supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

Acta Cryst. (2008). E64, m1488-m1489    [ doi:10.1107/S1600536808034983 ]

Bis(di-2-pyridylmethanediol-[kappa]3N,O,N')copper(II) DL-tartrate

J. Zhao, D.-S. Li, W.-W. Dong, D.-J. Wang and L. Guo

Abstract top

The reaction of di-2-pyridyl ketone with copper dichloride dihydrate and tartaric acid in water afforded the title compound, [Cu(C11H10N2O2)2]C4H4O6. The CuII atom lies on an inversion center N,O,N'-chelated by two di-2-pyridylmethanediol ligands in a tetragonally distorted octahedral geometry. The tartrate anion is also located on an inversion center and has disordered hydroxyl groups, each with an occupancy factor of 0.5. The hydroxyl groups of the complex cation are hydrogen bonded to the carboxylate groups of the anion, thus connecting the two building units.

Comment top

Di-2-pyridylketone (dpk) functions either as a bidentate N,N'-donor or as a tridentate N,O,N'-donor towards metal ions, depending on the reaction medium used in the synthesis of the complexes (Deveson et al., 1996), and several mononuclear and polynuclear transition metal–dpk complexes have been reported (Sommerer et al., 1993; Wang et al., 1986). The structural investigations clearly demonstrate that in each case hydration occurs across the ketone double bond in the ligand and that the resulting hydroxyl group coordinates to metal.

In the title compound, two dipyridin-2-yl-methanediol ligands, each in a tridentate fashion, are bonded to the CuII atom lying on an inversion center (Fig. 1). The pyridyl N atoms are strongly coordinated to the metal in the equatorial plane, while the hydroxyl groups are relatively weakly coordinated in the axial positions (Table 1). The two Cu—O(hydroxy) bonds [2.392 (2) Å], being in a trans arrangement, significantly exceed the Cu—N bond distances, a feature which can be attributed to the Jahn-Teller effect and usually manifests in d9 metal systems. The tartrate anion is located on an inversion center with disordered hydroxyl groups, each has an occupancy factor of 0.5. The hydroxyl groups of the complex cation as donors are involved in hydrogen bonds with the tartrate anion (Table 2).

Related literature top

For backgroung on di-2-pyridylketone complexes, see: Deveson et al. (1996); Sommerer et al. (1993); Wang et al. (1986).

Experimental top

A mixture of di-2-pyridylketone (0.184 g, 1 mmol), CuCl2.2H2O (0.067 g, 0.5 mmol), tartaric acid (0.075 g, 0.5 mmol) and water (18 ml) in a 25 ml Teflon-lined stainless steel reactor was heated from 298 to 453 K in 2 h and maintained at 453 K for 72 h. After the mixture was cooled to 298 K, blue crystals of the title compound were obtained.

