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Acta Cryst. (2007). E63, m3080-m3081    [ doi:10.1107/S1600536807058461 ]

catena-Poly[[[diaquacobalt(II)]-[mu]-(E)-1,2-bis(4-pyridyl)ethylene-[kappa]2N:N'] bis(4-aminobenzenesulfonate) hexahydrate]

Z.-X. Du and J.-X. Li

Abstract top

In the title compound, {[Co(C12H10N2)(H2O)2](C6H6NO3S)2·6H2O}n, a cobalt coordination polymer, the repeat unit comprises a cobalt complex cation, two 4-aminobenzenesulfonate anions and six uncoordinated water molecules. In the doubly charged cobalt cation, each Co atom lies on a center of symmetry and is six-coordinated in a distorted octahedral geometry formed by four O atoms of four coordinated water molecules, and two N atoms from two (E)-1,2-bis(4-pyridyl)ethylene (bpe) ligands. The bpe ligands bridge the Co atoms, forming a one-dimensional linear chain. Intermolecular O-H...O, O-H...N and N-H...O hydrogen-bonding interactions stabilize this chain structure.

Comment top

In the previous literatures, the complexes containing 4-aminobenzenesulfonate as monodentate ligand (Du & Li, 2007., Gunderman et al., 1996; Huang et al., 2004; Starynowicz, 1992) have been reported. In our paper, we describe another new compound (I) in which 4-aminobenzenesulfonate does not participate in coordination, (Fig. 1).

Compound (I) is a Co coordination polymer and the structural unit is comprised of a cobalt complex cation, two 4-aminobenzenesulfonate anions and six uncoordinated water molecules.

In the doubly charged cobalt cation, each Co symmetrical center has distorted octahedral geometry, formed by four O atoms of four coordinated water molecules, two N atoms from two (E)-1,2-bis(4-pyridyl)ethylene (bpe) ligands (Table 1). The bpe ligand plays as a bridging ligand linking neighbouring CoII atoms into a one-dimensional linear chain with the Co1···Co1(−x + 1, y, z) separation distance of 13.435 (2) Å.

4-Aaminobenzenesulfonate anions here does not take part in coordination but involve in intermolecular hydrogen bonds with coordinated and uncoordinated water molecules (Table 2). The chain structure is stabilized via these hydrogen bonding interactions and as well as electrostatic force (Fig. 2).

Related literature top

For related literature, see: Du & Li (2007); Gunderman et al. (1996); Huang et al. (2004); Starynowicz (1992).

Experimental top

A 10 ml water solution of Co(Cl)2·6H2O (0.238 g,1 mmol) was dropped into 10 ml me thanol solution of (E)-1,2-bis(4-pyridyl)ethylene (0.182 g,1 mmol) and 4-aminobenzenesulfonic acid (0.346 g, 2 mmol) and then the mixture was stirred for 5 h at 343 K·The filtrate was stayed in air for about two weeks to obtain red block-shaped crystals. Analysis, found (%): C 39.42, H 5.15, N 7.71, S 8.82. C24H38CoN4O14S2 requires(%): C 39.47, H 5.21, N 7.67, S 8.77. [CCDC: 656072].

Refinement top

H atoms bonded to C and N were positioned geometrically with C—H distance of 0.93Å and N—H of 0.86 Å, respectively, and treated as riding atoms, with Uiso(H) =1.2Ueq(C or N). The O—H hydrogen atoms were located in a difference Fourier map and refined isotropically, with O—H distance in the range of 0.8250–1.0288 Å.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL (Bruker, 2004).

