Unsymmetrically-substituted 2,4,6-trimercaptotriazine: Supramolecular self-assembly through C=S?H-N hydrogen bonds in the crystal structures of C3N3S3H2Na·3H2O and C3N3S3H2Cu(PPh3) 2

Article abstract of DOI:10.1016/S0020-1693(02)01468-8

The monosodium salt of trithiocyanuric acid, C₃N₃S₃H₂Na, has been isolated as its trihydrate (1) by partial neutralisation of C₃N₃S₃H₃ with NaOH. Each sodium in the structure displays a novel cis-S₂NaO₄ coordination sphere and is hydrogen bonded to the anion, which adopts its thione form. Compound 1 has been used to synthesise other unsymmetrically-metallated trithiocyanuric acid derivatives, typified by [C₃N₃S₃H₂Cu(PPh₃) ₂] and whose structure has also been determined. The nickel complex [C₃N₃S₃H₂NiCl(PPh₃) ₂]·0.5CH₂Cl₂ was also obtained, but only tri-substituted compounds C₃N₃S₃[Au(PPh₃)] ₃·2CH₂Cl₂ and C₃N₃S₃(SnMe₃)₃ were formed when 1 was reacted with (Ph₃P)AuCl and Me₃SnCl, respectively.

Full text of DOI:10.1016/S0020-1693(02)01468-8

Inorganica Chimica Acta 348 (2003) 75ꢁ81
/
www.elsevier.com/locate/ica
Unsymmetrically-substituted 2,4,6-trimercaptotriazine:
supramolecular self-assembly through CꢀSÁ Á ÁHꢁN hydrogen bonds
in the crystal structures of C3N3S3H2Na×3H2O and
C3N3S3H2Cu(PPh3)2
/
/
/
Mary F. Mahon a, Kieran C. Molloy a,*, Monica M. Venter a,1, Ionel Haiduc b
a Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK
b Department of Chemistry, Babes-Bolyai University, Cluj-Napoca RO-3400, Romania
Received 26 July 2002
Abstract
The monosodium salt of trithiocyanuric acid, C3N3S3H2Na, has been isolated as its trihydrate (1) by partial neutralisation of
C3N3S3H3 with NaOH. Each sodium in the structure displays a novel cis-S2NaO4 coordination sphere and is hydrogen bonded to
the anion, which adopts its thione form. Compound 1 has been used to synthesise other unsymmetrically-metallated trithiocyanuric
acid derivatives, typified by [C3N3S3H2Cu(PPh3)2] and whose structure has also been determined. The nickel complex
[C3N3S3H2NiCl(PPh3)2]×
/
0.5CH2Cl2 was also obtained, but only tri-substituted compounds C3N3S3[Au(PPh3)]3×
/2CH2Cl2 and
C3N3S3(SnMe3)3 were formed when 1 was reacted with (Ph3P)AuCl and Me3SnCl, respectively.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Trithiocyanuric acid; Sodium salt; Copper salt; X-ray; Cꢀ
/
SÁ Á ÁHꢁ/N hydrogen bonds
1. Introduction
chelating [9] or bridging [11ꢁ
work has furnished the structures of gold [(Ph3P)Au]3-
[C3N3S3] [12], (AuC3N3S3)(AuL)2]2 (LꢂMe2PhP [12],
tBuNC [13] [C3N3S3H2Au(PPh3)3](DMF) [14]), nickel
/
13] ligand. More recent
In this paper we wish to report further on the
chemistry of 1,3,5-triazine-2,4,6-trithiol (I) (also referred
to as 2,4,6-trimercaptotriazine or trithiocyanuric acid,
H3TMT). Compound I, which can exist in either thiol
(Ia) or thione (Ib) forms, is an analytical reagent which
has attracted renewed general interest in recent years
because of its use in removing heavy metals (Agꢀ,
/
[Ni(pmdien)(HC3N3S3)(H2O)] (pmdienꢂ
/
N,N,N?,N?,
Nƒ-pentamethyldiethylenetriamine) [15],
mercury
[(MeHg)3(C3N3S3)] [16] and copper derivatives
[(CuPPh3)3(C3N3S3)]2 [11], while we have synthesised
several organotin derivatives and determined the struc-
Hg2ꢀ, Cd2ꢀ, Pd2ꢀ, Cu2ꢀ) from waste waters [1ꢁ
3].
