Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104000605/sq1141sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104000605/sq1141Isup2.hkl |
CCDC reference: 233118
Treatment of a suspension of ZrCl4 (0.153 g, 0.656 mmol) in THF, chilled to 195 K, with a solution of lithiated carbazole (0.500 g, 2.00 mmol) in THF, previously formed by deprotonation of carbazole with a fourfold molar excess of lithium hydride, resulted in a reaction that, on warming to room temperature, afforded a yellow solution. After filtration and removal of solvent, a yellow powder was recovered. Thf was added to a small portion of the yellow powder until a saturated solution resulted, and over a period of a week, large crystals grew from the recrystallization solution. The compound has been characterized by one and two-dimensional 1H and 13C NMR spectroscopy at variable temperatures in solution. The spectroscopic data fully support the formation of this compound.
All H atoms were introduced at calculated positions and treated by applying a riding model [Uiso(H)=1.2Ueq(C), CCH2—H = 0.99 Å and Caromatic—H = 0.95 Å].
Data collection: SMART (Bruker 1997); cell refinement: SAINT (Bruker 1997); data reduction: SAINT; 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: SHELXTL.
[Li(C4H8O)4][ZrCl2(C12H8N)3(C4H8O)] | F(000) = 2152 |
Mr = 1028.16 | Dx = 1.332 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 14112 reflections |
a = 14.984 (5) Å | θ = 2.7–26.1° |
b = 27.435 (9) Å | µ = 0.37 mm−1 |
c = 13.574 (4) Å | T = 173 K |
β = 113.220 (5)° | Block, yellow |
V = 5128 (3) Å3 | 0.22 × 0.19 × 0.15 mm |
Z = 4 |
Bruker AXS CCD diffractometer | 5069 independent reflections |
Radiation source: fine-focus sealed tube | 4128 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: not measured pixels mm-1 | θmax = 26.1°, θmin = 1.5° |
ϕ and ω scans | h = −18→18 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −33→33 |
Tmin = 0.946, Tmax = 0.946 | l = −16→16 |
24554 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.038P)2 + 5.9992P] where P = (Fo2 + 2Fc2)/3 |
5069 reflections | (Δ/σ)max < 0.001 |
357 parameters | Δρmax = 0.75 e Å−3 |
30 restraints | Δρmin = −0.47 e Å−3 |
[Li(C4H8O)4][ZrCl2(C12H8N)3(C4H8O)] | V = 5128 (3) Å3 |
Mr = 1028.16 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 14.984 (5) Å | µ = 0.37 mm−1 |
b = 27.435 (9) Å | T = 173 K |
c = 13.574 (4) Å | 0.22 × 0.19 × 0.15 mm |
β = 113.220 (5)° |
Bruker AXS CCD diffractometer | 5069 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4128 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.946 | Rint = 0.037 |
24554 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 30 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.75 e Å−3 |
5069 reflections | Δρmin = −0.47 e Å−3 |
357 parameters |
Experimental. Data were collected using a Bruker AXS SMART 1000 diffractometer equipped with a CCD area detector and graphite monochromated Mo source operating with a Nicolet liquid nitrogen cooling system at 173 K. Data were measured using phi–omega scans of 0.3 degrees with an integration time of 20 s. A total of 2424 frames were collected, with the initial 606 frames recollected in the final run. |
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) | |
C1 | 0.22805 (15) | 0.41059 (7) | 0.90270 (16) | 0.0257 (4) | |
C2 | 0.21395 (15) | 0.37118 (8) | 0.95987 (16) | 0.0292 (5) | |
