1,2-Dibenzoylhydrazine

Article abstract of DOI:10.1107/S0108270100007010

In the crystal structure of the title compound, C₁₄H₁₂N₂O₂, the molecule lies about a twofold axis; two carbonyl groups and the H atoms of the N-N bond are in a trans orientation with respect to each other. In the crystal, each molecule is linked to the other and vice versa by intermolecular N-H···O hydrogen bonds between the amide hydrogen and the O atoms of neighbouring molecules to form two ten-membered rings, each of which has the graph-set motif C4R₂²(10). This extends as a polymeric chain along the c axis.

Full text of DOI:10.1107/S0108270100007010

organic compounds
Acta Crystallographica Section C
Crystal Structure
The bond lengths and angles are comparable with those of
N,N0-bis(picolinoyl)hydrazine (Shao et al., 1999), except for
Communications
C
O which is slightly longer and the NÐCÐC angle
ISSN 0108-2701
[114.7 (1)ꢀ] which is 2ꢀ larger, possibly due to the greater twist
along the NÐNi bond [torsion angle CÐNÐNiÐCi in Shao et
al. (1999) is 70.9 (2)ꢀ].
1,2-Dibenzoylhydrazine
S. Shanmuga Sundara Raj,a Bohari M. Yamin,b
Ahmed M. A. Boshaala,c M. T. H. Tarafder,c Karen A.
Crousec and Hoong-Kun Funa*
aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800
USM, Penang, Malaysia, bSchool of Chemical Sciences and Food Technology,
Universiti Kebangsaan Malaysia, 43650 Bangi, Selangor, Malaysia, and cDepartment
of Chemistry, Universiti Putra Malaysia, Serdang, Selangor, Malaysia
Correspondence e-mail: hkfun@usm.my
Received 28 April 2000
Accepted 8 May 2000
In the crystal structure of the title compound, C14H12N2O2, the
molecule lies about a twofold axis; two carbonyl groups and
the H atoms of the NÐN bond are in a trans orientation with
respect to each other. In the crystal, each molecule is linked to
the other and vice versa by intermolecular NÐHÁ Á ÁO
hydrogen bonds between the amide hydrogen and the O
atoms of neighbouring molecules to form two ten-membered
rings, each of which has the graph-set motif C4R22(10). This
extends as a polymeric chain along the c axis.
Figure 1
The structure of the title compound showing 50% probability displace-
ment ellipsoids and the atom-numbering scheme [symmetry code:
(i) x, y, 12 z].
In the crystal, each molecule is linked to another and vice
versa by intermolecular NÐHÁ Á ÁO hydrogen bonds between
the amide H atom and the O atoms of neighbouring molecules
to form two ten-membered rings, each of which has the graph-
set motif C4R22(10) (Bernstein et al., 1995). This extends as a
polymeric chain along the c axis.
Comment
Both S-methyldithiocarbazate and S-benzylcarbazate can be
prepared by the addition of chloromethane or benzyl chloride
to a mixture of hydrazine and carbon disul®de, respectively
(Lanfredi et al., 1977; Mattes & Weber, 1980; Ali & Tarafder,
1977). However, under the same conditions, 1,2-dibenzoyl
hydrazine, (I), was obtained instead of S-benzoyldithiocarb-
azate when benzoyl chloride was added to the reaction
mixture.
The dihedral angle of 24.0 (1)ꢀ between the phenyl ring and
the N1ÐC7 O1 group shows that the molecule is not planar.
The asymmetric unit contains half the molecule and the other
Figure 2
The polymeric chain of the packing of the title compound along the c axis.
half is related by a crystallographic twofold axis passing
through the N1ÐN1i bond [symmetry code: (i) x, y,
1
2
z].
Experimental
The symmetry-related group adopts an anticlinal orientation
with respect to the NÐN bond, the torsion angle C7ÐN1Ð
N1iÐC7i being 104.3 (2)ꢀ. The two carbonyl groups and the H
atoms of the NÐN bond are in a trans orientation with respect
to each other.
The title compound was prepared by adding benzoyl chloride to a
mixture of hydrazine, potassium hydroxide and carbon disul®de in
20% aqueous ethanol at 273 K. The precipitate was washed with
water and dried. The crystal used for analysis was obtained by
recrystallization from ethanol.
ꢁ
Acta Cryst. (2000). C56, 1011±1012
# 2000 International Union of Crystallography Printed in Great Britain ± all rights reserved 1011

