(E)-1-[2-(Methyl-sulfan-yl)phen-yl]-2-({(E)-2-[2-(methyl-sulfan-yl)phen-yl]hydrazinyl-idene}(nitro)-meth-yl)diazene.

In the title compound, C(15)H(15)N(5)O(2)S(2), 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 methyl-sulfanyl 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 intra-molecular N-H⋯N and N-H⋯S contacts, while the nitro O atoms are involved in inter-molecular 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 = 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

Δρmax = 0.31 e Å−3

Δρmin = −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 ▶).

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

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

Supplementary material file. DOI: 10.1107/S1600536811054080/zq2147Isup3.cml

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

C15H15N5O2S2	F(000) = 752
Mr = 361.44	Dx = 1.499 Mg m−3
Monoclinic, P21/c	Melting point: 417 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 4.7283 (2) Å	Cell parameters from 8473 reflections
b = 17.9791 (10) Å	θ = 2.3–28.3°
c = 19.3865 (8) Å	µ = 0.35 mm−1
β = 103.646 (2)°	T = 200 K
V = 1601.54 (13) Å3	Platelet, red
Z = 4	0.79 × 0.21 × 0.07 mm

Bruker APEXII CCD diffractometer	3960 independent reflections
Radiation source: sealed tube	3301 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→5
Tmin = 0.870, Tmax = 1.000	k = −23→23
14965 measured reflections	l = −25→25

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0396P)2 + 0.7279P] where P = (Fo2 + 2Fc2)/3
3960 reflections	(Δ/σ)max < 0.001
219 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.25 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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.

	x	y	z	Uiso*/Ueq
S1	−0.33810 (7)	−0.05295 (2)	0.125542 (19)	0.02859 (10)
S2	0.10204 (8)	0.22354 (2)	0.39420 (2)	0.03395 (11)
O1	0.2660 (3)	−0.13599 (7)	0.23524 (7)	0.0451 (3)
O2	0.6661 (3)	−0.11093 (7)	0.31138 (6)	0.0419 (3)
N1	−0.0436 (2)	0.06137 (7)	0.24775 (6)	0.0261 (2)
N2	0.0632 (2)	−0.00197 (7)	0.23768 (6)	0.0254 (2)
N3	0.4414 (3)	0.00974 (7)	0.34898 (6)	0.0262 (2)
N4	0.3493 (3)	0.07389 (7)	0.36783 (6)	0.0275 (3)
H4	0.2011	0.0966	0.3397	0.033*
N5	0.4207 (3)	−0.09471 (7)	0.27813 (6)	0.0288 (3)
C1	−0.6361 (3)	−0.08689 (10)	0.05684 (8)	0.0368 (3)
H1A	−0.8170	−0.0839	0.0731	0.055*
H1B	−0.5993	−0.1387	0.0460	0.055*
H1C	−0.6541	−0.0565	0.0141	0.055*
C2	0.2794 (4)	0.25326 (9)	0.32603 (9)	0.0364 (3)
H2A	0.4660	0.2766	0.3481	0.055*
H2B	0.1553	0.2892	0.2948	0.055*
H2C	0.3132	0.2101	0.2982	0.055*
C3	0.3021 (3)	−0.02142 (8)	0.29019 (7)	0.0244 (3)
C11	−0.2889 (3)	0.08284 (8)	0.19544 (7)	0.0242 (3)
C12	−0.4468 (3)	0.03812 (8)	0.13894 (7)	0.0241 (3)
C13	−0.6941 (3)	0.07045 (9)	0.09478 (8)	0.0292 (3)
H13	−0.8071	0.0420	0.0569	0.035*
C14	−0.7781 (3)	0.14243 (9)	0.10470 (8)	0.0326 (3)
H14	−0.9475	0.1623	0.0737	0.039*
C15	−0.6196 (3)	0.18619 (9)	0.15909 (8)	0.0321 (3)
H15	−0.6756	0.2361	0.1650	0.039*
C16	−0.3795 (3)	0.15564 (8)	0.20428 (8)	0.0292 (3)
H16	−0.2721	0.1847	0.2425	0.035*
C21	0.4883 (3)	0.10600 (8)	0.43295 (7)	0.0259 (3)
C22	0.3908 (3)	0.17503 (8)	0.45127 (7)	0.0264 (3)
C23	0.5239 (3)	0.20576 (9)	0.51675 (8)	0.0328 (3)
H23	0.4580	0.2523	0.5301	0.039*
C24	0.7501 (4)	0.16978 (10)	0.56265 (8)	0.0364 (3)
H24	0.8379	0.1913	0.6073	0.044*
C25	0.8481 (4)	0.10248 (10)	0.54336 (9)	0.0400 (4)
H25	1.0057	0.0780	0.5746	0.048*
C26	0.7182 (4)	0.07032 (9)	0.47872 (8)	0.0371 (4)
H26	0.7863	0.0239	0.4657	0.045*

