Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103027070/ta1428sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103027070/ta1428Isup2.hkl |
CCDC reference: 231035
A solution of dimethylformamide (10 ml) containing CoCl2·6H2O (0.5 mmol, 0.119 g) and H4TCB (0.5 mmol, 0.127 g) was added slowly to a solution of dimethylformamide (10 ml) containing 2,2'-bipyridine (0.5 mmol, 0.078 g). The mixture was stirred for 30 min and left to stand at room temperature for about three weeks. Deep-red prism-shaped crystals of (I) were obtained.
The positions and isotropic displacement parameters of the water H atoms, H12 and H13, were refined subject to O—H = 0.85 (1) Å. The other H atoms were positioned geometrically and allowed to ride on their parent atoms at distances of 0.93 Å, with Uiso(H) = 1.2Ueq(parent atom).
Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Co2(C10H2O8)(C10H8N2)2(H2O)2] | Z = 1 |
Mr = 716.38 | F(000) = 364 |
Triclinic, P1 | Dx = 1.766 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.5859 (8) Å | Cell parameters from 534 reflections |
b = 8.9838 (10) Å | θ = 2.4–23.0° |
c = 10.6729 (11) Å | µ = 1.30 mm−1 |
α = 80.441 (2)° | T = 273 K |
β = 72.913 (2)° | Prism, red |
γ = 77.096 (2)° | 0.31 × 0.21 × 0.12 mm |
V = 673.75 (12) Å3 |
Bruker SMART CCD area-detector diffractometer | 2406 independent reflections |
Radiation source: fine-focus sealed tube | 2273 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.015 |
ϕ and ω scans | θmax = 25.2°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −9→9 |
Tmin = 0.727, Tmax = 0.855 | k = −10→10 |
4962 measured reflections | l = −12→12 |
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)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.0362P)2 + 0.3213P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.023 |
2406 reflections | Δρmax = 0.31 e Å−3 |
217 parameters | Δρmin = −0.22 e Å−3 |
3 restraints | Extinction correction: SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00 (2) |
[Co2(C10H2O8)(C10H8N2)2(H2O)2] | γ = 77.096 (2)° |
Mr = 716.38 | V = 673.75 (12) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.5859 (8) Å | Mo Kα radiation |
b = 8.9838 (10) Å | µ = 1.30 mm−1 |
c = 10.6729 (11) Å | T = 273 K |
α = 80.441 (2)° | 0.31 × 0.21 × 0.12 mm |
β = 72.913 (2)° |
Bruker SMART CCD area-detector diffractometer | 2406 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2273 reflections with I > 2σ(I) |
Tmin = 0.727, Tmax = 0.855 | Rint = 0.015 |
4962 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 3 restraints |
wR(F2) = 0.071 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.31 e Å−3 |
2406 reflections | Δρmin = −0.22 e Å−3 |
217 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 | 0.83036 (3) | 0.35696 (3) | 0.22259 (2) | 0.02608 (12) | |
O1 | 0.7289 (2) | 0.19179 (17) | 0.16733 (15) | 0.0369 (4) | |
O2 | 0.4511 (2) | 0.3372 (2) | 0.1647 (2) | 0.0630 (6) | |
O3 | 0.1030 (2) | 0.14802 (19) | 0.26572 (15) | 0.0472 (4) | |
O4 | 0.0919 (2) | 0.31488 (17) | 0.09364 (15) | 0.0364 (4) | |
O5 | 0.7081 (2) | 0.52355 (19) | 0.10190 (18) | 0.0442 (4) | |