/
tures of (R3Sn)3(C3N3S3) (RꢂMe, Ph) [17]. The use of
/
metal complexes of I for the formation of nanoparticu-
late metal sulphides has also been noted [18].
Despite this, the structural chemistry of metallo-deriva-
tives of I remains limited (partly due to reasons of
solubility) [4,5] and is mainly confined to derivatives of
s-(Liꢀ, Naꢀ, Ca2ꢀ, Sr2ꢀ, Ba2ꢀ) [3,6ꢁ
elements [4,5,9ꢁ13] where it can behave as either a
/
8] and d-block
/
* Corresponding author. Tel.: ꢀ
826231.
E-mail address: chskcm@bath.ac.uk (K.C. Molloy).
/
44-1225-826382; fax: ꢀ44-1225-
/
Additional interest in I stems from the fact that
recrystallisation from polar solvents (DMSO, MeOH,
Me2CO) or in the presence of species such as melamine
1
On leave from Department of Chemistry, Babes-Bolyai
University, Cluj-Napoca RO-3400, Romania.
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(02)01468-8

76
M.F. Mahon et al. / Inorganica Chimica Acta 348 (2003) 75ꢁ81
/
or 4,4?-bipyridyl yields supramolecular arrays built up
from NꢁHÁ Á ÁO, NꢁHÁ Á ÁN, NꢁHÁ Á ÁS and SÁ Á ÁS inter-
actions [19ꢁ21]. Similarly, in addition to molecular
species such as ‘manxane’ M3C3N3S3 (MꢂR3Sn [17],
R3PAu [13]), metal derivatives of I e.g. [(AuC3N3-
2.2. Synthesis of C3N3S3H2Na×
/
3H2O (1)
/
/
/
/
A suspension of C3N3S3H3 (1 equiv.) in aqueous
NaOH (1 equiv.) solution was stirred at r.t. for 30 min
during which time almost complete dissolution oc-
curred. After removing the small amount of remaining
solid, the pale yellow filtrate was allowed to evaporate
slowly at r.t. to give the product as a yellow crystalline
solid, in satisfactory yield (66%), m.p. 280 8C (dec.).
/
t
S3)(AuL)2]2 (LꢂMe2PhP [12], BuNC [13]) can also
/
form supramolecular arrays. It was thus of interest to us
to study further the chemistry of partially metallated
species starting from either C3N3S3H2Na or
C3N3S3HNa2, the results of which we now report.
Both salts have previously been cited in patents
[22,23]. The only structural reports directly relevant to
Alternatively, an aqueous solution of C3N3S3Na3×
/
9H2O (1 equiv.) and HCl (2 equiv.) were stirred at r.t.
for 1 h. The resulting pale yellow clear solution was
allowed to evaporate slowly at r.t. to give the product as
yellow crystalline solid. Depending on the concentration
of the reaction mixture, the product might also deposit
during the reaction as a microcrystalline yellow pre-
cipitate. Yield: 80%. Anal. Found (Calc. for C3H8N3-
NaO3S3): C, 14.2 (14.2); H, 3.2 (3.2); N, 16.2 (16.6)%.
1H NMR (DMSO): 12.23 (s, broad, NH), 3.56 (s, H2O);
these findings are [C3N3S3H2]2M (Mꢂ/Mg, Ca, Sr, Ba)
[3,8], C3N3S3H2Li×
/
2HMPA [6] and [C3N3S3H2Au-
(PPh3)3](DMF) [14].
