N,N′-[2,2′-(Phenyl­aza­nedi­yl)bis­(ethane-2,1-di­yl)]dipicolinamide

Gao-Nan Li; Zhi-Gang Niu; Mei-Qi Huang; Ying Zou; Liang-Jiang Hu

doi:10.1107/S1600536813008696

. 2013 Apr 10;69(Pt 5):o677. doi: 10.1107/S1600536813008696

N,N′-[2,2′-(Phenylazanediyl)bis(ethane-2,1-diyl)]dipicolinamide

Gao-Nan Li ^a,^*, Zhi-Gang Niu ^a, Mei-Qi Huang ^a, Ying Zou ^a, Liang-Jiang Hu ^a

PMCID: PMC3647871 PMID: 23723837

Abstract

The asymmetric unit of the title compound, C₂₂H₂₃N₅O₂, contains two independent molecules with similar conformations; the terminal pyridine rings are oriented at dihedral angles of 23.99 (8) and 18.07 (8)° with respect to the central benzene ring in one molecule and 28.99 (8) and 23.22 (8)° in the other. In the crystal, N—H⋯O and weak C—H⋯O hydrogen bonds link the molecules into a three-dimensional supramolecular structure. Weak intermolecular C—H⋯π interactions are also observed in the crystal.

Related literature

For background to bis(pyridinecarboxamide) derivatives, see: Cornman et al. (1999 ▶); Song et al. (2010 ▶); Singh et al. (2008 ▶). For the synthesis, see: Jain et al. (2004 ▶); Lee et al. (2006 ▶); Barnes et al. (1978 ▶). For related structures, see: Adolph et al. (2012 ▶); Munro & Wilson (2010 ▶); Yan et al. (2012 ▶). graphic file with name e-69-0o677-scheme1.jpg

Experimental

Crystal data

C₂₂H₂₃N₅O₂
M _r = 389.45
Monoclinic,
a = 8.64349 (7) Å
b = 24.8210 (3) Å
c = 18.40861 (18) Å
β = 90.5648 (8)°
V = 3949.20 (7) Å³
Z = 8
Cu Kα radiation
μ = 0.70 mm⁻¹
T = 100 K
0.12 × 0.08 × 0.07 mm

Data collection

Agilent Xcalibur Atlas Gemini ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.886, T _max = 0.950
28468 measured reflections
7050 independent reflections
6128 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.097
S = 1.14
7050 reflections
523 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ▶).

Supplementary Material

Click here for additional data file.^{(28.6KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813008696/xu5691sup1.cif

e-69-0o677-sup1.cif^{(28.6KB, cif)}

Click here for additional data file.^{(345KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008696/xu5691Isup2.hkl

e-69-0o677-Isup2.hkl^{(345KB, hkl)}

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

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

Cg5 and Cg6 are the centroids of the C9–C14 benzene and C31–C36 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3	0.86	2.44	3.1099 (18)	135
N7—H7⋯O1ⁱ	0.86	2.42	3.0998 (18)	136
C24—H24⋯O2ⁱⁱ	0.93	2.48	3.311 (2)	149
C25—H25⋯O4ⁱⁱⁱ	0.93	2.54	3.213 (2)	129
C8—H8A⋯Cg6^iv	0.97	2.72	3.6468 (18)	161
C30—H30B⋯Cg5^v	0.97	2.74	3.6584 (18)	159

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

This work was supported financially by the Natural Science Foundation of Hainan Province, China (grant 212014) and the Scientific Research Foundation of Hainan Normal University.

supplementary crystallographic information

Comment

Bis(2-pyridinecarboxamide) derivatives comprise a large group of organic compounds that are ideal for the mono- or dinuclear chelation of metal ions (Cornman et al., 1999; Song et al., 2010; Singh et al., 2008). In order to explore coordination chemistry of bis(pyridinecarboxamide) ligands, we have synthesized the title compound (I) and report here its crystal structure.

The asymmetric unit of the title compound (I), C₂₂H₂₃N₅O₂, contains two independent molecules with the similar structure, two terminal pyridine rings are oriented with respect to the central benzene ring at 23.99 (8) and 18.07 (8)° in one molecule and at 28.99 (8) and 23.22 (8)° in the other (Fig. 1). Every independent molecule contains two symmetrical N-ethyl(pyridine-2-carboxiamide) moieties linked by a phenylamino bridge. It is noteworthy that the C═O bonds are oriented trans to the pyridine nitrogen atom, which are in accord with those reported for previous structures (Munro et al., 2010; Yan et al., 2012). In the crystal, intermolecular N–H···O (Fig. 2) and weak C—H···O hydrogen bonds (Fig. 3) link the molecules into the three-dimensional supramolecular structure. The crystal packing exhibits also weak intermolecular C–H···π interaction, proved by short distance C30–H30B···Cg5 [3.6584 (18) Å] and C8–H8A···Cg6 [3.6468 (18) Å], where Cg5 and Cg6 are the centroids of the C9–benzene and C31–benzene rings, respectively [symmetry code: (iv) x+1/2, –y+1/2, z+1/2; (v) x–1/2, –y+1/2, z–1/2] (Table 1).

Experimental

N-(3-Dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (EDCI, 375 mg, 1.95 mmol) and hydroxybenzotriazole (HOBt, 440 mg, 3.26 mmol) were added to a solution of picolinic acid (200 mg, 1.62 mmol) in dry DMF (10 ml) at room temperature. After the mixture was stirred for 30 min, N¹-(2-aminoethyl)-N¹-phenylethane-1,2-diamine (133 mg, 0.74 mmol) was added (Lee et al., 2006). The reaction mixture was stirred overnight under N₂ atmosphere. H₂O (30 ml) was added to quench the reaction, and the mixture was extracted with ethyl acetate (3×20 ml). The combined organic phase was washed with brine, dried over Na₂SO₄, filtrated and concentrated in vacuum. The residue was purified by column chromatography (PE:EA = 2:1~1:2) to give compound (I) (264 mg, yield: 91.8%) as a white solid. Colorless single crystals suitable for X-ray structural analysis were obtained by slow evaporation of a mixture solution of dichloromethane and methanol at room temperature. ¹H NMR (400 MHz, CDCl₃): 3.48~3.61 (m, 8H), 6.62 (t, J = 8.0 Hz, 1H), 6.85 (d, J = 7.2 Hz, 2H), 7.15 (t, J = 8.0 Hz, 2H), 7.28~7.32 (m, 2H), 7.73 (t, J = 8.0 Hz, 2H), 8.09 (d, J = 7.2 Hz, 2H), 8.30~8.40 (m, 4H).