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

Huang, X.-H.; Hong, P.-Z.; Song, W.-D.

doi:10.1107/S1600536807066044

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page m175

https://doi.org/10.1107/S1600536807066044

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

Xiang-Hu Huang,^a Peng-Zhi Hong ^b and Wen-Dong Song ^c ^*

^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 Cd^II 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 ).

Experimental

Crystal data

[Cd(C₈H₇O₂)₂(H₂O)₂]
M_r = 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 ) T_min = 0.702, T_max = 0.736
7419 measured reflections
1528 independent reflections
1462 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.062
S = 1.19
1528 reflections
106 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+2, y-1, -z+{\script{3\over 2}}]$ ; (ii) -x+2, -y, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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: SHELXL97 and XP.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807066044/lx2040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066044/lx2040Isup2.hkl

checkCIF report

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 Cd^II 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.

Structure description top

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

	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.]
	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
M_r = 418.70	D_x = 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 = 1.4–28°
b = 5.3542 (1) Å	µ = 1.36 mm⁻¹
c = 12.0625 (3) Å	T = 296 K
β = 107.414 (3)°	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)
Graphite monochromator	R_int = 0.026
Detector resolution: 10 pixels mm^-1	θ_max = 25.5°, θ_min = 1.6°
φ and ω scans	h = −32→32
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −6→6
T_min = 0.702, T_max = 0.736	l = −14→14
7419 measured reflections

Refinement top

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H-atom parameters constrained
S = 1.19	w = 1/[σ²(F_o²) + (0.0402P)² + 0.1795P] where P = (F_o² + 2F_c²)/3
1528 reflections	(Δ/σ)_max < 0.001
106 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

[Cd(C₈H₇O₂)₂(H₂O)₂]	V = 1638.21 (8) Å³
M_r = 418.70	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 26.5836 (8) Å	µ = 1.36 mm⁻¹
b = 5.3542 (1) Å	T = 296 K
c = 12.0625 (3) Å	0.28 × 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)
T_min = 0.702, T_max = 0.736	R_int = 0.026
7419 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.062	H-atom parameters constrained
S = 1.19	Δρ_max = 0.30 e Å⁻³
1528 reflections	Δρ_min = −0.74 e Å⁻³
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

	x	y	z	U_iso*/U_eq
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, º) 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 code: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) 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.

Experimental details

Crystal data
Chemical formula	[Cd(C₈H₇O₂)₂(H₂O)₂]
M_r	418.70
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	26.5836 (8), 5.3542 (1), 12.0625 (3)
β (°)	107.414 (3)
V (Å³)	1638.21 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.36
Crystal size (mm)	0.28 × 0.26 × 0.24

Data collection
Diffractometer	Bruker APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.702, 0.736
No. of measured, independent and observed [I > 2σ(I)] reflections	7419, 1528, 1462
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.062, 1.19
No. of reflections	1528
No. of parameters	106
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O1ⁱ	0.81	1.94	2.739 (2)	168.7
O1W—H1W···O2ⁱⁱ	0.80	1.97	2.757 (2)	169.6

Symmetry codes: (i) −x+2, y−1, −z+3/2; (ii) −x+2, −y, −z+1.

Acknowledgements

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

References

Bruker (2004). APEX2, SAINT and XP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar
Song, 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