Diaqua­tetra­chloridotin(IV)–diglyme (1/2)

Wardell, J.L.; Harrison, W.T.A.

doi:10.1107/S1600536808029917

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1297

doi:10.1107/S1600536808029917

Open

access

Diaquatetrachloridotin(IV)–diglyme (1/2)

James L. Wardell ^a and William T. A. Harrison ^b ^*

^aDepartamento de Quimica, Universidade Federal de Minas Gerais, UFMG, Avenida Antônio Carlos 6627, Belo Horizonte, MG, CEP 31270-901, Brazil, and ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 16 September 2008; accepted 17 September 2008; online 20 September 2008)

In the title 1:2 adduct, [SnCl₄(H₂O)₂]·2C₆H₁₄O₃, the Sn^IV 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.

Related literature

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

Crystal data

[SnCl₄(H₂O)₂]·2C₆H₁₄O₃
M_r = 564.86
Orthorhombic, P b c n
a = 8.4023 (2) Å
b = 17.1528 (3) Å
c = 15.9612 (4) Å
V = 2300.38 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.61 mm⁻¹
T = 120 (2) K
0.55 × 0.43 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.472, T_max = 0.795
20197 measured reflections
2643 independent reflections
2292 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.022
wR(F²) = 0.050
S = 1.04
2643 reflections
121 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Selected bond lengths (Å)

Sn1—O1	2.1343 (13)
Sn1—Cl1	2.3772 (4)
Sn1—Cl2	2.3853 (5)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H2⋯O2	0.77 (2)	1.88 (2)	2.6503 (18)	175 (2)
O1—H1⋯O4	0.82 (2)	1.91 (2)	2.7296 (18)	175 (2)

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808029917/bt2792sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029917/bt2792Isup2.hkl

checkCIF report

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%.

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

	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.
	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]·2C₆H₁₄O₃	F(000) = 1144
M_r = 564.86	D_x = 1.631 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 10481 reflections
a = 8.4023 (2) Å	θ = 2.9–27.5°
b = 17.1528 (3) Å	µ = 1.61 mm⁻¹
c = 15.9612 (4) Å	T = 120 K
V = 2300.38 (9) Å³	Slab, colourless
Z = 4	0.55 × 0.43 × 0.15 mm

Data collection top

Nonius KappaCCD diffractometer	2643 independent reflections
Radiation source: fine-focus sealed tube	2292 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ω and ϕ scans	θ_max = 27.6°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −10→10
T_min = 0.472, T_max = 0.795	k = −19→22
20197 measured reflections	l = −17→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap and geom
R[F² > 2σ(F²)] = 0.022	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.050	w = 1/[σ²(F_o²) + (0.0206P)² + 1.2513P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2643 reflections	Δρ_max = 0.56 e Å⁻³
121 parameters	Δρ_min = −0.50 e Å⁻³
0 restraints	Extinction correction: (SHELXL97; Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00095 (17)

Crystal data top

[SnCl₄(H₂O)₂]·2C₆H₁₄O₃	V = 2300.38 (9) Å³
M_r = 564.86	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 8.4023 (2) Å	µ = 1.61 mm⁻¹
b = 17.1528 (3) Å	T = 120 K
c = 15.9612 (4) Å	0.55 × 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)
T_min = 0.472, T_max = 0.795	R_int = 0.037
20197 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.050	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.56 e Å⁻³
2643 reflections	Δρ_min = −0.50 e Å⁻³
121 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.

