Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043978/gg2043sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043978/gg2043Isup2.hkl |
CCDC reference: 663603
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.004 Å
- R factor = 0.042
- wR factor = 0.103
- Data-to-parameter ratio = 15.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.95
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.270 0.490 Tmin and Tmax expected: 0.225 0.498 RR = 1.219 Please check that your absorption correction is appropriate. PLAT060_ALERT_3_C Ratio Tmax/Tmin (Exp-to-Rep) (too) Large ....... 1.26 PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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 4 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
The title compound is almost isostructural with the previous indenyl complex (Verguet et al., 2007) and its synthesis and structural discussion are closely related. For a related mixed (indenyl)(nacnac)ZrCl2 compound, see Rahim et al. (1998). A comparable coordination of the nacnac ligand can be found in the five-coordinated complexes reported by 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 ligands, see: Rahim et al. (1998); Vollmerhaus et al. (2000). For related literature, see: Fortuné et al. (2007); Faller et al. (1985); Lee et al. (1999).
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 0.086 g NaCp (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, 0.15 g (32%).
NMR 1H (300 MHz, C6D6), δ p.p.m.: 6.93–6.75 (m, 6H, CH [C6H3Me2]), 6.33 (s, 5H, H [Cp]), 5.35 (s, 1H, CH [nacnac]), 2.66 (s, 12H, CH3 [C6H3Me2]), 1.59 (s, 6H, CH3 [nacnac]). Elem. Anal. for C26H30N2Cl2Zr: clcd. C, 58.60%; H, 5.60%; N,5.30%. found C, 58.47%; H, 5.99%; N, 5.07%.
The H atoms were generated geometrically (C—H 0.95 to 0.98 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 cyclopentadienyl sodium. 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 dependent 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).
In contrast to these, the nacnac ligand adopts in the title complex (I), an intermediate, distorted coordination mode. An analogous coordination mode has already been observed and described for the analogous complex (Verguet et al., 2007), in which cyclopentadienyl was replaced by indenyl. The assignment of the coordination mode follows the same rational and we will point out in the following only shortly the necessary metrical data. The η3-coordinated enamito-moiety C2, C3 and N1 displays short Zr—C2 and Zr—C3 distances of 2.616 (2) and 2.620 (2) Å, respectively compared to a Zr—C4 distance of 2.826 (2) Å for the η1-coordinated imine-moiety. The C2═N1 bond is slighty longer than C4═N2 (1.354 (3) and 1.306 (3) Å, respectively). The metal center is nearly in the plane of the imine moiety (〈 (C5,C4,Zr) = 169.5 (2)°), while a more side-on coordination is observed for N1, C1–C3 (〈 (C1,C2,Zr) = 140.7 (2)°). An elongated C3—C4 distance in comparison with C2—C3 (1.462 (3) and 1.389 (3) Å, respectively) and a 44° angle between the least square planes through N1, C1–C3 and N2, C3–C5 agree with a slight loss of electron delocalization in the nacnac ligand.
Analogous to the corresponding indenyl complex (Verguet et al., 2007), 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 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 plane of the nacnac ligand was ascribed to steric reasons without any significant coordination of the carbon atoms to the metal center (Lee et al., 1999). However, a comparable nacnac coordination was observed in the five-coordinated complexes reported by Basuli et al. (2004) (CSD-codes: FAPBUU, FAPCAP, FAPCEF & FABCIJ), which was simply described as "sandwich-like".
