Poly[diaqua-μ(2)-isonicotinato-μ(2)-oxalato-terbium(III)].

In the crystal structure of the title complex, [Tb(C(6)H(4)NO(2))(C(2)O(4))(H(2)O)(2)](n), the Tb(III) cation is coordinated by four O atoms from two oxalate ligands, two O atoms from two isonicotinate ligands and two O atoms from water mol-ecules within a distorted square-anti-prismatic coordination. The Tb(III) cation, the isonicotinate anion and the two crystallographically independent water mol-ecules occupy general positions, whereas one of the two crystallographically independent oxalate anions is located on a center of inversion, and the second oxalate anion is located on a twofold rotation axis. The Tb(III) cations are linked by the oxalate and isonicotinate anions into layers, which are connected via inter-molecular hydrogen-bonding and π-π stacking [with centroid-to-centroid distances of 3.509 (2) and 3.343 (3) Å] inter-actions into a three-dimensional network.

Related literature

For general background on coordination polymers and open-framework materials, see: Yaghi et al. (1998 ▶, 2003 ▶); Serre et al. (2004 ▶); James (2003 ▶). For related structures, see: Xia et al. (2004 ▶); Feng et al. (2003 ▶). An independent determination of this structure is reported in the following paper, see: Fang et al. (2009 ▶).

Experimental

Crystal data

[Tb(C6H4NO2)(C2O4)(H2O)2]

M = 405.07

Monoclinic,

a = 17.7957 (6) Å

b = 9.9229 (4) Å

c = 12.9673 (5) Å

β = 112.407 (2)°

V = 2116.95 (14) Å3

Z = 8

Mo Kα radiation

μ = 6.72 mm−1

T = 273 (2) K

0.36 × 0.30 × 0.24 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.113, T max = 0.207

7256 measured reflections

1906 independent reflections

1618 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.053

S = 0.91

1906 reflections

145 parameters

6 restraints

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.88 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040518/nc2122sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040518/nc2122Isup2.hkl

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

[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
Hall symbol: -C 2yc	Cell parameters from 8000 reflections
a = 17.7957 (6) Å	θ = 1.7–26.0°
b = 9.9229 (4) Å	µ = 6.72 mm−1
c = 12.9673 (5) Å	T = 273 K
β = 112.407 (2)°	Block, colorless
V = 2116.95 (14) Å3	0.36 × 0.30 × 0.24 mm
Z = 8

Bruker APEXII area-detector diffractometer	1906 independent reflections
Radiation source: fine-focus sealed tube	1618 reflections with I > 2σ(I)
graphite	Rint = 0.034
φ and ω scans	θmax = 25.2°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→20
Tmin = 0.113, Tmax = 0.207	k = −11→11
7256 measured reflections	l = −15→15

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.053	H-atom parameters constrained
S = 0.91	w = 1/[σ2(Fo2) + (0.0299P)2 + 5.163P] where P = (Fo2 + 2Fc2)/3
1906 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.52 e Å−3
6 restraints	Δρmin = −0.88 e Å−3

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.

	x	y	z	Uiso*/Ueq
Tb1	0.323989 (12)	0.96756 (2)	0.074846 (17)	0.01399 (9)
O1	0.46185 (19)	1.0185 (4)	0.1051 (3)	0.0274 (9)
O2	0.3030 (2)	1.1497 (3)	−0.0596 (3)	0.0229 (8)
O5	0.3693 (2)	0.7501 (4)	0.1067 (3)	0.0331 (9)
C1	0.2585 (3)	1.2447 (5)	−0.0542 (4)	0.0172 (11)
C2	0.5146 (3)	1.0111 (5)	0.2013 (4)	0.0172 (11)
C7	0.5237 (3)	0.6498 (6)	0.1361 (4)	0.0231 (12)
H7	0.5190	0.7432	0.1348	0.028*
C8	0.3727 (3)	0.6297 (6)	0.0808 (4)	0.0196 (11)
C3	0.4558 (3)	0.5688 (5)	0.1108 (3)	0.0163 (11)
C6	0.5989 (3)	0.5889 (7)	0.1636 (4)	0.0281 (13)
H6	0.6444	0.6439	0.1807	0.034*
C4	0.4671 (3)	0.4306 (5)	0.1135 (4)	0.0220 (12)
H4	0.4228	0.3731	0.0961	0.026*
C5	0.54429 (8)	0.37835 (15)	0.14206 (11)	0.0281 (13)
H5	0.5508	0.2853	0.1440	0.034*
N1	0.60972 (8)	0.45622 (15)	0.16691 (11)	0.0279 (11)
O3	0.59033 (8)	1.00505 (15)	0.22872 (11)	0.0229 (8)
O4	0.22609 (8)	1.33232 (15)	−0.12763 (11)	0.0232 (8)
O6	0.31250 (8)	0.55572 (15)	0.03267 (11)	0.0301 (9)
O1W	0.25866 (8)	0.87408 (15)	0.19413 (11)	0.0208 (8)
H1W	0.2122	0.9030	0.1852	0.031*
H2W	0.2833	0.8622	0.2630	0.031*
O2W	0.33025 (8)	0.88114 (15)	−0.09693 (11)	0.0286 (9)
H3W	0.3550	0.9157	−0.1341	0.043*
H4W	0.2966	0.8264	−0.1394	0.043*

	U11	U22	U33	U12	U13	U23
Tb1	0.01048 (13)	0.01587 (15)	0.01480 (12)	0.00208 (11)	0.00389 (9)	0.00099 (11)
O1	0.0140 (17)	0.047 (3)	0.0180 (17)	−0.0045 (17)	0.0027 (14)	0.0043 (17)
O2	0.0294 (19)	0.023 (2)	0.0202 (17)	0.0082 (17)	0.0143 (15)	0.0022 (16)
O5	0.039 (2)	0.028 (2)	0.039 (2)	0.017 (2)	0.0227 (19)	0.0083 (19)
C1	0.013 (2)	0.019 (3)	0.021 (3)	0.001 (2)	0.007 (2)	0.001 (2)
C2	0.009 (2)	0.017 (3)	0.021 (2)	−0.002 (2)	0.002 (2)	0.000 (2)
C7	0.019 (3)	0.026 (3)	0.022 (3)	−0.004 (2)	0.005 (2)	−0.009 (2)
C8	0.020 (3)	0.030 (3)	0.012 (2)	0.008 (2)	0.008 (2)	0.010 (2)
C3	0.017 (2)	0.024 (3)	0.007 (2)	0.005 (2)	0.0035 (18)	−0.002 (2)
C6	0.016 (3)	0.047 (4)	0.022 (3)	−0.004 (3)	0.008 (2)	−0.006 (3)
C4	0.020 (3)	0.022 (3)	0.023 (3)	−0.002 (2)	0.007 (2)	−0.004 (2)
C5	0.028 (3)	0.026 (3)	0.034 (3)	0.013 (3)	0.016 (2)	0.007 (3)
N1	0.015 (2)	0.046 (4)	0.024 (2)	0.007 (2)	0.0081 (18)	0.003 (2)
O3	0.0175 (18)	0.033 (2)	0.0197 (17)	−0.0024 (16)	0.0089 (14)	0.0018 (15)
O4	0.032 (2)	0.020 (2)	0.0195 (17)	0.0121 (17)	0.0116 (15)	0.0052 (16)
O6	0.0095 (17)	0.050 (3)	0.0259 (18)	0.0005 (18)	0.0013 (14)	0.0006 (18)
O1W	0.0149 (16)	0.028 (2)	0.0201 (16)	0.0064 (16)	0.0076 (14)	0.0074 (16)
O2W	0.040 (2)	0.028 (2)	0.0232 (18)	−0.0068 (19)	0.0179 (17)	−0.0074 (17)

Tb1—O5	2.285 (4)	C7—H7	0.9300
Tb1—O6i	2.3055 (14)	C8—O6	1.251 (5)
Tb1—O4ii	2.3814 (14)	C8—C3	1.505 (6)
Tb1—O1	2.386 (3)	C3—C4	1.385 (7)
Tb1—O2W	2.4286 (13)	C6—N1	1.329 (7)
Tb1—O2	2.439 (3)	C6—H6	0.9300
Tb1—O1W	2.4444 (13)	C4—C5	1.380 (5)
Tb1—O3iii	2.4476 (13)	C4—H4	0.9300
O1—C2	1.245 (6)	C5—N1	1.3306
O2—C1	1.251 (5)	C5—H5	0.9300
O5—C8	1.249 (6)	O3—Tb1iii	2.4476 (13)
C1—O4	1.255 (5)	O4—Tb1ii	2.3814 (14)
C1—C1ii	1.549 (9)	O6—Tb1i	2.3055 (14)
C2—O3	1.257 (5)	O1W—H1W	0.8400
C2—C2iii	1.537 (9)	O1W—H2W	0.8400
C7—C3	1.382 (7)	O2W—H3W	0.8400
C7—C6	1.387 (7)	O2W—H4W	0.8400
O5—Tb1—O6i	103.43 (11)	O4—C1—C1ii	116.8 (5)
O5—Tb1—O4ii	151.65 (9)	O1—C2—O3	127.1 (4)
O6i—Tb1—O4ii	80.4	O1—C2—C2iii	117.5 (5)
O5—Tb1—O1	84.30 (13)	O3—C2—C2iii	115.4 (5)
O6i—Tb1—O1	154.26 (9)	C3—C7—C6	118.6 (5)
O4ii—Tb1—O1	104.49 (10)	C3—C7—H7	120.7
O5—Tb1—O2W	72.32 (10)	C6—C7—H7	120.7
O6i—Tb1—O2W	79.4	O5—C8—O6	125.1 (4)
O4ii—Tb1—O2W	135.3	O5—C8—C3	117.3 (5)
O1—Tb1—O2W	79.74 (9)	O6—C8—C3	117.6 (4)
O5—Tb1—O2	140.94 (11)	C7—C3—C4	117.7 (4)
O6i—Tb1—O2	78.63 (9)	C7—C3—C8	120.8 (5)
O4ii—Tb1—O2	67.37 (8)	C4—C3—C8	121.5 (4)
O1—Tb1—O2	80.13 (11)	N1—C6—C7	123.6 (5)
O2W—Tb1—O2	69.77 (8)	N1—C6—H6	118.2
O5—Tb1—O1W	75.35 (9)	C7—C6—H6	118.2
O6i—Tb1—O1W	72.49 (5)	C5—C4—C3	120.0 (4)
O4ii—Tb1—O1W	79.29 (5)	C5—C4—H4	120.0
O1—Tb1—O1W	133.11 (8)	C3—C4—H4	120.0
O2W—Tb1—O1W	130.20 (6)	N1—C5—C4	122.4 (2)
O2—Tb1—O1W	138.86 (8)	N1—C5—H5	118.8
O5—Tb1—O3iii	85.32 (10)	C4—C5—H5	118.8
O6i—Tb1—O3iii	137.68 (6)	C6—N1—C5	117.7 (2)
O4ii—Tb1—O3iii	74.2	C2—O3—Tb1iii	118.5 (2)
O1—Tb1—O3iii	66.61 (8)	C1—O4—Tb1ii	118.2 (2)
O2W—Tb1—O3iii	141.3	C8—O6—Tb1i	149.8 (3)
O2—Tb1—O3iii	119.75 (9)	Tb1—O1W—H1W	117.6
O1W—Tb1—O3iii	69.9	Tb1—O1W—H2W	123.0
C2—O1—Tb1	119.2 (3)	H1W—O1W—H2W	106.4
C1—O2—Tb1	116.5 (3)	Tb1—O2W—H3W	126.8
C8—O5—Tb1	154.8 (3)	Tb1—O2W—H4W	124.0
O2—C1—O4	126.6 (4)	H3W—O2W—H4W	106.6
O2—C1—C1ii	116.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···N1iv	0.84	1.83	2.665	177
O1W—H2W···O2v	0.84	2.19	2.992 (3)	159
O2W—H3W···O3vi	0.84	2.00	2.835 (3)	177
O2W—H4W···O1Wi	0.84	2.21	2.998 (3)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯N1i	0.84	1.83	2.665	177
O1W—H2W⋯O2ii	0.84	2.19	2.992 (3)	159
O2W—H3W⋯O3iii	0.84	2.00	2.835 (3)	177
O2W—H4W⋯O1Wiv	0.84	2.21	2.998 (3)	156

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