0554 (10)	0.0426 (9)	0.0067 (8)	0.0319 (9)	0.0097 (7)
N1	0.0356 (10)	0.0344 (9)	0.0252 (8)	−0.0013 (7)	0.0078 (7)	0.0025 (7)
N2	0.0349 (10)	0.0365 (9)	0.0283 (9)	−0.0011 (7)	0.0072 (8)	0.0056 (7)
C1	0.0306 (11)	0.0291 (10)	0.0248 (9)	−0.0050 (8)	0.0062 (8)	−0.0020 (7)
C2	0.0312 (11)	0.0300 (10)	0.0286 (10)	−0.0016 (8)	0.0064 (9)	−0.0005 (8)
C3	0.0427 (13)	0.0389 (12)	0.0285 (10)	−0.0066 (10)	0.0077 (10)	0.0024 (9)
C4	0.0451 (14)	0.0527 (14)	0.0331 (11)	−0.0102 (11)	0.0180 (10)	−0.0003 (10)
C5	0.0332 (13)	0.0532 (14)	0.0406 (12)	0.0014 (11)	0.0123 (11)	−0.0041 (10)
C6	0.0340 (12)	0.0407 (12)	0.0290 (10)	0.0009 (9)	0.0054 (9)	0.0016 (9)
C7	0.0322 (11)	0.0316 (10)	0.0253 (9)	−0.0023 (8)	0.0060 (8)	−0.0002 (8)
C8	0.0370 (12)	0.0327 (11)	0.0292 (10)	0.0017 (9)	0.0073 (9)	0.0021 (8)
C9	0.0435 (13)	0.0284 (10)	0.0258 (10)	−0.0005 (9)	0.0083 (9)	0.0014 (8)
C10	0.0472 (13)	0.0343 (11)	0.0296 (10)	−0.0027 (9)	0.0166 (10)	−0.0023 (8)
C11	0.0363 (13)	0.0474 (13)	0.0360 (11)	0.0074 (10)	0.0127 (10)	0.0020 (9)
C12	0.0360 (12)	0.0377 (11)	0.0286 (10)	0.0030 (9)	0.0049 (9)	0.0046 (9)
C13	0.0515 (16)	0.0360 (12)	0.0336 (11)	0.0015 (10)	0.0096 (11)	0.0048 (9)

Geometric parameters (Å, º)

Cl1—C2	1.733 (2)	C5—C6	1.373 (3)
O2—C13	1.213 (2)	C5—H5	0.94 (2)
O1—C10	1.348 (2)	C6—H6	0.87 (2)
O1—H1	0.95 (3)	C7—C8	1.383 (3)
N1—N2	1.255 (2)	C7—C12	1.395 (3)
N1—C1	1.427 (2)	C8—C9	1.402 (3)
N2—C7	1.422 (2)	C8—H8	1.00 (2)
C1—C6	1.391 (3)	C9—C10	1.395 (3)
C1—C2	1.397 (3)	C9—C13	1.461 (3)
C2—C3	1.384 (3)	C10—C11	1.400 (3)
C3—C4	1.369 (3)	C11—C12	1.370 (3)
C3—H3	0.95 (2)	C11—H11	0.92 (2)
C4—C5	1.386 (3)	C12—H12	0.96 (2)
C4—H4	0.88 (2)	C13—H13	0.98 (2)
C10—O1—H1	104.6 (17)	C8—C7—C12	119.2 (2)
N2—N1—C1	113.6 (2)	C8—C7—N2	115.95 (18)
N1—N2—C7	113.9 (2)	C12—C7—N2	124.8 (2)
C6—C1—C2	118.1 (2)	C7—C8—C9	120.5 (2)
C6—C1—N1	124.4 (2)	C7—C8—H8	120.6 (11)
C2—C1—N1	117.5 (2)	C9—C8—H8	119.0 (11)
C3—C2—C1	120.87 (18)	C10—C9—C8	119.55 (18)
C3—C2—Cl1	118.6 (2)	C10—C9—C13	121.49 (18)
C1—C2—Cl1	120.5 (1)	C8—C9—C13	119.0 (2)
C4—C3—C2	119.7 (2)	O1—C10—C9	123.0 (2)
C4—C3—H3	121.5 (14)	O1—C10—C11	117.4 (2)
C2—C3—H3	118.8 (14)	C9—C10—C11	119.6 (2)
C3—C4—C5	120.48 (19)	C12—C11—C10	120.0 (2)
C3—C4—H4	119.5 (15)	C12—C11—H11	122.2 (13)
C5—C4—H4	120.0 (15)	C10—C11—H11	117.8 (13)
C6—C5—C4	119.8 (2)	C11—C12—C7	121.15 (19)
C6—C5—H5	121.7 (14)	C11—C12—H12	118.3 (13)
C4—C5—H5	118.4 (14)	C7—C12—H12	120.4 (13)
C5—C6—C1	121.0 (2)	O2—C13—C9	124.5 (2)
C5—C6—H6	122.0 (15)	O2—C13—H13	121.6 (13)
C1—C6—H6	117.0 (15)	C9—C13—H13	113.8 (13)
C1—N1—N2—C7	179.8 (2)	C12—C7—C8—C9	1.0 (3)
N2—N1—C1—C6	5.5 (3)	N2—C7—C8—C9	−179.56 (17)
N2—N1—C1—C2	−174.78 (16)	C7—C8—C9—C10	0.1 (3)
C6—C1—C2—C3	1.0 (3)	C7—C8—C9—C13	−179.17 (19)
N1—C1—C2—C3	−178.71 (17)	C8—C9—C10—O1	178.95 (18)
C6—C1—C2—Cl1	−178.20 (15)	C13—C9—C10—O1	−1.8 (3)
N1—C1—C2—Cl1	2.1 (2)	C8—C9—C10—C11	−1.1 (3)
C1—C2—C3—C4	−0.7 (3)	C13—C9—C10—C11	178.2 (2)
Cl1—C2—C3—C4	178.50 (16)	O1—C10—C11—C12	−179.07 (19)
C2—C3—C4—C5	−0.2 (3)	C9—C10—C11—C12	1.0 (3)
C3—C4—C5—C6	0.7 (3)	C10—C11—C12—C7	0.1 (3)
C4—C5—C6—C1	−0.4 (3)	C8—C7—C12—C11	−1.1 (3)
C2—C1—C6—C5	−0.4 (3)	N2—C7—C12—C11	179.48 (19)
N1—C1—C6—C5	179.25 (18)	C10—C9—C13—O2	2.6 (3)
N1—N2—C7—C8	179.18 (17)	C8—C9—C13—O2	−178.1 (2)
N1—N2—C7—C12	−1.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.95 (3)	1.83 (3)	2.692 (2)	149 (2)
O1—H1···O2^i	0.95 (3)	2.38 (3)	2.952 (2)	118 (2)

Symmetry code: (i) −x+1, −y+1, −z+3.

