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In the title compound, [Zn(C
2H
3O
2)
2(C
2H
8N
2)], the Zn
II 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—H
O hydrogen bonding links the molecules into a three-dimensional network.
Supporting information
CCDC reference: 657642
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.003 Å
- R factor = 0.026
- wR factor = 0.067
- Data-to-parameter ratio = 20.0
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O5
Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 1.87
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
1 ALERT level C = Check and explain
1 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
1 ALERT type 5 Informative message, check
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.
Structure description
top
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).
Diacetato(ethylenediamine)zinc(II)
top
Crystal data top
[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 |
Data collection top
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 top
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 | |
Crystal data top
[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 |
Data collection top
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 | |
Refinement top
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 | |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | 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* | |
Atomic displacement parameters (Å2) top | 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) |
Geometric parameters (Å, º) top
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. |
Hydrogen-bond geometry (Å, º) top
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 |
Selected geometric parameters (Å, º) topZn1—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. |
Hydrogen-bond geometry (Å, º) top
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. |
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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.