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The title compound, [Zn2(C5H8NS2)4(C10H8N2)], consists of two bis(pyrrol­idine­dithio­carboxylato)­zinc molecules bridged by a 4,4′-bi­pyridine molecule, and has a 222 symmetry. Each Zn atom forms a five-coordinate pseudo-square-based pyramidal arrangement, with four Zn—S interactions and one Zn—N interaction; the Zn—N distance is 2.085 (3) Å and the Zn—S distances are in the range 2.3319 (8)–2.6290 (9) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199012706/bk1483sup1.cif
Contains datablocks (I), globle

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270199012706/bk1483Isup2.hkl
Contains datablock I

CCDC reference: 140934

Comment top

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.

Experimental top

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.

Refinement top

The C7 atom was found to be disordered and was refined as C7 and C7A with occupancies of 0.55 and 0.45, respectively.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. View of the title compound with the atomic numbering scheme and 30% probability ellipsoids.
µ-(4,4'-Bipyridine)-N:N'-bis[bis(pyrrolidinedithiocarboxylato-S,S')zinc(II)] top
Crystal data top
[Zn2(C5H8NS2)4(C10H8N2)]F(000) = 3600
Mr = 871.90Dx = 1.493 Mg m3
Orthorhombic, FdddMo Kα radiation, λ = 0.71073 Å
Hall symbol: -F 2uv 2vwCell parameters from 6152 reflections
a = 11.7643 (2) Åθ = 2.1–29.4°
b = 19.9965 (3) ŵ = 1.70 mm1
c = 32.9889 (3) ÅT = 293 K
V = 7760.5 (2) Å3Cut hexagonal block, yellow
Z = 80.20 × 0.20 × 0.18 mm
Data collection top
Siemens SMART CCD
diffractometer
2497 independent reflections
Radiation source: fine-focus sealed tube2009 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω scansθmax = 29.4°, θmin = 2.1°
Absorption correction: empirical (using intensity measurements) (SADABS; sheldrick, 1996)
?
h = 158
Tmin = 0.644, Tmax = 0.737k = 2727
11821 measured reflectionsl = 4543
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.08Calculated w = 1/[σ2(Fo2) + (0.0532P)2 + 18.0531P]
where P = (Fo2 + 2Fc2)/3
2497 reflections(Δ/σ)max < 0.001
115 parametersΔρmax = 0.62 e Å3
16 restraintsΔρmin = 0.33 e Å3
Crystal data top
[Zn2(C5H8NS2)4(C10H8N2)]V = 7760.5 (2) Å3
Mr = 871.90Z = 8
Orthorhombic, FdddMo Kα radiation
a = 11.7643 (2) ŵ = 1.70 mm1
b = 19.9965 (3) ÅT = 293 K
c = 32.9889 (3) Å0.20 × 0.20 × 0.18 mm
Data collection top
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 = 0.737Rint = 0.024
11821 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04616 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 1.08Δρmax = 0.62 e Å3
2497 reflectionsΔρmin = 0.33 e Å3
115 parameters
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 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Zn10.37500.37500.045213 (14)0.0587 (2)
S10.56323 (7)0.38695 (4)0.06616 (3)0.0707 (3)
S20.45846 (7)0.25380 (4)0.05343 (3)0.0782 (3)
N10.37500.37500.01799 (9)0.0495 (7)
N20.6784 (2)0.27358 (11)0.06687 (8)0.0634 (6)
C10.3430 (3)0.32096 (13)0.03915 (9)0.0572 (7)
H10.32070.282970.024950.069*
C20.3414 (2)0.31894 (12)0.08063 (8)0.0531 (6)
H20.31810.280390.094030.064*
