Poly[aqua­(μ5-2-oxido-4-sulfonato­benzoato)lanthanum(III)]

Zhu, C.-F.; Li, X.; Sheng, E.

doi:10.1107/S1600536809007879

metal-organic compounds

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Volume 65| Part 4| April 2009| Page m383

doi:10.1107/S1600536809007879

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Poly[aqua(μ₅-2-oxido-4-sulfonatobenzoato)lanthanum(III)]

Cheng-Feng Zhu,^a Xing Li ^b and Enhong Sheng ^a ^*

^aCollege of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241000, People's Republic of China, and ^bFaculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhengjiang 315211, People's Republic of China
^*Correspondence e-mail: shengeh@mail.ahnu.edu.cn

(Received 8 December 2008; accepted 4 March 2009; online 11 March 2009)

The title compound, [La(C₇H₃O₆S)(H₂O)]_n, forms a three-dimensional framework in which the asymmetric unit contains one La^III atom, one 5-sulfosalicylate (2-oxido-4-sulfonatobenzoate) ligand and one coordinated water molecule. The La^III atom is coordinated by nine O atoms from three carboxylate, three sulfonate and two hydroxyl groups, and one water molecule, forming a distorted trigonal-prismatic square-face tricapped geometry.

Related literature

For the use of rigid carboxylate ligands in the design and synthesis of a variety of structures, see: Cao et al. (2002 ); Li et al. (2004 , 2005 ). For the structure of the isotypic Nd compound, see: Wang et al. (2004 ).

Experimental

Crystal data

[La(C₇H₃O₆S)(H₂O)]
M_r = 372.08
Triclinic, $[P \overline 1]$
a = 6.2297 (7) Å
b = 8.2390 (8) Å
c = 9.9157 (9) Å
α = 111.587 (2)°
β = 94.325 (2)°
γ = 93.785 (2)°
V = 469.47 (8) Å³
Z = 2
Mo Kα radiation
μ = 4.79 mm⁻¹
T = 293 K
0.24 × 0.16 × 0.12 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.415, T_max = 0.563
2457 measured reflections
1633 independent reflections
1527 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.090
S = 1.07
1633 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.79 e Å⁻³
Δρ_min = −1.66 e Å⁻³

Table 1
Selected bond lengths (Å)

La1—O1ⁱ	2.676 (5)
La1—O2ⁱⁱ	2.449 (5)
La1—O2ⁱ	2.561 (5)
La1—O3ⁱⁱⁱ	2.478 (4)
La1—O3ⁱⁱ	2.499 (4)
La1—O4	2.573 (5)
La1—O5	2.970 (7)
La1—O6^iv	2.548 (5)
La1—O7	2.501 (5)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x, y, z+1; (iii) -x+2, -y+1, -z; (iv) -x+2, -y+2, -z+1.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1994 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809007879/is2373sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809007879/is2373Isup2.hkl

checkCIF report

Comment top

The carboxylate groups have a strong ability to bond various metal ions and afford abundant coordination modes, thus rigid carboxylate ligands have been widely used for the design and synthesis of a great variety of structures (Cao et al., 2002; Li et al., 2004). Introduction of a sulfonate group into rigid carboxylate ligands may result in the formation of unexpected frameworks as the sulfonic group has a different shape and properties in terms of its coordination ability compared to the carboxylate group (Li et al., 2005).

Studies on the coordination chemistry of mixed carboxylate-sulfonic ligands are not very common. By employing 5-sulfoisophthalic acid as an organic ligand, we have successfully prepared one new metal-organic polymer [La(C₇H₃O₆S)(H₂O)]_n with three dimensional framework by the bridging carboxylate and the sulfonate groups. Single X-ray diffraction analysis reveals that the title complex is isomorphous to the La-compound reported previously (Wang et al., 2004). As Fig. 1 shown, the lanthanum(III) atom is surrounded by nine oxygen atoms, of which three come from carboxylate groups, three from sulfonates, two from hydroxyl groups and one from the coordinated water. The sulfosalicylate ligands serve as µ₅-bridge linking five La(III) ions (Fig. 2), resulting in a three dimensional framework.

Related literature top

For the use of rigid carboxylate ligands in the design and synthesis of a variety of structures, see: Cao et al. (2002); Li et al. (2004, 2005). For the structure of an isomorphous La compound, see: Wang et al. (2004).

Experimental top

A mixture of 5-sulfosalicylic acid (0.60 mmol, 0.15 g), La₂O₃ (0.2 mmol, 0.065 g) and H₂O (15 ml) was sealed in a 25 ml stainless steel reactor with Teflon linear and heated 433 K for 72 h. After cooling to room temperature, colorless crystals were isolated by filtering (yield 35%).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the lanthanum ion coordination, Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The sulfosalicylate ligands linking fashion.

