2-{[Tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien-1(2H)-one and its 6-hydroxy and 6-methoxy derivatives

The title compounds, 2-{[tris­(hydroxy­methyl)­methyl]­amino­methyl­ene}cyclo­hexa-3,5-dien-1(2H)-one, C₁₁H₁₅NO₄, (I), 6-hydroxy-2-{[tris­(hydroxy­methyl)­methyl]­amino­methyl­ene}­cyclo­hexa-3,5-dien-1(2H)-one, C₁₁H₁₅NO₅, (II), and 6-methoxy-2-{[tris­(hydroxy­methyl)­methyl]­amino­methyl­ene}­cyclo­hexa-3,5-dien-1(2H)-one, C₁₂H₁₇NO₅, (III), adopt the keto–amine tautomeric form, with the formal hydroxy H atom located on the N atom, and the NH group and oxo O atom display a strong intramolecular N—H...O hydrogen bond. The N—H...O hydrogen-bonded rings are almost planar and coupled with the cyclo­hexa­diene rings. The carbonyl O atoms accept two other H atoms from the alcohol groups of adjacent mol­ecules in (I), and one from the alcohol and one from the phenol group in (II), but from only one alcohol H atom in (III).

S1. Comment

There is considerable interest in Schiff base ligands and their complexes with regard to their striking antitumour activities (Zhou et al., 2000). Among them, o-hydroxy Schiff base ligands and their complexes derived from the reaction of o-hydroxy aldehydes with aniline have been extensively studied (Steward & Lingafelter, 1959; Calligaris et al., 1972; Maslen & Waters, 1975) and a number of them have been used as models for biological systems (Costamagna et al., 1992, 1998). o-Hydroxy Schiff bases exist as enol (Yıldız et al., 1998; Elmalı et al., 1998, 1999; Elmalı & Elerman, 1998; Dey et al., 2001; Ünver, Yıldız et al., 2002; Yang & Vittal, 2003) or keto (Ünver, Kabak et al., 2002; Hökelek et al., 2000), or as enol/keto mixtures (Nazır et al., 2000; Szady-Chelmienicecka et al., 2001; Ogawa & Harada, 2003) as a result of H-atom transfer from the hydroxy O atom to the N atom. Such H-atom tautomerism plays an important role in many fields of chemistry and especially biochemistry (Zollinger, 1991; Hem et al., 2002). Molecules giving tautomers by intramolecular H-atom transfer are often used as laser dyes, in high-energy radiation detectors and molecular memory storage devices, as fluorescent probes and as polymer protectors (Sytnik & Del Valle, 1995; Nagaoka et al., 1983). Many o-hydroxyarylidene anilines, being relatively simple in structure and exhibiting intramolecular H-atom transfer, have, therefore, attracted considerable attention from both experimental (Kownacki et al., 1994; Grabowska et al., 1994; Guha et al., 2000; Ogawa et al., 2001) and theoretical (Zgierski & Grabowska, 2000) points of view. N-substituted o-hydroxy imines have been reported to display thermo- and photochromism in the solid state by H-atom transfer from the hydroxy O atom to the N atom (Hadjoudis et al., 1987; Xu et al., 1994). In the course of our ongoing studies of the synthesis and structural characterization of polyhydroxyazomethine derivatives, the title compounds, (I), (II) and (III), were synthesized, and we report their crystal structures here. \sch

As shown in Scheme 2, o-hydroxyarylidene Schiff bases display two possible tautomeric forms, namely, the phenol-imine and the keto-amine. In the solid state, the keto-amine tautomer has been found in naphthaldimine (Hökelek et al., 2000; Ünver, Kabak et al., 2002), while phenol-imine is found in salicylaldimine Schiff bases (Kaitner & Pavlović, 1996; Yıldız et al., 1998; Elmalı et al., 1998, 1999; Elmalı & Elerman, 1998; Dey et al., 2001; Yang & Vittal, 2003; Karadayı et al., 2003). Compounds (I), (II) and (III) are polyhydroxysalicylaldimines and the present X-ray investigation indicates that the keto-amine tautomer is favoured over the phenol-imine tautomer. The crystal structure of (I) has been reported several times, most recently by Cungen et al. (2000) at room temperature. Scheme 2

A view of the hydrogen-bonded structure of (I), as determined at 208 K, and its numbering scheme are shown in Fig. 1. Selected bond distances and angles are listed in Table 1. Compound (I) has strong N—H···O intramolecular [N···O 2.6181 (14) Å] and O—H···O [mean O···O 2.700 Å] intermolecular hydrogen bonds. Such strong intramolecular N···O hydrogen bonds are a common feature of o-hydroxysalicylidene systems (Nazır et al., 2000; Yıldız et al., 1998). The sum of the van der Waals radii of O and N is 3.07 Å (Bondi, 1964), and the intramolecular hydrogen bond in (I) is shorter than this. Apart from the intramolecular hydrogen bond, (I) displays strong intermolecular O···O hydrogen bonds (Table 2). It has been reported Please check added text (Pizzala et al., 2000) that these hydrogen bonds are indeed characterized by relatively short O···O distances (shorter than the sum of the van der Waals radii of two O atoms, 3.04 Å).

