Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015660/ac6011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015660/ac6011Isup2.hkl |
CCDC reference: 173961
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.012 Å
- R factor = 0.047
- wR factor = 0.109
- Data-to-parameter ratio = 14.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.04 From the CIF: _reflns_number_total 4626 Count of symmetry unique reflns 3149 Completeness (_total/calc) 146.90% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1477 Fraction of Friedel pairs measured 0.469 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
Li2[(1R,2R)-(-)-1,2-(NSiMe3)2-C6H10] can be translated to its sodium salt easily in hexane. When two equivalents of NaBut was added to the clear solution of dilithium salt at room temperature, a white precipitate formed immediately. The mixture was stirred overnight and filtered. The white precipitate which was isolated was dried in a vacuum to give Na2[(1R,2R)-(-)-1,2-(NSiMe3)2-C6H10]. Treatment of Na2[(1R,2R)-(-)-1,2-(NSiMe3)2-C6H10] with a half equivalent of ZrCl4 in toluene at low temperature gave a yellow solution. After filtering, the reaction afforded a colorless crystalline product in high yield. Spectroscopic analysis, 1H NMR (CDCl3, δ, p.p.m.): 0.02 (s, 36H, SiMe3), 1.15 (m, 8H, CH), 1.59 (m, 8H, CH), 3.56 (m, 4H, CH); 13C NMR (CDCl3, δ, p.p.m.): 2.42, 25.83, 36.26, 65.95.
All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry, with C—H distances of 0.98 Å and Uiso(H) = 1.5Ueq(C), but each group was allowed to rotate freely about its C—C bond. The position of the amine H atom was refined freely along with an isotropic displacement parameter. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.95–1.00 Å and Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[Zr(C12H28N2Si2)2] | Dx = 1.125 Mg m−3 |
Mr = 604.31 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, P31 | Cell parameters from 956 reflections |
a = 10.473 (5) Å | θ = 2.3–27.0° |
c = 28.166 (18) Å | µ = 0.46 mm−1 |
V = 2676 (2) Å3 | T = 298 K |
Z = 3 | Block, colorless |
F(000) = 972 | 0.35 × 0.30 × 0.10 mm |
Bruker SMART CCD area-detector diffractometer | 4626 independent reflections |
Radiation source: fine-focus sealed tube | 4526 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | h = −12→11 |
Tmin = 0.856, Tmax = 0.956 | k = −12→12 |
11157 measured reflections | l = −33→20 |
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)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.0337P)2 + 2.5967P] where P = (Fo2 + 2Fc2)/3 |
S = 1.28 | (Δ/σ)max = 0.003 |
4626 reflections | Δρmax = 0.48 e Å−3 |
310 parameters | Δρmin = −1.04 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 0000 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.03 (6) |
[Zr(C12H28N2Si2)2] | Z = 3 |
Mr = 604.31 | Mo Kα radiation |
Trigonal, P31 | µ = 0.46 mm−1 |