Figures top
[Figure 1] Fig. 1. The segment of the polymeric structure of (I) with atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The uncoordinated water molecules have been omitted. [Symmetry codes: (A) −x + 2, −y + 1, −z; (B) −x + 1, −y + 1, −z; (C) −1 + x, y, z.]
[Figure 2] Fig. 2. Packing diagram of (I), showing the hydrogen bonds as dashed lines. H atoms on C atoms have been omitted for clarity.
catena-Poly[[[diaquacobalt(II)]-µ-(E)-1,2-bis(4- pyridyl)ethylene-κ2N:N'] bis(4-aminobenzenesulfonate) hexahydrate] top
Crystal data top
[Co(C12H10N2)(H2O)2](C6H6NO3S)2·6H2OF000 = 762
Mr = 729.63Dx = 1.485 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2927 reflections
a = 13.4351 (15) Åθ = 2.7–24.2º
b = 7.9688 (9) ŵ = 0.72 mm−1
c = 15.7183 (18) ÅT = 291 (2) K
β = 104.1330 (10)ºBlock, red
V = 1631.9 (3) Å30.30 × 0.20 × 0.09 mm
Z = 2
Data collection top
Bruker APEX II CCD area-detector
diffractometer		3035 independent reflections
Radiation source: fine-focus sealed tube2395 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.033
T = 291(2) Kθmax = 25.5º
φ and ω scansθmin = 2.7º
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		h = −16→16
Tmin = 0.814, Tmax = 0.941k = −9→9
12048 measured reflectionsl = −19→19
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)] = 0.051H-atom parameters constrained
wR(F2) = 0.155  w = 1/[σ2(Fo2) + (0.0893P)2 + 1.4053P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
3035 reflectionsΔρmax = 0.83 e Å−3
205 parametersΔρmin = −0.49 e Å−3
144 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Co(C12H10N2)(H2O)2](C6H6NO3S)2·6H2OV = 1631.9 (3) Å3
Mr = 729.63Z = 2
Monoclinic, P21/cMo Kα
a = 13.4351 (15) ŵ = 0.72 mm−1
b = 7.9688 (9) ÅT = 291 (2) K
c = 15.7183 (18) Å0.30 × 0.20 × 0.09 mm
β = 104.1330 (10)º
Data collection top
Bruker APEX II CCD area-detector
diffractometer		3035 independent reflections
Absorption correction: multi-scan
SADABS (Sheldrick, 1996)		2395 reflections with I > 2σ(I)
Tmin = 0.814, Tmax = 0.941Rint = 0.033
12048 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051144 restraints
wR(F2) = 0.155H-atom parameters constrained
S = 1.05Δρmax = 0.83 e Å−3
3035 reflectionsΔρmin = −0.49 e Å−3
205 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
Co11.00000.50000.00000.0305 (2)
S10.20531 (8)−0.04540 (13)0.13300 (7)0.0519 (3)
O11.00684 (18)0.2545 (4)0.0220 (2)0.0587 (8)
H1W0.95890.1931−0.00390.088*
