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The title complexes, catena-poly[[aqua(1,10-phenanthroline-κ2N,N′)­cobalt(II)]-μ-benzene-1,4-di­carboxyl­ato-κ2O1:O4], [Co(C8H4O4)(C12H8N2)(H2O)], (I), and catena-poly[[[(di-2-pyridyl-κN-amine)copper(II)]-μ-benzene-1,4-di­carboxyl­ato-κ4O1,O1′:O4,O4′] hydrate], [Cu(C8H4O4)(C10H9N3)]·H2O, (II), take the form of zigzag chains, with the 1,4-benzene­di­carboxyl­ate ion acting as an amphimonodentate ligand in (I) and a bis-bidentate ligand in (II). The CoII ion in (I) is five-coordinate and has a distorted trigonal–bipyramidal geometry. The CuII ion in (II) is in a very distorted octahedral 4+2 environment, with the octahedron elongated along the trans O—Cu—O bonds and with a trans O—Cu—O angle of only 137.22 (8)°.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102004341/na1551sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004341/na1551Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004341/na1551IIsup3.hkl
Contains datablock II

CCDC references: 187902; 187903

Comment top

The dianion of 1,4-benzenedicarboxylic acid (or terephthalic acid, H2tpht), is a potential bis-bidentate and bridging ligand. Although an example of a copper(II) compound containing uncoordinated tpht has been described recently by Huaqiang et al. (1997), in the case of first-row transition metal complexes tpht ions typically act as bis-bidentate (Verdaguer et al., 1984; Deng et al., 1992; Cano et al., 1994; Sun et al., 2001), tridentate (Bakalbassis et al., 1992) or bidentate (Verdaguer et al., 1984; Chaudhuri et al., 1988; Bakalbassis et al., 1991; Cueto et al., 1991; Xanthopoulos et al., 1993; Rogan et al., 2000; Kim et al., 2001; Sun et al., 2001) ligands.

With the exception of rare discrete complexes (Rogan et al., 2000) where tpht is coordinated by only one of its COO groups, tpht complexes are binuclear or polymeric in nature. Interest in such complexes is related to molecular magnetism, a continually growing field of research in modern inorganic chemistry and materials science. It is well documented that two paramagnetic centres could interact through extended bridging ligands. In the case of Cu-tpht complexes, this was initially investigated by Verdaguer et al. (1984), but the magnetic interactions were weak. Very shortly afterwards, some binuclear CuII complexes with unexpectedly strong antiferromagnetic interactions were described (Bakalbassis et al., 1985; Chaudhuri et al., 1988). Hence magnetic properties, together with an orbital interpretation of the magnetic exchange mechanism, were also discussed in many of the papers cited above. Here, two ternary tpht complexes, [Co(H2O)(phen)(tpht)], (I), and [Cu(dipya)(tpht)]·H2O, (II), containing CoII or CuII ions and 1,10-phenanthroline (phen) or 2,2'-dipyridylamine (dipya), are presented. \sch

The structure of complex (I) has recently been solved using low-temperature data collected at 193.2 K (Sun et al., 2001). However, an unusually high S-value (2.52), some duplicated H atoms detected in the corresponding CIF and an inability to locate the water H atoms led us to prepare the same compound by a different procedure and to collect a set of data at room temperature. In addition, for reasons of comparison it was necessary to have both the structures described here studied at the same temperature.

The two reported structures of (I) are found to be essentially identical. The change of temperature caused very small variations of the unit-cell parameters (0.11% for a, -0.74% for b, -0.69% for c and -1.28% for the unit-cell volume). As expected, the atomic displacement parameters have lower values and more isotropic character in the low-temperature data set.

Due to the bridging role of the tpht ions, both (I) and (II) are polymeric and can be described as zigzag chains, with neighbouring diamine ligands trans to each other (Figs. 1 and 2). Very similar chains are found in [Zn(H2O)(phen)(tpht)], which is isostructural with (I), and in [Cu(phen)(tpht)] (Sun et al., 2001), as well as in [Cu(en)(H2O)(tpht)] (en is ethylenediamine; Bakalbassis et al., 1988). In all these complexes, the metal centres are bridged by tpht ions coordinated in an amphimonodentate fashion.

Although the orientation of the chains in (I) and (II) is quite different, being parallel to [211] in (I) and to [111] in (II), the unit-cell volumes (see Crystal data) are very similar; the volume of (I) is slightly larger, due to the bulkier phen ligand. Intrachain Co—Co distances in (I) are alternately 11.063(?) and 11.289(?)Å, while the shortest interchain Co—Co distance is 5.908(?)Å. The corresponding Cu—Cu distances in (II) are 10.706(?), 10.898(?) and 5.153(?)Å, respectively. These values are quite normal for tpht-bridged complexes, therefore both intra- and interchain magnetic interactions might be expected. The shortest intrachain metal-metal distances in [Co(H2O)(phen)(tpht)], [Zn(H2O)(phen)(tpht)] and [Cu(phen)(tpht)] are 11.040(?), 10.853(?) and 11.094(?)Å, respectively (Sun et al., 2001). Please provide nine missing s.u.s

In both complexes, two crystallographically different but chemically identical tpht ions exist. Since the crystallographic inversion centres coincide with the centres of the aromatic rings, only half of each tpht ion belongs to the asymmetric unit. The dihedral angles between the two tpht aromatic rings are almost identical for both compounds, with values of 79.3 (3)° in (I) and 79.0 (3)° in (II).

