Acta Cryst. (2007). E63, m2535 [ doi:10.1107/S1600536807044285 ]
![[mu]](/logos/entities/mu_rmgif.gif)
2-oxalato-![[kappa]](/logos/entities/kappa_rmgif.gif)
4O,O':O'',O'''-bis(pyridine-N)zinc(II)]The title compound, [Zn(C2O4)(C5H5N)2]n, was synthesized by the oxidation of pentaerythritol under solvothermal conditions. The backbone of the compound is formed from ZnII oxalate, with two pyridine ligands coordinated to each ZnII ion, giving it hexacoordination in a slightly distorted octahedral environment.
The compound was prepared by a solvothermal reaction of pentaerythritol (0.031 g), Zn(NO3)2·6H2O (0.027 g), using a solvent of pyridine (0.475 g). The mixture was sealed in a Pyrex glass tube with ca 10% filling, placed into a stainless-autoclave, and heated at 393 K for 6 days. After cooling naturally to ambient temperature, the products were washed with ethanol, and the yellow block crystals were obtained.
H atoms were positioned geometrically with C—H = 0.93 Å and allowed to ride during subsequent refinement with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SMART [or SAINT-Plus?] (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).
![[Figure 1]](./gw2024fig1thm.gif)
| Fig. 1. View of the molecular structure of (I) with the atom-labelling scheme and displacement ellipsoids drawn at the 30% probability level. Symmetry code:(i) 2 − x, −1 − y,-z + 1; (ii) −x + 1, −y − 1, −z + 1. H atoms have been omitted. |
![[Figure 2]](./gw2024fig2thm.gif)
| Fig. 2. Packing of the zigzag chains through interchain interdigitization of pyridine molecules in the compound. H atoms have been omitted. |
| [Zn(C2O4)(C5H5N)2] | F000 = 632 |
| Mr = 311.59 | Dx = 1.576 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| a = 9.4780 (9) Å | Cell parameters from 2981 reflections |
| b = 9.2118 (8) Å | θ = 2.5–26.3º |
| c = 15.0863 (13) Å | µ = 1.88 mm−1 |
| β = 94.402 (4)º | T = 293 (2) K |
| V = 1313.3 (2) Å3 | Block, yellow |
| Z = 4 | 0.30 × 0.25 × 0.20 mm |
| Bruker SMART APEX CCD diffractometer | 2981 independent reflections |
| Radiation source: fine-focus sealed tube | 2030 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.067 |
| T = 293(2) K | θmax = 27.4º |
| φ and ω scans | θmin = 2.5º |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −12→12 |
| Tmin = 0.602, Tmax = 0.705 | k = −11→11 |
| 15885 measured reflections | l = −19→19 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
| wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0391P)2 + 0.8316P] where P = (Fo2 + 2Fc2)/3 |
| S = 0.82 | (Δ/σ)max = 0.001 |
| 2981 reflections | Δρmax = 0.53 e Å−3 |
| 172 parameters | Δρmin = −0.33 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| [Zn(C2O4)(C5H5N)2] | V = 1313.3 (2) Å3 |
