Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010202019X/ta1395sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010202019X/ta1395Isup2.hkl |
CCDC reference: 201264
All chemicals and solvents were of reagent grade, and were used without further purification. 2,2'-Bipyridyl-3,3'-dicarboxylic acid (2,2'-binicotinic acid, H2bpdc) was prepared according to the literature method of Wimmer & Wimmer (1983). A mixture of CoCl2 (0.1298 g, 1.0 mmol) and H2bpdc (0.2560 g, 1.0 mmol) in a mole ratio of 1:1 was sealed in a 25 ml Teflon-lined stainless steel Parr bomb containing methanol (11.2 ml) and water (2.8 ml), heated at 433 K for 3 d, and then cooled to room temperature. Orange sheet-like crystals of (I) were isolated and washed in turn with water, ethanol and anhydrous ether. The reflectance spectrum of the compound was taken on a UV-3100 recording spectrophotometer from 250 to 2500 nm.
The H atoms on the water molecule were refined in fixed positions, while the others were refined in riding mode.
Data collection: SMART (Bruker, 1997-2000); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: SHELXL97.
[Co(C12H6N2O4)(H2O)2] | F(000) = 684 |
Mr = 337.15 | Dx = 1.938 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1437 reflections |
a = 11.373 (2) Å | θ = 3.2–31.2° |
b = 7.8632 (16) Å | µ = 1.52 mm−1 |
c = 13.162 (3) Å | T = 293 K |
β = 100.92 (3)° | Sheet, orange |
V = 1155.8 (4) Å3 | 0.2 × 0.1 × 0.05 mm |
Z = 4 |
Make Model CCD area-detector diffractometer | 2133 independent reflections |
Radiation source: fine-focus sealed tube | 1563 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 15 x 15 microns pixels mm-1 | θmax = 33.5°, θmin = 3.2° |
ϕ and ω scans | h = −17→17 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick 1996) | k = −7→11 |
Tmin = 0.764, Tmax = 0.927 | l = −20→19 |
5330 measured reflections |
Refinement on F2 | Primary atom site location: patt |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0624P)2 + 0.0074P] where P = (Fo2 + 2Fc2)/3 |
2133 reflections | (Δ/σ)max < 0.001 |
96 parameters | Δρmax = 0.69 e Å−3 |
2 restraints | Δρmin = −0.40 e Å−3 |
[Co(C12H6N2O4)(H2O)2] | V = 1155.8 (4) Å3 |
Mr = 337.15 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 11.373 (2) Å | µ = 1.52 mm−1 |
b = 7.8632 (16) Å | T = 293 K |
c = 13.162 (3) Å | 0.2 × 0.1 × 0.05 mm |
β = 100.92 (3)° |
Make Model CCD area-detector diffractometer | 2133 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick 1996) | 1563 reflections with I > 2σ(I) |
Tmin = 0.764, Tmax = 0.927 | Rint = 0.046 |
5330 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 2 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.69 e Å−3 |
2133 reflections | Δρmin = −0.40 e Å−3 |
96 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Co | 0.0000 | 0.70340 (7) | 0.2500 | 0.01833 (16) | |
O1 | −0.03905 (17) | 1.5087 (2) | 0.13819 (15) | 0.0217 (4) | |
O2 | 0.13384 (17) | 1.3653 (3) | 0.17289 (16) | 0.0252 (4) | |
O3 | −0.17466 (17) | 0.6908 (3) | 0.28347 (16) | 0.0258 (4) | |
H1 | −0.2314 | 0.7276 | 0.2450 | 0.031* | |
H2 | −0.1760 | 0.5889 | 0.2943 | 0.031* | |
N | −0.06589 (19) | 0.9130 (3) | 0.15830 (17) | 0.0181 (4) | |
C1 | −0.0290 (2) | 1.0679 (3) | 0.19373 (18) | 0.0147 (5) | |
C2 | −0.0425 (2) | 1.2080 (3) | 0.12723 (19) | 0.0157 (4) | |
C3 | −0.1105 (2) | 1.1878 (4) | 0.0281 (2) | 0.0203 (5) | |
H3 | −0.1250 | 1.2807 | −0.0162 | 0.024* | |
C4 | −0.1562 (2) | 1.0300 (4) | −0.0043 (2) | 0.0224 (5) | |
