(Z)-6-{[1,3-Dihydroxy-2-(hydroxymethyl)propan-2-yliminio]methyl}-2-ethoxyphenolate, (Z)-6-{[1,3-dihydr­oxy-2-(hydroxy­meth­yl)propan-2-yliminio]meth­yl}-4-nitratocyclohexa-2,4-dienone monohydrate and (R,E)-2-[(1-hydroxy­butan-2-ylimino)meth­yl]­phenol

The title compounds C₁₃H₁₉NO₅, C₁₁H₁₄N₂O₆·H₂O and C₁₁H₁₅NO₂, respectively, have been derived from 3-ethoxy­salicylaldehyde, 5-nitro­salicylaldehyde and salicylaldehyde, respectively. The C-O and N-C bond distances, and three hydrogen bonds formed by the phenolate O atom, show that the zwitterionic form exists in the first compound. The second compound is transformed to the quinoid form as a result of resonance between the zwitterionic form and the nitro group. The third compound exists in the phenol-imine form, with appropriate C-N and C-O bond distances.

S1. Comment

There is considerable interest in Schiff base ligands and their complexes because of their striking antitumour activities (Zhou et al., 2000). Schiff base compounds show photochromism and thermochromism in the solid state by proton transfer from the hydroxyl O atom to the imine N atom (Cohen et al., 1964), i.e. phenol–imine keto–amine tautomerism. It is known that the phenol–imine tautomer is dominant in salicylaldimine, while the keto–amine form is preferred in the naphthaldimine Schiff bases depending on the solvent polarities. Moreover, o-hydroxy Schiff bases can exist in different tautomeric forms. The configurations of these compounds are controlled by steric and electronic effects (Filarowski et al., 2002), and the phenol–imine (molecular or phenol) and keto–amine (or keto) tautomeric forms are the most common. The subtituents on the phenol ring affect the tautomeric equilibrium. The existence of electron attracting groups on the o- and p-positions to the OH increase the acidity and the stability of the keto amine form with the mesomeric and inductive effects (Filarowski et al., 2002) Studies made so far show that o-hydroxy Schiff bases with electron-attracting groups like Cl and NO₂ at the o- or p-position exhibit the keto–amine form (Wozniak et al., 1995). The zwitterionic form is rarely seen in the solid state (Krygowski et al., 1997).

In compound (I) (Fig. 1), there are two molecules in the asymmetric unit. Fig. 3 shows (II), with a water molecule of crystallization in the asymmetric unit, and Fig. 5 shows (III). By analysing the C1—C2, C2—O1, C1—C7 and C7—N1 bonds in Table 8, it can be concluded that the C1—C2 bond lengths in (I) and (II) are longer than that in compound (III), whilst the C2—O1 bond length of in compound (II) is longer than those in other two compounds. The longest C1—C7 bond is in compound (III), and those of (I) and (II) are nearly equal. The C7—N1 bond lengths in all three compounds indicate that these bonds are C=N double bonds. As a result of this analysis, it can be said that the structure of compounds (I), (II) and (III) are closest to (Ia) (scheme 2), (IIb) (scheme 3) and (IIIa) (scheme 4), respectively. For compound (I), the comparisons of the C—O and N—C bond distances with the corresponding values of Allen et al. (1987) and also the existence of three hydrogen bonds formed by the negative O1 atom show that the zwitterionic form is very important (Scheme 2). In (II), evaluating the N—C and C—O bonds, it can be concluded that the aroused zwitterionic form (IIb) is important, arising from the resonating effect of the nitro group (scheme 3). In the solid state, the phenol–imine tautomeric form exists in salicylaldimine Schiff bases (Kaitner & Pavlovic, 1996; Yıldız et al., 1998). Also, the position of proton and the bond distances of C—N and C—O indicate that the compound (III) is in phenol–imine tautomeric form, (IIIa) (scheme 4).

In compound (I), each molecule in the asymmetric unit has an intramolecular N—H···O hydrogen bond. In addition, molecules A and B in the asymmetric unit are linked by intermolecular O—H···O hydrogen bonds forming a three-dimensional network, as shown in Fig. 2; this figure also shows the two five-membered pseudo-rings formed by the two intermolecular hydrogen bonds (O4A—H4A···O1B and O4A—H4A···O2B; and O4B—H4B···O1A and O4B—H4B···O2A). In (II), there are two intramolecular hydrogen bonds, N1—H1···O1 and O6—H6···O7, and the water molecules form intermolecular hydrogen bonds with O4 and O6 (Table 4, Fig. 4). Compound (III) has one intramolecular hydrogen bond, O1—H1···N1, which is shown in Fig. 5 and there is also an intermolecular hydrogen bond, O2—H2···O2 (Table 6 and Fig. 6). In all three compounds, in addition to the intermolecular hydrogen bonds, there are π–π interactions (Table 7), leading to a three-dimensional network. Cg1 and Cg2 given in Table 2 and Table 7 are the centroids of the C1A–C6A and C1B–C6B rings for compound (I); Cg1 is the centroid of the C1–C6 ring for (II) and (III).

S2. Experimental

All three title compounds were prepared as described by Odabasoglu et al. (2003) using as starting materials 3-ethoxysalicylaldehyde and tris(hydroxymethyl)aminomethane for (I) (yield 92%, m.p. 437–439 K). 5-nitrosalicylaldehyde and tris(hydroxymethyl)aminomethane for (II) (yield 95%, m.p. 508–510 K), and salicylaldehyde and (R)-(-)-2-amino-1-butanol for (III) (yield 85%, m.p. 329–331 K).

S3. Refinement

For (I): Except the attached ones to N, all the H atoms were refined using a riding model with C—H distance of 0.93 A and U_iso values equal to 1.2U_eq of the parent atom.

For (II): Except the attached ones to O5 and O6, all H-atom parameters were freely refined, with C—H distance in the range 0.92 (2)–1.13 (2) Å and U_iso(H) values in the range 0.053 (6)–0.161 (15) Ų.

For (III): Except the attached ones to O1 and O2, all the H atoms were

refined using a riding model with C—H distance of 0.93 A and U_iso values equal to 1.2U_eq of the parent atom.

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. A view of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids. Dashed lines indicate hydrogen bonds.
	Fig. 2. The packing of (I). Dashed lines indicate hydrogen bonds and 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. 3. A view of (II), with the atom-numbering scheme and 50% probability displacement ellipsoids. Dashed lines indicate hydrogen bonds.
	Fig. 4. The packing of (II). Dashed lines indicate hydrogen bonds and π–π interactions. H atoms not involved in hydrogen bonding have been omitted for clarity.
	Fig. 5. A view of (III), with the atom-numbering scheme and 30% probability displacement ellipsoids. The dashed line indicates a hydrogen bond.
	Fig. 6. The packing of (III). Dashed lines indicate hydrogen bonds and π–π interactions. H atoms not involved in hydrogen bonding have been omitted for clarity.

