supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m2584    [ doi:10.1107/S1600536807045618 ]

Tris(N-acetylglycinato-[kappa]2O,O')triaquaterbium(III)

P. M. Kameshwar, A. Wadawale and V. R. Ajgaonkar

Abstract top

The title complex, [Tb(C4H6NO3)3(H2O)3], was prepared by reacting terbium carbonate with N-acetylglycine in aqueous medium. The TbIII atom is coordinated by nine O atoms, six of them belonging to the three carboxylate groups of the ligands and three to the water molecules. The molecule lies on a threefold rotation axis.

Comment top

Rare earth complexes of N-acetylglycine were synthesized and reported to be isostructural and hexagonal (Kamath & Udupa, 1983). However, the detailed structural analysis was not given. The crystal structures of neodymium, europium and erbium complexes of N-acetylglycine have been reported (Zeng & Pan, 1992). The compounds were found to be isostructural and trigonal.

The structure of the title compound contains a TbIII atom coordinated by six O atoms from three carboxylate groups and three O atoms from water molecules (Fig. 1). The three chelated carboxylate rings are completely staggered. The three Tb—O(water) bonds are also completely staggered with the same angle of 78.5 (1)° between two such bonds (Table 1). The angles O1—C1—O2 are 119.9 (3)°, while the angles subtended at Tb atom by the carboxylate O atoms (O2—Tb1—O1) is 51.97 (7)°. The bond distances between the two carboxylate O atoms and the Tb atom differ by only 0.04 Å. The bond lengths of the two carboxylate O atoms to the C atom differ by only 0.008 Å. The carboxylate group is thus resonance stabilized and functions symmetrically as a bidentate chelate. Apart from the carboxylate group, the bond distances and bond angles of N-acetylglycinate moiety in the title compound are not significantly different from those of free N-acetylglycine and its copper (Udupa and Krebs, 1978), neodymium, europium and erbium complexes (Zeng & Pan, 1992).

The title compound is isostructural with its samarium (Kameshwar et al., 2007), neodymium, europium and erbium analogues (Zeng & Pan, 1992). The coordination geometry of the title compound can be described in terms of a 4,4,4-tricapped triangular prism. The lattice parameters of the samarium and terbium complexes are in line with the well known lanthanide contraction. Interestingly, the terbium complex is found to be triboluminescent and emit green light on striking the crystals with a spatula or a glass rod when observed in dark.

Related literature top

For related compounds, see: Kamath & Udupa (1983); Kameshwar et al. (2007); Udupa & Krebs (1978); Zeng & Pan (1992).

Experimental top

The title compound was synthesized by adding terbium carbonate (0.397 g, 2.5 mmol) to N-acetylglycine (0.878 g, 7.5 mmol) dissolved in 50 ml water and allowing to react on a steam bath till the carbonate dissolved. A few mg of the carbonate was added to ensure that no unreacted acid was present. The unreacted carbonate was filtered off and the filtrate was evaporated naturally at ambient temperature. The crystals suitable for X-ray diffraction were picked up and dried in air. Analysis, calculated for C12H24N3O12Tb: C 25.68, H 4.31, N 7.49, Tb 28.32%; found: C 25.26, H 4.33, N 7.11, Tb 28.05%.

Refinement top

All H atoms were found in difference Fourier maps and refined isotropically.

