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Acta Cryst. (2010). E66, m1229    [ doi:10.1107/S1600536810035440 ]

catena-Poly[[(1,10-phenanthroline)copper(II)]-[mu]-oxalato]

J. Wang, Y. Hou and Z. Fang

Abstract top

In the title coordination polymer, [Cu(C2O4)(C12H8N2)]n, the CuII atom is six-coordinated by four O atoms from two oxalate ligands and two N atoms from one 1,10-phenanthroline (phen) ligand in a distorted octahedral coordination geometry. The oxalate anions act as bis-bidentate ligands, bridging the Cu-phen units in zigzag chains extending parallel to [100]. Interchain C-H...O hydrogen bonding and [pi]-[pi] stacking interactions [centroid-centroid distance = 3.7439 (17) Å] assemble neighboring chains, forming a three-dimensional supramolecular network.

Comment top

The design and construction of metal coordination polymers based on metal ions and multifunctional bridging ligands is of great interest due to their intriguing topologies and potential applications as functional materials (Benneli & Gatteschi, 2002; Qiu et al., 2007). Copper, with its variable coordination numbers and flexible coordination geometry, provides unique opportunities for the discovery of unusual networks in this interesting and challenging field (Qin et al., 2005). We chose oxalate ligands as organic spacers since this rigid molecule has proven to be able to establish a bridge between metal centers. Herein, we present the structure of the title compound, [Cu(C2O4)(C12H8N2)]n.

The CuII atom exhibits a distorted octahedral configuration coordinated by four oxygen atoms from two oxalate ligands (Cu—O = 1.9753 (18)-2.3135 (18) Å) and two nitrogen atoms from one 1,10-phenanthroline ligand (Cu—N = 2.024 (2) and 2.049 (2) Å) (Fig. 1). The oxalate ligands bridge adjacent Cu-phen units to form a one-dimensional zigzag chain along the a-axis of the unit cell. The Cu—Cu separation is 5.529 (2) Å. Interchain π-π stacking interactions between phen ligands in neighboring chainslead to the formation of sheets of connected chains in the ab-plane. The centroid to centroid distances between neighboring 1,10-phenanthroline ligands is 3.7439 (17) Å [ring (C4-C9) to ring (N2, C1 to C5) (symmetry code: –1/2+x, 3/2–y, z)]. C–H···O hydrogen bonds interconnect these sheets to extend to a three-dimensional supramolecular network motif (Table 1; Fig. 2).

Related literature top

For the topologies and potential applications as functional materials of metal coordination polymers, see: Benneli & Gatteschi (2002); Qin et al. (2005); Qiu et al. (2007).

Experimental top

A sample of cupric acetate (0.0399 g, 0.20 mmol), oxalic acid (0.1015 g, 0.50 mmol), 1,10-phenanthroline (0.2523 g, 0.50 mmol), were added to water (10 ml). The resultant mixture was sealed in a 25 ml stainless steel reactor with a Teflon liner and kept under autogenous pressure at 413 K for 78 h, and then cooled to room temperature at a rate of 0.5 K/min. Colorless blocky crystals of the title compound suitable for single-crystal X-ray diffraction analyses formed in a yield of approximately 65%.

Refinement top

All H atoms were placed at calculated positions and were treated as riding on the parent C atoms with C—H = 0.93 Å, and with Uiso(H) = 1.2 (C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. ORTEP represention of atom numbering diagram for the title complex, showing 30% probability displacement ellipsoids. Symmetry code: (i) –1/2 + x, 2.5–y, z.
[Figure 2] Fig. 2. View of the three-dimensional structure of the title compound.
catena-Poly[[(1,10-phenanthroline)copper(II)]-µ-oxalato] top
Crystal data top
[Cu(C2O4)(C12H8N2)]F(000) = 668
Mr = 331.76Dx = 1.782 Mg m−3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 2618 reflections
a = 9.1445 (8) Åθ = 2.5–27.0°
b = 10.1443 (9) ŵ = 1.78 mm−1
c = 13.3294 (11) ÅT = 298 K
V = 1236.50 (18) Å3Block, blue
Z = 40.42 × 0.35 × 0.29 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2618 independent reflections
Radiation source: fine-focus sealed tube2373 reflections with I > 2σ(I)
graphiteRint = 0.021
φ and ω scanθmax = 27.0°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)		h = −8→11
Tmin = 0.544, Tmax = 0.612k = −10→12
6811 measured reflectionsl = −16→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.059 w = 1/[σ2(Fo2) + (0.0289P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max = 0.001
2618 reflectionsΔρmax = 0.28 e Å−3
190 parametersΔρmin = −0.30 e Å−3
1 restraintAbsolute structure: Flack (1983), 1217 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.019 (14)
Crystal data top
[Cu(C2O4)(C12H8N2)]V = 1236.50 (18) Å3
Mr = 331.76Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 9.1445 (8) ŵ = 1.78 mm−1
b = 10.1443 (9) ÅT = 298 K
c = 13.3294 (11) Å0.42 × 0.35 × 0.29 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2618 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008)		2373 reflections with I > 2σ(I)
Tmin = 0.544, Tmax = 0.612Rint = 0.021
6811 measured reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.059Δρmax = 0.28 e Å−3
S = 1.04Δρmin = −0.30 e Å−3
2618 reflectionsAbsolute structure: Flack (1983), 1217 Friedel pairs
190 parametersFlack parameter: 0.019 (14)
1 restraint
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
C10.6938 (3)0.9764 (3)−0.04988 (19)0.0407 (6)
H10.66521.0617−0.06620.049*
Cu10.87241 (3)1.09675 (2)0.11815 (4)0.03062 (9)
N10.9474 (2)0.9310 (2)0.18929 (17)0.0352 (5)
O11.0814 (2)1.12990 (18)0.02682 (14)0.0377 (4)
C20.6422 (3)0.8724 (3)−0.1095 (2)0.0486 (7)
H20.58180.8883−0.16430.058*
N20.7802 (2)0.9598 (2)0.02762 (16)0.0325 (4)
O20.98329 (19)1.21773 (18)0.20589 (13)0.0377 (4)
C30.6829 (3)0.7475 (3)−0.0849 (2)0.0472 (7)
H30.65060.6770−0.12370.057*
O31.1635 (2)1.36277 (17)0.21108 (14)0.0358 (4)
C40.7727 (3)0.7242 (2)−0.0022 (2)0.0386 (6)
O41.2795 (2)1.25638 (18)0.04136 (14)0.0376 (4)
C50.8190 (3)0.8351 (2)0.05270 (19)0.0321 (5)
C60.9086 (2)0.8194 (2)0.13957 (17)0.0307 (6)
C70.9518 (3)0.6918 (3)0.1703 (2)0.0404 (6)
C80.9027 (3)0.5816 (2)0.1130 (4)0.0500 (7)
H80.92930.49710.13300.060*
C90.8186 (4)0.5967 (2)0.0306 (3)0.0485 (7)
H90.78990.5226−0.00550.058*
C101.0386 (3)0.6850 (3)0.2567 (2)0.0498 (7)
H101.07230.60380.27940.060*
C111.0740 (4)0.7970 (3)0.3077 (3)0.0555 (8)
H111.12950.79220.36600.067*
C121.0266 (3)0.9184 (3)0.2720 (2)0.0471 (7)
H121.05150.99400.30760.056*
C131.1578 (3)1.2130 (2)0.07154 (19)0.0303 (5)
C141.0979 (3)1.2700 (2)0.17167 (19)0.0288 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0439 (15)0.0420 (14)0.0362 (14)0.0018 (12)−0.0088 (12)−0.0036 (12)
Cu10.03102 (14)0.02964 (14)0.03119 (13)−0.00071 (10)−0.00153 (13)−0.00414 (16)
N10.0315 (11)0.0393 (11)0.0347 (12)0.0005 (9)−0.0041 (9)−0.0007 (9)
O10.0370 (10)0.0409 (9)0.0350 (10)−0.0020 (8)0.0025 (8)−0.0107 (8)
C20.0555 (19)0.0558 (17)0.0346 (15)0.0010 (14)−0.0120 (13)−0.0089 (13)
N20.0336 (10)0.0323 (10)0.0317 (11)0.0008 (8)−0.0013 (9)−0.0039 (9)
O20.0365 (11)0.0433 (10)0.0335 (10)−0.0101 (8)0.0092 (8)−0.0118 (9)
C30.0500 (18)0.0539 (17)0.0376 (16)−0.0090 (14)−0.0026 (14)−0.0157 (13)
O30.0382 (10)0.0329 (9)0.0361 (10)−0.0043 (8)0.0007 (8)−0.0064 (8)
C40.0393 (14)0.0370 (13)0.0395 (15)−0.0068 (11)0.0064 (11)−0.0096 (12)
O40.0363 (10)0.0388 (9)0.0377 (10)−0.0026 (8)0.0102 (8)−0.0030 (8)
C50.0320 (13)0.0337 (13)0.0307 (13)−0.0018 (11)0.0058 (11)−0.0035 (10)
C60.0288 (12)0.0328 (12)0.0305 (16)0.0004 (9)0.0055 (9)−0.0016 (9)
C70.0375 (14)0.0414 (15)0.0424 (15)0.0040 (12)0.0059 (12)0.0067 (12)
C80.0599 (17)0.0306 (12)0.0593 (18)0.0031 (10)0.011 (2)0.0032 (18)
C90.0581 (18)0.0317 (15)0.056 (2)−0.0092 (12)0.0074 (16)−0.0072 (13)
C100.0491 (18)0.0495 (18)0.0509 (19)0.0092 (13)0.0012 (14)0.0111 (14)
C110.0519 (19)0.068 (2)0.0465 (19)0.0056 (17)−0.0099 (15)0.0107 (17)
C120.0499 (17)0.0496 (16)0.0417 (16)0.0011 (13)−0.0124 (13)−0.0052 (13)
C130.0327 (13)0.0285 (12)0.0296 (12)0.0062 (10)−0.0010 (11)0.0017 (10)
C140.0293 (12)0.0297 (12)0.0274 (12)0.0011 (10)−0.0030 (10)−0.0022 (11)
Geometric parameters (Å, °) top
C1—N21.311 (3)O3—Cu1ii2.3135 (18)
C1—C21.403 (4)C4—C51.407 (3)
C1—H10.9300C4—C91.428 (4)
Cu1—O21.9753 (18)O4—C131.263 (3)
Cu1—O4i1.9973 (19)O4—Cu1ii1.9973 (19)
Cu1—N22.024 (2)C5—C61.428 (3)
Cu1—N12.049 (2)C6—C71.414 (3)
Cu1—O12.2909 (19)C7—C101.401 (4)
Cu1—O3i2.3135 (18)C7—C81.426 (5)
N1—C121.325 (4)C8—C91.350 (6)
N1—C61.359 (3)C8—H80.9300
O1—C131.247 (3)C9—H90.9300
C2—C31.360 (5)C10—C111.363 (4)
C2—H20.9300C10—H100.9300
N2—C51.356 (3)C11—C121.390 (4)
O2—C141.260 (3)C11—H110.9300
C3—C41.395 (4)C12—H120.9300
C3—H30.9300C13—C141.554 (3)
O3—C141.234 (3)
N2—C1—C2123.5 (2)C3—C4—C9124.7 (3)
N2—C1—H1118.3C5—C4—C9118.4 (3)
C2—C1—H1118.3C13—O4—Cu1ii118.13 (17)
O2—Cu1—O4i93.34 (8)N2—C5—C4122.6 (2)
O2—Cu1—N2173.31 (8)N2—C5—C6117.0 (2)
O4i—Cu1—N291.68 (9)C4—C5—C6120.4 (2)
O2—Cu1—N193.68 (8)N1—C6—C7123.3 (2)
O4i—Cu1—N1172.68 (8)N1—C6—C5116.9 (2)
N2—Cu1—N181.49 (9)C7—C6—C5119.8 (2)
O2—Cu1—O178.18 (7)C10—C7—C6116.2 (2)
O4i—Cu1—O188.46 (7)C10—C7—C8125.5 (3)
N2—Cu1—O197.55 (7)C6—C7—C8118.3 (3)
N1—Cu1—O195.01 (8)C9—C8—C7121.7 (3)
O2—Cu1—O3i89.80 (7)C9—C8—H8119.1
O4i—Cu1—O3i77.92 (7)C7—C8—H8119.1
N2—Cu1—O3i95.57 (7)C8—C9—C4121.3 (3)
N1—Cu1—O3i100.03 (8)C8—C9—H9119.3
O1—Cu1—O3i161.33 (6)C4—C9—H9119.3
C12—N1—C6117.9 (2)C11—C10—C7120.2 (3)
C12—N1—Cu1130.30 (19)C11—C10—H10119.9
C6—N1—Cu1111.77 (16)C7—C10—H10119.9
C13—O1—Cu1108.21 (16)C10—C11—C12119.6 (3)
C3—C2—C1118.2 (3)C10—C11—H11120.2
C3—C2—H2120.9C12—C11—H11120.2
C1—C2—H2120.9N1—C12—C11122.7 (3)
C1—N2—C5118.1 (2)N1—C12—H12118.6
C1—N2—Cu1129.22 (18)C11—C12—H12118.6
C5—N2—Cu1112.62 (16)O1—C13—O4125.2 (2)
C14—O2—Cu1118.30 (16)O1—C13—C14117.7 (2)
C2—C3—C4120.6 (3)O4—C13—C14117.1 (2)
C2—C3—H3119.7O3—C14—O2124.9 (2)
C4—C3—H3119.7O3—C14—C13118.5 (2)
C14—O3—Cu1ii108.00 (16)O2—C14—C13116.6 (2)
C3—C4—C5116.9 (2)
Symmetry codes: (i) x−1/2, −y+5/2, z; (ii) x+1/2, −y+5/2, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C11—H11···O4iii0.932.513.416 (4)166
C9—H9···O1iv0.932.493.160 (3)129
C2—H2···O2v0.932.523.136 (3)124
C1—H1···O4i0.932.563.072 (3)115
Symmetry codes: (iii) −x+5/2, y−1/2, z+1/2; (iv) x−1/2, −y+3/2, z; (v) −x+3/2, y−1/2, z−1/2; (i) x−1/2, −y+5/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C11—H11···O4i0.932.513.416 (4)166
C9—H9···O1ii0.932.493.160 (3)129
C2—H2···O2iii0.932.523.136 (3)124
C1—H1···O4iv0.932.563.072 (3)115
Symmetry codes: (i) −x+5/2, y−1/2, z+1/2; (ii) x−1/2, −y+3/2, z; (iii) −x+3/2, y−1/2, z−1/2; (iv) x−1/2, −y+5/2, z.
references
References top

Benneli, C. & Gatteschi, D. (2002). Chem. Rev. 102, 2369–2388.

Bruker (2004). APEX2 and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Qin, C., Wang, X. L., Wang, E. B. & Su, Z. M. (2005). Inorg. Chem. 44, 7122–7129.

Qiu, Y. C., Wang, K. N., Liu, Y., Deng, H., Sun, F. & Cai, Y. P. (2007). Inorg. Chim. Acta, 360, 1819–1824.

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