metal-organic compounds
(Cyanido-κC)(2,2-diphenylacetamido-κ2N,O)bis(η5-pentamethylcyclopentadienyl)zirconium(IV)
aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29A, 18059 Rostock, Germany
*Correspondence e-mail: lisanne.becker@catalysis.de
In the title compound, [Zr(C10H15)2(C14H12NO)(CN)], the ZrIV atom is coordinated by two pentamethylcyclopentadienyl ligands, the amidate ligand via the N and O atoms, and an additional C≡N ligand. The four-membered metallacycle is nearly planar (r.m.s. deviation = 0.008 Å). In the crystal, the molecules are connected into centrosymmetric dimers via pairs of N—H⋯N hydrogen bonds.
CCDC reference: 981857
Related literature
For structures of mononuclear group 4 metallocene complexes with κ2-N,O chelating amidate ligands without additional coordination of its substituents, see: Arndt et al. (1996); Gambarotta et al. (1985); Haehnel et al. (2013); Ruck & Bergman (2004). For structures of group 4 metallocene complexes with κ2N,O-chelating OC(P)N(R) ligands, see: Segerer et al. (2000); Frömel et al. (2013). For a similar complex, see: Becker et al. (2013).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2011); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 981857
10.1107/S1600536814001160/bt6957sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814001160/bt6957Isup2.hkl
To a stirred solution of Cp*2Zr(η2-Me3SiC2SiMe3) (0.266 g, 0.5 mmol) in 5 mL of toluene was added a solution of Ph2CH—CN (0.193 g, 1.0 mmol) in 10 mL of toluene. The solution was stirred for 2 h at room temperature and subsequently 24 h at 358 K till the color turned to orange. All volatiles were removed under vacuum and the residue was dissolved in n-hexane. After filtration the solution was allowed to stand at r. t.. Yellow crystals of the title compound were formed within 14 days. MS: m/z (CI): 596 [M]+ (3), 570 [M—CN]+ (1), 386 [Cp*2Zr(CN)]+ (1), 360 [Cp*2Zr]+ (1). IR: (ATR, cm-1): υ = 2900(w), 2133(vw), 1426 (m), 1259(s), 1019 (vs), 795(vs).
H1 and H2 could be found from the difference Fourier map and were refined freely. All other H atoms were placed in idealized positions with d(C—H) = 0.98 (CH3) and 0.95 Å (CH) and refined using a riding model with Uiso(H) fixed at 1.5 Ueq(C) for CH3 and 1.2 Ueq(C) for CH. In one of the both phenyl rings two distances (C5—C6 and C6—C7) were restrained to be equal (SADI).
We studied the reactions of several η2-Me3SiC2SiMe3) (Cp* = η5– pentamethylcyclopentadienyl, M = Ti, Zr) to synthesize and characterize new strained metallacycles with heteroatoms. In the reaction with diphenylacetonitrile the complex Cp*2Zr(N=CH-CHPh2)(N=C=CPh2) (Becker et al. (2013)) was formed after 4 h at 358 K. However a longer reaction time of 24 h led to the cleavage of the Ph2CH—CN bond upon partial oxidation thus forming the title compound. The zirconium(IV) atom is coordinated by two pentamethylcyclopentadienyl ligands in a η5-fashion, as well as by the N– and O-atoms of the amidate and an additional C≡N ligand. The four-membered ring is almost planar (mean deviation from the best plane defined by Zr1, O1, C1, N1 = 0.008 Å). The bond lengths O1—C1 1.290 (3) and N1—C1 1.294 (3) Å suggest the resonance form with electronic delocalization within the OCN unit. The molecules are connected to centrosymmetric dimers via N—H···N hydrogen bonds.
with metallocene precursors as Cp*2M(For structures of mononuclear group 4 metallocene complexes with κ2-N,O chelating amidate ligands without additional coordination of its substituents, see: Arndt et al. (1996); Gambarotta et al. (1985); Haehnel et al. (2013); Ruck & Bergman (2004). For structures of group 4 metallocene complexes with κ2-N,O chelating OC(P)N(R) ligands see: Segerer et al. (2000); Frömel et al. (2013). For a similar complex, see: Becker et al. (2013).
