Supplementary Material

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1 Supplementary Material Synthesis of bis-oxathiaaza[3.3.3]propellanes via nucleophilic addition of (1,ω-alkanediyl)bis(N'-organylthioureas) on dicyanomethylene-1,3-indanedione Alaa A. Hassan, a * Kamal M. A. El-Shaieb, a Amal S. Abd El-Aal, 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 Single crystal X-ray diffraction study was carried out on an Agilent Super Nova diffractometer at 173 K with EOS-detector and MoKα radiation (λ = Ǻ). Direct Methods (SHELXS-97 [Sheldrick, G.M., Acta Crystallogr., A64, ]) were used for structure solution and refinement was carried out using SHELXL-2013 [Sheldrick, G.M., Acta Crystallogr., A64, ] (full-matrix least-squares on F 2 ). Hydrogen atoms were localized by difference Fourier Synthesis map and refined using a riding model [H(N) free]. A semi-empirical absorption correction and an extinction correction were applied. Compound 7a: C 40 H 26 N 8 O 4 S 2 2 (C 3 H 7 NO), Mr = gmol -1, colorless plates, crystal size mm, triclinic, P-1 (no. 2), a = (5) Å, b = Å, c = Å, α = , β = (5), γ = , V = Å 3, Z = 1, D calcd = Mg m -3, F(000)= 466, µ = mm -1, T = 173 K, 7638 measured reflections (2θ max = 55 ), 4954 independent reflections (R int. = 0.016) 298 parameters, 2 restraints, R1 ( for 3998 I > 2σ(I)) = 0.044, wr 2 (for all data ) = 0.107, S = 1.03, largest diff. peak and hole = 0.35 ea -3, ea -3. Supplementary data Crystallographic data for the structure reported in this work have been deposited with Cambridge Crystallographic Data Center on supplementary publication no CCDC Copies of the data can be obtained free of charge on publication to the Director, CCDC, 12 Union Road, Cambridge CB2 IEZ,UK (fax:+44(1223)336033: deposit@ccdc.cam.ac.uk. Page S1

2 Figure 1. Molecular structure of 7a in the crystal (displacement parameters are drawn at 50% probability level). The crystallographic numbering does not reflect the systematic IUPAC numbering (SB651_HY). Figure 2. Crystal packing of 7a (in the voids are DMF). Page S2

3 Table 1. Crystal data for 7a Table 2. Data collection for 7a C 40 H 26 N 8 O 4 S 2 2(C 3 H 7 NO) Z = 1 M r = F(000) = 466 Triclinic, P-1 (no.2) D x = Mg m -3 a = (5) Å b = Å Mo Kα radiation, λ = Å Cell parameters from 2581 reflections c = Å θ = α = µ = 0.18 mm -1 β = (5) γ = T = 173 K Plates, colourless V = Å mm Agilent, SuperNova, Single source at offset, Eos diffractometer Radiation source: SuperNova (Mo) X-ray Source 4954 independent reflections 3998 reflections with I > 2σ(I) Detector resolution: pixels mm -1 R int = rotation in ω, 1 scans θ max = 27.5, θ min = 2.4 Absorption correction: multi-scan CrysAlis PRO, Agilent Technologies. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. h = T min = 0.858, T max = k = measured reflections l = Table 3. Refinement data for 7a Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = Secondary atom site location: difference Fourier map Hydrogen site location: difference Fourier map H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o 2 ) + (0.0373P) P] where P = (F o 2 + 2F c 2 )/3 Page S3

4 S = 1.03 ( /σ) max = reflections max = 0.31 e Å parameters min = e Å -3 2 restraints Extinction correction: SHELXL, Fc * =kfc[ xfc 2 λ 3 /sin(2θ)] -1/4 Primary atom site location: structure-invariant direct methods Extinction coefficient: Table 4. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) for 7a x y z U iso */U eq S (5) C N C (5) (3) C C (3) (3) (3) (4) (5) H * C (3) (3) H * C (3) (3) H * C (3) (5) H * C C O (4) (4) (4) Page S4

5 C C C N H14A H14B (3) O C N N C C (3) (3) (3) (4) (3) (4) 0.054* 0.054* (3) (4) (5) (3) (4) (5) H * C (3) (3) H * C (3) (3) H * C (3) (3) H * C (5) H * C (4) H25A * H25B * O1D (4) Page S5

6 C1D (3) (5) H1D * N1D C2D (4) (3) (5) H2D * H2D * H2D * C3D (3) (4) H3D * H3D * H3D * Table 7. Atomic displacement parameters Å 2 for 7a. U 11 U 22 U 33 U 12 U 13 U 23 S C N C C C C C C C (3) (5) (5) C Page S6

7 O C C C N O (5) C N N C C C C C C C O1D C1D N1D C2D C3D (5) (4) (4) Page S7

8 S1 C S1 C Geometric parameters (Å, º) for 7a N14 H14B C16 N C2 N N18 C C2 N C19 C (3) N3 C C19 C (3) N3 C C4 O C20 C (3) C20 H C4 C C21 C (4) C4 C C21 H C5 C C22 C (3) C5 C C22 H C6 C (3) C23 C (3) C6 H C23 H C7 C (3) C24 H C7 H C25 C25 i (3) C8 C (3) C25 H25A C8 H C25 H25B C9 C (3) O1D C1D (3) C9 H C1D N1D (3) C10 C C1D H1D C11 O N1D C2D (3) C11 C N1D C3D (3) C12 C C2D H2D C13 C C2D H2D C13 C C2D H2D C14 N C3D H3D C14 O C3D H3D N14 H14A C3D H3D C2 S1 C C14 N14 H14B N18 C2 N H14A N Page S8

