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

Beck, J.; Daniels, J.; Krieger-Beck, P.; Dittmann, G.; Oliveira, A.B. de

doi:10.1107/S1600536814019795

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

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

doi:10.1107/S1600536814019795

Open

access

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

Johannes Beck,^a ^* Jörg Daniels,^a Petra Krieger-Beck,^a Gertrud Dittmann ^a and Adriano Bof de Oliveira ^b

^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.

Keywords: charge-transfer composite compound; tetracyanopyrazine; thiosemicarbazone; crystal structure.

CCDC reference: 1022549

1. Related literature

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. (2012 7). 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 ).

2. Experimental

2.1. Crystal data

2C₁₁H₁₃N₃S·C₈N₆
M_r = 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 ) T_min = 0.987, T_max = 0.995
10255 measured reflections
2601 independent reflections
1775 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; 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 ).

Supporting information

CCDC reference: 1022549

Crystal structure: contains datablocks I, publication_text. DOI: 10.1107/S1600536814019795/hb7278sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814019795/hb7278Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814019795/hb7278Isup3.cml

checkCIF report

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

	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.
	Fig. 2. : Molecules of TTSC connected via N—H···S hydrogen bridges to an infinite ribbon. Bond lengths are given in Å.
	Fig. 3. : The arrangement of the molecules in the structure of the title compound in a perspective view along the b-axis.
	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.
	Fig. 5. : Photo of crystals of the title compound. The crystals are embedded in unreacted TCNP, which was used in excess.
	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·C₈N₆	Z = 1
M_r = 618.74	F(000) = 322
Triclinic, P1	D_x = 1.404 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1363 (4) Å	Cell parameters from 15334 reflections
b = 8.2574 (3) Å	θ = 2.9–27.5°
c = 15.3303 (9) Å	µ = 0.23 mm⁻¹
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 KappaCCD	1775 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.073
Detector resolution: 9 pixels mm^-1	θ_max = 25.1°, θ_min = 3.5°
CCD rotation images, thick slices scans	h = −7→7
Absorption correction: analytical (Alcock, 1970)	k = −9→9
T_min = 0.987, T_max = 0.995	l = −18→18
10255 measured reflections

Refinement top

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	All H-atom parameters refined
S = 1.08	w = 1/[σ²(F_o²) + (0.0321P)² + 0.1427P] where P = (F_o² + 2F_c²)/3
2601 reflections	(Δ/σ)_max < 0.001
251 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

2C₁₁H₁₃N₃S·C₈N₆	γ = 73.893 (3)°
M_r = 618.74	V = 731.95 (7) Å³
Triclinic, P1	Z = 1
a = 6.1363 (4) Å	Mo Kα radiation
b = 8.2574 (3) Å	µ = 0.23 mm⁻¹
c = 15.3303 (9) Å	T = 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)
T_min = 0.987, T_max = 0.995	R_int = 0.073
10255 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.096	All H-atom parameters refined
S = 1.08	Δρ_max = 0.26 e Å⁻³
2601 reflections	Δρ_min = −0.31 e Å⁻³
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

