Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102006352/sk1548sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102006352/sk1548Isup2.hkl |
CCDC reference: 188591
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.
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).
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.
[Cd(C14H8O5)(H2O)] | F(000) = 380 |
Mr = 386.62 | Dx = 1.929 Mg m−3 |
Monoclinic, P2/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ya | Cell parameters from 25 reflections |
a = 7.307 (3) Å | θ = 7.5–15° |
b = 6.453 (3) Å | µ = 1.67 mm−1 |
c = 14.423 (8) Å | T = 298 K |
β = 101.83 (3)° | Block, colorless |
V = 665.6 (6) Å3 | 0.45 × 0.33 × 0.27 mm |
Z = 2 |
Siemens R3m four-circle diffractometer | 1776 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 30.0°, θmin = 3.2° |
ω scans | h = 0→10 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→9 |
Tmin = 0.408, Tmax = 0.433 | l = −20→19 |
2078 measured reflections | 2 standard reflections every 200 reflections |
1939 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.067 | H 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 parameters | Δρmax = 0.43 e Å−3 |
2 restraints | Δρmin = −0.58 e Å−3 |
[Cd(C14H8O5)(H2O)] | V = 665.6 (6) Å3 |
Mr = 386.62 | Z = 2 |
Monoclinic, P2/a | Mo Kα radiation |
a = 7.307 (3) Å | µ = 1.67 mm−1 |
b = 6.453 (3) Å | T = 298 K |
c = 14.423 (8) Å | 0.45 × 0.33 × 0.27 mm |
β = 101.83 (3)° |
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 = 0.433 | 2 standard reflections every 200 reflections |
2078 measured reflections | intensity decay: none |
1939 independent reflections |
R[F2 > 2σ(F2)] = 0.025 | 2 restraints |
wR(F2) = 0.067 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.43 e Å−3 |
1939 reflections | Δρmin = −0.58 e Å−3 |
101 parameters |
x | y | z | Uiso*/Ueq | ||
Cd1 | 0.2500 | 0.65799 (3) | 0.0000 | 0.02996 (8) | |
O1 | 0.4021 (3) | 0.5911 (4) | 0.1448 (1) | 0.0516 (5) | |
O2 | 0.4801 (3) | 0.3173 (3) | 0.0695 (1) | 0.0387 (4) | |
O3 | 0.7500 | 0.0281 (4) | 0.5000 | 0.0396 (5) | |
O1W | 0.2500 | 1.0036 (4) | 0.0000 | 0.069 (1) | |
C1 | 0.4729 (3) | 0.4141 (4) | 0.1457 (2) | 0.0330 (4) | |
C2 | 0.5458 (3) | 0.3144 (3) | 0.2398 (2) | 0.0302 (4) | |
C3 | 0.6278 (3) | 0.1179 (4) | 0.2457 (2) | 0.0333 (4) | |
C4 | 0.6979 (3) | 0.0275 (4) | 0.3334 (1) | 0.0331 (4) | |
C5 | 0.6837 (3) | 0.1336 (3) | 0.4158 (2) | 0.0315 (4) | |
C6 | 0.5988 (4) | 0.3267 (4) | 0.4109 (2) | 0.0384 (5) | |
C7 | 0.5304 (3) | 0.4173 (4) | 0.3231 (2) | 0.0353 (5) | |
H1W | 0.342 (2) | 1.081 (3) | 0.025 (2) | 0.06 (1)* | |
H3 | 0.6356 | 0.0469 | 0.1906 | 0.040* | |
H4 | 0.7538 | −0.1026 | 0.3370 | 0.040* | |
H6 | 0.5877 | 0.3954 | 0.4662 | 0.046* | |
H7 | 0.4740 | 0.5470 | 0.3199 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd1 | 0.0379 (1) | 0.0271 (1) | 0.0237 (1) | 0.000 | 0.0035 (1) | 0.000 |
O1 | 0.058 (1) | 0.060 (1) | 0.036 (1) | 0.027 (1) | 0.006 (1) | 0.014 (1) |
O2 | 0.044 (1) | 0.047 (1) | 0.023 (1) | −0.013 (1) | 0.002 (1) | 0.002 (1) |
O3 | 0.057 (1) | 0.036 (1) | 0.020 (1) | 0.000 | −0.006 (1) | 0.000 |
O1W | 0.059 (2) | 0.025 (1) | 0.104 (3) | 0.000 | −0.027 (2) | 0.000 |
C1 | 0.027 (1) | 0.043 (1) | 0.027 (1) | 0.000 (1) | 0.002 (1) | 0.008 (1) |
C2 | 0.028 (1) | 0.037 (1) | 0.024 (1) | 0.003 (1) | 0.001 (1) | 0.002 (1) |
C3 | 0.040 (1) | 0.037 (1) | 0.022 (1) | 0.003 (1) | 0.005 (1) | −0.004 (1) |
