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Acta Crystallogr Sect E Struct Rep Online. 2010 November 1; 66(Pt 11): m1474.
Published online 2010 October 30. doi:  10.1107/S1600536810042704
PMCID: PMC3009107

Tris(N,N′-diisopropyl­benzamidinato)cerium(III)

Abstract

The title compound, [Ce(C13H19N2)3], was obtained in moderate yield (67%) by treatment of anhydrous cerium trichloride with three equivalents of Li[PhC(NiPr)2] in tetra­hydro­furan. It is the first homoleptic lanthanide complex of this amidinate ligand. The central CeIII ion is coordinated by three chelating benzamidinate anions in a distorted octa­hedral fashion, with Ce—N distances in the narrow range 2.482 (2)–2.492 (2) Å. The dihedral angles between the phenyl rings and the chelating N—C—N units are in the range 73.3–87.9°, thus preventing conjugation between the two π-systems. The mol­ecule is located on a twofold rotation axis, and one of the phenyl rings is equally disordered over two alternative symmetry-equivalent positions around this axis.

Related literature

For general background to lanthanide coordination complexes, see: Bailey & Pace (2001 [triangle]); Edelmann et al. (2002 [triangle]); Edelmann (2009 [triangle]). Wedler et al. (1992 [triangle]) describe complexes related to the title compound. For applications of homoleptic metal amid­inato complexes, see: Lim et al. (2003 [triangle]); Päiväsaari et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1474-scheme1.jpg

Experimental

Crystal data

  • [Ce(C13H19N2)3]
  • M r = 750.03
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1474-efi1.jpg
  • a = 14.1225 (4) Å
  • b = 18.5957 (6) Å
  • c = 15.6544 (4) Å
  • β = 98.324 (2)°
  • V = 4067.8 (2) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.15 mm−1
  • T = 133 K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Stoe IPDS 2T diffractometer
  • 32963 measured reflections
  • 5485 independent reflections
  • 5147 reflections with I > 2σ(I)
  • R int = 0.048

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 0.061
  • S = 1.11
  • 5485 reflections
  • 230 parameters
  • H-atom parameters constrained
  • Δρmax = 0.64 e Å−3
  • Δρmin = −1.00 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 [triangle]); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP (Siemens, 1994 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810042704/zl2316sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810042704/zl2316Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

Financial support of this work by the Otto-von-Guericke-Universität Magdeburg is gratefully acknowledged. PD thanks the Government of Sachsen-Anhalt for a PhD scholarship.

supplementary crystallographic information

Comment

A hot topic in current organolanthanide chemistry is the search for alternative spectator ligands other than cyclopentadienyls which are able to satisfy the coordination requirements of the large lanthanide cations (Edelmann et al., 2002). Among the most successful approaches in this field is the use of amidinate ligands of the general type [RC(NR')2]- (R = H, alkyl, aryl; R' = alkyl, cycloalkyl, aryl, SiMe3) which can be regarded as steric cyclopentadienyl equivalents (Bailey & Pace, 2001). Homoleptic lanthanide(III) tris(amidinates) are among the longest known lanthanide complexes containing these chelating ligands. The first lanthanide(III) amidinate complexes ever reported were homoleptic tris(amidinates) of the type [RC6H4C(NSiMe3)2]3Ln (Wedler et al., 1992). In 2002 it was discovered that homoleptic lanthanide tris(amidinate) complexes display extremely high activity for the ring-opening polymerization of e-caprolactone at room temperature. High catalytic activity of homoleptic lanthanide(III) tris(amidinate) has also been found for the polymerization of other polar monomers such as trimethylene carbonate (TMC), lactide, and methylmethacrylate (MMA) (Edelmann, 2009). Even more surprising was the finding that such complexes may turn out to be valuable precursors in materials science and nanotechnology (Edelmann, 2009). For example, pure metals can be deposited by using volatile homoleptic metal amidinato complexes of the type [{MeC(NR')2}nM]x (R = Me, But; R = Pri, But) and molecular hydrogen gas as the reactants (Lim et al., 2003). Lanthanide amidinate complexes have also been employed in the fabrication of lanthanide-doped inorganic phases by CVD methods (Päiväsaari et al., 2005). We report here the synthesis and structural characterization of a potentially useful homoleptic cerium amidinate, tris[N,N'-bis(isopropyl)benzamidinato]cerium(III). Besides X-ray crystallography, the title compound was also characterized by elemental analysis and spectroscopic methods. Due to the paramagnetic nature of the Ce3+ ion, the 1H NMR signals of the ortho-, meta- and para-phenyl protons appear well separated at δ 12.85, 9.30 and 8.69 p.p.m., respectively, while only broad singlets were observed for the isopropyl protons.