(II) 4-(2-chlorophenyldiazenyl)-2- {[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one

Crystal data

C17H18ClN3O4	F(000) = 760
Mr = 363.79	Dx = 1.430 Mg m^−3
Monoclinic, P21/c	Melting point = 479–481 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 16.122 (3) Å	Cell parameters from 3332 reflections
b = 8.3847 (12) Å	θ = 1.4–26.0°
c = 13.359 (2) Å	µ = 0.25 mm^−1
β = 110.689 (3)°	T = 213 K
V = 1689.4 (5) Å^3	Prism, orange
Z = 4	0.35 × 0.25 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3332 independent reflections
Radiation source: fine-focus sealed tube	2501 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω scans	θmax = 26.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −19→15
Tmin = 0.916, Tmax = 0.975	k = −8→10
10407 measured reflections	l = −16→16

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)] = 0.034	Hydrogen site location: difference Fourier map
wR(F^2) = 0.109	All H-atom parameters refined
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0674P)^2 + 0.0074P] where P = (Fo^2 + 2Fc^2)/3
3332 reflections	(Δ/σ)max < 0.001
298 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.33 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
Cl1	0.60359 (4)	0.35489 (7)	0.52771 (5)	0.0584 (2)
O1	0.10407 (7)	0.35993 (13)	0.06417 (9)	0.0268 (3)
O2	−0.12329 (9)	0.32805 (15)	−0.06353 (9)	0.0319 (3)
O4	−0.13144 (9)	0.27918 (16)	0.23544 (10)	0.0364 (3)
O3	−0.05874 (9)	−0.11636 (15)	0.08949 (10)	0.0341 (3)
N1	0.42847 (9)	0.21133 (18)	0.47415 (11)	0.0314 (3)
N2	0.34956 (9)	0.16842 (18)	0.45484 (11)	0.0323 (3)
N3	−0.01545 (9)	0.20702 (16)	0.12104 (10)	0.0217 (3)
C1	0.48879 (11)	0.1572 (2)	0.57426 (13)	0.0303 (4)
C2	0.57490 (12)	0.2178 (2)	0.60750 (14)	0.0360 (4)
C3	0.63803 (14)	0.1710 (3)	0.70347 (16)	0.0450 (5)
C4	0.61604 (14)	0.0615 (3)	0.76676 (16)	0.0482 (5)
C5	0.53168 (15)	−0.0016 (3)	0.73474 (16)	0.0466 (5)
C6	0.46863 (13)	0.0447 (2)	0.63908 (15)	0.0378 (4)
C7	0.29029 (11)	0.2201 (2)	0.35382 (13)	0.0278 (4)
C8	0.20345 (11)	0.1748 (2)	0.32736 (14)	0.0283 (4)
C9	0.13867 (11)	0.21684 (19)	0.22878 (13)	0.0244 (3)
C10	0.16284 (11)	0.31197 (18)	0.15440 (13)	0.0240 (3)
C11	0.25369 (12)	0.3535 (2)	0.18322 (14)	0.0319 (4)
C12	0.31529 (12)	0.3103 (2)	0.27925 (14)	0.0326 (4)
