Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103010035/na1614sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103010035/na1614Isup2.hkl |
CCDC reference: 214380
Single crystals were obtained by cooling from CH2Cl2 solution at 253 K. The crystal used in the analysis was sealed in a Lindemann capillary under a nitrogen atmosphere.
Reflections corresponding to systematic absences were not collected. All H atoms were positioned stereochemically, with the exception of the H atoms bonded to atoms N2 and C10, which were found from a difference Fourier synthesis. All H atoms were refined as riding, with Uiso values equal to Ueq of the carrier atom. The disorder of the CH2Cl2 solvent molecule has been modeled without constraints on the basis of three partially superimposed sites (A, B and C) with occupancy factors 0.4, 0.4 and 1/5, respectively. Seemingly, site B is obtained from site A by rotation around the Cl6A—C17A bond, and site C from site A by rotation around the Cl7A—C17A bond. Furthermore, if the solvent molecule and its nearest centrosymmetrically related molecule are considered, some of the possible relative orientations are not allowed because of the close contacts between Cl atoms.
Data collection: MACH3/PC & CAD-4-PC (Nonius, 1996); cell refinement: CELLFIT (Centore, 2002); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).
Fig. 1. A view of the cation and anion of (I), with displacement ellipsoids shown at the 30% probability level. One of the three positions of the solvent molecule is also shown. |
(C16H29N2Si)2[Zr2Cl10]·2CH2Cl2 | F(000) = 2560 |
Mr = 1261.80 | Dx = 1.463 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 25 reflections |
a = 19.61 (5) Å | θ = 28.2–29.4° |
b = 17.350 (2) Å | µ = 1.09 mm−1 |
c = 16.832 (2) Å | T = 293 K |
V = 5727 (15) Å3 | Prism, white |
Z = 4 | 0.60 × 0.50 × 0.30 mm |
Enraf Nonius MACH3 diffractometer | 4109 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 28.0°, θmin = 2.0° |
non–profiled ω/2θ scans | h = 0→25 |
Absorption correction: ϕ scan North et al. (1968). The number of ψ scan sets used was 3. Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied. | k = 0→22 |
Tmin = 0.503, Tmax = 0.721 | l = 0→22 |
6872 measured reflections | 1 standard reflections every 126 min |
6872 independent reflections | intensity decay: none |
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0624P)2 + 7.0008P] where P = (Fo2 + 2Fc2)/3 |
