Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014398/wn6044sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014398/wn6044Isup2.hkl |
CCDC reference: 175334
The title complex was synthesized in a single step. Samarium chloride solution (10 ml, 2 mmol) was mixed with acetylacetone (0.62 ml, 6 mmol) in the presence of 50 ml of ethanol. The solution was heated to boiling and 2 N sodium hydroxide was added to the hot solution (to achieve pH = 6–7), followed by the addition of 1,10-phenanthroline (0.396 g, 2 mmol) in 10 ml of ethanol. The mixture was stirred for 2 h at room temperature. The precipitate thus formed was filtered, washed with water and recrystallized from aqueous ethanol. Crystals were obtained by slow evaporation at low temperature from a solution in aqueous ethanol.
Data collection: CrystalClear (Rigaku, 1999); data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. View of the title Sm complex (Johnson, 1965) with the atomic numbering scheme. The displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. |
[Sm(C5H7O2)3(C12H8N2)] | F(000) = 1260 |
Mr = 627.87 | Dx = 1.45 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 9.432 (2) Å | Cell parameters from 23142 reflections |
b = 20.957 (5) Å | θ = 3.0–25.0° |
c = 14.728 (3) Å | µ = 2.08 mm−1 |
β = 98.899 (9)° | T = 173 K |
V = 2876 (1) Å3 | Prism, colourless |
Z = 4 | 0.20 × 0.20 × 0.20 mm |
Rigaku AFC8 coupled with mercury CCD diffractometer | 4253 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 3.0° |
Graphite monochromator | h = −11→10 |
ω scans | k = −24→24 |
23142 measured reflections | l = −15→17 |
23142 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.073 | w = 1/[σ2(Fo2) + 55.2376P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.201 | (Δ/σ)max = 0.005 |
S = 1.32 | Δρmax = 2.48 e Å−3 |
5098 reflections | Δρmin = −1.88 e Å−3 |
332 parameters |
[Sm(C5H7O2)3(C12H8N2)] | V = 2876 (1) Å3 |
Mr = 627.87 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.432 (2) Å | µ = 2.08 mm−1 |
b = 20.957 (5) Å | T = 173 K |
c = 14.728 (3) Å | 0.20 × 0.20 × 0.20 mm |
β = 98.899 (9)° |
Rigaku AFC8 coupled with mercury CCD diffractometer | 23142 independent reflections |
23142 measured reflections | 4253 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.073 | 0 restraints |
wR(F2) = 0.201 | H-atom parameters constrained |
S = 1.32 | w = 1/[σ2(Fo2) + 55.2376P] where P = (Fo2 + 2Fc2)/3 |
5098 reflections | Δρmax = 2.48 e Å−3 |
332 parameters | Δρmin = −1.88 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Sm1 | 0.41619 (4) | 0.154403 (16) | 0.16003 (2) | 0.02731 (12) | |
O1 | 0.2562 (5) | 0.1074 (2) | 0.0416 (3) | 0.0362 (12) | |
O2 | 0.4770 (5) | 0.0445 (2) | 0.1545 (3) | 0.0384 (12) | |
O3 | 0.5312 (5) | 0.2539 (2) | 0.2005 (3) | 0.0411 (12) | |
C12 | 0.7762 (7) | 0.1213 (3) | 0.1610 (5) | 0.0357 (17) | |
