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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): m11.
Published online 2007 December 6. doi:  10.1107/S1600536807062502
PMCID: PMC2914904

(Di-2-pyridyl sulfide-κ2 N,N′)diiodidozinc(II)

Abstract

The title compound, [ZnI2(C10H8N2S)], contains a six-membered chelate ring adopting a boat conformation in which the Zn atom is coordinated by two iodide ions and by the two pyridyl N atoms of a single di-2-pyridyl sulfide ligand within a slightly distorted tetra­hedron. The Zn, S and I atoms are located on a crystallographic mirror plane. As usual for this type of complex, the sulfide group does not participate in zinc coordination. The dihedral angle between the two pyridine rings is 60.1 (1)°.

Related literature

For related literature, see: Anderson & Steel (1998 [triangle]); Bhosekar et al. (2007 [triangle]); Kondo et al. (1995 [triangle]); Nicolò et al. (1996 [triangle]); Teles et al. (1999 [triangle]); Tresoldi et al. (1991 [triangle], 1992 [triangle]).

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Object name is e-64-00m11-scheme1.jpg

Experimental

Crystal data

  • [ZnI2(C10H8N2S)]
  • M r = 507.41
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-00m11-efi1.jpg
  • a = 13.9418 (8) Å
  • b = 10.9742 (10) Å
  • c = 9.1913 (6) Å
  • V = 1406.27 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 6.26 mm−1
  • T = 170 (2) K
  • 0.15 × 0.11 × 0.08 mm

Data collection

  • Stoe IPDS-1 diffractometer
  • Absorption correction: numerical (X-SHAPE; Stoe, 1998a [triangle]) T min = 0.352, T max = 0.464
  • 11604 measured reflections
  • 1784 independent reflections
  • 1535 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.029
  • wR(F 2) = 0.074
  • S = 1.02
  • 1784 reflections
  • 80 parameters
  • H-atom parameters constrained
  • Δρmax = 0.90 e Å−3
  • Δρmin = −0.86 e Å−3

Data collection: IPDS (Stoe, 1998b [triangle]); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: XP in SHELXTL (Bruker, 1998 [triangle]); software used to prepare material for publication: CIFTAB in SHELXTL.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807062502/bt2649sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062502/bt2649Isup2.hkl

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

Acknowledgments

This work was supported by the state of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (projekt No. NA 720/1-1). The authors are grateful to Professor Dr Wolfgang Bensch for the use of his experimental equipment.

supplementary crystallographic information

Comment

Recently, we are interested in the synthesis, structures and thermal properties of coordination polymers based on zinc(II) halides and N-donor ligands (Bhosekar et al., 2007). We have found for example that most of the ligand rich compounds can be transformed into ligand deficient compounds on heating. Starting from these findings we have initiated systematic investigations on this topic. In these investigations we have reacted zinc(II) iodine with 2,2'-bipyridyldisulfide. In this reaction, simultaneously a cleavage of the S—S bond takes place leading to the formation of di-2'pyridyl sulfide (dps). In further reaction with zinc(II) iodine the title compound (I) has been formed. To identify this product in further reaction by X-ray powder diffraction, a structure determination was performed.

In general dps is a versatile ambidentate ligand that, due to its conformational flexibility, can act in N,N'-bidentate (Tresoldi et al., 1992; Kondo et al., 1995 and Nicolò et al., 1996) or bridging (Tresoldi et al., 1991 and Teles et al., 1999) coordination modes toward many metals, resulting in complexes with different stereochemistry. When dps is connected to the metal atom as a chelate ligand, a six-membered ring in boat conformation is formed, differently from its rigid analogues 2,2'-bipyridine that generates a pentacyclic chelate in a planar arragement. In addition, in some cases dps can act as tridentate ligand in a N,N,S-coordination mode involving metal-sulfur interactions (Anderson & Steel, 1998).

In the crystal structure the coordination geometry about the Zn(II) ion is almost tetrahedral with bonds being formed to two iodine ions and the two pyridyl nitrogen atoms of a single dps ligand (Fig. 1). These latter interactions result in the formation of a six-membered chelate ring, which is in a boat conformation. The angles at Zn(II) range from 93.85 to 108.33°, the largest being N—Zn—I. The Zn—I and Zn—N distances are in the range of 2.5447 (6)–2.5473 (6) and 2.063 (3) Å. The structural parameters in the dps molecule are quite regular. In particular the C—S bond, 1.775 Å, is in good agreement with those expected for C(sp2)-S bonds (1.77 Å).

Experimental

ZnI2 and 2,2'-bipyridyldisulfide was obtained from Alfa Aesar and methanol was obtained from Fluka. 0.125 mmol (39.9 mg) zinc(II) iodine, 0.125 mmol (27.6 mg) 2,2'-bipyridyldisulfide and 3 ml of methanol were transfered in test-tube, which were closed and heated to 110 °C for four days. On cooling colourless block-shaped single crystals of (I) are obtained.

Refinement

All H atoms were located in difference map but were positioned with idealized geometry and were refined isotropic with Ueq(H) = 1.2 Ueq(C) of the parent atom using a riding model with C—H = 0.95 Å.

Figures

Fig. 1.
Crystal structure of compound I with labelling and displacement ellipsoids drawn at the 50% probability level. Symmetry code: i = x, -y + 1/2, z.

Crystal data

[ZnI2(C10H8N2S)]Dx = 2.397 Mg m3
Mr = 507.41Mo Kα radiation λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 8000 reflections
a = 13.9418 (8) Åθ = 11.2–26.1º
b = 10.9742 (10) ŵ = 6.26 mm1
c = 9.1913 (6) ÅT = 170 (2) K
V = 1406.27 (18) Å3Block, colourless
Z = 40.15 × 0.11 × 0.08 mm
F000 = 936

Data collection

Stoe IPDS-1 diffractometer1784 independent reflections
Radiation source: fine-focus sealed tube1535 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.029
T = 170(2) Kθmax = 28.1º
[var phi] scansθmin = 2.7º
Absorption correction: numerical(X-SHAPE; Stoe, 1998a)h = −18→16
Tmin = 0.352, Tmax = 0.464k = −14→14
11604 measured reflectionsl = −12→12

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.029  w = 1/[σ2(Fo2) + (0.0526P)2 + 0.1693P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.074(Δ/σ)max = 0.001
S = 1.03Δρmax = 0.90 e Å3
1784 reflectionsΔρmin = −0.86 e Å3
80 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0034 (4)
Secondary atom site location: difference Fourier map

Special details

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)

xyzUiso*/Ueq
Zn10.51405 (4)0.25000.14382 (5)0.02090 (14)
I10.33175 (2)0.25000.15746 (4)0.03580 (13)
I20.58755 (3)0.2500−0.10991 (4)0.03770 (13)
N10.57748 (16)0.3873 (2)0.2632 (3)0.0221 (5)
C10.5819 (2)0.3762 (3)0.4090 (4)0.0235 (6)
C20.6253 (2)0.4633 (3)0.4967 (4)0.0330 (7)
H20.62620.45430.59950.040*
C30.6670 (3)0.5630 (3)0.4311 (5)0.0413 (9)
H30.69690.62390.48870.050*
C40.6652 (3)0.5741 (3)0.2819 (5)0.0421 (9)
H40.69460.64180.23550.050*
C50.6195 (3)0.4844 (3)0.2005 (4)0.0318 (7)
H50.61800.49190.09760.038*
S10.52435 (9)0.25000.49261 (12)0.0301 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0163 (3)0.0259 (3)0.0205 (2)0.000−0.00265 (17)0.000
I10.01489 (17)0.0493 (2)0.0432 (2)0.000−0.00252 (12)0.000
I20.0333 (2)0.0592 (2)0.02065 (18)0.0000.00223 (11)0.000
N10.0176 (12)0.0218 (11)0.0268 (13)0.0006 (9)−0.0008 (10)−0.0019 (10)
C10.0157 (14)0.0288 (14)0.0259 (15)0.0046 (11)−0.0004 (11)−0.0062 (12)
C20.0242 (16)0.0354 (17)0.0393 (19)0.0040 (13)−0.0057 (15)−0.0157 (14)
C30.0300 (18)0.0322 (17)0.062 (3)0.0007 (14)−0.0065 (17)−0.0214 (18)
C40.0347 (19)0.0209 (15)0.071 (3)−0.0038 (13)0.0040 (19)−0.0020 (16)
C50.0303 (17)0.0251 (14)0.0400 (19)0.0002 (13)0.0018 (15)0.0039 (13)
S10.0313 (6)0.0379 (6)0.0210 (5)0.0000.0053 (4)0.000

Geometric parameters (Å, °)

Zn1—N12.063 (3)C2—C31.378 (6)
Zn1—N1i2.063 (3)C2—H20.9500
Zn1—I12.5447 (6)C3—C41.377 (7)
Zn1—I22.5473 (6)C3—H30.9500
N1—C51.346 (4)C4—C51.391 (5)
N1—C11.347 (4)C4—H40.9500
C1—C21.389 (4)C5—H50.9500
C1—S11.775 (3)S1—C1i1.775 (3)
N1—Zn1—N1i93.85 (14)C3—C2—H2120.8
N1—Zn1—I1113.69 (7)C1—C2—H2120.8
N1i—Zn1—I1113.69 (7)C4—C3—C2120.0 (3)
N1—Zn1—I2108.33 (8)C4—C3—H3120.0
N1i—Zn1—I2108.33 (8)C2—C3—H3120.0
I1—Zn1—I2116.54 (2)C3—C4—C5118.7 (3)
C5—N1—C1118.6 (3)C3—C4—H4120.6
C5—N1—Zn1122.5 (2)C5—C4—H4120.6
C1—N1—Zn1118.8 (2)N1—C5—C4122.0 (4)
N1—C1—C2122.3 (3)N1—C5—H5119.0
N1—C1—S1118.8 (2)C4—C5—H5119.0
C2—C1—S1118.8 (3)C1—S1—C1i102.5 (2)
C3—C2—C1118.4 (3)

Symmetry codes: (i) x, −y+1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2649).

References

  • Anderson, R. J. & Steel, P. J. (1998). Acta Cryst. C54, 223–225.
  • Bhosekar, G., Jess, I. & Näther, C. (2007). Inorg. Chem.43, 6508–6515. [PubMed]
  • Bruker (1998). SHELXTL Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Kondo, M., Kawata, S., Kitagawa, S., Kiso, H. & Munakata, M. (1995). Acta Cryst. C51, 567–569.
  • Nicolò, F., Bruno, G. & Tresoldi, G. (1996). Acta Cryst. C52, 2188–2191.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Stoe (1998a). X-SHAPE Version 1.03. Stoe & Cie, Darmstadt, Germany.
  • Stoe (1998b). IPDS Version 2.89. Stoe & Cie, Darmstadt, Germany.
  • Teles, W. M., Fernandes, N. G., Abras, A. & Filgueiras, C. A. L. (1999). Transit. Met. Chem.24, 321–325.
  • Tresoldi, G., Piraino, P., Rotondo, E. & Faraone, F. (1991). J. Chem. Soc.Dalton Trans. pp. 425–430.
  • Tresoldi, G., Rotondo, E., Piraino, P., Lanfranchi, M. & Tiripichio, A. (1992). Inorg. Chim. Acta, 194, 233–241.

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