3-Hydro­xy-6-[(4-hydroxy­phenyl­amino)­methyl­ene]­cyclo­hexa-2,4-dienone and 2-hydroxy-6-[(4-hydroxy­phenyl­amino)­methyl­ene]­cyclo­hexa-2,4-dienone

The title compounds, both C₁₃H₁₁NO₃, exist as the keto–amine tautomers, and the formal hydroxyl H atoms, which display strong intramolecular hydrogen bonds, are located on the N atoms. This is a verification of the preference for the keto–amine tautomeric form in the solid state. The 2-hydroxy isomer has two independent mol­ecules, with the mol­ecules linked by intramolecular N—H...O and O—H...O and intermolecular O—H...O hydrogen bonds into three-dimensional networks.

S1. Comment

O-Hydroxy Schiff bases, derived from the reaction of o-hydroxy aldehydes with aniline, have been extensively examined (Steward & Lingafelter, 1959; Calligaris et al., 1972; Maslen & Waters, 1975). These Schiff base compounds display interesting photochromic and thermochromic features and can be classified by them (Cohen et al., 1964; Moustakali-Mavridis et al., 1978; Hadjoudis et al., 1987). Photo- and thermochromism arise via H-atom transfer from the hydroxy O atom to the N atom (Hadjoudis et al., 1987; Xu et al., 1994).

There are two types of intramolecular hydrogen bonds in Schiff bases, namely keto-amine (N—H···O) and enol-imine (N···H—O) tautomeric forms. The present X-ray investigation shows that the title compounds, (I) and (II), respectively, prefer keto-amine tautomerism rather than enol-imine tautomerism. O-Hydroxy Schiff bases have been previously seen in the keto form (Ünver Kabak et al., 2002; Odabaşoğlu Albayrak Büyükgüngör & Goesmann, 2003; Koşar et al., 2004; Hökelek et al., 2000), as the enol form (Karadayı et al., 2003; Leardini et al., 1998; Ünver & Yıldız et al., 2002; Elmalı et al., 1998), or as enol/keto mixtures (Nazır et al., 2000), by means of H-atom transfer. Related to this phenomenon, we present here the structures of (I) and (II). \sch

The molecular structure of (I) is shown in Fig. 1, with the atom-numbering scheme. Selected bond lengths and angles are listed in Table 1. The C13—O2 and C7—N1 bond lengths verify the keto-amine form for compound (I). These distances agree with the corresponding distances in 2-([tris(hydroxymethyl)methyl]aminomethylene)cyclohexa-3,5-dien-1(2H)-one [1.3025 (16) and 1.2952 (18) Å; Odabaşoğlu Albayrak Büyükgüngör & Lönnecke, 2003] and 3-[(2-oxo-1-naphthylidene)-methylamino]benzoic acid [1.290 (2) and 1.319 (3) Å; Pavlović & Sosa, 2000], which also show the keto-amine tautomeric form. The same bonds are comparable with the corresponding distances in N-(2-fluoro-3-methoxy)salicylaldimine [1.347 (3) and 1.280 (3) Å; Ünver Kendi et al., 2002] and N-[3,5-bis(trifluoromethyl)phenyl]-3-methoxysalicylaldimine [1.352 (3) and 1.280 (4) Å; Karadayı et al., 2003], which exist in the enol-imine tautomeric form.

Compound (I) displays a strong intramolecular N—H···O hydrogen bond between atoms N1 and O2 (Table 2). This type of strong intramolecular hydrogen bond is a common feature of o-hydroxysalicylidene systems (Filarowski et al., 2003; Yıldız et al., 1998; Odabaşoğlu Albayrak Büyükgüngör & Lönnecke, 2003). The N—H···O hydrogen-bonded ring is coplanar with the adjacent ring, with an N1—C7—C8—C13 torsion angle of 0.0 (3)°.

Compound (II) is very similar to (I), with two independent molecules. Fig. 4 shows the positions of these two independent molecules relative to each other. Because of the distinct settling of the hydroxyl groups, there are more or less distinctions of the bond lengths and angles of (II). Please clarify. Fig. 3 shows the molecular structure of (II), with the atom-numbering scheme. Selected bond lengths and angles for (II) are listed in Table 3. Compound (II) has two strong intramolecular N—H···O hydrogen bonds and an intramolecular O—H···O hydrogen bond (Table 4). The N1—H1···O2 hydrogen-bonded ring of (II) is planar and the torsion angle with the adjacent ring is 0.2 (5)°. The N2—H4···O5 hydrogen-bonded ring is also planar and is coupled with the adjacent ring, with an N2—C20—C21—C26 torsion angle of 1.4 (5)°.

