1,2-Di­benzoyl­hydrazine

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 C4R(10). This extends as a polymeric chain along the c axis.

S1. Comment

Both S-methyldithiocarbazate and S-benzylcarbazate can be prepared by the addition of chloromethane or benzylchloride into a mixture of hydrazine and carbon disulfide, 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-benzoyldithiocarbazate when benzoylchloride was added to the reaction mixture. \sch

The dihedral angle of 24.0 (1)° between the phenyl ring and the N1—C7=O1 group shows that the molecule is not planar. The asymmetric unit contains half the molecule and the other half is related by a crystallographic twofold axis passing through N1—N1ⁱ bond [(i) = −x, y, 1/2 − z]. The symmetry-related group adopts anti-clinal orientation with respect to the NN bond; the torsion angle, C7—N1—N1ⁱ—C7ⁱ, being 104.3 (2)°. The two carbonyl groups and hydrogen atoms of the NN bond are in a trans orientation to each other.

The bond lengths and bond angles are comparable with those of N,N'-bis (picolinoyl)hydrazine (Shao et al., 1999) except for C═O which is slightly longer and N—C—C angle [114.7 (1)°] which is 2° larger, may be due to the more twist along the N—Nⁱ bond [torsion angle C—N—Nⁱ—Cⁱ in Shao et al. (1999) is −70.9 (2)°].

In the crystal, each molecule is linked to the other and vice-versa by intermolecular N—H···O hydrogen bondings between the amide hydrogen and the oxygen atom of the neighbouring molecules to form two ten-membered rings each of which has the graph-set motif of C4R₂²(10) (Bernstein et al., 1995). This extends as a polymeric chain along the c axis.

S2. Experimental

The compound was prepared by adding benzoylchloride into the mixture of hydrazine, potassium hydroxide and carbon disulfide in 20% aqueous ethanol at 273 K. The precipitate was washed with water and dried. The crystal was obtained by recrystallization from ethanol.

S3. Refinement

Data collection was as that followed by Shanmuga Sundara Raj et al. (1999).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT; data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PARST (Nardelli, 1995).

Figures

	Fig. 1. The structure of title compound showing 50% probability displacement ellipsoids and the atom-numbering scheme. (i = −x, y, 1/2 − z).
	Fig. 2. The polymeric chain of the packing along the c axis.

1,2,dibenzoylhydrazine

Crystal data

C14H12N2O2	F(000) = 504
Mr = 240.26	Dx = 1.339 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.5439 (2) Å	Cell parameters from 2038 reflections
b = 9.7314 (3) Å	θ = 3.0–28.3°
c = 9.0181 (3) Å	µ = 0.09 mm^−1
β = 110.938 (1)°	T = 293 K
V = 1192.07 (6) Å^3	Block, light yellow
Z = 4	0.32 × 0.30 × 0.28 mm

Data collection

Siemens SMART CCD area detector diffractometer	965 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.054
Graphite monochromator	θmax = 28.3°, θmin = 3.0°
Detector resolution: 8.33 pixels mm^-1	h = −19→14
ω scans	k = −12→12
4148 measured reflections	l = −10→12
1471 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.164	w = 1/[σ^2(Fo^2) + (0.0975P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.96	(Δ/σ)max < 0.001
1471 reflections	Δρmax = 0.30 e Å^−3
83 parameters	Δρmin = −0.28 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.021 (5)