C30.37500.37500.10258 (10)0.0420 (7)
C40.5772 (3)0.30107 (13)0.06273 (9)0.0565 (6)
C50.7844 (3)0.3118 (2)0.07296 (12)0.0730 (9)
H5A0.78240.33600.098420.088*
H5B0.79610.34340.051040.088*
C60.8764 (4)0.2597 (2)0.0734 (2)0.113 (2)
H6A0.94180.27530.05820.135*
H6B0.90010.25070.10100.135*
C70.8309 (7)0.2002 (4)0.0552 (3)0.092 (3)0.55
H7A0.86520.16070.06710.111*
H7B0.84540.19990.02620.111*
C80.7026 (3)0.2015 (2)0.06352 (14)0.0885 (11)
H8A0.66030.18140.041380.106*
H8B0.68430.17820.088490.106*
C7A0.8224 (10)0.1957 (5)0.0798 (4)0.100 (4)0.45
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0510 (3)0.0715 (3)0.0537 (3)0.0012 (2)0.0000.000
S10.0623 (5)0.0523 (4)0.0976 (6)0.0012 (3)0.0202 (4)0.0101 (4)
S20.0642 (5)0.0626 (5)0.1078 (7)0.0217 (4)0.0146 (4)0.0175 (4)
N10.048 (2)0.047 (2)0.053 (2)0.0037 (12)0.0000.000
N20.0578 (14)0.0439 (12)0.088 (2)0.0055 (10)0.0069 (13)0.0029 (11)
C10.068 (2)0.0447 (13)0.058 (2)0.0140 (12)0.0020 (13)0.0071 (11)
C20.066 (2)0.0368 (12)0.0570 (15)0.0117 (11)0.0060 (12)0.0004 (10)
C30.039 (2)0.0348 (15)0.052 (2)0.0005 (12)0.0000.000
C40.060 (2)0.0476 (13)0.062 (2)0.0091 (12)0.0035 (13)0.0039 (11)
C50.052 (2)0.061 (2)0.106 (3)0.0075 (13)0.008 (2)0.001 (2)
C60.067 (2)0.081 (3)0.190 (5)0.008 (2)0.008 (3)0.001 (3)
C70.081 (5)0.076 (5)0.120 (7)0.019 (4)0.008 (6)0.000 (5)
C80.087 (2)0.046 (2)0.132 (3)0.002 (2)0.015 (2)0.006 (2)
C7A0.096 (8)0.056 (5)0.148 (11)0.019 (5)0.022 (8)0.002 (7)
Geometric parameters (Å, º) top
Zn1—N12.085 (3)N2—C81.474 (4)
Zn1—S12.3319 (8)N2—C51.476 (4)
Zn1—S1i2.3319 (8)C1—C21.369 (4)
Zn1—S2i2.6290 (9)C2—C31.392 (3)
Zn1—S22.6290 (9)C3—C2i1.392 (3)
S1—C41.729 (3)C3—C3ii1.479 (7)
S2—C41.714 (3)C5—C61.502 (5)
N1—C11.340 (3)C6—C71.437 (10)
N1—C1i1.340 (3)C7—C81.535 (9)
N2—C41.318 (4)
N1—Zn1—S1107.23 (3)C4—N2—C8125.1 (3)
N1—Zn1—S1i107.23 (3)C4—N2—C5124.1 (2)
S1—Zn1—S1i145.53 (5)C8—N2—C5110.7 (3)
N1—Zn1—S2i95.92 (2)N1—C1—C2123.2 (2)
S1—Zn1—S2i103.28 (3)C1—C2—C3119.5 (2)
S1i—Zn1—S2i73.10 (3)C2i—C3—C2117.3 (3)
N1—Zn1—S295.92 (2)C2i—C3—C3ii121.4 (2)
S1—Zn1—S273.10 (3)C2—C3—C3ii121.4 (2)
S1i—Zn1—S2103.28 (3)N2—C4—S2121.6 (2)
S2i—Zn1—S2168.17 (5)N2—C4—S1119.6 (2)
C4—S1—Zn188.23 (10)S2—C4—S1118.8 (2)
C4—S2—Zn179.31 (10)N2—C5—C6104.5 (3)
C1—N1—C1i117.2 (3)C7—C6—C5107.6 (5)
C1—N1—Zn1121.4 (2)C6—C7—C8106.1 (5)
C1i—N1—Zn1121.4 (2)N2—C8—C7102.7 (4)
N1—Zn1—S1—C486.62 (10)N1—C1—C2—C30.4 (4)
S1i—Zn1—S1—C493.38 (10)C1—C2—C3—C2i0.2 (2)
S2i—Zn1—S1—C4172.78 (10)C1—C2—C3—C3ii179.8 (2)
S2—Zn1—S1—C44.45 (10)C8—N2—C4—S21.1 (5)
N1—Zn1—S2—C4101.69 (10)C5—N2—C4—S2177.0 (3)
S1—Zn1—S2—C44.56 (10)C8—N2—C4—S1178.2 (3)
S1i—Zn1—S2—C4149.01 (10)C5—N2—C4—S12.3 (4)
S2i—Zn1—S2—C478.31 (10)Zn1—S2—C4—N2172.6 (3)
S1—Zn1—N1—C1115.4 (2)Zn1—S2—C4—S16.7 (2)
S1i—Zn1—N1—C164.6 (2)Zn1—S1—C4—N2171.9 (2)
S2i—Zn1—N1—C1138.7 (2)Zn1—S1—C4—S27.5 (2)
S2—Zn1—N1—C141.3 (2)C4—N2—C5—C6176.6 (4)
S1—Zn1—N1—C1i64.6 (2)C8—N2—C5—C60.2 (5)
S1i—Zn1—N1—C1i115.4 (2)N2—C5—C6—C718.2 (7)
S2i—Zn1—N1—C1i41.3 (2)C5—C6—C7—C828.8 (8)
S2—Zn1—N1—C1i138.7 (2)C4—N2—C8—C7160.0 (5)
C1i—N1—C1—C20.2 (2)C5—N2—C8—C716.4 (6)
Zn1—N1—C1—C2179.8 (2)C6—C7—C8—N227.5 (8)
Symmetry codes: (i) x+3/4, y+3/4, z; (ii) x+3/4, y, z1/4.