(I) (Z)-6-{[1,3-Dihydroxy-2-(hydroxymethyl)propan-2-yliminio]methyl}- 2-ethoxyphenolate

Crystal data

C13H19NO5	Z = 4
Mr = 269.29	F(000) = 576
Triclinic, P1	Dx = 1.348 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7424 (8) Å	Cell parameters from 22555 reflections
b = 10.6073 (8) Å	θ = 2.1–29.0°
c = 14.4820 (11) Å	µ = 0.10 mm^−1
α = 102.592 (6)°	T = 296 K
β = 104.459 (6)°	Prism, yellow
γ = 105.840 (6)°	0.43 × 0.31 × 0.19 mm
V = 1326.7 (2) Å^3

Data collection

Stoe IPDS-II diffractometer	6080 independent reflections
Radiation source: fine-focus sealed tube	3597 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.051
Detector resolution: 6.67 pixels mm^-1	θmax = 27.5°, θmin = 2.1°
ω scans	h = −12→12
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→13
Tmin = 0.946, Tmax = 0.988	l = −18→18
22555 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 0.88	w = 1/[σ^2(Fo^2) + (0.0498P)^2] where P = (Fo^2 + 2Fc^2)/3
6080 reflections	(Δ/σ)max < 0.001
361 parameters	Δρmax = 0.14 e Å^−3
6 restraints	Δρmin = −0.17 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
C1A	0.30620 (17)	0.78245 (16)	0.35738 (11)	0.0350 (3)
C1B	−0.02877 (16)	−0.34129 (15)	0.12329 (11)	0.0340 (3)
C2A	0.33266 (17)	0.65711 (15)	0.35498 (11)	0.0347 (3)
C2B	−0.04911 (16)	−0.21183 (15)	0.13568 (11)	0.0339 (3)
C3A	0.23044 (17)	0.55769 (16)	0.38209 (11)	0.0375 (3)
C3B	0.06703 (17)	−0.10185 (16)	0.12875 (11)	0.0357 (3)
C4A	0.10705 (18)	0.58075 (17)	0.40102 (12)	0.0437 (4)
H2A	0.0409	0.5144	0.4172	0.052*
C4B	0.19155 (17)	−0.12250 (16)	0.11010 (12)	0.0393 (4)
H2B	0.2656	−0.0498	0.1053	0.047*
C5A	0.07808 (18)	0.70205 (17)	0.39664 (12)	0.0432 (4)
H8A	−0.0082	0.7142	0.4076	0.052*
C5B	0.20934 (17)	−0.25151 (17)	0.09813 (12)	0.0393 (4)
H8B	0.2945	−0.2637	0.0853	0.047*
C6A	0.17592 (17)	0.80151 (17)	0.37635 (11)	0.0390 (4)
H6A	0.1577	0.8828	0.3748	0.047*
C6B	0.10276 (17)	−0.35794 (16)	0.10520 (11)	0.0366 (3)
H6B	0.1157	−0.4428	0.0981	0.044*
C7A	0.40902 (17)	0.89210 (16)	0.34174 (11)	0.0367 (3)
H7A	0.3856	0.9714	0.3418	0.044*
C7B	−0.13550 (17)	−0.45466 (16)	0.13292 (11)	0.0367 (3)
H7B	−0.1152	−0.5361	0.1279	0.044*
C8A	0.64885 (16)	0.99457 (15)	0.30974 (11)	0.0347 (3)
C8B	−0.37344 (16)	−0.55637 (15)	0.16759 (11)	0.0359 (3)
C9A	0.64241 (18)	1.13715 (16)	0.34918 (12)	0.0406 (4)
H9A	0.6462	1.1545	0.4185	0.049*
H9B	0.7292	1.2060	0.3466	0.049*
C9B	−0.3673 (2)	−0.69896 (16)	0.12986 (13)	0.0468 (4)
H9C	−0.4519	−0.7668	0.1357	0.056*
H9D	−0.3752	−0.7194	0.0597	0.056*
C10A	0.61801 (17)	0.95061 (16)	0.19595 (11)	0.0378 (3)
H10A	0.6046	0.8537	0.1728	0.045*
H10B	0.5248	0.9623	0.1627	0.045*
C10B	−0.33988 (17)	−0.50974 (16)	0.28126 (12)	0.0386 (3)
H10C	−0.2462	−0.5210	0.3141	0.046*
H10D	−0.3263	−0.4127	0.3035	0.046*
C11A	0.80283 (18)	0.99254 (17)	0.36695 (13)	0.0434 (4)
H11A	0.8810	1.0539	0.3509	0.052*
H11B	0.8213	1.0269	0.4383	0.052*
C11B	−0.52858 (18)	−0.55692 (17)	0.11089 (13)	0.0436 (4)
H11C	−0.5475	−0.5917	0.0395	0.052*
H11D	−0.6053	−0.6190	0.1275	0.052*
C22A	0.1902 (2)	0.35134 (19)	0.42777 (15)	0.0569 (5)
H22A	0.0841	0.3104	0.3875	0.068*
H22B	0.1983	0.4003	0.4949	0.068*
C22B	0.14276 (18)	0.13258 (16)	0.12848 (14)	0.0442 (4)
H22C	0.1514	0.1077	0.0622	0.053*
H22D	0.2419	0.1593	0.1778	0.053*
C33A	0.2592 (3)	0.2417 (2)	0.43089 (17)	0.0743 (6)
H33A	0.2077	0.1780	0.4596	0.112*
H33B	0.3641	0.2832	0.4710	0.112*
H33C	0.2501	0.1935	0.3641	0.112*
C33B	0.0829 (2)	0.24890 (18)	0.14170 (14)	0.0509 (4)
H33D	0.1501	0.3272	0.1332	0.076*
H33E	0.0754	0.2729	0.2077	0.076*
H33F	−0.0153	0.2211	0.0927	0.076*
N1A	0.53427 (14)	0.88833 (14)	0.32724 (10)	0.0369 (3)
N1B	−0.25991 (14)	−0.45078 (14)	0.14838 (10)	0.0372 (3)
