research communications
Crystal structures of di-μ-bromido-bis{dibromido[η5-2-(dimethylamino)indenyl]zirconium(IV)} and dibromidobis[η5-2-(dimethylamino)indenyl]zirconium(IV)
aX-ray Structural Laboratory, A. N. Nesmeyanov Institute of Organoelement Compounds, Vavilova St. 28, GSP-1, Moscow 119991, V-334, Russian Federation, and bDepartment of Chemistry, Lomonosov Moscow State University, 1/3 Leninskie Gory, GSP-1, Moscow 119991, Russian Federation
*Correspondence e-mail: medvedev.m.g@gmail.com
In the title compounds, [Zr2Br6(C11H12N)2], (I) and [ZrBr2(C11H12N)2], (II), the positions of the η5-binding 2-dimethylaminoindenyl units are fixed by intramolecular C—H⋯Br interactions involving aromatic or dimethylamino H atoms. The binuclear molecule of (I) is located on a general position, while the mononuclear molecule of (II) is situated on a twofold rotation axis. Both ZrIV atoms in (I) are ligated by one cyclopentadienyl (CP) ring and four Br ligands (two bridging, two terminal), while in (II) the ZrIV atom is ligated by two CP rings and two terminal Br ligands. The crystal structures of both (I) and (II) comprise of strands of π–π- and N–π-bonded molecules, which in turn are linked by C—H⋯Br interactions.
Keywords: crystal structure; zirconium; organozirconium compounds.
1. Chemical context
In the course of a systematic study of the molecular and crystal structures of cyclopentadienyl-halogenide complexes of zirconium(IV) and hafnium(IV) bearing oxygen- and nitrogen-containing substituents at the cyclopentadienyl-type ligand(s) to understand possible intra- and intermolecular interactions between the ligands resulting in specific conformational properties of the complexes as well as to explain influences of the electronic properties of the involved fragments, we have determined several new crystal structures. These results are of importance for the understanding of possible intermolecular interactions in solutions of the compounds under investigation for their further use in catalysis. Here we report on synthesis and crystal structures of two ZrIV complexes with substituted indenyl ligands, [Zr2(C11H12N)2Br6], (I) and [Zr(C11H12N)2Br2], (II). Other zirconium(IV) complexes with indenyl ligands have been reported by Chirik (2010) and Pinkas & Lamač (2015).
2. Structural commentary
η5-ligands and the ZrIV atoms being above the centres of cyclopentadienyl (CP) rings. The 2-dimethylaminoindenyl units deviate from planarity, the highest deviations involving the N atoms in (I) [0.165 (3) Å for N1 in the first anion and 0.171 (3) Å for N2 in the second anion] and one C atom [0.187 (1) Å for C9] in (II). The Zr⋯centroid(CP) distances are 2.1815 (15) Å and 2.1823 (15) Å in (I) and 2.2278 (6) Å in (II). The dihedral angles between the planes of the indenyl units which belong to the same molecule are 3.70 (8)° in (I) and 44.25 (5)° in (II).
revealed that both title compounds are monomeric in the solid state, with the dimethylaminoindenyl anions acting asCompound (I) (Fig. 1) crystallizes with one binuclear complex molecule in the Each of the ZrIV atoms is coordinated by one CP and four Br ligands, with two Br ligands in a bridging and two in a terminal coordination mode. The Zr⋯Zr distance is 4.3359 (5) Å, a little longer than in a related complex with 2-(9H-carbazol-9-yl)indenyl ligands [4.3212 (7) Å; Lebedev et al., 2009]. The Zr—centroid(CP) distances found in (I) are virtually identical to those of the related complex [2.1812 (15) and 2.1845 (15) Å; Lebedev et al., 2009] and close to those of other similar complexes with Cl and Cp* ligands [2.176 (2) Å; Martín et al., 1994] or Cl and 1-[n-butyl(dimethyl)silyl]-2,3,4,5,6,7-hexamethylindenyl ligands [2.1896 (8) Å; Buffet et al., 2015]. In (I), the range of centroid(CP)—Zr—Br angles is 103–104° and 108–111° for bridging and terminal Br ligands, respectively. The Br—Zr—Br angles are 75.823 (13) and 76.248 (13)° for bridging Br ligands and 92.208 (16) and 90.069 (16)° for terminal Br ligands.
Compound (II) (Fig. 2) crystallizes with one half of the complex molecule in the the other half being completed by application of twofold rotation symmetry. Here the ZrIV atom is coordinated by two symmetry-related CP ligands and two symmetry-related terminal Br ligands. The Br—Zr—Br angle is 93.390 (7)°, smaller than in related structures with Cl ligands [95.04 (8) or 94.90 (8)°; Barsties et al., 1996; Luttikhedde et al., 1996]. Correspondingly, the centroid(CP)—Zr—centroid(CP) angle is a little bit larger at 133.42 (3)° versus 133.07 (12) and 132.77 (14)° in the related structures.
The positions of the 2-dimethylaminoindenyl units in the two structures are fixed by intramolecular C—H⋯Br interactions involving aromatic or dimethylamino H atoms (Tables 1 and 2).
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3. Supramolecular features
The crystal structures of both (I) and (II) (Figs. 3 and 4) comprise of infinite strands (along [100] for (I) and along [001] for (II)), of π–π- and N–π-bonded molecules, which in turn are linked by C—H⋯Br interactions. The plane-to-plane distances of the stacked dimethylaminoindenyl moieties are 3.656 (4) and 3.481 (3) Å for (I) and 3.6533 (10) Å for (II), with angles between the planes of 3.70 (8)° for (I) and 0° for (II). C—H⋯Br interactions are in the range 2.86–3.53 Å for both structures (Tables 1 and 2). The presence of the ternary amino function in the two structures plays a crucial role in the supramolecular architecture since dichlorido-bis(η5-2-dimethylaminoindenyl)zirconium(IV) (Barsties et al., 1996; Luttikhedde et al., 1996) also exhibits stacking interactions, but dichlorido-bis(η5-indenyl)zirconium(IV) (Repo et al., 1996) does not.
4. Synthesis and crystallization
Di[(μ-bromido)(η5-2-dimethylaminoindenyl)dibromidozirconium(IV)], (I), was obtained by reaction of Zr(NMe2)4 with one equivalent of 2-dimethylamino-1H-indene in toluene, followed by treatment of an excess of Me3SiBr. The crude product was recrystallized from toluene.
Bis(η5-2-dimethylaminoindenyl)dibromidozirconium(IV), (II), was obtained from the reaction of (I) with one equivalent (per Zr) of 2-dimethylaminoindenyllithium in tetrahydrofuran. The crude product was recrystallized from toluene.
