Bis(pyrene)metal complexes of vanadium, niobium and titanium: isolable homoleptic pyrene complexes of transition metals

Reduction of VCl₃(THF)₃ (THF is tetra­hydro­furan) and NbCl₄(THF)₂ by alkali metal pyrene radical anion salts in THF affords the paramagnetic sandwich complexes bis­[(1,2,3,3a,10a,10b-[eta])-pyrene]vanadium(0), [V(C₁₆H₁₀)₂], and bis­[(1,2,3,3a,10a,10b-[eta])-pyrene]niobium(0), [Nb(C₁₆H₁₀)₂]. Treat­ment of tris­(naphthalene)­titanate(2-) with pyrene provides the isoelectronic titanium species, isolated as an (18-crown-6)potassium salt, namely catena-poly[[(18-crown-6)potassium]-[mu]-[(1,2-[eta]:1,2,3,3a,10a,10b-[eta])-pyrene]-titanate(-I)-[mu]-[(1,2,3,3a,10a,10b-[eta]:6,7-[eta])-pyrene]], {[K(C₁₂H₂₄O₆)][Ti(C₁₆H₁₀)₂]}_n. The first two compounds have very similar packing, with neighboring mol­ecules arranged orthogonally to one another, such that aromatic donor-acceptor inter­actions are likely responsible for the specific arrangement. The asymmetric unit contains a half-occupancy metal center [eta]⁶-coordinated to one pyrene ligand, with the full M(pyrene)₂ mol­ecule generated by a crystallographic inversion center. In the titanium compound, the cations and anions are in alternating contact throughout the crystal structure, in one-dimensional chains along the [101] direction. As in the other two compounds, the asymmetric unit contains a half-occupancy Ti atom [eta]⁶-coordinated to one pyrene ligand. Additionally, the asymmetric unit contains one half of an (18-crown-6)potassium cation, located on a crystallographic inversion center coincident with the K atom. The full formula units are generated by those inversion centers. In all three structures, the pyrene ligands are eclipsed and sandwich the metals in one of two inversion-related sites. These species are of inter­est as the first isolable homoleptic pyrene transition metal complexes to be described in the scientific literature.

S1. Introduction

Bis(arene) metal complexes are well established for most transition metals as cationic, neutral or anionic substances, and have found applications in polymer synthesis, molecular-based magnets and crystal engineering, and in the preparation of new materials. Although such species are known for numerous mono- and polycyclic aromatic hydro­carbons (Pampaloni, 2010), surprisingly, bis­(pyrene)chromium(0) is the sole example of an isolable binary or homoleptic transition metal complex of pyrene, a classic polycyclic aromatic hydro­carbon (Harvey, 1997). Bis(pyrene)chromium(0) has been structurally characterized and obtained, in unspecified yield, by the co-condensation of chromium and pyrene vapors at 77 K in a metal-atom reactor (Elschenbroich, 2006). However, unfortunately, no details of this study are available in the primary literature, but were mentioned only at a conference (Vasil'kov et al., 2003). A recent synthesis and structural characterization of an unprecedented heteroleptic or mixed-ligand bis­(pyrene)metal complex, (η⁴-cyclo­octa­diene)bis­(η²-pyrene)cobaltate(1-) (Brennessel & Ellis, 2012a), suggested that homoleptic bis­(pyrene)metal complexes should also be available by similar conventional syntheses. These use normal laboratory equipment and, specifically, do not require specialized metal-atom reactor apparatus. The latter equipment is inaccessible to most chemists and employs procedures that are not easily scaled up (Young & Green, 1975).

We now report on the first conventional syntheses of homoleptic bis­(pyrene)metal complexes, including V(η⁶-pyrene)₂, (I) (Fig. 1), Nb(η⁶-pyrene)₂, (II), and [K(18-crown-6)][Ti(η⁶-pyrene)₂], (III) (Fig. 2). The niobium species, (II), is of inter­est because only one other Nb(0) complex has been prepared by a conventional procedure, bis­(mesitylene)niobium(0) (Calderazzo et al., 1991). Also, the titanate, (III), is a rare example of a compound containing titanium in an oxidation state of -1, precedented only by related bis­(arene)titanates(1-), for arene = benzene and toluene (Bandy et al., 1984), and bi­phenyl and 4,4'-di-tert-butyl­biphenyl (Blackburn et al., 1992). Unlike the prior diamagnetic Cr(η⁶-pyrene)₂ (Vasil'kov et al., 2003), (I), (II) and (III) are NMR-silent paramagnetic 17-electron complexes. Whereas (I) and (III) have been isolated as relatively pure bulk samples (see Synthesis and crystallization), characterization of (II) is based entirely on the single-crystal X-ray diffraction study reported herein. The chemical properties of these species have not been examined in any detail (Jilek, 2009). However, they and the presently unknown Zr, Hf and Ta analogs promise to be useful precursors to potentially exciting new classes of homo- and/or hetero-multimetallic sandwich complexes, possibly containing up to four metals. In this regard, recent studies of tetra­nuclear metal sandwich frameworks (Murahashi et al., 2012), and gas-phase studies of [Nb(pyrene)₂]⁺ and [Nb₂(pyrene)₂]⁺ (Foster et al., 2001), and iron-pyrene cluster anions (Li et al., 2011), are of inter­est.

S2. Experimental

S2.1. Synthesis and crystallization

All manipulations were carried out under argon using standard Schlenk techniques to maintain strictly anaerobic conditions. A glass-covered magnetic bar was used for stirring because Teflon is attacked by certain metallic salts. Solvents were dried using standard techniques, as described previously (Brennessel & Ellis, 2012b). Unless otherwise stated, reagents were obtained from commercial sources and used without further purification. Literature procedures were used to prepare VCl₃(THF)₃ (THF is tetra­hydro­furan), NbCl₄(THF)₄ (Manzer, 1982), and [K(18-crown-6)]₂[Ti(C₁₀H₈)₃] (C₁₀H₈ is naphthalene; Jilek et al., 2008).

S2.1.1. Preparation of V(η⁶-C₁₆H₁₀)₂, (I)

Initially, a dark orange–brown solution of sodium pyrene, NaC₁₆H₁₀, was prepared by stirring sublimed pyrene (1.662 g, 8.22 mmol) with sodium metal (0.190 g, 8.22 mmol) in THF (50 ml) for 6 h at 293 K. This solution was then cooled to 200 K, and to it was added, via cannula, a salmon-colored solution of VCl₃(THF)₃ (1.000 g, 2.68 mmol) in cold THF (50 ml, 200 K). The resulting red–brown solution was warmed to ambient temperature (ca 293 K) over an 18 h period. During this process, microcrystals of (I) formed in the reaction mixture. Addition of isoo­ctane (150 ml) resulted in precipitation of (I), along with NaCl. The resulting crude product was then extracted with boiling THF (150 ml) in a Soxhlet extractor for 65 h to remove the NaCl by-product. Treatment of the THF solution with pentane (250 ml) at 293 K afforded satisfactorily pure brown microcrystals of (I) [yield 0.543 g, 44%; m.p. 506 K (decomposition)]. Elemental analysis, calculated for C₃₂H₂₀V (%): C 84.39, H 4.41, found: C 84.27, H 4.70. Magnetic susceptibility (Evans balance): µ_eff (293 K) = 1.71 µ_B. X-ray quality crystals of (I) were grown as black needles by slow evaporation of a THF solution of (I) under strictly anaerobic conditions.

