The title compound was synthesized from the corresponding triisopropylcyclopentadiene by treatment with n-butyl-sec-butylmagnesium and crystallizes in the triclinic space group P
with half a molecule per asymmetric unit and a staggered arrangement of the cyclopentadienide ligands.
Keywords: crystal structure, magnesocene, cyclopentadienide
Abstract
The title compound, 3Cp2Mg or [Mg(C14H23)2], was synthesized from the corresponding triisopropylcyclopentadiene by treatment with n-butyl-sec-butylmagnesium. The structural characterization by single-crystal X-ray diffraction revealed that the compound crystallizes in the triclinic space group P
with half a molecule per asymmetric unit and a staggered arrangement of the cyclopentadienide ligands.
Chemical context
Magnesocene (Cp2Mg) was initially reported by Wilkinson and Fischer and co-workers in 1954, just a few years after the discovery of ferrocene (Wilkinson & Cotton, 1954 ▸; Fischer & Hafner, 1954 ▸). Although magnesocene exhibits distinctively different chemical properties, it is isostructural to ferrocene and marked the beginning of main-group metallocene chemistry. One of the key differences in reactivity between alkaline-earth metallocenes and ferrocenes is that the central atoms of the former exhibit Lewis acidic character. Therefore, many crystal structures of magnesocenes are actually of donor complexes, such as magnesocene mono- and bis(tetrahydrofuran) adduct, Cp2Mg·(thf) and Cp2Mg·(thf)2 (Lehmkuhl et al., 1986 ▸; Jaenschke et al., 2003 ▸; Kim et al., 2007 ▸). Nevertheless, solvent-free crystal structures are also known, especially in case of highly substituted magnesocenes (Morley et al., 1987 ▸; Gardiner et al., 1991 ▸; Weber et al., 2002 ▸; Vollet et al., 2003 ▸; Deacon et al., 2015 ▸; Müller et al., 2021 ▸). Hanusa and coworkers had reported the synthesis of 1,1′,2,2′,4,4′-hexaisopropylmagnesocene, 3Cp2Mg, -calcocene, 3Cp2Ca, -strontocene, 3Cp2Sr, and -barocene, 3Cp2Ba (the triisopropylcyclopentadienide ligand is commonly abbreviated as ‘3Cp’), via treatment of potassium 1,2,4-triisopropylcyclopentadienide, 3CpK, with the corresponding metal(II) bromide or iodide and described the magnesocene to be oily or waxy in composition (Burkey et al., 1993 ▸, 1994 ▸). Thus, no crystal structure was obtained of the title compound. We found that the title compound may also be obtained through treatment of an isomeric mixture of triisopropylcyclopentadiene with n-butyl-sec-butylmagnesium in hexane.
Structural commentary
The title compound crystallizes in the triclinic space group P
with half a molecule per asymmetric unit, due to an inversion center at the magnesium atom position (Fig. 1 ▸), resulting in C
2h
symmetry for the molecule. Accordingly, the Cp rings adopt a staggered arrangement with the single isopropyl group at the C4 position facing the two isopropyl groups at the C1 and C2 positions and are perfectly coplanar to each other (Fig. 2 ▸). The C—C bond lengths within the Cp ring are almost equal [C1—C2: 1.4237 (18) Å; C2—C3: 1.4268 (17) Å; C3—C4: 1.4172 (19) Å; C4—C5: 1.4220 (18) Å; C5—C1: 1.4277 (18) Å] implying a high degree of 6π electron aromaticity, and the Mg⋯Cpcentroid distance is 1.9852 (1) Å, which is within the normal range [e.g.: Cp2Mg: 1.9897 (5) Å] for magnesocenes (Bünder & Weiss, 1975 ▸).
Figure 1.
Asymmetric unit of the title compound (displacement ellipsoids are drawn at the 50% probability level).
Figure 2.
(a) Side view and (b) top view of the molecular structure of the title compound in the crystal. Symmetry code: (’) 1 − x, 1 − y, 1 − z. Displacement ellipsoids are drawn at the 50% probability level; H atoms omitted for clarity.