In (I), the tpht ions do not deviate very much from planarity, with an acute dihedral angle between the C14—C16 aromatic ring and the adjacent COO group of 6.8 (2)°. The corresponding angle for the C18—C20 ring is 7.3 (3)°. In (II), the analogous angles differ more; that for C12—C14 is 17.3 (2)° and that for C16—C18 is only 4.7 (3)°. In two recently published series of tpht complexes (Rogan et al., 2000; Sun et al., 2001), the corresponding angles are relatively small, ranging between 3.5 and 22.3°. Nevertheless, angles up to 51.9° are found in some Cu complexes containing additional triamine ligands (Verdaguer et al., 1984; Bakalbassis et al., 1991). Besides the presence of the four O atoms as potential donor sites, it seems that easy rotation around the Caromatic—Ccarboxylate bonds has a great influence on the coordination of tpht ions and the resulting structures, which cover a wide range from discrete mononuclear complex entities, through binuclear units and chains, up to three-dimensional network structures. According to Kaduk (Kaduk, 2000; Kaduk & Golab, 1999), the completely planar conformation of tpht ions has a minimum energy. However, an increase in the angle of (both) COO groups up to 30° requires an energy increase of less than 20 kJ mol-1. This amount could easily be compensated by more favorable coordination geometries and crystal packing.

The main difference between (I) and (II) is the denticity of the tpht ligands, which are bis-bidentate in (II) and only amphimonodentate in (I). As a result, the coordination polyhedra are also very different. In (I), the Co atom is surrounded by five atoms in a deformed trigonal-bipyramidal arrangement, with atoms O1, N1 and OW1 in the equatorial plane (Table 1). The large O1—Co—OW1 angle could be a consequence of the hydrogen bond mentioned below, with the participation of atoms O2 and OW1. A long Co···O2 contact of 2.653 (3) Å, which is not usually regarded as Co—O bond but which is significantly shorter than the sum of van der Waals radii, should also be mentioned. The dihedral angle between COO groups coordinated to the same Co atom is 80.2 (3)°. No significant variations are observed for the Co—O and Co—N bond distances in (I) and in the previously reported structure (Sun et al., 2001).

In (II), the Cu atoms are in a 4 + 2 environment (Table 3), which, under usual circumstances, should be close to an elongated octahedron. However, to our knowledge, this is the first example of a tpht complex with two COO groups chelating to the same central atom. Due to the constraints imposed by such coordination and the formation of two four-membered rings with O—Cu—O angles less than 60° (Table 3), the coordination polyhedron is highly deformed. For example, the O2—Cu—O4 angle is only 137.22 (8)° (the octahedron is elongated along O2—Cu—O4). In addition, the maximum displacement from the equatorial Cu/N1/N2/O1/O3 plane is 0.611 (2) Å (for atom N2) and the distribution of ligating atoms in the N1/N2/O1/O3 plane is strongly puckered, with an average displacement of 0.426 (2) Å. The coordinated COO groups are almost perpendicular to each other, with a dihedral angle of 88.9 (3)°.

The bond distances and angles within the ligands in (I) and (II) are similar to the values found in the free compounds (H2tpht: Bailey & Brown, 1967; phen: Nishigaki et al., 1978; dipya: Johnson & Jacobson, 1973) and will not be discussed in detail, although there are two points worthy of note. Firstly, the N1/C1—C4 segment of the phen ligand in (I), where, for example, atom C2 deviates from the plane of the ligand by 0.056 (4) Å (ca 13σ), should be mentioned. This could be accounted for by some thermal motion or slight disorder, but this part of the ligand is sandwiched between two other aromatic rings from neighbouring chains, and so van der Waals and/or π interactions cannot be excluded. Secondly, the dihedral angle between the two pyridine rings of dipya in (II) is 14.5 (1)°, which is less than in dipya alone (23°; Johnson & Jacobson, 1973), but within the range of values already found for copper(II) complexes (Poleti et al., 1990).

There are two hydrogen bonds in complex (I) and three in complex (II) (Tables 2 and 4). In (I), the coordinated water molecule is a double hydrogen-bond donor. One of the hydrogen bonds is intramolecular (Fig. 1 and Table 2), while the other connects adjacent chains. In (II), the water of crystallization acts as double hydrogen-bond donor to the carboxylate O atoms, and as a hydrogen-bond acceptor from the amine H atom of dipya (Fig. 2 and Table 4).

Experimental top

Because the title complexes are insoluble in all common solvents, single crystals were prepared by a modification of the slow diffusion method. Typically, a dilute dimethylsulfoxide (DMSO) solution (~0.02 mol dm-3), containing equimolar quantities of cobalt(II) or copper(II) nitrate, aromatic amine and H2tpht, was prepared in a small test tube. A dilute solution of Na2tpht in H2O was then stratified carefully and very slowly in order to minimize mixing of the solutions. After approximately one week, single crystals of suitable size were formed near the solution boundary. In the case of the copper(II) system, two kinds of crystals, one dark-blue and one green, were obtained. The dark-blue crystals slowly transform to the green phase and, according to their IR spectra, very probably contain DMSO as an additional constituent. Due to their instability, these crystals were not characterized further.

Refinement top

For compound (I), all H atoms were found in difference Fourier maps and refined isotropically with no constraints. For compound (II), all H atoms were found in difference Fourier maps and refined isotropically with no constraints. However, the final geometry of the H2O molecule was not satisfactory. Because of this, the positions of the water H atoms HW1 and HW2 were recalculated using the program HYDROGEN (Nardelli, 1999) after the last cycle of refinement.

