Bis(acetato-κO)bis­[2-(pyridin-2-yl)ethanol-κ2N,O]copper(II)

Lapanje, K.; Leban, I.; Lah, N.

doi:10.1107/S1600536812015747

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m599

doi:10.1107/S1600536812015747

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Bis(acetato-κO)bis[2-(pyridin-2-yl)ethanol-κ²N,O]copper(II)

Katja Lapanje,^a Ivan Leban ^a and Nina Lah ^a ^*

^aUniversity of Ljubljana, Faculty of Chemistry and Chemical Technology, Aškerčeva 5, 1000 Ljubljana, Slovenia
^*Correspondence e-mail: nina.lah@fkkt.uni-lj.si

(Received 5 April 2012; accepted 11 April 2012; online 18 April 2012)

The title compound, [Cu(CH₃COO)₂(C₇H₉NO)₂], is a monomeric complex with an octahedral geometry. The Cu^II atom is located on an inversion center and is coordinated by acetate and 2-(pyridin-2-yl)ethanol ligands. The acetate group is coordinated in a monodentate manner, while the 2-(pyridin-2-yl)ethanol is coordinated as a bidentate ligand involving the endocyclic N atom and the hydroxy O atom of the ligand side chain. An intramolecular hydrogen bond is observed between the hydroxy O atom and the non-coordinated acetate O atom. No classical intermolecular hydrogen-bond contacts were observed. However, the crystal packing is effected by C—H⋯O interactions, which link the mononuclear entities into layers parallel to the bc plane.

Related literature

For related structures, see: Pothiraja et al. (2011 ); Yilmaz et al. (2003 ). For copper halogenido complexes with 2-(pyridin-2-yl)ethanol, see: Hamamci et al. (2004 ); Lah & Leban (2010 ). For copper complexes with acetate and 2-(pyridin-2-yl)ethanol in its deprotonated form, see, for example: Mobin et al. (2010 ).

Experimental

Crystal data

[Cu(C₂H₃O₂)₂(C₇H₉NO)₂]
M_r = 427.93
Monoclinic, P 2₁ /c
a = 8.3521 (3) Å
b = 7.7547 (2) Å
c = 15.1953 (5) Å
β = 104.447 (3)°
V = 953.05 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.18 mm⁻¹
T = 150 K
0.2 × 0.18 × 0.15 mm

Data collection

Agilent SuperNova Dual/Cu at zero/Atlas diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.792, T_max = 1.0
5287 measured reflections
2178 independent reflections
1867 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.072
S = 1.05
2178 reflections
126 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9816 (12)
Cu1—N11	2.0324 (14)
Cu1—O3A	2.4218 (13)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O3Aⁱ	0.93	2.46	3.105 (2)	127
C13—H13⋯O1ⁱⁱ	0.93	2.51	3.424 (2)	168
C14—H14⋯O2ⁱⁱⁱ	0.93	2.53	3.050 (2)	115
O3A—H3A⋯O2	0.82	1.79	2.595 (2)	169
Symmetry codes: (i) -x+2, -y, -z+2; (ii) -x+2, -y+1, -z+2; (iii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812015747/bq2349sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812015747/bq2349Isup2.hkl

checkCIF report

Comment top

Simple pyridine alcohol ligands are commercially available substances which are of particular interest in coordination chemistry since they possess two functional groups, both capable to coordinate to metal centers. They can react as neutral ligands with a preserved alcohol function or as anionic (alkoxo) ligands with the OH group being deprotonated. The literature reports on some Cu^II species incorporating 2-(pyridin-2-yl)ethanol (2-pyEtOH) as a neutral ligand to copper atoms (i.e. Pothiraja et al., 2011; Yilmaz et al., 2003; Hamamci et al., 2004; Lah & Leban, 2010) and a series of Cu^II acetato compounds with 2-pyEtOH in its deprotonated form (Mobin et al., 2010). We report here the synthesis and crystal structure of new mononuclear Cu^II complex with 2-pyEtOH coordinated as a neutral ligand in a chelating manner using both functional groups. Cu atom is located on the inversion center and possesses a distorted octahedral environment with two O-atoms belonging to two acetato ligands, two O-atoms of the 2-pyEtOH side chains and two pyridine N atoms of the 2-pyEtOH ligands (Figure 1). An intramolecular hydrogen bond is observed between the hydroxy oxygen as a donor and the noncoordinated acetato oxygen as an acceptor. No classical intermolecular hydrogen-bond contacts were observed. However, crystal packing is effected by intermolecular C—H···O interactions involving aromatic C—H as donors and oxygen atoms of both ligands as acceptors. Thus, mononuclear units are linked into two-dimensional layers parallel to bc plane. See Table 2 for details.