S2.1.2. Preparation of Nb(η⁶-C₁₆H₁₀)₂, (II)

The synthesis of (II) is very similar to the procedure for (I). Reduction of NbCl₄(THF)₂ with four equivalents of KC₁₆H₁₀ in THF yielded a suspension of KCl and microcrystalline (II). Single black needles of (II) suitable for X-ray study were harvested directly from this reaction mixture. Unfortunately, niobium complex (II) is more prone to decomposition in solution than (I), so attempts to obtain a pure bulk sample of (II), free of KCl, have not been successful to date.

S2.1.3. Preparation of [K(18-crown-6)][Ti(η⁶-C₁₆H₁₀)₂], (III)

A colorless solution of pyrene (0.584 g, 2.89 mmol) in THF (25 ml, 210 K) was added to a red–brown slurry of [K(18-crown-6)]₂[Ti(C₁₀H₈)₃] (1.000 g, 0.962 mmol) in THF (25 ml, 210 K). The reaction mixture was warmed to about 293 K over a 16 h period. During this time, a dark-green microcrystalline solid formed. The product was isolated by filtration, washed with THF and dried under vacuum to afford forest-green microcrystals of (III) [yield 0.448 g, 62%; m.p. 451–453 K (decomposition)]. Elemental analysis, calculated for C₄₄H₄₄KO₆Ti (%): C 69.92, H 5.87, found: C 67.63, H 5.86. Magnetic susceptibility (Evans NMR method) in (Me₂N)₃PO: µ_eff (292 K) = 2.03 µ_B. Thus far, attempts have failed to obtain a sample which gives a satisfactory carbon analysis, perhaps as a result of the extraordinarily high air sensitivity of this species. A dark-red solution of (III) (0.300 g, 0.397 mmol) in (Me₂N)₃PO (8 ml) was slowly layered with Et₂O (15 ml) in a Schlenk tube. After 3 d at ca 290 K, dark metallic green blocks of (III) had deposited. One of these was harvested for the single-crystal X-ray study. Inter­estingly, attempts to obtain relatively pure (III) directly by the addition of a THF solution of TiCl₄(THF)₂ (Manzer, 1982) to five or six equivalents of KC₁₆H₁₀ in THF in the presence of 18-crown-6 were unsuccessful under a variety of conditions.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The transition metal in all three structures was refined with half occupancy because it is disordered over a crystallographic inversion center.

H atoms were placed geometrically and treated as riding atoms, with methyl­ene C—H = 0.99 Å and sp² C—H = 0.95 Å, and with U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

The structures of the bis­(pyrene)metal units in (I), (II), and (III) are closely related (Tables 2–4). In all cases, the pyrene ligands are eclipsed and the metal center is disordered (0.50:0.50, by symmetry) over a crystallographic inversion center. The average C—C distances in the three species are statistically identical, 1.413 (5) Å in (I), 1.416 (5) Å in (II) and 1.417 (6) Å in (III), and are inter­mediate between C—C single and C═ C double bonds, as expected. Also of inter­est are the M–centroid distances, viz. 1.727 Å in (I), 1.830 Å in (II) and 1.774 Å in (III). This last distance is essentially identical to the Ti–centroid distance of 1.780 Å reported for a structurally similar syn-rotamer of [Ti(η⁶-bi­phenyl)₂]^- (Blackburn et al., 1992). Although niobium and titanium have similar atomic radii, about 0.12 Å larger than that of vanadium (Emsley, 1998), the significantly longer Nb–centroid distance compared with the corresponding Ti–centroid value suggests the metal-arene inter­action is stronger in the titanium complex, consistent with the lower oxidation state of titanium and the Chatt–Dewar–Duncanson model for metal–arene δ-backbonding (Elschenbroich, 2006).

Compounds (I) and (II) have very similar packing motifs, with their molecules arranged nearly orthogonally to one another (Fig. 3) and angles between inter­molecular pyrene planes of 87.97 (2)° in (I) and 84.02 (3)° in (II). Inter­molecular aromatic donor–acceptor inter­actions are favored by this arrangement (Martinez & Iverson, 2012), and the closest H[pyrene]···plane[pyrene] distances are approximately 2.55 Å in (I) and 2.60 Å in (II). The cation in (III) is a normal [K(18-crown-6)]⁺ of approximately D_3d symmetry (Hossain et al., 2003). The axial positions of the macrocyclic cations are occupied by equivalent anions in an infinite linear alternating chain of cation (potassium) and anion (pyrene) (Fig. 4), a common structural motif in unsolvated [K(18-crown-6)]⁺ salts (Schlueter & Geiser, 2003). The formation of this strong crystalline structure undoubtedly contributes to the low solubility of the salt in THF.

Related literature

For related literature, see: Bandy et al. (1984); Blackburn et al. (1992); Brennessel & Ellis (2012a, 2012b); Calderazzo et al. (1991); Elschenbroich (2006); Emsley (1998); Foster et al. (2001); Harvey (1997); Hossain et al. (2003); Jilek (2009); Jilek et al. (2008); Li et al. (2011); Manzer (1982); Martinez & Iverson (2012); Murahashi et al. (2012); Pampaloni (2010); Schlueter & Geiser (2003); Vasil'kov, Elschenbroich & Harms (2003); Young & Green (1975).

Computing details

For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for (I), (II); SIR97 (Altomare et al., 1999) for (III). For all compounds, program(s) used to refine structure: SHELXL2014 (Sheldrick, 2014); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The structure of (I), showing the atom-numbering scheme, with displacement ellipsoids drawn at the 50% probability level. The molecule lies on a crystallographic inversion center with the symmetry-equivalent portion generated by the operation (-x + 1, -y + 1, -z + 1). The metal atom is half-occupancy because it is disordered over the center, and only one position is displayed. The above description applies equally to (II).
	Fig. 2. The structure of (III), showing the atom-numbering scheme, with displacement ellipsoids drawn at the 50% probability level. The cation and anion form a contact ion pair, and both are located on independent crystallographic inversion centers. The symmetry-equivalent portion of the cation is generated by the operation (-x, -y + 1, -z + 1), and that of the anion is generated by the operation (-x + 1, -y + 1, -z + 2). The K atom is on an inversion center and the Ti atom is half-occupancy because it is disordered over its proximal center, and only one position is displayed. [Meaning of dashed lines?]
	Fig. 3. Each bis(pyrene)metal molecule in (I) and (II) is orthogonal to its intermolecular neighbors, favoring aromatic donor–acceptor interactions. Only one position of the disordered metal centers is shown per molecule, and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 4. The molecular structure of (III), highlighting its polymeric crystalline structure. The chains lie along the [101] direction. Displacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. Crystallographic inversion centers are located at the K-atom positions and in the center of each pair of eclipsed pyrene ligands. Only one position of the disordered metal centers is shown per molecule.

