2. Experimental Crystal data

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data reports ISSN 2056-9890 Crystal structure of 5-(1,3-dithian-2-yl)- 2H-1,3-benzodioxole Julio Zukerman-Schpector, a * Ignez Caracelli, b Hélio A. Stefani, c Olga Gozhina c and Edward R. T.

1 data reports ISSN Crystal structure of 5-(1,3-dithian-2-yl)- 2H-1,3-benzodioxole Julio Zukerman-Schpector, a * Ignez Caracelli, b Hélio A. Stefani, c Olga Gozhina c and Edward R. T. Tiekink d a Departmento de Química, Universidade Federal de São Carlos, São Carlos, SP, Brazil, b Departmento de Física, Universidade Federal de São Carlos, São Carlos, SP, Brazil, c Departamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, São Paulo-SP, Brazil, and d Department of Chemistry, University of Malaya, Kuala Lumpur, Malaysia. *Correspondence julio@power.ufscar.br Received 4 February 2015; accepted 5 February Experimental 2.1. Crystal data C 11 H 12 O 2 S 2 M r = Monoclinic, P2 1 =c a = (3) Å b = (4) Å c = (2) Å = (1) V = (9) Å 3 Z =8 Mo K radiation = 0.45 mm 1 T = 296 K mm Edited by W. T. A. Harrison, University of Aberdeen, Scotland In the title compound, C 11 H 12 O 2 S 2, two independent but virtually superimposable molecules, A and B, comprise the asymmetric unit. In each molecule, the 1,3-dithiane ring has a chair conformation with the 1,4-disposed C atoms being above and below the plane through the remaining four atoms. The substituted benzene ring occupies an equatorial position in each case and forms dihedral angles of (9) (molecule A) and (8) (molecule B) with the least-squares plane through the 1,3-dithiane ring. The difference between the molecules rests in the conformation of the five-membered 1,3- dioxole ring which is an envelope in molecule A (the methylene C atom is the flap) and almost planar in molecule B (r.m.s. deviation = Å). In the crystal, molecules of A self-associate into supramolecular zigzag chains (generated by glide symmetry along the c axis) via methylene C H interactions. Molecules of B form similar chains. The chains pack with no specific directional intermolecular interactions between them. Keywords: crystal structure; 1,3-dithiane; conformation; 1,3-benzodioxole; C H interactions. CCDC reference: Related literature The title compound has been prepared previously, see: Ballesteros et al. (2005). For the structure of a related compound containing the same molecular skeleton as in the title compound, i.e. (19R,21R,25S)-( )-2-(2-menthyloxycarbonyl-3,4-methylenedioxyphenyl)1,3-dithiane, see: Ratajczak- Sitarz et al. (1996) Data collection Bruker APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.702, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections Table 1 Hydrogen-bond geometry (Å, ) measured reflections 4164 independent reflections 3759 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.29 e Å 3 min = 0.44 e Å 3 Cg1 and Cg2 are the centroids of the C5 C11 and C16 C21 rings, respectively. D HA D H HA DA D HA C4 H4bCg1 i (2) 170 C13 H13aCg2 ii (19) 165 Symmetry codes: (i) x; y þ 1 2 ; z 1 2 ; (ii) x; y 1 2 ; z 3 2. Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMOL (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010) and publcif (Westrip, 2010). Acknowledgements We thank Professor Regina H. A. Santos from IQSC USP for the X-ray data collection. The Brazilian agencies CNPq doi: /s Zukerman-Schpector et al. o167

2 data reports (305626/ to JZS, / to IC and / to HAS), FAPESP (2012/ and 2013/ ) and CAPES are acknowledged for financial support. Supporting information for this paper is available from the IUCr electronic archives (Reference: HB7361). References Ballesteros, L., Noguez, O., Arroyo, G., Velasco, B., Delgado, F. & Miranda, R. (2005). J. Mex. Chem. Soc. 49, Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Burla, M. C., Caliandro, R., Carrozzini, B., Cascarano, G. L., Cuocci, C., Giacovazzo, C., Mallamo, M., Mazzone, A. & Polidori, G. (2015). J. Appl. Cryst. 48, ChemAxon (2010). Marvinsketch. Farrugia, L. J. (2012). J. Appl. Cryst. 45, Gans, J. & Shalloway, D. (2001). J. Mol. Graph. Model. 19, Ratajczak-Sitarz, M., Naruszewicz, M., Kosturkiewicz, Z., Jozkowiak, J. & Rozwadowska, M. D. (1996). Pol. J. Chem. 70, Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2015). Acta Cryst. C71, 3 8. Westrip, S. P. (2010). J. Appl. Cryst. 43, o168 Zukerman-Schpector et al. C 11 H 12 O 2 S 2

3 supporting information [doi: /s ] Crystal structure of 5-(1,3-dithian-2-yl)-2H-1,3-benzodioxole Julio Zukerman-Schpector, Ignez Caracelli, Hélio A. Stefani, Olga Gozhina and Edward R. T. Tiekink S1. Experimental A solution of the corresponding 2H-1,3-benzodioxole-5-carbaldehyde (0.037 mol, 1 equiv.) in chloroform (20 ml) was combined with an equimolar amount of propane-1,3-dithiol (3.7 ml, mol) at room temperature. The solution was stirred for 1 h at this temperature, then cooled to -20 C after which BF 3 etherate (0.46 ml, mol, 0.1 equiv.) was added drop-wise. The reaction solution was allowed to warm to room temperature and stirred overnight. After this time, the solution was washed three times each with water, 10% aqueous KOH, then water followed by drying over MgSO 4. Evaporation of the solvent furnishes a pure product as colourless crystals in 97% yield. To obtain crystals suitable for X- ray analysis, the product was crystallized from CH 3 OH. The spectroscopic data matched those reported in the literature (Ballesteros et al., 2005). S2. Refinement Carbon-bound H-atoms were placed in calculated positions (C H = Å) and were included in the refinement in the riding model approximation, with U iso (H) = 1.2 U eq (C). sup-1

4 Figure 1 The molecular structures of the two independent molecules in title compound showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level. sup-2

5 Figure 2 Superimposition of the two independent molecules. Molecule A is shown in red and B in blue. The molecules have been superimposed such that the benzene rings are overlapped. sup-3

Figure 3 A view of the zigzag supramolecular chain comprising molecules of A along the c axis (glide symmetry) mediated by C H π interactions are shown as purple dashed lines.

6 Figure 3 A view of the zigzag supramolecular chain comprising molecules of A along the c axis (glide symmetry) mediated by C H π interactions are shown as purple dashed lines. Figure 4 A view in projection down the c axis of the unit-cell contents. The C H π interactions are shown as purple dashed lines. 5-(1,3-Dithian-2-yl)-2H-1,3-benzodioxole Crystal data C 11 H 12 O 2 S 2 M r = Monoclinic, P2 1 /c a = (3) Å sup-4

7 b = (4) Å c = (2) Å β = (1) V = (9) Å 3 Z = 8 F(000) = 1008 D x = Mg m 3 Data collection Bruker APEXII CCD diffractometer φ and ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.702, T max = measured reflections Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 271 parameters 0 restraints Mo Kα radiation, λ = Å Cell parameters from 9068 reflections θ = µ = 0.45 mm 1 T = 296 K Prism, colourless mm 4164 independent reflections 3759 reflections with I > 2σ(I) R int = θ max = 25.4, θ min = 1.8 h = k = l = 14 8 Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0459P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.29 e Å 3 Δρ min = 0.44 e Å 3 Special details 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. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq S (5) (3) (4) (16) S (5) (3) (4) (15) O (16) (13) (13) (6) O (15) (9) (12) (4) C (15) (10) (15) (4) H * C (2) (13) (16) (5) H2A * H2B * C (18) (12) (16) (5) H3A * H3B * C (2) (12) (17) (5) H4A * H4B * C (15) (11) (15) (4) sup-5

