Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102004766/sk1541sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102004766/sk1541Isup2.hkl |
CCDC reference: 187910
Colourless crystals of (I) were isolated from a solution of [Ce(Me3PO)4Cl3]·4H2O in nitromethane, which was allowed to evaporate in air over a period of three weeks.
Methyl-group H atoms were positioned geometrically, with C—H = 0.98 Å, and water H atoms were located in the difference electron-density map. The latter were not refined and all H atoms were given a fixed isotropic displacement parameter.
Data collection: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976).
[Ce(C3H9OP)4(H2O)4]Cl3·3H2O | Z = 2 |
Mr = 740.87 | F(000) = 758 |
Triclinic, P1 | Dx = 1.519 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.2753 (10) Å | Cell parameters from 12600 reflections |
b = 11.1003 (10) Å | θ = 2.9–27.5° |
c = 15.6822 (15) Å | µ = 1.89 mm−1 |
α = 70.406 (10)° | T = 120 K |
β = 82.483 (10)° | Block, colourless |
γ = 74.161 (10)° | 0.26 × 0.20 × 0.16 mm |
V = 1619.6 (3) Å3 |
Nonius KappaCCD area-detector diffractometer | 5444 independent reflections |
Radiation source: Nonius rotating anode | 4908 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
ϕ and ω scans | θmax = 25.0°, θmin = 3.2° |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | h = −12→11 |
Tmin = 0.656, Tmax = 0.739 | k = −13→13 |
18262 measured reflections | l = −18→18 |
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)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.064 | H-atom parameters not refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0184P)2 + 0.6782P] where P = (Fo2 + 2Fc2)/3 |
5444 reflections | (Δ/σ)max = 0.001 |
281 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.88 e Å−3 |
[Ce(C3H9OP)4(H2O)4]Cl3·3H2O | γ = 74.161 (10)° |
Mr = 740.87 | V = 1619.6 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.2753 (10) Å | Mo Kα radiation |
b = 11.1003 (10) Å | µ = 1.89 mm−1 |
c = 15.6822 (15) Å | T = 120 K |
α = 70.406 (10)° | 0.26 × 0.20 × 0.16 mm |
β = 82.483 (10)° |
Nonius KappaCCD area-detector diffractometer | 5444 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1997) | 4908 reflections with I > 2σ(I) |
Tmin = 0.656, Tmax = 0.739 | Rint = 0.073 |
18262 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.064 | H-atom parameters not refined |
S = 1.03 | Δρmax = 0.61 e Å−3 |
5444 reflections | Δρmin = −0.88 e Å−3 |
