Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012312/gs1105sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012312/gs1105Isup2.hkl |
CCDC reference: 156144
Complex (I) was hydrothermally synthesized from a mixture of cobalt(II) chloride hexahydrate, trimesic acid, potassium hydroxide and water in the molar ratio 1:1:1:60. The starting mixture was heated for 12 h at 453 K under autogenous pressure (final pH 2). The resulting solid phase, consisting of pink needles of (I), was filtered off and dried at room temperature. Query shape.
H atoms from water molecules were found via difference Fourier maps and isotropically refined. H atoms from the trimesate molecules were treated as riding (O—H 0.82 and C—H 0.93 Å). All H-atom positions (trimesate and water) could be deduced from difference Fourier maps. However, H atoms from the trimesate were placed in calculated positions in order to have a perfect sp2 geometry.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Co(C9H5O6)2(H2O)4] | F(000) = 562 |
Mr = 549.26 | Dx = 1.818 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 5.1160 (1) Å | Cell parameters from 5763 reflections |
b = 13.0080 (2) Å | θ = 2.1–29.8° |
c = 15.1890 (1) Å | µ = 0.95 mm−1 |
β = 96.853 (1)° | T = 296 K |
V = 1003.59 (3) Å3 | Parallelepiped, pink |
Z = 2 | 0.76 × 0.14 × 0.08 mm |
Siemens SMART 1K diffractometer | 2590 independent reflections |
Radiation source: fine-focus sealed tube | 2281 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
ω scans | θmax = 29.8°, θmin = 2.1° |
Absorption correction: semi-empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −6→7 |
Tmin = 0.533, Tmax = 0.928 | k = −17→14 |
6860 measured reflections | l = −20→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.025 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.073 | w = 1/[σ2(Fo2) + (0.042P)2 + 0.0785P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
2590 reflections | Δρmax = 0.36 e Å−3 |
179 parameters | Δρmin = −0.40 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.031 (2) |
[Co(C9H5O6)2(H2O)4] | V = 1003.59 (3) Å3 |
Mr = 549.26 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 5.1160 (1) Å | µ = 0.95 mm−1 |
b = 13.0080 (2) Å | T = 296 K |
c = 15.1890 (1) Å | 0.76 × 0.14 × 0.08 mm |
β = 96.853 (1)° |
Siemens SMART 1K diffractometer | 2590 independent reflections |
Absorption correction: semi-empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2281 reflections with I > 2σ(I) |
Tmin = 0.533, Tmax = 0.928 | Rint = 0.022 |
6860 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 0 restraints |
wR(F2) = 0.073 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.09 | Δρmax = 0.36 e Å−3 |
2590 reflections | Δρmin = −0.40 e Å−3 |
179 parameters |
Experimental. Blessing, R. H. (1995). Acta Cryst. A51, 33–38. |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 1/2 | 1 | 0 | 0.01799 (9) | |
O1 | 0.28141 (17) | 0.88421 (7) | 0.05566 (6) | 0.0236 (2) | |
O2 | 0.02902 (18) | 0.76498 (8) | −0.01636 (7) | 0.0303 (2) | |
O3 | 0.5219 (2) | 0.34736 (7) | 0.14601 (8) | 0.0365 (3) | |
O4 | 0.1612 (2) | 0.41152 (8) | 0.07056 (9) | 0.0445 (3) | |