H12 | 0.7567 | 0.0973 | 0.2124 | 0.043* | |
O4 | 0.2371 (5) | 0.2346 (2) | 0.1495 (3) | 0.0370 (12) | |
C4 | 0.6053 (9) | 0.2482 (3) | −0.0997 (5) | 0.0409 (19) | |
C1 | 0.3390 (8) | 0.2350 (3) | −0.0540 (5) | 0.0404 (19) | |
H1 | 0.2455 | 0.2315 | −0.0381 | 0.048* | |
C13 | 0.4191 (8) | −0.0047 (3) | 0.1132 (5) | 0.0389 (18) | |
C11 | 0.9171 (8) | 0.1225 (3) | 0.1439 (6) | 0.042 (2) | |
H11 | 0.9907 | 0.0994 | 0.1813 | 0.05* | |
C15 | 0.2301 (7) | 0.0510 (4) | 0.0103 (5) | 0.0362 (18) | |
N1 | 0.4474 (6) | 0.2098 (3) | 0.0033 (4) | 0.0294 (14) | |
C2 | 0.3529 (10) | 0.2663 (4) | −0.1355 (5) | 0.047 (2) | |
H2 | 0.2715 | 0.2823 | −0.1751 | 0.056* | |
C17 | 0.4882 (10) | −0.0675 (4) | 0.1437 (6) | 0.061 (3) | |
H17A | 0.5492 | −0.0622 | 0.2033 | 0.091* | |
H17B | 0.5467 | −0.0822 | 0.0982 | 0.091* | |
H17C | 0.4135 | −0.0992 | 0.1492 | 0.091* | |
C18 | 0.2343 (8) | 0.2952 (4) | 0.1499 (5) | 0.042 (2) | |
C22 | 0.0896 (9) | 0.3260 (4) | 0.1337 (7) | 0.064 (3) | |
H22A | 0.0426 | 0.3167 | 0.071 | 0.096* | |
H22B | 0.1002 | 0.3722 | 0.1418 | 0.096* | |
H22C | 0.031 | 0.3091 | 0.1777 | 0.096* | |
C5 | 0.5805 (7) | 0.2154 (3) | −0.0200 (5) | 0.0294 (17) | |
C6 | 0.6973 (7) | 0.1847 (3) | 0.0374 (5) | 0.0293 (16) | |
C16 | 0.1114 (9) | 0.0466 (4) | −0.0711 (5) | 0.055 (2) | |
H16A | 0.0233 | 0.0651 | −0.0548 | 0.083* | |
H16B | 0.0945 | 0.0017 | −0.0882 | 0.083* | |
H16C | 0.1393 | 0.07 | −0.1231 | 0.083* | |
C10 | 0.9460 (8) | 0.1583 (4) | 0.0711 (5) | 0.045 (2) | |
H10 | 1.042 | 0.1619 | 0.0596 | 0.054* | |
C9 | 0.7499 (10) | 0.2522 (4) | −0.1190 (6) | 0.059 (3) | |
H9 | 0.7683 | 0.2753 | −0.1714 | 0.071* | |
C8 | 0.8592 (10) | 0.2241 (4) | −0.0649 (6) | 0.056 (2) | |
H8 | 0.9534 | 0.2274 | −0.0797 | 0.067* | |
C7 | 0.8365 (7) | 0.1895 (4) | 0.0139 (5) | 0.0364 (18) | |
C21 | 0.6206 (10) | 0.3590 (4) | 0.1927 (7) | 0.078 (3) | |
H21A | 0.6881 | 0.3515 | 0.2493 | 0.117* | |
H21B | 0.583 | 0.4026 | 0.1931 | 0.117* | |
H21C | 0.6701 | 0.3534 | 0.1395 | 0.117* | |
C19 | 0.3540 (9) | 0.3339 (4) | 0.1634 (6) | 0.051 (2) | |
H19 | 0.34 | 0.3786 | 0.1564 | 0.061* | |
C14 | 0.3025 (9) | −0.0034 (4) | 0.0452 (6) | 0.047 (2) | |
H14 | 0.2682 | −0.0432 | 0.0198 | 0.056* | |
C20 | 0.4963 (9) | 0.3114 (4) | 0.1869 (5) | 0.046 (2) | |
O5 | 0.2609 (5) | 0.1120 (2) | 0.2587 (3) | 0.0405 (13) | |
O6 | 0.5553 (5) | 0.1351 (2) | 0.3041 (3) | 0.0390 (12) | |
N2 | 0.6685 (5) | 0.1508 (3) | 0.1116 (3) | 0.0271 (12) | |
C25 | 0.2860 (9) | 0.0777 (4) | 0.3312 (6) | 0.052 (2) | |
C23 | 0.5438 (9) | 0.0959 (4) | 0.3682 (6) | 0.048 (2) | |
C24 | 0.4162 (9) | 0.0687 (4) | 0.3837 (6) | 0.065 (3) | |
H24 | 0.4199 | 0.0414 | 0.4356 | 0.078* | |
C3 | 0.4862 (11) | 0.2729 (4) | −0.1559 (5) | 0.055 (2) | |
H3 | 0.4992 | 0.2951 | −0.2103 | 0.066* | |
C27 | 0.6803 (9) | 0.0784 (5) | 0.4296 (6) | 0.070 (3) | |
