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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o2970.
Published online 2009 November 4. doi:  10.1107/S1600536809044912
PMCID: PMC2972023

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

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 [triangle]). 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 [triangle]). Zhang, Du et al. (2004 [triangle]) and Zhang, Lu et al. (2004 [triangle]) also report the use of 1,2-di-4-pyridylethane N,N′-dioxide in the preparation of lanthanide coordination networks.

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Object name is e-65-o2970-scheme1.jpg

Experimental

Crystal data

  • C12H12N2O2·2C2H4O2
  • M r = 336.34
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2970-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.25 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

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.

Refinement

All H atoms were positioned geometrically and refined using a riding model with C—H = 0.95–0.99 Å and with Uiso(H) = 1.2 (1.5 for methyl groups) times Ueq(C), and O—H = 0.84 Å and Uiso(H) = 1.5 times Ueq(O).

Figures

Fig. 1.
The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids for non-H atoms.
Fig. 2.
π-π interactions between neighboring 1,2-di-4-pyridylethane N,N'-dioxide molecules.
Fig. 3.
O—H···O hydrogen bonded units made of one 1,2-di-4-pyridylethane N,N'-dioxide molecule and two acetic acid molecules. Hydrogen bonds are shown as dashed lines.
Fig. 4.
O—H···O and C—H···O hydrogen bonding interactions between 1,2-di-4-pyridylethane N,N'-dioxide and neighboring 1,2-di-4-pyridylethane N,N'-dioxide and acetic acid molecules. Hydrogen bonds ...
Fig. 5.
Packing of the title compound viewed down the b axis. Hydrogen bonds are shown as dashed lines.

Crystal data

C12H12N2O2·2C2H4O2Z = 1
Mr = 336.34F(000) = 178
Triclinic, P1Dx = 1.370 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1109 (6) ÅCell parameters from 3794 reflections
b = 7.1562 (6) Åθ = 3.2–30.5°
c = 9.2888 (7) ŵ = 0.11 mm1
α = 73.719 (1)°T = 173 K
β = 87.508 (1)°Block, colorless
γ = 64.424 (1)°0.55 × 0.45 × 0.37 mm
V = 407.62 (6) Å3

Data collection

Bruker SMART APEX CCD diffractometer2446 independent reflections
Radiation source: fine-focus sealed tube2228 reflections with I > 2σ(I)
graphiteRint = 0.011
ω scansθmax = 30.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −10→10
Tmin = 0.944, Tmax = 0.962k = −10→9
4857 measured reflectionsl = −13→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0796P)2 + 0.0824P] where P = (Fo2 + 2Fc2)/3
2446 reflections(Δ/σ)max = 0.001
114 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = −0.25 e Å3

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 (Å2)

xyzUiso*/Ueq
O10.13750 (10)0.89616 (12)0.18453 (8)0.02574 (15)
O20.65037 (13)1.15878 (12)0.46617 (9)0.03371 (18)
O30.86230 (12)0.87364 (12)0.65134 (8)0.02891 (16)
H30.84700.96930.69250.043*
N10.32388 (11)0.79711 (12)0.13545 (9)0.019
C10.48607 (14)0.64120 (15)0.23478 (10)0.022
H10.46740.60450.33910.026*
C20.67866 (13)0.53522 (15)0.18518 (10)0.02148 (17)
H20.79190.42670.25580.026*
C30.70835 (13)0.58611 (14)0.03222 (10)0.01794 (15)
C40.53728 (13)0.74729 (14)−0.06672 (10)0.01899 (16)
H40.55200.7860−0.17170.023*
C50.34614 (13)0.85159 (14)−0.01355 (10)0.01970 (16)
H50.23080.9614−0.08190.024*
C60.91767 (13)0.46745 (14)−0.02202 (10)0.01940 (16)
H6A0.90220.5004−0.13290.023*
H6B0.96620.30950.02220.023*
C70.76154 (14)0.96654 (16)0.51521 (10)0.02359 (18)
C80.80145 (17)0.80587 (18)0.42910 (12)0.0301 (2)
H8A0.69250.86860.34560.045*
H8B0.79930.67410.49630.045*
H8C0.93860.77000.38920.045*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0129 (3)0.0322 (4)0.0298 (3)−0.0051 (3)0.0056 (2)−0.0140 (3)
O20.0348 (4)0.0244 (4)0.0278 (4)−0.0039 (3)0.0014 (3)−0.0014 (3)
O30.0253 (3)0.0244 (3)0.0276 (4)−0.0027 (3)−0.0033 (3)−0.0063 (3)
N10.0120.0200.024−0.0050.003−0.008
C10.0170.0240.021−0.0060.001−0.006
C20.0149 (4)0.0216 (4)0.0235 (4)−0.0041 (3)0.0004 (3)−0.0061 (3)
C30.0131 (3)0.0171 (4)0.0241 (4)−0.0063 (3)0.0025 (3)−0.0073 (3)
C40.0157 (4)0.0184 (4)0.0214 (4)−0.0069 (3)0.0024 (3)−0.0046 (3)
C50.0148 (3)0.0184 (4)0.0233 (4)−0.0056 (3)0.0010 (3)−0.0047 (3)
C60.0136 (3)0.0195 (4)0.0260 (4)−0.0064 (3)0.0038 (3)−0.0096 (3)
C70.0177 (4)0.0260 (4)0.0224 (4)−0.0078 (3)0.0058 (3)−0.0036 (3)
C80.0292 (5)0.0314 (5)0.0272 (5)−0.0109 (4)0.0061 (4)−0.0093 (4)

