N,N′-(Pyridine-2,6-di­yl)dibenzamide

Abstract

The mol­ecule of the title compound, C₁₉H₁₅N₃O₂, is completed by the application of crystallographic twofold symmetry, with the pyridine N atom lying on the rotation axis. The mol­ecular structure is approximately planar, the dihedral angle between the mean planes of the pyridine and benzene rings being 7.53 (11)°. In the crystal, N—H⋯O hydrogen bonds link the mol­ecules into a two-dimensional array perpendicular to the c axis.

Related literature  

For metal complexes of carboxamide ligands, see: Adolph et al. (2012 ▶); Amiri et al. (2009 ▶).

Experimental  

Crystal data  

• C₁₉H₁₅N₃O₂

• M _r = 317.34

• Tetragonal,

• a = 5.0314 (1) Å

• c = 58.701 (3) Å

• V = 1486.02 (8) ų

• Z = 4

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 100 K

• 0.21 × 0.09 × 0.02 mm

Data collection  

• Oxford Diffraction Xcalibur Opal diffractometer

• Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.986, T _max = 1.000

• 1298 measured reflections

• 16463 independent reflections

• 1168 reflections with I > 2σ(I)

• R _int = 0.065

Refinement  

• R[F ² > 2σ(F ²)] = 0.044

• wR(F ²) = 0.090

• S = 1.23

• 1298 reflections

• 112 parameters

• H-atom parameters constrained

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.16 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: WinGX (Farrugia, 2012 ▶) and DIAMOND (Brandenburg & Putz, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1i	0.86	2.25	3.030 (2)	151

Symmetry code: (i) .

supplementary crystallographic information

Comment

Carboxamides are compounds which are prepared by the reaction of amines and acylhalides. They are important N,O-donor ligands and have widespread applications in fields such as in coordination chemistry (Adolph et al. 2012 & Amiri et al. 2009). As biologically active compounds, carboxamides find application in the treatment of diseases such as cancer, rheumatic disorders and inhibitors of calpain (calcium dependant cysteine proteases).

The molecular structure of the title compound is shown in Fig. 1. The molecule is approximately planar with the dihedral angle between the mean planes of the pyridine and benzene rings being 7.53 (11)°. Intermolecular N—H···O hydrogen bonds, with the carbonyl-O atoms acting as acceptors, link molecules into a two-dimensional array perpendicular to the c axis as illustrated in Fig. 2.

Experimental

All reagents were commercially available and used as received. To a magnetically stirred solution of 2,6-diaminopyridine (0.109 g, 1 mmol) and triethylamine (0.277 ml, 2 mmol) in dichloromethane (5 ml) was added drop-wise a mixture of benzoyl chloride (0.232 ml, 2 mmol) in dichloromethane (2 ml) at -10 °C over 15 min. The mixture was allowed to warm to room temperature and stirred for 48 h at room temperature. The solvent was removed under reduced pressure and the residue was purified by flash column chromatography (silica gel; petroleum ether-ethyl acetate) to give the title compound as a yellow powder. Crystals of the title compound were obtained from its methanol solution by slow solvent evaporation. Yield: 85%. Melting point: 407–408 K. Selected IR (KBr, cm^-1): 3245 (N—H), 3061 (C—H), 1653 (C═O_amide), 1584 (C═N), 1461 (C═C).

Refinement

The hydrogen atom of the N—H group was positioned geometrically and refined as a riding atoms with N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(N). The C—H hydrogen atoms were positioned geometrically and refined as riding atoms with C—H = 0.93 Å, and with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

Molecular structure of the title compound showing displacement ellipsoids at the 50% probability level. The molecule has twofold symmetry and the unlabelled atoms are related by the symmetry operation y, x, -z.

Fig. 2.

Hydrogen bonding in the title compound leading to supramolecular layers in the ab plane. The green dashed lines indicate N—H···O hydrogen bonds.