Supramolecular features
The molecules of the title compound are well separated from each other in the crystal structure, with one magnesocene molecule per unit cell. Each molecule has eight neighboring molecules, forming a distorted hexagonal bipyramidal coordination geometry (Fig. 3 ▸ a and 3b), with distances of d min (Mg1⋯Mg1i) = 8.7025 (4) Å, d max (Mg1⋯Mg1iii) = 9.3031 (3) Å and d axial (Mg1⋯Mg1iv) = 9.2033 (4) Å [symmetry codes: (i) −1 + x, y, z; (iii) 1 + x, −1 + y, z; (iv) x, y, 1 + z]. The angles between the equatorial Mg atoms, the central magnesium atom and the axial magnesium atom are between θmin = 90.68° (Mg1iii—Mg1—Mg1iv) and θmax = 99.17° (Mg1ii—Mg1—Mg1iv).
Figure 3.
(a) Supramolecular coordination geometry of the title compound in the crystal and (b) the corresponding polyhedron. Symmetry codes: (i) −1 + x, y, z; (ii) x, −1 + y, z; (iii) 1 + x, −1 + y, z; (iv) x, y, 1 + z. H atoms and isopropyl groups are omitted for clarity.
Each 3Cp2Mg moiety has eight neighboring molecules within the bc and ac planes (Fig. 4 ▸ a and 4b), but only six neighboring molecules within the ab plane, forming an almost hexagonal layer (γ = 63.00°), but with the layers being congruent to each other (Fig. 4 ▸ c).
Figure 4.
Arrangement of the layers of the title compound along the crystallographic a, b and c axes (H atoms and isopropyl groups omitted for clarity).
Database survey
A search in the Cambridge Structural Database (CSD, Version 5.42, update of September 2021; Groom et al., 2016 ▸) showed that 14 crystal structures of magnesocenes of the type (C5 R 5)2Mg had previously been reported. In this search, any type of donor complexes of magnesocenes of the form (C5 R 5)2Mg· Dn are not counted. The Mg⋯Cpcentroid bonding distances in these structures lie between 1.9562 (1) and 2.0628 (11) Å and the dihedral angles between the Cp planes are between 0° (co-planar geometry) and 17.892°. Thus, the bond distances and angles in the title compound are within normal ranges of known magnesocenes.
Synthesis and crystallization
Hanusa and coworkers had previously reported that 1,1′,2,2′,4,4′-hexaisopropylmagnesocene, 3Cp2Mg, could be obtained by the reaction of potassium 1,2,4-triisopropylcyclopentadienide with magnesium(II) bromide. However, in this work, we utilized dibutylmagnesium as a strong base to deprotonate the triisopropylcyclopentadiene (Fig. 5 ▸).
Figure 5.
Reaction scheme for the formation of the title compound 3Cp2Mg.
To a solution of 4.00 g (20.8 mmol) of an isomeric mixture of triisopropylcyclopentadiene in 100 mL of hexane were added 15.0 mL of a 0.7 M solution of n-butyl-sec-butylmagnesium in hexane (10.5 mmol). The light-yellow reaction solution was stirred at 333 K overnight. Subsequently, all volatiles were removed in vacuo and a yellow oil was obtained, from which the title compound crystallized over the course of one day at ambient temperature. The crystallized material was washed with small portions of hexane and dried in vacuo to obtain the title compound as a pure, colorless, crystalline solid in 43% yield (1.83 g; 4.50 mmol).
In addition to a structural characterization by single-crystal X-ray diffraction, the title compound was also characterized by 1H and 13C NMR spectroscopy: 1H NMR (400 MHz, C6D6, 295 K): δ (in ppm) = 1.07 [d, J = 7Hz, 12H, CH(CH3)2], 1.28 [d, J = 7Hz, 12H, CH(CH3)2], 1.36 [d, J = 7Hz, 12H, CH(CH3)2], 2.82–2.92 [m, 6H, CH(CH3)2], 5.77 (s, 4H, Cp-H); 1H NMR (400 MHz, DMSO-D6, 294 K): δ (in ppm) = 1.06 [d, J = 7Hz, 36H, CH(CH3)2], 2.68 [sep, J = 7Hz, 2H, CH(CH3)2], 2.76 [sep, J = 7Hz, 2H, CH(CH3)2], 4.94 (s, 4H, Cp-H); 13C{1H} NMR (101 MHz, C6D6, 295 K): δ (in ppm) = 24.0 ( i Pr), 24.4 ( i Pr), 26.4 ( i Pr), 26.6 ( i Pr), 28.7 ( i Pr), 98.7 (Cp), 125.3 (Cp), 128.6 (Cp); 13C{1H} NMR (101 MHz, DMSO-D6, 294 K): δ (in ppm) = 25.9 ( i Pr), 26.8 ( i Pr), 27.0 ( i Pr), 29.1 ( i Pr), 94.6 (Cp), 119.4 (Cp), 120.9 (Cp).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 1 ▸. All non H-atoms were located in the electron density maps and refined anisotropically. C-bound H atoms were placed in positions of optimized geometry and treated as riding atoms: C—H = 1.00 Å (CH), 0.98 Å (CH3), and with U iso(H) = kU eq(C), where k = 1.2 for CH and 1.5 for CH3.
