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The Schiff base enaminones (3Z)-4-(5-ethyl­sulfonyl-2-hy­droxy­anilino)pent-3-en-2-one, C13H17NO4S, (I), and (3Z)-4-(5-tert-butyl-2-hy­droxy­anilino)pent-3-en-2-one, C15H21NO2, (II), were studied by X-ray crystallography and density functional theory (DFT). Although the keto tautomer of these compounds is dominant, the O=C-C=C-N bond lengths are consistent with some electron delocalization and partial enol character. Both (I) and (II) are nonplanar, with the amino-phenol group canted relative to the rest of the mol­ecule; the twist about the N(enamine)-C(aryl) bond leads to dihedral angles of 40.5 (2) and -116.7 (1)° for (I) and (II), respectively. Compound (I) has a bifurcated intra­molecular hydrogen bond between the N-H group and the flanking carbonyl and hydroxy O atoms, as well as an inter­molecular hydrogen bond, leading to an infinite one-dimensional hydrogen-bonded chain. Compound (II) has one intra­molecular hydrogen bond and one inter­molecular C=O...H-O hydrogen bond, and consequently also forms a one-dimensional hydrogen-bonded chain. The DFT-calculated structures [in vacuo, B3LYP/6-311G(d,p) level] for the keto tautomers compare favourably with the X-ray crystal structures of (I) and (II), confirming the dominance of the keto tautomer. The simulations indicate that the keto tautomers are 20.55 and 18.86 kJ mol-1 lower in energy than the enol tautomers for (I) and (II), respectively.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113002369/yp3023sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113002369/yp3023Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113002369/yp3023IIsup3.hkl
Contains datablock II

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113002369/yp3023Isup4.cml
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113002369/yp3023IIsup5.cml
Supplementary material

CCDC references: 934563; 934564

Comment top

Schiff base enaminones have been widely studied, due to their diverse chemistry and various applications in coordination chemistry (Kim et al., 2001; Doherty et al., 1999; Xiu et al., 1997; Zhang & Zhu, 2008). Studies of the free ligands have shown that the OC—CC—N bond lengths reflect electron delocalization and the presence of keto and enol tautomeric forms (Shi et al., 2004; Gilli et al., 2000).

The structure of 4-amino-N-(2-hydroxyphenyl)pent-3-en-2-one, consisting of phenol and aminopent-3-en-2-one groups, has been studied previously by X-ray crystallography and AM1 calculations (Kabak et al., 1998). Both keto and enol tautomeric forms of this compound can exist, but the keto form is dominant in the enthalpically favoured nonplanar structure (in which the ketone bridge is canted relative to the aminophenol group). Nonplanarity in this system is brought about by nonbonded H···H repulsions, consistent with previous observations for N-benzylideneaniline and related compounds (Burgi & Dunitz, 1971). Interestingly, the latter study suggested that delocalization of the N-atom lone-pair electrons onto the aniline ring when the compound is in a nonplanar conformation possibly contributes to the stability of the observed molecular geometry. Studies of tridentate Schiff base compounds similar to those reported here, e.g. 2-hydroxy-N-(2-hydroxy-5-methylphenyl)benzaldehydeimine (Kabak et al., 1999), 3-(2-hydroxyphenylimino)-1-phenylbutan-1-one (Dey et al., 2009) and 4-chloro-2-(4-oxopent-2-en-2-ylamino)phenol (Arıcı et al., 1999), have likewise highlighted the occurrence of nonplanar conformations with a dominant keto tautomer. Planarity in the compound 3-methoxyphenylsalicylaldimine, which contains a meta-substituted methoxy group rather than the hydroxy group on the ring, has been attributed to a lack of nonbonded intramolecular repulsions (Elmali et al., 1999). From a more general perspective, the conformation of a Schiff base compound may dictate aspects of its physical behaviour and thus some of its potential applications. Thus, some planar Schiff base compounds are reportedly thermochromic in the solid state (the mechanism involves proton transfer), while those with a nonplanar geometry may exhibit photochromism (Hadjoudis et al., 1987; Moustakali-Mavridis et al., 1978).

Although interesting in its own right, the Schiff base 4-amino-N-(2-hydroxyphenyl)pent-3-en-2-one is a synthetically tractable tridentate ligand for metal ions and has been chelated to both NiII (Zhang & Zhu, 2008) and SiIV (Seiler et al., 2005). The ligand coordinates the metal ions via its hydroxyphenol O- and N-donor atoms and its enolate O-donor atom, thereby forming adjacent five- and six-membered chelate rings with the metal ion. In such complexes, the NC, C—O and C—C bond lengths of the bridge are consistent with the enolic form of the compound. The ligand itself is nonplanar due to the out-of-plane tilt of the phenyl group relative to the remainder of the molecule. Interestingly, although square-planar complexes are formed with such ligands and NiII, distorted trigonal–bipyramidal complexes are favoured with SiIV, in which the N atom of the ligand occupies an axial position while the O atoms bind in equatorial positions. Similar results are obtained for other tridentate derivatives chelated to CuII, NiII, CoII and FeIII, where the metal–ligand ratios vary from 1:1 to 1:2 (Sallam et al., 2002).

In this paper, we report the X-ray structures of the two title tridentate Schiff base enaminones, (I) and (II) (Fig. 1). Both (I) and (II) consist of a pent-3-en-2-one group (referred to as part A), comprising atoms C1–C5 and O1, and an aminophenol group (referred to as part B), comprising atoms C6–C11, N1 and O2. Compound (I) has an ethylsulfonyl group in the para position relative to the hydroxy group on the phenol ring, while (II) has a tert-butyl group in the para position.

