P4S3 and P,P′ or N,N′ donors as competitive building blocks in copper(I) coordination polymers

Article abstract of DOI:10.1002/ejic.201100444

The synthesis and characterization of hybrid polymers combining organic P,P′ (dppe) or N,N′ (pyrazine) ligands and inorganic donors (P ₄S₃) as cross-linkers between copper(I) halide aggregates is described. As a simple model system the reaction of a mixture of P ₄S₃, PEt₃, and CuX (X = Cl, Br, I) was studied. According to X-ray diffraction analysis, pseudotetrahedral monomers [CuX(PEt₃)₂(P₄S₃)] (1-3) were formed, in which P₄S₃ coordinates through the apical phosphorus atom. Layering a mixture of P₄S₃, Ph ₂PCH₂CH₂PPh₂ (dppe), and toluene with CuCl in MeCN under diffusion conditions gives 1D-[CuCl(dppe)(MeCN)] (6), which contains (Cu₂Cl₂)₂(μ-dppe)₂ clusters linked by another dppe ligand. The analogous reaction with CuI gives 1D-[CuI(P₄S₃)(dppe)] (7), which is built up of alternating trans-(Cu₂I₂)(P₄S₃)₂ units and dppe linkers. Hybrid polymers 2D-[CuX(P₄S ₃)(dppe)] [X = Br (8), I (9)] are formed if CH₂Cl ₂ is used instead of toluene. The 2D structures of 8 and 9 may be derived from that of 7 by connecting neighboring (CuX)(dppe) strands with pairs of inversely coordinated P₄S₃ cages. Replacement of dppe by pyrazine (pyz) yields 3D-[(CuCl)₄(P₄S₃) ₂(pyz)] (10) and 3D-[(CuBr)₃(P₄S ₃)(pyz)] (12), respectively. The structure of 10 comprises a 3D network composed of alternating, linked 2D-[(CuCl)₂(P ₄S₃)] and 2D-[CuCl(pyz)] layers. The structure of 12 contains cradles built from opposing (CuBr)₆ rings and pairwise pyz and P₄S₃ bridges. These cradles are organized into a 3D framework by condensation of the (CuBr)₆ rings, and the layers formed are linked by additional pyz molecules. The resulting voids are occupied by toluene molecules. The behavior of P₄S₃ and P,P′ or N,N′ ligands as competitive building blocks is also expressed by the formation of binary P₄S₃/CuX or pyz/CuX polymers.

Full text of DOI:10.1002/ejic.201100444

FULL PAPER
DOI: 10.1002/ejic.201100444
P4S3 and P,PЈ or N,NЈ Donors as Competitive Building Blocks in Copper(I)
Coordination Polymers
Andreas Biegerl,[a] Dmitry Piryazev,[b,c] Manfred Scheer,[a] Joachim Wachter,*[a]
Alexander Virovets,[c] and Manfred Zabel[a]
Keywords: Coordination polymers / Copper / Phosphorus / Sulfur / N ligands
The synthesis and characterization of hybrid polymers com- structures of 8 and 9 may be derived from that of 7 by con-
bining organic P,PЈ (dppe) or N,NЈ (pyrazine) ligands and in-
organic donors (P4S3) as cross-linkers between copper(I) ha-
lide aggregates is described. As a simple model system the
reaction of a mixture of P4S3, PEt3, and CuX (X = Cl, Br, I)
was studied. According to X-ray diffraction analysis, pseudo-
tetrahedral monomers [CuX(PEt3)2(P4S3)] (1–3) were formed,
in which P4S3 coordinates through the apical phosphorus
atom. Layering a mixture of P4S3, Ph2PCH2CH2PPh2 (dppe),
and toluene with CuCl in MeCN under diffusion conditions
gives 1D-[CuCl(dppe)(MeCN)] (6), which contains (Cu2Cl2)2-
(μ-dppe)2 clusters linked by another dppe ligand. The analo-
gous reaction with CuI gives 1D-[CuI(P4S3)(dppe)] (7), which
is built up of alternating trans-(Cu2I2)(P4S3)2 units and dppe
linkers. Hybrid polymers 2D-[CuX(P4S3)(dppe)] [X = Br (8), I
(9)] are formed if CH2Cl2 is used instead of toluene. The 2D
necting neighboring (CuX)(dppe) strands with pairs of in-
versely coordinated P4S3 cages. Replacement of dppe by pyr-
azine (pyz) yields 3D-[(CuCl)4(P4S3)2(pyz)] (10) and 3D-
[(CuBr)3(P4S3)(pyz)] (12), respectively. The structure of 10
comprises a 3D network composed of alternating, linked 2D-
[(CuCl)2(P4S3)] and 2D-[CuCl(pyz)] layers. The structure of
12 contains cradles built from opposing (CuBr)6 rings and
pairwise pyz and P4S3 bridges. These cradles are organized
into a 3D framework by condensation of the (CuBr)6 rings,
and the layers formed are linked by additional pyz mole-
cules. The resulting voids are occupied by toluene molecules.