a = 10.473 (5) Å | T = 298 K |
c = 28.166 (18) Å | 0.35 × 0.30 × 0.10 mm |
V = 2676 (2) Å3 |
Bruker SMART CCD area-detector diffractometer | 4626 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1997) | 4526 reflections with I > 2σ(I) |
Tmin = 0.856, Tmax = 0.956 | Rint = 0.038 |
11157 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.109 | Δρmax = 0.48 e Å−3 |
S = 1.28 | Δρmin = −1.04 e Å−3 |
4626 reflections | Absolute structure: Flack (1983), 0000 Friedel pairs |
310 parameters | Absolute structure parameter: 0.03 (6) |
1 restraint |
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 | ||
Zr1 | 0.27699 (5) | 0.22031 (6) | 0.23036 (2) | 0.04014 (14) | |
Si1 | 0.3511 (2) | 0.4663 (2) | 0.14258 (8) | 0.0591 (5) | |
Si2 | 0.0084 (2) | −0.1279 (2) | 0.25372 (8) | 0.0604 (5) | |
Si3 | 0.2034 (2) | 0.3955 (2) | 0.31761 (8) | 0.0642 (5) | |
Si4 | 0.5477 (2) | 0.1437 (2) | 0.20739 (7) | 0.0529 (4) | |
N1 | 0.2373 (5) | 0.2965 (5) | 0.16764 (18) | 0.0419 (11) | |
N2 | 0.0851 (5) | 0.0247 (5) | 0.21697 (19) | 0.0499 (12) | |
N3 | 0.3166 (5) | 0.3367 (6) | 0.29350 (19) | 0.0463 (12) | |
N4 | 0.4678 (5) | 0.2158 (5) | 0.24396 (17) | 0.0407 (11) | |
C1 | 0.1160 (7) | 0.1704 (6) | 0.1428 (2) | 0.0454 (14) | |
H1 | 0.1602 | 0.1233 | 0.1242 | 0.054* | |
C2 | 0.0296 (8) | 0.2101 (8) | 0.1083 (3) | 0.0620 (18) | |
H2A | 0.0971 | 0.2826 | 0.0859 | 0.074* | |
H2B | −0.0188 | 0.2540 | 0.1257 | 0.074* | |
C3 | −0.0865 (8) | 0.0746 (9) | 0.0812 (3) | 0.074 (2) | |
H3A | −0.1439 | 0.1029 | 0.0613 | 0.088* | |
H3B | −0.0376 | 0.0379 | 0.0607 | 0.088* | |
C4 | −0.1880 (9) | −0.0458 (9) | 0.1146 (3) | 0.084 (3) | |
H4A | −0.2529 | −0.1333 | 0.0964 | 0.101* | |
H4B | −0.2487 | −0.0146 | 0.1314 | 0.101* | |
C5 | −0.1031 (8) | −0.0839 (8) | 0.1507 (3) | 0.071 (2) | |
H5A | −0.1718 | −0.1575 | 0.1727 | 0.085* | |
H5B | −0.0506 | −0.1253 | 0.1344 | 0.085* | |
C6 | 0.0061 (6) | 0.0528 (7) | 0.1781 (2) | 0.0501 (15) | |
H6 | −0.0503 | 0.0939 | 0.1928 | 0.060* | |
C7 | 0.4256 (11) | 0.4550 (11) | 0.0833 (4) | 0.101 (3) | |
H7A | 0.4770 | 0.4010 | 0.0863 | 0.152* | |
H7B | 0.4923 | 0.5527 | 0.0720 | 0.152* | |
H7C | 0.3457 | 0.4056 | 0.0613 | 0.152* | |
C8 | 0.2634 (12) | 0.5829 (9) | 0.1356 (4) | 0.101 (3) | |
H8A | 0.1895 | 0.5420 | 0.1112 | 0.152* | |
H8B | 0.3372 | 0.6813 | 0.1269 | 0.152* | |
H8C | 0.2186 | 0.5854 | 0.1651 | 0.152* | |
C9 | 0.5089 (9) | 0.5618 (9) | 0.1851 (4) | 0.093 (3) | |
H9A | 0.4733 | 0.5771 | 0.2148 | 0.140* | |
H9B | 0.5807 | 0.6552 | 0.1721 | 0.140* | |
H9C | 0.5533 | 0.5020 | 0.1902 | 0.140* | |
C10 | −0.1699 (9) | −0.1626 (11) | 0.2808 (4) | 0.094 (3) | |
H10A | −0.1545 | −0.0758 | 0.2973 | 0.142* | |
H10B | −0.2046 | −0.2433 | 0.3027 | 0.142* | |
H10C | −0.2419 | −0.1864 | 0.2562 | 0.142* | |
C11 | −0.0191 (13) | −0.3010 (10) | 0.2233 (4) | 0.118 (4) | |
H11A | −0.0725 | −0.3153 | 0.1943 | 0.177* | |