281 parameters |
Experimental. The missing 4.5% of reflections presumably arose from the choice of frames recorded during the data collection on the area diffractometer. |
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 | ||
Ce1 | 0.170923 (14) | 0.447541 (15) | 0.236975 (10) | 0.00969 (7) | |
Cl1 | 0.66467 (8) | 0.13714 (8) | 0.95434 (5) | 0.02455 (18) | |
Cl2 | 0.79567 (7) | 0.46661 (8) | 0.46286 (5) | 0.02255 (18) | |
Cl3 | 0.81261 (8) | 0.15098 (7) | 0.27890 (5) | 0.02305 (18) | |
P1 | 0.45924 (7) | 0.53612 (8) | 0.30830 (5) | 0.01389 (17) | |
P2 | 0.13475 (8) | 0.27826 (8) | 0.07704 (5) | 0.01521 (17) | |
P3 | 0.21974 (8) | 0.12407 (8) | 0.43087 (5) | 0.01755 (18) | |
P4 | −0.02876 (8) | 0.78827 (7) | 0.21972 (5) | 0.01511 (17) | |
O1 | 0.31975 (19) | 0.54269 (19) | 0.28467 (13) | 0.0167 (4) | |
O2 | 0.1148 (2) | 0.38855 (19) | 0.11687 (13) | 0.0178 (5) | |
O3 | 0.2181 (2) | 0.2225 (2) | 0.33801 (13) | 0.0205 (5) | |
O4 | 0.0266 (2) | 0.66530 (18) | 0.19285 (13) | 0.0171 (4) | |
O5 | 0.2950 (2) | 0.57446 (19) | 0.09564 (13) | 0.0172 (5) | |
O6 | −0.0693 (2) | 0.3978 (2) | 0.28078 (13) | 0.0194 (5) | |
O7 | 0.0860 (2) | 0.4750 (2) | 0.38972 (13) | 0.0215 (5) | |
O8 | 0.3968 (2) | 0.30949 (19) | 0.20133 (14) | 0.0207 (5) | |
O9 | 0.6418 (2) | 0.3001 (2) | 0.09643 (14) | 0.0236 (5) | |
O10 | 0.5393 (2) | 0.0538 (2) | 0.28094 (14) | 0.0250 (5) | |
O11 | 0.4524 (2) | 0.0460 (2) | 0.86491 (15) | 0.0305 (6) | |
C1 | 0.5285 (3) | 0.3828 (3) | 0.3900 (2) | 0.0238 (7) | |
H1A | 0.4672 | 0.3691 | 0.4439 | 0.0419* | |
H1B | 0.6167 | 0.3835 | 0.4069 | 0.0419* | |
H1C | 0.5399 | 0.3112 | 0.3643 | 0.0419* | |
C2 | 0.5748 (3) | 0.5549 (3) | 0.2123 (2) | 0.0227 (7) | |
H2A | 0.5398 | 0.6390 | 0.1658 | 0.0419* | |
H2B | 0.5853 | 0.4822 | 0.1878 | 0.0419* | |
H2C | 0.6628 | 0.5540 | 0.2305 | 0.0419* | |
C3 | 0.4572 (3) | 0.6642 (3) | 0.3538 (2) | 0.0220 (7) | |
H3A | 0.4194 | 0.7501 | 0.3099 | 0.0419* | |
H3B | 0.5498 | 0.6595 | 0.3662 | 0.0419* | |
H3C | 0.4012 | 0.6532 | 0.4102 | 0.0419* | |
C4 | 0.1849 (3) | 0.1205 (3) | 0.1596 (2) | 0.0269 (8) | |
H4A | 0.2697 | 0.1136 | 0.1852 | 0.0419* | |
H4B | 0.1983 | 0.0516 | 0.1310 | 0.0419* | |
H4C | 0.1142 | 0.1095 | 0.2080 | 0.0419* | |
C5 | −0.0185 (3) | 0.2855 (3) | 0.0333 (2) | 0.0238 (7) | |
H5A | −0.0895 | 0.2798 | 0.0817 | 0.0419* | |
H5B | −0.0055 | 0.2118 | 0.0094 | 0.0419* | |
H5C | −0.0454 | 0.3690 | −0.0155 | 0.0419* | |
