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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 68| Part 1| January 2012| Pages 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 Mullera and Eric C. Hostenb

aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9300, South Africa, and bDepartment of Chemistry, Nelson Mandela Metropolitan University, PO Box 77000, Port Elizabeth 6031, South Africa
*Correspondence e-mail: veschwkg@ufs.ac.za

(Received 9 December 2011; accepted 15 December 2011; online 21 December 2011)

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[Irving, H. M. N. H. (1977). Dithizone. Analytical Sciences Monographs No. 5. London: The Chemical Society.]). For related structures, see: Laing (1977[Laing, M. (1977). J. Chem. Soc. Perkin Trans. 2, pp. 1248-1252.]); Mito et al. (1997[Mito, M., Takeda, K., Mukai, K., Azuma, N., Gleiter, M. R., Krieger, C. & Neugebaue, F. A. (1997). J. Phys. Chem. B, 101, 9517-9524.]); Gilroy et al. (2008[Gilroy, J. B., Otieno, P. O., Ferguson, M. J., McDonald, R. & Hicks, R. G. (2008). Inorg. Chem. 47, 1279-1286.]). For the synthesis of nitro­formazans, see: Pelkis et al. (1957[Pelkis, P. S., Dubenko, R. G. & Pupko, L. S. (1957). J. Org. Chem. USSR, 27, 2190-2194.]). For DFT and electrochemistry studies of dithizone, see: von Eschwege & Swarts (2010[Eschwege, K. G. von & Swarts, J. C. (2010). Polyhedron, 29, 1727-1733.]); von Eschwege, Conradie & Kuhn (2011[Eschwege, K. G. von, Conradie, J. & Kuhn, A. (2011). J. Phys. Chem. A. doi:10.1021/jp208212e.]).

[Scheme 1]

Experimental

Crystal data

  • C15H15N5O2S2

  • Mr = 361.44

  • Monoclinic, P 21 /c

  • 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[Bruker (2008). SADABS. Bruker Inc., Madison, Wisconsin, USA.]) Tmin = 0.870, Tmax = 1.000

  • 14965 measured reflections

  • 3960 independent reflections

  • 3301 reflections with I > 2σ(I)

  • Rint = 0.019
Refinement

  • R[F2 > 2σ(F2)] = 0.031

  • wR(F2) = 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

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) [-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]; (ii) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2010[Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2010[Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811054080/zq2147sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811054080/zq2147Isup3.cml

checkCIF report


Comment top

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.

Related literature top

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 top

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. λmax (dichloromethane) 320, 479 nm. δH (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)

Refinement top

All hydrogen positions were calculated after each cycle of refinement using a riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, with N—H = 0.88 Å and Uiso(H) = 1.2Ueq(N), and with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms. The H atoms of the methyl groups were allowed to rotate with a fixed angle around the C—C bond to best fit the experimental electron density [HFIX 137 in SHELXL97 (Sheldrick, 2008)].