C4 | 0.040 (1) | 0.033 (1) | 0.024 (1) | 0.006 (1) | 0.001 (1) | 0.000 (1) |
C5 | 0.033 (1) | 0.038 (1) | 0.020 (1) | 0.001 (1) | −0.001 (1) | 0.001 (1) |
C6 | 0.043 (1) | 0.046 (1) | 0.024 (1) | 0.009 (1) | 0.002 (1) | −0.006 (1) |
C7 | 0.037 (1) | 0.036 (1) | 0.030 (1) | 0.009 (1) | 0.002 (1) | −0.002 (1) |
Cd1—O1 | 2.198 (2) | C3—C4 | 1.392 (3) |
Cd1—O2i | 2.394 (2) | C4—C5 | 1.394 (3) |
Cd1—O1W | 2.231 (3) | C5—C6 | 1.387 (3) |
O1—C1 | 1.253 (3) | C6—C7 | 1.391 (3) |
O2—C1 | 1.275 (3) | O1W—H1W | 0.85 (1) |
O3—C5 | 1.389 (2) | C3—H3 | 0.93 |
C1—C2 | 1.497 (3) | C4—H4 | 0.93 |
C2—C7 | 1.398 (3) | C6—H6 | 0.93 |
C2—C3 | 1.397 (3) | C7—H7 | 0.93 |
O1—Cd1—O1ii | 157.4 (1) | C3—C2—C1 | 120.9 (2) |
O1—Cd1—O1W | 101.3 (1) | C4—C3—C2 | 120.6 (2) |
O1—Cd1—O2i | 96.4 (1) | C3—C4—C5 | 119.4 (2) |
O1—Cd1—O2iii | 85.1 (1) | C6—C5—O3 | 123.8 (2) |
O1ii—Cd1—O1W | 101.3 (1) | C6—C5—C4 | 120.6 (2) |
O1ii—Cd1—O2i | 85.1 (1) | O3—C5—C4 | 115.5 (2) |
O1ii—Cd1—O2iii | 96.4 (1) | C5—C6—C7 | 119.8 (2) |
O2i—Cd1—O1W | 86.2 (1) | C6—C7—C2 | 120.4 (2) |
O2i—Cd1—O2iii | 172.4 (1) | Cd1—O1W—H1W | 126 (1) |
O2iii—Cd1—O1W | 86.2 (1) | C4—C3—H3 | 119.7 |
C1—O1—Cd1 | 108.5 (2) | C2—C3—H3 | 119.7 |
C1—O2—Cd1i | 120.8 (1) | C3—C4—H4 | 120.3 |
C5—O3—C5iv | 121.4 (3) | C5—C4—H4 | 120.3 |
O1—C1—O2 | 121.8 (2) | C5—C6—H6 | 120.1 |
O1—C1—C2 | 118.1 (2) | C7—C6—H6 | 120.1 |
O2—C1—C2 | 120.1 (2) | C6—C7—H7 | 119.8 |
C7—C2—C3 | 119.2 (2) | C2—C7—H7 | 119.8 |
C7—C2—C1 | 119.9 (2) | ||
O1ii—Cd1—O1—C1 | 24.0 (2) | C7—C2—C3—C4 | −1.7 (3) |
O1W—Cd1—O1—C1 | −156.0 (2) | C1—C2—C3—C4 | 179.0 (2) |
O2i—Cd1—O1—C1 | −68.6 (2) | C2—C3—C4—C5 | 0.8 (4) |
O2iii—Cd1—O1—C1 | 118.9 (2) | C5iv—O3—C5—C6 | −30.3 (2) |
Cd1—O1—C1—O2 | 12.2 (3) | C5iv—O3—C5—C4 | 153.2 (2) |
Cd1—O1—C1—C2 | −166.3 (2) | C3—C4—C5—C6 | 0.7 (4) |
Cd1i—O2—C1—O1 | 93.0 (2) | C3—C4—C5—O3 | 177.4 (2) |
Cd1i—O2—C1—C2 | −88.5 (2) | O3—C5—C6—C7 | −177.6 (2) |
O1—C1—C2—C7 | 1.3 (3) | C4—C5—C6—C7 | −1.2 (4) |
O2—C1—C2—C7 | −177.2 (2) | C5—C6—C7—C2 | 0.3 (4) |
O1—C1—C2—C3 | −179.5 (2) | C3—C2—C7—C6 | 1.1 (4) |
O2—C1—C2—C3 | 2.0 (3) | C1—C2—C7—C6 | −179.6 (2) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1/2, y, −z; (iii) x−1/2, −y+1, z; (iv) −x+3/2, y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W···O2v | 0.85 (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)] |
Mr | 386.62 |
Crystal system, space group | Monoclinic, P2/a |
Temperature (K) | 298 |
a, b, c (Å) | 7.307 (3), 6.453 (3), 14.423 (8) |
β (°) | 101.83 (3) |
V (Å3) | 665.6 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.67 |
Crystal size (mm) | 0.45 × 0.33 × 0.27 |
Data collection | |
Diffractometer | Siemens R3m four-circle diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.408, 0.433 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2078, 1939, 1776 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.067, 1.05 |
No. of reflections | 1939 |
No. of parameters | 101 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.58 |
Computer programs: XSCANS (Siemens, 1990), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Cd1—O1 | 2.198 (2) | Cd1—O1W | 2.231 (3) |
Cd1—O2i | 2.394 (2) | ||
O1—Cd1—O1ii | 157.4 (1) | O1—Cd1—O2iii | 85.1 (1) |
O1—Cd1—O1W | 101.3 (1) | O2i—Cd1—O1W | 86.2 (1) |
O1—Cd1—O2i | 96.4 (1) | O2i—Cd1—O2iii | 172.4 (1) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1/2, y, −z; (iii) x−1/2, −y+1, z. |
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].