metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Crystal structure of a one-dimensional coordination polymer of tin(IV) bromide with 1,4-di­thiane

aInstitute of Chemistry of New Materials, University of Osnabrueck, Barbarstr. 7, 49069 Osnabrueck, Germany
*Correspondence e-mail: hreuter@uos.de

Edited by M. Nieger, University of Helsinki, Finland (Received 2 December 2015; accepted 12 December 2015; online 16 December 2015)

The title compound, [SnBr4(C4H8S2)] {systematic name: catena-poly[[tetrabromidotin(IV)]-μ-1,4-dithiane-κ2S:S′]}, represents the first 1,4-di­thiane complex with tin as coordination centre. The asymmetric unit consist of half a formula unit with the tin(IV) atom at the centre of symmetry at 0,0,1/2 (Wyckoff symbol b) and a centrosymmetric 1,4-di­thiane mol­ecule with the centre of symmetry in 1/2,0,1 (Wyckoff symbol c). The tin(IV) atom is coordinated in a distorted octa­hedral manner by the four bromine atoms and two sulfur atoms of two 1,4-di­thiane mol­ecules in a trans-position. Sn—Br [mean value: 2.561 (5) Å] and Sn—S distances [2.6546 (6) Å] are in the typical range for octa­hedrally coordinated tin(IV) atoms and the di­thiane mol­ecule adopts a chair conformation. The one-dimensional polymeric chains propagate along the [101] direction with weak inter­molecular Br⋯Br [3.5724 (4) Å] between parallel chains and weak Br⋯H inter­actions [2.944–2.993 Å] within the chains.

1. Related literature

For the structural parameters in macrocyclic thio­ether complexes with SnBr4, see: Levason et al. (2003[Levason, W., Matthews, M. L., Patel, R., Reid, G. & Webster, M. (2003). New J. Chem. 27, 1784-1788.]), and for di­thio­ether complexes with SnBr4, see: Dann et al. (1996[Dann, S. E., Genge, A. R. J., Levason, W. & Reid, G. (1996). J. Chem. Soc. Dalton Trans. pp. 4471-4478.]). For the oxidation of tin(II) to tin(IV), see: Deacon et al. (1997[Deacon, P. R., Mahon, M. F., Molloy, K. C. & Waterfield, P. C. (1997). J. Chem. Soc. Dalton Trans. pp. 3705-3712.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • [SnBr4(C4H8S2)]

  • Mr = 558.55

  • Monoclinic, P 21 /n

  • a = 7.1033 (4) Å

  • b = 12.0526 (8) Å

  • c = 7.4032 (5) Å

  • β = 112.144 (2)°

  • V = 587.06 (7) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 16.09 mm−1

  • T = 100 K

  • 0.16 × 0.06 × 0.06 mm

2.2. Data collection

  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.182, Tmax = 0.450

  • 22217 measured reflections

  • 1426 independent reflections

  • 1339 reflections with I > 2σ(I)

  • Rint = 0.066

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.017

  • wR(F2) = 0.036

  • S = 1.14

  • 1426 reflections

  • 54 parameters

  • H-atom parameters constrained

  • Δρmax = 0.72 e Å−3

  • Δρmin = −0.46 e Å−3

Table 1
Selected contacts (Å)

Br1⋯H11i 2.965
Br1⋯H21ii 2.993
Br2⋯H22iii 2.944
Br1⋯H12iv 3.078
Br1⋯H11v 3.079
Br1⋯Br2vi 3.5724 (4)
Symmetry codes: (i) -x, -y, -z+1; (ii) -x+1, -y, -z+2; (iii) x-1, y, z-1; (iv) x, y, z-1; (v) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]; (vi) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2009[Bruker (2009). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]); molecular graphics: DIAMOND (Brandenburg, 2006[Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.]) and Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

Supporting information


Synthesis and crystallization top

A mixture of 0.55 g (2 mmol) SnBr2 and 0.24 g (2 mmol) 1,4-di­thiane was heated in a closed ampule to 130 °C for 6 hours. No special care was taken to exclude oxygen or humidity. After cooling, the ampule was opened and its solid content inspected by optical microscopy. Only one fragment, a yellow needle-like crystal of the title compound proved to be suitable for single crystal X-ray diffraction. The presence of tin(IV) in the title compound instead of tin(II) demonstrates the complexity of reactions that must have taken place. Sensitivity of tin(II) compounds towards oxidation by air, however, is not unusual and well documented in literature (e.g. Deacon et al, 1997).

