An X-ray crystallographic and density functional theory study of (3Z)-4-(5-ethylsulfonyl-2-hydroxyanilino)pent-3-en-2-one and (3Z)-4-(5-tert-butyl-2-hydroxyanilino)pent-3-en-2-one

Article abstract of DOI:10.1107/S0108270113002369

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, C₁₅H ₂₁NO₂, (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. Copyright

Full text of DOI:10.1107/S0108270113002369

organic compounds
Acta Crystallographica Section C
Crystal Structure
delocalization and the presence of keto and enol tautomeric
forms (Shi et al., 2004; Gilli et al., 2000).
Communications
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 Hꢂ ꢂ ꢂH 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-phenyl-
butan-1-one (Dey et al., 2009) and 4-chloro-2-(4-oxopent-2-en-
2-ylamino)phenol (Arıcı et al., 1999), have likewise high-
lighted the occurrence of nonplanar conformations with a
dominant keto tautomer. Planarity in 3-methoxyphenylsali-
cylaldimine, 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 thermo-
chromic 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 syntheti-
cally 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 hy-
droxyphenol 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 N C,
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 posi-
tions. Similar results are obtained for other tridentate deri-
vatives chelated to CuII, NiII, CoII and FeIII, where the metal–
ligand ratios vary from 1:1 to 1:2 (Sallam et al., 2002).
ISSN 0108-2701
An X-ray crystallographic and
density functional theory study of
(3Z)-4-(5-ethylsulfonyl-2-hydroxy-
anilino)pent-3-en-2-one and
(3Z)-4-(5-tert-butyl-2-hydroxy-
anilino)pent-3-en-2-one
Kate J. Akerman* and Orde Q. Munro
School of Chemisty and Physics, University of KwaZulu-Natal, Private Bag X01,
Scottsville, Pietermaritzburg 3209, South Africa
Correspondence e-mail: 205503190@stu.ukzn.ac.za
Received 17 November 2012
Accepted 23 January 2013
Online 5 February 2013
The Schiff base enaminones (3Z)-4-(5-ethylsulfonyl-2-hy-
droxyanilino)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 intra-
molecular 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
Oꢂ ꢂ ꢂH—O hydrogen bond, and consequently also forms
a one-dimensional hydrogen-bonded chain. The DFT-calcu-
lated 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 molꢀ1 lower in energy than
the enol tautomers for (I) and (II), respectively.
Comment
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 O C—C C—N bond lengths reflect electron
In this paper, we report the X-ray structures of the two
tridentate Schiff base enaminones, (3Z)-4-(5-ethylsulfonyl-2-
hydroxyanilino)pent-3-en-2-one, (I), and (3Z)-4-(5-tert-butyl-
258 # 2013 International Union of Crystallography
doi:10.1107/S0108270113002369
Acta Cryst. (2013). C69, 258–262

organic compounds
˚
0.031 (1) A (for atom C6 of part B). The deviations from
2-hydroxyanilino)pent-3-en-2-one, (II) consisting 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 hy-
droxy group on the phenol ring, while (II) has a tert-butyl
group in the para position.
planarity exhibited by (II) are 0.036 (1) (for atom C3 of part
˚
A) and 0.045 (1) A (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 4)
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
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
intermediate between typical C—C single bonds and C
double bonds (Allen et al., 1987). Compounds (I) and (II)
C
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) A
˚
and an average S O bond length of 1.444 (2) A. 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 (Tables 2 and 5).
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—H100ꢂ ꢂ ꢂO1/O2 hydrogen bond is observed. The N1—
H100ꢂ ꢂ ꢂO1 hydrogen bond results in a six-membered ring,
while the N1—H100ꢂ ꢂ ꢂO2 hydrogen bond results in a five-
membered ring. There is also one intermolecular O2—
H200ꢂ ꢂ ꢂO1i hydrogen bond (Table 3). This hydrogen bond
links the molecules into extended one-dimensional columns
collinear with the b axis. There are two additional C—Hꢂ ꢂ ꢂO
interactions (C12—H12Bꢂ ꢂ ꢂO4iii and C1—H1Bꢂ ꢂ ꢂO2ii;
Table 3) 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.
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—H100ꢂ ꢂ ꢂO1 hydrogen bond (Table 6). The
intramolecular hydrogen bonds of (I) and (II) are both
Figure 1
Displacement ellipsoid plots (50% probability surfaces) of (a) (I) and (b)
(II). Intramolecular hydrogen bonds are shown as dashed lines.
ꢃ
Acta Cryst. (2013). C69, 258–262
Akerman and Munro
C13H17NO4S and C15H21NO2 259

organic compounds
Figure 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).
Figure 2
of theory used for the calculations [the r.m.s. differences are
(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 thin lines (purple in the electronic version of the paper). H
atoms not involved in hydrogen bonding have been omitted for clarity.
˚
˚
0.192 A for (I) and 0.190 A for (II)]. Moreover, the DFT-
calculated structures clearly show that the molecules are
nonplanar, with the C11—C6—N1—C4 torsion angle in (I)
measuring 29.81ꢀ for the keto tautomer and 29.58ꢀ for the enol
tautomer; the corresponding dihedral angles for (II) are
ꢁ120.97 and ꢁ123.29ꢀ. In both cases, the calculated confor-
mations are in good agreement with those determined
experimentally.
