Structural manipulation of hydrogen bond networks using sulfonated phosphane ligands and their complexes: Competition and interplay between strong and weak hydrogen bonds

Article abstract of DOI:10.1002/ejic.200390186

Using the sulfonated phosphane [PPh₂(C₆H₄-m-SO₃)]^-, L^-, we have demonstrated that metal centres can readily be incorporated into guanidinium sulfonate (GS) hydrogen-bonded networks, and tha

Full text of DOI:10.1002/ejic.200390186

FULL PAPER
Structural Manipulation of Hydrogen Bond Networks Using Sulfonated
Phosphane Ligands and Their Complexes: Competition and Interplay Between
Strong and Weak Hydrogen Bonds
Andrew D. Burrows,*[a] Ross W. Harrington,[a] Mary F. Mahon,[a] and Simon J. Teat[b]
Keywords: Crystal engineering / Phosphane ligands / Hydrogen bonds / X-ray crystal structures
Using the sulfonated phosphane [PPh2(C6H4-m-SO3)]−, L−,
we have demonstrated that metal centres can readily be in-
bonding motifs to be formed. The regular GS hydrogen
bonding patterns can also be disrupted by using an anion
corporated into guanidinium sulfonate (GS) hydrogen-bon- containing two sulfonate groups such as that in
ded networks, and that the increase in steric bulk on going [C(NH2)3]2{cis-[PdCl2(L)2]} (5). In this case the incorporation
from [C(NH2)3][L] (1) to [C(NH2)3][AuCl(L)] (2) leads to a flat-
tening of the GS sheets. The crystal structures of
[C(NH2)3][LS] 3 and [C(NH2)3][LSe] 4 (LS− = [SPPh2(C6H4-m-
SO3)]−, LSe− = [SePPh2(C6H4-m-SO3)]−) reveal disorder in
both the sulfonate groups and the guanidinium cations,
which is a consequence of pseudo-sixfold phenyl embraces
between the anions. These interactions, identical to those ob-
served in Ph3PS and Ph3PSe, position the sulfonate groups
too close together for regular quasihexagonal hydrogen
of two sulfonate groups from each anion into the same hydro-
gen-bonded sheet also serves to constrain the distance be-
tween the sulfur atoms to a value incommensurate with that
enabling a guanidinium cation to hydrogen bond to both
groups. In this case irregular GS sheets are formed involving
fewer N−H···O hydrogen bonds than in 1 and 2.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
tures incorporating disulfonates can be used to include
many guest molecules.[5] In this paper we show how mono-
sulfonated triphenylphosphane [PPh2(C6H4-m-SO3)]Ϫ, LϪ,
a ligand initially prepared for biphasic catalysis,[6] can be
incorporated into GS arrays, therefore providing a means
of introducing metal centres into hydrogen-bonded net-
works in which two dimensions are controlled by the hydro-
The use of intermolecular interactions in the design and
synthesis of solid-state structures — a process often referred
to as crystal engineering — has attracted enormous interest
over the past few years.[1] Previously, we have reported the
use of multiple hydrogen bonds to control the aggregation
of metal complex cations and anions containing comple-
mentary hydrogen bonding groups.[2] The incorporation of
two hydrogen bond donors (D) on each cation face and two
hydrogen bond acceptors (A) on each anion face, giving an
overall DD:AA interaction, ensures that secondary interac-
tions are all favourable, thus enhancing the total energy of
the interaction.
´
gen bonds. A recent communication from Katho and co-
workers[7] using guanidinium to crystallise sulfonated phos-
phanes has prompted us to report our findings.[8] To this
end, the syntheses and crystal structures of [C(NH2)3][L]
(1),
[C(NH2)3][LSe] (4) and [C(NH2)3]2{cis-[PdCl2(L)2]} (5)
are reported (LSϪ ϭ [SPPh2(C6H4-m-SO3)]Ϫ, LSeϪ
[C(NH2)3][AuCl(L)]
(2),
[C(NH2)3][LS]
(3),
ϭ
[SePPh2(C6H4-m-SO3)]Ϫ). Analysis of the structures reveals
that predetermination of the relative positions of the sulfon-
ate groups, either through interactions between the triphen-
ylphosphane groups or through coordination of two phos-
phane ligands to a metal centre, can lead either to disrup-
tion of the quasihexagonal hydrogen bonding motif or to
disorder in the GS sheets.
