(1E,2E)-1,2-Bis[1-(3-nitro­phen­yl)ethyl­idene]hydrazine

Asik, S.I.J.; Fun, H.-K.; Razak, I.A.; Jansrisewangwong, P.; Chantraproma, S.

doi:10.1107/S1600536812004722

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o643

doi:10.1107/S1600536812004722

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(1E,2E)-1,2-Bis[1-(3-nitrophenyl)ethylidene]hydrazine

Safra Izuani Jama Asik,^a Hoong-Kun Fun,^a ^*‡ Ibrahim Abdul Razak,^a Patcharaporn Jansrisewangwong ^b and Suchada Chantraproma ^b §

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bCrystal Materials Research Unit, Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand
^*Correspondence e-mail: hkfun@usm.my

(Received 31 January 2012; accepted 3 February 2012; online 10 February 2012)

The asymmetric unit of the title compound, C₁₆H₁₄N₄O₄, contains one half-molecule of (nitrophenyl)ethanimine and the complete molecule is generated by a crystallographic inversion centre. The molecule has an E conformation with respect to each C=N double bond. The central C=N—N=C plane is twisted from the benzene rings with a dihedral angle of 24.76 (11)°. In the crystal, C—H⋯O interactions link the molecules to form sheets that lie parallel to (10-4).

Related literature

For the biological acivity of hydrazones, see: Khanmohammadi et al. (2008 ); Luboch et al. (2009 ). For related structures, see: Chantrapromma et al. (2011 ); Fun, Jansrisewangwong et al. (2011 ); Fun, Nilwanna et al. (2011 ); Jansrisewangwong et al. (2010 ); Nilwanna et al. (2011 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₆H₁₄N₄O₄
M_r = 326.31
Monoclinic, P 2₁ /c
a = 3.9296 (3) Å
b = 7.4448 (5) Å
c = 26.3979 (19) Å
β = 94.022 (1)°
V = 770.37 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.34 × 0.17 × 0.10 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.966, T_max = 0.990
15392 measured reflections
2254 independent reflections
1686 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.146
S = 1.06
2254 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O1ⁱ	0.93	2.57	3.239 (2)	129
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812004722/is5067sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004722/is5067Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812004722/is5067Isup3.cml

checkCIF report

Comment top

Hydrazones have been intensively investigated mostly because of their potential applications as antibacterial and antifungal drugs (Khanmohammadi et al., 2008) and as fluorescent chemosensors for metal ions (Luboch et al., 2009). Owing to our medicinal chemistry research on hydrazones, we previously reported the synthesis and crystal structures of some hydrazone derivatives (Chantrapromma et al., 2011; Fun, Jansrisewangwong et al., 2011; Fun, Nilwanna et al., 2011; Jansrisewangwong et al., 2010; Nilwanna et al., 2011). The title compound was synthesized to study for antibacterial activity and fluorescence properties in order to get more detail on the structural activity relationship through comparing with other closely related compounds.

The asymmetric unit of (I) (Fig. 1), contains one half-molecule of (nitrophenyl)ethanimine and the complete molecule is generated by a crystallographic inversion centre (-x,-y + 1,-z). The molecule is in an E configuration with respect to C7═N1 double bond [1.2803 (17) Å] with the torsion angle N1A—N1—C7—C1 = 179.92 (10)°. The methyl groups are twisted from the planes of benzene (C1–C6 and C1A–C6A) rings and their orientations can be indicated by the torsion angles (C1—C6—C7—C8 and C1A—C6A—C7A—C8A) = 24.91 (19)°. The bond length are within the normal range (Allen et al., 1987) and are comparable with the related structures (Chantrapromma et al., 2011; Fun, Jansrisewangwong et al., 2011; Fun, Nilwanna et al., 2011; Jansrisewangwong et al., 2010; Nilwanna et al., 2011). In the crystal structure (Fig. 2), the C3—H3A···O1 interaction links the molecules into two-dimensional layers parallel to the (1 0 4) plane.

Related literature top

For the biological acivity of hydrazones, see: Khanmohammadi et al. (2008); Luboch et al. (2009). For related structures, see: Chantrapromma et al. (2011); Fun, Jansrisewangwong et al. (2011); Fun, Nilwanna et al. (2011); Jansrisewangwong et al. (2010); Nilwanna et al. (2011). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was synthesized by mixing a solution (1:2 molar ratio) of hydrazine hydrate (0.10 ml, 2 mmol) and 3-nitroacetophenone (0.66 g, 4 mmol) in ethanol (20 ml). The resulting solution was refluxed for 4 h, yielding the yellow crystalline solid. The resultant solid was filtered off and washed with methanol. Yellow block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystalized from acetone by slow evaporation of the solvent at room temperature over several days (m.p. 469–471 K).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The structure of the title compound, showing 50% probability displacement ellipsoids. H atoms are shown as spheres of arbitrary radius.
	Fig. 2. The crystal packing, viewed along the b-axis, showing the molecules linked into two-dimensional layers parallel to the (104) plane. H atoms that not involved in hydrogen bonding (dashed lines) are omitted for clarity.

