Crystal structure of di­chlorido­bis­(methyl isonicotinate-κN)copper(II)

Elaheh Ahadi; Hassan Hosseini-Monfared; Peter Mayer

doi:10.1107/S205698901500729X

. 2015 Apr 18;71(Pt 5):m112–m113. doi: 10.1107/S205698901500729X

Crystal structure of dichloridobis(methyl isonicotinate-κN)copper(II)

Elaheh Ahadi ^a, Hassan Hosseini-Monfared ^a,^*, Peter Mayer ^b

PMCID: PMC4420097 PMID: 25995890

Abstract

In the title compound, [CuCl₂(C₇H₇NO₂)₂], the square-planar-coordinated Cu^II ion lies on a centre of symmetry and is bonded to two monodentate methylisonicotinate ligands through their N atoms and by two chloride ligands. The molecules pack in a herringbone pattern. Perpendicular to [100] there are weak intermolecular C—H⋯Cl and C—H⋯O contacts. Along [100] there are infinite chains of edge-sharing octahedra linked through the chlorido ligands

Keywords: crystal structure, square-planar copper(II) complex, methyl isonicotinate

Related literature

For related structures, see: Vitorica-Yrezabal et al. (2011 ▸); Laing & Carr (1971 ▸); Chen & Mak (2006 ▸); Ge et al. (2006 ▸); Chen et al. (2011 ▸); Ma et al. (2010 ▸). For background to isonicotinate, see: Zhou et al. (2006 ▸); Bera et al. (2001 ▸); Cotton et al. (2007 ▸); Tella et al. (2014 ▸). For the synthesis of 4-(5-phenyl-1,3,4-oxadiazol-2-yl)pyridine, used in the preparation, see: Kangani & Day (2009 ▸).

Experimental

Crystal data

[CuCl₂(C₇H₇NO₂)₂]
M _r = 408.71
Monoclinic,
a = 3.7792 (4) Å
b = 29.891 (4) Å
c = 7.0139 (8) Å
β = 94.036 (10)°
V = 790.36 (16) Å³
Z = 2
Mo Kα radiation
μ = 1.74 mm⁻¹
T = 173 K
0.50 × 0.05 × 0.04 mm

Data collection

Oxford Diffraction Xcalibur 3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2011 ▸) T _min = 0.775, T _max = 1.000
4265 measured reflections
1617 independent reflections
1404 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.091
S = 1.09
1617 reflections
107 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2011 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008 ▸, 2015 ▸); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▸); software used to prepare material for publication: PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901500729X/cq2014sup1.cif

e-71-0m112-sup1.cif^{(158.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500729X/cq2014Isup2.hkl

e-71-0m112-Isup2.hkl^{(89.2KB, hkl)}

Click here for additional data file.^{(919.5KB, tif)}

x y z . DOI: 10.1107/S205698901500729X/cq2014fig1.tif

The molecular structure of the title compound (ellipsoids drawn at the 30% probability level). Symmetry code: i = 1 − x, −y, 1 − z. Non-labelled non-hydrogen atoms have been generated by symmetry i.

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S205698901500729X/cq2014fig2.tif

The unit cell viewed along [100] (ellipsoids drawn at the 50% probability level). Intermolecular C—H⋯Cl and C—H⋯O contacts are indicated by dashed lines.

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S205698901500729X/cq2014fig3.tif

Infinite strands along [100] formed by intermolecular Cu—Cl bonds (thin bond diameter) (drawn at the 30% ellipsoid probability level).

CCDC reference: 1059032

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C2H2Cl1ⁱ	0.95	2.83	3.517(3)	130
C7H7BO2ⁱⁱ	0.98	2.53	3.470(4)	161
C7H7CO1ⁱⁱⁱ	0.98	2.58	3.298(4)	130

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

Acknowledgments

The authors are grateful to the University of Zanjan and the School of Chemistry, Zanjan, and the Department of Chemistry of the LMU Munich for financial support.

supplementary crystallographic information

S1. Comment

Isonicotinate is a versatile ditopic ligand that has been used for various applications. The copper(II) isonicotinate (Cu(4–C₅H₄N-COO)₂(H₂O)₄) coordination polymer has been explored as a sorbent in flow injection solid-phase extraction for determination of trace polycyclic aromatic hydrocarbons in environmental matrices [Zhou et al. (2006)]. The incorporation of both dinuclear (M₂) and mononuclear (M') units into molecular squares has been achieved by reacting a triply bonded Re₂(II,II) complex possessing two cis isonicotinate donor ligands with Pt(II) containing molecules with substitutionally labile cis trifluoromethanesulfonate groups [Bera et al. (2001)]. Quadruply bonded Mo₂⁴⁺ species having isonicotinate ligands bound through the carboxylate group have been designed to act as 'anglers' by luring metal-containing Lewis acids to bind to the N-pyridyl group [Cotton et al. (2007)]. The copper-isonicotinate metal-organic frameworks [Cu(INA)₂] (INA = isonicotinate) (MOFs) have been prepared simply by mixing and heating solid reactants without milling. The adsorption of fluorescein dye on the as-synthesized [Cu(INA)₂] has also been investigated [Tella et al. (2014)].

The molecular structure of the title compound possessing a crystallographic centre of inversion is depicted in Fig. 1. The first coordination sphere of the Cu1 centre consists of two nitrogen atoms, from the isoniconate ligands, at a distance of 2.025 (2) Å and two chlorido ligands at a distance of 2.2962 (7) Å. The various N1—Cu1—Cl1 angles are close to 90° resulting in a square-planar first coordination sphere of Cu1. By coordination of two additional chlorido ligands from adjacent complexes at a distance of 2.9215 (7) Å from the Cu1 centre, the coordination sphere is expanded to a distorted octahedron. The pyridine ring and the Cu1—Cl1 bond are not coplanar, but enclose an angle of 59.00 (9)°. The Cu—N1 bond and the plane of the pyridine ring deviate from coplanarity by an angle of 5.05 (11)°.

The herringbone pattern of the packing of the title compound is shown in Fig. 2. Perpendicular to [100] there are weak intermolecular C—H···Cl and C—H···O contacts with donor-acceptor distances of 3.517 (3) Å, 3.470 (4) Å and 3.298 (4) Å (C2···Cl1, C7···O2 and C7···O1, respectively). Along [100] there are infinite chains of edge-sharing octahedra linked through the chlorido ligands (Fig.3). This structural feature is found in many copper complexes consisting of two chlorido ligands and two pyridine derivatives, e.g. Vitorica-Yrezabel et al. (2011), Laing et al. (1971), Chen et al. (2006), Ge et al. (2006), Chen et al. (2011), Ma et al. (2010). Each bridging chlorido ligand has a short (2.2962 (7) Å) and a longer (2.9215 (7) Å) bond distance to the two adjacent Cu-centers. The bond angle at the bridging chloride ions is 92.03 (2)°. A consequence of the formation of the strands along [100] is π-stacking between adjacent pyridine rings. The average distance between the centres of gravity of adjacent rings is a = 3.7792 Å.

S2. Experimental

The compound 4-(5-phenyl-1,3,4-oxadiazol-2-yl)pyridine (0.04 g, 0.18 mmol, synthesised by a previously reported method [Kangani et al. (2009)], and copper(II) chloride dihydrate (0.015 g, 0.09 mmol) were placed in the main arm of a branched tube. Methanol (13 ml) was carefully added to fill the arms, the tube was sealed and the reagent-containing arm immersed in an oil bath at 60 °C while the other arm was kept at ambient temperature. After two weeks, green, needle shaped crystals were deposited in the cooler arm. The crystals were filtered, washed with methanol and air dried. Yield 19% (7.0 mg).