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Acta Cryst. (2009). E65, m1555    [ doi:10.1107/S1600536809045255 ]

Poly[triaqua([mu]-butane-1,2,3,4-tetracarboxylato)dicadmium(II)]

C.-H. Ma and Y.-S. Yan

Abstract top

The asymmetric unit of the title CdII coordination polymer, [Cd2(C8H6O8)(H2O)3]n, contains two crystallographically independent CdII cations, one-half each of two independent anionic butane-1,2,3,4-tetracarboxylate units (L) and three water molecules. Both anionic units lie on inversion centers. One of the CdII ions is six-coordinated by four carboxylate O atoms from four L anions and two water O atoms in a distorted octahedral coordination environment. The other CdII ion is eight-coordinated by seven carboxylate O atoms from four L anions and one water O atom. The anionic units bridge neighboring CdII centers, forming a three-dimensional framework. O-H...O hydrogen-bonding interactions between the water molecules and carboxylate O atoms further stabilize the structure.

Comment top

Over years of intensive studies on tetracarboxylate ligands, transition metals and poly-carboxylates, a vast amount of data have been acquired. As an important family of multidentate O-donor ligands, organic tetracarboxylate ligands, such as 1,2,4,5-benzenetetracarboxylate, have been extensively employed in the preparation of such metal-organic compound (Yang et al., 2008). In this regard, butane-1,2,3,4-tetracarboxylatic acid (H4L) is also a good ligand in coordination chemistry due to its strong coordination ability and versatile coordination modes, so much attention has been paid to it in recent years (Liu et al., 2008). In this contribution, H4L was selected as a bridging ligand, and a new cadmium coordination polymer, namely [Cd2(L)(H2O)3], was obtained.

As shown in Fig. 1, the asymmetric unit of the title CdII coordination polymer, contains two crystallographically independent CdII cations, one-half each of two independent L anions and three water molecules. The L anions lie on inversion centers. One of the CdII ion, Cd1, is six-coordinated by four carboxylate oxygen atoms from L anions and two water oxygen atoms in a distorted octahedral coordination environment. Atom Cd2 is eight-coordinated by seven carboxylate oxygen atoms from L anions and one water oxygen atom. The L anions bridge neighboring CdII centers to form a complicated three-dimensional framework structure (Fig. 2). The hydrogen-bonding interactions between water molecules and carboxylate oxygen atoms further stabilize the three-dimensional framework structure of the title compound.

Related literature top

For coordination polymers with tetracarboxylate ligands, see: Liu et al. (2008); Yang et al. (2008).

Experimental top

A mixture of CdCl2.2H2O (0.10 mmol), H4L (0.05 mmol) and water (12 ml) was sealed in a Teflon reactor (15 ml), which was heated at 413 K for 3 d and then gradually cooled to room temperature. Purple crystals of the title compound were isolated (yield 68% based on Cd).