2. Experimental
The starting materials were purchased from a com-
mercial source (Aldrich). Spectra were recorded on the
following instruments: JEOL GX270 (1H, 13C NMR),
13C NMR: 176.9 (Cꢁ
/
S); IR (Nujol): 3458 s (br), 3100 m,
1623 w, 1588 w, 1554 s, 1276 w, 1239 s, 1149 vs, 882 m,
812 m, 774 w.
PerkinꢁElmer 599B (IR). For all compounds, infrared
/
spectra were recorded as nujol mulls on KBr plates and
all NMR data were recorded on saturated solutions at
room temperature (r.t.); chemical shifts are in ppm
relative to either Me4Si (1H, 13C) or H3PO3 (31P),
coupling constants are in Hz.
The starting materials were purchased from a com-
mercial source (Aldrich). (Ph3P)AuCl was prepared
according to literature methods [24].
2.3. Synthesis of [C3N3S3H2Cu(PPh3)2]×
/
CH2Cl2 (2)
C3N3S3H2Na×
/
3H2O (0.5 g, 2.0 mmol) was stirred as a
a
suspension in
CH2Cl2 solution (70 ml) of
(PPh3)4Cu(OAc) (2.3 g, 2.0 mmol) for 6 h at r.t. After
removing the solid residue, the yellow solution was
concentrated to low volume and stored at low tempera-
ture for 2ꢁ3 days to give the product as yellow crystal-
/
(Ph3P)4Cu(OAc) was obtained by the reaction of
line solid. Yield: 1.05 g, 62%, m.p. 180 8C (dec.).
As an alternative method, EtOH solution (30 ml) of
stoichiometric amounts of Cu(OAc)2×
/
H2O and PPh3 in
MeOH under reflux, followed by crystallisation from
C3N3S3H2Na×
/
3H2O (0.4 g, 1.6 mmol) was added drop-
MeOH at low temperature. Yield: 84%, m.p. 152 8C.
Anal. Found (Calc. for C74H63CuO2P4): C, 75.6 (75.9);
wise to (PPh3)4Cu(OAc) (1.8 g, 1.5 mmol) in EtOH (20
ml). Pale yellow solid precipitated at once. After stirring
the mixture at r.t. for 1 h, the mother liquid was
removed and the precipitate was washed with EtOH
and dried in vacuo. Yield: 0.80 g, 63%. Anal. Found
(Calc. for C40H34Cl2CuN3P2S3): C, 56.6 (56.6); H, 4.1
1
H, 5.4 (5.4)%. H NMR (CDCl3): 7.26ꢁ
/
7.10 (m, 30H,
Ph), 1.87 (s, 3H, CH3CO2). 13C NMR: 179.0
(CH3COO), 134.3, 123.1 (3-Ph), 130.1 (4-Ph), 129.0,
128.9 (2-Ph), 23.8 (CH3COO). 31P NMR: d 0.00. IR
(Nujol): 1583 m, 1571 m, 1549 s, 1476 vs, 1434 vs, 1338
w, 1178 w, 1156 w, 1118 w, 1094 s, 1068 w, 1026 m, 996
w, 926 w, 752 s, 742 s, 702 s, 694 vs, 666 s.
1
(4.0); N, 5.0 (5.0)%. H NMR (DMSO), recorded on a
sample re-crystallised from CH2Cl2/MeOH: 3.30 (s,
CH3, MeOH), 5.70 (s, CH2, CH2Cl2), 7.26 (s, broad,
30H, Ph), 13.33 (s, br, 2H, NH); 13C NMR: 55.2
(CH2Cl2), 128.9 (2-Ph), 130.2 (4-Ph), 133.6 (3-Ph); 31P
2.1. Synthesis of C3N3S3H3 (I)
NMR: ꢃ17.1; IR (Nujol): 3100 m, 1583 w, 1547 s, 1524
/
The reaction of C3N3S3Na3×
/
9H2O (1 equiv.) with
s, 1233 s, 1174 s, 1141 vs, 1117 s, 1094 m, 1049 w, 1024
w, 995 w, 892 w, 743 s, 693 vs.
concentrated HCl (3 equiv.) in aqueous solution gave
the product as a fine yellow precipitate, in good yield
(88%). A product of satisfactory purity can be obtained
by washing the precipitate with water and drying it at
2.4. Synthesis of [C3N3S3H2][(PPh3)2NiCl]×
/
0.5CH2Cl2 (3)
r.t. overnight. m.p.ꢀ290 8C. Anal. Found (Calc. for
/
C3H3N3S3): C, 20.3 (20.3); H, 1.7 (1.7); N, 23.3 (23.7)%.
