Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800019036/na6017sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800019036/na6017Isup2.hkl |
CCDC reference: 155839
Crystals of the title compound were obtained from an ethanol solution, originally charged with 1 mmol each of PrIII nitrate and 15-crown-5, that had been treated with carbon dioxide under reflux as part of a study of the chemical activation and reduction of carbon dioxide promoted by trivalent lanthanide ions. Analysis calculated for C10H20N3O14: C 21.94, H 3.88, N 7.68%; found: C 21.4, H 3.6, N 7.7%.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[Pr(NO3)3(C10H20O5)] | F(000) = 1088 |
Mr = 547.20 | Dx = 1.972 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3236 (5) Å | Cell parameters from 25 reflections |
b = 14.5789 (14) Å | θ = 24.3–25.8° |
c = 13.6184 (6) Å | µ = 2.72 mm−1 |
β = 95.361 (4)° | T = 293 K |
V = 1843.0 (2) Å3 | Plate, light green |
Z = 4 | 0.5 × 0.5 × 0.26 mm |
Enraf-Nonius CAD-4 diffractometer | 2940 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.042 |
Graphite monochromator | θmax = 26.0°, θmin = 2.1° |
θ/2θ scans | h = 0→11 |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | k = 0→17 |
Tmin = 0.227, Tmax = 0.426 | l = −16→16 |
3838 measured reflections | 2 standard reflections every 120 min |
3612 independent reflections | intensity decay: 5.1% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.027 | H-atom parameters constrained |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.0445P)2 + 0.7265P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = −0.001 |
3611 reflections | Δρmax = 1.23 e Å−3 |
254 parameters | Δρmin = −0.74 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0083 (4) |
[Pr(NO3)3(C10H20O5)] | V = 1843.0 (2) Å3 |
Mr = 547.20 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.3236 (5) Å | µ = 2.72 mm−1 |
b = 14.5789 (14) Å | T = 293 K |
c = 13.6184 (6) Å | 0.5 × 0.5 × 0.26 mm |
β = 95.361 (4)° |
Enraf-Nonius CAD-4 diffractometer | 2940 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ scan (North et al., 1968) | Rint = 0.042 |
Tmin = 0.227, Tmax = 0.426 | 2 standard reflections every 120 min |
3838 measured reflections | intensity decay: 5.1% |
3612 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.075 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.23 e Å−3 |
3611 reflections | Δρmin = −0.74 e Å−3 |
254 parameters |
Experimental. A light green crystal of the complex was removed from the mother liquor, rapidly cut to size and wedged into a thin-walled glass capillary which was then flame-sealed. General procedures for crystal alignment, unit cell determination and refinement and collection of intensity data have been published [Mague, J. T. & Lloyd, C. L. (1988). Organometallics 7, 983–993]. |
