The asymmetric unit of the title one-dimensional coordination polymer,
catena-poly[[μ-pyridine-2,3-dicarboxylato-1κ
O:2κ
2N,
O′-bis[diaquacobalt(II)]]-μ-pyridine-2,3-dicarboxylato-1κ
2N,
O:2κ
O′:1′κ
O′], [Co(C
7H
3NO
4)(H
2O)
2]
n, is composed of a cobalt(II) ion, a pyridine-2,3-dicarboxylate dianion and two water molecules. The polymer has a zigzag structure consisting of a chain of edge-fused rings, and the polymer chains are linked by O—H
O hydrogen bonds into a three-dimensional framework.
Supporting information
CCDC reference: 219549
Co(ClO4)2·6H2O (36.6 mg, 0.10 mmol), pyridine-2,3-dicarboxylic acid (16.7 mg, 0.10 mmol) and pyridine (0.4 cm3) were dissolved in a mixture of water (3 cm3) and ethanol (3 cm3), and the mixture was placed in a Teflon-lined stainless-steel vessel (25 cm3). The vessel was sealed and heated at 403 K for 3 d and then cooled to room temperature. Large red prismatic crystals were collected by filtration, followed by washing with water and ethanol.
H atoms bonded to C atoms were treated as riding, with Uiso(H) values equal to 1.2Ueq(C) and C—H distances of 0.93 Å. Water H atoms were located from difference maps and were refined subject to an O—H DFIX restraint of 0.82 (3) Å (eight restraints), and the Uiso(H) values were constrained to be 1.2Ueq(O).
Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2000).
catena- [diaqua(pyridine-2,3-dicarboxylato-
κ4N:
O,
O',
O')cobalt(II)]
top
Crystal data top
[Co(C7H3NO4)(H2O)2] | F(000) = 524 |
Mr = 260.07 | Dx = 2.007 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 7.7200 (15) Å | θ = 2.2–13.9° |
b = 15.620 (3) Å | µ = 2.00 mm−1 |
c = 7.8100 (16) Å | T = 298 K |
β = 113.95 (3)° | Prism, red |
V = 860.7 (4) Å3 | 0.37 × 0.24 × 0.20 mm |
Z = 4 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 1254 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 25.0°, θmin = 3.1° |
ω scans | h = 0→9 |
Absorption correction: psi scan XCAD4 (Harms & Wocadlo, 1995) | k = 0→18 |
Tmin = 0.470, Tmax = 0.670 | l = −9→8 |
1625 measured reflections | 3 standard reflections every 200 reflections |
1509 independent reflections | intensity decay: 1.1% |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0319P)2 + 0.385P] where P = (Fo2 + 2Fc2)/3 |
1509 reflections | (Δ/σ)max = 0.001 |
152 parameters | Δρmax = 0.28 e Å−3 |
4 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
[Co(C7H3NO4)(H2O)2] | V = 860.7 (4) Å3 |
Mr = 260.07 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.7200 (15) Å | µ = 2.00 mm−1 |
b = 15.620 (3) Å | T = 298 K |
c = 7.8100 (16) Å | 0.37 × 0.24 × 0.20 mm |
β = 113.95 (3)° | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 1254 reflections with I > 2σ(I) |
Absorption correction: psi scan XCAD4 (Harms & Wocadlo, 1995) | Rint = 0.017 |
Tmin = 0.470, Tmax = 0.670 | 3 standard reflections every 200 reflections |