H2 | 0.1519 | 0.3563 | 0.9388 | 0.035* | |
C3 | 0.29215 (16) | 0.35414 (8) | 1.04798 (17) | 0.0332 (5) | |
H3 | 0.2830 | 0.3273 | 1.0872 | 0.040* | |
C4 | 0.38387 (16) | 0.37526 (8) | 1.08076 (18) | 0.0356 (5) | |
H4 | 0.4358 | 0.3634 | 1.1427 | 0.043* | |
C5 | 0.39930 (16) | 0.41336 (8) | 1.02340 (18) | 0.0341 (5) | |
H5 | 0.4620 | 0.4274 | 1.0444 | 0.041* | |
C6 | 0.32164 (15) | 0.43108 (8) | 0.93399 (16) | 0.0286 (5) | |
C7 | 0.31350 (16) | 0.46892 (8) | 0.85762 (17) | 0.0311 (5) | |
C8 | 0.38098 (18) | 0.50074 (10) | 0.8452 (2) | 0.0438 (6) | |
H8 | 0.4470 | 0.5000 | 0.8941 | 0.053* | |
C9 | 0.3505 (2) | 0.53318 (10) | 0.7613 (2) | 0.0516 (7) | |
H9 | 0.3957 | 0.5552 | 0.7524 | 0.062* | |
C10 | 0.25322 (19) | 0.53400 (10) | 0.6887 (2) | 0.0474 (6) | |
H10 | 0.2335 | 0.5568 | 0.6313 | 0.057* | |
C11 | 0.18513 (17) | 0.50240 (9) | 0.69857 (18) | 0.0363 (5) | |
H11 | 0.1196 | 0.5030 | 0.6483 | 0.044* | |
C12 | 0.21506 (16) | 0.46947 (8) | 0.78441 (16) | 0.0295 (5) | |
C13 | 0.06033 (15) | 0.31511 (8) | 0.72147 (16) | 0.0288 (4) | |
C14 | 0.13402 (16) | 0.32748 (9) | 0.68802 (18) | 0.0363 (5) | |
H14 | 0.1484 | 0.3606 | 0.6801 | 0.044* | |
C15 | 0.18584 (18) | 0.29000 (10) | 0.6666 (2) | 0.0435 (6) | |
H15 | 0.2366 | 0.2978 | 0.6440 | 0.052* | |
C16 | 0.16548 (18) | 0.24104 (10) | 0.6772 (2) | 0.0457 (6) | |
H16 | 0.2025 | 0.2162 | 0.6621 | 0.055* | |
C17 | 0.09239 (17) | 0.22851 (9) | 0.70927 (18) | 0.0402 (6) | |
H17 | 0.0780 | 0.1952 | 0.7158 | 0.048* | |
C18 | 0.03924 (15) | 0.26571 (8) | 0.73230 (16) | 0.0312 (5) | |
C19 | −0.05791 (19) | 0.53906 (8) | 0.65815 (19) | 0.0397 (6) | |
H19A | −0.1272 | 0.5391 | 0.6476 | 0.048* | |
H19B | −0.0527 | 0.5276 | 0.5915 | 0.048* | |
C21 | 0.4067 (2) | 0.29132 (10) | 0.9026 (2) | 0.0486 (6) | |
H21A | 0.3533 | 0.3134 | 0.8594 | 0.058* | |
H21B | 0.4519 | 0.3096 | 0.9654 | 0.058* | |
C22 | 0.3668 (2) | 0.24759 (11) | 0.9387 (2) | 0.0520 (7) | |
H22A | 0.2956 | 0.2451 | 0.8987 | 0.062* | |
H22B | 0.3812 | 0.2495 | 1.0163 | 0.062* | |
C23 | 0.4182 (2) | 0.20439 (12) | 0.9143 (3) | 0.0667 (9) | |
H23A | 0.4490 | 0.1838 | 0.9788 | 0.080* | |
H23B | 0.3719 | 0.1842 | 0.8560 | 0.080* | |
C24 | 0.4919 (3) | 0.22601 (12) | 0.8812 (3) | 0.0804 (11) | |
H24A | 0.5549 | 0.2287 | 0.9434 | 0.096* | |
H24B | 0.5010 | 0.2056 | 0.8258 | 0.096* | |
C20 | −0.0141 (15) | 0.5892 (5) | 0.6885 (10) | 0.045 (3) | 0.38 (3) |
H20A | −0.0620 | 0.6150 | 0.6526 | 0.054* | 0.38 (3) |
H20B | 0.0435 | 0.5933 | 0.6708 | 0.054* | 0.38 (3) |
C25 | 0.3628 (16) | 0.3999 (8) | 0.6704 (19) | 0.082 (6) | 0.61 (4) |
H25A | 0.4148 | 0.4247 | 0.6978 | 0.099* | 0.61 (4) |
H25B | 0.3358 | 0.3944 | 0.7253 | 0.099* | 0.61 (4) |
C26 | 0.2817 (14) | 0.4178 (7) | 0.5642 (11) | 0.083 (5) | 0.54 (3) |
H26C | 0.2180 | 0.4178 | 0.5703 | 0.099* | 0.54 (3) |
H26D | 0.2958 | 0.4512 | 0.5469 | 0.099* | 0.54 (3) |
C27 | 0.2812 (11) | 0.3850 (8) | 0.4851 (14) | 0.100 (5) | 0.54 (3) |
H27A | 0.2901 | 0.4028 | 0.4262 | 0.120* | 0.54 (3) |
H27B | 0.2182 | 0.3676 | 0.4551 | 0.120* | 0.54 (3) |
C28 | 0.3613 (15) | 0.3495 (8) | 0.5340 (15) | 0.081 (5) | 0.61 (4) |
H28A | 0.3366 | 0.3158 | 0.5157 | 0.097* | 0.61 (4) |
H28B | 0.4126 | 0.3550 | 0.5063 | 0.097* | 0.61 (4) |
C20' | −0.0502 (10) | 0.5900 (3) | 0.7064 (11) | 0.068 (3) | 0.62 (3) |
H20C | −0.0570 | 0.6156 | 0.6524 | 0.081* | 0.62 (3) |
H20D | −0.1002 | 0.5951 | 0.7361 | 0.081* | 0.62 (3) |
C25' | 0.361 (2) | 0.4004 (9) | 0.682 (3) | 0.053 (5) | 0.39 (4) |
H25C | 0.3044 | 0.3922 | 0.6996 | 0.064* | 0.39 (4) |
H25D | 0.4110 | 0.4167 | 0.7447 | 0.064* | 0.39 (4) |
C26' | 0.332 (2) | 0.4306 (6) | 0.5852 (16) | 0.101 (5) | 0.46 (3) |
H26A | 0.2726 | 0.4492 | 0.5742 | 0.121* | 0.46 (3) |
H26B | 0.3847 | 0.4538 | 0.5907 | 0.121* | 0.46 (3) |
C27' | 0.316 (2) | 0.3969 (11) | 0.4990 (17) | 0.130 (9) | 0.46 (3) |
H27C | 0.2498 | 0.3827 | 0.4741 | 0.156* | 0.46 (3) |
H27D | 0.3240 | 0.4130 | 0.4378 | 0.156* | 0.46 (3) |
C28' | 0.383 (2) | 0.3631 (12) | 0.543 (2) | 0.066 (6) | 0.39 (4) |
H28C | 0.4444 | 0.3731 | 0.5362 | 0.079* | 0.39 (4) |
H28D | 0.3619 | 0.3320 | 0.5036 | 0.079* | 0.39 (4) |
Cl1 | 0.01009 (4) | 0.42858 (2) | 0.93441 (4) | 0.03433 (14) | |
Li1 | 0.5000 | 0.3143 (2) | 0.7500 | 0.0424 (13) | |
N1 | 0.15995 (12) | 0.43434 (6) | 0.81169 (13) | 0.0265 (4) | |
N2 | 0.0000 | 0.34652 (9) | 0.7500 | 0.0272 (5) | |
O1 | 0.0000 | 0.50794 (7) | 0.7500 | 0.0309 (5) | |
O2 | 0.45709 (14) | 0.27326 (6) | 0.83919 (14) | 0.0464 (4) | |
O3 | 0.40063 (14) | 0.35634 (7) | 0.64931 (14) | 0.0518 (5) | |
Zr1 | 0.0000 | 0.425522 (10) | 0.7500 | 0.02317 (9) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0276 (11) | 0.0260 (11) | 0.0249 (10) | 0.0008 (8) | 0.0119 (8) | −0.0024 (8) |
C2 | 0.0290 (11) | 0.0288 (11) | 0.0297 (11) | −0.0014 (9) | 0.0116 (9) | 0.0003 (9) |
C3 | 0.0355 (12) | 0.0297 (12) | 0.0327 (11) | 0.0028 (9) | 0.0118 (10) | 0.0048 (9) |
C4 | 0.0323 (12) | 0.0359 (13) | 0.0316 (11) | 0.0054 (10) | 0.0050 (9) | 0.0021 (10) |
C5 | 0.0267 (11) | 0.0348 (13) | 0.0357 (12) | −0.0039 (9) | 0.0069 (9) | −0.0058 (10) |
C6 | 0.0295 (11) | 0.0280 (11) | 0.0286 (10) | −0.0038 (9) | 0.0117 (9) | −0.0046 (9) |
C7 | 0.0315 (12) | 0.0319 (12) | 0.0299 (11) | −0.0059 (9) | 0.0121 (9) | −0.0020 (9) |
C8 | 0.0385 (13) | 0.0486 (15) | 0.0390 (13) | −0.0169 (11) | 0.0096 (11) | 0.0011 (11) |
C9 | 0.0505 (16) | 0.0532 (17) | 0.0486 (15) | −0.0263 (13) | 0.0170 (13) | 0.0057 (13) |
C10 | 0.0534 (16) | 0.0492 (16) | 0.0376 (13) | −0.0148 (12) | 0.0159 (12) | 0.0106 (11) |
C11 | 0.0383 (13) | 0.0394 (13) | 0.0310 (11) | −0.0061 (10) | 0.0134 (10) | 0.0040 (10) |
C12 | 0.0331 (12) | 0.0304 (12) | 0.0271 (10) | −0.0060 (9) | 0.0141 (9) | −0.0019 (9) |
C13 | 0.0254 (10) | 0.0309 (11) | 0.0258 (10) | 0.0008 (9) | 0.0056 (8) | −0.0061 (9) |
C14 | 0.0319 (12) | 0.0398 (13) | 0.0389 (12) | −0.0023 (10) | 0.0157 (10) | −0.0094 (10) |
C15 | 0.0342 (13) | 0.0550 (17) | 0.0421 (13) | 0.0025 (11) | 0.0159 (11) | −0.0131 (12) |
C16 | 0.0404 (14) | 0.0494 (16) | 0.0411 (13) | 0.0132 (12) | 0.0093 (11) | −0.0149 (12) |
C17 | 0.0425 (14) | 0.0324 (13) | 0.0329 (12) | 0.0056 (10) | 0.0014 (10) | −0.0062 (10) |
C18 | 0.0295 (11) | 0.0305 (12) | 0.0245 (10) | 0.0016 (9) | 0.0010 (9) | −0.0033 (9) |
C19 | 0.0468 (14) | 0.0321 (13) | 0.0372 (13) | 0.0070 (11) | 0.0132 (11) | 0.0116 (10) |
C21 | 0.0481 (15) | 0.0526 (17) | 0.0517 (15) | −0.0040 (12) | 0.0268 (13) | −0.0043 (13) |
C22 | 0.0526 (16) | 0.0651 (19) | 0.0402 (14) | −0.0121 (14) | 0.0203 (12) | 0.0026 (13) |
C23 | 0.073 (2) | 0.0557 (19) | 0.074 (2) | −0.0022 (16) | 0.0322 (18) | 0.0190 (16) |
C24 | 0.124 (3) | 0.059 (2) | 0.087 (2) | 0.024 (2) | 0.073 (2) | 0.0206 (18) |