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); 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 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and anistropic displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Inter- and intramolecular contacts in the crystal structure of the title compound (ellipsoids drawn at the 50% probability level). Symmetry operators: (i) = -x, y + 1/2, -z + 1/2; (ii) = -x + 2, -y, -z + 1.
[Figure 3] Fig. 3. Molecular packing of the title compound (anistropic displacement ellipsoids drawn at 50% probability level).
(E)-1-[2-(Methylsulfanyl)phenyl]-2-({(E)-2-[2- (methylsulfanyl)phenyl]hydrazinylidene}(nitro)methyl)diazene top
Crystal data top
C15H15N5O2S2F(000) = 752
Mr = 361.44Dx = 1.499 Mg m−3
Monoclinic, P21/cMelting point: 417 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 4.7283 (2) ÅCell parameters from 8473 reflections
b = 17.9791 (10) Åθ = 2.3–28.3°
c = 19.3865 (8) ŵ = 0.35 mm−1
β = 103.646 (2)°T = 200 K
V = 1601.54 (13) Å3Platelet, red
Z = 40.79 × 0.21 × 0.07 mm
Data collection top
Bruker APEXII CCD
diffractometer		3960 independent reflections
Radiation source: sealed tube3301 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ϕ and ω scansθmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −6→5
Tmin = 0.870, Tmax = 1.000k = −23→23
14965 measured reflectionsl = −25→25
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-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 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.25 e Å−3
Crystal data top
C15H15N5O2S2V = 1601.54 (13) Å3
Mr = 361.44Z = 4
Monoclinic, P21/cMo Kα radiation
a = 4.7283 (2) ŵ = 0.35 mm−1
b = 17.9791 (10) ÅT = 200 K
c = 19.3865 (8) Å0.79 × 0.21 × 0.07 mm
β = 103.646 (2)°
Data collection top
Bruker APEXII CCD
diffractometer		3960 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		3301 reflections with I > 2σ(I)
Tmin = 0.870, Tmax = 1.000Rint = 0.019
14965 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.086H-atom parameters constrained
S = 1.04Δρmax = 0.31 e Å−3
3960 reflectionsΔρmin = −0.25 e Å−3
219 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S1−0.33810 (7)−0.05295 (2)0.125542 (19)0.02859 (10)
S20.10204 (8)0.22354 (2)0.39420 (2)0.03395 (11)
O10.2660 (3)−0.13599 (7)0.23524 (7)0.0451 (3)
O20.6661 (3)−0.11093 (7)0.31138 (6)0.0419 (3)
N1−0.0436 (2)0.06137 (7)0.24775 (6)0.0261 (2)
N20.0632 (2)−0.00197 (7)0.23768 (6)0.0254 (2)
N30.4414 (3)0.00974 (7)0.34898 (6)0.0262 (2)
N40.3493 (3)0.07389 (7)0.36783 (6)0.0275 (3)
H40.20110.09660.33970.033*
N50.4207 (3)−0.09471 (7)0.27813 (6)0.0288 (3)
C1−0.6361 (3)−0.08689 (10)0.05684 (8)0.0368 (3)
H1A−0.8170−0.08390.07310.055*
H1B−0.5993−0.13870.04600.055*
H1C−0.6541−0.05650.01410.055*
C20.2794 (4)0.25326 (9)0.32603 (9)0.0364 (3)
H2A0.46600.27660.34810.055*
H2B0.15530.28920.29480.055*
H2C0.31320.21010.29820.055*
C30.3021 (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)
H13−0.80710.04200.05690.035*
C14−0.7781 (3)0.14243 (9)0.10470 (8)0.0326 (3)
H14−0.94750.16230.07370.039*
C15−0.6196 (3)0.18619 (9)0.15909 (8)0.0321 (3)
H15−0.67560.23610.16500.039*
C16−0.3795 (3)0.15564 (8)0.20428 (8)0.0292 (3)
H16−0.27210.18470.24250.035*
C210.4883 (3)0.10600 (8)0.43295 (7)0.0259 (3)
C220.3908 (3)0.17503 (8)0.45127 (7)0.0264 (3)
C230.5239 (3)0.20576 (9)0.51675 (8)0.0328 (3)
H230.45800.25230.53010.039*
C240.7501 (4)0.16978 (10)0.56265 (8)0.0364 (3)
H240.83790.19130.60730.044*
C250.8481 (4)0.10248 (10)0.54336 (9)0.0400 (4)
H251.00570.07800.57460.048*
C260.7182 (4)0.07032 (9)0.47872 (8)0.0371 (4)
H260.78630.02390.46570.045*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.02626 (18)0.02805 (19)0.02859 (18)−0.00116 (13)0.00074 (13)−0.00361 (13)
S20.02892 (19)0.0374 (2)0.0351 (2)0.01037 (15)0.00660 (14)−0.00065 (15)
O10.0362 (6)0.0348 (6)0.0586 (8)−0.0037 (5)−0.0001 (5)−0.0214 (6)
O20.0419 (6)0.0366 (6)0.0381 (6)0.0139 (5)−0.0090 (5)−0.0063 (5)
N10.0245 (6)0.0282 (6)0.0231 (5)−0.0008 (4)0.0008 (4)0.0003 (5)
N20.0238 (5)0.0268 (6)0.0234 (5)−0.0031 (4)0.0017 (4)0.0001 (4)
N30.0288 (6)0.0227 (6)0.0240 (5)0.0000 (4)0.0003 (4)−0.0006 (4)
