The title compound, [CoII(C10H8O6)(C10H8N2)(H2O)2]n, was obtained by the hydrothermal reaction of CoSO4 with benzene-1,4-dioxydiacetate [systematic name: p-phenylenebis(oxyacetate)] and 4,4′-bipyridine (4,4′-bpy). The Co atom lies at an inversion center and the benzene-1,4-dioxydiacetate and 4,4′-bipyridine moieties lie about other inversion centers. The benzene-1,4-dioxydiacetate ligands bridge the octahedral CoII coordination centers, forming a one-dimensional zigzag chain. The chains are further bridged by 4,4′-bpy ligands, forming a novel two-dimensional supramolecular architecture. Hydrogen-bonding interactions between the coordinated water molecules and the carboxylate O atoms lead to the formation of a three-dimensional network structure.
Supporting information
CCDC reference: 264776
The pH of a mixture of CoSO4·7H2O (0.50 mmol, 0.14 g), 4,4'-bpy (0.5 mmol, 0.078 g), benzene-1,4-dioxydiacetic acid (0.5 mmol, 0.113 g) and H2O (15 ml) was adjusted to 6–7 by 10% NaOH under vigorous stirring. The mixture was sealed in a Teflon-lined stainless steel vessel and heated at 393 K for 96 h, and then cooled slowly to 303 K at a rate of 1.39 K h−1. Deep-red crystals were obtained (yield 48%, based on Co).
The C-bound H atoms, except those on atoms C1 and C3?, were positioned geometrically and refined using a riding model [C—H = 0.93 and 0.97 Å, and Uiso(H) = 1.2Ueq(C)]. The aqua H atoms were located from difference maps and refined with an O—H distance restraint of 0.82 (s.u.?) Å? [Uiso(H) = 1.5Ueq(O)]. Treatment of H atoms bound to C1 and C3?
Data collection: SMART (Siemens, 1996); cell refinement: SMART and SAINT (Siemens, 1994); data reduction: SANT and? XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Poly[[diaquacobalt(II)]-µ-4,4'-bipyridine-
κ2N:
N'-µ-
p- phenylenebis(oxyacetato)-
κ2O:
O']
top
Crystal data top
[Co(C10H8O6)(C10H8N2)(H2O)2] | Z = 1 |
Mr = 475.31 | F(000) = 245 |
Triclinic, P1 | Dx = 1.676 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.760 (1) Å | Cell parameters from 1535 reflections |
b = 8.177 (1) Å | θ = 2.0–25.1° |
c = 10.639 (2) Å | µ = 0.97 mm−1 |
α = 106.10 (1)° | T = 293 K |
β = 96.91 (1)° | Prism, red |
γ = 97.40 (1)° | 0.60 × 0.38 × 0.30 mm |
V = 470.98 (14) Å3 | |
Data collection top
Siemens SMART CCD area-detector diffractometer | 1663 independent reflections |
Radiation source: fine-focus sealed tube | 1409 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
ϕ and ω scans | θmax = 25.1°, θmin = 2.0° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −6→6 |
Tmin = 0.650, Tmax = 0.748 | k = −9→6 |
2498 measured reflections | l = −11→12 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.072 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.183 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.049P)2 + 3.5833P] where P = (Fo2 + 2Fc2)/3 |