The cyclopentadienyl ligand displays an ideal η5-coordination (ΔM–C < 3σ, Faller et al., 1985).
The title compound is almost isostructural with the previous indenyl complex (Verguet et al., 2007) and its synthesis and structural discussion are closely related. For a related mixed (indenyl)(nacnac)ZrCl2 compound, see Rahim et al. (1998). A comparable coordination of the nacnac ligand can be found in the five-coordinated complexes reported by 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 ligands, see: Rahim et al. (1998); Vollmerhaus et al. (2000). For related literature, see: Fortuné et al. (2007); Faller et al. (1985); 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 the 50% probability level. |
[Zr(Cl)2(C21H25N2)(C5H5)] | Z = 2 |
Mr = 532.64 | F(000) = 548 |
Triclinic, P1 | Dx = 1.450 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 10.0163 (3) Å | Cell parameters from 13439 reflections |
b = 10.5990 (4) Å | θ = 3.5–71.3° |
c = 13.1392 (5) Å | µ = 5.82 mm−1 |
α = 73.803 (1)° | T = 150 K |
β = 78.869 (2)° | Plate, colorless |
γ = 66.178 (1)° | 0.30 × 0.26 × 0.12 mm |
V = 1220.27 (7) Å3 |
Bruker SMART 6000 diffractometer | 4561 independent reflections |
Radiation source: Rotating Anode | 4541 reflections with I > 2σ(I) |
Montel 200 optics monochromator | Rint = 0.036 |
Detector resolution: 5.5 pixels mm-1 | θmax = 71.8°, θmin = 3.5° |
ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −12→12 |
Tmin = 0.27, Tmax = 0.49 | l = −16→16 |
14734 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0762P)2 + 0.4394P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max = 0.002 |
4561 reflections | Δρmax = 0.75 e Å−3 |
287 parameters | Δρmin = −1.59 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0309 (9) |
[Zr(Cl)2(C21H25N2)(C5H5)] | γ = 66.178 (1)° |
Mr = 532.64 | V = 1220.27 (7) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.0163 (3) Å | Cu Kα radiation |
b = 10.5990 (4) Å | µ = 5.82 mm−1 |
c = 13.1392 (5) Å | T = 150 K |
α = 73.803 (1)° | 0.30 × 0.26 × 0.12 mm |
β = 78.869 (2)° |
Bruker SMART 6000 diffractometer | 4561 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4541 reflections with I > 2σ(I) |
Tmin = 0.27, Tmax = 0.49 | Rint = 0.036 |
14734 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.75 e Å−3 |
4561 reflections | Δρmin = −1.59 e Å−3 |
287 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 CHECKCIF-errors: All geometrically accessible data was collected. A data completeness of 0.95 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. |
x | y | z | Uiso*/Ueq | ||
Zr1 | 0.308862 (17) | 1.073009 (17) | 0.252603 (12) | 0.01780 (13) | |
Cl1 | 0.38706 (6) | 1.24068 (6) | 0.10173 (4) | 0.02458 (16) | |
Cl2 | 0.57167 (6) | 0.97220 (6) | 0.29131 (5) | 0.02741 (16) | |
N1 | 0.3069 (2) | 0.8588 (2) | 0.29919 (14) | 0.0201 (4) | |
N2 | 0.1471 (2) | 1.0924 (2) | 0.14178 (15) | 0.0188 (4) | |
C1 | 0.5300 (3) | 0.6836 (3) | 0.2257 (2) | 0.0318 (5) | |
H1A | 0.5924 | 0.6811 | 0.2758 | 0.048* | |
H1B | 0.5862 | 0.6758 | 0.1563 | 0.048* | |
H1C | 0.4963 | 0.6045 | 0.2527 | 0.048* | |
C2 | 0.3999 (2) | 0.8209 (2) | 0.21377 (19) | 0.0224 (5) | |
C3 | 0.3805 (3) | 0.9139 (2) | 0.11475 (18) | 0.0224 (5) | |
H3 | 0.4649 | 0.9149 | 0.0674 | 0.027* | |
C4 | 0.2365 (2) | 1.0103 (2) | 0.07984 (17) | 0.0205 (4) | |
C5 | 0.2026 (3) | 0.9982 (3) | −0.02249 (19) | 0.0285 (5) | |
H5A | 0.1018 | 1.0617 | −0.0364 | 0.043* | |
H5B | 0.2135 | 0.9004 | −0.0170 | 0.043* | |
H5C | 0.2704 | 1.0244 | −0.0809 | 0.043* | |
C6 | −0.0015 (2) | 1.1825 (2) | 0.11747 (18) | 0.0198 (4) | |
C7 | −0.0299 (3) | 1.2987 (2) | 0.02897 (19) | 0.0242 (5) | |
C8 | −0.1755 (3) | 1.3857 (3) | 0.0140 (2) | 0.0285 (5) | |
H8 | −0.1966 | 1.4641 | −0.0452 | 0.034* | |
