Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032552/hg2252sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032552/hg2252Isup2.hkl |
CCDC reference: 657546
H2L was prepared by the 2:1 condensation of 3-ethoxysalicylaldehyde and ethylenediamine in methanol. Complex (I) was obtained by the treatment of copper(II) acetate monohydrate (0.168 g, 1 mmol) with H2L(0.356 g, 1 mmol) in methanol solution (60 ml) under reflux for 3 h and then for another 3 h after the addition of neodymium(III) nitrate hexahydrate (0.438 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 C20H22CuN5NdO13: C 32.11, H 2.96, Cu 8.49, N 9.36,Nd 19.28%; found: C 32.00, H 2.86, Cu 8.53, N 9.47,Nd 19.30%. 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 CuII—NdIII complex with salen-type Schiff base N,N'-bis(3-ethoxysalicylidene) ethylenediamine(H2L).
Complex (I) crystallizes in the space group P212121, with copper and neodymium doubly bridged by two phenolate O atoms provided by a salen-type Schiff base ligand. The inner salen-type cavity is occupied by copper(II), while neodymium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand. The dihedral angles between the mean planes of Cu1/O1/O2 and Nd1/O1/O2 is 3.63 (14)° suggesting that the bridging moiety is almost planar; the deviation of atoms from the least squares Cu1/O1/O2/Nd1 plane being -0.0308 (3)Å for Cu, -0.0211 (2)Å for Nd, 0.0256 (3)Å for O1 and 0.0262 (3)Å for O2.
The neodymium(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 neodymium to complete the decacoordination. The three kinds of Nd—O bond distances are significantly different, the shortest being the Nd—O(phenolate) and longest being the Nd—O(ethoxy) separations.
The coordination of copper(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 0.0887 (2) Å, while Cu1 is 0.0395 (3)Å above this square plane.
Adjacent molecules are held together by weak interactions (O13···Cu1=3.169 (3) Å, C7—H7···O7i=3.277 (4) and C9—H9A···O7ii=3.290 (5); symmetry codes:(i)-x + 1, y - 1/2, 3/2 - z; (ii)1 + x, 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).
Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. | |
Fig. 2. The packing diagram of (I), viewed along the b axis; hydrogen bonds are shown as dashed lines. |
[CuNd(C20H22N2O4)(NO3)3] | F(000) = 1480 |
Mr = 748.21 | Dx = 1.962 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 19224 reflections |
a = 8.6439 (16) Å | θ = 1.8–28.3° |
