Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The two isomorphous title structures, formulated as {[Co(C10H4O8)(C12H10N2)(H2O)2]·C12H10N2}n, (I), and {[Co(C10H4O8)(C12H12N2)(H2O)2]·C12H12N2}n, (II), respectively, are reported. They crystallize in the space group P\overline{1} with only one formula unit in the asymmetric unit, so that the organic ligands lie about inversion centres and the Co atom lies on an inversion centre. The Co atoms are octa­hedrally coordinated by a carboxyl­ate O atom from 2,5-dicarboxy­benzene-1,4-dicarboxyl­ate (H2btc), one N atom from 1,2-di-4-pyridyl­ethene (L) in (I) or from 1,2-di-4-pyridylethane (L) in (II), and one coordinated water mol­ecule, plus their inversion-related species. This particular coordination results in a two-dimensional array, with an elemental unit in the shape of a parallelogram having the CoII cations at the corners, linked in one direction by L bridges and in the opposite direction by H2btc groups. The L solvent mol­ecules act as pillars between parallel planes, linking them by strong hydrogen bonds where the H atoms lie midway between the formal donor/acceptor atoms in a `shared' mode. Comparison is made with structures presenting the same structural motif, strongly suggesting that the two-dimensional arrangement reported here might be a very stable robust building block for mol­ecular engineering purposes.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108041541/fg3070sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108041541/fg3070Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108041541/fg3070IIsup3.hkl
Contains datablock II

pdf

Portable Document Format (PDF) file https://doi.org/10.1107/S0108270108041541/fg3070fig1asup4.pdf
Supplementary material

CCDC references: 718107; 718108

Comment top

The ab initio design of supramolecular materials starting from molecular building blocks is an active research field in molecular engineering. In particular, great effort is currently dedicated to the assembly of metal ions and organic ligands in polymeric complexes (Moulton & Zaworotko, 2001; Janiak, 2003), in a process which can in principle be understood as one where the `interactive' information carried by the ligands is to be `decoded' by the metal ions through the `algorithm' determined by their coordination capabilities (Lehn, 1995). This process can lead to the formation of reproducible primary structures, which can in turn be used as secondary building units in the construction of even more complex structures, and the usefulness of these relies heavily on their stability. If one such structure is shown to be robust enough to survive almost unchanged in a number of compounds where it is subject to a diversity of interaction environments, it can then be considered an interesting target for crystal engineering. We report here a structural investigation of the two title isomorphous cobalt complexes, (I) and (II), characterized by one such seemingly robust structural motif.

The title compounds are formulated as [Co(H2btc)(L)(H2O)2].L, where (H4btc) is benzyl tetracarboxylic acid, C10H6O8, in both structures, and L, the ligand differentiating them, is 1,2-bis(4-pyridyl)ethene, C10H10N2 (bpe1), in (I) and 1,2-bis(4-pyridyl)ethane, C10H12N2 (bpe2), in (II). For the sake of simplicity, we shall only discuss the (I) isologue as representative of both, commenting on the corresponding differences when significant.

Fig. 1 shows a molecular view of (I), while Tables 1 and 3 present some selected coordination parameters and Tables 2 and 4 the main hydrogen-bonding interactions for (I) and (II), respectively.

Compound (I) crystallizes in the triclinic space group P1 with only one formula unit per unit cell. Thus, the organic ligands lie about inversion centres and the Co atom lies on an inversion centre. The CoII cation has an octahedral coordination, provided by a carboxylate O atom from (H2btc), an N atom from (bpe1) and one coordinated water molecule, plus their inversion-related species. The O atoms define the square equatorial plane, with a tight Co—O span [2.0824 (10)–2.1171 (11) Å for (I) and 2.0819 (10)–2.0919 (9) Å for (II)], while the N atoms occupy the apical positions, with Co—N = 2.1251 (12) Å in (I) and 2.1316 (11) Å in (II). The angles are also quite regular, with departures from ideal values of less than 1.8° in (I) and 2.4° in (II).

The organic ligands are regular and show no unusual features. The only obvious difference between the two structures is due to the double/single bond character of the mid C—C' bonds in bpe1 and bpe2 and, correspondingly, the number of H atoms attached. The coordinated bpe1 and H2btc ligands act in a similar bridging mode, the former through its two N atoms and the latter via two opposite carboxylate O atoms, binding in its most outstretched fashion. The result is a two-dimensional array (Fig. 2) with an elemental unit presenting a parallelogram shape with the CoII cations at the corners, linked in one direction (horizontally in Fig. 2) by the bpe1 bridges and in the opposite one (vertically in Fig. 2) by H2btc groups. For clarity, Fig. 2 has been drawn in a `channelling' view, along the crystallographic b axis. However, the two-dimensional structures are not parallel to the projection plane but run in a slanted manner, parallel to the (111) planes instead. This particular view was chosen to make the mesh-like structure more clearly visible, as well as to make obvious the linking role of the bpe1 solvate molecule, which runs from top to bottom in Fig. 2 and acts as an acceptor of two extremely strong hydrogen bonds (see below for details) to carboxylate O—H groups in two adjacent planes (above and below the solvate), thus configuring a very tight hydrogen-bonded three-dimensional structure. Fig. 3 shows a lateral view of that presented in Fig. 2, showing the planes sideways (bold horizontal lines), connected by the interleaved bpe1 ligands, shown as weak quasi-vertical lines.