1664 reflections | (Δ/σ)max < 0.001 |
156 parameters | Δρmax = 0.61 e Å−3 |
2 restraints | Δρmin = −0.83 e Å−3 |
Crystal data top
[Co(C10H8O6)(C10H8N2)(H2O)2] | γ = 97.40 (1)° |
Mr = 475.31 | V = 470.98 (14) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.760 (1) Å | Mo Kα radiation |
b = 8.177 (1) Å | µ = 0.97 mm−1 |
c = 10.639 (2) Å | T = 293 K |
α = 106.10 (1)° | 0.60 × 0.38 × 0.30 mm |
β = 96.91 (1)° | |
Data collection top
Siemens SMART CCD area-detector diffractometer | 1663 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1409 reflections with I > 2σ(I) |
Tmin = 0.650, Tmax = 0.748 | Rint = 0.040 |
2498 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.072 | 2 restraints |
wR(F2) = 0.183 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.61 e Å−3 |
1664 reflections | Δρmin = −0.83 e Å−3 |
156 parameters | |
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 | x | y | z | Uiso*/Ueq | |
Co1 | 0.0000 | 0.0000 | 0.0000 | 0.0258 (4) | |
O1W | 0.3257 (8) | 0.1436 (6) | −0.0176 (4) | 0.0340 (10) | |
H1WB | 0.256 (13) | 0.213 (8) | −0.043 (8) | 0.051* | |
H1WA | 0.424 (11) | 0.112 (10) | −0.066 (6) | 0.051* | |
O1 | 0.5229 (8) | −0.2380 (6) | 0.2600 (4) | 0.0373 (11) | |
O2 | −0.0798 (8) | −0.3480 (6) | 0.1046 (5) | 0.0439 (12) | |
O3 | 0.2021 (7) | −0.1340 (5) | 0.0994 (4) | 0.0289 (10) | |
N1 | 0.0041 (9) | 0.1961 (6) | 0.1866 (5) | 0.0288 (11) | |
C1 | 0.6967 (12) | 0.0057 (10) | 0.4390 (7) | 0.0377 (16) | |
H1 | 0.827 (12) | 0.013 (9) | 0.390 (7) | 0.035 (18)* | |
C2 | 0.4983 (11) | −0.1217 (9) | 0.3782 (6) | 0.0333 (14) | |
C3 | 0.3004 (12) | −0.1247 (9) | 0.4394 (6) | 0.0354 (15) | |
H3 | 0.148 (11) | −0.219 (8) | 0.388 (6) | 0.025 (15)* | |
C4 | 0.3146 (12) | −0.3576 (9) | 0.1871 (7) | 0.0364 (15) | |
H4A | 0.2449 | −0.4144 | 0.2458 | 0.044* | |
H4B | 0.3599 | −0.4455 | 0.1168 | 0.044* | |
C5 | 0.1284 (11) | −0.2722 (8) | 0.1262 (6) | 0.0272 (13) | |
C6 | 0.1777 (11) | 0.2226 (8) | 0.2897 (6) | 0.0311 (14) | |
H6 | 0.3010 | 0.1597 | 0.2782 | 0.037* | |
C7 | 0.1815 (11) | 0.3394 (8) | 0.4123 (6) | 0.0318 (14) | |
H7 | 0.3054 | 0.3526 | 0.4809 | 0.038* | |
C8 | 0.0019 (10) | 0.4370 (7) | 0.4339 (5) | 0.0259 (13) | |
C9 | −0.1754 (12) | 0.4119 (9) | 0.3260 (6) | 0.0366 (16) | |
H9 | −0.2991 | 0.4749 | 0.3339 | 0.044* | |
C10 | −0.1655 (11) | 0.2915 (9) | 0.2062 (6) | 0.0375 (16) | |
H10 | −0.2855 | 0.2768 | 0.1352 | 0.045* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0285 (7) | 0.0272 (6) | 0.0192 (6) | 0.0064 (5) | 0.0042 (4) | 0.0020 (5) |
O1W | 0.031 (3) | 0.042 (3) | 0.031 (2) | 0.008 (2) | 0.0082 (19) | 0.012 (2) |
O1 | 0.032 (2) | 0.047 (3) | 0.031 (2) | 0.010 (2) | 0.0062 (19) | 0.006 (2) |
O2 | 0.032 (3) | 0.042 (3) | 0.061 (3) | 0.005 (2) | 0.011 (2) | 0.020 (2) |