b = 13.861 (3) Å | µ = 2.95 mm−1 |
c = 21.135 (4) Å | T = 293 K |
V = 2532.4 (8) Å3 | Block, red |
Z = 4 | 0.22 × 0.17 × 0.08 mm |
Bruker APEX II area-detector diffractometer | 6179 independent reflections |
Radiation source: fine-focus sealed tube | 4830 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 0 pixels mm-1 | θmax = 28.3°, θmin = 1.8° |
φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −18→18 |
Tmin = 0.570, Tmax = 0.794 | l = −28→27 |
19224 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)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.051 | w = 1/[σ2(Fo2) + (0.017P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
6179 reflections | Δρmax = 0.41 e Å−3 |
363 parameters | Δρmin = −0.85 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 2611 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.008 (10) |
[CuNd(C20H22N2O4)(NO3)3] | V = 2532.4 (8) Å3 |
Mr = 748.21 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.6439 (16) Å | µ = 2.95 mm−1 |
b = 13.861 (3) Å | T = 293 K |
c = 21.135 (4) Å | 0.22 × 0.17 × 0.08 mm |
Bruker APEX II area-detector diffractometer | 6179 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 4830 reflections with I > 2σ(I) |
Tmin = 0.570, Tmax = 0.794 | Rint = 0.030 |
19224 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | H-atom parameters constrained |
wR(F2) = 0.051 | Δρmax = 0.41 e Å−3 |
S = 1.01 | Δρmin = −0.85 e Å−3 |
6179 reflections | Absolute structure: Flack (1983), 2611 Friedel pairs |
363 parameters | Absolute structure parameter: −0.008 (10) |
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 | ||
C11 | 0.6447 (4) | 1.1718 (2) | 0.80399 (17) | 0.0393 (9) | |
O2 | 0.4613 (2) | 1.05648 (15) | 0.84587 (10) | 0.0361 (5) | |
C14 | 0.5175 (4) | 1.3051 (2) | 0.88820 (18) | 0.0446 (9) | |
H14 | 0.4767 | 1.3496 | 0.9166 | 0.053* | |
Nd1 | 0.241515 (18) | 0.999977 (13) | 0.904190 (7) | 0.03374 (5) | |
Cu1 | 0.56585 (5) | 0.94407 (3) | 0.81664 (2) | 0.03818 (10) | |
O1 | 0.4129 (3) | 0.87540 (14) | 0.86294 (11) | 0.0393 (6) | |
N3 | 0.3700 (4) | 0.9940 (3) | 1.03348 (15) | 0.0519 (7) | |
N2 | 0.6995 (3) | 1.0138 (2) | 0.76099 (13) | 0.0409 (7) | |
O9 | 0.4502 (3) | 0.9690 (2) | 0.98654 (12) | 0.0620 (8) | |
N1 | 0.6781 (4) | 0.8324 (2) | 0.79083 (14) | 0.0399 (8) | |
C1 | 0.4124 (4) | 0.7805 (2) | 0.87300 (16) | 0.0325 (8) | |
O3 | 0.1882 (3) | 0.81437 (15) | 0.93014 (11) | 0.0396 (6) | |