Data collection: APEX2 (Bruker, 2011); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of the title compound with 30% displacement ellipsoids. Hydrogen atoms (except H1 and H2) are omitted for clarity. |
[Zr(C10H15)2(C14H12NO)(CN)] | F(000) = 1256 |
Mr = 597.93 | Dx = 1.312 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 9874 reflections |
a = 11.8961 (3) Å | θ = 2.4–27.8° |
b = 12.0640 (3) Å | µ = 0.39 mm−1 |
c = 21.2489 (5) Å | T = 150 K |
β = 97.036 (1)° | Prism, red |
V = 3026.56 (13) Å3 | 0.26 × 0.13 × 0.10 mm |
Z = 4 |
Bruker Kappa APEXII DUO diffractometer | 6612 independent reflections |
Radiation source: fine-focus sealed tube | 5575 reflections with I > 2σ(I) |
Curved graphite monochromator | Rint = 0.047 |
Detector resolution: 8.3333 pixels mm-1 | θmax = 27.0°, θmin = 1.9° |
φ and ω scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | k = −15→15 |
Tmin = 0.92, Tmax = 1.00 | l = −27→26 |
82697 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0376P)2 + 3.2391P] where P = (Fo2 + 2Fc2)/3 |
6612 reflections | (Δ/σ)max = 0.001 |
370 parameters | Δρmax = 1.11 e Å−3 |
1 restraint | Δρmin = −0.46 e Å−3 |
[Zr(C10H15)2(C14H12NO)(CN)] | V = 3026.56 (13) Å3 |
Mr = 597.93 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.8961 (3) Å | µ = 0.39 mm−1 |
b = 12.0640 (3) Å | T = 150 K |
c = 21.2489 (5) Å | 0.26 × 0.13 × 0.10 mm |
β = 97.036 (1)° |
Bruker Kappa APEXII DUO diffractometer | 6612 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | 5575 reflections with I > 2σ(I) |
Tmin = 0.92, Tmax = 1.00 | Rint = 0.047 |
82697 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 1 restraint |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 1.11 e Å−3 |
6612 reflections | Δρmin = −0.46 e Å−3 |
370 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. |
x | y | z | Uiso*/Ueq | ||
N2 | 0.34293 (17) | −0.01561 (17) | −0.00689 (9) | 0.0328 (4) | |
C1 | 0.57641 (17) | 0.23133 (18) | 0.13538 (10) | 0.0249 (4) | |
C2 | 0.69873 (18) | 0.27295 (19) | 0.15050 (11) | 0.0287 (5) | |
C3 | 0.77338 (17) | 0.18091 (19) | 0.18260 (10) | 0.0263 (4) | |
C4 | 0.8135 (2) | 0.1921 (2) | 0.24651 (12) | 0.0380 (6) | |
H4 | 0.7986 | 0.2582 | 0.2683 | 0.046* | |
C5 | 0.8753 (2) | 0.1074 (2) | 0.27887 (12) | 0.0440 (7) | |
H5 | 0.9026 | 0.1160 | 0.3225 | 0.053* | |
C6 | 0.89672 (19) | 0.0113 (2) | 0.24769 (10) | 0.0385 (6) | |
H6 | 0.9376 | −0.0473 | 0.2699 | 0.046* | |
C7 | 0.85877 (19) | 0.0001 (2) | 0.18414 (11) | 0.0361 (5) | |
H7 | 0.8743 | −0.0660 | 0.1625 | 0.043* | |
C8 | 0.79802 (19) | 0.0848 (2) | 0.15157 (12) | 0.0327 (5) | |
H8 | 0.7731 | 0.0767 | 0.1076 | 0.039* | |
C9 | 0.74590 (17) | 0.32921 (19) | 0.09490 (11) | 0.0288 (5) | |
C10 | 0.7888 (2) | 0.4362 (2) | 0.10502 (14) | 0.0395 (6) | |