C20 | 0.066 (9) | 0.030 (4) | 0.040 (5) | 0.007 (5) | 0.023 (5) | 0.010 (3) |
C25 | 0.086 (10) | 0.072 (9) | 0.080 (9) | 0.021 (8) | 0.025 (7) | −0.021 (7) |
C26 | 0.093 (9) | 0.085 (9) | 0.080 (7) | 0.051 (7) | 0.045 (7) | 0.025 (6) |
C27 | 0.059 (7) | 0.157 (12) | 0.070 (6) | 0.060 (7) | 0.010 (5) | 0.006 (7) |
C28 | 0.100 (9) | 0.092 (9) | 0.030 (3) | 0.028 (6) | 0.005 (5) | −0.005 (5) |
C20' | 0.074 (6) | 0.031 (3) | 0.082 (7) | 0.006 (4) | 0.014 (4) | 0.002 (3) |
C25' | 0.069 (11) | 0.042 (9) | 0.075 (10) | 0.019 (8) | 0.057 (9) | 0.009 (7) |
C26' | 0.104 (13) | 0.069 (8) | 0.118 (10) | 0.023 (8) | 0.029 (10) | 0.013 (7) |
C27' | 0.125 (18) | 0.164 (16) | 0.078 (9) | 0.055 (15) | 0.014 (11) | 0.077 (11) |
C28' | 0.067 (9) | 0.086 (13) | 0.048 (9) | 0.042 (9) | 0.026 (8) | 0.000 (8) |
Cl1 | 0.0393 (3) | 0.0420 (3) | 0.0242 (3) | 0.0064 (2) | 0.0151 (2) | 0.0017 (2) |
Li1 | 0.053 (4) | 0.043 (3) | 0.036 (3) | 0.000 | 0.022 (3) | 0.000 |
N1 | 0.0285 (9) | 0.0271 (10) | 0.0244 (8) | −0.0010 (7) | 0.0112 (7) | 0.0026 (7) |
N2 | 0.0257 (13) | 0.0285 (13) | 0.0292 (12) | 0.000 | 0.0126 (10) | 0.000 |
O1 | 0.0369 (12) | 0.0260 (11) | 0.0271 (10) | 0.000 | 0.0097 (9) | 0.000 |
O2 | 0.0649 (12) | 0.0405 (10) | 0.0437 (10) | −0.0011 (9) | 0.0321 (9) | 0.0040 (8) |
O3 | 0.0608 (12) | 0.0527 (12) | 0.0418 (10) | 0.0181 (9) | 0.0201 (9) | −0.0016 (8) |
Zr1 | 0.02486 (15) | 0.02480 (16) | 0.02092 (14) | 0.000 | 0.01019 (11) | 0.000 |
C1—C2 | 1.395 (3) | C23—C24 | 1.472 (5) |
C1—C6 | 1.412 (3) | C23—H23A | 0.9900 |
C1—N1 | 1.413 (3) | C23—H23B | 0.9900 |
C2—C3 | 1.384 (3) | C24—O2 | 1.430 (4) |
C2—H2 | 0.9500 | C24—H24A | 0.9900 |
C3—C4 | 1.393 (3) | C24—H24B | 0.9900 |
C3—H3 | 0.9500 | C20—C20i | 1.55 (2) |
C4—C5 | 1.376 (3) | C20—H20A | 0.9900 |
C4—H4 | 0.9500 | C20—H20B | 0.9900 |
C5—C6 | 1.396 (3) | C25—O3 | 1.40 (2) |
C5—H5 | 0.9500 | C25—C26 | 1.55 (3) |
C6—C7 | 1.438 (3) | C25—H25A | 0.9900 |
C7—C8 | 1.395 (3) | C25—H25B | 0.9900 |
C7—C12 | 1.417 (3) | C26—C27 | 1.40 (2) |
C8—C9 | 1.375 (4) | C26—H26C | 0.9900 |
C8—H8 | 0.9500 | C26—H26D | 0.9900 |
C9—C10 | 1.401 (4) | C27—C28 | 1.48 (2) |
C9—H9 | 0.9500 | C27—H27A | 0.9900 |
C10—C11 | 1.385 (3) | C27—H27B | 0.9900 |
C10—H10 | 0.9500 | C28—O3 | 1.451 (18) |
C11—C12 | 1.401 (3) | C28—H28A | 0.9900 |
C11—H11 | 0.9500 | C28—H28B | 0.9900 |
C12—N1 | 1.410 (3) | C20'—C20'i | 1.50 (2) |
C13—C14 | 1.391 (3) | C20'—H20C | 0.9900 |
C13—N2 | 1.409 (3) | C20'—H20D | 0.9900 |
C13—C18 | 1.413 (3) | C25'—C26' | 1.47 (3) |
C14—C15 | 1.387 (3) | C25'—O3 | 1.49 (3) |
C14—H14 | 0.9500 | C25'—H25C | 0.9900 |
C15—C16 | 1.397 (4) | C25'—H25D | 0.9900 |
C15—H15 | 0.9500 | C26'—C27' | 1.43 (3) |
C16—C17 | 1.372 (4) | C26'—H26A | 0.9900 |
C16—H16 | 0.9500 | C26'—H26B | 0.9900 |
C17—C18 | 1.404 (3) | C27'—C28' | 1.33 (3) |
C17—H17 | 0.9500 | C27'—H27C | 0.9900 |
C18—C18i | 1.435 (4) | C27'—H27D | 0.9900 |
C19—C20 | 1.509 (13) | C28'—O3 | 1.38 (3) |
C19—C20' | 1.528 (10) | C28'—H28C | 0.9900 |
C19—H19A | 0.9900 | C28'—H28D | 0.9900 |
C19—H19B | 0.9900 | Li1—O2ii | 1.939 (4) |
C21—O2 | 1.438 (3) | Li1—O3ii | 1.952 (4) |
C21—C22 | 1.506 (4) | N2—C13i | 1.409 (3) |
C21—H21A | 0.9900 | N2—Zr1 | 2.167 (3) |
C21—H21B | 0.9900 | O1—C19i | 1.478 (2) |
C22—C23 | 1.519 (4) | O1—Zr1 | 2.261 (2) |
C22—H22A | 0.9900 | Zr1—N1i | 2.2185 (18) |
C22—H22B | 0.9900 | Zr1—Cl1i | 2.4488 (9) |
C2—C1—C6 | 119.46 (19) | H20A—C20—H20B | 109.3 |