Golden-yellow, highly air-sensitive, block-like single crystals of the title compound were obtained by slow cooling of a saturated solution in n-pentane to 278 K. In the solid state the molecule is located on a C2 rotation axis, and one of the phenyl rings is disordered over two alternative symmetry equivalent positions around this axis. The coordination geometry around the central cerium(3+) ion can be described as distorted octahedral. The average Ce—N distance is 2.487 Å. With 53.95 (5) - 54.11 (7) the N—Ce—N angles are in the range which is typical for homoleptic lanthanide tris(amidinate) complexes (Edelmann, 2009). The dihedral angles between the phenyl rings and the chelating N—C—N units are in the range of 73.3 - 87.9 °, thus preventing conjugation between the two π -systems.

Experimental

Preparation of tris[N,N'-bis(isopropyl)benzamidinato]cerium(III): A 100 ml Schlenk-flask was charged with lithium N,N'-bis(isopropyl)benzamidinate (3.00 g, 14.3 mmol), anhydrous cerium(III) trichloride (1.17 g, 4.8 mmol) and 100 ml of THF, and the mixture was stirred for 3 h at 333 K, causing the development of a bright yellow color. The mixture was evaporated to dryness and the residue was extracted with n-pentane (3 x 15 ml) followed by filtration. The clear filtrate was concentrated in vacuo to a total volume of ca 10 ml. Cooling to 237 K for 24 h afforded 2.42 g (67%) of tris[N,N'-bis(isopropyl)benzamidinato]cerium(III) as golden-yellow, block-like crystals. X-ray quality single crystals were grown from a saturated solution in n-pentane at 278 K. M. p. 486 K. Anal. calcd for C39H57CeN6 (750.03 g/mol): C 62.45, H 7.66, N 11.20; found: C 62.08, H 7.79, N 10.82%. IR (KBr pellet): νmax 3080 (w), 3061 (w), 3022 (w), 2957 (vs, nas CH3), 2916 (st), 2888 (st, nas CH3), 2861 (st), 1636 (m, NCN unit), 1600 (m, CH ring), 1578 (m, CH ring), 1453 (vsbr, das CH3), 1374 (vs, NCN unit), 1359 (vs), 1335 (vs), 1274 (w), 1208 (vs), 1166 (st, CH ring), 1133 (vs), 1122 (st), 1073 (w), 1005 (vs), 946 (w), 910 (w), 778 (st), 733 (m), 700 (vs, CH ring), 469 (w) cm-1. 1H NMR (400 MHz, C6D6, 298 K): δ = 12.85 (d, 3J = 4.7 Hz, 6H, Ar–H), 10.84 (s, 6H, ((CH3)2CHN)2CPh), 9.30 (s, 6H, Ar–H), 8.69 (t, 3J = 7.4 Hz, 3H, Ar–H), -3.29 (s br, 36H, ((CH3)2CHN)2CPh). 13C{1H} NMR (100.6 MHz, C6D6, 298 K): δ = 186.9 ((iPrN)2CPh), 148.52 (Ar-C), 132.8 (Ar-C), 131.6 (Ar-C), 130.3 (Ar-C), 52.8 ((CH3)2CHN)2CPh), 22.7 ((CH3)2CHN)2CPh). EI—MS: m/z 749.7 (40) [M]+, 546.3 (100) [M – (iPrN)2CPh]+, 203.2 (40) [(iPrN)2CPh]+, 104.1 (80) [HNCPh]+.

Refinement

One of the phenyl rings is disordered over two alternative symmetry equivalent positions around the two fold rotation axis the molecule is located on. The disordered phenyl ring was contrained to resemble an ideal hexagon with C—C distances of 1.39 Å. No restraints for atom positions or ADPs needed to be applied.

The hydrogen atoms were included using a riding model, with aromatic C—H = 0.95 Å, methyn C—H = 1.00 Å [Uiso(H) = 1.2Ueq(C)] and methyl C—H = 0.98 Å [Uiso(H) = 1.5Ueq(C)].

Figures

Fig. 1.
The molecule of the title compound in the crystal. Thermal ellipsoids represent 50% probability levels. The disorder of the phenyl ring C15 - C16A is omitted for clarity.

Crystal data

[Ce(C13H19N2)3]F(000) = 1564
Mr = 750.03Dx = 1.225 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 14.1225 (4) ÅCell parameters from 58857 reflections
b = 18.5957 (6) Åθ = 2.1–29.6°
c = 15.6544 (4) ŵ = 1.15 mm1
β = 98.324 (2)°T = 133 K
V = 4067.8 (2) Å3Prism, yellow
Z = 40.30 × 0.20 × 0.10 mm

Data collection

Stoe IPDS 2T diffractometer5147 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.048
plane graphiteθmax = 29.2°, θmin = 2.1°
Detector resolution: 6.67 pixels mm-1h = −19→19
rotation method scansk = −25→25
32963 measured reflectionsl = −21→20
5485 independent reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.11w = 1/[σ2(Fo2) + (0.031P)2 + 1.6552P] where P = (Fo2 + 2Fc2)/3
5485 reflections(Δ/σ)max = 0.002
230 parametersΔρmax = 0.64 e Å3
0 restraintsΔρmin = −1.00 e Å3

Special details

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. The phenyl ring with two carbon atoms located on the C2 rotation axis lies in two alternative symmetry related positions.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
Ce0.50000.699350 (7)0.75000.03398 (5)
N10.56280 (13)0.78730 (10)0.86347 (14)0.0595 (5)
N20.41661 (11)0.74104 (9)0.87036 (11)0.0465 (4)
N30.57059 (11)0.57999 (8)0.79492 (11)0.0471 (4)
C10.48506 (13)0.78591 (10)0.90212 (13)0.0444 (4)
C20.47606 (12)0.83394 (10)0.97814 (12)0.0413 (4)
C30.52818 (15)0.82015 (13)1.05786 (14)0.0526 (4)
H30.57000.77991.06480.063*
C40.52048 (16)0.86400 (15)1.12785 (15)0.0599 (5)
H40.55660.85361.18250.072*
C50.46115 (17)0.92218 (13)1.11859 (15)0.0592 (5)
H50.45540.95211.16670.071*
C60.40972 (18)0.93729 (12)1.03927 (16)0.0606 (5)
H60.36920.97831.03250.073*
C70.41652 (16)0.89307 (11)0.96895 (14)0.0521 (4)
H70.38010.90360.91450.062*
C80.33639 (13)0.72355 (12)0.91592 (13)0.0475 (4)
H80.33500.75860.96410.057*
C90.3499 (2)0.64907 (17)0.9530 (2)0.0829 (9)
H9A0.35750.61490.90680.124*
H9B0.29380.63570.97980.124*
H9C0.40710.64800.99660.124*
C100.24360 (16)0.7286 (2)0.85526 (17)0.0734 (7)
H10A0.23450.77800.83380.110*
H10B0.19040.71530.88600.110*
H10C0.24540.69580.80650.110*
C110.63744 (17)0.84142 (15)0.88303 (17)0.0688 (7)
H110.63140.86560.93910.083*
C120.6317 (3)0.89570 (16)0.8125 (3)0.1140 (15)
H12A0.64310.87210.75890.171*
H12B0.68030.93290.82800.171*
H12C0.56800.91780.80400.171*
C130.7336 (2)0.8035 (2)0.8890 (3)0.1099 (14)
H13A0.73610.76410.93090.165*
H13B0.78510.83780.90760.165*
H13C0.74140.78400.83220.165*
C140.50000.54307 (13)0.75000.0408 (5)
