Bimetallic multidimensional supramolecular coordination polymers containing triphenyltin cation and CuCN

Article abstract of DOI:10.1016/j.jorganchem.2010.04.024

The reaction of K₃[Cu(CN)₄] in H₂O with a solution of Ph₃SnCl and 4-methylpyrimidine (mpym) in acetonitrile affords, at room temperature, the white powder [(Ph₃Sn) ₃Cu(CN)₄.mpym·H₂O], II, precipitating in the mother liquor and colourless platelet crystals [(Ph₃Sn) ₂Cu(CN)₃], I, which was obtained from the filterate after two days. The copper site in I assumes distorted trigonal plane geometry. The network structure of I is constructed via 3D-puckered layers constructed of infinite parallel [CuCN-(μ-Ph₃Sn)-CN] chains forming waves where the CNSnPh₃ fragments locate the peak and bottom positions of the waves as side arms. The 2D-layers are connected by hydrogen bonds and π-π stacking. This is the first example for a Cu-coordination polymer containing the tetrahedral and bipyramidal configured tin atoms. The pyramidal tetrahedral [Cu(CN)₄]^3- anion, in II, are interconnected by two kinds of nanometer spacers; -CN→Sn(Ph₃)←O(H)H...NC- and -CN→Sn(Ph₃)-N(mpym)N-Sn(Ph₃)←NC- creating super-Prussian blue 3D-network structure. The reaction of K₃[Cu(CN) ₄] in H₂O with a solution of Ph₃SnCl and 4-methylpyrimidine (mpym) in acetonitrile affords, at room temperature, the white powder [(Ph₃Sn)₃Cu(CN)₄. mpym·H₂O], II, precipitating in the mother liquor and colourless platelet crystals [(Ph₃Sn)₂Cu(CN)₃], I, which was obtained from the filtrate after two days. The copper site in I assumes trigonal bipyramidal configuration. The network structure of I is constructed via 3D-puckered layers constructed of infinite parallel [CuCN-(μ-Ph₃Sn)-CN] chains forming waves where the CNSnPh ₃ fragments locate the peak and bottom positions of the waves as side arms.

Full text of DOI:10.1016/j.jorganchem.2010.04.024

Journal of Organometallic Chemistry 695 (2010) 1918e1923
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Bimetallic multidimensional supramolecular coordination polymers containing
triphenyltin cation and CuCN
*
Safaa Eldin H. Etaiw , Tarek A. Fayed, Safaa N. Abdou
Chemistry Department, Faculty of Science, Tanta University, El-gish Street, Tanta 31527, Egypt
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of K3[Cu(CN)4] in H2O with a solution of Ph3SnCl and 4-methylpyrimidine (mpym) in
acetonitrile affords, at room temperature, the white powder [(Ph3Sn)3Cu(CN)4.mpym$H2O], II, precipi-
tating in the mother liquor and colourless platelet crystals [(Ph3Sn)2Cu(CN)3], I, which was obtained from
the filterate after two days. The copper site in I assumes distorted trigonal plane geometry. The network
Received 9 March 2010
Received in revised form
20 April 2010
Accepted 21 April 2010
Available online 27 April 2010
structure of I is constructed via 3D-puckered layers constructed of infinite parallel [CuCN-(
chains forming waves where the CNSnPh3 fragments locate the peak and bottom positions of the waves
as side arms. The 2D-layers are connected by hydrogen bonds and stacking. This is the first example
m-Ph3Sn)-CN]
pep
Keywords:
Supramolecular coordination polymers
Organotin polymers
Copper cyanide polymers
4-Methylpyrimidine
for a Cu-coordination polymer containing the tetrahedral and bipyramidal configured tin atoms. The
pyramidal tetrahedral [Cu(CN)4]3ꢀ anion, in II, are interconnected by two kinds of nanometer spacers;
-C^N/Sn(Ph3))O(H)H.N^Ce and eC^N/Sn(Ph3)eN(mpym)NeSn(Ph3))N^Ce creating super-
Prussian blue 3D-network structure.
Ó 2010 Elsevier B.V. All rights reserved.