Computing details top

Data collection: SMART (Bruker, 1998) for (I); CAD-4 Software (Enraf-Nonius, 1989) for (II). Cell refinement: SMART or SAINT? (Siemens, 1996) for (I); CAD-4 Software for (II). Data reduction: SHELXTL (Bruker, 1997) for (I); local modification of MolEN (Fair, 1990) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEX8a (McArdle, 1995; Burnett & Johnson, 1996) for (I); ORTEX7e (McArdle, 1995; Burnett & Johnson, 1996) for (II). Software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1983, 1995) for (I); SHELXL97 and PARST (Nardelli, 1983; Nardelli, 1995) for (II).

Figures top
[Figure 1] Fig. 1. Part of the polymeric chain of complex (I) with the atom-numbering scheme. The intramolecular hydrogen bond is represented by a dashed line. Displacement ellipsoids are plotted at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. Part of the polymeric chain of complex (II) with the atom-numbering scheme. The N3—H···OW1 hydrogen bond is represented by dashed line. Displacement ellipsoids are plotted at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
(I) catena-poly-[[aqua(1,10-phenanthroline-κ2N,N')cobalt(II)]-µ-benzene- 1,4-dicarboxylato-κ2O1,O4] top
Crystal data top
[Co(C8H4O4)(C12H8N2)(H2O)]Z = 2
Mr = 421.26F(000) = 430
Triclinic, P1Dx = 1.571 Mg m3
a = 9.2688 (17) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.4550 (18) ÅCell parameters from 954 reflections
c = 11.349 (2) Åθ = 3.5–24.2°
α = 112.462 (3)°µ = 1.00 mm1
β = 94.924 (2)°T = 298 K
γ = 113.908 (2)°Irregular, brown-purple
V = 890.6 (3) Å30.27 × 0.22 × 0.18 mm
Data collection top
Make? model? CCD area-detector
diffractometer
3128 independent reflections
Radiation source: fine-focus sealed tube2012 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
Detector resolution: 81.92 pixels mm-1θmax = 25.5°, θmin = 3.5°
ϕ and ω scansh = 1110
Absorption correction: empirical (using intensity measurements)
(XPREP in SHELXTL; Bruker, 1997)
k = 1012
Tmin = 0.736, Tmax = 0.864l = 1013
4652 measured reflections
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: difference Fourier map
wR(F2) = 0.060All H-atom parameters refined
S = 0.88 w = 1/[σ2(Fo2) + (0.0171P)2]
where P = (Fo2 + 2Fc2)/3
3128 reflections(Δ/σ)max = 0.002
309 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
[Co(C8H4O4)(C12H8N2)(H2O)]γ = 113.908 (2)°
Mr = 421.26V = 890.6 (3) Å3
Triclinic, P1Z = 2
a = 9.2688 (17) ÅMo Kα radiation
b = 10.4550 (18) ŵ = 1.00 mm1
c = 11.349 (2) ÅT = 298 K
α = 112.462 (3)°0.27 × 0.22 × 0.18 mm
β = 94.924 (2)°
Data collection top
Make? model? CCD area-detector
diffractometer
3128 independent reflections
Absorption correction: empirical (using intensity measurements)
(XPREP in SHELXTL; Bruker, 1997)
2012 reflections with I > 2σ(I)
Tmin = 0.736, Tmax = 0.864Rint = 0.032
4652 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.060All H-atom parameters refined
S = 0.88Δρmax = 0.22 e Å3
3128 reflectionsΔρmin = 0.25 e Å3
309 parameters
Special details top

