1-(4-Bromo­phen­yl)-2-ethyl­sulfinyl-2-(phenyl­selan­yl)ethanone monohydrate

Julio Zukerman-Schpector; Carlos A De Simone; Paulo R Olivato; Carlos R Cerqueira, Jr; Edward R T Tiekink

doi:10.1107/S1600536811012712

. 2011 Apr 13;67(Pt 5):o1099–o1100. doi: 10.1107/S1600536811012712

1-(4-Bromophenyl)-2-ethylsulfinyl-2-(phenylselanyl)ethanone monohydrate

Julio Zukerman-Schpector ^a,^*, Carlos A De Simone ^b, Paulo R Olivato ^c, Carlos R Cerqueira Jr ^c, Edward R T Tiekink ^d

PMCID: PMC3089188 PMID: 21754419

Abstract

In the title hydrate, C₁₆H₁₅BrO₂SSe·H₂O, the sulfinyl O atom lies on the opposite side of the molecule to the Se and carbonyl O atoms. The benzene rings form a dihedral angle of 51.66 (17)° and are splayed with respect to each other. The observed conformation allows the water molecules to bridge sulfinyl O atoms via O—H⋯O hydrogen bonds, generating a linear supramolecular chain along the b axis; the chain is further stabilized by C—H⋯O contacts. The chains are held in place in the crystal structure by C⋯H⋯π and C—Br⋯π interactions.

Related literature

For background to β,β-bis-substituted-carbonyl compounds, see: Reis et al. (2006 ▶). For related structures, see: Olivato et al. (2004 ▶); Zukerman-Schpector et al. (2009 ▶, 2010 ▶). For details of the synthetic protocols, see: Long (1946 ▶); Leonard & Johnson (1962 ▶); Zoretic & Soja (1976 ▶).

Experimental

Crystal data

C₁₆H₁₅BrO₂SSe·H₂O
M _r = 448.23
Monoclinic,
a = 14.6942 (2) Å
b = 6.1103 (1) Å
c = 21.5717 (4) Å
β = 113.714 (1)°
V = 1773.30 (5) Å³
Z = 4
Mo Kα radiation
μ = 4.50 mm⁻¹
T = 290 K
0.36 × 0.19 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.291, T _max = 0.734
32063 measured reflections
3734 independent reflections
3177 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.095
S = 1.03
3734 reflections
200 parameters
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: MarvinSketch (Chemaxon, 2010 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811012712/hg5022sup1.cif

e-67-o1099-sup1.cif^{(19KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012712/hg5022Isup2.hkl

e-67-o1099-Isup2.hkl^{(179.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C5–C10 and C11–C16 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H1w⋯O2ⁱ	0.85	1.95	2.788 (4)	169
O1w—H2w⋯O2	0.84	1.99	2.810 (4)	165
C2—H2⋯O1wⁱ	0.98	2.40	3.334 (4)	159
C3—H3b⋯O1wⁱ	0.97	2.54	3.434 (4)	153
C9—H9⋯O1wⁱⁱ	0.93	2.55	3.320 (4)	141
C10—H10⋯O2ⁱⁱ	0.93	2.58	3.456 (4)	157
C14—H14⋯Cg1ⁱⁱⁱ	0.93	2.96	3.793 (5)	149
C8—Br⋯Cg2^iv	1.90 (1)	3.49 (1)	5.349 (3)	165 (1)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

We thank the Brazilian agencies FAPESP, CNPq (fellowships to JZS and PRO) and CAPES (808/2009 to JZS) for financial support.

supplementary crystallographic information

Comment

As part of our on-going research on the conformational and electronic interactions in some β,β-substituted-carbonyl compounds, e.g. 4'-substituted 2-(bromo)-2-(ethylsulfonyl)- and 4'-substituted 2-(methylthio)-2-(diethoxyphosphoryl)]-acetophenones, and 3,3-bis[(4'-chlorophenyl)thio]-1-methylpiperidin-2-one, using theoretical, spectroscopic and X-ray diffraction methods (Olivato et al., 2004; Reis et al., 2006; Zukerman-Schpector et al., 2009; Zukerman-Schpector et al., 2010), the title hydrate, (I), was synthesized and its crystal structure determined, Fig. 1.

With reference to the pyramidal-S atom, the sulfinyl-O lies to the opposite side of the molecule to each of the Se and carbonyl-O atoms. This conformation allows for the formation of supramolecular chains mediated by the sulfinyl-O and water molecules, see below. The benzene rings are splayed with respect to each other as seen in the value of the C1—C2—Se—C11 torsion angle of -27.7 (2) °; the dihedral angle formed between the rings is 51.66 (17) °.

In the crystal packing, the water molecules bridge sulfinyl-O atoms via O—H···O hydrogen bonds to form a linear supramolecular chain along the b axis, Fig. 2 and Table 1. Chains are stabilized by a series of C—H···O interactions, Table 1, and are held in place by C—H···π(aryl-Br) and C—Br···π(aryl-Se) interactions, Fig. 3 and Table 1.

Experimental

Following the procedure of Long (1946), a solution of potassium hydroxide (400 mg, 7.2 mmol) and ethanothiol (0.5 ml, 7.2 mmol) in ethanol (10 ml) was added to a solution of 2-bromo-4'-bromoacetophenone (2.0 g, 7.2 mmol) in ethanol, to give 2-ethylthio-4'-bromoacetophenone (1.6 g, yield = 86%). The product was isolated and oxidized with 12 ml of an aqueous solution of sodium periodate (0.5 M) in acetonitrile (16 ml), after Leonard & Johnson (1962), to give 2-ethylsulfinyl-4'-bromoacetophenone that was extracted with dichloromethane and dried over anhydrous magnesium sulfate. 2-Ethylsulfinyl-4'-bromoacetophenone (730 mg, 2.6 mmol) was added drop-wise to a cooled (195 K) solution of diisopropylamine (0.4 ml, 2.6 mmol) and butyllithium (2.3 ml, 2.6 mmol) in THF (20 ml). After 20 minutes, phenylselenilbromide (610 mg, 2.6 mmol) dissolved in THF (10 ml) was added drop-wise to the enolate solution (Zoretic and Soja, 1976). After stirring for 3 h at 195 K, water (50 ml) was added at room temperature and extraction with chloroform was performed. The organic layer was dried over anhydrous magnesium sulfate. After evaporation of solvent, a crude solid was obtained. Purification through flash chromatography with a solution of hexane and ethyl acetate in a 1:1 ratio gave a mixture of the two possible diastereoisomers (500 mg, yield = 45%). One of the diastereoisomers was separated by recrystallization at low temperature (283 K) from chloroform. Suitable crystals for X-ray analysis were obtained by vapour diffusion of n-hexane into its chloroform solution at 283 K; M.pt. 366–367 K. IR (cm^-1): ν(C=O) 1670, ν(S=O) 993. NMR (CDCl₃, p.p.m.): δ 1.42–1.45 (3H, t ³J = 7.5 Hz), 2.92–2.99 (1H, dq, ²J = 13 Hz, ³J = 7.5 Hz), 3.32–3.25 (1H, dq, ²J = 13 Hz, ³J = 7.5 Hz), 5.44 (1H, s), 7.29–7.33 (2H, m, Aryl-H), 7.38–7.41 (1H, m, Aryl-H), 7.52–7.55 (2H, m, Aryl-H), 7.59–7.62 (2H, m, Aryl-H), 7.75–7.73 (2H, m, Aryl-H). Analysis found: C 42.76, H 3.84%. C₁₆H₁₅BrO₂SSe.H₂O requires: C 42.87, H 3.82%.