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

Dröse, P.; Hrib, C.G.; Blaurock, S.; Edelmann, F.T.

doi:10.1107/S1600536810042704

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page m1474

https://doi.org/10.1107/S1600536810042704

Open

access

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

Peter Dröse,^a Cristian G. Hrib,^a Steffen Blaurock ^a and Frank T. Edelmann ^a ^*

^aChemisches Institut der Otto-von-Guericke-Universität, Universitätsplatz 2, D-39116 Magdeburg, Germany
^*Correspondence e-mail: frank.edelmann@ovgu.de

(Received 13 October 2010; accepted 20 October 2010; online 30 October 2010)

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 Ce^III 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 ); Edelmann et al. (2002 ); Edelmann (2009 ). Wedler et al. (1992 ) describe complexes related to the title compound. For applications of homoleptic metal amidinato complexes, see: Lim et al. (2003 ); Päiväsaari et al. (2005 ).

Experimental

Crystal data

[Ce(C₁₃H₁₉N₂)₃]
M_r = 750.03
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.026
wR(F²) = 0.061
S = 1.11
5485 reflections
230 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −1.00 e Å⁻³

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042704/zl2316Isup2.hkl

checkCIF report

Comment top

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, Bu^t; R = Prⁱ, Bu^t) 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.

Related literature top

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

Experimental top

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): ν_max 3080 (w), 3061 (w), 3022 (w), 2957 (vs, n_as CH₃), 2916 (st), 2888 (st, n_as CH₃), 2861 (st), 1636 (m, NCN unit), 1600 (m, CH ring), 1578 (m, CH ring), 1453 (vs_br, d_as 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]⁺.

Structure description top

Computing details top

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

Figures top

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.

Tris(N,N'-diisopropylbenzamidinato)cerium(III) top

Crystal data top

[Ce(C₁₃H₁₉N₂)₃]	F(000) = 1564
M_r = 750.03	D_x = 1.225 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.1225 (4) Å	Cell parameters from 58857 reflections
b = 18.5957 (6) Å	θ = 2.1–29.6°
c = 15.6544 (4) Å	µ = 1.15 mm⁻¹
β = 98.324 (2)°	T = 133 K
V = 4067.8 (2) Å³	Prism, yellow
Z = 4	0.30 × 0.20 × 0.10 mm

Data collection top

Stoe IPDS 2T diffractometer	5147 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.048
Plane graphite monochromator	θ_max = 29.2°, θ_min = 2.1°
Detector resolution: 6.67 pixels mm^-1	h = −19→19
rotation method scans	k = −25→25
32963 measured reflections	l = −21→20
5485 independent reflections

Refinement top

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.061	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.031P)² + 1.6552P] where P = (F_o² + 2F_c²)/3
5485 reflections	(Δ/σ)_max = 0.002
230 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −1.00 e Å⁻³

Crystal data top

[Ce(C₁₃H₁₉N₂)₃]	V = 4067.8 (2) Å³
M_r = 750.03	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.1225 (4) Å	µ = 1.15 mm⁻¹
b = 18.5957 (6) Å	T = 133 K
c = 15.6544 (4) Å	0.30 × 0.20 × 0.10 mm
β = 98.324 (2)°

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.061	H-atom parameters constrained
S = 1.11	Δρ_max = 0.64 e Å⁻³
5485 reflections	Δρ_min = −1.00 e Å⁻³
230 parameters

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.

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) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ce	0.5000	0.699350 (7)	0.7500	0.03398 (5)
N1	0.56280 (13)	0.78730 (10)	0.86347 (14)	0.0595 (5)
N2	0.41661 (11)	0.74104 (9)	0.87036 (11)	0.0465 (4)
N3	0.57059 (11)	0.57999 (8)	0.79492 (11)	0.0471 (4)
C1	0.48506 (13)	0.78591 (10)	0.90212 (13)	0.0444 (4)
C2	0.47606 (12)	0.83394 (10)	0.97814 (12)	0.0413 (4)
C3	0.52818 (15)	0.82015 (13)	1.05786 (14)	0.0526 (4)
H3	0.5700	0.7799	1.0648	0.063*
C4	0.52048 (16)	0.86400 (15)	1.12785 (15)	0.0599 (5)
H4	0.5566	0.8536	1.1825	0.072*
C5	0.46115 (17)	0.92218 (13)	1.11859 (15)	0.0592 (5)
H5	0.4554	0.9521	1.1667	0.071*
C6	0.40972 (18)	0.93729 (12)	1.03927 (16)	0.0606 (5)
H6	0.3692	0.9783	1.0325	0.073*
C7	0.41652 (16)	0.89307 (11)	0.96895 (14)	0.0521 (4)
H7	0.3801	0.9036	0.9145	0.062*
C8	0.33639 (13)	0.72355 (12)	0.91592 (13)	0.0475 (4)
H8	0.3350	0.7586	0.9641	0.057*
C9	0.3499 (2)	0.64907 (17)	0.9530 (2)	0.0829 (9)
H9A	0.3575	0.6149	0.9068	0.124*
H9B	0.2938	0.6357	0.9798	0.124*
H9C	0.4071	0.6480	0.9966	0.124*
C10	0.24360 (16)	0.7286 (2)	0.85526 (17)	0.0734 (7)
H10A	0.2345	0.7780	0.8338	0.110*
H10B	0.1904	0.7153	0.8860	0.110*
H10C	0.2454	0.6958	0.8065	0.110*
C11	0.63744 (17)	0.84142 (15)	0.88303 (17)	0.0688 (7)
H11	0.6314	0.8656	0.9391	0.083*
C12	0.6317 (3)	0.89570 (16)	0.8125 (3)	0.1140 (15)
H12A	0.6431	0.8721	0.7589	0.171*
H12B	0.6803	0.9329	0.8280	0.171*
H12C	0.5680	0.9178	0.8040	0.171*
C13	0.7336 (2)	0.8035 (2)	0.8890 (3)	0.1099 (14)
H13A	0.7361	0.7641	0.9309	0.165*
H13B	0.7851	0.8378	0.9076	0.165*
H13C	0.7414	0.7840	0.8322	0.165*
C14	0.5000	0.54307 (13)	0.7500	0.0408 (5)
C15	0.5009 (10)	0.46299 (10)	0.7603 (6)	0.0382 (13)	0.50
C16	0.4568 (8)	0.4312 (3)	0.8245 (4)	0.068 (2)	0.50
H16	0.4272	0.4603	0.8630	0.081*	0.50
C17	0.4559 (5)	0.3567 (3)	0.8326 (3)	0.088 (2)	0.50
H17	0.4258	0.3350	0.8765	0.105*	0.50
C18	0.4992 (6)	0.31412 (11)	0.7763 (4)	0.074 (2)	0.50
H18	0.4986	0.2633	0.7818	0.089*	0.50
C17A	0.5434 (4)	0.3460 (2)	0.7121 (3)	0.0754 (19)	0.50
H17A	0.5729	0.3168	0.6736	0.090*	0.50
C16A	0.5442 (7)	0.4204 (2)	0.7040 (4)	0.0574 (15)	0.50
H16A	0.5744	0.4421	0.6601	0.069*	0.50
C19	0.64510 (15)	0.54478 (12)	0.85451 (16)	0.0561 (5)
H19	0.6431	0.4920	0.8424	0.067*
C20	0.74139 (19)	0.5732 (2)	0.8419 (3)	0.0961 (11)
H20A	0.7531	0.5625	0.7830	0.144*
H20B	0.7909	0.5502	0.8833	0.144*
H20C	0.7432	0.6253	0.8511	0.144*
C21	0.6265 (3)	0.5570 (3)	0.9468 (2)	0.1027 (12)
H21A	0.6280	0.6086	0.9593	0.154*
H21B	0.6759	0.5326	0.9869	0.154*
H21C	0.5635	0.5376	0.9536	0.154*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ce	0.03793 (7)	0.03059 (7)	0.03552 (7)	0.000	0.01243 (5)	0.000
N1	0.0504 (9)	0.0655 (11)	0.0698 (12)	−0.0243 (8)	0.0333 (8)	−0.0329 (9)
N2	0.0442 (7)	0.0518 (9)	0.0486 (8)	−0.0133 (7)	0.0235 (7)	−0.0136 (7)
N3	0.0468 (8)	0.0351 (7)	0.0554 (9)	0.0003 (6)	−0.0058 (7)	0.0001 (6)
C1	0.0440 (8)	0.0453 (9)	0.0476 (9)	−0.0064 (7)	0.0195 (7)	−0.0107 (7)
C2	0.0411 (8)	0.0422 (9)	0.0439 (9)	−0.0063 (7)	0.0174 (7)	−0.0080 (7)
C3	0.0478 (10)	0.0607 (11)	0.0509 (11)	0.0047 (9)	0.0124 (8)	−0.0057 (9)
C4	0.0549 (11)	0.0809 (15)	0.0447 (10)	−0.0078 (11)	0.0102 (9)	−0.0118 (10)
C5	0.0656 (12)	0.0619 (13)	0.0543 (11)	−0.0135 (10)	0.0229 (10)	−0.0223 (10)
C6	0.0748 (14)	0.0459 (10)	0.0651 (13)	0.0059 (10)	0.0232 (11)	−0.0104 (10)
C7	0.0615 (11)	0.0483 (10)	0.0481 (10)	0.0035 (9)	0.0138 (8)	−0.0037 (8)
C8	0.0432 (9)	0.0557 (10)	0.0478 (10)	−0.0125 (8)	0.0215 (8)	−0.0093 (8)
C9	0.0660 (15)	0.0777 (18)	0.112 (2)	−0.0061 (13)	0.0372 (15)	0.0276 (17)
C10	0.0447 (11)	0.117 (2)	0.0627 (14)	−0.0066 (12)	0.0206 (10)	−0.0024 (15)
C11	0.0597 (12)	0.0783 (16)	0.0766 (15)	−0.0355 (12)	0.0377 (11)	−0.0441 (13)
C12	0.093 (2)	0.0517 (15)	0.193 (4)	−0.0297 (15)	0.006 (3)	0.003 (2)
C13	0.0566 (15)	0.127 (3)	0.139 (4)	−0.0321 (17)	−0.0075 (19)	0.001 (3)
C14	0.0412 (11)	0.0337 (11)	0.0476 (13)	0.000	0.0075 (10)	0.000
C15	0.0347 (11)	0.0388 (12)	0.041 (4)	0.004 (2)	0.005 (3)	−0.0062 (17)
C16	0.079 (4)	0.047 (3)	0.087 (6)	0.006 (3)	0.043 (5)	0.005 (3)
C17	0.097 (5)	0.056 (3)	0.120 (7)	0.005 (3)	0.053 (5)	0.017 (4)
C18	0.076 (3)	0.0347 (19)	0.113 (7)	−0.001 (2)	0.021 (5)	0.004 (2)
C17A	0.089 (4)	0.035 (3)	0.111 (6)	0.008 (3)	0.045 (4)	−0.013 (3)
C16A	0.071 (3)	0.038 (2)	0.070 (4)	0.003 (2)	0.035 (3)	−0.004 (2)
C19	0.0502 (10)	0.0450 (10)	0.0678 (13)	0.0025 (8)	−0.0093 (9)	0.0033 (9)
C20	0.0523 (13)	0.106 (2)	0.124 (3)	−0.0045 (14)	−0.0092 (15)	0.042 (2)
C21	0.098 (2)	0.143 (3)	0.0621 (17)	0.027 (2)	−0.0057 (16)	0.018 (2)

Geometric parameters (Å, º) top

Ce—N1	2.4820 (17)	C10—H10B	0.9800
Ce—N1ⁱ	2.4820 (17)	C10—H10C	0.9800
Ce—N2	2.4860 (14)	C11—C12	1.490 (5)
Ce—N2ⁱ	2.4860 (14)	C11—C13	1.521 (5)
Ce—N3ⁱ	2.4924 (15)	C11—H11	1.0000
Ce—N3	2.4924 (15)	C12—H12A	0.9800
Ce—C14	2.906 (2)	C12—H12B	0.9800
Ce—C1	2.9071 (18)	C12—H12C	0.9800
Ce—C1ⁱ	2.9071 (18)	C13—H13A	0.9800
N1—C1	1.328 (2)	C13—H13B	0.9800
N1—C11	1.458 (2)	C13—H13C	0.9800
N2—C1	1.319 (2)	C14—N3ⁱ	1.325 (2)
N2—C8	1.460 (2)	C14—C15ⁱ	1.498 (3)
N3—C14	1.325 (2)	C14—C15	1.498 (3)
N3—C19	1.457 (2)	C15—C16	1.3900
C1—C2	1.508 (2)	C15—C16A	1.3900
C2—C3	1.378 (3)	C16—C17	1.3900
C2—C7	1.379 (3)	C16—H16	0.9500
C3—C4	1.383 (3)	C17—C18	1.3900
C3—H3	0.9500	C17—H17	0.9500
C4—C5	1.363 (4)	C18—C17A	1.3900
C4—H4	0.9500	C18—H18	0.9500
C5—C6	1.374 (4)	C17A—C16A	1.3900
C5—H5	0.9500	C17A—H17A	0.9500
C6—C7	1.389 (3)	C16A—H16A	0.9500
C6—H6	0.9500	C19—C20	1.498 (4)
C7—H7	0.9500	C19—C21	1.522 (4)
C8—C9	1.503 (4)	C19—H19	1.0000
C8—C10	1.506 (3)	C20—H20A	0.9800
C8—H8	1.0000	C20—H20B	0.9800
C9—H9A	0.9800	C20—H20C	0.9800
C9—H9B	0.9800	C21—H21A	0.9800
C9—H9C	0.9800	C21—H21B	0.9800
C10—H10A	0.9800	C21—H21C	0.9800

