Divalent transition metal phosphonates with new structure containing hydrogen-bonded layers of phosphonate anions

Article abstract of DOI:10.1016/S0022-4596(03)00185-3

A series of divalent transition metal phosphonates containing hydrogen-bonded layers of phosphonate anions, namely [M(phen)₃]·C₆H₅PO ₃·11H₂O [M=Co(1), Ni(2), Cu(3)] and [Cd(phen)₃]·C₆H₅PO ₃H·Cl·7H₂O (4) have been synthesized, structurally characterized by single-crystal X-ray diffraction method. These compounds all crystallize in the triclinic system, space group P-1. The lattice parameters are a=12.1646(5), b=12.4155(6), c=15.4117(10)A, α=78.216(2), β=79.735(3), γ=77.8380(3)°, V=2205.1(2)A³, Z=2 for 1; a=12.097(2), b=12.606(3), c=15.742(3)A, α=76.66(3), β=80.04(3), γ=77.75(3)°, V=2263.4(8)A³, Z=2 for 2; a=12.058(2), b=12.518(3), c=15.781(3)A, α=77.77(3), β=80.02(3), γ=77.91(3)°, V=2255.5(8)A³, Z=2 for 3 and a=12.47680(10), b=12.6693(2), c=16.1504(3)A, α=82.600(1), β=71.122(1), γ=77.355(1)°, V=2352.37(6)A³, Z=2 for 4. All structures are refined by full-matrix least-squares methods [for 1, R1=0.0602 using 6458 independent reflections with I>2σ(I); for 2, R1=0.0632 using 4657 independent reflections with I>2σ(I); for 3, R1=0.0634 using 6221 independent reflections with I>2σ(I); for 4, R1=0.0400 using 7930 independent reflections with I>2σ(I)]. In the crystal structures, the phenylphosphonate anions and water molecules are hydrogen-bonded to form layers, and there exist the cationic species [M(phen)₃]²⁺ between the adjacent layers of anions and water. Luminescence, thermal analysis as well as IR spectroscopic studies are also presented.

Full text of DOI:10.1016/S0022-4596(03)00185-3

ARTICLE IN PRESS
Journal of Solid State Chemistry 174 (2003) 116–124
Divalent transition metal phosphonates with new structure containing
hydrogen-bonded layers of phosphonate anions
Jin Yang, Jian-Fang Ma,ꢀ Guo-Li Zheng, Li Li, Fang-Fang Li, Yong-Mei Zhang,
and Jing-Fu Liu
Department of Chemistry, Northeast Normal University, Changchun 130024, People’s Republic of China
Received 5 December 2002; received in revised form 20 March 2003; accepted 31 March 2003
Abstract
A series of divalent transition metal phosphonates containing hydrogen-bonded layers of phosphonate anions, namely
[M(phen)3] ꢁ C6H5PO3 ꢁ 11H2O [M=Co(1), Ni(2), Cu(3)] and [Cd(phen)3] ꢁ C6H5PO3H ꢁ Cl ꢁ 7H2O (4) have been synthesized,
structurally characterized by single-crystal X-ray diffraction method. These compounds all crystallize in the triclinic system,
space group P-1. The lattice parameters are a ¼ 12:1646ð5Þ; b ¼ 12:4155ð6Þ; c ¼ 15:4117ð10Þ A, a ¼ 78:216ð2Þ; b ¼ 79:735ð3Þ;
g ¼ 77:8380ð3Þꢂ; V ¼ 2205:1ð2Þ A3, Z ¼ 2 for 1; a ¼ 12:097ð2Þ; b ¼ 12:606ð3Þ; c ¼ 15:742ð3Þ A, a ¼ 76:66ð3Þ; b ¼ 80:04ð3Þ;
g ¼ 77:75ð3Þꢂ; V ¼ 2263:4ð8Þ A3, Z ¼ 2 for 2; a ¼ 12:058ð2Þ; b ¼ 12:518ð3Þ; c ¼ 15:781ð3Þ A, a ¼ 77:77ð3Þ; b ¼ 80:02ð3Þ;
g ¼ 77:91ð3Þꢂ; V ¼ 2255:5ð8Þ A3, Z ¼ 2 for 3 and a ¼ 12:47680ð10Þ; b ¼ 12:6693ð2Þ; c ¼ 16:1504ð3Þ A, a ¼ 82:600ð1Þ; b ¼
71:122ð1Þ; g ¼ 77:355ð1Þꢂ; V ¼ 2352:37ð6Þ A3, Z ¼ 2 for 4. All structures are refined by full-matrix least-squares methods [for 1,
R1 ¼ 0:0602 using 6458 independent reflections with I42sðIÞ; for 2, R1 ¼ 0:0632 using 4657 independent reflections with I42sðIÞ;
for 3, R1 ¼ 0:0634 using 6221 independent reflections with I42sðIÞ; for 4, R1 ¼ 0:0400 using 7930 independent reflections with
I42sðIÞ]. In the crystal structures, the phenylphosphonate anions and water molecules are hydrogen-bonded to form layers, and
there exist the cationic species [M(phen)3]2+ between the adjacent layers of anions and water. Luminescence, thermal analysis as well
as IR spectroscopic studies are also presented.
r 2003 Elsevier Science (USA). All rights reserved.
Keywords: Metal phosphonates; Crystal structure; IR spectroscopy; Luminescence; Thermal analysis
1. Introduction
hybrid materials. Organic components have been used as
structure-directing reagents in a wide range of materials
including zeolites, mesoporous materials of the MCM-41
class [9]. The study on metal phosphonate containing a
second neutral organic ligand is relatively rare [10–12],
and we are interested in an attractive approach to the
fabrication of newstructure. Here we present new
materials containing hydrogen-bonded layers of phenyl-
phosphonate anions and water molecules.
The field of metal phosphonate chemistry is expand-
ing at a rapid rate due to the interest in the structural
chemistry of their compounds and their potential
applications as hosts in intercalation reactions, proton
conductors, sorbents, ion exchangers, sensors and
catalysts [1–5]. Most of the divalent transition metal
phosphonates investigated are layered species where the
metal octahedra are bridged by phosphonic acid
tetrahedra to form two-dimensional layers [6,7]. Layered
phosphonates are found to have structurally and
chemically well-defined internal spaces and coordination
sites [8], providing relatively easy access to intercalating
reagents. The introduction of the second neutral organic
ligand into metal phosphonate phases provides a power-
ful method for synthesis of novel organic–inorganic
2. Experimental
2.1. General procedures
All materials were commercially available and used as
received. The FT-IR spectra were recorded from KBr
pellets in range 4000–400 cmÀ1 on a Mattson Alpha-
Centauri spectrometer. Elemental analyses were carried
out with a Perkin-Elmer 240 elemental analyzer. The
ꢀCorresponding author. Fax: +86-431-5684009.
E-mail address: jfma@public.cc.jl.cn (J.-F. Ma).
0022-4596/03/$ - see front matter r 2003 Elsevier Science (USA). All rights reserved.
doi:10.1016/S0022-4596(03)00185-3

ARTICLE IN PRESS
J. Yang et al. / Journal of Solid State Chemistry 174 (2003) 116–124
117
emission spectrum was recorded on a Varian Cary
Eclipse spectrometer. TGA was performed using a
Perkin-Elmer TG-7 analyzer in nitrogen.
based on Cu). Calc. for 3: C, 52.59; H, 5.32; N, 8.76.
Found: C, 52.68%; H, 5.14%; N, 8.89%. IR (cmÀ1
KBr): 3420(vs), 3053(w), 1650(w), 1518(s), 1508(w),
1427(vs), 1134(m), 1104(w), 1062(w), 849(s), 724(vs),
696(m), 559(v).
,
2.2. Syntheses
[Cd(phen)3] ꢁ C6H5PO3H ꢁ Cl ꢁ 7H2O 4: Crystals of
compound 4 were prepared analogously to 1 (58% yield
based on Cd). Calc. for 4: C, 50.02; H, 4.76; N, 8.34.
[Co(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 1: A solution of sodium
phenylphosphonate (0.200 g, 1 mmol) in 10 ml of water
was added to the solution of CoCl2 ꢁ 6H2O (0.238 g,
1 mmol) in 10 ml of water with constant stirring.
The suspension of cobalt phenylphosphonate was
obtained. Then o-phenanthroline (0.396 g, 2 mmol) was
added to the suspension with constant stirring at 80ꢂ for
30 min. Orange crystals were obtained by standing the
solution at room temperature for several weeks (67%
yield based on Co). Calc. for 1: C, 52.84; H, 5.35; N,
8.81. Found: C, 52.91%; H, 5.17%; N, 8.93%. IR
(cmÀ1, KBr): 3404(vs), 3050(w), 1653(w), 1624(m),
1517(s), 1425(vs), 1132(m), 1103(s), 1063(w), 847(m),
725(vs), 667(w), 590(w).