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

	x	y	z	U_iso*/U_eq
Sn1	0.0000	0.165876 (9)	0.7500	0.01280 (7)
Cl1	0.27717 (5)	0.17456 (3)	0.72161 (3)	0.02257 (11)
Cl2	0.04156 (6)	0.07342 (3)	0.85946 (3)	0.02251 (11)
O1	0.02883 (16)	0.25927 (8)	0.83704 (9)	0.0201 (3)
H1	−0.023 (2)	0.2999 (14)	0.8351 (14)	0.024*
H2	0.107 (3)	0.2655 (12)	0.8617 (14)	0.024*
C1	0.3671 (3)	0.19896 (12)	0.94703 (16)	0.0380 (6)
H1A	0.3444	0.1587	0.9051	0.057*
H1B	0.3199	0.1839	1.0008	0.057*
H1C	0.4826	0.2045	0.9535	0.057*
C2	0.3303 (2)	0.33246 (10)	0.97905 (12)	0.0211 (4)
H2A	0.4454	0.3351	0.9920	0.025*
H2B	0.2720	0.3220	1.0318	0.025*
C3	0.2759 (2)	0.40787 (10)	0.94202 (13)	0.0228 (4)
H3A	0.3058	0.4516	0.9793	0.027*
H3B	0.3273	0.4161	0.8869	0.027*
C4	0.0482 (2)	0.46917 (10)	0.88487 (13)	0.0254 (4)
H4A	0.1021	0.4714	0.8298	0.030*
H4B	0.0690	0.5187	0.9148	0.030*
C5	−0.1273 (2)	0.45811 (11)	0.87301 (13)	0.0257 (4)
H5A	−0.1798	0.4520	0.9281	0.031*
H5B	−0.1733	0.5044	0.8449	0.031*
C6	−0.3192 (2)	0.38022 (12)	0.80483 (15)	0.0327 (5)
H6A	−0.3336	0.3337	0.7700	0.049*
H6B	−0.3587	0.4261	0.7747	0.049*
H6C	−0.3786	0.3740	0.8573	0.049*
O2	0.30068 (16)	0.27173 (7)	0.92018 (9)	0.0260 (3)
O3	0.10705 (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

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.01400 (9)	0.00920 (10)	0.01519 (11)	0.000	−0.00062 (6)	0.000
Cl1	0.0149 (2)	0.0241 (2)	0.0287 (3)	0.00062 (16)	0.00141 (18)	−0.00129 (19)
Cl2	0.0303 (2)	0.0155 (2)	0.0217 (3)	0.00401 (17)	−0.00013 (18)	0.00507 (18)
O1	0.0210 (7)	0.0128 (6)	0.0265 (8)	0.0060 (5)	−0.0101 (6)	−0.0061 (6)
C1	0.0429 (13)	0.0233 (11)	0.0477 (15)	0.0116 (9)	−0.0239 (11)	−0.0025 (10)
C2	0.0193 (8)	0.0252 (10)	0.0187 (11)	−0.0034 (7)	−0.0042 (7)	−0.0030 (7)
C3	0.0215 (9)	0.0206 (9)	0.0263 (12)	−0.0066 (7)	−0.0017 (8)	−0.0031 (8)
C4	0.0341 (10)	0.0129 (9)	0.0291 (12)	−0.0003 (7)	−0.0054 (9)	0.0018 (8)
C5	0.0334 (11)	0.0165 (9)	0.0273 (12)	0.0086 (7)	−0.0029 (8)	−0.0030 (8)
C6	0.0214 (10)	0.0325 (11)	0.0441 (14)	0.0059 (8)	−0.0066 (9)	−0.0025 (10)
O2	0.0300 (7)	0.0179 (6)	0.0300 (8)	0.0067 (5)	−0.0164 (6)	−0.0047 (6)
O3	0.0199 (6)	0.0170 (6)	0.0260 (8)	−0.0009 (5)	−0.0016 (5)	0.0034 (5)
O4	0.0196 (6)	0.0183 (6)	0.0299 (8)	0.0052 (5)	−0.0034 (5)	−0.0035 (6)

Geometric parameters (Å, º) top

Sn1—O1	2.1343 (13)	C2—H2B	0.9900
Sn1—O1ⁱ	2.1343 (13)	C3—O3	1.428 (2)
Sn1—Cl1	2.3772 (4)	C3—H3A	0.9900
Sn1—Cl1ⁱ	2.3772 (4)	C3—H3B	0.9900
Sn1—Cl2ⁱ	2.3853 (5)	C4—O3	1.421 (2)
Sn1—Cl2	2.3853 (5)	C4—C5	1.499 (3)
O1—H1	0.82 (2)	C4—H4A	0.9900
O1—H2	0.77 (2)	C4—H4B	0.9900
C1—O2	1.433 (2)	C5—O4	1.429 (2)
C1—H1A	0.9800	C5—H5A	0.9900
C1—H1B	0.9800	C5—H5B	0.9900
C1—H1C	0.9800	C6—O4	1.429 (2)
C2—O2	1.425 (2)	C6—H6A	0.9800
C2—C3	1.494 (2)	C6—H6B	0.9800
C2—H2A	0.9900	C6—H6C	0.9800

