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Acta Cryst. (2007). E63, m2598    [ doi:10.1107/S1600536807046429 ]

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

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

Abstract top

The title complex, [Sm(C4H6NO3)3(H2O)3], was prepared by reacting samarium(III) carbonate with N-acetylglycine in an aqueous medium. The SmIII 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 coordination geometry can be described in terms of a 4,4,4-tricapped triangular prism. 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.

In the title compound, the SmIII atom, lying on a threefold rotation axis, is coordinated by six O atoms from three carboxylate groups and three O atoms from three water molecules (Fig. 1). The three chelated carboxylate rings are completely staggered. The three Sm—O(water) bonds are also completely staggered with the same angle of 78.2 (2)° between two such bonds (Table 1). The angle O1—C1—O2 is 120.8 (6)°, while the angle subtended at Sm by the carboxylate O atoms (O1—Sm1—O2) is 51.4 (1)°. The bond distances between the two carboxylate O atoms and the Sm atom differ by only 0.033 Å. The bond lengths of the two carboxylate O atoms to the C atom are almost identical. 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 & Krebs, 1978), neodymium, europium and erbium complexes (Zeng & Pan, 1992).

The title compound is isostructural with its terbium (Kameshwar et al., 2007), neodymium, europium and erbium analogues (Zeng & Pan, 1992). The coordination geometry in the title compound can be described in terms of a 4,4,4-tricapped triangular prism.

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 samarium carbonate (0.376 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 were 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 C12H24N3O12Sm: C 26.08, H 4.38, N 7.60, Sm 27.20%; found: C 25.89, H 4.31, N 7.42, Sm 26.91%.