Both (I) and (II) are nonplanar, but parts A and B of both compounds approach planarity. The maximum deviations from planarity in (I) are 0.013 (1) (for atom C4 of part A) and 0.031 (1) Å (for atom C6 of part B). The deviations from planarity exhibited by (II) are 0.036 (1) (for atom C3 of part A) and 0.045 (1) Å (for atom N1 of part B). In (I), the mean planes through parts A and B subtend an angle of 31.7 (5)°; this angle is reflected predominantly in a twist around the N1—C6 bond, with a C11—C6—N1—C4 torsion angle of 40.5 (2)°. Even with this out-of-plane twist, atoms O2, N1 and O1 all face each other, a geometry similar to that observed for the parent compound, 4-amino-N-(2-hydroxyphenyl)pent-3-en-2-one, for which the equivalent angle is 32.8 (1)° (Kabak et al., 1998). In (II), the mean planes through parts A and B are at a much wider angle of 67.5 (1)° to each other. The twist around the N1—N6 bond means that parts A and B of (II) are nearly perpendicular, with a C11—C6—N1—C4 torsion angle of -116.7 (1)°. The result of this angle is that, in contrast with (I) and the parent compound, atoms N1 and O1 face each other while atom O2 faces in the opposite direction. The three-atom mean plane through the ethylsulfonyl group of (I) is at an angle of 78.7 (4)° to the mean plane of part B, with a C9—C10—S1—C12 torsion angle of 100.1 (1)°.

The C2—O1 bond lengths for (I) and (II) (Tables 1 and 3) suggest that they have a bond order of 1.5, based on the standard values of single and double C—O bonds (Allen et al., 1987). This, coupled with short C3—C4 bonds for (I) and (II), indicates the presence of a significant contribution from the keto tautomer (as reported for the parent compound; Kabak et al., 1998). The C2—C3 bond lengths of (I) and (II) are intermediate between typical C—C single bonds and CC double bonds (Allen et al., 1987). Compounds (I) and (II) have C7—O2 bond lengths typical of a phenolic C—O bond. Compound (I) has an average C—S bond length of 1.771 (1) Å and an average SO bond length of 1.444 (2) Å. Compounds (I) and (II) have average O1—C—C angles of 120.9 (2) and 120.3 (1)°, respectively. These average angles highlight the sp2 hybridization of the C atom and are consistent with the values reported for the parent compound. The average O—S—C angle and C12—S1—C10 angles of (I) are 108.6 (7) and 103.8 (6)°, respectively.

As might be anticipated for phenolic compounds bearing additional groups with N and O heteroatoms, (I) and (II) exhibit interesting intra- and intermolecular hydrogen-bonding patterns (Fig. 2). In (I), a bifurcated intramolecular N1—H100···O1/O2 hydrogen bond is observed. The N1—H100···O1 hydrogen bond results in a six-membered ring, while the N1—H100···O2 hydrogen bond results in a five-membered ring. There is also one intermolecular O2—H200···O1i hydrogen bond. This hydrogen bond links the molecules into extended one-dimensional columns collinear with the b axis; the hydrogen-bond geometry is summarized in Table 2. There are two additional C—H···O interactions (C12—H12B···O4? and C1—H1B···O2? [Please provide missing symmetry codes]) which link the one-dimensional chains into a three-dimensional network. The three-dimensional network exhibits a herringbone pattern when viewed down the b axis. These interactions are all at least 0.2 Å shorter than the sum of the van der Waals radii of the interacting atoms (Standard reference?). Such short distances, coupled with the fact that the bond angles approach ideality, suggest that they are likely to be moderately strong interactions.

In contrast with (I), the N—H group of (II) is not involved in a bifurcated hydrogen bond; rather, there is a conventional intramolecular N1—H100···O1 hydrogen bond. The intramolecular hydrogen bonds of (I) and (II) are both considerably shorter than the sum of the van der Waals radii, although this gives little indication of bond strength as the lengths of the interactions are governed by the geometry of the molecule and not bond strength. In addition to an intramolecular hydrogen bond, atom O1 also acts as a hydrogen-bond acceptor for an intermolecular hydrogen bond from the O2—H200 group. This interaction results in a one-dimensional hydrogen-bonded chain collinear with the c axis; the hydrogen-bond geometry for (II) is summarized in Table 4. The intermolecular hydrogen bond is characterized by a short nonbonded contact distance and an interaction angle that approaches an ideal value, suggesting that the interaction is likely to be moderate to strong. The rotation about the N1—C6 bond of (II) compared with (I) allows for an intramolecular C5—H5B···O2 interaction involving the methyl group of the bridge.

Density functional theory (DFT) calculations were performed in vacuo using GAUSSIAN09W (Frisch et al., 2009) at the B3LYP (Becke, 1993; Lee et al., 1988; Vosko et al., 1980; Stephens et al., 1994) /6-311G(d,p) (McLean & Chandler, 1980; Raghavachari et al., 1980) level of theory to explore further the energy differences between the keto and enol tautomeric forms. The geometry-optimized structures and the energies of the two tautomeric forms were calculated for both (I) and (II) using the X-ray coordinates of the non-H atoms for the input structures. As portrayed in Fig. 3, the high degree of similitude for the least-squares fits (Mercury; Macrae et al., 2008) of the X-ray structures to the keto forms of the DFT-calculated structures confirms the appropriateness of the level of theory used for the calculations [the root mean-square differences, r.m.s.d.s, are 0.192 Å for (I) and 0.190 Å for (II)]. Moreover, the DFT-calculated structures clearly show that the molecules are nonplanar, with the torsion angle about the C6—N1 bond in (I) measuring 29.81° for the keto tautomer and 29.58° for the enol tautomer; the corresponding dihedral angles for (II) are -120.97 and -123.29°. In both cases, the calculated conformations are in good agreement with those determined experimentally.