Related literature top

For related structures, see: Pothiraja et al. (2011); Yilmaz et al. (2003). For copper halogenido complexes with 2-(pyridin-2-yl)ethanol, see: Hamamci et al. (2004); Lah & Leban (2010). For copper complexes with acetate and 2-(pyridin-2-yl)ethanol in its deprotonated form, see, for example: Mobin et al. (2010).

Experimental top

0,20 g of copper acetate hydrate was dissolved in 10,0 ml of methanol. 0,10 g of malonic acid and 0,10 ml of 2-(pyridin-2-yl)ethanol was added during intense stirring. The resulting blue solution was left at ambient condition to slowly evaporate the solvent. Within few days light blue crystals of the title compound appeared.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. An ORTEP view of the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Bis(acetato-κO)bis[2-(pyridin-2-yl)ethanol- κ²N,O]copper(II) top

Crystal data top

[Cu(C₂H₃O₂)₂(C₇H₉NO)₂]	F(000) = 446
M_r = 427.93	D_x = 1.491 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3095 reflections
a = 8.3521 (3) Å	θ = 3.0–30.6°
b = 7.7547 (2) Å	µ = 1.18 mm⁻¹
c = 15.1953 (5) Å	T = 150 K
β = 104.447 (3)°	Prismatic, blue
V = 953.05 (5) Å³	0.2 × 0.18 × 0.15 mm
Z = 2

Data collection top

Agilent SuperNova Dual/Cu at zero/Atlas diffractometer	2178 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1867 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.024
Detector resolution: 10.4933 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω–scans	h = −8→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −9→10
T_min = 0.792, T_max = 1.0	l = −19→10
5287 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.072	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0265P)² + 0.6754P] where P = (F_o² + 2F_c²)/3
2178 reflections	(Δ/σ)_max < 0.001
126 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Cu(C₂H₃O₂)₂(C₇H₉NO)₂]	V = 953.05 (5) Å³
M_r = 427.93	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3521 (3) Å	µ = 1.18 mm⁻¹
b = 7.7547 (2) Å	T = 150 K
c = 15.1953 (5) Å	0.2 × 0.18 × 0.15 mm
β = 104.447 (3)°

Data collection top

Agilent SuperNova Dual/Cu at zero/Atlas diffractometer	2178 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	1867 reflections with I > 2σ(I)
T_min = 0.792, T_max = 1.0	R_int = 0.024
5287 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.072	H-atom parameters constrained
S = 1.05	Δρ_max = 0.35 e Å⁻³
2178 reflections	Δρ_min = −0.40 e Å⁻³
126 parameters

Special details top

Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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

