Formation of thiosemicarbazone-functionalized complexes with (GeS 2)2 and (SnS2)2 units

Article abstract of DOI:10.1002/zaac.201200292

By reaction of organo-functionalized germanium or tin sesquisulfides [(R¹T)₄S₆] (T = Ge, Sn; R¹ = CMe₂CH₂COMe) with thiosemicarbazide or its methyl or phenyl derivative, a series of four compounds were obtained and structurally characterized that are based on an inorganic (TS₂)₂ unit with an extended organic chelate ligand CMe₂CH ₂CMeNNCSNHR′ (R′ = H, Me, Ph). The products combine a small, reactive metal chalcogenide moiety with a ligand system that allows for a variety of directed extensions at the terminal NHR′ group. Thus, this work represents the starting point to a multifaceted consecutive chemistry involving both the extension of the binary inorganic unit and further derivatization and/or coordination of the organic ligands. Copyright

Full text of DOI:10.1002/zaac.201200292

Job/Unit: Z12292
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Date: 27-08-12 17:46:23
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ARTICLE
DOI: 10.1002/zaac.201200292
Formation of Thiosemicarbazone-Functionalized Complexes with (GeS2)2
and (SnS2)2 Units
Jens P. Eußner[a] and Stefanie Dehnen*[a]
Keywords: Thiosemicarbazide; Tetrelchalcogenides; Inorganic-organic hybrid compounds; X-ray diffraction
Abstract. By reaction of organo-functionalized germanium or tin ses-
a small, reactive metal chalcogenide moiety with a ligand system that
quisulfides [(R1T)4S6] (T = Ge, Sn; R1 = CMe2CH2COMe) with allows for a variety of directed extensions at the terminal NHRЈ group.
thiosemicarbazide or its methyl or phenyl derivative, a series of four Thus, this work represents the starting point to a multifaceted consecu-
compounds were obtained and structurally characterized that are based
on an inorganic (TS2)2 unit with an extended organic chelate ligand
CMe2CH2CMeNNCSNHRЈ (RЈ = H, Me, Ph). The products combine
tive chemistry involving both the extension of the binary inorganic unit
and further derivatization and/or coordination of the organic ligands.
of the organic ligand with or without rearrangement of the in-
organic core.[9,10]
Introduction
Investigations of Group 14 chalcogenidometallates have in-
creasingly attracted attention due to potential technological ap-
plications requiring semiconducting, photoconducting, non-lin-
ear optical, catalytic or ion exchange properties.[1] Targeting
of respective organic derivatives involved the development of
synthetic methods for introduction of the organic ligands. In
order to enhance the variety of the desired compounds, to de-
sign and combine specific physical and chemical properties by
tuning the cluster moiety and storing desirable information in
the components by further organic reactions, the use of func-
tional ligands evolved to be a promising approach.[2]
Organotin and organogermanium sesquichalcogenide cages
[(RT)4E6] (T = Ge, Sn; E = S, Se, Te), exhibiting non-reactive
organic groups R = alkyl, aryl, CF3, C6F5, C(SiMe3)3 have
been known since 1903 and were first structurally charac-
terized in 1968.[3] They have been subject matter of numerous
investigations on structural, physical and chemical properties
since.[4,5] Recently, functionalized organic groups R1 and R2
were introduced to the sesquichalcogenide cages [(R1,2T)4S6]
(R1 = CMe2CH2COMe, R2 = CH2CH2COOH; T = Ge, Sn),[6]
that allowed for a further derivatization of the cages in two
ways. First, reactions with transition metal (M) compounds al-
lowed for an extension of the inorganic core toward ternary
M/T/E complexes with functionalized organic ligands[6b,7] or
toward chalcogenidometallate organic coordination frame-
works,[8] second, reactions with organic molecules exhibiting
a complementary functionality enabled the directed extension
Aiming at the modification of the organic groups towards
multifunctional complexes, we condensed thiosemicarbazide
and its methyl or phenyl dervative NH2NHCSNHRЈ (RЈ = H,
Me, Ph) with [(R1T)4S6] (T = Ge, Sn). Herein we report the
proof-of-principle for this approach, which follows a preferred
reaction pathway. During the reaction, the inorganic T4S6 core
is split up, while the organic ligands are extended by the
thiosemicarbazide molecules into a new chelating ligand,
CMe2CH2CMeNNCSNHRЈ. The latter additionally comprises
one sulfur atom that contributes to the TS moiety, thus repre-
senting a (TS2)2 fragment including a planar T2(µ-S)2 four-
membered ring structure. The resulting hydrazone complexes
[{(CMe2CH2CMeNNCSNHRЈ)T}2S4] bear terminal groups RЈ
which enable further functionalization, and which might act as
building blocks for new ternary complexes or hybrid-networks.
