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Acta Cryst. (2008). E64, m192-m193    [ doi:10.1107/S1600536807063507 ]

catena-Poly[[[tetraaquacadmium(II)]-[mu]-4,4'-bipyridine] fumarate tetrahydrate]

Y.-R. Pan

Abstract top

In the crystal structure of the title compound, [Cd(C10H8N2)(H2O)4](C4H2O4)·4H2O, the CdII atom, on an inversion centre, is six-coordinated by four O atoms from four water molecules and two N atoms from 4,4'-bpy molecules in a distorted octahedral coordination geometry. Weak C-H...O interactions between uncoordinated carboxylate O atoms of fumaric acid and water molecules contribute to the crystal packing stability.

Comment top

Recently, 4,4'-bipyridine (bpy) hve been used to construct coordination polymers (Tao et al., 2000; Dai et al., 2003). A few structures of copper (Dalai et al., 2002; Ying, Zheng & Zhou, 2004; Kang et al., 2004), manganese (Devereux et al., 2000; Ying, Zheng & Zhang, 2004), nickel (Zheng et al., 2002) and cobalt (Shen et al., 2004; Konar et al., 2003] fumarate complexes with 4,4'-bpy are known. Herein, we report the structure of the title complex with 4,4'-bpy and fumaric acid, [Cd(4,4'-bpy)(H2O)4](C4H2O4)(H2O)4 (I).

The structure of the title compound, shown in Fig. 1, consists of one [Cd(4,4'-bpy)(H2O)4]2+ cation, one uncoordination fumarate anion and four water molecules. The CdII ion is coordinated by one bpy and four water molecules in a distorted octahedral geometry to form a one-dimensional chain. Table 1 gives a listing of selected bond lengths and bond angles, which are comparable to those values found in other such complexes.

There are weak C—H···O hydrogen bonds between uncoordinated carboxylate O atoms of fumaric acid and lattice water molecules, which extend one-dimensional chain into three-dimensional supramolecular packing structure (Fig. 2, Table 2).

Related literature top

For related literature, see: Dai et al. (2003); Dalai et al. (2002); Devereux et al. (2000); Kang et al. (2004); Konar et al. (2003); Shen et al. (2004); Tao et al. (2000); Ying et al. (2004); Zheng et al. (2002).

Experimental top

Cadmium(II) acetate dihydrate (0.080 g, 0.3 mol), 4,4'-bipyridine (0.039 g, 0.2 mmol), fumaric acid (0.232 g, 0.2 mmol), sodium hydroxide (0.024 g, 0.4 mmol) and water (14 ml) were placed in a 23 ml Teflon-lined autoclave, and the autoclave was heated at 423 K for 3 d. After cooling slowly to room temperature at a rate of 10 K h-1, colorless crystals of (I) were obtained. Analysis found: C 31.78, H 5.02, N 5.29%; calculated for C14H26N2O12Cd: C 31.89, H 4.94, N 5.34%.

