Acta Cryst. (2008). E64, m315 [ doi:10.1107/S1600536808000081 ]
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2N,N')zinc(II)The molecule of the title compound, [ZnBr2(C10H8N2S)], contains a six-membered chelate ring in a boat conformation in which the Zn atom is coordinated by two Br atoms and by the two pyridyl N atoms of a single di-2-pyridyl sulfide (dps) ligand within a slightly distorted tetrahedron. The dihedral angle between the pyridine rings is 52.7 (1)°. As is usual for this type of complex, the sulfide group does not participate in the zinc coordination.
ZnBr2 and 2,2'-bipyridyldisulfide was obtained from Alfa Aesar, methanol was obtained from Fluka. 0.125 mmol (28.1 mg) zinc(II) bromide, 0.0312 mmol (6.87 mg) 2,2'-bipyridyldisulfide and 3 ml of methanol were transfered into a test-tube, which was closed and heated to 110 °C for three days. On cooling colourless block-shaped single crystals of the title compound were obtained.
All H atoms were located from the difference Fourier map but were positioned with idealized geometry and were refined isotropically with Ueq(H) = 1.2 Ueq(C) of the parent atom using a riding model with C—H = 0.97 Å.
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, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXTL (Bruker, 1998).
![[Figure 1]](./im2053fig1thm.gif)
| Fig. 1. : Crystal structure of compound I showing the labelling scheme, and displacement ellipsoids drawn at the 50% probability level. |
| [ZnBr2(C10H8N2S)] | F000 = 792 |
| Mr = 413.43 | Dx = 2.111 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 8000 reflections |
| a = 11.0385 (8) Å | θ = 13.8–24.9º |
| b = 8.9627 (5) Å | µ = 8.16 mm−1 |
| c = 13.157 (1) Å | T = 170 (2) K |
| β = 91.663 (9)º | Block, colourless |
| V = 1301.2 (2) Å3 | 0.14 × 0.10 × 0.07 mm |
| Z = 4 |
| Stoe IPDS-1 diffractometer | 3105 independent reflections |
| Radiation source: fine-focus sealed tube | 2534 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.041 |
| T = 170(2) K | θmax = 28.0º |
| Phi scans | θmin = 2.8º |
| Absorption correction: numerical (X-SHAPE; Stoe, 1998) | h = −14→14 |
| Tmin = 0.285, Tmax = 0.394 | k = −11→11 |
| 14781 measured reflections | l = −17→17 |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.033 | w = 1/[σ2(Fo2) + (0.0528P)2 + 0.9116P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.085 | (Δ/σ)max = 0.001 |
| S = 1.03 | Δρmax = 1.15 e Å−3 |
| 3105 reflections | Δρmin = −1.15 e Å−3 |
| 146 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0076 (6) |
| Secondary atom site location: difference Fourier map |
| [ZnBr2(C10H8N2S)] | V = 1301.2 (2) Å3 |
| Mr = 413.43 | Z = 4 |
| Monoclinic, P21/c | Mo Kα |
| a = 11.0385 (8) Å | µ = 8.16 mm−1 |
| b = 8.9627 (5) Å | T = 170 (2) K |
| c = 13.157 (1) Å | 0.14 × 0.10 × 0.07 mm |
| β = 91.663 (9)º |
| Stoe IPDS-1 diffractometer | 3105 independent reflections |
| Absorption correction: numerical (X-SHAPE; Stoe, 1998) | 2534 reflections with I > 2σ(I) |
| Tmin = 0.285, Tmax = 0.394 | Rint = 0.041 |
| 14781 measured reflections |
| R[F2 > 2σ(F2)] = 0.033 | 146 parameters |
| wR(F2) = 0.085 | H-atom parameters constrained |
| S = 1.03 | Δρmax = 1.15 e Å−3 |