O10 | 0.4244 (4) | 1.0009 (2) | 1.08698 (13) | 0.0815 (8) | |
C2 | 0.2910 (4) | 0.7440 (2) | 0.90989 (16) | 0.0357 (8) | |
C7 | 0.6500 (4) | 0.7459 (3) | 0.80840 (18) | 0.0413 (9) | |
H7 | 0.7161 | 0.6978 | 0.7939 | 0.050* | |
C5 | 0.5126 (4) | 0.6185 (2) | 0.86622 (18) | 0.0494 (10) | |
H5 | 0.5875 | 0.5756 | 0.8519 | 0.059* | |
O8 | 0.2296 (3) | 1.0111 (2) | 1.02179 (11) | 0.0565 (6) | |
C4 | 0.3961 (4) | 0.5855 (2) | 0.90305 (19) | 0.0513 (10) | |
H4 | 0.3925 | 0.5205 | 0.9139 | 0.062* | |
C10 | 0.7205 (4) | 1.1050 (3) | 0.76113 (16) | 0.0415 (8) | |
H10 | 0.7892 | 1.1305 | 0.7317 | 0.050* | |
C6 | 0.5231 (4) | 0.7166 (2) | 0.84912 (16) | 0.0367 (8) | |
C19 | 0.0527 (4) | 0.7830 (2) | 0.96501 (17) | 0.0446 (9) | |
H19A | 0.0097 | 0.8375 | 0.9878 | 0.053* | |
H19B | 0.0832 | 0.7348 | 0.9958 | 0.053* | |
O6 | 0.1803 (3) | 0.9675 (2) | 0.78716 (13) | 0.0539 (8) | |
O5 | 0.1368 (3) | 1.11173 (18) | 0.81937 (13) | 0.0523 (6) | |
N4 | 0.1369 (4) | 1.0515 (3) | 0.77486 (17) | 0.0520 (8) | |
C3 | 0.2823 (4) | 0.6474 (2) | 0.92465 (17) | 0.0448 (9) | |
H3 | 0.2008 | 0.6241 | 0.9489 | 0.054* | |
C8 | 0.8123 (4) | 0.8556 (3) | 0.75078 (18) | 0.0478 (9) | |
H8A | 0.8305 | 0.8042 | 0.7205 | 0.057* | |
H8B | 0.9043 | 0.8632 | 0.7766 | 0.057* | |
C9 | 0.7763 (4) | 0.9481 (3) | 0.71683 (16) | 0.0463 (9) | |
H9A | 0.8710 | 0.9772 | 0.7013 | 0.056* | |
H9B | 0.7093 | 0.9354 | 0.6810 | 0.056* | |
C20 | −0.0682 (5) | 0.7417 (3) | 0.9226 (2) | 0.0627 (12) | |
H20A | −0.1044 | 0.7907 | 0.8941 | 0.094* | |
H20B | −0.1531 | 0.7185 | 0.9476 | 0.094* | |
H20C | −0.0250 | 0.6892 | 0.8988 | 0.094* | |
O11 | −0.0411 (3) | 0.96243 (18) | 0.88817 (13) | 0.0575 (7) | |
O4 | 0.3447 (3) | 1.17580 (15) | 0.92475 (11) | 0.0390 (6) | |
O13 | −0.2383 (3) | 1.0394 (3) | 0.92662 (16) | 0.0963 (11) | |
C16 | 0.5209 (4) | 1.1451 (2) | 0.84417 (15) | 0.0334 (7) | |
O12 | −0.0021 (3) | 1.0835 (2) | 0.94837 (15) | 0.0706 (9) | |
O7 | 0.0968 (4) | 1.0759 (2) | 0.72145 (14) | 0.0835 (11) | |
C13 | 0.6365 (5) | 1.3318 (3) | 0.84766 (19) | 0.0536 (10) | |
H13 | 0.6748 | 1.3945 | 0.8492 | 0.064* | |
N5 | −0.0977 (4) | 1.0284 (2) | 0.92122 (16) | 0.0559 (9) | |
C15 | 0.4601 (4) | 1.2122 (2) | 0.88621 (16) | 0.0352 (8) | |
C12 | 0.6984 (4) | 1.2675 (3) | 0.80550 (19) | 0.0492 (11) | |
H12 | 0.7759 | 1.2872 | 0.7778 | 0.059* | |
C17 | 0.2725 (4) | 1.2405 (2) | 0.97093 (16) | 0.0447 (9) | |
H17A | 0.3520 | 1.2793 | 0.9910 | 0.054* | |