Refinement top

All hydrogen atoms could be localized in difference Fourier syntheses but were refined in geometric positions riding on the carbon atoms with C—H distances of 0.99 Å (-CH2-) and one common, free refined isotropic displacement factor.

Results and discussion top

Only some few coordination compounds of tin(IV) bromide with Lewis-bases containing two or more S-atoms as Lewis-base centers have been structurally characterized. The main structural features are one-dimensional chain structures in case of macrocyclic thio­ether complexes (Levason et al., 2003) with the Lewis-base molecules in a cis- , and trans-position, respectiveley, and the formation of monomeric complexes as a result of chelatization in case of open chain di­thio­ether molecules (Dann et al., 1996). In all cases, the tin atoms are o­cta­hedrally coordinated with similar Sn—Br and Sn—S bond lengths.

Related literature top

For the structural parameters in macrocyclic thioether complexes with SnBr4, see: Levason et al. (2003), and dithioether complexes with SnBr4, see: Dann et al. (1996). For the oxidation of tin(II) to tin(IV), see: Deacon et al. (1997).

Structure description top

Only some few coordination compounds of tin(IV) bromide with Lewis-bases containing two or more S-atoms as Lewis-base centers have been structurally characterized. The main structural features are one-dimensional chain structures in case of macrocyclic thio­ether complexes (Levason et al., 2003) with the Lewis-base molecules in a cis- , and trans-position, respectiveley, and the formation of monomeric complexes as a result of chelatization in case of open chain di­thio­ether molecules (Dann et al., 1996). In all cases, the tin atoms are o­cta­hedrally coordinated with similar Sn—Br and Sn—S bond lengths.

For the structural parameters in macrocyclic thioether complexes with SnBr4, see: Levason et al. (2003), and dithioether complexes with SnBr4, see: Dann et al. (1996). For the oxidation of tin(II) to tin(IV), see: Deacon et al. (1997).

Synthesis and crystallization top

A mixture of 0.55 g (2 mmol) SnBr2 and 0.24 g (2 mmol) 1,4-di­thiane was heated in a closed ampule to 130 °C for 6 hours. No special care was taken to exclude oxygen or humidity. After cooling, the ampule was opened and its solid content inspected by optical microscopy. Only one fragment, a yellow needle-like crystal of the title compound proved to be suitable for single crystal X-ray diffraction. The presence of tin(IV) in the title compound instead of tin(II) demonstrates the complexity of reactions that must have taken place. Sensitivity of tin(II) compounds towards oxidation by air, however, is not unusual and well documented in literature (e.g. Deacon et al, 1997).

