Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105022882/fa1144sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105022882/fa1144Isup2.hkl |
CCDC reference: 285644
In a typical synthesis, bpe (0.0921 g) and adipic acid (0.0731 g) were dissolved in CH3OH/H2O (1:1, v/v, 50 ml), and to the resulting solution, CoCl2·6H2O (0.1190 g) was added with stirring. The mixture was stirred for a further ca 30 min, yielding a red-colored solution, which was then maintained at room temperature; red crystals suitable for X-ray analysis were obtained after two weeks.
Compound (I) is triclinic; space group P1 was assumed and comfirmed by the analysis. H atoms associated with C atoms were positioned geometrically and refined using a riding model [C—H = 0.93 and 0.97 Å, and Uiso(H) = 1.2Ueq(C)], while H atoms of the aqua ligands and carboxyl group O3 were located from the difference Fourier syntheses with O—H distances refined.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[Co(C6H9O4)2(C12H12N2)(H2O)2] | Z = 1 |
Mr = 569.46 | F(000) = 299 |
Triclinic, P1 | Dx = 1.466 Mg m−3 |
Hall symbol: -P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.6928 (17) Å | Cell parameters from 25 reflections |
b = 8.8579 (18) Å | θ = 10–25° |
c = 9.6059 (19) Å | µ = 0.72 mm−1 |
α = 85.17 (3)° | T = 296 K |
β = 65.14 (3)° | Prism, red |
γ = 74.03 (3)° | 0.39 × 0.31 × 0.22 mm |
V = 644.8 (2) Å3 |
Bruker P4 diffractometer | 2670 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 27.5°, θmin = 2.3° |
θ/2θ scans | h = −1→11 |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | k = −11→11 |
Tmin = 0.818, Tmax = 0.853 | l = −11→12 |
3546 measured reflections | 3 standard reflections every 97 reflections |
2959 independent reflections | intensity decay: no |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0298P)2 + 0.2282P] where P = (Fo2 + 2Fc2)/3 |
2959 reflections | (Δ/σ)max < 0.001 |
182 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
[Co(C6H9O4)2(C12H12N2)(H2O)2] | γ = 74.03 (3)° |
Mr = 569.46 | V = 644.8 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.6928 (17) Å | Mo Kα radiation |
b = 8.8579 (18) Å | µ = 0.72 mm−1 |
c = 9.6059 (19) Å | T = 296 K |
α = 85.17 (3)° | 0.39 × 0.31 × 0.22 mm |
β = 65.14 (3)° |
Bruker P4 diffractometer | 2670 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | Rint = 0.024 |
Tmin = 0.818, Tmax = 0.853 | 3 standard reflections every 97 reflections |
3546 measured reflections | intensity decay: no |
2959 independent reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.25 e Å−3 |
2959 reflections | Δρmin = −0.24 e Å−3 |
182 parameters |
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 | ||
Co | 0.0000 | 0.5000 | 0.5000 | 0.02339 (9) | |
N1 | 0.01189 (18) | 0.65316 (15) | 0.65628 (14) | 0.0277 (3) | |
O1 | 0.21630 (17) | 0.20575 (15) | 0.64748 (15) | 0.0402 (3) | |
O2 | 0.26087 (15) | 0.36416 (14) | 0.45035 (12) | 0.0311 (2) | |
O3 | 0.4607 (2) | 0.25849 (19) | 1.16196 (15) | 0.0521 (4) | |
O4 | 0.31661 (18) | 0.45166 (16) | 1.06256 (14) | 0.0432 (3) | |
O5 | −0.10399 (17) | 0.35414 (14) | 0.68103 (14) | 0.0318 (2) | |
C1 | 0.3139 (2) | 0.26778 (18) | 0.53829 (17) | 0.0279 (3) | |
C2 | 0.5074 (2) | 0.2315 (2) | 0.50342 (19) | 0.0378 (4) | |
H2A | 0.5460 | 0.3263 | 0.4696 | 0.045* | |
