Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032564/hg2253sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032564/hg2253Isup2.hkl |
CCDC reference: 1293587
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.020
- wR factor = 0.048
- Data-to-parameter ratio = 17.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.89 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for O6 - N4 .. 6.49 su PLAT230_ALERT_2_C Hirshfeld Test Diff for O8 - N5 .. 6.82 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O5 .. 6.66 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O6 .. 7.60 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O8 .. 6.97 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O9 .. 5.16 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O11 .. 6.58 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O12 .. 5.63 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Zn1 - O2 .. 5.29 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O9 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O11 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O12 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Ce1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N5 PLAT480_ALERT_4_C Long H...A H-Bond Reported H17B .. O9 .. 2.87 Ang.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 28.35 From the CIF: _reflns_number_total 6211 Count of symmetry unique reflns 3586 Completeness (_total/calc) 173.20% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2625 Fraction of Friedel pairs measured 0.732 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT794_ALERT_5_G Check Predicted Bond Valency for Ce1 (3) 3.27 PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 2.33
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 17 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 16 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
H2L was prepared by the 2:1 condensation of 3-ethoxysalicylaldehyde and ethylenediamine in methanol. Complex (I) was obtained by the treatment of zinc(II) acetate dihydrate (0.188 g, 1 mmol) with H2L(0.356 g, 1 mmol) in methanol solution (80 ml) under reflux for 3 h and then for another 3 h after the addition of cerium(III) nitrate hexahydrate (0.434 g, 1 mmol). The reaction mixture was cooled and the resulting precipitate was filtered off, washed with diethyl ether and dried in vacuo. Single crystals of (I) suitable for X-ray analysis were obtained by slow evaporation at room temperature of a methanol solution. Analysis calculated for C20H22CeN5O13Zn: C 32.20, H 2.97, Ce 18.78, N 9.39,Zn 8.77%; found: C 32.00, H 2.85, Ce 18.10, N 9.40, Zn 8.68%. IR(KBr, cm-1): 1642(C=N), 1386,1490(nitrate).
The H atoms were positioned geometrically and treated as riding on their parent atoms, with C—H distances of 0.97 (methylene) and 0.96 Å (methyl), and with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.
The potential applications of trivalent lanthanide complexes as contrast agent for magnetic resonance imaging and stains for fluorescence imaging have prompted considerable interest in the preparation, magnetic and optical properties of 3 d-4f hetorometallic dinuclear complexes (Baggio et al., 2000; Caravan et al., 1999; Edder et al., 2000; Knoer et al., 2005). As part of our investigations into the structure and applications of 3 d-4f hetorometallic Schiff base complexes (Sui et al., 2006), we report here the synthesis and X-ray crystal structure analysis of the title complex, (I), a new ZnII—CeIII complex with salen-type Schiff base N,N'-bis(3-ethoxysalicylidene) ethylenediamine(H2L).
Complex (I) crystallizes in the space group P212121, with zinc and cerium doubly bridged by two phenolate O atoms provided by a salen-type Schiff base ligand. The inner salen-type cavity is occupied by zinc(II), while cerium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand. The dihedral angles between the mean planes of Zn1/O1/O2 and Ce1/O1/O2 is 3.62 (11)° suggesting that the bridging moiety is almost planar; the deviation of atoms from the least squares Zn1/O1/O2/Ce1 plane being 0.0310 (3)Å for Zn, 0.0208 (3)Å for Ce, -0.0262 (2)Å for O1 and -0.0256 (2)Å for O2.
The cerium(III) center in (I) has a decacoordination environment of O atoms. In addition to the phenolate ligands, two ethoxy O atoms coordinate to this metal center, two O atoms from each of the three nitrates chelate to cerium to complete the decacoordination. The three kinds of Ce—O bond distances are significantly different, the shortest being the Ce—O(phenolate) and longest being the Ce—O(ethoxy) separations.
The coordination of zinc(II) is approximately square planar. The donor centers are alternatively above and below the mean N2O2 plane with an average deviation from the plane of 0.0879 (2) Å, while Zn1 is 0.0453 (2)Å below this square plane.
Adjacent molecules are held together by weak interactions (O10···Zn1=3.156 (4) Å, C7—H7···O7i=3.275 (4) and C9—H9A···O7ii=3.286 (4); symmetry codes:(i)-x, y - 1/2, 1/2 - z; (ii)x - 1, y, z). these link the molecules into a two-dimensional zigzag sheet(Fig 2).