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 on F2 for ALL reflections except for 1 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion 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 | ||
Pr | 0.71279 (2) | 0.983235 (14) | 0.270874 (12) | 0.02341 (10) | |
O1 | 0.6130 (3) | 1.0524 (2) | 0.0928 (2) | 0.0371 (6) | |
O2 | 0.4943 (3) | 1.0952 (2) | 0.2557 (2) | 0.0341 (6) | |
O3 | 0.6330 (3) | 1.0649 (2) | 0.4326 (2) | 0.0323 (6) | |
O4 | 0.9050 (3) | 1.0828 (2) | 0.3816 (2) | 0.0356 (6) | |
O5 | 0.8638 (3) | 1.1128 (2) | 0.1852 (2) | 0.0367 (6) | |
C1 | 0.4899 (5) | 1.1123 (3) | 0.0847 (3) | 0.0442 (10) | |
H1A | 0.4346 (5) | 1.1038 (3) | 0.0215 (3) | 0.053* | |
H1B | 0.5208 (5) | 1.1758 (3) | 0.0900 (3) | 0.053* | |
C2 | 0.4002 (4) | 1.0890 (3) | 0.1664 (3) | 0.0402 (9) | |
H2A | 0.3208 (4) | 1.1318 (3) | 0.1678 (3) | 0.048* | |
H2B | 0.3614 (4) | 1.0275 (3) | 0.1579 (3) | 0.048* | |
C3 | 0.4185 (4) | 1.1131 (3) | 0.3414 (3) | 0.0433 (10) | |
H3A | 0.3652 (4) | 1.0592 (3) | 0.3585 (3) | 0.052* | |
H3B | 0.3511 (4) | 1.1634 (3) | 0.3284 (3) | 0.052* | |
C4 | 0.5286 (5) | 1.1375 (3) | 0.4234 (3) | 0.0422 (10) | |
H4A | 0.5748 (5) | 1.1950 (3) | 0.4092 (3) | 0.051* | |
H4B | 0.4837 (5) | 1.1444 (3) | 0.4844 (3) | 0.051* | |
C5 | 0.7490 (4) | 1.0842 (3) | 0.5068 (3) | 0.0380 (9) | |
H5A | 0.7882 (4) | 1.0272 (3) | 0.5346 (3) | 0.046* | |
H5B | 0.7133 (4) | 1.1198 (3) | 0.5596 (3) | 0.046* | |
C6 | 0.8641 (5) | 1.1365 (3) | 0.4622 (3) | 0.0433 (10) | |
H6A | 0.8281 (5) | 1.1958 (3) | 0.4391 (3) | 0.052* | |
H6B | 0.9460 (5) | 1.1459 (3) | 0.5105 (3) | 0.052* | |
C7 | 1.0183 (4) | 1.1243 (3) | 0.3321 (3) | 0.0401 (10) | |
H7A | 1.0834 (4) | 1.0773 (3) | 0.3124 (3) | 0.048* | |
H7B | 1.0730 (4) | 1.1662 (3) | 0.3766 (3) | 0.048* | |
C8 | 0.9555 (4) | 1.1752 (3) | 0.2435 (3) | 0.0408 (10) | |
H8A | 0.9003 (4) | 1.2273 (3) | 0.2631 (3) | 0.049* | |
H8B | 1.0315 (4) | 1.1974 (3) | 0.2056 (3) | 0.049* | |
C9 | 0.8174 (5) | 1.1527 (3) | 0.0914 (3) | 0.0436 (10) | |
H9A | 0.9001 (5) | 1.1678 (3) | 0.0562 (3) | 0.052* | |
H9B | 0.7637 (5) | 1.2086 (3) | 0.1003 (3) | 0.052* | |
C10 | 0.7241 (5) | 1.0841 (3) | 0.0341 (3) | 0.0424 (10) | |
H10A | 0.6805 (5) | 1.1121 (3) | −0.0261 (3) | 0.051* | |
H10B | 0.7821 (5) | 1.0326 (3) | 0.0162 (3) | 0.051* | |
N1 | 0.9535 (4) | 0.9039 (3) | 0.1729 (3) | 0.0478 (10) | |
O6 | 0.8265 (4) | 0.9077 (2) | 0.1318 (2) | 0.0483 (8) | |
