Acta Cryst. (2009). E65, m1522 [ doi:10.1107/S1600536809045693 ]
The title compound, [Zn(C2H8N2)3](SiF6), was synthesized ionothermally using choline chloride-imidazolidone as solvent and template provider. In the crystal structure, the anions and cations are located on special positions of site symmetry 3.2 and show a typical octahedral geometry. The ZnII ion is coordinated by six N atoms from three ethylenediamine molecules. The crystal structure displays weak hydrogen bonding between [SiF6]2- anions and the ethylenediamine NH hydrogen atoms.
A typical synthetic procedure for Zn(C2N2H8)3.SiF6 was as follows: a Teflon-lined autoclave (volume 15 ml) was charged with the ionic liquid [composed of choline chloride (1630 mg, 11.4 mmol) and imidazolidone (2.045 g, 22.8 mmol)], zinc acetate (168 mg, 0.74 mmol), NH4F (71 mg, 1.85 mmol), and silica (49 mg, 0.74 mmol) and heated in an oven at 180 °C for 3 days. Ethylenediamine(C2N2H8), derived from decomposition of the imidazolidone component of the deep-eutectic solvent (DES) itself, is delivered to the synthesis. The synthesized samples were washed with distilled water in an ultrasonic bath, then washed with acetone, and dried at room temperature in air. The colorless crystals of the title salt were abtained with suitable size for single-crystal X-ray analysis.
All H atoms were fixed geometrically (C—H = 0.99 Å, N—H = 0.92 Å) and treated as riding with Uiso(H) = 1.2Ueq of the parent atom.
Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear (Rigaku, 2004); data reduction: CrystalClear (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bt5123fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. |
| [Zn(C2H8N2)3](SiF6) | Dx = 1.804 Mg m−3 |
| Mr = 387.77 | Mo Kα radiation, λ = 0.71073 Å |
| Trigonal, P6322 | Cell parameters from 1402 reflections |
| Hall symbol: P 6c 2c | θ = 6.6–54.6° |
| a = 9.192 (2) Å | µ = 1.87 mm−1 |
| c = 9.755 (3) Å | T = 93 K |
| V = 713.8 (3) Å3 | Prism, colorless |
| Z = 2 | 0.10 × 0.10 × 0.10 mm |
| F(000) = 400 |
| Rigaku Mercury CCD diffractometer | 534 independent reflections |
| Radiation source: rotating anode | 499 reflections with I > 2σ(I) |
| confocal | Rint = 0.045 |
| Detector resolution: 0.83 pixels mm-1 | θmax = 27.4°, θmin = 3.3° |
| ω scans | h = −10→11 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2004) | k = −10→11 |
| Tmin = 0.835, Tmax = 0.835 | l = −11→9 |
| 4809 measured reflections |
| 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)] = 0.027 | H-atom parameters constrained |
| wR(F2) = 0.059 | w = 1/[σ2(Fo2) + (0.0158P)2 + 0.5912P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.11 | (Δ/σ)max < 0.001 |
| 534 reflections | Δρmax = 0.51 e Å−3 |
| 32 parameters | Δρmin = −0.38 e Å−3 |
| 0 restraints | Absolute structure: Flack (1983), 177 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.01 (3) |
| [Zn(C2H8N2)3](SiF6) | Z = 2 |
| Mr = 387.77 | Mo Kα radiation |
| Trigonal, P6322 | µ = 1.87 mm−1 |
| a = 9.192 (2) Å | T = 93 K |
| c = 9.755 (3) Å | 0.10 × 0.10 × 0.10 mm |
| V = 713.8 (3) Å3 |
| Rigaku Mercury CCD diffractometer | 534 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2004) | 499 reflections with I > 2σ(I) |
| Tmin = 0.835, Tmax = 0.835 | Rint = 0.045 |
| 4809 measured reflections | θmax = 27.4° |
| R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
| wR(F2) = 0.059 | Δρmax = 0.51 e Å−3 |
| S = 1.11 | Δρmin = −0.38 e Å−3 |
| 534 reflections | Absolute structure: Flack (1983), 177 Friedel pairs |
| 32 parameters | Flack parameter: 0.01 (3) |
| 0 restraints |
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 | ||
| Si1 | 0.3333 | 0.6667 | 0.7500 | 0.0135 (3) | |
| F1 | 0.48288 (18) | 0.6657 (2) | 0.85081 (14) | 0.0250 (3) | |
| Zn1 | 0.6667 | 0.3333 | 0.7500 | 0.01508 (18) | |
| N1 | 0.8544 (2) | 0.5434 (2) | 0.87149 (19) | 0.0191 (4) | |
| H1A | 0.8277 | 0.5243 | 0.9631 | 0.023* | |
| H1B | 0.9584 | 0.5539 | 0.8589 | 0.023* | |
| C1 | 0.8584 (4) | 0.6997 (3) | 0.8277 (2) | 0.0222 (5) | |
