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Acta Cryst. (2007). E63, m1967    [ doi:10.1107/S1600536807029789 ]

catena-Poly[[[diaqua(6-carboxypyridine-2-carboxylato-[kappa]3O,N,O')gadolinium(III)]-[mu]-pyridine-2,6-dicarboxylato-[kappa]4N,O,O':O''] tetrahydrate]

L.-J. Hao and T.-L. Yu

Abstract top

The title compound, [Gd(C7H3NO4)(C7H4NO4)(H2O)2]·4H2O, is isostructural with its LaIII, CeIII, PrIII, NdIII, SmIII and EuIII analogues. The GdIII ion is nine-coordinated by two O and one N atoms from a tridentate 6-carboxypyridine-2-carboxylate ligand, two O and one N atoms from a tridentate pyridine-2,6-dicarboxylate ligand, one O atom belonging to a neighboring pyridine-2,6-dicarboxylate ligand, and two water molecules. The bridging pyridine-2,6-dicarboxylate ligand gives rise to infinite chains.

Comment top

The title compound is isostructural with its LaIII (Guerriero et al., 1987; Ghosh & Bharadwaj, 2005), CeIII (Okabe et al., 2002; Ghosh & Bharadwaj, 2003; Rafizadeh et al., 2005; Ramezanipour et al., 2005), PrIII (Ghosh & Bharadwaj, 2003; Zhao et al., 2005), NdIII (Miao et al., 1992), SmIII (Liu et al., 2005; Liu et al., 2006; Rafizadeh et al., 2005; Song et al., 2005) and EuIII (Brayshaw et al., 2005) analogues.

The GdIII ion is nine-coordinated by four O and two N atoms from two independent tridentate pyridine-2,6-dicarboxylate ligands, one O atom belonging to a neighboring pyridine-2,6-dicarboxylate ligand and two water molecules (Fig. 1). The bridging pyridine-2,6-dicarboxylate ligand gives rise to infinite chains along the c-axis (Fig. 2). An extensive network of hydrogen bonds exists between the water molecules.

Related literature top

The isostructural lanthanide compounds are those with LaIII (Guerriero et al., 1987; Ghosh & Bharadwaj, 2005), CeIII (Okabe et al., 2002; Ghosh & Bharadwaj, 2003; Rafizadeh et al., 2005; Ramezanipour et al., 2005), PrIII (Ghosh & Bharadwaj, 2003; Zhao et al., 2005), NdIII (Miao et al., 1992), SmIII (Liu et al., 2005, 2006; Rafizadeh et al., 2005; Song et al., 2005) and EuIII (Brayshaw et al., 2005).

Experimental top

A mixture of GdCl3 (0.5 mmol), NaOH (0.5 mmol), pyridine-2,6-dicarboxylic acid (0.5 mmol), H2O (8 ml) and ethanol (8 ml) in a 25 ml Teflon-lined stainless steel autoclave was kept at 433 K for three days. Colourless crystals were obtained after cooling to room temperature with a yield of 36%. Elemental analysis calculated: C 28.16, H 3.18, N 4.69%; found: C 28.50, H 3.22, N 4.76%.

