N,N′-Bis(pyridin-2-yl)benzene-1,4-dicarboxamide

Tsai, T.-P.; Hsiao, H.-L.; Chen, J.-D.

doi:10.1107/S1600536810051172

organic compounds

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Volume 67| Part 1| January 2011| Page o63

https://doi.org/10.1107/S1600536810051172

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N,N′-Bis(pyridin-2-yl)benzene-1,4-dicarboxamide

Ta-Pin Tsai,^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 6 December 2010; accepted 6 December 2010; online 11 December 2010)

Molecules of the title compound, C₁₈H₁₄N₄O₂, are located around an inversion center and connected into chains in the crystal via intermolecular N—H⋯N hydrogen bonds generating an R₂²(8) motif.

Related literature

For N,N′-bis(pyridinyl) derivatives of 1,4-benzenedicarboxamide and their metal complexes, see: Tsai et al. (2010 ).

Experimental

Crystal data

C₁₈H₁₄N₄O₂
M_r = 318.33
Triclinic, $[P \overline 1]$
a = 5.7895 (4) Å
b = 7.8315 (6) Å
c = 8.8460 (5) Å
α = 82.906 (6)°
β = 74.083 (5)°
γ = 73.695 (6)°
V = 369.72 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.60 × 0.60 × 0.56 mm

Data collection

Siemens P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1995 ) T_min = 0.831, T_max = 0.851
1962 measured reflections
1787 independent reflections
1521 reflections with I > 2σ(I)
R_int = 0.013
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.112
S = 1.06
1787 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.86	2.34	3.1679 (15)	163
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: XSCANS (Siemens, 1995); cell refinement: XSCANS; data reduction: XSCANS and 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/S1600536810051172/gk2331sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051172/gk2331Isup2.hkl

checkCIF report

Comment top

Several Cu(II), Cd(II) and Hg(II) complexes containg N,N'-bis(2/3-aryl)-1,4-benzenedicarboxamide ligands have been reported, which show one-dimensional and two-dimensional structures (Tsai, et al., 2010). Within this project the crystal structure of the title compound was determined.

In its crystal structure intermolecular N—H···N hydrogen bonds are found (Tab. 1) and the molecule is located on a center of inversion (Fig. 1).

Related literature top

For N,N'-bis(pyridinyl) derivatives of 1,4-benzenedicarboxamide and their metal complexes, see: Tsai et al. (2010).

Experimental top

The title compound was prepared according to a published procedure (Tsai, et al., 2010). Block crystals suitable for X-ray crystallography were obtained by slow evaporization of the solvent from a solution of the title compound in methanol.

Structure description top

In its crystal structure intermolecular N—H···N hydrogen bonds are found (Tab. 1) and the molecule is located on a center of inversion (Fig. 1).

For N,N'-bis(pyridinyl) derivatives of 1,4-benzenedicarboxamide and their metal complexes, see: Tsai et al. (2010).

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 + 2,-y,-z.

N,N'-Bis(pyridin-2-yl)benzene-1,4-dicarboxamide top

Crystal data top

C₁₈H₁₄N₄O₂	Z = 1
M_r = 318.33	F(000) = 166
Triclinic, P1	D_x = 1.430 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.7895 (4) Å	Cell parameters from 50 reflections
b = 7.8315 (6) Å	θ = 4.8–15.0°
c = 8.8460 (5) Å	µ = 0.10 mm⁻¹
α = 82.906 (6)°	T = 298 K
β = 74.083 (5)°	Block, pale yellow
γ = 73.695 (6)°	0.60 × 0.60 × 0.56 mm
V = 369.72 (4) Å³

Data collection top

Bruker P4 diffractometer	1521 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.013
Graphite monochromator	θ_max = 28.0°, θ_min = 2.4°
ω scans	h = 0→7
Absorption correction: ψ scan (XSCANS; Siemens, 1995)	k = −9→10
T_min = 0.831, T_max = 0.851	l = −11→11
1962 measured reflections	3 standard reflections every 97 reflections
1787 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) = 0.112	w = 1/[σ²(F_o²) + (0.0468P)² + 0.1049P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1787 reflections	Δρ_max = 0.32 e Å⁻³
110 parameters	Δρ_min = −0.19 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: 0.193 (17)

