metal-organic compounds
Tetrakis(dicyclohexylamido)zirconium(IV)
aCarl von Ossietzky Universität Oldenburg, Fakultät V, Institut für Chemie, Carl-von-Ossietzky-Strasse 9-11, D-26129 Oldenburg, Germany
*Correspondence e-mail: ruediger.beckhaus@uol.de
The reaction of ZrCl4 with three equivalents of LiNCy2 (Cy is cyclohexyl) resulted in the formation of tris(dicyclohexylamido)zirconium chloride and the title compound, [Zr(C12H22N)4]. The latter is isotypic with its cerium(IV) analogue and crystallizes with three independent molecules in the One molecule is located about a twofold rotation axis, and the other two on fourfold inversion axes. In each molecule, the ZrIV atom has a distorted tetrahedral coordination environment. The crystal under investigation was twinned by inversion in a 1:1 ratio.
Keywords: crystal structure; zirconium; amide; isotypism.
CCDC reference: 2024547
Structure description
Amido complexes of group 4 metals play an important role in synthetic chemistry. They are widely used as catalysts in hydroaminoalkylation reactions (Roesky et al., 2009) or in the catalysis of olefin polymerization reactions (Shafir & Arnold, 2001; Motolko et al., 2017). Tetrakis(dialkylamido)zirconium(IV) compounds are commonly known as precursors of a variety of more complex zirconium-containing compounds (Diamond et al., 1995, 1996). Amido ligands are known for their ability to stabilize electron-deficient transition-metal complexes by N(pπ)—M(dπ) interactions (Yu et al., 2004). Combined with the possibility of double substitution at the nitrogen atom, which allows a broad variety in ligand design (Kasani et al., 1997), amido ligands appear to be an interesting alternative to Cp-based ligands (Kempe, 2000; Guérin et al., 2000). In particular, dicyclohexylamine seems to be useful due to its steric demand that is similar to cyclopentadienyl ligands (Duan et al., 1997). Additionally, dicyclohexylamido complexes of group 4 metals show close contacts between the central metal cation and the carbon atom of the CH group of one dicyclohexylamido ligand, which is an indicator for attractive agostic interactions (Duan et al., 1997; Adler et al., 2014b). The understanding of these interactions is very important (Scherer et al., 2010) because they are considered to be intermediates in C—H bond-activation processes.
The title compound, 1, crystallizes in the tetragonal P and is isostructural with tetrakis(dicyclohexylamido)cerium(IV) (Hitchcock et al., 2006). The structure of 1 exhibits three independent molecules, two of which lie on a fourfold inversion axis (Zr2, Zr3) as well as one (Zr1) lying on a twofold rotation axis. One of these molecules is shown in Fig. 1. In each molecule, the zirconium(IV) atom is coordinated in a slightly distorted tetrahedral fashion with bond angles around zirconium(IV) ranging from 104.53 (8) to 112.00 (4)°. The nitrogen atoms have a trigonal planar environment (sum of angles: N1: 359.2°, N2: 359.9°, N3: 359.6°, N4: 359.6°). The mean Zr—N bond length of 2.094 Å is slightly elongated compared to tris(dicyclohexylamido)zirconium(IV) chloride (mean 2.044 Å; Adler et al., 2014a) but still short for a Zr—N single bond, indicating N(pπ)—Zr(dπ) interactions (Pyykkö & Atsumi et al., 2009). The slight elongation can either be caused by a greater or by a less elctrophilic central metal atom in complex 1. The large Zr—N—C bond angles [e.g. Zr3—N4—C37 = 138.00 (10)°, Zr3—N4—C43 = 108.15 (9)°] indicate that agostic interactions are not present.
No significant supramolecular features are observed in the 1. The molecular packing (Fig. 2) appears to be dominated by van der Waals interactions only.
ofSynthesis and crystallization
All reactions were carried out under a dry nitrogen atmosphere using Schlenk techniques or in a n-butyllithium (2.5 M in n-hexane). Solvents were dried according to standard procedures over Na/K alloy with benzophenone as indicator and distilled under a nitrogen atmosphere.
Lithium dicyclohexylamide was synthesized by treatment of dicyclohexylamine with one equivalent ofZirconiumtetrachloride and three equivalents of lithium dicyclohexylamide were suspended in 50 ml of n-hexane. After 16 h the reaction mixture was filtered hot through a P4-frit and stored at 243 K overnight. The solvent was decanted. After renewed storage of the mother liquor at 243 K, the title compound 1 crystallized in form of colourless blocks as the minor product, besides the mainproduct tris(dicyclohexylamido)zirconium(IV) chloride.