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 the intra-
molecular hydrogen bond, atom O1 also acts as a hydrogen-
bond acceptor for an intermolecular hydrogen bond from the
O2—H200 group (O2—H200ꢂ ꢂ ꢂO1i; Table 6). This interaction
results in a one-dimensional hydrogen-bonded chain collinear
with the c axis. The intermolecular hydrogen bond is char-
acterized 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—H5Bꢂ ꢂ ꢂO2 interaction
involving the methyl group of the bridge.
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 length of 1.237 A, while the enol
˚
tautomer has a bond length of 1.323 A; the former matches
that observed for the X-ray structure [C2—O1
˚
=
1.2630 (18) A; 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 1.441 A, respectively, in
the DFT-calculated structures. As noted above, the X-ray
˚
structure of (I) has a C3—C4 bond length of 1.3937 (19) A and
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 similarity 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
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 1 and 4.
Collectively, the bond lengths of the calculated keto tautomers
of (I) and (II) are in excellent agreement with the corre-
sponding X-ray data, confirming that the keto tautomers are
favoured in the solid state. Interestingly, the present calcula-
tions show that the keto tautomers are favoured over the enol
tautomers by 20.55 and 18.86 kJ molꢁ1 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).
ꢃ
260 Akerman and Munro
C13H17NO4S and C15H21NO2
Acta Cryst. (2013). C69, 258–262

organic compounds
Table 1
Comparison of experimental and DFT-calculated bond lengths (A) for
(I).
Experimental
˚
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 crystals of (I) formed by slow evaporation
Bond
X-ray
Keto tautomer
Enol tautomer
C2—O1
C2—C3
C3—C4
C4—N1
N1—C6
1.2630 (18)
1.4165 (19)
1.3937 (19)
1.3441 (18)
1.4153 (17)
1.238
1.447
1.376
1.365
1.396
1.323
1.370
1.441
1.305
1.395
1
(yield: 1.565 g, 55%). H NMR (400 MHz, DMSO-d6, 303 K): ꢀ 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,
3
4
1H, aromatic CH), 7.50 (dd, J = 8.4 Hz, J = 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): ꢀ 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.
Table 2
Selected geometric parameters (A, ) for (I).
ꢀ
˚
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). 1H NMR (400 MHz, DMSO-d6, 303 K): ꢀ 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,
C7—O2
C10—S1
C12—S1
1.3530 (16)
1.7673 (14)
1.7745 (15)
O3—S1
O4—S1
1.4435 (11)
1.4441 (10)
O1—C2—C3
O1—C2—C1
C4—N1—C6
O3—S1—C10
122.55 (13)
119.35 (13)
130.38 (13)
107.85 (7)
O4—S1—C10
O3—S1—C12
O4—S1—C12
C10—S1—C12
109.53 (6)
108.61 (7)
108.25 (7)
103.81 (7)
Table 3
Hydrogen-bond geometry (A, ) for (I).
ꢀ
˚
4
aromatic CH), 7.09 (d, J= 2.5 Hz, 1H, aromatic CH), 9.62 (s, 1H,
OH), 12.10 (s, 1H, NH); 13C NMR (100 MHz, CDCl3, 303 K): ꢀ 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.
D—Hꢂ ꢂ ꢂA
D—H
Hꢂ ꢂ ꢂA
Dꢂ ꢂ ꢂA
D—Hꢂ ꢂ ꢂA
N1—H100ꢂ ꢂ ꢂO1
N1—H100ꢂ ꢂ ꢂO2
O2—H200ꢂ ꢂ ꢂO1i
C1—H1Bꢂ ꢂ ꢂO2ii
C12—H12Bꢂ ꢂ ꢂO4iii
C13—H13Bꢂ ꢂ ꢂO3iv
0.83 (2)
0.83 (2)
0.90 (2)
0.98
0.99
0.98
1.98 (2)
2.24 (2)
1.70 (2)
2.48
2.38
2.55
2.657 (2)
2.622 (2)
2.601 (1)
3.457 (2)
3.267 (2)
3.372 (2)
139 (2)
108 (2)
175 (2)
172
149
142
Compound (I)
Crystal data
1
2
1
2
1
2
1
2
1
2
1
2
Symmetry code: (i) ꢁx; y þ ; ꢁz þ ; (ii) ꢁx þ 1; y ꢁ ; ꢁz þ ; (iii) x þ ; ꢁy þ ; ꢁz;
3
˚
C13H17NO4S
Mr = 283.34
V = 1383.0 (2) A
Z = 4
(iv) x þ 1; y; z.
Orthorhombic, P212121
˚
Mo Kꢁ radiation
ꢂ = 0.24 mmꢁ1
T = 100 K
0.45 ꢄ 0.40 ꢄ 0.40 mm
a = 6.2335 (6) A
˚
Table 4
Comparison of experimental and DFT-calculated bond lengths (A) for
(II).
b = 8.9651 (8) A
˚
c = 24.747 (2) A
˚
Data collection
Bond
X-ray
Keto tautomer
Enol tautomer
Bruker APEX DUO diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
6386 measured reflections
2703 independent reflections
2673 reflections with I > 2ꢃ(I)
Rint = 0.014
C2—O1
C2—C3
C3—C4
C4—N1
N1—C6
1.2686 (15)
1.4116 (17)
1.3945 (17)
1.3356 (16)
1.4298 (15)
1.251
1.437
1.385
1.355
1.417
1.326
1.372
1.443
1.308
1.408
Tmin = 0.898, Tmax = 0.909
Refinement
ꢁ3
R[F2 > 2ꢃ(F2)] = 0.023
wR(F2) = 0.060
S = 1.11
2703 reflections
183 parameters
Áꢄmax = 0.21 e A
˚
ꢁ3
˚
Áꢄmin = ꢁ0.27 e A
Table 5
Selected geometric parameters (A, ) for (II).
