Synthesis and crystal structures of coordination polymers, networks and complexes of an adamantane shaped phosphorus-nitrogen cage ligand and cuprous chloride

Article abstract of DOI:10.1016/j.poly.2010.03.019

Reactions of cuprous chloride with the phosphorus-nitrogen cage ligand 2,4,6,8,9,10-hexamethyl2,4,6,8,9,10-hexaaza-l,3,5,7-tetraphosphaadamantane, P₄(NCH₃)₆, in acetonitrile form distinct solids depending on the ligand-to-metal ratio. Three structurally characterized compounds include: a solvated 3-D network of formula [P₄(NCH ₃)₆]₂(CuCl)₃(CH₃CN) ₂; a "ladder-type" polymer {[μ₂-P ₄(NCH₃)₆]₂ (CuCl)₂) _∞ and a monomelic complex [P₄(NCH₃) ₆]₂CuCl. Thermal decomposition of the solvated network results in formation of two more materials [P₄(NCH₃) ₆]₂(CuCl)₃, and [P₄(NCH ₃)₆](CuCl)₂ that are not isolated from solution reactions. The variety of products isolated based solely on ligand-to-metal ratio suggest that this system participates in solution equilibria common to many phosphorus(III) ligands and multiple solubility equilibria.

Full text of DOI:10.1016/j.poly.2010.03.019

Polyhedron 29 (2010) 2053–2060
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis and crystal structures of coordination polymers, networks and
complexes of an adamantane shaped phosphorus–nitrogen cage ligand
and cuprous chloride
a
b
a,*
Eric D. Leser , Bruce C. Noll , Roger D. Sommer
a
Department of Chemistry, DePaul University, 1110 W. Belden Ave., Chicago, IL 60614, USA
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556-5670, USA
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Reactions of cuprous chloride with the phosphorus–nitrogen cage ligand 2,4,6,8,9,10-hexamethyl-
Received 24 August 2009
Accepted 23 March 2010
Available online 30 March 2010
2
,4,6,8,9,10-hexaaza-1,3,5,7-tetraphosphaadamantane, P
depending on the ligand-to-metal ratio. Three structurally characterized compounds include: a solvated
-D network of formula [P (NCH (CuCl) (CH CN) ‘‘ladder-type” polymer {[ -P (NCH
CuCl) ; and a monomeric complex [P (NCH CuCl. Thermal decomposition of the solvated network
results in formation of two more materials [P (NCH (CuCl) , and [P (NCH ](CuCl) that are not iso-
4 3 6
(NCH ) , in acetonitrile form distinct solids
3
(
4
3
)
6
]
2
3
3
2
;
a
l
2
4
3 6 2
) ]
}
2 1
4
3 6 2
) ]
Keywords:
Coordination polymer
Copper(I)
4
3
6
) ]
2
3
4
)
3 6
2
lated from solution reactions. The variety of products isolated based solely on ligand-to-metal ratio sug-
gest that this system participates in solution equilibria common to many phosphorus(III) ligands and
multiple solubility equilibria.
Phosphorus–nitrogen ligand
Ó 2010 Elsevier Ltd. All rights reserved.
1
. Introduction
Great interest is currently focused on metal–organic frame-
metal centers [38–40]. The geometric similarities between TPHMI
and HMTA, evidence of its ability to bind multiple Lewis acids,
and its relatively easy synthesis make P (NCH ) an excellent can-
4 3 6
works (MOFs) as useful materials for their gas storage, catalytic,
and optical properties [1–7]. The vast majority of these frameworks
are linked by N or O donor atoms. There are considerably fewer
examples of coordination polymers and arrays linked by P-donor li-
gands [8–32]. This report describes some of the coordination poly-
mers and networks formed by the tetradentate, non-chelating
ligand, 2,4,6,8,9,10-hexamethyl-2,4,6,8,9,10-hexaaza-1,3,5,7-tetra-
didate as a bridging ligand for use in coordination polymers and
networks.
2
. Experimental
All reagents were purchased from Sigma–Aldrich or Fisher/Ac-
ros and used without further purification unless otherwise noted.
All solvents were dried, distilled, and stored over molecular sieves
in the glovebox. With the exception of ligand preparation, all reac-
tions were carried out inside a glovebox (nitrogen atmosphere) to
prevent exposure to oxygen or water vapor. Elemental analysis
was performed by Columbia Analytical Services, Tucson, AZ. Ther-
mogravimetric analysis was performed on a TAQ50 or 2050 instru-
ment. Typically, 10–20 mg samples were heated from 30 to 700 °C
at a ramp rate of 5 °C/min under a 60 mL/min stream of nitrogen.
