4,4′-Oxybis(2,6-di­methyl­pyridinium) bis­(tri­fluoro­methane­sulfonate)

Amanda W Stubbs; James A Golen; Arnold L Rheingold; David R Manke

doi:10.1107/S1600536813027505

. 2013 Oct 12;69(Pt 11):o1633–o1634. doi: 10.1107/S1600536813027505

4,4′-Oxybis(2,6-dimethylpyridinium) bis(trifluoromethanesulfonate)

Amanda W Stubbs ^a, James A Golen ^b, Arnold L Rheingold ^b, David R Manke ^a,^*

PMCID: PMC3884303 PMID: 24454079

Abstract

In the asymmetric unit of the title salt, C₁₄H₁₈N₂O²⁺·2CF₃O₃S⁻, the components are linked by two N—H⋯O and one C—H⋯O hydrogen bonds. The dipyridinium salt demonstrates a skew conformation based upon C—O—C—C torsion angles of 61.5 (3) and 15.1 (4)°. A C—O—C angle of 119.3 (2)° and C—O bond distances of 1.364 (3) and 1.389 (3) Å are consistent with other dipyridyl ethers. The planes of the pyridyl rings exhibit a twist angle of 67.89 (8)°. One of the trifluoromethanesulfonate ions shows disorder of the F atoms [in a 0.52 (7):0.48 (7) occupancy ratio] and an O atom [0.64 (8):0.36 (8) occupancy ratio]. In the crystal, the components are linked by C—H⋯O interactions, which form chains along [101].

Related literature

For the structure of the unsubstituted 4,4′-oxybisdipyridine, see: Dunne et al. (1996 ▶). For the structure of bis[4′-(2,2′:6′,2′′-terpyridinyl)]ether, see: Constable et al. (1995 ▶). For the stuctures of the neutral ether 9,9′-oxybisacridine and its dication, see: Maas (1985 ▶). For a description of conformations in bridged diphenyls, see: van der Heijden et al. (1975 ▶). graphic file with name e-69-o1633-scheme1.jpg

Experimental

Crystal data

C₁₄H₁₈N₂O²⁺·2CF₃O₃S⁻
M _r = 528.44
Monoclinic,
a = 12.7397 (18) Å
b = 11.3610 (16) Å
c = 15.611 (2) Å
β = 101.405 (4)°
V = 2214.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 100 K
0.24 × 0.18 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.925, T _max = 0.968
15390 measured reflections
4360 independent reflections
3546 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.125
S = 1.09
4360 reflections
316 parameters
53 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.94 e Å⁻³
Δρ_min = −1.04 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813027505/ff2121sup1.cif

e-69-o1633-sup1.cif^{(30.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813027505/ff2121Isup2.hkl

e-69-o1633-Isup2.hkl^{(213.7KB, hkl)}

Click here for additional data file.^{(8.3KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813027505/ff2121Isup3.cml

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
N1—H1N⋯O4	0.86 (2)	1.93 (2)	2.783 (3)	171 (3)
N2—H2N⋯O7	0.87 (2)	1.97 (2)	2.826 (3)	169 (3)
C2—H2A⋯O6ⁱ	0.95	2.36	3.170 (4)	142
C6—H6B⋯O6ⁱ	0.98	2.50	3.383 (4)	149
C7—H7B⋯O3ⁱⁱ	0.98	2.47	3.421 (4)	164
C9—H9A⋯O3ⁱⁱⁱ	0.95	2.44	3.293 (4)	149
C12—H12A⋯O5^iv	0.95	2.26	3.168 (4)	160
C14—H14A⋯O6	0.98	2.52	3.436 (4)	155

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

AWS thanks the Jean Dreyfus Boissevain Lectureship for Undergraduate Institutions, the UMass Dartmouth Office of Undergraduate Research Award, the Urban Massachusetts Louis Stokes Alliance for Minority Participation (UMLSAMP), the UMass Dartmouth Honors Program and the Northeast Section of the American Chemical Society Norris/Richards Summer Research Scholarship for funding. DRM gratefully acknowledges support from the UMass Dartmouth Chancellor’s Research Fund, the Joseph P. Healey Endowment and the National Science Foundation (CHE-1229339).

supplementary crystallographic information

1. Comment

The structures of bridged diaryls have been examined for many years and here we submit another structure into this data set. Based upon dissimilar C–O–C–C torsion angles of 61.5 (3)° and 15.1 (4)°, this structure exhibits a skew conformation (van der Heijden et al. 1975). The previously reported structures of 4,4'-oxybisdipyridyls and their cations (Dunne et al. 1996, Maas, 1985, Constable et al., 1995) have shown a twist structure, with torsion angles that are closer in size. Otherwise, the C–O–C angle of 119.3 (2)° and C–O bond distances of 1.364 (3) Å and 1.389 (3) Å are consistent with reported dipyridyl ethers

The structure of the title salt is shown in Figure 1. N–H···O hydrogen bonds between the dication and the two anions are seen between N1–H1N···O4 and N2–H2N···O7. There are no π-π interactions between pyridinium rings of the dications observed. One of the trifluoromethanesulfonate ions shows a disorder at the fluorines with a 52.0:48.0 percentage distribution and at one oxygen with a 64:36 percentage distribution.

2. Experimental

Colorless crystals of the title compound formed from the slow decomposition of neat 2,6-dimethyl-4-triflatopyridine.