H27A | 0.7415 | 0.0536 | 0.3947 | 0.105* | |
H27B | 0.6578 | 0.0529 | 0.4813 | 0.105* | |
H27C | 0.7307 | 0.1174 | 0.453 | 0.105* | |
C26 | 0.1510 (10) | 0.0466 (6) | 0.3589 (8) | 0.098 (4) | |
H26A | 0.0917 | 0.0794 | 0.382 | 0.147* | |
H26B | 0.1795 | 0.0148 | 0.4071 | 0.147* | |
H26C | 0.0958 | 0.0257 | 0.3052 | 0.147* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sm1 | 0.0261 (2) | 0.02621 (19) | 0.0293 (2) | −0.0001 (2) | 0.00346 (14) | −0.00154 (18) |
O1 | 0.032 (3) | 0.034 (3) | 0.042 (3) | −0.003 (2) | 0.004 (2) | −0.007 (2) |
O2 | 0.033 (3) | 0.031 (3) | 0.049 (3) | 0.002 (2) | 0.002 (2) | −0.002 (2) |
O3 | 0.048 (3) | 0.029 (3) | 0.044 (3) | −0.003 (2) | −0.003 (2) | −0.004 (2) |
C12 | 0.033 (5) | 0.039 (4) | 0.034 (4) | 0.009 (4) | −0.001 (4) | −0.008 (3) |
O4 | 0.038 (3) | 0.031 (3) | 0.042 (3) | 0.005 (2) | 0.005 (2) | −0.004 (2) |
C4 | 0.059 (5) | 0.033 (4) | 0.032 (5) | 0.002 (4) | 0.012 (4) | 0.001 (3) |
C1 | 0.036 (5) | 0.040 (5) | 0.042 (5) | 0.003 (4) | −0.002 (4) | −0.005 (4) |
C13 | 0.047 (5) | 0.032 (4) | 0.041 (5) | −0.007 (4) | 0.016 (4) | −0.006 (4) |
C11 | 0.031 (4) | 0.023 (4) | 0.066 (6) | 0.008 (4) | −0.007 (4) | −0.019 (4) |
C15 | 0.029 (4) | 0.043 (5) | 0.038 (4) | −0.012 (4) | 0.011 (3) | −0.007 (4) |
N1 | 0.030 (4) | 0.029 (3) | 0.028 (3) | 0.003 (3) | 0.001 (3) | 0.002 (3) |
C2 | 0.057 (6) | 0.048 (5) | 0.030 (5) | 0.013 (4) | −0.008 (4) | 0.011 (4) |
C17 | 0.078 (7) | 0.028 (5) | 0.076 (7) | 0.005 (4) | 0.012 (5) | −0.005 (4) |
C18 | 0.050 (5) | 0.041 (5) | 0.034 (5) | 0.014 (4) | 0.005 (4) | 0.002 (4) |
C22 | 0.065 (6) | 0.046 (6) | 0.084 (7) | 0.027 (4) | 0.021 (5) | 0.001 (5) |
C5 | 0.034 (4) | 0.024 (4) | 0.029 (4) | 0.000 (3) | 0.005 (3) | −0.008 (3) |
C6 | 0.029 (4) | 0.026 (4) | 0.031 (4) | 0.000 (3) | 0.001 (3) | −0.006 (3) |
C16 | 0.054 (5) | 0.055 (5) | 0.051 (5) | −0.005 (5) | −0.009 (4) | −0.013 (4) |
C10 | 0.030 (4) | 0.046 (5) | 0.059 (5) | −0.003 (4) | 0.011 (4) | −0.022 (5) |
C9 | 0.074 (7) | 0.059 (6) | 0.054 (6) | −0.010 (5) | 0.036 (5) | 0.004 (5) |
C8 | 0.048 (6) | 0.059 (6) | 0.066 (6) | −0.008 (5) | 0.029 (5) | −0.002 (5) |
C7 | 0.027 (4) | 0.042 (4) | 0.042 (5) | −0.006 (3) | 0.012 (4) | −0.013 (4) |
C21 | 0.069 (7) | 0.042 (6) | 0.113 (9) | −0.024 (5) | −0.014 (6) | −0.006 (5) |
C19 | 0.063 (6) | 0.030 (5) | 0.056 (5) | 0.004 (4) | −0.001 (4) | −0.001 (4) |
C14 | 0.052 (5) | 0.027 (4) | 0.058 (6) | −0.006 (4) | −0.003 (4) | −0.012 (4) |
C20 | 0.061 (6) | 0.039 (5) | 0.035 (5) | −0.011 (4) | 0.000 (4) | −0.009 (4) |
O5 | 0.037 (3) | 0.041 (3) | 0.044 (3) | 0.002 (2) | 0.008 (2) | 0.009 (3) |
O6 | 0.045 (3) | 0.041 (3) | 0.028 (3) | −0.010 (2) | −0.002 (2) | 0.006 (2) |
N2 | 0.014 (3) | 0.027 (3) | 0.037 (3) | 0.007 (3) | −0.006 (2) | −0.001 (3) |
C25 | 0.044 (5) | 0.053 (5) | 0.061 (6) | −0.006 (4) | 0.011 (4) | 0.023 (5) |
C23 | 0.047 (5) | 0.051 (5) | 0.043 (5) | −0.002 (4) | −0.001 (4) | 0.005 (4) |
C24 | 0.054 (6) | 0.073 (7) | 0.066 (6) | −0.007 (5) | 0.004 (5) | 0.041 (5) |
C3 | 0.084 (7) | 0.049 (5) | 0.030 (5) | 0.010 (5) | 0.004 (5) | 0.014 (4) |
C27 | 0.055 (6) | 0.090 (8) | 0.058 (6) | −0.015 (5) | −0.012 (5) | 0.037 (5) |
C26 | 0.057 (6) | 0.117 (10) | 0.121 (10) | 0.000 (6) | 0.015 (6) | 0.090 (8) |
Sm1—O1 | 2.341 (5) | C11—C10 | 1.369 (11) |
Sm1—O6 | 2.351 (5) | C15—C14 | 1.386 (10) |
Sm1—O4 | 2.372 (5) | C15—C16 | 1.512 (10) |
Sm1—O2 | 2.378 (5) | N1—C5 | 1.357 (8) |
Sm1—O3 | 2.383 (5) | C2—C3 | 1.345 (11) |
Sm1—O5 | 2.388 (5) | C18—C19 | 1.379 (11) |
Sm1—N2 | 2.589 (5) | C18—C22 | 1.495 (10) |
Sm1—N1 | 2.641 (5) | C5—C6 | 1.432 (9) |
O1—C15 | 1.278 (8) | C6—N2 | 1.366 (8) |
O2—C13 | 1.276 (8) | C6—C7 | 1.412 (9) |
O3—C20 | 1.257 (9) | C10—C7 | 1.392 (11) |
C12—N2 | 1.310 (8) | C9—C8 | 1.338 (12) |
C12—C11 | 1.391 (10) | C8—C7 | 1.411 (11) |
O4—C18 | 1.270 (9) | C21—C20 | 1.531 (11) |
C4—C3 | 1.389 (11) | C19—C20 | 1.414 (11) |
C4—C5 | 1.411 (10) | O5—C25 | 1.280 (9) |
C4—C9 | 1.438 (11) | O6—C23 | 1.269 (9) |
C1—N1 | 1.331 (9) | C25—C24 | 1.359 (11) |
C1—C2 | 1.391 (10) | C25—C26 | 1.541 (11) |
C13—C14 | 1.369 (11) | C23—C24 | 1.382 (11) |
C13—C17 | 1.507 (10) | C23—C27 | 1.500 (11) |
O1—Sm1—O6 | 143.70 (16) | O1—C15—C14 | 124.8 (7) |
O1—Sm1—O4 | 83.05 (16) | O1—C15—C16 | 114.8 (7) |
O6—Sm1—O4 | 118.26 (16) | C14—C15—C16 | 120.4 (7) |
O1—Sm1—O2 | 72.40 (16) | C1—N1—C5 | 117.1 (6) |
O6—Sm1—O2 | 76.16 (16) | C1—N1—Sm1 | 123.4 (5) |
O4—Sm1—O2 | 149.06 (16) | C5—N1—Sm1 | 119.4 (4) |
O1—Sm1—O3 | 140.45 (16) | C3—C2—C1 | 117.2 (7) |
O6—Sm1—O3 | 75.84 (16) | O4—C18—C19 | 124.8 (7) |
O4—Sm1—O3 | 71.83 (17) | O4—C18—C22 | 116.7 (7) |
O2—Sm1—O3 | 138.85 (17) | C19—C18—C22 | 118.5 (7) |
O1—Sm1—O5 | 84.90 (17) | N1—C5—C4 | 122.1 (7) |
O6—Sm1—O5 | 72.33 (17) | N1—C5—C6 | 118.0 (6) |
O4—Sm1—O5 | 78.80 (16) | C4—C5—C6 | 119.9 (6) |
O2—Sm1—O5 | 80.49 (16) | N2—C6—C7 | 122.8 (6) |
O3—Sm1—O5 | 118.13 (17) | N2—C6—C5 | 118.4 (6) |
O1—Sm1—N2 | 107.26 (16) | C7—C6—C5 | 118.9 (6) |
O6—Sm1—N2 | 80.50 (16) | C11—C10—C7 | 120.9 (7) |
O4—Sm1—N2 | 132.74 (17) | C8—C9—C4 | 121.6 (8) |
O2—Sm1—N2 | 74.04 (16) | C9—C8—C7 | 121.0 (8) |
O3—Sm1—N2 | 72.09 (17) | C10—C7—C8 | 123.2 (7) |
O5—Sm1—N2 | 146.42 (17) | C10—C7—C6 | 116.7 (7) |
O1—Sm1—N1 | 71.34 (16) | C8—C7—C6 | 120.2 (7) |
O6—Sm1—N1 | 137.93 (16) | C18—C19—C20 | 124.4 (7) |
O4—Sm1—N1 | 78.79 (16) | C13—C14—C15 | 125.5 (7) |
O2—Sm1—N1 | 109.60 (16) | O3—C20—C19 | 125.0 (7) |
O3—Sm1—N1 | 74.11 (17) | O3—C20—C21 | 115.9 (7) |
O5—Sm1—N1 | 148.99 (17) | C19—C20—C21 | 119.1 (7) |
N2—Sm1—N1 | 62.65 (16) | C25—O5—Sm1 | 131.7 (5) |
C15—O1—Sm1 | 136.4 (5) | C23—O6—Sm1 | 133.0 (5) |
C13—O2—Sm1 | 135.3 (5) | C12—N2—C6 | 117.2 (6) |
C20—O3—Sm1 | 134.5 (5) | C12—N2—Sm1 | 121.9 (4) |
N2—C12—C11 | 124.8 (7) | C6—N2—Sm1 | 120.7 (4) |
C18—O4—Sm1 | 136.4 (5) | O5—C25—C24 | 126.0 (7) |
C3—C4—C5 | 117.0 (7) | O5—C25—C26 | 113.9 (7) |
C3—C4—C9 | 124.4 (8) | C24—C25—C26 | 120.1 (7) |
C5—C4—C9 | 118.5 (7) | O6—C23—C24 | 124.6 (8) |
N1—C1—C2 | 124.7 (7) | O6—C23—C27 | 116.3 (7) |
O2—C13—C14 | 124.7 (7) | C24—C23—C27 | 119.1 (7) |
O2—C13—C17 | 115.5 (7) | C25—C24—C23 | 125.5 (8) |
C14—C13—C17 | 119.7 (7) | C2—C3—C4 | 121.8 (7) |
C10—C11—C12 | 117.7 (7) |
Experimental details
Crystal data | |
Chemical formula | [Sm(C5H7O2)3(C12H8N2)] |
Mr | 627.87 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 9.432 (2), 20.957 (5), 14.728 (3) |
β (°) | 98.899 (9) |
V (Å3) | 2876 (1) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.08 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC8 coupled with mercury CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23142, 23142, 4253 |
Rint | ? |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.073, 0.201, 1.32 |
No. of reflections | 5098 |
No. of parameters | 332 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + 55.2376P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 2.48, −1.88 |
Computer programs: CrystalClear (Rigaku, 1999), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Sm1—O1 | 2.341 (5) | Sm1—O3 | 2.383 (5) |
Sm1—O6 | 2.351 (5) | Sm1—O5 | 2.388 (5) |
Sm1—O4 | 2.372 (5) | Sm1—N2 | 2.589 (5) |
Sm1—O2 | 2.378 (5) | Sm1—N1 | 2.641 (5) |
O1—Sm1—O2 | 72.40 (16) | O6—Sm1—O5 | 72.33 (17) |
O4—Sm1—O3 | 71.83 (17) | N2—Sm1—N1 | 62.65 (16) |
In a continuation of work on the structures of MOCVD (metal-organic chemical vapour deposition) precursors (Patnaik et al., 1996; Urs et al., 2000, 2001), the structure of a samarium complex, (I), has been analysed. The crystal was found to be a non-merohedral twin with two components each. The twinning arises from a rotation of 180° around the normal to (100) in real space. This twin law was used to process the data using the program TwinSolve (Rigaku, 1999). The eightfold coordination of the Sm atom is in the form of a distorted square antiprism. The ligands span the opposite edges of the two square faces of the coordination antiprism (s edges) (Hoard & Silverton, 1963), as observed in rare earth metal complexes of europium (Watson et al., 1972), lanthanum (Kuz'mina et al., 1997), cerium and praseodymium (Christidis et al., 1998). The title complex has only one molecule in the asymmetric unit, as in the europium and praseodymium complexes, and is found to be isostructural with the praseodymium complex. The Sm—O bond distances are in the range 2.341 (5)–2.388 (5) Å and the Sm—N distances are 2.589 (5) and 2.641 (5) Å. The angle between the least-squares mean planes fitted to the two square faces of the coordination antiprism is 2.8 (1)° (Nardelli, 1995).