C13	0.04935 (11)	0.16657 (19)	0.20657 (13)	0.0248 (4)
C14	−0.10832 (10)	0.15382 (18)	0.08636 (12)	0.0215 (3)
C15	−0.16372 (12)	0.2836 (2)	0.01114 (13)	0.0268 (4)
C17	−0.13889 (12)	0.1321 (2)	0.18129 (13)	0.0255 (4)
C16	−0.11721 (12)	−0.00217 (19)	0.02397 (13)	0.0274 (4)
H22	−0.1163 (15)	0.430 (3)	−0.0611 (18)	0.055 (7)*
H44	−0.1297 (17)	0.259 (3)	0.292 (2)	0.060 (8)*
H33	−0.0689 (15)	−0.202 (3)	0.0509 (18)	0.052 (7)*
H1	−0.0041 (14)	0.272 (3)	0.0764 (16)	0.047 (6)*
H3	0.6928 (17)	0.213 (3)	0.7243 (18)	0.054 (6)*
H4	0.6577 (15)	0.029 (3)	0.8299 (18)	0.053 (6)*
H5	0.5206 (15)	−0.083 (3)	0.7765 (18)	0.052 (6)*
H6	0.4108 (15)	−0.002 (2)	0.6123 (16)	0.049 (6)*
H8	0.1903 (14)	0.111 (2)	0.3787 (17)	0.043 (6)*
H11	0.2715 (13)	0.421 (2)	0.1317 (15)	0.037 (5)*
H12	0.3755 (14)	0.343 (2)	0.2979 (15)	0.037 (5)*
H13	0.0387 (12)	0.099 (2)	0.2605 (15)	0.033 (5)*
H15A	−0.1704 (11)	0.378 (2)	0.0528 (14)	0.027 (5)*
H15B	−0.2240 (14)	0.242 (2)	−0.0289 (15)	0.037 (5)*
H17A	−0.2007 (13)	0.097 (2)	0.1530 (14)	0.028 (4)*
H17B	−0.1059 (12)	0.051 (2)	0.2260 (14)	0.024 (4)*
H16A	−0.1818 (13)	−0.037 (2)	0.0041 (14)	0.033 (5)*
H16B	−0.1029 (12)	0.018 (2)	−0.0409 (15)	0.036 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0344 (3)	0.0714 (4)	0.0619 (4)	−0.0117 (3)	0.0077 (2)	0.0179 (3)
O1	0.0286 (6)	0.0264 (6)	0.0249 (6)	−0.0011 (5)	0.0087 (5)	0.0033 (4)
O2	0.0483 (8)	0.0267 (7)	0.0230 (6)	0.0023 (6)	0.0154 (5)	0.0044 (5)
O4	0.0523 (9)	0.0369 (7)	0.0241 (7)	0.0017 (6)	0.0187 (6)	−0.0041 (5)
O3	0.0429 (8)	0.0259 (7)	0.0312 (7)	0.0060 (5)	0.0100 (6)	0.0003 (5)
N1	0.0246 (8)	0.0366 (8)	0.0305 (8)	0.0021 (6)	0.0063 (6)	−0.0017 (6)
N2	0.0242 (8)	0.0396 (9)	0.0313 (8)	0.0023 (6)	0.0075 (6)	0.0012 (6)
N3	0.0243 (7)	0.0231 (7)	0.0194 (7)	−0.0014 (5)	0.0097 (6)	0.0007 (5)
C1	0.0246 (9)	0.0380 (10)	0.0281 (9)	0.0048 (7)	0.0088 (7)	−0.0054 (7)
C2	0.0288 (9)	0.0443 (11)	0.0334 (10)	0.0028 (8)	0.0092 (8)	−0.0015 (8)
C3	0.0278 (10)	0.0608 (14)	0.0387 (11)	0.0012 (10)	0.0024 (9)	−0.0060 (9)
C4	0.0408 (12)	0.0668 (15)	0.0289 (10)	0.0147 (11)	0.0024 (9)	0.0043 (10)
C5	0.0459 (12)	0.0597 (14)	0.0346 (10)	0.0090 (10)	0.0148 (9)	0.0105 (9)
C6	0.0291 (10)	0.0495 (12)	0.0353 (10)	0.0032 (9)	0.0120 (8)	0.0023 (8)
