Bis(2-iodo­thio­phen-3-yl)methanone

Cheng, H.

doi:10.1107/S1600536811005472

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o691

doi:10.1107/S1600536811005472

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Bis(2-iodothiophen-3-yl)methanone

Hua Cheng ^a ^*

^aDepartment of Chemistry and Biology, Xiangfan University, Xiangfan 441053, People's Republic of China
^*Correspondence e-mail: hchengxf@126.com

(Received 10 February 2011; accepted 14 February 2011; online 23 February 2011)

In the title molecule, C₉H₄I₂OS₂, the two five-membered rings form a dihedral angle of 64.2 (2)°. In the crystal, weak intermolecular C—H⋯O hydrogen bonds link the molecules into layers parallel to the ab plane. The crystal packing exhibits short C⋯I contacts of 3.442 (5) Å between the molecules of adjacent layers.

Related literature

For general background to the synthesis of thiophene-based conjugated polymers, see: Cheng et al. (2009 ). For the synthesis of the title compound, see: Brzezinski & Reynolds (2002 ).

Experimental

Crystal data

C₉H₄I₂OS₂
M_r = 446.04
Monoclinic, P 2₁ /n
a = 10.1908 (9) Å
b = 11.4832 (10) Å
c = 10.9083 (10) Å
β = 107.600 (1)°
V = 1216.77 (19) Å³
Z = 4
Mo Kα radiation
μ = 5.48 mm⁻¹
T = 298 K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.474, T_max = 0.610
8022 measured reflections
3003 independent reflections
2541 reflections with I > 2σ(I)
R_int = 0.084

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.103
S = 1.11
3003 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 1.08 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1ⁱ	0.93	2.51	3.233 (7)	135
C8—H8⋯O1ⁱⁱ	0.93	2.40	3.324 (6)	172
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005472/cv5050sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005472/cv5050Isup2.hkl

checkCIF report

Comment top

The title compound, (I), is an important organic intermediate for the synthesis of conjugated polymers for organic solar cell applications (Brzezinski & Reynolds, 2002; Cheng et al., 2009). In (I) (Fig. 1), two five-membered rings form a dihedral angle of 64.2 (2)°. Weak intermolecular C—H···O hydrogen bonds link the molecules into layers parallel to ab plane. The crystal packing exhibits short C···I contacts of 3.442 (5) Å between the molecules from the neighbouring layers.

Related literature top

For general background to the synthesis of thiophene-based conjugated polymers, see: Cheng et al. (2009). For the synthesis of the title compound, see: Brzezinski & Reynolds (2002).

Experimental top

The title compound was synthesized according to the reported method by Brzezinski & Reynolds (2002). After being dissolved in the mixture of MeOH-Hexane (1:3) for seversal days, colourless crystals suitable for single-crystal X-ray diffraction were obtained.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The title molecule with the atom-numbering scheme. The displacement ellipsoids are drawn at the 50% probability level.

Bis(2-iodothiophen-3-yl)methanone top

Crystal data top

C₉H₄I₂OS₂	F(000) = 816
M_r = 446.04	D_x = 2.435 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2906 reflections
a = 10.1908 (9) Å	θ = 2.4–26.9°
b = 11.4832 (10) Å	µ = 5.48 mm⁻¹
c = 10.9083 (10) Å	T = 298 K
β = 107.600 (1)°	Block, colourless
V = 1216.77 (19) Å³	0.16 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3003 independent reflections
Radiation source: fine-focus sealed tube	2541 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.084
ϕ and ω scans	θ_max = 28.2°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→7
T_min = 0.474, T_max = 0.610	k = −15→12
8022 measured reflections	l = −14→14

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0342P)²] where P = (F_o² + 2F_c²)/3
3003 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 1.08 e Å⁻³
0 restraints	Δρ_min = −0.67 e Å⁻³

