Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037130/hg2269sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037130/hg2269Isup2.hkl |
CCDC reference: 1101490
H2L was prepared by the 2:1 condensation of 3-methoxysalicylaldehyde and ethylenediamine in methanol. Complex (I) was obtained by the treatment of nickel(II) acetate tetrahydrate (0.217 g, 1 mmol) with H2L(0.328 g, 1 mmol) in methanol solution (80 ml) under reflux for 3 h and then for another 3 h after the addition of samarium(III) nitrate hexahydrate (0.444 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 C19H22N5NiO14Sm: C 30.29, H 2.94, N 9.29, Ni 7.79, Sm 19.96%; found: C 30.01, H 2.98, N 9.40, Ni 7.78, Sm 19.68%. IR(KBr, cm-1): 1640(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 methyl group of methanol was constrainted as idealized non-rotating CH3 group. The hydroxyl H atom, H14A, was located in a difference Fourier map and refined with the O14—H14A restrained to 0.9 Å.
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; Sui et al., 2007), we report here the synthesis and X-ray crystal structure analysis of the title complex, (I), a new NiII—SmIII complex with salen-type Schiff base N,N'-bis(3-ethoxysalicylidene) ethylenediamine (H2L).
Complex (I) crystallizes in the space group P21/n, with nickel and samarium triply bridged by two phenolate O atoms provided by a salen-type Schiff base ligand and one nitrate. The inner salen-type cavity is occupied by nickel(II), while saramium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand.
The SmIII center has a decacoordination environment of O atoms, involving the phenolate O atoms, two methoxy O atoms, one methanol O atom, two O atoms from two nitrates and one from the bridging nitrate. The five kinds of Sm—O bond distances are significantly different, the longest being the Sm—O(methoxy) separations and the shortest being the Sm—O(phenolate) and Sm—O8(bridging nitrate).
The NiII is in a square-pyramidal geometry and is five-coordinated by two imine N atoms, two phenolate O atoms and one of the bridging nitrate O atoms. The Ni atom is 0.5860 (2)Å below the mean N2O2 plane with an average deviation from the plane of 0.0961 (3) Å, which construct the bottom of square-pyramid. The Ni—O9 (bridging nitrate) separation is 2.003 (3)Å and the angles of this Ni—O vector with the Ni—N or Ni—O bonds lie between 103.3 (5)° and 115.6 (6)°, which suggesting that the NiII is in a slightly distorted square-pyramidal conformation.
Adjacent molecules are held together by strong interactions (O14—H14A···O9i=2.691 (4); symmetry codes:(i)3/2 - x, 1/2 + y, 1/2 - z) and weak interactions (C7—H7···O11ii=3.379 (5) and C5—H5···O5ii=3.432 (6); symmetry codes: (ii)1/2 + x, 1/2 - y, 1/2 + z). these link the molecules into a two-dimensional layer structure (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, 2007).
