Gold complexes [Ph4Bi][Au(CN)2Hal2] (Hal = Cl, Br). Synthesis and structure

The interaction of tetraphenylbismuth bromide with potassium dichloro- and dibromodicyanoaurate in water followed by recrystallization from acetonitrile have synthesized gold complexes [Ph4Bi][Au(CN)2Cl2] (1) and [Ph4Bi][Au(CN)2Br2] (2). They have been structurally characterized. The X-ray diffraction pattern has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (Mo Kα -radiation, λ = 0.71073 Å, graphite monochromator) of crystals 1 [C26H20N2Cl2AuBi, M 837,29, the triclinic syngony, the symmetry group P -1; cell parameters: a 8,740(4), b 8,914(4), c 17,112(9) Å, α = 91,21(2) degrees, β = 94,47(2) degrees, γ = 90,36(2) degrees; V = 1328,8(10) Å3; the crystal size is 0,37×0,34×0,08 mm; intervals of reflection indexes are -13 ≤ h ≤ 13, -14 ≤ k ≤ 14, -27 ≤ l ≤ 27; total reflections 57659; independent reflections 10901; Rint 0,0879; GOOF 1,187; R 1 = 0,1892, wR 2 = 0,3575; residual electron density -3,27/4,68 e/Å3] and 2 [C26H20N2Br2AuBi, M 926,21, the triclinic syngony, the symmetry group P -1; cell parameters: a 8,735(3), b 8,889(3), c 17,081(5) Å, α = 91,408(15) degrees, β = 94,352(15) degrees, γ = 90,307(18) degrees; V = 1322,2(8)Å3; the crystal size is 0,59×0,29×0,06 mm; intervals of reflection indexes are -15 ≤ h ≤ 15, -15 ≤ k ≤ 15, -30 ≤ l ≤ 30; total reflections 74349; independent reflections 15328; Rint 0,1261; GOOF 1,254; R 1 = 0,2857, wR 2 = 0,3864; residual electron density -3,84/4,54 e/Å3], the bismuth atoms have a distorted tetrahedral coordination (the СBiС angles are 104,2(9)-113,8(10)° (1) and 103,2(11)-114,4(10)° (2); the Bi-С bond lengths are Bi-С 2,20(2)-2,23(2) Å (1), 2,19(3)-2,21(3) Å (2)). In square planar centrosymmetric crystallographically independent anions [Au(CN)2Hal2]- atoms of gold are tetra-coordinated ( trans- angles HalAuHal and CAuC are close to 180°; cis- angles CAuHal have the values 89,5(11)°-90,5(11)° (1), 87,5(10)°-92,5(10)° (2); bond lengths Au-Hal are 2,428(5), 2,434(5) Å (1), 2,426(5), 2.429(5) Å (2), Au-C are 2,10 Å (1), 2,07(4), 2,10(3) Å (2)). The structural organization of crystals 1 and 2 is controlled by intermolecular bonds С-H∙∙∙N≡C (2,59-2,74 Å) (1), (2,56-2,70 Å) (2). Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 1912236, 1912238; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).