H2B | 0.5728 | 0.1541 | 0.4191 | 0.045* | |
C3 | 0.5527 (2) | 0.1696 (2) | 0.63869 (19) | 0.0377 (4) | |
H3A | 0.5122 | 0.0759 | 0.6743 | 0.045* | |
H3B | 0.6795 | 0.1400 | 0.6038 | 0.045* | |
C4 | 0.4715 (2) | 0.2885 (2) | 0.77236 (19) | 0.0373 (4) | |
H4A | 0.5150 | 0.3809 | 0.7382 | 0.045* | |
H4B | 0.3449 | 0.3207 | 0.8059 | 0.045* | |
C5 | 0.5139 (3) | 0.2225 (2) | 0.90591 (19) | 0.0404 (4) | |
H5A | 0.4861 | 0.1219 | 0.9291 | 0.048* | |
H5B | 0.6394 | 0.2033 | 0.8748 | 0.048* | |
C6 | 0.4190 (2) | 0.3247 (2) | 1.04974 (18) | 0.0336 (3) | |
C7 | 0.0758 (2) | 0.59803 (19) | 0.76044 (19) | 0.0333 (3) | |
H7A | 0.1047 | 0.4900 | 0.7720 | 0.040* | |
C8 | 0.1013 (2) | 0.6920 (2) | 0.8517 (2) | 0.0356 (4) | |
H8A | 0.1464 | 0.6473 | 0.9224 | 0.043* | |
C9 | 0.0594 (2) | 0.85315 (19) | 0.83761 (18) | 0.0306 (3) | |
C10 | −0.0109 (2) | 0.91147 (19) | 0.73211 (19) | 0.0345 (4) | |
H10A | −0.0437 | 1.0193 | 0.7204 | 0.041* | |
C11 | −0.0320 (2) | 0.80941 (19) | 0.64446 (18) | 0.0321 (3) | |
H11A | −0.0789 | 0.8511 | 0.5741 | 0.038* | |
C12 | 0.0860 (2) | 0.9603 (2) | 0.9345 (2) | 0.0369 (4) | |
H12A | 0.1372 | 1.0398 | 0.8706 | 0.044* | |
H12B | 0.1676 | 0.8999 | 0.9759 | 0.044* | |
H3C | 0.405 (4) | 0.310 (3) | 1.243 (3) | 0.062 (8)* | |
H5D | −0.014 (4) | 0.300 (3) | 0.688 (3) | 0.054 (7)* | |
H5C | −0.170 (3) | 0.414 (3) | 0.762 (3) | 0.055 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.03023 (16) | 0.02187 (14) | 0.02134 (14) | −0.00585 (11) | −0.01357 (11) | −0.00389 (10) |
N1 | 0.0349 (7) | 0.0258 (6) | 0.0260 (6) | −0.0060 (5) | −0.0158 (5) | −0.0066 (5) |
O1 | 0.0386 (7) | 0.0409 (7) | 0.0424 (7) | −0.0108 (5) | −0.0196 (6) | 0.0122 (5) |
O2 | 0.0329 (6) | 0.0363 (6) | 0.0230 (5) | −0.0029 (5) | −0.0141 (5) | −0.0014 (4) |
O3 | 0.0564 (9) | 0.0617 (9) | 0.0250 (6) | 0.0115 (7) | −0.0200 (6) | −0.0056 (6) |
O4 | 0.0451 (7) | 0.0450 (7) | 0.0300 (6) | 0.0031 (6) | −0.0148 (5) | −0.0046 (5) |
O5 | 0.0350 (6) | 0.0312 (6) | 0.0290 (6) | −0.0088 (5) | −0.0127 (5) | −0.0015 (5) |
C1 | 0.0326 (8) | 0.0286 (7) | 0.0231 (7) | −0.0027 (6) | −0.0143 (6) | −0.0056 (6) |
C2 | 0.0321 (8) | 0.0535 (10) | 0.0241 (7) | −0.0026 (7) | −0.0126 (7) | −0.0033 (7) |
C3 | 0.0333 (9) | 0.0465 (10) | 0.0291 (8) | 0.0038 (7) | −0.0165 (7) | −0.0058 (7) |
C4 | 0.0426 (9) | 0.0401 (9) | 0.0313 (8) | −0.0020 (7) | −0.0222 (7) | −0.0027 (7) |
C5 | 0.0435 (10) | 0.0429 (10) | 0.0287 (8) | 0.0036 (8) | −0.0177 (7) | −0.0031 (7) |
C6 | 0.0317 (8) | 0.0438 (9) | 0.0245 (7) | −0.0074 (7) | −0.0123 (6) | 0.0007 (6) |
C7 | 0.0456 (9) | 0.0246 (7) | 0.0352 (8) | −0.0042 (7) | −0.0240 (7) | −0.0042 (6) |
C8 | 0.0460 (10) | 0.0343 (8) | 0.0340 (8) | −0.0052 (7) | −0.0258 (8) | −0.0060 (7) |
C9 | 0.0325 (8) | 0.0337 (8) | 0.0271 (7) | −0.0090 (6) | −0.0114 (6) | −0.0109 (6) |
C10 | 0.0486 (10) | 0.0240 (7) | 0.0342 (8) | −0.0090 (7) | −0.0197 (8) | −0.0048 (6) |
C11 | 0.0453 (9) | 0.0276 (7) | 0.0289 (7) | −0.0079 (7) | −0.0212 (7) | −0.0025 (6) |
C12 | 0.0404 (9) | 0.0403 (9) | 0.0351 (9) | −0.0124 (7) | −0.0168 (8) | −0.0134 (7) |
Co—O5i | 2.1102 (14) | C3—H3A | 0.9700 |
Co—O5 | 2.1102 (14) | C3—H3B | 0.9700 |
Co—O2 | 2.1223 (14) | C4—C5 | 1.509 (2) |
Co—O2i | 2.1223 (14) | C4—H4A | 0.9700 |
Co—N1 | 2.1576 (13) | C4—H4B | 0.9700 |
Co—N1i | 2.1576 (13) | C5—C6 | 1.500 (2) |
N1—C7 | 1.336 (2) | C5—H5A | 0.9700 |
N1—C11 | 1.339 (2) | C5—H5B | 0.9700 |
O1—C1 | 1.238 (2) | C7—C8 | 1.378 (2) |
O2—C1 | 1.2825 (19) | C7—H7A | 0.9300 |
O3—C6 | 1.320 (2) | C8—C9 | 1.383 (2) |
O3—H3C | 0.82 (3) | C8—H8A | 0.9300 |
O4—C6 | 1.205 (2) | C9—C10 | 1.388 (2) |
O5—H5D | 0.82 (3) | C9—C12 | 1.506 (2) |
O5—H5C | 0.86 (3) | C10—C11 | 1.382 (2) |
C1—C2 | 1.514 (2) | C10—H10A | 0.9300 |
C2—C3 | 1.528 (2) | C11—H11A | 0.9300 |
C2—H2A | 0.9700 | C12—C12ii | 1.517 (3) |
C2—H2B | 0.9700 | C12—H12A | 0.9700 |
C3—C4 | 1.521 (2) | C12—H12B | 0.9700 |
O5i—Co—O5 | 180.00 (5) | H3A—C3—H3B | 107.7 |
O5i—Co—O2 | 88.51 (6) | C5—C4—C3 | 112.01 (15) |
O5—Co—O2 | 91.49 (6) | C5—C4—H4A | 109.2 |
O5i—Co—O2i | 91.49 (6) | C3—C4—H4A | 109.2 |
O5—Co—O2i | 88.51 (6) | C5—C4—H4B | 109.2 |
O2—Co—O2i | 180.0 | C3—C4—H4B | 109.2 |
O5i—Co—N1 | 89.13 (5) | H4A—C4—H4B | 107.9 |
O5—Co—N1 | 90.87 (5) | C6—C5—C4 | 115.16 (15) |
O2—Co—N1 | 91.23 (6) | C6—C5—H5A | 108.5 |
O2i—Co—N1 | 88.77 (6) | C4—C5—H5A | 108.5 |
O5i—Co—N1i | 90.87 (5) | C6—C5—H5B | 108.5 |
O5—Co—N1i | 89.13 (5) | C4—C5—H5B | 108.5 |
O2—Co—N1i | 88.77 (6) | H5A—C5—H5B | 107.5 |
O2i—Co—N1i | 91.23 (6) | O4—C6—O3 | 123.68 (16) |
N1—Co—N1i | 180.000 (1) | O4—C6—C5 | 124.58 (15) |
C7—N1—C11 | 116.74 (13) | O3—C6—C5 | 111.74 (15) |
C7—N1—Co | 122.23 (10) | N1—C7—C8 | 123.78 (15) |
C11—N1—Co | 120.83 (10) | N1—C7—H7A | 118.1 |
C1—O2—Co | 127.23 (10) | C8—C7—H7A | 118.1 |
C6—O3—H3C | 113.2 (19) | C7—C8—C9 | 119.63 (15) |
Co—O5—H5D | 101.5 (18) | C7—C8—H8A | 120.2 |
Co—O5—H5C | 107.4 (17) | C9—C8—H8A | 120.2 |
H5D—O5—H5C | 110 (2) | C8—C9—C10 | 116.88 (14) |
O1—C1—O2 | 123.68 (15) | C8—C9—C12 | 121.43 (15) |
O1—C1—C2 | 119.85 (15) | C10—C9—C12 | 121.69 (15) |
O2—C1—C2 | 116.47 (15) | C11—C10—C9 | 120.02 (15) |
C1—C2—C3 | 114.48 (14) | C11—C10—H10A | 120.0 |
C1—C2—H2A | 108.6 | C9—C10—H10A | 120.0 |
C3—C2—H2A | 108.6 | N1—C11—C10 | 122.93 (15) |
C1—C2—H2B | 108.6 | N1—C11—H11A | 118.5 |
C3—C2—H2B | 108.6 | C10—C11—H11A | 118.5 |
H2A—C2—H2B | 107.6 | C9—C12—C12ii | 111.61 (18) |
C4—C3—C2 | 113.23 (15) | C9—C12—H12A | 109.3 |
C4—C3—H3A | 108.9 | C12ii—C12—H12A | 109.3 |
C2—C3—H3A | 108.9 | C9—C12—H12B | 109.3 |
C4—C3—H3B | 108.9 | C12ii—C12—H12B | 109.3 |
C2—C3—H3B | 108.9 | H12A—C12—H12B | 108.0 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5D···O1 | 0.82 (3) | 1.83 (4) | 2.624 (2) | 163 (3) |
O5—H5C···O4iii | 0.86 (3) | 1.89 (3) | 2.753 (2) | 179 (3) |
O3—H3C···O2iv | 0.82 (3) | 1.87 (3) | 2.658 (2) | 161 (3) |
Symmetry codes: (iii) −x, −y+1, −z+2; (iv) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co(C6H9O4)2(C12H12N2)(H2O)2] |
Mr | 569.46 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 8.6928 (17), 8.8579 (18), 9.6059 (19) |
α, β, γ (°) | 85.17 (3), 65.14 (3), 74.03 (3) |
V (Å3) | 644.8 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.72 |
Crystal size (mm) | 0.39 × 0.31 × 0.22 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.818, 0.853 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3546, 2959, 2670 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.078, 1.05 |
No. of reflections | 2959 |
No. of parameters | 182 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.24 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5D···O1 | 0.82 (3) | 1.83 (4) | 2.624 (2) | 163 (3) |