N1—Ce—N1ⁱ	97.57 (11)	C8—C9—H9C	109.5
N1—Ce—N2	53.95 (5)	H9A—C9—H9C	109.5
N1ⁱ—Ce—N2	100.23 (6)	H9B—C9—H9C	109.5
N1—Ce—N2ⁱ	100.23 (6)	C8—C10—H10A	109.5
N1ⁱ—Ce—N2ⁱ	53.95 (5)	C8—C10—H10B	109.5
N2—Ce—N2ⁱ	143.66 (8)	H10A—C10—H10B	109.5
N1—Ce—N3ⁱ	151.12 (7)	C8—C10—H10C	109.5
N1ⁱ—Ce—N3ⁱ	107.34 (7)	H10A—C10—H10C	109.5
N2—Ce—N3ⁱ	106.11 (6)	H10B—C10—H10C	109.5
N2ⁱ—Ce—N3ⁱ	106.13 (6)	N1—C11—C12	110.6 (2)
N1—Ce—N3	107.34 (7)	N1—C11—C13	107.7 (2)
N1ⁱ—Ce—N3	151.12 (7)	C12—C11—C13	108.2 (3)
N2—Ce—N3	106.13 (6)	N1—C11—H11	110.1
N2ⁱ—Ce—N3	106.11 (6)	C12—C11—H11	110.1
N3ⁱ—Ce—N3	54.12 (7)	C13—C11—H11	110.1
N1—Ce—C14	131.22 (6)	C11—C12—H12A	109.5
N1ⁱ—Ce—C14	131.22 (6)	C11—C12—H12B	109.5
N2—Ce—C14	108.17 (4)	H12A—C12—H12B	109.5
N2ⁱ—Ce—C14	108.17 (4)	C11—C12—H12C	109.5
N1ⁱ—Ce—C1	99.24 (7)	H12A—C12—H12C	109.5
N2ⁱ—Ce—C1	123.14 (6)	H12B—C12—H12C	109.5
N3ⁱ—Ce—C1	130.59 (6)	C11—C13—H13A	109.5
N3—Ce—C1	109.60 (6)	C11—C13—H13B	109.5
C14—Ce—C1	123.62 (4)	H13A—C13—H13B	109.5
N1—Ce—C1ⁱ	99.24 (7)	C11—C13—H13C	109.5
N2—Ce—C1ⁱ	123.14 (6)	H13A—C13—H13C	109.5
N3ⁱ—Ce—C1ⁱ	109.60 (6)	H13B—C13—H13C	109.5
N3—Ce—C1ⁱ	130.59 (6)	N3—C14—N3ⁱ	117.6 (2)
C14—Ce—C1ⁱ	123.62 (4)	N3—C14—C15ⁱ	124.5 (6)
C1—Ce—C1ⁱ	112.76 (8)	N3ⁱ—C14—C15ⁱ	117.6 (6)
C1—N1—C11	122.56 (17)	N3—C14—C15	117.6 (6)
C1—N1—Ce	94.58 (12)	N3ⁱ—C14—C15	124.5 (6)
C11—N1—Ce	141.07 (13)	N3—C14—Ce	58.81 (11)
C1—N2—C8	122.34 (16)	N3ⁱ—C14—Ce	58.81 (11)
C1—N2—Ce	94.66 (10)	C15ⁱ—C14—Ce	173.9 (3)
C8—N2—Ce	141.91 (12)	C15—C14—Ce	173.9 (3)
C14—N3—C19	121.67 (16)	C16—C15—C16A	120.0
C14—N3—Ce	94.14 (12)	C16—C15—C14	120.2 (5)
C19—N3—Ce	143.45 (13)	C16A—C15—C14	119.8 (5)
N2—C1—N1	116.73 (16)	C17—C16—C15	120.0
N2—C1—C2	122.10 (15)	C17—C16—H16	120.0
N1—C1—C2	121.17 (16)	C15—C16—H16	120.0
N2—C1—Ce	58.46 (9)	C16—C17—C18	120.0
N1—C1—Ce	58.33 (10)	C16—C17—H17	120.0
C2—C1—Ce	177.18 (14)	C18—C17—H17	120.0
C3—C2—C7	118.72 (18)	C17A—C18—C17	120.0
C3—C2—C1	120.63 (18)	C17A—C18—H18	120.0
C7—C2—C1	120.65 (18)	C17—C18—H18	120.0
C2—C3—C4	121.0 (2)	C18—C17A—C16A	120.0
C2—C3—H3	119.5	C18—C17A—H17A	120.0
C4—C3—H3	119.5	C16A—C17A—H17A	120.0
C5—C4—C3	120.1 (2)	C17A—C16A—C15	120.0
C5—C4—H4	120.0	C17A—C16A—H16A	120.0
C3—C4—H4	120.0	C15—C16A—H16A	120.0
C4—C5—C6	119.7 (2)	N3—C19—C20	110.0 (2)
C4—C5—H5	120.2	N3—C19—C21	109.4 (2)
C6—C5—H5	120.2	C20—C19—C21	111.0 (3)
C5—C6—C7	120.5 (2)	N3—C19—H19	108.8
C5—C6—H6	119.8	C20—C19—H19	108.8
C7—C6—H6	119.8	C21—C19—H19	108.8
C2—C7—C6	120.0 (2)	C19—C20—H20A	109.5
C2—C7—H7	120.0	C19—C20—H20B	109.5
C6—C7—H7	120.0	H20A—C20—H20B	109.5
N2—C8—C9	109.27 (18)	C19—C20—H20C	109.5
N2—C8—C10	110.12 (17)	H20A—C20—H20C	109.5
C9—C8—C10	110.5 (2)	H20B—C20—H20C	109.5
N2—C8—H8	109.0	C19—C21—H21A	109.5
C9—C8—H8	109.0	C19—C21—H21B	109.5
C10—C8—H8	109.0	H21A—C21—H21B	109.5
C8—C9—H9A	109.5	C19—C21—H21C	109.5
C8—C9—H9B	109.5	H21A—C21—H21C	109.5
H9A—C9—H9B	109.5	H21B—C21—H21C	109.5

N1ⁱ—Ce—N1—C1	95.52 (15)	C14—Ce—C1—N2	−61.08 (14)
N2—Ce—N1—C1	−1.66 (13)	C1ⁱ—Ce—C1—N2	118.92 (14)
N2ⁱ—Ce—N1—C1	150.12 (14)	N1ⁱ—Ce—C1—N1	−88.55 (18)
N3ⁱ—Ce—N1—C1	−54.1 (2)	N2—Ce—C1—N1	177.0 (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—N1	148.96 (14)
C1ⁱ—Ce—N1—C1	122.86 (14)	N3—Ce—C1—N1	89.91 (15)
N1ⁱ—Ce—N1—C11	−67.9 (3)	C14—Ce—C1—N1	115.96 (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—C3	107.5 (2)
N3ⁱ—Ce—N1—C11	142.4 (3)	N1—C1—C2—C3	−73.0 (3)
N3—Ce—N1—C11	97.3 (3)	N2—C1—C2—C7	−73.4 (3)
C14—Ce—N1—C11	112.1 (3)	N1—C1—C2—C7	106.2 (2)
C1—Ce—N1—C11	−163.4 (4)	C7—C2—C3—C4	0.7 (3)
C1ⁱ—Ce—N1—C11	−40.5 (3)	C1—C2—C3—C4	179.88 (19)
N1—Ce—N2—C1	1.67 (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—C7	1.1 (4)
N3ⁱ—Ce—N2—C1	158.16 (12)	C3—C2—C7—C6	−0.2 (3)
N3—Ce—N2—C1	101.64 (13)	C1—C2—C7—C6	−179.3 (2)
C14—Ce—N2—C1	129.90 (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—C9	58.8 (3)
N1ⁱ—Ce—N2—C8	102.8 (2)	C1—N2—C8—C10	132.7 (2)
N2ⁱ—Ce—N2—C8	143.0 (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—C12	55.4 (4)
C14—Ce—N2—C8	−37.0 (2)	C1—N1—C11—C13	137.2 (3)
C1—Ce—N2—C8	−166.9 (3)	Ce—N1—C11—C13	−62.6 (4)
C1ⁱ—Ce—N2—C8	118.5 (2)	C19—N3—C14—N3ⁱ	172.3 (2)
N1—Ce—N3—C14	155.00 (8)	C19—N3—C14—C15ⁱ	−13.8 (4)
N1ⁱ—Ce—N3—C14	−56.63 (17)	Ce—N3—C14—C15ⁱ	173.9 (3)
N2—Ce—N3—C14	98.47 (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—C14	126.50 (9)	C19—N3—C14—Ce	172.3 (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—N3	147.57 (11)
N1ⁱ—Ce—N3—C19	134.4 (2)	N2—Ce—C14—N3	−90.02 (10)
N2—Ce—N3—C19	−70.5 (3)	N2ⁱ—Ce—C14—N3	89.98 (10)
N2ⁱ—Ce—N3—C19	92.5 (3)	C1—Ce—C14—N3	−65.41 (11)
N3ⁱ—Ce—N3—C19	−169.0 (3)	C1ⁱ—Ce—C14—N3	114.59 (11)
C14—Ce—N3—C19	−169.0 (3)	N1—Ce—C14—N3ⁱ	147.57 (11)
C1—Ce—N3—C19	−42.5 (3)	N1ⁱ—Ce—C14—N3ⁱ	−32.43 (11)
C1ⁱ—Ce—N3—C19	105.3 (3)	N2—Ce—C14—N3ⁱ	89.98 (10)
C8—N2—C1—N1	167.7 (2)	N2ⁱ—Ce—C14—N3ⁱ	−90.02 (10)
Ce—N2—C1—N1	−2.8 (2)	C1—Ce—C14—N3ⁱ	114.59 (11)
C8—N2—C1—C2	−12.8 (3)	C1ⁱ—Ce—C14—N3ⁱ	−65.41 (11)
Ce—N2—C1—C2	176.75 (17)	N3—C14—C15—C16	88.9 (6)
C8—N2—C1—Ce	170.5 (2)	N3ⁱ—C14—C15—C16	−85.0 (5)
C11—N1—C1—N2	170.5 (2)	C15ⁱ—C14—C15—C16	−144 (5)
Ce—N1—C1—N2	2.8 (2)	N3—C14—C15—C16A	−92.6 (5)
C11—N1—C1—C2	−9.0 (4)	N3ⁱ—C14—C15—C16A	93.5 (6)
Ce—N1—C1—C2	−176.75 (17)	C15ⁱ—C14—C15—C16A	34 (4)
C11—N1—C1—Ce	167.7 (3)	C14—C15—C16—C17	178.5 (11)
N1—Ce—C1—N2	−177.0 (2)	C14—C15—C16A—C17A	−178.5 (11)
N1ⁱ—Ce—C1—N2	94.41 (13)	C14—N3—C19—C20	134.4 (2)
N2ⁱ—Ce—C1—N2	147.12 (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—C21	63.7 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Ce(C₁₃H₁₉N₂)₃]
M_r	750.03
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	133
a, b, c (Å)	14.1225 (4), 18.5957 (6), 15.6544 (4)
β (°)	98.324 (2)
V (Å³)	4067.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.15
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	32963, 5485, 5147
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.061, 1.11
No. of reflections	5485
No. of parameters	230
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −1.00

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP (Siemens, 1994).

Acknowledgements

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.

References

Bailey, P. J. & Pace, S. (2001). Coord. Chem. Rev. 214, 91–141. Web of Science CrossRef CAS Google Scholar
Edelmann, F. T. (2009). Chem. Soc. Rev. 38, 2253–2268. Web of Science CrossRef PubMed CAS Google Scholar
Edelmann, F. T., Freckmann, D. M. M. & Schumann, H. (2002). Chem. Rev. 102, 1851–1896. Web of Science CrossRef PubMed CAS Google Scholar
Lim, B. S., Rahtu, A., Park, J.-S. & Gordon, R. G. (2003). Inorg. Chem. 42, 7951–7958. Web of Science CSD CrossRef PubMed CAS Google Scholar
Päiväsaari, J., Dezelah, C. L., Back, D., El-Kaderi, H. M., Heeg, M. J., Putkonen, M., Niinistö, L. & Winter, C. H. (2005). J. Mater. Chem. 15, 4224–4233. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1994). XP. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Stoe & Cie (2002). X-AREA and X-RED. Stoe & Cie, Darmstadt, Germany. Google Scholar
Wedler, M., Knösel, F., Pieper, U., Stalke, D., Edelmann, F. T. & Amberger, H.-D. (1992). Chem. Ber. 125, 2171–2181. CrossRef CAS Web of Science Google Scholar