S2. Experimental

The title compounds were prepared as described by Odabaşoğlu et al. (2003) Which ref?, using 4-hydroxyaniline and 4-hydroxysalicylaldehyde as starting materials for (I), and 4-hydroxyaniline and 3-hydroxysalicylaldehyde for (II). Well shaped crystals were obtained by slow evaporation from ethanol solutions [for (I), yield 82%, m.p. 504–506 K; for (II), yield 85%, m.p. 464–466 K].

S3. Refinement

For (I), all H-atom parameters were freely refined. C—H distances were in the range 0.95 (2)–1.022 (18) Å, and U_iso(H) values were in the range 0.058 (5)–0.126 (9) Ų. For (II), all H atoms, except for H1, H4, H7, H20, H33, H44, H66 and H77, were treated using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(parent atom). The remaining H atoms were refined isotropically; the calculated C—H bond lengths were in the range 0.98 (4)–0.99 (4) Å.

Computing details

For both compounds, data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED (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 and 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A packing diagram for (I). Dashed lines indicate intra- and intermolecular hydrogen bonds.
	Fig. 3. A view of one molecule of (II), with the atom-numbering scheme and 50% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A view of (II), with the relative positions of the two independent molecules.

(I) 3-Hydroxy-6-[(4-hydroxyphenylamino)methylene]cyclohexa-2,4-dienone

Crystal data

C13H11NO3	F(000) = 960
Mr = 229.23	Dx = 1.426 Mg m^−3
Monoclinic, C2/c	Melting point = 504–506 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 13.2579 (11) Å	Cell parameters from 6435 reflections
b = 7.8772 (8) Å	θ = 2.0–27.7°
c = 20.4502 (15) Å	µ = 0.10 mm^−1
β = 91.369 (6)°	T = 293 K
V = 2135.1 (3) Å^3	Cylindrical, dark red
Z = 8	0.45 × 0.35 × 0.21 mm

Data collection

Stoe IPDS 2 diffractometer	2486 independent reflections
Radiation source: fine-focus sealed tube	1563 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
Detector resolution: 6.67 pixels mm^-1	θmax = 27.7°, θmin = 2.0°
ω scans	h = −17→17
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	k = −10→10
Tmin = 0.965, Tmax = 0.982	l = −24→26
10511 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.044	All H-atom parameters refined
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.0753P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.94	(Δ/σ)max < 0.001
2486 reflections	Δρmax = 0.16 e Å^−3
199 parameters	Δρmin = −0.16 e Å^−3
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0077 (14)