Found: C, 50.21%; H, 4.68%; N, 8.55%. IR (cmÀ1
,
KBr): 3432(vs), 3055(w), 1650(w), 2333(vs), 1645(m),
1625(m), 1426(s), 1138(m), 1066(w), 899(w), 851(m),
726(m), 672(w), 556(w).
2.3. X-ray crystallography
The structures of compounds 1; 2; 3 and 4 were
determined by single-crystal X-ray diffraction. Crystallo-
graphic data are shown in Table 1. The data collections
were performed on
a
Rigaku RAXIS-RAPID
diffractometer at 293 K, using graphite-monochromated
MoKa radiation (l ¼ 0:71069 A) by the o scan mode.
Empirical absorption corrections (multi-scan) were
applied in all cases. The structures were solved by
direct methods (SHELXS-97) [13] and refined by
full-matrix least squares on F2 (SHELXL-97) [14].
All non-hydrogen atoms were refined anisotropically,
and the positions of hydrogen atoms on carbon
atoms were calculated theoretically, the hydrogen
atoms of water molecules were not located.
[Ni(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 2: Crystals of com-
pound 2 were prepared analogously to 1 (72% yield
based on Ni). Calc. for 2: C, 52.85; H, 5.35; N, 8.81.
Found: C, 52.94%; H, 5.17%; N, 8.96%. IR (cmÀ1
,
KBr): 3493(vs), 3057(w), 1653(w), 1625(m), 1518(s),
1426(vs), 1139(s), 1105(m), 1045(m), 1022(w), 896(m),
869(m), 748(w), 727(vs), 696(m), 644(m), 556(m).
[Cu(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 3: Crystals of com-
pound 3 were prepared analogously to 1 (63% yield
Table 1
Crystal data and structure refinement for compounds 1–4
1
2
3
4
Formula
Formula weight
Crystal size (mm)
Crystal system
Space group
a (A)
C42H51CoN6O14
953.79
P
C42H51NiN6O14
953.57
P
C42H51CuN6O14
958.40
P
C42H48CdN6O12
1007.68
P
0.44 Â 0.31 Â 0.19
0.26 Â 0.31 Â 0.13
0.25 Â 0.42 Â 0.13
0.23 Â 0.38 Â 0.28
Triclinic
%
P1
Triclinic
%
P1
Triclinic
%
P1
Triclinic
%
P1
12.1646(5)
12.4155(6)
15.4117(10)
78.216(2)
79.735(3)
77.8380(10)
2205.1(2)
2
12.097(2)
12.606(3)
15.742(3) (3)
76.66(3)
80.04(3)
77.75(3)
2263.4(8)
2
12.058(2)
12.518(3)
15.781(3)
77.77(3)
80.02(3)
77.91(3)
2255.5(8)
2
12.47680(10)
12.6693(2)
16.1504(3)
82.6000(10)
71.1220(10)
77.3550(10)
2352.37(6)
2
b (A)
c (A)
a (deg)
b (deg)
g (deg)
V (A3)
Z
Dc (g cmÀ3
F(000)
)
1.436
998
1.399
1000
1.411
1002
1.423
1036
l (MoKa) (A)
0.71073
0.500
293
0.71073
0.536
293
0.71073
0.592
293
0.71073
0.620
293
m (mmÀ1
Temperature (K)
)
Reflections collected
Unique reflections
Observed reflections (I42sðIÞ)
R1 (I42sðIÞ)
15239
9734
6458
16482
10130
4657
16571
10242
6221
17403
10692
7930
0.0400
0.0602
0.1934
1.013
0.0632
0.1843
0.938
0.0634
0.1873
0.981
wR2 (I42sðIÞ)
0.1218
1.034
Goodness of fit

ARTICLE IN PRESS
J. Yang et al. / Journal of Solid State Chemistry 174 (2003) 116–124
118
Crystallographic data for the structure have been
deposited with the Cambridge Crystallographic Data
Center as supplementary publication no. CCDC-192807
for 1; CCDC-192808 for 2; CCDC-192809 for 3; and
CCDC-192810 for 4:
Table 2
Selected bond lengths (A) and angles (deg) for compounds 1–4
[Co(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 1
N(1)–Co(1)
N(3)–Co(1)
N(5)–Co(1)
2.158(3)
2.112(3)
2.150(3)
N(2)–Co(1)
N(4)–Co(1)
N(6)–Co(1)
2.118(3)
2.146(3)
2.126(3)
N(3)–Co(1)–N(2)
N(2)–Co(1)–N(6)
N(2)–Co(1)–N(4)
N(3)–Co(1)–N(5)
N(6)–Co(1)–N(5)
N(3)–Co(1)–N(1)
N(6)–Co(1)–N(1)
N(5)–Co(1)–N(1)
98.26(11)
164.49(11)
96.50(11)
168.02(11)
78.12(12)
94.22(11)
91.71(11)
94.99(10)
N(3)–Co(1)–N(6)
N(3)–Co(1)–N(4)
N(6)–Co(1)–N(4)
N(2)–Co(1)–N(5)
N(4)–Co(1)–N(5)
N(2)–Co(1)–N(1)
N(4)–Co(1)–N(1)
93.97(12)
78.07(12)
95.33(12)
91.15(11)
93.57(11)
77.96(11)
169.88(11)
3. Results and discussion
3.1. Crystal structures
Selected bond distances and angles for 124 are listed
in Table 2. Atomic coordinates, isotropic thermal
parameters and anisotropic thermal parameters are
listed in Tables 3 and 4, respectively. 1; 2 and 3 show
similar structure, each of them consists of cationic
species [M(phen)3]2+, in which metal anion is six-
coordinated by six nitrogen atoms from three o-
phenanthroline ligands (Fig. 1). Since –PO23À is a strong
ligand for divalent transition metal, in the reported
structure of divalent metal phenylphosphonate, –PO32À
group is directly bonded to metal cation to form
polymeric structure [6]. However, in compounds 1; 2
and 3; owing to the strong chelating role of o-
phenanthroline towards the metal cation (II), the
phenylphosphonate anion was segregated from the
central metal cation (II). Generally, metal phosphonates
possess layered solid state structures, where the
octahedrally coordinated metal cation is within
the polymeric layer and the organic moiety directed
into the interlamellar space [15–18]. The structures
of 1; 2 and 3 are not layered in traditional case,
but are better described as consisting of hydrogen-
bonded layers of phenylphosphonate anions and
water molecules with [M(phen)3]2+ cations locating
between the adjacent layers as presented in Fig. 2.
Within the layer of phenylphosphonate anions
and water molecules, there are rows of anions with
the orientations of –PO23À groups alternating up
and down, as shown in Fig. 3. There are some
lattice water molecules which are hydrogen-bonded
to phenylphosphonate anions to result in an interesting
two-dimensional hydrogen-bonding network (Fig. 3).
