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ISSN: 2056-9890
Volume 70| Part 10| October 2014| Pages o1090-o1091

Crystal structure of the charge-transfer complex 2-(1,2,3,4-tetra­hydro­naph­thal­en-1-yl­­idene)hydrazinecarbo­thio­amide–pyrazine-2,3,5,6-tetra­carbo­nitrile (2/1)

aInstitut für Anorganische Chemie, Universität Bonn, Gerhard-Domagk-Strasse 1, D-53121 Bonn, Germany, and bDepartamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, Campus, 49100-000 São Cristóvão-SE, Brazil
*Correspondence e-mail: unc40018@uni-bonn.de

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 30 August 2014; accepted 2 September 2014; online 6 September 2014)

The reaction of 2-(1,2,3,4-tetra­hydro­napthalen-1-yl­idene)hydrazinecarbo­thio­amide (TTSC) with pyrazine-2,3,5,6-tetra­carbo­nitrile (tetra­cyano­pyrazine, TCNP) yields the title 2:1 charge-transfer adduct, 2C11H12N3S·C6N8. The complete TCNP mol­ecule is generated by a crystallographic inversion centre and the non-aromatic ring in the TTSC mol­ecule adopts an envelope conformation with a methyl­ene C atom as the flap. In the crystal, the thio­semicarbazone mol­ecules are connected through inversion-related pairs of N—H⋯S inter­actions, building a polymeric chain along the b-axis direction. The TCNP mol­ecules are embedded in the structure, forming TTSC–TCNP–TTSC stacks with the aromatic rings of TTSC and the mol­ecular plane of TCNP in a parallel arrangement [centroid–centroid distance = 3.5558 (14) Å]. Charge-transfer (CT) via π-stacking is indicated by a CT band around 550 cm−1 in the single-crystal absorption spectrum.

1. Related literature

For one of the first reports of the synthesis of thio­semicarbazone derivatives, see: Freund & Schander (1902[Freund, M. & Schander, A. (1902). Chem. Ber. 35, 2602-2606.]). For the crystal structure of tetra­lone–thio­semicarbazone, see: de Oliveira et al. (2012[Oliveira, A. B. de, Silva, C. S., Feitosa, B. R. S., Näther, C. & Jess, I. (2012). Acta Cryst. E68, o2581.]7). For charge-transfer compounds involving TCNP, see: Rosokha et al. (2004[Rosokha, Y. S., Lindeman, S. V., Roskha, S. V. & Kochi, J. K. (2004). Angew. Chem. Int. Ed. 43, 4650-4652.]). Tetra­cyano­pyrazine was obtained by condensation of di­imino­succino­nitrile with di­amino­maleo­nitrile according to a literature procedure (Begland et al., 1974[Begland, R. W., Hartter, D. R., Donald, D. S., Cairncross, A. & Sheppard, W. A. (1974). J. Org. Chem. 39, 1235-1239.]) For bond lengths in neat TCNP, see: Rosokha et al. (2009[Rosokha, S. V., Lu, J., Han, B. & Kochi, J. K. (2009). New J. Chem. 33, 545-553.]) and for the electronic situation in the TCNP mol­ecule, see: Novoa et al. (2009[Novoa, J. J., Stephens, P. W., Weerasekare, M., Shum, W. W. & Miller, J. S. (2009). J. Am. Chem. Soc. 131, 9070-9075.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • 2C11H13N3S·C8N6

  • Mr = 618.74

  • Triclinic, [P \overline 1]

  • a = 6.1363 (4) Å

  • b = 8.2574 (3) Å

  • c = 15.3303 (9) Å

  • α = 86.659 (3)°

  • β = 78.751 (2)°

  • γ = 73.893 (3)°

  • V = 731.95 (7) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 0.23 mm−1

  • T = 293 K

  • 0.06 × 0.04 × 0.02 mm

2.2. Data collection

  • Nonius KappaCCD diffractometer

  • Absorption correction: analytical (Alcock, 1970[Alcock, N. W. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, p. 271. Copenhagen: Munksgaard, Denmark.]) Tmin = 0.987, Tmax = 0.995

  • 10255 measured reflections

  • 2601 independent reflections

  • 1775 reflections with I > 2σ(I)

  • Rint = 0.073

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.045

  • wR(F2) = 0.096

  • S = 1.08

  • 2601 reflections

  • 251 parameters

  • All H-atom parameters refined

  • Δρmax = 0.26 e Å−3

  • Δρmin = −0.31 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—HN2⋯S1i 0.89 (3) 2.57 (3) 3.450 (2) 173 (2)
N3—HN3A⋯S1ii 0.92 (3) 2.44 (3) 3.348 (2) 170 (3)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) -x+1, -y, -z+1.

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]) and SCALEPACK; 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: DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Structural commentary top

The title compound represents a charge-transfer adduct composite of tetra­hydro­naphtalene-thio­semicarbazone (TTSC) and the strong electron acceptor pyrazine­tetra­carbo­nitrile (tetra­cyano­pyrazine, TCNP) in stoichiometry 2:1 (Fig. 1). TTSC has the maximum deviation from the mean plane of the non-H atoms of 0.448 (2) Å for C3, which corresponds to an envelope conformation for the non-aromatic ring. The structure of the thio­semicarbazone derivative is quite similar to the structure reported in the literature (Oliveira et al., 2012). The molecule shows an E conformation for the atoms about the N1–N2 bond. The torsion angle at the atoms N1, N2, C11 and S1 amounts to 176.4 (2)°, building a slightly distorted planar environment. The molecules are connected through inversion centres via pairs of N1–H···S inter­actions (Fig. 2 and Table 1) forming a one-dimensional hydrogen-bonded polymer running along the b-axis (Fig. 2).

The TCNP molecule is essentially planar with the maximum deviation of 0.006 Å from the least squares plane through all atoms. Bond lengths differ less than 0.01 Å to neat TCNP (Rosokha et al. 2009). These non-significant differences show that the amount of charge-transfer is comparably small and the electronic situation of the TCNP molecule is mainly unaltered (Novoa et al., 2009).

The molecular planes of TTSC and TCNP molecules are parallel and arranged perpendicular to the [101] direction (Fig. 3). The TCNP molecules from stacks with each two neighboring TTSC molecules. The aromatic rings of two TTSC molecules and the TCNP planes are in an almost parallel arrangement. The shortest distances between the six-membered rings of 3.233 Å are observed between C7 of TTSC and C13 of TCNP (Fig. 4). As typical for weak to medium strong charge-transfer complexes between π systems, the normals through the midpoints of the aromatic rings are not coincident, instead the stack is slipped by about 15°.

The presence of a substantial charge-transfer in the title compound is indicated by the red colour, since the starting materials are light-yellow (TTSC) and colourless (TCNP) (Fig. 5). Moreover, the crystals are dichroitic and show a colour change in polarized light from red to light-brown.

In the single crystal absorption spectrum, the charge-transfer band is present in the range 500 -650 nm (Fig. 6). Depending on the incident angle of the plane of polarization a distinct change of the charge-transfer band both in intensity and energy is present, explaining the different colours.

Synthesis and crystallization top

The synthesis of 2-(1,2,3,4-tetra­hydro­naphthalen-1-yl­idene)hydrazinecarbo­thio­amide was adapted from a procedure reported over 100 years' ago (Freund & Schander, 1902). Tetra­cyano­pyrazine was obtained by condensation of di­imino­succino­nitrile with di­amino­maleo­nitrile according to literature (Begland et al., 1974). The title compound (TTSC)2(TCNP) is formed only if an excess of TCNP is present. Solutions of two molar equivalents of TNCP and of one molar equivalent of TTSC in aceto­nitrile are prepared. On mixing the solutions, no significant colour change is observed. Slow evaporation of the solvent affords crystals of (TTSC)2(TCNP) as thin light-red plates, embedded in a matrix of excess TCNP. Crystals of the title compound had to be separated mechanically.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. All hydrogen atoms were localized in a difference density Fourier map. Their positions and isotropic displacement parameters were refined.