6872 reflections | (Δ/σ)max = 0.002 |
261 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.55 e Å−3 |
(C16H29N2Si)2[Zr2Cl10]·2CH2Cl2 | V = 5727 (15) Å3 |
Mr = 1261.80 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 19.61 (5) Å | µ = 1.09 mm−1 |
b = 17.350 (2) Å | T = 293 K |
c = 16.832 (2) Å | 0.60 × 0.50 × 0.30 mm |
Enraf Nonius MACH3 diffractometer | 4109 reflections with I > 2σ(I) |
Absorption correction: ϕ scan North et al. (1968). The number of ψ scan sets used was 3. Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied. | Rint = 0.000 |
Tmin = 0.503, Tmax = 0.721 | 1 standard reflections every 126 min |
6872 measured reflections | intensity decay: none |
6872 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.67 e Å−3 |
6872 reflections | Δρmin = −0.55 e Å−3 |
261 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. 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. ******DISORDER OF THE SOLVENT MOLECULE****** The disorder of the CH2Cl2solvent molecule has been modeled on the basis of three partially superimposed sites (A, B, C) with occupancy factors 0.4, 0.4 and 0.2 respectively. Seemingly, site B is obtained from A by rotation around the bond CL6A—C17A, and site C from site A by rotation around the bond CL7A—C17A. Furthermore, if the molecule and its nearest centrosymmetrically related one are considered, not all the possible orientations of the three sites are allowed, but B—B, B—C and C—B are forbidden since they give too close contacts between CL atoms. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Zr1 | 0.96881 (2) | −0.54489 (2) | 0.10439 (3) | 0.03928 (12) | |
Si1 | 0.68405 (7) | −0.31647 (8) | 0.32674 (9) | 0.0538 (3) | |
Cl1 | 0.85645 (6) | −0.56518 (8) | 0.15514 (9) | 0.0617 (3) | |
Cl2 | 0.97332 (6) | −0.66989 (7) | 0.04251 (8) | 0.0585 (3) | |
Cl3 | 1.08104 (5) | −0.51165 (7) | 0.02703 (7) | 0.0470 (3) | |
Cl4 | 0.97128 (7) | −0.41410 (7) | 0.15402 (8) | 0.0605 (3) | |
Cl5 | 1.03420 (7) | −0.58774 (9) | 0.21637 (8) | 0.0689 (4) | |
Cl6A | 0.8717 (3) | −0.4551 (3) | 0.3642 (3) | 0.196 (2) | 0.40 |
Cl6B | 0.8717 (3) | −0.4551 (3) | 0.3642 (3) | 0.196 (2) | 0.40 |
Cl7A | 0.9820 (3) | −0.3630 (4) | 0.3818 (4) | 0.200 (3) | 0.40 |
Cl7C | 0.9820 (3) | −0.3630 (4) | 0.3818 (4) | 0.200 (3) | 0.20 |
Cl8 | 0.9965 (7) | −0.4607 (8) | 0.4376 (8) | 0.243 (5)* | 0.40 |
Cl9 | 0.9561 (10) | −0.5285 (12) | 0.4243 (13) | 0.184 (7)* | 0.20 |
N1 | 0.75165 (17) | −0.2529 (2) | 0.2899 (2) | 0.0427 (8) | |
