Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100012014/qd0035sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100012014/qd0035Isup2.hkl |
CCDC reference: 152648
The title compound was obtained in the attempted preparation of an erbium–NTA complex, by mixing 0.50 M ErIII and 0.50 M Na2NTA aqueous solutions in a 1:4 molar ratio. The pH of the solution was adjusted to 4.5. Colorless microcrystals of the title compound were obtained by slow evaporation.
Positional parameters of H atoms bonded to C atoms were calculated geometrically. The H atoms bonded to the N and O atoms were observed from difference syntheses and refined isotropically. The N—H and O—H bond lengths are 0.92 (2) Å and 0.81 (4)–0.90 (3) Å, respectively.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.
Na+·C6H8NO6−·2H2O | F(000) = 1040 |
Mr = 249.16 | Dx = 1.696 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 42 reflections |
a = 5.8620 (19) Å | θ = 6.8–12.6° |
b = 12.3986 (16) Å | µ = 0.19 mm−1 |
c = 26.854 (3) Å | T = 293 K |
V = 1951.8 (7) Å3 | Needle, colourless |
Z = 8 | 0.40 × 0.15 × 0.10 mm |
Bruker P4 diffractometer | 1731 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.035 |
Graphite monochromator | θmax = 27.5°, θmin = 3.0° |
2θ/ω scans | h = −7→7 |
Absorption correction: ψ scan (North et al., 1968) | k = −16→16 |
Tmin = 0.873, Tmax = 0.981 | l = −34→34 |
4474 measured reflections | 3 standard reflections every 97 reflections |
2239 independent reflections | intensity decay: 3.0% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0544P)2 + 0.3629P] where P = (Fo2 + 2Fc2)/3 |
2239 reflections | (Δ/σ)max < 0.001 |
169 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
Na+·C6H8NO6−·2H2O | V = 1951.8 (7) Å3 |
Mr = 249.16 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 5.8620 (19) Å | µ = 0.19 mm−1 |
b = 12.3986 (16) Å | T = 293 K |
c = 26.854 (3) Å | 0.40 × 0.15 × 0.10 mm |
Bruker P4 diffractometer | 1731 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.035 |
Tmin = 0.873, Tmax = 0.981 | 3 standard reflections every 97 reflections |
4474 measured reflections | intensity decay: 3.0% |
2239 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.26 e Å−3 |
2239 reflections | Δρmin = −0.31 e Å−3 |
169 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Na1 | 0.24682 (13) | 0.53495 (6) | 0.03123 (3) | 0.0303 (2) | |
N1 | 0.1742 (3) | 0.69269 (11) | 0.15172 (5) | 0.0175 (3) | |
OW1 | 0.0995 (3) | 0.37426 (11) | −0.00484 (6) | 0.0314 (3) | |
OW2 | 0.3847 (3) | 0.56365 (15) | −0.05472 (6) | 0.0400 (4) | |
O1 | 0.3778 (2) | 0.70744 (12) | 0.06396 (5) | 0.0298 (3) | |
O2 | 0.7320 (2) | 0.71312 (13) | 0.09511 (5) | 0.0324 (3) | |
O3 | 0.0453 (3) | 0.50908 (10) | 0.10571 (5) | 0.0302 (3) | |
O4 | −0.1266 (2) | 0.44076 (11) | 0.17261 (5) | 0.0302 (3) | |
O5 | 0.1241 (2) | 0.92952 (9) | 0.23208 (5) | 0.0236 (3) | |
O6 | 0.2442 (2) | 0.76159 (9) | 0.24822 (5) | 0.0236 (3) | |
C1 | 0.4274 (3) | 0.67261 (15) | 0.15004 (6) | 0.0228 (4) | |
H1A | 0.4581 | 0.5973 | 0.1571 | 0.027* | |
H1B | 0.5027 | 0.7159 | 0.1752 | 0.027* | |
C2 | 0.5209 (3) | 0.70163 (14) | 0.09849 (6) | 0.0222 (4) | |
C3 | 0.0433 (3) | 0.61089 (13) | 0.18141 (6) | 0.0201 (3) | |
H3A | −0.0959 | 0.6435 | 0.1938 | 0.024* | |
H3B | 0.1339 | 0.5886 | 0.2098 | 0.024* | |
