Rajesekharan-Nair Rajeev, Lutta Samuel T, Kennedy Alan R, Reglinski John, Spicer Mark D
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland.
Department of Chemistry and Biochemistry, Chepkoilel University College, Moi University, PO Box 1125, Eldoret, Kenya.
Acta Crystallogr C Struct Chem. 2014 May;70(Pt 5):421-7. doi: 10.1107/S2053229614005737. Epub 2014 Apr 8.
Reported here are the single-crystal X-ray structure analyses of bis-μ-methanol-κ(4)O:O-bis{hydrotris(3-phenyl-2-sulfanylidene-2,3-dihydro-1H-1,3-imidazol-1-yl)borato-κ(3)H,S,S'sodium(I)}, [Na2(C27H22BN6S3)2(CH4O)4] (NaTm(Ph)), bis-μ-methanol-κ(4)O:O-bis{hydrotris(3-isopropyl-2-sulfanylidene-2,3-dihydro-1H-1,3-imidazol-1-yl)borato-κ(3)H,S,S'sodium(I)}-diethyl ether-methanol (1/0.3333/0.0833), [Na2(C18H28BN6S3)2(CH4O)4]·0.3333C4H10O·0.0833CH3OH (NaTm(iPr)), and a novel anhydrous form of sodium hydrotris(methylthioimidazolyl)borate, poly[[μ-hydrotris(3-methyl-2-sulfanylidene-2,3-dihydro-1H-1,3-imidazol-1-yl)borato]sodium(I)], [Na(C12H16BN6S3)] ([NaTm(Me)]n). NaTm(iPr) and NaTm(Ph) have similar dimeric molecular structures with κ(3)H,S,S'-bonding, but they differ in that NaTm(Ph) is crystallographically centrosymmetric (Z' = 0.5) while NaTm(iPr) contains one crystallographically centrosymmetric dimer and one dimer positioned on a general position (Z' = 1.5). [NaTm(Me)]n is a one-dimensional coordination polymer that extends along the a direction and which contains a hitherto unseen side-on η(2)-C=S-to-Na bond type. An overview of the structural preferences of alkali metal soft scorpionate complexes is presented. This analysis suggests that these thione-based ligands will continue to be a rich source of interesting alkali metal motifs worthy of isolation and characterization.
本文报道了双-μ-甲醇-κ(4)O:O-双{三(3-苯基-2-硫代亚甲基-2,3-二氢-1H-1,3-咪唑-1-基)硼氢化钠-κ(3)H,S,S'钠(I)}，[Na₂(C₂₇H₂₂BN₆S₃)₂(CH₄O)₄] (NaTm(Ph))、双-μ-甲醇-κ(4)O:O-双{三(3-异丙基-2-硫代亚甲基-2,3-二氢-1H-1,3-咪唑-1-基)硼氢化钠-κ(3)H,S,S'钠(I)}-乙醚-甲醇(1/0.3333/0.0833)，[Na₂(C₁₈H₂₈BN₆S₃)₂(CH₄O)₄]·0.3333C₄H₁₀O·0.0833CH₃OH (NaTm(iPr))以及一种新型无水三(甲硫基咪唑基)硼酸钠，聚[[μ-三(3-甲基-2-硫代亚甲基-2,3-二氢-1H-1,3-咪唑-1-基)硼氢化钠(I)]，[Na(C₁₂H₁₆BN₆S₃)] ([NaTm(Me)]ₙ)的单晶X射线结构分析。NaTm(iPr)和NaTm(Ph)具有相似的通过κ(3)H,S,S'-键合的二聚体分子结构，但不同之处在于NaTm(Ph)在晶体学上是中心对称的(Z' = 0.5)，而NaTm(iPr)包含一个晶体学中心对称的二聚体和一个位于一般位置的二聚体(Z' = 1.5)。[NaTm(Me)]ₙ是一种沿a方向延伸的一维配位聚合物，其中包含一种迄今未见的侧基η(2)-C=S到Na的键型。本文还对碱金属软蝎形配合物的结构偏好进行了概述。该分析表明，这些基于硫酮的配体将继续是有趣的碱金属基序的丰富来源，值得分离和表征。
