Crystal structure of 1,1′,2,2′,4,4′-hexa­iso­propyl­magnesocene

Bachmann, N.; Wirtz, L.; Morgenstern, B.; Müller, C.; Schäfer, A.

doi:10.1107/S2056989022001189

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Volume 78| Part 3| March 2022| Pages 287-290

https://doi.org/10.1107/S2056989022001189

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Crystal structure of 1,1′,2,2′,4,4′-hexaisopropylmagnesocene

Nico Bachmann,^a Lisa Wirtz,^a Bernd Morgenstern,^a Carsten Müller ^a and André Schäfer ^a ^*

^aSaarland University, Faculty of Natural Sciences and Technology, Department of Chemistry, Campus Saarbrücken, 66123 Saarbrücken, Germany
^*Correspondence e-mail: andre.schaefer@uni-saarland.de

Edited by S. Parkin, University of Kentucky, USA (Received 5 January 2022; accepted 1 February 2022; online 3 February 2022)

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 $[\overline{1}]$ with half a molecule per asymmetric unit and a staggered arrangement of the cyclopentadienide ligands.

Keywords: crystal structure; magnesocene; cyclopentadienide.

CCDC reference: 2149608

1. 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.

2. Structural commentary

The title compound crystallizes in the triclinic space group P $[\overline{1}]$ 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⋯Cp^centroid 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.

3. 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. 3a 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⋯Mg1^iv) = 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 θ_min = 90.68° (Mg1ⁱⁱⁱ—Mg1—Mg1^iv) and θ_max = 99.17° (Mg1ⁱⁱ—Mg1—Mg1^iv).

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. 4a 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. 4c).

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).

4. 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 (C₅R₅)₂Mg had previously been reported. In this search, any type of donor complexes of magnesocenes of the form (C₅R₅)₂Mg·D_n are not counted. The Mg⋯Cp^centroid 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.

5. 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 (ⁱPr), 24.4 (ⁱPr), 26.4 (ⁱPr), 26.6 (ⁱPr), 28.7 (ⁱPr), 98.7 (Cp), 125.3 (Cp), 128.6 (Cp); ¹³C{¹H} NMR (101 MHz, DMSO-D₆, 294 K): δ (in ppm) = 25.9 (ⁱPr), 26.8 (ⁱPr), 27.0 (ⁱPr), 29.1 (ⁱPr), 94.6 (Cp), 119.4 (Cp), 120.9 (Cp).

6. 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 $[\overline{1}]$
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[F² > 2σ(F²)], wR(F²), S	0.041, 0.100, 1.06
No. of reflections	2808
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.20
Computer programs: APEX3 and SAINT (Bruker, 2019 ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), shelXle (Hübschle et al., 2011 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2149608

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989022001189/pk2661sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989022001189/pk2661Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b), shelXle (Hübschle et al., 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

1,1',2,2',4,4'-Hexaisopropylmagnesocene top

Crystal data top

[Mg(C₁₄H₂₃)₂]	Z = 1
M_r = 406.96	F(000) = 226
Triclinic, P1	D_x = 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 top

Bruker D8 Venture Photon II diffractometer	2339 reflections with I > 2σ(I)
Radiation source: INCOATEC IÂµS microfocus sealed tube	R_int = 0.046
φ and ω scans	θ_max = 27.1°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→11
T_min = 0.712, T_max = 0.746	k = −11→11
24343 measured reflections	l = −11→11
2808 independent reflections

Refinement top

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(F_o²) + (0.0357P)² + 0.2575P] where P = (F_o² + 2F_c²)/3
2808 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Special details top

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) top

	x	y	z	U_iso*/U_eq
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) top

	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) top

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.

Acknowledgements

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).

Funding information

Funding for this research was provided by: Deutsche Forschungsgemeinschaft (Emmy Noether program No. SCHA1915/3-1).

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