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 c axis; hydrogen bonds are shown as dashed lines. |
[NiSm(C18H18N2O4)(NO3)3(CH4O)] | F(000) = 1492 |
Mr = 753.48 | Dx = 1.883 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 6618 reflections |
a = 9.604 (2) Å | θ = 1.8–28.3° |
b = 13.805 (3) Å | µ = 2.97 mm−1 |
c = 20.049 (4) Å | T = 293 K |
β = 91.617 (3)° | Block, red |
V = 2657.3 (10) Å3 | 0.25 × 0.24 × 0.24 mm |
Z = 4 |
Bruker APEX II area-detector diffractometer | 6376 independent reflections |
Radiation source: fine-focus sealed tube | 5577 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
φ and ω scans | θmax = 28.3°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −12→12 |
Tmin = 0.524, Tmax = 0.540 | k = −18→18 |
19575 measured reflections | l = −26→26 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.124 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0827P)2 + 6.7464P] where P = (Fo2 + 2Fc2)/3 |
6376 reflections | (Δ/σ)max = 0.001 |
367 parameters | Δρmax = 2.54 e Å−3 |
1 restraint | Δρmin = −1.03 e Å−3 |
[NiSm(C18H18N2O4)(NO3)3(CH4O)] | V = 2657.3 (10) Å3 |
Mr = 753.48 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.604 (2) Å | µ = 2.97 mm−1 |
b = 13.805 (3) Å | T = 293 K |
c = 20.049 (4) Å | 0.25 × 0.24 × 0.24 mm |
β = 91.617 (3)° |
Bruker APEX II area-detector diffractometer | 6376 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 5577 reflections with I > 2σ(I) |
Tmin = 0.524, Tmax = 0.540 | Rint = 0.018 |
19575 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 1 restraint |
wR(F2) = 0.124 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 2.54 e Å−3 |
6376 reflections | Δρmin = −1.03 e Å−3 |
367 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 | ||
Sm1 | 0.72165 (2) | 0.221608 (16) | 0.113907 (10) | 0.02869 (9) | |
Ni1 | 0.68895 (5) | 0.12834 (4) | 0.27322 (2) | 0.02415 (12) | |
O1 | 0.8237 (3) | 0.2178 (2) | 0.22809 (14) | 0.0299 (6) | |
O5 | 0.7362 (4) | 0.1365 (3) | 0.00081 (16) | 0.0440 (8) | |
O2 | 0.5578 (3) | 0.1751 (2) | 0.19989 (15) | 0.0333 (6) | |
O3 | 0.9687 (3) | 0.3197 (3) | 0.14804 (15) | 0.0358 (7) | |
C1 | 0.9349 (4) | 0.2603 (3) | 0.2555 (2) | 0.0284 (8) | |
O6 | 0.9352 (3) | 0.1682 (3) | 0.04734 (18) | 0.0438 (8) | |
O4 | 0.4592 (3) | 0.1456 (3) | 0.08019 (17) | 0.0416 (8) | |
N2 | 0.5224 (5) | 0.1311 (3) | 0.3371 (2) | 0.0417 (9) | |
C6 | 0.9773 (5) | 0.2532 (4) | 0.3236 (2) | 0.0357 (9) | |
C11 | 0.3436 (5) | 0.1270 (3) | 0.2512 (3) | 0.0394 (10) | |