Crystal data top

C₉H₄I₂OS₂	V = 1216.77 (19) Å³
M_r = 446.04	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.1908 (9) Å	µ = 5.48 mm⁻¹
b = 11.4832 (10) Å	T = 298 K
c = 10.9083 (10) Å	0.16 × 0.12 × 0.10 mm
β = 107.600 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3003 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2541 reflections with I > 2σ(I)
T_min = 0.474, T_max = 0.610	R_int = 0.084
8022 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.11	Δρ_max = 1.08 e Å⁻³
3003 reflections	Δρ_min = −0.67 e Å⁻³
127 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	0.7428 (5)	0.3871 (4)	0.9017 (5)	0.0377 (10)
C2	0.6198 (5)	0.3657 (4)	0.8086 (4)	0.0328 (9)
C3	0.6258 (5)	0.2588 (4)	0.7431 (5)	0.0392 (11)
H3	0.5515	0.2291	0.6783	0.047*
C4	0.7482 (6)	0.2053 (5)	0.7835 (5)	0.0486 (13)
H4	0.7688	0.1359	0.7495	0.058*
C5	0.5029 (5)	0.4469 (4)	0.7705 (5)	0.0349 (10)
C6	0.3643 (5)	0.3977 (4)	0.7066 (5)	0.0350 (10)
C7	0.3112 (6)	0.2950 (4)	0.7492 (5)	0.0438 (12)
H7	0.3628	0.2488	0.8166	0.053*
C8	0.1801 (6)	0.2717 (5)	0.6827 (6)	0.0499 (13)
H8	0.1300	0.2093	0.6996	0.060*
C9	0.2680 (5)	0.4481 (4)	0.6055 (5)	0.0372 (10)
I1	0.79608 (5)	0.51950 (4)	1.03536 (4)	0.05838 (16)
I2	0.28839 (4)	0.58784 (3)	0.49276 (4)	0.05046 (14)
O1	0.5191 (4)	0.5512 (3)	0.7870 (5)	0.0569 (10)
S1	0.86152 (15)	0.28059 (13)	0.90534 (14)	0.0517 (4)
S2	0.11662 (14)	0.37150 (14)	0.56270 (15)	0.0512 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.043 (3)	0.035 (3)	0.034 (2)	0.002 (2)	0.012 (2)	0.0020 (19)
C2	0.036 (3)	0.033 (2)	0.030 (2)	0.0025 (19)	0.011 (2)	0.0009 (18)
C3	0.043 (3)	0.037 (3)	0.034 (2)	0.004 (2)	0.006 (2)	−0.003 (2)
C4	0.059 (4)	0.044 (3)	0.042 (3)	0.010 (2)	0.012 (3)	−0.006 (2)
C5	0.034 (2)	0.030 (2)	0.043 (3)	0.0002 (18)	0.014 (2)	0.000 (2)
C6	0.039 (3)	0.028 (2)	0.042 (2)	0.0007 (18)	0.018 (2)	−0.0017 (19)
C7	0.049 (3)	0.036 (3)	0.047 (3)	−0.002 (2)	0.014 (2)	0.006 (2)
C8	0.048 (3)	0.040 (3)	0.066 (4)	−0.011 (2)	0.023 (3)	0.003 (3)
C9	0.035 (3)	0.035 (2)	0.043 (3)	−0.0045 (19)	0.014 (2)	−0.002 (2)
I1	0.0753 (3)	0.0496 (2)	0.0436 (2)	−0.01260 (18)	0.0080 (2)	−0.01168 (16)
I2	0.0553 (3)	0.0435 (2)	0.0549 (2)	0.00141 (15)	0.02021 (19)	0.01160 (16)
O1	0.041 (2)	0.0288 (18)	0.094 (3)	0.0001 (15)	0.011 (2)	−0.005 (2)
S1	0.0430 (8)	0.0537 (9)	0.0501 (8)	0.0140 (6)	0.0018 (6)	0.0014 (6)
S2	0.0357 (7)	0.0542 (8)	0.0600 (8)	−0.0072 (6)	0.0092 (6)	0.0008 (7)