The salicylidene ring bond lengths in (I) follow the alternating sequence C1—C2 > C2—C3 > C3—C4 < C4—C5 > C5—C6 < C6—C1. Compound (I) exists primarily as the keto-amine tautomer, as indicated by the C2—O1, C1—C7, C7—N and C1—C2 bond lengths (Table 1). These bonds are 1.356 (3), 1.448 (3), 1.270 (3) and 1.288 (4) Å, respectively, in the phenol-imine tautomer of 1,8-bis(N-2-oxyphenylsalicylidene)-3,6-dioxaoctane (Yıldız et al., 1998) and 1.286 (3), 1.441 (3), 1.297 (3) and 1.436 (3) Å, respectively, in the keto-amine tautomer of 4-[(3-chlorophenyl)diazenyl]-2-{[tris(hydroxymethyl)methyl] aminomethylene}cyclohexa-3,5-dien-1(2H)-one (Odabaşoğlu et al., 2003). Our investigation shows that there is an elongation of C7—N1 compared with the normal value of a C═N double bond (Reference?), and of C1—C2, C2—C3, C4—C5 and C6—C1 compared with the normal values for a salicylidene ring (Reference?). Furthermore, the formal hydroxyl H atom is located on atom N1, thus confirming a preference for the keto-amine tautomer (the quinoid form) in the solid state. Formation of the quinoid form results in electron-localization distortion and so the C3—C4 and C5—C6 bonds are shortened in comparison with their normal values in a salicylidene ring. The N—H···O hydrogen-bonded ring in (I) is almost planar and coupled with the cyclohexadiene ring, with an N1—C7—C1—C2 torsion angle of 0.3 (2)°.

Molecular views of (II) and (III), and their numbering schemes, are shown in Figs. 2 and 3, respectively, and selected bond distances and angles are listed in Tables 3 and 5, respectively. The structures of (II) and (III) are similar to that of (I), with small differences for some bond lengths due to the OH and CH₃O groups attached to the cyclohexadiene ring (Tables 3 and 5). The O1—C2 bond lengths of 1.2968 (17) Å in (II) and 1.2892 (18) Å in (III) are somewhat shorter than the value of 1.3025 (16) Å in (I). Compound (II) has two strong intramolecular hydrogen bonds [N···O 2.5851 (16) and O···O 2.7000 (15) Å; Table 4].

Compounds (II) and (III), like compound (I), have strong intermolecular O···O hydrogen bonds (Tables 4 and 6). Atom O1 in (I) accepts two other H atoms from the alcoholic groups of adjacent molecules, viz. O1···O3^iv and O1···O4^iv [symmetry code: (iv) x, 1/2 − y, z + 1/2]. In (II), atom O1 accepts one H atom from the alcoholic group, O1···O3ⁱⁱ [symmetry code: (ii) 2 − x, −y, −z], and one from the phenolic group, O1···O5, but in (III), atom O1 accepts only one alcoholic H atom, O1···O4ⁱⁱⁱ [symmetry code: (iii) 1/2 − x, 1/2 + y, z].

The N—H···O hydrogen-bonded rings in (II) and (III) are almost planar-coupled with the cyclohexadiene rings, with N1—C7—C1—C2 torsion angles of 3.63 (1) and 0.8 (2)°, respectively (Tables 3 and 5).

S2. Experimental

For compound (I), a solution of tris(hydroxymethyl)aminomethane (2.42 g, 20 mmol) in butane-1-ol (75 ml) was added to a solution of salicylaldehyde (2.44 g, 20 mmol) in butane-1-ol (75 ml). The mixture was stirred at reflux temperature, and the water produced in the reaction was distilled out of the reaction mixture. The resulting yellow precipitate was filtered and recrystallized from ethyl alcohol by slow evaporation, and well shaped crystals of (I) were obtained. Compounds (II) and (III) were synthesized and crystallized using exactly the same procedure as for (I) Different starting materials?, but recrystallization was carried out in acetonitrile for (III) instead of ethyl alcohol. Yields: 95%, m.p. 422–423 K for (I), 90%, m.p. 415–417 K for (II) and 95%, m.p. 454–455 K for (III).

S3. Refinement

All H atoms were freely refined. For (I), C—H distances are in the range 0.938 (19)–1.011 (17) Å and U_iso(H) values are in the range 0.022 (4)–0.056 (6) Ų. For (II), C—H distances are in the range 0.974 (17)–1.007 (18) Å and U_iso(H) values are in the range 0.025 (4)–0.057 (7) Ų. For (III), C—H distances are in the range 0.95 (2)–1.02 (2) Å and U_iso(H) values are in the range 0.021 (4)–0.047 (6) Ų.

Computing details

For all 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: ORTEPIII (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the molecule of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids [symmetry codes: (ii) −x, y + 1/2, 1/2 − z; (iv) x, 1/2 − y, z + 1/2].
	Fig. 2. A view of the molecule of (II), with the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 3. A view of the molecule of (III), with the atom-numbering scheme and 50% probability displacement ellipsoids.

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

Crystal data

C11H15NO4	F(000) = 480
Mr = 225.24	Dx = 1.333 Mg m^−3
Monoclinic, P21/c	Melting point = 422–423 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.4437 (9) Å	Cell parameters from 986 reflections
b = 8.7029 (7) Å	θ = 2.8–26.6°
c = 12.6147 (11) Å	µ = 0.10 mm^−1
β = 101.801 (2)°	T = 208 K
V = 1122.32 (16) Å^3	Prism, colourless
Z = 4	0.30 × 0.30 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2226 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 28.0°, θmin = 2.0°
ω scans	h = −13→13
12824 measured reflections	k = −11→11
2701 independent 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)] = 0.044	Hydrogen site location: difference Fourier map
wR(F^2) = 0.111	All H-atom parameters refined
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0531P)^2 + 0.3161P] where P = (Fo^2 + 2Fc^2)/3
2701 reflections	(Δ/σ)max < 0.001
206 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.27644 (10)	0.47289 (11)	0.65317 (7)	0.0278 (2)
O2	0.53462 (11)	0.28376 (13)	0.57069 (8)	0.0325 (3)
O3	0.39387 (11)	0.00670 (11)	0.35914 (8)	0.0304 (3)
O4	0.23193 (12)	0.31687 (14)	0.21920 (8)	0.0363 (3)
N1	0.29931 (11)	0.37796 (12)	0.46098 (9)	0.0221 (2)
C1	0.15370 (13)	0.57931 (15)	0.48991 (10)	0.0223 (3)
C2	0.19332 (13)	0.57507 (15)	0.60510 (11)	0.0236 (3)
C3	0.13955 (16)	0.68809 (19)	0.66395 (12)	0.0343 (4)
C4	0.05145 (17)	0.79386 (19)	0.61230 (13)	0.0369 (4)
C5	0.00882 (15)	0.79419 (17)	0.49954 (13)	0.0307 (3)
C6	0.06057 (14)	0.68829 (16)	0.43998 (11)	0.0258 (3)
C7	0.21039 (13)	0.47852 (15)	0.42278 (11)	0.0232 (3)
C8	0.37286 (13)	0.27869 (14)	0.39986 (10)	0.0215 (3)
C9	0.51718 (14)	0.29251 (17)	0.45650 (11)	0.0271 (3)
C10	0.32288 (14)	0.11389 (15)	0.40903 (11)	0.0258 (3)
C11	0.36008 (15)	0.33264 (17)	0.28286 (11)	0.0276 (3)
H1N	0.3223 (16)	0.375 (2)	0.5350 (14)	0.030 (4)*
H2O	0.554 (2)	0.193 (3)	0.5903 (17)	0.051 (6)*
H3O	0.355 (2)	0.005 (2)	0.2878 (18)	0.049 (6)*
H4O	0.228 (2)	0.227 (3)	0.1896 (18)	0.056 (6)*
H3	0.1679 (18)	0.690 (2)	0.7424 (15)	0.041 (5)*
H4	0.017 (2)	0.869 (3)	0.6519 (16)	0.054 (6)*
H5	−0.0549 (18)	0.864 (2)	0.4654 (14)	0.039 (5)*
H6	0.0318 (16)	0.6853 (19)	0.3639 (13)	0.027 (4)*
H7	0.1814 (15)	0.4834 (18)	0.3459 (13)	0.022 (4)*
H9A	0.5507 (16)	0.397 (2)	0.4396 (13)	0.031 (4)*
H9B	0.5666 (17)	0.216 (2)	0.4289 (14)	0.032 (4)*
H10A	0.2263 (17)	0.1103 (19)	0.3756 (13)	0.027 (4)*
H10B	0.3356 (15)	0.0895 (19)	0.4868 (14)	0.028 (4)*
H11A	0.3831 (15)	0.445 (2)	0.2857 (13)	0.026 (4)*
H11B	0.4242 (15)	0.2736 (18)	0.2503 (12)	0.023 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0368 (5)	0.0255 (5)	0.0214 (5)	0.0064 (4)	0.0068 (4)	0.0042 (4)
O2	0.0426 (6)	0.0264 (6)	0.0252 (5)	0.0066 (5)	−0.0011 (4)	−0.0022 (4)
O3	0.0462 (6)	0.0203 (5)	0.0231 (5)	0.0069 (4)	0.0036 (4)	−0.0034 (4)
O4	0.0464 (7)	0.0335 (6)	0.0247 (5)	0.0086 (5)	−0.0030 (4)	−0.0057 (5)
N1	0.0294 (6)	0.0191 (5)	0.0183 (5)	0.0007 (4)	0.0060 (4)	−0.0015 (4)
C1	0.0256 (6)	0.0196 (6)	0.0223 (6)	−0.0009 (5)	0.0065 (5)	0.0001 (5)
C2	0.0281 (7)	0.0210 (6)	0.0230 (6)	−0.0001 (5)	0.0079 (5)	0.0020 (5)
C3	0.0431 (9)	0.0373 (8)	0.0229 (7)	0.0104 (7)	0.0076 (6)	−0.0031 (6)
C4	0.0434 (9)	0.0332 (8)	0.0351 (8)	0.0111 (7)	0.0100 (7)	−0.0079 (7)
C5	0.0331 (8)	0.0231 (7)	0.0356 (8)	0.0067 (6)	0.0059 (6)	0.0017 (6)
C6	0.0298 (7)	0.0245 (7)	0.0227 (6)	0.0000 (5)	0.0045 (5)	0.0022 (5)
C7	0.0274 (7)	0.0216 (6)	0.0204 (6)	−0.0011 (5)	0.0047 (5)	−0.0009 (5)
C8	0.0273 (6)	0.0183 (6)	0.0196 (6)	0.0007 (5)	0.0067 (5)	−0.0026 (5)
C9	0.0287 (7)	0.0260 (7)	0.0268 (7)	0.0001 (6)	0.0059 (6)	−0.0035 (6)
C10	0.0340 (8)	0.0197 (6)	0.0242 (6)	−0.0007 (5)	0.0074 (5)	−0.0020 (5)
C11	0.0380 (8)	0.0239 (7)	0.0217 (6)	0.0014 (6)	0.0076 (6)	−0.0005 (5)

Geometric parameters (Å, º)

O1—C2	1.3025 (16)	C4—C5	1.401 (2)
O2—C9	1.4166 (17)	C4—H4	0.94 (2)
O2—H2O	0.84 (2)	C5—C6	1.368 (2)
O3—C10	1.4166 (16)	C5—H5	0.938 (19)
O3—H3O	0.91 (2)	C6—H6	0.945 (16)
O4—C11	1.4196 (19)	C7—H7	0.957 (16)
O4—H4O	0.86 (2)	C8—C11	1.5283 (18)
N1—C7	1.2952 (18)	C8—C9	1.535 (2)
N1—C8	1.4741 (16)	C8—C10	1.5387 (19)
N1—H1N	0.915 (17)	C9—H9A	1.009 (17)
C1—C6	1.4113 (19)	C9—H9B	0.951 (18)
C1—C2	1.4276 (18)	C10—H10A	1.011 (17)
C1—C7	1.4290 (18)	C10—H10B	0.986 (17)
C2—C3	1.4158 (19)	C11—H11A	1.009 (17)
C3—C4	1.369 (2)	C11—H11B	0.997 (16)
C3—H3	0.973 (19)
C9—O2—H2O	108.8 (14)	C1—C7—H7	119.3 (9)
C10—O3—H3O	106.7 (13)	N1—C8—C11	111.91 (11)
C11—O4—H4O	106.8 (15)	N1—C8—C9	106.12 (10)
C7—N1—C8	127.74 (11)	C11—C8—C9	108.00 (11)
C7—N1—H1N	114.8 (11)	N1—C8—C10	106.61 (10)
C8—N1—H1N	117.3 (11)	C11—C8—C10	113.27 (11)
C6—C1—C2	120.10 (12)	C9—C8—C10	110.72 (11)
C6—C1—C7	118.64 (12)	O2—C9—C8	112.27 (11)
C2—C1—C7	121.22 (12)	O2—C9—H9A	106.6 (9)
O1—C2—C3	121.89 (12)	C8—C9—H9A	108.8 (9)
O1—C2—C1	121.22 (12)	O2—C9—H9B	111.6 (10)
C3—C2—C1	116.89 (12)	C8—C9—H9B	109.2 (10)
C4—C3—C2	121.18 (14)	H9A—C9—H9B	108.2 (14)
C4—C3—H3	120.4 (11)	O3—C10—C8	111.35 (11)
C2—C3—H3	118.4 (11)	O3—C10—H10A	111.2 (9)
C3—C4—C5	121.86 (14)	C8—C10—H10A	108.8 (9)
C3—C4—H4	120.6 (12)	O3—C10—H10B	108.9 (9)
C5—C4—H4	117.5 (12)	C8—C10—H10B	107.3 (10)
C6—C5—C4	118.49 (14)	H10A—C10—H10B	109.2 (13)
C6—C5—H5	120.5 (11)	O4—C11—C8	113.74 (12)
C4—C5—H5	121.0 (11)	O4—C11—H11A	107.7 (9)
C5—C6—C1	121.41 (13)	C8—C11—H11A	106.9 (9)
C5—C6—H6	119.8 (10)	O4—C11—H11B	110.6 (9)
C1—C6—H6	118.8 (10)	C8—C11—H11B	107.8 (9)
N1—C7—C1	123.15 (12)	H11A—C11—H11B	109.9 (13)
N1—C7—H7	117.5 (9)
C6—C1—C2—O1	178.12 (12)	C2—C1—C7—N1	0.3 (2)
C7—C1—C2—O1	−4.3 (2)	C7—N1—C8—C11	14.74 (19)
C6—C1—C2—C3	−2.8 (2)	C7—N1—C8—C9	132.31 (14)
C7—C1—C2—C3	174.79 (13)	C7—N1—C8—C10	−109.61 (15)
O1—C2—C3—C4	−179.43 (15)	N1—C8—C9—O2	44.58 (14)
C1—C2—C3—C4	1.5 (2)	C11—C8—C9—O2	164.73 (11)
C2—C3—C4—C5	1.0 (3)	C10—C8—C9—O2	−70.73 (14)
C3—C4—C5—C6	−2.1 (3)	N1—C8—C10—O3	−175.90 (10)
C4—C5—C6—C1	0.7 (2)	C11—C8—C10—O3	60.59 (15)
C2—C1—C6—C5	1.7 (2)	C9—C8—C10—O3	−60.90 (14)
C7—C1—C6—C5	−175.90 (13)	N1—C8—C11—O4	−67.18 (15)
C8—N1—C7—C1	−173.88 (12)	C9—C8—C11—O4	176.38 (11)
C6—C1—C7—N1	177.91 (13)	C10—C8—C11—O4	53.38 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.915 (17)	1.865 (17)	2.6181 (14)	138.1 (15)
O2—H2O···O3^i	0.84 (2)	1.89 (2)	2.7314 (15)	177 (2)
O3—H3O···O1^ii	0.91 (2)	1.74 (2)	2.6426 (14)	172 (2)
O4—H4O···O1^ii	0.86 (2)	1.90 (2)	2.7254 (15)	161 (2)

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

(II) 6-hydroxy-2-{[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien- 1(2H)-one

Crystal data

C11H15NO5	F(000) = 512
Mr = 241.24	Dx = 1.485 Mg m^−3
Monoclinic, P21/c	Melting point = 415–417 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 9.6807 (17) Å	Cell parameters from 560 reflections
b = 11.793 (2) Å	θ = 2.5–29.3°
c = 9.8373 (18) Å	µ = 0.12 mm^−1
β = 106.110 (3)°	T = 223 K
V = 1078.9 (3) Å^3	Prism, colourless
Z = 4	0.25 × 0.25 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2258 independent reflections
Radiation source: fine-focus sealed tube	1972 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 26.6°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −12→10
Tmin = 0.971, Tmax = 0.988	k = −14→13
6019 measured reflections	l = −11→12

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)] = 0.040	Hydrogen site location: difference Fourier map
wR(F^2) = 0.103	All H-atom parameters refined
S = 1.09	w = 1/[σ^2(Fo^2) + (0.051P)^2 + 0.326P] where P = (Fo^2 + 2Fc^2)/3
2258 reflections	(Δ/σ)max < 0.001
214 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.82522 (11)	0.59478 (9)	0.55685 (10)	0.0271 (3)
O2	0.95517 (12)	0.32126 (9)	0.15492 (12)	0.0307 (3)
O3	1.03815 (12)	0.59002 (9)	0.31064 (12)	0.0297 (3)
O4	0.63913 (12)	0.57956 (11)	−0.01010 (12)	0.0347 (3)
O5	0.74232 (13)	0.67352 (9)	0.77973 (11)	0.0302 (3)
N1	0.75693 (13)	0.53522 (10)	0.29369 (12)	0.0226 (3)
C1	0.58362 (15)	0.60323 (11)	0.40442 (14)	0.0224 (3)
C2	0.69014 (15)	0.61847 (11)	0.53614 (14)	0.0221 (3)
C3	0.64182 (16)	0.66043 (12)	0.65118 (14)	0.0233 (3)
C4	0.50029 (17)	0.68423 (12)	0.63639 (16)	0.0267 (3)
C5	0.39633 (16)	0.66842 (12)	0.50537 (16)	0.0266 (3)
C6	0.43763 (16)	0.62793 (12)	0.39208 (16)	0.0250 (3)
C7	0.62428 (15)	0.55787 (12)	0.28653 (15)	0.0233 (3)
C8	0.81826 (14)	0.48586 (12)	0.18571 (14)	0.0215 (3)
C9	0.87055 (16)	0.36642 (12)	0.24005 (16)	0.0247 (3)
C10	0.94335 (16)	0.56280 (12)	0.17637 (15)	0.0261 (3)
C11	0.70751 (16)	0.47559 (14)	0.04146 (15)	0.0275 (3)
H1N	0.820 (2)	0.5531 (17)	0.376 (2)	0.044 (5)*
H2O	0.949 (2)	0.250 (2)	0.158 (2)	0.056 (6)*
H3O	1.090 (2)	0.5297 (19)	0.344 (2)	0.052 (6)*
H4	0.4725 (19)	0.7116 (15)	0.7191 (19)	0.032 (4)*
H4O	0.683 (2)	0.6094 (19)	−0.063 (2)	0.054 (6)*
H5	0.2955 (19)	0.6846 (14)	0.4974 (18)	0.026 (4)*
H5O	0.829 (3)	0.6636 (19)	0.774 (2)	0.057 (7)*
H6	0.364 (2)	0.6157 (15)	0.300 (2)	0.037 (5)*
H7	0.553 (2)	0.5427 (16)	0.196 (2)	0.041 (5)*
H9A	0.7856 (19)	0.3186 (14)	0.2350 (18)	0.028 (4)*
H9B	0.9287 (18)	0.3710 (14)	0.3382 (19)	0.027 (4)*
H10A	0.9051 (18)	0.6359 (14)	0.1348 (18)	0.025 (4)*
H10B	0.9969 (19)	0.5244 (15)	0.1148 (18)	0.033 (4)*
H11A	0.6312 (18)	0.4235 (14)	0.0471 (17)	0.025 (4)*
H11B	0.760 (2)	0.4438 (16)	−0.022 (2)	0.035 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0223 (5)	0.0336 (6)	0.0242 (5)	0.0030 (4)	0.0045 (4)	−0.0016 (4)
O2	0.0332 (6)	0.0231 (6)	0.0378 (6)	0.0029 (4)	0.0133 (5)	−0.0039 (4)
O3	0.0253 (6)	0.0234 (5)	0.0357 (6)	−0.0010 (4)	0.0003 (4)	−0.0013 (4)
O4	0.0311 (6)	0.0448 (7)	0.0293 (6)	0.0096 (5)	0.0099 (5)	0.0114 (5)
O5	0.0273 (6)	0.0400 (6)	0.0242 (5)	−0.0013 (5)	0.0084 (4)	−0.0059 (4)
N1	0.0233 (6)	0.0250 (6)	0.0187 (6)	0.0009 (5)	0.0048 (5)	−0.0014 (5)
C1	0.0244 (7)	0.0204 (6)	0.0226 (7)	0.0017 (5)	0.0072 (5)	0.0036 (5)
C2	0.0237 (7)	0.0186 (6)	0.0248 (7)	0.0017 (5)	0.0077 (5)	0.0028 (5)
C3	0.0276 (7)	0.0197 (6)	0.0223 (7)	−0.0014 (5)	0.0066 (5)	0.0004 (5)
C4	0.0316 (8)	0.0219 (7)	0.0304 (8)	−0.0010 (6)	0.0150 (6)	−0.0017 (6)
C5	0.0232 (7)	0.0234 (7)	0.0349 (8)	0.0027 (6)	0.0111 (6)	0.0033 (6)
C6	0.0238 (7)	0.0239 (7)	0.0267 (7)	0.0004 (6)	0.0060 (6)	0.0044 (6)
C7	0.0240 (7)	0.0223 (7)	0.0228 (7)	0.0004 (5)	0.0054 (6)	0.0024 (5)
C8	0.0212 (7)	0.0233 (7)	0.0207 (6)	0.0011 (5)	0.0066 (5)	−0.0014 (5)
C9	0.0252 (7)	0.0225 (7)	0.0271 (7)	−0.0001 (6)	0.0083 (6)	−0.0003 (5)
C10	0.0276 (8)	0.0242 (7)	0.0269 (7)	−0.0017 (6)	0.0083 (6)	0.0009 (6)
C11	0.0266 (8)	0.0329 (8)	0.0217 (7)	0.0033 (6)	0.0048 (6)	−0.0027 (6)

Geometric parameters (Å, º)

O1—C2	1.2968 (17)	C3—C4	1.366 (2)
O2—C9	1.4271 (18)	C4—C5	1.410 (2)
O2—H2O	0.84 (2)	C4—H4	0.979 (19)
O3—C10	1.4203 (18)	C5—C6	1.370 (2)
O3—H3O	0.88 (2)	C5—H5	0.976 (18)
O4—C11	1.4185 (19)	C6—H6	1.000 (19)
O4—H4O	0.84 (2)	C7—H7	0.98 (2)
O5—C3	1.3737 (18)	C8—C11	1.5276 (19)
O5—H5O	0.87 (3)	C8—C10	1.536 (2)
N1—C7	1.2943 (19)	C8—C9	1.5414 (19)
N1—C8	1.4730 (17)	C9—H9A	0.987 (18)
N1—H1N	0.89 (2)	C9—H9B	0.975 (17)
C1—C6	1.415 (2)	C10—H10A	0.981 (17)
C1—C2	1.4258 (19)	C10—H10B	1.007 (18)
C1—C7	1.428 (2)	C11—H11A	0.974 (17)
C2—C3	1.4277 (19)	C11—H11B	0.980 (19)
C9—O2—H2O	107.0 (16)	N1—C7—H7	116.7 (12)
C10—O3—H3O	108.7 (14)	C1—C7—H7	121.6 (12)
C11—O4—H4O	108.6 (15)	N1—C8—C11	112.44 (11)
C3—O5—H5O	112.1 (16)	N1—C8—C10	106.97 (11)
C7—N1—C8	129.40 (12)	C11—C8—C10	110.67 (12)
C7—N1—H1N	115.0 (13)	N1—C8—C9	105.68 (11)
C8—N1—H1N	115.6 (13)	C11—C8—C9	109.15 (12)
C6—C1—C2	120.36 (13)	C10—C8—C9	111.84 (12)
C6—C1—C7	120.08 (13)	O2—C9—C8	108.92 (11)
C2—C1—C7	119.50 (13)	O2—C9—H9A	111.3 (10)
O1—C2—C1	124.00 (13)	C8—C9—H9A	108.4 (10)
O1—C2—C3	119.21 (13)	O2—C9—H9B	109.5 (10)
C1—C2—C3	116.78 (13)	C8—C9—H9B	109.7 (10)
C4—C3—O5	120.54 (13)	H9A—C9—H9B	109.0 (14)
C4—C3—C2	121.76 (13)	O3—C10—C8	113.23 (12)
O5—C3—C2	117.68 (13)	O3—C10—H10A	105.1 (10)
C3—C4—C5	120.69 (14)	C8—C10—H10A	109.3 (10)
C3—C4—H4	118.5 (11)	O3—C10—H10B	110.7 (10)
C5—C4—H4	120.8 (11)	C8—C10—H10B	108.4 (10)
C6—C5—C4	119.61 (14)	H10A—C10—H10B	110.0 (14)
C6—C5—H5	120.9 (10)	O4—C11—C8	113.65 (12)
C4—C5—H5	119.4 (10)	O4—C11—H11A	106.2 (10)
C5—C6—C1	120.79 (14)	C8—C11—H11A	110.2 (10)
C5—C6—H6	119.6 (11)	O4—C11—H11B	112.0 (11)
C1—C6—H6	119.6 (11)	C8—C11—H11B	105.6 (11)
N1—C7—C1	121.74 (13)	H11A—C11—H11B	109.2 (15)
C6—C1—C2—O1	178.02 (13)	C6—C1—C7—N1	179.38 (13)
C7—C1—C2—O1	0.9 (2)	C2—C1—C7—N1	−3.5 (2)
C6—C1—C2—C3	−0.75 (19)	C7—N1—C8—C11	8.4 (2)
C7—C1—C2—C3	−177.88 (12)	C7—N1—C8—C10	130.12 (15)
O1—C2—C3—C4	−178.41 (13)	C7—N1—C8—C9	−110.56 (16)
C1—C2—C3—C4	0.4 (2)	N1—C8—C9—O2	−169.27 (11)
O1—C2—C3—O5	−0.12 (19)	C11—C8—C9—O2	69.58 (15)
C1—C2—C3—O5	178.71 (12)	C10—C8—C9—O2	−53.22 (15)
O5—C3—C4—C5	−178.54 (13)	N1—C8—C10—O3	47.88 (15)
C2—C3—C4—C5	−0.3 (2)	C11—C8—C10—O3	170.69 (12)
C3—C4—C5—C6	0.5 (2)	C9—C8—C10—O3	−67.38 (15)
C4—C5—C6—C1	−0.9 (2)	N1—C8—C11—O4	55.60 (17)
C2—C1—C6—C5	1.0 (2)	C10—C8—C11—O4	−63.97 (16)
C7—C1—C6—C5	178.11 (13)	C9—C8—C11—O4	172.53 (12)
C8—N1—C7—C1	178.20 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.89 (2)	1.84 (2)	2.5851 (16)	140.0 (18)
O2—H2O···O3^i	0.84 (2)	1.91 (3)	2.7465 (16)	171 (2)
O3—H3O···O1^ii	0.88 (2)	1.83 (2)	2.6910 (15)	167 (2)
O4—H4O···O5^iii	0.84 (2)	1.95 (3)	2.7652 (17)	167 (2)
O5—H5O···O2^ii	0.87 (3)	2.02 (3)	2.8193 (17)	153 (2)
O5—H5O···O1	0.87 (3)	2.27 (2)	2.7000 (15)	110.3 (19)

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

(III) 6-methoxy-2-{[tris(hydroxymethyl)methyl]aminomethylene}cyclohexa-3,5-dien- 1(2H)-one

Crystal data

C12H17NO5	Dx = 1.418 Mg m^−3
Mr = 255.27	Melting point = 454–455 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 720 reflections
a = 10.6464 (7) Å	θ = 2.2–27.6°
b = 10.7749 (7) Å	µ = 0.11 mm^−1
c = 20.8540 (13) Å	T = 213 K
V = 2392.2 (3) Å^3	Needle, colourless
Z = 8	0.30 × 0.30 × 0.03 mm
F(000) = 1088

Data collection

Bruker SMART CCD area-detector diffractometer	2744 independent reflections
Radiation source: fine-focus sealed tube	2241 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −6→13
Tmin = 0.968, Tmax = 0.997	k = −13→14
12603 measured reflections	l = −26→27

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: difference Fourier map
wR(F^2) = 0.105	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0476P)^2 + 0.9405P] where P = (Fo^2 + 2Fc^2)/3
2744 reflections	(Δ/σ)max = 0.004
231 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.59626 (10)	0.09299 (10)	0.61618 (5)	0.0270 (3)
O5	0.36871 (11)	0.09491 (11)	0.66751 (6)	0.0335 (3)
O2	0.77267 (10)	0.08388 (10)	0.47120 (6)	0.0268 (3)
H2O	0.705 (2)	0.100 (2)	0.4521 (11)	0.055 (7)*
O3	1.09930 (11)	0.13505 (11)	0.52213 (6)	0.0339 (3)
H3O	1.140 (2)	0.070 (2)	0.5281 (10)	0.046 (6)*
O4	1.03769 (10)	0.38666 (11)	0.58199 (6)	0.0281 (3)
H4O	1.010 (2)	0.455 (2)	0.5969 (9)	0.043 (6)*
N1	0.78960 (11)	0.22397 (12)	0.57913 (6)	0.0214 (3)
H1N	0.741 (2)	0.1549 (19)	0.5784 (9)	0.042 (5)*
C1	0.64296 (14)	0.29492 (14)	0.65720 (7)	0.0226 (3)
C2	0.56490 (13)	0.18755 (14)	0.65051 (7)	0.0215 (3)
C3	0.44500 (14)	0.19299 (15)	0.68238 (7)	0.0254 (3)
C4	0.41485 (16)	0.28899 (17)	0.72215 (8)	0.0328 (4)
H4	0.333 (2)	0.2873 (19)	0.7451 (11)	0.053 (6)*
C5	0.49735 (17)	0.38915 (17)	0.73158 (9)	0.0369 (4)
H5	0.476 (2)	0.4539 (19)	0.7602 (10)	0.046 (6)*
C6	0.60765 (16)	0.39349 (16)	0.69873 (8)	0.0313 (4)
H6	0.6633 (18)	0.4618 (19)	0.7027 (9)	0.041 (5)*
C12	0.23936 (17)	0.1071 (2)	0.68447 (10)	0.0401 (4)
H12A	0.203 (2)	0.188 (2)	0.6663 (10)	0.047 (6)*
H12B	0.2279 (19)	0.1055 (18)	0.7307 (10)	0.041 (5)*
H12C	0.201 (2)	0.033 (2)	0.6650 (10)	0.045 (6)*
C7	0.75333 (14)	0.30753 (14)	0.61983 (7)	0.0228 (3)
H7	0.8017 (15)	0.3814 (15)	0.6239 (8)	0.021 (4)*
C8	0.89788 (13)	0.22774 (13)	0.53555 (7)	0.0205 (3)
C9	0.85050 (15)	0.19195 (15)	0.46847 (7)	0.0242 (3)
H9A	0.8027 (15)	0.2610 (16)	0.4508 (8)	0.022 (4)*
H9B	0.9239 (17)	0.1733 (16)	0.4419 (8)	0.028 (4)*
C10	0.99173 (14)	0.13295 (14)	0.56173 (8)	0.0244 (3)
H10A	0.9516 (15)	0.0508 (16)	0.5619 (8)	0.022 (4)*
H10B	1.0105 (17)	0.1558 (16)	0.6056 (9)	0.029 (5)*
C11	0.95707 (14)	0.35666 (14)	0.52966 (7)	0.0232 (3)
H11A	0.8904 (17)	0.4179 (16)	0.5254 (8)	0.026 (4)*
H11B	1.0061 (17)	0.3567 (16)	0.4901 (8)	0.026 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0229 (6)	0.0235 (5)	0.0347 (6)	−0.0018 (4)	0.0047 (5)	−0.0051 (4)
O5	0.0220 (6)	0.0349 (7)	0.0437 (7)	−0.0055 (5)	0.0054 (5)	−0.0012 (5)
O2	0.0185 (5)	0.0242 (6)	0.0376 (6)	0.0006 (4)	−0.0051 (5)	−0.0036 (5)
O3	0.0195 (6)	0.0271 (6)	0.0551 (8)	0.0062 (5)	0.0073 (5)	0.0035 (6)
O4	0.0208 (5)	0.0224 (6)	0.0410 (6)	−0.0006 (4)	0.0000 (5)	−0.0076 (5)
N1	0.0164 (6)	0.0211 (6)	0.0266 (6)	−0.0017 (5)	0.0014 (5)	−0.0007 (5)
C1	0.0184 (7)	0.0249 (7)	0.0245 (7)	0.0008 (6)	−0.0016 (6)	−0.0020 (6)
C2	0.0190 (7)	0.0249 (7)	0.0206 (7)	0.0021 (6)	−0.0012 (5)	0.0001 (6)
C3	0.0208 (7)	0.0294 (8)	0.0259 (7)	−0.0006 (6)	−0.0008 (6)	0.0023 (6)
C4	0.0234 (8)	0.0435 (10)	0.0316 (8)	0.0031 (7)	0.0060 (7)	−0.0042 (7)
C5	0.0322 (9)	0.0412 (10)	0.0374 (9)	0.0054 (8)	0.0036 (8)	−0.0164 (8)
C6	0.0262 (8)	0.0307 (9)	0.0370 (9)	−0.0004 (7)	−0.0014 (7)	−0.0118 (7)
C12	0.0220 (8)	0.0531 (12)	0.0453 (11)	−0.0062 (8)	0.0034 (8)	0.0057 (9)
C7	0.0190 (7)	0.0222 (7)	0.0273 (7)	−0.0005 (6)	−0.0029 (6)	−0.0018 (6)
C8	0.0149 (6)	0.0190 (7)	0.0275 (7)	0.0001 (5)	0.0018 (6)	0.0001 (6)
C9	0.0203 (7)	0.0249 (8)	0.0275 (7)	0.0008 (6)	0.0007 (6)	−0.0004 (6)
C10	0.0184 (7)	0.0211 (7)	0.0336 (8)	0.0009 (6)	−0.0006 (6)	0.0005 (6)
C11	0.0203 (7)	0.0197 (7)	0.0297 (8)	−0.0008 (6)	0.0025 (6)	0.0008 (6)

Geometric parameters (Å, º)

O1—C2	1.2892 (18)	C4—H4	1.00 (2)
O5—C3	1.3684 (19)	C5—C6	1.360 (3)
O5—C12	1.428 (2)	C5—H5	0.95 (2)
O2—C9	1.4304 (19)	C6—H6	0.95 (2)
O2—H2O	0.84 (2)	C12—H12A	1.02 (2)
O3—C10	1.4121 (19)	C12—H12B	0.97 (2)
O3—H3O	0.83 (2)	C12—H12C	0.98 (2)
O4—C11	1.4254 (19)	C7—H7	0.952 (17)
O4—H4O	0.85 (2)	C8—C10	1.529 (2)
N1—C7	1.2962 (19)	C8—C11	1.530 (2)
N1—C8	1.4685 (18)	C8—C9	1.536 (2)
N1—H1N	0.91 (2)	C9—H9A	0.974 (17)
C1—C7	1.417 (2)	C9—H9B	0.979 (18)
C1—C6	1.421 (2)	C10—H10A	0.983 (17)
C1—C2	1.431 (2)	C10—H10B	0.969 (18)
C2—C3	1.440 (2)	C11—H11A	0.973 (18)
C3—C4	1.364 (2)	C11—H11B	0.976 (18)
C4—C5	1.405 (3)
C3—O5—C12	116.44 (14)	H12A—C12—H12C	112.1 (17)
C9—O2—H2O	107.9 (16)	H12B—C12—H12C	110.2 (17)
C10—O3—H3O	108.8 (15)	N1—C7—C1	122.73 (14)
C11—O4—H4O	105.3 (14)	N1—C7—H7	118.6 (10)
C7—N1—C8	128.31 (13)	C1—C7—H7	118.7 (10)
C7—N1—H1N	114.3 (13)	N1—C8—C10	105.87 (12)
C8—N1—H1N	117.4 (13)	N1—C8—C11	113.45 (12)
C7—C1—C6	118.89 (14)	C10—C8—C11	111.46 (12)
C7—C1—C2	120.37 (13)	N1—C8—C9	107.39 (12)
C6—C1—C2	120.66 (14)	C10—C8—C9	111.83 (12)
O1—C2—C1	122.85 (13)	C11—C8—C9	106.86 (12)
O1—C2—C3	121.20 (13)	O2—C9—C8	111.00 (12)
C1—C2—C3	115.89 (13)	O2—C9—H9A	109.5 (10)
C4—C3—O5	125.71 (14)	C8—C9—H9A	109.0 (10)
C4—C3—C2	121.33 (15)	O2—C9—H9B	108.5 (10)
O5—C3—C2	112.95 (13)	C8—C9—H9B	107.8 (10)
C3—C4—C5	121.35 (15)	H9A—C9—H9B	111.1 (14)
C3—C4—H4	119.0 (12)	O3—C10—C8	108.09 (12)
C5—C4—H4	119.7 (12)	O3—C10—H10A	111.7 (9)
C6—C5—C4	119.71 (16)	C8—C10—H10A	108.6 (10)
C6—C5—H5	120.1 (13)	O3—C10—H10B	112.4 (11)
C4—C5—H5	120.2 (13)	C8—C10—H10B	107.6 (10)
C5—C6—C1	120.64 (16)	H10A—C10—H10B	108.3 (14)
C5—C6—H6	121.4 (12)	O4—C11—C8	113.10 (12)
C1—C6—H6	117.9 (12)	O4—C11—H11A	110.8 (10)
O5—C12—H12A	110.4 (12)	C8—C11—H11A	108.8 (10)
O5—C12—H12B	111.4 (12)	O4—C11—H11B	108.9 (11)
H12A—C12—H12B	109.6 (16)	C8—C11—H11B	106.8 (10)
O5—C12—H12C	103.0 (12)	H11A—C11—H11B	108.2 (14)
C7—C1—C2—O1	7.3 (2)	C8—N1—C7—C1	176.92 (13)
C6—C1—C2—O1	−176.11 (14)	C6—C1—C7—N1	−177.47 (15)
C7—C1—C2—C3	−169.99 (13)	C2—C1—C7—N1	−0.8 (2)
C6—C1—C2—C3	6.6 (2)	C7—N1—C8—C10	109.76 (16)
C12—O5—C3—C4	13.4 (2)	C7—N1—C8—C11	−12.8 (2)
C12—O5—C3—C2	−165.76 (14)	C7—N1—C8—C9	−130.63 (15)
O1—C2—C3—C4	175.58 (15)	N1—C8—C9—O2	−46.88 (16)
C1—C2—C3—C4	−7.1 (2)	C10—C8—C9—O2	68.86 (16)
O1—C2—C3—O5	−5.2 (2)	C11—C8—C9—O2	−168.92 (12)
C1—C2—C3—O5	172.15 (13)	N1—C8—C10—O3	−178.68 (12)
O5—C3—C4—C5	−176.39 (16)	C11—C8—C10—O3	−54.88 (16)
C2—C3—C4—C5	2.7 (3)	C9—C8—C10—O3	64.66 (16)
C3—C4—C5—C6	2.5 (3)	N1—C8—C11—O4	79.70 (15)
C4—C5—C6—C1	−2.9 (3)	C10—C8—C11—O4	−39.70 (17)
C7—C1—C6—C5	174.82 (16)	C9—C8—C11—O4	−162.15 (12)
C2—C1—C6—C5	−1.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.91 (2)	1.85 (2)	2.6125 (16)	139.7 (18)
O2—H2O···O4^i	0.84 (2)	1.92 (2)	2.7549 (16)	170 (2)
O3—H3O···O2^ii	0.83 (2)	1.91 (2)	2.7280 (17)	171 (2)
O4—H4O···O1^iii	0.85 (2)	1.91 (2)	2.7359 (16)	163 (2)
O4—H4O···O5^iii	0.85 (2)	2.47 (2)	3.0346 (16)	124.1 (17)

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