H4A | 0.1293 | 0.3505 | 0.0610 | 0.067* | |
O5 | 1.16179 (19) | 0.63394 (7) | 0.29025 (7) | 0.0294 (2) | |
O6 | 1.0432 (2) | 0.79506 (8) | 0.25379 (8) | 0.0374 (3) | |
H6A | 1.1773 | 0.8086 | 0.2869 | 0.056* | |
O7 | 0.81952 (19) | 0.97174 (8) | 0.09412 (7) | 0.0246 (2) | |
O8 | 0.3575 (2) | 1.10552 (8) | 0.08847 (7) | 0.0274 (2) | |
C1 | 0.3924 (2) | 0.70954 (9) | 0.08663 (8) | 0.0196 (2) | |
C2 | 0.3247 (2) | 0.60613 (9) | 0.07853 (8) | 0.0224 (3) | |
H2 | 0.1758 | 0.5867 | 0.0410 | 0.027* | |
C3 | 0.4779 (2) | 0.53088 (10) | 0.12621 (8) | 0.0219 (3) | |
C4 | 0.7028 (2) | 0.55907 (10) | 0.18195 (8) | 0.0225 (3) | |
H4 | 0.8070 | 0.5093 | 0.2130 | 0.027* | |
C5 | 0.7699 (2) | 0.66331 (9) | 0.19068 (8) | 0.0204 (2) | |
C6 | 0.6143 (2) | 0.73814 (9) | 0.14364 (8) | 0.0208 (2) | |
H6 | 0.6590 | 0.8072 | 0.1504 | 0.025* | |
C7 | 0.2232 (2) | 0.79123 (9) | 0.03745 (8) | 0.0192 (2) | |
C8 | 0.3939 (3) | 0.42090 (10) | 0.11620 (9) | 0.0253 (3) | |
C9 | 1.0096 (2) | 0.69466 (10) | 0.25019 (8) | 0.0216 (2) | |
H7A | 0.849 (5) | 1.0181 (18) | 0.1287 (16) | 0.054 (7)* | |
H7B | 0.967 (4) | 0.9479 (15) | 0.0807 (13) | 0.044 (5)* | |
H8A | 0.236 (4) | 1.1484 (15) | 0.0671 (13) | 0.049 (6)* | |
H8B | 0.467 (5) | 1.1345 (15) | 0.1226 (14) | 0.049 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01581 (13) | 0.01300 (14) | 0.02386 (14) | 0.00011 (7) | −0.00297 (8) | −0.00095 (8) |
O1 | 0.0214 (4) | 0.0136 (4) | 0.0345 (5) | −0.0010 (3) | −0.0013 (3) | 0.0013 (3) |
O2 | 0.0273 (5) | 0.0172 (5) | 0.0414 (5) | 0.0007 (3) | −0.0170 (4) | 0.0010 (4) |
O3 | 0.0318 (5) | 0.0176 (5) | 0.0543 (7) | 0.0023 (4) | −0.0188 (5) | 0.0042 (4) |
O4 | 0.0375 (6) | 0.0154 (5) | 0.0708 (8) | −0.0030 (4) | −0.0340 (5) | 0.0039 (5) |
O5 | 0.0252 (5) | 0.0266 (5) | 0.0327 (5) | −0.0031 (4) | −0.0112 (4) | 0.0079 (4) |
O6 | 0.0309 (5) | 0.0215 (5) | 0.0533 (7) | −0.0044 (4) | −0.0222 (5) | −0.0011 (4) |
O7 | 0.0197 (5) | 0.0212 (5) | 0.0309 (5) | 0.0022 (4) | −0.0056 (4) | −0.0041 (4) |
O8 | 0.0243 (5) | 0.0232 (5) | 0.0325 (5) | 0.0052 (4) | −0.0056 (4) | −0.0071 (4) |
C1 | 0.0183 (5) | 0.0157 (5) | 0.0235 (6) | 0.0003 (4) | −0.0026 (4) | 0.0015 (4) |
C2 | 0.0216 (6) | 0.0162 (6) | 0.0271 (6) | −0.0001 (4) | −0.0072 (5) | 0.0009 (4) |
C3 | 0.0217 (6) | 0.0153 (5) | 0.0266 (6) | 0.0003 (4) | −0.0056 (5) | 0.0008 (4) |
C4 | 0.0208 (6) | 0.0186 (6) | 0.0259 (6) | 0.0004 (4) | −0.0065 (5) | 0.0023 (4) |
C5 | 0.0185 (5) | 0.0178 (6) | 0.0231 (5) | −0.0008 (4) | −0.0048 (4) | 0.0008 (4) |
C6 | 0.0200 (6) | 0.0159 (6) | 0.0249 (6) | −0.0018 (4) | −0.0034 (4) | 0.0009 (4) |
C7 | 0.0174 (5) | 0.0151 (5) | 0.0241 (5) | 0.0001 (4) | −0.0010 (4) | 0.0020 (4) |
C8 | 0.0246 (6) | 0.0173 (6) | 0.0308 (6) | 0.0001 (5) | −0.0099 (5) | 0.0006 (5) |
C9 | 0.0202 (6) | 0.0206 (6) | 0.0226 (6) | −0.0029 (4) | −0.0036 (4) | 0.0011 (4) |
Co1—O7 | 2.0720 (9) | O7—H7B | 0.86 (2) |
Co1—O7i | 2.0720 (9) | O8—H8A | 0.87 (2) |
Co1—O8i | 2.111 (1) | O8—H8B | 0.81 (2) |
Co1—O8 | 2.111 (1) | C1—C2 | 1.391 (2) |
Co1—O1 | 2.1117 (9) | C1—C6 | 1.393 (2) |
Co1—O1i | 2.1117 (9) | C1—C7 | 1.511 (2) |
O1—C7 | 1.268 (2) | C2—C3 | 1.401 (2) |