For related literature, see: Baggio et al. (2000); Caravan et al. (1999); Edder et al. (2000); Knoer et al. (2005); Sui et al. (2006).
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: APEX2; software used to prepare material for publication: APEX2 and publCIF (Westrip, 2007).
[CeZn(C20H22N2O4)(NO3)3] | F(000) = 1476 |
Mr = 745.92 | Dx = 1.949 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 19190 reflections |
a = 8.6418 (14) Å | θ = 1.8–28.4° |
b = 13.904 (2) Å | µ = 2.79 mm−1 |
c = 21.157 (3) Å | T = 293 K |
V = 2542.2 (7) Å3 | Block, yellow |
Z = 4 | 0.31 × 0.22 × 0.20 mm |
Bruker APEX II area-detector diffractometer | 6211 independent reflections |
Radiation source: fine-focus sealed tube | 5407 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 0 pixels mm-1 | θmax = 28.4°, θmin = 1.8° |
φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −17→18 |
Tmin = 0.494, Tmax = 0.572 | l = −28→28 |
19190 measured reflections |
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)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.048 | w = 1/[σ2(Fo2) + (0.0226P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
6211 reflections | Δρmax = 0.39 e Å−3 |
363 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2611 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.017 (9) |
[CeZn(C20H22N2O4)(NO3)3] | V = 2542.2 (7) Å3 |
Mr = 745.92 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.6418 (14) Å | µ = 2.79 mm−1 |
b = 13.904 (2) Å | T = 293 K |
c = 21.157 (3) Å | 0.31 × 0.22 × 0.20 mm |
Bruker APEX II area-detector diffractometer | 6211 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 5407 reflections with I > 2σ(I) |
Tmin = 0.494, Tmax = 0.572 | Rint = 0.021 |
19190 measured reflections |
R[F2 > 2σ(F2)] = 0.020 | H-atom parameters constrained |
wR(F2) = 0.048 | Δρmax = 0.39 e Å−3 |
S = 1.01 | Δρmin = −0.36 e Å−3 |
6211 reflections | Absolute structure: Flack (1983), 2611 Friedel pairs |
363 parameters | Absolute structure parameter: 0.017 (9) |
0 restraints |
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 | ||
O3 | 0.1524 (2) | 1.17630 (12) | 0.07489 (8) | 0.0360 (4) | |
Ce1 | 0.258940 (14) | 0.999427 (11) | 0.094132 (6) | 0.03050 (4) | |
Zn1 | −0.06773 (4) | 0.94379 (2) | 0.182756 (15) | 0.03842 (8) | |
O1 | 0.03669 (19) | 1.05629 (13) | 0.15369 (8) | 0.0333 (4) | |
O2 | 0.0841 (2) | 0.87424 (12) | 0.13626 (8) | 0.0365 (4) | |
N1 | −0.2006 (2) | 1.01384 (18) | 0.23926 (10) | 0.0378 (5) | |
C2 | 0.2071 (3) | 0.74270 (18) | 0.09013 (12) | 0.0330 (5) | |
N3 | 0.1260 (3) | 0.9950 (2) | −0.03637 (11) | 0.0477 (5) | |