N2 | 0.82984 (19) | −0.2069 (2) | 0.1969 (2) | 0.0496 (9) | |
H2 | 0.8544 | −0.1943 | 0.2365 | 0.050* | |
C1 | 0.7767 (2) | −0.2503 (2) | 0.2168 (3) | 0.0418 (10) | |
C2 | 0.7461 (2) | −0.2976 (2) | 0.1533 (3) | 0.0402 (9) | |
C3 | 0.7802 (2) | −0.3618 (3) | 0.1248 (3) | 0.0514 (12) | |
H3 | 0.8226 | −0.3751 | 0.1455 | 0.051* | |
C4 | 0.7513 (3) | −0.4059 (3) | 0.0660 (3) | 0.0605 (13) | |
H4 | 0.7745 | −0.4486 | 0.0465 | 0.060* | |
C5 | 0.6884 (3) | −0.3872 (3) | 0.0358 (3) | 0.0641 (14) | |
H5 | 0.6682 | −0.4182 | −0.0026 | 0.064* | |
C6 | 0.6553 (3) | −0.3222 (3) | 0.0628 (3) | 0.0612 (14) | |
H6 | 0.6134 | −0.3086 | 0.0411 | 0.061* | |
C7 | 0.6833 (2) | −0.2774 (3) | 0.1214 (3) | 0.0504 (11) | |
H7 | 0.6605 | −0.2338 | 0.1395 | 0.050* | |
C8 | 0.7742 (2) | −0.1966 (3) | 0.3524 (3) | 0.0509 (11) | |
H8 | 0.7418 | −0.2030 | 0.3962 | 0.051* | |
C9 | 0.7673 (3) | −0.1129 (3) | 0.3270 (3) | 0.0650 (14) | |
H9A | 0.7224 | −0.1043 | 0.3062 | 0.065* | |
H9B | 0.8005 | −0.1016 | 0.2868 | 0.065* | |
H9C | 0.7746 | −0.0800 | 0.3721 | 0.065* | |
C10 | 0.8431 (3) | −0.2166 (4) | 0.3870 (3) | 0.0705 (16) | |
H10A | 0.8407 | −0.2637 | 0.4109 | 0.070* | |
H10B | 0.8552 | −0.1780 | 0.4271 | 0.070* | |
H10C | 0.8792 | −0.2200 | 0.3495 | 0.070* | |
C11 | 0.8519 (2) | −0.1865 (3) | 0.1151 (3) | 0.0510 (12) | |
H11 | 0.8236 | −0.2147 | 0.0770 | 0.051* | |
C12 | 0.8405 (3) | −0.1010 (3) | 0.1039 (4) | 0.0715 (16) | |
H12A | 0.7932 | −0.0892 | 0.1121 | 0.071* | |
H12B | 0.8534 | −0.0866 | 0.0509 | 0.071* | |
H12C | 0.8677 | −0.0729 | 0.1415 | 0.071* | |
C13 | 0.9247 (3) | −0.2092 (3) | 0.1035 (3) | 0.0714 (16) | |
H13A | 0.9291 | −0.2640 | 0.1093 | 0.071* | |
H13B | 0.9526 | −0.1838 | 0.1423 | 0.071* | |
H13C | 0.9392 | −0.1944 | 0.0512 | 0.071* | |
C14 | 0.6716 (3) | −0.4056 (3) | 0.2697 (4) | 0.0797 (19) | |
H14A | 0.6574 | −0.3931 | 0.2167 | 0.080* | |
H14B | 0.6372 | −0.4366 | 0.2948 | 0.080* | |
H14C | 0.7136 | −0.4339 | 0.2677 | 0.080* | |
C15 | 0.6081 (3) | −0.2556 (4) | 0.3301 (4) | 0.088 (2) | |
H15A | 0.6175 | −0.2102 | 0.3608 | 0.088* | |
H15B | 0.5713 | −0.2836 | 0.3541 | 0.088* | |
H15C | 0.5955 | −0.2409 | 0.2770 | 0.088* | |
C16 | 0.7107 (3) | −0.3478 (3) | 0.4273 (3) | 0.0772 (17) | |
H16A | 0.7183 | −0.3034 | 0.4601 | 0.077* | |
H16B | 0.7520 | −0.3772 | 0.4235 | 0.077* | |
H16C | 0.6755 | −0.3791 | 0.4504 | 0.077* | |
C17A | 0.9568 (10) | −0.4600 (11) | 0.3580 (6) | 0.256 (10) | 0.40 |