N4 | 0.8677 (5) | 0.1335 (4) | −0.0018 (2) | 0.0469 (10) | |
C3 | 1.1335 (5) | 0.3664 (4) | 0.2381 (3) | 0.0453 (12) | |
H3 | 1.1857 | 0.4040 | 0.2096 | 0.054* | |
C5 | 1.0959 (6) | 0.3041 (4) | 0.3469 (3) | 0.0482 (13) | |
H5 | 1.1225 | 0.3002 | 0.3918 | 0.058* | |
C2 | 1.0163 (4) | 0.3176 (3) | 0.2138 (2) | 0.0327 (9) | |
C7 | 0.9013 (6) | 0.1986 (4) | 0.3737 (2) | 0.0398 (11) | |
H7 | 0.9339 | 0.2020 | 0.4178 | 0.048* | |
C10 | 0.3940 (5) | 0.1308 (4) | 0.3192 (3) | 0.0437 (11) | |
H10 | 0.3285 | 0.1332 | 0.3525 | 0.052* | |
C12 | 0.2020 (5) | 0.1021 (4) | 0.2395 (3) | 0.0502 (14) | |
H12 | 0.1456 | 0.0919 | 0.2758 | 0.060* | |
C17 | 0.4074 (6) | 0.1210 (5) | 0.0148 (3) | 0.0565 (15) | |
H17A | 0.3856 | 0.0531 | 0.0131 | 0.085* | |
H17B | 0.4769 | 0.1353 | −0.0173 | 0.085* | |
H17C | 0.3249 | 0.1580 | 0.0045 | 0.085* | |
C4 | 1.1722 (6) | 0.3587 (4) | 0.3050 (3) | 0.0523 (14) | |
H4 | 1.2510 | 0.3910 | 0.3213 | 0.063* | |
C18 | 1.0641 (6) | 0.3586 (5) | 0.1011 (3) | 0.0491 (13) | |
H18A | 1.0714 | 0.4274 | 0.1071 | 0.074* | |
H18B | 1.0306 | 0.3449 | 0.0566 | 0.074* | |
H18C | 1.1540 | 0.3294 | 0.1083 | 0.074* | |
O7 | 0.9247 (6) | 0.0977 (6) | −0.0484 (3) | 0.103 (2) | |
O14 | 0.6425 (4) | 0.3820 (2) | 0.16112 (17) | 0.0381 (7) | |
O11 | 0.5703 (4) | 0.3179 (3) | 0.02337 (17) | 0.0428 (8) | |
O9 | 0.7472 (3) | −0.0033 (2) | 0.24259 (15) | 0.0364 (7) | |
O8 | 0.7648 (4) | 0.0492 (3) | 0.13872 (16) | 0.0432 (8) | |
O12 | 0.7876 (4) | 0.3554 (3) | 0.02657 (18) | 0.0457 (8) | |
N1 | 0.7946 (5) | 0.1470 (3) | 0.36130 (18) | 0.0399 (9) | |
N3 | 0.6690 (5) | 0.3680 (3) | 0.00024 (19) | 0.0399 (9) | |
N5 | 0.7780 (4) | −0.0145 (3) | 0.1815 (2) | 0.0425 (9) | |
C16 | 0.4261 (4) | 0.1447 (3) | 0.1950 (2) | 0.0322 (9) | |
C15 | 0.3665 (4) | 0.1312 (3) | 0.1316 (3) | 0.0364 (10) | |
C14 | 0.2282 (5) | 0.1055 (4) | 0.1216 (3) | 0.0472 (13) | |
H14 | 0.1909 | 0.0970 | 0.0787 | 0.057* | |
C13 | 0.1461 (5) | 0.0928 (4) | 0.1768 (4) | 0.0566 (16) | |
H13 | 0.0522 | 0.0777 | 0.1709 | 0.068* | |
C9 | 0.5660 (7) | 0.1387 (5) | 0.4080 (2) | 0.0524 (14) | |
H9A | 0.5053 | 0.0998 | 0.4350 | 0.063* | |
H9B | 0.5597 | 0.2055 | 0.4226 | 0.063* | |
C8 | 0.7147 (7) | 0.1033 (4) | 0.4163 (2) | 0.0510 (13) | |
H8A | 0.7540 | 0.1232 | 0.4592 | 0.061* | |
H8B | 0.7179 | 0.0332 | 0.4137 | 0.061* | |
C19 | 0.5000 (6) | 0.4105 (5) | 0.1618 (4) | 0.0596 (16) | |
H19A | 0.4732 | 0.4378 | 0.1193 | 0.071* | |
H19B | 0.4876 | 0.4578 | 0.1962 | 0.071* | |