Refinement top

H atoms bonded to C atoms were positioned geometrically (C-H = 0.97 or 0.98 Å) and refined as riding, with Uiso(H) = 1.2Ueq(carrier). The water H atoms were located in a difference Fourier map, and were refined with distance restraints of O-H = 0.85 (1) Å and H···H = 1.35 (1) Å; their Uiso values were tied to those of parent atoms by a factor of 1.5.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the local coordination of CdII cations in the title compound, showing the atom-numbering scheme. Displacement ellipsoids drawn at the 30% probability level. Symmetry codes: (i) -2-x, -y, 2-z; (ii) -2-x, 1-y, 1-z; (iii) x+1, y, z; (iv) -1-x, 1-y, 1-z); (v) -1-x, -y, 1-z; (vi) -2-x, -1-y, 2-z.
[Figure 2] Fig. 2. View of the three-dimensional framework structure of the title compound.
Poly[triaqua(µ-butane-1,2,3,4-tetracarboxylato)dicadmium(II)] top
Crystal data top
[Cd2(C8H6O8)(H2O)3]Z = 2
Mr = 508.98F(000) = 488
Triclinic, P1Dx = 2.729 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.499 (4) ÅCell parameters from 2847 reflections
b = 7.928 (4) Åθ = 3.0–29.1°
c = 11.982 (5) ŵ = 3.49 mm−1
α = 72.886 (4)°T = 293 K
β = 85.748 (4)°Block, colourless
γ = 65.666 (5)°0.27 × 0.22 × 0.20 mm
V = 619.4 (6) Å3
Data collection top
Bruker APEX CCD area-detector
diffractometer		2847 independent reflections
Radiation source: fine-focus sealed tube2225 reflections with I > 2σ(I)
graphiteRint = 0.024
ω scansθmax = 29.1°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→9
Tmin = 0.812, Tmax = 0.910k = −9→9
4846 measured reflectionsl = −16→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053H atoms treated by a mixture of independent and constrained refinement
S = 0.92 w = 1/[σ2(Fo2) + (0.024P)2]
where P = (Fo2 + 2Fc2)/3
2847 reflections(Δ/σ)max = 0.001
208 parametersΔρmax = 0.75 e Å−3
4 restraintsΔρmin = −0.85 e Å−3
Crystal data top
[Cd2(C8H6O8)(H2O)3]γ = 65.666 (5)°
Mr = 508.98V = 619.4 (6) Å3
Triclinic, P1Z = 2
a = 7.499 (4) ÅMo Kα radiation
b = 7.928 (4) ŵ = 3.49 mm−1
c = 11.982 (5) ÅT = 293 K
α = 72.886 (4)°0.27 × 0.22 × 0.20 mm
β = 85.748 (4)°
Data collection top
Bruker APEX CCD area-detector
diffractometer		2847 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2225 reflections with I > 2σ(I)
Tmin = 0.812, Tmax = 0.910Rint = 0.024
4846 measured reflectionsθmax = 29.1°
Refinement top
R[F2 > 2σ(F2)] = 0.026H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.053Δρmax = 0.75 e Å−3
S = 0.92Δρmin = −0.85 e Å−3
2847 reflectionsAbsolute structure: ?
208 parametersFlack parameter: ?
4 restraintsRogers parameter: ?
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
C1−1.1870 (5)−0.0435 (5)0.8775 (3)0.0222 (8)
C2−1.0228 (5)−0.2392 (5)0.9250 (4)0.0242 (9)
H2A−0.9498−0.23480.98680.029*
H2B−0.9344−0.26750.86320.029*
C3−1.0890 (5)−0.4024 (5)0.9729 (3)0.0195 (8)
H3−1.1514−0.41540.90870.023*
C4−1.2362 (5)−0.3626 (5)1.0672 (3)0.0180 (8)
C5−0.5128 (5)0.1885 (5)0.5710 (3)0.0157 (7)
C6−0.5234 (5)0.1089 (5)0.4728 (3)0.0138 (7)
H6−0.42370.12220.41750.017*
C7−0.7242 (5)0.2187 (5)0.4086 (3)0.0198 (8)
H7A−0.73130.15580.35180.024*
H7B−0.82340.21190.46430.024*
C8−0.7700 (5)0.4286 (5)0.3463 (3)0.0186 (8)
O1−1.1495 (4)0.1055 (4)0.8533 (2)0.0254 (6)
O2−1.3566 (4)−0.0238 (4)0.8590 (3)0.0316 (7)
O1W−0.7754 (4)0.6162 (4)0.6382 (3)0.0295 (7)
HW11−0.847 (7)0.565 (7)0.635 (4)0.044*
HW12−0.721 (7)0.639 (7)0.574 (4)0.044*
O3−0.6391 (4)0.2043 (4)0.6460 (2)0.0230 (6)
O2W−0.9660 (4)0.0105 (5)0.6309 (3)0.0293 (7)
HW22−0.916 (7)−0.104 (7)0.631 (4)0.044*
HW21−1.084 (3)0.058 (6)0.611 (4)0.044*
O4−0.3718 (4)0.2352 (4)0.5789 (2)0.0249 (6)
O3W−0.6465 (4)−0.1422 (4)0.8435 (3)0.0421 (9)
HW31−0.545 (5)−0.136 (6)0.864 (4)0.063*
HW32−0.628 (7)−0.259 (4)0.875 (4)0.063*
O5−1.2174 (4)−0.2778 (4)1.1353 (2)0.0322 (7)
O6−1.3702 (4)−0.4211 (4)1.0774 (2)0.0293 (7)
O7−0.6349 (4)0.4662 (4)0.2971 (3)0.0450 (9)
O8−0.9426 (4)0.5479 (4)0.3476 (3)0.0386 (8)
Cd1−0.89424 (4)0.14635 (4)0.75659 (2)0.01890 (8)
Cd2−0.48747 (4)0.31540 (4)0.76500 (2)0.01614 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.019 (2)0.0184 (19)0.021 (2)−0.0033 (16)0.0030 (16)−0.0005 (16)
C20.0179 (19)0.0178 (19)0.032 (2)−0.0057 (16)0.0038 (17)−0.0031 (17)
C30.0173 (19)0.0170 (19)0.020 (2)−0.0034 (16)0.0041 (16)−0.0056 (16)
C40.0171 (18)0.0115 (17)0.0177 (19)−0.0006 (15)0.0044 (15)−0.0020 (15)
C50.0149 (18)0.0066 (15)0.0194 (19)−0.0002 (14)−0.0035 (15)−0.0002 (14)
C60.0117 (17)0.0137 (17)0.0149 (18)−0.0045 (14)0.0010 (14)−0.0037 (14)
C70.0176 (19)0.0157 (18)0.022 (2)−0.0057 (15)−0.0049 (16)−0.0001 (15)
C80.020 (2)0.0136 (18)0.020 (2)−0.0054 (16)−0.0048 (16)−0.0029 (15)
O10.0239 (14)0.0194 (14)0.0319 (16)−0.0115 (12)0.0077 (13)−0.0038 (12)
O20.0195 (15)0.0229 (15)0.0472 (19)−0.0093 (12)−0.0054 (13)−0.0002 (14)
O1W0.0262 (16)0.0263 (16)0.0362 (18)−0.0125 (13)0.0027 (14)−0.0068 (14)
O30.0205 (14)0.0247 (14)0.0276 (15)−0.0101 (12)0.0100 (12)−0.0139 (12)
O2W0.0237 (15)0.0300 (16)0.0406 (18)−0.0120 (14)0.0021 (14)−0.0177 (15)
O40.0241 (14)0.0297 (15)0.0276 (15)−0.0160 (13)0.0017 (12)−0.0104 (12)
O3W0.0237 (17)0.0224 (16)0.073 (3)−0.0105 (14)−0.0142 (16)0.0028 (16)
O50.0320 (16)0.0449 (18)0.0316 (17)−0.0197 (14)0.0097 (13)−0.0241 (15)
O60.0237 (15)0.0331 (16)0.0367 (17)−0.0155 (13)0.0118 (13)−0.0150 (14)
O70.0289 (17)0.0218 (16)0.075 (3)−0.0138 (14)0.0029 (17)0.0039 (16)
O80.0228 (16)0.0213 (15)0.052 (2)0.0002 (13)0.0038 (15)0.0030 (14)
Cd10.01652 (15)0.01605 (14)0.02473 (16)−0.00788 (11)0.00187 (12)−0.00519 (12)
Cd20.01470 (14)0.01407 (14)0.01976 (15)−0.00613 (11)0.00438 (11)−0.00553 (11)
Geometric parameters (Å, °) top
C1—O21.245 (4)O1W—Cd22.601 (3)
C1—O11.272 (4)O1W—HW110.81 (5)
C1—C21.502 (5)O1W—HW120.85 (5)
C2—C31.517 (5)O3—Cd12.370 (3)
C2—H2A0.97O3—Cd22.430 (3)
C2—H2B0.97O2W—Cd12.295 (3)
C3—C41.528 (5)O2W—HW220.83 (5)
C3—C3i1.560 (7)O2W—HW210.831 (19)
C3—H30.98O4—Cd22.495 (3)
C4—O51.247 (4)O3W—Cd12.270 (3)
C4—O61.254 (4)O3W—HW310.842 (19)
C5—O31.251 (4)O3W—HW320.849 (19)
C5—O41.274 (4)O5—Cd1iv2.267 (3)
C5—C61.511 (5)O5—Cd2iv2.521 (3)
C6—C71.522 (5)O6—Cd2iv2.303 (3)
C6—C6ii1.549 (7)O7—Cd2v2.201 (3)
C6—H60.98O8—Cd1vi2.221 (3)
C7—C81.510 (5)Cd1—O8vi2.221 (3)
C7—H7A0.97Cd1—O5iv2.267 (3)
C7—H7B0.97Cd2—O7v2.201 (3)
C8—O71.232 (5)Cd2—O6iv2.303 (3)
C8—O81.252 (4)Cd2—O2vii2.381 (3)
O1—Cd12.252 (3)Cd2—O1vii2.490 (3)
O1—Cd2iii2.490 (3)Cd2—O5iv2.521 (3)
O2—Cd2iii2.381 (3)
O2—C1—O1119.4 (3)Cd1—O3W—HW32139 (3)
O2—C1—C2121.9 (3)HW31—O3W—HW32104 (3)
O1—C1—C2118.7 (3)C4—O5—Cd1iv165.6 (2)
C1—C2—C3114.3 (3)C4—O5—Cd2iv87.7 (2)
C1—C2—H2A108.7Cd1iv—O5—Cd2iv105.79 (11)
C3—C2—H2A108.7C4—O6—Cd2iv97.8 (2)
C1—C2—H2B108.7C8—O7—Cd2v146.3 (3)
C3—C2—H2B108.7C8—O8—Cd1vi132.2 (3)
H2A—C2—H2B107.6O8vi—Cd1—O197.13 (10)
C2—C3—C4111.4 (3)O8vi—Cd1—O5iv83.82 (13)
C2—C3—C3i110.8 (4)O1—Cd1—O5iv104.20 (10)
C4—C3—C3i108.2 (4)O8vi—Cd1—O3W161.95 (11)
C2—C3—H3108.8O1—Cd1—O3W100.36 (11)
C4—C3—H3108.8O5iv—Cd1—O3W87.57 (13)
C3i—C3—H3108.8O8vi—Cd1—O2W96.30 (13)
O5—C4—O6121.1 (3)O1—Cd1—O2W84.45 (11)
O5—C4—C3119.4 (3)O5iv—Cd1—O2W171.28 (10)
O6—C4—C3119.5 (3)O3W—Cd1—O2W89.84 (13)
O3—C5—O4119.9 (3)O8vi—Cd1—O379.76 (10)
O3—C5—C6120.3 (3)O1—Cd1—O3176.60 (9)
O4—C5—C6119.8 (3)O5iv—Cd1—O376.92 (10)
C5—C6—C7110.8 (3)O3W—Cd1—O382.86 (11)
C5—C6—C6ii107.5 (3)O2W—Cd1—O394.50 (10)
C7—C6—C6ii111.7 (3)O7v—Cd2—O6iv94.65 (12)
C5—C6—H6108.9O7v—Cd2—O2vii135.30 (11)
C7—C6—H6108.9O6iv—Cd2—O2vii98.61 (10)
C6ii—C6—H6108.9O7v—Cd2—O3127.03 (11)
C8—C7—C6113.6 (3)O6iv—Cd2—O3123.75 (9)
C8—C7—H7A108.8O2vii—Cd2—O378.14 (10)