Related literature top

For one of the first reports of the synthesis of thiosemicarbazone derivatives, see: Freund & Schander (1902). For the crystal structure of tetralone–thiosemicarbazone, see: de Oliveira et al. (20127). For charge-transfer compounds involving TCNP, see: Rosokha et al. (2004). Tetracyanopyrazine was obtained by condensation of diiminosuccinonitrile with diaminomaleonitrile according to a literature procedure (Begland et al., 1974) For bond lengths in neat TCNP, see: Rosokha et al. (2009) and for the electronic situation in the TCNP molecule, see: Novoa et al. (2009).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. : The two molecular constituents of the title compound with displacement ellipsoids drawn at the 70% probability level. Symmetry code: (i) 1- x, 1 - y ,-z.
[Figure 2] Fig. 2. : Molecules of TTSC connected via N—H···S hydrogen bridges to an infinite ribbon. Bond lengths are given in Å.
[Figure 3] Fig. 3. : The arrangement of the molecules in the structure of the title compound in a perspective view along the b-axis.
[Figure 4] Fig. 4. : Detail of the crystal structure of the title compound (TTSC)2TCNP). The TCNP molecules are embedded between two phenyl rings of adjacent TTSC molecules. The shortest distance amounts to C7···C13iii = 3.233 Å. Symmetry codes: (ii)-x,1 - y,1 - z, (iii)1 - x,y,1 + z, (iv)-1 - x,1 - y,2 - z.
[Figure 5] Fig. 5. : Photo of crystals of the title compound. The crystals are embedded in unreacted TCNP, which was used in excess.
[Figure 6] Fig. 6. : Crystal UV-vis absorption spectrum of the title compound recorded with light in horizontal and vertical polarization direction.
2-(1,2,3,4-Tetrahydronaphthalen-1-ylidene)hydrazinecarbothioamide–pyrazine-2,3,5,6-tetracarbonitrile (2/1) top
Crystal data top
2C11H13N3S·C8N6Z = 1
Mr = 618.74F(000) = 322
Triclinic, P1Dx = 1.404 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.1363 (4) ÅCell parameters from 15334 reflections
b = 8.2574 (3) Åθ = 2.9–27.5°
c = 15.3303 (9) ŵ = 0.23 mm1
α = 86.659 (3)°T = 293 K
β = 78.751 (2)°Plate, red
γ = 73.893 (3)°0.06 × 0.04 × 0.02 mm
V = 731.95 (7) Å3
Data collection top
Nonius KappaCCD
diffractometer
2601 independent reflections
Radiation source: fine-focus sealed tube, Nonius KappaCCD1775 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.073
Detector resolution: 9 pixels mm-1θmax = 25.1°, θmin = 3.5°
CCD rotation images, thick slices scansh = 77
Absorption correction: analytical
(Alcock, 1970)
k = 99
Tmin = 0.987, Tmax = 0.995l = 1818
10255 measured reflections
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096All H-atom parameters refined
S = 1.08 w = 1/[σ2(Fo2) + (0.0321P)2 + 0.1427P]
where P = (Fo2 + 2Fc2)/3
2601 reflections(Δ/σ)max < 0.001
251 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
2C11H13N3S·C8N6γ = 73.893 (3)°
Mr = 618.74V = 731.95 (7) Å3
Triclinic, P1Z = 1
a = 6.1363 (4) ÅMo Kα radiation
b = 8.2574 (3) ŵ = 0.23 mm1
c = 15.3303 (9) ÅT = 293 K
α = 86.659 (3)°0.06 × 0.04 × 0.02 mm
β = 78.751 (2)°
Data collection top
Nonius KappaCCD
diffractometer
2601 independent reflections
Absorption correction: analytical
(Alcock, 1970)
1775 reflections with I > 2σ(I)
Tmin = 0.987, Tmax = 0.995Rint = 0.073
10255 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.096All H-atom parameters refined
S = 1.08Δρmax = 0.26 e Å3
2601 reflectionsΔρmin = 0.31 e Å3
251 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
S10.57106 (12)0.24556 (8)0.49235 (5)0.0255 (2)
N10.0374 (4)0.4493 (2)0.63392 (13)0.0209 (5)
N20.1759 (4)0.4342 (3)0.58009 (13)0.0202 (5)
N30.2050 (4)0.1530 (3)0.57790 (17)0.0311 (6)
C10.1576 (4)0.5967 (3)0.66381 (15)0.0187 (6)
C20.0813 (5)0.7547 (3)0.64597 (19)0.0218 (6)
C30.2709 (5)0.9130 (3)0.67964 (19)0.0267 (6)
C40.3900 (5)0.8872 (3)0.77390 (18)0.0271 (6)
C50.4936 (4)0.7411 (3)0.77777 (16)0.0213 (6)
C100.3814 (4)0.6016 (3)0.72246 (15)0.0191 (6)
C90.4809 (4)0.4679 (3)0.72410 (17)0.0226 (6)
C80.6878 (5)0.4710 (3)0.78065 (17)0.0260 (6)
C70.7975 (5)0.6088 (3)0.83626 (19)0.0274 (6)
C60.7026 (5)0.7431 (3)0.83434 (17)0.0265 (6)
C110.3029 (4)0.2765 (3)0.55299 (16)0.0203 (6)
H2A0.030 (4)0.763 (3)0.5850 (16)0.012 (6)*
H2B0.059 (5)0.742 (3)0.6765 (17)0.030 (7)*
H3A0.383 (5)0.937 (3)0.6388 (19)0.039 (8)*
H3B0.205 (4)1.011 (3)0.6756 (16)0.028 (7)*
H4A0.509 (5)0.991 (3)0.7973 (17)0.034 (7)*
H4B0.275 (5)0.862 (3)0.8164 (17)0.032 (7)*
H60.404 (4)0.373 (3)0.6829 (17)0.032 (7)*
H70.754 (5)0.383 (3)0.7821 (17)0.030 (7)*
H80.933 (5)0.612 (3)0.8765 (19)0.038 (8)*
H90.779 (5)0.839 (3)0.8738 (18)0.035 (8)*
HN20.242 (5)0.518 (3)0.5664 (18)0.037 (8)*
HN3A0.283 (5)0.047 (4)0.5558 (19)0.044 (9)*
HN3B0.065 (6)0.176 (4)0.607 (2)0.053 (10)*
N40.2849 (4)0.4881 (3)0.04821 (14)0.0251 (5)
N50.1068 (4)0.8479 (3)0.17016 (16)0.0355 (6)
N60.2570 (4)0.1174 (3)0.02636 (15)0.0375 (6)
C120.3663 (4)0.6193 (3)0.05758 (16)0.0228 (6)