	x	y	z	U_iso*/U_eq
S1	0.57106 (12)	0.24556 (8)	0.49235 (5)	0.0255 (2)
N1	−0.0374 (4)	0.4493 (2)	0.63392 (13)	0.0209 (5)
N2	0.1759 (4)	0.4342 (3)	0.58009 (13)	0.0202 (5)
N3	0.2050 (4)	0.1530 (3)	0.57790 (17)	0.0311 (6)
C1	−0.1576 (4)	0.5967 (3)	0.66381 (15)	0.0187 (6)
C2	−0.0813 (5)	0.7547 (3)	0.64597 (19)	0.0218 (6)
C3	−0.2709 (5)	0.9130 (3)	0.67964 (19)	0.0267 (6)
C4	−0.3900 (5)	0.8872 (3)	0.77390 (18)	0.0271 (6)
C5	−0.4936 (4)	0.7411 (3)	0.77777 (16)	0.0213 (6)
C10	−0.3814 (4)	0.6016 (3)	0.72246 (15)	0.0191 (6)
C9	−0.4809 (4)	0.4679 (3)	0.72410 (17)	0.0226 (6)
C8	−0.6878 (5)	0.4710 (3)	0.78065 (17)	0.0260 (6)
C7	−0.7975 (5)	0.6088 (3)	0.83626 (19)	0.0274 (6)
C6	−0.7026 (5)	0.7431 (3)	0.83434 (17)	0.0265 (6)
C11	0.3029 (4)	0.2765 (3)	0.55299 (16)	0.0203 (6)
H2A	−0.030 (4)	0.763 (3)	0.5850 (16)	0.012 (6)*
H2B	0.059 (5)	0.742 (3)	0.6765 (17)	0.030 (7)*
H3A	−0.383 (5)	0.937 (3)	0.6388 (19)	0.039 (8)*
H3B	−0.205 (4)	1.011 (3)	0.6756 (16)	0.028 (7)*
H4A	−0.509 (5)	0.991 (3)	0.7973 (17)	0.034 (7)*
H4B	−0.275 (5)	0.862 (3)	0.8164 (17)	0.032 (7)*
H6	−0.404 (4)	0.373 (3)	0.6829 (17)	0.032 (7)*
H7	−0.754 (5)	0.383 (3)	0.7821 (17)	0.030 (7)*
H8	−0.933 (5)	0.612 (3)	0.8765 (19)	0.038 (8)*
H9	−0.779 (5)	0.839 (3)	0.8738 (18)	0.035 (8)*
HN2	0.242 (5)	0.518 (3)	0.5664 (18)	0.037 (8)*
HN3A	0.283 (5)	0.047 (4)	0.5558 (19)	0.044 (9)*
HN3B	0.065 (6)	0.176 (4)	0.607 (2)	0.053 (10)*
N4	0.2849 (4)	0.4881 (3)	0.04821 (14)	0.0251 (5)
N5	0.1068 (4)	0.8479 (3)	0.17016 (16)	0.0355 (6)
N6	0.2570 (4)	0.1174 (3)	−0.02636 (15)	0.0375 (6)
C12	0.3663 (4)	0.6193 (3)	0.05758 (16)	0.0228 (6)
C13	0.4196 (4)	0.3699 (3)	−0.00991 (16)	0.0231 (6)
C14	0.2226 (5)	0.7472 (3)	0.12048 (18)	0.0263 (6)
C15	0.3294 (5)	0.2286 (3)	−0.01969 (18)	0.0282 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0220 (4)	0.0187 (3)	0.0324 (4)	−0.0062 (3)	0.0051 (3)	−0.0043 (3)
N1	0.0186 (12)	0.0223 (11)	0.0218 (12)	−0.0064 (9)	−0.0019 (10)	−0.0011 (9)
N2	0.0174 (12)	0.0189 (12)	0.0232 (12)	−0.0073 (10)	0.0027 (10)	−0.0028 (9)
N3	0.0210 (15)	0.0194 (13)	0.0476 (16)	−0.0074 (11)	0.0105 (12)	−0.0064 (11)
C1	0.0198 (14)	0.0176 (13)	0.0185 (14)	−0.0044 (10)	−0.0040 (11)	−0.0006 (10)
C2	0.0202 (16)	0.0215 (14)	0.0207 (16)	−0.0030 (11)	0.0001 (13)	−0.0009 (11)
C3	0.0286 (17)	0.0185 (14)	0.0320 (17)	−0.0075 (12)	−0.0009 (14)	−0.0023 (11)
C4	0.0271 (17)	0.0229 (15)	0.0279 (16)	−0.0044 (12)	0.0007 (14)	−0.0047 (12)
C5	0.0207 (15)	0.0216 (13)	0.0198 (14)	−0.0029 (11)	−0.0044 (12)	0.0011 (10)
C10	0.0169 (14)	0.0227 (13)	0.0172 (14)	−0.0046 (11)	−0.0032 (11)	0.0004 (10)
C9	0.0221 (16)	0.0224 (14)	0.0244 (15)	−0.0076 (12)	−0.0049 (12)	0.0012 (11)
C8	0.0219 (16)	0.0306 (16)	0.0276 (16)	−0.0110 (13)	−0.0062 (13)	0.0067 (12)
C7	0.0171 (16)	0.0365 (16)	0.0242 (16)	−0.0033 (12)	0.0001 (13)	0.0035 (12)
C6	0.0223 (16)	0.0290 (15)	0.0233 (16)	−0.0011 (12)	−0.0007 (13)	−0.0016 (12)
C11	0.0186 (15)	0.0193 (13)	0.0224 (14)	−0.0064 (11)	0.0002 (11)	−0.0026 (10)
N4	0.0221 (13)	0.0290 (12)	0.0256 (13)	−0.0091 (10)	−0.0043 (10)	−0.0011 (10)
N5	0.0277 (15)	0.0353 (14)	0.0398 (16)	−0.0039 (11)	−0.0027 (12)	−0.0060 (12)
N6	0.0369 (16)	0.0411 (15)	0.0373 (15)	−0.0173 (13)	−0.0027 (12)	−0.0048 (11)
C12	0.0198 (15)	0.0278 (14)	0.0206 (14)	−0.0047 (11)	−0.0051 (12)	−0.0011 (11)
C13	0.0214 (15)	0.0282 (14)	0.0205 (14)	−0.0086 (12)	−0.0030 (12)	0.0000 (11)
C14	0.0217 (16)	0.0319 (15)	0.0267 (16)	−0.0098 (13)	−0.0042 (13)	0.0004 (12)
C15	0.0238 (16)	0.0319 (16)	0.0289 (16)	−0.0097 (13)	−0.0009 (13)	−0.0039 (12)

Geometric parameters (Å, º) top

S1—C11	1.684 (2)	C5—C6	1.398 (4)
N1—C1	1.292 (3)	C5—C10	1.402 (3)
N1—N2	1.382 (3)	C10—C9	1.399 (3)
N2—C11	1.360 (3)	C9—C8	1.385 (4)
N2—HN2	0.89 (3)	C9—H6	0.98 (3)
N3—C11	1.324 (3)	C8—C7	1.392 (4)
N3—HN3A	0.92 (3)	C8—H7	0.92 (3)
N3—HN3B	0.86 (3)	C7—C6	1.385 (4)
C1—C10	1.479 (3)	C7—H8	0.93 (3)
C1—C2	1.498 (3)	C6—H9	0.98 (3)
C2—C3	1.526 (3)	N4—C12	1.338 (3)
C2—H2A	0.93 (2)	N4—C13	1.340 (3)
C2—H2B	1.04 (3)	N5—C14	1.146 (3)
C3—C4	1.519 (4)	N6—C15	1.143 (3)
C3—H3A	0.99 (3)	C12—C13ⁱ	1.397 (4)
C3—H3B	0.99 (3)	C12—C14	1.447 (4)
C4—C5	1.505 (3)	C13—C12ⁱ	1.396 (4)
C4—H4A	0.99 (3)	C13—C15	1.450 (4)
C4—H4B	1.02 (3)

C1—N1—N2	118.6 (2)	C6—C5—C4	121.2 (2)
C11—N2—N1	117.3 (2)	C10—C5—C4	119.6 (2)
C11—N2—HN2	117.5 (18)	C9—C10—C5	119.7 (2)
N1—N2—HN2	124.9 (18)	C9—C10—C1	120.8 (2)
C11—N3—HN3A	117.4 (19)	C5—C10—C1	119.6 (2)
C11—N3—HN3B	120 (2)	C8—C9—C10	120.6 (2)
HN3A—N3—HN3B	122 (3)	C8—C9—H6	120.5 (16)
N1—C1—C10	115.3 (2)	C10—C9—H6	118.9 (16)
N1—C1—C2	124.8 (2)	C9—C8—C7	119.6 (3)
C10—C1—C2	119.9 (2)	C9—C8—H7	120.9 (17)
C1—C2—C3	113.1 (2)	C7—C8—H7	119.5 (17)
C1—C2—H2A	108.4 (13)	C6—C7—C8	120.4 (3)
C3—C2—H2A	110.3 (14)	C6—C7—H8	118.5 (16)
C1—C2—H2B	107.8 (13)	C8—C7—H8	121.1 (17)
C3—C2—H2B	109.8 (13)	C7—C6—C5	120.6 (2)
H2A—C2—H2B	107 (2)	C7—C6—H9	120.3 (16)
C4—C3—C2	110.8 (2)	C5—C6—H9	119.0 (16)
C4—C3—H3A	110.5 (16)	N3—C11—N2	116.4 (2)
C2—C3—H3A	107.6 (15)	N3—C11—S1	123.34 (19)
C4—C3—H3B	111.5 (14)	N2—C11—S1	120.27 (18)
C2—C3—H3B	109.8 (15)	C12—N4—C13	116.1 (2)
H3A—C3—H3B	106 (2)	N4—C12—C13ⁱ	121.5 (2)
C5—C4—C3	110.5 (2)	N4—C12—C14	116.4 (2)
C5—C4—H4A	110.8 (15)	C13ⁱ—C12—C14	122.1 (2)
C3—C4—H4A	111.5 (15)	N4—C13—C12ⁱ	122.5 (2)
C5—C4—H4B	107.9 (14)	N4—C13—C15	115.6 (2)
C3—C4—H4B	110.8 (15)	C12ⁱ—C13—C15	121.9 (2)
H4A—C4—H4B	105 (2)	N5—C14—C12	179.3 (3)
C6—C5—C10	119.1 (2)	N6—C15—C13	179.2 (3)