C4 | −0.0164 (3) | 0.51239 (13) | 0.15009 (6) | 0.0205 (3) | |
C5 | 0.1186 (3) | 0.80642 (13) | 0.16581 (6) | 0.0202 (4) | |
H5A | −0.0419 | 0.8198 | 0.1596 | 0.024* | |
H5B | 0.2063 | 0.8554 | 0.1451 | 0.024* | |
C6 | 0.1704 (3) | 0.82886 (13) | 0.21995 (6) | 0.0188 (3) | |
HN1 | 0.126 (4) | 0.6857 (18) | 0.1193 (9) | 0.031 (6)* | |
HO5 | 0.134 (5) | 0.934 (3) | 0.2696 (12) | 0.079 (10)* | |
HW1 | 0.147 (4) | 0.347 (2) | −0.0330 (10) | 0.040 (7)* | |
HW2 | 0.088 (5) | 0.324 (2) | 0.0178 (11) | 0.054 (8)* | |
HW3 | 0.264 (6) | 0.542 (2) | −0.0727 (11) | 0.056 (9)* | |
HW4 | 0.398 (7) | 0.629 (4) | −0.0572 (15) | 0.107 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Na1 | 0.0331 (4) | 0.0315 (4) | 0.0262 (4) | −0.0034 (3) | 0.0023 (3) | −0.0045 (3) |
N1 | 0.0205 (7) | 0.0159 (7) | 0.0161 (7) | −0.0003 (5) | 0.0001 (5) | −0.0003 (5) |
OW1 | 0.0428 (8) | 0.0254 (7) | 0.0259 (7) | 0.0019 (6) | 0.0050 (6) | 0.0001 (6) |
OW2 | 0.0421 (10) | 0.0408 (9) | 0.0371 (9) | −0.0030 (8) | −0.0012 (7) | 0.0031 (7) |
O1 | 0.0317 (7) | 0.0356 (7) | 0.0222 (6) | −0.0068 (6) | −0.0024 (6) | 0.0028 (5) |
O2 | 0.0248 (7) | 0.0421 (8) | 0.0303 (7) | −0.0011 (6) | 0.0063 (6) | −0.0038 (6) |
O3 | 0.0453 (8) | 0.0236 (6) | 0.0216 (6) | −0.0048 (6) | 0.0072 (6) | −0.0033 (5) |
O4 | 0.0406 (8) | 0.0232 (6) | 0.0269 (7) | −0.0125 (6) | 0.0036 (6) | 0.0004 (5) |
O5 | 0.0279 (7) | 0.0163 (6) | 0.0267 (6) | 0.0007 (5) | 0.0009 (5) | −0.0029 (5) |
O6 | 0.0256 (6) | 0.0211 (6) | 0.0242 (6) | 0.0014 (5) | −0.0053 (5) | 0.0007 (5) |
C1 | 0.0202 (9) | 0.0250 (9) | 0.0231 (9) | 0.0035 (7) | 0.0005 (7) | 0.0001 (7) |
C2 | 0.0250 (9) | 0.0179 (8) | 0.0235 (8) | −0.0006 (7) | 0.0033 (7) | −0.0041 (6) |
C3 | 0.0246 (8) | 0.0154 (7) | 0.0204 (8) | −0.0023 (7) | 0.0038 (7) | 0.0004 (6) |
C4 | 0.0217 (8) | 0.0166 (8) | 0.0232 (8) | 0.0010 (6) | 0.0014 (7) | 0.0002 (6) |
C5 | 0.0242 (9) | 0.0135 (7) | 0.0230 (8) | 0.0007 (6) | −0.0013 (7) | 0.0011 (6) |
C6 | 0.0159 (7) | 0.0164 (7) | 0.0241 (8) | −0.0029 (6) | 0.0002 (6) | −0.0013 (6) |
Na1—O3 | 2.3450 (15) | OW1—Na1i | 2.4271 (18) |
Na1—OW1 | 2.3778 (16) | OW2—Na1ii | 2.561 (2) |
Na1—OW1i | 2.4271 (18) | O1—C2 | 1.253 (2) |
Na1—O1 | 2.4362 (16) | O2—C2 | 1.249 (2) |
Na1—OW2 | 2.4712 (18) | O3—C4 | 1.246 (2) |
Na1—OW2ii | 2.561 (2) | O4—C4 | 1.254 (2) |
Na1—Na1i | 3.4552 (17) | O5—C6 | 1.318 (2) |
Na1—Na1ii | 3.5179 (17) | O6—C6 | 1.208 (2) |
N1—C5 | 1.496 (2) | C1—C2 | 1.532 (2) |
N1—C3 | 1.501 (2) | C3—C4 | 1.524 (2) |
N1—C1 | 1.505 (2) | C5—C6 | 1.511 (2) |
O3—Na1—OW1 | 92.86 (6) | O1—Na1—Na1ii | 97.03 (5) |
O3—Na1—OW1i | 83.74 (6) | OW2—Na1—Na1ii | 46.70 (4) |
OW1—Na1—OW1i | 88.04 (6) | OW2ii—Na1—Na1ii | 44.61 (4) |
O3—Na1—O1 | 88.35 (5) | Na1i—Na1—Na1ii | 114.42 (4) |
OW1—Na1—O1 | 175.53 (6) | C5—N1—C3 | 113.02 (13) |
OW1i—Na1—O1 | 87.81 (6) | C5—N1—C1 | 112.22 (13) |
O3—Na1—OW2 | 168.83 (7) | C3—N1—C1 | 114.09 (13) |
OW1—Na1—OW2 | 81.89 (6) | Na1—OW1—Na1i | 91.96 (6) |
OW1i—Na1—OW2 | 86.22 (6) | Na1—OW2—Na1ii | 88.69 (6) |
O1—Na1—OW2 | 96.17 (6) | C2—O1—Na1 | 115.32 (12) |
O3—Na1—OW2ii | 98.61 (6) | C4—O3—Na1 | 163.21 (13) |
OW1—Na1—OW2ii | 90.38 (6) | N1—C1—C2 | 109.94 (14) |
OW1i—Na1—OW2ii | 177.24 (6) | O2—C2—O1 | 127.10 (17) |
O1—Na1—OW2ii | 93.69 (6) | O2—C2—C1 | 116.57 (16) |
OW2—Na1—OW2ii | 91.31 (6) | O1—C2—C1 | 116.28 (16) |
O3—Na1—Na1i | 87.58 (5) | N1—C3—C4 | 111.45 (13) |