| Mr = 311.59 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 9.4780 (9) Å | µ = 1.88 mm−1 |
| b = 9.2118 (8) Å | T = 293 (2) K |
| c = 15.0863 (13) Å | 0.30 × 0.25 × 0.20 mm |
| β = 94.402 (4)º |
| Bruker SMART APEX CCD diffractometer | 2981 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | 2030 reflections with I > 2σ(I) |
| Tmin = 0.602, Tmax = 0.705 | Rint = 0.067 |
| 15885 measured reflections |
| R[F2 > 2σ(F2)] = 0.030 | 172 parameters |
| wR(F2) = 0.081 | H-atom parameters constrained |
| S = 0.82 | Δρmax = 0.53 e Å−3 |
| 2981 reflections | Δρmin = −0.33 e Å−3 |
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 | ||
| Zn1 | 0.75084 (3) | −0.34984 (3) | 0.504672 (15) | 0.02915 (10) | |
| O1 | 0.56734 (16) | −0.36565 (17) | 0.57297 (10) | 0.0330 (4) | |
| O2 | 0.92978 (16) | −0.36105 (18) | 0.43119 (9) | 0.0335 (4) | |
| O3 | 0.86912 (16) | −0.51562 (18) | 0.57471 (10) | 0.0359 (4) | |
| O4 | 0.63625 (16) | −0.51363 (18) | 0.42912 (10) | 0.0351 (4) | |
| N1 | 0.6728 (2) | −0.1855 (2) | 0.41113 (12) | 0.0361 (5) | |
| N2 | 0.8342 (2) | −0.1952 (2) | 0.60162 (12) | 0.0340 (5) | |
| C1 | 0.4796 (2) | −0.4570 (2) | 0.54165 (13) | 0.0267 (5) | |
| C2 | 1.0183 (2) | −0.4548 (3) | 0.45843 (12) | 0.0273 (5) | |
| C3 | 0.6379 (3) | −0.0519 (3) | 0.43339 (17) | 0.0508 (7) | |
| H3A | 0.6433 | −0.0276 | 0.4934 | 0.061* | |
| C4 | 0.5940 (4) | 0.0530 (4) | 0.37219 (19) | 0.0663 (9) | |
| H4A | 0.5703 | 0.1456 | 0.3907 | 0.080* | |
| C5 | 0.5860 (3) | 0.0183 (4) | 0.28352 (19) | 0.0618 (9) | |
| H5A | 0.5558 | 0.0865 | 0.2407 | 0.074* | |
| C6 | 0.6231 (4) | −0.1172 (4) | 0.25962 (18) | 0.0606 (9) | |
| H6A | 0.6201 | −0.1430 | 0.1999 | 0.073* | |
| C7 | 0.6655 (3) | −0.2167 (3) | 0.32437 (16) | 0.0481 (7) | |
| H7A | 0.6900 | −0.3097 | 0.3070 | 0.058* | |
| C8 | 0.9477 (3) | −0.1161 (3) | 0.58687 (16) | 0.0474 (7) | |
| H8A | 0.9903 | −0.1306 | 0.5340 | 0.057* | |
| C9 | 1.0050 (3) | −0.0147 (3) | 0.64543 (18) | 0.0575 (8) | |
| H9A | 1.0835 | 0.0391 | 0.6317 | 0.069* | |
| C10 | 0.9457 (3) | 0.0066 (3) | 0.72456 (17) | 0.0512 (7) | |
| H10A | 0.9831 | 0.0744 | 0.7656 | 0.061* | |
| C11 | 0.8304 (3) | −0.0743 (4) | 0.74121 (17) | 0.0556 (8) | |
| H11A | 0.7875 | −0.0626 | 0.7942 | 0.067* | |
| C12 | 0.7781 (3) | −0.1733 (3) | 0.67895 (16) | 0.0473 (7) | |
| H12A | 0.6995 | −0.2279 | 0.6914 | 0.057* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.02419 (15) | 0.03332 (17) | 0.03018 (15) | −0.00085 (13) | 0.00355 (10) | −0.00017 (12) |
| O1 | 0.0294 (9) | 0.0360 (10) | 0.0342 (8) | −0.0041 (8) | 0.0056 (6) | −0.0073 (7) |
| O2 | 0.0297 (9) | 0.0397 (10) | 0.0317 (7) | 0.0054 (8) | 0.0062 (6) | 0.0067 (7) |
| O3 | 0.0296 (9) | 0.0446 (11) | 0.0347 (8) | 0.0057 (8) | 0.0107 (7) | 0.0074 (7) |
| O4 | 0.0274 (9) | 0.0423 (10) | 0.0365 (8) | −0.0053 (8) | 0.0089 (7) | −0.0072 (7) |
