Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043966/gg2042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043966/gg2042Isup2.hkl |
CCDC reference: 663602
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.004 Å
- Disorder in solvent or counterion
- R factor = 0.032
- wR factor = 0.086
- Data-to-parameter ratio = 15.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT223_ALERT_4_C Large Solvent/Anion H Ueq(max)/Ueq(min) ... 3.70 Ratio PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 50.00 Perc.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 42
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 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
All operations were carried out under N2 atmosphere. Solvents have been dried by standard methods and de-oxygenized.
30 ml of toluene were added to a mixture of 0.5 g (0.87 mmol) (nacnac)ZrCl3(THF) (Fortuné et al., 2007) and 0.115 g indenyl lithium (0.96 mmol). After two days of stirring at room temperature, the obtained suspension is filtered and the precipitate washed with 8 ml of toluene. The volume of the combined filtrates was reduced to ca 10 ml and layered with 10 ml of hexane. After two weeks the product was isolated by decantation of the solvent as yellow microcrystals, 0.213 g (42%).
NMR 1H (300 MHz, C6D6), δ p.p.m.: 7.13–7.30 (m), 6.70 (br s, 1H), 6.46 (br s, 2H), 5.67 (s, 1H), 2.63 (s, 6H), 2.07 (s, 6H), 1.97 (s, 6H).
The H atoms were generated geometrically (C—H 0.93 to 0.98, N—H 0.86 and O—H 0.82 Å) and were included in the refinement in the riding model approximation, their temperature factors were set to 1.5 times those of the equivalent isotropic temperature factors of the parent site (methyl) and 1.2 times for others.
The title compound was synthesized by ligand metathesis starting from [bis(2,6-dimethylphenyl)nacnac]ZrCl3(THF) ("nacnac" = pentane-2,4-diiminato) and indenyl lithium. Layering of a toluene solution with hexane yielded crystals in sufficient quality for X-ray analysis.
Coordination of the nacnac ligand to group 4 metals differs strongly depending on the compound composition, the nature of the nacnac ligand and the metal center. An in-plane η2-coordination is often observed in octahedral coordinated compounds (Kakaliou et al., 1999; Qian et al.; 1999; Jin & Novak, 2000; Franceschini et al., 2003; Hamaki et al., 2006). With sterically less encumbered nacnac ligands, such as N,N'-diphenyl nacnac, and in particular in the presence of a second, η5-coordinated ligand such as cyclopentadienyl or indenyl, a cyclopentadienyl-like η5-coordination has been observed (Rahim et al., 1998; Vollmerhaus et al., 2000). One example of such is (Ind)(N,N'-diphenyl-nacnac)ZrCl2, which differs from the title compound (I) only by the lack of the 2,6-methyl substituents on the N-bonded phenyl rings (Rahim et al., 1998).
In contrast to these, the nacnac ligand adopts in (I), an intermediate, distorted coordination mode. The coordination of N1 and the carbon atoms C2 and C3 can be described as an η3-coordinated enamide, as evidenced by Zr—C distances of 2.617 (2) and 2.616 (2) Å, respectively, and an angle 〈 (C1,C2,Zr) of 140.7 (2)°. The Zr—C4 distance of 2.825 (2) Å, however, is significantly elongated in comparison to C2 and C3 and the methyl substituent at C4 is orientated away from the metal center with a bond angle 〈 (C5,C4,Zr) of 169.5 (2)°, indicating that the N lone pair, but not the C═N-bond is coordinated to the Zr center. (While we cannot completely exclude a π-coordination of C4 to the metal, the elongated Zr—C4 distance makes this improbable.) The coordination of the nacnac ligand can be thus broken down into two parts, an η3-enaminato coordination of C2, C3 and N1 and an η1-imine coordination of C4 and N2.
The planar coordination of the enaminato-moiety and the in-plane coordination of the imine-moiety results in a folding of the ligand backbone, which reduces its electron delocalization. The least-square planes through N1, C1–C3 and N2, C3–C5 display an angle of 41°. Bond distances observed in the ligand backbone agree with a slight separation of the π-system into an enaminato- and an imine-moiety. The proposed imine bond N2═C4 is shorter than the so-assigned enamine bond N1═C2 (1.303 (3) and 1.352 (3) Å, respectively). The C2—C3 distance of 1.394 (3) Å is comparable to the N—C distances, while the C3—C4 distance is significantly elongated to 1.454 (3) Å and can be assigned a higher single-bond character.
The coordination of the nacnac ligand observed here differs from the earlier described η2 or η5-coordination (see above) and from those observed, for example, in scandium complexes, where a placement of the Sc center outside of the ligand plane was ascribed to steric reasons without any significant coordination of the carbon atoms to the metal center (Lee et al., 1999). A comparable coordination, however, was observed for the nacnac ligand in the five-coordinated complexes reported by Basuli et al. (2004) (CSD-codes: FAPBUU, FAPCAP, FAPCEF & FABCIJ). Their coordination was described simply as "sandwich-like". Not surprisingly, the analogous compound in which indenyl is replaced by cyclopentadienyl is nearly isostructural (Verguet et al., 2007).
The indenyl ligand displays only a very slight deviation from ideal η5-coordination (ΔM–C = 0.11 Å and Ω = 4°˛ Faller et al., 1985).
For a related mixed (indenyl)(nacnac)ZrCl2 compound, see Rahim et al. (1998). For the analogous cyclopentadienyl compound, see Verguet et al. (2007). For comparable coordination of the nacnac ligand in five-coordinated complexes, see Basuli et al. (2004) [Cambridge Structural Database (Allen, 2002) refcodes FAPBUU, FAPCAP, FAPCEF and FABCIJ]. For Zr complexes containing η2-coordinated nacnac, see: Kakaliou et al. (1999); Qian et al. (1999); Jin & Novak (2000); Franceschini et al. (2003); Hamaki et al. (2006). For Zr complexes containing η5-like coordinated nacnac, see: Rahim et al. (1998); Vollmerhaus et al. (2000). For related literature, see: Faller et al. (1985); Fortuné et al. (2007); Lee et al. (1999).
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: SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (local program).