O1—Sn1—O1ⁱ	82.72 (8)	H2A—C2—H2B	108.4
O1—Sn1—Cl1	88.04 (4)	O3—C3—C2	108.66 (14)
O1ⁱ—Sn1—Cl1	86.57 (4)	O3—C3—H3A	110.0
O1—Sn1—Cl1ⁱ	86.57 (4)	C2—C3—H3A	110.0
O1ⁱ—Sn1—Cl1ⁱ	88.04 (4)	O3—C3—H3B	110.0
Cl1—Sn1—Cl1ⁱ	172.81 (2)	C2—C3—H3B	110.0
O1—Sn1—Cl2ⁱ	172.96 (4)	H3A—C3—H3B	108.3
O1ⁱ—Sn1—Cl2ⁱ	90.32 (4)	O3—C4—C5	108.18 (15)
Cl1—Sn1—Cl2ⁱ	92.608 (16)	O3—C4—H4A	110.1
Cl1ⁱ—Sn1—Cl2ⁱ	92.169 (17)	C5—C4—H4A	110.1
O1—Sn1—Cl2	90.32 (4)	O3—C4—H4B	110.1
O1ⁱ—Sn1—Cl2	172.96 (4)	C5—C4—H4B	110.1
Cl1—Sn1—Cl2	92.169 (16)	H4A—C4—H4B	108.4
Cl1ⁱ—Sn1—Cl2	92.608 (16)	O4—C5—C4	109.14 (14)
Cl2ⁱ—Sn1—Cl2	96.65 (2)	O4—C5—H5A	109.9
Sn1—O1—H1	123.4 (16)	C4—C5—H5A	109.9
Sn1—O1—H2	122.1 (16)	O4—C5—H5B	109.9
H1—O1—H2	111 (2)	C4—C5—H5B	109.9
O2—C1—H1A	109.5	H5A—C5—H5B	108.3
O2—C1—H1B	109.5	O4—C6—H6A	109.5
H1A—C1—H1B	109.5	O4—C6—H6B	109.5
O2—C1—H1C	109.5	H6A—C6—H6B	109.5
H1A—C1—H1C	109.5	O4—C6—H6C	109.5
H1B—C1—H1C	109.5	H6A—C6—H6C	109.5
O2—C2—C3	108.58 (15)	H6B—C6—H6C	109.5
O2—C2—H2A	110.0	C2—O2—C1	111.81 (14)
C3—C2—H2A	110.0	C4—O3—C3	112.30 (13)
O2—C2—H2B	110.0	C6—O4—C5	111.33 (14)
C3—C2—H2B	110.0

O2—C2—C3—O3	65.6 (2)	C5—C4—O3—C3	176.00 (15)
O3—C4—C5—O4	−64.9 (2)	C2—C3—O3—C4	−170.23 (16)
C3—C2—O2—C1	172.98 (17)	C4—C5—O4—C6	−175.75 (16)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2···O2	0.77 (2)	1.88 (2)	2.6503 (18)	175 (2)
O1—H1···O4	0.82 (2)	1.91 (2)	2.7296 (18)	175 (2)

Experimental details

Crystal data
Chemical formula	[SnCl₄(H₂O)₂]·2C₆H₁₄O₃
M_r	564.86
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	120
a, b, c (Å)	8.4023 (2), 17.1528 (3), 15.9612 (4)
V (Å³)	2300.38 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.61
Crystal size (mm)	0.55 × 0.43 × 0.15

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.472, 0.795
No. of measured, independent and observed [I > 2σ(I)] reflections	20197, 2643, 2292
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.050, 1.04
No. of reflections	2643
No. of parameters	121
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.50

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected bond lengths (Å) top

Sn1—O1	2.1343 (13)	Sn1—Cl2	2.3853 (5)
Sn1—Cl1	2.3772 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2···O2	0.77 (2)	1.88 (2)	2.6503 (18)	175 (2)
O1—H1···O4	0.82 (2)	1.91 (2)	2.7296 (18)	175 (2)

Acknowledgements

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Azadmehr, A., Amini, M. M., Tadjarodi, A., Taeb, A. & Ng, S. W. (2001). Main Group Met. Chem. 24, 459–460. CrossRef CAS Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192–197. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hough, E., Nicholson, D. G. & Vasudevan, A. K. (1986). J. Chem. Soc. Dalton Trans. pp. 2335–2337. CSD CrossRef Web of Science Google Scholar
Hutton, R. E. & Oakes, V. (1976). Adv. Chem. Ser. 157, 123–136. CrossRef CAS Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Valle, G., Cassol, A. & Russo, U. (1984). Inorg. Chim. Acta, 82, 81–84. CSD CrossRef CAS Web of Science Google Scholar