9 N18 C2 S N3 C2 S C2 N3 C C2 N3 C C4 N3 C N3 C4 O N3 C4 C O15 C4 C N3 C4 C O15 C4 C12 H14B C5 C4 C C6 C5 C C6 C5 C C10 C5 C C7 C6 C C14 O15 C N17 C16 C C2 N18 C C24 C19 C C24 C19 N C20 C19 N C21 C20 C C21 C20 H C19 C20 H C22 C21 C C22 C21 H C20 C21 H C23 C22 C C23 C22 H C21 C22 H C7 C6 H C22 C23 C C5 C6 H C22 C23 H C6 C7 C C24 C23 H C6 C7 H C19 C24 C C8 C7 H C19 C24 H C9 C8 C C23 C24 H C9 C8 H N3 C25 C25 i C7 C8 H N3 C25 H25A C8 C9 C C25 i C Page S9

10 H25A C8 C9 H N3 C25 H25B C10 C9 H C25 i C25 H25B C5 C10 C H25A C25 H25B C5 C10 C O1D C1D N1D C9 C10 C O1D C1D H1D O11 C11 C N1D C1D H1D O11 C11 C C1D N1D C2D C10 C11 C C1D N1D C3D C13 C12 C C2D N1D C3D C13 C12 C N1D C2D H2D1 C11 C12 C N1D C2D H2D2 C13 C12 S H2D1 C2D H2D2 C11 C12 S N1D C2D H2D3 C4 C12 S H2D1 C2D H2D3 C14 C13 C H2D2 C2D H2D3 C14 C13 C N1D C3D H3D1 C16 C13 C N1D C3D H3D2 N14 C14 O H3D1 C3D H3D2 N14 C14 C N1D C3D H3D3 O15 C14 C H3D1 C3D H3D3 C14 N14 H14A H3D2 C3D H3D3 Page S10

11 C12 S1 C2 N18 C12 S1 C2 N3 N18 C2 N3 C4 S1 C2 N3 C4 N18 C2 N3 C25 S1 C2 N3 C25 C2 N3 C4 O15 C25 N3 C4 O15 C2 N3 C4 C5 C25 N3 C4 C5 C2 N3 C4 C12 C25 N3 C4 C12 N3 C4 C5 C6 O15 C4 C5 C6 C12 C4 C5 C6 N3 C4 C5 C10 O15 C4 C5 C10 C12 C4 C5 C10 C10 C5 C6 C7 C4 C5 C6 C7 C5 C6 C7 C C5 C4 C12 C13 N3 C4 C12 C11 O15 C4 C12 C C5 C4 C12 C N3 C4 C12 S O15 C4 C12 S1 C5 C4 C12 S1 C2 S1 C12 C13 C2 S1 C12 C C2 S1 C12 C C11 C12 C13 C14 C4 C12 C13 C S1 C12 C13 C C11 C12 C13 C C4 C12 C13 C16 S1 C12 C13 C16 C16 C13 C14 N C12 C13 C14 N (3) C16 C13 C14 O C12 C13 C14 O (4) N14 C14 O15 C (3) C6 C7 0.9 (4) C13 C Page S11

12 C8 C9 O15 C4 C7 C8 C9 C (4) N3 C4 O15 C C6 C5 C10 C9 2.0 (3) C5 C4 O15 C C4 C5 C10 C C12 C4 O15 C C6 C5 C10 C N3 C2 N18 C C4 C5 C10 C S1 C2 N18 C C8 C9 C10 C5-0.4 (3) C2 N18 C19 C C8 C9 C10 C C2 N18 C19 C C5 C10 C11 O C24 C19 C20 C (3) C9 C10 C11 O (3) N18 C19 C20 C C5 C10 C11 C C19 C20 C21 C (4) C9 C10 C11 C C20 C21 C22 C (4) O11 C11 C12 C C21 C22 C23 C (4) C10 C11 C12 C C20 C19 C24 C (3) O11 C11 C12 C N18 C19 C24 C C10 C11 C12 C C22 C23 C24 C (3) O11 C11 C12 S C2 N3 C25 C25 i C10 C11 C12 S C4 N3 C C25 i N3 C4 C12 C O1D C1D N1D C2D O15 C4 C12 C O1D C1D N1D C3D 8.5 (3) Symmetry code: (i) -x+2, -y+2, -z+1. Hydrogen-bond geometry (Å, º) for 7a. Page S12

13 D H A D H H A D A D H A N H14A O1D ii N H14B N17 iii C H25B O15 i C3D H3D3 O (3) Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) x+1, y+1, z; (iii) -x+1, -y+2, -z. Page S13

14 1 H-NMR of (7a):- 13 C-NMR of (7a):- Page S14

15 1 H-NMR of (7b):- 13 C-NMR of (7b):- Page S15

16 ARKIVOC 2016 (v) S1-S H-NMR of (7c): C-NMR of (7c):- 4 Page S16

17 ARKIVOC 2016 (v) S1-S H-NMR of (7d): C-NMR of (7d):- 8 9 Page S17

18 ARKIVOC 2016 (v) S1-S H-NMR of (7e): C-NMR of (7e): Page S18