| 3105 reflections | Δρmin = −1.15 e Å−3 |
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. |
| x | y | z | Uiso*/Ueq | ||
| Zn1 | 0.74601 (4) | 0.84740 (4) | 0.50911 (3) | 0.01791 (12) | |
| Br1 | 0.72001 (4) | 1.08853 (4) | 0.57571 (3) | 0.03251 (13) | |
| Br2 | 0.76278 (4) | 0.82087 (5) | 0.33235 (3) | 0.03579 (13) | |
| N1 | 0.8929 (3) | 0.7499 (3) | 0.5825 (2) | 0.0174 (5) | |
| C1 | 0.8968 (3) | 0.6003 (4) | 0.5939 (2) | 0.0187 (6) | |
| C2 | 0.9955 (4) | 0.5287 (4) | 0.6405 (3) | 0.0258 (7) | |
| H2 | 0.9973 | 0.4231 | 0.6461 | 0.031* | |
| C3 | 1.0912 (4) | 0.6142 (5) | 0.6789 (3) | 0.0308 (8) | |
| H3 | 1.1597 | 0.5677 | 0.7106 | 0.037* | |
| C4 | 1.0854 (4) | 0.7682 (5) | 0.6702 (3) | 0.0323 (9) | |
| H4 | 1.1491 | 0.8289 | 0.6973 | 0.039* | |
| C5 | 0.9853 (3) | 0.8322 (4) | 0.6215 (3) | 0.0252 (7) | |
| H5 | 0.9818 | 0.9377 | 0.6153 | 0.030* | |
| S1 | 0.77889 (9) | 0.48727 (9) | 0.54086 (8) | 0.0262 (2) | |
| N11 | 0.6206 (3) | 0.7109 (3) | 0.5746 (2) | 0.0173 (5) | |
| C11 | 0.6435 (3) | 0.5653 (3) | 0.5880 (2) | 0.0175 (6) | |
| C12 | 0.5613 (3) | 0.4683 (4) | 0.6314 (3) | 0.0247 (7) | |
| H12 | 0.5790 | 0.3650 | 0.6384 | 0.030* | |
| C13 | 0.4528 (4) | 0.5268 (4) | 0.6640 (3) | 0.0291 (8) | |
| H13 | 0.3945 | 0.4635 | 0.6935 | 0.035* | |
| C14 | 0.4303 (4) | 0.6768 (5) | 0.6535 (3) | 0.0311 (8) | |
| H14 | 0.3569 | 0.7185 | 0.6767 | 0.037* | |
| C15 | 0.5160 (3) | 0.7667 (4) | 0.6085 (3) | 0.0240 (7) | |
| H15 | 0.5004 | 0.8705 | 0.6015 | 0.029* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Zn1 | 0.0211 (2) | 0.01532 (19) | 0.01722 (19) | −0.00099 (14) | −0.00055 (14) | 0.00326 (13) |
| Br1 | 0.0418 (3) | 0.01468 (17) | 0.0407 (2) | 0.00437 (14) | −0.00482 (17) | −0.00135 (13) |
| Br2 | 0.0492 (3) | 0.0418 (2) | 0.01642 (18) | −0.01221 (18) | 0.00179 (15) | 0.00378 (14) |
| N1 | 0.0158 (14) | 0.0174 (12) | 0.0192 (13) | 0.0002 (10) | 0.0023 (10) | −0.0007 (10) |
| C1 | 0.0196 (17) | 0.0198 (15) | 0.0171 (15) | 0.0046 (12) | 0.0062 (12) | −0.0003 (11) |
| C2 | 0.026 (2) | 0.0284 (17) | 0.0238 (17) | 0.0106 (14) | 0.0068 (14) | 0.0047 (13) |
| C3 | 0.0200 (19) | 0.049 (2) | 0.0232 (17) | 0.0120 (16) | 0.0013 (14) | 0.0013 (15) |
| C4 | 0.0188 (19) | 0.047 (2) | 0.0313 (19) | 0.0016 (16) | −0.0014 (15) | −0.0104 (17) |
| C5 | 0.0214 (19) | 0.0282 (17) | 0.0261 (18) | −0.0005 (14) | 0.0007 (14) | −0.0044 (14) |
| S1 | 0.0246 (5) | 0.0165 (4) | 0.0380 (5) | −0.0023 (3) | 0.0090 (4) | −0.0081 (3) |
| N11 | 0.0172 (14) | 0.0191 (12) | 0.0157 (12) | −0.0031 (10) | −0.0003 (10) | 0.0008 (10) |
| C11 | 0.0208 (18) | 0.0151 (13) | 0.0164 (14) | −0.0039 (12) | −0.0003 (12) | −0.0008 (11) |
| C12 | 0.0234 (19) | 0.0238 (16) | 0.0270 (18) | −0.0072 (14) | 0.0021 (14) | 0.0013 (13) |
| C13 | 0.027 (2) | 0.0340 (19) | 0.0269 (18) | −0.0118 (16) | 0.0030 (15) | 0.0007 (14) |
| C14 | 0.0142 (18) | 0.041 (2) | 0.038 (2) | −0.0009 (15) | 0.0047 (15) | −0.0051 (16) |
| C15 | 0.0164 (18) | 0.0251 (16) | 0.0305 (18) | 0.0017 (13) | 0.0014 (13) | −0.0014 (13) |
| Zn1—N11 | 2.055 (3) | C4—H4 | 0.9500 |
| Zn1—N1 | 2.058 (3) | C5—H5 | 0.9500 |
| Zn1—Br2 | 2.3504 (6) | S1—C11 | 1.778 (4) |
| Zn1—Br1 | 2.3527 (5) | N11—C11 | 1.340 (4) |
| N1—C5 | 1.348 (4) | N11—C15 | 1.347 (5) |
| N1—C1 | 1.350 (4) | C11—C12 | 1.391 (5) |
| C1—C2 | 1.391 (5) | C12—C13 | 1.387 (6) |
| C1—S1 | 1.776 (4) | C12—H12 | 0.9500 |
| C2—C3 | 1.388 (6) | C13—C14 | 1.373 (6) |
| C2—H2 | 0.9500 | C13—H13 | 0.9500 |
| C3—C4 | 1.386 (6) | C14—C15 | 1.388 (5) |
| C3—H3 | 0.9500 | C14—H14 | 0.9500 |
| C4—C5 | 1.385 (5) | C15—H15 | 0.9500 |
| N11—Zn1—N1 | 94.66 (11) | N1—C5—H5 | 118.9 |
| N11—Zn1—Br2 | 115.35 (8) | C4—C5—H5 | 118.9 |
| N1—Zn1—Br2 | 109.76 (8) | C1—S1—C11 | 104.63 (15) |
| N11—Zn1—Br1 | 107.43 (8) | C11—N11—C15 | 118.6 (3) |
| N1—Zn1—Br1 | 108.56 (8) | C11—N11—Zn1 | 120.5 (2) |
| Br2—Zn1—Br1 | 118.38 (2) | C15—N11—Zn1 | 120.8 (2) |
| C5—N1—C1 | 118.6 (3) | N11—C11—C12 | 122.7 (3) |
| C5—N1—Zn1 | 121.6 (2) | N11—C11—S1 | 119.7 (2) |
| C1—N1—Zn1 | 119.8 (2) | C12—C11—S1 | 117.5 (3) |
| N1—C1—C2 | 122.0 (3) | C13—C12—C11 | 118.0 (3) |
| N1—C1—S1 | 120.1 (3) | C13—C12—H12 | 121.0 |
| C2—C1—S1 | 117.8 (3) | C11—C12—H12 | 121.0 |
| C3—C2—C1 | 118.9 (3) | C14—C13—C12 | 119.7 (3) |
| C3—C2—H2 | 120.5 | C14—C13—H13 | 120.2 |
| C1—C2—H2 | 120.5 | C12—C13—H13 | 120.2 |
| C4—C3—C2 | 119.2 (3) | C13—C14—C15 | 119.1 (4) |
| C4—C3—H3 | 120.4 | C13—C14—H14 | 120.4 |
| C2—C3—H3 | 120.4 | C15—C14—H14 | 120.4 |
| C5—C4—C3 | 119.0 (4) | N11—C15—C14 | 121.8 (3) |
| C5—C4—H4 | 120.5 | N11—C15—H15 | 119.1 |
| C3—C4—H4 | 120.5 | C14—C15—H15 | 119.1 |
| N1—C5—C4 | 122.3 (3) |
| Zn1—N11 | 2.055 (3) | Zn1—Br2 | 2.3504 (6) |
| Zn1—N1 | 2.058 (3) | Zn1—Br1 | 2.3527 (5) |
| N11—Zn1—N1 | 94.66 (11) | N11—Zn1—Br1 | 107.43 (8) |
| N11—Zn1—Br2 | 115.35 (8) | N1—Zn1—Br1 | 108.56 (8) |
| N1—Zn1—Br2 | 109.76 (8) | Br2—Zn1—Br1 | 118.38 (2) |
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.
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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 started systematic investigation of their thermal behavior because we have demonstrated that new ligand-deficient coordination polymers can be conveniently prepared by thermal decomposition of suitable ligand-rich precursur compounds (Näther et al. 2003; Näther & Je\&s, 2006). In further investigations we have reacted zinc(II) bromide with 2,2'-bipyridyldisulfide (dpds). In this reaction a cleavage of the S—S bond takes place leading to the formation of di-2-pyridyl sulfide (dps) which in a concomitant reaction with zinc(II) bromide forms the title chelate-complex.
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 a 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 molecular structure the coordination geometry about the Zn atom is almost tetrahedral with bonds being formed to two Br atoms and the two pyridyl N atoms of a single dps ligand (Fig. 1). These interactions result in the formation of a six-membered chelate ring in a boat conformation. The X—Zn—X angles (X = Br, N) range from 94.7 (1) to 118.38 (2)°, the largest being Br—Zn—Br. The Zn—Br and Zn—N distances are in the range of 2.3504 (6)–2.3527 (5) and 2.055 (3)–2.058 (3) Å. The structural parameters in the bps molecule are quite regular. In particular the C—S bonds of 1.776 (4) Å (S1—C1) and 1.778 (4) Å (S1—C11) are in good agreement with those expected for C(sp2)—S bonds (1.77 Å, Tresoldi et al. 1992).