| H2A | 0.9655 | 0.7986 | 0.8566 | 0.027* | |
| H2B | 0.7651 | 0.7070 | 0.8716 | 0.027* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Si1 | 0.0151 (4) | 0.0151 (4) | 0.0102 (7) | 0.0076 (2) | 0.000 | 0.000 |
| F1 | 0.0260 (7) | 0.0352 (8) | 0.0183 (7) | 0.0186 (7) | −0.0057 (6) | −0.0011 (7) |
| Zn1 | 0.0169 (2) | 0.0169 (2) | 0.0115 (3) | 0.00843 (11) | 0.000 | 0.000 |
| N1 | 0.0185 (10) | 0.0240 (11) | 0.0137 (11) | 0.0097 (9) | −0.0018 (8) | 0.0003 (8) |
| C1 | 0.0234 (13) | 0.0195 (11) | 0.0225 (12) | 0.0099 (13) | −0.0031 (12) | −0.0037 (8) |
| Si1—F1i | 1.6938 (13) | Zn1—N1v | 2.186 (2) |
| Si1—F1ii | 1.6938 (13) | Zn1—N1viii | 2.1863 (19) |
| Si1—F1iii | 1.6938 (14) | Zn1—N1ix | 2.1863 (19) |
| Si1—F1iv | 1.6938 (14) | N1—C1 | 1.482 (3) |
| Si1—F1 | 1.6938 (13) | N1—H1A | 0.9200 |
| Si1—F1v | 1.6938 (13) | N1—H1B | 0.9200 |
| Zn1—N1vi | 2.1863 (19) | C1—C1viii | 1.523 (4) |
| Zn1—N1vii | 2.1863 (19) | C1—H2A | 0.9900 |
| Zn1—N1 | 2.186 (2) | C1—H2B | 0.9900 |
| F1i—Si1—F1ii | 90.69 (10) | N1vi—Zn1—N1viii | 93.40 (7) |
| F1i—Si1—F1iii | 89.68 (7) | N1vii—Zn1—N1viii | 170.67 (11) |
| F1ii—Si1—F1iii | 89.95 (10) | N1—Zn1—N1viii | 80.19 (10) |
| F1i—Si1—F1iv | 89.95 (10) | N1v—Zn1—N1viii | 93.40 (7) |
| F1ii—Si1—F1iv | 89.68 (7) | N1vi—Zn1—N1ix | 170.67 (11) |
| F1iii—Si1—F1iv | 179.47 (11) | N1vii—Zn1—N1ix | 93.40 (7) |
| F1i—Si1—F1 | 179.47 (11) | N1—Zn1—N1ix | 93.40 (7) |
| F1ii—Si1—F1 | 89.68 (7) | N1v—Zn1—N1ix | 80.19 (10) |
| F1iii—Si1—F1 | 90.69 (10) | N1viii—Zn1—N1ix | 93.74 (11) |
| F1iv—Si1—F1 | 89.68 (7) | C1—N1—Zn1 | 109.01 (14) |
| F1i—Si1—F1v | 89.68 (7) | C1—N1—H1A | 109.9 |
| F1ii—Si1—F1v | 179.47 (11) | Zn1—N1—H1A | 109.9 |
| F1iii—Si1—F1v | 89.68 (7) | C1—N1—H1B | 109.9 |
| F1iv—Si1—F1v | 90.69 (10) | Zn1—N1—H1B | 109.9 |
| F1—Si1—F1v | 89.95 (10) | H1A—N1—H1B | 108.3 |
| N1vi—Zn1—N1vii | 80.19 (10) | N1—C1—C1viii | 109.52 (17) |
| N1vi—Zn1—N1 | 93.74 (11) | N1—C1—H2A | 109.8 |
| N1vii—Zn1—N1 | 93.40 (7) | C1viii—C1—H2A | 109.8 |
| N1vi—Zn1—N1v | 93.40 (7) | N1—C1—H2B | 109.8 |
| N1vii—Zn1—N1v | 93.74 (11) | C1viii—C1—H2B | 109.8 |
| N1—Zn1—N1v | 170.67 (11) | H2A—C1—H2B | 108.2 |
| N1vi—Zn1—N1—C1 | 106.99 (17) | N1ix—Zn1—N1—C1 | −79.03 (19) |
| N1vii—Zn1—N1—C1 | −172.64 (16) | Zn1—N1—C1—C1viii | −39.9 (3) |
| N1viii—Zn1—N1—C1 | 14.19 (13) |
| Symmetry codes: (i) −x+y, y, −z+3/2; (ii) −y+1, x−y+1, z; (iii) x, x−y+1, −z+3/2; (iv) −x+y, −x+1, z; (v) −y+1, −x+1, −z+3/2; (vi) x, x−y, −z+3/2; (vii) −x+y+1, −x+1, z; (viii) −x+y+1, y, −z+3/2; (ix) −y+1, x−y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···F1x | 0.92 | 2.26 | 3.113 (3) | 155 |
| N1—H1A···F1xi | 0.92 | 2.49 | 3.239 (3) | 139 |
| N1—H1B···F1vii | 0.92 | 2.25 | 3.153 (3) | 166 |
| Symmetry codes: (x) y, x, −z+2; (xi) x−y+1, −y+1, −z+2; (vii) −x+y+1, −x+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···F1i | 0.92 | 2.26 | 3.113 (3) | 155 |
| N1—H1A···F1ii | 0.92 | 2.49 | 3.239 (3) | 139 |
| N1—H1B···F1iii | 0.92 | 2.25 | 3.153 (3) | 166 |
| Symmetry codes: (i) y, x, −z+2; (ii) x−y+1, −y+1, −z+2; (iii) −x+y+1, −x+1, z. |
The authors are grateful to the Engineering and Physical Science Research Council (EPSRC, UK) and the National Natural Science Funds of China (grant Nos. 20573077, 50672063) for financial support.
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A large number of salts with the general formula MG6LR6, where M is a bivalent metal, G may be water or ammonia, L is a quadrivalent element like Si, Sn, Ti or Zr, and R may be Cl, F or CN, (Ray et al., 1973), were studied. We report a similar type of the title salt containing organic molecules. The molecule of the title salt, shown in Fig. 1, consists of one Zn(C2N2H8)3 cation and one SiF6 anion. The coordination of ZnII centers through bridging-bidentate ethylenediamine groups forms a wind-stick-like cluster. The Zn(C2N2H8)3 cluster and SiF6 octahedra are stacked alternately along the threefold axis in approximately CsCl-type packing.