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Acta Cryst. (2007). E63, m1639    [ doi:10.1107/S160053680702243X ]

A one-dimensional coordination polymer: catena-poly[[diaqua(2,4-dihydroxybenzoato)cadmium(II)]-[mu]-2,4-dihydroxybenzoato]

Z.-L. Wang and Y.-P. Niu

Abstract top

The title compound, [Cd(C7H5O4)2(H2O)2]n, consists of a one-dimensional chain, in which the Cd2+ centre is coordinated by four O atoms from two bidentate carboxylate groups of two 2,4-dihydroxybenzoate anions, two water molecules, and one hydroxyl O atom of another 2,4-dihydroxybenzoate anion. This results in a distorted pentagonal-bipyramidal CdO7 polyhedron.

Comment top

Design and synthesis of metal coordination polymers based on benzene carboxylates have been attracting chemist's interests and constitutes an important area of research (Thirumurugan & Natarajan, 2004). During the past years, lots of novel benzene multicarboxylates base compounds have been reported (Tao et al., 2000; Zhang et al., 2005). However, in those reported literatures, the common features tried to construct predictable one-, two, three-dimensional coordination networks by changing the numbers or relative position of carboxylates. In contrast, benzene carboxylates containing the hydroxyl can be utilized to coordinate to metal ions and generate unusual structures have never been reported. Herein, we report the title compound (I).

The title compound (I) present a one-dimensional chain [Cd(C7O4H5)2(H2O)2]n, in which Cd2+ is coordinated by four oxygen atoms from two 2,4-dihydroxybenzoate anion, two water molecules, and one oxygen from the hydroxyl of another 2,4-dihydroxybenzoate anion. The environment of Cd ion is in a distorted pentagonal bipyramid (Fig. 1). In the equatorial plane, Cd1 ion is coordinated by four carboxylates oxygen (O1, O2, O5, O6) and one oxygen (O3b) of the hydroxyl. The Cd1—O distances range from 2.327 (2) to 2.459 (2)Å (Table 1). The mean deviation from the equatorial plane is 0.129 Å. The axial sites are occupied by two water oxygen atoms (O9 and O10) with Cd1—O lengths ranging from 2.196 (2) to 2.268 (3)Å (Table 1). The obvious differences of Cd1—O length show that the water more greatly interact with the Cd2+ ion than that of the carboxylate. The axial O9—Cd1—O10 bond angle is 177.80 (9) Å.

In addition, the intra-molecular hydrogen bonds exhibit in the compound, O7—H7 and O3—H31 acting as hydrogen bond donor, and O6 and O1 as hydrogen bond acceptor, constructing two S(6) rings (Fig. 1, Table 2). These units are linked into a one-dimensional chain-like structure by the hydroxyl oxygen atom O3 (Fig. 2).

Related literature top

For related literature, see: Tao et al. (2000), Thirumurugan & Natarajan (2004) and Zhang et al. (2005).

Experimental top

Solid CdCO3 (1 mmol, 0.172 g) was added to an aqueous solution (25 ml) of 2,4-dihydroxybenzoic acid (2.0 mmol, 0.308 g). The mixture was stirred for 10 minutes under the temperature of 373 K. The solution was filtered, and the filtrate was kept at the room temperature. After ten days weeks, colorless crystals of (I) were obtained.