5. Refinement
Crystal data, data collection and structure . H atoms were fixed geometrically and refined using a riding model with Uiso(H) = 1.2Ueq(C) for aromatic hydrogen atoms and Uiso(H) = 1.5Ueq(C) for hydrogen atoms associated with methyl groups.
details are summarized in Table 3
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Supporting information
For both compounds, data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).[Zr2Br6(C11H12N)2] | F(000) = 1840 |
Mr = 978.33 | Dx = 2.367 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.3275 (6) Å | Cell parameters from 9986 reflections |
b = 13.9365 (7) Å | θ = 2.3–35.3° |
c = 17.6082 (9) Å | µ = 9.51 mm−1 |
β = 99.028 (1)° | T = 100 K |
V = 2745.3 (2) Å3 | Plate, clear light yellow |
Z = 4 | 0.34 × 0.14 × 0.04 mm |
Bruker APEXII CCD diffractometer | 6465 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
φ and ω scans | θmax = 30.0°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −15→15 |
Tmin = 0.052, Tmax = 0.165 | k = −19→19 |
35046 measured reflections | l = −24→24 |
7921 independent reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.033 | H-atom parameters constrained |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.0301P)2 + 4.7762P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
7921 reflections | Δρmax = 1.23 e Å−3 |
293 parameters | Δρmin = −0.80 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Zr1 | 0.36393 (3) | 0.65228 (2) | 0.29842 (2) | 0.01182 (7) | |
Zr2 | 0.64736 (3) | 0.55177 (2) | 0.17911 (2) | 0.01153 (7) | |
Br1 | 0.48396 (3) | 0.48720 (2) | 0.26602 (2) | 0.01492 (7) | |
Br2 | 0.51643 (3) | 0.71490 (2) | 0.20438 (2) | 0.01584 (8) | |
Br3 | 0.39515 (3) | 0.58155 (3) | 0.43385 (2) | 0.01707 (8) | |
Br4 | 0.39478 (4) | 0.82303 (3) | 0.35560 (2) | 0.02100 (8) | |
Br5 | 0.61893 (3) | 0.60910 (3) | 0.04056 (2) | 0.01838 (8) | |
Br6 | 0.63720 (3) | 0.37380 (2) | 0.13784 (2) | 0.01671 (8) | |
N1 | 0.0895 (3) | 0.5840 (2) | 0.36083 (18) | 0.0173 (6) | |
N2 | 0.9189 (3) | 0.6378 (2) | 0.12242 (17) | 0.0140 (6) | |
C1 | 0.1401 (3) | 0.6093 (3) | 0.2990 (2) | 0.0147 (7) | |
C2 | 0.1957 (3) | 0.5458 (3) | 0.2516 (2) | 0.0146 (7) | |
H2 | 0.1972 | 0.4743 | 0.2561 | 0.018* | |
C3 | 0.2185 (3) | 0.5991 (3) | 0.1849 (2) | 0.0155 (7) | |
C4 | 0.2623 (3) | 0.5706 (3) | 0.1174 (2) | 0.0202 (8) | |
H4 | 0.2819 | 0.5055 | 0.1095 | 0.024* | |
C5 | 0.2755 (4) | 0.6392 (3) | 0.0640 (2) | 0.0244 (8) | |
H5 | 0.3036 | 0.6210 | 0.0181 | 0.029* | |
C6 | 0.2485 (4) | 0.7367 (3) | 0.0755 (2) | 0.0250 (9) | |
H6 | 0.2573 | 0.7821 | 0.0365 | 0.030* | |
C7 | 0.2100 (3) | 0.7672 (3) | 0.1412 (2) | 0.0210 (8) | |
H7 | 0.1950 | 0.8333 | 0.1490 | 0.025* | |
C8 | 0.1928 (3) | 0.6973 (3) | 0.1979 (2) | 0.0160 (7) | |
C9 | 0.1556 (3) | 0.7050 (3) | 0.2719 (2) | 0.0174 (7) | |
H9 | 0.1235 | 0.7644 | 0.2931 | 0.021* | |
C10 | 0.0968 (3) | 0.4848 (3) | 0.3864 (2) | 0.0219 (8) | |
H10A | 0.0764 | 0.4423 | 0.3419 | 0.033* | |
H10B | 0.0405 | 0.4743 | 0.4226 | 0.033* | |
H10C | 0.1782 | 0.4710 | 0.4119 | 0.033* | |
C11 | 0.0659 (4) | 0.6577 (3) | 0.4155 (2) | 0.0226 (8) | |
H11A | 0.0293 | 0.7137 | 0.3875 | 0.034* | |
H11B | 0.1411 | 0.6767 | 0.4473 | 0.034* | |
H11C | 0.0113 | 0.6321 | 0.4486 | 0.034* | |
C12 | 0.8679 (3) | 0.6084 (2) | 0.1826 (2) | 0.0141 (7) | |
C13 | 0.8056 (3) | 0.6676 (2) | 0.2300 (2) | 0.0144 (7) | |
H13 | 0.7982 | 0.7390 | 0.2261 | 0.017* | |
C14 | 0.7834 (3) | 0.6109 (2) | 0.2951 (2) | 0.0135 (6) | |
C15 | 0.7322 (3) | 0.6339 (3) | 0.3611 (2) | 0.0165 (7) | |
H15 | 0.7070 | 0.6975 | 0.3695 | 0.020* | |
C16 | 0.7198 (3) | 0.5621 (3) | 0.4129 (2) | 0.0160 (7) | |
H16 | 0.6874 | 0.5768 | 0.4581 | 0.019* | |
C17 | 0.7545 (3) | 0.4664 (3) | 0.4001 (2) | 0.0171 (7) | |
H17 | 0.7458 | 0.4186 | 0.4372 | 0.021* | |
C18 | 0.8005 (3) | 0.4412 (3) | 0.3351 (2) | 0.0167 (7) | |
H18 | 0.8206 | 0.3764 | 0.3262 | 0.020* | |
C19 | 0.8171 (3) | 0.5144 (3) | 0.2818 (2) | 0.0139 (6) | |
C20 | 0.8588 (3) | 0.5112 (3) | 0.2085 (2) | 0.0144 (7) | |
H20 | 0.8970 | 0.4544 | 0.1877 | 0.017* | |
C21 | 0.9014 (3) | 0.7371 (3) | 0.0964 (2) | 0.0200 (8) | |
H21A | 0.9215 | 0.7805 | 0.1403 | 0.030* | |
H21B | 0.8177 | 0.7466 | 0.0733 | 0.030* | |
H21C | 0.9532 | 0.7507 | 0.0581 | 0.030* | |
C22 | 0.9489 (3) | 0.5679 (3) | 0.0667 (2) | 0.0192 (7) | |
H22A | 0.9910 | 0.5135 | 0.0940 | 0.029* | |
H22B | 1.0004 | 0.5981 | 0.0338 | 0.029* | |
H22C | 0.8754 | 0.5451 | 0.0350 | 0.029* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr1 | 0.01160 (15) | 0.01065 (15) | 0.01307 (16) | −0.00015 (11) | 0.00149 (12) | 0.00016 (11) |
Zr2 | 0.01121 (15) | 0.01036 (15) | 0.01283 (15) | −0.00005 (11) | 0.00130 (12) | 0.00005 (11) |
Br1 | 0.01492 (16) | 0.01102 (16) | 0.01984 (17) | 0.00068 (12) | 0.00585 (13) | 0.00148 (12) |
Br2 | 0.01443 (16) | 0.01133 (16) | 0.02277 (19) | 0.00114 (12) | 0.00607 (13) | 0.00317 (13) |
Br3 | 0.01681 (17) | 0.02043 (18) | 0.01397 (16) | 0.00111 (13) | 0.00243 (13) | 0.00302 (13) |
Br4 | 0.0270 (2) | 0.01313 (17) | 0.02242 (19) | −0.00230 (14) | 0.00246 (15) | −0.00387 (13) |
Br5 | 0.01924 (18) | 0.02087 (18) | 0.01419 (17) | −0.00033 (13) | 0.00006 (13) | 0.00387 (13) |
Br6 | 0.02123 (18) | 0.01188 (16) | 0.01692 (17) | −0.00105 (13) | 0.00267 (13) | −0.00233 (12) |
N1 | 0.0170 (15) | 0.0188 (15) | 0.0169 (15) | 0.0014 (12) | 0.0047 (12) | 0.0013 (12) |
N2 | 0.0154 (14) | 0.0147 (14) | 0.0127 (14) | 0.0011 (11) | 0.0047 (11) | 0.0026 (11) |
C1 | 0.0122 (15) | 0.0188 (17) | 0.0128 (16) | 0.0002 (13) | 0.0010 (13) | −0.0004 (13) |
C2 | 0.0142 (16) | 0.0130 (16) | 0.0166 (17) | −0.0005 (12) | 0.0027 (13) | −0.0005 (12) |
C3 | 0.0126 (16) | 0.0187 (17) | 0.0141 (17) | −0.0021 (13) | −0.0013 (13) | 0.0005 (13) |
C4 | 0.0189 (18) | 0.025 (2) | 0.0162 (18) | −0.0028 (15) | 0.0012 (14) | −0.0048 (14) |
C5 | 0.0210 (19) | 0.037 (2) | 0.0150 (18) | −0.0037 (16) | 0.0025 (15) | 0.0000 (16) |
C6 | 0.0216 (19) | 0.033 (2) | 0.0192 (19) | −0.0021 (16) | 0.0001 (15) | 0.0117 (16) |
C7 | 0.0161 (18) | 0.0198 (19) | 0.026 (2) | −0.0018 (14) | −0.0017 (15) | 0.0083 (15) |
C8 | 0.0119 (16) | 0.0196 (18) | 0.0161 (17) | 0.0005 (13) | 0.0011 (13) | 0.0046 (13) |
C9 | 0.0162 (17) | 0.0152 (17) | 0.0194 (18) | 0.0022 (13) | −0.0011 (14) | −0.0006 (13) |
C10 | 0.0192 (18) | 0.024 (2) | 0.0224 (19) | −0.0052 (15) | 0.0041 (15) | 0.0063 (15) |
C11 | 0.0234 (19) | 0.027 (2) | 0.0189 (19) | 0.0055 (16) | 0.0072 (15) | −0.0007 (15) |
C12 | 0.0128 (16) | 0.0123 (16) | 0.0167 (17) | 0.0013 (12) | 0.0004 (13) | 0.0000 (12) |
C13 | 0.0130 (15) | 0.0125 (16) | 0.0175 (17) | −0.0011 (12) | 0.0018 (13) | 0.0000 (13) |
C14 | 0.0124 (15) | 0.0136 (16) | 0.0135 (16) | −0.0027 (12) | −0.0007 (12) | −0.0019 (12) |
C15 | 0.0172 (17) | 0.0165 (17) | 0.0161 (17) | −0.0014 (13) | 0.0031 (13) | −0.0028 (13) |
C16 | 0.0176 (17) | 0.0182 (18) | 0.0130 (16) | 0.0004 (13) | 0.0046 (13) | −0.0020 (13) |
C17 | 0.0185 (17) | 0.0179 (18) | 0.0146 (17) | −0.0010 (13) | 0.0013 (14) | 0.0039 (13) |
C18 | 0.0172 (17) | 0.0139 (17) | 0.0183 (18) | −0.0005 (13) | 0.0003 (14) | 0.0026 (13) |
C19 | 0.0112 (15) | 0.0145 (16) | 0.0145 (16) | −0.0009 (12) | −0.0025 (12) | −0.0016 (12) |
C20 | 0.0142 (16) | 0.0154 (16) | 0.0141 (16) | 0.0005 (13) | 0.0037 (13) | −0.0001 (13) |
C21 | 0.0165 (17) | 0.0186 (18) | 0.025 (2) | −0.0011 (14) | 0.0040 (15) | 0.0059 (15) |
C22 | 0.0208 (18) | 0.0223 (19) | 0.0150 (17) | 0.0024 (14) | 0.0045 (14) | −0.0013 (14) |
Zr1—Br1 | 2.7767 (5) | C6—H6 | 0.9500 |
Zr1—Br2 | 2.7176 (5) | C6—C7 | 1.367 (6) |
Zr1—Br3 | 2.5531 (5) | C7—H7 | 0.9500 |
Zr1—Br4 | 2.5862 (5) | C7—C8 | 1.430 (5) |
Zr1—C1 | 2.607 (3) | C8—C9 | 1.435 (5) |
Zr1—C2 | 2.453 (3) | C9—H9 | 1.0000 |
Zr1—C3 | 2.495 (4) | C10—H10A | 0.9800 |
Zr1—C8 | 2.491 (4) | C10—H10B | 0.9800 |
Zr1—C9 | 2.445 (4) | C10—H10C | 0.9800 |
Zr2—Br1 | 2.7325 (5) | C11—H11A | 0.9800 |
Zr2—Br2 | 2.7881 (5) | C11—H11B | 0.9800 |
Zr2—Br5 | 2.5391 (5) | C11—H11C | 0.9800 |
Zr2—Br6 | 2.5820 (5) | C12—C13 | 1.435 (5) |
Zr2—C12 | 2.611 (3) | C12—C20 | 1.437 (5) |
Zr2—C13 | 2.474 (3) | C13—H13 | 1.0000 |
Zr2—C14 | 2.497 (3) | C13—C14 | 1.445 (5) |
Zr2—C19 | 2.479 (3) | C14—C15 | 1.415 (5) |
Zr2—C20 | 2.436 (3) | C14—C19 | 1.427 (5) |
N1—C1 | 1.355 (5) | C15—H15 | 0.9500 |
N1—C10 | 1.452 (5) | C15—C16 | 1.376 (5) |
N1—C11 | 1.461 (5) | C16—H16 | 0.9500 |
N2—C12 | 1.348 (5) | C16—C17 | 1.418 (5) |
N2—C21 | 1.460 (5) | C17—H17 | 0.9500 |
N2—C22 | 1.460 (5) | C17—C18 | 1.374 (5) |
C1—C2 | 1.429 (5) | C18—H18 | 0.9500 |
C1—C9 | 1.436 (5) | C18—C19 | 1.420 (5) |
C2—H2 | 1.0000 | C19—C20 | 1.443 (5) |
C2—C3 | 1.446 (5) | C20—H20 | 1.0000 |
C3—C4 | 1.414 (5) | C21—H21A | 0.9800 |
C3—C8 | 1.426 (5) | C21—H21B | 0.9800 |
C4—H4 | 0.9500 | C21—H21C | 0.9800 |
C4—C5 | 1.366 (6) | C22—H22A | 0.9800 |
C5—H5 | 0.9500 | C22—H22B | 0.9800 |
C5—C6 | 1.414 (6) | C22—H22C | 0.9800 |
Br2—Zr1—Br1 | 76.248 (13) | C4—C3—C2 | 132.0 (3) |
Br3—Zr1—Br1 | 82.618 (15) | C4—C3—C8 | 120.8 (3) |
Br3—Zr1—Br2 | 133.232 (17) | C8—C3—Zr1 | 73.2 (2) |
Br3—Zr1—Br4 | 90.069 (16) | C8—C3—C2 | 107.2 (3) |
Br3—Zr1—C1 | 84.27 (8) | C3—C4—H4 | 120.9 |
Br4—Zr1—Br1 | 143.296 (17) | C5—C4—C3 | 118.2 (4) |
Br4—Zr1—Br2 | 83.207 (15) | C5—C4—H4 | 120.9 |
Br4—Zr1—C1 | 106.38 (8) | C4—C5—H5 | 119.1 |
C1—Zr1—Br1 | 108.57 (8) | C4—C5—C6 | 121.7 (4) |
C1—Zr1—Br2 | 141.97 (8) | C6—C5—H5 | 119.1 |
C2—Zr1—Br1 | 79.02 (8) | C5—C6—H6 | 119.2 |
C2—Zr1—Br2 | 121.59 (9) | C7—C6—C5 | 121.6 (4) |
C2—Zr1—Br3 | 93.84 (9) | C7—C6—H6 | 119.2 |
C2—Zr1—Br4 | 137.53 (8) | C6—C7—H7 | 120.8 |
C2—Zr1—C1 | 32.62 (11) | C6—C7—C8 | 118.4 (4) |
C2—Zr1—C3 | 33.97 (12) | C8—C7—H7 | 120.8 |
C2—Zr1—C8 | 55.74 (12) | C3—C8—Zr1 | 73.5 (2) |
C3—Zr1—Br1 | 82.66 (9) | C3—C8—C7 | 119.2 (3) |
C3—Zr1—Br2 | 90.58 (8) | C3—C8—C9 | 108.3 (3) |
C3—Zr1—Br3 | 127.65 (8) | C7—C8—Zr1 | 119.5 (2) |
C3—Zr1—Br4 | 128.11 (9) | C7—C8—C9 | 132.5 (4) |
C3—Zr1—C1 | 54.16 (11) | C9—C8—Zr1 | 71.3 (2) |
C8—Zr1—Br1 | 114.48 (9) | Zr1—C9—H9 | 125.1 |
C8—Zr1—Br2 | 89.10 (8) | C1—C9—Zr1 | 79.8 (2) |
C8—Zr1—Br3 | 137.66 (8) | C1—C9—H9 | 125.1 |
C8—Zr1—Br4 | 95.00 (9) | C8—C9—Zr1 | 74.9 (2) |
C8—Zr1—C1 | 53.97 (11) | C8—C9—C1 | 107.5 (3) |
C8—Zr1—C3 | 33.24 (12) | C8—C9—H9 | 125.1 |
C9—Zr1—Br1 | 134.33 (9) | N1—C10—H10A | 109.5 |
C9—Zr1—Br2 | 118.29 (9) | N1—C10—H10B | 109.5 |
C9—Zr1—Br3 | 106.39 (9) | N1—C10—H10C | 109.5 |
C9—Zr1—Br4 | 82.25 (9) | H10A—C10—H10B | 109.5 |
C9—Zr1—C1 | 32.83 (11) | H10A—C10—H10C | 109.5 |
C9—Zr1—C2 | 56.10 (12) | H10B—C10—H10C | 109.5 |
C9—Zr1—C3 | 55.98 (12) | N1—C11—H11A | 109.5 |
C9—Zr1—C8 | 33.79 (12) | N1—C11—H11B | 109.5 |
Br1—Zr2—Br2 | 75.823 (13) | N1—C11—H11C | 109.5 |
Br5—Zr2—Br1 | 130.298 (17) | H11A—C11—H11B | 109.5 |
Br5—Zr2—Br2 | 84.624 (15) | H11A—C11—H11C | 109.5 |
Br5—Zr2—Br6 | 92.208 (16) | H11B—C11—H11C | 109.5 |
Br5—Zr2—C12 | 84.51 (8) | N2—C12—Zr2 | 126.9 (2) |
Br6—Zr2—Br1 | 80.623 (14) | N2—C12—C13 | 126.3 (3) |
Br6—Zr2—Br2 | 145.776 (17) | N2—C12—C20 | 126.6 (3) |
Br6—Zr2—C12 | 107.29 (8) | C13—C12—Zr2 | 68.41 (19) |
C12—Zr2—Br1 | 144.67 (8) | C13—C12—C20 | 106.9 (3) |
C12—Zr2—Br2 | 106.31 (8) | C20—C12—Zr2 | 66.86 (19) |
C13—Zr2—Br1 | 121.87 (8) | Zr2—C13—H13 | 125.1 |
C13—Zr2—Br2 | 77.50 (8) | C12—C13—Zr2 | 79.0 (2) |
C13—Zr2—Br5 | 96.80 (8) | C12—C13—H13 | 125.1 |
C13—Zr2—Br6 | 136.60 (8) | C12—C13—C14 | 108.0 (3) |
C13—Zr2—C12 | 32.64 (11) | C14—C13—Zr2 | 74.00 (19) |
C13—Zr2—C14 | 33.80 (11) | C14—C13—H13 | 125.1 |
C13—Zr2—C19 | 55.77 (11) | C13—C14—Zr2 | 72.21 (19) |
C14—Zr2—Br1 | 92.08 (8) | C15—C14—Zr2 | 117.8 (2) |
C14—Zr2—Br2 | 82.87 (8) | C15—C14—C13 | 132.2 (3) |
C14—Zr2—Br5 | 130.59 (8) | C15—C14—C19 | 120.2 (3) |
C14—Zr2—Br6 | 122.81 (8) | C19—C14—Zr2 | 72.64 (19) |
C14—Zr2—C12 | 54.23 (12) | C19—C14—C13 | 107.5 (3) |
C19—Zr2—Br1 | 92.21 (8) | C14—C15—H15 | 120.7 |
C19—Zr2—Br2 | 115.21 (8) | C16—C15—C14 | 118.5 (3) |
C19—Zr2—Br5 | 137.19 (8) | C16—C15—H15 | 120.7 |
C19—Zr2—Br6 | 89.93 (8) | C15—C16—H16 | 119.4 |
C19—Zr2—C12 | 54.30 (11) | C15—C16—C17 | 121.3 (3) |
C19—Zr2—C14 | 33.33 (11) | C17—C16—H16 | 119.4 |
C20—Zr2—Br1 | 122.31 (8) | C16—C17—H17 | 119.2 |
C20—Zr2—Br2 | 133.25 (8) | C18—C17—C16 | 121.5 (3) |
C20—Zr2—Br5 | 104.43 (8) | C18—C17—H17 | 119.2 |
C20—Zr2—Br6 | 80.56 (8) | C17—C18—H18 | 120.9 |
C20—Zr2—C12 | 32.86 (11) | C17—C18—C19 | 118.3 (3) |
C20—Zr2—C13 | 56.07 (12) | C19—C18—H18 | 120.9 |
C20—Zr2—C14 | 56.14 (12) | C14—C19—Zr2 | 74.03 (19) |
C20—Zr2—C19 | 34.12 (12) | C14—C19—C20 | 108.0 (3) |
Zr2—Br1—Zr1 | 103.816 (15) | C18—C19—Zr2 | 117.7 (2) |
Zr1—Br2—Zr2 | 103.905 (15) | C18—C19—C14 | 120.2 (3) |
C1—N1—C10 | 119.1 (3) | C18—C19—C20 | 131.7 (3) |
C1—N1—C11 | 119.5 (3) | C20—C19—Zr2 | 71.29 (19) |
C10—N1—C11 | 118.2 (3) | Zr2—C20—H20 | 125.0 |
C12—N2—C21 | 118.8 (3) | C12—C20—Zr2 | 80.3 (2) |
C12—N2—C22 | 119.9 (3) | C12—C20—C19 | 107.7 (3) |
C22—N2—C21 | 117.1 (3) | C12—C20—H20 | 125.0 |
N1—C1—Zr1 | 126.7 (2) | C19—C20—Zr2 | 74.6 (2) |
N1—C1—C2 | 126.1 (3) | C19—C20—H20 | 125.0 |
N1—C1—C9 | 126.7 (3) | N2—C21—H21A | 109.5 |
C2—C1—Zr1 | 67.75 (19) | N2—C21—H21B | 109.5 |
C2—C1—C9 | 107.0 (3) | N2—C21—H21C | 109.5 |
C9—C1—Zr1 | 67.4 (2) | H21A—C21—H21B | 109.5 |
Zr1—C2—H2 | 125.0 | H21A—C21—H21C | 109.5 |
C1—C2—Zr1 | 79.6 (2) | H21B—C21—H21C | 109.5 |
C1—C2—H2 | 125.0 | N2—C22—H22A | 109.5 |
C1—C2—C3 | 107.9 (3) | N2—C22—H22B | 109.5 |
C3—C2—Zr1 | 74.6 (2) | N2—C22—H22C | 109.5 |
C3—C2—H2 | 125.0 | H22A—C22—H22B | 109.5 |
C2—C3—Zr1 | 71.4 (2) | H22A—C22—H22C | 109.5 |
C4—C3—Zr1 | 118.8 (2) | H22B—C22—H22C | 109.5 |
Zr1—C1—C2—C3 | −70.0 (2) | C6—C7—C8—C9 | 179.1 (4) |
Zr1—C1—C9—C8 | 70.4 (2) | C7—C8—C9—Zr1 | −113.2 (4) |
Zr1—C2—C3—C4 | 112.4 (4) | C7—C8—C9—C1 | 172.9 (4) |
Zr1—C2—C3—C8 | −65.0 (2) | C8—C3—C4—C5 | −2.1 (5) |
Zr1—C3—C4—C5 | −88.9 (4) | C9—C1—C2—Zr1 | 55.9 (2) |
Zr1—C3—C8—C7 | 115.0 (3) | C9—C1—C2—C3 | −14.0 (4) |
Zr1—C3—C8—C9 | −63.3 (2) | C10—N1—C1—Zr1 | −83.6 (4) |
Zr1—C8—C9—C1 | −73.9 (2) | C10—N1—C1—C2 | 4.1 (5) |
Zr2—C12—C13—C14 | 69.0 (2) | C10—N1—C1—C9 | −171.1 (3) |
Zr2—C12—C20—C19 | −70.3 (2) | C11—N1—C1—Zr1 | 75.6 (4) |
Zr2—C13—C14—C15 | −111.7 (4) | C11—N1—C1—C2 | 163.3 (3) |
Zr2—C13—C14—C19 | 64.5 (2) | C11—N1—C1—C9 | −11.9 (6) |
Zr2—C14—C15—C16 | 87.4 (4) | C12—C13—C14—Zr2 | −72.4 (2) |
Zr2—C14—C19—C18 | −113.1 (3) | C12—C13—C14—C15 | 175.9 (4) |
Zr2—C14—C19—C20 | 63.7 (2) | C12—C13—C14—C19 | −7.8 (4) |
Zr2—C19—C20—C12 | 74.2 (2) | C13—C12—C20—Zr2 | 56.7 (2) |
N1—C1—C2—Zr1 | −120.0 (4) | C13—C12—C20—C19 | −13.5 (4) |
N1—C1—C2—C3 | 170.0 (3) | C13—C14—C15—C16 | 178.1 (4) |
N1—C1—C9—Zr1 | 119.8 (4) | C13—C14—C19—Zr2 | −64.3 (2) |
N1—C1—C9—C8 | −169.8 (3) | C13—C14—C19—C18 | −177.4 (3) |
N2—C12—C13—Zr2 | 120.6 (4) | C13—C14—C19—C20 | −0.6 (4) |
N2—C12—C13—C14 | −170.4 (3) | C14—C15—C16—C17 | −1.5 (5) |
N2—C12—C20—Zr2 | −119.7 (4) | C14—C19—C20—Zr2 | −65.5 (2) |
N2—C12—C20—C19 | 170.1 (3) | C14—C19—C20—C12 | 8.8 (4) |
C1—C2—C3—Zr1 | 73.4 (2) | C15—C14—C19—Zr2 | 112.6 (3) |
C1—C2—C3—C4 | −174.1 (4) | C15—C14—C19—C18 | −0.6 (5) |
C1—C2—C3—C8 | 8.4 (4) | C15—C14—C19—C20 | 176.2 (3) |
C2—C1—C9—Zr1 | −56.2 (2) | C15—C16—C17—C18 | −0.8 (6) |
C2—C1—C9—C8 | 14.3 (4) | C16—C17—C18—C19 | 2.4 (5) |
C2—C3—C4—C5 | −179.2 (4) | C17—C18—C19—Zr2 | −88.6 (4) |
C2—C3—C8—Zr1 | 63.8 (2) | C17—C18—C19—C14 | −1.7 (5) |
C2—C3—C8—C7 | 178.8 (3) | C17—C18—C19—C20 | −177.6 (4) |
C2—C3—C8—C9 | 0.5 (4) | C18—C19—C20—Zr2 | 110.8 (4) |
C3—C4—C5—C6 | 1.0 (6) | C18—C19—C20—C12 | −174.9 (4) |
C3—C8—C9—Zr1 | 64.7 (2) | C19—C14—C15—C16 | 2.2 (5) |
C3—C8—C9—C1 | −9.1 (4) | C20—C12—C13—Zr2 | −55.8 (2) |
C4—C3—C8—Zr1 | −114.0 (3) | C20—C12—C13—C14 | 13.2 (4) |
C4—C3—C8—C7 | 1.0 (5) | C21—N2—C12—Zr2 | 82.5 (4) |
C4—C3—C8—C9 | −177.3 (3) | C21—N2—C12—C13 | −6.4 (5) |
C4—C5—C6—C7 | 1.3 (6) | C21—N2—C12—C20 | 169.3 (3) |
C5—C6—C7—C8 | −2.4 (6) | C22—N2—C12—Zr2 | −73.8 (4) |
C6—C7—C8—Zr1 | 88.0 (4) | C22—N2—C12—C13 | −162.6 (3) |
C6—C7—C8—C3 | 1.3 (5) | C22—N2—C12—C20 | 13.1 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Br4i | 1.00 | 2.96 | 3.694 (4) | 131 |
C4—H4···Br4i | 0.95 | 3.35 | 3.944 (4) | 123 |
C4—H4···Br5ii | 0.95 | 3.42 | 4.123 (4) | 132 |
C5—H5···Br5 | 0.95 | 3.53 | 3.998 (4) | 113 |
C5—H5···Br5ii | 0.95 | 3.52 | 4.182 (4) | 129 |
C5—H5···Br6ii | 0.95 | 2.93 | 3.840 (4) | 162 |
C10—H10C···Br3 | 0.98 | 2.88 | 3.613 (4) | 133 |
C11—H11A···Br6iii | 0.98 | 2.91 | 3.817 (4) | 154 |
C11—H11B···Br3 | 0.98 | 3.21 | 3.843 (4) | 124 |
C11—H11B···Br5iv | 0.98 | 3.44 | 3.919 (4) | 113 |
C13—H13···Br6v | 1.00 | 3.04 | 3.690 (4) | 124 |
C15—H15···Br6v | 0.95 | 3.04 | 3.655 (4) | 124 |
C16—H16···Br3 | 0.95 | 3.27 | 3.763 (4) | 114 |
C16—H16···Br3vi | 0.95 | 3.15 | 3.754 (4) | 123 |
C17—H17···Br3vi | 0.95 | 2.97 | 3.665 (4) | 131 |
C18—H18···Br2vii | 0.95 | 3.01 | 3.897 (4) | 155 |
C20—H20···Br4vii | 1.00 | 3.17 | 4.115 (4) | 158 |
C21—H21B···Br5 | 0.98 | 2.94 | 3.660 (4) | 131 |
C21—H21C···Br3viii | 0.98 | 3.20 | 3.811 (4) | 122 |
C22—H22A···Br4vii | 0.98 | 3.02 | 3.986 (4) | 167 |
C22—H22B···Br4viii | 0.98 | 3.36 | 3.974 (4) | 122 |
C22—H22C···Br5 | 0.98 | 3.06 | 3.738 (4) | 128 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) −x+1/2, y+1/2, −z+1/2; (iv) x−1/2, −y+3/2, z+1/2; (v) −x+3/2, y+1/2, −z+1/2; (vi) −x+1, −y+1, −z+1; (vii) −x+3/2, y−1/2, −z+1/2; (viii) x+1/2, −y+3/2, z−1/2. |
[ZrBr2(C11H12N)2] | F(000) = 1120 |
Mr = 567.47 | Dx = 1.834 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 18.4476 (5) Å | Cell parameters from 9893 reflections |
b = 8.3497 (2) Å | θ = 2.7–35.7° |
c = 14.3737 (4) Å | µ = 4.43 mm−1 |
β = 111.854 (1)° | T = 100 K |
V = 2054.90 (9) Å3 | Prism, yellow |
Z = 4 | 0.26 × 0.24 × 0.15 mm |
Bruker APEXII CCD diffractometer | 2876 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 30.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2008) | h = −25→25 |
Tmin = 0.552, Tmax = 0.747 | k = −11→11 |
13152 measured reflections | l = −20→20 |
3003 independent reflections |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.015 | H-atom parameters constrained |
wR(F2) = 0.039 | w = 1/[σ2(Fo2) + (0.0186P)2 + 2.1368P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
3003 reflections | Δρmax = 0.45 e Å−3 |
125 parameters | Δρmin = −0.42 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Zr1 | 0.5000 | 0.74647 (2) | 0.7500 | 0.00832 (4) | |
Br1 | 0.38964 (2) | 0.96156 (2) | 0.68020 (2) | 0.01412 (4) | |
N1 | 0.35083 (6) | 0.76823 (12) | 0.85552 (8) | 0.01326 (19) | |
C1 | 0.42107 (7) | 0.70340 (14) | 0.86778 (8) | 0.0114 (2) | |
C2 | 0.49565 (7) | 0.77305 (14) | 0.92202 (9) | 0.0116 (2) | |
H2 | 0.5045 | 0.8746 | 0.9616 | 0.014* | |
C3 | 0.55415 (7) | 0.65358 (14) | 0.93154 (8) | 0.0120 (2) | |
C4 | 0.63626 (7) | 0.65095 (16) | 0.98526 (9) | 0.0156 (2) | |
H4 | 0.6625 | 0.7421 | 1.0221 | 0.019* | |
C5 | 0.67705 (7) | 0.51419 (17) | 0.98303 (10) | 0.0175 (2) | |
H5 | 0.7319 | 0.5112 | 1.0190 | 0.021* | |
C6 | 0.63885 (7) | 0.37755 (16) | 0.92804 (9) | 0.0167 (2) | |
H6 | 0.6684 | 0.2839 | 0.9293 | 0.020* | |
C7 | 0.55973 (7) | 0.37769 (14) | 0.87287 (9) | 0.0148 (2) | |
H7 | 0.5348 | 0.2857 | 0.8358 | 0.018* | |