C17B | 0.9568 (10) | −0.4600 (11) | 0.3580 (6) | 0.256 (10) | 0.40 |
C17C | 0.9568 (10) | −0.4600 (11) | 0.3580 (6) | 0.256 (10) | 0.20 |
H17A | 0.9715 | −0.4741 | 0.3050 | 0.256* | 0.40 |
H18A | 0.9755 | −0.4964 | 0.3959 | 0.256* | 0.40 |
H17B | 0.9692 | −0.5054 | 0.3277 | 0.256* | 0.40 |
H18B | 0.9722 | −0.4154 | 0.3283 | 0.256* | 0.40 |
H17C | 0.9114 | −0.4569 | 0.3353 | 0.256* | 0.20 |
H18C | 0.9868 | −0.4769 | 0.3157 | 0.256* | 0.20 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr1 | 0.0370 (2) | 0.0354 (2) | 0.0455 (2) | −0.00041 (17) | 0.00024 (19) | 0.00417 (18) |
Si1 | 0.0500 (7) | 0.0499 (8) | 0.0613 (9) | −0.0133 (6) | 0.0114 (6) | 0.0051 (7) |
Cl1 | 0.0468 (6) | 0.0572 (7) | 0.0811 (9) | −0.0039 (5) | 0.0207 (6) | 0.0070 (7) |
Cl2 | 0.0621 (7) | 0.0390 (6) | 0.0745 (8) | −0.0052 (5) | 0.0088 (7) | −0.0079 (6) |
Cl3 | 0.0309 (5) | 0.0580 (7) | 0.0521 (6) | −0.0032 (5) | −0.0044 (5) | 0.0111 (5) |
Cl4 | 0.0674 (8) | 0.0406 (6) | 0.0734 (8) | −0.0017 (6) | −0.0021 (7) | −0.0068 (6) |
Cl5 | 0.0750 (9) | 0.0797 (9) | 0.0521 (7) | 0.0276 (7) | −0.0112 (7) | 0.0079 (7) |
Cl6A | 0.160 (3) | 0.257 (6) | 0.172 (4) | −0.051 (4) | 0.027 (3) | −0.054 (4) |
Cl6B | 0.160 (3) | 0.257 (6) | 0.172 (4) | −0.051 (4) | 0.027 (3) | −0.054 (4) |
Cl7A | 0.154 (4) | 0.206 (6) | 0.239 (7) | −0.014 (4) | 0.009 (4) | −0.115 (6) |
Cl7C | 0.154 (4) | 0.206 (6) | 0.239 (7) | −0.014 (4) | 0.009 (4) | −0.115 (6) |
N1 | 0.0402 (18) | 0.0426 (19) | 0.045 (2) | −0.0060 (16) | 0.0027 (17) | 0.0024 (17) |
N2 | 0.048 (2) | 0.060 (2) | 0.041 (2) | −0.0168 (18) | 0.0011 (17) | −0.0001 (19) |
C1 | 0.039 (2) | 0.037 (2) | 0.050 (3) | −0.0016 (18) | 0.000 (2) | 0.005 (2) |
C2 | 0.039 (2) | 0.033 (2) | 0.049 (2) | −0.0043 (17) | 0.003 (2) | −0.0002 (19) |
C3 | 0.043 (2) | 0.049 (3) | 0.062 (3) | 0.007 (2) | 0.003 (2) | −0.001 (2) |
C4 | 0.070 (3) | 0.040 (3) | 0.072 (3) | 0.002 (2) | 0.009 (3) | −0.011 (3) |
C5 | 0.077 (4) | 0.054 (3) | 0.061 (3) | −0.013 (3) | −0.011 (3) | −0.008 (3) |
C6 | 0.056 (3) | 0.050 (3) | 0.077 (4) | 0.002 (2) | −0.018 (3) | −0.002 (3) |
C7 | 0.047 (3) | 0.039 (2) | 0.065 (3) | 0.004 (2) | −0.005 (2) | 0.001 (2) |
C8 | 0.055 (3) | 0.055 (3) | 0.043 (3) | −0.013 (2) | 0.002 (2) | −0.001 (2) |
C9 | 0.079 (4) | 0.052 (3) | 0.065 (3) | −0.005 (3) | 0.003 (3) | −0.009 (3) |
C10 | 0.068 (4) | 0.077 (4) | 0.066 (4) | −0.020 (3) | −0.012 (3) | 0.009 (3) |
C11 | 0.053 (3) | 0.057 (3) | 0.043 (3) | −0.017 (2) | 0.007 (2) | 0.002 (2) |
