1-(2,5-Dichloro-3-thien­yl)ethanone: infinite sheets mediated by O⋯Cl halogen bonds

Harrison, W.T.A.; Chidan Kumar, C.S.; Yathirajan, H.S.; Mayekar, A.N.; Narayana, B.

doi:10.1107/S1600536810035154

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2480

doi:10.1107/S1600536810035154

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1-(2,5-Dichloro-3-thienyl)ethanone: infinite sheets mediated by O⋯Cl halogen bonds

William T. A. Harrison,^a ^* C. S. Chidan Kumar,^b H. S. Yathirajan,^b A. N. Mayekar ^b,^c and B. Narayana ^d

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^cSeQuent Scientific Limited, New Mangalore 575 011, India, and ^dDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, India
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 6 August 2010; accepted 31 August 2010; online 4 September 2010)

In the title compound, C₆H₄Cl₂OS, the acetyl group is almost coplanar with the thiophene ring [dihedral angle = 4.01 (2)°]. In the crystal, short intermolecular O⋯Cl contacts [2.9494 (14) and 3.1191 (14) Å] link the molecules into infinite (100) sheets and aromatic π–π stacking [centroid–centroid separation = 3.5422 (10) Å] consolidates the packing.

Related literature

For a related structure and background references, see: Jasinski et al. (2010 ). For a related structure, see: Wen & Rasmussen (2007 ). For reference structural data, see: Allen et al. (1987 ). For a discussion of halogen bonding, see: Metrangalo & Resnati (2001 ).

Experimental

Crystal data

C₆H₄Cl₂OS
M_r = 195.05
Orthorhombic, P b c a
a = 13.0980 (3) Å
b = 7.1790 (1) Å
c = 16.3290 (3) Å
V = 1535.42 (5) Å³
Z = 8
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 120 K
0.22 × 0.14 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.804, T_max = 0.922
12928 measured reflections
1758 independent reflections
1538 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.078
S = 1.07
1758 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor 1997), SCALEPACK and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810035154/jj2050sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810035154/jj2050Isup2.hkl

checkCIF report

Comment top

The structure of the title compound, (I), (Fig. 1), was determined as part of our ongoing studies (Jasinski et al., 2010) of thiophene derivatives as possible candidates for non-linear optical materials.

The five-membered ring in (I) is almost planar (r.m.s. deviation = 0.002 Å) and the pendant atoms deviate from the ring plane by 0.019 (1)Å (Cl1), 0.011 (1)Å (Cl2), 0.110 (1)Å (O1), 0.026 (2)Å (C5) and -0.045(20Å (C6). The dihedral angle between C1/C2/C3/C4/S1 and C5/C6/O1 is 4.01 (2)°. Otherwise, the bond lengths for (I) fall within their expected ranges (Allen et al., 1987) and are similar to those in related structures (Wen & Rasmussen, 2007).

In the crystal of (I), short O···Cl contacts of 2.9494 (14)Å and 3.1191 (14)Å are evident, compared to an expected van der Waals' separation of about 3.27Å for these atoms. If theses contacts are considered to be bonding interactions (Metrangalo & Resnati, 2001), then infinite (100) sheets result (Fig. 2). Seventeen-membered rings containining four O···Cl bonds are apparent within the sheet. The packing is consolidated by aromatic π-π stacking interactions, with a centroid–centroid separation of 3.5422 (10)Å between inversion-related thiophene rings.

Related literature top

For a related structure and background references, see: Jasinski et al. (2010). For a related structure, see: Wen & Rasmussen (2007). For reference structural data, see: Allen et al. (1987). For a discussion of halogen bonding, see: Metrangalo & Resnati (2001).

Experimental top

2,5-Dichloro-3-acetylthiophene was obtained as a gift sample from SeQuent Scientific Ltd., New Mangalore, India. Colourless blocks of (I) were grown by the slow evaporation of a methanol solution (M.P.: 314–316 K).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms).
	Fig. 2. Partial packing diagram for (I) showing part of a (100) sheet arising from short O···Cl contacts (H atoms omitted for clarity). Symmetry codes: (i) x, 3/2–y, 1/2 + z; (ii) x, 1 + y, z.

1-(2,5-Dichloro-3-thienyl)ethanone top

Crystal data top

C₆H₄Cl₂OS	F(000) = 784
M_r = 195.05	D_x = 1.688 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 12696 reflections
a = 13.0980 (3) Å	θ = 2.9–27.5°
b = 7.1790 (1) Å	µ = 1.04 mm⁻¹
c = 16.3290 (3) Å	T = 120 K
V = 1535.42 (5) Å³	Cut block, colourless
Z = 8	0.22 × 0.14 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	1758 independent reflections
Radiation source: fine-focus sealed tube	1538 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω and ϕ scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −17→17
T_min = 0.804, T_max = 0.922	k = −9→9
12928 measured reflections	l = −21→19

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.078	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0196P)² + 1.1699P] where P = (F_o² + 2F_c²)/3
1758 reflections	(Δ/σ)_max = 0.002
92 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₆H₄Cl₂OS	V = 1535.42 (5) Å³
M_r = 195.05	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 13.0980 (3) Å	µ = 1.04 mm⁻¹
b = 7.1790 (1) Å	T = 120 K
c = 16.3290 (3) Å	0.22 × 0.14 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	1758 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1538 reflections with I > 2σ(I)
T_min = 0.804, T_max = 0.922	R_int = 0.050
12928 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.078	H-atom parameters constrained
S = 1.07	Δρ_max = 0.34 e Å⁻³
1758 reflections	Δρ_min = −0.28 e Å⁻³
92 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.