Geometric parameters (Å, °)

O1—N11.3358 (9)C3—C61.5079 (11)
O2—C71.2107 (12)C4—C51.3859 (11)
O3—C71.3231 (12)C4—H40.9500
O3—H30.8400C5—H50.9500
N1—C51.3506 (12)C6—C6i1.5410 (17)
N1—C11.3530 (12)C6—H6A0.9900
C1—C21.3811 (12)C6—H6B0.9900
C1—H10.9500C7—C81.5021 (14)
C2—C31.3950 (13)C8—H8A0.9800
C2—H20.9500C8—H8B0.9800
C3—C41.3951 (12)C8—H8C0.9800
O1—N1—C1119.76 (8)C1—C2—H2119.7
C5—N1—C1120.99 (8)C2—C1—H1119.8
O1—N1—C5119.24 (7)C3—C2—H2119.7
N1—C1—C2120.31 (8)C3—C4—H4119.6
N1—C5—C4120.00 (8)C3—C6—H6A109.3
C1—C2—C3120.58 (8)C3—C6—H6B109.3
C2—C3—C4117.43 (8)C4—C5—H5120.0
C3—C4—C5120.70 (8)C5—C4—H4119.6
C4—C3—C6122.07 (8)C6i—C6—H6A109.3
C2—C3—C6120.50 (8)C6i—C6—H6B109.3
C3—C6—C6i111.43 (8)C7—C8—H8A109.5
O2—C7—O3123.73 (10)C7—C8—H8B109.5
O2—C7—C8124.14 (9)C7—C8—H8C109.5
O3—C7—C8112.13 (8)H6A—C6—H6B108.0
N1—C1—H1119.8H8A—C8—H8B109.5
N1—C5—H5120.0H8A—C8—H8C109.5
C7—O3—H3109.5H8B—C8—H8C109.5

Symmetry codes: (i) −x+2, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3···O1ii0.841.722.5393 (11)164
C1—H1···O2ii0.952.683.3915 (12)132
C2—H2···O3iii0.952.453.3489 (11)158
C5—H5···O1iv0.952.483.3341 (12)149
C6—H6B···O1v0.992.663.6309 (12)168
C8—H8C···O1vi0.982.523.3655 (13)145

Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) −x+2, −y+1, −z+1; (iv) −x, −y+2, −z; (v) x+1, y−1, z; (vi) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2243).

References

  • Barbour, L. J. (2001). J. Supramol. Chem 1, 189–191.
  • Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Lu, W. J., Zhang, L. P., Song, H. B., Wang, Q. M. & Mak, T. C. W. (2002). New J. Chem. 26, 775–781.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Simpson, P. G., Vinciguerra, A. & Quagliano, J. V. (1963). Inorg. Chem. 2, 282–286.
  • Zhang, L. P., Du, M., Lu, W. J. & Mak, T. C. W. (2004). Polyhedron, 23, 857–863.
  • Zhang, L. P., Lu, W. J. & Mak, T. C. W. (2004). Polyhedron, 23, 169–176.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography