Supplementary Material

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1 Supplementary Material Reactivity of 2-substituted hydrazinecarbothioamides towards tetracyanoethylene and convenient synthesis of (5-amino-2-diazenylthiazolylmethylene)malononitrile derivatives Alaa A. Hassan, a, * Nasr K. Mohamed, a Kamal M. A. El-Shaieb, a Hendawy N. Tawfeek, a Stefan Bräse, b and Martin Nieger c a Chemistry Department, Faculty of Science, Minia University, El-Minia, Egypt b Institute of Organic Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg 6, Karlsruhe, Germany c Laboratory of Inorganic Chemistry, Department of Chemistry, University of Helsinki P.O. Box 55 (A. I. Virtasen aukio 1), Helsinki, Finland alaahassan2001@mu.edu.eg Corresponding author: Prof. Dr. Alaa A. Hassan; alaahassan2001@mu.edu.eg; Chemistry Department, Faculty of Science, Minia University, El-Minia, Egypt Received [Dates will be filled in by the Editorial office] Single crystal X-ray structure determination of 3a Single crystals were obtained by recrystallization from acetonitrile. The single crystal X-ray diffraction study was carried out on a Bruker D8 Venture diffractometer with Photon100 detector at 123K using CuKα radiation (λ = Ǻ). Direct Methods (SHELXS-97) 32 were used for structure solution and refinement was carried out using SHELXL (full-matrix least-squares on F2). Hydrogen atoms bound to C-atoms were refined using a riding model whilst the NH-hydrogen atoms were refined freely. A semi-empirical absorption correction was applied. Page S1

2 Fig. S1: Molecular Structure of 3a in the crystal (TIF file). The crystallographic numbering does not reflect the systematic IUPAC numbering. Table S1. Crystal data for 3a. C13H9N7S Z = 2 Mr = F(000) = 304 Triclinic, P-1 (no.2) Dx = Mg m -3 a = (4) Å Cu K radiation, = Å b = (5) Å Cell parameters from 8992 reflections c = (7) Å = = (2) = 2.26 mm -1 = (2) = (2) V = (7) Å 3 T = 123 K Plates, red mm Table S2.data collection for 3a. Bruker D8 Venture diffractometer with Photon100 detector 2405 reflections with I > 2 (I) Radiation source: I S microfocus Rint = rotation in and, 1, shutterless scans max = 72.0, min = 3.9 Page S2

3 Absorption correction: multi-scan SADABS (Sheldrick, 2015) h = -9 9 Tmin = 0.814, Tmax = k = measured reflections l = independent reflections Refinement on F 1 Least-squares matrix: full Table S3. Refinement data for 3a. Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map R[F 2 > 2 (F 2 )] = Hydrogen site location: difference Fourier map wr(f 2 ) = S = 1.06 H atoms treated by a mixture of independent and constrained refinement W = 1/[ 2 (Fo 2 ) + (0.0215P) P] where P = (Fo 2 + 2Fc 2 )/ reflections ( / )max < parameters max = 0.27 e Å -3 4 restraints min = e Å -3 Table S4. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) for 3a. X Y Z Uiso*/Ueq S (4) (4) (3) (10) C (18) (16) (11) (3) N (15) (14) (9) (2) C (17) (16) (11) (2) C (18) (16) (11) (3) N (15) (14) (9) (2) N (15) (14) (9) (2) C (18) (17) (11) (3) C (19) (18) (13) (3) Page S3

4 H * C (2) (2) (14) (3) H * C (2) (2) (13) (3) H * C (2) (2) (12) (3) H * C (19) (19) (12) (3) H * N (17) (15) (10) (2) H41A (2) (19) (15) 0.024* H41B (2) (2) (13) 0.024* C (18) (16) (11) (3) C (18) (16) (11) (3) C (19) (17) (11) (3) N (17) (15) (10) (3) C (19) (17) (11) (3) N (18) (16) (11) (3) N (17) (15) (10) (2) H51A (2) (19) (15) 0.023* H51B (2) (2) (14) 0.023* Table S5. Atomic displacement parameters (Å2) for 3a. U 11 U 22 U 33 U 12 U 13 U 23 S (17) (16) (16) (12) (12) (11) C (6) (6) (6) (5) (5) (5) N (5) (5) (5) (4) (4) (4) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) Page S4

