1,2-Bis[(1,3-benzodioxol-5-yl)methyl­idene]hydrazine

Jasinski, J.P.; Golen, J.A.; Praveen, A.S.; Narayana, B.; Yathirajan, H.S.

doi:10.1107/S1600536811050793

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page o7

doi:10.1107/S1600536811050793

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1,2-Bis[(1,3-benzodioxol-5-yl)methylidene]hydrazine

Jerry P. Jasinski,^a ^* James A. Golen,^a A. S. Praveen,^b B. Narayana ^c and H. S. Yathirajan ^b

^aDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^cDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, 574 199, India
^*Correspondence e-mail: jjasinski@keene.edu

(Received 23 November 2011; accepted 25 November 2011; online 3 December 2011)

The complete molecule of the title compound, C₁₆H₁₂N₂O₄, is generated by the application of a centre of inversion. The (1,3-benzodioxol-5-yl)methylidene fused-ring system is approximately planar (r.m.s. deviation = 0.020 Å) and is essentially coplanar with the central hydrazine group [dihedral angle = 5.08 (9)°]. Weak π–π intermolecular interactions are observed [centroid–centroid distance = 3.8553 (8) Å], providing some packing stability.

Related literature

For the biological activity of Schiff bases, see: Aydogan et al. (2001 ); Desai et al. (2001 ); El-Masry et al. (2000 ); Hodnett & Dunn (1970 ); Pandey et al. (1999 ); Singh & Dash (1988 ); Taggi et al. (2002 ); Xu et al. (1997 ). For the crystallography and coordination chemistry of compounds containing the azine functionality or a diimine linkage, see: Xu et al. (1997); Kundu et al. (2005 ). For related structures, see: Liu et al. (2007 ); Odabaşoğlu et al. (2007 ); Zhang & Zheng (2008 ); Zheng et al. (2005a ,b ).

Experimental

Crystal data

C₁₆H₁₂N₂O₄
M_r = 296.28
Monoclinic, P 2₁ /c
a = 6.1835 (2) Å
b = 4.5970 (2) Å
c = 23.8487 (10) Å
β = 96.080 (4)°
V = 674.10 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 170 K
0.28 × 0.25 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.971, T_max = 0.992
4759 measured reflections
1746 independent reflections
1402 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.118
S = 1.04
1746 reflections
100 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 $[Oxford Diffraction (2010). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811050793/tk5026sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811050793/tk5026Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811050793/tk5026Isup3.cml

checkCIF report

Comment top

Schiff bases are used as substrates in the preparation of a number of industrial and biologically active compounds via ring closure, cycloaddition and replacement reactions. Moreover, Schiff bases are also known to have biological activities such as antimicrobial (El-Masry et al., 2000 & Pandey et al., 1999), antifungal (Singh & Dash, 1988), antitumor (Hodnett & Dunn, 1970; Desai et al., 2001), and as herbicides. Schiff bases have also been employed as ligands for complexation of metal ions (Aydogan et al., 2001). On the industrial scale, they have a wide range of applications such as dyes and pigments (Taggi et al., 2002). Compounds containing an azine functionality or a diimine linkage have been investigated in terms of their crystallography and coordination chemistry (Xu et al., 1997; Kundu et al., 2005).

The crystal structures of some Schiff base hydrazines, viz., 4-fluorobenzaldehyde [(E)-4-fluorobenzylidene]hydrazone (Odabaşoğlu et al., 2007), N,N'-bis(3 nitrobenzylidene)hydrazine (Zheng et al., 2005a), N,N'-bis(4-chlorobenzylidene)hydrazine (Zheng et al., 2005b), 1,2-bis(2-chlorobenzylidene)hydrazine (Zhang & Zheng, 2008), N,N'-bis(4-hydroxybenzylidene)hydrazine (Liu et al., 2007) have been reported. In view of the importance of Schiff base hydrazines, the crystal structure of title compound (I) is reported

In the crystal structure of the title compound, C₁₆H₁₂N₂O₄, the two 1,3-benzodioxol-5-ylmethylidene rings are planar to the hydrazine group and to each other (Fig. 1). Weak π–π intermolecular interactions are observed (centroid–centroid distance = 3.8553 (8) Å) providing some packing stability (Fig. 2).

Related literature top

For the biological activity of Schiff bases, see: Aydogan et al. (2001); Desai et al. (2001); El-Masry et al. (2000); Hodnett & Dunn (1970); Pandey et al. (1999); Singh & Dash (1988); Taggi et al. (2002); Xu et al. (1997). For the crystallography and coordination chemistry of compounds containing the azine functionality or a diimine linkage, see: Xu et al. (1997); Kundu et al. (2005). For related structures, see: Liu et al. (2007); Odabaşoğlu et al. (2007); Zhang & Zheng (2008); Zheng et al. (2005a,b).

Experimental top

A mixture of piperanal (3.0 g, 0.02 mol) and hydrazine hydrate (0.6 ml, 0.012 mol) was refluxed in 15 ml of absolute alcohol containing 2 drops of sulfuric acid, for about 3 hours. On cooling, the solid separated was filtered and dried. Single crystals were grown from DMF by slow evaporation. Yield: 81%. (M.pt.: 476 K).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis RED (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed along the b axis. The H atoms have been removed for clarity.

1,2-Bis[(1,3-benzodioxol-5-yl)methylidene]hydrazine top

Crystal data top

C₁₆H₁₂N₂O₄	F(000) = 308
M_r = 296.28	D_x = 1.460 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1659 reflections
a = 6.1835 (2) Å	θ = 3.4–30.1°
b = 4.5970 (2) Å	µ = 0.11 mm⁻¹
c = 23.8487 (10) Å	T = 170 K
β = 96.080 (4)°	Plate, yellow
V = 674.10 (5) Å³	0.28 × 0.25 × 0.08 mm
Z = 2

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	1746 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1402 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 16.1500 pixels mm^-1	θ_max = 30.1°, θ_min = 3.4°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = −5→6
T_min = 0.971, T_max = 0.992	l = −32→23
4759 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0592P)² + 0.1301P] where P = (F_o² + 2F_c²)/3
1746 reflections	(Δ/σ)_max < 0.001
100 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₁₂N₂O₄	V = 674.10 (5) Å³
M_r = 296.28	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.1835 (2) Å	µ = 0.11 mm⁻¹
b = 4.5970 (2) Å	T = 170 K
c = 23.8487 (10) Å	0.28 × 0.25 × 0.08 mm
β = 96.080 (4)°

Data collection top

Oxford Diffraction Xcalibur Eos Gemini diffractometer	1746 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	1402 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.992	R_int = 0.019
4759 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	Δρ_max = 0.20 e Å⁻³
1746 reflections	Δρ_min = −0.18 e Å⁻³
100 parameters

Special details top

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 > 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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.40433 (16)	0.1982 (3)	0.30379 (4)	0.0593 (4)
O2	0.05345 (15)	0.0196 (2)	0.29688 (4)	0.0480 (3)
N1	0.48668 (18)	0.9022 (3)	0.47706 (4)	0.0426 (3)
C1	0.2915 (2)	0.8116 (3)	0.46809 (5)	0.0382 (3)
H1A	0.1891	0.8790	0.4909	0.046*
C2	0.22381 (19)	0.6056 (3)	0.42323 (5)	0.0347 (3)
C3	0.0129 (2)	0.4965 (3)	0.41852 (5)	0.0400 (3)
H3A	−0.0823	0.5609	0.4435	0.048*
C4	−0.0601 (2)	0.2930 (3)	0.37729 (6)	0.0417 (3)
H4A	−0.2004	0.2178	0.3747	0.050*
C5	0.0850 (2)	0.2105 (3)	0.34108 (5)	0.0358 (3)
C6	0.2948 (2)	0.3188 (3)	0.34523 (5)	0.0367 (3)
C7	0.36960 (19)	0.5151 (3)	0.38540 (5)	0.0385 (3)
H7A	0.5111	0.5862	0.3877	0.046*
C8	0.2520 (2)	0.0174 (4)	0.27125 (6)	0.0469 (4)
H8A	0.3079	−0.1794	0.2701	0.056*
H8B	0.2271	0.0900	0.2329	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0448 (6)	0.0813 (9)	0.0538 (6)	−0.0115 (5)	0.0141 (5)	−0.0309 (6)
O2	0.0443 (5)	0.0526 (7)	0.0463 (6)	−0.0050 (4)	0.0008 (4)	−0.0174 (5)
N1	0.0472 (6)	0.0415 (7)	0.0384 (6)	−0.0023 (5)	0.0016 (5)	−0.0110 (5)
C1	0.0428 (7)	0.0355 (7)	0.0360 (6)	0.0014 (5)	0.0027 (5)	−0.0033 (5)
C2	0.0375 (6)	0.0323 (7)	0.0335 (6)	0.0014 (5)	−0.0005 (5)	−0.0003 (5)
C3	0.0372 (6)	0.0429 (8)	0.0406 (7)	0.0009 (5)	0.0067 (5)	−0.0035 (6)
C4	0.0321 (6)	0.0450 (8)	0.0476 (7)	−0.0035 (5)	0.0023 (5)	−0.0043 (6)
C5	0.0370 (6)	0.0340 (7)	0.0347 (6)	0.0006 (5)	−0.0036 (5)	−0.0020 (5)
C6	0.0356 (6)	0.0405 (7)	0.0342 (6)	0.0014 (5)	0.0039 (5)	−0.0020 (5)
C7	0.0327 (6)	0.0421 (8)	0.0402 (7)	−0.0036 (5)	0.0015 (5)	−0.0031 (5)
C8	0.0476 (8)	0.0507 (9)	0.0420 (7)	0.0016 (6)	0.0026 (6)	−0.0110 (6)

Geometric parameters (Å, º) top

O1—C6	1.3728 (15)	C3—C4	1.3970 (19)
O1—C8	1.4228 (17)	C3—H3A	0.9300
O2—C5	1.3697 (15)	C4—C5	1.3630 (18)
O2—C8	1.4284 (18)	C4—H4A	0.9300
N1—C1	1.2732 (17)	C5—C6	1.3836 (18)
N1—N1ⁱ	1.413 (2)	C6—C7	1.3607 (18)
C1—C2	1.4566 (18)	C7—H7A	0.9300
C1—H1A	0.9300	C8—H8A	0.9700
C2—C3	1.3907 (18)	C8—H8B	0.9700
C2—C7	1.4043 (18)

C6—O1—C8	106.27 (10)	C4—C5—O2	128.05 (12)
C5—O2—C8	105.97 (10)	C4—C5—C6	121.98 (12)
C1—N1—N1ⁱ	111.66 (14)	O2—C5—C6	109.97 (11)
N1—C1—C2	121.97 (12)	C7—C6—O1	128.17 (12)
N1—C1—H1A	119.0	C7—C6—C5	122.35 (12)
C2—C1—H1A	119.0	O1—C6—C5	109.48 (11)
C3—C2—C7	120.11 (12)	C6—C7—C2	117.09 (11)
C3—C2—C1	119.19 (12)	C6—C7—H7A	121.5
C7—C2—C1	120.69 (12)	C2—C7—H7A	121.5
C2—C3—C4	121.90 (12)	O1—C8—O2	108.17 (11)
C2—C3—H3A	119.1	O1—C8—H8A	110.1
C4—C3—H3A	119.1	O2—C8—H8A	110.1
C5—C4—C3	116.56 (12)	O1—C8—H8B	110.1
C5—C4—H4A	121.7	O2—C8—H8B	110.1
C3—C4—H4A	121.7	H8A—C8—H8B	108.4

N1ⁱ—N1—C1—C2	−179.47 (14)	C8—O1—C6—C5	2.58 (16)
N1—C1—C2—C3	174.71 (13)	C4—C5—C6—C7	−0.3 (2)
N1—C1—C2—C7	−4.6 (2)	O2—C5—C6—C7	179.55 (12)
C7—C2—C3—C4	1.0 (2)	C4—C5—C6—O1	179.77 (13)
C1—C2—C3—C4	−178.40 (13)	O2—C5—C6—O1	−0.38 (16)
C2—C3—C4—C5	−1.2 (2)	O1—C6—C7—C2	179.93 (13)
C3—C4—C5—O2	−178.96 (13)	C5—C6—C7—C2	0.0 (2)
C3—C4—C5—C6	0.9 (2)	C3—C2—C7—C6	−0.3 (2)
C8—O2—C5—C4	177.86 (14)	C1—C2—C7—C6	179.01 (12)
C8—O2—C5—C6	−1.98 (15)	C6—O1—C8—O2	−3.78 (16)
C8—O1—C6—C7	−177.34 (15)	C5—O2—C8—O1	3.55 (16)

Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₂N₂O₄
M_r	296.28
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	170
a, b, c (Å)	6.1835 (2), 4.5970 (2), 23.8487 (10)
β (°)	96.080 (4)
V (Å³)	674.10 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.28 × 0.25 × 0.08

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2010)
T_min, T_max	0.971, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	4759, 1746, 1402
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.118, 1.04
No. of reflections	1746
No. of parameters	100
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18

Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

ASP thanks the University of Mysore for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

References

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