(I) Bis[(1,2,3,3a,10a,10b-η)-pyrene]vanadium(0)

Crystal data

[V(C16H10)2]	F(000) = 470
Mr = 455.42	Dx = 1.485 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.4905 (8) Å	Cell parameters from 2538 reflections
b = 9.4969 (8) Å	θ = 2.6–25.3°
c = 11.4851 (10) Å	µ = 0.51 mm^−1
β = 100.306 (2)°	T = 173 K
V = 1018.45 (15) Å^3	Needle, black
Z = 2	0.50 × 0.15 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1599 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.041
ω scans	θmax = 26.4°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −11→11
Tmin = 0.786, Tmax = 0.951	k = −11→11
10868 measured reflections	l = −14→14
2087 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0442P)^2 + 0.5242P] where P = (Fo^2 + 2Fc^2)/3
2087 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.22 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.

Refinement. The vanadium atom is modeled as disordered over a crystallographic inversion center (0.50:0.50) by refining it with half occupancy.

All H atoms were placed geometrically and treated as riding atoms: C—H = 0.95 Å, with U_iso(H) = 1.2U_eq(C).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
V1	0.29452 (6)	0.59831 (6)	0.46449 (5)	0.01980 (18)	0.5
C1	0.1293 (2)	0.4299 (2)	0.42226 (17)	0.0316 (5)
H1	0.0558	0.4033	0.4641	0.038*
C2	0.1028 (2)	0.5353 (2)	0.33615 (18)	0.0349 (5)
H2	0.0112	0.5785	0.3191	0.042*
C3	0.2103 (2)	0.5772 (2)	0.27507 (17)	0.0314 (5)
H3	0.1919	0.6508	0.2184	0.038*
C4	0.34614 (19)	0.51178 (19)	0.29623 (16)	0.0248 (4)
C5	0.4594 (2)	0.5497 (2)	0.23440 (16)	0.0301 (4)
H5	0.4433	0.6223	0.1766	0.036*
C6	0.5878 (2)	0.4852 (2)	0.25607 (16)	0.0303 (4)
H6	0.6593	0.5128	0.2124	0.036*
C7	0.61989 (19)	0.37588 (19)	0.34317 (16)	0.0247 (4)
C8	0.7553 (2)	0.3103 (2)	0.37001 (17)	0.0326 (5)
H8	0.8286	0.3364	0.3276	0.039*
C9	0.7829 (2)	0.2076 (2)	0.45809 (18)	0.0347 (5)
H9	0.8747	0.1646	0.4752	0.042*
C10	0.6766 (2)	0.1678 (2)	0.52117 (17)	0.0328 (5)
H10	0.6971	0.0983	0.5813	0.039*
C11	0.53907 (19)	0.22931 (19)	0.49700 (16)	0.0254 (4)
C12	0.4261 (2)	0.1918 (2)	0.55979 (17)	0.0308 (4)
H12	0.4434	0.1213	0.6193	0.037*
C13	0.2967 (2)	0.2541 (2)	0.53655 (17)	0.0304 (4)
H13	0.2250	0.2257	0.5797	0.036*
C14	0.26389 (19)	0.36248 (19)	0.44801 (15)	0.0248 (4)
C15	0.37363 (18)	0.40397 (18)	0.38459 (15)	0.0207 (4)
C16	0.51109 (18)	0.33630 (18)	0.40833 (15)	0.0211 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0189 (3)	0.0199 (3)	0.0200 (3)	0.0012 (2)	0.0019 (2)	−0.0019 (2)
C1	0.0229 (9)	0.0386 (12)	0.0339 (11)	−0.0051 (8)	0.0068 (8)	−0.0102 (9)
C2	0.0240 (10)	0.0408 (12)	0.0361 (11)	0.0066 (9)	−0.0046 (8)	−0.0113 (9)
C3	0.0341 (10)	0.0291 (11)	0.0271 (10)	0.0066 (8)	−0.0054 (8)	−0.0024 (8)
C4	0.0278 (10)	0.0222 (9)	0.0223 (9)	0.0001 (7)	−0.0016 (7)	−0.0037 (7)
C5	0.0401 (11)	0.0261 (10)	0.0235 (10)	−0.0031 (8)	0.0035 (8)	0.0044 (8)
C6	0.0341 (11)	0.0336 (11)	0.0252 (10)	−0.0080 (9)	0.0108 (8)	−0.0012 (8)
C7	0.0246 (9)	0.0259 (10)	0.0235 (9)	−0.0021 (7)	0.0039 (7)	−0.0075 (7)
C8	0.0259 (10)	0.0415 (12)	0.0311 (10)	0.0030 (9)	0.0072 (8)	−0.0110 (9)
C9	0.0305 (10)	0.0362 (11)	0.0355 (11)	0.0133 (9)	0.0003 (9)	−0.0096 (9)
C10	0.0397 (12)	0.0251 (10)	0.0303 (10)	0.0090 (8)	−0.0029 (9)	−0.0024 (8)
C11	0.0316 (10)	0.0193 (9)	0.0237 (9)	0.0010 (7)	0.0008 (8)	−0.0034 (7)
C12	0.0418 (11)	0.0240 (10)	0.0261 (10)	−0.0041 (8)	0.0048 (8)	0.0037 (8)
C13	0.0349 (10)	0.0298 (10)	0.0287 (10)	−0.0107 (9)	0.0115 (8)	−0.0021 (8)
C14	0.0242 (9)	0.0247 (10)	0.0251 (9)	−0.0049 (7)	0.0038 (7)	−0.0067 (7)
C15	0.0224 (8)	0.0195 (9)	0.0193 (8)	−0.0023 (7)	0.0013 (7)	−0.0042 (7)
C16	0.0239 (9)	0.0190 (9)	0.0196 (8)	−0.0013 (7)	0.0015 (7)	−0.0045 (7)

Geometric parameters (Å, º)