1
NMR (DMSO): H: 13.7 (s, broad, NH), 3.39 (s, H2O);
C3N3S3H2Na×
black
CH2Cl2 solution (50 ml) of (PPh3)2NiCl2 (0.33 g, 0.5
/
3H2O (0.27 g, 1.07 mmol, 7% excess)
was stirred as a suspension in a dark greenishꢁ
/
13C: 172.2 (Cꢁ
vs, 1298 m, 1258 m, 1123 w, 983 w, 786 w, 744 ms.
/S); IR (Nujol): 3130 s (br), 1576 s, 1532
mmol) at r.t. for 6 h. After removing the solid residue,

M.F. Mahon et al. / Inorganica Chimica Acta 348 (2003) 75ꢁ
/
81
77
C6H14 was added to the dark brown solution (approxi-
mately 15 ml) and the mixture concentrated to low
volume to yield the product as a microcrystalline brick-
brown precipitate. The mother liquid was removed by
filtration and the product was dried in vacuo. Yield: 0.2
g, 40%. Anal. Found (Calc. for C39.5H31Cl2N3NiP2S3):
C, 56.4 (56.8); H, 4.0 (3.7); N, 5.9 (5.0)%. IR (nujol):
1586 w, 1573 w, 1543 s, 1438 vs, 1399 m, 1245 m, 1189 s,
1144 s, 1094 s, 1069 w, 1021 w, 998 w, 749 m, 741 m, 704
m, 692 vs, 668 m.
seen to been disordered in a 1:1 ratio between sites O(3)
and O(3A); this precluded location of the associated
hydrogen atoms which were therefore not included in
the final refinement. The hydrogen atoms in the
remaining 2 water molecules were readily located
˚
however, and refined at a distance of 0.89 A from the
˚
relevant parent atoms, and at a distance of 1.45 A from
each other in individual waters.
In 2, one of the chlorines in the solvate molecule also
exhibited disorder between positions Cl(2), Cl(2A) and
Cl(2B) in respective 48:32:20 ratios. In the final least-
squares cycles, these partial chlorines were restrained to
have similar distances from the carbon in the solvate,
C(4). The solvent hydrogens included in the refinement
are based on the position of the major disordered
chlorine component.
Non-hydrogen atoms were refined anisotropically
without exception. All data were corrected for Lorentz,
polarisation and extinction. An absorption correction
(multiscan) was applied to data for 2 (maximum and
minimum transmission factors 1.044, 0.949; respec-
tively). Software used: SHELXS-86 [25], SHELXL-97 [26],
ORTEX [27].
2.5. Synthesis of C3N3S3[Au(PPh3)]3×
/
2CH2Cl2 (4)
C3N3S3H2Na×3H2O (0.15 g, 0.6 mmol, approximately
/
20% excess) was stirred for 24 h as a suspension in a
CH2Cl2 solution (20 ml) of (PPh3)AuCl (0.23 g, 0.47
mmol). The solid residue was removed and the pale
yellow filtrate was mixed with C6H14 (1:1) and stored at
low temperature for 1ꢁ2 weeks to yield the product as
/
pale yellow microcrystalline solid. Yield: 0.1 g, 35%,
m.p. 174 8C. Anal. Found (Calc. for C59H49Au3-
Cl4N3P3S3): C, 41.1 (41.1); H, 2.8 (2.8); N, 2.8 (2.4)%.
3. Crystallography
4. Results and discussion
Crystallographic data for compounds 1 and 2 are
summarised in Table 1. In both cases, data collections
were implemented on a Nonius KappaCCD diffract-
ometer. One of the water molecules in compound 1 was
We have prepared and isolated C3N3S3H2Na as its
trihydrate (1) either from neutralisation of C3N3S3H3
with 1 equiv. of NaOH or by the addition of 2 equiv. of
HCl to C3N3S3Na3. Attempts to prepare C3N3S3HNa2
by the same routes failed. Reactions of both C3N3S3H3
(1 equiv.) with NaOH (2 equiv.) and C3N3S3Na3.9H2O
(1 equiv.) with HCl (1 equiv.), respectively gave the
Table 1
Crystallographic data for 1 and 2
monosodium salt 1 in satisfactory yield (66ꢁ80%). It has
/
been noted by others that the dianion [C3N3S3H]2ꢃ is
dominant in aqueous solutions of approximately pH 10
while the monoanion [C3N3S3H2]ꢃ is dominant at
approximately pH 7 [18].
1
2
Empirical formula
Formula weight
Temperature (K)
Crystal system
Space group
C3H8N3NaO3S3 C40H34Cl2CuN3P2S3
253.29
150(2)
849.26
150(2)
monoclinic
P21/a
monoclinic
P21/n
The structure of 1 is shown in Fig. 1; two of the water
molecules are well resolved while the third [based on
O(3)] is disordered. Within the disordered water, O(3)
˚
a (A)
7.7860(2)
12.6940(4)
10.3850(4)
109.087(3)
969.98(5)
4
14.9240(2)
16.2290(2)
16.6720(2)
102.1710(8)
3947.22(9)
4
˚
b (A)
and O(3A) are sited close to each other [O(3)ꢁ
/
O(3A):
˚
c (A)
˚
0.76(1) A] so only the coordination of O(3) will be
discussed further. The anion exists in its thione form
with two of the nitrogen atoms being protonated. The
b (8)
3
V (A )
˚
Z
Absorption coefficient
)
0.787
0.962
Cꢀ
/
S bonds are relatively short [S(1)ꢁ
/
C(1) 1.681(6),
(mmꢃ1
Reflections collected
˚
S(2)ꢁ C(3) 1.684(6) A] and overall
are shorter than those found in S-substituted species
/
C(2) 1.679(6), S(3)ꢁ
/
5613
2s) 1829
1944
61 287
7497
9029
Reflections observed (ꢀ
Independent
/
˚
such as C3N3S3(SnMe3)3 [1.743(3) A] [17]. Each sodium
adopts a cis-S2NaO4 coordination sphere in which the
reflections
Final R indices
[Rint
ꢂ
/
/
0.0416]
0.0729,
wR2ꢂ0.2221
R1ꢂ0.0758,
wR2ꢂ0.2234
1.350
[Rint
R1ꢂ
wR2ꢂ
R1ꢂ0.0459,
wR2ꢂ0.0894
0.979
ꢂ
/
/
0.0470]
0.0336,
0.0818
R1ꢂ
two soft sulphur atoms are more weakly bound [Na(1)ꢁ
/
[I ꢀ/2s(I)]
/
/
˚
S(1ƒ): 2.955(3); Na(1)ꢁ
hard oxygens [Na(1)ꢁ
2.384(5); Na(1)ꢁO(2?): 2.391(6); Na(1)ꢁ
2.401(11), 2.337(11) A]. This is a unique coordination
/
S(3) 3.186(3) A] than the four
O(1): 2.379(5); Na(1)ꢁO(1?):
O(3)/O(3A):
R indices (all data)
/
/
/
/
/
/
Goodness-of-fit on F2
/
/
˚

78
M.F. Mahon et al. / Inorganica Chimica Acta 348 (2003) 75ꢁ81
/
Fig. 1. The structure of 1 showing the atomic labelling; O(3A), the complimentary position for O(3) in the disordered water, has been omitted for
clarity. Thermal ellipsoids are at the 30% probability level. Selected metrical data: S(1)ꢁC(1) 1.681(6), S(2)ꢁC(2) 1.679(6), S(3)ꢁC(3) 1.684(6), N(1)ꢁ
C(2) 1.352(8), N(1)ꢁC(1) 1.375(8), N(2)ꢁC(2) 1.354(8), N(2)ꢁC(3) 1.384(8), N(3)ꢁC(1) 1.344(8), N(3)ꢁC(3) 1.346(8), Na(1)ꢁO(1) 2.379(5), Na(1)ꢁ
O(1?) 2.384(5), Na(1)ꢁO(2) 2.391(6), Na(1)ꢁO(3) 2.401(11), Na(1)ꢁS(1??): 2.955(3); Na(1)ꢁS(3) 3.186(3) A (symmetry operations: ?ꢃx, ꢃy, ꢃz; ƒ: 1/
2ꢀx, 1/2ꢃy, z).