Table 1. Experimental details.
| Crystal data | |
| Chemical formula | [Mg(C14H23)2] |
| M r | 406.96 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 133 |
| a, b, c (Å) | 8.7025 (4), 9.0903 (4), 9.2033 (4) |
| α, β, γ (°) | 80.829 (2), 81.151 (2), 63.004 (1) |
| V (Å3) | 637.68 (5) |
| Z | 1 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.08 |
| Crystal size (mm) | 0.27 × 0.20 × 0.07 |
| Data collection | |
| Diffractometer | Bruker D8 Venture Photon II |
| Absorption correction | Multi-scan (SADABS; Krause et al., 2015 ▸) |
| T min, T max | 0.712, 0.746 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 24343, 2808, 2339 |
| R int | 0.046 |
| (sin θ/λ)max (Å−1) | 0.642 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.041, 0.100, 1.06 |
| No. of reflections | 2808 |
| No. of parameters | 138 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.23, −0.20 |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022001189/pk2661sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022001189/pk2661Isup2.hkl
CCDC reference: 2149608
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
Instrumentation and technical assistance for this work were provided by the Service Center X-ray Diffraction, with financial support from Saarland University and the German Science Foundation (INST 256/506–1).
supplementary crystallographic information
Crystal data
| [Mg(C14H23)2] | Z = 1 |
| Mr = 406.96 | F(000) = 226 |
| Triclinic, P1 | Dx = 1.060 Mg m−3 |
| a = 8.7025 (4) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 9.0903 (4) Å | Cell parameters from 7985 reflections |
| c = 9.2033 (4) Å | θ = 2.5–27.1° |
| α = 80.829 (2)° | µ = 0.08 mm−1 |
| β = 81.151 (2)° | T = 133 K |
| γ = 63.004 (1)° | Plate, yellow |
| V = 637.68 (5) Å3 | 0.27 × 0.20 × 0.07 mm |
Data collection
| Bruker D8 Venture Photon II diffractometer | 2339 reflections with I > 2σ(I) |
| Radiation source: INCOATEC IµS microfocus sealed tube | Rint = 0.046 |
| φ and ω scans | θmax = 27.1°, θmin = 2.3° |
| Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→11 |
| Tmin = 0.712, Tmax = 0.746 | k = −11→11 |
| 24343 measured reflections | l = −11→11 |
| 2808 independent reflections |
Refinement
| 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.100 | H-atom parameters constrained |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0357P)2 + 0.2575P] where P = (Fo2 + 2Fc2)/3 |
| 2808 reflections | (Δ/σ)max < 0.001 |