| N1 | 0.0306 (11) | 0.0414 (13) | 0.0364 (10) | 0.0021 (10) | 0.0040 (8) | 0.0064 (9) |
| N2 | 0.0320 (11) | 0.0376 (12) | 0.0323 (9) | −0.0029 (9) | 0.0015 (8) | −0.0024 (9) |
| C1 | 0.0236 (12) | 0.0290 (13) | 0.0274 (10) | 0.0011 (10) | 0.0005 (9) | 0.0015 (9) |
| C2 | 0.0258 (12) | 0.0314 (14) | 0.0245 (10) | −0.0021 (11) | 0.0008 (9) | −0.0026 (9) |
| C3 | 0.0587 (19) | 0.0557 (19) | 0.0393 (13) | 0.0220 (16) | 0.0127 (12) | 0.0041 (13) |
| C4 | 0.081 (2) | 0.056 (2) | 0.0629 (18) | 0.0327 (19) | 0.0142 (17) | 0.0092 (16) |
| C5 | 0.066 (2) | 0.069 (2) | 0.0498 (16) | 0.0170 (18) | 0.0022 (14) | 0.0221 (16) |
| C6 | 0.075 (2) | 0.066 (2) | 0.0380 (14) | −0.0004 (18) | −0.0093 (14) | 0.0059 (14) |
| C7 | 0.0603 (18) | 0.0448 (17) | 0.0378 (13) | −0.0016 (15) | −0.0060 (12) | −0.0006 (12) |
| C8 | 0.0480 (17) | 0.0596 (19) | 0.0356 (12) | −0.0180 (14) | 0.0105 (11) | −0.0063 (12) |
| C9 | 0.0552 (19) | 0.066 (2) | 0.0514 (16) | −0.0291 (16) | 0.0068 (13) | −0.0085 (15) |
| C10 | 0.0556 (18) | 0.0557 (19) | 0.0414 (14) | −0.0129 (15) | −0.0027 (12) | −0.0137 (13) |
| C11 | 0.0555 (19) | 0.072 (2) | 0.0409 (14) | −0.0116 (17) | 0.0122 (13) | −0.0204 (14) |
| C12 | 0.0402 (15) | 0.063 (2) | 0.0397 (13) | −0.0138 (14) | 0.0107 (11) | −0.0091 (13) |
| Zn1—O1 | 2.0935 (15) | C12—C11 | 1.374 (4) |
| Zn1—O2 | 2.0987 (15) | C7—C6 | 1.377 (4) |
| Zn1—O3 | 2.1269 (16) | C10—C11 | 1.362 (4) |
| Zn1—O4 | 2.1365 (16) | C10—C9 | 1.372 (4) |
| Zn1—N2 | 2.1485 (19) | C8—C9 | 1.369 (4) |
| Zn1—N1 | 2.161 (2) | C5—C6 | 1.354 (4) |
| O2—C2 | 1.251 (3) | C5—C4 | 1.372 (4) |
| O1—C1 | 1.250 (3) | C4—C3 | 1.378 (4) |
| O4—C1i | 1.244 (3) | C3—H3A | 0.930 |
| O3—C2ii | 1.243 (3) | C4—H4A | 0.930 |
| N2—C12 | 1.334 (3) | C5—H5A | 0.930 |
| N2—C8 | 1.332 (3) | C6—H6A | 0.930 |
| C2—O3ii | 1.243 (3) | C7—H7A | 0.930 |
| C2—C2ii | 1.566 (4) | C8—H8A | 0.930 |
| C1—O4i | 1.244 (3) | C9—H9A | 0.930 |
| C1—C1i | 1.559 (4) | C10—H10A | 0.930 |
| N1—C3 | 1.324 (3) | C11—H11A | 0.930 |
| N1—C7 | 1.337 (3) | C12—H12A | 0.930 |
| O1—Zn1—O2 | 172.80 (6) | N2—C12—C11 | 123.6 (3) |
| O1—Zn1—O3 | 97.56 (6) | N1—C7—C6 | 122.8 (3) |
| O2—Zn1—O3 | 79.08 (6) | C11—C10—C9 | 118.0 (3) |
| O1—Zn1—O4 | 78.81 (6) | N2—C8—C9 | 123.4 (2) |
| O2—Zn1—O4 | 94.69 (6) | C10—C11—C12 | 119.3 (2) |
| O3—Zn1—O4 | 89.14 (7) | C6—C5—C4 | 118.6 (3) |
| O1—Zn1—N2 | 89.26 (6) | C5—C6—C7 | 119.5 (3) |
| O2—Zn1—N2 | 97.02 (7) | C8—C9—C10 | 119.4 (3) |
| O3—Zn1—N2 | 89.18 (7) | C3—C4—C5 | 118.8 (3) |
| O4—Zn1—N2 | 167.63 (6) | N1—C3—C4 | 123.4 (2) |
| O1—Zn1—N1 | 96.57 (7) | H3A—C3—N1 | 118.67 |
| O2—Zn1—N1 | 86.54 (7) | H3A—C3—C4 | 118.70 |
| O3—Zn1—N1 | 165.55 (7) | H4A—C4—C3 | 120.25 |
| O4—Zn1—N1 | 90.68 (7) | H4A—C4—C5 | 120.22 |
| N2—Zn1—N1 | 93.98 (8) | H5A—C5—C4 | 120.69 |
| C2—O2—Zn1 | 114.15 (13) | H5A—C5—C6 | 120.71 |
| C1—O1—Zn1 | 114.47 (13) | H6A—C6—C5 | 120.35 |
| C1i—O4—Zn1 | 113.00 (13) | H6A—C6—C7 | 120.35 |
| C2ii—O3—Zn1 | 113.18 (14) | H7A—C7—C6 | 118.22 |
| C12—N2—C8 | 116.4 (2) | H7A—C7—N1 | 118.28 |
| C12—N2—Zn1 | 123.04 (15) | H8A—C8—N2 | 118.38 |
| C8—N2—Zn1 | 120.56 (16) | H8A—C8—C9 | 118.39 |
| O3ii—C2—O2 | 126.43 (19) | H9A—C9—C8 | 120.51 |
| O3ii—C2—C2ii | 117.1 (2) | H9A—C9—C10 | 120.52 |
| O2—C2—C2ii | 116.5 (2) | H10A—C10—C9 | 120.59 |
| O4i—C1—O1 | 126.28 (19) | H10A—C10—C11 | 120.64 |
| O4i—C1—C1i | 117.1 (2) | H11A—C11—C10 | 120.53 |
| O1—C1—C1i | 116.6 (2) | H11A—C11—C12 | 120.57 |
| C3—N1—C7 | 117.0 (2) | H12A—C12—C11 | 118.34 |
| C3—N1—Zn1 | 124.40 (16) | H12A—C12—N2 | 118.41 |
| C7—N1—Zn1 | 118.55 (18) |
| Symmetry codes: (i) −x+1, −y−1, −z+1; (ii) −x+2, −y−1, −z+1. |
| Zn1—O1 | 2.0935 (15) | Zn1—O4 | 2.1365 (16) |
| Zn1—O2 | 2.0987 (15) | Zn1—N2 | 2.1485 (19) |
| Zn1—O3 | 2.1269 (16) | Zn1—N1 | 2.161 (2) |
| O1—Zn1—O2 | 172.80 (6) | O1—Zn1—O4 | 78.81 (6) |
| O1—Zn1—O3 | 97.56 (6) | O2—Zn1—O4 | 94.69 (6) |
| O2—Zn1—O3 | 79.08 (6) | O3—Zn1—O4 | 89.14 (7) |
The authors thank the Natural Science Foundation of China for financially supporting this work (grant No. 20671015).
Bruker (2001). SAINT-Plus (Version 6.45) and SMART (Version 5.628). Bruker AXS Inc., Madison, Wisconsin, USA.
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Synthesis of metal organic framework (MOF) structures by the modular approach is an area of intense research activity as potential zeolitic, optoelectronic, magnetic, and conducting materials(Chui et al., 1999; Kiang et al., 1999; Kahn & Martinez, 1998; Lin et al., 1999). While most of these products have been generated utilizing hydro(solvo)thermal techniques, it is often not possible to predict the structures of them with confidence (Evans & Lin, 2001; Ghosh et al., 2004). In this paper, we report our unexpected discovery of the synthesis of a new zinc oxalate coordination polymers by facile oxidation of pentaerythritol acid to oxalic acid under hydro(solvo)thermal conditions.
The structure of the compound consists of infinite one-dimensional zigzag chains where each metal ion is coordinated to two oxalate groups and two pyridine molecules showing hexacoordination with O4N2 donor set (Fig. 1). Coordination geometry around each metal center can be described as slightly distorted octahedral. The two pyridine molecules are similarly oriented with respect to the Zn-oxalate backbone. These infinite zigzag chains pack in the lattice through interdigitization involving the pyridine molecules (Fig. 2)·The Zn—O distances range from 2.0935 (15) Å to 2.1365 (16) Å, while the O—Zn—O angles between 78.81 (6)° and 172.80 (6) (Table 1).