Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101003559/gd1128sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003559/gd1128Isup2.hkl |
CCDC reference: 166959
For related literature, see: Allan et al. (1999); Allen & Kennard (1993); Armstrong et al. (2000); Brenner et al. (1995); Chiu & Huang (1993); Clegg et al. (1997); Gibson & Wass (1999); Henderson et al. (2000).
All manipulations were carried out under a dry oxygen-free argon atmosphere, using standard Schlenk techniques. ZrCl4 was purchased from Lancaster and used as received. [Mg{N(CH2Ph)2}2] was prepared as previously described (Clegg et al., 1997). Toluene and thf were distilled over sodium and used directly from the still.
ZrCl4 (1 mmol) and [Mg{N(CH2Ph)2}2] (1 mmol) were placed in a Schlenk tube and toluene (10 ml) added. The mixture was stirred at ambient temperature for 16 h, thf (2 ml) was then added to the mixture and the remaining white solid was removed by filtration. Crystals suitable for X-ray analysis were produced by layering the yellow solution with hexane and cooling the mixture to 250 K for several weeks. 1H NMR (C6D6): δ 7.81 (d, 4H, o-H), 7.23 (t, 4H, m-H), 7.11 (t, 2H, p-H), 4.91 (s, 4H, CH2Ph), 3.91 (m, 4H, OCH2), 1.26 (m, 4H, CH2—CH2O); 13C NMR: 141.63 (i-C, Ph), 130.58 (m-C, Ph), 128.10 (o-C, Ph), 126.27 (p-C, Ph), 72.48 (OCH2), 54.43 (CH2Ph), 26.09 (CH2CH2O).
All hydrogen atoms were placed in calculated positions and in riding modes. The C atoms of the toluene molecule and the C34—C35—C36 fragment of a thf ligand were disordered over two sites and refined isotropically. All other non-H atoms were refined anisotropically. The H atoms of the methyl group of the toluene solvate were not included and indeed there is evidence that this methyl group is further disordered over at least two more sites. However, this has not been included in the model.
Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft & Nonius, 1988); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. ORTEPII (Johnson, 1976) view of (I) with atoms as 50% ellipsoids. H atoms, the toluene solvate and one of the disordered components are omitted for clarity. |
[ZrCl2(C4H8O)2(C14H14N)2]·0.5C7H8 | F(000) = 3112 |
Mr = 744.92 | Dx = 1.305 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 29.2399 (4) Å | Cell parameters from 12920 reflections |
b = 12.5188 (2) Å | θ = 2.9–27.5° |
c = 23.8447 (4) Å | µ = 0.47 mm−1 |
β = 119.6495 (6)° | T = 150 K |
V = 7585.5 (2) Å3 | Block, colourless |
Z = 8 | 0.20 × 0.15 × 0.12 mm |
Nonius Kappa CCD diffractometer | 8596 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 5092 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.054 |
ϕ & ω scans to fill Ewald sphere | θmax = 27.5°, θmin = 3.0° |
Absorption correction: multi-scan (Blessing, 1997) | h = −37→37 |
Tmin = 0.910, Tmax = 0.946 | k = −16→16 |
19143 measured reflections | l = −30→30 |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.106 | See text |
S = 0.97 | w = 1/[σ2(Fo2) + (0.036P)2] where P = (Fo2 + 2Fc2)/3 |
