Tris(ethyl­enedi­amine)zinc(II) hexa­fluorido­silicate

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 Zn^II 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.

Related literature

For related structures, see: Ray et al. (1973); Bernhardt & Riley (2003); Cernak et al. (1984); Emsley et al. (1989); Cheng et al. (2008).

Experimental

Crystal data

• [Zn(C₂H₈N₂)₃](SiF₆)

• M_r = 387.77

• Hexagonal, P 6₃ 22

• a = 9.192 (2) Å

• c = 9.755 (3) Å

• V = 713.8 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 1.87 mm⁻¹

• T = 93 K

• 0.10 × 0.10 × 0.10 mm

Data collection

• Rigaku Mercury CCD diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2004) T_min = 0.835, T_max = 0.835

• 4809 measured reflections

• 534 independent reflections

• 499 reflections with I > 2σ(I)

• R_int = 0.045

Refinement

• R[F² > 2σ(F²)] = 0.027

• wR(F²) = 0.059

• S = 1.11

• 534 reflections

• 32 parameters

• H-atom parameters constrained

• Δρ_max = 0.51 e Å⁻³

• Δρ_min = −0.38 e Å⁻³

• Absolute structure: Flack (1983), 177 Friedel pairs

• Flack parameter: 0.01 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯F1^i	0.92	2.26	3.113 (3)	155
N1—H1A⋯F1^ii	0.92	2.49	3.239 (3)	139
N1—H1B⋯F1^iii	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.

Data collection: CrystalClear (Rigaku, 2004); cell refinement: CrystalClear; data reduction: CrystalClear; 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).

Supporting information

S1. Comment

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.

Related literature

For related structures, see: Ray et al. (1973); Bernhardt & Riley (2003); Cernak et al. (1984); Emsley et al. (1989); Cheng et al. (2008).

S2. Experimental

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.

S3. Refinement

All H atoms were fixed geometrically (C—H = 0.99 Å, N—H = 0.92 Å) and treated as riding with U_iso(H) = 1.2Ueq of the parent atom.

Computing details

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).

Figures

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Tris(ethylenediamine)zinc(II) hexafluoridosilicate

Crystal data

[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) Å^3	Prism, colorless
Z = 2	0.10 × 0.10 × 0.10 mm
F(000) = 400

Data collection

Rigaku Mercury CCD diffractometer	534 independent reflections
Radiation source: rotating anode	499 reflections with I > 2σ(I)
Confocal monochromator	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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.059	w = 1/[σ^2(Fo^2) + (0.0158P)^2 + 0.5912P] where P = (Fo^2 + 2Fc^2)/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	Absolute structure parameter: 0.01 (3)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Si1—F1^i	1.6938 (13)	Zn1—N1^v	2.186 (2)
Si1—F1^ii	1.6938 (13)	Zn1—N1^viii	2.1863 (19)
Si1—F1^iii	1.6938 (14)	Zn1—N1^ix	2.1863 (19)
Si1—F1^iv	1.6938 (14)	N1—C1	1.482 (3)
Si1—F1	1.6938 (13)	N1—H1A	0.9200
Si1—F1^v	1.6938 (13)	N1—H1B	0.9200
Zn1—N1^vi	2.1863 (19)	C1—C1^viii	1.523 (4)
Zn1—N1^vii	2.1863 (19)	C1—H2A	0.9900
Zn1—N1	2.186 (2)	C1—H2B	0.9900
F1^i—Si1—F1^ii	90.69 (10)	N1^vi—Zn1—N1^viii	93.40 (7)
F1^i—Si1—F1^iii	89.68 (7)	N1^vii—Zn1—N1^viii	170.67 (11)
F1^ii—Si1—F1^iii	89.95 (10)	N1—Zn1—N1^viii	80.19 (10)
F1^i—Si1—F1^iv	89.95 (10)	N1^v—Zn1—N1^viii	93.40 (7)
F1^ii—Si1—F1^iv	89.68 (7)	N1^vi—Zn1—N1^ix	170.67 (11)
F1^iii—Si1—F1^iv	179.47 (11)	N1^vii—Zn1—N1^ix	93.40 (7)
F1^i—Si1—F1	179.47 (11)	N1—Zn1—N1^ix	93.40 (7)
F1^ii—Si1—F1	89.68 (7)	N1^v—Zn1—N1^ix	80.19 (10)
F1^iii—Si1—F1	90.69 (10)	N1^viii—Zn1—N1^ix	93.74 (11)
F1^iv—Si1—F1	89.68 (7)	C1—N1—Zn1	109.01 (14)
F1^i—Si1—F1^v	89.68 (7)	C1—N1—H1A	109.9
F1^ii—Si1—F1^v	179.47 (11)	Zn1—N1—H1A	109.9
F1^iii—Si1—F1^v	89.68 (7)	C1—N1—H1B	109.9
F1^iv—Si1—F1^v	90.69 (10)	Zn1—N1—H1B	109.9
F1—Si1—F1^v	89.95 (10)	H1A—N1—H1B	108.3
N1^vi—Zn1—N1^vii	80.19 (10)	N1—C1—C1^viii	109.52 (17)
N1^vi—Zn1—N1	93.74 (11)	N1—C1—H2A	109.8
N1^vii—Zn1—N1	93.40 (7)	C1^viii—C1—H2A	109.8
N1^vi—Zn1—N1^v	93.40 (7)	N1—C1—H2B	109.8
N1^vii—Zn1—N1^v	93.74 (11)	C1^viii—C1—H2B	109.8
N1—Zn1—N1^v	170.67 (11)	H2A—C1—H2B	108.2
N1^vi—Zn1—N1—C1	106.99 (17)	N1^ix—Zn1—N1—C1	−79.03 (19)
N1^vii—Zn1—N1—C1	−172.64 (16)	Zn1—N1—C1—C1^viii	−39.9 (3)
N1^viii—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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···F1^x	0.92	2.26	3.113 (3)	155
N1—H1A···F1^xi	0.92	2.49	3.239 (3)	139
N1—H1B···F1^vii	0.92	2.25	3.153 (3)	166

Symmetry codes: (vii) −x+y+1, −x+1, z; (x) y, x, −z+2; (xi) x−y+1, −y+1, −z+2.