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Acta Cryst. (2008). E64, m1297    [ doi:10.1107/S1600536808029917 ]

Diaquatetrachloridotin(IV)-diglyme (1/2)

J. L. Wardell and W. T. A. Harrison

Abstract top

In the title 1:2 adduct, [SnCl4(H2O)2]·2C6H14O3, the SnIV atom (site symmetry 2) adopts a cis-SnO2Cl4 octahedral geometry. In the crystal structure, O-H...O hydrogen bonds lead to associations of one metal complex and two diglyme molecules.

Comment top

The title compound, (I), (Fig. 1) complements related adducts containing the same metal complex accompanied by various crown ethers (Valle et al., 1984; Hough et al., 1986; Azadmehr et al., 2001).

In (I), the tin(IV) atom lies on a crystallographic twofold rotation axis, and bonds to two water molecules and four chloride ions, with the water O atoms in cis conformation {O1—Sn1—O1i = 82.72 (8)°; i = -x, y, 3/2 - z]. Overall, a distorted octahedral coordination arises for the metal (Table 1). The bond valence sum (BVS) (Brese & O'Keeffe, 1991) for tin is 4.09 (expected value = 4.00).

In the crystal, the Sn(H2O)2Cl4 moiety links to two adjacent C6H14O3 (diglyme) molecules by way of O—H···O hydrogen bonds (Table 2), with each water molecule making two such bonds to the same diglyme species (Fig. 2). This hydrogen bonding pattern may correlate with the fact that the O—C—C—O torsion angles reflect gauche conformations about the C2—C3 and C4—C5 bonds [O2—C2—C3—O3 = 65.6 (2)°; O3—C4—C5—O4 = -64.9 (2)°], whereas the four C—C—O—C conformations are trans. Otherwise, the geometrical paramaters for (I) may be regarded as normal (Allen et al., 1987).

Related literature top

For related structures, see: Valle et al. (1984); Hough et al. (1986); Azadmehr et al. (2001). For further synthetic details, see: Hutton & Oakes (1976). For reference structural data, see: Allen et al. (1987). For bond valence sum calculations, see: Brese & O'Keeffe (1991).

Experimental top

Air-stable, colourless slabs of (I) were isolated from the slow evaporation of a methanolic solution (20 ml) containing 0.1 mmol C l3SnCH2CH2CO2H (Hutton & Oakes, 1976) and 0.1 mmol diglyme. M.P. 353–355 K. IR (KBr): 3500–2500, 1363, 1471, 1454, 1354,1287, 1250, 1141, 1102, 1079, 1105, 860, 834, 701, 617 cm-1 Anal: Calc: C 25.52; H 5.71%. Found: C 25.23; H 5.85%.

Refinement top

The water H atoms were located in a difference map and their positions were freely refined with the constraint Uiso(H) = 1.2Ueq(O). The C-bound H atoms were placed in calculated positions (C—H = 0.98–0.99 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl groups were allowed to rotate, but not to tip, to best fit the electron density.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids. The H atoms are drawn as spheres of arbitrary radius and the hydrogen bonds are shown as double-dashed lines. Symmetry code: (i) -x, y, 3/2 - z.
[Figure 2] Fig. 2. Unit cell packing for (I) showing the isolated hydrogen bonded assembiles of one metal complex and two diglyme molecules. Symmetry code: (i) -x, y, 3/2 - z. The C-bound H atoms are omitted for clarity.
Diaquatetrachloridotin(IV)–diglyme (1/2) top
Crystal data top
[SnCl4(H2O)2]·2C6H14O3F(000) = 1144
Mr = 564.86Dx = 1.631 Mg m−3
Orthorhombic, PbcnMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2abCell parameters from 10481 reflections
a = 8.4023 (2) Åθ = 2.9–27.5°
b = 17.1528 (3) ŵ = 1.61 mm−1
c = 15.9612 (4) ÅT = 120 K
V = 2300.38 (9) Å3Slab, colourless
Z = 40.55 × 0.43 × 0.15 mm
Data collection top
Nonius KappaCCD
diffractometer		2643 independent reflections
Radiation source: fine-focus sealed tube2292 reflections with I > 2σ(I)
graphiteRint = 0.037
ω and φ scansθmax = 27.6°, θmin = 3.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		h = −10→10
Tmin = 0.472, Tmax = 0.795k = −19→22
20197 measured reflectionsl = −17→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difmap and geom
R[F2 > 2σ(F2)] = 0.022H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.050 w = 1/[σ2(Fo2) + (0.0206P)2 + 1.2513P]
where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2643 reflectionsΔρmax = 0.56 e Å−3
121 parametersΔρmin = −0.50 e Å−3
0 restraintsExtinction correction: (SHELXL97; Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00095 (17)
Crystal data top
[SnCl4(H2O)2]·2C6H14O3V = 2300.38 (9) Å3
Mr = 564.86Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 8.4023 (2) ŵ = 1.61 mm−1
b = 17.1528 (3) ÅT = 120 K
c = 15.9612 (4) Å0.55 × 0.43 × 0.15 mm
Data collection top
Nonius KappaCCD
diffractometer		2643 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		2292 reflections with I > 2σ(I)
Tmin = 0.472, Tmax = 0.795Rint = 0.037
20197 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.022H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.050Δρmax = 0.56 e Å−3
S = 1.04Δρmin = −0.50 e Å−3
2643 reflectionsAbsolute structure: ?
121 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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.