8596 reflections | (Δ/σ)max = 0.001 |
406 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
[ZrCl2(C4H8O)2(C14H14N)2]·0.5C7H8 | V = 7585.5 (2) Å3 |
Mr = 744.92 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 29.2399 (4) Å | µ = 0.47 mm−1 |
b = 12.5188 (2) Å | T = 150 K |
c = 23.8447 (4) Å | 0.20 × 0.15 × 0.12 mm |
β = 119.6495 (6)° |
Nonius Kappa CCD diffractometer | 8596 independent reflections |
Absorption correction: multi-scan (Blessing, 1997) | 5092 reflections with I > 2σ(I) |
Tmin = 0.910, Tmax = 0.946 | Rint = 0.054 |
19143 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.106 | See text |
S = 0.97 | Δρmax = 0.52 e Å−3 |
8596 reflections | Δρmin = −0.47 e Å−3 |
406 parameters |
Experimental. Run at EPSRC service, Southampton April 2000 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zr1 | 0.190630 (10) | 0.40064 (2) | 0.139516 (14) | 0.02450 (10) | |
Cl1 | 0.20184 (3) | 0.20824 (6) | 0.12042 (4) | 0.0335 (2) | |
Cl2 | 0.21084 (3) | 0.59213 (6) | 0.16886 (4) | 0.03002 (19) | |
O1 | 0.27213 (7) | 0.37860 (15) | 0.23085 (9) | 0.0268 (5) | |
O2 | 0.24766 (7) | 0.42676 (16) | 0.09834 (9) | 0.0302 (5) | |
N1 | 0.15438 (8) | 0.36661 (19) | 0.19179 (11) | 0.0259 (6) | |
N2 | 0.12630 (8) | 0.43497 (18) | 0.05206 (11) | 0.0252 (6) | |
C1 | 0.17255 (10) | 0.2866 (2) | 0.24363 (14) | 0.0302 (8) | |
H1A | 0.1865 | 0.3241 | 0.2855 | 0.036* | |
H1B | 0.2018 | 0.2455 | 0.2445 | 0.036* | |
C2 | 0.13015 (11) | 0.2089 (2) | 0.23674 (15) | 0.0297 (8) | |
C3 | 0.10615 (11) | 0.1413 (2) | 0.18348 (15) | 0.0343 (8) | |
H3 | 0.1159 | 0.1444 | 0.1510 | 0.041* | |
C4 | 0.06783 (12) | 0.0693 (3) | 0.17780 (17) | 0.0416 (9) | |
H4 | 0.0520 | 0.0224 | 0.1418 | 0.050* | |
C5 | 0.05290 (13) | 0.0659 (3) | 0.2241 (2) | 0.0489 (10) | |
H5 | 0.0266 | 0.0168 | 0.2199 | 0.059* | |
C6 | 0.07556 (14) | 0.1326 (3) | 0.2760 (2) | 0.0524 (10) | |
H6 | 0.0649 | 0.1301 | 0.3077 | 0.063* | |
C7 | 0.11449 (12) | 0.2046 (3) | 0.28280 (16) | 0.0404 (9) | |
H7 | 0.1303 | 0.2507 | 0.3192 | 0.049* | |
C8 | 0.10768 (10) | 0.4250 (2) | 0.18250 (14) | 0.0279 (7) | |
H8A | 0.0779 | 0.3741 | 0.1671 | 0.033* | |
H8B | 0.0984 | 0.4788 | 0.1481 | 0.033* | |
C9 | 0.11340 (11) | 0.4816 (2) | 0.24225 (14) | 0.0255 (7) | |
C10 | 0.15770 (11) | 0.5393 (2) | 0.28268 (15) | 0.0312 (8) | |
H10 | 0.1864 | 0.5411 | 0.2745 | 0.037* | |
C11 | 0.16140 (12) | 0.5947 (2) | 0.33486 (15) | 0.0346 (8) | |
H11 | 0.1926 | 0.6328 | 0.3627 | 0.041* | |
C12 | 0.11920 (13) | 0.5946 (3) | 0.34655 (16) | 0.0382 (8) | |
H12 | 0.1208 | 0.6345 | 0.3814 | 0.046* | |
C13 | 0.07505 (12) | 0.5356 (3) | 0.30656 (16) | 0.0399 (9) | |
H13 | 0.0461 | 0.5343 | 0.3142 | 0.048* | |
C14 | 0.07250 (12) | 0.4787 (3) | 0.25567 (15) | 0.0347 (8) | |
H14 | 0.0422 | 0.4369 | 0.2294 | 0.042* | |
C15 | 0.07414 (10) | 0.3842 (2) | 0.02685 (14) | 0.0294 (8) | |
H15A | 0.0479 | 0.4406 | 0.0189 | 0.035* | |
H15B | 0.0753 | 0.3359 | 0.0604 | 0.035* | |
C16 | 0.05587 (11) | 0.3212 (3) | −0.03466 (15) | 0.0307 (8) | |
