Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807045618/hy2077sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807045618/hy2077Isup2.hkl |
CCDC reference: 663635
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%.
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.
For related compounds, see: Kamath & Udupa (1983); Kameshwar et al. (2007); Udupa & Krebs (1978); Zeng & Pan (1992).
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).
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.] |
[Tb(C4H6NO3)3(H2O)3] | Dx = 1.982 Mg m−3 Dm = 1.983 Mg m−3 Dm measured by floatation method |
Mr = 561.26 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 25 reflections |
Hall symbol: R 3 | θ = 12.7–16.8° |
a = 16.540 (4) Å | µ = 3.83 mm−1 |
c = 5.9554 (12) Å | T = 298 K |
V = 1411.0 (6) Å3 | Needle, colourless |
Z = 3 | 0.40 × 0.18 × 0.18 mm |
F(000) = 834 |
Rigaku AFC-7S diffractometer | 694 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 27.4°, θmin = 3.7° |
ω–2θ scans | h = −21→18 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→21 |
Tmin = 0.310, Tmax = 0.515 | l = −4→7 |
1384 measured reflections | 3 standard reflections every 150 reflections |
892 independent reflections | intensity decay: 1.8% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.015 | All H-atom parameters refined |
wR(F2) = 0.037 | w = 1/[σ2(Fo2) + (0.0321P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
892 reflections | Δρmax = 0.37 e Å−3 |
111 parameters | Δρmin = −0.76 e Å−3 |
7 restraints | Absolute structure: Flack (1983); 172 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.013 (11) |
[Tb(C4H6NO3)3(H2O)3] | Z = 3 |
Mr = 561.26 | Mo Kα radiation |
Trigonal, R3 | µ = 3.83 mm−1 |
a = 16.540 (4) Å | T = 298 K |
c = 5.9554 (12) Å | 0.40 × 0.18 × 0.18 mm |
V = 1411.0 (6) Å3 |
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 = 0.515 | 3 standard reflections every 150 reflections |
1384 measured reflections | intensity decay: 1.8% |
892 independent reflections |
R[F2 > 2σ(F2)] = 0.015 | All H-atom parameters refined |
wR(F2) = 0.037 | Δρmax = 0.37 e Å−3 |
S = 1.01 | Δρmin = −0.76 e Å−3 |
892 reflections | Absolute structure: Flack (1983); 172 Friedel pairs |
111 parameters | Absolute structure parameter: −0.013 (11) |
7 restraints |
x | y | z | Uiso*/Ueq | ||
C2 | 0.2261 (2) | 0.2052 (2) | 0.2356 (5) | 0.0230 (6) | |
N2 | 0.25512 (18) | 0.1769 (2) | 0.0361 (5) | 0.0238 (5) | |
C3 | 0.3229 (2) | 0.1546 (2) | 0.0448 (5) | 0.0242 (6) | |
O3 | 0.36586 (17) | 0.1634 (2) | 0.2220 (4) | 0.0336 (6) | |
C4 | 0.3410 (3) | 0.1165 (3) | −0.1642 (7) | 0.0343 (8) | |
O4 | −0.1128 (2) | −0.0928 (2) | 0.9043 (4) | 0.0257 (5) | |
H1 | 0.223 (3) | 0.169 (3) | −0.099 (9) | 0.039 (12)* | |
H2B | 0.280 (3) | 0.247 (3) | 0.335 (7) | 0.028 (10)* | |
H2A | 0.190 (3) | 0.234 (3) | 0.202 (8) | 0.041 (12)* | |
H4A | 0.314 (4) | 0.129 (4) | −0.301 (9) | 0.058 (15)* | |
H4C | 0.404 (5) | 0.140 (4) | −0.185 (11) | 0.08 (2)* | |
H4B | 0.314 (4) | 0.051 (4) | −0.169 (10) | 0.065 (18)* | |
H2W | −0.0975 | −0.1118 | 1.0376 | 0.048 (13)* | |
H1W | −0.1653 | −0.1002 | 0.8540 | 0.09 (3)* | |
Tb1 | 0.0000 | 0.0000 | 0.6338 | 0.01496 (6) | |
O1 | 0.11955 (16) | 0.04238 (17) | 0.3289 (4) | 0.0231 (4) | |
O2 | 0.14810 (16) | 0.14866 (16) | 0.5830 (4) | 0.0258 (5) | |
C1 | 0.1632 (3) | 0.1268 (2) | 0.3916 (5) | 0.0173 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C2 | 0.0198 (13) | 0.0239 (14) | 0.0214 (15) | 0.0080 (12) | 0.0025 (12) | 0.0027 (12) |
N2 | 0.0176 (11) | 0.0309 (14) | 0.0180 (12) | 0.0084 (11) | 0.0003 (10) | 0.0017 (11) |
C3 | 0.0170 (13) | 0.0237 (15) | 0.0241 (15) | 0.0043 (12) | 0.0038 (12) | 0.0040 (12) |
O3 | 0.0252 (12) | 0.0481 (15) | 0.0273 (13) | 0.0183 (11) | −0.0041 (10) | 0.0008 (12) |
C4 | 0.0286 (17) | 0.038 (2) | 0.032 (2) | 0.0134 (15) | 0.0061 (15) | −0.0041 (16) |
O4 | 0.0211 (13) | 0.0325 (14) | 0.0227 (12) | 0.0126 (12) | 0.0009 (11) | 0.0103 (11) |
Tb1 | 0.01651 (7) | 0.01651 (7) | 0.01186 (9) | 0.00826 (3) | 0.000 | 0.000 |
O1 | 0.0244 (11) | 0.0221 (11) | 0.0204 (10) | 0.0099 (9) | 0.0020 (9) | −0.0010 (9) |
O2 | 0.0280 (11) | 0.0260 (11) | 0.0175 (11) | 0.0092 (9) | 0.0041 (9) | −0.0025 (9) |
C1 | 0.0131 (14) | 0.0221 (15) | 0.0157 (13) | 0.0081 (13) | −0.0014 (12) | 0.0017 (12) |
C2—N2 | 1.445 (4) | Tb1—O4i | 2.359 (3) |
C2—C1 | 1.509 (4) | Tb1—O4ii | 2.359 (3) |
C2—H2B | 1.00 (4) | Tb1—O2i | 2.473 (2) |
C2—H2A | 0.95 (5) | Tb1—O2ii | 2.473 (2) |
N2—C3 | 1.345 (4) | Tb1—O2 | 2.473 (2) |
N2—H1 | 0.94 (5) | Tb1—O1i | 2.513 (2) |
C3—O3 | 1.239 (4) | Tb1—O1 | 2.513 (2) |
C3—C4 | 1.492 (5) | Tb1—O1ii | 2.513 (2) |
C4—H4A | 1.00 (6) | Tb1—C1i | 2.847 (3) |
C4—H4C | 0.92 (7) | Tb1—C1ii | 2.847 (3) |
C4—H4B | 0.94 (6) | Tb1—C1 | 2.847 (3) |
O4—H2W | 0.934 | O1—C1 | 1.266 (4) |
O4—H1W | 0.868 | O2—C1 | 1.258 (4) |
Tb1—O4 | 2.359 (3) | ||
N2—C2—C1 | 115.2 (3) | O1i—Tb1—O1 | 73.53 (8) |
N2—C2—H2B | 113 (2) | O4i—Tb1—O1ii | 93.22 (9) |
C1—C2—H2B | 103 (2) | O4ii—Tb1—O1ii | 158.57 (8) |
N2—C2—H2A | 113 (3) | O4—Tb1—O1ii | 119.55 (8) |
