4-(2,3-Di­hydro­thieno[3,4-b][1,4]dioxin-5-yl)aniline

Lauren A Mitchell; Bradley J Holliday

doi:10.1107/S1600536814014093

. 2014 Jun 21;70(Pt 7):o803. doi: 10.1107/S1600536814014093

4-(2,3-Dihydrothieno[3,4-b][1,4]dioxin-5-yl)aniline

Lauren A Mitchell ^a, Bradley J Holliday ^a,^*

PMCID: PMC4120538 PMID: 25161584

Abstract

In the title molecule, C₁₂H₁₁NO₂S, the dioxane-type ring adopts a half-chair conformation. The thiophene ring forms a dihedral angle of 12.53 (6)° with the benzene ring. In the crystal, N—H⋯O, hydrogen bonds link molecules, forming chains along the c-axis direction. A weak intramolecular C—H⋯O hydrogen bond is observed.

Keywords: crystal structure

Related literature

For related structures, see: Chen et al. (2011 ▶); Riehn et al. (2000 ▶); Sotzing & Reynolds (1996 ▶). For the properties of 4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)aniline see: Trippé-Allard & Lacroix (2013 ▶). graphic file with name e-70-0o803-scheme1.jpg

Experimental

Crystal data

C₁₂H₁₁NO₂S
M _r = 233.28
Orthorhombic,
a = 6.9117 (6) Å
b = 7.0898 (6) Å
c = 21.4784 (16) Å
V = 1052.50 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 100 K
0.29 × 0.27 × 0.08 mm

Data collection

Rigaku Saturn724+ diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 2001 ▶) T _min = 0.858, T _max = 1.000
11854 measured reflections
1853 independent reflections
1812 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.075
S = 0.86
1853 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.21 e Å⁻³
Absolute structure: Flack (1983 ▶), 743 Friedel pairs
Absolute structure parameter: 0.03 (8)

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 2012 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶), POV-RAY (Cason, 2004 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814014093/lh5708sup1.cif

e-70-0o803-sup1.cif^{(21.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814014093/lh5708Isup2.hkl

e-70-0o803-Isup2.hkl^{(89.4KB, hkl)}

Click here for additional data file.^{(4.5KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814014093/lh5708Isup3.cml

CCDC reference: 1008614

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H10A⋯O1ⁱ	0.88 (3)	2.52 (3)	3.352 (2)	160 (2)
C8—H8⋯O2	0.93	2.36	2.998 (2)	126

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Symmetry code: (i) Inline graphic .

Acknowledgments

The data were collected using instrumentation purchased with funds provided by the National Science Foundation (grant No. CHE-0741973). The Welch Foundation (grant No. F-1631) and the National Science Foundation (grant No. CHE-0847763) are acknowledged for financial support of this research.

supplementary crystallographic information

S1. Comment

The title compound is composed of an aniline moiety with a 3,4-ethylenedioxythiophene group appended at the 4-position, see Fig. 1. It has been used in the development of π-conjugated oligomers, which have low HOMO-LUMO gaps and are easily oxidized at low potentials, making them potential materials for photovoltaics and other optoelectronic applications (Trippé-Allard & Lacroix, 2013). The geometry of the ethylenedioxythiophene moiety is similar to other ethylenedioxythiophene containing compounds reported in the literature, which includes the six-membered dioxane-type ring in the half-chair conformation (Chen et al., 2011; Sotzing & Reynolds, 1996; Riehn et al., 2000). The dihedral angle between the thiophene and benzene rings is 12.53 (6)°. In the crystal, N1—H10A···O1ⁱ hydrogen bonds link molecules into chains along the c axis (Fig. 2). A weak intramolecular C—H···O hydrogen bond is also observed.

S2. Experimental

To a solution of dry toluene under N₂ was added tributyl(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)stannane (21.4 g, 49.5 mmol), 4-iodonitrobenzene (7.7 g, 30.9 mmol), trans-dichlorobis(triphenylphosphine) palladium (II) (0.3 g, 0.5 mmol), and copper (I) chloride (0.2 g, 1.1 mmol). The solution was refluxed at 383 K overnight. The black solution was exposed to atmosphere and conc. under reduced pressure. The solid was dissolved in dichloromethane and filtered over a bed of silica. The filtrate was conc. and recycrystallized in a dichloromethane/hexanes mixture to yield a bright yellow solid. The isolated yellow solid was added to a round bottom and dissolved in tetrahydrofuran (THF). Charcoal (8.39 g) and 5 ml of H₂O was added and the mixture was heated to 323 K. Sodium borohydride (2.66 g, 70.5 mmol) was added in four portions over 1 hr. The reaction was heated for an additional 30 min after the last addition. The mixture was cooled to room temp. and filtered, washing with THF. The solution was concentrated then re-dissolved in CH₂Cl₂ and washed with H₂O. The organic layer was concentrated to a third the original volume and mixed with an equal volume of hexanes. The solution was left standing overnight at 273 K and the orange crystals that precipitated were collected by vacuum filtration (4.63 g, 64% yield). These crystals were found suitable for X-ray diffraction. m.p. 376 K. ¹H NMR (300 MHz, CDCl₃): δ 7.51 (dt, J = 8.7, J = 2.1, 2H), 6.66 (dt, J = 8.7, J = 2.4, 2H), 6.19 (s, 1H), 4.25 – 4.18 (m, 4H), 3.64 (b, 2H); ¹³C{¹H} NMR (75 MHz, CDCl₃): δ 145.2, 142.1, 136.6, 127.2, 123.5, 117.9, 115.0, 95.5, 64.5, 64.4; Anal Calcd for C₁₂H₁₁NO₂S: C, 61.78; H, 4.75; N, 6.00. Found: C, 61.67; H, 4.07; N, 5.90.