Refinement top

The H atoms bonded to water were located in a difference synthesis and refined with distance restraints O—H = 0.82 (1) Å and H···H = 1.34 (2) Å and Uiso(H) = Ueq(O). The remaining H atoms were positioned geometrically, with C—H = 0.93 Å and O—H = 0.82 Å, and were refined as riding with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(O).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. For clarity, H atoms not involved in hydrogen bonds are omitted. [Symmetry code: (b) 1/2 + x, 1/2 - y, 1 - z]
[Figure 2] Fig. 2. One-dimensional structure of (I), For clarity, H atoms not involved in hydrogen bonds are omitted.
catena-poly[[diaqua(2,4-dihydroxybenzoato)cadmium(II)]-µ-2,4-dihydroxybenzoato] top
Crystal data top
[Cd(C7H5O4)2(H2O)2]F(000) = 1808
Mr = 454.65Dx = 1.912 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 5177 reflections
a = 11.964 (2) Åθ = 3.0–28.2°
b = 7.7882 (16) ŵ = 1.44 mm−1
c = 33.893 (7) ÅT = 292 K
V = 3158.1 (11) Å3Plate, colourless
Z = 80.35 × 0.20 × 0.04 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3063 independent reflections
Radiation source: fine-focus sealed tube2847 reflections with I > 2σ(I)
graphiteRint = 0.036
ω scansθmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		h = −14→14
Tmin = 0.633, Tmax = 0.945k = −9→9
19791 measured reflectionsl = −41→41
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)] = 0.029Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.069H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0295P)2 + 3.765P]
where P = (Fo2 + 2Fc2)/3
3063 reflections(Δ/σ)max = 0.002
248 parametersΔρmax = 0.48 e Å−3
18 restraintsΔρmin = −0.47 e Å−3
Crystal data top
[Cd(C7H5O4)2(H2O)2]V = 3158.1 (11) Å3
Mr = 454.65Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 11.964 (2) ŵ = 1.44 mm−1
b = 7.7882 (16) ÅT = 292 K
c = 33.893 (7) Å0.35 × 0.20 × 0.04 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		3063 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		2847 reflections with I > 2σ(I)
Tmin = 0.633, Tmax = 0.945Rint = 0.036
19791 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.029H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.069Δρmax = 0.48 e Å−3
S = 1.05Δρmin = −0.47 e Å−3
3063 reflectionsAbsolute structure: ?
248 parametersFlack parameter: ?
18 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
Cd10.903474 (16)0.23166 (3)0.448614 (5)0.02615 (9)
O10.75857 (17)0.2302 (3)0.50006 (5)0.0358 (5)
O20.93525 (17)0.2420 (3)0.51741 (6)0.0370 (5)
O30.60334 (16)0.2867 (4)0.54931 (6)0.0423 (6)
H310.635 (4)0.265 (5)0.5293 (14)0.063*
O40.69862 (19)0.4547 (4)0.67789 (7)0.0659 (8)
H4A0.75290.47010.69220.099*
O50.74055 (18)0.2508 (3)0.40614 (6)0.0383 (5)
O60.90716 (16)0.2860 (3)0.38111 (6)0.0411 (5)
O70.93668 (17)0.3721 (4)0.30975 (6)0.0560 (7)
H70.95430.34310.33220.084*
O80.62706 (19)0.4682 (4)0.22892 (7)0.0636 (8)
H80.56320.43260.22560.095*
O90.91561 (19)−0.0476 (3)0.44064 (8)0.0487 (6)
H910.9608 (19)−0.100 (3)0.4540 (8)0.033 (9)*
H920.871 (2)−0.113 (3)0.4305 (9)0.039 (9)*
O100.8982 (2)0.5205 (3)0.45687 (8)0.0489 (6)
H1010.949 (2)0.571 (4)0.4677 (8)0.049*
H1020.886 (3)0.551 (4)0.4348 (4)0.049*
C10.8319 (2)0.2536 (3)0.52658 (8)0.0288 (6)
C20.7975 (2)0.3003 (4)0.56677 (7)0.0260 (5)
C30.6847 (2)0.3185 (4)0.57667 (7)0.0274 (6)
C40.6530 (2)0.3707 (4)0.61387 (8)0.0373 (7)
H40.57780.38430.62000.045*
C50.7336 (2)0.4025 (4)0.64192 (8)0.0374 (7)
C60.8462 (2)0.3834 (5)0.63318 (8)0.0412 (8)
H60.90020.40360.65240.049*
C70.8769 (2)0.3343 (5)0.59590 (9)0.0383 (7)
H7A0.95240.32340.58990.046*
C80.8016 (2)0.2865 (4)0.37699 (8)0.0310 (6)
C90.7541 (2)0.3296 (4)0.33825 (8)0.0312 (6)
C100.8238 (2)0.3718 (4)0.30639 (8)0.0357 (7)
C110.7786 (2)0.4173 (5)0.27043 (8)0.0448 (8)
H110.82540.44770.24970.054*
C120.6648 (3)0.4178 (5)0.26516 (9)0.0432 (8)
C130.5936 (2)0.3759 (6)0.29596 (10)0.0500 (10)
H130.51650.37710.29240.060*
C140.6393 (2)0.3325 (5)0.33174 (9)0.0411 (8)
H140.59170.30380.35240.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.02635 (12)0.03452 (14)0.01758 (12)0.00370 (8)−0.00053 (7)−0.00107 (8)
O10.0321 (10)0.0571 (14)0.0182 (9)0.0013 (9)−0.0009 (8)−0.0076 (9)
O20.0271 (10)0.0589 (14)0.0249 (11)0.0110 (9)0.0036 (8)−0.0027 (9)
O30.0221 (11)0.0808 (18)0.0240 (12)−0.0032 (10)−0.0025 (8)−0.0144 (11)
O40.0374 (12)0.135 (3)0.0259 (12)−0.0068 (15)0.0072 (10)−0.0328 (14)
O50.0383 (11)0.0570 (14)0.0196 (10)0.0076 (10)0.0051 (9)0.0051 (9)
O60.0298 (11)0.0700 (16)0.0234 (11)0.0086 (10)−0.0049 (8)0.0051 (10)
O70.0200 (10)0.120 (2)0.0282 (11)−0.0045 (12)−0.0004 (9)0.0217 (14)
O80.0331 (12)0.129 (3)0.0284 (12)−0.0190 (14)−0.0113 (9)0.0305 (14)
O90.0404 (13)0.0364 (13)0.0692 (17)0.0016 (10)−0.0271 (12)−0.0001 (12)
O100.0490 (8)0.0467 (8)0.0511 (8)0.0002 (6)0.0005 (6)0.0001 (6)
C10.0294 (14)0.0336 (15)0.0234 (14)0.0049 (11)0.0006 (11)−0.0010 (11)
C20.0279 (13)0.0346 (15)0.0153 (12)0.0014 (11)0.0011 (10)−0.0032 (11)
C30.0222 (12)0.0388 (15)0.0213 (13)−0.0018 (11)−0.0021 (10)−0.0026 (11)
C40.0235 (14)0.063 (2)0.0249 (14)−0.0066 (13)0.0042 (11)−0.0097 (14)
C50.0331 (15)0.059 (2)0.0197 (13)−0.0068 (14)0.0023 (11)−0.0089 (13)
C60.0288 (15)0.071 (2)0.0233 (15)−0.0037 (14)−0.0057 (12)−0.0128 (14)
C70.0222 (13)0.065 (2)0.0281 (15)0.0025 (14)−0.0004 (11)−0.0082 (15)
C80.0316 (14)0.0402 (16)0.0212 (13)0.0064 (12)0.0003 (11)−0.0006 (11)
C90.0274 (13)0.0453 (17)0.0211 (13)0.0005 (12)0.0003 (11)0.0032 (12)
C100.0210 (13)0.061 (2)0.0251 (14)−0.0028 (13)−0.0016 (11)0.0046 (13)
C110.0273 (15)0.086 (3)0.0211 (14)−0.0115 (16)−0.0002 (11)0.0129 (15)
C120.0337 (16)0.074 (2)0.0219 (15)−0.0074 (15)−0.0075 (12)0.0116 (15)
C130.0219 (15)0.094 (3)0.0345 (18)−0.0077 (16)−0.0028 (12)0.0161 (18)
C140.0253 (14)0.073 (2)0.0253 (15)−0.0031 (15)0.0042 (11)0.0111 (15)
Geometric parameters (Å, °) top
Cd1—O92.196 (2)O10—H1010.809 (10)
Cd1—O102.268 (3)O10—H1020.798 (10)
Cd1—O62.327 (2)C1—C21.469 (4)
Cd1—O22.364 (2)C2—C71.396 (4)
Cd1—O3i2.397 (2)C2—C31.398 (4)
Cd1—O52.428 (2)C3—C41.378 (4)
Cd1—O12.459 (2)C4—C51.377 (4)
O1—C11.270 (3)C4—H40.9300
O2—C11.278 (4)C5—C61.387 (4)
O3—C31.367 (3)C6—C71.370 (4)
O3—Cd1ii2.397 (2)C6—H60.9300
O3—H310.80 (5)C7—H7A0.9300
O4—C51.352 (3)C8—C91.470 (4)
O4—H4A0.8200C9—C141.391 (4)
O5—C81.260 (3)C9—C101.403 (4)
O6—C81.270 (3)C10—C111.379 (4)
O7—C101.356 (3)C11—C121.373 (4)
O7—H70.8200C11—H110.9300
O8—C121.366 (3)C12—C131.386 (4)
O8—H80.8200C13—C141.372 (4)
O9—H910.813 (10)C13—H130.9300
O9—H920.812 (10)C14—H140.9300
O9—Cd1—O10177.80 (9)C7—C2—C1120.8 (2)
O9—Cd1—O693.31 (9)C3—C2—C1121.3 (2)
O10—Cd1—O686.65 (9)O3—C3—C4118.6 (2)
O9—Cd1—O298.31 (9)O3—C3—C2120.4 (2)
O10—Cd1—O281.31 (8)C4—C3—C2121.0 (2)
O6—Cd1—O2163.85 (8)C5—C4—C3119.5 (3)
O9—Cd1—O3i83.02 (9)C5—C4—H4120.3
O10—Cd1—O3i94.78 (9)C3—C4—H4120.3
O6—Cd1—O3i91.19 (7)O4—C5—C4117.4 (3)
O2—Cd1—O3i79.20 (7)O4—C5—C6121.7 (3)
O9—Cd1—O592.35 (8)C4—C5—C6120.9 (3)
O10—Cd1—O589.42 (8)C7—C6—C5119.2 (3)
O6—Cd1—O554.63 (7)C7—C6—H6120.4
O2—Cd1—O5135.39 (7)C5—C6—H6120.4
O3i—Cd1—O5145.31 (7)C6—C7—C2121.5 (3)
O9—Cd1—O197.43 (9)C6—C7—H7A119.2
O10—Cd1—O184.11 (8)C2—C7—H7A119.2
O6—Cd1—O1135.35 (7)O5—C8—O6119.3 (3)
O2—Cd1—O154.13 (7)O5—C8—C9121.8 (3)
O3i—Cd1—O1133.03 (7)O6—C8—C9118.9 (2)
O5—Cd1—O181.64 (7)O5—C8—Cd161.99 (15)
C1—O1—Cd190.81 (17)O6—C8—Cd157.45 (14)
C1—O2—Cd194.99 (17)C9—C8—Cd1174.7 (2)
C3—O3—Cd1ii134.54 (17)C14—C9—C10117.4 (2)
C3—O3—H31106 (3)C14—C9—C8121.8 (2)
Cd1ii—O3—H31120 (3)C10—C9—C8120.7 (3)
C5—O4—H4A109.5O7—C10—C11117.6 (2)
C8—O5—Cd190.73 (17)O7—C10—C9121.9 (2)
C8—O6—Cd195.15 (17)C11—C10—C9120.5 (3)
C10—O7—H7109.5C12—C11—C10120.3 (3)
C12—O8—H8109.5C12—C11—H11119.9
Cd1—O9—H91118.1 (18)C10—C11—H11119.9
Cd1—O9—H92128.9 (19)O8—C12—C11116.5 (3)
H91—O9—H92110.9 (17)O8—C12—C13122.8 (3)
Cd1—O10—H101121 (2)C11—C12—C13120.7 (3)
Cd1—O10—H102101 (2)C14—C13—C12118.6 (3)
H101—O10—H102114.2 (18)C14—C13—H13120.7
O1—C1—O2119.1 (3)C12—C13—H13120.7
O1—C1—C2119.9 (2)C13—C14—C9122.5 (3)
O2—C1—C2121.0 (2)C13—C14—H14118.8
C7—C2—C3117.9 (2)C9—C14—H14118.8
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x−1/2, −y+1/2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H31···O10.80 (5)1.80 (5)2.536 (3)154 (5)
O4—H4A···O8iii0.821.962.775 (3)173
O7—H7···O60.821.812.535 (3)147
O8—H8···O7iv0.821.992.732 (3)151
O9—H91···O2v0.81 (1)1.93 (1)2.738 (3)175 (3)
O9—H92···O5vi0.81 (1)1.90 (1)2.706 (3)175 (3)
O10—H101···O2vii0.81 (1)2.07 (2)2.855 (3)162 (3)
Symmetry codes: (iii) −x+3/2, −y+1, z+1/2; (iv) x−1/2, y, −z+1/2; (v) −x+2, −y, −z+1; (vi) −x+3/2, y−1/2, z; (vii) −x+2, −y+1, −z+1.
Table 1
Selected geometric parameters (Å) top
Cd1—O92.196 (2)Cd1—O3i2.397 (2)
Cd1—O102.268 (3)Cd1—O52.428 (2)
Cd1—O62.327 (2)Cd1—O12.459 (2)
Cd1—O22.364 (2)
Symmetry codes: (i) x+1/2, −y+1/2, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H31···O10.80 (5)1.80 (5)2.536 (3)154 (5)
O4—H4A···O8ii0.821.962.775 (3)173
O7—H7···O60.821.812.535 (3)147
O8—H8···O7iii0.821.992.732 (3)151
O9—H91···O2iv0.81 (1)1.93 (1)2.738 (3)175 (3)
O9—H92···O5v0.81 (1)1.90 (1)2.706 (3)175 (3)
O10—H101···O2vi0.81 (1)2.07 (2)2.855 (3)162 (3)
Symmetry codes: (ii) −x+3/2, −y+1, z+1/2; (iii) x−1/2, y, −z+1/2; (iv) −x+2, −y, −z+1; (v) −x+3/2, y−1/2, z; (vi) −x+2, −y+1, −z+1.
Acknowledgements top

This work was supported by the Basic Research Foundation for Natural Science of Henan University (grant No. 04YBRW053).

references
References top

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