(E)-N'-(3-Eth-oxy-4-hy-droxy-benzyl-idene)-4-meth-oxy-benzohydrazide.

Abstract

In the mol-ecule of the title benzohydrazide derivative, C(17)H(18)N(2)O(4), the dihedral angle between the benzene rings is 6.86 (11)°. The meth-oxy group of the 4-meth-oxy-phenyl fragment deviates slightly [C(methyl)-O-C-C = 10.0 (4)°] with respect to the benzene ring, whereas the eth-oxy group of the 3-eth-oxy-4-hy-droxy-phenyl fragment is is almost coplanar [C-O-C-C(methyl) = 178.5 (2)°]. In the crystal, mol-ecules are linked by N-H⋯O, O-H⋯O and C-H⋯O hydrogen bonds into a two-dimensional network parallel to the ab plane. C-H⋯π inter-actions and C⋯O [2.980 (3) Å] short contacts are also observed.

Full text

Page 1

(E)-N0 0 0-(3-Ethoxy-4-hydroxybenzylidene)-
4-methoxybenzohydrazide
Hoong-Kun Fun,a*‡Premrudee Promdet,bJirapa
Horkaew,bChatchanok Karalaiband Suchada
Chantraprommab§
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800
USM, Penang, Malaysia, andbCrystal Materials Research Unit, Department of
Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla
90112, Thailand
Correspondence e-mail: hkfun@usm.my
Received 14 February 2012; accepted 18 February 2012
Key indicators: single-crystal X-ray study; T = 297 K; mean ?(C–C) = 0.004 A ˚;
R factor = 0.051; wR factor = 0.154; data-to-parameter ratio = 12.6.
In the molecule of the title benzohydrazide derivative,
C17H18N2O4, the dihedral angle between the benzene rings
is 6.86 (11)?. The methoxy group of the 4-methoxyphenyl
fragment deviates slightly [Cmethyl—O—C—C = 10.0 (4)?] with
respect to the benzene ring, whereas the ethoxy group of the
3-ethoxy-4-hydroxyphenyl fragment is is almost coplanar [C—
O—C—Cmethyl = 178.5 (2)?]. In the crystal, molecules are
linked by N—H???O, O—H???O and C—H???O hydrogen
bonds into a two-dimensional network parallel to the ab plane.
C—H???? interactions and C???O [2.980 (3) A˚] short contacts
are also observed.
Related literature
For bond-length data, see: Allen et al. (1987). For hydrogen-
bond motifs, see: Bernstein et al. (1995). For related structures,
see: Fun et al. (2011); Horkaew et al. (2011); Promdet et al.
(2011). For background and applications to benzohydrazide
derivatives, see: Bedia et al. (2006); Loncle et al. (2004); Raj et
al. (2007).
Experimental
Crystal data
C17H18N2O4
Mr= 314.33
Orthorhombic, P212121
a = 5.0607 (9) A˚
b = 11.086 (2) A˚
c = 27.629 (5) A˚
V = 1550.1 (5) A˚3
Z = 4
Mo K? radiation
? = 0.10 mm?1
T = 297 K
0.56 ? 0.10 ? 0.07 mm
Data collection
Bruker APEX DUO CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
Tmin= 0.948, Tmax= 0.993
10252 measured reflections
2637 independent reflections
1921 reflections with I > 2?(I)
Rint= 0.100
Refinement
R[F2> 2?(F2)] = 0.051
wR(F2) = 0.154
S = 1.04
2637 reflections
210 parameters
H-atom parameters constrained
??max= 0.36 e A˚?3
??min= ?0.35 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
Cg1 is the centroid of the C9–C14 ring.
D—H???A
O4—H1O4???O3
O4—H1O4???O1i
N1—H1N1???O1ii
C10—H10A???O4iii
C16—H16B???Cg1i
Symmetry codes: (i) ?x þ 1;y þ1
D—HH???AD???AD—H???A
0.82
0.82
0.90
0.93
0.97
2.41
2.21
2.10
2.55
2.68
2.683 (2)
2.981 (2)
2.994 (3)
3.462 (3)
3.499 (2)
100
156
172
168
142
2;?z þ1
2; (ii) x ? 1;y;z; (iii) ?x þ 1;y ?1
2;?z þ1
2.
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT
(Bruker, 2009); data reduction: SAINT; program(s) used to solve
structure: SHELXTL (Sheldrick, 2008); program(s) used to refine
structure: SHELXTL; molecular graphics: SHELXTL; software used
to prepare material for publication: SHELXTL and PLATON (Spek,
2009).
PP thanks the Development and Promotion of Science and
Technology Talents Project for a fellowship. JH thanks the
Crystal Materials Research Unit, Prince of Songkla Univer-
sity, for financial support. PP and JH thank Dr Nawong
Boonnak for useful suggestions. Mr Teerasak Anantapong,
Department of Biotechnology, Faculty of Agro-Industry,
Prince of Songkla University, is acknowledged for baterial
assays. The authors thank the Prince of Songkla University
and the Universiti Sains Malaysia for the Research University
grant No. 1001/PFIZIK/811160.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: RZ2713).
References
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.
Bedia, K.-K., Elc ¸in, O., Seda, U., Fatma, K., Nathaly, S., Sevim, R. & Dimoglo,
A. (2006). Eur. J. Med. Chem. 41, 1253–1261.
organic compounds
Acta Cryst. (2012). E68, o849–o850doi:10.1107/S1600536812007374Fun et al.
o849
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368
‡ Thomson Reuters ResearcherID: A-3561-2009.
§ Thomson Reuters ResearcherID: A-5085-2009. Additional correspondence
author, e-mail: suchada.c@psu.ac.th.