H10 | 0.7859 | 0.4708 | 0.1450 | 0.047* | |
C11 | 0.8354 (2) | 0.4929 (2) | 0.05789 (17) | 0.0500 (8) | |
H11 | 0.8649 | 0.5654 | 0.0658 | 0.060* | |
C12 | 0.8391 (2) | 0.4447 (2) | −0.00014 (15) | 0.0476 (7) | |
H12 | 0.8710 | 0.4835 | −0.0326 | 0.057* | |
C13 | 0.7963 (2) | 0.3402 (3) | −0.01104 (13) | 0.0462 (7) | |
H13 | 0.7982 | 0.3069 | −0.0514 | 0.055* | |
C14 | 0.7503 (2) | 0.2821 (2) | 0.03594 (12) | 0.0376 (6) | |
H14 | 0.7216 | 0.2094 | 0.0276 | 0.045* | |
C15 | 0.34628 (17) | 0.04561 (18) | 0.03489 (10) | 0.0251 (4) | |
C16 | 0.24386 (18) | 0.02069 (19) | 0.16252 (11) | 0.0302 (5) | |
C17 | 0.2474 (2) | 0.1093 (2) | 0.20580 (12) | 0.0366 (6) | |
C18 | 0.3598 (3) | 0.1224 (2) | 0.23301 (11) | 0.0432 (7) | |
C19 | 0.4268 (2) | 0.0400 (2) | 0.20780 (12) | 0.0367 (6) | |
C20 | 0.35450 (19) | −0.02379 (18) | 0.16495 (11) | 0.0294 (5) | |
C21 | 0.1403 (2) | −0.0292 (3) | 0.12447 (16) | 0.0520 (8) | |
H21A | 0.1596 | −0.0533 | 0.0831 | 0.078* | |
H21B | 0.0800 | 0.0265 | 0.1184 | 0.078* | |
H21C | 0.1143 | −0.0929 | 0.1473 | 0.078* | |
C22 | 0.1453 (3) | 0.1632 (3) | 0.22946 (17) | 0.0641 (10) | |
H22A | 0.1349 | 0.1329 | 0.2711 | 0.096* | |
H22B | 0.0776 | 0.1482 | 0.1995 | 0.096* | |
H22C | 0.1573 | 0.2435 | 0.2330 | 0.096* | |
C23 | 0.3975 (4) | 0.2020 (3) | 0.28566 (14) | 0.0799 (13) | |
H23A | 0.3571 | 0.2724 | 0.2779 | 0.120* | |
H23B | 0.4792 | 0.2148 | 0.2874 | 0.120* | |
H23C | 0.3809 | 0.1708 | 0.3261 | 0.120* | |
C24 | 0.5490 (2) | 0.0163 (3) | 0.22950 (18) | 0.0754 (13) | |
H24A | 0.5546 | −0.0385 | 0.2638 | 0.113* | |
H24B | 0.5870 | 0.0849 | 0.2449 | 0.113* | |
H24C | 0.5852 | −0.0130 | 0.1940 | 0.113* | |
C25 | 0.3906 (3) | −0.1274 (2) | 0.13436 (15) | 0.0571 (9) | |
H25A | 0.4570 | −0.1117 | 0.1127 | 0.086* | |
H25B | 0.3286 | −0.1542 | 0.1035 | 0.086* | |
H25C | 0.4100 | −0.1842 | 0.1669 | 0.086* | |
C26 | 0.34767 (17) | 0.36419 (18) | 0.06928 (10) | 0.0254 (4) | |
C27 | 0.31732 (19) | 0.29185 (19) | 0.01829 (10) | 0.0286 (5) | |
C28 | 0.2112 (2) | 0.24409 (19) | 0.02668 (12) | 0.0321 (5) | |
C29 | 0.17714 (18) | 0.28634 (19) | 0.08314 (12) | 0.0304 (5) | |
C30 | 0.26353 (19) | 0.35821 (18) | 0.11072 (11) | 0.0272 (5) | |
C31 | 0.4448 (2) | 0.4441 (2) | 0.07480 (14) | 0.0426 (6) | |
H31A | 0.5096 | 0.4099 | 0.0579 | 0.064* | |
H31B | 0.4662 | 0.4633 | 0.1195 | 0.064* | |
H31C | 0.4223 | 0.5114 | 0.0507 | 0.064* | |
C32 | 0.3803 (3) | 0.2783 (3) | −0.03833 (13) | 0.0503 (8) | |
H32A | 0.3611 | 0.3394 | −0.0680 | 0.075* | |
H32B | 0.3590 | 0.2077 | −0.0594 | 0.075* | |
H32C | 0.4620 | 0.2787 | −0.0245 | 0.075* | |
C33 | 0.1360 (3) | 0.1774 (2) | −0.02120 (16) | 0.0569 (9) | |
H33A | 0.0978 | 0.1196 | 0.0006 | 0.085* | |
H33B | 0.1819 | 0.1431 | −0.0512 | 0.085* | |
