Literature DB >> 25484688

Crystal structure of the charge-transfer complex 2-(1,2,3,4-tetra-hydro-naph-thal-en-1-yl-idene)hydrazinecarbo-thio-amide-pyrazine-2,3,5,6-tetra-carbo-nitrile (2/1).

Johannes Beck1, Jörg Daniels1, Petra Krieger-Beck1, Gertrud Dittmann1, Adriano Bof de Oliveira2.   

Abstract

The reaction of 2-(1,2,3,4-tetra-hydro-napthalen-1-yl-idene)hydrazinecarbo-thio-amide (TTSC) with pyrazine-2,3,5,6-tetra-carbo-nitrile (tetra-cyano-pyrazine, TCNP) yields the title 2:1 charge-transfer adduct, 2C11H12N3S·C6N8. The complete TCNP mol-ecule is generated by a crystallographic inversion centre and the non-aromatic ring in the TTSC mol-ecule adopts an envelope conformation with a methyl-ene C atom as the flap. In the crystal, the thio-semicarbazone mol-ecules are connected through inversion-related pairs of N-H⋯S inter-actions, building a polymeric chain along the b-axis direction. The TCNP mol-ecules are embedded in the structure, forming TTSC-TCNP-TTSC stacks with the aromatic rings of TTSC and the mol-ecular 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.

Entities:  

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

Year:  2014        PMID： 25484688      PMCID： PMC4257178          DOI： 10.1107/S1600536814019795

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


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 ▶).

Experimental

Crystal data

2C11H13N3S·C8N6 M = 618.74 Triclinic, 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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.045 wR(F 2) = 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

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 ▶). Crystal structure: contains datablock(s) I, publication_text. DOI: 10.1107/S1600536814019795/hb7278sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814019795/hb7278Isup2.hkl Click here for additional data file. Supporting information file. DOI: 10.1107/S1600536814019795/hb7278Isup3.cml Click here for additional data file. x y z . DOI: 10.1107/S1600536814019795/hb7278fig1.tif 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. Click here for additional data file. via . DOI: 10.1107/S1600536814019795/hb7278fig2.tif Mol­ecules of TTSC connected via N—H⋯S hydrogen bridges to an infinite ribbon. Bond lengths are given in Å. Click here for additional data file. b . DOI: 10.1107/S1600536814019795/hb7278fig3.tif The arrangement of the mol­ecules in the structure of the title compound in a perspective view along the b-axis. Click here for additional data file. 2 iii x y z x y z x y z . DOI: 10.1107/S1600536814019795/hb7278fig4.tif 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. Click here for additional data file. . DOI: 10.1107/S1600536814019795/hb7278fig5.tif Photo of crystals of the title compound. The crystals are embedded in unreacted TCNP, which was used in excess. Click here for additional data file. . DOI: 10.1107/S1600536814019795/hb7278fig6.tif Crystal UV-vis absorption spectrum of the title compound recorded with light in horizontal and vertical polarization direction. CCDC reference: 1022549 Additional supporting information: crystallographic information; 3D view; checkCIF report
2C11H13N3S·C8N6Z = 1
Mr = 618.74F(000) = 322
Triclinic, P1Dx = 1.404 Mg m−3
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 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
Nonius KappaCCD diffractometer2601 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 = −7→7
Absorption correction: analytical (Alcock, 1970)k = −9→9
Tmin = 0.987, Tmax = 0.995l = −18→18
10255 measured reflections
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 = 1.08w = 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 Å−3
0 restraintsΔρmin = −0.31 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.
xyzUiso*/Ueq
S10.57106 (12)0.24556 (8)0.49235 (5)0.0255 (2)
N1−0.0374 (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)
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)
C110.3029 (4)0.2765 (3)0.55299 (16)0.0203 (6)
H2A−0.030 (4)0.763 (3)0.5850 (16)0.012 (6)*
H2B0.059 (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)*
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)
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)
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—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—C3172.5 (2)C1—C10—C9—C8178.4 (2)
C10—C1—C2—C3−10.1 (3)C10—C9—C8—C70.1 (4)
C1—C2—C3—C446.8 (3)C9—C8—C7—C60.9 (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—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—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—C12.6 (3)C13—N4—C12—C14−179.7 (2)
N1—C1—C10—C9−17.2 (3)C12—N4—C13—C12i0.6 (4)
C2—C1—C10—C9165.2 (2)C12—N4—C13—C15−179.9 (2)
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)
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A D—HH⋯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) ; (ii) .

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2.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

3.  The tetracyanopyrazinide dimer dianion, [TCNP]2(2-). 2-Electron 8-center bonding.

Authors:  Juan J Novoa; Peter W Stephens; Mahika Weerasekare; William W Shum; Joel S Miller
Journal:  J Am Chem Soc       Date:  2009-07-01       Impact factor: 15.419

4.  2-(1,2,3,4-Tetra-hydro-naphthalen-1-yl-idene)hydrazinecarbothio-amide.

Authors:  Adriano Bof de Oliveira; Cecília Santos Silva; Bárbara Regina Santos Feitosa; Christian Näther; Inke Jess
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2012-07-28
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