Finally, the DFT-calculated structures allow one to delineate cleanly between the keto and enol tautomers of the compound and to assign confidently the tautomer present in the X-ray structure. Thus, the DFT-calculated keto tautomer of (I) has a C2—O1 bond distance of 1.237 Å, while the enol tautomer has a bond distance of 1.323 Å; the former matches that observed for the X-ray structure [C2—O1 = 1.263 (2) Å; see above]. The keto form may be similarly assigned from the C3—C4 bond distances for the keto and enol tautomers, which are 1.376 and 1.440 Å, respectively, in the DFT-calculated structures. As noted above, the X-ray structure of (I) has a C3—C4 bond length of 1.394 (2) Å and is clearly the keto tautomer. The same conclusion may be drawn from a comparable analysis of the relevant bond distances for (II). The full lists of DFT-calculated and experimental bond lengths are shown in Tables 5 and 6. Collectively, the bond lengths of the calculated keto tautomers of (I) and (II) are in excellent agreement with the corresponding X-ray data, strongly confirming that the keto tautomers are favoured in the solid state. Interestingly, the present calculations show that the keto tautomers are favoured over the enol tautomers by 20.55 and 18.86 kJ mol-1 for (I) and (II), respectively. Lastly, the present DFT calculations support the conclusions drawn from the semi-empirical calculations performed on the parent compound (Kabak et al., 1998).

Related literature top

For related literature, see: Allen et al. (1987); Arıcı, Tahir, Ülkü & Atakol (1999); Becke (1993); Burgi & Dunitz (1971); Dey et al. (2009); Doherty et al. (1999); Elmali et al. (1999); Frisch (2009); Gilli et al. (2000); Hadjoudis et al. (1987); Kabak et al. (1998, 1999); Kim et al. (2001); Lee et al. (1988); Macrae et al. (2008); McLean & Chandler (1980); Moustakali-Mavridis, Hadjoudis & Mavridis (1978); Raghavachari et al. (1980); Sallam et al. (2002); Seiler et al. (2005); Shi et al. (2004); Stephens et al. (1994); Vosko et al. (1980); Xiu et al. (1997); Zhang & Zhu (2008).

Experimental top

Pentane-2,4-dione (1.00 g, 9.99 mmol) was added to 2-amino-4-(ethylsulfonyl)phenol (2.01 g, 9.99 mmol) in ethanol (30 ml) and the solution was refluxed for 1 h. The reaction mixture was then left undisturbed and brown [Orange in CIF tables - please clarify] crystals of (I) formed by slow evaporation (yield 1.565 g, 55%). Spectroscopic analysis: 1H NMR (400 MHz, DMSO-d6, 303 K, δ, p.p.m.): 1.08 (t, 3J = 7.3 Hz, 3H, CH2CH3), 2.00 (s, 3H, CH3), 2.04 (s, 3H, CH3), 3.21 (q, 3J = 7.4 Hz, 2H, CH2CH3), 5.29 (s, 1H, CH), 7.10 (d, 3J = 8.4 Hz, 1H, aromatic CH), 7.50 (dd, 3J = 8.4 Hz, 4J = 2.4 Hz, 1H, aromatic CH), 7.60 (d, 4J = 2.4 Hz, 1H, aromatic CH), 11.16 (s, 1H, OH), 12.22 (s, 1H, NH); 13C NMR (100 MHz, CDCl3, 303 K, δ, p.p.m.): 7.76, 20.04, 29.50, 49.94, 99.01, 116.16, 122.00, 126.33, 127.55, 128.91, 154.99, 159.31, 195.64.

Pentane-2,4-dione (0.607 g, 6.06 mmol) was added to 2-amino-4-tert-butylphenol (1.00 g, 6.05 mmol) in ethanol (30 ml) and the solution was refluxed for 2 h. The solution was then cooled to 273 K for 30 min, resulting in the formation of a cream precipitate. The precipitate was filtered off and air dried, yielding a cream-coloured powder of (II) (yield 0.752 g, 51%). Single colourless crystals were grown by liquid–liquid diffusion of hexane into a dichloromethane solution of (II). Spectroscopic analysis: 1H NMR (400 MHz, DMSO-d6, 303 K, δ, p.p.m.): 1.24 (s, 9H, CH3), 1.95 (s, 3H, CH3), 1.97 (s, 3H, CH3), 5.19 (s, 1H, CH), 6.83 (d, 3J = 8.5 Hz, 1H, aromatic CH), 7.04 (dd, 3J = 8.5 Hz, 4J = 2.5 Hz, 1H, aromatic CH), 7.09 (d, 4J= 2.5 Hz, 1H, aromatic CH), 9.62 (s, 1H, OH), 12.10 (s, 1H, NH); 13C NMR (100 MHz, CDCl3, 303 K), δ, p.p.m.): 19.81, 29.30, 31.74, 34.19, 97.37, 115.75, 122.97, 123.37, 125.77, 141.97, 148.70, 160.86, 194.55.