The hydrogen bonds in this study have been
considered with liberal distance cut-off criteria of
[Ni(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 2
N(1)–Ni(1)
N(3)–Ni(1)
N(5)–Ni(1)
2.110(3)
2.083(4)
2.098(4)
N(2)–Ni(1)
N(4)–Ni(1)
N(6)–Ni(1)
2.085(4)
2.098(4)
2.085(4)
N(3)–Ni(1)–N(2)
N(2)–Ni(1)–N(6)
N(2)–Ni(1)–N(5)
N(3)–Ni(1)–N(4)
N(6)–Ni(1)–N(4)
N(3)–Ni(1)–N(1)
N(6)–Ni(1)–N(1)
N(4)–Ni(1)–N(1)
94.99(14)
168.23(14)
92.44(14)
9.87(15)
N(3)–Ni(1)–N(6)
N(3)–Ni(1)–N(5)
N(6)–Ni(1)–N(5)
N(2)–Ni(1)–N(4)
N(5)–Ni(1)–N(4)
N(2)–Ni(1)–N(1)
N(5)–Ni(1)–N(1)
93.79(15)
170.31(14)
79.77(15)
94.50(14)
93.36(14)
79.23(14)
93.67(13)
94.75(14)
93.83(15)
92.39(14)
170.77(14)
[Cu(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 3
N(1)–Cu(1)
N(3)–Cu(1)
N(5)–Cu(1)
2.272(3)
2.051(3)
2.074(3)
N(2)–Cu(1)
N(4)–Cu(1)
N(6)–Cu(1)
2.082(3)
2.252(3)
2.089(3)
N(3)–Cu(1)–N(5)
N(5)–Cu(1)–N(2)
N(5)–Cu(1)–N(6)
N(3)–Cu(1)–N(4)
N(2)–Cu(1)–N(4)
N(3)–Cu(1)–N(1)
N(2)–Cu(1)–N(1)
N(4)–Cu(1)–N(1)
168.69(12)
92.86(12)
80.19(13)
77.96(12)
96.41(12)
95.63(12)
76.91(11)
170.42(12)
N(3)–Cu(1)–N(2)
N(3)–Cu(1)–N(6)
N(2)–Cu(1)–N(6)
N(5)–Cu(1)–N(4)
N(6)–Cu(1)–N(4)
N(5)–Cu(1)–N(1)
N(6)–Cu(1)–N(1)
95.10(12)
93.76(13)
165.34(11)
93.20(12)
96.86(12)
93.99(11)
90.62(11)
[Cd(phen)3] ꢁ C6H5PO3H ꢁ Cl ꢁ 7H2O 4
N(1)–Cd(1)
N(3)–Cd(1)
N(5)–Cd(1)
2.366(3)
2.372(3)
2.337(3)
N(2)–Cd(1)
N(4)–Cd(1)
N(6)–Cd(1)
2.340(3)
2.395(3)
2.361(3)
N(5)–Cd(1)–N(2)
N(2)–Cd(1)–N(6)
N(2)–Cd(1)–N(1)
N(5)–Cd(1)–N(3)
N(6)–Cd(1)–N(3)
N(5)–Cd(1)–N(4)
N(6)–Cd(1)–N(4)
N(3)–Cd(1)–N(4)
99.03(9)
112.99(10)
71.82(9)
N(5)–Cd(1)–N(6)
N(5)–Cd(1)–N(1)
N(6)–Cd(1)–N(1)
N(2)–Cd(1)–N(3)
N(1)–Cd(1)–N(3)
N(2)–Cd(1)–N(4)
N(1)–Cd(1)–N(4)
71.92(9)
160.51(10)
95.39(9)
90.26(9)
97.07(10)
155.26(10)
103.41(10)
89.69(9)
100.08(9)
152.19(10)
90.95(9)
70.97(9)
(
2:5oO?Oo3:0 A: In compound 1; the dihedral
angle between the benzene ring (C1–C6) of phenylpho-
sphonate anion and o-phenanthroline (C201–C212)
is 11.4ꢂ; and the distance between them is about
3.6 A. There may exist weak p2p stacking interaction
between them.
layers of 4 are composed of ClÀ, –PO3HÀ and water
molecules. The phenyl ring (C1–C6) of phenylpho-
sphonate anion and o-phenanthroline (C301–C312)
planes are almost parallel with a dihedral angle of 4.9ꢂ
and the distance between them is about 3.7 A. There
may also exist weak p2p stacking interaction between
them.
Compound 4 consists of [Cd(phen)3]2+ cations and
two kinds of un-coordinating anions: ClÀ and –PO3HÀ
(Fig. 4). The M–N average distance is much longer than
those observed in compounds 1; 2 and 3: Compound 4
shows a similar structure to 1; but the hydrogen-bonded

ARTICLE IN PRESS
J. Yang et al. / Journal of Solid State Chemistry 174 (2003) 116–124
119
Table 3
Atomic coordinates ( Â 104) and equivalent isotropic displacement
parameters (A Â 103) for 1À4: UðeqÞ is defined as one-third of the
trace of the orthogonalized Uij tensor
x
y
z
UðeqÞ
[Co(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 1
C(1)
C(2)
6773(3)
7520(4)
8565(4)
8890(4)
8160(5)
7092(4)
7778(3)
7389(3)
7958(4)
8909(3)
9581(4)
10507(4)
10832(3)
11763(3)
12026(3)
11352(3)
10200(3)
9232(3)
7278(3)
6497(4)
6645(4)
7597(4)
7842(5)
8792(6)
9593(4)
10630(5)
11336(4)
11006(3)
9366(3)
8354(3)
11652(3)
12332(4)
11886(4)
10740(4)
10227(6)
9141(6)
8483(4)
7350(5)
6823(4)
7397(3)
8987(3)
10135(3)
8678(2)
10451(2)
8199(3)
10060(3)
10586(2)
8446(3)
4834(3)
4724(2)
5671(3)
13022(2)
6292(3)
5306(4)
4466(4)
5056(5)
13876(3)
13583(3)
5040(10)
3670(3)
4007(4)
4215(5)
4084(4)
3785(5)
3590(4)
6830(4)
6142(4)
5066(4)
4674(3)
3580(3)
3243(3)
3955(3)
3640(4)
4388(4)
5437(3)
5036(3)
5402(3)
6643(4)
6603(4)
7056(4)
7561(4)
8046(5)
8475(5)
8468(4)
8882(4)
8856(4)
8440(4)
8035(3)
7556(3)
7527(4)
8002(4)
8960(4)
9480(4)
10466(4)
10928(4)
10431(4)
10877(4)
10382(4)
9405(4)
9441(3)
8947(3)
6481(3)
5770(2)
7111(3)
8026(3)
7978(3)
8928(3)
2957(3)
4498(3)
2548(3)
10993(2)
8809(3)
8023(4)
9290(4)
5840(4)
5475(4)
7445(5)
8991(8)
6300(3)
5547(3)
5614(3)
6453(4)
7200(4)
7128(3)
9140(2)
9913(3)
10117(3)
9539(2)
9709(3)
9129(3)
8324(3)
7688(3)
6931(3)
6804(3)
8137(2)
8764(2)
6893(3)
6339(4)
5475(4)
5116(3)
4192(3)
3885(3)
4459(3)
4170(3)
4765(3)
5671(3)
5367(2)
5702(2)
7992(2)
8389(3)
8707(3)
8622(3)
8935(4)
8828(3)
8389(3)
8247(4)
7779(4)
7461(3)
8069(2)
8201(2)
8568(2)
7379(2)
6582(2)
5967(2)
7892(2)
7609(2)
7085(2)
5771(2)
5539(2)
9568(1)
2463(2)
8277(3)
6692(3)
8767(3)
7562(4)
6244(3)
9743(5)
38(1)
54(1)
62(1)
62(1)
68(1)
54(1)
40(1)
48(1)
46(1)
38(1)
48(1)
47(1)
38(1)
48(1)
47(1)
39(1)
29(1)
30(1)
47(1)
59(1)
62(1)
50(1)
68(1)
71(2)
52(1)
65(1)
60(1)
46(1)
37(1)
37(1)
42(1)
52(1)
59(1)
49(1)
70(2)
71(2)
56(1)
67(1)
68(2)
51(1)
38(1)
35(1)
31(1)
30(1)
37(1)
36(1)
32(1)
37(1)
64(1)
62(1)
53(1)
32(1)
65(1)
100(1)
98(1)
106(2)
107(2)
115(2)
234(4)
C(3)
C(4)
C(5)
C(6)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
C(107)
C(108)
C(109)
C(110)
C(111)
C(112)
C(201)
C(202)
C(203)
C(204)
C(205)
C(206)
C(207)
C(208)
C(209)
C(210)
C(211)
C(212)
C(301)
C(302)
C(303)
C(304)
C(305)
C(306)
C(307)
C(308)
C(309)
C(310)
C(311)
C(312)
N(1)
Fig. 1. Asymmetric unit of 1 (the water molecules and hydrogen atoms
are omitted for clarity). Atoms are shown as 50% probability
ellipsoids.