Computing details top

Data collection: WinAFC (Rigaku/MSC, 2004); cell refinement: WinAFC (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) −x + y, −x, z; (ii) −y, x-y, z.]
Tris(N-acetylglycinato-κ2O,O')triaquaterbium(III) top
Crystal data top
[Tb(C4H6NO3)3(H2O)3]Z = 3
Mr = 561.26F000 = 834
Trigonal, R3Dx = 1.982 Mg m−3
Dm = 1.983 Mg m−3
Dm measured by floatation method
Hall symbol: R 3Mo Kα radiation
λ = 0.71073 Å
a = 16.540 (4) ÅCell parameters from 25 reflections
b = 16.540 (4) Åθ = 12.7–16.8º
c = 5.9554 (12) ŵ = 3.83 mm−1
α = 90ºT = 298 (2) K
β = 90ºNeedle, colourless
γ = 120º0.40 × 0.18 × 0.18 mm
V = 1411.0 (6) Å3
Data collection top
Rigaku AFC-7S
diffractometer		Rint = 0.019
Radiation source: fine-focus sealed tubeθmax = 27.4º
Monochromator: graphiteθmin = 3.7º
T = 298(2) Kh = −21→18
ω–2θ scansk = 0→21
Absorption correction: ψ scan
(North et al., 1968)		l = −4→7
Tmin = 0.310, Tmax = 0.5153 standard reflections
1384 measured reflections every 150 reflections
892 independent reflections intensity decay: 1.8%
694 reflections with I > 2σ(I)
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.015  w = 1/[σ2(Fo2) + (0.0321P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.037(Δ/σ)max < 0.001
S = 1.01Δρmax = 0.37 e Å−3
892 reflectionsΔρmin = −0.76 e Å−3
111 parametersExtinction correction: none
7 restraintsAbsolute structure: Flack (1983); 172 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.013 (11)
Secondary atom site location: difference Fourier map
Crystal data top
[Tb(C4H6NO3)3(H2O)3]γ = 120º
Mr = 561.26V = 1411.0 (6) Å3
Trigonal, R3Z = 3
a = 16.540 (4) ÅMo Kα
b = 16.540 (4) ŵ = 3.83 mm−1
c = 5.9554 (12) ÅT = 298 (2) K
α = 90º0.40 × 0.18 × 0.18 mm
β = 90º
Data collection top
Rigaku AFC-7S
diffractometer		694 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.019
Tmin = 0.310, Tmax = 0.5153 standard reflections
1384 measured reflections every 150 reflections
892 independent reflections intensity decay: 1.8%
Refinement top
R[F2 > 2σ(F2)] = 0.015All H-atom parameters refined
wR(F2) = 0.037Δρmax = 0.37 e Å−3
S = 1.01Δρmin = −0.76 e Å−3
892 reflectionsAbsolute structure: Flack (1983); 172 Friedel pairs
111 parametersFlack parameter: −0.013 (11)
7 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C20.2261 (2)0.2052 (2)0.2356 (5)0.0230 (6)
N20.25512 (18)0.1769 (2)0.0361 (5)0.0238 (5)
C30.3229 (2)0.1546 (2)0.0448 (5)0.0242 (6)
O30.36586 (17)0.1634 (2)0.2220 (4)0.0336 (6)
C40.3410 (3)0.1165 (3)−0.1642 (7)0.0343 (8)
O4−0.1128 (2)−0.0928 (2)0.9043 (4)0.0257 (5)
H10.223 (3)0.169 (3)−0.099 (9)0.039 (12)*
H2B0.280 (3)0.247 (3)0.335 (7)0.028 (10)*
H2A0.190 (3)0.234 (3)0.202 (8)0.041 (12)*
H4A0.314 (4)0.129 (4)−0.301 (9)0.058 (15)*
H4C0.404 (5)0.140 (4)−0.185 (11)0.08 (2)*
H4B0.314 (4)0.051 (4)−0.169 (10)0.065 (18)*
H2W−0.0975−0.11181.03760.048 (13)*
H1W−0.1653−0.10020.85400.09 (3)*
Tb10.00000.00000.63380.01496 (6)