C9 | −0.2902 (3) | 1.3617 (3) | 0.0825 (2) | 0.0308 (5) | |
H9 | −0.3883 | 1.4241 | 0.0711 | 0.037* | |
C10 | −0.2614 (3) | 1.2461 (3) | 0.1679 (2) | 0.0272 (5) | |
H10 | −0.3405 | 1.2287 | 0.2144 | 0.033* | |
C11 | −0.1171 (3) | 1.1545 (2) | 0.18677 (18) | 0.0222 (4) | |
C12 | 0.0889 (3) | 1.3325 (3) | −0.0499 (2) | 0.0296 (5) | |
H12A | 0.1084 | 1.2855 | −0.1086 | 0.044* | |
H12B | 0.1785 | 1.2990 | −0.0144 | 0.044* | |
H12C | 0.0569 | 1.4351 | −0.0778 | 0.044* | |
C13 | −0.0938 (3) | 1.0269 (3) | 0.2775 (2) | 0.0306 (5) | |
H13A | −0.1544 | 1.0555 | 0.3414 | 0.046* | |
H13B | 0.0097 | 0.9841 | 0.2914 | 0.046* | |
H13C | −0.1214 | 0.9578 | 0.2590 | 0.046* | |
C14 | 0.2780 (3) | 0.7493 (2) | 0.38273 (19) | 0.0227 (5) | |
C15 | 0.1997 (3) | 0.6783 (2) | 0.3584 (2) | 0.0272 (5) | |
C16 | 0.1606 (3) | 0.5787 (3) | 0.4393 (2) | 0.0330 (6) | |
H16 | 0.1060 | 0.5320 | 0.4239 | 0.040* | |
C17 | 0.1999 (3) | 0.5467 (3) | 0.5414 (2) | 0.0345 (6) | |
H17 | 0.1706 | 0.4802 | 0.5960 | 0.041* | |
C18 | 0.2819 (3) | 0.6121 (3) | 0.5633 (2) | 0.0305 (5) | |
H18 | 0.3098 | 0.5888 | 0.6333 | 0.037* | |
C19 | 0.3249 (3) | 0.7120 (2) | 0.48493 (19) | 0.0249 (5) | |
C20 | 0.1620 (3) | 0.7018 (3) | 0.2470 (2) | 0.0368 (6) | |
H20A | 0.2484 | 0.6487 | 0.2054 | 0.055* | |
H20B | 0.1306 | 0.8028 | 0.2132 | 0.055* | |
H20C | 0.0824 | 0.6690 | 0.2501 | 0.055* | |
C21 | 0.4278 (3) | 0.7660 (3) | 0.5126 (2) | 0.0302 (5) | |
H21A | 0.3766 | 0.8252 | 0.5643 | 0.045* | |
H21B | 0.4618 | 0.8222 | 0.4481 | 0.045* | |
H21C | 0.5120 | 0.6857 | 0.5436 | 0.045* | |
C22 | 0.0701 (3) | 1.2031 (3) | 0.3459 (2) | 0.0298 (5) | |
H22 | −0.0181 | 1.2071 | 0.3261 | 0.036* | |
C23 | 0.1387 (3) | 1.3008 (3) | 0.3012 (2) | 0.0319 (6) | |
H23 | 0.1053 | 1.3824 | 0.2455 | 0.038* | |
C24 | 0.2652 (3) | 1.2569 (3) | 0.3532 (2) | 0.0328 (6) | |
H24 | 0.3327 | 1.3034 | 0.3386 | 0.039* | |
C25 | 0.2746 (3) | 1.1325 (3) | 0.4306 (2) | 0.0312 (5) | |
H25 | 0.3488 | 1.0806 | 0.4781 | 0.037* | |
C26 | 0.1550 (3) | 1.0983 (3) | 0.42522 (19) | 0.0296 (5) | |
H26 | 0.1348 | 1.0183 | 0.4678 | 0.036* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr1 | 0.01333 (16) | 0.02266 (16) | 0.01805 (16) | −0.00592 (10) | −0.00042 (9) | −0.00736 (9) |
Cl1 | 0.0210 (3) | 0.0266 (3) | 0.0257 (3) | −0.0101 (2) | −0.0002 (2) | −0.0045 (2) |
Cl2 | 0.0156 (3) | 0.0351 (3) | 0.0303 (3) | −0.0096 (2) | −0.0041 (2) | −0.0040 (2) |
N1 | 0.0188 (9) | 0.0235 (9) | 0.0179 (9) | −0.0078 (7) | −0.0004 (7) | −0.0057 (7) |
N2 | 0.0147 (9) | 0.0238 (9) | 0.0191 (8) | −0.0077 (7) | −0.0009 (7) | −0.0064 (7) |
C1 | 0.0245 (12) | 0.0291 (12) | 0.0320 (13) | −0.0007 (10) | 0.0008 (10) | −0.0086 (10) |
C2 | 0.0183 (11) | 0.0244 (11) | 0.0251 (11) | −0.0066 (9) | −0.0009 (9) | −0.0091 (9) |
C3 | 0.0183 (11) | 0.0258 (11) | 0.0214 (11) | −0.0062 (9) | 0.0037 (9) | −0.0095 (9) |
C4 | 0.0209 (11) | 0.0240 (10) | 0.0185 (10) | −0.0105 (9) | 0.0013 (9) | −0.0065 (8) |
C5 | 0.0293 (12) | 0.0334 (12) | 0.0230 (11) | −0.0075 (10) | −0.0039 (10) | −0.0117 (9) |
C6 | 0.0175 (11) | 0.0231 (10) | 0.0207 (10) | −0.0064 (9) | −0.0040 (9) | −0.0080 (8) |
C7 | 0.0255 (12) | 0.0245 (11) | 0.0249 (11) | −0.0091 (9) | −0.0068 (10) | −0.0066 (9) |
C8 | 0.0301 (13) | 0.0223 (11) | 0.0322 (12) | −0.0049 (9) | −0.0120 (11) | −0.0057 (9) |
C9 | 0.0202 (11) | 0.0304 (12) | 0.0407 (14) | 0.0001 (9) | −0.0115 (11) | −0.0150 (11) |
C10 | 0.0170 (11) | 0.0358 (12) | 0.0313 (12) | −0.0074 (10) | −0.0002 (10) | −0.0163 (10) |
C11 | 0.0175 (10) | 0.0289 (11) | 0.0220 (11) | −0.0072 (9) | −0.0022 (9) | −0.0104 (9) |
C12 | 0.0313 (13) | 0.0307 (12) | 0.0265 (11) | −0.0142 (10) | −0.0073 (10) | 0.0013 (9) |
C13 | 0.0211 (11) | 0.0433 (14) | 0.0252 (12) | −0.0142 (10) | 0.0000 (10) | −0.0022 (10) |
