supplementary materials
Diaquabis(4-methylbenzoato-![[kappa]](/logos/entities/kappa_rmgif.gif)
2O,O')cadmium(II)
In the title mononuclear complex, [Cd(C8H7O2)2(H2O)2], the CdII atom possesses crystallographically imposed C2 site symmetry, and is coordinated by four O atoms from two 4-methylbenzoate ligands and two water molecules, displaying a distorted octahedral geometry. The molecules are assembled via intermolecular O-H
O hydrogen-bond interactions into a supramolecular architecture.
A mixture of cadmium chloride(183 mg, 1 mmol), 4-methylbenzoic acid (136 mg, 1 mmol), NaOH (60 mg, 1.5 mmol) and H2O (12 ml) was placed in a 23 ml Teflon
reactor, which was heated to 433 K for three days and then cooled to room
temperature at a rate of 10 K h-1. The crystals obtained were washed with
water and dryed in air.
Carbon-bound H atoms were placed at calculated positions and were treated as
riding on the parent C atoms with C—H = 0.93 Å, and with Uiso(H)
= 1.2 Ueq(C). Water H atoms were tentatively located in difference
Fourier maps and were refined with distance restraints of O–H = 0.82 Å and
H···H = 1.29 Å, each within a standard deviation of 0.01 Å and and with
Uiso(H) = 1.5 Ueq(O).
Data collection: APEXII (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker, 2004); software used to prepare material for publication: XP (Bruker, 2004).
Diaquabis(4-methylbenzoato-
κ2O,
O')cadmium(II)
top
Crystal data top
| [Cd(C8H7O2)2(H2O)2] | F000 = 840 |
| Mr = 418.70 | Dx = 1.698 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation
λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 3600 reflections |
| a = 26.5836 (8) Å | θ = 1.4–28º |
| b = 5.3542 (1) Å | µ = 1.36 mm−1 |
| c = 12.0625 (3) Å | T = 296 (2) K |
| β = 107.414 (3)º | Block, colorless |
| V = 1638.21 (8) Å3 | 0.28 × 0.26 × 0.24 mm |
| Z = 4 | |
Data collection top
Bruker APEXII
diffractometer | 1528 independent reflections |
| Radiation source: fine-focus sealed tube | 1462 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.026 |
| Detector resolution: 10 pixels mm-1 | θmax = 25.5º |
| T = 296(2) K | θmin = 1.6º |
| φ and ω scans | h = −32→32 |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | k = −6→6 |
| Tmin = 0.702, Tmax = 0.736 | l = −14→14 |
| 7419 measured reflections | |
Refinement top
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.024 | H-atom parameters constrained |
| wR(F2) = 0.062 | w = 1/[σ2(Fo2) + (0.0402P)2 + 0.1795P]
where P = (Fo2 + 2Fc2)/3 |
| S = 1.19 | (Δ/σ)max < 0.001 |
| 1528 reflections | Δρmax = 0.30 e Å−3 |