Fig. 1. ORTEP view of the title compound (I). Displacement ellipsoids are shown at 50% probability levels. Hydrogen atoms and the solvent molecule are omitted for clarity. |
[Zr(Cl)2(C21H25N2)(C9H7)]·0.5C7H8 | F(000) = 2600 |
Mr = 628.77 | Dx = 1.395 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -C 2yc | Cell parameters from 16709 reflections |
a = 25.6719 (7) Å | θ = 4.1–71.5° |
b = 12.2509 (3) Å | µ = 4.83 mm−1 |
c = 22.6278 (6) Å | T = 150 K |
β = 122.701 (1)° | Hexagonal prism, yellow |
V = 5988.6 (3) Å3 | 0.27 × 0.21 × 0.18 mm |
Z = 8 |
Bruker SMART 6000 diffractometer | 5814 independent reflections |
Radiation source: Rotating Anode | 5182 reflections with I > 2σ(I) |
Montel 200 optics monochromator | Rint = 0.036 |
Detector resolution: 5.5 pixels mm-1 | θmax = 71.8°, θmin = 4.1° |
ω scans | h = −31→31 |
Absorption correction: multi-scan (SADABS; Sheldrick,1996) | k = −15→14 |
Tmin = 0.322, Tmax = 0.419 | l = −27→27 |
36248 measured reflections |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.00 | w 1 /[σ2(Fo2) + (0.0655P)2] where P = (Fo2 + 2Fc2)/3 |
5814 reflections | (Δ/σ)max = 0.003 |
380 parameters | Δρmax = 0.48 e Å−3 |
42 restraints | Δρmin = −0.99 e Å−3 |
[Zr(Cl)2(C21H25N2)(C9H7)]·0.5C7H8 | V = 5988.6 (3) Å3 |
Mr = 628.77 | Z = 8 |
Monoclinic, C2/c | Cu Kα radiation |
a = 25.6719 (7) Å | µ = 4.83 mm−1 |
b = 12.2509 (3) Å | T = 150 K |
c = 22.6278 (6) Å | 0.27 × 0.21 × 0.18 mm |
β = 122.701 (1)° |
Bruker SMART 6000 diffractometer | 5814 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick,1996) | 5182 reflections with I > 2σ(I) |
Tmin = 0.322, Tmax = 0.419 | Rint = 0.036 |
36248 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 42 restraints |
wR(F2) = 0.086 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.48 e Å−3 |
5814 reflections | Δρmin = −0.99 e Å−3 |
380 parameters |
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. Half a molecule of toluene cocrystallized with the compound. The toluene was found disordered around a C2 axis. The disorder was resolved and the molecule refined isotropically with half occupancy and strong SIMU restraints. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zr | 0.143188 (7) | 0.483751 (13) | 0.008416 (9) | 0.01843 (7) | |
Cl1 | 0.03687 (2) | 0.47259 (4) | −0.09714 (3) | 0.02579 (12) | |
Cl2 | 0.12545 (3) | 0.68593 (4) | −0.00659 (3) | 0.03025 (13) | |
N1 | 0.19716 (8) | 0.51001 (13) | 0.12184 (9) | 0.0207 (4) | |
N2 | 0.11907 (8) | 0.32659 (13) | 0.04335 (9) | 0.0204 (3) | |
C1 | 0.14769 (10) | 0.64130 (18) | 0.16091 (12) | 0.0303 (5) | |
H1A | 0.1793 | 0.6329 | 0.2110 | 0.045* | |
H1B | 0.1071 | 0.6511 | 0.1546 | 0.045* | |
H1C | 0.1573 | 0.7053 | 0.1425 | 0.045* | |
C2 | 0.14666 (10) | 0.54086 (17) | 0.12195 (11) | 0.0213 (4) | |
C3 | 0.09133 (10) | 0.48371 (16) | 0.08108 (12) | 0.0226 (4) | |
H3 | 0.0518 | 0.5251 | 0.0617 | 0.027* | |
C4 | 0.08729 (9) | 0.36697 (17) | 0.06765 (11) | 0.0221 (4) | |
C5 | 0.04803 (11) | 0.30251 (18) | 0.08539 (14) | 0.0323 (5) | |
H5A | 0.0496 | 0.2251 | 0.0756 | 0.048* | |
H5B | 0.0052 | 0.3284 | 0.0570 | 0.048* | |
H5C | 0.0636 | 0.3118 | 0.1353 | 0.048* | |
C6 | 0.25771 (10) | 0.52759 (17) | 0.18412 (12) | 0.0242 (4) | |
C7 | 0.27341 (11) | 0.46406 (18) | 0.24365 (12) | 0.0277 (5) | |
C8 | 0.33397 (12) | 0.4680 (2) | 0.30195 (13) | 0.0358 (6) | |
H8 | 0.3455 | 0.4229 | 0.3414 | 0.043* | |
C9 | 0.37739 (12) | 0.5363 (2) | 0.30332 (14) | 0.0419 (6) | |
H9 | 0.4187 | 0.5367 | 0.3430 | 0.050* | |
C10 | 0.36058 (10) | 0.6040 (2) | 0.24692 (13) | 0.0391 (6) | |
H10 | 0.3902 | 0.6533 | 0.2493 | 0.047* | |
C11 | 0.30077 (10) | 0.60146 (19) | 0.18634 (12) | 0.0290 (5) | |
C12 | 0.22623 (11) | 0.3966 (2) | 0.24793 (12) | 0.0324 (5) | |
H12A | 0.2473 | 0.3378 | 0.2822 | 0.049* | |
H12B | 0.1966 | 0.3651 | 0.2017 | 0.049* | |
H12C | 0.2042 | 0.4432 | 0.2626 | 0.049* | |
C13 | 0.28577 (11) | 0.6822 (2) | 0.12911 (14) | 0.0358 (5) | |
H13A | 0.2997 | 0.7551 | 0.1496 | 0.054* | |
H13B | 0.2410 | 0.6833 | 0.0950 | 0.054* | |
H13C | 0.3069 | 0.6608 | 0.1055 | 0.054* | |
C14 | 0.12040 (10) | 0.21030 (16) | 0.03269 (11) | 0.0232 (4) | |
C15 | 0.17576 (10) | 0.15317 (17) | 0.07763 (11) | 0.0238 (4) | |
C16 | 0.17834 (12) | 0.04197 (19) | 0.06504 (13) | 0.0295 (5) | |
H16 | 0.2157 | 0.0028 | 0.0942 | 0.035* | |
C17 | 0.12726 (14) | −0.01187 (19) | 0.01081 (15) | 0.0387 (6) | |
H17 | 0.1298 | −0.0871 | 0.0026 | 0.046* | |
C18 | 0.07303 (12) | 0.0442 (2) | −0.03091 (14) | 0.0380 (6) | |
H18 | 0.0378 | 0.0063 | −0.0669 | 0.046* | |
C19 | 0.06834 (11) | 0.15637 (18) | −0.02168 (13) | 0.0307 (5) | |