Refinement top

The H atoms of the water molecule were located from difference Fourier maps and were refined with distance restraints of H···H = 1.38 (2)Å and O—H = 0.82 (2) Å. All other H atoms were placed in calculated positions with: a C—H bond distance of 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title compound showing 30% probability displacement ellipsoids for non-H atoms. Atom O8I is generated by the symmetry code: x, 1/2 - y, 1/2 + z.
[Figure 2] Fig. 2. Part of an infinite chain running along the c-axis.
catena-Poly[[[diaqua(6-carboxypyridine-2-carboxylato- κ3O,N,O')gadolinium(III)]-µ-pyridine- 2,6-dicarboxylato-κ4N,O,O':O''] tetrahydrate] top
Crystal data top
[Gd(C7H3NO4)(C7H4NO4)(H2O)2]·4H2OF(000) = 1172
Mr = 596.56Dx = 1.951 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3925 reflections
a = 14.1267 (3) Åθ = 1.5–26.0°
b = 11.2787 (2) ŵ = 3.34 mm−1
c = 13.0162 (2) ÅT = 293 K
β = 101.728 (1)°Cubic, colourless
V = 2030.59 (6) Å30.10 × 0.10 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		3925 independent reflections
Radiation source: fine-focus sealed tube3237 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
φ and ω scansθmax = 26.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −16→16
Tmin = 0.731, Tmax = 0.731k = −13→13
7168 measured reflectionsl = −7→15
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.134H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.1152P)2 + 2.6596P]
where P = (Fo2 + 2Fc2)/3
3925 reflections(Δ/σ)max < 0.001
317 parametersΔρmax = 1.05 e Å−3
0 restraintsΔρmin = −1.12 e Å−3
Crystal data top
[Gd(C7H3NO4)(C7H4NO4)(H2O)2]·4H2OV = 2030.59 (6) Å3
Mr = 596.56Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.1267 (3) ŵ = 3.34 mm−1
b = 11.2787 (2) ÅT = 293 K
c = 13.0162 (2) Å0.10 × 0.10 × 0.10 mm
β = 101.728 (1)°
Data collection top
Bruker SMART CCD
diffractometer		3925 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3237 reflections with I > 2σ(I)
Tmin = 0.731, Tmax = 0.731Rint = 0.033
7168 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.037H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.134Δρmax = 1.05 e Å−3
S = 1.00Δρmin = −1.12 e Å−3
3925 reflectionsAbsolute structure: ?
317 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Gd10.26984 (3)0.29481 (3)0.64844 (3)0.0182 (3)
C10.4427 (8)0.5000 (9)0.6318 (8)0.031 (2)
C20.5030 (7)0.3903 (10)0.6329 (8)0.032 (2)
C30.6014 (9)0.3898 (13)0.6353 (11)0.052 (3)
