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Acta Crystallogr Sect E Struct Rep Online. 2009 July 1; 65(Pt 7): m809.
Published online 2009 June 20. doi:  10.1107/S1600536809023186
PMCID: PMC2969329

Bis(2,4,6-trimethyl­phen­yl)zinc(II)

Abstract

The title compound, [Zn(C9H11)2] or Mes2Zn (Mes = mesityl = 2,4,6-trimethyl­phen­yl), crystallizes with a quarter of a mol­ecule in the asymmetric unit. The ZnII atom is in a strictly linear environment with a Zn—C bond length of 1.951 (5) Å. Due to the imposed 2/m symmetry, both aromatic rings are coplanar. One of the methyl groups is disordered over two equally occupied positions.

Related literature

For the first synthesis of dimesitylzinc, see: Seidel & Bürger (1981 [triangle]). For related structures, see: Brooker et al. (1992 [triangle]); Cole et al. (2003 [triangle]); Markies et al. (1990 [triangle]); Sun et al. (1998 [triangle]); Weidenbruch et al. (1989 [triangle]); Westerhausen et al. (2005 [triangle]).

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Object name is e-65-0m809-scheme1.jpg

Experimental

Crystal data

  • [Zn(C9H11)2]
  • M r = 303.73
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-65-0m809-efi1.jpg
  • a = 18.3059 (9) Å
  • c = 5.0494 (4) Å
  • V = 1692.08 (18) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.44 mm−1
  • T = 183 K
  • 0.05 × 0.05 × 0.04 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: none
  • 10286 measured reflections
  • 1016 independent reflections
  • 685 reflections with I > 2σ(I)
  • R int = 0.046

Refinement

  • R[F 2 > 2σ(F 2)] = 0.071
  • wR(F 2) = 0.270
  • S = 1.13
  • 1016 reflections
  • 53 parameters
  • H-atom parameters constrained
  • Δρmax = 1.33 e Å−3
  • Δρmin = −0.60 e Å−3

Data collection: COLLECT (Nonius, 1998 [triangle]); cell refinement: DENZO (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023186/bt2971sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023186/bt2971Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the Deutsche Forschungsgemeinschaft (DFG, Bonn–Band Godesberg, Germany) for generous financial support. We also acknowledge the funding of the Fonds der Chemischen Indunstrie (Frankfurt/Main, Germany). In addition, SK is very grateful to the Verband der Chemischen Industrie (VCI/FCI) for a PhD grant.

supplementary crystallographic information

Comment

After the first synthesis of dimesitylzinc by Seidel & Bürger (1981), its structure was determined more than 20 years later (Cole et al., 2003). Here we present another modification of this diarylzinc compound.

Whereas dialkylzinc is monomeric diphenylzinc crystallizes as a loose and unsymmetric dimer (Markies et al. (1990)). A planar molecule with a strictly two coordinated zinc centre is observed for bis(2,4,6-trimethylphenyl)zinc (dimesitylzinc) by Cole et al. (2003). Other substitution patterns of the arene ring also lead to monomeric, but not strictly linear molecules in the solid state. Sun et al. (1998) published the structure of bis(pentafluorophenyl)zinc and Brooker et al. (1992) reported the structure of bis[2,4,6-tris(rifluoromethyl)phenyl]zinc with a C—Zn—C bond angle of 170°. A The C—Zn—C angle decreases with increasing steric chain and a value of 165.9° was found in bis[2,4,6-tri(tert -butylphenyl]zinc by Westerhausen et al. (2005).

Experimental

All manipulations were performed in an atmosphere of argon using standard Schlenk techniques. THF and toluene were dried (Na/benzophenone) and distilled prior to use. Mes2Zn was prepared according to a literature procedure (Seidel & Bürger, 1981). Recrystallization of Mes2Zn from toluene at +4%C led to the formation of single crystals of the title compound.

Refinement

All hydrogen atoms were set to idealized positions and were refined with 1.2 times (1.5 for methyl groups) the isotropic displacement parameter of the corresponding carbon atom. One of the methyl groups is disordered over two equally occupied positions. The structure contains solvent accessible voids. But the final difference peak of 1.33 e/A3 is on a special position and could not be related to a solvent molecule.

Figures

Fig. 1.
Molecular structure of Mes2Zn, showing 40% probability displacement ellipsoides and the atom numbering scheme.

Crystal data

[Zn(C9H11)2]Dx = 1.192 Mg m3
Mr = 303.73Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/ncmCell parameters from 10286 reflections
Hall symbol: -P 4ac 2acθ = 3.2–27.5°
a = 18.3059 (9) ŵ = 1.44 mm1
c = 5.0494 (4) ÅT = 183 K
V = 1692.08 (18) Å3Octaeder, colourless
Z = 40.05 × 0.05 × 0.04 mm
F(000) = 640

Data collection

Nonius KappaCCD diffractometer685 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.046
graphiteθmax = 27.5°, θmin = 3.2°
[var phi] and ω scansh = −22→23
10286 measured reflectionsk = −23→23
1016 independent reflectionsl = −6→5

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.071H-atom parameters constrained
wR(F2) = 0.270w = 1/[σ2(Fo2) + (0.1807P)2 + 0.5133P] where P = (Fo2 + 2Fc2)/3
S = 1.13(Δ/σ)max < 0.001
1016 reflectionsΔρmax = 1.33 e Å3
53 parametersΔρmin = −0.60 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.041 (11)

Special details

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)

xyzUiso*/UeqOcc. (<1)
Zn10.00000.50000.00000.0388 (6)
C1−0.0524 (2)0.5524 (2)−0.2778 (9)0.0397 (13)
C2−0.1176 (2)0.5250 (2)−0.3816 (7)0.0413 (11)
C3−0.1542 (2)0.5623 (2)−0.5831 (8)0.0424 (11)
H3A−0.19870.5431−0.65000.051*
C4−0.1268 (2)0.6268 (2)−0.6875 (9)0.0432 (14)
C5−0.1687 (2)0.6687 (2)−0.8986 (11)0.0455 (14)
H5A−0.14180.7132−0.94520.068*0.50
H5B−0.21700.6820−0.83020.068*0.50
H5C−0.17430.6381−1.05630.068*0.50
C6−0.1516 (2)0.4566 (2)−0.2699 (8)0.0503 (12)
H6A−0.19330.4422−0.37990.075*
H6B−0.16830.4659−0.08860.075*
H6C−0.11530.4172−0.26870.075*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.0385 (7)0.0385 (7)0.0394 (9)0.0034 (3)−0.0015 (2)0.0015 (2)
C10.0435 (19)0.0435 (19)0.032 (2)0.008 (2)0.0036 (14)−0.0036 (14)
C20.043 (2)0.044 (2)0.038 (2)0.0059 (17)0.0021 (16)−0.0033 (16)
C30.046 (2)0.045 (2)0.0353 (19)0.0052 (16)0.0002 (16)−0.0052 (17)
C40.051 (2)0.051 (2)0.028 (2)0.010 (3)0.0028 (14)−0.0028 (14)
C50.054 (2)0.054 (2)0.029 (3)0.005 (3)−0.0019 (16)0.0019 (16)
C60.052 (3)0.045 (2)0.054 (2)−0.0005 (18)−0.0011 (19)0.0024 (19)

Geometric parameters (Å, °)

Zn1—C11.951 (5)C4—C3ii1.386 (5)
Zn1—C1i1.951 (5)C4—C51.522 (7)
C1—C2ii1.396 (5)C5—H5A0.9800
C1—C21.396 (5)C5—H5B0.9800
C2—C31.397 (6)C5—H5C0.9800
C2—C61.509 (6)C6—H6A0.9800
C3—C41.386 (5)C6—H6B0.9800
C3—H3A0.9500C6—H6C0.9800
C1—Zn1—C1i179.999 (1)C4—C5—H5A109.5
C2ii—C1—C2118.1 (5)C4—C5—H5B109.5
C2ii—C1—Zn1120.9 (2)H5A—C5—H5B109.5
C2—C1—Zn1120.9 (2)C4—C5—H5C109.5
C1—C2—C3120.6 (4)H5A—C5—H5C109.5
C1—C2—C6120.7 (4)H5B—C5—H5C109.5
C3—C2—C6118.7 (3)C2—C6—H6A109.5
C4—C3—C2121.3 (4)C2—C6—H6B109.5
C4—C3—H3A119.4H6A—C6—H6B109.5
C2—C3—H3A119.4C2—C6—H6C109.5
C3ii—C4—C3118.1 (5)H6A—C6—H6C109.5
C3ii—C4—C5120.9 (2)H6B—C6—H6C109.5
C3—C4—C5120.9 (2)

Symmetry codes: (i) −x, −y+1, −z; (ii) −y+1/2, −x+1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2971).

References

  • Brooker, S., Bertel, N., Stalke, D., Noltemeyer, M., Roesky, H. W., Sheldrick, G. M. & Edelmann, F. T. (1992). Organometallics, 11, 192–195.
  • Cole, S. C., Coles, M. P. & Hitchcock, P. B. (2003). Dalton Trans. pp. 3663–3664.
  • Markies, P. R., Schat, G., Akkermann, O. S. & Bickelhaupt, F. (1990). Organometallics, 9, 2243–2247.
  • Nonius (1998). 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.
  • Seidel, W. & Bürger, I. (1981). Z. Anorg. Allg. Chem.473, 166–170.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Sun, Y., Piers, W. E. & Parvez, M. (1998). Can. J. Chem.76, 513–517.
  • Weidenbruch, M., Herrndorf, M., Schäfer, A., Pohl, S. & Saak, W. (1989). J. Organomet. Chem.361, 139–145.
  • Westerhausen, M., Ossberger, M. W., Alexander, J. S. & Ruhlandt-Senge, K. (2005). Z. Anorg. Allg. Chem.631, 2836-2841.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography