Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033314/hg2256sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033314/hg2256Isup2.hkl |
CCDC reference: 1277975
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.025
- wR factor = 0.072
- Data-to-parameter ratio = 17.4
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT073_ALERT_1_A H-atoms ref, but _hydrogen_treatment reported as constr
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 3.14 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for O12 - N5 .. 5.84 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O3 .. 7.27 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O4 .. 5.70 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O8 .. 8.89 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O9 .. 6.18 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ce1 - O11 .. 6.25 su 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
Alert level G 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) 3.18 PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1 (2) 2.12 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 5
1 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 12 ALERT level C = Check and explain 5 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 10 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 1 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-methoxysalicylaldehyde and ethylenediamine in methanol. Complex (I) was obtained by the treatment of zinc(II) acetate dihydrate (0.188 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 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 C19H22CeN5O14Zn: C 30.43, H 2.96, Ce 18.68, N 9.34,Zn 8.72%; found: C 31.01, H 2.90, Ce 18.60, N 9.38, Zn 8.68%. IR (KBr, cm-1): 1641(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 no-rotating CH3 group.
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 ZnII–CeIII complex with salen-type Schiff base N,N'-bis(3-ethoxysalicylidene)ethylenediamine(H2L).
Complex (I) crystallizes in the space group P21/n, with zinc and cerium 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 zinc(II), while cerium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand.
The cerium(III) center in (I) has a decacoordination environment of O atoms. In addition to the phenolate ligands, two methoxy O atoms and one methanol O atoms coordinate to this metal center, two O atoms each from the two nitrates and one of the bridged nitrate O atoms chelate to cerium to complete the decacoordination. The five kinds of Ce—O bond distances are significantly different, the longest being the Ce—O(methoxy) separations and the shortest being the Ce—O(phenolate) and Ce—O11(bridged nitrate).