Fig. 2. [M(phen)3]2+ cations located between the adjacent layers of
phenylphosphonate anions and water molecules in compound 1:
N(2)
N(3)
N(4)
N(5)
N(6)
O(1)
O(2)
O(3)
OW1
OW2
OW3
OW4
OW5
OW6
OW7
OW8
Fig. 3. Two-dimensional network constructed by hydrogen bonds in
compound 1:

ARTICLE IN PRESS
J. Yang et al. / Journal of Solid State Chemistry 174 (2003) 116–124
120
Table 3 (continued)
Table 3 (continued)
x
y
z
UðeqÞ
x
y
z
UðeqÞ
OW9
OW10
OW11
P(1)
6033(4)
10339(4)
3748(5)
2643(4)
3370(1)
7371(1)
5510(3)
9557(4)
8846(2)
6168(1)
7315(1)
96(1)
116(2)
83(1)
39(1)
29(1)
OW6
OW7
OW8
OW9
OW10
OW11
P(1)
13803(5)
13565(5)
4688(7)
5832(6)
6435(7)
4650(9)
5411(1)
9412(1)
5400(6)
7380(11)
8725(6)
10471(6)
3254(7)
2768(8)
3464(2)
7433(1)
7761(5)
6289(5)
9837(5)
5594(4)
9502(4)
8639(7)
6122(1)
7345(1)
181(3)
322(8)
201(3)
188(3)
198(3)
276(5)
87(1)
6214(4)
4920(3)
5418(1)
9402(1)
Co(1)
[Ni(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 2
C(1)
C(2)
6773(4)
7557(5)
8609(5)
8863(6)
8062(7)
7046(6)
7862(4)
7454(5)
7984(5)
8899(4)
9529(5)
10419(5)
10764(4)
11676(4)
11935(4)
11300(4)
10153(4)
9238(4)
7315(4)
6545(5)
6714(6)
7669(5)
7966(8)
8925(8)
9679(6)
10689(7)
11360(6)
11019(4)
9412(5)
8407(4)
11637(4)
12308(5)
11869(6)
10728(5)
10181(7)
9118(7)
8495(5)
7372(6)
6814(5)
7408(5)
8983(4)
10127(4)
8723(3)
10433(3)
8220(3)
10076(3)
10578(3)
8451(3)
4913(5)
4667(4)
5621(7)
5505(10)
13010(2)
6422(4)
5314(4)
4408(6)
5136(5)
3709(4)
4010(5)
4212(6)
4090(5)
3832(6)
3640(5)
6898(4)
6208(5)
5144(5)
4744(4)
3631(4)
3289(4)
4022(4)
3709(4)
4470(5)
5537(4)
5126(3)
5481(3)
6692(4)
6632(5)
7042(6)
7524(5)
7958(6)
8384(6)
8444(5)
8875(5)
8901(5)
8513(4)
8043(4)
7564(4)
7527(4)
7976(5)
8919(5)
9449(4)
10441(5)
10913(5)
10414(4)
10866(5)
10363(5)
9394(4)
9453(4)
8943(4)
6553(3)
5872(3)
7151(3)
8088(3)
7986(3)
8942(3)
2808(5)
4557(5)
2543(7)
3532(12)
10988(2)
8787(4)
7844(5)
9240(5)
5632(6)
6277(4)
5558(4)
5639(5)
6481(6)
7218(5)
7093(4)
9132(3)
9901(3)
10075(3)
9495(3)
9629(4)
9073(4)
8276(3)
7657(4)
6916(4)
6809(3)
8115(3)
8740(3)
6955(4)
6399(5)
5531(5)
5189(4)
4266(5)
3963(4)
4540(3)
4271(4)
4866(4)
5772(3)
5453(3)
5772(3)
8029(3)
8439(4)
8724(4)
8611(3)
8899(4)
8776(4)
8330(3)
8169(4)
7715(4)
7427(3)
8037(3)
8195(3)
8561(2)
7375(2)
6651(2)
6054(2)
7909(2)
7582(2)
6937(4)
5915(4)
5570(5)
5082(8)
9519(2)
2504(3)
8356(4)
6827(5)
8911(4)
60(1)
81(2)
96(2)
98(2)
97(2)
79(2)
53(1)
61(1)
64(2)
47(1)
69(2)
63(1)
51(1)
61(1)
65(2)
51(1)
39(1)
38(1)
62(1)
83(2)
88(2)
70(2)
104(3)
100(3)
72(2)
88(2)
82(2)
62(1)
53(1)
52(1)
52(1)
69(2)
76(2)
62(1)
87(2)
89(2)
64(2)
87(2)
79(2)
63(1)
46(1)
46(1)
40(1)
40(1)
47(1)
47(1)
41(1)
44(1)
170(3)
147(2)
94(2)
101(4)
31(1)
115(2)
139(2)
196(3)
159(2)
Ni(1)
38(1)
C(3)
C(4)
[Cu(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 3
C(1)
C(2)
6792(3)
7553(4)
8615(4)
8905(5)
8133(5)
7084(5)
7771(4)
7398(4)
7962(4)
8893(3)
9564(4)
10471(4)
10780(3)
11695(4)
11925(4)
11270(3)
10136(3)
9201(3)
7388(4)
6609(4)
6726(5)
7674(5)
7888(7)
8848(8)
9680(5)
10683(7)
11398(6)
11106(4)
9448(4)
8454(3)
11618(4)
12283(4)
11837(5)
10680(5)
10155(6)
9045(8)
8399(5)
7262(6)
6734(5)
7338(4)
8929(4)
10082(3)
8642(3)
10397(2)
8286(3)
10159(3)
10550(3)
8404(3)
4886(4)
4674(3)
5634(5)
5561(10)
13076(2)
6402(3)
3679(3)
3990(5)
4184(5)
4037(5)
3762(5)
3578(4)
6830(4)
6099(5)
5045(4)
4678(3)
3578(4)
3258(4)
4000(3)
3709(4)
4455(4)
5506(4)
5091(3)
5436(3)
6674(4)
6585(5)
7019(5)
7524(4)
7985(6)
8427(6)
8476(4)
8925(5)
8935(5)
8509(4)
8055(3)
7565(3)
7568(4)
8030(5)
8945(5)
9461(4)
10448(5)
10900(5)
10391(4)
10813(4)
10299(4)
9352(4)
9441(3)
8951(3)
6495(3)
5833(2)
7141(3)
8087(3)
7995(3)
8918(3)
2831(5)
4532(4)
2527(5)
3496(13)
10975(2)
8818(3)
6250(3)
5530(3)
5631(4)
6453(5)
7168(4)
7059(3)
9204(3)
9972(3)
10129(3)
9533(2)
9660(3)
9080(3)
8294(3)
7656(3)
6929(3)
6835(3)
8148(2)
8778(2)
6902(3)
6385(5)
5541(5)
5172(3)
4269(4)
3936(4)
4494(3)
4199(4)
4765(4)
5651(3)
5390(2)
5731(2)
7997(3)
8396(3)
8703(3)
8615(3)
8909(4)
8814(4)
8369(3)
8221(4)
7763(4)
7461(3)
8055(2)
8197(2)
8624(2)
7412(2)
6600(2)
5958(2)
7894(2)
7596(2)
6936(4)
5885(4)
5511(4)
5035(9)
9485(1)
2528(3)
59(1)
81(1)
94(2)
99(2)
99(2)
83(1)
64(1)
79(1)
69(1)
57(1)
75(1)
69(1)
56(1)
71(1)
72(1)
61(1)
45(1)
45(1)
70(1)
92(2)
98(2)
79(1)
120(3)
120(3)
86(2)
113(2)
105(2)
80(1)
61(1)
57(1)
63(1)
81(1)
87(2)
72(1)
99(2)
110(2)
72(1)
95(2)
90(2)
70(1)
53(1)
54(1)
50(1)
47(1)
52(1)
59(1)
50(1)
54(1)
161(2)
143(2)
84(2)
134(4)
41(1)
107(1)
C(5)
C(6)
C(3)
C(4)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
C(107)
C(108)
C(109)
C(110)
C(111)
C(112)
C(201)
C(202)
C(203)
C(204)
C(205)
C(206)
C(207)
C(208)
C(209)
C(210)
C(211)
