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

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.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.028
• wR factor = 0.072
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          1
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1    --  O3A     ..        9.7 su
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          4
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu1     (II)          2.09

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

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 U_eq(H) = 1.2U_iso(C). H atoms bonded to O were permitted to ride with O—H = 0.820 Å and U_eq(H)=1.5_iso(O), those of the CH₂ group were constrained with C—H = 0.97 Å and U_eq(H)=1.2U_iso(C).

Computing details

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

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)

Crystal data

[Cu(C2H3O2)2(C7H9NO)2]	F(000) = 446
Mr = 427.93	Dx = 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) Å^3	0.2 × 0.18 × 0.15 mm
Z = 2

Data collection

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	Rint = 0.024
Detector resolution: 10.4933 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω–scans	h = −8→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −9→10
Tmin = 0.792, Tmax = 1.0	l = −19→10
5287 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0265P)^2 + 0.6754P] where P = (Fo^2 + 2Fc^2)/3
2178 reflections	(Δ/σ)max < 0.001
126 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Cu1—O1^i	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—N11^i	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
O1^i—Cu1—O1	180.0	N11—C16—C1A	119.08 (15)
O1^i—Cu1—N11	91.73 (5)	C15—C16—C1A	120.42 (16)
O1—Cu1—N11	88.27 (5)	C16—C1A—C2A	114.37 (15)
O1^i—Cu1—N11^i	88.27 (5)	C16—C1A—H1A1	108.7
O1—Cu1—N11^i	91.73 (5)	C2A—C1A—H1A1	108.7
N11—Cu1—N11^i	180.00 (7)	C16—C1A—H1A2	108.7
O1^i—Cu1—O3A^i	92.88 (5)	C2A—C1A—H1A2	108.7
O1—Cu1—O3A^i	87.12 (5)	H1A1—C1A—H1A2	107.6
N11—Cu1—O3A^i	92.49 (5)	O3A—C2A—C1A	110.80 (15)
N11^i—Cu1—O3A^i	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)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O3A^i	0.93	2.46	3.105 (2)	127
C13—H13···O1^ii	0.93	2.51	3.424 (2)	168
C14—H14···O2^iii	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.