Crystal structure of 2-(3-bromo­phen­yl)-1,3-di­thiane

Zukerman-Schpector, J.; Caracelli, I.; Stefani, H.A.; Gozhina, O.; Tiekink, E.R.T.

doi:10.1107/S2056989015002832

organic compounds

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Volume 71| Part 3| March 2015| Pages o179-o180

doi:10.1107/S2056989015002832

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Crystal structure of 2-(3-bromophenyl)-1,3-dithiane

Julio Zukerman-Schpector,^a ^* Ignez Caracelli,^b Hélio A. Stefani,^c Olga Gozhina ^c and Edward R. T. Tiekink ^d

^aDepartmento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, ^bDepartmento de Física, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, ^cDepartamento de Farmácia, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, 05508-900 São Paulo-SP, Brazil, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: julio@power.ufscar.br

Edited by P. C. Healy, Griffith University, Australia (Received 4 February 2015; accepted 10 February 2015; online 13 February 2015)

In the title compound, C₁₀H₁₁BrS₂, the 1,3-dithiane ring has a chair conformation with the 1,4-disposed C atoms being above and below the remaining four atoms. The bromobenzene ring occupies an equatorial position and forms a dihedral angle of 86.38 (12)° with the least-squares plane through the 1,3-dithiane ring. Thus, to a first approximation the molecule has mirror symmetry with the mirror containing the bromobenzene ring and the 1,4-disposed C atoms of the 1,3-dithiane ring. In the crystal, molecules associate via weak methylene–bromobenzene C—H⋯π and π–π [Cg⋯Cg = 3.7770 (14) Å for centrosymmetrically related bromobenzene rings] interactions, forming supramolecular layers parallel to [10-1]; these stack with no specific intermolecular interactions between them.

Keywords: crystal structure; 1,3-dithiane; conformation; C—H⋯π interactions; π–π interactions.

CCDC reference: 1048592

1. Related literature

For the original synthesis and characterization of the title compound, see: Ballesteros et al. (2005 ). For the structure of the unsubstituted parent compound which is virtually superimposable on the title compound, see: Kalff & Romers (1966 ).

2. Experimental

2.1. Crystal data

C₁₀H₁₁BrS₂
M_r = 275.22
Monoclinic, P 2₁ /c
a = 8.9821 (4) Å
b = 11.3871 (5) Å
c = 11.0550 (5) Å
β = 99.604 (3)°
V = 1114.86 (9) Å³
Z = 4
Mo Kα radiation
μ = 4.01 mm⁻¹
T = 296 K
0.33 × 0.28 × 0.16 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.374, T_max = 0.745
7307 measured reflections
2060 independent reflections
1820 reflections with I > 2σ(I)
R_int = 0.029

2.3. Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.082
S = 1.06
2060 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2b⋯Cg1ⁱ	0.97	2.83	3.668 (4)	146
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1048592

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015002832/hg5429sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015002832/hg5429Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015002832/hg5429Isup3.cml

checkCIF report

Related literature top

For the original synthesis and characterization of the title compound, see: Ballesteros et al. (2005). For the structure of the unsubstituted parent compound which is virtually superimposable on the title compound, see: Kalff & Romers (1966).

Experimental top

A solution of 3-bromobenzaldehyde (0.037 mol, 1 equiv.) in chloroform (20 ml) was combined with an equimolar amount of propane-1,3-dithiol (3.7 ml, 0.037 mol) at room temperature. The solution was stirred for 1 h at this temperature, then cooled to -20 °C after which BF₃ etherate (0.46 ml, 0.0037 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 MgSO₄. Evaporation of the solvent furnishes a pure product as colourless crystals in 90% yield. To obtain crystals suitable for X-ray analysis, the product was crystallized from CH₃OH. The spectroscopic data matched those reported in the literature (Ballesteros et al., 2005).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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) 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 the title compound showing the atom-labelling scheme and displacement ellipsoids at the 35% probability level.
	Fig. 2. A view of the supramolecular layer parallel to [101] mediated by C—H···π and π—π interactions shown as orange and purple dashed lines, respectively.
	Fig. 3. A view in projection down the b axis of the unit-cell contents. The C—H···π and π—π interactions shown as orange and purple dashed lines, respectively.