A completely analogous two-dimensional motif has recently been reported in poly[[diaquacobalt(II)]-µ-2,5-dicarboxybenzene-1,4-dicarboxylato-µ-di-4- pyridylethene (Xing & Li, 2006), [Co(H2btc)(L)(H2O)2], (III), which uses the same ligands disposed in a topologically similar way but does not have the additional L solvate ligand as in (I). This results in a comparable two-dimensional structure characterized by a unit mesh motif of 13.681 (1) × 11.420 (1) Å, 106.7 (1)°, compared with 13.578 (1) × 11.296 (1) Å, 101.5 (1)°, for (I) and 13.567 (1) × 11.201 (1) Å, 109.9 (1)°, for (II). This metric conservation suggests that the two-dimensional structure might be considered a robust building layer, in particular when other parameters in the corresponding structures are significantly different. There is nothing occupying the interplanar space in (III) and neighbouring planes are simply linked by strong hydrogen bonds mediated by the coordinated water molecules. This leads to an extremely short interplanar spacing of 3.18 (1) Å. In compounds (I) and (II), the planes are supported by slanting L molecules [the N···N axes subtend to the plane normals angles of 66.1 (1)° in (I) and 65.88 (1) in (II)], leading to interplanar spacings of 5.118 (1) and 5.052 (1) Å, respectively. This suggests that the planes might `sandwich' a variety of different molecules in a pre-designed fashion and so be a potentially useful tool for use in molecular engineering.

The hydrogen bond linking atoms O33 and N12 deserves some attention. In both (I) and (II) it presents the same delocalized character, with the H atom `shared' by both eventual donor/acceptor atoms. Difference map plots show these H atoms with prolate spheroid shapes in both cases, and free refinement of the low-temperature data takes atom H33A quite close to the midpoint between atoms O33 (the expected donor) and N12 (the expected acceptor). In the case of (I), the H atom lies even slightly nearer to N12 (Table 3). These hydrogen bonds might be considered a measure of the strength of the interaction and, accordingly, of the stability of the three-dimensional structure derived from it.

In order to assess how common this kind of D—H—A interaction could be, we looked for comparable cases in the Cambridge Structural Database (CSD, Version?; Allen, 2002) where the D—H···A hydrogen bond could be described as a hard D—H—A synthon with the H atom simultaneously bound to both neighbours. Very often (about 50% of the situations found), the whole group appears to be riding on a special position (inversion centre or twofold axis), thus forcing D and A to be of the same species with the bridging H atom appearing midway, on the special position. The most frequent case is that in which D = A = O (337 cases), followed by D = A = N (28 cases). However, the case with D = O and A = N (reported here) appears just twice, and in one of the occurrences, bis(1,2-bis(4-pyridyl)ethene (2R,3R)-tartaric acid (2R,3R)-tartrate (Farrell et al., 2002), the N atom corresponds to the bpe1 ligand, as in (I) reported here. The other case is 4-methylpyridine pentachlorophenol (Steiner et al., 2001).

In addition to the short O···H···N hydrogen bonds found in both (I) and (II), there are strong hydrogen bonds (H···O = 1.86–1.92 Å) involving the water H atoms and the uncoordinated H2btc carboxylate O atoms which, being internal to the two-dimensional structures, contribute even further to their overall stability (Fig. 1 and Tables 2 and 4).

Experimental top

An aqueous solution (50 ml) containing CoII acetate tetrahydrate (0.33 mmol) was added to an aqueous solution (50 ml) containg 1,2,4,5-benzene tetracarboxylic acid (0.33 mmol) and NaOH (1.33 mmol). The mixture was heated under reflux for 20 min. An ethanolic solution (20 ml) containing the ligand [0.33 mmol; bpe1 for (I), bpe2 for (II)] was added slowly and the final solution was maintained under reflux for 4 h. Single crystals adequate for X-ray diffraction studies were obtained by slow concentration of the solutions.

Refinement top

All H atoms were originally found in a difference Fourier map, but they were treated differently. H atoms bonded to C atoms were repositioned at their expected locations and allowed to ride, with C—H = 0.93–0.97 Å and Uiso(H) = 1.2 or 1.5Ueq(C). Water H atoms were refined with O—H restrained to 0.85 (1) Å but free Uiso(H). Finally, atom H33A, which forms a very strong O—H···N bond that forces it to lie essentially midway between the two atoms in a `shared' mode, was refined freely.

Computing details top

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms have been omitted for clarity. Independent atoms are shown with heavy bonds and filled ellipsoids, and symmetry-related atoms with simple bonds and empty ellipsoids. [Symmetry codes: (i) 1 + x, y, z; (ii) 2 - x, 1 - y, 1 - z; (iii) 1 - x, 1 - y, 1 - z.] The structure of (II) is analogous and is available with the deposited material. [Please check added text]

Fig. 2. A packing view of (I) along the b axis. Heavy lines show the slanting and perfectly overlapping two-dimensional structures parallel to (111). Thin lines show the interleaved bpe1 ligands bridging adjacent planes together through O33—H33A···N12 bonds.

Fig. 3. A side view of that presented in Fig. 2, showing the two-dimensional structures sideways (heavy lines) and the bridging bpe1 ligands (thin lines) in between.