The zinc(II) is in a square-pyramidal geometry and is five-coordinated by two imine N atoms, two phenolate O atoms and one of the bridged nitrate O atoms. The Zn atom is 0.5822 (2)Å above the mean N2O2 plane with an average deviation from the plane of 0.0961 (3) Å, which construct the bottom of square-pyramid. The Zn—O13(nitrate, bridged) separation is 2.0047 (19)Å and the angles of this Zn—O vector with the Zn—N or Zn—O bonds lie between 103.22 (8)° and 115.52 (9)°, which suggesting that the zinc(II) is in a slightly distorted square-pyramidal conformation.
Adjacent molecules are held together by strong interactions (O14—H14A···O13i = 2.689 (3); symmetry codes:(i) 3/2 - x, y - 1/2, 1/2 - z) and weak interactions (C7—H7···O8ii = 3.393 (3) and C5—H5···O3ii = 3.428 (4); 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. |
[CeZn(C18H18N2O4)(CH4O)(NO3)3] | F(000) = 1484 |
Mr = 749.91 | Dx = 1.876 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 19675 reflections |
a = 9.6011 (4) Å | θ = 1.8–28.3° |
b = 13.8046 (5) Å | µ = 2.67 mm−1 |
c = 20.0375 (7) Å | T = 293 K |
β = 91.629 (1)° | Block, yellow |
V = 2654.68 (17) Å3 | 0.28 × 0.20 × 0.13 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 6372 independent reflections |
Radiation source: fine-focus sealed tube | 5465 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
Detector resolution: 0 pixels mm-1 | θmax = 28.3°, θmin = 1.8° |
φ and ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −18→18 |
Tmin = 0.527, Tmax = 0.723 | l = −26→26 |
19675 measured reflections |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0469P)2 + 0.8352P] where P = (Fo2 + 2Fc2)/3 |
6372 reflections | (Δ/σ)max = 0.001 |
367 parameters | Δρmax = 0.74 e Å−3 |
5 restraints | Δρmin = −0.72 e Å−3 |
[CeZn(C18H18N2O4)(CH4O)(NO3)3] | V = 2654.68 (17) Å3 |
Mr = 749.91 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.6011 (4) Å | µ = 2.67 mm−1 |
b = 13.8046 (5) Å | T = 293 K |
c = 20.0375 (7) Å | 0.28 × 0.20 × 0.13 mm |
β = 91.629 (1)° |
Bruker APEXII area-detector diffractometer | 6372 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 5465 reflections with I > 2σ(I) |
Tmin = 0.527, Tmax = 0.723 | Rint = 0.020 |
19675 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 5 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.74 e Å−3 |
6372 reflections | Δρmin = −0.72 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 | ||
Ce1 | 0.721731 (14) | 0.278491 (10) | 0.113902 (6) | 0.02791 (5) | |
Zn1 | 0.68898 (3) | 0.37172 (2) | 0.273209 (14) | 0.03396 (8) | |
O1 | 0.82372 (19) | 0.28221 (13) | 0.22806 (9) | 0.0344 (4) | |
O2 | 0.55782 (18) | 0.32520 (14) | 0.19983 (9) | 0.0367 (4) | |
O3 | 0.7363 (2) | 0.36404 (16) | 0.00051 (10) | 0.0478 (5) | |
O7 | 0.4590 (2) | 0.35443 (16) | 0.08041 (10) | 0.0455 (5) | |
O6 | 0.96909 (19) | 0.18026 (15) | 0.14819 (9) | 0.0403 (4) | |
C1 | 0.9350 (3) | 0.23935 (19) | 0.25581 (13) | 0.0316 (5) | |
O4 | 0.9350 (2) | 0.33221 (17) | 0.04741 (11) | 0.0482 (5) | |
N1 | 0.7945 (3) | 0.35347 (18) | 0.36140 (11) | 0.0431 (6) | |
C11 | 0.3434 (3) | 0.37291 (19) | 0.25099 (16) | 0.0424 (7) | |
N2 | 0.5234 (3) | 0.36933 (18) | 0.33703 (12) | 0.0459 (6) | |
C16 | 0.4265 (3) | 0.35515 (18) | 0.19525 (14) | 0.0347 (5) | |
C6 | 0.9761 (3) | 0.2473 (2) | 0.32368 (14) | 0.0402 (6) | |
C12 | 0.2017 (3) | 0.3975 (2) | 0.2391 (2) | 0.0559 (9) | |
H12 | 0.1450 | 0.4072 | 0.2754 | 0.067* | |
N3 | 0.8670 (3) | 0.3669 (2) | −0.00159 (13) | 0.0507 (6) | |
C2 | 1.0167 (3) | 0.1824 (2) | 0.21410 (14) | 0.0368 (6) | |
C15 | 0.3671 (3) | 0.36920 (19) | 0.13120 (16) | 0.0399 (6) | |
C14 | 0.2281 (3) | 0.3946 (2) | 0.12134 (18) | 0.0513 (8) | |
H14 | 0.1905 | 0.4029 | 0.0784 | 0.062* | |
C5 | 1.0961 (3) | 0.1961 (3) | 0.34678 (17) | 0.0520 (8) | |
H5 | 1.1232 | 0.2002 | 0.3916 | 0.062* | |
C3 | 1.1328 (3) | 0.1340 (2) | 0.23810 (17) | 0.0490 (7) | |
H3 | 1.1850 | 0.0964 | 0.2095 | 0.059* | |
C7 | 0.9013 (3) | 0.3013 (2) | 0.37289 (14) | 0.0442 (7) | |
H7 | 0.9343 | 0.2976 | 0.4169 | 0.053* | |
C9 | 0.5654 (4) | 0.3618 (3) | 0.40743 (15) | 0.0566 (9) | |
H9A | 0.5584 | 0.2950 | 0.4221 | 0.068* | |
H9B | 0.5043 | 0.4009 | 0.4342 | 0.068* | |
C10 | 0.3950 (3) | 0.3688 (2) | 0.31924 (17) | 0.0486 (7) | |
H10 | 0.3299 | 0.3656 | 0.3526 | 0.058* | |
O5 | 0.9252 (3) | 0.4002 (3) | −0.04931 (16) | 0.1083 (13) | |
C8 | 0.7153 (4) | 0.3970 (2) | 0.41643 (15) | 0.0563 (9) | |
H8A | 0.7191 | 0.4672 | 0.4141 | 0.068* | |
H8B | 0.7541 | 0.3765 | 0.4594 | 0.068* | |
C13 | 0.1462 (3) | 0.4075 (2) | 0.1766 (2) | 0.0577 (9) | |
H13 | 0.0524 | 0.4230 | 0.1707 | 0.069* | |
O14 | 0.6427 (2) | 0.11821 (14) | 0.16096 (10) | 0.0422 (4) | |
O8 | 0.5705 (2) | 0.18208 (16) | 0.02343 (10) | 0.0459 (5) | |
O11 | 0.7636 (2) | 0.45076 (15) | 0.13802 (10) | 0.0477 (5) | |
O9 | 0.7877 (2) | 0.14445 (16) | 0.02635 (11) | 0.0485 (5) | |
N4 | 0.6690 (3) | 0.13210 (17) | 0.00004 (12) | 0.0453 (6) | |
C18 | 1.0647 (3) | 0.1421 (3) | 0.10137 (17) | 0.0554 (8) | |
H18A | 1.1526 | 0.1748 | 0.1066 | 0.083* | |
H18B | 1.0282 | 0.1519 | 0.0568 | 0.083* | |
H18C | 1.0775 | 0.0740 | 0.1093 | 0.083* | |
C17 | 0.4079 (4) | 0.3800 (3) | 0.01437 (17) | 0.0621 (9) | |
H17A | 0.3365 | 0.3352 | 0.0003 | 0.093* | |
