Diazido­{(S)-1-phenyl-N,N-bis­[(2-pyrid­yl)meth­yl]ethanamine}­copper(II)

Sankara Rao Rowthu; Jong Won Shin; Seung-Hui Kim; Jong Jin Kim; Kil Sik Min

doi:10.1107/S1600536811021234

. 2011 Jun 11;67(Pt 7):m873–m874. doi: 10.1107/S1600536811021234

Diazido{(S)-1-phenyl-N,N-bis[(2-pyridyl)methyl]ethanamine}copper(II)

Sankara Rao Rowthu ^a, Jong Won Shin ^a, Seung-Hui Kim ^a, Jong Jin Kim ^b, Kil Sik Min ^c,^*

PMCID: PMC3152144 PMID: 21836869

Abstract

In the title compound, [Cu(N₃)₂(C₂₀H₂₁N₃)], the Cu^II ion is coordinated by the three N atoms of the (S)-1-phenyl-N,N-bis[(2-pyridyl)methyl]ethanamine ligand and two N atoms from two azide anions, resulting in a distorted square-pyramidal environment. A weak intermolecular C—H⋯N hydrogen-bonding interaction between one pyridine group of the ligand and an azide N atom of an adjacent complex unit gives a one-dimensional chain structure parallel to the c axis.

Related literature

For the potential applications of chiral complexes in chiral recognition, chiral catalysis and enantioselective sorption, see: Lehn (1995 ▶); Seo et al. (2000 ▶). Chiral Ni^II macrocyclic complexes and two-dimensional chiral open-framework compounds have been described by Han et al. (2008 ▶); Ryoo et al. (2010 ▶). A homochiral metal–organic framework with a cerium(III) ion has been described by Dang et al. (2010 ▶). For the preparation of (S)-1-phenyl-N,N-[bis(2-pyridyl)methyl]ethanamine, see: Lucas et al. (2009 ▶).

Experimental

Crystal data

[Cu(N₃)₂(C₂₀H₂₁N₃)]
M _r = 451.00
Monoclinic,
a = 6.9972 (12) Å
b = 14.506 (3) Å
c = 10.2828 (17) Å
β = 98.413 (4)°
V = 1032.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 296 K
0.23 × 0.19 × 0.04 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.749, T _max = 0.958
7801 measured reflections
4630 independent reflections
2863 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.115
S = 1.09
4630 reflections
272 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.90 e Å⁻³
Absolute structure: Flack (1983 ▶), 1941 Friedel pairs
Flack parameter: 0.02 (3)

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SHELXTL (Sheldrick, 2008 ▶); 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/S1600536811021234/pk2326sup1.cif

e-67-0m873-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021234/pk2326Isup2.hkl

e-67-0m873-Isup2.hkl^{(222.2KB, 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
C3—H3⋯N6ⁱ	0.93	2.59	3.261 (11)	129

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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 (grant No. R01-2008-000-20955-0). The authors acknowledge the Korea Basic Science Institute for the X-ray data collection.

supplementary crystallographic information

Comment

Chiral complexes have attracted considerable interest because of their potential and practical applications, such as chiral recognition, chiral catalysis, and enantioselective sorption (Lehn, 1995; Seo et al., 2000). Very recently, a two-dimensional chiral open framework, [Ni(L^R,^R)]₃[C₆H₃(COO)₃]₂.12H₂O.CH₃CN [L^R^,^R=1,8-bis[(R)-α-methylbenzyl]-1,3,6,8,\ 10,13-\ hexaazacyclotetradecane] has been shown to have selective chiral recognition in rac-1,1'-bi-2-naphthol (Han et al., 2008; Ryoo et al., 2010). Furthermore, a homochiral metal-organic framework composed of a cerium(III) ion and chiral organic building block has large chiral one-dimensional channels and exhibited excellent catalytic activity and high enantioselectivity for the asymmetric cyanosilylation of aromatic aldehydes (Dang et al., 2010). Here, we report the synthesis and crystal structure of a five-coordinated Cu^II complex with (S)-1-phenyl-N,N-[bis(2-pyridyl)methyl]ethanamine (S-ppme), the title compound [Cu(S-ppme)(N₃)₂].

In the title compound (Fig. 1), the Cu^II ion is five-coordinated and shows a distorted square pyramidal geometry, the equatorial plane being defined by the three nitrogen atoms of the S-ppme ligand and one nitrogen atom of an azide ion. The coordination geometry is completed by the axial coordination of the nitrogen atom of the second azide anion. The Cu—L_eq bond lengths are in the range of 1.961 (6) and 2.178 (5) Å and the Cu—N_ax bond length is 1.978 (5) Å. Both azide ions are bonded in η¹-fashion and fully delocalized. The bond angles around the copper atom range from 76.95 (12) to 165.48 (15)°. The packing structure involves a weak C—H···N hydrogen bonding interaction between the one pyridine group of the S-ppme ligand and an azide N atom of an adjacent complex unit (Table 1), giving a one-dimensional chain structure parallel to the c axis (Fig. 2).

Experimental

(S)-1-phenyl-N,N-[bis(2-pyridyl)methyl]ethanamine (S-ppme) was prepared according to slightly modified literature procedure (Lucas et al., 2009) except that (S)-(-)-α-methylbenzylamine instead of benzylamine (yield: 0.86 g, 60%). A mixture of MeCN and H₂O (2:1, v/v, 3 ml) solution of CuCl₂.2H₂O (29 mg, 0.17 mmol) was added to an MeCN solution (3 ml) of S-ppme (51 mg, 0.17 mmol) and a MeOH solution (4 ml) of sodium azide (22 mg, 0.34 mmol). The resulting solution was stirred for 1 h at room temperature, resulting in a color change to blue-green. Diffusion of diethyl ether into the mixture gave green crystals of the title compound after a few days. These crystals were filtered and washed with diethyl ether and dried in air (yield: 42 mg, 56%).