Poly[lead(II)-μ2-aqua-μ4-terephthalato]

Article abstract of DOI:10.1107/S0108270103029573

The title compound, [Pb(C₈H₄O₄)(H ₂O)]_n, forms as an insoluble product in the reaction of sodium terephthalate(2-) with Pb(NO₃)₂ in water. Analysis has shown that the crystal structure is centrosymmetric, with the asymmetric unit containing one formula unit. The lead geometry is hemidir-ected seven-coordinate, with both monodentate and bidentate carboxylate coordination modes present. The combination of hydrogen bonds and coordination bonds produces a three-dimensional structure, including the first example, in a lead complex, of the common metal-coordinated carboxylate/water R₁ ¹(6) graph-set motif.

Full text of DOI:10.1107/S0108270103029573

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
II
Pb complex in water and organic solvents. However, the slow
diffusion of separate aqueous solutions of Pb(NO ) and
3
2
Na TA (formed from the reaction of H TA with two equiva-
2
2
ISSN 0108-2701
lents of NaOH) results in the formation of crystals of the title
compound, [Pb(TA)(H O)], (I).
The asymmetric unit of (I) contains one formula unit. The
2
Poly[lead(II)-l -aqua-l -tereph-
II
Pb cation is seven-coordinate (Fig. 1), having a hemidirected
2
4
coordination sphere (Shimoni-Livny et al., 1998). The water
II
thalato]
molecule asymmetrically bridges two symmetry-related Pb
centres, and the remaining ®ve coordination bonds on each Pb
Sophie H. Dale, Mark R. J. Elsegood* and Sarita Kainth
II
atom involve Pb±carboxylate interactions. Each Pb cation
2�
bonds to three symmetry-related TA anions via mono-
dentate coordination, while bidentate coordination is
Chemistry Department, Loughborough University, Leicestershire LE11 3TU, England
Correspondence e-mail: m.r.j.elsegood@lboro.ac.uk
2
observed for a fourth TA anion, having a bite angle of
�
II
1.07 (12) [the CSD range for bidentate Pb /Pb ±carboxyl-
IV
Received 9 December 2003
Accepted 22 December 2003
Online 31 January 2004
ꢀ
5
ꢀ
ꢀ
ate complexes is 45.82±58.33 , mean 51.3 (2) ]. The mono-
dentate Pb±carboxylate bond lengths in (I) lie in the range
Ê Ê
.492 (3)±2.751 (4) A [mean 2.658 A; the CSD range for all
2
Pb /Pb ±carboxylate interactions (monodentate and biden-
The title compound, [Pb(C H O )(H O)] , forms as an
2
8
4
4
n
II
IV
insoluble product in the reaction of sodium terephthalate(2� )
Ê
Ê
tate) is 2.148±3.075 A, mean 2.582 (8) A] and the bidentate
Pb±carboxylate bond lengths in (I) are 2.434 (4) and 2.650 (4)
with Pb(NO ) in water. Analysis has shown that the crystal
3
2
structure is centrosymmetric, with the asymmetric unit
containing one formula unit. The lead geometry is hemidir-
ected seven-coordinate, with both monodentate and bidentate
carboxylate coordination modes present. The combination of
hydrogen bonds and coordination bonds produces a three-
dimensional structure, including the ®rst example, in a lead
II
A [mean 2.542 A; the CSD range for bidentate Pb /Pb ±
IV
Ê
Ê
Ê
carboxylate interactions is 2.177±2.968 A, mean 2.532 (15) A].
Ê
Ê
The mean bridging water±Pb bond length is 2.661 A [the CSD
II
range for Pb /Pb ÐOH bond lengths is 2.354±2.974 A,
IV
Ê
2
Ê
mean 2.62 (2) A].
The TA anion bridges four symmetry-related Pb centres,
utilizing three of its O atoms, the fourth (O2) being involved in
2�
II
complex, of the common metal-coordinated carboxylate/water
1
R (6) graph-set motif.
1
2�
hydrogen bonding. While the TA
centres using both of its carboxylate groups in most of its
anion bridges metal
II
divalent transition metal complexes [for example, Mg , Mn
II
Comment
II
and Fe (Kaduk, 2002), Cd (Michaelides et al., 1998), and
II
As part of our recent study of monovalent and divalent metal
salts of terephthalic acid (benzene-1,4-dicarboxylic acid,
H TA; Dale & Elsegood, 2003a,b), we have investigated the
II
Zn (Edgar et al., 2001)], by contrast, in the structures of Cu
II
II
Kaduk, 2002), Ca (Dale & Elsegood, 2003a), and Sr and
II
(
2
II
2�
Ba (Groeneman & Atwood, 1999), the TA anions utilize
only one carboxylate group for coordination, while the second
forms hydrogen bonds with included water molecules.
2�
complexation of the TA anion to divalent lead, a known
environmental pollutant (Shimoni-Livny et al., 1998).
II
Previously, the Pb salt of trimesic acid (Foreman et al., 2000)
was the only structurally characterized example of this cation
complexed to the commonly used members of the benzene-
II
IV
polycarboxylic acid family, although Pb and Pb ±carboxyl-
ate complexes are well known in the literature, with 160
examples in the Cambridge Structural Database (CSD;
Version 5.25, November 2003 update; Allen, 2002).
Figure 1
A view of (I), showing the atom-labelling scheme and the Pb
II
coordination sphere. Displacement ellipsoids are drawn at the 50%
probability level and C atoms are shown as unshaded ellipsoids. H atoms
not involved in hydrogen bonding have been omitted for clarity and the
OÐHÁ Á ÁO hydrogen bond is shown as a dashed line. PbÐO coordination
bonds are highlighted as open bonds. [Symmetry codes: (i) 1 � x, � y,
Attempts to produce single crystals of the desired coordi-
II
nation complex via the direct reaction of Pb with H TA are
1
2
3
2
1
2
3
2
2
1 � z; (ii) 2 � x, y � , � z; (iii) 1 + x, y, z; (iv) 2 � x, + y, � z; (v)
hindered by the low solubility of both H TA and the resulting
2
x � 1, y, z.]
m76 # 2004 International Union of Crystallography
DOI: 10.1107/S0108270103029573
Acta Cryst. (2004). C60, m76±m78