C17 | 0.01610 (11) | 0.3593 (3) | −0.09315 (15) | 0.0375 (8) | |
H17 | 0.0016 | 0.4279 | −0.0948 | 0.045* | |
C18 | −0.00282 (14) | 0.2999 (3) | −0.14889 (17) | 0.0503 (10) | |
H18 | −0.0305 | 0.3272 | −0.1883 | 0.060* | |
C19 | 0.01815 (14) | 0.2024 (3) | −0.14751 (18) | 0.0546 (11) | |
H19 | 0.0053 | 0.1617 | −0.1860 | 0.065* | |
C20 | 0.05803 (14) | 0.1625 (3) | −0.0903 (2) | 0.0554 (11) | |
H20 | 0.0727 | 0.0944 | −0.0896 | 0.067* | |
C21 | 0.07711 (12) | 0.2218 (3) | −0.03341 (16) | 0.0435 (9) | |
H21 | 0.1045 | 0.1939 | 0.0060 | 0.052* | |
C22 | 0.12725 (10) | 0.5134 (2) | 0.00688 (14) | 0.0290 (8) | |
H22A | 0.1187 | 0.4760 | −0.0337 | 0.035* | |
H22B | 0.1635 | 0.5415 | 0.0254 | 0.035* | |
C23 | 0.08975 (10) | 0.6079 (2) | −0.00950 (15) | 0.0278 (7) | |
C24 | 0.08332 (11) | 0.6593 (3) | 0.03747 (15) | 0.0316 (8) | |
H24 | 0.1007 | 0.6326 | 0.0804 | 0.038* | |
C25 | 0.05181 (11) | 0.7492 (3) | 0.02266 (16) | 0.0370 (8) | |
H25 | 0.0478 | 0.7840 | 0.0554 | 0.044* | |
C26 | 0.02630 (12) | 0.7881 (3) | −0.03955 (18) | 0.0430 (9) | |
H26 | 0.0051 | 0.8503 | −0.0496 | 0.052* | |
C27 | 0.03160 (12) | 0.7366 (3) | −0.08709 (17) | 0.0468 (10) | |
H27 | 0.0134 | 0.7624 | −0.1302 | 0.056* | |
C28 | 0.06348 (11) | 0.6474 (3) | −0.07206 (15) | 0.0384 (9) | |
H28 | 0.0674 | 0.6128 | −0.1049 | 0.046* | |
C29 | 0.31142 (10) | 0.2991 (2) | 0.23802 (14) | 0.0313 (8) | |
H29A | 0.3184 | 0.3032 | 0.2015 | 0.038* | |
H29B | 0.2992 | 0.2261 | 0.2398 | 0.038* | |
C30 | 0.36037 (11) | 0.3264 (3) | 0.30073 (15) | 0.0416 (9) | |
H30A | 0.3826 | 0.3782 | 0.2937 | 0.050* | |
H30B | 0.3813 | 0.2616 | 0.3217 | 0.050* | |
C31 | 0.33861 (11) | 0.3753 (3) | 0.34087 (15) | 0.0403 (9) | |
H31A | 0.3647 | 0.4228 | 0.3748 | 0.048* | |
H31B | 0.3278 | 0.3194 | 0.3613 | 0.048* | |
C32 | 0.29136 (11) | 0.4382 (3) | 0.29103 (14) | 0.0340 (8) | |
H32A | 0.2639 | 0.4430 | 0.3037 | 0.041* | |
H32B | 0.3019 | 0.5114 | 0.2864 | 0.041* | |
C33 | 0.29067 (11) | 0.5043 (2) | 0.12059 (15) | 0.0347 (8) | |
H33A | 0.3076 | 0.5142 | 0.1679 | 0.042* | |
H33B | 0.2774 | 0.5743 | 0.0993 | 0.042* | |
C34 | 0.3183 (4) | 0.4750 (8) | 0.0837 (5) | 0.038 (3)* | 0.462 (12) |
H34A | 0.3473 | 0.4242 | 0.1086 | 0.046* | 0.462 (12) |
H34B | 0.3328 | 0.5393 | 0.0739 | 0.046* | 0.462 (12) |
C35 | 0.2760 (4) | 0.4239 (8) | 0.0223 (4) | 0.044 (3)* | 0.462 (12) |
H35A | 0.2914 | 0.3786 | 0.0018 | 0.053* | 0.462 (12) |
H35B | 0.2528 | 0.4783 | −0.0091 | 0.053* | 0.462 (12) |
C36 | 0.2464 (3) | 0.3573 (8) | 0.0471 (4) | 0.028 (3)* | 0.462 (12) |
H36A | 0.2098 | 0.3433 | 0.0126 | 0.034* | 0.462 (12) |
H36B | 0.2643 | 0.2884 | 0.0650 | 0.034* | 0.462 (12) |
C34A | 0.3296 (3) | 0.4576 (7) | 0.1022 (4) | 0.037 (2)* | 0.538 (12) |
H34C | 0.3435 | 0.5139 | 0.0854 | 0.044* | 0.538 (12) |
H34D | 0.3595 | 0.4232 | 0.1400 | 0.044* | 0.538 (12) |
C35A | 0.2981 (3) | 0.3759 (6) | 0.0503 (4) | 0.039 (2)* | 0.538 (12) |
H35C | 0.3114 | 0.3029 | 0.0655 | 0.046* | 0.538 (12) |
H35D | 0.3000 | 0.3906 | 0.0108 | 0.046* | 0.538 (12) |
C36A | 0.2409 (3) | 0.3875 (7) | 0.0371 (4) | 0.033 (2)* | 0.538 (12) |
