Full text of DOI:10.1107/S0108270100007459

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
4,5-Diazafluoren-9-one benzoyl-
hydrazone monohydrate
Zhong-Lin Lu,a Wen Xiao,a Zhong-Ning Chen,a Xiao-Yang
Gong,a S. Shanmuga Sundara Raj,b Ibrahim Abdul Razakb
and Hoong-Kun Funb*
Figure 1
The structure of (I) showing 50% probability displacement ellipsoids and
the atom-numbering scheme.
aThe Institute of Physical Chemistry, School of Chemistry and Chemical Engineering,
Zhongshan University, Guangzhou 510275, People's Republic of China, and bX-ray
Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM,
Penang, Malaysia
other benzoylhydrazine (Fun et al., 1997) and 4,5-diaza-
¯uorene derivatives (Lu et al., 1996). The molecule is in the
keto tautomeric form. The dihedral angle between the di-
aza¯uorene moiety and the phenyl ring is 11.3 (1)ꢀ, and the
two fragments make angles of 13.2 (1) and 23.2 (1)ꢀ, respec-
tively, with the central hydrazone moiety. In the solid state, the
molecules form in®nite chain-like structures via OÐHÁ Á ÁN
hydrogen bonds involving the water molecules and diaza-
¯uorene moieties.
We have observed previously that due to the possibility of
different charge concentrations between the two pyridyl N
atoms of the diaza¯uorene moiety, the one with greater charge
is involved in the stronger hydrogen bonds, whereas the other
may be involved in only a weak interaction (Fun et al., 1995;
Lu et al., 1995). However, in this structure, both the N atoms
are involved in a similar type of OÐHÁ Á ÁN hydrogen bond
with the water molecule. We also note that the aroylhydrazine
derivatives crystallize in hydrated forms only.
Correspondence e-mail: hkfun@usm.my
Received 12 May 2000
Accepted 19 May 2000
The title compound, C18H12N4OÁH2O, adopts the keto
tautomeric form and the azomethine C N double bond is
in the E con®guration. The dihedral angle between the planes
of the diaza¯uorene moiety and the phenyl ring is 11.3 (1)ꢀ. In
the solid state, the molecules form in®nite chain-like
structures via OÐHÁ Á ÁN hydrogen bonds involving the water
molecules and diaza¯uorene moieties.
Comment
Aroylhydrazones have continued to attract extensive atten-
tion from chemists because of their wide-ranging biological
activity and their strong ability to chelate to transition metal
ions, lanthanide metal ions and main-group metal ions forming
metal complexes (Fun et al., 1999; Lu et al., 1999; Sangeetha et
al., 1996; Ainscough et al., 1998). Furthermore, 4,5-diaza-
¯uoren-9-one and its derivatives are also strong chelating
agents and have been used as ligands to form functional
ruthenium complexes (Chao et al., 1999). The combination of
the two functional groups yielding ligands capable of forming
polymetallic complexes would therefore be of interest for
their potential multi-redox, catalytic, electronic and energy-
transfer properties. As part of studies on the synthesis and
characterization of new aroylhydrazone derivatives, we report
here the crystal structure of 4,5-diaza¯uoren-9-one benzoyl-
hydrazone monohydrate, (I).
Experimental
The synthesis of the title compound was carried out by reaction of
4,5-diaza¯uoren-9-one and benzoylhydrazine in ethanol solution
under re¯ux for 5 h. Single crystals were obtained by recrystallization
from ethanol.
Crystal data
3
C18H12N4OÁH2O
Dx = 1.375 Mg m
Mo Kꢁ radiation
Cell parameters from 3585
re¯ections
Mr = 318.33
Monoclinic, P21=n
Ê
a = 8.4880 (2) A
ꢂ = 1.79±28.34ꢀ
ꢃ = 0.093 mm
T = 293 (2) K
Ê
b = 22.7523 (2) A
1
Ê
c = 8.7810 (2) A
ꢀ = 114.929 (1)ꢀ
V = 1537.80 (5) A
Z = 4
3
Ê
Needle, yellow
0.38 Â 0.18 Â 0.12 mm
Data collection
Siemens SMART CCD area-
detector diffractometer
! scans
10723 measured re¯ections
3729 independent re¯ections
1870 re¯ections with I > 2ꢄ(I)
Rint = 0.078
ꢂmax = 28.31ꢀ
h = 9 ! 11
k = 29 ! 27
l = 11 ! 11
The bond lengths and angles observed in this structure are
normal and comparable with those found in the structures of
ꢁ
Acta Cryst. (2000). C56, 1017±1018
# 2000 International Union of Crystallography Printed in Great Britain ± all rights reserved 1017

organic compounds
Re®nement
structure: SHELXTL; molecular graphics: SHELXTL; software used
to prepare material for publication: SHELXTL and PLATON (Spek,
1990).
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.061
wR(F2) = 0.121
S = 0.930
3729 re¯ections
226 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[ꢄ2(Fo2) + (0.0695P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max < 0.001
3
Ê
Áꢅmax = 0.29 e A
The authors would like to thank the Malaysian Government
and Universiti Sains Malaysia for research grant R & D No.
305/p®zik/610942, the National Nature Science Foundation of
China and the China Postdoctoral Science Foundation. SSSR
thanks the Universiti Sains Malaysia for a Visiting Post-
doctoral Fellowship.
3
Ê
0.28 e A
Áꢅmin
=
Extinction correction: SHELXTL
(Sheldrick, 1997)
Extinction coef®cient: 0.014 (2)
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
N1ÐC1
N1ÐC11
N2ÐC10
N2ÐC9
1.339 (3)
1.340 (3)
1.332 (3)
1.339 (3)
N3ÐC5
N3ÐN4
N4ÐC12
O1ÐC12
1.290 (3)
1.371 (3)
1.378 (3)
1.216 (3)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1396). Services for accessing these data are
described at the back of the journal.
C5ÐN3ÐN4
N3ÐN4ÐC12
O1ÐC12ÐN4
119.4 (2)
116.5 (2)
122.0 (2)
O1ÐC12ÐC13
N4ÐC12ÐC13
121.8 (2)
116.1 (2)
References
Ainscough, W., Brodie, A. M., Dobbs, A. J., Ranford, J. D. & Waters, J. M.
(1998). Inorg. Chim. Acta, 267, 27±34.
Chao, H., Li, R.-H., Ye, B.-H., Li, H., Feng, X.-L., Cai, J.-W., Zhou, J.-Y. & Ji,
L.-N. (1999). J. Chem. Soc. Dalton Trans. pp. 3711±3717.
Fun, H.-K., Chinnakali, K., Razak, I. A., Lu, Z.-L. & Kang, B.-S. (1999). Acta
Cryst. C55, 574±576.
C5ÐN3ÐN4ÐC12
N3ÐN4ÐC12ÐO1
170.4 (2)
0.6 (3)
N3ÐN4ÐC12ÐC13
177.6 (2)
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., Zhu, D.-R. & You, X.-Z. (1995). Acta Cryst. C51,
2076±2078.
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Lu, Z.-L., Duan, C.-Y., Tian, Y.-P., You, X.-Z., Fun, H.-K. & Sivakumar, K.
(1995). Acta Cryst. C51, 2078±2080.
N4ÐH4AÁ Á ÁO1W
O1WÐH1W1Á Á ÁN1i
O1WÐH2W1Á Á ÁN2ii
0.86
0.94 (3)
0.89 (5)
2.21
2.00 (4)
2.04 (5)
2.921 (3)
2.886 (3)
2.907 (3)
140
157 (3)
163 (4)
Lu, Z.-L., Kang, B.-S., Fun, H.-K., Razak, I. A. & Chinnakali, K. (1999). Acta
Cryst. C55, 89±91.
Lu, Z.-L., Shan, B.-Z., Duan, C.-Y., Tian, Y.-P., You, X.-Z., Fun, H.-K. &
Sivakumar, K. (1996). Acta Cryst. C52, 1720±1722.
Sangeetha, N. R., Pal, C. K., Ghosh, P. & Pal, S. (1996). J. Chem. Soc. Dalton
Trans. pp. 3293±3298.
Symmetry codes: (i) 2 x; 1 y; z; (ii) x 1; y; z.
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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.
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
ꢁ
1018 Zhong-Lin Lu et al. C18H12N4OÁH2O
Acta Cryst. (2000). C56, 1017±1018