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	0.47885 (12)	0.04312 (18)	0.38194 (7)	0.0481 (4)
C2	0.41946 (13)	0.0346 (2)	0.43672 (8)	0.0549 (4)
C3	0.36464 (14)	−0.1097 (2)	0.44864 (8)	0.0568 (4)
C4	0.36660 (13)	−0.24587 (19)	0.40626 (8)	0.0531 (4)
C5	0.42554 (14)	−0.2375 (2)	0.35132 (8)	0.0548 (4)
C6	0.48178 (13)	−0.0942 (2)	0.33986 (8)	0.0537 (4)
C7	0.55882 (13)	0.3190 (2)	0.40342 (8)	0.0523 (4)
C8	0.61561 (12)	0.45820 (18)	0.38323 (7)	0.0484 (4)
C9	0.63712 (13)	0.5918 (2)	0.42783 (8)	0.0535 (4)
C10	0.69340 (13)	0.72785 (19)	0.41131 (7)	0.0520 (4)
C11	0.73387 (12)	0.73564 (17)	0.34762 (7)	0.0461 (4)
C12	0.71393 (12)	0.60878 (18)	0.30277 (7)	0.0482 (4)
C13	0.65495 (11)	0.46856 (17)	0.31863 (7)	0.0462 (4)
N1	0.53662 (10)	0.18849 (16)	0.36650 (6)	0.0519 (3)
O1	0.31075 (12)	−0.38408 (16)	0.42144 (6)	0.0773 (4)
O3	0.79215 (9)	0.86810 (13)	0.33348 (5)	0.0584 (3)
O2	0.63456 (9)	0.34721 (13)	0.27654 (5)	0.0597 (4)
H1	0.5664 (15)	0.200 (2)	0.3240 (10)	0.076 (6)*
H2	0.4170 (13)	0.133 (2)	0.4671 (9)	0.058 (5)*
H3	0.3231 (15)	−0.114 (2)	0.4860 (10)	0.072 (5)*
H5	0.4239 (13)	−0.340 (2)	0.3208 (9)	0.063 (5)*
H6	0.5236 (14)	−0.084 (2)	0.3010 (10)	0.070 (5)*
H7	0.5343 (14)	0.317 (2)	0.4473 (9)	0.064 (5)*
H9	0.6101 (14)	0.584 (2)	0.4729 (10)	0.071 (5)*
H10	0.7081 (13)	0.825 (2)	0.4411 (9)	0.058 (5)*
H11	0.3137 (18)	−0.469 (3)	0.3848 (12)	0.110 (8)*
H12	0.7423 (14)	0.616 (2)	0.2593 (9)	0.065 (5)*
H33	0.819 (2)	0.862 (3)	0.2911 (10)	0.126 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0498 (8)	0.0458 (7)	0.0489 (8)	−0.0043 (7)	0.0055 (7)	0.0021 (6)
C2	0.0628 (10)	0.0481 (8)	0.0545 (9)	−0.0080 (7)	0.0143 (8)	−0.0077 (7)
C3	0.0661 (10)	0.0537 (9)	0.0515 (9)	−0.0122 (7)	0.0154 (8)	−0.0044 (7)
C4	0.0621 (10)	0.0459 (8)	0.0516 (9)	−0.0097 (7)	0.0054 (8)	0.0012 (7)
C5	0.0662 (11)	0.0484 (8)	0.0498 (8)	−0.0056 (7)	0.0046 (8)	−0.0051 (7)
C6	0.0607 (10)	0.0550 (9)	0.0457 (8)	−0.0052 (7)	0.0082 (7)	−0.0011 (7)
C7	0.0593 (10)	0.0476 (8)	0.0505 (8)	−0.0045 (7)	0.0115 (7)	−0.0002 (7)
C8	0.0543 (8)	0.0445 (7)	0.0468 (8)	−0.0032 (7)	0.0113 (7)	−0.0007 (6)
C9	0.0668 (10)	0.0504 (8)	0.0441 (8)	−0.0058 (7)	0.0148 (7)	−0.0027 (6)
C10	0.0682 (10)	0.0458 (8)	0.0424 (7)	−0.0072 (7)	0.0094 (7)	−0.0030 (6)
C11	0.0555 (9)	0.0390 (7)	0.0442 (8)	−0.0022 (6)	0.0078 (7)	0.0022 (6)
C12	0.0592 (9)	0.0438 (8)	0.0423 (7)	−0.0025 (6)	0.0116 (7)	−0.0003 (6)
C13	0.0524 (8)	0.0417 (7)	0.0449 (8)	−0.0004 (6)	0.0087 (6)	−0.0042 (6)
N1	0.0563 (8)	0.0482 (7)	0.0519 (7)	−0.0087 (6)	0.0132 (6)	0.0008 (6)
O1	0.1127 (11)	0.0573 (7)	0.0632 (8)	−0.0355 (7)	0.0265 (8)	−0.0087 (6)
O3	0.0830 (8)	0.0448 (5)	0.0481 (6)	−0.0176 (5)	0.0177 (6)	−0.0030 (5)
O2	0.0783 (8)	0.0504 (6)	0.0516 (6)	−0.0157 (6)	0.0212 (6)	−0.0136 (5)

Geometric parameters (Å, º)

C1—C6	1.383 (2)	C8—C9	1.417 (2)
C1—C2	1.386 (2)	C8—C13	1.4343 (19)
C1—N1	1.4174 (19)	C9—C10	1.353 (2)
C2—C3	1.374 (2)	C9—H9	0.999 (19)
C2—H2	0.992 (17)	C10—C11	1.422 (2)
C3—C4	1.380 (2)	C10—H10	0.994 (18)
C3—H3	0.95 (2)	C11—O3	1.3342 (17)
C4—O1	1.3568 (18)	C11—C12	1.378 (2)
C4—C5	1.385 (2)	C12—C13	1.396 (2)
C5—C6	1.376 (2)	C12—H12	0.975 (19)
C5—H5	1.022 (18)	C13—O2	1.3101 (17)
C6—H6	0.982 (19)	N1—H1	0.967 (19)
C7—N1	1.305 (2)	O1—H11	1.01 (3)
C7—C8	1.398 (2)	O3—H33	0.947 (17)
C7—H7	0.961 (19)
C6—C1—C2	119.33 (14)	C7—C8—C13	121.79 (13)
C6—C1—N1	118.02 (13)	C9—C8—C13	118.59 (13)
C2—C1—N1	122.65 (14)	C10—C9—C8	122.08 (14)
C3—C2—C1	119.76 (15)	C10—C9—H9	119.4 (11)
C3—C2—H2	120.5 (9)	C8—C9—H9	118.5 (11)
C1—C2—H2	119.7 (9)	C9—C10—C11	119.03 (14)
C2—C3—C4	120.91 (14)	C9—C10—H10	123.8 (9)
C2—C3—H3	119.5 (11)	C11—C10—H10	117.1 (9)
C4—C3—H3	119.6 (11)	O3—C11—C12	121.73 (13)
O1—C4—C3	117.49 (14)	O3—C11—C10	117.74 (13)
O1—C4—C5	123.04 (14)	C12—C11—C10	120.53 (13)
C3—C4—C5	119.46 (14)	C11—C12—C13	121.26 (13)
C6—C5—C4	119.70 (14)	C11—C12—H12	119.5 (10)
C6—C5—H5	123.3 (10)	C13—C12—H12	119.2 (10)
C4—C5—H5	117.0 (10)	O2—C13—C12	122.19 (12)
C5—C6—C1	120.81 (14)	O2—C13—C8	119.33 (12)
C5—C6—H6	121.6 (11)	C12—C13—C8	118.49 (13)
C1—C6—H6	117.6 (11)	C7—N1—C1	128.54 (13)
N1—C7—C8	124.24 (14)	C7—N1—H1	110.8 (12)
N1—C7—H7	116.9 (10)	C1—N1—H1	120.7 (12)
C8—C7—H7	118.9 (10)	C4—O1—H11	109.4 (14)
C7—C8—C9	119.60 (13)	C11—O3—H33	113.2 (15)
C6—C1—C2—C3	0.2 (3)	C8—C9—C10—C11	−1.2 (3)
N1—C1—C2—C3	179.49 (16)	C9—C10—C11—O3	−177.56 (16)
C1—C2—C3—C4	−1.0 (3)	C9—C10—C11—C12	1.7 (2)
C2—C3—C4—O1	179.79 (17)	O3—C11—C12—C13	178.35 (15)
C2—C3—C4—C5	0.7 (3)	C10—C11—C12—C13	−0.9 (2)
O1—C4—C5—C6	−178.68 (17)	C11—C12—C13—O2	179.53 (15)
C3—C4—C5—C6	0.4 (3)	C11—C12—C13—C8	−0.4 (2)
C4—C5—C6—C1	−1.2 (3)	C7—C8—C13—O2	2.3 (2)
C2—C1—C6—C5	0.9 (3)	C9—C8—C13—O2	−179.06 (15)
N1—C1—C6—C5	−178.47 (16)	C7—C8—C13—C12	−177.80 (16)
N1—C7—C8—C9	−178.70 (16)	C9—C8—C13—C12	0.9 (2)
N1—C7—C8—C13	0.0 (3)	C8—C7—N1—C1	−179.09 (16)
C7—C8—C9—C10	178.65 (17)	C6—C1—N1—C7	−167.43 (17)
C13—C8—C9—C10	−0.1 (2)	C2—C1—N1—C7	13.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.967 (19)	1.77 (2)	2.5976 (16)	141.0 (17)
O1—H11···O3^i	1.01 (3)	1.68 (3)	2.6619 (16)	165 (2)
O3—H33···O2^ii	0.95 (2)	1.53 (2)	2.4775 (14)	178 (3)

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

(II) 2-Hydroxy-6-[(4-hydroxyphenylamino)methylene]cyclohexa-2,4-dienone

Crystal data

C13H11NO3	F(000) = 960
Mr = 229.23	Dx = 1.441 Mg m^−3
Monoclinic, P21/c	Melting point = 464–466 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.6440 (8) Å	Cell parameters from 22130 reflections
b = 8.3499 (3) Å	θ = 1.6–27.1°
c = 20.1529 (12) Å	µ = 0.10 mm^−1
β = 96.693 (5)°	T = 293 K
V = 2113.2 (2) Å^3	Shapeless, dark red
Z = 8	0.50 × 0.45 × 0.21 mm