/
/
/
/
/
/
/
/
/
/
/
˚
/
/
/
/
/
/
/
/
/
mode in TMT molecules of this type, though it
resembles the SNaO5 coordination in Na3(TMT)×
9H2O [7], and contrasts with the all-oxygen coordina-
C3N3H2Cu(PPh3)2. This precipitates directly when the
reaction is carried out in ethanol, or it crystallises slowly
as a 1:1 solvate with CH2Cl2 (2), in which it is soluble.
/
tion in Mg(H2O)6(TMTH2) [8], M(H2O)8(TMTH2)
Compound 2 has trigonal planar copper (sum anglesꢂ
/
(Mꢂ
/
Ca, Sr) [3] and various barium derivatives which
359.988) bonded to the heterocycle via nitrogen [Cu(1)ꢁ
/
˚
N(1) 2.019(2) A] while the remaining two nitrogens are
protonated (Fig. 3). The ligand thus exists in its thione
embrace S, N and O-donors [3,8]. Li(HMPA)2(TMTH2)
is monomeric with a four-coordinate lithium, attached
to the nitrogen of the heterocycle (thione form) [6].
The lattice structure of 1 is a self-assembled supra-
molecular achitecture made up of alternating layers of
[TMTH2]ꢃ and hydrated cations (Fig. 2a), which is
typical of s-block complexes containing TMT [3,8]. Also
common with these structures is a complex pattern of
form as with 1, with similar Cꢀ
1.677(2), S(2)ꢁC(2) 1.662(2), S(3)ꢁ
NꢁH units are involved in Cꢀ
/
S distances [S(1)ꢁ
/
C(1)
˚
C(3) 1.653(2) A]. The
/
/
/
/
SÁ Á ÁHꢁ
/
Nꢁ hydrogen
/
bonding leading to self-assembly into dimeric supramo-
lecules. The dimer is formed by hydrogen bonds
˚
S(1): 2.401 A] which
involving N(3)ꢁ
/
H(3)Á Á ÁS(1) [H(3)ꢁ
/
generates an eight-membered ring, graph set [
R22(8)]
/
hydrogen bonds (Fig. 2b; Table 2). The two Nꢁ
hydrogen bond to sulphur both to generate eight-
membered (SCNH)2 rings, graph set [
R22(8)]; and link
/H units
(Fig. 4), and which is also a component of the anionic
ribbons in 1.
The hydrogen associated with N(2) forms very weak
/
the [C3N3S3H2]ꢃ ions into ribbons. Rather surprisingly,
it is the sulphurs which engage in coordination to
sodium [S(1), S(3)] that are involved in these hydrogen
bonds. A dimeric sub-unit of these ribbons appears in
the structure of 2 (Fig. 4). The water based on O(1)
hydrogen bonds as a donor to the remaining sulphur
[S(2)] and H2O(2), while H2O(2) acts as a hydrogen
bond donor to the anionic nitrogen [N(3)] and H2O(3A).