H33C | 0.0793 | 0.2262 | −0.0443 | 0.085* | |
C34 | 0.0582 (2) | 0.2786 (3) | 0.10029 (18) | 0.0566 (9) | |
H34A | 0.0069 | 0.3209 | 0.0696 | 0.085* | |
H34B | 0.0559 | 0.3090 | 0.1429 | 0.085* | |
H34C | 0.0344 | 0.2008 | 0.0995 | 0.085* | |
C35 | 0.2603 (3) | 0.4316 (2) | 0.16760 (13) | 0.0468 (7) | |
H35A | 0.3304 | 0.4224 | 0.1965 | 0.070* | |
H35B | 0.1954 | 0.4113 | 0.1895 | 0.070* | |
H35C | 0.2529 | 0.5091 | 0.1539 | 0.070* | |
O1 | 0.50256 (12) | 0.27068 (13) | 0.16907 (7) | 0.0267 (3) | |
N1 | 0.53651 (15) | 0.15917 (15) | 0.09345 (9) | 0.0255 (4) | |
Zr1 | 0.357855 (15) | 0.171301 (16) | 0.116794 (9) | 0.01859 (7) | |
H1 | 0.696 (2) | 0.334 (2) | 0.1837 (13) | 0.036 (7)* | |
H2 | 0.580 (2) | 0.125 (2) | 0.0680 (13) | 0.040 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N2 | 0.0342 (10) | 0.0311 (10) | 0.0329 (11) | 0.0002 (8) | 0.0028 (8) | −0.0078 (9) |
C1 | 0.0241 (10) | 0.0236 (10) | 0.0260 (11) | 0.0015 (8) | −0.0010 (8) | 0.0046 (9) |
C2 | 0.0225 (10) | 0.0283 (12) | 0.0343 (12) | −0.0006 (9) | −0.0006 (9) | −0.0053 (10) |
C3 | 0.0170 (9) | 0.0332 (12) | 0.0282 (11) | −0.0026 (8) | 0.0017 (8) | 0.0012 (9) |
C4 | 0.0338 (12) | 0.0481 (15) | 0.0319 (13) | −0.0023 (11) | 0.0032 (10) | −0.0060 (11) |
C5 | 0.0350 (13) | 0.0678 (19) | 0.0278 (12) | 0.0033 (13) | −0.0014 (10) | 0.0094 (13) |
C6 | 0.0257 (11) | 0.0513 (16) | 0.0385 (13) | 0.0029 (11) | 0.0031 (10) | 0.0200 (12) |
C7 | 0.0258 (11) | 0.0368 (13) | 0.0447 (14) | 0.0020 (10) | 0.0009 (10) | 0.0025 (11) |
C8 | 0.0266 (11) | 0.0385 (13) | 0.0315 (12) | 0.0008 (10) | −0.0024 (9) | −0.0025 (10) |
C9 | 0.0155 (9) | 0.0278 (11) | 0.0415 (13) | 0.0017 (8) | −0.0028 (8) | 0.0055 (10) |
C10 | 0.0275 (11) | 0.0281 (12) | 0.0616 (17) | 0.0028 (10) | −0.0004 (11) | −0.0026 (12) |
C11 | 0.0345 (13) | 0.0229 (12) | 0.090 (2) | −0.0003 (10) | −0.0033 (14) | 0.0133 (14) |
C12 | 0.0319 (13) | 0.0497 (16) | 0.0590 (18) | −0.0039 (12) | −0.0038 (12) | 0.0322 (15) |
C13 | 0.0412 (14) | 0.0571 (18) | 0.0385 (14) | −0.0104 (13) | −0.0020 (11) | 0.0103 (13) |
C14 | 0.0357 (13) | 0.0349 (13) | 0.0410 (14) | −0.0109 (10) | −0.0005 (11) | 0.0026 (11) |
C15 | 0.0218 (10) | 0.0241 (10) | 0.0296 (11) | 0.0012 (8) | 0.0038 (8) | 0.0022 (9) |
C16 | 0.0260 (10) | 0.0280 (11) | 0.0378 (13) | −0.0022 (9) | 0.0086 (9) | 0.0112 (10) |
C17 | 0.0463 (14) | 0.0310 (13) | 0.0374 (13) | 0.0044 (11) | 0.0251 (11) | 0.0093 (11) |
C18 | 0.0728 (19) | 0.0369 (14) | 0.0213 (11) | −0.0169 (13) | 0.0112 (12) | 0.0030 (10) |
C19 | 0.0283 (11) | 0.0468 (15) | 0.0338 (13) | −0.0054 (10) | −0.0016 (10) | 0.0237 (11) |
C20 | 0.0343 (11) | 0.0244 (11) | 0.0316 (12) | 0.0044 (9) | 0.0129 (9) | 0.0110 (9) |
C21 | 0.0371 (14) | 0.0476 (17) | 0.069 (2) | −0.0163 (12) | −0.0024 (13) | 0.0180 (15) |
C22 | 0.084 (2) | 0.0479 (18) | 0.072 (2) | 0.0241 (17) | 0.0557 (19) | 0.0213 (16) |
C23 | 0.138 (4) | 0.073 (2) | 0.0282 (15) | −0.050 (2) | 0.0097 (19) | −0.0038 (15) |
C24 | 0.0341 (15) | 0.099 (3) | 0.087 (3) | −0.0100 (16) | −0.0154 (15) | 0.069 (2) |
C25 | 0.093 (2) | 0.0313 (14) | 0.0528 (18) | 0.0231 (15) | 0.0334 (17) | 0.0160 (13) |
C26 | 0.0232 (10) | 0.0228 (10) | 0.0293 (11) | 0.0040 (8) | −0.0003 (8) | 0.0076 (9) |
C27 | 0.0348 (12) | 0.0279 (11) | 0.0230 (11) | 0.0109 (9) | 0.0024 (9) | 0.0070 (9) |
C28 | 0.0324 (12) | 0.0236 (11) | 0.0364 (13) | 0.0061 (9) | −0.0121 (10) | 0.0009 (10) |
C29 | 0.0216 (10) | 0.0247 (11) | 0.0450 (14) | 0.0083 (9) | 0.0040 (9) | 0.0088 (10) |
C30 | 0.0312 (11) | 0.0208 (10) | 0.0295 (11) | 0.0083 (8) | 0.0036 (9) | 0.0042 (9) |
C31 | 0.0368 (13) | 0.0326 (13) | 0.0561 (17) | −0.0063 (11) | −0.0032 (12) | 0.0183 (12) |
C32 | 0.073 (2) | 0.0499 (17) | 0.0317 (14) | 0.0236 (15) | 0.0221 (13) | 0.0135 (12) |
C33 | 0.0587 (18) | 0.0383 (15) | 0.0634 (19) | 0.0060 (13) | −0.0336 (16) | −0.0080 (14) |
C34 | 0.0244 (12) | 0.0531 (18) | 0.094 (2) | 0.0121 (12) | 0.0138 (14) | 0.0289 (17) |
C35 | 0.073 (2) | 0.0287 (13) | 0.0398 (15) | 0.0130 (13) | 0.0124 (14) | −0.0039 (11) |
O1 | 0.0238 (7) | 0.0297 (8) | 0.0266 (8) | 0.0004 (6) | 0.0030 (6) | −0.0016 (6) |
N1 | 0.0214 (8) | 0.0266 (9) | 0.0290 (9) | 0.0017 (7) | 0.0047 (7) | −0.0027 (8) |
Zr1 | 0.01732 (10) | 0.01876 (10) | 0.02010 (10) | 0.00190 (7) | 0.00397 (7) | 0.00094 (8) |
N2—C15 | 1.152 (3) | C21—H21B | 0.9800 |
C1—O1 | 1.290 (3) | C21—H21C | 0.9800 |
C1—N1 | 1.294 (3) | C22—H22A | 0.9800 |
C1—C2 | 1.536 (3) | C22—H22B | 0.9800 |
C1—Zr1 | 2.681 (2) | C22—H22C | 0.9800 |
C2—C9 | 1.528 (3) | C23—H23A | 0.9800 |
C2—C3 | 1.529 (3) | C23—H23B | 0.9800 |
C2—H1 | 1.03 (3) | C23—H23C | 0.9800 |
C3—C8 | 1.383 (3) | C24—H24A | 0.9800 |
C3—C4 | 1.390 (3) | C24—H24B | 0.9800 |
C4—C5 | 1.389 (4) | C24—H24C | 0.9800 |
C4—H4 | 0.9500 | C25—H25A | 0.9800 |
C5—C6 | 1.375 (3) | C25—H25B | 0.9800 |
C5—H5 | 0.9500 | C25—H25C | 0.9800 |
C6—C7 | 1.377 (2) | C26—C27 | 1.404 (3) |
C6—H6 | 0.9500 | C26—C30 | 1.414 (3) |
C7—C8 | 1.386 (3) | C26—C31 | 1.499 (3) |
C7—H7 | 0.9500 | C26—Zr1 | 2.533 (2) |
C8—H8 | 0.9500 | C27—C28 | 1.419 (3) |
C9—C14 | 1.383 (4) | C27—C32 | 1.502 (3) |
C9—C10 | 1.395 (3) | C27—Zr1 | 2.546 (2) |
C10—C11 | 1.383 (4) | C28—C29 | 1.408 (4) |
C10—H10 | 0.9500 | C28—C33 | 1.503 (3) |
C11—C12 | 1.369 (4) | C28—Zr1 | 2.581 (2) |
C11—H11 | 0.9500 | C29—C30 | 1.415 (3) |
C12—C13 | 1.369 (4) | C29—C34 | 1.507 (3) |
C12—H12 | 0.9500 | C29—Zr1 | 2.585 (2) |
C13—C14 | 1.386 (4) | C30—C35 | 1.503 (3) |
C13—H13 | 0.9500 | C30—Zr1 | 2.515 (2) |
