(E)-1-[2-(Methyl­sulfan­yl)phen­yl]-2-({(E)-2-[2-(methyl­sulfan­yl)phen­yl]hydrazinyl­idene}(nitro)­meth­yl)diazene

Karel G von Eschwege; Fabian Muller; Eric C Hosten

doi:10.1107/S1600536811054080

. 2011 Dec 21;68(Pt 1):o199–o200. doi: 10.1107/S1600536811054080

(E)-1-[2-(Methylsulfanyl)phenyl]-2-({(E)-2-[2-(methylsulfanyl)phenyl]hydrazinylidene}(nitro)methyl)diazene

Karel G von Eschwege ^a,^*, Fabian Muller ^a, Eric C Hosten ^b

PMCID: PMC3254534 PMID: 22259480

Abstract

In the title compound, C₁₅H₁₅N₅O₂S₂, the phenyl rings make dihedral angles of 4.03 (4) and 9.77 (5)° with the plane defined by the central N—N—C—N—N atoms (r.m.s. deviation = 0.010 Å). The C—S—C—C torsion angles of the methylsulfanyl groups with their respective phenyl rings are −7.47 (13) and −72.07 (13)°. The shortest centroid–centroid distance of 3.707 Å occurs between the two π-systems N—N—C—N—N and the benzene ring in the diazene 1-position. The H atom bound to the N atom is involved in intramolecular N—H⋯N and N—H⋯S contacts, while the nitro O atoms are involved in intermolecular C—H⋯O contacts.

Related literature

For the chemistry of dithizone, see: Irving (1977 ▶). For related structures, see: Laing (1977 ▶); Mito et al. (1997 ▶); Gilroy et al. (2008 ▶). For the synthesis of nitroformazans, see: Pelkis et al. (1957 ▶). For DFT and electrochemistry studies of dithizone, see: von Eschwege & Swarts (2010 ▶); von Eschwege, Conradie & Kuhn (2011 ▶).

Experimental

Crystal data

C₁₅H₁₅N₅O₂S₂
M _r = 361.44
Monoclinic,
a = 4.7283 (2) Å
b = 17.9791 (10) Å
c = 19.3865 (8) Å
β = 103.646 (2)°
V = 1601.54 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 200 K
0.79 × 0.21 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.870, T _max = 1.000
14965 measured reflections
3960 independent reflections
3301 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.086
S = 1.04
3960 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); 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 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811054080/zq2147sup1.cif

e-68-0o199-sup1.cif^{(25.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811054080/zq2147Isup2.hkl

e-68-0o199-Isup2.hkl^{(194.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811054080/zq2147Isup3.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
N4—H4⋯S2	0.88	2.60	3.0248 (13)	110
N4—H4⋯N1	0.88	1.99	2.6229 (16)	128
C2—H2B⋯O1ⁱ	0.98	2.36	3.253 (2)	151
C25—H25⋯O2ⁱⁱ	0.95	2.45	3.1901 (19)	134

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

Acknowledgments

The research funds of the University of the Free State, the Nelson Mandela Metropolitan University and the National Research Foundation are gratefully acknowledged.

supplementary crystallographic information

Comment

During the synthesis of the versatile trace metal analysis dithizone reagent, aniline is first diazotized and then treated with nitromethane to form the bright orange-red nitroformazan product (Pelkis et al., 1957). Ammonia and hydrogen sulfide gas are used to substitute the nitro group with sulfur towards the formation of dithizone, the chemistry of which is extensively described in the literature (Irving, 1977). Single crystal X-ray structures of nitroformazan derivatives were determined by Gilroy et al. (2008), Mito et al. (1997) and the dithizone structure by Laing (1977), while we performed extensive DFT (von Eschwege et al., 2011) and electrochemistry studies (von Eschwege & Swarts, 2010) on the free ligand.

We recently embarked on a study during which we synthesized a series of electronically altered dithizones for the purpose of investigating its altered redox and structural properties. During this process, crystals of the title compound, suitable for X-ray crystallography, were grown from an acetone solution overlaid with n-hexane.

The least square planes defined by the phenyl rings with respect to the plane defined by the N1, N2, C3, N3 and N4 atoms enclose dihedral angles of 9.77 (5)° and 4.03 (4)° (Fig. 1). The torsion angles of the S-methyl groups with their respective phenyl rings are 7.47 (13)° and 72.07 (13)°. The shortest centroid-centroid distance of 3.707 Å occurs between the two π-systems N1—N2—C3—N3—N4 and C11—C12—C13—C14—C15—C16. The H atom bound to N4 is involved in intramolecular N—H···N and N—H···S contacts while the nitro O atoms have intermolecular C—H···O contacts (Fig. 2). The packing of the title compound in the crystal is shown in Figure 3.

Experimental

Solvents (AR) purchased from Merck and reagents from Sigma-Aldrich were used without further purification. The ortho-S-methyl derivative of nitroformazan was prepared according to the procedure reported by Pelkis et al. (1957). M.p. 144 °C. λ_max (dichloromethane) 320, 479 nm. δ_H (600 MHz, CDCl₃) 14.76 (1 H, 1 × s, 1 × NH), 2.50 (6 H, 1 × s, 2 × SCH₃), 8.03 – 7.34 (8 H, 3 × m, 2 × C₆H₄)