The role of O(3)/O(3A) is less clear as the disorder made
it impossible to locate the associated hydrogen atoms,
hydrogen bonds with the disordered dichloromethane
˚
Cl(2B): 3.010 A] but
solvent [(H(2)ꢁ
/
Cl(2A): 2.949; H(2)ꢁ
/
these interactions effectively cap the two extremes of the
dimer. Nevertheless, this dimer is clearly related to the
ribbons of hydrogen-bonded [C3N3S3H2]ꢃ anions visi-
ble in the structure of 1 (Fig. 2b).
The only compound directly comparable with 2 is
[C3N3S3H2Au(PPh3)3](DMF) [14] though in this species
the soft gold is S-bonded to the ligand which is in its
thiol form (Ia). Divalent metal complexes (C3N3S3-
H2)2M have also been prepared but lack structural
but the closest lattice contacts to O(3) are other water
˚
molecules [O(3)ꢁ
/
O(1): 3.190; O(3)ꢁO(3?): 3.067 A].
/
Attempts to utilise 1 as a precursor for other partially-
metallated derivatives of [C3N3S3H2]ꢃ proved only
moderately successful. From the reaction of 1 with
(Ph3P)4Cu(OAc) we have succeeded in isolating
characterisation in the cases where MꢂCu, Co [18]
/
while for the Group 2 metals such complexes are
largely ionic, as described above [3,8]. The structures
of the nickel compounds [Ni(bapen)(C3N3S3H)]×
/2H2O

M.F. Mahon et al. / Inorganica Chimica Acta 348 (2003) 75ꢁ
/
81
79
Fig. 2. The lattice structure of 1 showing (a) the alternating layers of hydrated cations and [TMTH2]ꢃ anions and (b) a stereo view of the cell in
which hydrogen bonds involving water molecules can be seen.
Table 2
Hydrogen bonding in 1
Dꢁ/H
A
d(Dꢁ
/
H)
d(Hꢁ/A)
d(DÁ Á ÁA)
ꢂDꢁ
/
HÁ Á ÁA
Symmetry
N1ꢁ
/
H1
S3
S1
0.880
0.880
0.896
0.894
0.879
0.885
2.409
2.468
2.449
1.937
2.250
1.934
3.266
3.326
3.323
2.826
2.916
2.809
164.9
165.1
165.3
172.4
132.4
169.6
ꢃ
/
xꢀ
xꢀ1/2, y-1/2, ꢃ
xꢀ1/2, y-1/2, ꢃzꢀ1
/
1/2, yꢀ
/
1/2, ꢃ
/
zꢀ1
/
/
N2ꢁ
O1ꢁ
O1ꢁ
O2ꢁ
O2ꢁ
/H2
ꢃ
/
/
/
zꢀ1
/
H1A
H1B
H2A
H2B
S2
ꢃ/
/
/
/
/
O2
O3A
N3
/
ꢃ
/
xꢀ
/
1, ꢃ
/
y, ꢃz
/
/
ꢃ
/
x, ꢃ
/
y, ꢃ
/
z
(bapenꢂ
[28], [Ni(taa)(C3N3S3H)] (taaꢂ
[29] [Ni(pmdien)(C3N3S3H)(H2O)] (pmdienꢂ
N?,N?,Nƒ-pentamethyldiethylenetriamine) [15], and
[Ni(dpta)(C3N3S3H)]×H2O (dptaꢂdipropylenetria-
mine) [30] have also been reported.
The reaction of 1 with (Ph3P)2NiCl2 afforded a
brownꢁblack product analysing most closely to
[C3N3S3H2][(PPh3)2NiCl]×0.5CH2Cl2 (3). Unfortu-
/
N,N?-bis(3-aminopropyl)ethylenediamine)
tris(2-aminoethylamine)
N,N,
gave a yellow powder. The product was extracted into
hexane (50 ml) and crystallised at low temperature to
afford C3N3S3(SnMe3)3 [17] as a colourless crystalline
solid, while the hexane insoluble material proved to be
C3N3S3H3.
/
/
/
/
/
/
5. Conclusions
nately, we have been unable to grow crystals of this
compound to authenticate its composition.