8 C (18) (15) (19) (6) H * C (2) (18) (2) (7) H * C (19) (14) (16) (6) C (17) (11) (15) (4) C (16) (10) (15) (4) H * C (3) (16) (18) (7) H11A * H11B * S (5) (2) (4) (14) S (4) (2) (4) (14) O (13) (10) (12) (4) O (14) (9) (12) (4) C (15) (9) (15) (4) H * C (19) (10) (16) (4) H13A * H13B * C (18) (11) (16) (4) H14A * H14B * C (19) (10) (16) (5) H15A * H15B * C (16) (9) (15) (4) C (17) (10) (18) (4) H * C (18) (11) (18) (5) H * C (18) (10) (16) (4) C (16) (10) (16) (4) C (16) (11) (15) (4) H * C (2) (14) (18) (5) H22A * H22B * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 S (4) (3) (3) (3) (2) (2) S (3) (3) (3) (2) (2) (2) O (11) (18) (7) (11) (7) (9) O (11) (11) (7) (8) (7) (7) C (9) (10) (9) (8) (7) (8) C (13) (13) (9) (10) (9) (9) sup-6

9 C (12) (12) (9) (9) (8) (8) C (13) (12) (11) (10) (9) (9) C (9) (11) (9) (8) (7) (8) C (11) (17) (12) (11) (9) (11) C (12) (2) (12) (14) (10) (13) C (11) (16) (10) (11) (8) (10) C (10) (11) (9) (8) (8) (8) C (9) (10) (8) (8) (7) (7) C (19) (18) (11) (15) (11) (11) S (3) (2) (3) (2) (2) (17) S (3) (2) (3) (19) (2) (18) O (8) (11) (7) (7) (6) (7) O (10) (9) (8) (8) (7) (7) C (9) (8) (9) (7) (7) (7) C (12) (9) (10) (8) (9) (7) C (11) (10) (9) (8) (8) (8) C (12) (10) (10) (9) (9) (8) C (9) (8) (9) (7) (8) (7) C (9) (9) (11) (7) (8) (8) C (11) (10) (13) (8) (10) (9) C (12) (9) (10) (8) (9) (7) C (10) (10) (9) (8) (8) (7) C (9) (11) (9) (8) (8) (8) C (15) (14) (10) (11) (10) (10) Geometric parameters (Å, º) S1 C (18) S3 C (18) S1 C (19) S3 C (17) S2 C (2) S4 C (19) S2 C (18) S4 C (17) O1 C (2) O3 C (2) O1 C (3) O3 C (2) O2 C (2) O4 C (2) O2 C (3) O4 C (3) C1 C (2) C12 C (2) C1 H C12 H C2 C (3) C13 C (3) C2 H2A C13 H13A C2 H2B C13 H13B C3 C (3) C14 C (3) C3 H3A C14 H14A C3 H3B C14 H14B C4 H4A C15 H15A C4 H4B C15 H15B C5 C (3) C16 C (2) C5 C (2) C16 C (2) C6 C (3) C17 C (3) sup-7

10 C6 H C17 H C7 C (3) C18 C (3) C7 H C18 H C8 C (3) C19 C (2) C9 C (2) C20 C (2) C10 H C21 H C11 H11A C22 H22A C11 H11B C22 H22B C2 S1 C (9) C13 S3 C (8) C4 S2 C (9) C15 S4 C (8) C8 O1 C (17) C20 O3 C (15) C9 O2 C (18) C19 O4 C (14) C5 C1 S (13) C16 C12 S (11) C5 C1 S (12) C16 C12 S (12) S1 C1 S (10) S3 C12 S (9) C5 C1 H C16 C12 H S1 C1 H S3 C12 H S2 C1 H S4 C12 H C3 C2 S (13) C14 C13 S (13) C3 C2 H2A C14 C13 H13A S1 C2 H2A S3 C13 H13A C3 C2 H2B C14 C13 H13B S1 C2 H2B S3 C13 H13B H2A C2 H2B H13A C13 H13B C4 C3 C (17) C13 C14 C (16) C4 C3 H3A C13 C14 H14A C2 C3 H3A C15 C14 H14A C4 C3 H3B C13 C14 H14B C2 C3 H3B C15 C14 H14B H3A C3 H3B H14A C14 H14B C3 C4 S (13) C14 C15 S (13) C3 C4 H4A C14 C15 H15A S2 C4 H4A S4 C15 H15A C3 C4 H4B C14 C15 H15B S2 C4 H4B S4 C15 H15B H4A C4 H4B H15A C15 H15B C6 C5 C (17) C17 C16 C (16) C6 C5 C (17) C17 C16 C (16) C10 C5 C (16) C21 C16 C (15) C5 C6 C (2) C16 C17 C (18) C5 C6 H C16 C17 H C7 C6 H C18 C17 H C8 C7 C (2) C19 C18 C (16) C8 C7 H C19 C18 H C6 C7 H C17 C18 H C7 C8 C (18) C18 C19 O (17) C7 C8 O (2) C18 C19 C (17) sup-8

