Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807046429/hy2078sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807046429/hy2078Isup2.hkl |
CCDC reference: 663646
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%.
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.
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.
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) 2 - y, 1 + x-y, z; (ii) 1 - x + y, 2 - x, z.] |
[Sm(C4H6NO3)3(H2O)3] | Dx = 1.935 Mg m−3 Dm = 1.932 Mg m−3 Dm measured by flotation method |
Mr = 552.69 | Mo Kα radiation, λ = 0.71069 Å |
Trigonal, R3 | Cell parameters from 25 reflections |
Hall symbol: R 3 | θ = 12.7–16.7° |
a = 16.580 (4) Å | µ = 3.16 mm−1 |
c = 5.978 (1) Å | T = 298 K |
V = 1423.2 (5) Å3 | Needle, colourless |
Z = 3 | 0.40 × 0.20 × 0.20 mm |
F(000) = 825 |
Rigaku AFC-7S diffractometer | 702 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 27.5°, θmin = 3.7° |
ω/2θ scans | h = −21→18 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→21 |
Tmin = 0.364, Tmax = 0.570 | l = −7→4 |
1396 measured reflections | 3 standard reflections every 150 reflections |
900 independent reflections | intensity decay: 0.6% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H 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 = 1.07 | Δρmax = 0.81 e Å−3 |
900 reflections | Δρmin = −1.21 e Å−3 |
107 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
3 restraints | Extinction coefficient: 0.0017 (4) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), with 176 Friedel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: −0.03 (2) |
[Sm(C4H6NO3)3(H2O)3] | Z = 3 |
Mr = 552.69 | Mo Kα radiation |
Trigonal, R3 | µ = 3.16 mm−1 |
a = 16.580 (4) Å | T = 298 K |
c = 5.978 (1) Å | 0.40 × 0.20 × 0.20 mm |
V = 1423.2 (5) Å3 |
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 = 0.570 | 3 standard reflections every 150 reflections |
1396 measured reflections | intensity decay: 0.6% |
900 independent reflections |
R[F2 > 2σ(F2)] = 0.020 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.051 | Δρmax = 0.81 e Å−3 |
S = 1.07 | Δρmin = −1.21 e Å−3 |
900 reflections | Absolute structure: Flack (1983), with 176 Friedel pairs |
107 parameters | Absolute structure parameter: −0.03 (2) |
3 restraints |
x | y | z | Uiso*/Ueq | ||
C4 | 0.7757 (5) | 0.6593 (4) | −0.1291 (10) | 0.0392 (13) | |
H4C | 0.7402 | 0.5934 | −0.1548 | 0.059* | |
H4A | 0.8165 | 0.6890 | −0.2538 | 0.059* | |
H4B | 0.7343 | 0.6836 | −0.1124 | 0.059* | |
