Hexa-kis-(dimethyl sulfoxide-κO)zinc(II) poly-iodide.

The title compound, [Zn{(CH3)2SO}6]I4, is a one-dimensional supra-molecular 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 I4 (2-) polyiodide anions (C-H⋯I = 3.168 Å). The Zn(II) ion in the cation has an octa-hedral coordination geometry, with all six Zn-O bond lengths being equivalent, at 2.111 (4) Å. The linear polyiodide anion contains a neutral I2 mol-ecule weakly coordinated to two iodide ions.

Related literature

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

Crystal data

[Zn(C2H6OS)6]I4

M = 1041.79

Triggonal,

a = 11.8399 (7) Å

c = 19.7110 (12) Å

V = 2393.0 (2) Å3

Z = 3

Mo Kα radiation

μ = 5.06 mm−1

T = 298 K

0.60 × 0.40 × 0.40 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T min = 0.126, T max = 0.132

3127 measured reflections

1512 independent reflections

1251 reflections with > 2.0σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.104

S = 1.17

1512 reflections

48 parameters

H-atom parameters constrained

Δρmax = 1.00 e Å−3

Δρmin = −1.23 e Å−3

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; 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 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813028377/fj2643sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813028377/fj2643Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zn(C2H6OS)6]I4	Dx = 2.169 Mg m−3
Mr = 1041.79	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 3127 reflections
Hall symbol: -R 3	θ = 3–30°
a = 11.8399 (7) Å	µ = 5.06 mm−1
c = 19.7110 (12) Å	T = 298 K
V = 2393.0 (2) Å3	Plate, 1orange
Z = 3	0.60 × 0.40 × 0.40 mm
F(000) = 1482

Nonius KappaCCD diffractometer	1251 reflections with > 2.0σ(I)
Graphite 002 monochromator	Rint = 0.036
ω scans	θmax = 30.0°, θmin = 2.9°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = 0→16
Tmin = 0.126, Tmax = 0.132	k = −14→0
3127 measured reflections	l = −27→27
1512 independent reflections

Refinement on F2	H-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) = 0.104	Δρmax = 1.00 e Å−3
S = 1.17	Δρmin = −1.23 e Å−3
1512 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008)
48 parameters	Extinction coefficient: 0.30E-02
0 restraints

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.

	x	y	z	Uiso*/Ueq
I1	0.6667	0.3333	0.59206 (4)	0.0430 (3)
I2	0.0000	0.0000	0.42791 (5)	0.0466 (3)
Zn1	0.6667	0.3333	0.3333	0.0258 (3)
S1	0.62508 (13)	0.54407 (13)	0.40794 (8)	0.0316 (3)
O1	0.7243 (4)	0.5025 (4)	0.3922 (2)	0.0324 (9)
C1	0.6592 (7)	0.6747 (6)	0.3515 (4)	0.0423 (15)
C2	0.6825 (8)	0.6355 (7)	0.4845 (3)	0.0478 (16)
H1A	0.7491	0.7411	0.3559	0.063*
H1B	0.6045	0.7105	0.3625	0.063*
H1C	0.6425	0.6428	0.3057	0.063*
H2A	0.6836	0.5804	0.5199	0.072*
H2B	0.6256	0.6680	0.4972	0.072*
H2C	0.7691	0.7074	0.4776	0.072*

	U11	U22	U33	U12	U13	U23
I1	0.0445 (3)	0.0445 (3)	0.0400 (4)	0.02223 (15)	0.0000	0.0000
I2	0.0356 (3)	0.0356 (3)	0.0688 (6)	0.01778 (14)	0.0000	0.0000
Zn1	0.0221 (4)	0.0221 (4)	0.0331 (8)	0.0111 (2)	0.0000	0.0000
S1	0.0264 (6)	0.0250 (6)	0.0409 (8)	0.0110 (5)	0.0057 (5)	−0.0013 (5)
O1	0.033 (2)	0.0274 (18)	0.040 (2)	0.0174 (16)	0.0017 (17)	−0.0037 (16)
C1	0.049 (4)	0.038 (3)	0.049 (4)	0.028 (3)	0.005 (3)	0.008 (3)
C2	0.066 (5)	0.044 (4)	0.037 (3)	0.030 (4)	0.003 (3)	−0.009 (3)

I2—I2i	2.8417 (18)	S1—C1	1.780 (6)
Zn1—O1ii	2.111 (4)	S1—C2	1.782 (7)
Zn1—O1iii	2.111 (4)	C1—H1A	0.9600
Zn1—O1iv	2.111 (4)	C1—H1B	0.9600
Zn1—O1	2.111 (4)	C1—H1C	0.9600
Zn1—O1v	2.111 (4)	C2—H2A	0.9600
Zn1—O1vi	2.111 (4)	C2—H2B	0.9600
S1—O1	1.515 (4)	C2—H2C	0.9600
O1ii—Zn1—O1iii	179.9980 (10)	O1—S1—C2	104.4 (3)
O1ii—Zn1—O1iv	87.29 (16)	C1—S1—C2	98.6 (3)
O1iii—Zn1—O1iv	92.71 (16)	S1—O1—Zn1	119.0 (2)
O1ii—Zn1—O1	87.29 (16)	S1—C1—H1A	109.50
O1iii—Zn1—O1	92.71 (16)	S1—C1—H1B	109.50
O1iv—Zn1—O1	92.71 (16)	H1A—C1—H1B	109.50
O1ii—Zn1—O1v	92.71 (16)	S1—C1—H1C	109.50
O1iii—Zn1—O1v	87.29 (16)	H1A—C1—H1C	109.50
O1iv—Zn1—O1v	179.9980 (10)	H1B—C1—H1C	109.50
O1—Zn1—O1v	87.29 (16)	S1—C2—H2A	109.50
O1ii—Zn1—O1vi	92.71 (16)	S1—C2—H2B	109.50
O1iii—Zn1—O1vi	87.29 (16)	H2A—C2—H2B	109.50
O1iv—Zn1—O1vi	87.29 (16)	S1—C2—H2C	109.50
O1—Zn1—O1vi	180.00	H2A—C2—H2C	109.50
O1v—Zn1—O1vi	92.71 (15)	H2B—C2—H2C	109.50
O1—S1—C1	106.1 (3)
C1—S1—O1—Zn1	−101.8 (3)	O1iv—Zn1—O1—S1	−48.4 (3)
C2—S1—O1—Zn1	154.6 (3)	O1v—Zn1—O1—S1	131.6 (3)
O1ii—Zn1—O1—S1	38.74 (19)	O1vi—Zn1—O1—S1	112 (10)
O1iii—Zn1—O1—S1	−141.26 (19)