ꢀ
1. Introduction
adamandoid Cu10 cages with Cu.Cu edges of 10.795 A [10]. While
[CuCN$Me3SnCN$0.5bpe] and [CuCN$Me3SnCN$0.5bpeH2] display
In the past few years, there has been considerable interest in the
design and elaboration of multidimensional Cu(I) coordination
polymers prepared by conventional solution routes or by the less
conventional solvothermal techniques. The products should be
either the [(Cu)n(CN)mxL] complexes [1e7] or the organo-
tinecopper(I) containing polymers [8e12]. The organometallic
layered structures with rhombic [Cu2(
building block. On the other hand, [CuCN$Me3SnCN$cpy] crystal-
lizes in a distorted-diamondoid structure N{Cu[
m-CN)2] motif as basic
3
m-CNSn(Me)3NC]
m-cpy} with four equivalent and independent, interlocking frame-
works [12]. These coordination polymers contain alkyl tin frag-
ments while there are no any derivatives containing the ph3Sn
fragments due to the difficulty for obtaining single crystals. In a trial
to extend this work to obtain new zeolite-like coordination poly-
mers containing ph3Sn fragments, different bipodal ligands are
used including mpym. Powder products are usually obtained while
mpym gives the colourless platelet crystals [(Ph3Sn)2Cu(CN)3], I,
and the crystalline [(Ph3Sn)3(CN)4mpym$H2O], II.
family [(R3E)3M(CN)6^[Mm-(CNE(R3)NC)3] with R ¼ alkyl and
E ¼ Sn or Pb was considered as super-prussian blue derivatives [11]
which are related to zeolites. Few examples of zeolite-like poly-
meric copper cyanides involving the charged bipodal ligands and
the likewise rod-like anionic [CN.Sn(R3)eNC]e acting as a nano-
meter-sized spacer ligand, are known [8e12]. The zeolite-like
[(Bu4N)(Et3Sn)2Cu(CN)4] was obtained by using Et3SnCl [8], while
the different [(Bu4N)(Me3Sn)Cu2(CN)4] was exclusively formed by
using Me3SnCl [11]. The (Bu4N)4ꢀ fragments act as guest ions. On
the other hand, planar sheets involving both 4- and 24- atomic
rings are interlinked in [CuCN$Me3Sn 0.5bpy] by almost perpen-
dicular bpy pillars to generate a very voluminous 3D-framwork
[9]. The novel supramolecular assembly [CuCN$Me3SnCN$pyz]
contains the basic building blocks constructed of distorted
2. Experimental
K3[Cu(CN)4] was prepared following the literature procedures
[13,14]. Triphenyltin chloride, mpym and solvents were purchased
from Aldrich, Merck or Fluka and used without further purification.
2.1. Synthesis of [(Ph3Sn)2Cu(CN)3], I and [(Ph3Sn)3Cu
(CN)4$mpym$H2O], II
A solution of 90 mg (0.31 mmol) of K3[Cu(CN)4] in 5 ml H2O was
added dropwise with stirring to a solution of 366 mg (0.95 mmol)
* Corresponding author. Tel.: +20 173837509.
E-mail address: safaaetaiw@hotmail.com (S.E.H. Etaiw).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.04.024

S.E.H. Etaiw et al. / Journal of Organometallic Chemistry 695 (2010) 1918e1923
1919
ꢀ
of Ph3SnCl and 29 mg (0.31 mmol) of mpym in 10 ml acetonitrile. A
white precipitate of II was formed at once. After filtration, subse-
quent washing with water and acetonitrile and overnight drying,
223 mg (54.4% referred to K3[Cu(CN)4]) of the white precipitate, II,
was obtained. Decomposition temperature is 190 ꢁC. Elemental
analysis data for C63H53N6Sn3$CuO are: Anal. Calc. C, 56.89; H, 3.98;
N, 6.30; Cu, 4.78 and Found C, 56.43; H, 4.12; N, 5.96; Cu, 4.63%.
The colourless solution of the filtrate was kept at room
temperature, where after two days, colourless platelet crystals
started growing from that filtrate. After filtration, washing with
water and acetonitrile and overnight drying, 55 mg (21% referred to
K3[Cu(CN)4]) of I was obtained. Decomposition temperature is
180 ꢁC. TGA thermogram of I exhibits three steps corresponding to
the release of one Ph3Sn unit and three cyanide groups in the
temperature range of 180e270 ꢁC, and three Phenyl groups in the
temperature range 270e400 ꢁC, with the formation of mixed
metals Cu þ Sn in the temperature range of 410e470 ꢁC. The
residue obtained after complete thermolysis (over 600 ꢁC) of I is
coincident with 0.5Sn þ0.5(SnO2) þ Cu [observed mass ¼ 23.99%
(201.74 g molꢀ1), calculated mass ¼ 23.57% (198.25 g molꢀ1)].
