catena-Poly[[(tetra­hydro­furan-[kappa]O)potassium]-[mu]-([eta]⁵:[eta]⁵)-2,3,4,5-tetra­methyl-1-n-pentyl­cyclo­penta­dien­yl]

The title compound, [K(C₁₄H₂₃)(C₄H₈O)]_n, comprises zigzag chains of alternating bridging 2,3,4,5-tetra­methyl-1-n-pentyl­cyclo­penta­dienyl ligands and potassium ions, with an ancillary tetra­hydro­furan ligand in the coordination environment of potassium. The coordination polymer strands so formed extend by 2₁ screw symmetry in the b-axis direction. The chemically modified cyclo­penta­dienyl ligand, with a tethered n-pentyl group, was synthesized from 2,3,4,5-tetra­methyl­cyclo­pent-2-enone by a Grignard reaction.

S1. Comment

Cyclopentadienyl (Cp) derivatives are among the most widely used classes of ligands in modern transition metal chemistry (Crabtree, 2009). Cp complexes of alkali metals are important precursors for the transfer of Cp ligands, and Cp–potassium complexes in particular are commonly used reagents in preparative organometallic chemistry. In a metathesis reaction of a Cp–potassium complex with a metal halide, the potassium halide by-product can be readily separated from the desired organometallic complex as a precipitate, owing to the high lattice energy. Cp complexes of alkali metals exhibit a wide structural diversity, including co-ligand stabilized neutral monomers, anionic metallocenes and polymeric solid-state arrays (Harder, 1998; Jutzi & Burford, 1999; Jutzi & Reumann, 2000; Rayon & Frenking, 2002; Budzelaar et al., 2003; Erker et al., 2008). Historically, it is interesting to note that Cp complexes of alkali metals were known long before the field of Cp–transition metal complexes was kick-started by the discovery and structural characterization of ferrocene in the early 1950s (Kealy & Pauson, 1951; Wilkinson et al., 1952). The preparation of KCp was reported as early as 1901 (Thiele, 1901), although its solid-state structure as determined by high-resolution powder X-ray diffraction was reported only in 1997 (Dinnebier et al., 1997).

In the course of our systematic studies of Cp-based low-valent group 13 metal coordination compounds (González-Gallardo et al., 2012; Bollermann et al., 2012), we have frequently used the 1,2,3,4,5-pentamethylcyclopentadienyl (Cp*) ligand. In general, Cp* complexes are more stable than those of the parent unsubstituted Cp, since Cp* is more electron-rich and thus a better donor than Cp. Furthermore, Cp* complexes usually exhibit better solubility in nonpolar solvents than the Cp analogues. We have now designed an n-pentyl-substituted Cp* derivative, namely 1-n-pentyl-2,3,4,5-tetramethylcyclopentadienyl (Cp'). It is expected that the presence of the n-pentyl group further enhances the solubility of the derived complexes in non-polar solvents. Moreover, the steric demand should affect the molecular structure and crystal packing of the derived complexes.

1-n-Pentyl-2,3,4,5-tetramethylcyclopentadiene (Cp') was obtained as a dark-orange oil by a Grignard reaction of 2,3,4,5-tetramethylcyclopent-2-enone with n-pentylmagnesium bromide. The procedure was essentially adapted from a convenient synthetic route to 1,2,3,4,5-pentymethylcyclopentadiene reported by Kohl & Jutzi (1983), using n-pentylmagnesium bromide instead of methylmagnesium iodide in the last step. The material so obtained was treated with potassium hydride in tetrahydofuran (THF). Colourless crystals of the title compound, (I), were obtained unintentionally during an attempt to synthesize an aluminium complex using the potassium salt as a reagent.

In the crystal structure, (I) forms one-dimensional coordination polymer strands of alternating K⁺ cations and µ-Cp' ligands, with a nonparallel and staggered arrangement of the five-membered rings (Fig. 1). The coordination environment of potassium (Fig. 2) accommodates an ancillary THF ligand. The zigzag chains thus formed are propagated by 2₁ screw symmetry in the b-axis direction of the monoclinic lattice. The centroid-to-centroid separation of the Cp' ligands thus corresponds to b/2 (ca 5.16 Å). A displacement ellipsoid plot of (I), showing the coordination environment of K1, is given in Fig. 2, and selected geometric parameters are listed in Table 1. A comparison of the K1—C distances in the Cp'—K—Cp'ⁱ group [symmetry code: (i) -x + 1/2, y - 1/2, -z + 1/2] reveals a slight displacement of atom K1 from the C₅ axis of the five-membered rings, which can mainly be attributed to the steric demand of the n-pentyl side chain. As expected, no significant perturbation of the five-membered Cp ring is observed (Jutzi & Burford, 1999). This is evident from the C—C bond lengths (Table 1) and the planarity of the five-membered ring (r.m.s. deviation 5 × 10 ^-4 Å). In comparison with the four methyl groups attached to the Cp ring, the α-methylene group (C10) of the n-pentyl chain exhibits the most significant displacement from the mean plane of the five-membered ring, at 0.087 (3) Å. The n-pentyl chain is non-disordered and exhibits an antiperiplanar conformation around each C—C bond. The α-methylene group (C11) of the n-pentyl group is oriented towards K1; the distance between K1 and each of the two methylene H atoms is approximately 3.2 Å.

