organic compounds
N,N′-(Pyridine-2,6-diyl)dibenzamide
aSama Technical and Vocational Training College, Islamic Azad University, Mamaghan Branch, Mamaghan, Iran, bDepartment of Chemistry, University of Zanjan, 45195-313 Zanjan, Iran, and cChemistry Department, The University of Warsaw, Pasteura 1, 02093 Warszawa, Poland
*Correspondence e-mail: nadernoshiranzadeh@yahoo.com
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
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Refinement
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Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell 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).
Supporting information
https://doi.org/10.1107/S1600536812050167/tk5180sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050167/tk5180Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812050167/tk5180Isup3.cml
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 ═Oamide), 1584 (C═N), 1461 (C═C).
(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 (CThe hydrogen atom of the N—H group was positioned geometrically and refined as a riding atoms with N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(N). The C—H hydrogen atoms were positioned geometrically and refined as riding atoms with C—H = 0.93 Å, and with Uiso(H) = 1.2Ueq(C).
Carboxamides are compounds which are prepared by the reaction of
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, 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.
For metal complexes of carboxamide ligands, see: Adolph et al. (2012); Amiri et al. (2009).
Data collection: CrysAlis CCD (Oxford Diffraction, 2010); cell
CrysAlis CCD (Oxford Diffraction, 2010); 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).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 |
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 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) |
C19H15N3O2 | Z = 4 |
Mr = 317.34 | Mo Kα radiation |
Tetragonal, P41212 | µ = 0.10 mm−1 |
a = 5.0314 (1) Å | T = 100 K |
c = 58.701 (3) Å | 0.21 × 0.09 × 0.02 mm |
V = 1486.02 (8) Å3 |
Oxford Diffraction Xcalibur Opal diffractometer | 1298 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010) | 1168 reflections with I > 2σ(I) |
Tmin = 0.986, Tmax = 1.000 | Rint = 0.065 |
16463 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.23 | Δρmax = 0.18 e Å−3 |
1298 reflections | Δρmin = −0.16 e Å−3 |
112 parameters |
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. |
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* |
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) |
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. |
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. |
Experimental details
Crystal data | |
Chemical formula | C19H15N3O2 |
Mr | 317.34 |
Crystal system, space group | Tetragonal, P41212 |
Temperature (K) | 100 |
a, c (Å) | 5.0314 (1), 58.701 (3) |
V (Å3) | 1486.02 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.21 × 0.09 × 0.02 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur Opal |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.986, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16463, 1298, 1168 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.593 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.090, 1.23 |
No. of reflections | 1298 |
No. of parameters | 112 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.16 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2010), CrysAlis RED (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 2012) and DIAMOND (Brandenburg & Putz, 2006), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1i | 0.86 | 2.25 | 3.030 (2) | 151.2 |
Symmetry code: (i) x−1, y, z. |
Footnotes
‡Additional correspondence author, e-mail: mahboubi_p@yahoo.com.
Acknowledgements
The authors are grateful to the University of Zanjan, Islamic Azad University (Mamagghan Branch) and the University of Warsaw for financial support.
References
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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.