Refinement top

All H atoms were positioned geometrically. Aromatic H atoms were refined as riding atoms, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). The other H atoms were fixed in the refinements, with Uiso(H) = 1.2Ueq(C,O).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. The hydroxyl groups (O5 and O6) of the tartrate anion are half-occupied. The disordered H atoms attached to C13 have been omitted. [Symmetry codes: (i) 2 - x, -y, -z; (ii) 1 - x, 1 - y, 1 - z.]
Bis(di-2-pyridylmethanediol-κ3N,O,N')copper(II) tartrate top
Crystal data top
[Cu(C11H10N2O2)2]C4H4O6Z = 1
Mr = 616.03F(000) = 317
Triclinic, P1Dx = 1.602 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.7893 (8) ÅCell parameters from 1352 reflections
b = 8.1068 (8) Åθ = 2.8–26.5°
c = 11.3136 (12) ŵ = 0.92 mm−1
α = 105.973 (1)°T = 293 K
β = 90.431 (1)°Prism, blue
γ = 110.584 (1)°0.45 × 0.30 × 0.18 mm
V = 638.65 (11) Å3
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2235 independent reflections
Radiation source: fine-focus sealed tube1978 reflections with I > 2σ(I)
graphiteRint = 0.015
φ and ω scansθmax = 25.1°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −9→9
Tmin = 0.726, Tmax = 0.850k = −9→8
3231 measured reflectionsl = −13→11
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0346P)2 + 0.5737P]
where P = (Fo2 + 2Fc2)/3
2235 reflections(Δ/σ)max < 0.001
196 parametersΔρmax = 0.37 e Å−3
0 restraintsΔρmin = −0.31 e Å−3
Crystal data top
[Cu(C11H10N2O2)2]C4H4O6γ = 110.584 (1)°
Mr = 616.03V = 638.65 (11) Å3
Triclinic, P1Z = 1
a = 7.7893 (8) ÅMo Kα radiation
b = 8.1068 (8) ŵ = 0.92 mm−1
c = 11.3136 (12) ÅT = 293 K
α = 105.973 (1)°0.45 × 0.30 × 0.18 mm
β = 90.431 (1)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2235 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1978 reflections with I > 2σ(I)
Tmin = 0.726, Tmax = 0.850Rint = 0.015
3231 measured reflectionsθmax = 25.1°
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.091Δρmax = 0.37 e Å−3
S = 1.03Δρmin = −0.31 e Å−3
2235 reflectionsAbsolute structure: ?
196 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu11.00000.00000.00000.03430 (17)
N10.9447 (3)0.0410 (3)0.1761 (2)0.0337 (5)
N20.8085 (3)0.1020 (3)−0.0329 (2)0.0357 (5)
O11.1369 (3)0.3273 (3)0.09003 (17)0.0394 (5)
H1A1.22670.36770.14730.047*
O21.0017 (3)0.5166 (3)0.21831 (19)0.0488 (6)
H2A1.09630.56310.26710.059*
O30.4119 (4)0.4426 (5)0.2591 (2)0.0951 (11)
O40.2982 (5)0.6254 (5)0.3782 (3)0.1005 (13)
O50.7064 (6)0.5609 (6)0.4214 (4)0.0507 (11)0.50
H50.68470.51430.34680.061*0.50
O60.5874 (7)0.7540 (6)0.5538 (4)0.0569 (12)0.50
H60.51460.79730.53660.068*0.50
C10.9098 (4)−0.0858 (4)0.2372 (3)0.0411 (7)
H10.9154−0.20040.19770.049*
C20.8658 (5)−0.0499 (5)0.3569 (3)0.0506 (8)
H20.8416−0.13910.39790.061*
C30.8583 (5)0.1207 (5)0.4150 (3)0.0538 (9)
H30.82740.14680.49550.065*
C40.8970 (4)0.2526 (5)0.3533 (3)0.0459 (8)
H40.89360.36850.39150.055*
C50.9407 (4)0.2086 (4)0.2340 (2)0.0339 (6)
