metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

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 CuII 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[Pothiraja, R., Sathiyendiran, M., Steiner, A. & Murugavel, R. (2011). Inorg. Chim. Acta, 372, 347-352.]); Yilmaz et al. (2003[Yilmaz, V. T., Hamamci, S. & Thone, C. (2003). J. Coord. Chem. 56, 787-795.]). For copper halogenido complexes with 2-(pyridin-2-yl)ethanol, see: Hamamci et al. (2004[Hamamci, S., Yilmaz, V. T. & Thöne, C. (2004). Acta Cryst. E60, m159-m161.]); Lah & Leban (2010[Lah, N. & Leban, I. (2010). Struct. Chem. 21, 263-267.]). For copper complexes with acetate and 2-(pyridin-2-yl)ethanol in its deprotonated form, see, for example: Mobin et al. (2010[Mobin, S. M., Srivastava, A. K., Mathur, P. & Lahiri, G. K. (2010). Dalton Trans. 39, 1447-1449.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu(C2H3O2)2(C7H9NO)2]

  • Mr = 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[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.]) Tmin = 0.792, Tmax = 1.0

  • 5287 measured reflections

  • 2178 independent reflections

  • 1867 reflections with I > 2σ(I)

  • Rint = 0.024

Refinement
  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.072

  • S = 1.05

  • 2178 reflections

  • 126 parameters

  • H-atom parameters constrained

  • Δρmax = 0.35 e Å−3

  • Δρmin = −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 DA 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[Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.]); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 CuII 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 CuII acetato compounds with 2-pyEtOH in its deprotonated form (Mobin et al., 2010). We report here the synthesis and crystal structure of new mononuclear CuII 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.

Refinement top

All H atoms were initially found in a Fourier-difference map, but they were repositioned to their calculated positions and were refined using a riding model. Aromatic H atoms were permitted to ride with C—H = 0.93 Å and Ueq(H) = 1.2Uiso(C). H atoms bonded to O were permitted to ride with O—H = 0.820 Å and Ueq(H)=1.5iso(O), those of the CH2 group were constrained with C—H = 0.97 Å and Ueq(H)=1.2Uiso(C).

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
[Figure 1] 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
Mr = 427.93Dx = 1.491 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3095 reflections
a = 8.3521 (3) Åθ = 3.0–30.6°
b = 7.7547 (2) ŵ = 1.18 mm1
c = 15.1953 (5) ÅT = 150 K
β = 104.447 (3)°Prismatic, blue
V = 953.05 (5) Å30.2 × 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 Source1867 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.024
Detector resolution: 10.4933 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω–scansh = 810
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 910
Tmin = 0.792, Tmax = 1.0l = 1910
5287 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0265P)2 + 0.6754P]
where P = (Fo2 + 2Fc2)/3
2178 reflections(Δ/σ)max < 0.001
126 parametersΔρmax = 0.35 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
[Cu(C2H3O2)2(C7H9NO)2]V = 953.05 (5) Å3
Mr = 427.93Z = 2
Monoclinic, P21/cMo Kα radiation
a = 8.3521 (3) ŵ = 1.18 mm1
b = 7.7547 (2) ÅT = 150 K
c = 15.1953 (5) Å0.2 × 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)
Tmin = 0.792, Tmax = 1.0Rint = 0.024
5287 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.072H-atom parameters constrained
S = 1.05Δρmax = 0.35 e Å3
2178 reflectionsΔρmin = 0.40 e Å3
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
xyzUiso*/Ueq
Cu11.00000.00001.00000.01445 (10)
N110.85389 (18)0.16632 (18)0.91187 (10)0.0167 (3)
C120.8605 (2)0.3316 (2)0.94034 (13)0.0192 (4)
H120.92010.35640.99930.023*
C130.7832 (2)0.4656 (2)0.88638 (13)0.0211 (4)
H130.78950.57770.90870.025*
C140.6963 (2)0.4293 (3)0.79849 (13)0.0224 (4)
H140.64420.51680.76010.027*
C150.6882 (2)0.2599 (2)0.76858 (13)0.0214 (4)
H150.63000.23330.70960.026*
C160.7665 (2)0.1294 (2)0.82624 (12)0.0175 (4)
C1A0.7575 (2)0.0547 (2)0.79380 (12)0.0210 (4)
H1A10.67640.06220.73580.025*
H1A20.71900.12630.83670.025*
C2A0.9212 (2)0.1272 (2)0.78271 (12)0.0223 (4)
H2A10.90080.23260.74730.027*
H2A20.97220.04480.75000.027*
O3A1.03055 (16)0.16208 (17)0.86893 (9)0.0223 (3)
H3A1.11910.11330.87240.033*
O11.19060 (15)0.15137 (15)0.99881 (9)0.0192 (3)
C21.4324 (3)0.2700 (3)0.96919 (16)0.0338 (5)
H2A1.50990.24781.02630.051*
H2B1.38460.38230.97060.051*
H2C1.48850.26560.92120.051*
C11.2976 (2)0.1355 (2)0.95261 (12)0.0217 (4)
O21.2994 (2)0.0195 (2)0.89625 (11)0.0378 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01415 (16)0.01239 (16)0.01711 (16)0.00139 (11)0.00446 (11)0.00008 (11)
N110.0160 (7)0.0153 (7)0.0190 (7)0.0021 (6)0.0047 (6)0.0003 (6)
C120.0192 (9)0.0174 (9)0.0210 (9)0.0027 (7)0.0050 (7)0.0019 (7)
C130.0201 (9)0.0169 (9)0.0280 (10)0.0006 (7)0.0090 (8)0.0011 (7)
C140.0201 (10)0.0233 (9)0.0254 (9)0.0025 (8)0.0085 (8)0.0078 (7)
C150.0184 (9)0.0275 (10)0.0179 (9)0.0005 (8)0.0036 (7)0.0024 (7)
C160.0135 (8)0.0208 (9)0.0196 (8)0.0021 (7)0.0069 (7)0.0004 (7)
C1A0.0206 (9)0.0215 (9)0.0193 (9)0.0031 (8)0.0020 (7)0.0032 (7)
C2A0.0245 (10)0.0232 (9)0.0191 (9)0.0007 (8)0.0050 (8)0.0049 (7)
O3A0.0200 (7)0.0248 (7)0.0221 (7)0.0007 (6)0.0052 (5)0.0005 (5)
O10.0183 (6)0.0168 (6)0.0240 (6)0.0035 (5)0.0081 (5)0.0016 (5)
C20.0280 (11)0.0401 (12)0.0374 (12)0.0155 (10)0.0156 (10)0.0041 (10)
C10.0188 (9)0.0278 (10)0.0184 (9)0.0030 (8)0.0046 (7)0.0021 (7)
O20.0285 (8)0.0553 (10)0.0339 (8)0.0153 (7)0.0159 (7)0.0229 (7)
Geometric parameters (Å, º) top
Cu1—O1i1.9816 (12)C16—C1A1.506 (3)
Cu1—O11.9816 (12)C1A—C2A1.526 (3)
