3,3′-Bis(quinolin-8-yl)-1,1′-[4,4′-methyl­enebis(4,1-phenyl­ene)]diurea

Avijit Pramanik; Tiffany H Russ; Douglas R Powell; Md Alamgir Hossain

doi:10.1107/S1600536811053220

. 2011 Dec 17;68(Pt 1):o158–o159. doi: 10.1107/S1600536811053220

3,3′-Bis(quinolin-8-yl)-1,1′-[4,4′-methylenebis(4,1-phenylene)]diurea

Avijit Pramanik ^a, Tiffany H Russ ^a, Douglas R Powell ^b, Md Alamgir Hossain ^a,^*

PMCID: PMC3254500 PMID: 22259443

Abstract

The title compound, C₃₃H₂₆N₆O₂, contains two 3-(quinolin-8-yl)urea groups linked to a diphenylmethane. The asymmetric unit contains two molecules, A and B. Each quinoline plane is essentially parallel to the attached urea unit [dihedral angles = 8.97 (18) and 8.81 (19) in molecule A and 18.47 (18) and 4.09 (19)° in molecule B]. The two benzene rings are twisted, making dihedral angles of 81.36 (8)° in A and 87.20 (9)° in B. The molecular structures are stabilized by intramolecular N—H⋯N hydrogen bonds. In the crystal, each urea O atom is involved in two N—H⋯O hydrogen bonds, generating two interpenetrating three-dimensional sets of molecules.

Related literature

For general background to urea-based compounds in supramolecular chemistry, see: Fan et al. (1993 ▶); Smith et al. (1992 ▶); Pramanik et al. (2011 ▶); Caltagirone et al. (2008 ▶); Custelcean et al. (2005 ▶). For related structures, see: Wu et al. (2008 ▶); Saeed et al. (2010 ▶).

Experimental

Crystal data

C₃₃H₂₆N₆O₂
M _r = 538.60
Tetragonal,
a = 18.1345 (6) Å
c = 17.1405 (11) Å
V = 5636.8 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.35 × 0.34 × 0.34 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.972, T _max = 0.973
65350 measured reflections
5737 independent reflections
4589 reflections with I > 2σ(I)
R _int = 0.104

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.104
S = 1.00
5737 reflections
767 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811053220/rk2320sup1.cif

e-68-0o158-sup1.cif^{(59.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053220/rk2320Isup2.hkl

e-68-0o158-Isup2.hkl^{(280.9KB, 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
N11A—H11A⋯N1A	0.74 (4)	2.27 (4)	2.625 (4)	110 (3)
N11A—H11A⋯O13Aⁱ	0.74 (4)	2.41 (4)	3.101 (3)	155 (4)
N14A—H14A⋯O13Aⁱ	0.86 (4)	1.97 (4)	2.810 (4)	166 (3)
N28A—H28A⋯O30Aⁱⁱ	0.78 (4)	2.05 (4)	2.827 (4)	170 (4)
N31A—H31A⋯O30Aⁱⁱ	0.88 (4)	2.56 (4)	3.293 (4)	141 (3)
N31A—H31A⋯N39A	0.88 (4)	2.14 (4)	2.635 (4)	114 (3)
N11B—H11B⋯N1B	0.90 (4)	2.13 (4)	2.645 (4)	116 (3)
N11B—H11B⋯O30Bⁱⁱⁱ	0.90 (4)	2.46 (4)	3.172 (4)	136 (3)
N14B—H14B⋯O30Bⁱⁱⁱ	0.80 (3)	1.98 (4)	2.772 (4)	167 (3)
N28B—H28B⋯O13B^iv	0.87 (4)	1.94 (4)	2.786 (4)	161 (4)
N31B—H31B⋯O13B^iv	0.90 (4)	2.36 (3)	3.115 (4)	141 (3)
N31B—H31B⋯N39B	0.90 (4)	2.14 (3)	2.647 (4)	115 (3)

Open in a new tab

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

Acknowledgments

The National Science Foundation is acknowledged for a CAREER award (CHE-1056927) to MAH. The work was supported by the National Institute of Health (G12RR013459). The NMR instrument used for this work was funded by the National Science Foundation (CHE-0821357).