1625 measured reflections | intensity decay: 1.1% |
1509 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.023 | 4 restraints |
wR(F2) = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.28 e Å−3 |
1509 reflections | Δρmin = −0.36 e Å−3 |
152 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 | |
Co | 0.35351 (4) | 0.55715 (2) | 0.07142 (4) | 0.01702 (12) | |
N1 | 0.5480 (3) | 0.60168 (12) | 0.3338 (3) | 0.0172 (4) | |
O1 | 0.5170 (2) | 0.56919 (10) | 0.8996 (2) | 0.0179 (4) | |
O2 | 0.4216 (3) | 0.70161 (11) | 0.8014 (3) | 0.0340 (5) | |
O3 | 0.1955 (3) | 0.57115 (13) | 0.5084 (3) | 0.0291 (4) | |
O4 | 0.1997 (2) | 0.54100 (11) | 0.2318 (2) | 0.0228 (4) | |
O1W | 0.2409 (3) | 0.68383 (12) | 0.0173 (3) | 0.0295 (4) | |
O2W | 0.1461 (3) | 0.51688 (13) | −0.1719 (3) | 0.0261 (4) | |
C1 | 0.4757 (3) | 0.60161 (14) | 0.4647 (3) | 0.0164 (5) | |
C2 | 0.5794 (3) | 0.62869 (15) | 0.6463 (3) | 0.0188 (5) | |
C3 | 0.7636 (4) | 0.65845 (16) | 0.6929 (3) | 0.0234 (6) | |
H3 | 0.8374 | 0.6766 | 0.8143 | 0.028* | |
C4 | 0.8349 (4) | 0.66065 (17) | 0.5579 (4) | 0.0259 (6) | |
H4 | 0.9565 | 0.6811 | 0.5856 | 0.031* | |
C5 | 0.7216 (4) | 0.63170 (16) | 0.3793 (4) | 0.0225 (5) | |
H5 | 0.7695 | 0.6334 | 0.2876 | 0.027* | |
C6 | 0.4965 (3) | 0.63277 (15) | 0.7909 (3) | 0.0193 (5) | |
C7 | 0.2737 (3) | 0.56924 (15) | 0.3987 (3) | 0.0186 (5) | |
H2WA | 0.144 (5) | 0.531 (2) | −0.273 (4) | 0.042 (10)* | |
H1WA | 0.280 (5) | 0.699 (2) | −0.060 (4) | 0.050 (11)* | |
H2WB | 0.039 (4) | 0.501 (3) | −0.178 (5) | 0.071 (13)* | |
H1WB | 0.296 (5) | 0.713 (2) | 0.114 (4) | 0.062 (12)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co | 0.01784 (18) | 0.02070 (18) | 0.01339 (18) | −0.00146 (14) | 0.00724 (13) | −0.00179 (13) |
N1 | 0.0185 (10) | 0.0175 (10) | 0.0171 (10) | 0.0000 (8) | 0.0088 (8) | −0.0020 (8) |
O1 | 0.0200 (8) | 0.0195 (8) | 0.0151 (8) | 0.0005 (7) | 0.0082 (7) | 0.0023 (7) |
O2 | 0.0591 (13) | 0.0215 (10) | 0.0323 (11) | 0.0098 (9) | 0.0299 (10) | 0.0048 (8) |
O3 | 0.0225 (9) | 0.0497 (12) | 0.0196 (9) | −0.0034 (8) | 0.0132 (8) | −0.0016 (8) |
O4 | 0.0206 (9) | 0.0322 (10) | 0.0168 (8) | −0.0065 (7) | 0.0089 (7) | −0.0049 (7) |
O1W | 0.0369 (11) | 0.0270 (10) | 0.0268 (11) | 0.0007 (9) | 0.0153 (10) | −0.0011 (9) |
O2W | 0.0189 (9) | 0.0427 (11) | 0.0157 (9) | −0.0089 (8) | 0.0059 (8) | −0.0039 (8) |
C1 | 0.0198 (12) | 0.0149 (11) | 0.0162 (12) | 0.0010 (10) | 0.0089 (10) | 0.0016 (9) |
C2 | 0.0219 (12) | 0.0163 (11) | 0.0181 (12) | −0.0002 (10) | 0.0081 (10) | 0.0027 (9) |
C3 | 0.0230 (13) | 0.0260 (13) | 0.0186 (12) | −0.0039 (10) | 0.0057 (11) | −0.0017 (10) |
C4 | 0.0208 (13) | 0.0270 (13) | 0.0293 (14) | −0.0040 (11) | 0.0097 (11) | −0.0015 (11) |
C5 | 0.0249 (13) | 0.0235 (13) | 0.0242 (13) | −0.0018 (11) | 0.0152 (11) | −0.0012 (10) |
