Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003243/qa0226sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003243/qa0226Isup2.hkl |
CCDC reference: 144685
All materials used were of reagent grade. NdCl3 and sodium acetate were purchased from Aldrich, and the NaLOMe ligand was prepared according to the literature procedure of Klaüi (1979). 1H NMR spectra were recorded on a Varian 300-NMR spectrometer at ambient temperature and chemical shifts were referenced to the internal standard tetramethylsilane. Elemental analyses were performed in the Chemical Analysis Laboratory of the Korea Basic Science Institute at Kyungpook National University. A mixture of NdCl3 (0.16 g, 0.64 mmol), NaLOMe (0.30 g, 0.64 mmol) and NaAc (0.10 g, 1.29 mmol) in 25 ml of dry THF was stirred for 2 d at room temperature. The resulting yellow suspension was dried in vacuo and extracted with methanol. The yellow solution was slowly evaporated to afford a crop of X-ray quality yellow crystals (0.24 g, 53% based on Nd). Analysis calculated for C30H58O26P6Co2Nd2: C 25.25, H 4.10%; found: C 25.10, H 4.11%. 1H NMR (CDCl3): δ 8.84 (br, Cp), 3.76 (br, OCH3), -0.62 (br, OOCCH3), -1.12 (br, OOCCH3).
The methoxy O5 and O7 atoms and the methyl C13 atom of the µ-O,O':O' acetato ligand were disordered and refined on Uiso with an occupancy factor of 0.5. The Cp ring was constrained as a regular pentagon on Uiso. H atoms were constrained using a riding model and with U(H) fixed at 1.5 (Me) or 1.2 (Cp) times Ueq of the parent atoms.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
[Co2Nd2(C5H5)2(C2H3O2)4(C2H6O3P)6] | F(000) = 1420 |
Mr = 1426.96 | Dx = 1.820 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
a = 14.0685 (9) Å | Cell parameters from 25 reflections |
b = 11.9199 (9) Å | θ = 11–13° |
c = 15.7428 (7) Å | µ = 2.85 mm−1 |
β = 99.541 (4)° | T = 293 K |
V = 2603.5 (3) Å3 | Tetragonal rod, yellow |
Z = 2 | 0.50 × 0.50 × 0.40 mm |
Enraf-Nonius CAD-4 diffractometer | 4212 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.013 |
Graphite monochromator | θmax = 26.0°, θmin = 1.3° |
ω/2θ scans | h = 0→17 |
Absorption correction: ψ scan (MolEN; Fair, 1990) | k = 0→14 |
Tmin = 0.273, Tmax = 0.320 | l = −19→19 |
5598 measured reflections | 2 standard reflections every 60 min |
4744 independent reflections | intensity decay: 0.1% |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0677P)2 + 14.444P] where P = (Fo2 + 2Fc2)/3 |
4744 reflections | (Δ/σ)max = 0.001 |
261 parameters | Δρmax = 2.46 e Å−3 |
0 restraints | Δρmin = −1.00 e Å−3 |
[Co2Nd2(C5H5)2(C2H3O2)4(C2H6O3P)6] | V = 2603.5 (3) Å3 |
Mr = 1426.96 | Z = 2 |
Monoclinic, P21/a | Mo Kα radiation |
a = 14.0685 (9) Å | µ = 2.85 mm−1 |
b = 11.9199 (9) Å | T = 293 K |
c = 15.7428 (7) Å | 0.50 × 0.50 × 0.40 mm |
β = 99.541 (4)° |
Enraf-Nonius CAD-4 diffractometer | 4212 reflections with I > 2σ(I) |
Absorption correction: ψ scan (MolEN; Fair, 1990) | Rint = 0.013 |
Tmin = 0.273, Tmax = 0.320 | 2 standard reflections every 60 min |
5598 measured reflections | intensity decay: 0.1% |
4744 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0677P)2 + 14.444P] where P = (Fo2 + 2Fc2)/3 |
4744 reflections | Δρmax = 2.46 e Å−3 |
261 parameters | Δρmin = −1.00 e Å−3 |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Nd | 0.05978 (2) | 0.01046 (2) | 0.123883 (17) | 0.02682 (12) | |
Co | 0.25044 (6) | −0.01019 (6) | 0.37413 (5) | 0.0318 (2) | |
P1 | 0.29866 (12) | −0.02220 (18) | 0.25050 (11) | 0.0457 (4) | |
P2 | 0.12888 (14) | −0.11986 (15) | 0.33473 (10) | 0.0429 (4) | |
P3 | 0.16400 (13) | 0.13490 (13) | 0.32970 (10) | 0.0393 (4) | |
O1 | 0.2281 (3) | −0.0176 (4) | 0.1676 (3) | 0.0418 (10) | |
O2 | 0.0653 (3) | −0.1019 (4) | 0.2502 (3) | 0.0455 (11) | |
O3 | 0.1034 (4) | 0.1366 (4) | 0.2428 (3) | 0.0476 (12) | |
O4 | 0.3745 (5) | 0.0806 (7) | 0.2519 (4) | 0.090 (2) | |
C4 | 0.4131 (9) | 0.1086 (12) | 0.1800 (7) | 0.107 (4) | |
H4A | 0.4594 | 0.0529 | 0.1704 | 0.161* | |
H4B | 0.4441 | 0.1804 | 0.1886 | 0.161* | |
H4C | 0.3626 | 0.1121 | 0.1309 | 0.161* | |
O5A | 0.3763 (7) | −0.1110 (8) | 0.2410 (6) | 0.039 (2)* | 0.50 |
O5B | 0.3470 (11) | −0.1517 (14) | 0.2529 (9) | 0.082 (4)* | 0.50 |
C5 | 0.3388 (8) | −0.2243 (9) | 0.1961 (7) | 0.089 (3) | |
H5A | 0.3091 | −0.2790 | 0.2277 | 0.133* | |
H5B | 0.3954 | −0.2548 | 0.1789 | 0.133* | |
H5C | 0.2936 | −0.2035 | 0.1450 | 0.133* | |
O6 | 0.1706 (5) | −0.2455 (5) | 0.3384 (4) | 0.087 (2) | |
C6 | 0.1171 (8) | −0.3333 (8) | 0.2949 (7) | 0.090 (3) | |
H6A | 0.0705 | −0.3594 | 0.3286 | 0.135* | |
H6B | 0.1595 | −0.3938 | 0.2862 | 0.135* | |
H6C | 0.0845 | −0.3071 | 0.2401 | 0.135* | |
O7A | 0.0553 (10) | −0.0975 (12) | 0.4097 (8) | 0.067 (3)* | 0.50 |
O7B | 0.0666 (7) | −0.1474 (9) | 0.4035 (6) | 0.042 (2)* | 0.50 |
C7 | −0.0358 (8) | −0.0935 (12) | 0.3924 (7) | 0.099 (4) | |
H7A | −0.0535 | −0.0657 | 0.3351 | 0.149* | |
H7B | −0.0440 | −0.0344 | 0.4328 | 0.149* | |
H7C | −0.0754 | −0.1558 | 0.4018 | 0.149* | |
O8 | 0.0957 (5) | 0.1564 (6) | 0.4007 (4) | 0.078 (2) | |
C8 | 0.0125 (7) | 0.2215 (10) | 0.3802 (7) | 0.090 (3) | |
H8A | 0.0300 | 0.2969 | 0.3679 | 0.136* | |
H8B | −0.0219 | 0.2219 | 0.4280 | 0.136* | |
H8C | −0.0278 | 0.1905 | 0.3306 | 0.136* | |
O9 | 0.2286 (5) | 0.2443 (5) | 0.3397 (4) | 0.082 (2) | |
C9 | 0.2317 (9) | 0.3242 (9) | 0.2750 (7) | 0.096 (4) | |
H9A | 0.2548 | 0.2897 | 0.2272 | 0.144* | |
H9B | 0.2742 | 0.3842 | 0.2972 | 0.144* | |
H9C | 0.1681 | 0.3535 | 0.2561 | 0.144* | |
O10 | 0.0390 (5) | −0.1808 (4) | 0.0766 (3) | 0.0710 (18) | |
O11 | 0.1032 (3) | 0.0030 (4) | −0.0196 (3) | 0.0491 (12) | |
O12 | −0.1090 (4) | 0.0374 (6) | 0.1535 (3) | 0.0719 (18) | |
O13 | 0.0317 (5) | 0.1951 (4) | 0.0609 (3) | 0.0596 (15) | |
C10 | 0.0031 (5) | −0.2346 (5) | 0.0111 (4) | 0.0452 (16) | |
C11 | 0.0004 (7) | −0.3595 (6) | 0.0212 (5) | 0.063 (2) | |
H11A | 0.0558 | −0.3834 | 0.0611 | 0.094* | |
H11B | 0.0008 | −0.3946 | −0.0336 | 0.094* | |
H11C | −0.0571 | −0.3804 | 0.0427 | 0.094* | |
C12 | −0.1492 (5) | 0.0246 (9) | 0.0774 (5) | 0.062 (2) | |
C13A | −0.2510 (12) | 0.0708 (15) | 0.0476 (11) | 0.060 (4)* | 0.50 |
H13A | −0.2473 | 0.1493 | 0.0348 | 0.090* | 0.50 |
H13B | −0.2888 | 0.0606 | 0.0925 | 0.090* | 0.50 |
H13C | −0.2806 | 0.0315 | −0.0031 | 0.090* | 0.50 |
C13B | −0.2570 (17) | 0.0022 (18) | 0.0615 (15) | 0.081 (6)* | 0.50 |
H13D | −0.2827 | 0.0161 | 0.0020 | 0.122* | 0.50 |
H13E | −0.2879 | 0.0509 | 0.0972 | 0.122* | 0.50 |
H13F | −0.2687 | −0.0745 | 0.0753 | 0.122* | 0.50 |
C1R | 0.3947 (5) | −0.0111 (6) | 0.4346 (5) | 0.085 (3)* | |
H1R | 0.4480 | −0.0051 | 0.4070 | 0.102* | |
C2R | 0.3459 (5) | 0.0793 (4) | 0.4675 (4) | 0.067 (2)* | |
H2R | 0.3618 | 0.1549 | 0.4653 | 0.081* | |
C3R | 0.2688 (5) | 0.0340 (6) | 0.5044 (5) | 0.077 (3)* | |
H3R | 0.2252 | 0.0747 | 0.5305 | 0.093* | |
C4R | 0.2698 (5) | −0.0844 (5) | 0.4942 (5) | 0.089 (3)* | |
H4R | 0.2270 | −0.1348 | 0.5126 | 0.107* | |
C5R | 0.3476 (6) | −0.1122 (4) | 0.4511 (5) | 0.090 (3)* | |
H5R | 0.3648 | −0.1841 | 0.4363 | 0.108* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Nd | 0.0300 (2) | 0.0282 (2) | 0.0198 (2) | 0.0012 (1) | −0.0032 (1) | −0.0011 (1) |
Co | 0.0347 (4) | 0.0346 (4) | 0.0222 (4) | 0.0002 (3) | −0.0064 (3) | 0.0023 (3) |
P1 | 0.0309 (8) | 0.072 (1) | 0.0317 (8) | 0.0084 (8) | −0.0021 (7) | −0.0050 (8) |
P2 | 0.050 (1) | 0.0468 (9) | 0.0280 (8) | −0.0133 (8) | −0.0046 (7) | 0.0118 (7) |
P3 | 0.054 (1) | 0.0340 (8) | 0.0251 (7) | 0.0064 (7) | −0.0081 (7) | −0.0060 (6) |
O1 | 0.030 (2) | 0.066 (3) | 0.028 (2) | 0.006 (2) | 0.0012 (17) | −0.0007 (19) |
O2 | 0.046 (3) | 0.052 (3) | 0.034 (2) | −0.018 (2) | −0.0054 (19) | 0.008 (2) |
O3 | 0.063 (3) | 0.040 (2) | 0.032 (2) | 0.015 (2) | −0.014 (2) | −0.0090 (19) |
O4 | 0.069 (4) | 0.152 (7) | 0.051 (3) | −0.051 (5) | 0.011 (3) | −0.014 (4) |
C4 | 0.101 (9) | 0.14 (1) | 0.091 (8) | −0.052 (8) | 0.041 (7) | −0.026 (8) |
C5 | 0.106 (8) | 0.063 (6) | 0.095 (8) | 0.032 (6) | 0.010 (6) | −0.006 (5) |
O6 | 0.108 (5) | 0.039 (3) | 0.093 (5) | −0.012 (3) | −0.044 (4) | 0.014 (3) |
C6 | 0.111 (8) | 0.055 (5) | 0.090 (7) | −0.009 (5) | −0.027 (6) | −0.004 (5) |
C7 | 0.081 (7) | 0.14 (1) | 0.090 (8) | −0.021 (7) | 0.044 (6) | −0.015 (7) |
O8 | 0.082 (4) | 0.103 (5) | 0.046 (3) | 0.050 (4) | 0.003 (3) | −0.013 (3) |
C8 | 0.077 (7) | 0.106 (8) | 0.088 (7) | 0.047 (6) | 0.012 (5) | 0.000 (6) |
O9 | 0.124 (6) | 0.039 (3) | 0.067 (4) | −0.020 (3) | −0.033 (4) | 0.006 (3) |
C9 | 0.113 (9) | 0.071 (6) | 0.097 (8) | −0.021 (6) | −0.002 (7) | 0.031 (6) |
O10 | 0.133 (6) | 0.031 (2) | 0.037 (3) | 0.000 (3) | −0.020 (3) | −0.001 (2) |
O11 | 0.034 (2) | 0.082 (4) | 0.030 (2) | −0.002 (2) | 0.0013 (19) | −0.008 (2) |
O12 | 0.044 (3) | 0.142 (6) | 0.030 (3) | 0.010 (3) | 0.006 (2) | −0.013 (3) |
O13 | 0.106 (5) | 0.032 (2) | 0.034 (3) | 0.000 (3) | −0.008 (3) | −0.0033 (19) |
C10 | 0.073 (5) | 0.027 (3) | 0.033 (3) | 0.000 (3) | 0.001 (3) | 0.000 (2) |
C11 | 0.098 (7) | 0.028 (3) | 0.058 (5) | −0.002 (4) | 0.001 (4) | 0.002 (3) |
C12 | 0.035 (4) | 0.118 (7) | 0.030 (4) | 0.003 (4) | 0.002 (3) | −0.006 (4) |
Nd—O1 | 2.378 (4) | P3—O3 | 1.487 (4) |
Nd—O2 | 2.388 (4) | P3—O9 | 1.583 (6) |
Nd—O3 | 2.400 (4) | P3—O8 | 1.611 (6) |
Nd—O10 | 2.400 (5) | O4—C4 | 1.375 (11) |
Nd—O13 | 2.419 (5) | O5A—C5 | 1.574 (14) |
Nd—O11 | 2.438 (5) | O5B—C5 | 1.235 (17) |
Nd—O12 | 2.515 (5) | O6—C6 | 1.400 (10) |
Nd—O11i | 2.594 (5) | O7A—C7 | 1.267 (16) |
Nd—C12 | 2.915 (7) | O7B—C7 | 1.561 (16) |
Nd—Ndi | 3.9913 (6) | O8—C8 | 1.396 (10) |
Co—C4R | 2.064 (8) | O9—C9 | 1.400 (10) |
Co—C5R | 2.066 (7) | O10—C10 | 1.248 (8) |
Co—C3R | 2.091 (7) | O11—C12i | 1.244 (9) |
Co—C1R | 2.093 (8) | O11—Ndi | 2.594 (5) |
Co—C2R | 2.109 (6) | O12—C12 | 1.247 (9) |
Co—P2 | 2.1603 (19) | O13—C10i | 1.249 (8) |
Co—P3 | 2.1628 (18) | C10—O13i | 1.249 (8) |
Co—P1 | 2.169 (2) | C10—C11 | 1.499 (9) |
P1—O1 | 1.503 (4) | C12—O11i | 1.244 (9) |
P1—O5A | 1.546 (9) | C12—C13B | 1.52 (2) |
P1—O4 | 1.622 (7) | C12—C13A | 1.533 (18) |
P1—O5B | 1.685 (16) | C1R—C2R | 1.4200 |
P2—O2 | 1.491 (4) | C1R—C5R | 1.4200 |
P2—O7B | 1.538 (10) | C2R—C3R | 1.4200 |
P2—O6 | 1.606 (6) | C3R—C4R | 1.4200 |
P2—O7A | 1.714 (13) | C4R—C5R | 1.4200 |
O1—Nd—O2 | 77.67 (16) | O1—P1—O5A | 108.4 (4) |
O1—Nd—O3 | 75.43 (16) | O1—P1—O4 | 108.8 (3) |
O2—Nd—O3 | 74.51 (16) | O5A—P1—O4 | 92.6 (5) |
O1—Nd—O10 | 91.2 (2) | O1—P1—O5B | 105.0 (5) |
O2—Nd—O10 | 73.23 (17) | O5A—P1—O5B | 23.9 (5) |
O3—Nd—O10 | 147.03 (16) | O4—P1—O5B | 115.5 (6) |
O1—Nd—O13 | 109.52 (19) | O1—P1—Co | 121.10 (19) |
O2—Nd—O13 | 146.29 (17) | O5A—P1—Co | 117.6 (4) |
O3—Nd—O13 | 75.70 (15) | O4—P1—Co | 103.9 (2) |
O10—Nd—O13 | 137.18 (17) | O5B—P1—Co | 103.0 (5) |
O1—Nd—O11 | 82.68 (15) | O2—P2—O7B | 109.4 (4) |
O2—Nd—O11 | 140.59 (17) | O2—P2—O6 | 109.1 (3) |
O3—Nd—O11 | 132.43 (17) | O7B—P2—O6 | 91.3 (5) |
O10—Nd—O11 | 73.38 (19) | O2—P2—O7A | 104.5 (5) |
O13—Nd—O11 | 72.71 (18) | O7B—P2—O7A | 21.4 (5) |
O1—Nd—O12 | 152.86 (16) | O6—P2—O7A | 112.3 (6) |
O2—Nd—O12 | 79.57 (19) | O2—P2—Co | 119.90 (19) |
O3—Nd—O12 | 84.42 (19) | O7B—P2—Co | 116.3 (4) |
O10—Nd—O12 | 96.3 (2) | O6—P2—Co | 106.7 (3) |
O13—Nd—O12 | 82.2 (2) | O7A—P2—Co | 104.3 (5) |
O11—Nd—O12 | 124.45 (16) | O3—P3—O9 | 108.2 (3) |
O1—Nd—O11i | 155.24 (15) | O3—P3—O8 | 108.6 (3) |
O2—Nd—O11i | 113.31 (15) | O9—P3—O8 | 101.5 (4) |
O3—Nd—O11i | 128.10 (15) | O3—P3—Co | 120.94 (19) |
O10—Nd—O11i | 72.30 (19) | O9—P3—Co | 110.1 (3) |
O13—Nd—O11i | 74.30 (18) | O8—P3—Co | 105.7 (2) |
O11—Nd—O11i | 75.08 (17) | P1—O1—Nd | 137.6 (3) |
O12—Nd—O11i | 50.38 (16) | P2—O2—Nd | 139.1 (3) |
O1—Nd—C12 | 174.7 (2) | P3—O3—Nd | 137.9 (3) |
O2—Nd—C12 | 97.7 (2) | C4—O4—P1 | 121.4 (7) |
O3—Nd—C12 | 106.1 (2) | P1—O5A—C5 | 116.2 (7) |
O10—Nd—C12 | 84.9 (3) | C5—O5B—P1 | 129.6 (12) |
O13—Nd—C12 | 75.8 (2) | O5B—C5—O5A | 24.5 (8) |
O11—Nd—C12 | 99.59 (18) | C6—O6—P2 | 121.0 (6) |
O12—Nd—C12 | 25.19 (18) | C7—O7A—P2 | 124.3 (11) |
O11i—Nd—C12 | 25.25 (18) | P2—O7B—C7 | 117.2 (8) |
O1—Nd—Ndi | 120.83 (11) | O7A—C7—O7B | 22.7 (7) |
O2—Nd—Ndi | 136.81 (11) | C8—O8—P3 | 120.1 (6) |
O3—Nd—Ndi | 144.41 (11) | C9—O9—P3 | 125.1 (6) |
O10—Nd—Ndi | 68.14 (12) | C10—O10—Nd | 139.1 (4) |
O13—Nd—Ndi | 69.06 (11) | C12i—O11—Nd | 158.0 (5) |
O11—Nd—Ndi | 38.91 (11) | C12i—O11—Ndi | 91.9 (4) |
O12—Nd—Ndi | 86.05 (12) | Nd—O11—Ndi | 104.92 (17) |
O11i—Nd—Ndi | 36.17 (10) | C12—O12—Nd | 95.6 (4) |
C12—Nd—Ndi | 60.92 (14) | C10i—O13—Nd | 136.6 (4) |
C4R—Co—C5R | 40.22 (13) | O10—C10—O13i | 126.9 (6) |
C4R—Co—C3R | 39.96 (14) | O10—C10—C11 | 115.8 (6) |
C5R—Co—C3R | 67.11 (16) | O13i—C10—C11 | 117.3 (6) |
C4R—Co—C1R | 67.09 (16) | O11i—C12—O12 | 121.8 (7) |
C5R—Co—C1R | 39.92 (13) | O11i—C12—C13B | 117.3 (11) |
C3R—Co—C1R | 66.61 (15) | O12—C12—C13B | 117.4 (11) |
C4R—Co—C2R | 66.81 (16) | O11i—C12—C13A | 116.4 (9) |
C5R—Co—C2R | 66.78 (16) | O12—C12—C13A | 120.1 (9) |
C3R—Co—C2R | 39.52 (11) | C13B—C12—C13A | 32.5 (9) |
C1R—Co—C2R | 39.50 (12) | O11i—C12—Nd | 62.8 (4) |
C4R—Co—P2 | 88.96 (18) | O12—C12—Nd | 59.2 (4) |
C5R—Co—P2 | 103.2 (2) | C13B—C12—Nd | 165.7 (10) |
C3R—Co—P2 | 113.39 (19) | C13A—C12—Nd | 161.7 (9) |
C1R—Co—P2 | 142.1 (2) | C2R—C1R—C5R | 108.0 |
C2R—Co—P2 | 152.71 (18) | C2R—C1R—Co | 70.8 (3) |
C4R—Co—P3 | 128.4 (2) | C5R—C1R—Co | 69.0 (3) |
C5R—Co—P3 | 160.47 (18) | C1R—C2R—C3R | 108.0 |
C3R—Co—P3 | 94.99 (19) | C1R—C2R—Co | 69.7 (3) |
C1R—Co—P3 | 127.0 (2) | C3R—C2R—Co | 69.6 (3) |
C2R—Co—P3 | 94.59 (17) | C4R—C3R—C2R | 108.0 |
P2—Co—P3 | 90.86 (8) | C4R—C3R—Co | 69.0 (3) |
C4R—Co—P1 | 141.3 (2) | C2R—C3R—Co | 70.9 (3) |
C5R—Co—P1 | 102.3 (2) | C5R—C4R—C3R | 108.0 |
C3R—Co—P1 | 152.91 (19) | C5R—C4R—Co | 70.0 (3) |
C1R—Co—P1 | 89.07 (18) | C3R—C4R—Co | 71.0 (3) |
C2R—Co—P1 | 113.63 (19) | C4R—C5R—C1R | 108.0 |
P2—Co—P1 | 93.03 (7) | C4R—C5R—Co | 69.8 (3) |
P3—Co—P1 | 90.30 (7) | C1R—C5R—Co | 71.1 (3) |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Co2Nd2(C5H5)2(C2H3O2)4(C2H6O3P)6] |
Mr | 1426.96 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 293 |
a, b, c (Å) | 14.0685 (9), 11.9199 (9), 15.7428 (7) |
β (°) | 99.541 (4) |
V (Å3) | 2603.5 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.85 |
Crystal size (mm) | 0.50 × 0.50 × 0.40 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (MolEN; Fair, 1990) |
Tmin, Tmax | 0.273, 0.320 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5598, 4744, 4212 |
Rint | 0.013 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.123, 1.03 |
No. of reflections | 4744 |
No. of parameters | 261 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0677P)2 + 14.444P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.46, −1.00 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.
Nd—O1 | 2.378 (4) | P1—O1 | 1.503 (4) |
Nd—O2 | 2.388 (4) | P2—O2 | 1.491 (4) |
Nd—O3 | 2.400 (4) | P3—O3 | 1.487 (4) |
Nd—O10 | 2.400 (5) | O10—C10 | 1.248 (8) |
Nd—O13 | 2.419 (5) | O11—C12i | 1.244 (9) |
Nd—O11 | 2.438 (5) | O12—C12 | 1.247 (9) |
Nd—O12 | 2.515 (5) | O13—C10i | 1.249 (8) |
Nd—O11i | 2.594 (5) | C10—O13i | 1.249 (8) |
Co—P2 | 2.1603 (19) | C10—C11 | 1.499 (9) |
Co—P3 | 2.1628 (18) | C12—O11i | 1.244 (9) |
Co—P1 | 2.169 (2) | ||
O1—Nd—O2 | 77.67 (16) | O3—Nd—O12 | 84.42 (19) |
O1—Nd—O3 | 75.43 (16) | O10—Nd—O12 | 96.3 (2) |
O2—Nd—O3 | 74.51 (16) | O13—Nd—O12 | 82.2 (2) |
O1—Nd—O10 | 91.2 (2) | O11—Nd—O12 | 124.45 (16) |
O2—Nd—O10 | 73.23 (17) | O1—Nd—O11i | 155.24 (15) |
O3—Nd—O10 | 147.03 (16) | O2—Nd—O11i | 113.31 (15) |
O1—Nd—O13 | 109.52 (19) | O3—Nd—O11i | 128.10 (15) |
O2—Nd—O13 | 146.29 (17) | O10—Nd—O11i | 72.30 (19) |
O3—Nd—O13 | 75.70 (15) | O13—Nd—O11i | 74.30 (18) |
O10—Nd—O13 | 137.18 (17) | O11—Nd—O11i | 75.08 (17) |
O1—Nd—O11 | 82.68 (15) | O12—Nd—O11i | 50.38 (16) |
O2—Nd—O11 | 140.59 (17) | P2—Co—P3 | 90.86 (8) |
O3—Nd—O11 | 132.43 (17) | P2—Co—P1 | 93.03 (7) |
O10—Nd—O11 | 73.38 (19) | P3—Co—P1 | 90.30 (7) |
O13—Nd—O11 | 72.71 (18) | O10—C10—O13i | 126.9 (6) |
O1—Nd—O12 | 152.86 (16) | O11i—C12—O12 | 121.8 (7) |
O2—Nd—O12 | 79.57 (19) |
Symmetry code: (i) −x, −y, −z. |
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Lanthanide complexes are of considerable interest for their potential application as luminescent probes in systems of biological relevance and as resonance-contrasting agents (Bunzli, 1989). In general, coordination numbers for lanthanide complexes are greater than for transition metal complexes, usually eight or more. The change in coordination number of lanthanoid(III) complexes in solution is of interest in connection with the anomalous behaviour (a double series or S-shaped) in their thermodynamic and physicochemical properties (Lauffer, 1987). Early transition metal and lanthanide complexes containing the O-donor tripodal ligand, LOMe = CpCo[P(O)(OMe)2]3, having stability and high π-donor ability, in comparison with cyclopentadienyl or polytris(pyrazol-1-yl)borate have not been reported extensively yet. In our recent investigation, we have synthesized various compounds such as (LOMe)2ML1–2, (LOMe)YL2 and [(LOMe)YL2]2 (Cho et al., 1995a,b; Kim et al., 1996; Han et al., 1999). The various coordination modes of carboxylate ligands binding to metals, such as anti or syn monodentate, symmetrical or asymmetrical bidentate chelating and monodentate or bidentate bridging, are of considerable interest in inorganic and organometallic chemistry (Rardin et al., 1991). [Y{HB(Pz)3}(O2CCH3)2]2 containing bidentate bridging carboxylate and hydrotris(pyrazol-1-yl)borate ligands has been reported (Reger et al., 1988). [Zn(C10H13N4S)(O2CCH3)]2 (Bresolin et al., 1997) and [Nd(Phen)(ONO)(O2CCH3)2]2 (Niu et al., 1997) having bridging and chelating acetato ligands were recently reported. More recently, we have reported [(LOMe)Y(O2CCH3)2]2 having µ-O:O'- and µ-O,O':O'-acetato coordination modes (Han et al., 1999). [Nd2(Acc6)6(H2O)6](ClO4)6·6H2O (Acc6 = 1-aminocyclohexane-1-carboxylic acid) containing both the monodentate carboxylato and the bridging carboxylato O atoms has been determined by X-ray diffraction (Aparna et al., 1997). [{NdL2(H2O)}n][ClO4]3n.xH2O complexes (L = N,N'-dicarboxymethyl- N,N,N',N'-tetramethyl-1,4-butanediammonium; x = 0, n) have been characterized by X-ray crystallograpy and their structures have a centrosymmetric paddle-wheel-like dimeric subunits and a distorted square antiprismatic geometry (Wei et al., 1997). However, the lack of structural studies in new early lanthanide(III) complexes prompted us to the synthesis and structure of new neodymium(III) complexes containing strongly π-donor tripod and acetate ligands.
We discuss herein the structure of [η5-CpCo{P(O)(OMe)2}3Nd(O2CCH3)2]2, (I). This molecule possesses an inversion centre. Each Nd atom is surrounded by O1, O2 and O3 of LOMe and O10, O11, O12, O13 and O11i of acetato having two different coordination modes, µ-O:O' and µ-O,O':O', and the coordination geometry of Nd at the centre is a distorted square antiprism eight coordination [sysmmetry code: (i) -x, -y, -z]. The average of Nd—O [2.443 (5) Å] is ca 0.1 Å longer than that [2.345 (5) Å] of isomorphous [(LOMe)Y(O2CCH3)2]2 (Han et al., 1999). The difference between Nd—O11 and Ndi—O11 [2.438 (5) and 2.594 (5) Å, respectively] at the µ2-bridging acetato ligand of the title compound is smaller than those [2.370 (5) and 2.707 (3) Å] of [Nd(Phen)(ONO)(O2CCH3)2]2 (Niu et al., 1997), but the distance of Nd···Nd [3.9913 (6) Å] is similar to that [3.974 (1) Å] found in the above Nd complex. O12—C12—O11i [121.8 (7)°] at the µ-O:O'-acetato ligand and O10—C10—O13i [126.9 (6)°] at the µ-O,O':O'-acetato ligand are comparable to the bond angles found in yttrium [120.6 (6) and 126.4 (7)°] and neodymium [120.8 (7) and 129 (2)°] acetato complexes (Han et al., 1999; Niu et al., 1997).