O1A	0.44364 (12)	0.63210 (11)	0.33041 (9)	0.0443 (3)
O1B	−0.16637 (12)	−0.19203 (11)	0.15402 (9)	0.0452 (3)
O2A	0.26921 (13)	0.44390 (11)	0.38499 (9)	0.0463 (3)
O2B	0.03846 (12)	0.01887 (11)	0.14138 (9)	0.0452 (3)
O3A	0.50771 (13)	1.14768 (12)	0.29112 (9)	0.0467 (3)
O3B	−0.23044 (15)	−0.70647 (13)	0.18605 (12)	0.0638 (4)
O4A	0.73646 (13)	1.02752 (12)	0.16903 (9)	0.0486 (3)
O4B	−0.45729 (13)	−0.58538 (11)	0.31012 (9)	0.0464 (3)
O5A	0.81233 (14)	0.85944 (13)	0.34382 (9)	0.0492 (3)
O5B	−0.54130 (14)	−0.42492 (13)	0.13334 (10)	0.0516 (3)
H1A	0.5467 (19)	0.809 (2)	0.3255 (13)	0.050 (5)*
H1B	−0.272 (2)	−0.370 (2)	0.1517 (13)	0.055 (5)*
H3A	0.519 (2)	1.2337 (17)	0.3025 (16)	0.082*
H3B	−0.240 (3)	−0.7900 (17)	0.1760 (17)	0.082*
H4A	0.791 (2)	0.981 (2)	0.1612 (17)	0.082*
H4B	−0.505 (2)	−0.531 (2)	0.3254 (16)	0.082*
H5A	0.831 (3)	0.843 (2)	0.2897 (13)	0.082*
H5B	−0.556 (3)	−0.408 (2)	0.1893 (13)	0.082*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.0372 (8)	0.0371 (8)	0.0345 (8)	0.0136 (7)	0.0160 (7)	0.0126 (6)
C1B	0.0356 (8)	0.0318 (8)	0.0381 (8)	0.0120 (6)	0.0168 (7)	0.0118 (6)
C2A	0.0371 (8)	0.0346 (8)	0.0354 (8)	0.0130 (7)	0.0163 (7)	0.0107 (6)
C2B	0.0336 (8)	0.0354 (8)	0.0367 (8)	0.0123 (7)	0.0171 (7)	0.0117 (6)
C3A	0.0429 (9)	0.0329 (8)	0.0374 (8)	0.0114 (7)	0.0159 (7)	0.0114 (7)
C3B	0.0373 (8)	0.0333 (8)	0.0392 (8)	0.0130 (7)	0.0156 (7)	0.0118 (7)
C4A	0.0394 (9)	0.0444 (10)	0.0478 (9)	0.0081 (7)	0.0212 (8)	0.0157 (8)
C4B	0.0323 (8)	0.0390 (9)	0.0487 (9)	0.0085 (7)	0.0179 (7)	0.0174 (7)
C5A	0.0365 (9)	0.0515 (11)	0.0459 (9)	0.0174 (8)	0.0189 (8)	0.0142 (8)
C5B	0.0330 (8)	0.0458 (9)	0.0444 (9)	0.0164 (7)	0.0178 (7)	0.0148 (7)
C6A	0.0402 (9)	0.0399 (9)	0.0422 (9)	0.0185 (7)	0.0165 (7)	0.0133 (7)
C6B	0.0390 (8)	0.0363 (9)	0.0397 (8)	0.0173 (7)	0.0170 (7)	0.0115 (7)
C7A	0.0426 (9)	0.0349 (8)	0.0400 (8)	0.0181 (7)	0.0180 (7)	0.0149 (7)
C7B	0.0404 (9)	0.0334 (8)	0.0434 (9)	0.0162 (7)	0.0202 (7)	0.0137 (7)
C8A	0.0346 (8)	0.0286 (8)	0.0461 (9)	0.0118 (6)	0.0175 (7)	0.0152 (7)
C8B	0.0361 (8)	0.0310 (8)	0.0474 (9)	0.0114 (7)	0.0218 (7)	0.0165 (7)
C9A	0.0411 (9)	0.0337 (9)	0.0490 (9)	0.0147 (7)	0.0161 (8)	0.0132 (7)
C9B	0.0564 (11)	0.0317 (9)	0.0625 (11)	0.0152 (8)	0.0351 (9)	0.0162 (8)
C10A	0.0370 (8)	0.0357 (9)	0.0480 (9)	0.0148 (7)	0.0202 (7)	0.0169 (7)
C10B	0.0402 (8)	0.0351 (9)	0.0490 (9)	0.0161 (7)	0.0209 (7)	0.0180 (7)
C11A	0.0400 (9)	0.0393 (9)	0.0515 (10)	0.0164 (7)	0.0129 (8)	0.0143 (8)
C11B	0.0420 (9)	0.0418 (10)	0.0498 (10)	0.0123 (7)	0.0184 (8)	0.0187 (8)
C22A	0.0726 (13)	0.0482 (11)	0.0600 (11)	0.0163 (10)	0.0334 (10)	0.0286 (9)
C22B	0.0368 (8)	0.0374 (9)	0.0595 (11)	0.0089 (7)	0.0161 (8)	0.0217 (8)
C33A	0.0993 (17)	0.0591 (13)	0.0844 (15)	0.0330 (13)	0.0381 (14)	0.0441 (12)
C33B	0.0499 (10)	0.0393 (10)	0.0654 (12)	0.0151 (8)	0.0180 (9)	0.0212 (9)
N1A	0.0408 (7)	0.0301 (7)	0.0478 (8)	0.0150 (6)	0.0214 (6)	0.0161 (6)
N1B	0.0394 (7)	0.0293 (7)	0.0520 (8)	0.0134 (6)	0.0243 (6)	0.0171 (6)
O1A	0.0489 (7)	0.0378 (6)	0.0642 (7)	0.0222 (5)	0.0351 (6)	0.0223 (5)
O1B	0.0432 (6)	0.0365 (6)	0.0724 (8)	0.0186 (5)	0.0367 (6)	0.0226 (6)
O2A	0.0521 (7)	0.0372 (6)	0.0596 (7)	0.0156 (5)	0.0283 (6)	0.0228 (5)
O2B	0.0427 (6)	0.0337 (6)	0.0693 (8)	0.0146 (5)	0.0290 (6)	0.0212 (6)
O3A	0.0442 (6)	0.0345 (6)	0.0673 (8)	0.0194 (5)	0.0177 (6)	0.0204 (6)
O3B	0.0626 (8)	0.0407 (7)	0.1151 (12)	0.0304 (7)	0.0481 (8)	0.0391 (8)
O4A	0.0557 (7)	0.0402 (7)	0.0764 (8)	0.0264 (6)	0.0434 (7)	0.0318 (6)
O4B	0.0622 (8)	0.0371 (7)	0.0639 (7)	0.0252 (6)	0.0422 (6)	0.0273 (6)
O5A	0.0564 (7)	0.0472 (7)	0.0597 (8)	0.0318 (6)	0.0244 (6)	0.0230 (6)
O5B	0.0542 (7)	0.0562 (8)	0.0627 (8)	0.0315 (6)	0.0265 (6)	0.0292 (7)

