• Oxley, Benjamin M.
• Mash, Brandon
• Banziger, Susannah
• Zeller, Matthias
• Ren, Tong

Abstract

<jats:p>Reported in this contribution are the synthesis and crystal structures of new mono- and bis-phenylacetylides based on Co<jats:sup>III</jats:sup>(DMC) (DMC is 5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane). Chlorido(5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane)(phenylethynyl)cobalt(III) chloride–acetonitrile–methanol (1/1/1), [Co(C<jats:sub>8</jats:sub>H<jats:sub>5</jats:sub>)Cl(C<jats:sub>12</jats:sub>H<jats:sub>28</jats:sub>N<jats:sub>4</jats:sub>)]Cl·CH<jats:sub>3</jats:sub>CN·CH<jats:sub>3</jats:sub>OH, <jats:bold>1</jats:bold>, and (5,12-dimethyl-1,4,8,11-tetraazacyclotetradecane)bis(phenylethynyl)cobalt(III) trifluoromethanesulfonate–dichloromethane (2/1), [Co(C<jats:sub>8</jats:sub>H<jats:sub>5</jats:sub>)<jats:sub>2</jats:sub>(C<jats:sub>12</jats:sub>H<jats:sub>28</jats:sub>N<jats:sub>4</jats:sub>)]<jats:sub>2</jats:sub>(CF<jats:sub>3</jats:sub>SO<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>·CH<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>, <jats:bold>2</jats:bold>, were prepared under weak-base conditions in satisfactory yields. Single-crystal X-ray diffraction studies revealed that both <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold> adopt a pseudo-octahedral symmetry in which the Cl—Co—C angles of <jats:bold>1</jats:bold> and C—Co—C of <jats:bold>2</jats:bold> range from 177.7 (2) to 178.0 (2)° and from 177.67 (9) to 179.67 (9)°, respectively. In both structures, the Co<jats:sup>III</jats:sup> metal center is coordinated in the equatorial plane by four N atoms, in which the N—Co—N angles range from 85.6 (3) to 94.4 (3)°. The structure of <jats:bold>1</jats:bold> features two crystallographically independent molecules in its triclinic cell (<jats:italic>Z</jats:italic>′ = 2), which are related to each other by pseudo-monoclinic symmetry. The crystal investigated was twinned by a symmetry operator of the approximate double-volume <jats:italic>C</jats:italic>-centered cell (180° rotation around [201] of the actual triclinic cell), with a refined twin ratio of 0.798 (3) to 0.202 (3). Both methanol solvent molecules in <jats:bold>1</jats:bold> are disordered, the major occupancy rates refined to 0.643 (16) and 0.357 (16). Compound <jats:bold>2</jats:bold> also contains two molecules in the asymmetric unit, together with two trifluoromethanesulfonate anions [of which one is disordered; occupancy values of 0.503 (16) and 0.497 (16)] and a disordered dichloromethane [occupancy values of 0.545 (12) and 0.455 (12)].</jats:p>

Topics

• impedance spectroscopy
• compound
• x-ray diffraction
• cobalt
• twinned