The guanidinium sulfonate (GS) system is another case
in which the cations and anions are linked together by pairs
of hydrogen bonds in the DD:AA arrangement, though,
since both cations and anions contain three hydrogen bond-
ing faces, the hydrogen bond interactions in this system lead
to quasihexagonal arrays and the formation of infinite two-
dimensional sheets.[3,4] These GS sheets are particularly ro-
bust to changes in the steric and electronic properties of the
sulfonate substituents, and bilayer or pillared-brick struc-
Results and Discussion
[a]
Department of Chemistry, University of Bath,
Claverton Down, Bath BA2 7AY, UK
E-mail: a.d.burrows@bath.ac.uk
Metathesis of Na[L] with guanidinium chloride in meth-
anol gave colourless crystals of [C(NH2)3][L] (1) suitable for
analysis by X-ray crystallography. The asymmetric unit of
[b]
CLRC Daresbury Laboratory,
Daresbury, Warrington WA4 4AD, UK
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Eur. J. Inorg. Chem. 2003, 1433Ϫ1439  2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/03/0407Ϫ1433 $ 20.00ϩ.50/0

A. D. Burrows, R. W. Harrington, M. F. Mahon, S. J. Teat
FULL PAPER
1 showed the presence of two independent guanidinium cat- the inter-sheet space. The major interaction between these
ions and two independent triphenylphosphane sulfonate an- groups involves pairs of [L]Ϫ anions, based on P(1) and P(2)
ions. Hydrogen bond interactions between the cations and
anions lead to the formation of the anticipated quasihexa-
gonal GS arrays [Figure 1 (top)], despite the steric bulk of
the triphenylphosphane group. A single-layer sheet struc-
ture is adopted, with PPh3 groups located on both sides of
the GS sheets. The sheets are corrugated, with a ‘‘hinge’’
between hydrogen-bonded ribbons [Figure 1 (bottom)], and
this is reflected in an inter-ribbon angle of 103°, based on
the angle between guanidinium planes in neighbouring rib-
bons. Similar distortions to GS sheets have been observed
previously,[3] and occur as a means of minimising void
space within the structure.
in neighbouring sheets, which adopt sixfold phenyl em-
braces (6PEs).[9] Two CϪH···O interactions are also evident
˚
[C(8)···O(1)
3.548(10),
H(8)···O(1)
2.66(1)
A,
C(8)ϪH(8)···O(1) 160.8(5)°; and C(36)···O(6) 3.639(10),
˚
H(36)···O(6) 2.75(1) A, C(36)ϪH(36)···O(6) 161.0(5)°].
The gold complex Na[AuCl(L)] was formed from the re-
action of [AuCl(SC4H8)] and Na[L] in acetone, and recrys-
tallised from methanol. Metathesis of Na[AuCl(L)] with gu-
anidinium chloride in methanol gave colourless crystals of
[C(NH2)3][AuCl(L)] (2) which were suitable for X-ray crys-
tallography. The structural analysis of 2 showed the pres-
ence of one guanidinium cation and one [AuCl(L)]Ϫ anion
in the asymmetric unit. As in 1, the sulfonate groups form
quasihexagonal hydrogen-bonded arrays through NϪH···O
interactions with guanidinium cations, and these lead to the
formation of GS sheets [Figure 2 (top)]. Although the inter-
actions within the sheets are similar to those in 1, there are
two main differences. Firstly, the presence of the AuCl
group coordinated to each phosphane serves to flatten the
sheets, and the inter-ribbon angle in 2 is increased to 161°
[Figure 2 (bottom)]. In other GS sheet structures, increase
in steric bulk or inclusion of guest molecules can have the
effect of reducing the degree of distortion from planarity,
hence the AuCl group can be regarded as a ‘‘guest’’ within
the [C(NH2)3][L] lattice, albeit one with a directional coor-
dination binding site. Secondly, the quasihexagonal sheets
are distorted such that the intra-ribbon S···S distance is in-
The single-layer sheet structure ensures that triphenyl-
phosphane groups from neighbouring sheets project into
˚
creased to 8.105 A, equal to the unit cell parameter a. In
simple guanidinium sulfonate structures[3,4] closest S···S dis-
˚
tances within the GS sheets range from 6.57 to 7.77 A. The
distortion of the GS sheets in 2 is also apparent in the
values of the NϪH···O angles.