	U11	U22	U33	U12	U13	U23
S1	0.02626 (18)	0.02805 (19)	0.02859 (18)	−0.00116 (13)	0.00074 (13)	−0.00361 (13)
S2	0.02892 (19)	0.0374 (2)	0.0351 (2)	0.01037 (15)	0.00660 (14)	−0.00065 (15)
O1	0.0362 (6)	0.0348 (6)	0.0586 (8)	−0.0037 (5)	−0.0001 (5)	−0.0214 (6)
O2	0.0419 (6)	0.0366 (6)	0.0381 (6)	0.0139 (5)	−0.0090 (5)	−0.0063 (5)
N1	0.0245 (6)	0.0282 (6)	0.0231 (5)	−0.0008 (4)	0.0008 (4)	0.0003 (5)
N2	0.0238 (5)	0.0268 (6)	0.0234 (5)	−0.0031 (4)	0.0017 (4)	0.0001 (4)
N3	0.0288 (6)	0.0227 (6)	0.0240 (5)	0.0000 (4)	0.0003 (4)	−0.0006 (4)
N4	0.0288 (6)	0.0243 (6)	0.0244 (6)	0.0029 (5)	−0.0037 (4)	−0.0018 (5)
N5	0.0322 (6)	0.0251 (6)	0.0273 (6)	−0.0010 (5)	0.0034 (5)	−0.0023 (5)
C1	0.0343 (8)	0.0377 (9)	0.0340 (8)	−0.0035 (6)	−0.0008 (6)	−0.0093 (7)
C2	0.0401 (8)	0.0297 (8)	0.0382 (8)	0.0071 (6)	0.0068 (7)	0.0080 (6)
C3	0.0261 (6)	0.0221 (7)	0.0235 (6)	−0.0010 (5)	0.0024 (5)	−0.0001 (5)
C11	0.0214 (6)	0.0281 (7)	0.0217 (6)	−0.0020 (5)	0.0026 (5)	0.0018 (5)
C12	0.0225 (6)	0.0274 (7)	0.0223 (6)	−0.0025 (5)	0.0052 (5)	0.0011 (5)
C13	0.0251 (7)	0.0344 (8)	0.0249 (6)	−0.0026 (5)	−0.0003 (5)	0.0013 (6)
C14	0.0286 (7)	0.0358 (8)	0.0302 (7)	0.0039 (6)	0.0006 (5)	0.0066 (6)
C15	0.0333 (8)	0.0290 (8)	0.0330 (7)	0.0043 (6)	0.0056 (6)	0.0028 (6)
C16	0.0294 (7)	0.0298 (8)	0.0266 (6)	−0.0012 (6)	0.0032 (5)	−0.0025 (6)
C21	0.0263 (7)	0.0252 (7)	0.0235 (6)	−0.0021 (5)	0.0003 (5)	−0.0014 (5)
C22	0.0265 (7)	0.0278 (7)	0.0248 (6)	−0.0009 (5)	0.0057 (5)	−0.0001 (5)
C23	0.0393 (8)	0.0304 (8)	0.0295 (7)	−0.0020 (6)	0.0098 (6)	−0.0060 (6)
C24	0.0430 (9)	0.0376 (9)	0.0248 (7)	−0.0078 (7)	0.0002 (6)	−0.0059 (6)
C25	0.0422 (9)	0.0386 (9)	0.0303 (7)	0.0031 (7)	−0.0090 (6)	−0.0022 (7)
C26	0.0413 (8)	0.0301 (8)	0.0316 (8)	0.0070 (6)	−0.0080 (6)	−0.0051 (6)