H11B | −0.0740 | −0.3842 | 0.2438 | 0.177* | |
H11C | 0.0751 | −0.2913 | 0.2165 | 0.177* | |
C12 | 0.1440 (9) | −0.0853 (10) | 0.3022 (3) | 0.077 (2) | |
H12A | 0.2396 | −0.0532 | 0.2888 | 0.115* | |
H12B | 0.1145 | −0.1721 | 0.3210 | 0.115* | |
H12C | 0.1479 | −0.0085 | 0.3219 | 0.115* | |
C13 | 0.4331 (6) | 0.3223 (7) | 0.3186 (2) | 0.0448 (14) | |
H13 | 0.3847 | 0.2280 | 0.3356 | 0.054* | |
C14 | 0.5178 (8) | 0.4452 (8) | 0.3560 (3) | 0.0645 (18) | |
H14A | 0.5729 | 0.5398 | 0.3403 | 0.077* | |
H14B | 0.4483 | 0.4501 | 0.3776 | 0.077* | |
C15 | 0.6230 (10) | 0.4127 (9) | 0.3838 (3) | 0.076 (2) | |
H15A | 0.6792 | 0.4926 | 0.4059 | 0.092* | |
H15B | 0.5666 | 0.3230 | 0.4020 | 0.092* | |
C16 | 0.7270 (10) | 0.3951 (11) | 0.3514 (3) | 0.089 (3) | |
H16A | 0.7859 | 0.3656 | 0.3699 | 0.107* | |
H16B | 0.7932 | 0.4893 | 0.3367 | 0.107* | |
C17 | 0.6456 (8) | 0.2808 (9) | 0.3127 (3) | 0.0659 (19) | |
H17A | 0.5878 | 0.1843 | 0.3271 | 0.079* | |
H17B | 0.7166 | 0.2774 | 0.2914 | 0.079* | |
C18 | 0.5441 (6) | 0.3184 (6) | 0.2845 (2) | 0.0441 (14) | |
H18 | 0.6046 | 0.4177 | 0.2715 | 0.053* | |
C19 | 0.1210 (12) | 0.3026 (12) | 0.3753 (3) | 0.106 (3) | |
H19A | 0.0340 | 0.2094 | 0.3693 | 0.159* | |
H19B | 0.0955 | 0.3637 | 0.3937 | 0.159* | |
H19C | 0.1912 | 0.2868 | 0.3924 | 0.159* | |
C20 | 0.2951 (12) | 0.5980 (10) | 0.3254 (4) | 0.109 (3) | |
H20A | 0.3817 | 0.6308 | 0.3446 | 0.163* | |
H20B | 0.2286 | 0.6229 | 0.3408 | 0.163* | |
H20C | 0.3225 | 0.6451 | 0.2950 | 0.163* | |
C21 | 0.0532 (10) | 0.3464 (12) | 0.2739 (4) | 0.103 (3) | |
H21A | 0.0940 | 0.3691 | 0.2424 | 0.155* | |
H21B | 0.0048 | 0.4018 | 0.2805 | 0.155* | |
H21C | −0.0168 | 0.2429 | 0.2761 | 0.155* | |
C22 | 0.7322 (8) | 0.2875 (10) | 0.1855 (3) | 0.077 (2) | |
H22A | 0.7276 | 0.3729 | 0.1757 | 0.116* | |
H22B | 0.7607 | 0.2495 | 0.1591 | 0.116* | |
H22C | 0.8034 | 0.3143 | 0.2105 | 0.116* | |
C23 | 0.4228 (10) | 0.0661 (11) | 0.1551 (3) | 0.087 (3) | |
H23A | 0.3229 | 0.0070 | 0.1659 | 0.131* | |
H23B | 0.4503 | 0.0062 | 0.1369 | 0.131* | |
H23C | 0.4309 | 0.1452 | 0.1357 | 0.131* | |
C24 | 0.5645 (11) | −0.0086 (10) | 0.2349 (4) | 0.094 (3) | |
H24A | 0.6541 | 0.0319 | 0.2530 | 0.140* | |
H24B | 0.5664 | −0.0715 | 0.2104 | 0.140* | |
H24C | 0.4818 | −0.0648 | 0.2554 | 0.140* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr1 | 0.0392 (3) | 0.0448 (3) | 0.0367 (3) | 0.0212 (3) | −0.0049 (3) | −0.0025 (3) |
Si1 | 0.0565 (11) | 0.0578 (11) | 0.0561 (12) | 0.0234 (9) | 0.0005 (10) | 0.0135 (10) |
Si2 | 0.0561 (10) | 0.0488 (10) | 0.0645 (13) | 0.0174 (8) | 0.0017 (9) | 0.0103 (9) |
Si3 | 0.0790 (13) | 0.0715 (13) | 0.0574 (13) | 0.0490 (11) | 0.0055 (11) | −0.0091 (10) |
Si4 | 0.0527 (10) | 0.0657 (11) | 0.0515 (11) | 0.0380 (9) | −0.0026 (8) | −0.0057 (9) |
N1 | 0.038 (2) | 0.050 (3) | 0.040 (3) | 0.024 (2) | −0.005 (2) | 0.000 (2) |
