Acta Cryst. (2008). E64, m1635 [ doi:10.1107/S1600536808039585 ]
The title complex, [Zn(C2H3O3)2(H2O)2], was prepared and the crystal structure determined as part of a 67Zn solid state nuclear magnetic resonance study. In the title complex, the Zn atom has a disorted octahedral coordination comprising two bidentate glycolate ligands and two water molecules. The water molecules are cis to each other; one is trans to a carboxylate O atom and the other trans to an alcohol O atom. The crystal structure has an extensive O-H
O hydrogen-bond network.
Glycolic acid (100 mg, 3 mmol), purchased from Sigma-Aldrich (99%), was dissolved in 5 ml of deionized water. Basic zinc carbonate (80 mg, 2 mmol) was added and the mixture stirred for 10 minutes while heating to ca. 60°C. The resulting mixture was filtered, and the filtrate left to stand at room temperature until large needle-like crystals grew by slow evaporation of the water.
The alcohol and water H-atoms were placed at the locations identified in a difference Fourier map and were held fixed, with Uiso(H) set to 0.05 A2: O-H = 0.8293 - 0.9135 Å. The C-bound H-atoms were included in calculated positions and treated as riding atoms: C-H = 0.97 Å with Uiso(H) = 1.2Ueq(parent C-atom).
Data collection: XSCANS (Bruker, 2000); cell refinement: XSCANS (Bruker, 2000); data reduction: XSCANS (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./su2079fig1thm.gif)
| Fig. 1. A view of the molecular structure of compound (I), showing the atom numbering scheme and dispacement ellipsods drawn at the 50% probability level. |
| [Zn(C2H3O3)2(H2O)2] | F(000) = 512 |
| Mr = 251.49 | Dx = 2.002 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 20 reflections |
| a = 11.391 (2) Å | θ = 9.6–17.4° |
| b = 5.857 (1) Å | µ = 2.96 mm−1 |
| c = 12.511 (2) Å | T = 273 K |
| β = 91.198 (9)° | Needle, colorless |
| V = 834.5 (2) Å3 | 0.3 × 0.3 × 0.1 mm |
| Z = 4 |
| Bruker P4 diffractometer | 1751 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.0000 |
| graphite | θmax = 28.5°, θmin = 3.3° |
| 2θ/ω scans | h = −15→15 |
| Absorption correction: ψ scan (SADABS; Bruker, 2000) | k = 0→7 |
| Tmin = 0.425, Tmax = 0.744 | l = 0→16 |
| 2102 measured reflections | 3 standard reflections every 97 reflections |
| 2102 independent reflections | intensity decay: none |
| 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) = 0.072 | w = 1/[σ2(Fo2) + (0.0337P)2 + 0.5879P] where P = (Fo2 + 2Fc2)/3 |
| S = 0.99 | (Δ/σ)max = 0.030 |
| 2102 reflections | Δρmax = 0.45 e Å−3 |
| 119 parameters | Δρmin = −0.50 e Å−3 |
| 0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0094 (8) |
| [Zn(C2H3O3)2(H2O)2] | V = 834.5 (2) Å3 |