Data collection

Stoe IPDS 2 diffractometer	4610 independent reflections
Radiation source: fine-focus sealed tube	3305 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
Detector resolution: 6.67 pixels mm^-1	θmax = 27.0°, θmin = 1.6°
ω scans	h = −16→16
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	k = −10→10
Tmin = 0.950, Tmax = 0.985	l = −25→25
32250 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0592P)^2] where P = (Fo^2 + 2Fc^2)/3
4610 reflections	(Δ/σ)max < 0.001
339 parameters	Δρmax = 0.21 e Å^−3
2 restraints	Δρmin = −0.15 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	−0.0008 (2)	0.3052 (4)	0.62303 (14)	0.0369 (6)
C2	−0.0798 (3)	0.1913 (4)	0.61224 (15)	0.0421 (7)
H2	−0.0936	0.1426	0.5706	0.051*
C3	−0.1385 (3)	0.1494 (4)	0.66353 (16)	0.0428 (7)
H3	−0.1913	0.0718	0.6564	0.051*
C4	−0.1189 (2)	0.2224 (4)	0.72512 (15)	0.0393 (7)
C5	−0.0382 (3)	0.3334 (4)	0.73661 (16)	0.0464 (8)
H5	−0.0232	0.3803	0.7785	0.056*
C6	0.0202 (3)	0.3746 (4)	0.68545 (16)	0.0456 (8)
H6	0.0743	0.4500	0.6931	0.055*
C7	0.0655 (3)	0.2914 (4)	0.51594 (15)	0.0412 (7)
C8	0.1307 (2)	0.3521 (4)	0.46839 (14)	0.0387 (7)
C9	0.1352 (3)	0.2697 (4)	0.40780 (15)	0.0472 (8)
H9	0.0929	0.1796	0.3980	0.057*
C10	0.2014 (3)	0.3213 (4)	0.36333 (16)	0.0502 (8)
H10	0.2036	0.2667	0.3233	0.060*
C11	0.2656 (3)	0.4555 (4)	0.37768 (15)	0.0461 (8)
H11	0.3113	0.4887	0.3474	0.055*
C12	0.2621 (2)	0.5391 (4)	0.43600 (15)	0.0413 (7)
C13	0.1930 (2)	0.4912 (4)	0.48274 (14)	0.0388 (7)
C14	0.4561 (2)	0.1462 (4)	0.40719 (14)	0.0384 (7)
C15	0.5280 (3)	0.2697 (4)	0.40289 (15)	0.0436 (7)
H15	0.5396	0.3442	0.4372	0.052*
C16	0.5825 (3)	0.2822 (4)	0.34782 (16)	0.0440 (7)
H16	0.6315	0.3645	0.3453	0.053*
C17	0.5646 (2)	0.1726 (4)	0.29609 (15)	0.0406 (7)
C18	0.4926 (3)	0.0501 (4)	0.30019 (15)	0.0470 (8)
H18	0.4800	−0.0232	0.2654	0.056*
C19	0.4394 (3)	0.0362 (4)	0.35565 (16)	0.0461 (8)
H19	0.3919	−0.0478	0.3586	0.055*
C20	0.4032 (3)	0.2071 (4)	0.51721 (16)	0.0441 (7)
C21	0.3415 (3)	0.1677 (4)	0.56900 (15)	0.0407 (7)
C22	0.3480 (3)	0.2610 (4)	0.62764 (17)	0.0515 (8)
H22	0.3925	0.3500	0.6319	0.062*
C23	0.2899 (3)	0.2224 (4)	0.67815 (17)	0.0537 (9)
H23	0.2942	0.2859	0.7163	0.064*
C24	0.2241 (3)	0.0878 (4)	0.67287 (16)	0.0486 (8)
H24	0.1846	0.0618	0.7075	0.058*
C25	0.2175 (2)	−0.0057 (4)	0.61718 (15)	0.0424 (7)
C26	0.2743 (2)	0.0304 (4)	0.56259 (14)	0.0391 (7)
N1	0.0604 (2)	0.3593 (3)	0.57287 (12)	0.0401 (6)
N2	0.3989 (2)	0.1228 (3)	0.46264 (12)	0.0414 (6)
O1	−0.18331 (19)	0.1816 (3)	0.77327 (12)	0.0491 (6)
O2	0.1889 (2)	0.5753 (3)	0.53811 (11)	0.0508 (6)
O3	0.3262 (2)	0.6695 (3)	0.44918 (13)	0.0561 (7)
O4	0.6154 (2)	0.1805 (3)	0.24005 (12)	0.0532 (6)
O5	0.2637 (2)	−0.0606 (3)	0.50998 (10)	0.0493 (6)
O6	0.1550 (2)	−0.1422 (3)	0.61175 (12)	0.0540 (6)
H1	0.098 (5)	0.448 (7)	0.580 (3)	0.14 (2)*
H4	0.343 (4)	0.031 (6)	0.464 (2)	0.083 (14)*
H7	0.025 (3)	0.192 (4)	0.5044 (17)	0.046 (9)*