H17B | 0.2223 | 1.2024 | 1.0035 | 0.054* | |
C18 | 0.1549 (5) | 1.3063 (3) | 0.9406 (2) | 0.0595 (12) | |
H18A | 0.2071 | 1.3539 | 0.9155 | 0.089* | |
H18B | 0.0952 | 1.3377 | 0.9729 | 0.089* | |
H18C | 0.0873 | 1.2690 | 0.9140 | 0.089* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C11 | 0.036 (2) | 0.0354 (18) | 0.047 (2) | −0.0048 (15) | 0.0028 (17) | −0.0019 (18) |
O2 | 0.0360 (12) | 0.0246 (10) | 0.0477 (13) | −0.0027 (10) | 0.0114 (11) | −0.0024 (11) |
C14 | 0.048 (2) | 0.0276 (18) | 0.058 (2) | −0.0006 (14) | −0.0061 (19) | −0.0105 (17) |
Nd1 | 0.03385 (8) | 0.02793 (7) | 0.03943 (8) | 0.00136 (11) | 0.00417 (8) | −0.00230 (9) |
Cu1 | 0.0381 (2) | 0.02996 (18) | 0.0464 (2) | 0.00145 (18) | 0.0109 (2) | −0.0040 (2) |
O1 | 0.0419 (14) | 0.0237 (10) | 0.0523 (15) | 0.0026 (10) | 0.0147 (12) | 0.0001 (10) |
N3 | 0.067 (2) | 0.0368 (15) | 0.0518 (19) | 0.001 (2) | −0.0018 (16) | 0.007 (2) |
N2 | 0.0382 (14) | 0.0444 (18) | 0.0401 (15) | −0.0006 (13) | 0.0055 (11) | −0.0015 (15) |
O9 | 0.0502 (15) | 0.084 (2) | 0.0516 (15) | 0.0084 (14) | 0.0009 (14) | 0.0027 (14) |
N1 | 0.0384 (17) | 0.0395 (17) | 0.0417 (18) | 0.0031 (13) | 0.0055 (14) | −0.0102 (15) |
C1 | 0.037 (2) | 0.0277 (16) | 0.0329 (18) | 0.0005 (14) | −0.0024 (16) | −0.0024 (15) |
O3 | 0.0354 (13) | 0.0328 (12) | 0.0506 (15) | −0.0020 (10) | 0.0100 (11) | 0.0016 (11) |
O10 | 0.114 (2) | 0.0766 (19) | 0.0540 (17) | 0.012 (2) | −0.0269 (17) | −0.002 (2) |
C2 | 0.0441 (19) | 0.0260 (15) | 0.0369 (18) | −0.0003 (13) | −0.0045 (16) | −0.0048 (15) |
C7 | 0.038 (2) | 0.0379 (19) | 0.048 (2) | 0.0122 (15) | −0.0037 (18) | −0.0101 (18) |
C5 | 0.056 (2) | 0.0292 (18) | 0.063 (3) | 0.0116 (16) | −0.003 (2) | −0.0040 (18) |
O8 | 0.0605 (17) | 0.0622 (17) | 0.0469 (13) | 0.0087 (17) | 0.0071 (12) | −0.0003 (13) |
C4 | 0.066 (3) | 0.0263 (17) | 0.061 (2) | 0.0002 (16) | −0.012 (2) | −0.0049 (18) |
C10 | 0.039 (2) | 0.047 (2) | 0.0385 (19) | −0.0080 (17) | 0.0035 (16) | 0.0003 (17) |
C6 | 0.041 (2) | 0.0271 (16) | 0.0415 (19) | 0.0031 (14) | −0.0063 (17) | −0.0028 (16) |
C19 | 0.0379 (19) | 0.0436 (19) | 0.052 (2) | −0.0067 (16) | 0.0101 (19) | 0.0034 (18) |
O6 | 0.0582 (18) | 0.0578 (17) | 0.0457 (16) | −0.0026 (13) | 0.0010 (13) | −0.0126 (13) |
O5 | 0.0603 (17) | 0.0462 (14) | 0.0503 (16) | −0.0021 (12) | −0.0057 (14) | 0.0040 (15) |
N4 | 0.0408 (18) | 0.069 (2) | 0.046 (2) | −0.0183 (19) | −0.0010 (16) | 0.012 (2) |