O11 | 0.2673 (2) | 1.01379 (16) | −0.02545 (9) | 0.0552 (6) | |
N2 | −0.1791 (3) | 0.83178 (18) | 0.20894 (11) | 0.0369 (6) | |
O12 | 0.0487 (2) | 0.96785 (17) | 0.01035 (9) | 0.0582 (6) | |
C1 | 0.0857 (3) | 0.77948 (18) | 0.12660 (12) | 0.0308 (6) | |
O13 | 0.0704 (3) | 1.00237 (19) | −0.08932 (9) | 0.0772 (7) | |
C10 | −0.2207 (3) | 1.1039 (2) | 0.23934 (12) | 0.0386 (6) | |
H10 | −0.2889 | 1.1292 | 0.2691 | 0.046* | |
C8 | −0.3148 (3) | 0.8559 (2) | 0.24897 (14) | 0.0460 (7) | |
H8A | −0.3351 | 0.8045 | 0.2788 | 0.055* | |
H8B | −0.4061 | 0.8649 | 0.2229 | 0.055* | |
C7 | −0.1515 (3) | 0.7458 (2) | 0.19162 (14) | 0.0390 (7) | |
H7 | −0.2175 | 0.6979 | 0.2064 | 0.047* | |
C6 | −0.0260 (3) | 0.71665 (19) | 0.15084 (12) | 0.0342 (6) | |
C9 | −0.2763 (3) | 0.9481 (2) | 0.28377 (12) | 0.0442 (7) | |
H9A | −0.3701 | 0.9772 | 0.3002 | 0.053* | |
H9B | −0.2078 | 0.9345 | 0.3190 | 0.053* | |
O4 | 0.3101 (2) | 0.81227 (13) | 0.06922 (9) | 0.0375 (4) | |
O6 | 0.3652 (2) | 1.11280 (15) | 0.17999 (11) | 0.0512 (5) | |
O5 | 0.3227 (3) | 0.96826 (17) | 0.21283 (10) | 0.0547 (6) | |
N4 | 0.3655 (3) | 1.0532 (2) | 0.22490 (12) | 0.0499 (7) | |
C3 | 0.2149 (4) | 0.6458 (2) | 0.07543 (13) | 0.0423 (7) | |
H3 | 0.2962 | 0.6222 | 0.0512 | 0.051* | |
O8 | 0.5474 (2) | 0.96187 (15) | 0.11091 (10) | 0.0549 (5) | |
O7 | 0.4055 (3) | 1.0771 (2) | 0.27813 (10) | 0.0801 (9) | |
C19 | 0.4453 (3) | 0.7805 (2) | 0.03486 (13) | 0.0432 (7) | |
H19A | 0.4880 | 0.8343 | 0.0115 | 0.052* | |
H19B | 0.4150 | 0.7315 | 0.0046 | 0.052* | |
C17 | 0.2251 (3) | 1.2415 (2) | 0.02918 (12) | 0.0421 (7) | |
H17A | 0.1457 | 1.2807 | 0.0095 | 0.051* | |
H17B | 0.2742 | 1.2037 | −0.0038 | 0.051* | |
C4 | 0.1003 (4) | 0.5844 (2) | 0.09727 (14) | 0.0494 (7) | |
H4 | 0.1033 | 0.5195 | 0.0867 | 0.059* | |
O9 | 0.5073 (3) | 1.08024 (19) | 0.04820 (11) | 0.0674 (7) | |
C16 | −0.0230 (3) | 1.14433 (18) | 0.15577 (11) | 0.0313 (6) | |
N5 | 0.6032 (3) | 1.0273 (2) | 0.07704 (12) | 0.0531 (8) | |
C5 | −0.0159 (4) | 0.6184 (2) | 0.13382 (14) | 0.0452 (7) | |
H5 | −0.0912 | 0.5760 | 0.1482 | 0.054* | |
C14 | −0.0200 (3) | 1.3047 (2) | 0.11232 (14) | 0.0424 (7) | |
H14 | 0.0197 | 1.3489 | 0.0836 | 0.051* | |
C20 | 0.5678 (4) | 0.7401 (2) | 0.07790 (16) | 0.0581 (9) | |
H20A | 0.5984 | 0.7884 | 0.1079 | 0.087* | |
H20B | 0.6559 | 0.7210 | 0.0533 | 0.087* | |
H20C | 0.5273 | 0.6854 | 0.1000 | 0.087* | |
C11 | −0.1455 (3) | 1.1711 (2) | 0.19646 (13) | 0.0372 (7) | |
C12 | −0.1973 (4) | 1.2667 (2) | 0.19550 (15) | 0.0455 (8) | |
H12 | −0.2734 | 1.2863 | 0.2238 | 0.055* | |
C15 | 0.0375 (3) | 1.21237 (18) | 0.11412 (12) | 0.0319 (6) | |
