N,N′-p-Phenyl­enediisonicotinamide monohydrate

Li Song; Wenxiang Chai; Junwei Lan

doi:10.1107/S1600536809024684

. 2009 Jul 4;65(Pt 8):o1749. doi: 10.1107/S1600536809024684

N,N′-p-Phenylenediisonicotinamide monohydrate

Li Song ^a,^*, Wenxiang Chai ^b, Junwei Lan ^a

PMCID: PMC2977464 PMID: 21583460

Abstract

The organic molecule of the title compound, C₁₈H₁₄N₄O₂·H₂O, lies on a center of inversion located at the centre of the central phenylene ring. There are two half-molecules in the asymmetric unit. In the crystal, the molecules are linked through by N—H⋯O and O—H⋯N hydrogen bonds involving the water molecule, forming a layer structure. The layers interact by π–π interactions between the aromatic rings.

Related literature

For background to N,N′-p-phenylenediisonicotinamide complexes, see: Burchell et al. (2003 ▶, 2004 ▶); Niu et al. (2004 ▶); Pansanel et al. (2006 ▶).

Experimental

Crystal data

C₁₈H₁₄N₄O₂·H₂O
M _r = 336.35
Triclinic,
a = 6.9936 (14) Å
b = 10.852 (2) Å
c = 11.285 (2) Å
α = 95.98 (3)°
β = 106.36 (3)°
γ = 94.68 (3)°
V = 811.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.32 × 0.21 × 0.13 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (CrystalStructure; Rigaku/MSC, 2004 ▶) T _min = 0.976, T _max = 0.987
7994 measured reflections
3671 independent reflections
1782 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.163
S = 1.10
3671 reflections
235 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809024684/ng2603sup1.cif

e-65-o1749-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024684/ng2603Isup2.hkl

e-65-o1749-Isup2.hkl^{(180KB, hkl)}

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—H2A⋯O3ⁱ	0.88	2.00	2.847 (3)	160
N4—H4A⋯O1	0.88	2.12	2.968 (3)	161
O3—H15⋯N1	0.94 (4)	1.92 (4)	2.845 (3)	168 (3)
O3—H16⋯N3ⁱⁱ	0.87 (4)	2.01 (4)	2.849 (3)	162 (4)

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

We are grateful for financial support from the Scientific Research Fund of Zhejiang Provincial Education Department (grant No. 20070358), the Analysis and Testing Foundation of Zhejiang Province (grant Nos. 2008F70034 and 2008F70053), the National Natural Science Foundation of China (grant No. 20803070) and the Young Scientists Fund of the Key Laboratory of Advanced Textile Materials and Manufacturing Technology of the Ministry of Education (grant No. 2007QN01).

supplementary crystallographic information

Comment

The incorporation of amide groups into organic ligands are of interests because of the existence of great and typical intermolecular hydrogen bondings. Furthermore, the bridging bis(pyridyl) ligands are good donors for building metal-organic frameworks (MOFs). As one example of bis(pyridyl) ligands with amide groups, N,N'-(biphenyl-4,4'-diyl)diisonicotinamide has been very less studied. Only a few examples built upon N,N'-(biphenyl-4,4'-diyl)diisonicotinamide and Cu(II), Hg(I) salts have been reported. However, the crystal structure of the ligand, N,N'-(biphenyl-4,4'-diyl)diisonicotinamide, has not been described in detail. Herein, we report the crystal structure and characterization of the title compound N,N'-(biphenyl-4,4'-diyl)diisonicotinamide.

The compound crystallizes in triclinic form in the space group P-1. As shown in Figure 1, the title compound, C18H14N4O2.H2O, contains an N,N'-(biphenyl-4,4'-diyl)diisonicotinamide molecule and a water solvent molecule. The bond lengths of the two independent parts of the C18H14N4O2 molecule display slight differences. The two C=O bonds of the amide groups are 1.223 (3) Å and 1.232 (3) Å long respectively. Individual molecules are connected through intermolecular N—H···O=C hydrogen bonds between amide groups The H(4 A)···O(1) distance is 2.12 Å and the N(4)···O(1) distance is 2.968 (3) Å. The N(4)—H(4 A)···O(1) angle is 161.3 °.

As shown in Figure 2, The molecules and the solvent water molecules are connected through the O—H···N hydrogen bonds between the water molecules and the pyridine groups or the amide groups (N(2)···O(3) = 2.847 (3) Å, O(3)···N(1) = 2.845 (3) Å, O(3)···N(3) = 2.849 (3) Å) to form a layer. The hydrogen bond geometry is listed in table 1. The layers pack viaπ-π interactions among the phenyl rings (Figure 3).

Experimental

The synthesis of compound 1 was modified with reference to the literature methods (R. J. Puddephatt and H. W. Hou). Isonicotinic acid (4.924 g, 40.0 mmol) was refluxed in thionyl chloride (20 ml) for 4 h. Excess thionyl chloride was removed under vacuum leaving a colorless solid. The solid was suspended in tetrahydrofuran (80 ml) and then a solution of 1,4-phenylenediamine (1.622 g, 0.015 mol) in tetrahydrofuran (20 ml) was added. After 15 minutes of stirring, triethylamine (15.0 ml) was added. The solution was refluxed at 70 ?C for 6 h and cooled to room temperature. Removal of the excess solvents results in a great deal of light-yellow solid. A solution of K2CO3 (6.910 g, 50 mmol) in water (40 ml) was added into the solid. After 10 minutes of stirring, the white products were filtered, washed with water and ethanol. Yield: ca 82%. Well shaped colorless crystals were obtained by slow evaporation of DMF/THF solution. 1H NMR (400 MHz, DMSO): ¹H 7.781 (s, 4H), 7.879 (d, 4H), 8.786 (d, 4H), 10.527 (s, 2H). Anal. Calcd for C18H16N4O3: C 64.28, H 4.79, N 16.66. Found (%): C 64.12, H 4.91, N 16.78. IR (KBr pellet, cm^-1): 3329(s), 1647(s), 1611(m), 1593(sh), 1547(s), 1522(s), 1506(sh), 1485(w), 1413(m), 1321(m), 1276(w), 1219(w), 1066(w), 827(m), 756(w), 667(m).