N,N′-Bis(6-methyl-2-pyrid­yl)oxamide

Cheng, P.-C.; Wu, C.-J.; Chen, J.-D.

doi:10.1107/S1600536809040902

organic compounds

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N,N′-Bis(6-methyl-2-pyridyl)oxamide

Pei-Chi Cheng,^a Chia-Jun Wu ^a and Jhy-Der Chen ^a ^*

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

(Received 5 October 2009; accepted 7 October 2009; online 17 October 2009)

In the crystal structure of the title compound, C₁₄H₁₄N₄O₂, the molecules are almost planar (mean deviation 0.028 Å) and a weak intramolecular N—H⋯O hydrogen bond between the H atom bound to an oxamide N atom and a carbonyl O atom is found. The asymmetric unit consits of one half-molecule which is located on a centre of inversion.

Related literature

For the synthesis, see: Siedel et al. (1970 ). For a series of Ag(I) coordination polymers containing N¹,N²-bis(2-pyridyl)oxamide ligands, see: Hsu & Chen (2004 ); Hu et al. (2004 ).

Experimental

Crystal data

C₁₄H₁₄N₄O₂
M_r = 270.29
Monoclinic, P 2₁ /c
a = 3.8925 (6) Å
b = 15.964 (2) Å
c = 10.8353 (14) Å
β = 94.461 (13)°
V = 671.26 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.4 × 0.2 × 0.1 mm

Data collection

Bruker P4 diffractometer
Absorption correction: multi-scan (XSCANS; Siemens, 1995 ) T_min = 0.741, T_max = 0.762
1867 measured reflections
1190 independent reflections
767 reflections with I > 2σ(I)
R_int = 0.028
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.101
S = 1.01
1190 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Oⁱ	0.86	2.24	2.6718 (18)	111
Symmetry code: (i) -x+1, -y+1, -z+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/S1600536809040902/nc2161sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040902/nc2161Isup2.hkl

checkCIF report

Comment top

A series of Ag(I) coordination polymers containg N¹,N²-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 coordination polymers, we have synthesized the title compound. Within this project its crystal structure was determined.

In its crystal structure weak intramolecular N-H···O hydrogen bonding is found (Tab. 1) and the molecules are almost planar (Fig. 1).

Related literature top

For the synthesis, see: Siedel et al. (1970). For a series of Ag(I) coordination polymers containg N¹,N²-bis(2-pyridyl)oxamide ligands, see: Hsu et al. (2004); Hu et al. (2004).

Experimental top

2-Amino-6-methylpyridine (6.2 g, 57.3 mmol) was dissolved in 200 ml CH₂Cl₂, followed by addition of triethyl amine (10.0 ml, 72.1 mmol) at 0° C. The mixture was then stirred for 10 min. Oxalyl chloride (2.5 ml, 28.7 mmol) in 10 ml CH₂Cl₂ was then added slowly to the above mixture. After continuous stirring for 3 h at 0° give maximu[C, 200 ml hexanes was added to the mixture to induce precipitate. The solid was filtered, washed with water to give a white product. Yield: 2.8 g (36%). Coloress plate crystals suitable for X-ray crystallography were obtained by slow evaporization of the solvent from a solution in CH₂Cl₂.

Structure description top

In its crystal structure weak intramolecular N-H···O hydrogen bonding is found (Tab. 1) and the molecules are almost planar (Fig. 1).

For the synthesis, see: Siedel et al. (1970). For a series of Ag(I) coordination polymers containg N¹,N²-bis(2-pyridyl)oxamide ligands, 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 labeling and displacement ellipsoids drawn at the 30% probability level. Symmetry code: i = -x + 1, -y + 1, -z + 2. The disorder is shown with open bonds.

