Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108010706/sq3137sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108010706/sq3137Isup2.hkl |
CCDC reference: 692649
All commercially obtained reagent-grade chemicals were used without further purification. An aqueous solution (10 ml) of [Mg(H2O)6][CoII(1,3-pdta)].2H2O (1.50 g, 2.83 mmol), prepared as described by Radanović et al. (2003), was passed through a column packed with Merck I cation exchanger in the Li+ form. The eluate was evaporated at room temperature to a volume of 2 ml and the Li2[CoII(1,3-pdta)].5H2O complex was crystallized after addition of ethanol and cooling in a refrigerator for 2 d. The red–violet crystals were removed by filtration and air-dried (0.92 g). The complex was checked by UV–Vis spectroscopy and its spectrum compared with that obtained for the [Mg(H2O)6][CoII(1,3-pdta)].2H2O complex (Radanović et al., 2003). Analysis, calculated for Li2[CoII(1,3-pdta)].5H2O, C11H24O13N2Li2Co (FW = 465.13): C 28.40, H 5.20, N 6.02%; found: C 28.44, H 5.10, N 6.00%.
H atoms attached to C atoms were placed in calculated positions and refined using a riding model, with C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C). H atoms attached to hydroxyl groups and water molecules were located in subsequent difference Fourier maps, their O—H distances were standardized to 0.85 Å and they were thereafter refined using a riding model with Uiso(H) = 1.2Ueq(O). The absolute configuration of the complex was established as Λ on the basis of the Flack absolute structure parameter (Flack, 1983), which refined to a value of -0.017 (12).
Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2008).
[CoLi2(C11H14N2O8)(H2O)3]·2H2O | F(000) = 482 |
Mr = 465.13 | Dx = 1.648 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 4043 reflections |
a = 7.8767 (4) Å | θ = 2.2–28.1° |
b = 12.7381 (6) Å | µ = 0.99 mm−1 |
c = 9.3440 (4) Å | T = 293 K |
β = 90.756 (4)° | Plate, light-violet |
V = 937.44 (8) Å3 | 0.20 × 0.15 × 0.08 mm |
Z = 2 |
Kuma KM4 CCD κ-geometry diffractometer | 3069 independent reflections |
Radiation source: fine-focus sealed tube | 2487 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω and ϕ scans | θmax = 25.0°, θmin = 3.2° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007) | h = −9→9 |
Tmin = 0.846, Tmax = 0.924 | k = −15→14 |
7554 measured reflections | l = −10→11 |
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)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.052 | w = 1/[σ2(Fo2) + (0.0239P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
3069 reflections | Δρmax = 0.28 e Å−3 |
262 parameters | Δρmin = −0.25 e Å−3 |
1 restraint | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.017 (12) |
[CoLi2(C11H14N2O8)(H2O)3]·2H2O | V = 937.44 (8) Å3 |
Mr = 465.13 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.8767 (4) Å | µ = 0.99 mm−1 |
b = 12.7381 (6) Å | T = 293 K |
c = 9.3440 (4) Å | 0.20 × 0.15 × 0.08 mm |
β = 90.756 (4)° |
Kuma KM4 CCD κ-geometry diffractometer | 3069 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007) | 2487 reflections with I > 2σ(I) |