Cu1—N112.0324 (14)C1A—H1A10.9700
Cu1—N11i2.0324 (14)C1A—H1A20.9700
Cu1—O3A2.4218 (13)C2A—O3A1.424 (2)
N11—C121.349 (2)C2A—H2A10.9700
N11—C161.354 (2)C2A—H2A20.9700
C12—C131.380 (3)O3A—H3A0.8200
C12—H120.9300O1—C11.273 (2)
C13—C141.381 (3)C2—C11.509 (3)
C13—H130.9300C2—H2A0.9600
C14—C151.386 (3)C2—H2B0.9600
C14—H140.9300C2—H2C0.9600
C15—C161.390 (3)C1—O21.245 (2)
C15—H150.9300
O1i—Cu1—O1180.0N11—C16—C1A119.08 (15)
O1i—Cu1—N1191.73 (5)C15—C16—C1A120.42 (16)
O1—Cu1—N1188.27 (5)C16—C1A—C2A114.37 (15)
O1i—Cu1—N11i88.27 (5)C16—C1A—H1A1108.7
O1—Cu1—N11i91.73 (5)C2A—C1A—H1A1108.7
N11—Cu1—N11i180.00 (7)C16—C1A—H1A2108.7
O1i—Cu1—O3Ai92.88 (5)C2A—C1A—H1A2108.7
O1—Cu1—O3Ai87.12 (5)H1A1—C1A—H1A2107.6
N11—Cu1—O3Ai92.49 (5)O3A—C2A—C1A110.80 (15)
N11i—Cu1—O3Ai87.51 (5)O3A—C2A—H2A1109.5
C12—N11—C16118.56 (15)C1A—C2A—H2A1109.5
C12—N11—Cu1114.94 (12)O3A—C2A—H2A2109.5
C16—N11—Cu1126.15 (12)C1A—C2A—H2A2109.5
N11—C12—C13123.31 (17)H2A1—C2A—H2A2108.1
N11—C12—H12118.3C2A—O3A—H3A109.5
C13—C12—H12118.3C1—O1—Cu1128.62 (12)
C12—C13—C14118.42 (17)C1—C2—H2A109.5
C12—C13—H13120.8C1—C2—H2B109.5
C14—C13—H13120.8H2A—C2—H2B109.5
C13—C14—C15118.79 (17)C1—C2—H2C109.5
C13—C14—H14120.6H2A—C2—H2C109.5
C15—C14—H14120.6H2B—C2—H2C109.5
C14—C15—C16120.41 (17)O2—C1—O1125.43 (18)
C14—C15—H15119.8O2—C1—C2118.56 (18)
C16—C15—H15119.8O1—C1—C2116.01 (17)
N11—C16—C15120.49 (16)
Symmetry code: (i) x+2, y, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O3Ai0.932.463.105 (2)127
C13—H13···O1ii0.932.513.424 (2)168
C14—H14···O2iii0.932.533.050 (2)115
O3A—H3A···O20.821.792.595 (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]
Mr427.93
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)8.3521 (3), 7.7547 (2), 15.1953 (5)
β (°) 104.447 (3)
V3)953.05 (5)
Z2
Radiation typeMo Kα
µ (mm1)1.18
Crystal size (mm)0.2 × 0.18 × 0.15
Data collection
DiffractometerAgilent SuperNova Dual/Cu at zero/Atlas
diffractometer
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2011)
Tmin, Tmax0.792, 1.0
No. of measured, independent and
observed [I > 2σ(I)] reflections
5287, 2178, 1867
Rint0.024
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.072, 1.05
No. of reflections2178
No. of parameters126
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—O11.9816 (12)Cu1—O3A2.4218 (13)
Cu1—N112.0324 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O3Ai0.932.463.105 (2)126.8
C13—H13···O1ii0.932.513.424 (2)167.6
C14—H14···O2iii0.932.533.050 (2)115.3
O3A—H3A···O20.821.792.595 (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

First citationAgilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England.  Google Scholar
First citationHamamci, S., Yilmaz, V. T. & Thöne, C. (2004). Acta Cryst. E60, m159–m161.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationLah, N. & Leban, I. (2010). Struct. Chem. 21, 263–267.  Web of Science CSD CrossRef CAS Google Scholar
First citationMobin, S. M., Srivastava, A. K., Mathur, P. & Lahiri, G. K. (2010). Dalton Trans. 39, 1447–1449.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationPothiraja, R., Sathiyendiran, M., Steiner, A. & Murugavel, R. (2011). Inorg. Chim. Acta, 372, 347–352.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationYilmaz, V. T., Hamamci, S. & Thone, C. (2003). J. Coord. Chem. 56, 787–795.  Web of Science CSD CrossRef CAS Google Scholar

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