Fig. 4. FOR DEPOSIT. The molecular structure of (II). All drawing conventions and symmetry codes are as for (I) in Fig. 1.
(I) poly[[diaqua-µ-2,5-dicarboxybenzene-1,4-dicarboxylato- µ-1,2-di-4-pyridylethene-cobalt(II)] 1,2-di-4-pyridylethene solvate] top
Crystal data top
[Co(C10H4O8)(C12H10N2)(H2O)2]·C12H10N2Z = 1
Mr = 711.53F(000) = 367
Triclinic, P1Dx = 1.562 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.0283 (2) ÅCell parameters from 6054 reflections
b = 9.6152 (2) Åθ = 2.2–27.8°
c = 10.1064 (3) ŵ = 0.64 mm1
α = 93.1051 (14)°T = 150 K
β = 113.8441 (13)°Polyhedron, pink
γ = 106.2234 (14)°0.55 × 0.42 × 0.23 mm
V = 756.41 (3) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
3331 independent reflections
Radiation source: fine-focus sealed tube3132 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.017
CCD rotation images, thin slices scansθmax = 27.8°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
h = 1111
Tmin = 0.70, Tmax = 0.86k = 1211
12370 measured reflectionsl = 1212
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0432P)2 + 0.4048P]
where P = (Fo2 + 2Fc2)/3
3331 reflections(Δ/σ)max < 0.001
235 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
[Co(C10H4O8)(C12H10N2)(H2O)2]·C12H10N2γ = 106.2234 (14)°
Mr = 711.53V = 756.41 (3) Å3
Triclinic, P1Z = 1
a = 9.0283 (2) ÅMo Kα radiation
b = 9.6152 (2) ŵ = 0.64 mm1
c = 10.1064 (3) ÅT = 150 K
α = 93.1051 (14)°0.55 × 0.42 × 0.23 mm
β = 113.8441 (13)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3331 independent reflections
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
3132 reflections with I > 2σ(I)
Tmin = 0.70, Tmax = 0.86Rint = 0.017
12370 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.04Δρmax = 0.38 e Å3
3331 reflectionsΔρmin = 0.25 e Å3
235 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co11.00000.50000.50000.01298 (9)
N111.01957 (16)0.65228 (13)0.67162 (13)0.0167 (2)
C111.03383 (19)0.61342 (16)0.80048 (16)0.0192 (3)
H111.03830.51740.81410.023*
C211.0424 (2)0.70658 (17)0.91461 (16)0.0201 (3)
H211.05670.67581.00550.024*
C311.02991 (19)0.84579 (16)0.89522 (16)0.0180 (3)
C411.0187 (2)0.88780 (16)0.76216 (16)0.0190 (3)
H411.01360.98300.74530.023*
C511.01496 (19)0.78910 (16)0.65568 (16)0.0191 (3)
H511.00880.81950.56620.023*
C611.0239 (2)0.94025 (17)1.01034 (16)0.0199 (3)
H611.05600.91501.10520.024*
N120.62629 (16)0.59521 (14)0.84960 (14)0.0199 (3)
C120.5584 (2)0.68283 (18)0.76311 (18)0.0270 (3)
H120.53300.66430.66170.032*
C220.5238 (2)0.79944 (18)0.81624 (18)0.0279 (4)
H220.47670.86040.75210.034*
C320.55852 (19)0.82723 (17)0.96460 (17)0.0208 (3)
C420.6294 (2)0.73470 (18)1.05249 (17)0.0257 (3)
H420.65580.75001.15430.031*
C520.6615 (2)0.62079 (18)0.99221 (18)0.0245 (3)
H520.71010.55871.05390.029*
C620.5236 (2)0.94623 (18)1.03210 (18)0.0240 (3)
H620.53600.94621.13000.029*
C130.65820 (18)0.11433 (15)0.55886 (15)0.0143 (3)
C230.51484 (18)0.14047 (15)0.56273 (15)0.0151 (3)
C330.35838 (18)0.02575 (15)0.50243 (15)0.0158 (3)
H330.26030.04360.50320.019*
C430.82592 (18)0.23614 (15)0.60063 (15)0.0151 (3)
C530.52051 (18)0.28671 (16)0.63096 (16)0.0172 (3)
O130.81410 (13)0.34150 (11)0.53333 (11)0.0168 (2)
O230.96182 (13)0.21851 (12)0.68884 (12)0.0217 (2)
O330.65657 (14)0.35861 (12)0.74754 (12)0.0219 (2)
H33A0.642 (4)0.485 (3)0.799 (3)0.077 (9)*
O430.39350 (15)0.32596 (13)0.57317 (14)0.0306 (3)
O1W1.19427 (14)0.43673 (12)0.66059 (12)0.0178 (2)
H1WB1.258 (3)0.410 (3)0.635 (3)0.041 (6)*
H1WA1.136 (3)0.361 (3)0.675 (2)0.036 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.01582 (14)0.01038 (14)0.01430 (14)0.00455 (10)0.00801 (11)0.00171 (10)
N110.0200 (6)0.0139 (6)0.0185 (6)0.0065 (5)0.0101 (5)0.0017 (5)
C110.0248 (7)0.0162 (7)0.0204 (7)0.0090 (6)0.0119 (6)0.0045 (6)
C210.0274 (8)0.0199 (7)0.0179 (7)0.0105 (6)0.0124 (6)0.0055 (6)
C310.0201 (7)0.0173 (7)0.0180 (7)0.0070 (6)0.0093 (6)0.0015 (5)
C410.0263 (7)0.0139 (7)0.0205 (7)0.0085 (6)0.0124 (6)0.0037 (5)
