Chloridobis(1,2,3,4-tetra­hydro-1,4,6,11-tetra­aza­naphthacene-κN 6)copper(I)

Xing-Shun Chen; Jing-Jing Zhang; Tai-Ke Duan; Qun Chen; Qian-Feng Zhang

doi:10.1107/S1600536812005582

. 2012 Feb 17;68(Pt 3):m297. doi: 10.1107/S1600536812005582

Chloridobis(1,2,3,4-tetrahydro-1,4,6,11-tetraazanaphthacene-κN ⁶)copper(I)

Xing-Shun Chen ^a, Jing-Jing Zhang ^a, Tai-Ke Duan ^a, Qun Chen ^b, Qian-Feng Zhang ^a,^b,^*

PMCID: PMC3297250 PMID: 22412440

Abstract

In the title complex, [CuCl(C₁₄H₁₂N₄)₂], the Cu^I atom, lying on a twofold rotation axis, is coordinated by two N atoms of two 1,2,3,4-tetrahydro-1,4,6,11-tetraazanaphthacene ligands and one Cl atom, also lying on the twofold rotation axis, in a distorted trigonal-planar geometry. The complex molecules are connected into a one-dimensional structure along [001] via N—H⋯N hydrogen bonds and further into a three-dimensional structure via N—H⋯Cl hydrogen bonds. π–π interactions between the pyrazine and benzene rings and between the benzene rings [centroid–centroid distances = 3.5635 (15) and 3.9128 (16) Å] are present.

Related literature

For transition metal complexes with heterocyclic ligands, see: Dai et al. (2007 ▶); Grove et al. (2000 ▶, 2001 ▶); Näther & Beck (2004 ▶); Xu et al. (2011 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[CuCl(C₁₄H₁₂N₄)₂]
M _r = 571.54
Monoclinic,
a = 16.987 (4) Å
b = 11.606 (3) Å
c = 14.487 (4) Å
β = 118.492 (3)°
V = 2510 (1) Å³
Z = 4
Mo Kα radiation
μ = 1.01 mm⁻¹
T = 296 K
0.29 × 0.24 × 0.06 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.758, T _max = 0.942
7571 measured reflections
2839 independent reflections
2476 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.105
S = 1.03
2839 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536812005582/hy2514sup1.cif

e-68-0m297-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005582/hy2514Isup2.hkl

e-68-0m297-Isup2.hkl^{(139.5KB, 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—H3N⋯N2ⁱ	0.86	2.22	2.986 (2)	148
N4—H4N⋯Cl1ⁱⁱ	0.86	2.76	3.4952 (18)	145

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

Acknowledgments

This project was supported by the Program for New Century Excellent Talents in Universities of China (grant No. NCET-08–0618).

supplementary crystallographic information

Comment

The heterocyclic compounds involving aromatic system with condensed pyrazine, pyridine and piperidine rings have been shown to occur as a rigid bridge in transition metal complexes, which are expected to be good building blocks for creating coordination polymers due to the flexibility of the heterocyclic ligands (Grove et al., 2000, 2001). We have recently been studying the coordination chemistry of polyamines to transition metal halides (Dai et al., 2007, Xu et al., 2011). In the course of this work, we have synthesized the title copper(I) complex with a new 1,2,3,4-tetrahydro-1,4,6,11-tetraazanaphthacene ligand formed from the condensing reaction of phenazine and ethane-1,2-diamine under hydrothermal conditions. Here we report the crystal structure of the mononuclear copper(I) complex.

The molecular structure of the title complex is depicted in Fig. 1. The Cu^I atom, lying on a twofold rotation axis, is coordinated by two N atoms of two organic ligands and one Cl atom. The Cu—N bond length of 1.9927 (15) Å and the Cu—Cl bond length of 2.2229 (10) Å are in the range of those found in related structures retrieved from the Cambridge Structural Database (Allen, 2002). The N—Cu—N and N—Cu—Cl angles are 123.94 (9) and 118.03 (4)°. The Cu atom shows a distorted trigonal-planar coordination geometry (Näther & Beck, 2004). In the crystal, the discrete complex molecules are connected by N—H···N and N—H···Cl hydrogen bonds (Table 1) into a three-dimensional structure (Fig. 2). π–π interactions between the pyrazine and benzene rings and between the benzene rings [centroid–centroid distances = 3.5635 (15) and 3.9128 (16) Å] are present.

Experimental

CuCl (99 mg, 1 mmol), phenazine (360 mg, 2 mmol) and ethane-1,2-diamine (300 mg, 5 mmol) were mixed in water (ca. 3 g) and placed in a 23 ml Teflon-lined stainless steel autoclave and stirred for 20 min. The vessel was sealed and heated to 140°C for 2 d and then cooled to room temperature. Yellow flake crystals were obtained and air dried (yield: 64% based on CuCl). Analysis, calculated for C₂₈H₂₄ClCuN₈: C 58.84, H 4.23, N 19.61%; found: C 58.76, H 4.18, N 19.55%.