Crystal data top

C₁₈H₁₄N₄O₂	γ = 73.695 (6)°
M_r = 318.33	V = 369.72 (4) Å³
Triclinic, P1	Z = 1
a = 5.7895 (4) Å	Mo Kα radiation
b = 7.8315 (6) Å	µ = 0.10 mm⁻¹
c = 8.8460 (5) Å	T = 298 K
α = 82.906 (6)°	0.60 × 0.60 × 0.56 mm
β = 74.083 (5)°

Data collection top

Bruker P4 diffractometer	1521 reflections with I > 2σ(I)
Absorption correction: ψ scan (XSCANS; Siemens, 1995)	R_int = 0.013
T_min = 0.831, T_max = 0.851	3 standard reflections every 97 reflections
1962 measured reflections	intensity decay: none
1787 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.112	H-atom parameters constrained
S = 1.06	Δρ_max = 0.32 e Å⁻³
1787 reflections	Δρ_min = −0.19 e Å⁻³
110 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
O	1.1101 (2)	0.21659 (16)	0.30550 (13)	0.0497 (3)
N1	0.7461 (2)	0.13586 (16)	0.41052 (13)	0.0369 (3)
H1A	0.6695	0.0611	0.3982	0.044*
N2	0.4263 (2)	0.20173 (15)	0.63054 (13)	0.0353 (3)
C1	0.6435 (2)	0.23152 (17)	0.54787 (14)	0.0316 (3)
C2	0.7512 (3)	0.35023 (19)	0.59089 (16)	0.0393 (3)
H2B	0.9066	0.3632	0.5336	0.047*
C3	0.6200 (3)	0.4479 (2)	0.72110 (18)	0.0434 (4)
H3A	0.6853	0.5296	0.7523	0.052*
C4	0.3907 (3)	0.42384 (19)	0.80528 (17)	0.0422 (3)
H4A	0.2982	0.4900	0.8924	0.051*
C5	0.3035 (3)	0.29915 (19)	0.75631 (16)	0.0381 (3)
H5A	0.1507	0.2816	0.8138	0.046*
C6	0.9524 (2)	0.14708 (17)	0.29436 (15)	0.0322 (3)
C7	0.9716 (2)	0.06764 (16)	0.14401 (14)	0.0290 (3)
C8	1.2030 (2)	−0.03051 (17)	0.06322 (14)	0.0314 (3)
H8A	1.3391	−0.0509	0.1057	0.038*
C9	1.2324 (2)	−0.09833 (17)	−0.08032 (15)	0.0321 (3)
H9A	1.3876	−0.1641	−0.1340	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O	0.0418 (6)	0.0697 (7)	0.0464 (6)	−0.0318 (5)	−0.0005 (5)	−0.0194 (5)
N1	0.0417 (6)	0.0460 (6)	0.0291 (5)	−0.0261 (5)	−0.0008 (5)	−0.0092 (5)
N2	0.0366 (6)	0.0411 (6)	0.0302 (5)	−0.0166 (5)	−0.0041 (4)	−0.0045 (4)
C1	0.0368 (6)	0.0353 (6)	0.0256 (6)	−0.0148 (5)	−0.0065 (5)	−0.0023 (5)
C2	0.0426 (7)	0.0445 (8)	0.0364 (7)	−0.0224 (6)	−0.0055 (6)	−0.0067 (6)
C3	0.0532 (9)	0.0383 (7)	0.0443 (8)	−0.0182 (6)	−0.0115 (7)	−0.0100 (6)
C4	0.0491 (8)	0.0360 (7)	0.0382 (7)	−0.0074 (6)	−0.0055 (6)	−0.0110 (5)
C5	0.0360 (7)	0.0401 (7)	0.0353 (7)	−0.0101 (6)	−0.0029 (5)	−0.0041 (5)
C6	0.0332 (6)	0.0359 (6)	0.0298 (6)	−0.0144 (5)	−0.0052 (5)	−0.0039 (5)
C7	0.0300 (6)	0.0323 (6)	0.0259 (6)	−0.0139 (5)	−0.0030 (4)	−0.0015 (4)
C8	0.0267 (6)	0.0384 (7)	0.0308 (6)	−0.0119 (5)	−0.0068 (5)	−0.0011 (5)
C9	0.0263 (6)	0.0359 (6)	0.0320 (6)	−0.0084 (5)	−0.0020 (5)	−0.0057 (5)

