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Synthesis and Structural Characterization of a New Cyanomanganate(III) Complex, Heptapotassium µ-Oxo-bis[pentacyanomanganate(III)]cyanide

Ziolo, Ronald F. and Stanford, Richard H. and Rossman, George R. and Gray, Harry B. (1974) Synthesis and Structural Characterization of a New Cyanomanganate(III) Complex, Heptapotassium µ-Oxo-bis[pentacyanomanganate(III)]cyanide. Journal of the American Chemical Society, 96 (26). pp. 7910-7915. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20131127-071921404

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Abstract

The final product resulting from the reaction of KMnO_4 and KCN in saturated aqueous solution is a gold-brown compound K_7[(CN)_5MnOMn(CN)_5]CN, as established by a single-crystal X-ray diffraction study. Full-matrix leastsquares refinement included anisotropic temperature parameters for all atoms and converged with a final R index (on F) of 0.091. The structure contains the oxo bridged [Mn_2O(CN)_(10)]^(6-) ion, which has 2/m crystallographic symmetry with the bridging oxygen atom lying at a center of symmetry. The ion exists in an eclipsed rotomeric configuration. The Mn-O distance is relatively short, 1.723 (4) Å. Crystallographically independent potassium ions are coordinated to the nitrogen ends of cyanide groups in trigonal prismatic, octahedral, and square antiprismatic geometries. Crystal data are as follows: orthorhombic; space group Ibɑm; ɑ = 12.397 (8), b = 12.772 (8), c = 14.618 (7) A (temperature 23°); Z = 4; d_(obsd) = 1.98, d_(calcd) = 1.97 g/cm^3. The synthesis, isolation, and physical characteristics of K_7[Mn_2O(CN)_(10)]CN are reported along with spectral and magnetic data. The principal features in the infrared spectrum are cyanide stretching bands centered around 2090 cm^(-1). The optical absorption spectrum in a KBr pellet consists of a primary band at 370 nm with a prominent shoulder at 410 nm and a weak shoulder at approximately 610 nm. The gold-brown crystals are strongly pleochroic, the crystals being colorless when the E vector is parallel to the long needle axis. This characteristic serves as a convenient means of identification for this substance. At room temperature K_7[Mn_2O(CN)_(10)]CN is diamagnetic.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja00833a011DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00833a011PublisherArticle
ORCID:
AuthorORCID
Rossman, George R.0000-0002-4571-6884
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 1974 American Chemical Society. Publication Date: December 1974. We thank Drs. D. D. Titus and F. Fronczek for helpful discussions. This research was supported by the National Science Foundation.
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Issue or Number:26
Record Number:CaltechAUTHORS:20131127-071921404
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20131127-071921404
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:42745
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:27 Nov 2013 16:47
Last Modified:22 Nov 2019 09:58

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