2-(3-Bromophenyl)-1,3-dithiane top

Crystal data top

C₁₀H₁₁BrS₂	F(000) = 552
M_r = 275.22	D_x = 1.640 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.9821 (4) Å	Cell parameters from 4286 reflections
b = 11.3871 (5) Å	θ = 2.6–25.4°
c = 11.0550 (5) Å	µ = 4.01 mm⁻¹
β = 99.604 (3)°	T = 296 K
V = 1114.86 (9) Å³	Prism, colourless
Z = 4	0.33 × 0.28 × 0.16 mm

Data collection top

Bruker APEXII CCD diffractometer	1820 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.029
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θ_max = 25.4°, θ_min = 2.3°
T_min = 0.374, T_max = 0.745	h = −9→10
7307 measured reflections	k = −13→12
2060 independent reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0384P)² + 0.6522P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.002
2060 reflections	Δρ_max = 0.54 e Å⁻³
118 parameters	Δρ_min = −0.65 e Å⁻³

Crystal data top

C₁₀H₁₁BrS₂	V = 1114.86 (9) Å³
M_r = 275.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.9821 (4) Å	µ = 4.01 mm⁻¹
b = 11.3871 (5) Å	T = 296 K
c = 11.0550 (5) Å	0.33 × 0.28 × 0.16 mm
β = 99.604 (3)°

Data collection top

Bruker APEXII CCD diffractometer	2060 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1820 reflections with I > 2σ(I)
T_min = 0.374, T_max = 0.745	R_int = 0.029
7307 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.06	Δρ_max = 0.54 e Å⁻³
2060 reflections	Δρ_min = −0.65 e Å⁻³
118 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.71577 (4)	1.19362 (3)	1.06788 (3)	0.06773 (15)
S1	0.60308 (9)	0.70880 (7)	0.76097 (6)	0.0565 (2)
S2	0.86833 (7)	0.65738 (6)	0.96061 (6)	0.04880 (19)
C1	0.7115 (3)	0.7543 (2)	0.9063 (2)	0.0373 (5)
H1	0.6439	0.7542	0.9674	0.045*
C2	0.5426 (4)	0.5670 (3)	0.8068 (3)	0.0657 (8)
H2A	0.4799	0.5784	0.8692	0.079*
H2B	0.4805	0.5306	0.7366	0.079*
C3	0.6689 (4)	0.4839 (3)	0.8560 (3)	0.0649 (8)
H3A	0.6262	0.4076	0.8690	0.078*
H3B	0.7342	0.4746	0.7950	0.078*
C4	0.7631 (3)	0.5247 (3)	0.9752 (3)	0.0587 (7)
H4A	0.8331	0.4628	1.0065	0.070*
H4B	0.6969	0.5378	1.0349	0.070*
C5	0.7677 (2)	0.8778 (2)	0.8960 (2)	0.0377 (5)
C6	0.7265 (3)	0.9638 (2)	0.9723 (2)	0.0382 (5)
H6	0.6661	0.9450	1.0301	0.046*
C7	0.7754 (3)	1.0778 (2)	0.9623 (2)	0.0432 (6)
C8	0.8665 (3)	1.1081 (3)	0.8788 (2)	0.0526 (7)
H8	0.8994	1.1851	0.8733	0.063*
C9	0.9078 (3)	1.0224 (3)	0.8039 (2)	0.0575 (7)
H9	0.9692	1.0417	0.7469	0.069*
C10	0.8598 (3)	0.9074 (3)	0.8115 (2)	0.0496 (6)
H10	0.8892	0.8503	0.7602	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0883 (3)	0.0415 (2)	0.0730 (2)	0.00622 (14)	0.01259 (18)	−0.00728 (13)
S1	0.0631 (5)	0.0554 (4)	0.0434 (4)	−0.0065 (3)	−0.0132 (3)	0.0005 (3)
S2	0.0406 (3)	0.0434 (4)	0.0579 (4)	0.0002 (3)	−0.0047 (3)	0.0017 (3)
C1	0.0393 (12)	0.0381 (13)	0.0343 (12)	0.0000 (10)	0.0053 (9)	−0.0026 (10)
C2	0.0624 (18)	0.0590 (19)	0.0669 (18)	−0.0188 (15)	−0.0145 (15)	−0.0067 (15)
C3	0.075 (2)	0.0415 (16)	0.073 (2)	−0.0107 (14)	−0.0016 (16)	−0.0100 (14)
C4	0.0611 (18)	0.0409 (15)	0.0682 (18)	−0.0039 (13)	−0.0062 (14)	0.0077 (13)
C5	0.0353 (12)	0.0419 (13)	0.0339 (11)	−0.0019 (10)	−0.0002 (9)	0.0037 (10)
C6	0.0390 (12)	0.0402 (13)	0.0348 (11)	−0.0006 (10)	0.0043 (9)	0.0028 (10)
C7	0.0449 (14)	0.0395 (13)	0.0412 (13)	−0.0015 (10)	−0.0041 (10)	0.0014 (10)
C8	0.0559 (16)	0.0479 (16)	0.0507 (15)	−0.0157 (13)	−0.0007 (12)	0.0100 (12)
C9	0.0554 (17)	0.072 (2)	0.0476 (15)	−0.0166 (14)	0.0153 (13)	0.0098 (14)
C10	0.0502 (15)	0.0592 (17)	0.0414 (13)	−0.0046 (13)	0.0130 (11)	−0.0015 (12)