O2 | 0.9222 (3) | 0.8784 (3) | 0.3629 (7) | 0.0286 (8) | |
O1 | 0.9998 (3) | 0.8499 (3) | 0.6168 (6) | 0.0296 (8) | |
C1 | 0.9635 (6) | 0.8361 (5) | 0.4255 (11) | 0.0244 (14) | |
O4 | 1.0216 (3) | 1.1147 (4) | 0.9427 (7) | 0.0309 (9) | |
H1 | 0.938 (6) | 0.771 (5) | −0.046 (13) | 0.05 (2)* | |
H2A | 0.968 (5) | 0.716 (5) | 0.371 (11) | 0.035 (17)* | |
H2B | 1.039 (5) | 0.808 (4) | 0.214 (10) | 0.029 (16)* | |
H2W | 0.997 (8) | 1.109 (9) | 1.064 (10) | 0.11 (5)* | |
H1W | 1.051 (7) | 1.1708 (19) | 0.921 (17) | 0.04 (3)* | |
Sm1 | 1.0000 | 1.0000 | 0.6673 | 0.01945 (14) | |
N1 | 0.9221 (3) | 0.7447 (3) | 0.0689 (8) | 0.0284 (10) | |
O3 | 0.7980 (3) | 0.6347 (3) | 0.2547 (7) | 0.0371 (10) | |
C3 | 0.8321 (4) | 0.6779 (3) | 0.0787 (9) | 0.0285 (11) | |
C2 | 0.9797 (4) | 0.7734 (4) | 0.2680 (9) | 0.0282 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C4 | 0.046 (3) | 0.037 (3) | 0.031 (3) | 0.018 (3) | −0.009 (3) | −0.004 (2) |
O2 | 0.034 (2) | 0.0271 (19) | 0.0256 (19) | 0.0162 (18) | −0.0032 (17) | 0.0001 (15) |
O1 | 0.039 (2) | 0.032 (2) | 0.0205 (19) | 0.0195 (17) | −0.0054 (15) | −0.0001 (15) |
C1 | 0.025 (3) | 0.022 (3) | 0.021 (3) | 0.009 (2) | 0.002 (2) | 0.004 (2) |
O4 | 0.037 (2) | 0.028 (2) | 0.022 (2) | 0.011 (2) | 0.0082 (18) | −0.0022 (19) |
Sm1 | 0.02189 (15) | 0.02189 (15) | 0.01455 (18) | 0.01095 (8) | 0.000 | 0.000 |
N1 | 0.039 (3) | 0.022 (2) | 0.018 (2) | 0.0109 (19) | 0.0003 (18) | −0.0006 (17) |
O3 | 0.041 (2) | 0.030 (2) | 0.030 (2) | 0.0095 (18) | 0.0049 (18) | 0.0062 (16) |
C3 | 0.037 (3) | 0.017 (2) | 0.028 (3) | 0.011 (2) | 0.000 (2) | −0.0023 (19) |
C2 | 0.034 (3) | 0.024 (2) | 0.025 (2) | 0.013 (2) | 0.002 (2) | −0.001 (2) |
C4—C3 | 1.491 (8) | Sm1—O4ii | 2.403 (4) |
C4—H4C | 0.9600 | Sm1—O1i | 2.505 (4) |
C4—H4A | 0.9600 | Sm1—O1ii | 2.505 (4) |
C4—H4B | 0.9600 | Sm1—O2ii | 2.538 (4) |
O2—C1 | 1.258 (8) | Sm1—O2i | 2.538 (4) |
O2—Sm1 | 2.538 (4) | Sm1—C1ii | 2.863 (8) |
O1—C1 | 1.258 (9) | Sm1—C1i | 2.863 (8) |
O1—Sm1 | 2.505 (4) | N1—C3 | 1.342 (7) |
C1—C2 | 1.522 (9) | N1—C2 | 1.450 (7) |
C1—Sm1 | 2.863 (8) | N1—H1 | 0.79 (7) |
O4—Sm1 | 2.403 (4) | O3—C3 | 1.239 (6) |
O4—H2W | 0.81 (8) | C2—H2A | 1.06 (7) |
O4—H1W | 0.82 (2) | C2—H2B | 0.91 (6) |
Sm1—O4i | 2.403 (4) | ||
C3—C4—H4C | 109.5 | O1i—Sm1—O2i | 51.42 (12) |
C3—C4—H4A | 109.5 | O1ii—Sm1—O2i | 124.04 (13) |
H4C—C4—H4A | 109.5 | O1—Sm1—O2i | 78.72 (14) |
C3—C4—H4B | 109.5 | O2—Sm1—O2i | 74.26 (14) |
H4C—C4—H4B | 109.5 | O2ii—Sm1—O2i | 74.26 (14) |
H4A—C4—H4B | 109.5 | O4—Sm1—C1 | 166.99 (15) |
C1—O2—Sm1 | 91.6 (4) | O4i—Sm1—C1 | 90.7 (2) |
C1—O1—Sm1 | 93.1 (4) | O4ii—Sm1—C1 | 92.91 (19) |
O2—C1—O1 | 120.8 (6) | O1i—Sm1—C1 | 120.94 (17) |
O2—C1—C2 | 121.9 (6) | O1ii—Sm1—C1 | 101.65 (19) |
O1—C1—C2 | 117.1 (6) | O1—Sm1—C1 | 26.03 (17) |
O2—C1—Sm1 | 62.4 (4) | O2—Sm1—C1 | 26.05 (18) |
O1—C1—Sm1 | 60.9 (3) | O2ii—Sm1—C1 | 98.17 (17) |
C2—C1—Sm1 | 159.2 (5) | O2i—Sm1—C1 | 70.74 (18) |
Sm1—O4—H2W | 131 (9) | O4—Sm1—C1ii | 90.7 (2) |
Sm1—O4—H1W | 124 (7) | O4i—Sm1—C1ii | 92.9 (2) |
H2W—O4—H1W | 104 (10) | O4ii—Sm1—C1ii | 166.99 (15) |
O4—Sm1—O4i | 78.2 (2) | O1i—Sm1—C1ii | 101.65 (19) |
O4—Sm1—O4ii | 78.2 (2) | O1ii—Sm1—C1ii | 26.03 (17) |
O4i—Sm1—O4ii | 78.2 (2) | O1—Sm1—C1ii | 120.94 (17) |
O4—Sm1—O1i | 67.44 (15) | O2—Sm1—C1ii | 70.74 (18) |
O4i—Sm1—O1i | 142.61 (16) | O2ii—Sm1—C1ii | 26.05 (18) |
O4ii—Sm1—O1i | 80.61 (16) | O2i—Sm1—C1ii | 98.17 (17) |
O4—Sm1—O1ii | 80.61 (16) | C1—Sm1—C1ii | 96.75 (18) |
O4i—Sm1—O1ii | 67.44 (15) | O4—Sm1—C1i | 92.9 (2) |
O4ii—Sm1—O1ii | 142.61 (16) | O4i—Sm1—C1i | 166.99 (16) |
O1i—Sm1—O1ii | 118.57 (4) | O4ii—Sm1—C1i | 90.7 (2) |
O4—Sm1—O1 | 142.61 (16) | O1i—Sm1—C1i | 26.03 (17) |
O4i—Sm1—O1 | 80.61 (16) | O1ii—Sm1—C1i | 120.94 (17) |
O4ii—Sm1—O1 | 67.44 (15) | O1—Sm1—C1i | 101.65 (19) |
O1i—Sm1—O1 | 118.57 (4) | O2—Sm1—C1i | 98.17 (17) |
O1ii—Sm1—O1 | 118.57 (4) | O2ii—Sm1—C1i | 70.74 (18) |
O4—Sm1—O2 | 159.32 (14) | O2i—Sm1—C1i | 26.05 (18) |
O4i—Sm1—O2 | 93.23 (15) | C1—Sm1—C1i | 96.75 (18) |
O4ii—Sm1—O2 | 118.80 (14) | C1ii—Sm1—C1i | 96.75 (18) |
O1i—Sm1—O2 | 124.04 (13) | C3—N1—C2 | 120.9 (5) |
O1ii—Sm1—O2 | 78.72 (14) | C3—N1—H1 | 115 (6) |
O1—Sm1—O2 | 51.42 (12) | C2—N1—H1 | 123 (6) |
O4—Sm1—O2ii | 93.23 (15) | O3—C3—N1 | 120.8 (5) |
O4i—Sm1—O2ii | 118.80 (14) | O3—C3—C4 | 122.0 (5) |
O4ii—Sm1—O2ii | 159.32 (14) | N1—C3—C4 | 117.2 (5) |
O1i—Sm1—O2ii | 78.72 (14) | N1—C2—C1 | 114.8 (5) |
O1ii—Sm1—O2ii | 51.42 (12) | N1—C2—H2A | 112 (4) |
O1—Sm1—O2ii | 124.04 (13) | C1—C2—H2A | 103 (4) |
O2—Sm1—O2ii | 74.26 (14) | N1—C2—H2B | 104 (4) |
O4—Sm1—O2i | 118.80 (14) | C1—C2—H2B | 107 (4) |
O4i—Sm1—O2i | 159.32 (14) | H2A—C2—H2B | 115 (6) |
O4ii—Sm1—O2i | 93.23 (15) | ||
Sm1—O2—C1—O1 | 17.9 (7) | O1—C1—Sm1—O4ii | 11.7 (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—C2 | 156.5 (5) | O1—C1—Sm1—O1i | 92.5 (3) |
C1—O1—Sm1—O4 | 167.7 (4) | C2—C1—Sm1—O1i | 2.4 (14) |
C1—O1—Sm1—O4i | 111.6 (5) | O2—C1—Sm1—O1ii | 28.8 (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—O1ii | 136.2 (13) |
C1—O1—Sm1—O1ii | 53.8 (4) | O2—C1—Sm1—O1 | 162.5 (7) |
C1—O1—Sm1—O2 | 9.7 (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—O2 | 107.4 (14) |
C1—O1—Sm1—C1ii | 23.8 (5) | O2—C1—Sm1—O2ii | −23.4 (4) |
C1—O1—Sm1—C1i | −81.5 (5) | O1—C1—Sm1—O2ii | 174.2 (4) |
C1—O2—Sm1—O4 | −149.6 (4) | C2—C1—Sm1—O2ii | 84.1 (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—O2i | 104.1 (4) |
C1—O2—Sm1—O1i | 91.8 (4) | C2—C1—Sm1—O2i | 14.0 (13) |
C1—O2—Sm1—O1ii | −151.3 (4) | O2—C1—Sm1—C1ii | 2.9 (4) |
C1—O2—Sm1—O1 | −9.7 (4) | O1—C1—Sm1—C1ii | −159.6 (4) |
C1—O2—Sm1—O2ii | 155.9 (4) | C2—C1—Sm1—C1ii | 110.3 (12) |
C1—O2—Sm1—O2i | 78.2 (5) | O2—C1—Sm1—C1i | −94.8 (3) |
C1—O2—Sm1—C1ii | −177.0 (4) | O1—C1—Sm1—C1i | 102.8 (5) |
C1—O2—Sm1—C1i | 88.7 (3) | C2—C1—Sm1—C1i | 12.7 (14) |
O2—C1—Sm1—O4 | 127.5 (8) | C2—N1—C3—O3 | −5.1 (8) |
O1—C1—Sm1—O4 | −34.9 (12) | C2—N1—C3—C4 | 174.2 (5) |
C2—C1—Sm1—O4 | −125.0 (12) | C3—N1—C2—C1 | −76.6 (7) |
O2—C1—Sm1—O4i | 95.9 (4) | O2—C1—C2—N1 | −17.3 (9) |
O1—C1—Sm1—O4i | −66.6 (4) | O1—C1—C2—N1 | 168.2 (6) |
C2—C1—Sm1—O4i | −156.7 (13) | Sm1—C1—C2—N1 | −112.9 (13) |
O2—C1—Sm1—O4ii | 174.1 (5) |
Symmetry codes: (i) −y+2, x−y+1, z; (ii) −x+y+1, −x+2, z. |
Experimental details
Crystal data | |
Chemical formula | [Sm(C4H6NO3)3(H2O)3] |
Mr | 552.69 |
Crystal system, space group | Trigonal, R3 |
Temperature (K) | 298 |
a, c (Å) | 16.580 (4), 5.978 (1) |
V (Å3) | 1423.2 (5) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 3.16 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-7S |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.364, 0.570 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1396, 900, 702 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.051, 1.07 |
No. of reflections | 900 |
No. of parameters | 107 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.81, −1.21 |
Absolute structure | Flack (1983), with 176 Friedel pairs |
Absolute structure parameter | −0.03 (2) |
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).
O2—Sm1 | 2.538 (4) | O4—Sm1 | 2.403 (4) |
O1—Sm1 | 2.505 (4) | ||
O4—Sm1—O4i | 78.2 (2) | O4—Sm1—O2 | 159.32 (14) |
O4—Sm1—O1 | 142.61 (16) | O4i—Sm1—O2 | 93.23 (15) |
O4i—Sm1—O1 | 80.61 (16) | O4ii—Sm1—O2 | 118.80 (14) |
O4ii—Sm1—O1 | 67.44 (15) | O1—Sm1—O2 | 51.42 (12) |
Symmetry codes: (i) −y+2, x−y+1, z; (ii) −x+y+1, −x+2, 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.
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.