4 3 6
phosphaadamantane (P (NCH ) or TPHMI in Scheme 1) and cu-
prous chloride. This ligand can be viewed as a ‘‘soft” analogue to
hexamethylenetetramine (HMTA), a common bridging ligand in
coordination polymers and networks [33]. Preliminary studies have
yielded one structurally characterized coordination polymer of
P (NCH ) paired with CuI [34]. Here we build on that result with
4 3 6
a study of the cuprous chloride system in an effort to develop some
principles for rational design of coordination polymers and frame-
4 3 6
works bridged by P (NCH ) .
Tetraphosphorushexamethylimide (TPHMI) and its chalcogen
derivatives were originally synthesized by Holmes [35,36] and
later studied by Cotton and others looking for insight into the
4 3 6
2.1. Ligand preparation P (NCH )
d
p
–p
p
character in the P–N bond [37]. Several other studies
Crude ligand was prepared according to the procedure of
Holmes and Forstner [36]. Methylamine for the procedure was dis-
tilled from a saturated aqueous solution through a column packed
with glass beads [41]. The gas was dried further by passing it
through a one foot column of potassium hydroxide pellets. The
anhydrous methylamine was then condensed into the reaction
showed that TPHMI was a Lewis base that could bind multiple
*
Corresponding author. Tel.: +1 773 325 7322; fax: +1 773 325 7421.
E-mail address: rsommer@depaul.edu (R.D. Sommer).
0
277-5387/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2010.03.019

2
054
E.D. Leser et al. / Polyhedron 29 (2010) 2053–2060
Table 1
Crystallographic details for structures 1 through 3.
Compound
1
2
3
CSD#
743993
743994
743995
Formula
Formula weight
C
16
H
42Cl
975.37
P2 /n
3 3 14 8 12 2 2 12 8 12 8
Cu N P C H36Cl Cu N P C H36ClCuN12P
794.27
P1ꢀ
695.28
Fdd2
Space group
1
0
1
4.2863(5)
5.3649(5)
10.8351(4)
11.1744(4)
12.6817(4)
14.7536
a ( ÅA )
0
1
48.9841
7.9413
b ( AÅ )
0
Scheme 1. The tetradentate non-chelating ligand P
4 3 6
(NCH ) , TPHMI.
17.8721(6)
c ( AÅ )
a
(°)
b (°)
(°0)
90
103.9222(19)
91.235(2)
102.718(2)
1449.27(9)
90
90
90
5739.11
111.478(2)
90
vessel at ꢀ78 °C. Phosphorus trichloride was added slowly while
stirring the mixture with a mechanical stirrer. After warming over
two days, the reaction mixture was extracted with dry hexanes, fil-
tered, and evaporated to yield crude product. Vacuum sublimation
c
3
3650.6(2)
V ( AÅ )
Z
q
4
2
8
calc (g cm 3
ꢀ
)
1.775
1976
2.338
1.820
808
2.124
0.71073
1.609
2864
1.329
0.71073
31
1
F(0 0 0)
l
at 85–100 °C yields pure ligand: P{ H} NMR, singlet, d 82.2 ppm.
(Mo K
a
)
0
0.71073
k ( AÅ )
T (°C)
R; wR
Goodness-of-fit
GOF)
2
2
.2. Preparation of complexes
ꢀ173
ꢀ173
ꢀ173
0.0288; 0.0611
1.016
0.0207; 0.0510
1.029
0.0208; 0.0540
1.171
.2.1. Synthesis of 1 [P
A solution of 0.059 g (0.60 mmol) of cuprous chloride in 6.0 mL
of dry acetonitrile was added to 6.0 mL of solution containing
.177 g (0.594 mmol) of [P (NCH ]. Dropwise addition produced
4
(NCH
3
6
) ]
2
(CuCl)
3
(CH
3
CN)
2
(
0
4
3 6
)
a transient precipitate that redissolved after a few seconds. Once
half of the metal solution was added, the precipitate persisted.
Large amounts of flocculent precipitate formed as addition was
completed. Over a 90 min period, the precipitate settled and be-
came a free-flowing powder in the bottom of the reaction mixture.
Vacuum filtration separated a white solid that was washed with
dry acetonitrile. Yield: 0.222 g (76%). Samples of 1 dried at 60 °C
under vacuum lost 9% of their mass, consistent with the presence
of two acetonitrile molecules in the lattice. Elemental Anal. Calc.
for: C, 19.70; H, 4.34; N, 20.11; Cu, 19.54. Found: C, 19.01; H,
observable change. The solid product was filtered and washed with
acetonitrile then dried briefly. Yield: 0.302 g (94%). Elemental Anal.
Calc. for: C, 10.38; H, 2.61; N, 12.11; Cu, 36.61; P, 17.85. Found: C,
9.69; H, 2.81; N, 10.86; Cu, 36.0; P, 17.2%.