Absolute structure: Flack (1983),
with 1051 Friedel pairs
Flack parameter: 0.13 (6)
ꢀ
˚
O2—C7
1.3570 (14)
H atoms treated by a mixture of
independent and constrained
refinement
C4—N1—C6
O1—C2—C3
126.89 (11)
122.63 (11)
O1—C2—C1
117.96 (11)
Compound (II)
Crystal data
Table 6
Hydrogen-bond geometry (A, ) for (II).
ꢀ
˚
3
˚
V = 1404.62 (14) A
Z = 4
Mo Kꢁ radiation
ꢂ = 0.08 mmꢁ1
T = 100 K
C15H21NO2
Mr = 247.33
D—Hꢂ ꢂ ꢂA
D—H
Hꢂ ꢂ ꢂA
Dꢂ ꢂ ꢂA
D—Hꢂ ꢂ ꢂA
Monoclinic, P21=c
˚
a = 12.3617 (7) A
N1—H100ꢂ ꢂ ꢂO1
0.89 (2)
0.92 (2)
1.89 (2)
1.72 (2)
2.628 (2)
2.633 (1)
138 (2)
172 (2)
˚
b = 8.3063 (5) A
O2—H200ꢂ ꢂ ꢂO1i
˚
c = 14.1054 (8) A
0.40 ꢄ 0.25 ꢄ 0.18 mm
ꢅ = 104.114 (2)ꢀ
1
2
1
2
Symmetry code: (i) x; ꢁy þ ; z þ .
ꢃ
Acta Cryst. (2013). C69, 258–262
Akerman and Munro
C13H17NO4S and C15H21NO2 261

organic compounds
¨
Arıcı, C., Tahir, M. N., Ulku, D. & Atakol, O. (1999). Acta Cryst. C55, 1691–
1692.
¨
Data collection
Bruker APEX DUO diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
10867 measured reflections
2709 independent reflections
2476 reflections with I > 2ꢃ(I)
Rint = 0.016
Becke, A. D. (1993). J. Chem. Phys. 98, 5648–5652.
Bruker (2010). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Burgi, H. B. & Dunitz, J. D. (1971). Helv. Chim. Acta, 54, 1255–1266.
Dey, D. K., Dey, S. P., Karan, N. K., Datta, A., Lycka, A. & Rosair, G. M.
(2009). J. Organomet. Chem. 694, 2434–2441.
Tmin = 0.970, Tmax = 0.986
Refinement
R[F2 > 2ꢃ(F2)] = 0.038
wR(F2) = 0.100
S = 1.06
2709 reflections
176 parameters
H atoms treated by a mixture of
independent and constrained
refinement
Doherty, S., Errington, R. J., Housley, N., Ridland, J., Clegg, W. & Elsegood,
M. R. J. (1999). Organometallics, 18, 1018–1029.
Elmali, A., Kabak, M. & Elerman, Y. (1999). J. Mol. Struct. 484, 229–234.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
ꢁ3
˚
Áꢄmax = 0.28 e A
ꢁ3
˚
Áꢄmin = ꢁ0.24 e A
Frisch, M. J., et al. (2009). GAUSSIAN. Gaussian Inc., Wallingford, Connecti-
cut, USA.
Gilli, P., Bertolasi, V., Ferretti, V. & Gilli, G. (2000). J. Am. Chem. Soc. 122,
10405–10412.
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hedron, 43, 1345–1360.
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J. Organomet. Chem. 620, 1–7.
The positions of all C-bonded H atoms were calculated using a
˚
standard riding model, with aromatic C—H = 0.95 A and Uiso(H) =
˚
1.2Ueq(C), methylene C—H = 0.99 A and Uiso(H) = 1.2Ueq(C), and
˚
methyl C—H = 0.96 A and Uiso(H) = 1.5Ueq(C). The amino and
hydroxy H atoms were located in difference density maps and
allowed to refine isotropically.
For both compounds, data collection: APEX2 (Bruker, 2010); cell
refinement: SAINT (Bruker, 2010); data reduction: SAINT;
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).
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3709–3715.
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Met. Chem. 27, 447–453.
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11, 7379–7386.
The authors thank the University of KwaZulu–Natal for
financial support and the use of facilities, and the National
Research Foundation (South Africa) for funding.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Shi, Y.-C., Yang, H.-M., Shen, W.-B., Yan, C.-G. & Hu, X.-Y. (2004). Poly-
hedron, 23, 15–21.
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Phys. 98, 11623–11627.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: YP3023). Services for accessing these data are
described at the back of the journal.
Vosko, S. H., Wilk, L. & Nusair, M. (1980). Can. J. Phys. 58, 1200–1211.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
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R.-X. (1997). Polyhedron, 16, 2991–3001.
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References
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J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
ꢃ
262 Akerman and Munro
C13H17NO4S and C15H21NO2
Acta Cryst. (2013). C69, 258–262

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 258-262 [doi:10.1107/S0108270113002369]
An X-ray crystallographic and density functional theory study of (3Z)-4-(5-ethyl-
sulfonyl-2-hydroxyanilino)pent-3-en-2-one and (3Z)-4-(5-tert-butyl-2-hydroxy-
anilino)pent-3-en-2-one
Kate J. Akerman and Orde Q. Munro
(I) (3Z)-4-(5-Ethylsulfonyl-2-hydroxyanilino)pent-3-en-2-one
Crystal data
C13H17NO4S
Mr = 283.34
F(000) = 600
Dx = 1.361 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2673 reflections
θ = 1.6–26.4°
Orthorhombic, P212121
Hall symbol: P 2ac 2ab
a = 6.2335 (6) Å
b = 8.9651 (8) Å
c = 24.747 (2) Å
V = 1383.0 (2) Å3
Z = 4
µ = 0.24 mm−1
T = 100 K
Block, brown
0.45 × 0.40 × 0.40 mm
Data collection
Bruker APEX DUO
diffractometer
Radiation source: Incoatec Microsource
Graphite monochromator
φ and ω scans
6386 measured reflections
2703 independent reflections
2673 reflections with I > 2σ(I)
Rint = 0.014
θ
max = 26.4°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
h = −7→7
k = −10→11
l = −23→30
T
min = 0.898, Tmax = 0.909
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.023
wR(F2) = 0.060
S = 1.11
2703 reflections
Hydrogen site location: inferred from
neighbouring sites
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0281P)2 + 0.3817P]
where P = (Fo2 + 2Fc2)/3
183 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
(Δ/σ)max = 0.001
Δρmax = 0.21 e Å−3
Δρmin = −0.27 e Å−3
Absolute structure: Flack (1983), with 1051
Friedel pairs
Flack parameter: 0.13 (6)
Acta Cryst. (2013). C69, 258-262
sup-1

supplementary materials
Special details
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)
x
y
z
Uiso*/Ueq
H100
H200
C1
0.227 (3)
−0.052 (4)
0.4679 (3)
0.3649
−0.114 (2)
0.095 (2)
0.1744 (8)
0.2469 (9)
0.21444 (6)
0.2407
0.038 (5)*
0.047 (6)*
0.0201 (3)
0.030*
−0.51084 (15)
−0.5502
H1A
H1B
H1C
C2
0.6099
−0.5036
0.2312
0.030*
0.4752
−0.5778
0.1832
0.030*
0.3968 (2)
0.5422 (2)
0.6789
−0.35844 (16)
−0.27171 (15)
−0.3137
0.19618 (5)
0.16540 (5)
0.1579
0.0152 (3)
0.0146 (3)
0.018*
C3
H3
C4
0.5001 (2)
0.6695 (2)
0.6372
−0.12949 (15)
−0.04891 (16)
−0.0536
0.14527 (5)
0.11455 (6)
0.0758
0.0142 (3)
0.0213 (3)
0.032*
C5
H5A
H5B
H5C
C6
0.8090
−0.0956
0.1214
0.032*
0.6737
0.0555
0.1262
0.032*
0.2341 (2)
0.0890 (2)
0.0004 (2)
−0.0949
0.07980 (14)
0.13863 (16)
0.27918 (15)
0.3189
0.14310 (5)
0.18152 (5)
0.17414 (6)
0.2004
0.0140 (3)
0.0145 (3)
0.0179 (3)
0.022*
C7
C8
H8
C9
0.0506 (2)
−0.0101
0.36179 (16)
0.4579
0.12850 (6)
0.1233
0.0180 (3)
0.022*
H9
C10
C11
H11
C12
H12A
H12B
C13
H13A
H13B
H13C
N1
0.1906 (2)
0.2823 (2)
0.3761
0.30273 (16)
0.16203 (14)
0.1228
0.09038 (5)
0.09684 (5)
0.0701
0.0155 (3)
0.0149 (3)
0.018*
0.5068 (2)
0.4995
0.48763 (15)
0.5397
0.04731 (6)
0.0825
0.0181 (3)
0.022*
0.6152
0.4073
0.0503
0.022*
0.5745 (3)
0.5657
0.59713 (18)
0.5487
0.00375 (7)
−0.0317
0.0270 (3)
