Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704322X/om2160sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704322X/om2160Isup2.hkl |
CCDC reference: 667224
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.004 Å
- Disorder in main residue
- R factor = 0.031
- wR factor = 0.088
- Data-to-parameter ratio = 16.9
checkCIF/PLATON results
No syntax errors found Datablock: I
Alert level B PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.95 PLAT201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) ....... 1
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.500 0.640 Tmin and Tmax expected: 0.417 0.641 RR = 1.200 Please check that your absorption correction is appropriate. CELLV02_ALERT_1_C The supplied cell volume s.u. differs from that calculated from the cell parameter s.u.'s by > 2 Calculated cell volume su = 18.57 Cell volume su given = 16.00 PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.20 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C24 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C25A PLAT301_ALERT_3_C Main Residue Disorder ......................... 2.00 Perc. PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of . 36.00 A 3
Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 72.08 From the CIF: _reflns_number_total 9929 From the CIF: _diffrn_reflns_limit_ max hkl 16. 16. 19. From the CIF: _diffrn_reflns_limit_ min hkl -16. -14. -20. TEST1: Expected hkl limits for theta max Calculated maximum hkl 16. 18. 20. Calculated minimum hkl -16. -18. -20. PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 11
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For other zirconium complexes containing an κ2–coordinated nacnac ligand, see: Rahim et al. (1998); Kakaliou et al. (1999); Qian et al. (1999); Jin & Novak (2000); Franceschini et al. (2003); Hamaki et al. (2006). For zirconium complexes containing nacnac ligands in other coordination modes, see: Rahim et al. (1998); Vollmerhaus et al. (2000); Basuli et al. (2004); Verguet, Fortuné et al. (2007); Verguet, Oguadinma & Schaper (2007).
For related literature, see: Spek (2000).
To a solution of 7.8 g (25 mmol) nacnacH in THF, 11.5 ml n-BuLi in hexane (2.7 M, 27.5 mmol) were added at -78°C. The solution was allowed to warm to room temperature over night. Evaporation of the solvent yield a red-brown residue, which was washed two times with hexane to give 7.3 g nacnacLi(THF) (76%) as a yellow powder.
RMN 1H (300 MHz, C6D6): 7.08–6.92 (m, 6H, CH [C6H3Me2]), 4.97 (s, 1H, CH [nacnac]), 2.93 (br s, 4H, THF), 2.21 (s, 12H, CH3 [C6H3Me2]), 1.81 (s, 6H, CH3 [nacnac]), 0.92 (br s, 4H, THF).
A solution of 2.94 g ZrCl4(THF)2 (7.8 mmol) in 20 ml toluene were added to a solution of 3.0 g nacnacLi(THF) (7.8 mmol) in 20 ml toluene. After stirring at room temperature for two hours the brown suspension is filtered and the precipitate washed with 4 ml toluene. The filtrates were combined and their volume reduced to 15 ml. 15 ml hexane were layered on top of the solution. After several days 4.0 g (89%) of the title compound were isolated as yellow-brown microcrystals.
RMN 1H (300 MHz, C6D6): δ 6.94 (m, 6H, CH [C6H3Me2]), 5.55 (s, 1H, CH [nacnac]), 3.80 (br s, 4H, THF), 2.44 (s, 12H, CH3 [C6H3Me2]), 1.45 (s, 6H, CH3 [nacnac]), 1.01 (br s, 4H, THF).
All non-H atoms were refined by full-matrix least-squares with anisotropic displacement parameters. The THF molecule in one of the two independent molecules in the asymmetric unit was found to be disordered. The disorder was resolved and refined isotropic with appropriate restraints. Relative occupancies refined to 0.57:0.43. Although the neighbouring atoms C24 and O1 show slightly enlarged thermal ellipsoids, no disorder was refined for those atoms. The atoms C25A and C25B were refined with isotropic thermal parameters. 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. A final verification of possible voids was performed using the VOID routine of the PLATON program (Spek, 2000).
The title compound was first synthesized by Jin & Novak (2000), although no experimental or spectroscopic data was provided. Our synthesis followed the same procedure described there and for the synthesis of other (nacnac)ZrCl3(THF) complexes (Kakaliou et al., 1999), i.e. reaction of the deprotonated nacnac ligand (nacnac = pentane-2,4-diiminato) with ZrCl4(THF)2.
Two identical, independent molecules are present in the asymmetric unit. Only the geometry of one of those is described in detail. Apart from the missing disorder of the THF molecule, no significant differences were observed in the second molecule.
The zirconium center has a slightly distorted octahedral coordination geometry with L–Zr–L bond angles ranging from 83° to 99°. The coordination of the nanac ligand is best described as an in-plane η2-coordination via the nitrogen lone pairs. The ligand backbone is nearly planar, with a slight bending of the methyl groups and the central carbon atom C3 out of the ligand plane, probalby due to steric interaction with each other. Bond distances in the ligand backbone are in agreement with a strong electron delocalization. The zirconium center is slightly bend out of the ligand mean plane (〈 (Zr1,N1,N2),(N1,N2,C2–C4)=41°), a common feature for η2-coordinated nacnac ligands in penta-coordinated or octahedral complexes (Rahim et al., 1998; Qian et al., 1999; Kakaliou et al., 1999; Franceschini et al., 2003; Hamaki et al., 2006). Long Zr—C distances for C2–C4 (> 3.1 Å) indicate, however, that this is not due to coordination of the ligand π-system to the metal center, but rather to the steric strain introduced by the in-plane coordination of the metal center. This is further supported by a N–Zr–N angle smaller than 90° (〈(N1–Zr1–N2)=83.11 (7)°) and slightly widened C3–C–N angles (〈(N1–C2–C3)=123.5 (2)°, 〈(N2–C4–C3)=123.6 (2)°).
One THF molecule, coordinated trans to N2, completes the octahedral coordination of the metal center. Although penta-coordinated (nacnac)ZrCl3 complexes can be isolated in the absence of THF, coordination of THF to a (nacnac)ZrCl3 fragment has been reported before (Kakaliou et al., 1999; Jin & Novak, 2000). In all cases, THF preferred a coordination trans to nitrogen. As also observed in these complexes, the Zr—N2 distance in the title compound is slightly longer than Zr—N1 (2.218 (2) and 2.176 (2) Å, respectively), in agreement with a stronger trans effect of chlorine compared to oxygen.
Of the two possible coordination modes of the nacnac ligand (η2–in plane or ηx–side on), the η2-coordination seems to be preferred when an octahedral coordination of the metal center can be achieved (Franceschini et al., 2003 (BEDLUS, BEDMAZ), Kakaliou et al., 1999 (LIRDOF), Rahim et al., 1998 (SEQXER, SEQXIV), Hamaki et al., 2006 (DEGWIW), Jin & Novak, 2000). For penta-coordinated zirconium complexes both, η2–coordination (LIRCIY, LIRCOE, LIRDUL: Kakaliou et al., 1999; MAPJIW, MAPJUI: Qian et al., 1999) and higher coordination modes (FAPBUU, FAPCEF, FAPCAB, FAPCIJ: Basuli et al., 2004) have been observed. When a second, planar coordinated ligand such as cyclopentadienyl or indenyl is present, the nacnac ligand always prefers higher coordination modes (Vollmerhaus et al., 2000 (QIPGUR); Rahim et al., 1998 (SEQXOB); Verguet, Fortuné et al., 2007; Verguet, Oguadinma & Schaper, 2007). (Codes refer to entries in the Cambridge Structural Database). It should be noted that a "higher coordination mode" does not necessarily correspond to a cyclopentadienyl–like η5–coordination (Verguet, Fortuné et al., 2007).
For other zirconium complexes containing an κ2–coordinated nacnac ligand, see: Rahim et al. (1998); Kakaliou et al. (1999); Qian et al. (1999); Jin & Novak (2000); Franceschini et al. (2003); Hamaki et al. (2006). For zirconium complexes containing nacnac ligands in other coordination modes, see: Rahim et al. (1998); Vollmerhaus et al. (2000); Basuli et al. (2004); Verguet, Fortuné et al. (2007); Verguet, Oguadinma & Schaper (2007).
For related literature, see: Spek (2000).
Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (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 (Marris, 2004).
[Zr(C21H25N2)Cl3(C4H8O)] | Z = 4 |
Mr = 575.10 | F(000) = 1184 |
Triclinic, P1 | Dx = 1.446 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 13.6082 (5) Å | Cell parameters from 16709 reflections |
b = 14.5970 (5) Å | θ = 4.1–71.5° |
c = 16.3293 (6) Å | µ = 6.35 mm−1 |
α = 114.948 (2)° | T = 150 K |
β = 98.898 (2)° | Plate, yellow |
γ = 107.951 (2)° | 0.16 × 0.16 × 0.07 mm |
V = 2641.04 (16) Å3 |
Bruker Smart 6000 diffractometer | 9929 independent reflections |
Radiation source: Rotating Anode | 9305 reflections with I > 2σ(I) |
Montel 200 optics monochromator | Rint = 0.036 |
Detector resolution: 5.5 pixels mm-1 | θmax = 72.1°, θmin = 3.2° |
ω scans | h = −16→16 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→16 |
Tmin = 0.50, Tmax = 0.64 | l = −20→19 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0601P)2 + 1.3844P] where P = (Fo2 + 2Fc2)/3 |
9929 reflections | (Δ/σ)max = 0.001 |
589 parameters | Δρmax = 0.61 e Å−3 |
11 restraints | Δρmin = −1.25 e Å−3 |
[Zr(C21H25N2)Cl3(C4H8O)] | γ = 107.951 (2)° |
Mr = 575.10 | V = 2641.04 (16) Å3 |
Triclinic, P1 | Z = 4 |
a = 13.6082 (5) Å | Cu Kα radiation |
b = 14.5970 (5) Å | µ = 6.35 mm−1 |
c = 16.3293 (6) Å | T = 150 K |
α = 114.948 (2)° | 0.16 × 0.16 × 0.07 mm |
β = 98.898 (2)° |
Bruker Smart 6000 diffractometer | 9929 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 9305 reflections with I > 2σ(I) |
Tmin = 0.50, Tmax = 0.64 | Rint = 0.036 |
36248 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 11 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.61 e Å−3 |
9929 reflections | Δρmin = −1.25 e Å−3 |
589 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. Comments on remaining CHECKCIF errors: All geometrically accessible data was collected. A data completeness of 0.96 was due to geometrical constraints of the instrument (particularly severe for triclinic space groups) and could not be improved. Errors in the Tmax/Tmin ratio are probably due to inaccurate determination of crystal dimensions. Supplied e.s.d. values for the cell parameters are correct. Differences between calculated and supplied values arise most probably from the rounding of cell parameters in the CIF file. No additional electron density was found in solvent accessible voids. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | 0.31188 (13) | 0.27645 (15) | 0.82802 (11) | 0.0356 (4) | |
O2 | 0.83397 (13) | 0.29499 (14) | 0.37605 (12) | 0.0300 (3) | |
Zr1 | 0.168238 (14) | 0.257712 (14) | 0.883656 (11) | 0.02274 (6) | |
Zr2 | 0.690471 (13) | 0.266619 (14) | 0.429264 (11) | 0.02207 (6) | |
Cl1 | 0.81986 (5) | 0.40340 (5) | 0.58818 (4) | 0.04192 (15) | |
Cl2 | 0.72529 (4) | 0.11247 (5) | 0.42947 (4) | 0.03114 (12) | |
Cl3 | 0.67650 (4) | 0.41924 (4) | 0.41025 (4) | 0.02919 (11) | |
Cl4 | 0.09555 (5) | 0.06236 (5) | 0.76288 (4) | 0.03778 (13) | |
Cl5 | 0.27106 (4) | 0.22364 (5) | 0.99607 (4) | 0.03309 (12) | |
Cl6 | 0.26375 (4) | 0.45918 (4) | 0.99344 (4) | 0.03234 (12) | |
N1 | 0.02755 (15) | 0.25160 (15) | 0.93244 (13) | 0.0255 (4) | |
N2 | 0.08358 (14) | 0.29748 (15) | 0.78438 (12) | 0.0246 (4) | |
N3 | 0.56673 (14) | 0.14635 (14) | 0.28439 (12) | 0.0234 (3) | |
N4 | 0.55027 (14) | 0.22025 (14) | 0.47524 (12) | 0.0232 (3) | |
C1 | −0.1057 (2) | 0.3230 (2) | 0.9896 (2) | 0.0385 (6) | |
H1A | −0.0695 | 0.3429 | 1.0552 | 0.058* | |
H1B | −0.1689 | 0.2510 | 0.9584 | 0.058* | |
H1C | −0.1302 | 0.3799 | 0.9910 | 0.058* | |
C2 | −0.02606 (18) | 0.31564 (18) | 0.93455 (16) | 0.0286 (4) | |
C3 | −0.01605 (19) | 0.37371 (19) | 0.88523 (17) | 0.0315 (5) | |
H3A | −0.0418 | 0.4305 | 0.9048 | 0.038* | |
C4 | 0.02727 (19) | 0.35953 (19) | 0.80996 (16) | 0.0306 (5) | |
C5 | 0.0018 (3) | 0.4131 (3) | 0.7534 (2) | 0.0503 (7) | |
H5A | 0.0702 | 0.4645 | 0.7561 | 0.075* | |
H5B | −0.0408 | 0.4542 | 0.7806 | 0.075* | |
H5C | −0.0407 | 0.3557 | 0.6867 | 0.075* | |
C6 | −0.00780 (18) | 0.18171 (19) | 0.97429 (16) | 0.0276 (4) | |
C7 | 0.04394 (19) | 0.22239 (19) | 1.07150 (16) | 0.0304 (5) | |
C8 | 0.0062 (2) | 0.1533 (2) | 1.10877 (18) | 0.0353 (5) | |
H8A | 0.0417 | 0.1778 | 1.1738 | 0.042* | |
C9 | −0.0812 (2) | 0.0505 (2) | 1.05422 (19) | 0.0377 (5) | |
H9A | −0.1059 | 0.0056 | 1.0817 | 0.045* | |
C10 | −0.1324 (2) | 0.0136 (2) | 0.95944 (19) | 0.0359 (5) | |
H10A | −0.1931 | −0.0568 | 0.9221 | 0.043* | |
C11 | −0.09697 (19) | 0.07760 (19) | 0.91753 (17) | 0.0310 (5) | |
C12 | 0.1335 (2) | 0.3371 (2) | 1.13648 (17) | 0.0391 (6) | |
H12A | 0.2005 | 0.3316 | 1.1615 | 0.059* | |
H12B | 0.1113 | 0.3780 | 1.1898 | 0.059* | |
H12C | 0.1471 | 0.3764 | 1.1005 | 0.059* | |
C13 | −0.1544 (2) | 0.0350 (2) | 0.81371 (18) | 0.0393 (6) | |
H13A | −0.2242 | −0.0288 | 0.7907 | 0.059* | |
H13B | −0.1083 | 0.0122 | 0.7759 | 0.059* | |
H13C | −0.1680 | 0.0941 | 0.8070 | 0.059* | |
C14 | 0.09836 (18) | 0.26843 (18) | 0.69140 (15) | 0.0267 (4) | |
C15 | 0.01671 (18) | 0.17145 (19) | 0.61125 (16) | 0.0282 (4) | |
C16 | 0.0319 (2) | 0.1401 (2) | 0.52222 (16) | 0.0330 (5) | |
H16A | −0.0212 | 0.0734 | 0.4674 | 0.040* | |
C17 | 0.1227 (2) | 0.2045 (2) | 0.51282 (17) | 0.0380 (5) | |
H17A | 0.1324 | 0.1814 | 0.4520 | 0.046* | |
C18 | 0.1996 (2) | 0.3029 (2) | 0.59173 (18) | 0.0384 (5) | |
H18A | 0.2609 | 0.3477 | 0.5841 | 0.046* | |
C19 | 0.18867 (19) | 0.3376 (2) | 0.68276 (16) | 0.0316 (5) | |
C20 | −0.08737 (18) | 0.1047 (2) | 0.61822 (16) | 0.0332 (5) | |
H20A | −0.0697 | 0.0846 | 0.6670 | 0.050* | |
H20B | −0.1305 | 0.0370 | 0.5562 | 0.050* | |
H20C | −0.1298 | 0.1491 | 0.6359 | 0.050* | |
C21 | 0.2722 (2) | 0.4483 (2) | 0.76503 (18) | 0.0409 (6) | |
H21A | 0.2528 | 0.4625 | 0.8232 | 0.061* | |
H21B | 0.2736 | 0.5072 | 0.7505 | 0.061* | |
H21C | 0.3447 | 0.4472 | 0.7749 | 0.061* | |
C22 | 0.42639 (17) | 0.34392 (19) | 0.89300 (16) | 0.0337 (5) | |
H22A | 0.4299 | 0.3727 | 0.9607 | 0.040* | |
H22B | 0.4622 | 0.4074 | 0.8838 | 0.040* | |
C23 | 0.4789 (2) | 0.2648 (2) | 0.8651 (2) | 0.0418 (6) | |
H23A | 0.4721 | 0.2255 | 0.9022 | 0.050* | |
H23B | 0.5574 | 0.3041 | 0.8759 | 0.050* | |
C24 | 0.4168 (2) | 0.1845 (3) | 0.7601 (2) | 0.0582 (8) | |
H24A | 0.4654 | 0.1901 | 0.7215 | 0.070* | 0.579 (15) |
H24B | 0.3858 | 0.1072 | 0.7476 | 0.070* | 0.579 (15) |
H24C | 0.4544 | 0.2099 | 0.7214 | 0.070* | 0.421 (15) |
H24D | 0.4137 | 0.1099 | 0.7435 | 0.070* | 0.421 (15) |
C25A | 0.3286 (4) | 0.2173 (5) | 0.7364 (2) | 0.0260 (13)* | 0.579 (15) |
H25A | 0.3507 | 0.2666 | 0.7094 | 0.031* | 0.579 (15) |
H25B | 0.2608 | 0.1511 | 0.6896 | 0.031* | 0.579 (15) |
C25B | 0.3054 (4) | 0.1789 (7) | 0.7393 (4) | 0.040 (2)* | 0.421 (15) |
H25C | 0.2514 | 0.1081 | 0.7286 | 0.048* | 0.421 (15) |
H25D | 0.2849 | 0.1861 | 0.6822 | 0.048* | 0.421 (15) |
C26 | 0.3907 (2) | 0.0875 (2) | 0.48075 (18) | 0.0361 (5) | |
H26A | 0.4328 | 0.0964 | 0.5401 | 0.054* | |
H26B | 0.3376 | 0.0100 | 0.4393 | 0.054* | |
H26C | 0.3520 | 0.1359 | 0.4958 | 0.054* | |
C27 | 0.46727 (17) | 0.11865 (18) | 0.43008 (15) | 0.0257 (4) | |
C28 | 0.44382 (18) | 0.03930 (17) | 0.33490 (15) | 0.0274 (4) | |
H28A | 0.3950 | −0.0344 | 0.3151 | 0.033* | |
C29 | 0.48297 (17) | 0.05433 (17) | 0.26492 (15) | 0.0258 (4) | |
C30 | 0.4222 (2) | −0.03666 (19) | 0.16210 (16) | 0.0339 (5) | |
H30A | 0.4749 | −0.0524 | 0.1298 | 0.051* | |
H30B | 0.3777 | −0.0126 | 0.1296 | 0.051* | |
H30C | 0.3747 | −0.1040 | 0.1601 | 0.051* | |
C31 | 0.55240 (18) | 0.30167 (17) | 0.56685 (15) | 0.0255 (4) | |
C32 | 0.49824 (18) | 0.36925 (18) | 0.56688 (16) | 0.0277 (4) | |
C33 | 0.5087 (2) | 0.45453 (19) | 0.65476 (17) | 0.0334 (5) | |
H33A | 0.4732 | 0.5016 | 0.6562 | 0.040* | |
C34 | 0.5702 (2) | 0.47140 (19) | 0.73990 (17) | 0.0370 (5) | |
H34A | 0.5786 | 0.5312 | 0.7991 | 0.044* | |
C35 | 0.6193 (2) | 0.4010 (2) | 0.73850 (16) | 0.0354 (5) | |
H35A | 0.6598 | 0.4120 | 0.7973 | 0.043* | |
C36 | 0.61043 (19) | 0.31394 (19) | 0.65228 (16) | 0.0300 (5) | |
C37 | 0.6616 (2) | 0.2368 (2) | 0.65460 (17) | 0.0359 (5) | |
H37A | 0.7303 | 0.2789 | 0.7085 | 0.054* | |
H37B | 0.6766 | 0.2026 | 0.5947 | 0.054* | |
H37C | 0.6113 | 0.1786 | 0.6621 | 0.054* | |
C38 | 0.42865 (19) | 0.3507 (2) | 0.47521 (16) | 0.0324 (5) | |
H38A | 0.3917 | 0.4007 | 0.4902 | 0.049* | |
H38B | 0.3739 | 0.2734 | 0.4377 | 0.049* | |
H38C | 0.4751 | 0.3658 | 0.4381 | 0.049* | |
C39 | 0.58412 (18) | 0.16308 (17) | 0.20537 (14) | 0.0258 (4) | |
C40 | 0.65758 (19) | 0.13058 (19) | 0.16161 (15) | 0.0298 (5) | |
C41 | 0.6829 (2) | 0.1631 (2) | 0.09567 (16) | 0.0359 (5) | |
H41A | 0.7336 | 0.1432 | 0.0662 | 0.043* | |
C42 | 0.6353 (2) | 0.2239 (2) | 0.07270 (16) | 0.0369 (5) | |
H42A | 0.6564 | 0.2490 | 0.0304 | 0.044* | |
C43 | 0.5570 (2) | 0.2483 (2) | 0.11125 (16) | 0.0340 (5) | |
H43A | 0.5217 | 0.2867 | 0.0924 | 0.041* | |
C44 | 0.52891 (18) | 0.21755 (18) | 0.17737 (15) | 0.0286 (4) | |
C45 | 0.44014 (19) | 0.2404 (2) | 0.21513 (16) | 0.0326 (5) | |
H45A | 0.4094 | 0.2756 | 0.1850 | 0.049* | |
H45B | 0.4707 | 0.2902 | 0.2846 | 0.049* | |
H45C | 0.3823 | 0.1704 | 0.2004 | 0.049* | |
C46 | 0.7061 (2) | 0.0582 (2) | 0.17975 (18) | 0.0365 (5) | |
H46A | 0.7001 | 0.0611 | 0.2397 | 0.055* | |
H46B | 0.7834 | 0.0852 | 0.1844 | 0.055* | |
H46C | 0.6664 | −0.0186 | 0.1269 | 0.055* | |
C47 | 0.9279 (2) | 0.2706 (3) | 0.4043 (2) | 0.0419 (6) | |
H47A | 0.9063 | 0.1894 | 0.3727 | 0.050* | |
H47B | 0.9547 | 0.3021 | 0.4745 | 0.050* | |
C48 | 1.0156 (2) | 0.3246 (2) | 0.3719 (2) | 0.0421 (6) | |
H48A | 1.0529 | 0.2762 | 0.3446 | 0.050* | |
H48B | 1.0708 | 0.3972 | 0.4258 | 0.050* | |
C49 | 0.9530 (2) | 0.3393 (2) | 0.29589 (17) | 0.0350 (5) | |
H49A | 1.0012 | 0.4001 | 0.2889 | 0.042* | |
H49B | 0.9192 | 0.2699 | 0.2331 | 0.042* | |
C50 | 0.8673 (2) | 0.3683 (2) | 0.33600 (17) | 0.0314 (5) | |
H50A | 0.8983 | 0.4475 | 0.3863 | 0.038* | |
H50B | 0.8046 | 0.3534 | 0.2851 | 0.038* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0294 (8) | 0.0529 (10) | 0.0224 (8) | 0.0190 (8) | 0.0109 (7) | 0.0148 (7) |
O2 | 0.0288 (8) | 0.0374 (9) | 0.0352 (8) | 0.0165 (7) | 0.0152 (7) | 0.0242 (7) |
Zr1 | 0.02394 (10) | 0.02405 (10) | 0.01852 (10) | 0.01080 (7) | 0.00542 (7) | 0.00919 (8) |
Zr2 | 0.02249 (10) | 0.02244 (10) | 0.01938 (10) | 0.00790 (7) | 0.00445 (7) | 0.01071 (7) |
Cl1 | 0.0381 (3) | 0.0412 (3) | 0.0247 (3) | 0.0000 (2) | −0.0037 (2) | 0.0145 (2) |
Cl2 | 0.0351 (3) | 0.0340 (3) | 0.0347 (3) | 0.0189 (2) | 0.0122 (2) | 0.0224 (2) |
Cl3 | 0.0326 (3) | 0.0247 (2) | 0.0317 (3) | 0.0131 (2) | 0.0095 (2) | 0.0149 (2) |
Cl4 | 0.0485 (3) | 0.0285 (3) | 0.0281 (3) | 0.0201 (2) | 0.0034 (2) | 0.0074 (2) |
Cl5 | 0.0348 (3) | 0.0435 (3) | 0.0258 (2) | 0.0196 (2) | 0.0075 (2) | 0.0198 (2) |
Cl6 | 0.0344 (3) | 0.0264 (3) | 0.0240 (2) | 0.0071 (2) | 0.0067 (2) | 0.0071 (2) |
N1 | 0.0274 (9) | 0.0251 (9) | 0.0252 (9) | 0.0114 (7) | 0.0107 (7) | 0.0126 (7) |
N2 | 0.0253 (9) | 0.0265 (9) | 0.0220 (8) | 0.0102 (7) | 0.0066 (7) | 0.0129 (7) |
N3 | 0.0257 (9) | 0.0229 (8) | 0.0188 (8) | 0.0103 (7) | 0.0045 (7) | 0.0089 (7) |
N4 | 0.0255 (9) | 0.0225 (9) | 0.0202 (8) | 0.0093 (7) | 0.0074 (7) | 0.0101 (7) |
C1 | 0.0403 (13) | 0.0370 (13) | 0.0497 (15) | 0.0226 (11) | 0.0267 (12) | 0.0228 (12) |
C2 | 0.0291 (11) | 0.0252 (10) | 0.0288 (11) | 0.0114 (9) | 0.0108 (9) | 0.0108 (9) |
C3 | 0.0351 (12) | 0.0286 (11) | 0.0334 (12) | 0.0184 (10) | 0.0118 (10) | 0.0140 (9) |
C4 | 0.0346 (12) | 0.0287 (11) | 0.0287 (11) | 0.0150 (9) | 0.0072 (9) | 0.0143 (9) |
C5 | 0.077 (2) | 0.0609 (18) | 0.0466 (15) | 0.0501 (17) | 0.0298 (15) | 0.0371 (14) |
C6 | 0.0300 (11) | 0.0282 (11) | 0.0314 (11) | 0.0150 (9) | 0.0169 (9) | 0.0161 (9) |
C7 | 0.0350 (12) | 0.0342 (12) | 0.0292 (11) | 0.0189 (10) | 0.0177 (10) | 0.0163 (10) |
C8 | 0.0457 (14) | 0.0459 (14) | 0.0331 (12) | 0.0293 (12) | 0.0242 (11) | 0.0245 (11) |
C9 | 0.0468 (14) | 0.0406 (13) | 0.0506 (15) | 0.0276 (12) | 0.0320 (12) | 0.0318 (12) |
C10 | 0.0363 (13) | 0.0315 (12) | 0.0479 (14) | 0.0167 (10) | 0.0225 (11) | 0.0218 (11) |
C11 | 0.0311 (11) | 0.0292 (11) | 0.0360 (12) | 0.0140 (9) | 0.0151 (10) | 0.0167 (10) |
C12 | 0.0426 (14) | 0.0407 (14) | 0.0253 (11) | 0.0138 (11) | 0.0137 (10) | 0.0110 (10) |
C13 | 0.0325 (12) | 0.0355 (13) | 0.0378 (13) | 0.0052 (10) | 0.0080 (10) | 0.0155 (11) |
C14 | 0.0309 (11) | 0.0297 (11) | 0.0231 (10) | 0.0138 (9) | 0.0082 (9) | 0.0157 (9) |
C15 | 0.0302 (11) | 0.0301 (11) | 0.0263 (11) | 0.0138 (9) | 0.0061 (9) | 0.0161 (9) |
C16 | 0.0376 (12) | 0.0325 (12) | 0.0240 (11) | 0.0136 (10) | 0.0054 (9) | 0.0123 (9) |
C17 | 0.0501 (15) | 0.0439 (14) | 0.0282 (12) | 0.0229 (12) | 0.0172 (11) | 0.0212 (11) |
C18 | 0.0381 (13) | 0.0447 (14) | 0.0363 (13) | 0.0128 (11) | 0.0159 (11) | 0.0252 (11) |
C19 | 0.0339 (12) | 0.0322 (12) | 0.0286 (11) | 0.0109 (10) | 0.0089 (9) | 0.0176 (10) |
C20 | 0.0280 (11) | 0.0351 (12) | 0.0275 (11) | 0.0069 (9) | 0.0027 (9) | 0.0145 (10) |
C21 | 0.0423 (14) | 0.0344 (13) | 0.0362 (13) | 0.0034 (11) | 0.0092 (11) | 0.0195 (11) |
C22 | 0.0265 (11) | 0.0371 (13) | 0.0319 (12) | 0.0096 (10) | 0.0087 (9) | 0.0153 (10) |
C23 | 0.0308 (12) | 0.0367 (13) | 0.0516 (15) | 0.0130 (10) | 0.0101 (11) | 0.0186 (12) |
C24 | 0.0487 (17) | 0.0466 (17) | 0.0540 (18) | 0.0241 (14) | 0.0106 (14) | 0.0031 (14) |
C26 | 0.0375 (13) | 0.0300 (12) | 0.0345 (12) | 0.0066 (10) | 0.0164 (10) | 0.0145 (10) |
C27 | 0.0266 (10) | 0.0244 (10) | 0.0264 (10) | 0.0105 (8) | 0.0076 (8) | 0.0135 (9) |
C28 | 0.0285 (11) | 0.0209 (10) | 0.0261 (10) | 0.0071 (8) | 0.0055 (9) | 0.0096 (8) |
C29 | 0.0268 (10) | 0.0216 (10) | 0.0234 (10) | 0.0102 (8) | 0.0033 (8) | 0.0082 (8) |
C30 | 0.0374 (12) | 0.0256 (11) | 0.0234 (11) | 0.0075 (9) | 0.0043 (9) | 0.0052 (9) |
C31 | 0.0288 (11) | 0.0211 (10) | 0.0217 (10) | 0.0070 (8) | 0.0087 (8) | 0.0090 (8) |
C32 | 0.0285 (11) | 0.0266 (11) | 0.0288 (11) | 0.0107 (9) | 0.0113 (9) | 0.0144 (9) |
C33 | 0.0391 (13) | 0.0253 (11) | 0.0351 (12) | 0.0148 (10) | 0.0156 (10) | 0.0123 (10) |
C34 | 0.0475 (14) | 0.0258 (11) | 0.0275 (11) | 0.0116 (10) | 0.0139 (10) | 0.0069 (9) |
C35 | 0.0444 (14) | 0.0314 (12) | 0.0213 (10) | 0.0113 (10) | 0.0068 (10) | 0.0099 (9) |
C36 | 0.0344 (12) | 0.0276 (11) | 0.0248 (11) | 0.0095 (9) | 0.0093 (9) | 0.0130 (9) |
C37 | 0.0479 (14) | 0.0386 (13) | 0.0279 (11) | 0.0204 (11) | 0.0122 (10) | 0.0206 (10) |
C38 | 0.0343 (12) | 0.0359 (12) | 0.0313 (12) | 0.0188 (10) | 0.0121 (10) | 0.0171 (10) |
C39 | 0.0294 (11) | 0.0242 (10) | 0.0167 (9) | 0.0093 (8) | 0.0034 (8) | 0.0070 (8) |
C40 | 0.0348 (12) | 0.0293 (11) | 0.0197 (10) | 0.0132 (9) | 0.0075 (9) | 0.0082 (9) |
C41 | 0.0427 (13) | 0.0381 (13) | 0.0241 (11) | 0.0167 (11) | 0.0137 (10) | 0.0125 (10) |
C42 | 0.0478 (14) | 0.0368 (13) | 0.0201 (10) | 0.0124 (11) | 0.0088 (10) | 0.0136 (10) |
C43 | 0.0434 (13) | 0.0299 (12) | 0.0231 (10) | 0.0149 (10) | 0.0030 (9) | 0.0116 (9) |
C44 | 0.0310 (11) | 0.0273 (11) | 0.0186 (10) | 0.0099 (9) | 0.0019 (8) | 0.0076 (8) |
C45 | 0.0345 (12) | 0.0331 (12) | 0.0280 (11) | 0.0169 (10) | 0.0045 (9) | 0.0134 (9) |
C46 | 0.0459 (14) | 0.0387 (13) | 0.0337 (12) | 0.0256 (11) | 0.0189 (11) | 0.0180 (11) |
C47 | 0.0323 (13) | 0.0599 (17) | 0.0544 (16) | 0.0260 (12) | 0.0191 (12) | 0.0397 (14) |
C48 | 0.0327 (13) | 0.0541 (16) | 0.0454 (14) | 0.0173 (11) | 0.0170 (11) | 0.0290 (13) |
C49 | 0.0335 (12) | 0.0381 (13) | 0.0327 (12) | 0.0126 (10) | 0.0150 (10) | 0.0175 (10) |
C50 | 0.0373 (12) | 0.0316 (12) | 0.0313 (11) | 0.0142 (10) | 0.0167 (10) | 0.0189 (10) |
O1—C25a | 1.473 (3) | C22—H22a | 0.99 |
O1—C22 | 1.478 (2) | C22—H22b | 0.99 |
O1—C25b | 1.508 (4) | C23—C24 | 1.508 (4) |
O1—Zr1 | 2.2694 (16) | C23—H23a | 0.99 |
O2—C50 | 1.470 (3) | C23—H23b | 0.99 |
O2—C47 | 1.487 (3) | C24—C25b | 1.471 (4) |
O2—Zr2 | 2.2517 (15) | C24—C25a | 1.479 (4) |
Zr1—N1 | 2.1759 (18) | C24—H24a | 0.99 |
Zr1—N2 | 2.2182 (17) | C24—H24b | 0.99 |
Zr1—Cl4 | 2.4316 (6) | C24—H24c | 0.99 |
Zr1—Cl5 | 2.4453 (5) | C24—H24d | 0.99 |
Zr1—Cl6 | 2.4551 (5) | C25a—H25a | 0.99 |
Zr2—N4 | 2.1766 (17) | C25a—H25b | 0.99 |
Zr2—N3 | 2.2262 (17) | C25b—H25c | 0.99 |
Zr2—Cl1 | 2.4227 (6) | C25b—H25d | 0.99 |
Zr2—Cl3 | 2.4336 (5) | C26—C27 | 1.506 (3) |
Zr2—Cl2 | 2.4395 (5) | C26—H26a | 0.98 |
N1—C2 | 1.345 (3) | C26—H26b | 0.98 |
N1—C6 | 1.458 (3) | C26—H26c | 0.98 |
N2—C4 | 1.338 (3) | C27—C28 | 1.400 (3) |
N2—C14 | 1.459 (3) | C28—C29 | 1.402 (3) |
N3—C29 | 1.337 (3) | C28—H28a | 0.95 |
N3—C39 | 1.451 (3) | C29—C30 | 1.510 (3) |
N4—C27 | 1.344 (3) | C30—H30a | 0.98 |
N4—C31 | 1.455 (3) | C30—H30b | 0.98 |
C1—C2 | 1.512 (3) | C30—H30c | 0.98 |
C1—H1a | 0.98 | C31—C36 | 1.401 (3) |
C1—H1b | 0.98 | C31—C32 | 1.401 (3) |
C1—H1c | 0.98 | C32—C33 | 1.396 (3) |
C2—C3 | 1.387 (3) | C32—C38 | 1.507 (3) |
C3—C4 | 1.409 (3) | C33—C34 | 1.385 (4) |
C3—H3a | 0.95 | C33—H33a | 0.95 |
C4—C5 | 1.504 (3) | C34—C35 | 1.382 (4) |
C5—H5a | 0.98 | C34—H34a | 0.95 |
C5—H5b | 0.98 | C35—C36 | 1.399 (3) |
C5—H5c | 0.98 | C35—H35a | 0.95 |
C6—C11 | 1.403 (3) | C36—C37 | 1.505 (3) |
C6—C7 | 1.403 (3) | C37—H37a | 0.98 |
C7—C8 | 1.395 (3) | C37—H37b | 0.98 |
C7—C12 | 1.503 (3) | C37—H37c | 0.98 |
C8—C9 | 1.380 (4) | C38—H38a | 0.98 |
C8—H8a | 0.95 | C38—H38b | 0.98 |
C9—C10 | 1.379 (4) | C38—H38c | 0.98 |
C9—H9a | 0.95 | C39—C40 | 1.401 (3) |
C10—C11 | 1.392 (3) | C39—C44 | 1.405 (3) |
C10—H10a | 0.95 | C40—C41 | 1.396 (3) |
C11—C13 | 1.508 (3) | C40—C46 | 1.507 (3) |
C12—H12a | 0.98 | C41—C42 | 1.380 (4) |
C12—H12b | 0.98 | C41—H41a | 0.95 |
C12—H12c | 0.98 | C42—C43 | 1.383 (4) |
C13—H13a | 0.98 | C42—H42a | 0.95 |
C13—H13b | 0.98 | C43—C44 | 1.395 (3) |
C13—H13c | 0.98 | C43—H43a | 0.95 |
C14—C19 | 1.400 (3) | C44—C45 | 1.502 (3) |
C14—C15 | 1.403 (3) | C45—H45a | 0.98 |
C15—C16 | 1.398 (3) | C45—H45b | 0.98 |
C15—C20 | 1.503 (3) | C45—H45c | 0.98 |
C16—C17 | 1.378 (4) | C46—H46a | 0.98 |
C16—H16a | 0.95 | C46—H46b | 0.98 |
C17—C18 | 1.383 (4) | C46—H46c | 0.98 |
C17—H17a | 0.95 | C47—C48 | 1.514 (3) |
C18—C19 | 1.403 (3) | C47—H47a | 0.99 |
C18—H18a | 0.95 | C47—H47b | 0.99 |
C19—C21 | 1.507 (3) | C48—C49 | 1.524 (4) |
C20—H20a | 0.98 | C48—H48a | 0.99 |
C20—H20b | 0.98 | C48—H48b | 0.99 |
C20—H20c | 0.98 | C49—C50 | 1.508 (3) |
C21—H21a | 0.98 | C49—H49a | 0.99 |
C21—H21b | 0.98 | C49—H49b | 0.99 |
C21—H21c | 0.98 | C50—H50a | 0.99 |
C22—C23 | 1.490 (3) | C50—H50b | 0.99 |
C25A—O1—C22 | 100.8 (2) | C22—C23—H23A | 110.9 |
C22—O1—C25B | 110.0 (2) | C24—C23—H23A | 110.9 |
C25A—O1—ZR1 | 135.7 (2) | C22—C23—H23B | 110.9 |
C22—O1—ZR1 | 122.05 (12) | C24—C23—H23B | 110.9 |
C25B—O1—ZR1 | 119.1 (3) | H23A—C23—H23B | 108.9 |
C50—O2—C47 | 108.24 (17) | C25B—C24—C23 | 108.9 (3) |
C50—O2—ZR2 | 126.32 (13) | C25A—C24—C23 | 105.4 (2) |
C47—O2—ZR2 | 122.94 (13) | C25B—C24—H24A | 126.4 |
N1—ZR1—N2 | 83.11 (7) | C25A—C24—H24A | 110.7 |
N1—ZR1—O1 | 174.03 (7) | C23—C24—H24A | 110.7 |
N2—ZR1—O1 | 91.54 (6) | C25B—C24—H24B | 89 |
N1—ZR1—CL4 | 97.72 (5) | C25A—C24—H24B | 110.7 |
N2—ZR1—CL4 | 92.34 (5) | C23—C24—H24B | 110.7 |
O1—ZR1—CL4 | 85.10 (5) | H24A—C24—H24B | 108.8 |
N1—ZR1—CL5 | 98.86 (5) | C25A—C24—H24C | 91.2 |
N2—ZR1—CL5 | 176.67 (5) | C23—C24—H24C | 109.9 |
O1—ZR1—CL5 | 86.36 (4) | C25B—C24—H24D | 109.9 |
CL4—ZR1—CL5 | 90.06 (2) | C25A—C24—H24D | 129.9 |
N1—ZR1—CL6 | 91.09 (5) | C23—C24—H24D | 109.9 |
N2—ZR1—CL6 | 86.50 (5) | H24A—C24—H24D | 88.8 |
O1—ZR1—CL6 | 85.93 (5) | H24C—C24—H24D | 108.3 |
CL4—ZR1—CL6 | 170.91 (2) | O1—C25A—C24 | 105.0 (2) |
CL5—ZR1—CL6 | 90.77 (2) | O1—C25A—H25A | 110.7 |
N4—ZR2—N3 | 82.65 (6) | C24—C25A—H25A | 110.7 |
N4—ZR2—O2 | 173.55 (6) | O1—C25A—H25B | 110.7 |
N3—ZR2—O2 | 94.92 (6) | C24—C25A—H25B | 110.7 |
N4—ZR2—CL1 | 96.00 (5) | H25A—C25A—H25B | 108.8 |
N3—ZR2—CL1 | 177.03 (5) | C24—C25B—O1 | 103.6 (3) |
O2—ZR2—CL1 | 86.69 (5) | C24—C25B—H25C | 111 |
N4—ZR2—CL3 | 100.57 (5) | O1—C25B—H25C | 111 |
N3—ZR2—CL3 | 89.58 (5) | C24—C25B—H25D | 111 |
O2—ZR2—CL3 | 85.35 (4) | O1—C25B—H25D | 111 |
CL1—ZR2—CL3 | 88.06 (2) | H25C—C25B—H25D | 109 |
N4—ZR2—CL2 | 89.39 (5) | C27—C26—H26A | 109.5 |
N3—ZR2—CL2 | 88.26 (5) | C27—C26—H26B | 109.5 |
O2—ZR2—CL2 | 84.55 (4) | H26A—C26—H26B | 109.5 |
CL1—ZR2—CL2 | 94.37 (2) | C27—C26—H26C | 109.5 |
CL3—ZR2—CL2 | 169.458 (19) | H26A—C26—H26C | 109.5 |
C2—N1—C6 | 115.53 (18) | H26B—C26—H26C | 109.5 |
C2—N1—ZR1 | 124.55 (15) | N4—C27—C28 | 123.38 (19) |
C6—N1—ZR1 | 119.68 (13) | N4—C27—C26 | 119.86 (19) |
C4—N2—C14 | 116.36 (17) | C28—C27—C26 | 116.70 (19) |
C4—N2—ZR1 | 122.39 (14) | C27—C28—C29 | 128.5 (2) |
C14—N2—ZR1 | 120.82 (13) | C27—C28—H28A | 115.8 |
C29—N3—C39 | 118.24 (17) | C29—C28—H28A | 115.8 |
C29—N3—ZR2 | 123.43 (14) | N3—C29—C28 | 123.48 (19) |
C39—N3—ZR2 | 118.04 (13) | N3—C29—C30 | 119.20 (19) |
C27—N4—C31 | 117.46 (17) | C28—C29—C30 | 117.23 (19) |
C27—N4—ZR2 | 124.81 (14) | C29—C30—H30A | 109.5 |
C31—N4—ZR2 | 117.39 (13) | C29—C30—H30B | 109.5 |
C2—C1—H1A | 109.5 | H30A—C30—H30B | 109.5 |
C2—C1—H1B | 109.5 | C29—C30—H30C | 109.5 |
H1A—C1—H1B | 109.5 | H30A—C30—H30C | 109.5 |
C2—C1—H1C | 109.5 | H30B—C30—H30C | 109.5 |
H1A—C1—H1C | 109.5 | C36—C31—C32 | 121.5 (2) |
H1B—C1—H1C | 109.5 | C36—C31—N4 | 120.4 (2) |
N1—C2—C3 | 123.5 (2) | C32—C31—N4 | 118.11 (19) |
N1—C2—C1 | 119.8 (2) | C33—C32—C31 | 118.3 (2) |
C3—C2—C1 | 116.7 (2) | C33—C32—C38 | 120.0 (2) |
C2—C3—C4 | 128.5 (2) | C31—C32—C38 | 121.7 (2) |
C2—C3—H3A | 115.7 | C34—C33—C32 | 120.9 (2) |
C4—C3—H3A | 115.7 | C34—C33—H33A | 119.5 |
N2—C4—C3 | 123.6 (2) | C32—C33—H33A | 119.5 |
N2—C4—C5 | 119.8 (2) | C35—C34—C33 | 119.8 (2) |
C3—C4—C5 | 116.5 (2) | C35—C34—H34A | 120.1 |
C4—C5—H5A | 109.5 | C33—C34—H34A | 120.1 |
C4—C5—H5B | 109.5 | C34—C35—C36 | 121.3 (2) |
H5A—C5—H5B | 109.5 | C34—C35—H35A | 119.4 |
C4—C5—H5C | 109.5 | C36—C35—H35A | 119.4 |
H5A—C5—H5C | 109.5 | C35—C36—C31 | 117.9 (2) |
H5B—C5—H5C | 109.5 | C35—C36—C37 | 119.3 (2) |
C11—C6—C7 | 121.5 (2) | C31—C36—C37 | 122.8 (2) |
C11—C6—N1 | 119.0 (2) | C36—C37—H37A | 109.5 |
C7—C6—N1 | 119.4 (2) | C36—C37—H37B | 109.5 |
C8—C7—C6 | 117.4 (2) | H37A—C37—H37B | 109.5 |
C8—C7—C12 | 119.6 (2) | C36—C37—H37C | 109.5 |
C6—C7—C12 | 123.0 (2) | H37A—C37—H37C | 109.5 |
C9—C8—C7 | 122.1 (2) | H37B—C37—H37C | 109.5 |
C9—C8—H8A | 119 | C32—C38—H38A | 109.5 |
C7—C8—H8A | 119 | C32—C38—H38B | 109.5 |
C10—C9—C8 | 119.4 (2) | H38A—C38—H38B | 109.5 |
C10—C9—H9A | 120.3 | C32—C38—H38C | 109.5 |
C8—C9—H9A | 120.3 | H38A—C38—H38C | 109.5 |
C9—C10—C11 | 121.3 (2) | H38B—C38—H38C | 109.5 |
C9—C10—H10A | 119.4 | C40—C39—C44 | 121.2 (2) |
C11—C10—H10A | 119.4 | C40—C39—N3 | 120.88 (19) |
C10—C11—C6 | 118.4 (2) | C44—C39—N3 | 117.81 (19) |
C10—C11—C13 | 120.1 (2) | C41—C40—C39 | 118.2 (2) |
C6—C11—C13 | 121.5 (2) | C41—C40—C46 | 119.1 (2) |
C7—C12—H12A | 109.5 | C39—C40—C46 | 122.7 (2) |
C7—C12—H12B | 109.5 | C42—C41—C40 | 121.0 (2) |
H12A—C12—H12B | 109.5 | C42—C41—H41A | 119.5 |
C7—C12—H12C | 109.5 | C40—C41—H41A | 119.5 |
H12A—C12—H12C | 109.5 | C41—C42—C43 | 120.0 (2) |
H12B—C12—H12C | 109.5 | C41—C42—H42A | 120 |
C11—C13—H13A | 109.5 | C43—C42—H42A | 120 |
C11—C13—H13B | 109.5 | C42—C43—C44 | 121.0 (2) |
H13A—C13—H13B | 109.5 | C42—C43—H43A | 119.5 |
C11—C13—H13C | 109.5 | C44—C43—H43A | 119.5 |
H13A—C13—H13C | 109.5 | C43—C44—C39 | 118.2 (2) |
H13B—C13—H13C | 109.5 | C43—C44—C45 | 120.1 (2) |
C19—C14—C15 | 121.7 (2) | C39—C44—C45 | 121.7 (2) |
C19—C14—N2 | 120.79 (19) | C44—C45—H45A | 109.5 |
C15—C14—N2 | 117.50 (19) | C44—C45—H45B | 109.5 |
C16—C15—C14 | 118.2 (2) | H45A—C45—H45B | 109.5 |
C16—C15—C20 | 119.9 (2) | C44—C45—H45C | 109.5 |
C14—C15—C20 | 121.9 (2) | H45A—C45—H45C | 109.5 |
C17—C16—C15 | 121.0 (2) | H45B—C45—H45C | 109.5 |
C17—C16—H16A | 119.5 | C40—C46—H46A | 109.5 |
C15—C16—H16A | 119.5 | C40—C46—H46B | 109.5 |
C16—C17—C18 | 120.1 (2) | H46A—C46—H46B | 109.5 |
C16—C17—H17A | 119.9 | C40—C46—H46C | 109.5 |
C18—C17—H17A | 119.9 | H46A—C46—H46C | 109.5 |
C17—C18—C19 | 121.1 (2) | H46B—C46—H46C | 109.5 |
C17—C18—H18A | 119.4 | O2—C47—C48 | 105.6 (2) |
C19—C18—H18A | 119.4 | O2—C47—H47A | 110.6 |
C14—C19—C18 | 117.8 (2) | C48—C47—H47A | 110.6 |
C14—C19—C21 | 123.6 (2) | O2—C47—H47B | 110.6 |
C18—C19—C21 | 118.6 (2) | C48—C47—H47B | 110.6 |
C15—C20—H20A | 109.5 | H47A—C47—H47B | 108.7 |
C15—C20—H20B | 109.5 | C47—C48—C49 | 104.0 (2) |
H20A—C20—H20B | 109.5 | C47—C48—H48A | 111 |
C15—C20—H20C | 109.5 | C49—C48—H48A | 111 |
H20A—C20—H20C | 109.5 | C47—C48—H48B | 111 |
H20B—C20—H20C | 109.5 | C49—C48—H48B | 111 |
C19—C21—H21A | 109.5 | H48A—C48—H48B | 109 |
C19—C21—H21B | 109.5 | C50—C49—C48 | 102.18 (19) |
H21A—C21—H21B | 109.5 | C50—C49—H49A | 111.3 |
C19—C21—H21C | 109.5 | C48—C49—H49A | 111.3 |
H21A—C21—H21C | 109.5 | C50—C49—H49B | 111.3 |
H21B—C21—H21C | 109.5 | C48—C49—H49B | 111.3 |
O1—C22—C23 | 103.91 (18) | H49A—C49—H49B | 109.2 |
O1—C22—H22A | 111 | O2—C50—C49 | 103.61 (18) |
C23—C22—H22A | 111 | O2—C50—H50A | 111 |
O1—C22—H22B | 111 | C49—C50—H50A | 111 |
C23—C22—H22B | 111 | O2—C50—H50B | 111 |
H22A—C22—H22B | 109 | C49—C50—H50B | 111 |
C22—C23—C24 | 104.3 (2) | H50A—C50—H50B | 109 |
C25A—O1—ZR1—N2 | −65.5 (3) | C19—C14—C15—C16 | 5.1 (3) |
C22—O1—ZR1—N2 | 131.26 (17) | N2—C14—C15—C16 | −177.44 (19) |
C25B—O1—ZR1—N2 | −84.5 (4) | C19—C14—C15—C20 | −172.0 (2) |
C25A—O1—ZR1—CL4 | 26.7 (3) | N2—C14—C15—C20 | 5.5 (3) |
C22—O1—ZR1—CL4 | −136.52 (16) | C14—C15—C16—C17 | −2.1 (3) |
C25B—O1—ZR1—CL4 | 7.7 (4) | C20—C15—C16—C17 | 175.0 (2) |
C25A—O1—ZR1—CL5 | 117.0 (3) | C15—C16—C17—C18 | −1.2 (4) |
C22—O1—ZR1—CL5 | −46.14 (16) | C16—C17—C18—C19 | 1.7 (4) |
C25B—O1—ZR1—CL5 | 98.1 (4) | C15—C14—C19—C18 | −4.6 (3) |
C25A—O1—ZR1—CL6 | −151.9 (3) | N2—C14—C19—C18 | 178.0 (2) |
C22—O1—ZR1—CL6 | 44.89 (16) | C15—C14—C19—C21 | 173.5 (2) |
C25B—O1—ZR1—CL6 | −170.9 (4) | N2—C14—C19—C21 | −3.9 (4) |
C50—O2—ZR2—N3 | 80.13 (17) | C17—C18—C19—C14 | 1.2 (4) |
C47—O2—ZR2—N3 | −119.98 (18) | C17—C18—C19—C21 | −177.0 (2) |
C50—O2—ZR2—CL1 | −97.37 (16) | C25A—O1—C22—C23 | −44.4 (3) |
C47—O2—ZR2—CL1 | 62.52 (18) | C25B—O1—C22—C23 | −23.3 (5) |
C50—O2—ZR2—CL3 | −9.05 (16) | ZR1—O1—C22—C23 | 123.79 (18) |
C47—O2—ZR2—CL3 | 150.84 (18) | O1—C22—C23—C24 | 30.0 (3) |
C50—O2—ZR2—CL2 | 167.91 (17) | C22—C23—C24—C25B | −27.4 (6) |
C47—O2—ZR2—CL2 | −32.20 (17) | C22—C23—C24—C25A | −4.0 (4) |
N2—ZR1—N1—C2 | −33.21 (18) | C22—O1—C25A—C24 | 41.9 (4) |
CL4—ZR1—N1—C2 | −124.64 (17) | C25B—O1—C25A—C24 | −75.2 (5) |
CL5—ZR1—N1—C2 | 144.08 (17) | ZR1—O1—C25A—C24 | −123.6 (3) |
CL6—ZR1—N1—C2 | 53.14 (17) | C25B—C24—C25A—O1 | 78.5 (5) |
N2—ZR1—N1—C6 | 152.64 (16) | C23—C24—C25A—O1 | −23.6 (5) |
CL4—ZR1—N1—C6 | 61.20 (16) | C25A—C24—C25B—O1 | −72.0 (5) |
CL5—ZR1—N1—C6 | −30.07 (16) | C23—C24—C25B—O1 | 12.9 (7) |
CL6—ZR1—N1—C6 | −121.02 (15) | C25A—O1—C25B—C24 | 75.1 (5) |
N1—ZR1—N2—C4 | 35.98 (17) | C22—O1—C25B—C24 | 6.5 (7) |
O1—ZR1—N2—C4 | −141.36 (17) | ZR1—O1—C25B—C24 | −141.6 (4) |
CL4—ZR1—N2—C4 | 133.48 (17) | C31—N4—C27—C28 | 168.1 (2) |
CL6—ZR1—N2—C4 | −55.54 (17) | ZR2—N4—C27—C28 | −18.8 (3) |
N1—ZR1—N2—C14 | −151.80 (16) | C31—N4—C27—C26 | −9.0 (3) |
O1—ZR1—N2—C14 | 30.85 (16) | ZR2—N4—C27—C26 | 164.13 (16) |
CL4—ZR1—N2—C14 | −54.30 (15) | N4—C27—C28—C29 | −14.0 (4) |
CL6—ZR1—N2—C14 | 116.67 (15) | C26—C27—C28—C29 | 163.1 (2) |
N4—ZR2—N3—C29 | −34.50 (16) | C39—N3—C29—C28 | −166.3 (2) |
O2—ZR2—N3—C29 | 139.49 (16) | ZR2—N3—C29—C28 | 20.0 (3) |
CL3—ZR2—N3—C29 | −135.21 (16) | C39—N3—C29—C30 | 10.2 (3) |
CL2—ZR2—N3—C29 | 55.11 (16) | ZR2—N3—C29—C30 | −163.49 (16) |
N4—ZR2—N3—C39 | 151.81 (15) | C27—C28—C29—N3 | 12.9 (4) |
O2—ZR2—N3—C39 | −34.21 (15) | C27—C28—C29—C30 | −163.7 (2) |
CL3—ZR2—N3—C39 | 51.09 (14) | C27—N4—C31—C36 | 92.5 (2) |
CL2—ZR2—N3—C39 | −118.59 (14) | ZR2—N4—C31—C36 | −81.2 (2) |
N3—ZR2—N4—C27 | 34.00 (17) | C27—N4—C31—C32 | −89.7 (2) |
CL1—ZR2—N4—C27 | −148.66 (16) | ZR2—N4—C31—C32 | 96.7 (2) |
CL3—ZR2—N4—C27 | 122.20 (16) | C36—C31—C32—C33 | 3.9 (3) |
CL2—ZR2—N4—C27 | −54.32 (17) | N4—C31—C32—C33 | −173.97 (19) |
N3—ZR2—N4—C31 | −152.88 (15) | C36—C31—C32—C38 | −175.3 (2) |
CL1—ZR2—N4—C31 | 24.46 (15) | N4—C31—C32—C38 | 6.9 (3) |
CL3—ZR2—N4—C31 | −64.68 (15) | C31—C32—C33—C34 | −0.6 (3) |
CL2—ZR2—N4—C31 | 118.80 (14) | C38—C32—C33—C34 | 178.5 (2) |
C6—N1—C2—C3 | −169.4 (2) | C32—C33—C34—C35 | −2.0 (4) |
ZR1—N1—C2—C3 | 16.2 (3) | C33—C34—C35—C36 | 1.6 (4) |
C6—N1—C2—C1 | 8.0 (3) | C34—C35—C36—C31 | 1.6 (4) |
ZR1—N1—C2—C1 | −166.40 (17) | C34—C35—C36—C37 | −177.6 (2) |
N1—C2—C3—C4 | 15.9 (4) | C32—C31—C36—C35 | −4.3 (3) |
C1—C2—C3—C4 | −161.6 (2) | N4—C31—C36—C35 | 173.5 (2) |
C14—N2—C4—C3 | 164.9 (2) | C32—C31—C36—C37 | 174.8 (2) |
ZR1—N2—C4—C3 | −22.6 (3) | N4—C31—C36—C37 | −7.4 (3) |
C14—N2—C4—C5 | −11.5 (3) | C29—N3—C39—C40 | −94.8 (2) |
ZR1—N2—C4—C5 | 161.0 (2) | ZR2—N3—C39—C40 | 79.2 (2) |
C2—C3—C4—N2 | −11.8 (4) | C29—N3—C39—C44 | 88.2 (2) |
C2—C3—C4—C5 | 164.7 (3) | ZR2—N3—C39—C44 | −97.80 (19) |
C2—N1—C6—C11 | 85.2 (2) | C44—C39—C40—C41 | 6.1 (3) |
ZR1—N1—C6—C11 | −100.1 (2) | N3—C39—C40—C41 | −170.8 (2) |
C2—N1—C6—C7 | −91.3 (3) | C44—C39—C40—C46 | −171.2 (2) |
ZR1—N1—C6—C7 | 83.4 (2) | N3—C39—C40—C46 | 11.9 (3) |
C11—C6—C7—C8 | 2.6 (3) | C39—C40—C41—C42 | −1.2 (3) |
N1—C6—C7—C8 | 178.96 (19) | C46—C40—C41—C42 | 176.2 (2) |
C11—C6—C7—C12 | −174.8 (2) | C40—C41—C42—C43 | −3.5 (4) |
N1—C6—C7—C12 | 1.5 (3) | C41—C42—C43—C44 | 3.4 (4) |
C6—C7—C8—C9 | −2.4 (3) | C42—C43—C44—C39 | 1.3 (3) |
C12—C7—C8—C9 | 175.1 (2) | C42—C43—C44—C45 | −177.3 (2) |
C7—C8—C9—C10 | 0.9 (4) | C40—C39—C44—C43 | −6.2 (3) |
C8—C9—C10—C11 | 0.6 (4) | N3—C39—C44—C43 | 170.87 (19) |
C9—C10—C11—C6 | −0.5 (3) | C40—C39—C44—C45 | 172.5 (2) |
C9—C10—C11—C13 | 179.9 (2) | N3—C39—C44—C45 | −10.5 (3) |
C7—C6—C11—C10 | −1.2 (3) | C50—O2—C47—C48 | −4.6 (3) |
N1—C6—C11—C10 | −177.57 (19) | ZR2—O2—C47—C48 | −167.62 (16) |
C7—C6—C11—C13 | 178.5 (2) | O2—C47—C48—C49 | −20.3 (3) |
N1—C6—C11—C13 | 2.1 (3) | C47—C48—C49—C50 | 36.9 (3) |
C4—N2—C14—C19 | 89.4 (3) | C47—O2—C50—C49 | 27.9 (2) |
ZR1—N2—C14—C19 | −83.3 (2) | ZR2—O2—C50—C49 | −169.80 (14) |
C4—N2—C14—C15 | −88.1 (2) | C48—C49—C50—O2 | −39.7 (2) |
ZR1—N2—C14—C15 | 99.2 (2) |
Experimental details
Crystal data | |
Chemical formula | [Zr(C21H25N2)Cl3(C4H8O)] |
Mr | 575.10 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 13.6082 (5), 14.5970 (5), 16.3293 (6) |
α, β, γ (°) | 114.948 (2), 98.898 (2), 107.951 (2) |
V (Å3) | 2641.04 (16) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 6.35 |
Crystal size (mm) | 0.16 × 0.16 × 0.07 |
Data collection | |
Diffractometer | Bruker Smart 6000 |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.50, 0.64 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36248, 9929, 9305 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.088, 0.99 |
No. of reflections | 9929 |
No. of parameters | 589 |
No. of restraints | 11 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.61, −1.25 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), UdMX (Marris, 2004).
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The title compound was first synthesized by Jin & Novak (2000), although no experimental or spectroscopic data was provided. Our synthesis followed the same procedure described there and for the synthesis of other (nacnac)ZrCl3(THF) complexes (Kakaliou et al., 1999), i.e. reaction of the deprotonated nacnac ligand (nacnac = pentane-2,4-diiminato) with ZrCl4(THF)2.
Two identical, independent molecules are present in the asymmetric unit. Only the geometry of one of those is described in detail. Apart from the missing disorder of the THF molecule, no significant differences were observed in the second molecule.
The zirconium center has a slightly distorted octahedral coordination geometry with L–Zr–L bond angles ranging from 83° to 99°. The coordination of the nanac ligand is best described as an in-plane η2-coordination via the nitrogen lone pairs. The ligand backbone is nearly planar, with a slight bending of the methyl groups and the central carbon atom C3 out of the ligand plane, probalby due to steric interaction with each other. Bond distances in the ligand backbone are in agreement with a strong electron delocalization. The zirconium center is slightly bend out of the ligand mean plane (〈 (Zr1,N1,N2),(N1,N2,C2–C4)=41°), a common feature for η2-coordinated nacnac ligands in penta-coordinated or octahedral complexes (Rahim et al., 1998; Qian et al., 1999; Kakaliou et al., 1999; Franceschini et al., 2003; Hamaki et al., 2006). Long Zr—C distances for C2–C4 (> 3.1 Å) indicate, however, that this is not due to coordination of the ligand π-system to the metal center, but rather to the steric strain introduced by the in-plane coordination of the metal center. This is further supported by a N–Zr–N angle smaller than 90° (〈(N1–Zr1–N2)=83.11 (7)°) and slightly widened C3–C–N angles (〈(N1–C2–C3)=123.5 (2)°, 〈(N2–C4–C3)=123.6 (2)°).
One THF molecule, coordinated trans to N2, completes the octahedral coordination of the metal center. Although penta-coordinated (nacnac)ZrCl3 complexes can be isolated in the absence of THF, coordination of THF to a (nacnac)ZrCl3 fragment has been reported before (Kakaliou et al., 1999; Jin & Novak, 2000). In all cases, THF preferred a coordination trans to nitrogen. As also observed in these complexes, the Zr—N2 distance in the title compound is slightly longer than Zr—N1 (2.218 (2) and 2.176 (2) Å, respectively), in agreement with a stronger trans effect of chlorine compared to oxygen.
Of the two possible coordination modes of the nacnac ligand (η2–in plane or ηx–side on), the η2-coordination seems to be preferred when an octahedral coordination of the metal center can be achieved (Franceschini et al., 2003 (BEDLUS, BEDMAZ), Kakaliou et al., 1999 (LIRDOF), Rahim et al., 1998 (SEQXER, SEQXIV), Hamaki et al., 2006 (DEGWIW), Jin & Novak, 2000). For penta-coordinated zirconium complexes both, η2–coordination (LIRCIY, LIRCOE, LIRDUL: Kakaliou et al., 1999; MAPJIW, MAPJUI: Qian et al., 1999) and higher coordination modes (FAPBUU, FAPCEF, FAPCAB, FAPCIJ: Basuli et al., 2004) have been observed. When a second, planar coordinated ligand such as cyclopentadienyl or indenyl is present, the nacnac ligand always prefers higher coordination modes (Vollmerhaus et al., 2000 (QIPGUR); Rahim et al., 1998 (SEQXOB); Verguet, Fortuné et al., 2007; Verguet, Oguadinma & Schaper, 2007). (Codes refer to entries in the Cambridge Structural Database). It should be noted that a "higher coordination mode" does not necessarily correspond to a cyclopentadienyl–like η5–coordination (Verguet, Fortuné et al., 2007).