Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807061508/at2499sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807061508/at2499Isup2.hkl |
CCDC reference: 672774
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.012 Å
- R factor = 0.045
- wR factor = 0.084
- Data-to-parameter ratio = 16.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 49 Perc. PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT230_ALERT_2_C Hirshfeld Test Diff for O9 - N4 .. 5.35 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Sm1 - O9 .. 5.55 su PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 12
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 28.20 From the CIF: _reflns_number_total 6073 Count of symmetry unique reflns 3485 Completeness (_total/calc) 174.26% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2588 Fraction of Friedel pairs measured 0.743 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 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 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 nickel(II) acetate tetrahydrate (0.217 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 samarium(III) nitrate hexahydrate (0.445 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 C20H22N5NiO13Sm: C 32.05, H 2.96, N 9.34, Ni 7.83, Sm 20.06%; found: C 32.15, H 2.98, N 9.22, Ni 7.88, Sm 20.22%. 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 in the range 0.93 - 0.97 Å, and with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: APEX2 (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: APEX2 (Bruker, 2004); software used to prepare material for publication: APEX2 and publCIF (Westrip, 2007).
[NiSm(C20H22N2O4)(NO3)3] | F(000) = 1484 |
Mr = 749.49 | Dx = 1.992 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 4344 reflections |
a = 8.6097 (14) Å | θ = 1.9–28.2° |
b = 13.750 (2) Å | µ = 3.16 mm−1 |
c = 21.113 (3) Å | T = 293 K |
V = 2499.4 (7) Å3 | Block, red |
Z = 4 | 0.26 × 0.14 × 0.07 mm |
Bruker APEXII area-detector diffractometer | 6073 independent reflections |
Radiation source: fine-focus sealed tube | 2970 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.089 |
Detector resolution: 0 pixels mm-1 | θmax = 28.2°, θmin = 1.9° |
ϕ and ω scan | h = −11→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | k = −17→18 |
Tmin = 0.494, Tmax = 0.821 | l = −28→27 |
18707 measured reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.045 | w = 1/[σ2(Fo2) + (0.010P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.084 | (Δ/σ)max = 0.001 |
S = 1.00 | Δρmax = 1.58 e Å−3 |
6073 reflections | Δρmin = −1.58 e Å−3 |
362 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.00131 (15) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 2588 Freidel pairs |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.007 (19) |
[NiSm(C20H22N2O4)(NO3)3] | V = 2499.4 (7) Å3 |
Mr = 749.49 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.6097 (14) Å | µ = 3.16 mm−1 |
b = 13.750 (2) Å | T = 293 K |
c = 21.113 (3) Å | 0.26 × 0.14 × 0.07 mm |
Bruker APEXII area-detector diffractometer | 6073 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | 2970 reflections with I > 2σ(I) |
Tmin = 0.494, Tmax = 0.821 | Rint = 0.089 |
18707 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.084 | Δρmax = 1.58 e Å−3 |
S = 1.00 | Δρmin = −1.58 e Å−3 |
6073 reflections | Absolute structure: Flack (1983), 2588 Freidel pairs |
362 parameters | Absolute structure parameter: 0.007 (19) |
1 restraint |
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 | 0.74822 (5) | 0.49875 (3) | 0.904649 (15) | 0.04039 (13) | |
Ni1 | 1.06957 (11) | 0.43994 (7) | 0.81466 (5) | 0.0377 (3) | |
O2 | 0.9712 (5) | 0.5510 (4) | 0.8455 (2) | 0.0368 (12) | |
O1 | 0.9232 (7) | 0.3732 (3) | 0.8629 (2) | 0.0429 (14) | |
C16 | 1.0300 (9) | 0.6379 (6) | 0.8438 (4) | 0.040 (2) | |
N2 | 1.1979 (6) | 0.5089 (5) | 0.7614 (3) | 0.0415 (17) | |
O5 | 0.7374 (7) | 0.5086 (5) | 1.0229 (2) | 0.0609 (14) | |
C1 | 0.9166 (11) | 0.2794 (6) | 0.8738 (4) | 0.039 (2) | |
O6 | 0.9601 (6) | 0.4659 (4) | 0.9879 (3) | 0.0578 (18) | |
O3 | 0.6921 (6) | 0.3156 (4) | 0.9304 (2) | 0.0418 (15) | |
N1 | 1.1761 (8) | 0.3307 (5) | 0.7897 (3) | 0.040 (2) | |
C11 | 1.1493 (10) | 0.6679 (6) | 0.8038 (4) | 0.039 (2) | |
C2 | 0.7939 (8) | 0.2430 (5) | 0.9086 (4) | 0.039 (2) | |
C12 | 1.2037 (9) | 0.7641 (6) | 0.8051 (4) | 0.046 (2) | |
H12 | 1.2781 | 0.7845 | 0.7761 | 0.056* | |
C7 | 1.1482 (10) | 0.2432 (7) | 0.8103 (5) | 0.050 (3) | |
H7 | 1.2178 | 0.1952 | 0.7977 | 0.060* | |
C19 | 0.5526 (9) | 0.2857 (6) | 0.9639 (4) | 0.047 (2) | |
H19A | 0.5074 | 0.3418 | 0.9848 | 0.057* | |
H19B | 0.5803 | 0.2387 | 0.9962 | 0.057* | |
C6 | 1.0246 (9) | 0.2123 (5) | 0.8494 (4) | 0.0364 (19) | |
O4 | 0.8532 (6) | 0.6719 (4) | 0.9247 (2) | 0.0404 (14) | |
C15 | 0.9653 (10) | 0.7080 (6) | 0.8862 (4) | 0.037 (2) | |
C4 | 0.8980 (11) | 0.0817 (6) | 0.9028 (4) | 0.054 (2) | |
H4 | 0.8940 | 0.0164 | 0.9142 | 0.064* | |
N3 | 0.8787 (9) | 0.4933 (6) | 1.0341 (3) | 0.0523 (17) | |
C10 | 1.2268 (11) | 0.5986 (6) | 0.7611 (4) | 0.048 (2) | |
H10 | 1.3003 | 0.6221 | 0.7327 | 0.058* | |
O7 | 0.9325 (7) | 0.4984 (5) | 1.0867 (3) | 0.0793 (17) | |
C20 | 0.4353 (10) | 0.2419 (6) | 0.9207 (4) | 0.064 (3) | |
H20A | 0.4092 | 0.2877 | 0.8881 | 0.096* | |
H20B | 0.3437 | 0.2256 | 0.9444 | 0.096* | |
H20C | 0.4774 | 0.1841 | 0.9018 | 0.096* | |
C5 | 1.0135 (10) | 0.1148 (6) | 0.8660 (4) | 0.048 (2) | |
H5 | 1.0880 | 0.0713 | 0.8512 | 0.058* | |
C13 | 1.1476 (11) | 0.8275 (6) | 0.8488 (4) | 0.058 (2) | |
H13 | 1.1907 | 0.8893 | 0.8519 | 0.070* | |
O11 | 0.6799 (7) | 0.4591 (5) | 0.7895 (3) | 0.0548 (19) | |
O9 | 0.4640 (7) | 0.4655 (4) | 0.8904 (3) | 0.0610 (18) | |
N5 | 0.6398 (9) | 0.5460 (7) | 0.7739 (4) | 0.054 (2) | |
O12 | 0.6472 (7) | 0.6093 (4) | 0.8170 (3) | 0.0569 (16) | |
O8 | 0.5117 (7) | 0.5881 (5) | 0.9497 (3) | 0.0611 (19) | |
N4 | 0.4132 (9) | 0.5368 (6) | 0.9234 (4) | 0.053 (2) | |
O10 | 0.2729 (8) | 0.5498 (6) | 0.9315 (3) | 0.083 (2) | |
C17 | 0.7801 (9) | 0.7381 (5) | 0.9708 (3) | 0.043 (2) | |
H17A | 0.8603 | 0.7760 | 0.9916 | 0.051* | |
H17B | 0.7275 | 0.6999 | 1.0029 | 0.051* | |
C3 | 0.7828 (10) | 0.1467 (6) | 0.9240 (4) | 0.045 (2) | |
H3 | 0.7001 | 0.1243 | 0.9483 | 0.054* | |
C8 | 1.3125 (10) | 0.3502 (7) | 0.7503 (4) | 0.055 (3) | |
H8A | 1.3308 | 0.2971 | 0.7211 | 0.066* | |
H8B | 1.4043 | 0.3589 | 0.7764 | 0.066* | |
C9 | 1.2742 (10) | 0.4432 (6) | 0.7147 (3) | 0.050 (2) | |
H9A | 1.3680 | 0.4728 | 0.6982 | 0.060* | |
H9B | 1.2047 | 0.4296 | 0.6797 | 0.060* | |
C14 | 1.0292 (9) | 0.8018 (6) | 0.8880 (4) | 0.047 (2) | |
H14 | 0.9899 | 0.8472 | 0.9164 | 0.057* | |
O13 | 0.5995 (7) | 0.5672 (5) | 0.7215 (3) | 0.083 (2) | |
C18 | 0.6670 (10) | 0.8050 (6) | 0.9409 (4) | 0.058 (3) | |
H18A | 0.7186 | 0.8434 | 0.9093 | 0.087* | |
H18B | 0.6235 | 0.8470 | 0.9726 | 0.087* | |
H18C | 0.5854 | 0.7679 | 0.9214 | 0.087* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sm1 | 0.0467 (2) | 0.03015 (18) | 0.04428 (19) | 0.0004 (3) | 0.0029 (3) | −0.0022 (2) |
Ni1 | 0.0425 (6) | 0.0292 (5) | 0.0414 (5) | −0.0002 (5) | 0.0048 (5) | −0.0048 (5) |
O2 | 0.043 (3) | 0.023 (3) | 0.045 (3) | −0.003 (3) | 0.005 (3) | 0.002 (3) |
O1 | 0.062 (4) | 0.021 (3) | 0.046 (3) | −0.004 (3) | 0.007 (3) | 0.002 (2) |
C16 | 0.049 (5) | 0.041 (5) | 0.030 (4) | −0.006 (4) | −0.002 (4) | −0.008 (4) |
N2 | 0.050 (4) | 0.028 (4) | 0.047 (4) | −0.008 (4) | 0.005 (3) | −0.004 (4) |
O5 | 0.075 (4) | 0.071 (4) | 0.037 (3) | 0.007 (6) | 0.011 (3) | 0.009 (3) |
C1 | 0.040 (5) | 0.025 (5) | 0.051 (5) | −0.004 (4) | −0.007 (5) | −0.007 (4) |
O6 | 0.044 (3) | 0.075 (5) | 0.054 (4) | 0.008 (3) | 0.002 (3) | 0.005 (3) |
O3 | 0.051 (4) | 0.027 (3) | 0.048 (3) | −0.009 (3) | 0.015 (3) | 0.008 (2) |
N1 | 0.044 (5) | 0.034 (4) | 0.043 (5) | 0.003 (4) | 0.005 (4) | −0.011 (4) |
C11 | 0.048 (6) | 0.026 (5) | 0.044 (6) | 0.000 (4) | 0.000 (5) | 0.000 (4) |
C2 | 0.047 (6) | 0.024 (4) | 0.044 (5) | 0.000 (4) | −0.007 (4) | 0.000 (4) |
C12 | 0.048 (6) | 0.036 (5) | 0.055 (6) | −0.011 (4) | 0.013 (4) | 0.000 (4) |
C7 | 0.044 (6) | 0.042 (6) | 0.064 (6) | 0.018 (5) | 0.002 (5) | −0.024 (5) |
C19 | 0.044 (5) | 0.047 (5) | 0.052 (6) | −0.006 (5) | 0.004 (5) | 0.005 (4) |
C6 | 0.039 (5) | 0.025 (4) | 0.045 (5) | 0.007 (4) | −0.007 (5) | −0.003 (4) |
O4 | 0.054 (4) | 0.026 (3) | 0.041 (3) | −0.001 (3) | 0.008 (3) | −0.010 (2) |
C15 | 0.046 (6) | 0.028 (5) | 0.039 (5) | 0.002 (4) | −0.006 (4) | −0.004 (4) |
C4 | 0.077 (7) | 0.027 (5) | 0.057 (5) | 0.006 (5) | −0.004 (5) | 0.005 (4) |
N3 | 0.065 (5) | 0.043 (4) | 0.049 (5) | −0.005 (5) | 0.001 (4) | 0.011 (5) |
C10 | 0.042 (6) | 0.064 (6) | 0.038 (5) | −0.012 (5) | 0.000 (5) | 0.001 (4) |
O7 | 0.120 (5) | 0.069 (4) | 0.049 (4) | 0.011 (6) | −0.026 (4) | 0.002 (5) |
C20 | 0.057 (6) | 0.057 (6) | 0.078 (7) | −0.018 (6) | −0.014 (6) | 0.019 (5) |
C5 | 0.055 (6) | 0.034 (5) | 0.055 (6) | 0.006 (4) | −0.001 (5) | −0.002 (4) |
C13 | 0.074 (6) | 0.029 (5) | 0.072 (6) | −0.024 (5) | 0.003 (6) | 0.002 (5) |
O11 | 0.066 (4) | 0.058 (4) | 0.040 (4) | 0.013 (4) | 0.000 (3) | −0.021 (3) |
O9 | 0.068 (4) | 0.037 (4) | 0.078 (5) | 0.003 (3) | 0.013 (4) | −0.012 (3) |
N5 | 0.043 (5) | 0.065 (6) | 0.053 (6) | −0.007 (5) | −0.004 (4) | −0.004 (5) |
O12 | 0.070 (4) | 0.041 (4) | 0.060 (4) | −0.008 (3) | −0.014 (4) | 0.001 (3) |
O8 | 0.056 (4) | 0.058 (5) | 0.069 (4) | 0.017 (3) | −0.004 (3) | −0.025 (3) |
N4 | 0.039 (5) | 0.060 (6) | 0.059 (5) | −0.006 (4) | −0.001 (4) | 0.015 (4) |
O10 | 0.052 (4) | 0.099 (5) | 0.098 (5) | 0.009 (5) | 0.003 (4) | −0.013 (4) |
C17 | 0.059 (7) | 0.032 (4) | 0.038 (5) | 0.006 (5) | 0.006 (4) | −0.011 (3) |
C3 | 0.050 (7) | 0.033 (5) | 0.051 (5) | −0.012 (5) | −0.009 (4) | 0.003 (3) |
C8 | 0.045 (6) | 0.061 (7) | 0.060 (6) | 0.005 (5) | 0.010 (5) | −0.014 (5) |
C9 | 0.061 (6) | 0.044 (5) | 0.045 (4) | 0.001 (5) | −0.001 (5) | −0.009 (4) |
C14 | 0.043 (6) | 0.034 (5) | 0.065 (7) | 0.001 (4) | −0.006 (5) | −0.016 (4) |
O13 | 0.097 (5) | 0.106 (5) | 0.045 (4) | −0.039 (5) | −0.024 (4) | 0.023 (4) |
C18 | 0.062 (6) | 0.037 (5) | 0.076 (7) | 0.008 (5) | 0.003 (5) | 0.003 (5) |
Sm1—O1 | 2.455 (5) | C19—H19A | 0.9700 |
Sm1—O2 | 2.401 (5) | C19—H19B | 0.9700 |
Sm1—O3 | 2.621 (5) | C6—C5 | 1.390 (10) |
Sm1—O4 | 2.581 (5) | O4—C15 | 1.356 (9) |
Sm1—O5 | 2.503 (4) | O4—C17 | 1.473 (8) |
Sm1—O6 | 2.573 (5) | C15—C14 | 1.404 (11) |
Sm1—O8 | 2.561 (5) | C4—C5 | 1.341 (10) |
Sm1—O9 | 2.507 (6) | C4—C3 | 1.408 (10) |
Sm1—O11 | 2.560 (5) | C4—H4 | 0.9300 |
Sm1—O12 | 2.548 (6) | N3—O7 | 1.205 (7) |
Ni1—O1 | 1.861 (5) | C10—H10 | 0.9300 |
Ni1—O2 | 1.863 (5) | C20—H20A | 0.9600 |
Ni1—N1 | 1.837 (7) | C20—H20B | 0.9600 |
Ni1—N2 | 1.840 (6) | C20—H20C | 0.9600 |
O2—C16 | 1.298 (9) | C5—H5 | 0.9300 |
O1—C1 | 1.312 (8) | C13—C14 | 1.359 (11) |
C16—C11 | 1.391 (10) | C13—H13 | 0.9300 |
C16—C15 | 1.429 (10) | O11—N5 | 1.287 (9) |
N2—C10 | 1.257 (9) | O9—N4 | 1.279 (9) |
N2—C9 | 1.490 (9) | N5—O13 | 1.195 (9) |
O5—N3 | 1.257 (8) | N5—O12 | 1.261 (9) |
C1—C2 | 1.381 (10) | O8—N4 | 1.235 (8) |
C1—C6 | 1.407 (11) | N4—O10 | 1.233 (9) |
O6—N3 | 1.259 (7) | C17—C18 | 1.481 (10) |
O3—C2 | 1.405 (8) | C17—H17A | 0.9700 |
O3—C19 | 1.453 (9) | C17—H17B | 0.9700 |
N1—C7 | 1.303 (10) | C3—H3 | 0.9300 |
N1—C8 | 1.463 (10) | C8—C9 | 1.519 (11) |
C11—C12 | 1.404 (10) | C8—H8A | 0.9700 |
C11—C10 | 1.472 (11) | C8—H8B | 0.9700 |
C2—C3 | 1.368 (10) | C9—H9A | 0.9700 |
C12—C13 | 1.357 (11) | C9—H9B | 0.9700 |
C12—H12 | 0.9300 | C14—H14 | 0.9300 |
C7—C6 | 1.412 (11) | C18—H18A | 0.9600 |
C7—H7 | 0.9300 | C18—H18B | 0.9600 |
C19—C20 | 1.488 (11) | C18—H18C | 0.9600 |
O2—Sm1—O1 | 62.13 (17) | C13—C12—H12 | 120.0 |
O2—Sm1—O5 | 122.20 (18) | C11—C12—H12 | 120.0 |
O1—Sm1—O5 | 114.80 (19) | N1—C7—C6 | 127.7 (8) |
O2—Sm1—O9 | 140.61 (17) | N1—C7—H7 | 116.1 |
O1—Sm1—O9 | 115.33 (19) | C6—C7—H7 | 116.1 |
O5—Sm1—O9 | 95.3 (2) | O3—C19—C20 | 112.2 (7) |
O2—Sm1—O12 | 73.54 (18) | O3—C19—H19A | 109.2 |
O1—Sm1—O12 | 111.58 (17) | C20—C19—H19A | 109.2 |
O5—Sm1—O12 | 132.8 (2) | O3—C19—H19B | 109.2 |
O9—Sm1—O12 | 71.85 (18) | C20—C19—H19B | 109.2 |
O2—Sm1—O11 | 75.72 (17) | H19A—C19—H19B | 107.9 |
O1—Sm1—O11 | 69.51 (19) | C5—C6—C1 | 119.7 (8) |
O5—Sm1—O11 | 161.9 (2) | C5—C6—C7 | 119.3 (7) |
O9—Sm1—O11 | 67.87 (19) | C1—C6—C7 | 121.0 (7) |
O12—Sm1—O11 | 50.1 (2) | C15—O4—C17 | 118.3 (6) |
O2—Sm1—O8 | 133.3 (2) | C15—O4—Sm1 | 119.2 (4) |
O1—Sm1—O8 | 163.45 (19) | C17—O4—Sm1 | 121.9 (4) |
O5—Sm1—O8 | 64.8 (2) | O4—C15—C14 | 126.9 (8) |
O9—Sm1—O8 | 49.90 (19) | O4—C15—C16 | 114.0 (7) |
O12—Sm1—O8 | 73.3 (2) | C14—C15—C16 | 118.9 (8) |
O11—Sm1—O8 | 105.78 (19) | C5—C4—C3 | 119.4 (7) |
O2—Sm1—O6 | 80.85 (17) | C5—C4—H4 | 120.3 |
O1—Sm1—O6 | 71.76 (18) | C3—C4—H4 | 120.3 |
O5—Sm1—O6 | 49.78 (18) | O7—N3—O5 | 122.4 (7) |
O9—Sm1—O6 | 137.87 (18) | O7—N3—O6 | 121.2 (8) |
O12—Sm1—O6 | 147.46 (18) | O5—N3—O6 | 116.3 (7) |
O11—Sm1—O6 | 140.73 (19) | N2—C10—C11 | 122.9 (8) |
O8—Sm1—O6 | 113.23 (19) | N2—C10—H10 | 118.6 |
O2—Sm1—O4 | 61.93 (16) | C11—C10—H10 | 118.6 |
O1—Sm1—O4 | 119.50 (17) | C19—C20—H20A | 109.5 |
O5—Sm1—O4 | 78.42 (18) | C19—C20—H20B | 109.5 |
O9—Sm1—O4 | 121.96 (18) | H20A—C20—H20B | 109.5 |
O12—Sm1—O4 | 71.87 (17) | C19—C20—H20C | 109.5 |
O11—Sm1—O4 | 115.66 (19) | H20A—C20—H20C | 109.5 |
O8—Sm1—O4 | 77.00 (19) | H20B—C20—H20C | 109.5 |
O6—Sm1—O4 | 78.55 (17) | C4—C5—C6 | 121.6 (8) |
O2—Sm1—O3 | 122.88 (16) | C4—C5—H5 | 119.2 |
O1—Sm1—O3 | 60.80 (16) | C6—C5—H5 | 119.2 |
O5—Sm1—O3 | 80.69 (18) | C12—C13—C14 | 120.9 (8) |
O9—Sm1—O3 | 70.72 (17) | C12—C13—H13 | 119.5 |
O12—Sm1—O3 | 131.34 (17) | C14—C13—H13 | 119.5 |
O11—Sm1—O3 | 87.11 (19) | N5—O11—Sm1 | 96.2 (5) |
O8—Sm1—O3 | 103.73 (19) | N4—O9—Sm1 | 97.4 (5) |
O6—Sm1—O3 | 79.66 (17) | O13—N5—O12 | 120.9 (10) |
O4—Sm1—O3 | 156.43 (16) | O13—N5—O11 | 122.8 (9) |
N1—Ni1—N2 | 86.9 (3) | O12—N5—O11 | 116.2 (8) |
N1—Ni1—O1 | 95.3 (3) | N5—O12—Sm1 | 97.5 (5) |
N2—Ni1—O1 | 174.1 (3) | N4—O8—Sm1 | 96.0 (5) |
N1—Ni1—O2 | 175.6 (3) | O10—N4—O8 | 121.8 (9) |
N2—Ni1—O2 | 93.7 (3) | O10—N4—O9 | 121.5 (9) |
O1—Ni1—O2 | 84.6 (2) | O8—N4—O9 | 116.6 (8) |
C16—O2—Ni1 | 124.6 (5) | O4—C17—C18 | 112.5 (6) |
C16—O2—Sm1 | 127.0 (5) | O4—C17—H17A | 109.1 |
Ni1—O2—Sm1 | 107.4 (2) | C18—C17—H17A | 109.1 |
C1—O1—Ni1 | 127.6 (6) | O4—C17—H17B | 109.1 |
C1—O1—Sm1 | 127.0 (5) | C18—C17—H17B | 109.1 |
Ni1—O1—Sm1 | 105.4 (2) | H17A—C17—H17B | 107.8 |
O2—C16—C11 | 125.3 (7) | C2—C3—C4 | 119.3 (7) |
O2—C16—C15 | 116.8 (7) | C2—C3—H3 | 120.3 |
C11—C16—C15 | 117.9 (7) | C4—C3—H3 | 120.3 |
C10—N2—C9 | 120.3 (7) | N1—C8—C9 | 105.1 (7) |
C10—N2—Ni1 | 128.8 (6) | N1—C8—H8A | 110.7 |
C9—N2—Ni1 | 110.8 (5) | C9—C8—H8A | 110.7 |
N3—O5—Sm1 | 98.2 (4) | N1—C8—H8B | 110.7 |
O1—C1—C2 | 118.9 (8) | C9—C8—H8B | 110.7 |
O1—C1—C6 | 123.5 (8) | H8A—C8—H8B | 108.8 |
C2—C1—C6 | 117.6 (7) | N2—C9—C8 | 106.2 (6) |
N3—O6—Sm1 | 94.7 (4) | N2—C9—H9A | 110.5 |
C2—O3—C19 | 118.3 (6) | C8—C9—H9A | 110.5 |
C2—O3—Sm1 | 119.9 (4) | N2—C9—H9B | 110.5 |
C19—O3—Sm1 | 121.7 (4) | C8—C9—H9B | 110.5 |
C7—N1—C8 | 120.5 (7) | H9A—C9—H9B | 108.7 |
C7—N1—Ni1 | 124.6 (6) | C13—C14—C15 | 121.1 (8) |
C8—N1—Ni1 | 114.5 (6) | C13—C14—H14 | 119.4 |
C16—C11—C12 | 120.9 (8) | C15—C14—H14 | 119.4 |
C16—C11—C10 | 120.9 (7) | C17—C18—H18A | 109.5 |
C12—C11—C10 | 118.1 (8) | C17—C18—H18B | 109.5 |
C3—C2—C1 | 122.1 (7) | H18A—C18—H18B | 109.5 |
C3—C2—O3 | 124.5 (7) | C17—C18—H18C | 109.5 |
C1—C2—O3 | 113.2 (6) | H18A—C18—H18C | 109.5 |
C13—C12—C11 | 120.0 (8) | H18B—C18—H18C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20A···O9 | 0.96 | 2.49 | 3.150 (10) | 126 |
C20—H20C···O7i | 0.96 | 2.55 | 3.308 (12) | 136 |
C17—H17A···O8ii | 0.97 | 2.59 | 3.536 (9) | 164 |
C9—H9A···O13iii | 0.97 | 2.43 | 3.283 (11) | 147 |
C7—H7···O13iv | 0.93 | 2.39 | 3.320 (10) | 173 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+2; (ii) x+1/2, −y+3/2, −z+2; (iii) x+1, y, z; (iv) −x+2, y−1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [NiSm(C20H22N2O4)(NO3)3] |
Mr | 749.49 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 8.6097 (14), 13.750 (2), 21.113 (3) |
V (Å3) | 2499.4 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 3.16 |
Crystal size (mm) | 0.26 × 0.14 × 0.07 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.494, 0.821 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18707, 6073, 2970 |
Rint | 0.089 |
(sin θ/λ)max (Å−1) | 0.665 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.084, 1.00 |
No. of reflections | 6073 |
No. of parameters | 362 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.58, −1.58 |
Absolute structure | Flack (1983), 2588 Freidel pairs |
Absolute structure parameter | 0.007 (19) |
Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), APEX2 and publCIF (Westrip, 2007).
Sm1—O1 | 2.455 (5) | Sm1—O9 | 2.507 (6) |
Sm1—O2 | 2.401 (5) | Sm1—O11 | 2.560 (5) |
Sm1—O3 | 2.621 (5) | Sm1—O12 | 2.548 (6) |
Sm1—O4 | 2.581 (5) | Ni1—O1 | 1.861 (5) |
Sm1—O5 | 2.503 (4) | Ni1—O2 | 1.863 (5) |
Sm1—O6 | 2.573 (5) | Ni1—N1 | 1.837 (7) |
Sm1—O8 | 2.561 (5) | Ni1—N2 | 1.840 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
C20—H20A···O9 | 0.96 | 2.49 | 3.150 (10) | 125.8 |
C20—H20C···O7i | 0.96 | 2.55 | 3.308 (12) | 135.8 |
C17—H17A···O8ii | 0.97 | 2.59 | 3.536 (9) | 164.0 |
C9—H9A···O13iii | 0.97 | 2.43 | 3.283 (11) | 146.7 |
C7—H7···O13iv | 0.93 | 2.39 | 3.320 (10) | 173.1 |
Symmetry codes: (i) x−1/2, −y+1/2, −z+2; (ii) x+1/2, −y+3/2, −z+2; (iii) x+1, y, z; (iv) −x+2, y−1/2, −z+3/2. |
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), 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 P212121, with nickel and samarium doubly bridged by two phenolate O atoms provided by a salen-type Schiff base ligand. The inner salen-type cavity is occupied by nickel(II), while samarium(III) is present in the open and larger portion of the dinucleating compartmental Schiff base ligand. The dihedral angles between the mean planes of Ni1/O1/O2 and Sm1/O1/O2 is 6.28 (29)° suggesting that the bridging moiety is almost planar, with the deviation of atoms from the least squares Ni1/O1/O2/Sm1 plane being -0.0535 (2)Å for Ni, -0.0354 (3)Å for Sm, 0.0437 (2)Å for O1 and 0.0451 (2)Å for O2.
The samarium(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 samarium to complete the decacoordination. The three kinds of Sm—O bond distances are significantly different, the shortest being the Sm—O(phenolate) and longest being the Sm—O(ethoxy) separations.
The coordination of nickel(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 0.0798 (2) Å, while Ni1 is 0.0093 (2)Å below this square plane.
Adjacent molecules are held together by weak interactions (O10···Ni1 = 3.381 (4) Å, C7—H7···O13i = 3.320 (10), C9—H9A···O13ii = 3.283 (11), C17—H17A···O8iii=3.536 (9) and C20—H20c···O7iv = 3.308 (12); symmetry codes: (i) -x + 2, y - 1/2, -z + 3/2; (ii) 1 + x, y, z; (iii) 1/2 + x, 3/2 - y, 2 - z; (iv) x - 1/2, 1/2 - y, 2 - z.) these link the molecules into a two-dimensional zigzag sheet (Fig 2).