Refinement top

The positions of all C-bonded H atoms were calculated using a standard riding model, with aromatic C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C), methylene C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C), and methyl C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C). The amino and hydroxy H atoms were located in difference density maps and allowed to refine isotropically.

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid plots (50% probability surfaces) of (a) (I) and (b) (II). Intramolecular hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. (a) The extended one-dimensional hydrogen-bonded chain formed in (I), viewed down the c axis. (b) The extended one-dimensional hydrogen-bonded chain formed in (II), viewed down the b axis. Hydrogen bonds are shown as dashed lines.
[Figure 3] Fig. 3. An overlay of the DFT-calculated (yellow in the electronic version of the paper) and experimental (blue) structures of the keto tautomer for (a) (I) and (b) (II).
(I) (3Z)-4-(5-Ethylsulfonyl-2-hydroxyanilino)pent-3-en-2-one top
Crystal data top
C13H17NO4SF(000) = 600
Mr = 283.34Dx = 1.361 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 2673 reflections
a = 6.2335 (6) Åθ = 1.6–26.4°
b = 8.9651 (8) ŵ = 0.24 mm1
c = 24.747 (2) ÅT = 100 K
V = 1383.0 (2) Å3Block, brown
Z = 40.45 × 0.40 × 0.40 mm
Data collection top
Bruker APEX DUO
diffractometer
2703 independent reflections
Radiation source: Incoatec Microsource2673 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.014
ϕ and ω scansθmax = 26.4°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
h = 77
Tmin = 0.898, Tmax = 0.909k = 1011
6386 measured reflectionsl = 2330
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.060 w = 1/[σ2(Fo2) + (0.0281P)2 + 0.3817P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max = 0.001
2703 reflectionsΔρmax = 0.21 e Å3
183 parametersΔρmin = 0.27 e Å3
0 restraintsAbsolute structure: Flack (1983), with 1051 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.13 (6)
Crystal data top
C13H17NO4SV = 1383.0 (2) Å3
Mr = 283.34Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 6.2335 (6) ŵ = 0.24 mm1
b = 8.9651 (8) ÅT = 100 K
c = 24.747 (2) Å0.45 × 0.40 × 0.40 mm
Data collection top
Bruker APEX DUO
diffractometer
2703 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
2673 reflections with I > 2σ(I)
Tmin = 0.898, Tmax = 0.909Rint = 0.014
6386 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.023H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.060Δρmax = 0.21 e Å3
S = 1.11Δρmin = 0.27 e Å3
2703 reflectionsAbsolute structure: Flack (1983), with 1051 Friedel pairs
183 parametersAbsolute structure parameter: 0.13 (6)
0 restraints
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Å2) top
xyzUiso*/Ueq
H1000.227 (3)0.114 (2)0.1744 (8)0.038 (5)*
H2000.052 (4)0.095 (2)0.2469 (9)0.047 (6)*
C10.4679 (3)0.51084 (15)0.21444 (6)0.0201 (3)
H1A0.36490.55020.24070.030*
H1B0.60990.50360.23120.030*
H1C0.47520.57780.18320.030*
C20.3968 (2)0.35844 (16)0.19618 (5)0.0152 (3)
C30.5422 (2)0.27171 (15)0.16540 (5)0.0146 (3)
H30.67890.31370.15790.018*
C40.5001 (2)0.12949 (15)0.14527 (5)0.0142 (3)
C50.6695 (2)0.04891 (16)0.11455 (6)0.0213 (3)
H5A0.63720.05360.07580.032*
H5B0.80900.09560.12140.032*
H5C0.67370.05550.12620.032*
C60.2341 (2)0.07980 (14)0.14310 (5)0.0140 (3)
C70.0890 (2)0.13863 (16)0.18152 (5)0.0145 (3)
C80.0004 (2)0.27918 (15)0.17414 (6)0.0179 (3)
H80.09490.31890.20040.022*
C90.0506 (2)0.36179 (16)0.12850 (6)0.0180 (3)
H90.01010.45790.12330.022*
C100.1906 (2)0.30273 (16)0.09038 (5)0.0155 (3)
C110.2823 (2)0.16203 (14)0.09684 (5)0.0149 (3)
H110.37610.12280.07010.018*
C120.5068 (2)0.48763 (15)0.04731 (6)0.0181 (3)
H12A0.49950.53970.08250.022*
H12B0.61520.40730.05030.022*
C130.5745 (3)0.59713 (18)0.00375 (7)0.0270 (3)
H13A0.56570.54870.03170.040*
H13B0.72240.62940.01040.040*
H13C0.47910.68400.00440.040*
N10.30742 (19)0.06660 (13)0.15389 (5)0.0150 (2)
O10.21083 (16)0.31335 (11)0.20818 (4)0.0205 (2)