C12 | 0.073 (4) | 0.068 (4) | 0.073 (4) | 0.006 (3) | 0.009 (3) | 0.025 (3) |
C13 | 0.078 (4) | 0.065 (3) | 0.072 (4) | 0.005 (3) | 0.027 (3) | 0.004 (3) |
C14 | 0.097 (4) | 0.059 (3) | 0.084 (4) | −0.034 (3) | 0.017 (4) | 0.009 (3) |
C15 | 0.050 (3) | 0.096 (5) | 0.117 (6) | −0.003 (3) | 0.019 (3) | 0.009 (4) |
C16 | 0.092 (4) | 0.070 (4) | 0.070 (4) | −0.023 (3) | 0.014 (3) | 0.017 (3) |
C17A | 0.35 (2) | 0.34 (2) | 0.072 (6) | 0.240 (19) | 0.003 (9) | −0.021 (9) |
C17B | 0.35 (2) | 0.34 (2) | 0.072 (6) | 0.240 (19) | 0.003 (9) | −0.021 (9) |
C17C | 0.35 (2) | 0.34 (2) | 0.072 (6) | 0.240 (19) | 0.003 (9) | −0.021 (9) |
Zr1—Cl1 | 2.389 (5) | C8—C9 | 1.519 (7) |
Zr1—Cl2 | 2.408 (6) | C8—H8 | 0.9800 |
Zr1—Cl3 | 2.622 (5) | C9—H9A | 0.9600 |
Zr1—Cl3i | 2.610 (7) | C9—H9B | 0.9600 |
Zr1—Cl4 | 2.419 (6) | C9—H9C | 0.9600 |
Zr1—Cl5 | 2.398 (6) | C10—H10A | 0.9128 |
Si1—C15 | 1.827 (7) | C10—H10B | 0.9801 |
Si1—N1 | 1.833 (4) | C10—H10C | 0.9494 |
Si1—C14 | 1.837 (6) | C11—C13 | 1.493 (8) |
Si1—C16 | 1.853 (6) | C11—C12 | 1.512 (7) |
Cl3—Zr1i | 2.610 (7) | C11—H11 | 0.9800 |
Cl6A—C17A | 1.674 (18) | C12—H12A | 0.9600 |
Cl7A—C17A | 1.80 (2) | C12—H12B | 0.9600 |
Cl8—C17A | 1.550 (18) | C12—H12C | 0.9600 |
Cl9—C17A | 1.63 (2) | C13—H13A | 0.9600 |
N1—C1 | 1.325 (5) | C13—H13B | 0.9600 |
N1—C8 | 1.503 (6) | C13—H13C | 0.9600 |
N2—C1 | 1.329 (6) | C14—H14A | 0.9600 |
N2—C11 | 1.485 (6) | C14—H14B | 0.9600 |
N2—H2 | 0.8502 | C14—H14C | 0.9600 |
C1—C2 | 1.474 (6) | C15—H15A | 0.9600 |
C2—C3 | 1.385 (6) | C15—H15B | 0.9600 |
C2—C7 | 1.389 (7) | C15—H15C | 0.9600 |
C3—C4 | 1.373 (7) | C16—H16A | 0.9600 |
C3—H3 | 0.9300 | C16—H16B | 0.9600 |
C4—C5 | 1.373 (8) | C16—H16C | 0.9600 |
C4—H4 | 0.9300 | C17A—H17A | 0.9700 |
C5—C6 | 1.378 (7) | C17A—H18A | 0.9699 |
C5—H5 | 0.9300 | C17A—H17B | 0.9700 |
C6—C7 | 1.371 (7) | C17A—H18B | 0.9700 |
C6—H6 | 0.9300 | C17A—H17C | 0.9701 |
C7—H7 | 0.9300 | C17A—H18C | 0.9701 |
C8—C10 | 1.512 (8) | ||
Cl1—Zr1—Cl5 | 99.58 (5) | C8—C10—H10A | 109.3 |
Cl1—Zr1—Cl2 | 93.20 (5) | C8—C10—H10B | 109.0 |
Cl5—Zr1—Cl2 | 92.36 (5) | H10A—C10—H10B | 108.7 |
Cl1—Zr1—Cl4 | 91.91 (5) | C8—C10—H10C | 115.1 |
Cl5—Zr1—Cl4 | 90.50 (5) | H10A—C10—H10C | 105.9 |
Cl2—Zr1—Cl4 | 173.66 (5) | H10B—C10—H10C | 108.7 |
Cl1—Zr1—Cl3i | 90.74 (11) | N2—C11—C13 | 109.7 (4) |
Cl5—Zr1—Cl3i | 169.46 (5) | N2—C11—C12 | 107.8 (4) |
Cl2—Zr1—Cl3i | 89.17 (5) | C13—C11—C12 | 112.5 (4) |
Cl4—Zr1—Cl3i | 87.00 (4) | N2—C11—H11 | 108.9 |