C20 | 0.23056 (10) | 0.20341 (18) | 0.14176 (12) | 0.0283 (5) | |
H20A | 0.2290 | 0.1860 | 0.1831 | 0.042* | |
H20B | 0.2296 | 0.2828 | 0.1359 | 0.042* | |
H20C | 0.2688 | 0.1742 | 0.1481 | 0.042* | |
C21 | 0.00696 (12) | 0.2117 (2) | −0.07102 (15) | 0.0465 (7) | |
H21A | 0.0119 | 0.2909 | −0.0641 | 0.070* | |
H21B | −0.0238 | 0.1858 | −0.0613 | 0.070* | |
H21C | −0.0069 | 0.1942 | −0.1197 | 0.070* | |
C22 | 0.24844 (10) | 0.45664 (19) | 0.03229 (12) | 0.0273 (5) | |
H22 | 0.2828 | 0.4709 | 0.0784 | 0.033* | |
C23 | 0.21781 (10) | 0.35619 (17) | 0.00798 (12) | 0.0252 (4) | |
H23 | 0.2261 | 0.2922 | 0.0354 | 0.030* | |
C24 | 0.17205 (10) | 0.36687 (18) | −0.06511 (11) | 0.0244 (4) | |
C25 | 0.13063 (11) | 0.29092 (19) | −0.11733 (13) | 0.0309 (5) | |
H25 | 0.1287 | 0.2174 | −0.1054 | 0.037* | |
C26 | 0.09397 (12) | 0.3268 (2) | −0.18478 (14) | 0.0383 (6) | |
H26 | 0.0667 | 0.2767 | −0.2202 | 0.046* | |
C27 | 0.09525 (12) | 0.4366 (2) | −0.20382 (13) | 0.0381 (6) | |
H27 | 0.0689 | 0.4582 | −0.2515 | 0.046* | |
C28 | 0.13362 (12) | 0.5117 (2) | −0.15509 (13) | 0.0316 (5) | |
H28 | 0.1337 | 0.5853 | −0.1682 | 0.038* | |
C29 | 0.17358 (11) | 0.47757 (17) | −0.08417 (12) | 0.0250 (5) | |
C30 | 0.21977 (10) | 0.53284 (16) | −0.02299 (12) | 0.0265 (5) | |
H30 | 0.2297 | 0.6082 | −0.0198 | 0.032* | |
C31 | 0.50653 (10) | 0.57281 (16) | 0.26223 (12) | 0.0489 (14) | 0.50 |
C32 | 0.47229 (10) | 0.61465 (16) | 0.19443 (12) | 0.051 (2) | 0.50 |
H32 | 0.4540 | 0.5658 | 0.1557 | 0.062* | 0.50 |
C33 | 0.4645 (5) | 0.7226 (9) | 0.1824 (5) | 0.056 (3) | 0.50 |
H33 | 0.4387 | 0.7487 | 0.1357 | 0.067* | 0.50 |
C34 | 0.4928 (5) | 0.7944 (6) | 0.2360 (4) | 0.047 (2) | 0.50 |
H34 | 0.4888 | 0.8706 | 0.2266 | 0.057* | 0.50 |
C35 | 0.5272 (4) | 0.7581 (6) | 0.3039 (5) | 0.0307 (17) | 0.50 |
H35 | 0.5452 | 0.8091 | 0.3415 | 0.037* | 0.50 |
C36 | 0.5356 (3) | 0.6497 (6) | 0.3179 (4) | 0.0341 (14) | 0.50 |
H36 | 0.5611 | 0.6251 | 0.3650 | 0.041* | 0.50 |
C37 | 0.5191 (5) | 0.4517 (6) | 0.2769 (5) | 0.091 (3) | 0.50 |
H37A | 0.4873 | 0.4191 | 0.2827 | 0.137* | 0.50 |
H37B | 0.5599 | 0.4411 | 0.3200 | 0.137* | 0.50 |
H37C | 0.5183 | 0.4165 | 0.2375 | 0.137* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr | 0.01806 (11) | 0.01647 (11) | 0.02401 (11) | 0.00228 (6) | 0.01350 (8) | −0.00109 (6) |
Cl1 | 0.0198 (2) | 0.0313 (3) | 0.0267 (3) | 0.00414 (19) | 0.0128 (2) | −0.00094 (19) |
Cl2 | 0.0332 (3) | 0.0180 (2) | 0.0404 (3) | 0.0040 (2) | 0.0205 (2) | 0.0020 (2) |
N1 | 0.0185 (8) | 0.0204 (8) | 0.0241 (9) | −0.0002 (7) | 0.0121 (7) | −0.0022 (7) |
N2 | 0.0178 (8) | 0.0164 (8) | 0.0266 (9) | 0.0010 (6) | 0.0117 (7) | −0.0013 (6) |
C1 | 0.0284 (11) | 0.0281 (11) | 0.0362 (12) | 0.0015 (9) | 0.0187 (10) | −0.0098 (9) |
C2 | 0.0225 (10) | 0.0197 (9) | 0.0253 (10) | 0.0032 (8) | 0.0154 (8) | 0.0010 (8) |
C3 | 0.0224 (11) | 0.0197 (10) | 0.0308 (11) | 0.0019 (8) | 0.0177 (9) | −0.0018 (8) |
C4 | 0.0167 (9) | 0.0206 (10) | 0.0284 (10) | 0.0019 (8) | 0.0119 (8) | 0.0004 (8) |
C5 | 0.0314 (12) | 0.0254 (11) | 0.0514 (15) | −0.0005 (9) | 0.0299 (11) | 0.0002 (10) |
C6 | 0.0204 (10) | 0.0254 (11) | 0.0282 (11) | 0.0012 (8) | 0.0140 (9) | −0.0066 (8) |
C7 | 0.0267 (11) | 0.0291 (11) | 0.0277 (11) | 0.0054 (9) | 0.0149 (10) | −0.0051 (9) |
C8 | 0.0308 (13) | 0.0418 (14) | 0.0290 (12) | 0.0090 (11) | 0.0122 (10) | −0.0049 (10) |
C9 | 0.0233 (12) | 0.0507 (16) | 0.0379 (14) | 0.0031 (11) | 0.0076 (10) | −0.0112 (12) |
C10 | 0.0233 (12) | 0.0450 (15) | 0.0452 (15) | −0.0065 (11) | 0.0160 (11) | −0.0149 (12) |
C11 | 0.0235 (10) | 0.0310 (11) | 0.0349 (12) | −0.0034 (9) | 0.0175 (10) | −0.0096 (9) |
C12 | 0.0355 (12) | 0.0351 (12) | 0.0294 (11) | 0.0058 (10) | 0.0194 (10) | 0.0028 (10) |
C13 | 0.0324 (12) | 0.0359 (13) | 0.0433 (14) | −0.0128 (10) | 0.0232 (11) | −0.0089 (11) |
C14 | 0.0247 (10) | 0.0171 (9) | 0.0308 (11) | 0.0010 (8) | 0.0169 (9) | −0.0021 (8) |
C15 | 0.0269 (10) | 0.0222 (10) | 0.0294 (11) | 0.0043 (9) | 0.0199 (9) | 0.0031 (8) |
C16 | 0.0388 (13) | 0.0233 (10) | 0.0379 (13) | 0.0081 (10) | 0.0282 (11) | 0.0047 (9) |
C17 | 0.0564 (17) | 0.0199 (11) | 0.0538 (17) | 0.0012 (11) | 0.0389 (15) | −0.0034 (10) |
C18 | 0.0416 (14) | 0.0249 (11) | 0.0466 (15) | −0.0080 (11) | 0.0233 (12) | −0.0125 (11) |
C19 | 0.0279 (11) | 0.0230 (11) | 0.0376 (12) | −0.0006 (9) | 0.0153 (10) | −0.0042 (9) |
C20 | 0.0261 (11) | 0.0308 (11) | 0.0292 (11) | 0.0075 (9) | 0.0156 (9) | 0.0037 (9) |
C21 | 0.0266 (12) | 0.0334 (13) | 0.0524 (16) | −0.0044 (11) | 0.0036 (11) | −0.0094 (12) |
C22 | 0.0208 (10) | 0.0353 (12) | 0.0315 (11) | 0.0038 (9) | 0.0177 (9) | −0.0025 (9) |
C23 | 0.0259 (10) | 0.0252 (10) | 0.0329 (11) | 0.0072 (9) | 0.0215 (9) | 0.0000 (9) |
C24 | 0.0241 (10) | 0.0262 (11) | 0.0313 (11) | 0.0037 (9) | 0.0204 (9) | −0.0020 (9) |
C25 | 0.0313 (11) | 0.0290 (11) | 0.0419 (13) | 0.0001 (10) | 0.0259 (11) | −0.0074 (10) |
C26 | 0.0308 (12) | 0.0481 (15) | 0.0394 (14) | −0.0040 (11) | 0.0212 (11) | −0.0168 (11) |
C27 | 0.0342 (13) | 0.0554 (16) | 0.0285 (12) | 0.0078 (12) | 0.0194 (11) | 0.0007 (11) |
C28 | 0.0327 (13) | 0.0357 (12) | 0.0351 (13) | 0.0073 (10) | 0.0240 (11) | 0.0058 (10) |
C29 | 0.0250 (11) | 0.0274 (11) | 0.0319 (12) | 0.0039 (8) | 0.0214 (10) | 0.0000 (8) |
C30 | 0.0260 (11) | 0.0267 (11) | 0.0350 (12) | −0.0004 (9) | 0.0219 (10) | −0.0026 (9) |
C31 | 0.071 (3) | 0.033 (2) | 0.067 (4) | −0.014 (3) | 0.053 (3) | −0.012 (3) |
C32 | 0.051 (4) | 0.073 (6) | 0.038 (3) | −0.025 (4) | 0.030 (3) | −0.027 (4) |
C33 | 0.041 (4) | 0.084 (7) | 0.031 (4) | −0.001 (6) | 0.012 (3) | 0.011 (5) |
C34 | 0.035 (5) | 0.055 (3) | 0.044 (7) | 0.012 (4) | 0.016 (5) | 0.028 (3) |
C35 | 0.034 (4) | 0.022 (3) | 0.038 (5) | 0.003 (2) | 0.020 (4) | 0.006 (2) |
C36 | 0.039 (3) | 0.023 (3) | 0.036 (3) | −0.008 (2) | 0.017 (2) | 0.004 (2) |
C37 | 0.122 (7) | 0.043 (3) | 0.130 (7) | −0.008 (4) | 0.081 (6) | −0.007 (4) |
Zr—N1 | 2.1836 (18) | C15—C20 | 1.503 (3) |
Zr—N2 | 2.2900 (17) | C16—C17 | 1.386 (4) |
Zr—C22 | 2.475 (2) | C16—H16 | 0.9500 |
Zr—Cl1 | 2.4758 (5) | C17—C18 | 1.372 (4) |
Zr—C23 | 2.4763 (19) | C17—H17 | 0.9500 |
Zr—C30 | 2.498 (2) | C18—C19 | 1.404 (3) |
Zr—Cl2 | 2.5081 (5) | C18—H18 | 0.9500 |
Zr—C24 | 2.588 (2) | C19—C21 | 1.513 (3) |
Zr—C29 | 2.602 (2) | C20—H20A | 0.9800 |
Zr—C3 | 2.616 (2) | C20—H20B | 0.9800 |
Zr—C2 | 2.617 (2) | C20—H20C | 0.9800 |
Zr—C4 | 2.825 (2) | C21—H21A | 0.9800 |
N1—C2 | 1.352 (3) | C21—H21B | 0.9800 |
N1—C6 | 1.443 (3) | C21—H21C | 0.9800 |
N2—C4 | 1.303 (3) | C22—C23 | 1.403 (3) |
N2—C14 | 1.448 (2) | C22—C30 | 1.408 (3) |
C1—C2 | 1.506 (3) | C22—H22 | 0.9500 |
C1—H1A | 0.9800 | C23—C24 | 1.426 (3) |
C1—H1B | 0.9800 | C23—H23 | 0.9500 |
C1—H1C | 0.9800 | C24—C25 | 1.427 (3) |
C2—C3 | 1.394 (3) | C24—C29 | 1.430 (3) |
C3—C4 | 1.454 (3) | C25—C26 | 1.362 (4) |
C3—H3 | 1.0000 | C25—H25 | 0.9500 |
C4—C5 | 1.496 (3) | C26—C27 | 1.418 (4) |
C5—H5A | 0.9800 | C26—H26 | 0.9500 |
C5—H5B | 0.9800 | C27—C28 | 1.364 (4) |
C5—H5C | 0.9800 | C27—H27 | 0.9500 |
C6—C11 | 1.408 (3) | C28—C29 | 1.422 (3) |
C6—C7 | 1.413 (3) | C28—H28 | 0.9500 |
C7—C8 | 1.394 (3) | C29—C30 | 1.417 (3) |
C7—C12 | 1.512 (3) | C30—H30 | 0.9500 |
C8—C9 | 1.381 (4) | C31—C32 | 1.3900 |
C8—H8 | 0.9500 | C31—C36 | 1.419 (7) |
C9—C10 | 1.381 (4) | C31—C37 | 1.517 (7) |
C9—H9 | 0.9500 | C32—C33 | 1.343 (12) |
C10—C11 | 1.401 (3) | C32—H32 | 0.9500 |
C10—H10 | 0.9500 | C33—C34 | 1.350 (11) |
C11—C13 | 1.505 (3) | C33—H33 | 0.9500 |
C12—H12A | 0.9800 | C34—C35 | 1.368 (11) |
C12—H12B | 0.9800 | C34—H34 | 0.9500 |
C12—H12C | 0.9800 | C35—C36 | 1.355 (9) |
C13—H13A | 0.9800 | C35—H35 | 0.9500 |
C13—H13B | 0.9800 | C36—H36 | 0.9500 |
C13—H13C | 0.9800 | C37—H37A | 0.9800 |
C14—C19 | 1.400 (3) | C37—H37B | 0.9800 |
C14—C15 | 1.408 (3) | C37—H37C | 0.9800 |
C15—C16 | 1.401 (3) | ||
N1—Zr—N2 | 80.58 (6) | C8—C9—C10 | 119.8 (2) |
N1—Zr—C22 | 80.71 (7) | C8—C9—H9 | 120.1 |
N2—Zr—C22 | 106.18 (7) | C10—C9—H9 | 120.1 |
N1—Zr—Cl1 | 144.17 (5) | C9—C10—C11 | 121.4 (2) |
N2—Zr—Cl1 | 85.63 (4) | C9—C10—H10 | 119.3 |
C22—Zr—Cl1 | 135.05 (5) | C11—C10—H10 | 119.3 |
N1—Zr—C23 | 95.55 (7) | C10—C11—C6 | 118.2 (2) |
N2—Zr—C23 | 79.91 (7) | C10—C11—C13 | 117.6 (2) |
C22—Zr—C23 | 32.92 (7) | C6—C11—C13 | 124.1 (2) |
Cl1—Zr—C23 | 114.41 (5) | C7—C12—H12A | 109.5 |
N1—Zr—C30 | 101.64 (7) | C7—C12—H12B | 109.5 |
N2—Zr—C30 | 134.56 (6) | H12A—C12—H12B | 109.5 |
C22—Zr—C30 | 32.89 (7) | C7—C12—H12C | 109.5 |
Cl1—Zr—C30 | 111.45 (5) | H12A—C12—H12C | 109.5 |
C23—Zr—C30 | 54.65 (7) | H12B—C12—H12C | 109.5 |
N1—Zr—Cl2 | 88.12 (5) | C11—C13—H13A | 109.5 |
N2—Zr—Cl2 | 144.48 (4) | C11—C13—H13B | 109.5 |
C22—Zr—Cl2 | 105.01 (6) | H13A—C13—H13B | 109.5 |
Cl1—Zr—Cl2 | 84.204 (18) | C11—C13—H13C | 109.5 |
C23—Zr—Cl2 | 134.99 (5) | H13A—C13—H13C | 109.5 |
C30—Zr—Cl2 | 80.62 (5) | H13B—C13—H13C | 109.5 |
N1—Zr—C24 | 128.09 (7) | C19—C14—C15 | 120.80 (19) |
N2—Zr—C24 | 88.94 (6) | C19—C14—N2 | 120.89 (19) |
C22—Zr—C24 | 53.71 (7) | C15—C14—N2 | 118.30 (19) |
Cl1—Zr—C24 | 84.18 (5) | C16—C15—C14 | 118.5 (2) |
C23—Zr—C24 | 32.61 (7) | C16—C15—C20 | 118.2 (2) |
C30—Zr—C24 | 53.68 (7) | C14—C15—C20 | 123.16 (19) |
Cl2—Zr—C24 | 123.60 (5) | C17—C16—C15 | 121.1 (2) |
N1—Zr—C29 | 132.44 (7) | C17—C16—H16 | 119.4 |
N2—Zr—C29 | 120.54 (6) | C15—C16—H16 | 119.4 |
C22—Zr—C29 | 53.48 (7) | C18—C17—C16 | 119.6 (2) |
Cl1—Zr—C29 | 82.85 (5) | C18—C17—H17 | 120.2 |
C23—Zr—C29 | 53.80 (7) | C16—C17—H17 | 120.2 |
C30—Zr—C29 | 32.18 (7) | C17—C18—C19 | 121.6 (2) |
Cl2—Zr—C29 | 91.79 (5) | C17—C18—H18 | 119.2 |
C24—Zr—C29 | 31.99 (6) | C19—C18—H18 | 119.2 |
N1—Zr—C3 | 58.43 (7) | C14—C19—C18 | 118.3 (2) |
N2—Zr—C3 | 57.21 (6) | C14—C19—C21 | 123.8 (2) |
C22—Zr—C3 | 136.82 (7) | C18—C19—C21 | 117.9 (2) |
Cl1—Zr—C3 | 86.34 (5) | C15—C20—H20A | 109.5 |
C23—Zr—C3 | 131.29 (7) | C15—C20—H20B | 109.5 |
C30—Zr—C3 | 157.65 (7) | H20A—C20—H20B | 109.5 |
Cl2—Zr—C3 | 88.19 (4) | C15—C20—H20C | 109.5 |
C24—Zr—C3 | 145.45 (6) | H20A—C20—H20C | 109.5 |
C29—Zr—C3 | 169.13 (7) | H20B—C20—H20C | 109.5 |
N1—Zr—C2 | 31.06 (6) | C19—C21—H21A | 109.5 |
N2—Zr—C2 | 76.00 (6) | C19—C21—H21B | 109.5 |
C22—Zr—C2 | 111.56 (7) | H21A—C21—H21B | 109.5 |
Cl1—Zr—C2 | 113.38 (5) | C19—C21—H21C | 109.5 |
C23—Zr—C2 | 123.81 (7) | H21A—C21—H21C | 109.5 |
C30—Zr—C2 | 126.88 (7) | H21B—C21—H21C | 109.5 |
Cl2—Zr—C2 | 77.08 (5) | C23—C22—C30 | 108.7 (2) |
C24—Zr—C2 | 155.38 (7) | C23—C22—Zr | 73.59 (12) |
C29—Zr—C2 | 158.77 (7) | C30—C22—Zr | 74.47 (12) |
C3—Zr—C2 | 30.90 (6) | C23—C22—H22 | 125.7 |
N1—Zr—C4 | 71.30 (6) | C30—C22—H22 | 125.7 |
N2—Zr—C4 | 27.01 (6) | Zr—C22—H22 | 118.2 |
C22—Zr—C4 | 127.08 (7) | C22—C23—C24 | 108.1 (2) |
Cl1—Zr—C4 | 81.48 (4) | C22—C23—Zr | 73.49 (12) |
C23—Zr—C4 | 105.94 (7) | C24—C23—Zr | 78.02 (12) |
C30—Zr—C4 | 159.45 (6) | C22—C23—H23 | 126.0 |
Cl2—Zr—C4 | 117.57 (4) | C24—C23—H23 | 126.0 |
C24—Zr—C4 | 114.83 (7) | Zr—C23—H23 | 114.8 |
C29—Zr—C4 | 144.83 (6) | C23—C24—C25 | 132.8 (2) |
C3—Zr—C4 | 30.70 (6) | C23—C24—C29 | 107.3 (2) |
C2—Zr—C4 | 54.99 (6) | C25—C24—C29 | 119.9 (2) |
C2—N1—C6 | 119.00 (18) | C23—C24—Zr | 69.37 (11) |
C2—N1—Zr | 92.48 (13) | C25—C24—Zr | 123.30 (14) |
C6—N1—Zr | 146.58 (14) | C29—C24—Zr | 74.52 (12) |
C4—N2—C14 | 121.34 (17) | C26—C25—C24 | 118.2 (2) |
C4—N2—Zr | 100.03 (13) | C26—C25—H25 | 120.9 |
C14—N2—Zr | 137.26 (13) | C24—C25—H25 | 120.9 |
C2—C1—H1A | 109.5 | C25—C26—C27 | 122.1 (2) |
C2—C1—H1B | 109.5 | C25—C26—H26 | 119.0 |
H1A—C1—H1B | 109.5 | C27—C26—H26 | 119.0 |
C2—C1—H1C | 109.5 | C28—C27—C26 | 121.3 (2) |
H1A—C1—H1C | 109.5 | C28—C27—H27 | 119.3 |
H1B—C1—H1C | 109.5 | C26—C27—H27 | 119.3 |
N1—C2—C3 | 119.52 (18) | C27—C28—C29 | 118.7 (2) |
N1—C2—C1 | 121.07 (19) | C27—C28—H28 | 120.7 |
C3—C2—C1 | 119.23 (18) | C29—C28—H28 | 120.7 |
N1—C2—Zr | 56.46 (11) | C30—C29—C28 | 132.4 (2) |
C3—C2—Zr | 74.47 (12) | C30—C29—C24 | 107.7 (2) |
C1—C2—Zr | 140.69 (15) | C28—C29—C24 | 119.9 (2) |
C2—C3—C4 | 124.38 (19) | C30—C29—Zr | 69.89 (12) |
C2—C3—Zr | 74.62 (12) | C28—C29—Zr | 123.55 (15) |
C4—C3—Zr | 82.64 (12) | C24—C29—Zr | 73.49 (12) |
C2—C3—H3 | 117.8 | C22—C30—C29 | 108.12 (18) |
C4—C3—H3 | 117.8 | C22—C30—Zr | 72.64 (12) |
Zr—C3—H3 | 117.8 | C29—C30—Zr | 77.93 (12) |
N2—C4—C3 | 118.12 (19) | C22—C30—H30 | 125.9 |
N2—C4—C5 | 125.40 (19) | C29—C30—H30 | 125.9 |
C3—C4—C5 | 116.45 (18) | Zr—C30—H30 | 115.6 |
N2—C4—Zr | 52.96 (11) | C32—C31—C36 | 116.8 (3) |
C3—C4—Zr | 66.66 (12) | C32—C31—C37 | 122.4 (4) |
C5—C4—Zr | 169.51 (15) | C36—C31—C37 | 120.5 (5) |
C4—C5—H5A | 109.5 | C33—C32—C31 | 121.5 (4) |
C4—C5—H5B | 109.5 | C33—C32—H32 | 119.3 |
H5A—C5—H5B | 109.5 | C31—C32—H32 | 119.3 |
C4—C5—H5C | 109.5 | C32—C33—C34 | 120.8 (8) |
H5A—C5—H5C | 109.5 | C32—C33—H33 | 119.6 |
H5B—C5—H5C | 109.5 | C34—C33—H33 | 119.6 |
C11—C6—C7 | 120.4 (2) | C33—C34—C35 | 120.3 (6) |
C11—C6—N1 | 122.8 (2) | C33—C34—H34 | 119.9 |
C7—C6—N1 | 116.81 (19) | C35—C34—H34 | 119.9 |
C8—C7—C6 | 118.8 (2) | C36—C35—C34 | 120.4 (9) |
C8—C7—C12 | 118.7 (2) | C36—C35—H35 | 119.8 |
C6—C7—C12 | 122.4 (2) | C34—C35—H35 | 119.8 |
C9—C8—C7 | 121.1 (3) | C35—C36—C31 | 120.2 (7) |
C9—C8—H8 | 119.5 | C35—C36—H36 | 119.9 |
C7—C8—H8 | 119.5 | C31—C36—H36 | 119.9 |
N2—Zr—N1—C2 | −78.47 (12) | C15—C16—C17—C18 | −0.6 (4) |
C22—Zr—N1—C2 | 173.26 (13) | C16—C17—C18—C19 | 2.2 (4) |
Cl1—Zr—N1—C2 | −9.68 (16) | C15—C14—C19—C18 | −1.0 (4) |
C23—Zr—N1—C2 | −157.25 (12) | N2—C14—C19—C18 | 177.9 (2) |
C30—Zr—N1—C2 | 147.74 (12) | C15—C14—C19—C21 | 178.7 (2) |
Cl2—Zr—N1—C2 | 67.72 (12) | N2—C14—C19—C21 | −2.5 (4) |
C24—Zr—N1—C2 | −159.62 (11) | C17—C18—C19—C14 | −1.4 (4) |
C29—Zr—N1—C2 | 158.42 (11) | C17—C18—C19—C21 | 179.0 (3) |
C3—Zr—N1—C2 | −21.32 (11) | N1—Zr—C22—C23 | 115.65 (14) |
C4—Zr—N1—C2 | −52.28 (12) | N2—Zr—C22—C23 | 38.37 (14) |
N2—Zr—N1—C6 | 120.3 (2) | Cl1—Zr—C22—C23 | −61.91 (16) |
C22—Zr—N1—C6 | 12.1 (2) | C30—Zr—C22—C23 | −115.34 (19) |
Cl1—Zr—N1—C6 | −170.9 (2) | Cl2—Zr—C22—C23 | −158.84 (12) |
C23—Zr—N1—C6 | 41.6 (2) | C24—Zr—C22—C23 | −37.92 (12) |
C30—Zr—N1—C6 | −13.5 (3) | C29—Zr—C22—C23 | −77.95 (14) |
Cl2—Zr—N1—C6 | −93.5 (2) | C3—Zr—C22—C23 | 97.39 (15) |
C24—Zr—N1—C6 | 39.2 (3) | C2—Zr—C22—C23 | 119.38 (13) |
C29—Zr—N1—C6 | −2.8 (3) | C4—Zr—C22—C23 | 57.72 (15) |
C3—Zr—N1—C6 | 177.5 (3) | N1—Zr—C22—C30 | −129.00 (14) |
C2—Zr—N1—C6 | −161.2 (3) | N2—Zr—C22—C30 | 153.71 (12) |
C4—Zr—N1—C6 | 146.5 (3) | Cl1—Zr—C22—C30 | 53.43 (16) |
N1—Zr—N2—C4 | 67.03 (13) | C23—Zr—C22—C30 | 115.34 (19) |
C22—Zr—N2—C4 | 144.41 (13) | Cl2—Zr—C22—C30 | −43.50 (13) |
Cl1—Zr—N2—C4 | −79.78 (12) | C24—Zr—C22—C30 | 77.43 (14) |
C23—Zr—N2—C4 | 164.45 (14) | C29—Zr—C22—C30 | 37.39 (12) |
C30—Zr—N2—C4 | 164.14 (12) | C3—Zr—C22—C30 | −147.27 (12) |
Cl2—Zr—N2—C4 | −6.12 (17) | C2—Zr—C22—C30 | −125.27 (13) |
C24—Zr—N2—C4 | −164.03 (13) | C4—Zr—C22—C30 | 173.06 (11) |
C29—Zr—N2—C4 | −158.83 (12) | C30—C22—C23—C24 | 4.3 (2) |
C3—Zr—N2—C4 | 8.67 (12) | Zr—C22—C23—C24 | 71.07 (14) |
C2—Zr—N2—C4 | 35.63 (13) | C30—C22—C23—Zr | −66.79 (14) |
N1—Zr—N2—C14 | −127.1 (2) | N1—Zr—C23—C22 | −63.35 (14) |
C22—Zr—N2—C14 | −49.7 (2) | N2—Zr—C23—C22 | −142.73 (14) |
Cl1—Zr—N2—C14 | 86.1 (2) | Cl1—Zr—C23—C22 | 136.81 (12) |
C23—Zr—N2—C14 | −29.7 (2) | C30—Zr—C23—C22 | 36.99 (13) |
C30—Zr—N2—C14 | −30.0 (2) | Cl2—Zr—C23—C22 | 29.53 (16) |
Cl2—Zr—N2—C14 | 159.74 (16) | C24—Zr—C23—C22 | 113.19 (19) |
C24—Zr—N2—C14 | 1.8 (2) | C29—Zr—C23—C22 | 76.92 (14) |
C29—Zr—N2—C14 | 7.0 (2) | C3—Zr—C23—C22 | −115.41 (14) |
C3—Zr—N2—C14 | 174.5 (2) | C2—Zr—C23—C22 | −77.25 (15) |
C2—Zr—N2—C14 | −158.5 (2) | C4—Zr—C23—C22 | −135.46 (13) |
C4—Zr—N2—C14 | 165.9 (3) | N1—Zr—C23—C24 | −176.54 (13) |
C6—N1—C2—C3 | −149.8 (2) | N2—Zr—C23—C24 | 104.08 (13) |
Zr—N1—C2—C3 | 41.9 (2) | C22—Zr—C23—C24 | −113.19 (19) |
C6—N1—C2—C1 | 35.1 (3) | Cl1—Zr—C23—C24 | 23.62 (14) |
Zr—N1—C2—C1 | −133.18 (18) | C30—Zr—C23—C24 | −76.19 (14) |
C6—N1—C2—Zr | 168.3 (2) | Cl2—Zr—C23—C24 | −83.65 (14) |
N2—Zr—C2—N1 | 94.99 (12) | C29—Zr—C23—C24 | −36.26 (12) |
C22—Zr—C2—N1 | −7.15 (14) | C3—Zr—C23—C24 | 131.40 (12) |
Cl1—Zr—C2—N1 | 173.85 (10) | C2—Zr—C23—C24 | 169.56 (12) |
C23—Zr—C2—N1 | 27.60 (15) | C4—Zr—C23—C24 | 111.35 (13) |
C30—Zr—C2—N1 | −40.81 (15) | C22—C23—C24—C25 | 175.2 (2) |
Cl2—Zr—C2—N1 | −108.40 (12) | Zr—C23—C24—C25 | −116.8 (2) |
C24—Zr—C2—N1 | 41.1 (2) | C22—C23—C24—C29 | −2.6 (2) |
C29—Zr—C2—N1 | −48.6 (2) | Zr—C23—C24—C29 | 65.43 (14) |
C3—Zr—C2—N1 | 142.91 (19) | C22—C23—C24—Zr | −67.99 (14) |
C4—Zr—C2—N1 | 113.84 (13) | N1—Zr—C24—C23 | 4.38 (16) |
N1—Zr—C2—C3 | −142.91 (19) | N2—Zr—C24—C23 | −72.77 (13) |
N2—Zr—C2—C3 | −47.92 (12) | C22—Zr—C24—C23 | 38.30 (13) |
C22—Zr—C2—C3 | −150.06 (12) | Cl1—Zr—C24—C23 | −158.48 (13) |
Cl1—Zr—C2—C3 | 30.93 (13) | C30—Zr—C24—C23 | 79.43 (14) |
C23—Zr—C2—C3 | −115.32 (13) | Cl2—Zr—C24—C23 | 122.44 (12) |
C30—Zr—C2—C3 | 176.27 (11) | C29—Zr—C24—C23 | 115.71 (19) |
Cl2—Zr—C2—C3 | 108.69 (12) | C3—Zr—C24—C23 | −83.63 (17) |
C24—Zr—C2—C3 | −101.77 (18) | C2—Zr—C24—C23 | −21.2 (2) |
C29—Zr—C2—C3 | 168.53 (17) | C4—Zr—C24—C23 | −80.68 (13) |
C4—Zr—C2—C3 | −29.08 (11) | N1—Zr—C24—C25 | 132.76 (18) |
N1—Zr—C2—C1 | 99.7 (3) | N2—Zr—C24—C25 | 55.62 (19) |
N2—Zr—C2—C1 | −165.4 (2) | C22—Zr—C24—C25 | 166.7 (2) |
C22—Zr—C2—C1 | 92.5 (2) | Cl1—Zr—C24—C25 | −30.10 (18) |
Cl1—Zr—C2—C1 | −86.5 (2) | C23—Zr—C24—C25 | 128.4 (3) |
C23—Zr—C2—C1 | 127.3 (2) | C30—Zr—C24—C25 | −152.2 (2) |
C30—Zr—C2—C1 | 58.8 (3) | Cl2—Zr—C24—C25 | −109.17 (18) |
Cl2—Zr—C2—C1 | −8.7 (2) | C29—Zr—C24—C25 | −115.9 (2) |
C24—Zr—C2—C1 | 140.8 (2) | C3—Zr—C24—C25 | 44.8 (2) |
C29—Zr—C2—C1 | 51.1 (3) | C2—Zr—C24—C25 | 107.2 (2) |
C3—Zr—C2—C1 | −117.4 (3) | C4—Zr—C24—C25 | 47.7 (2) |
C4—Zr—C2—C1 | −146.5 (3) | N1—Zr—C24—C29 | −111.33 (14) |
N1—C2—C3—C4 | 34.3 (3) | N2—Zr—C24—C29 | 171.53 (13) |
C1—C2—C3—C4 | −150.6 (2) | C22—Zr—C24—C29 | −77.41 (14) |
Zr—C2—C3—C4 | 69.6 (2) | Cl1—Zr—C24—C29 | 85.81 (13) |
N1—C2—C3—Zr | −35.28 (17) | C23—Zr—C24—C29 | −115.71 (19) |
C1—C2—C3—Zr | 139.88 (19) | C30—Zr—C24—C29 | −36.28 (13) |
N1—Zr—C3—C2 | 21.42 (11) | Cl2—Zr—C24—C29 | 6.74 (15) |
N2—Zr—C3—C2 | 121.06 (14) | C3—Zr—C24—C29 | 160.66 (14) |
C22—Zr—C3—C2 | 42.71 (16) | C2—Zr—C24—C29 | −136.88 (17) |
Cl1—Zr—C3—C2 | −151.79 (12) | C4—Zr—C24—C29 | 163.61 (12) |
C23—Zr—C3—C2 | 88.54 (14) | C23—C24—C25—C26 | −176.7 (2) |
C30—Zr—C3—C2 | −7.9 (2) | C29—C24—C25—C26 | 0.9 (3) |
Cl2—Zr—C3—C2 | −67.48 (12) | Zr—C24—C25—C26 | 91.4 (2) |