C3 | 0.053 (2) | 0.0341 (17) | 0.048 (2) | −0.0029 (16) | −0.0019 (18) | 0.0059 (16) |
C8 | 0.038 (2) | 0.057 (2) | 0.049 (2) | 0.0061 (17) | 0.0084 (18) | −0.0130 (19) |
C9 | 0.046 (2) | 0.0496 (19) | 0.0436 (19) | −0.0016 (18) | 0.0120 (17) | −0.0123 (18) |
C20 | 0.057 (3) | 0.052 (2) | 0.079 (3) | −0.013 (2) | −0.003 (2) | 0.009 (2) |
O11 | 0.0442 (15) | 0.0472 (15) | 0.081 (2) | 0.0035 (12) | 0.0041 (14) | −0.0056 (14) |
O4 | 0.0468 (14) | 0.0273 (11) | 0.0431 (14) | 0.0019 (10) | 0.0070 (11) | −0.0051 (11) |
O13 | 0.0380 (16) | 0.139 (3) | 0.113 (3) | 0.022 (2) | 0.0050 (18) | −0.003 (2) |
C16 | 0.0365 (19) | 0.0275 (16) | 0.0362 (17) | 0.0000 (13) | −0.0041 (15) | 0.0000 (15) |
O12 | 0.0493 (18) | 0.086 (2) | 0.077 (2) | 0.0160 (15) | 0.0005 (16) | −0.0320 (19) |
O7 | 0.087 (2) | 0.115 (3) | 0.0478 (16) | −0.047 (2) | −0.0185 (17) | 0.0250 (19) |
C13 | 0.055 (2) | 0.0370 (19) | 0.069 (3) | −0.0125 (18) | −0.001 (2) | −0.001 (2) |
N5 | 0.0396 (19) | 0.072 (3) | 0.057 (2) | 0.0079 (16) | 0.0062 (16) | 0.0123 (17) |
C15 | 0.036 (2) | 0.0303 (17) | 0.0387 (19) | 0.0008 (14) | −0.0041 (16) | 0.0029 (15) |
C12 | 0.044 (2) | 0.0382 (19) | 0.065 (3) | −0.0093 (16) | 0.007 (2) | 0.0051 (19) |
C17 | 0.060 (2) | 0.0344 (17) | 0.0399 (19) | 0.0043 (17) | 0.0102 (19) | −0.0106 (15) |
C18 | 0.063 (3) | 0.044 (2) | 0.071 (3) | 0.0109 (19) | 0.019 (2) | 0.004 (2) |
C11—C12 | 1.407 (5) | C5—C4 | 1.353 (5) |
C11—C16 | 1.415 (5) | C5—C6 | 1.409 (4) |
C11—C10 | 1.451 (5) | C5—H5 | 0.9300 |
O2—C16 | 1.333 (3) | C4—C3 | 1.383 (5) |
C14—C15 | 1.380 (4) | C4—H4 | 0.9300 |
C14—C13 | 1.389 (5) | C10—H10 | 0.9300 |
C14—H14 | 0.9300 | C19—C20 | 1.492 (5) |
Nd1—O1 | 2.437 (2) | C19—H19A | 0.9700 |
Nd1—O3 | 2.671 (2) | C19—H19B | 0.9700 |
Nd1—O4 | 2.631 (2) | O6—N4 | 1.250 (4) |
Nd1—O5 | 2.536 (3) | O5—N4 | 1.258 (4) |
Nd1—O6 | 2.569 (3) | N4—O7 | 1.229 (4) |
Nd1—O8 | 2.493 (2) | C3—H3 | 0.9300 |
Nd1—O9 | 2.543 (3) | C8—C9 | 1.502 (5) |
Nd1—O11 | 2.521 (3) | C8—H8A | 0.9700 |
Nd1—O12 | 2.578 (3) | C8—H8B | 0.9700 |
O2—Cu1 | 1.904 (2) | C9—H9A | 0.9700 |
O2—Nd1 | 2.396 (2) | C9—H9B | 0.9700 |
Cu1—O1 | 1.900 (2) | C20—H20A | 0.9600 |
Cu1—N1 | 1.906 (3) | C20—H20B | 0.9600 |
Cu1—N2 | 1.911 (3) | C20—H20C | 0.9600 |
O1—C1 | 1.333 (3) | O11—N5 | 1.250 (4) |
N3—O10 | 1.228 (4) | O4—C15 | 1.383 (4) |
N3—O9 | 1.259 (4) | O4—C17 | 1.465 (4) |
N3—O8 | 1.261 (4) | O13—N5 | 1.230 (4) |
N2—C10 | 1.278 (4) | C16—C15 | 1.390 (4) |
