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Acta Cryst. (2007). E63, m1492-m1493    [ doi:10.1107/S1600536807018417 ]

Poly[trans-diaquabis([mu]2-3-pyridylacetato)copper(II)]

S.-N. Qin, F.-P. Liang, Z.-L. Chen and W.-H. Yan

Abstract top

The title copperII coordination polymer, trans-[Cu(C7H6NO2)2(H2O)2]n, was obtained from a solvothermal reaction of 3-pyridylacetic acid hydrochloride with Cu(ClO4)2·6H2O. The molecule is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral geometry. The CuII center is coordinated by two water molecules [Cu-O = 2.424 (4) Å], two pyridyl N atoms [Cu-N = 2.031 (4) Å], and two carboxylate O atoms [Cu-O1 = 1.968 (4) Å]. All Ocarboxylate-Cu-Ocarboxylate, Owater-Cu-Owater and N-Cu-N bond angles are 180° due to the inversion symmetry of the complexes. Each 3-pyridylacetate anion uses its pyridine N atom and one carboxylate O atom to connect two CuII ions, generating two-dimensional sheets parallel to (212). Each complex exhibits two intramolecular O-H...O hydrogen bonds with angles at hydrogen of 156°. Adjacent two-dimensional layers are connected via intermolecular O-H...O and weak C-H...O hydrogen-bonding contacts, resulting in a three-dimensional framework structure with oxygen as a trifurcated acceptor atom.

Comment top

Pyridinecarboxylic acids have been extensively used in the preparation of metal complexes because of their versatile coordination modes. These ligands can connect different metal ions to form robust networks or some porous coordination polymers. Though various metal-pyridinepolycarboxylate complexes have been reported (Evans et al., 2002; Aakeröy et al., 1999; Tong et al., 2003; Li et al., 2004; Du et al., 2006), complexes of 3-pyridylacetate are very limited. Only complexes of nickel and cobalt have been published recently up to now (Martin et al., 2007). In this paper, we report a new two-dimensional coordination polymer, [Cu(3-pyridylacetato)2(H2O)2]n, (I).

The molecule of the title complex, which is similar to that previously described for [M(Hpya)2(H2O)2]n (M = Cu, Co, Mn, Ni, Zn, Cd; Hpya = 4-pyridylacetic acid) (Li et al., 2004; Du et al., 2006) and [M(3-pyridylacetato)2(H2O)2]n (M = Ni, Co) (Martin et al., 2007), is centrosymmetric, so pairs of equivalent ligands lie trans to each other in a slightly distorted octahedral geometry. The CuII center is six-coordinated by two water molecules in the axial positions, two pyridyl nitrogen atoms and two carboxylate oxygen atoms from four 3-pyridylacetate ligands in the equatorial plane. Each 3-pyridylacetate anion uses its pyridine nitrogen atom and one carboxylate oxygen atom to connect two CuII ions. Four 3-pyridylacetate anionic ligands and four CuII ions form a tetragon with a side length of 8.405 Å and a diagonal measurement of 14.443 * 8.602 Å based on the Cu—Cu distances. The tetragon is further extended into a two-dimensional framework parallel to (212) with a rhombic grid through sharing CuII ions, 3-pyridylacetate anionic ligands and intramolecular O3—H1···O2 hydrogen bonds (Fig. 1).

Adjacent two-dimensional layers are connected via intermolecular O—H···O and weak C—H···O hydrogen-bonding contacts, resulting in a three-dimensional framework structure with oxygen as a trifurcated acceptor atom (Fig. 2).

Related literature top

The six-coordinate complex of 4-pyridylacetate ligands has similar octahedral geometry (Li et al., 2004; Du et al., 2006).

For related literature, see: Aakeröy et al. (1999); Evans & Lin (2002); Tong et al. (2003).

Experimental top

A mixture of 3-pyridylacetic acid hydrochloride (0.0434 g, 0.25 mmol), Cu(ClO4)2.6H2O(0.0555 g, 0.15 mmol), NaClO4.6H2O (0.0300 g, 0.13 mmol), NaOH (0.0200 g, 0.5 mmol), THF (10 ml) and water (5 ml) was sealed in a 25 ml Teflon-lined stainless-steel reactor and heated to 333 K for 96 h, yielding blue crystals of (I) suitable for X-ray analysis. Elemental analysis for C14H16CuN2O6, calculated: C 45.22, H 4.34, N 7.53%; found: C 44.61, H 5.44, N 7.13%.

Refinement top

H atoms of the water molecules were located in a difference map. H atoms bonded to C atoms were placed at calulated positions and treated using a riding-model approximation [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)].

