DOI: 10.1021/cg100170t
Alkali Metal Ion Complexes with Pyrazinetetracarboxylate: Two- and Three-Dimensional Frameworks
2010, Vol. 10 2004–2010
Bernardo Masci,*,† Sara Pasquale,† and Pierre Thuery*,‡ †
Dipartimento di Chimica and IMC-CNR, Sapienza - Universit a di Roma, P.le Aldo Moro 5, at. 125, 00185 Roma, Italy, and ‡CEA, IRAMIS, UMR 3299 CEA/CNRS SIS2M, LCCEf, B^ 91191 Gif-sur-Yvette, France Received February 3, 2010; Revised Manuscript Received February 22, 2010
ABSTRACT: Three novel polymeric assemblages have been obtained from alkali metal salts of pyrazinetetracarboxylic acid (H4PZTC). In the complexes [Na2(H2PZTC)(H2O)2] (1), [K(H3PZTC)] (2), and [Cs2(H2PZTC)] (3), the cations are chelated in the O,N,O site of one (1) or two ligands (2 and 3),and further carboxylic/ate complexation results in the formation of two- (1) or three-dimensional (2 and 3) compact assemblages with alternate rows or planes of cations and ligands. The H4-xPZTCx- ligand is bound to 6, 4, and 12 cations in 1-3, respectively, with four oxygen atoms in the last case being coordinated to as many as four cesium atoms each. The crystal structure of complex 3 is particularly remarkable, with the cesium cation having a coordination number of 12 and a hexagonal prismatic environment. The Cs 3 3 3 Cs contacts in this compound are among the shortest reported. These compounds further illustrate the potential of H4PZTC for the building of metal-organic frameworks.
Introduction Although polymeric coordination complexes incorporating s-block metal ions have been known for a long time, the use of these cations in the present metal-organic frameworks (MOFs) studies is less prominent than that of d-block metal ions; it is nevertheless the object of some interest and has been recently reviewed.1 Considering the alkali metal subset, polymeric assemblages of varied dimensionality are very numerous, as can be seen from the complexes reported in the Cambridge Structural Database (CSD, version 5.31),2 and it has even been shown that an open framework could be synthesized with Naþ ions and ligands as simple as acetate and perchlorate.3 The quite undirectional coordination geometry preferences of the largest of these ions, particularly cesium ions, which are in this respect comparable to 4f metal ions, prevent as accurate crystal engineering as can be attained with some d-block species, but, on the other hand, the large coordination numbers which can be reached with the Csþ cation makes it a powerful assembler. The propensity of alkali metal ions, particularly the largest ones, to be involved in cation-π interactions can also be put to use in the synthesis of polymeric species, as exemplified by calixarene4 and aromatic polycarboxylate5 complexes. Among the latter, the carboxylate derivatives of pyridine are widely used in the synthesis of MOFs, and several frameworks with Liþ and Naþ ions have been reported.6 Several alkali metal ion complexes obtained with pyrazine-2,3-dicarboxylic acid are also polymeric,7 while some polymeric complexes of d-block metal8 or uranyl ions9 with pyrazine mono- and dicarboxylate derivatives contain alkali metal ions as well. We have recently been interested in pyrazinetetracarboxylic acid, denoted H4PZTC hereafter, as an assembler ligand in uranyl-organic frameworks, and we have reported several compounds comprising both uranyl and alkali metal ions.10 Among the complexes of H4-xPZTCxwith first and second row transition metal ions,11 several also *To whom correspondence should be addressed. E-mail: bernardo.masci@ uniroma1.it; Email:
[email protected]. pubs.acs.org/crystal
Published on Web 03/10/2010
