metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Di­aqua­bis­(4-methyl­benzoato-κ2O,O′)cadmium(II)

aCollege of Fisheries, Guang Dong Ocean University, Zhan Jiang 524088, People's Republic of China, bSchool of Food Science and Technology, Guang Dong Ocean University, Zhan Jiang 524088, People's Republic of China, and cCollege of Science, Guang Dong Ocean University, Zhanjiang 524088, People's Republic of China
*Correspondence e-mail: songwd60@126.com

(Received 19 November 2007; accepted 7 December 2007; online 12 December 2007)

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.

Related literature

For the crystal structure of 4-methyl­benzoic acid, see: Song et al. (2007[Song, W.-D., Gu, C.-S., Hao, X.-M. & Liu, J.-W. (2007). Acta Cryst. E63, m1023-m1024.]).

[Scheme 1]

Experimental

Crystal data
  • [Cd(C8H7O2)2(H2O)2]

  • Mr = 418.70

  • Monoclinic, C 2/c

  • a = 26.5836 (8) Å

  • b = 5.3542 (1) Å

  • c = 12.0625 (3) Å

  • β = 107.414 (3)°

  • V = 1638.21 (8) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.36 mm−1

  • T = 296 (2) K

  • 0.28 × 0.26 × 0.24 mm

Data collection
  • Bruker APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.702, Tmax = 0.736

  • 7419 measured reflections

  • 1528 independent reflections

  • 1462 reflections with I > 2σ(I)

  • Rint = 0.026

Refinement
  • R[F2 > 2σ(F2)] = 0.024

  • wR(F2) = 0.062

  • S = 1.19

  • 1528 reflections

  • 106 parameters

  • H-atom parameters constrained

  • Δρmax = 0.30 e Å−3

  • Δρmin = −0.74 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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+{\script{3\over 2}}]; (ii) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2, SAINT and XP. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2, SAINT and XP. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.]); molecular graphics: XP (Bruker, 2004[Bruker (2004). APEX2, SAINT and XP. Bruker AXS Inc., Madison, Wisconsin, USA.]); software used to prepare material for publication: SHELXL97 and XP.

Supporting information


Comment top

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).

Related literature top

For the crystal structure of 4-methylbenzoic acid, see: Song et al. (2007).

Experimental top

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.

Refinement top

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).

Structure description top

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).

For the crystal structure of 4-methylbenzoic acid, see: Song et al. (2007).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, showing the atomic numbering scheme. Non-H atoms are shown with 30% probability displacement ellipsoids. [Symmetry code: (i) 2 - x, y, -z + 3/2.]
[Figure 2] Fig. 2. A packing view of the title compound. The intermolecluar hydrogen bonds are shown as dashed lines.
Diaquabis(4-methylbenzoato-κ2O,O')cadmium(II) top
Crystal data top
[Cd(C8H7O2)2(H2O)2]F(000) = 840
Mr = 418.70Dx = 1.698 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3600 reflections
a = 26.5836 (8) Åθ = 1.4–28°
b = 5.3542 (1) ŵ = 1.36 mm1
c = 12.0625 (3) ÅT = 296 K
β = 107.414 (3)°Block, colorless
V = 1638.21 (8) Å30.28 × 0.26 × 0.24 mm
Z = 4
Data collection top
Bruker APEXII
diffractometer
1528 independent reflections
Radiation source: fine-focus sealed tube1462 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
Detector resolution: 10 pixels mm-1θmax = 25.5°, θmin = 1.6°
φ and ω scansh = 3232
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
k = 66
Tmin = 0.702, Tmax = 0.736l = 1414
7419 measured reflections
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)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.062H-atom parameters constrained
S = 1.19 w = 1/[σ2(Fo2) + (0.0402P)2 + 0.1795P]
where P = (Fo2 + 2Fc2)/3
1528 reflections(Δ/σ)max < 0.001
106 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = 0.74 e Å3
Crystal data top
[Cd(C8H7O2)2(H2O)2]V = 1638.21 (8) Å3
Mr = 418.70Z = 4
Monoclinic, C2/cMo Kα radiation
a = 26.5836 (8) ŵ = 1.36 mm1
b = 5.3542 (1) ÅT = 296 K
c = 12.0625 (3) Å0.28 × 0.26 × 0.24 mm
β = 107.414 (3)°
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 = 0.736Rint = 0.026
7419 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.062H-atom parameters constrained
S = 1.19Δρmax = 0.30 e Å3
1528 reflectionsΔρmin = 0.74 e Å3
106 parameters
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
Cd1.00000.07846 (3)0.75000.03171 (11)
O10.93430 (7)0.3608 (3)0.71337 (13)0.0357 (3)
O20.95598 (6)0.2636 (3)0.55703 (12)0.0396 (4)
O1W1.03133 (8)0.2139 (3)0.66052 (13)0.0501 (5)
H1W1.03120.22140.59430.075*
H2W1.04380.34280.69150.075*
C10.92908 (9)0.3898 (4)0.60582 (19)0.0311 (5)
C20.89107 (10)0.5837 (4)0.5416 (2)0.0324 (5)
C30.89229 (10)0.6742 (5)0.4358 (2)0.0454 (6)
H30.91740.61370.40310.054*
C40.85694 (11)0.8530 (6)0.3773 (2)0.0489 (6)
H40.85820.90830.30510.059*
C50.81971 (11)0.9516 (5)0.4240 (2)0.0434 (6)
C60.81879 (12)0.8613 (6)0.5309 (3)0.0565 (7)
H60.79380.92320.56380.068*
C70.85403 (10)0.6813 (6)0.5901 (2)0.0477 (6)
H70.85290.62570.66230.057*
C80.78203 (12)1.1528 (6)0.3609 (3)0.0601 (7)
H8A0.74851.13030.37450.090*
H8B0.77761.14180.27910.090*
H8C0.79601.31380.38900.090*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd0.04502 (18)0.02220 (15)0.03014 (15)0.0000.01461 (11)0.000
O10.0501 (10)0.0346 (7)0.0261 (8)0.0036 (7)0.0173 (7)0.0045 (6)
O20.0552 (10)0.0377 (8)0.0283 (7)0.0131 (7)0.0162 (7)0.0004 (6)
O1W0.0907 (14)0.0338 (9)0.0352 (8)0.0196 (9)0.0329 (9)0.0057 (7)
C10.0400 (12)0.0263 (10)0.0283 (11)0.0038 (9)0.0122 (10)0.0043 (8)
C20.0378 (13)0.0327 (13)0.0272 (11)0.0011 (8)0.0103 (10)0.0027 (8)
C30.0589 (16)0.0480 (14)0.0371 (12)0.0187 (12)0.0264 (11)0.0090 (11)
C40.0630 (17)0.0490 (14)0.0395 (13)0.0171 (13)0.0226 (12)0.0120 (12)
C50.0429 (14)0.0393 (13)0.0417 (14)0.0073 (10)0.0029 (11)0.0040 (10)
C60.0528 (16)0.0713 (17)0.0522 (16)0.0241 (14)0.0261 (14)0.0045 (14)
C70.0494 (14)0.0644 (16)0.0358 (12)0.0155 (13)0.0225 (11)0.0068 (12)
C80.0557 (17)0.0515 (15)0.0629 (18)0.0172 (15)0.0021 (14)0.0002 (15)
Geometric parameters (Å, º) top
Cd—O1W2.202 (2)C3—H30.9300
Cd—O12.252 (2)C4—C51.382 (4)
Cd—O22.478 (1)C4—H40.9300
Cd—C12.719 (2)C5—C61.383 (4)
O1—C11.272 (3)C5—C81.512 (4)
O2—C11.251 (3)C6—C71.384 (4)
O1W—H1W0.7994C6—H60.9300
O1W—H2W0.8075C7—H70.9300
C1—C21.493 (3)C8—H8A0.9600
C2—C31.375 (3)C8—H8B0.9600
C2—C71.389 (3)C8—H8C0.9600
C3—C41.379 (4)
O1W—Cd—O1Wi89.36 (9)O1—C1—Cd55.3 (1)
O1W—Cd—O1i100.87 (7)C2—C1—Cd171.8 (2)
O1W—Cd—O1140.02 (6)C3—C2—C7118.3 (2)
O1i—Cd—O195.64 (9)C3—C2—C1121.8 (2)
O1W—Cd—O2i127.11 (6)C7—C2—C1119.9 (2)
O1—Cd—O2i92.08 (6)C2—C3—C4121.2 (2)
O1W—Cd—O288.02 (5)C2—C3—H3119.4
O1—Cd—O255.00 (5)C4—C3—H3119.4
O2i—Cd—O2132.83 (7)C3—C4—C5121.2 (2)
O1W—Cd—C1i117.25 (7)C3—C4—H4119.4
O1i—Cd—C1i27.66 (6)C5—C4—H4119.4
O1—Cd—C1i93.58 (6)C4—C5—C6117.4 (2)
O2i—Cd—C1i27.36 (6)C4—C5—C8120.9 (3)
O2—Cd—C1i113.43 (6)C6—C5—C8121.6 (3)
O1W—Cd—C1114.45 (6)C5—C6—C7121.7 (2)
O1—Cd—C127.66 (6)C5—C6—H6119.1
O2—Cd—C127.36 (6)C7—C6—H6119.1
C1i—Cd—C1104.39 (9)C6—C7—C2120.0 (2)
C1—O1—Cd97.09 (13)C6—C7—H7120.0
C1—O2—Cd87.13 (13)C2—C7—H7120.0
Cd—O1W—H1W129.6C5—C8—H8A109.5
Cd—O1W—H2W123.0C5—C8—H8B109.5
H1W—O1W—H2W107.3H8A—C8—H8B109.5
O2—C1—O1120.7 (2)C5—C8—H8C109.5
O2—C1—C2121.6 (2)H8A—C8—H8C109.5
O1—C1—C2117.7 (2)H8B—C8—H8C109.5
O2—C1—Cd65.5 (2)
O1W—Cd—O1—C127.42 (18)C1i—Cd—C1—O2113.42 (14)
O1Wi—Cd—O1—C1129.62 (13)O1W—Cd—C1—O1161.03 (13)
O1i—Cd—O1—C186.96 (13)O1Wi—Cd—C1—O158.30 (15)
O2i—Cd—O1—C1141.99 (13)O1i—Cd—C1—O195.31 (15)
O2—Cd—O1—C11.63 (12)O2i—Cd—C1—O142.12 (15)
C1i—Cd—O1—C1114.64 (14)O2—Cd—C1—O1177.1 (2)
O1W—Cd—O2—C1165.40 (14)C1i—Cd—C1—O169.48 (13)
O1Wi—Cd—O2—C177.70 (14)O2—C1—C2—C315.4 (4)
O1i—Cd—O2—C193.79 (13)O1—C1—C2—C3162.9 (2)
O1—Cd—O2—C11.64 (12)O2—C1—C2—C7166.1 (2)
O2i—Cd—O2—C152.29 (12)O1—C1—C2—C715.6 (3)
C1i—Cd—O2—C175.63 (17)C7—C2—C3—C41.6 (4)
Cd—O2—C1—O12.8 (2)C1—C2—C3—C4179.9 (2)
Cd—O2—C1—C2175.45 (19)C2—C3—C4—C51.4 (5)
Cd—O1—C1—O23.1 (2)C3—C4—C5—C60.9 (5)
Cd—O1—C1—C2175.22 (17)C3—C4—C5—C8178.3 (3)
O1W—Cd—C1—O216.06 (15)C4—C5—C6—C70.8 (5)
O1Wi—Cd—C1—O2118.79 (13)C8—C5—C6—C7178.5 (3)
O1i—Cd—C1—O287.59 (13)C5—C6—C7—C21.0 (5)
O1—Cd—C1—O2177.1 (2)C3—C2—C7—C61.4 (4)
O2i—Cd—C1—O2140.78 (11)C1—C2—C7—C6179.9 (3)
Symmetry code: (i) x+2, y, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H2W···O1ii0.811.942.739 (2)169
O1W—H1W···O2iii0.801.972.757 (2)170
Symmetry codes: (ii) x+2, y1, z+3/2; (iii) x+2, y, z+1.