C14 | 0.0190 (11) | 0.0225 (10) | 0.0232 (11) | −0.0059 (9) | 0.0028 (9) | −0.0058 (9) |
C15 | 0.0240 (12) | 0.0245 (11) | 0.0319 (12) | −0.0071 (9) | −0.0012 (10) | −0.0085 (9) |
C16 | 0.0280 (12) | 0.0279 (12) | 0.0427 (14) | −0.0114 (10) | 0.0050 (11) | −0.0112 (11) |
C17 | 0.0326 (14) | 0.0251 (12) | 0.0371 (14) | −0.0093 (10) | 0.0089 (11) | −0.0041 (10) |
C18 | 0.0270 (12) | 0.0291 (12) | 0.0243 (11) | −0.0035 (10) | 0.0008 (10) | −0.0019 (9) |
C19 | 0.0178 (10) | 0.0240 (10) | 0.0259 (11) | −0.0019 (8) | −0.0010 (9) | −0.0046 (9) |
C20 | 0.0401 (15) | 0.0432 (15) | 0.0389 (14) | −0.0234 (13) | −0.0047 (12) | −0.0144 (12) |
C21 | 0.0260 (12) | 0.0394 (13) | 0.0241 (11) | −0.0103 (10) | −0.0054 (10) | −0.0058 (10) |
C22 | 0.0191 (11) | 0.0438 (14) | 0.0277 (12) | −0.0056 (10) | 0.0018 (10) | −0.0219 (11) |
C23 | 0.0310 (13) | 0.0289 (12) | 0.0307 (12) | −0.0002 (10) | −0.0008 (11) | −0.0168 (10) |
C24 | 0.0317 (13) | 0.0381 (14) | 0.0368 (14) | −0.0139 (11) | 0.0004 (11) | −0.0221 (12) |
C25 | 0.0274 (12) | 0.0445 (14) | 0.0230 (11) | −0.0079 (11) | −0.0048 (10) | −0.0161 (10) |
C26 | 0.0283 (12) | 0.0400 (13) | 0.0218 (11) | −0.0124 (11) | 0.0044 (10) | −0.0139 (10) |
Zr1—N1 | 2.1879 (19) | C10—H10 | 0.95 |
Zr1—N2 | 2.2944 (19) | C11—C13 | 1.503 (3) |
Zr1—C26 | 2.500 (2) | C12—H12A | 0.98 |
Zr1—C23 | 2.502 (2) | C12—H12B | 0.98 |
Zr1—Cl1 | 2.5022 (5) | C12—H12C | 0.98 |
Zr1—C24 | 2.503 (2) | C13—H13A | 0.98 |
Zr1—C22 | 2.504 (2) | C13—H13B | 0.98 |
Zr1—Cl2 | 2.5043 (5) | C13—H13C | 0.98 |
Zr1—C25 | 2.514 (2) | C14—C19 | 1.406 (3) |
Zr1—C2 | 2.616 (2) | C14—C15 | 1.412 (3) |
Zr1—C3 | 2.620 (2) | C15—C16 | 1.393 (4) |
Zr1—C4 | 2.826 (2) | C15—C20 | 1.511 (4) |
N2—C4 | 1.306 (3) | C16—C17 | 1.383 (4) |
N2—C6 | 1.447 (3) | C16—H16 | 0.95 |
N1—C2 | 1.354 (3) | C17—C18 | 1.378 (4) |
N1—C14 | 1.440 (3) | C17—H17 | 0.95 |
C5—C4 | 1.499 (3) | C18—C19 | 1.399 (3) |
C5—H5A | 0.98 | C18—H18 | 0.95 |
C5—H5B | 0.98 | C19—C21 | 1.503 (3) |
C5—H5C | 0.98 | C20—H20A | 0.98 |
C4—C3 | 1.462 (3) | C20—H20B | 0.98 |
C3—C2 | 1.389 (3) | C20—H20C | 0.98 |
C3—H3 | 0.95 | C21—H21A | 0.98 |
C2—C1 | 1.504 (3) | C21—H21B | 0.98 |
C1—H1A | 0.98 | C21—H21C | 0.98 |
C1—H1B | 0.98 | C22—C23 | 1.403 (4) |
C1—H1C | 0.98 | C22—C26 | 1.406 (4) |
C6—C11 | 1.406 (3) | C22—H22 | 0.95 |
C6—C7 | 1.413 (3) | C23—C24 | 1.404 (4) |
C7—C8 | 1.393 (3) | C23—H23 | 0.95 |
C7—C12 | 1.510 (3) | C24—C25 | 1.404 (4) |
C8—C9 | 1.379 (4) | C24—H24 | 0.95 |
C8—H8 | 0.95 | C25—C26 | 1.404 (4) |
C9—C10 | 1.384 (4) | C25—H25 | 0.95 |
C9—H9 | 0.95 | C26—H26 | 0.95 |
C10—C11 | 1.402 (3) | ||
N1—Zr1—N2 | 79.32 (7) | C2—C1—H1A | 109.5 |
N1—Zr1—C26 | 83.28 (8) | C2—C1—H1B | 109.5 |
N2—Zr1—C26 | 103.18 (8) | H1A—C1—H1B | 109.5 |
N1—Zr1—C23 | 132.68 (8) | C2—C1—H1C | 109.5 |
N2—Zr1—C23 | 90.58 (8) | H1A—C1—H1C | 109.5 |
C26—Zr1—C23 | 54.01 (9) | H1B—C1—H1C | 109.5 |
N1—Zr1—Cl1 | 142.40 (5) | C11—C6—C7 | 120.8 (2) |
N2—Zr1—Cl1 | 85.52 (5) | C11—C6—N2 | 118.1 (2) |
C26—Zr1—Cl1 | 133.94 (6) | C7—C6—N2 | 121.0 (2) |
C23—Zr1—Cl1 | 81.18 (7) | C8—C7—C6 | 117.9 (2) |
N1—Zr1—C24 | 133.71 (8) | C8—C7—C12 | 118.7 (2) |
N2—Zr1—C24 | 123.08 (8) | C6—C7—C12 | 123.5 (2) |
C26—Zr1—C24 | 53.96 (9) | C9—C8—C7 | 122.1 (2) |
C23—Zr1—C24 | 32.57 (9) | C9—C8—H8 | 118.9 |
Cl1—Zr1—C24 | 83.13 (7) | C7—C8—H8 | 118.9 |
N1—Zr1—C22 | 100.32 (8) | C8—C9—C10 | 119.6 (2) |
N2—Zr1—C22 | 79.26 (7) | C8—C9—H9 | 120.2 |
C26—Zr1—C22 | 32.63 (9) | C10—C9—H9 | 120.2 |
C23—Zr1—C22 | 32.54 (9) | C9—C10—C11 | 120.8 (2) |
Cl1—Zr1—C22 | 110.42 (7) | C9—C10—H10 | 119.6 |
C24—Zr1—C22 | 53.92 (9) | C11—C10—H10 | 119.6 |
N1—Zr1—Cl2 | 89.10 (5) | C10—C11—C6 | 118.7 (2) |
N2—Zr1—Cl2 | 145.66 (5) | C10—C11—C13 | 118.1 (2) |
C26—Zr1—Cl2 | 107.45 (6) | C6—C11—C13 | 123.1 (2) |
C23—Zr1—Cl2 | 119.98 (7) | C7—C12—H12A | 109.5 |
Cl1—Zr1—Cl2 | 84.333 (18) | C7—C12—H12B | 109.5 |
C24—Zr1—Cl2 | 88.08 (7) | H12A—C12—H12B | 109.5 |
C22—Zr1—Cl2 | 134.92 (6) | C7—C12—H12C | 109.5 |
N1—Zr1—C25 | 101.61 (8) | H12A—C12—H12C | 109.5 |
N2—Zr1—C25 | 132.79 (8) | H12B—C12—H12C | 109.5 |
C26—Zr1—C25 | 32.52 (8) | C11—C13—H13A | 109.5 |
C23—Zr1—C25 | 53.89 (9) | C11—C13—H13B | 109.5 |
Cl1—Zr1—C25 | 113.76 (7) | H13A—C13—H13B | 109.5 |
C24—Zr1—C25 | 32.49 (9) | C11—C13—H13C | 109.5 |
C22—Zr1—C25 | 53.89 (8) | H13A—C13—H13C | 109.5 |
Cl2—Zr1—C25 | 81.06 (6) | H13B—C13—H13C | 109.5 |
N1—Zr1—C2 | 31.15 (7) | C19—C14—C15 | 120.1 (2) |
N2—Zr1—C2 | 75.52 (7) | C19—C14—N1 | 122.6 (2) |
C26—Zr1—C2 | 114.33 (8) | C15—C14—N1 | 117.3 (2) |
C23—Zr1—C2 | 159.80 (9) | C16—C15—C14 | 118.9 (2) |
Cl1—Zr1—C2 | 111.65 (5) | C16—C15—C20 | 118.7 (2) |
C24—Zr1—C2 | 158.19 (9) | C14—C15—C20 | 122.4 (2) |
C22—Zr1—C2 | 128.32 (8) | C17—C16—C15 | 121.3 (2) |
Cl2—Zr1—C2 | 77.97 (5) | C17—C16—H16 | 119.4 |
C25—Zr1—C2 | 127.19 (8) | C15—C16—H16 | 119.4 |
N1—Zr1—C3 | 58.30 (7) | C18—C17—C16 | 119.5 (2) |
N2—Zr1—C3 | 57.41 (7) | C18—C17—H17 | 120.3 |
C26—Zr1—C3 | 138.28 (8) | C16—C17—H17 | 120.3 |
C23—Zr1—C3 | 145.88 (8) | C17—C18—C19 | 121.6 (2) |
Cl1—Zr1—C3 | 84.54 (5) | C17—C18—H18 | 119.2 |
C24—Zr1—C3 | 167.55 (9) | C19—C18—H18 | 119.2 |
C22—Zr1—C3 | 133.33 (8) | C18—C19—C14 | 118.5 (2) |
Cl2—Zr1—C3 | 88.97 (5) | C18—C19—C21 | 117.9 (2) |
C25—Zr1—C3 | 157.90 (8) | C14—C19—C21 | 123.5 (2) |
C2—Zr1—C3 | 30.77 (7) | C15—C20—H20A | 109.5 |
N1—Zr1—C4 | 70.63 (7) | C15—C20—H20B | 109.5 |
N2—Zr1—C4 | 27.09 (7) | H20A—C20—H20B | 109.5 |
C26—Zr1—C4 | 125.55 (7) | C15—C20—H20C | 109.5 |
C23—Zr1—C4 | 115.63 (8) | H20A—C20—H20C | 109.5 |
Cl1—Zr1—C4 | 80.25 (4) | H20B—C20—H20C | 109.5 |
C24—Zr1—C4 | 146.60 (8) | C19—C21—H21A | 109.5 |
C22—Zr1—C4 | 106.02 (7) | C19—C21—H21B | 109.5 |
Cl2—Zr1—C4 | 118.61 (5) | H21A—C21—H21B | 109.5 |
C25—Zr1—C4 | 157.86 (8) | C19—C21—H21C | 109.5 |
C2—Zr1—C4 | 54.74 (7) | H21A—C21—H21C | 109.5 |
C3—Zr1—C4 | 30.85 (7) | H21B—C21—H21C | 109.5 |
C4—N2—C6 | 121.83 (19) | C23—C22—C26 | 107.9 (2) |
C4—N2—Zr1 | 99.75 (14) | C23—C22—Zr1 | 73.64 (14) |
C6—N2—Zr1 | 137.20 (14) | C26—C22—Zr1 | 73.50 (14) |
C2—N1—C14 | 118.35 (19) | C23—C22—H22 | 126 |
C2—N1—Zr1 | 92.15 (14) | C26—C22—H22 | 126 |
C14—N1—Zr1 | 147.43 (15) | Zr1—C22—H22 | 118.7 |
C4—C5—H5A | 109.5 | C22—C23—C24 | 108.0 (2) |
C4—C5—H5B | 109.5 | C22—C23—Zr1 | 73.82 (14) |
H5A—C5—H5B | 109.5 | C24—C23—Zr1 | 73.75 (14) |
C4—C5—H5C | 109.5 | C22—C23—H23 | 126 |
H5A—C5—H5C | 109.5 | C24—C23—H23 | 126 |
H5B—C5—H5C | 109.5 | Zr1—C23—H23 | 118.4 |
N2—C4—C3 | 118.3 (2) | C23—C24—C25 | 108.1 (2) |
N2—C4—C5 | 126.0 (2) | C23—C24—Zr1 | 73.68 (14) |
C3—C4—C5 | 115.61 (19) | C25—C24—Zr1 | 74.20 (14) |
N2—C4—Zr1 | 53.16 (11) | C23—C24—H24 | 125.9 |
C3—C4—Zr1 | 66.77 (12) | C25—C24—H24 | 125.9 |
C5—C4—Zr1 | 170.65 (16) | Zr1—C24—H24 | 118.1 |
C2—C3—C4 | 123.2 (2) | C24—C25—C26 | 107.9 (2) |
C2—C3—Zr1 | 74.45 (13) | C24—C25—Zr1 | 73.31 (14) |
C4—C3—Zr1 | 82.37 (13) | C26—C25—Zr1 | 73.16 (14) |
C2—C3—H3 | 118.4 | C24—C25—H25 | 126.1 |
C4—C3—H3 | 118.4 | C26—C25—H25 | 126.1 |
Zr1—C3—H3 | 114.9 | Zr1—C25—H25 | 119.3 |
N1—C2—C3 | 119.7 (2) | C25—C26—C22 | 108.1 (2) |
N1—C2—C1 | 120.9 (2) | C25—C26—Zr1 | 74.32 (14) |
C3—C2—C1 | 119.2 (2) | C22—C26—Zr1 | 73.87 (13) |
N1—C2—Zr1 | 56.70 (11) | C25—C26—H26 | 126 |
C3—C2—Zr1 | 74.77 (13) | C22—C26—H26 | 126 |
C1—C2—Zr1 | 140.72 (17) | Zr1—C26—H26 | 117.8 |
N1—Zr1—N2—C4 | −68.14 (14) | C12—C7—C8—C9 | 179.9 (2) |
C26—Zr1—N2—C4 | −148.56 (14) | C7—C8—C9—C10 | −1.4 (4) |
C23—Zr1—N2—C4 | 158.40 (14) | C8—C9—C10—C11 | 1.1 (4) |
Cl1—Zr1—N2—C4 | 77.30 (13) | C9—C10—C11—C6 | 0.3 (3) |
C24—Zr1—N2—C4 | 156.10 (14) | C9—C10—C11—C13 | −176.9 (2) |
C22—Zr1—N2—C4 | −170.92 (15) | C7—C6—C11—C10 | −1.5 (3) |
Cl2—Zr1—N2—C4 | 4.16 (18) | N2—C6—C11—C10 | 176.1 (2) |
C25—Zr1—N2—C4 | −164.14 (14) | C7—C6—C11—C13 | 175.6 (2) |
C2—Zr1—N2—C4 | −36.43 (13) | N2—C6—C11—C13 | −6.8 (3) |
C3—Zr1—N2—C4 | −9.08 (13) | C2—N1—C14—C19 | 112.3 (2) |
N1—Zr1—N2—C6 | 125.2 (2) | Zr1—N1—C14—C19 | −45.2 (4) |
C26—Zr1—N2—C6 | 44.8 (2) | C2—N1—C14—C15 | −67.5 (3) |
C23—Zr1—N2—C6 | −8.3 (2) | Zr1—N1—C14—C15 | 135.0 (2) |
Cl1—Zr1—N2—C6 | −89.4 (2) | C19—C14—C15—C16 | 4.7 (3) |
C24—Zr1—N2—C6 | −10.6 (2) | N1—C14—C15—C16 | −175.5 (2) |
C22—Zr1—N2—C6 | 22.4 (2) | C19—C14—C15—C20 | −172.7 (2) |
Cl2—Zr1—N2—C6 | −162.52 (17) | N1—C14—C15—C20 | 7.0 (3) |
C25—Zr1—N2—C6 | 29.2 (3) | C14—C15—C16—C17 | −1.4 (4) |
C2—Zr1—N2—C6 | 156.9 (2) | C20—C15—C16—C17 | 176.1 (2) |
C3—Zr1—N2—C6 | −175.8 (2) | C15—C16—C17—C18 | −1.4 (4) |
C4—Zr1—N2—C6 | −166.7 (3) | C16—C17—C18—C19 | 0.9 (4) |
N2—Zr1—N1—C2 | 79.63 (13) | C17—C18—C19—C14 | 2.3 (4) |
C26—Zr1—N1—C2 | −175.54 (14) | C17—C18—C19—C21 | −173.4 (2) |
C23—Zr1—N1—C2 | 160.44 (14) | C15—C14—C19—C18 | −5.2 (3) |
Cl1—Zr1—N1—C2 | 11.66 (17) | N1—C14—C19—C18 | 175.1 (2) |
C24—Zr1—N1—C2 | −154.33 (14) | C15—C14—C19—C21 | 170.3 (2) |
C22—Zr1—N1—C2 | 156.51 (14) | N1—C14—C19—C21 | −9.4 (3) |
Cl2—Zr1—N1—C2 | −67.85 (13) | N1—Zr1—C22—C23 | 174.62 (15) |
C25—Zr1—N1—C2 | −148.53 (14) | N2—Zr1—C22—C23 | −108.45 (16) |
C3—Zr1—N1—C2 | 21.50 (13) | C26—Zr1—C22—C23 | 114.9 (2) |
C4—Zr1—N1—C2 | 53.02 (13) | Cl1—Zr1—C22—C23 | −27.39 (16) |
N2—Zr1—N1—C14 | −120.1 (3) | C24—Zr1—C22—C23 | 37.20 (16) |
C26—Zr1—N1—C14 | −15.2 (3) | Cl2—Zr1—C22—C23 | 75.47 (17) |
C23—Zr1—N1—C14 | −39.2 (3) | C25—Zr1—C22—C23 | 77.71 (17) |
Cl1—Zr1—N1—C14 | 172.0 (2) | C2—Zr1—C22—C23 | −170.14 (14) |
C24—Zr1—N1—C14 | 6.0 (3) | C3—Zr1—C22—C23 | −129.61 (15) |
C22—Zr1—N1—C14 | −43.2 (3) | C4—Zr1—C22—C23 | −112.74 (15) |
Cl2—Zr1—N1—C14 | 92.5 (3) | N1—Zr1—C22—C26 | 59.68 (16) |
C25—Zr1—N1—C14 | 11.8 (3) | N2—Zr1—C22—C26 | 136.61 (16) |
C2—Zr1—N1—C14 | 160.3 (4) | C23—Zr1—C22—C26 | −114.9 (2) |
C3—Zr1—N1—C14 | −178.2 (3) | Cl1—Zr1—C22—C26 | −142.33 (14) |
C4—Zr1—N1—C14 | −146.7 (3) | C24—Zr1—C22—C26 | −77.75 (17) |
C6—N2—C4—C3 | −174.92 (19) | Cl2—Zr1—C22—C26 | −39.48 (19) |
Zr1—N2—C4—C3 | 15.7 (2) | C25—Zr1—C22—C26 | −37.24 (15) |
C6—N2—C4—C5 | 1.0 (3) | C2—Zr1—C22—C26 | 74.91 (17) |
Zr1—N2—C4—C5 | −168.4 (2) | C3—Zr1—C22—C26 | 115.45 (16) |
C6—N2—C4—Zr1 | 169.4 (2) | C4—Zr1—C22—C26 | 132.32 (15) |
N1—Zr1—C4—N2 | 104.83 (14) | C26—C22—C23—C24 | −0.3 (3) |
C26—Zr1—C4—N2 | 38.63 (17) | Zr1—C22—C23—C24 | −66.38 (17) |
C23—Zr1—C4—N2 | −24.10 (16) | C26—C22—C23—Zr1 | 66.04 (17) |
Cl1—Zr1—C4—N2 | −99.32 (13) | N1—Zr1—C23—C22 | −7.2 (2) |
C24—Zr1—C4—N2 | −38.1 (2) | N2—Zr1—C23—C22 | 68.76 (15) |
C22—Zr1—C4—N2 | 9.28 (15) | C26—Zr1—C23—C22 | −37.18 (15) |
Cl2—Zr1—C4—N2 | −177.33 (12) | Cl1—Zr1—C23—C22 | 154.13 (15) |
C25—Zr1—C4—N2 | 32.2 (3) | C24—Zr1—C23—C22 | −114.8 (2) |
C2—Zr1—C4—N2 | 135.23 (16) | Cl2—Zr1—C23—C22 | −127.69 (14) |
C3—Zr1—C4—N2 | 165.0 (2) | C25—Zr1—C23—C22 | −77.70 (16) |
N1—Zr1—C4—C3 | −60.15 (13) | C2—Zr1—C23—C22 | 22.9 (3) |
N2—Zr1—C4—C3 | −165.0 (2) | C3—Zr1—C23—C22 | 87.8 (2) |
C26—Zr1—C4—C3 | −126.35 (14) | C4—Zr1—C23—C22 | 79.47 (16) |
C23—Zr1—C4—C3 | 170.93 (13) | N1—Zr1—C23—C24 | 107.62 (17) |
Cl1—Zr1—C4—C3 | 95.70 (12) | N2—Zr1—C23—C24 | −176.42 (17) |
C24—Zr1—C4—C3 | 156.96 (17) | C26—Zr1—C23—C24 | 77.64 (18) |
C22—Zr1—C4—C3 | −155.69 (13) | Cl1—Zr1—C23—C24 | −91.05 (16) |
Cl2—Zr1—C4—C3 | 17.70 (14) | C22—Zr1—C23—C24 | 114.8 (2) |
C25—Zr1—C4—C3 | −132.8 (2) | Cl2—Zr1—C23—C24 | −12.87 (19) |
C2—Zr1—C4—C3 | −29.74 (13) | C25—Zr1—C23—C24 | 37.12 (16) |
N2—C4—C3—C2 | 52.1 (3) | C2—Zr1—C23—C24 | 137.7 (2) |
C5—C4—C3—C2 | −124.2 (2) | C3—Zr1—C23—C24 | −157.42 (17) |
Zr1—C4—C3—C2 | 65.7 (2) | C4—Zr1—C23—C24 | −165.71 (15) |
N2—C4—C3—Zr1 | −13.63 (19) | C22—C23—C24—C25 | −0.3 (3) |
C5—C4—C3—Zr1 | 170.06 (18) | Zr1—C23—C24—C25 | −66.77 (18) |
N1—Zr1—C3—C2 | −21.75 (13) | C22—C23—C24—Zr1 | 66.43 (17) |
N2—Zr1—C3—C2 | −119.59 (15) | N1—Zr1—C24—C23 | −104.21 (18) |
C26—Zr1—C3—C2 | −47.67 (19) | N2—Zr1—C24—C23 | 4.3 (2) |
C23—Zr1—C3—C2 | −142.33 (17) | C26—Zr1—C24—C23 | −77.83 (18) |
Cl1—Zr1—C3—C2 | 152.24 (13) | Cl1—Zr1—C24—C23 | 84.35 (16) |
C24—Zr1—C3—C2 | 144.1 (4) | C22—Zr1—C24—C23 | −37.16 (16) |
C22—Zr1—C3—C2 | −94.70 (16) | Cl2—Zr1—C24—C23 | 168.87 (16) |
Cl2—Zr1—C3—C2 | 67.84 (13) | C25—Zr1—C24—C23 | −114.8 (2) |
C25—Zr1—C3—C2 | 5.1 (3) | C2—Zr1—C24—C23 | −141.3 (2) |
C4—Zr1—C3—C2 | −127.6 (2) | C3—Zr1—C24—C23 | 92.5 (4) |
N1—Zr1—C3—C4 | 105.90 (14) | C4—Zr1—C24—C23 | 23.9 (2) |
N2—Zr1—C3—C4 | 8.06 (11) | N1—Zr1—C24—C25 | 10.6 (2) |
C26—Zr1—C3—C4 | 79.97 (17) | N2—Zr1—C24—C25 | 119.10 (16) |
C23—Zr1—C3—C4 | −14.7 (2) | C26—Zr1—C24—C25 | 37.00 (15) |
Cl1—Zr1—C3—C4 | −80.11 (12) | C23—Zr1—C24—C25 | 114.8 (2) |
C24—Zr1—C3—C4 | −88.2 (4) | Cl1—Zr1—C24—C25 | −160.82 (16) |
C22—Zr1—C3—C4 | 32.95 (17) | C22—Zr1—C24—C25 | 77.67 (17) |
Cl2—Zr1—C3—C4 | −164.52 (12) | Cl2—Zr1—C24—C25 | −76.30 (15) |
C25—Zr1—C3—C4 | 132.7 (2) | C2—Zr1—C24—C25 | −26.5 (3) |
C2—Zr1—C3—C4 | 127.6 (2) | C3—Zr1—C24—C25 | −152.7 (3) |
C14—N1—C2—C3 | 149.3 (2) | C4—Zr1—C24—C25 | 138.68 (16) |
Zr1—N1—C2—C3 | −42.6 (2) | C23—C24—C25—C26 | 0.9 (3) |
C14—N1—C2—C1 | −34.8 (3) | Zr1—C24—C25—C26 | −65.52 (17) |
Zr1—N1—C2—C1 | 133.3 (2) | C23—C24—C25—Zr1 | 66.42 (17) |
C14—N1—C2—Zr1 | −168.1 (2) | N1—Zr1—C25—C24 | −172.18 (15) |
C4—C3—C2—N1 | −33.8 (3) | N2—Zr1—C25—C24 | −86.05 (18) |
Zr1—C3—C2—N1 | 35.90 (19) | C26—Zr1—C25—C24 | −115.2 (2) |
C4—C3—C2—C1 | 150.2 (2) | C23—Zr1—C25—C24 | −37.22 (16) |
Zr1—C3—C2—C1 | −140.1 (2) | Cl1—Zr1—C25—C24 | 20.88 (17) |
C4—C3—C2—Zr1 | −69.7 (2) | C22—Zr1—C25—C24 | −77.80 (17) |
N2—Zr1—C2—N1 | −93.29 (14) | Cl2—Zr1—C25—C24 | 100.60 (15) |
C26—Zr1—C2—N1 | 4.86 (16) | C2—Zr1—C25—C24 | 168.00 (14) |
C23—Zr1—C2—N1 | −45.5 (3) | C3—Zr1—C25—C24 | 164.76 (19) |
Cl1—Zr1—C2—N1 | −172.38 (11) | C4—Zr1—C25—C24 | −105.3 (2) |
C24—Zr1—C2—N1 | 57.4 (3) | N1—Zr1—C25—C26 | −57.02 (17) |
C22—Zr1—C2—N1 | −29.99 (17) | N2—Zr1—C25—C26 | 29.1 (2) |
Cl2—Zr1—C2—N1 | 108.76 (13) | C23—Zr1—C25—C26 | 77.95 (17) |
C25—Zr1—C2—N1 | 39.93 (17) | Cl1—Zr1—C25—C26 | 136.04 (14) |
C3—Zr1—C2—N1 | −142.5 (2) | C24—Zr1—C25—C26 | 115.2 (2) |
C4—Zr1—C2—N1 | −112.63 (15) | C22—Zr1—C25—C26 | 37.37 (16) |
N1—Zr1—C2—C3 | 142.5 (2) | Cl2—Zr1—C25—C26 | −144.24 (16) |
N2—Zr1—C2—C3 | 49.17 (13) | C2—Zr1—C25—C26 | −76.83 (18) |
C26—Zr1—C2—C3 | 147.32 (14) | C3—Zr1—C25—C26 | −80.1 (3) |
C23—Zr1—C2—C3 | 97.0 (3) | C4—Zr1—C25—C26 | 9.8 (3) |
Cl1—Zr1—C2—C3 | −29.92 (14) | C24—C25—C26—C22 | −1.1 (3) |
C24—Zr1—C2—C3 | −160.1 (2) | Zr1—C25—C26—C22 | −66.73 (17) |
C22—Zr1—C2—C3 | 112.47 (15) | C24—C25—C26—Zr1 | 65.62 (17) |
Cl2—Zr1—C2—C3 | −108.78 (13) | C23—C22—C26—C25 | 0.9 (3) |
C25—Zr1—C2—C3 | −177.61 (13) | Zr1—C22—C26—C25 | 67.03 (17) |
C4—Zr1—C2—C3 | 29.82 (12) | C23—C22—C26—Zr1 | −66.13 (17) |
N1—Zr1—C2—C1 | −99.7 (3) | N1—Zr1—C26—C25 | 124.17 (16) |
N2—Zr1—C2—C1 | 167.0 (3) | N2—Zr1—C26—C25 | −158.49 (15) |
C26—Zr1—C2—C1 | −94.9 (3) | C23—Zr1—C26—C25 | −77.53 (18) |
C23—Zr1—C2—C1 | −145.2 (3) | Cl1—Zr1—C26—C25 | −61.92 (18) |
Cl1—Zr1—C2—C1 | 87.9 (3) | C24—Zr1—C26—C25 | −36.96 (16) |
C24—Zr1—C2—C1 | −42.3 (4) | C22—Zr1—C26—C25 | −114.6 (2) |
C22—Zr1—C2—C1 | −129.7 (3) | Cl2—Zr1—C26—C25 | 37.24 (17) |
Cl2—Zr1—C2—C1 | 9.0 (3) | C2—Zr1—C26—C25 | 121.64 (16) |
C25—Zr1—C2—C1 | −59.8 (3) | C3—Zr1—C26—C25 | 146.17 (15) |
C3—Zr1—C2—C1 | 117.8 (3) | C4—Zr1—C26—C25 | −175.47 (14) |
C4—Zr1—C2—C1 | 147.7 (3) | N1—Zr1—C26—C22 | −121.23 (16) |
C4—N2—C6—C11 | 114.9 (2) | N2—Zr1—C26—C22 | −43.89 (16) |
Zr1—N2—C6—C11 | −80.6 (3) | C23—Zr1—C26—C22 | 37.07 (15) |
C4—N2—C6—C7 | −67.5 (3) | Cl1—Zr1—C26—C22 | 52.68 (18) |
Zr1—N2—C6—C7 | 97.0 (3) | C24—Zr1—C26—C22 | 77.64 (17) |
C11—C6—C7—C8 | 1.2 (3) | Cl2—Zr1—C26—C22 | 151.84 (14) |
N2—C6—C7—C8 | −176.3 (2) | C25—Zr1—C26—C22 | 114.6 (2) |
C11—C6—C7—C12 | −178.5 (2) | C2—Zr1—C26—C22 | −123.76 (15) |
N2—C6—C7—C12 | 4.0 (3) | C3—Zr1—C26—C22 | −99.23 (17) |
C6—C7—C8—C9 | 0.2 (4) | C4—Zr1—C26—C22 | −60.86 (17) |
Experimental details
Crystal data | |
Chemical formula | [Zr(Cl)2(C21H25N2)(C5H5)] |
Mr | 532.64 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 10.0163 (3), 10.5990 (4), 13.1392 (5) |
α, β, γ (°) | 73.803 (1), 78.869 (2), 66.178 (1) |
V (Å3) | 1220.27 (7) |
Z | 2 |
Radiation type | Cu Kα |
µ (mm−1) | 5.82 |
Crystal size (mm) | 0.30 × 0.26 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART 6000 |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.27, 0.49 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14734, 4561, 4541 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.103, 1.13 |
No. of reflections | 4561 |
No. of parameters | 287 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.75, −1.59 |
Computer programs: APEX2 (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), UdMX (local program).
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The title compound was synthesized by ligand metathesis starting from [bis(2,6-dimethylphenyl)nacnac]ZrCl3(THF) ("nacnac" = pentane-2,4-diiminato) and cyclopentadienyl sodium. 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 dependent 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).
In contrast to these, the nacnac ligand adopts in the title complex (I), an intermediate, distorted coordination mode. An analogous coordination mode has already been observed and described for the analogous complex (Verguet et al., 2007), in which cyclopentadienyl was replaced by indenyl. The assignment of the coordination mode follows the same rational and we will point out in the following only shortly the necessary metrical data. The η3-coordinated enamito-moiety C2, C3 and N1 displays short Zr—C2 and Zr—C3 distances of 2.616 (2) and 2.620 (2) Å, respectively compared to a Zr—C4 distance of 2.826 (2) Å for the η1-coordinated imine-moiety. The C2═N1 bond is slighty longer than C4═N2 (1.354 (3) and 1.306 (3) Å, respectively). The metal center is nearly in the plane of the imine moiety (〈 (C5,C4,Zr) = 169.5 (2)°), while a more side-on coordination is observed for N1, C1–C3 (〈 (C1,C2,Zr) = 140.7 (2)°). An elongated C3—C4 distance in comparison with C2—C3 (1.462 (3) and 1.389 (3) Å, respectively) and a 44° angle between the least square planes through N1, C1–C3 and N2, C3–C5 agree with a slight loss of electron delocalization in the nacnac ligand.
Analogous to the corresponding indenyl complex (Verguet et al., 2007), 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 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 plane of the nacnac ligand was ascribed to steric reasons without any significant coordination of the carbon atoms to the metal center (Lee et al., 1999). However, a comparable nacnac coordination was observed in the five-coordinated complexes reported by Basuli et al. (2004) (CSD-codes: FAPBUU, FAPCAP, FAPCEF & FABCIJ), which was simply described as "sandwich-like".
The cyclopentadienyl ligand displays an ideal η5-coordination (ΔM–C < 3σ, Faller et al., 1985).