| 138 parameters | Δρmax = 0.23 e Å−3 |
| 0 restraints | Δρmin = −0.20 e Å−3 |
Special details
| 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | ||
| Mg1 | 0.500000 | 0.500000 | 0.500000 | 0.02198 (16) | |
| C1 | 0.58902 (16) | 0.29370 (15) | 0.34104 (14) | 0.0220 (3) | |
| C2 | 0.68748 (15) | 0.38509 (15) | 0.29476 (14) | 0.0222 (3) | |
| C3 | 0.78805 (16) | 0.36201 (16) | 0.41245 (14) | 0.0230 (3) | |
| H3 | 0.876899 | 0.404101 | 0.408093 | 0.028* | |
| C4 | 0.75424 (15) | 0.25725 (15) | 0.53102 (14) | 0.0223 (3) | |
| C5 | 0.63013 (16) | 0.21621 (15) | 0.48667 (14) | 0.0232 (3) | |
| H5 | 0.587559 | 0.136717 | 0.544119 | 0.028* | |
| C6 | 0.47318 (17) | 0.27043 (16) | 0.24895 (15) | 0.0257 (3) | |
| H6 | 0.444736 | 0.359348 | 0.164188 | 0.031* | |
| C7 | 0.30301 (19) | 0.2858 (2) | 0.33539 (19) | 0.0371 (4) | |
| H7A | 0.233030 | 0.269800 | 0.271125 | 0.056* | |
| H7B | 0.327426 | 0.201156 | 0.420434 | 0.056* | |
| H7C | 0.239326 | 0.396273 | 0.370110 | 0.056* | |
| C8 | 0.5672 (2) | 0.10251 (19) | 0.18531 (18) | 0.0368 (4) | |
| H8A | 0.491531 | 0.091596 | 0.123487 | 0.055* | |
| H8B | 0.597174 | 0.012997 | 0.266371 | 0.055* | |
| H8C | 0.673219 | 0.095503 | 0.125346 | 0.055* | |
| C9 | 0.69613 (17) | 0.47897 (17) | 0.14521 (15) | 0.0261 (3) | |
| H9 | 0.585123 | 0.513065 | 0.101394 | 0.031* | |
| C10 | 0.7151 (2) | 0.6358 (2) | 0.15456 (18) | 0.0422 (4) | |
| H10A | 0.719212 | 0.692389 | 0.055076 | 0.063* | |
| H10B | 0.822300 | 0.606089 | 0.198629 | 0.063* | |
| H10C | 0.615986 | 0.709829 | 0.215971 | 0.063* | |
| C11 | 0.8434 (2) | 0.3681 (2) | 0.04173 (17) | 0.0401 (4) | |
| H11A | 0.843621 | 0.430001 | −0.055715 | 0.060* | |
| H11B | 0.827146 | 0.270336 | 0.032239 | 0.060* | |
| H11C | 0.954060 | 0.332769 | 0.082140 | 0.060* | |
| C12 | 0.82800 (17) | 0.20815 (17) | 0.68044 (15) | 0.0274 (3) | |
| H12 | 0.750729 | 0.296459 | 0.745989 | 0.033* | |
| C13 | 1.00801 (19) | 0.1994 (2) | 0.66748 (18) | 0.0408 (4) | |
| H13A | 1.087252 | 0.112649 | 0.604724 | 0.061* | |
| H13B | 1.049205 | 0.173474 | 0.765945 | 0.061* | |
| H13C | 1.003708 | 0.306602 | 0.623400 | 0.061* | |
| C14 | 0.8308 (3) | 0.0458 (2) | 0.75386 (19) | 0.0463 (4) | |
| H14A | 0.712755 | 0.055338 | 0.767566 | 0.069* | |
| H14B | 0.876845 | 0.019984 | 0.850239 | 0.069* | |
| H14C | 0.904440 | −0.043197 | 0.691324 | 0.069* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Mg1 | 0.0202 (3) | 0.0207 (3) | 0.0236 (3) | −0.0070 (2) | 0.0002 (2) | −0.0067 (2) |
| C1 | 0.0213 (6) | 0.0189 (6) | 0.0243 (6) | −0.0064 (5) | −0.0012 (5) | −0.0066 (5) |
| C2 | 0.0195 (6) | 0.0222 (6) | 0.0227 (6) | −0.0066 (5) | 0.0004 (5) | −0.0063 (5) |
| C3 | 0.0183 (6) | 0.0259 (6) | 0.0246 (6) | −0.0088 (5) | −0.0004 (5) | −0.0064 (5) |
| C4 | 0.0191 (6) | 0.0209 (6) | 0.0238 (6) | −0.0049 (5) | −0.0011 (5) | −0.0065 (5) |
| C5 | 0.0247 (6) | 0.0196 (6) | 0.0247 (6) | −0.0089 (5) | −0.0015 (5) | −0.0040 (5) |
| C6 | 0.0281 (7) | 0.0234 (6) | 0.0278 (7) | −0.0116 (5) | −0.0063 (5) | −0.0040 (5) |
| C7 | 0.0287 (7) | 0.0408 (8) | 0.0478 (9) | −0.0168 (6) | −0.0016 (6) | −0.0174 (7) |
| C8 | 0.0358 (8) | 0.0375 (8) | 0.0415 (9) | −0.0151 (7) | −0.0044 (7) | −0.0184 (7) |
| C9 | 0.0246 (6) | 0.0300 (7) | 0.0236 (7) | −0.0123 (5) | −0.0010 (5) | −0.0027 (5) |
| C10 | 0.0609 (11) | 0.0354 (8) | 0.0335 (8) | −0.0274 (8) | 0.0068 (7) | −0.0033 (7) |
| C11 | 0.0467 (9) | 0.0395 (8) | 0.0274 (8) | −0.0156 (7) | 0.0090 (7) | −0.0075 (6) |
| C12 | 0.0268 (7) | 0.0270 (6) | 0.0246 (7) | −0.0071 (5) | −0.0034 (5) | −0.0059 (5) |
| C13 | 0.0298 (8) | 0.0566 (10) | 0.0338 (8) | −0.0146 (7) | −0.0090 (6) | −0.0067 (7) |
| C14 | 0.0652 (11) | 0.0427 (9) | 0.0356 (9) | −0.0270 (9) | −0.0204 (8) | 0.0085 (7) |
Geometric parameters (Å, º)
| Mg1—C3i | 2.3136 (12) | C7—H7B | 0.9800 |
| Mg1—C3 | 2.3136 (12) | C7—H7C | 0.9800 |
| Mg1—C5 | 2.3148 (12) | C8—H8A | 0.9800 |
| Mg1—C5i | 2.3148 (12) | C8—H8B | 0.9800 |
| Mg1—C4 | 2.3253 (12) | C8—H8C | 0.9800 |
| Mg1—C4i | 2.3253 (12) | C9—C11 | 1.5239 (19) |
| Mg1—C2i | 2.3355 (12) | C9—C10 | 1.525 (2) |
| Mg1—C2 | 2.3355 (12) | C9—H9 | 1.0000 |
| Mg1—C1i | 2.3375 (12) | C10—H10A | 0.9800 |
| Mg1—C1 | 2.3376 (12) | C10—H10B | 0.9800 |
| C1—C2 | 1.4237 (18) | C10—H10C | 0.9800 |
| C1—C5 | 1.4277 (18) | C11—H11A | 0.9800 |
| C1—C6 | 1.5143 (17) | C11—H11B | 0.9800 |
| C2—C3 | 1.4268 (17) | C11—H11C | 0.9800 |
| C2—C9 | 1.5101 (18) | C12—C14 | 1.514 (2) |
| C3—C4 | 1.4172 (19) | C12—C13 | 1.519 (2) |
| C3—H3 | 1.0000 | C12—H12 | 1.0000 |
| C4—C5 | 1.4220 (18) | C13—H13A | 0.9800 |
| C4—C12 | 1.5226 (18) | C13—H13B | 0.9800 |
| C5—H5 | 1.0000 | C13—H13C | 0.9800 |
| C6—C7 | 1.527 (2) | C14—H14A | 0.9800 |
| C6—C8 | 1.5317 (18) | C14—H14B | 0.9800 |
| C6—H6 | 1.0000 | C14—H14C | 0.9800 |
| C7—H7A | 0.9800 | ||
| C3i—Mg1—C3 | 180.0 | C5—C4—C12 | 126.88 (12) |
| C3i—Mg1—C5 | 121.04 (5) | C3—C4—Mg1 | 71.76 (7) |
| C3—Mg1—C5 | 58.96 (5) | C5—C4—Mg1 | 71.75 (7) |
| C3i—Mg1—C5i | 58.96 (5) | C12—C4—Mg1 | 118.67 (8) |
| C3—Mg1—C5i | 121.04 (5) | C4—C5—C1 | 109.12 (11) |
| C5—Mg1—C5i | 180.0 | C4—C5—Mg1 | 72.56 (7) |
| C3i—Mg1—C4 | 144.42 (5) | C1—C5—Mg1 | 73.00 (7) |
| C3—Mg1—C4 | 35.58 (5) | C4—C5—H5 | 125.3 |
| C5—Mg1—C4 | 35.69 (4) | C1—C5—H5 | 125.3 |
| C5i—Mg1—C4 | 144.31 (4) | Mg1—C5—H5 | 125.3 |
| C3i—Mg1—C4i | 35.58 (5) | C1—C6—C7 | 112.68 (11) |
| C3—Mg1—C4i | 144.42 (5) | C1—C6—C8 | 110.81 (11) |
| C5—Mg1—C4i | 144.31 (4) | C7—C6—C8 | 109.65 (12) |
| C5i—Mg1—C4i | 35.69 (4) | C1—C6—H6 | 107.8 |
| C4—Mg1—C4i | 180.0 | C7—C6—H6 | 107.8 |
| C3i—Mg1—C2i | 35.74 (4) | C8—C6—H6 | 107.8 |
| C3—Mg1—C2i | 144.26 (4) | C6—C7—H7A | 109.5 |
| C5—Mg1—C2i | 120.74 (5) | C6—C7—H7B | 109.5 |
| C5i—Mg1—C2i | 59.26 (5) | H7A—C7—H7B | 109.5 |
| C4—Mg1—C2i | 120.27 (4) | C6—C7—H7C | 109.5 |
| C4i—Mg1—C2i | 59.73 (4) | H7A—C7—H7C | 109.5 |
| C3i—Mg1—C2 | 144.26 (4) | H7B—C7—H7C | 109.5 |
| C3—Mg1—C2 | 35.74 (4) | C6—C8—H8A | 109.5 |
| C5—Mg1—C2 | 59.26 (5) | C6—C8—H8B | 109.5 |
| C5i—Mg1—C2 | 120.74 (5) | H8A—C8—H8B | 109.5 |
| C4—Mg1—C2 | 59.73 (4) | C6—C8—H8C | 109.5 |
| C4i—Mg1—C2 | 120.27 (4) | H8A—C8—H8C | 109.5 |
| C2i—Mg1—C2 | 180.0 | H8B—C8—H8C | 109.5 |
| C3i—Mg1—C1i | 59.17 (4) | C2—C9—C11 | 110.83 (11) |
| C3—Mg1—C1i | 120.83 (4) | C2—C9—C10 | 112.69 (11) |
| C5—Mg1—C1i | 144.26 (4) | C11—C9—C10 | 109.89 (12) |
| C5i—Mg1—C1i | 35.74 (4) | C2—C9—H9 | 107.7 |
| C4—Mg1—C1i | 120.28 (4) | C11—C9—H9 | 107.7 |
| C4i—Mg1—C1i | 59.72 (4) | C10—C9—H9 | 107.7 |
| C2i—Mg1—C1i | 35.48 (4) | C9—C10—H10A | 109.5 |
| C2—Mg1—C1i | 144.52 (4) | C9—C10—H10B | 109.5 |
| C3i—Mg1—C1 | 120.83 (4) | H10A—C10—H10B | 109.5 |
| C3—Mg1—C1 | 59.17 (4) | C9—C10—H10C | 109.5 |
| C5—Mg1—C1 | 35.74 (4) | H10A—C10—H10C | 109.5 |
| C5i—Mg1—C1 | 144.26 (4) | H10B—C10—H10C | 109.5 |
| C4—Mg1—C1 | 59.72 (4) | C9—C11—H11A | 109.5 |
| C4i—Mg1—C1 | 120.28 (4) | C9—C11—H11B | 109.5 |
| C2i—Mg1—C1 | 144.52 (4) | H11A—C11—H11B | 109.5 |
| C2—Mg1—C1 | 35.48 (4) | C9—C11—H11C | 109.5 |
| C1i—Mg1—C1 | 180.0 | H11A—C11—H11C | 109.5 |
| C2—C1—C5 | 107.47 (11) | H11B—C11—H11C | 109.5 |
| C2—C1—C6 | 126.57 (12) | C14—C12—C13 | 110.23 (13) |
| C5—C1—C6 | 125.78 (12) | C14—C12—C4 | 112.14 (12) |
| C2—C1—Mg1 | 72.18 (7) | C13—C12—C4 | 111.48 (12) |
| C5—C1—Mg1 | 71.26 (7) | C14—C12—H12 | 107.6 |
| C6—C1—Mg1 | 125.75 (8) | C13—C12—H12 | 107.6 |