Tmin = 0.846, Tmax = 0.924 | Rint = 0.034 |
7554 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.052 | Δρmax = 0.28 e Å−3 |
S = 0.94 | Δρmin = −0.25 e Å−3 |
3069 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
262 parameters | Absolute structure parameter: −0.017 (12) |
1 restraint |
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 | ||
Co1 | 0.90239 (5) | 0.37587 (3) | 0.31058 (4) | 0.02235 (10) | |
O1 | 0.7179 (3) | 0.33828 (14) | 0.4668 (2) | 0.0292 (5) | |
O2 | 0.6791 (3) | 0.21375 (16) | 0.6339 (2) | 0.0401 (6) | |
O3 | 0.8794 (3) | 0.53616 (18) | 0.2858 (3) | 0.0320 (7) | |
O4 | 0.9508 (3) | 0.66371 (15) | 0.1365 (2) | 0.0344 (6) | |
O5 | 1.0681 (2) | 0.3811 (2) | 0.48744 (17) | 0.0284 (4) | |
O6 | 1.3315 (3) | 0.41722 (16) | 0.5574 (2) | 0.0363 (6) | |
O7 | 0.7634 (3) | 0.35384 (16) | 0.1212 (2) | 0.0396 (7) | |
O8 | 0.6293 (3) | 0.23161 (19) | −0.0096 (3) | 0.0439 (7) | |
N1 | 1.1343 (3) | 0.41023 (16) | 0.2050 (2) | 0.0210 (6) | |
N2 | 0.8974 (4) | 0.2090 (2) | 0.2996 (3) | 0.0250 (8) | |
C1 | 1.1960 (4) | 0.3173 (2) | 0.1281 (3) | 0.0298 (8) | |
H1A | 1.3074 | 0.3325 | 0.0900 | 0.036* | |
H1B | 1.1201 | 0.3030 | 0.0478 | 0.036* | |
C2 | 1.2080 (4) | 0.2190 (2) | 0.2232 (3) | 0.0319 (8) | |
H2A | 1.2966 | 0.1737 | 0.1869 | 0.038* | |
H2B | 1.2411 | 0.2402 | 0.3192 | 0.038* | |
C3 | 1.0448 (5) | 0.1569 (3) | 0.2307 (4) | 0.0433 (10) | |
H3A | 1.0112 | 0.1378 | 0.1339 | 0.052* | |
H3B | 1.0684 | 0.0922 | 0.2820 | 0.052* | |
C4 | 0.8731 (4) | 0.1781 (2) | 0.4495 (3) | 0.0284 (8) | |
H4A | 0.9811 | 0.1816 | 0.5003 | 0.034* | |
H4B | 0.8333 | 0.1061 | 0.4530 | 0.034* | |
C5 | 0.7475 (4) | 0.2480 (3) | 0.5221 (3) | 0.0284 (8) | |
C6 | 0.9641 (4) | 0.5724 (3) | 0.1808 (4) | 0.0255 (8) | |
C7 | 1.0870 (4) | 0.4984 (2) | 0.1086 (3) | 0.0247 (7) | |
H7A | 1.0350 | 0.4708 | 0.0218 | 0.030* | |
H7B | 1.1884 | 0.5366 | 0.0823 | 0.030* | |
C8 | 1.2591 (4) | 0.4457 (2) | 0.3139 (3) | 0.0264 (7) | |
H8A | 1.2645 | 0.5218 | 0.3119 | 0.032* | |
H8B | 1.3702 | 0.4192 | 0.2888 | 0.032* | |
C9 | 1.2188 (4) | 0.4107 (2) | 0.4643 (3) | 0.0257 (7) | |
C10 | 0.7101 (4) | 0.2610 (3) | 0.0979 (3) | 0.0326 (8) | |
C11 | 0.7419 (5) | 0.1813 (2) | 0.2160 (3) | 0.0389 (9) | |
H11A | 0.6451 | 0.1795 | 0.2791 | 0.047* | |
H11B | 0.7550 | 0.1120 | 0.1745 | 0.047* | |
O1W | 0.6351 (3) | 0.43034 (17) | 0.7634 (2) | 0.0342 (6) | |
H1WA | 0.7415 | 0.4352 | 0.7783 | 0.041* | |
H1WB | 0.5917 | 0.4781 | 0.8147 | 0.041* | |
O2W | 0.3424 (3) | 0.26157 (19) | 0.7674 (3) | 0.0539 (7) | |
H2WA | 0.2555 | 0.2242 | 0.7844 | 0.065* | |
H2WB | 0.2925 | 0.3140 | 0.7294 | 0.065* | |
O3W | 0.6155 (3) | 0.57686 (18) | 0.4663 (2) | 0.0456 (7) | |
H3WA | 0.6978 | 0.5780 | 0.4083 | 0.055* | |
H3WB | 0.5726 | 0.6380 | 0.4605 | 0.055* | |
O4W | 0.9672 (2) | 0.3774 (2) | 0.77715 (18) | 0.0404 (5) | |
H4WA | 1.0186 | 0.3803 | 0.6978 | 0.048* | |
H4WB | 0.9695 | 0.3155 | 0.8111 | 0.048* | |
O5W | 0.5433 (3) | 0.5277 (2) | 1.0095 (3) | 0.0672 (9) | |
H5WA | 0.5720 | 0.5103 | 1.0943 | 0.081* | |