O10 | 0.7407 (3) | 1.0400 (3) | 0.07259 (14) | 0.0962 (9) | |
C13 | −0.1373 (4) | 1.3313 (2) | 0.15352 (15) | 0.0516 (8) | |
H13 | −0.1755 | 1.3938 | 0.1525 | 0.062* | |
C18 | 0.3432 (4) | 1.3058 (2) | 0.05866 (16) | 0.0563 (9) | |
H18A | 0.2930 | 1.3498 | 0.0870 | 0.084* | |
H18B | 0.3959 | 1.3413 | 0.0262 | 0.084* | |
H18C | 0.4166 | 1.2677 | 0.0817 | 0.084* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O3 | 0.0427 (10) | 0.0243 (10) | 0.0411 (10) | −0.0017 (8) | 0.0064 (8) | 0.0068 (8) |
Ce1 | 0.03051 (6) | 0.02503 (7) | 0.03596 (7) | −0.00109 (8) | 0.00364 (5) | 0.00254 (7) |
Zn1 | 0.03818 (16) | 0.03034 (16) | 0.04675 (16) | −0.00153 (14) | 0.00994 (14) | 0.00350 (15) |
O1 | 0.0324 (9) | 0.0221 (9) | 0.0455 (10) | 0.0025 (8) | 0.0094 (7) | 0.0046 (8) |
O2 | 0.0391 (10) | 0.0214 (9) | 0.0489 (11) | −0.0013 (8) | 0.0137 (9) | 0.0013 (8) |
N1 | 0.0370 (10) | 0.0386 (15) | 0.0377 (11) | 0.0013 (10) | 0.0053 (8) | 0.0027 (10) |
C2 | 0.0382 (13) | 0.0242 (13) | 0.0366 (14) | −0.0008 (10) | −0.0052 (11) | 0.0029 (11) |
N3 | 0.0623 (15) | 0.0346 (13) | 0.0461 (13) | 0.0027 (14) | −0.0048 (11) | −0.0069 (14) |
O11 | 0.0560 (13) | 0.0659 (16) | 0.0437 (10) | −0.0115 (13) | 0.0044 (9) | −0.0018 (9) |
N2 | 0.0352 (13) | 0.0366 (14) | 0.0389 (13) | −0.0050 (10) | 0.0038 (10) | 0.0097 (10) |
O12 | 0.0476 (12) | 0.0795 (18) | 0.0475 (12) | −0.0123 (11) | −0.0001 (10) | −0.0032 (10) |
C1 | 0.0335 (14) | 0.0242 (13) | 0.0346 (13) | −0.0009 (11) | −0.0038 (11) | 0.0027 (10) |
O13 | 0.1096 (19) | 0.0728 (17) | 0.0491 (12) | −0.0055 (18) | −0.0273 (12) | −0.0007 (15) |
C10 | 0.0377 (15) | 0.0407 (17) | 0.0375 (14) | 0.0074 (13) | 0.0058 (11) | −0.0004 (12) |
C8 | 0.0364 (15) | 0.055 (2) | 0.0471 (17) | −0.0042 (14) | 0.0103 (13) | 0.0123 (14) |
C7 | 0.0364 (15) | 0.0335 (16) | 0.0471 (17) | −0.0108 (12) | −0.0027 (13) | 0.0137 (13) |
C6 | 0.0385 (15) | 0.0267 (14) | 0.0375 (14) | −0.0044 (11) | −0.0045 (11) | 0.0048 (11) |
C9 | 0.0444 (16) | 0.0456 (17) | 0.0426 (14) | 0.0042 (14) | 0.0121 (12) | 0.0091 (13) |
O4 | 0.0355 (10) | 0.0300 (11) | 0.0469 (11) | 0.0012 (8) | 0.0088 (8) | −0.0020 (8) |
O6 | 0.0581 (13) | 0.0451 (13) | 0.0503 (12) | 0.0004 (10) | −0.0065 (11) | −0.0019 (11) |
O5 | 0.0580 (14) | 0.0570 (16) | 0.0490 (12) | 0.0053 (11) | 0.0024 (10) | 0.0148 (10) |
N4 | 0.0385 (13) | 0.065 (2) | 0.0465 (16) | 0.0180 (14) | −0.0025 (11) | −0.0092 (15) |
C3 | 0.0536 (18) | 0.0287 (15) | 0.0448 (15) | 0.0051 (13) | −0.0058 (13) | −0.0029 (12) |
O8 | 0.0402 (11) | 0.0460 (13) | 0.0787 (15) | 0.0012 (10) | 0.0019 (10) | 0.0088 (11) |