O3 | 0.028 (2) | 0.034 (2) | 0.023 (2) | 0.0085 (18) | 0.0004 (17) | 0.0072 (18) |
N1 | 0.024 (3) | 0.029 (3) | 0.027 (3) | 0.003 (2) | 0.002 (2) | −0.002 (2) |
C1 | 0.030 (4) | 0.055 (4) | 0.034 (4) | 0.010 (3) | 0.011 (3) | 0.018 (3) |
C2 | 0.030 (3) | 0.039 (4) | 0.037 (4) | 0.013 (3) | 0.007 (3) | 0.019 (3) |
C3 | 0.032 (4) | 0.044 (4) | 0.029 (3) | 0.004 (3) | 0.004 (3) | 0.011 (3) |
C4 | 0.039 (4) | 0.036 (4) | 0.036 (4) | 0.015 (3) | 0.006 (3) | 0.010 (3) |
C5 | 0.031 (3) | 0.029 (3) | 0.021 (3) | 0.010 (3) | 0.006 (2) | 0.003 (2) |
C6 | 0.036 (4) | 0.029 (3) | 0.025 (3) | 0.010 (3) | 0.004 (3) | 0.000 (2) |
C7 | 0.035 (4) | 0.035 (3) | 0.019 (3) | 0.012 (3) | −0.005 (2) | −0.001 (2) |
C8 | 0.030 (3) | 0.026 (3) | 0.019 (3) | 0.002 (2) | 0.001 (2) | 0.004 (2) |
C9 | 0.035 (4) | 0.049 (4) | 0.023 (3) | 0.022 (3) | 0.000 (3) | 0.001 (3) |
C10 | 0.028 (3) | 0.049 (4) | 0.025 (3) | 0.008 (3) | −0.005 (3) | −0.002 (3) |
Geometric parameters (Å, º) top
Co1—O3i | 2.086 (4) | C1—H1 | 0.97 (7) |
Co1—O3 | 2.086 (4) | C2—C3 | 1.380 (9) |
Co1—O1W | 2.138 (5) | C3—C1ii | 1.383 (10) |
Co1—O1Wi | 2.138 (5) | C3—H3 | 1.07 (6) |
Co1—N1i | 2.174 (5) | C4—C5 | 1.528 (8) |
Co1—N1 | 2.174 (5) | C4—H4A | 0.9700 |
O1W—H1WB | 0.82 (7) | C4—H4B | 0.9700 |
O1W—H1WA | 0.83 (6) | C6—C7 | 1.382 (8) |
O1—C2 | 1.386 (8) | C6—H6 | 0.9300 |
O1—C4 | 1.432 (8) | C7—C8 | 1.388 (8) |
O2—C5 | 1.240 (7) | C7—H7 | 0.9300 |
O3—C5 | 1.274 (7) | C8—C9 | 1.392 (8) |
N1—C10 | 1.327 (8) | C8—C8iii | 1.499 (11) |
N1—C6 | 1.341 (8) | C9—C10 | 1.390 (9) |
C1—C3ii | 1.383 (10) | C9—H9 | 0.9300 |
C1—C2 | 1.396 (10) | C10—H10 | 0.9300 |
| | | |
O3i—Co1—O3 | 180.0 (3) | O1—C2—C1 | 115.2 (6) |
O3i—Co1—O1W | 92.23 (17) | C2—C3—C1ii | 119.9 (6) |
O3—Co1—O1W | 87.77 (17) | C2—C3—H3 | 117 (3) |
O3i—Co1—O1Wi | 87.77 (17) | C1ii—C3—H3 | 123 (3) |
O3—Co1—O1Wi | 92.23 (17) | O1—C4—C5 | 113.1 (5) |
O1W—Co1—O1Wi | 180.0 (2) | O1—C4—H4A | 109.0 |
O3i—Co1—N1i | 90.18 (17) | C5—C4—H4A | 109.0 |
O3—Co1—N1i | 89.82 (17) | O1—C4—H4B | 109.0 |
O1W—Co1—N1i | 91.88 (18) | C5—C4—H4B | 109.0 |
O1Wi—Co1—N1i | 88.12 (18) | H4A—C4—H4B | 107.8 |
O3i—Co1—N1 | 89.82 (17) | O2—C5—O3 | 126.6 (6) |
O3—Co1—N1 | 90.18 (17) | O2—C5—C4 | 116.2 (6) |
O1W—Co1—N1 | 88.12 (18) | O3—C5—C4 | 117.2 (5) |
O1Wi—Co1—N1 | 91.88 (18) | N1—C6—C7 | 122.9 (6) |
N1i—Co1—N1 | 180.00 (19) | N1—C6—H6 | 118.5 |
Co1—O1W—H1WB | 92 (6) | C7—C6—H6 | 118.5 |
Co1—O1W—H1WA | 129 (6) | C6—C7—C8 | 120.6 (5) |
H1WB—O1W—H1WA | 110 (8) | C6—C7—H7 | 119.7 |
C2—O1—C4 | 116.7 (5) | C8—C7—H7 | 119.7 |
C5—O3—Co1 | 126.7 (4) | C7—C8—C9 | 116.4 (5) |
C10—N1—C6 | 116.6 (5) | C7—C8—C8iii | 122.1 (6) |
C10—N1—Co1 | 122.5 (4) | C9—C8—C8iii | 121.5 (7) |
C6—N1—Co1 | 120.8 (4) | C10—C9—C8 | 119.2 (6) |
C3ii—C1—C2 | 121.1 (6) | C10—C9—H9 | 120.4 |
C3ii—C1—H1 | 121 (4) | C8—C9—H9 | 120.4 |
C2—C1—H1 | 117 (4) | N1—C10—C9 | 124.2 (6) |
C3—C2—O1 | 125.7 (6) | N1—C10—H10 | 117.9 |
C3—C2—C1 | 119.0 (6) | C9—C10—H10 | 117.9 |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z+1; (iii) −x, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O2i | 0.83 (6) | 1.79 (7) | 2.609 (7) | 174 (8) |
O1W—H1WB···O3i | 0.83 (6) | 2.59 (7) | 3.045 (6) | 116 (7) |
O1W—H1WA···O3iv | 0.82 (7) | 2.22 (4) | 2.958 (6) | 149 (7) |
O1W—H1WA···O1iv | 0.82 (7) | 2.58 (7) | 3.078 (6) | 120 (7) |
Symmetry codes: (i) −x, −y, −z; (iv) −x+1, −y, −z. |
Experimental details
Crystal data |
Chemical formula | [Co(C10H8O6)(C10H8N2)(H2O)2] |
Mr | 475.31 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 5.760 (1), 8.177 (1), 10.639 (2) |
α, β, γ (°) | 106.10 (1), 96.91 (1), 97.40 (1) |
V (Å3) | 470.98 (14) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.97 |
Crystal size (mm) | 0.60 × 0.38 × 0.30 |
|
Data collection |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.650, 0.748 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2498, 1663, 1409 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.596 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.072, 0.183, 1.11 |
No. of reflections | 1664 |
No. of parameters | 156 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.61, −0.83 |
Selected geometric parameters (Å, º) topCo1—O3i | 2.086 (4) | Co1—N1i | 2.174 (5) |
Co1—O1W | 2.138 (5) | | |
| | | |
O3i—Co1—O1W | 92.23 (17) | O1W—Co1—N1i | 91.88 (18) |
O3i—Co1—N1i | 90.18 (17) | | |
Symmetry code: (i) −x, −y, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O2i | 0.83 (6) | 1.79 (7) | 2.609 (7) | 174 (8) |
O1W—H1WB···O3i | 0.83 (6) | 2.59 (7) | 3.045 (6) | 116 (7) |
O1W—H1WA···O3ii | 0.82 (7) | 2.22 (4) | 2.958 (6) | 149 (7) |
O1W—H1WA···O1ii | 0.82 (7) | 2.58 (7) | 3.078 (6) | 120 (7) |
Symmetry codes: (i) −x, −y, −z; (ii) −x+1, −y, −z. |
In recent years, the crystal engineering and construction of metal-organic coordination polymers with fascinating structural topologies have attracted great attention owing to the potential functions of these compounds as microporous solids for molecular adsorption, ion exchange and heterogeneous catalysis (Matsumoto et al., 1999; Chui et al., 1999). The majority of reported work is based on the use of multidentate ligands to bind to the d-block transition metal ions through self-assembly processes. It has also been proved that the careful selection of appropriate ligands is crucial to the construction of specific supramolecular architectures. This concept is demonstrated by the great variety of structural topologies of discrete supramolecular complexes or infinite supramolecular arrays, such as molecular grids, racks, bricks, rings, boxes, honeycombs and helicates (Fei et al., 2000; Caradoc-Davies, 2000). In general, (i) the multiple coordination sites of the ligand