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Acta Cryst. (2008). E64, m83    [ doi:10.1107/S1600536807063556 ]

Dibromido(di-2-pyridyl disulfide-[kappa]2N,N')zinc(II)

M. Wriedt, I. Jess and C. Näther

Abstract top

The molecular structure of the title compound, [ZnBr2(C10H8N2S2)], contains a seven-membered chelate ring in which the zinc atom is coordinated by two bromide ions and by the two pyridyl N atoms of a single 2,2'-dipyridyldisulfide (dpds) ligand within a slightly distorted tetrahedron. As is usual for this type of complex, the disulfide group does not participate in zinc coordination. The chelate complexes are connected via weak intermolecular C-H...Br hydrogen bonding into chains, which extend in the [010] direction.

Comment top

In our ongoing investigation on the synthesis, structures and properties of new coordination polymers based on zinc(II) halides and N-donor ligands (Bhosekar et al. 2007), we have startet systematic investigation of their thermal behavior because we have demonstrated that new ligand-deficient coordination polymers can be conveniently prepared by thermal decompisition of suitable ligand-rich precursur compounds (Näther et al. 2003; Näther & Jess, 2006). In further investigations we have reacted zinc(II) bromine with 2,2'-bipyridyldisulfide (dpds). In this reaction the title chelate-complex has been formed by accident.

The versatile coordination properties of dpds enables a series of different chelate-complexes and coordination polymers. It can act in N,N'-bidentate (Kinoshita et al., 2003; Kadooka et al. 1976 & Pickardtet al. 2005) or bridging (Kubo et al. 1998 & Kinoshita et al. 2003) coordination modes toward many metals. When dpds is connected to the metal atom as a chelate ligand, a seven-membered ring is formed.

The title compound is isotypic to that of the corresponding chloride compound reported by Pickardt et al. in 2005. In the crystal structure the coordination geometry about the Zn(II) ion is almost tetrahedral with bonds being formed to two bromine ions and the two pyridyl nitrogen atoms of a single dpds ligand (Fig. 1). These latter interactions result in the formation of a seven-membered chelate ring. As usual for this type of complexes, the disulfide group does not participate in zinc-coordination. Moreover the chelate-complexes form infinite weak C—H···Br intermolecular hydrogen bonded chains along the [0 1 0] direction (C12—H12: 0.95 Å, H12···Br2i: 2.84 (2) Å, C12···Br2i: 3.74 (3), C12—H12···Bri: 160 °, see Fig. 2). The Zn—Br and Zn—N distances are in the range of 2.3664 (10)–2.3897 (10) and 2.042 (5)–2.091 (5) Å. The angles at Zn(II) range from 100.99 (15) to 119.06 (4)°, the largest being Br—Zn—Br (Tab. 1). The structural parameters in the dpds molecule are quite regular. In particular the C—S bond, 1.784 (7)–1.783 (6) Å, is in good agreement with those expected for C(sp2)—S bonds (1.77 Å). The S—S bond length, 2.050 (3) Å, is somewhat longer than that found in the structure of the free ligand, 2.016 (2) Å (Raghavan & Seff, 1977).

Related literature top

For related literature, see: Bhosekar et al. (2007); Kinoshita et al. (2003); Kadooka et al. (1976); Kubo et al. (1998); Näther & Jess (2006); Näther et al. (2003); Pickardt et al. (2005); Raghavan & Seff (1977).

Experimental top

ZnBr2 and dpds was obtained from Alfa Aesar and methanol was obtained from Fluka. 0.125 mmol (28.15 mg) zinc(II) bromine, 0.125 mmol (27.5 mg) dpds and 3 ml of methanol were transfered in a test-tube, which were closed and heated to 110 °C for four days. On cooling colourless block-shaped single crystals of (I) were obtained.

Refinement top

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.