C7	0.0247 (8)	0.0286 (9)	0.0285 (8)	0.0025 (7)	0.0072 (7)	0.0010 (7)
C8	0.0277 (9)	0.0293 (9)	0.0273 (9)	−0.0007 (7)	0.0088 (7)	0.0043 (7)
C9	0.0243 (8)	0.0235 (8)	0.0256 (8)	−0.0006 (6)	0.0092 (7)	−0.0014 (6)
C10	0.0269 (8)	0.0205 (8)	0.0244 (8)	0.0009 (6)	0.0088 (7)	−0.0021 (6)
C11	0.0289 (9)	0.0357 (10)	0.0337 (9)	−0.0032 (7)	0.0141 (8)	0.0043 (8)
C12	0.0234 (9)	0.0367 (10)	0.0373 (10)	−0.0020 (7)	0.0104 (8)	0.0014 (8)
C13	0.0270 (9)	0.0250 (8)	0.0234 (8)	−0.0015 (7)	0.0102 (7)	0.0006 (6)
C14	0.0217 (8)	0.0240 (8)	0.0185 (7)	−0.0021 (6)	0.0067 (6)	−0.0008 (6)
C15	0.0295 (9)	0.0278 (9)	0.0227 (8)	0.0025 (7)	0.0087 (7)	0.0023 (7)
C17	0.0256 (9)	0.0300 (9)	0.0227 (8)	−0.0017 (7)	0.0109 (7)	0.0006 (7)
C16	0.0308 (9)	0.0260 (9)	0.0234 (8)	−0.0008 (7)	0.0071 (7)	−0.0023 (6)

Geometric parameters (Å, º)

Cl1—C2	1.737 (2)	C5—H5	0.93 (2)
O1—C10	1.306 (2)	C6—H6	0.96 (2)
O2—C15	1.421 (2)	C7—C8	1.371 (2)
O2—H22	0.86 (3)	C7—C12	1.418 (2)
O4—C17	1.413 (2)	C8—C9	1.406 (2)
O4—H44	0.77 (3)	C8—H8	0.95 (2)
O3—C16	1.410 (2)	C9—C13	1.427 (2)
O3—H33	0.86 (2)	C9—C10	1.431 (2)
N1—N2	1.258 (2)	C10—C11	1.420 (2)
N1—C1	1.422 (2)	C11—C12	1.365 (2)
N2—C7	1.418 (2)	C11—H11	1.01 (2)
N3—C13	1.292 (2)	C12—H12	0.95 (2)
N3—C14	1.471 (2)	C13—H13	0.98 (2)
N3—H1	0.87 (2)	C14—C17	1.525 (2)
C1—C6	1.394 (3)	C14—C16	1.530 (2)
C1—C2	1.396 (2)	C14—C15	1.535 (2)
C2—C3	1.383 (3)	C15—H15A	0.995 (18)
C3—C4	1.376 (3)	C15—H15B	0.99 (2)
C3—H3	0.90 (2)	C17—H17A	0.98 (2)
C4—C5	1.379 (3)	C17—H17B	0.94 (2)
C4—H4	0.92 (2)	C16—H16A	1.02 (2)
C5—C6	1.378 (3)	C16—H16B	0.99 (2)
C15—O2—H22	108.7 (15)	O1—C10—C9	121.7 (2)
C17—O4—H44	106.3 (19)	C11—C10—C9	117.14 (15)
C16—O3—H33	104.3 (15)	C12—C11—C10	121.86 (16)
N2—N1—C1	114.1 (2)	C12—C11—H11	120.2 (11)
N1—N2—C7	113.6 (1)	C10—C11—H11	117.9 (11)
C13—N3—C14	127.9 (1)	C11—C12—C7	120.59 (16)
C13—N3—H1	117.9 (14)	C11—C12—H12	120.2 (12)
C14—N3—H1	114.2 (14)	C7—C12—H12	119.2 (12)
C6—C1—C2	118.2 (2)	N3—C13—C9	123.2 (2)
C6—C1—N1	124.6 (2)	N3—C13—H13	120.4 (11)
C2—C1—N1	117.1 (2)	C9—C13—H13	116.4 (11)
C3—C2—C1	121.01 (19)	N3—C14—C17	111.5 (1)
C3—C2—Cl1	119.2 (2)	N3—C14—C16	108.6 (1)
C1—C2—Cl1	119.8 (1)	C17—C14—C16	110.80 (13)
C4—C3—C2	119.6 (2)	N3—C14—C15	106.5 (1)
C4—C3—H3	120.5 (15)	C17—C14—C15	110.17 (13)
C2—C3—H3	119.9 (15)	C16—C14—C15	109.18 (13)
