Bis(2-{2-[2-(benzyl­carbamo­yl)phen­oxy]acetamido}­eth­yl)ammonium nitrate ethanol disolvate

Jiaji Liu; Xiaoliang Tang; Zhengdan Lu; Guolin Zhang; Weisheng Liu

doi:10.1107/S1600536810052670

. 2010 Dec 24;67(Pt 1):o203–o204. doi: 10.1107/S1600536810052670

Bis(2-{2-[2-(benzylcarbamoyl)phenoxy]acetamido}ethyl)ammonium nitrate ethanol disolvate

Jiaji Liu ^a, Xiaoliang Tang ^a, Zhengdan Lu ^a, Guolin Zhang ^a,^*, Weisheng Liu ^a

PMCID: PMC3050242 PMID: 21522705

Abstract

In the title compound, C₃₆H₄₀N₅O₆ ⁺·NO₃ ⁻·2C₂H₅OH, the nitrate anion is disordered over the two orientations of equal occupancy while the solvent molecule reveals large displacement parameters. The cation is formed by protonation of the N atom of a secondary amine in the middle of the flexible chain and the whole compound has crystallographically imposed C-2 symmetry with the crystallographic b axis. An O atom of the nitrate anion links the acidic H atoms of the cation via N—H⋯O hydrogen bonding. In addition, neighbouring cations are connected by intermolecular N—H⋯O hydrogen bonds and π–π interactions between the benzamide groups of the cations [centroid–centroid distance = 4.000 (3) Å], forming a chain along [001]. The ethanol solvent molecules are arranged on the side of the chain through O—H⋯O hydrogen bonds.

Related literature

Luminescent lanthanide complexes have attracted intense research interest due to their very narrow emission bands and large Stokes shifts, see: Wang et al. (2009 ▶); Bunzli & Piguet (2005 ▶); Stein & Wurzberg (1975 ▶). For amide-type open-chain ligands, see: Liu et al. (2009 ▶); Yi et al. (2007 ▶); Hamann et al. (2004 ▶).

Experimental

Crystal data

C₃₆H₄₀N₅O₆ ⁺·NO₃ ⁻·2C₂H₆O
M _r = 792.88
Monoclinic,
a = 16.978 (3) Å
b = 11.405 (2) Å
c = 11.164 (2) Å
β = 108.04 (3)°
V = 2055.6 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.22 × 0.18 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T _min = 0.980, T _max = 0.984
4901 measured reflections
1995 independent reflections
1334 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.190
S = 1.03
1995 reflections
277 parameters
45 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; 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/S1600536810052670/kp2291sup1.cif

e-67-0o203-sup1.cif^{(23KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052670/kp2291Isup2.hkl

e-67-0o203-Isup2.hkl^{(98.2KB, 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
N3—HN3⋯O5ⁱ	0.95 (4)	2.49 (5)	2.905 (9)	106 (3)
N3—HN3⋯O5ⁱⁱ	0.95 (4)	2.41 (5)	2.905 (9)	112 (3)
N3—HN3⋯O1ⁱⁱ	0.95 (4)	2.01 (4)	2.780 (3)	137 (4)
O4—H4A⋯O3ⁱⁱⁱ	0.85	1.89	2.740 (11)	178
N1—H1A⋯O2	0.86	1.99	2.645 (5)	132
N2—H2A⋯O5ⁱⁱ	0.86	2.14	2.813 (9)	135
N2—H2A⋯O6ⁱ	0.86	2.35	3.185 (9)	163

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

Acknowledgments

This work was supported financially by the National Natural Science Foundation of China (grant Nos. 20771048, 20931003, 21001059) and the Fundamental Research Funds for the Central Universities (lzujbky-2009-k06, lzujbky-2009–114).

supplementary crystallographic information

Comment

Luminescent lanthanide complexes have attracted intense research interest from both material and biological science mainly due to their very narrow emission bands and large Stokes shifts, etc (Wang et al., 2009; Bunzli & Piguet, 2005; Stein & Wurzberg, 1975). Since the lanthanides have low absorptivities and poor quantum yields, fluorescence enhancement has generally been achieved through ligand sensitisation. Among various kinds of ligands, amide type open-chain ligands have drawn much attention in past ten years, mainly due to their flexible structure, selective coordinating capacity and hard binding sites, which could stabilise their lanthanide complexes, acquire novel coordination structure and shield the encapsulated ion from interaction with the surroundings (Liu et al., 2009; Yi et al., 2007; Hamann et al., 2004). There is a need to prepare a new series of amide type ligands to further widen the scope of research on the chemical and physical properties of lanthanide complexes. In this paper, we present the structure of the title compound, a nitrate salt of a free ligand. The asymmetric unit comprises a half of cation C₃₆H₄₀N₅O₆⁺ nitrate anion, and ethanol molecule(Fig. 1). In C₃₆H₄₀N₅O₆⁺cation, the N atom of secondary amine in the middle of flexible chain is protonated adding more hydrogen bondind donor sites. An O atom of nitrate anion links the acidic H atoms and adjacent one of amide groups via N–H···O hydrogen bonding (Table 1) forming the S-shape organic cation. The carbonyl groups of benzamide at both ends of organic cation are involved in intermolecular N–H···O hydrogen bonds connecting acidic H atoms of neighbouring C₃₆H₄₀N₅O₆⁺cations to form a chain. The chain is further stabilised by π–π interactions between the benzamide groups from cations (Fig. 2). Ethanol molecules are arranged on the side of the chain and linked the O atoms of the acetamide groups via O–H···O hydrogen bonds.

Experimental

Ethyl 2-(2-(benzylcarbamoyl)phenoxy)acetate was firstly synthesised as a white solid via a simple prepared by reaction of N-benzylsalicylamide (2.27 g, 10.0 mmol) with ethyl chloroacetate (1.83 g, 15.0 mmol) in 80% yield using an excess amount of anhydrous potassium carbonate in refluxing acetone. Then the ligand, N,N'-iminodiethylenebis{[(2'-benzylaminoformyl)phenoxyl]acetamide}, was obtained in 18% yield by treating the ethyl 2-(2-(benzylcarbamoyl)phenoxy)acetate (1.88 g, 6 mmol) with 0.5 equiv of diethylenetriamine (0.258 g,2.5 mmol) in methanol at 333-338 K for 8 h (m.p. 372-374 K). Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution (6 mL) containing Tb(NO₃)₃.6H₂O (67.9 mg, 0.15 mmol) and N,N'-iminodiethylenebis{[(2'-benzylaminoformyl)phenoxyl]acetamide} (95.6 mg, 0.15 mmol) after two weeks at room temperature in 75% yield. The preparation was aimed to obtain an Tb(III) nitrate complex with the title ligand but instead the ligand was crystallised.