| Mr = 251.49 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.391 (2) Å | µ = 2.96 mm−1 |
| b = 5.857 (1) Å | T = 273 K |
| c = 12.511 (2) Å | 0.3 × 0.3 × 0.1 mm |
| β = 91.198 (9)° |
| Bruker P4 diffractometer | 1751 reflections with I > 2σ(I) |
| Absorption correction: ψ scan (SADABS; Bruker, 2000) | Rint = 0.0000 |
| Tmin = 0.425, Tmax = 0.744 | θmax = 28.5° |
| 2102 measured reflections | 3 standard reflections every 97 reflections |
| 2102 independent reflections | intensity decay: none |
| R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
| wR(F2) = 0.072 | Δρmax = 0.45 e Å−3 |
| S = 0.99 | Δρmin = −0.50 e Å−3 |
| 2102 reflections | Absolute structure: ? |
| 119 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| Zn | 0.76227 (2) | 0.14144 (5) | 0.65837 (2) | 0.02431 (11) | |
| O1 | 0.73409 (15) | 0.0926 (3) | 0.82160 (13) | 0.0323 (4) | |
| O2 | 0.91409 (16) | 0.3091 (3) | 0.69490 (15) | 0.0349 (4) | |
| O3 | 0.82248 (17) | −0.1945 (3) | 0.64048 (13) | 0.0307 (4) | |
| O4 | 0.80776 (17) | 0.1349 (3) | 0.49645 (13) | 0.0310 (4) | |
| O5 | 0.90455 (17) | −0.0608 (4) | 0.37503 (13) | 0.0367 (4) | |
| O6 | 0.58388 (16) | 0.0302 (3) | 0.63177 (15) | 0.0339 (4) | |
| O7 | 0.66840 (15) | 0.4419 (3) | 0.64627 (14) | 0.0299 (4) | |
| O8 | 0.49499 (15) | 0.6096 (3) | 0.62300 (13) | 0.0275 (4) | |
| C1 | 0.8665 (2) | −0.2479 (4) | 0.53732 (19) | 0.0297 (5) | |
| H1A | 0.8215 | −0.3727 | 0.5062 | 0.036* | |
| H1B | 0.9477 | −0.2968 | 0.5444 | 0.036* | |
| C2 | 0.8588 (2) | −0.0423 (4) | 0.46432 (18) | 0.0242 (5) | |
| C3 | 0.4989 (2) | 0.2052 (4) | 0.62244 (18) | 0.0242 (5) | |
| H2A | 0.4422 | 0.1896 | 0.6787 | 0.029* | |
| H2B | 0.4575 | 0.1927 | 0.5542 | 0.029* | |
| C4 | 0.5587 (2) | 0.4364 (4) | 0.63092 (16) | 0.0218 (4) | |
| H3 | 0.7697 | −0.2865 | 0.6547 | 0.050* | |
| H4 | 0.5587 | −0.1048 | 0.6293 | 0.050* | |
| H5 | 0.9803 | 0.2654 | 0.6719 | 0.050* | |
| H6 | 0.9284 | 0.3898 | 0.7563 | 0.050* | |
| H7 | 0.6612 | 0.0892 | 0.8427 | 0.050* | |
| H8 | 0.7688 | 0.1759 | 0.8742 | 0.050* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn | 0.02730 (16) | 0.01890 (15) | 0.02686 (15) | 0.00221 (12) | 0.00378 (10) | −0.00151 (11) |
| O1 | 0.0314 (9) | 0.0381 (10) | 0.0275 (8) | −0.0050 (8) | 0.0044 (7) | −0.0032 (7) |
| O2 | 0.0280 (9) | 0.0360 (10) | 0.0408 (10) | −0.0002 (8) | 0.0038 (7) | −0.0114 (8) |
| O3 | 0.0452 (10) | 0.0204 (8) | 0.0269 (8) | 0.0026 (8) | 0.0121 (7) | 0.0011 (7) |
| O4 | 0.0404 (10) | 0.0270 (9) | 0.0260 (8) | 0.0094 (8) | 0.0063 (7) | 0.0037 (7) |
| O5 | 0.0435 (11) | 0.0390 (11) | 0.0280 (9) | 0.0100 (9) | 0.0116 (8) | 0.0036 (8) |
| O6 | 0.0327 (10) | 0.0161 (8) | 0.0527 (11) | 0.0002 (8) | −0.0013 (8) | −0.0041 (8) |
| O7 | 0.0268 (9) | 0.0174 (8) | 0.0457 (10) | 0.0012 (7) | 0.0026 (7) | −0.0014 (8) |
