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

Abstract

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,

• a = 17.7919 (18) Å

• b = 9.9259 (10) Å

• c = 12.9670 (13) Å

• β = 112.4140 (10)°

• V = 2117.0 (4) ų

• 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[F ² > 2σ(F ²)] = 0.025

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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⋯O6iv	0.84	2.01	2.836 (5)	172

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The Water H atoms were located in difference Fourier maps, their bond lengths were set to ideal values of O–H = 0.84 and finally they were refined isotropic using a riding model with U_iso(H) = 1.5 U_eq(O). C-H 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 U_iso(H) = 1.2 U_eq(C).

Figures

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.

Crystal data

[Tb(C6H4NO2)(C2O4)(H2O)2]	F(000) = 1536
Mr = 405.07	Dx = 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

Bruker APEXII area-detector diffractometer	1674 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
φ and ω scans	θmax = 25.2°, θmin = 2.4°
Absorption correction: multi-scan (APEX2; Bruker, 2004)	h = −21→20
Tmin = 0.241, Tmax = 0.272	k = −5→11
5243 measured reflections	l = −15→15
1907 independent reflections

Refinement

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(Fo2) + (0.0363P)2] where P = (Fo2 + 2Fc2)/3
1907 reflections	(Δ/σ)max = 0.002
163 parameters	Δρmax = 1.40 e Å−3
6 restraints	Δρmin = −1.31 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O3iv	0.84	2.22	2.992 (5)	153
O2W—H4W···O1Wi	0.84	2.19	3.003 (5)	163
O1W—H1W···N1v	0.84	1.83	2.661 (5)	167
O2W—H3W···O6vi	0.84	2.01	2.836 (5)	172

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