C6 | 0.0208 (12) | 0.0217 (12) | 0.0138 (12) | −0.0049 (10) | 0.0055 (10) | −0.0030 (10) |
C7 | 0.0193 (12) | 0.0192 (12) | 0.0172 (12) | 0.0015 (10) | 0.0074 (10) | 0.0024 (9) |
Geometric parameters (Å, º) top
Co—O2W | 2.025 (2) | O1W—H1WB | 0.84 (3) |
Co—O4 | 2.0613 (17) | O2W—H2WA | 0.81 (2) |
Co—N1 | 2.107 (2) | O2W—H2WB | 0.85 (3) |
Co—O1W | 2.133 (2) | C1—C2 | 1.382 (3) |
Co—O1i | 2.1821 (16) | C1—C7 | 1.517 (3) |
Co—O1ii | 2.1920 (17) | C2—C3 | 1.396 (3) |
N1—C5 | 1.325 (3) | C2—C6 | 1.508 (3) |
N1—C1 | 1.348 (3) | C3—C4 | 1.374 (4) |
O1—C6 | 1.274 (3) | C3—H3 | 0.9300 |
O2—C6 | 1.239 (3) | C4—C5 | 1.387 (4) |
O3—C7 | 1.232 (3) | C4—H4 | 0.9300 |
O4—C7 | 1.271 (3) | C5—H5 | 0.9300 |
O1W—H1WA | 0.81 (2) | | |
| | | |
O2W—Co—O4 | 95.81 (7) | Co—O2W—H2WA | 122 (2) |
O2W—Co—N1 | 174.31 (8) | Co—O2W—H2WB | 122 (3) |
O4—Co—N1 | 78.94 (7) | H2WA—O2W—H2WB | 113 (3) |
O2W—Co—O1W | 89.93 (8) | N1—C1—C2 | 122.2 (2) |
O4—Co—O1W | 86.84 (8) | N1—C1—C7 | 115.3 (2) |
N1—Co—O1W | 87.63 (8) | C2—C1—C7 | 122.5 (2) |
O2W—Co—O1i | 88.34 (7) | C1—C2—C3 | 118.3 (2) |
O4—Co—O1i | 100.30 (6) | C1—C2—C6 | 122.4 (2) |
N1—Co—O1i | 94.70 (7) | C3—C2—C6 | 119.2 (2) |
O1W—Co—O1i | 172.79 (7) | C4—C3—C2 | 119.4 (2) |
O2W—Co—O1ii | 83.37 (7) | C4—C3—H3 | 120.3 |
O4—Co—O1ii | 177.89 (6) | C2—C3—H3 | 120.3 |
N1—Co—O1ii | 101.96 (7) | C3—C4—C5 | 118.5 (2) |
O1W—Co—O1ii | 95.09 (7) | C3—C4—H4 | 120.7 |
O1i—Co—O1ii | 77.75 (6) | C5—C4—H4 | 120.7 |
C5—N1—C1 | 118.8 (2) | N1—C5—C4 | 122.8 (2) |
C5—N1—Co | 128.41 (16) | N1—C5—H5 | 118.6 |
C1—N1—Co | 112.72 (15) | C4—C5—H5 | 118.6 |
C6—O1—Coi | 134.59 (15) | O2—C6—O1 | 124.6 (2) |
C6—O1—Coiii | 121.89 (15) | O2—C6—C2 | 115.9 (2) |
Coi—O1—Coiii | 102.25 (6) | O1—C6—C2 | 119.3 (2) |
C7—O4—Co | 116.81 (15) | O3—C7—O4 | 125.3 (2) |
Co—O1W—H1WA | 100 (3) | O3—C7—C1 | 118.8 (2) |
Co—O1W—H1WB | 108 (3) | O4—C7—C1 | 115.8 (2) |
H1WA—O1W—H1WB | 108 (4) | | |
| | | |
O4—Co—N1—C5 | −180.0 (2) | C1—C2—C3—C4 | 0.6 (4) |
O1W—Co—N1—C5 | −92.7 (2) | C6—C2—C3—C4 | −175.3 (2) |
O1i—Co—N1—C5 | 80.5 (2) | C2—C3—C4—C5 | −1.0 (4) |
O1ii—Co—N1—C5 | 2.0 (2) | C1—N1—C5—C4 | 2.1 (4) |
O4—Co—N1—C1 | −3.09 (15) | Co—N1—C5—C4 | 178.81 (19) |
O1W—Co—N1—C1 | 84.15 (16) | C3—C4—C5—N1 | −0.3 (4) |
O1i—Co—N1—C1 | −102.69 (16) | Coi—O1—C6—O2 | −177.61 (18) |
O1ii—Co—N1—C1 | 178.86 (15) | Coiii—O1—C6—O2 | 17.8 (3) |
O2W—Co—O4—C7 | −172.09 (17) | Coi—O1—C6—C2 | −2.2 (3) |
N1—Co—O4—C7 | 5.72 (17) | Coiii—O1—C6—C2 | −166.81 (16) |
O1W—Co—O4—C7 | −82.48 (17) | C1—C2—C6—O2 | −90.6 (3) |
O1i—Co—O4—C7 | 98.55 (17) | C3—C2—C6—O2 | 85.1 (3) |
C5—N1—C1—C2 | −2.6 (3) | C1—C2—C6—O1 | 93.6 (3) |
Co—N1—C1—C2 | −179.76 (18) | C3—C2—C6—O1 | −90.7 (3) |
C5—N1—C1—C7 | 177.8 (2) | Co—O4—C7—O3 | 173.87 (19) |
Co—N1—C1—C7 | 0.6 (2) | Co—O4—C7—C1 | −7.0 (3) |
