Bis(chloro­acetato)-κ2O,O′;κO-methanol-κO-bis­(2-methyl­furo[3,2-c]pyridine-κN)copper(II)

Mikloš, D.; Miklovič, J.; Mrázová, V.; Moncol, J.; Segľa, P.

doi:10.1107/S1600536808008404

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Pages m610-m611

doi:10.1107/S1600536808008404

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Bis(chloroacetato)-κ²O,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 ^* and Peter Segľa ^a

^aDepartment of Inorganic Chemistry, Slovak Technical University, Radlinského 9, SK-812 37, Bratislava, Slovakia, and ^bDepartment of Chemistry, Faculty of Natural Science, University of St. Cyril and Methodius, SK-91701 Trnava, Slovakia
^*Correspondence e-mail: jan.moncol@stuba.sk

(Received 17 March 2008; accepted 28 March 2008; online 2 April 2008)

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, C 2/c
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[F² > 2σ(F²)] = 0.043
wR(F²) = 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

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)

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
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+1, z+{\script{1\over 2}}]$ ; (v) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[x, -y+1, z-{\script{1\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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^-); 1605m ν(C?N)_Mefpy; 654m δ(py)_Mefpy; 428m χ(py)_Mefpy; 1041m ν(C–O)_methanol. UV-VIS: 645 nm.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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).

Figures top

	Fig. 1. Perspective view of the title compound, with the atom numbering scheme and thermal ellipsoids drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound with C–H···O hydrogen bonds, Cl···Cl contacts and π-π stacking interactions. Symmetry codes: (ii) -x + 3/2, y - 1/2, -z + 1/2; (iii) -x + 1, y, -z + 1/2; (v) -x + 3/2, y + 1/2, -z + 1/2; (vi) -x + 2, y, -z + 1/2].
	Fig. 3. The C–H···O hydrogen bonds and CH/π interactions in crystal structure of the title compound. Symmetry codes: (i) -x + 3/2, -y + 3/2, -z + 1; (v) -x + 3/2, y + 1/2, -z + 1/2].

Bis(chloroacetato)-κ²O,O';κO-methanol-κO-bis(2- methylfuro[3,2-c]pyridine-κN)copper(II) top

Crystal data top

[Cu(C₂H₂ClO₂)₂(C₈H₇NO)₂(CH₄O)]	F(000) = 2248
M_r = 548.86	D_x = 1.585 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C2yc	Cell parameters from 4021 reflections
a = 19.860 (3) Å	θ = 2.3–25.0°
b = 15.576 (3) Å	µ = 1.23 mm⁻¹
c = 15.017 (3) Å	T = 173 K
β = 97.917 (3)°	Block, green
V = 4600.9 (15) Å³	0.26 × 0.20 × 0.16 mm
Z = 8

Data collection top

Nonius KappaCCD area-detector diffractometer	4021 independent reflections
Radiation source: Enraf–Nonius FR590	3093 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.076
Detector resolution: 9 pixels mm^-1	θ_max = 25.0°, θ_min = 2.3°
ω and ϕ scans	h = −21→23
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −16→18
T_min = 0.776, T_max = 0.891	l = −16→17
16690 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0452P)² + 8.8488P] where P = (F_o² + 2F_c²)/3
4021 reflections	(Δ/σ)_max = 0.001
300 parameters	Δρ_max = 1.08 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Cu(C₂H₂ClO₂)₂(C₈H₇NO)₂(CH₄O)]	V = 4600.9 (15) Å³
M_r = 548.86	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 19.860 (3) Å	µ = 1.23 mm⁻¹
b = 15.576 (3) Å	T = 173 K
c = 15.017 (3) Å	0.26 × 0.20 × 0.16 mm
β = 97.917 (3)°

