1,2-Di-4-pyridylethane N,N′-dioxide–acetic acid (1/2)

Elaine P Boron; Jacqueline M Knaust

doi:10.1107/S1600536809044912

. 2009 Nov 4;65(Pt 12):o2970. doi: 10.1107/S1600536809044912

1,2-Di-4-pyridylethane N,N′-dioxide–acetic acid (1/2)

Elaine P Boron ^a, Jacqueline M Knaust ^a,^*

PMCID: PMC2972023 PMID: 21578711

Abstract

The title compound, C₁₂H₁₂N₂O₂·2C₂H₄O₂, was prepared from 1,2-di-4-pyridylethane, acetic acid, and hydrogen peroxide. The 1,2-di-4-pyridylethane N,N′-dioxide molecule is located on an inversion center. π–π stacking interactions between neighboring 1,2-di-4-pyridylethane N,N′-dioxide molecules are observed with a centroid–centroid distance of 3.613 Å, an interplanar distance of 3.317 Å, and a slippage of 1.433 Å. O—H⋯O hydrogen-bonding interactions between 1,2-di-4-pyridylethane N,N′-dioxide and acetic acid molecules result in distinct hydrogen-bonded units made of one N-oxide and two acetic acid molecules. These units are then linked into a three-dimensional network through weaker C—H⋯O hydrogen-bonding interactions.

Related literature

For the synthesis of 2,2′-bipyridine N,N′-dioxide, see: Simpson et al. (1963 ▶). For the synthesis of 1,2-di-4-pyridylethane N,N′-dioxide peroxide disolvate and its use in the synthesis of lanthanide coordination networks, see: Lu et al. (2002 ▶). Zhang, Du et al. (2004 ▶) and Zhang, Lu et al. (2004 ▶) also report the use of 1,2-di-4-pyridylethane N,N′-dioxide in the preparation of lanthanide coordination networks. graphic file with name e-65-o2970-scheme1.jpg

Experimental

Crystal data

C₁₂H₁₂N₂O₂·2C₂H₄O₂
M _r = 336.34
Triclinic,
a = 7.1109 (6) Å
b = 7.1562 (6) Å
c = 9.2888 (7) Å
α = 73.719 (1)°
β = 87.508 (1)°
γ = 64.424 (1)°
V = 407.62 (6) Å³
Z = 1
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 173 K
0.55 × 0.45 × 0.37 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.944, T _max = 0.962
4857 measured reflections
2446 independent reflections
2228 reflections with I > 2σ(I)
R _int = 0.011

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.133
S = 1.09
2446 reflections
114 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: X-SEED.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044912/zl2243sup1.cif

e-65-o2970-sup1.cif^{(13.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044912/zl2243Isup2.hkl

e-65-o2970-Isup2.hkl^{(120.1KB, hkl)}

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
O3—H3⋯O1ⁱ	0.84	1.72	2.5393 (11)	164
C1—H1⋯O2ⁱ	0.95	2.68	3.3915 (12)	132
C2—H2⋯O3ⁱⁱ	0.95	2.45	3.3489 (11)	158
C5—H5⋯O1ⁱⁱⁱ	0.95	2.48	3.3341 (12)	149
C6—H6B⋯O1^iv	0.99	2.66	3.6309 (12)	168
C8—H8C⋯O1^v	0.98	2.52	3.3655 (13)	145

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

Acknowledgments

The authors are grateful to Allegheny College for providing funding in support of this research. The diffractometer was funded by the NSF (grant No. 0087210), the Ohio Board of Regents (grant No. CAP-491) and by Youngstown State University. The authors would also like to acknowledge the STaRBURSTT CyberInstrumentation Consortium for assistance with the crystallography.

supplementary crystallographic information

Comment

The use of aromatic N,N'-dioxide ligands in the synthesis of coordination networks has been of recent interest (Lu et al. (2002), Zhang, Du et al. (2004) and Zhang, Lu et al. (2004)). The title compound was prepared using the reaction conditions described by Simpson et al. (1963) to prepare 2,2'-bipyridine N,N'-dioxide. The molar ratios of reactants used to form the title compound were 1:20:3 (1,2-di-4-pyridylethane, acetic acid, and peroxide), and the reaction mixture was heated for 21 h. However, when precipitation of the product did not occur following the addition of acetone as described by Simpson et al. (1963), the solution was cooled to 273 K, and crystals of the title compound slowly formed. Lu et al. (2002) described the synthesis of 1,2-di-4-pyridylethane N,N'-dioxide peroxide disolvate using a slightly modified version of the conditions described by Simpson et al. (1963). The molar ratios of reactants used by Lu et al. (2002) are 1:13:8, and the reaction was heated for 12 h. Lu et al. (2002) removed all excess acetic acid and water under vacuum before adding acetone to the resulting oil to precipitate the crude product; the crude product was washed to remove unreacted 1,2-di-4-pyridylethane and recrystallized to give 1,2-di-4-pyridylethane N,N'-dioxide peroxide disolvate. Presumably, the formation of the acetic acid adduct versus the peroxide adduct is due to the difference in reaction and crystallization conditions. The title compound is formed with a high 1,2-di-4-pyridylethane to acetic acid ratio and crystallization directly from the reaction solution. Whereas the peroxide adduct is formed with a high 1,2-di-4-pyridylethane to peroxide ratio and removal of excess acetic acid before crystallization.

The asymmetric unit of the title compound contains half of a 1,2-di-4-pyridylethane N,N'-dioxide molecule and one acetic acid molecule (Figure 1). The 1,2-di-4-pyridylethane N,N'-dioxide sits on a center of inversion. π-π stacking interactions with a centroid to centroid distance of 3.6133 Å, an interplanar distance of 3.3171 Å, and a slippage of 1.433 Å. are observed between neighboring N-oxide molecules [symmetry code: -x + 1, -y + 1, -z] (Figure 2). The title compound forms distinct O—H···O hydrogen bonded units made of one N-oxide molecule and two acetic acid molecules (Figure 3). Weaker O—H···O hydrogen bonding interactions are also observed between N-oxide and acetic acid molecules and between neighboring N-oxide molecules (Figure 4). As seen in the packing diagram, the N-oxide and acetic acid molecules are linked into a three-dimensional hydrogen-bonding network (Figure 5).

Experimental

1,2-Di-4-pyridylethane (11.7918 g, 64.0 mmol), acetic acid (75 ml), and 35% hydrogen peroxide (11.1 ml) were heated at 343–353K (70–80 °C) for 3 h. Additional hydrogen peroxide (7.8 ml) was added, and heating was continued. After an additional 19 h of heating the solution was cooled to room temperature. Crystals formed upon the addition of acetone (1L) and cooling to 273 K.