| C1—C2—C3 | 107.35 (11) | C4—C12—H12 | 107.6 |
| C1—C2—C9 | 126.99 (11) | C12—C13—H13A | 109.5 |
| C3—C2—C9 | 125.51 (12) | C12—C13—H13B | 109.5 |
| C1—C2—Mg1 | 72.34 (7) | H13A—C13—H13B | 109.5 |
| C3—C2—Mg1 | 71.29 (7) | C12—C13—H13C | 109.5 |
| C9—C2—Mg1 | 125.19 (8) | H13A—C13—H13C | 109.5 |
| C4—C3—C2 | 109.38 (11) | H13B—C13—H13C | 109.5 |
| C4—C3—Mg1 | 72.66 (7) | C12—C14—H14A | 109.5 |
| C2—C3—Mg1 | 72.97 (7) | C12—C14—H14B | 109.5 |
| C4—C3—H3 | 125.2 | H14A—C14—H14B | 109.5 |
| C2—C3—H3 | 125.2 | C12—C14—H14C | 109.5 |
| Mg1—C3—H3 | 125.2 | H14A—C14—H14C | 109.5 |
| C3—C4—C5 | 106.69 (11) | H14B—C14—H14C | 109.5 |
| C3—C4—C12 | 126.32 (12) | ||
| C5—C1—C2—C3 | 0.18 (13) | C2—C1—C5—C4 | −0.49 (13) |
| C6—C1—C2—C3 | −175.17 (11) | C6—C1—C5—C4 | 174.90 (11) |
| Mg1—C1—C2—C3 | 63.12 (8) | Mg1—C1—C5—C4 | −64.04 (8) |
| C5—C1—C2—C9 | 175.90 (11) | C2—C1—C5—Mg1 | 63.55 (8) |
| C6—C1—C2—C9 | 0.6 (2) | C6—C1—C5—Mg1 | −121.06 (12) |
| Mg1—C1—C2—C9 | −121.16 (12) | C2—C1—C6—C7 | −138.10 (13) |
| C5—C1—C2—Mg1 | −62.94 (8) | C5—C1—C6—C7 | 47.38 (17) |
| C6—C1—C2—Mg1 | 121.71 (12) | Mg1—C1—C6—C7 | −44.39 (16) |
| C1—C2—C3—C4 | 0.21 (14) | C2—C1—C6—C8 | 98.62 (15) |
| C9—C2—C3—C4 | −175.60 (11) | C5—C1—C6—C8 | −75.90 (16) |
| Mg1—C2—C3—C4 | 64.02 (9) | Mg1—C1—C6—C8 | −167.68 (10) |
| C1—C2—C3—Mg1 | −63.81 (8) | C1—C2—C9—C11 | −90.94 (15) |
| C9—C2—C3—Mg1 | 120.39 (12) | C3—C2—C9—C11 | 84.04 (16) |
| C2—C3—C4—C5 | −0.50 (13) | Mg1—C2—C9—C11 | 175.25 (10) |
| Mg1—C3—C4—C5 | 63.71 (8) | C1—C2—C9—C10 | 145.44 (13) |
| C2—C3—C4—C12 | −176.84 (11) | C3—C2—C9—C10 | −39.58 (18) |
| Mg1—C3—C4—C12 | −112.63 (12) | Mg1—C2—C9—C10 | 51.63 (15) |
| C2—C3—C4—Mg1 | −64.21 (8) | C3—C4—C12—C14 | −155.61 (13) |
| C3—C4—C5—C1 | 0.61 (13) | C5—C4—C12—C14 | 28.78 (18) |
| C12—C4—C5—C1 | 176.92 (11) | Mg1—C4—C12—C14 | 116.73 (12) |
| Mg1—C4—C5—C1 | 64.33 (8) | C3—C4—C12—C13 | −31.46 (18) |
| C3—C4—C5—Mg1 | −63.71 (8) | C5—C4—C12—C13 | 152.93 (13) |
| C12—C4—C5—Mg1 | 112.60 (12) | Mg1—C4—C12—C13 | −119.13 (11) |
Symmetry code: (i) −x+1, −y+1, −z+1.
Funding Statement
This work was funded by Deutsche Forschungsgemeinschaft grant SCHA1915/3-1.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022001189/pk2661sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022001189/pk2661Isup2.hkl
CCDC reference: 2149608
Additional supporting information: crystallographic information; 3D view; checkCIF report