2.2.5. Isolation of 5 and 6 from TGA residue
Samples of 1 were placed in a balance pan of the TGA and
heated to 120 and 200 °C, respectively. Each sample was held at
temperature for 10 min. The resulting powders were removed
and subjected to elemental analysis. Some charring and copper
metal was noted after 200 °C. Samples heated beyond 450 °C
showed significant charring, decomposition, and the presence of
copper metal in the pan.
4
.45; N, 19.19; Cu, 19.7%.
2 4 3 6 2 2 1
2.2.2. Synthesis of 2 {[l -P (NCH ) ] (CuCl) }
0
.607 g (2.04 mmol) of TPHMI was dissolved in 10 mL of dry
acetonitrile. This solution was treated with 3 mL of solution con-
taining 0.050 g (0.51 mmol) of CuCl. An initial precipitate redis-
solved to give a clear solution. The reaction mixture was allowed
to stand for two days. At the end of this time a white solid depos-
ited on the bottom and sides of the vial. The product was filtered
from the reaction mixture and washed with ether. Yield: 0.091 g
2.3. X-ray crystallography
Crystals were handled under oil and the specimen crystals were
affixed to the aperture of a MiTeGen MicroMount mounted to a ta-
pered copper pin. This assembly was placed onto the goniometer of
a Bruker KAPPA APEX II CCD diffractometer equipped with an Ox-
ford Cryosystems Cryostream series 700 low-temperature appara-
tus operating at 100 K. The unit cell and orientation matrix were
determined using reflections harvested from three sets of 12 0.5°
(
45%). Elemental Anal. Calc. for: C, 18.14; H, 4.57; N, 21.17; Cu,
1
2
6.00; P, 31.19. Found: C, 18.13; H, 4.79; N, 20.04; Cu, 13.7; P,
9.9%.
u scans, such that I > 2r(I). Final unit cell parameters were deter-
2
.2.3. Crystal growth of 3 [P
Single crystals of 3 grew from long standing reaction mixtures
4
(NCH
3
)
6 2
] CuCl
mined using reflections harvested from each entire data set. All
data were corrected for Lorenz and polarization effects, as well as
for absorption.
Structure solution and refinement utilized the SHELXTL software
package as implemented in the APEX2 software suite [42]. Figures
were constructed and rendered using ORTEP-3 for Windows [43]
and POV-RAY for Windows 3.6 [44]. A summary of crystallographic
data for all compounds is provided in Table 1.
where L:M is in excess of 8:1. However, bulk samples of pure 3
were not obtained from reaction mixtures with stoichiometries
up to 10:1. Reactions of excess ligand with CuCl were performed
as above for 1 and 2, but all reactants remain in solution. Removal
of solvent under vacuum yields a white solid that is mostly ligand.
Washing with hexanes removes excess ligand and leaves behind a
solid mixture of 2 and 3.
3
. Results
2
.2.4. Synthesis of 4 [P
Reactions with L:M ratios of 1:4 or lower yield the same com-
pound. Cuprous chloride (0.183 mg, 1.85 mmol) was dissolved in
mL of dry acetonitrile. A solution of ligand in acetonitrile
0.132 g, 0.443 mmol) was added dropwise to the metal solution.
4 3 6 4
(NCH ) ](CuCl)
3.1. Structures of 1, 2 and 3
7
(
3.1.1. 3-D network
X-ray quality crystals of 1 grow from reaction mixtures contain-
ing a ligand-to-metal ratio of 2:1. A single crystal was chosen from
the reaction mixture and mounted on a thin fiber. The structure of
A thick white precipitate formed immediately. After a few minutes,
the thick precipitate became a free-flowing powder at the bottom
of the flask. The reaction mixture was stirred for six days with no
3 4 3 6 2 3
1 is a three-dimensional array of formula [l -P (NCH ) ] (CuCl)

E.D. Leser et al. / Polyhedron 29 (2010) 2053–2060
2055
CH
3
CN]ꢁCH
3
CN. The asymmetric unit of 1 is shown in Fig. 1, and
Cu3 arises from coordination by P7 and P8 from different ligands
and a terminal chloride, Cl3. Fig. 3 shows propagation of the
exhibits the three different coordination environments for copper.
Expansion of the structure about an inversion center generates the
L Cu
4 4
ring structure along the a-axis, yielding a linear chain linked
Cl dimers. The third environment for copper in 1 is
4
L Cu
4
ring shown in Fig. 2. The tetrahedral coordination environ-
by shared Cu
2
2
ment of Cu1 consists of P1 and P5 from different ligands and two
symmetry equivalent Cl1 ions. Trigonal planar environment of
tetrahedral, and consists of P3, P4 of an adjacent TPHMI, a terminal
chloride, and N-bound acetonitrile. The result is Cu2 cross-linking
4 4 1
the (L Cu ) chains to form a three-dimensional network. A pack-
ing diagram, viewed down the a-axis of the unit cell, is shown in
Fig. 4. The bond distances for copper atoms are typical for each
of the three geometries observed.
