Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803004744/lh6037sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803004744/lh6037Isup2.hkl |
CCDC reference: 209880
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.010 Å
- R factor = 0.031
- wR factor = 0.078
- Data-to-parameter ratio = 11.6
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level B:
THETM_01 Alert B The value of sine(theta_max)/wavelength is less than 0.575 Calculated sin(theta_max)/wavelength = 0.5563
Author response: ... See _publ_section_exptl_refinement in CIF file or "Experimental Section in TEXT" |
Alert Level C:
PLAT_731 Alert C Bond Calc 0.88(5), Rep 0.88(2) .... 2.50 su-Ratio O1 -H1A 1.555 1.555 PLAT_731 Alert C Bond Calc 0.89(6), Rep 0.89(2) .... 3.00 su-Ratio O1 -H1B 1.555 1.555 PLAT_731 Alert C Bond Calc 1.24(4), Rep 1.248(19) .... 2.11 su-Ratio N3 -C21 1.555 1.555 PLAT_735 Alert C D-H Calc 0.88(5), Rep 0.88(2) .... 2.50 su-Ratio O1 -H1A 1.555 1.555 PLAT_735 Alert C D-H Calc 0.89(6), Rep 0.89(2) .... 3.00 su-Ratio O1 -H1B 1.555 1.555
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
5 Alert Level C = Please check
Pr(CCl3COO)3·6H2O (0.3 mmol) was dissolved in a mixture of ethanol (10 ml) and water (4 ml). A solution of 1,10-phenanthroline (0.84 mmol), 8-hydroxyquinoline (HQ, 1.0 mmol) and 6 mol l-1 CH3COOH (3 ml) in a mixture of ethanol (10 ml) and N,N'-dimethylformamide (3 ml) was added to the above solution. After 3 d, crystals were obtained. Analysis calculated for C21H20Cl6N3O8Pr: C 31.69, H 2.53, N 5.28, Pr 17.70%; found: C 31.48, H 2.47, N 4.62, Pr 17.43%. HQ is a key factor in the formation of quaternary complexes. In the absence of HQ in the synthetic system, no product could be obtained because of the strong acidity. HQ can decrease the solution acidity and form H2Q+ with H+, which is difficult to bind Ln3+, and keep the solution a certain amount of CH3COO- to partly replace CCl3COO- the anion.
All H atoms were included in calculated positions with C—H distances of 0.93 for most H atoms and 0.96 Å for methyl. They were then included in the refinement in riding-motion approximation with Uiso fixed at 0.08 Å2. H atoms bonded to O atoms were refined independently with isotropic displacement parameters. The optimal maximum 2θ limit (Mo Kα radiation) for data collection is 50°, and although the crytal use here diffracted well, the 2θmax for data used in this determination is only 46.6°. The exclusion of some potentially available data restricts the precision of the results. The use of room-temperature data may be the reason the anisotropic displacement parameters of some of the atoms in the title complex (as well as the atoms of the solvent molecule) have refined to unusually large values.
Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXP97 (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
[Pr2(C4Cl6O4)4(C2H3O2)2(C12H8N2)2(H2O)2]·2C3H7NO | Z = 1 |
Mr = 1592.02 | F(000) = 784 |
Triclinic, P1 | Dx = 1.817 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.351 (3) Å | Cell parameters from 7133 reflections |
b = 12.475 (3) Å | θ = 1.8–23.3° |
c = 13.424 (4) Å | µ = 2.27 mm−1 |
α = 113.89 (3)° | T = 293 K |
β = 102.18 (2)° | Prism, green |
γ = 102.786 (18)° | 0.30 × 0.20 × 0.20 mm |
V = 1455.0 (7) Å3 |
Bruker SMART CCD area-detector diffractometer | 4163 independent reflections |
Radiation source: fine-focus sealed tube | 3874 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.014 |
ϕ and ω scans | θmax = 23.3°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→11 |
Tmin = 0.549, Tmax = 0.659 | k = −13→13 |
7133 measured reflections | l = −14→11 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0368P)2 + 3.6925P] where P = (Fo2 + 2Fc2)/3 |
4163 reflections | (Δ/σ)max < 0.001 |
360 parameters | Δρmax = 1.07 e Å−3 |
2 restraints | Δρmin = −0.76 e Å−3 |
[Pr2(C4Cl6O4)4(C2H3O2)2(C12H8N2)2(H2O)2]·2C3H7NO | γ = 102.786 (18)° |
Mr = 1592.02 | V = 1455.0 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.351 (3) Å | Mo Kα radiation |
b = 12.475 (3) Å | µ = 2.27 mm−1 |
c = 13.424 (4) Å | T = 293 K |
α = 113.89 (3)° | 0.30 × 0.20 × 0.20 mm |
β = 102.18 (2)° |
Bruker SMART CCD area-detector diffractometer | 4163 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3874 reflections with I > 2σ(I) |
Tmin = 0.549, Tmax = 0.659 | Rint = 0.014 |
7133 measured reflections | θmax = 23.3° |
R[F2 > 2σ(F2)] = 0.031 | 2 restraints |
wR(F2) = 0.078 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 1.07 e Å−3 |
4163 reflections | Δρmin = −0.76 e Å−3 |
360 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 | ||
Pr1 | 0.12942 (2) | 0.66798 (2) | 0.027032 (19) | 0.03210 (10) | |
Cl1 | −0.0356 (3) | 0.2865 (3) | −0.42151 (19) | 0.1231 (9) | |
Cl2 | −0.3201 (2) | 0.2697 (2) | −0.44801 (14) | 0.1128 (9) | |
Cl3 | −0.1202 (2) | 0.48897 (17) | −0.41123 (14) | 0.0922 (6) | |
Cl4 | 0.1017 (3) | 1.19173 (17) | 0.33217 (17) | 0.1010 (7) | |
Cl5 | 0.07827 (19) | 1.0018 (2) | 0.39825 (15) | 0.0857 (5) | |
Cl6 | 0.34111 (15) | 1.11792 (18) | 0.38636 (14) | 0.0818 (5) | |
O1 | −0.0148 (4) | 0.7591 (4) | −0.0675 (3) | 0.0552 (9) | |
H1A | −0.005 (7) | 0.838 (3) | −0.029 (5) | 0.09 (2)* | |
H1B | −0.096 (5) | 0.713 (6) | −0.125 (5) | 0.11 (3)* | |
O2 | −0.0020 (3) | 0.5184 (3) | −0.1826 (3) | 0.0440 (8) | |