Experimental details

Crystal data
Chemical formula[Zn2(C5H8NS2)4(C10H8N2)]
Mr871.90
Crystal system, space groupOrthorhombic, Fddd
Temperature (K)293
a, b, c (Å)11.7643 (2), 19.9965 (3), 32.9889 (3)
V3)7760.5 (2)
Z8
Radiation typeMo Kα
µ (mm1)1.70
Crystal size (mm)0.20 × 0.20 × 0.18
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionEmpirical (using intensity measurements) (SADABS; Sheldrick, 1996)
Tmin, Tmax0.644, 0.737
No. of measured, independent and
observed [I > 2σ(I)] reflections
11821, 2497, 2009
Rint0.024
(sin θ/λ)max1)0.690
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.121, 1.08
No. of reflections2497
No. of parameters115
No. of restraints16
H-atom treatmentH-atom parameters constrained
Calculated w = 1/[σ2(Fo2) + (0.0532P)2 + 18.0531P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)0.62, 0.33

Computer programs: SMART (Siemens, 1996a), SAINT (Siemens, 1996a), SAINT, SHELXS86 (Sheldrick, 1990), SHELXTL (Siemens, 1996b), SHELXTL.

Selected geometric parameters (Å, º) top
Zn1—N12.085 (3)N2—C51.476 (4)
Zn1—S12.3319 (8)C1—C21.369 (4)
Zn1—S22.6290 (9)C2—C31.392 (3)
S1—C41.729 (3)C3—C3i1.479 (7)
S2—C41.714 (3)C5—C61.502 (5)
N1—C11.340 (3)C6—C71.437 (10)
N2—C41.318 (4)C7—C81.535 (9)
N2—C81.474 (4)
N1—Zn1—S1107.23 (3)S1—Zn1—S273.10 (3)
S1—Zn1—S1ii145.53 (5)S1ii—Zn1—S2103.28 (3)
N1—Zn1—S295.92 (2)S2ii—Zn1—S2168.17 (5)
Symmetry codes: (i) x+3/4, y, z1/4; (ii) x+3/4, y+3/4, z.
 

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