The crystal and molecular structure of trans,trans-3,5-heptadien-2-ol–iron tricarbonyl: the hydrolysate of the syn,syn-1,5-dimethylpentadienyliron tricarbonyl cation

Abstract

The crystal structure of trans, trans-3,5-heptadien-2-ol-iron tricarbonyl, (C7H120)Fe(CO)3, the hydrolysate of the syn,syn-l,5-dimethylpentadienyliron tricarbonyl cation, has been determined by singlecrystal X-ray diffraction techniques using three-dimensional data gathered at ca -32°C by counter methods. The irregularly shaped yellow crystals obtained by vacuum sublimation are monoclinic, space group P21/c, and at ca -32°C,a = 16"885 (3), b = 17"831 (3), c= 8-275 (2) A, fl= 111"91 (1) °. At ca -32°C the calculated density for eight formula units of (CTHI20)Fe(CO)3 per unit cell is 1.455 g cm -3, in adequate agreement with the measured value (at 22°C) of 1-430 (1) g cm -3. The structure consists of monomeric (CTH120)Fe(CO)3 molecules linked by hydrogen bonds between the hydroxyl groups. Each Fe atom is coordinated by three CO ligands and the planar butadiene residue of a dimethylpentadienyl moiety. The hydrolysis (yielding the alcohol complex) is stereospecific, giving a racemic mixture of the alcohol with configurations RR and SS. Full-matrix least-squares refinement has converged with a weighted R index (on IFI) of 0"033 for the 2791 symmetry-independent reflections with I0>2"0cr(I0).

Chiral aggregation phenomena. 2. Evidence for partial "two-dimensional resolution" in a chiral monolayer

“…0 Yields determined by GC and expressed as percentages based on starting hypohalite. 6 Selectivity calculated from the molar ratio (CHC12 X/neo-C s ,, X) times (12 neopentane hydrogens/2 CH2C12 hydrogens) to account for the statistical factor. 0 (mmol of C02 + mmol of halogenated product/mmol of AcOX) 100. d Yield of methyl bromide was 75%; yield of acetic acid was 25%.…”

Triligating 11-membered rings containing tert-phosphino sites. Synthesis and structure

“…The measured intensities were reduced and assigned standard deviations as described elsewhere. 18 No absorption corrections were applied, and in only one case, 9, was a time-dependent correction for crystal decay (maximum value 2%) deemed necessary. scattering factors for S, P, O, C,20 and H21 were used in these calculations, and the real ( /') and imaginary ( /") corrections20 for anomalous dispersion were applied to the S and P scattering curves.…”

“…Chem., 78,1913 (1974). (18) S. Harada, Y. Uchida, M. Hlraishi, H, L. Kuo, and T. Yasunaga, Inorg. Chem., 17, 3371 (1978).…”