Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807036616/bm3031sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807036616/bm3031Isup2.hkl |
CCDC reference: 657642
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.
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.
For general background see: Amendola et al. (2006); Yang et al. (2000); Xu et al. (2006); Evans et al. (2006).
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).
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 |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.28 e Å−3 |
1221 reflections | Δρmin = −0.34 e Å−3 |
61 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. |
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 code: (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. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C2H3O2)2(C2H8N2)] |
Mr | 243.56 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 295 |
a, b, c (Å) | 12.1335 (4), 7.7866 (2), 10.4078 (3) |
V (Å3) | 983.32 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.48 |
Crystal size (mm) | 0.12 × 0.12 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.745, 0.758 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5391, 1221, 867 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.067, 0.99 |
No. of reflections | 1221 |
No. of parameters | 61 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.34 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
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 code: (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. |
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.