Experimental details

Crystal data
Chemical formula[Cd(C8H7O2)2(H2O)2]
Mr418.70
Crystal system, space groupMonoclinic, C2/c
Temperature (K)296
a, b, c (Å)26.5836 (8), 5.3542 (1), 12.0625 (3)
β (°) 107.414 (3)
V3)1638.21 (8)
Z4
Radiation typeMo Kα
µ (mm1)1.36
Crystal size (mm)0.28 × 0.26 × 0.24
Data collection
DiffractometerBruker APEXII
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.702, 0.736
No. of measured, independent and
observed [I > 2σ(I)] reflections
7419, 1528, 1462
Rint0.026
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.062, 1.19
No. of reflections1528
No. of parameters106
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.30, 0.74

Computer programs: APEXII (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Bruker, 2004).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1W—H2W···O1i0.811.942.739 (2)168.7
O1W—H1W···O2ii0.801.972.757 (2)169.6
Symmetry codes: (i) x+2, y1, z+3/2; (ii) x+2, y, z+1.
 

Acknowledgements

The authors acknowledge Guang Dong Ocean University for supporting this work.

References

First citationBruker (2004). APEX2, SAINT and XP. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany.  Google Scholar
First citationSong, W.-D., Gu, C.-S., Hao, X.-M. & Liu, J.-W. (2007). Acta Cryst. E63, m1023–m1024.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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