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.07908 (9)	0.87939 (14)	0.10828 (13)	0.0480 (4)
N1	0.05005 (10)	1.00954 (16)	0.29345 (16)	0.0449 (5)
H1A	0.0736	1.0562	0.3798	0.054*
C1	0.21547 (11)	0.92445 (18)	0.34607 (17)	0.0364 (4)
C2	0.26157 (14)	1.0190 (2)	0.4632 (2)	0.0475 (5)
H2A	0.2267	1.0939	0.4796	0.057*
C3	0.36046 (15)	1.0019 (2)	0.5567 (2)	0.0599 (6)
H3A	0.3917	1.0659	0.6351	0.072*
C4	0.41221 (15)	0.8902 (2)	0.5335 (2)	0.0581 (6)
H4A	0.4784	0.8797	0.5954	0.070*
C5	0.36629 (15)	0.7951 (2)	0.4196 (2)	0.0535 (6)
H5A	0.4009	0.7188	0.4059	0.064*
C6	0.26837 (14)	0.8120 (2)	0.32478 (19)	0.0464 (5)
H6A	0.2378	0.7477	0.2463	0.056*
C7	0.11007 (12)	0.93454 (18)	0.23956 (17)	0.0364 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0420 (7)	0.0675 (9)	0.0314 (6)	−0.0041 (6)	0.0094 (5)	−0.0060 (5)
N1	0.0281 (8)	0.0723 (11)	0.0315 (7)	−0.0012 (7)	0.0073 (6)	−0.0065 (6)
C1	0.0310 (9)	0.0493 (10)	0.0304 (8)	−0.0025 (7)	0.0129 (7)	0.0047 (7)
C2	0.0346 (10)	0.0607 (12)	0.0464 (10)	−0.0023 (8)	0.0136 (8)	−0.0070 (8)
C3	0.0370 (11)	0.0832 (15)	0.0526 (11)	−0.0073 (10)	0.0075 (9)	−0.0137 (10)
C4	0.0320 (10)	0.0893 (16)	0.0491 (11)	0.0059 (10)	0.0097 (8)	0.0064 (10)
C5	0.0472 (11)	0.0663 (13)	0.0499 (11)	0.0157 (9)	0.0208 (9)	0.0096 (9)
C6	0.0455 (11)	0.0544 (11)	0.0402 (9)	0.0023 (8)	0.0164 (8)	0.0003 (8)
C7	0.0325 (9)	0.0482 (9)	0.0287 (8)	−0.0051 (7)	0.0111 (6)	0.0041 (6)

Geometric parameters (Å, º)

O1—C7	1.229 (2)	C2—H2A	0.9300
N1—C7	1.354 (2)	C3—C4	1.380 (3)
N1—N1^i	1.385 (3)	C3—H3A	0.9300
N1—H1A	0.8600	C4—C5	1.367 (3)
C1—C2	1.380 (2)	C4—H4A	0.9300
C1—C6	1.390 (3)	C5—C6	1.384 (3)
C1—C7	1.493 (2)	C5—H5A	0.9300
C2—C3	1.393 (3)	C6—H6A	0.9300
C7—N1—N1^i	118.6 (1)	C5—C4—C3	120.06 (18)
C7—N1—H1A	120.7	C5—C4—H4A	120.0
N1^i—N1—H1A	120.7	C3—C4—H4A	120.0
C2—C1—C6	119.26 (16)	C4—C5—C6	120.16 (19)
C2—C1—C7	123.69 (16)	C4—C5—H5A	119.9
C6—C1—C7	117.04 (16)	C6—C5—H5A	119.9
C1—C2—C3	119.86 (18)	C5—C6—C1	120.41 (17)
C1—C2—H2A	120.1	C5—C6—H6A	119.8
C3—C2—H2A	120.1	C1—C6—H6A	119.8
C4—C3—C2	120.22 (19)	O1—C7—N1	121.3 (2)
C4—C3—H3A	119.9	O1—C7—C1	122.0 (2)
C2—C3—H3A	119.9	N1—C7—C1	116.7 (1)
C6—C1—C2—C3	0.9 (3)	C7—C1—C6—C5	−179.59 (15)
C7—C1—C2—C3	−179.67 (16)	N1^i—N1—C7—O1	7.9 (2)
C1—C2—C3—C4	−0.5 (3)	N1^i—N1—C7—C1	−173.15 (13)
C2—C3—C4—C5	−0.7 (3)	C2—C1—C7—O1	156.00 (17)
C3—C4—C5—C6	1.5 (3)	C6—C1—C7—O1	−24.6 (2)
C4—C5—C6—C1	−1.1 (3)	C2—C1—C7—N1	−23.0 (2)
C2—C1—C6—C5	−0.2 (3)	C6—C1—C7—N1	156.41 (15)

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
N1—H1A···O1^ii	0.86	2.13	2.924 (2)	154

Symmetry code: (ii) x, −y+2, z+1/2.