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

	x	y	z	U_iso*/U_eq
Cu1	1.0000	0.0000	1.0000	0.01445 (10)
N11	0.85389 (18)	0.16632 (18)	0.91187 (10)	0.0167 (3)
C12	0.8605 (2)	0.3316 (2)	0.94034 (13)	0.0192 (4)
H12	0.9201	0.3564	0.9993	0.023*
C13	0.7832 (2)	0.4656 (2)	0.88638 (13)	0.0211 (4)
H13	0.7895	0.5777	0.9087	0.025*
C14	0.6963 (2)	0.4293 (3)	0.79849 (13)	0.0224 (4)
H14	0.6442	0.5168	0.7601	0.027*
C15	0.6882 (2)	0.2599 (2)	0.76858 (13)	0.0214 (4)
H15	0.6300	0.2333	0.7096	0.026*
C16	0.7665 (2)	0.1294 (2)	0.82624 (12)	0.0175 (4)
C1A	0.7575 (2)	−0.0547 (2)	0.79380 (12)	0.0210 (4)
H1A1	0.6764	−0.0622	0.7358	0.025*
H1A2	0.7190	−0.1263	0.8367	0.025*
C2A	0.9212 (2)	−0.1272 (2)	0.78271 (12)	0.0223 (4)
H2A1	0.9008	−0.2326	0.7473	0.027*
H2A2	0.9722	−0.0448	0.7500	0.027*
O3A	1.03055 (16)	−0.16208 (17)	0.86893 (9)	0.0223 (3)
H3A	1.1191	−0.1133	0.8724	0.033*
O1	1.19060 (15)	0.15137 (15)	0.99881 (9)	0.0192 (3)
C2	1.4324 (3)	0.2700 (3)	0.96919 (16)	0.0338 (5)
H2A	1.5099	0.2478	1.0263	0.051*
H2B	1.3846	0.3823	0.9706	0.051*
H2C	1.4885	0.2656	0.9212	0.051*
C1	1.2976 (2)	0.1355 (2)	0.95261 (12)	0.0217 (4)
O2	1.2994 (2)	0.0195 (2)	0.89625 (11)	0.0378 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01415 (16)	0.01239 (16)	0.01711 (16)	−0.00139 (11)	0.00446 (11)	−0.00008 (11)
N11	0.0160 (7)	0.0153 (7)	0.0190 (7)	−0.0021 (6)	0.0047 (6)	−0.0003 (6)
C12	0.0192 (9)	0.0174 (9)	0.0210 (9)	−0.0027 (7)	0.0050 (7)	−0.0019 (7)
C13	0.0201 (9)	0.0169 (9)	0.0280 (10)	−0.0006 (7)	0.0090 (8)	0.0011 (7)
C14	0.0201 (10)	0.0233 (9)	0.0254 (9)	0.0025 (8)	0.0085 (8)	0.0078 (7)
C15	0.0184 (9)	0.0275 (10)	0.0179 (9)	−0.0005 (8)	0.0036 (7)	0.0024 (7)
C16	0.0135 (8)	0.0208 (9)	0.0196 (8)	−0.0021 (7)	0.0069 (7)	−0.0004 (7)
C1A	0.0206 (9)	0.0215 (9)	0.0193 (9)	−0.0031 (8)	0.0020 (7)	−0.0032 (7)
C2A	0.0245 (10)	0.0232 (9)	0.0191 (9)	−0.0007 (8)	0.0050 (8)	−0.0049 (7)
O3A	0.0200 (7)	0.0248 (7)	0.0221 (7)	−0.0007 (6)	0.0052 (5)	−0.0005 (5)
O1	0.0183 (6)	0.0168 (6)	0.0240 (6)	−0.0035 (5)	0.0081 (5)	−0.0016 (5)
C2	0.0280 (11)	0.0401 (12)	0.0374 (12)	−0.0155 (10)	0.0156 (10)	−0.0041 (10)
C1	0.0188 (9)	0.0278 (10)	0.0184 (9)	−0.0030 (8)	0.0046 (7)	0.0021 (7)
O2	0.0285 (8)	0.0553 (10)	0.0339 (8)	−0.0153 (7)	0.0159 (7)	−0.0229 (7)

Geometric parameters (Å, º) top

Cu1—O1ⁱ	1.9816 (12)	C16—C1A	1.506 (3)
Cu1—O1	1.9816 (12)	C1A—C2A	1.526 (3)
Cu1—N11	2.0324 (14)	C1A—H1A1	0.9700
Cu1—N11ⁱ	2.0324 (14)	C1A—H1A2	0.9700
Cu1—O3A	2.4218 (13)	C2A—O3A	1.424 (2)
N11—C12	1.349 (2)	C2A—H2A1	0.9700
N11—C16	1.354 (2)	C2A—H2A2	0.9700
C12—C13	1.380 (3)	O3A—H3A	0.8200
C12—H12	0.9300	O1—C1	1.273 (2)
C13—C14	1.381 (3)	C2—C1	1.509 (3)
C13—H13	0.9300	C2—H2A	0.9600
C14—C15	1.386 (3)	C2—H2B	0.9600
C14—H14	0.9300	C2—H2C	0.9600
C15—C16	1.390 (3)	C1—O2	1.245 (2)
C15—H15	0.9300

