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The crystal of the title complex, [Sm(C5H7O2)3(C12H8N2)], was found to be a non-merohedral twin. The samarium coordination is in the form of a distorted square antiprism, with the six O and two N atoms of the ligands lying at the apices.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014398/wn6044sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014398/wn6044Isup2.hkl
Contains datablock I

CCDC reference: 175334

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.012 Å
  • R factor = 0.073
  • wR factor = 0.201
  • Data-to-parameter ratio = 15.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.04 From the CIF: _reflns_number_total 23142 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 5098 Completeness (_total/calc) 453.94% Alert A: > 15% excess reflns - sys abs data present?
Author response: The extra reflections are due to the fact that we collected both sets of twin reflections but many of these reflections are allocated to only one or the other of the two twins.

1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check

Comment top

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).

Experimental top

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.

Computing details top

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).

Figures top
[Figure 1] 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.
tris(2,4-pentadionato)(1,10-phenanthroline)samarium(III) top
Crystal data top
[Sm(C5H7O2)3(C12H8N2)]F(000) = 1260
Mr = 627.87Dx = 1.45 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
a = 9.432 (2) ÅCell parameters from 23142 reflections
b = 20.957 (5) Åθ = 3.0–25.0°
c = 14.728 (3) ŵ = 2.08 mm1
β = 98.899 (9)°T = 173 K
V = 2876 (1) Å3Prism, colourless
Z = 40.20 × 0.20 × 0.20 mm
Data collection top
Rigaku AFC8 coupled with mercury CCD
diffractometer
4253 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 3.0°
Graphite monochromatorh = 1110
ω scansk = 2424
23142 measured reflectionsl = 1517
23142 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-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 = 1.32Δρmax = 2.48 e Å3
5098 reflectionsΔρmin = 1.88 e Å3
332 parameters
Crystal data top
[Sm(C5H7O2)3(C12H8N2)]V = 2876 (1) Å3
Mr = 627.87Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.432 (2) ŵ = 2.08 mm1
b = 20.957 (5) ÅT = 173 K
c = 14.728 (3) Å0.20 × 0.20 × 0.20 mm
β = 98.899 (9)°
Data collection top
Rigaku AFC8 coupled with mercury CCD
diffractometer
23142 independent reflections
23142 measured reflections4253 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0730 restraints