H30.63540.46050.63620.063*
C40.6477 (11)0.2826 (13)0.6365 (17)0.041 (3)
H40.71410.28010.63990.084*
C50.5952 (9)0.1780 (13)0.6325 (13)0.055 (4)
H50.62530.10490.63130.066*
C60.4975 (7)0.1849 (9)0.6305 (8)0.027 (2)
C70.4325 (7)0.0764 (9)0.6274 (8)0.026 (2)
C80.1194 (6)0.5248 (8)0.6735 (7)0.0199 (18)
C90.1269 (6)0.5389 (7)0.5597 (6)0.0150 (15)
C100.0915 (7)0.6395 (8)0.5001 (7)0.0239 (19)
H100.06410.70260.52980.029*
C110.0990 (7)0.6412 (8)0.3934 (7)0.026 (2)
H110.07720.70680.35200.031*
C120.1382 (6)0.5472 (7)0.3510 (6)0.0206 (17)
H120.14110.54630.28030.025*
C130.1740 (6)0.4515 (7)0.4171 (6)0.0163 (16)
C140.2257 (6)0.3477 (7)0.3807 (7)0.0167 (17)
N10.4519 (6)0.2884 (6)0.6323 (6)0.0227 (18)
N20.1687 (5)0.4485 (6)0.5185 (5)0.0140 (13)
O10.3562 (5)0.4925 (6)0.6348 (5)0.0286 (15)
O20.4846 (6)0.5978 (7)0.6261 (7)0.049 (2)
H20.44910.65580.62260.073*
O30.3440 (5)0.0970 (6)0.6299 (5)0.0265 (14)
O40.4693 (5)−0.0207 (6)0.6241 (7)0.0424 (19)
O50.0799 (6)0.6041 (6)0.7145 (5)0.0329 (16)
O60.1550 (5)0.4297 (5)0.7180 (4)0.0245 (14)
O70.2736 (5)0.2815 (5)0.4534 (5)0.0202 (14)
O80.2190 (5)0.3336 (6)0.2838 (4)0.0216 (13)
O90.1254 (5)0.1838 (6)0.5631 (5)0.0284 (15)
O100.3672 (6)0.3476 (7)0.8247 (5)0.0405 (19)
O110.9704 (6)0.0577 (6)0.5986 (6)0.0370 (18)
O120.7979 (9)0.4016 (10)0.9161 (12)0.090 (4)
O130.3766 (9)0.7743 (10)0.6153 (14)0.092 (4)
O140.0414 (5)0.3081 (6)0.8505 (6)0.0277 (16)
H210.125 (12)0.205 (12)0.503 (5)0.080*
H220.085 (9)0.134 (11)0.573 (10)0.080*
H230.407 (8)0.401 (11)0.839 (10)0.080*
H240.335 (10)0.333 (15)0.868 (9)0.080*
H250.968 (12)0.086 (10)0.655 (6)0.080*
H260.954 (12)−0.014 (6)0.588 (10)0.080*
H270.855 (4)0.419 (16)0.918 (10)0.080*
H280.786 (10)0.398 (17)0.978 (6)0.080*
H290.383 (11)0.828 (12)0.660 (11)0.080*
H300.323 (6)0.744 (14)0.603 (13)0.080*
H310.005 (11)0.252 (10)0.843 (11)0.080*
H320.067 (11)0.324 (13)0.802 (8)0.080*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Gd10.0194 (4)0.0192 (4)0.0153 (4)0.00107 (14)0.0021 (2)0.00124 (13)
C10.039 (6)0.023 (5)0.032 (5)−0.006 (4)0.006 (4)0.004 (4)
C20.026 (5)0.036 (6)0.032 (5)−0.012 (4)0.004 (4)0.002 (4)
C30.031 (6)0.054 (8)0.075 (9)−0.016 (6)0.019 (6)−0.006 (6)
C40.038 (5)0.037 (5)0.046 (5)−0.001 (5)0.007 (5)−0.001 (5)
C50.024 (6)0.051 (7)0.093 (11)−0.001 (6)0.019 (7)−0.015 (8)
C60.014 (5)0.033 (5)0.033 (5)−0.002 (4)0.001 (4)−0.003 (4)
C70.016 (5)0.032 (5)0.030 (5)−0.001 (4)0.003 (4)0.001 (4)
C80.019 (4)0.022 (4)0.018 (4)0.001 (3)0.004 (3)−0.001 (3)
