6,6′-Dimethyl-2,2′-[oxalylbis(aza­nedi­yl)]dipyridinium dichloride acetonitrile solvate

Hu, H.-L.; Cheng, P.-C.; Wu, C.-J.; Chen, J.-D.

doi:10.1107/S1600536810033519

organic compounds

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Volume 66| Part 9| September 2010| Page o2386

https://doi.org/10.1107/S1600536810033519

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6,6′-Dimethyl-2,2′-[oxalylbis(azanediyl)]dipyridinium dichloride acetonitrile solvate

Hui-Ling Hu,^a Pei-Chi Cheng,^b Chia-Jun Wu ^b and Jhy-Der Chen ^b ^*

^aDepartment of Chemical and Materials Engineering, Nanya Institute of Technology, Chung-Li, Taiwan, and ^bDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li, Taiwan
^*Correspondence e-mail: jdchen@cycu.edu.tw

(Received 2 August 2010; accepted 19 August 2010; online 25 August 2010)

In the crystal structure of the title compound, C₁₄H₁₆N₄O₂²⁺·2Cl⁻·CH₃CN, weak intermolecular N—H⋯Cl hydrogen bonds are found between the H atoms bound to the pyridine and amine N atoms and the chloride anions. The asymmetric unit consits of one half cationic molecule which is located on a centre of inversion, one chloride anion in a general position and one half acetonitrile molecule which is located on a twofold axis. Because of symmetry, the C—H hydrogens of the acetonitrile solvent molecule are disordered over two orientations.

Related literature

For Ag(I) complexes incorporating N,N′-bis(2-pyridyl)oxamide ligands which show one- and two-dimensional structures, see: Hsu & Chen (2004 ); Hu et al. (2004 ). For the synthesis of the starting reactant, see: Cheng et al. (2009 ).

Experimental

Crystal data

C₁₄H₁₆N₄O₂²⁺·2Cl⁻·C₂H₃N
M_r = 384.26
Monoclinic, P 2/c
a = 10.6740 (19) Å
b = 8.7637 (5) Å
c = 10.370 (3) Å
β = 109.83 (2)°
V = 912.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 295 K
0.6 × 0.2 × 0.1 mm

Data collection

Bruker P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1995 ) T_min = 0.823, T_max = 0.922
2165 measured reflections
1619 independent reflections
1308 reflections with I > 2σ(I)
R_int = 0.023
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.094
S = 1.07
1619 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Clⁱ	0.86	2.14	2.9772 (16)	165
N2—H2A⋯Clⁱ	0.86	2.43	3.2057 (17)	150
Symmetry code: (i) x, y+1, z.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810033519/nc2195sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810033519/nc2195Isup2.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 steric effect of the alkyl groups on the structural type of such complexes, we have synthesized N,N'-bis(6-methyl-2-pyridyl)oxamide (Cheng, et al., 2009) and reacted with metal salts. Within this project the crystal structure of the title compound was determined.

In the crystal structure the cationic molecules are almost planar and the O atoms are trans-oriented (Fig. 1). The N,N'-Bis(6-methyl-2-pyridinium)oxamide cations and the chloride anions are connected by weak intermolecular N—H···Cl hydrogen bonding (Tab. 1).

Related literature top

For Ag(I) complexes containg N,N'-bis(2-pyridyl)oxamide ligands which show one- and two-dimensional structures, see: Hsu et al. (2004); Hu et al. (2004). For the synthesis of the starting reactand, see: Cheng et al. (2009).

Experimental top

N,N'-bis(6-methyl-2-pyridyl)oxamide (0.30 g, 1.1 mmol) (Cheng, et al., 2009) and CuCl₂ (0.15 g, 1.1 mmol) were placed in a flask containing 10 ml CH₂Cl₂, which was refluxed for 8 h. The precipitate was then filtered and dried in vacuum. Coloress plate crystals of the title compound suitable for X-ray crystallography were obtained by slow evaporization of the solvent from a solution of the precipitate in CH₃CN.

Structure description top

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 labeling and displacement ellipsoids drawn at the 30% probability level. Symmetry code: i = -x + 1,-y + 2,-z + 1. Disordering is shown as full and open bonds.