O7 | 0.9731 (3) | 0.9289 (2) | 0.2625 (2) | 0.0459 (7) | |
O8 | 1.0543 (5) | 0.8766 (3) | 0.1293 (3) | 0.0866 (15) | |
N2 | 0.7816 (3) | 0.8157 (2) | 0.3962 (2) | 0.0342 (7) | |
O9 | 0.7866 (3) | 0.8967 (2) | 0.4296 (2) | 0.0373 (6) | |
O10 | 0.7475 (3) | 0.8064 (2) | 0.3048 (2) | 0.0372 (6) | |
O11 | 0.8086 (4) | 0.7502 (2) | 0.4498 (3) | 0.0626 (10) | |
N3 | 0.4549 (3) | 0.8586 (2) | 0.2500 (2) | 0.0344 (7) | |
O12 | 0.5204 (3) | 0.8806 (2) | 0.1760 (2) | 0.0381 (6) | |
O13 | 0.4923 (3) | 0.9016 (2) | 0.3295 (2) | 0.0391 (7) | |
O14 | 0.3629 (3) | 0.7999 (2) | 0.2451 (3) | 0.0598 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pr | 0.02571 (13) | 0.02156 (14) | 0.02326 (13) | 0.00014 (7) | 0.00389 (7) | −0.00068 (7) |
O1 | 0.043 (2) | 0.036 (2) | 0.0320 (13) | −0.0008 (13) | 0.0017 (11) | 0.0040 (12) |
O2 | 0.0301 (13) | 0.039 (2) | 0.0329 (13) | 0.0070 (11) | 0.0033 (10) | 0.0025 (12) |
O3 | 0.0343 (13) | 0.032 (2) | 0.0308 (13) | 0.0001 (11) | 0.0071 (10) | −0.0064 (11) |
O4 | 0.0334 (14) | 0.042 (2) | 0.0326 (14) | −0.0135 (12) | 0.0089 (11) | −0.0092 (12) |
O5 | 0.042 (2) | 0.036 (2) | 0.0322 (14) | −0.0114 (12) | 0.0023 (11) | 0.0054 (12) |
C1 | 0.057 (3) | 0.038 (3) | 0.036 (2) | 0.007 (2) | −0.009 (2) | 0.005 (2) |
C2 | 0.032 (2) | 0.039 (2) | 0.047 (2) | 0.008 (2) | −0.009 (2) | 0.004 (2) |
C3 | 0.034 (2) | 0.050 (3) | 0.048 (2) | 0.014 (2) | 0.015 (2) | 0.004 (2) |
C4 | 0.050 (3) | 0.041 (3) | 0.039 (2) | 0.013 (2) | 0.017 (2) | −0.002 (2) |
C5 | 0.041 (2) | 0.045 (3) | 0.028 (2) | −0.004 (2) | 0.004 (2) | −0.012 (2) |
C6 | 0.043 (2) | 0.049 (3) | 0.040 (2) | −0.010 (2) | 0.009 (2) | −0.020 (2) |
C7 | 0.026 (2) | 0.055 (3) | 0.040 (2) | −0.012 (2) | 0.006 (2) | −0.003 (2) |
C8 | 0.039 (2) | 0.040 (3) | 0.044 (2) | −0.014 (2) | 0.007 (2) | 0.000 (2) |
C9 | 0.057 (3) | 0.038 (3) | 0.035 (2) | −0.009 (2) | 0.006 (2) | 0.011 (2) |
C10 | 0.057 (3) | 0.044 (3) | 0.027 (2) | −0.003 (2) | 0.005 (2) | 0.011 (2) |
N1 | 0.059 (2) | 0.034 (2) | 0.055 (2) | 0.015 (2) | 0.029 (2) | 0.008 (2) |
O6 | 0.062 (2) | 0.046 (2) | 0.039 (2) | 0.010 (2) | 0.0114 (14) | −0.0021 (14) |
O7 | 0.041 (2) | 0.044 (2) | 0.055 (2) | 0.0079 (13) | 0.0129 (14) | −0.0013 (15) |
O8 | 0.086 (3) | 0.103 (4) | 0.079 (3) | 0.048 (3) | 0.052 (2) | 0.009 (2) |
N2 | 0.032 (2) | 0.028 (2) | 0.040 (2) | −0.0017 (13) | −0.0071 (14) | 0.0073 (14) |
O9 | 0.050 (2) | 0.025 (2) | 0.0352 (14) | −0.0005 (12) | −0.0046 (12) | 0.0005 (11) |
O10 | 0.045 (2) | 0.031 (2) | 0.0340 (14) | 0.0022 (12) | −0.0024 (12) | −0.0015 (12) |
O11 | 0.088 (3) | 0.034 (2) | 0.060 (2) | −0.008 (2) | −0.026 (2) | 0.017 (2) |
