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Acta Cryst. (2007). E63, m1847    [ doi:10.1107/S1600536807027183 ]

Bis{2-[(dimethylamino-[kappa]N)methyl]benzenethiolato-[kappa]S}zinc(II)

L. S. von Chrzanowski, M. Lutz, A. L. Spek, H. Kleijn and G. van Koten

Abstract top

In the title compound, [Zn(C9H12NS)2], the ZnII center is located on a twofold rotation axis and is coordinated in a distorted tetrahedral environment in a bidentate fashion by anionic thiolate S and neutral amino N atoms of two 2-[(dimethylamino)methyl]benzenethiolate ligands. All the molecules are in the [Delta] form. The chosen crystal can thus be considered enantiomerically pure. Intermolecular C-H...[pi] contacts connect the molecules into a two-dimensional network.

Comment top

The title compound, (I), crystallizes enantiomerically pure in space group P21212. The absolute structure of the crystal chosen could be determined from the Flack parameter of −0.013 (9) (Flack, 1983). The unit cell consists of two chiral Zn(C9H12NS)2 molecules, in which the ZnII complex appears in the Δ form (Ernst et al., 1967).

The ZnII center occupies a special position, located on a twofold axis at [1/2, 0, z]. The coordination geometry at the ZnII is defined by two monoanionic, S,N-bonded 2-[(dimethylamino)methyl]benzenethiolato ligands (Fig. 1). The ligand coordinates to the metal in a bidentate fashion via the anionic thiolato S1 [Zn1—S1 = 2.2811 (4) Å] and the neutral amino N1 [Zn1—N1 = 2.1129 (14) Å]. These distances compare well with those observed in the related Zn(SC6H4CH(Me)NMe2-2)2 complex reported by Rijnberg et al. (1997), with Zn—S of 2.284 (3) and 2.260 (2) Å, and Zn—N of 2.146 (8) and 2.096 (6) Å.

The four coordinated ZnII atom has a distorted-tetrahedral geometry, which is apparent from the S—Zn—N angles of 101.76 (8) and 102.41 (4)°. This can also be seen from the values for the quadratic elongation of 1.052 and for the angle variance of 168.05 Deg2 (Robinson et al., 1971). A conformational analysis of the ring puckering results in a coefficient of 92.6% for the cosine form of the six membered N1—Zn1—S1—C1—C2—C7 chelate ring (Evans & Boeyens, 1989). Therefore the ring is best described as a boat conformation.

The C1—S1—Zn1 angle of 102.47 (5)° indicates a distorted-tetrahedral geometry of the S atom, the distance C1—S1 is 1.7743 (17)Å and again agrees well with the C—S distance found in the Zn(SC6H4CH(Me)NMe2-2)2 complex with C—S = 1.76 (1)Å (Rijnberg et al., 1997). The geometry of the amino N atom is tetrahedral, with angles ranging from 107.63 (13) [C9—N1—C7] to 111.70 (11)° [C9—N1—Zn1].

There is an intermolecular C—H···π contact of H8C to the C1—C6 aromatic ring (centroid Cg), with H8C···Cgi = 2.96Å [symmetry code (i) 1 − x, −y, z], which connects the molecules into a two dimensional network perpendicular to c (Fig. 2).

Related literature top

A related structure was reported by Rijnberg et al. (1997). For related literature concerning the geometrical features see: Ernst et al. (1967); Evans & Boeyens (1989); Robinson et al. (1971).

Experimental top

In order to synthesize mixed zinc complexes with isopropyllactate and aminoarenethiolate ligands, the title compound, (I), was formed by disproportionation of the mixed zinc compound.

To a mixture of 2.8 mMol EtZn(SC6H4CMe2NMe2-2) and 2.8 mMol (L)-isopropyllactate was added dry diethyl ether. The reaction mixture was stirred for 1 h. At the bottom of the reaction vessel a sticky solid was deposed. After removal of the clear solution, this solid was dried in vacuo. Yellow, needle shaped crystals for data collection were obtained by recrystallization from C6D6/CDCl3 (ratio 1:1).

