1,2-Bis(3-thien­yloxy)ethane: a thio­phene-based precursor for thio­phene-based aza­cryptand Mannich bases

Labat, G.; Halfpenny, J.

doi:10.1107/S1600536805024529

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 61| Part 9| September 2005| Pages o2815-o2816

https://doi.org/10.1107/S1600536805024529

1,2-Bis(3-thienyloxy)ethane: a thiophene-based precursor for thiophene-based azacryptand Mannich bases

Gaël Labat ^a and Joan Halfpenny ^b ^*

^aInstitut de Chimie, Université de Neuchâtel, Avenue de Bellevaux 51, CH-2007 Neuchâtel, Switzerland, and ^bDepartment of Chemistry and Physics, Nottingham Trent University, Clifton Lane, Nottingham NG11 8NS, England
^*Correspondence e-mail: gael.labat@unine.ch

(Received 26 July 2005; accepted 1 August 2005; online 6 August 2005)

The title compound, C₁₀H₁₂O₂S₂, is composed of two thiophene rings bridged by an –O(CH₂)₂O– chain in a trans arrangement. The molecule possesses C₂ symmetry with the twofold axis bisecting the central C—C bond. In the crystal structure, molecules related by a centre of symmetry are bridged by C—H⋯O hydrogen bonds, forming a zigzag one-dimensional chain extending in the c-axis direction.

Comment

The preparation of a range of open-chain cryptand-like structures, incorporating thiophene rings, as precursors for azacryptand Mannich bases, has been described by Barker et al. (1993 ) and Chaffin et al. (2001 , 2002 ). The title compound, (I), was prepared by the reaction of methyl 3-hydroxythiophene-2-carboxylate with 1,2-dichloroethane and anhydrous potassium carbonate in anhydrous N,N-dimethylformamide, followed by saponification and decarboxylation.

The molecular structure of (I) is illustrated in Fig. 1, and selected bond distances and angles are given in Table 1. In compound (I), two thiophene rings are bridged by an –O(CH₂)₂O– chain in a trans arrangement. A twofold axis bisects the central ethane bond [C5—C5(1 − x, y, $[{1\over 2}]$ − z)] and each half of the molecule is almost planar, with C5—O1—C2—C1 and C5—O1—C2—C3 torsion angles of 0.00 (18) and −178.45 (11)°, respectively. The bond lengths and angles (Table 1) are similar to those in an unsubstituted thiophene described by Bonham & Momany (1963 ).

The crystal packing of compound (I) is illustrated in Fig. 2. The molecules related by centres of symmetry are linked by C—H⋯O hydrogen bonds; details are given in Table 2. It can be seen that the molecules are arranged in a such a way as to form a zigzag one-dimensional polymer extending in the crystallographic c-axis direction.

Figure 1
View of compound (I)

, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (a) 1 − x, y, $[{1\over 2}]$ − z.]

Figure 2
The crystal packing of compound (I)

, viewed down the b axis. C—H⋯O hydrogen bonds are shown as dashed lines (details are given in Table 2

Experimental

Compound (I) was synthesized according to the procedure described by Chaffin et al. (2001). Suitable crystals for X-ray crystallography analysis were obtained by slow evaporation of a 1:1 ethanol–dichloromethane solution.

Crystal data

C₁₀H₁₀O₂S₂
M_r = 226.30
Monoclinic, C 2/c
a = 22.175 (3) Å
b = 5.3918 (4) Å
c = 9.0831 (11) Å
β = 111.362 (9)°
V = 1011.39 (19) Å³
Z = 4
D_x = 1.486 Mg m⁻³
Mo Kα radiation
Cell parameters from 9090 reflections
θ = 1.9–29.6°
μ = 0.49 mm⁻¹
T = 153 (2) K
Plate, colourless
0.5 × 0.5 × 0.2 mm

Data collection

Stoe IPDS-II diffractometer
ω scans
Absorption correction: none
9441 measured reflections
1398 independent reflections
1302 reflections with I > 2σ(I)
R_int = 0.053
θ_max = 29.4°
h = −30 → 30
k = −7 → 7
l = −11 → 12

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.090
S = 1.03
1398 reflections
64 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0472P)² + 1.0038P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

S1—C4	1.7129 (14)
S1—C1	1.7178 (13)
O1—C2	1.3597 (15)
O1—C5	1.4288 (15)
C3—C4	1.3674 (19)
C3—C2	1.4227 (17)
C2—C1	1.3672 (17)
C5—C5ⁱ	1.500 (2)

C4—S1—C1	92.55 (6)
C2—O1—C5	115.12 (10)
C4—C3—C2	111.88 (11)
C1—C2—O1	127.57 (12)
C1—C2—C3	113.59 (12)
O1—C2—C3	118.83 (11)
C3—C4—S1	111.56 (10)
O1—C5—C5ⁱ	108.13 (9)
C2—C1—S1	110.43 (10)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱⁱ	1.00	2.41	3.3940 (16)	170
Symmetry code: (ii) -x+1, -y, -z.

H atoms were located in difference Fourier maps and held fixed with U_iso(H) = 0.05 Å² and C—H = 0.94–1.05 Å.