H19C | 0.4431 | 0.3549 | 0.1704 | 0.071* | |
O13 | 0.6481 (6) | 0.4245 (4) | −0.0455 (2) | 0.0724 (14) | |
O10 | 0.8398 (7) | −0.1098 (4) | 0.1618 (3) | 0.0878 (17) | |
H14A | 0.692 (5) | 0.418 (4) | 0.190 (2) | 0.051 (17)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sm1 | 0.03071 (13) | 0.03499 (14) | 0.02022 (12) | −0.00078 (8) | −0.00193 (8) | 0.00131 (7) |
Ni1 | 0.0302 (2) | 0.0283 (3) | 0.0140 (2) | 0.00120 (19) | 0.00213 (18) | 0.00104 (17) |
O1 | 0.0287 (14) | 0.0416 (17) | 0.0191 (13) | −0.0049 (11) | −0.0057 (11) | 0.0014 (11) |
O5 | 0.0440 (18) | 0.063 (2) | 0.0245 (15) | −0.0011 (16) | −0.0026 (13) | −0.0083 (15) |
O2 | 0.0250 (13) | 0.0447 (18) | 0.0303 (15) | −0.0056 (13) | 0.0021 (11) | 0.0071 (13) |
O3 | 0.0308 (14) | 0.0480 (19) | 0.0282 (15) | −0.0093 (14) | −0.0035 (12) | 0.0056 (13) |
C1 | 0.0271 (18) | 0.034 (2) | 0.0237 (18) | 0.0030 (16) | −0.0047 (15) | −0.0061 (16) |
O6 | 0.0338 (16) | 0.056 (2) | 0.0421 (19) | 0.0026 (15) | −0.0003 (14) | −0.0086 (16) |
O4 | 0.0329 (15) | 0.058 (2) | 0.0328 (16) | −0.0091 (15) | −0.0084 (13) | 0.0064 (15) |
N2 | 0.053 (2) | 0.046 (2) | 0.0271 (18) | 0.0022 (19) | 0.0142 (17) | 0.0003 (16) |
C6 | 0.035 (2) | 0.048 (2) | 0.024 (2) | 0.004 (2) | −0.0086 (17) | −0.0068 (19) |
C11 | 0.033 (2) | 0.033 (2) | 0.053 (3) | 0.0020 (18) | 0.015 (2) | 0.002 (2) |
N4 | 0.050 (2) | 0.055 (3) | 0.036 (2) | −0.001 (2) | 0.0101 (19) | −0.0092 (19) |
C3 | 0.037 (2) | 0.046 (3) | 0.053 (3) | −0.008 (2) | −0.007 (2) | −0.008 (2) |
C5 | 0.046 (3) | 0.061 (3) | 0.037 (3) | 0.002 (3) | −0.018 (2) | −0.016 (2) |
C2 | 0.032 (2) | 0.037 (2) | 0.029 (2) | 0.0011 (17) | −0.0048 (16) | −0.0045 (17) |
C7 | 0.051 (3) | 0.050 (3) | 0.0179 (18) | 0.011 (2) | −0.0103 (18) | −0.0029 (18) |
C10 | 0.044 (3) | 0.039 (3) | 0.050 (3) | −0.001 (2) | 0.025 (2) | 0.003 (2) |
C12 | 0.032 (2) | 0.040 (3) | 0.080 (4) | 0.000 (2) | 0.025 (3) | 0.004 (3) |
C17 | 0.054 (3) | 0.073 (4) | 0.042 (3) | −0.013 (3) | −0.017 (2) | 0.000 (3) |
C4 | 0.043 (3) | 0.060 (3) | 0.052 (3) | −0.010 (2) | −0.016 (2) | −0.018 (3) |
C18 | 0.044 (3) | 0.063 (3) | 0.040 (3) | −0.016 (2) | 0.003 (2) | 0.008 (2) |
O7 | 0.083 (4) | 0.157 (6) | 0.069 (3) | −0.001 (4) | 0.033 (3) | −0.061 (4) |
O14 | 0.0402 (17) | 0.0355 (17) | 0.0384 (17) | 0.0038 (14) | −0.0019 (14) | −0.0097 (14) |
O11 | 0.0460 (18) | 0.049 (2) | 0.0326 (16) | −0.0007 (16) | −0.0131 (14) | 0.0041 (15) |
O9 | 0.0513 (19) | 0.0316 (15) | 0.0264 (14) | 0.0037 (13) | 0.0031 (13) | 0.0027 (12) |