Experimental. For complex (I), preliminary cell constants were obtained from 180 frames (0.3° in ω). Final cell parameters were determined in a global refinement of data obtained after integration of intensities. Data collection nominally covered a hemisphere of reciprocal space by a combination of five sets of exposures (ω and ϕ scans). Each exposure of 10 s covered 0.3° in ω. The crystal-to-detector distance was 6.18 cm.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles. Correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co0.48616 (5)0.89276 (5)0.71582 (4)0.03683 (15)
O10.6905 (2)1.0993 (2)0.76184 (17)0.0480 (6)
O20.6103 (2)1.1559 (2)0.94286 (18)0.0541 (6)
O30.3173 (2)0.9240 (2)0.62329 (18)0.0449 (5)
O40.1766 (2)0.9539 (2)0.77342 (19)0.0546 (6)
OW10.3172 (3)0.7923 (2)0.8026 (2)0.0444 (6)
N10.5205 (3)0.7662 (2)0.5357 (2)0.0359 (6)
N20.6386 (3)0.8084 (2)0.7780 (2)0.0405 (6)
C10.4644 (4)0.7520 (4)0.4169 (3)0.0439 (8)
C20.5080 (5)0.6784 (4)0.3062 (3)0.0562 (10)
C30.6096 (5)0.6167 (4)0.3171 (3)0.0540 (10)
C40.6720 (4)0.6304 (3)0.4401 (3)0.0423 (8)
C50.7823 (4)0.5732 (4)0.4635 (4)0.0565 (10)
C60.8429 (5)0.5955 (4)0.5849 (4)0.0574 (10)
C70.7984 (4)0.6753 (3)0.6971 (3)0.0474 (8)
C80.8586 (5)0.7047 (4)0.8276 (4)0.0621 (11)
C90.8100 (5)0.7826 (4)0.9279 (4)0.0628 (11)
C100.6993 (4)0.8318 (4)0.8988 (3)0.0523 (10)
C110.6884 (3)0.7306 (3)0.6780 (3)0.0371 (7)
C120.6241 (3)0.7078 (3)0.5477 (3)0.0358 (7)
C130.7102 (3)1.1933 (3)0.8795 (3)0.0355 (7)
C140.8598 (3)1.3524 (3)0.9413 (2)0.0303 (7)
C150.9787 (4)1.3873 (3)0.8773 (3)0.0422 (8)
C160.8823 (4)1.4680 (4)1.0651 (3)0.0428 (9)
C170.2049 (4)0.9510 (3)0.6664 (3)0.0375 (7)
C180.0991 (3)0.9771 (3)0.5811 (3)0.0302 (7)
C190.1137 (4)0.9550 (3)0.4548 (3)0.0349 (8)
C200.0147 (4)0.9768 (3)0.3747 (3)0.0357 (8)
HC10.387 (3)0.792 (3)0.407 (2)0.051 (9)*
HC20.465 (3)0.670 (3)0.232 (2)0.034 (9)*
HC30.636 (3)0.566 (3)0.242 (3)0.054 (9)*
HC50.817 (3)0.524 (3)0.389 (3)0.065 (10)*
HC60.910 (3)0.554 (3)0.605 (3)0.057 (10)*
HC80.931 (3)0.671 (3)0.839 (3)0.054 (10)*
HC90.848 (3)0.806 (3)1.018 (3)0.068 (11)*
HC100.666 (3)0.885 (3)0.964 (2)0.038 (8)*
HC150.962 (3)1.304 (3)0.791 (2)0.048 (8)*
HC160.801 (3)1.445 (3)1.107 (2)0.044 (9)*
HC190.190 (3)0.921 (2)0.425 (2)0.027 (7)*
HC200.025 (3)0.966 (2)0.289 (2)0.031 (7)*
HW10.254 (4)0.841 (3)0.799 (3)0.073 (13)*
HW20.349 (5)0.808 (4)0.885 (4)0.14 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.0362 (3)0.0399 (3)0.0377 (2)0.0189 (2)0.01328 (19)0.01953 (19)
O10.0480 (14)0.0409 (12)0.0356 (12)0.0146 (11)0.0113 (10)0.0063 (10)
O20.0432 (14)0.0591 (14)0.0410 (13)0.0062 (12)0.0119 (11)0.0243 (11)
O30.0438 (14)0.0699 (15)0.0464 (12)0.0385 (12)0.0209 (11)0.0365 (11)
O40.0592 (15)0.0897 (17)0.0395 (13)0.0488 (14)0.0236 (12)0.0363 (12)
OW10.0468 (15)0.0506 (14)0.0431 (15)0.0230 (12)0.0182 (12)0.0274 (11)
N10.0369 (15)0.0365 (15)0.0334 (14)0.0168 (13)0.0071 (12)0.0165 (11)
N20.0447 (17)0.0443 (16)0.0333 (15)0.0219 (14)0.0089 (13)0.0180 (12)
C10.040 (2)0.049 (2)0.042 (2)0.0208 (18)0.0087 (17)0.0205 (16)
C20.067 (3)0.062 (2)0.033 (2)0.028 (2)0.009 (2)0.0195 (19)
C30.067 (3)0.048 (2)0.041 (2)0.027 (2)0.022 (2)0.0139 (17)
C40.043 (2)0.0367 (18)0.044 (2)0.0171 (17)0.0149 (17)0.0164 (15)
C50.064 (3)0.048 (2)0.061 (3)0.032 (2)0.028 (2)0.0196 (19)
C60.060 (3)0.060 (2)0.069 (3)0.042 (2)0.019 (2)0.031 (2)
C70.046 (2)0.049 (2)0.054 (2)0.0264 (18)0.0133 (18)0.0249 (17)
C80.061 (3)0.078 (3)0.069 (3)0.047 (2)0.012 (2)0.040 (2)
C90.069 (3)0.079 (3)0.047 (2)0.040 (2)0.005 (2)0.031 (2)
C100.064 (3)0.058 (2)0.041 (2)0.034 (2)0.016 (2)0.0215 (18)
C110.0364 (19)0.0316 (17)0.0452 (19)0.0164 (16)0.0111 (15)0.0193 (14)
C120.0352 (19)0.0290 (17)0.0379 (18)0.0112 (15)0.0082 (15)0.0151 (14)
C130.0315 (19)0.0435 (19)0.0360 (18)0.0192 (17)0.0050 (15)0.0220 (15)
C140.0286 (18)0.0311 (17)0.0295 (16)0.0135 (15)0.0065 (14)0.0133 (13)
C150.043 (2)0.0347 (19)0.0319 (18)0.0124 (18)0.0139 (16)0.0054 (15)
C160.043 (2)0.045 (2)0.0400 (19)0.0197 (18)0.0248 (18)0.0180 (16)