O10.11955 (16)0.04238 (17)0.3289 (4)0.0231 (4)
O20.14810 (16)0.14866 (16)0.5830 (4)0.0258 (5)
C10.1632 (3)0.1268 (2)0.3916 (5)0.0173 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C20.0198 (13)0.0239 (14)0.0214 (15)0.0080 (12)0.0025 (12)0.0027 (12)
N20.0176 (11)0.0309 (14)0.0180 (12)0.0084 (11)0.0003 (10)0.0017 (11)
C30.0170 (13)0.0237 (15)0.0241 (15)0.0043 (12)0.0038 (12)0.0040 (12)
O30.0252 (12)0.0481 (15)0.0273 (13)0.0183 (11)−0.0041 (10)0.0008 (12)
C40.0286 (17)0.038 (2)0.032 (2)0.0134 (15)0.0061 (15)−0.0041 (16)
O40.0211 (13)0.0325 (14)0.0227 (12)0.0126 (12)0.0009 (11)0.0103 (11)
Tb10.01651 (7)0.01651 (7)0.01186 (9)0.00826 (3)0.0000.000
O10.0244 (11)0.0221 (11)0.0204 (10)0.0099 (9)0.0020 (9)−0.0010 (9)
O20.0280 (11)0.0260 (11)0.0175 (11)0.0092 (9)0.0041 (9)−0.0025 (9)
C10.0131 (14)0.0221 (15)0.0157 (13)0.0081 (13)−0.0014 (12)0.0017 (12)
Geometric parameters (Å, °) top
C2—N21.445 (4)Tb1—O4i2.359 (3)
C2—C11.509 (4)Tb1—O4ii2.359 (3)
C2—H2B1.00 (4)Tb1—O2i2.473 (2)
C2—H2A0.95 (5)Tb1—O2ii2.473 (2)
N2—C31.345 (4)Tb1—O22.473 (2)
N2—H10.94 (5)Tb1—O1i2.513 (2)
C3—O31.239 (4)Tb1—O12.513 (2)
C3—C41.492 (5)Tb1—O1ii2.513 (2)
C4—H4A1.00 (6)Tb1—C1i2.847 (3)
C4—H4C0.92 (7)Tb1—C1ii2.847 (3)
C4—H4B0.94 (6)Tb1—C12.847 (3)
O4—H2W0.934O1—C11.266 (4)
O4—H1W0.868O2—C11.258 (4)
Tb1—O42.359 (3)
N2—C2—C1115.2 (3)O1i—Tb1—O173.53 (8)
N2—C2—H2B113 (2)O4i—Tb1—O1ii93.22 (9)
C1—C2—H2B103 (2)O4ii—Tb1—O1ii158.57 (8)
N2—C2—H2A113 (3)O4—Tb1—O1ii119.55 (8)
C1—C2—H2A103 (3)O2i—Tb1—O1ii123.70 (7)
H2B—C2—H2A109 (4)O2ii—Tb1—O1ii51.97 (7)
C3—N2—C2121.0 (3)O2—Tb1—O1ii78.21 (8)
C3—N2—H1119 (3)O1i—Tb1—O1ii73.53 (8)
C2—N2—H1120 (3)O1—Tb1—O1ii73.53 (8)
O3—C3—N2120.6 (3)O4i—Tb1—C1i167.21 (8)
O3—C3—C4122.4 (3)O4ii—Tb1—C1i93.26 (10)
N2—C3—C4117.1 (3)O4—Tb1—C1i90.32 (11)
C3—C4—H4A113 (3)O2i—Tb1—C1i26.15 (8)
C3—C4—H4C111 (4)O2ii—Tb1—C1i101.31 (9)
H4A—C4—H4C109 (5)O2—Tb1—C1i121.02 (9)
C3—C4—H4B115 (4)O1i—Tb1—C1i26.40 (8)
H4A—C4—H4B102 (5)O1—Tb1—C1i70.24 (9)
H4C—C4—H4B106 (5)O1ii—Tb1—C1i97.76 (8)
Tb1—O4—H2W122.7O4i—Tb1—C1ii90.32 (11)
Tb1—O4—H1W105.44O4ii—Tb1—C1ii167.21 (8)
H2W—O4—H1W131.8O4—Tb1—C1ii93.26 (10)
O4i—Tb1—O4ii78.52 (11)O2i—Tb1—C1ii121.02 (9)
O4i—Tb1—O478.52 (11)O2ii—Tb1—C1ii26.15 (8)
O4ii—Tb1—O478.52 (11)O2—Tb1—C1ii101.31 (9)
O4i—Tb1—O2i142.98 (9)O1i—Tb1—C1ii70.24 (9)
O4ii—Tb1—O2i67.66 (8)O1—Tb1—C1ii97.76 (8)
O4—Tb1—O2i80.36 (9)O1ii—Tb1—C1ii26.40 (8)
O4i—Tb1—O2ii80.36 (9)C1i—Tb1—C1ii96.60 (9)
O4ii—Tb1—O2ii142.98 (9)O4i—Tb1—C193.26 (10)
O4—Tb1—O2ii67.66 (8)O4ii—Tb1—C190.32 (11)
O2i—Tb1—O2ii118.52 (2)O4—Tb1—C1167.21 (8)
O4i—Tb1—O267.66 (8)O2i—Tb1—C1101.31 (9)
O4ii—Tb1—O280.36 (9)O2ii—Tb1—C1121.02 (9)
O4—Tb1—O2142.98 (9)O2—Tb1—C126.15 (8)
O2i—Tb1—O2118.52 (2)O1i—Tb1—C197.76 (8)
O2ii—Tb1—O2118.52 (2)O1—Tb1—C126.40 (8)
O4i—Tb1—O1i158.57 (8)O1ii—Tb1—C170.24 (9)
O4ii—Tb1—O1i119.55 (8)C1i—Tb1—C196.60 (9)
O4—Tb1—O1i93.22 (9)C1ii—Tb1—C196.60 (9)
O2i—Tb1—O1i51.97 (7)C1—O1—Tb191.7 (2)