The internal structure of the P N cage is distorted slightly from
4 6
the ideal tetrahedral geometry. The P–N bonds range in length
from 1.679(2) to 1.722(2) Å. Bonds that contain a P bound to Cu
(
e.g. P–N bonds to P1) are noticeably shorter (0.03 Å on average)
than those where P does not interact with a metal. This shortening
is compensated for by minor elongation of the adjacent N–P bonds
(
e.g. N1–P2). The sum of bond angles around N atoms in the cage
varies from 357.9° to 343.5° and shows no correlation with the
adjacent P atoms being bound to Cu.
3
.1.2. Ladder
Compound 2 crystallizes in the P1 space group, forming a lad-
der-type structure. A segment of the polymer is shown in Fig. 5.
The Cu Cl dimers are linked by P atoms from TPHMI. The structure
ꢀ
2
2
extends into polymer by coordination of a second P atom from a
neighboring dimer. The packing diagram in Fig. 6 shows the paral-
lel arrangement of polymer strands in the solid. Both copper atoms
are tetrahedrally coordinated with Cu–Cl bond lengths in a narrow
range of 2.3863(4)–2.4018(4) Å. The P–N bond lengths range in
length from 1.6881(12) to 1.7230(12) Å, with the shortest dis-
tances where P is bound to Cu (0.02 Å shorter than average for
other P–N bonds). The sum of the angle around N atoms in the cage
range from 348.8° to 359.4° with no clear pattern related to bond-
ing at adjacent P atoms.
3.1.3. Monomer
Compound 3 crystallizes as a monomeric complex, shown in
Fig. 7, in the orthorhombic space group Fdd2. The coordination
geometry around Cu1 is planar with a P–Cu–P bond angle of
Fig. 1. Thermal ellipsoid plot of the asymmetric unit of 1. Ellipsoids drawn at 50%
probablility. Hydrogen atoms and the unbound solvent molecule are removed for
clarity.
1
26.6° and a Cl–Cu–P, angle of 116.7°. The average P–N bond
Fig. 2. Structure of 1 expanded to show the Cu
4
L
4
ring and (CuCl)
2
dimer. Symmetry operations: (i) ꢀx, ꢀy, ꢀz + 2; (ii) ꢀx + 1, ꢀy, ꢀz + 2; (iii) x + 1/2, ꢀy + 1/2, z + 1/2;
(
iv) x ꢀ 1/2, ꢀy + 1/2, z ꢀ 1/2. Thermal ellipsoids drawn at 50% probability. Methyl groups are removed for clarity.

2
056
E.D. Leser et al. / Polyhedron 29 (2010) 2053–2060
Fig. 3. The extended chain of L
4
Cu
4
rings along the a-axis. Thermal ellipsoids drawn at 50% probability. Methyl groups and solvent molecules removed for clarity.
Fig. 4. Partial packing diagram for 1 viewed down a-axis of the unit cell. Thermal ellipsoids drawn at 50% probability. Hydrogen atoms removed for clarity.
lengths for P1 (bonded to Cu) are 0.03°Å shorter than the average
for adjacent P–N bonds. Of the three N atoms bound to P1, only
N3 has planar geometry. The P1–N3 bond is also the shortest of
the three.

E.D. Leser et al. / Polyhedron 29 (2010) 2053–2060
2057
Fig. 5. A segment of coordination polymer compound 2. Symmetry equivalent ligands generated by (i) ꢀx + 1, y, ꢀz + 1, (ii) ꢀx + 2, ꢀy + 1, ꢀz + 1. Thermal ellipsoids drawn at
5
0% probablility. Hydrogen atoms removed for clarity.
Selected bond lengths and angles for all structures are pre-
sented in Table 2.
polymer 2, precipitates. Higher L:M ratios result in a mixture of
products containing 2 and the monomeric compound 3. Reactions
4 3 6
of P (NCH ) with CuCl in ratios less than 1 seem to yield a smaller
3
.2. Thermogravimetric analysis of 1
range of products. Reactions with L:M ratios between 0.5 and 1
yield impure samples of 1. Reactions where L:M is less than 0.25
all yield the same compound, 4, tentatively assigned the formula
Thermogravimetric traces for compounds 1, 2 and 4 are shown
in Fig. 8. When compound 1 is subjected to thermogravimetric
analysis, the sample shows a mass loss event at 110 °C consistent
with vaporization of the solvent molecules. The result is compound
4 3 6 4
P (NCH ) (CuCl) . Attempts to grow X-ray quality crystals of 4
have been unsuccessful to date.
Structural characterization of 1–3 show that they are typical
examples of both the coordination chemistry of copper chloride
5, with the L:M ratio of 2:3. A second loss of mass is observed at
1
70 °C that is consistent with vaporization of 1/2 of one equivalent
4 3 6
and the internal bonding of the P (NCH ) ligand system. The P–
of ligand, resulting in compound 6 with L:M ratio of 1:2. Samples of
both 5 and 6 were subjected to elemental analysis as support for
the TGA results. The percent compositions were consistent, but
N bond lengths of P (NCH are variable, and influenced by crystal
4
3 6
)
packing forces, and the other atoms bonded to P [37,45]. In this
series of compounds, P–N bond lengths in the cage range as much
as 0.04 Å, depending on proximity to a P–Cu bond. These effects are
small when compared to those observed for the chalcogen deriva-
not precise matches, to formulations of P
and P (NCH (CuCl) for 6. These results are collected in Table 3.
X-ray powder diffraction measurements also suggest that little of
remains in the sample of 5, and that 6 is free of contamination
from 1 or 5. Further heating causes a rapid loss of mass at
4 3 6 3
(NCH ) (CuCl) for 5
4
3
)
6
2
4 3 6 3
tives [45–47] or the methylphosphonium P (NCH ) CH I structure
1
[48].
It is interesting to note that in all reactions where L:M P 1 there
is instantaneous formation of an amorphous precipitate that disap-
pears with stirring. In reactions where L:M < 1, the immediate
product does not redissolve, but the consistency changes from
globular to free-flowing powder over several minutes. Observation
of this type of ‘‘kinetic product” has been noted previously in sim-
ilar nitrogen bridged systems [49].
2
80 °C, resulting in decomposition.
Mass losses for compounds 2 and 4 are less well defined. Com-
pound 2 undergoes a 20% mass loss at 180 °C, consistent with the
loss of one quarter of the ligand from the sample. No further anal-
ysis of TGA data was attempted.
Isolation of multiple products from Cu(I)–phosphine systems
based on different L:M ratios is well-documented in the literature
4
. Discussion
[
50,51]. Studies of the solution phase equilibria for copper halide
complexes of tertiary phosphines (Ph P and Ph MeP) have shown
that L CuCl is the dominant species in solution when L:M > 3,
and that multiple equilibria for ligand dissociation and halide
bridging give rise to a wide variety of species in solution [52]. Mul-
TPHMI reacts with cuprous chloride in acetonitrile to form a
series of compounds. Depending on the stoichiometry of the reac-
tion mixture, products with ligand-to-metal (L:M) ratios ranging
from 1:4 to 2:1 have been observed. An equimolar reaction of li-
gand and metal yields a solvated product with a 2:3:2 (L:M:sol-
vent) ratio 1. With L:M > 3 the ‘‘ladder-type” coordination
3
2
2
4 3 6
tiple equilibria are also observed in the reaction of P (NCH ) with

2
058
E.D. Leser et al. / Polyhedron 29 (2010) 2053–2060
Fig. 6. Partial packing diagram for 2 viewed parallel to the polymer chains. Thermal ellipsoids drawn at 50% probability. Hydrogen atoms removed for clarity.
Fig. 7. Thermal ellipsoid plot of 3 drawn at 50% probability. Symmetry equivalent ligand generated by (i) ꢀx + 3/2, ꢀy + 1/2, z. Hydrogen atoms removed for clarity.
Lewis acids, where intermediates can be observed by 31P NMR
39,40,53,54]. In the case of 1, it appears that the multiple solution
equilibria and the low solubility of the coordination network lead
to a product that displays multiple coordination environments
for copper. Attempts to study the P (NCH /CuCl equilibria by
solution NMR are complicated by precipitation of the products,
[
4
3 6
)

E.D. Leser et al. / Polyhedron 29 (2010) 2053–2060
2059
Table 2
Selected bond lengths and angles for 1 through 3.