The behavior of P4S3 and P,PЈ or N,NЈ ligands as competitive
building blocks is also expressed by the formation of binary
P4S3/CuX or pyz/CuX polymers.
The supramolecular chemistry of multidentate ligands
other than O and N donors is less developed.[10] Initial re-
sults obtained with bidentate bis(diphenylphosphane)-
alkanes and AgI or CuI compounds demonstrate the great
structural flexibility of polymers with P,PЈ donors.[11] Re-
cent developments focus on the construction of organic–
inorganic hybrid materials from bifunctional P,N or S,N
ligands.[12,13] Inorganic polymers of a completely different
nature have been developed using the multifunctional P,Q
building block P4Q3 (Q = S,[14,15] Se[16]).
The combination of organic and inorganic donors as
cross-linking ligands with copper halide aggregates has not
yet been explored. In this context it is worthwhile to explore
the potential of P4S3 as building block in MOFs. We report
the stepwise formation of organic–inorganic hybrid poly-
mers from mono- or bidentate phosphanes and P4S3 with
CuX (X = Cl, Br, I) in competitive reactions and on the
effects observed when replacing the conformational flexible
dppe ligand with the rigid pyz linker.
Introduction
Coordination polymers are a class of intensively studied
solid-state materials with infinite structures constructed
from metal ions and organic spacer ligands.[1] The combina-
tion of copper halide aggregates as inorganic connectors
with bridging ligands by crystal engineering methods pro-
duces a wide range of discrete oligomers and 1-, 2-, and 3D
architectures.[2] A particular role is devoted to bifunctional
organic ligands, which, as secondary building units, offer
new perspectives for the development of metal–organic
frameworks (MOFs).[3] Common linkers in MOFs are poly-
carboxylates,[4] multidentate N-donor ligands, and combi-
nations of both.[3] The tuneable flexibility of the coordina-
tion geometry and conformation make MOFs interesting
for numerous applications, e.g. gas adsorption,[5] catalytic
activity,[6] luminescent[7] and magnetic[8] materials, and tem-
plates for hosting nanoparticles.[9]
[a] Institut für Anorganische Chemie der Universität Regensburg,
93040 Regensburg, Germany
Results and Discussion
Fax: +49-941-943-4439
E-mail: Joachim.Wachter@chemie.uni-regensburg.de
[b] Nikolaev Institute of Inorganic Chemistry SB RAS,
Ak. Lavrentiev prosp. 3, Novosibirsk 630090, Russia
[c] Novosibirsk State University,
The System P4S3, PR3, and CuX (X = Cl, Br, I)
The reaction of a mixture of CuX (X = Cl, Br, I), trieth-
ylphosphane, and P4S3 (molar ratio 1:2.5:1) in acetonitrile/
Pirogova str. 2, Novosibirsk 630090, Russia
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Competitive Building Blocks in Copper(I) Coordination Polymers
toluene at room temperature gave an orange-yellow solu-
tion, which after concentration and cooling gave colorless
needles of 1–3 in 80% yield. The composition
[CuX(P4S3)(PEt3)2] was confirmed by elemental analysis
and X-ray crystallography.
Reaction of PMe(iPr)2 with CuCl or PCy3 (Cy = C6H11)
with CuI under analogous conditions selectively gave
[CuCl(P4S3){PMe(iPr)2}2] (4) and [CuI(P4S3){PCy3}2] (5),
respectively [Equation (1)]. The homogeneity and composi-
tion of 4 and 5 were deduced from their 31P NMR spectra
(Table 1). Comparing the chemical shifts of 1–5 with those
of the free P4S3 cage, the apical P atoms are more shifted
towards low field than the basal atoms, probably as a conse-
quence of copper coordination. It is striking that the hal-
ogens do not seem to contribute significantly to the shifts
in 1–3. 31P31P-coupling between the trialkylphosphanes and
P4S3 was not observed. A broadening of these signals may
be explained by the quadrupole moments of the 63Cu and
65Cu nuclei.
Figure 1. Molecular structure of [CuX(P4S3)(PEt3)2] [X = Cl (1),
Br (2), I (3)]. The disorder of the ethyl groups is not shown (see
text).
Table 2. Selected distances [Å] for 1–3.
1
2
3
S1–P1
S1–P2
S2–P1
S2–P3
S3–P1
S3–P4
P2–P4
P2–P3
P3–P4
Cu1–X1
Cu1–P1
Cu1–P5
Cu1–P6
2.096(2)
2.103(2)
2.095(2)
2.103(2)
2.103(2)
2.103(2)
2.238(2)
2.236(2)
2.249(2)
2.331(2)
2.266(2)
2.276(2)
2.275(2)
2.097(2)
2.099(2)
2.101(2)
2.097(2)
2.102(2)
2.096(2)
2.240(2)
2.248(2)
2.241(2)
2.479(1)
2.267(2)
2.267(2)
2.273(2)
2.102(2)
2.102(2)
2.104(2)
2.103(2)
2.106(2)
2.105(2)
2.245(2)
2.248(2)
2.246(2)
2.641(1)
2.260(2)
2.266(2)
2.272(2)
(1)
Table 1. 31P NMR chemical shifts (δ in ppm, C6D6) and coupling
2
constants JP,P [Hz] of 1–5 and P4S3.
