1,2-Bis[1-(3-methyl­sulfanyl-1,2,4-triazin-5-yl)ethyl­idene]diazane

Mariusz Mojzych; Zbigniew Karczmarzyk; Zofia Urbańczyk-Lipkowska; Przemysław Kalicki

doi:10.1107/S1600536809025033

. 2009 Jul 4;65(Pt 8):o1772. doi: 10.1107/S1600536809025033

1,2-Bis[1-(3-methylsulfanyl-1,2,4-triazin-5-yl)ethylidene]diazane

Mariusz Mojzych ^a,^*, Zbigniew Karczmarzyk ^a, Zofia Urbańczyk-Lipkowska ^b, Przemysław Kalicki ^b

PMCID: PMC2977495 PMID: 21583480

Abstract

The molecule of the title compound, C₁₂H₁₄N₈S₂, has an N—N gauche conformation. The triazine rings are nearly coplanar with respect to the imide bonds [C—C—C—N torsion angles = −15.3 (3) and −15.8 (3)°] and they are twisted by 77.88 (7)°. The overall conformation of the molecule is stabilized by intramolecular C—H⋯N hydrogen bonding. The molecular packing is influenced by π–π interactions of the triazine systems with a shortest centroid–centroid separation of 3.5242 (12) Å.

Related literature

For the biological activity of hydrazones, see: Rollas et al. (2002 ▶); Terzioglu & Gürsoy (2003 ▶); Bedia et al. (2006 ▶). For the synthesis, see: Karczmarzyk et al. (2000 ▶); Rykowski et al. (2000 ▶); Mojzych & Rykowski (2003 ▶). For related structures, see: Lewis et al. (2000 ▶); Sauro & Workentin (2001 ▶); Tai et al. (2008 ▶).

Experimental

Crystal data

C₁₂H₁₄N₈S₂
M _r = 334.43
Monoclinic,
a = 14.4962 (4) Å
b = 7.0814 (2) Å
c = 15.6619 (5) Å
β = 107.465 (2)°
V = 1533.63 (8) Å³
Z = 4
Cu Kα radiation
μ = 3.24 mm⁻¹
T = 293 K
0.32 × 0.22 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.474, T _max = 0.753
5750 measured reflections
2635 independent reflections
2200 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.117
S = 1.03
2635 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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: SHELXL97, WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025033/kp2223sup1.cif

e-65-o1772-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025033/kp2223Isup2.hkl

e-65-o1772-Isup2.hkl^{(126.8KB, 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
C19—H193⋯N4	0.96	2.48	2.875 (3)	104
C20—H202⋯N8	0.96	2.46	2.816 (3)	101

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supplementary crystallographic information

Comment

Hydrazones have been found to possess antimicrobial, anticonvulsant, analgesic, antiinflammatory, antiplatelet, antitubercular, anticancer and antitumoral activities (Rollas et al., 2002; Terzioglu & Gürsoy, 2003; Bedia et al., 2006). Recently, we reported several aryl hydrazones of 5-acyl-1,2,4-triazine as important building blocks for the synthesis of N-1 substituted pyrazolo[4,3-e][1,2,4]triazines (Karczmarzyk et al., 2000; Rykowski et al., 2000). In continuation of work in this area we report herein the crystal structure of the title compound as intermediate for the construction of N-1 unsubstituted pyrazolo[4,3-e][1,2,4]triazines (Mojzych & Rykowski, 2003) and as a ligand for the synthesis of novel organometallic compounds with expected biological activity and other material applications (Sauro & Workentin, 2001).

In the title molecule, the C—N imide bonds of 1.283 (3) and 1.279 (3) Å and N—N hydrazine bond of 1.370 (2) Å are very similar to those reported for other related structures (Lewis et al., 2000; Tai et al., 2008). The molecule of (I) has an N—N gauche conformation with C7—N8—N9—C10 torsion angle of 114.8 (2)°. The triazine rings are nearly coplanar with the respective imide bonds [C6—C5—C7—N8 = -15.3 (3)° and C16—-C15—C10—N9 = -15.8 (3)°] and they are twisted by 77.88 (7)° with respect to each other. This conformation is stabilized by the intramolecular C19—H193···N4 and C20—H202···N8 hydrogen bonds (Table 1). The methylsulfanyl groups are in different conformations in respect to the mother triazine rings with the torsion angles N4—C3—S17—C18 and N14—C13—S21—C22 of 179.03 (15) and 7.0 (2)°, respectively. Significant π-π interactions are observed in the packing (Spek, 2009). The triazine N1···C6 rings form molecular stacks in the [010] direction with centroid-to-centroid separations of 3.5242 (12) (1 - x, -y, 1 - z) and 3.6473 (12) Å (1 - x, 1 - y, 1 - z) (Fig. 2) and slippages of 0.898 and 1.615 Å, respectively.

Experimental

The synthesis of compound (I) and its analytical data (IR, ¹H NMR) were described by Mojzych & Rykowski (2003). Crystals suitable for X-ray diffraction analysis were grown by slow evaporation of an ethanol solution.