O2ii—Tb1—O1i78.21 (8)C1—O2—Tb193.8 (2)
O2—Tb1—O1i123.70 (8)O2—C1—O1119.9 (3)
O4i—Tb1—O1119.55 (8)O2—C1—C2117.5 (3)
O4ii—Tb1—O193.22 (9)O1—C1—C2122.3 (3)
O4—Tb1—O1158.57 (8)O2—C1—Tb160.08 (17)
O2i—Tb1—O178.21 (8)O1—C1—Tb161.90 (18)
O2ii—Tb1—O1123.70 (7)C2—C1—Tb1159.6 (2)
O2—Tb1—O151.97 (7)
C1—C2—N2—C3−77.5 (4)O4ii—Tb1—C1—O2−67.0 (2)
C2—N2—C3—O3−4.4 (5)O4—Tb1—C1—O2−37.9 (5)
C2—N2—C3—C4173.7 (3)O2i—Tb1—C1—O2−134.22 (18)
O4i—Tb1—O1—C1−5.6 (3)O2ii—Tb1—C1—O292.27 (16)
O4ii—Tb1—O1—C1−84.2 (2)O1i—Tb1—C1—O2173.14 (19)
O4—Tb1—O1—C1−150.5 (2)O1—Tb1—C1—O2−163.6 (3)
O2i—Tb1—O1—C1−150.6 (2)O1ii—Tb1—C1—O2103.8 (2)
O2ii—Tb1—O1—C192.8 (2)C1i—Tb1—C1—O2−160.3 (2)
O2—Tb1—O1—C1−9.12 (19)C1ii—Tb1—C1—O2102.3 (2)
O1i—Tb1—O1—C1155.9 (2)O4i—Tb1—C1—O1175.1 (2)
O1ii—Tb1—O1—C178.6 (2)O4ii—Tb1—C1—O196.60 (19)
C1i—Tb1—O1—C1−176.5 (2)O4—Tb1—C1—O1125.6 (4)
C1ii—Tb1—O1—C189.20 (15)O2i—Tb1—C1—O129.3 (2)
O4i—Tb1—O2—C1−167.5 (2)O2ii—Tb1—C1—O1−104.2 (2)
O4ii—Tb1—O2—C1111.0 (2)O2—Tb1—C1—O1163.6 (3)
O4—Tb1—O2—C1166.95 (19)O1i—Tb1—C1—O1−23.3 (2)
O2i—Tb1—O2—C153.1 (2)O1ii—Tb1—C1—O1−92.6 (2)
O2ii—Tb1—O2—C1−102.93 (19)C1i—Tb1—C1—O13.3 (2)
O1i—Tb1—O2—C1−8.2 (2)C1ii—Tb1—C1—O1−94.18 (15)
O1—Tb1—O2—C19.20 (19)O4i—Tb1—C1—C2−77.4 (6)
O1ii—Tb1—O2—C1−69.0 (2)O4ii—Tb1—C1—C2−155.9 (6)
C1i—Tb1—O2—C123.0 (2)O4—Tb1—C1—C2−126.9 (6)
C1ii—Tb1—O2—C1−81.9 (2)O2i—Tb1—C1—C2136.8 (6)
Tb1—O2—C1—O1−16.7 (4)O2ii—Tb1—C1—C23.3 (7)
Tb1—O2—C1—C2156.9 (3)O2—Tb1—C1—C2−88.9 (7)
Tb1—O1—C1—O216.4 (3)O1i—Tb1—C1—C284.2 (6)
Tb1—O1—C1—C2−156.8 (3)O1—Tb1—C1—C2107.5 (7)
N2—C2—C1—O2168.9 (3)O1ii—Tb1—C1—C214.9 (6)
N2—C2—C1—O1−17.6 (5)C1i—Tb1—C1—C2110.8 (6)
N2—C2—C1—Tb1−113.4 (6)C1ii—Tb1—C1—C213.3 (7)
O4i—Tb1—C1—O211.56 (19)
Symmetry codes: (i) −x+y, −x, z; (ii) −y, x−y, z.
Table 1
Selected geometric parameters (Å, °) top
Tb1—O42.359 (3)Tb1—O12.513 (2)
Tb1—O22.473 (2)
O4i—Tb1—O478.52 (11)O4i—Tb1—O193.22 (9)
O4—Tb1—O2i67.66 (8)O4—Tb1—O1158.57 (8)
O4i—Tb1—O280.36 (9)O2—Tb1—O151.97 (7)
O4—Tb1—O2142.98 (9)O4—Tb1—O1i119.55 (8)
Symmetry codes: (i) −y, x−y, z.
Acknowledgements top

The authors are grateful to Dr Vimal K. Jain, Head of Synthesis & Pure Materials Section, Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai, for extending the single-crystal X-ray diffraction facility and for helpful comments. PMK gratefully acknowledges financial support from University of Mumbai.

references
References top

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Kamath, P. & Udupa, M. R. (1983). Indian J. Chem. 22A, 218–220.

Kameshwar, P. M., Wadawale, A. & Ajgaonkar, V. R. (2007). submitted to Acta Cryst. E. [Paper reference hy2078].

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

Rigaku/MSC (2004). WinAFC and CrystalStructure (Version 3.7.0). Rigaku/MSC, The Woodlands, Texas, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Udupa, M. R. & Krebs, B. (1978). Inorg. Chim. Acta, 31, 251–255.

Zeng, H. & Pan, K. (1992). Jiegou Huaxue, 11, 388–392.