Room-temperature, single-crystal X-ray structure determinations are recorded for alkaline earth metal
picrates , M( pic )2.nH2O(M = Mg, Sr , Ba ; Hpic = 2,4,6-trinitrophenol, HOC6H2(NO2)3),
all crystallized from aqueous solution. Magnesium picrate ,shown to be the nonahydrate,
Mg( pic )2.9H2O, forms monoclinic crystals, space group P21/c, a 15.023(3), b
6.718(4), c 26.516(2) Ǻ, β 109.55(1)°, Z = 4 f.u .,conventional R on |F| was 0.049
for No = 4062 'observed' (I > 3σ(I)) reflections. The structure, unusually among the main group metal picrates
studied so far, has no coordinative interaction between the metal and the picrate anion; the complex may be formulated as [Mg(OH2)6]
( pic )2.3H2O, with the metal present as the hexaaqua species (Mg-O
2.043(2)-2.077(2)Ǻ). The picrate ions are stacked end to end, presumably as a result of charge-transfer interactions,
parallel to b, with side-by-side stacks forming a sheet along ab, and successive sheets are interleaved by layers of cations and water molecules. The strontium salt is a pentahydrate , monoclinic, C2/c, a 24.515(6), b 10.142(6), c
17.932(4) Ǻ, β 98.76(2)°, Z = 8 f.u .; R was 0.046 for No 2731.
The complex is a linear polymer, [(H2O)3Sr(O,O′- pic )2(μ-OH2)](∞|∞).H2O,
with eight-coordinate (SrO8) strontium. The barium salt is a hexahydrate , also a linear polymer [(H2O)5Ba(O,O′-pic )( O,O′,μ-O″-pic )]∞|∞).H2O,
the ten-coordinate (BaO10) barium environment comprising the five
water molecules, a pair of picrates, bidentate /chelating via the phenolic
oxygen and a 2-nitro group oxygen, with one of the picrates
from an adjacent metal atom offering an additional 4-nitro group oxygen, this
bridging successive barium atoms. The complex is triclinic, Pī ,
a 15.120(5), b 11.633(3), c 6.766(3) Ǻ, α 87.24(3), β 79.16(3),
γ 84.88(2)°, Z = 2 f.u .; R was 0.027 for No
3904. Repeated attempts to obtain crystals of beryllium picrate suitable for an X-ray structure determination were unsuccessful.