O2—C7 | 1.256 (2) | C2—H2 | 0.93 |
O3—C8 | 1.216 (2) | C3—C4 | 1.394 (2) |
O4—C8 | 1.310 (2) | C3—C8 | 1.496 (2) |
O4—H4A | 0.82 | C4—C5 | 1.401 (2) |
O5—C9 | 1.219 (2) | C4—H4 | 0.93 |
O6—C9 | 1.317 (2) | C5—C6 | 1.399 (2) |
O6—H6A | 0.82 | C5—C9 | 1.491 (2) |
O7—H7A | 0.80 (2) | C6—H6 | 0.93 |
O7—Co1—O7i | 180.0 | C6—C1—C7 | 119.71 (10) |
O7—Co1—O8i | 91.14 (4) | C1—C2—C3 | 120.79 (11) |
O7i—Co1—O8i | 88.86 (4) | C1—C2—H2 | 119.6 |
O7—Co1—O8 | 88.86 (4) | C3—C2—H2 | 119.6 |
O7i—Co1—O8 | 91.14 (4) | C4—C3—C2 | 120.05 (11) |
O8i—Co1—O8 | 180.0 | C4—C3—C8 | 121.30 (11) |
O7—Co1—O1 | 90.52 (4) | C2—C3—C8 | 118.65 (10) |
O7i—Co1—O1 | 89.48 (4) | C3—C4—C5 | 119.16 (11) |
O8i—Co1—O1 | 91.76 (4) | C3—C4—H4 | 120.4 |
O8—Co1—O1 | 88.24 (4) | C5—C4—H4 | 120.4 |
O7—Co1—O1i | 89.48 (4) | C6—C5—C4 | 120.47 (10) |
O7i—Co1—O1i | 90.52 (4) | C6—C5—C9 | 119.76 (11) |
O8i—Co1—O1i | 88.24 (4) | C4—C5—C9 | 119.77 (10) |
O8—Co1—O1i | 91.76 (4) | C1—C6—C5 | 120.23 (11) |
O1—Co1—O1i | 180.00 (5) | C1—C6—H6 | 119.9 |
C7—O1—Co1 | 135.62 (8) | C5—C6—H6 | 119.9 |
C8—O4—H4A | 109.5 | O2—C7—O1 | 123.24 (11) |
C9—O6—H6A | 109.5 | O2—C7—C1 | 119.51 (11) |
Co1—O7—H7A | 112.9 (17) | O1—C7—C1 | 117.20 (10) |
Co1—O7—H7B | 122.8 (13) | O3—C8—O4 | 122.60 (12) |
H7A—O7—H7B | 109 (2) | O3—C8—C3 | 125.39 (11) |
Co1—O8—H8A | 117.8 (13) | O4—C8—C3 | 112.00 (10) |
Co1—O8—H8B | 116.4 (16) | O5—C9—O6 | 123.30 (12) |
H8A—O8—H8B | 111 (2) | O5—C9—C5 | 123.74 (11) |
C2—C1—C6 | 119.28 (11) | O6—C9—C5 | 112.95 (11) |
C2—C1—C7 | 120.95 (10) |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O2ii | 0.82 | 1.80 | 2.589 (2) | 161 |
O6—H6A···O3iii | 0.82 | 1.81 | 2.631 (2) | 175 |
O7—H7A···O5iii | 0.80 (2) | 1.95 (3) | 2.740 (2) | 168 |
O7—H7B···O1iv | 0.86 (2) | 1.89 (2) | 2.748 (2) | 175 |
O8—H8A···O2v | 0.87 (2) | 1.86 (3) | 2.726 (2) | 177 |
Symmetry codes: (ii) −x, −y+1, −z; (iii) −x+2, y+1/2, −z+1/2; (iv) x+1, y, z; (v) −x, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C9H5O6)2(H2O)4] |
Mr | 549.26 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 5.1160 (1), 13.0080 (2), 15.1890 (1) |
β (°) | 96.853 (1) |
V (Å3) | 1003.59 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.95 |
Crystal size (mm) | 0.76 × 0.14 × 0.08 |
Data collection | |
Diffractometer | Siemens SMART 1K diffractometer |
Absorption correction | Semi-empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.533, 0.928 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6860, 2590, 2281 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.699 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.073, 1.09 |
No. of reflections | 2590 |
No. of parameters | 179 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.36, −0.40 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Siemens, 1994), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
Co1—O7 | 2.0720 (9) | O7—H7B | 0.86 (2) |
Co1—O7i | 2.0720 (9) | O8—H8A | 0.87 (2) |
Co1—O8i | 2.111 (1) | O8—H8B | 0.81 (2) |
Co1—O8 | 2.111 (1) | C1—C2 | 1.391 (2) |
Co1—O1 | 2.1117 (9) | C1—C6 | 1.393 (2) |
Co1—O1i | 2.1117 (9) | C1—C7 | 1.511 (2) |
O1—C7 | 1.268 (2) | C2—C3 | 1.401 (2) |
