Degradation versus expansion of the AgX frameworks: Formation of oligomeric and polymeric silver complexes from reactions of bulk AgX with N, N-bis(diphenylphosphanylmethyl)-2-aminopyridine

Article abstract of DOI:10.1021/cg4002048

Reactions of N,N-bis(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy) with [Ag(MeCN)₄]ClO₄ or AgX (X = Cl, Br, I, SCN, CN) afforded a family of oligomeric and polymeric complexes: [Ag₂(MeOH) (bdppmapy)₂](ClO₄)₂ (1), [AgCl(bdppmapy)] (2), [AgBr(bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN(bdppmapy)] (5), [{(η²-bdppmapy)Ag(μ-CN)AgCN}₂(μ-bdppmapy)] (6), [Ag₄(μ-CN)₄(μ-bdppmapy)] (7), and [Ag ₂(μ-CN)(μ-bdppmapy)₂][Ag₅(μ-CN) ₆] (8). Compounds 1-8 were characterized by elemental analyses, IR spectra, ¹H and ³¹P{¹H} NMR, electrospray ionization (ESI) mass spectra, powder X-ray diffraction (XRD), and single-crystal X-ray diffraction. Compounds 1-3 and 5 hold a one-dimensional (1D) chain in which [Ag(MeOH)]⁺ or [AgX] motifs are linked by bdppmapy bridges. Compound 6 has a tetrameric framework in which two linear [(η²-bdppmapy)Ag(μ-CN)AgCN] fragments are connected by a μ-bdppmapy ligand. Compound 7 contains a 1D staircase chain in which two zigzag [Ag(μ-CN)]_n chains are linked by pairs of μ-bdppmapy bridges. Compound 8 possesses an unprecedented three-dimensional (3D) structure in which the channels of one 3D anionic [Ag₁₀(μ-CN) ₁₂]_n^2n- net are plugged with 1D cationic [Ag₄(μ-CN)₂(μ-bdppmapy)₄] _n²ⁿ⁺ chains. The degradation versus expansion of the bulk AgX frameworks do affect the formation of [Ag_aX_b]-based oligomers and polymers when AgX is treated with bdppmapy. The photoluminescent properties of 1-8 in the solid state were also investigated.

Full text of DOI:10.1021/cg4002048

Article
pubs.acs.org/crystal
Degradation versus Expansion of the AgX Frameworks: Formation of
Oligomeric and Polymeric Silver Complexes from Reactions of Bulk
AgX with N,N‑Bis(diphenylphosphanylmethyl)-2-aminopyridine
Ju-Hua Yang,†,‡ Xin-Yi Wu,† Run-Tian He,† Zhi-Gang Ren,*,†,§ Hong-Xi Li,† Hui-Fang Wang,†
̈
and Jian-Ping Lang*,†,‡
†College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People’s Republic of
China
‡
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, People’s Republic of China
§Institute of Materials Research and Engineering, Agency for Science, Technology and Research, 3 Research Link, Singapore 117602,
Singapore
S
* Supporting Information
A B S T R A C T : R e a c t i o n s o f N , N - b i s -
(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy)
with [Ag(MeCN)4]ClO4 or AgX (X = Cl, Br, I, SCN, CN)
afforded a family of oligomeric and polymeric complexes:
[Ag2(MeOH)(bdppmapy)2](ClO4)2 (1), [AgCl(bdppmapy)]
(2), [AgBr(bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN-
(bdppmapy)] (5), [{(η2-bdppmapy)Ag(μ-CN)AgCN}2(μ-
bdppmapy)] (6), [Ag4(μ-CN)4(μ-bdppmapy)] (7), and
[Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-CN)6] (8). Compounds
1
1−8 were characterized by elemental analyses, IR spectra, H
and 31P{1H} NMR, electrospray ionization (ESI) mass spectra,
powder X-ray diffraction (XRD), and single-crystal X-ray diffraction. Compounds 1−3 and 5 hold a one-dimensional (1D) chain
in which [Ag(MeOH)]+ or [AgX] motifs are linked by bdppmapy bridges. Compound 6 has a tetrameric framework in which
two linear [(η2-bdppmapy)Ag(μ-CN)AgCN] fragments are connected by a μ-bdppmapy ligand. Compound 7 contains a 1D
staircase chain in which two zigzag [Ag(μ-CN)]n chains are linked by pairs of μ-bdppmapy bridges. Compound 8 possesses an
2n−
unprecedented three-dimensional (3D) structure in which the channels of one 3D anionic [Ag10(μ-CN)12]n net are plugged
2n+
with 1D cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n chains. The degradation versus expansion of the bulk AgX frameworks do
affect the formation of [AgaXb]-based oligomers and polymers when AgX is treated with bdppmapy. The photoluminescent
properties of 1−8 in the solid state were also investigated.
AgCN consists of rows of linear [AgCN]n chains parallel to
[001] with alternating long Ag−C and short Ag−N
distances.10e Cracking its framework through phosphine ligands
form discrete [Aga(CN)b]-based and one-dimensional (1D)
[Aga(CN)b]n-based complexes.12 Che et al. reported that
reactions of AgCN with equimolar tricyclohexylphosphine
(PCy3) produced one 1D polymer [(Cy3P)Ag(NCAgCN)]n,
whose structure contains a 1D [AgCN]n backbone, while
employment of excess PCy3 yielded one discrete complex
[(Cy3P)2Ag(NCAgCN)], which has a discrete [Ag2(CN)2]
species in the structure. However, no reports have described
the framework expansion of AgX (e.g., the 1D chain of bulk
AgCN) to the 2D or 3D [AgaXb]-based net, when it reacts with
phosphine ligands.
INTRODUCTION
■
In the past decades, the coordination chemistry of silver(I)
halides and pseudohalides of various phosphine ligands has
attracted much interest due to not only interesting structural
diversity1−3 but also many potential applications in catalysis,4
potential antitumor agents,5 and luminescent materials.6 These
complexes are usually prepared through their reactions with
monophosphine ligands (e.g., PPh3),7 diphosphine ligands (e.g.,
bis(diphenylphosphino)methane (dppm))8,3a and polyphos-
p h i n e l i g a n d s ( e . g . , N , N , N ′ , N ′ - t e t r a -
(diphenylphosphanylmethyl) ethylene diamine (dppeda)).9 As
we know, bulk AgX (X = halide and pseudohalide) shows
different frameworks in the solid state,10 and its framework
always tends to be degraded into one or more small [AgaXb]-
based structural motifs in solution when it reacts with
phosphine ligands. Such motifs are further combined by these
ligands to generate oligomeric and polymeric [AgaXb]/
phosphine complexes.8,11 For example, the structure of bulk
Received: February 2, 2013
Revised: March 19, 2013
Published: March 20, 2013
© 2013 American Chemical Society
2124
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design
Article
Scheme 1. Reactions of bdppmapy with Ag(I) Salts
Besides the silver(I) phosphine complexes, it is well-known
that the coordination chemistry of the silver(I) complexes of
nitrogen donor ligands are also abundant.13 The combination
of both N and P ends in one ligand may make its silver(I)
chemistry more interesting as such Ag(I) complexes showed
unique molecular architectures and physicochemical proper-
ties.14 We have been involved in the design and coordination
chemistry of some tetra amino-phosphine and phosphine-
pyridyl ligands.15 A group of Cu(I) and Ag(I) complexes of
these ligands with interesting structures including the dinuclear
complexes and 1D and 2D polymeric complexes have been
isolated. For example, the reactions of AgX (X = Cl, Br, I, CN,
SCN, and dicyanamide (dca)) with N-diphenylphosphanyl-
methyl-4-aminopyridine (dppmapy) afforded a set of 1D or 2D
[Ag2X2]-based coordination polymers.15a In these reactions, the
framework of the bulk AgX was all broken into a [Ag2X2]
species in the presence of dppmapy. The cyanide complex
contains a linear [(CN)Ag(μ-CN)Ag] motif while other
complexes all hold a rhombic [Ag(μ-X)2Ag] motif. Could
other phosphine-pyridyl ligands induce the framework
expansion of the bulk AgX to form 2D or 3D Ag/X/P
coordination polymers with unique structures? In this work, we
chose another P/N hybrid ligand, N, N-bis-
(diphenylphosphanylmethyl)-2-aminopyridine (bdppmapy),
because it has different P atom numbers and steric hindrance
from dppmapy and may coordinate Ag atoms via both N atom
of this pyridyl group and P atoms of the two phosphanyl
groups. When it reacted with AgX (X = ClO4, Cl, Br, I, SCN,
and CN), a set of 1D polymeric complexes, [Ag2(MeOH)-
(bdppmapy)2](ClO4)2 (1), [AgCl(bdppmapy)] (2), [AgBr-
(bdppmapy)] (3), [AgI(bdppmapy)] (4), [AgSCN-
(bdppmapy)] (5), one discrete complex [{(η2-bdppmapy)Ag-
(μ-CN)AgCN}2(μ-bdppmapy)] (6), one 1D polymeric
complex [Ag4(μ-CN)4(μ-bdppmapy)] (7), and one 3D
polymeric complex [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-
CN)6] (8), were isolated. Although in the structures of 1−3
and 5−8, the AgX framework was degraded into small
structural motifs like the [AgX] unit in 2−5, the [Ag(μ-
CN)AgCN] unit in 6, and the [Ag2(μ-CN)]+ cationic unit in 8,
or reformed into the 1D [Ag(μ-CN)]n chain in 7, compound 8
witnessed an unprecedented framework expansion from the 1D
chain of AgCN to a 3D [Ag10(μ-CN12)n2n−-based net. Herein,
we report their isolation, structural characterization, and
luminescent properties.