C510.0259 (7)0.0171 (7)0.0184 (7)0.0085 (6)0.0125 (6)0.0044 (6)
C610.0254 (7)0.0190 (7)0.0169 (7)0.0076 (6)0.0108 (6)0.0019 (5)
N120.0213 (6)0.0162 (6)0.0207 (6)0.0064 (5)0.0084 (5)0.0012 (5)
C120.0394 (9)0.0225 (8)0.0199 (7)0.0134 (7)0.0119 (7)0.0016 (6)
C220.0404 (9)0.0216 (8)0.0229 (8)0.0178 (7)0.0099 (7)0.0051 (6)
C320.0211 (7)0.0173 (7)0.0227 (7)0.0071 (6)0.0083 (6)0.0007 (6)
C420.0356 (9)0.0256 (8)0.0190 (7)0.0157 (7)0.0113 (7)0.0025 (6)
C520.0299 (8)0.0223 (8)0.0229 (8)0.0139 (7)0.0097 (6)0.0041 (6)
C620.0298 (8)0.0224 (8)0.0215 (7)0.0122 (6)0.0109 (6)0.0018 (6)
C130.0168 (6)0.0128 (6)0.0147 (6)0.0050 (5)0.0080 (5)0.0030 (5)
C230.0189 (7)0.0117 (6)0.0165 (6)0.0054 (5)0.0094 (5)0.0031 (5)
C330.0170 (7)0.0146 (7)0.0196 (7)0.0065 (5)0.0108 (6)0.0037 (5)
C430.0183 (7)0.0128 (6)0.0158 (6)0.0044 (5)0.0099 (5)0.0001 (5)
C530.0204 (7)0.0134 (7)0.0226 (7)0.0056 (5)0.0143 (6)0.0028 (5)
O130.0173 (5)0.0137 (5)0.0208 (5)0.0044 (4)0.0098 (4)0.0047 (4)
O230.0175 (5)0.0200 (5)0.0259 (6)0.0056 (4)0.0075 (4)0.0092 (4)
O330.0237 (5)0.0176 (5)0.0219 (5)0.0081 (4)0.0076 (4)0.0028 (4)
O430.0242 (6)0.0244 (6)0.0384 (7)0.0133 (5)0.0071 (5)0.0067 (5)
O1W0.0187 (5)0.0162 (5)0.0216 (5)0.0069 (4)0.0109 (4)0.0050 (4)
Geometric parameters (Å, º) top
Co1—O132.0824 (10)C22—C321.396 (2)
Co1—O13i2.0824 (10)C22—H220.9500
Co1—O1Wi2.1171 (11)C32—C421.391 (2)
Co1—O1W2.1171 (11)C32—C621.471 (2)
Co1—N112.1251 (12)C42—C521.379 (2)
Co1—N11i2.1251 (12)C42—H420.9500
N11—C111.3403 (19)C52—H520.9500
N11—C511.3440 (19)C62—C62iii1.330 (3)
C11—C211.384 (2)C62—H620.9500
C11—H110.9500C13—C33iv1.3936 (19)
C21—C311.392 (2)C13—C231.4006 (19)
C21—H210.9500C13—C431.5105 (19)
C31—C411.398 (2)C23—C331.394 (2)
C31—C611.465 (2)C23—C531.5105 (19)
C41—C511.379 (2)C33—C13iv1.3936 (19)
C41—H410.9500C33—H330.9500
C51—H510.9500C43—O131.2557 (17)
C61—C61ii1.334 (3)C43—O231.2558 (18)
C61—H610.9500C53—O431.2340 (19)
N12—C121.336 (2)C53—O331.2814 (18)
N12—C521.336 (2)O33—H33A1.35 (3)
N12—H33A1.22 (3)O1W—H1WB0.81 (3)
C12—C221.382 (2)O1W—H1WA0.83 (2)
C12—H120.9500
O13—Co1—O13i180.00 (5)N12—C12—C22122.19 (15)
O13—Co1—O1Wi89.99 (4)N12—C12—H12118.9
O13i—Co1—O1Wi90.01 (4)C22—C12—H12118.9
O13—Co1—O1W90.01 (4)C12—C22—C32119.67 (15)
O13i—Co1—O1W89.99 (4)C12—C22—H22120.2
O1Wi—Co1—O1W180.0C32—C22—H22120.2
O13—Co1—N1188.87 (4)C42—C32—C22117.08 (14)
O13i—Co1—N1191.13 (4)C42—C32—C62118.69 (14)
O1Wi—Co1—N1191.65 (4)C22—C32—C62124.24 (14)
O1W—Co1—N1188.35 (4)C52—C42—C32120.15 (15)
O13—Co1—N11i91.13 (4)C52—C42—H42119.9
O13i—Co1—N11i88.87 (4)C32—C42—H42119.9
O1Wi—Co1—N11i88.35 (4)N12—C52—C42121.93 (15)
O1W—Co1—N11i91.65 (4)N12—C52—H52119.0
N11—Co1—N11i180.0C42—C52—H52119.0
C11—N11—C51117.22 (12)C62iii—C62—C32125.63 (19)
C11—N11—Co1120.58 (10)C62iii—C62—H62117.2
C51—N11—Co1122.19 (10)C32—C62—H62117.2
N11—C11—C21123.09 (14)C33iv—C13—C23119.33 (13)
N11—C11—H11118.5C33iv—C13—C43117.50 (12)
C21—C11—H11118.5C23—C13—C43122.71 (12)
C11—C21—C31119.47 (14)C33—C23—C13118.83 (13)
C11—C21—H21120.3C33—C23—C53117.70 (12)
C31—C21—H21120.3C13—C23—C53123.47 (13)
C21—C31—C41117.52 (13)C13iv—C33—C23121.83 (13)
C21—C31—C61119.91 (13)C13iv—C33—H33119.1
C41—C31—C61122.54 (13)C23—C33—H33119.1
C51—C41—C31119.05 (14)O13—C43—O23126.62 (13)
C51—C41—H41120.5O13—C43—C13114.91 (12)
C31—C41—H41120.5O23—C43—C13118.26 (12)
N11—C51—C41123.55 (14)O43—C53—O33125.13 (13)
N11—C51—H51118.2O43—C53—C23118.05 (13)
C41—C51—H51118.2O33—C53—C23116.80 (12)
C61ii—C61—C31123.80 (18)C43—O13—Co1130.15 (9)
C61ii—C61—H61118.1C53—O33—H33A110.3 (13)
C31—C61—H61118.1Co1—O1W—H1WB117.5 (17)
C12—N12—C52118.97 (13)Co1—O1W—H1WA100.8 (15)
C12—N12—H33A121.5 (14)H1WB—O1W—H1WA105 (2)
C52—N12—H33A119.2 (14)
O13—Co1—N11—C1147.47 (11)C62—C32—C42—C52179.10 (16)
O13i—Co1—N11—C11132.53 (11)C12—N12—C52—C420.2 (2)
O1Wi—Co1—N11—C11137.42 (11)C32—C42—C52—N120.1 (3)
O1W—Co1—N11—C1142.58 (11)C42—C32—C62—C62iii171.3 (2)
O13—Co1—N11—C51131.22 (12)C22—C32—C62—C62iii9.2 (3)