C14—H14 | 0.9500 | C31—H31A | 0.9800 |
C15—Zr1 | 2.300 (2) | C31—H31B | 0.9800 |
C16—C17 | 1.407 (4) | C31—H31C | 0.9800 |
C16—C20 | 1.416 (3) | C32—H32A | 0.9800 |
C16—C21 | 1.513 (4) | C32—H32B | 0.9800 |
C16—Zr1 | 2.531 (2) | C32—H32C | 0.9800 |
C17—C18 | 1.399 (4) | C33—H33A | 0.9800 |
C17—C22 | 1.518 (4) | C33—H33B | 0.9800 |
C17—Zr1 | 2.544 (2) | C33—H33C | 0.9800 |
C18—C19 | 1.419 (4) | C34—H34A | 0.9800 |
C18—C23 | 1.501 (4) | C34—H34B | 0.9800 |
C18—Zr1 | 2.536 (2) | C34—H34C | 0.9800 |
C19—C20 | 1.403 (4) | C35—H35A | 0.9800 |
C19—C24 | 1.497 (4) | C35—H35B | 0.9800 |
C19—Zr1 | 2.556 (2) | C35—H35C | 0.9800 |
C20—C25 | 1.496 (4) | O1—Zr1 | 2.2729 (15) |
C20—Zr1 | 2.569 (2) | N1—Zr1 | 2.2455 (18) |
C21—H21A | 0.9800 | N1—H2 | 0.89 (3) |
O1—C1—N1 | 114.36 (19) | C32—C27—Zr1 | 122.23 (16) |
O1—C1—C2 | 117.13 (19) | C29—C28—C27 | 108.3 (2) |
N1—C1—C2 | 128.5 (2) | C29—C28—C33 | 124.1 (2) |
O1—C1—Zr1 | 57.79 (10) | C27—C28—C33 | 126.7 (3) |
N1—C1—Zr1 | 56.59 (11) | C29—C28—Zr1 | 74.33 (13) |
C2—C1—Zr1 | 174.91 (16) | C27—C28—Zr1 | 72.56 (12) |
C9—C2—C3 | 114.79 (18) | C33—C28—Zr1 | 127.75 (16) |
C9—C2—C1 | 114.33 (18) | C28—C29—C30 | 107.7 (2) |
C3—C2—C1 | 109.85 (18) | C28—C29—C34 | 124.1 (2) |
C9—C2—H1 | 104.9 (15) | C30—C29—C34 | 126.4 (2) |
C3—C2—H1 | 106.4 (15) | C28—C29—Zr1 | 74.05 (12) |
C1—C2—H1 | 105.7 (15) | C30—C29—Zr1 | 71.18 (12) |
C8—C3—C4 | 118.6 (2) | C34—C29—Zr1 | 132.34 (17) |
C8—C3—C2 | 122.8 (2) | C26—C30—C29 | 107.9 (2) |
C4—C3—C2 | 118.5 (2) | C26—C30—C35 | 124.1 (2) |
C5—C4—C3 | 120.7 (2) | C29—C30—C35 | 127.2 (2) |
C5—C4—H4 | 119.7 | C26—C30—Zr1 | 74.46 (12) |
C3—C4—H4 | 119.7 | C29—C30—Zr1 | 76.63 (12) |
C6—C5—C4 | 120.0 (2) | C35—C30—Zr1 | 122.86 (16) |
C6—C5—H5 | 120.0 | C26—C31—H31A | 109.5 |
C4—C5—H5 | 120.0 | C26—C31—H31B | 109.5 |
C5—C6—C7 | 119.8 (2) | H31A—C31—H31B | 109.5 |
C5—C6—H6 | 120.1 | C26—C31—H31C | 109.5 |
C7—C6—H6 | 120.1 | H31A—C31—H31C | 109.5 |
C6—C7—C8 | 120.4 (2) | H31B—C31—H31C | 109.5 |
C6—C7—H7 | 119.8 | C27—C32—H32A | 109.5 |
C8—C7—H7 | 119.8 | C27—C32—H32B | 109.5 |
C3—C8—C7 | 120.5 (2) | H32A—C32—H32B | 109.5 |
C3—C8—H8 | 119.7 | C27—C32—H32C | 109.5 |
C7—C8—H8 | 119.7 | H32A—C32—H32C | 109.5 |
C14—C9—C10 | 117.8 (2) | H32B—C32—H32C | 109.5 |
C14—C9—C2 | 125.2 (2) | C28—C33—H33A | 109.5 |
C10—C9—C2 | 117.0 (2) | C28—C33—H33B | 109.5 |
C11—C10—C9 | 121.1 (3) | H33A—C33—H33B | 109.5 |
C11—C10—H10 | 119.4 | C28—C33—H33C | 109.5 |
C9—C10—H10 | 119.4 | H33A—C33—H33C | 109.5 |
C12—C11—C10 | 120.2 (2) | H33B—C33—H33C | 109.5 |
C12—C11—H11 | 119.9 | C29—C34—H34A | 109.5 |
C10—C11—H11 | 119.9 | C29—C34—H34B | 109.5 |
C11—C12—C13 | 119.4 (3) | H34A—C34—H34B | 109.5 |
C11—C12—H12 | 120.3 | C29—C34—H34C | 109.5 |
C13—C12—H12 | 120.3 | H34A—C34—H34C | 109.5 |
C12—C13—C14 | 121.0 (3) | H34B—C34—H34C | 109.5 |
C12—C13—H13 | 119.5 | C30—C35—H35A | 109.5 |
C14—C13—H13 | 119.5 | C30—C35—H35B | 109.5 |
C9—C14—C13 | 120.5 (2) | H35A—C35—H35B | 109.5 |
C9—C14—H14 | 119.8 | C30—C35—H35C | 109.5 |
C13—C14—H14 | 119.8 | H35A—C35—H35C | 109.5 |
N2—C15—Zr1 | 177.97 (19) | H35B—C35—H35C | 109.5 |
C17—C16—C20 | 108.1 (2) | C1—O1—Zr1 | 93.51 (12) |
C17—C16—C21 | 127.5 (2) | C1—N1—Zr1 | 94.67 (14) |
C20—C16—C21 | 124.1 (2) | C1—N1—H2 | 122.6 (18) |
C17—C16—Zr1 | 74.40 (13) | Zr1—N1—H2 | 142.7 (18) |
C20—C16—Zr1 | 75.33 (12) | N1—Zr1—O1 | 57.43 (6) |
C21—C16—Zr1 | 121.31 (17) | N1—Zr1—C15 | 76.14 (7) |
C18—C17—C16 | 107.8 (2) | O1—Zr1—C15 | 133.57 (6) |
C18—C17—C22 | 125.3 (3) | N1—Zr1—C30 | 118.39 (7) |
C16—C17—C22 | 125.5 (3) | O1—Zr1—C30 | 81.87 (6) |
C18—C17—Zr1 | 73.72 (13) | C15—Zr1—C30 | 124.57 (7) |
C16—C17—Zr1 | 73.40 (12) | N1—Zr1—C16 | 127.16 (7) |
C22—C17—Zr1 | 128.88 (17) | O1—Zr1—C16 | 126.89 (7) |
C17—C18—C19 | 108.5 (2) | C15—Zr1—C16 | 80.32 (8) |
C17—C18—C23 | 124.3 (3) | C30—Zr1—C16 | 113.99 (7) |
C19—C18—C23 | 126.8 (3) | N1—Zr1—C26 | 88.41 (7) |
C17—C18—Zr1 | 74.31 (14) | O1—Zr1—C26 | 72.94 (6) |
C19—C18—Zr1 | 74.59 (13) | C15—Zr1—C26 | 107.97 (7) |
C23—C18—Zr1 | 122.88 (19) | C30—Zr1—C26 | 32.52 (7) |
C20—C19—C18 | 107.5 (2) | C16—Zr1—C26 | 144.15 (7) |
C20—C19—C24 | 126.2 (3) | N1—Zr1—C18 | 107.68 (9) |
C18—C19—C24 | 125.9 (3) | O1—Zr1—C18 | 74.38 (7) |
C20—C19—Zr1 | 74.59 (13) | C15—Zr1—C18 | 125.16 (8) |
C18—C19—Zr1 | 73.05 (14) | C30—Zr1—C18 | 102.10 (9) |
C24—C19—Zr1 | 124.10 (17) | C16—Zr1—C18 | 53.18 (8) |
C19—C20—C16 | 108.0 (2) | C26—Zr1—C18 | 126.59 (8) |
C19—C20—C25 | 123.6 (2) | N1—Zr1—C17 | 137.22 (8) |
C16—C20—C25 | 128.0 (3) | O1—Zr1—C17 | 102.76 (7) |
C19—C20—Zr1 | 73.63 (13) | C15—Zr1—C17 | 112.35 (8) |
C16—C20—Zr1 | 72.43 (12) | C30—Zr1—C17 | 91.95 (8) |
C25—C20—Zr1 | 124.99 (16) | C16—Zr1—C17 | 32.20 (8) |
C16—C21—H21A | 109.5 | C26—Zr1—C17 | 124.23 (7) |
C16—C21—H21B | 109.5 | C18—Zr1—C17 | 31.98 (9) |
H21A—C21—H21B | 109.5 | N1—Zr1—C27 | 86.83 (7) |
C16—C21—H21C | 109.5 | O1—Zr1—C27 | 98.99 (7) |
H21A—C21—H21C | 109.5 | C15—Zr1—C27 | 76.51 (8) |
H21B—C21—H21C | 109.5 | C30—Zr1—C27 | 53.65 (7) |
C17—C22—H22A | 109.5 | C16—Zr1—C27 | 132.01 (8) |
C17—C22—H22B | 109.5 | C26—Zr1—C27 | 32.08 (7) |
H22A—C22—H22B | 109.5 | C18—Zr1—C27 | 155.74 (9) |
C17—C22—H22C | 109.5 | C17—Zr1—C27 | 135.74 (8) |
H22A—C22—H22C | 109.5 | N1—Zr1—C19 | 84.38 (7) |
H22B—C22—H22C | 109.5 | O1—Zr1—C19 | 78.67 (7) |
C18—C23—H23A | 109.5 | C15—Zr1—C19 | 98.49 (9) |
C18—C23—H23B | 109.5 | C30—Zr1—C19 | 133.98 (8) |
H23A—C23—H23B | 109.5 | C16—Zr1—C19 | 53.28 (7) |
C18—C23—H23C | 109.5 | C26—Zr1—C19 | 150.00 (8) |
H23A—C23—H23C | 109.5 | C18—Zr1—C19 | 32.36 (9) |
H23B—C23—H23C | 109.5 | C17—Zr1—C19 | 53.30 (8) |
C19—C24—H24A | 109.5 | C27—Zr1—C19 | 170.73 (8) |
C19—C24—H24B | 109.5 | N1—Zr1—C20 | 95.14 (7) |
H24A—C24—H24B | 109.5 | O1—Zr1—C20 | 109.66 (7) |
C19—C24—H24C | 109.5 | C15—Zr1—C20 | 72.23 (7) |
H24A—C24—H24C | 109.5 | C30—Zr1—C20 | 144.43 (7) |
H24B—C24—H24C | 109.5 | C16—Zr1—C20 | 32.24 (7) |
C20—C25—H25A | 109.5 | C26—Zr1—C20 | 176.37 (7) |
C20—C25—H25B | 109.5 | C18—Zr1—C20 | 52.96 (8) |
H25A—C25—H25B | 109.5 | C17—Zr1—C20 | 53.11 (7) |
C20—C25—H25C | 109.5 | C27—Zr1—C20 | 147.17 (8) |
H25A—C25—H25C | 109.5 | C19—Zr1—C20 | 31.78 (8) |
H25B—C25—H25C | 109.5 | N1—Zr1—C28 | 115.49 (8) |
C27—C26—C30 | 108.32 (19) | O1—Zr1—C28 | 125.85 (7) |
C27—C26—C31 | 125.7 (2) | C15—Zr1—C28 | 71.97 (7) |
C30—C26—C31 | 125.6 (2) | C30—Zr1—C28 | 53.14 (7) |
C27—C26—Zr1 | 74.44 (13) | C16—Zr1—C28 | 100.58 (8) |
C30—C26—Zr1 | 73.02 (12) | C26—Zr1—C28 | 52.91 (7) |
C31—C26—Zr1 | 124.11 (15) | C18—Zr1—C28 | 136.57 (9) |
C26—C27—C28 | 107.7 (2) | C17—Zr1—C28 | 106.73 (8) |
C26—C27—C32 | 125.4 (2) | C27—Zr1—C28 | 32.12 (8) |
C28—C27—C32 | 126.5 (2) | C19—Zr1—C28 | 153.78 (8) |
C26—C27—Zr1 | 73.47 (12) | C20—Zr1—C28 | 124.41 (8) |
C28—C27—Zr1 | 75.32 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···N2i | 0.89 (3) | 2.14 (3) | 3.014 (3) | 168 (3) |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···N2i | 0.89 (3) | 2.14 (3) | 3.014 (3) | 168 (3) |
Symmetry code: (i) −x+1, −y, −z. |
Acknowledgements
We thank our technical staff, in particular Kathleen Schubert, for assistance. This work was supported by the Deutsche Forschungsgemeinschaft (RO1269/8–1).
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We studied the reactions of several nitriles with metallocene precursors as Cp*2M(η2-Me3SiC2SiMe3) (Cp* = η5– pentamethylcyclopentadienyl, M = Ti, Zr) to synthesize and characterize new strained metallacycles with heteroatoms. In the reaction with diphenylacetonitrile the complex Cp*2Zr(N=CH-CHPh2)(N=C=CPh2) (Becker et al. (2013)) was formed after 4 h at 358 K. However a longer reaction time of 24 h led to the cleavage of the Ph2CH—CN bond upon partial oxidation thus forming the title compound. The zirconium(IV) atom is coordinated by two pentamethylcyclopentadienyl ligands in a η5-fashion, as well as by the N– and O-atoms of the amidate and an additional C≡N ligand. The four-membered ring is almost planar (mean deviation from the best plane defined by Zr1, O1, C1, N1 = 0.008 Å). The bond lengths O1—C1 1.290 (3) and N1—C1 1.294 (3) Å suggest the resonance form with electronic delocalization within the OCN unit. The molecules are connected to centrosymmetric dimers via N—H···N hydrogen bonds.