H17B | 0.4831 | 0.3775 | −0.0162 | 0.093* | |
H17C | 0.3701 | 0.4444 | 0.0150 | 0.093* | |
C4 | 1.1720 (4) | 0.1415 (3) | 0.30533 (18) | 0.0579 (9) | |
H4 | 1.2506 | 0.1088 | 0.3217 | 0.069* | |
O13 | 0.7477 (2) | 0.50345 (14) | 0.24266 (9) | 0.0413 (4) | |
N5 | 0.7785 (3) | 0.51482 (18) | 0.18155 (12) | 0.0470 (6) | |
O10 | 0.6498 (3) | 0.0758 (2) | −0.04574 (13) | 0.0771 (8) | |
O12 | 0.8398 (4) | 0.6105 (2) | 0.16137 (19) | 0.1030 (11) | |
C19 | 0.5004 (4) | 0.0893 (3) | 0.1620 (2) | 0.0657 (10) | |
H19A | 0.4721 | 0.0840 | 0.2074 | 0.099* | |
H19B | 0.4896 | 0.0277 | 0.1402 | 0.099* | |
H19C | 0.4437 | 0.1367 | 0.1391 | 0.099* | |
H14A | 0.695 (3) | 0.087 (2) | 0.1905 (13) | 0.049 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ce1 | 0.03009 (8) | 0.03429 (8) | 0.01915 (8) | 0.00086 (5) | −0.00257 (5) | −0.00135 (5) |
Zn1 | 0.04075 (17) | 0.03836 (16) | 0.02282 (14) | −0.00119 (12) | 0.00205 (12) | −0.00123 (11) |
O1 | 0.0325 (9) | 0.0470 (10) | 0.0234 (9) | 0.0066 (7) | −0.0050 (7) | −0.0011 (7) |
O2 | 0.0292 (9) | 0.0485 (11) | 0.0323 (10) | 0.0051 (8) | 0.0012 (8) | −0.0059 (8) |
O3 | 0.0449 (11) | 0.0668 (14) | 0.0314 (10) | 0.0013 (10) | −0.0046 (9) | 0.0087 (9) |
O7 | 0.0364 (10) | 0.0628 (13) | 0.0369 (11) | 0.0104 (9) | −0.0079 (9) | −0.0069 (10) |
O6 | 0.0380 (10) | 0.0523 (11) | 0.0303 (10) | 0.0091 (9) | −0.0044 (8) | −0.0048 (8) |
C1 | 0.0313 (12) | 0.0369 (12) | 0.0260 (12) | −0.0040 (10) | −0.0072 (10) | 0.0062 (10) |
O4 | 0.0363 (10) | 0.0616 (13) | 0.0468 (12) | −0.0019 (9) | 0.0006 (9) | 0.0098 (10) |
N1 | 0.0595 (15) | 0.0469 (13) | 0.0228 (11) | −0.0059 (11) | −0.0012 (11) | −0.0014 (10) |
C11 | 0.0387 (14) | 0.0346 (13) | 0.0548 (18) | −0.0020 (11) | 0.0161 (13) | −0.0040 (12) |
N2 | 0.0579 (16) | 0.0469 (13) | 0.0337 (12) | 0.0002 (11) | 0.0154 (12) | 0.0005 (10) |
C16 | 0.0278 (12) | 0.0322 (12) | 0.0442 (15) | −0.0009 (9) | 0.0031 (11) | −0.0056 (11) |
C6 | 0.0394 (14) | 0.0504 (14) | 0.0300 (14) | −0.0069 (12) | −0.0106 (11) | 0.0108 (12) |
C12 | 0.0385 (16) | 0.0444 (16) | 0.086 (3) | −0.0001 (13) | 0.0260 (17) | −0.0071 (17) |
N3 | 0.0537 (16) | 0.0603 (16) | 0.0384 (14) | −0.0004 (12) | 0.0092 (12) | 0.0094 (12) |
C2 | 0.0341 (13) | 0.0390 (13) | 0.0368 (14) | −0.0009 (11) | −0.0063 (11) | 0.0040 (11) |
C15 | 0.0295 (13) | 0.0385 (13) | 0.0513 (17) | 0.0006 (10) | −0.0024 (12) | −0.0082 (12) |
C14 | 0.0320 (14) | 0.0501 (17) | 0.071 (2) | 0.0031 (12) | −0.0101 (15) | −0.0068 (15) |
C5 | 0.0490 (18) | 0.068 (2) | 0.0384 (16) | 0.0002 (15) | −0.0166 (14) | 0.0136 (15) |
C3 | 0.0408 (15) | 0.0500 (16) | 0.056 (2) | 0.0112 (13) | −0.0082 (14) | 0.0076 (14) |