O13i—Co1—N11—C5148.78 (12)C33iv—C13—C23—C331.2 (2)
O1Wi—Co1—N11—C5141.26 (12)C43—C13—C23—C33170.81 (13)
O1W—Co1—N11—C51138.74 (12)C33iv—C13—C23—C53177.99 (13)
C51—N11—C11—C210.5 (2)C43—C13—C23—C5310.0 (2)
Co1—N11—C11—C21178.23 (11)C13—C23—C33—C13iv1.2 (2)
N11—C11—C21—C312.3 (2)C53—C23—C33—C13iv178.01 (13)
C11—C21—C31—C413.5 (2)C33iv—C13—C43—O13118.33 (14)
C11—C21—C31—C61174.74 (14)C23—C13—C43—O1353.78 (18)
C21—C31—C41—C512.0 (2)C33iv—C13—C43—O2356.73 (18)
C61—C31—C41—C51176.16 (14)C23—C13—C43—O23131.16 (15)
C11—N11—C51—C412.1 (2)C33—C23—C53—O4335.65 (19)
Co1—N11—C51—C41176.61 (11)C13—C23—C53—O43145.19 (15)
C31—C41—C51—N110.8 (2)C33—C23—C53—O33142.57 (14)
C21—C31—C61—C61ii165.20 (19)C13—C23—C53—O3336.6 (2)
C41—C31—C61—C61ii12.9 (3)O23—C43—O13—Co115.1 (2)
C52—N12—C12—C220.2 (3)C13—C43—O13—Co1159.49 (9)
N12—C12—C22—C320.7 (3)O1Wi—Co1—O13—C43167.20 (12)
C12—C22—C32—C420.8 (3)O1W—Co1—O13—C4312.80 (12)
C12—C22—C32—C62178.72 (16)N11—Co1—O13—C43101.15 (12)
C22—C32—C42—C520.4 (2)N11i—Co1—O13—C4378.85 (12)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y+2, z+2; (iii) x+1, y+2, z+2; (iv) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O33—H33A···N121.35 (3)1.22 (3)2.5759 (16)177 (3)
O1W—H1WB···O43v0.81 (3)1.92 (3)2.7210 (16)174 (2)
O1W—H1WA···O230.83 (2)1.83 (2)2.6414 (16)165 (2)
Symmetry code: (v) x+1, y, z.
(II) poly[[diaqua-µ-2,5-dicarboxybenzene-1,4-dicarboxylato- µ-1,2-di-4-pyridylethene-cobalt(II)] 1,2-di-4-pyridylethane solvate] top
Crystal data top
[Co(C10H4O8)(C12H12N2)(H2O)2]·C12H12N2Z = 1
Mr = 715.57F(000) = 371
Triclinic, P1Dx = 1.544 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.0933 (4) ÅCell parameters from 6988 reflections
b = 9.5887 (5) Åθ = 2.2–27.7°
c = 10.0058 (5) ŵ = 0.63 mm1
α = 92.2999 (7)°T = 150 K
β = 111.9705 (6)°Polyhedron, yellow
γ = 105.6443 (7)°0.29 × 0.21 × 0.18 mm
V = 769.33 (7) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
3442 independent reflections
Radiation source: fine-focus sealed tube3363 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
CCD rotation images, thin slices scansθmax = 27.9°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
h = 1111
Tmin = 0.84, Tmax = 0.89k = 1212
16531 measured reflectionsl = 1213
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0432P)2 + 0.4048P]
where P = (Fo2 + 2Fc2)/3
3442 reflections(Δ/σ)max < 0.001
235 parametersΔρmax = 0.43 e Å3
0 restraintsΔρmin = 0.27 e Å3
Crystal data top
[Co(C10H4O8)(C12H12N2)(H2O)2]·C12H12N2γ = 105.6443 (7)°
Mr = 715.57V = 769.33 (7) Å3
Triclinic, P1Z = 1
a = 9.0933 (4) ÅMo Kα radiation
b = 9.5887 (5) ŵ = 0.63 mm1
c = 10.0058 (5) ÅT = 150 K
α = 92.2999 (7)°0.29 × 0.21 × 0.18 mm
β = 111.9705 (6)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3442 independent reflections
Absorption correction: multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
3363 reflections with I > 2σ(I)
Tmin = 0.84, Tmax = 0.89Rint = 0.015
16531 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.076H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.43 e Å3
3442 reflectionsΔρmin = 0.27 e Å3
235 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co11.00000.50000.50000.01268 (8)
N111.00772 (14)0.64830 (12)0.66911 (12)0.0166 (2)
C111.01890 (18)0.60773 (15)0.79794 (15)0.0206 (3)
H111.01450.50910.80990.025*
C211.03664 (18)0.70288 (15)0.91484 (15)0.0221 (3)
H211.04690.66991.00520.026*
C311.03933 (18)0.84696 (15)0.89905 (15)0.0205 (3)
C411.02532 (19)0.88863 (15)0.76420 (15)0.0228 (3)
H411.02550.98560.74800.027*
C511.01111 (18)0.78745 (15)0.65403 (15)0.0199 (3)
H511.00340.81800.56310.024*
C611.0565 (2)0.95237 (17)1.02381 (15)0.0267 (3)
H61A1.17361.01611.07120.032*
H61B1.03030.89601.09710.032*
N120.61075 (15)0.58527 (13)0.84643 (13)0.0207 (2)
C120.52451 (19)0.66391 (16)0.76178 (16)0.0248 (3)
H120.48680.64080.65890.030*
C220.4878 (2)0.77847 (16)0.81846 (16)0.0276 (3)
H220.42530.83190.75490.033*
C320.54274 (17)0.81441 (15)0.96850 (15)0.0207 (3)