O7 | 0.0849 (18) | 0.111 (2) | 0.0440 (12) | 0.0480 (17) | −0.0205 (12) | −0.0234 (14) |
C19 | 0.0379 (15) | 0.0417 (17) | 0.0500 (17) | 0.0051 (13) | 0.0093 (13) | −0.0039 (13) |
C17 | 0.0559 (18) | 0.0301 (15) | 0.0404 (14) | −0.0031 (13) | 0.0087 (13) | 0.0099 (11) |
C4 | 0.064 (2) | 0.0234 (15) | 0.0608 (19) | −0.0002 (13) | −0.0094 (16) | −0.0015 (13) |
O9 | 0.0461 (13) | 0.087 (2) | 0.0695 (15) | −0.0173 (12) | 0.0004 (11) | 0.0304 (14) |
C16 | 0.0346 (14) | 0.0236 (14) | 0.0358 (13) | 0.0012 (10) | −0.0050 (10) | 0.0010 (10) |
N5 | 0.0366 (13) | 0.069 (2) | 0.0537 (15) | −0.0074 (13) | 0.0065 (11) | −0.0126 (13) |
C5 | 0.0583 (19) | 0.0249 (15) | 0.0525 (17) | −0.0106 (13) | −0.0065 (14) | 0.0050 (12) |
C14 | 0.0429 (16) | 0.0293 (16) | 0.0550 (18) | 0.0002 (12) | −0.0027 (13) | 0.0076 (13) |
C20 | 0.0496 (18) | 0.052 (2) | 0.073 (2) | 0.0172 (17) | −0.0047 (17) | −0.0103 (16) |
C11 | 0.0381 (15) | 0.0324 (15) | 0.0412 (17) | 0.0037 (12) | 0.0019 (12) | 0.0015 (12) |
C12 | 0.0413 (17) | 0.0392 (18) | 0.0559 (19) | 0.0105 (13) | 0.0077 (13) | −0.0042 (14) |
C15 | 0.0316 (14) | 0.0264 (14) | 0.0376 (14) | −0.0017 (11) | −0.0039 (10) | −0.0021 (11) |
O10 | 0.0352 (12) | 0.146 (3) | 0.107 (2) | −0.0259 (16) | 0.0072 (13) | 0.000 (2) |
C13 | 0.0542 (19) | 0.0285 (16) | 0.072 (2) | 0.0148 (14) | −0.0005 (16) | −0.0035 (15) |
C18 | 0.062 (2) | 0.043 (2) | 0.064 (2) | −0.0126 (16) | 0.0158 (16) | −0.0037 (16) |
O3—C15 | 1.388 (3) | C6—C5 | 1.416 (4) |
O3—C17 | 1.467 (3) | C9—H9A | 0.9700 |
Ce1—O1 | 2.4293 (16) | C9—H9B | 0.9700 |
Ce1—O2 | 2.4712 (17) | O4—C19 | 1.445 (3) |
Ce1—O4 | 2.6917 (18) | O6—N4 | 1.261 (3) |
Ce1—O5 | 2.607 (2) | O5—N4 | 1.264 (4) |
Ce1—O6 | 2.575 (2) | N4—O7 | 1.224 (3) |
Ce1—O8 | 2.571 (2) | C3—C4 | 1.387 (4) |
Ce1—O9 | 2.610 (2) | C3—H3 | 0.9300 |
Ce1—O11 | 2.539 (2) | O8—N5 | 1.255 (3) |
Ce1—O12 | 2.576 (2) | C19—C20 | 1.505 (4) |
O3—Ce1 | 2.6572 (18) | C19—H19A | 0.9700 |
Zn1—O1 | 1.9078 (18) | C19—H19B | 0.9700 |
Zn1—O2 | 1.9039 (18) | C17—C18 | 1.493 (4) |
Zn1—N1 | 1.922 (2) | C17—H17A | 0.9700 |
Zn1—N2 | 1.913 (2) | C17—H17B | 0.9700 |
O1—C16 | 1.329 (3) | C4—C5 | 1.352 (4) |
O2—C1 | 1.333 (3) | C4—H4 | 0.9300 |
N1—C10 | 1.264 (3) | O9—N5 | 1.265 (3) |
N1—C9 | 1.466 (3) | C16—C15 | 1.395 (3) |
C2—C3 | 1.384 (4) | C16—C11 | 1.414 (4) |
C2—O4 | 1.387 (3) | N5—O10 | 1.205 (3) |
C2—C1 | 1.399 (4) | C5—H5 | 0.9300 |
N3—O13 | 1.223 (3) | C14—C15 | 1.376 (4) |
N3—O12 | 1.251 (3) | C14—C13 | 1.388 (4) |
N3—O11 | 1.269 (3) | C14—H14 | 0.9300 |
N2—C7 | 1.273 (4) | C20—H20A | 0.9600 |
N2—C8 | 1.485 (4) | C20—H20B | 0.9600 |
C1—C6 | 1.399 (4) | C20—H20C | 0.9600 |