C90.015 (4)0.012 (4)0.017 (4)0.002 (3)0.003 (3)−0.001 (3)
C100.031 (5)0.020 (4)0.021 (4)0.008 (4)0.006 (4)0.001 (3)
C110.033 (5)0.024 (5)0.018 (4)0.007 (4)−0.003 (4)0.006 (3)
C120.027 (5)0.021 (4)0.012 (4)0.006 (3)0.001 (3)0.002 (3)
C130.016 (4)0.017 (4)0.015 (4)−0.003 (3)0.001 (3)−0.002 (3)
C140.017 (4)0.017 (4)0.015 (4)0.001 (3)0.002 (3)−0.001 (3)
N10.020 (4)0.028 (4)0.019 (4)0.000 (3)0.002 (3)0.000 (3)
N20.014 (3)0.014 (3)0.013 (3)0.003 (3)0.001 (3)0.002 (3)
O10.028 (4)0.020 (3)0.036 (4)−0.008 (3)0.001 (3)0.003 (3)
O20.049 (5)0.037 (4)0.052 (5)−0.022 (4)−0.009 (4)0.008 (4)
O30.027 (4)0.018 (3)0.034 (4)0.001 (3)0.004 (3)0.002 (3)
O40.033 (4)0.023 (4)0.069 (5)0.013 (3)0.005 (4)−0.002 (4)
O50.052 (5)0.024 (3)0.027 (3)0.016 (3)0.018 (3)0.002 (3)
O60.038 (4)0.023 (3)0.015 (3)0.012 (3)0.010 (3)0.004 (2)
O70.027 (4)0.022 (3)0.012 (3)0.011 (2)0.003 (3)0.002 (2)
O80.029 (4)0.021 (3)0.013 (3)0.006 (3)0.001 (3)−0.002 (2)
O90.032 (4)0.037 (4)0.015 (3)−0.010 (3)0.002 (3)0.005 (3)
O100.046 (5)0.056 (5)0.017 (3)−0.032 (4)0.000 (3)−0.001 (3)
O110.051 (5)0.034 (4)0.032 (4)−0.014 (3)0.025 (4)−0.002 (3)
O120.062 (7)0.047 (6)0.148 (12)0.013 (5)−0.011 (7)−0.004 (7)
O130.066 (8)0.043 (6)0.163 (14)0.000 (5)0.013 (9)−0.004 (7)
O140.026 (4)0.033 (4)0.023 (4)−0.002 (3)0.002 (3)0.001 (3)
Geometric parameters (Å, º) top
Gd1—O92.458 (7)C9—N21.343 (10)
Gd1—O32.497 (6)C9—C101.408 (11)
Gd1—O8i2.496 (6)C10—C111.414 (12)
Gd1—O102.496 (6)C10—H100.930
Gd1—O62.523 (6)C11—C121.363 (13)
Gd1—O72.554 (6)C11—H110.930
Gd1—O12.566 (6)C12—C131.409 (11)
Gd1—N12.624 (9)C12—H120.930
Gd1—N22.631 (6)C13—N21.338 (10)
C1—O11.232 (13)C13—C141.506 (11)
C1—O21.261 (13)C14—O81.256 (10)
C1—C21.501 (15)C14—O71.285 (10)
C2—N11.356 (12)O2—H20.820
C2—C31.383 (16)O8—Gd1ii2.496 (6)
C3—C41.37 (2)O9—H210.82 (9)
C3—H30.930O9—H220.83 (12)
C4—C51.39 (2)O10—H230.82 (13)
C4—H40.930O10—H240.81 (13)
C5—C61.377 (16)O11—H250.81 (9)
C5—H50.930O11—H260.85 (7)
C6—N11.335 (13)O12—H270.83 (9)
C6—C71.526 (13)O12—H280.86 (9)
C7—O41.216 (12)O13—H290.83 (15)
C7—O31.278 (12)O13—H300.82 (10)
C8—O51.232 (11)O14—H310.81 (12)
C8—O61.273 (10)O14—H320.81 (14)
C8—C91.515 (11)
O9—Gd1—O380.1 (2)C6—C5—H5120.7
O9—Gd1—O8i72.1 (2)N1—C6—C5122.2 (11)
O3—Gd1—O8i74.7 (2)N1—C6—C7114.4 (9)
O9—Gd1—O10142.0 (2)C5—C6—C7123.4 (10)
O3—Gd1—O1098.0 (3)O4—C7—O3126.3 (9)
O8i—Gd1—O1070.9 (2)O4—C7—C6117.6 (9)
O9—Gd1—O686.2 (2)O3—C7—C6116.0 (8)
O3—Gd1—O6152.5 (2)O5—C8—O6125.9 (8)