Data collection top

Nonius KappaCCD area-detector diffractometer	4021 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	3093 reflections with I > 2σ(I)
T_min = 0.776, T_max = 0.891	R_int = 0.076
16690 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.02	Δρ_max = 1.08 e Å⁻³
4021 reflections	Δρ_min = −0.53 e Å⁻³
300 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.68144 (2)	0.73110 (3)	0.32031 (2)	0.02193 (13)
Cl1	0.47011 (5)	0.61664 (6)	0.48363 (6)	0.0391 (2)
Cl2	0.91758 (6)	0.91134 (8)	0.26724 (8)	0.0570 (3)
O1	0.70672 (12)	0.67987 (16)	0.18435 (15)	0.0311 (6)
H1O	0.7475	0.6953	0.1961	0.042*
O4	0.60027 (12)	0.65827 (15)	0.31521 (14)	0.0245 (5)
O5	0.58725 (13)	0.72145 (16)	0.44549 (15)	0.0329 (6)
O8	0.75801 (11)	0.81089 (15)	0.34186 (15)	0.0255 (5)
O9	0.82188 (13)	0.76344 (17)	0.24003 (16)	0.0346 (6)
O17	0.85280 (12)	0.44366 (15)	0.51707 (14)	0.0260 (5)
O27	0.51950 (12)	1.02340 (16)	0.12018 (15)	0.0308 (6)
N11	0.73795 (14)	0.63899 (18)	0.39349 (17)	0.0239 (6)
N21	0.62599 (14)	0.82756 (18)	0.25534 (17)	0.0234 (6)
C1	0.7054 (2)	0.5932 (3)	0.1550 (3)	0.0401 (10)
H1A	0.7410	0.5605	0.1921	0.060*
H1B	0.7131	0.5908	0.0920	0.060*
H1C	0.6609	0.5684	0.1609	0.060*
C2	0.51644 (18)	0.6003 (2)	0.3912 (2)	0.0281 (8)
H2A	0.5376	0.5426	0.3965	0.034*
H2B	0.4844	0.6017	0.3346	0.034*
C3	0.57154 (17)	0.6670 (2)	0.3861 (2)	0.0241 (7)
C6	0.86409 (19)	0.8740 (2)	0.3437 (2)	0.0336 (9)
H6A	0.8924	0.8462	0.3951	0.040*
H6B	0.8411	0.9237	0.3674	0.040*
C7	0.81103 (17)	0.8109 (2)	0.3028 (2)	0.0261 (8)
C12	0.72171 (17)	0.5554 (2)	0.3792 (2)	0.0249 (7)
H12	0.6819	0.5407	0.3395	0.030*
C13	0.76207 (17)	0.4910 (2)	0.4212 (2)	0.0232 (7)
C14	0.76156 (18)	0.3984 (2)	0.4209 (2)	0.0275 (8)
H14	0.7293	0.3623	0.3866	0.033*
C15	0.81551 (18)	0.3731 (2)	0.4786 (2)	0.0266 (8)
C16	0.84283 (19)	0.2884 (2)	0.5111 (2)	0.0315 (8)
H16A	0.8411	0.2836	0.5759	0.047*
H16B	0.8900	0.2830	0.4996	0.047*
H16C	0.8154	0.2426	0.4794	0.047*
C18	0.81968 (17)	0.5148 (2)	0.4800 (2)	0.0244 (7)
C19	0.83756 (17)	0.5989 (2)	0.4963 (2)	0.0243 (7)
H19	0.8771	0.6147	0.5360	0.029*
C20	0.79452 (17)	0.6590 (2)	0.4514 (2)	0.0238 (7)
H20	0.8051	0.7180	0.4617	0.029*
C22	0.63954 (17)	0.9106 (2)	0.2739 (2)	0.0246 (7)
H22	0.6757	0.9250	0.3197	0.030*
C23	0.60218 (17)	0.9759 (2)	0.2279 (2)	0.0226 (7)
C24	0.60092 (18)	1.0681 (2)	0.2304 (2)	0.0263 (8)
H24	0.6297	1.1042	0.2701	0.032*
C25	0.55152 (18)	1.0935 (2)	0.1662 (2)	0.0275 (8)
C26	0.5241 (2)	1.1790 (3)	0.1366 (3)	0.0374 (9)
H26A	0.5440	1.2229	0.1791	0.056*
H26B	0.4746	1.1790	0.1347	0.056*
H26C	0.5356	1.1917	0.0766	0.056*
C28	0.55083 (18)	0.9522 (2)	0.1590 (2)	0.0266 (8)
C29	0.53615 (18)	0.8676 (2)	0.1379 (2)	0.0301 (8)
