在溴代-(吡咯烷-κN)金(I)双-(吡咯烷-κN)金(I)溴化物中,[AuBr(pyr)]·[Au(pyr)2]Br(pyr=吡咯烷,C4H9N),如图2所示,交替的[AuBr(pyr)]摩尔离子和[Au(pyr)2]+阳离子通过无亲接触连接以形成平行于b轴的无限残基链。链通过三个N-H-Br-氢键和Au-Br接触交联,形成平行于ab平面的层结构。三氯-(哌啶-κN)金(III),[AuCl3(pip)](pip=哌啶,C5H11N),3,由在金原子上具有预期的平方平面配位的摩尔分子组成,它们通过N-H→Cl氢键和Au→Cl触点连接,形成平行于ac平面的层结构。双-(哌啶)四-氯-金酸(III)氯化物的结构,(pipH)2[AuCl4]Cl,4,和溴化双-(吡咯烷鎓)四-溴代金酸(III),(pyrH)2[AuBr4]Br,6,密切相关,但不是同种型。化合物6在空间群Ibam中结晶;阴离子的Au和两个Br原子位于镜面x中,y,0,而溴离子占据特殊位置0、0.5、0和0、0.5、0.25,位点对称性为2/m。NH2基团与一个溴离子形成氢键,以及与另一个溴原子和金属键合的Br原子的三中心氢键。填料包括氢键键合的吡咯烷鎓和溴离子的链,平行于c轴,结合[AuBr4]-和溴阴离子的层结构,平行于ab平面,涉及Au→Br和Br→Br接触。然而,化合物4,在空间群Iba2中伪对称结晶;阴离子的两个氯原子位于双轴0.5,0.5,z,并且有两个独立的阳离子。填料与6的填料非常相似,但没有N-H-Cl氢键与金属键合的氯。在6中,Au→Cl的接触距离明显长于它们的Au→Br对应物,而Cl→Cl的接触比6中的Br→Br短得多。三溴-(哌啶-κN)金(III)结晶为其二氯甲烷溶剂化物,[AuBr3(pip)]·CH2Cl2,7.它在金原子处也显示出方形平面配位。填料涉及氢键N-H→Br,通过Au^Br触点堆叠相邻的AuBr3单元,和短Br-Br接触;这些结合形成平行于ac平面的层结构。
In bromido-(
pyrrolidine-κN)gold(I) bis-(
pyrrolidine-κN)gold(I) bromide, [AuBr(pyr)]·[Au(pyr)2]Br (pyr =
pyrrolidine, C4H9N), 2, alternating [AuBr(pyr)] mol-ecules and [Au(pyr)2]+ cations are connected by aurophilic contacts to form infinite chains of residues parallel to the b axis. The chains are cross-linked by three N-H⋯Br- hydrogen bonds and an Au⋯Br contact to form a layer structure parallel to the ab plane. Tri-chlorido-(piperidine-κN)gold(III), [AuCl3(pip)] (pip = piperidine, C5H11N), 3, consists of mol-ecules with the expected square-planar coordination at the gold atom, which are connected by an N-H⋯Cl hydrogen bond and an Au⋯Cl contact to form a layer structure parallel to the ac plane. The structures of bis-(piperidinium) tetra-chlorido-aurate(III) chloride, (pipH)2[AuCl4]Cl, 4, and bis-(pyrrolidinium) tetra-bromido-aurate(III) bromide, (pyrH)2[AuBr4]Br, 6, are closely related but not isotypic. Compound 6 crystallizes in space group Ibam; the Au and two Br atoms of the anion lie in the mirror plane x, y, 0, whereas the bromide ions occupy special positions 0, 0.5, 0 and 0, 0.5, 0.25, with site symmetry 2/m. The NH2 group forms a hydrogen bond to one bromide ion, and also a three-centre hydrogen bond to the other bromide atom and to a metal-bonded Br atom. The packing involves chains of hydrogen-bonded pyrrolidinium and bromide ions parallel to the c axis, combined with a layer structure of [AuBr4]- and bromide anions, parallel to the ab plane and involving Au⋯Br and Br⋯Br contacts. Compound 4, however, crystallizes pseudosymmetrically in space group Iba2; two chlorine atoms of the anion lie on the twofold axis 0.5, 0.5, z, and there are two independent cations. The packing is closely similar to that of 6, but there are no N-H⋯Cl hydrogen bonds to metal-bonded chlorines. The contact distances Au⋯Cl are appreciably longer than their Au⋯Br counterparts in 6, whereas the Cl⋯Cl contact is much shorter than Br⋯Br in 6. Tri-bromido-(piperidine-κN)gold(III) crystallizes as its di-chloro-methane solvate, [AuBr3(pip)]·CH2Cl2, 7. It too displays a square-planar coordination at the gold atom. The packing involves hydrogen bonds N-H⋯Br, stacking of neighbouring AuBr3 units by Au⋯Br contacts, and a short Br⋯Br contact; these combine to form a layer structure parallel to the ac plane.