0.040*
0.7224
0.6294
0.0104
0.040*
0.4791
0.6840
0.0044
0.040*
0.30742 (19)
0.21083 (16)
0.04168 (17)
0.09742 (17)
0.27808 (18)
0.25292 (6)
−0.06660 (13)
−0.31335 (11)
0.05041 (11)
0.52721 (12)
0.30992 (11)
0.40846 (3)
0.15389 (5)
0.20818 (4)
0.22424 (4)
0.02798 (5)
−0.01354 (4)
0.032180 (13)
0.0150 (2)
0.0205 (2)
0.0188 (2)
0.0251 (2)
0.0207 (2)
0.01536 (9)
O1
O2
O3
O4
S1
Acta Cryst. (2013). C69, 258-262
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supplementary materials
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
N1
O1
O2
O3
O4
S1
0.0209 (7)
0.0175 (7)
0.0147 (7)
0.0161 (6)
0.0159 (6)
0.0132 (6)
0.0136 (6)
0.0156 (7)
0.0186 (7)
0.0155 (7)
0.0148 (7)
0.0170 (7)
0.0190 (7)
0.0172 (6)
0.0209 (6)
0.0204 (5)
0.0185 (5)
0.0258 (6)
0.01550 (16)
0.0172 (7)
0.0161 (6)
0.0155 (6)
0.0162 (6)
0.0202 (7)
0.0135 (6)
0.0160 (6)
0.0182 (7)
0.0139 (6)
0.0164 (6)
0.0158 (6)
0.0143 (6)
0.0209 (7)
0.0128 (5)
0.0182 (5)
0.0188 (5)
0.0246 (5)
0.0209 (5)
0.01435 (15)
0.0221 (7)
0.0120 (6)
0.0137 (6)
0.0103 (6)
0.0279 (8)
0.0153 (6)
0.0138 (6)
0.0200 (7)
0.0215 (7)
0.0145 (6)
0.0140 (6)
0.0230 (7)
0.0411 (9)
0.0150 (5)
0.0223 (5)
0.0173 (5)
0.0321 (6)
0.0154 (5)
0.01623 (15)
0.0003 (6)
−0.0003 (5)
0.0026 (5)
−0.0016 (5)
0.0007 (6)
−0.0005 (6)
−0.0011 (5)
0.0030 (6)
0.0040 (5)
−0.0010 (5)
0.0001 (5)
−0.0011 (6)
−0.0022 (7)
0.0010 (5)
0.0022 (4)
0.0042 (4)
0.0047 (5)
−0.0056 (5)
−0.00002 (14)
−0.0018 (6)
−0.0016 (5)
0.0023 (5)
0.0002 (5)
0.0048 (6)
−0.0011 (5)
0.0011 (5)
0.0037 (6)
−0.0016 (6)
−0.0023 (5)
0.0000 (5)
−0.0034 (6)
0.0015 (7)
0.0047 (5)
0.0087 (4)
0.0070 (4)
0.0010 (5)
−0.0028 (4)
−0.00236 (14)
0.0054 (6)
−0.0022 (5)
−0.0008 (5)
−0.0021 (5)
0.0076 (6)
−0.0017 (5)
−0.0007 (5)
−0.0026 (6)
0.0000 (6)
0.0012 (5)
−0.0004 (5)
−0.0015 (6)
0.0069 (7)
0.0024 (4)
0.0044 (4)
0.0024 (4)
0.0125 (5)
0.0016 (4)
0.00376 (11)
Geometric parameters (Å, º)
C1—C2
C1—H1A
C1—H1B
C1—H1C
C2—O1
C2—C3
C3—C4
C3—H3
C4—N1
C4—C5
C5—H5A
C5—H5B
C5—H5C
C6—C11
C6—C7
C6—N1
C7—O2
C7—C8
1.5057 (19)
C8—C9
1.387 (2)
0.9800
C8—H8
0.9500
0.9800
C9—C10
1.390 (2)
0.9500
0.9800
C9—H9
1.2630 (18)
1.4165 (19)
1.3937 (19)
0.9500
C10—C11
C10—S1
1.3941 (19)
1.7673 (14)
0.9500
C11—H11
C12—C13
C12—S1
1.518 (2)
1.7745 (15)
0.9900
1.3441 (18)
1.4879 (19)
0.9800
C12—H12A
C12—H12B
C13—H13A
C13—H13B
C13—H13C
N1—H100
O2—H200
O3—S1
0.9900
0.9800
0.9800
0.9800
0.9800
1.3944 (18)
1.4141 (19)
1.4153 (17)
1.3530 (16)
1.388 (2)
0.9800
0.83 (2)
0.90 (2)
1.4435 (11)
1.4441 (10)
O4—S1
C2—C1—H1A
C2—C1—H1B
H1A—C1—H1B
C2—C1—H1C
H1A—C1—H1C
H1B—C1—H1C
109.5
109.5
109.5
109.5
109.5
109.5
C8—C9—H9
120.3
C10—C9—H9
C9—C10—C11
C9—C10—S1
C11—C10—S1
C10—C11—C6
120.3
121.61 (13)
119.14 (11)
119.25 (11)
118.96 (12)
Acta Cryst. (2013). C69, 258-262
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supplementary materials
O1—C2—C3
O1—C2—C1
C3—C2—C1
C4—C3—C2
C4—C3—H3
C2—C3—H3
N1—C4—C3
N1—C4—C5
C3—C4—C5
C4—C5—H5A
C4—C5—H5B
H5A—C5—H5B
C4—C5—H5C
H5A—C5—H5C
H5B—C5—H5C
C11—C6—C7
C11—C6—N1
C7—C6—N1
O2—C7—C8
O2—C7—C6
C8—C7—C6
C9—C8—C7
C9—C8—H8
C7—C8—H8
C8—C9—C10
122.55 (13)
119.35 (13)
118.10 (13)
125.03 (13)
117.5
C10—C11—H11
C6—C11—H11
C13—C12—S1
120.5
120.5
110.90 (10)
109.5
C13—C12—H12A
S1—C12—H12A
C13—C12—H12B
S1—C12—H12B
109.5
117.5
109.5
119.68 (13)
120.76 (13)
119.56 (13)
109.5
109.5
H12A—C12—H12B
C12—C13—H13A
C12—C13—H13B
H13A—C13—H13B
C12—C13—H13C
H13A—C13—H13C
H13B—C13—H13C
C4—N1—C6
108.0
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
130.38 (13)
115.0 (14)
113.3 (14)
111.5 (14)
117.88 (7)
107.85 (7)
109.53 (6)
108.61 (7)
108.25 (7)
103.81 (7)
119.51 (12)
125.14 (12)
115.19 (12)
123.15 (12)
116.54 (12)
120.31 (13)
120.15 (13)
119.9
C4—N1—H100
C6—N1—H100
C7—O2—H200
O3—S1—O4
O3—S1—C10
O4—S1—C10
O3—S1—C12
O4—S1—C12
119.9
C10—S1—C12
119.43 (13)
O1—C2—C3—C4
C1—C2—C3—C4
C2—C3—C4—N1
C2—C3—C4—C5
C11—C6—C7—O2
N1—C6—C7—O2
C11—C6—C7—C8
N1—C6—C7—C8
O2—C7—C8—C9
C6—C7—C8—C9
C7—C8—C9—C10
C8—C9—C10—C11
C8—C9—C10—S1
C9—C10—C11—C6
S1—C10—C11—C6
0.3 (2)
C7—C6—C11—C10
N1—C6—C11—C10
C3—C4—N1—C6
C5—C4—N1—C6
C11—C6—N1—C4
C7—C6—N1—C4
C9—C10—S1—O3
C11—C10—S1—O3
C9—C10—S1—O4
C11—C10—S1—O4
C9—C10—S1—C12
C11—C10—S1—C12
C13—C12—S1—O3
C13—C12—S1—O4
C13—C12—S1—C10
1.86 (19)
179.55 (13)
−1.3 (2)
177.04 (13)
172.26 (13)
−7.6 (2)
178.54 (13)
177.09 (12)
1.45 (18)
−2.0 (2)
40.5 (2)
−144.18 (14)
−15.06 (13)
164.72 (11)
−144.52 (11)
35.25 (13)
100.05 (12)
−80.17 (12)
−59.05 (12)
70.04 (12)
−173.62 (11)
−177.69 (12)
−177.90 (13)
1.2 (2)
−0.1 (2)
0.0 (2)
179.75 (11)
−0.8 (2)
179.38 (10)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H100···O1
N1—H100···O2
O2—H200···O1i
C1—H1B···O2ii
0.83 (2)
0.83 (2)
0.90 (2)
0.98
1.98 (2)
2.24 (2)
1.70 (2)
2.48
2.657 (2)
2.622 (2)
2.601 (1)
3.457 (2)
139 (2)
108 (2)
175 (2)
172
Acta Cryst. (2013). C69, 258-262
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supplementary materials
C12—H12B···O4iii
C13—H13B···O3iv
0.99
0.98
2.38
2.55
3.267 (2)
3.372 (2)
149
142
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −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
Crystal data
C15H21NO2
Mr = 247.33
F(000) = 536
Dx = 1.170 Mg m−3
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 12.3617 (7) Å
b = 8.3063 (5) Å
c = 14.1054 (8) Å
β = 104.114 (2)°
V = 1404.62 (14) Å3
Z = 4
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2476 reflections
θ = 1.7–26.0°
µ = 0.08 mm−1
T = 100 K
Needle, colourless
0.40 × 0.25 × 0.18 mm
Data collection
Bruker APEX DUO
diffractometer
Radiation source: Incoatec microsource
Graphite monochromator
φ and ω scans
10867 measured reflections
2709 independent reflections
2476 reflections with I > 2σ(I)
Rint = 0.016
θ
max = 26.0°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2010)
h = −15→12
k = −9→10
l = −11→17
T
min = 0.970, Tmax = 0.986
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.038
wR(F2) = 0.100
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.06
2709 reflections
176 parameters
0 restraints
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0425P)2 + 0.825P]
where P = (Fo2 + 2Fc2)/3
Primary atom site location: structure-invariant
direct methods
(Δ/σ)max = 0.010
Δρmax = 0.28 e Å−3
Δρmin = −0.24 e Å−3
Special details
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.