wR(F2) = 0.201H-atom parameters constrained
S = 1.32 w = 1/[σ2(Fo2) + 55.2376P]
where P = (Fo2 + 2Fc2)/3
5098 reflectionsΔρmax = 2.48 e Å3
332 parametersΔρmin = 1.88 e Å3
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sm10.41619 (4)0.154403 (16)0.16003 (2)0.02731 (12)
O10.2562 (5)0.1074 (2)0.0416 (3)0.0362 (12)
O20.4770 (5)0.0445 (2)0.1545 (3)0.0384 (12)
O30.5312 (5)0.2539 (2)0.2005 (3)0.0411 (12)
C120.7762 (7)0.1213 (3)0.1610 (5)0.0357 (17)
H120.75670.09730.21240.043*
O40.2371 (5)0.2346 (2)0.1495 (3)0.0370 (12)
C40.6053 (9)0.2482 (3)0.0997 (5)0.0409 (19)
C10.3390 (8)0.2350 (3)0.0540 (5)0.0404 (19)
H10.24550.23150.03810.048*
C130.4191 (8)0.0047 (3)0.1132 (5)0.0389 (18)
C110.9171 (8)0.1225 (3)0.1439 (6)0.042 (2)
H110.99070.09940.18130.05*
C150.2301 (7)0.0510 (4)0.0103 (5)0.0362 (18)
N10.4474 (6)0.2098 (3)0.0033 (4)0.0294 (14)
C20.3529 (10)0.2663 (4)0.1355 (5)0.047 (2)
H20.27150.28230.17510.056*
C170.4882 (10)0.0675 (4)0.1437 (6)0.061 (3)
H17A0.54920.06220.20330.091*
H17B0.54670.08220.09820.091*
H17C0.41350.09920.14920.091*
C180.2343 (8)0.2952 (4)0.1499 (5)0.042 (2)
C220.0896 (9)0.3260 (4)0.1337 (7)0.064 (3)
H22A0.04260.31670.0710.096*
H22B0.10020.37220.14180.096*
H22C0.0310.30910.17770.096*
C50.5805 (7)0.2154 (3)0.0200 (5)0.0294 (17)
C60.6973 (7)0.1847 (3)0.0374 (5)0.0293 (16)
C160.1114 (9)0.0466 (4)0.0711 (5)0.055 (2)
H16A0.02330.06510.05480.083*
H16B0.09450.00170.08820.083*
H16C0.13930.070.12310.083*
C100.9460 (8)0.1583 (4)0.0711 (5)0.045 (2)
H101.0420.16190.05960.054*
C90.7499 (10)0.2522 (4)0.1190 (6)0.059 (3)
H90.76830.27530.17140.071*
C80.8592 (10)0.2241 (4)0.0649 (6)0.056 (2)
H80.95340.22740.07970.067*
C70.8365 (7)0.1895 (4)0.0139 (5)0.0364 (18)
C210.6206 (10)0.3590 (4)0.1927 (7)0.078 (3)
H21A0.68810.35150.24930.117*
H21B0.5830.40260.19310.117*
H21C0.67010.35340.13950.117*
C190.3540 (9)0.3339 (4)0.1634 (6)0.051 (2)
H190.340.37860.15640.061*
C140.3025 (9)0.0034 (4)0.0452 (6)0.047 (2)
H140.26820.04320.01980.056*
C200.4963 (9)0.3114 (4)0.1869 (5)0.046 (2)
O50.2609 (5)0.1120 (2)0.2587 (3)0.0405 (13)
O60.5553 (5)0.1351 (2)0.3041 (3)0.0390 (12)
N20.6685 (5)0.1508 (3)0.1116 (3)0.0271 (12)
C250.2860 (9)0.0777 (4)0.3312 (6)0.052 (2)
C230.5438 (9)0.0959 (4)0.3682 (6)0.048 (2)
C240.4162 (9)0.0687 (4)0.3837 (6)0.065 (3)
H240.41990.04140.43560.078*
C30.4862 (11)0.2729 (4)0.1559 (5)0.055 (2)
H30.49920.29510.21030.066*
C270.6803 (9)0.0784 (5)0.4296 (6)0.070 (3)
H27A0.74150.05360.39470.105*
H27B0.65780.05290.48130.105*
H27C0.73070.11740.4530.105*
C260.1510 (10)0.0466 (6)0.3589 (8)0.098 (4)
H26A0.09170.07940.3820.147*
H26B0.17950.01480.40710.147*
H26C0.09580.02570.30520.147*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sm10.0261 (2)0.02621 (19)0.0293 (2)0.0001 (2)0.00346 (14)0.00154 (18)
O10.032 (3)0.034 (3)0.042 (3)0.003 (2)0.004 (2)0.007 (2)
O20.033 (3)0.031 (3)0.049 (3)0.002 (2)0.002 (2)0.002 (2)
O30.048 (3)0.029 (3)0.044 (3)0.003 (2)0.003 (2)0.004 (2)
C120.033 (5)0.039 (4)0.034 (4)0.009 (4)0.001 (4)0.008 (3)
O40.038 (3)0.031 (3)0.042 (3)0.005 (2)0.005 (2)0.004 (2)
C40.059 (5)0.033 (4)0.032 (5)0.002 (4)0.012 (4)0.001 (3)
C10.036 (5)0.040 (5)0.042 (5)0.003 (4)0.002 (4)0.005 (4)
C130.047 (5)0.032 (4)0.041 (5)0.007 (4)0.016 (4)0.006 (4)
C110.031 (4)0.023 (4)0.066 (6)0.008 (4)0.007 (4)0.019 (4)
C150.029 (4)0.043 (5)0.038 (4)0.012 (4)0.011 (3)0.007 (4)
N10.030 (4)0.029 (3)0.028 (3)0.003 (3)0.001 (3)0.002 (3)
C20.057 (6)0.048 (5)0.030 (5)0.013 (4)0.008 (4)0.011 (4)
C170.078 (7)0.028 (5)0.076 (7)0.005 (4)0.012 (5)0.005 (4)
C180.050 (5)0.041 (5)0.034 (5)0.014 (4)0.005 (4)0.002 (4)
C220.065 (6)0.046 (6)0.084 (7)0.027 (4)0.021 (5)0.001 (5)
C50.034 (4)0.024 (4)0.029 (4)0.000 (3)0.005 (3)0.008 (3)
C60.029 (4)0.026 (4)0.031 (4)0.000 (3)0.001 (3)0.006 (3)
C160.054 (5)0.055 (5)0.051 (5)0.005 (5)0.009 (4)0.013 (4)
C100.030 (4)0.046 (5)0.059 (5)0.003 (4)0.011 (4)0.022 (5)
C90.074 (7)0.059 (6)0.054 (6)0.010 (5)0.036 (5)0.004 (5)
C80.048 (6)0.059 (6)0.066 (6)0.008 (5)0.029 (5)0.002 (5)
C70.027 (4)0.042 (4)0.042 (5)0.006 (3)0.012 (4)0.013 (4)
C210.069 (7)0.042 (6)0.113 (9)0.024 (5)0.014 (6)0.006 (5)
C190.063 (6)0.030 (5)0.056 (5)0.004 (4)0.001 (4)0.001 (4)
C140.052 (5)0.027 (4)0.058 (6)0.006 (4)0.003 (4)0.012 (4)
C200.061 (6)0.039 (5)0.035 (5)0.011 (4)0.000 (4)0.009 (4)
O50.037 (3)0.041 (3)0.044 (3)0.002 (2)0.008 (2)0.009 (3)
O60.045 (3)0.041 (3)0.028 (3)0.010 (2)0.002 (2)0.006 (2)
N20.014 (3)0.027 (3)0.037 (3)0.007 (3)0.006 (2)0.001 (3)
C250.044 (5)0.053 (5)0.061 (6)0.006 (4)0.011 (4)0.023 (5)
C230.047 (5)0.051 (5)0.043 (5)0.002 (4)0.001 (4)0.005 (4)
C240.054 (6)0.073 (7)0.066 (6)0.007 (5)0.004 (5)0.041 (5)
C30.084 (7)0.049 (5)0.030 (5)0.010 (5)0.004 (5)0.014 (4)
C270.055 (6)0.090 (8)0.058 (6)0.015 (5)0.012 (5)0.037 (5)
C260.057 (6)0.117 (10)0.121 (10)0.000 (6)0.015 (6)0.090 (8)
Geometric parameters (Å, º) top
Sm1—O12.341 (5)C11—C101.369 (11)
Sm1—O62.351 (5)C15—C141.386 (10)
Sm1—O42.372 (5)C15—C161.512 (10)
Sm1—O22.378 (5)N1—C51.357 (8)
Sm1—O32.383 (5)C2—C31.345 (11)
Sm1—O52.388 (5)C18—C191.379 (11)
Sm1—N22.589 (5)C18—C221.495 (10)
Sm1—N12.641 (5)C5—C61.432 (9)
O1—C151.278 (8)C6—N21.366 (8)
O2—C131.276 (8)C6—C71.412 (9)
O3—C201.257 (9)C10—C71.392 (11)
C12—N21.310 (8)C9—C81.338 (12)
C12—C111.391 (10)C8—C71.411 (11)
O4—C181.270 (9)C21—C201.531 (11)
C4—C31.389 (11)C19—C201.414 (11)
C4—C51.411 (10)O5—C251.280 (9)
C4—C91.438 (11)O6—C231.269 (9)