C170.035 (2)0.0361 (18)0.0348 (18)0.0159 (16)0.0076 (16)0.0122 (14)
C180.0261 (17)0.0317 (16)0.0289 (16)0.0130 (14)0.0039 (13)0.0117 (13)
C190.0297 (19)0.0411 (19)0.0365 (19)0.0212 (16)0.0118 (15)0.0150 (14)
C200.0353 (19)0.0408 (19)0.0278 (18)0.0174 (16)0.0114 (15)0.0132 (14)
Geometric parameters (Å, º) top
Co—O32.013 (2)C6—C71.429 (4)
Co—O12.044 (2)C6—HC60.95 (3)
Co—OW12.061 (2)C7—C111.399 (4)
Co—N12.102 (2)C7—C81.404 (4)
Co—N22.142 (2)C8—C91.356 (5)
O1—C131.261 (3)C8—HC80.89 (3)
O2—C131.251 (3)C9—C101.388 (4)
O3—C171.275 (3)C9—HC90.95 (3)
O4—C171.256 (3)C10—HC100.90 (2)
OW1—HW10.93 (3)C11—C121.436 (4)
OW1—HW20.89 (4)C13—C141.501 (3)
N1—C11.332 (3)C14—C151.374 (4)
N1—C121.352 (3)C14—C161.388 (3)
N2—C101.325 (3)C15—C16i1.377 (4)
N2—C111.360 (3)C15—HC150.98 (2)
C1—C21.391 (4)C16—C15i1.377 (4)
C1—HC10.98 (3)C16—HC160.92 (2)
C2—C31.361 (4)C17—C181.493 (4)
C2—HC20.85 (2)C18—C20ii1.383 (3)
C3—C41.396 (4)C18—C191.391 (3)
C3—HC30.92 (2)C19—C201.380 (4)
C4—C121.405 (3)C19—HC190.95 (2)
C4—C51.429 (4)C20—C18ii1.383 (3)
C5—C61.336 (4)C20—HC200.95 (2)
C5—HC50.96 (3)
O3—Co—O199.03 (8)C8—C7—C6124.8 (3)
O3—Co—OW189.2 (1)C9—C8—C7120.5 (4)
O1—Co—OW1140.21 (8)C9—C8—HC8124 (2)
O3—Co—N192.54 (9)C7—C8—HC8116 (2)
O1—Co—N194.22 (8)C8—C9—C10118.7 (4)
OW1—Co—N1124.44 (8)C8—C9—HC9123 (2)
O3—Co—N2167.33 (8)C10—C9—HC9118 (2)
O1—Co—N290.04 (8)N2—C10—C9123.8 (3)
OW1—Co—N289.5 (1)N2—C10—HC10116 (2)
N1—Co—N277.89 (9)C9—C10—HC10120 (2)
C13—O1—Co106.4 (2)N2—C11—C7123.4 (3)
C17—O3—Co127.1 (2)N2—C11—C12116.8 (3)
Co—OW1—HW198 (2)C7—C11—C12119.8 (3)
Co—OW1—HW2121 (3)N1—C12—C4122.9 (3)
HW1—OW1—HW2110 (3)N1—C12—C11117.2 (3)
C1—N1—C12118.3 (3)C4—C12—C11119.9 (3)
C1—N1—Co126.7 (2)O2—C13—O1121.7 (3)
C12—N1—Co114.7 (2)O2—C13—C14121.1 (3)
C10—N2—C11117.2 (3)O1—C13—C14117.2 (3)
C10—N2—Co129.4 (2)C15—C14—C16118.2 (3)
C11—N2—Co113.2 (2)C15—C14—C13121.0 (2)
N1—C1—C2122.0 (3)C16—C14—C13120.8 (3)
N1—C1—HC1119 (2)C14—C15—C16i121.1 (3)
C2—C1—HC1119 (2)C14—C15—HC15117 (2)
C3—C2—C1120.0 (4)C16i—C15—HC15122 (2)
C3—C2—HC2122 (2)C15i—C16—C14120.7 (3)
C1—C2—HC2117 (2)C15i—C16—HC16121 (2)
C2—C3—C4119.7 (3)C14—C16—HC16118 (2)
C2—C3—HC3119 (2)O4—C17—O3124.4 (3)
C4—C3—HC3121 (2)O4—C17—C18118.8 (3)
C3—C4—C12117.1 (3)O3—C17—C18116.9 (3)
C3—C4—C5124.4 (3)C20ii—C18—C19118.7 (3)
C12—C4—C5118.5 (3)C20ii—C18—C17121.2 (3)
C6—C5—C4121.5 (3)C19—C18—C17120.1 (3)
C6—C5—HC5121 (2)C20—C19—C18120.4 (3)
C4—C5—HC5117 (2)C20—C19—HC19122 (2)
C5—C6—C7121.6 (4)C18—C19—HC19118 (2)
C5—C6—HC6125 (2)C19—C20—C18ii120.9 (3)
C7—C6—HC6113 (2)C19—C20—HC20122 (1)
C11—C7—C8116.5 (3)C18ii—C20—HC20118 (1)
C11—C7—C6118.7 (3)
Symmetry codes: (i) x+2, y+3, z+2; (ii) x, y+2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
OW1—HW1···O40.93 (4)1.70 (4)2.608 (4)164 (4)
OW1—HW2···O2iii0.88 (5)1.82 (5)2.696 (3)172 (4)
Symmetry code: (iii) x+1, y+2, z+2.
(II) catena-poly-[[[(di-2-pyridyl-κN-amine)copper(II)]-µ-benzene-1,4- dicarboxylato-κ4O1,O1',O4,O4'] hydrate] top
Crystal data top
[Cu(C8H4O4)(C10H9N3)]·H2OZ = 2
Mr = 416.87F(000) = 426
Triclinic, P1Dx = 1.572 Mg m3
a = 9.009 (4) ÅMo Kα radiation, λ = 0.71069 Å
b = 9.289 (3) ÅCell parameters from 23 reflections
c = 11.171 (6) Åθ = 13.2–16.2°
α = 99.11 (4)°µ = 1.28 mm1
β = 106.64 (4)°T = 293 K
γ = 92.39 (3)°Prism, green
V = 880.6 (7) Å30.31 × 0.18 × 0.08 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.012
Radiation source: fine-focus sealed tubeθmax = 27.0°, θmin = 1.9°
Graphite monochromatorh = 010
ω/2θ scansk = 1111
4069 measured reflectionsl = 1413
3746 independent reflections2 standard reflections every 1 min
2814 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: heavy-atom method
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: difference Fourier map
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.01 w = 1/[σ2(Fo2) + (0.0512P)2]
where P = (Fo2 + 2Fc2)/3
3746 reflections(Δ/σ)max = 0.001
296 parametersΔρmax = 0.37 e Å3
0 restraintsΔρmin = 0.51 e Å3
Crystal data top
[Cu(C8H4O4)(C10H9N3)]·H2Oγ = 92.39 (3)°
Mr = 416.87V = 880.6 (7) Å3
Triclinic, P1Z = 2
a = 9.009 (4) ÅMo Kα radiation
b = 9.289 (3) ŵ = 1.28 mm1
c = 11.171 (6) ÅT = 293 K
α = 99.11 (4)°0.31 × 0.18 × 0.08 mm
β = 106.64 (4)°
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.012
4069 measured reflections2 standard reflections every 1 min
3746 independent reflections intensity decay: none
2814 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.100H atoms treated by a mixture of independent and constrained refinement
S = 1.01Δρmax = 0.37 e Å3
3746 reflectionsΔρmin = 0.51 e Å3
296 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R- factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu0.58844 (4)0.88776 (4)0.70282 (3)0.03472 (12)
O10.4034 (2)0.9937 (2)0.69257 (18)0.0420 (5)
O20.3712 (2)0.8448 (2)0.51176 (19)0.0502 (5)
O30.4810 (2)0.7077 (2)0.74281 (18)0.0430 (5)
O40.6471 (2)0.8310 (2)0.91647 (19)0.0460 (5)
OW11.2808 (3)0.9267 (3)0.8948 (3)0.0563 (7)
N10.7429 (3)0.7659 (2)0.6589 (2)0.0394 (5)
N20.7433 (2)1.0623 (2)0.7691 (2)0.0333 (5)
N30.9546 (3)0.9154 (3)0.8053 (2)0.0374 (5)
C10.6892 (4)0.6389 (4)0.5753 (4)0.0548 (8)
C20.7804 (5)0.5305 (4)0.5571 (4)0.0722 (12)
C30.9367 (5)0.5504 (4)0.6294 (4)0.0694 (11)
C40.9939 (4)0.6780 (3)0.7111 (4)0.0524 (8)
C50.8943 (3)0.7872 (3)0.7237 (3)0.0365 (6)
C60.8935 (3)1.0484 (3)0.8213 (2)0.0324 (5)
C70.9972 (3)1.1676 (3)0.8939 (3)0.0478 (7)
C80.9437 (4)1.3023 (4)0.9058 (4)0.0681 (11)
C90.7895 (5)1.3181 (4)0.8493 (4)0.0704 (12)
C100.6929 (4)1.1967 (3)0.7826 (3)0.0473 (7)
C110.3198 (3)0.9323 (3)0.5808 (3)0.0368 (6)
C120.1541 (3)0.9685 (3)0.5393 (2)0.0338 (6)
C130.0478 (3)0.8786 (3)0.4392 (3)0.0397 (6)
C140.1054 (3)0.9083 (3)0.3996 (3)0.0408 (7)
C150.5511 (3)0.7239 (3)0.8600 (3)0.0355 (6)
C160.5222 (3)0.6086 (3)0.9319 (2)0.0349 (6)
C170.5959 (4)0.6262 (3)1.0620 (3)0.0456 (7)
C180.4259 (3)0.4816 (3)0.8709 (3)0.0442 (7)
HN31.042 (4)0.919 (3)0.837 (3)0.042 (9)*
HC10.585 (4)0.631 (4)0.532 (4)0.070 (11)*
HC20.748 (4)0.447 (4)0.510 (3)0.059 (10)*
HC30.999 (4)0.473 (4)0.623 (3)0.066 (11)*
HC41.091 (4)0.687 (4)0.764 (3)0.062 (11)*
HC71.091 (4)1.154 (3)0.929 (3)0.049 (9)*
HC81.019 (4)1.379 (4)0.953 (4)0.072 (11)*
HC90.751 (5)1.395 (5)0.847 (4)0.093 (15)*
HC100.573 (4)1.206 (4)0.747 (3)0.065 (10)*
HC130.077 (3)0.802 (3)0.398 (3)0.031 (7)*
HC140.173 (4)0.847 (4)0.338 (3)0.060 (10)*
HC170.658 (3)0.711 (3)1.101 (3)0.044 (8)*
HC180.375 (4)0.473 (3)0.777 (3)0.050 (9)*
HW11.326610.987800.961870.050*
HW21.321490.942220.837590.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.02231 (17)0.03968 (19)0.03831 (19)0.00055 (12)0.00473 (12)0.00449 (13)
O10.0245 (9)0.0520 (12)0.0415 (11)0.0029 (8)0.0000 (8)0.0034 (9)
O20.0403 (11)0.0690 (14)0.0395 (11)0.0179 (10)0.0079 (9)0.0083 (10)
O30.0376 (11)0.0511 (12)0.0373 (11)0.0052 (9)0.0046 (8)0.0139 (9)
O40.0427 (12)0.0454 (11)0.0445 (11)0.0098 (9)0.0049 (9)0.0108 (9)
OW10.0347 (12)0.0703 (17)0.0548 (15)0.0033 (12)0.0085 (11)0.0058 (14)
N10.0320 (12)0.0371 (12)0.0470 (13)0.0021 (9)0.0130 (10)0.0008 (10)
N20.0272 (11)0.0352 (11)0.0365 (12)0.0030 (9)0.0078 (9)0.0065 (9)
N30.0226 (12)0.0406 (13)0.0437 (13)0.0043 (10)0.0020 (10)0.0061 (10)
C10.0425 (18)0.0507 (18)0.063 (2)0.0062 (15)0.0155 (16)0.0088 (15)
C20.061 (2)0.049 (2)0.095 (3)0.0088 (17)0.027 (2)0.024 (2)
C30.060 (2)0.0441 (19)0.107 (3)0.0117 (17)0.036 (2)0.002 (2)
C40.0382 (17)0.0435 (17)0.074 (2)0.0084 (13)0.0149 (16)0.0083 (16)
C50.0320 (14)0.0355 (14)0.0436 (15)0.0002 (11)0.0124 (12)0.0104 (11)
C60.0277 (12)0.0359 (13)0.0317 (13)0.0009 (10)0.0077 (10)0.0034 (10)
C70.0301 (15)0.0512 (18)0.0518 (18)0.0003 (13)0.0035 (13)0.0041 (14)
C80.0432 (19)0.0423 (18)0.097 (3)0.0028 (15)0.0070 (19)0.0224 (18)
C90.052 (2)0.0374 (18)0.107 (3)0.0080 (16)0.013 (2)0.0116 (19)
C100.0368 (16)0.0394 (16)0.063 (2)0.0071 (13)0.0119 (14)0.0056 (14)
C110.0299 (14)0.0436 (15)0.0350 (14)0.0033 (11)0.0035 (11)0.0131 (12)
C120.0257 (13)0.0410 (14)0.0318 (13)0.0031 (11)0.0024 (10)0.0097 (11)
C130.0351 (14)0.0396 (15)0.0389 (15)0.0069 (12)0.0038 (12)0.0037 (12)
C140.0318 (14)0.0436 (16)0.0364 (15)0.0001 (12)0.0040 (12)0.0033 (12)