H20	0.452 (3)	0.298 (5)	0.5241 (18)	0.057 (10)*
H33	0.301 (4)	0.733 (7)	0.481 (3)	0.103 (18)*
H44	0.676 (4)	0.240 (7)	0.249 (2)	0.097 (17)*
H66	0.169 (4)	−0.198 (7)	0.577 (3)	0.101 (18)*
H77	−0.164 (4)	0.243 (6)	0.810 (2)	0.089 (15)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0394 (15)	0.0364 (15)	0.0360 (15)	0.0018 (13)	0.0097 (12)	0.0025 (11)
C2	0.0467 (17)	0.0448 (17)	0.0358 (15)	−0.0044 (14)	0.0085 (13)	−0.0039 (12)
C3	0.0427 (16)	0.0421 (17)	0.0451 (17)	−0.0051 (14)	0.0111 (13)	−0.0005 (13)
C4	0.0407 (15)	0.0399 (16)	0.0394 (15)	0.0077 (13)	0.0137 (12)	0.0065 (12)
C5	0.0501 (18)	0.0535 (19)	0.0368 (16)	−0.0020 (16)	0.0106 (13)	−0.0078 (14)
C6	0.0462 (17)	0.0482 (18)	0.0438 (17)	−0.0096 (15)	0.0114 (14)	−0.0081 (13)
C7	0.0462 (17)	0.0379 (16)	0.0406 (16)	−0.0003 (14)	0.0101 (13)	−0.0001 (13)
C8	0.0438 (16)	0.0382 (16)	0.0352 (14)	0.0025 (13)	0.0093 (12)	0.0030 (12)
C9	0.059 (2)	0.0423 (18)	0.0412 (16)	−0.0030 (15)	0.0115 (14)	−0.0036 (13)
C10	0.068 (2)	0.0482 (19)	0.0370 (16)	0.0052 (17)	0.0168 (15)	−0.0023 (14)
C11	0.0513 (18)	0.052 (2)	0.0382 (15)	0.0062 (15)	0.0178 (14)	0.0073 (14)
C12	0.0409 (16)	0.0428 (17)	0.0412 (16)	0.0013 (13)	0.0082 (13)	0.0061 (13)
C13	0.0436 (16)	0.0405 (16)	0.0330 (14)	0.0030 (13)	0.0079 (12)	0.0026 (12)
C14	0.0393 (15)	0.0411 (16)	0.0353 (15)	0.0019 (13)	0.0071 (12)	0.0026 (12)
C15	0.0512 (18)	0.0401 (17)	0.0406 (16)	−0.0024 (14)	0.0105 (13)	−0.0036 (13)
C16	0.0478 (17)	0.0396 (17)	0.0462 (17)	−0.0045 (14)	0.0126 (14)	0.0016 (13)
C17	0.0408 (16)	0.0451 (17)	0.0367 (15)	0.0059 (13)	0.0087 (12)	0.0032 (12)
C18	0.0491 (18)	0.052 (2)	0.0398 (16)	−0.0042 (15)	0.0071 (13)	−0.0100 (14)
C19	0.0457 (17)	0.0473 (19)	0.0460 (17)	−0.0087 (14)	0.0076 (14)	−0.0039 (14)
C20	0.0489 (18)	0.0416 (17)	0.0429 (17)	−0.0022 (15)	0.0099 (14)	−0.0004 (13)
C21	0.0459 (17)	0.0386 (16)	0.0388 (15)	0.0024 (13)	0.0095 (13)	0.0019 (12)
C22	0.062 (2)	0.0424 (18)	0.0523 (19)	−0.0047 (16)	0.0154 (16)	−0.0083 (15)
C23	0.067 (2)	0.051 (2)	0.0460 (18)	0.0019 (17)	0.0177 (16)	−0.0104 (15)
C24	0.0543 (19)	0.0517 (19)	0.0424 (17)	0.0051 (16)	0.0173 (14)	0.0022 (14)
C25	0.0432 (17)	0.0430 (17)	0.0418 (16)	0.0015 (14)	0.0079 (13)	0.0059 (13)
C26	0.0437 (16)	0.0408 (16)	0.0326 (14)	0.0038 (13)	0.0042 (12)	0.0035 (12)
N1	0.0450 (14)	0.0398 (14)	0.0372 (13)	−0.0025 (12)	0.0118 (11)	0.0012 (11)
N2	0.0447 (14)	0.0430 (14)	0.0377 (13)	−0.0027 (12)	0.0104 (11)	0.0029 (11)
O1	0.0546 (14)	0.0513 (14)	0.0459 (13)	0.0041 (11)	0.0242 (11)	0.0048 (11)
O2	0.0658 (15)	0.0485 (13)	0.0409 (12)	−0.0134 (11)	0.0181 (10)	−0.0081 (10)
O3	0.0578 (15)	0.0611 (16)	0.0526 (14)	−0.0166 (13)	0.0207 (12)	−0.0046 (12)
O4	0.0561 (15)	0.0641 (16)	0.0424 (13)	0.0000 (13)	0.0190 (11)	−0.0017 (11)
O5	0.0640 (15)	0.0481 (13)	0.0365 (11)	−0.0123 (11)	0.0080 (10)	−0.0028 (10)
O6	0.0624 (15)	0.0569 (15)	0.0457 (13)	−0.0154 (12)	0.0190 (11)	−0.0013 (11)