O20.04168 (17)0.05041 (11)0.22424 (4)0.0188 (2)
O30.09742 (17)0.52721 (12)0.02798 (5)0.0251 (2)
O40.27808 (18)0.30992 (11)0.01354 (4)0.0207 (2)
S10.25292 (6)0.40846 (3)0.032180 (13)0.01536 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0209 (7)0.0172 (7)0.0221 (7)0.0003 (6)0.0018 (6)0.0054 (6)
C20.0175 (7)0.0161 (6)0.0120 (6)0.0003 (5)0.0016 (5)0.0022 (5)
C30.0147 (7)0.0155 (6)0.0137 (6)0.0026 (5)0.0023 (5)0.0008 (5)
C40.0161 (6)0.0162 (6)0.0103 (6)0.0016 (5)0.0002 (5)0.0021 (5)
C50.0159 (6)0.0202 (7)0.0279 (8)0.0007 (6)0.0048 (6)0.0076 (6)
C60.0132 (6)0.0135 (6)0.0153 (6)0.0005 (6)0.0011 (5)0.0017 (5)
C70.0136 (6)0.0160 (6)0.0138 (6)0.0011 (5)0.0011 (5)0.0007 (5)
C80.0156 (7)0.0182 (7)0.0200 (7)0.0030 (6)0.0037 (6)0.0026 (6)
C90.0186 (7)0.0139 (6)0.0215 (7)0.0040 (5)0.0016 (6)0.0000 (6)
C100.0155 (7)0.0164 (6)0.0145 (6)0.0010 (5)0.0023 (5)0.0012 (5)
C110.0148 (7)0.0158 (6)0.0140 (6)0.0001 (5)0.0000 (5)0.0004 (5)
C120.0170 (7)0.0143 (6)0.0230 (7)0.0011 (6)0.0034 (6)0.0015 (6)
C130.0190 (7)0.0209 (7)0.0411 (9)0.0022 (7)0.0015 (7)0.0069 (7)
N10.0172 (6)0.0128 (5)0.0150 (5)0.0010 (5)0.0047 (5)0.0024 (4)
O10.0209 (6)0.0182 (5)0.0223 (5)0.0022 (4)0.0087 (4)0.0044 (4)
O20.0204 (5)0.0188 (5)0.0173 (5)0.0042 (4)0.0070 (4)0.0024 (4)
O30.0185 (5)0.0246 (5)0.0321 (6)0.0047 (5)0.0010 (5)0.0125 (5)
O40.0258 (6)0.0209 (5)0.0154 (5)0.0056 (5)0.0028 (4)0.0016 (4)
S10.01550 (16)0.01435 (15)0.01623 (15)0.00002 (14)0.00236 (14)0.00376 (11)
Geometric parameters (Å, º) top
C1—C21.5057 (19)C8—C91.387 (2)
C1—H1A0.9800C8—H80.9500
C1—H1B0.9800C9—C101.390 (2)
C1—H1C0.9800C9—H90.9500
C2—O11.2630 (18)C10—C111.3941 (19)
C2—C31.4165 (19)C10—S11.7673 (14)
C3—C41.3937 (19)C11—H110.9500
C3—H30.9500C12—C131.518 (2)
C4—N11.3441 (18)C12—S11.7745 (15)
C4—C51.4879 (19)C12—H12A0.9900
C5—H5A0.9800C12—H12B0.9900
C5—H5B0.9800C13—H13A0.9800
C5—H5C0.9800C13—H13B0.9800
C6—C111.3944 (18)C13—H13C0.9800
C6—C71.4141 (19)N1—H1000.83 (2)
C6—N11.4153 (17)O2—H2000.90 (2)
C7—O21.3530 (16)O3—S11.4435 (11)
C7—C81.388 (2)O4—S11.4441 (10)
C2—C1—H1A109.5C8—C9—H9120.3
C2—C1—H1B109.5C10—C9—H9120.3
H1A—C1—H1B109.5C9—C10—C11121.61 (13)
C2—C1—H1C109.5C9—C10—S1119.14 (11)
H1A—C1—H1C109.5C11—C10—S1119.25 (11)
H1B—C1—H1C109.5C10—C11—C6118.96 (12)
O1—C2—C3122.55 (13)C10—C11—H11120.5
O1—C2—C1119.35 (13)C6—C11—H11120.5
C3—C2—C1118.10 (13)C13—C12—S1110.90 (10)
C4—C3—C2125.03 (13)C13—C12—H12A109.5
C4—C3—H3117.5S1—C12—H12A109.5
C2—C3—H3117.5C13—C12—H12B109.5
N1—C4—C3119.68 (13)S1—C12—H12B109.5
N1—C4—C5120.76 (13)H12A—C12—H12B108.0
C3—C4—C5119.56 (13)C12—C13—H13A109.5
C4—C5—H5A109.5C12—C13—H13B109.5
C4—C5—H5B109.5H13A—C13—H13B109.5
H5A—C5—H5B109.5C12—C13—H13C109.5
C4—C5—H5C109.5H13A—C13—H13C109.5
H5A—C5—H5C109.5H13B—C13—H13C109.5
H5B—C5—H5C109.5C4—N1—C6130.38 (13)
C11—C6—C7119.51 (12)C4—N1—H100115.0 (14)
C11—C6—N1125.14 (12)C6—N1—H100113.3 (14)
C7—C6—N1115.19 (12)C7—O2—H200111.5 (14)
O2—C7—C8123.15 (12)O3—S1—O4117.88 (7)
O2—C7—C6116.54 (12)O3—S1—C10107.85 (7)
C8—C7—C6120.31 (13)O4—S1—C10109.53 (6)
C9—C8—C7120.15 (13)O3—S1—C12108.61 (7)
C9—C8—H8119.9O4—S1—C12108.25 (7)
C7—C8—H8119.9C10—S1—C12103.81 (7)
C8—C9—C10119.43 (13)
O1—C2—C3—C40.3 (2)C7—C6—C11—C101.86 (19)
C1—C2—C3—C4179.55 (13)N1—C6—C11—C10177.04 (13)
C2—C3—C4—N11.3 (2)C3—C4—N1—C6172.26 (13)
C2—C3—C4—C5178.54 (13)C5—C4—N1—C67.6 (2)
C11—C6—C7—O2177.09 (12)C11—C6—N1—C440.5 (2)
N1—C6—C7—O21.45 (18)C7—C6—N1—C4144.18 (14)
C11—C6—C7—C82.0 (2)C9—C10—S1—O315.06 (13)
N1—C6—C7—C8177.69 (12)C11—C10—S1—O3164.72 (11)
O2—C7—C8—C9177.90 (13)C9—C10—S1—O4144.52 (11)
C6—C7—C8—C91.2 (2)C11—C10—S1—O435.25 (13)
C7—C8—C9—C100.1 (2)C9—C10—S1—C12100.05 (12)
C8—C9—C10—C110.0 (2)C11—C10—S1—C1280.17 (12)
C8—C9—C10—S1179.75 (11)C13—C12—S1—O359.05 (12)
C9—C10—C11—C60.8 (2)C13—C12—S1—O470.04 (12)
S1—C10—C11—C6179.38 (10)C13—C12—S1—C10173.62 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H100···O10.83 (2)1.98 (2)2.657 (2)139 (2)
N1—H100···O20.83 (2)2.24 (2)2.622 (2)108 (2)
O2—H200···O1i0.90 (2)1.70 (2)2.601 (1)175 (2)
C1—H1B···O2ii0.982.483.457 (2)172
