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In the title complex, [Co2(C10H2O8)(C10H8N2)2(H2O)2], the four carboxyl­ate groups are fully deprotonated and coordinate to four CoII cations in a monodentate fashion, forming a one-dimensional ribbon-like double-chain structure, with centrosymmetric [Co2(C10H2O8)(C10H8N2)2(H2O)2] repeating units and a cavity of approximately 6.8 × 6.6 Å. Moreover, a three-dimensional supramolecular structure is formed by face-to-face [pi]-[pi] interactions between the aromatic rings of the 2,2'-bi­pyridine moieties of two adjacent chains, and by hydrogen-bonding interactions between the coordinated aqua O atom and the coordinated carboxyl O atom from different chains.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103027070/ta1428sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270103027070/ta1428Isup2.hkl
Contains datablock I

CCDC reference: 231035

Comment top

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 ππ interactions of approximately 3.78 Å between the aromatic rings of the 2,2'-bipy ligands of two adjacent chains (Fig. 3).

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The coordination environment of the CoII ion in (I), with the atom-numbering scheme, showing displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. The double-chain structure of (I), showing the cavities.
[Figure 3] Fig. 3. The three-dimensional network structure of (I).
catena-Poly[bis[aqua(2,2-bipyridine-κ2N,N')cobalt(II)]-µ-1,2,4,5- benzenetetracarboxylato-κ4O1:O2:O3:O4] top
Crystal data top
[Co2(C10H2O8)(C10H8N2)2(H2O)2]Z = 1
Mr = 716.38F(000) = 364
Triclinic, P1Dx = 1.766 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.5859 (8) ÅCell parameters from 534 reflections
b = 8.9838 (10) Åθ = 2.4–23.0°
c = 10.6729 (11) ŵ = 1.30 mm1
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
Data collection top
Bruker SMART CCD area-detector
diffractometer
2406 independent reflections
Radiation source: fine-focus sealed tube2273 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.015
ϕ and ω scansθmax = 25.2°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 99
Tmin = 0.727, Tmax = 0.855k = 1010
4962 measured reflectionsl = 1212
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H 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 reflectionsΔρmax = 0.31 e Å3
217 parametersΔρmin = 0.22 e Å3
3 restraintsExtinction correction: SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00 (2)
Crystal data top
[Co2(C10H2O8)(C10H8N2)2(H2O)2]γ = 77.096 (2)°
Mr = 716.38V = 673.75 (12) Å3
Triclinic, P1Z = 1
a = 7.5859 (8) ÅMo Kα radiation
b = 8.9838 (10) ŵ = 1.30 mm1
c = 10.6729 (11) ÅT = 273 K
α = 80.441 (2)°0.31 × 0.21 × 0.12 mm
β = 72.913 (2)°
Data collection top
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 = 0.855Rint = 0.015
4962 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0273 restraints
wR(F2) = 0.071H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 0.31 e Å3
2406 reflectionsΔρmin = 0.22 e Å3
217 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
Co0.83036 (3)0.35696 (3)0.22259 (2)0.02608 (12)
O10.7289 (2)0.19179 (17)0.16733 (15)0.0369 (4)
O20.4511 (2)0.3372 (2)0.1647 (2)0.0630 (6)
O30.1030 (2)0.14802 (19)0.26572 (15)0.0472 (4)
O40.0919 (2)0.31488 (17)0.09364 (15)0.0364 (4)
O50.7081 (2)0.52355 (19)0.10190 (18)0.0442 (4)
N10.8709 (2)0.5479 (2)0.30335 (17)0.0307 (4)
N20.7186 (2)0.31094 (18)0.42295 (16)0.0270 (4)
C10.6565 (3)0.1807 (2)0.4767 (2)0.0350 (5)
H10.65720.11100.42110.042*
C20.5914 (3)0.1450 (3)0.6109 (2)0.0411 (5)
H20.55280.05190.64540.049*
C30.5852 (3)0.2508 (3)0.6922 (2)0.0422 (6)
H30.53860.23130.78300.051*
C40.6483 (3)0.3856 (3)0.6385 (2)0.0365 (5)
H40.64380.45830.69260.044*
C50.7187 (3)0.4121 (2)0.50289 (19)0.0276 (4)
C60.8006 (3)0.5484 (2)0.4349 (2)0.0282 (4)
C70.8073 (3)0.6683 (3)0.4998 (2)0.0364 (5)
H70.76050.66560.59090.044*
C80.8839 (3)0.7907 (3)0.4273 (3)0.0421 (6)
H80.89230.87080.46920.051*
C90.9481 (4)0.7942 (3)0.2924 (3)0.0464 (6)
H90.99500.87850.24160.056*
C100.9416 (3)0.6699 (3)0.2338 (2)0.0415 (5)
H100.98800.67110.14280.050*
C110.5715 (3)0.2196 (2)0.14186 (19)0.0292 (4)
C120.5312 (3)0.1026 (2)0.07308 (17)0.0221 (4)
C130.3478 (3)0.1008 (2)0.07097 (17)0.0217 (4)
C140.3203 (3)0.0012 (2)0.00293 (18)0.0233 (4)
H140.19900.00160.00560.028*
C150.1734 (3)0.1956 (2)0.15196 (19)0.0268 (4)
H120.775 (3)0.573 (3)0.0368 (18)0.049 (8)*
H130.618 (3)0.493 (3)0.087 (2)0.062 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co0.02650 (17)0.02814 (18)0.02342 (17)0.00710 (11)0.00116 (11)0.00953 (11)
O10.0416 (9)0.0344 (8)0.0462 (9)0.0110 (7)0.0230 (7)0.0101 (7)
O20.0294 (9)0.0561 (11)0.1128 (17)0.0016 (8)0.0097 (10)0.0605 (12)
O30.0474 (10)0.0476 (10)0.0321 (9)0.0049 (8)0.0110 (7)0.0090 (7)
O40.0276 (7)0.0335 (8)0.0421 (9)0.0040 (6)0.0050 (6)0.0086 (7)
O50.0396 (9)0.0411 (9)0.0571 (11)0.0138 (7)0.0223 (8)0.0068 (8)
N10.0315 (9)0.0312 (9)0.0301 (9)0.0074 (7)0.0053 (7)0.0086 (7)
N20.0255 (8)0.0264 (9)0.0279 (8)0.0008 (7)0.0064 (7)0.0063 (7)
C10.0375 (12)0.0311 (11)0.0361 (12)0.0055 (9)0.0093 (9)0.0049 (9)
C20.0425 (13)0.0355 (12)0.0401 (13)0.0065 (10)0.0081 (10)0.0038 (10)
C30.0419 (13)0.0482 (14)0.0270 (11)0.0003 (10)0.0043 (9)0.0013 (10)
C40.0392 (12)0.0396 (12)0.0283 (11)0.0042 (9)0.0096 (9)0.0116 (9)
C50.0235 (10)0.0299 (10)0.0269 (10)0.0050 (8)0.0075 (8)0.0085 (8)
C60.0241 (9)0.0299 (10)0.0314 (11)0.0025 (8)0.0107 (8)0.0101 (8)
C70.0336 (11)0.0371 (12)0.0417 (12)0.0038 (9)0.0152 (9)0.0180 (10)
C80.0410 (13)0.0329 (12)0.0604 (16)0.0008 (10)0.0221 (11)0.0192 (11)
C90.0461 (14)0.0351 (13)0.0634 (16)0.0157 (10)0.0185 (12)0.0025 (11)
C100.0464 (13)0.0418 (13)0.0387 (12)0.0164 (10)0.0078 (10)0.0059 (10)
C110.0274 (10)0.0332 (11)0.0287 (10)0.0099 (8)0.0016 (8)0.0124 (8)
C120.0242 (9)0.0235 (9)0.0195 (9)0.0060 (7)0.0046 (7)0.0051 (7)
C130.0224 (9)0.0218 (9)0.0197 (9)0.0039 (7)0.0030 (7)0.0042 (7)
C140.0196 (9)0.0274 (10)0.0242 (9)0.0062 (7)0.0050 (7)0.0052 (8)
C150.0220 (9)0.0265 (10)0.0340 (11)0.0071 (8)0.0032 (8)0.0133 (8)
Geometric parameters (Å, º) top
Co—O52.0495 (16)C3—C41.375 (3)
Co—O4i2.0510 (14)C3—H30.9300
Co—O12.0520 (14)C4—C51.388 (3)
Co—N22.0640 (17)C4—H40.9300
Co—N12.1590 (17)C5—C61.480 (3)
O1—C111.263 (3)C6—C71.392 (3)
O2—C111.238 (3)C7—C81.373 (3)
O3—C151.221 (2)C7—H70.9300
O4—C151.275 (2)C8—C91.375 (4)
O4—Coii2.0510 (14)C8—H80.9300
O5—H120.854 (9)C9—C101.384 (3)
O5—H130.855 (10)C9—H90.9300
N1—C101.341 (3)C10—H100.9300
N1—C61.348 (3)C11—C121.506 (3)
N2—C11.336 (3)C12—C14iii1.390 (3)
N2—C51.346 (3)C12—C131.402 (3)
C1—C21.378 (3)C13—C141.388 (3)
C1—H10.9300C13—C151.514 (2)
C2—C31.375 (3)C14—C12iii1.390 (3)
C2—H20.9300C14—H140.9300
O5—Co—O4i97.22 (7)N2—C5—C4121.0 (2)
O5—Co—O191.01 (6)N2—C5—C6114.92 (17)
O4i—Co—O195.50 (6)C4—C5—C6124.13 (19)
O5—Co—N2125.01 (7)N1—C6—C7121.7 (2)
O4i—Co—N2135.72 (6)N1—C6—C5114.76 (17)
O1—Co—N296.32 (7)C7—C6—C5123.55 (19)
O5—Co—N184.62 (7)C8—C7—C6119.0 (2)
O4i—Co—N197.24 (6)C8—C7—H7120.5
O1—Co—N1166.95 (7)C6—C7—H7120.5
N2—Co—N176.39 (6)C7—C8—C9119.6 (2)
C11—O1—Co121.96 (13)C7—C8—H8120.2
C15—O4—Coii102.50 (12)C9—C8—H8120.2
Co—O5—H12121.0 (17)C8—C9—C10118.7 (2)
Co—O5—H13109.3 (18)C8—C9—H9120.6
H12—O5—H13115.9 (16)C10—C9—H9120.6
C10—N1—C6118.42 (18)N1—C10—C9122.5 (2)
C10—N1—Co125.98 (15)N1—C10—H10118.8
C6—N1—Co115.25 (14)C9—C10—H10118.8
C1—N2—C5118.83 (18)O2—C11—O1125.37 (19)
C1—N2—Co122.50 (14)O2—C11—C12117.58 (18)
C5—N2—Co118.55 (13)O1—C11—C12117.00 (17)
N2—C1—C2123.0 (2)C14iii—C12—C13119.24 (17)
N2—C1—H1118.5C14iii—C12—C11119.38 (16)
C2—C1—H1118.5C13—C12—C11121.24 (16)
C3—C2—C1118.2 (2)C14—C13—C12118.80 (17)
C3—C2—H2120.9C14—C13—C15116.69 (16)
C1—C2—H2120.9C12—C13—C15124.36 (16)
C2—C3—C4119.6 (2)C13—C14—C12iii121.95 (17)
C2—C3—H3120.2C13—C14—H14119.0
C4—C3—H3120.2C12iii—C14—H14119.0
C3—C4—C5119.4 (2)O3—C15—O4121.58 (18)
C3—C4—H4120.3O3—C15—C13119.83 (18)
C5—C4—H4120.3O4—C15—C13118.08 (17)
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z; (iii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H12···O4iv0.85 (1)1.77 (1)2.623 (2)177 (3)
O5—H13···O20.86 (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]
Mr716.38
Crystal system, space groupTriclinic, 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)
V3)673.75 (12)
Z1
Radiation typeMo Kα
µ (mm1)1.30
Crystal size (mm)0.31 × 0.21 × 0.12
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.727, 0.855
No. of measured, independent and
observed [I > 2σ(I)] reflections
4962, 2406, 2273
Rint0.015
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.027, 0.071, 1.08
No. of reflections2406
No. of parameters217
No. of restraints3
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.31, 0.22

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O5—H12···O4i0.854 (9)1.770 (10)2.623 (2)177 (3)
O5—H13···O20.855 (10)2.010 (17)2.715 (2)139 (2)
Symmetry code: (i) x+1, y+1, z.
 

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