Poly[aqua(µ₅-2-oxido-4-sulfonatobenzoato)lanthanum(III)] top

Crystal data top

[La(C₇H₃O₆S)(H₂O)]	Z = 2
M_r = 372.08	F(000) = 352
Triclinic, P1	D_x = 2.632 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.2297 (7) Å	Cell parameters from 2088 reflections
b = 8.2390 (8) Å	θ = 2.2–25.1°
c = 9.9157 (9) Å	µ = 4.79 mm⁻¹
α = 111.587 (2)°	T = 293 K
β = 94.325 (2)°	Block, colorless
γ = 93.785 (2)°	0.24 × 0.16 × 0.12 mm
V = 469.47 (8) Å³

Data collection top

Siemens SMART CCD area-detector diffractometer	1633 independent reflections
Radiation source: fine-focus sealed tube	1527 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 25.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→7
T_min = 0.415, T_max = 0.563	k = −9→9
2457 measured reflections	l = −11→11

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.090	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0456P)² + 4.598P] where P = (F_o² + 2F_c²)/3
1633 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.79 e Å⁻³
0 restraints	Δρ_min = −1.66 e Å⁻³

Crystal data top

[La(C₇H₃O₆S)(H₂O)]	γ = 93.785 (2)°
M_r = 372.08	V = 469.47 (8) Å³
Triclinic, P1	Z = 2
a = 6.2297 (7) Å	Mo Kα radiation
b = 8.2390 (8) Å	µ = 4.79 mm⁻¹
c = 9.9157 (9) Å	T = 293 K
α = 111.587 (2)°	0.24 × 0.16 × 0.12 mm
β = 94.325 (2)°

Data collection top

Siemens SMART CCD area-detector diffractometer	1633 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1527 reflections with I > 2σ(I)
T_min = 0.415, T_max = 0.563	R_int = 0.029
2457 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.090	H-atom parameters constrained
S = 1.07	Δρ_max = 0.79 e Å⁻³
1633 reflections	Δρ_min = −1.66 e Å⁻³
145 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
La1	0.76441 (5)	0.64763 (5)	0.46004 (4)	0.01280 (16)
S1	0.9837 (3)	0.8865 (2)	0.28204 (17)	0.0167 (4)
O1	0.4823 (8)	0.4571 (7)	−0.2043 (5)	0.0258 (12)
O2	0.5737 (8)	0.5722 (7)	−0.3605 (5)	0.0215 (11)
O3	1.0224 (7)	0.6040 (6)	−0.3536 (5)	0.0139 (9)
O4	1.0612 (9)	0.7528 (6)	0.3353 (5)	0.0229 (11)
O5	0.7603 (9)	0.9023 (8)	0.3122 (6)	0.0360 (14)
O6	1.1278 (9)	1.0487 (6)	0.3439 (5)	0.0237 (11)
O7	0.4427 (9)	0.8190 (7)	0.5052 (7)	0.0332 (13)
H7A	0.3472	0.7722	0.4375	0.040*
H7B	0.4185	0.9029	0.5766	0.040*
C1	0.6163 (12)	0.5488 (9)	−0.2412 (7)	0.0181 (14)
C2	0.8185 (11)	0.6385 (9)	−0.1475 (7)	0.0150 (13)
C3	0.8153 (11)	0.7035 (9)	0.0033 (7)	0.0153 (13)
H3A	0.6938	0.6777	0.0437	0.018*
C4	0.9937 (11)	0.8069 (9)	0.0930 (7)	0.0168 (14)
C5	1.1779 (12)	0.8448 (10)	0.0340 (7)	0.0210 (15)
H5A	1.2964	0.9148	0.0953	0.025*
C6	1.1846 (11)	0.7790 (9)	−0.1142 (8)	0.0192 (14)
H6A	1.3085	0.8041	−0.1526	0.023*
C7	1.0069 (11)	0.6740 (8)	−0.2089 (7)	0.0141 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
La1	0.0098 (2)	0.0143 (2)	0.0121 (2)	−0.00092 (15)	0.00131 (14)	0.00277 (16)
S1	0.0185 (8)	0.0174 (8)	0.0098 (8)	−0.0033 (7)	0.0027 (6)	0.0005 (6)
O1	0.023 (3)	0.034 (3)	0.019 (3)	−0.016 (2)	−0.001 (2)	0.012 (2)
O2	0.017 (2)	0.031 (3)	0.016 (3)	−0.009 (2)	−0.005 (2)	0.012 (2)
O3	0.015 (2)	0.015 (2)	0.009 (2)	0.0004 (18)	0.0007 (18)	0.0012 (18)
O4	0.034 (3)	0.019 (2)	0.017 (3)	−0.002 (2)	0.005 (2)	0.009 (2)
O5	0.025 (3)	0.047 (4)	0.022 (3)	0.001 (3)	0.008 (2)	−0.004 (3)
O6	0.031 (3)	0.014 (2)	0.020 (3)	−0.010 (2)	−0.001 (2)	0.001 (2)
O7	0.023 (3)	0.030 (3)	0.037 (3)	0.010 (2)	0.003 (2)	0.000 (3)
C1	0.024 (4)	0.014 (3)	0.014 (3)	0.000 (3)	0.004 (3)	0.002 (3)
C2	0.014 (3)	0.018 (3)	0.014 (3)	0.004 (3)	0.003 (3)	0.005 (3)
C3	0.017 (3)	0.019 (3)	0.012 (3)	0.003 (3)	0.007 (3)	0.007 (3)
C4	0.022 (3)	0.018 (3)	0.008 (3)	−0.002 (3)	0.001 (3)	0.003 (3)
C5	0.019 (3)	0.028 (4)	0.010 (3)	−0.003 (3)	−0.001 (3)	0.001 (3)
C6	0.017 (3)	0.020 (3)	0.017 (3)	−0.003 (3)	0.008 (3)	0.002 (3)
C7	0.019 (3)	0.014 (3)	0.008 (3)	−0.001 (3)	0.002 (3)	0.003 (3)

Geometric parameters (Å, º) top

La1—O1ⁱ	2.676 (5)	O2—C1	1.279 (9)
La1—O2ⁱⁱ	2.449 (5)	O3—C7	1.349 (8)
La1—O2ⁱ	2.561 (5)	O7—H7A	0.8200
La1—O3ⁱⁱⁱ	2.478 (4)	O7—H7B	0.8200
La1—O3ⁱⁱ	2.499 (4)	C1—C2	1.480 (10)
La1—O4	2.573 (5)	C2—C3	1.393 (9)
La1—O5	2.970 (7)	C2—C7	1.424 (9)
La1—O6^iv	2.548 (5)	C3—C4	1.385 (10)
La1—O7	2.501 (5)	C3—H3A	0.9300
S1—O4	1.478 (5)	C4—C5	1.395 (10)
S1—O5	1.450 (6)	C5—C6	1.372 (10)
S1—O6	1.457 (5)	C5—H5A	0.9300
S1—C4	1.751 (7)	C6—C7	1.405 (10)
O1—C1	1.251 (9)	C6—H6A	0.9300

O2ⁱⁱ—La1—O3ⁱⁱⁱ	103.65 (16)	O6—S1—O4	110.7 (3)
O2ⁱⁱ—La1—O3ⁱⁱ	68.47 (15)	O5—S1—C4	109.1 (3)
O3ⁱⁱⁱ—La1—O3ⁱⁱ	67.24 (16)	O6—S1—C4	107.0 (3)
O2ⁱⁱ—La1—O7	72.75 (19)	O4—S1—C4	107.5 (3)
O3ⁱⁱⁱ—La1—O7	158.70 (17)	C1—O1—La1ⁱ	93.1 (4)
O3ⁱⁱ—La1—O7	127.17 (17)	C1—O2—La1^v	139.2 (4)
O2ⁱⁱ—La1—O6^iv	87.98 (17)	C1—O2—La1ⁱ	97.8 (4)
O3ⁱⁱⁱ—La1—O6^iv	131.23 (16)	La1^v—O2—La1ⁱ	116.49 (18)
O3ⁱⁱ—La1—O6^iv	74.06 (16)	C7—O3—La1ⁱⁱⁱ	121.3 (4)
O7—La1—O6^iv	70.05 (18)	C7—O3—La1^v	123.5 (4)
O2ⁱⁱ—La1—O2ⁱ	63.51 (18)	La1ⁱⁱⁱ—O3—La1^v	112.76 (16)
O3ⁱⁱⁱ—La1—O2ⁱ	86.88 (16)	S1—O4—La1	110.1 (3)
O3ⁱⁱ—La1—O2ⁱ	116.96 (15)	S1—O5—La1	93.3 (3)
O7—La1—O2ⁱ	72.64 (18)	S1—O6—La1^iv	151.0 (3)
O6^iv—La1—O2ⁱ	138.33 (17)	La1—O7—H7A	109.5
O2ⁱⁱ—La1—O4	162.22 (17)	La1—O7—H7B	130.5
O3ⁱⁱⁱ—La1—O4	73.55 (15)	H7A—O7—H7B	119.7
O3ⁱⁱ—La1—O4	94.76 (16)	O1—C1—O2	119.2 (6)
O7—La1—O4	116.21 (18)	O1—C1—C2	122.1 (6)
O6^iv—La1—O4	81.48 (16)	O2—C1—C2	118.6 (6)
O2ⁱ—La1—O4	132.71 (16)	C3—C2—C7	120.0 (6)
O2ⁱⁱ—La1—O1ⁱ	110.68 (15)	C3—C2—C1	118.6 (6)
O3ⁱⁱⁱ—La1—O1ⁱ	88.69 (16)	C7—C2—C1	121.1 (6)
O3ⁱⁱ—La1—O1ⁱ	154.12 (16)	C4—C3—C2	119.7 (6)
O7—La1—O1ⁱ	73.65 (18)	C4—C3—H3A	120.1
O6^iv—La1—O1ⁱ	131.55 (17)	C2—C3—H3A	120.1
O2ⁱ—La1—O1ⁱ	49.19 (15)	C3—C4—C5	120.7 (6)
O4—La1—O1ⁱ	86.95 (15)	C3—C4—S1	118.5 (5)
O2ⁱⁱ—La1—O5	139.80 (16)	C5—C4—S1	120.8 (5)
O3ⁱⁱⁱ—La1—O5	115.64 (15)	C6—C5—C4	120.1 (6)
O3ⁱⁱ—La1—O5	134.13 (15)	C6—C5—H5A	120.0
O7—La1—O5	67.57 (18)	C4—C5—H5A	120.0
O6^iv—La1—O5	72.93 (16)	C5—C6—C7	120.9 (6)
O2ⁱ—La1—O5	108.88 (15)	C5—C6—H6A	119.5
O4—La1—O5	49.58 (16)	C7—C6—H6A	119.5
O1ⁱ—La1—O5	64.08 (16)	O3—C7—C6	119.5 (6)
O5—S1—O6	115.5 (3)	O3—C7—C2	122.0 (6)
O5—S1—O4	106.9 (3)	C6—C7—C2	118.4 (6)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y, z+1; (iii) −x+2, −y+1, −z; (iv) −x+2, −y+2, −z+1; (v) x, y, z−1.

Experimental details

Crystal data
Chemical formula	[La(C₇H₃O₆S)(H₂O)]
M_r	372.08
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	6.2297 (7), 8.2390 (8), 9.9157 (9)
α, β, γ (°)	111.587 (2), 94.325 (2), 93.785 (2)
V (Å³)	469.47 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.79
Crystal size (mm)	0.24 × 0.16 × 0.12

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.415, 0.563
No. of measured, independent and observed [I > 2σ(I)] reflections	2457, 1633, 1527
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.090, 1.07
No. of reflections	1633
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.79, −1.66

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

La1—O1ⁱ	2.676 (5)	La1—O4	2.573 (5)
La1—O2ⁱⁱ	2.449 (5)	La1—O5	2.970 (7)
La1—O2ⁱ	2.561 (5)	La1—O6^iv	2.548 (5)
La1—O3ⁱⁱⁱ	2.478 (4)	La1—O7	2.501 (5)
La1—O3ⁱⁱ	2.499 (4)

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

Acknowledgements

The work was supported by the Natural Science Foundation of Anhui Province (grant No. KJ2008B166), the Ningbo Municipal Natural Science Foundation (grant No. 2008 A610048) and the Scientific Research Fund of Ningbo University (grant No. 2006050), and sponsored by the K. C. Wong Magna Fund of Ningbo University.

References

Cao, R., Sun, D. F., Liang, Y.-C., Hong, M.-C., Tatsumi, K. & Shi, Q. (2002). Inorg. Chem. 41, 2087–2094. Web of Science CSD CrossRef PubMed CAS Google Scholar
Li, X., Cao, R., Bi, W.-H., Yuan, D.-Q. & Sun, D.-F. (2005). Eur. J. Inorg. Chem. pp. 3156–3166. Web of Science CSD CrossRef Google Scholar
Li, X., Shi, Q., Sun, D.-F., Bi, W.-H. & Cao, R. (2004). Eur. J. Inorg. Chem. pp. 2747–2753. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1994). SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Siemens (1996). SMART. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Wang, X.-Q., Zhang, J., Li, Z.-J., Wen, Y.-H., Cheng, J.-K. & Yao, Y.-G. (2004). Acta Cryst. C60, m657–m658. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar