Hydrogen bonding due to regioisomerism and its effect on the supramolecular architecture of diethyl 2-[(2/4-hydroxyanilino)methylidene]malonates

Article abstract of DOI:10.1107/S0108270112047257

Diethyl 2-[(2-hydroxyanilino)methylidene]malonate, (I), and diethyl 2-[(4-hydroxyanilino)methylidene]malonate, (II), both C₁₄H ₁₇NO5, crystallize in centrosymmetric orthorhombic and monoclinic crystal systems, respectively. Compound

Full text of DOI:10.1107/S0108270112047257

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
inorganic metal complexes and in the detection of amino acids.
BECV–amine derivatives are mainly used as building blocks
for the synthesis of a variety of bioactive nitrogen-containing
ISSN 0108-2701
Hydrogen bonding due to regio-
isomerism and its effect on the supra-
molecular architecture of diethyl
2-[(2/4-hydroxyanilino)methylidene]-
malonates
heterocycles such as pyrazoles, 4-oxoquinoline-3-carboxylic
acid esters, pyrimidines, pyrimido[1,2-a]pyrimidines, 3H,5H-
pyrrolo[3,2-d]pyrimidines and pyrido[2,3-d]pyrimidines (John-
son & Ambler, 1911; Fustero et al., 2011; Niedermeier et al.,
2009; Yang et al., 2009; Candeias et al., 2009; Petric et al., 1983;
Furneaux & Tyler, 1999).
Andivelu Ilangovan,* Perumal Venkatesan and Rajendran
Ganesh Kumar
School of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu,
India
Correspondence e-mail: ilangovanbdu@yahoo.com
Received 10 September 2012
Accepted 16 November 2012
Online 13 December 2012
Diethyl 2-[(2-hydroxyanilino)methylidene]malonate, (I), and
diethyl 2-[(4-hydroxyanilino)methylidene]malonate, (II), both
C14H17NO5, crystallize in centrosymmetric orthorhombic and
monoclinic crystal systems, respectively. Compound (I) resides
on a crystallographic mirror plane and displays bifurcated
intramolecular hydrogen bonding, as well as intermolecular
hydrogen bonding due to the position of the hydroxy group.
Compound (II) has a single intramolecular N—Hꢀ ꢀ ꢀO
hydrogen bond. Infinite one-dimensional head-to-tail chains
formed by O—Hꢀ ꢀ ꢀO hydrogen bonding are present in both
structures. The molecular packing is mainly influenced by the
intermolecular O—Hꢀ ꢀ ꢀO interactions. Additionally, C—
Hꢀ ꢀ ꢀO interactions crosslinking the chains are found in (II).
Comment
Hydrogen bonding is an important force central to the func-
tioning of several complex and large biomolecules such as
enzymes, DNA and RNA. It plays a major role in the design of
novel supramolecular architectures and allows recognition
among many organic molecules. Crystal engineering pertains
to the directionality of hydrogen bonds and the ways in which
hydrogen bonding influences crystal geometries depending on
their strengths (Desiraju, 2011; Adam et al., 2010). Phenol
compounds can exhibit inter- and intramolecular hydrogen
bonding depending on the nature and position of additional
functional groups. The electronic nature and the ortho, para or
meta position of the substituent strongly influences the acidity
of the phenolic H atom and hence the strength of the
hydrogen bond.
Figure 1
Perspective views of (a) compound (I) and (b) compound (II), showing
the atom-numbering schemes. Displacement ellipsoids are drawn at the
50% probability level and H atoms are shown as small spheres of
arbitrary radii.
2,2-Bis(ethoxycarbonyl)vinyl (BECV) derivatives are im-
portant intermediates useful in the synthesis of various
nitrogen- and oxygen-containing heterocycles, as ligands in
70 # 2013 International Union of Crystallography
doi:10.1107/S0108270112047257
Acta Cryst. (2013). C69, 70–73

organic compounds
Figure 2
The one-dimensional hydrogen-bonded chains extending along the b axis in compound (I), viewed (a) down the c axis and (b) down the a axis. Dashed
lines indicate the hydrogen-bonding interactions.
Figure 3
The one-dimensional hydrogen-bonded chain along the a axis in compound (II), viewed approximately down the c axis. Dashed lines indicate the
hydrogen-bonding interactions.
Simple diethyl 2-[(alkyl/aryl)aminomethylidene]malonate
(N-BECV) derivatives are biologically active compounds.
Steck (1962) observed that N-BECV derivatives of diisopro-
pylamine, piperidine {diethyl 2-[(piperidin-1-yl)methylidene]-
malonate, see (1) in Scheme 2}, pyrrolidine and morpholine
idene)malonate [see (2) in Scheme 2] and diethyl 2-{[(di-
phenylmethoxy)amino]methylidene}malonate [see (3) in
Scheme 2], and established their muscle relaxation and seda-
tive properties. In addition, N-BECV derivatives show a very
low cytotoxicity to normal cells.
Recently, we have demonstrated that N-BECV can be used
as a chemo-selective amine-protecting group useful for several
sensitive organic functional group transformations (Ilangovan
& Ganesh Kumar, 2010). In a continuation of this work, we
studied the crystal structures of diethyl 2-[(2-hydroxy-
anilino)methylidene]malonate, (I), and diethyl 2-[(4-hy-
droxyanilino)methylidene]malonate, (II), and the effect of
hydroxy-group substitution on their supramolecular archi-
tectures. To the best of our knowledge, single-crystal struc-
tures of BECV derivatives have not been reported previously.