Data collection: X-AREA (Stoe & Cie, 2002 ); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805024529/is6112sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805024529/is6112Isup2.hkl

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

1,2-Bis(3-thienyloxy)ethane top

Crystal data top

C₁₀H₁₀O₂S₂	F(000) = 472
M_r = 226.30	D_x = 1.486 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 9090 reflections
a = 22.175 (3) Å	θ = 1.9–29.6°
b = 5.3918 (4) Å	µ = 0.49 mm⁻¹
c = 9.0831 (11) Å	T = 153 K
β = 111.362 (9)°	Plate, colourless
V = 1011.39 (19) Å³	0.5 × 0.5 × 0.2 mm
Z = 4

Data collection top

Stoe IPDS-II diffractometer	1302 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.053
Graphite monochromator	θ_max = 29.4°, θ_min = 2.0°
Detector resolution: 0.81Å pixels mm^-1	h = −30→30
ω scans	k = −7→7
9441 measured reflections	l = −11→12
1398 independent reflections

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) = 0.090	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0472P)² + 1.0038P] where P = (F_o² + 2F_c²)/3
1398 reflections	(Δ/σ)_max = 0.001
64 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

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
S1	0.705495 (15)	0.30108 (6)	0.11836 (4)	0.02820 (13)
O1	0.53539 (5)	0.28858 (18)	0.14777 (11)	0.0259 (2)
C3	0.59883 (6)	0.0614 (2)	0.02934 (16)	0.0261 (3)
H3	0.5630	−0.0585	−0.0223	0.050*
C2	0.59236 (6)	0.2606 (2)	0.12527 (14)	0.0216 (2)
C4	0.65818 (7)	0.0611 (2)	0.01542 (16)	0.0282 (3)
H4	0.6733	−0.0522	−0.0426	0.050*
C5	0.53252 (6)	0.4969 (2)	0.24223 (15)	0.0247 (3)
H5A	0.5691	0.4837	0.3545	0.050*
H5B	0.5403	0.6558	0.1910	0.050*
C1	0.64618 (6)	0.4075 (2)	0.18219 (14)	0.0236 (2)
H1	0.6573	0.5546	0.2544	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02423 (18)	0.0307 (2)	0.0318 (2)	−0.00172 (11)	0.01271 (14)	−0.00265 (12)
O1	0.0246 (4)	0.0290 (5)	0.0272 (5)	−0.0060 (3)	0.0133 (4)	−0.0087 (3)
C3	0.0301 (6)	0.0217 (5)	0.0275 (6)	−0.0026 (5)	0.0119 (5)	−0.0034 (5)
C2	0.0240 (5)	0.0222 (5)	0.0194 (5)	−0.0016 (4)	0.0091 (4)	0.0006 (4)
C4	0.0323 (6)	0.0231 (6)	0.0306 (6)	0.0008 (5)	0.0132 (5)	−0.0032 (5)
C5	0.0280 (6)	0.0258 (6)	0.0224 (5)	−0.0027 (5)	0.0118 (5)	−0.0040 (4)
C1	0.0245 (5)	0.0252 (6)	0.0222 (5)	−0.0031 (4)	0.0098 (4)	−0.0023 (4)

Geometric parameters (Å, º) top

S1—C4	1.7129 (14)	C2—C1	1.3672 (17)
S1—C1	1.7178 (13)	C4—H4	0.9445
O1—C2	1.3597 (15)	C5—C5ⁱ	1.500 (2)
O1—C5	1.4288 (15)	C5—H5A	1.0489
C3—C4	1.3674 (19)	C5—H5B	1.0193
C3—C2	1.4227 (17)	C1—H1	1.0012
C3—H3	0.9989

C4—S1—C1	92.55 (6)	S1—C4—H4	121.5
C2—O1—C5	115.12 (10)	O1—C5—C5ⁱ	108.13 (9)
C4—C3—C2	111.88 (11)	O1—C5—H5A	110.0
C4—C3—H3	125.7	C5ⁱ—C5—H5A	109.8
C2—C3—H3	122.4	O1—C5—H5B	109.6
C1—C2—O1	127.57 (12)	C5ⁱ—C5—H5B	111.8
C1—C2—C3	113.59 (12)	H5A—C5—H5B	107.5
O1—C2—C3	118.83 (11)	C2—C1—S1	110.43 (10)
C3—C4—S1	111.56 (10)	C2—C1—H1	132.8
C3—C4—H4	127.0	S1—C1—H1	116.7

C5—O1—C2—C1	0.00 (18)	C1—S1—C4—C3	−0.11 (11)
C5—O1—C2—C3	−178.45 (11)	C2—O1—C5—C5ⁱ	−178.84 (11)
C4—C3—C2—C1	0.06 (17)	O1—C2—C1—S1	−178.66 (10)
C4—C3—C2—O1	178.73 (12)	C3—C2—C1—S1	−0.14 (14)
C2—C3—C4—S1	0.05 (15)	C4—S1—C1—C2	0.14 (10)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱⁱ	1.00	2.41	3.3940 (16)	170

Symmetry code: (ii) −x+1, −y, −z.

Acknowledgements

The authors thank Professor Helen Stoeckli-Evans (Université de Neuchâtel) for making available the Stoe IPDS diffractometer for data collection.

References

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