Poly[diaqua-μ2-isonicotinato-μ2-oxalato-terbium(III)]

Fang, Z.-Q.; Zeng, R.-H.; Li, Y.-T.; Yang, S.; Song, Z.-F.

doi:10.1107/S1600536808042682

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page m118

doi:10.1107/S1600536808042682

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Poly[diaqua-μ₂-isonicotinato-μ₂-oxalato-terbium(III)]

Zhan-Qiang Fang,^a ^* Rong-Hua Zeng,^a Yan-Ting Li,^a Shuo Yang ^a and Zhao-Feng Song ^a

^aSchool of Chemistry and the Environment, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: zhqfang77@yahoo.com.cn

(Received 21 October 2008; accepted 15 December 2008; online 20 December 2008)

In the crystal structure of the title complex, [Tb(C₆H₄NO₂)(C₂O₄)(H₂O)₂]_n, the Tb^III ion is coordinated by two O atoms from two isonicotinate (inic) anions, four O atoms of two oxalate anions, and two water molecules, displaying a distorted square-antiprismatic geometry. The Tb^III ion, the inic anion and the water molecules occupy general positions. One of the two crystallographically independent oxalate anions is located on a center of inversion, whereas the second is located on the twofold rotation axis. The carboxylate groups of the inic and oxalate anions link the terbium metal centres into layers. These layers are connected by O—H⋯O and N—H⋯O hydrogen bonding into a three-dimensional network.

Related literature

For background, see: Eddaoudi et al. (2001 ); Rizk et al. (2005 ). An independent determination of this structure is reported in the preceeding paper, see: Song et al. (2009 ).

Experimental

Crystal data

[Tb(C₆H₄NO₂)(C₂O₄)(H₂O)₂]
M_r = 405.07
Monoclinic, C 2/c
a = 17.7919 (18) Å
b = 9.9259 (10) Å
c = 12.9670 (13) Å
β = 112.4140 (10)°
V = 2117.0 (4) Å³
Z = 8
Mo Kα radiation
μ = 6.72 mm⁻¹
T = 296 (2) K
0.23 × 0.22 × 0.20 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (APEX2; Bruker, 2004 ) T_min = 0.241, T_max = 0.272
5243 measured reflections
1907 independent reflections
1674 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.063
S = 1.01
1907 reflections
163 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 1.40 e Å⁻³
Δρ_min = −1.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯O3ⁱ	0.84	2.22	2.992 (5)	153
O2W—H4W⋯O1Wⁱⁱ	0.84	2.19	3.003 (5)	163
O1W—H1W⋯N1ⁱⁱⁱ	0.84	1.83	2.661 (5)	167
O2W—H3W⋯O6^iv	0.84	2.01	2.836 (5)	172
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) -x+1, -y, -z+1; (iv) -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, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042682/nc2118sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808042682/nc2118Isup2.hkl

checkCIF report

Comment top

The design, synthesis, characterization and properties of coordination networks formed by functionalized organic molecules or anionas as bridges between metal centers are of great interest(Rizk et al., 2005; Eddaoudi et al., 2001). As a building block, isonicotinic acid and oxalic acid are excellent candidates for the construction of such compounds. In our ongoing investigations in this field the title compound was prepared and structurally characterized.

In the crystal structure of the title compound each Tb^III centre is coordinated by six oxygen atoms from two symmetry related inic anions, two crystallographically independent oxalate anions and two crystallographically independent water molecules within a distorted bicapped trigonal prismatic geometry (Fig. 1) . The Tb^III ions are linked by the inic and oxalate anions into layers, which are parallel to the b-c-plane (Fig. 2). Tb···Tb separations amount to 6.177 (4) and 5.047 (5) Å, respectively. These layers are connected via O—H···O and N—H···O hydrogen bonding between the water H atoms and the inic and one of the two crystallographically independent oxalate anions into three-dimensional network (Table 1).

Related literature top

For background, see: Eddaoudi et al. (2001); Rizk et al. (2005). An independent determination of this structure is reported in the preceeding paper, see: Song et al. (2009).

Experimental top

A mixture of Tb₄O₇ (0.189 g; 0.25 mmol), isonicotinic acid (0.135 g; 1.5 mmol), oxalic acid(0.135 g; 1.5 mmol), water (10 mL) and HNO₃ (0.385 mmol; 0.92g/ml) were stirred for 20 min and then sealed in a 20 mL Teflon-lined stainless-steel autoclave. The autoclave was heated to 433K for 3 days, and then cooled to room temperature at 5 K h^-1. By this procedure colorless block-like crystals of the title compound were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Part of the crystal structure of the title compound with labelling and displacement ellipsoids drawn at the 30% probabbility level. Symmetry codes: (i)1.5-x, 0.5-y, 1-z; (ii)1.5-x, -0.5-y, 1-z; (iii)2-x, y, 1.5-z;
	Fig. 2. Crystal structure of the title compound with view along the c-axis.

