(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

The title compounds, (Z)-4-(2,6-dichloro­phenyl­diazen­yl)-6-{[1,3-dihydr­oxy-2-(hydroxy­meth­yl)propan-2-ylamino]methyl­ene}-2-methoxy­cyclo­hexa-2,4-dienone, C₁₈H₁₉Cl₂N₃O₅, (I), (Z)-6-{[1,3-dihydr­oxy-2-(hydroxy­meth­yl)propan-2-yl­amino]­methyl­ene}-2-meth­oxy-4-(3-methoxy­phenyl­diazen­yl)cyclo­hexa-2,4-dienone, C₁₉H₂₃N₃O₆, (II), and (Z)-6-{[1,3-di­hydr­oxy-2-(hydroxy­meth­yl)propan-2-ylamino]methyl­ene}-2-meth­oxy-4-(4-methoxy­phenyl­diazen­yl)cyclo­hexa-2,4-dienone, C₁₉H₂₃N₃O₆, (III), all adopt the keto–amine tautomeric form, and the hydroxy H atoms are located on the N atom in all three compounds. Strong intra­molecular N—H...O hydrogen bonds arise as a result of the shifts achieved by the hydroxy H atoms of the Schiff bases to the N atoms. Positional disorder was observed in mol­ecules (II) and (III). In all three compounds, C—H...π and π–π inter­actions affect the packing of the mol­ecules. The compounds exhibit trans geometry with respect to the azo N=N double bond, and the mol­ecules are linked by O—H...O hydrogen bonds to form three-dimensional networks.

S1. Comment

Azo compounds are the most widely used class of dyes owing to their versatile application in various fields, such as the dyeing of textiles and fibers, the coloring of different materials, and high-technology areas, such as electro-optical devices and ink-jet printers (Peters & Freeman, 1991). Most Schiff bases have antibacterial, anticancer, antinflammatory and antitoxic properties (Williams, 1972). Two characteristic properties of Schiff bases are photochromism and thermochromism (Cohen et al., 1964; Moustakali-Mavridis et al., 1978). These properties are caused by proton transfer from the hydroxy O atom to the imine N atom (Hadjoudis et al., 1987; Xu et al., 1994). 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), (II) and (III), have been determined. The molecular structures of (I), (II) and (III), with the atom-labelling schemes, are shown in Figs. 1, 2 and 3, respectively, and selected bond lengths and angles are given in Tables 1, 3 and 5, respectively.

In all three molecules (I), (II) and (III), the keto–amine tautomer is favoured over the phenol–imine form, as indicated by the C10—O3, C13—N3, C11—C13 and C10—C11 bond lengths (Figs. 1, 2 and 3, and Tables 1, 3 and 5). Furthermore, these data show that there are significant elongations of the C13—N3 bond and contraction of the C10—O3 bond. A similar effect was observed for 4-[(3-chloropheny)diazeniyl]-2-{[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one [C10—O3 = 1.286 (2) Å, C13—N3 = 1.298 (3) Å, C11—C13 = 1.411 (3) Å and C10—C11 = 1.436 (3) Å; Odabaşoǧlu et al., 2003]. The H atom was located on N1, thus confirming a preference for the keto–amine tautomer in the solid state. The N1—C1 and N2—C7 bond lengths are approximately the same in (I), (II) and (III), and these lengths indicate single-bond character, whereas the N═N bond lengths are indicative of significant double-bond character. The high s.u. values and high displacement parameters of some atoms in the molecules of both (II) and (III) are probably caused by positional and orientational disorder. In (II), C18 is observed at two different positions owing to a positional disorder, with occupancy factors of 0.64 (7) and 0.36 (7). In (III), atom O1 shows positional disorder with occupancy factors of 0.409 (7) and 0.591 (7). At the same time, the phenyl rings also show orientational disorder with the same occupancy factors (Fig. 3).

In (I), the C—Cl bond distance is consistent with that in 5-(2-chlorophenyldiazenyl)salicylaldehyde and 4-(2-chlorophenyldiazenyl)- 2-{[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one (Albayrak et al., 2004). The dihedral angles between the C1–C6 and C7–C12 rings are 58.91 (13), 8.89 (11) and 21.57 (3)° (the average of the two angles for the orientationally disordered phenyl ring) for (I), (II) and (III), respectively.

The intra- and intermolecular hydrogen bonds are shown in the packing diagram of (I), (II) and (III) in Figs. 4–6, respectively. In all three structure, these O—H···O hydrogen bonds generate edge-fused R₂²(5), R₃²(19) and R₂²(12) rings. Atom H33 bonded to N3 form a strong intramolecular hydrogen bond with atom O3, as observed in similar compounds (Odabaşoǧlu et al., 2003; Albayrak et al., 2004). In (I), (II) and (III), the molecules are linked by C—H···π interactions (Tables 2, 4 and 6, and Figs. 4–6). In addition to these interactions, all three compounds contain π–π interactions. Details of these π–π interactions are given in Table 7 and they are shown in Figs. 4–6.

S2. Experimental

Compounds (I), (II) and (III) were prepared as described in the literature (Odabaşoǧlu et al., Albayrak, Büyükgüngör & Lönnecke, 2003)?????? using o-vanillin, 2.6-dichloroaniline for (I), 3-methoxyaniline for (II), 4-methoxyaniline for (III) and tris(hydroxymethyl)aminomethane as starting materials. The product was crystallized from ethanol, and well shaped crystals were obtained by slow evaporation of a ethanol solution [yield 74%, m.p. 480–482 K for (I); yield 76%, m.p. 462–463 K for (II);

yield 78%, m.p. 489–490 K for (III)].

S3. Refinement

H atoms attached to N and O atoms were refined freely. All remaining H atoms were refined using a riding model, with C—H distances of 0.93–0.97 Å. In (III), the H atoms of C18 were refined at two different positions owing to disorder, with 0.5 occupancy for each component. The U_iso(H) values are 1.5U_eq(C) for the methyl H atoms and 1.2U_eq(C) for the remaining C-bound H atoms.

Computing details

For all compounds, 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. An ORTEP-3 (Farrugia, 1997) view of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids. The dashed line indicates the intramolecular hydrogen bond.
	Fig. 2. An ORTEP-3 (Farrugia, 1997) view of (II), with the atom-numbering scheme and 50% probability displacement ellipsoids. The dashed line indicates the intramolecular hydrogen bond.
	Fig. 3. An ORTEP-3 (Farrugia, 1997) view of (III), with the atom-numbering scheme and 50% probability displacement ellipsoids. The dashed line indicates the intramolecular hydrogen bond.
	Fig. 4. An ORTEP-3 (Farrugia, 1997) packing diagram of (I). Dashed lines indicate hydrogen bonds, C—H···π and π–π interactions. H atoms not involved in hydrogen bonding or C—H···π interactions have been omitted for clarity.
	Fig. 5. An ORTEP-3 (Farrugia, 1997) packing diagram of (II). Dashed lines indicate hydrogen bonds, C—H···π and π–π interactions. H atoms not involved in hydrogen bonding or C—H···π interactions have been omitted for clarity.
	Fig. 6. An ORTEP-3 (Farrugia, 1997) packing diagram of (III). Dashed lines indicate hydrogen bonds, C—H···π and π–π interactions. H atoms not involved in hydrogen bonding or C—H···π interactions have been omitted for clarity.

