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

Hsu, W.; Hsiao, H.-L.; Chen, J.-D.

doi:10.1107/S1600536810041760

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2873

https://doi.org/10.1107/S1600536810041760

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

Wayne Hsu,^a Hui-Lin Hsiao ^a and Jhy-Der Chen ^a ^*

^aDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li, Taiwan
^*Correspondence e-mail: jdchen@cycu.edu.tw

(Received 14 October 2010; accepted 15 October 2010; online 20 October 2010)

In the title molecular salt, C₁₂H₁₂N₄O₂²⁺·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 ); Hu et al. (2004 ).

Experimental

Crystal data

C₁₂H₁₂N₄O₂²⁺·2ClO₄⁻
M_r = 443.16
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.051
wR(F²) = 0.119
S = 1.03
1450 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4	0.86	2.21	2.950 (4)	144
N1—H1A⋯O3ⁱ	0.86	2.35	2.966 (5)	129
N2—H2A⋯O2ⁱⁱ	0.86	2.14	2.975 (5)	162
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810041760/gk2310Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

Data collection: XSCANS (Siemens, 1995); cell refinement: XSCANS (Siemens, 1995); data reduction: SHELXTL (Sheldrick, 2008); 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 (Sheldrick, 2008).

Figures top

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.

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

Crystal data top

C₁₂H₁₂N₄O₂²⁺·2ClO₄⁻	F(000) = 452
M_r = 443.16	D_x = 1.768 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 7.873 (1) Å	θ = 5.6–14.2°
b = 9.3728 (15) Å	µ = 0.46 mm⁻¹
c = 11.3205 (16) Å	T = 295 K
β = 94.827 (10)°	Plate, colorless
V = 832.4 (2) Å³	0.6 × 0.4 × 0.2 mm
Z = 2

Data collection top

Bruker P4 diffractometer	921 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
Graphite monochromator	θ_max = 25.0°, θ_min = 2.8°
ω scans	h = −9→1
Absorption correction: ψ scan (XSCANS; Siemens, 1995)	k = −1→11
T_min = 0.919, T_max = 0.982	l = −13→13
2017 measured reflections	3 standard reflections every 97 reflections
1450 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0424P)² + 0.6192P] where P = (F_o² + 2F_c²)/3
1450 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₂H₁₂N₄O₂²⁺·2ClO₄⁻	V = 832.4 (2) Å³
M_r = 443.16	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.873 (1) Å	µ = 0.46 mm⁻¹
b = 9.3728 (15) Å	T = 295 K
c = 11.3205 (16) Å	0.6 × 0.4 × 0.2 mm
β = 94.827 (10)°

Data collection top

Bruker P4 diffractometer	921 reflections with I > 2σ(I)
Absorption correction: ψ scan (XSCANS; Siemens, 1995)	R_int = 0.038
T_min = 0.919, T_max = 0.982	3 standard reflections every 97 reflections
2017 measured reflections	intensity decay: none
1450 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.03	Δρ_max = 0.31 e Å⁻³
1450 reflections	Δρ_min = −0.30 e Å⁻³
127 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
C1	0.3752 (6)	1.1939 (5)	0.5833 (3)	0.0381 (11)
H1B	0.3929	1.2868	0.5582	0.046*
C2	0.4314 (5)	1.1532 (5)	0.6960 (3)	0.0326 (10)
H2C	0.4865	1.2182	0.7482	0.039*
C3	0.4053 (5)	1.0143 (4)	0.7310 (3)	0.0248 (9)
C4	0.2689 (6)	0.9652 (5)	0.5391 (3)	0.0382 (11)
H4B	0.2127	0.9029	0.4851	0.046*
C5	0.3260 (5)	0.9182 (5)	0.6505 (3)	0.0327 (10)
H5A	0.3118	0.8234	0.6718	0.039*
C6	0.4772 (5)	1.0472 (4)	0.9445 (3)	0.0288 (9)
N1	0.2943 (5)	1.0996 (4)	0.5092 (3)	0.0376 (9)
H1A	0.2575	1.1276	0.4394	0.045*
N2	0.4560 (4)	0.9647 (4)	0.8451 (2)	0.0285 (8)
H2A	0.4754	0.8748	0.8533	0.034*
O1	0.4640 (4)	1.1740 (3)	0.9511 (2)	0.0426 (8)
Cl	0.07220 (14)	0.92622 (11)	0.21648 (8)	0.0338 (3)
O2	0.0153 (5)	0.8460 (4)	0.3141 (2)	0.0579 (10)
O3	0.1889 (4)	0.8433 (4)	0.1564 (3)	0.0653 (11)
O4	0.1543 (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) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.057 (3)	0.031 (2)	0.027 (2)	0.002 (2)	0.005 (2)	0.0014 (19)
C2	0.040 (3)	0.034 (3)	0.0221 (18)	0.000 (2)	−0.0045 (19)	−0.0037 (18)
C3	0.027 (2)	0.031 (2)	0.0155 (18)	0.000 (2)	−0.0032 (16)	0.0006 (17)
C4	0.047 (3)	0.041 (3)	0.025 (2)	0.000 (2)	−0.0038 (19)	−0.003 (2)
C5	0.040 (2)	0.031 (2)	0.0267 (19)	0.001 (2)	−0.0010 (18)	0.001 (2)
C6	0.032 (2)	0.032 (3)	0.0213 (19)	0.001 (2)	−0.0044 (17)	−0.0023 (19)
N1	0.047 (2)	0.046 (2)	0.0185 (15)	0.002 (2)	−0.0052 (15)	0.0025 (17)
N2	0.039 (2)	0.0258 (19)	0.0195 (16)	0.0027 (16)	−0.0035 (14)	−0.0014 (14)
O1	0.071 (2)	0.0297 (18)	0.0259 (15)	0.0076 (17)	−0.0039 (14)	−0.0017 (13)
Cl	0.0438 (6)	0.0314 (6)	0.0252 (5)	0.0015 (6)	−0.0035 (4)	−0.0029 (5)
O2	0.087 (3)	0.051 (2)	0.0344 (15)	−0.015 (2)	−0.0001 (17)	0.0134 (16)
O3	0.061 (2)	0.077 (3)	0.058 (2)	0.019 (2)	0.0025 (18)	−0.034 (2)
O4	0.082 (2)	0.035 (2)	0.0436 (17)	−0.0117 (18)	0.0001 (17)	−0.0096 (15)
O5	0.0471 (19)	0.080 (3)	0.0489 (18)	0.005 (2)	−0.0158 (16)	0.0135 (19)

Geometric parameters (Å, º) top

C1—N1	1.342 (5)	C5—H5A	0.9300
C1—C2	1.368 (5)	C6—O1	1.196 (5)
C1—H1B	0.9300	C6—N2	1.363 (4)
C2—C3	1.382 (6)	C6—C6ⁱ	1.555 (7)
C2—H2C	0.9300	N1—H1A	0.8600
C3—C5	1.391 (5)	N2—H2A	0.8600
C3—N2	1.399 (4)	Cl—O3	1.419 (3)
C4—N1	1.324 (5)	Cl—O4	1.423 (3)
C4—C5	1.375 (5)	Cl—O5	1.425 (3)
C4—H4B	0.9300	Cl—O2	1.439 (3)

N1—C1—C2	119.9 (4)	O1—C6—N2	127.6 (4)
N1—C1—H1B	120.0	O1—C6—C6ⁱ	122.0 (4)
C2—C1—H1B	120.0	N2—C6—C6ⁱ	110.4 (4)
C1—C2—C3	119.1 (4)	C4—N1—C1	122.7 (3)
C1—C2—H2C	120.5	C4—N1—H1A	118.6
C3—C2—H2C	120.5	C1—N1—H1A	118.6
C2—C3—C5	119.4 (3)	C6—N2—C3	125.3 (3)
C2—C3—N2	122.7 (3)	C6—N2—H2A	117.3
C5—C3—N2	117.9 (4)	C3—N2—H2A	117.3
N1—C4—C5	119.6 (4)	O3—Cl—O4	109.7 (2)
N1—C4—H4B	120.2	O3—Cl—O5	109.6 (2)
C5—C4—H4B	120.2	O4—Cl—O5	110.7 (2)
C4—C5—C3	119.2 (4)	O3—Cl—O2	109.7 (2)
C4—C5—H5A	120.4	O4—Cl—O2	108.32 (18)
C3—C5—H5A	120.4	O5—Cl—O2	108.8 (2)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4	0.86	2.21	2.950 (4)	144
N1—H1A···O3ⁱⁱ	0.86	2.35	2.966 (5)	129
N2—H2A···O2ⁱⁱⁱ	0.86	2.14	2.975 (5)	162

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₄O₂²⁺·2ClO₄⁻
M_r	443.16
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	7.873 (1), 9.3728 (15), 11.3205 (16)
β (°)	94.827 (10)
V (Å³)	832.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.6 × 0.4 × 0.2

Data collection
Diffractometer	Bruker P4
Absorption correction	ψ scan (XSCANS; Siemens, 1995)
T_min, T_max	0.919, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	2017, 1450, 921
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.119, 1.03
No. of reflections	1450
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.30

Computer programs: XSCANS (Siemens, 1995), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4	0.86	2.21	2.950 (4)	144
N1—H1A···O3ⁱ	0.86	2.35	2.966 (5)	129
N2—H2A···O2ⁱⁱ	0.86	2.14	2.975 (5)	162

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

Acknowledgements

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.

References

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