These distortions are related to the interactions between
the (triphenylphosphane)gold chloride units. Dance and
Scudder have shown[10] the importance of interactions be-
tween multiple phenyl groups in the crystal structures of
PPh3 complexes. In 2, pseudo-sixfold phenyl embraces serve
to link the AuCl(PPh3) units into chains running perpendic-
ular to the direction of the hydrogen-bonded ribbons (Fig-
ure 3). In these pseudo-sixfold phenyl embraces, the AuCl
unit acts in a similar manner to a phenyl group, so that
each embrace involves three phenyl rings on one anion and
two phenyl rings and the AuCl group on the other. These
interactions bring the phosphorus atoms on closest phos-
Figure 1. (top) Quasihexagonal hydrogen-bonded GS sheets in the
˚
˚
phane groups to within 6.49 A of each other, and position
crystal structure of [C(NH2)3][L] (1); hydrogen bond lengths (A)
and angles (°): N(1)···O(1) 2.974, H(1A)···O(1) 2.12,
N(1)ϪH(1A)···O(1) 176; N(1)···O(5) 3.056, H(1B)···O(5) 2.24,
N(1)ϪH(1B)···O(5) 158; N(2)···O(5) 3.010, H(2A)···O(5) 2.16,
N(2)ϪH(2A)···O(5) 170; N(2)···O(2) 3.008, H(2B)···O(2) 2.15,
N(2)ϪH(2B)···O(2) 176; N(3)···O(4) 3.061, H(3A)···O(4) 2.20,
N(3)ϪH(3A)···O(4) 177; N(3)···O(6) 3.038, H(3B)···O(6) 2.20,
N(3)ϪH(3B)···O(6) 165; N(4)···O(3) 3.050, H(4A)···O(3) 2.21,
N(4)ϪH(4A)···O(3) 167; N(4)···O(4) 3.053, H(4B)···O(4) 2.20,
N(4)ϪH(4B)···O(4) 175; N(5)···O(6) 2.981, H(5A)···O(6) 2.12,
N(5)ϪH(5A)···O(6) 174; N(5)···O(3) 3.046, H(5B)···O(3) 2.20,
N(5)ϪH(5B)···O(3) 166; N(6)···O(2) 3.021, H(6A)···O(2) 2.18,
N(6)ϪH(6A)···O(2) 166; N(6)···O(1) 2.981, H(6B)···O(1) 2.13,
N(6)ϪH(6B)···O(1) 171; (bottom) side-on view of one of the GS
sheets in the structure of 1
˚
sulfur atoms from the same sheet at 11.29 A, equal to the
unit cell parameter b, from each other. Pseudo-sixfold
phenyl embraces in which gold-containing groups are in-
volved have been shown to be recurrent structural motifs in
the crystal structures of gold-PPh3 complexes.[11] Au···Au
interactions have previously been exploited as crystal engin-
eering tools in conjunction with hydrogen bond net-
works.[12] However, in the crystal structure of 2 there are no
aurophilic interactions, the shortest Au···Au distance being
˚
7.35 A.
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Eur. J. Inorg. Chem. 2003, 1433Ϫ1439

Structural Manipulation of Hydrogen Bond Networks
FULL PAPER
Figure 2. (top) Quasihexagonal hydrogen-bonded GS sheets in the crystal structure of [C(NH2)3][AuCl(L)] (2); hydrogen bond lengths
˚
(A) and angles (°): N(1)···O(1) 2.988, H(1A)···O(1) 2.16, N(1)ϪH(1A)···O(1) 157; N(1)···O(3) 3.030, H(1B)···O(3) 2.19, N(1)ϪH(1B)···O(3)
160; N(2)···O(2) 3.024, H(2A)···O(2) 2.19, N(2)ϪH(2A)···O(2) 159; N(2)···O(1) 2.907, H(2B)···O(1) 2.03, N(2)ϪH(2B)···O(1) 175;
N(3)···O(3) 2.913, H(3A)···O(3) 2.05, N(3)ϪH(3A)···O(3) 169; N(3)···O(2) 3.049, H(3B)···O(2) 2.23, N(3)ϪH(3B)···O(2) 155; (bottom)
side-on view of one of the GS sheets in the structure of 2
The compounds Na[LS] and Na[LSe] were prepared from the presence of this disorder makes an unambiguous evalu-
the oxidation of Na[L] with elemental sulfur or selenium in ation of the inter-ribbon angle impossible, though estimated
methanol. Metathesis with [C(NH2)3]Cl in methanol gave values of 150° for 3 and 153° for 4 suggest that, as anticip-
colourless crystals of [C(NH2)3][LS] (3) and [C(NH2)3][LSe] ated, the Group 16 atom is less sterically demanding than
(4) respectively. X-ray structural analyses of 3 and 4 showed the AuCl fragment [Figure 4 (bottom)]. The disorder in
that both compounds possess one cation and one anion in these structures can be rationalised by consideration of the
their asymmetric units, and that they are essentially isos- interactions between the triphenylphosphane sulfide (or se-
tructural. Both 3 and 4 are disordered with regard to the lenide) units.