H2W1.04970.20170.05880.088*
O20.7714 (5)0.9228 (9)0.0977 (4)0.160 (2)
H3W0.81840.88140.13860.240*
H4W0.69460.93820.09490.240*
O30.0514 (2)0.5633 (4)0.1577 (2)0.0614 (8)
H5W0.10100.62840.16360.092*
H6W0.05340.51590.20580.092*
O40.0764 (3)0.2844 (5)0.2693 (3)0.1046 (13)
H7W0.10930.19200.26430.157*
H8W0.01850.25820.27560.157*
O50.1560 (3)0.1016 (5)0.1560 (3)0.0924 (12)
O60.1664 (3)−0.0819 (6)0.0398 (2)0.0910 (12)
O70.1974 (2)−0.1889 (4)0.1860 (2)0.0788 (10)
N10.6514 (3)0.0765 (6)0.2018 (3)0.0829 (13)
H1A0.68240.13290.24720.099*
H1B0.68580.03320.16780.099*
N20.8530 (2)0.4986 (3)0.0078 (2)0.0392 (7)
C10.5415 (3)0.4745 (5)0.0290 (3)0.0447 (9)
H1D0.53200.42620.08030.054*
C20.6476 (3)0.4871 (4)0.0201 (3)0.0412 (8)
C30.6745 (3)0.5588 (5)−0.0527 (3)0.0457 (9)
H30.62410.6045−0.09810.055*
C40.7758 (3)0.5612 (5)−0.0566 (3)0.0436 (8)
H40.79200.6080−0.10570.052*
C50.8270 (3)0.4325 (5)0.0778 (2)0.0435 (8)
H50.87870.38960.12320.052*
C60.7273 (3)0.4256 (5)0.0855 (3)0.0445 (8)
H60.71330.37870.13550.053*
C70.3369 (3)0.0009 (4)0.1491 (3)0.0453 (9)
C80.3922 (3)−0.0651 (5)0.0940 (3)0.0513 (10)
H80.3588−0.12660.04510.062*
C90.4968 (3)−0.0405 (6)0.1107 (3)0.0560 (10)
H90.5338−0.08720.07370.067*
C100.5476 (3)0.0555 (6)0.1838 (3)0.0554 (10)
C110.4897 (3)0.1229 (5)0.2368 (3)0.0590 (11)
H110.52210.18790.28470.071*
C120.3864 (3)0.0969 (5)0.2209 (3)0.0544 (10)
H120.34930.14310.25800.065*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0108 (3)0.0324 (4)0.0491 (4)−0.0001 (2)0.0086 (2)0.0038 (3)
S10.0409 (6)0.0450 (6)0.0632 (7)−0.0035 (4)0.0003 (5)0.0099 (4)
O10.0310 (14)0.0484 (16)0.088 (2)−0.0015 (11)−0.0011 (13)0.0101 (14)
O20.145 (5)0.218 (6)0.127 (4)0.059 (4)0.053 (4)0.037 (4)
O30.0460 (16)0.0704 (18)0.0687 (19)−0.0153 (14)0.0159 (14)0.0019 (15)
O40.130 (3)0.093 (3)0.105 (3)−0.007 (3)0.056 (3)0.009 (2)
O50.066 (2)0.071 (2)0.142 (3)0.0020 (18)0.030 (2)−0.008 (2)
O60.059 (2)0.131 (3)0.068 (2)−0.034 (2)−0.0116 (17)0.011 (2)
O70.0564 (19)0.064 (2)0.103 (2)−0.0148 (15)−0.0042 (17)0.0334 (18)
N10.056 (2)0.101 (3)0.086 (3)−0.032 (2)0.006 (2)−0.008 (3)
N20.0248 (14)0.0424 (16)0.0510 (17)−0.0017 (11)0.0105 (12)0.0015 (13)
C10.0292 (18)0.054 (2)0.053 (2)−0.0032 (15)0.0133 (15)0.0029 (17)
C20.0265 (17)0.0450 (19)0.054 (2)−0.0030 (14)0.0146 (15)−0.0021 (15)
C30.0240 (17)0.058 (2)0.054 (2)0.0029 (15)0.0083 (15)0.0109 (18)
C40.0272 (17)0.053 (2)0.051 (2)0.0019 (15)0.0106 (15)0.0101 (17)
C50.0260 (17)0.053 (2)0.052 (2)0.0009 (15)0.0094 (15)0.0081 (17)
C60.0273 (17)0.056 (2)0.050 (2)−0.0014 (16)0.0099 (15)0.0059 (17)
C70.044 (2)0.0371 (19)0.048 (2)−0.0065 (15)−0.0004 (16)0.0065 (15)
C80.052 (2)0.050 (2)0.047 (2)−0.0099 (18)0.0013 (17)−0.0044 (17)
C90.055 (2)0.064 (2)0.047 (2)−0.011 (2)0.0091 (18)0.0040 (18)
C100.047 (2)0.055 (2)0.057 (2)−0.0178 (19)0.0005 (19)0.0111 (19)
C110.058 (2)0.053 (2)0.056 (2)−0.0100 (19)−0.004 (2)−0.0114 (19)
C120.052 (2)0.051 (2)0.055 (2)−0.0014 (18)0.0025 (18)−0.0072 (18)
Geometric parameters (Å, °) top
Co1—O1i1.985 (3)N2—C41.354 (5)
Co1—O11.985 (3)C1—C1ii1.321 (8)
Co1—N2i2.009 (3)C1—C21.469 (5)
Co1—N2i2.009 (3)C1—H1D0.9300
Co1—O3ii2.458 (3)C2—C61.380 (5)
Co1—O3ii2.458 (3)C2—C31.403 (5)
S1—O71.434 (3)C3—C41.378 (5)
S1—O51.435 (4)C3—H30.9300
S1—O61.460 (4)C4—H40.9300
S1—C71.763 (4)C5—C61.375 (5)
O1—H1W0.8319C5—H50.9300
O1—H2W0.8250C6—H60.9300
O2—H3W0.8496C7—C81.376 (6)
O2—H4W1.0288C7—C121.391 (5)
O3—H5W0.8322C8—C91.379 (6)
O3—H6W0.8390C8—H80.9300
O4—H7W0.8721C9—C101.411 (6)
O4—H8W0.8349C9—H90.9300
N1—C101.364 (6)C10—C111.378 (7)
N1—H1A0.8600C11—C121.365 (6)
N1—H1B0.8600C11—H110.9300
N2—C51.341 (5)C12—H120.9300
O1i—Co1—O1179.998 (1)C6—C2—C1120.0 (3)
O1i—Co1—N2i89.33 (11)C3—C2—C1123.6 (3)
O1—Co1—N2i90.67 (11)C4—C3—C2119.7 (3)
O1i—Co1—N290.67 (11)C4—C3—H3120.2
O1—Co1—N289.33 (11)C2—C3—H3120.2
N2i—Co1—N2180.0N2—C4—C3123.1 (3)
O1—Co1—N289.33 (11)N2—C4—H4118.4
N2i—Co1—N2180.0C3—C4—H4118.4
O3ii—Co1—O3ii180.0N2—C5—C6122.8 (3)
O3ii—Co1—N2i88.75 (11)N2—C5—H5118.6
O3—Co1—N2i172.76 (9)C6—C5—H5118.6
O7—S1—O5113.6 (3)C5—C6—C2121.1 (4)
O7—S1—O6111.4 (2)C5—C6—H6119.5
O5—S1—O6110.0 (3)C2—C6—H6119.5
O7—S1—C7107.27 (18)C8—C7—C12119.8 (4)
O5—S1—C7107.6 (2)C8—C7—S1120.4 (3)
O6—S1—C7106.7 (2)C12—C7—S1119.7 (3)
Co1—O1—H1W119.9C7—C8—C9120.5 (4)
Co1—O1—H2W128.3C7—C8—H8119.8
H1W—O1—H2W111.5C9—C8—H8119.8
H3W—O2—H4W129.1C8—C9—C10120.0 (4)
H5W—O3—H6W109.4C8—C9—H9120.0
H7W—O4—H8W107.9C10—C9—H9120.0
C10—N1—H1A120.0N1—C10—C11121.7 (4)
C10—N1—H1B120.0N1—C10—C9120.1 (5)
H1A—N1—H1B120.0C11—C10—C9118.2 (4)
C5—N2—C4116.9 (3)C12—C11—C10121.9 (4)
C5—N2—Co1120.6 (2)C12—C11—H11119.0
C4—N2—Co1122.5 (2)C10—C11—H11119.0
C1ii—C1—C2126.1 (5)C11—C12—C7119.6 (4)
C1ii—C1—H1D116.9C11—C12—H12120.2
C2—C1—H1D116.9C7—C12—H12120.2
C6—C2—C3116.4 (3)
O1i—Co1—N2—C5−126.6 (3)C1—C2—C6—C5178.6 (4)
O1—Co1—N2—C553.4 (3)O7—S1—C7—C892.7 (4)
N2i—Co1—N2—C513 (10)O5—S1—C7—C8−144.7 (4)
O1i—Co1—N2—C454.1 (3)O6—S1—C7—C8−26.8 (4)
O1—Co1—N2—C4−125.9 (3)O7—S1—C7—C12−83.6 (4)
N2i—Co1—N2—C4−166 (10)O5—S1—C7—C1238.9 (4)
C1ii—C1—C2—C6−178.8 (5)O6—S1—C7—C12156.8 (3)
C1ii—C1—C2—C30.9 (8)C12—C7—C8—C91.8 (6)
C6—C2—C3—C41.4 (6)S1—C7—C8—C9−174.6 (3)
C1—C2—C3—C4−178.3 (4)C7—C8—C9—C10−1.2 (6)
C5—N2—C4—C3−0.2 (6)C8—C9—C10—N1178.3 (4)
Co1—N2—C4—C3179.0 (3)C8—C9—C10—C11−0.2 (6)
C2—C3—C4—N2−0.8 (6)N1—C10—C11—C12−177.4 (4)
C4—N2—C5—C60.6 (6)C9—C10—C11—C121.0 (7)
Co1—N2—C5—C6−178.7 (3)C10—C11—C12—C7−0.5 (7)
N2—C5—C6—C20.1 (6)C8—C7—C12—C11−0.9 (6)
C3—C2—C6—C5−1.1 (6)S1—C7—C12—C11175.5 (3)
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···O6iii0.831.862.674 (4)164
O1—H2W···O5iv0.831.992.806 (5)173
O2—H3W···O4v0.851.922.771 (7)179
O2—H4W···N1vi1.032.202.841 (8)118
O3—H5W···O7vi0.831.922.743 (4)168
O3—H6W···O40.842.082.800 (5)143
O4—H7W···O50.872.082.714 (6)129
O4—H8W···O3vii0.832.212.886 (5)139
N1—H1A···O7v0.862.212.997 (5)152
N1—H1B···O2viii0.861.982.841 (8)175
Symmetry codes: (iii) −x+1, −y, −z; (iv) x+1, y, z; (v) −x+1, y+1/2, −z+1/2; (vi) x, y+1, z; (vii) −x, y−1/2, −z+1/2; (viii) x, y−1, z.
Table 1
Selected geometric parameters (Å, °) top
Co1—O11.985 (3)Co1—O3ii2.458 (3)
Co1—N2i2.009 (3)
O1i—Co1—O1179.998 (1)O3ii—Co1—O3ii180.0
O1—Co1—N2i90.67 (11)O3ii—Co1—N2i88.75 (11)
O1—Co1—N289.33 (11)O3—Co1—N2i172.76 (9)
N2i—Co1—N2180.0
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+1, −y+1, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1W···O6iii0.831.862.674 (4)164
O1—H2W···O5iv0.831.992.806 (5)173
O2—H3W···O4v0.851.922.771 (7)179
O2—H4W···N1vi1.032.202.841 (8)118
O3—H5W···O7vi0.831.922.743 (4)168
O3—H6W···O40.842.082.800 (5)143
O4—H7W···O50.872.082.714 (6)129
O4—H8W···O3vii0.832.212.886 (5)139
N1—H1A···O7v0.862.212.997 (5)152
N1—H1B···O2viii0.861.982.841 (8)175
Symmetry codes: (iii) −x+1, −y, −z; (iv) x+1, y, z; (v) −x+1, y+1/2, −z+1/2; (vi) x, y+1, z; (vii) −x, y−1/2, −z+1/2; (viii) x, y−1, z.
Acknowledgements top

This work was supported by the National Natural Science Foundation of China (No. 20471026) and the Natural Science Foundation of Henan province (No. 0311021200).

references
References top

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Gunderman, B. J., Squattrito, P. J. & Dubey, S. N. (1996). Acta Cryst. C52, 1131–1134.

Huang, M.-H., Bi, L.-H. & Dong, S.-J. (2004). Acta Cryst. C60, m30–m32.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Starynowicz, P. (1992). Acta Cryst. C48, 1414–1416.