Poly[diaqua-µ₂-isonicotinato-µ₂-oxalato-terbium(III)] top

Crystal data top

[Tb(C₆H₄NO₂)(C₂O₄)(H₂O)₂]	F(000) = 1536
M_r = 405.07	D_x = 2.542 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.7919 (18) Å	Cell parameters from 2410 reflections
b = 9.9259 (10) Å	θ = 2.4–27.7°
c = 12.9670 (13) Å	µ = 6.72 mm⁻¹
β = 112.414 (1)°	T = 296 K
V = 2117.0 (4) Å³	Block, colourless
Z = 8	0.23 × 0.22 × 0.20 mm

Data collection top

Bruker APEXII area-detector diffractometer	1674 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
ϕ and ω scans	θ_max = 25.2°, θ_min = 2.4°
Absorption correction: multi-scan (APEX2; Bruker, 2004)	h = −21→20
T_min = 0.241, T_max = 0.272	k = −5→11
5243 measured reflections	l = −15→15
1907 independent 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.063	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0363P)²] where P = (F_o² + 2F_c²)/3
1907 reflections	(Δ/σ)_max = 0.002
163 parameters	Δρ_max = 1.40 e Å⁻³
6 restraints	Δρ_min = −1.31 e Å⁻³

Crystal data top

[Tb(C₆H₄NO₂)(C₂O₄)(H₂O)₂]	V = 2117.0 (4) Å³
M_r = 405.07	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 17.7919 (18) Å	µ = 6.72 mm⁻¹
b = 9.9259 (10) Å	T = 296 K
c = 12.9670 (13) Å	0.23 × 0.22 × 0.20 mm
β = 112.414 (1)°

Data collection top

Bruker APEXII area-detector diffractometer	1907 independent reflections
Absorption correction: multi-scan (APEX2; Bruker, 2004)	1674 reflections with I > 2σ(I)
T_min = 0.241, T_max = 0.272	R_int = 0.031
5243 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	6 restraints
wR(F²) = 0.063	H-atom parameters constrained
S = 1.01	Δρ_max = 1.40 e Å⁻³
1907 reflections	Δρ_min = −1.31 e Å⁻³
163 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Tb1	0.824056 (12)	0.03238 (2)	0.574780 (18)	0.01553 (10)
O5	0.9618 (2)	−0.0185 (4)	0.6050 (3)	0.0289 (9)
O2	0.6877 (2)	0.0558 (4)	0.4672 (3)	0.0326 (9)
O3	0.8029 (2)	−0.1491 (3)	0.4403 (3)	0.0239 (8)
C8	1.0149 (3)	−0.0110 (5)	0.7019 (4)	0.0192 (11)
O6	1.0905 (2)	−0.0055 (4)	0.7291 (3)	0.0272 (9)
C1	0.6278 (3)	0.1294 (5)	0.4198 (4)	0.0215 (11)
C2	0.5442 (3)	0.0692 (5)	0.3902 (4)	0.0172 (10)
C3	0.4756 (3)	0.1501 (6)	0.3627 (4)	0.0264 (12)
H3	0.4800	0.2434	0.3618	0.032*
C6	0.5336 (3)	−0.0690 (5)	0.3874 (4)	0.0241 (11)
H6	0.5781	−0.1263	0.4050	0.029*
C4	0.4010 (3)	0.0890 (6)	0.3366 (4)	0.0315 (13)
H4	0.3556	0.1438	0.3206	0.038*
C5	0.4563 (3)	−0.1211 (5)	0.3584 (5)	0.0314 (13)
H5	0.4500	−0.2142	0.3564	0.038*
N1	0.3903 (3)	−0.0438 (5)	0.3330 (4)	0.0309 (11)
C7	0.7582 (3)	−0.2447 (5)	0.4457 (4)	0.0201 (11)
O4	0.7261 (2)	−0.3320 (3)	0.3724 (3)	0.0252 (8)
O1	0.6308 (2)	0.2507 (4)	0.3926 (3)	0.0334 (9)
O1W	0.75857 (19)	0.1250 (3)	0.6941 (3)	0.0228 (8)
H1W	0.7146	0.0877	0.6885	0.034*
H2W	0.7794	0.1546	0.7598	0.034*
O2W	0.8300 (2)	0.1188 (4)	0.4029 (3)	0.0312 (9)
H3W	0.8554	0.0794	0.3691	0.047*
H4W	0.8051	0.1834	0.3631	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tb1	0.01241 (14)	0.01564 (15)	0.01830 (15)	−0.00225 (9)	0.00558 (10)	−0.00106 (9)
O5	0.0153 (18)	0.048 (2)	0.023 (2)	0.0038 (17)	0.0067 (16)	−0.0063 (18)
O2	0.0144 (18)	0.052 (3)	0.028 (2)	0.0001 (18)	0.0045 (16)	0.001 (2)
O3	0.0271 (19)	0.0201 (18)	0.0287 (19)	−0.0097 (16)	0.0153 (16)	−0.0047 (16)
C8	0.017 (3)	0.018 (2)	0.019 (3)	0.003 (2)	0.003 (2)	0.000 (2)
O6	0.0132 (18)	0.040 (2)	0.027 (2)	0.0019 (16)	0.0068 (16)	−0.0024 (17)
C1	0.019 (3)	0.031 (3)	0.016 (2)	−0.006 (2)	0.009 (2)	−0.007 (2)
C2	0.017 (2)	0.021 (3)	0.014 (2)	−0.005 (2)	0.0058 (19)	0.001 (2)
C3	0.023 (3)	0.028 (3)	0.033 (3)	0.004 (2)	0.017 (2)	0.008 (2)
C6	0.019 (3)	0.022 (3)	0.031 (3)	−0.003 (2)	0.010 (2)	0.001 (2)
C4	0.019 (3)	0.049 (4)	0.030 (3)	0.007 (3)	0.014 (2)	0.008 (3)
C5	0.036 (3)	0.022 (3)	0.040 (3)	−0.013 (3)	0.018 (3)	−0.004 (3)
N1	0.023 (2)	0.044 (3)	0.026 (2)	−0.009 (2)	0.010 (2)	−0.001 (2)
C7	0.019 (2)	0.017 (3)	0.023 (3)	0.004 (2)	0.006 (2)	0.002 (2)
O4	0.033 (2)	0.0225 (18)	0.0218 (18)	−0.0081 (16)	0.0128 (16)	−0.0050 (16)
O1	0.038 (2)	0.027 (2)	0.041 (2)	−0.0189 (18)	0.0211 (19)	−0.0120 (19)
O1W	0.0180 (17)	0.027 (2)	0.0260 (18)	−0.0064 (15)	0.0116 (15)	−0.0071 (16)
O2W	0.049 (2)	0.024 (2)	0.029 (2)	0.0045 (18)	0.0241 (18)	0.0045 (17)

Geometric parameters (Å, º) top

Tb1—O1ⁱ	2.280 (3)	C2—C3	1.389 (7)
Tb1—O2	2.303 (3)	C3—C4	1.379 (7)
Tb1—O5	2.383 (3)	C3—H3	0.9300
Tb1—O4ⁱⁱ	2.385 (3)	C6—C5	1.380 (7)
Tb1—O2W	2.427 (3)	C6—H6	0.9300
Tb1—O3	2.435 (3)	C4—N1	1.330 (8)
Tb1—O6ⁱⁱⁱ	2.443 (4)	C4—H4	0.9300
Tb1—O1W	2.443 (3)	C5—N1	1.335 (7)
O5—C8	1.254 (6)	C5—H5	0.9300
O2—C1	1.244 (6)	C7—O4	1.251 (6)
O3—C7	1.259 (6)	C7—C7ⁱⁱ	1.545 (10)
C8—O6	1.256 (6)	O4—Tb1ⁱⁱ	2.385 (3)
C8—C8ⁱⁱⁱ	1.529 (10)	O1—Tb1ⁱ	2.280 (3)
O6—Tb1ⁱⁱⁱ	2.443 (4)	O1W—H1W	0.8429
C1—O1	1.261 (6)	O1W—H2W	0.8420
C1—C2	1.511 (6)	O2W—H3W	0.8367
C2—C6	1.383 (7)	O2W—H4W	0.8365