C130.4196 (4)0.3699 (3)0.00991 (16)0.0231 (6)
C140.2226 (5)0.7472 (3)0.12048 (18)0.0263 (6)
C150.3294 (5)0.2286 (3)0.01969 (18)0.0282 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0220 (4)0.0187 (3)0.0324 (4)0.0062 (3)0.0051 (3)0.0043 (3)
N10.0186 (12)0.0223 (11)0.0218 (12)0.0064 (9)0.0019 (10)0.0011 (9)
N20.0174 (12)0.0189 (12)0.0232 (12)0.0073 (10)0.0027 (10)0.0028 (9)
N30.0210 (15)0.0194 (13)0.0476 (16)0.0074 (11)0.0105 (12)0.0064 (11)
C10.0198 (14)0.0176 (13)0.0185 (14)0.0044 (10)0.0040 (11)0.0006 (10)
C20.0202 (16)0.0215 (14)0.0207 (16)0.0030 (11)0.0001 (13)0.0009 (11)
C30.0286 (17)0.0185 (14)0.0320 (17)0.0075 (12)0.0009 (14)0.0023 (11)
C40.0271 (17)0.0229 (15)0.0279 (16)0.0044 (12)0.0007 (14)0.0047 (12)
C50.0207 (15)0.0216 (13)0.0198 (14)0.0029 (11)0.0044 (12)0.0011 (10)
C100.0169 (14)0.0227 (13)0.0172 (14)0.0046 (11)0.0032 (11)0.0004 (10)
C90.0221 (16)0.0224 (14)0.0244 (15)0.0076 (12)0.0049 (12)0.0012 (11)
C80.0219 (16)0.0306 (16)0.0276 (16)0.0110 (13)0.0062 (13)0.0067 (12)
C70.0171 (16)0.0365 (16)0.0242 (16)0.0033 (12)0.0001 (13)0.0035 (12)
C60.0223 (16)0.0290 (15)0.0233 (16)0.0011 (12)0.0007 (13)0.0016 (12)
C110.0186 (15)0.0193 (13)0.0224 (14)0.0064 (11)0.0002 (11)0.0026 (10)
N40.0221 (13)0.0290 (12)0.0256 (13)0.0091 (10)0.0043 (10)0.0011 (10)
N50.0277 (15)0.0353 (14)0.0398 (16)0.0039 (11)0.0027 (12)0.0060 (12)
N60.0369 (16)0.0411 (15)0.0373 (15)0.0173 (13)0.0027 (12)0.0048 (11)
C120.0198 (15)0.0278 (14)0.0206 (14)0.0047 (11)0.0051 (12)0.0011 (11)
C130.0214 (15)0.0282 (14)0.0205 (14)0.0086 (12)0.0030 (12)0.0000 (11)
C140.0217 (16)0.0319 (15)0.0267 (16)0.0098 (13)0.0042 (13)0.0004 (12)
C150.0238 (16)0.0319 (16)0.0289 (16)0.0097 (13)0.0009 (13)0.0039 (12)
Geometric parameters (Å, º) top
S1—C111.684 (2)C5—C61.398 (4)
N1—C11.292 (3)C5—C101.402 (3)
N1—N21.382 (3)C10—C91.399 (3)
N2—C111.360 (3)C9—C81.385 (4)
N2—HN20.89 (3)C9—H60.98 (3)
N3—C111.324 (3)C8—C71.392 (4)
N3—HN3A0.92 (3)C8—H70.92 (3)
N3—HN3B0.86 (3)C7—C61.385 (4)
C1—C101.479 (3)C7—H80.93 (3)
C1—C21.498 (3)C6—H90.98 (3)
C2—C31.526 (3)N4—C121.338 (3)
C2—H2A0.93 (2)N4—C131.340 (3)
C2—H2B1.04 (3)N5—C141.146 (3)
C3—C41.519 (4)N6—C151.143 (3)
C3—H3A0.99 (3)C12—C13i1.397 (4)
C3—H3B0.99 (3)C12—C141.447 (4)
C4—C51.505 (3)C13—C12i1.396 (4)
C4—H4A0.99 (3)C13—C151.450 (4)
C4—H4B1.02 (3)
C1—N1—N2118.6 (2)C6—C5—C4121.2 (2)
C11—N2—N1117.3 (2)C10—C5—C4119.6 (2)
C11—N2—HN2117.5 (18)C9—C10—C5119.7 (2)