Refinement
Crystal data, data collection and structure . The crystal under investigation was twinned by inversion in a 1:1 ratio.
details are summarized in Table 1Structural data
CCDC reference: 2024547
https://doi.org/10.1107/S2414314620011451/wm5575sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620011451/wm5575Isup3.hkl
Data collection: APEX3 (Bruker, 2015); cell
SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).[Zr(C12H22N)4] | Dx = 1.191 Mg m−3 |
Mr = 812.44 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P4 | Cell parameters from 9855 reflections |
a = 21.0321 (7) Å | θ = 2.2–36.3° |
c = 10.2412 (5) Å | µ = 0.28 mm−1 |
V = 4530.2 (4) Å3 | T = 100 K |
Z = 4 | Block, colourless |
F(000) = 1776 | 0.15 × 0.11 × 0.07 mm |
Bruker Photon III CPAD diffractometer | 20806 reflections with I > 2σ(I) |
Radiation source: IµS microfocus | Rint = 0.047 |
φ and ω scans | θmax = 36.3°, θmin = 1.4° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −34→35 |
Tmin = 0.936, Tmax = 1.000 | k = −35→35 |
350034 measured reflections | l = −17→17 |
21937 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.045P)2 + 0.9P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
21937 reflections | Δρmax = 2.50 e Å−3 |
479 parameters | Δρmin = −0.42 e Å−3 |
0 restraints | Absolute structure: Refined as an inversion twin. |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.491 (17) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | ||
Zr1 | 0.500000 | 0.000000 | 0.15631 (2) | 0.00900 (3) | |
N1 | 0.42803 (6) | 0.03193 (6) | 0.03168 (12) | 0.01353 (19) | |
N2 | 0.53112 (6) | 0.07285 (6) | 0.27997 (12) | 0.01322 (19) | |
C1 | 0.39758 (6) | −0.02236 (7) | −0.03612 (14) | 0.0134 (2) | |
H1 | 0.413064 | −0.061668 | 0.008681 | 0.016* | |
C2 | 0.41569 (7) | −0.02952 (7) | −0.18129 (15) | 0.0163 (2) | |
H2A | 0.401743 | 0.008770 | −0.229671 | 0.020* | |
H2B | 0.462503 | −0.032626 | −0.189091 | 0.020* | |
C3 | 0.38522 (7) | −0.08849 (8) | −0.24255 (17) | 0.0195 (3) | |
H3A | 0.396690 | −0.090539 | −0.336209 | 0.023* | |
H3B | 0.402176 | −0.127059 | −0.199467 | 0.023* | |
C4 | 0.31327 (8) | −0.08745 (9) | −0.22921 (17) | 0.0223 (3) | |
H4A | 0.295261 | −0.127056 | −0.266107 | 0.027* | |
H4B | 0.295784 | −0.051109 | −0.279063 | 0.027* | |
C5 | 0.29407 (8) | −0.08151 (9) | −0.08555 (17) | 0.0217 (3) | |
H5A | 0.247231 | −0.078131 | −0.078933 | 0.026* | |
H5B | 0.307581 | −0.120080 | −0.037598 | 0.026* | |
C6 | 0.32481 (7) | −0.02284 (8) | −0.02371 (16) | 0.0180 (2) | |
H6A | 0.313233 | −0.021210 | 0.069932 | 0.022* | |
H6B | 0.307492 | 0.015779 | −0.066020 | 0.022* | |
C7 | 0.40759 (7) | 0.09482 (7) | −0.01821 (15) | 0.0164 (2) | |
H7 | 0.387575 | 0.087786 | −0.105595 | 0.020* | |
C8 | 0.35773 (8) | 0.12664 (8) | 0.06910 (16) | 0.0203 (3) | |
H8A | 0.319517 | 0.099238 | 0.073568 | 0.024* | |
H8B | 0.374995 | 0.130846 | 0.158614 | 0.024* | |
C9 | 0.33865 (11) | 0.19220 (10) | 0.0188 (2) | 0.0315 (4) | |
H9A | 0.308303 | 0.211950 | 0.080587 | 0.038* | |
H9B | 0.317119 | 0.187739 | −0.066653 | 0.038* | |
C10 | 0.39710 (13) | 0.23528 (10) | 0.0037 (2) | 0.0360 (5) | |
H10A | 0.383906 | 0.276766 | −0.033078 | 0.043* | |
H10B | 0.416321 | 0.243068 | 0.090488 | 0.043* | |
C11 | 0.44601 (12) | 0.20469 (9) | −0.0856 (2) | 0.0321 (4) | |
H11A | 0.484383 | 0.231896 | −0.089201 | 0.039* | |
H11B | 0.428358 | 0.201710 | −0.174997 | 0.039* | |
C12 | 0.46478 (8) | 0.13813 (7) | −0.03852 (17) | 0.0205 (3) | |
H12A | 0.493600 | 0.118537 | −0.103513 | 0.025* | |
H12B | 0.488376 | 0.141923 | 0.044763 | 0.025* | |
C13 | 0.47597 (7) | 0.10288 (7) | 0.34634 (14) | 0.0134 (2) | |
H13 | 0.437144 | 0.086612 | 0.300953 | 0.016* | |
C14 | 0.47425 (7) | 0.17561 (7) | 0.33277 (15) | 0.0163 (2) | |
H14A | 0.476775 | 0.186916 | 0.239075 | 0.020* | |
H14B | 0.511975 | 0.193844 | 0.376808 | 0.020* | |
C15 | 0.41395 (8) | 0.20536 (8) | 0.39145 (17) | 0.0187 (3) | |
H15A | 0.416967 | 0.252264 | 0.386074 | 0.022* | |
H15B | 0.376491 | 0.191799 | 0.339954 | 0.022* | |
C16 | 0.40488 (8) | 0.18573 (8) | 0.53359 (17) | 0.0206 (3) | |
H16A | 0.438860 | 0.204958 | 0.587585 | 0.025* | |
H16B | 0.363511 | 0.201918 | 0.565547 | 0.025* | |
C17 | 0.40676 (8) | 0.11366 (7) | 0.54837 (17) | 0.0190 (3) | |
H17A | 0.369648 | 0.094844 | 0.503191 | 0.023* | |
H17B | 0.403796 | 0.102488 | 0.642077 | 0.023* | |
C18 | 0.46806 (7) | 0.08557 (7) | 0.49133 (15) | 0.0163 (2) | |
H18A | 0.467168 | 0.038726 | 0.500637 | 0.020* | |
H18B | 0.505004 | 0.101798 | 0.541109 | 0.020* | |
C19 | 0.59346 (7) | 0.09533 (7) | 0.32831 (15) | 0.0140 (2) | |
H19 | 0.585789 | 0.118139 | 0.412521 | 0.017* | |
C20 | 0.62529 (7) | 0.14248 (7) | 0.23477 (16) | 0.0165 (2) | |
H20A | 0.629973 | 0.122311 | 0.147959 | 0.020* | |
H20B | 0.597560 | 0.180189 | 0.224499 | 0.020* | |
C21 | 0.69080 (8) | 0.16400 (8) | 0.28315 (17) | 0.0199 (3) | |
H21A | 0.710560 | 0.191981 | 0.216860 | 0.024* | |
H21B | 0.685718 | 0.188867 | 0.364562 | 0.024* | |
C22 | 0.73425 (7) | 0.10744 (8) | 0.30895 (18) | 0.0201 (3) | |
H22A | 0.775288 | 0.122574 | 0.344652 | 0.024* | |
H22B | 0.742873 | 0.084843 | 0.226011 | 0.024* | |
C23 | 0.70308 (7) | 0.06202 (8) | 0.40578 (16) | 0.0190 (3) | |
H23A | 0.697908 | 0.083749 | 0.490876 | 0.023* | |
H23B | 0.731086 | 0.024760 | 0.419236 | 0.023* | |
C24 | 0.63806 (7) | 0.03938 (7) | 0.35741 (16) | 0.0165 (2) | |
H24A | 0.618450 | 0.011776 | 0.424551 | 0.020* | |
H24B | 0.643759 | 0.013773 | 0.277151 | 0.020* | |
Zr2 | 0.000000 | 0.000000 | 0.500000 | 0.00830 (5) | |
N3 | 0.02989 (5) | 0.07316 (5) | 0.37512 (13) | 0.01094 (19) | |
C25 | −0.02635 (6) | 0.10124 (6) | 0.30879 (14) | 0.01102 (19) | |
H25 | −0.064700 | 0.083485 | 0.353538 | 0.013* | |
C26 | −0.03299 (7) | 0.08426 (6) | 0.16306 (13) | 0.0131 (2) | |
H26A | 0.004274 | 0.100798 | 0.114754 | 0.016* | |
H26B | −0.033604 | 0.037445 | 0.153159 | 0.016* | |
C27 | −0.09397 (8) | 0.11227 (7) | 0.10426 (16) | 0.0173 (2) | |
H27A | −0.096220 | 0.101243 | 0.010391 | 0.021* | |
H27B | −0.131371 | 0.093295 | 0.148158 | 0.021* | |
C28 | −0.09609 (8) | 0.18446 (7) | 0.11954 (17) | 0.0193 (3) | |
H28A | −0.061017 | 0.203850 | 0.068839 | 0.023* | |
H28B | −0.136779 | 0.200844 | 0.084477 | 0.023* | |
C29 | −0.08982 (8) | 0.20312 (7) | 0.26268 (16) | 0.0170 (2) | |
H29A | −0.127795 | 0.188354 | 0.311098 | 0.020* | |
H29B | −0.087898 | 0.250028 | 0.269813 | 0.020* | |
C30 | −0.02993 (7) | 0.17417 (6) | 0.32438 (15) | 0.0136 (2) | |
H30A | −0.029115 | 0.184846 | 0.418515 | 0.016* | |
H30B | 0.008068 | 0.193517 | 0.283440 | 0.016* | |
C31 | 0.09123 (6) | 0.09799 (6) | 0.32725 (14) | 0.0122 (2) | |
H31 | 0.082512 | 0.120210 | 0.242805 | 0.015* | |
C32 | 0.12070 (7) | 0.14711 (7) | 0.41949 (15) | 0.0145 (2) | |
H32A | 0.126836 | 0.127523 | 0.506477 | 0.017* | |
H32B | 0.090924 | 0.183228 | 0.429740 | 0.017* | |
C33 | 0.18483 (7) | 0.17221 (7) | 0.36974 (18) | 0.0187 (3) | |
H33A | 0.178124 | 0.196300 | 0.287836 | 0.022* | |
H33B | 0.203137 | 0.201631 | 0.435169 | 0.022* | |
C34 | 0.23144 (7) | 0.11790 (8) | 0.34465 (16) | 0.0188 (3) | |
H34A | 0.271448 | 0.135068 | 0.307915 | 0.023* | |
H34B | 0.241576 | 0.096291 | 0.427972 | 0.023* | |
C35 | 0.20235 (7) | 0.07030 (8) | 0.24929 (16) | 0.0180 (3) | |
H35A | 0.232214 | 0.034445 | 0.236673 | 0.022* | |
H35B | 0.196087 | 0.091219 | 0.163647 | 0.022* | |
C36 | 0.13850 (7) | 0.04449 (7) | 0.29786 (15) | 0.0150 (2) | |
H36A | 0.120230 | 0.015980 | 0.230724 | 0.018* | |
H36B | 0.145525 | 0.019146 | 0.378032 | 0.018* | |
Zr3 | 0.500000 | 0.500000 | 0.500000 | 0.01251 (5) | |
N4 | 0.49034 (6) | 0.42185 (6) | 0.62514 (14) | 0.0149 (2) | |
C37 | 0.52996 (7) | 0.36924 (7) | 0.67418 (16) | 0.0166 (2) | |
H37 | 0.509870 | 0.353480 | 0.756545 | 0.020* | |
C38 | 0.59725 (8) | 0.39077 (8) | 0.70820 (17) | 0.0202 (3) | |
H38A | 0.595089 | 0.423826 | 0.776885 | 0.024* | |
H38B | 0.617112 | 0.410036 | 0.629997 | 0.024* | |
C39 | 0.63894 (8) | 0.33570 (9) | 0.75637 (18) | 0.0236 (3) | |
H39A | 0.682655 | 0.351483 | 0.771725 | 0.028* | |
H39B | 0.622067 | 0.319897 | 0.840579 | 0.028* | |
C40 | 0.64117 (9) | 0.28090 (9) | 0.65863 (18) | 0.0237 (3) | |
H40A | 0.666174 | 0.245312 | 0.695612 | 0.028* | |
H40B | 0.662338 | 0.295150 | 0.577397 | 0.028* | |
C41 | 0.57382 (9) | 0.25823 (8) | 0.62754 (19) | 0.0233 (3) | |
H41A | 0.554484 | 0.239663 | 0.707006 | 0.028* | |
H41B | 0.575640 | 0.224634 | 0.559928 | 0.028* | |
C42 | 0.53237 (8) | 0.31323 (7) | 0.57869 (17) | 0.0194 (3) | |
H42A | 0.549182 | 0.328324 | 0.493887 | 0.023* | |
H42B | 0.488620 | 0.297426 | 0.563883 | 0.023* | |
C43 | 0.42730 (7) | 0.42635 (7) | 0.69037 (16) | 0.0168 (2) | |
H43 | 0.403459 | 0.460602 | 0.643590 | 0.020* | |
C44 | 0.38717 (8) | 0.36572 (8) | 0.67626 (18) | 0.0211 (3) | |
H44A | 0.409026 | 0.330265 | 0.721293 | 0.025* | |
H44B | 0.383867 | 0.354579 | 0.582577 | 0.025* | |
C45 | 0.31995 (8) | 0.37302 (10) | 0.73308 (19) | 0.0266 (3) | |
H45A | 0.295738 | 0.403788 | 0.679399 | 0.032* | |
H45B | 0.297744 | 0.331577 | 0.728571 | 0.032* | |
C46 | 0.32096 (9) | 0.39577 (10) | 0.87375 (19) | 0.0253 (3) | |
H46A | 0.338704 | 0.361896 | 0.930138 | 0.030* | |
H46B | 0.276953 | 0.404482 | 0.902988 | 0.030* | |
C47 | 0.36079 (8) | 0.45570 (9) | 0.88819 (19) | 0.0244 (3) | |
H47A | 0.363015 | 0.467713 | 0.981542 | 0.029* | |
H47B | 0.340163 | 0.490970 | 0.840199 | 0.029* | |
C48 | 0.42844 (8) | 0.44587 (8) | 0.83523 (16) | 0.0203 (3) | |
H48A | 0.450040 | 0.412428 | 0.886828 | 0.024* | |
H48B | 0.452947 | 0.485771 | 0.845052 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr1 | 0.00815 (7) | 0.01012 (8) | 0.00874 (6) | −0.00008 (6) | 0.000 | 0.000 |
N1 | 0.0123 (4) | 0.0157 (5) | 0.0125 (4) | 0.0019 (4) | −0.0011 (4) | 0.0002 (4) |
N2 | 0.0118 (4) | 0.0142 (5) | 0.0137 (5) | −0.0003 (4) | −0.0008 (4) | −0.0020 (4) |
C1 | 0.0111 (5) | 0.0170 (5) | 0.0120 (5) | 0.0009 (4) | −0.0015 (4) | 0.0005 (4) |
C2 | 0.0138 (5) | 0.0207 (6) | 0.0144 (5) | −0.0005 (5) | 0.0003 (5) | −0.0002 (5) |
C3 | 0.0145 (6) | 0.0245 (7) | 0.0196 (6) | 0.0006 (5) | −0.0016 (5) | −0.0062 (5) |
C4 | 0.0141 (6) | 0.0334 (8) | 0.0194 (7) | −0.0025 (5) | −0.0041 (5) | −0.0048 (6) |
C5 | 0.0137 (6) | 0.0308 (8) | 0.0205 (7) | −0.0053 (5) | −0.0012 (5) | −0.0016 (6) |
C6 | 0.0122 (5) | 0.0261 (7) | 0.0155 (6) | −0.0005 (5) | 0.0003 (5) | −0.0007 (5) |
C7 | 0.0167 (6) | 0.0176 (6) | 0.0148 (6) | 0.0042 (5) | −0.0003 (5) | 0.0003 (5) |
C8 | 0.0184 (6) | 0.0239 (7) | 0.0187 (6) | 0.0075 (5) | 0.0002 (5) | −0.0021 (5) |
C9 | 0.0356 (10) | 0.0307 (9) | 0.0282 (9) | 0.0200 (8) | −0.0068 (8) | −0.0043 (7) |
C10 | 0.0607 (15) | 0.0201 (8) | 0.0271 (9) | 0.0162 (9) | 0.0058 (9) | 0.0028 (6) |
C11 | 0.0532 (13) | 0.0188 (7) | 0.0243 (8) | 0.0049 (8) | 0.0107 (9) | 0.0047 (6) |
C12 | 0.0258 (7) | 0.0151 (6) | 0.0205 (7) | 0.0020 (5) | 0.0085 (6) | 0.0005 (5) |
C13 | 0.0130 (5) | 0.0136 (5) | 0.0135 (5) | 0.0004 (4) | −0.0010 (4) | −0.0011 (4) |
C14 | 0.0189 (6) | 0.0143 (6) | 0.0156 (6) | 0.0013 (4) | 0.0004 (5) | −0.0004 (4) |
C15 | 0.0205 (7) | 0.0169 (6) | 0.0188 (6) | 0.0045 (5) | −0.0001 (5) | −0.0017 (5) |
C16 | 0.0250 (7) | 0.0169 (6) | 0.0201 (7) | 0.0021 (5) | 0.0040 (6) | −0.0033 (5) |
C17 | 0.0204 (6) | 0.0166 (6) | 0.0200 (7) | 0.0009 (5) | 0.0058 (5) | −0.0004 (5) |
C18 | 0.0172 (6) | 0.0169 (6) | 0.0148 (6) | 0.0010 (5) | 0.0008 (4) | 0.0004 (4) |
C19 | 0.0130 (5) | 0.0144 (5) | 0.0146 (5) | −0.0015 (4) | −0.0002 (4) | −0.0005 (4) |
C20 | 0.0153 (6) | 0.0156 (6) | 0.0186 (6) | −0.0022 (4) | −0.0002 (5) | 0.0020 (5) |
C21 | 0.0175 (6) | 0.0189 (6) | 0.0232 (7) | −0.0053 (5) | −0.0002 (5) | −0.0007 (5) |
C22 | 0.0137 (6) | 0.0256 (7) | 0.0208 (7) | −0.0032 (5) | −0.0009 (5) | −0.0013 (6) |
C23 | 0.0145 (6) | 0.0238 (7) | 0.0187 (6) | −0.0011 (5) | −0.0032 (5) | 0.0015 (5) |
C24 | 0.0127 (5) | 0.0170 (6) | 0.0197 (6) | −0.0004 (4) | −0.0016 (5) | 0.0023 (5) |
Zr2 | 0.00851 (6) | 0.00851 (6) | 0.00787 (10) | 0.000 | 0.000 | 0.000 |
N3 | 0.0097 (4) | 0.0107 (4) | 0.0124 (5) | −0.0004 (3) | 0.0007 (4) | 0.0017 (4) |
C25 | 0.0125 (5) | 0.0089 (5) | 0.0116 (5) | 0.0001 (4) | 0.0009 (4) | 0.0004 (4) |
C26 | 0.0164 (5) | 0.0107 (5) | 0.0122 (5) | 0.0001 (4) | −0.0007 (4) | −0.0001 (4) |
C27 | 0.0208 (6) | 0.0139 (5) | 0.0173 (6) | 0.0003 (5) | −0.0063 (5) | 0.0011 (5) |
C28 | 0.0268 (7) | 0.0128 (5) | 0.0182 (6) | 0.0022 (5) | −0.0060 (5) | 0.0026 (5) |
C29 | 0.0194 (6) | 0.0125 (5) | 0.0192 (6) | 0.0032 (5) | −0.0019 (5) | 0.0002 (5) |
C30 | 0.0154 (5) | 0.0101 (5) | 0.0152 (5) | −0.0002 (4) | −0.0003 (4) | −0.0001 (4) |
C31 | 0.0114 (5) | 0.0118 (5) | 0.0135 (5) | −0.0022 (4) | −0.0002 (4) | −0.0011 (4) |
C32 | 0.0145 (5) | 0.0136 (5) | 0.0154 (6) | −0.0024 (4) | 0.0010 (4) | −0.0019 (4) |
C33 | 0.0158 (6) | 0.0155 (6) | 0.0249 (7) | −0.0045 (4) | 0.0002 (5) | −0.0006 (5) |
C34 | 0.0133 (6) | 0.0227 (7) | 0.0203 (7) | −0.0029 (5) | 0.0007 (5) | 0.0007 (5) |
C35 | 0.0143 (6) | 0.0228 (7) | 0.0170 (6) | 0.0001 (5) | 0.0031 (5) | −0.0015 (5) |