Papical
δ
Pbasal
δ
PR3
2JP,P
2JP,P
Coordination Polymers with dppe
P4S3
65.0
85.6
89.2
89.3
96.6
94.1
71
62
61
62
57
57
–126.0
–115.9
–115.0
–115.9
–109.8
–111.8
71
62
61
62
57
57
1
2
3
4
5
–11.0
–11.9
–14.6
–1.1
Layering of a mixture of P4S3, dppe, and toluene with a
solution of CuCl in acetonitrile gave colorless rods of 1D-
[CuCl(dppe)(CH3CN)] (6) along with crystals that could
not be identified. The composition of 6 was determined by
X-ray diffraction analysis. An analogous experiment, but
with a threefold excess of copper(I) iodide gave bright yel-
low platelets of 7 after 5 d [Equation (2)]. These were ana-
lyzed with 31P magic angle spinning (MAS) NMR spec-
troscopy and X-ray diffraction to give the composition
[CuI(P4S3)(dppe)].
12.6
Compound 1 crystallizes in the acentric orthorhombic
space group P212121. The central feature of the molecule is
a tetrahedral copper atom bearing a P4S3, chloride and two
triethylphosphane ligands. The cage is coordinated through
its apical P atom (Figure 1). The geometry of the cage does
not change significantly on coordination (Table 2). In the
crystal structure of 1 there are disordered ethyl groups with
an occupation factor of 70:30. In isostructural 2 and 3 only
one phosphane ligand contains disordered ethyl groups
with a ratio of 50:50. A comparison of the distances in 1–
3, particularly the P–Cu and the P–S bonds, does not indi-
cate any significant influence of the halogen atoms.
In all complexes the basal P atoms of P4S3 should be
accessible for attack by excess copper(I) halide. In a typical
experiment diffusion of a solution of CuI in CH3CN into
(2)
The diffusion reaction of an equimolar mixture of P4S3
and dppe in CH2Cl2 with CuX in acetonitrile gave yellow
[17]
the solution of 3 in toluene gave crystals of (CuI)3P4S3
and [(CuI)4(PEt3)4].[18] A related reaction of 3 with CuCl prisms of 2D-[(CuX)2(P4S3)(dppe)] [X = Br (8), I(9)] [Equa-
gave (CuCl)7(P4S3)3.[17] This means that in MeCN new bi- tion (2)]. As by-products bright yellow, fine needles of
[19]
[17]
nary compounds are formed after dissociation of 3 into the (CuBr)7(P4S3)3 and (CuI)P4S3 were identified.
ligands and their subsequent reaction with the correspond-
ing copper halide.
¯
Compound 6 crystallizes in the triclinic space group P1.
The structure is characterized by two planar Cu2Cl2 rings
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as part of (Cu2Cl2)2(μ-dppe)2 clusters, which are linked by
The 31P MAS NMR spectrum of 7 is shown in Figure 4.
another dppe bridge. The resulting 1D ribbon (Figure 2) The multiplet at δ = 96.7 ppm (1JP,Cu = 778 Hz) may be
bears acetonitrile as an additional ligand. Related polymers assigned to the apical P atom of the P4S3 cage, which is
from CuX, dppe, and MeCN are known, but the formation coordinated to copper as well as the P atoms of the bridging
of a (Cu2Cl2)2(μ-dppe)2 cluster as part of a polymer seems dppe ligand, which give rise to another multiplet at δ =
to be unique.[11] Chelating coordination behavior of the –11.4 ppm (1JP,Cu
= 1473 Hz). The singlet at δ =
dppe ligand has been observed in [Cu2(SePh)2(dppe)(4,4Ј- –105.5 ppm is typical of the atoms of the P3 base of P4S3.[17]
bipyridine)].[20]
Figure 4. 31P MAS NMR spectrum of 7. Spinning side bands are
marked by ϫ.
Figure 2. Section of the structure of 6; H atoms omitted. Selected
distances [Å]: Cu1–Cl1 2.419(1), Cu2–Cl1 2.385(1), Cu1–Cl2
2.400(1) Cu2–Cl2 2.370(1), Cu1–P2 2.254(1), Cu2–P1 2.212(1),
Cu1–P3 2.256(1), Cu2–N1 2.047(3), Cu1···Cu2 3.149(1).