Compounds (I) and (II) (Fig. 1) are regioisomers.
Compound (I) occupies a crystallographic mirror plane and is
are central nervous system stimulants. Similarly, Santilli et al.
(1964) prepared a number of enamine derivatives containing
the N-BECV unit, such as a 4-(aminomethyl)benzoic acid
derivative, diethyl 2-({[3-(dimethylamino)propyl]amino}methyl-
ꢁ
Acta Cryst. (2013). C69, 70–73
Ilangovan et al.
Two isomers of C14H17NO5 71

organic compounds
Figure 4
Different hydrogen-bonding interactions in compound (II). (a) The macrocyclic head-to-tail hydrogen-bonded dimer viewed along the b axis [symmetry
code: (c) ꢄx + 3, ꢄy + 2, ꢄz]. (b) The hydrogen-bonded ladder viewed down the b axis.
totally planar, with the exception of a disordered ethoxy group
where atom C13 occupies alternate positions just off the
mirror plane. The benzene ring in compound (II) is not
constrained to be planar by any crystallographic symmetry,
but is essentially planar, with an r.m.s. deviation of the ring
bond between the hydroxy group and the carbonyl O atom of
the second ester group in an adjacent molecule. This interac-
tion has a graph-set motif of C(9). No interactions are
observed between the chains.
In the case of (II), two hydrogen-bond interactions (N1—
H1Nꢀ ꢀ ꢀO4 and O1—H1Oꢀ ꢀ ꢀO2i; symmetry code as in Table 3)
are observed, the former intramolecular interaction gives rise
to an S(6) ring motif (Table 3). The latter interaction gives rise
to an extended chain which runs parallel to the a axis and has a
graph-set motif of C(11) (Fig. 3). In addition to head-to-tail
hydrogen bonding, there is a macrocyclic R22(26) dimer motif
formed by a C11—H11Cꢀ ꢀ ꢀO1ii interaction (Table 3) between
two adjacent one-dimensional chains (Fig. 4). This gives rise to
a ladder-like structure (Figs. 4b and 5). Neither compound
shows any significant centroid–centroid or C—Hꢀ ꢀ ꢀꢀ inter-
actions.
In conclusion, we have studied crystal structure properties
such as motifs, chains, the nature of hydrogen bonding and
other interactions of the title compounds (I) and (II). Varia-
tions in the ortho and para substitution of hydroxy groups was
analysed. The presence of an –OH group adjacent to an –NH
group favours bifurcated hydrogen bonding and the formation
of S(6) and S(5) ring motifs, and gives rise to strict planarity
for compound (I). In a supramolecular framework it gives rise
to a layer-like structure. In the case of compound (II), a S(6)
ring and a macrocyclic R22(26) ring motif were observed
between chains. Both compounds form a head-to-tail one-
dimensional hydrogen-bonded chain. We believe that this
study will be helpful in understanding the ability of these
molecules to interact with biological systems. The compounds
may be useful synthons in the formation of metal complexes
and different hereocyclic compounds.
˚
atoms from their mean plane of 0.016 A. The angles between
the plane of the aminophenol ring and the plane of the vinylic
double bond are 0 and 33.59 (12)ꢂ in (I) and (II), respectively.
In both compounds, the C1—N1 (Car—N) bonds (Table 1) are
˚
shorter than a normal N—C bond (1.336 A; Allen et al.. 1987)
because of conjugation between ꢀ-electrons in the vinylic
double bond and the lone pair electrons of the N atom. The
vinylic C7—C8 bond lengths are similarly longer than normal
˚
vinylic C—C bonds (1.316 A; Allen et al.. 1987).
The presence of a phenolic –OH group at the ortho position
to the amine group in compound (I) favours strong bifurcated
intramolecular hydrogen bonds between the amine group and
the hydroxy O atom, O1, and one of the ester carbonyl O
atoms, O4 (Table 2). This gives rise to S(6) and S(5) ring motifs
(Fig. 2) (Bernstein et al., 1995) and helps in achieving rigorous
planarity. The molecules are linked into extended chains,
which run parallel to the b axis, by an intermolecular hydrogen
Experimental
Diethyl 2-(ethoxymethylidene)malonate (1 equivalent) was added to
a solution of 2- or 4-aminophenol (1 equivalent) in ethanol (5 ꢃ w/v)
and the resulting solution stirred for 15 min at room temperature
(301 K) (Ilangovan & Ganesh Kumar, 2010). After completion of the
reaction, the ethanol was evaporated under reduced pressure to give
compound (I) or (II) as a white solid in quantitative yield [99%
yields; m.p. 402 and 412 K for (I) and (II), respectively]. Good quality
single crystals of (I) and (II) suitable for diffraction analysis were
obtained from hexane and ethyl acetate mixtures (8:2 v/v).
Figure 5
The packing of molecules of compound (II) along (a) the c axis.
ꢁ
72 Ilangovan et al.
Two isomers of C14H17NO5
Acta Cryst. (2013). C69, 70–73

organic compounds
Table 1
Comparison of selected bond lengths (A) in (I) and (II).
Compound (I)
˚
Crystal data
(I)
(II)
3
˚
V = 1453.54 (7) A
Z = 4
Mo Kꢁ radiation
ꢂ = 0.10 mmꢄ1
T = 296 K
C14H17NO5
Mr = 279.29
N1—C1
N1—C7
C7—C8
1.404 (3)
1.330 (3)
1.364 (3)
1.4259 (13)
1.3232 (15)
1.3844 (14)
Orthorhombic, Pbcm
˚
a = 11.3011 (3) A
˚
b = 19.2760 (4) A
˚
c = 6.6725 (2) A
0.22 ꢃ 0.22 ꢃ 0.20 mm
Table 2
Hydrogen-bond geometry (A, ) for (I).
Data collection
ꢂ
˚
Bruker SMART CCD area-detector
diffractometer
7641 measured reflections
1690 independent reflections
1165 reflections with I > 2ꢃ(I)
Rint = 0.027
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1Nꢀ ꢀ ꢀO1
N1—H1Nꢀ ꢀ ꢀO4
O1—H1Oꢀ ꢀ ꢀO2i
Symmetry code: (i) ꢄx þ 2; y þ ; z.
0.84 (3)
0.84 (3)
0.86 (4)
2.28 (3)
1.95 (3)
1.81 (4)
2.606 (2)
2.640 (3)
2.661 (2)
103 (2)
139 (2)
178 (3)
Refinement
R[F2 > 2ꢃ(F2)] = 0.049
wR(F2) = 0.154
S = 1.05
1690 reflections
132 parameters
H atoms treated by a mixture of
independent and constrained
refinement
1
2
ꢄ3
˚
Áꢄmax = 0.23 e A
ꢄ3
˚
Áꢄmin = ꢄ0.20 e A
Table 3
Hydrogen-bond geometry (A, ) for (II).
ꢂ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
Compound (II)
N1—H1Nꢀ ꢀ ꢀO4
O1—H1Oꢀ ꢀ ꢀO2i
C11—H11Cꢀ ꢀ ꢀO1ii
Symmetry code: (i) x þ 1; y; z; (ii) ꢄx þ 3; ꢄy þ 2; ꢄz.
0.86
0.82
0.96
2.06
1.91
2.60
2.6936 (13)
2.7268 (13)
3.472 (2)
130
174
152
Crystal data
3
˚
V = 1424.5 (2) A
Z = 4
C14H17NO5
Mr = 279.29
Monoclinic, P21=n
Mo Kꢁ radiation
ꢂ = 0.10 mmꢄ1
T = 296 K
0.25 ꢃ 0.25 ꢃ 0.20 mm
˚
˚
a = 10.9970 (11) A
b = 10.8919 (11) A
400 MHz NMR facility at the School of Chemistry, Bhar-
athidasan University.
˚
c = 12.3244 (12) A
ꢅ = 105.206 (1)ꢂ
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FN3116). Services for accessing these data are
described at the back of the journal.
Data collection
Bruker SMART CCD area-detector
diffractometer
12064 measured reflections
3297 independent reflections
2826 reflections with I > 2ꢃ(I)
Rint = 0.027
References
Refinement
Adam, D. M., Karel, J. H., Alexandre, N. S. & Colin, L. R. (2010). Cryst.
Growth Des. 10, 5302–5306.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
R[F2 > 2ꢃ(F2)] = 0.038
wR(F2) = 0.117
S = 1.05
182 parameters
H-atom parameteꢄrs3 constrained
˚
Áꢄmax = 0.25 e A
ꢄ3
˚
3297 reflections
Áꢄmin = ꢄ0.17 e A
Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Candeias, N. R., Branco, L. C., Gois, P. M. P., Afonso, C. A. M. & Trindade, A.
F. (2009). Chem. Rev. 109, 2703–2802.
For compound (I), the amino and hydroxy H atoms were located in
a difference map and refined isotropically. All other H atoms, were
placed in their geometrically idealized positions and refined using a
Desiraju, G. R. (2011). Cryst. Growth Des. 11, 896–898.
Furneaux, R. H. & Tyler, P. C. (1999). J. Org. Chem. 64, 8411–8412.
Fustero, S., Rosello, M. S., Barrio, P. & Fuentes, A. S. (2011). Chem. Rev. 111,
6984–7034.
Ilangovan, A. & Ganesh Kumar, R. (2010). Chem. Eur. J. 16, 2938–2943.
Johnson, T. B. & Ambler, J. A. (1911). J. Am. Chem. Soc. 33, 978–985.
Niedermeier, S., Singethan, K., Rohrer, S. G., Matz, M., Kossner, M.,
Diederich, S., Maisner, A., Schmitz, J., Hiltensperger, G., Baumann, K.,
Holzgrabe, U. & Schaulies, J. S. (2009). J. Med. Chem. 52, 4257–4265.
Petric, A., Stanovnik, B. & Tyler, M. (1983). J. Org. Chem. 48, 4132–4135.
Santilli, A. A., Bruce, W. F. & Osdene, T. S. (1964). J. Med. Chem. 7, 68–72.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
˚
riding model, with C—H = 0.93 (aromatic and methyl) or 0.97 A
˚
˚
(methylene), O—H = 0.82 A and N—H = 0.86 A, and with Uiso(H) =
1.5Ueq(C,O) for the methyl groups and the hydroxy group in (II), and
Uiso(H) = 1.2Ueq(C,N) otherwise.
For both compounds, data collection: SMART (Bruker, 2008); cell
refinement: SMART; data reduction: SAINT (Bruker, 2008);
program(s) used to solve structure: SHELXTL (Sheldrick, 2008);
program(s) used to refine structure: SHELXL97 (Sheldrick, 2008);
molecular graphics: PLATON (Spek, 2009); software used to prepare
material for publication: PLATON.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
Steck, E. A. (1962). J. Org. Chem. 27, 306–308.
Yang, W., Ruan, Z., Wang, Y., Kirk, K. V., Ma, Z., Arey, B. J., Cooper, C. B.,
Seethala, R., Feyen, J. H. M. & Dickson, J. K. Jr (2009). J. Med. Chem. 52,
1204–1208.
The authors thank the DST–India (FIST programme) for
use of the Bruker SMART APEXII diffractometer and the
ꢁ
Acta Cryst. (2013). C69, 70–73
Ilangovan et al.
Two isomers of C14H17NO5 73

supplementary materials
supplementary materials
Acta Cryst. (2013). C69, 70-73 [doi:10.1107/S0108270112047257]
Hydrogen bonding due to regioisomerism and its effect on the supramolecular
architecture of diethyl 2-[(2/4-hydroxyanilino)methylidene]malonates
Andivelu Ilangovan, Perumal Venkatesan and Rajendran Ganesh Kumar
(I) Diethyl 2-[(2-hydroxyanilino)methylidene]malonate
Crystal data
C14H17NO5
Mr = 279.29
F(000) = 592
Dx = 1.276 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2008 reflections
θ = 3.1–25.2°
Orthorhombic, Pbcm
Hall symbol: -P 2c 2b
a = 11.3011 (3) Å
b = 19.2760 (4) Å
c = 6.6725 (2) Å
V = 1453.54 (7) Å3
Z = 4
µ = 0.10 mm−1
T = 296 K
Plate, yellow
0.22 × 0.22 × 0.20 mm
Data collection
Bruker SMART CCD area-detector
diffractometer
1165 reflections with I > 2σ(I)
Rint = 0.027
Radiation source: fine-focus sealed tube
Graphite monochromator
phi and ω scans
7641 measured reflections
1690 independent reflections
θmax = 26.8°, θmin = 1.8°
h = −11→14
k = −24→24
l = −7→8
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.049
wR(F2) = 0.154
S = 1.05
1690 reflections
Hydrogen site location: inferred from
neighbouring sites
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0764P)2 + 0.2553P]
where P = (Fo2 + 2Fc2)/3
132 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
(Δ/σ)max < 0.001
Δρmax = 0.23 e Å−3
Δρmin = −0.20 e Å−3
Extinction correction: SHELXL97 (Sheldrick,
2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.0072 (16)
Acta Cryst. (2013). C69, 70-73
sup-1

supplementary materials
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds 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 (Å2)
x
y
z
Uiso*/Ueq
Occ. (<1)
O1
0.93175 (16)
1.12614 (17)
1.20132 (18)
0.86035 (15)
1.05136 (16)
0.8942 (2)
0.7941 (2)
0.8167 (2)
0.7241 (3)
0.7390
0.39737 (8)
0.24764 (10)
0.14140 (9)
0.06136 (8)
0.03504 (7)
0.26400 (9)
0.30708 (11)
0.37835 (11)
0.42457 (14)
0.4720
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.1323
0.3677
0.2500
0.3504
0.2787
0.1208
0.2500
0.2500
0.3680
0.1320
0.2500
0.2500
0.1325
0.3675
0.2500
0.2500
0.2500
0.0719 (6)
0.0973 (8)
0.1018 (8)
0.0689 (5)
0.0770 (6)
0.0609 (6)
0.0571 (6)
0.0573 (6)
0.0724 (8)
0.087*
O4
O5
O3
O2
N1
C1
C2
C3
H3
C4
0.6101 (3)
0.5475
0.40078 (16)
0.4321
0.0918 (10)
0.110*
H4
C5
0.5875 (3)
0.5098
0.33043 (17)
0.3145
0.0931 (10)
0.112*
H5
C6
0.6789 (3)
0.6632
0.28407 (14)
0.2367
0.0749 (8)
0.090*
H6
C7
0.8954 (2)
0.9933 (2)
1.1103 (3)
1.3185 (3)
1.3277
0.19499 (11)
0.15357 (10)
0.18519 (12)
0.17212 (17)
0.2012
0.0572 (6)
0.0584 (6)
0.0737 (8)
0.159 (2)
0.191*
C8
C12
C13
H13A
H13B
C14
H14A
H14B
H14C
C9
0.50
0.50
1.3277
0.2012
0.191*
1.4055 (3)
1.3874
0.1209 (2)
0.0869
0.1268 (15)
0.190*
0.50
0.50
0.50
1.4810
0.1415
0.190*
1.4082
0.0990
0.190*
0.9745 (2)
0.8306 (2)
0.8627
0.07839 (11)
−0.01136 (12)
−0.0339
0.0569 (6)
0.0701 (7)
0.084*
C10
H10A
H10B
C11
H11A
H11B
H11C
H1O
H1N
H7
0.50
0.50
0.8627
−0.0339
0.084*
0.6988 (3)
0.6752
−0.01584 (16)
−0.0637
0.0891 (9)
0.134*
0.6682
0.0066
0.134*
0.50
0.50
0.6682
0.0066
0.134*
0.939 (3)
0.963 (3)
0.818 (2)
0.4416 (19)
0.2803 (13)
0.1746 (12)
0.112 (11)*
0.075 (9)*
0.055 (6)*
Acta Cryst. (2013). C69, 70-73
sup-2

supplementary materials
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O1
O4
O5
O3
O2
N1
C1
0.0698 (12)
0.0854 (13)
0.0682 (12)
0.0659 (11)
0.0664 (11)
0.0690 (14)
0.0705 (15)
0.0659 (14)
0.0755 (18)
0.072 (2)
0.0349 (8)
0.0402 (8)
0.0469 (10)
0.0405 (9)
0.0337 (8)
0.0368 (10)
0.0415 (11)
0.0426 (11)
0.0494 (12)
0.0776 (19)
0.082 (2)
0.1110 (15)
0.166 (2)
0.0018 (8)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
−0.0118 (10)
−0.0076 (9)
−0.0064 (7)
−0.0012 (8)
−0.0001 (9)
0.0020 (11)
0.0027 (10)
0.0104 (12)
0.0148 (15)
−0.0057 (15)
−0.0059 (13)
−0.0033 (11)
−0.0029 (10)
−0.0058 (12)
−0.0150 (17)
−0.028 (2)
0.190 (2)
0.1001 (13)
0.1309 (17)
0.0767 (14)
0.0592 (14)
0.0634 (14)
0.092 (2)
C2
C3
C4
0.126 (3)
C5
0.0661 (17)
0.0738 (18)
0.0737 (16)
0.0695 (15)
0.0782 (18)
0.071 (2)
0.131 (3)
C6
0.0538 (14)
0.0392 (11)
0.0347 (10)
0.0403 (12)
0.0586 (18)
0.128 (3)
0.097 (2)
C7
0.0587 (14)
0.0711 (15)
0.103 (2)
C8
C12
C13
C14
C9
0.348 (7)
0.085 (2)
0.167 (4)
0.0653 (15)
0.0707 (16)
0.0776 (19)
0.0372 (10)
0.0446 (12)
0.0799 (19)
0.0683 (15)
0.0949 (19)
0.110 (2)
−0.0036 (10)
−0.0137 (11)
−0.0232 (16)
C10
C11
Geometric parameters (Å, º)
O1—C2
O1—H1O
O4—C12
O5—C12
O5—C13i
O5—C13
O3—C9
O3—C10
O2—C9
N1—C7
N1—C1
N1—H1N
C1—C6
C1—C2
C2—C3
C3—C4
C3—H3
C4—C5
C4—H4
1.351 (3)
0.86 (4)
C5—C6
1.366 (4)
C5—H5
C6—H6
C7—C8
C7—H7
C8—C12
C8—C9
C13—C14
0.9300
0.9300
1.217 (3)
1.331 (3)
1.451 (4)
1.451 (4)
1.331 (3)
1.442 (3)
1.205 (3)
1.330 (3)
1.404 (3)
0.84 (3)
1.364 (3)
0.96 (2)
1.456 (4)
1.465 (3)
1.393 (5)
0.9700
C13—H13A
C13—H13B
C14—H14A
C14—H14B
C14—H14C
C10—C11
0.9700
0.9600
0.9600
1.375 (4)
1.398 (3)
1.374 (3)
1.368 (4)
0.9300
0.9600
1.492 (4)
0.9700
C10—H10A
C10—H10B
C11—H11A
C11—H11B
C11—H11C
0.9700
0.9600
1.380 (4)
0.9300
0.9600
0.9600
C2—O1—H1O
C12—O5—C13i
C12—O5—C13
C13i—O5—C13
111 (2)
C8—C7—H7
C7—C8—C12
C7—C8—C9
C12—C8—C9
120.0 (14)
119.4 (2)
117.5 (2)
123.1 (2)
116.5 (2)
116.5 (2)
0.0 (2)
Acta Cryst. (2013). C69, 70-73
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supplementary materials
C9—O3—C10
C7—N1—C1
C7—N1—H1N
C1—N1—H1N
C6—C1—C2
C6—C1—N1
C2—C1—N1
O1—C2—C3
O1—C2—C1
C3—C2—C1
C4—C3—C2
C4—C3—H3
C2—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
C6—C5—C4
C6—C5—H5
C4—C5—H5
C5—C6—C1
C5—C6—H6
C1—C6—H6
N1—C7—C8
N1—C7—H7
117.77 (19)
126.8 (2)
111.4 (18)
121.7 (18)
119.4 (2)
124.9 (2)
115.7 (2)
123.8 (2)
116.3 (2)
119.9 (2)
120.0 (3)
120.0
O4—C12—O5
120.9 (3)
123.2 (3)
115.9 (2)
110.8 (3)
109.5
O4—C12—C8
O5—C12—C8
C14—C13—O5
C14—C13—H13A
O5—C13—H13A
C14—C13—H13B
O5—C13—H13B
109.5
109.5
109.5
H13A—C13—H13B
O2—C9—O3
108.1
121.8 (2)
125.6 (2)
112.6 (2)
106.8 (2)
110.4
O2—C9—C8
O3—C9—C8
120.0
O3—C10—C11
120.2 (3)
119.9
O3—C10—H10A
C11—C10—H10A
O3—C10—H10B
C11—C10—H10B
H10A—C10—H10B
C10—C11—H11A
C10—C11—H11B
H11A—C11—H11B
C10—C11—H11C
H11A—C11—H11C
H11B—C11—H11C
110.4
119.9
110.4
120.2 (3)
119.9
110.4
108.6
119.9
109.5
120.3 (2)
119.8
109.5
109.5
119.8
109.5
126.4 (2)
113.6 (14)
109.5
109.5
C7—N1—C1—C6
C7—N1—C1—C2
C6—C1—C2—O1
N1—C1—C2—O1
C6—C1—C2—C3
N1—C1—C2—C3
O1—C2—C3—C4
C1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—C6
C4—C5—C6—C1
C2—C1—C6—C5
N1—C1—C6—C5
C1—N1—C7—C8
N1—C7—C8—C12
N1—C7—C8—C9
C13i—O5—C12—O4
0.0
C13—O5—C12—O4
C13i—O5—C12—C8
C13—O5—C12—C8
C7—C8—C12—O4
C9—C8—C12—O4
C7—C8—C12—O5
C9—C8—C12—O5
C12—O5—C13—C14
C13i—O5—C13—C14
C10—O3—C9—O2
C10—O3—C9—C8
C7—C8—C9—O2
C12—C8—C9—O2
C7—C8—C9—O3
C12—C8—C9—O3
C9—O3—C10—C11
0.0
180.0
180.0
0.0
180.0
180.0
0.0
0.0
180.0
180.0
0.0
180.0
180.0
0.0
180.0
0 (100)
0.0
0.0
0.0
0.0
180.0
180.0
0.0
0.0
180.0
180.0
0.0
0.0
180.0
180.0
180.0
0.0
Symmetry code: (i) x, y, −z+1/2.
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
103 (2)
N1—H1N···O1
0.84 (3)
2.28 (3)
2.606 (2)
Acta Cryst. (2013). C69, 70-73
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supplementary materials
N1—H1N···O4
O1—H1O···O2ii
0.84 (3)
0.86 (4)
1.95 (3)
1.81 (4)
2.640 (3)
2.661 (2)
139 (2)
178 (3)
Symmetry code: (ii) −x+2, y+1/2, z.
(II) Diethyl 2-[(4-hydroxyanilino)methylidene]malonate
Crystal data
C14H17NO5
Mr = 279.29
F(000) = 592
Dx = 1.302 Mg m−3
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 10.9970 (11) Å
b = 10.8919 (11) Å
c = 12.3244 (12) Å
β = 105.206 (1)°
V = 1424.5 (2) Å3
Z = 4
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 7526 reflections
θ = 2.2–27.6°
µ = 0.10 mm−1
T = 296 K
Plate, yellow
0.25 × 0.25 × 0.20 mm
Data collection
Bruker SMART CCD area-detector
diffractometer
2826 reflections with I > 2σ(I)
Rint = 0.027
Radiation source: fine-focus sealed tube
Graphite monochromator
phi and ω scans
θ
max = 27.6°, θmin = 2.2°
h = −14→14
k = −14→13
12064 measured reflections
3297 independent reflections
l = −15→16
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.038
wR(F2) = 0.117
S = 1.05
3297 reflections
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0643P)2 + 0.2345P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.25 e Å−3
Δρmin = −0.17 e Å−3
182 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Extinction correction: SHELXL97 (Sheldrick,
2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.033 (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.
Acta Cryst. (2013). C69, 70-73
sup-5

supplementary materials
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
O2
0.89430 (8)
1.76120 (8)
1.7967
0.89700 (9)
1.11032 (9)
1.0435
0.10761 (8)
0.09308 (8)
0.0990
0.0515 (2)
0.0526 (2)
0.079*
O1
H1O
O3
1.06830 (8)
1.29994 (9)
1.2826
0.80048 (8)
1.08073 (9)
1.1387
0.09127 (8)
0.19856 (9)
0.2395
0.0496 (2)
0.0444 (2)
0.053*
N1
H1N
O5
0.96576 (8)
1.41932 (10)
1.58631 (11)
1.6213
1.04595 (8)
1.08441 (10)
1.20500 (11)
1.2813
0.29964 (7)
0.17351 (9)
0.13509 (10)
0.1276
0.0456 (2)
0.0377 (2)
0.0433 (3)
0.052*
C1
C3
H3
C4
1.64991 (10)
1.59877 (10)
1.6416
1.09859 (10)
0.98497 (10)
0.9135
0.12128 (9)
0.13553 (10)
0.1269
0.0383 (2)
0.0416 (3)
0.050*
C5
H5
C2
1.47084 (11)
1.4276
1.19783 (11)
1.2693
0.15998 (10)
0.1677
0.0427 (3)
0.051*
H2
O4
1.11922 (9)
1.48409 (10)
1.4508
1.17548 (9)
0.97759 (10)
0.9014
0.28488 (10)
0.16256 (10)
0.1733
0.0615 (3)
0.0414 (3)
0.050*
C6
H6
C9
1.00865 (10)
1.09731 (10)
1.21404 (10)
1.2340
0.89389 (10)
0.98743 (10)
0.99437 (11)
0.9323
0.12661 (10)
0.18571 (10)
0.16325 (10)
0.1190
0.0395 (3)
0.0392 (3)
0.0403 (3)
0.048*
C8
C7
H7
C12
C14
H14A
H14B
H14C
C13
H13A
H13B
C10
H10A
H10B
C11
H11A
H11B
H11C
1.06250 (10)
0.82810 (14)
0.7956
1.07905 (11)
1.07958 (17)
1.1397
0.25894 (10)
0.41761 (14)
0.4596
0.0412 (3)
0.0667 (4)
0.100*
0.8706
1.0162
0.4674
0.100*
0.7599
1.0443
0.3611
0.100*
0.91915 (13)
0.8773
1.13979 (14)
1.2044
0.36247 (12)
0.3123
0.0551 (3)
0.066*
0.9885
1.1758
0.4189
0.066*
0.99000 (14)
0.9289
0.71243 (13)
0.7547
0.01554 (13)
−0.0438
0.0566 (3)
0.068*
0.9451
0.6608
0.0562
0.068*
1.07613 (18)
1.0277
0.63637 (14)
0.5766
−0.03301 (16)
−0.0836
0.0726 (5)
0.109*
1.1362
0.5952
0.0265
0.109*
1.1198
0.6885
−0.0731
0.109*
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
O2
O1
O3
N1
O5
C1
0.0363 (4)
0.0402 (4)
0.0427 (4)
0.0389 (5)
0.0457 (4)
0.0343 (5)
0.0528 (5)
0.0524 (5)
0.0434 (5)
0.0461 (5)
0.0461 (5)
0.0417 (6)
0.0674 (6)
−0.0014 (3)
−0.0024 (4)
−0.0042 (3)
−0.0041 (4)
−0.0001 (3)
−0.0024 (4)
0.0169 (4)
0.0251 (4)
0.0238 (4)
0.0201 (4)
0.0250 (4)
0.0118 (4)
−0.0126 (4)
0.0081 (4)
0.0711 (6)
0.0679 (6)
0.0526 (6)
0.0518 (5)
0.0384 (5)
−0.0179 (4)
−0.0109 (4)
−0.0096 (4)
−0.0032 (4)
Acta Cryst. (2013). C69, 70-73
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supplementary materials
C3
0.0431 (6)
0.0333 (5)
0.0380 (5)
0.0431 (6)
0.0564 (5)
0.0403 (6)
0.0398 (5)
0.0375 (5)
0.0396 (5)
0.0370 (5)
0.0558 (8)
0.0529 (7)
0.0583 (8)
0.0962 (12)
0.0353 (5)
0.0431 (6)
0.0367 (6)
0.0352 (5)
0.0506 (5)
0.0357 (6)
0.0391 (6)
0.0394 (6)
0.0418 (6)
0.0423 (6)
0.0920 (12)
0.0594 (8)
0.0473 (7)
0.0515 (8)
0.0514 (7)
0.0387 (5)
0.0517 (6)
0.0500 (6)
0.0872 (7)
0.0502 (6)
0.0439 (6)
0.0440 (6)
0.0427 (6)
0.0464 (6)
0.0611 (9)
0.0593 (8)
0.0673 (9)
0.0874 (11)
−0.0057 (4)
−0.0019 (4)
0.0021 (4)
0.0013 (4)
−0.0113 (4)
−0.0034 (4)
−0.0001 (4)
−0.0003 (4)
−0.0009 (4)
0.0019 (4)
0.0019 (7)
0.0033 (6)
−0.0124 (6)
−0.0186 (8)
0.0124 (5)
0.0095 (4)
0.0148 (5)
0.0128 (5)
0.0359 (5)
0.0154 (5)
0.0188 (5)
0.0168 (4)
0.0164 (5)
0.0148 (5)
0.0312 (7)
0.0260 (6)
0.0222 (6)
0.0549 (10)
0.0029 (5)
0.0040 (4)
0.0019 (5)
−0.0040 (4)
−0.0265 (5)
0.0028 (4)
−0.0026 (4)
−0.0047 (4)
−0.0047 (4)
−0.0053 (5)
−0.0147 (8)
−0.0193 (6)
−0.0175 (6)
−0.0250 (8)
C4
C5
C2
O4
C6
C9
C8
C7
C12
C14
C13
C10
C11
Geometric parameters (Å, º)
O2—C9
O1—C4
O1—H1O
O3—C9
O3—C10
N1—C1
N1—C7
N1—H1N
O5—C12
O5—C13
C1—C2
C1—C6
C3—C2
C3—C4
C3—H3
C4—C5
C5—C6
C5—H5
C2—H2
1.2177 (13)
O4—C12
1.2206 (15)
1.3631 (13)
0.8200
C6—H6
0.9300
C9—C8
1.4651 (16)
1.3844 (14)
1.4623 (15)
0.9300
1.3435 (13)
1.4527 (15)
1.4259 (13)
1.3232 (15)
0.8600
C7—C8
C8—C12
C7—H7
C14—C13
C14—H14A
C14—H14B
C14—H14C
C13—H13A
C13—H13B
C10—C11
C10—H10A
C10—H10B
C11—H11A
C11—H11B
C11—H11C
1.500 (2)
0.9600
1.3391 (13)
1.4544 (14)
1.3872 (16)
1.3891 (16)
1.3845 (16)
1.3870 (16)
0.9300
0.9600
0.9600
0.9700
0.9700
1.496 (2)
0.9700
0.9700
1.3894 (15)
1.3887 (15)
0.9300
0.9600
0.9600
0.9600
0.9300
C4—O1—H1O
C9—O3—C10
C7—N1—C1
C7—N1—H1N
C1—N1—H1N
C12—O5—C13
C2—C1—C6
C2—C1—N1
C6—C1—N1
C2—C3—C4
C2—C3—H3
C4—C3—H3
O1—C4—C3
109.5
N1—C7—C8
126.34 (10)
116.8
116.79 (10)
124.56 (10)
117.7
N1—C7—H7
C8—C7—H7
116.8
O4—C12—O5
122.36 (10)
123.39 (10)
114.19 (10)
109.5
117.7
O4—C12—C8
115.83 (10)
119.88 (10)
118.64 (10)
121.48 (10)
120.09 (10)
120.0
O5—C12—C8
C13—C14—H14A
C13—C14—H14B
H14A—C14—H14B
C13—C14—H14C
H14A—C14—H14C
H14B—C14—H14C
O5—C13—C14
109.5
109.5
109.5
109.5
120.0
109.5
117.93 (10)
107.71 (12)
Acta Cryst. (2013). C69, 70-73
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supplementary materials
O1—C4—C5
C3—C4—C5
C6—C5—C4
C6—C5—H5
C4—C5—H5
C3—C2—C1
C3—C2—H2
C1—C2—H2
C5—C6—C1
C5—C6—H6
C1—C6—H6
O2—C9—O3
O2—C9—C8
O3—C9—C8
C7—C8—C12
C7—C8—C9
C12—C8—C9
122.41 (10)
119.66 (10)
120.34 (10)
119.8
O5—C13—H13A
C14—C13—H13A
O5—C13—H13B
C14—C13—H13B
110.2
110.2
110.2
110.2
119.8
H13A—C13—H13B
O3—C10—C11
108.5
106.96 (11)
110.3
110.3
110.3
110.3
108.6
109.5
109.5
109.5
109.5
109.5
109.5
120.27 (10)
119.9
O3—C10—H10A
C11—C10—H10A
O3—C10—H10B
C11—C10—H10B
H10A—C10—H10B
C10—C11—H11A
C10—C11—H11B
H11A—C11—H11B
C10—C11—H11C
H11A—C11—H11C
H11B—C11—H11C
119.9
119.73 (10)
120.1
120.1
121.74 (10)
126.53 (10)
111.71 (9)
119.52 (10)
118.01 (10)
122.25 (9)
C7—N1—C1—C2
C7—N1—C1—C6
C2—C3—C4—O1
C2—C3—C4—C5
O1—C4—C5—C6
C3—C4—C5—C6
C4—C3—C2—C1
C6—C1—C2—C3
N1—C1—C2—C3
C4—C5—C6—C1
C2—C1—C6—C5
N1—C1—C6—C5
C10—O3—C9—O2
C10—O3—C9—C8
O2—C9—C8—C7
146.18 (12)
−33.82 (18)
177.81 (10)
−1.73 (18)
−178.99 (10)
0.53 (18)
O3—C9—C8—C7
O2—C9—C8—C12
O3—C9—C8—C12
C1—N1—C7—C8
C12—C8—C7—N1
C9—C8—C7—N1
C13—O5—C12—O4
C13—O5—C12—C8
C7—C8—C12—O4
C9—C8—C12—O4
C7—C8—C12—O5
C9—C8—C12—O5
C12—O5—C13—C14
C9—O3—C10—C11
23.12 (15)
19.09 (19)
−162.32 (11)
179.95 (11)
−2.79 (19)
171.93 (12)
9.38 (18)
1.32 (18)
0.30 (18)
−173.38 (11)
14.69 (19)
−179.70 (10)
1.08 (18)
−159.79 (12)
−162.52 (11)
23.00 (17)
−1.49 (18)
178.51 (11)
8.69 (17)
−170.17 (11)
166.88 (12)
−169.97 (11)
−155.47 (12)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
N1—H1N···O4
C7—H7···O3
O1—H1O···O2i
0.86
0.93
0.82
2.06
2.27
1.91
2.6936 (13)
2.6589 (14)
2.7268 (13)
130
104
174
Symmetry code: (i) x+1, y, z.
Comparison of selected bond lengths (Å) in (I) and (II).
(I)
(II)
N1—C1
N1—C7
C7—C8
1.404 (3)
1.330 (3)
1.364 (3)
1.4259 (13)
1.3232 (15)
1.3844 (14)
Acta Cryst. (2013). C69, 70-73
sup-8