N40.0288 (6)0.0243 (6)0.0244 (6)0.0029 (5)−0.0037 (4)−0.0018 (5)
N50.0322 (6)0.0251 (6)0.0273 (6)−0.0010 (5)0.0034 (5)−0.0023 (5)
C10.0343 (8)0.0377 (9)0.0340 (8)−0.0035 (6)−0.0008 (6)−0.0093 (7)
C20.0401 (8)0.0297 (8)0.0382 (8)0.0071 (6)0.0068 (7)0.0080 (6)
C30.0261 (6)0.0221 (7)0.0235 (6)−0.0010 (5)0.0024 (5)−0.0001 (5)
C110.0214 (6)0.0281 (7)0.0217 (6)−0.0020 (5)0.0026 (5)0.0018 (5)
C120.0225 (6)0.0274 (7)0.0223 (6)−0.0025 (5)0.0052 (5)0.0011 (5)
C130.0251 (7)0.0344 (8)0.0249 (6)−0.0026 (5)−0.0003 (5)0.0013 (6)
C140.0286 (7)0.0358 (8)0.0302 (7)0.0039 (6)0.0006 (5)0.0066 (6)
C150.0333 (8)0.0290 (8)0.0330 (7)0.0043 (6)0.0056 (6)0.0028 (6)
C160.0294 (7)0.0298 (8)0.0266 (6)−0.0012 (6)0.0032 (5)−0.0025 (6)
C210.0263 (7)0.0252 (7)0.0235 (6)−0.0021 (5)0.0003 (5)−0.0014 (5)
C220.0265 (7)0.0278 (7)0.0248 (6)−0.0009 (5)0.0057 (5)−0.0001 (5)
C230.0393 (8)0.0304 (8)0.0295 (7)−0.0020 (6)0.0098 (6)−0.0060 (6)
C240.0430 (9)0.0376 (9)0.0248 (7)−0.0078 (7)0.0002 (6)−0.0059 (6)
C250.0422 (9)0.0386 (9)0.0303 (7)0.0031 (7)−0.0090 (6)−0.0022 (7)
C260.0413 (8)0.0301 (8)0.0316 (8)0.0070 (6)−0.0080 (6)−0.0051 (6)
Geometric parameters (Å, º) top
S1—C121.7538 (15)C11—C161.400 (2)
S1—C11.8018 (15)C11—C121.4205 (18)
S2—C221.7710 (14)C12—C131.4018 (19)
S2—C21.8050 (17)C13—C141.381 (2)
O1—N51.2208 (16)C13—H130.9500
O2—N51.2226 (16)C14—C151.385 (2)
N1—N21.2793 (17)C14—H140.9500
N1—C111.4028 (17)C15—C161.374 (2)
N2—C31.3754 (17)C15—H150.9500
N3—C31.3009 (17)C16—H160.9500
N3—N41.3148 (17)C21—C261.387 (2)
N4—C211.4029 (17)C21—C221.399 (2)
N4—H40.8800C22—C231.391 (2)
N5—C31.4720 (18)C23—C241.380 (2)
C1—H1A0.9800C23—H230.9500
C1—H1B0.9800C24—C251.379 (2)
C1—H1C0.9800C24—H240.9500
C2—H2A0.9800C25—C261.385 (2)
C2—H2B0.9800C25—H250.9500
C2—H2C0.9800C26—H260.9500
C12—S1—C1102.72 (7)C11—C12—S1121.56 (10)
C22—S2—C2100.39 (7)C14—C13—C12121.98 (13)
N2—N1—C11115.05 (11)C14—C13—H13119.0
N1—N2—C3113.46 (11)C12—C13—H13119.0
C3—N3—N4119.26 (12)C13—C14—C15121.09 (14)
N3—N4—C21119.70 (11)C13—C14—H14119.5
N3—N4—H4120.1C15—C14—H14119.5
C21—N4—H4120.1C16—C15—C14118.39 (14)
O1—N5—O2123.76 (13)C16—C15—H15120.8
O1—N5—C3117.59 (12)C14—C15—H15120.8
O2—N5—C3118.65 (11)C15—C16—C11121.74 (13)
S1—C1—H1A109.5C15—C16—H16119.1
S1—C1—H1B109.5C11—C16—H16119.1
H1A—C1—H1B109.5C26—C21—C22120.22 (13)
S1—C1—H1C109.5C26—C21—N4121.02 (13)
H1A—C1—H1C109.5C22—C21—N4118.76 (12)
H1B—C1—H1C109.5C23—C22—C21118.61 (13)
S2—C2—H2A109.5C23—C22—S2119.38 (12)
S2—C2—H2B109.5C21—C22—S2122.01 (10)
H2A—C2—H2B109.5C24—C23—C22121.13 (14)
S2—C2—H2C109.5C24—C23—H23119.4
H2A—C2—H2C109.5C22—C23—H23119.4
H2B—C2—H2C109.5C25—C24—C23119.69 (14)
N3—C3—N2134.15 (13)C25—C24—H24120.2
N3—C3—N5113.05 (11)C23—C24—H24120.2
N2—C3—N5112.77 (11)C24—C25—C26120.40 (15)
C16—C11—N1113.16 (12)C24—C25—H25119.8
C16—C11—C12120.20 (12)C26—C25—H25119.8
N1—C11—C12126.61 (13)C25—C26—C21119.93 (15)
C13—C12—C11116.57 (13)C25—C26—H26120.0
C13—C12—S1121.87 (11)C21—C26—H26120.0
C11—N1—N2—C3−179.60 (11)C12—C13—C14—C150.2 (2)
C3—N3—N4—C21176.56 (13)C13—C14—C15—C16−1.6 (2)
N4—N3—C3—N21.0 (2)C14—C15—C16—C111.6 (2)
N4—N3—C3—N5−176.84 (12)N1—C11—C16—C15−178.69 (13)
N1—N2—C3—N31.7 (2)C12—C11—C16—C15−0.4 (2)
N1—N2—C3—N5179.48 (11)N3—N4—C21—C26−1.4 (2)
O1—N5—C3—N3161.94 (13)N3—N4—C21—C22178.64 (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—C23178.25 (13)
O2—N5—C3—N2163.80 (13)C26—C21—C22—S2179.03 (12)
N2—N1—C11—C16−173.42 (12)N4—C21—C22—S2−1.06 (19)
N2—N1—C11—C128.4 (2)C2—S2—C22—C23108.63 (13)
C16—C11—C12—C13−0.93 (19)C2—S2—C22—C21−72.07 (13)
N1—C11—C12—C13177.12 (13)C21—C22—C23—C240.8 (2)
C16—C11—C12—S1179.31 (11)S2—C22—C23—C24−179.83 (12)
N1—C11—C12—S1−2.65 (19)C22—C23—C24—C250.5 (2)
C1—S1—C12—C13−7.47 (13)C23—C24—C25—C26−0.9 (3)
C1—S1—C12—C11172.28 (12)C24—C25—C26—C210.1 (3)
C11—C12—C13—C141.0 (2)C22—C21—C26—C251.2 (2)
S1—C12—C13—C14−179.22 (11)N4—C21—C26—C25−178.72 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···S20.882.603.0248 (13)110
N4—H4···N10.881.992.6229 (16)128
C2—H2B···O1i0.982.363.253 (2)151
C25—H25···O2ii0.952.453.1901 (19)134
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+2, −y, −z+1.