N2—C9 | 1.463 (4) | O12—N5 | 1.263 (4) |
N1—C7 | 1.280 (4) | C13—C12 | 1.369 (5) |
N1—C8 | 1.472 (4) | C13—H13 | 0.9300 |
C1—C6 | 1.398 (4) | C12—H12 | 0.9300 |
C1—C2 | 1.402 (5) | C17—C18 | 1.509 (5) |
O3—C2 | 1.387 (4) | C17—H17A | 0.9700 |
O3—C19 | 1.450 (4) | C17—H17B | 0.9700 |
C2—C3 | 1.376 (4) | C18—H18A | 0.9600 |
C7—C6 | 1.452 (5) | C18—H18B | 0.9600 |
C7—H7 | 0.9300 | C18—H18C | 0.9600 |
C12—C11—C16 | 118.8 (3) | O3—C2—C1 | 113.4 (3) |
C12—C11—C10 | 117.8 (3) | N1—C7—C6 | 125.3 (3) |
C16—C11—C10 | 123.3 (3) | N1—C7—H7 | 117.4 |
C16—O2—Cu1 | 124.18 (19) | C6—C7—H7 | 117.4 |
C16—O2—Nd1 | 128.46 (19) | C4—C5—C6 | 121.5 (3) |
Cu1—O2—Nd1 | 106.00 (9) | C4—C5—H5 | 119.3 |
C15—C14—C13 | 119.8 (3) | C6—C5—H5 | 119.3 |
C15—C14—H14 | 120.1 | N3—O8—Nd1 | 98.3 (2) |
C13—C14—H14 | 120.1 | C5—C4—C3 | 120.6 (3) |
O2—Nd1—O1 | 64.25 (7) | C5—C4—H4 | 119.7 |
O2—Nd1—O8 | 121.70 (8) | C3—C4—H4 | 119.7 |
O1—Nd1—O8 | 115.21 (8) | N2—C10—C11 | 124.6 (3) |
O2—Nd1—O11 | 140.06 (8) | N2—C10—H10 | 117.7 |
O1—Nd1—O11 | 113.26 (8) | C11—C10—H10 | 117.7 |
O8—Nd1—O11 | 96.12 (9) | C1—C6—C5 | 118.3 (3) |
O2—Nd1—O5 | 73.72 (8) | C1—C6—C7 | 123.7 (3) |
O1—Nd1—O5 | 113.39 (8) | C5—C6—C7 | 118.0 (3) |
O8—Nd1—O5 | 130.71 (9) | O3—C19—C20 | 112.1 (3) |
O11—Nd1—O5 | 71.65 (8) | O3—C19—H19A | 109.2 |
O2—Nd1—O9 | 81.07 (9) | C20—C19—H19A | 109.2 |
O1—Nd1—O9 | 72.18 (9) | O3—C19—H19B | 109.2 |
O8—Nd1—O9 | 50.01 (8) | C20—C19—H19B | 109.2 |
O11—Nd1—O9 | 138.13 (9) | H19A—C19—H19B | 107.9 |
O5—Nd1—O9 | 147.13 (9) | N4—O6—Nd1 | 95.7 (2) |
O2—Nd1—O6 | 74.05 (8) | N4—O5—Nd1 | 97.1 (2) |
O1—Nd1—O6 | 69.91 (9) | O7—N4—O6 | 122.2 (4) |
O8—Nd1—O6 | 164.25 (9) | O7—N4—O5 | 120.3 (4) |
O11—Nd1—O6 | 68.60 (9) | O6—N4—O5 | 117.6 (3) |
O5—Nd1—O6 | 49.68 (8) | C2—C3—C4 | 119.4 (3) |
O9—Nd1—O6 | 140.84 (9) | C2—C3—H3 | 120.3 |
O2—Nd1—O12 | 133.41 (9) | C4—C3—H3 | 120.3 |
O1—Nd1—O12 | 160.81 (9) | N1—C8—C9 | 107.3 (3) |
O8—Nd1—O12 | 64.99 (9) | N1—C8—H8A | 110.3 |
O11—Nd1—O12 | 49.43 (9) | C9—C8—H8A | 110.3 |
O5—Nd1—O12 | 71.96 (10) | N1—C8—H8B | 110.3 |
O9—Nd1—O12 | 114.04 (9) | C9—C8—H8B | 110.3 |
O6—Nd1—O12 | 105.02 (10) | H8A—C8—H8B | 108.5 |
O2—Nd1—O4 | 60.89 (7) | N2—C9—C8 | 108.7 (3) |
O1—Nd1—O4 | 120.62 (7) | N2—C9—H9A | 110.0 |
O8—Nd1—O4 | 77.98 (8) | C8—C9—H9A | 110.0 |
O11—Nd1—O4 | 122.82 (8) | N2—C9—H9B | 110.0 |
O5—Nd1—O4 | 70.86 (8) | C8—C9—H9B | 110.0 |
O9—Nd1—O4 | 78.62 (8) | H9A—C9—H9B | 108.3 |
O6—Nd1—O4 | 113.02 (8) | C19—C20—H20A | 109.5 |
O12—Nd1—O4 | 78.54 (9) | C19—C20—H20B | 109.5 |
O2—Nd1—O3 | 123.87 (7) | H20A—C20—H20B | 109.5 |
O1—Nd1—O3 | 59.71 (7) | C19—C20—H20C | 109.5 |
O8—Nd1—O3 | 81.25 (8) | H20A—C20—H20C | 109.5 |
O11—Nd1—O3 | 70.21 (8) | H20B—C20—H20C | 109.5 |
O5—Nd1—O3 | 132.22 (8) | N5—O11—Nd1 | 98.8 (2) |
O9—Nd1—O3 | 79.59 (8) | C15—O4—C17 | 118.4 (2) |
O6—Nd1—O3 | 89.63 (8) | C15—O4—Nd1 | 119.02 (18) |
O12—Nd1—O3 | 102.54 (9) | C17—O4—Nd1 | 122.19 (19) |
O4—Nd1—O3 | 156.47 (8) | O2—C16—C15 | 117.0 (3) |
O1—Cu1—O2 | 84.99 (9) | O2—C16—C11 | 123.3 (3) |
O1—Cu1—N1 | 95.44 (11) | C15—C16—C11 | 119.7 (3) |
O2—Cu1—N1 | 177.03 (12) | N5—O12—Nd1 | 95.7 (2) |
O1—Cu1—N2 | 172.22 (12) | C12—C13—C14 | 121.1 (3) |
O2—Cu1—N2 | 94.18 (11) | C12—C13—H13 | 119.4 |
N1—Cu1—N2 | 85.79 (13) | C14—C13—H13 | 119.4 |
C1—O1—Cu1 | 125.4 (2) | O13—N5—O11 | 122.0 (4) |
C1—O1—Nd1 | 129.8 (2) | O13—N5—O12 | 121.9 (4) |
Cu1—O1—Nd1 | 104.61 (8) | O11—N5—O12 | 116.1 (3) |
O10—N3—O9 | 122.4 (3) | C14—C15—O4 | 125.6 (3) |
O10—N3—O8 | 122.3 (3) | C14—C15—C16 | 120.5 (3) |
O9—N3—O8 | 115.3 (3) | O4—C15—C16 | 113.9 (3) |
C10—N2—C9 | 123.6 (3) | C13—C12—C11 | 120.0 (4) |
C10—N2—Cu1 | 125.8 (3) | C13—C12—H12 | 120.0 |
C9—N2—Cu1 | 110.6 (2) | C11—C12—H12 | 120.0 |
N3—O9—Nd1 | 95.9 (2) | O4—C17—C18 | 111.9 (3) |
C7—N1—C8 | 121.4 (3) | O4—C17—H17A | 109.2 |
C7—N1—Cu1 | 125.6 (3) | C18—C17—H17A | 109.2 |
C8—N1—Cu1 | 112.9 (2) | O4—C17—H17B | 109.2 |
O1—C1—C6 | 124.4 (3) | C18—C17—H17B | 109.2 |
O1—C1—C2 | 116.6 (3) | H17A—C17—H17B | 107.9 |
C6—C1—C2 | 119.0 (3) | C17—C18—H18A | 109.5 |
C2—O3—C19 | 117.6 (2) | C17—C18—H18B | 109.5 |
C2—O3—Nd1 | 120.25 (18) | H18A—C18—H18B | 109.5 |
C19—O3—Nd1 | 122.16 (18) | C17—C18—H18C | 109.5 |
C3—C2—O3 | 125.4 (3) | H18A—C18—H18C | 109.5 |
C3—C2—C1 | 121.2 (3) | H18B—C18—H18C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O7i | 0.93 | 2.36 | 3.277 (4) | 168 |
C9—H9A···O7ii | 0.97 | 2.42 | 3.290 (5) | 149 |
C20—H20A···O11 | 0.96 | 2.45 | 3.154 (5) | 130 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [CuNd(C20H22N2O4)(NO3)3] |
Mr | 748.21 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 8.6439 (16), 13.861 (3), 21.135 (4) |
V (Å3) | 2532.4 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.95 |
Crystal size (mm) | 0.22 × 0.17 × 0.08 |
Data collection | |