H36C | 0.2209 | 0.4391 | 0.0018 | 0.040* | 0.538 (12) |
H36D | 0.2225 | 0.3179 | 0.0255 | 0.040* | 0.538 (12) |
C37 | 0.3013 (3) | 0.2868 (6) | 0.4855 (4) | 0.059 (2)* | 0.50 |
H37 | 0.3363 | 0.2922 | 0.4928 | 0.071* | 0.50 |
C38 | 0.26325 (18) | 0.3495 (4) | 0.4349 (2) | 0.0957 (16)* | |
H38 | 0.2686 | 0.3892 | 0.4047 | 0.115* | 0.50 |
C39 | 0.2127 (3) | 0.3431 (6) | 0.4366 (4) | 0.056 (2)* | 0.50 |
H39 | 0.1844 | 0.3876 | 0.4081 | 0.068* | 0.50 |
C40 | 0.20576 (14) | 0.2807 (3) | 0.47456 (18) | 0.0541 (10)* | |
H40 | 0.1712 | 0.2763 | 0.4686 | 0.065* | |
C41 | 0.2441 (3) | 0.2196 (6) | 0.5232 (4) | 0.056 (2)* | 0.50 |
H41 | 0.2379 | 0.1805 | 0.5529 | 0.068* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr1 | 0.02317 (15) | 0.02491 (18) | 0.02634 (18) | 0.00029 (14) | 0.01294 (13) | −0.00178 (14) |
Cl1 | 0.0308 (4) | 0.0281 (5) | 0.0407 (5) | 0.0004 (4) | 0.0170 (4) | −0.0061 (4) |
Cl2 | 0.0304 (4) | 0.0255 (4) | 0.0334 (5) | 0.0001 (4) | 0.0152 (3) | −0.0026 (4) |
O1 | 0.0243 (10) | 0.0273 (12) | 0.0280 (12) | 0.0026 (9) | 0.0123 (9) | −0.0040 (9) |
O2 | 0.0290 (11) | 0.0346 (13) | 0.0308 (13) | −0.0060 (10) | 0.0178 (10) | −0.0081 (10) |
N1 | 0.0247 (12) | 0.0250 (14) | 0.0286 (15) | −0.0001 (12) | 0.0137 (11) | 0.0008 (12) |
N2 | 0.0261 (13) | 0.0245 (14) | 0.0261 (15) | −0.0003 (11) | 0.0138 (11) | 0.0015 (12) |
C1 | 0.0261 (15) | 0.0330 (19) | 0.0300 (19) | 0.0037 (15) | 0.0127 (14) | 0.0029 (15) |
C2 | 0.0266 (15) | 0.0255 (18) | 0.035 (2) | 0.0076 (15) | 0.0135 (15) | 0.0059 (16) |
C3 | 0.0323 (17) | 0.0262 (19) | 0.040 (2) | 0.0078 (16) | 0.0142 (16) | 0.0035 (16) |
C4 | 0.0335 (18) | 0.029 (2) | 0.054 (3) | 0.0019 (16) | 0.0149 (18) | 0.0032 (17) |
C5 | 0.038 (2) | 0.031 (2) | 0.083 (3) | −0.0037 (17) | 0.034 (2) | 0.009 (2) |
C6 | 0.053 (2) | 0.049 (3) | 0.074 (3) | −0.002 (2) | 0.046 (2) | 0.009 (2) |
C7 | 0.0445 (19) | 0.039 (2) | 0.043 (2) | 0.0026 (18) | 0.0262 (18) | 0.0051 (17) |
C8 | 0.0243 (15) | 0.0287 (19) | 0.0298 (19) | 0.0047 (14) | 0.0128 (14) | 0.0051 (14) |
C9 | 0.0315 (16) | 0.0207 (17) | 0.0297 (19) | 0.0048 (15) | 0.0192 (15) | 0.0061 (14) |
C10 | 0.0350 (17) | 0.0277 (19) | 0.039 (2) | 0.0029 (16) | 0.0244 (16) | 0.0030 (16) |
C11 | 0.0436 (19) | 0.0310 (19) | 0.035 (2) | −0.0025 (17) | 0.0243 (16) | 0.0011 (16) |
C12 | 0.052 (2) | 0.039 (2) | 0.033 (2) | 0.0023 (18) | 0.0282 (17) | 0.0002 (17) |
C13 | 0.0401 (19) | 0.047 (2) | 0.046 (2) | 0.0063 (18) | 0.0320 (18) | 0.0036 (19) |
C14 | 0.0345 (17) | 0.040 (2) | 0.038 (2) | 0.0021 (16) | 0.0238 (16) | 0.0022 (17) |
C15 | 0.0282 (16) | 0.035 (2) | 0.0261 (18) | 0.0001 (15) | 0.0143 (14) | −0.0002 (15) |
C16 | 0.0246 (16) | 0.039 (2) | 0.033 (2) | −0.0086 (16) | 0.0177 (15) | −0.0037 (16) |
C17 | 0.0365 (18) | 0.040 (2) | 0.035 (2) | −0.0092 (17) | 0.0167 (17) | −0.0008 (17) |
C18 | 0.056 (2) | 0.054 (3) | 0.034 (2) | −0.023 (2) | 0.0172 (19) | −0.001 (2) |
C19 | 0.060 (2) | 0.063 (3) | 0.040 (2) | −0.022 (2) | 0.025 (2) | −0.017 (2) |