C(212)
C(301)
C(302)
C(303)
C(304)
C(305)
C(306)
C(307)
C(308)
C(309)
C(310)
C(311)
C(312)
N(1)
C(5)
C(6)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
C(107)
C(108)
C(109)
C(110)
C(111)
C(112)
C(201)
C(202)
C(203)
C(204)
C(205)
C(206)
C(207)
C(208)
C(209)
C(210)
C(211)
C(212)
C(301)
C(302)
C(303)
C(304)
C(305)
C(306)
C(307)
C(308)
C(309)
C(310)
C(311)
C(312)
N(1)
N(2)
N(3)
N(4)
N(5)
N(2)
N(3)
N(6)
O(1)
N(4)
N(5)
O(2)
O(3)
O(30)
N(6)
O(1)
OW1
OW2
O(2)
O(3)
O(30)
OW3
OW4
OW5
OW1
OW2

ARTICLE IN PRESS
J. Yang et al. / Journal of Solid State Chemistry 174 (2003) 116–124
121
Table 3 (continued)
Table 3 (continued)
x
y
z
UðeqÞ
x
y
z
UðeqÞ
OW3
OW4
OW5
OW6
OW7
OW8
OW9
OW10
OW11
P(1)
5303(4)
7792(5)
9195(5)
5608(6)
5447(6)
7356(9)
8713(6)
10403(6)
3268(6)
2786(7)
3417(1)
7421(1)
8314(4)
6815(4)
8889(4)
7696(5)
6296(4)
9767(5)
5543(5)
9542(4)
8594(6)
6096(1)
7331(1)
151(2)
175(2)
192(3)
182(3)
249(5)
191(3)
193(3)
181(2)
254(4)
83(1)
OW1
OW2
OW3
OW4
OW5
OW6
OW7
OW8
OW9
P(1)
4010(3)
À3914(3)
4900(3)
8268(3)
941(2)
1011(2)
672(2)
81(1)
68(1)
72(1)
141(2)
83(1)
103(1)
135(2)
96(1)
67(1)
46(1)
40(1)
69(1)
4480(6)
5146(6)
13843(5)
13610(5)
4735(6)
5836(6)
6341(6)
4685(8)
5419(1)
9411(1)
À542(2)
64(5)
186(2)
1885(2)
3814(3)
3298(2)
1936(3)
3594(3)
5170(3)
2569(2)
1299(1)
2241(1)
4628(1)
À1406(4)
2979(3)
1691(3)
À1529(3)
À662(4)
173(3)
977(4)
À3631(3)
À3301(3)
À947(1)
2830(1)
À1320(2)
316(1)
Cu(1)
43(1)
Cd(1)
Cl(1)
4195(1)
À1963(1)
À4025(1)
[Cd(phen)]3 ꢁ C6H5PO3H ꢁ Cl ꢁ 7H2O 4
C(1)
C(2)
À776(3)
À752(5)
À588(6)
À390(6)
À421(5)
À618(4)
3099(3)
3502(4)
4369(4)
4841(3)
5773(4)
6231(4)
5790(3)
6249(4)
5803(4)
4866(3)
4865(3)
4390(3)
1823(4)
1041(4)
À40(4)
1694(3)
2066(4)
3129(5)
3786(5)
3419(4)
2387(3)
6496(3)
7156(3)
6718(3)
5615(3)
5104(4)
4041(5)
3374(3)
2271(4)
1702(3)
2214(3)
3836(3)
4987(3)
2658(3)
2306(3)
2908(3)
3867(3)
4558(3)
5485(3)
5774(3)
6706(3)
6936(3)
6241(3)
5110(2)
4141(2)
1961(3)
1305(3)
1688(3)
2710(3)
3171(4)
4186(4)
4826(3)
5878(3)
6425(3)
5931(3)
4385(2)
3322(2)
5441(2)
3255(2)
3538(2)
5353(2)
2942(2)
4952(2)
À73(2)
334(2)
1326(3)
2076(4)
2083(5)
1308(6)
572(5)
52(1)
85(1)
116(2)
115(2)
100(2)
74(1)
51(1)
64(1)
67(1)
56(1)
78(1)
79(1)
57(1)
75(1)
73(1)
58(1)
42(1)
41(1)
58(1)
71(1)
67(1)
50(1)
60(1)
61(1)
50(1)
67(1)
71(1)
56(1)
40(1)
39(1)
64(1)
80(1)
74(1)
58(1)
74(1)
73(1)
54(1)
65(1)
63(1)
51(1)
42(1)
44(1)
42(1)
44(1)
45(1)
43(1)
47(1)
42(1)
65(1)
53(1)
56(1)
C(3)
C(4)
C(5)
C(6)
3.2. Luminescence
572(3)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
C(107)
C(108)
C(109)
C(110)
C(111)
C(112)
C(201)
C(202)
C(203)
C(204)
C(205)
C(206)
C(207)
C(208)
C(209)
C(210)
C(211)
C(212)
C(301)
C(302)
C(303)
C(304)
C(305)
C(306)
C(307)
C(308)
C(309)
C(310)
C(311)
C(312)
N(1)
2883(2)
3276(3)
3627(3)
3575(2)
3915(3)
3830(3)
3411(2)
3294(3)
2884(3)
2576(3)
3084(2)
3164(2)
4032(3)
4812(3)
5079(3)
4591(2)
4874(3)
4400(3)
3579(2)
3054(3)
2291(3)
2041(3)
3284(2)
3821(2)
1579(3)
985(4)
Among the four complexes, compound 4 shows
luminescent property. The emission spectrum exhibits
two peaks at 365 and 382 nm upon photoexcitation at
320 nm. These emission bands may be attributed to o-
phenanthroline pꢀ-p transition. Compound 4 may be a
potential luminescent material.
3.3. FT-IR spectra
In the IR spectra, all compounds showabsorption
bands at 3404–3493 cmÀ1, corresponding to the presence
of water. The C–H stretching modes for the phenyl rings
are relatively weak and are observed at about
3055 cmÀ1. The multiple bands in the region of 900–
1150 cmÀ1 are phosphonate P–O vibrations [19,20]. A
series of characteristic peaks in the 1425–1520 cmÀ1
range are attributed to o-phenanthroline molecules [21].
À350(3)
À1452(3)
À1724(3)
À915(3)
À1174(4)
À388(4)
684(3)
182(3)
477(3)
3.4. Thermal analysis
2515(4)
2380(4)
2478(4)
2742(3)
2820(4)
3057(4)
3234(3)
3484(4)
3689(4)
3630(3)
3173(3)
2892(3)
3518(2)
4414(2)
1555(2)
973(2)
In order to characterize more fully these compounds
in terms of thermal stability, the thermal behavior of
compound 3 was studied using TGA (Fig. 5). Com-
pound 3 was heated from 35ꢂC to 800ꢂC in N2. When
the crystals were removed from the mother liquor, they
immediately lost part of the water molecules. TGA was
performed after part of their water molecules had
evaporated. A weight loss corresponding to the remain-
ing water was observed over the wide temperature range
35–120ꢂC. From 195ꢂC to 700ꢂC, the anhydrous
compound decomposes with stepwise loss of the organic
portion. However, it is difficult to determine these
weight losses accurately as these processes are over-
lapped with the weight losses due to the dissociation of
the organic fractions.