(I) (Z)-4-(2,6-dichlorophenyldiazenyl)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan- 2-ylamino]methylene}-2-methoxycyclohexa-2,4-dienone

Crystal data

C18H19Cl2N3O5	F(000) = 888
Mr = 428.26	Dx = 1.474 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 12750 reflections
a = 16.8445 (15) Å	θ = 1.9–28.4°
b = 10.7259 (5) Å	µ = 0.37 mm^−1
c = 11.1126 (9) Å	T = 296 K
β = 106.037 (7)°	Stick, red
V = 1929.6 (2) Å^3	0.78 × 0.33 × 0.05 mm
Z = 4

Data collection

STOE IPDS-II diffractometer	3782 independent reflections
Radiation source: fine-focus sealed tube	2715 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 2.3°
ω scans	h = −20→20
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −11→13
Tmin = 0.871, Tmax = 0.977	l = −13→12
10068 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0754P)^2 + 0.1273P] where P = (Fo^2 + 2Fc^2)/3
3782 reflections	(Δ/σ)max < 0.001
269 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

Experimental. 135 frames, detector distance = 110 mm

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	0.58033 (15)	0.5549 (2)	0.2111 (2)	0.0460 (6)
C2	0.50018 (17)	0.5839 (3)	0.2154 (3)	0.0551 (7)
C3	0.44778 (19)	0.6504 (3)	0.1201 (3)	0.0706 (9)
H3	0.3948	0.6698	0.1243	0.085*
C4	0.4730 (2)	0.6877 (3)	0.0203 (3)	0.0801 (10)
H4	0.4375	0.7343	−0.0425	0.096*
C5	0.5509 (2)	0.6575 (3)	0.0099 (3)	0.0690 (8)
H5	0.5677	0.6820	−0.0595	0.083*
C6	0.60314 (17)	0.5899 (3)	0.1060 (2)	0.0544 (6)
C7	0.70689 (13)	0.4967 (2)	0.5165 (2)	0.0389 (5)
C8	0.71827 (13)	0.5702 (2)	0.6250 (2)	0.0405 (5)
H8	0.6919	0.6470	0.6195	0.049*
C9	0.76720 (13)	0.5310 (2)	0.7379 (2)	0.0393 (5)
C10	0.80919 (12)	0.4135 (2)	0.7498 (2)	0.0350 (5)
C11	0.80026 (13)	0.3442 (2)	0.6365 (2)	0.0362 (5)
C12	0.74816 (14)	0.3857 (2)	0.5217 (2)	0.0399 (5)
H12	0.7417	0.3382	0.4496	0.048*
C13	0.84882 (13)	0.2351 (2)	0.6384 (2)	0.0373 (5)
H13	0.8428	0.1909	0.5644	0.045*
C14	0.95897 (13)	0.09159 (19)	0.75662 (19)	0.0340 (4)
C15	0.96751 (14)	0.0380 (2)	0.6337 (2)	0.0399 (5)
H15A	0.9701	0.1060	0.5774	0.048*
H15B	1.0189	−0.0082	0.6499	0.048*
C16	0.92724 (14)	−0.0049 (2)	0.8336 (2)	0.0389 (5)
H16A	0.9245	0.0315	0.9122	0.047*
H16B	0.8722	−0.0321	0.7880	0.047*
C17	1.04417 (13)	0.1429 (2)	0.8285 (2)	0.0403 (5)
H17A	1.0817	0.0740	0.8587	0.048*
H17B	1.0664	0.1924	0.7723	0.048*
C18	0.7495 (2)	0.7156 (3)	0.8462 (3)	0.0683 (8)
H18A	0.7598	0.7457	0.9305	0.102*
H18B	0.6910	0.7121	0.8078	0.102*
H18C	0.7745	0.7710	0.7994	0.102*
Cl1	0.46378 (5)	0.52727 (10)	0.33563 (8)	0.0797 (3)
Cl2	0.70005 (5)	0.54926 (9)	0.09348 (8)	0.0764 (3)
N1	0.63785 (13)	0.4885 (2)	0.31082 (19)	0.0498 (5)
N2	0.65194 (12)	0.55064 (18)	0.40892 (19)	0.0435 (5)
N3	0.90058 (11)	0.19559 (17)	0.73893 (18)	0.0352 (4)
O1	0.78373 (12)	0.59483 (17)	0.84753 (16)	0.0551 (5)
O3	0.85420 (10)	0.37752 (14)	0.85661 (14)	0.0420 (4)
O4	1.03869 (11)	0.21784 (17)	0.93174 (15)	0.0443 (4)
O5	0.98183 (12)	−0.10746 (16)	0.85653 (19)	0.0531 (5)
O6	0.90118 (12)	−0.04188 (16)	0.57467 (18)	0.0471 (4)
H33	0.9027 (16)	0.237 (3)	0.799 (3)	0.051 (8)*
H44	1.0575 (17)	0.280 (3)	0.929 (3)	0.050 (8)*
H55	0.979 (2)	−0.140 (3)	0.920 (3)	0.068 (10)*
H66	0.8821 (17)	−0.022 (3)	0.513 (3)	0.043 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0480 (13)	0.0433 (13)	0.0390 (12)	−0.0016 (10)	−0.0010 (10)	−0.0006 (10)
C2	0.0516 (14)	0.0561 (15)	0.0520 (15)	−0.0015 (12)	0.0052 (12)	−0.0032 (12)
C3	0.0573 (17)	0.0675 (19)	0.075 (2)	0.0084 (14)	−0.0016 (15)	0.0042 (17)
C4	0.083 (2)	0.066 (2)	0.068 (2)	0.0027 (17)	−0.0173 (17)	0.0144 (17)
C5	0.083 (2)	0.0666 (18)	0.0476 (16)	−0.0127 (16)	0.0010 (14)	0.0128 (14)
C6	0.0557 (14)	0.0570 (15)	0.0447 (14)	−0.0117 (12)	0.0042 (11)	−0.0016 (12)
C7	0.0376 (11)	0.0376 (11)	0.0389 (12)	0.0030 (9)	0.0060 (9)	0.0064 (10)
C8	0.0388 (11)	0.0363 (11)	0.0444 (13)	0.0076 (9)	0.0084 (9)	0.0028 (10)
C9	0.0399 (11)	0.0387 (12)	0.0391 (12)	0.0051 (9)	0.0107 (9)	−0.0013 (9)
C10	0.0335 (10)	0.0360 (11)	0.0352 (11)	0.0001 (8)	0.0093 (8)	0.0016 (9)
C11	0.0391 (11)	0.0331 (10)	0.0349 (11)	0.0014 (9)	0.0076 (8)	0.0016 (9)
C12	0.0433 (12)	0.0390 (12)	0.0343 (11)	0.0014 (9)	0.0056 (9)	−0.0010 (9)
C13	0.0429 (11)	0.0336 (10)	0.0346 (11)	0.0022 (9)	0.0091 (9)	−0.0014 (9)
C14	0.0403 (11)	0.0279 (10)	0.0331 (11)	0.0047 (8)	0.0092 (8)	0.0025 (8)
C15	0.0478 (12)	0.0375 (11)	0.0354 (11)	0.0075 (9)	0.0130 (9)	0.0024 (9)
C16	0.0497 (12)	0.0339 (11)	0.0335 (11)	0.0009 (9)	0.0118 (9)	0.0023 (9)
C17	0.0434 (12)	0.0372 (11)	0.0397 (12)	0.0016 (9)	0.0106 (9)	0.0034 (9)
C18	0.096 (2)	0.0484 (15)	0.0555 (16)	0.0269 (15)	0.0134 (15)	−0.0101 (13)
Cl1	0.0630 (5)	0.1070 (7)	0.0731 (5)	−0.0062 (4)	0.0257 (4)	0.0000 (5)
Cl2	0.0646 (5)	0.1003 (6)	0.0664 (5)	−0.0108 (4)	0.0216 (4)	−0.0097 (4)
N1	0.0538 (12)	0.0466 (11)	0.0432 (11)	0.0050 (9)	0.0037 (9)	−0.0004 (9)
N2	0.0414 (10)	0.0441 (10)	0.0408 (11)	−0.0002 (8)	0.0042 (8)	0.0021 (9)
N3	0.0419 (10)	0.0309 (9)	0.0326 (9)	0.0049 (7)	0.0097 (7)	0.0002 (8)
O1	0.0714 (11)	0.0492 (10)	0.0392 (9)	0.0244 (8)	0.0062 (8)	−0.0073 (8)
O3	0.0496 (9)	0.0415 (9)	0.0326 (8)	0.0110 (7)	0.0073 (7)	0.0013 (7)
O4	0.0562 (10)	0.0336 (9)	0.0402 (9)	−0.0076 (8)	0.0082 (7)	0.0001 (7)
O5	0.0787 (13)	0.0352 (9)	0.0476 (10)	0.0140 (8)	0.0212 (9)	0.0115 (8)
O6	0.0642 (11)	0.0398 (9)	0.0318 (9)	0.0029 (8)	0.0042 (8)	−0.0021 (7)

Geometric parameters (Å, º)