| 106 parameters | Δρmin = −0.74 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
Crystal data top
| [Cd(C8H7O2)2(H2O)2] | V = 1638.21 (8) Å3 |
| Mr = 418.70 | Z = 4 |
| Monoclinic, C2/c | Mo Kα |
| a = 26.5836 (8) Å | µ = 1.36 mm−1 |
| b = 5.3542 (1) Å | T = 296 (2) K |
| c = 12.0625 (3) Å | 0.28 × 0.26 × 0.24 mm |
| β = 107.414 (3)º | |
Data collection top
Bruker APEXII
diffractometer | 1528 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | 1462 reflections with I > 2σ(I) |
| Tmin = 0.702, Tmax = 0.736 | Rint = 0.026 |
| 7419 measured reflections | |
Refinement top
| R[F2 > 2σ(F2)] = 0.024 | 106 parameters |
| wR(F2) = 0.062 | H-atom parameters constrained |
| S = 1.19 | Δρmax = 0.30 e Å−3 |
| 1528 reflections | Δρmin = −0.74 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| | x | y | z | Uiso*/Ueq | |
| Cd | 1.0000 | 0.07846 (3) | 0.7500 | 0.03171 (11) | |
| O1 | 0.93430 (7) | 0.3608 (3) | 0.71337 (13) | 0.0357 (3) | |
| O2 | 0.95598 (6) | 0.2636 (3) | 0.55703 (12) | 0.0396 (4) | |
| O1W | 1.03133 (8) | −0.2139 (3) | 0.66052 (13) | 0.0501 (5) | |
| H1W | 1.0312 | −0.2214 | 0.5943 | 0.075* | |
| H2W | 1.0438 | −0.3428 | 0.6915 | 0.075* | |
| C1 | 0.92908 (9) | 0.3898 (4) | 0.60582 (19) | 0.0311 (5) | |
| C2 | 0.89107 (10) | 0.5837 (4) | 0.5416 (2) | 0.0324 (5) | |
| C3 | 0.89229 (10) | 0.6742 (5) | 0.4358 (2) | 0.0454 (6) | |
| H3 | 0.9174 | 0.6137 | 0.4031 | 0.054* | |
| C4 | 0.85694 (11) | 0.8530 (6) | 0.3773 (2) | 0.0489 (6) | |
| H4 | 0.8582 | 0.9083 | 0.3051 | 0.059* | |
| C5 | 0.81971 (11) | 0.9516 (5) | 0.4240 (2) | 0.0434 (6) | |
| C6 | 0.81879 (12) | 0.8613 (6) | 0.5309 (3) | 0.0565 (7) | |
| H6 | 0.7938 | 0.9232 | 0.5638 | 0.068* | |
| C7 | 0.85403 (10) | 0.6813 (6) | 0.5901 (2) | 0.0477 (6) | |
| H7 | 0.8529 | 0.6257 | 0.6623 | 0.057* | |
| C8 | 0.78203 (12) | 1.1528 (6) | 0.3609 (3) | 0.0601 (7) | |
| H8A | 0.7485 | 1.1303 | 0.3745 | 0.090* | |
| H8B | 0.7776 | 1.1418 | 0.2791 | 0.090* | |
| H8C | 0.7960 | 1.3138 | 0.3890 | 0.090* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Cd | 0.04502 (18) | 0.02220 (15) | 0.03014 (15) | 0.000 | 0.01461 (11) | 0.000 |
| O1 | 0.0501 (10) | 0.0346 (7) | 0.0261 (8) | 0.0036 (7) | 0.0173 (7) | 0.0045 (6) |
| O2 | 0.0552 (10) | 0.0377 (8) | 0.0283 (7) | 0.0131 (7) | 0.0162 (7) | 0.0004 (6) |
| O1W | 0.0907 (14) | 0.0338 (9) | 0.0352 (8) | 0.0196 (9) | 0.0329 (9) | 0.0057 (7) |
| C1 | 0.0400 (12) | 0.0263 (10) | 0.0283 (11) | −0.0038 (9) | 0.0122 (10) | −0.0043 (8) |
| C2 | 0.0378 (13) | 0.0327 (13) | 0.0272 (11) | 0.0011 (8) | 0.0103 (10) | −0.0027 (8) |