Diffractometer | Bruker APEX II area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.570, 0.794 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19224, 6179, 4830 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.051, 1.01 |
No. of reflections | 6179 |
No. of parameters | 363 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.85 |
Absolute structure | Flack (1983), 2611 Friedel pairs |
Absolute structure parameter | −0.008 (10) |
Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), APEX2 and publCIF (Westrip, 2007).
Nd1—O1 | 2.437 (2) | Nd1—O11 | 2.521 (3) |
Nd1—O3 | 2.671 (2) | Nd1—O12 | 2.578 (3) |
Nd1—O4 | 2.631 (2) | O2—Cu1 | 1.904 (2) |
Nd1—O5 | 2.536 (3) | O2—Nd1 | 2.396 (2) |
Nd1—O6 | 2.569 (3) | Cu1—O1 | 1.900 (2) |
Nd1—O8 | 2.493 (2) | Cu1—N1 | 1.906 (3) |
Nd1—O9 | 2.543 (3) | Cu1—N2 | 1.911 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···O7i | 0.93 | 2.36 | 3.277 (4) | 168.3 |
C9—H9A···O7ii | 0.97 | 2.42 | 3.290 (5) | 148.8 |
C20—H20A···O11 | 0.96 | 2.45 | 3.154 (5) | 130.4 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (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 CuII—NdIII complex with salen-type Schiff base N,N'-bis(3-ethoxysalicylidene) ethylenediamine(H2L).
Complex (I) crystallizes in the space group P212121, with copper and neodymium doubly bridged by two phenolate O atoms provided by a salen-type Schiff base ligand. The inner salen-type cavity is occupied by copper(II), while neodymium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand. The dihedral angles between the mean planes of Cu1/O1/O2 and Nd1/O1/O2 is 3.63 (14)° suggesting that the bridging moiety is almost planar; the deviation of atoms from the least squares Cu1/O1/O2/Nd1 plane being -0.0308 (3)Å for Cu, -0.0211 (2)Å for Nd, 0.0256 (3)Å for O1 and 0.0262 (3)Å for O2.
The neodymium(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 neodymium to complete the decacoordination. The three kinds of Nd—O bond distances are significantly different, the shortest being the Nd—O(phenolate) and longest being the Nd—O(ethoxy) separations.
The coordination of copper(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 0.0887 (2) Å, while Cu1 is 0.0395 (3)Å above this square plane.
Adjacent molecules are held together by weak interactions (O13···Cu1=3.169 (3) Å, C7—H7···O7i=3.277 (4) and C9—H9A···O7ii=3.290 (5); symmetry codes:(i)-x + 1, y - 1/2, 3/2 - z; (ii)1 + x, y, z). these link the molecules into a two-dimensional zigzag sheet(Fig 2).