C1—N11.331 (9)C25—C241.359 (11)
C1—C21.391 (10)C25—C261.541 (11)
C13—C141.369 (11)C23—C241.382 (11)
C13—C171.507 (10)C23—C271.500 (11)
O1—Sm1—O6143.70 (16)O1—C15—C14124.8 (7)
O1—Sm1—O483.05 (16)O1—C15—C16114.8 (7)
O6—Sm1—O4118.26 (16)C14—C15—C16120.4 (7)
O1—Sm1—O272.40 (16)C1—N1—C5117.1 (6)
O6—Sm1—O276.16 (16)C1—N1—Sm1123.4 (5)
O4—Sm1—O2149.06 (16)C5—N1—Sm1119.4 (4)
O1—Sm1—O3140.45 (16)C3—C2—C1117.2 (7)
O6—Sm1—O375.84 (16)O4—C18—C19124.8 (7)
O4—Sm1—O371.83 (17)O4—C18—C22116.7 (7)
O2—Sm1—O3138.85 (17)C19—C18—C22118.5 (7)
O1—Sm1—O584.90 (17)N1—C5—C4122.1 (7)
O6—Sm1—O572.33 (17)N1—C5—C6118.0 (6)
O4—Sm1—O578.80 (16)C4—C5—C6119.9 (6)
O2—Sm1—O580.49 (16)N2—C6—C7122.8 (6)
O3—Sm1—O5118.13 (17)N2—C6—C5118.4 (6)
O1—Sm1—N2107.26 (16)C7—C6—C5118.9 (6)
O6—Sm1—N280.50 (16)C11—C10—C7120.9 (7)
O4—Sm1—N2132.74 (17)C8—C9—C4121.6 (8)
O2—Sm1—N274.04 (16)C9—C8—C7121.0 (8)
O3—Sm1—N272.09 (17)C10—C7—C8123.2 (7)
O5—Sm1—N2146.42 (17)C10—C7—C6116.7 (7)
O1—Sm1—N171.34 (16)C8—C7—C6120.2 (7)
O6—Sm1—N1137.93 (16)C18—C19—C20124.4 (7)
O4—Sm1—N178.79 (16)C13—C14—C15125.5 (7)
O2—Sm1—N1109.60 (16)O3—C20—C19125.0 (7)
O3—Sm1—N174.11 (17)O3—C20—C21115.9 (7)
O5—Sm1—N1148.99 (17)C19—C20—C21119.1 (7)
N2—Sm1—N162.65 (16)C25—O5—Sm1131.7 (5)
C15—O1—Sm1136.4 (5)C23—O6—Sm1133.0 (5)
C13—O2—Sm1135.3 (5)C12—N2—C6117.2 (6)
C20—O3—Sm1134.5 (5)C12—N2—Sm1121.9 (4)
N2—C12—C11124.8 (7)C6—N2—Sm1120.7 (4)
C18—O4—Sm1136.4 (5)O5—C25—C24126.0 (7)
C3—C4—C5117.0 (7)O5—C25—C26113.9 (7)
C3—C4—C9124.4 (8)C24—C25—C26120.1 (7)
C5—C4—C9118.5 (7)O6—C23—C24124.6 (8)
N1—C1—C2124.7 (7)O6—C23—C27116.3 (7)
O2—C13—C14124.7 (7)C24—C23—C27119.1 (7)
O2—C13—C17115.5 (7)C25—C24—C23125.5 (8)
C14—C13—C17119.7 (7)C2—C3—C4121.8 (7)
C10—C11—C12117.7 (7)

Experimental details

Crystal data
Chemical formula[Sm(C5H7O2)3(C12H8N2)]
Mr627.87
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)9.432 (2), 20.957 (5), 14.728 (3)
β (°) 98.899 (9)
V3)2876 (1)
Z4
Radiation typeMo Kα
µ (mm1)2.08
Crystal size (mm)0.20 × 0.20 × 0.20
Data collection
DiffractometerRigaku 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)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.073, 0.201, 1.32
No. of reflections5098
No. of parameters332
H-atom treatmentH-atom parameters constrained
w = 1/[σ2(Fo2) + 55.2376P]
where P = (Fo2 + 2Fc2)/3
Δρmax, Δρmin (e Å3)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).

Selected geometric parameters (Å, º) top
Sm1—O12.341 (5)Sm1—O32.383 (5)
Sm1—O62.351 (5)Sm1—O52.388 (5)
Sm1—O42.372 (5)Sm1—N22.589 (5)
Sm1—O22.378 (5)Sm1—N12.641 (5)
O1—Sm1—O272.40 (16)O6—Sm1—O572.33 (17)
O4—Sm1—O371.83 (17)N2—Sm1—N162.65 (16)
 

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