Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012706/bk1483sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012706/bk1483Isup2.hkl |
CCDC reference: 140934
Bis(pyrrolidinedithiocarboxylate)zinc (Wang & Marshall, 1996) and 4,4'-bipyridine were dissolved in dimethylformamide (DMF) and refluxed for 1 h. The yellow microcrystals which formed were collected by concentrating the DMF solution. Single crystals suitable for X-ray analysis were obtained by recrystallization from CH3CN.
The C7 atom was found to be disordered and was refined as C7 and C7A with occupancies of 0.55 and 0.45, respectively.
Data collection: SMART (Siemens, 1996a); cell refinement: SAINT (Siemens, 1996a); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXTL (Siemens, 1996b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. View of the title compound with the atomic numbering scheme and 30% probability ellipsoids. |
[Zn2(C5H8NS2)4(C10H8N2)] | F(000) = 3600 |
Mr = 871.90 | Dx = 1.493 Mg m−3 |
Orthorhombic, Fddd | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -F 2uv 2vw | Cell parameters from 6152 reflections |
a = 11.7643 (2) Å | θ = 2.1–29.4° |
b = 19.9965 (3) Å | µ = 1.70 mm−1 |
c = 32.9889 (3) Å | T = 293 K |
V = 7760.5 (2) Å3 | Cut hexagonal block, yellow |
Z = 8 | 0.20 × 0.20 × 0.18 mm |
Siemens SMART CCD diffractometer | 2497 independent reflections |
Radiation source: fine-focus sealed tube | 2009 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ω scans | θmax = 29.4°, θmin = 2.1° |
Absorption correction: empirical (using intensity measurements) (SADABS; sheldrick, 1996) ? | h = −15→8 |
Tmin = 0.644, Tmax = 0.737 | k = −27→27 |
11821 measured reflections | l = −45→43 |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.08 | Calculated w = 1/[σ2(Fo2) + (0.0532P)2 + 18.0531P] where P = (Fo2 + 2Fc2)/3 |
2497 reflections | (Δ/σ)max < 0.001 |
115 parameters | Δρmax = 0.62 e Å−3 |
16 restraints | Δρmin = −0.33 e Å−3 |
[Zn2(C5H8NS2)4(C10H8N2)] | V = 7760.5 (2) Å3 |
Mr = 871.90 | Z = 8 |
Orthorhombic, Fddd | Mo Kα radiation |
a = 11.7643 (2) Å | µ = 1.70 mm−1 |
b = 19.9965 (3) Å | T = 293 K |
c = 32.9889 (3) Å | 0.20 × 0.20 × 0.18 mm |
Siemens SMART CCD diffractometer | 2497 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; sheldrick, 1996) ? | 2009 reflections with I > 2σ(I) |
Tmin = 0.644, Tmax = 0.737 | Rint = 0.024 |
11821 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 16 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.62 e Å−3 |
2497 reflections | Δρmin = −0.33 e Å−3 |
115 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 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. The structure was solved by direct methods and refined by full-matrix least-squares techniques. The H atoms of the main molecules were located from difference maps and refined isotropically. H atoms were found geometrically and refined using riding model. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zn1 | 0.3750 | 0.3750 | 0.045213 (14) | 0.0587 (2) | |
S1 | 0.56323 (7) | 0.38695 (4) | 0.06616 (3) | 0.0707 (3) | |
S2 | 0.45846 (7) | 0.25380 (4) | 0.05343 (3) | 0.0782 (3) | |
N1 | 0.3750 | 0.3750 | −0.01799 (9) | 0.0495 (7) | |
N2 | 0.6784 (2) | 0.27358 (11) | 0.06687 (8) | 0.0634 (6) | |
C1 | 0.3430 (3) | 0.32096 (13) | −0.03915 (9) | 0.0572 (7) | |
H1 | 0.3207 | 0.28297 | −0.02495 | 0.069* | |
C2 | 0.3414 (2) | 0.31894 (12) | −0.08063 (8) | 0.0531 (6) | |
H2 | 0.3181 | 0.28039 | −0.09403 | 0.064* | |
C3 | 0.3750 | 0.3750 | −0.10258 (10) | 0.0420 (7) | |
C4 | 0.5772 (3) | 0.30107 (13) | 0.06273 (9) | 0.0565 (6) | |
C5 | 0.7844 (3) | 0.3118 (2) | 0.07296 (12) | 0.0730 (9) | |
H5A | 0.7824 | 0.3360 | 0.09842 | 0.088* | |
H5B | 0.7961 | 0.3434 | 0.05104 | 0.088* | |
C6 | 0.8764 (4) | 0.2597 (2) | 0.0734 (2) | 0.113 (2) | |
H6A | 0.9418 | 0.2753 | 0.0582 | 0.135* | |
H6B | 0.9001 | 0.2507 | 0.1010 | 0.135* | |
C7 | 0.8309 (7) | 0.2002 (4) | 0.0552 (3) | 0.092 (3) | 0.55 |
H7A | 0.8652 | 0.1607 | 0.0671 | 0.111* | |
H7B | 0.8454 | 0.1999 | 0.0262 | 0.111* | |
C8 | 0.7026 (3) | 0.2015 (2) | 0.06352 (14) | 0.0885 (11) | |
H8A | 0.6603 | 0.1814 | 0.04138 | 0.106* | |
H8B | 0.6843 | 0.1782 | 0.08849 | 0.106* | |
C7A | 0.8224 (10) | 0.1957 (5) | 0.0798 (4) | 0.100 (4) | 0.45 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.0510 (3) | 0.0715 (3) | 0.0537 (3) | −0.0012 (2) | 0.000 | 0.000 |
S1 | 0.0623 (5) | 0.0523 (4) | 0.0976 (6) | −0.0012 (3) | −0.0202 (4) | −0.0101 (4) |
S2 | 0.0642 (5) | 0.0626 (5) | 0.1078 (7) | −0.0217 (4) | −0.0146 (4) | 0.0175 (4) |
N1 | 0.048 (2) | 0.047 (2) | 0.053 (2) | −0.0037 (12) | 0.000 | 0.000 |
N2 | 0.0578 (14) | 0.0439 (12) | 0.088 (2) | −0.0055 (10) | −0.0069 (13) | 0.0029 (11) |
C1 | 0.068 (2) | 0.0447 (13) | 0.058 (2) | −0.0140 (12) | −0.0020 (13) | 0.0071 (11) |
C2 | 0.066 (2) | 0.0368 (12) | 0.0570 (15) | −0.0117 (11) | −0.0060 (12) | 0.0004 (10) |
C3 | 0.039 (2) | 0.0348 (15) | 0.052 (2) | 0.0005 (12) | 0.000 | 0.000 |
C4 | 0.060 (2) | 0.0476 (13) | 0.062 (2) | −0.0091 (12) | −0.0035 (13) | 0.0039 (11) |
C5 | 0.052 (2) | 0.061 (2) | 0.106 (3) | −0.0075 (13) | −0.008 (2) | −0.001 (2) |
C6 | 0.067 (2) | 0.081 (3) | 0.190 (5) | 0.008 (2) | −0.008 (3) | 0.001 (3) |
C7 | 0.081 (5) | 0.076 (5) | 0.120 (7) | 0.019 (4) | 0.008 (6) | 0.000 (5) |
C8 | 0.087 (2) | 0.046 (2) | 0.132 (3) | −0.002 (2) | −0.015 (2) | 0.006 (2) |
C7A | 0.096 (8) | 0.056 (5) | 0.148 (11) | 0.019 (5) | −0.022 (8) | 0.002 (7) |
Zn1—N1 | 2.085 (3) | N2—C8 | 1.474 (4) |
Zn1—S1 | 2.3319 (8) | N2—C5 | 1.476 (4) |
Zn1—S1i | 2.3319 (8) | C1—C2 | 1.369 (4) |
Zn1—S2i | 2.6290 (9) | C2—C3 | 1.392 (3) |
Zn1—S2 | 2.6290 (9) | C3—C2i | 1.392 (3) |
S1—C4 | 1.729 (3) | C3—C3ii | 1.479 (7) |
S2—C4 | 1.714 (3) | C5—C6 | 1.502 (5) |
N1—C1 | 1.340 (3) | C6—C7 | 1.437 (10) |
N1—C1i | 1.340 (3) | C7—C8 | 1.535 (9) |
N2—C4 | 1.318 (4) | ||
N1—Zn1—S1 | 107.23 (3) | C4—N2—C8 | 125.1 (3) |
N1—Zn1—S1i | 107.23 (3) | C4—N2—C5 | 124.1 (2) |
S1—Zn1—S1i | 145.53 (5) | C8—N2—C5 | 110.7 (3) |
N1—Zn1—S2i | 95.92 (2) | N1—C1—C2 | 123.2 (2) |
S1—Zn1—S2i | 103.28 (3) | C1—C2—C3 | 119.5 (2) |
S1i—Zn1—S2i | 73.10 (3) | C2i—C3—C2 | 117.3 (3) |
N1—Zn1—S2 | 95.92 (2) | C2i—C3—C3ii | 121.4 (2) |
S1—Zn1—S2 | 73.10 (3) | C2—C3—C3ii | 121.4 (2) |
S1i—Zn1—S2 | 103.28 (3) | N2—C4—S2 | 121.6 (2) |
S2i—Zn1—S2 | 168.17 (5) | N2—C4—S1 | 119.6 (2) |
C4—S1—Zn1 | 88.23 (10) | S2—C4—S1 | 118.8 (2) |
C4—S2—Zn1 | 79.31 (10) | N2—C5—C6 | 104.5 (3) |
C1—N1—C1i | 117.2 (3) | C7—C6—C5 | 107.6 (5) |
C1—N1—Zn1 | 121.4 (2) | C6—C7—C8 | 106.1 (5) |
C1i—N1—Zn1 | 121.4 (2) | N2—C8—C7 | 102.7 (4) |
N1—Zn1—S1—C4 | −86.62 (10) | N1—C1—C2—C3 | 0.4 (4) |
S1i—Zn1—S1—C4 | 93.38 (10) | C1—C2—C3—C2i | −0.2 (2) |
S2i—Zn1—S1—C4 | 172.78 (10) | C1—C2—C3—C3ii | 179.8 (2) |
S2—Zn1—S1—C4 | 4.45 (10) | C8—N2—C4—S2 | 1.1 (5) |
N1—Zn1—S2—C4 | 101.69 (10) | C5—N2—C4—S2 | 177.0 (3) |
S1—Zn1—S2—C4 | −4.56 (10) | C8—N2—C4—S1 | −178.2 (3) |
S1i—Zn1—S2—C4 | −149.01 (10) | C5—N2—C4—S1 | −2.3 (4) |
S2i—Zn1—S2—C4 | −78.31 (10) | Zn1—S2—C4—N2 | −172.6 (3) |
S1—Zn1—N1—C1 | 115.4 (2) | Zn1—S2—C4—S1 | 6.7 (2) |
S1i—Zn1—N1—C1 | −64.6 (2) | Zn1—S1—C4—N2 | 171.9 (2) |
S2i—Zn1—N1—C1 | −138.7 (2) | Zn1—S1—C4—S2 | −7.5 (2) |
S2—Zn1—N1—C1 | 41.3 (2) | C4—N2—C5—C6 | −176.6 (4) |
S1—Zn1—N1—C1i | −64.6 (2) | C8—N2—C5—C6 | −0.2 (5) |
S1i—Zn1—N1—C1i | 115.4 (2) | N2—C5—C6—C7 | 18.2 (7) |
S2i—Zn1—N1—C1i | 41.3 (2) | C5—C6—C7—C8 | −28.8 (8) |
S2—Zn1—N1—C1i | −138.7 (2) | C4—N2—C8—C7 | 160.0 (5) |
C1i—N1—C1—C2 | −0.2 (2) | C5—N2—C8—C7 | −16.4 (6) |
Zn1—N1—C1—C2 | 179.8 (2) | C6—C7—C8—N2 | 27.5 (8) |
Symmetry codes: (i) −x+3/4, −y+3/4, z; (ii) −x+3/4, y, −z−1/4. |
Experimental details
Crystal data | |
Chemical formula | [Zn2(C5H8NS2)4(C10H8N2)] |
Mr | 871.90 |
Crystal system, space group | Orthorhombic, Fddd |
Temperature (K) | 293 |
a, b, c (Å) | 11.7643 (2), 19.9965 (3), 32.9889 (3) |
V (Å3) | 7760.5 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.70 |
Crystal size (mm) | 0.20 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.644, 0.737 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11821, 2497, 2009 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.690 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.121, 1.08 |
No. of reflections | 2497 |
No. of parameters | 115 |
No. of restraints | 16 |
H-atom treatment | H-atom parameters constrained |
Calculated w = 1/[σ2(Fo2) + (0.0532P)2 + 18.0531P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.62, −0.33 |
Computer programs: SMART (Siemens, 1996a), SAINT (Siemens, 1996a), SAINT, SHELXS86 (Sheldrick, 1990), SHELXTL (Siemens, 1996b), SHELXTL.
Zn1—N1 | 2.085 (3) | N2—C5 | 1.476 (4) |
Zn1—S1 | 2.3319 (8) | C1—C2 | 1.369 (4) |
Zn1—S2 | 2.6290 (9) | C2—C3 | 1.392 (3) |
S1—C4 | 1.729 (3) | C3—C3i | 1.479 (7) |
S2—C4 | 1.714 (3) | C5—C6 | 1.502 (5) |
N1—C1 | 1.340 (3) | C6—C7 | 1.437 (10) |
N2—C4 | 1.318 (4) | C7—C8 | 1.535 (9) |
N2—C8 | 1.474 (4) | ||
N1—Zn1—S1 | 107.23 (3) | S1—Zn1—S2 | 73.10 (3) |
S1—Zn1—S1ii | 145.53 (5) | S1ii—Zn1—S2 | 103.28 (3) |
N1—Zn1—S2 | 95.92 (2) | S2ii—Zn1—S2 | 168.17 (5) |
Symmetry codes: (i) −x+3/4, y, −z−1/4; (ii) −x+3/4, −y+3/4, z. |
Recently, bis(dialkyldithiocarbamates) of zinc and cadmium have found use as single-molecule precursors in the growth of Group II–Group VI materials by low-pressure metal-organic chemical vapour deposition (Lp-MOCVD), leading to a renewed interest in their chemistry and further crystallographic investigations (O'Brien et al., 1996). In general, the formation of the adduct breaks the parent dimeric dithiocarbamate into a monomeric species (Airolidi et al., 1990; Zeng et al., 1994). However, this is not the case for the N,N,N',N'-tetramethylethylenediamine (TMED) adduct of the asymmetric dithiocarbamate species [Zn(S2CNMeiPr)2], which was reported as consisting of two bis(N-methylisopropyldithiocarbamato)zinc molecules bridged by a TMED molecule (Malik et al., 1997). We report here the crystal structure of µ-(4,4'-bipyridine)-N:N'-bis[bis(pyrrolidinedithiocarboxylato-S,S')zinc(II)], (I), composed of two bis(pyrrolidinedithiocarboxylato)zinc(II) moieties bridged by a 4,4'-bipyridine (4,4'-bipy) molecule.
Compound (I) (Fig. 1) has a 222 symmetry and each Zn atom has a distorted rectangular pyramidal geometry. Zn atoms are linked to two bidentate –S2CNR2 ligands in the basal plane and are bridged by a 4,4'-bipy ligand at the apex. The 4,4'-bipy ligand is not planar and the dihedral angle between the two pyridine rings is 38.6°. There are two shorter [2.3319 (8) Å] and two longer Zn—S bond lengths [2.6290 (9) Å], which are similar to the distances found in [(MeiPrNCS2)2Zn]2.TMED (Malik et al., 1997) of 2.349 (2) and 2.5640 (7)/2.6103 (7) Å, respectively. The shorter Zn—S bonds are associated with the longer S—C distances. This indicates that the dithiocarbamate ligand is asymmetrically linked to zinc. The Zn—N bond length [2.085 (3) Å] is shorter than that of [(MeiPrNCS2)2Zn]2.TMED [2.137 (5) Å] and longer than that of [(MeiPrNCS2)Zn].pyridine [2.069 (2) Å; REFERENCE]. This difference may be attributed to the very different steric characters of the N-containing bridged ligands.