Refinement details top

All hydrogen atoms could be localized in difference Fourier syntheses but were refined in geometric positions riding on the carbon atoms with C—H distances of 0.99 Å (-CH2-) and one common, free refined isotropic displacement factor.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Ball-and-stick model of the asymmetric unit of the title compound with the atomic numbering scheme used. For a better understanding the asymmetric unit of the 1,4-dithiane molecule has been extended by its symmetry-related atoms generated by the centre of symmetry i (black dot) at 1/2,0,1. With exception of the H atoms, which are shown as spheres of arbitrary radius, all atoms are drawn as displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. Part of the one-dimensional coordination polymer showing two complete building units.
[Figure 3] Fig. 3. Perspective view of the crystal structure looking down the a axis.
[Figure 4] Fig. 4. Shortest intrachain H···Br (blue) and interchain Br···Br (red) interactions.
[Figure 5] Fig. 5. Three-dimensional representation of the contact surface (probe radius = 0.2 Å, outside color = yellow, inside color = brown) within the unit cell visualizing Br···Br interactions (red) between neighboring chains through holes in the surface.
catena-Poly[[tetrabromidotin(IV)]-µ-1,4-dithiane-κ2S:S'] top
Crystal data top
[SnBr4(C4H8S2)]F(000) = 508
Mr = 558.55Dx = 3.160 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 7.1033 (4) ÅCell parameters from 9935 reflections
b = 12.0526 (8) Åθ = 3.4–28.7°
c = 7.4032 (5) ŵ = 16.09 mm1
β = 112.144 (2)°T = 100 K
V = 587.06 (7) Å3Needle, yellow
Z = 20.16 × 0.06 × 0.06 mm
Data collection top
Bruker APEXII CCD
diffractometer
1339 reflections with I > 2σ(I)
φ and ω scansRint = 0.066
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
θmax = 28.0°, θmin = 3.4°
Tmin = 0.182, Tmax = 0.450h = 99
22217 measured reflectionsk = 1515
1426 independent reflectionsl = 99
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.017H-atom parameters constrained
wR(F2) = 0.036 w = 1/[σ2(Fo2) + (0.0043P)2 + 0.5753P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max < 0.001
1426 reflectionsΔρmax = 0.72 e Å3
54 parametersΔρmin = 0.46 e Å3
0 restraintsExtinction correction: SHELXL2014/7 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0042 (3)
Crystal data top
[SnBr4(C4H8S2)]V = 587.06 (7) Å3
Mr = 558.55Z = 2
Monoclinic, P21/nMo Kα radiation
a = 7.1033 (4) ŵ = 16.09 mm1
b = 12.0526 (8) ÅT = 100 K
c = 7.4032 (5) Å0.16 × 0.06 × 0.06 mm
β = 112.144 (2)°
Data collection top
Bruker APEXII CCD
diffractometer
1426 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
1339 reflections with I > 2σ(I)
Tmin = 0.182, Tmax = 0.450Rint = 0.066
22217 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0170 restraints
wR(F2) = 0.036H-atom parameters constrained
S = 1.14Δρmax = 0.72 e Å3
1426 reflectionsΔρmin = 0.46 e Å3
54 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn10.00000.00000.50000.00740 (7)
Br10.17963 (4)0.12497 (2)0.33464 (3)0.01109 (8)