H29	0.5011	0.8515	0.0913	0.036*
C30	0.57544 (18)	0.8075 (2)	0.1887 (2)	0.0282 (8)
H30	0.5665	0.7485	0.1761	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0215 (2)	0.0189 (2)	0.0251 (2)	−0.00278 (18)	0.00206 (15)	0.00040 (16)
Cl1	0.0352 (5)	0.0397 (6)	0.0453 (6)	−0.0002 (4)	0.0153 (4)	0.0061 (4)
Cl2	0.0403 (6)	0.0577 (8)	0.0748 (8)	−0.0195 (6)	0.0142 (5)	0.0131 (6)
O1	0.0346 (15)	0.0283 (15)	0.0303 (13)	−0.0045 (12)	0.0037 (10)	−0.0056 (10)
O4	0.0244 (13)	0.0213 (13)	0.0276 (13)	−0.0045 (10)	0.0031 (9)	−0.0003 (9)
O5	0.0376 (15)	0.0274 (15)	0.0333 (14)	−0.0084 (12)	0.0033 (11)	−0.0046 (11)
O8	0.0220 (13)	0.0193 (13)	0.0346 (13)	−0.0003 (10)	0.0023 (10)	0.0006 (10)
O9	0.0335 (15)	0.0354 (15)	0.0353 (14)	−0.0043 (12)	0.0065 (11)	−0.0019 (11)
O17	0.0273 (13)	0.0228 (13)	0.0265 (12)	−0.0005 (11)	−0.0017 (9)	0.0015 (10)
O27	0.0319 (14)	0.0308 (15)	0.0277 (13)	0.0050 (12)	−0.0028 (10)	0.0045 (10)
N11	0.0246 (16)	0.0272 (17)	0.0199 (14)	−0.0026 (13)	0.0030 (11)	−0.0017 (11)
N21	0.0215 (15)	0.0263 (17)	0.0224 (14)	−0.0026 (12)	0.0036 (11)	0.0001 (11)
C1	0.051 (3)	0.030 (2)	0.040 (2)	−0.0026 (19)	0.0080 (18)	−0.0042 (17)
C2	0.028 (2)	0.0220 (19)	0.0347 (19)	−0.0048 (16)	0.0075 (15)	−0.0013 (14)
C3	0.0235 (19)	0.0196 (19)	0.0277 (19)	0.0012 (14)	−0.0017 (14)	0.0036 (14)
C6	0.026 (2)	0.029 (2)	0.046 (2)	−0.0072 (16)	0.0048 (16)	0.0026 (16)
C7	0.0230 (19)	0.0218 (19)	0.032 (2)	0.0004 (15)	−0.0009 (15)	0.0089 (15)
C12	0.0256 (19)	0.024 (2)	0.0245 (17)	−0.0046 (15)	0.0002 (13)	−0.0020 (14)
C13	0.0274 (19)	0.0249 (19)	0.0171 (16)	−0.0026 (15)	0.0020 (13)	−0.0008 (13)
C14	0.031 (2)	0.026 (2)	0.0242 (18)	−0.0025 (16)	−0.0014 (14)	−0.0038 (14)
C15	0.035 (2)	0.0222 (19)	0.0237 (18)	0.0001 (16)	0.0072 (14)	−0.0005 (13)
C16	0.034 (2)	0.027 (2)	0.034 (2)	0.0018 (16)	0.0025 (15)	0.0015 (15)
C18	0.0265 (19)	0.027 (2)	0.0197 (17)	0.0022 (16)	0.0033 (13)	0.0028 (13)
C19	0.0238 (19)	0.025 (2)	0.0236 (17)	−0.0045 (15)	0.0007 (13)	−0.0014 (13)
C20	0.0247 (19)	0.0228 (19)	0.0239 (17)	−0.0055 (15)	0.0030 (13)	−0.0022 (13)
C22	0.0252 (19)	0.025 (2)	0.0235 (17)	−0.0052 (15)	0.0030 (13)	−0.0008 (13)
C23	0.0227 (18)	0.0249 (19)	0.0196 (17)	−0.0006 (15)	0.0012 (12)	0.0015 (13)
C24	0.0263 (19)	0.024 (2)	0.0282 (18)	−0.0022 (15)	0.0024 (14)	0.0000 (14)
C25	0.026 (2)	0.027 (2)	0.0302 (19)	−0.0004 (16)	0.0081 (15)	0.0017 (14)
C26	0.038 (2)	0.035 (2)	0.038 (2)	0.0091 (19)	0.0036 (17)	0.0105 (16)
C28	0.0270 (19)	0.031 (2)	0.0220 (18)	0.0021 (16)	0.0052 (14)	0.0024 (14)
C29	0.026 (2)	0.034 (2)	0.0280 (19)	−0.0029 (16)	−0.0042 (14)	−0.0020 (15)
C30	0.028 (2)	0.027 (2)	0.0298 (19)	−0.0072 (16)	0.0023 (14)	−0.0049 (15)

Geometric parameters (Å, º) top

Cu1—O8	1.956 (2)	C14—C15	1.341 (5)
Cu1—O4	1.964 (2)	C14—H14	0.9500
Cu1—N21	2.031 (3)	C15—O17	1.404 (4)
Cu1—N11	2.046 (3)	C15—C16	1.484 (5)
Cu1—O1	2.311 (2)	C16—H16A	0.9800
Cu1—O5	2.833 (2)	C16—H16B	0.9800
Cl1—C2	1.786 (3)	C16—H16C	0.9800
Cl2—C6	1.767 (4)	O17—C18	1.367 (4)
Cl2—Cl2ⁱ	3.384 (2)	C18—C19	1.371 (5)
O1—C1	1.419 (4)	C19—C20	1.380 (5)
O1—H1O	0.84	C19—H19	0.9500
C1—H1A	0.9800	C20—H20	0.9500
C1—H1B	0.9800	N21—C22	1.343 (4)
C1—H1C	0.9800	N21—C30	1.353 (4)
O4—C3	1.282 (4)	C22—C23	1.385 (5)
O5—C3	1.239 (4)	C22—H22	0.9500
C2—C3	1.519 (5)	C23—C28	1.399 (5)
C2—H2A	0.9900	C23—C24	1.438 (5)
C2—H2B	0.9900	C24—C25	1.337 (5)
O8—C7	1.273 (4)	C24—H24	0.9500
O9—C7	1.240 (4)	C25—O27	1.398 (4)
C6—C7	1.509 (5)	C25—C26	1.483 (5)
C6—H6A	0.9900	C26—H26A	0.9800
C6—H6B	0.9900	C26—H26B	0.9800
N11—C12	1.351 (4)	C26—H26C	0.9800
N11—C20	1.359 (4)	O27—C28	1.362 (4)
C12—C13	1.382 (5)	C28—C29	1.378 (5)
C12—H12	0.9500	C29—C30	1.379 (5)
C13—C18	1.396 (5)	C29—H29	0.9500
C13—C14	1.442 (5)	C30—H30	0.9500

O8—Cu1—O4	171.36 (9)	C15—C14—C13	106.7 (3)
O8—Cu1—N21	88.12 (10)	C15—C14—H14	126.7
O4—Cu1—N21	91.19 (10)	C13—C14—H14	126.7
O8—Cu1—N11	90.01 (10)	C14—C15—O17	111.4 (3)
O4—Cu1—N11	90.14 (10)	C14—C15—C16	134.2 (3)
N21—Cu1—N11	176.10 (10)	O17—C15—C16	114.3 (3)
O8—Cu1—O1	96.14 (9)	C15—C16—H16A	109.5
O4—Cu1—O1	92.47 (9)	C15—C16—H16B	109.5
N21—Cu1—O1	90.02 (10)	H16A—C16—H16B	109.5
N11—Cu1—O1	93.59 (10)	C15—C16—H16C	109.5
O8—Cu1—O5	119.56 (8)	H16A—C16—H16C	109.5
O4—Cu1—O5	51.81 (8)	H16B—C16—H16C	109.5
N21—Cu1—O5	89.66 (9)	C18—O17—C15	105.6 (3)
N11—Cu1—O5	88.28 (9)	O17—C18—C19	127.1 (3)
O1—Cu1—O5	144.26 (8)	O17—C18—C13	110.4 (3)
C1—O1—Cu1	127.3 (2)	C19—C18—C13	122.4 (3)
C1—O1—H1O	108.3	C18—C19—C20	115.7 (3)
Cu1—O1—H1O	92.0	C18—C19—H19	122.1
O1—C1—H1A	109.8	C20—C19—H19	122.1
O1—C1—H1B	109.7	N11—C20—C19	124.0 (3)
H1A—C1—H1B	109.5	N11—C20—H20	118.0
O1—C1—H1C	109.0	C19—C20—H20	118.0
H1A—C1—H1C	109.5	C22—N21—C30	118.9 (3)
H1B—C1—H1C	109.5	C22—N21—Cu1	122.2 (2)
C3—O4—Cu1	111.3 (2)	C30—N21—Cu1	118.8 (2)
C3—O5—Cu1	71.48 (19)	N21—C22—C23	121.7 (3)
C3—C2—Cl1	113.2 (2)	N21—C22—H22	119.1
C3—C2—H2A	108.9	C23—C22—H22	119.1
Cl1—C2—H2A	108.9	C22—C23—C28	117.5 (3)
C3—C2—H2B	108.9	C22—C23—C24	136.9 (3)
Cl1—C2—H2B	108.9	C28—C23—C24	105.6 (3)
H2A—C2—H2B	107.8	C25—C24—C23	106.9 (3)
O5—C3—O4	125.0 (3)	C25—C24—H24	126.6
O5—C3—C2	122.9 (3)	C23—C24—H24	126.6
O4—C3—C2	112.1 (3)	C24—C25—O27	111.4 (3)
C7—O8—Cu1	126.7 (2)	C24—C25—C26	133.1 (3)
C7—C6—Cl2	113.5 (3)	O27—C25—C26	115.5 (3)
C7—C6—H6A	108.8	C25—C26—H26A	109.5
Cl2—C6—H6A	108.8	C25—C26—H26B	109.5
C7—C6—H6B	109.0	H26A—C26—H26B	109.5
Cl2—C6—H6B	108.9	C25—C26—H26C	109.5
H6A—C6—H6B	107.7	H26A—C26—H26C	109.5
O9—C7—O8	126.2 (3)	H26B—C26—H26C	109.5
O9—C7—C6	120.9 (3)	C28—O27—C25	105.9 (3)
O8—C7—C6	112.8 (3)	O27—C28—C29	127.7 (3)
C12—N11—C20	118.8 (3)	O27—C28—C23	110.2 (3)
C12—N11—Cu1	119.3 (2)	C29—C28—C23	122.1 (3)
C20—N11—Cu1	121.8 (2)	C28—C29—C30	115.9 (3)
N11—C12—C13	121.1 (3)	C28—C29—H29	122.0
N11—C12—H12	119.5	C30—C29—H29	122.0
C13—C12—H12	119.5	N21—C30—C29	123.9 (3)
C12—C13—C18	118.0 (3)	N21—C30—H30	118.1
C12—C13—C14	136.2 (3)	C29—C30—H30	118.1
C18—C13—C14	105.8 (3)

O8—Cu1—O1—C1	136.2 (3)	C13—C14—C15—C16	177.9 (4)
O4—Cu1—O1—C1	−44.5 (3)	C14—C15—O17—C18	−0.4 (4)
N21—Cu1—O1—C1	−135.7 (3)	C16—C15—O17—C18	−179.2 (3)
N11—Cu1—O1—C1	45.8 (3)	C15—O17—C18—C19	−179.3 (3)
O5—Cu1—O1—C1	−46.2 (3)	C15—O17—C18—C13	1.3 (3)
N21—Cu1—O4—C3	−92.4 (2)	C12—C13—C18—O17	178.7 (3)
N11—Cu1—O4—C3	83.9 (2)	C14—C13—C18—O17	−1.7 (4)
O1—Cu1—O4—C3	177.5 (2)	C12—C13—C18—C19	−0.7 (5)
O5—Cu1—O4—C3	−3.75 (19)	C14—C13—C18—C19	178.9 (3)
O8—Cu1—O5—C3	−176.77 (19)	O17—C18—C19—C20	−178.7 (3)
O4—Cu1—O5—C3	3.81 (19)	C13—C18—C19—C20	0.6 (5)
N21—Cu1—O5—C3	95.6 (2)	C12—N11—C20—C19	0.9 (5)
N11—Cu1—O5—C3	−87.7 (2)	Cu1—N11—C20—C19	−174.1 (2)
O1—Cu1—O5—C3	6.0 (3)	C18—C19—C20—N11	−0.7 (5)
Cu1—O5—C3—O4	−5.6 (3)	O8—Cu1—N21—C22	−26.3 (3)
Cu1—O5—C3—C2	172.3 (3)	O4—Cu1—N21—C22	145.1 (3)
Cu1—O4—C3—O5	8.2 (4)	O1—Cu1—N21—C22	−122.5 (3)
Cu1—O4—C3—C2	−169.9 (2)	O5—Cu1—N21—C22	93.3 (3)
Cl1—C2—C3—O5	7.2 (4)	O8—Cu1—N21—C30	151.0 (2)
Cl1—C2—C3—O4	−174.6 (2)	O4—Cu1—N21—C30	−37.6 (2)
N21—Cu1—O8—C7	−106.4 (3)	O1—Cu1—N21—C30	54.8 (2)
N11—Cu1—O8—C7	77.0 (3)	O5—Cu1—N21—C30	−89.4 (2)
O1—Cu1—O8—C7	−16.6 (3)	C30—N21—C22—C23	1.5 (5)
O5—Cu1—O8—C7	165.0 (2)	Cu1—N21—C22—C23	178.7 (2)
Cl2ⁱ—Cl2—C6—C7	−117.3 (3)	N21—C22—C23—C28	−2.0 (5)
Cu1—O8—C7—O9	4.8 (5)	N21—C22—C23—C24	178.3 (4)
Cu1—O8—C7—C6	−172.6 (2)	C22—C23—C24—C25	179.6 (4)
Cl2—C6—C7—O9	29.4 (4)	C28—C23—C24—C25	0.0 (4)
Cl2—C6—C7—O8	−153.1 (3)	C23—C24—C25—O27	−0.2 (4)
O8—Cu1—N11—C12	−156.7 (2)	C23—C24—C25—C26	178.3 (4)
O4—Cu1—N11—C12	31.9 (2)	C24—C25—O27—C28	0.4 (4)
O1—Cu1—N11—C12	−60.6 (2)	C26—C25—O27—C28	−178.4 (3)
O5—Cu1—N11—C12	83.7 (2)	C25—O27—C28—C29	178.6 (3)
O8—Cu1—N11—C20	18.3 (3)	C25—O27—C28—C23	−0.4 (3)
O4—Cu1—N11—C20	−153.1 (2)	C22—C23—C28—O27	−179.4 (3)
O1—Cu1—N11—C20	114.4 (2)	C24—C23—C28—O27	0.3 (4)
O5—Cu1—N11—C20	−101.3 (2)	C22—C23—C28—C29	1.5 (5)
C20—N11—C12—C13	−1.0 (5)	C24—C23—C28—C29	−178.8 (3)
Cu1—N11—C12—C13	174.2 (2)	O27—C28—C29—C30	−179.3 (3)
N11—C12—C13—C18	0.9 (5)	C23—C28—C29—C30	−0.4 (5)
N11—C12—C13—C14	−178.6 (3)	C22—N21—C30—C29	−0.3 (5)
C12—C13—C14—C15	−179.1 (4)	Cu1—N21—C30—C29	−177.6 (3)
C18—C13—C14—C15	1.4 (4)	C28—C29—C30—N21	−0.3 (5)
C13—C14—C15—O17	−0.6 (4)

Symmetry code: (i) −x+2, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

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···O5ⁱⁱ	0.99	2.60	3.510 (4)	154
C16—H16C···O1ⁱⁱⁱ	0.98	2.63	3.413 (4)	137
C14—H14···O9ⁱⁱⁱ	0.95	2.55	3.450 (4)	159
C20—H20···O5ⁱⁱ	0.95	2.57	3.221 (4)	126
C29—H29···O5^iv	0.95	2.69	3.451 (4)	138
C19—H19···O5ⁱⁱ	0.95	2.65	3.235 (4)	120
C16—H16A···O9^v	0.98	2.65	3.610 (4)	167
C24—H24···O9^vi	0.95	2.67	3.408 (4)	135
C1—H1B···C14^vii	0.98	2.87	3.834 (4)	168

Symmetry codes: (ii) −x+3/2, −y+3/2, −z+1; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+1, y, −z+1/2; (v) x, −y+1, z+1/2; (vi) −x+3/2, y+1/2, −z+1/2; (vii) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₂ClO₂)₂(C₈H₇NO)₂(CH₄O)]
M_r	548.86
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	19.860 (3), 15.576 (3), 15.017 (3)
β (°)	97.917 (3)
V (Å³)	4600.9 (15)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.23
Crystal size (mm)	0.26 × 0.20 × 0.16

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.776, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	16690, 4021, 3093
R_int	0.076
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.103, 1.02
No. of reflections	4021
No. of parameters	300
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.08, −0.53

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), enCIFer (Allen et al., 2004).

Selected bond lengths (Å) top

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O9	0.84	1.86	2.664 (3)	158.7
C12—H12···O4	0.95	2.44	2.944 (4)	113.1
C20—H20···O8	0.95	2.40	2.915 (4)	114.1
C22—H22···O8	0.95	2.41	2.886 (4)	110.9
C30—H30···O4	0.95	2.53	3.000 (4)	110.6
C6—H6A···O5ⁱ	0.99	2.60	3.510 (4)	153.6
C16—H16C···O1ⁱⁱ	0.98	2.63	3.413 (4)	137.4
C14—H14···O9ⁱⁱ	0.95	2.55	3.450 (4)	159.0
C20—H20···O5ⁱ	0.95	2.57	3.221 (4)	126.3
C29—H29···O5ⁱⁱⁱ	0.95	2.69	3.451 (4)	137.8
C19—H19···O5ⁱ	0.95	2.65	3.235 (4)	120.1
C16—H16A···O9^iv	0.98	2.65	3.610 (4)	166.7
C24—H24···O9^v	0.95	2.67	3.408 (4)	134.7
C1—H1B···C14^vi	0.98	2.87	3.834 (4)	168

Symmetry codes: (i) −x+3/2, −y+3/2, −z+1; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+1, y, −z+1/2; (iv) x, −y+1, z+1/2; (v) −x+3/2, y+1/2, −z+1/2; (vi) x, −y+1, z−1/2.