Geometric parameters (Å, º) top

C1—C2	1.376 (7)	C5—C6	1.485 (7)
C1—S1	1.712 (5)	C6—C9	1.364 (7)
C1—I1	2.063 (5)	C6—C7	1.433 (6)
C2—C3	1.431 (7)	C7—C8	1.339 (8)
C2—C5	1.471 (7)	C7—H7	0.9300
C3—C4	1.339 (8)	C8—S2	1.713 (6)
C3—H3	0.9300	C8—H8	0.9300
C4—S1	1.709 (6)	C9—S2	1.714 (5)
C4—H4	0.9300	C9—I2	2.070 (5)
C5—O1	1.215 (6)

C2—C1—S1	111.7 (4)	C9—C6—C7	111.2 (4)
C2—C1—I1	129.8 (4)	C9—C6—C5	124.6 (4)
S1—C1—I1	118.5 (3)	C7—C6—C5	124.1 (4)
C1—C2—C3	110.8 (4)	C8—C7—C6	113.7 (5)
C1—C2—C5	125.1 (4)	C8—C7—H7	123.2
C3—C2—C5	123.8 (4)	C6—C7—H7	123.2
C4—C3—C2	113.9 (5)	C7—C8—S2	111.4 (4)
C4—C3—H3	123.1	C7—C8—H8	124.3
C2—C3—H3	123.1	S2—C8—H8	124.3
C3—C4—S1	111.6 (4)	C6—C9—S2	111.8 (4)
C3—C4—H4	124.2	C6—C9—I2	129.3 (4)
S1—C4—H4	124.2	S2—C9—I2	118.7 (3)
O1—C5—C2	121.4 (4)	C4—S1—C1	92.1 (3)
O1—C5—C6	120.8 (4)	C8—S2—C9	92.0 (3)
C2—C5—C6	117.8 (4)

S1—C1—C2—C3	1.2 (5)	C2—C5—C6—C7	44.7 (7)
I1—C1—C2—C3	−175.7 (4)	C9—C6—C7—C8	−0.8 (6)
S1—C1—C2—C5	−172.4 (4)	C5—C6—C7—C8	175.3 (5)
I1—C1—C2—C5	10.6 (7)	C6—C7—C8—S2	1.6 (6)
C1—C2—C3—C4	−1.6 (6)	C7—C6—C9—S2	−0.3 (5)
C5—C2—C3—C4	172.2 (5)	C5—C6—C9—S2	−176.4 (4)
C2—C3—C4—S1	1.2 (6)	C7—C6—C9—I2	−173.7 (4)
C1—C2—C5—O1	24.2 (7)	C5—C6—C9—I2	10.1 (7)
C3—C2—C5—O1	−148.6 (5)	C3—C4—S1—C1	−0.4 (5)
C1—C2—C5—C6	−158.0 (5)	C2—C1—S1—C4	−0.5 (4)
C3—C2—C5—C6	29.2 (7)	I1—C1—S1—C4	176.8 (3)
O1—C5—C6—C9	38.0 (7)	C7—C8—S2—C9	−1.5 (5)
C2—C5—C6—C9	−139.7 (5)	C6—C9—S2—C8	1.0 (4)
O1—C5—C6—C7	−137.6 (5)	I2—C9—S2—C8	175.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.93	2.51	3.233 (7)	135
C8—H8···O1ⁱⁱ	0.93	2.40	3.324 (6)	172

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

Experimental details

Crystal data
Chemical formula	C₉H₄I₂OS₂
M_r	446.04
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	10.1908 (9), 11.4832 (10), 10.9083 (10)
β (°)	107.600 (1)
V (Å³)	1216.77 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.48
Crystal size (mm)	0.16 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.474, 0.610
No. of measured, independent and observed [I > 2σ(I)] reflections	8022, 3003, 2541
R_int	0.084
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.103, 1.11
No. of reflections	3003
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.08, −0.67

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1ⁱ	0.93	2.51	3.233 (7)	135
C8—H8···O1ⁱⁱ	0.93	2.40	3.324 (6)	172

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

Acknowledgements

The author acknowledges financial support from Xiangfan University.

References

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