The reaction of Pb[CO3] with an aqueous solution of (H3O)2[B10H10] in an equimolar ratio leads to two lead(II) decahydro‐closo‐decaborate hydrates both as triclinic, pale yellow single crystals. The water‐rich compound with the formula [Pb(H2O)3]2Pb[B10H10]3·5.5H2O crystallizes in the space group P1 (a = 711.72(4), b = 1243.14(8), c = 2064.83(12) pm, α = 81.806(3), β = 83.795(3), γ = 80.909(3)°) with Z = 2. The compound with the lower water content, [Pb(H2O)3]Pb[B10H10]2·1.5H2O, also crystallizes in P1 (a = 718.46(4), b = 1288.75(8), c = 1279.91(8) pm, α = 70.145(3), β = 75.976(3), γ = 80.324(3)°) with Z = 2. Both structures can be described as layered arrangements and contain one Pb2+ cation each, which is only coordinated by the hydridic hydrogen atoms of the hydroborate anions. All the others are primarily surrounded by three water molecules in a non‐planar fashion and additional hydrogen atoms of [B10H10]2– anions. The non‐lead‐bonded crystal water molecules in both structures are all connected via hydrogen bonds to the water molecules, which coordinate the Pb2+ cations, as well as via non‐classical hydrogen bonds to the cluster anions and reside between the layers. The [B10H10]2– anions show only slight distortions from their ideal shape as bicapped square antiprisms.
Thallium(I) decahydro-closo-decaborate Tl2[B10H10] and thallium(I) dodecahydro-closo-dodecaborate Tl2[B12H12] are readily available as microcrystalline powders from reactions of thallium(I) carbonate Tl2[CO3] with aqueous solutions of the respective free acid (H3O)2[B10H10] or (H3O)2[B12H12]. Tl2[B12H12] crystallizes with an anti-fluorite related structure (cubic, F m 3 ‾ $Fm\overline{3}$ , a = 1074.23(8) pm, Z = 4). Each Tl+ cation is coordinated by four icosahedral [B12H12]2– anions (d(B–B) = 180–181 pm) providing a twelvefold coordination sphere of hydrogen atoms (d(Tl–H) = 296 pm). Tl2[B10H10] crystallizes monoclinically in the space group P21/n with a = 704.03(5), b = 1111.45(8), c = 1281.16(9) pm and β = 94.912(3)° for Z = 4. The bicapped square antiprismatic [B10H10]2– anions (d(B–B) = 147–176 pm to the two apical boron atoms, d(B–B) = 161–199 pm within the corpus) again form distorted tetrahedra around the (Tl1)+, but square pyramids around the (Tl2)+ cations. Thus (Tl1)+ is coordinated by 12 hydrogen atoms (d(Tl1–H) = 275–315 pm), but (Tl2)+ only by 11 of them (d(Tl2–H) = 267–357 pm). Both compounds show a greenish-yellow photoluminescence caused by an interconfigurational 6sp –6s 2 emission (3Pn→1S0, n = 0–2) at the Tl+ cation.
Single crystals of [Cr(H2O)6]2 [B12H12]3·15H2O and [In(H2O)6]2 [B12H12]3·15H2O are obtained by reactions of aqueous solutions of the acid (H3O)2[B12H12] with Cr(OH)3 and In, respectively.
Single crystals of Sn(H2O)3[B10H10] · 3 H2O and Sn(H2O)3[B12H12] · 4 H2O are easily accessible by reactions of aqueous solutions of the acids (H3O)2[B10H10] and (H3O)2[B12H12] with an excess of tin metal powder after isothermal evaporation of the clear brines. Both compounds crystallize with similar structures in the triclinic system with space group P$$\bar{1 }$$ 1 ¯ and Z = 2. The crystallographic main features are electroneutral $${}_{\infty }^{1} \{$$ ∞ 1 { Sn(H2O)3/1[B10H10]3/3} and $${}_{\infty }^{1} \{$$ ∞ 1 { Sn(H2O)3/1[B12H12]3/3} double chains running along the a-axes. Each Sn2+ cation is coordinated by three water molecules of hydration (d(Sn–O) = 221–225 pm for the B10 and d(Sn–O) = 222–227 pm for the B12 compound) and additionally by hydridic hydrogen atoms of the three nearest boron clusters (d(Sn–H) = 281–322 pm for the B10 and d(Sn–H) = 278–291 pm for the B12 compound), which complete the coordination sphere. Between these tin(II)-bonded water and the three or four interstitial crystal water molecules, classical bridging hydrogen bonds are found, connecting the double chains to each other. Furthermore, there is also non-classical hydrogen bonding between the anionic [BnHn]2− (n = 10 and 12) clusters and the crystal water molecules pursuant to B–Hδ−$$\cdots$$ ⋯ δ+H–O interactions often called dihydrogen bonds.
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