Refinement top

H atoms of the methyl group were positioned geometrically and refined as riding atoms, with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C). The other H atoms were found in a difference Fourier map 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) 2 − y, 1 + x-y, z; (ii) 1 − x + y, 2 − x, z.]
Tris(N-acetylglycinato-κ2O,O')triaquasamarium(III) top
Crystal data top
[Sm(C4H6NO3)3(H2O)3]Z = 3
Mr = 552.69F000 = 825
Trigonal, R3Dx = 1.935 Mg m−3
Dm = 1.932 Mg m−3
Dm measured by flotation method
Hall symbol: R 3Mo Kα radiation
λ = 0.71069 Å
a = 16.580 (4) ÅCell parameters from 25 reflections
b = 16.580 (4) Åθ = 12.7–16.7º
c = 5.978 (1) ŵ = 3.16 mm−1
α = 90ºT = 298 (2) K
β = 90ºNeedle, colourless
γ = 120º0.40 × 0.20 × 0.20 mm
V = 1423.2 (5) Å3
Data collection top
Rigaku AFC-7S
diffractometer		Rint = 0.029
Radiation source: fine-focus sealed tubeθmax = 27.5º
Monochromator: graphiteθmin = 3.7º
T = 298(2) Kh = −21→18
ω/2θ scansk = 0→21
Absorption correction: ψ scan
(North et al., 1968)		l = −7→4
Tmin = 0.364, Tmax = 0.5703 standard reflections
1396 measured reflections every 150 reflections
900 independent reflections intensity decay: 0.6%
702 reflections with I > 2σ(I)
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.020  w = 1/[σ2(Fo2) + (0.0395P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.051(Δ/σ)max < 0.001
S = 1.07Δρmax = 0.81 e Å−3
900 reflectionsΔρmin = −1.21 e Å−3
107 parametersExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
3 restraintsExtinction coefficient: 0.0017 (4)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with 176 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.03 (2)
Crystal data top
[Sm(C4H6NO3)3(H2O)3]γ = 120º
Mr = 552.69V = 1423.2 (5) Å3
Trigonal, R3Z = 3
a = 16.580 (4) ÅMo Kα
b = 16.580 (4) ŵ = 3.16 mm−1
c = 5.978 (1) ÅT = 298 (2) K
α = 90º0.40 × 0.20 × 0.20 mm
β = 90º
Data collection top
Rigaku AFC-7S
diffractometer		702 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.029
Tmin = 0.364, Tmax = 0.5703 standard reflections
1396 measured reflections every 150 reflections
900 independent reflections intensity decay: 0.6%
Refinement top
R[F2 > 2σ(F2)] = 0.020H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.051Δρmax = 0.81 e Å−3
S = 1.07Δρmin = −1.21 e Å−3
900 reflectionsAbsolute structure: Flack (1983), with 176 Friedel pairs
107 parametersFlack parameter: −0.03 (2)
3 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C40.7757 (5)0.6593 (4)−0.1291 (10)0.0392 (13)
H4C0.74020.5934−0.15480.059*
H4A0.81650.6890−0.25380.059*
H4B0.73430.6836−0.11240.059*
O20.9222 (3)0.8784 (3)0.3629 (7)0.0286 (8)
O10.9998 (3)0.8499 (3)0.6168 (6)0.0296 (8)
C10.9635 (6)0.8361 (5)0.4255 (11)0.0244 (14)