V1—C3	2.1885 (19)	C6—H6	0.9500
V1—C2	2.210 (2)	C7—C8	1.412 (3)
V1—C8^i	2.2162 (19)	C7—C16	1.430 (2)
V1—C7^i	2.2266 (19)	C7—V1^i	2.2266 (18)
V1—C16^i	2.2268 (17)	C8—C9	1.396 (3)
V1—C9^i	2.227 (2)	C8—V1^i	2.2162 (19)
V1—C1	2.231 (2)	C8—H8	0.9500
V1—C4	2.2335 (19)	C9—C10	1.396 (3)
V1—C10^i	2.240 (2)	C9—V1^i	2.227 (2)
V1—C15	2.2492 (18)	C9—H9	0.9500
V1—C14	2.2620 (19)	C10—C11	1.411 (3)
V1—C11^i	2.2628 (19)	C10—V1^i	2.240 (2)
C1—C2	1.397 (3)	C10—H10	0.9500
C1—C14	1.412 (3)	C11—C16	1.429 (2)
C1—H1	0.9500	C11—C12	1.440 (3)
C2—C3	1.396 (3)	C11—V1^i	2.2628 (19)
C2—H2	0.9500	C12—C13	1.346 (3)
C3—C4	1.412 (2)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.441 (3)
C4—C15	1.432 (2)	C13—H13	0.9500
C4—C5	1.436 (3)	C14—C15	1.429 (2)
C5—C6	1.347 (3)	C15—C16	1.436 (2)
C5—H5	0.9500	C16—V1^i	2.2268 (17)
C6—C7	1.436 (3)
C3—V1—C2	37.00 (7)	C3—C2—H2	119.9
C3—V1—C8^i	142.42 (7)	C1—C2—H2	119.9
C2—V1—C8^i	113.68 (7)	V1—C2—H2	129.4
C3—V1—C7^i	178.94 (8)	C2—C3—C4	121.00 (18)
C2—V1—C7^i	143.36 (8)	C2—C3—V1	72.32 (11)
C8^i—V1—C7^i	37.06 (7)	C4—C3—V1	73.12 (10)
C3—V1—C16^i	142.17 (8)	C2—C3—H3	119.5
C2—V1—C16^i	179.13 (8)	C4—C3—H3	119.5
C8^i—V1—C16^i	66.87 (7)	V1—C3—H3	127.1
C7^i—V1—C16^i	37.45 (6)	C3—C4—C15	118.77 (17)
C3—V1—C9^i	112.63 (8)	C3—C4—C5	123.06 (17)
C2—V1—C9^i	101.50 (8)	C15—C4—C5	118.16 (16)
C8^i—V1—C9^i	36.61 (7)	C3—C4—V1	69.65 (10)
C7^i—V1—C9^i	66.47 (7)	C15—C4—V1	71.96 (10)
C16^i—V1—C9^i	78.53 (7)	C5—C4—V1	129.43 (13)
C3—V1—C1	66.47 (8)	C6—C5—C4	121.82 (17)
C2—V1—C1	36.68 (8)	C6—C5—H5	119.1
C8^i—V1—C1	102.57 (8)	C4—C5—H5	119.1
C7^i—V1—C1	114.33 (7)	C5—C6—C7	121.96 (17)
C16^i—V1—C1	144.09 (8)	C5—C6—H6	119.0
C9^i—V1—C1	114.24 (8)	C7—C6—H6	119.0
C3—V1—C4	37.22 (7)	C8—C7—C16	118.97 (17)
C2—V1—C4	66.73 (7)	C8—C7—C6	122.82 (17)
C8^i—V1—C4	178.52 (8)	C16—C7—C6	118.16 (16)
C7^i—V1—C4	143.26 (7)	C8—C7—V1^i	71.07 (10)
C16^i—V1—C4	112.70 (7)	C16—C7—V1^i	71.28 (10)
C9^i—V1—C4	142.08 (8)	C6—C7—V1^i	127.29 (13)
C1—V1—C4	78.61 (7)	C9—C8—C7	120.78 (18)
C3—V1—C10^i	100.49 (8)	C9—C8—V1^i	72.13 (11)
C2—V1—C10^i	113.15 (8)	C7—C8—V1^i	71.87 (10)
C8^i—V1—C10^i	65.85 (8)	C9—C8—H8	119.6
C7^i—V1—C10^i	78.45 (7)	C7—C8—H8	119.6
C16^i—V1—C10^i	66.37 (7)	V1^i—C8—H8	128.7
C9^i—V1—C10^i	36.41 (7)	C10—C9—C8	120.41 (18)
C1—V1—C10^i	142.99 (8)	C10—C9—V1^i	72.30 (11)
C4—V1—C10^i	112.67 (8)	C8—C9—V1^i	71.26 (11)
C3—V1—C15	66.94 (7)	C10—C9—H9	119.8
C2—V1—C15	78.50 (7)	C8—C9—H9	119.8
C8^i—V1—C15	144.03 (8)	V1^i—C9—H9	129.0
C7^i—V1—C15	113.95 (7)	C9—C10—C11	121.00 (18)
C16^i—V1—C15	101.46 (6)	C9—C10—V1^i	71.29 (12)
C9^i—V1—C15	179.29 (8)	C11—C10—V1^i	72.61 (11)
C1—V1—C15	66.17 (7)	C9—C10—H10	119.5
C4—V1—C15	37.27 (6)	C11—C10—H10	119.5
C10^i—V1—C15	142.95 (8)	V1^i—C10—H10	129.0
C3—V1—C14	78.90 (7)	C10—C11—C16	118.79 (17)
C2—V1—C14	66.28 (7)	C10—C11—C12	122.99 (17)
C8^i—V1—C14	114.55 (8)	C16—C11—C12	118.20 (16)
C7^i—V1—C14	102.16 (7)	C10—C11—V1^i	70.87 (11)
C16^i—V1—C14	114.21 (7)	C16—C11—V1^i	70.07 (10)
C9^i—V1—C14	143.71 (8)	C12—C11—V1^i	129.58 (13)
C1—V1—C14	36.62 (7)	C13—C12—C11	121.80 (18)
C4—V1—C14	66.93 (7)	C13—C12—H12	119.1
C10^i—V1—C14	179.37 (8)	C11—C12—H12	119.1
C15—V1—C14	36.93 (6)	C12—C13—C14	121.87 (17)
C3—V1—C11^i	112.24 (8)	C12—C13—H13	119.1
C2—V1—C11^i	142.10 (8)	C14—C13—H13	119.1
C8^i—V1—C11^i	78.33 (7)	C1—C14—C15	118.85 (17)
C7^i—V1—C11^i	66.95 (7)	C1—C14—C13	123.03 (17)
C16^i—V1—C11^i	37.12 (6)	C15—C14—C13	118.11 (16)
C9^i—V1—C11^i	65.92 (7)	C1—C14—V1	70.50 (11)
C1—V1—C11^i	178.70 (8)	C15—C14—V1	71.05 (10)
C4—V1—C11^i	100.47 (7)	C13—C14—V1	129.78 (13)
C10^i—V1—C11^i	36.52 (7)	C14—C15—C4	120.08 (16)
C15—V1—C11^i	113.65 (7)	C14—C15—C16	120.00 (16)
C14—V1—C11^i	143.85 (7)	C4—C15—C16	119.91 (16)
C2—C1—C14	120.98 (18)	C14—C15—V1	72.02 (10)
C2—C1—V1	70.83 (11)	C4—C15—V1	70.77 (10)
C14—C1—V1	72.88 (11)	C16—C15—V1	130.39 (12)
C2—C1—H1	119.5	C11—C16—C7	120.02 (16)
C14—C1—H1	119.5	C11—C16—C15	120.00 (16)
V1—C1—H1	129.2	C7—C16—C15	119.98 (16)
C3—C2—C1	120.29 (18)	C11—C16—V1^i	72.81 (10)
C3—C2—V1	70.68 (11)	C7—C16—V1^i	71.27 (10)
C1—C2—V1	72.49 (11)	C15—C16—V1^i	128.15 (12)
C14—C1—C2—C3	−1.0 (3)	C12—C13—C14—C15	−0.3 (3)
V1—C1—C2—C3	54.12 (17)	C12—C13—C14—V1	−88.4 (2)
C14—C1—C2—V1	−55.09 (16)	C1—C14—C15—C4	−0.3 (2)
C1—C2—C3—C4	1.9 (3)	C13—C14—C15—C4	−179.68 (16)
V1—C2—C3—C4	56.84 (16)	V1—C14—C15—C4	−53.98 (14)
C1—C2—C3—V1	−54.97 (17)	C1—C14—C15—C16	−179.49 (16)
C2—C3—C4—C15	−1.9 (3)	C13—C14—C15—C16	1.1 (2)
V1—C3—C4—C15	54.52 (15)	V1—C14—C15—C16	126.82 (15)
C2—C3—C4—C5	179.01 (18)	C1—C14—C15—V1	53.69 (15)
V1—C3—C4—C5	−124.53 (17)	C13—C14—C15—V1	−125.70 (16)
C2—C3—C4—V1	−56.46 (16)	C3—C4—C15—C14	1.1 (2)
C3—C4—C5—C6	−179.76 (18)	C5—C4—C15—C14	−179.76 (16)
C15—C4—C5—C6	1.2 (3)	V1—C4—C15—C14	54.56 (14)
V1—C4—C5—C6	90.3 (2)	C3—C4—C15—C16	−179.65 (16)
C4—C5—C6—C7	−0.8 (3)	C5—C4—C15—C16	−0.6 (2)
C5—C6—C7—C8	−177.79 (18)	V1—C4—C15—C16	−126.24 (15)
C5—C6—C7—C16	−0.3 (3)	C3—C4—C15—V1	−53.42 (15)
C5—C6—C7—V1^i	−87.4 (2)	C5—C4—C15—V1	125.68 (16)
C16—C7—C8—C9	0.5 (3)	C10—C11—C16—C7	2.1 (2)
C6—C7—C8—C9	177.93 (18)	C12—C11—C16—C7	−179.47 (16)
V1^i—C7—C8—C9	55.18 (16)	V1^i—C11—C16—C7	55.45 (14)
C16—C7—C8—V1^i	−54.71 (15)	C10—C11—C16—C15	−177.96 (16)
C6—C7—C8—V1^i	122.75 (17)	C12—C11—C16—C15	0.5 (2)
C7—C8—C9—C10	0.1 (3)	V1^i—C11—C16—C15	−124.61 (15)
V1^i—C8—C9—C10	55.16 (17)	C10—C11—C16—V1^i	−53.35 (15)
C7—C8—C9—V1^i	−55.06 (16)	C12—C11—C16—V1^i	125.08 (16)
C8—C9—C10—C11	0.5 (3)	C8—C7—C16—C11	−1.6 (2)
V1^i—C9—C10—C11	55.13 (17)	C6—C7—C16—C11	−179.16 (16)
C8—C9—C10—V1^i	−54.67 (17)	V1^i—C7—C16—C11	−56.19 (14)
C9—C10—C11—C16	−1.6 (3)	C8—C7—C16—C15	178.49 (16)
V1^i—C10—C11—C16	52.97 (15)	C6—C7—C16—C15	0.9 (2)
C9—C10—C11—C12	−179.90 (18)	V1^i—C7—C16—C15	123.87 (15)
V1^i—C10—C11—C12	−125.37 (18)	C8—C7—C16—V1^i	54.61 (15)
C9—C10—C11—V1^i	−54.53 (17)	C6—C7—C16—V1^i	−122.97 (16)
C10—C11—C12—C13	178.69 (18)	C14—C15—C16—C11	−1.2 (2)
C16—C11—C12—C13	0.3 (3)	C4—C15—C16—C11	179.60 (16)
V1^i—C11—C12—C13	87.0 (2)	V1—C15—C16—C11	90.1 (2)
C11—C12—C13—C14	−0.4 (3)	C14—C15—C16—C7	178.74 (15)
C2—C1—C14—C15	0.2 (3)	C4—C15—C16—C7	−0.5 (2)
V1—C1—C14—C15	−53.95 (15)	V1—C15—C16—C7	−89.9 (2)
C2—C1—C14—C13	179.55 (17)	C14—C15—C16—V1^i	−92.32 (19)
V1—C1—C14—C13	125.40 (17)	C4—C15—C16—V1^i	88.48 (19)
C2—C1—C14—V1	54.14 (16)	V1—C15—C16—V1^i	−1.0 (2)
C12—C13—C14—C1	−179.69 (18)