O8 | 0.067 (2) | 0.0351 (17) | 0.0281 (15) | 0.0040 (16) | 0.0016 (15) | 0.0017 (13) |
O12 | 0.0441 (18) | 0.052 (2) | 0.0405 (18) | −0.0019 (16) | −0.0026 (15) | 0.0127 (16) |
N1 | 0.059 (3) | 0.043 (2) | 0.0177 (16) | 0.0049 (19) | −0.0009 (16) | 0.0040 (15) |
N3 | 0.055 (2) | 0.039 (2) | 0.0259 (17) | 0.0008 (18) | −0.0054 (17) | 0.0031 (15) |
N5 | 0.046 (2) | 0.039 (2) | 0.043 (2) | −0.0066 (18) | 0.0049 (18) | −0.0002 (18) |
C16 | 0.0237 (18) | 0.030 (2) | 0.043 (2) | 0.0001 (15) | 0.0066 (17) | 0.0062 (18) |
C15 | 0.0259 (19) | 0.035 (2) | 0.048 (3) | −0.0022 (16) | −0.0030 (18) | 0.0068 (19) |
C14 | 0.027 (2) | 0.043 (3) | 0.071 (4) | −0.0040 (18) | −0.008 (2) | 0.004 (2) |
C13 | 0.025 (2) | 0.045 (3) | 0.100 (5) | −0.004 (2) | 0.006 (3) | 0.005 (3) |
C9 | 0.076 (4) | 0.057 (3) | 0.025 (2) | −0.007 (3) | 0.020 (2) | −0.004 (2) |
C8 | 0.081 (4) | 0.051 (3) | 0.021 (2) | −0.003 (3) | 0.006 (2) | 0.008 (2) |
C19 | 0.045 (3) | 0.066 (4) | 0.068 (4) | 0.018 (3) | 0.000 (3) | −0.015 (3) |
O13 | 0.094 (3) | 0.070 (3) | 0.052 (2) | −0.006 (3) | −0.020 (2) | 0.035 (2) |
O10 | 0.125 (5) | 0.061 (3) | 0.079 (4) | 0.012 (3) | 0.029 (3) | 0.001 (3) |
Sm1—O1 | 2.465 (3) | C5—C4 | 1.358 (9) |
Sm1—O2 | 2.452 (3) | C5—H5 | 0.9300 |
Sm1—O3 | 2.801 (3) | C7—N1 | 1.267 (7) |
Sm1—O4 | 2.795 (3) | C7—H7 | 0.9300 |
Sm1—O5 | 2.561 (3) | C10—H10 | 0.9300 |
Sm1—O6 | 2.586 (3) | C12—C13 | 1.359 (9) |
Sm1—O8 | 2.465 (3) | C12—H12 | 0.9300 |
Sm1—O11 | 2.651 (3) | C17—H17A | 0.9600 |
Sm1—O12 | 2.635 (4) | C17—H17B | 0.9600 |
Sm1—O14 | 2.533 (3) | C17—H17C | 0.9600 |
Ni1—N1 | 2.028 (4) | C4—H4 | 0.9300 |
Ni1—N2 | 2.078 (4) | C18—H18A | 0.9600 |
Ni1—O1 | 2.021 (3) | C18—H18B | 0.9600 |
Ni1—O2 | 2.015 (3) | C18—H18C | 0.9600 |
Ni1—O9 | 2.003 (3) | O14—C19 | 1.424 (6) |
O1—C1 | 1.324 (5) | O14—H14A | 0.89 (2) |
O5—N4 | 1.266 (6) | O11—N3 | 1.271 (6) |
O2—C16 | 1.333 (5) | O9—N5 | 1.277 (5) |
O3—C2 | 1.383 (5) | O8—N5 | 1.233 (5) |
O3—C18 | 1.435 (6) | O12—N3 | 1.254 (5) |
C1—C2 | 1.405 (6) | N1—C8 | 1.488 (6) |
C1—C6 | 1.417 (6) | N3—O13 | 1.216 (5) |
O6—N4 | 1.259 (6) | N5—O10 | 1.501 (7) |
O4—C15 | 1.395 (6) | C16—C15 | 1.392 (7) |
O4—C17 | 1.431 (6) | C15—C14 | 1.384 (6) |
N2—C10 | 1.275 (7) | C14—C13 | 1.388 (9) |
N2—C9 | 1.474 (6) | C14—H14 | 0.9300 |
C6—C5 | 1.407 (7) | C13—H13 | 0.9300 |
C6—C7 | 1.468 (7) | C9—C8 | 1.514 (9) |
C11—C16 | 1.416 (6) | C9—H9A | 0.9700 |
C11—C12 | 1.416 (7) | C9—H9B | 0.9700 |
C11—C10 | 1.436 (8) | C8—H8A | 0.9700 |
N4—O7 | 1.202 (6) | C8—H8B | 0.9700 |
C3—C4 | 1.387 (8) | C19—H19A | 0.9600 |
C3—C2 | 1.387 (6) | C19—H19B | 0.9600 |
C3—H3 | 0.9300 | C19—H19C | 0.9600 |
O2—Sm1—O8 | 73.31 (11) | O7—N4—O5 | 121.5 (5) |
O2—Sm1—O1 | 65.66 (10) | O6—N4—O5 | 116.6 (4) |
O8—Sm1—O1 | 74.45 (11) | C4—C3—C2 | 119.7 (5) |
O2—Sm1—O14 | 76.16 (11) | C4—C3—H3 | 120.1 |
O8—Sm1—O14 | 145.02 (11) | C2—C3—H3 | 120.1 |
O1—Sm1—O14 | 77.71 (10) | C4—C5—C6 | 121.2 (5) |
O2—Sm1—O5 | 123.67 (11) | C4—C5—H5 | 119.4 |
O8—Sm1—O5 | 73.88 (12) | C6—C5—H5 | 119.4 |
O1—Sm1—O5 | 141.46 (11) | O3—C2—C3 | 124.6 (4) |
O14—Sm1—O5 | 139.15 (12) | O3—C2—C1 | 113.8 (4) |
O2—Sm1—O6 | 145.31 (12) | C3—C2—C1 | 121.6 (4) |
O8—Sm1—O6 | 72.39 (12) | N1—C7—C6 | 124.7 (4) |
O1—Sm1—O6 | 99.96 (11) | N1—C7—H7 | 117.6 |
O14—Sm1—O6 | 133.86 (12) | C6—C7—H7 | 117.6 |
O5—Sm1—O6 | 49.33 (11) | N2—C10—C11 | 124.4 (4) |
O2—Sm1—O12 | 145.26 (11) | N2—C10—H10 | 117.8 |
O8—Sm1—O12 | 140.28 (12) | C11—C10—H10 | 117.8 |
O1—Sm1—O12 | 122.36 (11) | C13—C12—C11 | 121.9 (5) |
O14—Sm1—O12 | 73.49 (12) | C13—C12—H12 | 119.1 |
O5—Sm1—O12 | 73.34 (12) | C11—C12—H12 | 119.1 |
O6—Sm1—O12 | 69.39 (12) | O4—C17—H17A | 109.5 |
O2—Sm1—O11 | 105.22 (11) | O4—C17—H17B | 109.5 |
O8—Sm1—O11 | 135.12 (12) | H17A—C17—H17B | 109.5 |
O1—Sm1—O11 | 147.40 (11) | O4—C17—H17C | 109.5 |
O14—Sm1—O11 | 69.69 (11) | H17A—C17—H17C | 109.5 |
O5—Sm1—O11 | 70.53 (12) | H17B—C17—H17C | 109.5 |
O6—Sm1—O11 | 102.54 (12) | C5—C4—C3 | 120.4 (5) |
O12—Sm1—O11 | 47.97 (11) | C5—C4—H4 | 119.8 |
O2—Sm1—O4 | 58.64 (10) | C3—C4—H4 | 119.8 |
O8—Sm1—O4 | 80.30 (12) | O3—C18—H18A | 109.5 |
O1—Sm1—O4 | 123.28 (10) | O3—C18—H18B | 109.5 |
O14—Sm1—O4 | 98.07 (11) | H18A—C18—H18B | 109.5 |
O5—Sm1—O4 | 71.65 (11) | O3—C18—H18C | 109.5 |
O6—Sm1—O4 | 119.41 (11) | H18A—C18—H18C | 109.5 |
O12—Sm1—O4 | 109.54 (11) | H18B—C18—H18C | 109.5 |
O11—Sm1—O4 | 63.23 (11) | C19—O14—Sm1 | 122.9 (3) |
O2—Sm1—O3 | 120.73 (10) | C19—O14—H14A | 110 (4) |
O8—Sm1—O3 | 106.34 (12) | Sm1—O14—H14A | 125 (4) |
O1—Sm1—O3 | 58.09 (9) | N3—O11—Sm1 | 97.1 (3) |
O14—Sm1—O3 | 75.35 (11) | N5—O9—Ni1 | 118.6 (3) |
O5—Sm1—O3 | 111.78 (11) | N5—O8—Sm1 | 147.5 (3) |
O6—Sm1—O3 | 65.48 (11) | N3—O12—Sm1 | 98.3 (3) |
O12—Sm1—O3 | 66.76 (10) | C7—N1—C8 | 120.9 (4) |
O11—Sm1—O3 | 111.66 (10) | C7—N1—Ni1 | 128.6 (3) |
O4—Sm1—O3 | 173.05 (11) | C8—N1—Ni1 | 109.8 (3) |
O9—Ni1—O2 | 103.96 (13) | O13—N3—O12 | 122.3 (5) |
O9—Ni1—O1 | 103.26 (13) | O13—N3—O11 | 121.0 (5) |