C3—C4—C5	120.35 (19)	O2—C15—C14	109.9 (1)
C3—C4—H4	120.2 (14)	O2—C15—H15A	110.6 (10)
C5—C4—H4	119.4 (14)	C14—C15—H15A	110.5 (10)
C6—C5—C4	120.2 (2)	O2—C15—H15B	108.6 (11)
C6—C5—H5	121.6 (14)	C14—C15—H15B	109.6 (11)
C4—C5—H5	118.0 (14)	H15A—C15—H15B	107.6 (15)
C5—C6—C1	120.61 (19)	O4—C17—C14	109.1 (1)
C5—C6—H6	122.3 (13)	O4—C17—H17A	110.4 (10)
C1—C6—H6	117.0 (12)	C14—C17—H17A	107.4 (10)
C8—C7—C12	118.9 (2)	O4—C17—H17B	112.4 (10)
C8—C7—N2	116.4 (2)	C14—C17—H17B	109.8 (10)
C12—C7—N2	124.6 (2)	H17A—C17—H17B	107.5 (15)
C7—C8—C9	121.66 (16)	O3—C16—C14	109.2 (1)
C7—C8—H8	115.9 (13)	O3—C16—H16A	111.4 (10)
C9—C8—H8	122.4 (13)	C14—C16—H16A	106.0 (10)
C8—C9—C13	118.79 (15)	O3—C16—H16B	110.4 (11)
C8—C9—C10	119.70 (15)	C14—C16—H16B	109.0 (11)
C13—C9—C10	121.49 (15)	H16A—C16—H16B	110.7 (14)
O1—C10—C11	121.1 (1)
C1—N1—N2—C7	−178.7 (1)	C8—C9—C10—C11	2.7 (2)
N2—N1—C1—C6	10.7 (2)	C13—C9—C10—C11	−178.97 (15)
N2—N1—C1—C2	−171.56 (15)	O1—C10—C11—C12	177.08 (16)
C6—C1—C2—C3	−1.7 (3)	C9—C10—C11—C12	−2.4 (3)
N1—C1—C2—C3	−179.62 (17)	C10—C11—C12—C7	0.6 (3)
C6—C1—C2—Cl1	178.56 (14)	C8—C7—C12—C11	1.0 (3)
N1—C1—C2—Cl1	0.6 (2)	N2—C7—C12—C11	179.33 (17)
C1—C2—C3—C4	0.7 (3)	C14—N3—C13—C9	175.38 (14)
Cl1—C2—C3—C4	−179.51 (16)	C8—C9—C13—N3	175.93 (15)
C2—C3—C4—C5	0.2 (3)	C10—C9—C13—N3	−2.4 (2)
C3—C4—C5—C6	−0.1 (3)	C13—N3—C14—C17	36.1 (2)
C4—C5—C6—C1	−0.9 (3)	C13—N3—C14—C16	−86.32 (18)
C2—C1—C6—C5	1.8 (3)	C13—N3—C14—C15	156.22 (15)
N1—C1—C6—C5	179.51 (17)	N3—C14—C15—O2	46.31 (17)
N1—N2—C7—C8	178.97 (15)	C17—C14—C15—O2	167.32 (13)
N1—N2—C7—C12	0.6 (2)	C16—C14—C15—O2	−70.79 (17)
C12—C7—C8—C9	−0.6 (3)	N3—C14—C17—O4	60.08 (17)
N2—C7—C8—C9	−179.10 (15)	C16—C14—C17—O4	−178.79 (13)
C7—C8—C9—C13	−179.63 (15)	C15—C14—C17—O4	−57.86 (18)
C7—C8—C9—C10	−1.3 (3)	N3—C14—C16—O3	57.76 (17)
C8—C9—C10—O1	−176.76 (15)	C17—C14—C16—O3	−65.03 (18)
C13—C9—C10—O1	1.6 (2)	C15—C14—C16—O3	173.46 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H22···O1^i	0.86 (3)	1.78 (3)	2.635 (2)	177 (2)
O4—H44···O2^ii	0.77 (3)	2.03 (3)	2.791 (2)	172 (3)
O3—H33···O1^iii	0.86 (2)	1.96 (2)	2.803 (2)	167 (2)
N3—H1···O1	0.87 (2)	1.95 (2)	2.640 (2)	134.6 (19)
N3—H1···O2	0.87 (2)	2.21 (2)	2.665 (2)	112.4 (18)

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