Compound 7 crystallizes in the monoclinic space group
P21/c. The structure is composed of 1D strands, which are
formed by an alternating arrangement of planar Cu2I2 rings
and trans coordinated dppe ligands. The coordination
sphere around the Cu1 atoms is completed by apically coor-
dinated P4S3 (Figure 3). No basal P atoms are involved in
the coordination, which is in contrast to the structures ob-
served for binary polymers formed from P4S3 and CuI.[17]
The distances within the P4S3 ligand are only slightly affec-
ted by the coordination to copper. The parallel strands are
organized in the crystal structure into stacks along the a
axis.
Figure 5. Section of the crystal structure of [(CuX)2(P4S3)(dppe)]
[X = Br (8), I (9)]. Only the ipso C atoms of the phenyl groups are
shown.
Table 3. Selected distances [Å] for 8 and 9.
8
9
S1–P3
S1–P4
S2–P3
S2–P5
S3–P3
S3–P6
P4–P5
P4–P6
2.104(1)
2.101(1)
2.099(2)
2.097(1)
2.089(1)
2.094(1)
2.242(2)
2.239(1)
2.226(2)
2.484(1)
2.455(1)
2.500(1)
2.489(1)
2.262(1)
2.279(1)
2.244(1)
2.373(1)
3.115(1)
2.104(2)
2.097(2)
2.098(2)
2.091(2)
2.087(2)
2.092(2)
2.243(2)
2.238(2)
2.229(2)
2.648(2)
2.638(2)
2.638(1)
2.607(1)
2.264(2)
2.281(2)
2.252(2)
2.354(2)
3.131(2)
P5–P6
Cu1–X1
Cu2–X2
Cu1–X2
Cu2–X1
Cu1–P2
Cu1–P3
Cu2–P1
Cu2–P4
Cu1–Cu2
Figure 3. Section of the crystal structure of 7. Selected distances
[Å]: S1–P1 2.089(1), S1–P2 2.098(1), S2–P1 2.090(1), S2–P3
2.090(2), S3–P1 2.098(1), S3–P4 2.102(1), P2–P4 2.249(2), P2–P3
2.242(2), P3–P4 2.236(2), Cu1–P1 2.271(1), Cu1–P5 2.262(1), Cu1–
Cu1a 2.875(1), Cu1–I1 2.637(1)–2.664(1).
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Competitive Building Blocks in Copper(I) Coordination Polymers
The ratio of integrals of Papical/Pdppe/Pbasal is 1:2:3, which is pyz N atoms to accomplish a 3D network. In this way, or-
in agreement with the crystal structure determination.
ganic and inorganic building blocks are organized into
Isostructural 8 and 9 crystallize in the triclinic space alternating planar layers orthogonal to the ac plane (Fig-
¯
group P1. Characteristic of both structures are planar ure 7). The C atoms of the pyz ligands are disordered in a
Cu2X2 rings, which are trans connected by dppe ligands to 68:32 ratio. Compared to free P4S3, only the P–P distances
form 1D strands (Figure 5). Contrary to the structure of 7, of the P3 basis are slightly affected. Compound 10 can for-
two P4S3 ligands are coordinated through one of their api- mally be described as a mixed polymer constructed from
cal atoms (P3) and one of the basal atoms (P4). The oppo- sections of 2D-[(CuCl)3(P4S3)2][17] and 2D-[CuCl-
site phosphorus sites of the cage molecules coordinate to (C4H4N2)].[21]
neighboring strands to give 2D networks. The distances
within the P4S3 cage are only slightly affected by the coordi-
nation (Table 3).
The System P4S3, CuX (X = Cl, Br) and pyz
In the following experiments, the replacement of the con-
formational flexible dppe ligand by the rigid pyz ligand in
the interdiffusion experiments was investigated. Layering a
solution of P4S3 and pyz in CH2Cl2 with CuCl in CH3CN
gave a mixture of flat yellow and red prisms. The yellow
prisms were identified by X-ray crystallography as a hybrid
polymer of composition [(CuCl)4(P4S3)2(pyz)] (10), whereas
the red prisms were the P4S3-free coordination polymer
[(CuCl)(pyz)].[21] Although an orange-red photolumines-
cence was observed for [(CuCl)(pyz)] upon irradiation at
254 nm, no emission was observed for 10.
Figure 7. Section of the crystal structure of 10 projected on the ac
plane.