O2—Ni1—O1 | 82.67 (12) | O12—N3—O11 | 116.7 (4) |
O9—Ni1—N1 | 104.17 (15) | O8—N5—O9 | 124.0 (4) |
O2—Ni1—N1 | 151.86 (16) | O8—N5—O10 | 118.4 (4) |
O1—Ni1—N1 | 90.09 (15) | O9—N5—O10 | 117.5 (4) |
O9—Ni1—N2 | 115.62 (15) | O2—C16—C15 | 118.3 (4) |
O2—Ni1—N2 | 88.16 (15) | O2—C16—C11 | 123.1 (4) |
O1—Ni1—N2 | 141.12 (15) | C15—C16—C11 | 118.5 (4) |
N1—Ni1—N2 | 80.53 (18) | C14—C15—C16 | 122.4 (5) |
C1—O1—Ni1 | 127.2 (3) | C14—C15—O4 | 124.0 (5) |
C1—O1—Sm1 | 132.1 (3) | C16—C15—O4 | 113.6 (4) |
Ni1—O1—Sm1 | 100.72 (12) | C15—C14—C13 | 118.7 (5) |
N4—O5—Sm1 | 97.5 (3) | C15—C14—H14 | 120.6 |
C16—O2—Ni1 | 121.7 (3) | C13—C14—H14 | 120.6 |
C16—O2—Sm1 | 131.1 (3) | C12—C13—C14 | 120.5 (5) |
Ni1—O2—Sm1 | 101.33 (11) | C12—C13—H13 | 119.7 |
C2—O3—C18 | 115.6 (4) | C14—C13—H13 | 119.7 |
C2—O3—Sm1 | 118.5 (3) | N2—C9—C8 | 108.9 (4) |
C18—O3—Sm1 | 124.9 (3) | N2—C9—H9A | 109.9 |
O1—C1—C2 | 117.3 (4) | C8—C9—H9A | 109.9 |
O1—C1—C6 | 125.1 (4) | N2—C9—H9B | 109.9 |
C2—C1—C6 | 117.5 (4) | C8—C9—H9B | 109.9 |
N4—O6—Sm1 | 96.5 (3) | H9A—C9—H9B | 108.3 |
C15—O4—C17 | 115.5 (4) | N1—C8—C9 | 107.0 (4) |
C15—O4—Sm1 | 117.7 (3) | N1—C8—H8A | 110.3 |
C17—O4—Sm1 | 126.8 (3) | C9—C8—H8A | 110.3 |
C10—N2—C9 | 121.2 (4) | N1—C8—H8B | 110.3 |
C10—N2—Ni1 | 125.6 (3) | C9—C8—H8B | 110.3 |
C9—N2—Ni1 | 113.1 (3) | H8A—C8—H8B | 108.6 |
C5—C6—C1 | 119.6 (5) | O14—C19—H19A | 109.5 |
C5—C6—C7 | 116.3 (4) | O14—C19—H19B | 109.5 |
C1—C6—C7 | 124.1 (4) | H19A—C19—H19B | 109.5 |
C16—C11—C12 | 117.9 (5) | O14—C19—H19C | 109.5 |
C16—C11—C10 | 124.6 (4) | H19A—C19—H19C | 109.5 |
C12—C11—C10 | 117.5 (5) | H19B—C19—H19C | 109.5 |
O7—N4—O6 | 121.9 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O14—H14A···O9i | 0.89 (2) | 1.82 (2) | 2.691 (4) | 166 (6) |
C5—H5···O5ii | 0.93 | 2.57 | 3.432 (6) | 155 |
C7—H7···O11ii | 0.93 | 2.47 | 3.379 (5) | 164 |
C17—H17B···O5 | 0.96 | 2.51 | 3.186 (7) | 128 |
C18—H18B···O12 | 0.96 | 2.40 | 3.011 (7) | 121 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [NiSm(C18H18N2O4)(NO3)3(CH4O)] |
Mr | 753.48 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.604 (2), 13.805 (3), 20.049 (4) |
β (°) | 91.617 (3) |
V (Å3) | 2657.3 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.97 |
Crystal size (mm) | 0.25 × 0.24 × 0.24 |
Data collection | |
Diffractometer | Bruker APEX II area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.524, 0.540 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19575, 6376, 5577 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.668 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.124, 1.01 |
