Sodium and Potassium Triisopropylbenzenethiolates: Influence on Solid-State Structure by Metal and Donor

The synthesis and characterization of a family of sodium and
potassium thiolates [A(donor)S(Trip)]n (A
= Na,
K; Trip = 2,4,6-i-Pr3C6H2,
n = 1−∞) is described.
[Na(PMDTA)S(Trip)]2, 1 (PMDTA
=
N,N,N‘,N‘‘,N‘‘-pentamethyldiethylenetriamine),
[(NaS(Trip))2(Na(Et2O)S(Trip))4]·0.5
solvent, 2, [Na(TMEDA)S(Trip)]∞,
3
(TMEDA =
N,N,N‘,N‘-tetramethylethylenediamine),
[Na(THF)S(Trip)]n, 4
(n = 6 or ∞), [K(dibenzo-18-crown-6)(THF)S(Trip)]·THF, 5,
[(KS(Trip))2(K(THF)S(Trip))2(K(THF)2S(Trip))2],
6, [K(THF)S(Trip)]∞, 7,
[(K(THF)S(Trip))2(K(TMEDA)S(Trip))2(KS(Trip))2]·THF,
8, and [K(PMDTA)S(Trip)]∞,
9, were synthesized by treatment
of HS(Trip) with NaH or KH along with the addition of various
donors. The target molecules were characterized
by IR, 1H NMR, and depending on solubility, 13C
NMR spectroscopy and melting point. Compounds
1−3 and
5−9 were also characterized by single-crystal
X-ray crystallography. Analysis of structural data clearly
indicates
that the structural chemistry of the target molecules can be influenced
by donor choice, as exemplified by the
large structural diversity observed in the target molecules:  the use
of a crown ether allowed the isolation of the
monomeric species 5, whereas the use of a monodentate donor,
such as THF, led to the isolation of the ladder-type polymer 7 or the discrete hexameric compounds
2 and 6. Addition of the bidentate donor
TMEDA to a
solution of [NaS(Trip)]∞ resulted in the formation
of the one-dimensional zigzag polymer 3, whereas
utilization
of the tridentate donor PMDTA allowed the isolation of the dimer
1. Changing from sodium to potassium and
utilization of the tridentate donor PMDTA yielded the one-dimensional
zigzag polymer 9, while employment of
a mixture of mono- and bidentate donors (THF and TMEDA) resulted in the
asymmetrically coordinate hexamer
8. Crystal data with Mo Kα (λ = 0.710 73 Å) at
150 K are as follows:  1, a = 13.2300(1)
Å, b = 10.6176(1)
Å, c = 19.6262(3) Å, β = 100.449(1)°,
V = 2711.19(5) Å3, Z = 4,
monoclinic, space group P21/n, 6309
independent
reflections, R1 (all data) = 0.1004; 2, a =
14.4178(3) Å, b = 17.6498(4) Å, c
= 26.2052(6) Å, α = 89.847(1)°,
β = 77.475(1)°, γ = 70.189(1)°, V =
6106.3(2) Å3, Z = 2, triclinic, space
group P1̄, 25 722 independent
reflections,
R1 (all data) = 0.1311; 3, a = 9.2702(1)
Å, b = 20.1017(2) Å, c =
25.9256(4) Å, V = 4831.15(10) Å3,
Z = 8,
orthorhombic, space group Pbca, 5032 independent
reflections, R1 (all data) = 0.1125; 5, a =
14.196(3) Å, b =
15.429(3) Å, c = 22.562(5) Å, α =
101.92(2)°, β = 97.31(3)°, γ = 114.19(3)°,
V = 4313(2) Å3, Z = 4,
triclinic,
space group P1̄, 6592 (I >
2σ(I)) data, R = 0.074; 6,
a = 15.071(3) Å, b = 25.301 (5) Å,
c = 17.866(4) Å, β
= 113.01(3)°, V = 6270(3) Å3,
Z = 2, monoclinic, space group
P21/n, 2332 (I >
2σ(I)) data, R = 0.103; 7,
a =
11.9079(2) Å, b = 14.7672(2) Å, c
= 24.0448(1) Å, β = 98.220(1)°, V =
4184.75(9) Å3, Z = 4,
monoclinic,
space group P21/c, 9693 independent
reflections, R1 (all data) = 0.1324; 8, a =
18.324(4) Å, b = 14.323(3),
c
= 26.300(5) Å, β = 106.39(3)°, V =
6622(3) Å3, Z = 2, monoclinic, space
group P21/c, 4511 (I
>3σ(I)) data,
R = 0.105; 9, a = 10.4903(2)
Å, b = 20.1551(5) Å, c =
26.4295(4) Å, V = 5588.1(2) Å3,
Z = 8, orthorhombic,
space group Pbca, 6649 independent reflections, R1 (all
data) = 0.146.