supplementary crystallographic information

Comment

In supramolecular chemistry, urea-based compounds are known to effectively bind anions in which a urea group acts as H-bond donors. For examples, acyclic urea hosts containing one or two binding sites were able to form complexes with phosphonates, sulfates and carboxylates in CHCl₃ (Smith et al., 1992) or acetate and glutarate in DMSO (Fan et al., 1993). Tren-based urea receptors with three urea units were recently reported showing high affinity and selectivity for various inorganic anions (Custelcean et al., 2005; Wu et al., 2008; Caltagirone et al., 2008). In an earlier paper, we reported a seven-coordinated hydrogen sulfate formed with three tren-based ureas via six NH···O bonds (d_N···O = 2.85-3.09Å) and one OH···O bond (d_O···O = 2.57Å) (Pramanik et al., 2011). In an effort to design selective receptors with a rigid framework, we synthesized a dipodal receptor consisting of a diphenylmethane linked with two quinoline groups. The title bis-urea compound contains two urea binding sites that could be an effective receptor for binding of variety of anions.

The bis-urea receptor crystallized in the tetragonal space group P4₃ with two molecules (Fig. 1) in the asymmetric unit. The asymmetric unit contains two molecules - A and B. As shown in Fig. 1, the two carbonyls of the two urea fragments of each molecule are oriented in the same direction. Two phenyl rings are twisted giving dihedral angles of 81.36 (8)° for A and 87.20 (9)° for B. Each pyridine nitrogen of the quinoline groups is involved in strong intramolecular hydrogen bonding with one NH group with N···N distances ranging from 2.625 (4)Å to 2.647 (4)Å. Each quinoline plane is nearly parallel with the attached urea group. There was no intermolecular hydrogen bonding between the two molecules. Each oxygen atom is bonded with two intermolecular NH···O hydrogen bonds with N···O distances ranging from 2.772 (4)Å to 3.293 (4)Å. Similar H-bonding interactions were observed in a related bis urea receptor (Saeed et al., 2010). In the extended structure viewed along the c axis, quinoline planes are found to be antiparallel (Fig. 2). No π···π stacking was observed between the aromatic groups.

Experimental

Synthesis of 1: 4,4'-methylenebis(phenylisocyanate) (500 mg, 1.99 mmol) was reacted with 8-aminoquinoline (576 mg, 3.99 mmol) in dichloromethane (500 ml) at room temperature under constant stirring. The mixture was refluxed for 5 h. A white precipitate was formed which collected by filtration. The precipitate washed by dichloromethane in several times and dried under vacuum to give a white solid (1.022 g, 95% yield). δ_H (500 MHz; DMSO-d₆) 9.80 (2H, s, Ar–NH), 9.66 (2H, s, Ar–NH), 8.91 (2H, d, J = 4.15 Hz, ArH), 8.54 (2H, dd, J1 = 3.1 Hz, J2 = 3.25 Hz, J3 = 3.55 Hz, ArH), 8.38 (2H, d, J = 8.25 Hz, ArH), 7.62 (2H, dd, J1 = 4.15 Hz, J2 = 3.95 Hz, J3 = 4.2 Hz, ArH) 7.55 (2H, d, J = 2 Hz, ArH), 7.54 (2H, d, J = 0.55 Hz, ArH), 7.41 (4H, d, J = 7.6 Hz, ArH), 7.15 (2H, d, J = 5.75 Hz, ArH) 3.84 (4H, s, αH). δ_C (125 MHz; DMSO-d₆₎δ 152.4 (CO), 148.3 (CAr), 137.744 (CHAr), 137.7 (CHAr), 136.616 (CHAr), 135.9 (CHAr), 135.1 (CHAr), 129.0 (CHAr), 127.907 (CHAr), 127.2 (CHAr), 122.018 (CHAr), 119.7 (CHAr), 118.3 (CHAr), 114.3 (CHAr). ESI-MS(+ve): m/z 539.2 (MH⁺).