Results and Discussion
Synthesis
The title compounds were prepared according to
Scheme 1 and obtained as single crystals. In each case, the
organo-functionalized sesquichalcogenide cage [(R1T)4S6]
* Prof. Dr. S. Dehnen
Fax: 49 6421 28 25653
E-Mail: dehnen@chemie.uni-marburg.de
[a] Fachbereich Chemie and Wissenschaftliches Zentrum für
Materialwissenschaften (WZMW)
Philipps-Universität Marburg
Scheme 1. Reaction scheme for the generation of compounds 1–4.
T = Ge (1) or Sn (2–4), R1 = CMe2CH2COMe, RЈ = H (1, 2), Me (3),
or Ph (4). More details on the workup procedures are provided in the
Experimental Section.
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(T = Ge, Sn) is split into two smaller fragments. These frag- tion of gaseous hydrogen sulfide upon T–(µ-S) bond cleavage,
ments exhibit
and bear
CMe2CH2CMeNNCSNHRЈ (RЈ = H, Me, Ph) each.
a
two
planar T2(µ-S)2 four-membered ring shifting the chemical equilibrium toward the fragments. The
chelating
C,N,S-tridentate
ligands production of H2S was proven by formation of AgS upon con-
ducting the reaction atmosphere through an aqueous solution
Noteworthy is the fact that the condensation of thiosemicar- of silver nitrate. In fact, the driving force for this type of reac-
bazides NH2NHCSNHRЈ (RЈ = H, Me, Ph) does not simply tion seems to be even strong enough to afford the rarely ob-
lead to an extension of the organic decoration under preserva- served coordination number of five at the germanium atoms.
tion of the [T4S6] core, such as observed at the reaction of
[(R1Ge)4S6] with phenyl hydrazine, for instance. Here the orig-
inal [Ge4S6] adamantane complex is retained while the ligands
undergo the condensation into the hydrazones.[6b] The reac-
Crystal Structures of Compounds 1–4
tions presented in this work resemble more the reaction path-
Compounds [{(CMe2CH2CMeNNCSNHRЈ)T}2S4] (1: RЈ,
way that was observed upon reaction of [(R1Ge)4S6] with hy- T = H, Ge; 2: RЈ, T = H, Sn; 3: RЈ, T = Me, Sn; 4: RЈ, T =
drazine hydrate, which resulted in the formation of a hydra- Ph, Sn) were characterized by spectroscopy and by means of
zonium salt of a hydrazone functionalized, smaller thioger- X-ray diffraction.[13] The analyses reveal the presence of re-
manate complex, namely (NH3NH2)2[{RNGe}2(µ-S)2S2] (RN = lated complexes that differ in the nature of the terminal group
CMe2CH2CMeNNH2) is formed under cleavage of the [Ge4S6] RЈ at the thiosemicarbazone fragment (Figure 1). Crystallo-
precursor cage.[7a]
The formation of the C,N,S-tridentate ligands in the title summarizes selected structural parameters.
graphic and refinement details are given in Table 1. Table 2
compounds is similar to the formation of other metal thiosemi-
All compounds have inversion symmetry and comprise a
carbazone complexes.[11] The π-system of the thiosemicarbaz- planar T2(µ-S)2 four-membered ring. The tetrel (Ge, Sn) atoms
ide unit is delocalized, which can be represented in the canoni- exhibit trigonal bipyramidal coordination geometry. The three
cal thiol form. Thiosemicarbazone ligands show a strong affec- equatorial positions, i.e. those with shorter bonds to the T
tion to coordinate metals via the sulfur atom, as reported for atom, are occupied by one bridging sulfur atom (S1), one sul-
several thiosemicarbazone tin complexes.[12] However, thio- fur atom of the thiosemicarbazone ligand (S2) and one carbon
semicarbazone complexes with germanium have not yet been atom (C1). The axial positions, i.e. those with longer bonds to
structurally characterized.
the T atom, are occupied by the other bridging sulfur atom
During the generation of the C,N,S-tridentate ligand in the (S1a) and one nitrogen atom of the thiosemicarbazone ligand
reactions repoted herein, the formation of the new T–S bond, (N1) in a slightly declined fashion (µ-Si–T–N = 160.80(14)–
via coordination of the T atom by the thiosemicarbazone unit, 168.69(9)°). The intramolecular distances in 1 are in agree-
initiates a T–(µ-S) bond cleavage within the [T4S6] precursor ment with other reported hydrazone functionalized thioger-
complex. Obviously, the latter is preferred over the substitution manate complexes, like (NH3NH2)2[{RNGe}2(µ-S)2S2] (RN =
of an S for an N donor ligand at the T atom while retaining CMe2CH2CMeNNH2),[7a] and with other reported Ge–(µ-S)
the [T4S6] cage. The thermodynamic driving force for the ob- bond lenghts.[4b,14] The structural parameters of complexes 2–
served reaction pathway (Scheme 2) is apparently the forma- 4 also correlate well with values found in the literature.[6a,9b,15]
Scheme 2. Suggested reaction pathway leading to the formation of compounds 2–4. An according pathway is anticipated for T = Ge (1).
2
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Thiosemicarbazone-Functionalized Complexes with (GeS2)2 and (SnS2)2 Units
Figure 1. Thermal ellipsoid plots (50% probability) of the molecular structures of 1–4. Selected bond lengths and angles are summarized in
Table 2. Hydrogen atoms are shown as isotropic white spheres.
Table 1. Crystallographic and refinement details of 1–4 at 100 K (Mo-Kα radiation, λ = 0.71073 Å).
compound
1·2MeOH
2
3·MeOH
4
empirical formula
fw /g·mol–1
crystal color and shape
crystal size /mm3
crystal system
space group
C16H34Ge2N6O2S4
616.02
colorless block
0.04ϫ0.03ϫ0.01
monoclinic
P21/c
C14H26N6S4Sn2
644.08
colorless block
0.12ϫ0.04ϫ0.03
monoclinic
P21/n
C17H34N6OS4Sn2
704.20
colorless needle
0.25ϫ0.08ϫ0.06
monoclinic
C2/c
C26H34N6S4Sn2
796.27
colorless block
0.10ϫ0.04ϫ0.04
monoclinic
C2/c
a /Å
b /Å
c /Å
7.6959(15)
15.283(3)
11.093(2)
103.28(3)
1269.8(4)
2
9.1701(18)
12.524(3)
9.998(2)
93.38(3)
1146.2(4)
2
18.150(4)
12.070(2)
13.060(3)
98.21(3)
2831.8(10)
4
21.261(4)
10.978(2)
14.998(3)
120.14(3)
3027.5(11)
4
β /deg
V /Å3
Z
ρcalcd /g·cm–3
μ(Mo-Kα) /mm–1
absorption correction type
min./max. transmission
2θ range /deg
no. of measured reflns.
R(int)
1.611
2.72
numerical
0.875/0.974
9.24–50.00
6653
1.866
2.55
numerical
0.804/0.947
6.22–50.00
6706
1.652
2.08
numerical
0.835/0.960
9.90–50.00
6669
1.747
1.95
numerical
0.839/0.962
9.30–50.00
6038
0.1870
0.0777
0.0640
0.0822
indep. reflns.
2217
2016
2470
2615
indep. reflns. [IϾ2σ(I)]
no. of parameters
R1 [IϾ2σ(I)]/wR2 (all data)
S (all data)
1031
144
0.0603/0.1101
0.723
0.56/–0.53
1585
127
0.0327/0.0586
0.963
0.68/–0.66
2062
150
0.0171/0.0349
0.929
0.31/–0.36
1635
178
0.0452/0.0572
0.872
0.62 /–0.52
max. peak/hole/ e–·Å–3
The backbone of the C,N,S-tridentate ligands is almost
The bond lengths including the C,N,S-tridentate ligands are
planar under formation of a bicyclus of two five membered typical for TIV–C, TIV–S and TIV–imine bonds. The bonding
rings, T–C–C–C–N and T–N–N–C–S, that share one N–T situation for 2–4 is thus similar to known thiosemicarbazone
edge. As a result of the molecular inversion symmetry, the tin complexes.[12,16] In comparison to thiosemicarbazides
spatial arrangement of the two C,N,S-tridentate ligands is re- NH2NHCSNHRЈ, the distances N2–C7 (1.288(8)–1.327(6) Å)
verse to each other.
and C7–S2 (1.766(2)–1.769(10) Å) in 1–4 are consistent with
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Table 2. Selected structural parameters /Å, ° of 1–4. SSC denotes the thiosemicarbazone sulfur atom.
Compound
1 (T = Ge, RЈ = H)
2 (T = Sn, RЈ = H)
3 (T = Sn, RЈ = Me)
4 (T = Sn, RЈ = Ph)
T–µ-S
2.206(3)
2.409(3)
2.290(3)
2.018(9)
2.133(8)
1.769(10)
1.331(12)
1.313(13)
1.394(11)
86.30(9)
93.70(9)
113.10(10)
89.32(10)
98.3(2)
2.4050(12)
2.5072(13)
2.4670(12)
2.178(5)
2.294(4)
1.768(5)
1.328(6)
1.327(6)
1.385(5)
86.89(4)
2.3932(7)
2.5103(7)
2.4671(8)
2.186(2)
2.2809(18)
1.766(2)
1.337(3)
1.308(3)
1.395(2)
84.52(3)
95.48(3)
110.06(2)
92.01(2)
101.65(5)
160.83(5)
115.78(6)
103.16(6)
98.66(8)
2.399(2)
2.5206(18)
2.4521(14)
2.187(7)
2.337(5)
1.767(6)
1.372(6)
1.288(8)
1.386(6)
85.54(6)
94.46(6)
111.62(7)
92.83(6)
103.39(14)
160.80(14)
113.5(2)
T–µ-Si
T–SSC
T–C
T–N
SSC–C
C–N(HRЈ)
CCS=N(N)
N–N
T–µ-S–Ti
µ-S–T–µ-Si
µ-S–T–SSC
µ-Si–T–SSC
µ-S–T–N
µ-Si–T–N
µ-S–T–C
µ-Si–T–C
T–SSC–C
93.11(4)
114.95(5)
95.27(5)
96.02(9)
165.5(2)
114.3(3)
102.0(3)
98.6(3)
168.68(9)
113.79(12)
106.52(14)
99.44(16)
103.27(19)
99.53(18)
Symmetry code: [i] for 1: –x, 1–y, 1–z; 2: 1–x, –y, 1–z; 3: 1/2–x, 1/2–y, 2–z; 4: 1–x, 1–y, 1–z.
increasing single bond or double bond character, respec- an additional O–H···S interaction (O···S = 3.370(8) Å) leading
tively.[17,18] The crystal structures of compounds 1 and 2 indi- to the formation of a three dimensional network.
cate intermolecular, self-complementary hydrogen bonding
The organic ligands at compounds 1–4 allow for further
with N–H···N interactions (N···N = 3.001(6)–3.101(11) Å), that derivatization. Primary as well as secondary amines are suit-
generate one-dimensional chains (Figure 2 and Figure 3). In able for further organic reactions with molecules bearing com-
compounds 1 and 3, one observes also strong intermolecular plementary functionality; furthermore, they can be used for the
hydrogen bonds N–H···O to the solvent methanol molecules generation of tailor-made ligands for transition metal com-
(N···O = 2.835(4)–3.063(4) Å). In compound 1, the latter and plexes and clusters, and they may act as linkers or connectors,
respectively, for the construction of inorganic-organic hybrid
networks.
Conclusions
Four complexes that are based on [T2(µ-S)2] (T = Ge, Sn)
four membered rings have been synthesized and structurally
characterized. These complexes bear novel C,N,S-tridentate li-
gands (CMe2CH2CMeNNCSNHRЈ, RЈ = H, Me, Ph), the for-
mation of which includes a thermodynamically favored frag-
Figure 2. Intermolecular hydrogen bonding within compound 1, re- mentation of the originally reacted [T4S6] cages. Future work
sulting in one-dimensional chains extended along the crystallographic
will include the specific terminal functionalization of the NR2
[110] direction. Thermal ellipsoids of the non-hydrogen atoms are
group at the C,N,S-tridentate ligands for further organic reac-
shown at 50% probability ([a] = –1–x, 1–y, –z; N3–N2a = 3.101(11) Å,
tions or coordination to metal centers, with the aim to use these
N3–H2N3–N2a = 156°; [b] = –x, 0.5–y, 0.5–z; N3–O1b = 2.981(11) Å,
complexes as precursors to form larger clusters and hybrid net-
works.
N3–H1N3–O1b = 169(10)°.
Experimental Section
General. All synthesis steps were performed under argon. All solvents
were dried and freshly distilled prior to use. [(R1T)4S6]
(R1 = CMe2CH2COMe; T = Ge, Sn) were prepared according to the
reported method.[6b] 1H NMR, 13C NMR and 119Sn NMR measure-
ments were carried out using a Bruker DRX 300 MHz and DRX 400
MHz spectrometer at 25ºC. The chemical shifts were quoted in ppm
Figure 3. Intermolecular hydrogen bonding within compound 2, re-
sulting in zig-zag chains extended along the crystallographic [101] di-
rection. Thermal ellipsoids of the non-hydrogen atoms are shown at
50% probability ([a]: 1–x, 1–y, 1–z). N3–N2a = 2.999(6) Å, N3–
H2N3–N2a = 161(4)°.
1
relative to the residual protons of deuterated solvents in H NMR and
13C NMR. Me4Sn was used as internal standard for 119Sn NMR mea-
surements. Infrared (IR) spectra were recorded on a Bruker IFS 88
spectrometer (KBr, Nujol mull in polyethylene windows), Raman
4
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Thiosemicarbazone-Functionalized Complexes with (GeS2)2 and (SnS2)2 Units
spectra on a Jobin Yvon Labram HR 800. Melting points were mea-
sured in a sealed glass tube on a Krüss KSP1N melting point apparatus.
Elemental analysis was performed on an Elementar vario micro appa-
ratus.
ν˜ = 3362.8 (s), 2956.1 (m), 2936.2 (m), 2883.7 (m), 2847.6 (m),
1593.5 (m), 1645.0 (m), 1526.2 (s), 1486.0 (m), 1456.0 (w),
1399.0 (m), 1364.7 (w), 1333.7 (w), 1264.7 (m), 1239.7 (w), 1210.4
(m), 1177.9 (m), 1139.9 (w), 1122.9 (w), 1017.3 (w), 959.4 (w), 791.1
(m), 612.8 (m), 491.7 (w), 471.9 (w), 432.4 (w), 357.5 (m), 326.4 (w),
297.3 (m), 247.0 (w), 222.1 (w), 174.5 (w) 152.5 (w), 132.0
(w) cm–1. Raman: ν˜ = 3366.6 (w), 2999.0 (w), 2960.9 (w), 2936.6
(w), 2914.0 (m), 2886.3 (m), 2867.2 (m), 2815.2 (w), 2718.2 (w),
1647.8 (m), 1517.5 (m), 1419.0 (m), 1399.6 (w), 1388.5 (w), 1317.8
(m), 1270.7 (m), 1244.4 (m), 1212.5 (w), 1179.2 (m), 1143.2 (m),
1125.2 (m), 1089.1 (m), 845.1 (w), 823.0 (w), 515.2 (m), 505.2 (m),
478.9 (w), 374.4 (m), 359.0 (s), 353.5 (s), 317.2 (m), 278.5 (m), 249.9
(m), 225.1 (m), 125.4 (s), 106.0 (s) cm–1. Elemental analyses found
(calcd) for C17H34N6OS4Sn2: C, 28.24 (29.00); H, 4.61 (4.87); N,
11.75 (11.93); S, 17.63 (18.21) %.
Synthesis of [{(CMe2CH2CMeNNCSNH2)Ge}2S4] (1): [(R1Ge)4S6]
(0.050 g, 0.057 mmol) and thiosemicarbazide (0.021 g, 0.23 mmol)
were placed in a flask in a solvent mixture of dichloromethane/meth-
anol (3/3 mL). The mixture was refluxed for 8 h. The solvent was
evaporated and the residue was washed with a little amount of meth-
anol. Crystals of 1 were formed by layering the reaction mixture with
n-hexane within 7 d. Yield: 0.059 g (0.107 mmol, 94%). Mp: 178 °C
(dec.). HRMS (ESI): m/z (calc. [M + H]+) = 522.9609, m/z (exp.) =
522.9604. 1H NMR (300 MHz, [D6]DMSO, 25 °C): δ = 1.35 (s, 12H,
Me2), 2.14 (s, 6H, Me), 2.75 (s, 4H, CH2), 7.13 (s, 4H, NH2) ppm.
13C NMR (75 MHz, [D6]DMSO, 25 °C): δ = 21.9, 25.0, 31.7, 31.8,
48.0, 206.5 ppm. FT-IR: ν˜ = 3380.0 (s), 3264.5 (s), 3165.6 (s), 2963.1
(m), 2917.5 (w), 1719.2 (m), 1643.6 (m), 1625.0 (s), 1521.8 (s), 1458.9
(m), 1356.2 (m), 1315.5 (m), 1261.6 (m), 1222.2 (w), 1180.6 (m),
1122.4 (m), 1016.3 (m), 802.6 (m), 737.1 (m), 597.5 (m), 417.6 (m),
326.2 (w), 302.9 (w), 287.7 (w), 250.8 (w), 185.0 (w), 154.1 (w) cm–1.
Raman: ν˜ = 3389.0 (w), 3259.8 (w), 3182.4 (w), 2968.7 (w), 2948.4
(w), 2911.8 (m), 2895.6 (m), 2863.8 (w), 2720.2 (w), 1658.2 (m),
1505.0 (w), 1316.5 (w), 1187.1 (w), 1127.1 (m), 846.6 (w), 669.5 (w),
611.6 (w), 530.1 (m), 400.3 (m), 350.2 (s), 280.4 (w), 122.4 (s) cm–1.
Elemental analyses found (calcd) for C16H34Ge2N6O2S4: C, 30.75
(31.20); H, 4.98 (5.56); N, 15.83 (13.64); S, 21.73 (20.82) %.
Synthesis of [{(CMe2CH2CMeNNCSNHPh)Sn}2S4] (4): [(R1Sn)4S6]
(0.050 g, 0.046 mmol) and 4-phenylthiosemicarbazide (0.030 g, 0.18
mmol) were placed in a flask in a solvent mixture of dichloromethane/
methanol (3/3 mL). The mixture was stirred for 3 d at room tempera-
ture. The solvent was evaporated and the residue was washed with a
little amount of methanol. Crystals of 4 were formed by solving the
precipitate in tetrahydrofuran and layering with n-hexane within 7 d.
