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

Reuter, H.; Röwekamp-Krugley, N.; Imwalle, M.; Keil, S.; Reichelt, M.

doi:10.1107/S2056989015023932

metal-organic compounds

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Volume 71| Part 12| December 2015| Pages m267-m268

https://doi.org/10.1107/S2056989015023932

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

Hans Reuter,^a ^* Natalia Röwekamp-Krugley,^a Marius Imwalle,^a Simona Keil ^a and Martin Reichelt ^a

^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.

Keywords: crystal structure; tin(IV) bromide; 1,4-dithiane; coordination polymer; Br⋯Br interactions; Br⋯H interactions.

CCDC reference: 1442283

1. Related literature

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

2. Experimental

2.1. Crystal data

[SnBr₄(C₄H₈S₂)]
M_r = 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 ) T_min = 0.182, T_max = 0.450
22217 measured reflections
1426 independent reflections
1339 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Selected contacts (Å)

Br1⋯H11ⁱ	2.965
Br1⋯H21ⁱⁱ	2.993
Br2⋯H22ⁱⁱⁱ	2.944
Br1⋯H12^iv	3.078
Br1⋯H11^v	3.079
Br1⋯Br2^vi	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); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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).

Supporting information

CCDC reference: 1442283

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015023932/nr2064sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015023932/nr2064Isup2.hkl

checkCIF report

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

Synthesis and crystallization top

Refinement details top

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

	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.
	Fig. 2. Part of the one-dimensional coordination polymer showing two complete building units.
	Fig. 3. Perspective view of the crystal structure looking down the a axis.
	Fig. 4. Shortest intrachain H···Br (blue) and interchain Br···Br (red) interactions.
	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
M_r = 558.55	D_x = 3.160 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.1033 (4) Å	Cell parameters from 9935 reflections
b = 12.0526 (8) Å	θ = 3.4–28.7°
c = 7.4032 (5) Å	µ = 16.09 mm⁻¹
β = 112.144 (2)°	T = 100 K
V = 587.06 (7) Å³	Needle, yellow
Z = 2	0.16 × 0.06 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	1339 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.066
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θ_max = 28.0°, θ_min = 3.4°
T_min = 0.182, T_max = 0.450	h = −9→9
22217 measured reflections	k = −15→15
1426 independent reflections	l = −9→9

Refinement top

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)] = 0.017	H-atom parameters constrained
wR(F²) = 0.036	w = 1/[σ²(F_o²) + (0.0043P)² + 0.5753P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max < 0.001
1426 reflections	Δρ_max = 0.72 e Å⁻³
54 parameters	Δρ_min = −0.46 e Å⁻³
0 restraints	Extinction correction: SHELXL2014/7 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0042 (3)

Crystal data top

[SnBr₄(C₄H₈S₂)]	V = 587.06 (7) Å³
M_r = 558.55	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.1033 (4) Å	µ = 16.09 mm⁻¹
b = 12.0526 (8) Å	T = 100 K
c = 7.4032 (5) Å	0.16 × 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)
T_min = 0.182, T_max = 0.450	R_int = 0.066
22217 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.017	0 restraints
wR(F²) = 0.036	H-atom parameters constrained
S = 1.14	Δρ_max = 0.72 e Å⁻³
1426 reflections	Δρ_min = −0.46 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Sn1	0.0000	0.0000	0.5000	0.00740 (7)
Br1	0.17963 (4)	−0.12497 (2)	0.33464 (3)	0.01109 (8)
Br2	0.04504 (4)	0.16589 (2)	0.30464 (4)	0.01267 (8)
S1	0.36282 (9)	0.04681 (5)	0.76832 (9)	0.01033 (13)
C1	0.3132 (4)	0.0756 (2)	0.9867 (3)	0.0119 (5)
H11	0.2349	0.1455	0.9686	0.015 (4)*
H12	0.2295	0.0151	1.0078	0.015 (4)*
C2	0.5088 (4)	0.0860 (2)	1.1657 (4)	0.0129 (5)
H21	0.4771	0.1146	1.2764	0.015 (4)*
H22	0.6002	0.1399	1.1388	0.015 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.00749 (13)	0.00663 (12)	0.00903 (13)	0.00013 (8)	0.00420 (9)	0.00008 (8)
Br1	0.01171 (14)	0.01121 (13)	0.01229 (14)	0.00266 (9)	0.00672 (10)	−0.00103 (9)
Br2	0.01522 (15)	0.00948 (13)	0.01585 (14)	0.00006 (9)	0.00873 (11)	0.00347 (9)
S1	0.0096 (3)	0.0106 (3)	0.0110 (3)	0.0001 (2)	0.0041 (2)	0.0002 (2)
C1	0.0122 (12)	0.0131 (12)	0.0102 (12)	0.0027 (10)	0.0041 (10)	−0.0012 (10)
C2	0.0121 (12)	0.0117 (12)	0.0124 (12)	0.0029 (10)	0.0017 (10)	−0.0038 (10)