Cl1—Zr1—Cl3 | 169.82 (5) | C13—C11—H11 | 108.9 |
Cl5—Zr1—Cl3 | 90.56 (4) | C12—C11—H11 | 108.9 |
Cl2—Zr1—Cl3 | 87.28 (4) | C11—C12—H12A | 109.5 |
Cl4—Zr1—Cl3 | 87.04 (4) | C11—C12—H12B | 109.5 |
Cl3i—Zr1—Cl3 | 79.09 (12) | H12A—C12—H12B | 109.5 |
C15—Si1—N1 | 104.6 (3) | C11—C12—H12C | 109.5 |
C15—Si1—C14 | 113.2 (3) | H12A—C12—H12C | 109.5 |
N1—Si1—C14 | 115.2 (2) | H12B—C12—H12C | 109.5 |
C15—Si1—C16 | 111.8 (3) | C11—C13—H13A | 109.5 |
N1—Si1—C16 | 106.4 (2) | C11—C13—H13B | 109.5 |
C14—Si1—C16 | 105.5 (3) | H13A—C13—H13B | 109.5 |
Zr1i—Cl3—Zr1 | 100.91 (12) | C11—C13—H13C | 109.5 |
C1—N1—C8 | 121.2 (4) | H13A—C13—H13C | 109.5 |
C1—N1—Si1 | 127.1 (3) | H13B—C13—H13C | 109.5 |
C8—N1—Si1 | 111.5 (3) | Si1—C14—H14A | 109.5 |
C1—N2—C11 | 126.6 (4) | Si1—C14—H14B | 109.5 |
C1—N2—H2 | 113.1 | H14A—C14—H14B | 109.5 |
C11—N2—H2 | 120.0 | Si1—C14—H14C | 109.5 |
N1—C1—N2 | 122.9 (4) | H14A—C14—H14C | 109.5 |
N1—C1—C2 | 120.2 (4) | H14B—C14—H14C | 109.5 |
N2—C1—C2 | 116.9 (4) | Si1—C15—H15A | 109.5 |
C3—C2—C7 | 119.8 (4) | Si1—C15—H15B | 109.5 |
C3—C2—C1 | 120.2 (4) | H15A—C15—H15B | 109.5 |
C7—C2—C1 | 120.0 (4) | Si1—C15—H15C | 109.5 |
C4—C3—C2 | 119.9 (5) | H15A—C15—H15C | 109.5 |
C4—C3—H3 | 120.1 | H15B—C15—H15C | 109.5 |
C2—C3—H3 | 120.1 | Si1—C16—H16A | 109.5 |
C5—C4—C3 | 120.4 (5) | Si1—C16—H16B | 109.5 |
C5—C4—H4 | 119.8 | H16A—C16—H16B | 109.5 |
C3—C4—H4 | 119.8 | Si1—C16—H16C | 109.5 |
C4—C5—C6 | 119.6 (5) | H16A—C16—H16C | 109.5 |
C4—C5—H5 | 120.2 | H16B—C16—H16C | 109.5 |
C6—C5—H5 | 120.2 | Cl8—C17A—Cl6A | 116.6 (10) |
C7—C6—C5 | 120.8 (5) | Cl9—C17A—Cl7A | 122.2 (11) |
C7—C6—H6 | 119.6 | Cl6A—C17A—Cl7A | 102.3 (7) |
C5—C6—H6 | 119.6 | Cl6A—C17A—H17A | 111.5 |
C6—C7—C2 | 119.4 (4) | Cl7A—C17A—H17A | 111.1 |
C6—C7—H7 | 120.3 | Cl6A—C17A—H18A | 111.7 |
C2—C7—H7 | 120.3 | Cl7A—C17A—H18A | 111.0 |
N1—C8—C10 | 112.6 (4) | H17A—C17A—H18A | 109.1 |
N1—C8—C9 | 113.5 (4) | Cl8—C17A—H17B | 108.7 |
C10—C8—C9 | 114.0 (4) | Cl6A—C17A—H17B | 109.0 |
N1—C8—H8 | 105.2 | Cl8—C17A—H18B | 107.2 |
C10—C8—H8 | 105.2 | Cl6A—C17A—H18B | 107.7 |
C9—C8—H8 | 105.2 | H17B—C17A—H18B | 107.4 |
C8—C9—H9A | 109.5 | Cl9—C17A—H17C | 107.6 |
C8—C9—H9B | 109.5 | Cl7A—C17A—H17C | 106.8 |
H9A—C9—H9B | 109.5 | Cl9—C17A—H18C | 106.7 |
C8—C9—H9C | 109.5 | Cl7A—C17A—H18C | 106.2 |
H9A—C9—H9C | 109.5 | H17C—C17A—H18C | 106.5 |
H9B—C9—H9C | 109.5 | ||
Cl1—Zr1—Cl3—Zr1i | −3.2 (3) | C7—C2—C3—C4 | −1.0 (7) |
Cl5—Zr1—Cl3—Zr1i | −177.98 (5) | C1—C2—C3—C4 | 179.6 (4) |