Geometric parameters (Å, º) top

O—C6	1.2169 (16)	C4—C5	1.377 (2)
N1—C6	1.3614 (16)	C4—H4A	0.9300
N1—C1	1.4034 (16)	C5—H5A	0.9300
N1—H1A	0.8600	C6—C7	1.5009 (17)
N2—C1	1.3375 (17)	C7—C8	1.3888 (17)
N2—C5	1.3403 (17)	C7—C9ⁱ	1.3936 (17)
C1—C2	1.3932 (18)	C8—C9	1.3860 (17)
C2—C3	1.378 (2)	C8—H8A	0.9300
C2—H2B	0.9300	C9—C7ⁱ	1.3936 (17)
C3—C4	1.384 (2)	C9—H9A	0.9300
C3—H3A	0.9300

C6—N1—C1	127.85 (11)	N2—C5—C4	123.77 (13)
C6—N1—H1A	116.1	N2—C5—H5A	118.1
C1—N1—H1A	116.1	C4—C5—H5A	118.1
C1—N2—C5	117.11 (11)	O—C6—N1	124.94 (12)
N2—C1—C2	123.38 (12)	O—C6—C7	120.89 (11)
N2—C1—N1	112.88 (11)	N1—C6—C7	114.16 (11)
C2—C1—N1	123.70 (12)	C8—C7—C9ⁱ	119.81 (11)
C3—C2—C1	117.84 (13)	C8—C7—C6	118.37 (11)
C3—C2—H2B	121.1	C9ⁱ—C7—C6	121.72 (11)
C1—C2—H2B	121.1	C9—C8—C7	120.42 (12)
C2—C3—C4	119.75 (13)	C9—C8—H8A	119.8
C2—C3—H3A	120.1	C7—C8—H8A	119.8
C4—C3—H3A	120.1	C8—C9—C7ⁱ	119.77 (11)
C5—C4—C3	118.06 (13)	C8—C9—H9A	120.1
C5—C4—H4A	121.0	C7ⁱ—C9—H9A	120.1
C3—C4—H4A	121.0

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱⁱ	0.86	2.34	3.1679 (15)	163

Symmetry code: (ii) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₄N₄O₂
M_r	318.33
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	5.7895 (4), 7.8315 (6), 8.8460 (5)
α, β, γ (°)	82.906 (6), 74.083 (5), 73.695 (6)
V (Å³)	369.72 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.60 × 0.60 × 0.56

Data collection
Diffractometer	Bruker P4
Absorption correction	ψ scan (XSCANS; Siemens, 1995)
T_min, T_max	0.831, 0.851
No. of measured, independent and observed [I > 2σ(I)] reflections	1962, 1787, 1521
R_int	0.013
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.112, 1.06
No. of reflections	1787
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.19

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···N2ⁱ	0.86	2.34	3.1679 (15)	163

Symmetry code: (i) −x+1, −y, −z+1.

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

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
Tsai, T.-P., Huang, Y.-T., Ray, U., Chang, Y.-J., Cheng, P.-C., Wu, C.-J., Chen, J.-D. & Wang, J. C. (2010). Polyhedron, pp. 3081–3088. Web of Science CSD CrossRef Google Scholar