C10—C11 | 1.456 (4) | C11—C12 | 1.403 (4) |
C10—H10 | 0.9300 | C12—C13 | 1.365 (4) |
C8—C9 | 1.515 (4) | C12—H12 | 0.9300 |
C8—H8A | 0.9700 | C13—H13 | 0.9300 |
C8—H8B | 0.9700 | C18—H18A | 0.9600 |
C7—C6 | 1.444 (4) | C18—H18B | 0.9600 |
C7—H7 | 0.9300 | C18—H18C | 0.9600 |
C15—O3—C17 | 118.5 (2) | N2—C8—H8A | 110.3 |
C15—O3—Ce1 | 119.39 (14) | C9—C8—H8A | 110.3 |
C17—O3—Ce1 | 121.63 (15) | N2—C8—H8B | 110.3 |
O1—Ce1—O2 | 63.82 (6) | C9—C8—H8B | 110.3 |
O1—Ce1—O11 | 120.91 (6) | H8A—C8—H8B | 108.5 |
O2—Ce1—O11 | 115.61 (7) | N2—C7—C6 | 125.1 (3) |
O1—Ce1—O8 | 139.54 (6) | N2—C7—H7 | 117.4 |
O2—Ce1—O8 | 113.57 (7) | C6—C7—H7 | 117.4 |
O11—Ce1—O8 | 97.24 (7) | C1—C6—C5 | 117.8 (3) |
O1—Ce1—O6 | 73.55 (7) | C1—C6—C7 | 124.2 (2) |
O2—Ce1—O6 | 113.26 (6) | C5—C6—C7 | 118.0 (2) |
O11—Ce1—O6 | 130.15 (7) | N1—C9—C8 | 108.3 (2) |
O8—Ce1—O6 | 71.40 (7) | N1—C9—H9A | 110.0 |
O1—Ce1—O12 | 81.65 (7) | C8—C9—H9A | 110.0 |
O2—Ce1—O12 | 72.36 (7) | N1—C9—H9B | 110.0 |
O11—Ce1—O12 | 49.29 (7) | C8—C9—H9B | 110.0 |
O8—Ce1—O12 | 138.08 (7) | H9A—C9—H9B | 108.4 |
O6—Ce1—O12 | 147.30 (7) | C2—O4—C19 | 117.8 (2) |
O1—Ce1—O5 | 73.83 (7) | C2—O4—Ce1 | 120.42 (14) |
O2—Ce1—O5 | 70.41 (7) | C19—O4—Ce1 | 121.82 (15) |
O11—Ce1—O5 | 165.21 (7) | N4—O6—Ce1 | 97.47 (18) |
O8—Ce1—O5 | 68.19 (7) | N4—O5—Ce1 | 95.80 (17) |
O6—Ce1—O5 | 49.22 (7) | O7—N4—O6 | 121.0 (3) |
O12—Ce1—O5 | 141.58 (7) | O7—N4—O5 | 121.5 (3) |
O1—Ce1—O9 | 134.68 (8) | O6—N4—O5 | 117.5 (3) |
O2—Ce1—O9 | 160.08 (7) | C2—C3—C4 | 119.3 (3) |
O11—Ce1—O9 | 64.65 (7) | C2—C3—H3 | 120.3 |
O8—Ce1—O9 | 48.83 (7) | C4—C3—H3 | 120.3 |
O6—Ce1—O9 | 72.88 (8) | N5—O8—Ce1 | 98.45 (17) |
O12—Ce1—O9 | 113.40 (7) | O4—C19—C20 | 112.2 (2) |
O5—Ce1—O9 | 104.85 (8) | O4—C19—H19A | 109.2 |
O1—Ce1—O3 | 60.29 (6) | C20—C19—H19A | 109.2 |
O2—Ce1—O3 | 119.69 (6) | O4—C19—H19B | 109.2 |
O11—Ce1—O3 | 77.55 (6) | C20—C19—H19B | 109.2 |
O8—Ce1—O3 | 123.02 (6) | H19A—C19—H19B | 107.9 |
O6—Ce1—O3 | 70.43 (6) | O3—C17—C18 | 112.8 (2) |
O12—Ce1—O3 | 78.93 (7) | O3—C17—H17A | 109.0 |
O5—Ce1—O3 | 112.00 (6) | C18—C17—H17A | 109.0 |
O9—Ce1—O3 | 80.18 (7) | O3—C17—H17B | 109.0 |
O1—Ce1—O4 | 123.10 (6) | C18—C17—H17B | 109.0 |
O2—Ce1—O4 | 59.35 (5) | H17A—C17—H17B | 107.8 |
O11—Ce1—O4 | 82.89 (6) | C5—C4—C3 | 120.3 (3) |
O8—Ce1—O4 | 70.81 (6) | C5—C4—H4 | 119.8 |
O6—Ce1—O4 | 132.18 (6) | C3—C4—H4 | 119.8 |
O12—Ce1—O4 | 79.42 (7) | N5—O9—Ce1 | 96.24 (16) |
O5—Ce1—O4 | 89.61 (7) | O1—C16—C15 | 117.3 (2) |
O9—Ce1—O4 | 102.01 (7) | O1—C16—C11 | 123.6 (2) |
O3—Ce1—O4 | 157.17 (6) | C15—C16—C11 | 119.1 (2) |
O2—Zn1—O1 | 85.63 (7) | O10—N5—O8 | 122.0 (3) |