Symmetry code: (i) −x+1, −y+1, −z+1.

(II) Bis[(1,2,3,3a,10a,10b-η)-pyrene]niobium(0)

Crystal data

[Nb(C16H10)2]	F(000) = 506
Mr = 497.39	Dx = 1.615 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.5838 (12) Å	Cell parameters from 2133 reflections
b = 9.5974 (13) Å	θ = 2.5–25.1°
c = 12.8876 (18) Å	µ = 0.61 mm^−1
β = 105.554 (2)°	T = 123 K
V = 1022.8 (2) Å^3	Needle, black
Z = 2	0.30 × 0.05 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer	1360 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.059
ω scans	θmax = 25.1°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008)	h = −10→10
Tmin = 0.839, Tmax = 0.970	k = −11→11
9829 measured reflections	l = −15→15
1814 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0302P)^2 + 1.0797P] where P = (Fo^2 + 2Fc^2)/3
1814 reflections	(Δ/σ)max = 0.001
154 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.29 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.

Refinement. The niobium atom is modeled as disordered over a crystallographic inversion center (0.50:0.50) by refining it with half occupancy.

All H atoms were placed geometrically and treated as riding atoms: C—H = 0.95 Å, with U_iso(H) = 1.2U_eq(C).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Nb1	0.73045 (6)	0.58271 (5)	0.60072 (4)	0.01324 (15)	0.5
C1	0.7240 (3)	0.8181 (3)	0.5674 (2)	0.0228 (7)
H1	0.7252	0.8900	0.6183	0.027*
C2	0.8707 (4)	0.7637 (3)	0.5566 (2)	0.0230 (7)
H2	0.9703	0.8011	0.5984	0.028*
C3	0.8708 (3)	0.6547 (3)	0.4846 (2)	0.0210 (7)
H3	0.9710	0.6173	0.4796	0.025*
C4	0.7249 (3)	0.5991 (3)	0.4192 (2)	0.0178 (6)
C5	0.7199 (3)	0.4864 (3)	0.3446 (2)	0.0182 (6)
H5	0.8185	0.4472	0.3382	0.022*
C6	0.5787 (3)	0.4353 (3)	0.2837 (2)	0.0195 (6)
H6	0.5805	0.3603	0.2360	0.023*
C7	0.4249 (3)	0.4911 (3)	0.2889 (2)	0.0178 (6)
C8	0.2766 (3)	0.4382 (3)	0.2254 (2)	0.0230 (7)
H8	0.2760	0.3640	0.1765	0.028*
C9	0.1305 (4)	0.4948 (3)	0.2342 (2)	0.0244 (7)
H9	0.0313	0.4584	0.1910	0.029*
C10	0.1280 (3)	0.6043 (3)	0.3057 (2)	0.0215 (7)
H10	0.0275	0.6416	0.3102	0.026*
C11	0.2747 (3)	0.6596 (3)	0.3712 (2)	0.0174 (6)
C12	0.2800 (3)	0.7694 (3)	0.4494 (2)	0.0203 (6)
H12	0.1814	0.8071	0.4572	0.024*
C13	0.4211 (3)	0.8193 (3)	0.5111 (2)	0.0195 (6)
H13	0.4191	0.8912	0.5613	0.023*
C14	0.5746 (3)	0.7672 (3)	0.5035 (2)	0.0179 (6)
C15	0.5754 (3)	0.6560 (3)	0.4288 (2)	0.0153 (6)
C16	0.4246 (3)	0.6022 (3)	0.3633 (2)	0.0145 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Nb1	0.0147 (2)	0.0125 (3)	0.0122 (2)	−0.0003 (2)	0.00303 (18)	0.0007 (2)
C1	0.0317 (17)	0.0194 (16)	0.0164 (16)	−0.0015 (13)	0.0046 (14)	−0.0014 (12)
C2	0.0241 (16)	0.0214 (16)	0.0194 (15)	−0.0016 (13)	−0.0012 (13)	0.0006 (13)
C3	0.0224 (16)	0.0193 (15)	0.0204 (16)	0.0005 (13)	0.0040 (13)	0.0055 (13)
C4	0.0202 (14)	0.0165 (15)	0.0169 (14)	0.0001 (12)	0.0052 (11)	0.0034 (12)
C5	0.0192 (15)	0.0185 (15)	0.0196 (15)	0.0029 (12)	0.0096 (12)	0.0021 (13)
C6	0.0269 (15)	0.0151 (15)	0.0176 (14)	0.0009 (13)	0.0076 (12)	−0.0021 (13)
C7	0.0226 (15)	0.0147 (15)	0.0167 (15)	0.0000 (12)	0.0066 (12)	0.0027 (12)
C8	0.0275 (16)	0.0187 (16)	0.0200 (15)	−0.0003 (13)	0.0012 (13)	−0.0001 (13)
C9	0.0222 (16)	0.0238 (17)	0.0237 (17)	−0.0045 (13)	0.0003 (13)	0.0039 (13)
C10	0.0187 (14)	0.0231 (17)	0.0230 (15)	0.0043 (12)	0.0062 (12)	0.0067 (13)
C11	0.0231 (15)	0.0140 (15)	0.0166 (15)	0.0010 (12)	0.0079 (13)	0.0040 (12)
C12	0.0254 (16)	0.0168 (15)	0.0210 (15)	0.0054 (13)	0.0104 (13)	0.0026 (13)
C13	0.0294 (17)	0.0113 (14)	0.0195 (15)	0.0032 (12)	0.0095 (13)	0.0000 (12)
C14	0.0243 (15)	0.0129 (14)	0.0169 (15)	0.0004 (12)	0.0064 (12)	0.0029 (12)
C15	0.0206 (15)	0.0128 (14)	0.0124 (14)	−0.0007 (12)	0.0043 (11)	0.0024 (12)
C16	0.0187 (14)	0.0117 (14)	0.0128 (13)	0.0004 (11)	0.0035 (11)	0.0044 (11)

Geometric parameters (Å, º)

Nb1—C3	2.266 (3)	C6—H6	0.9500
Nb1—C8^i	2.267 (3)	C7—C8	1.410 (4)
Nb1—C9^i	2.268 (3)	C7—C16	1.435 (4)
Nb1—C2	2.271 (3)	C7—Nb1^i	2.307 (3)
Nb1—C1	2.297 (3)	C8—C9	1.399 (4)
Nb1—C7^i	2.307 (3)	C8—Nb1^i	2.267 (3)
Nb1—C10^i	2.317 (3)	C8—H8	0.9500
Nb1—C4	2.333 (3)	C9—C10	1.401 (4)
Nb1—C16^i	2.338 (3)	C9—Nb1^i	2.268 (3)
Nb1—C11^i	2.356 (3)	C9—H9	0.9500
Nb1—C14	2.365 (3)	C10—C11	1.419 (4)
Nb1—C15	2.366 (3)	C10—Nb1^i	2.317 (3)
C1—C2	1.404 (4)	C10—H10	0.9500
C1—C14	1.413 (4)	C11—C16	1.428 (4)
C1—H1	0.9500	C11—C12	1.450 (4)
C2—C3	1.399 (4)	C11—Nb1^i	2.356 (3)
C2—H2	0.9500	C12—C13	1.346 (4)
C3—C4	1.413 (4)	C12—H12	0.9500
C3—H3	0.9500	C13—C14	1.437 (4)
C4—C15	1.431 (4)	C13—H13	0.9500
C4—C5	1.440 (4)	C14—C15	1.439 (4)
C5—C6	1.347 (4)	C15—C16	1.437 (4)
C5—H5	0.9500	C16—Nb1^i	2.338 (3)
C6—C7	1.443 (4)
C3—Nb1—C8^i	147.11 (11)	C3—C2—H2	119.9
C3—Nb1—C9^i	118.70 (11)	C1—C2—H2	119.9
C8^i—Nb1—C9^i	35.95 (10)	Nb1—C2—H2	127.1
C3—Nb1—C2	35.91 (10)	C2—C3—C4	121.4 (3)
C8^i—Nb1—C2	118.14 (11)	C2—C3—Nb1	72.24 (17)
C9^i—Nb1—C2	107.74 (11)	C4—C3—Nb1	74.70 (16)
C3—Nb1—C1	64.34 (11)	C2—C3—H3	119.3
C8^i—Nb1—C1	105.45 (11)	C4—C3—H3	119.3
C9^i—Nb1—C1	118.58 (11)	Nb1—C3—H3	125.5
C2—Nb1—C1	35.79 (10)	C3—C4—C15	118.5 (3)
C3—Nb1—C7^i	176.88 (10)	C3—C4—C5	123.0 (3)
C8^i—Nb1—C7^i	35.91 (10)	C15—C4—C5	118.5 (2)
C9^i—Nb1—C7^i	64.32 (10)	C3—C4—Nb1	69.55 (16)
C2—Nb1—C7^i	145.31 (11)	C15—C4—Nb1	73.53 (16)
C1—Nb1—C7^i	115.37 (10)	C5—C4—Nb1	127.4 (2)
C3—Nb1—C10^i	106.42 (10)	C6—C5—C4	121.6 (3)
C8^i—Nb1—C10^i	64.26 (10)	C6—C5—H5	119.2
C9^i—Nb1—C10^i	35.56 (11)	C4—C5—H5	119.2
C2—Nb1—C10^i	118.92 (10)	C5—C6—C7	121.9 (3)
C1—Nb1—C10^i	147.36 (10)	C5—C6—H6	119.0
C7^i—Nb1—C10^i	75.53 (10)	C7—C6—H6	119.0
C3—Nb1—C4	35.76 (10)	C8—C7—C16	119.5 (3)
C8^i—Nb1—C4	177.13 (10)	C8—C7—C6	122.3 (3)
C9^i—Nb1—C4	145.79 (11)	C16—C7—C6	118.2 (2)
C2—Nb1—C4	64.34 (10)	C8—C7—Nb1^i	70.52 (17)
C1—Nb1—C4	75.70 (10)	C16—C7—Nb1^i	73.21 (15)
C7^i—Nb1—C4	141.23 (10)	C6—C7—Nb1^i	127.01 (19)
C10^i—Nb1—C4	116.20 (10)	C9—C8—C7	120.1 (3)
C3—Nb1—C16^i	142.57 (10)	C9—C8—Nb1^i	72.04 (17)
C8^i—Nb1—C16^i	64.49 (10)	C7—C8—Nb1^i	73.57 (17)
C9^i—Nb1—C16^i	75.49 (10)	C9—C8—H8	119.9
C2—Nb1—C16^i	176.77 (10)	C7—C8—H8	119.9
C1—Nb1—C16^i	142.85 (10)	Nb1^i—C8—H8	126.3
C7^i—Nb1—C16^i	35.97 (10)	C8—C9—C10	121.1 (3)
C10^i—Nb1—C16^i	63.62 (9)	C8—C9—Nb1^i	72.01 (17)
C4—Nb1—C16^i	112.98 (10)	C10—C9—Nb1^i	74.12 (17)
C3—Nb1—C11^i	115.96 (10)	C8—C9—H9	119.4
C8^i—Nb1—C11^i	75.77 (10)	C10—C9—H9	119.4
C9^i—Nb1—C11^i	63.83 (10)	Nb1^i—C9—H9	126.3
C2—Nb1—C11^i	145.76 (10)	C9—C10—C11	120.3 (3)
C1—Nb1—C11^i	177.30 (10)	C9—C10—Nb1^i	70.32 (17)
C7^i—Nb1—C11^i	64.17 (10)	C11—C10—Nb1^i	73.85 (16)
C10^i—Nb1—C11^i	35.34 (10)	C9—C10—H10	119.8
C4—Nb1—C11^i	102.97 (10)	C11—C10—H10	119.8
C16^i—Nb1—C11^i	35.42 (9)	Nb1^i—C10—H10	128.2
C3—Nb1—C14	75.36 (10)	C10—C11—C16	119.1 (3)
C8^i—Nb1—C14	115.39 (10)	C10—C11—C12	122.9 (3)
C9^i—Nb1—C14	145.42 (11)	C16—C11—C12	118.0 (2)
C2—Nb1—C14	63.73 (10)	C10—C11—Nb1^i	70.81 (16)
C1—Nb1—C14	35.23 (10)	C16—C11—Nb1^i	71.62 (15)
C7^i—Nb1—C14	102.60 (10)	C12—C11—Nb1^i	127.52 (19)
C10^i—Nb1—C14	177.28 (10)	C13—C12—C11	121.6 (3)
C4—Nb1—C14	64.00 (9)	C13—C12—H12	119.2
C16^i—Nb1—C14	113.70 (10)	C11—C12—H12	119.2
C11^i—Nb1—C14	142.08 (10)	C12—C13—C14	122.2 (3)
C3—Nb1—C15	63.64 (10)	C12—C13—H13	118.9
C8^i—Nb1—C15	142.65 (10)	C14—C13—H13	118.9
C9^i—Nb1—C15	177.25 (10)	C1—C14—C13	123.1 (3)
C2—Nb1—C15	75.00 (10)	C1—C14—C15	118.7 (3)
C1—Nb1—C15	63.46 (10)	C13—C14—C15	118.2 (3)
C7^i—Nb1—C15	113.32 (10)	C1—C14—Nb1	69.75 (16)
C10^i—Nb1—C15	143.43 (10)	C13—C14—Nb1	128.53 (19)
C4—Nb1—C15	35.45 (9)	C15—C14—Nb1	72.31 (15)
C16^i—Nb1—C15	101.77 (9)	C4—C15—C16	120.0 (2)
C11^i—Nb1—C15	114.09 (10)	C4—C15—C14	120.4 (2)
C14—Nb1—C15	35.41 (9)	C16—C15—C14	119.6 (2)
C2—C1—C14	120.8 (3)	C4—C15—Nb1	71.02 (15)
C2—C1—Nb1	71.09 (18)	C16—C15—Nb1	129.41 (18)
C14—C1—Nb1	75.01 (17)	C14—C15—Nb1	72.28 (15)
C2—C1—H1	119.6	C11—C16—C7	119.8 (2)
C14—C1—H1	119.6	C11—C16—C15	120.4 (2)
Nb1—C1—H1	126.2	C7—C16—C15	119.8 (2)
C3—C2—C1	120.2 (3)	C11—C16—Nb1^i	72.97 (15)
C3—C2—Nb1	71.85 (17)	C7—C16—Nb1^i	70.81 (15)
C1—C2—Nb1	73.13 (17)	C15—C16—Nb1^i	128.82 (18)
C14—C1—C2—C3	−2.1 (4)	C12—C13—C14—C15	−1.4 (4)
Nb1—C1—C2—C3	56.4 (3)	C12—C13—C14—Nb1	−90.6 (3)
C14—C1—C2—Nb1	−58.5 (3)	C3—C4—C15—C16	179.9 (2)
C1—C2—C3—C4	1.7 (4)	C5—C4—C15—C16	−1.1 (4)
Nb1—C2—C3—C4	58.7 (2)	Nb1—C4—C15—C16	−125.2 (2)
C1—C2—C3—Nb1	−57.0 (3)	C3—C4—C15—C14	0.0 (4)
C2—C3—C4—C15	−0.6 (4)	C5—C4—C15—C14	179.0 (2)
Nb1—C3—C4—C15	56.9 (2)	Nb1—C4—C15—C14	54.9 (2)
C2—C3—C4—C5	−179.6 (3)	C3—C4—C15—Nb1	−54.9 (2)
Nb1—C3—C4—C5	−122.1 (3)	C5—C4—C15—Nb1	124.1 (2)
C2—C3—C4—Nb1	−57.5 (2)	C1—C14—C15—C4	−0.4 (4)
C3—C4—C5—C6	179.7 (3)	C13—C14—C15—C4	−179.1 (2)
C15—C4—C5—C6	0.7 (4)	Nb1—C14—C15—C4	−54.3 (2)
Nb1—C4—C5—C6	91.2 (3)	C1—C14—C15—C16	179.7 (2)
C4—C5—C6—C7	0.6 (4)	C13—C14—C15—C16	1.0 (4)
C5—C6—C7—C8	180.0 (3)	Nb1—C14—C15—C16	125.8 (2)
C5—C6—C7—C16	−1.4 (4)	C1—C14—C15—Nb1	53.9 (2)
C5—C6—C7—Nb1^i	−91.1 (3)	C13—C14—C15—Nb1	−124.8 (2)
C16—C7—C8—C9	0.6 (4)	C10—C11—C16—C7	0.7 (4)
C6—C7—C8—C9	179.2 (3)	C12—C11—C16—C7	178.5 (2)
Nb1^i—C7—C8—C9	57.1 (3)	Nb1^i—C11—C16—C7	55.1 (2)
C16—C7—C8—Nb1^i	−56.5 (2)	C10—C11—C16—C15	−179.9 (2)
C6—C7—C8—Nb1^i	122.1 (3)	C12—C11—C16—C15	−2.1 (4)
C7—C8—C9—C10	0.0 (4)	Nb1^i—C11—C16—C15	−125.5 (2)
Nb1^i—C8—C9—C10	57.9 (3)	C10—C11—C16—Nb1^i	−54.5 (2)
C7—C8—C9—Nb1^i	−57.9 (2)	C12—C11—C16—Nb1^i	123.4 (2)
C8—C9—C10—C11	−0.3 (4)	C8—C7—C16—C11	−1.0 (4)
Nb1^i—C9—C10—C11	56.5 (2)	C6—C7—C16—C11	−179.6 (2)
C8—C9—C10—Nb1^i	−56.9 (3)	Nb1^i—C7—C16—C11	−56.1 (2)
C9—C10—C11—C16	0.0 (4)	C8—C7—C16—C15	179.6 (2)
Nb1^i—C10—C11—C16	54.8 (2)	C6—C7—C16—C15	1.0 (4)
C9—C10—C11—C12	−177.8 (3)	Nb1^i—C7—C16—C15	124.4 (2)
Nb1^i—C10—C11—C12	−122.9 (3)	C8—C7—C16—Nb1^i	55.2 (2)
C9—C10—C11—Nb1^i	−54.9 (2)	C6—C7—C16—Nb1^i	−123.5 (2)
C10—C11—C12—C13	179.5 (3)	C4—C15—C16—C11	−179.1 (2)
C16—C11—C12—C13	1.7 (4)	C14—C15—C16—C11	0.8 (4)
Nb1^i—C11—C12—C13	89.3 (3)	Nb1—C15—C16—C11	91.5 (3)
C11—C12—C13—C14	0.0 (4)	C4—C15—C16—C7	0.3 (4)
C2—C1—C14—C13	−179.9 (3)	C14—C15—C16—C7	−179.8 (2)
Nb1—C1—C14—C13	123.5 (3)	Nb1—C15—C16—C7	−89.0 (3)
C2—C1—C14—C15	1.5 (4)	C4—C15—C16—Nb1^i	88.8 (3)
Nb1—C1—C14—C15	−55.2 (2)	C14—C15—C16—Nb1^i	−91.3 (3)
C2—C1—C14—Nb1	56.6 (3)	Nb1—C15—C16—Nb1^i	−0.5 (4)
C12—C13—C14—C1	179.9 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