N,N'-Bis(6-methyl-2-pyridyl)oxamide top

Crystal data top

C₁₄H₁₄N₄O₂	F(000) = 284
M_r = 270.29	D_x = 1.337 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 23 reflections
a = 3.8925 (6) Å	θ = 7.5–12.6°
b = 15.964 (2) Å	µ = 0.09 mm⁻¹
c = 10.8353 (14) Å	T = 295 K
β = 94.461 (13)°	Plate, colorless
V = 671.26 (16) Å³	0.4 × 0.2 × 0.1 mm
Z = 2

Data collection top

Bruker P4 diffractometer	767 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 25.0°, θ_min = 2.3°
ω scans	h = −1→4
Absorption correction: multi-scan (XSCANS; Siemens, 1995)	k = −1→18
T_min = 0.741, T_max = 0.762	l = −12→12
1867 measured reflections	3 standard reflections every 97 reflections
1190 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)] = 0.040	H-atom parameters constrained
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0467P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1190 reflections	Δρ_max = 0.14 e Å⁻³
93 parameters	Δρ_min = −0.12 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: 0.021 (4)

Crystal data top

C₁₄H₁₄N₄O₂	V = 671.26 (16) Å³
M_r = 270.29	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.8925 (6) Å	µ = 0.09 mm⁻¹
b = 15.964 (2) Å	T = 295 K
c = 10.8353 (14) Å	0.4 × 0.2 × 0.1 mm
β = 94.461 (13)°

Data collection top

Bruker P4 diffractometer	767 reflections with I > 2σ(I)
Absorption correction: multi-scan (XSCANS; Siemens, 1995)	R_int = 0.028
T_min = 0.741, T_max = 0.762	3 standard reflections every 97 reflections
1867 measured reflections	intensity decay: none
1190 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.01	Δρ_max = 0.14 e Å⁻³
1190 reflections	Δρ_min = −0.12 e Å⁻³
93 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)
O	0.2331 (4)	0.50956 (7)	0.86392 (12)	0.0677 (5)
N1	0.4420 (4)	0.25146 (8)	0.92913 (12)	0.0454 (4)
N2	0.4631 (4)	0.39274 (9)	0.95953 (12)	0.0487 (5)
H2A	0.5892	0.3784	1.0248	0.058*
C1	0.4561 (6)	0.10020 (12)	0.92021 (19)	0.0675 (6)
H1A	0.6045	0.1096	0.9939	0.101*	0.50
H1B	0.5773	0.0685	0.8621	0.101*	0.50
H1C	0.2560	0.0696	0.9407	0.101*	0.50
H1D	0.3540	0.0556	0.8706	0.101*	0.50
H1E	0.3812	0.0967	1.0024	0.101*	0.50
H1F	0.7025	0.0955	0.9237	0.101*	0.50
C2	0.3474 (5)	0.18289 (10)	0.86378 (16)	0.0482 (5)
C3	0.1571 (5)	0.18820 (12)	0.75053 (17)	0.0548 (6)
H3A	0.0947	0.1399	0.7064	0.066*
C4	0.0617 (5)	0.26555 (11)	0.70415 (17)	0.0552 (6)
H4A	−0.0665	0.2698	0.6283	0.066*
C5	0.1561 (5)	0.33684 (12)	0.77004 (15)	0.0489 (5)
H5A	0.0949	0.3899	0.7405	0.059*
C6	0.3460 (5)	0.32573 (10)	0.88206 (15)	0.0421 (5)
C7	0.4079 (5)	0.47496 (11)	0.94694 (16)	0.0460 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O	0.0921 (11)	0.0427 (8)	0.0626 (9)	0.0079 (7)	−0.0296 (8)	0.0000 (6)
N1	0.0530 (10)	0.0360 (9)	0.0464 (9)	0.0001 (8)	−0.0011 (7)	−0.0017 (7)
N2	0.0639 (11)	0.0342 (9)	0.0452 (8)	0.0019 (8)	−0.0138 (7)	−0.0021 (7)
C1	0.0770 (16)	0.0412 (12)	0.0839 (14)	0.0009 (11)	0.0040 (12)	−0.0021 (10)
C2	0.0500 (12)	0.0391 (10)	0.0562 (11)	−0.0025 (9)	0.0076 (9)	−0.0051 (9)
C3	0.0605 (13)	0.0481 (12)	0.0558 (11)	−0.0083 (10)	0.0035 (10)	−0.0146 (9)
C4	0.0585 (13)	0.0594 (13)	0.0461 (10)	−0.0065 (11)	−0.0056 (9)	−0.0078 (9)
C5	0.0549 (12)	0.0467 (11)	0.0438 (9)	0.0028 (10)	−0.0052 (9)	0.0006 (9)
C6	0.0470 (11)	0.0371 (10)	0.0419 (9)	−0.0002 (9)	0.0016 (8)	−0.0026 (8)
C7	0.0551 (12)	0.0377 (11)	0.0441 (10)	0.0024 (9)	−0.0038 (9)	0.0005 (8)

Geometric parameters (Å, º) top

O—C7	1.217 (2)	C1—H1E	0.9600
N1—C6	1.333 (2)	C1—H1F	0.9600
N1—C2	1.340 (2)	C2—C3	1.386 (3)
N2—C7	1.335 (2)	C3—C4	1.373 (3)
N2—C6	1.413 (2)	C3—H3A	0.9300
N2—H2A	0.8600	C4—C5	1.378 (2)
C1—C2	1.502 (3)	C4—H4A	0.9300
C1—H1A	0.9600	C5—C6	1.383 (2)
C1—H1B	0.9600	C5—H5A	0.9300
C1—H1C	0.9600	C7—C7ⁱ	1.532 (3)
C1—H1D	0.9600

C6—N1—C2	117.86 (14)	H1C—C1—H1F	141.1
C7—N2—C6	129.90 (15)	H1D—C1—H1F	109.5
C7—N2—H2A	115.1	H1E—C1—H1F	109.5
C6—N2—H2A	115.1	N1—C2—C3	121.61 (16)
C2—C1—H1A	109.5	N1—C2—C1	116.48 (16)
C2—C1—H1B	109.5	C3—C2—C1	121.91 (16)
H1A—C1—H1B	109.5	C4—C3—C2	119.32 (17)
C2—C1—H1C	109.5	C4—C3—H3A	120.3
H1A—C1—H1C	109.5	C2—C3—H3A	120.3
H1B—C1—H1C	109.5	C3—C4—C5	119.96 (17)
C2—C1—H1D	109.5	C3—C4—H4A	120.0
H1A—C1—H1D	141.1	C5—C4—H4A	120.0
H1B—C1—H1D	56.3	C4—C5—C6	116.85 (16)
H1C—C1—H1D	56.3	C4—C5—H5A	121.6
C2—C1—H1E	109.5	C6—C5—H5A	121.6
H1A—C1—H1E	56.3	N1—C6—C5	124.40 (15)
H1B—C1—H1E	141.1	N1—C6—N2	112.23 (14)
H1C—C1—H1E	56.3	C5—C6—N2	123.37 (15)
H1D—C1—H1E	109.5	O—C7—N2	126.71 (17)
C2—C1—H1F	109.5	O—C7—C7ⁱ	121.3 (2)
H1A—C1—H1F	56.3	N2—C7—C7ⁱ	111.96 (19)
H1B—C1—H1F	56.3

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Oⁱ	0.86	2.24	2.6718 (18)	111

Symmetry code: (i) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₄N₄O₂
M_r	270.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	3.8925 (6), 15.964 (2), 10.8353 (14)
β (°)	94.461 (13)
V (Å³)	671.26 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.4 × 0.2 × 0.1

Data collection
Diffractometer	Bruker P4
Absorption correction	Multi-scan (XSCANS; Siemens, 1995)
T_min, T_max	0.741, 0.762
No. of measured, independent and observed [I > 2σ(I)] reflections	1867, 1190, 767
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.101, 1.01
No. of reflections	1190
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.12

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
N2—H2A···Oⁱ	0.86	2.24	2.6718 (18)	111.3

Symmetry code: (i) −x+1, −y+1, −z+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 the specific research fields in Chung-Yuan Christian University, Taiwan, under grant No. CYCU-98-CR—CH.

References

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
Siedel, M. C., Tuyle, G. C. V. & Weir, W. D. (1970). J. Org. Chem. 35, 1662–1664. 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

Volume 65| Part 11| November 2009| Page o2734

https://doi.org/10.1107/S1600536809040902

Open

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