D0092

SYNTHESES AND STRUCTURES OF [Pb₃Cl₁₀]^4- AND [PbBr₃]-. H. Miyamae, K. Nagae, G. Hihara, Department of Chemistry, Josai University, Keyakidai 1-1, Sakado-shi, Saitama 350-02, Japan

We found two new types of halogenoplumbate(II) of the formula, [Pb₃Cl₁₀]^4-(a) and [PbBr₃]-(b). They are obtained from DMF solution of PbX₂ (X=Cl or Br) with N,N,N',N'-tetramethylethylenediamine (me4pn).

There are two independent Pb atoms in (a). One at the center of symmetry is in regular octahedral coordination of six Cl atoms (Pb-Cl distances are in the range of 2.91~2.99 Å), while the other at general position is in square pyramid (Pb-Cl: 2.68~2.97 Å) with sixth Cl atom at 3.29Å.

The Pb atom in (b) has ₃ symmetry as in the case of [PbI₃]- of [hmtaH][PbI₃] (hmta=hexamethylenetetramine; H. Miyamae, H. Nishikawa, K. Hagimoto, G. Hihara, & M. Nagata, Chem. Lett., 1907-1910 (1988)) with Pb-Br distance of 3.00 Å. These two anions form infinite chain. The infinite chain in (a) is supported by [me4pnH₂]²⁺ ions with two independent N-H...Cl hydrogen bonds.

Crystal data: (a) [me4pnH₂]₂[Pb₃Cl₁₀], Mr 1240.6, monoclinic, space group P2₁/c (No. 14), a=11.290(3), b=15.164(2), c=11.477(2) Å, b=117.70(1)deg., V=1739.7(5) Å³, Z=2, Dx=2.367 g cm^-3, u(Mo K[[alpha]])=15.38 mm^-1, F(000)=1136.

(b) [me4pnH][PbBr₃], Mr 578.2, hexagonal, space group P6₃ (No. 173) or P6₃/m (No. 176), a=10.399(2), c=7.945(3) Å, V=744.0(5) Å³, Z=2, Dx=2.780 g cm^-3, u(Mo K[[alpha]])=19.38 mm^-1, F(000)=524.