C2—C1—N1 | 128.91 (19) | O3—C25—C26 | 108.2 (16) |
C6—C1—N1 | 111.62 (18) | O3—C25—H25A | 110.1 |
C3—C2—C1 | 118.7 (2) | C26—C25—H25A | 110.1 |
C3—C2—H2 | 120.7 | O3—C25—H25B | 110.1 |
C1—C2—H2 | 120.7 | C26—C25—H25B | 110.1 |
C2—C3—C4 | 121.9 (2) | H25A—C25—H25B | 108.4 |
C2—C3—H3 | 119.1 | C27—C26—C25 | 105.9 (12) |
C4—C3—H3 | 119.1 | C27—C26—H26C | 110.5 |
C5—C4—C3 | 120.0 (2) | C25—C26—H26C | 110.6 |
C5—C4—H4 | 120.0 | C27—C26—H26D | 110.6 |
C3—C4—H4 | 120.0 | C25—C26—H26D | 110.6 |
C4—C5—C6 | 119.2 (2) | H26C—C26—H26D | 108.7 |
C4—C5—H5 | 120.4 | C26—C27—C28 | 108.7 (13) |
C6—C5—H5 | 120.4 | C26—C27—H27A | 110.0 |
C5—C6—C1 | 120.7 (2) | C28—C27—H27A | 110.0 |
C5—C6—C7 | 133.1 (2) | C26—C27—H27B | 110.0 |
C1—C6—C7 | 106.19 (18) | C28—C27—H27B | 110.0 |
C8—C7—C12 | 120.8 (2) | H27A—C27—H27B | 108.3 |
C8—C7—C6 | 132.8 (2) | O3—C28—C27 | 108.1 (13) |
C12—C7—C6 | 106.39 (18) | O3—C28—H28A | 110.1 |
C9—C8—C7 | 119.0 (2) | C27—C28—H28A | 110.1 |
C9—C8—H8 | 120.5 | O3—C28—H28B | 110.1 |
C7—C8—H8 | 120.5 | C27—C28—H28B | 110.1 |
C8—C9—C10 | 120.5 (2) | H28A—C28—H28B | 108.4 |
C8—C9—H9 | 119.8 | C20'i—C20'—C19 | 102.7 (8) |
C10—C9—H9 | 119.8 | C20'i—C20'—H20C | 111.2 |
C11—C10—C9 | 121.6 (2) | C19—C20'—H20C | 111.2 |
C11—C10—H10 | 119.2 | C20'i—C20'—H20D | 111.2 |
C9—C10—H10 | 119.2 | C19—C20'—H20D | 111.2 |
C10—C11—C12 | 118.5 (2) | H20C—C20'—H20D | 109.1 |
C10—C11—H11 | 120.7 | C26'—C25'—O3 | 101 (2) |
C12—C11—H11 | 120.7 | C26'—C25'—H25C | 111.5 |
C11—C12—N1 | 129.1 (2) | O3—C25'—H25C | 111.5 |
C11—C12—C7 | 119.57 (19) | C26'—C25'—H25D | 111.5 |
N1—C12—C7 | 111.34 (18) | O3—C25'—H25D | 111.5 |
C14—C13—N2 | 128.2 (2) | H25C—C25'—H25D | 109.3 |
C14—C13—C18 | 120.5 (2) | C27'—C26'—C25' | 105.4 (18) |
N2—C13—C18 | 111.35 (19) | C27'—C26'—H26A | 110.7 |
C15—C14—C13 | 118.0 (2) | C25'—C26'—H26A | 110.7 |
C15—C14—H14 | 121.0 | C27'—C26'—H26B | 110.7 |
C13—C14—H14 | 121.0 | C25'—C26'—H26B | 110.7 |
C14—C15—C16 | 121.9 (2) | H26A—C26'—H26B | 108.8 |
C14—C15—H15 | 119.1 | C28'—C27'—C26' | 103.2 (18) |
C16—C15—H15 | 119.1 | C28'—C27'—H27C | 111.1 |
C17—C16—C15 | 120.5 (2) | C26'—C27'—H27C | 111.1 |
C17—C16—H16 | 119.8 | C28'—C27'—H27D | 111.1 |
C15—C16—H16 | 119.8 | C26'—C27'—H27D | 111.1 |
C16—C17—C18 | 118.8 (2) | H27C—C27'—H27D | 109.1 |
C16—C17—H17 | 120.6 | C27'—C28'—O3 | 110.9 (17) |
C18—C17—H17 | 120.6 | C27'—C28'—H28C | 109.5 |
C17—C18—C13 | 120.3 (2) | O3—C28'—H28C | 109.5 |
C17—C18—C18i | 133.35 (15) | C27'—C28'—H28D | 109.5 |
C13—C18—C18i | 106.34 (12) | O3—C28'—H28D | 109.5 |
O1—C19—C20 | 104.4 (6) | H28C—C28'—H28D | 108.1 |
O1—C19—C20' | 104.3 (4) | O2ii—Li1—O2 | 109.0 (3) |
O1—C19—H19A | 110.9 | O2ii—Li1—O3ii | 115.53 (8) |
C20—C19—H19A | 110.9 | O2—Li1—O3ii | 104.78 (8) |
C20'—C19—H19A | 87.6 | O2ii—Li1—O3 | 104.78 (8) |
O1—C19—H19B | 110.9 | O2—Li1—O3 | 115.53 (8) |
C20—C19—H19B | 110.9 | O3ii—Li1—O3 | 107.6 (3) |
C20'—C19—H19B | 131.5 | C12—N1—C1 | 104.41 (17) |
H19A—C19—H19B | 108.9 | C12—N1—Zr1 | 129.24 (14) |
O2—C21—C22 | 106.8 (2) | C1—N1—Zr1 | 125.44 (13) |
O2—C21—H21A | 110.4 | C13—N2—C13i | 104.6 (2) |
C22—C21—H21A | 110.4 | C13—N2—Zr1 | 127.70 (12) |
O2—C21—H21B | 110.4 | C13i—N2—Zr1 | 127.70 (12) |
C22—C21—H21B | 110.4 | C19i—O1—C19 | 109.4 (2) |
H21A—C21—H21B | 108.6 | C19i—O1—Zr1 | 125.30 (12) |
C21—C22—C23 | 104.5 (2) | C19—O1—Zr1 | 125.30 (12) |
C21—C22—H22A | 110.9 | C24—O2—C21 | 105.6 (2) |
C23—C22—H22A | 110.9 | C24—O2—Li1 | 128.1 (2) |
C21—C22—H22B | 110.9 | C21—O2—Li1 | 123.7 (2) |
C23—C22—H22B | 110.9 | C28'—O3—C25 | 100.2 (13) |
H22A—C22—H22B | 108.9 | C25—O3—C28 | 107.8 (12) |
C24—C23—C22 | 104.9 (3) | C28'—O3—C25' | 105.9 (14) |
C24—C23—H23A | 110.8 | C28—O3—C25' | 112.8 (15) |
C22—C23—H23A | 110.8 | C28'—O3—Li1 | 126.1 (8) |
C24—C23—H23B | 110.8 | C25—O3—Li1 | 128.3 (10) |
C22—C23—H23B | 110.8 | C28—O3—Li1 | 123.5 (7) |
H23A—C23—H23B | 108.8 | C25'—O3—Li1 | 123.6 (14) |
O2—C24—C23 | 106.7 (3) | N2—Zr1—N1i | 96.26 (4) |
O2—C24—H24A | 110.4 | N1—Zr1—N1i | 167.49 (9) |
C23—C24—H24A | 110.4 | N2—Zr1—O1 | 180.0 |
O2—C24—H24B | 110.4 | N1i—Zr1—O1 | 83.74 (4) |
C23—C24—H24B | 110.4 | N2—Zr1—Cl1 | 91.965 (15) |
H24A—C24—H24B | 108.6 | N1i—Zr1—Cl1 | 90.24 (4) |
C19—C20—C20i | 101.4 (7) | N2—Zr1—Cl1i | 91.965 (15) |
C19—C20—H20A | 111.5 | N1—Zr1—Cl1i | 90.24 (4) |
C20i—C20—H20A | 111.5 | N1i—Zr1—Cl1i | 89.33 (4) |
C19—C20—H20B | 111.5 | O1—Zr1—Cl1i | 88.035 (15) |
C20i—C20—H20B | 111.5 | Cl1—Zr1—Cl1i | 176.07 (3) |
C6—C1—C2—C3 | 1.8 (3) | C20'—C19—O1—C19i | −12.6 (7) |
N1—C1—C2—C3 | −179.5 (2) | C20—C19—O1—Zr1 | −166.1 (7) |
C1—C2—C3—C4 | 0.1 (3) | C20'—C19—O1—Zr1 | 167.4 (7) |
C2—C3—C4—C5 | −1.7 (3) | C23—C24—O2—C21 | 35.0 (4) |
C3—C4—C5—C6 | 1.4 (3) | C23—C24—O2—Li1 | −163.0 (2) |
C4—C5—C6—C1 | 0.4 (3) | C22—C21—O2—C24 | −29.7 (3) |
C4—C5—C6—C7 | −178.9 (2) | C22—C21—O2—Li1 | 167.32 (17) |
C2—C1—C6—C5 | −2.1 (3) | O2ii—Li1—O2—C24 | 31.1 (3) |
N1—C1—C6—C5 | 178.98 (19) | O3ii—Li1—O2—C24 | −93.1 (4) |
C2—C1—C6—C7 | 177.41 (19) | O3—Li1—O2—C24 | 148.7 (3) |
N1—C1—C6—C7 | −1.5 (2) | O2ii—Li1—O2—C21 | −169.9 (2) |
C5—C6—C7—C8 | 1.2 (4) | O3ii—Li1—O2—C21 | 65.9 (2) |
C1—C6—C7—C8 | −178.2 (2) | O3—Li1—O2—C21 | −52.3 (3) |
C5—C6—C7—C12 | 179.7 (2) | C27'—C28'—O3—C25 | −19 (3) |
C1—C6—C7—C12 | 0.3 (2) | C27'—C28'—O3—C28 | 96 (5) |
C12—C7—C8—C9 | 0.7 (4) | C27'—C28'—O3—C25' | −18 (4) |
C6—C7—C8—C9 | 179.0 (3) | C27'—C28'—O3—Li1 | −175 (2) |
C7—C8—C9—C10 | −0.5 (4) | C26—C25—O3—C28' | 28.1 (18) |
C8—C9—C10—C11 | −0.2 (4) | C26—C25—O3—C28 | 9.7 (17) |
C9—C10—C11—C12 | 0.8 (4) | C26—C25—O3—C25' | −139 (21) |
C10—C11—C12—N1 | 179.6 (2) | C26—C25—O3—Li1 | −177.1 (9) |
C10—C11—C12—C7 | −0.7 (3) | C27—C28—O3—C28' | −81 (4) |
C8—C7—C12—C11 | −0.1 (3) | C27—C28—O3—C25 | −12.0 (19) |
C6—C7—C12—C11 | −178.8 (2) | C27—C28—O3—C25' | −9 (2) |
C8—C7—C12—N1 | 179.7 (2) | C27—C28—O3—Li1 | 174.4 (12) |
C6—C7—C12—N1 | 1.0 (2) | C26'—C25'—O3—C28' | −5 (3) |
N2—C13—C14—C15 | 178.40 (18) | C26'—C25'—O3—C25 | 8 (19) |
C18—C13—C14—C15 | −0.4 (3) | C26'—C25'—O3—C28 | −25 (2) |
C13—C14—C15—C16 | 0.3 (3) | C26'—C25'—O3—Li1 | 152.4 (15) |
C14—C15—C16—C17 | 0.2 (4) | O2ii—Li1—O3—C28' | −14 (2) |
C15—C16—C17—C18 | −0.7 (3) | O2—Li1—O3—C28' | −134.2 (19) |
C16—C17—C18—C13 | 0.6 (3) | O3ii—Li1—O3—C28' | 109.2 (19) |
C16—C17—C18—C18i | −179.4 (3) | O2ii—Li1—O3—C25 | −163.1 (11) |
C14—C13—C18—C17 | −0.1 (3) | O2—Li1—O3—C25 | 77.0 (12) |
N2—C13—C18—C17 | −179.06 (17) | O3ii—Li1—O3—C25 | −39.6 (11) |
C14—C13—C18—C18i | 179.9 (2) | O2ii—Li1—O3—C28 | 9.2 (12) |
N2—C13—C18—C18i | 1.0 (3) | O2—Li1—O3—C28 | −110.8 (12) |
O2—C21—C22—C23 | 13.2 (3) | O3ii—Li1—O3—C28 | 132.6 (12) |
C21—C22—C23—C24 | 7.6 (3) | O2ii—Li1—O3—C25' | −167.4 (10) |
C22—C23—C24—O2 | −26.1 (4) | O2—Li1—O3—C25' | 72.6 (10) |