C420.6322 (2)0.73079 (16)1.05508 (15)0.0251 (3)
H420.67190.75151.15830.030*
C520.6632 (2)0.61772 (16)0.99128 (16)0.0257 (3)
H520.72370.56121.05210.031*
C620.5060 (2)0.93506 (16)1.04066 (16)0.0266 (3)
H62A0.59480.97111.14000.032*
H62B0.39960.89281.05110.032*
C130.65325 (16)0.11282 (13)0.55581 (13)0.0145 (2)
C230.51056 (16)0.13905 (13)0.56013 (14)0.0154 (2)
C330.35951 (16)0.02621 (14)0.50310 (14)0.0159 (2)
H330.26250.04470.50450.019*
C430.81693 (16)0.23255 (13)0.59562 (13)0.0149 (2)
C530.51163 (17)0.28302 (14)0.62758 (15)0.0176 (3)
O130.80913 (11)0.34027 (10)0.52823 (10)0.01647 (19)
O230.94715 (12)0.21110 (11)0.68265 (11)0.0219 (2)
O330.64417 (12)0.35290 (11)0.74026 (11)0.0221 (2)
H33A0.636 (3)0.468 (3)0.791 (3)0.076 (9)*
O430.38682 (13)0.32279 (12)0.57544 (13)0.0301 (3)
O1W1.17975 (12)0.42847 (11)0.65954 (10)0.01734 (19)
H1WB1.248 (3)0.402 (2)0.632 (2)0.035 (5)*
H1WA1.124 (3)0.356 (2)0.672 (2)0.033 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.01498 (13)0.01026 (12)0.01364 (13)0.00431 (9)0.00641 (9)0.00109 (8)
N110.0194 (5)0.0141 (5)0.0178 (5)0.0058 (4)0.0087 (4)0.0009 (4)
C110.0279 (7)0.0162 (6)0.0208 (6)0.0085 (5)0.0120 (5)0.0035 (5)
C210.0317 (7)0.0220 (7)0.0177 (6)0.0113 (6)0.0132 (6)0.0051 (5)
C310.0266 (7)0.0206 (6)0.0175 (6)0.0114 (5)0.0096 (5)0.0009 (5)
C410.0356 (8)0.0169 (6)0.0201 (6)0.0131 (6)0.0121 (6)0.0030 (5)
C510.0290 (7)0.0179 (6)0.0171 (6)0.0110 (5)0.0110 (5)0.0038 (5)
C610.0409 (9)0.0274 (7)0.0168 (6)0.0195 (7)0.0110 (6)0.0002 (5)
N120.0225 (6)0.0166 (5)0.0225 (6)0.0066 (4)0.0085 (5)0.0013 (4)
C120.0333 (8)0.0197 (7)0.0198 (6)0.0096 (6)0.0084 (6)0.0006 (5)
C220.0375 (8)0.0223 (7)0.0214 (7)0.0167 (6)0.0051 (6)0.0016 (5)
C320.0242 (7)0.0157 (6)0.0222 (7)0.0080 (5)0.0082 (5)0.0002 (5)
C420.0343 (8)0.0244 (7)0.0177 (6)0.0153 (6)0.0077 (6)0.0013 (5)
C520.0324 (8)0.0238 (7)0.0223 (7)0.0167 (6)0.0068 (6)0.0021 (5)
C620.0398 (8)0.0210 (7)0.0240 (7)0.0175 (6)0.0128 (6)0.0018 (6)
C130.0168 (6)0.0129 (5)0.0149 (5)0.0044 (5)0.0075 (5)0.0023 (4)
C230.0186 (6)0.0126 (5)0.0170 (6)0.0056 (5)0.0088 (5)0.0023 (4)
C330.0173 (6)0.0145 (6)0.0194 (6)0.0062 (5)0.0099 (5)0.0030 (5)
C430.0174 (6)0.0131 (5)0.0157 (6)0.0045 (5)0.0088 (5)0.0003 (4)
C530.0207 (6)0.0134 (6)0.0227 (6)0.0050 (5)0.0132 (5)0.0017 (5)
O130.0165 (4)0.0138 (4)0.0196 (4)0.0043 (3)0.0079 (4)0.0040 (3)
O230.0170 (4)0.0202 (5)0.0262 (5)0.0047 (4)0.0061 (4)0.0095 (4)
O330.0230 (5)0.0180 (5)0.0234 (5)0.0079 (4)0.0068 (4)0.0039 (4)
O430.0233 (5)0.0238 (5)0.0390 (6)0.0124 (4)0.0058 (5)0.0080 (4)
O1W0.0171 (4)0.0155 (4)0.0204 (5)0.0058 (4)0.0079 (4)0.0035 (4)
Geometric parameters (Å, º) top
Co1—O132.0990 (9)C22—C321.388 (2)
Co1—O13i2.0991 (9)C22—H220.9500
Co1—O1Wi2.1049 (9)C32—C421.3910 (19)
Co1—O1W2.1049 (9)C32—C621.5142 (18)
Co1—N112.1341 (11)C42—C521.3811 (19)
Co1—N11i2.1341 (11)C42—H420.9500
N11—C111.3368 (17)C52—H520.9500
N11—C511.3422 (17)C62—C62iii1.521 (3)
C11—C211.3857 (19)C62—H62A0.9900
C11—H110.9500C62—H62B0.9900
C21—C311.3916 (19)C13—C33iv1.3930 (17)
C21—H210.9500C13—C231.4020 (17)
C31—C411.3923 (19)C13—C431.5133 (17)
C31—C611.5074 (18)C23—C331.3948 (18)
C41—C511.3831 (18)C23—C531.5082 (17)
C41—H410.9500C33—C13iv1.3930 (17)
C51—H510.9500C33—H330.9500
C61—C61ii1.514 (3)C43—O231.2557 (16)
C61—H61A0.9900C43—O131.2594 (15)
C61—H61B0.9900C53—O431.2297 (17)
N12—C121.3320 (19)C53—O331.2883 (17)
N12—C521.3384 (19)O33—H33A1.23 (3)
N12—H33A1.34 (3)O1W—H1WB0.85 (2)
C12—C221.389 (2)O1W—H1WA0.79 (2)
C12—H120.9500
O13—Co1—O13i180.00 (4)N12—C12—C22122.38 (13)
O13—Co1—O1Wi89.85 (4)N12—C12—H12118.8
O13i—Co1—O1Wi90.15 (4)C22—C12—H12118.8
O13—Co1—O1W90.15 (4)C32—C22—C12119.64 (13)
O13i—Co1—O1W89.85 (4)C32—C22—H22120.2
O1Wi—Co1—O1W180.0C12—C22—H22120.2
O13—Co1—N1189.34 (4)C22—C32—C42117.15 (12)
O13i—Co1—N1190.66 (4)C22—C32—C62123.61 (13)
O1Wi—Co1—N1191.35 (4)C42—C32—C62119.21 (13)
O1W—Co1—N1188.65 (4)C52—C42—C32120.14 (13)
O13—Co1—N11i90.66 (4)C52—C42—H42119.9
O13i—Co1—N11i89.34 (4)C32—C42—H42119.9
O1Wi—Co1—N11i88.65 (4)N12—C52—C42122.03 (13)
O1W—Co1—N11i91.35 (4)N12—C52—H52119.0
N11—Co1—N11i180.000 (1)C42—C52—H52119.0
C11—N11—C51117.35 (11)C32—C62—C62iii114.79 (15)
C11—N11—Co1120.74 (9)C32—C62—H62A108.6
C51—N11—Co1121.81 (9)C62iii—C62—H62A108.6
N11—C11—C21123.04 (12)C32—C62—H62B108.6
N11—C11—H11118.5C62iii—C62—H62B108.6
C21—C11—H11118.5H62A—C62—H62B107.5
C11—C21—C31119.62 (12)C33iv—C13—C23118.93 (11)
C11—C21—H21120.2C33iv—C13—C43117.48 (11)
C31—C21—H21120.2C23—C13—C43123.18 (11)
C21—C31—C41117.31 (12)C33—C23—C13119.16 (11)
C21—C31—C61120.77 (12)C33—C23—C53117.40 (11)
C41—C31—C61121.92 (12)C13—C23—C53123.41 (11)
C51—C41—C31119.36 (12)C13iv—C33—C23121.90 (12)
C51—C41—H41120.3C13iv—C33—H33119.1
C31—C41—H41120.3C23—C33—H33119.1
N11—C51—C41123.29 (12)O23—C43—O13126.34 (12)
N11—C51—H51118.4O23—C43—C13117.96 (11)
C41—C51—H51118.4O13—C43—C13115.47 (11)
C31—C61—C61ii112.98 (15)O43—C53—O33125.00 (12)
C31—C61—H61A109.0O43—C53—C23118.74 (12)
C61ii—C61—H61A109.0O33—C53—C23116.21 (11)
C31—C61—H61B109.0C43—O13—Co1129.42 (8)
C61ii—C61—H61B109.0C53—O33—H33A112.8 (13)
H61A—C61—H61B107.8Co1—O1W—H1WB116.0 (14)
C12—N12—C52118.67 (12)Co1—O1W—H1WA101.5 (15)
C12—N12—H33A122.1 (12)H1WB—O1W—H1WA105 (2)
C52—N12—H33A119.1 (12)
O13—Co1—N11—C1150.41 (11)C62—C32—C42—C52178.30 (15)
O13i—Co1—N11—C11129.59 (11)C12—N12—C52—C420.7 (2)
O1Wi—Co1—N11—C11140.24 (11)C32—C42—C52—N120.5 (3)
O1W—Co1—N11—C1139.76 (11)C22—C32—C62—C62iii32.6 (3)
O13—Co1—N11—C51133.41 (11)C42—C32—C62—C62iii149.39 (18)
O13i—Co1—N11—C5146.59 (11)C33iv—C13—C23—C331.1 (2)
O1Wi—Co1—N11—C5143.58 (11)C43—C13—C23—C33171.44 (12)
O1W—Co1—N11—C51136.42 (11)C33iv—C13—C23—C53177.10 (12)
C51—N11—C11—C211.2 (2)C43—C13—C23—C5310.34 (19)
Co1—N11—C11—C21175.12 (11)C13—C23—C33—C13iv1.2 (2)
N11—C11—C21—C311.6 (2)C53—C23—C33—C13iv177.18 (12)
C11—C21—C31—C410.6 (2)C33iv—C13—C43—O2356.23 (16)
C11—C21—C31—C61179.29 (14)C23—C13—C43—O23131.12 (13)
C21—C31—C41—C510.6 (2)C33iv—C13—C43—O13118.61 (13)
C61—C31—C41—C51179.54 (14)C23—C13—C43—O1354.04 (17)
C11—N11—C51—C410.0 (2)C33—C23—C53—O4333.79 (18)
Co1—N11—C51—C41176.34 (11)C13—C23—C53—O43147.96 (14)
C31—C41—C51—N110.9 (2)C33—C23—C53—O33143.98 (12)
C21—C31—C61—C61ii138.30 (18)C13—C23—C53—O3334.27 (18)
C41—C31—C61—C61ii41.6 (3)O23—C43—O13—Co113.17 (19)
C52—N12—C12—C220.2 (2)C13—C43—O13—Co1161.17 (8)
N12—C12—C22—C320.4 (2)O1Wi—Co1—O13—C43168.07 (11)
C12—C22—C32—C420.6 (2)O1W—Co1—O13—C4311.93 (11)
C12—C22—C32—C62178.65 (15)N11—Co1—O13—C43100.58 (11)
C22—C32—C42—C520.1 (2)N11i—Co1—O13—C4379.42 (11)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y+2, z+2; (iii) x+1, y+2, z+2; (iv) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O33—H33A···N121.23 (3)1.34 (3)2.5695 (15)174 (3)
O1W—H1WB···O43v0.85 (2)1.87 (2)2.7252 (14)174 (2)
O1W—H1WA···O230.79 (2)1.86 (2)2.6265 (14)164 (2)
Symmetry code: (v) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formula[Co(C10H4O8)(C12H10N2)(H2O)2]·C12H10N2[Co(C10H4O8)(C12H12N2)(H2O)2]·C12H12N2
Mr711.53715.57
Crystal system, space groupTriclinic, P1Triclinic, P1
Temperature (K)150150
a, b, c (Å)9.0283 (2), 9.6152 (2), 10.1064 (3)9.0933 (4), 9.5887 (5), 10.0058 (5)
α, β, γ (°)93.1051 (14), 113.8441 (13), 106.2234 (14)92.2999 (7), 111.9705 (6), 105.6443 (7)
V3)756.41 (3)769.33 (7)
Z11
Radiation typeMo KαMo Kα
µ (mm1)0.640.63
Crystal size (mm)0.55 × 0.42 × 0.230.29 × 0.21 × 0.18
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Bruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS in SAINT-NT; Bruker, 2002)
Multi-scan
(SADABS in SAINT-NT; Bruker, 2002)
Tmin, Tmax0.70, 0.860.84, 0.89
No. of measured, independent and
observed [I > 2σ(I)] reflections
12370, 3331, 3132 16531, 3442, 3363
Rint0.0170.015
(sin θ/λ)max1)0.6570.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.078, 1.04 0.028, 0.076, 1.05
No. of reflections33313442
No. of parameters235235
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.38, 0.250.43, 0.27