O2—Zn1—N2 | 94.75 (9) | O10—N5—O9 | 121.5 (3) |
O1—Zn1—N2 | 177.44 (9) | O8—N5—O9 | 116.4 (2) |
O2—Zn1—N1 | 171.99 (9) | C4—C5—C6 | 121.9 (3) |
O1—Zn1—N1 | 93.87 (9) | C4—C5—H5 | 119.0 |
N2—Zn1—N1 | 86.10 (11) | C6—C5—H5 | 119.0 |
C16—O1—Zn1 | 124.13 (15) | C15—C14—C13 | 119.7 (3) |
C16—O1—Ce1 | 128.59 (15) | C15—C14—H14 | 120.2 |
Zn1—O1—Ce1 | 105.92 (8) | C13—C14—H14 | 120.2 |
C1—O2—Zn1 | 126.02 (16) | C19—C20—H20A | 109.5 |
C1—O2—Ce1 | 129.39 (16) | C19—C20—H20B | 109.5 |
Zn1—O2—Ce1 | 104.48 (7) | H20A—C20—H20B | 109.5 |
C10—N1—C9 | 123.7 (2) | C19—C20—H20C | 109.5 |
C10—N1—Zn1 | 125.8 (2) | H20A—C20—H20C | 109.5 |
C9—N1—Zn1 | 110.48 (18) | H20B—C20—H20C | 109.5 |
C3—C2—O4 | 125.2 (2) | C12—C11—C16 | 118.7 (3) |
C3—C2—C1 | 121.1 (2) | C12—C11—C10 | 118.3 (3) |
O4—C2—C1 | 113.7 (2) | C16—C11—C10 | 123.0 (2) |
O13—N3—O12 | 122.6 (3) | C13—C12—C11 | 120.7 (3) |
O13—N3—O11 | 121.8 (3) | C13—C12—H12 | 119.6 |
O12—N3—O11 | 115.6 (2) | C11—C12—H12 | 119.6 |
N3—O11—Ce1 | 97.92 (15) | C14—C15—O3 | 125.3 (2) |
C7—N2—C8 | 121.6 (3) | C14—C15—C16 | 121.0 (2) |
C7—N2—Zn1 | 126.0 (2) | O3—C15—C16 | 113.6 (2) |
C8—N2—Zn1 | 112.23 (19) | C12—C13—C14 | 120.7 (3) |
N3—O12—Ce1 | 96.64 (15) | C12—C13—H13 | 119.6 |
O2—C1—C6 | 123.6 (2) | C14—C13—H13 | 119.6 |
O2—C1—C2 | 116.9 (2) | C17—C18—H18A | 109.5 |
C6—C1—C2 | 119.4 (2) | C17—C18—H18B | 109.5 |
N1—C10—C11 | 125.0 (3) | H18A—C18—H18B | 109.5 |
N1—C10—H10 | 117.5 | C17—C18—H18C | 109.5 |
C11—C10—H10 | 117.5 | H18A—C18—H18C | 109.5 |
N2—C8—C9 | 107.1 (2) | H18B—C18—H18C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O7i | 0.93 | 2.36 | 3.275 (4) | 168 |
C9—H9A···O7ii | 0.97 | 2.43 | 3.286 (4) | 147 |
C17—H17B···O9 | 0.97 | 2.87 | 3.337 (4) | 111 |
C20—H20A···O8 | 0.96 | 2.45 | 3.166 (4) | 131 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [CeZn(C20H22N2O4)(NO3)3] |
Mr | 745.92 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 8.6418 (14), 13.904 (2), 21.157 (3) |
V (Å3) | 2542.2 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.79 |
Crystal size (mm) | 0.31 × 0.22 × 0.20 |
Data collection | |
Diffractometer | Bruker APEX II area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.494, 0.572 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19190, 6211, 5407 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.020, 0.048, 1.01 |
No. of reflections | 6211 |
No. of parameters | 363 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.36 |
Absolute structure | Flack (1983), 2611 Friedel pairs |
Absolute structure parameter | 0.017 (9) |
Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), APEX2 and publCIF (Westrip, 2007).
