Acta Cryst. (2007). E63, m2239-m2240 [ doi:10.1107/S1600536807036616 ]
In the title compound, [Zn(C2H3O2)2(C2H8N2)], the ZnII atom is coordinated by two N atoms of one bidentate ethylenediamine ligand and two O atoms of two acetate anions in a distorted tetrahedral geometry. The compound displays [4+2] coordination, the `4' representing the distorted tetrahedral coordination, while the `2' refers to the two much longer Zn
O(uncoordinated) distances of 2.594 (2) Å. The asymmetry of the acetate coordination is reflected in the different C-O distances of 1.229 (2) and 1.280 (2) Å. The Zn atom lies on a crystallographic twofold rotation axis. The dihedral angles between the N/Zn/N' plane and the two O/Zn/O' planes are 85.54 (7) and 29.96 (7)°, where the prime denotes the atom related by operation of the twofold axis. N-HO hydrogen bonding links the molecules into a three-dimensional network.
A solution of zinc acetate (2.195 g, 10.0 mmol) and ethylenediamine (0.601 g, 10.0 mmol) in absolute ethanol (50 ml) was stirred for 8 hrs at room temperature under a nitrogen atmosphere. The resulting colorless solution was allowed to stand at room temperature for two weeks to produce colorless crystals (yield 65.0%) suitable for X-ray diffraction.
Apart from those of sp2-bound methyl groups, which were located in ΔF syntheses, H atoms were positioned geometrically. Thereafter they were constrained to ride on their carrier atoms, with N—H = 0.90 Å and Uiso(H) = 1.2Uiso(N) for NH2, C—H = 0.97 Å and Uiso(H) = 1.2Uiso(C) for CH2, and C—H = 0.96 Å and Uiso(H) = 1.5Uiso(C) for CH3 groups.
Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./bm3031fig1thm.gif)
| Fig. 1. Molecular structure of (I), showing the atom-numbering scheme and 30% probability ellipsoids. |
| [Zn(C2H3O2)2(C2H8N2)] | F(000) = 504 |
| Mr = 243.56 | Dx = 1.645 Mg m−3 |
| Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2n 2ab | Cell parameters from 1923 reflections |
| a = 12.1335 (4) Å | θ = 3.1–26.9° |
| b = 7.7866 (2) Å | µ = 2.48 mm−1 |
| c = 10.4078 (3) Å | T = 295 K |
| V = 983.32 (5) Å3 | Block, colourless |
| Z = 4 | 0.12 × 0.12 × 0.11 mm |
| Bruker SMART CCD area-detector diffractometer | 867 reflections with I > 2σ(I) |
| φ and ω scans | Rint = 0.028 |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | θmax = 28.3°, θmin = 3.1° |
| Tmin = 0.745, Tmax = 0.758 | h = −16→11 |
| 5391 measured reflections | k = −7→10 |
| 1221 independent reflections | l = −9→13 |
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.03P)2 + 0.232P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.067 | (Δ/σ)max < 0.001 |
| S = 0.99 | Δρmax = 0.28 e Å−3 |
| 1221 reflections | Δρmin = −0.34 e Å−3 |
| 61 parameters |
| [Zn(C2H3O2)2(C2H8N2)] | V = 983.32 (5) Å3 |
| Mr = 243.56 | Z = 4 |
| Orthorhombic, Pbcn | Mo Kα radiation |
| a = 12.1335 (4) Å | µ = 2.48 mm−1 |