Acknowledgements

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.

References

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CrossRef CAS IUCr Journals Google Scholar
Baran, P., Boča, M., Boča, R., Krutošíková, A., Miklovič, J., Pelikán, J. & Titiš, J. (2005). Polyhedron, 24, 1510–1516. Web of Science CSD CrossRef CAS Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Borel, M.-M., Boniak, L., Busnot, F. & Leclaire, A. (1978). Rev. Chim. Miner. 15, 397–405. CAS Google Scholar
Desiraju, G. R. (1995). Angew. Chem. Int. Ed. Engl. 34, 2311–2327. CrossRef CAS Web of Science Google Scholar
Eloy, F. & Deryckere, A. (1971). J. Heterocycl. Chem. 8, 57–60. CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Ivaniková, R., Boča, R., Dlháň, Ľ., Fuess, H., Mašlejová, A., Mrázová, V., Svoboda, I. & Titiš, J. (2006). Polyhedron, 25, 3261–3268. Google Scholar
Janiak, C. (2000). J. Chem. Soc. Dalton Trans. pp. 3885–3896. Web of Science CrossRef Google Scholar
Mikloš, D., Jašková, J., Segľa, P., Miklovič, J., Mrázová, V., Kaliňaková, B., Hudecová, D., Sillanpää, R., Lis, T. & Melník, M. (2005). Advances in Coordination, Bioinorganic and Inorganic Chemistry, Vol. 7, edited by M. Melník, J. Šima & M. Tatarko, pp. 201–217. Bratislava: Slovak Technical University Press. Google Scholar
Miklovič, J., Krutošíková, A. & Baran, P. (2004). Acta Cryst. C60, m227–m230. Web of Science CSD CrossRef IUCr Journals Google Scholar
Moncol, J., Segľa, P., Jašková, J., Fischer, A. & Melník, M. (2007). Acta Cryst. E63, m698–m700. Web of Science CSD CrossRef IUCr Journals Google Scholar
New, J. S., Christopher, W. L., Yevich, J. P., Butler, R., Schlemmer, R. F. Jr, van der Maelen, C. P. & Cipolline, J. A. (1989). J. Med. Chem. 32, 1147–1156. CrossRef CAS PubMed Web of Science Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Segľa, P., Jašková, J., Mikloš, D., Kaliňaková, B., Hudecová, D., Miklovič, J., Mrázová, V., Švorec, J., Lis, T. & Melník, M. (2005). Advances in Coordination, Bioinorganic and Inorganic Chemistry, Vol. 7, edited by M. Melník, J. Šima & M. Tatarko, pp. 323–340. Bratislava: Slovak Technical University Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Suezawa, H., Yoshida, T., Umezawa, Y., Tsuboyama, S. & Nishio, M. (2002). Eur. J. Inorg. Chem. pp. 3148–3155. CrossRef Google Scholar
Titiš, J., Boča, R., Dlháň, Ľ., Ďurčeková, T., Fuess, H., Ivaniková, R., Mrázová, V., Papánková, B. & Svoboda, I. (2007). Polyhedron, 26, 1523–1530. Google Scholar
Vrábel, V., Švorc, Ľ., Juristová, N., Miklovič, J. & Kožíšek, J. (2007a). Acta Cryst. E63, m2112–m2113. Web of Science CSD CrossRef IUCr Journals Google Scholar
Vrábel, V., Švorc, Ľ., Juristová, N., Miklovič, J. & Kožíšek, J. (2007b). Acta Cryst. E63, m2427–m2428. Web of Science CSD CrossRef IUCr Journals Google Scholar
Wang, P., Dong, Y.-B., Ma, J.-P., Huang, R.-Q. & Smith, M. D. (2005). Inorg. Chem. Commun. 8, 596–599. Web of Science CSD CrossRef CAS Google Scholar

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