Crystal data

C19H15N3O2	Dx = 1.418 Mg m−3
Mr = 317.34	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P41212	Cell parameters from 3266 reflections
Hall symbol: P 4abw 2nw	θ = 1.7–28.5°
a = 5.0314 (1) Å	µ = 0.10 mm−1
c = 58.701 (3) Å	T = 100 K
V = 1486.02 (8) Å3	Block, yellow
Z = 4	0.21 × 0.09 × 0.02 mm
F(000) = 664

Data collection

Oxford Diffraction Xcalibur Opal diffractometer	1298 independent reflections
Radiation source: fine-focus sealed tube	1168 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
Detector resolution: 8.4441 pixels mm-1	θmax = 24.9°, θmin = 2.8°
ω scan	h = 0→5
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010)	k = 0→4
Tmin = 0.986, Tmax = 1.000	l = −64→68
16463 measured reflections

Refinement

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)] = 0.044	H-atom parameters constrained
wR(F2) = 0.090	w = 1/[σ2(Fo2) + (0.P)2 + 0.9748P] where P = (Fo2 + 2Fc2)/3
S = 1.23	(Δ/σ)max < 0.001
1298 reflections	Δρmax = 0.18 e Å−3
112 parameters	Δρmin = −0.16 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: 0.0091 (16)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.3618 (3)	0.6195 (3)	0.04884 (3)	0.0204 (4)
N1	0.8073 (4)	0.8073 (4)	0.0000	0.0135 (6)
N2	0.9407 (4)	0.6428 (4)	0.03476 (3)	0.0143 (5)
H2	0.7819	0.5819	0.0362	0.017*
C7	1.0307 (5)	0.3655 (5)	0.06778 (4)	0.0144 (5)
C5	0.9853 (5)	0.8265 (5)	0.01690 (3)	0.0138 (5)
C8	0.8160 (5)	0.1943 (5)	0.06481 (4)	0.0171 (5)
H8	0.7180	0.1997	0.0514	0.020*
C3	1.1969 (5)	1.1969 (5)	0.0000	0.0159 (7)
H3	1.3276	1.3276	0.0000	0.019*
C6	1.1258 (5)	0.5538 (5)	0.04983 (4)	0.0143 (5)
C12	1.1738 (5)	0.3566 (5)	0.08806 (4)	0.0168 (5)
H12	1.3187	0.4690	0.0901	0.020*
C4	1.1857 (5)	1.0149 (5)	0.01758 (4)	0.0154 (5)
H4	1.3082	1.0188	0.0294	0.018*
C11	1.1026 (5)	0.1821 (5)	0.10523 (4)	0.0210 (6)
H11	1.1967	0.1802	0.1189	0.025*
C9	0.7480 (5)	0.0157 (5)	0.08184 (4)	0.0186 (6)
H9	0.6066	−0.1007	0.0797	0.022*
C10	0.8902 (5)	0.0100 (5)	0.10204 (4)	0.0200 (6)
H10	0.8434	−0.1091	0.1135	0.024*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0118 (9)	0.0265 (10)	0.0231 (9)	−0.0002 (7)	−0.0012 (7)	0.0046 (8)
N1	0.0144 (9)	0.0144 (9)	0.0118 (13)	0.0035 (12)	0.0000 (8)	0.0000 (8)
N2	0.0115 (11)	0.0178 (11)	0.0135 (9)	−0.0022 (9)	−0.0010 (8)	0.0016 (8)
C7	0.0149 (12)	0.0137 (12)	0.0147 (12)	0.0023 (10)	0.0005 (10)	−0.0025 (10)
C5	0.0164 (12)	0.0140 (13)	0.0110 (11)	0.0045 (10)	0.0008 (10)	−0.0007 (9)
C8	0.0165 (13)	0.0180 (13)	0.0167 (12)	0.0031 (11)	−0.0013 (10)	−0.0004 (10)
C3	0.0157 (11)	0.0157 (11)	0.0162 (17)	−0.0016 (14)	0.0011 (10)	−0.0011 (10)
C6	0.0175 (13)	0.0160 (13)	0.0094 (11)	0.0022 (10)	0.0003 (10)	−0.0033 (9)
C12	0.0197 (13)	0.0164 (13)	0.0143 (11)	−0.0016 (11)	−0.0006 (10)	−0.0013 (10)
C4	0.0144 (13)	0.0181 (13)	0.0136 (11)	0.0018 (10)	−0.0018 (10)	−0.0024 (10)
C11	0.0262 (14)	0.0210 (14)	0.0158 (12)	0.0011 (11)	−0.0039 (10)	0.0007 (11)
C9	0.0175 (13)	0.0173 (13)	0.0211 (12)	0.0003 (11)	0.0018 (11)	−0.0015 (10)
C10	0.0254 (14)	0.0162 (13)	0.0184 (12)	0.0024 (11)	0.0062 (11)	0.0038 (11)

Geometric parameters (Å, º)

O1—C6	1.234 (3)	C3—C4i	1.381 (3)
N1—C5	1.340 (3)	C3—C4	1.381 (3)
N1—C5i	1.340 (3)	C3—H3	0.9300
N2—C6	1.360 (3)	C12—C11	1.384 (3)
N2—C5	1.415 (3)	C12—H12	0.9300
N2—H2	0.8600	C4—H4	0.9300
C7—C12	1.392 (3)	C11—C10	1.388 (3)
C7—C8	1.393 (3)	C11—H11	0.9300
C7—C6	1.496 (3)	C9—C10	1.385 (3)
C5—C4	1.385 (3)	C9—H9	0.9300
C8—C9	1.387 (3)	C10—H10	0.9300
C8—H8	0.9300
C5—N1—C5i	116.9 (3)	O1—C6—C7	120.7 (2)
C6—N2—C5	126.0 (2)	N2—C6—C7	116.6 (2)
C6—N2—H2	117.0	C11—C12—C7	120.6 (2)
C5—N2—H2	117.0	C11—C12—H12	119.7
C12—C7—C8	119.2 (2)	C7—C12—H12	119.7
C12—C7—C6	117.2 (2)	C3—C4—C5	117.5 (2)
C8—C7—C6	123.5 (2)	C3—C4—H4	121.2
N1—C5—C4	123.9 (2)	C5—C4—H4	121.2
N1—C5—N2	113.3 (2)	C12—C11—C10	119.8 (2)
C4—C5—N2	122.8 (2)	C12—C11—H11	120.1
C9—C8—C7	120.1 (2)	C10—C11—H11	120.1
C9—C8—H8	119.9	C10—C9—C8	120.2 (2)
C7—C8—H8	119.9	C10—C9—H9	119.9
C4i—C3—C4	120.3 (3)	C8—C9—H9	119.9
C4i—C3—H3	119.9	C9—C10—C11	120.0 (2)
C4—C3—H3	119.9	C9—C10—H10	120.0
O1—C6—N2	122.7 (2)	C11—C10—H10	120.0
C5i—N1—C5—C4	−0.84 (17)	C8—C7—C6—N2	28.4 (3)
C5i—N1—C5—N2	176.1 (2)	C8—C7—C12—C11	−0.7 (4)
C6—N2—C5—N1	156.80 (19)	C6—C7—C12—C11	−178.2 (2)
C6—N2—C5—C4	−26.3 (3)	C4i—C3—C4—C5	−0.75 (15)
C12—C7—C8—C9	−0.6 (3)	N1—C5—C4—C3	1.6 (3)
C6—C7—C8—C9	176.7 (2)	N2—C5—C4—C3	−174.99 (17)
C5—N2—C6—O1	−2.8 (4)	C7—C12—C11—C10	1.5 (4)
C5—N2—C6—C7	178.16 (19)	C7—C8—C9—C10	1.2 (3)
C12—C7—C6—O1	26.8 (3)	C8—C9—C10—C11	−0.4 (4)
C8—C7—C6—O1	−150.6 (2)	C12—C11—C10—C9	−0.9 (4)
C12—C7—C6—N2	−154.2 (2)

Symmetry code: (i) y, x, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ii	0.86	2.25	3.030 (2)	151

Symmetry code: (ii) x−1, y, z.