Bis(2-iodo­thio­phen-3-yl)methanone

Abstract

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,

• a = 10.1908 (9) Å

• b = 11.4832 (10) Å

• c = 10.9083 (10) Å

• β = 107.600 (1)°

• V = 1216.77 (19) ų

• 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[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 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

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.

Supplementary Material

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

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

All hydrogen atoms were positioned geometrically (C—H = 0.93 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.2 U_eq(C).

Figures

Fig. 1.

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

Crystal data

C9H4I2OS2	F(000) = 816
Mr = 446.04	Dx = 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

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

Refinement

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(Fo2) + (0.0342P)2] where P = (Fo2 + 2Fc2)/3
3003 reflections	(Δ/σ)max = 0.001
127 parameters	Δρmax = 1.08 e Å−3
0 restraints	Δρmin = −0.67 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.