sulfonate oxygen atom positions (1:1 ratio between two sets
In a similar manner to the (triphenylphosphane)gold
of positions) and the guanidinium cations (2:1:1 ratio be- chloride units in 2, the triphenylphosphane sulfides and se-
tween three positions in 3, 50:37:13 between similar posi- lenides form pseudo-sixfold phenyl embraces involving three
tions in 4). Although GS sheets are formed [Figure 4 (top)], phenyl rings on one anion and two phenyl rings and the
Eur. J. Inorg. Chem. 2003, 1433Ϫ1439
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A. D. Burrows, R. W. Harrington, M. F. Mahon, S. J. Teat
FULL PAPER
Figure 3. Pseudo-sixfold phenyl embraces linking the anions into
chains in the crystal structures of [C(NH2)3][AuCl(L)] (2) and
[C(NH2)3][LSe] (4)
Group 16 atom on the other. These embraces lead to the
formation of chains running in the same direction as the
hydrogen-bonded ribbons, which possess closest P···P dis-
˚
˚
tances of 6.17 A for 3 and 6.27 A for 4 (Figure 3). This
chain formation ensures that sulfonate groups within the
˚
same sheet are positioned with S···S distances of 9.27 A for
˚
3 and 9.49 A for 4, in both cases equal to the respective
unit cell parameter b. In addition to these interactions, each
triphenylphosphane sulfide or selenide unit forms a second
pseudo-sixfold phenyl embrace, approximately perpendic-
ular to the first, in this case arising from neighbouring cen-
trosymmetrically related pairs of anions, and involving two
Figure 4. (top) GS sheet formation in [C(NH2)3][LS] (3); for the
guanidinium cations only two of the three positions are shown for
clarity; (bottom) side-on view of one of the GS sheets in the struc-
ture of 3
phenyl rings and the Group 16 atom. This interaction leads trate in the same solvent mix gave several products includ-
˚
˚
to P···P distances of 5.75 A and 5.90 A for 3 and 4, respect- ing small, yellow crystals of [C(NH2)3]2{cis-[PdCl2(L)2]} (5)
ively. Both types of pseudo-sixfold phenyl embrace are also suitable for analysis at the SRS facility. The structural ana-
observed in the crystal structures of Ph3PS[13] and lysis of 5 showed the presence of GS sheets [Figure 5 (top)],
Ph3PSe,[14] and together they serve to dictate the relative with both of the sulfonate groups from each complex anion
positions of the sulfonate groups in 3 and 4. These groups incorporated into the same sheet. The hydrogen bonding
are too close together for the guanidinium cations to form patterns in 5 are less regular than those observed in 1 and
regular hydrogen bonding patterns, and as a consequence 2. Only two of the six independent guanidinium faces are
the cations are disordered. In one of the three orientations, involved in DD:AA interactions. Of the remaining faces,
NϪH groups are directed out of the plane of the GS sheets, two form R12(6) rings with sulfonate oxygen atoms whereas
and form NϪH···S or NϪH···Se hydrogen bonds to the sul- another forms bifurcated NϪH···O hydrogen bonds. The
fide or selenide together with R12(6) rings [N(1B)···S(1) final guanidinium face is not involved in any NϪH···O hy-
˚
3.35(1), H(1B2)···S(1) 2.52(1) A, N(1B)ϪH(1B2)···S(1) drogen bonding, instead forming NϪH···Cl interactions to
157(1)° and N(3B)···S(1) 3.41(1), H(3B1)···S(1) 2.61(1) A, the metal-bound chlorides.[15] The distortions from the
˚
N(3B)ϪH(3B1)···S(1) 151(1)° for 3; N(1B)···Se(1) 3.29(2), regular pattern observed for 1 and 2 are a consequence of
˚
H(1B1)···Se(1) 2.46(2) A, N(1B)ϪH(1B1)···Se(1) 158(1)° the distance constraint imposed by virtue of the two sulfon-
˚
˚
and N(3B)···Se(1) 3.44(3), H(3B2)···Se(1) 2.67(2) A, ate groups arising from the same anion (S···S 9.21 A)
N(3B)ϪH(3B2)···Se(1) 148(2)° for 4].