O1ⁱ—Tb1—O2	103.43 (14)	O6—C8—C8ⁱⁱⁱ	116.0 (5)
O1ⁱ—Tb1—O5	84.39 (13)	C8—O6—Tb1ⁱⁱⁱ	118.3 (3)
O2—Tb1—O5	154.22 (14)	O2—C1—O1	125.4 (5)
O1ⁱ—Tb1—O4ⁱⁱ	151.43 (12)	O2—C1—C2	117.9 (5)
O2—Tb1—O4ⁱⁱ	80.50 (13)	O1—C1—C2	116.7 (5)
O5—Tb1—O4ⁱⁱ	104.46 (13)	C6—C2—C3	118.0 (4)
O1ⁱ—Tb1—O2W	72.60 (12)	C6—C2—C1	120.7 (4)
O2—Tb1—O2W	79.21 (13)	C3—C2—C1	121.3 (5)
O5—Tb1—O2W	79.88 (13)	C4—C3—C2	118.6 (5)
O4ⁱⁱ—Tb1—O2W	135.25 (12)	C4—C3—H3	120.7
O1ⁱ—Tb1—O3	141.11 (12)	C2—C3—H3	120.7
O2—Tb1—O3	78.56 (13)	C5—C6—C2	119.4 (5)
O5—Tb1—O3	80.16 (12)	C5—C6—H6	120.3
O4ⁱⁱ—Tb1—O3	67.43 (11)	C2—C6—H6	120.3
O2W—Tb1—O3	69.67 (11)	N1—C4—C3	123.8 (5)
O1ⁱ—Tb1—O6ⁱⁱⁱ	85.24 (13)	N1—C4—H4	118.1
O2—Tb1—O6ⁱⁱⁱ	137.67 (13)	C3—C4—H4	118.1
O5—Tb1—O6ⁱⁱⁱ	66.65 (12)	N1—C5—C6	122.9 (5)
O4ⁱⁱ—Tb1—O6ⁱⁱⁱ	74.06 (12)	N1—C5—H5	118.6
O2W—Tb1—O6ⁱⁱⁱ	141.48 (12)	C6—C5—H5	118.6
O3—Tb1—O6ⁱⁱⁱ	119.77 (12)	C4—N1—C5	117.4 (4)
O1ⁱ—Tb1—O1W	75.34 (12)	O4—C7—O3	126.5 (5)
O2—Tb1—O1W	72.48 (13)	O4—C7—C7ⁱⁱ	117.1 (5)
O5—Tb1—O1W	133.16 (12)	O3—C7—C7ⁱⁱ	116.4 (5)
O4ⁱⁱ—Tb1—O1W	79.12 (11)	C7—O4—Tb1ⁱⁱ	118.1 (3)
O2W—Tb1—O1W	130.27 (12)	C1—O1—Tb1ⁱ	154.0 (4)
O3—Tb1—O1W	138.71 (11)	Tb1—O1W—H1W	115.5
O6ⁱⁱⁱ—Tb1—O1W	69.91 (12)	Tb1—O1W—H2W	129.8
C8—O5—Tb1	119.1 (3)	H1W—O1W—H2W	106.0
C1—O2—Tb1	149.9 (4)	Tb1—O2W—H3W	122.5
C7—O3—Tb1	116.5 (3)	Tb1—O2W—H4W	129.8
O5—C8—O6	127.0 (5)	H3W—O2W—H4W	107.4
O5—C8—C8ⁱⁱⁱ	117.0 (5)

Symmetry codes: (i) −x+3/2, −y+1/2, −z+1; (ii) −x+3/2, −y−1/2, −z+1; (iii) −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···O3^iv	0.84	2.22	2.992 (5)	153
O2W—H4W···O1Wⁱ	0.84	2.19	3.003 (5)	163
O1W—H1W···N1^v	0.84	1.83	2.661 (5)	167
O2W—H3W···O6^vi	0.84	2.01	2.836 (5)	172

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

Experimental details

Crystal data
Chemical formula	[Tb(C₆H₄NO₂)(C₂O₄)(H₂O)₂]
M_r	405.07
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	17.7919 (18), 9.9259 (10), 12.9670 (13)
β (°)	112.414 (1)
V (Å³)	2117.0 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	6.72
Crystal size (mm)	0.23 × 0.22 × 0.20

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (APEX2; Bruker, 2004)
T_min, T_max	0.241, 0.272
No. of measured, independent and observed [I > 2σ(I)] reflections	5243, 1907, 1674
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.063, 1.01
No. of reflections	1907
No. of parameters	163
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.40, −1.31

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003) and SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O3ⁱ	0.84	2.22	2.992 (5)	153.3
O2W—H4W···O1Wⁱⁱ	0.84	2.19	3.003 (5)	163.2
O1W—H1W···N1ⁱⁱⁱ	0.84	1.83	2.661 (5)	167.3
O2W—H3W···O6^iv	0.84	2.01	2.836 (5)	171.6

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

Acknowledgements

The authors acknowledge South China Normal University for supporting this work.

References

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