2-Amino-3-[(E)-(2-hy­droxy-3-methyl­benzyl­idene)amino]­but-2-ene­dinitrile

Elham S Aazam; Orhan Büyükgüngör

doi:10.1107/S1600536812015243

. 2012 Apr 18;68(Pt 5):o1406. doi: 10.1107/S1600536812015243

2-Amino-3-[(E)-(2-hydroxy-3-methylbenzylidene)amino]but-2-enedinitrile

Elham S Aazam ^a,^*, Orhan Büyükgüngör ^b

PMCID: PMC3344532 PMID: 22590294

Abstract

The title compound, C₁₂H₁₀N₄O, is a Schiff base obtained from the condensation of diaminomaleonitrile and 2-hydroxy-3-methylbenzaldehyde. The molecule is roughly planar, with an r.m.s. deviation of 0.0354 Å, and adopts the phenol–imine tautomeric form. An intramolecular O—H⋯N hydrogen bond involving the O—H group and the azomethine N atom generates an S(6) ring. In the crystal, there are two N—H⋯N hydrogen bonds.

Related literature

For the biological properties of Schiff bases see: Da Silva et al. (2011 ▶) and for their use in coordination chemistry, see: Aazam et al. (2011 ▶); Kargar et al. (2009 ▶); Yeap et al. (2009 ▶). For graph-set notation, see: Bernstein et al., (1995 ▶). For related structures, see: Aazam & Büyükgüngör (2010 ▶); Hökelek et al. (2000 ▶); Odabaşoğlu et al. (2005 ▶); Rivera et al. (2006 ▶).

Experimental

Crystal data

C₁₂H₁₀N₄O
M _r = 226.24
Monoclinic,
a = 6.9041 (6) Å
b = 11.8791 (7) Å
c = 14.0282 (11) Å
β = 101.600 (7)°
V = 1127.02 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.76 × 0.48 × 0.03 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.949, T _max = 0.996
16504 measured reflections
2336 independent reflections
1700 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.132
S = 1.14
2336 reflections
168 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2001 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812015243/go2051sup1.cif

e-68-o1406-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812015243/go2051Isup2.hkl

e-68-o1406-Isup2.hkl^{(112.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812015243/go2051Isup3.cml

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
O1—H1⋯N1	0.88 (3)	1.83 (3)	2.643 (2)	153 (3)
N2—H2A⋯N4ⁱ	0.89 (3)	2.40 (3)	3.156 (3)	142 (2)
N2—H2B⋯N3ⁱⁱ	0.88 (3)	2.26 (3)	3.098 (3)	159 (2)

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

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the diffractometer (purchased under grant F. 279 of University Research Fund) and King Abdulaziz University and the Deanship of Scientific Research for financial support (grant No. 17–013/430).

supplementary crystallographic information

Comment

Tetrameric HCN (diaminomaleonitrile, DAMN) is one of the most versatile reagents in organic chemistry. It has been used as a precursor for producing nucleotides and for synthesizing a wide variety of heterocyclic compounds. These compounds are important as synthetic intermediates and they are also used in pharmacology (Da Silva et al., 2011; Rivera et al., 2006).

Schiff bases derived from DAMN have also been used as versatile ligands in coordination chemistry (Aazam et al., 2011; Kargar et al., 2009; Yeap et al., 2009). There are two types of intra-molecular hydrogen bonds in Schiff bases, which may be stabilized either in keto-amine (N—H···O hydrogen bond) (Hökelek et al., 2000) or phenol-imine (N···H—O hydrogen bond) tautomeric forms (Odabaşoǧlu et al., 2005; Aazam & Büyükgüngör, 2010). The present X-ray investigation shows that the title compound is a Schiff base and exists in the phenol-imine form in the solid-state.

The molecular structure of the title compound is shown in Figure 1. An intramolecular O1—H1···N1 hydrogen bond, a characteristic hydrogen bond for Schiff bases, leads to the formation of a S(6) six-membered ring (Figure 1) (Bernstein et al., 1995).

The N2—H2A···N4ⁱ (i; -x, y - 1/2, -z + 1/2) and N2—H2B···N3ⁱⁱ (ii; x, -y + 3/2, z - 1/2) hydrogen bonds generate a C(5) zigzag chain running parallel to the b axis and a C(6) chain running parallel to the c axis, respectively, (Figure 2–3). The intersection of the C(5) and C(6) chains produce alternating R₄⁴(18) and R₄⁴(22) ring motives, (Figure 4), (Bernstein et al., 1995) which link the molecules into corrugated sheets which lie in the b,c plane. Details of the hydrogen bonds are given in Table 1.