Computing details top

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

Figures top
[Figure 1] Fig. 1. : Molecular structure of the title compund with labelling and displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. : Crystal structure of the title compound with view along the [0 1 0] direction. Intermolecular C—H···Br hydrogen bonding is shown as dashed lines. Symmetry code: i = x, -1 + y, z.
Dibromido(di-2-pyridyl disulfide-κ2N,N')zinc(II) top
Crystal data top
[ZnBr2(C10H8N2S2)]Z = 2
Mr = 445.49F000 = 428
Triclinic, P1Dx = 2.177 Mg m−3
a = 7.7610 (8) ÅMo Kα radiation
λ = 0.71073 Å
b = 8.2962 (8) ÅCell parameters from 8000 reflections
c = 12.3576 (13) Åθ = 2.9–28.1º
α = 95.488 (12)ºµ = 7.97 mm−1
β = 107.161 (12)ºT = 170 (2) K
γ = 112.950 (11)ºBlock, colourless
V = 679.70 (12) Å30.09 × 0.09 × 0.08 mm
Data collection top
STOE IPDS-1
diffractometer		2167 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.054
Monochromator: graphiteθmax = 26.0º
T = 170(2) Kθmin = 2.9º
Phi scansh = −9→9
Absorption correction: nonek = −10→10
6076 measured reflectionsl = −15→15
2609 independent reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.046  w = 1/[σ2(Fo2) + (0.0684P)2 + 2.046P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.120(Δ/σ)max < 0.001
S = 1.06Δρmax = 1.31 e Å−3
2609 reflectionsΔρmin = −1.43 e Å−3
155 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0071 (16)
Secondary atom site location: difference Fourier map
Crystal data top
[ZnBr2(C10H8N2S2)]γ = 112.950 (11)º
Mr = 445.49V = 679.70 (12) Å3
Triclinic, P1Z = 2
a = 7.7610 (8) ÅMo Kα
b = 8.2962 (8) ŵ = 7.97 mm−1
c = 12.3576 (13) ÅT = 170 (2) K
α = 95.488 (12)º0.09 × 0.09 × 0.08 mm
β = 107.161 (12)º
Data collection top
STOE IPDS-1
diffractometer		2609 independent reflections
Absorption correction: none2167 reflections with I > 2σ(I)
6076 measured reflectionsRint = 0.054
Refinement top
R[F2 > 2σ(F2)] = 0.046155 parameters
wR(F2) = 0.120H-atom parameters constrained
S = 1.06Δρmax = 1.31 e Å−3
2609 reflectionsΔρmin = −1.43 e Å−3
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. 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) top
xyzUiso*/Ueq
Br10.99364 (9)0.75728 (8)0.23015 (6)0.0193 (2)
Br20.38203 (9)0.48414 (9)0.12968 (6)0.0197 (2)
Zn10.70460 (10)0.50584 (9)0.22904 (6)0.0143 (2)
S10.7276 (3)0.2365 (2)0.44635 (15)0.0223 (4)
N10.7378 (8)0.5577 (7)0.4048 (5)0.0167 (11)
C20.7679 (9)0.5176 (10)0.5987 (6)0.0222 (14)
H20.76850.44180.65170.027*
C50.7566 (10)0.7263 (9)0.4404 (5)0.0190 (13)
H50.74730.79740.38500.023*
C10.7414 (9)0.4556 (9)0.4828 (5)0.0166 (13)
C30.7933 (10)0.6913 (10)0.6347 (6)0.0248 (15)
H30.81340.73730.71310.030*
C40.7888 (10)0.7975 (10)0.5545 (7)0.0263 (15)
H40.80770.91750.57770.032*
S20.5117 (2)0.1119 (2)0.28313 (15)0.0213 (4)
N110.7411 (7)0.2888 (7)0.1671 (5)0.0151 (10)
C150.8390 (9)0.2991 (9)0.0928 (5)0.0183 (13)
H150.90640.41330.07850.022*
C110.6512 (9)0.1280 (8)0.1897 (5)0.0156 (12)
C140.8465 (10)0.1511 (10)0.0359 (6)0.0237 (15)
H140.91460.1632−0.01750.028*
C130.7523 (10)−0.0148 (9)0.0587 (6)0.0225 (14)
H130.7544−0.11890.02090.027*
C120.6535 (10)−0.0270 (9)0.1385 (6)0.0227 (14)
H120.5899−0.13860.15700.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0160 (3)0.0134 (4)0.0251 (4)0.0025 (3)0.0079 (3)0.0054 (2)
Br20.0136 (3)0.0182 (4)0.0257 (4)0.0065 (3)0.0050 (3)0.0070 (3)
Zn10.0137 (4)0.0105 (4)0.0198 (4)0.0056 (3)0.0067 (3)0.0045 (3)
S10.0257 (9)0.0218 (9)0.0254 (9)0.0145 (7)0.0097 (7)0.0113 (7)
N10.015 (3)0.018 (3)0.019 (3)0.008 (2)0.006 (2)0.006 (2)
C20.016 (3)0.035 (4)0.017 (3)0.013 (3)0.006 (3)0.007 (3)
C50.025 (3)0.018 (3)0.017 (3)0.012 (3)0.008 (3)0.005 (3)
C10.011 (3)0.021 (3)0.021 (3)0.009 (3)0.005 (2)0.007 (3)
C30.022 (3)0.038 (4)0.013 (3)0.013 (3)0.006 (3)0.001 (3)
C40.020 (3)0.021 (4)0.040 (4)0.010 (3)0.013 (3)0.006 (3)
S20.0147 (8)0.0164 (8)0.0303 (9)0.0024 (6)0.0108 (7)0.0054 (7)
N110.012 (2)0.011 (3)0.021 (3)0.005 (2)0.004 (2)0.003 (2)
C150.016 (3)0.020 (3)0.020 (3)0.009 (3)0.008 (3)0.005 (3)
C110.009 (3)0.014 (3)0.021 (3)0.005 (2)0.001 (2)0.006 (2)
C140.020 (3)0.026 (4)0.028 (4)0.014 (3)0.009 (3)0.003 (3)
C130.023 (3)0.023 (4)0.018 (3)0.013 (3)0.003 (3)−0.006 (3)
C120.025 (4)0.015 (3)0.025 (3)0.010 (3)0.004 (3)0.004 (3)
Geometric parameters (Å, °) top
Br1—Zn12.3897 (10)C3—H30.9500
Br2—Zn12.3664 (10)C4—H40.9500
Zn1—N112.042 (5)S2—C111.783 (6)
Zn1—N12.091 (5)N11—C111.343 (8)
S1—C11.784 (7)N11—C151.344 (8)
S1—S22.050 (3)C15—C141.385 (9)
N1—C11.344 (8)C15—H150.9500
N1—C51.362 (8)C11—C121.387 (9)
C2—C31.385 (10)C14—C131.386 (11)
C2—C11.401 (9)C14—H140.9500
C2—H20.9500C13—C121.406 (10)
C5—C41.385 (10)C13—H130.9500
C5—H50.9500C12—H120.9500
C3—C41.389 (11)
N11—Zn1—N1117.2 (2)C5—C4—C3119.2 (6)
N11—Zn1—Br2112.77 (15)C5—C4—H4120.4
N1—Zn1—Br2103.61 (14)C3—C4—H4120.4
N11—Zn1—Br1103.35 (15)C11—S2—S1104.0 (2)
N1—Zn1—Br1100.99 (15)C11—N11—C15118.2 (5)
Br2—Zn1—Br1119.06 (4)C11—N11—Zn1121.2 (4)
C1—S1—S2106.7 (2)C15—N11—Zn1120.3 (4)
C1—N1—C5118.1 (5)N11—C15—C14123.2 (6)
C1—N1—Zn1131.4 (4)N11—C15—H15118.4
C5—N1—Zn1110.4 (4)C14—C15—H15118.4
C3—C2—C1118.8 (6)N11—C11—C12122.8 (6)
C3—C2—H2120.6N11—C11—S2118.3 (4)
C1—C2—H2120.6C12—C11—S2118.8 (5)
N1—C5—C4122.2 (6)C15—C14—C13118.5 (6)
N1—C5—H5118.9C15—C14—H14120.8
C4—C5—H5118.9C13—C14—H14120.8
N1—C1—C2122.5 (6)C14—C13—C12119.1 (6)
N1—C1—S1121.5 (5)C14—C13—H13120.5
C2—C1—S1115.9 (5)C12—C13—H13120.5
C2—C3—C4119.1 (6)C11—C12—C13118.3 (6)
C2—C3—H3120.5C11—C12—H12120.9
C4—C3—H3120.5C13—C12—H12120.9
Table 1
Selected geometric parameters (Å, °) top
Br1—Zn12.3897 (10)S1—C11.784 (7)
Br2—Zn12.3664 (10)S1—S22.050 (3)
Zn1—N112.042 (5)S2—C111.783 (6)
Zn1—N12.091 (5)
N11—Zn1—N1117.2 (2)N11—Zn1—Br1103.35 (15)
N11—Zn1—Br2112.77 (15)N1—Zn1—Br1100.99 (15)
N1—Zn1—Br2103.61 (14)Br2—Zn1—Br1119.06 (4)
Acknowledgements top