O5—H5C···O4i | 0.86 (3) | 1.89 (3) | 2.753 (2) | 179 (3) |
O3—H3C···O2ii | 0.82 (3) | 1.87 (3) | 2.658 (2) | 161 (3) |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) x, y, z+1. |
Investigation of coordination polymers has been expanded over the past decade (Moulton & Zaworotko, 2001) because of their intriguing structural motifs and their potential applications in catalysis, host–guest chemistry and magnetism (Leininger et al., 2000; Hagrman et al., 1999; Zhang et al., 2002; Feng & Xu, 2001; Yuan et al., 2002), and the rational design and syntheses of coordination polymers have been focused on the use of benzene di- and polycarboxylates as rigid bridging spacers (Li et al., 1999; Chui et al., 1999). On the other hand, utilization of aliphatic α,ω-dicarboxylates to construct supramolecular aggregates is of growing interest (Rao et al., 2004; Kitagawa et al., 2004). Our recent research effort has been intensively concentrated on construction of coordination polymers with specific topologies based on co-bridging of rigid 4,4'-bipyridine and α,ω-dicarboxylates (Zheng et al., 2004; Zheng & Ying, 2005). However, investigation of coordination polymers using 1,2-di-4-pyridylethane (bpe) and dicarboxylate anions to co-bridge metal ions has been very limited (Mukherjee et al., 2003). We report here a novel coordination polymer, [Co(C6H9O4)2(H2O)2(anti-bpe)], (I), which was obtained by reaction of bpe, adipic acid and CoCl2·6H2O in CH3OH/H2O (1:1, v:v).
In (I), the Co atoms sit on crystallographic inversion centers, and each Co atom is octahedrally coordinated by two N atoms of different anti-bpe ligands, four O atoms of two carboxypentanoate ligands and two aqua ligands. The Co—O bond distances are 2.1102 (14) and 2.1223 (14) Å, and the Co—N distance is 2.1576 (13) Å, with the cis bond angles in the range 88.51 (6)–91.49 (6)°. The anti-bpe ligands bridge the Co atoms along the [110] direction to generate one-dimensional 1∞{Co(Hadipa)2(H2O)2](bpe)2/2} chains, as shown in Fig. 1, which exhibit a relatively strong intrachain hydrogen bond between the aqua O atom and uncoordinated carboxylate atom O1 [O···O = 2.624 (2) Å and O—H···O = 163 (3)°]. Additionally (Table 1), aqua ligand O5 and carboxylic acid group O3 donate H atoms, respectively, to carboxylate atom O4i [symmetry code: (i) −x, 1 − y, 2 − z] and the coordinating carboxylate atom O2ii [symmetry code: (ii) x, y, z + 1] of neighboring chains, to form interchain hydrogen bonds [O···O = 2.753 (2) and 2.658 (2) Å, and O—H···O = 179 (3) and 161 (3)°]. The polymeric chains are linked through these bonds to form two-dimensional layers parallel to (100). The resulting layers are further stabilized by weak interchain hydrogen bonds between atom C12 of one anti-bpe ligand and uncoordinated carboxylate atom O1iii [symmetry code: (iii) x, y + 1, z]. The twisted carboxypentanoate ligands of one layer protrude into the grooves of the neighboring layers, as shown in Fig. 2. The carboxypentanoate ligands exhibit normal geometry (Ying et al., 2004), and the C6—O4 distance [1.205 (2) Å] is distinctly shorter than the C6—O3 distance [1.320 (2) Å], indicating C6═O4 double-bond character.