| C3 | 0.0589 (16) | 0.0480 (14) | 0.0371 (12) | 0.0187 (12) | 0.0264 (11) | 0.0090 (11) |
| C4 | 0.0630 (17) | 0.0490 (14) | 0.0395 (13) | 0.0171 (13) | 0.0226 (12) | 0.0120 (12) |
| C5 | 0.0429 (14) | 0.0393 (13) | 0.0417 (14) | 0.0073 (10) | 0.0029 (11) | −0.0040 (10) |
| C6 | 0.0528 (16) | 0.0713 (17) | 0.0522 (16) | 0.0241 (14) | 0.0261 (14) | 0.0045 (14) |
| C7 | 0.0494 (14) | 0.0644 (16) | 0.0358 (12) | 0.0155 (13) | 0.0225 (11) | 0.0068 (12) |
| C8 | 0.0557 (17) | 0.0515 (15) | 0.0629 (18) | 0.0172 (15) | 0.0021 (14) | 0.0002 (15) |
Geometric parameters (Å, °) top
| Cd—O1W | 2.202 (2) | C3—H3 | 0.9300 |
| Cd—O1 | 2.252 (2) | C4—C5 | 1.382 (4) |
| Cd—O2 | 2.478 (1) | C4—H4 | 0.9300 |
| Cd—C1 | 2.719 (2) | C5—C6 | 1.383 (4) |
| O1—C1 | 1.272 (3) | C5—C8 | 1.512 (4) |
| O2—C1 | 1.251 (3) | C6—C7 | 1.384 (4) |
| O1W—H1W | 0.7994 | C6—H6 | 0.9300 |
| O1W—H2W | 0.8075 | C7—H7 | 0.9300 |
| C1—C2 | 1.493 (3) | C8—H8A | 0.9600 |
| C2—C3 | 1.375 (3) | C8—H8B | 0.9600 |
| C2—C7 | 1.389 (3) | C8—H8C | 0.9600 |
| C3—C4 | 1.379 (4) | | |
| | | |
| O1W—Cd—O1Wi | 89.36 (9) | O1—C1—Cd | 55.3 (1) |
| O1W—Cd—O1i | 100.87 (7) | C2—C1—Cd | 171.8 (2) |
| O1W—Cd—O1 | 140.02 (6) | C3—C2—C7 | 118.3 (2) |
| O1i—Cd—O1 | 95.64 (9) | C3—C2—C1 | 121.8 (2) |
| O1W—Cd—O2i | 127.11 (6) | C7—C2—C1 | 119.9 (2) |
| O1—Cd—O2i | 92.08 (6) | C2—C3—C4 | 121.2 (2) |
| O1W—Cd—O2 | 88.02 (5) | C2—C3—H3 | 119.4 |
| O1—Cd—O2 | 55.00 (5) | C4—C3—H3 | 119.4 |
| O2i—Cd—O2 | 132.83 (7) | C3—C4—C5 | 121.2 (2) |
| O1W—Cd—C1i | 117.25 (7) | C3—C4—H4 | 119.4 |
| O1i—Cd—C1i | 27.66 (6) | C5—C4—H4 | 119.4 |
| O1—Cd—C1i | 93.58 (6) | C4—C5—C6 | 117.4 (2) |
| O2i—Cd—C1i | 27.36 (6) | C4—C5—C8 | 120.9 (3) |
| O2—Cd—C1i | 113.43 (6) | C6—C5—C8 | 121.6 (3) |
| O1W—Cd—C1 | 114.45 (6) | C5—C6—C7 | 121.7 (2) |
| O1—Cd—C1 | 27.66 (6) | C5—C6—H6 | 119.1 |
| O2—Cd—C1 | 27.36 (6) | C7—C6—H6 | 119.1 |
| C1i—Cd—C1 | 104.39 (9) | C6—C7—C2 | 120.0 (2) |
| C1—O1—Cd | 97.09 (13) | C6—C7—H7 | 120.0 |
| C1—O2—Cd | 87.13 (13) | C2—C7—H7 | 120.0 |
| Cd—O1W—H1W | 129.6 | C5—C8—H8A | 109.5 |
| Cd—O1W—H2W | 123.0 | C5—C8—H8B | 109.5 |
| H1W—O1W—H2W | 107.3 | H8A—C8—H8B | 109.5 |
| O2—C1—O1 | 120.7 (2) | C5—C8—H8C | 109.5 |
| O2—C1—C2 | 121.6 (2) | H8A—C8—H8C | 109.5 |
| O1—C1—C2 | 117.7 (2) | H8B—C8—H8C | 109.5 |
| O2—C1—Cd | 65.5 (2) | | |
| | | |
| O1W—Cd—O1—C1 | −27.42 (18) | C1i—Cd—C1—O2 | 113.42 (14) |
| O1Wi—Cd—O1—C1 | −129.62 (13) | O1W—Cd—C1—O1 | 161.03 (13) |
| O1i—Cd—O1—C1 | 86.96 (13) | O1Wi—Cd—C1—O1 | 58.30 (15) |
| O2i—Cd—O1—C1 | 141.99 (13) | O1i—Cd—C1—O1 | −95.31 (15) |
| O2—Cd—O1—C1 | −1.63 (12) | O2i—Cd—C1—O1 | −42.12 (15) |