include alkali metal ions11c,d and the Ca(II) complex of PZTC4-, which is a three-dimensional framework, has recently been described.12 We now report on structures of complexes formed by this ligand with alkali metal ions alone, which present the interesting feature of bringing together a ligand of potential high denticity, with an array of 10 donor atoms, and metal ions with preferences for quite large, or, in the case of Csþ, very large coordination numbers. Experimental Section Synthesis. Elemental analyses were performed by either Analytische Laboratorien GmbH at Lindlar, Germany, or Servizio di Microanalisi del Dipartimento di Chimica, Sapienza - Universit a di Roma, Italy. Pyrazinetetracarboxylic Acid (H4PZTC). Pyrazinetetracarboxylic acid was synthesized according to a literature procedure.10,13 [Na2(H2PZTC)(H2O)2] (1). This was isolated while attempting to prepare a mixed Naþ-UO22þ complex of pyrazinetetracarboxylic acid in nonhydrothermal conditions.10 A solution of UO2(NO3)2 3 6H2O (54 mg, 0.11 mmol) in MeOH (1 mL) was added dropwise to a stirred and heated solution of pyrazinetetracarboxylic acid (28 mg, 1.1 mmol) and NaOH (15 mg, 0.38 mmol) in water (4 mL) and methanol (4 mL). After heating for 10 min, the solution was allowed to stand, and colorless single crystals of 1 were collected after 6 days (6.0 mg, 16% yield). Anal. Calcd. for C8H6N2Na2O10: C, 28.59; H, 1.80; N, 8.33. Found: C, 28.31; H, 2.22; N, 8.05%. [K(H3PZTC)] (2). According to the reported synthesis of pyrazinetetracarboxylic acid through oxidation of phenazine with KMnO4 and KOH,13 the formed MnO2 was removed through filtration and the crude precipitate obtained after concentrating the filtrate was purified through recrystallization from 20% HCl. The resulting mother liquors were left standing, and large colorless single crystals were collected from the solid material formed after 3 months. The crystals were found to correspond to complex 2. Anal. Calcd. for C8H3KN2O8: C, 32.66; H, 1.03; N, 9.52; K, 13.29. Found: C, 32.50; H, 1.07; N, 9.52; K, 13.10%. [Cs2(H2PZTC)] (3). Aqueous CsOH (0.46 mL of a 0.30 M solution, 0.14 mmol) was added to pyrazinetetracarboxylic acid (28 mg, 1.1 mmol) in water (2 mL). After heating and stirring for 10 min, the solution was allowed to stand and single crystals of 3 were collected after 4 days (10 mg, 17% yield). Anal. Calcd. for r 2010 American Chemical Society
Article
Crystal Growth & Design, Vol. 10, No. 4, 2010
C8H2Cs2N2O8: C, 18.48; H, 0.39; N, 5.39. Found: C, 18.26; H, 0.80; N, 5.01%. Crystallography. The data were collected at 100(2) K on a Nonius Kappa-CCD area detector diffractometer14 using graphite-monochromated Mo-KR radiation (λ 0.71073 A˚). The crystals were introduced into glass capillaries with a protecting “Paratone-N” oil (Hampton Research) coating. The unit cell parameters were determined from 10 frames, then refined on all data. The data (combinations of j- and ω-scans giving complete data sets up to θ = 25.7° and a minimum redundancy of 4 for 90% of the reflections) were processed with HKL2000.15 The structures were solved by direct methods with SHELXS-97, expanded by subsequent Fourier-difference synthesis and refined by full-matrix leastsquares on F2 with SHELXL-97.16 Absorption effects in 3 were corrected empirically with the program SCALEPACK.15 All nonhydrogen atoms were refined with anisotropic displacement parameters. In compounds 1 and 2, the hydrogen atoms bound to oxygen atoms were found on Fourier-difference maps, and they were treated as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom. In compound 2, the proton of O3 was given an occupancy factor of 0.5 for charge balance and also because of its closeness to its image by symmetry (the corresponding two oxygen atoms being thus hydrogen bonded to one another by a disordered hydrogen atom). The protons in 3, necessarily disordered, were not found. Crystal data and structure refinement parameters are given in Table 1 and selected bond lengths and angles are given in Table 2. The molecular plots were drawn with SHELXTL16 and Balls & Sticks.17 The topological analysis was done with the program TOPOS.18
Table 1. Crystal Data and Structure Refinement Details chemical formula M (g mol-1) cryst syst space group a (A˚) b (A˚) c (A˚) β (°) V (A˚3) Z Dcalcd (g cm-3) μ (Mo KR) (mm-1) F(000) reflns collcd indep reflns obsd reflns [I > 2σ(I)] Rint params refined R1 wR2 S ΔFmin (e A˚-3) ΔFmax (e A˚-3)
1
2
3
C8H6N2Na2O10 336.13 monoclinic P21/n 9.9581(14) 6.3822(6) 10.2433(15) 117.424(7) 577.85(13) 2 1.932 0.239 340 18682 1052 923 0.020 100 0.063 0.173 1.023 -0.39 0.61
C8H3KN2O8 294.22 orthorhombic Pbcn 5.6654(3) 11.7553(4) 15.1266(9)