C20 | 0.052 (2) | 0.040 (2) | 0.075 (3) | −0.007 (2) | 0.033 (2) | −0.024 (2) |
C21 | 0.0334 (18) | 0.045 (2) | 0.044 (2) | −0.0030 (18) | 0.0128 (17) | −0.0127 (18) |
C22 | 0.0298 (16) | 0.032 (2) | 0.0266 (18) | −0.0014 (15) | 0.0146 (14) | 0.0000 (15) |
C23 | 0.0217 (15) | 0.0303 (19) | 0.0272 (18) | −0.0030 (15) | 0.0089 (14) | 0.0011 (15) |
C24 | 0.0264 (16) | 0.034 (2) | 0.0289 (19) | 0.0010 (15) | 0.0096 (15) | 0.0033 (16) |
C25 | 0.0293 (16) | 0.040 (2) | 0.038 (2) | −0.0018 (17) | 0.0135 (16) | −0.0028 (17) |
C26 | 0.0337 (18) | 0.037 (2) | 0.052 (3) | 0.0074 (17) | 0.0169 (18) | 0.0051 (19) |
C27 | 0.043 (2) | 0.048 (2) | 0.039 (2) | 0.0107 (19) | 0.0132 (18) | 0.0132 (19) |
C28 | 0.0344 (17) | 0.044 (2) | 0.033 (2) | 0.0011 (18) | 0.0137 (16) | 0.0024 (17) |
C29 | 0.0283 (16) | 0.0279 (19) | 0.039 (2) | 0.0068 (15) | 0.0175 (15) | 0.0013 (15) |
C30 | 0.0278 (17) | 0.035 (2) | 0.050 (2) | 0.0030 (16) | 0.0105 (17) | −0.0020 (17) |
C31 | 0.0363 (18) | 0.039 (2) | 0.033 (2) | 0.0026 (16) | 0.0077 (16) | −0.0026 (16) |
C32 | 0.0331 (17) | 0.036 (2) | 0.0280 (19) | −0.0027 (16) | 0.0114 (15) | −0.0064 (15) |
C33 | 0.0374 (17) | 0.034 (2) | 0.041 (2) | −0.0075 (16) | 0.0255 (17) | −0.0064 (16) |
Zr1—N1 | 2.041 (2) | C15—C16 | 1.512 (4) |
Zr1—N2 | 2.047 (2) | C16—C21 | 1.384 (4) |
Zr1—O1 | 2.3158 (17) | C16—C17 | 1.386 (4) |
Zr1—O2 | 2.3391 (19) | C17—C18 | 1.377 (4) |
Zr1—Cl2 | 2.4853 (8) | C18—C19 | 1.359 (5) |
Zr1—Cl1 | 2.5027 (8) | C19—C20 | 1.376 (5) |
O1—C32 | 1.461 (3) | C20—C21 | 1.398 (5) |
O1—C29 | 1.465 (3) | C22—C23 | 1.527 (4) |
O2—C36A | 1.460 (8) | C23—C24 | 1.382 (4) |
O2—C33 | 1.465 (3) | C23—C28 | 1.388 (4) |
O2—C36 | 1.485 (9) | C24—C25 | 1.385 (4) |
N1—C8 | 1.466 (3) | C25—C26 | 1.378 (4) |
N1—C1 | 1.471 (3) | C26—C27 | 1.377 (4) |
N2—C22 | 1.468 (3) | C27—C28 | 1.384 (4) |
N2—C15 | 1.478 (3) | C29—C30 | 1.511 (4) |
C1—C2 | 1.519 (4) | C30—C31 | 1.516 (4) |
C2—C7 | 1.384 (4) | C31—C32 | 1.522 (4) |
C2—C3 | 1.393 (4) | C33—C34 | 1.504 (9) |
C3—C4 | 1.392 (4) | C33—C34A | 1.525 (8) |
C4—C5 | 1.374 (5) | C34—C35 | 1.515 (11) |
C5—C6 | 1.363 (5) | C35—C36 | 1.516 (12) |
C6—C7 | 1.397 (4) | C34A—C35A | 1.516 (10) |
C8—C9 | 1.524 (4) | C35A—C36A | 1.545 (11) |
C9—C10 | 1.377 (4) | C37—C40i | 1.363 (8) |
C9—C14 | 1.383 (4) | C37—C38 | 1.409 (8) |
C10—C11 | 1.381 (4) | C38—C39 | 1.500 (8) |
C11—C12 | 1.393 (4) | C39—C40 | 1.286 (8) |
C12—C13 | 1.380 (4) | C40—C41 | 1.378 (8) |
C13—C14 | 1.377 (4) | C41—C40i | 1.442 (8) |
N1—Zr1—N2 | 99.95 (9) | C14—C9—C8 | 119.8 (3) |
N1—Zr1—O1 | 90.25 (8) | C9—C10—C11 | 121.5 (3) |
N2—Zr1—O1 | 169.26 (8) | C10—C11—C12 | 119.8 (3) |
N1—Zr1—O2 | 168.22 (8) | C13—C12—C11 | 118.7 (3) |
N2—Zr1—O2 | 91.70 (8) | C14—C13—C12 | 120.7 (3) |
O1—Zr1—O2 | 78.22 (7) | C13—C14—C9 | 121.0 (3) |
N1—Zr1—Cl2 | 98.76 (7) | N2—C15—C16 | 114.7 (2) |
N2—Zr1—Cl2 | 93.15 (7) | C21—C16—C17 | 118.4 (3) |
O1—Zr1—Cl2 | 81.92 (5) | C21—C16—C15 | 120.6 (3) |
O2—Zr1—Cl2 | 82.17 (5) | C17—C16—C15 | 121.0 (3) |
N1—Zr1—Cl1 | 93.70 (7) | C18—C17—C16 | 121.4 (3) |
