supporting information

Acta Cryst. (2013). E69, m618    [ doi:10.1107/S1600536813028377 ]

Hexa­kis­(dimethyl sulfoxide-[kappa]O)zinc(II) poly­iodide

L. Garzón-Tovar, Á. Duarte-Ruiz and P. E. Fanwick

CCDC reference: 966631

Abstract top

The title compound, [Zn{(CH3)2SO}6]I4, is a one-dimensional supra­molecular polymer along a threefold rotation axis of the space group. It is built up from discrete [Zn{(CH3)2SO}6]2+ units connected through non-classical hydrogen bonds to linear I42- polyiodide anions (C-H...I = 3.168 Å). The ZnII ion in the cation has an octa­hedral coordination geometry, with all six Zn-O bond lengths being equivalent, at 2.111 (4) Å. The linear polyiodide anion contains a neutral I2 mol­ecule weakly coordinated to two iodide ions.

Comment top

Supramolecular polymers are defined as polymeric systems that extend beyond the molecule by a process of self-assembly between monomer units directed by noncovalent interactions (Huang & Scherman, 2012). These noncovalent forces, such as hydrogen bonding, coordination bonds, ππ stacking and electrostatic forces act as driving forces to construct a well defined supramolecular architectures (Fromm, 2001); however, there are a few examples where non-classical hydrogen bonds such as C—H···I are used to construct these structures (Youm et al., 2006). Previous studies have suggested that a coordination complex with DMSO such as [Cu(DMSO)6]2+ acts as monomeric units connected through a self-assembly process with tetraiodide ions driven by weak non-classical hydrogen bonds C—H···I to form a one-dimensional supramolecular polymer (Garzón-Tovar et al., 2013). Herein we report the synthesis and structural characterization of a new supramolecular polymer.

In the title compound, [Zn{(CH3)2SO}6]I4, the Zn(II) ion is located on a 3-fold inversion axis being coordinated by six equidistant oxygen-bonded dimethyl sulfoxide ligands (Fig. 1). The Zn—O bond distances in the [Zn(DMSO)6]2+ complex are 2.111 (4) Å and 87.28 (16), 92.71 (16) ° bond angles. The linear tetraiodide chain presents a neutral I—I molecule with bond distance of 2.8417 (18) Å, weakly coordinated with two iodide (I-) anions (bond distance 3.335 (1) Å). This result is in agreement with other studies, where the I42- correspond to interaction of two I- anions with one I2 molecule (Iδ-(I—I)Iδ-) (Long et al.,1999). The two end-iodide anions build up three weak hydrogen bonds to the hydrogen atoms of the methyl groups with distances of 3.167 Å (Fig. 2) to form a one-dimensional supramolecular polymer.

Related literature top

For related structures, see Garzón-Tovar et al. (2013); Long et al. (1999); Tkachev et al. (1994). For supramolecular polymers formed by non-classical hydrogen bonds, see: Fromm (2001); Huang & Scherman (2012); Youm et al. (2006). For polyiodide compounds, see: Svensson & Kloo (2003).

Experimental top

Zinc (II) chloride (1.1404 g, 8.3659 mmol) was added to a DMSO (16.506 g, 211.26 mmol) and distilled water (0.199 g, 11.1 mmol) solution. After colorless mixture was ultrasonicated for 20 min, CH3I (3.420 g, 24.09 mmol) was added, and ultrasonication was continued for an additional 20 min. The resulting yellow solution was kept at 20°C for 8 d, with continuous agitation. The mixture was filtered, and the filtrate was refrigerated at 4°C for 30 d, after which blue crystals with a metallic luster formed. The crystals of [Zn{(CH3)2SO}6]I4 were filtered and dried under vacuum. The yield obtained was 0.3231 g.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms represented by small spheres of arbitrary radii.
[Figure 2] Fig. 2. The crystal packing of the title compound viewed along the b axis. The C—H···I hydrogen bonds are shown as dashed lines.
Hexakis(dimethyl sulfoxide-κO)zinc(II) polyiodide top
Crystal data top
[Zn(C2H6OS)6]I4Dx = 2.169 Mg m3
Mr = 1041.79Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 3127 reflections
Hall symbol: -R 3θ = 3–30°
a = 11.8399 (7) ŵ = 5.06 mm1
c = 19.7110 (12) ÅT = 298 K
V = 2393.0 (2) Å3Plate, 1orange
Z = 30.60 × 0.40 × 0.40 mm
F(000) = 1482
Data collection top
Nonius KappaCCD
1251 reflections with > 2.0σ(I)
Graphite 002 monochromatorRint = 0.036
ω scansθmax = 30.0°, θmin = 2.9°
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
h = 016
Tmin = 0.126, Tmax = 0.132k = 140
3127 measured reflectionsl = 2727
1512 independent reflections
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full 1/[σ2(Fo2) + (0.P)2 + 55.1589P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.047(Δ/σ)max < 0.001
wR(F2) = 0.104Δρmax = 1.00 e Å3
S = 1.17Δρmin = 1.23 e Å3
1512 reflectionsExtinction correction: SHELXL97 (Sheldrick, 2008)
48 parametersExtinction coefficient: 0.30E-02
0 restraints
Crystal data top
[Zn(C2H6OS)6]I4Z = 3
Mr = 1041.79Mo Kα radiation
Trigonal, R3µ = 5.06 mm1
a = 11.8399 (7) ÅT = 298 K
c = 19.7110 (12) Å0.60 × 0.40 × 0.40 mm
V = 2393.0 (2) Å3
Data collection top
Nonius KappaCCD
1512 independent reflections
Absorption correction: multi-scan
(SCALEPACK; Otwinowski & Minor, 1997)
1251 reflections with > 2.0σ(I)
Tmin = 0.126, Tmax = 0.132Rint = 0.036
3127 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.104H-atom parameters constrained
S = 1.17 1/[σ2(Fo2) + (0.P)2 + 55.1589P]
where P = (Fo2 + 2Fc2)/3
1512 reflectionsΔρmax = 1.00 e Å3
48 parametersΔρmin = 1.23 e Å3
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. Outlier data were removed using a local program based on the method of Prince and Nicholson.