No. of reflections | 6376 |
No. of parameters | 367 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 2.54, −1.03 |
Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), APEX2 and publCIF (Westrip, 2007).
D—H···A | D—H | H···A | D···A | D—H···A |
O14—H14A···O9i | 0.89 (2) | 1.82 (2) | 2.691 (4) | 166 (6) |
C5—H5···O5ii | 0.93 | 2.57 | 3.432 (6) | 154.5 |
C7—H7···O11ii | 0.93 | 2.47 | 3.379 (5) | 164.4 |
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x+1/2, −y+1/2, z+1/2. |
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; Sui et al., 2007), we report here the synthesis and X-ray crystal structure analysis of the title complex, (I), a new NiII—SmIII complex with salen-type Schiff base N,N'-bis(3-ethoxysalicylidene) ethylenediamine (H2L).
Complex (I) crystallizes in the space group P21/n, with nickel and samarium triply bridged by two phenolate O atoms provided by a salen-type Schiff base ligand and one nitrate. The inner salen-type cavity is occupied by nickel(II), while saramium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand.
The SmIII center has a decacoordination environment of O atoms, involving the phenolate O atoms, two methoxy O atoms, one methanol O atom, two O atoms from two nitrates and one from the bridging nitrate. The five kinds of Sm—O bond distances are significantly different, the longest being the Sm—O(methoxy) separations and the shortest being the Sm—O(phenolate) and Sm—O8(bridging nitrate).
The NiII is in a square-pyramidal geometry and is five-coordinated by two imine N atoms, two phenolate O atoms and one of the bridging nitrate O atoms. The Ni atom is 0.5860 (2)Å below the mean N2O2 plane with an average deviation from the plane of 0.0961 (3) Å, which construct the bottom of square-pyramid. The Ni—O9 (bridging nitrate) separation is 2.003 (3)Å and the angles of this Ni—O vector with the Ni—N or Ni—O bonds lie between 103.3 (5)° and 115.6 (6)°, which suggesting that the NiII is in a slightly distorted square-pyramidal conformation.
Adjacent molecules are held together by strong interactions (O14—H14A···O9i=2.691 (4); symmetry codes:(i)3/2 - x, 1/2 + y, 1/2 - z) and weak interactions (C7—H7···O11ii=3.379 (5) and C5—H5···O5ii=3.432 (6); symmetry codes: (ii)1/2 + x, 1/2 - y, 1/2 + z). these link the molecules into a two-dimensional layer structure (Fig 2).