C60.9820 (4)0.3391 (4)0.1516 (3)0.0361 (6)
C70.8205 (4)0.2618 (4)0.0498 (3)0.0365 (6)
C80.6957 (4)0.3441 (4)0.0418 (3)0.0472 (8)
H80.70370.45220.10170.057*
C90.5585 (4)0.2637 (5)−0.0563 (3)0.0540 (9)
H90.47290.3174−0.06380.065*
C100.5493 (4)0.1036 (5)−0.1432 (3)0.0483 (8)
H100.45930.0492−0.21110.058*
C110.6747 (4)0.0247 (4)−0.1282 (3)0.0420 (7)
H110.6665−0.0854−0.18580.050*
C120.4060 (4)0.5461 (4)0.3591 (3)0.0436 (7)
C130.5422 (4)0.5732 (4)0.4673 (3)0.0406 (7)
H13A0.57130.69940.52710.049*0.50
H13B0.65680.55970.43490.049*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0397 (3)0.0388 (3)0.0277 (3)0.0214 (2)0.0000 (2)0.0060 (2)
N10.0388 (13)0.0359 (13)0.0302 (12)0.0188 (11)0.0011 (10)0.0092 (10)
N20.0385 (13)0.0404 (13)0.0289 (12)0.0186 (11)−0.0017 (10)0.0063 (10)
O10.0425 (11)0.0413 (11)0.0322 (10)0.0143 (9)−0.0019 (9)0.0090 (9)
O20.0607 (14)0.0365 (12)0.0458 (13)0.0235 (10)−0.0110 (11)0.0002 (9)
O30.0785 (19)0.152 (3)0.0442 (15)0.076 (2)−0.0195 (14)−0.0292 (17)
O40.130 (3)0.121 (3)0.0594 (18)0.100 (2)−0.0409 (17)−0.0290 (17)
O50.041 (2)0.062 (3)0.051 (3)0.019 (2)0.001 (2)0.019 (2)
O60.068 (3)0.043 (3)0.047 (3)0.011 (2)−0.012 (2)0.006 (2)
C10.0428 (17)0.0410 (17)0.0433 (17)0.0191 (14)0.0003 (14)0.0136 (14)
C20.053 (2)0.062 (2)0.0462 (19)0.0234 (17)0.0046 (15)0.0292 (17)
C30.062 (2)0.078 (2)0.0307 (16)0.0362 (19)0.0097 (15)0.0165 (17)
C40.0552 (19)0.0545 (19)0.0335 (16)0.0310 (16)0.0035 (14)0.0077 (14)
C50.0353 (15)0.0404 (16)0.0290 (14)0.0200 (13)−0.0005 (12)0.0070 (12)
C60.0447 (16)0.0324 (15)0.0325 (15)0.0193 (13)0.0014 (13)0.0053 (12)
C70.0409 (16)0.0378 (16)0.0357 (16)0.0178 (13)0.0031 (13)0.0143 (13)
C80.0534 (19)0.0406 (17)0.054 (2)0.0253 (15)0.0002 (16)0.0138 (15)
C90.0451 (19)0.058 (2)0.069 (2)0.0278 (17)−0.0049 (17)0.0218 (18)
C100.0428 (17)0.057 (2)0.0441 (18)0.0197 (16)−0.0083 (14)0.0121 (16)
C110.0409 (17)0.0451 (17)0.0363 (16)0.0159 (14)−0.0037 (13)0.0062 (13)
C120.0466 (18)0.0448 (18)0.0353 (17)0.0162 (15)0.0008 (14)0.0062 (14)
C130.0396 (16)0.0404 (17)0.0375 (16)0.0135 (13)−0.0019 (13)0.0066 (13)
Geometric parameters (Å, °) top
Cu1—N1i2.003 (2)C1—C21.377 (4)
Cu1—N12.003 (2)C1—H10.9300
Cu1—N2i2.019 (2)C2—C31.380 (5)
Cu1—N22.019 (2)C2—H20.9300
Cu1—O1i2.3920 (19)C3—C41.382 (5)
Cu1—O12.3920 (19)C3—H30.9300
N1—C11.344 (4)C4—C51.375 (4)
N1—C51.348 (3)C4—H40.9300
N2—C111.339 (4)C5—C61.549 (4)
N2—C71.345 (4)C6—C71.526 (4)
O1—C61.417 (3)C7—C81.373 (4)
O1—H1A0.8554C8—C91.376 (5)
O2—C61.382 (3)C8—H80.9300
O2—H2A0.8209C9—C101.374 (5)
O3—C121.222 (4)C9—H90.9300
O4—C121.213 (4)C10—C111.374 (4)
O5—C131.409 (5)C10—H100.9300
O5—H50.8134C11—H110.9300
O5—H13B0.4145C12—C131.530 (4)
O6—C131.440 (5)C13—C13ii1.527 (6)
O6—H60.8117C13—H13A1.0044
O6—H13A0.4359C13—H13B0.9970
N1i—Cu1—N1180.0N1—C5—C4121.9 (3)
N1i—Cu1—N2i88.92 (9)N1—C5—C6113.5 (2)
N1—Cu1—N2i91.08 (9)C4—C5—C6124.6 (3)
N1i—Cu1—N291.08 (9)O2—C6—O1113.9 (2)
N1—Cu1—N288.92 (9)O2—C6—C7109.4 (2)
N2i—Cu1—N2180.0O1—C6—C7105.5 (2)
N1i—Cu1—O1i75.89 (8)O2—C6—C5111.9 (2)
