Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103017633/fr1434sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103017633/fr1434Isup2.hkl |
CCDC reference: 226100
Zinc acetate dihydrate (219.5 mg, 1 mmol; Fisher Scientific) was dissolved in hot ethanol (10 ml) and to this solution was added a room-temperature solution of 1,2-benzenedithiol (142.2 mg, 1 mmol; Aldrich) in ethanol (5 ml), dropwise with stirring. The resulting white precipitate was dissolved by the dropwise addition of dimethylformamide (DMF) followed by the dropwise addition of 2,2-bipyridine (bipy) (156.2 mg, 1 mmol; Aldrich) dissolved in hot ethanol (10 ml). The resulting deep yellow solution was refluxed for 10 min and allowed to cool slowly for a period of 24 h. The orange crystalline solid that formed was collected by vacuum filtration and dried in vacuo (yield 70.9%). Analysis calculated for C32H24N4S4Zn2: C 53.11, H 3.34, N 7.74%; found: C 52.8, H 3.1, N 7.6%.
H atoms were included in calculated positions (C—H = 0.95 Å) as riding contributions, with isotropic displacement parameters 1.2 times those of the attached C atoms. The largest residual density peak is located 0.82 Å from Zn.
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
[Zn2(C6H4S2)2(C10H8N2)2] | F(000) = 736 |
Mr = 723.54 | Dx = 1.673 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7279 reflections |
a = 10.859 (1) Å | θ = 2.3–28.3° |
b = 9.523 (1) Å | µ = 1.99 mm−1 |
c = 13.910 (1) Å | T = 100 K |
β = 93.18 (1)° | Plate, yellow |
V = 1436.2 (2) Å3 | 0.31 × 0.20 × 0.12 mm |
Z = 2 |
Bruker SMART APEX CCD area-detector diffractometer | 3355 independent reflections |
Radiation source: fine-focus sealed tube | 3154 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ϕ and ω scans | θmax = 27.7°, θmin = 2.3° |
Absorption correction: multi-scan SADABS (Sheldrick, 2002) | h = −14→14 |
Tmin = 0.577, Tmax = 0.796 | k = −12→12 |
12291 measured reflections | l = −17→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0344P)2 + 0.9504P] where P = (Fo2 + 2Fc2)/3 |
3355 reflections | (Δ/σ)max = 0.002 |
190 parameters | Δρmax = 0.91 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
[Zn2(C6H4S2)2(C10H8N2)2] | V = 1436.2 (2) Å3 |
Mr = 723.54 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.859 (1) Å | µ = 1.99 mm−1 |
b = 9.523 (1) Å | T = 100 K |
c = 13.910 (1) Å | 0.31 × 0.20 × 0.12 mm |
β = 93.18 (1)° |
Bruker SMART APEX CCD area-detector diffractometer | 3355 independent reflections |
Absorption correction: multi-scan SADABS (Sheldrick, 2002) | 3154 reflections with I > 2σ(I) |
Tmin = 0.577, Tmax = 0.796 | Rint = 0.022 |
12291 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.91 e Å−3 |
3355 reflections | Δρmin = −0.23 e Å−3 |
190 parameters |
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 | ||
Zn | 0.123273 (17) | 0.10028 (2) | 0.961146 (13) | 0.01320 (7) | |
S1 | −0.08750 (4) | 0.04958 (4) | 0.89878 (3) | 0.01365 (9) | |
S2 | 0.20087 (4) | −0.00921 (4) | 0.83074 (3) | 0.01550 (10) | |
N1 | 0.29770 (12) | 0.17126 (15) | 1.03069 (10) | 0.0143 (3) | |
N2 | 0.11999 (12) | 0.32455 (15) | 0.94799 (10) | 0.0147 (3) | |
C1 | 0.38165 (15) | 0.08518 (18) | 1.07275 (13) | 0.0157 (3) | |
H1 | 0.3705 | −0.0133 | 1.0655 | 0.019* | |
C2 | 0.48413 (16) | 0.13347 (19) | 1.12645 (12) | 0.0174 (3) | |
H2 | 0.5430 | 0.0697 | 1.1545 | 0.021* | |
C3 | 0.49877 (16) | 0.27753 (19) | 1.13831 (13) | 0.0192 (4) | |
H3 | 0.5667 | 0.3139 | 1.1765 | 0.023* | |
C4 | 0.41316 (16) | 0.36746 (19) | 1.09374 (13) | 0.0186 (3) | |
H4 | 0.4222 | 0.4663 | 1.0999 | 0.022* | |
C5 | 0.31347 (15) | 0.31040 (17) | 1.03966 (12) | 0.0142 (3) | |
C6 | 0.21845 (16) | 0.39647 (17) | 0.98561 (12) | 0.0148 (3) | |
C7 | 0.23249 (17) | 0.53924 (19) | 0.97023 (13) | 0.0191 (4) | |
H7 | 0.3018 | 0.5879 | 0.9984 | 0.023* | |
C8 | 0.14416 (18) | 0.60991 (19) | 0.91332 (13) | 0.0220 (4) | |
H8 | 0.1526 | 0.7075 | 0.9012 | 0.026* | |
C9 | 0.04350 (17) | 0.5366 (2) | 0.87437 (13) | 0.0208 (4) | |
H9 | −0.0184 | 0.5829 | 0.8352 | 0.025* | |
C10 | 0.03458 (16) | 0.39453 (18) | 0.89351 (12) | 0.0178 (3) | |
H10 | −0.0349 | 0.3444 | 0.8670 | 0.021* | |
C11 | −0.05294 (15) | −0.06764 (17) | 0.80483 (12) | 0.0137 (3) | |
C12 | 0.06863 (15) | −0.08914 (16) | 0.77633 (12) | 0.0132 (3) | |
C13 | 0.08616 (15) | −0.18078 (18) | 0.69941 (12) | 0.0154 (3) | |
H13 | 0.1674 | −0.1963 | 0.6795 | 0.018* | |
C14 | −0.01168 (16) | −0.24935 (18) | 0.65158 (12) | 0.0170 (3) | |
H14 | 0.0028 | −0.3098 | 0.5991 | 0.020* | |
C15 | −0.13133 (16) | −0.22966 (19) | 0.68044 (13) | 0.0182 (3) | |
H15 | −0.1987 | −0.2778 | 0.6488 | 0.022* | |
C16 | −0.15061 (15) | −0.13893 (19) | 0.75592 (12) | 0.0169 (3) | |
H16 | −0.2323 | −0.1245 | 0.7751 | 0.020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn | 0.01153 (11) | 0.01316 (11) | 0.01469 (11) | 0.00025 (7) | −0.00134 (7) | −0.00178 (7) |
S1 | 0.01120 (19) | 0.0154 (2) | 0.01421 (19) | 0.00100 (14) | −0.00091 (14) | −0.00180 (15) |
S2 | 0.01051 (18) | 0.0187 (2) | 0.0171 (2) | −0.00120 (15) | −0.00023 (15) | −0.00336 (15) |
N1 | 0.0133 (6) | 0.0150 (7) | 0.0144 (7) | −0.0001 (5) | 0.0000 (5) | 0.0004 (5) |
N2 | 0.0143 (7) | 0.0147 (7) | 0.0150 (7) | 0.0014 (5) | 0.0000 (5) | −0.0007 (5) |
C1 | 0.0137 (8) | 0.0147 (8) | 0.0190 (8) | 0.0004 (6) | 0.0024 (6) | 0.0010 (6) |
C2 | 0.0139 (8) | 0.0208 (8) | 0.0173 (8) | 0.0024 (6) | −0.0008 (6) | 0.0017 (7) |
C3 | 0.0158 (8) | 0.0230 (9) | 0.0182 (8) | −0.0021 (7) | −0.0035 (6) | −0.0023 (7) |
C4 | 0.0187 (8) | 0.0163 (8) | 0.0204 (9) | −0.0027 (7) | −0.0023 (7) | −0.0023 (7) |
C5 | 0.0142 (8) | 0.0146 (8) | 0.0138 (8) | 0.0005 (6) | 0.0020 (6) | −0.0001 (6) |
C6 | 0.0154 (8) | 0.0158 (8) | 0.0132 (8) | 0.0009 (6) | 0.0009 (6) | −0.0016 (6) |
C7 | 0.0204 (9) | 0.0161 (8) | 0.0206 (9) | −0.0015 (7) | −0.0008 (7) | −0.0002 (7) |
C8 | 0.0279 (10) | 0.0167 (9) | 0.0215 (9) | 0.0022 (7) | 0.0019 (7) | 0.0041 (7) |
C9 | 0.0232 (9) | 0.0223 (9) | 0.0165 (8) | 0.0069 (7) | −0.0014 (7) | 0.0033 (7) |
C10 | 0.0173 (8) | 0.0205 (9) | 0.0152 (8) | 0.0021 (6) | −0.0016 (6) | −0.0018 (6) |
C11 | 0.0148 (8) | 0.0130 (7) | 0.0132 (8) | 0.0002 (6) | −0.0009 (6) | 0.0004 (6) |
C12 | 0.0131 (8) | 0.0121 (7) | 0.0142 (8) | −0.0017 (6) | −0.0011 (6) | 0.0013 (6) |
C13 | 0.0161 (8) | 0.0148 (8) | 0.0153 (8) | −0.0003 (6) | 0.0021 (6) | 0.0009 (6) |
C14 | 0.0210 (8) | 0.0153 (8) | 0.0148 (8) | −0.0022 (6) | 0.0006 (6) | −0.0020 (6) |
C15 | 0.0182 (8) | 0.0194 (9) | 0.0168 (8) | −0.0058 (7) | −0.0022 (6) | −0.0018 (6) |
C16 | 0.0124 (8) | 0.0201 (8) | 0.0182 (8) | −0.0019 (6) | −0.0002 (6) | −0.0003 (7) |
Zn—N2 | 2.1436 (15) | C5—C6 | 1.489 (2) |
Zn—N1 | 2.1857 (14) | C6—C7 | 1.386 (2) |
Zn—S2 | 2.2929 (5) | C7—C8 | 1.384 (3) |
Zn—S1 | 2.4504 (5) | C7—H7 | 0.9500 |
Zn—S1i | 2.4634 (5) | C8—C9 | 1.382 (3) |
S1—C11 | 1.7746 (17) | C8—H8 | 0.9500 |
S1—Zni | 2.4634 (5) | C9—C10 | 1.383 (3) |
S2—C12 | 1.7589 (17) | C9—H9 | 0.9500 |
N1—C1 | 1.336 (2) | C10—H10 | 0.9500 |
N1—C5 | 1.341 (2) | C11—C16 | 1.403 (2) |
N2—C10 | 1.342 (2) | C11—C12 | 1.414 (2) |
N2—C6 | 1.351 (2) | C12—C13 | 1.402 (2) |
C1—C2 | 1.384 (2) | C13—C14 | 1.385 (2) |
C1—H1 | 0.9500 | C13—H13 | 0.9500 |
C2—C3 | 1.390 (3) | C14—C15 | 1.394 (2) |
C2—H2 | 0.9500 | C14—H14 | 0.9500 |
C3—C4 | 1.385 (2) | C15—C16 | 1.385 (2) |
C3—H3 | 0.9500 | C15—H15 | 0.9500 |
C4—C5 | 1.394 (2) | C16—H16 | 0.9500 |
C4—H4 | 0.9500 | ||
N2—Zn—N1 | 74.91 (5) | C4—C5—C6 | 123.63 (16) |
N2—Zn—S2 | 112.99 (4) | N2—C6—C7 | 121.95 (16) |
N1—Zn—S2 | 98.24 (4) | N2—C6—C5 | 115.35 (15) |
N2—Zn—S1 | 98.93 (4) | C7—C6—C5 | 122.61 (16) |
N1—Zn—S1 | 170.81 (4) | C8—C7—C6 | 119.12 (17) |
S2—Zn—S1 | 90.420 (16) | C8—C7—H7 | 120.4 |
N2—Zn—S1i | 129.95 (4) | C6—C7—H7 | 120.4 |
N1—Zn—S1i | 89.99 (4) | C9—C8—C7 | 119.12 (17) |
S2—Zn—S1i | 116.317 (17) | C9—C8—H8 | 120.4 |
S1—Zn—S1i | 88.896 (15) | C7—C8—H8 | 120.4 |
C11—S1—Zn | 98.81 (6) | C8—C9—C10 | 118.74 (17) |
C11—S1—Zni | 105.50 (6) | C8—C9—H9 | 120.6 |
Zn—S1—Zni | 91.104 (15) | C10—C9—H9 | 120.6 |
C12—S2—Zn | 102.13 (6) | N2—C10—C9 | 122.74 (17) |
C1—N1—C5 | 119.00 (15) | N2—C10—H10 | 118.6 |