C1—C2—H2A | 103 (3) | O2i—Tb1—O1ii | 123.70 (7) |
H2B—C2—H2A | 109 (4) | O2ii—Tb1—O1ii | 51.97 (7) |
C3—N2—C2 | 121.0 (3) | O2—Tb1—O1ii | 78.21 (8) |
C3—N2—H1 | 119 (3) | O1i—Tb1—O1ii | 73.53 (8) |
C2—N2—H1 | 120 (3) | O1—Tb1—O1ii | 73.53 (8) |
O3—C3—N2 | 120.6 (3) | O4i—Tb1—C1i | 167.21 (8) |
O3—C3—C4 | 122.4 (3) | O4ii—Tb1—C1i | 93.26 (10) |
N2—C3—C4 | 117.1 (3) | O4—Tb1—C1i | 90.32 (11) |
C3—C4—H4A | 113 (3) | O2i—Tb1—C1i | 26.15 (8) |
C3—C4—H4C | 111 (4) | O2ii—Tb1—C1i | 101.31 (9) |
H4A—C4—H4C | 109 (5) | O2—Tb1—C1i | 121.02 (9) |
C3—C4—H4B | 115 (4) | O1i—Tb1—C1i | 26.40 (8) |
H4A—C4—H4B | 102 (5) | O1—Tb1—C1i | 70.24 (9) |
H4C—C4—H4B | 106 (5) | O1ii—Tb1—C1i | 97.76 (8) |
Tb1—O4—H2W | 122.7 | O4i—Tb1—C1ii | 90.32 (11) |
Tb1—O4—H1W | 105.44 | O4ii—Tb1—C1ii | 167.21 (8) |
H2W—O4—H1W | 131.8 | O4—Tb1—C1ii | 93.26 (10) |
O4i—Tb1—O4ii | 78.52 (11) | O2i—Tb1—C1ii | 121.02 (9) |
O4i—Tb1—O4 | 78.52 (11) | O2ii—Tb1—C1ii | 26.15 (8) |
O4ii—Tb1—O4 | 78.52 (11) | O2—Tb1—C1ii | 101.31 (9) |
O4i—Tb1—O2i | 142.98 (9) | O1i—Tb1—C1ii | 70.24 (9) |
O4ii—Tb1—O2i | 67.66 (8) | O1—Tb1—C1ii | 97.76 (8) |
O4—Tb1—O2i | 80.36 (9) | O1ii—Tb1—C1ii | 26.40 (8) |
O4i—Tb1—O2ii | 80.36 (9) | C1i—Tb1—C1ii | 96.60 (9) |
O4ii—Tb1—O2ii | 142.98 (9) | O4i—Tb1—C1 | 93.26 (10) |
O4—Tb1—O2ii | 67.66 (8) | O4ii—Tb1—C1 | 90.32 (11) |
O2i—Tb1—O2ii | 118.52 (2) | O4—Tb1—C1 | 167.21 (8) |
O4i—Tb1—O2 | 67.66 (8) | O2i—Tb1—C1 | 101.31 (9) |
O4ii—Tb1—O2 | 80.36 (9) | O2ii—Tb1—C1 | 121.02 (9) |
O4—Tb1—O2 | 142.98 (9) | O2—Tb1—C1 | 26.15 (8) |
O2i—Tb1—O2 | 118.52 (2) | O1i—Tb1—C1 | 97.76 (8) |
O2ii—Tb1—O2 | 118.52 (2) | O1—Tb1—C1 | 26.40 (8) |
O4i—Tb1—O1i | 158.57 (8) | O1ii—Tb1—C1 | 70.24 (9) |
O4ii—Tb1—O1i | 119.55 (8) | C1i—Tb1—C1 | 96.60 (9) |
O4—Tb1—O1i | 93.22 (9) | C1ii—Tb1—C1 | 96.60 (9) |
O2i—Tb1—O1i | 51.97 (7) | C1—O1—Tb1 | 91.7 (2) |
O2ii—Tb1—O1i | 78.21 (8) | C1—O2—Tb1 | 93.8 (2) |
O2—Tb1—O1i | 123.70 (8) | O2—C1—O1 | 119.9 (3) |
O4i—Tb1—O1 | 119.55 (8) | O2—C1—C2 | 117.5 (3) |
O4ii—Tb1—O1 | 93.22 (9) | O1—C1—C2 | 122.3 (3) |
O4—Tb1—O1 | 158.57 (8) | O2—C1—Tb1 | 60.08 (17) |
O2i—Tb1—O1 | 78.21 (8) | O1—C1—Tb1 | 61.90 (18) |
O2ii—Tb1—O1 | 123.70 (7) | C2—C1—Tb1 | 159.6 (2) |
O2—Tb1—O1 | 51.97 (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—C4 | 173.7 (3) | O2i—Tb1—C1—O2 | −134.22 (18) |
O4i—Tb1—O1—C1 | −5.6 (3) | O2ii—Tb1—C1—O2 | 92.27 (16) |
O4ii—Tb1—O1—C1 | −84.2 (2) | O1i—Tb1—C1—O2 | 173.14 (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—O2 | 103.8 (2) |
O2ii—Tb1—O1—C1 | 92.8 (2) | C1i—Tb1—C1—O2 | −160.3 (2) |