Geometric parameters (Å, º) top

Sn1—Br2ⁱ	2.5574 (3)	Br1—H11^v	3.0788
Sn1—Br2	2.5574 (3)	Br1—Br2^vi	3.5724 (4)
Sn1—Br1	2.5638 (2)	S1—C1	1.813 (2)
Sn1—Br1ⁱ	2.5638 (3)	S1—C2ⁱⁱ	1.816 (3)
Sn1—S1ⁱ	2.6546 (6)	C1—C2	1.521 (3)
Sn1—S1	2.6546 (6)	C1—H11	0.9900
Br1—H11ⁱ	2.9646	C1—H12	0.9900
Br1—H21ⁱⁱ	2.9932	C2—S1ⁱⁱ	1.816 (3)
Br2—H22ⁱⁱⁱ	2.9438	C2—H21	0.9900
Br1—H12^iv	3.0783	C2—H22	0.9900

Br2ⁱ—Sn1—Br2	180.0	H21ⁱⁱ—Br1—H11^v	68.8
Br2ⁱ—Sn1—Br1	90.092 (9)	H12^iv—Br1—H11^v	143.5
Br2—Sn1—Br1	89.908 (9)	Sn1—Br1—Br2^vi	167.821 (10)
Br2ⁱ—Sn1—Br1ⁱ	89.908 (9)	H11ⁱ—Br1—Br2^vi	102.6
Br2—Sn1—Br1ⁱ	90.092 (9)	H21ⁱⁱ—Br1—Br2^vi	88.3
Br1—Sn1—Br1ⁱ	180.0	H12^iv—Br1—Br2^vi	85.5
Br2ⁱ—Sn1—S1ⁱ	87.931 (15)	H11^v—Br1—Br2^vi	58.0
Br2—Sn1—S1ⁱ	92.069 (15)	Sn1—Br2—H22ⁱⁱⁱ	79.0
Br1—Sn1—S1ⁱ	92.027 (15)	C1—S1—C2ⁱⁱ	100.11 (12)
Br1ⁱ—Sn1—S1ⁱ	87.973 (15)	C1—S1—Sn1	104.35 (8)
Br2ⁱ—Sn1—S1	92.069 (15)	C2ⁱⁱ—S1—Sn1	105.15 (8)
Br2—Sn1—S1	87.931 (15)	C2—C1—S1	111.83 (17)
Br1—Sn1—S1	87.973 (15)	C2—C1—H11	109.2
Br1ⁱ—Sn1—S1	92.027 (15)	S1—C1—H11	109.2
S1ⁱ—Sn1—S1	180.00 (3)	C2—C1—H12	109.2
Sn1—Br1—H11ⁱ	83.1	S1—C1—H12	109.2
Sn1—Br1—H21ⁱⁱ	83.6	H11—C1—H12	107.9
H11ⁱ—Br1—H21ⁱⁱ	161.5	C1—C2—S1ⁱⁱ	111.25 (17)
Sn1—Br1—H12^iv	106.2	C1—C2—H21	109.4
H11ⁱ—Br1—H12^iv	80.0	S1ⁱⁱ—C2—H21	109.4
H21ⁱⁱ—Br1—H12^iv	116.1	C1—C2—H22	109.4
Sn1—Br1—H11^v	110.3	S1ⁱⁱ—C2—H22	109.4
H11ⁱ—Br1—H11^v	104.2	H21—C2—H22	108.0

Br2ⁱ—Sn1—S1—C1	−60.87 (9)	Br1—Sn1—S1—C2ⁱⁱ	−46.00 (9)
Br2—Sn1—S1—C1	119.13 (9)	Br1ⁱ—Sn1—S1—C2ⁱⁱ	134.00 (9)
Br1—Sn1—S1—C1	−150.89 (9)	Sn1—S1—C1—C2	170.73 (16)
Br1ⁱ—Sn1—S1—C1	29.11 (9)	S1—C1—C2—S1ⁱⁱ	−69.0 (2)
Br2ⁱ—Sn1—S1—C2ⁱⁱ	44.02 (9)	C1—C2—S1ⁱⁱ—C1ⁱⁱ	61.7 (2)
Br2—Sn1—S1—C2ⁱⁱ	−135.98 (9)	C2ⁱⁱ—S1—C1—C2	62.1 (2)

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+1/2, y−1/2, −z+3/2; (vi) −x+1/2, y−1/2, −z+1/2.

Selected bond lengths (Å) top

Br1—H11ⁱ	2.9646	Br1—H12^iv	3.0783
Br1—H21ⁱⁱ	2.9932	Br1—H11^v	3.0788
Br2—H22ⁱⁱⁱ	2.9438	Br1—Br2^vi	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+1/2, y−1/2, −z+3/2; (vi) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

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

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 12| December 2015| Pages m267-m268

https://doi.org/10.1107/S2056989015023932

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

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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