O3 | −0.1723 (3) | 0.3525 (3) | −0.2084 (3) | 0.0434 (8) | |
O4 | 0.1384 (4) | 0.8664 (3) | 0.1796 (3) | 0.0596 (10) | |
O5 | 0.0645 (6) | 0.9912 (4) | 0.1196 (4) | 0.0813 (14) | |
O6 | 0.2932 (4) | 0.5459 (3) | −0.0231 (4) | 0.0570 (10) | |
O7 | 0.0981 (3) | 0.4342 (3) | −0.0239 (3) | 0.0405 (7) | |
O8 | −0.2843 (7) | 0.6175 (8) | −0.1992 (8) | 0.161 (4) | |
N1 | 0.3960 (4) | 0.8176 (4) | 0.1469 (3) | 0.0453 (10) | |
N2 | 0.2786 (4) | 0.7552 (4) | −0.0785 (3) | 0.0446 (10) | |
N3 | −0.5093 (7) | 0.5029 (7) | −0.2962 (6) | 0.0916 (19) | |
C1 | 0.4523 (6) | 0.8537 (5) | 0.2585 (5) | 0.0610 (15) | |
H1 | 0.3943 | 0.8327 | 0.2969 | 0.080* | |
C2 | 0.5947 (7) | 0.9216 (6) | 0.3208 (6) | 0.0747 (19) | |
H2 | 0.6302 | 0.9448 | 0.3990 | 0.080* | |
C3 | 0.6803 (6) | 0.9534 (6) | 0.2672 (7) | 0.076 (2) | |
H3 | 0.7753 | 0.9993 | 0.3086 | 0.080* | |
C4 | 0.6272 (5) | 0.9178 (5) | 0.1497 (6) | 0.0581 (15) | |
C5 | 0.4816 (5) | 0.8495 (4) | 0.0918 (5) | 0.0445 (12) | |
C6 | 0.4199 (5) | 0.8152 (4) | −0.0277 (5) | 0.0445 (12) | |
C7 | 0.5061 (6) | 0.8476 (5) | −0.0865 (6) | 0.0600 (15) | |
C8 | 0.4413 (9) | 0.8156 (6) | −0.2008 (6) | 0.079 (2) | |
H8 | 0.4949 | 0.8347 | −0.2429 | 0.080* | |
C9 | 0.2999 (9) | 0.7564 (6) | −0.2521 (5) | 0.077 (2) | |
H9 | 0.2561 | 0.7356 | −0.3287 | 0.080* | |
C10 | 0.2213 (7) | 0.7272 (5) | −0.1879 (5) | 0.0605 (15) | |
H10 | 0.1246 | 0.6863 | −0.2236 | 0.080* | |
C11 | 0.7110 (6) | 0.9477 (6) | 0.0860 (8) | 0.076 (2) | |
H11 | 0.8070 | 0.9917 | 0.1231 | 0.080* | |
C12 | 0.6542 (7) | 0.9139 (6) | −0.0243 (8) | 0.077 (2) | |
H12 | 0.7119 | 0.9336 | −0.0634 | 0.080* | |
C13 | −0.1031 (5) | 0.4190 (4) | −0.2397 (4) | 0.0371 (11) | |
C14 | −0.1444 (6) | 0.3682 (5) | −0.3737 (4) | 0.0490 (13) | |
C15 | 0.1151 (5) | 0.9631 (5) | 0.1928 (4) | 0.0436 (12) | |
C16 | 0.1561 (5) | 1.0641 (5) | 0.3206 (4) | 0.0471 (12) | |
C17 | 0.2139 (5) | 0.4431 (5) | −0.0430 (4) | 0.0449 (12) | |
C18 | 0.2490 (8) | 0.3271 (6) | −0.0920 (7) | 0.082 (2) | |
H18A | 0.1754 | 0.2582 | −0.1009 | 0.080* | |
H18B | 0.3362 | 0.3375 | −0.0405 | 0.080* | |
H18C | 0.2578 | 0.3109 | −0.1660 | 0.080* | |
C19 | −0.3834 (15) | 0.5827 (12) | −0.2552 (13) | 0.169 (6) | |
H19 | −0.3847 | 0.6285 | −0.2952 | 0.080* | |
C20 | −0.602 (3) | 0.4880 (16) | −0.3831 (17) | 0.41 (2) | |
H20A | −0.6887 | 0.4264 | −0.3986 | 0.080* | |
H20B | −0.5720 | 0.4606 | −0.4492 | 0.080* | |
H20C | −0.6172 | 0.5657 | −0.3678 | 0.080* | |
C21 | −0.540 (4) | 0.444 (3) | −0.244 (3) | 0.384 (19) | |
H21A | −0.6357 | 0.3867 | −0.2842 | 0.080* | |
H21B | −0.5316 | 0.5007 | −0.1667 | 0.080* | |
H21C | −0.4781 | 0.3974 | −0.2404 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pr1 | 0.03545 (16) | 0.02792 (15) | 0.02367 (15) | 0.00148 (10) | 0.00612 (10) | 0.01046 (11) |
Cl1 | 0.169 (2) | 0.149 (2) | 0.0788 (13) | 0.105 (2) | 0.0680 (15) | 0.0406 (14) |
Cl2 | 0.0829 (12) | 0.1394 (18) | 0.0407 (8) | −0.0511 (12) | −0.0161 (8) | 0.0375 (10) |
Cl3 | 0.1304 (16) | 0.0735 (11) | 0.0454 (8) | −0.0032 (10) | −0.0019 (9) | 0.0381 (8) |
Cl4 | 0.1422 (18) | 0.0625 (11) | 0.0751 (12) | 0.0530 (12) | 0.0145 (12) | 0.0130 (9) |
Cl5 | 0.0843 (11) | 0.1093 (14) | 0.0641 (10) | 0.0165 (10) | 0.0410 (9) | 0.0423 (10) |
Cl6 | 0.0439 (8) | 0.0974 (13) | 0.0545 (9) | −0.0031 (8) | 0.0042 (7) | 0.0107 (9) |
O1 | 0.064 (2) | 0.046 (2) | 0.043 (2) | 0.015 (2) | 0.0025 (19) | 0.0184 (19) |
O2 | 0.052 (2) | 0.0343 (18) | 0.0262 (16) | −0.0035 (16) | 0.0037 (15) | 0.0105 (14) |
O3 | 0.0493 (19) | 0.0396 (18) | 0.0284 (16) | −0.0010 (15) | 0.0056 (15) | 0.0164 (15) |
O4 | 0.070 (3) | 0.045 (2) | 0.043 (2) | 0.0227 (19) | 0.0023 (19) | 0.0088 (17) |
O5 | 0.123 (4) | 0.069 (3) | 0.045 (2) | 0.043 (3) | 0.014 (2) | 0.021 (2) |
O6 | 0.046 (2) | 0.047 (2) | 0.081 (3) | 0.0112 (17) | 0.0278 (19) | 0.032 (2) |
O7 | 0.0399 (18) | 0.0387 (18) | 0.0401 (18) | 0.0090 (14) | 0.0149 (15) | 0.0177 (15) |
O8 | 0.070 (4) | 0.163 (8) | 0.156 (7) | 0.008 (4) | −0.012 (4) | 0.033 (6) |
N1 | 0.042 (2) | 0.038 (2) | 0.043 (2) | 0.0010 (18) | 0.0054 (19) | 0.018 (2) |
N2 | 0.059 (3) | 0.033 (2) | 0.035 (2) | 0.0041 (19) | 0.018 (2) | 0.0147 (18) |
N3 | 0.066 (4) | 0.094 (5) | 0.078 (4) | 0.019 (3) | 0.007 (3) | 0.020 (4) |
C1 | 0.053 (3) | 0.056 (3) | 0.051 (3) | −0.002 (3) | −0.002 (3) | 0.024 (3) |
C2 | 0.054 (4) | 0.067 (4) | 0.068 (4) | −0.001 (3) | −0.014 (3) | 0.028 (3) |
C3 | 0.037 (3) | 0.058 (4) | 0.103 (6) | 0.000 (3) | −0.009 (3) | 0.035 (4) |
C4 | 0.037 (3) | 0.039 (3) | 0.093 (5) | 0.012 (2) | 0.017 (3) | 0.030 (3) |
C5 | 0.040 (3) | 0.030 (2) | 0.063 (3) | 0.011 (2) | 0.019 (3) | 0.021 (2) |
C6 | 0.050 (3) | 0.029 (2) | 0.055 (3) | 0.010 (2) | 0.025 (3) | 0.018 (2) |
C7 | 0.074 (4) | 0.040 (3) | 0.081 (4) | 0.021 (3) | 0.051 (4) | 0.030 (3) |
C8 | 0.121 (6) | 0.052 (4) | 0.082 (5) | 0.023 (4) | 0.073 (5) | 0.034 (4) |
C9 | 0.124 (6) | 0.053 (4) | 0.048 (3) | 0.010 (4) | 0.042 (4) | 0.023 (3) |
C10 | 0.082 (4) | 0.046 (3) | 0.043 (3) | 0.001 (3) | 0.021 (3) | 0.022 (3) |
C11 | 0.042 (3) | 0.058 (4) | 0.131 (7) | 0.014 (3) | 0.036 (4) | 0.045 (4) |
C12 | 0.066 (4) | 0.059 (4) | 0.125 (7) | 0.023 (3) | 0.066 (5) | 0.046 (4) |
C13 | 0.042 (3) | 0.037 (3) | 0.026 (2) | 0.011 (2) | 0.006 (2) | 0.014 (2) |
C14 | 0.057 (3) | 0.045 (3) | 0.027 (2) | 0.001 (2) | 0.009 (2) | 0.011 (2) |
C15 | 0.036 (3) | 0.044 (3) | 0.037 (3) | 0.006 (2) | 0.009 (2) | 0.012 (2) |
C16 | 0.048 (3) | 0.043 (3) | 0.039 (3) | 0.010 (2) | 0.014 (2) | 0.013 (2) |
C17 | 0.048 (3) | 0.042 (3) | 0.045 (3) | 0.015 (2) | 0.016 (2) | 0.021 (2) |
C18 | 0.086 (5) | 0.061 (4) | 0.126 (6) | 0.037 (4) | 0.065 (5) | 0.047 (4) |
C19 | 0.119 (10) | 0.109 (9) | 0.187 (14) | 0.048 (8) | 0.018 (10) | −0.004 (9) |
C20 | 0.51 (4) | 0.159 (15) | 0.221 (19) | 0.17 (2) | −0.20 (2) | −0.086 (14) |
C21 | 0.55 (5) | 0.40 (4) | 0.48 (4) | 0.20 (3) | 0.38 (4) | 0.34 (4) |
Pr1—O7i | 2.399 (3) | N3—C19 | 1.293 (14) |
Pr1—O4 | 2.458 (4) | C1—C2 | 1.394 (8) |
Pr1—O1 | 2.500 (4) | C1—H1 | 0.9300 |
Pr1—O2 | 2.502 (3) | C2—C3 | 1.344 (10) |
Pr1—O3i | 2.507 (3) | C2—H2 | 0.9300 |
Pr1—O6 | 2.538 (4) | C3—C4 | 1.396 (10) |
Pr1—O7 | 2.636 (3) | C3—H3 | 0.9300 |
Pr1—N2 | 2.646 (4) | C4—C5 | 1.415 (7) |
Pr1—N1 | 2.665 (4) | C4—C11 | 1.432 (9) |
Pr1—C17 | 2.969 (5) | C5—C6 | 1.434 (7) |
Pr1—Pr1i | 4.1249 (13) | C6—C7 | 1.407 (7) |
Cl1—C14 | 1.732 (6) | C7—C8 | 1.384 (10) |
Cl2—C14 | 1.751 (5) | C7—C12 | 1.439 (10) |
Cl3—C14 | 1.757 (5) | C8—C9 | 1.359 (10) |
Cl4—C16 | 1.763 (6) | C8—H8 | 0.9300 |
Cl5—C16 | 1.753 (5) | C9—C10 | 1.399 (8) |
Cl6—C16 | 1.770 (5) | C9—H9 | 0.9300 |
O1—H1A | 0.88 (2) | C10—H10 | 0.9300 |
O1—H1B | 0.89 (2) | C11—C12 | 1.316 (10) |
O2—C13 | 1.240 (5) | C11—H11 | 0.9300 |
O3—C13 | 1.235 (5) | C12—H12 | 0.9300 |
O3—Pr1i | 2.507 (3) | C13—C14 | 1.566 (6) |
O4—C15 | 1.233 (6) | C15—C16 | 1.554 (7) |
O5—C15 | 1.227 (6) | C17—C18 | 1.490 (8) |
O6—C17 | 1.246 (6) | C18—H18A | 0.9600 |
O7—C17 | 1.268 (6) | C18—H18B | 0.9600 |
O7—Pr1i | 2.399 (3) | C18—H18C | 0.9600 |
O8—C19 | 1.009 (13) | C19—H19 | 0.9300 |
N1—C1 | 1.324 (7) | C20—H20A | 0.9600 |
N1—C5 | 1.360 (6) | C20—H20B | 0.9600 |
N2—C10 | 1.325 (7) | C20—H20C | 0.9600 |
N2—C6 | 1.358 (6) | C21—H21A | 0.9600 |
N3—C21 | 1.248 (19) | C21—H21B | 0.9600 |
N3—C20 | 1.263 (17) | C21—H21C | 0.9600 |
O7i—Pr1—O4 | 90.27 (13) | C3—C2—H2 | 120.2 |
O7i—Pr1—O1 | 80.29 (12) | C1—C2—H2 | 120.2 |
O4—Pr1—O1 | 72.29 (13) | C2—C3—C4 | 120.2 (5) |
O7i—Pr1—O2 | 76.03 (11) | C2—C3—H3 | 119.9 |
O4—Pr1—O2 | 140.05 (12) | C4—C3—H3 | 119.9 |
O1—Pr1—O2 | 68.52 (12) | C3—C4—C5 | 117.3 (6) |
O7i—Pr1—O3i | 74.23 (11) | C3—C4—C11 | 123.8 (6) |
O4—Pr1—O3i | 74.11 (12) | C5—C4—C11 | 118.9 (6) |
O1—Pr1—O3i | 137.28 (13) | N1—C5—C4 | 122.0 (5) |
O2—Pr1—O3i | 134.02 (10) | N1—C5—C6 | 118.2 (4) |
O7i—Pr1—O6 | 119.84 (11) | C4—C5—C6 | 119.8 (5) |
O4—Pr1—O6 | 138.47 (13) | N2—C6—C7 | 122.7 (5) |
O1—Pr1—O6 | 136.05 (13) | N2—C6—C5 | 118.0 (4) |
O2—Pr1—O6 | 78.71 (13) | C7—C6—C5 | 119.3 (5) |
O3i—Pr1—O6 | 86.63 (12) | C8—C7—C6 | 117.2 (6) |
O7i—Pr1—O7 | 70.10 (12) | C8—C7—C12 | 124.2 (6) |
O4—Pr1—O7 | 142.68 (12) | C6—C7—C12 | 118.6 (6) |
O1—Pr1—O7 | 131.09 (12) | C9—C8—C7 | 120.4 (5) |
O2—Pr1—O7 | 67.10 (10) | C9—C8—H8 | 119.8 |
O3i—Pr1—O7 | 70.18 (10) | C7—C8—H8 | 119.8 |
O6—Pr1—O7 | 49.79 (10) | C8—C9—C10 | 119.0 (6) |
O7i—Pr1—N2 | 147.63 (12) | C8—C9—H9 | 120.5 |
O4—Pr1—N2 | 99.32 (13) | C10—C9—H9 | 120.5 |
O1—Pr1—N2 | 73.49 (14) | N2—C10—C9 | 122.8 (6) |
O2—Pr1—N2 | 76.90 (11) | N2—C10—H10 | 118.6 |
O3i—Pr1—N2 | 138.13 (12) | C9—C10—H10 | 118.6 |
O6—Pr1—N2 | 71.12 (12) | C12—C11—C4 | 121.0 (6) |
O7—Pr1—N2 | 114.36 (11) | C12—C11—H11 | 119.5 |
O7i—Pr1—N1 | 149.46 (12) | C4—C11—H11 | 119.5 |
O4—Pr1—N1 | 70.02 (13) | C11—C12—C7 | 122.4 (6) |
O1—Pr1—N1 | 113.46 (13) | C11—C12—H12 | 118.8 |
O2—Pr1—N1 | 133.86 (12) | C7—C12—H12 | 118.8 |
O3i—Pr1—N1 | 77.94 (12) | O3—C13—O2 | 130.6 (4) |
O6—Pr1—N1 | 70.14 (13) | O3—C13—C14 | 115.6 (4) |
O7—Pr1—N1 | 111.70 (11) | O2—C13—C14 | 113.7 (4) |
N2—Pr1—N1 | 61.44 (13) | C13—C14—Cl1 | 108.1 (4) |
O7i—Pr1—C17 | 95.25 (13) | C13—C14—Cl2 | 112.4 (3) |
O4—Pr1—C17 | 149.68 (13) | Cl1—C14—Cl2 | 109.2 (3) |
O1—Pr1—C17 | 138.03 (13) | C13—C14—Cl3 | 112.2 (3) |
O2—Pr1—C17 | 69.91 (13) | Cl1—C14—Cl3 | 107.4 (3) |
O3i—Pr1—C17 | 78.77 (13) | Cl2—C14—Cl3 | 107.3 (3) |
O6—Pr1—C17 | 24.59 (12) | O5—C15—O4 | 129.3 (5) |
O7—Pr1—C17 | 25.27 (12) | O5—C15—C16 | 115.4 (5) |
N2—Pr1—C17 | 91.83 (13) | O4—C15—C16 | 115.3 (5) |
N1—Pr1—C17 | 91.42 (14) | C15—C16—Cl5 | 110.9 (4) |
O7i—Pr1—Pr1i | 36.94 (8) | C15—C16—Cl4 | 112.4 (4) |
O4—Pr1—Pr1i | 120.73 (10) | Cl5—C16—Cl4 | 107.1 (3) |
O1—Pr1—Pr1i | 108.78 (10) | C15—C16—Cl6 | 108.8 (3) |
O2—Pr1—Pr1i | 67.10 (8) | Cl5—C16—Cl6 | 108.3 (3) |
O3i—Pr1—Pr1i | 67.99 (8) | Cl4—C16—Cl6 | 109.3 (3) |
O6—Pr1—Pr1i | 82.92 (8) | O6—C17—O7 | 120.2 (5) |
O7—Pr1—Pr1i | 33.16 (7) | O6—C17—C18 | 121.9 (5) |
N2—Pr1—Pr1i | 139.02 (9) | O7—C17—C18 | 117.8 (5) |
N1—Pr1—Pr1i | 137.51 (9) | O6—C17—Pr1 | 57.9 (3) |
C17—Pr1—Pr1i | 58.35 (10) | O7—C17—Pr1 | 62.5 (2) |
Pr1—O1—H1A | 119 (4) | C18—C17—Pr1 | 173.5 (4) |
Pr1—O1—H1B | 123 (5) | C17—C18—H18A | 109.5 |
H1A—O1—H1B | 114 (7) | C17—C18—H18B | 109.5 |
C13—O2—Pr1 | 136.7 (3) | H18A—C18—H18B | 109.5 |
C13—O3—Pr1i | 134.0 (3) | C17—C18—H18C | 109.5 |
C15—O4—Pr1 | 141.1 (3) | H18A—C18—H18C | 109.5 |
C17—O6—Pr1 | 97.5 (3) | H18B—C18—H18C | 109.5 |
C17—O7—Pr1i | 157.1 (3) | O8—C19—N3 | 147.9 (19) |
C17—O7—Pr1 | 92.2 (3) | O8—C19—H19 | 106.0 |
Pr1i—O7—Pr1 | 109.90 (12) | N3—C19—H19 | 106.0 |
C1—N1—C5 | 118.1 (4) | N3—C20—H20A | 109.5 |
C1—N1—Pr1 | 121.6 (3) | N3—C20—H20B | 109.5 |
C5—N1—Pr1 | 120.1 (3) | H20A—C20—H20B | 109.5 |
C10—N2—C6 | 117.8 (4) | N3—C20—H20C | 109.5 |
C10—N2—Pr1 | 120.8 (3) | H20A—C20—H20C | 109.5 |
C6—N2—Pr1 | 120.8 (3) | H20B—C20—H20C | 109.5 |
C21—N3—C20 | 119 (2) | N3—C21—H21A | 109.5 |
C21—N3—C19 | 118.1 (19) | N3—C21—H21B | 109.5 |
C20—N3—C19 | 122.3 (18) | H21A—C21—H21B | 109.5 |
N1—C1—C2 | 122.9 (6) | N3—C21—H21C | 109.5 |
N1—C1—H1 | 118.5 | H21A—C21—H21C | 109.5 |
C2—C1—H1 | 118.5 | H21B—C21—H21C | 109.5 |
C3—C2—C1 | 119.6 (6) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O5 | 0.88 (2) | 1.96 (4) | 2.748 (6) | 149 (6) |
O1—H1B···O8 | 0.89 (2) | 1.84 (4) | 2.690 (8) | 159 (8) |
Experimental details
Crystal data | |
Chemical formula | [Pr2(C4Cl6O4)4(C2H3O2)2(C12H8N2)2(H2O)2]·2C3H7NO |
Mr | 1592.02 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.351 (3), 12.475 (3), 13.424 (4) |
α, β, γ (°) | 113.89 (3), 102.18 (2), 102.786 (18) |
V (Å3) | 1455.0 (7) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.27 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.549, 0.659 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7133, 4163, 3874 |
Rint | 0.014 |
θmax (°) | 23.3 |
(sin θ/λ)max (Å−1) | 0.556 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.078, 1.06 |
No. of reflections | 4163 |
No. of parameters | 360 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.07, −0.76 |
Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXP97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
Pr1—O7i | 2.399 (3) | Pr1—O6 | 2.538 (4) |
Pr1—O4 | 2.458 (4) | Pr1—O7 | 2.636 (3) |
Pr1—O1 | 2.500 (4) | Pr1—N2 | 2.646 (4) |
Pr1—O2 | 2.502 (3) | Pr1—N1 | 2.665 (4) |
Pr1—O3i | 2.507 (3) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O5 | 0.88 (2) | 1.96 (4) | 2.748 (6) | 149 (6) |
O1—H1B···O8 | 0.89 (2) | 1.84 (4) | 2.690 (8) | 159 (8) |
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Numerous quaternary complexes of lanthanides bearing heterocycle amines have been extensively reported since 1960 (Forsberg, 1973). In recent years, efforts have been actively made to synthesize novel quaternary, mixed anion complexes because of their interesting structures, coordination modes and functional properties (Dong et al., 1993; Rogers & Rollins, 1995; Niu et al., 1997; Li et al., 2002; Zhu et al., 1999, 2001). In general, the two anions in these complexes were based on nitrate and aliphatic or aromatic carboxylate ligands. However, systems containing two anions of aliphatic or aromatic carboxylates may show more interesting coordination modes. We report here an example of a quaternary complex, (I), with two anions of aliphatic carboxylates.
The complex is a dimer with a Pr···Pr separation of 4.125 (1) Å and possesses a center of symmetry. Each Pr atom is nine-coordinate with a monocapped square antiprism geometry and involves six O atoms from three CCl3COO- and three CH3COO- groups, two N atoms from one phen and one O atom from one water molecule. The four CCl3COO- anions in the dimer complex show two coordination modes, viz. one mode bonds to two Pr atoms through O2 and O3 and the other mode is monodentately coordinated to the Pr atom. The acetate anions are chelated to one Pr atom through atoms O6 and O7 and simultaneously O7 binds to another Pr atom with distances of 2.636 (3) and 2.399 (3) Å for O7—Pr1 and O7—Pr1i [symmetry code: (i) -x, 1 - y, -z], respectively. The Pr—O(H2O) bond length is similar to that of bridging Pr—O(CCl3COO-) and the Pr—N distances are longer than the Pr—O distances (see Table 1). The phen ligands are situated in vacant sites and the complex therefore has little steric exclusion. As expected, the Pr—N distances agree with those of the two ternary complexes bearing similar building blocks, like the monomer complex [Pr(CCl3COO)3(2,2'-bipy)2], (II) (Wang et al., 1991), and the dimer complex [Pr(CCl3COO)3(phen)(C2H5OH)]2, (III) (Dong et al., 1990). In (II), all the trichloroacetate ligands are coordinated to the metal in chelating mode and the mean Pr—O bond length is 2.582 (4) Å, which is longer than that of (I) and (III). In complex (III), two coordination modes for the trichloroacetate groups were observed and the Pr—O distances for the chelating mode are similar to that in (I), while the Pr—O(CCl3COO-) distance for the monodentate mode is shorter than that of (I).
In recent years, weak interactions, such as the Cl···Cl interactions observed in (I), have been the focus of increased interest (Cui et al., 2001). The Cl atom of the monodentate CCl3COO- group has a weak interaction with another Cl atom of a bridging CCl3COO- ligand from a neighboring molecule and the distance is 3.34 Å (see Fig. 2), which is shorter than the sum of the van der Waals radii of Cl···Cl (3.5 Å). Meanwhile, two phen rings from neighboring molecules are parallel to each other and result in significant π–π stacking with an interplanar distance of 3.38 Å.