N2—Zr1—Cl1 | 98.85 (7) | C19—C18—C17 | 120.0 (3) |
O1—Zr1—Cl1 | 83.69 (5) | C18—C19—C20 | 120.0 (4) |
O2—Zr1—Cl1 | 82.73 (5) | C19—C20—C21 | 120.3 (4) |
Cl2—Zr1—Cl1 | 160.95 (3) | C16—C21—C20 | 119.8 (3) |
C32—O1—C29 | 109.5 (2) | N2—C22—C23 | 115.7 (2) |
C32—O1—Zr1 | 125.45 (16) | C24—C23—C28 | 118.7 (3) |
C29—O1—Zr1 | 124.99 (15) | C24—C23—C22 | 121.4 (3) |
C36A—O2—C33 | 104.6 (3) | C28—C23—C22 | 119.8 (3) |
C36A—O2—C36 | 16.9 (5) | C23—C24—C25 | 120.7 (3) |
C33—O2—C36 | 110.7 (4) | C26—C25—C24 | 119.9 (3) |
C36A—O2—Zr1 | 127.0 (3) | C27—C26—C25 | 120.0 (3) |
C33—O2—Zr1 | 127.11 (16) | C26—C27—C28 | 120.0 (3) |
C36—O2—Zr1 | 122.0 (3) | C27—C28—C23 | 120.6 (3) |
C8—N1—C1 | 112.9 (2) | O1—C29—C30 | 105.4 (2) |
C8—N1—Zr1 | 122.02 (18) | C29—C30—C31 | 103.2 (2) |
C1—N1—Zr1 | 125.07 (17) | C30—C31—C32 | 102.6 (3) |
C22—N2—C15 | 112.3 (2) | O1—C32—C31 | 105.2 (2) |
C22—N2—Zr1 | 123.13 (17) | O2—C33—C34 | 103.9 (4) |
C15—N2—Zr1 | 124.58 (18) | O2—C33—C34A | 105.8 (4) |
N1—C1—C2 | 114.1 (2) | C34—C33—C34A | 17.3 (5) |
C7—C2—C3 | 119.0 (3) | C33—C34—C35 | 104.5 (6) |
C7—C2—C1 | 120.8 (3) | C34—C35—C36 | 101.9 (7) |
C3—C2—C1 | 120.2 (3) | O2—C36—C35 | 102.3 (6) |
C4—C3—C2 | 120.0 (3) | C35A—C34A—C33 | 104.6 (5) |
C5—C4—C3 | 120.2 (3) | C34A—C35A—C36A | 105.3 (6) |
C6—C5—C4 | 120.4 (3) | O2—C36A—C35A | 103.3 (5) |
C5—C6—C7 | 120.2 (3) | C40i—C37—C38 | 128.0 (6) |
C2—C7—C6 | 120.3 (3) | C37—C38—C39 | 108.6 (6) |
N1—C8—C9 | 115.3 (2) | C40—C39—C38 | 123.6 (6) |
C10—C9—C14 | 118.3 (3) | C39—C40—C41 | 125.7 (6) |
C10—C9—C8 | 121.9 (3) | C40—C41—C40i | 114.9 (6) |
N1—Zr1—O1—C32 | −58.0 (2) | C8—C9—C10—C11 | 176.7 (3) |
N2—Zr1—O1—C32 | 104.0 (5) | C9—C10—C11—C12 | −1.4 (5) |
O2—Zr1—O1—C32 | 124.5 (2) | C10—C11—C12—C13 | 2.2 (5) |
Cl2—Zr1—O1—C32 | 40.8 (2) | C11—C12—C13—C14 | −0.6 (5) |
Cl1—Zr1—O1—C32 | −151.7 (2) | C12—C13—C14—C9 | −1.8 (5) |
N1—Zr1—O1—C29 | 119.1 (2) | C10—C9—C14—C13 | 2.6 (5) |
N2—Zr1—O1—C29 | −78.9 (5) | C8—C9—C14—C13 | −175.1 (3) |
O2—Zr1—O1—C29 | −58.44 (19) | C22—N2—C15—C16 | 62.0 (3) |
Cl2—Zr1—O1—C29 | −142.1 (2) | Zr1—N2—C15—C16 | −117.7 (2) |
Cl1—Zr1—O1—C29 | 25.42 (19) | N2—C15—C16—C21 | 75.4 (4) |
N1—Zr1—O2—C36A | 127.0 (6) | N2—C15—C16—C17 | −107.2 (3) |
N2—Zr1—O2—C36A | −44.7 (5) | C21—C16—C17—C18 | 1.0 (5) |
O1—Zr1—O2—C36A | 139.1 (5) | C15—C16—C17—C18 | −176.4 (3) |
Cl2—Zr1—O2—C36A | −137.6 (5) | C16—C17—C18—C19 | −1.1 (5) |
Cl1—Zr1—O2—C36A | 54.0 (5) | C17—C18—C19—C20 | 0.5 (5) |
N1—Zr1—O2—C33 | −67.9 (5) | C18—C19—C20—C21 | 0.2 (5) |
N2—Zr1—O2—C33 | 120.4 (2) | C17—C16—C21—C20 | −0.3 (5) |
O1—Zr1—O2—C33 | −55.8 (2) | C15—C16—C21—C20 | 177.1 (3) |
Cl2—Zr1—O2—C33 | 27.5 (2) | C19—C20—C21—C16 | −0.2 (5) |
Cl1—Zr1—O2—C33 | −140.9 (2) | C15—N2—C22—C23 | 61.2 (3) |
N1—Zr1—O2—C36 | 107.4 (6) | Zr1—N2—C22—C23 | −119.2 (2) |
N2—Zr1—O2—C36 | −64.3 (5) | N2—C22—C23—C24 | 42.2 (4) |
O1—Zr1—O2—C36 | 119.4 (5) | N2—C22—C23—C28 | −141.3 (3) |
Cl2—Zr1—O2—C36 | −157.3 (5) | C28—C23—C24—C25 | −0.8 (4) |
Cl1—Zr1—O2—C36 | 34.4 (5) | C22—C23—C24—C25 | 175.7 (3) |