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 (Å2) top
xyzUiso*/Ueq
Sn10.00000.165876 (9)0.75000.01280 (7)
Cl10.27717 (5)0.17456 (3)0.72161 (3)0.02257 (11)
Cl20.04156 (6)0.07342 (3)0.85946 (3)0.02251 (11)
O10.02883 (16)0.25927 (8)0.83704 (9)0.0201 (3)
H1−0.023 (2)0.2999 (14)0.8351 (14)0.024*
H20.107 (3)0.2655 (12)0.8617 (14)0.024*
C10.3671 (3)0.19896 (12)0.94703 (16)0.0380 (6)
H1A0.34440.15870.90510.057*
H1B0.31990.18391.00080.057*
H1C0.48260.20450.95350.057*
C20.3303 (2)0.33246 (10)0.97905 (12)0.0211 (4)
H2A0.44540.33510.99200.025*
H2B0.27200.32201.03180.025*
C30.2759 (2)0.40787 (10)0.94202 (13)0.0228 (4)
H3A0.30580.45160.97930.027*
H3B0.32730.41610.88690.027*
C40.0482 (2)0.46917 (10)0.88487 (13)0.0254 (4)
H4A0.10210.47140.82980.030*
H4B0.06900.51870.91480.030*
C5−0.1273 (2)0.45811 (11)0.87301 (13)0.0257 (4)
H5A−0.17980.45200.92810.031*
H5B−0.17330.50440.84490.031*
C6−0.3192 (2)0.38022 (12)0.80483 (15)0.0327 (5)
H6A−0.33360.33370.77000.049*
H6B−0.35870.42610.77470.049*
H6C−0.37860.37400.85730.049*
O20.30068 (16)0.27173 (7)0.92018 (9)0.0260 (3)
O30.10705 (14)0.40525 (7)0.93230 (8)0.0210 (3)
O4−0.15401 (14)0.39017 (7)0.82313 (8)0.0226 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.01400 (9)0.00920 (10)0.01519 (11)0.000−0.00062 (6)0.000
Cl10.0149 (2)0.0241 (2)0.0287 (3)0.00062 (16)0.00141 (18)−0.00129 (19)
Cl20.0303 (2)0.0155 (2)0.0217 (3)0.00401 (17)−0.00013 (18)0.00507 (18)
O10.0210 (7)0.0128 (6)0.0265 (8)0.0060 (5)−0.0101 (6)−0.0061 (6)
C10.0429 (13)0.0233 (11)0.0477 (15)0.0116 (9)−0.0239 (11)−0.0025 (10)
C20.0193 (8)0.0252 (10)0.0187 (11)−0.0034 (7)−0.0042 (7)−0.0030 (7)
C30.0215 (9)0.0206 (9)0.0263 (12)−0.0066 (7)−0.0017 (8)−0.0031 (8)
C40.0341 (10)0.0129 (9)0.0291 (12)−0.0003 (7)−0.0054 (9)0.0018 (8)
C50.0334 (11)0.0165 (9)0.0273 (12)0.0086 (7)−0.0029 (8)−0.0030 (8)
C60.0214 (10)0.0325 (11)0.0441 (14)0.0059 (8)−0.0066 (9)−0.0025 (10)
O20.0300 (7)0.0179 (6)0.0300 (8)0.0067 (5)−0.0164 (6)−0.0047 (6)
O30.0199 (6)0.0170 (6)0.0260 (8)−0.0009 (5)−0.0016 (5)0.0034 (5)
O40.0196 (6)0.0183 (6)0.0299 (8)0.0052 (5)−0.0034 (5)−0.0035 (6)
Geometric parameters (Å, °) top
Sn1—O12.1343 (13)C2—H2B0.9900