Refinement top

All hydrogen atoms were introduced in geometrically idealized positions (C—H = 0.95–0.99 Å) and refined with a riding model. Methyl hydrogen atoms where refined to behave as a rigid rotator using the SHELXL97 (Sheldrick, 1997) command AFIX 137. The isotropic displacement parameters of the hydrogen atoms were constrained with Uiso(H) = 1.2Ueq(C) for H atoms of CH and CH2 moieties and with Uiso(H) = 1.5Ueq(C) for methyl H atoms.

Computing details top

Data collection: COLLECT (Nonius, 1999); cell refinement: HKL-2000 (Otwinowski & Minor, (1997); data reduction: HKL-2000; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: manual editing of the SHELXL97 output.

Figures top
[Figure 1] Fig. 1. : Displacement ellipsoid plot and atomic numbering scheme of (I). Ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) 1 − x, −y, z]
[Figure 2] Fig. 2. : C—H···π interaction in (I), view along the crystallographic c axis. The C—H···π contacts are shown as dashed lines. [Symmetry codes: (i) 1 − x, −y, z; (ii) x − 1/2, 1/2 − y, 1 − z; (iii) 1/2 + x, 1/2 − y, −z; (iv) 1/2 − x, 1/2 + y, −z; (v) 1 − x, 1 − y, z; (vi) 3/2 − x, 1/2 + y, 1 − z; (vii) x, 1 + y, z]
Bis{2-[(dimethylamino-κN)methyl]benzenethiolato-κS}zinc(II) top
Crystal data top
[Zn(C9H12NS)2]F000 = 416
Mr = 397.88Dx = 1.416 Mg m−3
Orthorhombic, P21212Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2 2abCell parameters from 10982 reflections
a = 10.1731 (2) Åθ = 1.0–27.5º
b = 14.1431 (2) ŵ = 1.54 mm−1
c = 6.4862 (1) ÅT = 150 (2) K
V = 933.23 (3) Å3Needle, yellow
Z = 20.36 × 0.12 × 0.09 mm
Data collection top
Nonius KappaCCD
diffractometer		2143 independent reflections
Radiation source: rotating anode2001 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.037
T = 150(2) Kθmax = 27.5º
φ and ω scansθmin = 2.5º
Absorption correction: multi-scan
(MULABS routine of PLATON; Spek, 2003)		h = −12→13
Tmin = 0.82, Tmax = 0.87k = −12→18
11294 measured reflectionsl = −8→8
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.020  w = 1/[σ2(Fo2) + (0.0182P)2 + 0.1166P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.047(Δ/σ)max = 0.001
S = 1.06Δρmax = 0.20 e Å−3
2143 reflectionsΔρmin = −0.18 e Å−3
107 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 880 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.013 (9)
Crystal data top
[Zn(C9H12NS)2]V = 933.23 (3) Å3
Mr = 397.88Z = 2
Orthorhombic, P21212Mo Kα
a = 10.1731 (2) ŵ = 1.54 mm−1
b = 14.1431 (2) ÅT = 150 (2) K
c = 6.4862 (1) Å0.36 × 0.12 × 0.09 mm
Data collection top
Nonius KappaCCD
diffractometer		2143 independent reflections
Absorption correction: multi-scan