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 > σ(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	0.36993 (13)	0.4974 (3)	0.44792 (10)	0.0181 (4)
C2	0.36763 (13)	0.5824 (2)	0.52170 (11)	0.0178 (4)
H2	0.3618	0.7134	0.5285	0.021*
C3	0.37494 (12)	0.4537 (2)	0.58881 (10)	0.0153 (4)
C4	0.38165 (13)	0.2736 (2)	0.56061 (11)	0.0172 (4)
C5	0.37563 (13)	0.5245 (3)	0.67461 (11)	0.0181 (4)
C6	0.37733 (14)	0.3927 (3)	0.74569 (11)	0.0227 (4)
H6A	0.3730	0.4634	0.7969	0.034*
H6B	0.4410	0.3210	0.7448	0.034*
H6C	0.3191	0.3074	0.7418	0.034*
O1	0.37515 (11)	0.69263 (19)	0.68546 (8)	0.0299 (3)
S1	0.38011 (3)	0.25777 (6)	0.45563 (3)	0.02062 (14)
Cl1	0.36483 (4)	0.60020 (7)	0.35316 (3)	0.02524 (14)
Cl2	0.39243 (4)	0.06821 (6)	0.61358 (3)	0.02400 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0175 (9)	0.0234 (10)	0.0134 (9)	−0.0004 (7)	−0.0011 (6)	0.0017 (7)
C2	0.0191 (9)	0.0176 (8)	0.0168 (9)	0.0001 (7)	0.0000 (7)	0.0017 (7)
C3	0.0154 (8)	0.0162 (8)	0.0144 (9)	0.0004 (6)	0.0010 (6)	0.0010 (7)
C4	0.0174 (9)	0.0179 (8)	0.0163 (8)	−0.0007 (7)	0.0008 (7)	0.0006 (7)
C5	0.0190 (9)	0.0198 (8)	0.0154 (9)	0.0003 (7)	0.0005 (6)	−0.0007 (7)
C6	0.0310 (11)	0.0227 (10)	0.0145 (10)	0.0001 (7)	0.0021 (7)	0.0022 (7)
O1	0.0548 (10)	0.0174 (7)	0.0175 (7)	0.0006 (6)	−0.0007 (6)	−0.0024 (6)
S1	0.0244 (3)	0.0215 (3)	0.0160 (3)	−0.00193 (17)	0.00004 (17)	−0.00486 (17)
Cl1	0.0251 (3)	0.0372 (3)	0.0134 (2)	0.00171 (19)	−0.00100 (16)	0.00583 (18)
Cl2	0.0332 (3)	0.0138 (2)	0.0250 (3)	0.00051 (17)	−0.00035 (19)	0.00208 (17)

Geometric parameters (Å, º) top

C1—C2	1.351 (2)	C4—Cl2	1.7151 (18)
C1—Cl1	1.7156 (18)	C4—S1	1.7181 (19)
C1—S1	1.7303 (19)	C5—O1	1.220 (2)
C2—C3	1.437 (2)	C5—C6	1.498 (2)
C2—H2	0.9500	C6—H6A	0.9800
C3—C4	1.376 (2)	C6—H6B	0.9800
C3—C5	1.490 (2)	C6—H6C	0.9800

C2—C1—Cl1	127.54 (15)	Cl2—C4—S1	116.58 (10)
C2—C1—S1	112.71 (13)	O1—C5—C3	118.28 (16)
Cl1—C1—S1	119.75 (10)	O1—C5—C6	120.83 (16)
C1—C2—C3	112.84 (16)	C3—C5—C6	120.88 (16)
C1—C2—H2	123.6	C5—C6—H6A	109.5
C3—C2—H2	123.6	C5—C6—H6B	109.5
C4—C3—C2	110.71 (15)	H6A—C6—H6B	109.5
C4—C3—C5	129.40 (16)	C5—C6—H6C	109.5
C2—C3—C5	119.88 (15)	H6A—C6—H6C	109.5
C3—C4—Cl2	130.13 (14)	H6B—C6—H6C	109.5
C3—C4—S1	113.28 (13)	C4—S1—C1	90.45 (8)

Cl1—C1—C2—C3	−179.10 (13)	C4—C3—C5—O1	175.49 (17)
S1—C1—C2—C3	0.4 (2)	C2—C3—C5—O1	−3.7 (3)
C1—C2—C3—C4	−0.5 (2)	C4—C3—C5—C6	−4.2 (3)
C1—C2—C3—C5	178.80 (15)	C2—C3—C5—C6	176.57 (15)
C2—C3—C4—Cl2	179.62 (14)	C3—C4—S1—C1	−0.14 (14)
C5—C3—C4—Cl2	0.4 (3)	Cl2—C4—S1—C1	−179.47 (11)
C2—C3—C4—S1	0.40 (19)	C2—C1—S1—C4	−0.18 (14)
C5—C3—C4—S1	−178.85 (14)	Cl1—C1—S1—C4	179.40 (11)

Experimental details

Crystal data
Chemical formula	C₆H₄Cl₂OS
M_r	195.05
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	120
a, b, c (Å)	13.0980 (3), 7.1790 (1), 16.3290 (3)
V (Å³)	1535.42 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.04
Crystal size (mm)	0.22 × 0.14 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.804, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	12928, 1758, 1538
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.078, 1.07
No. of reflections	1758
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.28

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor 1997), and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Acknowledgements

CSC thanks the University of Mysore for providing research facilities. HSY thanks the University of Mysore for sanctioning sabbatical leave.

References

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