coupled with the triangular shape of the guanidinium cat-
The complex Na2{cis-[PdCl2(L)2]} was formed from the ion. It is not possible to orientate the cation to enable it to
reaction of [PdCl2(cod)] with Na[L] in acetonitrile/meth- form two NϪH···O hydrogen bonds with both sulfonates as
anol. Metathesis of this sodium salt with guanidinium ni- the groups are too far apart.
1436
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Structural Manipulation of Hydrogen Bond Networks
FULL PAPER
˚
Figure 5. (top) GS sheet formation in [C(NH2)3]2{cis-[PdCl2(L)2] (5); hydrogen bond lengths (A) and angles (°): N(1)···O(1) 2.911,
H(1A)···O(1) 2.06, N(1)ϪH(1A)···O(1) 162; N(1)···O(4) 2.893, H(1B)···O(4) 2.12, N(1)ϪH(1B)···O(4) 146; N(1)···O(6) 3.219, H(1B)···O(6)
2.43, N(1)ϪH(1B)···O(6) 150; N(2)···O(2) 2.902, H(2A)···O(2) 2.04, N(2)ϪH(2A)···O(2) 168; N(2)···Cl(1) 3.253, H(2B)···Cl(1) 2.56,
N(2)ϪH(2B)···Cl(1) 136; N(3)···O(6) 3.140, H(3A)···O(6) 2.32, N(3)ϪH(3A)···O(6) 154; N(3)···O(6) 3.003, H(3A)···O(6) 2.50,
N(3)ϪH(3A)···O(6) 117; N(4)···O(4) 2.810, H(4A)···O(4) 1.94, N(4)ϪH(4A)···O(4) 168; N(4)···O(3) 2.855, H(4B)···O(3) 2.11,
N(4)ϪH(4B)···O(3) 142; N(5)···O(5) 2.923, H(5A)···O(5) 2.05, N(5)ϪH(5A)···O(5) 171; N(5)···O(2) 2.994, H(5B)···O(2) 2.19,
N(5)ϪH(5B)···O(2) 153; N(6)···O(2) 3.079, H(6A)···O(2) 2.30, N(6)ϪH(6A)···O(2) 147; N(6)···O(3) 2.927, H(6B)···O(3) 2.21,
N(6)ϪH(6B)···O(3) 139; (bottom) side-on view of one of the GS sheets in the structure of 5; for clarity only the ipso carbon atoms on
the unfunctionalised phenyl rings are shown
As with compounds 1Ϫ4, the phosphanes are located on positioned too closely to each other, guanidinium cations
either side of the GS sheets [Figure 5 (bottom)]. Parallel are unable to form regular hydrogen bonding patterns, and
fourfold phenyl embraces (P4PEs) link centrosymmetrically disorder in both the cation and the anion sulfonate groups
related pairs of phosphanes based on P(1), and pairs of is observed. In contrast, when the S···S distance is con-
phosphanes based on P(2), and, as in the structures of 2Ϫ4, strained by having two sulfonate groups from the same
these interactions serve to constrain the distances between complex incorporated into the same sheet, significant dis-
sulfonate groups.
tortions from the quasihexagonal array may result.
The structures reported in this paper clearly demonstrate
Taken together, these structural analyses demonstrate
that sulfonated phosphane ligands and their metal com- that supramolecular interactions that are generally consid-
plexes can be incorporated into hydrogen-bonded networks ered weak can compete effectively with strong hydrogen
based on guanidinium sulfonate sheets. This system is suffi- bonds in determining gross structures. Clearly, the disorder
ciently robust to cope with the increased steric bulk that and the distortions observed in the GS networks in 3, 4 and
accompanies inclusion of a coordination centre. The inter- 5 occur with loss of some, but not all, of the stabilisation
actions between phosphane groups Ϫ involving CϪH···π energy. Non-disordered structures in the cases of 3 and 4
interactions and pseudo-sixfold phenyl embraces Ϫ ob- would involve either steric clashes or voids within the struc-
served in the crystal structures of molecules such as Ph3PS ture, both of which are energetically unfavourable. Similarly,
and Ph3PSe can be preserved in their guanidinium sulfonate non-distorted GS sheets in 5 would result in unfavourable
adducts, and these are important in determining the relative bond lengths and/or angles within the anions, which would
positions of the sulfonate groups. Although the GS motif is also be energetically less favourable than the loss of hydro-
flexible to a range of S···S distances, if the sulfonates are gen bonding in the distorted GS network.
Eur. J. Inorg. Chem. 2003, 1433Ϫ1439
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A. D. Burrows, R. W. Harrington, M. F. Mahon, S. J. Teat
FULL PAPER
crude yellow-orange solid recrystallised from methanol. Yield
0.235 g (74%). 31P NMR (CD3OD): δ ϭ 25.6 (s) ppm. IR: ν(SO3)
1641s cmϪ1 (br), 1536s.
We are currently exploring the use of bis(phosphane)
complexes containing unsaturated metal centres to bridge
between GS sheets with a view to exploring the reversible
coordination of small molecules.
Synthesis of [C(NH2)3][L] (1): Na[L] (0.100 g, 0.27 mmol) and
[C(NH2)3]Cl (0.026 g, 0.27 mmol) were dissolved in methanol (10
cm3), and the solvent allowed to slowly evaporate. After two weeks
colourless crystals were harvested. Yield 0.077 g (70%).
C19H20N3O3PS (401.4): calcd. C 56.9, H 5.02, N 10.5; found C
57.2, H 4.99, N 10.0. IR: ν(NH) 3380s cmϪ1 (br), 3195s (br);
ν(SO3)/δ(NH2) 1684s, 1571s, 1431m.
Experimental Section
Synthesis of metal complexes of [L]Ϫ were routinely carried out
using Schlenk-line techniques under pure dry dinitrogen using di-
oxygen-free solvents. Metathesis reactions were carried out with no
special precautions to exclude air. Microanalyses (C, H and N)
were carried out by Mr. Alan Carver (University of Bath Microan-
alytical Service). Infrared spectra were recorded on a Nicolet Nexus
FT-IR spectrometer as KBr pellets. The compounds Na[L][16] and
[AuCl(SC4H8)][17] was prepared according to the literature
methods.
Synthesis of [C(NH2)3][AuCl(L)] (2): Na[AuCl(L)] (0.100 g,
0.17 mmol) and [C(NH2)3]Cl (0.016 g, 0.17 mmol) were dissolved
in methanol (10 cm3), and the solvent allowed to slowly evaporate.
After one week colourless crystals were harvested. Yield 0.085 g
(80%). C19H20AuClN3O3PS (633.8): calcd. C 36.0, H 3.18, N 6.63;
found C 36.0, H 3.16, N 6.44. IR: ν(NH) 3400s cmϪ1 (br), 3273s,
3202s; ν(SO3)/δ(NH2) 1684s, 1569m, 1479m.
Synthesis of Na[AuCl(L)]: Na[L] (0.182 g, 0.50 mmol), dissolved in
acetone (10 cm3) was added to a solution of [AuCl(SC4H8)]
(0.158 g, 0.50 mmol) in acetone (10 cm3). The resultant solution
was stirred for 2 h, filtered, and the solvent removed in vacuo.
Recrystallisation from methanol gave a colourless crystalline mat-
erial. Yield 0.188 g (64%). 31P NMR (CD3OD): δ ϭ 46.0 (s) ppm.
IR: ν(SO3) 1670s cmϪ1 (br).
Synthesis of [C(NH2)3][LS] (3): Na[LS] (0.100 g, 0.25 mmol) and
[C(NH2)3]Cl (0.024 g, 0.23 mmol) were dissolved in methanol (10
cm3), and the solvent allowed to slowly evaporate. After two weeks
colourless crystals were harvested. Yield 0.085 g (80%).
C19H20N3O3PS2 (433.5): calcd. C 52.2, H 4.65, N 9.70; found C
52.6, H 4.51, N 9.60. IR: ν(NH) 3388s cmϪ1 (br), 3208s (br);
ν(SO3)/δ(NH2) 1664s, 1577s, 1431s.