C150.0270 (13)0.0379 (14)0.0423 (15)0.0034 (11)0.0100 (11)0.0096 (11)
C160.0279 (13)0.0389 (14)0.0357 (14)0.0013 (11)0.0057 (11)0.0072 (11)
C170.0448 (17)0.0424 (16)0.0411 (16)0.0114 (13)0.0023 (13)0.0055 (13)
C180.0401 (16)0.0527 (17)0.0330 (14)0.0071 (13)0.0009 (12)0.0092 (12)
Geometric parameters (Å, º) top
Cu—N11.951 (2)C4—C51.399 (4)
Cu—O11.955 (2)C4—HC40.90 (4)
Cu—N21.991 (2)C6—C71.398 (4)
Cu—O32.070 (2)C7—C81.359 (5)
Cu—O22.412 (2)C7—HC70.85 (3)
Cu—O42.440 (2)C8—C91.377 (5)
O1—C111.285 (3)C8—HC80.94 (4)
O2—C111.228 (3)C9—C101.366 (5)
O3—C151.261 (3)C9—HC90.81 (4)
O4—C151.247 (3)C10—HC101.05 (4)
OW1—HW10.85C11—C121.500 (4)
OW1—HW20.85C12—C131.374 (4)
N1—C51.338 (4)C12—C14i1.391 (4)
N1—C11.357 (4)C13—C141.378 (4)
N2—C61.332 (3)C13—HC130.88 (3)
N2—C101.348 (4)C14—C12i1.391 (4)
N3—C51.365 (4)C14—HC140.88 (3)
N3—C61.380 (3)C15—C161.493 (4)
N3—HN30.76 (3)C16—C181.389 (4)
C1—C21.353 (5)C16—C171.394 (4)
C1—HC10.92 (4)C17—C18ii1.382 (4)
C2—C31.396 (6)C17—HC170.91 (3)
C2—HC20.86 (3)C18—C17ii1.382 (4)
C3—C41.356 (5)C18—HC181.01 (3)
C3—HC30.94 (4)
N1—Cu—O1162.91 (9)N3—C5—C4118.4 (3)
N1—Cu—N291.8 (1)N2—C6—N3121.5 (2)
O1—Cu—N296.59 (9)N2—C6—C7121.8 (2)
N1—Cu—O389.80 (9)N3—C6—C7116.7 (2)
O1—Cu—O391.12 (9)C8—C7—C6118.6 (3)
N2—Cu—O3147.15 (9)C8—C7—HC7122 (2)
N1—Cu—O2103.9 (1)C6—C7—HC7119 (2)
O1—Cu—O259.29 (8)C7—C8—C9119.9 (3)
N2—Cu—O2127.75 (9)C7—C8—HC8115 (2)
O3—Cu—O283.35 (9)C9—C8—HC8125 (2)
N1—Cu—O493.3 (1)C10—C9—C8118.8 (3)
O1—Cu—O4101.57 (9)C10—C9—HC9115 (3)
N2—Cu—O489.67 (9)C8—C9—HC9126 (3)
O3—Cu—O457.48 (8)N2—C10—C9122.4 (3)
O2—Cu—O4137.22 (8)N2—C10—HC10118 (2)
C11—O1—Cu99.0 (2)C9—C10—HC10119 (2)
C11—O2—Cu79.6 (2)O2—C11—O1121.8 (2)
C15—O3—Cu98.6 (2)O2—C11—C12121.0 (2)
C15—O4—Cu81.9 (2)O1—C11—C12117.1 (2)
HW1—OW1—HW2108O2—C11—Cu71.5 (2)
C5—N1—C1118.6 (3)O1—C11—Cu50.5 (1)
C5—N1—Cu123.0 (2)C12—C11—Cu166.0 (2)
C1—N1—Cu117.2 (2)C13—C12—C14i119.1 (2)
C6—N2—C10118.5 (2)C13—C12—C11119.7 (2)
C6—N2—Cu121.2 (2)C14i—C12—C11121.2 (2)
C10—N2—Cu119.2 (2)C12—C13—C14121.0 (3)
C5—N3—C6131.1 (2)C12—C13—HC13120 (2)
C5—N3—HN3114 (2)C14—C13—HC13118 (2)
C6—N3—HN3114 (2)C13—C14—C12i119.9 (3)
C2—C1—N1123.1 (3)C13—C14—HC14120 (2)
C2—C1—HC1122 (2)C12i—C14—HC14120 (2)
N1—C1—HC1115 (2)O4—C15—O3121.9 (2)
C1—C2—C3118.0 (3)O4—C15—C16119.1 (2)
C1—C2—HC2125 (2)O3—C15—C16118.9 (2)
C3—C2—HC2117 (2)C18—C16—C17119.1 (3)
C4—C3—C2119.9 (3)C18—C16—C15121.2 (2)
C4—C3—HC3121 (2)C17—C16—C15119.7 (2)
C2—C3—HC3119 (2)C18ii—C17—C16120.4 (3)
C3—C4—C5119.4 (3)C18ii—C17—HC17122 (2)
C3—C4—HC4120 (2)C16—C17—HC17118 (2)
C5—C4—HC4120 (2)C17ii—C18—C16120.5 (3)
N1—C5—N3120.6 (2)C17ii—C18—HC18123 (2)
N1—C5—C4120.9 (3)C16—C18—HC18117 (2)
Symmetry codes: (i) x, y+2, z+1; (ii) x+1, y+1, z+2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—HN3···OW10.76 (3)2.06 (3)2.812 (4)171 (4)
OW1—HW1···O4iii0.851.952.743 (4)155
OW1—HW2···O1iv0.852.072.920 (4)174
Symmetry codes: (iii) x+2, y+2, z+2; (iv) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formula[Co(C8H4O4)(C12H8N2)(H2O)][Cu(C8H4O4)(C10H9N3)]·H2O
Mr421.26416.87
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)298293
a, b, c (Å)9.2688 (17), 10.4550 (18), 11.349 (2)9.009 (4), 9.289 (3), 11.171 (6)
α, β, γ (°)112.462 (3), 94.924 (2), 113.908 (2)99.11 (4), 106.64 (4), 92.39 (3)
V3)890.6 (3)880.6 (7)
Z22
Radiation typeMo KαMo Kα
µ (mm1)1.001.28
Crystal size (mm)0.27 × 0.22 × 0.180.31 × 0.18 × 0.08
Data collection
DiffractometerMake? model? CCD area-detector
diffractometer
Enraf-Nonius CAD-4
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(XPREP in SHELXTL; Bruker, 1997)
Tmin, Tmax0.736, 0.864
No. of measured, independent and
observed [I > 2σ(I)] reflections
4652, 3128, 2012 4069, 3746, 2814
Rint0.0320.012
(sin θ/λ)max1)0.6060.638
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.060, 0.88 0.039, 0.100, 1.01
No. of reflections31283746
No. of parameters309296
H-atom treatmentAll H-atom parameters refinedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.22, 0.250.37, 0.51