radiation [
l
Mo K
a
] ¼ 0.71073 A]. The well developed crystal of I
was mounted on glass fibers, and the measurements were made at
25 ꢂ 2 ꢁC. The structure was solved using direct-methods and all of
the non-hydrogen atoms were located from the initial solution or
from subsequent electron density difference maps during the initial
stages of the refinement. After locating all of the non-hydrogen
atoms in each structure the models were refined against F2, first
using isotropic and finally anisotropic thermal displacement
parameters unless otherwise stated. The positions of the hydrogen
atoms were then calculated and refined isotropically, and a final
cycle of refinements was performed. The refinement of the struc-
ture of I was performed anisotropically for the non-hydrogen atoms
giving R factor 0.058. However, it was observed that the carbon
atoms of the phenyl groups are not stable due to their large
temperature factors suggesting substantial mobility. So, the struc-
ture of I was refined anisotropically for the heavy metals (Sn and
Cu) and the cyanide groups while the atoms of the phenyl groups
were refined isotropically giving R factor 0.065. The structure in this
case is stable at room temperature. This observation supports the
opinion that the phenyl groups attached to the tin atoms act freely
in the structure because they are not connected to any atom in the
lattice giving rise to high amplitude of displacement factor. On the
other hand, all cyanide atoms are ordered since the nitrogen ends
are coordinated to the Sn atoms.
IR spectrum of I n(C^N) 2113 cmꢀ1
, n(C]C) phenyl 1578 and
1481 cmꢀ1 n(SneC) 550 cmꢀ1 and n(CueC) 405 cmꢀ1.1H NMR spectrum
of I displays only two broad multiplet peaks at 7.45 and 7.76 ppm due
to the protons of the phenyl groups indicating the presence of the
ph3Sn units and the absence of the mpym ligand. The ESIþ mass
spectrum of I, exhibits the base peak at m/z 351 corresponding to the
Ph3Snþ isotopomer of the molecular ion. The interpretation of the
positive and negative ion polarity mass spectra for the SCP I was
listed in Table 1 indicating its polymeric nature. Elemental analysis
data for C39H30N3Sn2Cu; are Anal. Calc. C, 55.65; H, 3.56; N, 4.99; Cu,
7.55 and Found C, 55.38; H, 3.46; N, 5.27; Cu, 7.39%.
3. Results and discussion
The crystals of I were found to have the chemical formula 3N[Cu
(CN)3-m-(Ph3Sn)Ph3Sn] which is quite different than the molecular
formula and the structure of the white powder II (vide infra). The
crystal data and structure refinement parameters of I are summa-
rized in Table 2.
The ORTEP plot of I shows one copper (I) site coordinated to the
ordered cyanide groups representing the building blocks of the
structure of I, Fig. 1. The copper site assumes distorted trigonal
plane (TP-3) geometry with angles approximately equal to 360ꢁ,
Table 3. These Cu(CN)3 building blocks are bridged by one Ph3Sn(1)
unit while the other Ph3Sn(2) unit is only bonded to the nitrogen
end of the N(9)^C(49) group. Thus, the copper atom is coordinated
to the carbon ends of the cyanide groups while the tin atoms are
coordinated to the nitrogen ends of the cyanide groups. The Sn(l)
2.2. Physical measurements
Microanalyses (C, H, N) were carried out with a PerkineElmer
2400 automatic elemental analyzer, while copper was determined
using PerkineElmer 2380 atomic absorption spectrometer. Infrared
spectra were recorded on a Bruker Vector 22 spectrophotometer as
KBr discs in the range of 400e4000 cmꢀ1 1H NMR spectra were
.
recorded on a Bruker DPX 200 spectrometer, using DMSO-d6 as
a solvent. Mass spectra were recorded on Finnigan MAT SSQ 7000
spectrometer. The thermogravimetric analyses were carried out on
TGA-50 H thermal analyzer (under N2 atmosphere), in the range of
25 ꢁC to 800 ꢁC at a heating rate 20 ꢁC/min using 0.3e2 mg of the
samples. X-ray powder diffraction patterns were recorded using
a Diang Corporation diffractometer equipped with Co Ka radiation,
tube operated at 45 Kv, 9 mA and single crystal X-ray diffraction
measurements were carried out on a Kappa CCd Enaraf Nonius FR
Table 2
Crystal data and structure refinement parameters of I.
Empirical formula
C39H30N3CuSn2
841.616
298
0.71073
Orthorhombic
Pca21
26.1038(10)
9.5374(3)
15.3152(4)
90.00
90.00
90.00
3812.9 (2)/4
1.466
1.88
Formula weight (g molꢀ1
Temperature (K)
)
ꢀ
Wavelength (A)
Crystal system
Space group
90 four circle goniometer with graphite monochromatic Mo K
a
ꢀ
a (A)
ꢀ
b (A)
ꢀ
Table 1
c (A)
Interpretation of the mass spectra of the positive and negative ion polarity (ESIþ)
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
and (ESIꢀ), respectively for [(Ph3Sn)2Cu(CN)3], I.
Ion
m/z
Ion
m/z
717
817
905
1154
1579
562
652
741
830
921
3
ꢀ
V (A ); Z
Snþ
120
197
274
351
377
392
115
204
295
384
473
(Ph3Sn)2Oþ
r )
calc. (Mg mꢀ3
PhSnþ
[(Ph3Sn)2Cu(CN)2]þ
[(Ph3Sn)2Cu2(CN)3]þ
[(Ph3Sn)2Cu(CN)3PhSnCu(CN)2]þ
[(Ph3Sn)2Cu(CN)3Ph3SnPh2SnCu(CN)2]þ
Cu6(CN)ꢀ7
Absorption coefficient (mmꢀ1
F(000)
)
Ph2Snþ
1656
Ph3Snþ
Reflections collected/unique
R int
5096/1910
0.033
Ph3SnCNþ
[Ph2SnCu(CN)2]þ
Cu(CN)ꢀ2
Cu2(CN)ꢀ3
Cu3(CN)ꢀ4
Cu4(CN)ꢀ5
Cu5(CN)ꢀ6
Data/restraints/parameters
1910/0/266
4.476
0.065/0.147
Cu7(CN)ꢀ8
Goodness-of-fit on F2
Cu8(CN)ꢀ9
R indices [I >3
s
(I)]R1/wR2
Cu9(CN)ꢀ10
W ¼ 1/s2(Fo2) þ 0.1000 ꢃ F2o)
Cu10(CN)ꢀ11
R indices (all data)
0.091/0.152
3
ꢀ
Largest difference peak and hole
1.61/ꢀ0.80 e A

1920
S.E.H. Etaiw et al. / Journal of Organometallic Chemistry 695 (2010) 1918e1923
Fig. 1. Perspective view of the asymmetric unit of I, showing the atom labeling scheme and 50% thermal ellipsoids.
atom forms trigonal bipyramidal (TBPY-5) configuration where the
three phenyl groups occupy the corners of a distorted TP-3, while
the two cyanide groups occupy axial positions, Table 3. The angles
of these cyanide groups at the axial positions defined by the TP-3 of
Sn(l) site deviate slightly from the ideal value of 90ꢁ and conse-
quently the angle of N(5)eSn(l)eN(5) equals to 176.5ꢁ. The Ph3Sn
(1) fragment connects the Cu(CN)3 building blocks forming corru-
gated 1D-Polymeric chain with Cu9N9Sn2(ph3) fragments located
on both sides of the chain as side arms, Fig. 2. The Sn(2) atom is
coordinated to the three phenyl rings and the nitrogen end of one
cyanide group; N(9)eC(49), forming pseudo tetrahedral (PT-4)
structure, Table 3. Also, it was observed that the bond lengths of the
TP-3 assumed by the Sn(l) site are more or less equal,
chemically and crystallographically different. This is the first
example for a Cu-coordination polymer containing the PT-4
configured and the TBPY-5-configured tin atoms as far as we know.
It is worth mentioning that the argument of presence of non
bridging PT-4 configured R3SnNC units in the structure of some
organotin-cyano metallate polymers like [(Me3Sn)4M(CN)6];
M ¼ Fe, Ru or Os, could not be ruled out by solid state 13C and 119Sn
NMR spectra [15]. However, the presence of both PT-4 and TBPY-
5-configured R3SnOn (n ¼ 2 or 1) units has been confirmed by
crystallography and by solid state NMR for two ID-polymeric
carbonates [(R3Sn)2Co3]N, R ¼ Me and Bu [16]. The phenyl rings
occupying the positions of TP-3 and of PT-4 formed by the Sn(l) and
Sn(2) atoms, respectively, are crystallographically equivalent
ꢀ
2.104e2.147 A, while the axial bonds suffer elongation giving Sn(l)e
ꢀ
ꢀ
N(5) ¼ 2.242 A and Sn(l)eN(50) ¼ 2.316 A, the case which supports
the TBPY-5-configured structure of the Sn(l) site. On the other hand,
all the bond lengths of the PT-4 configured structure of the Sn(2)
site are nearly equal supporting the PT-4 configured structure of the
Sn(2) site, Table 3. Thus, the two tin atoms in the structure of I are
Table 3
ꢁ
ꢀ
Selected bond lengths (A) and bond angles ( ) for I.
Sn(1)eN(5)
Sn(1)eC(7)
Sn(1)eC(8)
2.242(7)
2.137(7)
2.104(8)
2.146(7)
2.316(7)
2.172(8)
2.132(9)
2.157(9)
2.075(8)
2.056(10)
1.866(10)
1.969(11)
1.104(10)
1.199(10)
115.2(3)
122.1(3)
108.8(3)
N(5)eSn(1)eC(7)
N(5)eSn(1)eC(8)
N(5)eSn(1)eC(14)
N(5)eSn(1)eC(50)
C(7)eSn(1)eC(8)
C(7)eSn(1)eC(14)
C(7)eSn(1)eN(50)
C(8)eSn(1)eC(14)
C(8)eSn(1)eN(50)
C(14)eSn(1)eN(50)
N(9)eSn(2)eC(11)
N(9)eSn(2)eC(12)
N(9)eSn(2)eC(17)
C(11)eSn(2)eC(12)
C(12)eSn(2)eC(17)
C(49)eCu(3)eC(51)
Cu(3)eC(6)eN(5)
89.6(3)
87.6(3)
92.3(3)
176.5(3)
113.6(3)
118.5(3)
92.4(3)
127.9(3)
89.0(3)
89.3(3)
94.1(3)
95.1(3)
101.6(3)
120.4(3)
120.2(3)
128.7(3)
173.0(3)
Sn(1)eC(14)
Sn(1)eN(50)
Sn(2)eN(9)
Sn(2)eC(11)
Sn(2)eC(12)
Sn(2)eC(17)
Cu(3)eC(6)
Cu(3)eC(49)
Cu(3)eC(51)
N(4)eC(6)
N(9)eC(49)
C(11)eSn(2)eC(17)
C(6)eCu(3)eC(49)
C(6)eCu(3)eC(51)
Fig. 2. A view of portion of the network structure of I, showing the arrangement of
some phenyl groups into the wide channels of I. Hydrogen atoms are omitted for
clarity.

S.E.H. Etaiw et al. / Journal of Organometallic Chemistry 695 (2010) 1918e1923
1921
Table 5
around room temperature owning to rapid rotation about their
Wavenumbers of the different vibrational modes of the SCP II.
individual trigonal axes. This conclusion is further substantiated by
the previous solid state 13C NMR [15] and 2D-EXSY [17] studies
which confirmed the rapid rotation of the alkyl groups (on the NMR
time scale) about their individual trigonal axes. It is, also, observed
that the angles of C(6)eCu(3)eC(49),C(49)eCu(3)eC(51) and C(6)e
Cu(3)C(51) forming the distorted TP-3 trigonal plane geometry of
Cu(I) site have the values 122.1ꢁ, 128.7ꢁ and 108.8ꢁ, respectively.
This situation results to decrease the steric hindrance between the
phenyl groups of both tin atoms [Sn(l) and Sn(2)] and consequently
the Ph3Sn(2) unit seems to locate far away the {Ph3Sn(l)
NCeCueCN Ph3Sn(l)}N fragment.
Peak, cmꢀ1 Assignment
Peak,
cmꢀ1
Assignment Peak,
cmꢀ1
Assignment
3447b
3136w
nH
1648 m dH
1189w nCeN
857w
680w
2O
2 O
nCH (pym)
1598w
1577w
1544w
1516m
1480s
nC]C
gCH (mpym)
2
3064m
3047m
2932m
2860m
2111s
nCH (aromatic)
nCH (m)
nC]C (Ph)
729s
694s
gCH (Ph)
1438w
dCH (mpym) 541b
nSneC
nC^N
1428s
dCH (Ph) 451s
Vib. of
Ph ring
nCueC
The cyanide bond lengths are in the normal range of
1334m
ꢀ
1956w
1883w
1815w
1771w
1705m
Overtones and 1391 m dCH (mpym) 413w
1.1160e1.1910 A, Table 3. The CNeCu and the CNeSn angles deviate
from 180ꢁ usually acquired by the CNeM angle being in the range of
162e172.1ꢁ. As a result of the values of these angles, the structure of I
gives rise to comparatively compact 3D-puckered chains of infinite
extension in the bc-plane, Fig. 2. The network structure of I is con-
combinations
of the phenyl
groups
Pym ¼ pyrimidine, m ¼ methyl, ph ¼ phenyl, mpym ¼ methylpyrimidine, b ¼ broad,
s ¼ strong, m ¼ medium and w ¼ weak.
structed via puckered chains constructed of infinite [CuCN-m-
(Ph3Sn)eCN] units. These infinite puckered chains are parallel
forming waves where the CNSn(2)Ph3 fragments locate the peak and
bottompositions of thewavesas sidearms. In betweenthese parallel
puckered chains, there are channels wide enough to accommodate
the bulky phenyl groups, Fig. 2. The phenyl groups are arranged face-
spectrum of II shows the characteristic bands of mpym, Table 5,
which are absent in the IR spectrum of I. These data indicate that the
structure of II contains non-linearchains constructed bythe Cu(CN)4
building blocks bridged by the [Ph3Sn)OH2] or the
[Ph3Sn)mpym/Ph3Sn] spacers. The broad band at 541 cmꢀ1 due
to asymmetric nSn-C advocates the presence of trigonal plane Ph3Sn
units owing to their axial anchoring to two cyanide nitrogen atoms.
The presence of mpym in the network structure of II is supported by
to-face causing stabilization of the 2D-network structure by
pep
ꢀ
stacking (3.0 A) as well as H-bonds between the H-atoms of the
phenyl rings and the -cloud of another phenyl ring in the neigh-
p
boring layer and between H-atoms and the cyanide groups, Table 4.
the medꢀiu1m and weak bands at 3136 cmꢀ1
(nCH(pym)), 2932 and
3.1. Spectral characterization and structure of II
2860 cm
(
nCH(m)), 1598, 1544 and 1516 cmꢀ1
(
(
nC]C), 1438,
gCH).
1391 cmꢀ1
(
dCH), 1261 cmꢀ1
(
nCeN), 857 and 680 cmꢀ1
As single crystals of II were not obtained so far. Several experi-
mental techniques were used to accomplish a definitive character-
ization of its structure. The presence of ternary adducts; Ph3Sn
cation, cyanide groups and mpym in the structure of II was
confirmed by elemental analysis, TGA and spectroscopic methods.
Consulting the IR spectrum of II, Table 5, and that of I (vide supra)
indicates that they contain the Ph3Sn and CuCN fragments. In
consequence of bridging the tetrahedral Cu(CN)4 building blocks by
the Ph3Sn units via an essential covalent CueC^N/Sn bond, one
can realize the presence of nC^N band (2111 cmꢀ1) at higher wave-
numbers than the band of the genuine salt of the corresponding [Cu
(CN)4]3ꢀ anion (2076 cmꢀ1) [18], which contains non-bridged
cyanide groups. In addition, the stretching frequencies much higher
than those of the genuine salts; K3[Cu(CN)4] and [(nBu4N)3Cu(CN)4],
have been assigned to linear bridging between metal centers, while
frequencies near those of the salts are associated with terminal or
non-linear bridging CN groups [8,19,20]. It is also worth mentioning
that the cyanide band of II locates at more or less the same position
as that of the prototype I. On the other hand, the IR spectrum of II
exhibits a broad band at 3447 cmꢀ1 corresponding to nOH of the
water molecule. The broadening of this band indicates participation
of the water molecules in hydrogen bonds while TGA indicated
coordination of the water molecules to some tin atoms as they
release at temperature above 160 ꢁC (vide infra). Also the IR
The 1H NMR spectrum of II shows two broad overlapping peaks at
7.92 and 7.96 ppm corresponding to the aromatic protons of mpym,
while the methyl protons absorb at 2.05 ppm. This assignment was
supported by consulting the 1H NMR spectrum of mpym, which
exhibits sharp singlet, two doublets and one broad singlet at 8.95, 8.60,
7.45 and 2.30 ppm corresponding to H(2), H(6), H(5) and CH3,
respectively. The peaks are shifted upfield supporting the participation
of mpym in the formation of II. The 1H NMR spectrum of II exhibits
also, three broad peaksat 7.45, 7.76 and 7.78 ppm due tothe absorption
of the phenyl protons. These peaks are different in shape and position
than those observed in the 1H NMR spectrum of Ph3SnCl which appear
as well resolved multiplets in the range of 6.2e8.5 ppm. This obser-
vation indicates participation of the Ph3Snunits intheformation of the
structure of II. In addition to the peaks due to mpym and the Ph3Sn
units, aweak broad peak appears at 8.15 ppm corresponding to awater
molecule. This peak disappears on deuteriation by D2O. This down
field chemical shift indicates the coordination of the water molecules
and the presence of strong intramolecular hydrogen bonding between
the water protons and the cyanide nitrogen atoms. Thus, 1H NMR
spectra of mpym, Ph3SnCl and II support the presence of mpym, Ph3Sn
units and H2O in the structure of II.
The mass spectrum of II exhibits the base peak at m/z ¼ 351
corresponding to ph3Snþ isotopomer of the molecular ion. The
interpretation of the positive ion and negative ion polarity mass
spectra for II is listed in Table 6. The most important ion peak
appears at m/z ¼ 1584 corresponding to [(Ph3Sn)3Cu(CN)3(mpym)
CueC^N.H2O/SnPh3]þ which supports the participation of
mpym and the water molecule in the formation of the network
structure of II. On the other hand, the ESIꢀ mass spectrum of II
Table 4
ꢀ
Selected hydrogen bond lengths (A) for I.
N(5)eH(23)
N(5)eH(28)
N(5)eH(29)
N(9)eH(21)
C(6)eH(28)
2.858(7)
2.507(7)
2.804(6)
2.821(7)
2.618(9)
C(20)eH(21)
C(42)eH(18)
N(50)eH(19)
C(51)eH(22)
e
2.924(12)
2.979(11)
2.865(8)
2.999(8)
e
displays more than eleven peaks of [Cun(CN)nþ1]
ꢀ units, where the
base peak observed at m/z ¼ 564 corresponds to [Cu6(CN)7]ꢀ iso-
topomer of the molecular ion, indicating the polymeric nature of
the Cu(CN)4 building blocks.

1922
S.E.H. Etaiw et al. / Journal of Organometallic Chemistry 695 (2010) 1918e1923
Table 6
Ph3Sn units, CuCN fragments and the bipodal base; mpym as well as
the interlayer H2O.
The X-ray powder diffractograms of (I and II) which are the
products of the same ternary adducts, are very rich in sharp discrete
Interpretation of the mass spectra of the positive and negative ion polarity (ESIþ
)
and (ESIꢀ), respectively for [(Ph3Sn)3Cu(CN)4$mpym$H2O], II.
Ion
m/z
Ion
m/z
561
886
1001
1194
1584
652
741
830
921
1010
Snþ
120
197
274
351
719
115
206
295
384
473
564
[Ph3SnCu(CN)2mpym]þ
[(Ph3Sn)2CuCNmpym]þ
[(Ph3Sn)2Cu2(CN)3mpym]þ
[(Ph3Sn)3Cu(CN)3]þ
[(Ph3Sn)3Cu(CN)3mpymCuCNPhSnOH2]þ
Cu7(CN)ꢀ8
lines. They are quite different exhibiting different 2q values and
PhSnþ
different lattice constants. Thus, I and II are chemically and struc-
turally different. The structure of II contains the PT-4 [Cu(CN)4]3ꢀ
anion which is considered the main building block in construction
of growing number of coordination polymers [8,11]. It can bridge
the ph3Sn cations in much the same fashion that CNꢀ anions do,
except that the greater complexity of the [Cu(CN)4]3ꢀ ion leads to
three-dimensional polymers. Now, the point is investigating the
role of mpym and the water molecule that should act either as
guest molecules in the cavities of the three-dimensional framework
of the [(Ph3Sn)3Cu(CN)4] fragment, or as coordinated spacers to
provide wide enough space to accommodate the bulky phenyl
groups. Regarding the first case, it is well known that no coordi-
nation polymer is directly obtained as a material with empty
cavities (pores) large enough for guest incorporation since nature
tends to avoid empty space. Also, the guest molecules can be seen
as templates which are not covalently bond to the framework and
could, in principle, be removed if they are neutral.
In the case of II the nine phenyl groups per molecule acquire
wide space for incorporation and also, to avoid steric hindrance
which should arise between the phenyl groups of other molecules.
In the network of II, mpym and H2O could not be removed either
chemically or by heating up to 160 ꢁC. TGA analysis provides the
decomposition of II at 160 ꢁC, and shows that mpym and H2O are
released along with 1.5(Ph3SnCN) in the temperature range
160e280 ꢁC. Thus, mpym and H2O can be considered as coordi-
nated spacers in the network structure of II to provide cavities wide
enough for the bulky phenyl rings. Thus, the structure of II is built
up of PT-4 [Cu(CN)4]3ꢀ building blocks that are interconnected by
the (Ph3Sn) cations which acquire TBPY-5-configured structure.