Br20.04504 (4)0.16589 (2)0.30464 (4)0.01267 (8)
S10.36282 (9)0.04681 (5)0.76832 (9)0.01033 (13)
C10.3132 (4)0.0756 (2)0.9867 (3)0.0119 (5)
H110.23490.14550.96860.015 (4)*
H120.22950.01511.00780.015 (4)*
C20.5088 (4)0.0860 (2)1.1657 (4)0.0129 (5)
H210.47710.11461.27640.015 (4)*
H220.60020.13991.13880.015 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.00749 (13)0.00663 (12)0.00903 (13)0.00013 (8)0.00420 (9)0.00008 (8)
Br10.01171 (14)0.01121 (13)0.01229 (14)0.00266 (9)0.00672 (10)0.00103 (9)
Br20.01522 (15)0.00948 (13)0.01585 (14)0.00006 (9)0.00873 (11)0.00347 (9)
S10.0096 (3)0.0106 (3)0.0110 (3)0.0001 (2)0.0041 (2)0.0002 (2)
C10.0122 (12)0.0131 (12)0.0102 (12)0.0027 (10)0.0041 (10)0.0012 (10)
C20.0121 (12)0.0117 (12)0.0124 (12)0.0029 (10)0.0017 (10)0.0038 (10)
Geometric parameters (Å, º) top
Sn1—Br2i2.5574 (3)Br1—H11v3.0788
Sn1—Br22.5574 (3)Br1—Br2vi3.5724 (4)
Sn1—Br12.5638 (2)S1—C11.813 (2)
Sn1—Br1i2.5638 (3)S1—C2ii1.816 (3)
Sn1—S1i2.6546 (6)C1—C21.521 (3)
Sn1—S12.6546 (6)C1—H110.9900
Br1—H11i2.9646C1—H120.9900
Br1—H21ii2.9932C2—S1ii1.816 (3)
Br2—H22iii2.9438C2—H210.9900
Br1—H12iv3.0783C2—H220.9900
Br2i—Sn1—Br2180.0H21ii—Br1—H11v68.8
Br2i—Sn1—Br190.092 (9)H12iv—Br1—H11v143.5
Br2—Sn1—Br189.908 (9)Sn1—Br1—Br2vi167.821 (10)
Br2i—Sn1—Br1i89.908 (9)H11i—Br1—Br2vi102.6
Br2—Sn1—Br1i90.092 (9)H21ii—Br1—Br2vi88.3
Br1—Sn1—Br1i180.0H12iv—Br1—Br2vi85.5
Br2i—Sn1—S1i87.931 (15)H11v—Br1—Br2vi58.0
Br2—Sn1—S1i92.069 (15)Sn1—Br2—H22iii79.0
Br1—Sn1—S1i92.027 (15)C1—S1—C2ii100.11 (12)
Br1i—Sn1—S1i87.973 (15)C1—S1—Sn1104.35 (8)
Br2i—Sn1—S192.069 (15)C2ii—S1—Sn1105.15 (8)
Br2—Sn1—S187.931 (15)C2—C1—S1111.83 (17)
Br1—Sn1—S187.973 (15)C2—C1—H11109.2
Br1i—Sn1—S192.027 (15)S1—C1—H11109.2
S1i—Sn1—S1180.00 (3)C2—C1—H12109.2
Sn1—Br1—H11i83.1S1—C1—H12109.2
Sn1—Br1—H21ii83.6H11—C1—H12107.9
H11i—Br1—H21ii161.5C1—C2—S1ii111.25 (17)
Sn1—Br1—H12iv106.2C1—C2—H21109.4
H11i—Br1—H12iv80.0S1ii—C2—H21109.4
H21ii—Br1—H12iv116.1C1—C2—H22109.4
Sn1—Br1—H11v110.3S1ii—C2—H22109.4
H11i—Br1—H11v104.2H21—C2—H22108.0
Br2i—Sn1—S1—C160.87 (9)Br1—Sn1—S1—C2ii46.00 (9)
Br2—Sn1—S1—C1119.13 (9)Br1i—Sn1—S1—C2ii134.00 (9)
Br1—Sn1—S1—C1150.89 (9)Sn1—S1—C1—C2170.73 (16)
Br1i—Sn1—S1—C129.11 (9)S1—C1—C2—S1ii69.0 (2)
Br2i—Sn1—S1—C2ii44.02 (9)C1—C2—S1ii—C1ii61.7 (2)
Br2—Sn1—S1—C2ii135.98 (9)C2ii—S1—C1—C262.1 (2)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+2; (iii) x1, y, z1; (iv) x, y, z1; (v) x+1/2, y1/2, z+3/2; (vi) x+1/2, y1/2, z+1/2.
Selected bond lengths (Å) top
Br1—H11i2.9646Br1—H12iv3.0783
Br1—H21ii2.9932Br1—H11v3.0788
Br2—H22iii2.9438Br1—Br2vi3.5724 (4)
Symmetry codes: (i) x, y, z+1; (ii) x+1, y, z+2; (iii) x1, y, z1; (iv) x, y, z1; (v) x+1/2, y1/2, z+3/2; (vi) x+1/2, y1/2, z+1/2.
 

Acknowledgements

We thanks the state of Lower-Saxony and the Deutsche Forschungsgemeinschaft for funding the diffractometer.

References

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First citationMacrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar

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