organic compounds
Crystal data
Data collection was as as described in Shanmuga Sundara Raj et al.
(1999).
3
C14H12N2O2
Mr = 240.26
Monoclinic, C2=c
Ê
a = 14.5439 (2) A
b = 9.7314 (3) A
c = 9.0181 (3) A
ꢀ = 110.938 (1)ꢀ
V = 1192.07 (6) A
Z = 4
Dx = 1.339 Mg m
Mo Kꢁ radiation
Data collection: SMART (Siemens, 1996); cell re®nement: SAINT;
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 and PARST (Nardelli,
1995).
Cell parameters from 2038
re¯ections
ꢂ = 3.00±28.29ꢀ
Ê
Ê
1
ꢃ = 0.092 mm
T = 293 (2) K
3
Ê
Block, light yellow
0.32 Â 0.30 Â 0.28 mm
Data collection
Siemens SMART CCD area-
detector diffractometer
! scans
4148 measured re¯ections
1471 independent re¯ections
965 re¯ections with I > 2ꢄ(I)
Rint = 0.054
max = 28.30ꢀ
h = 19 ! 14
k = 12 ! 12
l = 10 ! 12
The authors would like to thank the Malaysian Govern-
ment, Universiti Kebangsaan Malaysia, Universiti Putra
Malaysia and Universiti Sains Malaysia for research grant
R&D Nos. 03±02±02±005 and 305/p®zik/610942. SSSR thanks
the Universiti Sains Malaysia for a Visiting Postdoctoral
Fellowship.
ꢂ
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.053
wR(F2) = 0.164
S = 0.959
1471 re¯ections
w = 1/[ꢄ2(Fo2) + (0.0975P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max < 0.001
3
Ê
Áꢅmax = 0.30 e A
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: NA1474). Services for accessing these data are
described at the back of the journal.
3
Ê
0.28 e A
Áꢅmin
=
83 parameters
H-atom parameters constrained
Extinction correction: SHELXTL
(Sheldrick, 1997)
Extinction coef®cient: 0.021 (5)
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
References
O1ÐC7
N1ÐC7
1.229 (2)
1.354 (2)
N1ÐN1i
1.385 (3)
Ali, M. A. & Tarafder, M. T. H. (1977). J. Inorg. Nucl. Chem. 39, 1785±1788.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555±1573.
Lanfredi, A. M. M., Tiripiccio, A., Camellini, M. T., Monaci, A. & Tarli, S.
(1977). J. Chem. Soc. Dalton Trans. pp. 417±422.
C7ÐN1ÐN1i
O1ÐC7ÐN1
118.6 (1)
121.3 (2)
O1ÐC7ÐC1
N1ÐC7ÐC1
122.0 (2)
116.7 (1)
Symmetry code: (i) x; y; 12 z.
Mattes, R. & Weber, H. (1980). J. Chem. Soc. Dalton Trans. pp. 423±425.
Nardelli, M. (1995). J. Appl. Cryst. 28, 659.
Shanmuga Sundara Raj, S., Renganayaki, S., Subramanian, E. & Fun, H.-K.
(1999). Acta Cryst. C55, 2182±2184.
Shao, S.-C., Zhu, D.-R., Song, Y., You, X.-Z., Shanmuga Sundara Raj, S. &
Fun, H.-K. (1999). Acta Cryst. C55, 1841±1843.
Sheldrick, G. M. (1997). SHELXTL. Version 5.1. Bruker AXS Inc., Madison,
Wisconsin, USA.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
N1ÐH1AÁ Á ÁO1i
DÐH
HÁ Á ÁA
2.13
DÁ Á ÁA
DÐHÁ Á ÁA
0.86
2.924 (2)
154
Symmetry code: (i) x; 2 y; 12 ‡ z.
ꢁ
1012 S. Shanmuga Sundara Raj et al. C14H12N2O2
Acta Cryst. (2000). C56, 1011±1012