Acta Cryst. (2013). C69, 258-262
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supplementary materials
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
O2
0.83957 (7)
0.86652 (7)
0.78093 (8)
0.29802 (10)
0.3083
0.29365 (12)
0.10651 (11)
0.09934 (13)
0.25200 (18)
0.3645
0.98641 (7)
0.66786 (6)
0.82105 (8)
0.85609 (10)
0.8393
0.0192 (2)
0.0169 (2)
0.0148 (2)
0.0236 (3)
0.035*
O1
N1
C15
H15A
H15B
H15C
C12
C10
C11
H11
C6
0.3118
0.2414
0.9272
0.035*
0.2215
0.2184
0.8255
0.035*
0.38003 (10)
0.50147 (10)
0.58701 (10)
0.5680
0.14538 (15)
0.19556 (15)
0.12996 (15)
0.0609
0.81904 (10)
0.86262 (9)
0.82546 (9)
0.7702
0.0186 (3)
0.0157 (3)
0.0156 (3)
0.019*
0.69864 (10)
0.86111 (10)
0.93860 (10)
0.9953
0.16257 (15)
−0.00646 (15)
−0.05218 (15)
−0.1263
0.86668 (9)
0.85914 (9)
0.80706 (9)
0.8368
0.0146 (3)
0.0150 (3)
0.0158 (3)
0.019*
C4
C3
H3
C2
0.93769 (10)
1.02283 (11)
0.9849
0.00529 (15)
−0.05663 (19)
−0.1138
0.71269 (9)
0.66153 (10)
0.6019
0.0153 (3)
0.0250 (3)
0.038*
C1
H1A
H1B
H1C
C13
H13A
H13B
H13C
C9
1.0739
−0.1304
0.7049
0.038*
1.0652
0.0340
0.6444
0.038*
0.36577 (12)
0.3834
−0.02851 (18)
−0.0338
0.85116 (14)
0.9227
0.0337 (4)
0.051*
0.4163
−0.0995
0.8268
0.051*
0.2885
−0.0631
0.8244
0.051*
0.53385 (10)
0.4780
0.29864 (15)
0.3468
0.94273 (9)
0.9693
0.0166 (3)
0.020*
H9
C8
0.64531 (10)
0.6642
0.33288 (15)
0.4037
0.98480 (9)
1.0392
0.0166 (3)
0.020*
H8
C7
0.72958 (10)
0.86327 (11)
0.8799
0.26451 (15)
−0.07976 (17)
0.0038
0.94800 (9)
0.95670 (9)
1.0072
0.0150 (3)
0.0200 (3)
0.030*
C5
H5A
H5B
H5C
C14
H14A
H14B
H14C
H100
H200
0.9209
−0.1633
0.9716
0.030*
0.7904
−0.1278
0.9551
0.030*
0.35188 (11)
0.2731
0.15514 (19)
0.1282
0.70700 (10)
0.6806
0.0262 (3)
0.039*
0.3986
0.0789
0.6818
0.039*
0.3660
0.2646
0.6870
0.039*
0.7804 (13)
0.8488 (16)
0.133 (2)
0.7608 (13)
1.0476 (16)
0.027 (4)*
0.046 (5)*
0.338 (2)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O2
O1
N1
C15
0.0148 (4)
0.0166 (4)
0.0153 (5)
0.0149 (6)
0.0276 (5)
0.0208 (5)
0.0192 (5)
0.0289 (7)
0.0156 (5)
0.0136 (4)
0.0105 (5)
0.0264 (7)
−0.0046 (4)
0.0018 (3)
0.0006 (4)
0.0032 (5)
0.0046 (3)
0.0040 (3)
0.0045 (4)
0.0040 (5)
−0.0064 (4)
0.0018 (3)
−0.0009 (4)
0.0003 (6)
Acta Cryst. (2013). C69, 258-262
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supplementary materials
C12
C10
C11
C6
0.0142 (6)
0.0155 (6)
0.0181 (6)
0.0162 (6)
0.0144 (6)
0.0138 (6)
0.0127 (5)
0.0223 (7)
0.0198 (7)
0.0173 (6)
0.0210 (6)
0.0154 (6)
0.0202 (6)
0.0171 (6)
0.0166 (6)
0.0137 (6)
0.0145 (6)
0.0161 (6)
0.0165 (6)
0.0176 (6)
0.0165 (6)
0.0316 (8)
0.0203 (7)
0.0156 (6)
0.0150 (6)
0.0169 (6)
0.0244 (7)
0.0340 (8)
0.0243 (7)
0.0173 (6)
0.0136 (6)
0.0124 (6)
0.0128 (6)
0.0150 (6)
0.0161 (6)
0.0240 (7)
0.0580 (11)
0.0185 (6)
0.0143 (6)
0.0129 (6)
0.0151 (6)
0.0246 (7)
0.0008 (5)
0.0015 (5)
0.0007 (5)
0.0015 (5)
−0.0029 (4)
0.0016 (5)
−0.0021 (5)
0.0065 (6)
−0.0022 (5)
0.0031 (5)
0.0001 (5)
−0.0016 (5)
0.0002 (5)
−0.0006 (6)
0.0033 (5)
0.0031 (5)
0.0029 (5)
0.0054 (5)
0.0004 (4)
0.0014 (5)
0.0028 (5)
0.0113 (5)
0.0036 (7)
0.0072 (5)
0.0053 (5)
0.0038 (4)
0.0038 (5)
−0.0004 (5)
0.0013 (5)
0.0038 (5)
−0.0003 (5)
0.0013 (5)
−0.0016 (5)
−0.0010 (5)
−0.0030 (5)
0.0014 (6)
0.0090 (7)
0.0017 (5)
−0.0019 (5)
0.0022 (5)
0.0030 (5)
−0.0070 (6)
C4
C3
C2
C1
C13
C9
C8
C7
C5
C14
Geometric parameters (Å, º)
O2—C7
1.3570 (14)
C3—C2
1.4116 (17)
O2—H200
O1—C2
0.92 (2)
C3—H3
0.9500
1.2686 (15)
1.3356 (16)
1.4298 (15)
0.894 (18)
1.5309 (18)
0.9800
C2—C1
1.5045 (17)
0.9800
N1—C4
