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

Zukerman-Schpector, J.; De Simone, C.A.; Olivato, P.R.; Cerqueira, C.R.; Tiekink, E.R.T.

doi:10.1107/S1600536811012712

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Pages o1099-o1100

doi:10.1107/S1600536811012712

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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 and Edward R. T. Tiekink ^d

^aDepartment of Chemistry, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, ^bInstituto de Química e Biotecnologia, Universidade Federal de Alagoas, 57072-970 Maceió, AL, Brazil, ^cChemistry Institute, Universidade de São Paulo, 05508-000 São Paulo-SP, Brazil, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: julio@power.ufscar.br

(Received 3 April 2011; accepted 5 April 2011; online 13 April 2011)

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, P 2₁ /c
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[F² > 2σ(F²)] = 0.037
wR(F²) = 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

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)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y-{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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%.

Computing details top

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).

Figures top

	Fig. 1. The molecular structure of (I) showing atom labelling scheme and displacement ellipsoids at the 35% probability level (arbitrary spheres for the H atoms).
	Fig. 2. Supramolecular linear chain along the b axis in (I) mediated by O—H···O hydrogen bonding (orange dashed lines).
	Fig. 3. View of the unit-cell contents in projection down the b axis in (I). Chains shown in Fig. 2, sustained by O–H···O hydrogen bonding (orange dashed lines), are held in place by C—H···π and C—Br···π contacts, shown as blue and purple dashed lines, respectively.

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

Crystal data top

C₁₆H₁₅BrO₂SSe·H₂O	F(000) = 888
M_r = 448.23	D_x = 1.679 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 23524 reflections
a = 14.6942 (2) Å	θ = 2.6–26.7°
b = 6.1103 (1) Å	µ = 4.50 mm⁻¹
c = 21.5717 (4) Å	T = 290 K
β = 113.714 (1)°	Plate, colourless
V = 1773.30 (5) Å³	0.36 × 0.19 × 0.16 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	3734 independent reflections
Radiation source: sealed tube	3177 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
CCD rotation images scans	θ_max = 26.7°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
T_min = 0.291, T_max = 0.734	k = −7→7
32063 measured reflections	l = −27→25

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0428P)² + 1.5141P] where P = (F_o² + 2F_c²)/3
3734 reflections	(Δ/σ)_max < 0.001
200 parameters	Δρ_max = 0.80 e Å⁻³
0 restraints	Δρ_min = −0.55 e Å⁻³

Crystal data top

C₁₆H₁₅BrO₂SSe·H₂O	V = 1773.30 (5) Å³
M_r = 448.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.6942 (2) Å	µ = 4.50 mm⁻¹
b = 6.1103 (1) Å	T = 290 K
c = 21.5717 (4) Å	0.36 × 0.19 × 0.16 mm
β = 113.714 (1)°