(MULABS routine of PLATON; Spek, 2003)		2001 reflections with I > 2σ(I)
Tmin = 0.82, Tmax = 0.87Rint = 0.037
11294 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.020H-atom parameters constrained
wR(F2) = 0.047Δρmax = 0.20 e Å−3
S = 1.06Δρmin = −0.18 e Å−3
2143 reflectionsAbsolute structure: Flack (1983), 880 Friedel pairs
107 parametersFlack parameter: −0.013 (9)
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
Zn10.50000.00000.11091 (3)0.02267 (8)
S10.34728 (4)0.09804 (3)0.25447 (7)0.02740 (10)
N10.61791 (13)0.09749 (11)−0.0526 (2)0.0260 (3)
C10.43649 (15)0.20488 (12)0.2857 (2)0.0232 (3)
C20.52665 (15)0.23934 (12)0.1408 (2)0.0256 (4)
C30.59119 (17)0.32491 (12)0.1791 (3)0.0331 (4)
H30.65300.34800.08160.040*
C40.56685 (18)0.37667 (13)0.3565 (3)0.0382 (5)
H40.61220.43430.38140.046*
C50.47595 (18)0.34349 (13)0.4964 (3)0.0351 (4)
H50.45770.37890.61750.042*
C60.41102 (17)0.25888 (13)0.4619 (3)0.0291 (4)
H60.34820.23720.55940.035*
C70.54904 (17)0.19101 (13)−0.0639 (2)0.0294 (4)
H7A0.46280.1815−0.13140.035*
H7B0.60120.2338−0.15280.035*
C80.74530 (16)0.10835 (13)0.0541 (3)0.0344 (4)
H8A0.79350.04840.04910.052*
H8B0.73000.12610.19810.052*
H8C0.79700.1577−0.01420.052*
C90.6432 (2)0.06543 (15)−0.2681 (3)0.0419 (5)
H9A0.70970.1063−0.33150.063*
H9B0.56150.0690−0.34790.063*
H9C0.67490.0000−0.26640.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.01809 (12)0.02763 (14)0.02228 (12)−0.00127 (13)0.0000.000
S10.0215 (2)0.0304 (2)0.0303 (2)−0.00084 (18)0.00561 (18)−0.00021 (19)
N10.0218 (7)0.0309 (8)0.0253 (7)−0.0020 (6)0.0054 (5)0.0016 (6)
C10.0199 (7)0.0251 (9)0.0245 (8)0.0039 (7)−0.0040 (6)0.0046 (7)
C20.0217 (9)0.0271 (9)0.0282 (8)0.0037 (7)−0.0020 (6)0.0056 (7)
C30.0252 (9)0.0305 (11)0.0435 (10)0.0017 (8)0.0024 (7)0.0086 (9)
C40.0308 (10)0.0285 (10)0.0552 (12)−0.0001 (8)−0.0053 (9)−0.0055 (9)
C50.0356 (12)0.0327 (10)0.0370 (10)0.0066 (8)−0.0043 (8)−0.0059 (8)
C60.0271 (9)0.0335 (10)0.0267 (8)0.0074 (8)−0.0020 (7)0.0021 (8)
C70.0281 (8)0.0348 (10)0.0255 (9)0.0012 (8)0.0025 (7)0.0100 (7)
C80.0195 (8)0.0350 (11)0.0487 (11)−0.0043 (8)−0.0013 (8)0.0065 (9)
C90.0400 (11)0.0532 (13)0.0325 (10)−0.0058 (10)0.0172 (9)−0.0035 (9)
Geometric parameters (Å, °) top
Zn1—N1i2.1128 (14)C4—C51.378 (3)
Zn1—N12.1129 (14)C4—H40.9500
Zn1—S1i2.2811 (4)C5—C61.385 (2)
Zn1—S12.2811 (4)C5—H50.9500
S1—C11.7743 (17)C6—H60.9500
N1—C81.477 (2)C7—H7A0.9900
N1—C91.492 (2)C7—H7B0.9900
N1—C71.499 (2)C8—H8A0.9800
C1—C61.398 (2)C8—H8B0.9800
C1—C21.401 (2)C8—H8C0.9800
C2—C31.399 (2)C9—H9A0.9800
C2—C71.510 (2)C9—H9B0.9800
C3—C41.386 (2)C9—H9C0.9800
C3—H30.9500
N1i—Zn1—N1119.76 (8)C4—C5—C6120.53 (17)
N1i—Zn1—S1i101.23 (4)C4—C5—H5119.7
N1—Zn1—S1i102.41 (4)C6—C5—H5119.7