O2—C7 | 1.256 (2) | C2—H2 | 0.93 |
O3—C8 | 1.216 (2) | C3—C4 | 1.394 (2) |
O4—C8 | 1.310 (2) | C3—C8 | 1.496 (2) |
O4—H4A | 0.82 | C4—C5 | 1.401 (2) |
O5—C9 | 1.219 (2) | C4—H4 | 0.93 |
O6—C9 | 1.317 (2) | C5—C6 | 1.399 (2) |
O6—H6A | 0.82 | C5—C9 | 1.491 (2) |
O7—H7A | 0.80 (2) | C6—H6 | 0.93 |
O7—Co1—O7i | 180.0 | O8i—Co1—O1 | 91.76 (4) |
O7—Co1—O8i | 91.14 (4) | O8—Co1—O1 | 88.24 (4) |
O7i—Co1—O8i | 88.86 (4) | O7—Co1—O1i | 89.48 (4) |
O7—Co1—O8 | 88.86 (4) | O7i—Co1—O1i | 90.52 (4) |
O7i—Co1—O8 | 91.14 (4) | O8i—Co1—O1i | 88.24 (4) |
O8i—Co1—O8 | 180.0 | O8—Co1—O1i | 91.76 (4) |
O7—Co1—O1 | 90.52 (4) | O1—Co1—O1i | 180.00 (5) |
O7i—Co1—O1 | 89.48 (4) |
Symmetry code: (i) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O2ii | 0.82 | 1.80 | 2.589 (2) | 161 |
O6—H6A···O3iii | 0.82 | 1.81 | 2.631 (2) | 175 |
O7—H7A···O5iii | 0.80 (2) | 1.95 (3) | 2.740 (2) | 168 |
O7—H7B···O1iv | 0.86 (2) | 1.89 (2) | 2.748 (2) | 175 |
O8—H8A···O2v | 0.87 (2) | 1.86 (3) | 2.726 (2) | 177 |
Symmetry codes: (ii) −x, −y+1, −z; (iii) −x+2, y+1/2, −z+1/2; (iv) x+1, y, z; (v) −x, −y+2, −z. |
Over the last decade, significant research effort has focused on using organic molecular building blocks to generate three-dimensional porous solids, via hydrogen bonding or copolymerization of metal ions (Palmans et al., 1997; Livage et al., 1998, 1999). Trimesic acid (benzene-1,3,5-tricarboxylic acid, TMA) has successfully been used to design organic supramolecular networks by several authors (Kolotuchin et al., 1999; Sharma & Zaworotko, 1996; Melendez et al., 1996). Its geometry and hydrogen-bonding capability (three carboxylic acid groups) make it an interesting tool for crystal engineering. Condensation of TMA with metal ions was first developed by Yaghi et al. (1996, 1997, 1998) to generate coordination polymers (Chui, Siu & Williams, 1999; Chui, Los et al., 1999; Daiguebonne et al., 1999; Li et al., 1999). Herein, we describe the synthesis and crystal structure of a new cobalt(II)-TMA complex, the title compound, (I), and we demonstrate that this species can be used as synthon to generate supramolecular networks. \sch
The centrosymmetric complex of (I) is shown with the atom-labelling scheme in Fig. 1. Two unidentate carboxylate groups and four water molecules octahedrally coordinate the Co atom. Each trimesate ligand presents one bonding and two dangling protonated carboxylate groups, leading to a single negative charge on the ligand. The TMA− and two of the coordinated water molecules lie in planes, the Co atom being located in between these planes. A network of strong hydrogen bonds (Table 2), between TMA− and between TMA− and water molecules, provides the basis of this two-dimensional network (Fig. 2a). The Co atom ensures the three-dimensionality of the architecture by linking adjacent layers (Fig. 2 b).
These results illustrate the clear tendency of trimesate complexes to pack into planes in order to maximize hydrogen bonding. The solid-state arrangement is therefore dominated by the formation of trimesate layers, as previously described for lanthanide complexes by Daiguebonne et al. (1999).