C8H2Cs2N2O8 519.94 orthorhombic Pbam 11.2006(7) 5.8263(3) 8.6056(3)
1007.41(9) 4 1.940 0.573 592 21961 953 878 0.022 87 0.029 0.077 1.070 -0.34 0.26
561.59(5) 2 3.075 6.536 476 12097 573 561 0.012 49 0.015 0.039 1.113 -0.63 0.58
Table 2. Environment of the Alkali Metal Atoms in Compounds 1-3: Selected Bond Lengths (A˚)a Na-O1 Na-O3 Na-N1 Na-O100 Na-O3000 Na-O5 Na-O5000 K-O1 K-O3 K-N1 K-O4000 Cs-O1 Cs-O1# Cs-O1$ Cs-O1C Cs-O2$ Cs-N1#
1
Results and Discussion The crystal structure of complex 1, [Na2(H2PZTC)(H2O)2], is represented in Figure 1. The asymmetric unit comprises one sodium ion, half a doubly deprotonated ligand located on an inversion center, and one coordinated water molecule. The sodium ion is chelated in the O,N,O site of one H2PZTC2molecule, which was occupied by the d-block or 5f ion in the previous examples of PZTC complexes including alkali metal ions,10,11c,11d with Na-N1 and average Na-O bond lengths of 2.582(3) and 2.37(4) A˚, respectively. The only examples of sodium ions in a comparable O,N,O site are found in the complexes obtained with pyridine-2,6-dicarboxylic acid, in which the average Na-N and Na-O bond lengths are 2.47(3) and 2.53(9) A˚, respectively.19 In all cases, the Na-O bond lengths are quite asymmetric, particularly in the latter examples in which some of the oxygen donors are protonated and differences in bond lengths as large as 0.28 A˚ are observed (0.08 A˚ only in 1); this may indicate that this cation is somewhat too small to perfectly fit the tridentate coordination site. The main difference between these complexes is however the reversal of the order between Na-N and Na-O bond lengths, which is probably to be ascribed to the differences in the location of the cation with respect to the mean ligand plane. In 1, the coordinated oxygen atoms do not deviate from the mean aromatic plane by more than 0.062(9) A˚, and the sodium atom is at 0.043(7) A˚ from this plane, whereas it is much more displaced, by as much as 0.66 A˚, in the complexes with pyridine-2,6-dicarboxylic acid. The sodium ion in 1 is also bound to two carboxylic/ate groups from two more ligands, the coordinated oxygen atoms O1 and O3 being thus bridging (Scheme 1), with the nonchelating bonds being larger [average bond length 2.496(9) A˚]. The sodium coordination sphere is completed by two bridging water molecules [average bond length 2.37(3) A˚, in agreement with the mean value of 2.42(8) A˚ for similar cases in the CSD], which results in a coordination number of seven. The sodium environment is
2005
2
3
2.410(3) 2.330(3) 2.582(3) 2.505(3) 2.487(3) 2.393(3) 2.338(3) 2.7951(11) 3.1398(13) 2.8669(13) 2.6861(11) 3.1649(16) 3.2476(18) 3.2492(18) 3.1562(16) 3.5091(17) 3.493(2)
Symmetry codes: 1 00 = 1.5 - x, y - 1/2, 1/2 - z; 000 = 1.5 - x, y þ 1/2, 1/2 - z. 2 000 = x - 1/2, y - 1/2, 1/2 - z. 3 # = 1/2 - x, y - 1/2, -z; $ = 1/2 - x, y þ 1/2, -z; C = x - 1/2, 1/2 - y, -z. a
pentagonal bipyramidal (point symmetry D5h) with the atoms from the three H2PZTC2- molecules defining the basal plane with a root mean squares (rms) deviation of 0.12 A˚ and the line defined by the two water oxygen atoms at the apexes making an angle of 13° with the normal to the plane (Figure 2). The chelate N-Na-O angles [average value 63.3(2)°] are smaller than the O-Na-O angles in the same plane [average value 78(6)°], the angle O100 -Na-O3000 being the largest, at 86.09(9)°, while the O5-Na-O5000 angle is 161.16(7)°, the bending being toward the largest basal angle. Each sodium ion shares one triangular face with each of its two neighbors. The two protons of the H2PZTC2- ligand are involved in two intramolecular hydrogen bonds with uncoordinated oxygen atoms of the neighboring carboxylate groups (Table 3). This arrangement, in which each cation is bound to three H2PZTC2- ligands and each ligand to six cations, gives rise to the formation of a two-dimensional framework parallel to the (1 0 1) plane, in which rows of triply bridged sodium ions [Na 3 3 3 Na separation 3.2803(19) A˚] directed along the b axis alternate with rows of H2PZTC2- ligands. The shortest interlayer distances correspond to the hydrogen bonds between the water molecule and carboxylate oxygen atoms.