Geometric parameters (Å, º)

C1—C2	1.378 (4)	C15—C16	1.377 (4)
C1—C6	1.382 (4)	C15—H15	0.9300
C1—N1	1.416 (4)	C16—C17	1.386 (5)
C2—C3	1.386 (4)	C16—H16	0.9300
C2—H2	0.9300	C17—O4	1.364 (4)
C3—C4	1.379 (4)	C17—C18	1.378 (5)
C3—H3	0.9300	C18—C19	1.375 (4)
C4—C5	1.378 (5)	C18—H18	0.9300
C4—O1	1.381 (3)	C19—H19	0.9300
C5—C6	1.380 (4)	C20—N2	1.301 (4)
C5—H5	0.9300	C20—C21	1.413 (4)
C6—H6	0.9300	C20—H20	0.98 (4)
C7—N1	1.288 (4)	C21—C22	1.410 (4)
C7—C8	1.428 (4)	C21—C26	1.423 (4)
C7—H7	0.99 (4)	C22—C23	1.361 (5)
C8—C9	1.409 (4)	C22—H22	0.9300
C8—C13	1.415 (4)	C23—C24	1.396 (5)
C9—C10	1.365 (5)	C23—H23	0.9300
C9—H9	0.9300	C24—C25	1.362 (5)
C10—C11	1.394 (5)	C24—H24	0.9300
C10—H10	0.9300	C25—O6	1.384 (4)
C11—C12	1.372 (4)	C25—C26	1.415 (4)
C11—H11	0.9300	C26—O5	1.298 (4)
C12—O3	1.365 (4)	N1—H1	0.88 (5)
C12—C13	1.415 (4)	N2—H4	1.04 (5)
C13—O2	1.324 (4)	O1—H77	0.90 (5)
C14—C15	1.384 (4)	O3—H33	0.92 (5)
C14—C19	1.384 (4)	O4—H44	0.91 (5)
C14—N2	1.414 (4)	O6—H66	0.88 (5)
C2—C1—C6	119.4 (3)	C14—C15—H15	120.0
C2—C1—N1	123.6 (3)	C15—C16—C17	120.2 (3)
C6—C1—N1	116.9 (3)	C15—C16—H16	119.9
C1—C2—C3	119.9 (3)	C17—C16—H16	119.9
C1—C2—H2	120.1	O4—C17—C18	117.6 (3)
C3—C2—H2	120.1	O4—C17—C16	122.6 (3)
C4—C3—C2	120.3 (3)	C18—C17—C16	119.8 (3)
C4—C3—H3	119.9	C19—C18—C17	120.0 (3)
C2—C3—H3	119.9	C19—C18—H18	120.0
C5—C4—C3	120.0 (3)	C17—C18—H18	120.0
C5—C4—O1	122.3 (3)	C18—C19—C14	120.5 (3)
C3—C4—O1	117.7 (3)	C18—C19—H19	119.7
C4—C5—C6	119.5 (3)	C14—C19—H19	119.7
C4—C5—H5	120.3	N2—C20—C21	121.7 (3)
C6—C5—H5	120.3	N2—C20—H20	120 (2)
C5—C6—C1	120.9 (3)	C21—C20—H20	118 (2)
C5—C6—H6	119.6	C22—C21—C20	120.5 (3)
C1—C6—H6	119.6	C22—C21—C26	119.8 (3)
N1—C7—C8	122.3 (3)	C20—C21—C26	119.7 (3)
N1—C7—H7	120 (2)	C23—C22—C21	120.8 (3)
C8—C7—H7	118 (2)	C23—C22—H22	119.6
C9—C8—C13	120.0 (3)	C21—C22—H22	119.6
C9—C8—C7	119.5 (3)	C22—C23—C24	120.2 (3)
C13—C8—C7	120.4 (3)	C22—C23—H23	119.9
C10—C9—C8	120.3 (3)	C24—C23—H23	119.9
C10—C9—H9	119.9	C25—C24—C23	120.2 (3)
C8—C9—H9	119.9	C25—C24—H24	119.9
C9—C10—C11	120.3 (3)	C23—C24—H24	119.9
C9—C10—H10	119.9	C24—C25—O6	121.1 (3)
C11—C10—H10	119.9	C24—C25—C26	122.0 (3)
C12—C11—C10	120.7 (3)	O6—C25—C26	116.8 (3)
C12—C11—H11	119.7	O5—C26—C25	119.8 (3)
C10—C11—H11	119.7	O5—C26—C21	123.3 (3)