Synthesis of Na[AuCl(LS)]: An excess of elemental sulfur was ad-
ded to a solution of Na[L] (0.200 g, 0.55 mmol) in wet methanol
(30 cm3) and the mixture stirred vigorously for 3 h. Unreacted sul-
fur was removed by filtration, then the solvent was removed in
vacuo and the crude solid recrystallised from methanol. Yield
0.191 g (88%). 31P NMR (CD3OD): δ ϭ 46.3 (s) ppm.
Crystals of [C(NH2)3][LSe] 4 were prepared in a similar manner
from Na[LSe] and [C(NH2)3]Cl.
Synthesis of [C(NH2)3]2{cis-[PdCl2(L)2]} (5): Na2{cis-[PdCl2(L)2]}
(0.050 g, 0.045 mmol) in methanol (5 cm3) was added to
[C(NH2)3]NO3 (0.013 g, 0.10 mmol) in acetonitrile (5 cm3). The
solvent was allowed to slowly evaporate, and after two weeks small
yellow crystals were obtained.
Na[AuCl(LSe)] was prepared in an analogous manner using ele-
mental selenium.
Crystallography
Synthesis of Na2{cis-[PdCl2(L)2]}: A solution of Na[L] (0.276 g,
0.70 mmol) in methanol (25 cm3) was added dropwise with stirring Single crystals of compounds 1Ϫ5 were prepared by the methods
to a solution of [PdCl2(cod)] (0.100 g, 0.35 mmol) in acetonitrile
above. Data were collected using a EnrafϪNonius CAD4 auto-
(30 cm3) giving a slight darkening of colour. Stirring was continued matic four-circle diffractometer for 1 and a Nonius Kappa CCD
for 45 min, and then the solvent was removed in vacuo and the
diffractometer for 2, 3 and 4. Crystals of 5 were too small to ana-
Table 1. Crystal data for compounds 1Ϫ5
Complex
1
2
3
4
5
Empirical formula
M
C19H20N3O3PS
401.41
296(2)
Orthorhombic
Pca21
19.4240(10)
7.969(5)
C19H20AuClN3O3PS
633.83
170(2)
Monoclinic
P21
8.1050(4)
11.2910(5)
12.1120(6)
C19H20N3O3PS2
433.47
150(2)
Monoclinic
P21/n
14.3160(4)
9.2710(3)
16.1200(7)
C19H20N3O3PSSe
480.37
150(2)
Monoclinic
P21/n
14.4130(2)
9.49200(10)
16.0910(2)
C38H40Cl2N6O6P2PdS2
980.12
150(2)
Temperature/K
Crystal system
Space group
Triclinic
¯
P1
˚
a (A)
10.145(2)
12.763(3)
17.019(4)
85.125(9)
84.163(9)
79.192(9)
2148.4(9)
2
˚
b (A)
˚
c (A)
25.621(4)
α (°)
β (°)
γ (°)
98.475(3)
108.1670(10)
107.9850(10)
3
˚
V (A )
3966(3)
8
0.268
1096.31(9)
2
7.025
2032.85(12)
4
0.366
2093.81(4)
4
1.994
Z
µ(Mo-Kα) (mmϪ1
)
0.780
Reflections collected
Independent reflections
R(int)
R1, wR2 [I Ͼ 2σ(I)]
R indices (all data)
3733
3571
0.0089
0.0541, 0.1357
0.0788, 0.1486
13383
4567
0.0495
0.0345, 0.0762
0.0374, 0.0773
29789
3543
0.0931
0.0482, 0.1071
0.0809, 0.1230
19837
3698
0.0782
0.0410, 0.0898
0.0787, 0.1056
11184
7062
0.0322
0.0578, 0.1294
0.0706, 0.1352
1438
Eur. J. Inorg. Chem. 2003, 1433Ϫ1439

Structural Manipulation of Hydrogen Bond Networks
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2 and 5 but in the final least-squares cycles they were included at
calculated positions throughout.
CCDC-191297 (1), -191298 (2), -191299 (3), -191300 (4) and
-191301 (5) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (internat.) ϩ44-1223/336-033; E-mail:
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Eur. J. Inorg. Chem. 2003, 1433Ϫ1439
1439