N,N,N′,N′-Tetra­kis(pyridin-4-yl)methane­diamine monohydrate

Jong Won Shin; Kil Sik Min

doi:10.1107/S1600536812019010

. 2012 May 2;68(Pt 6):o1600. doi: 10.1107/S1600536812019010

N,N,N′,N′-Tetrakis(pyridin-4-yl)methanediamine monohydrate

Jong Won Shin ^a, Kil Sik Min ^b,^*

PMCID: PMC3379210 PMID: 22719408

Abstract

In the title compound, C₂₁H₁₈N₆·H₂O, two 4,4′-dipyridylamine groups are linked by a methylene C atom, which sits on a twofold axis. The lattice water molecule is located slightly off a twofold axis, and is therefore disordered over two positions. In the crystal, the organic molecules and the water molecule are linked by O—H⋯N hydrogen bonds. The organic molecules exhibit extensive offset face-to-face π–π interactions to symmetry equivalents [centroid–centroid distances = 3.725 (3) and 4.059 (3) Å].

Related literature

For metal-organic frameworks including 4,4′-dipyridylamine, see: Braverman & LaDuca (2007 ▶); Shyu et al. (2009 ▶). For the catalysis of multidimensional metal-organic frameworks, see: Welbes & Borovik (2005 ▶). For self-assembled metal-organic networks and their luminescent properties, see: Shin et al. (2012 ▶); Zeng et al. (2010 ▶).

Experimental

Crystal data

C₂₁H₁₈N₆·H₂O
M _r = 372.42
Monoclinic,
a = 13.9048 (11) Å
b = 13.7637 (11) Å
c = 10.0569 (8) Å
β = 109.142 (2)°
V = 1818.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 K
0.34 × 0.26 × 0.25 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.973, T _max = 0.978
6540 measured reflections
2241 independent reflections
1313 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.163
S = 1.09
2241 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812019010/pk2409sup1.cif

e-68-o1600-sup1.cif^{(15.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812019010/pk2409Isup2.hkl

e-68-o1600-Isup2.hkl^{(108KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812019010/pk2409Isup3.cml

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
O1—H1W⋯N2ⁱ	1.02	1.88	2.869 (2)	161

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Symmetry code: (i) Inline graphic .

Acknowledgments

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2010–0003672). The authors acknowledge the Korea Basic Science Institute for the X-ray data collection.

supplementary crystallographic information

Comment

Polypyridyl ligands have attracted considerable attention in materials science because they can be used for the construction of multidimensional metal-organic frameworks. These have potential applications in catalysis and as luminescent materials (Shin et al., 2012; Welbes & Borovik, 2005; Zeng et al., 2010). For example, as a building block, bis(4-pyridyl)amine (bpa) has been extensively used for self-assembly of multidimensional coordination polymers, because the ligand has significant functionalities, e.g. hydrogen bonding capability (Braverman & LaDuca, 2007; Shyu, et al., 2009). Thus, we have made a new ligand, N,N,N',N'-tetra-4-pyridyl-methylenediamine (TPMD), which can be used as a building unit for self-assembly of potential luminescent materials and catalysts. Here, we report the synthesis and crystal structure of N,N,N',N'-tetra-4-pyridyl-methylenediamine monohydrate.

The title compound in its crystalline state is centrosymmetric (Fig. 1). The dihedral angle between neighboring pyridyl rings is 63.74 (7)°, and the angle of N1—C11—N1(-x, y, 1.5 - z) is 114.5 (2)°. The water molecule appears to be slightly off a 2-fold axis, and was refined using a disordered model, which gave a lower R value and a flatter difference map compared to a non-disordered model. The crystal packing is stabilized by strong intermolecular O—H···N hydrogen bonds (Table 1) that connect pairs of organic molecules by water molecules into chains along the (101) direction (Fig. 2). The crystal is also stabilized by intermolecular offset face-to-face π-π interactions [centroid-centroid distances = 3.725 (3) Å (-x + 1/2, -y + 1/2, 2 - z) and 4.059 (3) Å (-x + 1/2, -y + 1/2, 1 - z)] (Fig. 3).

Experimental

The title compound was prepared as follows. NaH (0.561 g, 0.0234 mol) was added carefully to a DMF solution (50 ml) of 4,4'-dipyridylamine (2.00 g, 0.0117 mol) and stirred for 2 days at room temperature. To the mixture was added dropwise dichloromethane (20 ml) and the mixture solution was again stirred for 2 days, which resulted in a dark red solution. Then the mixture was quenched with H₂O (50 ml), and the organic layer was extracted with CHCl₃ (3 times, 100 ml). The extract was washed with NaCl solution to purify and then dried with Na₂SO₄. After removing the organic solvent, a pale yellow oil was obtained, from which colorless crystals formed in 1 day. The crystals were filtered and washed with n-hexane and acetonitrile. Yield: 0.86 g (42%). Anal. Calcd. for C₂₁H₂₀N₆O: C, 67.73; H, 5.41; N, 22.57. Found: C, 67.63; H, 5.23; N, 22.51. ¹H NMR (400 MHz, DMSO-d⁶, 300 K): δ = 8.35 (dd, J = 1.52, 1.52 Hz, 8 H), 6.91 (dd, J = 1.56, 1.60 Hz, 8 H), 5.95 (s, 2H). GC—MS: m/z = 354.1 (M⁺). IR (KBr, cm^-1): 3425, 3050, 3024, 1601, 1581, 1497, 1207, 1068, 850, 602.