Refinement on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R_factor_obs 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
I10.66670.33330.59206 (4)0.0430 (3)
I20.00000.00000.42791 (5)0.0466 (3)
Zn10.66670.33330.33330.0258 (3)
S10.62508 (13)0.54407 (13)0.40794 (8)0.0316 (3)
O10.7243 (4)0.5025 (4)0.3922 (2)0.0324 (9)
C10.6592 (7)0.6747 (6)0.3515 (4)0.0423 (15)
C20.6825 (8)0.6355 (7)0.4845 (3)0.0478 (16)
Atomic displacement parameters (Å2) top
I10.0445 (3)0.0445 (3)0.0400 (4)0.02223 (15)0.00000.0000
I20.0356 (3)0.0356 (3)0.0688 (6)0.01778 (14)0.00000.0000
Zn10.0221 (4)0.0221 (4)0.0331 (8)0.0111 (2)0.00000.0000
S10.0264 (6)0.0250 (6)0.0409 (8)0.0110 (5)0.0057 (5)0.0013 (5)
O10.033 (2)0.0274 (18)0.040 (2)0.0174 (16)0.0017 (17)0.0037 (16)
C10.049 (4)0.038 (3)0.049 (4)0.028 (3)0.005 (3)0.008 (3)
C20.066 (5)0.044 (4)0.037 (3)0.030 (4)0.003 (3)0.009 (3)
Geometric parameters (Å, º) top
I2—I2i2.8417 (18)S1—C11.780 (6)
Zn1—O1ii2.111 (4)S1—C21.782 (7)
Zn1—O1iii2.111 (4)C1—H1A0.9600
Zn1—O1iv2.111 (4)C1—H1B0.9600
Zn1—O12.111 (4)C1—H1C0.9600
Zn1—O1v2.111 (4)C2—H2A0.9600
Zn1—O1vi2.111 (4)C2—H2B0.9600
S1—O11.515 (4)C2—H2C0.9600
O1ii—Zn1—O1iii179.9980 (10)O1—S1—C2104.4 (3)
O1ii—Zn1—O1iv87.29 (16)C1—S1—C298.6 (3)
O1iii—Zn1—O1iv92.71 (16)S1—O1—Zn1119.0 (2)
O1ii—Zn1—O187.29 (16)S1—C1—H1A109.50
O1iii—Zn1—O192.71 (16)S1—C1—H1B109.50
O1iv—Zn1—O192.71 (16)H1A—C1—H1B109.50
O1ii—Zn1—O1v92.71 (16)S1—C1—H1C109.50
O1iii—Zn1—O1v87.29 (16)H1A—C1—H1C109.50
O1iv—Zn1—O1v179.9980 (10)H1B—C1—H1C109.50
O1—Zn1—O1v87.29 (16)S1—C2—H2A109.50
O1ii—Zn1—O1vi92.71 (16)S1—C2—H2B109.50
O1iii—Zn1—O1vi87.29 (16)H2A—C2—H2B109.50
O1iv—Zn1—O1vi87.29 (16)S1—C2—H2C109.50
O1v—Zn1—O1vi92.71 (15)H2B—C2—H2C109.50
O1—S1—C1106.1 (3)
C1—S1—O1—Zn1101.8 (3)O1iv—Zn1—O1—S148.4 (3)
C2—S1—O1—Zn1154.6 (3)O1v—Zn1—O1—S1131.6 (3)
O1ii—Zn1—O1—S138.74 (19)O1vi—Zn1—O1—S1112 (10)
O1iii—Zn1—O1—S1141.26 (19)
Symmetry codes: (i) x, y, z+1; (ii) xy+1/3, x1/3, z+2/3; (iii) x+y+1, x+1, z; (iv) y+1, xy, z; (v) y+1/3, x+y+2/3, z+2/3; (vi) x+4/3, y+2/3, z+2/3.

Experimental details

Crystal data
Chemical formula[Zn(C2H6OS)6]I4
Crystal system, space groupTrigonal, R3
Temperature (K)298
a, c (Å)11.8399 (7), 19.7110 (12)
V3)2393.0 (2)
Radiation typeMo Kα
µ (mm1)5.06
Crystal size (mm)0.60 × 0.40 × 0.40
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
(SCALEPACK; Otwinowski & Minor, 1997)
Tmin, Tmax0.126, 0.132
No. of measured, independent and
observed [ > 2.0σ(I)] reflections
3127, 1512, 1251
(sin θ/λ)max1)0.703
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.104, 1.17
No. of reflections1512
No. of parameters48
H-atom treatmentH-atom parameters constrained
1/[σ2(Fo2) + (0.P)2 + 55.1589P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)1.00, 1.23

Computer programs: COLLECT (Nonius, 1998), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Acknowledgements top

We would like to acknowledge the financial support given by the Universidad Nacional de Colombia, Bogotá.