Data collection top

Nonius KappaCCD diffractometer	3734 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3177 reflections with I > 2σ(I)
T_min = 0.291, T_max = 0.734	R_int = 0.076
32063 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.03	Δρ_max = 0.80 e Å⁻³
3734 reflections	Δρ_min = −0.55 e Å⁻³
200 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.27316 (19)	0.2209 (5)	0.25810 (14)	0.0424 (6)
C2	0.36493 (19)	0.1572 (5)	0.32017 (13)	0.0419 (6)
H2	0.4114	0.0804	0.3055	0.050*
C3	0.5393 (2)	0.2846 (6)	0.42271 (17)	0.0593 (8)
H3A	0.5269	0.1896	0.4545	0.071*
H3B	0.5683	0.1973	0.3977	0.071*
C4	0.6102 (3)	0.4646 (8)	0.4605 (2)	0.0811 (12)
H4A	0.5806	0.5522	0.4844	0.122*
H4B	0.6243	0.5547	0.4290	0.122*
H4C	0.6709	0.4014	0.4922	0.122*
C5	0.23970 (19)	0.0756 (5)	0.19795 (14)	0.0409 (6)
C6	0.1669 (2)	0.1548 (5)	0.13798 (15)	0.0488 (6)
H6	0.1396	0.2925	0.1373	0.059*
C7	0.1349 (2)	0.0315 (5)	0.07957 (16)	0.0544 (7)
H7	0.0868	0.0854	0.0395	0.065*
C8	0.1756 (2)	−0.1734 (5)	0.08164 (15)	0.0503 (7)
C9	0.2473 (2)	−0.2565 (5)	0.14005 (16)	0.0506 (7)
H9	0.2736	−0.3952	0.1405	0.061*
C10	0.2796 (2)	−0.1304 (5)	0.19819 (15)	0.0470 (6)
H10	0.3287	−0.1843	0.2379	0.056*
C11	0.1967 (2)	0.0520 (5)	0.36178 (14)	0.0468 (6)
C12	0.1754 (3)	0.2435 (6)	0.38661 (18)	0.0612 (8)
H12	0.2261	0.3392	0.4116	0.073*
C13	0.0772 (3)	0.2921 (7)	0.3739 (2)	0.0709 (10)
H13	0.0618	0.4222	0.3900	0.085*
C14	0.0026 (3)	0.1487 (8)	0.33776 (19)	0.0722 (10)
H14	−0.0631	0.1809	0.3298	0.087*
C15	0.0248 (3)	−0.0399 (8)	0.3137 (2)	0.0713 (10)
H15	−0.0259	−0.1368	0.2894	0.086*
C16	0.1217 (2)	−0.0899 (6)	0.32472 (17)	0.0577 (8)
H16	0.1362	−0.2181	0.3073	0.069*
O1	0.22999 (15)	0.3895 (3)	0.25913 (11)	0.0532 (5)
O2	0.45208 (18)	0.5313 (4)	0.31552 (12)	0.0643 (6)
O1W	0.4391 (2)	0.4022 (4)	0.18722 (14)	0.0729 (7)
H1W	0.4651	0.2794	0.1849	0.088*
H2W	0.4411	0.4158	0.2263	0.088*
S	0.42388 (5)	0.40496 (12)	0.36491 (4)	0.04610 (18)
Se	0.33094 (2)	−0.03515 (6)	0.380920 (17)	0.05674 (12)
Br	0.13073 (3)	−0.34569 (7)	0.001765 (19)	0.07905 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0385 (13)	0.0460 (15)	0.0428 (15)	−0.0001 (11)	0.0165 (11)	0.0043 (11)
C2	0.0366 (13)	0.0488 (15)	0.0393 (14)	0.0033 (11)	0.0143 (11)	−0.0005 (11)
C3	0.0458 (16)	0.077 (2)	0.0477 (17)	−0.0005 (15)	0.0116 (13)	−0.0088 (16)
C4	0.054 (2)	0.114 (3)	0.067 (2)	−0.015 (2)	0.0156 (18)	−0.030 (2)
C5	0.0351 (12)	0.0465 (14)	0.0402 (14)	−0.0005 (11)	0.0144 (11)	0.0018 (11)
C6	0.0438 (14)	0.0497 (16)	0.0474 (16)	0.0058 (12)	0.0127 (12)	0.0029 (12)
C7	0.0494 (16)	0.0604 (18)	0.0426 (16)	0.0017 (14)	0.0073 (13)	0.0028 (13)
C8	0.0491 (15)	0.0589 (18)	0.0440 (15)	−0.0071 (13)	0.0199 (13)	−0.0048 (13)
C9	0.0498 (15)	0.0490 (16)	0.0527 (17)	0.0008 (13)	0.0203 (13)	−0.0028 (13)
C10	0.0410 (14)	0.0505 (16)	0.0442 (15)	0.0017 (12)	0.0116 (12)	0.0036 (12)
C11	0.0484 (15)	0.0545 (16)	0.0403 (15)	−0.0053 (12)	0.0207 (12)	0.0044 (12)
C12	0.0638 (19)	0.062 (2)	0.0597 (19)	−0.0092 (16)	0.0271 (16)	−0.0088 (16)
C13	0.078 (2)	0.077 (2)	0.070 (2)	0.0102 (19)	0.043 (2)	−0.0010 (19)
C14	0.0531 (19)	0.109 (3)	0.061 (2)	0.003 (2)	0.0298 (17)	0.014 (2)
C15	0.0543 (19)	0.099 (3)	0.062 (2)	−0.0205 (19)	0.0248 (17)	−0.007 (2)
C16	0.0591 (18)	0.0643 (19)	0.0530 (18)	−0.0161 (15)	0.0260 (15)	−0.0090 (15)
O1	0.0507 (11)	0.0509 (11)	0.0526 (12)	0.0099 (9)	0.0149 (9)	−0.0012 (9)
O2	0.0661 (14)	0.0659 (14)	0.0611 (14)	−0.0174 (11)	0.0258 (12)	0.0026 (11)
O1W	0.0846 (17)	0.0675 (15)	0.0766 (17)	0.0192 (13)	0.0428 (14)	0.0114 (13)
S	0.0449 (4)	0.0504 (4)	0.0427 (4)	−0.0023 (3)	0.0172 (3)	−0.0049 (3)
Se	0.05056 (19)	0.0595 (2)	0.0579 (2)	0.00582 (13)	0.01947 (15)	0.01869 (14)
Br	0.0929 (3)	0.0816 (3)	0.0526 (2)	−0.0047 (2)	0.01875 (19)	−0.02037 (18)