N1i—Zn1—S1102.41 (4)C5—C6—C1121.03 (17)
N1—Zn1—S1101.24 (4)C5—C6—H6119.5
S1i—Zn1—S1131.82 (2)C1—C6—H6119.5
C1—S1—Zn1102.47 (5)N1—C7—C2115.27 (13)
C8—N1—C9108.61 (14)N1—C7—H7A108.5
C8—N1—C7109.96 (14)C2—C7—H7A108.5
C9—N1—C7107.63 (13)N1—C7—H7B108.5
C8—N1—Zn1109.33 (11)C2—C7—H7B108.5
C9—N1—Zn1111.70 (11)H7A—C7—H7B107.5
C7—N1—Zn1109.58 (10)N1—C8—H8A109.5
C6—C1—C2118.66 (16)N1—C8—H8B109.5
C6—C1—S1117.63 (13)H8A—C8—H8B109.5
C2—C1—S1123.67 (13)N1—C8—H8C109.5
C3—C2—C1119.26 (15)H8A—C8—H8C109.5
C3—C2—C7118.49 (15)H8B—C8—H8C109.5
C1—C2—C7122.08 (15)N1—C9—H9A109.5
C4—C3—C2121.38 (17)N1—C9—H9B109.5
C4—C3—H3119.3H9A—C9—H9B109.5
C2—C3—H3119.3N1—C9—H9C109.5
C5—C4—C3119.12 (18)H9A—C9—H9C109.5
C5—C4—H4120.4H9B—C9—H9C109.5
C3—C4—H4120.4
N1i—Zn1—S1—C1−154.00 (7)S1—C1—C2—C3179.43 (12)
N1—Zn1—S1—C1−29.82 (7)C6—C1—C2—C7−173.28 (15)
S1i—Zn1—S1—C188.32 (5)S1—C1—C2—C74.3 (2)
N1i—Zn1—N1—C8−141.01 (12)C1—C2—C3—C4−0.6 (3)
S1i—Zn1—N1—C8−30.18 (11)C7—C2—C3—C4174.74 (15)
S1—Zn1—N1—C8107.53 (11)C2—C3—C4—C5−0.8 (3)
N1i—Zn1—N1—C9−20.77 (10)C3—C4—C5—C60.9 (3)
S1i—Zn1—N1—C990.06 (12)C4—C5—C6—C10.4 (3)
S1—Zn1—N1—C9−132.23 (11)C2—C1—C6—C5−1.8 (2)
N1i—Zn1—N1—C798.41 (10)S1—C1—C6—C5−179.50 (13)
S1i—Zn1—N1—C7−150.76 (10)C8—N1—C7—C2−56.26 (18)
S1—Zn1—N1—C7−13.05 (10)C9—N1—C7—C2−174.41 (15)
Zn1—S1—C1—C6−143.07 (11)Zn1—N1—C7—C263.93 (16)
Zn1—S1—C1—C239.38 (14)C3—C2—C7—N1114.67 (17)
C6—C1—C2—C31.9 (2)C1—C2—C7—N1−70.1 (2)
Symmetry codes: (i) −x+1, −y, z.
Table 1
Selected geometric parameters (Å, °) top
Zn1—N12.1129 (14)S1—C11.7743 (17)
Zn1—S12.2811 (4)
N1i—Zn1—N1119.76 (8)S1i—Zn1—S1131.82 (2)
N1—Zn1—S1i102.41 (4)C1—S1—Zn1102.47 (5)
N1—Zn1—S1101.24 (4)
Symmetry codes: (i) −x+1, −y, z.
Table 2
C—H···π interaction (Å, °) top
X—H···CgX—HH···CgX···CgX—H···Cg
C8—H8C···Cgi0.982.963.8324 (19)149
Cg is the centroid of the C1–C6 aromatic ring. [Symmetry code: (i) 1 − x, −y, z]
Acknowledgements top

This work was supported by the Council for Chemical Sciences of the Netherlands Organization for Scientific Research (CW-NWO).

references
References top

Ernst, R. E., O'Conner, M. J. & Holm, R. H. (1967). J. Am. Chem. Soc. 89, 6104–6113.

Evans, D. G. & Boeyens, J. C. A. (1989). Acta Cryst. B45, 581–590.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Nonius (1999). COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Rijnberg, E., Hovestad, N. J., Kleij, A. W., Jastrzebski, J. T. B. H., Boersma, J., Janssen, M. D., Spek, A. L. & van Koten, G. (1997). Organometallics, 16, 2847–2857.

Robinson, K., Gibbs, G. V. & Ribbe, P. H. (1971). Science, 172, 567–570.

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

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.