N1—N2—HN2124.9 (18)C9—C10—C1120.8 (2)
C11—N3—HN3A117.4 (19)C5—C10—C1119.6 (2)
C11—N3—HN3B120 (2)C8—C9—C10120.6 (2)
HN3A—N3—HN3B122 (3)C8—C9—H6120.5 (16)
N1—C1—C10115.3 (2)C10—C9—H6118.9 (16)
N1—C1—C2124.8 (2)C9—C8—C7119.6 (3)
C10—C1—C2119.9 (2)C9—C8—H7120.9 (17)
C1—C2—C3113.1 (2)C7—C8—H7119.5 (17)
C1—C2—H2A108.4 (13)C6—C7—C8120.4 (3)
C3—C2—H2A110.3 (14)C6—C7—H8118.5 (16)
C1—C2—H2B107.8 (13)C8—C7—H8121.1 (17)
C3—C2—H2B109.8 (13)C7—C6—C5120.6 (2)
H2A—C2—H2B107 (2)C7—C6—H9120.3 (16)
C4—C3—C2110.8 (2)C5—C6—H9119.0 (16)
C4—C3—H3A110.5 (16)N3—C11—N2116.4 (2)
C2—C3—H3A107.6 (15)N3—C11—S1123.34 (19)
C4—C3—H3B111.5 (14)N2—C11—S1120.27 (18)
C2—C3—H3B109.8 (15)C12—N4—C13116.1 (2)
H3A—C3—H3B106 (2)N4—C12—C13i121.5 (2)
C5—C4—C3110.5 (2)N4—C12—C14116.4 (2)
C5—C4—H4A110.8 (15)C13i—C12—C14122.1 (2)
C3—C4—H4A111.5 (15)N4—C13—C12i122.5 (2)
C5—C4—H4B107.9 (14)N4—C13—C15115.6 (2)
C3—C4—H4B110.8 (15)C12i—C13—C15121.9 (2)
H4A—C4—H4B105 (2)N5—C14—C12179.3 (3)
C6—C5—C10119.1 (2)N6—C15—C13179.2 (3)
C1—N1—N2—C11177.1 (2)N1—C1—C10—C5162.0 (2)
N2—N1—C1—C10178.73 (19)C2—C1—C10—C515.5 (3)
N2—N1—C1—C21.3 (3)C5—C10—C9—C80.8 (4)
N1—C1—C2—C3172.5 (2)C1—C10—C9—C8178.4 (2)
C10—C1—C2—C310.1 (3)C10—C9—C8—C70.1 (4)
C1—C2—C3—C446.8 (3)C9—C8—C7—C60.9 (4)
C2—C3—C4—C558.8 (3)C8—C7—C6—C51.1 (4)
C3—C4—C5—C6144.3 (2)C10—C5—C6—C70.3 (4)
C3—C4—C5—C1034.5 (3)C4—C5—C6—C7179.1 (2)
C6—C5—C10—C90.6 (4)N1—N2—C11—N32.8 (3)
C4—C5—C10—C9178.1 (2)N1—N2—C11—S1176.37 (16)
C6—C5—C10—C1178.7 (2)C13—N4—C12—C13i0.6 (4)
C4—C5—C10—C12.6 (3)C13—N4—C12—C14179.7 (2)
N1—C1—C10—C917.2 (3)C12—N4—C13—C12i0.6 (4)
C2—C1—C10—C9165.2 (2)C12—N4—C13—C15179.9 (2)
Symmetry code: (i) x+1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—HN2···S1ii0.89 (3)2.57 (3)3.450 (2)173 (2)
N3—HN3A···S1iii0.92 (3)2.44 (3)3.348 (2)170 (3)
Symmetry codes: (ii) x+1, y+1, z+1; (iii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—HN2···S1i0.89 (3)2.57 (3)3.450 (2)173 (2)
N3—HN3A···S1ii0.92 (3)2.44 (3)3.348 (2)170 (3)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1, y, z+1.
 

Acknowledgements

We gratefully acknowledge financial support by the German Research Foundation (DFG) through the Collaborative Research Center SFB 813, Chemistry at Spin Centers, and by FAPITEC/SE/FUNTEC/CNPq through the PPP Program 04/ 2011.

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Volume 70| Part 10| October 2014| Pages o1090-o1091
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