C12—H12B···O4iii0.992.383.267 (2)149
C13—H13B···O3iv0.982.553.372 (2)142
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2; (iii) x+1/2, y+1/2, z; (iv) x+1, y, z.
(II) (3Z)-4-(5-tert-Butyl-2-hydroxyanilino)pent-3-en-2-one top
Crystal data top
C15H21NO2F(000) = 536
Mr = 247.33Dx = 1.170 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2476 reflections
a = 12.3617 (7) Åθ = 1.7–26.0°
b = 8.3063 (5) ŵ = 0.08 mm1
c = 14.1054 (8) ÅT = 100 K
β = 104.114 (2)°Needle, colourless
V = 1404.62 (14) Å30.40 × 0.25 × 0.18 mm
Z = 4
Data collection top
Bruker APEX DUO
diffractometer
2709 independent reflections
Radiation source: Incoatec microsource2476 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ϕ and ω scansθmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
h = 1512
Tmin = 0.970, Tmax = 0.986k = 910
10867 measured reflectionsl = 1117
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.0425P)2 + 0.825P]
where P = (Fo2 + 2Fc2)/3
2709 reflections(Δ/σ)max = 0.010
176 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C15H21NO2V = 1404.62 (14) Å3
Mr = 247.33Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.3617 (7) ŵ = 0.08 mm1
b = 8.3063 (5) ÅT = 100 K
c = 14.1054 (8) Å0.40 × 0.25 × 0.18 mm
β = 104.114 (2)°
Data collection top
Bruker APEX DUO
diffractometer
2709 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
2476 reflections with I > 2σ(I)
Tmin = 0.970, Tmax = 0.986Rint = 0.016
10867 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.28 e Å3
2709 reflectionsΔρmin = 0.24 e Å3
176 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Å2) top
xyzUiso*/Ueq
O20.83957 (7)0.29365 (12)0.98641 (7)0.0192 (2)
O10.86652 (7)0.10651 (11)0.66786 (6)0.0169 (2)
N10.78093 (8)0.09934 (13)0.82105 (8)0.0148 (2)
C150.29802 (10)0.25200 (18)0.85609 (10)0.0236 (3)
H15A0.30830.36450.83930.035*
H15B0.31180.24140.92720.035*
H15C0.22150.21840.82550.035*
C120.38003 (10)0.14538 (15)0.81904 (10)0.0186 (3)
C100.50147 (10)0.19556 (15)0.86262 (9)0.0157 (3)
C110.58701 (10)0.12996 (15)0.82546 (9)0.0156 (3)
H110.56800.06090.77020.019*
C60.69864 (10)0.16257 (15)0.86668 (9)0.0146 (3)
C40.86111 (10)0.00646 (15)0.85914 (9)0.0150 (3)
C30.93860 (10)0.05218 (15)0.80706 (9)0.0158 (3)
H30.99530.12630.83680.019*
C20.93769 (10)0.00529 (15)0.71269 (9)0.0153 (3)
C11.02283 (11)0.05663 (19)0.66153 (10)0.0250 (3)
H1A0.98490.11380.60190.038*
H1B1.07390.13040.70490.038*
H1C1.06520.03400.64440.038*
C130.36577 (12)0.02851 (18)0.85116 (14)0.0337 (4)
H13A0.38340.03380.92270.051*
H13B0.41630.09950.82680.051*
H13C0.28850.06310.82440.051*
C90.53385 (10)0.29864 (15)0.94273 (9)0.0166 (3)
H90.47800.34680.96930.020*
C80.64531 (10)0.33288 (15)0.98480 (9)0.0166 (3)
H80.66420.40371.03920.020*
C70.72958 (10)0.26451 (15)0.94800 (9)0.0150 (3)
C50.86327 (11)0.07976 (17)0.95670 (9)0.0200 (3)
H5A0.87990.00381.00720.030*
H5B0.92090.16330.97160.030*
H5C0.79040.12780.95510.030*
C140.35188 (11)0.15514 (19)0.70700 (10)0.0262 (3)
H14A0.27310.12820.68060.039*
H14B0.39860.07890.68180.039*
H14C0.36600.26460.68700.039*
H1000.7804 (13)0.133 (2)0.7608 (13)0.027 (4)*
H2000.8488 (16)0.338 (2)1.0476 (16)0.046 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0148 (4)0.0276 (5)0.0156 (5)0.0046 (4)0.0046 (3)0.0064 (4)
O10.0166 (4)0.0208 (5)0.0136 (4)0.0018 (3)0.0040 (3)0.0018 (3)
N10.0153 (5)0.0192 (5)0.0105 (5)0.0006 (4)0.0045 (4)0.0009 (4)
C150.0149 (6)0.0289 (7)0.0264 (7)0.0032 (5)0.0040 (5)0.0003 (6)
C120.0142 (6)0.0166 (6)0.0243 (7)0.0008 (5)0.0033 (5)0.0013 (5)
C100.0155 (6)0.0137 (6)0.0173 (6)0.0015 (5)0.0031 (5)0.0038 (5)
C110.0181 (6)0.0145 (6)0.0136 (6)0.0007 (5)0.0029 (5)0.0003 (5)
C60.0162 (6)0.0161 (6)0.0124 (6)0.0015 (5)0.0054 (5)0.0013 (5)
C40.0144 (6)0.0165 (6)0.0128 (6)0.0029 (4)0.0004 (4)0.0016 (5)
C30.0138 (6)0.0176 (6)0.0150 (6)0.0016 (5)0.0014 (5)0.0010 (5)
C20.0127 (5)0.0165 (6)0.0161 (6)0.0021 (5)0.0028 (5)0.0030 (5)
C10.0223 (7)0.0316 (8)0.0240 (7)0.0065 (6)0.0113 (5)0.0014 (6)
C130.0198 (7)0.0203 (7)0.0580 (11)0.0022 (5)0.0036 (7)0.0090 (7)
C90.0173 (6)0.0156 (6)0.0185 (6)0.0031 (5)0.0072 (5)0.0017 (5)
C80.0210 (6)0.0150 (6)0.0143 (6)0.0001 (5)0.0053 (5)0.0019 (5)
C70.0154 (6)0.0169 (6)0.0129 (6)0.0016 (5)0.0038 (4)0.0022 (5)
C50.0202 (6)0.0244 (7)0.0151 (6)0.0002 (5)0.0038 (5)0.0030 (5)
C140.0171 (6)0.0340 (8)0.0246 (7)0.0006 (6)0.0004 (5)0.0070 (6)
Geometric parameters (Å, º) top
O2—C71.3570 (14)C3—C21.4116 (17)
O2—H2000.92 (2)C3—H30.9500
O1—C21.2686 (15)C2—C11.5045 (17)
N1—C41.3356 (16)C1—H1A0.9800
N1—C61.4298 (15)C1—H1B0.9800
N1—H1000.894 (18)C1—H1C0.9800
C15—C121.5309 (18)C13—H13A0.9800
C15—H15A0.9800C13—H13B0.9800
C15—H15B0.9800C13—H13C0.9800
C15—H15C0.9800C9—C81.3903 (17)
C12—C101.5346 (17)C9—H90.9500
C12—C141.5353 (19)C8—C71.3931 (17)
C12—C131.5367 (19)C8—H80.9500
C10—C91.3962 (18)C5—H5A0.9800
C10—C111.4001 (17)C5—H5B0.9800
C11—C61.3873 (17)C5—H5C0.9800
C11—H110.9500C14—H14A0.9800
C6—C71.4018 (17)C14—H14B0.9800
C4—C31.3945 (17)C14—H14C0.9800
C4—C51.4991 (17)
C7—O2—H200109.2 (12)C2—C1—H1A109.5
C4—N1—C6126.89 (11)C2—C1—H1B109.5
C4—N1—H100115.0 (11)H1A—C1—H1B109.5
C6—N1—H100118.1 (10)C2—C1—H1C109.5
C12—C15—H15A109.5H1A—C1—H1C109.5
C12—C15—H15B109.5H1B—C1—H1C109.5
H15A—C15—H15B109.5C12—C13—H13A109.5
C12—C15—H15C109.5C12—C13—H13B109.5
H15A—C15—H15C109.5H13A—C13—H13B109.5
H15B—C15—H15C109.5C12—C13—H13C109.5
C15—C12—C10111.75 (11)H13A—C13—H13C109.5
C15—C12—C14108.55 (11)H13B—C13—H13C109.5
C10—C12—C14110.61 (10)C8—C9—C10121.98 (11)
C15—C12—C13108.06 (11)C8—C9—H9119.0
C10—C12—C13107.97 (10)C10—C9—H9119.0
C14—C12—C13109.85 (12)C9—C8—C7120.73 (11)
C9—C10—C11116.61 (11)C9—C8—H8119.6
C9—C10—C12123.38 (11)C7—C8—H8119.6
C11—C10—C12119.91 (11)O2—C7—C8123.09 (11)
C6—C11—C10122.14 (11)O2—C7—C6118.77 (11)
C6—C11—H11118.9C8—C7—C6118.13 (11)
C10—C11—H11118.9C4—C5—H5A109.5
C11—C6—C7120.40 (11)C4—C5—H5B109.5
C11—C6—N1118.93 (11)H5A—C5—H5B109.5
C7—C6—N1120.54 (10)C4—C5—H5C109.5
N1—C4—C3120.33 (11)H5A—C5—H5C109.5
N1—C4—C5118.81 (11)H5B—C5—H5C109.5
C3—C4—C5120.81 (11)C12—C14—H14A109.5
C4—C3—C2123.79 (11)C12—C14—H14B109.5
C4—C3—H3118.1H14A—C14—H14B109.5
C2—C3—H3118.1C12—C14—H14C109.5
O1—C2—C3122.63 (11)H14A—C14—H14C109.5
O1—C2—C1117.96 (11)H14B—C14—H14C109.5
C3—C2—C1119.41 (11)
C15—C12—C10—C914.20 (17)N1—C4—C3—C21.04 (19)
C14—C12—C10—C9135.27 (13)C5—C4—C3—C2176.43 (11)
C13—C12—C10—C9104.50 (15)C4—C3—C2—O11.24 (19)
C15—C12—C10—C11169.52 (11)C4—C3—C2—C1177.78 (12)
C14—C12—C10—C1148.46 (16)C11—C10—C9—C81.00 (18)
C13—C12—C10—C1171.77 (15)C12—C10—C9—C8175.39 (11)
C9—C10—C11—C61.15 (18)C10—C9—C8—C70.05 (19)
C12—C10—C11—C6175.38 (11)C9—C8—C7—O2179.87 (11)
C10—C11—C6—C70.24 (19)C9—C8—C7—C60.98 (18)
C10—C11—C6—N1176.12 (11)C11—C6—C7—O2179.98 (11)
C4—N1—C6—C11116.71 (14)N1—C6—C7—O24.21 (17)
C4—N1—C6—C767.42 (17)C11—C6—C7—C80.83 (18)
C6—N1—C4—C3177.34 (11)N1—C6—C7—C8174.98 (11)
C6—N1—C4—C55.14 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H100···O10.89 (2)1.89 (2)2.628 (2)138 (2)
O2—H200···O1i0.92 (2)1.72 (2)2.633 (1)172 (2)
Symmetry code: (i) x, y+1/2, z+1/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC13H17NO4SC15H21NO2
Mr283.34247.33
Crystal system, space groupOrthorhombic, P212121Monoclinic, P21/c
Temperature (K)100100
a, b, c (Å)6.2335 (6), 8.9651 (8), 24.747 (2)12.3617 (7), 8.3063 (5), 14.1054 (8)
α, β, γ (°)90, 90, 9090, 104.114 (2), 90
V3)1383.0 (2)1404.62 (14)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.240.08
Crystal size (mm)0.45 × 0.40 × 0.400.40 × 0.25 × 0.18
Data collection
DiffractometerBruker APEX DUO
diffractometer
Bruker APEX DUO
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2010)
Multi-scan
(SADABS; Bruker, 2010)
Tmin, Tmax0.898, 0.9090.970, 0.986
No. of measured, independent and
observed [I > 2σ(I)] reflections
6386, 2703, 2673 10867, 2709, 2476
Rint0.0140.016
(sin θ/λ)max1)0.6250.618
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.060, 1.11 0.038, 0.100, 1.06
No. of reflections27032709
No. of parameters183176
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.21, 0.270.28, 0.24
Absolute structureFlack (1983), with 1051 Friedel pairs?
Absolute structure parameter0.13 (6)?