Geometric parameters (Å, º) top

Br1—C7	1.897 (3)	C4—H4A	0.9700
S1—C2	1.803 (3)	C4—H4B	0.9700
S1—C1	1.810 (2)	C5—C6	1.383 (3)
S2—C4	1.803 (3)	C5—C10	1.389 (4)
S2—C1	1.811 (2)	C6—C7	1.381 (3)
C1—C5	1.505 (3)	C6—H6	0.9300
C1—H1	0.9800	C7—C8	1.375 (4)
C2—C3	1.507 (4)	C8—C9	1.371 (4)
C2—H2A	0.9700	C8—H8	0.9300
C2—H2B	0.9700	C9—C10	1.385 (4)
C3—C4	1.515 (4)	C9—H9	0.9300
C3—H3A	0.9700	C10—H10	0.9300
C3—H3B	0.9700

C2—S1—C1	98.61 (12)	S2—C4—H4A	108.8
C4—S2—C1	98.59 (13)	C3—C4—H4B	108.8
C5—C1—S1	109.74 (15)	S2—C4—H4B	108.8
C5—C1—S2	110.01 (16)	H4A—C4—H4B	107.7
S1—C1—S2	113.16 (13)	C6—C5—C10	119.2 (2)
C5—C1—H1	107.9	C6—C5—C1	119.3 (2)
S1—C1—H1	107.9	C10—C5—C1	121.5 (2)
S2—C1—H1	107.9	C7—C6—C5	119.7 (2)
C3—C2—S1	114.8 (2)	C7—C6—H6	120.1
C3—C2—H2A	108.6	C5—C6—H6	120.1
S1—C2—H2A	108.6	C8—C7—C6	121.5 (3)
C3—C2—H2B	108.6	C8—C7—Br1	120.0 (2)
S1—C2—H2B	108.6	C6—C7—Br1	118.53 (19)
H2A—C2—H2B	107.5	C9—C8—C7	118.6 (3)
C4—C3—C2	113.5 (3)	C9—C8—H8	120.7
C4—C3—H3A	108.9	C7—C8—H8	120.7
C2—C3—H3A	108.9	C8—C9—C10	121.2 (3)
C4—C3—H3B	108.9	C8—C9—H9	119.4
C2—C3—H3B	108.9	C10—C9—H9	119.4
H3A—C3—H3B	107.7	C9—C10—C5	119.8 (3)
C3—C4—S2	113.8 (2)	C9—C10—H10	120.1
C3—C4—H4A	108.8	C5—C10—H10	120.1

C2—S1—C1—C5	−175.91 (19)	S2—C1—C5—C10	66.0 (3)
C2—S1—C1—S2	60.79 (17)	C10—C5—C6—C7	0.9 (3)
C4—S2—C1—C5	175.20 (17)	C1—C5—C6—C7	−179.0 (2)
C4—S2—C1—S1	−61.65 (17)	C5—C6—C7—C8	−0.9 (4)
C1—S1—C2—C3	−58.8 (3)	C5—C6—C7—Br1	179.66 (17)
S1—C2—C3—C4	65.2 (4)	C6—C7—C8—C9	0.5 (4)
C2—C3—C4—S2	−65.7 (4)	Br1—C7—C8—C9	179.9 (2)
C1—S2—C4—C3	60.0 (3)	C7—C8—C9—C10	−0.2 (4)
S1—C1—C5—C6	120.8 (2)	C8—C9—C10—C5	0.3 (4)
S2—C1—C5—C6	−114.1 (2)	C6—C5—C10—C9	−0.7 (4)
S1—C1—C5—C10	−59.1 (3)	C1—C5—C10—C9	179.3 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2b···Cg1ⁱ	0.97	2.83	3.668 (4)	146

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2b···Cg1ⁱ	0.97	2.83	3.668 (4)	146

Symmetry code: (i) −x+1, y−1/2, −z+3/2.

Acknowledgements

We thank Professor Regina H. A. Santos from IQSC–USP for the X-ray data collection. The Brazilian agencies CNPq (305626/2013-2 to JZS, 306121/2013-2 to IC and 308320/2010-7 to HAS), FAPESP (2012/00424-2 and 2013/21925-2) and CAPES are acknowledged for financial support.

References

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 3| March 2015| Pages o179-o180

doi:10.1107/S2056989015002832

Open

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