N1—C1—C2—C3 | 1.2 (3) | N1—C1—C7—O3 | −176.6 (2) |
C7—C1—C2—C3 | −179.2 (2) | C2—C1—C7—O3 | 3.8 (3) |
N1—C1—C2—C6 | 177.0 (2) | N1—C1—C7—O4 | 4.2 (3) |
C7—C1—C2—C6 | −3.4 (4) | C2—C1—C7—O4 | −175.4 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z−1; (iii) x, y, z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O2iv | 0.84 (3) | 1.92 (3) | 2.749 (3) | 168 (4) |
O1W—H1WA···O2ii | 0.81 (2) | 1.83 (3) | 2.604 (3) | 160 (4) |
O2W—H2WA···O3ii | 0.81 (2) | 2.01 (2) | 2.806 (3) | 168 (3) |
O2W—H2WB···O4v | 0.85 (3) | 1.84 (3) | 2.674 (3) | 170 (4) |
Symmetry codes: (ii) x, y, z−1; (iv) x, −y+3/2, z−1/2; (v) −x, −y+1, −z. |
Experimental details
Crystal data |
Chemical formula | [Co(C7H3NO4)(H2O)2] |
Mr | 260.07 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 7.7200 (15), 15.620 (3), 7.8100 (16) |
β (°) | 113.95 (3) |
V (Å3) | 860.7 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.00 |
Crystal size (mm) | 0.37 × 0.24 × 0.20 |
|
Data collection |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Psi scan XCAD4 (Harms & Wocadlo, 1995) |
Tmin, Tmax | 0.470, 0.670 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1625, 1509, 1254 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.062, 1.00 |
No. of reflections | 1509 |
No. of parameters | 152 |
No. of restraints | 4 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.36 |
Selected geometric parameters (Å, º) topCo—O2W | 2.025 (2) | Co—O1i | 2.1821 (16) |
Co—O4 | 2.0613 (17) | Co—O1ii | 2.1920 (17) |
Co—N1 | 2.107 (2) | N1—C1 | 1.348 (3) |
Co—O1W | 2.133 (2) | O4—C7 | 1.271 (3) |
| | | |
O2W—Co—O4 | 95.81 (7) | N1—Co—O1i | 94.70 (7) |
O2W—Co—N1 | 174.31 (8) | O2W—Co—O1ii | 83.37 (7) |
O4—Co—N1 | 78.94 (7) | N1—Co—O1ii | 101.96 (7) |
O2W—Co—O1W | 89.93 (8) | O1i—Co—O1ii | 77.75 (6) |
O4—Co—O1W | 86.84 (8) | C1—N1—Co | 112.72 (15) |
N1—Co—O1W | 87.63 (8) | Coi—O1—Coiii | 102.25 (6) |
O2W—Co—O1i | 88.34 (7) | C7—O4—Co | 116.81 (15) |
| | | |
C1—C2—C6—O2 | −90.6 (3) | C1—C2—C6—O1 | 93.6 (3) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y, z−1; (iii) x, y, z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O2iv | 0.84 (3) | 1.92 (3) | 2.749 (3) | 168 (4) |
O1W—H1WA···O2ii | 0.81 (2) | 1.83 (3) | 2.604 (3) | 160 (4) |
O2W—H2WA···O3ii | 0.81 (2) | 2.01 (2) | 2.806 (3) | 168 (3) |
O2W—H2WB···O4v | 0.85 (3) | 1.84 (3) | 2.674 (3) | 170 (4) |
Symmetry codes: (ii) x, y, z−1; (iv) x, −y+3/2, z−1/2; (v) −x, −y+1, −z. |
The design and synthesis of coordination polymers is one of the most stimulating research frontiers in contemporary chemistry, owing to the intriguing crystallographic structure and the functional properties of these compounds as potential applications in materials (Eddaoudi et al., 2001; Seo et al., 2000; Perles et al., 2003). Based on the nature of the metal and the coordination behaviour of the ligand, the "node and spacer" approach has been remarkably successful at producing predicatable coordination-polymer architectures (Batten & Robson, 1998). Many coordination polymers can be generated by using metal ions as the "node" and linking them with linear "spacer" ligands such as 1,4-benzenedicarboxylate, 4-pyridinecarboxylate and 4,4'-bipyridine (Li et al., 1999; Hagrman et al., 1999; Lu & Babb, 2001). We present here the structure of a one-dimensional zigzag-type coordination polymer, namely catena-poly [diaqua(pyridine-2,3-dicarboxylato-κ4N:O,O',O')cobalt(II)], (I).
The coordination motif of the CoII atom is a distorted octahedron (Table 1, Fig. 1) in which pyridyl atom N1, three carboxylate O atoms [O4, O1i and O1ii; symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, y, z − 1] and two water oxygen atoms (O1W and O2W) occupy the vertices. Thus, one cobalt(II) ion is bound to three pyridine-2,3-dicarboxylate ligands. One of these ligands chelates to the CoII atom via the pyridine N atom and one of the O atoms of the carboxylate group in the 2-position, thus generating a five-membered chelating ring (–C1—N1—Co—O4—C7-). The other carboxylate group (in the 3-position) lies almost perpendicular to the pyridine plane because of steric interaction between the two carboxylate groups. The O1—C6—O2 dihedral angle between the pyridine ring and the carboxyl is 88.40 (13)°. One of the O atoms of this ligand acts as a bridge to connect two CoII atoms in µ2-O mode, thus forming a rhomboidal Co2O2 ring. The Co···Coi [symmetry code: (i) 1 − x, 1 − y, 1 − z] distance is 3.4052 (8) Å, and the dihedral angle between the rhomboid ring and the five-membered chelating ring is 86.46 (7)°.
Along the c axis, two antiparallel ligands connect a pair of neighbouring CoII atoms in a head-to-tail fashion, thus generating a chain of edge-fused rings; alternatively, the structure may be regarded as a pair of zigzag chains that are joined together via the common Co2O2 rhomboid unit. The two parallel zigzag chains are related by inversion centres.
There are two intrachain hydrogen bonds, viz. O1W—H1WA···O2ii and O2W—H2WA···O3ii [symmetry code: (ii) x, y, z − 1], which may exert some influence on the overall conformation of the chain. The chains are arranged in a parallel fashion along the a axis and in a zigzag fasion along the b direction. As a result, along the a axis, the chains are connected by interchain O2W—H2WB···O4v hydrogen bonds [symmetry code: (v) −x, 1 − y, −z] to form a (010) sheet. Meanwhile, along the b axis, an interchain O1W—H1WB···O2iv hydrogen bond [symmetry code: (iv) x, 1.5 − y, −0.5 + z], links the chains into puckered (100) sheets. The combination of the (100) and (010) sheets links all of the polymer chains into a three-dimensional hydrogen-bonded framework.