N3 | 0.029 (2) | 0.031 (2) | 0.043 (2) | 0.0007 (13) | 0.0016 (14) | 0.0048 (14) |
O12 | 0.045 (2) | 0.040 (2) | 0.0285 (14) | −0.0089 (13) | −0.0013 (12) | 0.0006 (12) |
O13 | 0.039 (2) | 0.043 (2) | 0.0364 (15) | −0.0067 (13) | 0.0087 (12) | −0.0007 (13) |
O14 | 0.047 (2) | 0.049 (2) | 0.083 (2) | −0.025 (2) | 0.006 (2) | −0.006 (2) |
Pr—O6 | 2.509 (3) | O4—C6 | 1.428 (5) |
Pr—O9 | 2.542 (3) | O4—C7 | 1.439 (4) |
Pr—O7 | 2.566 (3) | O5—C9 | 1.434 (5) |
Pr—O13 | 2.567 (3) | O5—C8 | 1.435 (5) |
Pr—O12 | 2.587 (3) | C1—C2 | 1.492 (6) |
Pr—O2 | 2.603 (3) | C3—C4 | 1.487 (6) |
Pr—O10 | 2.634 (3) | C5—C6 | 1.491 (6) |
Pr—O4 | 2.663 (3) | C7—C8 | 1.489 (6) |
Pr—O3 | 2.670 (2) | C9—C10 | 1.496 (6) |
Pr—O5 | 2.687 (3) | N1—O8 | 1.224 (5) |
Pr—O1 | 2.709 (3) | N1—O6 | 1.263 (5) |
Pr—N1 | 2.952 (4) | N1—O7 | 1.270 (5) |
O1—C1 | 1.438 (5) | N2—O11 | 1.214 (4) |
O1—C10 | 1.443 (5) | N2—O10 | 1.263 (4) |
O2—C2 | 1.434 (5) | N2—O9 | 1.264 (4) |
O2—C3 | 1.444 (5) | N3—O14 | 1.210 (4) |
O3—C4 | 1.436 (5) | N3—O12 | 1.267 (4) |
O3—C5 | 1.437 (4) | N3—O13 | 1.271 (4) |
O6—Pr—O9 | 108.92 (10) | O13—Pr—N1 | 128.60 (11) |
O6—Pr—O7 | 50.42 (10) | O12—Pr—N1 | 93.94 (11) |
O9—Pr—O7 | 72.69 (10) | O2—Pr—N1 | 146.33 (9) |
O6—Pr—O13 | 116.01 (10) | O10—Pr—N1 | 67.01 (10) |
O9—Pr—O13 | 70.52 (9) | O4—Pr—N1 | 88.26 (11) |
O7—Pr—O13 | 131.24 (10) | O3—Pr—N1 | 146.07 (10) |
O6—Pr—O12 | 72.03 (10) | O5—Pr—N1 | 68.16 (10) |
O9—Pr—O12 | 104.93 (9) | O1—Pr—N1 | 87.33 (10) |
O7—Pr—O12 | 114.44 (10) | C1—O1—C10 | 111.8 (3) |
O13—Pr—O12 | 49.38 (8) | C1—O1—Pr | 120.0 (2) |
O6—Pr—O2 | 126.72 (9) | C10—O1—Pr | 114.3 (2) |
O9—Pr—O2 | 121.75 (9) | C2—O2—C3 | 113.0 (3) |
O7—Pr—O2 | 157.90 (10) | C2—O2—Pr | 116.1 (2) |
O13—Pr—O2 | 70.83 (9) | C3—O2—Pr | 119.2 (2) |
O12—Pr—O2 | 79.75 (9) | C4—O3—C5 | 112.1 (3) |
O6—Pr—O10 | 69.47 (10) | C4—O3—Pr | 119.7 (2) |
O9—Pr—O10 | 49.15 (8) | C5—O3—Pr | 114.7 (2) |
O7—Pr—O10 | 66.69 (10) | C6—O4—C7 | 113.0 (3) |
O13—Pr—O10 | 65.20 (9) | C6—O4—Pr | 121.3 (2) |
O12—Pr—O10 | 65.77 (9) | C7—O4—Pr | 116.7 (2) |
O2—Pr—O10 | 135.23 (9) | C9—O5—C8 | 110.5 (3) |
O6—Pr—O4 | 110.93 (10) | C9—O5—Pr | 123.1 (2) |
O9—Pr—O4 | 71.00 (9) | C8—O5—Pr | 121.0 (2) |
O7—Pr—O4 | 66.69 (10) | O1—C1—C2 | 107.7 (3) |
O13—Pr—O4 | 126.37 (8) | O2—C2—C1 | 106.1 (3) |
O12—Pr—O4 | 175.46 (8) | O2—C3—C4 | 107.1 (3) |
O2—Pr—O4 | 100.56 (9) | O3—C4—C3 | 107.8 (3) |
O10—Pr—O4 | 111.67 (9) | O3—C5—C6 | 109.7 (3) |
O6—Pr—O3 | 171.15 (9) | O4—C6—C5 | 106.7 (3) |
O9—Pr—O3 | 66.03 (9) | O4—C7—C8 | 109.8 (3) |
O7—Pr—O3 | 120.80 (9) | O5—C8—C7 | 107.6 (3) |
O13—Pr—O3 | 69.94 (9) | O5—C9—C10 | 107.8 (3) |
O12—Pr—O3 | 115.86 (8) | O1—C10—C9 | 109.8 (3) |