In general, the metal–ligand interaction in Cp complexes of alkali metals is considered mainly ionic (Lambert & von Raque Schleyer, 1994). The Cp_centroid—metal distance manifests the relative strengths of the interaction between the Cp ligand and the metal ion. The Cp_centroid—K distances in (I) (2.72 Å) are typical of Cp–potassium complexes (Jutzi & Burford, 1999). The Cp_centroid—K1—Cp_centroidⁱ angle in (I) is 143.2°. The Cp_centroid—K—Cp_centroid angles in polymeric chains of equimolar Cp–potassium complexes with a zigzag pattern vary over a wide range. In the structure of the parent solvent-free KCp [Cambridge Structural Database (CSD; Allen, 2002) refcode NIBSOG; Dinnebier et al., 1997], the Cp_centroid—K—Cp_centroid angle exhibits a value of 138°. With sterically demanding µ-Cp ligands, e.g. pentakis(4-n-butylphenyl)Cp (DOWKIK; Harder & Ruspic, 2009) or 1,2,4-tris(trimethylsilyl)Cp (XEPFUT; Harvey et al., 2001), Cp_centroid—K—Cp_centroid angles close to linearity are observed.

It has been proposed that the bent angle in polymeric alkali metal µ-Cp complexes depends on packing effects (Dinnebier et al., 2005). A nonparallel arrangement of the five-membered rings of the µ-Cp ligands essentially makes two additional coordination sites of the metal ion accessible for binding ancillary ligands. In NIBSOG and in KC₅H₄Si(CH₃)₃ (FOGMET; Jutzi et al., 1987), two rare examples of solvent-free polymeric potassium complexes with non-bulky µ-Cp ligands, interchain Cp—K interactions complete the coordination environment of potassium. In connection with (I), it is interesting to note that a mono- and a ditetrahydrofuran adduct of KCp*, i.e. [K(µ-Cp*(THF)]_n (CAKTEO) and [K(Cp*(THF)₂]_n (CAKTIS), were isolated and structurally characterized (Evans et al., 2002). For (I), accommodation of a second ancillary THF ligand in the coordination environment of potassium seems unfavourable, owing to the steric demand of the n-pentyl side chain of the Cp' ligand.

In conclusion, the new Cp' ligand, a Cp* derivative with a tethered n-pentyl group, was synthesized by a Grignard reaction. Chemical modification of ligands is a useful strategy to tune the structure and properties of the derived complexes. Single-crystal X-ray analysis of the THF adduct of the potassium complex, (I), revealed a zigzag polymeric array of alternating µ-Cp' ligands and potassium ions bearing THF as an ancillary ligand, which is characteristic of this class of compound. [There is a chunk of hkl data in the CIF, and it does not appear to match the separate hkl file. Please clarify.]

Related literature

For related literature, see: Allen (2002); Bollermann et al. (2012); Budzelaar et al. (2003); Crabtree (2009); Dinnebier et al. (1997, 2005); Erker et al. (2008); Evans et al. (2002); González-Gallardo, Bollermann, Fischer & Murugavel (2012); Harder (1998); Harder & Ruspic (2009); Harvey et al. (2001); Jutzi & Burford (1999); Jutzi & Reumann (2000); Jutzi et al. (1987); Kealy & Pauson (1951); Kohl & Jutzi (1983); Lambert & von Raque Schleyer (1994); Rayon & Frenking (2002); Thiele (1901); Wilkinson et al. (1952).

S2. Experimental

Starting materials were obtained from commercial sources and were used as received, unless otherwise stated. All manipulations were carried out under an atmosphere of purified argon, using standard Schlenk and glove-box techniques. Solvents were dried using an mBraun solvent purification system. The final water content was checked by Karl–Fischer titration and did not exceed 10 p.p.m. 2,3,4,5-Tetramethylcyclopent-2-enone was prepared following the literature procedure of Kohl & Jutzi (1983). Magnesium turnings were dried in a heater. Potassium hydride was purchased from Acros Organics as a dispersion in mineral oil. To obtain pure potassium hydride, the dispersion was loaded onto a frit and washed with plenty of n-hexane. After drying in a vacuum, the purified potassium hydride so obtained was stored and handled under argon in a glove-box. The ¹H NMR spectrum was recorded on a Bruker DPX-250 NMR spectrometer (abbreviations: s = singlet, m = multiplet). The residual solvent peak of C₆D₆ (δ = 7.16 p.p.m.) was used as an internal standard.

Magnesium turnings (10 g, 0.412 mol) were placed in a two-necked 500 ml flask equipped with a reflux condenser and a dropping funnel. Diethyl ether (200 ml) was added and, subsequently, n-pentyl bromide (51 ml, 0.412 mol) was added dropwise with stirring. The mixture turned cloudy and to a grey colour and started to boil. After complete addition of the n-pentyl bromide, the colour of the mixture was dark grey; stirring was continued for 30 min. Afterwards, 2,3,4,5-tetramethylcyclopent-2-enone (50 g, 0.362 mol) was added dropwise over a period of 45 min, during which the colour of the mixture became pale-green. After stirring overnight, the mixture was poured onto ice and treated with hydrochloric acid (35%, ca 100 ml) until the aqueous phase was acidic. The phases were separated and the yellow–orange aqueous phase was extracted several times with diethyl ether until it was colourless. The organic phases were combined and dried over anhydrous magnesium sulfate. The solvent was then removed with a rotary evaporator and the resulting dark-orange oil was distilled over a Vigreux column (ca 10 cm) in a vacuum (b.p. 395–405 K/~10² mm Hg) to yield 52.61 g of 1-n-pentyl-2,3,4,5-tetramethylcyclopentadiene (0.274 mol, 76%).

1-n-Pentyl-2,3,4,5-tetramethylcyclopentadiene (12.93 g, 0.067 mol) and potassium hydride (2.32 g, 0.058 mol) were placed in a flask and tetrahydrofuran (THF; 150 ml) was added. After stirring the mixture for 24 h at room temperature, the white precipitate was filtered off, washed with n-hexane and dried under a high vacuum overnight to give KCp' (yield 10 g, 0.043 mol, 74%). ¹H NMR (C₆D₆, δ, p.p.m.): 2.34 (m, 2H, n-pentyl-1 CH₂), 1.99 (s, 6H, Cp CH₃), 1.96 (s, 6H, Cp CH₃), 1.54–1.32 (m, 4H, n-pentyl-2,3 CH₂), 1.23–1.09 (m, 2H, n-pentyl-4 CH₂), 1.01 (m, 3H, n-pentyl-5 CH₃).

A small colourless crystal of (I) suitable for X-ray diffraction was obtained unintentionally during attempts to react KCp' with dichlorido(hydrido)aluminium in refluxing THF, after allowing the mixture to cool to room temperature.

S3. Refinement

The tetrahydrofuran molecule was found to be disordered over two positions and was described by a split model, which was refined with standard similar distance restraints, as well as rigid-bond and similarity restraints, and restraints towards isotropy on the displacement parameters. Refinement of the occupancies by means of a free variable yielded a ratio of 0.70 (1):0.30 (1). H atoms were placed in geometrically calculated positions and refined with the appropriate riding model, with C—H = 0.98 for methyl H atoms or 0.99 Å for methylene groups, and with U_iso(H) = 1.5U_eq(C) for methyl H atoms or 1.2U_eq(C) otherwise. The initial torsion angles of the methyl groups were determined via difference Fourier syntheses and subsequently refined while holding the tetrahedral geometry. One of the methyl groups attached to the Cp ring shows rotational disorder of the H atoms, which was taken into account by the split model. The ratio of the occupancies of the two sites refined to 0.53 (3):0.47 (3).

Computing details

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures

	Fig. 1. (a) The coordination polymer strand of (I), projected along the [101] direction. (b) The arrangement of two adjacent strands in the monoclinic unit cell, viewed along the [010] direction. For the sake of clarity, H atoms and the minor disordered component of the disordered THF ligand are not shown.
	Fig. 2. Displacement ellipsoid plot (50% probalility level) of (I), showing the coordination environment of atom K1. The minor disordered component of the disordered THF ligand is represented by empty ellipsoids and open bonds. H atoms have been omitted for clarity. [Symmetry code: (i) -x + 1/2, y - 1/2, -z + 1/2.]

catena-Poly[[(tetrahydrofuran-κO)potassium]-µ-(η⁵:η⁵)-2,3,4,5-tetramethyl-1-n-pentylcyclopentadienyl]

Crystal data

[K(C14H23)(C4H8O)]	F(000) = 664
Mr = 302.53	Dx = 1.083 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54184 Å
a = 11.5883 (3) Å	Cell parameters from 9137 reflections
b = 10.3101 (2) Å	θ = 3.8–74.2°
c = 15.5888 (4) Å	µ = 2.45 mm^−1
β = 94.891 (3)°	T = 112 K
V = 1855.72 (8) Å^3	Prism, colourless
Z = 4	0.08 × 0.06 × 0.04 mm

Data collection

Agilent SuperNova diffractometer	3112 reflections with I > 2σ(I)
Detector resolution: 10.4372 pixels mm^-1	Rint = 0.052
ω scans	θmax = 74.3°, θmin = 4.6°
Absorption correction: multi-scan (ABSPACK in CrysAlis PRO; Agilent, 2012)	h = −9→13
Tmin = 0.680, Tmax = 1.000	k = −12→12
20699 measured reflections	l = −19→19
3715 independent reflections