C6 | 0.2602 (4) | 0.2892 (4) | −0.0131 (3) | 0.0413 (10) | |
H6A | 0.3463 | 0.2853 | 0.0094 | 0.0419* | |
H6B | 0.2317 | 0.3728 | −0.0615 | 0.0419* | |
H6C | 0.2716 | 0.2155 | −0.0368 | 0.0419* | |
C7 | 0.2723 (3) | −0.0406 (3) | 0.4263 (2) | 0.0251 (7) | |
H7A | 0.2114 | −0.0532 | 0.3885 | 0.0419* | |
H7B | 0.2693 | −0.1027 | 0.4876 | 0.0419* | |
H7C | 0.3649 | −0.0565 | 0.4001 | 0.0419* | |
C8 | 0.0585 (4) | 0.1418 (3) | 0.4892 (2) | 0.0331 (9) | |
H8A | −0.0083 | 0.1347 | 0.4530 | 0.0419* | |
H8B | 0.0311 | 0.2282 | 0.4988 | 0.0419* | |
H8C | 0.0639 | 0.0721 | 0.5479 | 0.0419* | |
C9 | 0.3347 (4) | 0.1376 (4) | 0.5003 (2) | 0.0327 (9) | |
H9A | 0.4253 | 0.1281 | 0.4707 | 0.0419* | |
H9B | 0.3372 | 0.0682 | 0.5590 | 0.0419* | |
H9C | 0.3050 | 0.2242 | 0.5097 | 0.0419* | |
C10 | −0.0588 (3) | 0.9334 (3) | 0.1237 (2) | 0.0219 (7) | |
H10A | 0.0254 | 0.9383 | 0.0867 | 0.0419* | |
H10B | −0.0903 | 1.0113 | 0.1441 | 0.0419* | |
H10C | −0.1280 | 0.9303 | 0.0875 | 0.0419* | |
C11 | 0.0850 (3) | 0.8126 (3) | 0.2858 (2) | 0.0225 (7) | |
H11A | 0.1724 | 0.8139 | 0.2525 | 0.0419* | |
H11B | 0.0976 | 0.7405 | 0.3433 | 0.0419* | |
H11C | 0.0472 | 0.8968 | 0.2979 | 0.0419* | |
C12 | −0.1849 (3) | 0.7866 (3) | 0.2831 (2) | 0.0285 (8) | |
H12A | −0.1729 | 0.7079 | 0.3367 | 0.0419* | |
H12B | −0.2531 | 0.7851 | 0.2454 | 0.0419* | |
H12C | −0.2148 | 0.8657 | 0.3022 | 0.0419* | |
H5X | 0.3027 | 0.6592 | 0.0926 | 0.030* | |
H5Y | 0.2778 | 0.5928 | 0.0405 | 0.030* | |
H6X | −0.1092 | 0.4167 | 0.3234 | 0.030* | |
H6Y | −0.0969 | 0.3283 | 0.2802 | 0.030* | |
H7X | 0.0018 | 0.4834 | 0.4183 | 0.030* | |
H7Y | 0.1436 | 0.4850 | 0.4297 | 0.030* | |
H8X | 0.4244 | 0.2223 | 0.2363 | 0.030* | |
H8Y | 0.4698 | 0.3282 | 0.1634 | 0.030* | |
H9X | 0.6823 | 0.2483 | 0.1518 | 0.030* | |
H9Y | 0.6558 | 0.2215 | 0.0834 | 0.030* | |
H10X | 0.6168 | 0.0787 | 0.2753 | 0.030* | |
H10Y | 0.5488 | 0.0223 | 0.2325 | 0.030* | |
H11X | 0.4221 | −0.0040 | 0.9144 | 0.030* | |
H11Y | 0.5332 | 0.0363 | 0.8929 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ce1 | 0.00884 (11) | 0.01139 (10) | 0.01005 (10) | −0.00222 (6) | −0.00039 (6) | −0.00514 (7) |
Cl1 | 0.0271 (5) | 0.0225 (4) | 0.0279 (4) | −0.0097 (3) | 0.0001 (3) | −0.0104 (3) |
Cl2 | 0.0144 (4) | 0.0417 (5) | 0.0187 (4) | −0.0116 (3) | 0.0030 (3) | −0.0163 (4) |
Cl3 | 0.0224 (4) | 0.0231 (4) | 0.0274 (4) | −0.0058 (3) | −0.0008 (3) | −0.0126 (3) |
P1 | 0.0103 (4) | 0.0203 (4) | 0.0143 (4) | −0.0066 (3) | 0.0004 (3) | −0.0077 (3) |