C7 | 0.0552 (18) | 0.0539 (16) | 0.0228 (13) | −0.0127 (14) | −0.0128 (13) | 0.0054 (12) |
C9 | 0.080 (2) | 0.0605 (19) | 0.0304 (15) | 0.0050 (17) | 0.0204 (16) | 0.0008 (14) |
C10 | 0.0523 (18) | 0.0437 (15) | 0.0511 (18) | −0.0002 (13) | 0.0241 (15) | −0.0033 (13) |
O5 | 0.091 (2) | 0.162 (3) | 0.073 (2) | 0.005 (2) | 0.0358 (18) | 0.061 (2) |
C8 | 0.091 (3) | 0.0515 (17) | 0.0264 (14) | 0.0017 (17) | 0.0052 (16) | −0.0077 (13) |
C13 | 0.0290 (14) | 0.0503 (17) | 0.094 (3) | 0.0056 (12) | 0.0038 (17) | −0.0045 (18) |
O14 | 0.0444 (11) | 0.0419 (10) | 0.0403 (11) | −0.0039 (9) | −0.0016 (9) | 0.0099 (9) |
O8 | 0.0478 (11) | 0.0537 (12) | 0.0354 (11) | 0.0032 (10) | −0.0122 (9) | −0.0040 (9) |
O11 | 0.0688 (14) | 0.0416 (10) | 0.0328 (9) | −0.0041 (9) | 0.0045 (10) | −0.0023 (7) |
O9 | 0.0470 (11) | 0.0557 (12) | 0.0426 (12) | 0.0034 (9) | −0.0028 (10) | −0.0162 (9) |
N4 | 0.0637 (16) | 0.0421 (13) | 0.0297 (12) | −0.0017 (11) | −0.0074 (12) | −0.0025 (10) |
C18 | 0.0492 (18) | 0.071 (2) | 0.0459 (18) | 0.0189 (15) | 0.0047 (15) | −0.0093 (16) |
C17 | 0.059 (2) | 0.082 (2) | 0.0434 (18) | 0.0169 (18) | −0.0169 (16) | −0.0039 (17) |
C4 | 0.0501 (18) | 0.068 (2) | 0.054 (2) | 0.0132 (16) | −0.0196 (16) | 0.0164 (17) |
O13 | 0.0551 (12) | 0.0358 (9) | 0.0330 (8) | −0.0046 (8) | 0.0030 (9) | −0.0026 (7) |
N5 | 0.0596 (15) | 0.0440 (12) | 0.0374 (10) | 0.0027 (11) | 0.0040 (11) | −0.0026 (9) |
O10 | 0.103 (2) | 0.0703 (16) | 0.0568 (15) | 0.0007 (15) | −0.0205 (15) | −0.0352 (13) |
O12 | 0.140 (3) | 0.0671 (18) | 0.104 (3) | −0.0115 (19) | 0.035 (2) | 0.0014 (18) |
C19 | 0.0525 (19) | 0.074 (2) | 0.070 (2) | −0.0207 (17) | −0.0022 (18) | 0.0150 (19) |
Ce1—O1 | 2.4630 (18) | C12—H12 | 0.9300 |
Ce1—O2 | 2.4517 (17) | N3—O5 | 1.212 (3) |
Ce1—O3 | 2.568 (2) | C2—C3 | 1.375 (4) |
Ce1—O4 | 2.583 (2) | C15—C14 | 1.388 (4) |
Ce1—O6 | 2.8033 (19) | C14—C13 | 1.388 (5) |
Ce1—O7 | 2.7957 (19) | C14—H14 | 0.9300 |
Ce1—O8 | 2.649 (2) | C5—C4 | 1.351 (5) |
Ce1—O9 | 2.639 (2) | C5—H5 | 0.9300 |
Ce1—O11 | 2.457 (2) | C3—C4 | 1.392 (5) |
Ce1—O14 | 2.5301 (19) | C3—H3 | 0.9300 |
Zn1—O1 | 2.0212 (17) | C7—H7 | 0.9300 |
Zn1—O2 | 2.0136 (19) | C9—C8 | 1.525 (5) |
Zn1—O13 | 2.0047 (19) | C9—H9A | 0.9700 |
Zn1—N1 | 2.028 (2) | C9—H9B | 0.9700 |
Zn1—N2 | 2.068 (2) | C10—H10 | 0.9300 |
O1—C1 | 1.329 (3) | C8—H8A | 0.9700 |
O2—C16 | 1.328 (3) | C8—H8B | 0.9700 |
O3—N3 | 1.258 (3) | C13—H13 | 0.9300 |
O7—C15 | 1.381 (3) | O14—C19 | 1.423 (4) |
O7—C17 | 1.442 (4) | O14—H14A | 0.875 (18) |
O6—C2 | 1.385 (3) | O8—N4 | 1.270 (3) |
O6—C18 | 1.432 (3) | O11—N5 | 1.248 (3) |
C1—C2 | 1.403 (4) | O9—N4 | 1.254 (3) |
C1—C6 | 1.409 (4) | N4—O10 | 1.212 (3) |
O4—N3 | 1.258 (3) | C18—H18A | 0.9600 |
N1—C7 | 1.268 (4) | C18—H18B | 0.9600 |
N1—C8 | 1.484 (4) | C18—H18C | 0.9600 |
C11—C16 | 1.412 (4) | C17—H17A | 0.9600 |
C11—C12 | 1.415 (4) | C17—H17B | 0.9600 |
C11—C10 | 1.442 (5) | C17—H17C | 0.9600 |
N2—C10 | 1.274 (4) | C4—H4 | 0.9300 |
N2—C9 | 1.460 (4) | O13—N5 | 1.278 (3) |
C16—C15 | 1.403 (4) | N5—O12 | 1.506 (4) |
C6—C5 | 1.418 (4) | C19—H19A | 0.9600 |
C6—C7 | 1.444 (4) | C19—H19B | 0.9600 |
C12—C13 | 1.354 (5) | C19—H19C | 0.9600 |
O2—Ce1—O11 | 73.26 (6) | O2—C16—C11 | 123.8 (3) |
O2—Ce1—O1 | 65.70 (6) | C15—C16—C11 | 118.4 (2) |
O11—Ce1—O1 | 74.86 (6) | C1—C6—C5 | 118.6 (3) |
O2—Ce1—O14 | 76.29 (7) | C1—C6—C7 | 124.6 (3) |
O11—Ce1—O14 | 145.29 (7) | C5—C6—C7 | 116.7 (3) |
O1—Ce1—O14 | 77.74 (6) | C13—C12—C11 | 122.1 (3) |
O2—Ce1—O3 | 123.54 (7) | C13—C12—H12 | 118.9 |
O11—Ce1—O3 | 73.52 (7) | C11—C12—H12 | 118.9 |
O1—Ce1—O3 | 141.44 (7) | O5—N3—O3 | 121.4 (3) |
O14—Ce1—O3 | 139.14 (7) | O5—N3—O4 | 121.3 (3) |
O2—Ce1—O4 | 145.16 (7) | O3—N3—O4 | 117.2 (2) |
O11—Ce1—O4 | 72.31 (7) | C3—C2—O6 | 124.4 (3) |
O1—Ce1—O4 | 99.96 (7) | C3—C2—C1 | 121.7 (3) |
O14—Ce1—O4 | 133.94 (7) | O6—C2—C1 | 113.9 (2) |
O3—Ce1—O4 | 49.29 (7) | O7—C15—C14 | 124.4 (3) |
O2—Ce1—O9 | 145.30 (7) | O7—C15—C16 | 113.7 (2) |
O11—Ce1—O9 | 140.19 (7) | C14—C15—C16 | 122.0 (3) |
O1—Ce1—O9 | 122.37 (6) | C13—C14—C15 | 118.9 (3) |
O14—Ce1—O9 | 73.43 (7) | C13—C14—H14 | 120.6 |
O3—Ce1—O9 | 73.39 (7) | C15—C14—H14 | 120.6 |
O4—Ce1—O9 | 69.50 (7) | C4—C5—C6 | 121.7 (3) |
O2—Ce1—O8 | 105.22 (6) | C4—C5—H5 | 119.2 |
O11—Ce1—O8 | 134.76 (7) | C6—C5—H5 | 119.2 |
O1—Ce1—O8 | 147.33 (6) | C2—C3—C4 | 119.8 (3) |
O14—Ce1—O8 | 69.59 (7) | C2—C3—H3 | 120.1 |
O3—Ce1—O8 | 70.61 (7) | C4—C3—H3 | 120.1 |
O4—Ce1—O8 | 102.61 (7) | N1—C7—C6 | 125.8 (3) |
O9—Ce1—O8 | 47.93 (7) | N1—C7—H7 | 117.1 |
O2—Ce1—O7 | 58.48 (6) | C6—C7—H7 | 117.1 |
O11—Ce1—O7 | 79.96 (7) | N2—C9—C8 | 109.0 (2) |
O1—Ce1—O7 | 123.18 (6) | N2—C9—H9A | 109.9 |
O14—Ce1—O7 | 98.00 (7) | C8—C9—H9A | 109.9 |
O3—Ce1—O7 | 71.74 (6) | N2—C9—H9B | 109.9 |
O4—Ce1—O7 | 119.44 (7) | C8—C9—H9B | 109.9 |
O9—Ce1—O7 | 109.59 (6) | H9A—C9—H9B | 108.3 |
O8—Ce1—O7 | 63.32 (6) | N2—C10—C11 | 124.7 (3) |
O2—Ce1—O6 | 120.75 (6) | N2—C10—H10 | 117.7 |
O11—Ce1—O6 | 106.70 (7) | C11—C10—H10 | 117.7 |
O1—Ce1—O6 | 58.05 (6) | N1—C8—C9 | 106.5 (3) |
O14—Ce1—O6 | 75.33 (6) | N1—C8—H8A | 110.4 |
O3—Ce1—O6 | 111.86 (6) | C9—C8—H8A | 110.4 |
O4—Ce1—O6 | 65.60 (6) | N1—C8—H8B | 110.4 |
O9—Ce1—O6 | 66.80 (6) | C9—C8—H8B | 110.4 |
O8—Ce1—O6 | 111.63 (6) | H8A—C8—H8B | 108.6 |
