Cooper et al.
493
Johnson Matthey Gouy balance. Microanalyses were by Mr
A. Saunders of the University of East Anglia (CHN) or by
Southern Science, Falmer Laboratories, East Sussex (met-
als).
(mm s–1): IS 0.58, QS 2.04 (rel. intensity 1); IS 0.32, QS 1.39
(rel. intensity 2). µeff = 1.72 µB. IR (cm–1): 2098, 2065
(NϵC). Anal. calcd. for C22H42Fe3N4S6: C 36.6, H 5.8, N
7.8; found: C 36.7, H 5.6, N 7.7.
Preparation of [Fe{Fe(NS3)(CNCy)}2-S,S′] (2c)
Syntheses
This was made similarly using CyNC in ether, in 82%
yield with respect to Fe. Mössbauer (mm s–1): IS 0.67, QS
Preparation of Et4N[Fe(NS3)(CNMe)]·MeCN (1a)
[Fe(acac)3] (0.71 g, 2.0 mmol), Et4NOAc·4H2O (0.65 g,
2.5 mmol), and MeNC (0.4 g, 10 mmol) were stirred in
MeCN (10 mL) for a few minutes, then NS3H3 (0.6 g,
3 mmol) in MeCN (5 mL) was added, whereupon the solu-
tion turned blue. After 1 h it was filtered and MeCN (5 mL)
and ether (20 mL) were added as a layer. After 3 days large
blue crystals deposited, which were filtered off, washed with
MeCN:ether and then ether, and dried in a vacuum; yield
2.01 (rel. intensity 1); IS 0.30, QS 1.47 (rel. intensity 2). µeff
=
1.72 µB. IR (cm–1): 2084, 2060 (NϵC). Anal. calcd. for
C26H46Fe3N4S6: C 40.3, H 5.9, N 7.2; found: C 40.4, H 5.9,
N 7.4.
Preparation of [Co{Fe(NS3)(CNMe)}2-S,S′] (3)
[CoCl2(DMSO)3] (0.10 g, 0.3 mmol) in methanol (10 mL)
was added to Et4N[Fe(NS3)(CNMe)] (0.24, 0.6 mmol) in
methanol (20 mL). A black precipitate formed. The next day
this was filtered off, washed with methanol and ether, and
dried in a vacuum (yield: 0.06 g, 34%). Mössbauer (mm s–1):
IS 0.29, QS 1.52. IR (cm–1): 2105 (NϵC). Anal. calcd. for
C16H30CoFe2N4S6: C 30.0, H 4.7, N 8.7, Co 9.2, Fe 17.5;
found: C 29.7, H 4.9, N 8.2, Co 9.9, Fe 17.3.
0.35 g (38%). Mössbauer (mm s–1): IS 0.36, QS 1.27. µeff
=
2.61 µB (S = 1). IR (cm–1): 2291, 2246 (CϵN), 2061 (NϵC).
Anal. calcd. for C18H38FeN4S3: C 46.8, H 8.2, N 12.1;
found: C 46.3, H 8.2, N 11.7.
Preparation of Et4N[Fe(NS3)(CN-t-Bu)] (1b)
Et4N[FeCl(NS3] (0.83 g, 2 mmol) was treated with so-
dium amalgam (70 g, 0.5% Na) in MeCN (20 mL). After
20 min the solution became yellow and was filtered through
Celite™. t-BuNC (0.8 g, 10 mmol) was added immediately
to the filtrate, which became blue. Ether (60 mL) was then
added as a layer to give, after 2 h, dark blue microcrystals
(0.14 g, 15%), which were filtered off, washed with ether,
and dried in a vacuum. Mössbauer (mm s–1): IS 0.32, QS
1.30. µeff = 2.58 µB (S = 1). IR (cm–1): 1975 (NϵC). Anal.
calcd. for C19H41FeN3S3: C 49.2, H 8.9, N 9.1; found: C
48.1, H 8.9, N 8.7.
Preparation of [Ni{Fe(NS3)(CNMe)}2-S,S′] (4)
This was made similarly from [NiCl2(DMSO)3] in 76%
yield. Mössbauer (mm s–1): IS 0.27, QS 1.61. µeff = 2.26 µB.
IR (cm–1): 2103 (NϵC). Anal. calcd. for C16H30Fe2N4NiS6:
C 30.0, H 4.7, N 8.7, Fe 17.5, Nil 9.2; found: C 30.0, H 4.9,
N 8.2, Fe 15.6, Nil 9.1.
Crystal structure analyses
NEt4[Fe(NS3)(CNMe)]·MeCN (1a)
Crystal data: C8H20N·C8H15FeN2S3·C2H3N, MW = 462.5.
Orthorhombic, space group P212121 (No. 19), a = 16.664(2),
b = 14.2340(12), c = 9.929(2) Å, V = 2355.1(6) Å3, Z = 4,
Dc = 1.31 g cm–3, F(000) = 992, T = 140 K, µ (Mo Kα) =
9.2 cm–1, λ (Mo Kα) = 0.71069 Å.
Preparation of Et4N[Fe(NS3)(CNCy)] (1c)
This was made similarly from reduced Et4N[FeCl(NS3)]
by treatment with CyNC, in 35% yield. A good analysis was
not obtained (see text). Mössbauer (mm s–1): IS 0.33, QS
1.29. IR (cm–1): 2023, 1940 (NϵC). Anal. calcd. for
C21H43FeN3S3: C 51.5, H 8.8, N 8.6; found: C 49.1, H 8.2,
N 9.1.
Crystals are black, irregular octahedra; in thin section they
are blue, decomposing in air to orange over two to three
days. Most are twinned, and from preliminary photographic
examination, some crystals show small variations in cell pa-
rameters and diffraction intensities. One, ca. 0.83 × 0.48 ×
0.48 mm, sealed in a capillary tube, was mounted on an
Enraf–Nonius CAD4 diffractometer (with monochromated
radiation) for determination, at room temperature, of accu-
rate cell parameters (from the settings of 25 reflections, θ =
10 to 11°, each centred in four orientations). The sample,
shown to be twinned, was then cooled to 140 K, the cell pa-
rameters were re-determined, and diffraction intensities of
the major twin were recorded. Of the 3825 unique reflec-
tions to θmax = 30°, 3537 were “observed” with I > 2σI; the
00l reflections, common to both twins, were removed from
the data set, leaving 3819 and 3532 reflections, respectively.
During processing, corrections were applied for Lorentz
polarization effects, absorption (by semi empirical ψ-scan
methods), and to eliminate negative net intensities (by
Bayesian statistical methods). No deterioration correction
was necessary. The structure was determined by the direct
methods routines in the SHELXS program (12) and refined
by full-matrix least-squares methods, on F2’s, in SHELXL
(13). There is disorder in the N-bonded methylene groups in
Preparation of [Fe{Fe(NS3)(CNMe)}2-S,S′] (2a)
[Fe(acac)3] (0.71 g, 2 mmol) and MeNC (0.4 g, 10 mmol)
were dissolved in MeCN (40 mL), and NS3H3 (0.6 g,
3 mmol) in MeCN (5 mL) was added. The solution turned
dark red, but within 30 min it turned dark green and depos-
ited black needles after 3 h which were filtered off, washed
with ether, and dried in a vacuum (yield: 0.13 g, 0.2 mmol,
30% with respect to iron). Mössbauer (mm s–1): IS 0.59, QS
2.06 (rel. intensity 1); IS 0.33, QS 1.38 (rel. intensity 2). µeff
=
2.92 µB. IR (cm–1): 2099 (NϵC). Anal. calcd. for
C16H30Fe3N4S6: C 30.1, H 4.6, N 8.8; found: C 30.1, H 4.6,
N 8.9.
Preparation of [Fe{Fe(NS3)(CN-t-Bu)}2-S,S′] (2b)
[Fe(acac)3] (2.13 g, 6 mmol) and t-BuNC (3 g, 36 mmol)
were dissolved in ether (40 mL) and NS3H3 (1.2 g, 6 mmol)
was added. The mixture was stirred overnight and a brown
precipitate was formed which turned dark green on standing
overnight. It was filtered off, washed with ether, and dried in
a vacuum; yield 1.0 g (70% with respect to Fe). Mössbauer
© 2001 NRC Canada