RESULTS AND DISCUSSION
■
Synthetic and Spectral Aspects. Treatment of bdppmapy
with [Ag(MeCN)4]ClO4 (molar ratio = 1: 1) in MeOH for 0.5
h at ambient temperature followed by filtration and diffusion of
Et2O into the filtrate or evaporation of solvents from the filtrate
led to the formation of 1 (51% yield) (Scheme 1). Analogous
reactions of bdppmapy and equimolar AgX (X = Cl, Br, I) for 1
2125
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design
Article
h followed by filtration and evaporation of solvents from the
filtrate formed 2, 3, and 4 with less than 10% yields, which may
be due to the low solubility of AgX in MeCN. Increasing the
bdppmapy/AgX molar ratio to 1.5:1 at the same conditions
could generate the same products 2 (79% yield), 3 (78% yield),
and 4 (84% yield) (Scheme 1). Refluxing the MeCN solution
containing bdppmapy and AgX (molar ratio = 1.5: 1) followed
by a similar workup gave rise to white powders of 2−4
(confirmed by IR and powder XRD analyses (Supplementary
Figure S1) with slightly improved yields. Treatment of a
CH2Cl2 solution of bdppmapy with a suspension of equimolar
AgSCN in EtOH at ambient temperature followed by filtration
and diffusion of Et2O into the filtrate afforded 5 in 60% yield
(Scheme 1). As discussed later in this article, the MeOH
molecules are weakly coordinated at Ag centers in the cationic
chain of 1. They might be replaced by other halides or
pseudohalides. Complex 1 was thus mixed with two equiv of
NH4X (X = Cl, Br, I, SCN) in MeCN. The resulting solution
was stirred for 0.5 h at room temperature. Fast evaporation of
MeCN from the solution could afford 2 (75% yield), 3 (72%
yield), 4 (76% yield), and 5 (66% yield), respectively (Scheme
1). Their structures were confirmed by elemental analyses
(Supplementary Table S1), IR spectra (Supplementary Figure
part of the AgCN chain was broken into a [Ag2(μ-CN)]+
cationic unit, while another part was expanded into a rare 3D
2n−
anionic [Ag10(μ-CN)12]n
net. These in situ-generated
different [Aga(μ-CN)b] structural motifs are further combined
by bdppmapy ligands, thereby forming the aforementioned
products 6−8.
Compounds 1−8 are stable toward air and moisture.
Compound 1 is soluble in MeOH, MeCN, DMF, and
DMSO, while 2−8 are slightly soluble in MeCN and DMSO
but insoluble in other organic solvents. The elemental analyses
are consistent with their chemical formula. In their IR spectra,
the stretching vibration at 1097 cm−1 in 1 is assignable to the
uncoordinated perchlorides, while a strong peak at 2090 cm−1
in 5 is the characteristic stretching vibration of the S-bonded
thiocyanate. In the cases of 6−8, the CN stretching
vibrations of the cyanides are located at 2138 (6), 2150 (7),
and 2199/2142 (8) cm−1, respectively. Such differences may be
due to the different coordination environments for the
1
cyanides. The H NMR spectra of 1−8 in DMSO-d6 at room
temperature all show the signals of the bdppmapy ligands
including a multiplet at 7.00−7.80 ppm for the phenyl groups, a
doublet at 5.60−7.00 ppm and a multiplet at 5.60−7.00 ppm
for the pyridyl group, and a singlet at 4.60−5.30 ppm for the
methylene group. For 1, a singlet at 3.17 ppm for the methyl
group in MeOH is also discovered. In the 31P{1H}NMR spectra
of 2−5, 7, and 8, only a broad peak (−4.66 ppm for 2, −2.19
ppm for 3, −8.29 ppm for 4, −1.61 ppm for 5, −1.72 ppm for
7, and 1.63 ppm for 8) is clearly observed, while in those of 1
and 6, two broad peaks (−1.14 and 1.79 ppm for 1 and −8.35
and −6.37 ppm for 6) are found, which may be related to the
different coordination environments of bdppmapy ligands.
Relative to that of bdppmapy (−22.811 ppm), these chemical
shifts are larger, which may be due to the coupling between
107Ag (109Ag) and 31P nuclei.
1
S2), H NMR (Supplementary Figure S3), and powder X-ray
diffraction (Supplementary Figure S4). However, attempts of
analogous transformations in solid state by grinding complex 1
and two equiv of NH4X (X = Cl, Br, I, SCN) in an agate mortar
for 25 min failed to generate 2−5. This is because 1 was
decomposed during the period of its grinding with NH4X,
which was confirmed by PXRD (Supplementary Figure S5).
Intriguingly, reactions of a suspension of AgCN in MeCN
with a solution of equimolar bdppmapy in CH2Cl2 at ambient
temperature for 1 h followed by filtration and diffusion of Et2O
into the filtrate produced a discrete tetranuclear complex 6 in
50% yield. Refluxing the MeCN solution containing bdppmapy
and AgCN (molar ratio = 1:2) for 2 h followed by a standard
workup produced a 1D polymeric complex 7 (colorless
rhombic crystals) in 33% yield and several long column
crystals of 8, which were separated under microscopy.
However, extending the reflux time to 4 h for the above
reactions produced a rare 3D polymeric complex 8 in 31% yield
and 7 (38% yield). Further elongated reflux time did not
change the ratio of 7 and 8 in this system, implying that 7 could
not be converted into 8 and vice versa. In fact, we refluxed the
solution of 6 or 7 (with or without bdppmapy) in MeCN for
2−4 h and could not isolate any crystals of 8. Increasing the
molar ratios of bdppmapy/AgCN such as 1:4 did not form
either 7 or 8, but yielded very thin plates of an unknown
complex. Its PXRD patterns (Supplementary Figure S1g) could
not match those of 7 and 8, implying that it might be a new
compound. The poor crystal quality of this compound excluded
our efforts to determine its crystal structure. These results
showed the framework of the bulk AgCN could be degraded
into various[Aga(CN)b]-based structural motifs in this reaction
system, which definitely depends on the reaction time and the
bdppmapy/AgCN molar ratios. Rational control of these
conditions and careful crystallization could generate various
bdppmapy/AgCN oligomeric and polymeric complexes with
different topological structures. As described later in this article,
in the cases of 2−5, the 3D framework of AgX was cleaved into
the smallest motif [AgX]. In the case of AgCN, its linear chain
was degraded into two [Ag(μ-CN)AgCN] units in 6 or
reformed into two 1D zigzag [Ag(μ-CN)]n chains in 7. In 8,
The positive-ion ESI mass spectra of 1−8 in MeCN
(Supplementary Figure S6) were measured to obtain some
information about their behaviors in solution. The assignments
were made by inspection of peak positions and isotopic
distributions. In the positive-ion ESI-MS of 1, 3, and 5, two
cationic peaks were found at m/z = 597.1 for the [Ag-
(bdppmapy)]+ cation (Figure 1a) and at m/z = 1089.3 for the
[Ag(bdppmapy)2]+ cation (Figure 1b), respectively. However,
in the ESI-MS of 2, 4, and 6−8, only one peak at m/z = 1089.3
for the [Ag(bdppmapy)2]+ cation was discovered. The
existence of these cationic fragments in the positive-ion ESI-
MS of 1−8 implied that their frameworks may partially
dissociate into various small cationic fragments under the ESI
mass conditions. For 4, attempts to grow single crystals suitable
for X-ray analysis failed. However, its PXRD patterns are similar
to those of 2−3 (Supplementary Figure S1b), which, along with
1
its data of IR, elemental analysis, and H NMR, suggested that
4 may have a similar structure to that of 2, 3, and 5. The
identities of 1−3, 5, 6·CH2Cl2, 7·MeCN, and 8 were further
confirmed by single-crystal X-ray diffraction.
Crystal Structure of [Ag2(MeOH)(bdppmapy)2](ClO4)2
(1). Compound 1 crystallizes in the triclinic space group P1,
̅
and its asymmetric unit contains one [(Ag0.5)2(bdppmapy)2Ag-
(MeOH)]2+ dication and two discrete ClO4− anions. As shown
in Figure 2, Ag1 is coordinated with two P atoms from two
neighboring bdppmapy ligands and one O atom of the MeOH
molecule, forming an approximately trigonal planar geometry.
In addition, there exists a weak interaction between Ag1 and
N1 of the o-pyridyl group (2.789 Å). Both Ag2 and Ag3 adopt a
2126
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design
Article
by two P atoms from neighboring bdppmapy ligands and one
Cl (2) or Br (3) atom or one S atom from the terminal
thiocyanide (5). The Ag atoms in 2, 3, and 5 are connected by
the bdppmapy bridges to form a 1D chain extending along the
b (for 2 and 3) (Supplementary Figures S7 and S8) and a (for
5) axis. For 2 or 3, the contact between Ag1 and the N1 is
3.775 and 3.742 Å, respectively, implying the N atom of the o-
pyridyl group of bdppmapy in 2 or 3 remains intact. For 5, the
N1 atom of the o-pyridyl group of bdppmapy in one chain
keeps intact (Ag1···N1 = 3.088 Å), while the N6 atom of the o-
pyridyl of bdppmapy in the other chain weakly binds to Ag2
(2.778 Å). The mean Ag−P bond length (2.4253(10) Å for 2,
2.4248(11) Å for 3, and 2.4422(13) Å for 5) (Table 1) is
longer than that of 1 but somewhat shorter than those of the
corresponding ones in the trigonally coordinated Ag(I)
complexes such as [Ag(P(C6H11)3)2Cl] (2.471(3) Å), [Ag(P-
( C 6 H 1 1 ) 3 ) 2 B r ] ( 2 . 4 7 3 4 ( 9 ) Å ) , 1 6 b a n d
[(PPh2(CH2)6PPh2)2Ag2(SCN)2]n (2.517(12) Å).17c The
Ag−X bond lengths (2.4756(10) Å for X = Cl (2);
2.5890(7) Å for X = Br (3); 2.5364(15) Å for X = S(SCN)
(5)) are shorter than those of the corresponding ones in
[Ag(P(C6H11)3)2Cl] (2.489(1) Å), [Ag(P(C6H11)3)2Br]
(2.618(1) Å), and [(PPh2(CH2)6PPh2)2Ag2(SCN)2]n
(2.677(2) Å).
Figure 1. (a) Observed (top) and calculated (bottom) isotopic
patterns for the [Ag(bdppmapy)]+ cation. (b) Observed (top) and
calculated (bottom) isotopic patterns for the [Ag(bdppmapy)2]+
cation.
Crystal Structure of [{(η2-bdppmapy)Ag(μ-CN)-
AgCN}2(μ-bdppmapy)]·CH2Cl2 (6·CH2Cl2). Compound
6·CH2Cl2 crystallizes in the monoclinic space group P2/c,
and its asymmetric unit contains half a [{(η2-bdppmapy)Ag(μ-
CN)AgCN}2(μ-bdppmapy)] molecule and half a CH2Cl2
solvent molecule. As shown in Figure 4, three bdppmapy
ligands in 6 reveal two different coordination modes. One
mode is that bdppmapy chelates at Ag1 via the two P (P1 and
P2) ends (η2-bdppmapy), whereas the other is that bdppmapy
works as a bridge to link two Ag1 atoms via P3 (μ-bdppmapy).
The four Ag atoms also exhibit different coordination
geometries. Ag1 (or Ag1A) is tetrahedrally coordinated by
three P atoms from two different bdppmapy ligands and one N
atom from a cyanide. Ag2 is linearly coordinated by two C
atoms from two cyanides. There is no interaction between Ag
center and the N1 atom of the o-pyridyl group of bdppmapy in
6. The tetranuclear structure of 6 may be viewed as being built
of two linear [(η2-bdppmapy)Ag(μ-CN)AgCN] fragments
bridged by a μ-bdppmapy ligand. There is a 2-fold axis running
through the N4, C32, and C35 atoms. The mean Ag−P bond
length (2.4871(16) Å) (Table 1) in 6 is shorter than those
containing tetrahedrally coordinated Ag such as [Ag-
(PPh2Cy)3(CN)]·5H2O (2.5214(14) Å, Cy = cyclohexyl)18a
and [Ag(PPh3)3(dca)]·C6H5Cl (2.556(2) Å).18b The Ag1−N5
bond length (2.369(6) Å) is comparable to that of [Ag-
(PPh3)3(dca)]·C6H5Cl (2.338(2) Å),18b but longer than that
found in [Ag2(μ-CN)(PPh3)3][Ag(CN)2]·py (2.260(2) Å).12b
The [(μ-CN)AgCN]− ion binds to [(η2-bdppmapy)Ag]+ with
the C50−Ag2−C49, Ag2−C50−N6, and Ag2−C49−N5 angles
being 175.1(3)°, 177.4(9)°, and 174.3(7)°, suggesting the
geometry of the [(μ-CN)AgCN]− moiety remains close to
linearity. The Ag2−C49 and Ag2−C50 bond lengths in 6 are
normal relative to those of [(Cy3P)2Ag(NCAgCN)].12a
Figure 2. View of a section of the 1D chain (extending along the
(−1,1,1) direction) of 1 with a labeling scheme and 30% thermal
ellipsoids. All hydrogen atoms are omitted for clarity. Symmetry code
A: 1 − x, 1 − y, 1 − z.
linear geometry, coordinated with two P atoms from two
neighboring bdppmapy ligands. There is a crystallographic
inversion center being at Ag2. Each bdppmapy alternatively
links the two-coordinated and three-coordinated Ag atoms to
form a 1D cationic chain extending along the (−1,1,1)
direction. The mean two-coordinated Ag−P bond length
(2.374(2) Å) (Table 1) is slightly shorter than that found in
the two-coordinated Ag(I) complex [(Ph3P)2Ag]BF4
(2.4198(13) Å).16a The mean trigonally coordinated Ag−P
bond length (2.3984(16) Å) is shorter than those observed in
the trigonally coordinated Ag(I) complexes such as [Ag(P-
(C6H11)3)2Cl] (2.471(3) Å),16b [AgL(PPh3)2] (2.448(2) Å, L
= 2,4,6-trichlorophenolate),17a and [Ag(H2O)L2]BF4 (2.426(3)
Å, L = tris(2-furyl)phosphine).17b The Ag1−O1 bond length
(2.529(5) Å) in 1 is much longer than those found in
[AgL(PPh3)2] (2.235(3) Å, L = 2,4,6-trichlorophenolate) and
[Ag(H2O)L2]BF4 (2.365(2) Å, L = tris(2-furyl)phosphine),
indicating that the interaction of Ag(I) center with the MeOH
molecule is relatively weak.
Crystal Structures of [AgX(bdppmapy)] (2, X = Cl; 3, X
= Br; 5, X = SCN). Compounds 2, 3, and 5 crystallize in the
orthorhombic space group Pbca, and their asymmetric units
contain one discrete [AgX(bdppmapy)] (2, X = Cl; 3, X = Br)
molecule or two independent [AgSCN(bdppmapy)] molecules.
Because their molecules are structurally similar, only the view of
a section of one of the two independent 1D chains of 5 is
presented in Figure 3. Each Ag1 atom is trigonally coordinated
Crystal Structure of [Ag4(μ-CN)4(μ-bdppmapy)]·MeCN
(7·MeCN). Compound 7·MeCN crystallizes in the monoclinic
space group C2/c, and its asymmetric unit contains half a
[Ag4(μ-CN)4(bdppmapy)] molecule and half a MeCN solvent
molecule. Compound 7 may be viewed as having a 1D staircase
chain (extending along the (1,1,1/2) direction) (Figure 5) in
2127
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design
Article
a
Table 1. Selected Bond Lengths (Å) and Angles (deg) for 1−3 and 5−8
compound 1
Ag(1)−P(1)
Ag(1)−P(3)
Ag(3)−P(4)
2.4084(17)
2.3884(16)
2.374(2)
Ag(2)−P(2)
Ag(2)−P(2A)
Ag(3)−P(4A)
2.3744(14)
2.3744(14)
2.374(2)
Ag(1)−O(1)
2.529(5)
P(3)−Ag(1)−P(1)
P(4)−Ag(3)−P(4A)
P(1)−Ag(1)−O(1)
152.75(5)
180.00(16)
95.83(13)
P(2)−Ag(2)−P(2A)
P(3)−Ag(1)−O(1)
180.00(1)
111.03(13)
compound 2
compound 3
compound 5
compound 6
Ag(1)−P(1)
Ag(1)−Cl(1)
P(1)−Ag(1)−P(2A)
P(1)−Ag(1)−Cl(1)
2.4186(9)
2.4756(10)
127.57(3)
117.88(3)
Ag(1)−P(2A)
2.4319(10)
113.26(3)
P(2A)−Ag(1)−Cl(1)
Ag(1)−P(1)
Ag(1)−Br(1)
P(1)−Ag(1)−P(2A)
P(1)−Ag(1)−Br(1)
2.4172(11)
2.5890(7)
128.32(4)
117.63(3)
Ag(1)−P(2A)
2.4323(11)
113.07(3)
P(2A)−Ag(1)−Br(1)
Ag(1)−P(1)
Ag(1)−S(1)
P(2A)−Ag(1)−P(1)
P(2A)−Ag(1)−S(1)
2.4473(14)
2.5351(16)
130.50(5)
117.59(5)
Ag(1)−P(2A)
2.4332(13)
111.02(5)
P(1)−Ag(1)−S(1)
Ag(1)−P(1)
Ag(1)−P(3)
Ag(2)−C(50)
P(2)−Ag(1)−P(1)
P(3)−Ag(1)−P(2)
N(5)−Ag(1)−P(2)
C(50)−Ag(2)−C(49)
Ag(2)−C(49)−N(5)
2.5097(16)
2.4488(16)
2.031(10)
93.87(6)
Ag(1)−P(2)
Ag(1)−N(5)
Ag(2)−C(49)
P(3)−Ag(1)−P(1)
N(5)−Ag(1)−P(1)
N(5)−Ag(1)−P(3)
Ag(1)−N(5)−C(49)
Ag(2)−C(50)−N(6)
2.5027(18)
2.370(6)
2.051(8)
132.54(5)
102.22(16)
103.59(17)
151.9(6)
121.30(5)
97.05(17)
175.1(3)
174.3(7)
177.4(9)
compound 7
compound 8
Ag(1)−P(1)
Ag(2)−C(18)
Ag(1)−N(4)
N(3)−Ag(1)−P(1)
N(3)−Ag(1)−N(4)
2.396(2)
2.093(9)
2.248(7)
129.65(19)
107.9(3)
Ag(1)−N(3)
Ag(2)−C(19A)
2.210(7)
2.054(8)
N(4)−Ag(1)−P(1)
C(19A)−Ag(2)−C(18)
121.35(19)
178.1(3)
Ag(1)−P(1)
Ag(2)−N(3)
Ag(2)−N(6)
Ag(3)−C(34)
Ag(4)−C(33A)
N(5)−Ag(1)−P(1)
N(6)−Ag(2)−N(3)
C(34)−Ag(3)−N(7)
2.4509(17)
2.291(8)
2.128(7)
2.044(10)
2.048(9)
122.50(17)
110.5(3)
173.0(3)
Ag(1)−N(5)
Ag(2)−N(4)
Ag(3)−N(7)
Ag(4)−C(33)
Ag(2)−Ag(4E)
N(6)−Ag(2)−N(4)
N(4)−Ag(2)−N(3)
C(33)−Ag(4)−C(33A)
2.181(5)
2.140(8)
2.054(7)
2.048(9)
3.3138(11)
137.1(3)
112.3(2)
171.7(4)
a
Symmetry codes for 1 A, 1 − x, 1 − y, 1 − z; for 2 and 3 A, 1/2 − x, 1/2 + y, z; for 5 A, − 1/2 + x, y, 3/2 − z; for 7 A, x, − y, − 1/2 + z; for 8 A,
−x, y, 3/2 − z; B, − x, 1 − y, 1 − z; E, − x, 1 − y, 1 − z.
which each 24-membered [Ag6(μ-CN)4(bdppmapy)2] macro-
metallocycle unit (Figure 5) is fused by sharing four silver ions
and two bdppmapy ligands. Alternatively, this structure may be
considered as being built of two parallel 1D zigzag [Ag(μ-
CN)]n chains linked by the μ-bdppmapy bridges on the Ag1
atom and its symmetry-related Ag centers. The Ag centers in 7
show two different coordination geometries. Ag1 is trigonally
coordinated by one P atom from the bdppmapy ligand and two
N atoms from two cyanides. In addition, a weak interaction
(2.916 Å) between Ag1 and N1 of the o-pyridyl group of the
ligand is observed. Ag2 is linearly coordinated by two C atoms
from two cyanides. The Ag1−P1 bond length (2.396(2) Å)
(Table 1) in 7 is almost the same as that of 1 but shorter than
those of the corresponding ones of 2, 3, and 5. The mean Ag1−
N bond length (2.229(7) Å) is close to the corresponding one
in [(Cy3P)Ag(NCAgCN)]n (2.235(5) Å) but shorter than that
found in [(Cy3P)2Ag(NCAgCN)] (2.627(14) Å).12a The
2128
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design
Article
Crystal Structure of [Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-
CN)6] (8). Compound 8 crystallizes in the monoclinic space
group C2/c and its asymmetric unit consists of half a [Ag2(μ-
CN)(μ-bdppmapy)2]+ cation and half a [Ag5(μ-CN)6]− anion.
As shown in Figure 6a, two [Ag2(μ-CN)]+ fragments are linked
by a pair of bdppmapy bridges to form one 18-membered
cationic [Ag4(μ-CN)2(μ-bdppmapy)2]2+ macrometallocycle
unit. Such a unit is further connected to other equivalent
ones by two couples of bdppmapy bridges to yield a 1D ladder-
2n+
type cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n chain extended
Figure 3. View of a section of the 1D chain (extending along the a
axis) of 5 with a labeling scheme and 30% thermal ellipsoids. All
hydrogen atoms are omitted for clarity. Symmetry code A: − 1/2 + x,
y, 3/2 − z.
along the c axis (Figure 6b). Ag1 in this chain is trigonally
coordinated with two P atoms from the neighboring bdppmapy
ligands and a C(N) atom from a cyanide. The mean Ag−P
bond length (2.4618(17) Å) (Table 1) in 8 is in-between that
of 1 (or 7) and that of [Ag(CN)(P(C6H11)3)2] (2.4803(9)
Å).16b The Ag1···N1 contact is ca. 3.448 Å, suggesting no
interaction between Ag1 and N1 of the o-pyridyl group of
bdppmapy. The mean Ag1−C and Ag1−N bond lengths are
normal.
As shown in Figure 6c, 12 silver (I) ions combine 12
cyanides to form a 36-membered [Ag12(μ-CN)12] macro-
metallocycle unit (Figure 6c). The Ag atoms in the unit show
two different coordination modes. Ag2 is trigonally coordinated
by two N and one C(N) atoms from three cyanides, while Ag3
and Ag4 are two-coordinated by one C atom and one C(N)
atom from two cyanides. Such a unit is further fused with its
equivalent ones to create a 2D (6,3) anionic [Ag10(μ-
2n−
CN)12]n corrugated network extending along the ac plane
Figure 4. View of the molecular structure of 6 with a labeling scheme
and 30% thermal ellipsoids. All hydrogen atoms are omitted for clarity.
Symmetry code A: − x, y, −1/2 − z.
(Figure 6d). Interestingly, this 2D network is interpenetrated
with its symmetry-related ones to generate a unique 3D
2n−
[Ag10(μ-CN)12]n net with 1D rhombic channels extending
along the c axis (Figure 6e). The volume of these channels is
calculated to be 5913.2 Å3 (84.8%) per unit cell (calculated by
using Platon program19). Each channel has a section area of
17.37 × 12.93 Å2 and is filled with one ladder-shaped cationic
[Ag(μ-CN)2]− unit is approximately linear and the Ag2−C
bond lengths are also normal relative to those of 6.
Figure 5. View of a section of the 1D staircase chain (extending along the (1,1,1/2) direction) of 7. The circled part shows one 24-membered
[Ag6(μ-CN)4(μ-bdppmapy)2] macrometallocycle of 7, with a labeling scheme and 30% thermal ellipsoids. All H atoms are omitted for clarity. Atom
color codes: Ag, turquiose; P, pink; N, blue; C, black. Symmetry codes: A, x, − y, − 1/2 + z; B, 1 − x, y, 3/2 − z; C, 1 − x, − y, 1 − z.
2129
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design
Article
Figure 6. (a) View of the 18-membered cationic [Ag4(μ-CN)2(μ-bdppmapy)2]2+ macrometallocycle in 8. Symmetry codes: A, x, 1 − y, −1/2 + z; B,
1 − x, 1 − y, 1 − z; C, 1 − x, y, 3/2 − z. (b) View of a portion of the 1D ladder-type cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chain (extending
along the c axis) in 8. (c) View of the 36-membered [Ag12(μ-CN)12] macrometallocycle in 8. Symmetry codes: A −x, y, 3/2 − z; B 1/2 − x, 3/2 − y,
1 − z; C 1/2 + x, 3/2 − y, 1/2 − z; D −x, y, 1/2 − z. (d) View of the 2D (6,3) anionic [Ag10(μ-CN)12]n2n− corrugated network in 8 along the ac
plane. See Figure 5 for color codes. (e) View of the 3D anionic [Ag10(μ-CN)12]n2n− net formed by interpenetration of the 2D networks in 8. (f) View
2n−
of the 1D channels of the 3D anionic [Ag10(μ-CN)12]n net filled by the 1D cationic [Ag4(μ-CN)2(μ-bdppmapy)4]n2n+ chains in 8. All hydrogen
atoms are omitted for clarity.