11 C9 C8 O (2) O4 C19 C (17) C10 C9 O (18) C21 C20 O (16) C10 C9 C (18) C21 C20 C (17) O2 C9 C (16) O3 C20 C (16) C9 C10 C (17) C20 C21 C (16) C9 C10 H C20 C21 H C5 C10 H C16 C21 H O1 C11 O (18) O4 C22 O (16) O1 C11 H11A O4 C22 H22A O2 C11 H11A O3 C22 H22A O1 C11 H11B O4 C22 H22B O2 C11 H11B O3 C22 H22B H11A C11 H11B H22A C22 H22B C2 S1 C1 C (12) C13 S3 C12 C (13) C2 S1 C1 S (11) C13 S3 C12 S (11) C4 S2 C1 C (13) C15 S4 C12 C (12) C4 S2 C1 S (11) C15 S4 C12 S (11) C1 S1 C2 C (17) C12 S3 C13 C (16) S1 C2 C3 C (2) S3 C13 C14 C (2) C2 C3 C4 S (2) C13 C14 C15 S (2) C1 S2 C4 C (18) C12 S4 C15 C (16) S1 C1 C5 C (18) S3 C12 C16 C (16) S2 C1 C5 C (18) S4 C12 C16 C (15) S1 C1 C5 C (19) S3 C12 C16 C (19) S2 C1 C5 C (2) S4 C12 C16 C (19) C10 C5 C6 C7 0.9 (3) C21 C16 C17 C (3) C1 C5 C6 C (2) C12 C16 C17 C (16) C5 C6 C7 C8 0.3 (4) C16 C17 C18 C (3) C6 C7 C8 C9 0.3 (4) C17 C18 C19 O (18) C6 C7 C8 O (2) C17 C18 C19 C (3) C11 O1 C8 C (3) C22 O4 C19 C (2) C11 O1 C8 C9 7.8 (3) C22 O4 C19 C (2) C11 O2 C9 C (2) C22 O3 C20 C (2) C11 O2 C9 C8 7.3 (2) C22 O3 C20 C (2) C7 C8 C9 C (3) C18 C19 C20 C (3) O1 C8 C9 C (18) O4 C19 C20 C (17) C7 C8 C9 O (2) C18 C19 C20 O (17) O1 C8 C9 O2 0.3 (2) O4 C19 C20 O3 0.8 (2) O2 C9 C10 C (18) O3 C20 C21 C (18) C8 C9 C10 C5 0.2 (3) C19 C20 C21 C (3) C6 C5 C10 C9 0.8 (3) C17 C16 C21 C (3) C1 C5 C10 C (16) C12 C16 C21 C (16) C8 O1 C11 O (3) C19 O4 C22 O3 7.3 (2) C9 O2 C11 O (2) C20 O3 C22 O4 6.8 (2) sup-9

12 Hydrogen-bond geometry (Å, º) Cg1 and Cg2 are the centroids of the C5 C11 and C16 C21 rings, respectively. D H A D H H A D A D H A C4 H4b Cg1 i (2) 170 C13 H13a Cg2 ii (19) 165 Symmetry codes: (i) x, y+1/2, z 1/2; (ii) x, y 1/2, z 3/2. sup-10

Experimental. Crystal data

Experimental. Crystal data organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 4-Bromo-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-(4-methoxybenzylideneamino)-1H-pyrazole-3-carbonitrile Guohui