H4 | −0.2051 | 1.0159 | −0.0688 | 0.027* | |
C5 | −0.1275 (2) | 0.8947 (4) | 0.0615 (2) | 0.0216 (5) | |
H5 | −0.1515 | 0.7863 | 0.0381 | 0.026* | |
C6 | 0.0224 (2) | 1.3746 (3) | 0.14944 (18) | 0.0174 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.0193 (3) | 0.0105 (2) | 0.0242 (3) | 0.000 | 0.00149 (18) | 0.000 |
O1 | 0.0247 (9) | 0.0127 (9) | 0.0256 (10) | 0.0034 (7) | −0.0003 (7) | −0.0004 (8) |
O2 | 0.0193 (9) | 0.0164 (10) | 0.0381 (11) | 0.0010 (8) | 0.0006 (8) | 0.0004 (9) |
O3 | 0.0210 (9) | 0.0188 (10) | 0.0374 (12) | 0.0024 (8) | 0.0048 (8) | 0.0059 (9) |
N | 0.0188 (10) | 0.0114 (10) | 0.0230 (11) | −0.0009 (8) | 0.0013 (8) | −0.0021 (9) |
C1 | 0.0154 (11) | 0.0111 (11) | 0.0175 (11) | 0.0006 (8) | 0.0030 (8) | −0.0034 (9) |
C2 | 0.0173 (10) | 0.0103 (10) | 0.0194 (11) | 0.0015 (9) | 0.0029 (8) | −0.0009 (10) |
C3 | 0.0243 (12) | 0.0170 (12) | 0.0180 (12) | 0.0028 (10) | −0.0004 (9) | 0.0034 (10) |
C4 | 0.0213 (12) | 0.0238 (14) | 0.0204 (12) | −0.0010 (11) | −0.0009 (9) | −0.0027 (11) |
C5 | 0.0216 (12) | 0.0160 (12) | 0.0257 (13) | −0.0029 (10) | 0.0008 (10) | −0.0038 (11) |
C6 | 0.0245 (12) | 0.0140 (12) | 0.0135 (10) | −0.0017 (10) | 0.0026 (9) | 0.0002 (9) |
Co—N | 2.096 (2) | C1—C2 | 1.398 (3) |
Co—O1i | 2.112 (2) | C1—C1ii | 1.504 (5) |
Co—O3 | 2.116 (2) | C2—C3 | 1.395 (4) |
O1—C6 | 1.258 (3) | C2—C6 | 1.505 (4) |
O2—C6 | 1.249 (3) | C3—C4 | 1.382 (4) |
O3—H1 | 0.7959 | C3—H3 | 0.9300 |
O3—H2 | 0.815 | C4—C5 | 1.372 (4) |
N—C5 | 1.342 (3) | C4—H4 | 0.9300 |
N—C1 | 1.343 (3) | C5—H5 | 0.9300 |
Nii—Co—N | 76.35 (12) | N—C1—C1ii | 113.12 (15) |
N—Co—O1i | 99.38 (8) | C2—C1—C1ii | 126.37 (15) |
N—Co—O1iii | 167.59 (8) | C3—C2—C1 | 118.2 (2) |
O1i—Co—O1iii | 87.09 (11) | C3—C2—C6 | 116.5 (2) |
N—Co—O3ii | 99.49 (9) | C1—C2—C6 | 124.9 (2) |
N—Co—O3 | 84.75 (8) | C4—C3—C2 | 120.1 (2) |
O1i—Co—O3 | 91.63 (8) | C4—C3—H3 | 120.0 |
O1iii—Co—O3 | 84.49 (8) | C2—C3—H3 | 120.0 |
O3ii—Co—O3 | 174.65 (12) | C5—C4—C3 | 118.1 (2) |
C6—O1—Coiv | 119.07 (16) | C5—C4—H4 | 121.0 |
Co—O3—H1 | 122.14 | C3—C4—H4 | 121.0 |
Co—O3—H2 | 97.55 | N—C5—C4 | 122.4 (3) |
H1—O3—H2 | 115.4 | N—C5—H5 | 118.8 |
C5—N—C1 | 120.0 (2) | C4—C5—H5 | 118.8 |
C5—N—Co | 121.93 (18) | O2—C6—O1 | 126.4 (2) |
C1—N—Co | 117.28 (16) | O2—C6—C2 | 115.8 (2) |
N—C1—C2 | 120.5 (2) | O1—C6—C2 | 117.7 (2) |
Symmetry codes: (i) x, y−1, z; (ii) −x, y, −z+1/2; (iii) −x, y−1, −z+1/2; (iv) x, y+1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1···O2v | 0.80 | 1.97 | 2.748 (3) | 166 |
O3—H2···O2iii | 0.82 | 1.85 | 2.645 (3) | 164 |
Symmetry codes: (iii) −x, y−1, −z+1/2; (v) x−1/2, y−1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C12H6N2O4)(H2O)2] |
Mr | 337.15 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.373 (2), 7.8632 (16), 13.162 (3) |
β (°) | 100.92 (3) |
V (Å3) | 1155.8 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.52 |
Crystal size (mm) | 0.2 × 0.1 × 0.05 |
Data collection | |
Diffractometer | Make Model CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick 1996) |
Tmin, Tmax | 0.764, 0.927 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5330, 2133, 1563 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.776 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.132, 1.04 |
No. of reflections | 2133 |
No. of parameters | 96 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.69, −0.40 |
Computer programs: SMART (Bruker, 1997-2000), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1990), SHELXL97.