| C1i—Cd—O1—C1 | 114.64 (14) | O2—Cd—C1—O1 | 177.1 (2) |
| O1W—Cd—O2—C1 | 165.40 (14) | C1i—Cd—C1—O1 | −69.48 (13) |
| O1Wi—Cd—O2—C1 | 77.70 (14) | O2—C1—C2—C3 | −15.4 (4) |
| O1i—Cd—O2—C1 | −93.79 (13) | O1—C1—C2—C3 | 162.9 (2) |
| O1—Cd—O2—C1 | 1.64 (12) | O2—C1—C2—C7 | 166.1 (2) |
| O2i—Cd—O2—C1 | −52.29 (12) | O1—C1—C2—C7 | −15.6 (3) |
| C1i—Cd—O2—C1 | −75.63 (17) | C7—C2—C3—C4 | −1.6 (4) |
| Cd—O2—C1—O1 | −2.8 (2) | C1—C2—C3—C4 | 179.9 (2) |
| Cd—O2—C1—C2 | 175.45 (19) | C2—C3—C4—C5 | 1.4 (5) |
| Cd—O1—C1—O2 | 3.1 (2) | C3—C4—C5—C6 | −0.9 (5) |
| Cd—O1—C1—C2 | −175.22 (17) | C3—C4—C5—C8 | 178.3 (3) |
| O1W—Cd—C1—O2 | −16.06 (15) | C4—C5—C6—C7 | 0.8 (5) |
| O1Wi—Cd—C1—O2 | −118.79 (13) | C8—C5—C6—C7 | −178.5 (3) |
| O1i—Cd—C1—O2 | 87.59 (13) | C5—C6—C7—C2 | −1.0 (5) |
| O1—Cd—C1—O2 | −177.1 (2) | C3—C2—C7—C6 | 1.4 (4) |
| O2i—Cd—C1—O2 | 140.78 (11) | C1—C2—C7—C6 | 179.9 (3) |
| Symmetry codes: (i) −x+2, y, −z+3/2. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H2W···O1ii | 0.81 | 1.94 | 2.739 (2) | 169 |
| O1W—H1W···O2iii | 0.80 | 1.97 | 2.757 (2) | 170 |
| Symmetry codes: (ii) −x+2, y−1, −z+3/2; (iii) −x+2, −y, −z+1. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1W—H2W···O1i | 0.81 | 1.94 | 2.739 (2) | 169 |
| O1W—H1W···O2ii | 0.80 | 1.97 | 2.757 (2) | 170 |
| Symmetry codes: (i) −x+2, y−1, −z+3/2; (ii) −x+2, −y, −z+1. |
The authors acknowledge Guang Dong Ocean University for supporting this work.
Bruker (2004). APEXII (Version 7.23A), SAINT (Version 7.23A) and XP (Version ?). Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.
Song, W.-D., Gu, C.-S., Hao, X.-M. & Liu, J.-W. (2007). Acta Cryst. E63, m1023–m1024.
![[Figure 1]](./lx2040fig1thm.gif)
![[Figure 2]](./lx2040fig2thm.gif)
In the structural investigation of 4-methylbenzate complexes, it has been found that the 4-methylbenzoic acid functions as a multidentate ligand (Song et al. 2007), with versatile binding and coordination modes. In this paper, we report the crystal structure of the title compound (Fig. 1), a new Cd complex obtained by the reaction of 4-methylbenzoic acid with cadmium chloride in alkaline aqueous solution.
As illustrated in Fig. 1, the CdII atom, possesses crystallogarphically imposed C2 symmetry, which is coordinated by four O atoms from two 4-methylbenzate ligands and two water molecules, and displaying a distorted octahedral geometry. Intermolecular O—H···O hydrogen bond interactions (Table 1) between the coordinated water molecules and the carboxyl O atoms of 4-methylbenzate ligands stabilize the structural packing (Fig. 2).