2n+
[Ag4(μ-CN)2(μ-bdppmapy)4]n
chain (Figure 6f). To our
Photoluminescent Properties. The photoluminescent
properties of 1−8 along with bdppmapy in the solid state at
room temperature were studied (Figure 7). Upon excitation at
244 (1), 320 (2 and 3), 345 (4), 320 (5), 334 (6), and 340 nm
(7 and 8), 1−8 exhibited photoluminescence with emission
maxima at 386 (1), 372 (2), 374 (3), 389 (4), 366 (5), 366 (6),
369 (7), and 371 nm (8), respectively. The emission maxima of
5−8 are red-shifted relative to those of 2−4. When compared
to the emission peak of bdppmapy at 370 nm, those of 1−4 are
knowledge, this is the first example that one ladder-shaped
cationic chain is encapsulated into the channels of a 3D anionic
2n−
[Ag10(μ-CN)12]n
net. This Ag2···Ag4E separation
(3.3138(11) Å; symmetry code for E, − x, 1 − y, 1 − z)
between 2D networks is longer than those found in [Ag2(μ-
dcpm)(μ-O2CCF3)2] (2.889(1) Å, dcpm = bis-
(dicyclohexylphosphino)methane),20 suggesting no existence
of a metal−metal interaction in 8.
2130
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design
Article
expanded. It is understandable that AgCN could undergo its
framework expansion to a 3D net in 8 because it has a 1D linear
chain. The degradation versus expansion of the AgCN
framework depends on many factors. The different structural
frameworks of 6−8 might be ascribed to the ways of the
rearrangement of the resulting [Aga(CN)b] species and the
ways of bdppmapy ligands linking these species. The reaction
temperature and time are also very critical in the formation of
these three complexes. Of course, other factors such as AgCN/
bdppmapy molar ratios and solvents that affect their formation
may not be ruled out. The photoluminescent properties of
these complexes were influenced by the different electron-
donating abilities of halides or pesudohalides. The method-
ology reported in this article is anticipated to apply in the
preparation of new metal cyanide-based oligomers and
polymers through cooperative degradation and expansion of
the polydimensional frameworks of metal cyanides such as
AuCN, CuCN, and Pt(CN)2 via the P and N hybrid ligands like
bdppmapy. Further work in this direction is in progress.
Figure 7. Emission spectra of 1−8 and bdppmapy in the solid state.
red-shifted, while those of 5−8 are blue-shifted. Compared with
other halides and pseudohalides, cyanide is the strongest
electron-withdrawing and weakest electron-donating group,
which generates the largest transition energy and thus exhibits
the shortest λmax at 366−371 nm in 6−8. As iodide and the O
atom of the coordinated MeOH molecule are stronger
electron-donating groups than chloride and bromide, the
emission maxima of 1 and 4 are red-shifted relative to those
of 2 and 3. Currently, it is difficult to find obvious relations
among the topological structures and the photoluminescent
properties of 1−8. Their emission origins may be assignable to
be halide (or pseudohalide)-to-ligand charge-transfer
(XLCT).21a,b
EXPERIMENTAL SECTION
■
General Procedures. All manipulations were carried out in open
air. The ligand bdppmapy was prepared according to the literature
method.21c Other chemicals were obtained from commercial sources
and used as received. IR spectra were recorded on a Varian Scamiter-
1000 spectrometer (4000−400 cm−1) with a KBr disk. The elemental
analyses for C, H, N were performed on a Carlo-Erba CHNO-S
microanalyzer. 1H and 31P{1H} NMR spectra were recorded at
ambient temperature on a Varian UNITY-300 spectrometer. Chemical
shifts are quoted relative to the solvent signal in DMSO-d6 (1H) or to
H3PO4 (85%) (31P external). ESI mass spectra were performed on an
Aglinent 1200/6200 mass spectrometer using MeCN as the mobile
phase. (Caution! Perchlorate salts of metal complexes with organic ligands
are potentially explosive. A small amount was used in all the reactions and
handled with great caution. All perchlorate compounds were tested and
found to be resistant to shock.)
CONCLUSIONS
■
In this article, we demonstrated the reactivity of a P,N-
containing ligand bdppmapy toward various Ag(I) salts.
Treatment of [Ag(MeCN)4]ClO4 with bdppmapy generated
one 1D cationic polymer 1. When the bulk AgX (X = Cl, Br, I,
SCN) reacted with bdppmapy, their 3D structures were broken
into [AgX] units that are linked by bdppmapy to form 1D
polymers 2−5. In these cases, only the framework degradation
of the bulk AgX was observed, which is probably due to the fact
that, relative to cyanide, halides and thiocyanide are weaker
donor ligands and easily replaced by bdppmapy. Intriguingly,
the linear chain of AgCN was cleaved into a [Ag(μ-CN)AgCN]
species in the tetramer 6 when it reacted with bdppmapy at
room temperature. Refluxing a mixture of AgCN and
bdppmapy for 2 or 4 h yielded a 1D polymer 7 and a 3D
polymer 8, respectively. In the former case, the linear chain of
AgCN was turned into a zigzag chain, two of which are linked
by bdppmapy bridges to form a 1D staircase chain. Such a chain
reformation may be ascribed to the steric hindrance caused by
introducing the bulky bdppmapy ligands between the two
zigzag chains. In the latter case, the framework of AgCN
undergoes very complicated structural changes. First, its linear
chain was partly cleaved into [Ag2(μ-CN)]+ cationic units,
which are picked up by pairs of bdppmapy to afford a 1D
ladder-type cationic chain. Second, the AgCN chain was partly
broken into various [Aga(CN)b] species, which are rearranged
into a 2D anionic [Ag10(μ-CN)12]n2n− wavelike network, which
is further interpenetrated with other equivalent ones to form a
3D [Ag10(μ-CN)12]n2n−-based net. This process conveys an
unprecedented framework expansion from the 1D chain of bulk
AgCN to the 3D [Ag10(μ-CN)12]n2n−-based anionic net. Third,
the 1D cationic chain was enclosed into the channels of the 3D
anionic net, which makes the AgCN framework be more
Synthesis. [Ag2(bdppmapy)2(MeOH)](ClO4)2 (1). To a solution of
[Ag(MeCN)4]ClO4 (37 mg, 0.1 mmol) in MeOH (5 mL) was added a
solution of bdppmapy (49 mg, 0.1 mmol) in MeOH (5 mL). The
mixture was stirred for 30 min and then filtered. Diethyl ether (20 mL)
was allowed to diffuse into the filtrate to form colorless blocks of 1 one
week later, which were collected by filtration, washed by Et2O, and
dried in vacuo. Yield: 45 mg (51% based on Ag). Anal. Calcd. for
C63H60Ag2Cl2N4O9P4: C, 53.00; H, 4.24; N, 3.92. Found: C, 52.59; H,
3.83; N, 4.03. IR (KBr disk): 3052 (w), 1592 (m), 1477 (s), 1435 (s),
1378 (w), 1323 (w), 1223 (m), 1163 (w), 1097 (s), 999 (w), 867 (w),
743 (m), 695 (m), 623 (m), 510 (m), 473 (w). 1H NMR (DMSO-d6,
300 MHz, ppm): δ 3.17 (s, 3H, −CH3), 5.00 (s, 4H, −CH2−), 6.37 (s,
3H, −py), 7.24−7.49 (m, 20H, −Ph), 7.70 (s 1H, −py). 31P{1H}
NMR (300 MHz, ppm): δ −1.14 (br), 1.79 (br).
[AgCl(bdppmapy)] (2). To a solution of bdppmapy (74 mg, 0.15
mmol) in MeCN (10 mL) was added AgCl (14 mg, 0.1 mmol). The
mixture was stirred for 1 h and then filtered. Slow evaporation of the
solvents from the filtrate afforded colorless prisms of 2 after 3 days,
which were collected by filtration, washed by Et2O, and dried in vacuo.
Yield: 50 mg (79% based on Ag). Anal. Calcd. for C31H28AgClN2P2: C,
58.74; H, 4.45; N, 4.42. Found: C, 58.63; H, 4.24; N, 4.54. IR (KBr
disk): 2910 (w), 1591 (s), 1476 (s), 1434 (s), 1384 (w), 1319 (m),
1278 (w), 1158 (m), 1096 (m), 1037 (w), 852 (m), 743 (s), 693 (s),
617 (w), 546 (w), 511 (m), 472 (w). 1H NMR (DMSO-d6, 300 MHz,
ppm): δ 4.97 (s, 4H, −CH2−), 5.97 (s, 1H, −py), 6.34 (d, 1H, −py),
6.92 (t, 1H, −py), 7.31−7.42 (m, 20H, −Ph), 7.63 (s, 1H, −py).
31P{1H} NMR (300 MHz, ppm): δ −4.66 (br).
[AgBr(bdppmapy)] (3). Compound 3 was prepared as colorless
blocks in a similar manner to that used for the preparation of 2, using
bdppmapy (74 mg, 0.15 mmol) and AgBr (19 mg, 0.1 mmol). Yield:
53 mg (78% based on Ag). Anal. Calcd. for C31H28AgBrN2P2: C,
2131
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design
Article
Table 2. Crystal Data and Structure Refinement Parameters for 1−3, 5, 6·CH2Cl2, 7·MeCN, and 8
1
2
3
chemical formula
formula weight
crystal system
space group
a (Å)
C63H60Ag2Cl2N4O9P4
1427.67
C31H28AgClN2P2
633.81
C31H28AgBrN2P2
678.27
triclinic
orthorhombic
Pbca
orthorhombic
Pbca
P1
̅
10.936(2)
16.060(3)
19.474(4)
77.21(3)
76.03(3)
72.09(3)
3117.9(10)
2
20.415(4)
13.369(3)
20.967(4)
20.619(4)
13.453(3)
21.059(4)
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
5722(2)
5841(2)
8
Z
8
T/K
223(2)
223(2)
223(2)
1.542
0.71073
2.190
2720
Dcalcd (g cm−3
)
1.521
1.471
λ(Mo Kα) (Å)
μ (mm−1
0.71073
0.876
0.71073
0.933
)
F(000)
1452
2576
no. of reflns collected
no. of unique reflns
no. of obsd. reflns
no. of variables
28710
21464
31687
14036 (Rint = 0.0437)
9903 (I > 2.00σ(I))
815
6514 (Rint = 0.034)
5764 (I > 2.00σ(I))
334
6649 (Rint = 0.0517)
5914 (I > 2.00σ(I))
334
a
R
0.0829
0.0534
0.0559
0.1064
1.244
8
b
wR
0.1648
0.0922
c
GOF
1.101
1.189
5
6·CH2Cl2
7·MeCN
chemical formula
formula weight
crystal system
space group
a (Å)
C64H56Ag2N6P4S2
1312.89
C98H86Ag4Cl2N10P6
2091.97
C37H31Ag4N7P2
1067.11
C69H56Ag7N11P4
1918.22
monoclinic
C2/c
orthorhombic
Pbca
monoclinic
P2/c
monoclinic
C2/c
13.815(3)
20.767(4)
41.214(8)
20.499(4)
11.142(2)
26.080(10)
123.51(2)
4967(2)
2
24.932(4)
11.2178(7)
18.016(3)
129.11(3)
3909.5(9)
4
26.794(5)
20.802(4)
14.632(3)
121.21(3)
6975(2)
4
b (Å)
c (Å)
α (deg)
β (deg)
11824(4)
γ (deg)
V (Å3)
8
223(2)
223(2)
223(2)
223(2)
Z
1.475
1.399
1.813
1.827
T (K)
0.71073
0.71073
0.71073
0.71073
2.065
Dcalcd (g cm−3
F(000)
)
0.887
0.976
2.092
5344
2112
2080
3744
no. of reflns collected
no. of unique reflns
no. of obsd. reflns
no. of variables
33290
38005
7564
15562
12515 (Rint = 0.0416)
8615 (Rint = 0.0644)
7112 (I > 2.00σ(I))
447
3443 (Rint = 0.0514)
2684 (I > 2.00σ(I))
196
6135 (Rint = 0.0551)
4046 (I > 2.00σ(I))
381
5482 (I > 2.00σ(I))
703
a
R
0.0665
0.1368
1.191
0.0685
0.0743
0.0554
b
wR
0.1758
0.1832
0.0971
c
GOF
1.074
1.054
1.022
a
b
c
2
R = Σ∥Fo| − |Fc∥/Σ|Fo|. wR = {Σw(Fo2 − Fc2)2/Σw(Fo )2}1/2. GOF = {Σw((Fo2 − Fc2)2)/(n − p)}1/2, where n = number of reflections and p =
total numbers of parameters refined.
54.89; H, 4.16; N, 4.13. Found: C, 54.85; H, 3.93; N, 4.17. IR (KBr
disk): 2912 (w), 1592 (s), 1476 (s), 1434 (s), 1380 (w), 1318 (m),
1278(w), 1222 (m), 1159 (m), 1097 (m), 854 (m), 742 (s), 694 (s),
625 (w), 504 (m), 477 (m). 1H NMR (DMSO-d6, 300 MHz, ppm): δ
4.91 (s, 4H, −CH2−), 6.15 (d, 1H, −py), 6.39 (s, 1H, −py), 7.03 (s,
1H, −py), 7.33−7.69 (m, 21H, −Ph and −py). 31P{1H} NMR (300
MHz, ppm): δ −2.19 (br).
[AgI(bdppmapy)] (4). Compound 4 was prepared as white powder
in a similar manner to that used for the preparation of 2, using
bdppmapy (74 mg, 0.15 mmol) and AgI (23 mg, 0.1 mmol). Yield: 60
mg (84% based on Ag). Anal. Calcd. for C31H28AgIN2P2: C, 51.34; H,
3.89; N, 3.86. Found: C, 51.37; H, 3.75; N, 3.99. IR (KBr disk): 1594
(s), 1472 (s), 1433 (s), 1376 (m), 1307 (w), 1275 (m), 1223 (m),
1160 (w), 1095 (m), 1026 (w), 914 (w), 853 (m), 745 (s), 692 (s),
493 (m). 1H NMR (DMSO-d6, 300 MHz, ppm): δ 5.02 (s, 4H,
−CH2−), 5.88 (d, 1H, −py), 6.34 (s, 1H, −py), 6.90 (d, 1H, −py),
7.27−7.61 (m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz, ppm):
δ −8.29 (br).
[AgSCN(bdppmapy)] (5). To a suspension of AgSCN (17 mg, 0.1
mmol) in EtOH (5 mL) was added a solution of bdppmapy (49 mg,
0.1 mmol) in CH2Cl2 (5 mL). The mixture was stirred for 30 min and
then filtered. Diethyl ether (20 mL) was allowed to diffuse into the
2132
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design
Article
filtrate to form colorless blocks of 5 after two weeks, which were
collected by filtration, washed by Et2O, and dried in vacuo. Yield: 40
mg (60% based on Ag). Anal. Calcd. for C32H28AgN3P2S: C, 58.55; H,
4.30; N, 6.40. Found: C, 58.09; H, 4.18; N, 6.21. IR (KBr disk): 2922
(w), 2090 (s), 1593 (s), 1480 (s), 1433 (s), 1379 (w), 1320 (w), 1276
(w), 1224 (m), 1159 (m), 1096 (m), 856 (m), 741 (m), 694 (s), 625
a Rigaku Mercury CCD X-ray diffractometer by using graphite
monochromated Mo Kα (λ = 0.71073 Å) radiation. Each single crystal
was mounted with grease at the top of a glass fiber and cooled at 223 K
in a liquid nitrogen stream. Cell parameters were refined by using the
program Crystalclear (Rigaku and MSc, Ver. 1.3, 2001) on all observed
reflections. The collected data were reduced by using the program
CrystalClear (Rigaku and MSc, Ver. 1.3, 2001), and an absorption
correction (multiscan) was applied. The reflection data were also
corrected for Lorentz and polarization effects.
1
(w), 507 (m), 473(w). H NMR (DMSO-d6, 300 MHz, ppm): δ 4.96
(s, 4H, −CH2−), 5.93 (d, 1H, −py), 6.34 (d, 1H, −py), 6.90 (s, 1H,
−py), 7.35−7.63 (m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz,
ppm): δ −1.61 (br).
All crystal structures were solved by direct methods and refined on
F2 by full-matrix least-squares methods with the SHELXTL-97
program.22 There were complicated disorder problems in the
structures of these compounds. For 1, one phenyl group of the
−PPh2 is disordered over two sites with the occupancy factor of 0.60/
0.40 for C57−C62/C57A−C62A. For 6·CH2Cl2, one pyridyl group is
disordered over two positions (C32−C35−C34A−N3/C32A−
C35A−C34−N3) by rotating about the N4−C32 bond with equal
occupancy factors. Besides, the CH2Cl2 solvent molecule is also
disordered over two orientations with equal occupancy factors for
Cl1−Cl2/Cl2−Cl2A. For 7·MeCN, one phenyl group of the −PPh2 is
disordered over two sites with equal occupancy factors for C6−C11/
C6A−C11A. One pyridyl group (C1−C4, C3A, and N1) is also
disordered over two positions by rotating about the N2−C1 bond with
equal occupancy factors, while, in the case of 8, three cyanides are
disordered over two orientations with equal occupancy factors for
C32−N5A/C32A−N5, C35−N6A/C35A−N6 and C36−N7A/
C36A/N7. All non-hydrogen atoms were refined anisotropically
except for those of the disordered CH2Cl2 molecule in 6·CH2Cl2,
and the phenyl group in 7·MeCN were refined isotropically. The
hydrogen atoms of the MeOH molecule in 1, the disordered CH2Cl2
solvent molecule, and the C33 atom of the disordered pyridine group
in 6 were not located. All other hydrogen atoms were placed in
geometrically idealized positions (C−H = 0.97 Å for methyl groups,
C−H = 0.95 Å for pyridyl, phenyl, and ethylene groups, C−H = 0.99
Å for methylene groups, and N−H = 0.87 Å for −NH− groups) and
constrained to ride on their parent atoms with Uiso(H) = 1.2−
1.5Ueq(C,N). Important crystal data and collection and refinement
parameters for 1−3, 5, 6·CH2Cl2, 7·MeCN, and 8 are given in Table 2.
[{(η2-bdppmapy)Ag(μ-CN)AgCN}2(μ-bdppmapy)] (6). To a sus-
pension of AgCN (14 mg, 0.1 mmol) in MeCN (5 mL) was added a
solution of bdppmapy (49 mg, 0.1 mmol) in CH2Cl2 (5 mL). The
mixture was stirred for 1 h and then filtered. Diethyl ether (20 mL)
was allowed to diffuse into the filtrate to form colorless blocks of
6·CH2Cl2 after 5 days, which were collected by filtration, washed by
Et2O, and dried in vacuo. Yield: 27 mg (50% based on Ag). Anal.
Calcd. for C97H84Ag4N10P6: C, 58.05; H, 4.22; N, 6.98. Found: C,
57.87; H, 4.61; N, 6.54. IR (KBr disk): 3050 (w), 2138 (w), 1597 (s),
1481 (s), 1434 (s), 1380 (m), 1318 (w), 1279 (w), 1225 (m), 1163
(m), 1101 (m), 1000 (w), 854 (m), 746 (s), 691 (s), 506 (w), 475
1
(w). H NMR (DMSO-d6, 300 MHz, ppm): δ 5.03 (s, 4H, −CH2−),
5.76 (s, 1H, −py), 5.93 (d, 1H, −py), 6.34 (s, 1H, −py), 6.91−7.40
(m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz, ppm): δ −8.35
(br), −6.37 (br).
[Ag4(μ-CN)4(μ-bdppmapy)] (7). The mixture of bdppmapy (49 mg,
0.1 mmol) and AgCN (27 mg, 0.2 mmol) in MeCN (5 mL) was
refluxed for 2 h. Then, the resulting solution was cooled to room
temperature and filtered. Diethyl ether (20 mL) was allowed to diffuse
into the filtrate to form colorless rhombic crystals of 7·MeCN mixed
with several long columns of 8 after three days, which were collected
by filtration and separated under microscopy. Crystals of 7·MeCN
were further washed by Et2O and dried in vacuo. Yield: 17 mg (33%
based on Ag). Anal. Calcd. for C35H28Ag4N6P2: C, 40.97; H, 2.75; N,
8.19. Found: C, 41.33; H, 2.34; N, 8.52. IR (KBr disk): 3049 (w),
2931 (w), 2150 (m), 1592 (s), 1481 (s), 1434 (s), 1370 (w), 1320
(m), 1277 (w), 1213 (w), 1159 (m), 1096 (m), 1037 (w), 858 (m),
1
739 (m), 692 (s), 503 (m). H NMR (DMSO-d6, 400 MHz, ppm): δ
4.71 (s, 4H, −CH2−), 6.32−6.44 (d, 2H, −py), 7.09 (s, 1H, −py),
7.44−7.61 (m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz, ppm):
δ −1.72 (br).
ASSOCIATED CONTENT
■
[Ag2(μ-CN)(μ-bdppmapy)2][Ag5(μ-CN)6] (8). A mixture containing
bdppmapy (49 mg, 0.1 mmol) and AgCN (27 mg, 0.2 mmol) in
MeCN (5 mL) was refluxed for 4 h. It was then cooled to room
temperature and filtered. Diethyl ether (20 mL) was allowed to diffuse
into the filtrate to form colorless long columns of 8 mixed with
rhombic crystals of 7·MeCN after three days, which were collected by
filtration and separated under microscopy. Crystals of 8 and 7·MeCN
were washed by Et2O and dried in vacuo. Yield for 7: 20 mg (38%
based on Ag). Yield for 8: 17 mg (31% based on Ag). Anal. Calcd. for
C69H56Ag7N11P4: C, 43.20; H, 2.94; N, 8.03. Found: C, 42.83; H, 2.69;
N, 8.50. IR (KBr disk): 3053 (w), 2928 (w), 2199 (w), 2142 (m),
1636 (w), 1595 (m), 1479 (s), 1434 (s), 1384 (m), 1314 (w), 1219
(w), 1158 (w), 1097 (m), 998 (w), 865 (m), 743 (s), 696 (s), 507
S
* Supporting Information
Crystallographic data of 1, 2, 3, 5, 6·CH2Cl2, 7·MeCN, and 8
(CIF). This material is available free of charge via the Internet
at http://pubs.acs.org.
AUTHOR INFORMATION
■
Corresponding Author
*(J.-P.L.) E-mail: jplang@suda.edu.cn. (Z.-G.R.) E-mail:
renzhigang@suda.edu.cn.
Notes
1
(m), 471 (w). H NMR (DMSO-d6, 300 MHz, ppm): δ 4.83 (s, 4H,
The authors declare no competing financial interest.
−CH2−), 6.18 (d, 1H, −py), 6.40 (s, 1H, −py), 7.02 (s, 1H, −py),
7.41−7.62 (m, 21H, −Ph and −py). 31P{1H} NMR (300 MHz, ppm):
δ −1.63 (br).
ACKNOWLEDGMENTS
■
Conversion of 1 to 2−5. To a solution of 1 (143 mg, 0.1 mmol)
in MeCN (10 mL) was added NH4Cl (11 mg, 0.2 mmol). The mixture
was stirred for 30 min to produce white powder of 2, which were
collected by filtration, washed by Et2O, and dried in air. Yield: 95 mg
(75% based on 1). Compounds 3−5 could be prepared in a similar
manner to that used for the preparation of 2, using 1 (143 mg, 0.1
mmol) and NH4Br (20 mg, 0.2 mmol), NH4I (29 mg, 0.2 mmol), or
NH4SCN (15 mg, 0.2 mmol) in MeCN (10 mL). Yield: 98 mg for 3
(72%), 109 mg for 4 (76%), and 87 mg (66%) for 5.
We thank the National Natural Science Foundation of China
(20901054, 21271134, and 21171124) and the State Key
Laboratory of Organometallic Chemistry of Shanghai Institute
of Organic Chemistry (201201006) for financial support. J.-P.L.
also highly appreciates the support for the Qin-Lan Project and
the “333” Project of Jiangsu Province, the Priority Academic
Program Development of Jiangsu Higher Education Institu-
tions, and the “SooChow Scholar” Program of Suzhou
University. We are also greatly thankful for the helpful
comments from the editor and the reviewers.
X-ray Structure Determinations. Single crystals of 1-3, 5,
6·CH2Cl2, 7·MeCN, and 8 suitable for X-ray analysis were obtained
directly from the above preparations. All measurements were made on
2133
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134

Crystal Growth & Design
Article
Reid, J. C.; Richard, C. E. F.; Skelton, B. W.; White, A. H. J. Chem. Soc.,
Dalton Trans. 1996, 2139.
REFERENCES
■
(1) (a) Mayer, H. A.; Kaska, W. C. Chem. Rev. 1994, 94, 1239.
(b) Meijboom, R.; Bowen, R. J.; Berners-Price, S. J. Coord. Chem. Rev.
2009, 253, 325. (c) Swor, C. D.; Tyler, D. R. Coord. Chem. Rev. 2011,
255, 2860. (d) Muetterties, E. L.; Alegranti, C. W. J. Am. Chem. Soc.
1972, 94, 6386. (e) Xu, X. L.; Nieuwenhuyzen, M.; James, S. L. Angew.
Chem., Int. Ed. 2002, 41, 764. (f) Yam, V. W. W.; Lo, K. K. W. Chem.
Soc. Rev. 1999, 28, 323. (g) Maggini, S. Coord. Chem. Rev. 2009, 253,
1793.
(2) (a) Miller, P. W.; Nieuwenhuyzen, M.; Charmant, J. P. H.; James,
S. L. Inorg. Chem. 2008, 47, 8367. (b) Rodriguez-Zubiri, M.; Gallo, V.;
Rose, J.; Welter, R.; Braunstein, P. Chem. Commun. 2008, 64.
(c) Hierso, J. C.; Fihri, A.; Ivanov, V. V.; Hanquet, B.; Pirio, N.;
Donnadieu, B.; Rebiere, B.; Amardeil, R.; Meunier, P. J. Am. Chem. Soc.
2004, 126, 11077. (d) Zhang, J.; Nieuwenhuyzen, M.; Charmant, J. P.
H.; James, S. L. Chem. Commun. 2004, 2808. (e) Zhang, J.; Xu, X. L.;
James, S. L. Chem. Commun. 2006, 4218. (f) Song, H. B.; Zhang, Z. Z.;
Mak, T. C. W. J. Chem. Soc., Dalton Trans. 2002, 1336. (g) Durran, S.
E.; Smith, M. B.; Slawinb, A. M. Z.; Steed, J. W. J. Chem. Soc., Dalton
Trans. 2000, 2771. (h) Eisler, D. J.; Kirby, C. W.; Puddephatt, R. J.
Inorg. Chem. 2003, 42, 7626.
(13) (a) Akhbari, K.; Morsali, A. Cryst. Growth Des. 2007, 7, 2024.
(b) Akhbari, K.; Morsali, A. CrystEngComm 2010, 12, 3394. (c) Zhang,
J.; Lin, Y.; Huang, X.; Chen, X. Inorg. Chem. 2005, 44, 3146.
(d) Zheng, S.; Tong, M.; Tan, S.; Wang, Y.; Shi, J.; Tong, Y.; Lee, H.;
Chen, X. Organometallics 2001, 20, 5319. (e) Akhbari, K.; Morsali, A.;
Retailleau, P. Polyhedron 2010, 29, 3304. (f) Akhbari, K.; Morsali, A.;
Zeller, M. J. Organomet. Chem. 2007, 692, 3788. (g) Bashiri, R.;
Akhbari, K.; Morsali, A.; Zeller, M. J. Organomet. Chem. 2008, 693,
1903. (h) Wang, P.; Dong, Y. B.; Ma, J. P.; Huang, R. Q.; Smith, M. D.
Cryst. Growth Des. 2005, 5, 701. (i) Dong, Y. B.; Geng, Y.; Ma, J. P.;
Huang, R. Q. Organometallics 2006, 25, 447. (j) Dong, Y. B.; Zhang,
Q.; Wang, L.; Ma, J. P.; Huang, R. Q.; Shen, D. Z.; Chen, D. Z. Inorg.
Chem. 2005, 44, 6591.
(14) (a) Espinet, P.; Soulantica, K. Coord. Chem. Rev. 1999, 293, 499.
(b) James, S. L. Chem. Soc. Rev. 2009, 38, 1744.
(15) (a) Li, N. Y.; Ren, Z. G.; Liu, D.; Yuan, R. X.; Wei, L. P.; Zhang,
L.; Li, H. X.; Lang, J. P. Dalton Trans. 2010, 39, 4213. (b) Li, N. Y.;
Ren, Z. G.; Liu, D.; Wang, J.; Dai, M.; Li, H. X.; Lang, J. P. Inorg.
Chem. Commun. 2009, 12, 1031. (c) Li, L.; Ren, Z. G.; Li, N. Y.;
Zhang, Y.; Lang, J. P. Inorg. Chim. Acta 2009, 362, 3910.
(16) (a) Bachman, R. E.; Andretta, D. F. Inorg. Chem. 1998, 37, 5657.
(b) Bowmaker, G. A.; Effendy; Harvey, P. J.; Healy, P. C.; Skelton, B.
W.; White, A. H. J. Chem. Soc., Dalton Trans. 1996, 2449.
(17) (a) Wulfsberg, G.; Jackson, D.; Iisley, W.; Dou, S.; Weiss, A.;
Gagliardi, J. J. Z. Naturforsch., A: Phys. Sci. 1992, 47, 75. (b) Bachechi,
F.; Burini, A.; Galassi, R.; Pietroni, B. R.; Tesei, D. Eur. J. Inorg. Chem.
2002, 2086. (c) Effendy; Nicola, C. D.; Fianchini, M.; Pettinari, C.;
Skelton, B. W.; Somers, N.; White, A. H. Inorg. Chim. Acta 2005, 358,
763.
(3) (a) Healy, P. C.; Loughrey, B. T.; Williams, M. L. Aust. J. Chem.
2012, 65, 811. (b) Bowmaker, G. A.; Nicola, C. D.; Effendy; Hanna, J.
V.; Healy, P. C.; King, S. P.; Marchetti, F.; Pettinari, C.; Robinson, W.
̆ ̆
T.; Skelton, B. W.; Sobolev, A. N.; Tabacaru, A.; White, A. H. Dalton
Trans. 2013, 42, 277. (c) Li, Y. J.; Deng, Z. Y.; Xu, X. F.; Wu, H. B.;
Cao, Z. X.; Wang, Q. M. Chem. Commun. 2011, 47, 9179. (d) Zhang, J.
F.; Fu, W. F.; Gan, X.; Chen, J. H. Dalton Trans. 2008, 3093.
(e) Engelhardt, L. M.; Gotsis, S.; Healy, P. C.; Kildea, J. D.; Skelton, B.
W.; White, A. H. Aust. J. Chem. 1989, 42, 149. (f) Clarke, D. A.; Miller,
P. W.; Long, N. J.; White, A. J. Dalton Trans. 2007, 4556. (g) Van
Calcar, P. M.; Olmstead, M. M.; Balch, A. L. Chem. Commun. 1996,
2597.
(18) (a) Altaf, M.; Stoeckli-Evans, H. Polyhedron 2010, 29, 701.
(b) Bessler, K. E.; Romualdo, L. L.; Deflon, V. M.; Hagenbach, A. Z.
Anorg. Allg. Chem. 2000, 626, 1942.
(4) Gu, X.; Xu, Z. J.; Lo, V. K. Y.; Che, C. M. Synthesis 2012, 44,
3307.
(19) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7.
(20) Che, C. M.; Tse, M. C.; Chan, M. C. W.; Cheung, K. K.;
Phillips, D. L.; Leung, K. H. J. Am. Chem. Soc. 2000, 122, 2464.
(21) (a) Blake, A. J.; Brooks, N. R.; Champness, N. R.; Cooke, P. A.;
Crew, M.; Deveson, A. M.; Hanton, L. R.; Hubberstey, P.; Dieter, F.;
(5) (a) Berners-Price, S. J.; Bowen, R. J.; Harvey, P. J.; Healy, P. C.;
Koutsantonis, G. A. J. Chem. Soc., Dalton Trans. 1998, 1743. (b) Liu, J.
J.; Galettis, P.; Farr, A.; Maharaj, L.; Samarasinha, H.; McGechan, A.
C.; Baguley, B. C.; Bowen, R. J.; Berners-Price, S. J.; McKeage, M. J. J.
Inorg. Biochem. 2008, 102, 303.
(6) (a) Yu, Y. B.; Fan, S. L.; Zhang, X. G. Chem.Eur. J. 2012, 46,
14643. (b) Ntoras, C.; Cox, P. J.; Aslanidis, P. Polyhedron 2012, 34,
171. (c) Hu, J. A.; Nguyen, M. H.; Yip, J. H. K. Inorg. Chem. 2011, 50,
7429. (d) Meyer, N.; Schuh, E.; Seeger, H.; Mohr, F. Annu. Rep. Prog.
Chem., Sect. A: Inorg. Chem. 2012, 108, 230. (e) Chao, H. Y.; Lu, W.;
Li, Y.; Chan, M. C. W.; Che, C. M.; Cheung, K. K.; Zhu, N. J. Am.
Chem. Soc. 2002, 124, 14696. (f) Barbieri, A.; Accorsi, G.; Armaroli, N.
Chem. Commun. 2008, 2185.
Schroder, M. Cryst. Eng. 1999, 2, 181. (b) Vitale, M.; Ryu, C. K.; Palke,
̈
W. E.; Ford, P. C. Inorg. Chem. 1994, 33, 561. (c) Zhang, J. F.; Gan, X.;
Fu, W. F.; Han, X.; Li, L. Inorg. Chim. Acta 2010, 363, 338.
(22) (a) Sheldrick, G. M. SHELXS-97, Program for Solution of
Crystal Structures; University of Gottingen: Gottingen, Germany,
̈
̈
1997. (b) Sheldrick, G. M. SHELXL-97, Program for Refinement of
Crystal Structures; University of Gottingen: Gottingen, Germany,
̈
̈
1997.
(7) Teo, B. K.; Calabrese, J. C. J. Chem. Soc., Chem. Commun. 1976,
185.
́
́
(8) Perez-Lourido, P. A.; Garcıa-Vazquez, J. A.; Romero, J.; Louro,
́
M. S.; Sousa, A.; Chen, Q.; Chang, Y.; Zubieta, J. J. Chem. Soc., Dalton
Trans. 1996, 2047.
(9) Mason, M. R.; Duff, C. M.; Miller, L. L.; Jacobson, R. A.; Verkade,
J. G. Inorg. Chem. 1992, 31, 2746.
(10) (a) Swanson, H. E.; Fuyat, R. K.; Ugrinic, G. M. National Bureau
of Standards (U.S.), Circular, 1955. (b) Takahashi, H.; Tamaki, S.; Sato,
S. J. Phys. Soc. Jpn. 1987, 56, 3593. (c) Wright, A. F.; Fender, B. E. F. J.
Phys. C: Solid State Phys. 1977, 10, 2261. (d) Cotton, F. A.; Wilkinson,
G. Advanced Inorganic Chemistry, 5th ed; Wiley-Interscience:
Singapore, 1988; Vol. 18, p 940. (e) Bachman, R. E.; Andretta, D.
F. Inorg. Chem. 1998, 37, 5657.
(11) (a) Teo, B. K.; Calabrese, J. C. Inorg. Chem. 1976, 15, 2474.
(b) Alcock, N. W.; Moore, P.; Lampe, P. A.; Mok, K. F. J. Chem. Soc.,
Dalton Trans. 1982, 207. (c) Bowmaker, G. A.; Effendy; Hanna, J. V.;
Healy, P. C.; Skelton, B. W.; White, A. H. J. Chem. Soc., Dalton Trans.
1993, 1387.
(12) (a) Lin, Y. Y.; Lai, S. W.; Che, C. M.; Fu, W. F.; Zhou, Z. Y.;
Zhu, N. Y. Inorg. Chem. 2005, 44, 1511. (b) Bowmaker, G. A.; Effendy;
2134
dx.doi.org/10.1021/cg4002048 | Cryst. Growth Des. 2013, 13, 2124−2134