149(4)
À140(3)
À1004(3)
À1261(3)
À662(2)
À890(3)
À301(3)
536(2)
202(2)
484(2)
2820(2)
2678(2)
3546(2)
2516(2)
1321(2)
786(2)
N(2)
N(3)
N(4)
N(5)
2769(3)
3359(2)
À1633(3)
À1542(2)
284(2)
N(6)
O(1)
2183(2)
591(2)
985(2)
In summary, the divalent transition metal phenyl-
phosphonate complexes with o-phenanthroline ligand
O(2)
O(3)
À361(2)

ARTICLE IN PRESS
J. Yang et al. / Journal of Solid State Chemistry 174 (2003) 116–124
122
Table 4 (continued)
Table 4
Anisotropic displacement parameters (A2 Â 103) for 1–4
U11
U22
U33
37(1)
29(1)
U23
U13
U12
U11
U22
U33
U23
U13
U12
P(1)
Co(1)
28(1)
23(1)
48(1)
32(1)
0(1)
À4(1)
À1(1)
À2(1)
À7(1)
À5(1)
[Co(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 1
C(1)
C(2)
34(2)
41(2)
39(2)
39(2)
75(3)
62(3)
30(2)
37(2)
49(2)
38(2)
59(3)
54(3)
30(2)
33(2)
32(2)
31(2)
24(2)
28(2)
30(2)
35(2)
48(3)
48(2)
84(4)
106(5)
69(3)
88(4)
57(3)
37(2)
42(2)
37(2)
31(2)
42(2)
66(3)
65(3)
109(5)
123(5)
76(3)
75(3)
44(2)
34(2)
47(2)
42(2)
25(1)
24(1)
31(2)
32(2)
29(1)
30(2)
49(2)
32(2)
46(2)
46(1)
57(2)
69(3)
98(3)
135(4)
50(2)
57(2)
322(12)
98(3)
105(4)
80(3)
34(2)
78(3)
88(4)
64(3)
71(3)
61(3)
47(2)
64(3)
55(3)
45(2)
39(2)
30(2)
35(2)
37(2)
51(3)
48(2)
29(2)
36(2)
53(2)
61(3)
66(3)
49(3)
67(3)
64(3)
45(2)
59(3)
63(3)
50(2)
32(2)
32(2)
57(3)
66(3)
68(3)
44(2)
44(3)
37(3)
35(2)
43(3)
49(3)
43(2)
30(2)
34(2)
38(2)
35(2)
39(2)
37(2)
39(2)
34(2)
101(3)
65(2)
64(2)
23(1)
63(2)
110(4)
79(3)
109(4)
130(4)
217(6)
209(9)
80(3)
144(5)
103(3)
43(2)
49(2)
67(3)
92(4)
65(3)
41(2)
39(2)
41(2)
33(2)
36(2)
47(2)
59(3)
50(2)
71(3)
60(3)
38(2)
36(2)
30(2)
63(3)
91(4)
83(4)
57(3)
58(3)
40(2)
35(2)
34(2)
49(3)
45(2)
33(2)
42(2)
36(2)
52(2)
54(3)
41(2)
69(3)
55(3)
45(2)
70(3)
86(4)
66(3)
32(2)
29(2)
29(1)
32(1)
40(2)
36(2)
27(1)
42(2)
41(2)
72(2)
55(2)
23(1)
71(2)
117(4)
115(4)
80(3)
163(5)
71(3)
136(6)
114(3)
112(4)
63(2)
À7(2)
À1(2)
À3(2)
[Ni(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 2
À24(2)
À35(3)
7(2) À20(2)
15(2) À28(2)
C(1)
C(2)
47(3)
59(4)
55(4)
78(5)
104(6)
85(5)
47(3)
61(4)
73(4)
51(3)
85(4)
72(4)
49(3)
46(3)
41(3)
42(3)
34(2)
37(3)
45(3)
48(4)
67(5)
78(4)
151(8)
153(8)
99(5)
125(7)
80(5)
54(3)
67(4)
56(3)
43(3)
57(4)
89(5)
89(4)
121(6)
143(7)
79(4)
112(6)
62(4)
55(4)
58(3)
55(3)
36(2)
34(2)
38(2)
46(2)
37(2)
35(2)
98(4)
52(3)
95(6)
61(3)
118(5)
137(6)
83(5)
102(5)
83(4)
54(3)
71(4)
65(4)
43(3)
58(4)
38(3)
41(3)
48(3)
71(4)
57(3)
38(2)
36(2)
65(4)
87(5)
96(5)
66(4)
94(6)
94(5)
60(4)
70(4)
72(4)
58(3)
42(3)
47(3)
62(3)
80(4)
75(4)
51(3)
67(4)
55(4)
43(3)
51(4)
56(4)
53(3)
35(2)
41(3)
43(2)
41(2)
51(2)
44(2)
45(2)
40(2)
177(6)
132(5)
99(6)
68(3)
77(4)
110(5)
152(7)
90(5)
70(4)
53(3)
49(3)
50(3)
48(3)
60(3)
76(4)
66(3)
89(4)
86(4)
54(3)
49(3)
43(2)
84(4)
131(6)
116(6)
74(4)
73(5)
45(3)
44(3)
46(3)
69(4)
61(3)
44(3)
54(3)
49(3)
77(4)
80(4)
58(3)
86(4)
81(4)
62(3)
85(4)
99(5)
72(4)
43(2)
43(2)
38(2)
43(2)
53(2)
47(2)
40(2)
50(2)
204(6)
208(6)
103(6)
105(9)
38(1)
123(4)
170(5)
224(7)
150(5)
À9(3) À12(3)
À1(3)
C(3)
C(4)
À40(4)
À54(5)
À7(3) À16(4)
9(4) À35(4)
À22(3) À14(3) À16(2)
3(3) À30(3) À28(3)
6(2) À13(2) À27(2)
C(3)
C(4)
C(5)
C(6)
À46(5) À57(5)
À2(4)
C(5)
C(6)
2(4) À43(5) À31(5)
2(3) À24(3) À26(4)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
C(107)
C(108)
C(109)
C(110)
C(111)
C(112)
C(201)
C(202)
C(203)
C(204)
C(205)
C(206)
C(207)
C(208)
C(209)
C(210)
C(211)
C(212)
C(301)
C(302)
C(303)
C(304)
C(305)
C(306)
C(307)
C(308)
C(309)
C(310)
C(311)
C(312)
N(1)
À9(2)
À13(2)
À3(2)
3(2)
À3(2)
9(2) À12(2)
4(2) À21(2)
À5(2) À21(2)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
C(107)
C(108)
C(109)
C(110)
C(111)
C(112)
C(201)
C(202)
C(203)
C(204)
C(205)
C(206)
C(207)
C(208)
C(209)
C(210)
C(211)
C(212)
C(301)
C(302)
C(303)
C(304)
C(305)
C(306)
C(307)
C(308)
C(309)
C(310)
C(311)
C(312)
N(1)
À11(2)
À11(3)
7(3)
0(2)
À4(2)
12(3) À21(3)
1(3) À30(3)
À6(2) À16(2)
À9(3) À28(3)
À2(2)
5(2) À11(2) À20(2)
0(2)
9(3)
À3(2) À17(2)
À7(2)
À4(2)
5(2)
À12(2)
À20(2)
À25(2)
À15(2)
À9(1)
À9(2)
À5(2)
4(2)
0(3) À22(3)
À4(3)
À8(2)
5(2)
À10(2) À20(3)
À23(3) À11(3)
À3(2)
À8(2)
À5(1)
6(2)
À5(1)
À39(3)
À14(2)
5(3)
2(2)
À1(3)
À9(2)
À8(2)
À6(1)
À5(1) À10(2)
À6(2) À16(2)
À9(2) À14(2)
À13(2)
À6(2) À11(2) À11(2)
À25(3) À13(3) À12(3)
À48(4) À28(4) À11(3)
À29(3) À15(2) À10(2)
À31(3) À37(3)
À20(2) À24(2)
À15(2) À39(3)
À6(2) À28(3)
À3(2) À11(2)
7(2)
5(2)
1(3)
4(3)
1(2)
À47(5) À48(4)
À30(3) À42(3)
À26(4) À66(5)
À7(3) À38(5)
6(4)
12(3)
18(5)
9(5)
7(2)
8(2)
6(2) À13(3)
10(2) À16(2)
À1(2) À12(2)
À4(3)
7(3)
À9(3)
11(4)
17(4)
8(3)
À7(4)
À9(3)
5(2)
À2(1)
10(3)
6(3)
À6(2)
3(2)
0(2)
6(3) À13(3)
À9(2) À12(2)
À5(2) À14(3)
À15(2) À19(3)
4(2)
4(2)
À3(2)
À5(2) À14(2)
À3(2) À13(2) À23(2)
À1(2) À22(2) À35(3)
À1(2)
À9(2) À14(3)
0(3) À29(3) À31(3)
À4(3) À33(3) À46(4)
À5(3) À27(3) À26(3)
À21(3) À40(4) À23(4)
À33(3) À24(4) À12(4)
À5(2)
À9(2) À20(2)
À15(2) À33(3) À18(3)
À23(2)
À5(2)
À9(2)
7(3)
À6(3)
8(2)
7(3)
À9(3)
1(2)
4(2)
À4(3)
À7(3)
À2(3)
3(4)
6(3)
À2(2)
4(2)
16(2)
À3(2)
À7(2)
À19(3)
10(4)
À5(3) À10(3)
0(3) À12(3)
3(2)
20(3)
À2(3)
À1(1)
À3(1)
À9(1)
À9(1)
À8(1)