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Principal connectivity of the coordination polymer two-dimensional structure (I) on (2 1 2), showing 50% probability displacement ellipsoids. All H atoms except H1 have been omitted for clarity. Symmetry codes: (i) -x + 1,-y + 1,-z + 1.
[Figure 2] Fig. 2. Intermolecular hydrogen bonding contacts between the two-dimensional polymer layers in ac plane. For clarity, only H1, H2, and H5 were used. Symmetry codes: (ii) x - 1/2,-y + 3/2,z - 1/2; (iii) 1 - x,2 - y,1 - z; (iv) -x,2 - y,1 - z..
Poly[trans-diaquabis(µ2-3-pyridylacetato)copper(II)] top
Crystal data top
[Cu(C7H6NO2)2(H2O)2]nF(000) = 382
Mr = 371.83Dx = 1.682 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 748 reflections
a = 9.0672 (18) Åθ = 2.8–25.1°
b = 8.6022 (17) ŵ = 1.52 mm−1
c = 9.601 (2) ÅT = 298 K
β = 101.335 (3)°Block, blue
V = 734.2 (3) Å30.70 × 0.38 × 0.09 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		1284 independent reflections
Radiation source: fine-focus sealed tube821 reflections with I > σ(I)
graphiteRint = 0.071
φ and ω scansθmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −10→9
Tmin = 0.416, Tmax = 0.875k = −10→10
3558 measured reflectionsl = −9→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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0387P)2 + 0.9264P]
where P = (Fo2 + 2Fc2)/3
1284 reflections(Δ/σ)max < 0.001
106 parametersΔρmax = 0.79 e Å−3
0 restraintsΔρmin = −0.72 e Å−3
Crystal data top
[Cu(C7H6NO2)2(H2O)2]nV = 734.2 (3) Å3
Mr = 371.83Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.0672 (18) ŵ = 1.52 mm−1
b = 8.6022 (17) ÅT = 298 K
c = 9.601 (2) Å0.70 × 0.38 × 0.09 mm
β = 101.335 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1284 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		821 reflections with I > σ(I)
Tmin = 0.416, Tmax = 0.875Rint = 0.071
3558 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.117Δρmax = 0.79 e Å−3
S = 1.07Δρmin = −0.72 e Å−3
1284 reflectionsAbsolute structure: ?
106 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.