N2 | 0.038 (3) | 0.051 (3) | 0.048 (3) | 0.012 (2) | −0.002 (2) | 0.000 (2) |
N3 | 0.046 (3) | 0.052 (3) | 0.040 (3) | 0.023 (2) | 0.001 (2) | −0.006 (2) |
N4 | 0.038 (2) | 0.049 (3) | 0.038 (3) | 0.024 (2) | −0.007 (2) | −0.003 (2) |
C1 | 0.053 (3) | 0.053 (3) | 0.035 (3) | 0.030 (3) | −0.004 (3) | −0.005 (3) |
C2 | 0.062 (4) | 0.075 (4) | 0.054 (4) | 0.037 (4) | −0.009 (3) | 0.002 (4) |
C3 | 0.071 (5) | 0.091 (6) | 0.053 (5) | 0.038 (4) | −0.024 (4) | −0.015 (4) |
C4 | 0.070 (5) | 0.088 (6) | 0.074 (6) | 0.024 (4) | −0.038 (4) | −0.020 (5) |
C5 | 0.059 (4) | 0.064 (4) | 0.063 (5) | 0.011 (3) | −0.009 (4) | 0.000 (4) |
C6 | 0.037 (3) | 0.062 (4) | 0.043 (4) | 0.018 (3) | −0.016 (3) | −0.015 (3) |
C7 | 0.098 (7) | 0.120 (8) | 0.088 (7) | 0.057 (6) | 0.040 (6) | 0.037 (6) |
C8 | 0.140 (8) | 0.063 (5) | 0.112 (8) | 0.060 (6) | −0.013 (7) | 0.012 (5) |
C9 | 0.070 (5) | 0.059 (5) | 0.117 (8) | 0.007 (4) | 0.000 (5) | 0.026 (5) |
C10 | 0.061 (5) | 0.111 (7) | 0.090 (7) | 0.027 (5) | 0.013 (5) | 0.035 (6) |
C11 | 0.158 (10) | 0.062 (5) | 0.124 (10) | 0.048 (6) | −0.007 (8) | −0.001 (6) |
C12 | 0.064 (5) | 0.091 (6) | 0.075 (6) | 0.038 (4) | 0.016 (4) | 0.033 (5) |
C13 | 0.045 (3) | 0.044 (3) | 0.038 (3) | 0.016 (3) | −0.008 (3) | −0.002 (3) |
C14 | 0.076 (5) | 0.061 (4) | 0.046 (4) | 0.027 (4) | −0.012 (4) | −0.017 (3) |
C15 | 0.090 (6) | 0.074 (5) | 0.050 (5) | 0.031 (4) | −0.029 (4) | −0.011 (4) |
C16 | 0.081 (5) | 0.115 (7) | 0.070 (6) | 0.049 (5) | −0.030 (5) | −0.007 (5) |
C17 | 0.065 (4) | 0.092 (5) | 0.058 (5) | 0.052 (4) | −0.017 (4) | −0.005 (4) |
C18 | 0.042 (3) | 0.047 (3) | 0.039 (3) | 0.019 (3) | −0.009 (3) | 0.000 (3) |
C19 | 0.130 (8) | 0.129 (8) | 0.073 (6) | 0.075 (7) | 0.042 (6) | 0.009 (6) |
C20 | 0.150 (9) | 0.091 (6) | 0.114 (9) | 0.082 (7) | −0.020 (7) | −0.022 (6) |
C21 | 0.096 (6) | 0.142 (8) | 0.111 (8) | 0.089 (7) | −0.006 (6) | −0.035 (7) |
C22 | 0.073 (5) | 0.102 (6) | 0.061 (5) | 0.047 (4) | 0.017 (4) | 0.003 (4) |
C23 | 0.096 (6) | 0.122 (7) | 0.062 (6) | 0.068 (6) | −0.024 (5) | −0.040 (5) |
C24 | 0.115 (7) | 0.090 (6) | 0.106 (8) | 0.074 (6) | 0.004 (6) | 0.005 (6) |
Zr1—N4 | 2.058 (4) | C9—H9A | 0.9600 |
Zr1—N2 | 2.064 (5) | C9—H9B | 0.9600 |
Zr1—N1 | 2.064 (5) | C9—H9C | 0.9600 |
Zr1—N3 | 2.077 (5) | C10—H10A | 0.9600 |
Si1—N1 | 1.721 (5) | C10—H10B | 0.9600 |
Si1—C8 | 1.870 (8) | C10—H10C | 0.9600 |
Si1—C7 | 1.870 (9) | C11—H11A | 0.9600 |
Si1—C9 | 1.874 (9) | C11—H11B | 0.9600 |
Si2—N2 | 1.728 (5) | C11—H11C | 0.9600 |
Si2—C12 | 1.857 (9) | C12—H12A | 0.9600 |
Si2—C10 | 1.877 (8) | C12—H12B | 0.9600 |
Si2—C11 | 1.892 (10) | C12—H12C | 0.9600 |
Si3—N3 | 1.726 (5) | C13—C18 | 1.524 (9) |
Si3—C20 | 1.852 (9) | C13—C14 | 1.554 (8) |
Si3—C21 | 1.857 (10) | C13—H13 | 0.9800 |
Si3—C19 | 1.868 (9) | C14—C15 | 1.522 (10) |
Si4—N4 | 1.721 (5) | C14—H14A | 0.9700 |
Si4—C24 | 1.859 (8) | C14—H14B | 0.9700 |
Si4—C22 | 1.864 (8) | C15—C16 | 1.501 (12) |
Si4—C23 | 1.864 (8) | C15—H15A | 0.9700 |
N1—C1 | 1.473 (7) | C15—H15B | 0.9700 |
N2—C6 | 1.488 (8) | C16—C17 | 1.524 (11) |
N3—C13 | 1.481 (8) | C16—H16A | 0.9700 |
N4—C18 | 1.497 (7) | C16—H16B | 0.9700 |
C1—C2 | 1.521 (8) | C17—C18 | 1.527 (8) |
C1—C6 | 1.553 (9) | C17—H17A | 0.9700 |
C1—H1 | 0.9800 | C17—H17B | 0.9700 |
C2—C3 | 1.533 (10) | C18—H18 | 0.9800 |
C2—H2A | 0.9700 | C19—H19A | 0.9600 |
C2—H2B | 0.9700 | C19—H19B | 0.9600 |
C3—C4 | 1.505 (12) | C19—H19C | 0.9600 |
C3—H3A | 0.9700 | C20—H20A | 0.9600 |
C3—H3B | 0.9700 | C20—H20B | 0.9600 |
C4—C5 | 1.530 (11) | C20—H20C | 0.9600 |
C4—H4A | 0.9700 | C21—H21A | 0.9600 |
C4—H4B | 0.9700 | C21—H21B | 0.9600 |
C5—C6 | 1.522 (9) | C21—H21C | 0.9600 |
C5—H5A | 0.9700 | C22—H22A | 0.9600 |
C5—H5B | 0.9700 | C22—H22B | 0.9600 |
C6—H6 | 0.9800 | C22—H22C | 0.9600 |
C7—H7A | 0.9600 | C23—H23A | 0.9600 |
C7—H7B | 0.9600 | C23—H23B | 0.9600 |
C7—H7C | 0.9600 | C23—H23C | 0.9600 |
C8—H8A | 0.9600 | C24—H24A | 0.9600 |
C8—H8B | 0.9600 | C24—H24B | 0.9600 |
C8—H8C | 0.9600 | C24—H24C | 0.9600 |
N4—Zr1—N2 | 119.06 (18) | Si1—C9—H9C | 109.5 |
N4—Zr1—N1 | 123.59 (19) | H9A—C9—H9C | 109.5 |
N2—Zr1—N1 | 86.8 (2) | H9B—C9—H9C | 109.5 |
N4—Zr1—N3 | 86.72 (19) | Si2—C10—H10A | 109.5 |
N2—Zr1—N3 | 123.3 (2) | Si2—C10—H10B | 109.5 |
N1—Zr1—N3 | 121.71 (19) | H10A—C10—H10B | 109.5 |
N1—Si1—C8 | 113.9 (4) | Si2—C10—H10C | 109.5 |
N1—Si1—C7 | 113.3 (4) | H10A—C10—H10C | 109.5 |
C8—Si1—C7 | 107.7 (5) | H10B—C10—H10C | 109.5 |
N1—Si1—C9 | 105.1 (3) | Si2—C11—H11A | 109.5 |
C8—Si1—C9 | 108.0 (5) | Si2—C11—H11B | 109.5 |
C7—Si1—C9 | 108.7 (5) | H11A—C11—H11B | 109.5 |
N2—Si2—C12 | 105.8 (3) | Si2—C11—H11C | 109.5 |
N2—Si2—C10 | 112.3 (4) | H11A—C11—H11C | 109.5 |
C12—Si2—C10 | 108.4 (4) | H11B—C11—H11C | 109.5 |
N2—Si2—C11 | 113.1 (4) | Si2—C12—H12A | 109.5 |
C12—Si2—C11 | 107.1 (5) | Si2—C12—H12B | 109.5 |
C10—Si2—C11 | 109.8 (5) | H12A—C12—H12B | 109.5 |
N3—Si3—C20 | 113.6 (4) | Si2—C12—H12C | 109.5 |
N3—Si3—C21 | 106.1 (3) | H12A—C12—H12C | 109.5 |
C20—Si3—C21 | 106.2 (5) | H12B—C12—H12C | 109.5 |
N3—Si3—C19 | 112.1 (4) | N3—C13—C18 | 112.4 (5) |
C20—Si3—C19 | 109.5 (5) | N3—C13—C14 | 113.5 (5) |
C21—Si3—C19 | 109.0 (5) | C18—C13—C14 | 108.8 (5) |
N4—Si4—C24 | 113.8 (4) | N3—C13—H13 | 107.3 |
N4—Si4—C22 | 112.2 (3) | C18—C13—H13 | 107.3 |
C24—Si4—C22 | 109.0 (4) | C14—C13—H13 | 107.3 |
N4—Si4—C23 | 105.9 (3) | C15—C14—C13 | 109.9 (6) |
C24—Si4—C23 | 107.6 (5) | C15—C14—H14A | 109.7 |
C22—Si4—C23 | 108.0 (4) | C13—C14—H14A | 109.7 |
C1—N1—Si1 | 125.0 (4) | C15—C14—H14B | 109.7 |
C1—N1—Zr1 | 108.0 (4) | C13—C14—H14B | 109.7 |
Si1—N1—Zr1 | 125.5 (3) | H14A—C14—H14B | 108.2 |
C6—N2—Si2 | 125.2 (4) | C16—C15—C14 | 111.5 (7) |
C6—N2—Zr1 | 107.4 (4) | C16—C15—H15A | 109.3 |
Si2—N2—Zr1 | 125.5 (3) | C14—C15—H15A | 109.3 |