O1—C19—C20—C20i | −35.0 (17) | O3ii—Li1—O3—C25' | −44.0 (10) |
C20'—C19—C20—C20i | 58.1 (14) | C13—N2—Zr1—N1 | −39.04 (11) |
O3—C25—C26—C27 | −4 (2) | C13i—N2—Zr1—N1 | 140.96 (11) |
C25—C26—C27—C28 | −4 (2) | C13—N2—Zr1—N1i | 140.96 (11) |
C26—C27—C28—O3 | 10 (2) | C13i—N2—Zr1—N1i | −39.04 (11) |
O1—C19—C20'—C20'i | 33.2 (18) | C13—N2—Zr1—Cl1 | −128.58 (10) |
C20—C19—C20'—C20'i | −60.4 (17) | C13i—N2—Zr1—Cl1 | 51.42 (10) |
O3—C25'—C26'—C27' | 25 (2) | C13—N2—Zr1—Cl1i | 51.42 (10) |
C25'—C26'—C27'—C28' | −36 (3) | C13i—N2—Zr1—Cl1i | −128.58 (10) |
C26'—C27'—C28'—O3 | 34 (3) | C12—N1—Zr1—N2 | 142.95 (16) |
C11—C12—N1—C1 | 177.9 (2) | C1—N1—Zr1—N2 | −49.66 (16) |
C7—C12—N1—C1 | −1.9 (2) | C1—N1—Zr1—N1i | 130.34 (15) |
C11—C12—N1—Zr1 | −12.7 (3) | C12—N1—Zr1—O1 | −37.05 (16) |
C7—C12—N1—Zr1 | 167.53 (14) | C1—N1—Zr1—O1 | 130.34 (16) |
C2—C1—N1—C12 | −176.7 (2) | C12—N1—Zr1—Cl1 | −125.14 (17) |
C6—C1—N1—C12 | 2.1 (2) | C1—N1—Zr1—Cl1 | 42.24 (15) |
C2—C1—N1—Zr1 | 13.3 (3) | C12—N1—Zr1—Cl1i | 50.95 (17) |
C6—C1—N1—Zr1 | −167.84 (13) | C1—N1—Zr1—Cl1i | −141.67 (15) |
C14—C13—N2—C13i | −179.3 (3) | C19i—O1—Zr1—N1 | −51.40 (13) |
C18—C13—N2—C13i | −0.38 (10) | C19i—O1—Zr1—N1i | 128.60 (13) |
C14—C13—N2—Zr1 | 0.7 (3) | C19i—O1—Zr1—Cl1 | 38.15 (13) |
C18—C13—N2—Zr1 | 179.62 (10) | C19i—O1—Zr1—Cl1i | −141.85 (13) |
C20—C19—O1—C19i | 13.9 (7) | C19—O1—Zr1—Cl1i | 38.15 (13) |
Symmetry codes: (i) −x, y, −z+3/2; (ii) −x+1, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Li(C4H8O)4][ZrCl2(C12H8N)3(C4H8O)] |
Mr | 1028.16 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 173 |
a, b, c (Å) | 14.984 (5), 27.435 (9), 13.574 (4) |
β (°) | 113.220 (5) |
V (Å3) | 5128 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.37 |
Crystal size (mm) | 0.22 × 0.19 × 0.15 |
Data collection | |
Diffractometer | Bruker AXS CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.946, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24554, 5069, 4128 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.088, 1.07 |
No. of reflections | 5069 |
No. of parameters | 357 |
No. of restraints | 30 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.75, −0.47 |
Computer programs: SMART (Bruker 1997), SAINT (Bruker 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
Li1—O2i | 1.939 (4) | O1—Zr1 | 2.261 (2) |
Li1—O3i | 1.952 (4) | Zr1—N1ii | 2.2185 (18) |
N2—Zr1 | 2.167 (3) | Zr1—Cl1ii | 2.4488 (9) |
N2—Zr1—N1ii | 96.26 (4) | Cl1—Zr1—Cl1ii | 176.07 (3) |
N1—Zr1—N1ii | 167.49 (9) | ||
C25—C26—C27—C28 | −4 (2) | C25'—C26'—C27'—C28' | −36 (3) |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x, y, −z+3/2. |
Trisamide complexes of transition metals show a wide and varied reactivity, and the synthesis and exploration of this class of compound have been the focus of considerable research in recent years in the inorganic community (Cummins et al., 1988, 1991, 1998a; Yandulov et al., 2002). These studies have used electronically hard ligands, often for the formation of low-coordinate metal complexes with a view to small molecule activation (Cummins, 1998a). The merit of the study of complexes of this type has been demonstrated by the catalytic reduction of N2 to NH3 (Yandulov et al., 2002, 2003). Recently, complexes with softer non-innocent ligands have been reported (Nygren et al., 2003a, 2003b; Tanski & Parkin, 2003).