P2 | 0.0155 (4) | 0.0194 (4) | 0.0157 (4) | −0.0070 (3) | 0.0026 (3) | −0.0109 (3) |
P3 | 0.0192 (5) | 0.0146 (4) | 0.0155 (4) | −0.0039 (3) | 0.0027 (3) | −0.0019 (3) |
P4 | 0.0154 (4) | 0.0127 (4) | 0.0168 (4) | −0.0002 (3) | −0.0013 (3) | −0.0065 (3) |
O1 | 0.0105 (11) | 0.0263 (12) | 0.0193 (11) | −0.0070 (9) | 0.0016 (8) | −0.0138 (9) |
O2 | 0.0235 (12) | 0.0175 (11) | 0.0168 (11) | −0.0050 (8) | −0.0040 (9) | −0.0099 (9) |
O3 | 0.0187 (12) | 0.0170 (11) | 0.0177 (11) | 0.0007 (8) | 0.0025 (9) | −0.0004 (9) |
O4 | 0.0196 (12) | 0.0123 (11) | 0.0205 (11) | 0.0002 (8) | −0.0039 (9) | −0.0085 (9) |
O5 | 0.0236 (12) | 0.0164 (11) | 0.0115 (10) | −0.0082 (9) | 0.0009 (8) | −0.0024 (9) |
O6 | 0.0155 (12) | 0.0266 (12) | 0.0230 (12) | −0.0097 (9) | 0.0041 (9) | −0.0149 (10) |
O7 | 0.0163 (12) | 0.0406 (14) | 0.0178 (11) | −0.0156 (10) | 0.0067 (8) | −0.0182 (10) |
O8 | 0.0124 (12) | 0.0158 (11) | 0.0264 (12) | 0.0009 (8) | 0.0076 (9) | −0.0035 (9) |
O9 | 0.0251 (13) | 0.0254 (12) | 0.0199 (12) | −0.0063 (9) | 0.0040 (9) | −0.0082 (10) |
O10 | 0.0203 (13) | 0.0239 (12) | 0.0269 (13) | −0.0014 (9) | 0.0005 (9) | −0.0065 (10) |
O11 | 0.0337 (15) | 0.0392 (15) | 0.0224 (13) | −0.0162 (11) | −0.0049 (10) | −0.0073 (11) |
C1 | 0.0238 (19) | 0.0272 (19) | 0.0211 (17) | −0.0111 (14) | −0.0079 (14) | −0.0021 (14) |
C2 | 0.0167 (18) | 0.0309 (19) | 0.0208 (17) | −0.0081 (13) | 0.0044 (13) | −0.0088 (15) |
C3 | 0.0184 (18) | 0.0321 (19) | 0.0252 (18) | −0.0123 (14) | 0.0018 (13) | −0.0176 (15) |
C4 | 0.0264 (19) | 0.0191 (18) | 0.038 (2) | −0.0005 (14) | −0.0096 (15) | −0.0130 (15) |
C5 | 0.029 (2) | 0.0237 (18) | 0.0216 (17) | −0.0098 (14) | −0.0082 (14) | −0.0055 (14) |
C6 | 0.039 (2) | 0.058 (3) | 0.040 (2) | −0.0261 (19) | 0.0216 (17) | −0.030 (2) |
C7 | 0.0264 (19) | 0.0177 (17) | 0.0301 (19) | −0.0046 (13) | −0.0001 (14) | −0.0071 (15) |
C8 | 0.029 (2) | 0.0250 (19) | 0.033 (2) | −0.0040 (15) | 0.0158 (15) | −0.0027 (16) |
C9 | 0.047 (2) | 0.030 (2) | 0.0212 (18) | −0.0129 (17) | −0.0093 (16) | −0.0023 (16) |
C10 | 0.0262 (19) | 0.0161 (17) | 0.0217 (17) | −0.0006 (13) | −0.0039 (13) | −0.0062 (14) |
C11 | 0.031 (2) | 0.0150 (16) | 0.0238 (18) | −0.0025 (13) | −0.0077 (14) | −0.0092 (14) |
C12 | 0.023 (2) | 0.0257 (19) | 0.0297 (19) | 0.0009 (14) | 0.0048 (14) | −0.0076 (15) |
Ce1—O1 | 2.3926 (19) | O11—H11Y | 0.9526 |
Ce1—O2 | 2.372 (2) | C1—H1A | 0.9800 |
Ce1—O3 | 2.4230 (19) | C1—H1B | 0.9800 |
Ce1—O4 | 2.3896 (19) | C1—H1C | 0.9800 |
Ce1—O5 | 2.5827 (18) | C2—H2A | 0.9800 |
Ce1—O6 | 2.6300 (19) | C2—H2B | 0.9800 |
Ce1—O7 | 2.528 (2) | C2—H2C | 0.9800 |
Ce1—O8 | 2.518 (2) | C3—H3A | 0.9800 |
P1—O1 | 1.503 (2) | C3—H3B | 0.9800 |
P1—C1 | 1.778 (3) | C3—H3C | 0.9800 |
P1—C2 | 1.782 (3) | C4—H4A | 0.9800 |
P1—C3 | 1.786 (3) | C4—H4B | 0.9800 |
P2—O2 | 1.508 (2) | C4—H4C | 0.9800 |
P2—C5 | 1.770 (3) | C5—H5A | 0.9800 |
P2—C6 | 1.780 (3) | C5—H5B | 0.9800 |
P2—C4 | 1.780 (3) | C5—H5C | 0.9800 |
P3—O3 | 1.498 (2) | C6—H6A | 0.9800 |
P3—C9 | 1.774 (3) | C6—H6B | 0.9800 |
P3—C8 | 1.779 (3) | C6—H6C | 0.9800 |
P3—C7 | 1.783 (3) | C7—H7A | 0.9800 |
P4—O4 | 1.505 (2) | C7—H7B | 0.9800 |
P4—C12 | 1.774 (3) | C7—H7C | 0.9800 |
P4—C10 | 1.784 (3) | C8—H8A | 0.9800 |
P4—C11 | 1.786 (3) | C8—H8B | 0.9800 |
O5—H5X | 0.9502 | C8—H8C | 0.9800 |
O5—H5Y | 0.8502 | C9—H9A | 0.9800 |
O6—H6X | 0.7960 | C9—H9B | 0.9800 |
O6—H6Y | 0.8949 | C9—H9C | 0.9800 |
O7—H7X | 0.9166 | C10—H10A | 0.9800 |
O7—H7Y | 0.9675 | C10—H10B | 0.9800 |
O8—H8X | 0.9235 | C10—H10C | 0.9800 |
O8—H8Y | 0.9195 | C11—H11A | 0.9800 |
O9—H9X | 0.9420 | C11—H11B | 0.9800 |
O9—H9Y | 0.9314 | C11—H11C | 0.9800 |
O10—H10X | 0.8966 | C12—H12A | 0.9800 |
O10—H10Y | 0.9215 | C12—H12B | 0.9800 |
O11—H11X | 0.8661 | C12—H12C | 0.9800 |
O2—Ce1—O4 | 95.04 (7) | P1—C1—H1B | 109.5 |
O2—Ce1—O1 | 145.66 (7) | H1A—C1—H1B | 109.5 |
O4—Ce1—O1 | 85.72 (7) | P1—C1—H1C | 109.5 |
O2—Ce1—O3 | 93.30 (7) | H1A—C1—H1C | 109.5 |
O4—Ce1—O3 | 149.91 (7) | H1B—C1—H1C | 109.5 |
O1—Ce1—O3 | 103.12 (7) | P1—C2—H2A | 109.5 |
O2—Ce1—O8 | 79.32 (7) | P1—C2—H2B | 109.5 |
O4—Ce1—O8 | 143.01 (6) | H2A—C2—H2B | 109.5 |
O1—Ce1—O8 | 79.73 (7) | P1—C2—H2C | 109.5 |
O3—Ce1—O8 | 67.02 (6) | H2A—C2—H2C | 109.5 |
O2—Ce1—O7 | 142.93 (7) | H2B—C2—H2C | 109.5 |
O4—Ce1—O7 | 78.93 (7) | P1—C3—H3A | 109.5 |
O1—Ce1—O7 | 70.96 (6) | P1—C3—H3B | 109.5 |
O3—Ce1—O7 | 77.05 (7) | H3A—C3—H3B | 109.5 |
O8—Ce1—O7 | 126.33 (7) | P1—C3—H3C | 109.5 |
O2—Ce1—O5 | 75.65 (7) | H3A—C3—H3C | 109.5 |
O4—Ce1—O5 | 75.84 (7) | H3B—C3—H3C | 109.5 |
O1—Ce1—O5 | 71.26 (6) | P2—C4—H4A | 109.5 |
O3—Ce1—O5 | 134.25 (7) | P2—C4—H4B | 109.5 |
O8—Ce1—O5 | 67.32 (6) | H4A—C4—H4B | 109.5 |
O7—Ce1—O5 | 135.61 (6) | P2—C4—H4C | 109.5 |
O2—Ce1—O6 | 73.50 (7) | H4A—C4—H4C | 109.5 |
O4—Ce1—O6 | 78.80 (7) | H4B—C4—H4C | 109.5 |
O1—Ce1—O6 | 139.51 (6) | P2—C5—H5A | 109.5 |
O3—Ce1—O6 | 75.99 (7) | P2—C5—H5B | 109.5 |
O8—Ce1—O6 | 132.16 (7) | H5A—C5—H5B | 109.5 |
O7—Ce1—O6 | 69.45 (6) | P2—C5—H5C | 109.5 |
O5—Ce1—O6 | 137.71 (6) | H5A—C5—H5C | 109.5 |
O1—P1—C1 | 111.31 (13) | H5B—C5—H5C | 109.5 |
O1—P1—C2 | 112.50 (13) | P2—C6—H6A | 109.5 |
C1—P1—C2 | 107.30 (16) | P2—C6—H6B | 109.5 |
O1—P1—C3 | 111.37 (13) | H6A—C6—H6B | 109.5 |
C1—P1—C3 | 107.75 (16) | P2—C6—H6C | 109.5 |
C2—P1—C3 | 106.32 (15) | H6A—C6—H6C | 109.5 |
O2—P2—C5 | 110.01 (14) | H6B—C6—H6C | 109.5 |
O2—P2—C6 | 111.54 (16) | P3—C7—H7A | 109.5 |
C5—P2—C6 | 107.84 (18) | P3—C7—H7B | 109.5 |
O2—P2—C4 | 111.84 (14) | H7A—C7—H7B | 109.5 |
C5—P2—C4 | 107.58 (15) | P3—C7—H7C | 109.5 |
C6—P2—C4 | 107.85 (19) | H7A—C7—H7C | 109.5 |
O3—P3—C9 | 111.92 (14) | H7B—C7—H7C | 109.5 |
O3—P3—C8 | 112.77 (14) | P3—C8—H8A | 109.5 |
C9—P3—C8 | 106.80 (19) | P3—C8—H8B | 109.5 |
O3—P3—C7 | 111.25 (14) | H8A—C8—H8B | 109.5 |
C9—P3—C7 | 106.34 (17) | P3—C8—H8C | 109.5 |
C8—P3—C7 | 107.40 (16) | H8A—C8—H8C | 109.5 |
O4—P4—C12 | 112.02 (15) | H8B—C8—H8C | 109.5 |
O4—P4—C10 | 112.05 (13) | P3—C9—H9A | 109.5 |
C12—P4—C10 | 106.79 (15) | P3—C9—H9B | 109.5 |
O4—P4—C11 | 112.62 (13) | H9A—C9—H9B | 109.5 |
C12—P4—C11 | 107.56 (17) | P3—C9—H9C | 109.5 |
C10—P4—C11 | 105.37 (15) | H9A—C9—H9C | 109.5 |
P1—O1—Ce1 | 149.58 (12) | H9B—C9—H9C | 109.5 |
P2—O2—Ce1 | 144.83 (12) | P4—C10—H10A | 109.5 |
P3—O3—Ce1 | 151.31 (13) | P4—C10—H10B | 109.5 |
P4—O4—Ce1 | 144.27 (12) | H10A—C10—H10B | 109.5 |
Ce1—O5—H5X | 117.6 | P4—C10—H10C | 109.5 |
Ce1—O5—H5Y | 127.2 | H10A—C10—H10C | 109.5 |
H5X—O5—H5Y | 97.5 | H10B—C10—H10C | 109.5 |
Ce1—O6—H6X | 116.9 | P4—C11—H11A | 109.5 |
Ce1—O6—H6Y | 129.1 | P4—C11—H11B | 109.5 |
H6X—O6—H6Y | 104.6 | H11A—C11—H11B | 109.5 |
Ce1—O7—H7X | 132.4 | P4—C11—H11C | 109.5 |
Ce1—O7—H7Y | 122.4 | H11A—C11—H11C | 109.5 |
H7X—O7—H7Y | 105.1 | H11B—C11—H11C | 109.5 |
Ce1—O8—H8X | 119.6 | P4—C12—H12A | 109.5 |
Ce1—O8—H8Y | 133.9 | P4—C12—H12B | 109.5 |
H8X—O8—H8Y | 105.9 | H12A—C12—H12B | 109.5 |
H9X—O9—H9Y | 86.5 | P4—C12—H12C | 109.5 |
H10X—O10—H10Y | 101.2 | H12A—C12—H12C | 109.5 |
H11X—O11—H11Y | 91.3 | H12B—C12—H12C | 109.5 |
P1—C1—H1A | 109.5 | ||
C1—P1—O1—Ce1 | −52.0 (3) | C9—P3—O3—Ce1 | −65.7 (3) |
C2—P1—O1—Ce1 | 68.5 (3) | C8—P3—O3—Ce1 | 54.8 (3) |
C3—P1—O1—Ce1 | −172.3 (2) | C7—P3—O3—Ce1 | 175.5 (2) |
O2—Ce1—O1—P1 | −66.8 (3) | O2—Ce1—O3—P3 | −147.3 (3) |
O4—Ce1—O1—P1 | −159.4 (2) | O4—Ce1—O3—P3 | −41.3 (3) |
O3—Ce1—O1—P1 | 49.7 (2) | O1—Ce1—O3—P3 | 63.1 (3) |
O8—Ce1—O1—P1 | −13.6 (2) | O8—Ce1—O3—P3 | 135.8 (3) |
O7—Ce1—O1—P1 | 120.8 (2) | O7—Ce1—O3—P3 | −3.5 (3) |
O5—Ce1—O1—P1 | −82.9 (2) | O5—Ce1—O3—P3 | 139.6 (2) |
O6—Ce1—O1—P1 | 133.4 (2) | O6—Ce1—O3—P3 | −75.2 (3) |
C5—P2—O2—Ce1 | 141.6 (2) | C12—P4—O4—Ce1 | −91.7 (2) |
C6—P2—O2—Ce1 | −98.8 (2) | C10—P4—O4—Ce1 | 148.4 (2) |
C4—P2—O2—Ce1 | 22.1 (3) | C11—P4—O4—Ce1 | 29.8 (3) |
O4—Ce1—O2—P2 | −175.4 (2) | O2—Ce1—O4—P4 | 174.0 (2) |
O1—Ce1—O2—P2 | 94.8 (2) | O1—Ce1—O4—P4 | −40.5 (2) |
O3—Ce1—O2—P2 | −24.4 (2) | O3—Ce1—O4—P4 | 68.4 (3) |
O8—Ce1—O2—P2 | 41.5 (2) | O8—Ce1—O4—P4 | −107.1 (2) |
O7—Ce1—O2—P2 | −97.1 (2) | O7—Ce1—O4—P4 | 30.9 (2) |
O5—Ce1—O2—P2 | 110.6 (2) | O5—Ce1—O4—P4 | −112.2 (2) |
O6—Ce1—O2—P2 | −98.7 (2) | O6—Ce1—O4—P4 | 101.9 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5X···Cl1i | 0.95 | 2.24 | 3.161 (2) | 164 |
O5—H5Y···O9ii | 0.85 | 2.25 | 2.933 (3) | 137 |
O6—H6X···Cl2iii | 0.80 | 2.45 | 3.242 (2) | 173 |
O6—H6Y···Cl3iii | 0.89 | 2.40 | 3.295 (2) | 176 |
O7—H7X···Cl2iii | 0.92 | 2.18 | 3.067 (2) | 163 |
O7—H7Y···Cl2i | 0.97 | 2.14 | 3.068 (2) | 160 |
O8—H8X···O10 | 0.92 | 1.87 | 2.755 (3) | 159 |
O8—H8Y···O9 | 0.92 | 1.94 | 2.818 (3) | 160 |
O9—H9X···Cl3 | 0.94 | 2.32 | 3.250 (2) | 168 |
O9—H9Y···Cl1iv | 0.93 | 2.48 | 3.260 (2) | 141 |
O10—H10X···Cl3 | 0.90 | 2.37 | 3.265 (2) | 172 |
O10—H10Y···O11v | 0.92 | 1.92 | 2.840 (3) | 173 |
O11—H11X···Cl1vi | 0.87 | 2.33 | 3.193 (2) | 179 |
O11—H11Y···Cl1 | 0.95 | 2.43 | 3.271 (2) | 147 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x, y, z−1; (v) −x+1, −y, −z+1; (vi) −x+1, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Ce(C3H9OP)4(H2O)4]Cl3·3H2O |
Mr | 740.87 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 10.2753 (10), 11.1003 (10), 15.6822 (15) |
α, β, γ (°) | 70.406 (10), 82.483 (10), 74.161 (10) |
V (Å3) | 1619.6 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.89 |
Crystal size (mm) | 0.26 × 0.20 × 0.16 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1997) |
Tmin, Tmax | 0.656, 0.739 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18262, 5444, 4908 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.064, 1.03 |
No. of reflections | 5444 |
No. of parameters | 281 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.61, −0.88 |
Computer programs: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997), COLLECT and DENZO, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976).
Ce1—O1 | 2.3926 (19) | Ce1—O5 | 2.5827 (18) |
Ce1—O2 | 2.372 (2) | Ce1—O6 | 2.6300 (19) |
Ce1—O3 | 2.4230 (19) | Ce1—O7 | 2.528 (2) |
Ce1—O4 | 2.3896 (19) | Ce1—O8 | 2.518 (2) |
O2—Ce1—O1 | 145.66 (7) | O2—Ce1—O6 | 73.50 (7) |
O4—Ce1—O3 | 149.91 (7) | O7—Ce1—O6 | 69.45 (6) |
O3—Ce1—O8 | 67.02 (6) | P1—O1—Ce1 | 149.58 (12) |
O1—Ce1—O7 | 70.96 (6) | P2—O2—Ce1 | 144.83 (12) |
O4—Ce1—O5 | 75.84 (7) | P3—O3—Ce1 | 151.31 (13) |
O8—Ce1—O5 | 67.32 (6) | P4—O4—Ce1 | 144.27 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5X···Cl1i | 0.95 | 2.24 | 3.161 (2) | 164 |
O5—H5Y···O9ii | 0.85 | 2.25 | 2.933 (3) | 137 |
O6—H6X···Cl2iii | 0.80 | 2.45 | 3.242 (2) | 173 |
O6—H6Y···Cl3iii | 0.89 | 2.40 | 3.295 (2) | 176 |
O7—H7X···Cl2iii | 0.92 | 2.18 | 3.067 (2) | 163 |
O7—H7Y···Cl2i | 0.97 | 2.14 | 3.068 (2) | 160 |
O8—H8X···O10 | 0.92 | 1.87 | 2.755 (3) | 159 |
O8—H8Y···O9 | 0.92 | 1.94 | 2.818 (3) | 160 |
O9—H9X···Cl3 | 0.94 | 2.32 | 3.250 (2) | 168 |
O9—H9Y···Cl1iv | 0.93 | 2.48 | 3.260 (2) | 141 |
O10—H10X···Cl3 | 0.90 | 2.37 | 3.265 (2) | 172 |
O10—H10Y···O11v | 0.92 | 1.92 | 2.840 (3) | 173 |
O11—H11X···Cl1vi | 0.87 | 2.33 | 3.193 (2) | 179 |
O11—H11Y···Cl1 | 0.95 | 2.43 | 3.271 (2) | 147 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x−1, y, z; (iv) x, y, z−1; (v) −x+1, −y, −z+1; (vi) −x+1, −y, −z+2. |
During attempts to synthesize octahedral [Ln(Me3PO)6]3+ cations (Ln is a lanthanide), the reaction of CeCl3·6H2O with eight molar equivalents of Me3PO in methanol was investigated. The product isolated was [Ce(Me3PO)4Cl3]·4H2O, as identified by analysis and IR spectroscopy, and, significantly, the complex was a non-electrolyte in freshly prepared nitromethane solution (Leung, 2001). Colourless crystals were isolated from a solution of this complex in nitromethane, which was allowed to evaporate in air over a period of three weeks. The structure showed that the crystals contained the title complex, [Ce(Me3PO)4(H2O)4]Cl3·3H2O, (I), showing that the initial complex had been converted into the mixed phosphine oxide-aqua complex on standing in the polar solvent, the extra water coming from the atmosphere. Complexes of the type [Ln(Me3PO)6][PF6]3 have since been isolated from the reaction of LnCl3.xH2O, Me3PO and NH4PF6 in 1:8:3 molar ratios in methanol (Hill et al., 2002). The structure of (I) is presented here. \sch
The structure of (I) consists of a distorted eight-coordinate CeIII cation composed of four O-donor phosphine oxide ligands and four water molecules. The Ce—O(P) distances are shorter [2.372 (2)–2.423 (2) Å] than the Ce—O(H2) distances [2.518 (2)–2.630 (2) Å]. The oxygen geometry at the Ce atom is, to a good approximation, a triangulated dodecahedron (bisdisphenoid) with idealized D2 d symmetry. Of the two interpenetrating tetrahedra, the flattened tetrahedron is formed by the four Me3PO groups and the elongated one by the four H2O ligands. The two trapezoidal planes often used to describe this geometry are similar, and are formed by atoms O1, O2, O6 and O7, and O3, O4, O5 and O8, respectively (Table 1 and Fig. 1).
The M—O—P angles in phosphine oxide complexes are highly variable and, in the present case, are in the range 144.27 (12)–151.31 (13)°. All the O—P—C angles are larger than the idealized tetrahedral angles (by an average of 2°) and the C—P—C angles are correspondingly smaller.
Both H atoms of each water molecule are involved in hydrogen bonding, either to a Cl atom or to an O atom. The shortest OH···Cl distance involves atom O7 and the shortest OH···O distance is between a coordinated water and a hydrate water molecule (Table 2).
There are no reports of structurally characterized lanthanide phosphine oxide complexes with the same stoichiometry as (I), but the structures of two CeIII complexes of triphenylphosphine oxide, the nine-coordinate [Ce(Ph3PO)3(NO3)3] (Lin et al., 1994) and [Ce(Ph3PO)2(EtOH)(NO3)3] (Levason et al., 2000), have been reported. The structure of the six-coordinate arsine oxide complex [Ce(Ph3AsO)3Cl3]·MeCN has also been described (Ryan et al., 1987).