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
xyzUiso*/Ueq
Cu10.50000.50000.50000.0263 (3)
N10.3098 (5)0.5766 (6)0.5596 (5)0.0278 (11)
O10.5329 (4)0.7068 (4)0.4238 (4)0.0316 (10)
O20.6976 (4)0.8160 (5)0.5997 (4)0.0444 (11)
O30.6312 (4)0.5530 (5)0.7405 (4)0.0418 (12)
H10.67160.63650.71900.063*
H20.68900.49050.79410.063*
C10.6225 (6)0.8136 (7)0.4763 (6)0.0280 (14)
C20.6336 (7)0.9518 (7)0.3801 (6)0.0384 (17)
H2A0.54281.01360.37190.046*
H2B0.71761.01630.42440.046*
C30.2837 (6)0.5449 (7)0.6883 (5)0.0293 (15)
H30.35530.48850.75090.035*
C40.1545 (6)0.5920 (6)0.7331 (6)0.0263 (13)
C50.0475 (6)0.6698 (7)0.6372 (6)0.0353 (15)
H5−0.04280.69870.66200.042*
C60.0737 (6)0.7049 (8)0.5056 (6)0.0402 (16)
H60.00370.76140.44150.048*
C70.2058 (6)0.6550 (7)0.4693 (6)0.0338 (15)
H70.22280.67670.37890.041*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0300 (5)0.0278 (6)0.0254 (5)−0.0014 (6)0.0157 (4)−0.0012 (5)
N10.029 (3)0.029 (3)0.027 (3)−0.002 (2)0.011 (2)−0.002 (2)
O10.041 (2)0.027 (3)0.029 (2)−0.009 (2)0.0141 (18)−0.0047 (18)
O20.048 (2)0.044 (3)0.039 (3)−0.005 (2)0.003 (2)0.003 (2)
O30.043 (2)0.045 (3)0.035 (2)−0.003 (2)0.0032 (19)−0.0014 (18)
C10.029 (3)0.035 (4)0.026 (3)0.008 (3)0.019 (3)0.002 (3)
C20.044 (3)0.044 (5)0.034 (3)−0.004 (3)0.022 (3)−0.002 (3)
C30.030 (3)0.036 (4)0.023 (3)0.004 (3)0.008 (2)0.003 (2)
C40.031 (3)0.021 (3)0.032 (3)−0.003 (3)0.017 (3)−0.002 (3)
C50.027 (3)0.043 (4)0.038 (4)0.002 (3)0.013 (3)−0.004 (3)
C60.034 (3)0.049 (5)0.038 (4)0.010 (3)0.008 (3)0.005 (3)
C70.041 (3)0.038 (4)0.024 (3)−0.001 (3)0.010 (3)0.001 (3)
Geometric parameters (Å, °) top
Cu1—O1i1.968 (4)C2—C4ii1.508 (7)
Cu1—O11.968 (4)C2—H2A0.9700
Cu1—N1i2.031 (4)C2—H2B0.9700
Cu1—N12.031 (4)C3—C41.385 (7)
Cu1—O3i2.424 (4)C3—H30.9300
Cu1—O32.424 (4)C4—C51.373 (7)
N1—C31.331 (6)C4—C2iii1.508 (7)
N1—C71.332 (7)C5—C61.364 (7)
O1—C11.263 (7)C5—H50.9300
O2—C11.245 (6)C6—C71.380 (7)
O3—H10.8500C6—H60.9300
O3—H20.8500C7—H70.9300
C1—C21.521 (8)
O1i—Cu1—O1180.00 (10)O2—C1—C2118.4 (5)
O1i—Cu1—N1i90.59 (17)O1—C1—C2116.1 (5)
O1—Cu1—N1i89.41 (17)C4ii—C2—C1114.1 (5)
O1i—Cu1—N189.41 (17)C4ii—C2—H2A108.7
O1—Cu1—N190.59 (17)C1—C2—H2A108.7
N1i—Cu1—N1180.000 (1)C4ii—C2—H2B108.7
O1i—Cu1—O3i95.85 (14)C1—C2—H2B108.7
O1—Cu1—O3i84.15 (14)H2A—C2—H2B107.6
N1i—Cu1—O3i87.45 (15)N1—C3—C4122.9 (5)
N1—Cu1—O3i92.55 (15)N1—C3—H3118.5
O1i—Cu1—O384.15 (14)C4—C3—H3118.5
O1—Cu1—O395.85 (14)C5—C4—C3117.6 (5)
N1i—Cu1—O392.55 (15)C5—C4—C2iii123.2 (5)
N1—Cu1—O387.45 (15)C3—C4—C2iii119.1 (5)
O3i—Cu1—O3180.000 (1)C6—C5—C4120.0 (5)
C3—N1—C7118.4 (5)C6—C5—H5120.0
C3—N1—Cu1120.7 (4)C4—C5—H5120.0
C7—N1—Cu1120.8 (4)C5—C6—C7118.8 (6)
C1—O1—Cu1129.9 (4)C5—C6—H6120.6
Cu1—O3—H194.7C7—C6—H6120.6
Cu1—O3—H2125.9N1—C7—C6122.1 (5)
H1—O3—H2116.0N1—C7—H7118.9
O2—C1—O1125.5 (5)C6—C7—H7118.9
O1i—Cu1—N1—C346.4 (4)Cu1—O1—C1—C2172.3 (3)
O1—Cu1—N1—C3−133.6 (4)O2—C1—C2—C4ii133.6 (5)
O3i—Cu1—N1—C3142.2 (4)O1—C1—C2—C4ii−48.2 (7)
O3—Cu1—N1—C3−37.8 (4)C7—N1—C3—C4−1.2 (8)
O1i—Cu1—N1—C7−131.1 (4)Cu1—N1—C3—C4−178.8 (4)
O1—Cu1—N1—C748.9 (4)N1—C3—C4—C52.5 (8)
O3i—Cu1—N1—C7−35.3 (4)N1—C3—C4—C2iii179.0 (5)
O3—Cu1—N1—C7144.7 (4)C3—C4—C5—C6−3.2 (9)
N1i—Cu1—O1—C1−78.0 (4)C2iii—C4—C5—C6−179.6 (6)
N1—Cu1—O1—C1102.0 (4)C4—C5—C6—C72.8 (9)
O3i—Cu1—O1—C1−165.5 (4)C3—N1—C7—C60.6 (9)
O3—Cu1—O1—C114.5 (4)Cu1—N1—C7—C6178.2 (4)
Cu1—O1—C1—O2−9.7 (8)C5—C6—C7—N1−1.4 (9)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1/2, −y+3/2, z−1/2; (iii) x−1/2, −y+3/2, z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H1···O20.851.962.762 (6)156
O3—H2···O2iv0.851.982.826 (6)170
C5—H5···O2v0.932.523.366 (7)151
Symmetry codes: (iv) −x+3/2, y−1/2, −z+3/2; (v) x−1, y, z.
Table 1
Selected geometric parameters (Å, °) top
Cu1—O11.968 (4)Cu1—O32.424 (4)
Cu1—N12.031 (4)
O1i—Cu1—O1180.00 (10)N1—Cu1—O387.45 (15)
O1—Cu1—N1i89.41 (17)O3i—Cu1—O3180.000 (1)
O1—Cu1—N190.59 (17)C3—N1—Cu1120.7 (4)
N1i—Cu1—N1180.000 (1)C7—N1—Cu1120.8 (4)
N1—Cu1—O3i92.55 (15)C1—O1—Cu1129.9 (4)
O1i—Cu1—O384.15 (14)Cu1—O3—H194.7
O1—Cu1—O395.85 (14)Cu1—O3—H2125.9
Symmetry codes: (i) −x+1, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H1···O20.851.962.762 (6)156
O3—H2···O2ii0.851.982.826 (6)170
C5—H5···O2iii0.932.523.366 (7)151
Symmetry codes: (ii) −x+3/2, y−1/2, −z+3/2; (iii) x−1, y, z.
Acknowledgements top

We acknowledge financial support from the Program for Hundred Outstanding Young Teachers in Higher Education Institutions of Guangxi, China.

references
References top

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