This work is supported by the state of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (Projekt No. NA 720/1–1). We are very grateful to Professor Dr Wolfgang Bensch for the facility to use his experimental equipment.

references
References top

Bhosekar, G., Je\&s, I. & Näther, C. (2007). Inorg. Chem. 43, 6508–6515.

Bruker (1998). SHELXTL. Version 5.1 Bruker AXS, Madison, Wisconsin, USA.

Kadooka, M. M., Warner, L. G. & Seff, K. (1976). Inorg. Chem. 15, 4, 812–816.

Kinoshita, I., Wright, L. J., Kubo, S., Kimura, K., Sakata, A., Yano, T., Miyamoto, R., Nishioka, T. & Isobe, K. (2003). Dalton Trans. pp. 1993–2003.

Kubo, S., Nishioka, T., Ishikawa, K., Kinoshita, I. & Isobe, K. (1998). Chem. Lett. 27, 1067–1068.

Näther, C. & Jess, I. (2006). Inorg. Chem. 45, 7446–7454.

Näther, C., Wriedt, M. & Jess, I. (2003). Inorg. Chem. 42, 2391–2397.

Pickardt, J., von Chrzanowski, J., Steudel, R., Borowski, M. & Beck, S. (2005). Z. Naturforsch. Teil B, 60, 373–376.

Raghavan, N. V. & Seff, K. (1977). Acta Cryst. B33, 386–391.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Stoe (1998). IPDS Program Package (Version 2.89). Stoe & Cie, Darmstadt, Germany.