C1—C6	1.378 (4)	C13—N3	1.284 (3)
C1—C2	1.399 (4)	C13—H13	0.9300
C1—N1	1.443 (3)	C14—N3	1.464 (3)
C2—C3	1.375 (4)	C14—C15	1.525 (3)
C2—Cl1	1.727 (3)	C14—C16	1.530 (3)
C3—C4	1.354 (5)	C14—C17	1.538 (3)
C3—H3	0.9300	C15—O6	1.417 (3)
C4—C5	1.387 (5)	C15—H15A	0.9700
C4—H4	0.9300	C15—H15B	0.9700
C5—C6	1.386 (4)	C16—O5	1.411 (3)
C5—H5	0.9300	C16—H16A	0.9700
C6—Cl2	1.732 (3)	C16—H16B	0.9700
C7—C12	1.372 (3)	C17—O4	1.425 (3)
C7—C8	1.409 (3)	C17—H17A	0.9700
C7—N2	1.417 (3)	C17—H17B	0.9700
C8—C9	1.364 (3)	C18—O1	1.417 (3)
C8—H8	0.9300	C18—H18A	0.9600
C9—O1	1.357 (3)	C18—H18B	0.9600
C9—C10	1.434 (3)	C18—H18C	0.9600
C10—O3	1.279 (3)	N1—N2	1.243 (3)
C10—C11	1.434 (3)	N3—H33	0.79 (3)
C11—C12	1.406 (3)	O4—H44	0.74 (3)
C11—C13	1.425 (3)	O5—H55	0.80 (4)
C12—H12	0.9300	O6—H66	0.70 (3)
C6—C1—C2	117.8 (2)	N3—C14—C15	113.15 (17)
C6—C1—N1	120.0 (2)	N3—C14—C16	105.37 (17)
C2—C1—N1	122.2 (2)	C15—C14—C16	112.28 (18)
C3—C2—C1	120.6 (3)	N3—C14—C17	107.04 (17)
C3—C2—Cl1	119.2 (2)	C15—C14—C17	107.13 (18)
C1—C2—Cl1	120.0 (2)	C16—C14—C17	111.82 (18)
C4—C3—C2	120.3 (3)	O6—C15—C14	112.68 (19)
C4—C3—H3	119.9	O6—C15—H15A	109.1
C2—C3—H3	119.9	C14—C15—H15A	109.1
C3—C4—C5	121.2 (3)	O6—C15—H15B	109.1
C3—C4—H4	119.4	C14—C15—H15B	109.1
C5—C4—H4	119.4	H15A—C15—H15B	107.8
C6—C5—C4	118.2 (3)	O5—C16—C14	108.52 (19)
C6—C5—H5	120.9	O5—C16—H16A	110.0
C4—C5—H5	120.9	C14—C16—H16A	110.0
C1—C6—C5	122.0 (3)	O5—C16—H16B	110.0
C1—C6—Cl2	119.3 (2)	C14—C16—H16B	110.0
C5—C6—Cl2	118.8 (3)	H16A—C16—H16B	108.4
C12—C7—C8	120.16 (19)	O4—C17—C14	111.17 (18)
C12—C7—N2	126.5 (2)	O4—C17—H17A	109.4
C8—C7—N2	113.35 (19)	C14—C17—H17A	109.4
C9—C8—C7	121.3 (2)	O4—C17—H17B	109.4
C9—C8—H8	119.3	C14—C17—H17B	109.4
C7—C8—H8	119.3	H17A—C17—H17B	108.0
O1—C9—C8	126.3 (2)	O1—C18—H18A	109.5
O1—C9—C10	112.76 (19)	O1—C18—H18B	109.5
C8—C9—C10	120.9 (2)	H18A—C18—H18B	109.5
O3—C10—C9	120.1 (2)	O1—C18—H18C	109.5
O3—C10—C11	123.37 (19)	H18A—C18—H18C	109.5
C9—C10—C11	116.44 (18)	H18B—C18—H18C	109.5
C12—C11—C13	119.0 (2)	N2—N1—C1	109.5 (2)
C12—C11—C10	121.38 (19)	N1—N2—C7	116.28 (19)
C13—C11—C10	119.47 (18)	C13—N3—C14	129.6 (2)
C7—C12—C11	119.6 (2)	C13—N3—H33	114 (2)
C7—C12—H12	120.2	C14—N3—H33	116 (2)
C11—C12—H12	120.2	C9—O1—C18	118.02 (19)
N3—C13—C11	122.2 (2)	C17—O4—H44	111 (2)
N3—C13—H13	118.9	C16—O5—H55	107 (2)
C11—C13—H13	118.9	C15—O6—H66	111 (2)
C6—C1—C2—C3	−3.1 (4)	C8—C7—C12—C11	1.6 (3)
N1—C1—C2—C3	178.2 (3)	N2—C7—C12—C11	−179.4 (2)
C6—C1—C2—Cl1	172.6 (2)	C13—C11—C12—C7	−174.0 (2)
N1—C1—C2—Cl1	−6.2 (3)	C10—C11—C12—C7	2.1 (3)
C1—C2—C3—C4	0.6 (5)	C12—C11—C13—N3	176.5 (2)
Cl1—C2—C3—C4	−175.1 (3)	C10—C11—C13—N3	0.3 (3)
C2—C3—C4—C5	1.6 (5)	N3—C14—C15—O6	−78.6 (2)
C3—C4—C5—C6	−1.2 (5)	C16—C14—C15—O6	40.5 (2)
C2—C1—C6—C5	3.4 (4)	C17—C14—C15—O6	163.68 (17)
N1—C1—C6—C5	−177.7 (2)	N3—C14—C16—O5	−178.82 (18)
C2—C1—C6—Cl2	−176.9 (2)	C15—C14—C16—O5	57.6 (2)
N1—C1—C6—Cl2	1.9 (3)	C17—C14—C16—O5	−62.9 (2)
C4—C5—C6—C1	−1.4 (4)	N3—C14—C17—O4	46.1 (2)
C4—C5—C6—Cl2	179.0 (2)	C15—C14—C17—O4	167.76 (17)
C12—C7—C8—C9	−2.9 (4)	C16—C14—C17—O4	−68.8 (2)
N2—C7—C8—C9	178.0 (2)	C6—C1—N1—N2	119.3 (3)
C7—C8—C9—O1	178.7 (2)	C2—C1—N1—N2	−62.0 (3)
C7—C8—C9—C10	0.3 (4)	C1—N1—N2—C7	179.2 (2)
O1—C9—C10—O3	2.1 (3)	C12—C7—N2—N1	2.7 (4)
C8—C9—C10—O3	−179.3 (2)	C8—C7—N2—N1	−178.3 (2)
O1—C9—C10—C11	−175.4 (2)	C11—C13—N3—C14	−175.4 (2)
C8—C9—C10—C11	3.2 (3)	C15—C14—N3—C13	10.7 (3)
O3—C10—C11—C12	178.1 (2)	C16—C14—N3—C13	−112.3 (2)
C9—C10—C11—C12	−4.5 (3)	C17—C14—N3—C13	128.5 (2)
O3—C10—C11—C13	−5.7 (3)	C8—C9—O1—C18	−2.0 (4)
C9—C10—C11—C13	171.7 (2)	C10—C9—O1—C18	176.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H33···O3	0.79 (3)	1.90 (3)	2.587 (2)	144 (3)
O4—H44···O6^i	0.74 (3)	2.04 (3)	2.777 (3)	174 (3)
O5—H55···O4^ii	0.80 (4)	1.94 (4)	2.740 (3)	176 (3)
O6—H66···O1^iii	0.70 (3)	2.25 (3)	2.802 (2)	137 (3)
O6—H66···O3^iii	0.70 (3)	2.28 (3)	2.923 (2)	153 (3)
C17—H17A···G1^iv	0.97 (1)	2.95 (1)	3.798 (2)	147 (1)

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

(II) (Z)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxy- 4-(3-methoxyphenyldiazenyl)cyclohexa-2,4-dienone

Crystal data

C19H23N3O6	F(000) = 824
Mr = 389.40	Dx = 1.352 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 13037 reflections
a = 16.3722 (11) Å	θ = 1.8–28.9°
b = 10.4506 (5) Å	µ = 0.10 mm^−1
c = 11.3239 (7) Å	T = 296 K
β = 99.180 (5)°	Prism, red
V = 1912.7 (2) Å^3	0.42 × 0.33 × 0.25 mm
Z = 4

Data collection

STOE IPDS-II diffractometer	3744 independent reflections
Radiation source: fine-focus sealed tube	2778 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.040
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 2.3°
ω scans	h = −20→20
Absorption correction: integration STOE X-RED (Stoe & Cie, 2002)	k = −12→12
Tmin = 0.970, Tmax = 0.982	l = −13→13
13464 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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0982P)^2 + 0.2314P] where P = (Fo^2 + 2Fc^2)/3
3744 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.83 e Å^−3
3 restraints	Δρmin = −0.32 e Å^−3