N1—Cu1—O1i104.11 (8)O1—C6—C5108.2 (2)
N2i—Cu1—O1i73.63 (8)C7—C6—C5107.6 (2)
N2—Cu1—O1i106.37 (8)N2—C7—C8122.0 (3)
N1i—Cu1—O1104.11 (8)N2—C7—C6113.9 (2)
N1—Cu1—O175.89 (8)C8—C7—C6124.1 (3)
N2i—Cu1—O1106.37 (8)C7—C8—C9118.8 (3)
N2—Cu1—O173.63 (8)C7—C8—H8120.6
O1i—Cu1—O1180.00 (10)C9—C8—H8120.6
C1—N1—C5119.4 (2)C10—C9—C8119.4 (3)
C1—N1—Cu1124.79 (19)C10—C9—H9120.3
C5—N1—Cu1115.84 (18)C8—C9—H9120.3
C11—N2—C7118.8 (2)C9—C10—C11119.1 (3)
C11—N2—Cu1125.7 (2)C9—C10—H10120.5
C7—N2—Cu1115.45 (18)C11—C10—H10120.5
C6—O1—Cu193.97 (15)N2—C11—C10121.8 (3)
C6—O1—H1A105.5N2—C11—H11119.1
Cu1—O1—H1A116.8C10—C11—H11119.1
C6—O2—H2A109.5O4—C12—O3124.4 (3)
C13—O5—H5108.0O4—C12—C13118.5 (3)
C13—O5—H13B5.1O3—C12—C13117.1 (3)
H5—O5—H13B107.4O5—C13—O6107.9 (3)
C13—O6—H6108.0O5—C13—C12108.8 (3)
C13—O6—H13A2.7O6—C13—C12110.1 (3)
H6—O6—H13A105.4O5—C13—C13ii110.6 (3)
N1—C1—C2121.5 (3)O6—C13—C13ii109.6 (3)
N1—C1—H1119.3C12—C13—C13ii109.9 (3)
C2—C1—H1119.3O5—C13—H13A108.8
C1—C2—C3119.0 (3)O6—C13—H13A1.2
C1—C2—H2120.5C12—C13—H13A109.0
C3—C2—H2120.5C13ii—C13—H13A109.7
C2—C3—C4119.8 (3)O5—C13—H13B2.1
C2—C3—H3120.1O6—C13—H13B109.5
C4—C3—H3120.1C12—C13—H13B109.1
C5—C4—C3118.5 (3)C13ii—C13—H13B108.6
C5—C4—H4120.7H13A—C13—H13B110.5
C3—C4—H4120.7
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O3iii0.851.732.582 (3)178
O2—H2A···O4iii0.821.842.648 (3)170
O5—H5···O30.822.152.641 (5)119
O6—H6···O40.822.222.693 (5)118
C2—H2···O5iv0.932.383.249 (6)156
C3—H3···O4ii0.932.503.217 (4)134
C4—H4···O50.932.453.258 (5)146
Symmetry codes: (iii) x+1, y, z; (iv) x, y−1, z; (ii) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N12.003 (2)Cu1—O12.3920 (19)
Cu1—N22.019 (2)
N1—Cu1—N2i91.08 (9)N2—Cu1—O1i106.37 (8)
N1—Cu1—N288.92 (9)N1—Cu1—O175.89 (8)
N1—Cu1—O1i104.11 (8)N2—Cu1—O173.63 (8)
Symmetry codes: (i) −x+2, −y, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···O3ii0.851.732.582 (3)178
O2—H2A···O4ii0.821.842.648 (3)170
O5—H5···O30.822.152.641 (5)119
O6—H6···O40.822.222.693 (5)118
C2—H2···O5iii0.932.383.249 (6)156
C3—H3···O4iv0.932.503.217 (4)134
C4—H4···O50.932.453.258 (5)146
Symmetry codes: (ii) x+1, y, z; (iii) x, y−1, z; (iv) −x+1, −y+1, −z+1.
Acknowledgements top

This work was supported financially by the National Natural Science Foundation of China (grant No. 20773104), the Program for New Century Excellent Talents in Universities (NCET-06–0891), the Key Project of the Chinese Ministry of Education (grant No. 208143) and the Important Project of Hubei Provincial Education Office (09HB81).

references
References top

Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Deveson, A. C., Heath, S. L., Harding, C. J. & Powell, A. K. (1996). J. Chem. Soc. Dalton Trans. pp. 3173–3177.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Sommerer, S. O., Baker, J. D., Jensen, W. P., Hamza, A. & Jacobson, R. A. (1993). Inorg. Chim. Acta, 210, 173–176.

Wang, S. L., Richardson, J. W., Briggs, S. J. & Jacobson, R. A. (1986). Inorg. Chim. Acta, 111, 67–72.