Geometric parameters (Å, º) top

C1—O1	1.215 (3)	C8—Br	1.897 (3)
C1—C5	1.483 (4)	C9—C10	1.383 (4)
C1—C2	1.520 (4)	C9—H9	0.9300
C2—S	1.817 (3)	C10—H10	0.9300
C2—Se	1.969 (3)	C11—C12	1.375 (5)
C2—H2	0.9800	C11—C16	1.377 (4)
C3—C4	1.509 (5)	C11—Se	1.920 (3)
C3—S	1.809 (3)	C12—C13	1.388 (5)
C3—H3A	0.9700	C12—H12	0.9300
C3—H3B	0.9700	C13—C14	1.375 (6)
C4—H4A	0.9600	C13—H13	0.9300
C4—H4B	0.9600	C14—C15	1.357 (6)
C4—H4C	0.9600	C14—H14	0.9300
C5—C10	1.388 (4)	C15—C16	1.380 (5)
C5—C6	1.392 (4)	C15—H15	0.9300
C6—C7	1.378 (4)	C16—H16	0.9300
C6—H6	0.9300	O2—S	1.503 (2)
C7—C8	1.380 (4)	O1W—H1W	0.8525
C7—H7	0.9300	O1W—H2W	0.8362
C8—C9	1.374 (4)

O1—C1—C5	122.1 (2)	C9—C8—Br	119.1 (2)
O1—C1—C2	119.1 (3)	C7—C8—Br	119.1 (2)
C5—C1—C2	118.8 (2)	C8—C9—C10	118.8 (3)
C1—C2—S	108.62 (19)	C8—C9—H9	120.6
C1—C2—Se	111.50 (17)	C10—C9—H9	120.6
S—C2—Se	109.77 (14)	C9—C10—C5	120.8 (3)
C1—C2—H2	109.0	C9—C10—H10	119.6
S—C2—H2	109.0	C5—C10—H10	119.6
Se—C2—H2	109.0	C12—C11—C16	120.4 (3)
C4—C3—S	109.2 (3)	C12—C11—Se	121.9 (2)
C4—C3—H3A	109.8	C16—C11—Se	117.6 (2)
S—C3—H3A	109.8	C11—C12—C13	119.2 (3)
C4—C3—H3B	109.8	C11—C12—H12	120.4
S—C3—H3B	109.8	C13—C12—H12	120.4
H3A—C3—H3B	108.3	C14—C13—C12	120.2 (4)
C3—C4—H4A	109.5	C14—C13—H13	119.9
C3—C4—H4B	109.5	C12—C13—H13	119.9
H4A—C4—H4B	109.5	C15—C14—C13	119.9 (3)
C3—C4—H4C	109.5	C15—C14—H14	120.0
H4A—C4—H4C	109.5	C13—C14—H14	120.0
H4B—C4—H4C	109.5	C14—C15—C16	120.8 (3)
C10—C5—C6	118.9 (3)	C14—C15—H15	119.6
C10—C5—C1	123.3 (2)	C16—C15—H15	119.6
C6—C5—C1	117.7 (2)	C11—C16—C15	119.4 (3)
C7—C6—C5	120.8 (3)	C11—C16—H16	120.3
C7—C6—H6	119.6	C15—C16—H16	120.3
C5—C6—H6	119.6	H1W—O1W—H2W	108.1
C6—C7—C8	118.8 (3)	O2—S—C3	104.37 (15)
C6—C7—H7	120.6	O2—S—C2	105.07 (13)
C8—C7—H7	120.6	C3—S—C2	98.16 (14)
C9—C8—C7	121.8 (3)	C11—Se—C2	101.82 (11)

O1—C1—C2—S	−28.1 (3)	C16—C11—C12—C13	0.1 (5)
C5—C1—C2—S	151.4 (2)	Se—C11—C12—C13	−176.7 (3)
O1—C1—C2—Se	93.0 (3)	C11—C12—C13—C14	0.9 (5)
C5—C1—C2—Se	−87.5 (2)	C12—C13—C14—C15	−0.8 (6)
O1—C1—C5—C10	−171.6 (3)	C13—C14—C15—C16	−0.3 (6)
C2—C1—C5—C10	8.9 (4)	C12—C11—C16—C15	−1.1 (5)
O1—C1—C5—C6	10.6 (4)	Se—C11—C16—C15	175.8 (3)
C2—C1—C5—C6	−168.9 (2)	C14—C15—C16—C11	1.3 (6)
C10—C5—C6—C7	−0.2 (4)	C4—C3—S—O2	64.1 (3)
C1—C5—C6—C7	177.7 (3)	C4—C3—S—C2	172.0 (3)
C5—C6—C7—C8	0.7 (5)	C1—C2—S—O2	−61.3 (2)
C6—C7—C8—C9	−0.5 (5)	Se—C2—S—O2	176.53 (14)
C6—C7—C8—Br	179.2 (2)	C1—C2—S—C3	−168.7 (2)
C7—C8—C9—C10	−0.2 (5)	Se—C2—S—C3	69.18 (16)
Br—C8—C9—C10	−179.9 (2)	C12—C11—Se—C2	−76.2 (3)
C8—C9—C10—C5	0.7 (4)	C16—C11—Se—C2	106.9 (2)
C6—C5—C10—C9	−0.5 (4)	C1—C2—Se—C11	−27.7 (2)
C1—C5—C10—C9	−178.3 (3)	S—C2—Se—C11	92.67 (15)

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) −x, y+1/2, −z+1/2; (iv) x, −y−1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₅BrO₂SSe·H₂O
M_r	448.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	14.6942 (2), 6.1103 (1), 21.5717 (4)
β (°)	113.714 (1)
V (Å³)	1773.30 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.50
Crystal size (mm)	0.36 × 0.19 × 0.16

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.291, 0.734
No. of measured, independent and observed [I > 2σ(I)] reflections	32063, 3734, 3177
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.095, 1.03
No. of reflections	3734
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.55

Computer programs: COLLECT (Nonius, 1999), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), MarvinSketch (Chemaxon, 2010) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

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	1.897 (3)	3.4921 (16)	5.349 (3)	165.34 (10)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) −x, y+1/2, −z+1/2; (iv) x, −y−1/2, z−1/2.

Acknowledgements

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

References

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Volume 67| Part 5| May 2011| Pages o1099-o1100

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