1,1′-(Propane-1,3-di­yl)bis­(3-phenyl­urea)

Pramod Pansuriya; Hariska Naidu; Holger B Friedrich; Glenn E M Maguire

doi:10.1107/S1600536811035343

. 2011 Sep 3;67(Pt 10):o2552. doi: 10.1107/S1600536811035343

1,1′-(Propane-1,3-diyl)bis(3-phenylurea)

Pramod Pansuriya ^a, Hariska Naidu ^a, Holger B Friedrich ^a, Glenn E M Maguire ^a,^*

PMCID: PMC3201411 PMID: 22064870

Abstract

The title compound, C₁₇H₂₀N₄O₂, has crystallographic inversion symmetry. In the crystal structure, intermolecular hydrogen bonding between adjacent urea groups gives rise to infinite polymeric chains diagonally across the bc plane. With a centroid–centroid distance of 3.295 (2) Å, π–π stacking is present in the crystal along the same plane.

Related literature

For applications of ureas, see: Park et al. (2011 ▶); Ahmed et al. (2011 ▶); Sharma et al. (2010 ▶); Vos et al. (2010 ▶); Dawn et al. (2011 ▶). For related structures, see: Koevoets et al. (2005 ▶). graphic file with name e-67-o2552-scheme1.jpg

Experimental

Crystal data

C₁₇H₂₀N₄O₂
M _r = 312.37
Monoclinic,
a = 33.811 (7) Å
b = 4.598 (1) Å
c = 9.891 (2) Å
β = 98.957 (4)°
V = 1518.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.50 × 0.21 × 0.02 mm

Data collection

Bruker Kappa DUO APEXII diffractometer
Absorption correction: multi-scan (TWINABS; Sheldrick, 2007 ▶)T _min = 0.955, T _max = 0.998
1930 measured reflections
1930 independent reflections
1811 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.092
S = 1.05
1930 reflections
114 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811035343/hg5067sup1.cif

e-67-o2552-sup1.cif^{(14.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035343/hg5067Isup2.hkl

e-67-o2552-Isup2.hkl^{(95.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811035343/hg5067Isup3.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
N1—H1N⋯O1ⁱ	0.834 (18)	2.124 (18)	2.8742 (14)	149.7 (13)
N2—H2N⋯O1ⁱ	0.864 (18)	2.119 (18)	2.8904 (14)	148.4 (15)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors wish to thank Dr Hong Su from the the University of the Cape Town for his assistance with the data collection and refinement and the National Research Foundation c*change for support.

supplementary crystallographic information

Comment

Bis-ureas have been employed as ligands for metal complexes used in hydrolytic kinetic resolution of epoxides (Park et al., 2011) and as chromogenic and fluorogenic receptors (Ahmed et al., 2011). These molecules have also been found to be useful as epigenetic modulators (Sharma et al., 2010), in surfactant self-assembies (Vos et al., 2010), and photo dimerizing agent for coumarins (Dawn et al., 2011).

The closest reported structures are 3,3'-bis-phenyl-(butylene-1,4)-bisurea and 3,3'-bis-phenyl-(heptylene-1,7)-bisurea (Koevoets et al., 2005). In the butylene derivatives a transoid arrangement is evident whereas the heptylene molecule adopts a cisoid arrangement of the two urea groups. The title compound has an odd number of carbons in its aliphatic chain (propylene). This leads to a cisoid arrangement of the two urea groups (Fig. 1).

The asymmetric unit of the title compund, C₁₇H₂₀N₄O₂, contains half molecule of 1,1'-(propane-1,3-diyl)bis(3-phenylurea) and the complete molecule is generated by inversion symmetry (i) : 1-x, y, 1.5-z. Intermolecular hydrogen bonding between adjacent urea groups N1–H1–O1, 2.8742 (14) Å and N2–H2–O1, 2.8904 (14) Å gives rise to infinite polymeric chains across the bc plane (Fig. 2), The spacing between the two hydrogen-bonded urea groups is 4.59 Å in the title compound, while it is 4.64 Å for the even butylene spacer and 4.63 Å for the odd heptylene spacer. With a centroid distance of less than 3.5 Å, π-π stacking is present in the crystal along the same plane.

Experimental

A solution of phenyl isocyanate (6.76 g, 50 mmol) in diethylether (15 ml) was added dropwise at 15 °C to a vigorously stirred solution of anhydrous propane-1,3-diamine (7.41 g, 100 mmol) in isopropyl alcohol (100 ml) over a period of 30 min.The reaction mixture was stirred for 2 hrs at room temperature and quenched with water (200 ml). The reaction mixture was maintained overnight at room temperature. Then the reaction mixture was acidified with conc. HCl to pH 2.6. The solvents were evaporated under vacuum, the residue was suspended in hot water for 30 min and the resulting precipitate was filtered. The product was washed with ice cold water and dried. The yield was 2.70 g (40%).

Crystals suitable for single-crystal X-ray diffraction were grown in methanol: methylenechloride (1:2) at room temperature. M.p. = 504 K.