OW1—Na1—Na1i | 44.59 (4) | O3—C4—O4 | 125.98 (16) |
OW1i—Na1—Na1i | 43.45 (4) | O3—C4—C3 | 119.19 (15) |
O1—Na1—Na1i | 131.24 (5) | O4—C4—C3 | 114.83 (14) |
OW2—Na1—Na1i | 81.75 (5) | N1—C5—C6 | 111.92 (13) |
OW2ii—Na1—Na1i | 134.93 (6) | O6—C6—O5 | 124.90 (16) |
O3—Na1—Na1ii | 142.95 (6) | O6—C6—C5 | 123.34 (15) |
OW1—Na1—Na1ii | 84.59 (5) | O5—C6—C5 | 111.76 (14) |
OW1i—Na1—Na1ii | 132.91 (5) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | Na+·C6H8NO6−·2H2O |
Mr | 249.16 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 5.8620 (19), 12.3986 (16), 26.854 (3) |
V (Å3) | 1951.8 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.40 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.873, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4474, 2239, 1731 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.109, 1.05 |
No. of reflections | 2239 |
No. of parameters | 169 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.26, −0.31 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL (Siemens, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL.
Na1—O3 | 2.3450 (15) | Na1—O1 | 2.4362 (16) |
Na1—OW1 | 2.3778 (16) | Na1—OW2 | 2.4712 (18) |
Na1—OW1i | 2.4271 (18) | Na1—OW2ii | 2.561 (2) |
O3—Na1—OW1 | 92.86 (6) | O3—Na1—OW2ii | 98.61 (6) |
O3—Na1—OW1i | 83.74 (6) | OW1—Na1—OW2ii | 90.38 (6) |
OW1—Na1—OW1i | 88.04 (6) | OW1i—Na1—OW2ii | 177.24 (6) |
O3—Na1—O1 | 88.35 (5) | O1—Na1—OW2ii | 93.69 (6) |
OW1—Na1—O1 | 175.53 (6) | OW2—Na1—OW2ii | 91.31 (6) |
OW1i—Na1—O1 | 87.81 (6) | Na1—OW1—Na1i | 91.96 (6) |
O3—Na1—OW2 | 168.83 (7) | Na1—OW2—Na1ii | 88.69 (6) |
OW1—Na1—OW2 | 81.89 (6) | C2—O1—Na1 | 115.32 (12) |
OW1i—Na1—OW2 | 86.22 (6) | C4—O3—Na1 | 163.21 (13) |
O1—Na1—OW2 | 96.17 (6) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z. |
Recently, much attention has been paid to nitrilotriacetate acid (NTA), a multidentate complexing ligand with high specificity for various polyvalent metal ions. The trivalent NTA anion normally coordinates with alkali earth and transition metal ions as tetradentate ligands, binding with an N atom and three acetate O atoms to the metal (Barnett & Uchtman, 1979; Kaneyoshi et al., 1999). However, for a few complexes, NTA is hexadentate or heptadentate (Martin & Jacobson, 1972). The structure of trisodium nitrilotriacetate has been proposed as polymeric with seven O atoms and one N atom coordinated to three sodium ions (Dely, 1967).
The crystal structure of the title compound contains Na ions chelated by NTA molecules via two Na—O bonds [2.436 (2) and 2.345 (2) Å]. The observed Na—O bond distances are within the range 2.28–2.67 Å, reported by Dely (1976). The O—Na—O angle is 88.35 (5)°. Two water molecules are involved in each molecular unit and bridge two adjacent sodium ions, with one water O atom coordinated to Na and Nai, and the other to Na and Naii [symmetry codes: (i) −x, 1 − y, −z; (ii) 1 − x, 1 − y, −z]. The four Na—OW bond distances are in the range 2.345 (2)–2.561 (2) Å and the two OW—Na—OW angles are 91.36 (6) and 88.04 (6)°. The geometry around the sodium ion can be described as slightly distorted octahedral. The infinite crystal network is formed via four-membered Na—OW—Na—OW rings between two layers and via hydrogen bonds between two adjacent molecular units in a given layer.