Special details

Experimental. 180 frames, detector distance = 100 mm

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	Occ. (<1)
C1	0.52543 (13)	0.3349 (2)	0.4226 (2)	0.0519 (5)
C2	0.48686 (16)	0.2193 (3)	0.4415 (3)	0.0682 (7)
H2	0.5041	0.1736	0.5115	0.082*
C3	0.42448 (17)	0.1724 (3)	0.3592 (3)	0.0748 (8)
C4	0.39987 (16)	0.2401 (3)	0.2573 (3)	0.0801 (9)
H4	0.3571	0.2089	0.2006	0.096*
C5	0.43803 (17)	0.3562 (4)	0.2363 (3)	0.0793 (9)
H5	0.4209	0.4008	0.1656	0.095*
C6	0.50125 (15)	0.4050 (3)	0.3205 (2)	0.0623 (6)
H6	0.5264	0.4825	0.3081	0.075*
C7	0.69341 (12)	0.49355 (19)	0.59813 (17)	0.0418 (4)
C8	0.70470 (13)	0.4220 (2)	0.70539 (19)	0.0479 (5)
H8	0.6738	0.3481	0.7104	0.058*
C9	0.75977 (13)	0.4594 (2)	0.80069 (17)	0.0454 (5)
C10	0.80727 (11)	0.57554 (17)	0.79880 (16)	0.0380 (4)
C11	0.79952 (12)	0.64124 (17)	0.68721 (16)	0.0370 (4)
C12	0.74184 (12)	0.59894 (19)	0.58899 (17)	0.0423 (4)
H12	0.7366	0.6432	0.5169	0.051*
C13	0.84989 (12)	0.74918 (17)	0.67492 (16)	0.0387 (4)
H13	0.8448	0.7902	0.6013	0.046*
C14	0.96009 (12)	0.89996 (16)	0.76805 (15)	0.0361 (4)
C15	1.04588 (12)	0.85128 (18)	0.82383 (17)	0.0415 (4)
H15A	1.0686	0.7993	0.7659	0.050*
H15B	1.0825	0.9236	0.8444	0.050*
C16	0.92688 (13)	0.99893 (17)	0.84776 (16)	0.0416 (4)
H16A	0.8722	1.0269	0.8108	0.050*
H16B	0.9224	0.9611	0.9247	0.050*
C17	0.96765 (13)	0.95486 (18)	0.64533 (16)	0.0415 (4)
H17A	1.0184	1.0040	0.6516	0.050*
H17B	0.9714	0.8849	0.5902	0.050*
C18A	0.7450 (17)	0.268 (2)	0.9174 (13)	0.094 (4)	0.64 (7)
H18A	0.7616	0.2370	0.9975	0.141*	0.64 (7)
H18B	0.7667	0.2125	0.8623	0.141*	0.64 (7)
H18C	0.6857	0.2693	0.8990	0.141*	0.64 (7)
C18B	0.725 (2)	0.298 (4)	0.9220 (17)	0.081 (6)	0.36 (7)
H18D	0.7413	0.2606	0.9997	0.121*	0.36 (7)
H18E	0.7286	0.2343	0.8617	0.121*	0.36 (7)
H18F	0.6695	0.3288	0.9147	0.121*	0.36 (7)
C19	0.3212 (2)	0.0104 (4)	0.3150 (4)	0.1198 (15)
H19A	0.2745	0.0641	0.3211	0.180*
H19B	0.3098	−0.0753	0.3381	0.180*
H19C	0.3315	0.0104	0.2339	0.180*
N1	0.58852 (11)	0.36940 (18)	0.51846 (16)	0.0505 (4)
N2	0.63259 (11)	0.46281 (16)	0.49844 (15)	0.0462 (4)
N3	0.90261 (10)	0.79222 (14)	0.76302 (14)	0.0372 (4)
O1	0.39043 (17)	0.0567 (3)	0.3900 (2)	0.1122 (9)
O2	0.77720 (12)	0.39743 (16)	0.90751 (15)	0.0679 (5)
O3	0.85535 (9)	0.61238 (13)	0.89346 (11)	0.0445 (4)
O4	1.04182 (10)	0.77718 (13)	0.92855 (12)	0.0459 (4)
O5	0.98120 (11)	1.10454 (13)	0.86388 (13)	0.0543 (4)
O6	0.90017 (10)	1.03429 (13)	0.59828 (12)	0.0483 (4)
H33	0.9020 (14)	0.751 (2)	0.828 (2)	0.049 (6)*
H44	1.0605 (16)	0.7055 (19)	0.919 (2)	0.070 (8)*
H55	0.9770 (17)	1.144 (2)	0.9268 (19)	0.072 (8)*
H66	0.8772 (16)	1.003 (3)	0.5358 (19)	0.070 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0416 (11)	0.0629 (14)	0.0513 (12)	−0.0114 (10)	0.0075 (9)	−0.0190 (10)
C2	0.0619 (15)	0.0732 (16)	0.0691 (15)	−0.0238 (13)	0.0099 (12)	−0.0196 (13)
C3	0.0614 (15)	0.0865 (19)	0.0757 (18)	−0.0238 (15)	0.0090 (14)	−0.0278 (16)
C4	0.0463 (13)	0.099 (2)	0.091 (2)	−0.0131 (14)	0.0005 (13)	−0.0468 (18)
C5	0.0619 (16)	0.113 (2)	0.0592 (15)	0.0141 (17)	−0.0016 (12)	−0.0168 (15)
C6	0.0509 (13)	0.0771 (16)	0.0573 (13)	−0.0010 (12)	0.0039 (11)	−0.0133 (12)
C7	0.0417 (10)	0.0415 (10)	0.0405 (10)	−0.0043 (8)	0.0009 (8)	−0.0045 (8)
C8	0.0480 (11)	0.0414 (10)	0.0527 (12)	−0.0118 (9)	0.0027 (9)	0.0007 (9)
C9	0.0467 (11)	0.0434 (10)	0.0439 (10)	−0.0076 (9)	0.0009 (9)	0.0083 (8)
C10	0.0399 (10)	0.0355 (9)	0.0373 (9)	−0.0010 (8)	0.0026 (8)	−0.0005 (7)
C11	0.0416 (10)	0.0316 (8)	0.0363 (9)	−0.0024 (8)	0.0014 (8)	−0.0009 (7)
C12	0.0496 (11)	0.0402 (10)	0.0353 (9)	−0.0041 (8)	0.0008 (8)	−0.0002 (8)
C13	0.0489 (11)	0.0324 (9)	0.0333 (9)	−0.0022 (8)	0.0024 (8)	0.0003 (7)
C14	0.0461 (10)	0.0282 (8)	0.0330 (8)	−0.0047 (7)	0.0027 (7)	−0.0007 (7)
C15	0.0462 (11)	0.0354 (9)	0.0412 (9)	−0.0037 (8)	0.0020 (8)	−0.0010 (8)
C16	0.0564 (12)	0.0324 (9)	0.0350 (9)	−0.0014 (8)	0.0047 (8)	−0.0012 (7)
C17	0.0534 (11)	0.0355 (9)	0.0351 (9)	−0.0057 (8)	0.0055 (8)	0.0014 (7)
C18A	0.092 (8)	0.058 (7)	0.118 (8)	−0.037 (6)	−0.023 (4)	0.044 (4)
C18B	0.122 (14)	0.055 (10)	0.054 (8)	−0.021 (9)	−0.020 (6)	0.041 (5)
C19	0.081 (2)	0.133 (3)	0.146 (4)	−0.050 (2)	0.018 (2)	−0.049 (3)
N1	0.0474 (10)	0.0517 (10)	0.0511 (10)	−0.0107 (8)	0.0041 (8)	−0.0117 (8)
N2	0.0455 (9)	0.0452 (9)	0.0463 (9)	−0.0083 (8)	0.0028 (7)	−0.0094 (7)
N3	0.0469 (9)	0.0308 (8)	0.0324 (8)	−0.0044 (7)	0.0017 (7)	0.0013 (6)
O1	0.1119 (18)	0.1044 (18)	0.1134 (19)	−0.0588 (16)	−0.0033 (15)	−0.0215 (14)
O2	0.0788 (11)	0.0611 (10)	0.0564 (9)	−0.0313 (9)	−0.0118 (8)	0.0256 (8)
O3	0.0502 (8)	0.0441 (8)	0.0364 (7)	−0.0094 (6)	−0.0021 (6)	0.0035 (6)
O4	0.0633 (9)	0.0330 (7)	0.0384 (7)	0.0060 (7)	−0.0009 (6)	−0.0010 (6)
O5	0.0830 (11)	0.0341 (7)	0.0461 (8)	−0.0134 (7)	0.0113 (8)	−0.0103 (6)
O6	0.0701 (10)	0.0361 (7)	0.0342 (7)	−0.0017 (7)	−0.0058 (7)	0.0013 (6)

Geometric parameters (Å, º)

C1—C6	1.372 (4)	C14—C16	1.529 (3)
C1—C2	1.396 (3)	C14—C15	1.532 (3)
C1—N1	1.420 (3)	C15—O4	1.427 (2)
C2—C3	1.359 (4)	C15—H15A	0.9700
C2—H2	0.9300	C15—H15B	0.9700
C3—C4	1.359 (5)	C16—O5	1.411 (2)
C3—O1	1.399 (4)	C16—H16A	0.9700
C4—C5	1.403 (5)	C16—H16B	0.9700
C4—H4	0.9300	C17—O6	1.416 (3)
C5—C6	1.387 (4)	C17—H17A	0.9700
C5—H5	0.9300	C17—H17B	0.9700
C6—H6	0.9300	C18A—O2	1.463 (16)
C7—C12	1.371 (3)	C18A—H18A	0.9600
C7—C8	1.413 (3)	C18A—H18B	0.9600
C7—N2	1.418 (3)	C18A—H18C	0.9600
C8—C9	1.349 (3)	C18B—O2	1.37 (2)
C8—H8	0.9300	C18B—H18D	0.9600
C9—O2	1.362 (2)	C18B—H18E	0.9600
C9—C10	1.443 (3)	C18B—H18F	0.9600
C10—O3	1.284 (2)	C19—O1	1.391 (4)
C10—C11	1.426 (3)	C19—H19A	0.9600
C11—C12	1.410 (3)	C19—H19B	0.9600
C11—C13	1.417 (3)	C19—H19C	0.9600
C12—H12	0.9300	N1—N2	1.256 (2)
C13—N3	1.291 (2)	N3—H33	0.86 (2)
C13—H13	0.9300	O4—H44	0.824 (17)
C14—N3	1.463 (2)	O5—H55	0.836 (17)
C14—C17	1.527 (2)	O6—H66	0.815 (17)
C6—C1—C2	121.0 (2)	O4—C15—H15A	109.4
C6—C1—N1	125.8 (2)	C14—C15—H15A	109.4
C2—C1—N1	113.2 (2)	O4—C15—H15B	109.4
C3—C2—C1	121.0 (3)	C14—C15—H15B	109.4
C3—C2—H2	119.5	H15A—C15—H15B	108.0
C1—C2—H2	119.5	O5—C16—C14	109.24 (16)
C4—C3—C2	118.9 (3)	O5—C16—H16A	109.8
C4—C3—O1	125.8 (3)	C14—C16—H16A	109.8
C2—C3—O1	115.2 (3)	O5—C16—H16B	109.8
C3—C4—C5	120.9 (2)	C14—C16—H16B	109.8
C3—C4—H4	119.5	H16A—C16—H16B	108.3
C5—C4—H4	119.5	O6—C17—C14	113.02 (16)
C6—C5—C4	120.3 (3)	O6—C17—H17A	109.0
C6—C5—H5	119.8	C14—C17—H17A	109.0
C4—C5—H5	119.8	O6—C17—H17B	109.0
C1—C6—C5	117.8 (3)	C14—C17—H17B	109.0
C1—C6—H6	121.1	H17A—C17—H17B	107.8
C5—C6—H6	121.1	O2—C18A—H18A	109.5
C12—C7—C8	119.48 (18)	O2—C18A—H18B	109.5
C12—C7—N2	117.59 (17)	H18A—C18A—H18B	109.5
C8—C7—N2	122.92 (18)	O2—C18A—H18C	109.5
C9—C8—C7	120.88 (19)	H18A—C18A—H18C	109.5
C9—C8—H8	119.6	H18B—C18A—H18C	109.5
C7—C8—H8	119.6	O2—C18B—H18D	109.5
C8—C9—O2	126.24 (18)	O2—C18B—H18E	109.5
C8—C9—C10	121.66 (18)	H18D—C18B—H18E	109.5
O2—C9—C10	112.10 (17)	O2—C18B—H18F	109.5
O3—C10—C11	123.48 (16)	H18D—C18B—H18F	109.5
O3—C10—C9	119.99 (16)	H18E—C18B—H18F	109.5
C11—C10—C9	116.49 (16)	O1—C19—H19A	109.5
C12—C11—C13	119.93 (17)	O1—C19—H19B	109.5
C12—C11—C10	120.11 (17)	H19A—C19—H19B	109.5
C13—C11—C10	119.96 (16)	O1—C19—H19C	109.5
C7—C12—C11	121.00 (17)	H19A—C19—H19C	109.5
C7—C12—H12	119.5	H19B—C19—H19C	109.5
C11—C12—H12	119.5	N2—N1—C1	115.35 (19)
N3—C13—C11	121.94 (17)	N1—N2—C7	112.53 (17)
N3—C13—H13	119.0	C13—N3—C14	130.15 (16)
C11—C13—H13	119.0	C13—N3—H33	113.0 (15)
N3—C14—C17	113.51 (15)	C14—N3—H33	116.9 (16)
N3—C14—C16	104.87 (15)	C19—O1—C3	117.8 (3)
C17—C14—C16	111.80 (15)	C9—O2—C18B	114.9 (9)
N3—C14—C15	107.59 (14)	C9—O2—C18A	118.8 (6)
C17—C14—C15	107.33 (15)	C15—O4—H44	108.2 (19)
C16—C14—C15	111.73 (15)	C16—O5—H55	111 (2)
O4—C15—C14	111.20 (16)	C17—O6—H66	108 (2)
C6—C1—C2—C3	0.3 (4)	C12—C11—C13—N3	178.97 (18)
N1—C1—C2—C3	179.4 (2)	C10—C11—C13—N3	−1.1 (3)
C1—C2—C3—C4	0.0 (4)	N3—C14—C15—O4	−46.68 (19)
C1—C2—C3—O1	−179.1 (2)	C17—C14—C15—O4	−169.18 (15)
C2—C3—C4—C5	0.2 (4)	C16—C14—C15—O4	67.92 (19)
O1—C3—C4—C5	179.3 (3)	N3—C14—C16—O5	176.68 (15)
C3—C4—C5—C6	−0.8 (4)	C17—C14—C16—O5	−59.9 (2)
C2—C1—C6—C5	−0.8 (4)	C15—C14—C16—O5	60.41 (19)
N1—C1—C6—C5	−179.8 (2)	N3—C14—C17—O6	77.8 (2)
C4—C5—C6—C1	1.0 (4)	C16—C14—C17—O6	−40.6 (2)
C12—C7—C8—C9	3.1 (3)	C15—C14—C17—O6	−163.42 (15)
N2—C7—C8—C9	−175.8 (2)	C6—C1—N1—N2	−10.5 (3)
C7—C8—C9—O2	−178.6 (2)	C2—C1—N1—N2	170.4 (2)
C7—C8—C9—C10	2.1 (3)	C1—N1—N2—C7	179.06 (17)
C8—C9—C10—O3	175.70 (19)	C12—C7—N2—N1	−176.11 (18)
O2—C9—C10—O3	−3.7 (3)	C8—C7—N2—N1	2.8 (3)
C8—C9—C10—C11	−6.5 (3)	C11—C13—N3—C14	179.28 (17)
O2—C9—C10—C11	174.16 (18)	C17—C14—N3—C13	−10.9 (3)
O3—C10—C11—C12	−176.37 (18)	C16—C14—N3—C13	111.4 (2)
C9—C10—C11—C12	5.9 (3)	C15—C14—N3—C13	−129.5 (2)
O3—C10—C11—C13	3.7 (3)	C4—C3—O1—C19	−5.2 (5)
C9—C10—C11—C13	−174.08 (17)	C2—C3—O1—C19	173.8 (3)
C8—C7—C12—C11	−3.6 (3)	C8—C9—O2—C18B	−9 (2)
N2—C7—C12—C11	175.32 (18)	C10—C9—O2—C18B	170 (2)
C13—C11—C12—C7	178.93 (18)	C8—C9—O2—C18A	10.9 (16)
C10—C11—C12—C7	−1.0 (3)	C10—C9—O2—C18A	−169.8 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H33···O3	0.86 (2)	1.84 (2)	2.584 (2)	144 (2)
O4—H44···O6^i	0.82 (2)	1.92 (2)	2.744 (2)	177 (3)
O5—H55···O4^ii	0.84 (2)	1.90 (2)	2.734 (2)	174 (3)
O6—H66···O3^iii	0.82 (2)	2.00 (2)	2.7792 (19)	160 (3)
O6—H66···O2^iii	0.82 (2)	2.26 (3)	2.800 (2)	124 (2)
C15—H15B···G1^iv	0.93 (1)	3.05)	3.861 (2)	142 (1)

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

(III) (Z)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylamino]methylene}-2-methoxy- 4-(4-methoxyphenyldiazenyl)cyclohexa-2,4-dienone

Crystal data

C19H23N3O6	F(000) = 824
Mr = 389.40	Dx = 1.369 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 17273 reflections
a = 16.9333 (9) Å	θ = 1.9–28.8°
b = 10.7124 (6) Å	µ = 0.10 mm^−1
c = 10.5476 (6) Å	T = 296 K
β = 98.966 (4)°	Plate, red
V = 1889.92 (18) Å^3	0.35 × 0.23 × 0.09 mm
Z = 4

Data collection

STOE IPD-II diffractometer	3714 independent reflections
Radiation source: fine-focus sealed tube	2438 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.116
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 2.3°
ω scans	h = −20→20
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→13
Tmin = 0.973, Tmax = 0.993	l = −12→12
17746 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.135	w = 1/[σ^2(Fo^2) + (0.0684P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
3714 reflections	Δρmax = 0.23 e Å^−3
311 parameters	Δρmin = −0.18 e Å^−3
42 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.009 (2)

Special details

Experimental. 243 frames, detector distance = 100 mm

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	Occ. (<1)
C1	0.47825 (17)	0.4219 (2)	0.6766 (3)	0.0612 (7)
C2A	0.5108 (8)	0.3170 (11)	0.7251 (11)	0.137 (2)	0.409 (7)
H2A	0.4955	0.2430	0.6822	0.164*	0.409 (7)
C2B	0.5420 (3)	0.3368 (6)	0.6687 (5)	0.0555 (14)	0.591 (7)
H2B	0.5410	0.2848	0.5979	0.067*	0.591 (7)
C3A	0.5666 (9)	0.3103 (10)	0.8364 (13)	0.1364 (6)	0.409 (7)
H3A	0.5778	0.2347	0.8788	0.164*	0.409 (7)
C3B	0.6052 (3)	0.3334 (5)	0.7687 (5)	0.0588 (14)	0.591 (7)
H3B	0.6483	0.2804	0.7653	0.071*	0.591 (7)
C4	0.6036 (2)	0.4146 (3)	0.8809 (3)	0.0800 (10)
C5A	0.5640 (6)	0.5219 (10)	0.8497 (8)	0.067 (2)	0.591 (7)
H5A	0.5776	0.5933	0.8985	0.081*	0.591 (7)
C5B	0.5440 (8)	0.4927 (14)	0.8831 (12)	0.062 (3)	0.409 (7)
H5B	0.5441	0.5468	0.9521	0.075*	0.409 (7)
C6A	0.5031 (5)	0.5271 (8)	0.7457 (8)	0.067 (2)	0.591 (7)
H6A	0.4786	0.6032	0.7222	0.080*	0.591 (7)
C6B	0.4811 (8)	0.4942 (11)	0.7822 (10)	0.060 (3)	0.409 (7)
H6B	0.4385	0.5478	0.7873	0.073*	0.409 (7)
C7	0.30538 (15)	0.5163 (2)	0.46511 (19)	0.0447 (5)
C8	0.29236 (15)	0.4275 (2)	0.3637 (2)	0.0462 (6)
H8	0.3224	0.3544	0.3689	0.055*
C9	0.23633 (15)	0.44917 (18)	0.25949 (18)	0.0403 (5)
C10	0.19049 (13)	0.56275 (18)	0.24400 (17)	0.0355 (5)
C11	0.20056 (13)	0.64624 (17)	0.35168 (18)	0.0371 (5)
C12	0.25884 (15)	0.6205 (2)	0.45999 (19)	0.0456 (6)
H12	0.2655	0.6757	0.5289	0.055*
C13	0.15416 (13)	0.75538 (18)	0.35053 (18)	0.0373 (5)
H13	0.1626	0.8073	0.4221	0.045*
C14	0.04710 (13)	0.89617 (16)	0.24302 (16)	0.0327 (5)
C15	−0.03672 (13)	0.85092 (18)	0.18749 (17)	0.0366 (5)
H15A	−0.0591	0.8050	0.2527	0.044*
H15B	−0.0708	0.9224	0.1626	0.044*
C16	0.08007 (14)	0.98723 (17)	0.15268 (17)	0.0385 (5)
H16A	0.1347	1.0095	0.1870	0.046*
H16B	0.0795	0.9491	0.0691	0.046*
C17	0.04120 (14)	0.95798 (17)	0.37162 (16)	0.0350 (5)
H17A	−0.0080	1.0056	0.3634	0.042*
H17B	0.0385	0.8935	0.4353	0.042*
C18	0.6817 (2)	0.4947 (5)	1.0700 (3)	0.1046 (13)
H18A	0.7079	0.4688	1.1532	0.157*	0.50
H18B	0.6413	0.5554	1.0799	0.157*	0.50
H18C	0.7201	0.5310	1.0231	0.157*	0.50
H18D	0.6717	0.5680	1.0176	0.157*	0.50
H18E	0.7383	0.4814	1.0909	0.157*	0.50
H18F	0.6594	0.5058	1.1476	0.157*	0.50
C19	0.2502 (2)	0.2484 (3)	0.1693 (3)	0.0892 (12)
H19A	0.2320	0.2019	0.0925	0.134*
H19B	0.2339	0.2067	0.2415	0.134*
H19C	0.3075	0.2544	0.1816	0.134*
N1	0.41502 (15)	0.42043 (19)	0.5698 (2)	0.0607 (6)
N2	0.36663 (13)	0.50856 (18)	0.57222 (18)	0.0521 (5)
N3	0.10037 (11)	0.78718 (14)	0.25490 (15)	0.0347 (4)
O1A	0.6473 (7)	0.3947 (13)	1.0053 (11)	0.096 (4)	0.409 (7)
O1B	0.6754 (4)	0.4066 (9)	0.9636 (7)	0.0733 (17)	0.591 (7)
O2	0.21672 (12)	0.36987 (14)	0.15796 (15)	0.0579 (5)
O3	0.14223 (10)	0.58546 (12)	0.14174 (12)	0.0414 (4)
O4	−0.03509 (11)	0.77273 (13)	0.07885 (12)	0.0418 (4)
O5	0.03106 (13)	1.09466 (13)	0.14145 (15)	0.0539 (5)
O6	0.10637 (10)	1.03845 (12)	0.41583 (12)	0.0415 (4)
H33	0.0970 (16)	0.732 (2)	0.188 (2)	0.056 (7)*
H44	−0.0647 (17)	0.711 (2)	0.085 (3)	0.074 (10)*
H55	0.035 (2)	1.136 (3)	0.078 (3)	0.114 (14)*
H66	0.1294 (15)	1.017 (2)	0.4899 (18)	0.055 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0573 (18)	0.0550 (14)	0.0635 (15)	0.0142 (13)	−0.0151 (13)	0.0064 (11)
C2A	0.150	0.071 (7)	0.150	0.044 (8)	−0.101 (6)	−0.037 (7)
C2B	0.047 (3)	0.048 (3)	0.070 (3)	0.008 (2)	0.004 (2)	0.004 (2)
C3A	0.150	0.070	0.150	0.039 (6)	−0.099 (6)	0.000 (7)
C3B	0.041 (3)	0.053 (3)	0.078 (3)	0.009 (2)	−0.006 (2)	0.007 (2)
C4	0.072 (2)	0.0658 (18)	0.087 (2)	0.0112 (16)	−0.0337 (17)	0.0044 (15)
C5A	0.057 (6)	0.087 (5)	0.053 (5)	0.009 (4)	−0.003 (3)	−0.008 (4)
C5B	0.042 (6)	0.104 (9)	0.040 (5)	0.023 (6)	0.004 (4)	0.004 (4)
C6A	0.062 (5)	0.068 (4)	0.064 (5)	0.014 (4)	−0.012 (3)	0.006 (3)
C6B	0.052 (6)	0.082 (8)	0.046 (5)	0.025 (5)	0.002 (4)	0.006 (4)
C7	0.0486 (14)	0.0419 (11)	0.0390 (10)	0.0070 (10)	−0.0075 (10)	0.0019 (8)
C8	0.0500 (15)	0.0373 (11)	0.0488 (12)	0.0090 (10)	−0.0007 (11)	0.0008 (9)
C9	0.0485 (14)	0.0329 (10)	0.0378 (10)	0.0025 (9)	0.0019 (9)	−0.0062 (8)
C10	0.0379 (12)	0.0327 (10)	0.0336 (9)	−0.0005 (9)	−0.0018 (9)	−0.0001 (7)
C11	0.0434 (13)	0.0309 (9)	0.0338 (9)	0.0037 (9)	−0.0039 (9)	−0.0024 (7)
C12	0.0541 (15)	0.0407 (11)	0.0369 (10)	0.0059 (10)	−0.0084 (10)	−0.0041 (8)
C13	0.0432 (13)	0.0325 (10)	0.0328 (9)	0.0016 (9)	−0.0045 (9)	−0.0032 (7)
C14	0.0452 (13)	0.0262 (9)	0.0248 (8)	0.0061 (8)	−0.0009 (8)	0.0005 (7)
C15	0.0453 (13)	0.0311 (9)	0.0313 (9)	0.0027 (9)	−0.0006 (9)	0.0006 (7)
C16	0.0535 (14)	0.0332 (10)	0.0275 (9)	−0.0001 (9)	0.0022 (9)	0.0013 (7)
C17	0.0462 (13)	0.0309 (9)	0.0266 (8)	0.0042 (9)	0.0021 (8)	−0.0002 (7)
C18	0.074 (2)	0.156 (4)	0.073 (2)	0.018 (3)	−0.0236 (18)	−0.018 (2)
C19	0.118 (3)	0.0473 (15)	0.092 (2)	0.0254 (17)	−0.016 (2)	−0.0311 (15)
N1	0.0623 (15)	0.0518 (12)	0.0608 (12)	0.0145 (11)	−0.0129 (11)	0.0036 (9)
N2	0.0528 (13)	0.0497 (11)	0.0479 (10)	0.0122 (10)	−0.0102 (9)	0.0042 (8)
N3	0.0449 (11)	0.0283 (8)	0.0288 (8)	0.0039 (7)	−0.0006 (7)	−0.0021 (6)
O1A	0.088 (9)	0.094 (5)	0.086 (7)	0.013 (6)	−0.049 (5)	0.007 (5)
O1B	0.048 (3)	0.079 (3)	0.084 (4)	0.010 (3)	−0.019 (2)	0.007 (3)
O2	0.0773 (14)	0.0408 (8)	0.0499 (9)	0.0161 (8)	−0.0084 (8)	−0.0161 (7)
O3	0.0488 (10)	0.0393 (7)	0.0318 (7)	0.0061 (7)	−0.0073 (6)	−0.0055 (5)
O4	0.0608 (11)	0.0299 (7)	0.0314 (7)	−0.0069 (7)	−0.0031 (7)	−0.0011 (5)
O5	0.0885 (14)	0.0326 (8)	0.0411 (8)	0.0127 (8)	0.0114 (8)	0.0100 (6)
O6	0.0592 (11)	0.0341 (7)	0.0266 (6)	−0.0020 (7)	−0.0070 (7)	−0.0005 (5)

Geometric parameters (Å, º)

C1—C2A	1.319 (11)	C12—H12	0.9300
C1—C6B	1.352 (13)	C13—N3	1.295 (3)
C1—C6A	1.372 (9)	C13—H13	0.9300
C1—C2B	1.425 (7)	C14—N3	1.469 (2)
C1—N1	1.428 (3)	C14—C17	1.527 (2)
C2A—C3A	1.389 (13)	C14—C15	1.528 (3)
C2A—H2A	0.9300	C14—C16	1.529 (3)
C2B—C3B	1.381 (7)	C15—O4	1.423 (2)
C2B—H2B	0.9300	C15—H15A	0.9700
C3A—C4	1.331 (12)	C15—H15B	0.9700
C3A—H3A	0.9300	C16—O5	1.413 (3)
C3B—C4	1.472 (6)	C16—H16A	0.9700
C3B—H3B	0.9300	C16—H16B	0.9700
C4—C5B	1.314 (15)	C17—O6	1.420 (3)
C4—C5A	1.346 (11)	C17—H17A	0.9700
C4—O1B	1.385 (9)	C17—H17B	0.9700
C4—O1A	1.419 (11)	C18—O1A	1.353 (14)
C5A—C6A	1.385 (14)	C18—O1B	1.458 (10)
C5A—H5A	0.9300	C18—H18A	0.9600
C5B—C6B	1.38 (2)	C18—H18B	0.9600
C5B—H5B	0.9300	C18—H18C	0.9600
C6A—H6A	0.9300	C18—H18D	0.9600
C6B—H6B	0.9300	C18—H18E	0.9600
C7—C12	1.363 (3)	C18—H18F	0.9600
C7—N2	1.412 (3)	C19—O2	1.417 (3)
C7—C8	1.422 (3)	C19—H19A	0.9600
C8—C9	1.356 (3)	C19—H19B	0.9600
C8—H8	0.9300	C19—H19C	0.9600
C9—O2	1.367 (2)	N1—N2	1.253 (3)
C9—C10	1.439 (3)	N3—H33	0.92 (3)
C10—O3	1.271 (2)	O4—H44	0.837 (18)
C10—C11	1.435 (3)	O5—H55	0.815 (19)
C11—C13	1.408 (3)	O6—H66	0.850 (17)
C11—C12	1.416 (3)
C2A—C1—C6B	102.1 (7)	C17—C14—C15	107.03 (18)
C2A—C1—C6A	114.8 (6)	N3—C14—C16	106.34 (16)
C6B—C1—C2B	119.0 (6)	C17—C14—C16	110.97 (15)
C6A—C1—C2B	112.6 (5)	C15—C14—C16	111.79 (15)
C2A—C1—N1	120.9 (5)	O4—C15—C14	111.23 (18)
C6B—C1—N1	125.6 (6)	O4—C15—H15A	109.4
C6A—C1—N1	123.9 (4)	C14—C15—H15A	109.4
C2B—C1—N1	115.3 (3)	O4—C15—H15B	109.4
C1—C2A—C3A	124.1 (10)	C14—C15—H15B	109.4
C1—C2A—H2A	118.0	H15A—C15—H15B	108.0
C3A—C2A—H2A	118.0	O5—C16—C14	107.77 (17)
C3B—C2B—C1	118.4 (5)	O5—C16—H16A	110.2
C3B—C2B—H2B	120.8	C14—C16—H16A	110.2
C1—C2B—H2B	120.8	O5—C16—H16B	110.2
C4—C3A—C2A	118.4 (9)	C14—C16—H16B	110.2
C4—C3A—H3A	120.8	H16A—C16—H16B	108.5
C2A—C3A—H3A	120.8	O6—C17—C14	113.57 (17)
C2B—C3B—C4	119.3 (5)	O6—C17—H17A	108.9
C2B—C3B—H3B	120.3	C14—C17—H17A	108.9
C4—C3B—H3B	120.3	O6—C17—H17B	108.9
C5B—C4—C3A	102.7 (10)	C14—C17—H17B	108.9
C3A—C4—C5A	116.2 (6)	H17A—C17—H17B	107.7
C5B—C4—O1B	129.1 (8)	O1A—C18—H18A	109.5
C3A—C4—O1B	119.3 (6)	O1B—C18—H18A	118.9
C5A—C4—O1B	124.2 (6)	O1A—C18—H18B	109.5
C5B—C4—O1A	111.8 (9)	O1B—C18—H18B	123.6
C3A—C4—O1A	110.4 (8)	H18A—C18—H18B	109.5
C5A—C4—O1A	121.5 (8)	O1A—C18—H18C	109.5
C5B—C4—C3B	120.0 (7)	O1B—C18—H18C	80.7
C5A—C4—C3B	112.3 (5)	H18A—C18—H18C	109.5
O1B—C4—C3B	110.2 (5)	H18B—C18—H18C	109.5
O1A—C4—C3B	125.6 (6)	O1A—C18—H18D	109.5
C4—C5A—C6A	120.6 (9)	O1B—C18—H18D	95.7
C4—C5A—H5A	119.7	H18A—C18—H18D	141.1
C6A—C5A—H5A	119.7	H18B—C18—H18D	56.3
C4—C5B—C6B	119.7 (13)	H18C—C18—H18D	56.3
C4—C5B—H5B	120.2	O1A—C18—H18E	109.5
C6B—C5B—H5B	120.2	O1B—C18—H18E	91.7
C1—C6A—C5A	121.1 (8)	H18A—C18—H18E	56.3
C1—C6A—H6A	119.5	H18B—C18—H18E	141.1
C5A—C6A—H6A	119.5	H18C—C18—H18E	56.3
C1—C6B—C5B	123.5 (11)	H18D—C18—H18E	109.5
C1—C6B—H6B	118.3	O1A—C18—H18F	109.5
C5B—C6B—H6B	118.3	O1B—C18—H18F	138.2
C12—C7—N2	115.33 (19)	H18A—C18—H18F	56.3
C12—C7—C8	119.8 (2)	H18B—C18—H18F	56.3
N2—C7—C8	124.8 (2)	H18C—C18—H18F	141.1
C9—C8—C7	120.1 (2)	H18D—C18—H18F	109.5
C9—C8—H8	119.9	H18E—C18—H18F	109.5
C7—C8—H8	119.9	O2—C19—H19A	109.5
C8—C9—O2	125.7 (2)	O2—C19—H19B	109.5
C8—C9—C10	122.27 (18)	H19A—C19—H19B	109.5
O2—C9—C10	112.07 (18)	O2—C19—H19C	109.5
O3—C10—C11	122.26 (18)	H19A—C19—H19C	109.5
O3—C10—C9	121.49 (17)	H19B—C19—H19C	109.5
C11—C10—C9	116.22 (17)	N2—N1—C1	112.8 (2)
C13—C11—C12	119.13 (17)	N1—N2—C7	115.4 (2)
C13—C11—C10	120.90 (18)	C13—N3—C14	128.58 (16)
C12—C11—C10	119.96 (18)	C13—N3—H33	112.5 (17)
C7—C12—C11	121.18 (19)	C14—N3—H33	118.9 (17)
C7—C12—H12	119.4	C18—O1A—C4	118.0 (10)
C11—C12—H12	119.4	C4—O1B—C18	113.3 (6)
N3—C13—C11	123.31 (18)	C9—O2—C19	117.35 (19)
N3—C13—H13	118.3	C15—O4—H44	109 (2)
C11—C13—H13	118.3	C16—O5—H55	113 (3)
N3—C14—C17	113.17 (15)	C17—O6—H66	110.9 (18)
N3—C14—C15	107.58 (15)
C6B—C1—C2A—C3A	−27.9 (15)	C8—C9—C10—C11	−7.0 (3)
C6A—C1—C2A—C3A	−0.6 (16)	O2—C9—C10—C11	173.55 (19)
C2B—C1—C2A—C3A	94.7 (17)	O3—C10—C11—C13	2.9 (3)
N1—C1—C2A—C3A	−173.2 (11)	C9—C10—C11—C13	−175.1 (2)
C2A—C1—C2B—C3B	−71.7 (9)	O3—C10—C11—C12	−175.9 (2)
C6B—C1—C2B—C3B	−1.3 (8)	C9—C10—C11—C12	6.0 (3)
C6A—C1—C2B—C3B	29.9 (6)	N2—C7—C12—C11	173.6 (2)
N1—C1—C2B—C3B	179.9 (4)	C8—C7—C12—C11	−3.8 (4)
C1—C2A—C3A—C4	−16 (2)	C13—C11—C12—C7	−179.7 (2)
C1—C2B—C3B—C4	1.7 (7)	C10—C11—C12—C7	−0.9 (4)
C2A—C3A—C4—C5B	50.5 (15)	C12—C11—C13—N3	179.0 (2)
C2A—C3A—C4—C5A	26.2 (17)	C10—C11—C13—N3	0.2 (3)
C2A—C3A—C4—O1B	−159.3 (10)	N3—C14—C15—O4	−47.77 (19)
C2A—C3A—C4—O1A	169.9 (11)	C17—C14—C15—O4	−169.68 (14)
C2A—C3A—C4—C3B	−69.7 (12)	C16—C14—C15—O4	68.62 (19)
C2B—C3B—C4—C5B	−2.6 (9)	N3—C14—C16—O5	−178.70 (16)
C2B—C3B—C4—C3A	74.4 (7)	C17—C14—C16—O5	−55.2 (2)
C2B—C3B—C4—C5A	−31.0 (8)	C15—C14—C16—O5	64.2 (2)
C2B—C3B—C4—O1B	−173.9 (5)	N3—C14—C17—O6	80.6 (2)
C2B—C3B—C4—O1A	157.7 (7)	C15—C14—C17—O6	−161.11 (15)
C5B—C4—C5A—C6A	−85 (3)	C16—C14—C17—O6	−38.9 (2)
C3A—C4—C5A—C6A	−20.7 (13)	C2A—C1—N1—N2	147.9 (8)
O1B—C4—C5A—C6A	165.1 (7)	C6B—C1—N1—N2	11.1 (7)
O1A—C4—C5A—C6A	−160.1 (8)	C6A—C1—N1—N2	−24.0 (6)
C3B—C4—C5A—C6A	28.2 (9)	C2B—C1—N1—N2	−170.2 (3)
C3A—C4—C5B—C6B	−41.5 (13)	C1—N1—N2—C7	176.4 (2)
C5A—C4—C5B—C6B	83 (2)	C12—C7—N2—N1	−172.2 (2)
O1B—C4—C5B—C6B	172.4 (8)	C8—C7—N2—N1	5.0 (4)
O1A—C4—C5B—C6B	−159.9 (10)	C11—C13—N3—C14	178.5 (2)
C3B—C4—C5B—C6B	2.9 (13)	C17—C14—N3—C13	−16.8 (3)
C2A—C1—C6A—C5A	6.6 (11)	C15—C14—N3—C13	−134.9 (2)
C6B—C1—C6A—C5A	75.4 (15)	C16—C14—N3—C13	105.2 (2)
C2B—C1—C6A—C5A	−34.1 (8)	O1B—C18—O1A—C4	−66.7 (14)
N1—C1—C6A—C5A	178.9 (5)	C5B—C4—O1A—C18	−59.5 (13)
C4—C5A—C6A—C1	4.1 (11)	C3A—C4—O1A—C18	−173.2 (10)
C2A—C1—C6B—C5B	37.3 (13)	C5A—C4—O1A—C18	−31.8 (14)
C6A—C1—C6B—C5B	−82.7 (19)	O1B—C4—O1A—C18	73.0 (17)
C2B—C1—C6B—C5B	1.7 (13)	C3B—C4—O1A—C18	138.8 (8)
N1—C1—C6B—C5B	−179.7 (8)	C5B—C4—O1B—C18	3.3 (11)
C4—C5B—C6B—C1	−2.6 (16)	C3A—C4—O1B—C18	−138.1 (10)
C12—C7—C8—C9	3.0 (4)	C5A—C4—O1B—C18	36.0 (9)
N2—C7—C8—C9	−174.1 (2)	O1A—C4—O1B—C18	−58.6 (16)
C7—C8—C9—O2	−178.0 (2)	C3B—C4—O1B—C18	173.6 (4)
C7—C8—C9—C10	2.5 (4)	O1A—C18—O1B—C4	64.8 (14)
C8—C9—C10—O3	175.0 (2)	C8—C9—O2—C19	8.4 (4)
O2—C9—C10—O3	−4.5 (3)	C10—C9—O2—C19	−172.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H33···O3	0.92 (3)	1.84 (3)	2.619 (2)	141 (2)
O5—H55···O4^i	0.82 (2)	1.92 (2)	2.733 (2)	174 (4)
O4—H44···O6^ii	0.84 (2)	1.98 (2)	2.789 (2)	163 (3)
O6—H66···O3^iii	0.85 (2)	1.92 (2)	2.7125 (18)	154 (2)
O6—H66···O2^iii	0.85 (2)	2.45 (2)	3.081 (2)	132 (2)
C3—H3···G1^iv	0.93 (1)	3.32 (1)	3.463 (7)	91 (1)

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