Co—N | 2.096 (2) | C1—C2 | 1.398 (3) |
Co—O1i | 2.112 (2) | C1—C1ii | 1.504 (5) |
Co—O3 | 2.116 (2) | C2—C3 | 1.395 (4) |
O1—C6 | 1.258 (3) | C2—C6 | 1.505 (4) |
O2—C6 | 1.249 (3) | C3—C4 | 1.382 (4) |
N—C5 | 1.342 (3) | C4—C5 | 1.372 (4) |
N—C1 | 1.343 (3) | ||
Nii—Co—N | 76.35 (12) | N—Co—O3 | 84.75 (8) |
N—Co—O1i | 99.38 (8) | O1i—Co—O3 | 91.63 (8) |
N—Co—O1iii | 167.59 (8) | O1iii—Co—O3 | 84.49 (8) |
O1i—Co—O1iii | 87.09 (11) | O3ii—Co—O3 | 174.65 (12) |
N—Co—O3ii | 99.49 (9) |
Symmetry codes: (i) x, y−1, z; (ii) −x, y, −z+1/2; (iii) −x, y−1, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1···O2iv | 0.80 | 1.97 | 2.748 (3) | 166 |
O3—H2···O2iii | 0.82 | 1.85 | 2.645 (3) | 164 |
Symmetry codes: (iii) −x, y−1, −z+1/2; (iv) x−1/2, y−1/2, z. |
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Transition metal coordination polymers of one-, two- and three-dimensional infinite frameworks have been an attractive research area because of their diverse structures and useful properties (Davis, 2002; Hagrman et al., 1999). Polydentate ligands, which are used as bridges in the construction of coordination polymers, are quite important in the crystal engineering of supramolecular architectures organized by coordinate covalent or hydrogen bonding (Moulton & Zaworotko, 2001).
2,2'-Bipyridyl-3,3'-dicarboxylate (bpdc) is a potential bridging ligand in view of its functional groups. However, it usually acts as an N,N'-bidentate ligand, forming a chelate with one metal centre in the corresponding discrete complex molecules (Goddard et al., 1990; Ravikumar et al., 1997; Yoo et al., 1997; Menon et al., 1997). Only a few metal coordination polymers bridged by bpdc have been reported to date. For example, bpdc acts as an O,O'-bidentate µ2 ligand to bridge two metal centres via one O atom of its two carboxyl groups in the polymer [Mn(bpdc)(H2O)4]n (Swamy et al., 1998). The monoprotonated bpdc in [Ag(µ3-Hbpdc)(H2O)]n (Tong et al., 2000) coordinates as an N,N',O-tridentate µ3 ligand to form three bridges, N—Ag, N'-Ag and O—Ag. Furthermore, in [Cu(µ2-bpdc)(H2O)2]n, bpdc also coordinates in an N,N',O-tridentate fashion, but as a µ2 ligand to bridge two CuII ions through one N—Cu—N' chelating system and one O—Cu coordinate bond (Zhuang et al., 1994; Ravikumar et al., 1995). The title complex, [Co(µ2-bpdc)(H2O)2]n, (I), reported here is another one-dimensional coordination polymer, in which bpdc acts as a µ2 ligand in the N,N':O,O'-tetradentate fashion to form two chelate bridges. \sch
In complex (I), the bpdc chelates one CoII cation, which lies on a twofold axis, via its two pyridyl N atoms (N and N'), and another CoII cation via its two carboxyl O atoms (O1 and O1'). Each CoII cation is octahedrally coordinated, where the equatorial plane comprises the two N atoms of one bpdc ligand on one side and two carboxyl O atoms from different carboxyl groups of a second bpdc ligand on the other side. The apical positions are occupied by the O atoms of the two coordinated water molecules (Fig 1). This octahedron is distorted (Table 1).
The crystal structure of (I) consists of linear polymeric chains of [Co(µ2-bpdc)(H2O)2] units. The chains incorporate a twofold axis along the chain direction, which is parallel to b. The chains are interconnected by hydrogen bonding involving atom H1 between adjacent chains, via the coordinated H2O molecules of one chain and the non-coordinated carboxyl O atoms of the adjacent chain, forming a layer parallel to (001). There is one intrachain hydrogen bond involving atom H2 (Fig. 2 and Table 2). These layers stack along the c axis to build up the whole crystal structure.
Complex (I) has the same chemical components as [Cu(µ-bpdc)(H2O)2]n, but it has a totally different crystal structure to that reported for the latter. The different structures are a result of bpdc acting as a tetradentate ligand in the Co complex and as a tridentate ligand in the Cu complex.
In order to explore the conductivity of (I), the Kubelka-Munk function, F = (1-Rinf)2/2Rinf, was converted from the recorded diffuse reflectance data for (I), where Rinf is the relative diffuse reflectance of an infinitely thick layer (Wendlandt & Hecht, 1966). The plot of the Kubelka-Munk function versus energy (eV) displayed a steep absorption edge in the UV-vis region, from which a band gap of about 2.7 eV was estimated (McCarthy et al., 1993). This suggests that the crystal of (I) is possibly a semiconductor.