Sn1—O1i2.1343 (13)C3—O31.428 (2)
Sn1—Cl12.3772 (4)C3—H3A0.9900
Sn1—Cl1i2.3772 (4)C3—H3B0.9900
Sn1—Cl2i2.3853 (5)C4—O31.421 (2)
Sn1—Cl22.3853 (5)C4—C51.499 (3)
O1—H10.82 (2)C4—H4A0.9900
O1—H20.77 (2)C4—H4B0.9900
C1—O21.433 (2)C5—O41.429 (2)
C1—H1A0.9800C5—H5A0.9900
C1—H1B0.9800C5—H5B0.9900
C1—H1C0.9800C6—O41.429 (2)
C2—O21.425 (2)C6—H6A0.9800
C2—C31.494 (2)C6—H6B0.9800
C2—H2A0.9900C6—H6C0.9800
O1—Sn1—O1i82.72 (8)H2A—C2—H2B108.4
O1—Sn1—Cl188.04 (4)O3—C3—C2108.66 (14)
O1i—Sn1—Cl186.57 (4)O3—C3—H3A110.0
O1—Sn1—Cl1i86.57 (4)C2—C3—H3A110.0
O1i—Sn1—Cl1i88.04 (4)O3—C3—H3B110.0
Cl1—Sn1—Cl1i172.81 (2)C2—C3—H3B110.0
O1—Sn1—Cl2i172.96 (4)H3A—C3—H3B108.3
O1i—Sn1—Cl2i90.32 (4)O3—C4—C5108.18 (15)
Cl1—Sn1—Cl2i92.608 (16)O3—C4—H4A110.1
Cl1i—Sn1—Cl2i92.169 (17)C5—C4—H4A110.1
O1—Sn1—Cl290.32 (4)O3—C4—H4B110.1
O1i—Sn1—Cl2172.96 (4)C5—C4—H4B110.1
Cl1—Sn1—Cl292.169 (16)H4A—C4—H4B108.4
Cl1i—Sn1—Cl292.608 (16)O4—C5—C4109.14 (14)
Cl2i—Sn1—Cl296.65 (2)O4—C5—H5A109.9
Sn1—O1—H1123.4 (16)C4—C5—H5A109.9
Sn1—O1—H2122.1 (16)O4—C5—H5B109.9
H1—O1—H2111 (2)C4—C5—H5B109.9
O2—C1—H1A109.5H5A—C5—H5B108.3
O2—C1—H1B109.5O4—C6—H6A109.5
H1A—C1—H1B109.5O4—C6—H6B109.5
O2—C1—H1C109.5H6A—C6—H6B109.5
H1A—C1—H1C109.5O4—C6—H6C109.5
H1B—C1—H1C109.5H6A—C6—H6C109.5
O2—C2—C3108.58 (15)H6B—C6—H6C109.5
O2—C2—H2A110.0C2—O2—C1111.81 (14)
C3—C2—H2A110.0C4—O3—C3112.30 (13)
O2—C2—H2B110.0C6—O4—C5111.33 (14)
C3—C2—H2B110.0
O2—C2—C3—O365.6 (2)C5—C4—O3—C3176.00 (15)
O3—C4—C5—O4−64.9 (2)C2—C3—O3—C4−170.23 (16)
C3—C2—O2—C1172.98 (17)C4—C5—O4—C6−175.75 (16)
Symmetry codes: (i) −x, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H2···O20.77 (2)1.88 (2)2.6503 (18)175 (2)
O1—H1···O40.82 (2)1.91 (2)2.7296 (18)175 (2)
Table 1
Selected geometric parameters (Å) top
Sn1—O12.1343 (13)Sn1—Cl22.3853 (5)
Sn1—Cl12.3772 (4)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H2···O20.77 (2)1.88 (2)2.6503 (18)175 (2)
O1—H1···O40.82 (2)1.91 (2)2.7296 (18)175 (2)
Acknowledgements top

We thank the EPSRC UK National Crystallography Service (University of Southampton) for the data collection.

references
References top

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