Refinement

Refinement on F^2	105 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.121	w = 1/[σ^2(Fo^2) + (0.0601P)^2 + 0.7513P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.001
3715 reflections	Δρmax = 0.34 e Å^−3
224 parameters	Δρmin = −0.20 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
K1	0.25288 (3)	0.25519 (3)	0.19524 (2)	0.02947 (14)
C1	0.19979 (16)	0.47217 (16)	0.31318 (11)	0.0271 (4)
C2	0.31918 (16)	0.48124 (16)	0.30266 (12)	0.0293 (4)
C3	0.33164 (16)	0.52339 (16)	0.21734 (12)	0.0304 (4)
C4	0.21973 (17)	0.54040 (16)	0.17569 (11)	0.0292 (4)
C5	0.13796 (15)	0.50886 (16)	0.23475 (11)	0.0269 (4)
C6	0.14663 (18)	0.43185 (19)	0.39406 (12)	0.0363 (4)
H6A	0.1283	0.3391	0.3912	0.054*
H6B	0.0755	0.4815	0.3994	0.054*
H6C	0.2015	0.4487	0.4442	0.054*
C7	0.41709 (18)	0.4470 (2)	0.36891 (14)	0.0429 (5)
H7A	0.3880	0.4439	0.4261	0.064*
H7B	0.4781	0.5127	0.3684	0.064*
H7C	0.4487	0.3620	0.3552	0.064*
C8	0.44444 (18)	0.5409 (2)	0.17701 (15)	0.0436 (5)
H8A	0.5083	0.5457	0.2223	0.065*
H8B	0.4415	0.6213	0.1433	0.065*
H8C	0.4567	0.4672	0.1392	0.065*
C9	0.1920 (2)	0.58236 (19)	0.08359 (12)	0.0395 (5)
H9A	0.2634	0.5849	0.0542	0.059*	0.47 (3)
H9B	0.1569	0.6689	0.0824	0.059*	0.47 (3)
H9C	0.1377	0.5206	0.0543	0.059*	0.47 (3)
H9D	0.1086	0.5980	0.0731	0.059*	0.53 (3)
H9E	0.2151	0.5140	0.0448	0.059*	0.53 (3)
H9F	0.2343	0.6623	0.0729	0.059*	0.53 (3)
C10	0.00870 (16)	0.50556 (17)	0.21511 (12)	0.0325 (4)
H10A	−0.0141	0.5757	0.1737	0.039*
H10B	−0.0286	0.5234	0.2687	0.039*
C11	−0.03700 (16)	0.37592 (17)	0.17752 (12)	0.0313 (4)
H11A	−0.0011	0.3593	0.1232	0.038*
H11B	−0.0123	0.3056	0.2183	0.038*
C12	−0.16787 (16)	0.37031 (18)	0.15949 (12)	0.0330 (4)
H12A	−0.1918	0.4344	0.1142	0.040*
H12B	−0.2039	0.3959	0.2123	0.040*
C13	−0.21378 (18)	0.23758 (19)	0.13087 (13)	0.0373 (4)
H13A	−0.1905	0.1733	0.1762	0.045*
H13B	−0.1780	0.2117	0.0780	0.045*
C14	−0.34505 (19)	0.2349 (2)	0.11298 (15)	0.0443 (5)
H14A	−0.3812	0.2547	0.1661	0.066*
H14B	−0.3695	0.1485	0.0924	0.066*
H14C	−0.3689	0.2997	0.0690	0.066*
O1	0.26257 (14)	0.25972 (14)	0.02404 (9)	0.0427 (4)
C15	0.3583 (10)	0.2716 (10)	−0.0213 (5)	0.050 (2)	0.698 (11)
H15A	0.4161	0.2043	−0.0027	0.060*	0.698 (11)
H15B	0.3943	0.3579	−0.0108	0.060*	0.698 (11)
C16	0.3188 (4)	0.2551 (6)	−0.1185 (3)	0.0437 (11)	0.698 (11)
H16A	0.2964	0.3387	−0.1463	0.052*	0.698 (11)
H16B	0.3788	0.2125	−0.1503	0.052*	0.698 (11)
C17	0.2148 (5)	0.1673 (7)	−0.1100 (4)	0.0462 (15)	0.698 (11)
H17A	0.2384	0.0767	−0.0967	0.055*	0.698 (11)
H17B	0.1601	0.1691	−0.1623	0.055*	0.698 (11)
C18	0.1638 (13)	0.2331 (15)	−0.0332 (7)	0.045 (2)	0.698 (11)
H18A	0.1226	0.3141	−0.0512	0.054*	0.698 (11)
H18B	0.1096	0.1746	−0.0064	0.054*	0.698 (11)
C15'	0.361 (3)	0.300 (2)	−0.0323 (13)	0.046 (4)	0.302 (11)
H15C	0.3491	0.3883	−0.0572	0.056*	0.302 (11)
H15D	0.4388	0.2940	−0.0010	0.056*	0.302 (11)
C16'	0.3381 (7)	0.1921 (13)	−0.1000 (6)	0.043 (2)	0.302 (11)
H16C	0.3834	0.2056	−0.1503	0.052*	0.302 (11)
H16D	0.3558	0.1053	−0.0751	0.052*	0.302 (11)
C17'	0.2117 (11)	0.209 (2)	−0.1231 (9)	0.055 (4)	0.302 (11)
H17C	0.1787	0.1363	−0.1585	0.066*	0.302 (11)
H17D	0.1947	0.2920	−0.1539	0.066*	0.302 (11)
C18'	0.168 (3)	0.210 (4)	−0.0328 (16)	0.043 (4)	0.302 (11)
H18C	0.0988	0.2666	−0.0315	0.052*	0.302 (11)
H18D	0.1467	0.1213	−0.0155	0.052*	0.302 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
K1	0.0407 (2)	0.0210 (2)	0.0268 (2)	0.00022 (14)	0.00370 (16)	−0.00021 (12)
C1	0.0327 (9)	0.0195 (7)	0.0293 (8)	0.0001 (6)	0.0035 (7)	−0.0007 (6)
C2	0.0323 (9)	0.0206 (8)	0.0342 (9)	0.0021 (7)	−0.0022 (7)	−0.0041 (7)
C3	0.0325 (9)	0.0217 (8)	0.0378 (9)	−0.0033 (7)	0.0087 (8)	−0.0044 (7)
C4	0.0400 (10)	0.0198 (7)	0.0279 (8)	0.0000 (7)	0.0032 (7)	−0.0013 (6)
C5	0.0309 (9)	0.0212 (7)	0.0287 (8)	0.0001 (6)	0.0024 (7)	0.0001 (6)
C6	0.0450 (11)	0.0339 (9)	0.0305 (9)	−0.0019 (8)	0.0054 (8)	0.0035 (7)
C7	0.0387 (11)	0.0391 (10)	0.0488 (12)	0.0041 (8)	−0.0091 (9)	−0.0016 (9)
C8	0.0400 (11)	0.0381 (10)	0.0549 (12)	−0.0051 (9)	0.0161 (9)	−0.0077 (9)
C9	0.0584 (13)	0.0304 (9)	0.0301 (9)	−0.0013 (9)	0.0054 (9)	0.0037 (7)
C10	0.0320 (10)	0.0298 (9)	0.0351 (9)	0.0039 (7)	0.0005 (7)	0.0000 (7)
C11	0.0316 (9)	0.0331 (9)	0.0291 (8)	−0.0004 (7)	0.0019 (7)	0.0004 (7)
C12	0.0326 (10)	0.0374 (9)	0.0286 (9)	−0.0001 (8)	0.0000 (7)	0.0038 (7)
C13	0.0351 (10)	0.0432 (11)	0.0331 (10)	−0.0032 (8)	0.0000 (8)	0.0003 (8)
C14	0.0368 (11)	0.0564 (13)	0.0395 (11)	−0.0112 (9)	0.0021 (9)	−0.0020 (9)
O1	0.0453 (9)	0.0539 (9)	0.0286 (7)	−0.0008 (7)	0.0013 (6)	−0.0024 (6)
C15	0.035 (3)	0.078 (5)	0.038 (3)	−0.020 (3)	0.001 (2)	−0.009 (3)
C16	0.0376 (19)	0.057 (3)	0.0372 (18)	−0.0075 (18)	0.0069 (14)	−0.0049 (16)
C17	0.045 (2)	0.059 (3)	0.035 (2)	−0.018 (2)	0.0023 (16)	−0.009 (2)
C18	0.038 (3)	0.065 (5)	0.033 (3)	−0.006 (3)	0.006 (2)	−0.003 (2)
C15'	0.043 (6)	0.056 (7)	0.043 (6)	−0.009 (5)	0.016 (5)	−0.002 (5)
C16'	0.037 (4)	0.053 (5)	0.040 (4)	0.004 (3)	0.009 (3)	−0.001 (4)
C17'	0.043 (5)	0.095 (12)	0.028 (5)	0.011 (5)	0.009 (3)	−0.007 (5)
C18'	0.033 (7)	0.057 (9)	0.040 (6)	−0.009 (6)	0.006 (5)	−0.009 (5)