Geometric parameters (Å, º)

C1A—C7A	1.414 (2)	C9A—H9B	0.9700
C1A—C2A	1.417 (2)	C9B—O3B	1.411 (2)
C1A—C6A	1.420 (2)	C9B—H9C	0.9700
C1B—C7B	1.418 (2)	C9B—H9D	0.9700
C1B—C6B	1.4188 (19)	C10A—O4A	1.4138 (17)
C1B—C2B	1.420 (2)	C10A—H10A	0.9700
C2A—O1A	1.2936 (16)	C10A—H10B	0.9700
C2A—C3A	1.435 (2)	C10B—O4B	1.4180 (17)
C2B—O1B	1.2952 (16)	C10B—H10C	0.9700
C2B—C3B	1.428 (2)	C10B—H10D	0.9700
C3A—O2A	1.3653 (18)	C11A—O5A	1.4123 (19)
C3A—C4A	1.370 (2)	C11A—H11A	0.9700
C3B—O2B	1.3669 (18)	C11A—H11B	0.9700
C3B—C4B	1.370 (2)	C11B—O5B	1.413 (2)
C4A—C5A	1.402 (2)	C11B—H11C	0.9700
C4A—H2A	0.9300	C11B—H11D	0.9700
C4B—C5B	1.405 (2)	C22A—O2A	1.4252 (18)
C4B—H2B	0.9300	C22A—C33A	1.497 (3)
C5A—C6A	1.354 (2)	C22A—H22A	0.9700
C5A—H8A	0.9300	C22A—H22B	0.9700
C5B—C6B	1.352 (2)	C22B—O2B	1.4304 (18)
C5B—H8B	0.9300	C22B—C33B	1.498 (2)
C6A—H6A	0.9300	C22B—H22C	0.9700
C6B—H6B	0.9300	C22B—H22D	0.9700
C7A—N1A	1.2983 (18)	C33A—H33A	0.9600
C7A—H7A	0.9300	C33A—H33B	0.9600
C7B—N1B	1.2960 (18)	C33A—H33C	0.9600
C7B—H7B	0.9300	C33B—H33D	0.9600
C8A—N1A	1.4695 (18)	C33B—H33E	0.9600
C8A—C9A	1.520 (2)	C33B—H33F	0.9600
C8A—C11A	1.530 (2)	N1A—H1A	0.878 (19)
C8A—C10A	1.538 (2)	N1B—H1B	0.887 (19)
C8B—N1B	1.4726 (18)	O3A—H3A	0.861 (16)
C8B—C9B	1.515 (2)	O3B—H3B	0.841 (16)
C8B—C11B	1.527 (2)	O4A—H4A	0.831 (15)
C8B—C10B	1.533 (2)	O4B—H4B	0.860 (15)
C9A—O3A	1.4183 (19)	O5A—H5A	0.839 (15)
C9A—H9A	0.9700	O5B—H5B	0.845 (15)
C7A—C1A—C2A	121.01 (13)	C8B—C9B—H9D	109.6
C7A—C1A—C6A	118.26 (14)	H9C—C9B—H9D	108.1
C2A—C1A—C6A	120.73 (13)	O4A—C10A—C8A	112.39 (13)
C7B—C1B—C6B	118.58 (13)	O4A—C10A—H10A	109.1
C7B—C1B—C2B	121.00 (13)	C8A—C10A—H10A	109.1
C6B—C1B—C2B	120.37 (13)	O4A—C10A—H10B	109.1
O1A—C2A—C1A	122.40 (13)	C8A—C10A—H10B	109.1
O1A—C2A—C3A	120.81 (13)	H10A—C10A—H10B	107.9
C1A—C2A—C3A	116.78 (13)	O4B—C10B—C8B	112.23 (13)
O1B—C2B—C1B	122.15 (13)	O4B—C10B—H10C	109.2
O1B—C2B—C3B	120.62 (13)	C8B—C10B—H10C	109.2
C1B—C2B—C3B	117.23 (12)	O4B—C10B—H10D	109.2
O2A—C3A—C4A	126.12 (14)	C8B—C10B—H10D	109.2
O2A—C3A—C2A	113.46 (13)	H10C—C10B—H10D	107.9
C4A—C3A—C2A	120.41 (14)	O5A—C11A—C8A	112.59 (13)
O2B—C3B—C4B	125.92 (13)	O5A—C11A—H11A	109.1
O2B—C3B—C2B	113.45 (12)	C8A—C11A—H11A	109.1
C4B—C3B—C2B	120.63 (14)	O5A—C11A—H11B	109.1
C3A—C4A—C5A	121.55 (14)	C8A—C11A—H11B	109.1
C3A—C4A—H2A	119.2	H11A—C11A—H11B	107.8
C5A—C4A—H2A	119.2	O5B—C11B—C8B	112.84 (14)
C3B—C4B—C5B	121.17 (14)	O5B—C11B—H11C	109.0
C3B—C4B—H2B	119.4	C8B—C11B—H11C	109.0
C5B—C4B—H2B	119.4	O5B—C11B—H11D	109.0
C6A—C5A—C4A	119.86 (14)	C8B—C11B—H11D	109.0
C6A—C5A—H8A	120.1	H11C—C11B—H11D	107.8
C4A—C5A—H8A	120.1	O2A—C22A—C33A	108.00 (15)
C6B—C5B—C4B	120.06 (14)	O2A—C22A—H22A	110.1
C6B—C5B—H8B	120.0	C33A—C22A—H22A	110.1
C4B—C5B—H8B	120.0	O2A—C22A—H22B	110.1
C5A—C6A—C1A	120.39 (14)	C33A—C22A—H22B	110.1
C5A—C6A—H6A	119.8	H22A—C22A—H22B	108.4
C1A—C6A—H6A	119.8	O2B—C22B—C33B	107.19 (13)
C5B—C6B—C1B	120.54 (14)	O2B—C22B—H22C	110.3
C5B—C6B—H6B	119.7	C33B—C22B—H22C	110.3
C1B—C6B—H6B	119.7	O2B—C22B—H22D	110.3
N1A—C7A—C1A	123.74 (14)	C33B—C22B—H22D	110.3
N1A—C7A—H7A	118.1	H22C—C22B—H22D	108.5
C1A—C7A—H7A	118.1	C22A—C33A—H33A	109.5
N1B—C7B—C1B	123.48 (14)	C22A—C33A—H33B	109.5
N1B—C7B—H7B	118.3	H33A—C33A—H33B	109.5
C1B—C7B—H7B	118.3	C22A—C33A—H33C	109.5
N1A—C8A—C9A	111.76 (12)	H33A—C33A—H33C	109.5
N1A—C8A—C11A	106.66 (12)	H33B—C33A—H33C	109.5
C9A—C8A—C11A	108.67 (13)	C22B—C33B—H33D	109.5
N1A—C8A—C10A	105.68 (12)	C22B—C33B—H33E	109.5
C9A—C8A—C10A	112.46 (12)	H33D—C33B—H33E	109.5
C11A—C8A—C10A	111.46 (12)	C22B—C33B—H33F	109.5
N1B—C8B—C9B	112.15 (12)	H33D—C33B—H33F	109.5
N1B—C8B—C11B	107.17 (12)	H33E—C33B—H33F	109.5
C9B—C8B—C11B	108.17 (14)	C7A—N1A—C8A	128.68 (13)
N1B—C8B—C10B	105.30 (12)	C7A—N1A—H1A	112.9 (11)
C9B—C8B—C10B	112.26 (13)	C8A—N1A—H1A	118.4 (11)
C11B—C8B—C10B	111.70 (12)	C7B—N1B—C8B	128.84 (13)
O3A—C9A—C8A	110.41 (13)	C7B—N1B—H1B	113.0 (11)
O3A—C9A—H9A	109.6	C8B—N1B—H1B	118.0 (11)
C8A—C9A—H9A	109.6	C3A—O2A—C22A	117.20 (12)
O3A—C9A—H9B	109.6	C3B—O2B—C22B	117.69 (11)
C8A—C9A—H9B	109.6	C9A—O3A—H3A	108.0 (15)
H9A—C9A—H9B	108.1	C9B—O3B—H3B	108.1 (16)
O3B—C9B—C8B	110.13 (14)	C10A—O4A—H4A	107.9 (16)
O3B—C9B—H9C	109.6	C10B—O4B—H4B	106.3 (15)
C8B—C9B—H9C	109.6	C11A—O5A—H5A	108.4 (16)
O3B—C9B—H9D	109.6	C11B—O5B—H5B	108.0 (16)
C7A—C1A—C2A—O1A	−5.9 (2)	N1A—C8A—C9A—O3A	−68.60 (16)
C6A—C1A—C2A—O1A	174.57 (14)	C11A—C8A—C9A—O3A	173.97 (12)
C7A—C1A—C2A—C3A	173.62 (14)	C10A—C8A—C9A—O3A	50.08 (16)
C6A—C1A—C2A—C3A	−5.9 (2)	N1B—C8B—C9B—O3B	66.88 (17)
C7B—C1B—C2B—O1B	−1.5 (2)	C11B—C8B—C9B—O3B	−175.14 (12)
C6B—C1B—C2B—O1B	−178.79 (14)	C10B—C8B—C9B—O3B	−51.45 (16)
C7B—C1B—C2B—C3B	177.49 (14)	N1A—C8A—C10A—O4A	−168.39 (12)
C6B—C1B—C2B—C3B	0.2 (2)	C9A—C8A—C10A—O4A	69.42 (16)
O1A—C2A—C3A—O2A	3.9 (2)	C11A—C8A—C10A—O4A	−52.90 (16)
C1A—C2A—C3A—O2A	−175.58 (13)	N1B—C8B—C10B—O4B	168.24 (12)
O1A—C2A—C3A—C4A	−175.30 (15)	C9B—C8B—C10B—O4B	−69.46 (16)
C1A—C2A—C3A—C4A	5.2 (2)	C11B—C8B—C10B—O4B	52.24 (16)
O1B—C2B—C3B—O2B	−1.1 (2)	N1A—C8A—C11A—O5A	52.16 (17)
C1B—C2B—C3B—O2B	179.89 (13)	C9A—C8A—C11A—O5A	172.80 (12)
O1B—C2B—C3B—C4B	179.52 (14)	C10A—C8A—C11A—O5A	−62.72 (17)
C1B—C2B—C3B—C4B	0.5 (2)	N1B—C8B—C11B—O5B	−53.05 (16)
O2A—C3A—C4A—C5A	179.56 (15)	C9B—C8B—C11B—O5B	−174.17 (12)
C2A—C3A—C4A—C5A	−1.3 (2)	C10B—C8B—C11B—O5B	61.80 (16)
O2B—C3B—C4B—C5B	−179.86 (15)	C1A—C7A—N1A—C8A	179.63 (15)
C2B—C3B—C4B—C5B	−0.5 (2)	C9A—C8A—N1A—C7A	22.5 (2)
C3A—C4A—C5A—C6A	−2.1 (2)	C11A—C8A—N1A—C7A	141.16 (16)
C3B—C4B—C5B—C6B	−0.2 (2)	C10A—C8A—N1A—C7A	−100.12 (17)
C4A—C5A—C6A—C1A	1.3 (2)	C1B—C7B—N1B—C8B	−174.65 (15)
C7A—C1A—C6A—C5A	−176.76 (15)	C9B—C8B—N1B—C7B	−22.1 (2)
C2A—C1A—C6A—C5A	2.8 (2)	C11B—C8B—N1B—C7B	−140.72 (16)
C4B—C5B—C6B—C1B	0.9 (2)	C10B—C8B—N1B—C7B	100.22 (17)
C7B—C1B—C6B—C5B	−178.26 (15)	C4A—C3A—O2A—C22A	−11.4 (2)
C2B—C1B—C6B—C5B	−0.9 (2)	C2A—C3A—O2A—C22A	169.38 (14)
C2A—C1A—C7A—N1A	−2.0 (2)	C33A—C22A—O2A—C3A	−175.37 (16)
C6A—C1A—C7A—N1A	177.53 (14)	C4B—C3B—O2B—C22B	3.8 (2)
C6B—C1B—C7B—N1B	−179.21 (14)	C2B—C3B—O2B—C22B	−175.52 (13)
C2B—C1B—C7B—N1B	3.5 (2)	C33B—C22B—O2B—C3B	177.54 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3A—H3A···O4B^i	0.86 (2)	1.85 (2)	2.7011 (15)	173 (2)
O3B—H3B···O4A^ii	0.84 (2)	1.86 (2)	2.6994 (16)	173 (2)
O4A—H4A···O1B^iii	0.83 (2)	1.98 (2)	2.7300 (15)	150 (2)
O4A—H4A···O2B^iii	0.83 (2)	2.43 (2)	3.0894 (15)	137 (2)
O4B—H4B···O1A^iv	0.86 (2)	1.92 (2)	2.7205 (15)	154 (2)
O4B—H4B···O2A^iv	0.86 (2)	2.52 (2)	3.1811 (15)	134 (2)
O5A—H5A···O1B^iii	0.84 (2)	1.93 (2)	2.7548 (16)	169 (2)
O5B—H5B···O1A^iv	0.85 (2)	2.00 (2)	2.8351 (16)	171 (2)
N1A—H1A···O1A	0.878 (19)	1.898 (19)	2.6331 (17)	140.3 (15)
N1B—H1B···O1B	0.887 (19)	1.876 (19)	2.6210 (17)	140.4 (16)
C9A—H9A···Cg1^v	0.97	2.84	3.7045 (17)	149
C33B—H33F···Cg2^vi	0.96	2.97	3.628 (2)	127

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

(II) (Z)-6-{[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yliminio]methyl}- 4-nitratocyclohexa-2,4-dienone monohydrate

Crystal data

C11H14N2O6·H2O	F(000) = 608
Mr = 288.26	Dx = 1.482 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11553 reflections
a = 16.9205 (11) Å	θ = 1.9–28.8°
b = 10.7034 (6) Å	µ = 0.13 mm^−1
c = 7.2308 (5) Å	T = 296 K
β = 99.518 (5)°	Plate, yellow
V = 1291.52 (14) Å^3	0.38 × 0.25 × 0.08 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	2877 independent reflections
Radiation source: fine-focus sealed tube	1898 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.059
Detector resolution: 6.67 pixels mm^-1	θmax = 27.5°, θmin = 2.3°
ω scans	h = −21→21
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→13
Tmin = 0.955, Tmax = 0.989	l = −9→9
11553 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)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.107	w = 1/[σ^2(Fo^2) + (0.0623P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max < 0.001
2877 reflections	Δρmax = 0.30 e Å^−3
214 parameters	Δρmin = −0.32 e Å^−3
2 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: 0.053 (4)

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	0.14865 (9)	0.67746 (12)	0.3596 (2)	0.0316 (3)
C2	0.18202 (9)	0.79887 (14)	0.3327 (2)	0.0341 (4)
C3	0.12911 (11)	0.90282 (15)	0.3381 (3)	0.0405 (4)
C4	0.05203 (11)	0.88724 (15)	0.3619 (3)	0.0400 (4)
C5	0.02170 (9)	0.76740 (14)	0.3870 (2)	0.0352 (4)
C6	0.06965 (9)	0.66455 (14)	0.3869 (2)	0.0344 (4)
C7	0.19745 (9)	0.56849 (14)	0.3731 (2)	0.0332 (4)
C8	0.33033 (9)	0.46906 (13)	0.3950 (2)	0.0319 (3)
C9	0.28957 (9)	0.34190 (14)	0.3605 (3)	0.0389 (4)
H9A	0.2485	0.3327	0.4386	0.047*
H9B	0.2644	0.3347	0.2303	0.047*
C10	0.36916 (9)	0.48493 (14)	0.6009 (2)	0.0364 (4)
H10A	0.4121	0.4246	0.6311	0.044*
H10B	0.3923	0.5679	0.6189	0.044*
C11	0.39198 (10)	0.48684 (15)	0.2657 (3)	0.0421 (4)
H11A	0.4368	0.4305	0.3020	0.051*
H11B	0.3680	0.4679	0.1375	0.051*
N1	0.27144 (8)	0.57004 (12)	0.3532 (2)	0.0331 (3)
N2	−0.05935 (8)	0.75260 (14)	0.4191 (2)	0.0435 (4)
O1	0.25388 (7)	0.81207 (10)	0.30752 (19)	0.0454 (3)
O2	−0.10117 (8)	0.84614 (14)	0.4203 (3)	0.0681 (5)
O3	−0.08391 (8)	0.64744 (13)	0.4466 (2)	0.0622 (4)
O4	0.34854 (7)	0.24826 (10)	0.40463 (19)	0.0483 (3)
H4A	0.3276	0.1792	0.3879	0.072*
O5	0.31300 (7)	0.46812 (10)	0.72336 (17)	0.0419 (3)
H5A	0.2769	0.5196	0.6989	0.063*
O6	0.41917 (8)	0.61161 (11)	0.2783 (2)	0.0506 (4)
O7	0.48561 (10)	0.68839 (15)	−0.0087 (3)	0.0630 (4)
H1	0.2918 (12)	0.640 (2)	0.327 (3)	0.051 (6)*
H2	0.1488 (13)	0.982 (2)	0.319 (3)	0.065 (6)*
H3	0.0153 (12)	0.952 (2)	0.360 (3)	0.058 (6)*
H4	0.0493 (12)	0.5849 (18)	0.410 (3)	0.050 (5)*
H5	0.1737 (10)	0.4898 (17)	0.408 (3)	0.040 (5)*
H6	0.4431 (16)	0.632 (2)	0.183 (4)	0.076 (8)*
H7A	0.4601 (15)	0.747 (2)	−0.062 (4)	0.082 (9)*
H7B	0.5317 (12)	0.714 (3)	0.030 (4)	0.098 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0350 (7)	0.0262 (7)	0.0340 (8)	0.0018 (6)	0.0073 (7)	0.0010 (6)
C2	0.0393 (8)	0.0301 (7)	0.0344 (9)	0.0008 (6)	0.0108 (7)	0.0039 (6)
C3	0.0500 (10)	0.0272 (7)	0.0465 (10)	0.0029 (6)	0.0143 (8)	0.0050 (6)
C4	0.0454 (9)	0.0323 (8)	0.0434 (10)	0.0099 (7)	0.0107 (8)	0.0014 (7)
C5	0.0330 (8)	0.0377 (8)	0.0353 (9)	0.0036 (6)	0.0066 (7)	−0.0008 (6)
C6	0.0348 (8)	0.0307 (7)	0.0374 (9)	−0.0003 (6)	0.0051 (7)	−0.0001 (6)
C7	0.0321 (7)	0.0285 (7)	0.0391 (9)	−0.0011 (6)	0.0066 (7)	−0.0006 (6)
C8	0.0302 (7)	0.0245 (7)	0.0422 (9)	0.0024 (5)	0.0099 (7)	−0.0022 (6)
C9	0.0371 (8)	0.0268 (7)	0.0526 (11)	0.0014 (6)	0.0068 (8)	−0.0038 (7)
C10	0.0363 (8)	0.0317 (7)	0.0428 (9)	0.0027 (6)	0.0106 (7)	−0.0027 (6)
C11	0.0433 (9)	0.0366 (8)	0.0500 (11)	−0.0010 (7)	0.0183 (8)	−0.0052 (7)
N1	0.0333 (7)	0.0252 (6)	0.0418 (8)	0.0002 (5)	0.0090 (6)	0.0027 (5)
N2	0.0350 (7)	0.0455 (8)	0.0496 (9)	0.0046 (6)	0.0064 (6)	−0.0078 (6)
O1	0.0429 (6)	0.0311 (6)	0.0668 (9)	−0.0014 (5)	0.0223 (6)	0.0083 (5)
O2	0.0422 (7)	0.0560 (8)	0.1087 (14)	0.0142 (6)	0.0204 (8)	−0.0125 (8)
O3	0.0424 (7)	0.0506 (8)	0.0972 (12)	−0.0077 (6)	0.0219 (7)	−0.0022 (7)
O4	0.0487 (7)	0.0265 (5)	0.0667 (9)	0.0057 (5)	0.0010 (6)	−0.0081 (5)
O5	0.0534 (7)	0.0289 (5)	0.0478 (7)	0.0077 (5)	0.0217 (6)	0.0049 (5)
O6	0.0548 (8)	0.0435 (7)	0.0598 (9)	−0.0127 (6)	0.0279 (7)	−0.0041 (6)
O7	0.0572 (9)	0.0626 (9)	0.0728 (11)	0.0036 (8)	0.0215 (8)	0.0215 (8)

Geometric parameters (Å, º)