O3—C12—C11	119.6 (3)	C25—C26—C21	116.9 (3)
O3—C12—C13	119.7 (3)	C7—N1—C1	125.7 (3)
C11—C12—C13	120.7 (3)	C7—N1—H1	115 (4)
O2—C13—C12	120.0 (3)	C1—N1—H1	119 (4)
O2—C13—C8	122.1 (3)	C20—N2—C14	128.2 (3)
C12—C13—C8	117.9 (3)	C20—N2—H4	110 (2)
C15—C14—C19	119.4 (3)	C14—N2—H4	122 (2)
C15—C14—N2	123.6 (3)	C4—O1—H77	107 (3)
C19—C14—N2	117.0 (3)	C12—O3—H33	111 (3)
C16—C15—C14	120.1 (3)	C17—O4—H44	109 (3)
C16—C15—H15	120.0	C25—O6—H66	110 (4)
C6—C1—C2—C3	1.1 (5)	C15—C16—C17—O4	179.2 (3)
N1—C1—C2—C3	−177.6 (3)	C15—C16—C17—C18	−0.5 (5)
C1—C2—C3—C4	0.6 (5)	O4—C17—C18—C19	179.8 (3)
C2—C3—C4—C5	−2.2 (5)	C16—C17—C18—C19	−0.5 (5)
C2—C3—C4—O1	176.9 (3)	C17—C18—C19—C14	1.2 (5)
C3—C4—C5—C6	2.1 (5)	C15—C14—C19—C18	−0.8 (5)
O1—C4—C5—C6	−177.0 (3)	N2—C14—C19—C18	−179.6 (3)
C4—C5—C6—C1	−0.4 (5)	N2—C20—C21—C22	179.8 (3)
C2—C1—C6—C5	−1.2 (5)	N2—C20—C21—C26	1.4 (5)
N1—C1—C6—C5	177.6 (3)	C20—C21—C22—C23	−179.1 (3)
N1—C7—C8—C9	178.2 (3)	C26—C21—C22—C23	−0.6 (5)
N1—C7—C8—C13	0.2 (5)	C21—C22—C23—C24	1.0 (6)
C13—C8—C9—C10	1.4 (5)	C22—C23—C24—C25	−0.1 (5)
C7—C8—C9—C10	−176.5 (3)	C23—C24—C25—O6	178.2 (3)
C8—C9—C10—C11	0.4 (5)	C23—C24—C25—C26	−1.2 (5)
C9—C10—C11—C12	−1.1 (5)	C24—C25—C26—O5	−178.6 (3)
C10—C11—C12—O3	179.5 (3)	O6—C25—C26—O5	2.0 (4)
C10—C11—C12—C13	−0.2 (5)	C24—C25—C26—C21	1.5 (5)
O3—C12—C13—O2	1.8 (5)	O6—C25—C26—C21	−177.9 (3)
C11—C12—C13—O2	−178.5 (3)	C22—C21—C26—O5	179.5 (3)
O3—C12—C13—C8	−177.7 (3)	C20—C21—C26—O5	−2.0 (5)
C11—C12—C13—C8	2.0 (5)	C22—C21—C26—C25	−0.6 (5)
C9—C8—C13—O2	177.9 (3)	C20—C21—C26—C25	177.9 (3)
C7—C8—C13—O2	−4.1 (5)	C8—C7—N1—C1	−178.9 (3)
C9—C8—C13—C12	−2.6 (5)	C2—C1—N1—C7	−13.9 (5)
C7—C8—C13—C12	175.4 (3)	C6—C1—N1—C7	167.4 (3)
C19—C14—C15—C16	−0.2 (5)	C21—C20—N2—C14	−179.3 (3)
N2—C14—C15—C16	178.5 (3)	C15—C14—N2—C20	−0.5 (5)
C14—C15—C16—C17	0.8 (5)	C19—C14—N2—C20	178.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H4···O5	1.04 (5)	1.64 (5)	2.561 (3)	145 (4)
N1—H1···O2	0.88 (5)	1.84 (4)	2.578 (3)	141 (6)
O6—H66···O5	0.88 (5)	2.22 (5)	2.686 (3)	112 (4)
O1—H77···O6^i	0.90 (5)	1.85 (5)	2.733 (4)	167 (4)
O6—H66···O2^ii	0.88 (5)	2.07 (6)	2.846 (4)	146 (5)
O4—H44···O1^iii	0.91 (5)	1.90 (5)	2.803 (4)	167 (5)
O3—H33···O5^iv	0.92 (5)	1.89 (6)	2.727 (4)	150 (5)

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