However, when 1 was reacted with (Ph3P)AuCl the
C3N3S3H2Na (1) has been isolated as its trihydrate
and has proved moderately successful in allowing other
partially-metallated derivatives such as C3N3H2Cu-
only product isolated was C3N3S3[(Ph3P)Au]3×
/
2CH2Cl2
(4). The IR spectrum or 4 lacks the bands in the 1550ꢁ
/
(PPh3)2 and [C3N3S3H2][(PPh3)2NiCl]×/0.5CH2Cl2 to be
1500 cmꢃ1 region characteristic of the [C3N3S3H2]ꢃ
group and shows a strong band at approximately 850
cmꢃ1 typical of a fully substituted [C3N3S3]3ꢃ moiety.
synthesised. However, such systems are often in equili-
brium with fully-metallated species and C3N3S3-
[(Ph3P)Au]3×/2CH2Cl2 and C3N3S3(SnMe3)3 are the key
Similarly, after a methanol solution of C3N3S3H2Na×
/
products isolated in reactions of 1 with (Ph3P)AuCl and
Me3SnCl. Similarly, we have so far been unable to
isolate C3N3S3HNa2.
3H2O and Me3SnCl (1:1) was stirred at room tempera-
ture for 2 h, slow evaporation of the resulting solution

80
M.F. Mahon et al. / Inorganica Chimica Acta 348 (2003) 75ꢁ81
/
Fig. 3. The structure of 2 showing the atomic labelling. Thermal ellipsoids are at the 30% probability level. Selected metrical data: Cu(1)ꢁ
2.019(2), Cu(1)ꢁP(1) 2.2318(5), Cu(1)ꢁP(2) 2.2526(5), S(1)ꢁC(1) 1.677(2), S(2)ꢁC(2) 1.662(2), S(3)ꢁC(3) 1.653(2), N(1)ꢁC(1) 1.347(2), N(1)ꢁ
1.348(3), N(2)ꢁC(2) 1.384(3), N(2)ꢁC(3) 1.362(3), N(3)ꢁC(1) 1.369(2), N(3)ꢁC(3) 1.359(2) A; N(1)ꢁCu(1)ꢁP(1) 121.28(5), N(1)ꢁCu(1)ꢁ
111.06(5), P(1)ꢁCu(1)ꢁP(2) 127.64(2)8.
/
N(1)
C(2)
P(2)
/
/
/
/
/
/
/
˚
/
/
/
/
/
/
/
/
/
/
Fig. 4. The hydrogen-bonded dimer of 2; phenyl groups attached to phosphorus and the CH2Cl2 solvent molecules have been omitted for clarity.
6. Supplementary material
(fax:
ac.uk or www: http://www.ccdc.cam.ac.uk).
ꢀ44-1223-336-033; e-mail: deposit@ccdc.cam.
/
Crystallographic data for structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC Nos. 189198 and 198199, com-
pounds 1 and 2, respectively. Copies of this information
can be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
Acknowledgements
We wish to thank NATO and the Royal Society for a
Fellowship (to M.M.V.) and NATO for a Collaborative

M.F. Mahon et al. / Inorganica Chimica Acta 348 (2003) 75ꢁ
/
81
81
[14] Y. Zhao, W. Su, R. Cao, M. Hong, Acta Crystallogr., C 56 (2000)
e331.
Research Grant (to K.C.M. and I.H.). JREI/EPSRC are
also thanked for funding the purchase of the diffract-
ometer.
[15] P. Kopel, Z. Travnicek, L. Kvitek, M. Biler, M. Pavlicek, Z.
Sindelar, J. Marek, Trans. Met. Chem. 26 (2001) 282.
[16] F. Cecconi, C.A. Ghilardi, S. Midollini, A. Orlandini, J.
Organomet. Chem. 645 (2002) 101.
[17] I. Haiduc, M.F. Mahon, K.C. Molloy, M.M. Venter, J. Organo-
met. Chem. 627 (2001) 6.
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