C1—C6	1.390 (2)	C9—O4	1.4131 (18)
C1—C7	1.423 (2)	C9—H9A	0.9700
C1—C2	1.443 (2)	C9—H9B	0.9700
C2—O1	1.2666 (19)	C10—O5	1.414 (2)
C2—C3	1.433 (2)	C10—H10A	0.9700
C3—C4	1.354 (3)	C10—H10B	0.9700
C3—H2	0.93 (2)	C11—O6	1.4105 (19)
C4—C5	1.404 (2)	C11—H11A	0.9700
C4—H3	0.93 (2)	C11—H11B	0.9700
C5—C6	1.368 (2)	N1—H1	0.86 (2)
C5—N2	1.437 (2)	N2—O2	1.2269 (19)
C6—H4	0.94 (2)	N2—O3	1.227 (2)
C7—N1	1.284 (2)	O4—H4A	0.8200
C7—H5	0.983 (18)	O5—H5A	0.8200
C8—N1	1.4673 (18)	O6—H6	0.88 (3)
C8—C11	1.524 (2)	O7—H7A	0.819 (17)
C8—C9	1.528 (2)	O7—H7B	0.829 (18)
C8—C10	1.534 (2)
C6—C1—C7	118.00 (13)	O4—C9—H9A	110.1
C6—C1—C2	121.04 (13)	C8—C9—H9A	110.1
C7—C1—C2	120.79 (14)	O4—C9—H9B	110.1
O1—C2—C3	122.44 (14)	C8—C9—H9B	110.1
O1—C2—C1	121.75 (13)	H9A—C9—H9B	108.4
C3—C2—C1	115.82 (14)	O5—C10—C8	111.68 (13)
C4—C3—C2	121.82 (15)	O5—C10—H10A	109.3
C4—C3—H2	120.5 (14)	C8—C10—H10A	109.3
C2—C3—H2	117.7 (14)	O5—C10—H10B	109.3
C3—C4—C5	120.63 (15)	C8—C10—H10B	109.3
C3—C4—H3	124.0 (13)	H10A—C10—H10B	107.9
C5—C4—H3	115.4 (13)	O6—C11—C8	109.13 (13)
C6—C5—C4	120.36 (15)	O6—C11—H11A	109.9
C6—C5—N2	119.57 (14)	C8—C11—H11A	109.9
C4—C5—N2	120.04 (14)	O6—C11—H11B	109.9
C5—C6—C1	120.31 (14)	C8—C11—H11B	109.9
C5—C6—H4	119.6 (12)	H11A—C11—H11B	108.3
C1—C6—H4	120.1 (12)	C7—N1—C8	127.51 (13)
N1—C7—C1	123.18 (14)	C7—N1—H1	118.1 (13)
N1—C7—H5	119.1 (10)	C8—N1—H1	113.8 (13)
C1—C7—H5	117.5 (10)	O2—N2—O3	122.43 (16)
N1—C8—C11	106.98 (13)	O2—N2—C5	118.55 (15)
N1—C8—C9	110.47 (12)	O3—N2—C5	119.01 (14)
C11—C8—C9	110.33 (13)	C9—O4—H4A	109.5
N1—C8—C10	106.61 (12)	C10—O5—H5A	109.5
C11—C8—C10	110.78 (13)	C11—O6—H6	111.4 (16)
C9—C8—C10	111.51 (13)	H7A—O7—H7B	107 (3)
O4—C9—C8	108.19 (12)
C6—C1—C2—O1	−179.94 (16)	C11—C8—C9—O4	62.53 (18)
C7—C1—C2—O1	4.9 (2)	C10—C8—C9—O4	−61.02 (17)
C6—C1—C2—C3	0.6 (2)	N1—C8—C10—O5	64.27 (15)
C7—C1—C2—C3	−174.57 (15)	C11—C8—C10—O5	−179.68 (12)
O1—C2—C3—C4	178.85 (17)	C9—C8—C10—O5	−56.38 (16)
C1—C2—C3—C4	−1.7 (3)	N1—C8—C11—O6	50.34 (17)
C2—C3—C4—C5	1.6 (3)	C9—C8—C11—O6	170.55 (13)
C3—C4—C5—C6	−0.3 (3)	C10—C8—C11—O6	−65.48 (17)
C3—C4—C5—N2	177.69 (17)	C1—C7—N1—C8	168.79 (15)
C4—C5—C6—C1	−0.8 (2)	C11—C8—N1—C7	152.37 (16)
N2—C5—C6—C1	−178.79 (15)	C9—C8—N1—C7	32.3 (2)
C7—C1—C6—C5	175.90 (15)	C10—C8—N1—C7	−89.06 (19)
C2—C1—C6—C5	0.6 (2)	C6—C5—N2—O2	179.38 (17)
C6—C1—C7—N1	−178.96 (16)	C4—C5—N2—O2	1.4 (3)
C2—C1—C7—N1	−3.6 (3)	C6—C5—N2—O3	0.3 (2)
N1—C8—C9—O4	−179.39 (14)	C4—C5—N2—O3	−177.72 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O5^i	0.82	1.97	2.6801 (15)	145
O5—H5A···O1^ii	0.82	2.03	2.6661 (15)	134
O7—H7A···O6^iii	0.82 (2)	1.96 (2)	2.765 (2)	167 (3)
O7—H7B···O4^iv	0.83 (2)	2.04 (2)	2.855 (2)	169 (3)
N1—H1···O1	0.86 (2)	1.95 (2)	2.6221 (17)	134.6 (18)
O6—H6···O7	0.88 (3)	1.77 (3)	2.649 (2)	173 (2)

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

(III) (R,E)-2-[(1-hydroxybutan-2-ylimino)methyl]phenol

Crystal data

C11H15NO2	Dx = 1.039 Mg m^−3
Mr = 193.24	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 2997 reflections
Hall symbol: R3	θ = 1.7–25.7°
a = 23.561 (4) Å	µ = 0.07 mm^−1
c = 5.7823 (8) Å	T = 296 K
V = 2779.8 (8) Å^3	Prism, yellow
Z = 9	0.50 × 0.37 × 0.23 mm
F(000) = 936