The purity of 10 with respect to other phosphorus con-
taining compounds was checked by 31P MAS NMR spec-
troscopy. The spectrum contains two groups of signals. The
multiplet at δ = 92.2 ppm is typical of the apical atom P2,[17]
the coordination to copper giving rise to a 31P63,65Cu cou-
pling of 1102 Hz (Figure 8). The signals at δ = –72.5 (1JP,Cu
= 1190 Hz) and –83.4 ppm (1JP,Cu = 894 Hz) may be as-
signed to the atoms P1 and P4 of the P3 base, both bound
to copper. The singlet at δ = –97.1 ppm is in agreement
with P3 of the P3 base. Thus, the spectrum supports the
Compound 10 crystallizes in the monoclinic space group
P21/c. The central structural features are castellated
(CuCl)n chains running along the c axis (Figure 6), to which
P4S3 cages and pyrazine molecules are coordinated. A more
detailed inspection of the structure reveals that one of the
(Cu1Cl1)n chains, which are twisted by 12°, is surrounded
by P4S3 molecules, which connect neighboring pairs of
(CuCl)n chains through their basal P1 and P4 atoms. The
resulting (CuCl)2(P4S3)2 sheet is confined by the apical P2
atoms. Neighboring apical P atoms of the sheet are linked
by slightly twisted (8°) (Cu2Cl2)n chains. Similar (CuCl)n
chains are part of the structure of [CuCl(μ2-2-Etpyz-N-
NЈ)].[21] The coordination spheres of Cu2 are completed by
Figure 6. Section of the crystal structure of 10 viewed along the c
axis. The C atoms of the pyz ligands are disordered, 68% occu-
pancy is shown. Selected distances [Å]: S1–P1 2.092(2), S1–P2
2.108(2), S2–P3 2.101(2), S3–P4 2.082(2), S3–P2 2.096(2), P1–P3
2.250(2), P1–P4 2.217(2), P3–P4 2.267(2), Cu1–P1 2.267(2), Cu1– Figure 8. 31P MAS NMR spectra of 10. a) Experimental spectrum;
P4 2.300(2), Cu2–P2 2.177(2), Cu2–N1 2.053(3), Cu1–Cl1
2.287(2)–2.335(2), Cu2–Cl2 2.324(2)–2.335(2).
b) sum of simulated spectra c–e) showing individual components.
Spinning side bands are marked by x.
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crystallographic result well, and other phosphorus contain-
ing species are not present.
The analogous reaction of CuBr with the mixture of
P4S3, pyrazine, and CH2Cl2 gave the known binary poly-
[19]
mers (CuBr)7(P4S3)3 and [CuBr(pyz)].[22] However, when
a P4S3/pyz/toluene mixture was layered with CuBr/CH3CN
yellow rods of (CuBr)2(P4S3)2 (11), red prisms of [CuBr-
(pyz)],[22] and yellow-orange prisms of [(CuBr)3(P4S3)(pyz)]
(12) crystallized, which were characterized by X-ray diffrac-
tion analysis. The products may be distinguished by the red
luminescence of [CuBr(pyz)], whereas compounds 11 and
12 do not emit in the visible spectrum. Selective formation
of 12 by modifying the concentrations or the ratios of the
reactants could not be achieved. In the system P4S3/pyz/CuI
only orange crystals of (CuI)3(P4S3) were found.[17]
Figure 10. Section of the crystal structure of 12. Three of the “N1”
pyrazine rings are omitted for the sake of clarity. Selected distances
[Å]: S1–P1 2.101(2), S1–P2 2.088(2), S2–P3 2.088(2), S3–P1
2.109(2), S3–P4 2.107(2), P2–P4 2.271(2), P2–P3 2.219(2), P3–P4
2.263(2), Cu1–Br1 2.460(1), Cu1–Br2 2.425(1), Cu2–Br2 2.423(1),
Cu2–Br3 2.478(1), Cu3–Br3 2.453(1)–2.508(1), Cu1–P1 2.191(2),
Cu2–P2 2.308(2), Cu2–P3 2.293(2), Cu1–N1 2.048(3), Cu3–N2
2.005(4), Cu3···Cu3a 2.875.
¯
Compound 11 crystallizes in the triclinic space group P1.
The structure is characterized by castellated (CuBr)n chains
running along the a axis. Pairs of these chains are bridged
by P6 and P7 of the tridentate P4S3 cage (P5–P8), and P5
of the same cage binds to Cu2 of the next ribbon. In this
manner a layer parallel to ab is formed, which is confined
by pendent monodentate P4S3 cages (P1–P4) (Figure 9).
The 2D structure of 11 extends the known structures of the
P4S3/CuBr system.[19]
Figure 9. Section of the crystal structure of 11 viewed along the a
axis. Selected distances [Å]: S–P 2.084(2)–2.110(2), P–P 2.215(2)–
2.266(2), Cu–Br 2.417(1)–2.465(1).
Figure 11. Section of the crystal structure of 12 projected on the
ac plane. The solvent molecules are omitted for the sake of clarity.
¯
Compound 12 crystallizes in the triclinic space group P1.
The outstanding structural feature is a cradle composed of
two nearly planar (torsion angle Cu2–Br2/Cu3–Br3 = 16°)
twelve-membered Cu6Br6 rings bridged by two opposing
pyz and two P4S3 ligands. Neighboring Cu6Br6 units are
Conclusions
Access to a new class of hybrid polymers by combining
connected by four-membered Cu2Br2 rings (Cu3Br3). Such organic P,PЈ or N,NЈ donors and a multidentate inorganic
a (CuBr)n substructure is unprecedented.[2] Each ring is cage molecule as cross-linkers with copper(I) halide aggre-
trans-annular spanned by the basal atoms P2 and P3 of a gates of variable size has been described. The nature of the
P4S3 cage, and the apical atom P1 of the same cage is bound products, which range from mononuclear complexes to 3D
to the next ring. Another cage molecule serves as linker in frameworks, depends on the size and steric requirements
the opposite direction. Two pyz molecules bridge opposing, of the organic ligands. The role of the P4S3 ligand may be
slightly displaced Cu6Br6 rings through the N2 atom (Fig- characterized by its nearly spherical geometry, which allows
ure 10). A cage-like substructure is formed in this manner.
reorientational coordination around the C3 axis of the cage.
The sequence of cradles and condensed Cu6Br6 rings In spite of the already well known tendencies of P4S3 or pyz
forms layers parallel to the ab plane. As these layers are to form binary polymers with copper(I) halides, the simul-
linked by “N1” pyz molecules, a 3D framework is built up taneous coordination of P,PЈ or N,NЈ donors and P4S3 is
(Figure 11). The shortest distance between parallel “N1” shown to possess an important synthetic potential. If one
pyz molecules is ca. 9 Å, and that between P4S3 molecules considers the enormous variety of multifunctional organic
of neighboring layers is ca. 5 Å. The resulting cavities are donor ligands numerous and exciting new polymeric archi-
occupied by toluene molecules.
tectures may be expected.
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Competitive Building Blocks in Copper(I) Coordination Polymers
3 H), 1.40 (m, 2 H) ppm. 31P{1H} NMR (121 MHz, C6D6): δ =
89.2 (q; JP,P = 61 Hz), –11.9 (s), –115.0 (d; JP,P = 61 Hz) ppm.
Experimental Section
2
2
General: All manipulations were carried out under nitrogen and
with dry solvents. Diffusion experiments were carried out in
Schlenk tubes of 3.0 cm diameter. P4S3 was synthesized according
to literature methods.[23] 1H and 31P NMR spectra were recorded
with Bruker Avance 300 and Avance 400 spectrometers. 31P MAS
3: C12H30CuIP6S3 (646.80): calcd. C 22.28, H 4.67, S 14.87; found
C 22.27, H 4.50, S 14.57. 1H NMR (300 MHz, C6D6): δ = 0.97 (m,
3 H), 1.44 (m, 2 H) ppm. 31P{1H} NMR (121 MHz, C6D6): δ =
2
2
89.3 (q; JP,P = 62 Hz), –14.6 (s), –115.9 (d; JP,P = 62 Hz) ppm.
1
NMR spectra were recorded with
a Bruker Avance 300
4: H NMR (300 MHz, C6D6): δ = 0.91 (m, 12 H), 1.08 (m, 3 H),
1.63 (m, 2 H) ppm. 31P{1H} NMR (121 MHz, C6D6): δ = 96.6 (q;
(121.495 MHz) spectrometer using a double resonance 2.5 mm
MAS probe. All spectra were acquired at a MAS rotation fre-
quency of 30 kHz, a 90° pulse length of 2.3 μs and with a relaxation
delay of 450 s. For spectrum simulation the program DMFIT was
used.[24]
2
2JP,P = 57 Hz), –1.1 (s), –109.8 (d; JP,P = 57 Hz) ppm.
5: 1H NMR (300 MHz, C6D6): δ = 1.5 (m, 33 H) ppm. 31P{1H}
NMR (121 MHz, C6D6): δ = 94.1 (q; 2JP,P = 57 Hz), 12.6 (s), –111.8
2
(d; JP,P = 57 Hz) ppm.
[CuX(P4S3)(PRRЈ2)2] [R = RЈ = Et, X = Cl (1), Br (2), I (3); R =
Me, RЈ = iPr, X = Cl (4); R = RЈ = Cy: X = I (5)]: A mixture of
CuX (0.454 mmol), phosphane (1.135 mmol), and CH3CN (10 mL)
was combined with a solution of P4S3 (100 mg, 0.454 mmol) in tol-
uene (50 mL) and stirred for 12 h at room temperature. After evap-
oration of the solvent, the oily residue was dissolved in toluene
(3 mL) and cooled to –20 °C. Compounds 1–3 crystallized as color-
less needles in 80% yield, compounds 4 and 5 were obtained as
oils.
[CuCl(dppe)(CH3CN)] (6): Layering a solution of P4S3 (50 mg,
0.227 mmol) and dppe (90 mg, 0.227 mmol) in toluene (10 mL,
22.7 mmolL–1) with a solution of CuCl (36 mg, 0.368 mmol) in
CH3CN (10 mL, 36.8 mmolL–1) gave colorless platelets of 6 and
yellow needles of (CuCl)7(P4S3)3.