C36 | 0.0152 (5) | 0.0146 (5) | 0.0152 (6) | 0.0003 (4) | 0.0019 (4) | −0.0018 (4) |
Zr3 | 0.01181 (7) | 0.01181 (7) | 0.01390 (12) | 0.000 | 0.000 | 0.000 |
N4 | 0.0132 (5) | 0.0144 (5) | 0.0170 (5) | 0.0013 (4) | 0.0008 (4) | 0.0030 (4) |
C37 | 0.0163 (6) | 0.0166 (6) | 0.0170 (6) | 0.0008 (4) | −0.0007 (5) | 0.0009 (5) |
C38 | 0.0180 (6) | 0.0190 (6) | 0.0237 (7) | 0.0016 (5) | −0.0041 (5) | −0.0027 (5) |
C39 | 0.0211 (7) | 0.0252 (7) | 0.0244 (7) | 0.0050 (6) | −0.0062 (6) | −0.0023 (6) |
C40 | 0.0221 (7) | 0.0220 (7) | 0.0269 (8) | 0.0058 (6) | −0.0012 (6) | −0.0002 (6) |
C41 | 0.0268 (8) | 0.0160 (6) | 0.0271 (8) | 0.0026 (5) | −0.0026 (6) | 0.0000 (6) |
C42 | 0.0215 (7) | 0.0151 (6) | 0.0214 (7) | 0.0003 (5) | −0.0037 (5) | −0.0003 (5) |
C43 | 0.0152 (5) | 0.0189 (6) | 0.0162 (5) | 0.0002 (4) | 0.0001 (5) | 0.0033 (5) |
C44 | 0.0180 (6) | 0.0231 (7) | 0.0222 (7) | −0.0040 (5) | 0.0010 (5) | 0.0023 (6) |
C45 | 0.0182 (7) | 0.0359 (9) | 0.0258 (8) | −0.0066 (6) | 0.0015 (6) | 0.0037 (7) |
C46 | 0.0205 (7) | 0.0312 (8) | 0.0242 (8) | −0.0012 (6) | 0.0029 (6) | 0.0075 (7) |
C47 | 0.0203 (7) | 0.0286 (8) | 0.0245 (7) | 0.0019 (6) | 0.0054 (6) | 0.0004 (6) |
C48 | 0.0180 (6) | 0.0240 (7) | 0.0188 (7) | 0.0009 (5) | 0.0012 (5) | 0.0003 (5) |
Zr1—N1i | 2.0908 (12) | Zr2—N3iv | 2.0973 (12) |
Zr1—N1 | 2.0908 (12) | Zr2—N3 | 2.0973 (12) |
Zr1—N2 | 2.0928 (12) | N3—C31 | 1.4756 (18) |
Zr1—N2i | 2.0929 (12) | N3—C25 | 1.4863 (18) |
N1—C7 | 1.4816 (19) | C25—C26 | 1.541 (2) |
N1—C1 | 1.4821 (19) | C25—C30 | 1.5441 (18) |
N2—C19 | 1.4790 (18) | C25—H25 | 1.0000 |
N2—C13 | 1.4854 (19) | C26—C27 | 1.534 (2) |
C1—C6 | 1.536 (2) | C26—H26A | 0.9900 |
C1—C2 | 1.542 (2) | C26—H26B | 0.9900 |
C1—H1 | 1.0000 | C27—C28 | 1.527 (2) |
C2—C3 | 1.530 (2) | C27—H27A | 0.9900 |
C2—H2A | 0.9900 | C27—H27B | 0.9900 |
C2—H2B | 0.9900 | C28—C29 | 1.523 (2) |
C3—C4 | 1.520 (2) | C28—H28A | 0.9900 |
C3—H3A | 0.9900 | C28—H28B | 0.9900 |
C3—H3B | 0.9900 | C29—C30 | 1.535 (2) |
C4—C5 | 1.531 (3) | C29—H29A | 0.9900 |
C4—H4A | 0.9900 | C29—H29B | 0.9900 |
C4—H4B | 0.9900 | C30—H30A | 0.9900 |
C5—C6 | 1.530 (2) | C30—H30B | 0.9900 |
C5—H5A | 0.9900 | C31—C32 | 1.531 (2) |
C5—H5B | 0.9900 | C31—C36 | 1.531 (2) |
C6—H6A | 0.9900 | C31—H31 | 1.0000 |
C6—H6B | 0.9900 | C32—C33 | 1.536 (2) |
C7—C12 | 1.523 (2) | C32—H32A | 0.9900 |
C7—C8 | 1.532 (2) | C32—H32B | 0.9900 |
C7—H7 | 1.0000 | C33—C34 | 1.527 (2) |
C8—C9 | 1.526 (3) | C33—H33A | 0.9900 |
C8—H8A | 0.9900 | C33—H33B | 0.9900 |
C8—H8B | 0.9900 | C34—C35 | 1.527 (2) |
C9—C10 | 1.535 (4) | C34—H34A | 0.9900 |
C9—H9A | 0.9900 | C34—H34B | 0.9900 |
C9—H9B | 0.9900 | C35—C36 | 1.531 (2) |
C10—C11 | 1.519 (3) | C35—H35A | 0.9900 |
C10—H10A | 0.9900 | C35—H35B | 0.9900 |
C10—H10B | 0.9900 | C36—H36A | 0.9900 |
C11—C12 | 1.532 (2) | C36—H36B | 0.9900 |
C11—H11A | 0.9900 | Zr3—N4v | 2.0940 (13) |
C11—H11B | 0.9900 | Zr3—N4vi | 2.0940 (13) |
C12—H12A | 0.9900 | Zr3—N4vii | 2.0940 (13) |
C12—H12B | 0.9900 | Zr3—N4 | 2.0940 (13) |
C13—C14 | 1.536 (2) | N4—C37 | 1.473 (2) |
C13—C18 | 1.538 (2) | N4—C43 | 1.488 (2) |
C13—H13 | 1.0000 | C37—C38 | 1.526 (2) |
C14—C15 | 1.537 (2) | C37—C42 | 1.532 (2) |
C14—H14A | 0.9900 | C37—H37 | 1.0000 |
C14—H14B | 0.9900 | C38—C39 | 1.534 (2) |
C15—C16 | 1.525 (2) | C38—H38A | 0.9900 |
C15—H15A | 0.9900 | C38—H38B | 0.9900 |
C15—H15B | 0.9900 | C39—C40 | 1.527 (3) |
C16—C17 | 1.524 (2) | C39—H39A | 0.9900 |
C16—H16A | 0.9900 | C39—H39B | 0.9900 |
C16—H16B | 0.9900 | C40—C41 | 1.528 (3) |
C17—C18 | 1.534 (2) | C40—H40A | 0.9900 |
C17—H17A | 0.9900 | C40—H40B | 0.9900 |
C17—H17B | 0.9900 | C41—C42 | 1.532 (2) |
C18—H18A | 0.9900 | C41—H41A | 0.9900 |
C18—H18B | 0.9900 | C41—H41B | 0.9900 |
C19—C20 | 1.533 (2) | C42—H42A | 0.9900 |
C19—C24 | 1.534 (2) | C42—H42B | 0.9900 |
C19—H19 | 1.0000 | C43—C44 | 1.536 (2) |
C20—C21 | 1.532 (2) | C43—C48 | 1.539 (2) |
C20—H20A | 0.9900 | C43—H43 | 1.0000 |
C20—H20B | 0.9900 | C44—C45 | 1.537 (2) |
C21—C22 | 1.523 (2) | C44—H44A | 0.9900 |
C21—H21A | 0.9900 | C44—H44B | 0.9900 |
C21—H21B | 0.9900 | C45—C46 | 1.518 (3) |
C22—C23 | 1.525 (2) | C45—H45A | 0.9900 |
C22—H22A | 0.9900 | C45—H45B | 0.9900 |
C22—H22B | 0.9900 | C46—C47 | 1.521 (3) |
C23—C24 | 1.530 (2) | C46—H46A | 0.9900 |
C23—H23A | 0.9900 | C46—H46B | 0.9900 |
C23—H23B | 0.9900 | C47—C48 | 1.537 (2) |
C24—H24A | 0.9900 | C47—H47A | 0.9900 |
C24—H24B | 0.9900 | C47—H47B | 0.9900 |
Zr2—N3ii | 2.0973 (12) | C48—H48A | 0.9900 |
Zr2—N3iii | 2.0973 (12) | C48—H48B | 0.9900 |
N1i—Zr1—N1 | 104.75 (7) | N3ii—Zr2—N3 | 104.85 (7) |
N1i—Zr1—N2 | 112.22 (5) | N3iii—Zr2—N3 | 111.83 (4) |
N1—Zr1—N2 | 111.14 (5) | N3iv—Zr2—N3 | 111.83 (4) |
N1i—Zr1—N2i | 111.14 (5) | C31—N3—C25 | 113.79 (11) |
N1—Zr1—N2i | 112.22 (5) | C31—N3—Zr2 | 136.41 (9) |
N2—Zr1—N2i | 105.53 (7) | C25—N3—Zr2 | 109.37 (8) |
C7—N1—C1 | 113.64 (11) | N3—C25—C26 | 115.01 (11) |
C7—N1—Zr1 | 135.02 (10) | N3—C25—C30 | 112.72 (11) |
C1—N1—Zr1 | 110.57 (9) | C26—C25—C30 | 109.02 (11) |
C19—N2—C13 | 113.77 (11) | N3—C25—H25 | 106.5 |
C19—N2—Zr1 | 135.54 (9) | C26—C25—H25 | 106.5 |
C13—N2—Zr1 | 110.12 (8) | C30—C25—H25 | 106.5 |
N1—C1—C6 | 113.38 (12) | C27—C26—C25 | 111.53 (12) |
N1—C1—C2 | 114.84 (12) | C27—C26—H26A | 109.3 |
C6—C1—C2 | 108.99 (12) | C25—C26—H26A | 109.3 |
N1—C1—H1 | 106.3 | C27—C26—H26B | 109.3 |
C6—C1—H1 | 106.3 | C25—C26—H26B | 109.3 |
C2—C1—H1 | 106.3 | H26A—C26—H26B | 108.0 |
C3—C2—C1 | 111.77 (13) | C28—C27—C26 | 111.46 (12) |
C3—C2—H2A | 109.3 | C28—C27—H27A | 109.3 |
C1—C2—H2A | 109.3 | C26—C27—H27A | 109.3 |
C3—C2—H2B | 109.3 | C28—C27—H27B | 109.3 |
C1—C2—H2B | 109.3 | C26—C27—H27B | 109.3 |
H2A—C2—H2B | 107.9 | H27A—C27—H27B | 108.0 |
C4—C3—C2 | 111.63 (13) | C29—C28—C27 | 110.63 (13) |
C4—C3—H3A | 109.3 | C29—C28—H28A | 109.5 |
C2—C3—H3A | 109.3 | C27—C28—H28A | 109.5 |
C4—C3—H3B | 109.3 | C29—C28—H28B | 109.5 |
C2—C3—H3B | 109.3 | C27—C28—H28B | 109.5 |
H3A—C3—H3B | 108.0 | H28A—C28—H28B | 108.1 |
C3—C4—C5 | 110.50 (13) | C28—C29—C30 | 111.40 (13) |
C3—C4—H4A | 109.5 | C28—C29—H29A | 109.3 |
C5—C4—H4A | 109.5 | C30—C29—H29A | 109.3 |
C3—C4—H4B | 109.5 | C28—C29—H29B | 109.3 |
C5—C4—H4B | 109.5 | C30—C29—H29B | 109.3 |
H4A—C4—H4B | 108.1 | H29A—C29—H29B | 108.0 |
C6—C5—C4 | 110.62 (14) | C29—C30—C25 | 113.05 (11) |
C6—C5—H5A | 109.5 | C29—C30—H30A | 109.0 |
C4—C5—H5A | 109.5 | C25—C30—H30A | 109.0 |
C6—C5—H5B | 109.5 | C29—C30—H30B | 109.0 |
C4—C5—H5B | 109.5 | C25—C30—H30B | 109.0 |
H5A—C5—H5B | 108.1 | H30A—C30—H30B | 107.8 |
C5—C6—C1 | 113.08 (13) | N3—C31—C32 | 112.82 (11) |
C5—C6—H6A | 109.0 | N3—C31—C36 | 111.90 (11) |
C1—C6—H6A | 109.0 | C32—C31—C36 | 110.75 (11) |
C5—C6—H6B | 109.0 | N3—C31—H31 | 107.0 |
C1—C6—H6B | 109.0 | C32—C31—H31 | 107.0 |
H6A—C6—H6B | 107.8 | C36—C31—H31 | 107.0 |
N1—C7—C12 | 110.60 (12) | C31—C32—C33 | 112.51 (12) |
N1—C7—C8 | 112.79 (13) | C31—C32—H32A | 109.1 |
C12—C7—C8 | 111.04 (13) | C33—C32—H32A | 109.1 |
N1—C7—H7 | 107.4 | C31—C32—H32B | 109.1 |
C12—C7—H7 | 107.4 | C33—C32—H32B | 109.1 |
C8—C7—H7 | 107.4 | H32A—C32—H32B | 107.8 |
C9—C8—C7 | 112.20 (15) | C34—C33—C32 | 111.26 (12) |
C9—C8—H8A | 109.2 | C34—C33—H33A | 109.4 |
C7—C8—H8A | 109.2 | C32—C33—H33A | 109.4 |
C9—C8—H8B | 109.2 | C34—C33—H33B | 109.4 |
C7—C8—H8B | 109.2 | C32—C33—H33B | 109.4 |
H8A—C8—H8B | 107.9 | H33A—C33—H33B | 108.0 |
C8—C9—C10 | 110.91 (16) | C35—C34—C33 | 109.93 (13) |
C8—C9—H9A | 109.5 | C35—C34—H34A | 109.7 |
C10—C9—H9A | 109.5 | C33—C34—H34A | 109.7 |
C8—C9—H9B | 109.5 | C35—C34—H34B | 109.7 |
C10—C9—H9B | 109.5 | C33—C34—H34B | 109.7 |
H9A—C9—H9B | 108.0 | H34A—C34—H34B | 108.2 |
C11—C10—C9 | 110.67 (18) | C34—C35—C36 | 112.09 (13) |
C11—C10—H10A | 109.5 | C34—C35—H35A | 109.2 |
C9—C10—H10A | 109.5 | C36—C35—H35A | 109.2 |
C11—C10—H10B | 109.5 | C34—C35—H35B | 109.2 |
C9—C10—H10B | 109.5 | C36—C35—H35B | 109.2 |
H10A—C10—H10B | 108.1 | H35A—C35—H35B | 107.9 |
C10—C11—C12 | 111.84 (16) | C31—C36—C35 | 111.88 (12) |
C10—C11—H11A | 109.2 | C31—C36—H36A | 109.2 |
C12—C11—H11A | 109.2 | C35—C36—H36A | 109.2 |
C10—C11—H11B | 109.2 | C31—C36—H36B | 109.2 |
C12—C11—H11B | 109.2 | C35—C36—H36B | 109.2 |
H11A—C11—H11B | 107.9 | H36A—C36—H36B | 107.9 |
C7—C12—C11 | 112.70 (16) | N4v—Zr3—N4vi | 112.00 (4) |
C7—C12—H12A | 109.1 | N4v—Zr3—N4vii | 112.00 (4) |
C11—C12—H12A | 109.1 | N4vi—Zr3—N4vii | 104.53 (8) |
C7—C12—H12B | 109.1 | N4v—Zr3—N4 | 104.53 (8) |
C11—C12—H12B | 109.1 | N4vi—Zr3—N4 | 112.00 (4) |
H12A—C12—H12B | 107.8 | N4vii—Zr3—N4 | 112.00 (4) |
N2—C13—C14 | 113.60 (12) | C37—N4—C43 | 113.49 (12) |
N2—C13—C18 | 115.19 (12) | C37—N4—Zr3 | 138.00 (10) |
C14—C13—C18 | 108.70 (12) | C43—N4—Zr3 | 108.15 (9) |
N2—C13—H13 | 106.2 | N4—C37—C38 | 112.30 (13) |
C14—C13—H13 | 106.2 | N4—C37—C42 | 112.25 (13) |
C18—C13—H13 | 106.2 | C38—C37—C42 | 110.07 (13) |
C13—C14—C15 | 112.93 (13) | N4—C37—H37 | 107.3 |
C13—C14—H14A | 109.0 | C38—C37—H37 | 107.3 |
C15—C14—H14A | 109.0 | C42—C37—H37 | 107.3 |
C13—C14—H14B | 109.0 | C37—C38—C39 | 112.30 (14) |
C15—C14—H14B | 109.0 | C37—C38—H38A | 109.1 |
H14A—C14—H14B | 107.8 | C39—C38—H38A | 109.1 |
C16—C15—C14 | 111.48 (13) | C37—C38—H38B | 109.1 |
C16—C15—H15A | 109.3 | C39—C38—H38B | 109.1 |
C14—C15—H15A | 109.3 | H38A—C38—H38B | 107.9 |
C16—C15—H15B | 109.3 | C40—C39—C38 | 112.12 (14) |
C14—C15—H15B | 109.3 | C40—C39—H39A | 109.2 |
H15A—C15—H15B | 108.0 | C38—C39—H39A | 109.2 |
C17—C16—C15 | 111.16 (13) | C40—C39—H39B | 109.2 |
C17—C16—H16A | 109.4 | C38—C39—H39B | 109.2 |
C15—C16—H16A | 109.4 | H39A—C39—H39B | 107.9 |
C17—C16—H16B | 109.4 | C39—C40—C41 | 110.09 (14) |
C15—C16—H16B | 109.4 | C39—C40—H40A | 109.6 |
H16A—C16—H16B | 108.0 | C41—C40—H40A | 109.6 |
C16—C17—C18 | 111.54 (13) | C39—C40—H40B | 109.6 |
C16—C17—H17A | 109.3 | C41—C40—H40B | 109.6 |
C18—C17—H17A | 109.3 | H40A—C40—H40B | 108.2 |
C16—C17—H17B | 109.3 | C40—C41—C42 | 111.09 (14) |
C18—C17—H17B | 109.3 | C40—C41—H41A | 109.4 |
H17A—C17—H17B | 108.0 | C42—C41—H41A | 109.4 |
C17—C18—C13 | 111.56 (13) | C40—C41—H41B | 109.4 |
C17—C18—H18A | 109.3 | C42—C41—H41B | 109.4 |
C13—C18—H18A | 109.3 | H41A—C41—H41B | 108.0 |
C17—C18—H18B | 109.3 | C37—C42—C41 | 113.01 (14) |
C13—C18—H18B | 109.3 | C37—C42—H42A | 109.0 |
H18A—C18—H18B | 108.0 | C41—C42—H42A | 109.0 |
N2—C19—C20 | 112.63 (12) | C37—C42—H42B | 109.0 |
N2—C19—C24 | 111.22 (11) | C41—C42—H42B | 109.0 |
C20—C19—C24 | 110.52 (12) | H42A—C42—H42B | 107.8 |
N2—C19—H19 | 107.4 | N4—C43—C44 | 113.25 (13) |
C20—C19—H19 | 107.4 | N4—C43—C48 | 115.83 (13) |
C24—C19—H19 | 107.4 | C44—C43—C48 | 108.70 (13) |
C21—C20—C19 | 112.44 (13) | N4—C43—H43 | 106.1 |
C21—C20—H20A | 109.1 | C44—C43—H43 | 106.1 |
C19—C20—H20A | 109.1 | C48—C43—H43 | 106.1 |
C21—C20—H20B | 109.1 | C43—C44—C45 | 112.76 (15) |
C19—C20—H20B | 109.1 | C43—C44—H44A | 109.0 |
H20A—C20—H20B | 107.8 | C45—C44—H44A | 109.0 |
C22—C21—C20 | 111.40 (13) | C43—C44—H44B | 109.0 |
C22—C21—H21A | 109.3 | C45—C44—H44B | 109.0 |
C20—C21—H21A | 109.3 | H44A—C44—H44B | 107.8 |
C22—C21—H21B | 109.3 | C46—C45—C44 | 112.21 (15) |
C20—C21—H21B | 109.3 | C46—C45—H45A | 109.2 |
H21A—C21—H21B | 108.0 | C44—C45—H45A | 109.2 |
C21—C22—C23 | 110.12 (13) | C46—C45—H45B | 109.2 |
C21—C22—H22A | 109.6 | C44—C45—H45B | 109.2 |
C23—C22—H22A | 109.6 | H45A—C45—H45B | 107.9 |
C21—C22—H22B | 109.6 | C45—C46—C47 | 111.17 (15) |
C23—C22—H22B | 109.6 | C45—C46—H46A | 109.4 |
H22A—C22—H22B | 108.2 | C47—C46—H46A | 109.4 |
C22—C23—C24 | 111.62 (13) | C45—C46—H46B | 109.4 |
C22—C23—H23A | 109.3 | C47—C46—H46B | 109.4 |
C24—C23—H23A | 109.3 | H46A—C46—H46B | 108.0 |
C22—C23—H23B | 109.3 | C46—C47—C48 | 111.36 (15) |
C24—C23—H23B | 109.3 | C46—C47—H47A | 109.4 |
H23A—C23—H23B | 108.0 | C48—C47—H47A | 109.4 |
C23—C24—C19 | 111.76 (13) | C46—C47—H47B | 109.4 |
C23—C24—H24A | 109.3 | C48—C47—H47B | 109.4 |
C19—C24—H24A | 109.3 | H47A—C47—H47B | 108.0 |
C23—C24—H24B | 109.3 | C47—C48—C43 | 111.19 (14) |
C19—C24—H24B | 109.3 | C47—C48—H48A | 109.4 |
H24A—C24—H24B | 107.9 | C43—C48—H48A | 109.4 |
N3ii—Zr2—N3iii | 111.83 (4) | C47—C48—H48B | 109.4 |
N3ii—Zr2—N3iv | 111.83 (4) | C43—C48—H48B | 109.4 |
N3iii—Zr2—N3iv | 104.85 (7) | H48A—C48—H48B | 108.0 |
C7—N1—C1—C6 | −60.51 (16) | C31—N3—C25—C26 | 66.47 (15) |
Zr1—N1—C1—C6 | 128.03 (11) | Zr2—N3—C25—C26 | −107.23 (11) |
C7—N1—C1—C2 | 65.70 (15) | C31—N3—C25—C30 | −59.35 (15) |
Zr1—N1—C1—C2 | −105.76 (11) | Zr2—N3—C25—C30 | 126.95 (10) |
N1—C1—C2—C3 | 177.00 (12) | N3—C25—C26—C27 | 177.03 (11) |
C6—C1—C2—C3 | −54.55 (16) | C30—C25—C26—C27 | −55.26 (14) |
C1—C2—C3—C4 | 56.96 (18) | C25—C26—C27—C28 | 57.80 (17) |
C2—C3—C4—C5 | −56.6 (2) | C26—C27—C28—C29 | −56.56 (18) |
C3—C4—C5—C6 | 55.6 (2) | C27—C28—C29—C30 | 54.61 (18) |
C4—C5—C6—C1 | −56.12 (19) | C28—C29—C30—C25 | −54.78 (17) |
N1—C1—C6—C5 | −175.90 (13) | N3—C25—C30—C29 | −176.80 (12) |
C2—C1—C6—C5 | 54.84 (17) | C26—C25—C30—C29 | 54.21 (15) |
C1—N1—C7—C12 | −134.13 (13) | C25—N3—C31—C32 | 102.30 (13) |
Zr1—N1—C7—C12 | 34.53 (19) | Zr2—N3—C31—C32 | −86.34 (15) |
C1—N1—C7—C8 | 100.85 (15) | C25—N3—C31—C36 | −132.02 (12) |
Zr1—N1—C7—C8 | −90.50 (16) | Zr2—N3—C31—C36 | 39.35 (18) |
N1—C7—C8—C9 | 178.24 (14) | N3—C31—C32—C33 | 179.41 (12) |