Cl2—Zr1—Cl3—Zr1i | 89.68 (5) | C2—C3—C4—C5 | −0.8 (8) |
Cl4—Zr1—Cl3—Zr1i | −87.51 (5) | C3—C4—C5—C6 | 2.4 (8) |
Cl3i—Zr1—Cl3—Zr1i | 0.0 | C4—C5—C6—C7 | −2.2 (9) |
C17A—Cl7A—Cl8—Cl9 | −20.0 (14) | C5—C6—C7—C2 | 0.4 (8) |
Cl7A—Cl8—Cl9—C17A | 19.0 (12) | C3—C2—C7—C6 | 1.2 (7) |
C17A—Cl8—Cl9—Cl6A | −36.5 (7) | C1—C2—C7—C6 | −179.5 (4) |
Cl7A—Cl8—Cl9—Cl6A | −17.5 (15) | C1—N1—C8—C10 | −78.0 (5) |
C17A—Cl6A—Cl9—Cl8 | 45.8 (11) | Si1—N1—C8—C10 | 106.0 (4) |
C15—Si1—N1—C1 | −101.8 (4) | C1—N1—C8—C9 | 53.4 (6) |
C14—Si1—N1—C1 | 23.1 (5) | Si1—N1—C8—C9 | −122.6 (4) |
C16—Si1—N1—C1 | 139.7 (4) | C1—N2—C11—C13 | −124.9 (5) |
C15—Si1—N1—C8 | 73.9 (4) | C1—N2—C11—C12 | 112.2 (5) |
C14—Si1—N1—C8 | −161.2 (3) | Cl7A—Cl8—C17A—Cl9 | −161.8 (12) |
C16—Si1—N1—C8 | −44.6 (4) | Cl9—Cl8—C17A—Cl6A | 67.2 (16) |
C8—N1—C1—N2 | 10.7 (7) | Cl7A—Cl8—C17A—Cl6A | −94.7 (11) |
Si1—N1—C1—N2 | −174.0 (3) | Cl9—Cl8—C17A—Cl7A | 161.8 (12) |
C8—N1—C1—C2 | −170.2 (4) | Cl6A—Cl9—C17A—Cl8 | 124.5 (11) |
Si1—N1—C1—C2 | 5.1 (6) | Cl8—Cl9—C17A—Cl6A | −124.5 (11) |
C11—N2—C1—N1 | −165.4 (4) | Cl8—Cl9—C17A—Cl7A | −20.4 (14) |
C11—N2—C1—C2 | 15.4 (7) | Cl6A—Cl9—C17A—Cl7A | 104.1 (10) |
N1—C1—C2—C3 | −107.1 (5) | Cl9—Cl6A—C17A—Cl8 | −47.9 (11) |
N2—C1—C2—C3 | 72.1 (6) | Cl9—Cl6A—C17A—Cl7A | −122.8 (11) |
N1—C1—C2—C7 | 73.6 (6) | Cl8—Cl7A—C17A—Cl9 | 17.2 (12) |
N2—C1—C2—C7 | −107.2 (5) | Cl8—Cl7A—C17A—Cl6A | 114.2 (10) |
Symmetry code: (i) −x+2, −y−1, −z. |
Experimental details
Crystal data | |
Chemical formula | (C16H29N2Si)2[Zr2Cl10]·2CH2Cl2 |
Mr | 1261.80 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 19.61 (5), 17.350 (2), 16.832 (2) |
V (Å3) | 5727 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.09 |
Crystal size (mm) | 0.60 × 0.50 × 0.30 |
Data collection | |
Diffractometer | Enraf Nonius MACH3 diffractometer |
Absorption correction | ϕ scan North et al. (1968). The number of ψ scan sets used was 3. Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied. |
Tmin, Tmax | 0.503, 0.721 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6872, 6872, 4109 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.660 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.147, 1.02 |
No. of reflections | 6872 |
No. of parameters | 261 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.55 |
Computer programs: MACH3/PC & CAD-4-PC (Nonius, 1996), CELLFIT (Centore, 2002), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).
