metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
double bond. Also structurally characterized are species
where protonated 4,6-dimethylpyrimidine-2(1H)-thione plays
the role of cation with halide or polyhalide (MXn) anions
(Gaye et al., 2009). Meanwhile, thiourea is most commonly
encountered as a raw material in organic syntheses, but can
also play a role in coordination chemistry. Structural reports of
thiourea-coordinated Zn complexes, with carboxylic acid
derivatives (Burrows et al., 2004) or chloride anions as addi-
tional ligands, are known, though the latter are rare and only
two examples exist to date (Bombicz et al., 2007; Wu et al.,
2004). In all of these complexes, multiple thiourea ligands are
coordinated to Zn. To the best of our knowledge, a
monothiourea-coordinated Zn complex has not yet been
structurally described. Combining these topics, the crystal
structure of the title compound, (I), is reported herein and
compared with other related structures, including that of
bis(4,6-dimethyl-2-sulfanylidenepyrimidinium) tetrachlorido-
zinc(II) monohydrate (Godino-Salido et al., 1995), where an
additional chloride ligand replaces the thiourea molecule
of (I).
ISSN 0108-2701
(4,6-Dimethyl-2-sulfanylidenepyrimi-
din-1-ium) trichlorido(thiourea-jS)-
zinc(II)
Wei-Wei Fu,* Man-Sheng Chen, Yang Liu and Fu-Xing
Zhang
Key Laboratory of Functional Organometallic Materials, of General Colleges and
Universities in Hunan Province, Department of Chemistry and Materials Science,
Hengyang Normal University, Hengyang 421008, People’s Republic of China
Received 17 November 2012
Accepted 5 March 2013
The title compound, (C6H9N2S)[ZnCl3{SC(NH2)2}], exists as a
zincate where the zinc(II) centre is coordinated by three
chloride ligands and a thiourea ligand to form the anion. The
organic cation adopts the protonated 4,6-dimethyl-2-sulfanyl-
idenepyrimidin-1-ium (L) form of 4,6-dimethylpyrimidine-
2(1H)-thione. Two short N—Hꢀ ꢀ ꢀCl hydrogen bonds involving
the pyrimidine H atoms and the [ZnCl3L]ꢁ anion form a
crystallographically centrosymmetric dimeric unit consisting
of two anions and two cations. The packing structure is
completed by longer-range hydrogen bonds donated by the
thiourea NH2 groups to chloride ligand hydrogen-bond
acceptors.
In (I) (Fig. 1), the ZnII centre is coordinated by three Clꢁ
anions and one thiourea molecule (the thiourea is believed to
originate as an impurity carried over from the prior synthesis
of the sulfanylidenepyridinium starting material). The
distances between the Zn and Cl atoms are given in Table 1,
along with other selected geometric parameters. These bond
distances are similiar to those in related compounds, such as
bis(4,6-dimethyl-2-sulfanylidenepyrimidinium) tetrachlorido-
Comment
In recent decades, coordination compounds, and in particular
supramolecular coordination compounds, have received much
attention. This is not only because of the diversity of their
structures, but also because of their potentially useful prop-
erties, such as luminescent or magnetic behaviour. A further
source of interest is their chemical activity in fields such as
biomedicine and catalysis (Cui et al., 2012; Kurmoo, 2009;
Horcajada et al., 2012; Lee et al., 2009). Substituted pyrimi-
dine-2-thiols, which possess both nitrogen and sulfur potential
coordination sites, have been widely used in the preparation of
traditional metal complexes and their coordination modes
have been thoroughly investigated. In most cases, they are
found as the anion and coordinate to metal centres through
˚
zincate(II) (2.241, 2.277, 2.270 and 2.267 A; Godino-Salido et
al., 1995), dichloridobis(thiourea)zinc(II) bis(4,5-diazafluor-
˚
en-9-one) [2.2475 (19) and 2.2685 (9) A; Wu et al., 2004] and
˚
dichloridobis(thiourea-ꢀS)zinc(II) (2.310 and 2.273 A; Bom-
bicz et al., 2007), though they are slightly longer than most of
these literature cases. The distance between Zn and the S atom
˚
in (I) is 2.3252 (4) A, which is also similiar to, if slightly shorter
than, those in dichloridobis(thiourea-ꢀS)zinc(II) (2.341 A;
˚
´
both S and N atoms (see, for example, Rodrıguez et al., 2011).
Other coordination modes are found more rarely. These are
anionic species where only sulfur is coordinated to the metal
(Vergara et al., 2011) and neutral thione tautomers where
again only sulfur is coordinated to the metal centre (Das et al.,
2011). Note that 4,6-dimethylpyrimidine-2(1H)-thione is the
isomer of 4,6-dimethylpyrimidine-2-thiol with an H atom
Figure 1
A view of the contents of the asymmetric unit of (I), showing the atom-
numbering scheme. Displacement ellipsoids are drawn at the 30%
probability level.
bound to an N rather than to the S atom and thus has an S
C
384 # 2013 International Union of Crystallography
doi:10.1107/S0108270113006380
Acta Cryst. (2013). C69, 384–387