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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): o2873.
Published online 2010 October 20. doi:  10.1107/S1600536810041760
PMCID: PMC3008989

4,4′-[Oxalylbis(azanediyl)]dipyridinium bis(perchlorate)

Abstract

In the title molecular salt, C12H12N4O2 2+·2ClO4 , the complete cation is generated by crystallographic inversion symmetry. In the crystal, the cations and anions are linked via N—H(...)O and N—H(...)(O,O) hydrogen bonds, forming a three-dimensional framework.

Related literature

For the applications of N,N′-bis­(pyrid­yl)oxamides, see: Hsu et al. (2004 [triangle]); Hu et al. (2004 [triangle]).

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Object name is e-66-o2873-scheme1.jpg

Experimental

Crystal data

  • C12H12N4O2 2+·2ClO4
  • M r = 443.16
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2873-efi1.jpg
  • a = 7.873 (1) Å
  • b = 9.3728 (15) Å
  • c = 11.3205 (16) Å
  • β = 94.827 (10)°
  • V = 832.4 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.46 mm−1
  • T = 295 K
  • 0.6 × 0.4 × 0.2 mm

Data collection

  • Bruker P4 diffractometer
  • Absorption correction: ψ scan (XSCANS; Siemens, 1995 [triangle]) T min = 0.919, T max = 0.982
  • 2017 measured reflections
  • 1450 independent reflections
  • 921 reflections with I > 2σ(I)
  • R int = 0.038
  • 3 standard reflections every 97 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.051
  • wR(F 2) = 0.119
  • S = 1.03
  • 1450 reflections
  • 127 parameters
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: XSCANS (Siemens, 1995 [triangle]); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810041760/gk2310sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041760/gk2310Isup2.hkl

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

Acknowledgments

We are grateful to the National Science Council of the Republic of China for support. This research was also supported by the project of specific research fields in Chung-Yuan Christian University, Taiwan, under grant No. CYCU-98-CR—CH.

supplementary crystallographic information

Comment

Several Ag(I) complexes containg N,N'-bis(2-pyridyl)oxamide ligands have been prepared, which show one-dimensional and two-dimensional structures (Hsu, et al., 2004; Hu, et al., 2004). To investigate the effect of ligand-isomerism on the structural type of such complexes, the ligand N,N'-bis(4-pyridyl)oxamide was synthesized and reacted with AgClO4 in CH2Cl2. The reaction resulted unexpectedly in the perchlorate salt of the organic ligand. Within this project the crystal structure of the title compound was determined.

Experimental

N,N'-bis(4-pyridyl)oxamide (0.24 g, 1.0 mmol) and AgClO4 (0.21 g, 1.0 mmol) were placed in a flask containing 10 ml CH2Cl2. The mixture was then reflux for 12 h. The resulting solution was then filtered and then layered with diethyl ether to afford coloress plate crystals of the title compound suitable for X-ray crystallography.

Refinement

All the hydrogen atoms were placed in idealized positions and refined using the riding model approximation with C—H = 0.93 — 0.96 Å, N—H = 0.86 Å and Uiso(H) = 1.2 Ueq(C, N).

Figures

Fig. 1.
Crystal structure of the title compound with atom labeling and displacement ellipsoids drawn at the 30% probability level. Symmetry code: i =-x + 1,-y + 2,-z + 2.

Crystal data

C12H12N4O22+·2ClO4F(000) = 452
Mr = 443.16Dx = 1.768 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 7.873 (1) Åθ = 5.6–14.2°
b = 9.3728 (15) ŵ = 0.46 mm1
c = 11.3205 (16) ÅT = 295 K
β = 94.827 (10)°Plate, colorless
V = 832.4 (2) Å30.6 × 0.4 × 0.2 mm
Z = 2

Data collection

Bruker P4 diffractometer921 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.038
graphiteθmax = 25.0°, θmin = 2.8°
ω scansh = −9→1
Absorption correction: ψ scan (XSCANS; Siemens, 1995)k = −1→11
Tmin = 0.919, Tmax = 0.982l = −13→13
2017 measured reflections3 standard reflections every 97 reflections
1450 independent reflections intensity decay: none

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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.0424P)2 + 0.6192P] where P = (Fo2 + 2Fc2)/3
1450 reflections(Δ/σ)max < 0.001
127 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = −0.30 e Å3

Special details

Experimental. 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.
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
C10.3752 (6)1.1939 (5)0.5833 (3)0.0381 (11)
H1B0.39291.28680.55820.046*
C20.4314 (5)1.1532 (5)0.6960 (3)0.0326 (10)
H2C0.48651.21820.74820.039*
C30.4053 (5)1.0143 (4)0.7310 (3)0.0248 (9)
C40.2689 (6)0.9652 (5)0.5391 (3)0.0382 (11)
H4B0.21270.90290.48510.046*
C50.3260 (5)0.9182 (5)0.6505 (3)0.0327 (10)
H5A0.31180.82340.67180.039*
C60.4772 (5)1.0472 (4)0.9445 (3)0.0288 (9)
N10.2943 (5)1.0996 (4)0.5092 (3)0.0376 (9)
H1A0.25751.12760.43940.045*
N20.4560 (4)0.9647 (4)0.8451 (2)0.0285 (8)
H2A0.47540.87480.85330.034*
O10.4640 (4)1.1740 (3)0.9511 (2)0.0426 (8)
Cl0.07220 (14)0.92622 (11)0.21648 (8)0.0338 (3)
O20.0153 (5)0.8460 (4)0.3141 (2)0.0579 (10)
O30.1889 (4)0.8433 (4)0.1564 (3)0.0653 (11)
O40.1543 (4)1.0522 (3)0.2623 (2)0.0539 (9)
O5−0.0718 (4)0.9610 (4)0.1369 (3)0.0598 (10)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.057 (3)0.031 (2)0.027 (2)0.002 (2)0.005 (2)0.0014 (19)
C20.040 (3)0.034 (3)0.0221 (18)0.000 (2)−0.0045 (19)−0.0037 (18)
C30.027 (2)0.031 (2)0.0155 (18)0.000 (2)−0.0032 (16)0.0006 (17)
C40.047 (3)0.041 (3)0.025 (2)0.000 (2)−0.0038 (19)−0.003 (2)
C50.040 (2)0.031 (2)0.0267 (19)0.001 (2)−0.0010 (18)0.001 (2)
C60.032 (2)0.032 (3)0.0213 (19)0.001 (2)−0.0044 (17)−0.0023 (19)
N10.047 (2)0.046 (2)0.0185 (15)0.002 (2)−0.0052 (15)0.0025 (17)
N20.039 (2)0.0258 (19)0.0195 (16)0.0027 (16)−0.0035 (14)−0.0014 (14)
O10.071 (2)0.0297 (18)0.0259 (15)0.0076 (17)−0.0039 (14)−0.0017 (13)
Cl0.0438 (6)0.0314 (6)0.0252 (5)0.0015 (6)−0.0035 (4)−0.0029 (5)
O20.087 (3)0.051 (2)0.0344 (15)−0.015 (2)−0.0001 (17)0.0134 (16)
O30.061 (2)0.077 (3)0.058 (2)0.019 (2)0.0025 (18)−0.034 (2)
O40.082 (2)0.035 (2)0.0436 (17)−0.0117 (18)0.0001 (17)−0.0096 (15)
O50.0471 (19)0.080 (3)0.0489 (18)0.005 (2)−0.0158 (16)0.0135 (19)

Geometric parameters (Å, °)

C1—N11.342 (5)C5—H5A0.9300
C1—C21.368 (5)C6—O11.196 (5)
C1—H1B0.9300C6—N21.363 (4)
C2—C31.382 (6)C6—C6i1.555 (7)
C2—H2C0.9300N1—H1A0.8600
C3—C51.391 (5)N2—H2A0.8600
C3—N21.399 (4)Cl—O31.419 (3)
C4—N11.324 (5)Cl—O41.423 (3)
C4—C51.375 (5)Cl—O51.425 (3)
C4—H4B0.9300Cl—O21.439 (3)
N1—C1—C2119.9 (4)O1—C6—N2127.6 (4)
N1—C1—H1B120.0O1—C6—C6i122.0 (4)
C2—C1—H1B120.0N2—C6—C6i110.4 (4)
C1—C2—C3119.1 (4)C4—N1—C1122.7 (3)
C1—C2—H2C120.5C4—N1—H1A118.6
C3—C2—H2C120.5C1—N1—H1A118.6
C2—C3—C5119.4 (3)C6—N2—C3125.3 (3)
C2—C3—N2122.7 (3)C6—N2—H2A117.3
C5—C3—N2117.9 (4)C3—N2—H2A117.3
N1—C4—C5119.6 (4)O3—Cl—O4109.7 (2)
N1—C4—H4B120.2O3—Cl—O5109.6 (2)
C5—C4—H4B120.2O4—Cl—O5110.7 (2)
C4—C5—C3119.2 (4)O3—Cl—O2109.7 (2)
C4—C5—H5A120.4O4—Cl—O2108.32 (18)
C3—C5—H5A120.4O5—Cl—O2108.8 (2)

Symmetry codes: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O40.862.212.950 (4)144
N1—H1A···O3ii0.862.352.966 (5)129
N2—H2A···O2iii0.862.142.975 (5)162

Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, −y+3/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2310).

References

  • Hsu, Y.-F. & Chen, J.-D. (2004). Eur. J. Inorg. Chem. pp. 1488–1493.
  • Hu, H.-L., Yeh, C.-W. & Chen, J.-D. (2004). Eur. J. Inorg. Chem. pp. 4696–4701.
  • Sheldrick, G. M. (2008). Acta Cryst A64, 112–122. [PubMed]
  • Siemens (1995). XSCANS Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

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