Refinement top

Water H atoms were located in a difference Fourier map and refined as riding in their as-found relative positions; Uiso(H) = 1.5Ueq(O). Other H atoms were placed at calculated positions with C—H = 0.93Å and refined in riding mode;Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. View of the local coordination of Cd(II) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry code: (i) -x,-y,-z + 2.
[Figure 2] Fig. 2. A packing diagram for the two-dimensional supramolecular hydrogen-bonding framework via C—H···O interactions. The view shows a layer parallel to the ac plane; the view direction is parallel to the b axis. Hydrogen bonds are indicated by dashed lines.
catena-Poly[[[tetraaquacadmium(II)]-µ-4,4'-bipyridine] fumarate tetrahydrate] top
Crystal data top
[Cd(C10H8N2)(H2O)4](C4H2O4)·4H2OZ = 1
Mr = 526.77F000 = 268
Triclinic, P1Dx = 1.646 Mg m−3
Hall symbol: -p 1Mo Kα radiation
λ = 0.71069 Å
a = 7.183 (5) ÅCell parameters from 3394 reflections
b = 7.802 (5) Åθ = 2.1–28.0º
c = 10.038 (5) ŵ = 1.09 mm−1
α = 80.434 (5)ºT = 293 (2) K
β = 87.791 (5)ºBlock, colorless
γ = 73.288 (5)º0.21 × 0.19 × 0.15 mm
V = 531.3 (6) Å3
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2378 independent reflections
Radiation source: fine-focus sealed tube2363 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.045
Detector resolution: 10 pixels mm-1θmax = 28.2º
T = 293(2) Kθmin = 2.1º
ω scanh = −9→9
Absorption correction: multi-scan
(Higashi, 1995)		k = −10→10
Tmin = 0.804, Tmax = 0.854l = −13→10
3414 measured reflections
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)] = 0.028H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.072  w = 1/[σ2(Fo2) + (0.0549P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max = 0.001
2378 reflectionsΔρmax = 0.58 e Å−3
165 parametersΔρmin = −1.30 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cd(C10H8N2)(H2O)4](C4H2O4)·4H2Oγ = 73.288 (5)º
Mr = 526.77V = 531.3 (6) Å3
Triclinic, P1Z = 1
a = 7.183 (5) ÅMo Kα
b = 7.802 (5) ŵ = 1.09 mm−1
c = 10.038 (5) ÅT = 293 (2) K
α = 80.434 (5)º0.21 × 0.19 × 0.15 mm
β = 87.791 (5)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2378 independent reflections
Absorption correction: multi-scan
(Higashi, 1995)		2363 reflections with I > 2σ(I)
Tmin = 0.804, Tmax = 0.854Rint = 0.045
3414 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028165 parameters
wR(F2) = 0.072H atoms treated by a mixture of
independent and constrained refinement
S = 1.08Δρmax = 0.58 e Å−3
2378 reflectionsΔρmin = −1.30 e Å−3
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
Cd10.00000.00001.00000.03262 (9)
O1W−0.1754 (3)−0.1628 (3)0.9055 (2)0.0469 (4)
O2W0.2890 (3)−0.1665 (3)0.9317 (2)0.0554 (5)
O3W0.4251 (4)0.9783 (3)0.3137 (2)0.0540 (5)
O4W0.5895 (3)0.7407 (3)0.1154 (2)0.0492 (4)
O10.6065 (3)0.1946 (3)0.4185 (2)0.0531 (4)
O20.6400 (4)0.3942 (3)0.2406 (2)0.0606 (5)
N1−0.0243 (3)0.1980 (2)0.80060 (18)0.0371 (4)
C10.5988 (3)0.3514 (3)0.3622 (2)0.0387 (4)
C20.5375 (4)0.5053 (3)0.4404 (2)0.0424 (5)
H20.55450.61620.40070.051*
C30.0421 (4)0.1372 (3)0.6866 (2)0.0465 (5)
H30.08230.01260.68730.056*
C40.0540 (4)0.2496 (3)0.5679 (2)0.0468 (5)
H40.10140.20050.49070.056*
C5−0.0050 (3)0.4372 (3)0.56279 (19)0.0317 (4)
C6−0.0735 (4)0.4991 (3)0.6825 (2)0.0438 (5)
H6−0.11350.62290.68520.053*
C7−0.0823 (4)0.3778 (3)0.7969 (2)0.0449 (5)
H7−0.13070.42270.87540.054*
H1WA−0.248 (6)−0.192 (6)0.955 (5)0.087 (15)*
H1WB−0.233 (5)−0.117 (5)0.847 (4)0.052 (10)*
H2WA0.366 (4)−0.196 (4)0.983 (3)0.036 (7)*
H2WB0.300 (5)−0.218 (5)0.877 (4)0.058 (10)*
H3WA0.406 (5)0.923 (5)0.392 (4)0.058 (9)*
H3WB0.493 (6)1.030 (6)0.324 (4)0.081 (13)*
H4WA0.615 (5)0.651 (5)0.147 (4)0.053 (10)*
H4WB0.555 (6)0.805 (6)0.167 (5)0.076 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.04199 (14)0.02980 (13)0.02433 (12)−0.00900 (8)0.00253 (8)−0.00217 (7)
O1W0.0558 (10)0.0477 (10)0.0416 (10)−0.0201 (8)−0.0010 (9)−0.0096 (8)
O2W0.0517 (10)0.0647 (12)0.0434 (10)0.0051 (9)−0.0049 (8)−0.0284 (9)
O3W0.0781 (13)0.0511 (11)0.0409 (10)−0.0323 (10)−0.0092 (9)−0.0037 (8)
O4W0.0629 (11)0.0454 (11)0.0406 (10)−0.0186 (9)−0.0017 (8)−0.0044 (8)
O10.0835 (13)0.0395 (9)0.0421 (9)−0.0222 (9)0.0074 (9)−0.0167 (7)
O20.0999 (15)0.0437 (10)0.0431 (10)−0.0239 (10)0.0203 (10)−0.0195 (8)
N10.0459 (9)0.0343 (9)0.0284 (8)−0.0105 (7)0.0014 (7)0.0002 (7)
C10.0462 (11)0.0358 (10)0.0389 (11)−0.0145 (8)0.0051 (8)−0.0158 (9)
C20.0583 (13)0.0353 (10)0.0387 (11)−0.0171 (9)0.0089 (9)−0.0151 (8)
C30.0692 (15)0.0313 (10)0.0334 (11)−0.0084 (10)0.0050 (10)−0.0011 (8)
C40.0710 (15)0.0336 (11)0.0300 (11)−0.0079 (10)0.0097 (10)−0.0033 (8)
C50.0350 (9)0.0318 (9)0.0268 (9)−0.0094 (7)−0.0010 (7)−0.0003 (8)
C60.0656 (14)0.0310 (10)0.0317 (10)−0.0099 (9)0.0056 (9)−0.0043 (8)
C70.0636 (14)0.0370 (11)0.0297 (10)−0.0091 (10)0.0065 (9)−0.0035 (8)
Geometric parameters (Å, °) top
Cd1—O2Wi2.259 (2)O2—C11.257 (3)
Cd1—O2W2.259 (2)N1—C31.331 (3)
Cd1—N1i2.295 (2)N1—C71.338 (3)
Cd1—N12.295 (2)C1—C21.495 (3)
Cd1—O1W2.348 (2)C2—C2ii1.293 (5)
Cd1—O1Wi2.348 (2)C2—H20.9300
O1W—H1WA0.76 (5)C3—C41.373 (3)
O1W—H1WB0.71 (4)C3—H30.9300
O2W—H2WA0.73 (3)C4—C51.394 (3)
O2W—H2WB0.72 (4)C4—H40.9300
O3W—H3WA0.85 (4)C5—C61.390 (3)
O3W—H3WB0.74 (4)C5—C5iii1.476 (4)
O4W—H4WA0.70 (4)C6—C71.373 (3)
O4W—H4WB0.77 (4)C6—H60.9300
O1—C11.246 (3)C7—H70.9300
O2Wi—Cd1—O2W180.0C3—N1—Cd1120.40 (15)
O2Wi—Cd1—N1i89.00 (8)C7—N1—Cd1121.73 (15)
O2W—Cd1—N1i91.00 (8)O1—C1—O2124.9 (2)
O2Wi—Cd1—N191.00 (8)O1—C1—C2120.0 (2)
O2W—Cd1—N189.00 (8)O2—C1—C2115.1 (2)
N1i—Cd1—N1180.0C2ii—C2—C1124.4 (3)
O2Wi—Cd1—O1W86.81 (9)C2ii—C2—H2117.8
O2W—Cd1—O1W93.19 (9)C1—C2—H2117.8
N1i—Cd1—O1W89.40 (8)N1—C3—C4123.1 (2)
N1—Cd1—O1W90.60 (8)N1—C3—H3118.4
O2Wi—Cd1—O1Wi93.19 (9)C4—C3—H3118.4
O2W—Cd1—O1Wi86.81 (9)C3—C4—C5120.1 (2)
N1i—Cd1—O1Wi90.60 (8)C3—C4—H4120.0
N1—Cd1—O1Wi89.40 (8)C5—C4—H4120.0
O1W—Cd1—O1Wi180.0C6—C5—C4116.28 (18)
Cd1—O1W—H1WA112 (3)C6—C5—C5iii121.9 (2)
Cd1—O1W—H1WB117 (3)C4—C5—C5iii121.8 (2)
H1WA—O1W—H1WB103 (4)C7—C6—C5120.1 (2)
Cd1—O2W—H2WA115 (2)C7—C6—H6119.9
Cd1—O2W—H2WB124 (3)C5—C6—H6119.9
H2WA—O2W—H2WB117 (4)N1—C7—C6123.0 (2)
H3WA—O3W—H3WB106 (4)N1—C7—H7118.5
H4WA—O4W—H4WB111 (4)C6—C7—H7118.5
C3—N1—C7117.36 (19)
O2Wi—Cd1—N1—C3−144.1 (2)C7—N1—C3—C40.3 (4)
O2W—Cd1—N1—C335.9 (2)Cd1—N1—C3—C4−171.6 (2)
O1W—Cd1—N1—C3−57.3 (2)N1—C3—C4—C50.0 (4)
O1Wi—Cd1—N1—C3122.7 (2)C3—C4—C5—C60.2 (4)
O2Wi—Cd1—N1—C744.3 (2)C3—C4—C5—C5iii−179.8 (3)
O2W—Cd1—N1—C7−135.7 (2)C4—C5—C6—C7−0.7 (3)
O1W—Cd1—N1—C7131.1 (2)C5iii—C5—C6—C7179.3 (3)
O1Wi—Cd1—N1—C7−48.9 (2)C3—N1—C7—C6−0.8 (4)
O1—C1—C2—C2ii−10.8 (5)Cd1—N1—C7—C6171.0 (2)
O2—C1—C2—C2ii169.3 (3)C5—C6—C7—N11.0 (4)
Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O3Wiii0.71 (4)2.10 (4)2.811 (3)175 (4)
O1W—H1WA···O4Wiv0.76 (5)2.04 (5)2.790 (3)168 (5)
O4W—H4WB···O3W0.77 (4)2.16 (4)2.929 (3)173 (4)
O3W—H3WB···O1v0.74 (4)2.06 (4)2.759 (3)157 (4)
O4W—H4WA···O20.70 (4)2.02 (4)2.714 (3)170 (4)
O3W—H3WA···O1ii0.85 (4)1.98 (4)2.833 (3)172 (3)
O2W—H2WB···O2vi0.72 (4)1.91 (4)2.615 (3)168 (4)
O2W—H2WA···O4Wvii0.73 (3)2.02 (3)2.748 (3)175 (3)
Symmetry codes: (iii) −x, −y+1, −z+1; (iv) x−1, y−1, z+1; (v) x, y+1, z; (ii) −x+1, −y+1, −z+1; (vi) −x+1, −y, −z+1; (vii) x, y−1, z+1.
Table 1
Selected geometric parameters (Å, °) top
Cd1—O2W2.259 (2)Cd1—O1W2.348 (2)
Cd1—N12.295 (2)
O2Wi—Cd1—O2W180.0O2Wi—Cd1—O1W86.81 (9)
O2Wi—Cd1—N191.00 (8)O2W—Cd1—O1W93.19 (9)
O2W—Cd1—N189.00 (8)N1i—Cd1—O1W89.40 (8)
N1i—Cd1—N1180.0N1—Cd1—O1W90.60 (8)
Symmetry codes: (i) −x, −y, −z+2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WB···O3Wii0.71 (4)2.10 (4)2.811 (3)175 (4)
O1W—H1WA···O4Wiii0.76 (5)2.04 (5)2.790 (3)168 (5)
O4W—H4WB···O3W0.77 (4)2.16 (4)2.929 (3)173 (4)
O3W—H3WB···O1iv0.74 (4)2.06 (4)2.759 (3)157 (4)
O4W—H4WA···O20.70 (4)2.02 (4)2.714 (3)170 (4)
O3W—H3WA···O1v0.85 (4)1.98 (4)2.833 (3)172 (3)
O2W—H2WB···O2vi0.72 (4)1.91 (4)2.615 (3)168 (4)
O2W—H2WA···O4Wvii0.73 (3)2.02 (3)2.748 (3)175 (3)
Symmetry codes: (ii) −x, −y+1, −z+1; (iii) x−1, y−1, z+1; (iv) x, y+1, z; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y, −z+1; (vii) x, y−1, z+1.
Acknowledgements top

The author thanks Tong Hua Teachers' College for financial support.

references
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