1
2
3
Cu1–P1
Cu1–P5
Cu1–Cl1
Cu1–Cl1(i)
Cu2–N13
Cu2–P3
Cu2–P4
Cu2–Cl2
Cu3–Cl3
2.2570(7)
2.2598(7)
2.4017(7)
2.4203(7)
2.042(2)
2.2364(7)
2.2422(7)
2.3015(7)
2.2032(8)
2.2036(7)
2.2278(7)
Cu1–P1
2.2754(4)
2.2764(4)
2.4018(4)
2.3863(4)
2.2756(4)
2.2780(4)
2.3995(4)
2.3983(4)
Cu1–P1
Cu1–Cl1
2.2187(4)
2.2060(7)
Cu1–P7(ii)
Cu1–Cl1
Cu1–Cl2
Cu2–P5
Cu2–P3(ii)
Cu2–Cl1
Cu2–Cl2
Cu3–P8
Cu3–P7
P1–Cu1–P5
P1–Cu1–Cl1
P5–Cu1–Cl1
P1–Cu1–Cl1(ii)
P5–Cu1–Cl1(ii)
Cl1–Cu1–Cl1(ii)
N13–Cu2–P3
N13–Cu2–P4(iv)
P3–Cu2–P4(iv)
N13–Cu2–Cl2
P3–Cu2–Cl2
P4(iv)–Cu2–Cl2
Cl3–Cu3–P8
Cl3–Cu3–P7(i)
P8–Cu3–P7(i)
Cu1–Cl1–Cu1(ii)
121.03(3)
P1–Cu1–P7(i)
P1–Cu1–Cl2
P7(i)–Cu1–Cl2
P1–Cu1–Cl1
P7(i)–Cu1–Cl1
Cl2–Cu1–Cl1
P5–Cu2–P3(ii)
P5–Cu2–Cl2
P3(ii)–Cu2–Cl2
P5–Cu2–Cl1
117.381(14)
107.812(13)
117.425(13)
112.870(13)
109.054(13)
88.906(12)
117.319(14)
108.349(13)
115.807(14)
114.771(13)
108.584(13)
88.680(12)
90.993(12)
91.399(12)
Cl1–Cu1–P1
P1–Cu1–P1(i)
116.708(11)
126.58(2)
105.03(3)
114.32(3)
112.53(3)
110.40(3)
88.89(2)
104.14(7)
102.32(7)
133.57(3)
108.78(7)
100.38(3)
106.24(3)
116.87(3)
117.56(3)
125.36(3)
91.11(2)
P3(ii)–Cu2–Cl1
Cl2–Cu2–Cl1
Cu2–Cl1–Cu1
Cu1–Cl2–Cu2
Thermogravimetric traces for compounds 1, 2 and 4
illustrated by the isolation of mixtures of 2 and 3 during attempts
to collect pure bulk samples of 3. A similar mixture of 1 and 4 is
isolated when a L:M reaction ratio of 1:2 is employed in attempted
100
2
preparation of (TPHMI)(CuCl) . The presence of a small amount of 3
9
0
0
0
0
0
0
0
in samples of compound 2 could explain the poor results for phos-
phorus analysis. Decomposition during thermal analysis of 1 pro-
duced some copper metal, which was not included in samples of
8
7
6
5
4
3
Compound1
compound 2
Compound4
5
and 6 submitted for analysis. These products were recovered un-
der aerobic conditions, providing a possibility of further decompo-
sition during sample transfer.
Thermogravimetric analysis of 1 displays aspects similar to N-
bridged networks of copper halides [49]. Solvent molecules are lost
at relatively low-temperatures with subsequent loss of ligand to
yield materials of new composition. Heating a sample of 1 provides
a route to isolating compounds 5 and 6 that were otherwise not
isolated from solution reactions. This is particularly interesting in
the case of 6, since solution reactions of L:M = 0.5 do not produce
0
100
200
300
400
500
600
700
Temperature (deg C)
Fig. 8. Thermogravimetric traces for compounds 1, 2 and 4.
2
L(CuCl) , but do yield impure 1 mixed with 4.
To our knowledge, there are currently no structural examples of
HMTA/CuCl based coordination polymers to compare with the
P (NCH ) /CuCl system. But a similar variety of coordination
4 3 6
Table 3
Thermogravimetric analysis of [P
4
(NCH
3
)
6
]
2
(CuCl)
3
CH
3
CNꢁCH
3
CN (1).
Temperature Resulting
Analysis %C, %H,
%N, %P, %Cu
Theory %C, %H, %N,
%P, %Cu
modes is found in a number of HMTA-containing systems when
paired with silver ions [33,55]. The one structure found for the
analogous HMTA/AgCl series displays three different coordination
environments for the metal [56]. So far, reactions of P (NCH )
4 3 6
with silver salts have resulted only in reduction of the Ag(I) to sil-
ver metal.
(
mass loss) °C (%) material
1
10 (9.2)
(L) (CuCl)
compound 5
(L)(CuCl)
compound 6
2
3
16.46, 3.69,
18.55, 26.9, 20.4
14.34, 3.30,
16.13, 4.06, 18.82,
27.74, 21.34
14.52, 3.66, 16.94,
24.97, 25.61
1
71 (15.5)
2
16.10, 23.7, 23.9
and the quadrupolar moment of Cu. Studies of cuprous ions coor-
5. Conclusion
dinated to modified cage ligands P
propyl) and the use of non-bridging anions like PF
4
(NR)
6
where R = ethyl and n-
ꢀ
6
are underway.