Ce1—O1 | 2.4293 (16) | Ce1—O11 | 2.539 (2) |
Ce1—O2 | 2.4712 (17) | Ce1—O12 | 2.576 (2) |
Ce1—O4 | 2.6917 (18) | O3—Ce1 | 2.6572 (18) |
Ce1—O5 | 2.607 (2) | Zn1—O1 | 1.9078 (18) |
Ce1—O6 | 2.575 (2) | Zn1—O2 | 1.9039 (18) |
Ce1—O8 | 2.571 (2) | Zn1—N1 | 1.922 (2) |
Ce1—O9 | 2.610 (2) | Zn1—N2 | 1.913 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O7i | 0.93 | 2.36 | 3.275 (4) | 167.8 |
C9—H9A···O7ii | 0.97 | 2.43 | 3.286 (4) | 146.7 |
C17—H17B···O9 | 0.97 | 2.87 | 3.337 (4) | 110.9 |
C20—H20A···O8 | 0.96 | 2.45 | 3.166 (4) | 130.9 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x−1, y, z. |
The potential applications of trivalent lanthanide complexes as contrast agent for magnetic resonance imaging and stains for fluorescence imaging have prompted considerable interest in the preparation, magnetic and optical properties of 3 d-4f hetorometallic dinuclear complexes (Baggio et al., 2000; Caravan et al., 1999; Edder et al., 2000; Knoer et al., 2005). As part of our investigations into the structure and applications of 3 d-4f hetorometallic Schiff base complexes (Sui et al., 2006), we report here the synthesis and X-ray crystal structure analysis of the title complex, (I), a new ZnII—CeIII complex with salen-type Schiff base N,N'-bis(3-ethoxysalicylidene) ethylenediamine(H2L).
Complex (I) crystallizes in the space group P212121, with zinc and cerium doubly bridged by two phenolate O atoms provided by a salen-type Schiff base ligand. The inner salen-type cavity is occupied by zinc(II), while cerium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand. The dihedral angles between the mean planes of Zn1/O1/O2 and Ce1/O1/O2 is 3.62 (11)° suggesting that the bridging moiety is almost planar; the deviation of atoms from the least squares Zn1/O1/O2/Ce1 plane being 0.0310 (3)Å for Zn, 0.0208 (3)Å for Ce, -0.0262 (2)Å for O1 and -0.0256 (2)Å for O2.
The cerium(III) center in (I) has a decacoordination environment of O atoms. In addition to the phenolate ligands, two ethoxy O atoms coordinate to this metal center, two O atoms from each of the three nitrates chelate to cerium to complete the decacoordination. The three kinds of Ce—O bond distances are significantly different, the shortest being the Ce—O(phenolate) and longest being the Ce—O(ethoxy) separations.
The coordination of zinc(II) is approximately square planar. The donor centers are alternatively above and below the mean N2O2 plane with an average deviation from the plane of 0.0879 (2) Å, while Zn1 is 0.0453 (2)Å below this square plane.
Adjacent molecules are held together by weak interactions (O10···Zn1=3.156 (4) Å, C7—H7···O7i=3.275 (4) and C9—H9A···O7ii=3.286 (4); symmetry codes:(i)-x, y - 1/2, 1/2 - z; (ii)x - 1, y, z). these link the molecules into a two-dimensional zigzag sheet(Fig 2).