À2(1)
À4(1)
À1(1)
7(2)
À2(2) À11(2)
À3(2)
À2(2) À11(2)
0(1)
1(1)
À4(1)
À6(1)
À4(1)
À7(1)
À8(1)
À4(1)
0(2) À13(2) À17(2)
N(2)
N(3)
À8(2)
À7(2)
0(2)
À8(2)
À8(2)
À6(2)
À4(2)
À6(2)
À7(1)
À3(1)
À1(1)
2(1)
N(2)
N(3)
N(4)
N(5)
À14(2) À10(2)
N(4)
N(5)
À3(2)
À3(2)
0(2)
À6(2)
N(6)
O(1)
À8(2) À11(2)
1(1) À33(2)
N(6)
O(1)
À5(2)
À1(2)
O(2)
O(3)
9(2)
À1(2)
5(1)
93(5) À52(4) À76(4)
0(3)
À14(2) À12(1) À15(2)
O(2)
O(3)
O(30)
60(4) À29(3)
OW1
OW2
À4(1)
10(1)
0(2) À15(2)
À7(1)
À8(2)
À18(5) À38(5) À32(5)
À47(8) À40(7) À36(8)
95(9) 133(11)
OW3
OW4
À12(3)
À34(3)
À4(3) À26(3)
12(3) À18(2)
OW1
OW2
39(2)
101(4)
84(4)
20(1)
104(4)
162(5)
115(5)
182(6)
222(7)
À16(1) À12(1)
1(3) À26(3)
1(1)
À1(3)
OW5
OW6
À16(3) À20(3) À32(3)
OW3
OW4
À40(4) À12(4) À20(4)
À92(4)
À3(3)
À1(2) À15(3)
18(8)
À7(3) À20(2)
À19(3) À27(3) À45(3)
À27(2) 15(2) À18(2)
À9(2)
191(7)
165(6)
87(4)
À23(5)
87(6)
À56(4) À39(4) À38(5)
À4(4)
OW7
OW8
À39(3)
OW5
OW6
À36(6) À12(7)
266(8) À131(6) À26(5)
À6(4)
OW9
OW10
OW11
À29(3)
OW7
OW8
60(4) 760(20)
214(8) 161(6)
138(6) À115(9)
228(8)
À3(4) À46(8)
À68(6) À68(6)
28(6)

ARTICLE IN PRESS
J. Yang et al. / Journal of Solid State Chemistry 174 (2003) 116–124
123
Table 4 (continued)
Table 4 (continued)
U11
U22
U33
U23
U13
U12
U11
U22
U33
171(5)
U23
U13
U12
OW9
OW10
OW11
P(1)
159(6)
244(8)
231(8)
226(8)
153(6)
139(5)
À24(5)
À11(5) À44(6) À86(7)
130(9) À78(8)
À1(5) À19(6)
OW5
OW6
OW7
OW8
OW9
OW10
OW11
P(1)
226(7)
107(4)
79(3) 514(15)
201(7)
À43(5) À56(5) À57(6)
204(6)
257(7) À104(5) À30(4) À13(4)
283(11) 259(10) 277(10) À135(9)
146(5)
229(7)
191(6)
154(5)
À85(7) À10(3) À21(6)
47(1)
35(1)
121(2)
39(1)
89(1)
39(1)
À11(1) À13(1) À15(1)
182(6)
182(6)
206(6)
241(9)
50(1)
160(5)
194(6)
204(6)
269(9)
114(1)
44(1)
À57(5) À49(5)
À54(5) 0(5)
14(5)
À9(5)
Ni(1)
À5(1)
À5(1)
À7(1)
À27(4) À41(4) À77(5)
[Cu(phen)3] ꢁ C6H5PO3 ꢁ 11H2O 3
254(8) À125(7)
108(7) À90(7)
C(1)
C(2)
49(2)
60(3)
60(3)
76(4)
111(5)
83(3)
52(2)
66(3)
71(3)
60(2)
93(4)
79(3)
55(2)
50(2)
50(2)
53(2)
43(2)
43(2)
50(2)
57(3)
73(3)
86(3)
165(7)
195(8)
122(5)
145(6)
98(5)
64(3)
77(3)
61(2)
50(2)
64(3)
100(4)
100(4)
137(6)
195(8)
99(4)
109(5)
72(3)
55(3)
67(2)
66(2)
47(2)
44(2)
47(2)
59(2)
49(2)
52(2)
103(3)
56(2)
78(4)
61(3)
111(4)
124(5)
87(4)
105(5)
93(4)
67(3)
104(4)
70(3)
56(2)
58(3)
43(2)
45(2)
59(3)
85(3)
67(3)
44(2)
46(2)
72(3)
94(4)
109(5)
77(3)
115(5)
99(5)
66(3)
87(4)
79(4)
63(3)
46(2)
52(2)
79(3)
93(4)
93(4)
60(3)
71(4)
57(3)
47(2)
61(3)
68(3)
68(3)
42(2)
47(2)
52(2)
49(2)
54(2)
51(2)
51(2)
51(2)
173(5)
134(4)
84(4)
66(2)
77(3)
111(4)
154(6)
93(4)
73(3)
71(3)
70(3)
64(3)
57(2)
74(3)
85(3)
74(2)
104(3)
82(3)
63(2)
53(2)
49(2)
93(3)
143(5)
132(5)
82(3)
85(4)
53(3)
53(2)
70(4)
105(5)
98(3)
51(2)
58(2)
62(2)
90(3)
88(3)
66(3)
103(4)
89(4)
64(3)
92(4)
111(4)
79(3)
46(2)
48(2)
52(2)
48(2)
57(2)
62(2)
47(2)
55(2)
184(5)
196(5)
100(4)
À11(2) À13(2)
À2(2)
83(1)
46(1)
À16(1) À13(1) À14(1)
À34(3)
À50(4)
À5(2) À16(3)
7(3) À30(3)
Cu(1)
38(1)
À7(1)
À9(1)
À6(1)
C(3)
C(4)
À41(4) À51(4)
À7(3)
[Cd(phen)3] ꢁ C6H5PO3H ꢁ Cl ꢁ 7H2O 4
C(5)
C(6)
2(3) À49(4) À40(4)
2(3) À21(3) À25(3)
C(1)
C(2)
40(2)
87(4)
117(5)
99(5)
105(4)
77(3)
61(2)
84(3)
82(3)
56(2)
74(3)
60(3)
46(2)
53(3)
69(3)
54(2)
38(2)
42(2)
59(2)
75(3)
66(3)
49(2)
47(2)
38(2)
42(2)
47(2)
66(3)
52(2)
40(2)
40(2)
77(3)
81(3)
80(3)
51(2)
71(3)
76(3)
48(2)
65(3)
67(3)
59(2)
37(2)
40(2)
48(2)
39(2)
49(2)
41(2)
51(2)
48(2)
65(2)
47(1)
48(2)
99(3)
54(2)
97(3)
109(5)
64(3)
60(3)
57(2)
36(2)
40(2)
63(2)
68(2)
100(4)
115(4)
68(2)
85(3)
50(2)
40(2)
47(2)
46(2)
43(2)
54(2)
69(2)
52(2)
75(3)
73(2)
52(2)
59(2)
52(2)
50(2)
37(1)
37(1)
36(2)
38(2)
51(2)
57(2)
90(3)
97(3)
66(2)
73(2)
51(2)
42(2)
44(2)
41(2)
35(1)
37(1)
35(1)
39(1)
34(1)
36(1)
74(2)
59(1)
58(1)
75(2)
62(2)
86(3)
145(6)
191(8)
139(5)
90(3)
56(2)
73(3)
68(3)
51(2)
79(3)
72(3)
47(2)
71(3)
79(3)
68(2)
36(2)
34(2)
60(2)
67(3)
55(2)
48(2)
54(2)
70(3)
60(2)
89(3)
87(3)
62(2)
50(2)
42(2)
84(3)
128(5)
104(4)
69(3)
67(3)
46(2)
42(2)
45(2)
62(2)
50(2)
41(2)
52(2)
43(2)
47(2)
47(2)
49(2)
59(2)
42(2)
51(2)
59(2)
56(2)
85(2)
À13(2) À15(2)
À6(2)
À22(3) À28(3) À34(3)
À65(5) À41(5) À31(4)
À25(4) À48(5) À18(3)
14(3) À44(4) À28(3)
1(2) À31(3) À15(2)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
C(107)
C(108)
C(109)
C(110)
C(111)
C(112)
C(201)
C(202)
C(203)
C(204)
C(205)
C(206)
C(207)
C(208)
C(209)
C(210)
C(211)
C(212)
C(301)
C(302)
C(303)
C(304)
C(305)
C(306)
C(307)
C(308)
C(309)
C(310)
C(311)
C(312)
N(1)
À19(2)
À28(3)
À1(2)
À6(2)
À1(2)
C(3)
C(4)
13(2) À26(3)
1(2) À27(2)
À9(2) À23(2)
C(5)
C(6)
À2(2)
10(2) À22(3) À31(3)
À2(2) À24(3) À10(2)
C(101)
C(102)
C(103)
C(104)
C(105)
C(106)
C(107)
C(108)
C(109)
C(110)
C(111)
C(112)
C(201)
C(202)
C(203)
C(204)
C(205)
C(206)
C(207)
C(208)
C(209)
C(210)
C(211)
C(212)
C(301)
C(302)
C(303)
C(304)
C(305)
C(306)
C(307)
C(308)
C(309)
C(310)
C(311)
C(312)
N(1)
À3(1) À19(2)
À6(2)
À10(2) À22(2) À17(2)
À16(2) À25(2) À30(2)
À9(2) À19(2) À18(2)
À17(3) À44(3) À15(3)
À15(2) À25(2)
À30(2) À15(2)
À5(2)
5(2)
À32(3)
À19(2)
5(2)
3(2) À12(2)
À8(2)
À5(3) À41(2)
3(2) À14(2)
11(2) À20(2)
À2(2) À15(2)