O8i—Gd1—O678.4 (2)O5—C8—C9118.4 (8)
O10—Gd1—O678.5 (3)O6—C8—C9115.7 (7)
O9—Gd1—O772.8 (2)N2—C9—C10121.9 (7)
O3—Gd1—O776.0 (2)N2—C9—C8115.7 (7)
O8i—Gd1—O7137.3 (2)C10—C9—C8122.3 (7)
O10—Gd1—O7144.0 (2)C11—C10—C9117.5 (8)
O6—Gd1—O7122.46 (19)C11—C10—H10121.2
O9—Gd1—O1140.7 (2)C9—C10—H10121.3
O3—Gd1—O1123.7 (2)C12—C11—C10120.3 (8)
O8i—Gd1—O1139.7 (2)C12—C11—H11119.9
O10—Gd1—O171.0 (2)C10—C11—H11119.8
O6—Gd1—O181.4 (2)C11—C12—C13118.3 (8)
O7—Gd1—O182.9 (2)C11—C12—H12120.8
O9—Gd1—N1133.4 (2)C13—C12—H12120.9
O3—Gd1—N162.0 (2)N2—C13—C12122.4 (7)
O8i—Gd1—N1117.9 (2)N2—C13—C14114.8 (7)
O10—Gd1—N173.4 (3)C12—C13—C14122.7 (7)
O6—Gd1—N1139.3 (2)O8—C14—O7125.9 (7)
O7—Gd1—N172.5 (2)O8—C14—C13118.2 (7)
O1—Gd1—N162.0 (2)O7—C14—C13115.9 (7)
O9—Gd1—N275.7 (2)C6—N1—C2118.9 (9)
O3—Gd1—N2135.2 (2)C6—N1—Gd1120.6 (6)
O8i—Gd1—N2129.7 (2)C2—N1—Gd1120.4 (6)
O10—Gd1—N2124.0 (3)C9—N2—C13119.4 (7)
O6—Gd1—N261.85 (19)C9—N2—Gd1118.0 (5)
O7—Gd1—N261.20 (19)C13—N2—Gd1121.2 (5)
O1—Gd1—N265.6 (2)C1—O1—Gd1123.4 (6)
N1—Gd1—N2112.3 (2)C1—O2—H2114.00
O1—C1—O2122.8 (10)C7—O3—Gd1126.7 (6)
O1—C1—C2120.5 (9)C8—O6—Gd1124.6 (5)
O2—C1—C2116.7 (10)C14—O7—Gd1125.7 (5)
N1—C2—C3121.8 (11)C14—O8—Gd1ii144.0 (5)
N1—C2—C1113.4 (8)Gd1—O9—H2198 (10)
C3—C2—C1124.7 (10)Gd1—O9—H22144 (9)
C2—C3—C4118.6 (12)H21—O9—H22118 (13)
C2—C3—H3120.8Gd1—O10—H23127 (10)
C4—C3—H3120.6Gd1—O10—H24108 (10)
C5—C4—C3119.8 (14)H23—O10—H24117 (7)
C5—C4—H4120.1H25—O11—H26118 (6)
C3—C4—H4120.1H27—O12—H28111 (13)
C4—C5—C6118.6 (13)H29—O13—H30114 (16)
C4—C5—H5120.7H31—O14—H32118 (7)
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O130.821.682.495 (9)180
O9—H21···O14ii0.82 (9)2.09 (10)2.782 (10)141 (13)
O9—H22···O11iii0.83 (12)1.92 (13)2.728 (10)165 (16)
O10—H23···O4iv0.82 (13)1.93 (12)2.713 (10)160 (17)
O10—H24···O7i0.81 (13)2.01 (8)2.752 (9)152 (17)
O11—H25···O5v0.81 (9)1.96 (7)2.719 (9)156 (14)
O11—H26···O14v0.85 (7)2.15 (9)2.905 (10)147 (13)
O12—H27···O11i0.83 (9)2.59 (12)3.072 (15)119 (11)
O12—H28···O13v0.86 (9)2.75 (15)2.810 (18)85 (10)
O13—H29···O4vi0.83 (15)2.20 (14)2.649 (14)114 (13)
O13—H30···O12iv0.82 (10)2.44 (16)2.810 (18)108 (14)
O14—H31···O5vii0.81 (12)2.10 (13)2.891 (10)165 (13)
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x−1, y, z; (iv) −x+1, y+1/2, −z+3/2; (v) −x+1, y−1/2, −z+3/2; (vi) x, y+1, z; (vii) −x, y−1/2, −z+3/2.
Acknowledgements top

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references
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