incline to forming higher dimensions and (ii) the long chain of the ligand may generate a larger cavity or channel in the assembly reaction with metal ions. On the basis of the above considerations, we chose benzene-1,4-dioxydiacetic acid and 4,4'-bpy as bridge ligands in this work. We report here the novel two-dimensional framework structure [CoII(C8N2H8)(C8H8O6)(H2O)2]n,(I), which is built up by connecting the crystallographically unique CoII atom with its neighbors via bridging 4,4'-bpy ligands and benzene-1,4-dioxydiacetate. To the best of our knowledge, although benzene-1,4-dioxydiacetic acid is a multidentate ligand in that it has the potential to coordinate to metals in a number of different ways, few compounds of benzene-1,4-dioxydiacetic acid have been reported.
The single-crystal X-ray diffraction study reveals that polymer (I), which crystallizes in space group P-1, consists of an infinite grid-like layer. The molecular structure, with the atomic labeling scheme, is presented in Fig. 1. The CoII ion lies at the cell origin and is octahedrally coordinated by two N atoms from two 4,4'-bpy ligands, two identical monodentate carboxylate groups and two water molecules, which are all in trans arrangements. It can be seen that the CoII ion is coplanar with the plane defined by atoms O3, O3a, OW1 and OW1a. The Co—O distances range from 2.086 (4) to 2.138 (5) Å and the Co—N distance is 2.174 (5) Å; these distances are similar to those in related cobalt complexes (Wu et al., 2002; Zhu et al., 2003). Each benzene-1,4-dioxydiacetate ligand in a µ2-bridging mode links two metal centers, and each metal center connects two benzene-1,4-dioxydiacetate ligands to form a zigzag chain structure. Each 4,4'-bpy ligand bridges two CoII atoms from two neighboring zigzag chains, resulting in a two-dimensional lamellar.
The structure of (I) contains 44-membered macrometallacyclic rings, comprising four CoII ions at the corners, two 4,4'-bpy ligands and two benzene-1,4-dioxydiacetate ligands as the edges (see Fig. 2).
There are extensive hydrogen-bonding and short-contact interactions, namely (i) intramolecular hydrogen-bonding between the coordinated water molecules and the uncoordinated carboxyl O atoms, with an O···O distance of 2.609 (7) Å; (ii) interlayer hydrogen-bonding interactions between the coordinated water molecules and the coordinated carboxyl O atoms, with an O···O distance of 2.958 (6) Å; and (iii) weak short-contact interactions between the coordinated water molecular and carboxyl O atoms, with O···O distances ranging from 3.045 (6) to 3.078 (6) Å. As stated above, the structure contains a two-dimensional coordination polymer. However, the hydrogen bonding in the structure allows the formation of an extended three-dimensional supramolecular framework (see Fig. 3).