The crystal and molecular structures of rosebengal derivatives and organometallic compounds containing mercury, rhodium, silver and silicon

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1988
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Janakiraman, Musiri
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Robert A. Jacobson
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Chemistry

The Department of Chemistry seeks to provide students with a foundation in the fundamentals and application of chemical theories and processes of the lab. Thus prepared they me pursue careers as teachers, industry supervisors, or research chemists in a variety of domains (governmental, academic, etc).

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The crystal and molecular structures of three rose bengal derivatives and four selected organometallic compounds have been determined by X-ray single crystal method. A brief description of the structural results for each compound is given below;C[subscript]20H[subscript]4CL[subscript]4I[subscript]4O[subscript]5· 11[over]2C[subscript]4H[subscript]8O[subscript]2 (1) crystallizes in the triclinic space group P1 with a = 12.669(6), b = 12.989(2), c = 10.693(4) A and [alpha] = 92.60(4), [beta] = 111.04(5), [gamma] = 102.32(5)°. The lactoid form is clearly revealed. The length of the lactonic bond is found to be 1.469(7) A;C[subscript]34H[subscript]16CL[subscript]4I[subscript]4O[subscript]5 (2) crystallizes in the triclinic space group P1 with a = 13.637(5), b = 15.284(6), c = 9.021(3) A, [alpha] = 102.38(3), [beta] = 96.59, [gamma] = 108.11(4)°. Careful analyses of electron density and difference electron density maps point to 2 being a dibenzyl ester;C[subscript]32H[subscript]34CL[subscript]4I[subscript]4N[subscript]2O[subscript]5 (3) crystallizes in the triclinic space group P1 with a = 18.293(8) b = 18.907(6), c = 13.534(3) A, [alpha] = 95.76(3), [beta] = 90.99(3), [gamma] = 61.32(3)°. Unlike the case of 2, the quinoidic end of the molecule has some phenoxide character; (CLC[subscript]6H[subscript]12NHgCL) HgCL[subscript]3 (4) crystallizes in the monoclinic space group Pc with a = 10.532(6), b = 9.866(2), c = 14.093(7) A, [beta] = 99.23(6)°. An interesting feature of the molecular structure is that of the hitherto unobserved discrete HgCL[subscript]3[superscript]- anion which shows a distorted trigonal geometry;RhCL (P(C[subscript]6H[subscript]6)[subscript]3) [subscript]2C[subscript]9H[subscript]12 (5) crystallizes in the orthorhombic space group Pbca with a = 23.629(6), b = 23.91(3), c = 13.173(8) A. The coordination around the rhodium atom is essentially square planar. The central [pi] bond of the cumulene ligand is lengthened (1.36 A) relative to the distance in the free ligand (1.27 A). The cumulene ligand shows an interesting "flapping" disorder; (Ag ([eta][superscript]5-C[subscript]5H[subscript]5)[subscript]2Fe[subscript]2(CO)[subscript]3CS[subscript]3) BF[subscript]4 (6) crystallizes in the triclinic space group P1 with a = 13.771(4), b = 15.047(7), c = 12,544(4) A, [alpha] = 109.55(3), [beta] = 93.77(3), [gamma] = 90.76(3)°. The coordination around the silver atom is essentially trigonal;SiO[subscript]4NC[subscript]8H[subscript]17 (7) crystallizes in the monoclinic space group P2[subscript]1/n with a = 10.956(4), b = 11.187(2), c = 17.638(8) A, [beta] = 95.84(4)°. The coordination around the silicon atom is nearly trigonal bipyramidal. The length of the N→Si bond distance is 2.152 A. ftn*DOE Report IS-T-1340. This work was performed under contract No. W-7405-Eng-82 with the U.S. Department of Energy.

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Fri Jan 01 00:00:00 UTC 1988