Universität zu Köln

Fiolka, Christoph, Pantenburg, Ingo and Meyer, Gerd ORCID: 0000-0003-1000-9001 (2011). Transition-Metal(II)-Crown-Ether-Polyiodides. Cryst. Growth Des., 11 (11). S. 5159 - 5166. WASHINGTON: AMER CHEMICAL SOC. ISSN 1528-7505

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Abstract

The crown-ethers 12-crown-4 (12c4) and benzo-12-crown-4 (b12c4) encapsulate divalent manganese, iron, cobalt, and nickel cations building large sandwich-type dications with square-antiprismatic coordination polyhedra; benzo-15-crown-5 (b15c5) forms in-cavity complexes with six-plus-one coordinate Mn(11) and Co(II). The anions are a variety of polyiodides, I-3(-), I-5(-), I-7(-), I-12(2-), I-16(2-), and I-18(4-). The crystal. structures of 12 new compounds have been determined, 8 of which contain 12-crown-4: [Mn(12c4)(2)](I-3)(2)(12c4) (1) and [Co(12c4)(2)](I-3)(2)(12c4) (2) are isotypic (monoclinic, C2/c, No. IS) and contain isolated triiodide anions. Isotypic [Mn(12c4)(2)](I-5)(2) (3) and [Ni(12c4)(2)] (I-5)(2) (4) (monoclinic, Cm, No. 8) feature V/L-shaped I-5(-) anions which are connected to zigzag chains. The hexadecaiodides, built of nonaiodide and heptaiodide subunits, in the isotypic compounds [Mn(12c4)(2)](I-16) (5), [Fe(12c4)(2)](I-16) (6), [Co(12c4)(2))(I-16) (7) (orthorhombic, Pna2(1), No. 33) exhibit a new structural motif for I-16(2-) anions. The elusive octadecaiodide I-18(4-) in [Co(12c4)(2)](2)(I-18) (8) (monoclinic, C2/c, No 15) consists of a linear pentaiodide to which iodine and triiodide are attached Analogous reactions with benzo-12-crown-4 yielded the pentaiodides [Mn(b12c4)(2)](I-5)(2) (9) and [Co(b12c4)(2)](I-5)(2) ( 10). 9 features a trans-pentaiodide,chain to which an additional pentaiodide is connected; it also contains an isolated pentaiodide anion. The crystal structure of 10 contains isolated V/L-shaped pentaiodide anions exclusively. The anionic parts in [Co(b15c5)(2)(MeCN)(H2O)] (I-7)(2) (11) (monoclinic, Cc, No. 9) and [Mn(b15c5)(2)(H2O)(2)](I-12) (12) (monoclinic, P2(1)/c, No. 14) are determined by polymeric pyramidal heptaiodides in 11 and by a two-dimensional network of dodecaiodide anions with twisted sawhorse geometry in 12.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Fiolka, Christoph UNSPECIFIED UNSPECIFIED UNSPECIFIED Pantenburg, Ingo UNSPECIFIED UNSPECIFIED UNSPECIFIED Meyer, Gerd UNSPECIFIED orcid.org/0000-0003-1000-9001 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-486297
DOI:	10.1021/cg201198t
Journal or Publication Title:	Cryst. Growth Des.
Volume:	11
Number:	11
Page Range:	S. 5159 - 5166
Date:	2011
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1528-7505
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language POLYHALIDES; POLYIODIDE; CATIONS Multiple languages Chemistry, Multidisciplinary; Crystallography; Materials Science, Multidisciplinary Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/48629