O2—Tb1—O1—C1 | −9.12 (19) | C1ii—Tb1—C1—O2 | 102.3 (2) |
O1i—Tb1—O1—C1 | 155.9 (2) | O4i—Tb1—C1—O1 | 175.1 (2) |
O1ii—Tb1—O1—C1 | 78.6 (2) | O4ii—Tb1—C1—O1 | 96.60 (19) |
C1i—Tb1—O1—C1 | −176.5 (2) | O4—Tb1—C1—O1 | 125.6 (4) |
C1ii—Tb1—O1—C1 | 89.20 (15) | O2i—Tb1—C1—O1 | 29.3 (2) |
O4i—Tb1—O2—C1 | −167.5 (2) | O2ii—Tb1—C1—O1 | −104.2 (2) |
O4ii—Tb1—O2—C1 | 111.0 (2) | O2—Tb1—C1—O1 | 163.6 (3) |
O4—Tb1—O2—C1 | 166.95 (19) | O1i—Tb1—C1—O1 | −23.3 (2) |
O2i—Tb1—O2—C1 | 53.1 (2) | O1ii—Tb1—C1—O1 | −92.6 (2) |
O2ii—Tb1—O2—C1 | −102.93 (19) | C1i—Tb1—C1—O1 | 3.3 (2) |
O1i—Tb1—O2—C1 | −8.2 (2) | C1ii—Tb1—C1—O1 | −94.18 (15) |
O1—Tb1—O2—C1 | 9.20 (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—C1 | 23.0 (2) | O4—Tb1—C1—C2 | −126.9 (6) |
C1ii—Tb1—O2—C1 | −81.9 (2) | O2i—Tb1—C1—C2 | 136.8 (6) |
Tb1—O2—C1—O1 | −16.7 (4) | O2ii—Tb1—C1—C2 | 3.3 (7) |
Tb1—O2—C1—C2 | 156.9 (3) | O2—Tb1—C1—C2 | −88.9 (7) |
Tb1—O1—C1—O2 | 16.4 (3) | O1i—Tb1—C1—C2 | 84.2 (6) |
Tb1—O1—C1—C2 | −156.8 (3) | O1—Tb1—C1—C2 | 107.5 (7) |
N2—C2—C1—O2 | 168.9 (3) | O1ii—Tb1—C1—C2 | 14.9 (6) |
N2—C2—C1—O1 | −17.6 (5) | C1i—Tb1—C1—C2 | 110.8 (6) |
N2—C2—C1—Tb1 | −113.4 (6) | C1ii—Tb1—C1—C2 | 13.3 (7) |
O4i—Tb1—C1—O2 | 11.56 (19) |
Symmetry codes: (i) −x+y, −x, z; (ii) −y, x−y, z. |
Experimental details
Crystal data | |
Chemical formula | [Tb(C4H6NO3)3(H2O)3] |
Mr | 561.26 |
Crystal system, space group | Trigonal, R3 |
Temperature (K) | 298 |
a, c (Å) | 16.540 (4), 5.9554 (12) |
V (Å3) | 1411.0 (6) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 3.83 |
Crystal size (mm) | 0.40 × 0.18 × 0.18 |
Data collection | |
Diffractometer | Rigaku AFC-7S |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.310, 0.515 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1384, 892, 694 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.015, 0.037, 1.01 |
No. of reflections | 892 |
No. of parameters | 111 |
No. of restraints | 7 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.37, −0.76 |
Absolute structure | Flack (1983); 172 Friedel pairs |
Absolute structure parameter | −0.013 (11) |
Computer programs: WinAFC (Rigaku/MSC, 2004), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Tb1—O4 | 2.359 (3) | Tb1—O1 | 2.513 (2) |
Tb1—O2 | 2.473 (2) | ||
O4i—Tb1—O4 | 78.52 (11) | O4i—Tb1—O1 | 93.22 (9) |
O4—Tb1—O2i | 67.66 (8) | O4—Tb1—O1 | 158.57 (8) |
O4i—Tb1—O2 | 80.36 (9) | O2—Tb1—O1 | 51.97 (7) |
O4—Tb1—O2 | 142.98 (9) | O4—Tb1—O1i | 119.55 (8) |
Symmetry code: (i) −y, x−y, z. |
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.