Computer programs: SMART (Bruker, 1998), CAD-4 Software (Enraf-Nonius, 1989), SMART or SAINT? (Siemens, 1996), CAD-4 Software, SHELXTL (Bruker, 1997), local modification of MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX8a (McArdle, 1995; Burnett & Johnson, 1996), ORTEX7e (McArdle, 1995; Burnett & Johnson, 1996), SHELXL97 and PARST (Nardelli, 1983, 1995), SHELXL97 and PARST (Nardelli, 1983; Nardelli, 1995).

Selected geometric parameters (Å, º) for (I) top
Co—O32.013 (2)Co—N12.102 (2)
Co—O12.044 (2)Co—N22.142 (2)
Co—OW12.061 (2)
O3—Co—O199.03 (8)OW1—Co—N1124.44 (8)
O3—Co—OW189.2 (1)O3—Co—N2167.33 (8)
O1—Co—OW1140.21 (8)O1—Co—N290.04 (8)
O3—Co—N192.54 (9)OW1—Co—N289.5 (1)
O1—Co—N194.22 (8)N1—Co—N277.89 (9)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
OW1—HW1···O40.93 (4)1.70 (4)2.608 (4)164 (4)
OW1—HW2···O2i0.88 (5)1.82 (5)2.696 (3)172 (4)
Symmetry code: (i) x+1, y+2, z+2.
Selected geometric parameters (Å, º) for (II) top
Cu—N11.951 (2)Cu—O32.070 (2)
Cu—O11.955 (2)Cu—O22.412 (2)
Cu—N21.991 (2)Cu—O42.440 (2)
N1—Cu—O1162.91 (9)N2—Cu—O2127.75 (9)
N1—Cu—N291.8 (1)O3—Cu—O283.35 (9)
O1—Cu—N296.59 (9)N1—Cu—O493.3 (1)
N1—Cu—O389.80 (9)O1—Cu—O4101.57 (9)
O1—Cu—O391.12 (9)N2—Cu—O489.67 (9)
N2—Cu—O3147.15 (9)O3—Cu—O457.48 (8)
N1—Cu—O2103.9 (1)O2—Cu—O4137.22 (8)
O1—Cu—O259.29 (8)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N3—HN3···OW10.76 (3)2.06 (3)2.812 (4)171 (4)
OW1—HW1···O4i0.851.952.743 (4)155
OW1—HW2···O1ii0.852.072.920 (4)174
Symmetry codes: (i) x+2, y+2, z+2; (ii) x+1, y, z.
 

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