Geometric parameters (Å, º)

K1—O1	2.6812 (15)	C10—C11	1.535 (2)
K1—C3	2.9231 (17)	C10—H10A	0.9900
K1—C2	2.9337 (17)	C10—H10B	0.9900
K1—C2^i	2.9463 (17)	C11—C12	1.520 (3)
K1—C3^i	2.9589 (18)	C11—H11A	0.9900
K1—C1^i	2.9740 (17)	C11—H11B	0.9900
K1—C4	2.9778 (17)	C12—C13	1.521 (3)
K1—C4^i	2.9907 (17)	C12—H12A	0.9900
K1—C1	2.9927 (17)	C12—H12B	0.9900
K1—C5^i	3.0010 (17)	C13—C14	1.523 (3)
K1—C5	3.0220 (17)	C13—H13A	0.9900
C1—C2	1.410 (3)	C13—H13B	0.9900
C1—C5	1.415 (2)	C14—H14A	0.9800
C1—C6	1.508 (3)	C14—H14B	0.9800
C1—K1^ii	2.9740 (16)	C14—H14C	0.9800
C2—C3	1.418 (3)	O1—C15	1.371 (12)
C2—C7	1.510 (3)	O1—C18	1.417 (16)
C2—K1^ii	2.9463 (17)	O1—C18'	1.45 (4)
C3—C4	1.411 (3)	O1—C15'	1.56 (3)
C3—C8	1.509 (3)	C15—C16	1.555 (8)
C3—K1^ii	2.9589 (18)	C15—H15A	0.9900
C4—C5	1.414 (3)	C15—H15B	0.9900
C4—C9	1.508 (2)	C16—C17	1.523 (6)
C4—K1^ii	2.9907 (17)	C16—H16A	0.9900
C5—C10	1.503 (3)	C16—H16B	0.9900
C5—K1^ii	3.0009 (17)	C17—C18	1.537 (8)
C6—H6A	0.9800	C17—H17A	0.9900
C6—H6B	0.9800	C17—H17B	0.9900
C6—H6C	0.9800	C18—H18A	0.9900
C7—H7A	0.9800	C18—H18B	0.9900
C7—H7B	0.9800	C15'—C16'	1.543 (14)
C7—H7C	0.9800	C15'—H15C	0.9900
C8—H8A	0.9800	C15'—H15D	0.9900
C8—H8B	0.9800	C16'—C17'	1.489 (13)
C8—H8C	0.9800	C16'—H16C	0.9900
C9—H9A	0.9800	C16'—H16D	0.9900
C9—H9B	0.9800	C17'—C18'	1.539 (14)
C9—H9C	0.9800	C17'—H17C	0.9900
C9—H9D	0.9800	C17'—H17D	0.9900
C9—H9E	0.9800	C18'—H18C	0.9900
C9—H9F	0.9800	C18'—H18D	0.9900
O1—K1—C3	93.54 (5)	C2—C7—H7C	109.5
O1—K1—C2	121.55 (5)	H7A—C7—H7C	109.5
C3—K1—C2	28.03 (5)	H7B—C7—H7C	109.5
O1—K1—C2^i	93.65 (5)	C3—C8—H8A	109.5
C3—K1—C2^i	172.53 (5)	C3—C8—H8B	109.5
C2—K1—C2^i	144.68 (2)	H8A—C8—H8B	109.5
O1—K1—C3^i	121.07 (5)	C3—C8—H8C	109.5
C3—K1—C3^i	145.29 (2)	H8A—C8—H8C	109.5
C2—K1—C3^i	117.36 (5)	H8B—C8—H8C	109.5
C2^i—K1—C3^i	27.79 (5)	C4—C9—H9A	109.5
O1—K1—C1^i	87.11 (5)	C4—C9—H9B	109.5
C3—K1—C1^i	151.22 (5)	H9A—C9—H9B	109.5
C2—K1—C1^i	139.85 (5)	C4—C9—H9C	109.5
C2^i—K1—C1^i	27.55 (5)	H9A—C9—H9C	109.5
C3^i—K1—C1^i	45.37 (5)	H9B—C9—H9C	109.5
O1—K1—C4	84.08 (5)	C4—C9—H9D	109.5
C3—K1—C4	27.65 (5)	H9A—C9—H9D	141.1
C2—K1—C4	45.51 (5)	H9B—C9—H9D	56.3
C2^i—K1—C4	156.01 (5)	H9C—C9—H9D	56.3
C3^i—K1—C4	143.12 (5)	C4—C9—H9E	109.5
C1^i—K1—C4	170.76 (5)	H9A—C9—H9E	56.3
O1—K1—C4^i	132.18 (5)	H9B—C9—H9E	141.1
C3—K1—C4^i	127.38 (5)	H9C—C9—H9E	56.3
C2—K1—C4^i	101.34 (5)	H9D—C9—H9E	109.5
C2^i—K1—C4^i	45.30 (5)	C4—C9—H9F	109.5
C3^i—K1—C4^i	27.43 (5)	H9A—C9—H9F	56.3
C1^i—K1—C4^i	45.07 (5)	H9B—C9—H9F	56.3
C4—K1—C4^i	143.65 (3)	H9C—C9—H9F	141.1
O1—K1—C1	128.81 (5)	H9D—C9—H9F	109.5
C3—K1—C1	45.49 (5)	H9E—C9—H9F	109.5
C2—K1—C1	27.51 (5)	C5—C10—C11	113.74 (15)
C2^i—K1—C1	129.53 (5)	C5—C10—H10A	108.8
C3^i—K1—C1	103.14 (5)	C11—C10—H10A	108.8
C1^i—K1—C1	143.99 (3)	C5—C10—H10B	108.8
C4—K1—C1	45.03 (5)	C11—C10—H10B	108.8
C4^i—K1—C1	98.96 (5)	H10A—C10—H10B	107.7
O1—K1—C5^i	108.94 (5)	C12—C11—C10	114.20 (15)
C3—K1—C5^i	129.79 (5)	C12—C11—H11A	108.7
C2—K1—C5^i	112.52 (5)	C10—C11—H11A	108.7
C2^i—K1—C5^i	45.23 (5)	C12—C11—H11B	108.7
C3^i—K1—C5^i	45.15 (5)	C10—C11—H11B	108.7
C1^i—K1—C5^i	27.39 (5)	H11A—C11—H11B	107.6
C4—K1—C5^i	156.87 (5)	C11—C12—C13	114.01 (16)
C4^i—K1—C5^i	27.31 (5)	C11—C12—H12A	108.8
C1—K1—C5^i	120.77 (5)	C13—C12—H12A	108.8
O1—K1—C5	104.15 (5)	C11—C12—H12B	108.8
C3—K1—C5	45.24 (5)	C13—C12—H12B	108.8
C2—K1—C5	45.14 (5)	H12A—C12—H12B	107.6
C2^i—K1—C5	134.20 (5)	C12—C13—C14	112.89 (17)
C3^i—K1—C5	115.86 (5)	C12—C13—H13A	109.0
C1^i—K1—C5	160.78 (5)	C14—C13—H13A	109.0
C4—K1—C5	27.26 (5)	C12—C13—H13B	109.0
C4^i—K1—C5	121.81 (5)	C14—C13—H13B	109.0
C1—K1—C5	27.20 (4)	H13A—C13—H13B	107.8
C5^i—K1—C5	146.899 (16)	C13—C14—H14A	109.5
C2—C1—C5	108.14 (16)	C13—C14—H14B	109.5
C2—C1—C6	126.17 (16)	H14A—C14—H14B	109.5
C5—C1—C6	125.68 (17)	C13—C14—H14C	109.5
C2—C1—K1^ii	75.13 (9)	H14A—C14—H14C	109.5
C5—C1—K1^ii	77.37 (9)	H14B—C14—H14C	109.5
C6—C1—K1^ii	113.42 (11)	C15—O1—C18	109.8 (4)
C2—C1—K1	73.92 (9)	C18'—O1—C15'	107.8 (10)
C5—C1—K1	77.55 (10)	C15—O1—K1	128.3 (3)
C6—C1—K1	115.31 (11)	C18—O1—K1	121.6 (3)
K1^ii—C1—K1	131.14 (6)	C18'—O1—K1	120.6 (8)
C1—C2—C3	107.98 (15)	C15'—O1—K1	131.4 (7)
C1—C2—C7	126.34 (18)	O1—C15—C16	108.0 (6)
C3—C2—C7	125.64 (18)	O1—C15—H15A	110.1
C1—C2—K1	78.58 (9)	C16—C15—H15A	110.1
C3—C2—K1	75.57 (10)	O1—C15—H15B	110.1
C7—C2—K1	110.46 (11)	C16—C15—H15B	110.1
C1—C2—K1^ii	77.32 (9)	H15A—C15—H15B	108.4
C3—C2—K1^ii	76.60 (10)	C17—C16—C15	98.5 (5)
C7—C2—K1^ii	114.45 (11)	C17—C16—H16A	112.1
K1—C2—K1^ii	135.01 (6)	C15—C16—H16A	112.1
C4—C3—C2	107.86 (16)	C17—C16—H16B	112.1
C4—C3—C8	126.03 (18)	C15—C16—H16B	112.1
C2—C3—C8	126.05 (18)	H16A—C16—H16B	109.7
C4—C3—K1	78.33 (10)	C16—C17—C18	99.5 (7)
C2—C3—K1	76.40 (10)	C16—C17—H17A	111.9
C8—C3—K1	109.71 (12)	C18—C17—H17A	111.9
C4—C3—K1^ii	77.54 (10)	C16—C17—H17B	111.9
C2—C3—K1^ii	75.61 (10)	C18—C17—H17B	111.9
C8—C3—K1^ii	115.31 (12)	H17A—C17—H17B	109.6
K1—C3—K1^ii	134.92 (7)	O1—C18—C17	103.4 (8)
C3—C4—C5	108.20 (16)	O1—C18—H18A	111.1
C3—C4—C9	125.94 (18)	C17—C18—H18A	111.1
C5—C4—C9	125.85 (18)	O1—C18—H18B	111.1
C3—C4—K1	74.02 (10)	C17—C18—H18B	111.1
C5—C4—K1	78.11 (10)	H18A—C18—H18B	109.0
C9—C4—K1	113.33 (11)	C16'—C15'—O1	95.7 (13)
C3—C4—K1^ii	75.03 (10)	C16'—C15'—H15C	112.6
C5—C4—K1^ii	76.75 (10)	O1—C15'—H15C	112.6
C9—C4—K1^ii	115.46 (11)	C16'—C15'—H15D	112.6
K1—C4—K1^ii	131.07 (6)	O1—C15'—H15D	112.6
C4—C5—C1	107.82 (16)	H15C—C15'—H15D	110.1
C4—C5—C10	125.72 (16)	C17'—C16'—C15'	100.8 (13)
C1—C5—C10	126.32 (16)	C17'—C16'—H16C	111.6
C4—C5—K1^ii	75.94 (10)	C15'—C16'—H16C	111.6
C1—C5—K1^ii	75.24 (9)	C17'—C16'—H16D	111.6
C10—C5—K1^ii	118.36 (11)	C15'—C16'—H16D	111.6
C4—C5—K1	74.63 (10)	H16C—C16'—H16D	109.4
C1—C5—K1	75.24 (10)	C16'—C17'—C18'	100.1 (14)
C10—C5—K1	112.81 (10)	C16'—C17'—H17C	111.8
K1^ii—C5—K1	128.84 (6)	C18'—C17'—H17C	111.8
C1—C6—H6A	109.5	C16'—C17'—H17D	111.8
C1—C6—H6B	109.5	C18'—C17'—H17D	111.8
H6A—C6—H6B	109.5	H17C—C17'—H17D	109.5
C1—C6—H6C	109.5	O1—C18'—C17'	105.6 (18)
H6A—C6—H6C	109.5	O1—C18'—H18C	110.6
H6B—C6—H6C	109.5	C17'—C18'—H18C	110.6
C2—C7—H7A	109.5	O1—C18'—H18D	110.6
C2—C7—H7B	109.5	C17'—C18'—H18D	110.6
H7A—C7—H7B	109.5	H18C—C18'—H18D	108.8

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2.