Quinquedentate Coordination of 6-Methyl-1,11-dithia-4,8-diazacyclotetradecan-6-amine to Cobalt(III). X-Ray Crystal Structure of the [Co(N3S2)(OOCCH3)] (ClO4)2.H2O Complex

The pendant arm macrocycle 6-methyl-1,11-dithia-4,8-diazacyclotetradecan-6-amine (7) can coordinate to cobalt(III) as a quinquedentate N3S2 ligand . Spectroscopy indicated a geometry with the macrocycle folded and the pendant amine and the unidentate donor in cis dispositions for the [Co(7) Cl ]2+ and [Co(7)(OOCCH3)]2+ products isolated. An X-ray crystal structure analysis of [Co(7)(OOCCH3)](ClO4)2.H2O characterized the cis stereochemistry. The complex crystallized in the Pbca space group, a 10.620(9), b 13.926(9), c 32.35(2)Ǻ, and analysis defined a distorted octahedral geometry with the primary and two secondary nitrogen donors occupying an octahedral face with relatively short Co-N bonds [1.937(7)-1.950(7)Ǻ], the acetate ion [Co-O 1.905(6)Ǻ] trans to one of the secondary amine donors and thioether donors [Co-S 2.223(3), 2.227(3)Ǻ] trans to the other nitrogen donors. Significant angle distortions occur around the metal ion. Base hydrolysis of the chloro complex is slow and stereoretentive , with a rate constant of 1.08×103 dm3 mol-1 s-1 at 25°C, 15-fold faster than for the pentaaza analogue.

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Metal-Directed Synthesis of Dithia Diaza Macrocycles Carrying Pendant Alcohol and Also Nitro or Carboxylate Groups

Australian Journal of Chemistry ◽

10.1071/ch9950825 ◽

1995 ◽

Vol 48 (4) ◽

pp. 825 ◽

Cited By ~ 8

Author(s):

G Wei ◽

CC Allen ◽

TW Hambley ◽

GA Lawrance ◽

M Maeder

Keyword(s):

Crystal Structure ◽

Copper Ion ◽

Crystal Structure Analysis ◽

Donor Group ◽

Alcohol Group ◽

X Ray ◽

Carboxylate Groups ◽

Directed Synthesis ◽

Ethyl Malonate ◽

Group A

Copper(II)-directed condensation of 1,9-diamino-3,7-dithianonan-5-ol with nitroethane or di-ethyl malonate yields (6-methyl-6-nitro-1,11-dithia-4,8-diazacyclotetradecan-13-ol)copper(II) and (diethyl 13-hydroxy-1,11-dithia-4,8-diazacyclotetradecane-6,6-dicarboxylate)copper(II) respectively in good yields, with the latter readily converted by decarboxylation into the complex of ethyl 13-hydroxy-1,11-dithia-4,8-diazacyclotetradecane-6-carboxylate. Analogues without the alcohol group based on 3,7-dithianonane-1,9-diamine are also described. The pendant alcohol group fused directly to a macrocyclic ring carbon can act as an axial donor group, as illustrated in the X-ray crystal structure analysis of (diethyl 13-hydroxy-1,11-dithia-4,8-diazacyclotetradecane-6,6-dicarboxylate)copper(II) perchlorate . This complex crystallizes in the P21/c space group, a 12.650(3), b 8.620(1), c 24.382(4) Ǻ, β 96.10(2)°. The copper ion lies in a distorted square-based pyramidal environment of two sulfur donors (average Cu-S 2.338 A), two nitrogen donors (average Cu-N 2.035 Ǻ) and the pendant alcohol donor [Cu-O 2.319(6) Ǻ], with the copper ion displaced slightly (0.043 Ǻ) out of the macrocycle donor plane towards the pendant alcohol donor.

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Crystal Structure of a Luminescent Europium(III) Complex: Probing the Active Species in Dissociation-Enhanced Lanthanide Fluoroimmunoassay

Australian Journal of Chemistry ◽

10.1071/ch9930577 ◽

1993 ◽

Vol 46 (4) ◽

pp. 577 ◽

Cited By ~ 6

Author(s):

CM Dearie ◽

RM Dyson ◽

TW Hambley ◽

GA Lawrance ◽

M Maeder ◽

...

Keyword(s):

Crystal Structure ◽

Single Crystal ◽

Structure Determination ◽

Active Species ◽

Crystal Structure Analysis ◽

Trioctylphosphine Oxide ◽

X Ray ◽

Two Component ◽

Group A ◽

Long Chain

The highly luminescent complex [ Eu ( fnac )2( topo )2(NO3)], which contains the two component ligands [ fnac, the anion of 4,4,4-trifluoro-1-(2-naphthyl)butane-1,3-dione, and topo, trioctylphosphine oxide] of the luminescent species in the dissociation-enhanced lanthanide fluoroimmunoassay method, has been prepared and defined by an X-ray crystal structure analysis. The complex crystallizes in the Ccmm space group, a 17.064(18), b 30.254(21) and c 16.391(4) Ǻ, Z = 4, and a single-crystal X-ray structure determination refined to R 0.056 for 1772 independent 'observed' reflections. The complex exhibits a dodecahedral EuO8 structure with bidentate nitrate ion [ Eu -O 2.512(10)Ǻ], two bidentate substituted acetylacetonate ( fnac )[ Eu -O 2.379(9), 2.400(9)Ǻ], and two monodentate long-chain phospine oxide ( topo ) ligands [ Eu -O 2.295(9)Ǻ].

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Preparative-scale HPLC Resolution of Metallacyclic η3-Allyltricarbonyliron Complexes and Determination of the Absolute Configuration by X-Ray Crystal Structure Analysis

Journal of Chemical Research ◽

10.1177/174751989902300930 ◽

1999 ◽

Vol 23 (9) ◽

pp. 578-579

Author(s):

Rainer Schobert ◽

Hermann Pfab ◽

Jutta Böhmer ◽

Frank Hampel ◽

Andreas Werner

Keyword(s):

Crystal Structure ◽

Silica Gel ◽

Structure Analysis ◽

Absolute Configuration ◽

Crystal Structure Analysis ◽

Preparative Scale ◽

X Ray ◽

The Absolute

Racemates of (η3-allyl)tricarbonyliron lactone complex Fe(CO)3{η1:η3-C(O)XCH2CHCMeCH2} 1a (X = O) and (η3-allyl)tricarbonyliron lactam complex 2a (X = NMe) are resolved on a preparative scale by HPLC on cellulose tris(3,5-dimethylphenyl)carbamate/silica gel RP-8 and the absolute configuration of (-)-2a is determined by X-ray crystal structure analysis.

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