6,6'-Dimethyl-2,2'-[oxalylbis(azanediyl)]dipyridinium dichloride acetonitrile solvate top

Crystal data top

C₁₄H₁₆N₄O₂²⁺·2Cl⁻·C₂H₃N	F(000) = 400
M_r = 384.26	D_x = 1.399 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 28 reflections
a = 10.6740 (19) Å	θ = 4.7–12.5°
b = 8.7637 (5) Å	µ = 0.38 mm⁻¹
c = 10.370 (3) Å	T = 295 K
β = 109.83 (2)°	Plate, colourless
V = 912.5 (3) Å³	0.6 × 0.2 × 0.1 mm
Z = 2

Data collection top

Bruker P4 diffractometer	1308 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.023
Graphite monochromator	θ_max = 25.0°, θ_min = 2.0°
ω scans	h = −12→12
Absorption correction: ψ scan (XSCANS; Siemens, 1995)	k = −10→1
T_min = 0.823, T_max = 0.922	l = −12→1
2165 measured reflections	3 standard reflections every 97 reflections
1619 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0401P)² + 0.2279P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1619 reflections	Δρ_max = 0.20 e Å⁻³
118 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0090 (15)

Crystal data top

C₁₄H₁₆N₄O₂²⁺·2Cl⁻·C₂H₃N	V = 912.5 (3) Å³
M_r = 384.26	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 10.6740 (19) Å	µ = 0.38 mm⁻¹
b = 8.7637 (5) Å	T = 295 K
c = 10.370 (3) Å	0.6 × 0.2 × 0.1 mm
β = 109.83 (2)°

Data collection top

Bruker P4 diffractometer	1308 reflections with I > 2σ(I)
Absorption correction: ψ scan (XSCANS; Siemens, 1995)	R_int = 0.023
T_min = 0.823, T_max = 0.922	3 standard reflections every 97 reflections
2165 measured reflections	intensity decay: none
1619 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.07	Δρ_max = 0.20 e Å⁻³
1619 reflections	Δρ_min = −0.17 e Å⁻³
118 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 esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
Cl	0.23722 (6)	0.11398 (6)	0.09664 (5)	0.0569 (2)
O	0.55710 (15)	0.81506 (16)	0.54656 (14)	0.0542 (4)
N1	0.27012 (15)	0.78055 (18)	0.15297 (15)	0.0400 (4)
H1A	0.2513	0.8715	0.1212	0.048*
N2	0.39872 (16)	0.90108 (18)	0.34987 (15)	0.0424 (4)
H2A	0.3653	0.9837	0.3073	0.051*
N3	1.0000	0.6381 (4)	0.2500	0.0953 (12)
C1	0.1214 (2)	0.7019 (3)	−0.0703 (2)	0.0596 (6)
H1B	0.0933	0.6103	−0.1230	0.089*
H1C	0.1660	0.7672	−0.1153	0.089*
H1D	0.0450	0.7538	−0.0626	0.089*
C2	0.2141 (2)	0.6624 (2)	0.0687 (2)	0.0443 (5)
C3	0.2463 (2)	0.5175 (2)	0.1183 (2)	0.0521 (5)
H3A	0.2118	0.4336	0.0627	0.062*
C4	0.3305 (2)	0.4971 (3)	0.2514 (2)	0.0567 (6)
H4A	0.3514	0.3985	0.2851	0.068*
C5	0.3847 (2)	0.6201 (2)	0.3363 (2)	0.0522 (5)
H5A	0.4406	0.6054	0.4262	0.063*
C6	0.35325 (19)	0.7650 (2)	0.28310 (18)	0.0395 (4)
C7	0.4915 (2)	0.9157 (2)	0.47672 (19)	0.0420 (5)
C8	1.0000	0.7663 (4)	0.2500	0.0583 (8)
C9	1.0000	0.9293 (4)	0.2500	0.0666 (9)
H9B	1.0894	0.9658	0.2704	0.100*	0.50
H9A	0.9650	0.9658	0.3182	0.100*	0.50
H9C	0.9456	0.9658	0.1614	0.100*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0769 (4)	0.0307 (3)	0.0530 (3)	0.0030 (2)	0.0089 (3)	0.0052 (2)
O	0.0635 (9)	0.0404 (9)	0.0450 (7)	0.0124 (7)	0.0005 (7)	0.0022 (6)
N1	0.0498 (9)	0.0268 (8)	0.0401 (8)	0.0023 (7)	0.0112 (7)	0.0022 (6)
N2	0.0546 (10)	0.0297 (9)	0.0373 (8)	0.0057 (7)	0.0082 (7)	0.0012 (6)
N3	0.107 (3)	0.052 (2)	0.136 (3)	0.000	0.054 (3)	0.000
C1	0.0696 (15)	0.0438 (13)	0.0510 (12)	−0.0032 (11)	0.0017 (11)	−0.0076 (10)
C2	0.0499 (11)	0.0326 (10)	0.0494 (11)	−0.0034 (9)	0.0155 (9)	−0.0053 (8)
C3	0.0604 (14)	0.0300 (11)	0.0625 (13)	−0.0045 (9)	0.0166 (11)	−0.0053 (10)
C4	0.0689 (14)	0.0289 (10)	0.0680 (14)	0.0042 (10)	0.0178 (12)	0.0110 (10)
C5	0.0639 (13)	0.0361 (11)	0.0491 (11)	0.0044 (10)	0.0095 (10)	0.0071 (9)
C6	0.0465 (10)	0.0334 (10)	0.0382 (9)	0.0016 (8)	0.0140 (8)	0.0010 (8)
C7	0.0472 (11)	0.0398 (11)	0.0364 (10)	0.0059 (9)	0.0109 (8)	−0.0008 (8)
C8	0.0587 (19)	0.053 (2)	0.066 (2)	0.000	0.0248 (16)	0.000
C9	0.080 (2)	0.0492 (19)	0.068 (2)	0.000	0.0212 (18)	0.000

Geometric parameters (Å, º) top

O—C7	1.204 (2)	C2—C3	1.370 (3)
N1—C6	1.347 (2)	C3—C4	1.380 (3)
N1—C2	1.356 (2)	C3—H3A	0.9300
N1—H1A	0.8600	C4—C5	1.388 (3)
N2—C7	1.358 (2)	C4—H4A	0.9300
N2—C6	1.382 (2)	C5—C6	1.379 (3)
N2—H2A	0.8600	C5—H5A	0.9300
N3—C8	1.123 (5)	C7—C7ⁱ	1.545 (4)
C1—C2	1.486 (3)	C8—C9	1.429 (5)
C1—H1B	0.9600	C9—H9B	0.9600
C1—H1C	0.9600	C9—H9A	0.9600
C1—H1D	0.9600	C9—H9C	0.9600

C6—N1—C2	124.41 (17)	C3—C4—H4A	119.2
C6—N1—H1A	117.8	C5—C4—H4A	119.2
C2—N1—H1A	117.8	C6—C5—C4	117.98 (19)
C7—N2—C6	125.72 (16)	C6—C5—H5A	121.0
C7—N2—H2A	117.1	C4—C5—H5A	121.0
C6—N2—H2A	117.1	N1—C6—C5	118.82 (18)
C2—C1—H1B	109.5	N1—C6—N2	114.49 (16)
C2—C1—H1C	109.5	C5—C6—N2	126.69 (17)
H1B—C1—H1C	109.5	O—C7—N2	126.70 (18)
C2—C1—H1D	109.5	O—C7—C7ⁱ	122.0 (2)
H1B—C1—H1D	109.5	N2—C7—C7ⁱ	111.3 (2)
H1C—C1—H1D	109.5	N3—C8—C9	180.000 (2)
N1—C2—C3	117.77 (18)	C8—C9—H9B	109.5
N1—C2—C1	116.77 (18)	C8—C9—H9A	109.5
C3—C2—C1	125.46 (19)	H9B—C9—H9A	109.5
C2—C3—C4	119.4 (2)	C8—C9—H9C	109.5
C2—C3—H3A	120.3	H9B—C9—H9C	109.5
C4—C3—H3A	120.3	H9A—C9—H9C	109.5
C3—C4—C5	121.6 (2)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Clⁱⁱ	0.86	2.14	2.9772 (16)	165
N2—H2A···Clⁱⁱ	0.86	2.43	3.2057 (17)	150

Symmetry code: (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N₄O₂²⁺·2Cl⁻·C₂H₃N
M_r	384.26
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	295
a, b, c (Å)	10.6740 (19), 8.7637 (5), 10.370 (3)
β (°)	109.83 (2)
V (Å³)	912.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.6 × 0.2 × 0.1

Data collection
Diffractometer	Bruker P4
Absorption correction	ψ scan (XSCANS; Siemens, 1995)
T_min, T_max	0.823, 0.922
No. of measured, independent and observed [I > 2σ(I)] reflections	2165, 1619, 1308
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.094, 1.07
No. of reflections	1619
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17

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···Clⁱ	0.86	2.14	2.9772 (16)	164.6
N2—H2A···Clⁱ	0.86	2.43	3.2057 (17)	149.8

Symmetry code: (i) x, y+1, z.

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 the specific research fields in Chung-Yuan Christian University, Taiwan, under grant No. CYCU-98-CR—CH.

References

Cheng, P.-C., Wu, C.-J. & Chen, J.-D. (2009). Acta Cryst. E65, o2734. Web of Science CrossRef IUCr Journals Google Scholar
Hsu, Y.-F. & Chen, J.-D. (2004). Eur. J. Inorg. Chem. pp. 1488–1493. Web of Science CSD CrossRef Google Scholar
Hu, H.-L., Yeh, C.-W. & Chen, J.-D. (2004). Eur. J. Inorg. Chem. pp. 4696–4701. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1995). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

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https://doi.org/10.1107/S1600536810033519

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6,6′-Di­methyl-2,2′-[oxalylbis(aza­nedi­yl)]dipyridinium dichloride aceto­nitrile solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

6,6′-Dimethyl-2,2′-[oxalylbis(azanediyl)]dipyridinium dichloride acetonitrile solvate