catena-Poly[[(2,2′-bipyrimidine-κ2 N 1,N 1′)diperchloratocopper(II)]-μ-4,4′-bipyridine-κ2 N:N′]

Wei Xu; Jian-Li Lin; Hong-Zhen Xie

doi:10.1107/S1600536808021296

. 2008 Jul 16;64(Pt 8):m1031. doi: 10.1107/S1600536808021296

catena-Poly[[(2,2′-bipyrimidine-κ² N ¹,N ^1′)diperchloratocopper(II)]-μ-4,4′-bipyridine-κ² N:N′]

Wei Xu ^a,^*, Jian-Li Lin ^a, Hong-Zhen Xie ^a

PMCID: PMC2961952 PMID: 21203022

Abstract

The central CuN₄O₂ motif of the title compound, [Cu(ClO₄)₂(C₈H₆N₄)(C₁₀H₈N₂)]_n, exhibits a Jahn–Teller-distorted octahedral geometry around the metal centre, showing a considerably long Cu—O bond distance of 2.634 (4) Å towards the second perchlorate group occupying the sixth coordination site, giving a (4+1+1)-type coordination mode. The 4,4′-bipyridine (bipy) ligands are highly twisted with respect to each other, the dihedral angle between the two pyridyl ring planes being 38.9 (2)°. The bipy ligands act as bridging ligands between [Cu(ClO₄)₂(2,2′-bpym)] (2,2′-bpym is 2,2′-bipyrimidine) units, generating an infinite one-dimensional zigzag chain along [010]. Intra- and intermolecular C—H⋯O hydrogen bonds are present in the crystal structure.

Related literature

For related literature, see: Biradha & Fujita (2000 ▶); Eddaoudi et al. (2001 ▶); Hathaway (1973 ▶); Kaye & Long (2008 ▶); Kitagawa et al. (2006 ▶); Subramanian & Zaworotko (1995 ▶).

Experimental

Crystal data

[Cu(ClO₄)₂(C₈H₆N₄)(C₁₀H₈N₂)]
M _r = 576.75
Monoclinic,
a = 11.334 (2) Å
b = 14.266 (3) Å
c = 13.299 (3) Å
β = 96.55 (3)°
V = 2136.3 (8) Å³
Z = 4
Mo Kα radiation
μ = 1.33 mm⁻¹
T = 295 (2) K
0.32 × 0.26 × 0.15 mm

Data collection

Bruker P4 diffractometer
Absorption correction: ψ scan (XSCANS; Siemens, 1996 ▶) T _min = 0.664, T _max = 0.815
4265 measured reflections
3686 independent reflections
2896 reflections with I > 2σ(I)
R _int = 0.045
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.160
S = 1.06
3686 reflections
317 parameters
H-atom parameters constrained
Δρ_max = 0.93 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021296/im2074sup1.cif

e-64-m1031-sup1.cif^{(20.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808021296/im2074Isup2.hkl

e-64-m1031-Isup2.hkl^{(180.8KB, 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
C1—H1⋯O6ⁱ	0.93	2.59	3.415 (9)	147
C6—H6⋯O2ⁱⁱ	0.93	2.58	3.425 (7)	151
C7—H7⋯O3ⁱⁱⁱ	0.93	2.58	3.189 (7)	124
C9—H9⋯O3	0.93	2.56	3.480 (7)	171
C9—H9⋯O4	0.93	2.49	3.185 (6)	132
C11—H11⋯O2^iv	0.93	2.46	3.342 (6)	159
C16—H16⋯O4^v	0.93	2.57	3.299 (6)	135
C17—H17⋯O8^v	0.93	2.47	3.082 (6)	124

Open in a new tab

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

Acknowledgments

This project was sponsored by the K. C. Wong Magna Fund of Ningbo University, the Expert Project of Key Basic Research of the Ministry of Science and Technology of China (grant No. 2003CCA00800), the Ningbo Municipal Natural Science Foundation (grant No. 2006 A610061) and the Newer Training Program Foundation for Talents of the Science and Technology Department of Zhejiang Province (grant No. 2007R40G2070020).

supplementary crystallographic information

Comment

A great deal of interest in self-assembly of coordination complexes with specific frameworks is expanding rapidly in view of their potentially useful magnetic, catalytic and nonlinear optical properties (Eddaoudi, et al., 2001; Kitagawa, et al., 2006; Kaye & Long, 2008). The ligand 4,4'-bipyridine is an ideal bridging ligand between transition metal atoms to establish coordination networks due to itss two potential binding sites that are arranged in a divergent (exo) fashion and its a rigid structure helping to predict network geometries (Subramanian & Zaworotko, 1995; Biradha & Fujita, 2000). 2,2'-bipyrimidine also is a versatile blocking and bridging ligand due to its N₂ chelating sites on both sides of the ligand. Herein, we report a new complex with one-dimensional zigzag chains, (I), obtained by self-assembly from Cu(ClO₄)₂, 4,4'-bpy and 2,2'-bpym in DMF solution. 2,2'-bpym acts as a bidentate ligand with the second chelating site not coodinating the metal atom.

In the title compound, the Cu atom is located in a Jahn-Teller distorted octahedral coordination environment with four N atoms from one 2,2'-bpym ligand (N1, N2) and two 4,4'-bpy ligands [N5, N6^#1 (#1 = 1/2 - x, 1/2 + y, 1/2 - z)] adopting a planar arrangement (d(Cu—N) = 1.998 (4)–2.008 (4) Å). The Cu(II) centre is displaced out of the N₄ plane by 0.062 (2) Å in the direction of one of perchlorate ligand with d(Cu—O8) = 2.421 (4) Å. The O atom of the second perchlorate group occupies a sixth coordination site at a longer distance of 2.634 (4) Å, completing the overall (4 + 1 + 1) type coordination. O4 is situated slightly off the axial direct of the square pyramid, nevertheless it is close enough to the Cu atom (Hathaway, 1973). The complex can thus be interpreted of consisting of [(2,2'-bpym)Cu(ClO₄)₂] units attached to each other via 4,4'-bpy to give a zigzag one-dimensional chain along [010] with the chelating 2,2'-bpym ligands extending outwards. The pyrimidine rings of the 2,2'-bpym ligand are twisted relative to each other at 8.7 (1)°, while the dihedral angel of the pyridine rings of the 4,4'-bpy ligand is 38.9 (2)°. Another interesting feature of the structure is that the backbone of the 2,2'-bpym ligand extends sideways from either face of the 4,4'-bpy ribbon and intimately interlocks the interchain region that separates adjacent 4,4'-bpy ribbons (Fig. 2). The perchlorate groups exhibit weak intramolecular hydrogen bonds between the O atoms and the C atoms of the 4,4'-bpy ligands with d(C···O) = 3.082 (6)–3.480 (7) Å and <(C—H···O) = 124–171° (Table 1.). In addition, intermolecular C—H···O hydrogen bonds between the C atoms of the 2,2'-bpym and 4,4'-bpy ligands and the O atoms of the perchlorate groups (d(C···O) = 3.189 (7)–3.425 (7) Å and <(C—H···O) = 124–159°) are observed that are responsible for the three-dimensional supramolecular assembly.

Experimental

Addition of 0.372 g (1.0 mmol) Cu(ClO₄)₂, 0.158 g (1.0 mmol) 4,4'-bipyridine and 0.158 g (1.0 mmol) 2,2'-bipyrimidine to a stirred DMF solution (30 ml) yielde a purple precipitate, which was refluxed for 2 h at 403 K followed by filtration after cooling. The resulting light-green filtrate was maintained at room temperature, slow evaporation afforded a small amount of purple block crystals two weeks later.