[CuI(P4S3)(dppe)] (7): A solution of P4S3 (50 mg, 0.227 mmol) and
dppe (90 mg, 0.227 mmol) in toluene (10 mL, c = 45.4 mmolL–1)
was layered carefully with a solution of CuI (70 mg, 0.368 mmol)
in CH3CN (10 mL, 36.8 mmolL–1). A few bright yellow platelets
of 7 crystallized after about 5 d. 31P MAS NMR: δ = 96.7 (m,
1: C12H30ClCuP6S3 (555.35): calcd. C 25.95, H 5.44, S 17.32; found
C 26.14, H 5.47, S 16.60. 1H NMR (300 MHz, C6D6): δ = 1.00 (m,
3 H), 1.38 (m, 2 H) ppm. 31P{1H} NMR (121 MHz, C6D6): δ =
1
1JP,Cu = 778 Hz), –11.4 (m, JP,Cu = 1473 Hz), –105.5 (s) ppm.
2
2
85.6 (q; JP,P = 62 Hz), –11.0 (s), –115.9 (d; JP,P = 62 Hz) ppm.
[(CuX)2(P4S3)(dppe)] [X = Br (8), I (9)]: P4S3 (50 mg, 0.227 mmol)
2: C12H30BrCuP6S3 (599.84): calcd. C 24.03, H 5.04, S 16.04; found
C 24.41, H 5.04, S 15.51. 1H NMR (300 MHz, C6D6): δ = 0.98 (m,
and dppe (90 mg, 0.227 mmol) were dissolved in CH2Cl2 (10 mL,
c
=
45.4 mmolL–1) and layered with
a
solution of CuX
Table 4. Crystal data and structure refinements for compounds 1–3 and 6–9.
1
2
3
6
7
8
9
Formula
Mw
C
555.39
12H30ClCuP6S3 C12H30BrCuP6S3 C12H30CuIP6S3
599.81 646.80
0.16ϫ0.08 ϫ0.06 0.22ϫ0.15ϫ0.07 0.16ϫ0.07ϫ0.04 0.17ϫ0.03ϫ0.02 0.130.09ϫ0.05
C41H39Cl2Cu2NP3 C13H12CuIP5S3 C26H24Br2Cu2P6S3 C26H24Cu2I2P6S3
836.64 609.74 905.38 999.38
0.21ϫ0.12ϫ0.09 0.07ϫ0.05ϫ0.02
Crystal size
[mm3]
Crystal system orthorhombic
orthorhombic
P212121
7.698(1)
16.470(1)
19.141(1)
–
orthorhombic
P212121
7.821(2)
16.301(1)
19.504(1)
–
triclinic
P1
monoclinic
P21/c
9.472(1)
18.782(1)
11.772(1)
–
109.3(1)
–
1976.5(2)
4
triclinic
P1
triclinic
P1
9.722(1)
13.355(1)
14.177(1)
66.8(1)
82.5(1)
88.0(1)
1676.8(2)
2
1.979
¯
¯
¯
Space group
P212121
7.740(2)
16.617(1)
18.685(1)
–
a [Å]
b [Å]
c [Å]
α
13.462(1)
13.575(1)
13.808(1)
103.2(1)
108.1(1)
111.2(1)
2062.4(2)
2
9.684(1)
13.264(1)
14.070(1)
66.4(1)
83.4(1)
89.4(1)
1643.2(2)
2
1.830
9.139
1.54184
–
SuperNova
295
β
–
–
–
–
–
γ
–
V [Å3]
Z
2403.3(1)
4
1.535
2426.6(2)
4
1.642
2486.6(1)
4
1.728
ρcalcd. [gcm–3
]
1.347
3.777
2.049
μ [mm–1
]
8.488
9.323
16.964
20.573
1.54178
–
SuperNova
123
20.621
λ (Å)
1.54178
empirical
SuperNova
123
3.56ϽΘϽ-73.60 3.54ϽΘϽ72.75
4555 / 3785
1.54178
empirical
Gemini Ultra
123
1.54178
analytical
SuperNova
123
3.53ϽΘϽ73.63
6348 / 3830
1.54184
analytical
SuperNova
173
3.65ϽΘϽ62.18
17518 / 5318
1.54180
analytical
SuperNova
123
3.42ϽΘϽ73.16
17506 / 6051
Abs. corr.
Instrument
Temp. [K]
Scan range
Refl. col-
4.62ϽΘϽ69.14 3.64ϽΘϽ71.36
9883 / 3255
4357 / 3939
17744 / 5658
lected / unique
Parameters
GOF in F2
Residual den-
318
1.035
0.542 / –0.316
250
0.999
0.542 / –0.354
318
0.993
0.717 / –0.582
461
1.071
0.818 / –0.509
208
0.989
0.330 / –0.353
352
1.029
0.930 / –0.710
352
1.032
1.052 / –0.784
sity [eÅ–3
]
R1, wR2 (I
Ͼ2σ)
R1, wR2 (all
data)
Flack param-
eter
0.033, 0.081
0.038, 0.084
0.48(4)
0.031, 0.076
0.035/0.082
0.37(4)
0.027, 0.066
0.031, 0.066
–0.016(5)
0.032, 0.086
0.038, 0.088
–
0.019, 0.046
0.022, 0.047
–
0.023/0.059
0.025/0.060
–
0.022, 0.055
0.025, 0.056
–
Eur. J. Inorg. Chem. 2011, 4248–4255
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4253

J. Wachter et al.
FULL PAPER
Table 5. Crystal data and structure refinements for compounds 10–12.