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 2012), publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) for (I) top
C2—O11.2630 (18)C7—O21.3530 (16)
C2—C31.4165 (19)C10—S11.7673 (14)
C3—C41.3937 (19)C12—S11.7745 (15)
C4—N11.3441 (18)O3—S11.4435 (11)
C6—N11.4153 (17)O4—S11.4441 (10)
O1—C2—C3122.55 (13)O4—S1—C10109.53 (6)
O1—C2—C1119.35 (13)O3—S1—C12108.61 (7)
C4—N1—C6130.38 (13)O4—S1—C12108.25 (7)
O3—S1—C10107.85 (7)C10—S1—C12103.81 (7)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H100···O10.83 (2)1.98 (2)2.657 (2)139 (2)
N1—H100···O20.83 (2)2.24 (2)2.622 (2)108 (2)
O2—H200···O1i0.90 (2)1.70 (2)2.601 (1)175 (2)
C1—H1B···O2ii0.982.483.457 (2)172
C12—H12B···O4iii0.992.383.267 (2)149
C13—H13B···O3iv0.982.553.372 (2)142
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2; (iii) x+1/2, y+1/2, z; (iv) x+1, y, z.
Comparison of experimental and DFT-calculated bond lengths (Å) for (I) top
BondX-rayKeto tautomerEnol tautomer
C2—O11.263 (2)1.2381.323
C2—C31.416 (2)1.4471.370
C3—C41.394 (2)1.3761.441
C4—N11.344 (2)1.3651.305
N1—C61.415 (2)1.3961.395
Selected geometric parameters (Å, º) for (II) top
O2—C71.3570 (14)N1—C61.4298 (15)
O1—C21.2686 (15)C4—C31.3945 (17)
N1—C41.3356 (16)C3—C21.4116 (17)
C4—N1—C6126.89 (11)O1—C2—C1117.96 (11)
O1—C2—C3122.63 (11)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H100···O10.89 (2)1.89 (2)2.628 (2)138 (2)
O2—H200···O1i0.92 (2)1.72 (2)2.633 (1)172 (2)
Symmetry code: (i) x, y+1/2, z+1/2.
Comparison of experimental and DFT-calculated bond lengths (Å) for (II) top
BondX-rayKeto tautomerEnol tautomer
C2—O11.268 (1)1.2511.326
C2—C31.411 (2)1.4371.372
C3—C41.395 (2)1.3851.443
C4—N11.335 (2)1.3551.308
N1—C61.430 (2)1.4171.408
 

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