C1—N1—N2—C11	177.1 (2)	N1—C1—C10—C5	162.0 (2)
N2—N1—C1—C10	−178.73 (19)	C2—C1—C10—C5	−15.5 (3)
N2—N1—C1—C2	−1.3 (3)	C5—C10—C9—C8	−0.8 (4)
N1—C1—C2—C3	172.5 (2)	C1—C10—C9—C8	178.4 (2)
C10—C1—C2—C3	−10.1 (3)	C10—C9—C8—C7	0.1 (4)
C1—C2—C3—C4	46.8 (3)	C9—C8—C7—C6	0.9 (4)
C2—C3—C4—C5	−58.8 (3)	C8—C7—C6—C5	−1.1 (4)
C3—C4—C5—C6	−144.3 (2)	C10—C5—C6—C7	0.3 (4)
C3—C4—C5—C10	34.5 (3)	C4—C5—C6—C7	179.1 (2)
C6—C5—C10—C9	0.6 (4)	N1—N2—C11—N3	2.8 (3)
C4—C5—C10—C9	−178.1 (2)	N1—N2—C11—S1	−176.37 (16)
C6—C5—C10—C1	−178.7 (2)	C13—N4—C12—C13ⁱ	−0.6 (4)
C4—C5—C10—C1	2.6 (3)	C13—N4—C12—C14	−179.7 (2)
N1—C1—C10—C9	−17.2 (3)	C12—N4—C13—C12ⁱ	0.6 (4)
C2—C1—C10—C9	165.2 (2)	C12—N4—C13—C15	−179.9 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—HN2···S1ⁱⁱ	0.89 (3)	2.57 (3)	3.450 (2)	173 (2)
N3—HN3A···S1ⁱⁱⁱ	0.92 (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···A	D—H	H···A	D···A	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.

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.

References

Alcock, N. W. (1970). Crystallographic Computing, edited by F. R. Ahmed, S. R. Hall & C. P. Huber, p. 271. Copenhagen: Munksgaard, Denmark. Google Scholar
Begland, R. W., Hartter, D. R., Donald, D. S., Cairncross, A. & Sheppard, W. A. (1974). J. Org. Chem. 39, 1235–1239. CrossRef CAS Web of Science Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Freund, M. & Schander, A. (1902). Chem. Ber. 35, 2602–2606. CrossRef CAS Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Novoa, J. J., Stephens, P. W., Weerasekare, M., Shum, W. W. & Miller, J. S. (2009). J. Am. Chem. Soc. 131, 9070–9075. Web of Science CSD CrossRef PubMed CAS Google Scholar
Oliveira, A. B. de, Silva, C. S., Feitosa, B. R. S., Näther, C. & Jess, I. (2012). Acta Cryst. E68, o2581. CSD CrossRef IUCr Journals Google Scholar
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. Google Scholar
Rosokha, Y. S., Lindeman, S. V., Roskha, S. V. & Kochi, J. K. (2004). Angew. Chem. Int. Ed. 43, 4650–4652. Web of Science CSD CrossRef CAS Google Scholar
Rosokha, S. V., Lu, J., Han, B. & Kochi, J. K. (2009). New J. Chem. 33, 545–553. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

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

doi:10.1107/S1600536814019795

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

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

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

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