S1—C12	1.7538 (15)	C11—C16	1.400 (2)
S1—C1	1.8018 (15)	C11—C12	1.4205 (18)
S2—C22	1.7710 (14)	C12—C13	1.4018 (19)
S2—C2	1.8050 (17)	C13—C14	1.381 (2)
O1—N5	1.2208 (16)	C13—H13	0.9500
O2—N5	1.2226 (16)	C14—C15	1.385 (2)
N1—N2	1.2793 (17)	C14—H14	0.9500
N1—C11	1.4028 (17)	C15—C16	1.374 (2)
N2—C3	1.3754 (17)	C15—H15	0.9500
N3—C3	1.3009 (17)	C16—H16	0.9500
N3—N4	1.3148 (17)	C21—C26	1.387 (2)
N4—C21	1.4029 (17)	C21—C22	1.399 (2)
N4—H4	0.8800	C22—C23	1.391 (2)
N5—C3	1.4720 (18)	C23—C24	1.380 (2)
C1—H1A	0.9800	C23—H23	0.9500
C1—H1B	0.9800	C24—C25	1.379 (2)
C1—H1C	0.9800	C24—H24	0.9500
C2—H2A	0.9800	C25—C26	1.385 (2)
C2—H2B	0.9800	C25—H25	0.9500
C2—H2C	0.9800	C26—H26	0.9500
C12—S1—C1	102.72 (7)	C11—C12—S1	121.56 (10)
C22—S2—C2	100.39 (7)	C14—C13—C12	121.98 (13)
N2—N1—C11	115.05 (11)	C14—C13—H13	119.0
N1—N2—C3	113.46 (11)	C12—C13—H13	119.0
C3—N3—N4	119.26 (12)	C13—C14—C15	121.09 (14)
N3—N4—C21	119.70 (11)	C13—C14—H14	119.5
N3—N4—H4	120.1	C15—C14—H14	119.5
C21—N4—H4	120.1	C16—C15—C14	118.39 (14)
O1—N5—O2	123.76 (13)	C16—C15—H15	120.8
O1—N5—C3	117.59 (12)	C14—C15—H15	120.8
O2—N5—C3	118.65 (11)	C15—C16—C11	121.74 (13)
S1—C1—H1A	109.5	C15—C16—H16	119.1
S1—C1—H1B	109.5	C11—C16—H16	119.1
H1A—C1—H1B	109.5	C26—C21—C22	120.22 (13)
S1—C1—H1C	109.5	C26—C21—N4	121.02 (13)
H1A—C1—H1C	109.5	C22—C21—N4	118.76 (12)
H1B—C1—H1C	109.5	C23—C22—C21	118.61 (13)
S2—C2—H2A	109.5	C23—C22—S2	119.38 (12)
S2—C2—H2B	109.5	C21—C22—S2	122.01 (10)
H2A—C2—H2B	109.5	C24—C23—C22	121.13 (14)
S2—C2—H2C	109.5	C24—C23—H23	119.4
H2A—C2—H2C	109.5	C22—C23—H23	119.4
H2B—C2—H2C	109.5	C25—C24—C23	119.69 (14)
N3—C3—N2	134.15 (13)	C25—C24—H24	120.2
N3—C3—N5	113.05 (11)	C23—C24—H24	120.2
N2—C3—N5	112.77 (11)	C24—C25—C26	120.40 (15)
C16—C11—N1	113.16 (12)	C24—C25—H25	119.8
C16—C11—C12	120.20 (12)	C26—C25—H25	119.8
N1—C11—C12	126.61 (13)	C25—C26—C21	119.93 (15)
C13—C12—C11	116.57 (13)	C25—C26—H26	120.0
C13—C12—S1	121.87 (11)	C21—C26—H26	120.0
C11—N1—N2—C3	−179.60 (11)	C12—C13—C14—C15	0.2 (2)
C3—N3—N4—C21	176.56 (13)	C13—C14—C15—C16	−1.6 (2)
N4—N3—C3—N2	1.0 (2)	C14—C15—C16—C11	1.6 (2)
N4—N3—C3—N5	−176.84 (12)	N1—C11—C16—C15	−178.69 (13)
N1—N2—C3—N3	1.7 (2)	C12—C11—C16—C15	−0.4 (2)
N1—N2—C3—N5	179.48 (11)	N3—N4—C21—C26	−1.4 (2)
O1—N5—C3—N3	161.94 (13)	N3—N4—C21—C22	178.64 (13)
O2—N5—C3—N3	−17.90 (19)	C26—C21—C22—C23	−1.7 (2)
O1—N5—C3—N2	−16.36 (18)	N4—C21—C22—C23	178.25 (13)
O2—N5—C3—N2	163.80 (13)	C26—C21—C22—S2	179.03 (12)
N2—N1—C11—C16	−173.42 (12)	N4—C21—C22—S2	−1.06 (19)
N2—N1—C11—C12	8.4 (2)	C2—S2—C22—C23	108.63 (13)
C16—C11—C12—C13	−0.93 (19)	C2—S2—C22—C21	−72.07 (13)
N1—C11—C12—C13	177.12 (13)	C21—C22—C23—C24	0.8 (2)
C16—C11—C12—S1	179.31 (11)	S2—C22—C23—C24	−179.83 (12)
N1—C11—C12—S1	−2.65 (19)	C22—C23—C24—C25	0.5 (2)
C1—S1—C12—C13	−7.47 (13)	C23—C24—C25—C26	−0.9 (3)
C1—S1—C12—C11	172.28 (12)	C24—C25—C26—C21	0.1 (3)
C11—C12—C13—C14	1.0 (2)	C22—C21—C26—C25	1.2 (2)
S1—C12—C13—C14	−179.22 (11)	N4—C21—C26—C25	−178.72 (15)

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.

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

Symmetry codes: (i) ; (ii) .