10
11
12
Formula
C2H2Cl2Cu2NP4S3
Br2Cu2P8S6
727.08
C4H4Br3Cu3N2P4S3, 0.5 C7H8
776.57
Mw
458.14
0.15ϫ0.11ϫ0.06
monoclinic
P21/c
Crystal size [mm3]
0.25ϫ0.03ϫ0.01
triclinic
0.16ϫ0.04ϫ0.02
triclinic
Crystal system
Space group
¯
P1
¯
P1
a [Å]
b [Å]
c [Å]
α
19.090(1)
11.122(1)
6.175(1)
–
94.1(1)
–
6.310(1)
9.226(1)
15.505(1)
99.6(1)
97.7(1)
106.3(1)
838.6(1)
2
9.210(1)
9.288(1)
12.557(2)
106.4(1)
108.9(2)
94.9(1)
955.8(1)
2
β
γ
V [Å3]
1307.8(2)
4
Z
D
2.327
2.880
2.698
ρcalcd. [gcm–3]
μ [mm–1]
16.579
22.753
17.423
λ [Å]
1.54184
–
SuperNova
123
4.60ϽΘϽ73.07
5015 / 2373
128
1.54178
–
Gemini Ultra
123
5.11ϽΘϽ65.06
6872 / 2678
163
1.54184
Absorption correction
Instrument
Temperature [K]
Scan range
analytical
SuperNova
123
5.06ϽΘϽ70.86
5991 / 3085
209
Reflections collected / unique
Parameters
GOF in F2
1.113
1.040
0.961
Residual density [eÅ–3]
R1, wR2 (I Ͼ2σ)
R1, wR2 (all data)
0.401 / –0.532
0.027, 0.070
0.030, 0.072
1.180 / –0.698
0.025, 0.063
0.027, 0.064
0.603 / –0.683
0.026, 0.067
0.032/0.069
(0.368 mmol) in CH3CN (10 mL, 36.8 mmolL–1). After 5 d yellow
needles of 8 or 9 and yellow (CuBr)7(P4S3)3 and (CuI)(P4S3),
respectively, crystallized, which could not be separated quantita-
tively.
structure in the acentric space group P1 was unsuccessful because
all atoms apart from the solvent clearly follow centrosymmetric
requirements. Hence the toluene molecule was necessarily refined
with disorder.
¯
CCDC-826120 (for 1), -826121 (for 2), -826122 (for 3), -826123 (for
6), -826124 (for 7), -826125 (for 8), -826126 (for 9), -826127 (for
10), -826128 (for 11), and -826129 (for 12) contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
[(CuCl)4(P4S3)2(pyz)] (10): P4S3 (30 mg, 0.136 mmol) and C4H4N2
(11 mg, 0.136 mmol) were dissolved in CH2Cl2 (10 mL,
27.2 mmolL–1) and layered with a solution of CuCl (40 mg,
0.408 mmol) in CH3CN (5 mL, 81.6 mmolL–1). After 3 d flat yel-
low prisms of 10 and yellow needles of [CuCl(pyz)] crystallized,
which were separated manually for crystallographic examination.
1
1
31P MAS NMR: δ = 92.2 (m, JP,Cu = 1102 Hz), –72.5 (m, JP,Cu
1
= 1190 Hz), –83.4 (m, JP,Cu = 894 Hz), –97.4 (s) ppm.
Acknowledgments
Reaction of P4S3/pyz with CuBr: A solution of P4S3 (30 mg,
0.136 mmol) and C4H4N2 (22 mg, 0.272 mmol) in toluene (10 mL,
40.8 mmolL–1) was layered with a solution of CuBr (59 mg,
0.408 mmol) in CH3CN (5 mL, 81.6 mmolL–1). Crystalline mate-
rial appeared after 4 d consisting of yellow rods of (CuBr)2(P4S3)2
(11), red prisms of [CuBr(pyz)], and yellow-orange prisms of
[(CuBr)3(P4S3)(pyz)·0.5C7H8] (12), which were separated manually
for X-ray diffraction analysis.
This work was supported by the Deutsche Forschungsgemeinschaft
(DFG) (Wa 486/11-1). The authors also acknowledge the COST
action CM0802 (PhosSciNet) for general support. We thank Dr. C.
Gröger for recording the 31P MAS NMR spectra.
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Received: April 27, 2011
Published Online: August 9, 2011
Eur. J. Inorg. Chem. 2011, 4248–4255
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4255