Structurally characterized carbazolyl complexes of the transition metals that are σ-bound are rare (Lopez et al., 2002); most of the known examples (Riley et al., 1998, 1999, 2001) are for groups 4B and 5B. In most previous reports of group 4B metal complexes containing carbazolyl ligands, the metal center is surrounded by other nitrogen-containing ligands, such as dimethylamine (Riley et al., 1999, 2001).
The molecular structure of (I) is shown in Fig. 1. Examination of the Cambridge Structural Database (CSD; Allen, 2002; Bruno et al., 2002) revealed that the Zr—N bond lengths [Zr—Navg = 2.202 (3) Å] of the carbazolyl ligands are well within the range of normal Zr—N bond lengths (Zr—Navg = 2.241 Å) reported in the literature. The Zr—Cl bond lengths are also well within the typical range (2.287–2.734 Å) reported for the first coordination sphere of zirconium consisting of two Cl atoms, three N atoms and one O-containing ligand. This search also revealed that the first coordination sphere of zirconium consisting of three N atoms, one O atom and two Cl atoms is rare in the structural chemistry of group 4B metals, with only eight examples in the database.
In the THF molecule, which ligates the zirconium center, atoms C20 and C20A are disordered over two sites, with relative occupancies of approximately 0.4 and 0.6. Similarly, in the Li(thf)4 moiety, the thf molecule consisting of atoms C25, C26, C27 and C28, and the symmetry-generated thf molecule, are disordered over two sites, hereafter termed the thf and thf` molecules, where the prime denotes a separate molecule with fractional population. The disorders in the C25 and C28 postions were treated identically, i.e. as a group, and the disorders in the C26 and C27 positions were treated in a similar manner. Atoms C25 and C28, and C25` and C28`, were modeled with opposing populations, leading to occupancies of approximately 0.6 and approximately 0.4, respectively, for both atom sets. Atoms C26 and C27 were also modeled as being distributed over two sites, giving the pairs C26 and C26`, and C27 and C27`. The occupancies in this case are 0.5 for both sites of both atom pairs. The thf molecule composed of atoms O3 and C25–C28 has a bent conformation, the C25—C26—C27—C28 torsion angle being 4(2)°, whereas for the second component of the disordered model, thf`, the torsion angle is 36 (3)°. These torsion angles are well within the normal range for thf coordinated to a metal center, as shown by a search of the CSD. For this torsion angle, 94.9% of the observed angles lie between +40 and −40°, [mean 0.487 (8)°]. Although this solution may not be a perfect disorder model, it is the best fit given the quality of the data.
Recently, we reported the crystal structure of the related potassium salt (tetrahydrofuran)potassium mer-[tris(carbazolyl)-trans-dichloro(tetrahydrofurano)zirconate] (Nygren et al., 2003a). The trans-carbazolyl ligands in (I) deviate from linearity [167.49 (9)°] to a greater extent than those in the corresponding potassium complex [171.90 (7)°]. However, the Cl—Zr—Cl angle is more linear [176.08 (3)°] in (I) than in the potassium analog [171.38 (2)°]. In (I), there is very little interaction between the tetrakis(tetrahydrofuran)lithium segment of the structure and the zirconium fragment. The closest contact distance between the carbazolyl ligands and the cation is approximately 4.44 Å. By contrast, in the potassium complex, the cation is bound to two of the carbazolyl ligands in an η2 and an η6 fashion. This interaction, however, has very little effect on the structure of the zirconium anion. A slight difference may be seen in the intramolecular angles. The cis-carbazolyls that are most affected by the presence of the cation differ in the N—Zr—N angle by 3.03° [96.26 (5) and 93.23 (7)° for lithium and potassium, respectively]. Further comparison of the structures of the anions in both structures show that the type of cation has little influence on the overall anion structure. Given the close coordination of the K(THF) ion to the Zr complex, this is surprising. However, the site between the rings that is occupied by the K atom is occupied by a thf moiety of the Li(THF)4 cation in (I).