| b = 7.7866 (2) Å | T = 295 K |
| c = 10.4078 (3) Å | 0.12 × 0.12 × 0.11 mm |
| Bruker SMART CCD area-detector diffractometer | 1221 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 867 reflections with I > 2σ(I) |
| Tmin = 0.745, Tmax = 0.758 | Rint = 0.028 |
| 5391 measured reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
| wR(F2) = 0.067 | Δρmax = 0.28 e Å−3 |
| S = 0.99 | Δρmin = −0.34 e Å−3 |
| 1221 reflections | Absolute structure: ? |
| 61 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. |
| x | y | z | Uiso*/Ueq | ||
| Zn1 | 0.5 | 0.61106 (4) | 0.75 | 0.03233 (13) | |
| N1 | 0.39968 (13) | 0.4143 (2) | 0.68272 (16) | 0.0361 (4) | |
| H1A | 0.3286 | 0.4352 | 0.7017 | 0.043* | |
| H1B | 0.4064 | 0.4028 | 0.597 | 0.043* | |
| C2 | 0.43883 (19) | 0.2582 (3) | 0.7493 (2) | 0.0531 (7) | |
| H2A | 0.412 | 0.1568 | 0.7051 | 0.064* | |
| H2B | 0.4109 | 0.2562 | 0.8366 | 0.064* | |
| O3 | 0.56408 (11) | 0.71701 (18) | 0.59300 (13) | 0.0405 (4) | |
| C4 | 0.63853 (17) | 0.8189 (3) | 0.6350 (2) | 0.0364 (5) | |
| O5 | 0.66115 (15) | 0.8299 (2) | 0.74983 (13) | 0.0513 (4) | |
| C6 | 0.6980 (2) | 0.9260 (3) | 0.5362 (2) | 0.0526 (6) | |
| H6A | 0.7507 | 0.9984 | 0.5783 | 0.079* | |
| H6B | 0.6453 | 0.9962 | 0.4912 | 0.079* | |
| H6C | 0.7348 | 0.8523 | 0.4763 | 0.079* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.0364 (2) | 0.0318 (2) | 0.02885 (18) | 0 | 0.00367 (14) | 0 |
| N1 | 0.0369 (10) | 0.0397 (11) | 0.0316 (9) | −0.0031 (8) | −0.0019 (8) | 0.0034 (7) |
| C2 | 0.0726 (17) | 0.0370 (13) | 0.0495 (13) | −0.0147 (12) | −0.0162 (14) | 0.0061 (11) |
| O3 | 0.0420 (9) | 0.0408 (9) | 0.0386 (8) | −0.0132 (7) | 0.0047 (7) | 0.0014 (6) |
| C4 | 0.0424 (13) | 0.0280 (11) | 0.0386 (11) | 0.0004 (10) | 0.0077 (10) | −0.0027 (9) |
| O5 | 0.0634 (11) | 0.0538 (10) | 0.0367 (8) | −0.0129 (9) | 0.0037 (7) | −0.0030 (8) |
| C6 | 0.0665 (16) | 0.0486 (14) | 0.0427 (12) | −0.0260 (13) | 0.0051 (12) | 0.0027 (11) |
| Zn1—N1 | 2.0784 (16) | C2—H2B | 0.97 |
| Zn1—O3 | 1.9887 (13) | O3—C4 | 1.280 (2) |
| N1—C2 | 1.477 (3) | C4—O5 | 1.229 (2) |
| N1—H1A | 0.90 | C4—C6 | 1.508 (3) |
| N1—H1B | 0.90 | C6—H6A | 0.96 |
| C2—C2i | 1.485 (5) | C6—H6B | 0.96 |
| C2—H2A | 0.97 | C6—H6C | 0.96 |
| N1—Zn1—N1i | 85.01 (9) | C2i—C2—H2B | 109.9 |
| N1—Zn1—O3 | 104.95 (6) | H2A—C2—H2B | 108.3 |
| N1i—Zn1—O3 | 110.71 (6) | C4—O3—Zn1 | 104.61 (12) |
| C2—N1—Zn1 | 105.09 (12) | O5—C4—O3 | 122.23 (19) |
| C2—N1—H1A | 110.7 | O5—C4—C6 | 121.2 (2) |
| Zn1—N1—H1A | 110.7 | O3—C4—C6 | 116.56 (18) |
| C2—N1—H1B | 110.7 | C4—C6—H6A | 109.5 |
| Zn1—N1—H1B | 110.7 | C4—C6—H6B | 109.5 |
| H1A—N1—H1B | 108.8 | H6A—C6—H6B | 109.5 |
| N1—C2—C2i | 109.05 (16) | C4—C6—H6C | 109.5 |
| N1—C2—H2A | 109.9 | H6A—C6—H6C | 109.5 |
| C2i—C2—H2A | 109.9 | H6B—C6—H6C | 109.5 |
| N1—C2—H2B | 109.9 |
| Symmetry codes: (i) −x+1, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1B···O3ii | 0.90 | 2.22 | 3.078 (2) | 160 |
| N1—H1A···O5iii | 0.90 | 2.25 | 3.050 (2) | 148 |
| Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x−1/2, y−1/2, −z+3/2. |
| Zn1—N1 | 2.0784 (16) | O3—C4 | 1.280 (2) |
| Zn1—O3 | 1.9887 (13) | C4—O5 | 1.229 (2) |
| N1—C2 | 1.477 (3) | ||
| N1—Zn1—N1i | 85.01 (9) | N1i—Zn1—O3 | 110.71 (6) |
| N1—Zn1—O3 | 104.95 (6) |
| Symmetry codes: (i) −x+1, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1B···O3ii | 0.90 | 2.22 | 3.078 (2) | 160 |
| N1—H1A···O5iii | 0.90 | 2.25 | 3.050 (2) | 148 |
| Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x−1/2, y−1/2, −z+3/2. |
This work was supported by a grant from the Ministry of Commerce, Industry and Energy, and the Korea Industrial Technology Foundaton. X-ray data were collected at the Center for Research Facilities at Chungnam National University.
Amendola, V., Fabbrizzi, L., Foti, F., Licchelli, M., Mangano, C., Pallavicini, P., Poggi, A., Sacchi, D. & Taglietti, A. (2006). Coord. Chem. Rev. 250, 273–299.
Bruker (2002). SADABS (Version 2.03), SAINT (Version 6.02) and SMART (Version 5.62). Bruker AXS Inc., Madison, Wisconsin, USA.
Evans, R. C., Douglas, P. & Winscom, C. J. (2006). Coord. Chem. Rev. 250, 2093–2126.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.
Sheldrick, G. M. (2002). SADABS. University of Göttingen, Germany.
Xu, Y., Chen, B., Gong, Y., Yuan, D., Jiang, F. & Hong, M. (2006). J. Mol. Struct. 789, 220–224.
Yang, W., Schmider, H., Wu, Q., Zhang, Y.-S. & Wang, S. (2000). Inorg. Chem. 39, 2397–2404.
Luminescent coordination compounds have been investigated extensively due to their various potential applications in material sciences (Amendola et al. 2006). Many Zn(II) complexes are known to exhibit an intense fluorescence at room temperature (Yang, et al. 2000; Xu, et al. 2006), and they are proposed as candidates for the fluorescent based organic light-emitting diods (OLED) devices (Evans, et al. 2006). The title compound displays distorted tetrahedral coordination, with two N atoms from ethylenediamine and two O atoms from two acetate ligands. The title compound displays [4 + 2] coordination: the "4" represnets the distorted tetrahedral coordination, while the "2" means the two much longer Zn1—O5 distances of 2.594 (2) Å. The asymmetry of the acetate coordination is reflected in the different C—O distances of 1.229 (2) and 1.280 (2) Å. The Zn1 lies on a crystallographic twofold axis. The dihedral angle between N1—Zn1—N1' and O3—Zn1—O3' planes is 85.54 (7) °, where the prime denotes the symetry operation about the twofold axis. While the dihedral angle between N1—Zn1—N1' and O5—Zn1—O5' planes is 29.96 (7) °. N—H···O hydrogen bonding links molecules into a three-dimensional network. The title compound exhibits an intense blue emission at 444 nm in CHCl3 upon 368 nm excitation.