2006
Crystal Growth & Design, Vol. 10, No. 4, 2010
Masci et al. Scheme 1. The Coordination Mode of H4-xPZTCx- in Compounds 1-3
Figure 1. Top: View of the complex [Na2(H2PZTC)(H2O)2] 1. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. Symmetry codes: 0 = 1 - x, -y, 1 - z; 00 = 1.5 - x, y - 1/2, 1/2 - z; 000 = 1.5 - x, y þ 1/2, 1/2 - z. Middle and bottom: Two views of the two-dimensional arrangement. Hydrogen atoms are omitted.
The structure is quite compact, as indicated by the packing index of 0.80 (evaluation with PLATON20) and does not contain voids or channels. The total point symbol18b for the trinodal network is (46.66.83)(47.63)2(4)2, with the three symbols corresponding to the nodes occupied by H2PZTC2-, Naþ, and H2O, respectively. No other example of this topology is present in the databases included in the TOPOS package.18a A simplified view of the network, with the H2PZTC2- ligand replaced by its centroid, is given in Figure 3. The potassium complex [K(H3PZTC)] (2) is represented in Figure 4. The asymmetric unit contains half a potassium ion, located on the binary axis (0 y 1/4) and half a singly deprotonated ligand located on an inversion center. Owing to its size being larger than that of Naþ, Kþ can be chelated in the O,N, O sites of two ligands, with K-N1 and average K-O bond lengths of 2.8669(13) and 2.97(17) A˚, respectively, and a dihedral angle of 76.29(6)° between the two groups of three donor atoms. Only one comparable example, in which potassium is chelated by one pyridine-2,6-dicarboxylato ligand, is present in the CSD, with K-N and average K-O bond
lengths of 2.889(3) and 2.84(10) A˚, respectively.21 As in the case of sodium, the K-O bonds are quite asymmetric in both cases. The H3PZTC ligand in 2 is much further from planar than H3PZTC in 1, the carboxylate groups being tilted and making dihedral angles of 21.2(2)° (O1, O2) and 70.64(9)° (O3, O4) with the mean aromatic plane. The potassium atom is displaced by 0.980(3) A˚ from the latter plane; its coordination sphere is completed by two oxygen atoms from two different ligands, but, in contrast with compound 1, these atoms are not bridging, each of the corresponding carboxylic groups being doubly monodentate and coordinated in the syn/ anti mode, with a K-O4 bond length of 2.6861(11) A˚, which is the shortest of all. The potassium coordination number is thus eight and the environment geometry can best be seen as a distorted dodecahedron (point symmetry D2d) with the three atoms of one O,N,O site and one O atom from a second, monodentate ligand in each trapezium (rms deviation 0.106 A˚), a displacement of the potassium atom of 0.0941(8) A˚ from the trapezium plane and a dihedral angle of 86.42(2)° between the two trapezia (Figure 2). The distortion of the dodecahedron arises from the angles around the metal atom in each trapezium being much smaller for the atoms of the chelate site [56.79(3) and 56.82(3)°] than with the fourth atom [76.33(3)°]. The polyhedra of neighboring cations are separated from one another, since no donor atom is bridging. Each potassium ion is bound to four ligands and each ligand to four cations, and a three-dimensional coordination polymer is formed which, in projection on the bc plane, appears as an assemblage of undulated ribbons of alternate ligands and chelated cations running along the c axis linked to one another by the monodentate oxygen atoms. However, the latter bonds link each ribbon to neighbors located above and below it along the a axis, which results in the three-dimensional extension of the
Article
Crystal Growth & Design, Vol. 10, No. 4, 2010
Figure 2. Arrangement of the H4-xPZTCx- ligands around the metal ion coordination polyhedron in compounds 1 (top), 2 (middle), and 3 (bottom). Table 3. Hydrogen Bonding Geometry in Compounds 1-3: Distances (A˚) and Angles (°) O2 3 O5 3 O5 3 O1 3 O3 3 O1 3
1 2 3a
3 3 3 3 3 3
0
3 O400 3 O3000 3 O40 3 O400 3 O30 3 O1
D3 3 3A 2.410(3) 2.856(3) 3.095(4) 2.6415(15) 2.415(2) 2.870(5)
D-H 0.84 0.89 0.96 0.89 0.81
H3 3 3A 1.57 1.97 2.22 1.76 1.63
D-H 3 3 3 A 177 173 151 171 162
Disordered hydrogen atom not found. Symmetry codes: 1 0 = 1 - x, -y, 1 - z; 00 = x - 1/2, -y - 1/2, z - 1/2; 000 = 1.5 - x, y þ 1/2, 1/2 - z. 2 0 = -x - 1/2, y - 1/2, z; 00 = 1 - x, y, 1/2 - z. 3 0 = x, y, -z. a
2007
Figure 3. Simplified views of the networks in compounds 1 (top), 2 (middle), and 3 (bottom). The metal centers are in dark blue and the ligand centroids in light blue; the bridging water ligands in 1 are represented in red. All views are down the a axis, with the b axis vertical.