C8 | 0.51605 (7) | 0.51796 (14) | 0.87243 (9) | 0.0116 (2) | |
C9 | 0.43396 (7) | 0.55692 (14) | 0.82397 (9) | 0.0119 (2) | |
H9 | 0.3922 | 0.4798 | 0.7851 | 0.014* | |
C10 | 0.34843 (7) | 0.92403 (15) | 0.89929 (10) | 0.0166 (2) | |
H10A | 0.3813 | 0.9222 | 0.9708 | 0.025* | |
H10B | 0.2945 | 0.9492 | 0.8911 | 0.025* | |
H10C | 0.3678 | 1.0058 | 0.8655 | 0.025* | |
C11 | 0.28038 (7) | 0.69950 (17) | 0.78212 (10) | 0.0184 (2) | |
H11A | 0.2784 | 0.5848 | 0.7953 | 0.028* | |
H11B | 0.2807 | 0.7148 | 0.7147 | 0.028* | |
H11C | 0.2345 | 0.7526 | 0.7868 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr1 | 0.00882 (7) | 0.00802 (7) | 0.00796 (7) | 0.000 | 0.00294 (5) | 0.000 |
Br1 | 0.01459 (6) | 0.01476 (6) | 0.01381 (6) | 0.00574 (4) | 0.00618 (4) | 0.00414 (4) |
N1 | 0.0113 (4) | 0.0155 (5) | 0.0137 (4) | −0.0001 (4) | 0.0054 (4) | −0.0013 (4) |
C1 | 0.0125 (5) | 0.0128 (5) | 0.0098 (5) | −0.0001 (4) | 0.0054 (4) | 0.0011 (4) |
C2 | 0.0119 (5) | 0.0130 (5) | 0.0097 (5) | −0.0002 (4) | 0.0041 (4) | −0.0013 (4) |
C3 | 0.0134 (5) | 0.0132 (5) | 0.0095 (5) | 0.0007 (4) | 0.0043 (4) | 0.0015 (4) |
C4 | 0.0139 (5) | 0.0193 (6) | 0.0119 (5) | 0.0001 (4) | 0.0028 (4) | 0.0008 (4) |
C5 | 0.0132 (5) | 0.0230 (6) | 0.0150 (5) | 0.0037 (5) | 0.0037 (4) | 0.0046 (5) |
C6 | 0.0190 (6) | 0.0163 (6) | 0.0163 (5) | 0.0067 (4) | 0.0082 (5) | 0.0058 (4) |
C7 | 0.0192 (5) | 0.0120 (5) | 0.0142 (5) | 0.0025 (4) | 0.0076 (4) | 0.0029 (4) |
C8 | 0.0133 (5) | 0.0115 (5) | 0.0103 (5) | 0.0007 (4) | 0.0048 (4) | 0.0022 (4) |
C9 | 0.0125 (5) | 0.0115 (5) | 0.0115 (5) | −0.0011 (4) | 0.0045 (4) | 0.0003 (4) |
C10 | 0.0169 (5) | 0.0177 (6) | 0.0168 (5) | 0.0035 (4) | 0.0081 (4) | −0.0015 (4) |
C11 | 0.0112 (5) | 0.0225 (6) | 0.0200 (6) | −0.0021 (5) | 0.0042 (4) | −0.0007 (5) |
Zr1—Br1 | 2.6183 (2) | C3—C4 | 1.4215 (16) |
Zr1—Br1i | 2.6183 (2) | C3—C8 | 1.4330 (16) |
Zr1—C1 | 2.6365 (11) | C4—H4 | 0.9500 |
Zr1—C1i | 2.6365 (11) | C4—C5 | 1.3745 (18) |
Zr1—C2 | 2.5134 (11) | C5—H5 | 0.9500 |
Zr1—C2i | 2.5134 (11) | C5—C6 | 1.4171 (19) |
Zr1—C3i | 2.5432 (11) | C6—H6 | 0.9500 |
Zr1—C3 | 2.5432 (11) | C6—C7 | 1.3775 (17) |
Zr1—C8 | 2.5371 (11) | C7—H7 | 0.9500 |
Zr1—C8i | 2.5371 (11) | C7—C8 | 1.4203 (16) |
Zr1—C9 | 2.4666 (12) | C8—C9 | 1.4488 (16) |
Zr1—C9i | 2.4665 (12) | C9—H9 | 1.0000 |
N1—C1 | 1.3538 (15) | C10—H10A | 0.9800 |
N1—C10 | 1.4529 (16) | C10—H10B | 0.9800 |
N1—C11 | 1.4528 (16) | C10—H10C | 0.9800 |
C1—C2 | 1.4284 (16) | C11—H11A | 0.9800 |
C1—C9 | 1.4355 (16) | C11—H11B | 0.9800 |
C2—H2 | 1.0000 | C11—H11C | 0.9800 |
C2—C3 | 1.4382 (16) | ||
Br1i—Zr1—Br1 | 93.390 (7) | C9—Zr1—C8i | 82.39 (4) |
Br1i—Zr1—C1 | 112.58 (3) | C9i—Zr1—C8 | 82.39 (4) |
Br1i—Zr1—C1i | 78.64 (3) | C9i—Zr1—C8i | 33.62 (4) |
Br1—Zr1—C1 | 78.64 (3) | C9i—Zr1—C9 | 100.17 (6) |
Br1—Zr1—C1i | 112.58 (3) | C1—N1—C10 | 118.92 (10) |
C1—Zr1—C1i | 164.32 (5) | C1—N1—C11 | 119.38 (10) |
C2i—Zr1—Br1i | 90.65 (3) | C11—N1—C10 | 120.33 (10) |
C2—Zr1—Br1i | 82.39 (3) | N1—C1—Zr1 | 126.33 (8) |
C2—Zr1—Br1 | 90.65 (3) | N1—C1—C2 | 126.08 (11) |
C2i—Zr1—Br1 | 82.39 (3) | N1—C1—C9 | 126.19 (11) |
C2—Zr1—C1 | 32.09 (4) | C2—C1—Zr1 | 69.20 (6) |
C2i—Zr1—C1i | 32.09 (4) | C2—C1—C9 | 107.64 (10) |
C2—Zr1—C1i | 150.61 (4) | C9—C1—Zr1 | 67.25 (6) |
C2i—Zr1—C1 | 150.61 (4) | Zr1—C2—H2 | 125.2 |
C2—Zr1—C2i | 169.87 (5) | C1—C2—Zr1 | 78.70 (6) |
C2—Zr1—C3i | 153.14 (4) | C1—C2—H2 | 125.2 |
C2i—Zr1—C3 | 153.14 (4) | C1—C2—C3 | 107.80 (10) |
C2—Zr1—C3 | 33.04 (4) | C3—C2—Zr1 | 74.62 (6) |
C2i—Zr1—C3i | 33.04 (4) | C3—C2—H2 | 125.2 |
C2—Zr1—C8i | 135.28 (4) | C2—C3—Zr1 | 72.34 (6) |
C2—Zr1—C8 | 54.71 (4) | C4—C3—Zr1 | 119.62 (8) |
C2i—Zr1—C8 | 135.28 (4) | C4—C3—C2 | 132.26 (11) |
C2i—Zr1—C8i | 54.71 (4) | C4—C3—C8 | 119.88 (11) |
C3—Zr1—Br1i | 82.16 (3) | C8—C3—Zr1 | 73.38 (6) |
C3i—Zr1—Br1 | 82.16 (3) | C8—C3—C2 | 107.86 (10) |
C3—Zr1—Br1 | 123.69 (3) | C3—C4—H4 | 120.6 |
C3i—Zr1—Br1i | 123.69 (3) | C5—C4—C3 | 118.83 (12) |
C3—Zr1—C1 | 53.09 (4) | C5—C4—H4 | 120.6 |
C3i—Zr1—C1i | 53.09 (4) | C4—C5—H5 | 119.4 |
C3i—Zr1—C1 | 121.15 (4) | C4—C5—C6 | 121.26 (11) |
C3—Zr1—C1i | 121.16 (4) | C6—C5—H5 | 119.4 |
C3—Zr1—C3i | 144.49 (5) | C5—C6—H6 | 119.3 |
C8i—Zr1—Br1 | 112.13 (3) | C7—C6—C5 | 121.39 (11) |
C8i—Zr1—Br1i | 130.91 (3) | C7—C6—H6 | 119.3 |
C8—Zr1—Br1i | 112.13 (3) | C6—C7—H7 | 120.6 |
C8—Zr1—Br1 | 130.91 (3) | C6—C7—C8 | 118.75 (11) |
C8i—Zr1—C1i | 53.26 (4) | C8—C7—H7 | 120.6 |
C8—Zr1—C1 | 53.26 (4) | C3—C8—Zr1 | 73.85 (6) |
C8—Zr1—C1i | 113.14 (4) | C3—C8—C9 | 107.57 (10) |
C8i—Zr1—C1 | 113.14 (4) | C7—C8—Zr1 | 122.88 (8) |
C8i—Zr1—C3 | 112.47 (4) | C7—C8—C3 | 119.78 (11) |
C8—Zr1—C3i | 112.47 (4) | C7—C8—C9 | 132.61 (11) |
C8—Zr1—C3 | 32.77 (4) | C9—C8—Zr1 | 70.52 (6) |
C8i—Zr1—C3i | 32.77 (4) | Zr1—C9—H9 | 125.1 |
C8i—Zr1—C8 | 82.46 (5) | C1—C9—Zr1 | 80.30 (7) |
C9i—Zr1—Br1i | 99.61 (3) | C1—C9—C8 | 107.14 (10) |
C9—Zr1—Br1 | 99.61 (3) | C1—C9—H9 | 125.1 |
C9—Zr1—Br1i | 135.50 (3) | C8—C9—Zr1 | 75.86 (7) |
C9i—Zr1—Br1 | 135.50 (3) | C8—C9—H9 | 125.1 |
C9—Zr1—C1i | 131.97 (4) | N1—C10—H10A | 109.5 |
C9—Zr1—C1 | 32.46 (4) | N1—C10—H10B | 109.5 |
C9i—Zr1—C1 | 131.97 (4) | N1—C10—H10C | 109.5 |
C9i—Zr1—C1i | 32.46 (4) | H10A—C10—H10B | 109.5 |
C9—Zr1—C2i | 133.04 (4) | H10A—C10—H10C | 109.5 |
C9i—Zr1—C2 | 133.04 (4) | H10B—C10—H10C | 109.5 |
C9—Zr1—C2 | 55.31 (4) | N1—C11—H11A | 109.5 |
C9i—Zr1—C2i | 55.31 (4) | N1—C11—H11B | 109.5 |
C9—Zr1—C3 | 55.28 (4) | N1—C11—H11C | 109.5 |
C9i—Zr1—C3 | 100.26 (4) | H11A—C11—H11B | 109.5 |
C9i—Zr1—C3i | 55.28 (4) | H11A—C11—H11C | 109.5 |
C9—Zr1—C3i | 100.26 (4) | H11B—C11—H11C | 109.5 |
C9—Zr1—C8 | 33.62 (4) | ||
Zr1—C1—C2—C3 | −69.62 (8) | C3—C8—C9—Zr1 | 65.07 (8) |
Zr1—C1—C9—C8 | 71.81 (8) | C3—C8—C9—C1 | −9.88 (13) |
Zr1—C2—C3—C4 | 114.30 (13) | C4—C3—C8—Zr1 | −115.04 (10) |
Zr1—C2—C3—C8 | −65.30 (8) | C4—C3—C8—C7 | 3.99 (17) |
Zr1—C3—C4—C5 | −90.04 (13) | C4—C3—C8—C9 | −177.92 (10) |
Zr1—C3—C8—C7 | 119.04 (11) | C4—C5—C6—C7 | 1.52 (19) |
Zr1—C3—C8—C9 | −62.88 (8) | C5—C6—C7—C8 | −0.58 (18) |
Zr1—C8—C9—C1 | −74.95 (8) | C6—C7—C8—Zr1 | 87.19 (13) |
N1—C1—C2—Zr1 | −120.49 (11) | C6—C7—C8—C3 | −2.14 (17) |
N1—C1—C2—C3 | 169.89 (11) | C6—C7—C8—C9 | −179.66 (12) |
N1—C1—C9—Zr1 | 119.29 (11) | C7—C8—C9—Zr1 | −117.19 (13) |
N1—C1—C9—C8 | −168.89 (11) | C7—C8—C9—C1 | 167.86 (12) |
C1—C2—C3—Zr1 | 72.44 (8) | C8—C3—C4—C5 | −3.07 (17) |
C1—C2—C3—C4 | −173.26 (12) | C9—C1—C2—Zr1 | 56.29 (8) |
C1—C2—C3—C8 | 7.14 (13) | C9—C1—C2—C3 | −13.33 (13) |
C2—C1—C9—Zr1 | −57.49 (8) | C10—N1—C1—Zr1 | −88.58 (12) |
C2—C1—C9—C8 | 14.32 (12) | C10—N1—C1—C2 | 0.89 (17) |
C2—C3—C4—C5 | 177.38 (12) | C10—N1—C1—C9 | −175.32 (11) |
C2—C3—C8—Zr1 | 64.61 (8) | C11—N1—C1—Zr1 | 78.11 (13) |
C2—C3—C8—C7 | −176.35 (10) | C11—N1—C1—C2 | 167.58 (11) |
C2—C3—C8—C9 | 1.73 (13) | C11—N1—C1—C9 | −8.63 (18) |
C3—C4—C5—C6 | 0.36 (18) |
Symmetry code: (i) −x+1, y, −z+3/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···Br1ii | 0.95 | 2.98 | 3.8960 (13) | 163 |
C6—H6···Br1iii | 0.95 | 3.10 | 3.7621 (13) | 128 |
C7—H7···Br1iii | 0.95 | 3.09 | 3.7493 (12) | 128 |
C10—H10A···Br1iv | 0.98 | 3.11 | 3.9381 (13) | 143 |
C10—H10C···Br1 | 0.98 | 2.86 | 3.5178 (13) | 125 |
C11—H11A···Br1v | 0.98 | 3.41 | 3.9170 (13) | 115 |
C11—H11B···Br1 | 0.98 | 3.04 | 3.6325 (13) | 120 |
Symmetry codes: (ii) x+1/2, −y+3/2, z+1/2; (iii) −x+1, y−1, −z+3/2; (iv) x, −y+2, z+1/2; (v) −x+1/2, y−1/2, −z+3/2. |
Acknowledgements
This work was supported by the Russian Ministry of Education and Science (project No. 2015–14-585–0002, unique identifier RFMEFI61315X0041).
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