Experimental details

Crystal data
Chemical formulaC15H15N5O2S2
Mr361.44
Crystal system, space groupMonoclinic, P21/c
Temperature (K)200
a, b, c (Å)4.7283 (2), 17.9791 (10), 19.3865 (8)
β (°) 103.646 (2)
V (Å3)1601.54 (13)
Z4
Radiation typeMo Kα
µ (mm−1)0.35
Crystal size (mm)0.79 × 0.21 × 0.07
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.870, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections		14965, 3960, 3301
Rint0.019
(sin θ/λ)max (Å−1)0.668
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.086, 1.04
No. of reflections3960
No. of parameters219
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.31, −0.25

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···S20.882.603.0248 (13)110.4
N4—H4···N10.881.992.6229 (16)128.2
C2—H2B···O1i0.982.363.253 (2)151.1
C25—H25···O2ii0.952.453.1901 (19)134.1
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+2, −y, −z+1.
 

Acknowledgements

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

References

First citationBruker (2008). SADABS. Bruker Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationBruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationEschwege, K. G. von, Conradie, J. & Kuhn, A. (2011). J. Phys. Chem. A. doi:10.1021/jp208212e.  Google Scholar
 First citationEschwege, K. G. von & Swarts, J. C. (2010). Polyhedron, 29, 1727–1733.  Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationGilroy, J. B., Otieno, P. O., Ferguson, M. J., McDonald, R. & Hicks, R. G. (2008). Inorg. Chem. 47, 1279–1286.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationIrving, H. M. N. H. (1977). Dithizone. Analytical Sciences Monographs No. 5. London: The Chemical Society.  Google Scholar
 First citationLaing, M. (1977). J. Chem. Soc. Perkin Trans. 2, pp. 1248–1252.  CSD CrossRef Google Scholar
 First citationMacrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationMito, M., Takeda, K., Mukai, K., Azuma, N., Gleiter, M. R., Krieger, C. & Neugebaue, F. A. (1997). J. Phys. Chem. B, 101, 9517–9524.  CSD CrossRef CAS Web of Science Google Scholar
 First citationPelkis, P. S., Dubenko, R. G. & Pupko, L. S. (1957). J. Org. Chem. USSR, 27, 2190–2194.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
Volume 68| Part 1| January 2012| Pages o199-o200
doi:10.1107/S1600536811054080
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