5 N (5) (5) (5) (4) (4) (4) N (5) (5) (5) (4) (4) (4) C (6) (7) (6) (5) (5) (5) C (7) (7) (7) (5) (5) (6) C (7) (8) (8) (6) (6) (7) C (7) (9) (7) (6) (6) (7) C (7) (9) (6) (6) (5) (6) C (6) (7) (6) (5) (5) (5) N (6) (5) (5) (4) (5) (4) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) N (6) (6) (6) (5) (5) (5) C (7) (6) (6) (5) (5) (5) N (7) (6) (6) (5) (5) (5) N (6) (5) (5) (4) (5) (4) Table S6. Geometric parameters (Å, º) for 3a. S1 C (13) C26 C (2) S1 C (13) C26 H C2 N (17) C27 C (2) C2 N (16) C27 H N3 C (16) C28 H C4 C (18) N41 C (17) C4 C (18) N41 H41A (14) C5 N (17) N41 H41B (14) N21 N (15) C41 C (17) N22 C (16) C42 C (18) Page S5

6 C23 C (19) C42 C (18) C23 C (19) C43 N (18) C24 C (2) C44 N (18) C24 H N51 H51A (14) C25 C (2) N51 H51B (14) C25 H C5 S1 C (6) C25 C26 H N3 C2 N (11) C27 C26 H N3 C2 S (9) C28 C27 C (14) N21 C2 S (9) C28 C27 H C2 N3 C (10) C26 C27 H N3 C4 C (11) C27 C28 C (14) N3 C4 C (11) C27 C28 H C5 C4 C (11) C23 C28 H N51 C5 C (12) C41 N41 H41A (11) N51 C5 S (10) C41 N41 H41B (11) C4 C5 S (9) H41A N41 H41B (16) N22 N21 C (10) N41 C41 C (12) N21 N22 C (11) N41 C41 C (11) C24 C23 C (12) C42 C41 C (11) C24 C23 N (12) C41 C42 C (11) C28 C23 N (12) C41 C42 C (12) C25 C24 C (13) C43 C42 C (11) C25 C24 H N43 C43 C (13) C23 C24 H N44 C44 C (14) C26 C25 C (14) C5 N51 H51A (12) C26 C25 H C5 N51 H51B (11) C24 C25 H H51A N51 H51B (16) Page S6

7 C25 C26 C (13) C5 S1 C2 N (10) C28 C23 C24 C (2) C5 S1 C2 N (11) N22 C23 C24 C (12) N21 C2 N3 C (11) C23 C24 C25 C (2) S1 C2 N3 C (14) C24 C25 C26 C (2) C2 N3 C4 C (15) C25 C26 C27 C (2) C2 N3 C4 C (11) C26 C27 C28 C (2) N3 C4 C5 N (12) C24 C23 C28 C (19) C41 C4 C5 N (2) N22 C23 C28 C (12) N3 C4 C5 S (14) N3 C4 C41 N (17) C41 C4 C5 S (10) C5 C4 C41 N (13) C2 S1 C5 N (11) N3 C4 C41 C (12) C2 S1 C5 C (9) C5 C4 C41 C (19) N3 C2 N21 N (11) N41 C41 C42 C (19) S1 C2 N21 N (14) C4 C41 C42 C (12) C2 N21 N22 C (10) N41 C41 C42 C (12) N21 N22 C23 C (11) C4 C41 C42 C (19) N21 N22 C23 C (18) Table S7. Hydrogen-bond geometry (Å, º)For 3a. D H A D H H A D A D H A N41 H41A S1i 0.88 (1) 2.89 (2) (12) 138 (1) N41 H41B N3ii 0.88 (1) 2.39 (2) (15) 143 (2) N51 H51A N43iii 0.87 (1) 2.24 (2) (16) 155 (2) N51 H51B N43iv 0.88 (1) 2.26 (2) (16) 153 (2) Symmetry codes: (i) x, y-1, z; (ii) -x, -y, -z+1; (iii) x, y+1, z; (iv) -x, -y, -z+2. Document origin: publcif [Westrip, S. P. (2010). J. Apply. Cryst., 43, ]. Page S7

8 1 H-NMR of 3a 1 H and 13 C-NMR spectrums of 3a-d 13 C-NMR of 3a Page S8

9 1 H-NMR of 3b 13 C-NMR of 3b Page S9

10 1 H-NMR of 3c 13 C-NMR of 3c Page S10

11 1 H-NMR of 3d 13 C-NMR of 3d Page S11

12 1 H-NMR of 3e 13 C-NMR of 3e Page S12