(E)-1-(2,4-Dinitro­phen­yl)-2-[1-(thio­phen-2-yl)ethyl­idene]hydrazine

Hoong-Kun Fun; Patcharaporn Jansrisewangwong; Suchada Chantrapromma

doi:10.1107/S1600536811011135

. 2011 Apr 7;67(Pt 5):o1034–o1035. doi: 10.1107/S1600536811011135

(E)-1-(2,4-Dinitrophenyl)-2-[1-(thiophen-2-yl)ethylidene]hydrazine

Hoong-Kun Fun ^a,^*,^‡, Patcharaporn Jansrisewangwong ^b, Suchada Chantrapromma ^b,^§

PMCID: PMC3089201 PMID: 21754363

Abstract

The molecule of the title compound, C₁₂H₁₀N₄O₄S, is slightly twisted, with a dihedral angle of 8.23 (9)° between the benzene and thiophene rings. One nitro group is co-planar [O—N—C—C torsion angles = −0.5 (3) and −1.9 (3)°] whereas the other is slightly twisted with respect to the benzene ring [O—N—C—C torsion angles = −5.1 (3) and −5.7 (3)°]. In the crystal, the molecules are linked by weak C—H⋯O interactions into screw chains along the b axis. The molecular conformation is consolidated by an intramolecular N—H⋯O hydrogen bond.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For related structures, see: Chantrapromma et al. (2010 ▶); Fun et al. (2010 ▶); Jansrisewangwong et al. (2010 ▶); Shan et al. (2008 ▶). For background to and the biological activity of hydrazones, see: Baughman et al. (2004 ▶); Bedia et al. (2006 ▶); El-Tabl et al. (2008) ▶; Ramamohan et al. (1995 ▶); Rollas & Küçükgüzel (2007 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₂H₁₀N₄O₄S
M _r = 306.30
Monoclinic,
a = 9.4868 (5) Å
b = 15.3912 (8) Å
c = 8.9756 (4) Å
β = 91.672 (2)°
V = 1310.00 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 100 K
0.60 × 0.19 × 0.16 mm

Data collection

Bruker APEXII CCD area detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.854, T _max = 0.959
10366 measured reflections
2414 independent reflections
2176 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.109
S = 1.08
2414 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.44 e Å⁻³

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 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011135/rz2573sup1.cif

e-67-o1034-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011135/rz2573Isup2.hkl

e-67-o1034-Isup2.hkl^{(118.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1	0.79 (3)	2.00 (3)	2.618 (3)	134 (2)
C6—H6A⋯O2ⁱ	0.93	2.45	3.099 (3)	127
C9—H9A⋯O4ⁱⁱ	0.93	2.47	3.147 (2)	129
C11—H11A⋯O3ⁱ	0.93	2.57	3.240 (3)	129

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

PJ thanks the Graduate School, Prince of Songkla University, for partial financial support. The authors thank the Prince of Songkla University for financial support through the Crystal Materials Research Unit (CMRU), and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Hydrazones are an important class of compounds which are used in numerous biological and pharmacological applications as insecticidal, antitumor, antioxidant, antifungal, antibacterial, antiviral and antituberculosis compounds (Bedia et al., 2006; El-Tabl et al., 2008; Ramamohan et al., 1995; Rollas & Küçükgüzel, 2007). Several of them also exhibit good nonlinear optical properties (Baughman et al., 2004). In our previous studies we reported the syntheses and crystal structures of some hydrazone derivatives (Chantrapromma et al., 2010; Fun et al., 2010; Jansrisewangwong et al., 2010). The title compound (I) was synthesized as part of our on going research on biological activities of hydrazones.

The molecule of (I), (Fig. 1), is slightly twisted with the dihedral angle between the benzene and thiophene rings of 8.23 (9)°. The middle ethylidinehydrazine unit (N1/N2/C7/C12) is planar with the r.m.s. 0.0033 (2) Å and the torsion angle N2–N1–C7–C12 = -1.1 (3)°. This N—N=C—C bridge makes dihedral angles of 6.62 (11) and 2.14 (12)° with the benzene and thiophene rings, respectively. The nitro group at atom C2 is co-planar [torsion angles O1–N3–C2–C1 = -0.5 (3)° and O2–N3–C2–C3 = -1.9 (3)°] whereby that at atom C4 is slightly twisted with respect to the benzene ring [torsion angles O3–N4–C4–C3 = -5.1 (3)° and O4–N4–C4–C5 = -5.7 (3)°]. The bond distances are of normal values (Allen et al., 1987) and comparable with those found in related structures (Jansrisewangwong et al., 2010; Shan et al., 2008).

In the crystal structure (Fig. 2), the molecules are linked by C—H···O weak interactions (Table 1) into screw chains along the b axis. The molecular conformation is consolidated by an intramolecular N—H···O hydrogen bonding interaction (Table 1). C···N^{iii, iv}[3.219 (3)–3.232 (3) Å], C···O^{iii, v,vi}[3.099 (3)–3.187 (2) Å] and N···O^vii[2.971 (2) Å] short contacts are also observed [symmetry codes: (iii) x, 1/2 - y, -1/2 + z; (iv) 1 + x, 1/2 - y, -1/2 + z; (v) 1 - x, 1/2 + y, 3/2 - z; (vi) 1 + x, y, -1 + z and (vii) 1 - x, 1 - y, 2 - z].

Experimental

The title compound was synthesized by dissolving 2,4-dinitrophenylhydrazine (0.40 g, 2 mmol) in ethanol (10 ml) and H₂SO₄ (conc.) (98%, 0.5 ml) was slowly added with stirring. Then 2-acetylthiophene (0.20 ml, 2 mmol) was added to the solution with continuous stirring. The solution was refluxed for 30 min yielding an orange-red solid, which was filtered off and washed with methanol. Orange block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystalized from ethanol by slow evaporation of the solvent at room temperature over several days. Mp. 516–518 K.