O41.0216 (3)1.1147 (4)0.9427 (7)0.0309 (9)
H10.938 (6)0.771 (5)−0.046 (13)0.05 (2)*
H2A0.968 (5)0.716 (5)0.371 (11)0.035 (17)*
H2B1.039 (5)0.808 (4)0.214 (10)0.029 (16)*
H2W0.997 (8)1.109 (9)1.064 (10)0.11 (5)*
H1W1.051 (7)1.1708 (19)0.921 (17)0.04 (3)*
Sm11.00001.00000.66730.01945 (14)
N10.9221 (3)0.7447 (3)0.0689 (8)0.0284 (10)
O30.7980 (3)0.6347 (3)0.2547 (7)0.0371 (10)
C30.8321 (4)0.6779 (3)0.0787 (9)0.0285 (11)
C20.9797 (4)0.7734 (4)0.2680 (9)0.0282 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C40.046 (3)0.037 (3)0.031 (3)0.018 (3)−0.009 (3)−0.004 (2)
O20.034 (2)0.0271 (19)0.0256 (19)0.0162 (18)−0.0032 (17)0.0001 (15)
O10.039 (2)0.032 (2)0.0205 (19)0.0195 (17)−0.0054 (15)−0.0001 (15)
C10.025 (3)0.022 (3)0.021 (3)0.009 (2)0.002 (2)0.004 (2)
O40.037 (2)0.028 (2)0.022 (2)0.011 (2)0.0082 (18)−0.0022 (19)
Sm10.02189 (15)0.02189 (15)0.01455 (18)0.01095 (8)0.0000.000
N10.039 (3)0.022 (2)0.018 (2)0.0109 (19)0.0003 (18)−0.0006 (17)
O30.041 (2)0.030 (2)0.030 (2)0.0095 (18)0.0049 (18)0.0062 (16)
C30.037 (3)0.017 (2)0.028 (3)0.011 (2)0.000 (2)−0.0023 (19)
C20.034 (3)0.024 (2)0.025 (2)0.013 (2)0.002 (2)−0.001 (2)
Geometric parameters (Å, °) top
C4—C31.491 (8)Sm1—O4ii2.403 (4)
C4—H4C0.9600Sm1—O1i2.505 (4)
C4—H4A0.9600Sm1—O1ii2.505 (4)
C4—H4B0.9600Sm1—O2ii2.538 (4)
O2—C11.258 (8)Sm1—O2i2.538 (4)
O2—Sm12.538 (4)Sm1—C1ii2.863 (8)
O1—C11.258 (9)Sm1—C1i2.863 (8)
O1—Sm12.505 (4)N1—C31.342 (7)
C1—C21.522 (9)N1—C21.450 (7)
C1—Sm12.863 (8)N1—H10.79 (7)
O4—Sm12.403 (4)O3—C31.239 (6)
O4—H2W0.81 (8)C2—H2A1.06 (7)
O4—H1W0.82 (2)C2—H2B0.91 (6)
Sm1—O4i2.403 (4)
C3—C4—H4C109.5O1i—Sm1—O2i51.42 (12)
C3—C4—H4A109.5O1ii—Sm1—O2i124.04 (13)
H4C—C4—H4A109.5O1—Sm1—O2i78.72 (14)
C3—C4—H4B109.5O2—Sm1—O2i74.26 (14)
H4C—C4—H4B109.5O2ii—Sm1—O2i74.26 (14)
H4A—C4—H4B109.5O4—Sm1—C1166.99 (15)
C1—O2—Sm191.6 (4)O4i—Sm1—C190.7 (2)
C1—O1—Sm193.1 (4)O4ii—Sm1—C192.91 (19)
O2—C1—O1120.8 (6)O1i—Sm1—C1120.94 (17)
O2—C1—C2121.9 (6)O1ii—Sm1—C1101.65 (19)
O1—C1—C2117.1 (6)O1—Sm1—C126.03 (17)
O2—C1—Sm162.4 (4)O2—Sm1—C126.05 (18)
O1—C1—Sm160.9 (3)O2ii—Sm1—C198.17 (17)
C2—C1—Sm1159.2 (5)O2i—Sm1—C170.74 (18)
Sm1—O4—H2W131 (9)O4—Sm1—C1ii90.7 (2)
Sm1—O4—H1W124 (7)O4i—Sm1—C1ii92.9 (2)
H2W—O4—H1W104 (10)O4ii—Sm1—C1ii166.99 (15)
O4—Sm1—O4i78.2 (2)O1i—Sm1—C1ii101.65 (19)
O4—Sm1—O4ii78.2 (2)O1ii—Sm1—C1ii26.03 (17)
O4i—Sm1—O4ii78.2 (2)O1—Sm1—C1ii120.94 (17)
O4—Sm1—O1i67.44 (15)O2—Sm1—C1ii70.74 (18)
O4i—Sm1—O1i142.61 (16)O2ii—Sm1—C1ii26.05 (18)
O4ii—Sm1—O1i80.61 (16)O2i—Sm1—C1ii98.17 (17)
O4—Sm1—O1ii80.61 (16)C1—Sm1—C1ii96.75 (18)
O4i—Sm1—O1ii67.44 (15)O4—Sm1—C1i92.9 (2)
O4ii—Sm1—O1ii142.61 (16)O4i—Sm1—C1i166.99 (16)
O1i—Sm1—O1ii118.57 (4)O4ii—Sm1—C1i90.7 (2)
O4—Sm1—O1142.61 (16)O1i—Sm1—C1i26.03 (17)
O4i—Sm1—O180.61 (16)O1ii—Sm1—C1i120.94 (17)
O4ii—Sm1—O167.44 (15)O1—Sm1—C1i101.65 (19)
O1i—Sm1—O1118.57 (4)O2—Sm1—C1i98.17 (17)
O1ii—Sm1—O1118.57 (4)O2ii—Sm1—C1i70.74 (18)
O4—Sm1—O2159.32 (14)O2i—Sm1—C1i26.05 (18)
O4i—Sm1—O293.23 (15)C1—Sm1—C1i96.75 (18)
O4ii—Sm1—O2118.80 (14)C1ii—Sm1—C1i96.75 (18)
O1i—Sm1—O2124.04 (13)C3—N1—C2120.9 (5)
O1ii—Sm1—O278.72 (14)C3—N1—H1115 (6)
O1—Sm1—O251.42 (12)C2—N1—H1123 (6)
O4—Sm1—O2ii93.23 (15)O3—C3—N1120.8 (5)
O4i—Sm1—O2ii118.80 (14)O3—C3—C4122.0 (5)
O4ii—Sm1—O2ii159.32 (14)N1—C3—C4117.2 (5)
O1i—Sm1—O2ii78.72 (14)N1—C2—C1114.8 (5)
O1ii—Sm1—O2ii51.42 (12)N1—C2—H2A112 (4)
O1—Sm1—O2ii124.04 (13)C1—C2—H2A103 (4)
O2—Sm1—O2ii74.26 (14)N1—C2—H2B104 (4)
O4—Sm1—O2i118.80 (14)C1—C2—H2B107 (4)
O4i—Sm1—O2i159.32 (14)H2A—C2—H2B115 (6)
O4ii—Sm1—O2i93.23 (15)
Sm1—O2—C1—O117.9 (7)O1—C1—Sm1—O4ii11.7 (4)
Sm1—O2—C1—C2−156.5 (6)C2—C1—Sm1—O4ii−78.4 (13)
Sm1—O1—C1—O2−18.1 (7)O2—C1—Sm1—O1i−105.1 (4)
Sm1—O1—C1—C2156.5 (5)O1—C1—Sm1—O1i92.5 (3)
C1—O1—Sm1—O4167.7 (4)C2—C1—Sm1—O1i2.4 (14)
C1—O1—Sm1—O4i111.6 (5)O2—C1—Sm1—O1ii28.8 (4)
C1—O1—Sm1—O4ii−167.4 (4)O1—C1—Sm1—O1ii−133.7 (4)
C1—O1—Sm1—O1i−102.7 (4)C2—C1—Sm1—O1ii136.2 (13)
C1—O1—Sm1—O1ii53.8 (4)O2—C1—Sm1—O1162.5 (7)
C1—O1—Sm1—O29.7 (4)C2—C1—Sm1—O1−90.1 (14)
C1—O1—Sm1—O2ii−7.0 (4)O1—C1—Sm1—O2−162.5 (7)
C1—O1—Sm1—O2i−69.0 (4)C2—C1—Sm1—O2107.4 (14)
C1—O1—Sm1—C1ii23.8 (5)O2—C1—Sm1—O2ii−23.4 (4)
C1—O1—Sm1—C1i−81.5 (5)O1—C1—Sm1—O2ii174.2 (4)
C1—O2—Sm1—O4−149.6 (4)C2—C1—Sm1—O2ii84.1 (13)
C1—O2—Sm1—O4i−85.0 (4)O2—C1—Sm1—O2i−93.5 (5)
C1—O2—Sm1—O4ii−6.7 (5)O1—C1—Sm1—O2i104.1 (4)
C1—O2—Sm1—O1i91.8 (4)C2—C1—Sm1—O2i14.0 (13)
C1—O2—Sm1—O1ii−151.3 (4)O2—C1—Sm1—C1ii2.9 (4)
C1—O2—Sm1—O1−9.7 (4)O1—C1—Sm1—C1ii−159.6 (4)
C1—O2—Sm1—O2ii155.9 (4)C2—C1—Sm1—C1ii110.3 (12)
C1—O2—Sm1—O2i78.2 (5)O2—C1—Sm1—C1i−94.8 (3)
C1—O2—Sm1—C1ii−177.0 (4)O1—C1—Sm1—C1i102.8 (5)
C1—O2—Sm1—C1i88.7 (3)C2—C1—Sm1—C1i12.7 (14)
O2—C1—Sm1—O4127.5 (8)C2—N1—C3—O3−5.1 (8)
O1—C1—Sm1—O4−34.9 (12)C2—N1—C3—C4174.2 (5)
C2—C1—Sm1—O4−125.0 (12)C3—N1—C2—C1−76.6 (7)
O2—C1—Sm1—O4i95.9 (4)O2—C1—C2—N1−17.3 (9)
O1—C1—Sm1—O4i−66.6 (4)O1—C1—C2—N1168.2 (6)
C2—C1—Sm1—O4i−156.7 (13)Sm1—C1—C2—N1−112.9 (13)
O2—C1—Sm1—O4ii174.1 (5)
Symmetry codes: (i) −y+2, x−y+1, z; (ii) −x+y+1, −x+2, z.
Table 1
Selected geometric parameters (Å, °) top
O2—Sm12.538 (4)O4—Sm12.403 (4)
O1—Sm12.505 (4)
O4—Sm1—O4i78.2 (2)O4—Sm1—O2159.32 (14)
O4—Sm1—O1142.61 (16)O4i—Sm1—O293.23 (15)
O4i—Sm1—O180.61 (16)O4ii—Sm1—O2118.80 (14)
O4ii—Sm1—O167.44 (15)O1—Sm1—O251.42 (12)
Symmetry codes: (i) −y+2, x−y+1, z; (ii) −x+y+1, −x+2, z.
Acknowledgements top

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

references
References top

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