4 3 6
The tetradentate ligand P (NCH ) forms at least four coordina-
Elemental analysis of compounds presented in this work pro-
vides only approximate matches for many of the compounds. The
likely presence of multiple equilibria in solution and the observed
co-precipitation of multiple products from reaction mixtures sug-
gest that any bulk sample isolated from this reaction system is
likely to contain impurities of the other phases. This problem is
tion compounds with cuprous chloride in acetonitrile at room tem-
perature and atmospheric pressure. The composition of these
products ranges in ligand-to-metal ratio from 1:4 to 2:1. Structur-
ally characterized forms include a monomeric compound, a poly-
meric ladder structure, and a three-dimensional structure of
4 3 6
cross-linked chains. These observations show that P (NCH ) has

2
060
E.D. Leser et al. / Polyhedron 29 (2010) 2053–2060
the potential to be a useful building block for the synthesis of phos-
phorus(III)-bridged MOFs. Changes to solvent system, temperature
and pressure are currently under investigation in attempts to ob-
[15] K.K. Klausmeyer, R.P. Feazell, J.H. Reibenspies, Inorg. Chem. 43 (2004) 1130.
[
[
[
16] H. Krishna, S.S. Krishnamurthy, Inorg. Chim. Acta 360 (2007) 3462.
17] E. Lozano, M. Nieuwenhuyzen, S.L. James, Chem.-Eur. J. 7 (2001) 2644.
18] P.W. Miller, M. Nieuwenhuyzen, J.P.H. Charmant, S.L. James, Inorg. Chem. 47
(2008) 8367.
4 3 6
serve more phases of the P (NCH ) /CuCl. Still more variations of
[
[
[
19] J.M.J. Paulusse, J.P.J. Huijbers, R.P. Sijbesma, Macromolecules 38 (2005) 6290.
20] Z. Qin, M.C. Jennings, R.J. Puddephatt, Chem.-Eur. J. 8 (2002) 735.
21] X. Xu, E.J. MacLean, S.J. Teat, M. Nieuwenhuyzen, M. Chambers, S.L. James,
Chem. Commun. (2002) 78.
the networks formed by this ligand are possible through addition
of auxiliary ligands to the metal center and use of other counteri-
ons for Cu(I).
[
[
22] X. Xu, M. Nieuwenhuyzen, S.L. James, Angew. Chem., Int. Ed. 41 (2002) 764.
23] X. Xu, J. Zhang, A. Pichon, A.L. Garay, S.L. James, Polym. Prepr. (Am. Chem. Soc.,
Div. Polym. Chem.) 48 (2007) 566.
6
. Supplementary data
[
[
24] J. Bai, A.V. Virovets, M. Scheer, Angew. Chem., Int. Ed. 41 (2002) 1737.
25] P.D. Harvey, in: A.S. Abd-El-Aziz, I. Manners (Eds.), Frontiers in Transition
Metal-Containing Polymers, John Wiley and Sons, Hoboken, NJ, 2007, p. 321.
26] D. Samar, J.-F. Fortin, D. Fortin, A. Decken, P.D. Harvey, J. Inorg. Organomet.
Polym. Mater. 15 (2006) 411.
27] P.D. Harvey, E. Fournier, ACS Symp. Ser. 928 (2006) 472.
28] E. Fournier, S. Sicard, A. Decken, P.D. Harvey, Inorg. Chem. 43 (2004) 1491.
29] P.D. Harvey, Macromol. Symp. 196 (2003) 173.
CCDC 743993, 743994 and 743995 contain the supplementary
crystallographic data for compounds 1, 2 and 3. These data can
be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/
retrieving.html, or from the Cambridge Crystallographic Data Cen-
tre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-
[
[
[
[
0
33; or e-mail: deposit@ccdc.cam.ac.uk.
[30] M.A. Fox, D.A. Chandler, Adv. Mater. (Weinheim, Ger.) 3 (1991) 381.
[
31] R.D. Pike, B.A. Reinecke, M.E. Dellinger, A.B. Wiles, J.D. Harper, J.R. Cole, K.A.
Dendramis, B.D. Borne, J.L. Harris, W.T. Pennington, Organometallics 23 (2004)
Acknowledgements
1
986.
32] C. Sivasankar, M. Nethaji, A.G. Samuelson, Inorg. Chem. Commun. 7 (2004)
38.
[
2
This work was supported by DePaul University, College of Liber-
al Arts and Sciences, Undergraduate Summer Research Program,
Undergraduate Research Assistantship Program, and Faculty Sum-
mer Research and Development grants. NMR instrumentation
[
[
33] S.-L. Zheng, M.-L. Tong, X.-M. Chen, Coord. Chem. Rev. 246 (2003) 185.
34] R.D. Sommer, A.L. Rheingold, Acta Crystallogr., Sect. E: Struct. Rep. Online E62
(2006) m74.
[
[
[
35] R.R. Holmes, J. Am. Chem. Soc. 83 (1961) 1334.
36] R.R. Holmes, J.A. Forstner, Inorg. Synth. 8 (1966) 63.