architecture. The carboxylic protons are involved in interribbons hydrogen bonding, one of them being disordered between O3 and its image by symmetry (see Experimental Section). With 79.3% filled space, compound 2 has a packing index identical to that of 1 and is a compact assemblage with no empty space of significant size. The binodal network has the total point symbol (65.10)(65.8), with the first symbol corresponding to the nodes occupied by the ligand and the second to those occupied by the metal centers (Figure 3). The crystal structure of the third complex in this series, [Cs2(H2PZTC)] (3), is represented in Figure 5. The asymmetric
2008
Crystal Growth & Design, Vol. 10, No. 4, 2010
Masci et al.
Figure 4. Top: View of the complex [K(H3PZTC)] 2. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: 0 = -x, 1 - y, 1 - z; 00 = -x, y, 1/2 - z; 000 = x - 1/2, y - 1/2, 1/2 - z; 0000 = 1/2 - x, y - 1/2, z. Bottom: Projection of the three-dimensional arrangement down the a axis. Hydrogen atoms are omitted.
unit comprises half a cesium cation, located on the mirror plane (x y 0), and a quarter of the H2PZTC2- ligand, with the nitrogen atom on the 2-fold axis [1/2 1/2 z], and with a mirror plane perpendicular to this axis. Two cesium cations are chelated by each O,N,O site, one on each side of the aromatic ring plane, with Cs-N and average Cs-O bond lengths of 3.493(2) and 3.20(5) A˚. The only other comparable structure, with Csþ chelated in the O,N,O site of pyridine-2,6-dicarboxylic acid, is given as a private communication in the CSD.22 The bond lengths are much smaller in this structure [3.230 and 3.033(16) A˚ for Cs-N and average Cs-O, respectively], which is due to the single cation being located in the aromatic ring plane, whereas the two cations in 3 are displaced by 1.8880(4) A˚ on each side of the plane. Each cesium cation in 3 is also chelated in the O,N,O site of a second ligand, related to the first by the mirror plane, and bound to two O,O-chelating carboxylic/ate groups and two oxygen atoms from four different molecules, which results in a large coordination number of 12. The chelating -COO groups correspond to an average bond length of 3.38(13) A˚, in agreement with the mean value of 3.3(2) A˚ for analogous motifs in the CSD and with the average bond length of 3.29(15) A˚ found in the mixed uranyl/cesium complex of pyridine-2,6-dicarboxylate.23 The bond length for the other two oxygen atoms is shorter, at 3.1649(16) A˚. Overall, the Cs-O bond lengths are in the range 3.16-3.51 A˚, which is narrower than those in the mixed uranyl/cesium complexes with pyrazine-2,3-dicarboxylate (3.04-3.74 A˚)9 and pyridine2,6-dicarboxylate (3.04-3.72 A˚).23 The two O,N,O-chelating sites are coplanar and the six atoms define an elongated hexagon [side lengths 2.616(2) and 2.870(5) A˚, within and between the two ligands, respectively]. The other six coordinated atoms also roughly define an hexagon, with an rms deviation of 0.268 A˚, which is nearly parallel to the first
Figure 5. Top: View of the complex [Cs2(H2PZTC)] 3. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes: 0 = 1 - x, 1 - y, z; 00 = x, y, 1 - z; 000 = 1 - x, 1 - y, 1 - z; # = 1/2 - x, y - 1/2, -z; $= 1/2 - x, y þ 1/2, -z; % = x þ 1/2, 1/2 - y, z; A = x, y, -z; B = x - 1/2, 1/2 - y, z; C=x - 1/2, 1/2 - y, -z; D= 1/2 - x, y - 1/2, z; E = 1/2 - x, y þ 1/2, z. Bottom: View of the threedimensional assemblage down the b axis.
[dihedral angle 7.80(8)°], but with irregular side lengths, the shortest corresponding to the chelating -COO groups [2.206(3) A˚] and the others much larger [2.870(4) and 3.309(5) A˚]. The cesium atom is located in between these two hexagons, at 1.8952(2) A˚ from the first and 1.8149(10) A˚ from the second. As a result, the cesium coordination environment polyhedron is a distorted hexagonal prism, of ideal point symmetry D6h (Figure 2). 12-Coordination, which is the maximum observed for cesium ions, is frequently encountered in cesium sandwich or multiple-decker complexes with 18-crown-6 and its derivatives, in which the coordination polyhedron is generally hexagonal antiprismatic; however, cases in which it is hexagonal prismatic and more regular than
Article
Crystal Growth & Design, Vol. 10, No. 4, 2010
that in complex 3 have been reported.24 The most regular arrangement is found with unsubstituted 18-crown-6, in which the hexagon sides are all close to 2.8 A˚ in length. Each cesium atom in 3 shares the hexagonal face corresponding to bis-O,N,O-chelation with its neighbor, thus giving rise to linear ribbon subunits running along the c axis in which the bis-chelating ligands alternate with groups of two cations, whereas four atoms of the other hexagon correspond to a quadrangular side face of a neighboring prism (and, conversely, two side faces of each prism are part of two hexagonal faces of adjacent prisms). A very compact packing of cesium ions is thus built in the ab plane, with each prism sharing one face with its four neighbors and a shortest Cs 3 3 3 Cs separation of 3.7928(4) A˚ between cations sharing a hexagonal face, smaller than is usually the case in 18-crown-6 complexes (3.84-4.66 A˚).24b,25 In fact, this Cs 3 3 3 Cs separation is one of the shortest in the CSD for undisordered structures; a value of 3.75 A˚ has recently been reported and it was remarked that it was shorter than the distance in three-dimensional cesium acetate and comparable to twice the 12-coordinated cesium ionic radius.26 Similar values, as small as 3.71 A˚, are found for metal-metal bonds in cesium suboxides of the Cs11O3 type.27 The cesium layers in 3 are separated by organic layers of H2PZTC2- molecules, the successive cesium layers being separated by one c axis unit length, 8.6056(3) A˚. The resulting three-dimensional framework has 74.9% filled space. The aromatic rings in the organic layer are organized in herringbone fashion, with possible hydrogen bonds involving the disordered protons linking one organic layer to the next through association of the oxygen atoms from the two O,N, O-chelating groups around each cesium atom. The binodal network is associated with the total point symbol (415)2(448.618) (Figure 3), which corresponds to the topological type alb, for which the single example given in the TOPOS package is that of the complex catena[(μ8-phenoxyphenyl-4,40 -bis(phosphonato))-dicopper(II)],28 in which, however, Cu-O bond lengths as long as 2.77 A˚ have to be taken into account in order to get a connectivity analogous to that in 3. Conclusion The crystal structures described herein associate the highdenticity, nearly planar ligand H4-xPZTCx- and three alkali metal ions of varying ionic radii (1.12, 1.51, and 1.88 A˚ for Naþ, Kþ, and Csþ with coordination numbers of 7, 8, and 12, respectively).29 In all cases, the cation is chelated in the O,N,O site of one (1) or two (2 and 3) ligands to give either dinuclear [Na2(H2PZTC)], polymeric (undulated ribbons) [K(H3PZTC)]n, or polymeric (linear ribbons) [Cs2(H2PZTC)]n subunits. This coordination mode is at variance with that in the Ca(II) complex of PZTC4-,12 in which the metal atoms are O,N-chelated only, although the ionic radius of Ca(II) with the observed coordination numbers of 7 or 8 is identical to that of Na(I) with a coordination number of 7. The case of Csþ is peculiar since two cations are bound to each chelate site, with a very short Cs 3 3 3 Cs separation. The dimensionality of the assemblage is extended by further coordination of the carboxylic/ate groups, which are either O-bridging (1), O,O-bismonodentate (2), or both bridging and O,O-chelating (3). As a result, the ligand is bound to 6 Naþ, 4 Kþ, or 12 Csþ ions, the latter value being much larger than that of 7 in the mixed uranyl/rubidium complex of H2PZTC2-, in which the O,N,O site is occupied by uranyl.10 All 10 donor atoms are coordinated in complex 3 (as in the calcium complex), with four
2009
oxygen atoms bound to as many as four cations, whereas four or two oxygen atoms are left uncoordinated in 1 and 2, respectively. In complex 3, each ligand is bound to four cations through O,N,O-chelation and four through O,O-chelation, and it can thus be seen as an 8-fold chelating species. Tightly packed two- or three-dimensional assemblages are formed in 1-3, as could be expected to result from the association of cations with a preference for medium to large coordination numbers and a ligand with a propensity to act as a multitopic assembler. As a matter of fact, such a system would be unsuitable for the synthesis of porous materials, but it illustrates further the remarkable potential of the little used H4PZTC molecule for the synthesis of metal-organic frameworks. Supporting Information Available: Tables of crystal data, atomic positions and displacement parameters, anisotropic displacement parameters, and bond lengths and bond angles in CIF format. This information is available free of charge via the Internet at http:// pubs.acs.org.
References (1) Fromm, K. M. Coord. Chem. Rev. 2008, 252, 856. (2) Allen, F. H. Acta Crystallogr., Sect. B 2002, 58, 380. (3) Lavalette, A.; Lawrance, G. A.; Alcock, N. W.; Hannon, M. J. Eur. J. Inorg. Chem. 2004, 3981. (4) (a) Thuery, P.; Asfari, Z.; Vicens, J.; Lamare, V.; Dozol, J. F. Polyhedron 2002, 21, 2497. (b) Hanna, T. A.; Liu, L.; Angeles-Boza, A. M.; Kou, X.; Gutsche, C. D.; Ejsmont, K.; Watson, W. H.; Zakharov, L. N.; Incarvito, C. D.; Rheingold, A. L. J. Am. Chem. Soc. 2003, 125, 6228. (c) Asfari, Z.; Harrowfield, J.; Thuery, P.; Vicens, J. Supramol. Chem. 2003, 15, 69. (d) Mendoza-Espinosa, D.; Martinez-Ortega, B. A.; Quiroz-Guzman, M.; Golen, J. A.; Rheingold, A. L.; Hanna, T. A. J. Organomet. Chem. 2009, 694, 1509. (5) Burnet, S.; Hall, A. K.; Harrowfield, J. M.; Koutsantonis, G. A.; Sanford, V.; Sauter, D.; Skelton, B. W.; White, A. H. Supramol. Chem. 2003, 15, 291. (6) (a) Odoko, M.; Kusano, A.; Oya, N.; Okabe, N. Acta Crystallogr., Sect. C 2002, 58, m215. (b) Huang, W.; Xie, X.; Cui, K.; Gou, S.; Li, Y. Inorg. Chim. Acta 2005, 358, 875. (c) Forsyth, C. M.; Dean, P. M.; MacFarlane, D. R. Acta Crystallogr., Sect. C 2007, 63, m169. (7) (a) Tombul, M.; G€ uven, K.; Alkis-, N. Acta Crystallogr., Sect. E 2006, 62, m945. (b) Tombul, M.; G€uven, K.; B€uy€ukg€ung€or, O. Acta Crystallogr., Sect. E 2007, 63, m1783. (c) Tombul, M.; G€uven, K.; Svoboda, I. Acta Crystallogr., Sect. E 2008, 64, m246. (d) Tombul, M.; G€uven, K.; B€uy€ukg€ung€or, O. Acta Crystallogr., Sect. E 2008, 64, m491. (e) Tombul, M.; G€uven, K. Acta Crystallogr., Sect. E 2009, 65, m213. (8) (a) Sharma, R. P.; Bhasin, K. K.; Tiekink, E. R. T. Acta Crystallogr., Sect. C 1996, 52, 2140. (b) Wang, M. S.; Cai, L. Z.; Zhou, G. W.; Guo, G. C.; Mao, J. G.; Huang, J. S. Acta Crystallogr., Sect. E 2003, 59, m212. (c) Castillo, O.; Beobide, G.; Luque, A.; Roman, P. Acta Crystallogr., Sect. E 2003, 59, m800. (d) Zhao, M. G.; Shi, J. M.; Yu, W. T.; Wu, C. J.; Zhang, X. J. Coord. Chem. 2003, 56, 1351. (e) Tanase, S.; Marques Gallego, P.; Bouwman, E.; Long, G. J.; Rebbouh, L.; Grandjean, F.; de Gelder, R.; Mutikainen, I.; Turpeinen, U.; Reedijk, J. Dalton Trans. 2006, 1675. (9) Masci, B.; Thuery, P. CrystEngComm 2008, 10, 1082. (10) Masci, B.; Thuery, P. Cryst. Growth Des. 2008, 8, 1689. (11) (a) Marioni, P. A.; Stoeckli-Evans, H.; Marty, W.; G€ udel, H. U.; Williams, A. F. Helv. Chim. Acta 1986, 69, 1004. (b) G€uthner, T.; Thewalt, U. J. Organomet. Chem. 1989, 371, 43. (c) Graf, M.; Stoeckli-Evans, H.; Whitaker, C.; Marioni, P. A.; Marty, W. Chimia 1993, 47, 202. (d) Marioni, P. A.; Marty, W.; Stoeckli-Evans, H.; Whitaker, C. Inorg. Chim. Acta 1994, 219, 161. (e) Alfonso, M.; Neels, A.; Stoeckli-Evans, H. Acta Crystallogr., Sect. C 2001, 57, 1144. (f) Ghosh, S. K.; Bharadwaj, P. K. Inorg. Chem. 2004, 43, 6887. (g) Ghosh, S. K.; Bharadwaj, P. K. Eur. J. Inorg. Chem. 2005, 4880. (h) Ghosh, S. K.; El Fallah, M. S.; Ribas, J.; Bharadwaj, P. K. Inorg. Chim. Acta 2006, 359, 468. (12) Starosta, W.; Leciejewicz, J. J. Coord. Chem. 2008, 61, 490. (13) Vishweshwar, P.; Babu, N. J.; Nangia, A.; Mason, S. A.; Pushmann, H.; Mondal, R.; Howard, J. A. K. J. Phys. Chem. A 2004, 108, 9406.