C13—N3—Si3 | 126.6 (4) | C16—C15—H15B | 109.3 |
C13—N3—Zr1 | 106.4 (4) | C14—C15—H15B | 109.3 |
Si3—N3—Zr1 | 125.1 (3) | H15A—C15—H15B | 108.0 |
C18—N4—Si4 | 124.7 (4) | C15—C16—C17 | 112.1 (7) |
C18—N4—Zr1 | 107.6 (3) | C15—C16—H16A | 109.2 |
Si4—N4—Zr1 | 126.1 (3) | C17—C16—H16A | 109.2 |
N1—C1—C2 | 115.0 (5) | C15—C16—H16B | 109.2 |
N1—C1—C6 | 111.8 (5) | C17—C16—H16B | 109.2 |
C2—C1—C6 | 108.6 (5) | H16A—C16—H16B | 107.9 |
N1—C1—H1 | 107.0 | C16—C17—C18 | 110.9 (6) |
C2—C1—H1 | 107.0 | C16—C17—H17A | 109.5 |
C6—C1—H1 | 107.0 | C18—C17—H17A | 109.5 |
C1—C2—C3 | 111.7 (6) | C16—C17—H17B | 109.5 |
C1—C2—H2A | 109.3 | C18—C17—H17B | 109.5 |
C3—C2—H2A | 109.3 | H17A—C17—H17B | 108.0 |
C1—C2—H2B | 109.3 | N4—C18—C13 | 111.1 (5) |
C3—C2—H2B | 109.3 | N4—C18—C17 | 113.8 (5) |
H2A—C2—H2B | 107.9 | C13—C18—C17 | 108.6 (5) |
C4—C3—C2 | 111.4 (6) | N4—C18—H18 | 107.7 |
C4—C3—H3A | 109.3 | C13—C18—H18 | 107.7 |
C2—C3—H3A | 109.3 | C17—C18—H18 | 107.7 |
C4—C3—H3B | 109.3 | Si3—C19—H19A | 109.5 |
C2—C3—H3B | 109.3 | Si3—C19—H19B | 109.5 |
H3A—C3—H3B | 108.0 | H19A—C19—H19B | 109.5 |
C3—C4—C5 | 112.0 (6) | Si3—C19—H19C | 109.5 |
C3—C4—H4A | 109.2 | H19A—C19—H19C | 109.5 |
C5—C4—H4A | 109.2 | H19B—C19—H19C | 109.5 |
C3—C4—H4B | 109.2 | Si3—C20—H20A | 109.5 |
C5—C4—H4B | 109.2 | Si3—C20—H20B | 109.5 |
H4A—C4—H4B | 107.9 | H20A—C20—H20B | 109.5 |
C6—C5—C4 | 110.6 (6) | Si3—C20—H20C | 109.5 |
C6—C5—H5A | 109.5 | H20A—C20—H20C | 109.5 |
C4—C5—H5A | 109.5 | H20B—C20—H20C | 109.5 |
C6—C5—H5B | 109.5 | Si3—C21—H21A | 109.5 |
C4—C5—H5B | 109.5 | Si3—C21—H21B | 109.5 |
H5A—C5—H5B | 108.1 | H21A—C21—H21B | 109.5 |
N2—C6—C5 | 114.6 (6) | Si3—C21—H21C | 109.5 |
N2—C6—C1 | 111.3 (5) | H21A—C21—H21C | 109.5 |
C5—C6—C1 | 109.4 (6) | H21B—C21—H21C | 109.5 |
N2—C6—H6 | 107.0 | Si4—C22—H22A | 109.5 |
C5—C6—H6 | 107.0 | Si4—C22—H22B | 109.5 |
C1—C6—H6 | 107.0 | H22A—C22—H22B | 109.5 |
Si1—C7—H7A | 109.5 | Si4—C22—H22C | 109.5 |
Si1—C7—H7B | 109.5 | H22A—C22—H22C | 109.5 |
H7A—C7—H7B | 109.5 | H22B—C22—H22C | 109.5 |
Si1—C7—H7C | 109.5 | Si4—C23—H23A | 109.5 |
H7A—C7—H7C | 109.5 | Si4—C23—H23B | 109.5 |
H7B—C7—H7C | 109.5 | H23A—C23—H23B | 109.5 |
Si1—C8—H8A | 109.5 | Si4—C23—H23C | 109.5 |
Si1—C8—H8B | 109.5 | H23A—C23—H23C | 109.5 |
H8A—C8—H8B | 109.5 | H23B—C23—H23C | 109.5 |
Si1—C8—H8C | 109.5 | Si4—C24—H24A | 109.5 |
H8A—C8—H8C | 109.5 | Si4—C24—H24B | 109.5 |
H8B—C8—H8C | 109.5 | H24A—C24—H24B | 109.5 |
Si1—C9—H9A | 109.5 | Si4—C24—H24C | 109.5 |
Si1—C9—H9B | 109.5 | H24A—C24—H24C | 109.5 |
H9A—C9—H9B | 109.5 | H24B—C24—H24C | 109.5 |
C8—Si1—N1—C1 | 76.0 (6) | N1—Zr1—N4—C18 | 116.0 (4) |
C7—Si1—N1—C1 | −47.6 (6) | N3—Zr1—N4—C18 | −10.5 (4) |
C9—Si1—N1—C1 | −166.1 (5) | N2—Zr1—N4—Si4 | 56.9 (4) |
C8—Si1—N1—Zr1 | −119.5 (5) | N1—Zr1—N4—Si4 | −50.0 (4) |
C7—Si1—N1—Zr1 | 116.9 (5) | N3—Zr1—N4—Si4 | −176.5 (3) |
C9—Si1—N1—Zr1 | −1.6 (5) | Si1—N1—C1—C2 | −37.8 (7) |
N4—Zr1—N1—C1 | 112.9 (4) | Zr1—N1—C1—C2 | 155.4 (5) |
N2—Zr1—N1—C1 | −10.2 (4) | Si1—N1—C1—C6 | −162.2 (4) |
N3—Zr1—N1—C1 | −137.8 (3) | Zr1—N1—C1—C6 | 31.0 (5) |
N4—Zr1—N1—Si1 | −53.8 (4) | N1—C1—C2—C3 | 175.6 (6) |
N2—Zr1—N1—Si1 | −176.9 (3) | C6—C1—C2—C3 | −58.2 (8) |
N3—Zr1—N1—Si1 | 55.5 (4) | C1—C2—C3—C4 | 55.0 (9) |
C12—Si2—N2—C6 | −168.6 (5) | C2—C3—C4—C5 | −52.8 (9) |
C10—Si2—N2—C6 | −50.6 (6) | C3—C4—C5—C6 | 55.8 (9) |
C11—Si2—N2—C6 | 74.4 (7) | Si2—N2—C6—C5 | −37.4 (8) |
C12—Si2—N2—Zr1 | −6.4 (5) | Zr1—N2—C6—C5 | 157.7 (5) |
C10—Si2—N2—Zr1 | 111.7 (5) | Si2—N2—C6—C1 | −162.2 (4) |
C11—Si2—N2—Zr1 | −123.4 (5) | Zr1—N2—C6—C1 | 32.9 (6) |
N4—Zr1—N2—C6 | −140.0 (4) | C4—C5—C6—N2 | 175.0 (6) |
N1—Zr1—N2—C6 | −12.9 (4) | C4—C5—C6—C1 | −59.2 (8) |
N3—Zr1—N2—C6 | 113.4 (4) | N1—C1—C6—N2 | −44.0 (7) |
N4—Zr1—N2—Si2 | 55.2 (4) | C2—C1—C6—N2 | −172.0 (5) |
N1—Zr1—N2—Si2 | −177.8 (4) | N1—C1—C6—C5 | −171.7 (5) |
N3—Zr1—N2—Si2 | −51.4 (4) | C2—C1—C6—C5 | 60.3 (7) |
C20—Si3—N3—C13 | 77.3 (6) | Si3—N3—C13—C18 | −160.6 (4) |
C21—Si3—N3—C13 | −166.4 (6) | Zr1—N3—C13—C18 | 34.5 (5) |
C19—Si3—N3—C13 | −47.4 (6) | Si3—N3—C13—C14 | −36.6 (8) |
C20—Si3—N3—Zr1 | −120.5 (5) | Zr1—N3—C13—C14 | 158.5 (5) |
C21—Si3—N3—Zr1 | −4.2 (5) | N3—C13—C14—C15 | 173.7 (6) |
C19—Si3—N3—Zr1 | 114.7 (5) | C18—C13—C14—C15 | −60.3 (8) |
N4—Zr1—N3—C13 | −13.0 (4) | C13—C14—C15—C16 | 55.9 (9) |
N2—Zr1—N3—C13 | 110.0 (4) | C14—C15—C16—C17 | −53.6 (10) |
N1—Zr1—N3—C13 | −141.0 (3) | C15—C16—C17—C18 | 55.5 (10) |
N4—Zr1—N3—Si3 | −178.1 (4) | Si4—N4—C18—C13 | −161.8 (4) |
N2—Zr1—N3—Si3 | −55.2 (4) | Zr1—N4—C18—C13 | 31.9 (5) |
N1—Zr1—N3—Si3 | 53.8 (4) | Si4—N4—C18—C17 | −39.0 (7) |
C24—Si4—N4—C18 | 76.3 (6) | Zr1—N4—C18—C17 | 154.8 (5) |
C22—Si4—N4—C18 | −48.0 (6) | N3—C13—C18—N4 | −45.9 (7) |
C23—Si4—N4—C18 | −165.7 (5) | C14—C13—C18—N4 | −172.5 (5) |
C24—Si4—N4—Zr1 | −120.0 (4) | N3—C13—C18—C17 | −171.8 (5) |
C22—Si4—N4—Zr1 | 115.7 (4) | C14—C13—C18—C17 | 61.7 (7) |
C23—Si4—N4—Zr1 | −2.0 (5) | C16—C17—C18—N4 | 176.3 (6) |
N2—Zr1—N4—C18 | −137.1 (3) | C16—C17—C18—C13 | −59.4 (8) |
Experimental details
Crystal data | |
Chemical formula | [Zr(C12H28N2Si2)2] |
Mr | 604.31 |
Crystal system, space group | Trigonal, P31 |
Temperature (K) | 298 |
a, c (Å) | 10.473 (5), 28.166 (18) |
V (Å3) | 2676 (2) |
Z | 3 |
Radiation type | Mo Kα |
µ (mm−1) | 0.46 |
Crystal size (mm) | 0.35 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1997) |
Tmin, Tmax | 0.856, 0.956 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11157, 4626, 4526 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.109, 1.28 |
No. of reflections | 4626 |
No. of parameters | 310 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.48, −1.04 |
Absolute structure | Flack (1983), 0000 Friedel pairs |
Absolute structure parameter | 0.03 (6) |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
Zr1—N4 | 2.058 (4) | Zr1—N1 | 2.064 (5) |
Zr1—N2 | 2.064 (5) | Zr1—N3 | 2.077 (5) |
N4—Zr1—N2 | 119.06 (18) | N4—Zr1—N3 | 86.72 (19) |
N4—Zr1—N1 | 123.59 (19) | N2—Zr1—N3 | 123.3 (2) |
N2—Zr1—N1 | 86.8 (2) | N1—Zr1—N3 | 121.71 (19) |
N2—Zr1—N1—C1 | −10.2 (4) | N3—Zr1—N4—C18 | −10.5 (4) |
N1—Zr1—N2—C6 | −12.9 (4) | N1—C1—C6—N2 | −44.0 (7) |
N4—Zr1—N3—C13 | −13.0 (4) | N3—C13—C18—N4 | −45.9 (7) |
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Group 4 metal complexes containing bidentate bis(amide) or tetradentate bis(amidinate) ligands are promising systems for applications in catalysis because of their relationship to the well studied metallocene analogues Cp2MX2, bis(amide) (R2N)2MX2 (Minhas et al., 1996), and bis(amidinate) [N(R)C(R')N(R)]2MX2 (Bambirra et al., 2001; Foley et al., 2000). An attractive goal in this area is to develop chiral metal complexes for exploitation in stereoselective catalysis (Hagadorn & Arnold, 1998). The (1R,2R)-DACH served as broad-range chiral reagents has been proved a useful building block (Larrow et al., 1994). Recently, we reported the chemistry of its lithium derivatives, including mono- and dilithium (1R,2R)-(-)-1,2-(NHSiMe3)2-C6H10, and grew single crystals suitable for X-ray diffraction analysis (Li et al., 2002). Using this approach for the preparation of transition-metal complexes, we now reported the syntheses and structures of zirconium bis(amide) tetra-dentate complex, (I).
The molecular structure of (I) is shown in Fig. 1. The two cyclohexyl groups adopt chair conformations. The molecule of (I) is located on a crstallographic twofold axis, which passes through the Zr atom and the center of the N2—N1 and N3—N4 bonds, and therefore has high symmetry (Fig. 2). The structure can be viewed as a tetrahedron, with the metal ion in the center bonded to two bidentate ligands.
All the amide N atoms are sp2-hybridized (for example, the sum of the angles around N1 is 358.5°). The geometry around Zr is distorted tetrahedral, with the four Zr—N bond distances in the range 2.058 (4)–2.077 (5) Å and similar to the literature values (Lee et al., 2000). The five-membered Zr—N—C—C—N ring adopts an envelope conformation. From Table 1, we note that the intraannular N—Zr—N' angles, N1—Zr1—N2 [86.8 (2)°] and N3—Zr1—N4 [86.72 (19)°], are significantly smaller than the ideal tetrahedral value due to chelation, while the other two N—Zr—N' angles between the two chelate rings, N1—Zr1—N3 [121.71 (19)°] and N2—Zr1—N4 [119.06 (18)°] are correspondingly larger. The N1—Zr1—N2 and N3—Zr1—N4 planes are almost vertical and the dihedral angle is 92.8°. In addition, the two NSiMe3 groups related by the crystallographically imposed C2 axis are symmetrically placed above and below the opposite N—Zr—N' plane, similar to the complex {(±)-trans-1,2-(NSiMe3)2-C6H10}TiI2 (Tsuie et al., 1997).