N1 | 0.8709 (2) | 0.5479 (2) | 0.30335 (17) | 0.0307 (4) | |
N2 | 0.7186 (2) | 0.31094 (18) | 0.42295 (16) | 0.0270 (4) | |
C1 | 0.6565 (3) | 0.1807 (2) | 0.4767 (2) | 0.0350 (5) | |
H1 | 0.6572 | 0.1110 | 0.4211 | 0.042* | |
C2 | 0.5914 (3) | 0.1450 (3) | 0.6109 (2) | 0.0411 (5) | |
H2 | 0.5528 | 0.0519 | 0.6454 | 0.049* | |
C3 | 0.5852 (3) | 0.2508 (3) | 0.6922 (2) | 0.0422 (6) | |
H3 | 0.5386 | 0.2313 | 0.7830 | 0.051* | |
C4 | 0.6483 (3) | 0.3856 (3) | 0.6385 (2) | 0.0365 (5) | |
H4 | 0.6438 | 0.4583 | 0.6926 | 0.044* | |
C5 | 0.7187 (3) | 0.4121 (2) | 0.50289 (19) | 0.0276 (4) | |
C6 | 0.8006 (3) | 0.5484 (2) | 0.4349 (2) | 0.0282 (4) | |
C7 | 0.8073 (3) | 0.6683 (3) | 0.4998 (2) | 0.0364 (5) | |
H7 | 0.7605 | 0.6656 | 0.5909 | 0.044* | |
C8 | 0.8839 (3) | 0.7907 (3) | 0.4273 (3) | 0.0421 (6) | |
H8 | 0.8923 | 0.8708 | 0.4692 | 0.051* | |
C9 | 0.9481 (4) | 0.7942 (3) | 0.2924 (3) | 0.0464 (6) | |
H9 | 0.9950 | 0.8785 | 0.2416 | 0.056* | |
C10 | 0.9416 (3) | 0.6699 (3) | 0.2338 (2) | 0.0415 (5) | |
H10 | 0.9880 | 0.6711 | 0.1428 | 0.050* | |
C11 | 0.5715 (3) | 0.2196 (2) | 0.14186 (19) | 0.0292 (4) | |
C12 | 0.5312 (3) | 0.1026 (2) | 0.07308 (17) | 0.0221 (4) | |
C13 | 0.3478 (3) | 0.1008 (2) | 0.07097 (17) | 0.0217 (4) | |
C14 | 0.3203 (3) | −0.0012 (2) | −0.00293 (18) | 0.0233 (4) | |
H14 | 0.1990 | −0.0016 | −0.0056 | 0.028* | |
C15 | 0.1734 (3) | 0.1956 (2) | 0.15196 (19) | 0.0268 (4) | |
H12 | 0.775 (3) | 0.573 (3) | 0.0368 (18) | 0.049 (8)* | |
H13 | 0.618 (3) | 0.493 (3) | 0.087 (2) | 0.062 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co | 0.02650 (17) | 0.02814 (18) | 0.02342 (17) | −0.00710 (11) | −0.00116 (11) | −0.00953 (11) |
O1 | 0.0416 (9) | 0.0344 (8) | 0.0462 (9) | −0.0110 (7) | −0.0230 (7) | −0.0101 (7) |
O2 | 0.0294 (9) | 0.0561 (11) | 0.1128 (17) | −0.0016 (8) | −0.0097 (10) | −0.0605 (12) |
O3 | 0.0474 (10) | 0.0476 (10) | 0.0321 (9) | −0.0049 (8) | 0.0110 (7) | −0.0090 (7) |
O4 | 0.0276 (7) | 0.0335 (8) | 0.0421 (9) | 0.0040 (6) | −0.0050 (6) | −0.0086 (7) |
O5 | 0.0396 (9) | 0.0411 (9) | 0.0571 (11) | −0.0138 (7) | −0.0223 (8) | 0.0068 (8) |
N1 | 0.0315 (9) | 0.0312 (9) | 0.0301 (9) | −0.0074 (7) | −0.0053 (7) | −0.0086 (7) |
N2 | 0.0255 (8) | 0.0264 (9) | 0.0279 (8) | −0.0008 (7) | −0.0064 (7) | −0.0063 (7) |
C1 | 0.0375 (12) | 0.0311 (11) | 0.0361 (12) | −0.0055 (9) | −0.0093 (9) | −0.0049 (9) |
C2 | 0.0425 (13) | 0.0355 (12) | 0.0401 (13) | −0.0065 (10) | −0.0081 (10) | 0.0038 (10) |
C3 | 0.0419 (13) | 0.0482 (14) | 0.0270 (11) | 0.0003 (10) | −0.0043 (9) | 0.0013 (10) |
C4 | 0.0392 (12) | 0.0396 (12) | 0.0283 (11) | 0.0042 (9) | −0.0096 (9) | −0.0116 (9) |
C5 | 0.0235 (10) | 0.0299 (10) | 0.0269 (10) | 0.0050 (8) | −0.0075 (8) | −0.0085 (8) |
C6 | 0.0241 (9) | 0.0299 (10) | 0.0314 (11) | 0.0025 (8) | −0.0107 (8) | −0.0101 (8) |
C7 | 0.0336 (11) | 0.0371 (12) | 0.0417 (12) | 0.0038 (9) | −0.0152 (9) | −0.0180 (10) |
C8 | 0.0410 (13) | 0.0329 (12) | 0.0604 (16) | −0.0008 (10) | −0.0221 (11) | −0.0192 (11) |
C9 | 0.0461 (14) | 0.0351 (13) | 0.0634 (16) | −0.0157 (10) | −0.0185 (12) | −0.0025 (11) |
C10 | 0.0464 (13) | 0.0418 (13) | 0.0387 (12) | −0.0164 (10) | −0.0078 (10) | −0.0059 (10) |
C11 | 0.0274 (10) | 0.0332 (11) | 0.0287 (10) | −0.0099 (8) | −0.0016 (8) | −0.0124 (8) |
C12 | 0.0242 (9) | 0.0235 (9) | 0.0195 (9) | −0.0060 (7) | −0.0046 (7) | −0.0051 (7) |
C13 | 0.0224 (9) | 0.0218 (9) | 0.0197 (9) | −0.0039 (7) | −0.0030 (7) | −0.0042 (7) |
C14 | 0.0196 (9) | 0.0274 (10) | 0.0242 (9) | −0.0062 (7) | −0.0050 (7) | −0.0052 (8) |
C15 | 0.0220 (9) | 0.0265 (10) | 0.0340 (11) | −0.0071 (8) | −0.0032 (8) | −0.0133 (8) |
Co—O5 | 2.0495 (16) | C3—C4 | 1.375 (3) |
Co—O4i | 2.0510 (14) | C3—H3 | 0.9300 |
Co—O1 | 2.0520 (14) | C4—C5 | 1.388 (3) |
Co—N2 | 2.0640 (17) | C4—H4 | 0.9300 |
Co—N1 | 2.1590 (17) | C5—C6 | 1.480 (3) |
O1—C11 | 1.263 (3) | C6—C7 | 1.392 (3) |
O2—C11 | 1.238 (3) | C7—C8 | 1.373 (3) |
O3—C15 | 1.221 (2) | C7—H7 | 0.9300 |
O4—C15 | 1.275 (2) | C8—C9 | 1.375 (4) |
O4—Coii | 2.0510 (14) | C8—H8 | 0.9300 |
O5—H12 | 0.854 (9) | C9—C10 | 1.384 (3) |
O5—H13 | 0.855 (10) | C9—H9 | 0.9300 |
N1—C10 | 1.341 (3) | C10—H10 | 0.9300 |
N1—C6 | 1.348 (3) | C11—C12 | 1.506 (3) |
N2—C1 | 1.336 (3) | C12—C14iii | 1.390 (3) |
N2—C5 | 1.346 (3) | C12—C13 | 1.402 (3) |
C1—C2 | 1.378 (3) | C13—C14 | 1.388 (3) |
C1—H1 | 0.9300 | C13—C15 | 1.514 (2) |
C2—C3 | 1.375 (3) | C14—C12iii | 1.390 (3) |
C2—H2 | 0.9300 | C14—H14 | 0.9300 |
O5—Co—O4i | 97.22 (7) | N2—C5—C4 | 121.0 (2) |
O5—Co—O1 | 91.01 (6) | N2—C5—C6 | 114.92 (17) |
O4i—Co—O1 | 95.50 (6) | C4—C5—C6 | 124.13 (19) |
O5—Co—N2 | 125.01 (7) | N1—C6—C7 | 121.7 (2) |
O4i—Co—N2 | 135.72 (6) | N1—C6—C5 | 114.76 (17) |
O1—Co—N2 | 96.32 (7) | C7—C6—C5 | 123.55 (19) |
O5—Co—N1 | 84.62 (7) | C8—C7—C6 | 119.0 (2) |
O4i—Co—N1 | 97.24 (6) | C8—C7—H7 | 120.5 |
O1—Co—N1 | 166.95 (7) | C6—C7—H7 | 120.5 |
N2—Co—N1 | 76.39 (6) | C7—C8—C9 | 119.6 (2) |
C11—O1—Co | 121.96 (13) | C7—C8—H8 | 120.2 |
C15—O4—Coii | 102.50 (12) | C9—C8—H8 | 120.2 |
Co—O5—H12 | 121.0 (17) | C8—C9—C10 | 118.7 (2) |
Co—O5—H13 | 109.3 (18) | C8—C9—H9 | 120.6 |
H12—O5—H13 | 115.9 (16) | C10—C9—H9 | 120.6 |
C10—N1—C6 | 118.42 (18) | N1—C10—C9 | 122.5 (2) |
C10—N1—Co | 125.98 (15) | N1—C10—H10 | 118.8 |
C6—N1—Co | 115.25 (14) | C9—C10—H10 | 118.8 |
C1—N2—C5 | 118.83 (18) | O2—C11—O1 | 125.37 (19) |
C1—N2—Co | 122.50 (14) | O2—C11—C12 | 117.58 (18) |
C5—N2—Co | 118.55 (13) | O1—C11—C12 | 117.00 (17) |
N2—C1—C2 | 123.0 (2) | C14iii—C12—C13 | 119.24 (17) |
N2—C1—H1 | 118.5 | C14iii—C12—C11 | 119.38 (16) |
C2—C1—H1 | 118.5 | C13—C12—C11 | 121.24 (16) |
C3—C2—C1 | 118.2 (2) | C14—C13—C12 | 118.80 (17) |
C3—C2—H2 | 120.9 | C14—C13—C15 | 116.69 (16) |
C1—C2—H2 | 120.9 | C12—C13—C15 | 124.36 (16) |
C2—C3—C4 | 119.6 (2) | C13—C14—C12iii | 121.95 (17) |
C2—C3—H3 | 120.2 | C13—C14—H14 | 119.0 |
C4—C3—H3 | 120.2 | C12iii—C14—H14 | 119.0 |
C3—C4—C5 | 119.4 (2) | O3—C15—O4 | 121.58 (18) |
C3—C4—H4 | 120.3 | O3—C15—C13 | 119.83 (18) |
C5—C4—H4 | 120.3 | O4—C15—C13 | 118.08 (17) |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H12···O4iv | 0.85 (1) | 1.77 (1) | 2.623 (2) | 177 (3) |
O5—H13···O2 | 0.86 (1) | 2.01 (2) | 2.715 (2) | 139 (2) |
Symmetry code: (iv) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Co2(C10H2O8)(C10H8N2)2(H2O)2] |
Mr | 716.38 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 273 |
a, b, c (Å) | 7.5859 (8), 8.9838 (10), 10.6729 (11) |
α, β, γ (°) | 80.441 (2), 72.913 (2), 77.096 (2) |
V (Å3) | 673.75 (12) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.30 |
Crystal size (mm) | 0.31 × 0.21 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.727, 0.855 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4962, 2406, 2273 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.071, 1.08 |
No. of reflections | 2406 |
No. of parameters | 217 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.22 |
Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H12···O4i | 0.854 (9) | 1.770 (10) | 2.623 (2) | 177 (3) |
O5—H13···O2 | 0.855 (10) | 2.010 (17) | 2.715 (2) | 139 (2) |
Symmetry code: (i) −x+1, −y+1, −z. |
Coordinate polymer solids with a variety of cavities or channels are currently under intensive study because of the scope they offer for the generation by design of new materials with a range of potentially useful properties (Yaghi et al., 1998; Stein et al., 1993). Popular bridging ligands in this field are 1,2,4,5-benzenetetracarboxylic acid (H4TCB) and 4,4'-bipyridine, and their derivatives (Eddaoudi et al., 2001). In our group, we have studied some transition metal complexes bridged by TCB4− or H2TCB2− anions, such as CoII (Wang et al., 2000), NiII (Cheng et al., 2001) and CuII (Hu et al., 2003). In the course of our continuing efforts in this series of research studies, the title novel infinite one-dimensional coordination polymer, [Co2(TCB)(2,2'-bipy)2(H2O)2]n, (I) (2,2'-bipy is 2,2'-bipyridine), is reported here. It should be noted that synthetic conditions, such as H-atom receptors, temperature and solvents, etc., play an imporant role in determining the compositions of these complexes. \sch
In title complex, (I), each CoII cation has a five-coordination environment, completed by two carboxyl O atoms belonging to two TCB4− anions, one aqua O atom and two N atoms from one 2,2'-bipy ligand (Fig. 1). The Co—O bond lengths are all about 2.05 Å, while the Co—N1 bond [2.1590 (17) Å] is longer than the Co—N2 bond [2.0640 (17) Å]. An infinite one-dimensional polymer with a double-chain structure is formed by the CoII cations, the µ4-bridging TCB4− anions, the aqua molecules and the terminal 2,2'-bipy ligands (Fig. 2).
The coordination mode of the TCB4− anion in (I) is similar to that in [Cu2(TCB)(phen)2]n.nH2O (Shi et al., 2001). Four carboxylate groups are all deprotonated and coordinate to four CoII cations in a monodentate fashion, forming a one-dimensional ribbon-like double-chain structure with cavities of approximately 6.8 × 6.6 Å. Intermolecular hydrogen-bonding interactions of 2.623 (2) Å are found between the coordinated aqua O atom and the coordinated carboxyl O atom from different chains, resulting in a two-dimensional supramolecular structure. Furthermore, a three-dimensional network structure is formed by face-to-face π–π interactions of approximately 3.78 Å between the aromatic rings of the 2,2'-bipy ligands of two adjacent chains (Fig. 3).