(1E,2E)-1,2-Bis[1-(3-nitrophenyl)ethylidene]hydrazine top

Crystal data top

C₁₆H₁₄N₄O₄	F(000) = 340
M_r = 326.31	D_x = 1.407 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4585 reflections
a = 3.9296 (3) Å	θ = 2.8–28.3°
b = 7.4448 (5) Å	µ = 0.10 mm⁻¹
c = 26.3979 (19) Å	T = 296 K
β = 94.022 (1)°	Block, yellow
V = 770.37 (10) Å³	0.34 × 0.17 × 0.10 mm
Z = 2

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	2254 independent reflections
Radiation source: fine-focus sealed tube	1686 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 30.1°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
T_min = 0.966, T_max = 0.990	k = −10→10
15392 measured reflections	l = −37→37

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.069P)² + 0.1466P] where P = (F_o² + 2F_c²)/3
2254 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₁₆H₁₄N₄O₄	V = 770.37 (10) Å³
M_r = 326.31	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.9296 (3) Å	µ = 0.10 mm⁻¹
b = 7.4448 (5) Å	T = 296 K
c = 26.3979 (19) Å	0.34 × 0.17 × 0.10 mm
β = 94.022 (1)°

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	2254 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1686 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.990	R_int = 0.028
15392 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
2254 reflections	Δρ_min = −0.18 e Å⁻³
110 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 > 2sigma(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	0.9642 (5)	0.1248 (2)	0.20045 (5)	0.1005 (6)
O2	0.8102 (4)	0.06399 (18)	0.12349 (5)	0.0867 (5)
N1	0.0796 (3)	0.47453 (16)	0.02358 (4)	0.0461 (3)
N2	0.8220 (3)	0.16404 (18)	0.15972 (5)	0.0572 (3)
C1	0.3995 (4)	0.6788 (2)	0.14058 (5)	0.0507 (3)
H1A	0.3117	0.7942	0.1362	0.061*
C2	0.5585 (4)	0.6293 (2)	0.18705 (6)	0.0583 (4)
H2A	0.5726	0.7113	0.2137	0.070*
C3	0.6956 (4)	0.4607 (2)	0.19421 (5)	0.0525 (4)
H3A	0.8039	0.4272	0.2252	0.063*
C4	0.6669 (3)	0.34261 (18)	0.15379 (5)	0.0429 (3)
C5	0.5072 (3)	0.38640 (17)	0.10740 (4)	0.0400 (3)
H5A	0.4914	0.3029	0.0811	0.048*
C6	0.3697 (3)	0.55758 (17)	0.10032 (4)	0.0390 (3)
C7	0.1991 (3)	0.60690 (18)	0.05020 (5)	0.0399 (3)
C8	0.1829 (5)	0.7991 (2)	0.03461 (6)	0.0643 (4)
H8A	0.1410	0.8068	−0.0016	0.096*
H8B	0.3956	0.8567	0.0447	0.096*
H8C	0.0016	0.8578	0.0507	0.096*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1420 (14)	0.0814 (10)	0.0708 (9)	0.0246 (9)	−0.0438 (9)	0.0216 (7)
O2	0.1242 (12)	0.0551 (7)	0.0763 (9)	0.0281 (7)	−0.0242 (8)	−0.0045 (6)
N1	0.0550 (6)	0.0460 (6)	0.0357 (5)	0.0002 (5)	−0.0080 (4)	0.0071 (4)
N2	0.0638 (8)	0.0518 (7)	0.0535 (7)	0.0030 (6)	−0.0133 (6)	0.0126 (6)
C1	0.0561 (8)	0.0465 (7)	0.0488 (8)	0.0046 (6)	−0.0020 (6)	−0.0061 (6)
C2	0.0696 (10)	0.0617 (9)	0.0424 (7)	−0.0022 (7)	−0.0053 (6)	−0.0130 (6)
C3	0.0576 (8)	0.0632 (9)	0.0350 (6)	−0.0071 (7)	−0.0088 (5)	0.0015 (6)
C4	0.0440 (6)	0.0450 (7)	0.0388 (6)	−0.0030 (5)	−0.0044 (5)	0.0058 (5)
C5	0.0430 (6)	0.0426 (7)	0.0338 (6)	−0.0013 (5)	−0.0024 (4)	0.0006 (5)
C6	0.0383 (6)	0.0425 (6)	0.0357 (6)	0.0002 (5)	−0.0007 (4)	0.0015 (5)
C7	0.0391 (6)	0.0426 (7)	0.0376 (6)	0.0045 (5)	0.0003 (4)	0.0042 (5)
C8	0.0847 (11)	0.0450 (8)	0.0600 (9)	0.0046 (8)	−0.0171 (8)	0.0064 (7)

Geometric parameters (Å, º) top

O1—N2	1.2121 (16)	C3—C4	1.3808 (19)
O2—N2	1.2105 (19)	C3—H3A	0.9300
N1—C7	1.2803 (17)	C4—C5	1.3756 (17)
N1—N1ⁱ	1.406 (2)	C5—C6	1.3916 (18)
N2—C4	1.4663 (19)	C5—H5A	0.9300
C1—C2	1.387 (2)	C6—C7	1.4867 (17)
C1—C6	1.3930 (19)	C7—C8	1.489 (2)
C1—H1A	0.9300	C8—H8A	0.9600
C2—C3	1.374 (2)	C8—H8B	0.9600
C2—H2A	0.9300	C8—H8C	0.9600

C7—N1—N1ⁱ	113.69 (14)	C4—C5—C6	119.02 (12)
O2—N2—O1	122.84 (15)	C4—C5—H5A	120.5
O2—N2—C4	118.75 (12)	C6—C5—H5A	120.5
O1—N2—C4	118.38 (14)	C5—C6—C1	118.67 (11)
C2—C1—C6	120.76 (14)	C5—C6—C7	119.49 (11)
C2—C1—H1A	119.6	C1—C6—C7	121.84 (12)
C6—C1—H1A	119.6	N1—C7—C6	115.05 (11)
C3—C2—C1	120.81 (14)	N1—C7—C8	125.53 (12)
C3—C2—H2A	119.6	C6—C7—C8	119.41 (12)
C1—C2—H2A	119.6	C7—C8—H8A	109.5
C2—C3—C4	117.74 (12)	C7—C8—H8B	109.5
C2—C3—H3A	121.1	H8A—C8—H8B	109.5
C4—C3—H3A	121.1	C7—C8—H8C	109.5
C5—C4—C3	122.99 (13)	H8A—C8—H8C	109.5
C5—C4—N2	118.04 (12)	H8B—C8—H8C	109.5
C3—C4—N2	118.94 (12)

C6—C1—C2—C3	1.1 (2)	C4—C5—C6—C1	0.12 (19)
C1—C2—C3—C4	−0.5 (2)	C4—C5—C6—C7	179.49 (11)
C2—C3—C4—C5	−0.3 (2)	C2—C1—C6—C5	−0.9 (2)
C2—C3—C4—N2	177.71 (14)	C2—C1—C6—C7	179.72 (13)
O2—N2—C4—C5	1.6 (2)	N1ⁱ—N1—C7—C6	−179.90 (13)
O1—N2—C4—C5	179.73 (15)	N1ⁱ—N1—C7—C8	−0.7 (2)
O2—N2—C4—C3	−176.58 (16)	C5—C6—C7—N1	24.84 (17)
O1—N2—C4—C3	1.6 (2)	C1—C6—C7—N1	−155.80 (13)
C3—C4—C5—C6	0.5 (2)	C5—C6—C7—C8	−154.43 (14)
N2—C4—C5—C6	−177.55 (11)	C1—C6—C7—C8	24.9 (2)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O1ⁱⁱ	0.93	2.57	3.239 (2)	129

Symmetry code: (ii) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄N₄O₄
M_r	326.31
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	3.9296 (3), 7.4448 (5), 26.3979 (19)
β (°)	94.022 (1)
V (Å³)	770.37 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.34 × 0.17 × 0.10

Data collection
Diffractometer	Bruker APEX DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.966, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	15392, 2254, 1686
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.146, 1.06
No. of reflections	2254
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.18

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O1ⁱ	0.9300	2.5700	3.239 (2)	129.00

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5085-2009. Additional correspondence author e-mail: suchada.c@psu.ac.th.

Acknowledgements

HKF, IAR and SIJA thank the Malaysian Government and Universiti Sains Malaysia for Research University grants (Nos. 1001/PFIZIK/811160 and 1001/PFIZIK/811151). PJ and SC thank the Prince of Songkla University for financial support through the Crystal Materials Research Unit.

References

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