The four-coordinate copper(I) sites are interconnected by two kinds
of non-linear spacers; eC^N/Sn(Ph3))O(H)eH.N^Ce and
eC^N/Sn(Ph3)eN(mpym)NeSn(Ph3))N^Ce, Scheme 1. The
Ph2Snþ
Ph3Snþ
(Ph3Sn)2OHþ2
Cu(CN)ꢀ2
Cu2(CN)ꢀ3
Cu3(CN)ꢀ4
Cu4(CN)ꢀ5
Cu5(CN)ꢀ6
Cu6(CN)ꢀ7
Cu8(CN)ꢀ9
Cu9(CN)ꢀ10
Cu10(CN)ꢀ11
Cu11(CN)ꢀ12
3.2. Thermogravimetric analysis of II
The thermogram shows the first step at 160e280 ꢁC, which
corresponds to the decomposition of 1.5(Ph3SnCN) and the mpym
molecule as well as the releasing of the interlayer water molecule
[observed
D
m ¼ ꢀ50.90% (676.32 g molꢀ1), calculated
m ¼ ꢀ50.84%
D
(675.55 g molꢀ1)]. This step indicates that the water molecule is
coordinated to some tin atoms O/Sn and may form hydrogen
bonding with the cyanide group. The weight loss in the second step at
300e400 ꢁC, is due to the loss of ½ Ph3SnCN [observed
D
m ¼ - 14.22%
(188.97 g molꢀ1), calculated
D
m ¼ ꢀ14.14% (187.85 g molꢀ1)]. The
residue at 400e640 ꢁC was Ph3SnCu(CN)2 which was found to be
stable at higher temperatures [19] under dry pure nitrogen atmo-
sphere [observed mass ¼ 34.87% (463.34 g molꢀ1), calculated
mass ¼ 35.01% (465.25 g molꢀ1)]. At higher temperatures over 750 ꢁC
and in the presence of the contaminated oxygen, II undergoes
complete decomposition and oxidation to give the final product of
mixed oxides. The molecular weight of the residue obtained after
complete thermolysis of II is coincident with 2(SnO2) þ Cu2O
[observed mass ¼ 34.00% (451.74 g molꢀ1), calculated mass ¼ 33.45%
(444.5 g molꢀ1)]. Consultingthethermogravimetricdataof II, leads to
the conclusion that the structure of II contains the ternary adducts;
C
Cu
C
C
C
Ph
Ph
Ph
Ph
N
Ph
N
Ph
Sn
Sn
Ph
Sn
N
Sn
Ph
L
N
N
Ph
L
Ph
C
H
Ph
Ph
C
Cu
C
Cu
C
O(H)
Ph
Ph
Sn Ph
N
N
N
C
H
H
O(H)
O(H)
Ph
Ph
Ph
Ph
Cu
C
Sn Ph
N
Sn Ph
C
Ph
Sn
Ph
C
Ph
Ph
Sn
N
Ph
Sn
Ph
N
L
N
C
Sn
Ph
N
Ph
L
Ph
N
N
C
Ph
Ph
C
Ph
H
C
Cu
Cu
O(H)
Ph
Ph
Sn Ph
N
C
Cu
Scheme 1. Schematic representation of the proposed structure of the SCP II; L ¼ (mpym).

S.E.H. Etaiw et al. / Journal of Organometallic Chemistry 695 (2010) 1918e1923
1923
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presence of these non-linear spacers was confirmed by IR spectrum
that display nC^N at higher frequencies than those of the genuine
salt anion, [Cu(CN)4]3ꢀ. Also, the presence of the band of the
asymmetric stretching of SneC bonds indicates the presence of
TBPY-5 Ph3Sn units and confirms the bridging nature of these
groups. It is a matter of fact that the actual structure of II cannot be
defined categorically, but its structure was predicated by compar-
ison with the prototype, early reported, compounds [21,22].
Appendix A. Supplementary data
CCDC 773506 contains the supplementary crystallographic data
for I. These data can be obtained free of charge via http://www.
ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,
UK; fax: þ44 1223 336 033; or e-mail: deposit@ccdc.cam.ac.uk.
[13] J.W. Eastes, W.M. Burgess, J. Am. Chem. Soc. 64 (1942) 1187.
[14] J.W. Eastes, W.M. Burgess, J. Am. Chem. Soc. 64 (1942) 2715.
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K. Harris, Organometallics 12 (1993) 3232.
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Commun. (1992) 740.
[18] R.A. Penneman, L.H. Jones, J. Chem. Phys. 24 (1956) 293.
[19] A.M.A. Ibrahim, J. Organomet. Chem. 556 (1998) 1.
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