C6—C7—H7A108.8O7v—Cd2—O1vii82.94 (11)
C8—C7—H7B108.8O6iv—Cd2—O1vii98.91 (10)
C6—C7—H7B108.8O2vii—Cd2—O1vii52.95 (8)
H7A—C7—H7B107.7O3—Cd2—O1vii119.71 (9)
O7—C8—O8126.0 (3)O7v—Cd2—O484.40 (11)
O7—C8—C7117.0 (3)O6iv—Cd2—O4172.55 (9)
O8—C8—C7116.9 (3)O2vii—Cd2—O487.15 (10)
C1—O1—Cd1127.2 (2)O3—Cd2—O452.67 (8)
C1—O1—Cd2iii90.8 (2)O1vii—Cd2—O488.32 (9)
Cd1—O1—Cd2iii118.95 (12)O7v—Cd2—O5iv140.00 (11)
C1—O2—Cd2iii96.6 (2)O6iv—Cd2—O5iv53.43 (9)
Cd2—O1W—HW1199 (3)O2vii—Cd2—O5iv78.81 (10)
Cd2—O1W—HW12101 (3)O3—Cd2—O5iv71.26 (9)
HW11—O1W—HW12111 (5)O1vii—Cd2—O5iv121.41 (10)
C5—O3—Cd1157.2 (2)O4—Cd2—O5iv123.88 (8)
C5—O3—Cd295.5 (2)O7v—Cd2—O1W76.29 (11)
Cd1—O3—Cd2105.53 (10)O6iv—Cd2—O1W86.09 (11)
Cd1—O2W—HW22128 (3)O2vii—Cd2—O1W146.80 (9)
Cd1—O2W—HW21114 (3)O3—Cd2—O1W72.16 (10)
HW22—O2W—HW21109 (5)O1vii—Cd2—O1W158.98 (9)
C5—O4—Cd291.9 (2)O4—Cd2—O1W86.51 (10)
Cd1—O3W—HW31116 (3)O5iv—Cd2—O1W77.91 (11)
Symmetry codes: (i) −x−2, −y−1, −z+2; (ii) −x−1, −y, −z+1; (iii) x−1, y, z; (iv) −x−2, −y, −z+2; (v) −x−1, −y+1, −z+1; (vi) −x−2, −y+1, −z+1; (vii) x+1, y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—HW11···O8vi0.81 (5)2.08 (5)2.877 (4)169 (5)
O1W—HW12···O4v0.85 (5)2.04 (5)2.866 (4)166 (5)
O2W—HW22···O1Wviii0.83 (5)2.00 (5)2.828 (5)175 (5)
O2W—HW21···O4iii0.83 (2)2.02 (2)2.825 (4)163 (4)
O3W—HW31···O2vii0.84 (2)1.95 (2)2.736 (4)156 (4)
O3W—HW32···O6i0.85 (2)2.43 (2)3.260 (5)165 (4)
Symmetry codes: (vi) −x−2, −y+1, −z+1; (v) −x−1, −y+1, −z+1; (viii) x, y−1, z; (iii) x−1, y, z; (vii) x+1, y, z; (i) −x−2, −y−1, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—HW11···O8i0.81 (5)2.08 (5)2.877 (4)169 (5)
O1W—HW12···O4ii0.85 (5)2.04 (5)2.866 (4)166 (5)
O2W—HW22···O1Wiii0.83 (5)2.00 (5)2.828 (5)175 (5)
O2W—HW21···O4iv0.83 (2)2.02 (2)2.825 (4)163 (4)
O3W—HW31···O2v0.84 (2)1.95 (2)2.736 (4)156 (4)
O3W—HW32···O6vi0.85 (2)2.43 (2)3.260 (5)165 (4)
Symmetry codes: (i) −x−2, −y+1, −z+1; (ii) −x−1, −y+1, −z+1; (iii) x, y−1, z; (iv) x−1, y, z; (v) x+1, y, z; (vi) −x−2, −y−1, −z+2.
Acknowledgements top

The authors thank Jiangsu University and Jilin Normal University for support.

references
References top

Bruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Liu, Y.-Y., Ma, J.-F., Yang, J., Ma, J.-C. & Su, Z.-M. (2008). CrystEngComm, 10, 894–904.

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

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yang, J., Ma, J.-F., Batten, S. R. & Su, Z.-M. (2008). Chem. Commun. pp. 2233–2235.