O7—Ce1—O6 | 173.00 (6) | C12—C13—C14 | 120.5 (3) |
O13—Zn1—O2 | 103.99 (8) | C12—C13—H13 | 119.7 |
O13—Zn1—O1 | 103.22 (8) | C14—C13—H13 | 119.7 |
O2—Zn1—O1 | 82.71 (7) | C19—O14—Ce1 | 123.3 (2) |
O13—Zn1—N1 | 103.95 (9) | C19—O14—H14A | 112 (2) |
O2—Zn1—N1 | 152.06 (9) | Ce1—O14—H14A | 121 (2) |
O1—Zn1—N1 | 90.21 (9) | N4—O8—Ce1 | 97.26 (15) |
O13—Zn1—N2 | 115.52 (9) | N5—O11—Ce1 | 146.97 (17) |
O2—Zn1—N2 | 88.33 (9) | N4—O9—Ce1 | 98.18 (16) |
O1—Zn1—N2 | 141.25 (9) | O10—N4—O9 | 121.5 (3) |
N1—Zn1—N2 | 80.39 (11) | O10—N4—O8 | 121.9 (3) |
C1—O1—Zn1 | 127.01 (16) | O9—N4—O8 | 116.6 (2) |
C1—O1—Ce1 | 132.29 (16) | O6—C18—H18A | 109.5 |
Zn1—O1—Ce1 | 100.71 (7) | O6—C18—H18B | 109.5 |
C16—O2—Zn1 | 121.61 (16) | H18A—C18—H18B | 109.5 |
C16—O2—Ce1 | 131.35 (17) | O6—C18—H18C | 109.5 |
Zn1—O2—Ce1 | 101.31 (7) | H18A—C18—H18C | 109.5 |
N3—O3—Ce1 | 97.10 (16) | H18B—C18—H18C | 109.5 |
C15—O7—C17 | 115.6 (2) | O7—C17—H17A | 109.5 |
C15—O7—Ce1 | 118.02 (16) | O7—C17—H17B | 109.5 |
C17—O7—Ce1 | 126.38 (18) | H17A—C17—H17B | 109.5 |
C2—O6—C18 | 115.6 (2) | O7—C17—H17C | 109.5 |
C2—O6—Ce1 | 118.50 (15) | H17A—C17—H17C | 109.5 |
C18—O6—Ce1 | 124.90 (17) | H17B—C17—H17C | 109.5 |
O1—C1—C2 | 117.1 (2) | C5—C4—C3 | 120.0 (3) |
O1—C1—C6 | 124.7 (2) | C5—C4—H4 | 120.0 |
C2—C1—C6 | 118.2 (2) | C3—C4—H4 | 120.0 |
N3—O4—Ce1 | 96.36 (16) | N5—O13—Zn1 | 118.62 (17) |
C7—N1—C8 | 121.6 (3) | O11—N5—O13 | 123.9 (2) |
C7—N1—Zn1 | 127.6 (2) | O11—N5—O12 | 118.2 (2) |
C8—N1—Zn1 | 110.1 (2) | O13—N5—O12 | 117.9 (2) |
C16—C11—C12 | 118.0 (3) | O14—C19—H19A | 109.5 |
C16—C11—C10 | 123.8 (3) | O14—C19—H19B | 109.5 |
C12—C11—C10 | 118.1 (3) | H19A—C19—H19B | 109.5 |
C10—N2—C9 | 120.6 (3) | O14—C19—H19C | 109.5 |
C10—N2—Zn1 | 125.6 (2) | H19A—C19—H19C | 109.5 |
C9—N2—Zn1 | 113.8 (2) | H19B—C19—H19C | 109.5 |
O2—C16—C15 | 117.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O14—H14A···O13i | 0.88 (2) | 1.84 (2) | 2.689 (3) | 162 (3) |
C7—H7···O8ii | 0.93 | 2.49 | 3.393 (3) | 165 |
C5—H5···O3ii | 0.93 | 2.57 | 3.428 (4) | 154 |
C17—H17B···O3 | 0.96 | 2.45 | 3.180 (4) | 133 |
C18—H18B···O9 | 0.96 | 2.37 | 3.018 (4) | 124 |
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 | [CeZn(C18H18N2O4)(CH4O)(NO3)3] |
Mr | 749.91 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.6011 (4), 13.8046 (5), 20.0375 (7) |
β (°) | 91.629 (1) |
V (Å3) | 2654.68 (17) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.67 |
Crystal size (mm) | 0.28 × 0.20 × 0.13 |
Data collection | |
Diffractometer | Bruker APEXII area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.527, 0.723 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19675, 6372, 5465 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.072, 1.00 |
No. of reflections | 6372 |
No. of parameters | 367 |
No. of restraints | 5 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.74, −0.72 |
Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), APEX2 and publCIF (Westrip, 2007).
Ce1—O1 | 2.4630 (18) | Ce1—O11 | 2.457 (2) |
Ce1—O2 | 2.4517 (17) | Ce1—O14 | 2.5301 (19) |
Ce1—O3 | 2.568 (2) | Zn1—O1 | 2.0212 (17) |
Ce1—O4 | 2.583 (2) | Zn1—O2 | 2.0136 (19) |
Ce1—O6 | 2.8033 (19) | Zn1—O13 | 2.0047 (19) |
Ce1—O7 | 2.7957 (19) | Zn1—N1 | 2.028 (2) |
Ce1—O8 | 2.649 (2) | Zn1—N2 | 2.068 (2) |
Ce1—O9 | 2.639 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O14—H14A···O13i | 0.875 (18) | 1.84 (2) | 2.689 (3) | 162 (3) |
C7—H7···O8ii | 0.93 | 2.49 | 3.393 (3) | 164.6 |
C5—H5···O3ii | 0.93 | 2.57 | 3.428 (4) | 154.1 |
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 ZnII–CeIII complex with salen-type Schiff base N,N'-bis(3-ethoxysalicylidene)ethylenediamine(H2L).
Complex (I) crystallizes in the space group P21/n, with zinc and cerium 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 zinc(II), while cerium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand.
The cerium(III) center in (I) has a decacoordination environment of O atoms. In addition to the phenolate ligands, two methoxy O atoms and one methanol O atoms coordinate to this metal center, two O atoms each from the two nitrates and one of the bridged nitrate O atoms chelate to cerium to complete the decacoordination. The five kinds of Ce—O bond distances are significantly different, the longest being the Ce—O(methoxy) separations and the shortest being the Ce—O(phenolate) and Ce—O11(bridged nitrate).
The zinc(II) is in a square-pyramidal geometry and is five-coordinated by two imine N atoms, two phenolate O atoms and one of the bridged nitrate O atoms. The Zn atom is 0.5822 (2)Å above the mean N2O2 plane with an average deviation from the plane of 0.0961 (3) Å, which construct the bottom of square-pyramid. The Zn—O13(nitrate, bridged) separation is 2.0047 (19)Å and the angles of this Zn—O vector with the Zn—N or Zn—O bonds lie between 103.22 (8)° and 115.52 (9)°, which suggesting that the zinc(II) is in a slightly distorted square-pyramidal conformation.
Adjacent molecules are held together by strong interactions (O14—H14A···O13i = 2.689 (3); symmetry codes:(i) 3/2 - x, y - 1/2, 1/2 - z) and weak interactions (C7—H7···O8ii = 3.393 (3) and C5—H5···O3ii = 3.428 (4); symmetry codes: (ii) 1/2 + x, 1/2 - y, 1/2 + z). these link the molecules into a two-dimensional layer structure (Fig. 2).