2010
Crystal Growth & Design, Vol. 10, No. 4, 2010
(14) Hooft, R. W. W. COLLECT; Nonius BV: Delft, The Netherlands, 1998. (15) Otwinowski, Z.; Minor, W. Methods Enzymol. 1997, 276, 307. (16) Sheldrick, G. M. Acta Crystallogr., Sect. A 2008, 64, 112. (17) Ozawa, T. C.; Kang, S. J. J. Appl. Crystallogr. 2004, 37, 679. (18) (a) Blatov, V. A.; Shevchenko, A. P.; Serezhkin, V. N. J. Appl. Crystallogr. 2000, 33, 1193. (b) Blatov, V. A.; O'Keeffe, M.; Proserpio, D. M. CrystEngComm 2010, 12, 44. (19) (a) Laine, P.; Gourdon, A.; Launay, J. P. Inorg. Chem. 1995, 34, 5129. (b) Browning, K.; Abboud, K. A.; Palenik, G. J. J. Chem. Cryst. 1995, 25, 851. (c) Azadmeher, A.; Amini, M. M.; Hadipour, N.; Khavasi, H. R.; Fun, H. K.; Chen, C. J. Appl. Organomet. Chem. 2008, 22, 19. (20) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7. (21) Ma, C.; Chen, C.; Chen, F.; Zhang, X.; Zhu, H.; Liu, Q.; Liao, D.; Li, L. Bull. Chem. Soc. Jpn. 2003, 76, 301. (22) Odoko, M.; Kusano, A.; Oya, N.; Okabe, N. CSD, private communication, CCDC reference code OCUMUU, 2001.
Masci et al. (23) Harrowfield, J. M.; Lugan, N.; Shahverdizadeh, G. H.; Soudi, A. A.; Thuery, P. Eur. J. Inorg. Chem. 2006, 389. (24) (a) Baldas, J.; Colmanet, S. F.; Williams, G. A. Chem. Commun. 1991, 954. (b) Domasevitch, K. V.; Rusanova, J. A.; Vassilyeva, O. Y.; Kokozay, V. N.; Squattrito, P. J.; Sieler, J.; Raithby, P. R. J. Chem. Soc., Dalton Trans. 1999, 3087. (c) Wong, A.; Sham, S.; Wang, S.; Wu, G. Can. J. Chem. 2000, 78, 975. (25) Means, C. M.; Means, N. C.; Bott, S. G.; Atwood, J. L. J. Am. Chem. Soc. 1984, 106, 7627. (26) Saalfrank, R. W.; Scheurer, A.; Puchta, R.; Hampel, F.; Maid, H.; Heinemann, F. W. Angew. Chem., Int. Ed. 2007, 46, 265. (27) Simon, A.; Br€amer, W.; Deiseroth, H. J. Inorg. Chem. 1978, 17, 875. (28) G omez-Alcantara, M. M.; Cabeza, A.; Martı´ nez-Lara, M.; Aranda, M. A. G.; Suau, R.; Bhuvanesh, N.; Clearfield, A. Inorg. Chem. 2004, 43, 5283. (29) Shannon, R. D. Acta Crystallogr., Sect. A 1976, 32, 751.