C12—C7—C8—C9 | 53.45 (19) | C36—C31—C32—C33 | 53.10 (16) |
C7—C8—C9—C10 | −56.0 (2) | C31—C32—C33—C34 | −55.50 (18) |
C8—C9—C10—C11 | 56.4 (2) | C32—C33—C34—C35 | 56.09 (18) |
C9—C10—C11—C12 | −55.2 (3) | C33—C34—C35—C36 | −56.52 (18) |
N1—C7—C12—C11 | −177.98 (14) | N3—C31—C36—C35 | −179.52 (12) |
C8—C7—C12—C11 | −51.97 (19) | C32—C31—C36—C35 | −52.70 (16) |
C10—C11—C12—C7 | 53.7 (2) | C34—C35—C36—C31 | 55.46 (17) |
C19—N2—C13—C14 | 59.28 (16) | C43—N4—C37—C38 | −130.74 (14) |
Zr1—N2—C13—C14 | −127.95 (10) | Zr3—N4—C37—C38 | 41.3 (2) |
C19—N2—C13—C18 | −67.03 (15) | C43—N4—C37—C42 | 104.61 (15) |
Zr1—N2—C13—C18 | 105.75 (12) | Zr3—N4—C37—C42 | −83.35 (18) |
N2—C13—C14—C15 | 174.94 (12) | N4—C37—C38—C39 | −178.72 (14) |
C18—C13—C14—C15 | −55.41 (16) | C42—C37—C38—C39 | −52.88 (18) |
C13—C14—C15—C16 | 54.66 (18) | C37—C38—C39—C40 | 55.3 (2) |
C14—C15—C16—C17 | −53.20 (19) | C38—C39—C40—C41 | −55.7 (2) |
C15—C16—C17—C18 | 55.06 (19) | C39—C40—C41—C42 | 55.5 (2) |
C16—C17—C18—C13 | −57.60 (18) | N4—C37—C42—C41 | 179.54 (13) |
N2—C13—C18—C17 | −174.76 (12) | C38—C37—C42—C41 | 53.66 (18) |
C14—C13—C18—C17 | 56.47 (16) | C40—C41—C42—C37 | −55.8 (2) |
C13—N2—C19—C20 | −103.47 (14) | C37—N4—C43—C44 | −58.69 (18) |
Zr1—N2—C19—C20 | 86.23 (16) | Zr3—N4—C43—C44 | 126.91 (12) |
C13—N2—C19—C24 | 131.82 (13) | C37—N4—C43—C48 | 67.88 (17) |
Zr1—N2—C19—C24 | −38.48 (19) | Zr3—N4—C43—C48 | −106.52 (13) |
N2—C19—C20—C21 | −178.17 (12) | N4—C43—C44—C45 | −174.77 (14) |
C24—C19—C20—C21 | −53.08 (17) | C48—C43—C44—C45 | 54.97 (18) |
C19—C20—C21—C22 | 55.22 (18) | C43—C44—C45—C46 | −53.7 (2) |
C20—C21—C22—C23 | −56.17 (18) | C44—C45—C46—C47 | 52.7 (2) |
C21—C22—C23—C24 | 56.95 (18) | C45—C46—C47—C48 | −55.2 (2) |
C22—C23—C24—C19 | −56.19 (18) | C46—C47—C48—C43 | 58.40 (19) |
N2—C19—C24—C23 | 179.23 (12) | N4—C43—C48—C47 | 174.08 (13) |
C20—C19—C24—C23 | 53.35 (17) | C44—C43—C48—C47 | −57.09 (17) |
Symmetry codes: (i) −x+1, −y, z; (ii) −x, −y, z; (iii) y, −x, −z+1; (iv) −y, x, −z+1; (v) −x+1, −y+1, z; (vi) y, −x+1, −z+1; (vii) −y+1, x, −z+1. |
Funding information
Funding for this research was provided by: Deutsche Forschungsgemeinschaft (GRK No. 2226).
References
Adler, C., Bekurdts, A., Haase, D., Saak, W., Schmidtmann, M. & Beckhaus, R. (2014b). Eur. J. Inorg. Chem. pp. 1289–1302. Web of Science CSD CrossRef Google Scholar
Adler, C., Tomaschun, G., Schmidtmann, M. & Beckhaus, R. (2014a). Organometallics, 33, 7011–7014. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. & Putz, H. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2015). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Diamond, G. M., Jordan, R. F. & Petersen, J. L. (1996). Organometallics, 15, 4030–4037. CSD CrossRef CAS Web of Science Google Scholar
Diamond, G. M., Rodewald, S. & Jordan, R. F. (1995). Organometallics, 14, 5–7. CrossRef CAS Web of Science Google Scholar
Duan, Z., Thomas, L. M. & Verkade, J. G. (1997). Polyhedron, 16, 635–641. CSD CrossRef CAS Web of Science Google Scholar
Guérin, F., Stewart, J. C., Beddie, C. & Stephan, D. W. (2000). Organometallics, 19, 2994–3000. Google Scholar
Hitchcock, P. B., Lappert, M. F. & Protchenko, A. V. (2006). Chem. Commun. pp. 3546–3548. Web of Science CSD CrossRef Google Scholar
Kasani, A., Gambarotta, S. & Bensimon, C. (1997). Can. J. Chem. 75, 1494–1499. Web of Science CSD CrossRef CAS Google Scholar
Kempe, R. (2000). Angew. Chem. Int. Ed. 39, 468–493. CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Motolko, K. S. A., Price, J. S., Emslie, D. J. H., Jenkins, H. A. & Britten, J. F. (2017). Organometallics, 36, 3084–3093. Web of Science CSD CrossRef CAS Google Scholar
Pyykkö, P. & Atsumi, M. (2009). Chem. Eur. J. 15, 12770–12779. Web of Science CrossRef PubMed Google Scholar
Roesky, P. W. (2009). Angew. Chem. Int. Ed. 48, 4892–4894. Web of Science CrossRef CAS Google Scholar
Scherer, W., Wolstenholme, D. J., Herz, V., Eickerling, G., Brück, A., Benndorf, P. & Roesky, P. W. (2010). Angew. Chem. Int. Ed. 49, 2242–2246. Web of Science CSD CrossRef CAS Google Scholar
Shafir, A. & Arnold, A. (2001). J. Am. Chem. Soc. 123, 9212–9213. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yu, X., Bi, S., Guzei, I. A., Lin, Z. & Xue, Z.-L. (2004). Inorg. Chem. 43, 7111–7119. Web of Science CSD CrossRef PubMed CAS Google Scholar
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