À5(2) À11(2)
À9(3)
3(2)
À9(2) À14(2) À10(2)
À6(1) À13(1) À13(2)
14(2)
17(2)
4(2)
À26(2) À13(2)
À8(2)
À51(4) À28(3) À12(3)
À59(4) À57(3)
À37(2) À46(3)
À34(4) À76(5)
À6(3) À48(4)
11(3)
17(3)
30(5)
18(5)
8(3)
2(1)
À9(1)
À4(1)
0(1) À10(1) À11(1)
4(2) À11(2)
22(2) À13(2)
0(2)
À6(2)
À3(2)
14(3)
10(3)
5(2)
À8(3)
11(2)
À2(2) À14(2) À12(2)
À5(2) À20(2)
26(4)
1(4)
33(4) À10(3)
À5(2)
À8(2) À14(2)
0(2)
À8(2)
8(2)
12(2)
À18(2) À15(2)
À7(2) À20(2)
À4(2) À26(2)
15(2) À32(3)
11(2) À19(2)
À8(1) À20(2)
À6(1) À13(1)
À2(2)
À5(2)
11(2)
5(2)
À6(2) À16(2)
À18(2) À26(2)
À5(2)
À7(2) À21(2)
À1(3) À23(2) À30(3)
À5(3) À35(3) À54(3)
À11(2) À22(2) À29(3)
À21(3) À48(4) À24(4)
À31(3) À35(4) À16(4)
À6(2)
À6(1)
À8(1)
4(2) À31(2) À18(2)
À17(2) À35(3) À16(2)
À4(2) À10(2)
9(3)
À5(2)
12(3)
19(3)
À2(2)
À33(2) À38(3)
À28(2) À19(2)
À40(2) À23(2)
À6(2)
À4(2)
À4(2)
À13(3)
À7(3) À11(3)
1(2) À16(2)
À14(2) À16(2) À13(3)
À2(2)
À2(2) À11(2)
À10(2)
11(2)
8(2)
À5(2)
À9(2)
1(2) À11(2) À19(2)
À5(2) À19(2)
À4(2) À20(2)
À11(1)
À6(1)
À8(1)
À9(1)
À6(1)
À9(1)
À5(1)
À4(2)
N(2)
N(3)
0(2) À11(2) À17(2)
À17(1) À11(1)
0(2) À15(2)
À7(1)
À8(1)
À5(1)
À2(1)
À6(1)
1(1)
N(4)
N(5)
À15(1) À15(2)
À3(1) À14(1)
À4(1)
À3(1)
À7(1) À10(1)
À7(1) À10(2)
N(6)
O(1)
N(2)
N(3)
À3(1)
À9(1)
78(4) À39(3) À72(3)
2(1) À15(1)
2(1) À16(1)
À4(1) À20(2)
À5(1)
À4(1)
À9(1)
O(2)
O(3)
O(30)
58(3) À24(3)
À5(2)
N(4)
N(5)
À19(3) À32(3) À20(3)
101(8) 184(13) 159(11) À78(10) À55(8) À44(9)
N(6)
O(1)
À2(1)
À9(1) À11(1)
OW1
OW2
50(1)
96(3)
98(3)
31(1)
100(3)
189(5)
119(4)
46(1)
117(3)
168(5)
207(6)
À14(1) À13(1)
À3(2) À29(2)
À4(1)
À7(2)
5(1) À10(1) À17(1)
À6(1) À24(1) À11(1)
O(2)
O(3)
OW3
OW4
À47(4) À13(3) À20(3)
À4(1) À20(1)
4(1)
6(2) À46(2) À24(2)
178(6)
À36(4)
20(5) À14(4)
OW1

ARTICLE IN PRESS
J. Yang et al. / Journal of Solid State Chemistry 174 (2003) 116–124
124
Table 4 (continued)
display newremarkable structure containing hydrogen-
bonded layers of anions and water molecules. The
introduction of o-phenanthroline into the divalent
transition metal phosphonates in the present work not
only displays the function of tailoring the microstructure
of layered metal phosphonate, but also provides the
methods to extend the knowledge of the chemistry of
layered metal phosphonates by introducing organic
amine ligand.
U11
U22
62(2)
U33
73(2)
U23
U13
U12
OW2
OW3
OW4
OW5
OW6
OW7
OW8
OW9
P(1)
71(2)
72(2)
139(4)
93(2)
89(3)
100(3)
87(3)
70(2)
44(1)
43(1)
68(1)
3(1) À28(2) À10(1)
3(2) À27(2) À27(2)
82(2)
188(5)
65(2)
87(2)
161(4)
97(2)
64(2)
48(1)
34(1)
70(1)
71(2)
83(3)
85(2)
139(3)
140(4)
113(3)
70(2)
44(1)
43(1)
66(1)
23(3) À44(3)
À3(3)
À4(2)
À5(2) À28(2)
41(2) À63(2) À16(2)
12(3) À38(3) À26(3)
À15(2) À48(2)
À2(1) À27(2)
À2(1) À13(1)
À2(1) À14(1)
À14(1) À17(1)
À5(2)
À9(1)
À7(1)
À6(1)
À6(1)
Cd(1)
Cl(1)
Acknowledgments
The anisotropic displacement factor exponent takes the form:
2
À2p2½ðhaꢀÞ U11 þ ? þ 2hkaꢀbꢀU12ꢃ:
We thank the Fok Ying Tung Education Foundation
and the Ministry of Education of China for Support.
References
[1] J.D. Wang, A. Clearfield, G.Z. Peng, Mater. Chem. Phys. 35
(1993) 208–216.
[2] B.Z. Wan, R.G. Anthony, G.Z. Peng, A. Cleafield, J. Catal. 101
(1986) 19–27.
[3] H. Byrd, A. Cleafield, D.M. Poojary, K.P. Reis, M.E. Thompson,
Chem. Mater. 8 (1996) 2239–2246.
[4] D. Deniaud, B. Schollorn, D. Mansuy, J. Rouxel, P. Battioni, B.
Bujoli, Chem. Mater. 7 (1995) 995–1000.
[5] G. Alberti, M. Casciola, R. Palombari, Solid State Ion. 61 (1993)
241–244.
[6] A. Clearfield, Curr. Opin. Solid State Mater. Sci. 1 (1996)
268–278.
[7] G. Cao, H. Hong, T.E. Mallouk, Acc. Chem. Res. 25 (1992)
420–427.
[8] G. Cao, T.E. Mallouk, Inorg. Chem. 30 (1991) 1434–1438.
[9] P.J. Zapf, R.C. Haushalter, J. Zubieta, Chem. Commun. (1997)
321–322 and references therein.
[10] J. Morizzi, M. Hobday, C. Rix, J. Mater. Chem. 11 (2001)
794–798.
Fig. 4. Asymmetric unit of 4 (the water molecules and hydrogen atoms
are omitted for clarity). Atoms are shown as 50% probability
ellipsoids.
[11] R.C. Finn, J. Zubieta, Inorg. Chem. 40 (2001) 2466–2467.
[12] R.C. Finn, R.S. Rarig Jr, J. Zubieta, Inorg. Chem. 41 (2002)
2109–2123.
[13] G.M. Sheldrick, Program for crystal structure solution,
University of Gottingen, 1997.
[14] G.M. Sheldrick, Program for crystal structure refinement,
University of Gottingen, 1997.
[15] G. Cao, H. Lee, V.M. Lynch, T.E. Mallouk, Inorg. Chem. 27
(1988) 2781–2785.
[16] D.M. Poojary, B. Zhang, A. Cabeza, M.A.G. Aranda, S. Bruque,
A. Clearfield, J. Mater. Chem. 6 (1996) 639–644.
[17] G. Cao, V.M. Lynch, L.N. Yacullo, Chem. Mater. 5 (1993)
1000–1006.
[18] Y.P. Zhang, A. Clearfield, Inorg. Chem. 31 (1992) 2821–2826.
[19] A. Cabeza, X.Q. Yang, C.V.K. Sharma, M.A.G. Aranda,
S. Bruque, A. Clearfield, Inorg. Chem. 41 (2002) 2325–2333.
[20] H.S. Martinez-Tapia, A. Cabeza, S. Bruque, P. Pertierra,
S. Garcia-Granda, M.A.G. Abranda, J. Solid State Chem.
151 (2000) 122–129.
[21] Y.G. Li, E.B. Wang, H. Zhang, G.Y. Luan, C.W. Hu, N.H. Hu,
H.Q. Jia, J. Solid State Chem. 163 (2002) 10–16.
Fig. 5. TGA curve for [Cu(phen)3] ꢁ C6H5PO3 ꢁ 11H2O in N2.