p-methoxybenzaldehyde benzoylhydrazone monohydrate

Article abstract of DOI:10.1107/S010827010000799X

The crystal structure of the title compound, C₁₅H₁₄N₂O₂·H₂O, is in the keto tautomeric form and the configuration at the azomethine C double bond N double bond is E. The molecule is non-planar, with a dihedral angle of 27.3 (1)° between the aromatic rings. The crystal structure is stabilized by extensive hydrogen bonding involving the water molecule and hydrazone moiety.

Full text of DOI:10.1107/S010827010000799X

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
compounds. The keto group is in the plane of the central
hydrazone bridge.
The asymmetry of the exocyclic angles at C5 is small [C4Ð
Ê
ꢀ
ISSN 0108-2701
C5ÐC8 = 122.3 (2) A and C6ÐC5ÐC8 = 120.0 (2) ], while
Ê
that at C2 is larger [C3ÐC2ÐO1 = 114.7 (2) A and C7ÐC2Ð
ꢀ
O1 = 125.0 (2) ], is similar to that usually found in anisoles,
p-Methoxybenzaldehyde benzoyl-
hydrazone monohydrate
and is caused by the tendency the methoxy group has to be
coplanar with the phenyl ring. Conjugation of oxygen with
phenyl, which is responsible for this coplanarity (Domiano et
al., 1979), also causes some shortening of the C2ÐO1 bond.
Some asymmetry is observed also for the exocyclic angles at
a
a
S. Shanmuga Sundara Raj, Hoong-Kun Fun, * Zhong-Lin
b
b
b
c
ꢀ
Lu, Wen Xiao, Xiao-Yang Gong and Chang-Ming Gen
C10 [C9ÐC10ÐC11 = 118.2 (2) and C9ÐC10ÐC15 =
ꢀ
1
2
22.0 (2) ], probably caused by the contacts H11Á Á ÁO2 of
a
X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800
Ê
Ê
.72 A and H15Á Á ÁN2 of 2.74 A. The torsion angles C4ÐC5Ð
b
USM, Penang, Malaysia, The Institute of Physical Chemistry, School of Chemistry
and Chemical Engineering, Zhongshan University, Guangzhou 510275, People's
ꢀ
ꢀ
C8ÐN1 of 11.7 (4) and N2ÐC9ÐC10ÐC15 of � 44.7 (3)
c
indicate that the methoxyphenyl and phenyl substituents are
in synperiplanar and synclinal orientations with respect to the
central hydrazone plane. The methoxyphenyl ring makes a
Republic of China, and Anli China Company, Guangzhou, People's Republic of
China
Correspondence e-mail: hkfun@usm.my
ꢀ
dihedral angle of 16.4 (1) with the hydrazone bridge and the
ꢀ
Received 8 May 2000
Accepted 30 May 2000
phenyl ring is twisted by an angle of 43.1 (1) with respect to
the plane of the central hydrazone linkage.
The water and hydrazone group are involved in NÐHÁ Á ÁO
and OÐHÁ Á ÁO hydrogen bonds forming a two-dimensional
network. The H1W atom is involved in a three-center
hydrogen bond.
The crystal structure of the title compound, C H N O ÁH O,
1
5
14
2
2
2
is in the keto tautomeric form and the con®guration at the
azomethine C N double bond is E. The molecule is non-
ꢀ
planar, with a dihedral angle of 27.3 (1) between the aromatic
rings. The crystal structure is stabilized by extensive hydrogen
bonding involving the water molecule and hydrazone moiety.
Comment
Aroylhydrazone compounds are being studied extensively
because of the strong coordinating hydrazone group which is
capable of forming polynuclear complexes. As a continuation
of our work on the synthesis and characterization of aroyl-
hydrazone compounds (Fun et al., 1996, 1997, 1999; Lu et al.,
1999; Shanmuga Sundara Raj et al., 1999), we report the
crystal structure of the title compound, (I).
Figure 1
The structure of (I) showing 50% probability displacement ellipsoids and
the atom-numbering scheme.
Experimental
The synthesis of the title compound was carried out by reaction of p-
methoxybenzaldehyde and benzoylhydrazine in ethanol solution
under re¯ux for 3 h. Single crystals were obtained by recrystallization
from ethanol.
The molecule is non-planar with a dihedral angle of
ꢀ
2
7.3 (1) between the aromatic rings. The N1ÐN2 and
C9ÐO2 bond distances, which are consistent with those in the
related compounds p-methoxybenzaldehyde isonicotinoyl-
hydrazone monohydrate (Shanmuga Sundara Raj et al., 1999)
and its dihydrate derivative (Fun et al., 1996), indicate that
these bonds correspond to single and double bonds. Thus, the
molecule is in the keto tautomeric form. Also, the con®gura-
tion at the azomethine N1ÐC8 double bond is E (Fig. 1). The
C1ÐO1 and O1ÐC2 bond lengths in the hydroxyphenyl
Crystal data
�
3
C
15
H
14
N
2
O
2
2
ÁH O
D
x
= 1.251 Mg m
M = 272.30
r
Mo Kꢁ radiation
Monoclinic, P2 =c
Cell parameters from 3248
re¯ections
1
Ê
a = 11.9398 (6) A
Ê
ꢀ
b = 11.8595 (6) A
ꢂ = 1.90±29.37
Ê
c = 11.3972 (6) A
� 1
ꢃ = 0.088 mm
T = 293 (2) K
ꢀ
ꢀ
= 116.389 (1)
moiety are consistent with those [1.432 (2) and 1.370 (1), and
Ê
Ê
3
V = 1445.68 (13) A
Z = 4
Slab, colorless
0.40 Â 0.24 Â 0.16 mm
1
.436 (2) and 1.367 (2) A, respectively] in the above related
Acta Cryst. (2000). C56, 1013±1014
# 2000 International Union of Crystallography ꢁ Printed in Great Britain ± all rights reserved 1013