Zr1—Cl1 | 2.389 (5) | Zr1—Cl5 | 2.398 (6) |
Zr1—Cl2 | 2.408 (6) | Si1—N1 | 1.833 (4) |
Zr1—Cl3 | 2.622 (5) | N1—C1 | 1.325 (5) |
Zr1—Cl3i | 2.610 (7) | N2—C1 | 1.329 (6) |
Zr1—Cl4 | 2.419 (6) | C1—C2 | 1.474 (6) |
Cl1—Zr1—Cl5 | 99.58 (5) | Cl3i—Zr1—Cl3 | 79.09 (12) |
Cl5—Zr1—Cl3i | 169.46 (5) | Zr1i—Cl3—Zr1 | 100.91 (12) |
Cl1—Zr1—Cl3 | 169.82 (5) | ||
N2—C1—C2—C3 | 72.1 (6) | N1—C1—C2—C7 | 73.6 (6) |
Symmetry code: (i) −x+2, −y−1, −z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
- Information on subscribing
- Sample issue
- Purchase subscription
- Reduced-price subscriptions
- If you have already subscribed, you may need to register
Mono(amidinate) complexes of group IV transition metals (Ti, Zr), when activated by methylaluminoxane (MAO), are active in Ziegler–Natta polymerization of ethylene, propylene and styrene (Flores, Chien & Rausch, 1995a, 1995b).
While trying to isolate, from the CH2Cl2 solution of the reaction products, the mono(amidinate) complex {C6H5—C[N—CH(CH3)2]2}ZrCl3, prepared as reported by Fenske et al. (1988) according to Scheme 1, we obtained, a crystalline compound as a by-product. 1H NMR (CD2Cl2 at room temperature): δ 0.07 (s, 9H), 1.33 (d, 6H), 1.69 (d, 6H), 3.51 (m, 1H), 4.18 (m, 1H), 6.59 (s, 1H), 7.2–8 (m, 5H). The singlet at δ 0.07 (chemical shift from TMS), which is unequivocally attributable to a trimethyl silyl group, and the wide singlet at δ 6.59 suggest that an unexpected compound was isolated, probably as a result of partial hydrolysis of ZrCl4, due to contamination of the reaction solvent with H2O traces. A similar behaviour of ZrCl4 has been reported for reaction with 1,3,5-trimethoxybenzene (Coles et al., 1999).
Crystal structure analysis of the new compound has shown that it corresponds to the chemical formula reported in Scheme 2.
An ORTEP-3 (Farrugia, 1997) diagram is shown in Fig. 1 (a partially disordered solvent molecule, CH2Cl2, is also present in the crystallographically independent unit), and selected bond lengths and angles are reported in Table 1.
The di-µ-chloro-bis[tetrachlorozirconate(IV)] anion (Zr2Cl102−) is dimeric through bridging Cl atoms across crystallographic inversion centres, and the coordination around the metal atom is substantially octahedral. As expected, the Zr—Cl bond distances are longer (ca 0.2 Å) in the case of bridging Cl atoms.
The cation is at variance with the case reported in the literature (Coles et al., 1999), in which protonation and cation formation were only inferred. In the present case, the location of the H atom is certain; in fact, it was clearly identified in a difference Fourier map as bonded to atom N2, so that the cation can be indivituated as an amidinium ion. The two C—N bond distances are equivalent, as reported in a similar amidinium cation (Schmidt & Arnold, 2002), and the N—Si bond length is considerably longer than, for example, the value reported for N,N-dimethyl-(trimethylsilyl)amine (1.72 Å; Blake et al., 1986). The latter observation suggests little evidence? of pπ–dπ bond contributions between N and Si atoms in the present case, so that the double bond is? delocalized over the N1—C1—N2 system only (delocalization toward the phenyl ring can be excluded since the plane of the ring forms a dihedral angle of 72.8 (3)° with the C1/N1/N2 plane). Actually, the formation of the three centered pπ–pπ conjugated system is probably the reason why protonation occurs on N2 instead of N1.