37] F.A. Cotton, J.G. Riess, B.R. Stults, Inorg. Chem. 22 (1983) 133.
(
Bruker Avance 300) acquired under National Science Foundation
CCLI A&I program Grant No. DUE-0310624. X-ray instrumentation
acquired under US NSF Grant CHE-0443233 (University of Notre
Dame).
[38] J. Reiss, J.R.V. Wazer, Bull. Soc. Chim. Fr. (1966) 1846.
[39] J.G. Riess, J.R. Van Wazer, J. Organomet. Chem. 8 (1967) 347.
[
[
[
40] J.G. Riess, J.R. Van Wazer, Bull. Soc. Chim. Fr. (1968) 3087.
41] R.W.L. Kimber, I.F. Fergus, Fert. Res. 5 (1984) 245.
42] Bruker AXS Inc., Madison, WI 53719, USA, 2004.
References
[43] L.J. Farrugia, J. Appl. Crystallogr. 30 (1997) 565.
[
[
44] Persistence of Vision Raytracer, Version 3.6, Retrieved from: <http://
www.povray.org/download/>, 2004.
45] F. Casabianca, F.A. Cotton, J.G. Riess, C.E. Rice, B.R. Stults, Inorg. Chem. 17
[
[
[
[
[
1] C.A. Bayse, T.P. Brewster, R.D. Pike, Inorg. Chem. 48 (2009) 174.
2] M. Dinca, J.R. Long, Angew. Chem., Int. Ed. 47 (2008) 6766.
3] S. Horike, M. Dinca, K. Tamaki, J.R. Long, J. Am. Chem. Soc. 130 (2008) 5854.
4] S.S. Kaye, J.R. Long, J. Am. Chem. Soc. 130 (2008) 806.
5] M.J. Lim, C.A. Murray, T.A. Tronic, K.E. deKrafft, A.N. Ley, J.C. deButts, R.D. Pike,
H. Lu, H.H. Patterson, Inorg. Chem. 47 (2008) 6931.
(
1978) 3232.
[
[
[
[
46] F.A. Cotton, J.G. Riess, C.E. Rice, B.R. Stults, Inorg. Chem. 21 (1982) 3123.
47] A. Wolff, J.G. Riess, Bull. Soc. Chim. Fr. (1973) 1587.
48] G.W. Hunt, A.W. Cordes, Inorg. Chem. 13 (1974) 1688.
49] P.M. Graham, R.D. Pike, M. Sabat, R.D. Bailey, W.T. Pennington, Inorg. Chem. 39
[
[
6] J.L.C. Rowsell, O.M. Yaghi, Angew. Chem., Int. Ed. 44 (2005) 4670.
7] T.A. Tronic, K.E. De Krafft, M.J. Lim, A.N. Ley, R.D. Pike, Inorg. Chem. 46 (2007)
(
2000) 5121.
[
50] J.T. Gill, J.J. Mayerle, P.S. Welcker, D.F. Lewis, D.A. Ucko, D.J. Barton, D. Stowens,
S.J. Lippard, Inorg. Chem. 15 (1976) 1155.
8
897.
[
[
8] M.-C. Brandys, R.J. Puddephatt, J. Am. Chem. Soc. 124 (2002) 3946.
9] T.J. Burchell, D.J. Eisler, M.C. Jennings, R.J. Puddephatt, Chem. Commun. (2003)
[
[
[
[
[
51] S.J. Lippard, J.J. Mayerle, Inorg. Chem. 11 (1972) 753.
52] D.J. Fife, W.M. Moore, K.W. Morse, Inorg. Chem. 23 (1984) 1684.
53] J.C. Elkaim, A. Wolff, J.G. Riess, Phosphorus Relat. Group V Elem. 2 (1973) 249.
54] J.G. Riess, A. Wolff, Chem. Commun. (1972) 1050.
2
228.
[
[
[
[
[
10] R.P. Feazell, C.E. Carson, K.K. Klausmeyer, Inorg. Chem. 44 (2005) 996.
11] F. Hung-Low, K.K. Klausmeyer, J.B. Gary, Inorg. Chim. Acta 362 (2009) 426.
12] W.J. Hunks, M.C. Jennings, R.J. Puddephatt, Chem. Commun. (2002) 1834.
13] S.L. James, X. Xu, R.V. Law, Macromol. Symp. 196 (2003) 187.
14] S.L. James, X. Xu, M. Nieuwenhuyzen, Polym. Prepr. (Am. Chem. Soc., Div.
Polym. Chem.) 45 (2004) 423.
55] V.V. Kinzhibalo, M.G. Mys’kiv, V.N. Davydov, Russ. J. Coord. Chem. 28 (2002)
867.
[
56] T.C.W. Mak, Inorg. Chim. Acta 84 (1984) 19.