Page 2

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison,
Wisconsin, USA.
Fun, H.-K., Horkaew, J. & Chantrapromma, S. (2011). Acta Cryst. E67, o2644–
o2645.
Horkaew, J., Chantrapromma, S. & Fun, H.-K. (2011). Acta Cryst. E67, o2985.
Loncle, C., Brunel, J. M., Vidal, N., Dherbomez, M. & Letourneux, Y. (2004).
Eur. J. Med. Chem. 39, 1067–1071.
Promdet, P., Horkaew, J., Chantrapromma, S. & Fun, H.-K. (2011). Acta Cryst.
E67, o3224.
Raj, K. K. V., Narayana, B., Ashalatha, B. V., Kumari, N. S. & Sarojini, B. K.
(2007). Eur. J. Med. Chem. 42, 425–429.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
organic compounds
o850
Fun et al.
? C17H18N2O4
Acta Cryst. (2012). E68, o849–o850

Page 3

supplementary materials
sup-1
Acta Cryst. (2012). E68, o849–o850
supplementary materials
Acta Cryst. (2012). E68, o849–o850 [doi:10.1107/S1600536812007374]
(E)-N′-(3-Ethoxy-4-hydroxybenzylidene)-4-methoxybenzohydrazide
Hoong-Kun Fun, Premrudee Promdet, Jirapa Horkaew, Chatchanok Karalai and Suchada
Chantrapromma
Comment
During the course of our on-going research on benzohydrazide derivatives, which have been reported to possess various
biological properties such as antibacterial and antifungal (Loncle et al., 2004), antitubercular (Bedia et al., 2006) and
antiproliferative (Raj et al., 2007) activities, the synthesis and crystal structures of benzohydrazide derivatives have been
reported (Fun et al., 2011; Horkaew et al., 2011; Promdet et al., 2011). The title compound was synthesized and tested for
its antioxidant and antibacterial activities and found to be inactive.
The molecule of the title benzohydrazide derivative (Fig. 1) exists in a trans-configuration with respect to the C8═N2
bond [1.286 (4) Å], as indicated by the torsion angle N1–N2–C8–C9 = -178.2 (2)°. The molecule is slightly twisted with
the dihedral angle between the two benzene rings of 6.86 (11)°. The middle bridge fragment (O1/C7/N1/N2/C8) is planar
with the torsion angle N2–N1–C7–O1 = 0.8 (4)° and the r.m.s. of 0.0360 (2) Å for the five non-H atoms. The mean plane
through this bridge makes dihedral angles of 28.94 (15) and 26.51 (15)° with the C1–C6 and C9–C14 phenyl rings,
respectively. The methoxy group of 4-methoxyphenyl is slightly twisted with respect to its bound benzene ring [torsion
angle C15–O2–C4–C5 = 10.0 (4)°], whereas the ethoxy group of 3-ethoxy-4-hydroxyphenyl is co-planar with the torsion
angle C11–O3–C16–C17 = 178.5 (2)°.
An intramolecular O4—H1O4···O3 hydrogen bond generates a S(5) ring motif (Bernstein et al., 1995). Bond distances
are of normal values (Allen et al., 1987) and are comparable with those found in related structures (Fun et al., 2011;
Horkaew et al., 2011; Promdet et al., 2011).
In the crystal packing (Fig. 2), the molecules are linked by N—H···O and O—H···O hydrogen bonds and weak C—H···O
interactions (Table 1) into a two-dimensional network paralell to the ab plane. The crystal is further stabilized by C—
H···π weak interaction (Table 1). A C8···O4iv [2.980 (3) Å: (iv) = -x, 1/2+y, 1/2+z] short contact was observed.
Experimental
The title compound was prepared by dissolving 4-methoxybenzohydrazide (2 mmol, 0.30 g) in ethanol (10 ml). A
solution of 3-ethoxy-4-hydroxybenzaldehyde (2 mmol, 0.30 g) in ethanol (10 ml) was then added slowly to the reaction.
The mixture was refluxed for about 5 h and a white solid appeared. The mixture was then cooled to room temperature
and filtered. Colourless needle-shaped single crystals of the title compound suitable for X-ray structure determination
were recrystallized from methanol by slow evaporation of the solvent at room temperature after several days. M. p.
486-488 K.
Refinement
All H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(N-H) = 0.90 Å, d(O-H) =
0.82 Å, d(C-H) = 0.93 Å for aromatic and CH, 0.97 for CH2 and 0.96 Å for CH3 atoms. The Uiso values were constrained

Page 4

supplementary materials
sup-2
Acta Cryst. (2012). E68, o849–o850
to be 1.5Ueq(C, N, O) for methyl, hydroxy and amine H atoms and 1.2Ueq(C) for the remaining H atoms. A rotating group
model was used for the methyl groups. 1879 Friedel pairs were merged. Three outliers (2 1 1, 1 4 0, 3 2 12) were omitted
for the final refinement.
Computing details
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009);
program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL
(Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication:
SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
Figure 1
The molecular structure of the title compound, showing 45% probability displacement ellipsoids. Hydrogen bond are
drawn as dashed line.
Figure 2
The crystal packing of the title compound viewed along the a axis. Hydrogen bonds are drawn as dashed lines.

Page 5

supplementary materials
sup-3
Acta Cryst. (2012). E68, o849–o850
(E)-N′-(3-Ethoxy-4-hydroxybenzylidene)-4-methoxybenzohydrazide
Crystal data
C17H18N2O4
Mr = 314.33
Orthorhombic, P212121
Hall symbol: P 2ac 2ab
a = 5.0607 (9) Å
b = 11.086 (2) Å
c = 27.629 (5) Å
V = 1550.1 (5) Å3
Z = 4
F(000) = 664
Dx = 1.347 Mg m−3
Melting point = 486–488 K
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2637 reflections
θ = 1.5–30.1°
µ = 0.10 mm−1
T = 297 K
Needle, colorless
0.56 × 0.10 × 0.07 mm
Data collection
Bruker APEX DUO CCD area-detector
diffractometer
Radiation source: sealed tube
Graphite monochromator
φ and ω scans
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
Tmin = 0.948, Tmax = 0.993
10252 measured reflections
2637 independent reflections
1921 reflections with I > 2σ(I)
Rint = 0.100
θmax = 30.1°, θmin = 1.5°
h = −7→7
k = −15→15
l = −38→29
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.051
wR(F2) = 0.154
S = 1.04
2637 reflections
210 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0865P)2 + 0.0494P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.36 e Å−3
Δρmin = −0.35 e Å−3
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 > 2sigma(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)
xyzUiso*/Ueq
O1
O2
O3
O4
H1O4
0.7066 (4)
0.2255 (5)
0.5434 (4)
0.2111 (4)
0.2354
0.1645 (2)
−0.16566 (19)
0.52128 (16)
0.70975 (15)
0.6755
0.40465 (7)
0.57022 (7)
0.19944 (6)
0.20065 (7)
0.1747
0.0575 (5)
0.0623 (6)
0.0450 (4)
0.0499 (5)
0.075*