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) for (I) top
Co1—O132.0824 (10)Co1—N112.1251 (12)
Co1—O1W2.1171 (11)
O13—Co1—O1W90.01 (4)O1W—Co1—N1188.35 (4)
O13—Co1—N1188.87 (4)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O33—H33A···N121.35 (3)1.22 (3)2.5759 (16)177 (3)
O1W—H1WB···O43i0.81 (3)1.92 (3)2.7210 (16)174 (2)
O1W—H1WA···O230.83 (2)1.83 (2)2.6414 (16)165 (2)
Symmetry code: (i) x+1, y, z.
Selected geometric parameters (Å, º) for (II) top
Co1—O132.0990 (9)Co1—N112.1341 (11)
Co1—O1W2.1049 (9)
O13—Co1—O1W90.15 (4)O1W—Co1—N1188.65 (4)
O13—Co1—N1189.34 (4)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O33—H33A···N121.23 (3)1.34 (3)2.5695 (15)174 (3)
O1W—H1WB···O43i0.85 (2)1.87 (2)2.7252 (14)174 (2)
O1W—H1WA···O230.79 (2)1.86 (2)2.6265 (14)164 (2)
Symmetry code: (i) x+1, y, z.
 

Subscribe to Acta Crystallographica Section C: Structural Chemistry

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds