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The Cd atom in the polymeric title compound, [Cd(C14H8O5)(H2O)]n, is linked to four carboxyl O atoms and a water mol­ecule in a five-coordinate coordination polyhedron that is midway between a square pyramid and a trigonal bipyramid. The Cd atom and the water molecules both lie on the same twofold axis and the central O atom of the 4,4'-oxydibenzoate moiety lies on another twofold axis. Covalent Cd-O bonds lead to the formation of a layer architecture perpendicular to the twofold axis, the layers being held together by hydrogen bonds in the third direction.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102006352/sk1548sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006352/sk1548Isup2.hkl
Contains datablock I

CCDC reference: 188591

Comment top

The study of diaqua[4,4'-(ethylenedioxy)dibenzoato]cadmium has documented the chelating mode of the two carboxyl ends of the dicarboxylate group [Cd—O = 2.241 (3) and 2.537 (3) Å], which links the six-coordinate Cd atoms into a zigzag chain (Liu et al., 2001). The omission of the flexible –CH2CH2O– linkage in the dicarboxylate unit furnishes the more tightly-packed title compound, (I) (Fig. 1). The dicarboxylate group of (I) lies on a crystallographic twofold axis, and both carboxyl O atoms are engaged in bonding to one metal atom [Cd—O = 2.198 (2) and 2.394 (2) Å] to furnish a layer structure. The layers are held together by hydrogen bonds [Owater···O = 2.690 (3) Å]. The five-coordinate geometry is completed by the water ligand [Cd—O = 2.231 (3) Å].

A search using the the Cambridge Structural Database (Allen et al., 1983) did not locate the parent carboxylic acid; only two metal complexes have been documented, a cobalt(II) and a copper(II) derivative. The dicarboxylate group functions as a bichelate in the cobalt complex, which adopts a chain structure (Skakle et al., 2001). In the copper complex, both carboxyl ends are monodentate to Cu atoms; the double-bonded O atoms are engaged in hydrogen bonding with the lattice methanol molecules (Burger et al., 1995). As no cadmium derivative of the parent acid appears to have been synthesized, the structure of (I) can only be compared with related structures, such as, for example, the malonate analog. The Cd—O distances are similar to distances found in these carboxylates. On the other hand, the Cd—Owater distance compares well with the distances in the trigonal [2.277 (7) Å; Post & Trotter, 1974] and rhombohedral modifications [2.283 (3) Å; Naumov et al., 2001] of cadmium malonate.

The d10 electron configuration of cadmium(II) allows the ion to exist in a variety of stereochemical environments, with the six-coordinate geometry accounting for 56% of examples; five-coordinate geometry is found in only 8% of examples (Siegel & Martin, 1994). The geometry of the Cd atom in (I) is approximately midway between a square pyramid and a trigonal bipyramid, as calculated by PLATON (Spek, 1990). Additionally, two somewhat long interactions of 2.824 (2) Å implicate a trigonal-prismatic geometry whose rectangular face is capped (Fig. 2). A five-coordinate geometry is found in the anionic complexes [(C2H5)2NCS2]CdX (X = NCS, Cl or Br). The geometry of the X = Cl derivative also lies midway along the Berry pseudorotation pathway. However, there are no important contacts (Baggio et al., 1996) that could raise the coordination number. The unambiguous seven-coordinate geometry found in cadmium diacetate dihydrate shows a smaller spread of distances for the square base-trigonal cap polyhedron [2.294 (4)–2.597 (4) Å; Harrison & Trotter, 1972].

Experimental top

Cadmium nitrate tetrahydrate (0.31 g, 1 mmol) and 4,4'-oxydibenzoic acid (0.26 g, 1 mmol) were heated in a small volume of methanol/water (50:50) until they dissolved completely. Ammonium hydroxide was then added dropwise until the solution had a pH of 6.0. Colorless crystals were deposited from the solution after it had been set aside for several weeks.

Refinement top

Aqua H atom was refined with the distance restraints O—H = 0.85 (1) Å and H···H = 1.39 (1) Å. The remaining H atoms were treated as riding (C—H 0.93 Å).

Computing details top

Data collection: XSCANS (Siemens, 1990); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. ORTEPII plot (Johnson, 1976) of the title compound at the 50% probability level illustrating the five-coordinate geometry of the Cd atom. H atoms are drawn as spheres of arbitrary radii.
[Figure 2] Fig. 2. ORTEPII plot (Johnson, 1976) showing the five-coordinate square-pyramidal/trigonal-bipryamidal intermediate geometry that is distorted to a seven-coordinate geometry, in which one rectangular face of the trigonal prism is capped. Symmetry-related atoms are not labeled.
Aqua(4,4'-oxydibenzoato-κO)cadmium(II) top
Crystal data top
[Cd(C14H8O5)(H2O)]F(000) = 380
Mr = 386.62Dx = 1.929 Mg m3
Monoclinic, P2/aMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yaCell parameters from 25 reflections
a = 7.307 (3) Åθ = 7.5–15°
b = 6.453 (3) ŵ = 1.67 mm1
c = 14.423 (8) ÅT = 298 K
β = 101.83 (3)°Block, colorless
V = 665.6 (6) Å30.45 × 0.33 × 0.27 mm
Z = 2
Data collection top
Siemens R3m four-circle
diffractometer
1776 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
Graphite monochromatorθmax = 30.0°, θmin = 3.2°
ω scansh = 010
Absorption correction: ψ scan
(North et al., 1968)
k = 09
Tmin = 0.408, Tmax = 0.433l = 2019
2078 measured reflections2 standard reflections every 200 reflections
1939 independent reflections intensity decay: none
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)] = 0.025Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0389P)2 + 0.3373P]
where P = (Fo2 + 2Fc2)/3
1939 reflections(Δ/σ)max < 0.001
101 parametersΔρmax = 0.43 e Å3
2 restraintsΔρmin = 0.58 e Å3
Crystal data top
[Cd(C14H8O5)(H2O)]V = 665.6 (6) Å3
Mr = 386.62Z = 2
Monoclinic, P2/aMo Kα radiation
a = 7.307 (3) ŵ = 1.67 mm1
b = 6.453 (3) ÅT = 298 K
c = 14.423 (8) Å0.45 × 0.33 × 0.27 mm
β = 101.83 (3)°
Data collection top
Siemens R3m four-circle
diffractometer
1776 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.017
Tmin = 0.408, Tmax = 0.4332 standard reflections every 200 reflections
2078 measured reflections intensity decay: none
1939 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0252 restraints
wR(F2) = 0.067H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.43 e Å3
1939 reflectionsΔρmin = 0.58 e Å3
101 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cd10.25000.65799 (3)0.00000.02996 (8)
O10.4021 (3)0.5911 (4)0.1448 (1)0.0516 (5)
O20.4801 (3)0.3173 (3)0.0695 (1)0.0387 (4)
O30.75000.0281 (4)0.50000.0396 (5)
O1W0.25001.0036 (4)0.00000.069 (1)
C10.4729 (3)0.4141 (4)0.1457 (2)0.0330 (4)
C20.5458 (3)0.3144 (3)0.2398 (2)0.0302 (4)
C30.6278 (3)0.1179 (4)0.2457 (2)0.0333 (4)
C40.6979 (3)0.0275 (4)0.3334 (1)0.0331 (4)
C50.6837 (3)0.1336 (3)0.4158 (2)0.0315 (4)
C60.5988 (4)0.3267 (4)0.4109 (2)0.0384 (5)
C70.5304 (3)0.4173 (4)0.3231 (2)0.0353 (5)
H1W0.342 (2)1.081 (3)0.025 (2)0.06 (1)*
H30.63560.04690.19060.040*
H40.75380.10260.33700.040*
H60.58770.39540.46620.046*
H70.47400.54700.31990.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0379 (1)0.0271 (1)0.0237 (1)0.0000.0035 (1)0.000
O10.058 (1)0.060 (1)0.036 (1)0.027 (1)0.006 (1)0.014 (1)
O20.044 (1)0.047 (1)0.023 (1)0.013 (1)0.002 (1)0.002 (1)
O30.057 (1)0.036 (1)0.020 (1)0.0000.006 (1)0.000
O1W0.059 (2)0.025 (1)0.104 (3)0.0000.027 (2)0.000
C10.027 (1)0.043 (1)0.027 (1)0.000 (1)0.002 (1)0.008 (1)
C20.028 (1)0.037 (1)0.024 (1)0.003 (1)0.001 (1)0.002 (1)
C30.040 (1)0.037 (1)0.022 (1)0.003 (1)0.005 (1)0.004 (1)
C40.040 (1)0.033 (1)0.024 (1)0.006 (1)0.001 (1)0.000 (1)
C50.033 (1)0.038 (1)0.020 (1)0.001 (1)0.001 (1)0.001 (1)
C60.043 (1)0.046 (1)0.024 (1)0.009 (1)0.002 (1)0.006 (1)
C70.037 (1)0.036 (1)0.030 (1)0.009 (1)0.002 (1)0.002 (1)
Geometric parameters (Å, º) top
Cd1—O12.198 (2)C3—C41.392 (3)
Cd1—O2i2.394 (2)C4—C51.394 (3)
Cd1—O1W2.231 (3)C5—C61.387 (3)
O1—C11.253 (3)C6—C71.391 (3)
O2—C11.275 (3)O1W—H1W0.85 (1)
O3—C51.389 (2)C3—H30.93
C1—C21.497 (3)C4—H40.93
C2—C71.398 (3)C6—H60.93
C2—C31.397 (3)C7—H70.93
O1—Cd1—O1ii157.4 (1)C3—C2—C1120.9 (2)
O1—Cd1—O1W101.3 (1)C4—C3—C2120.6 (2)
O1—Cd1—O2i96.4 (1)C3—C4—C5119.4 (2)
O1—Cd1—O2iii85.1 (1)C6—C5—O3123.8 (2)
O1ii—Cd1—O1W101.3 (1)C6—C5—C4120.6 (2)
O1ii—Cd1—O2i85.1 (1)O3—C5—C4115.5 (2)
O1ii—Cd1—O2iii96.4 (1)C5—C6—C7119.8 (2)
O2i—Cd1—O1W86.2 (1)C6—C7—C2120.4 (2)
O2i—Cd1—O2iii172.4 (1)Cd1—O1W—H1W126 (1)
O2iii—Cd1—O1W86.2 (1)C4—C3—H3119.7
C1—O1—Cd1108.5 (2)C2—C3—H3119.7
C1—O2—Cd1i120.8 (1)C3—C4—H4120.3
C5—O3—C5iv121.4 (3)C5—C4—H4120.3
O1—C1—O2121.8 (2)C5—C6—H6120.1
O1—C1—C2118.1 (2)C7—C6—H6120.1
O2—C1—C2120.1 (2)C6—C7—H7119.8
C7—C2—C3119.2 (2)C2—C7—H7119.8
C7—C2—C1119.9 (2)
O1ii—Cd1—O1—C124.0 (2)C7—C2—C3—C41.7 (3)
O1W—Cd1—O1—C1156.0 (2)C1—C2—C3—C4179.0 (2)
O2i—Cd1—O1—C168.6 (2)C2—C3—C4—C50.8 (4)
O2iii—Cd1—O1—C1118.9 (2)C5iv—O3—C5—C630.3 (2)
Cd1—O1—C1—O212.2 (3)C5iv—O3—C5—C4153.2 (2)
Cd1—O1—C1—C2166.3 (2)C3—C4—C5—C60.7 (4)
Cd1i—O2—C1—O193.0 (2)C3—C4—C5—O3177.4 (2)
Cd1i—O2—C1—C288.5 (2)O3—C5—C6—C7177.6 (2)
O1—C1—C2—C71.3 (3)C4—C5—C6—C71.2 (4)
O2—C1—C2—C7177.2 (2)C5—C6—C7—C20.3 (4)
O1—C1—C2—C3179.5 (2)C3—C2—C7—C61.1 (4)
O2—C1—C2—C32.0 (3)C1—C2—C7—C6179.6 (2)
Symmetry codes: (i) x+1, y+1, z; (ii) x+1/2, y, z; (iii) x1/2, y+1, z; (iv) x+3/2, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H1W···O2v0.85 (1)1.87 (1)2.690 (3)161 (2)
Symmetry code: (v) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Cd(C14H8O5)(H2O)]
Mr386.62
Crystal system, space groupMonoclinic, P2/a
Temperature (K)298
a, b, c (Å)7.307 (3), 6.453 (3), 14.423 (8)
β (°) 101.83 (3)
V3)665.6 (6)
Z2
Radiation typeMo Kα
µ (mm1)1.67
Crystal size (mm)0.45 × 0.33 × 0.27
Data collection
DiffractometerSiemens R3m four-circle
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.408, 0.433
No. of measured, independent and
observed [I > 2σ(I)] reflections
2078, 1939, 1776
Rint0.017
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.025, 0.067, 1.05
No. of reflections1939
No. of parameters101
No. of restraints2
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.43, 0.58

Computer programs: XSCANS (Siemens, 1990), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
Cd1—O12.198 (2)Cd1—O1W2.231 (3)
Cd1—O2i2.394 (2)
O1—Cd1—O1ii157.4 (1)O1—Cd1—O2iii85.1 (1)
O1—Cd1—O1W101.3 (1)O2i—Cd1—O1W86.2 (1)
O1—Cd1—O2i96.4 (1)O2i—Cd1—O2iii172.4 (1)
Symmetry codes: (i) x+1, y+1, z; (ii) x+1/2, y, z; (iii) x1/2, y+1, z.
 

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