organic compounds
Data collection
The collection of intensity data was as described by Shanmuga
Sundara Raj et al. (1999). The H atoms of the water molecule were
re®ned isotropically while all the others were ®xed geometrically and
allowed to ride on their parent atoms.
Siemens SMART CCD area-
detector diffractometer
R
int = 0.067
ꢀ
ꢂ
max = 29.34
!
scans
h = � 16 ! 14
k = � 12 ! 16
l = � 14 ! 15
1
3
1
0036 measured re¯ections
650 independent re¯ections
704 re¯ections with I > 2ꢄ(I)
Data collection: SMART (Siemens, 1996); cell re®nement: SAINT
Siemens, 1996); data reduction: SAINT; program(s) used to solve
(
structure: SHELXTL (Sheldrick, 1997); program(s) used to re®ne
structure: SHELXTL; molecular graphics: SHELXTL; software used
to prepare material for publication: SHELXTL, PARST (Nardelli,
Re®nement
2
2
2
2
Re®nement on F
2
w = 1/[ꢄ (F
where P = (F
(Á/ꢄ)max < 0.001
o
) + (0.0764P) ]
2
2 2
R[F > 2ꢄ(F )] = 0.053
wR(F ) = 0.120
S = 0.925
o c
+ 2F )/3
1995) and PLATON (Spek, 1990).
2
Ê
� 3
Áꢅmax = 0.23 e A
Ê
� 3
2
1
833 re¯ections
90 parameters
Áꢅmin = � 0.21 e A
The authors would like to thank the Malaysian Government
and Universiti Sains Malaysia for research grant R&D No.
05/p®zik/610942 and the National Nature Science Founda-
Extinction correction: SHELXTL
(Sheldrick, 1997)
Extinction coef®cient: 0.013 (3)
H atoms: see below
3
tion of China and China Postdoctoral Science Foundation.
SSSR thanks the Universiti Sains Malaysia for a Visiting
Postdoctoral Fellowship.
Table 1
Selected geometric parameters (A, ).
Ê
ꢀ
O1ÐC2
O1ÐC1
O2ÐC9
N1ÐC8
1.371 (2)
1.434 (3)
1.236 (2)
1.274 (3)
N1ÐN2
N2ÐC9
C5ÐC8
C10ÐC15
1.392 (2)
1.346 (3)
1.459 (3)
1.368 (3)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA1476). Services for accessing these data are
described at the back of the journal.
C8ÐN1ÐN2
C9ÐN2ÐN1
O2ÐC9ÐN2
115.3 (2)
119.1 (2)
122.7 (2)
O2ÐC9ÐC10
N2ÐC9ÐC10
121.6 (2)
115.7 (2)
References
Domiano, P., Nardelli, M., Balsamo, A., Macchia, B. & Macchia, F. (1979). Acta
Cryst. B35, 1363±1372.
Fun, H.-K., Chinnakali, K., Razak, I. A., Lu, Z.-L. & Kang, B.-S. (1999). Acta
Cryst. C55, 574±576.
Fun, H.-K., Lu, Z.-L., Duan, C.-Y., Tian, Y.-P., You, X.-Z., Gong, X.-Y. & Guo,
Y.-M. (1997). Acta Cryst. C53, 1454±1455.
Fun, H.-K., Sivakumar, K., Lu, Z.-L., Duan, C.-Y., Tian, Y.-P. & You, X.-Z.
C8ÐN1ÐN2ÐC9
N2ÐN1ÐC8ÐC5
� 173.6 (2)
� 179.9 (2)
N1ÐN2ÐC9ÐC10
178.7 (2)
(
1996). Acta Cryst. C52, 986±988.
Lu, Z.-L., Kang, B.-S., Fun, H.-K., Razak, I. A. & Chinnakali, K. (1999). Acta
Cryst. C55, 89±91.
Nardelli, M. (1995). J. Appl. Cryst. 28, 659.
Shanmuga Sundara Raj, S., Fun, H.-K., Lu, Z.-L., Xiao, W., Tong, Y.-X. &
Kang, B.-S. (1999). Acta Cryst. C55, 942±944.
Shanmuga Sundara Raj, S., Renganayaki, S., Subramanian, E. & Fun, H.-K.
Table 2
Hydrogen-bonding geometry (A, ).
Ê
ꢀ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
(
1999). Acta Cryst. C55, 2182±2184.
O1WÐH1WÁ Á ÁN1
O1WÐH1WÁ Á ÁO2
0.90 (3)
0.90 (3)
0.86
2.53 (2)
2.05 (4)
1.99
3.257 (2)
2.858 (3)
2.829 (2)
2.825 (2)
138 (3)
150 (3)
165
Sheldrick, G. M. (1997). SHELXTL Software Reference Manual. Version 5.1.
Bruker AXS Inc., Madison, Wisconsin, USA.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Spek, A. L. (1990). Acta Cryst. A46, C-34.
i
N2ÐH2Á Á ÁO1W
ii
O1WÐH2WÁ Á ÁO2
Symmetry codes: (i) x; � y; ‡ z; (ii) 1 � x; � y; 1 � z.
0.89 (3)
1.95 (3)
169 (3)
1
2
1
2
1
014 S. Shanmuga Sundara Raj et al. ꢁ
C
15
H
14
N
O
ÁH
O
Acta Cryst. (2000). C56, 1013±1014
2
2
2