| O8 | 0.0294 (9) | 0.0198 (8) | 0.0333 (9) | 0.0036 (7) | 0.0046 (7) | 0.0029 (7) |
| C1 | 0.0414 (14) | 0.0203 (11) | 0.0277 (12) | 0.0026 (11) | 0.0100 (10) | −0.0006 (10) |
| C2 | 0.0216 (11) | 0.0255 (12) | 0.0257 (11) | −0.0017 (10) | 0.0017 (8) | 0.0014 (9) |
| C3 | 0.0294 (12) | 0.0196 (10) | 0.0238 (10) | −0.0008 (10) | −0.0008 (9) | −0.0002 (9) |
| C4 | 0.0284 (11) | 0.0185 (10) | 0.0188 (9) | −0.0011 (9) | 0.0049 (8) | 0.0010 (8) |
| Zn—O2 | 2.0325 (19) | O4—C2 | 1.259 (3) |
| Zn—O7 | 2.0630 (17) | O5—C2 | 1.247 (3) |
| Zn—O1 | 2.0935 (17) | O6—C3 | 1.412 (3) |
| Zn—O3 | 2.0974 (18) | O6—H4 | 0.8417 |
| Zn—O4 | 2.1019 (17) | O7—C4 | 1.261 (3) |
| Zn—O6 | 2.1531 (19) | O8—C4 | 1.250 (3) |
| O1—H7 | 0.8768 | C1—C2 | 1.513 (3) |
| O1—H8 | 0.9037 | C1—H1A | 0.9700 |
| O2—H5 | 0.8522 | C1—H1B | 0.9700 |
| O2—H6 | 0.9135 | C3—C4 | 1.518 (3) |
| O3—C1 | 1.429 (3) | C3—H2A | 0.9700 |
| O3—H3 | 0.8293 | C3—H2B | 0.9700 |
| O2—Zn—O7 | 92.38 (7) | C2—O4—Zn | 116.58 (15) |
| O2—Zn—O1 | 89.65 (7) | C3—O6—Zn | 115.85 (14) |
| O7—Zn—O1 | 95.65 (7) | C3—O6—H4 | 116.5 |
| O2—Zn—O3 | 101.47 (8) | Zn—O6—H4 | 127.6 |
| O7—Zn—O3 | 164.27 (7) | C4—O7—Zn | 120.00 (16) |
| O1—Zn—O3 | 91.89 (7) | O3—C1—C2 | 110.72 (19) |
| O2—Zn—O4 | 89.99 (7) | O3—C1—H1A | 109.5 |
| O7—Zn—O4 | 94.74 (7) | C2—C1—H1A | 109.5 |
| O1—Zn—O4 | 169.61 (7) | O3—C1—H1B | 109.5 |
| O3—Zn—O4 | 78.01 (7) | C2—C1—H1B | 109.5 |
| O2—Zn—O6 | 167.62 (7) | H1A—C1—H1B | 108.1 |
| O7—Zn—O6 | 76.15 (7) | O5—C2—O4 | 124.2 (2) |
| O1—Zn—O6 | 86.90 (7) | O5—C2—C1 | 116.8 (2) |
| O3—Zn—O6 | 90.53 (7) | O4—C2—C1 | 119.00 (19) |
| O4—Zn—O6 | 95.53 (7) | O6—C3—C4 | 109.64 (19) |
| Zn—O1—H7 | 117.5 | O6—C3—H2A | 109.7 |
| Zn—O1—H8 | 124.3 | C4—C3—H2A | 109.7 |
| H7—O1—H8 | 101.3 | O6—C3—H2B | 109.7 |
| Zn—O2—H5 | 122.2 | C4—C3—H2B | 109.7 |
| Zn—O2—H6 | 125.1 | H2A—C3—H2B | 108.2 |
| H5—O2—H6 | 107.2 | O8—C4—O7 | 124.3 (2) |
| C1—O3—Zn | 115.05 (14) | O8—C4—C3 | 117.4 (2) |
| C1—O3—H3 | 108.8 | O7—C4—C3 | 118.3 (2) |
| Zn—O3—H3 | 110.3 | ||
| O2—Zn—O3—C1 | −84.29 (19) | O2—Zn—O7—C4 | −174.79 (18) |
| O7—Zn—O3—C1 | 67.0 (3) | O1—Zn—O7—C4 | −84.91 (18) |
| O1—Zn—O3—C1 | −174.31 (18) | O3—Zn—O7—C4 | 33.4 (4) |
| O4—Zn—O3—C1 | 3.24 (18) | O4—Zn—O7—C4 | 95.01 (18) |
| O6—Zn—O3—C1 | 98.77 (18) | O6—Zn—O7—C4 | 0.47 (17) |
| O2—Zn—O4—C2 | 94.74 (19) | Zn—O3—C1—C2 | 0.1 (3) |
| O7—Zn—O4—C2 | −172.86 (19) | Zn—O4—C2—O5 | −170.4 (2) |
| O1—Zn—O4—C2 | 6.7 (5) | Zn—O4—C2—C1 | 9.4 (3) |
| O3—Zn—O4—C2 | −6.98 (18) | O3—C1—C2—O5 | 173.5 (2) |
| O6—Zn—O4—C2 | −96.36 (19) | O3—C1—C2—O4 | −6.3 (3) |
| O2—Zn—O6—C3 | 21.4 (5) | Zn—O6—C3—C4 | 1.6 (2) |
| O7—Zn—O6—C3 | −1.22 (16) | Zn—O7—C4—O8 | 179.73 (17) |
| O1—Zn—O6—C3 | 95.41 (17) | Zn—O7—C4—C3 | 0.3 (3) |
| O3—Zn—O6—C3 | −172.75 (16) | O6—C3—C4—O8 | 179.2 (2) |
| O4—Zn—O6—C3 | −94.73 (17) | O6—C3—C4—O7 | −1.3 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H8···O4i | 0.90 | 1.93 | 2.821 (3) | 167 |
| O1—H7···O8ii | 0.88 | 1.84 | 2.716 (3) | 174 |
| O2—H6···O5i | 0.91 | 1.82 | 2.697 (3) | 161 |
| O2—H5···O5iii | 0.85 | 1.88 | 2.688 (3) | 158 |
| O6—H4···O8iv | 0.84 | 1.82 | 2.665 (2) | 177 |
| O3—H3···O7iv | 0.83 | 1.97 | 2.761 (3) | 160 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+2, −y, −z+1; (iv) x, y−1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H8···O4i | 0.90 | 1.93 | 2.821 (3) | 167 |
| O1—H7···O8ii | 0.88 | 1.84 | 2.716 (3) | 174 |
| O2—H6···O5i | 0.91 | 1.82 | 2.697 (3) | 161 |
| O2—H5···O5iii | 0.85 | 1.88 | 2.688 (3) | 158 |
| O6—H4···O8iv | 0.84 | 1.82 | 2.665 (2) | 177 |
| O3—H3···O7iv | 0.83 | 1.97 | 2.761 (3) | 160 |
| Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, y−1/2, −z+3/2; (iii) −x+2, −y, −z+1; (iv) x, y−1, z. |
The authors thank the Research Corporation (CC6447) for financial support and the National Science Foundation for grant No. ILI8951058.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Bruker (2000). XSCANS and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Fischinger, A. J. & Webb, L. E. (1969). Chem. Commun. pp. 407–408.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
As part of a Zinc-67 solid state nuclear magnetic resonance study the title complex, (I), was prepared and the crystal structure determined. The structure of this complex was first report by Fischinger & Webb (1969) but no fractional crystal coordinates were reported.
The molecular structure of (I) is illustrated in Fig. 1. The zinc atom has a distorted octahedral coordination sphere composed of two bidentate gylcolato ligands and two water molecules. The water molecules are cis to each other; one (O1) is trans to a carboxylate O-atom (O4), and the other, (O2), is trans to an alcohol O-atom (O6). The bond distances and angles are normal for zinc(II) complexes (Allen et al., 1987)
In the crystal structure of (I) there in an extensive O—H···O hydrogen bonding network (Table 1). The two water molecules (O1 and O2) bond to the two oxygens (O4 and O5) of a carboxylate group related by the c-glide. The two alcohol groups (O3 and O6) form hydrogen bonds with the other carboxylate group (atoms O7 and O8) translated by one unit cell along the b axis. The carbonyl oxygen O8 of this ligand also makes a two dimensional hydrogen bonded network with one of the waters (O1) around the inversion center. The other water molecule, (O2), forms an H-bond with a carbonyl oxygen (O5) related by the 2-fold screw axis.