O2—Pr—O3 | 60.64 (8) | O8—N1—O6 | 122.0 (4) |
O10—Pr—O3 | 109.31 (8) | O8—N1—O7 | 120.8 (4) |
O4—Pr—O3 | 60.94 (8) | O6—N1—O7 | 117.2 (3) |
O6—Pr—O5 | 72.87 (10) | O8—N1—Pr | 175.7 (3) |
O9—Pr—O5 | 127.37 (9) | O6—N1—Pr | 57.4 (2) |
O7—Pr—O5 | 70.22 (10) | O7—N1—Pr | 60.0 (2) |
O13—Pr—O5 | 158.21 (9) | N1—O6—Pr | 97.5 (2) |
O12—Pr—O5 | 123.85 (8) | N1—O7—Pr | 94.6 (2) |
O2—Pr—O5 | 87.86 (9) | O11—N2—O10 | 121.8 (4) |
O10—Pr—O5 | 134.72 (9) | O11—N2—O9 | 121.3 (3) |
O4—Pr—O5 | 60.67 (8) | O10—N2—O9 | 116.9 (3) |
O3—Pr—O5 | 104.03 (8) | O11—N2—Pr | 177.5 (3) |
O6—Pr—O1 | 67.78 (9) | O10—N2—Pr | 60.6 (2) |
O9—Pr—O1 | 171.48 (9) | O9—N2—Pr | 56.4 (2) |
O7—Pr—O1 | 108.80 (9) | N2—O9—Pr | 99.1 (2) |
O13—Pr—O1 | 103.46 (9) | N2—O10—Pr | 94.8 (2) |
O12—Pr—O1 | 66.68 (9) | O14—N3—O12 | 121.8 (4) |
O2—Pr—O1 | 59.67 (8) | O14—N3—O13 | 122.2 (3) |
O10—Pr—O1 | 123.20 (9) | O12—N3—O13 | 116.0 (3) |
O4—Pr—O1 | 117.43 (9) | O14—N3—Pr | 171.9 (3) |
O3—Pr—O1 | 118.27 (8) | O12—N3—Pr | 58.8 (2) |
O5—Pr—O1 | 59.99 (8) | O13—N3—Pr | 57.9 (2) |
O6—Pr—N1 | 25.11 (11) | N3—O12—Pr | 96.5 (2) |
O9—Pr—N1 | 91.89 (10) | N3—O13—Pr | 97.3 (2) |
O7—Pr—N1 | 25.39 (11) |
Experimental details
Crystal data | |
Chemical formula | [Pr(NO3)3(C10H20O5)] |
Mr | 547.20 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.3236 (5), 14.5789 (14), 13.6184 (6) |
β (°) | 95.361 (4) |
V (Å3) | 1843.0 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.72 |
Crystal size (mm) | 0.5 × 0.5 × 0.26 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ scan (North et al., 1968) |
Tmin, Tmax | 0.227, 0.426 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3838, 3612, 2940 |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.075, 1.04 |
No. of reflections | 3611 |
No. of parameters | 254 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.23, −0.74 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, XCAD4 (Harms & Wocadlo, 1987), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
We have earlier reported on the conversion of carbon dioxide into oxalate in the presence of PrIII salts (Barrett et al., 1998). As part of a continuing study of this process, the action of carbon dioxide on an ethanolic solution of PrIII nitrate and 15-crown-5 was studied. The crystals obtained at the end of the reaction proved to be [Pr(15-crown-5)(NO3)3], (I). The structure of the complex is the same as found for the La (Lu et al., 1983; Rogers & Rollins, 1990), Ce (Lin & Xing, 1983), Eu (Bunzli et al., 1982) and Nd (Lu et al., 1983) analogs with the metal ion 11-coordinate and all three nitrate ligands on the same side of the metal.