Bis(chloro­acetato)-κ2 O,O′;κO-methanol-κO-bis­(2-methyl­furo[3,2-c]pyridine-κN)copper(II)

Dušan Mikloš; Jozef Miklovič; Viera Mrázová; Jan Moncol; Peter Segľa

doi:10.1107/S1600536808008404

. 2008 Apr 2;64(Pt 5):m610–m611. doi: 10.1107/S1600536808008404

Bis(chloroacetato)-κ² O,O′;κO-methanol-κO-bis(2-methylfuro[3,2-c]pyridine-κN)copper(II)

Dušan Mikloš ^a, Jozef Miklovič ^b, Viera Mrázová ^b, Jan Moncol ^a,^*, Peter Segľa ^a

PMCID: PMC2961079 PMID: 21202169

Abstract

In the title compound, [Cu(C₂H₂ClO₂)₂(C₈H₇NO)₂(CH₄O)], the Cu²⁺ ion has a highly distorted square-bipyramidal (4 + 1 + 1) coordination environment and is bonded to three carboxylate O atoms of two chloroacetate anions (monodentate and asymmetrically bidentate), two pyridine N atoms of 2-methylfuro[3,2-c]pyridine and one methanol O atom. There is an intramolecular O—H⋯O hydrogen bond. Intermolecular C—H⋯O hydrogen bonds result in the formation of a three-dimensional network and π–π stacking interactions [3.44–3.83 Å] are observed between symmetry-related rings of 2-methylfuro[3,2-c]pyridine. Further interactions in the crystal structure are a short Cl⋯Cl interaction [3.384 (2)Å] and C—H⋯π interactions between 2-methylfuro[3,2-c]pyridine rings.

Related literature

For general background, see: Desiraju (1995 ▶); Janiak (2000 ▶); Suezawa et al. (2002 ▶). For related literature, see: Baran et al. (2005 ▶); Eloy & Deryckere (1971 ▶); Ivaniková et al. (2006 ▶); Mikloš et al. (2005 ▶); Miklovič et al. (2004 ▶); New et al. (1989 ▶); Segľa et al. (2005 ▶); Titiš et al. (2007 ▶); Vrábel et al. (2007a ▶,b ▶). For similar structures, see: Borel et al. (1978 ▶); Moncol et al. (2007 ▶); Wang et al. (2005 ▶).

Experimental

Crystal data

[Cu(C₂H₂ClO₂)₂(C₈H₇NO)₂(CH₄O)]
M _r = 548.86
Monoclinic,
a = 19.860 (3) Å
b = 15.576 (3) Å
c = 15.017 (3) Å
β = 97.917 (3)°
V = 4600.9 (15) Å³
Z = 8
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 173 (2) K
0.26 × 0.20 × 0.16 mm

Data collection

Nonius KappaCCD area-detector diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ▶) T _min = 0.776, T _max = 0.891 (expected range = 0.716–0.822)
16690 measured reflections
4021 independent reflections
3093 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.103
S = 1.02
4021 reflections
300 parameters
H-atom parameters constrained
Δρ_max = 1.08 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; 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: enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808008404/om2220sup1.cif

e-64-0m610-sup1.cif^{(25.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008404/om2220Isup2.hkl

e-64-0m610-Isup2.hkl^{(193.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Cu1—O8	1.956 (2)
Cu1—O4	1.964 (2)
Cu1—N21	2.031 (3)
Cu1—N11	2.046 (3)
Cu1—O1	2.311 (2)
Cu1—O5	2.833 (2)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O9	0.84	1.86	2.664 (3)	159
C12—H12⋯O4	0.95	2.44	2.944 (4)	113
C20—H20⋯O8	0.95	2.40	2.915 (4)	114
C22—H22⋯O8	0.95	2.41	2.886 (4)	111
C30—H30⋯O4	0.95	2.53	3.000 (4)	111
C6—H6A⋯O5ⁱ	0.99	2.60	3.510 (4)	154
C16—H16C⋯O1ⁱⁱ	0.98	2.63	3.413 (4)	137
C14—H14⋯O9ⁱⁱ	0.95	2.55	3.450 (4)	159
C20—H20⋯O5ⁱ	0.95	2.57	3.221 (4)	126
C29—H29⋯O5ⁱⁱⁱ	0.95	2.69	3.451 (4)	138
C19—H19⋯O5ⁱ	0.95	2.65	3.235 (4)	120
C16—H16A⋯O9^iv	0.98	2.65	3.610 (4)	167
C24—H24⋯O9^v	0.95	2.67	3.408 (4)	135
C1—H1B⋯C14^vi	0.98	2.87	3.834 (4)	168

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

Acknowledgments

We thank Professor R. Sillanpää for measuring the diffraction data and the Scientific Grant Agency of the Ministry of Education of the Slovak Republic and the Slovak Academy of Sciences (1/4454/07 and 1/0353/08) for financial support.

supplementary crystallographic information

Comment

Furopyridines are components of many biologically active compounds, for example the furo[3,2-c]pyridine ring system has potential antipsychotic activity (New et al., 1989). The furo[3,2-c]pyridine and its derivatives can be readily coordinated to metal centers through the pyridine N-donor atom (Baran et al., 2005; Ivaniková et al., 2006; Mikloš et al. (2005); Miklovič et al., 2004; Segľa et al. (2005); Titiš et al., 2007; Vrábel et al., 2007a,b). As part of our efforts to investigate metal(II) complexes based on furo[3,2-c]pyridine derivatives, we describe the X-ray characterization of the title compound.