H5WB | 0.5100 | 0.5906 | 1.0204 | 0.081* | |
Li1 | 0.5734 (7) | 0.2796 (5) | 0.8018 (6) | 0.0368 (15) | |
Li2 | 0.5715 (7) | 0.4461 (5) | 0.5621 (6) | 0.0328 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0262 (2) | 0.01847 (18) | 0.0224 (2) | 0.0002 (2) | 0.00060 (15) | 0.0017 (3) |
O1 | 0.0266 (13) | 0.0273 (13) | 0.0338 (13) | 0.0025 (9) | 0.0027 (10) | 0.0013 (10) |
O2 | 0.0550 (16) | 0.0336 (14) | 0.0320 (14) | −0.0061 (11) | 0.0141 (12) | 0.0031 (11) |
O3 | 0.0435 (16) | 0.0230 (15) | 0.0299 (15) | 0.0082 (11) | 0.0176 (13) | 0.0077 (11) |
O4 | 0.0452 (15) | 0.0228 (12) | 0.0355 (14) | 0.0059 (10) | 0.0087 (11) | 0.0124 (10) |
O5 | 0.0270 (11) | 0.0385 (11) | 0.0197 (10) | −0.0066 (15) | 0.0025 (8) | 0.0013 (15) |
O6 | 0.0287 (13) | 0.0504 (15) | 0.0296 (12) | −0.0061 (10) | −0.0082 (11) | 0.0082 (10) |
O7 | 0.0498 (15) | 0.0303 (18) | 0.0384 (13) | −0.0104 (12) | −0.0142 (11) | 0.0119 (12) |
O8 | 0.0520 (17) | 0.0517 (15) | 0.0275 (14) | −0.0056 (13) | −0.0128 (13) | 0.0057 (12) |
N1 | 0.0274 (15) | 0.0202 (14) | 0.0154 (13) | 0.0037 (10) | 0.0004 (11) | 0.0009 (11) |
N2 | 0.0309 (18) | 0.0202 (17) | 0.0238 (18) | 0.0066 (13) | 0.0004 (14) | 0.0028 (13) |
C1 | 0.039 (2) | 0.0275 (19) | 0.0233 (19) | 0.0028 (16) | 0.0053 (16) | −0.0002 (15) |
C2 | 0.032 (2) | 0.0257 (17) | 0.038 (2) | 0.0115 (16) | 0.0086 (17) | −0.0015 (16) |
C3 | 0.061 (3) | 0.030 (2) | 0.040 (2) | 0.0037 (19) | 0.017 (2) | −0.0021 (17) |
C4 | 0.041 (2) | 0.0234 (17) | 0.0209 (18) | −0.0019 (16) | 0.0062 (16) | 0.0010 (14) |
C5 | 0.030 (2) | 0.0281 (19) | 0.0274 (19) | −0.0063 (16) | −0.0043 (16) | −0.0051 (17) |
C6 | 0.026 (2) | 0.0248 (19) | 0.026 (2) | −0.0032 (15) | −0.0004 (16) | 0.0041 (16) |
C7 | 0.0315 (19) | 0.0221 (17) | 0.0205 (18) | −0.0025 (16) | 0.0045 (15) | 0.0069 (14) |
C8 | 0.0255 (18) | 0.0262 (17) | 0.0274 (18) | −0.0011 (15) | 0.0007 (14) | 0.0015 (15) |
C9 | 0.0305 (19) | 0.0198 (16) | 0.0268 (18) | 0.0002 (13) | 0.0018 (15) | 0.0004 (13) |
C10 | 0.035 (2) | 0.043 (2) | 0.0199 (19) | −0.0004 (17) | 0.0013 (16) | 0.0055 (17) |
C11 | 0.058 (3) | 0.0300 (18) | 0.029 (2) | −0.0095 (17) | −0.0082 (18) | −0.0011 (16) |
O1W | 0.0315 (14) | 0.0337 (13) | 0.0374 (14) | −0.0006 (10) | −0.0001 (11) | −0.0064 (11) |
O2W | 0.0330 (15) | 0.0658 (18) | 0.0629 (17) | −0.0072 (13) | −0.0014 (12) | 0.0243 (14) |
O3W | 0.0453 (16) | 0.0386 (13) | 0.0535 (16) | 0.0115 (11) | 0.0177 (13) | 0.0149 (12) |
O4W | 0.0461 (13) | 0.0446 (11) | 0.0306 (11) | 0.0075 (18) | 0.0034 (9) | 0.0029 (17) |
O5W | 0.085 (2) | 0.0709 (19) | 0.0461 (18) | 0.0285 (18) | −0.0016 (16) | 0.0019 (16) |
Li1 | 0.041 (4) | 0.037 (4) | 0.033 (3) | −0.001 (3) | 0.002 (3) | 0.008 (3) |
Li2 | 0.026 (3) | 0.041 (3) | 0.031 (3) | −0.003 (3) | 0.003 (2) | 0.003 (3) |
Co1—O3 | 2.063 (2) | C3—H3B | 0.9700 |
Co1—O7 | 2.088 (2) | C4—C5 | 1.500 (4) |
Co1—O5 | 2.0932 (17) | C4—H4A | 0.9700 |
Co1—O1 | 2.128 (2) | C4—H4B | 0.9700 |
Co1—N2 | 2.129 (3) | C6—C7 | 1.515 (4) |
Co1—N1 | 2.133 (2) | C7—H7A | 0.9700 |
O1—C5 | 1.280 (3) | C7—H7B | 0.9700 |
O1—Li2 | 2.009 (6) | C8—C9 | 1.512 (4) |
O2—C5 | 1.260 (4) | C8—H8A | 0.9700 |
O2—Li1 | 1.973 (6) | C8—H8B | 0.9700 |
O3—C6 | 1.281 (4) | C10—C11 | 1.518 (4) |
O4—C6 | 1.238 (3) | C11—H11A | 0.9700 |
O5—C9 | 1.267 (3) | C11—H11B | 0.9700 |
O6—C9 | 1.238 (3) | O1W—Li2 | 1.950 (6) |
O6—Li2i | 1.926 (6) | O1W—Li1 | 2.014 (6) |
O7—C10 | 1.273 (4) | O1W—H1WA | 0.8500 |
O8—C10 | 1.240 (4) | O1W—H1WB | 0.8500 |
O8—Li1ii | 1.911 (6) | O2W—Li1 | 1.857 (6) |
N1—C1 | 1.471 (3) | O2W—H2WA | 0.8500 |
N1—C8 | 1.476 (3) | O2W—H2WB | 0.8500 |
N1—C7 | 1.484 (3) | O3W—Li2 | 1.924 (6) |
N2—C4 | 1.469 (4) | O3W—H3WA | 0.8500 |
N2—C11 | 1.486 (4) | O3W—H3WB | 0.8501 |
N2—C3 | 1.491 (4) | O4W—H4WA | 0.8500 |
C1—C2 | 1.538 (4) | O4W—H4WB | 0.8500 |
C1—H1A | 0.9700 | O5W—H5WA | 0.8500 |
C1—H1B | 0.9700 | O5W—H5WB | 0.8499 |
C2—C3 | 1.512 (5) | Li1—O8iii | 1.911 (6) |
C2—H2A | 0.9700 | Li1—Li2 | 3.085 (7) |
C2—H2B | 0.9700 | Li2—O6iv | 1.926 (6) |
C3—H3A | 0.9700 | ||
O3—Co1—O7 | 89.64 (9) | O1—C5—C4 | 117.9 (3) |
O3—Co1—O5 | 96.31 (10) | O4—C6—O3 | 123.5 (3) |
O7—Co1—O5 | 171.14 (9) | O4—C6—C7 | 119.2 (3) |
O3—Co1—O1 | 103.88 (8) | O3—C6—C7 | 117.3 (3) |
O7—Co1—O1 | 101.31 (9) | N1—C7—C6 | 111.0 (2) |
O5—Co1—O1 | 83.68 (7) | N1—C7—H7A | 109.4 |
O3—Co1—N2 | 169.01 (8) | C6—C7—H7A | 109.4 |
O7—Co1—N2 | 79.38 (9) | N1—C7—H7B | 109.4 |
O5—Co1—N2 | 94.64 (10) | C6—C7—H7B | 109.4 |
O1—Co1—N2 | 78.23 (9) | H7A—C7—H7B | 108.0 |
O3—Co1—N1 | 79.60 (9) | N1—C8—C9 | 113.8 (2) |
O7—Co1—N1 | 94.49 (8) | N1—C8—H8A | 108.8 |
O5—Co1—N1 | 80.20 (8) | C9—C8—H8A | 108.8 |
O1—Co1—N1 | 163.80 (8) | N1—C8—H8B | 108.8 |
N2—Co1—N1 | 101.43 (9) | C9—C8—H8B | 108.8 |
C5—O1—Li2 | 122.6 (3) | H8A—C8—H8B | 107.7 |
C5—O1—Co1 | 110.9 (2) | O6—C9—O5 | 124.4 (3) |
Li2—O1—Co1 | 123.44 (19) | O6—C9—C8 | 118.4 (3) |
C5—O2—Li1 | 134.6 (3) | O5—C9—C8 | 117.1 (3) |
C6—O3—Co1 | 113.4 (2) | O8—C10—O7 | 125.7 (3) |
C9—O5—Co1 | 116.77 (17) | O8—C10—C11 | 117.7 (3) |
C9—O6—Li2i | 136.3 (3) | O7—C10—C11 | 116.5 (3) |
C10—O7—Co1 | 115.98 (19) | N2—C11—C10 | 110.5 (3) |
C10—O8—Li1ii | 139.4 (3) | N2—C11—H11A | 109.5 |
C1—N1—C8 | 111.2 (2) | C10—C11—H11A | 109.5 |
C1—N1—C7 | 113.2 (2) | N2—C11—H11B | 109.5 |
C8—N1—C7 | 110.2 (2) | C10—C11—H11B | 109.5 |
C1—N1—Co1 | 110.60 (17) | H11A—C11—H11B | 108.1 |
C8—N1—Co1 | 108.12 (16) | Li2—O1W—Li1 | 102.2 (3) |
C7—N1—Co1 | 103.08 (17) | Li2—O1W—H1WA | 113.0 |
C4—N2—C11 | 108.7 (3) | Li1—O1W—H1WA | 106.2 |
C4—N2—C3 | 113.9 (3) | Li2—O1W—H1WB | 111.7 |
C11—N2—C3 | 108.0 (3) | Li1—O1W—H1WB | 118.8 |
C4—N2—Co1 | 102.91 (19) | H1WA—O1W—H1WB | 105.0 |
C11—N2—Co1 | 106.07 (19) | Li1—O2W—H2WA | 145.7 |
C3—N2—Co1 | 116.8 (2) | Li1—O2W—H2WB | 114.9 |
N1—C1—C2 | 113.0 (2) | H2WA—O2W—H2WB | 98.6 |
N1—C1—H1A | 109.0 | Li2—O3W—H3WA | 117.0 |
C2—C1—H1A | 109.0 | Li2—O3W—H3WB | 138.4 |
N1—C1—H1B | 109.0 | H3WA—O3W—H3WB | 104.5 |
C2—C1—H1B | 109.0 | H4WA—O4W—H4WB | 110.9 |
H1A—C1—H1B | 107.8 | H5WA—O5W—H5WB | 102.3 |
C3—C2—C1 | 114.0 (3) | O2W—Li1—O8iii | 109.5 (3) |
C3—C2—H2A | 108.7 | O2W—Li1—O2 | 103.4 (3) |
C1—C2—H2A | 108.7 | O8iii—Li1—O2 | 120.2 (3) |
C3—C2—H2B | 108.7 | O2W—Li1—O1W | 109.0 (3) |
C1—C2—H2B | 108.7 | O8iii—Li1—O1W | 114.6 (3) |
H2A—C2—H2B | 107.6 | O2—Li1—O1W | 99.1 (3) |
N2—C3—C2 | 117.1 (3) | O2W—Li1—Li2 | 87.9 (2) |
N2—C3—H3A | 108.0 | O8iii—Li1—Li2 | 152.7 (3) |
C2—C3—H3A | 108.0 | O2—Li1—Li2 | 73.3 (2) |
N2—C3—H3B | 108.0 | O1W—Li1—Li2 | 38.16 (16) |
C2—C3—H3B | 108.0 | O3W—Li2—O6iv | 109.7 (3) |
H3A—C3—H3B | 107.3 | O3W—Li2—O1W | 119.5 (3) |
N2—C4—C5 | 111.5 (3) | O6iv—Li2—O1W | 104.0 (3) |
N2—C4—H4A | 109.3 | O3W—Li2—O1 | 106.1 (3) |
C5—C4—H4A | 109.3 | O6iv—Li2—O1 | 115.3 (3) |
N2—C4—H4B | 109.3 | O1W—Li2—O1 | 102.4 (3) |
C5—C4—H4B | 109.3 | O3W—Li2—Li1 | 159.0 (3) |
H4A—C4—H4B | 108.0 | O6iv—Li2—Li1 | 83.1 (2) |
O2—C5—O1 | 124.6 (3) | O1W—Li2—Li1 | 39.66 (17) |
O2—C5—C4 | 117.5 (3) | O1—Li2—Li1 | 81.6 (2) |
O3—Co1—O1—C5 | −162.22 (19) | Li1—O2—C5—C4 | 155.7 (3) |
O7—Co1—O1—C5 | 105.33 (19) | Li2—O1—C5—O2 | 6.0 (4) |
O5—Co1—O1—C5 | −67.26 (19) | Co1—O1—C5—O2 | 166.5 (3) |
N2—Co1—O1—C5 | 28.84 (19) | Li2—O1—C5—C4 | −173.6 (3) |
N1—Co1—O1—C5 | −61.6 (4) | Co1—O1—C5—C4 | −13.1 (3) |
O3—Co1—O1—Li2 | −1.9 (2) | N2—C4—C5—O2 | 160.1 (3) |
O7—Co1—O1—Li2 | −94.3 (2) | N2—C4—C5—O1 | −20.2 (4) |
O5—Co1—O1—Li2 | 93.1 (2) | Co1—O3—C6—O4 | 170.5 (2) |
N2—Co1—O1—Li2 | −170.8 (2) | Co1—O3—C6—C7 | −9.6 (4) |
N1—Co1—O1—Li2 | 98.7 (3) | C1—N1—C7—C6 | 157.7 (2) |
O7—Co1—O3—C6 | −69.2 (2) | C8—N1—C7—C6 | −77.0 (3) |
O5—Co1—O3—C6 | 104.2 (2) | Co1—N1—C7—C6 | 38.2 (3) |
O1—Co1—O3—C6 | −170.8 (2) | O4—C6—C7—N1 | 158.5 (3) |
N2—Co1—O3—C6 | −71.0 (5) | O3—C6—C7—N1 | −21.3 (4) |
N1—Co1—O3—C6 | 25.4 (2) | C1—N1—C8—C9 | −99.8 (3) |
O3—Co1—O5—C9 | −71.5 (2) | C7—N1—C8—C9 | 133.8 (3) |
O1—Co1—O5—C9 | −174.8 (2) | Co1—N1—C8—C9 | 21.8 (3) |
N2—Co1—O5—C9 | 107.6 (2) | Li2i—O6—C9—O5 | 173.6 (3) |
N1—Co1—O5—C9 | 6.8 (2) | Li2i—O6—C9—C8 | −9.9 (5) |
O3—Co1—O7—C10 | −166.8 (2) | Co1—O5—C9—O6 | −179.5 (2) |
O1—Co1—O7—C10 | −62.7 (2) | Co1—O5—C9—C8 | 3.9 (3) |
N2—Co1—O7—C10 | 12.9 (2) | N1—C8—C9—O6 | 165.2 (2) |
N1—Co1—O7—C10 | 113.7 (2) | N1—C8—C9—O5 | −18.1 (4) |
O3—Co1—N1—C1 | −155.0 (2) | Li1ii—O8—C10—O7 | 14.2 (7) |
O7—Co1—N1—C1 | −66.17 (18) | Li1ii—O8—C10—C11 | −168.9 (4) |
O5—Co1—N1—C1 | 106.68 (19) | Co1—O7—C10—O8 | −178.2 (3) |
O1—Co1—N1—C1 | 101.0 (3) | Co1—O7—C10—C11 | 4.9 (4) |
N2—Co1—N1—C1 | 13.9 (2) | C4—N2—C11—C10 | 146.2 (3) |
O3—Co1—N1—C8 | 83.04 (18) | C3—N2—C11—C10 | −89.8 (3) |
O7—Co1—N1—C8 | 171.85 (17) | Co1—N2—C11—C10 | 36.1 (3) |
O5—Co1—N1—C8 | −15.30 (17) | O8—C10—C11—N2 | 154.0 (3) |
O1—Co1—N1—C8 | −21.0 (4) | O7—C10—C11—N2 | −28.9 (4) |
N2—Co1—N1—C8 | −108.10 (18) | C5—O2—Li1—O2W | 103.7 (4) |
O3—Co1—N1—C7 | −33.67 (16) | C5—O2—Li1—O8iii | −133.9 (4) |
O7—Co1—N1—C7 | 55.14 (17) | C5—O2—Li1—O1W | −8.4 (5) |
O5—Co1—N1—C7 | −132.01 (18) | C5—O2—Li1—Li2 | 20.0 (4) |
O1—Co1—N1—C7 | −137.7 (3) | Li2—O1W—Li1—O2W | −60.1 (3) |
N2—Co1—N1—C7 | 135.19 (16) | Li2—O1W—Li1—O8iii | 176.9 (3) |
O3—Co1—N2—C4 | −138.8 (4) | Li2—O1W—Li1—O2 | 47.6 (3) |
O7—Co1—N2—C4 | −140.6 (2) | Li1—O1W—Li2—O3W | −176.9 (3) |
O5—Co1—N2—C4 | 46.0 (2) | Li1—O1W—Li2—O6iv | 60.4 (3) |
O1—Co1—N2—C4 | −36.5 (2) | Li1—O1W—Li2—O1 | −60.0 (3) |
N1—Co1—N2—C4 | 126.9 (2) | C5—O1—Li2—O3W | 165.0 (3) |
O3—Co1—N2—C11 | −24.6 (6) | Co1—O1—Li2—O3W | 6.9 (3) |
O7—Co1—N2—C11 | −26.4 (2) | C5—O1—Li2—O6iv | −73.3 (4) |
O5—Co1—N2—C11 | 160.1 (2) | Co1—O1—Li2—O6iv | 128.6 (2) |
O1—Co1—N2—C11 | 77.6 (2) | C5—O1—Li2—O1W | 38.9 (4) |
N1—Co1—N2—C11 | −118.9 (2) | Co1—O1—Li2—O1W | −119.2 (2) |
O3—Co1—N2—C3 | 95.7 (5) | C5—O1—Li2—Li1 | 4.9 (3) |
O7—Co1—N2—C3 | 93.9 (2) | Co1—O1—Li2—Li1 | −153.14 (16) |
O5—Co1—N2—C3 | −79.5 (2) | O2W—Li1—Li2—O3W | 132.6 (8) |
O1—Co1—N2—C3 | −162.0 (2) | O8iii—Li1—Li2—O3W | 1.5 (12) |
N1—Co1—N2—C3 | 1.4 (2) | O2—Li1—Li2—O3W | −122.7 (8) |
C8—N1—C1—C2 | 67.7 (3) | O1W—Li1—Li2—O3W | 7.7 (7) |
C7—N1—C1—C2 | −167.5 (2) | O2W—Li1—Li2—O6iv | 3.1 (2) |
Co1—N1—C1—C2 | −52.4 (3) | O8iii—Li1—Li2—O6iv | −127.9 (6) |
N1—C1—C2—C3 | 86.7 (3) | O2—Li1—Li2—O6iv | 107.8 (2) |
C4—N2—C3—C2 | −98.6 (4) | O1W—Li1—Li2—O6iv | −121.8 (3) |
C11—N2—C3—C2 | 140.6 (3) | O2W—Li1—Li2—O1W | 124.9 (3) |
Co1—N2—C3—C2 | 21.3 (4) | O8iii—Li1—Li2—O1W | −6.1 (6) |
C1—C2—C3—N2 | −65.3 (4) | O2—Li1—Li2—O1W | −130.4 (3) |
C11—N2—C4—C5 | −71.2 (3) | O2W—Li1—Li2—O1 | −113.8 (3) |
C3—N2—C4—C5 | 168.3 (3) | O8iii—Li1—Li2—O1 | 115.1 (6) |
Co1—N2—C4—C5 | 41.0 (3) | O2—Li1—Li2—O1 | −9.16 (19) |
Li1—O2—C5—O1 | −23.9 (5) | O1W—Li1—Li2—O1 | 121.2 (3) |
Symmetry codes: (i) x+1, y, z; (ii) x, y, z−1; (iii) x, y, z+1; (iv) x−1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4W | 0.85 | 1.92 | 2.703 (3) | 152 |
O1W—H1WB···O5W | 0.85 | 1.97 | 2.720 (3) | 147 |
O2W—H2WA···O4v | 0.85 | 1.95 | 2.784 (3) | 165 |
O2W—H2WB···O6iv | 0.85 | 2.10 | 2.790 (3) | 138 |
O3W—H3WA···O3 | 0.85 | 1.92 | 2.743 (3) | 163 |
O3W—H3WB···O2vi | 0.85 | 2.37 | 3.041 (3) | 137 |
O4W—H4WA···O5 | 0.85 | 2.01 | 2.832 (2) | 163 |
O4W—H4WB···O4vii | 0.85 | 2.09 | 2.910 (3) | 162 |
O5W—H5WA···O7iii | 0.85 | 2.51 | 2.992 (3) | 117 |
O5W—H5WB···O8vi | 0.85 | 2.11 | 2.931 (3) | 164 |
Symmetry codes: (iii) x, y, z+1; (iv) x−1, y, z; (v) −x+1, y−1/2, −z+1; (vi) −x+1, y+1/2, −z+1; (vii) −x+2, y−1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [CoLi2(C11H14N2O8)(H2O)3]·2H2O |
Mr | 465.13 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 7.8767 (4), 12.7381 (6), 9.3440 (4) |
β (°) | 90.756 (4) |
V (Å3) | 937.44 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.99 |
Crystal size (mm) | 0.20 × 0.15 × 0.08 |
Data collection | |
Diffractometer | Kuma KM4 CCD κ-geometry diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2007) |
Tmin, Tmax | 0.846, 0.924 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7554, 3069, 2487 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.052, 0.94 |
No. of reflections | 3069 |
No. of parameters | 262 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.25 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | −0.017 (12) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis PRO (Oxford Diffraction, 2007), SHELXS86 (Sheldrick, 2008), Stereochemical Workstation Operation Manual (Siemens, 1989) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2008).
Co1—O3 | 2.063 (2) | Co1—O1 | 2.128 (2) |
Co1—O7 | 2.088 (2) | Co1—N2 | 2.129 (3) |
Co1—O5 | 2.0932 (17) | Co1—N1 | 2.133 (2) |
O3—Co1—O1 | 103.88 (8) | O1—Co1—N2 | 78.23 (9) |
O7—Co1—O1 | 101.31 (9) | O3—Co1—N1 | 79.60 (9) |
O3—Co1—N2 | 169.01 (8) | O1—Co1—N1 | 163.80 (8) |
O7—Co1—N2 | 79.38 (9) | N2—Co1—N1 | 101.43 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WA···O4W | 0.85 | 1.92 | 2.703 (3) | 151.7 |
O1W—H1WB···O5W | 0.85 | 1.97 | 2.720 (3) | 146.7 |
O2W—H2WA···O4i | 0.85 | 1.95 | 2.784 (3) | 165.4 |
O2W—H2WB···O6ii | 0.85 | 2.10 | 2.790 (3) | 137.7 |
O3W—H3WA···O3 | 0.85 | 1.92 | 2.743 (3) | 162.9 |
O3W—H3WB···O2iii | 0.85 | 2.37 | 3.041 (3) | 136.8 |
O4W—H4WA···O5 | 0.85 | 2.01 | 2.832 (2) | 162.6 |
O4W—H4WB···O4iv | 0.85 | 2.09 | 2.910 (3) | 162.0 |
O5W—H5WA···O7v | 0.85 | 2.51 | 2.992 (3) | 116.9 |
O5W—H5WB···O8iii | 0.85 | 2.11 | 2.931 (3) | 163.7 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x−1, y, z; (iii) −x+1, y+1/2, −z+1; (iv) −x+2, y−1/2, −z+1; (v) x, y, z+1. |
This work is a continuation of our study concerning the structural characteristics of 1,3-pdta complexes containing different metal(II) ions. The title compound, (I), constitutes the first example of a metal(II) complex of 1,3-propanediaminetetraacetate (1,3-pdta) with a monovalent metal as the charge-compensating ion. Our previous attempts to obtain M2[CoII(1,3-pdta)] complexes (where M is a alkali metal ion) using the same synthetic method as that used for the preparation of the series [M(H2O)6][M'(1,3-pdta)].2H2O (M = CoII, MgII or ZnII; M'= CoII, ZnII, CuII, NiII or MgII) (Rychlewska et al., 2000, 2005; Radanović et al., 2001, 2003, 2004) were unsuccessful. More specifically, from a reaction mixture containing equivalent amounts of Ba[CoII(1,3-pdta)].8H2O and Li2SO4 or Na2SO4, only the homometallic complex salt [CoII(H2O)6][CoII(1,3-pdta)].2H2O crystallized. Therefore, in order to obtain Li2[CoII(1,3-pdta)].5H2O, the ion-exchange column technique was applied. However, attempts to use the same technique for the preparation of the analogous M2[CoII(1,3-pdta)] salts with M = Na+, K+, NH4+ or Cs+ always yielded the corresponding [CoIII(1,3-pdta)]- complex.
As expected, the solution that was eluted from the lithium-exchange column did not show any properties of rotation of polarisation, which indicates that the sample obtained is a racemate containing both right-handed (Δ) and left-handed (Λ) enantiomers. Upon crystallization, however, the compound underwent spontaneous resolution. This phenomenon has recently been reviewed by Perez-Garcia & Amabilino (2007). The solution obtained by dissolving a randomly selected group of crystals was optically active and did not undergo racemization for a period of several days. This points to the significant stability of the Li2[Co(1,3 pdta)] complex and indicates that, at the macroscopic level, groups of crystals are formed which have predominantly one enantiomer, hence leading to chiral colonies. The chiral crystal of which the structure is reported in this paper contains molecules that display the Λ helicity.
The structure is built of two tetrahedrally coordinated Li+ cations, an octahedral [Co(1,3-pdta)]2- anion and five water molecules, two of which are solvent water molecules. The coordination around the CoII cation is octahedral and the 1,3-pdta acts as a hexadentate ligand (Fig. 1). The in-plane cis bond angles are in a wide range, 79.60 (9)–103.88 (8)°, and the in-plane trans bonds are bent by ca 1 and 6°, respectively (Table 1). The conformations of the glycinate rings are envelope for the more puckered G rings and half-chair for the less puckered R rings (see Fig. 1 for ring definitions). The six-membered diamine ring (T) approaches a half-chair form; the Cremer & Pople (1975) parameters (PARST; Nardelli, 1983) are QT = 0.596 (3) Å, ϕ = -24.0 (2)° and θ = 124.2 (2)°.
The octahedral coordination of the CoII ion by 1,3-pdta has previously been observed in two isostructural crystals with either hexaaquamagnesium(II) [Cambridge Structural Database (CSD; Allen, 2002) refcode IMAFOR] or hexaaquacobalt(II) (CSD refcode IMAFIL) complexes as counter-ions (Radanović et al., 2003). Comparison of these two crystal structures (determined at 120 K) with that of (I) (determined at room temperature) reveals significant differences at both the molecular and supramolecular levels. While the former [Co(1,3-pdta)]2- complexes display C2 molecular symmetry, the complex in (I) is asymmetric. The asymmetry is introduced to the system by Li+ cations which are coordinated to three out of four carboxylate groups (one equatorial and two axial). This asymmetry is particularly well reflected in the variation in the values of the Co—Oequatorial bond lengths which represent, respectively, the longest [2.128 (2) Å] and shortest [2.063 (2) Å] Co—O bonds in this complex. The longest Co—O bond is formed to the O atom that is simultaneously coordinated to the Li+ cation, while the shortest involves the only carboxylate O atom that is exclusively coordinated to the CoII cation. The analogous Co—Oequatorial bond length observed in the C2 symmetrical [Co(1,3-pdta)]2- complexes, in which the carboxylate groups are only coordinated to the central CoII, is 2.055 (2) Å (average of two independent measurements).
The Li+ cations each display a tetrahedral environment but the coordination form differs (Fig. 1). Atom Li1 is surrounded by two water molecules (O1W and O2W) and two carboxylate O atoms [O2 and O8iii; symmetry code: (iii) x, y, z + 1] that are not directly coordinated to the Co atom, while atom Li2 is bonded to two water molecules (O1W and O3W) and to two carboxylate O atoms [O6iv and O1; symmetry code: (iv) x - 1, y, z], of which the former is not coordinated to Co while the latter is. The Li—O bond lengths and angles in the two LiO4 tetrahedra display rather wide ranges of 1.857 (6)–2.014 (6) Å and 99.1 (3)–120.2 (3)°, respectively. The two Li+ cations are joined via the mediating water molecule O1W; the distance between the water-bridged Li+ cations is only 3.085 (8) Å and the angle at the O atom is 102.2 (2)°. The two Li+ cations are additionally bridged by one of the two equatorial carboxylate groups (O1—C5—O2). This leads to the formation of the puckered six-membered ring shown in Fig. 1. Simultaneous bridging of Li+ ions by a carboxylate group and a water molecule has also been observed in crystalline phases of other lithium complexes, including the simplest one, i.e. lithium fumarate (Kansikas & Hermansson, 1989). A search of the CSD yielded 20 such structures, displaying a significant variation of the ring puckering.
The ions connected by coordinate bonds form uncharged two-dimensional layers parallel to (010) (Fig. 2). The layer construction is further supported by a system of O—H···O hydrogen bonds, in which water molecules act as the proton donors and the acceptors are either carboxylate O atoms or uncoordinated water molecules (Table 2). The layers are both chiral and polar. There are two such layers per unit cell, related by the twofold screw axis along the b direction (Fig. 3). Neighbouring layers are anti-parallel, as required by the twofold symmetry, and are joined by hydrogen bonds. This supramolecular arrangement differs dramatically from the packing observed in the analogous [M(H2O)6][CoII(1,3-pdta)].2H2O complexes mentioned above [M = MgII (CSD refcode IMAFOR) or CoII (CSD refcode IMAFIL); Radanović et al., 2003], which form centrosymmetric crystal structures containing distinct octahedral cationic and anionic species. A somewhat similar layered arrangement of complex anions to that present in (I) has been observed in those [MIII(1,3-pdta)]- complexes which also underwent enantiomer separation during the crystallization process, i.e. those with M = CrIII (CSD refcode BACRUS; Herak et al., 1984), FeIII (CSD refcode JEPKEU; Okamoto et al., 1990) and VIII (CSD refcode PATZIT; Robles et al., 1993), all containing Na+ as the counter-ion. As in (I), the Na+ ions in these crystals are coordinated to three out of four carboxylate groups of the 1,3-pdta ligand but are situated in between rather than within the anionic layers. A somewhat similar, though more symmetrical, mode of cation/anion bonding is observed in the K[Co(1,3-pdta)] complex (CSD refcode TMACOK; Nagao et al., 1972), which also forms chiral crystals. This analogy in packing prompts us to propose that a possible cause of enantiomer separation during the crystallization process might be the rigidification and polarization of the M(1,3-pdta) core, resulting from the direct coordination of the alkali metal counter-ions to the carboxylate groups constituting the 1,3-pdta ligand. This rigidification may account for the occurrence of one particular orientation and chirality of the constituent complex anions in a layer and cause the non-centrosymmetric packing of neighbouring layers to be energetically preferable.