O1ⁱ—Cu1—O1	180.0	N11—C16—C1A	119.08 (15)
O1ⁱ—Cu1—N11	91.73 (5)	C15—C16—C1A	120.42 (16)
O1—Cu1—N11	88.27 (5)	C16—C1A—C2A	114.37 (15)
O1ⁱ—Cu1—N11ⁱ	88.27 (5)	C16—C1A—H1A1	108.7
O1—Cu1—N11ⁱ	91.73 (5)	C2A—C1A—H1A1	108.7
N11—Cu1—N11ⁱ	180.00 (7)	C16—C1A—H1A2	108.7
O1ⁱ—Cu1—O3Aⁱ	92.88 (5)	C2A—C1A—H1A2	108.7
O1—Cu1—O3Aⁱ	87.12 (5)	H1A1—C1A—H1A2	107.6
N11—Cu1—O3Aⁱ	92.49 (5)	O3A—C2A—C1A	110.80 (15)
N11ⁱ—Cu1—O3Aⁱ	87.51 (5)	O3A—C2A—H2A1	109.5
C12—N11—C16	118.56 (15)	C1A—C2A—H2A1	109.5
C12—N11—Cu1	114.94 (12)	O3A—C2A—H2A2	109.5
C16—N11—Cu1	126.15 (12)	C1A—C2A—H2A2	109.5
N11—C12—C13	123.31 (17)	H2A1—C2A—H2A2	108.1
N11—C12—H12	118.3	C2A—O3A—H3A	109.5
C13—C12—H12	118.3	C1—O1—Cu1	128.62 (12)
C12—C13—C14	118.42 (17)	C1—C2—H2A	109.5
C12—C13—H13	120.8	C1—C2—H2B	109.5
C14—C13—H13	120.8	H2A—C2—H2B	109.5
C13—C14—C15	118.79 (17)	C1—C2—H2C	109.5
C13—C14—H14	120.6	H2A—C2—H2C	109.5
C15—C14—H14	120.6	H2B—C2—H2C	109.5
C14—C15—C16	120.41 (17)	O2—C1—O1	125.43 (18)
C14—C15—H15	119.8	O2—C1—C2	118.56 (18)
C16—C15—H15	119.8	O1—C1—C2	116.01 (17)
N11—C16—C15	120.49 (16)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O3Aⁱ	0.93	2.46	3.105 (2)	127
C13—H13···O1ⁱⁱ	0.93	2.51	3.424 (2)	168
C14—H14···O2ⁱⁱⁱ	0.93	2.53	3.050 (2)	115
O3A—H3A···O2	0.82	1.79	2.595 (2)	169

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

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₃O₂)₂(C₇H₉NO)₂]
M_r	427.93
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	8.3521 (3), 7.7547 (2), 15.1953 (5)
β (°)	104.447 (3)
V (Å³)	953.05 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.18
Crystal size (mm)	0.2 × 0.18 × 0.15

Data collection
Diffractometer	Agilent SuperNova Dual/Cu at zero/Atlas diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.792, 1.0
No. of measured, independent and observed [I > 2σ(I)] reflections	5287, 2178, 1867
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.072, 1.05
No. of reflections	2178
No. of parameters	126
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.40

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—O1	1.9816 (12)	Cu1—O3A	2.4218 (13)
Cu1—N11	2.0324 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O3Aⁱ	0.93	2.46	3.105 (2)	126.8
C13—H13···O1ⁱⁱ	0.93	2.51	3.424 (2)	167.6
C14—H14···O2ⁱⁱⁱ	0.93	2.53	3.050 (2)	115.3
O3A—H3A···O2	0.82	1.79	2.595 (2)	168.6

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

Acknowledgements

The work was supported by the Slovenian Ministry of Education, Science, Culture and Sport through grant No. P1–0175. EN-FIST Centre of Excellence, Dunajska 156, 1000 Ljubljana, Slovenia is acknowledged for the use of the Supernova diffractometer.

References

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