C1—H1A
C1—H1B
C1—H1C
C13—H13A
C13—H13B
C13—H13C
C9—C8
N1—C6
0.9800
N1—H100
C15—C12
C15—H15A
C15—H15B
C15—H15C
C12—C10
C12—C14
C12—C13
C10—C9
C10—C11
C11—C6
C11—H11
C6—C7
0.9800
0.9800
0.9800
0.9800
0.9800
0.9800
1.3903 (17)
0.9500
1.5346 (17)
1.5353 (19)
1.5367 (19)
1.3962 (18)
1.4001 (17)
1.3873 (17)
0.9500
C9—H9
C8—C7
1.3931 (17)
0.9500
C8—H8
C5—H5A
C5—H5B
C5—H5C
C14—H14A
C14—H14B
C14—H14C
0.9800
0.9800
0.9800
0.9800
1.4018 (17)
1.3945 (17)
1.4991 (17)
0.9800
C4—C3
0.9800
C4—C5
C7—O2—H200
109.2 (12)
126.89 (11)
115.0 (11)
118.1 (10)
109.5
C2—C1—H1A
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
C4—N1—C6
C2—C1—H1B
C4—N1—H100
H1A—C1—H1B
C2—C1—H1C
C6—N1—H100
C12—C15—H15A
C12—C15—H15B
H15A—C15—H15B
C12—C15—H15C
H15A—C15—H15C
H15B—C15—H15C
C15—C12—C10
C15—C12—C14
H1A—C1—H1C
H1B—C1—H1C
C12—C13—H13A
C12—C13—H13B
H13A—C13—H13B
C12—C13—H13C
H13A—C13—H13C
H13B—C13—H13C
109.5
109.5
109.5
109.5
109.5
111.75 (11)
108.55 (11)
Acta Cryst. (2013). C69, 258-262
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supplementary materials
C10—C12—C14
C15—C12—C13
C10—C12—C13
C14—C12—C13
C9—C10—C11
C9—C10—C12
C11—C10—C12
C6—C11—C10
C6—C11—H11
C10—C11—H11
C11—C6—C7
C11—C6—N1
C7—C6—N1
110.61 (10)
108.06 (11)
107.97 (10)
109.85 (12)
116.61 (11)
123.38 (11)
119.91 (11)
122.14 (11)
118.9
C8—C9—C10
C8—C9—H9
121.98 (11)
119.0
C10—C9—H9
C9—C8—C7
119.0
120.73 (11)
119.6
C9—C8—H8
C7—C8—H8
119.6
O2—C7—C8
123.09 (11)
118.77 (11)
118.13 (11)
109.5
O2—C7—C6
C8—C7—C6
118.9
C4—C5—H5A
C4—C5—H5B
H5A—C5—H5B
C4—C5—H5C
H5A—C5—H5C
H5B—C5—H5C
C12—C14—H14A
C12—C14—H14B
120.40 (11)
118.93 (11)
120.54 (10)
120.33 (11)
118.81 (11)
120.81 (11)
123.79 (11)
118.1
109.5
109.5
109.5
N1—C4—C3
109.5
N1—C4—C5
109.5
C3—C4—C5
109.5
C4—C3—C2
109.5
C4—C3—H3
H14A—C14—H14B
C12—C14—H14C
H14A—C14—H14C
H14B—C14—H14C
109.5
109.5
109.5
109.5
C2—C3—H3
118.1
O1—C2—C3
122.63 (11)
117.96 (11)
119.41 (11)
O1—C2—C1
C3—C2—C1
C15—C12—C10—C9
C14—C12—C10—C9
C13—C12—C10—C9
C15—C12—C10—C11
C14—C12—C10—C11
C13—C12—C10—C11
C9—C10—C11—C6
C12—C10—C11—C6
C10—C11—C6—C7
C10—C11—C6—N1
C4—N1—C6—C11
C4—N1—C6—C7
14.20 (17)
N1—C4—C3—C2
C5—C4—C3—C2
C4—C3—C2—O1
C4—C3—C2—C1
C11—C10—C9—C8
C12—C10—C9—C8
C10—C9—C8—C7
C9—C8—C7—O2
C9—C8—C7—C6
C11—C6—C7—O2
N1—C6—C7—O2
C11—C6—C7—C8
N1—C6—C7—C8
−1.04 (19)
176.43 (11)
1.24 (19)
135.27 (13)
−104.50 (15)
−169.52 (11)
−48.46 (16)
71.77 (15)
−177.78 (12)
−1.00 (18)
175.39 (11)
−0.05 (19)
−179.87 (11)
0.98 (18)
1.15 (18)
−175.38 (11)
−0.24 (19)
−176.12 (11)
−116.71 (14)
67.42 (17)
179.98 (11)
−4.21 (17)
−0.83 (18)
174.98 (11)
C6—N1—C4—C3
−177.34 (11)
5.14 (18)
C6—N1—C4—C5
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H100···O1
O2—H200···O1i
0.89 (2)
0.92 (2)
1.89 (2)
1.72 (2)
2.628 (2)
2.633 (1)
138 (2)
172 (2)
Symmetry code: (i) x, −y+1/2, z+1/2.
Comparison of experimental and DFT-calculated bond lengths (Å) for (I)
Bond
X-ray
Keto tautomer
1.238
Enol tautomer
C2—O1
C2—C3
1.263 (2)
1.416 (2)
1.323
1.370
1.447
Acta Cryst. (2013). C69, 258-262
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supplementary materials
C3—C4
C4—N1
N1—C6
1.394 (2)
1.344 (2)
1.415 (2)
1.376
1.365
1.396
1.441
1.305
1.395
Comparison of experimental and DFT-calculated bond lengths (Å) for (II)
Bond
X-ray
Keto tautomer
1.251
Enol tautomer
1.326
C2—O1
C2—C3
C3—C4
C4—N1
N1—C6
1.268 (1)
1.411 (2)
1.395 (2)
1.335 (2)
1.430 (2)
1.437
1.372
1.385
1.443
1.355
1.308
1.417
1.408
Acta Cryst. (2013). C69, 258-262
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