In the title compound, the Cu^II atom is six-coordinated by two carboxylate O atoms of the asymmetrically chelating bidentate chloroacetate anion [Cu1–O4 = 1.964 (2) and Cu–O5 = 2.833 (2) Å], one carboxylate O atom of the monodentate chloroacetate anion [Cu1–O8 = 1.956 (2) Å], two N atoms of pyridine rings of 2-methylfuro[3,2-c]pyridine [Cu1–N11 = 2.046 (3) and Cu1–N21 = 2.031 (3) Å] and one O atom of methanol molecule [Cu1–O1 = 2.311 (2) Å], resulting in highly distorted square-bipyramidal geometry (Fig. 1). The intramolecular O–H···O hydrogen bond forms a six-membered metallocycle (Fig. 1).

The bond lengths and angles may be compared with the corresponding values in similar complexes, with axial water molecule [aquabis(benzoato)bis(γ-picoline)copper(II) (II) (refcode: BZGPCU10, Borel et al., 1978); aquabis(3-pyridylacrylato)bis(3-pyridylmethanol)copper(II) (III), (refcode: XEYTAX, Moncol et al., 2007); aquabis(acetato)bis(2-(3-pyridyl)-5-(4-pyridyl)-1,3,4-oxadiazole)copper(II) (IV), (refcode: QAQNOM, Wang et al., 2005)]. In the molecular structure of all three complexes (II–IV), there is highly distorted square-bipyramidal (4 + 1 + 1) coordination environment, the longer Cu–O bond distances for asymmetrically chelating bidentate carboxylate anions are in the range of 2.61–2.78 Å.

The hydrogen-bond parameters of the title compound are listed in Table 2. The molecules of the title compound are linked through weak C–H···O hydrogen-bonding interactions (Figures 2 and 3), where acceptor atoms of hydrogen-bonds are carboxylate O atoms (O5 and O9). As can be seen in Figure 2, there are observed also short Cl2···Cl2^vi [symmetry code: (vi) -x + 2, y, -z + 1/2] contacts (Desiraju, 1995) of 3.384 (2)Å between the molecules of the title compound. The additional interactions are the π-π stacking interactions (Janiak, 2000), between the two adjacent furo[3,2-c]pyridine rings, [N21/C22—C25/O27/C28—C30] (π_a) and [N11/C12—C15/O17/C18—C20] (π_b). Four 2-methylfuro[3,2-c]pyridine rings are stacked in the order π_b-π_a···π_a-π_a···π_a-π_b (Figure 2). The distances between π_a-π_aⁱⁱⁱ and π_a-π_b^vii [symmetry codes: (iii) -x + 1, y, -z + 1/2, (vii) -x + 3/2, y + 1/2, -z + 1/2] 2-methylfuro[3,2-c]pyridine rings are in ranges 3.44–3.66 Å and 3.45–3.83 Å, respectively. The CH/π interaction (Suezawa et al., 2002) is also observed between methyl H atom of the methanol ligand and furan ring of 2-methylfuro[3,2-c]pyridine [C1–H1B···π_b^viii, symmetry code: (viii) x, -y + 1, z - 1/2] (Figure 3). The distances D_atm (interatomic distance H1B/C14) and D_pln (H/π-plane distance) (Suezawa et al., 2002) are 2.77 and 2.85 Å, respectively.

Experimental

The organic compounds 2-methylfuro[3,2-c]pyridine (Mefpy) has been prepared using procedure described in Eloy & Deryckere (1971). Complex Cu(C₂H₂ClO₂)₂.2H₂O (0.002 mol, 0.57 g) was dissolved in 30 cm³ of methanol and treated with a methanolic solution of Mefpy (0.004 mol, 0.53 g, 10 cm³ me thanol) in a molar ratio of 1:2. The mixture was stirred and left to stand at room temperature giving a crystalline compound of [Cu(C₂H₂ClO₂)₂(C₈H₇NO)₂(CH₄O)]. The Anal. Calc.: C, 45.95; H, 4.04; N, 5.10; Cu, 11.58; Found: C, 45.57; H, 3.87; N, 5.00; Cu, 11.45. IR (KBr) cm^-1: 1640vs,br ν_as(COO^-); 1371vs ν_s(COO^-); 1605mν(C?N)_Mefpy; 654mδ(py)_Mefpy; 428mχ(py)_Mefpy; 1041mν(C–O)_methanol. UV-VIS: 645 nm.