Yield: 0.041 g (0.052 mmol, 57%). Mp: 157 °C (dec.). HRMS (ESI):
m/z (calc. [M + H]+) = 796.9842, m/z (exp.) = 796.9833. 1H-NMR
(300 MHz, [D6]DMSO, 25 °C): δ = 1.41 (s, 12H, Me2), 2.20 (s, 6H,
Me), 2.66 (s, 4H, CH2), 6.94–7.00 (m, 2H), 7.24–7.31 (m, 4H), 7.71–
7.76 (m, 4H), 9.67 (br s, 2H, NH) ppm. 119Sn-NMR (149 MHz, THF):
δ = –90 ppm. FT-IR: ν˜ = 3281.4 (m), 2922.1 (m), 2849.3 (m), 1693.6
(s), 1639.0 (w), 1601.7 (m), 1509.0 (s), 1456.7 (w), 1436.2 (s), 1362.1
(m), 1317.6 (m), 1258.9 (m), 1181.6 (m), 1122.4 (m), 1093.0 (m),
1018.9 (m), 957.8 (w), 893.1 (w), 806.0 (m), 750.3 (m), 689.2 (m),
610.9 (m), 500.5 (w), 360.9 (m), 326.0 (w), 285.7 (w), 249.5 (w),
220.7 (w), 198.7 (w), 151.6 (w), 134.0 (w), 114.2 (w) cm–1. Raman:
ν˜ = 3056.8 (w), 2915.2 (m), 2886.5 (m), 2867.9 (m), 2854.8 (m),
2719.9 (w), 1640.6 (m), 1604.1 (m), 1550.6 (m), 1541.6 (w), 1541.6
(w), 1510.0 (w), 1315.0 (m), 1261.0 (w), 1241.5 (w), 1184.5 (w),
1177.0 (w), 1139.0 (w), 1123.5 (m), 1095.0 (w), 1030.7 (w), 998.0
(m), 869.0 (w), 840.3 (m), 617.4 (w), 584.2 (w), 515.8 (s), 445.5 (w),
372.9 (s), 357.0 (s), 316.1 (s), 298.5 (w), 266.3 (w), 251.2 (m), 228.2
(w), 210.1 (w), 147.9 (m), 124.9 (s), 101.1 (s) cm–1. Elemental analy-
ses found (calcd) for C26H34N6S4Sn2: C, 38.28 (39.22); H, 4.14 (4.30);
N, 9.80 (10.55); S, 16.79 (16.11) %.
Synthesis of [{(CMe2CH2CMeNNCSNH2)Sn}2S4] (2): [(R1Sn)4S6]
(0.050 g, 0.046 mmol) and thiosemicarbazide (0.017 g, 0.19 mmol)
were placed in a flask in a solvent mixture of dichloromethane/meth-
anol (5/5 mL). The mixture was stirred for 3 d at room temperature.
The solvent was evaporated and the residue was washed with a little
amount of methanol. Crystals of 2 were formed by layering the con-
centrated reaction mixture with diethylether within 2 d. Yield: 0.055 g
(0.085 mmol, 92%). Mp: 180 °C (dec.). HRMS (ESI): m/z (calc.
1
[M + H]+) = 644.9213, m/z (exp.) = 644.9219. H NMR (300 MHz,
[D6]DMSO, 25 °C): δ = 1.38 (s, 12H, CMe2), 2.10 (s, 6H, Me), 2.60
(s, 4H, CH2), 7.17 (s, 4H, NH2) ppm. 119Sn NMR (149 MHz, THF):
δ = –80 ppm. FT-IR: ν˜ = 3375.5 (m), 3267.7 (m), 3146.6 (m), 2954.9
(w), 1693.7 (m), 1644.7 (m), 1621.8 (m), 1597.3 (m), 1512,8 (s),
1453.2 (w), 1348.9 (m), 1261.2 (m), 1217.7 (w), 1180.8 (m), 1109.3
(m), 1025.2 (s), 1003.3 (s), 866.1 (w), 802.4 (m), 760.2 (w), 737.0 (m),
579.7 (m), 361.1 (m), 311.9 (w), 295.6 (m), 249.9 (w), 228.2 (w),
173.3 (w), 152.5 (w), 112.4 (w) cm–1. Raman: ν˜ = 2960.5 (w), 2937.6
(m), 2908.4 (m), 2883.1 (m), 2852.3 (w), 1645.6 (m), 1497.4 (m),
1314.1 (m), 1220.5 (m), 1121.0 (m), 820.3 (w), 601.7 (w), 521.8 (w),
507.0 (m), 477.4 (w), 439.0 (w), 366.0 (s), 537.5 (s), 352.0 (s), 315.0
(m), 277.6 (s), 227.3 (m), 159.8 (m) cm–1. Elemental analyses found
(calcd) for C14H26N6S4Sn2: C, 25.86 (26.11); H, 4.07 (4.07); N, 12.53
(13.05); S, 19.59 (19.91) %.
X-Ray Structure Determination
Data were collected on a diffractometer equipped with a STOE im-
aging plate detector system IPDS2T, using graphite-monochromized
Mo-Kα radiation (λ = 0.71073 Å) at 100 K. Structure solution and
refinement were performed by direct methods and full-matrix least-
Synthesis of [{(CMe2CH2CMeNNCSNHMe)Sn}2S4] (3): [(R1Sn)4S6] squares on F2, respectively, using SHELXTL software.[13] Where pos-
(0.050 g, 0.046 mmol) and 4-methylthiosemicarbazide (0.019 g, sible, hydrogen atoms were inserted, assuming idealized geometry and
0.18 mmol) were placed in a flask in a solvent mixture of dichloro-
methane/methanol (3/3 mL). The mixture was stirred for 3 d at room
refined as riding on their parent atoms (with Uiso(H) = nUeq(parent
atom), where n = 1.2 for hydrogen atoms of methylene groups and
temperature. The solvent was evaporated and the residue was washed phenyl rings; n = 1.5 for hydrogen atoms of methyl groups). Hydrogen
with a little amount of methanol. Crystals of 3 were formed by layering atoms of the hydroxy group of methanol molecules (in 1 and 3) were
the reaction mixture with n-hexane within 7 d. Yield: 0.031 g found on the difference Fourier map. By using the AFIX 147 con-
(0.046 mmol, 50%). Mp: 156 °C (dec.). HRMS (ESI): m/z (calc.
straint, they were allowed to rotate but not to tip and were refined with
1
[M + H]+) = 672.9526, m/z (exp.) = 672.9545; H NMR (300 MHz, Uiso(H) = 1.5Ueq(parent atom). The hydrogen atoms of the amine
[D6]DMSO, 25 °C): δ = 1.41 (s, 12H, CMe2), 2.16 (s, 6H, Me), 2.64 groups were also found on the Fourier map and refined with
(s, 4H, CH2), 2.84 (d, J = 4.8 Hz, 6H, NMe), 7.50 (q, J = 4.8 Hz, 2H,
NH) ppm. 119Sn NMR (149 MHz, THF): δ = –85 ppm. FT-IR:
Uiso(H) = 1.5Ueq(parent atom). Restraints were imposed on N–H bond
lengths at 0.88 Å using DFIX. Final crystallographic data and values
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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Job/Unit: Z12292
/KAP1
Date: 27-08-12 17:46:23
Pages: 7
J. P. Eußner, S. Dehnen
ARTICLE
Inorg. Chem. 2009, 48, 7373–7377; b) M. R. Halvagar, Z. Has-
sanzadeh Fard, S. Dehnen, Chem. Commun. 2010, 46, 4716–
4718.
of R1 and wR2 are listed in Table 1. Selected bond lengths and bond
angles are provided in Table 2.
[8] Z. Hassanzadeh Fard, R. Clérac, S. Dehnen, Chem. Eur. J. 2010,
16, 2050–2053.
Acknowledgment
[9] Z. Hassanzadeh Fard, M. R. Halvagar, S. Dehnen, J. Am. Chem.
Soc. 2010, 132, 2848–2849.
[10] M. R. Halvagar, Z. Hassanzadeh Fard, S. Dehnen, Chem. Eur. J.
2011, 17, 4371–4373.
[11] a) S. D. Khanye, B. Wan, S. G. Franzblau, J. Gut, P. J. Rosenthal,
G. S. Smith, K. J. Chibale, J. Organomet. Chem. 2011, 696,
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ueira, A. Fernández, J. M. Vila, Eur. J. Inorg. Chem. 2011, 368–
376.
The authors thank the Deutsche Forschungsgemeinschaft (DFG) for
financial support and Dr. M. R. Halvagar for supervision of the experi-
mental work.
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Received: June 24, 2012
[7] a) M. R. Halvagar, Z. Hassanzadeh Fard, L. Xiong, S. Dehnen,
Published Online: ᭿
6
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Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z12292
/KAP1
Date: 27-08-12 17:46:23
Pages: 7
Thiosemicarbazone-Functionalized Complexes with (GeS2)2 and (SnS2)2 Units
J. P. Eußner, S. Dehnen* ................................................... 1–7
Formation of Thiosemicarbazone-Functionalized Complexes
with (GeS2)2 and (SnS2)2 Units
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
7