Data collection

Stoe IPDS-II diffractometer	1209 independent reflections
Radiation source: fine-focus sealed tube	646 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.039
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 1.7°
ω scans	h = −29→29
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −29→29
Tmin = 0.967, Tmax = 0.982	l = −7→7
2997 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 0.81	w = 1/[σ^2(Fo^2) + (0.055P)^2] where P = (Fo^2 + 2Fc^2)/3
1209 reflections	(Δ/σ)max < 0.001
134 parameters	Δρmax = 0.08 e Å^−3
3 restraints	Δρmin = −0.10 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	0.33506 (16)	0.15248 (14)	0.5014 (4)	0.0752 (7)
C2	0.32212 (17)	0.12026 (13)	0.7141 (5)	0.0847 (8)
C3	0.3604 (3)	0.09421 (18)	0.7873 (6)	0.1054 (11)
H3	0.3516	0.0722	0.9280	0.127*
C4	0.4103 (3)	0.1006 (2)	0.6558 (8)	0.1214 (13)
H4	0.4360	0.0835	0.7091	0.146*
C5	0.4246 (2)	0.1317 (2)	0.4446 (7)	0.1153 (12)
H5	0.4587	0.1347	0.3540	0.138*
C6	0.38714 (18)	0.15821 (18)	0.3707 (5)	0.0966 (9)
H6	0.3970	0.1804	0.2303	0.116*
C7	0.29508 (16)	0.17864 (14)	0.4153 (5)	0.0782 (7)
H7	0.3050	0.1995	0.2723	0.094*
C8	0.20890 (17)	0.20209 (19)	0.4316 (6)	0.0984 (10)
H8	0.2262	0.2206	0.2787	0.118*
C9	0.2165 (2)	0.2560 (2)	0.5928 (6)	0.1102 (12)
H9A	0.1873	0.2715	0.5427	0.132*
H9B	0.2032	0.2381	0.7471	0.132*
C10	0.1372 (2)	0.1489 (3)	0.4093 (10)	0.1527 (17)
H10A	0.1212	0.1284	0.5589	0.183*
H10B	0.1116	0.1688	0.3627	0.183*
C11	0.1276 (3)	0.0972 (4)	0.2357 (14)	0.221 (3)
H11A	0.0818	0.0654	0.2240	0.331*
H11B	0.1513	0.0759	0.2849	0.331*
H11C	0.1437	0.1172	0.0875	0.331*
N1	0.24712 (13)	0.17407 (13)	0.5286 (4)	0.0845 (7)
O1	0.27283 (14)	0.11369 (12)	0.8504 (3)	0.1060 (7)
O2	0.28091 (17)	0.30953 (13)	0.6018 (5)	0.1139 (8)
H2	0.307 (2)	0.302 (2)	0.733 (8)	0.144 (14)*
H1	0.246 (3)	0.130 (3)	0.757 (11)	0.21 (2)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.092 (2)	0.0631 (15)	0.0793 (16)	0.0452 (15)	−0.0077 (15)	−0.0074 (13)
C2	0.109 (2)	0.0676 (18)	0.0850 (18)	0.0494 (18)	−0.0133 (18)	−0.0070 (15)
C3	0.150 (4)	0.093 (2)	0.100 (2)	0.081 (3)	−0.023 (2)	−0.0047 (17)
C4	0.152 (4)	0.128 (3)	0.130 (3)	0.103 (3)	−0.038 (3)	−0.014 (3)
C5	0.129 (3)	0.129 (3)	0.128 (3)	0.094 (3)	−0.006 (2)	−0.015 (2)
C6	0.113 (3)	0.094 (2)	0.101 (2)	0.066 (2)	−0.0005 (19)	−0.0005 (17)
C7	0.092 (2)	0.0701 (18)	0.0796 (15)	0.0456 (16)	−0.0056 (16)	−0.0011 (13)
C8	0.094 (2)	0.115 (2)	0.109 (2)	0.069 (2)	−0.0024 (17)	0.0146 (19)
C9	0.128 (3)	0.138 (4)	0.107 (2)	0.099 (3)	0.010 (2)	0.013 (2)
C10	0.102 (3)	0.165 (4)	0.194 (4)	0.070 (3)	−0.021 (3)	0.005 (4)
C11	0.164 (5)	0.203 (7)	0.269 (8)	0.072 (5)	−0.068 (5)	−0.072 (6)
N1	0.0905 (17)	0.0840 (17)	0.0882 (14)	0.0505 (15)	0.0017 (14)	0.0077 (12)
O1	0.132 (2)	0.1028 (17)	0.0945 (13)	0.0675 (16)	0.0155 (14)	0.0245 (12)
O2	0.143 (3)	0.1032 (19)	0.1137 (16)	0.075 (2)	0.0041 (18)	0.0095 (14)

Geometric parameters (Å, º)

C1—C6	1.389 (4)	C8—C9	1.513 (5)
C1—C2	1.397 (4)	C8—C10	1.524 (6)
C1—C7	1.448 (4)	C8—H8	0.9800
C2—O1	1.347 (4)	C9—O2	1.408 (5)
C2—C3	1.387 (5)	C9—H9A	0.9700
C3—C4	1.344 (6)	C9—H9B	0.9700
C3—H3	0.9300	C10—C11	1.506 (8)
C4—C5	1.377 (6)	C10—H10A	0.9700
C4—H4	0.9300	C10—H10B	0.9700
C5—C6	1.380 (5)	C11—H11A	0.9600
C5—H5	0.9300	C11—H11B	0.9600
C6—H6	0.9300	C11—H11C	0.9600
C7—N1	1.263 (4)	O1—H1	1.04 (7)
C7—H7	0.9300	O2—H2	1.04 (5)
C8—N1	1.468 (4)
C6—C1—C2	118.3 (3)	N1—C8—H8	109.5
C6—C1—C7	120.2 (3)	C9—C8—H8	109.5
C2—C1—C7	121.5 (3)	C10—C8—H8	109.5
O1—C2—C3	119.0 (3)	O2—C9—C8	113.4 (3)
O1—C2—C1	121.3 (3)	O2—C9—H9A	108.9
C3—C2—C1	119.7 (3)	C8—C9—H9A	108.9
C4—C3—C2	120.3 (4)	O2—C9—H9B	108.9
C4—C3—H3	119.9	C8—C9—H9B	108.9
C2—C3—H3	119.9	H9A—C9—H9B	107.7
C3—C4—C5	122.0 (3)	C11—C10—C8	112.2 (5)
C3—C4—H4	119.0	C11—C10—H10A	109.2
C5—C4—H4	119.0	C8—C10—H10A	109.2
C4—C5—C6	118.3 (4)	C11—C10—H10B	109.2
C4—C5—H5	120.9	C8—C10—H10B	109.2
C6—C5—H5	120.9	H10A—C10—H10B	107.9
C5—C6—C1	121.4 (3)	C10—C11—H11A	109.5
C5—C6—H6	119.3	C10—C11—H11B	109.5
C1—C6—H6	119.3	H11A—C11—H11B	109.5
N1—C7—C1	122.0 (3)	C10—C11—H11C	109.5
N1—C7—H7	119.0	H11A—C11—H11C	109.5
C1—C7—H7	119.0	H11B—C11—H11C	109.5
N1—C8—C9	107.5 (3)	C7—N1—C8	119.2 (3)
N1—C8—C10	109.8 (3)	C2—O1—H1	107 (3)
C9—C8—C10	111.1 (4)	C9—O2—H2	110 (2)
C6—C1—C2—O1	179.2 (3)	C7—C1—C6—C5	−177.6 (3)
C7—C1—C2—O1	−1.7 (4)	C6—C1—C7—N1	179.6 (3)
C6—C1—C2—C3	−1.0 (4)	C2—C1—C7—N1	0.5 (4)
C7—C1—C2—C3	178.1 (3)	N1—C8—C9—O2	65.7 (4)
O1—C2—C3—C4	−179.4 (3)	C10—C8—C9—O2	−174.1 (3)
C1—C2—C3—C4	0.8 (5)	N1—C8—C10—C11	−65.6 (6)
C2—C3—C4—C5	−1.2 (6)	C9—C8—C10—C11	175.6 (5)
C3—C4—C5—C6	1.6 (6)	C1—C7—N1—C8	179.6 (3)
C4—C5—C6—C1	−1.8 (5)	C9—C8—N1—C7	−116.9 (3)
C2—C1—C6—C5	1.4 (5)	C10—C8—N1—C7	122.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O2^i	1.04 (5)	1.65 (5)	2.675 (4)	170 (4)
O1—H1···N1	1.04 (7)	1.67 (7)	2.591 (3)	145 (5)

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