C24—Zr—C3—C2 | 134.01 (13) | C24—C25—C26—C27 | −1.1 (3) |
C29—Zr—C3—C2 | −157.5 (3) | C25—C26—C27—C28 | 0.1 (4) |
C4—Zr—C3—C2 | 128.76 (19) | C26—C27—C28—C29 | 1.0 (4) |
N1—Zr—C3—C4 | −107.34 (13) | C27—C28—C29—C30 | 176.8 (2) |
N2—Zr—C3—C4 | −7.71 (11) | C27—C28—C29—C24 | −1.2 (3) |
C22—Zr—C3—C4 | −86.05 (15) | C27—C28—C29—Zr | −90.5 (2) |
Cl1—Zr—C3—C4 | 79.45 (12) | C23—C24—C29—C30 | −0.1 (2) |
C23—Zr—C3—C4 | −40.22 (16) | C25—C24—C29—C30 | −178.21 (18) |
C30—Zr—C3—C4 | −136.62 (17) | Zr—C24—C29—C30 | 61.92 (14) |
Cl2—Zr—C3—C4 | 163.76 (12) | C23—C24—C29—C28 | 178.34 (19) |
C24—Zr—C3—C4 | 5.24 (19) | C25—C24—C29—C28 | 0.2 (3) |
C29—Zr—C3—C4 | 73.7 (4) | Zr—C24—C29—C28 | −119.6 (2) |
C2—Zr—C3—C4 | −128.76 (19) | C23—C24—C29—Zr | −62.03 (13) |
C14—N2—C4—C3 | 176.21 (19) | C25—C24—C29—Zr | 119.86 (18) |
Zr—N2—C4—C3 | −15.0 (2) | N1—Zr—C29—C30 | −19.93 (16) |
C14—N2—C4—C5 | −1.7 (3) | N2—Zr—C29—C30 | −126.30 (12) |
Zr—N2—C4—C5 | 167.14 (19) | C22—Zr—C29—C30 | −38.26 (12) |
C14—N2—C4—Zr | −168.8 (2) | Cl1—Zr—C29—C30 | 153.08 (12) |
C2—C3—C4—N2 | −52.7 (3) | C23—Zr—C29—C30 | −79.46 (14) |
Zr—C3—C4—N2 | 12.98 (18) | Cl2—Zr—C29—C30 | 69.15 (12) |
C2—C3—C4—C5 | 125.4 (2) | C24—Zr—C29—C30 | −116.46 (19) |
Zr—C3—C4—C5 | −168.95 (17) | C3—Zr—C29—C30 | 158.9 (3) |
C2—C3—C4—Zr | −65.6 (2) | C2—Zr—C29—C30 | 11.7 (2) |
N1—Zr—C4—N2 | −106.47 (13) | C4—Zr—C29—C30 | −142.85 (12) |
C22—Zr—C4—N2 | −44.47 (16) | N1—Zr—C29—C28 | −148.19 (17) |
Cl1—Zr—C4—N2 | 97.14 (12) | N2—Zr—C29—C28 | 105.43 (18) |
C23—Zr—C4—N2 | −15.93 (14) | C22—Zr—C29—C28 | −166.5 (2) |
C30—Zr—C4—N2 | −33.7 (3) | Cl1—Zr—C29—C28 | 24.82 (18) |
Cl2—Zr—C4—N2 | 175.99 (11) | C23—Zr—C29—C28 | 152.3 (2) |
C24—Zr—C4—N2 | 17.65 (15) | C30—Zr—C29—C28 | −128.3 (2) |
C29—Zr—C4—N2 | 32.68 (18) | Cl2—Zr—C29—C28 | −59.11 (19) |
C3—Zr—C4—N2 | −165.6 (2) | C24—Zr—C29—C28 | 115.3 (2) |
C2—Zr—C4—N2 | −136.36 (15) | C3—Zr—C29—C28 | 30.6 (4) |
N1—Zr—C4—C3 | 59.15 (12) | C2—Zr—C29—C28 | −116.6 (2) |
N2—Zr—C4—C3 | 165.6 (2) | C4—Zr—C29—C28 | 88.9 (2) |
C22—Zr—C4—C3 | 121.16 (13) | N1—Zr—C29—C24 | 96.53 (14) |
Cl1—Zr—C4—C3 | −97.23 (12) | N2—Zr—C29—C24 | −9.85 (15) |
C23—Zr—C4—C3 | 149.70 (13) | C22—Zr—C29—C24 | 78.19 (14) |
C30—Zr—C4—C3 | 131.9 (2) | Cl1—Zr—C29—C24 | −90.46 (13) |
Cl2—Zr—C4—C3 | −18.38 (13) | C23—Zr—C29—C24 | 36.99 (12) |
C24—Zr—C4—C3 | −176.73 (12) | C30—Zr—C29—C24 | 116.46 (19) |
C29—Zr—C4—C3 | −161.69 (13) | Cl2—Zr—C29—C24 | −174.39 (12) |
C2—Zr—C4—C3 | 29.27 (12) | C3—Zr—C29—C24 | −84.7 (4) |
N1—Zr—C4—C5 | 168.7 (8) | C2—Zr—C29—C24 | 128.14 (18) |
N2—Zr—C4—C5 | −84.8 (8) | C4—Zr—C29—C24 | −26.39 (19) |
C22—Zr—C4—C5 | −129.3 (8) | C23—C22—C30—C29 | −4.4 (2) |
Cl1—Zr—C4—C5 | 12.3 (8) | Zr—C22—C30—C29 | −70.56 (15) |
C23—Zr—C4—C5 | −100.8 (8) | C23—C22—C30—Zr | 66.21 (14) |
C30—Zr—C4—C5 | −118.5 (8) | C28—C29—C30—C22 | −175.5 (2) |
Cl2—Zr—C4—C5 | 91.1 (8) | C24—C29—C30—C22 | 2.7 (2) |
C24—Zr—C4—C5 | −67.2 (8) | Zr—C29—C30—C22 | 66.98 (14) |
C29—Zr—C4—C5 | −52.2 (8) | C28—C29—C30—Zr | 117.6 (2) |
C3—Zr—C4—C5 | 109.5 (8) | C24—C29—C30—Zr | −64.27 (14) |
C2—Zr—C4—C5 | 138.8 (8) | N1—Zr—C30—C22 | 51.54 (14) |
C2—N1—C6—C11 | −113.5 (2) | N2—Zr—C30—C22 | −36.65 (17) |
Zr—N1—C6—C11 | 44.9 (3) | Cl1—Zr—C30—C22 | −142.44 (12) |
C2—N1—C6—C7 | 68.5 (2) | C23—Zr—C30—C22 | −37.03 (13) |
Zr—N1—C6—C7 | −133.1 (2) | Cl2—Zr—C30—C22 | 137.64 (13) |
C11—C6—C7—C8 | −6.2 (3) | C24—Zr—C30—C22 | −77.53 (14) |
N1—C6—C7—C8 | 171.90 (19) | C29—Zr—C30—C22 | −113.58 (18) |
C11—C6—C7—C12 | 170.5 (2) | C3—Zr—C30—C22 | 76.7 (2) |
N1—C6—C7—C12 | −11.4 (3) | C2—Zr—C30—C22 | 71.68 (14) |
C6—C7—C8—C9 | 3.0 (3) | C4—Zr—C30—C22 | −15.9 (3) |
C12—C7—C8—C9 | −173.8 (2) | N1—Zr—C30—C29 | 165.12 (12) |
C7—C8—C9—C10 | 1.6 (4) | N2—Zr—C30—C29 | 76.93 (15) |
C8—C9—C10—C11 | −3.1 (4) | C22—Zr—C30—C29 | 113.58 (18) |
C9—C10—C11—C6 | −0.1 (3) | Cl1—Zr—C30—C29 | −28.85 (13) |
C9—C10—C11—C13 | 176.9 (2) | C23—Zr—C30—C29 | 76.56 (13) |
C7—C6—C11—C10 | 4.7 (3) | Cl2—Zr—C30—C29 | −108.78 (12) |
N1—C6—C11—C10 | −173.3 (2) | C24—Zr—C30—C29 | 36.06 (11) |
C7—C6—C11—C13 | −172.1 (2) | C3—Zr—C30—C29 | −169.71 (16) |
N1—C6—C11—C13 | 9.9 (3) | C2—Zr—C30—C29 | −174.74 (11) |
C4—N2—C14—C19 | 71.3 (3) | C4—Zr—C30—C29 | 97.6 (2) |
Zr—N2—C14—C19 | −92.4 (3) | C36—C31—C32—C33 | −3.4 (8) |
C4—N2—C14—C15 | −109.9 (2) | C37—C31—C32—C33 | −176.3 (9) |
Zr—N2—C14—C15 | 86.5 (3) | C31—C32—C33—C34 | 3.9 (14) |
C19—C14—C15—C16 | 2.4 (3) | C32—C33—C34—C35 | −4 (2) |
N2—C14—C15—C16 | −176.45 (19) | C33—C34—C35—C36 | 3 (2) |
C19—C14—C15—C20 | −172.6 (2) | C34—C35—C36—C31 | −2.9 (14) |
N2—C14—C15—C20 | 8.5 (3) | C32—C31—C36—C35 | 2.9 (9) |
C14—C15—C16—C17 | −1.6 (3) | C37—C31—C36—C35 | 176.0 (9) |
C20—C15—C16—C17 | 173.7 (2) |
Experimental details
Crystal data | |
Chemical formula | [Zr(Cl)2(C21H25N2)(C9H7)]·0.5C7H8 |
Mr | 628.77 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 25.6719 (7), 12.2509 (3), 22.6278 (6) |
β (°) | 122.701 (1) |
V (Å3) | 5988.6 (3) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 4.83 |
Crystal size (mm) | 0.27 × 0.21 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART 6000 |
Absorption correction | Multi-scan (SADABS; Sheldrick,1996) |
Tmin, Tmax | 0.322, 0.419 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36248, 5814, 5182 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.086, 1.00 |
No. of reflections | 5814 |
No. of parameters | 380 |
No. of restraints | 42 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.99 |
Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), UdMX (local program).
The title compound was synthesized by ligand metathesis starting from [bis(2,6-dimethylphenyl)nacnac]ZrCl3(THF) ("nacnac" = pentane-2,4-diiminato) and indenyl lithium. Layering of a toluene solution with hexane yielded crystals in sufficient quality for X-ray analysis.
Coordination of the nacnac ligand to group 4 metals differs strongly depending on the compound composition, the nature of the nacnac ligand and the metal center. An in-plane η2-coordination is often observed in octahedral coordinated compounds (Kakaliou et al., 1999; Qian et al.; 1999; Jin & Novak, 2000; Franceschini et al., 2003; Hamaki et al., 2006). With sterically less encumbered nacnac ligands, such as N,N'-diphenyl nacnac, and in particular in the presence of a second, η5-coordinated ligand such as cyclopentadienyl or indenyl, a cyclopentadienyl-like η5-coordination has been observed (Rahim et al., 1998; Vollmerhaus et al., 2000). One example of such is (Ind)(N,N'-diphenyl-nacnac)ZrCl2, which differs from the title compound (I) only by the lack of the 2,6-methyl substituents on the N-bonded phenyl rings (Rahim et al., 1998).
In contrast to these, the nacnac ligand adopts in (I), an intermediate, distorted coordination mode. The coordination of N1 and the carbon atoms C2 and C3 can be described as an η3-coordinated enamide, as evidenced by Zr—C distances of 2.617 (2) and 2.616 (2) Å, respectively, and an angle 〈 (C1,C2,Zr) of 140.7 (2)°. The Zr—C4 distance of 2.825 (2) Å, however, is significantly elongated in comparison to C2 and C3 and the methyl substituent at C4 is orientated away from the metal center with a bond angle 〈 (C5,C4,Zr) of 169.5 (2)°, indicating that the N lone pair, but not the C═N-bond is coordinated to the Zr center. (While we cannot completely exclude a π-coordination of C4 to the metal, the elongated Zr—C4 distance makes this improbable.) The coordination of the nacnac ligand can be thus broken down into two parts, an η3-enaminato coordination of C2, C3 and N1 and an η1-imine coordination of C4 and N2.
The planar coordination of the enaminato-moiety and the in-plane coordination of the imine-moiety results in a folding of the ligand backbone, which reduces its electron delocalization. The least-square planes through N1, C1–C3 and N2, C3–C5 display an angle of 41°. Bond distances observed in the ligand backbone agree with a slight separation of the π-system into an enaminato- and an imine-moiety. The proposed imine bond N2═C4 is shorter than the so-assigned enamine bond N1═C2 (1.303 (3) and 1.352 (3) Å, respectively). The C2—C3 distance of 1.394 (3) Å is comparable to the N—C distances, while the C3—C4 distance is significantly elongated to 1.454 (3) Å and can be assigned a higher single-bond character.
The coordination of the nacnac ligand observed here differs from the earlier described η2 or η5-coordination (see above) and from those observed, for example, in scandium complexes, where a placement of the Sc center outside of the ligand plane was ascribed to steric reasons without any significant coordination of the carbon atoms to the metal center (Lee et al., 1999). A comparable coordination, however, was observed for the nacnac ligand in the five-coordinated complexes reported by Basuli et al. (2004) (CSD-codes: FAPBUU, FAPCAP, FAPCEF & FABCIJ). Their coordination was described simply as "sandwich-like". Not surprisingly, the analogous compound in which indenyl is replaced by cyclopentadienyl is nearly isostructural (Verguet et al., 2007).
The indenyl ligand displays only a very slight deviation from ideal η5-coordination (ΔM–C = 0.11 Å and Ω = 4°˛ Faller et al., 1985).