C150.5009 (10)0.46299 (10)0.7603 (6)0.0382 (13)0.50
C160.4568 (8)0.4312 (3)0.8245 (4)0.068 (2)0.50
H160.42720.46030.86300.081*0.50
C170.4559 (5)0.3567 (3)0.8326 (3)0.088 (2)0.50
H170.42580.33500.87650.105*0.50
C180.4992 (6)0.31412 (11)0.7763 (4)0.074 (2)0.50
H180.49860.26330.78180.089*0.50
C17A0.5434 (4)0.3460 (2)0.7121 (3)0.0754 (19)0.50
H17A0.57290.31680.67360.090*0.50
C16A0.5442 (7)0.4204 (2)0.7040 (4)0.0574 (15)0.50
H16A0.57440.44210.66010.069*0.50
C190.64510 (15)0.54478 (12)0.85451 (16)0.0561 (5)
H190.64310.49200.84240.067*
C200.74139 (19)0.5732 (2)0.8419 (3)0.0961 (11)
H20A0.75310.56250.78300.144*
H20B0.79090.55020.88330.144*
H20C0.74320.62530.85110.144*
C210.6265 (3)0.5570 (3)0.9468 (2)0.1027 (12)
H21A0.62800.60860.95930.154*
H21B0.67590.53260.98690.154*
H21C0.56350.53760.95360.154*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Ce0.03793 (7)0.03059 (7)0.03552 (7)0.0000.01243 (5)0.000
N10.0504 (9)0.0655 (11)0.0698 (12)−0.0243 (8)0.0333 (8)−0.0329 (9)
N20.0442 (7)0.0518 (9)0.0486 (8)−0.0133 (7)0.0235 (7)−0.0136 (7)
N30.0468 (8)0.0351 (7)0.0554 (9)0.0003 (6)−0.0058 (7)0.0001 (6)
C10.0440 (8)0.0453 (9)0.0476 (9)−0.0064 (7)0.0195 (7)−0.0107 (7)
C20.0411 (8)0.0422 (9)0.0439 (9)−0.0063 (7)0.0174 (7)−0.0080 (7)
C30.0478 (10)0.0607 (11)0.0509 (11)0.0047 (9)0.0124 (8)−0.0057 (9)
C40.0549 (11)0.0809 (15)0.0447 (10)−0.0078 (11)0.0102 (9)−0.0118 (10)
C50.0656 (12)0.0619 (13)0.0543 (11)−0.0135 (10)0.0229 (10)−0.0223 (10)
C60.0748 (14)0.0459 (10)0.0651 (13)0.0059 (10)0.0232 (11)−0.0104 (10)
C70.0615 (11)0.0483 (10)0.0481 (10)0.0035 (9)0.0138 (8)−0.0037 (8)
C80.0432 (9)0.0557 (10)0.0478 (10)−0.0125 (8)0.0215 (8)−0.0093 (8)
C90.0660 (15)0.0777 (18)0.112 (2)−0.0061 (13)0.0372 (15)0.0276 (17)
C100.0447 (11)0.117 (2)0.0627 (14)−0.0066 (12)0.0206 (10)−0.0024 (15)
C110.0597 (12)0.0783 (16)0.0766 (15)−0.0355 (12)0.0377 (11)−0.0441 (13)
C120.093 (2)0.0517 (15)0.193 (4)−0.0297 (15)0.006 (3)0.003 (2)
C130.0566 (15)0.127 (3)0.139 (4)−0.0321 (17)−0.0075 (19)0.001 (3)
C140.0412 (11)0.0337 (11)0.0476 (13)0.0000.0075 (10)0.000
C150.0347 (11)0.0388 (12)0.041 (4)0.004 (2)0.005 (3)−0.0062 (17)
C160.079 (4)0.047 (3)0.087 (6)0.006 (3)0.043 (5)0.005 (3)
C170.097 (5)0.056 (3)0.120 (7)0.005 (3)0.053 (5)0.017 (4)
C180.076 (3)0.0347 (19)0.113 (7)−0.001 (2)0.021 (5)0.004 (2)
C17A0.089 (4)0.035 (3)0.111 (6)0.008 (3)0.045 (4)−0.013 (3)
C16A0.071 (3)0.038 (2)0.070 (4)0.003 (2)0.035 (3)−0.004 (2)
C190.0502 (10)0.0450 (10)0.0678 (13)0.0025 (8)−0.0093 (9)0.0033 (9)
C200.0523 (13)0.106 (2)0.124 (3)−0.0045 (14)−0.0092 (15)0.042 (2)
C210.098 (2)0.143 (3)0.0621 (17)0.027 (2)−0.0057 (16)0.018 (2)

Geometric parameters (Å, °)

Ce—N12.4820 (17)C10—H10B0.9800
Ce—N1i2.4820 (17)C10—H10C0.9800
Ce—N22.4860 (14)C11—C121.490 (5)
Ce—N2i2.4860 (14)C11—C131.521 (5)
Ce—N3i2.4924 (15)C11—H111.0000
Ce—N32.4924 (15)C12—H12A0.9800
Ce—C142.906 (2)C12—H12B0.9800
Ce—C12.9071 (18)C12—H12C0.9800
Ce—C1i2.9071 (18)C13—H13A0.9800
N1—C11.328 (2)C13—H13B0.9800
N1—C111.458 (2)C13—H13C0.9800
N2—C11.319 (2)C14—N3i1.325 (2)
N2—C81.460 (2)C14—C15i1.498 (3)
N3—C141.325 (2)C14—C151.498 (3)
N3—C191.457 (2)C15—C161.3900
C1—C21.508 (2)C15—C16A1.3900
C2—C31.378 (3)C16—C171.3900
C2—C71.379 (3)C16—H160.9500
C3—C41.383 (3)C17—C181.3900
C3—H30.9500C17—H170.9500
C4—C51.363 (4)C18—C17A1.3900
C4—H40.9500C18—H180.9500
C5—C61.374 (4)C17A—C16A1.3900
C5—H50.9500C17A—H17A0.9500
C6—C71.389 (3)C16A—H16A0.9500
C6—H60.9500C19—C201.498 (4)
C7—H70.9500C19—C211.522 (4)
C8—C91.503 (4)C19—H191.0000
C8—C101.506 (3)C20—H20A0.9800
C8—H81.0000C20—H20B0.9800
C9—H9A0.9800C20—H20C0.9800
C9—H9B0.9800C21—H21A0.9800
C9—H9C0.9800C21—H21B0.9800
C10—H10A0.9800C21—H21C0.9800
N1—Ce—N1i97.57 (11)C8—C9—H9C109.5
N1—Ce—N253.95 (5)H9A—C9—H9C109.5
N1i—Ce—N2100.23 (6)H9B—C9—H9C109.5
N1—Ce—N2i100.23 (6)C8—C10—H10A109.5
N1i—Ce—N2i53.95 (5)C8—C10—H10B109.5
N2—Ce—N2i143.66 (8)H10A—C10—H10B109.5
N1—Ce—N3i151.12 (7)C8—C10—H10C109.5
N1i—Ce—N3i107.34 (7)H10A—C10—H10C109.5
N2—Ce—N3i106.11 (6)H10B—C10—H10C109.5
N2i—Ce—N3i106.13 (6)N1—C11—C12110.6 (2)
N1—Ce—N3107.34 (7)N1—C11—C13107.7 (2)
N1i—Ce—N3151.12 (7)C12—C11—C13108.2 (3)
N2—Ce—N3106.13 (6)N1—C11—H11110.1
N2i—Ce—N3106.11 (6)C12—C11—H11110.1
N3i—Ce—N354.12 (7)C13—C11—H11110.1
N1—Ce—C14131.22 (6)C11—C12—H12A109.5
N1i—Ce—C14131.22 (6)C11—C12—H12B109.5
N2—Ce—C14108.17 (4)H12A—C12—H12B109.5
N2i—Ce—C14108.17 (4)C11—C12—H12C109.5
N1i—Ce—C199.24 (7)H12A—C12—H12C109.5
N2i—Ce—C1123.14 (6)H12B—C12—H12C109.5
N3i—Ce—C1130.59 (6)C11—C13—H13A109.5
N3—Ce—C1109.60 (6)C11—C13—H13B109.5
C14—Ce—C1123.62 (4)H13A—C13—H13B109.5
N1—Ce—C1i99.24 (7)C11—C13—H13C109.5
N2—Ce—C1i123.14 (6)H13A—C13—H13C109.5
N3i—Ce—C1i109.60 (6)H13B—C13—H13C109.5
N3—Ce—C1i130.59 (6)N3—C14—N3i117.6 (2)
C14—Ce—C1i123.62 (4)N3—C14—C15i124.5 (6)
C1—Ce—C1i112.76 (8)N3i—C14—C15i117.6 (6)
C1—N1—C11122.56 (17)N3—C14—C15117.6 (6)
C1—N1—Ce94.58 (12)N3i—C14—C15124.5 (6)
C11—N1—Ce141.07 (13)N3—C14—Ce58.81 (11)
C1—N2—C8122.34 (16)N3i—C14—Ce58.81 (11)
C1—N2—Ce94.66 (10)C15i—C14—Ce173.9 (3)
C8—N2—Ce141.91 (12)C15—C14—Ce173.9 (3)
C14—N3—C19121.67 (16)C16—C15—C16A120.0
C14—N3—Ce94.14 (12)C16—C15—C14120.2 (5)
C19—N3—Ce143.45 (13)C16A—C15—C14119.8 (5)
N2—C1—N1116.73 (16)C17—C16—C15120.0
N2—C1—C2122.10 (15)C17—C16—H16120.0
N1—C1—C2121.17 (16)C15—C16—H16120.0
N2—C1—Ce58.46 (9)C16—C17—C18120.0
N1—C1—Ce58.33 (10)C16—C17—H17120.0
C2—C1—Ce177.18 (14)C18—C17—H17120.0
C3—C2—C7118.72 (18)C17A—C18—C17120.0
C3—C2—C1120.63 (18)C17A—C18—H18120.0
C7—C2—C1120.65 (18)C17—C18—H18120.0
C2—C3—C4121.0 (2)C18—C17A—C16A120.0
C2—C3—H3119.5C18—C17A—H17A120.0
C4—C3—H3119.5C16A—C17A—H17A120.0
C5—C4—C3120.1 (2)C17A—C16A—C15120.0
C5—C4—H4120.0C17A—C16A—H16A120.0
C3—C4—H4120.0C15—C16A—H16A120.0
C4—C5—C6119.7 (2)N3—C19—C20110.0 (2)
C4—C5—H5120.2N3—C19—C21109.4 (2)
C6—C5—H5120.2C20—C19—C21111.0 (3)
C5—C6—C7120.5 (2)N3—C19—H19108.8
C5—C6—H6119.8C20—C19—H19108.8
C7—C6—H6119.8C21—C19—H19108.8
C2—C7—C6120.0 (2)C19—C20—H20A109.5
C2—C7—H7120.0C19—C20—H20B109.5
C6—C7—H7120.0H20A—C20—H20B109.5
N2—C8—C9109.27 (18)C19—C20—H20C109.5
N2—C8—C10110.12 (17)H20A—C20—H20C109.5
C9—C8—C10110.5 (2)H20B—C20—H20C109.5
N2—C8—H8109.0C19—C21—H21A109.5
C9—C8—H8109.0C19—C21—H21B109.5
C10—C8—H8109.0H21A—C21—H21B109.5
C8—C9—H9A109.5C19—C21—H21C109.5
C8—C9—H9B109.5H21A—C21—H21C109.5
H9A—C9—H9B109.5H21B—C21—H21C109.5
N1i—Ce—N1—C195.52 (15)C14—Ce—C1—N2−61.08 (14)
N2—Ce—N1—C1−1.66 (13)C1i—Ce—C1—N2118.92 (14)
N2i—Ce—N1—C1150.12 (14)N1i—Ce—C1—N1−88.55 (18)
N3i—Ce—N1—C1−54.1 (2)N2—Ce—C1—N1177.0 (2)
N3—Ce—N1—C1−99.29 (15)N2i—Ce—C1—N1−35.84 (17)
C14—Ce—N1—C1−84.48 (15)N3i—Ce—C1—N1148.96 (14)
C1i—Ce—N1—C1122.86 (14)N3—Ce—C1—N189.91 (15)
N1i—Ce—N1—C11−67.9 (3)C14—Ce—C1—N1115.96 (14)
N2—Ce—N1—C11−165.1 (3)C1i—Ce—C1—N1−64.04 (14)
N2i—Ce—N1—C11−13.3 (3)N2—C1—C2—C3107.5 (2)
N3i—Ce—N1—C11142.4 (3)N1—C1—C2—C3−73.0 (3)
N3—Ce—N1—C1197.3 (3)N2—C1—C2—C7−73.4 (3)
C14—Ce—N1—C11112.1 (3)N1—C1—C2—C7106.2 (2)
C1—Ce—N1—C11−163.4 (4)C7—C2—C3—C40.7 (3)
C1i—Ce—N1—C11−40.5 (3)C1—C2—C3—C4179.88 (19)
N1—Ce—N2—C11.67 (13)C2—C3—C4—C5−0.4 (4)
N1i—Ce—N2—C1−90.29 (14)C3—C4—C5—C6−0.5 (4)
N2i—Ce—N2—C1−50.10 (12)C4—C5—C6—C71.1 (4)
N3i—Ce—N2—C1158.16 (12)C3—C2—C7—C6−0.2 (3)
N3—Ce—N2—C1101.64 (13)C1—C2—C7—C6−179.3 (2)
C14—Ce—N2—C1129.90 (12)C5—C6—C7—C2−0.8 (4)
C1i—Ce—N2—C1−74.56 (17)C1—N2—C8—C9−105.7 (3)
N1—Ce—N2—C8−165.3 (3)Ce—N2—C8—C958.8 (3)
N1i—Ce—N2—C8102.8 (2)C1—N2—C8—C10132.7 (2)
N2i—Ce—N2—C8143.0 (2)Ce—N2—C8—C10−62.8 (3)
N3i—Ce—N2—C8−8.8 (2)C1—N1—C11—C12−104.8 (3)
N3—Ce—N2—C8−65.3 (2)Ce—N1—C11—C1255.4 (4)
C14—Ce—N2—C8−37.0 (2)C1—N1—C11—C13137.2 (3)
C1—Ce—N2—C8−166.9 (3)Ce—N1—C11—C13−62.6 (4)
C1i—Ce—N2—C8118.5 (2)C19—N3—C14—N3i172.3 (2)
N1—Ce—N3—C14155.00 (8)C19—N3—C14—C15i−13.8 (4)
N1i—Ce—N3—C14−56.63 (17)Ce—N3—C14—C15i173.9 (3)
N2—Ce—N3—C1498.47 (9)C19—N3—C14—C15−2.0 (4)
N2i—Ce—N3—C14−98.51 (9)Ce—N3—C14—C15−174.3 (3)
C1—Ce—N3—C14126.50 (9)C19—N3—C14—Ce172.3 (2)
C1i—Ce—N3—C14−85.72 (11)N1—Ce—C14—N3−32.43 (11)
N1—Ce—N3—C19−14.0 (3)N1i—Ce—C14—N3147.57 (11)
N1i—Ce—N3—C19134.4 (2)N2—Ce—C14—N3−90.02 (10)
N2—Ce—N3—C19−70.5 (3)N2i—Ce—C14—N389.98 (10)
N2i—Ce—N3—C1992.5 (3)C1—Ce—C14—N3−65.41 (11)
N3i—Ce—N3—C19−169.0 (3)C1i—Ce—C14—N3114.59 (11)
C14—Ce—N3—C19−169.0 (3)N1—Ce—C14—N3i147.57 (11)
C1—Ce—N3—C19−42.5 (3)N1i—Ce—C14—N3i−32.43 (11)
C1i—Ce—N3—C19105.3 (3)N2—Ce—C14—N3i89.98 (10)
C8—N2—C1—N1167.7 (2)N2i—Ce—C14—N3i−90.02 (10)
Ce—N2—C1—N1−2.8 (2)C1—Ce—C14—N3i114.59 (11)
C8—N2—C1—C2−12.8 (3)C1i—Ce—C14—N3i−65.41 (11)
Ce—N2—C1—C2176.75 (17)N3—C14—C15—C1688.9 (6)
C8—N2—C1—Ce170.5 (2)N3i—C14—C15—C16−85.0 (5)
C11—N1—C1—N2170.5 (2)C15i—C14—C15—C16−144 (5)
Ce—N1—C1—N22.8 (2)N3—C14—C15—C16A−92.6 (5)
C11—N1—C1—C2−9.0 (4)N3i—C14—C15—C16A93.5 (6)
Ce—N1—C1—C2−176.75 (17)C15i—C14—C15—C16A34 (4)
C11—N1—C1—Ce167.7 (3)C14—C15—C16—C17178.5 (11)
N1—Ce—C1—N2−177.0 (2)C14—C15—C16A—C17A−178.5 (11)
N1i—Ce—C1—N294.41 (13)C14—N3—C19—C20134.4 (2)
N2i—Ce—C1—N2147.12 (11)Ce—N3—C19—C20−58.5 (4)
N3i—Ce—C1—N2−28.07 (16)C14—N3—C19—C21−103.4 (3)
N3—Ce—C1—N2−87.12 (13)Ce—N3—C19—C2163.7 (3)

Symmetry codes: (i) −x+1, y, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2316).

References

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