C1—N1—Zn | 123.88 (11) | C9—C10—H10 | 118.6 |
C5—N1—Zn | 116.73 (11) | C16—C11—C12 | 119.09 (15) |
C10—N2—C6 | 118.33 (15) | C16—C11—S1 | 118.45 (13) |
C10—N2—Zn | 123.41 (12) | C12—C11—S1 | 122.44 (13) |
C6—N2—Zn | 117.59 (11) | C13—C12—C11 | 118.20 (15) |
N1—C1—C2 | 122.75 (16) | C13—C12—S2 | 117.11 (13) |
N1—C1—H1 | 118.6 | C11—C12—S2 | 124.70 (13) |
C2—C1—H1 | 118.6 | C14—C13—C12 | 121.80 (16) |
C1—C2—C3 | 118.38 (16) | C14—C13—H13 | 119.1 |
C1—C2—H2 | 120.8 | C12—C13—H13 | 119.1 |
C3—C2—H2 | 120.8 | C13—C14—C15 | 120.04 (16) |
C4—C3—C2 | 119.19 (16) | C13—C14—H14 | 120.0 |
C4—C3—H3 | 120.4 | C15—C14—H14 | 120.0 |
C2—C3—H3 | 120.4 | C16—C15—C14 | 119.01 (16) |
C3—C4—C5 | 118.85 (16) | C16—C15—H15 | 120.5 |
C3—C4—H4 | 120.6 | C14—C15—H15 | 120.5 |
C5—C4—H4 | 120.6 | C15—C16—C11 | 121.85 (16) |
N1—C5—C4 | 121.79 (16) | C15—C16—H16 | 119.1 |
N1—C5—C6 | 114.56 (15) | C11—C16—H16 | 119.1 |
Symmetry code: (i) −x, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C6H4S2)2(C10H8N2)2] |
Mr | 723.54 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 10.859 (1), 9.523 (1), 13.910 (1) |
β (°) | 93.18 (1) |
V (Å3) | 1436.2 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.99 |
Crystal size (mm) | 0.31 × 0.20 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan SADABS (Sheldrick, 2002) |
Tmin, Tmax | 0.577, 0.796 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12291, 3355, 3154 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.655 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.065, 1.06 |
No. of reflections | 3355 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.91, −0.23 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT-Plus (Bruker, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
Zn—N2 | 2.1436 (15) | Zn—S1 | 2.4504 (5) |
Zn—N1 | 2.1857 (14) | Zn—S1i | 2.4634 (5) |
Zn—S2 | 2.2929 (5) | S1—Zni | 2.4634 (5) |
N2—Zn—N1 | 74.91 (5) | N2—Zn—S1i | 129.95 (4) |
N2—Zn—S2 | 112.99 (4) | N1—Zn—S1i | 89.99 (4) |
N1—Zn—S2 | 98.24 (4) | S2—Zn—S1i | 116.317 (17) |
N2—Zn—S1 | 98.93 (4) | S1—Zn—S1i | 88.896 (15) |
N1—Zn—S1 | 170.81 (4) | Zn—S1—Zni | 91.104 (15) |
S2—Zn—S1 | 90.420 (16) |
Symmetry code: (i) −x, −y, −z+2. |
There have been numerous investigations of heteroleptic d10 complexes involving ZnII or CdII compounds that employ N,N'-heterocycles and either two monothiolate ligands or one dithiolate ligand (Koester, 1975; Crosby et al., 1985; Kutal, 1990). These highly colored and luminescent compounds exhibit strong absorptions in the visible region of the spectrum, which have been assigned as a metal-mediated ligand-to-ligand charge transfer (LLCT) transition (Muresan & Muresan, 1979; Fernandez & Kisch, 1984; Highland & Crosby, 1985; Truesdell & Crosby, 1985; Highland et al., 1986; Reddy et al., 1992; Galin et al., 1993; Gronlund, Burt & Wacholtz, 1995; Zemskova et al., 1998). It has been reported, that mononuclear tetrahedral complexes of ZnII are generally obtained when the motionally restricted benzenedithiolate (bdt) ligand is used with more sterically hindered N,N-heterocycles (Yam et al., 1999; Lowther et al., 2001). When non-substituted N,N'- heterocyclic ligands are employed with the bdt ligand, unusual multinuclear complexes are observed with both the zinc(II) and the cadmium(II) systems (Gronlund, Wacholtz & Mague, 1995; Halvorsen et al., 1995; Wang et al., 2000; Lowther et al., 2001; Hatch et al., 2003). The geometry of these complexes has been reported to depend on the planarity of the ligands used. We report here that the addition of 1,2-benzenedithiol (bdt) and 2,2'- bipyridine (bipy) to zinc(II) acetate dihydrate in hot ethanol /dimethylformamide forms the dinuclear complex [Zn(bdt)(bipy)]2, (I).
Complex (I) has crystallographically imposed centrosymmetry, with the ZnII atom exhibiting a modestly distorted trigonal- bipyramidal coordinate geometry. The major distortions involve the N1—Zn—N2 and S1—Zn—S2 angles (see Table 1) and result from the geometrical constraints of the bipy and bdt ligands. Also of note is the N1—Zn—S1 angle, which deviates from linearity by only about 10°. This contrasts with the closely related complex [Cd(bdt)(ophen)]2 (ophen = 1,10-phenanthroline) in which the corresponding angle is 154.40 (4)° (Lowther et al., 2001). In the latter complex, the angles between the formally equatorial substituents corresponding to the S2—Zn—N2, S2—Zn—S1' and N2—Zn—S1' angles in (I) are, respectively, 140.00 (4), 121.74 (2) and 97.09 (4)°, so that the coordination sphere of the cadmium complex is considerably more distorted from trigonal bipyramidal than is that of (I). The mean planes of the two halves of the bipy ligand in (I) are inclined at 12.80 (8)°, and the ring containing atom N2 shows a weak π-stacking interaction with the counterpart ring at 1 − x, −y, 1 − z. These rings are parallel, with a separation of 3.315 (3) Å. Also present is a possible weak C—H····S hydrogen bond between atom H2 and atom S2 in the asymmetric unit located at (2 − x, 1 − y, 1 − z) (H····S = 2.84 Å, C····S = 3.637 (2) Å and C—H····S = 143 °). These values can be compared with the values (H····S = 2.63 Å, C····S = 3.53 Å and C—H····S = 158°) attributed to a C—H····S hydrogen bond between a solvent chloroform molecule and (η4-Me8taa)GeS (Me8taa is the octamethyldibenzotetraaza[14]annulene dianion; Kuchta & Parkin, 1994; Steiner, 1998).