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首页> 外文期刊>Acta Crystallographica Section E: Crystallographic Communications >Coordination compounds containing bis-di-thiol-ene-chelated molybdenum(IV) and oxalate: comparison of terminal with bridging oxalate
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Coordination compounds containing bis-di-thiol-ene-chelated molybdenum(IV) and oxalate: comparison of terminal with bridging oxalate

机译：含双-二硫醇-螯合的钼（IV）和草酸盐的配位化合物：草酸盐与桥联末端的比较

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Two coordination compounds containing tetra-n-butyl-ammonium cations and bis-tfd-chelated molybdenum(IV) [tfd2? = S2C2(CF3)22?] and oxalate (ox2?, C2O42?) in complex anions are reported, namely bis-(tetra-n-butyl-ammonium) bis-(1,1,1,4,4,4-hexa-fluoro-but-2-ene-2,3-di-thiol-ato)oxalatomolybdate(IV)–chloro-form–oxalic acid (1/1/1), (C16H36N)2[Mo(C4F6S2)2(C2O4)]·CHCl3·C2H2O4 or (NnBu4)2[Mo(tfd)2(ox)]·CHCl3·C2H2O4, and bis-(tetra-n-butyl-ammonium) μ-oxalato-bis-[bis-(1,1,1,4,4,4-hexa-fluoro-but-2-ene-2,3-di-thiol-ato)molybdate(IV)], (C16H36N)2[Mo2(C4F6S2)4(C2O4)] or (NnBu4)2[(tfd)2Mo(μ-ox)Mo(tfd)2]. They contain a terminal oxalate ligand in the first compound and a bridging oxalate ligand in the second compound. Anion 12? is [Mo(tfd)2(ox)]2? and anion 22?, formally generated by adding a Mo(tfd)2 fragment onto 12?, is [(tfd)2Mo(μ-ox)Mo(tfd)2]2?. The crystalline material containing 12? is (NnBu4)2-1·CHCl3·oxH2, while the material containing 22? is (NnBu4)2-2. Anion 22? lies across an inversion centre. The complex anions afford a rare opportunity to compare terminal oxalate with bridging oxalate, coordinated to the same metal fragment, here (tfd)2MoIV. C—O bond-length alternation is observed for the terminal oxalate ligand in 12?: the difference between the C—O bond length involving the metal-coordinating O atom and the C—O bond length involving the uncoordinating O atom is 0.044?(12)??. This bond-length alternation is significant but is smaller than the bond-length alternation observed for oxalic acid in the co-crystallized oxalic acid in (NnBu4)2-1·CHCl3·oxH2, where a difference (for C=O versus C—OH) of 0.117?(14)?? was observed. In the bridging oxalate ligand in 22?, the C—O bond lengths are equalized, within the error margin of one bond-length determination (0.006??). It is concluded that oxalic acid contains a localized π-system in its carb-oxy-lic acid groups, that the bridging oxalate ligand in 22? contains a delocalized π-system and that the terminal oxalate ligand in 12? contains an only partially localized π-system. In (NnBu4)2-1·CHCl3·oxH2, the F atoms of two of the –CF3 groups in 12? are disordered over two sets of sites, as are the N and eight of the C atoms of one of the NnBu4 cations. In (NnBu4)2-2, the whole of the unique NnBu4+ cation is disordered over two sets of sites. Also, in (NnBu4)2-2, a region of disordered electron density was treated with the SQUEEZE routine in PLATON [Spek (2015). Acta Cryst. C71, 9–18].
机译：两种含有四正丁基铵阳离子和双-tfd-螯合的钼（IV）的配位化合物[tfd2？ ＝ S2C2（CF3）22′和草酸盐（ox2′，C2O42′）在复合阴离子中被报道，即双-（四正丁基铵）双-（1,1,1,4,4,4-六氟丁-2-烯-2,3-二硫醇基-草酰钼（IV）-氯仿-草酸（1/1/1），（C16H36N）2 [Mo（C4F6S2）2（ C2O4）]·CHCl3·C2H2O4或（NnBu4）2 [Mo（tfd）2（ox）]·CHCl3·C2H2O4和双-（四正丁基铵）μ-草酸双-[-（1 ，1,1,4,4,4-六氟丁-2-烯-2,3-二硫醇基）钼酸盐（IV）]，（C16H36N）2 [Mo2（C4F6S2）4（C2O4） ]或（NnBu4）2 [（tfd）2Mo（μ-ox）Mo（tfd）2]。它们在第一化合物中包含末端草酸酯配体，在第二化合物中包含桥联草酸酯配体。阴离子12？是[Mo（tfd）2（ox）] 2吗？通过将Mo（tfd）2片段加到12′上而正式产生的阴离子22′是[（tfd）2 Mo（μ-ox）Mo（tfd）2] 2。晶体中含有12？是（NnBu4）2-1·CHCl3·oxH2，而该材料含有22？是（NnBu4）2-2。负离子22？位于反演中心。络合阴离子提供了难得的机会，可以将草酸末端与桥接草酸进行比较，草酸与相同的金属片段（此处为（tfd）2MoIV）配位。在12′中观察到末端草酸酯配体的CO键长度交替：涉及金属配位O原子的CO键长度与涉及不配位O原子的CO键长度之间的差为0.044Ω（ 12）??。该键长交替是显着的，但小于在（NnBu4）2-1·CHCl3·oxH2中共结晶的草酸中草酸的键长交替，其中差异（对于C = O与C- OH）为0.117？（14）??被观测到。在22′中桥联的草酸酯配体中，在一个键长确定的误差范围内（0.006′′），CO键的长度相等。结论是草酸在其碳-氧-酸基团中含有一个局部的π系统，草酸盐的配体在22？包含一个离域的π系统，并且末端的草酸盐配体在12？包含仅局部局部的π系统。在（NnBu4）2-1·CHCl3·oxH2中，12？中两个–CF3基团的F原子在两个位点处无序排列，一个NnBu4阳离子的N和8个C原子也无序。在（NnBu4）2-2中，整个独特的NnBu4 +阳离子在两组位点上无序。此外，在（NnBu4）2-2中，在PLATON中使用SQUEEZE程序处理了电子密度混乱的区域[Spek（2015）。 Acta Cryst。 C71，9-18]。

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