N2—Zr1—N1—C8 | −36.9 (2) | C23—C24—C25—C26 | 0.3 (4) |
O1—Zr1—N1—C8 | 139.8 (2) | C24—C25—C26—C27 | 0.9 (5) |
O2—Zr1—N1—C8 | 151.6 (3) | C25—C26—C27—C28 | −1.5 (5) |
Cl2—Zr1—N1—C8 | 57.9 (2) | C26—C27—C28—C23 | 0.9 (5) |
Cl1—Zr1—N1—C8 | −136.53 (19) | C24—C23—C28—C27 | 0.2 (4) |
N2—Zr1—N1—C1 | 145.9 (2) | C22—C23—C28—C27 | −176.4 (3) |
O1—Zr1—N1—C1 | −37.5 (2) | C32—O1—C29—C30 | −10.9 (3) |
O2—Zr1—N1—C1 | −25.7 (5) | Zr1—O1—C29—C30 | 171.60 (18) |
Cl2—Zr1—N1—C1 | −119.3 (2) | O1—C29—C30—C31 | 30.2 (3) |
Cl1—Zr1—N1—C1 | 46.2 (2) | C29—C30—C31—C32 | −37.4 (3) |
N1—Zr1—N2—C22 | 147.7 (2) | C29—O1—C32—C31 | −12.9 (3) |
O1—Zr1—N2—C22 | −14.0 (6) | Zr1—O1—C32—C31 | 164.62 (18) |
O2—Zr1—N2—C22 | −34.0 (2) | C30—C31—C32—O1 | 31.2 (3) |
Cl2—Zr1—N2—C22 | 48.3 (2) | C36A—O2—C33—C34 | −20.1 (7) |
Cl1—Zr1—N2—C22 | −116.9 (2) | C36—O2—C33—C34 | −3.5 (7) |
N1—Zr1—N2—C15 | −32.7 (2) | Zr1—O2—C33—C34 | 172.2 (5) |
O1—Zr1—N2—C15 | 165.6 (3) | C36A—O2—C33—C34A | −37.9 (7) |
O2—Zr1—N2—C15 | 145.6 (2) | C36—O2—C33—C34A | −21.3 (7) |
Cl2—Zr1—N2—C15 | −132.1 (2) | Zr1—O2—C33—C34A | 154.4 (4) |
Cl1—Zr1—N2—C15 | 62.7 (2) | O2—C33—C34—C35 | 27.3 (7) |
C8—N1—C1—C2 | 53.0 (3) | C34A—C33—C34—C35 | 126 (2) |
Zr1—N1—C1—C2 | −129.5 (2) | C33—C34—C35—C36 | −40.5 (9) |
N1—C1—C2—C7 | −117.4 (3) | C36A—O2—C36—C35 | 50.1 (17) |
N1—C1—C2—C3 | 62.2 (4) | C33—O2—C36—C35 | −21.4 (9) |
C7—C2—C3—C4 | −1.3 (4) | Zr1—O2—C36—C35 | 162.7 (5) |
C1—C2—C3—C4 | 179.1 (2) | C34—C35—C36—O2 | 37.1 (9) |
C2—C3—C4—C5 | 1.1 (5) | O2—C33—C34A—C35A | 19.4 (6) |
C3—C4—C5—C6 | −0.2 (5) | C34—C33—C34A—C35A | −66.7 (19) |
C4—C5—C6—C7 | −0.4 (5) | C33—C34A—C35A—C36A | 5.1 (8) |
C3—C2—C7—C6 | 0.6 (4) | C33—O2—C36A—C35A | 40.4 (7) |
C1—C2—C7—C6 | −179.8 (3) | C36—O2—C36A—C35A | −73.2 (18) |
C5—C6—C7—C2 | 0.2 (5) | Zr1—O2—C36A—C35A | −151.8 (4) |
C1—N1—C8—C9 | 56.3 (3) | C34A—C35A—C36A—O2 | −27.7 (9) |
Zr1—N1—C8—C9 | −121.2 (2) | C40i—C37—C38—C39 | 8.0 (10) |
N1—C8—C9—C10 | 43.9 (4) | C37—C38—C39—C40 | −6.7 (9) |
N1—C8—C9—C14 | −138.5 (3) | C38—C39—C40—C41 | 7.1 (11) |
C14—C9—C10—C11 | −1.0 (5) | C39—C40—C41—C40i | −6.9 (9) |
Symmetry code: (i) −x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [ZrCl2(C4H8O)2(C14H14N)2]·0.5C7H8 |
Mr | 744.92 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 150 |
a, b, c (Å) | 29.2399 (4), 12.5188 (2), 23.8447 (4) |
β (°) | 119.6495 (6) |
V (Å3) | 7585.5 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.47 |
Crystal size (mm) | 0.20 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Nonius Kappa CCD diffractometer |
Absorption correction | Multi-scan (Blessing, 1997) |
Tmin, Tmax | 0.910, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19143, 8596, 5092 |
Rint | 0.054 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.106, 0.97 |
No. of reflections | 8596 |
No. of parameters | 406 |
H-atom treatment | See text |
Δρmax, Δρmin (e Å−3) | 0.52, −0.47 |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft & Nonius, 1988), DENZO and COLLECT, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXL97.
Zr1—N1 | 2.041 (2) | Zr1—O2 | 2.3391 (19) |
Zr1—N2 | 2.047 (2) | Zr1—Cl2 | 2.4853 (8) |
Zr1—O1 | 2.3158 (17) | Zr1—Cl1 | 2.5027 (8) |
N1—Zr1—N2 | 99.95 (9) | O1—Zr1—Cl2 | 81.92 (5) |
N1—Zr1—O1 | 90.25 (8) | O2—Zr1—Cl2 | 82.17 (5) |
N2—Zr1—O1 | 169.26 (8) | N1—Zr1—Cl1 | 93.70 (7) |
N1—Zr1—O2 | 168.22 (8) | N2—Zr1—Cl1 | 98.85 (7) |
N2—Zr1—O2 | 91.70 (8) | O1—Zr1—Cl1 | 83.69 (5) |
O1—Zr1—O2 | 78.22 (7) | O2—Zr1—Cl1 | 82.73 (5) |
N1—Zr1—Cl2 | 98.76 (7) | Cl2—Zr1—Cl1 | 160.95 (3) |
N2—Zr1—Cl2 | 93.15 (7) |
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Interest in zirconium complexes has risen in recent years due to their utility in a number of processes, most notably as catalysts in olefin polymerization (Gibson & Wass, 1999) and as precursors for chemical vapour deposition (Chiu & Huang, 1993). We have recently been interested in the ability of zirconium amides to catalyse ethylene polymerization (Armstrong et al., 2000), and as part of this study we have prepared and structurally characterized the complex [{(PhCH2)2N}2ZrCl2(thf)2], (I), as a hemi-toluene solvate. A search of the Cambridge Structural Database (Allen & Kennard, 1993) revealed only two complexes closely related to (I), namely [(Me2N)2ZrCl2(thf)2], (II) and [(Et2N)2ZrCl2(thf)2], (III) (Brenner et al., 1995). Both of these complexes were formed by the ligand redistribution reaction of ZrCl4 with equimolar amounts of the appropriate tetraamide, Zr(NR2)4. In contrast, the synthesis of (I) was achieved by the treatment of ZrCl4 with the rather unusual reagent [Mg{N(CH2Ph)2}2] (Clegg et al., 1997). Despite the current interest in the ability of magnesium bisamides to act as strong bases in deprotonation reactions (Henderson et al., 2000; Allan et al., 1999) this is, to our knowledge, the first example of using such compounds as ligand transfer reagents. \sch
The molecular structure of (I) is similar to those of (II) and (III) in that the Zr atom exists in a distorted octahedral enviroment with mutually trans chloro ligands [Cl1—Zr1—Cl2 160.96 (3)°], mutually cis amides [N1—Zr1—N2 99.98 (9)°] and mutually cis thf ligands [O1—Zr1—O2 78.27 (7)°]. It is obvious from these angles, and the others given in Table 1, that the distortion from an octahedral geometry is steric in nature, with the angles involving the bulky amide ligands widening and the angles between the smaller ligands being compressed to compensate. A comparison with the corresponding distortions found for the NMe2 and NEt2 analogues (II) and (III) is interesting. The Cl—Zr—Cl, N—Zr—N and O—Zr—O angles in (II) are 163.14 (3), 98.37 (12) and 81.45 (8)°, respectively. These are, as expected, all closer to ideal octahedral values than those found for the bulkier (I). However, the corresponding values for III are 163.11 (10), 101.5 (3) and 76.8 (2)°, respectively. These much greater distortions from octahedral geometry than found in (II) were explained by Brenner et al. (1995) as being due to the increased steric bulk of ethyl over methyl. As (I) shows values intermediate between those of (II) and (III) (despite its greater steric requirements) this raises the possibility that the observed large differences between (II) and (III) are not solely due to considerations of size but result from a combination of intra and intermolecular interactions and the disorder present in all the organic parts of (III). This is further supported in that the Cl—Zr—Cl angle of (III), which is not directly affected by disorder, shows the expected smaller distortion from 180° than that found in (I). Although the Zr to O distances are slightly asymmetrical [Zr1—O1 2.3158 (17), Zr1—O2 2.3391 (19) Å] all the bond lengths found in (I) are unexceptional and both the N and the O atoms have essentially planar coordination geometries. There is some peripheral disorder present. The toluene solvate is disordered about a crystallographic inversion centre and the atoms C34 C35 and C36 of one of the thf ligands are also modeled over two sets of sites, with refined site-occupation factors 0.462 (12) and 0.538 (12).