metal-organic compounds
hydrogen bonds (Table 2) between the water molecules and
4
carboxy groups also create R (8) ring motifs (Fig. 2).
2
The three-dimensional network of coordination and
Ê
hydrogen bonds in (I) (Fig. 3) results in a distance of ꢁ3.7 A
between the centroids of the aromatic rings of adjacent,
2
�
II
slightly offset, TA anions, which bridge the same two Pb
centres. This conformation leads to the non-planar geometry
2�
of the TA anions, the carboxy C atoms of which deviate
(
II
towards the Pb centres) from coplanarity with the aromatic
Ê
ring by 0.080 (9) and 0.177 (9) A for atoms C7 and C8,
respectively.
Experimental
Figure 2
X-Ray quality colourless crystals of (I) were obtained in quantitaive
yield by diffusing together separate aqueous solutions (1:1 ratio) of
A view of the hydrogen-bonding motifs in (I). Aromatic H atoms have
been omitted for clarity. Open circles represent C atoms, shaded circles O
atoms and dotted circles Pb atoms. PbÐO coordination bonds are shown
lead(II) nitrate and sodium terephthalate (Na
reaction of H TA with two equivalents of NaOH in water). IR (KBr,
cm ): ꢀmax 3425 (br, OH), 3063 and 2924 (aromatic CÐH), 1524
2
TA; formed from the
1
2
3
1
2
as open bonds. [Symmetry codes: (iv) 2 � x, + y, 2 � z; (vi) x, � y,
2
�
1
1
2
z � ; (vii) 2 � x, 1 � y, 1 � z; (viii) x, y + 1, z.]
�
�
(asymmetric CO
CÐH), 521.
2
), 1358 (symmetric CO
2
), 818 and 748 (aromatic
II
The bridging of two Pb centres each by the unique water
molecule and carboxy atom O1 creates four-membered rings
in which the OÐPbÐO bond angles are 68.13 (11) and
Crystal data
[Pb(C
M = 389.32
8
H
4
O
4
)(H
2
O)]
Mo Kꢂ radiation
Cell parameters from 3310
re¯ections
r
ꢀ
Monoclinic, P2 =c
Ê
a = 10.6661 (7) A
b = 7.5042 (5) A
c = 11.1260 (8) AÊ
6
2.12 (11) (Fig. 2 and Table 1). The combination of PbÐO
1
ꢀ
ꢃ = 3.3±28.9
ꢄ = 20.08 mm
T = 150 (2) K
coordination bonds (Table 1) and a carboxy±water OÐHÁ Á ÁO
� 1
Ê
hydrogen bond (Table 2) results in the formation of a six-
membered ring, which can be described by the graph-set
ꢀ
ꢁ
= 109.404 (2)
Column, colourless
0.24 Â 0.09 Â 0.06 mm
Ê
3
1
1
V = 839.95 (10) A
Z = 4
x
D = 3.079 Mg m
notation R (6) (Etter, 1990; Etter & MacDonald, 1990;
Bernstein et al., 1995). While a search of the CSD shows that
�
3
1
1
the R (6) carboxylate/metal/water motif has not yet been
Data collection
characterized in complexes containing lead, a total of 494
structures (containing any metal cation other than lead) do
contain the motif (the limits applied to the search were
Bruker SMART 1000 CCD area-
detector diffractometer
! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
1637 independent re¯ections
1496 re¯ections with I > 2ꢅ(I)
Rint = 0.033
Ê
Ê
ꢀ
OÁ Á ÁO = 2.0±3.5 A, HÁ Á ÁO = 1.0±2.5 A and OÐHÁ Á ÁO = 120±
ꢃ
max = 26.0
ꢀ
180 ). The results of this search are shown in Table 3, and it
1
can be seen that the geometry of the R (6) motif in (I) shows
h = � 8 ! 13
k = � 9 ! 9
l = � 13 ! 10
Tmin = 0.068, Tmax = 0.300
408 measured re¯ections
1
4
good agreement with the literature examples. OÐHÁ Á ÁO
Re®nement
2
2
2
2
Re®nement on F
2
w = 1/[ꢅ (F ) + (0.0297P)
o
2
R[F > 2ꢅ(F )] = 0.023
wR(F ) = 0.057
S = 1.04
+ 0.2788P]
where P = (F + 2F )/3
o c
(Á/ꢅ)max = 0.002
2
2
2
Ê
� 3
1
1
637 re¯ections
34 parameters
Áꢆmax = 1.63 e A
Ê
� 3
Áꢆmin = � 2.11 e A
H atoms treated by a mixture of
restrained and constrained
re®nement
Extinction correction: SHELXL97
Extinction coef®cient: 0.0017 (2)
Table 1
Selected geometric parameters (A, ).
Ê
ꢀ
i
Pb1ÐO1
Pb1ÐO1
Pb1ÐO3
Pb1ÐO3
2.492 (3)
2.731 (4)
2.434 (4)
2.751 (4)
Pb1ÐO4
Pb1ÐO5
Pb1ÐO5
2.650 (4)
2.563 (4)
2.759 (4)
ii
i
ii
iii
Figure 3
ii
O1ÐPb1ÐO5
i
O3 ÐPb1ÐO4
68.13 (11)
51.07 (12)
O1ÐPb1ÐO5
ii
O1 ÐPb1ÐO5
76.97 (11)
62.12 (11)
A packing plot of (I), viewed along the bc diagonal of the cell. Aromatic
H atoms have been omitted for clarity. Open circles represent C atoms,
shaded circles O atoms and dotted circles Pb atoms.
i
ii
1
3
Symmetry codes: (i) 1 � x; � y; 1 � z; (ii) 2 � x; y �
;
� z; (iii) 1 ‡ x; y; z.
2
2
ꢂ
Acta Cryst. (2004). C60, m76±m78
Sophie H. Dale et al.
8 4
[Pb(C H O
4 2
)(H O)] m77

metal-organic compounds
Table 2
Hydrogen-bonding geometry (A, ).
Data collection: SMART (Bruker, 2001); cell re®nement: SAINT
Bruker, 2001); data reduction: SAINT; program(s) used to solve
Ê
ꢀ
(
structure: SHELXTL (Sheldrick, 2000); program(s) used to re®ne
structure: SHELXTL; molecular graphics: SHELXTL; software used
to prepare material for publication: SHELXTL and local programs.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
iv
vi
O5ÐH5BÁ Á ÁO2
0.90 (2)
0.92 (2)
1.97 (2)
1.79 (2)
2.728 (5)
2.678 (5)
140 (2)
160 (2)
O5ÐH5AÁ Á ÁO2
The authors would like to acknowledge the EPSRC for the
provision of a studentship (SHD).
1
2
3
2
1
2
1
Symmetry codes: (iv) 2 � x; ‡ y; � z; (vi) x; � y; z �
.
2
Table 3
Ê
ꢀ
1
1
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: BM1557). Services for accessing these data are
described at the back of the journal.
Comparison of molecular geometry (A, ) for R ꢃ6† motifs containing
carboxylate and water ligands on any metal cation.
Limits applied to the search of the CSD (November 2003 update):
Ê
Ê
ꢀ
OÁ Á ÁO = 2.0±3.5 A, HwaterÁ Á ÁOcarboxy = 1.0±2.5 A and OÐHÁ Á ÁO = 120±180 .
Redeterminations were included. Where more than one population range was
obvious within the limits applied, the range and mean for each population are
given.
References
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Range (CSD)
Mean (CSD)
(I)
OÁ Á ÁO
2.429±2.983
1.280±2.458
130.29±179.74
2.680 (4)
1.871 (8)
157.0 (4)
2.728 (5)
1.97 (2)
140 (2)
H
waterÁ Á ÁOcarboxy
OÐHÁ Á ÁO
MÐcarboxylate
1.929±2.290
2.123 (4)
2.438 (7)
2.82 (3)
2.160 (5)
2.814 (19)
74.6 (3)
2
2
.291±2.637
.693±3.094
2.492 (3)
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1.903±2.428
.467±3.049
65.75±81.80
2.78±106.20
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2
2.759 (4)
76.97 (11)
OÐMÐO
8
91.0 (2)
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(
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Ê
Aromatic H atoms were placed geometrically (CÐH = 0.95 A)
and treated using a riding model, while the coordinates of the water H
atoms were found in a difference Fourier map and subsequently
re®ned using geometric restraints. Uiso(H) values were set at
1
.2Ueq(C) for aryl H atoms and at 1.5Ueq(O) for O-bound H atoms.
ꢂ
m78 Sophie H. Dale et al.
8 4
[Pb(C H O
4 2
)(H O)]
Acta Cryst. (2004). C60, m76±m78