(III) catena-Poly[[(18-crown-6)potassium]-µ-[(1,2-η:1,2,3,3a,10a,10b-η)-pyrene]-titanate(I)-µ-[(1,2,3,3a,10a,10b-η:6,7-η)-pyrene]]

Crystal data

[KTi(C16H10)2(C12H24O6)]	F(000) = 794
Mr = 755.79	Dx = 1.453 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.3934 (13) Å	Cell parameters from 2393 reflections
b = 15.682 (2) Å	θ = 2.2–26.9°
c = 11.3559 (14) Å	µ = 0.42 mm^−1
β = 111.084 (2)°	T = 173 K
V = 1727.0 (4) Å^3	Block, green
Z = 2	0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2929 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	Rint = 0.046
ω scans	θmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2012)	h = −13→13
Tmin = 0.617, Tmax = 0.746	k = −20→20
19900 measured reflections	l = −14→14
3941 independent reflections

Refinement

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0529P)^2 + 0.8538P] where P = (Fo^2 + 2Fc^2)/3
3941 reflections	(Δ/σ)max < 0.001
241 parameters	Δρmax = 0.38 e Å^−3
0 restraints	Δρmin = −0.26 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.

Refinement. The titanium atom is modeled as disordered over a crystallographic inversion center (0.50:0.50) by refining it with half occupancy.

All H atoms were placed geometrically and treated as riding atoms: methylene, C—H = 0.99 Å, and sp², C—H = 0.95 Å, with U_iso(H) = 1.2U_eq(C).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ti1	0.29151 (6)	0.47176 (4)	0.97136 (6)	0.01825 (16)	0.5
K1	0.0000	0.5000	0.5000	0.02600 (16)
O1	−0.22886 (13)	0.51617 (8)	0.56481 (13)	0.0264 (3)
O2	−0.10153 (14)	0.66619 (9)	0.52264 (13)	0.0274 (3)
O3	0.15945 (14)	0.64358 (9)	0.50731 (13)	0.0281 (3)
C1	0.1979 (2)	0.39747 (13)	0.78780 (18)	0.0280 (4)
H1A	0.1638	0.3407	0.7748	0.034*
C2	0.1098 (2)	0.46328 (14)	0.79049 (18)	0.0306 (5)
H2A	0.0170	0.4510	0.7806	0.037*
C3	0.1568 (2)	0.54749 (14)	0.80761 (18)	0.0287 (4)
H3A	0.0956	0.5920	0.8099	0.034*
C4	0.29462 (18)	0.56742 (12)	0.82169 (17)	0.0226 (4)
C5	0.3478 (2)	0.65211 (13)	0.84138 (19)	0.0290 (4)
H5A	0.2878	0.6977	0.8417	0.035*
C6	0.4815 (2)	0.66965 (12)	0.85969 (19)	0.0288 (4)
H6A	0.5126	0.7271	0.8733	0.035*
C7	0.57661 (19)	0.60426 (13)	0.85910 (17)	0.0246 (4)
C8	0.7182 (2)	0.62056 (14)	0.88240 (18)	0.0302 (5)
H8A	0.7515	0.6775	0.8947	0.036*
C9	0.8091 (2)	0.55380 (15)	0.88743 (19)	0.0336 (5)
H9A	0.9035	0.5658	0.9035	0.040*
C10	0.7622 (2)	0.46964 (15)	0.86903 (19)	0.0312 (5)
H10A	0.8255	0.4250	0.8733	0.037*
C11	0.62154 (19)	0.44959 (13)	0.84401 (17)	0.0250 (4)
C12	0.5685 (2)	0.36466 (13)	0.82663 (19)	0.0287 (4)
H12A	0.6289	0.3188	0.8285	0.034*
C13	0.4341 (2)	0.34735 (13)	0.80748 (18)	0.0288 (4)
H13A	0.4034	0.2898	0.7961	0.035*
C14	0.33817 (19)	0.41306 (12)	0.80411 (17)	0.0232 (4)
C15	0.38682 (18)	0.49937 (12)	0.82161 (16)	0.0200 (4)
C16	0.52845 (19)	0.51779 (12)	0.84106 (17)	0.0211 (4)
C17	−0.29514 (19)	0.59705 (13)	0.54602 (19)	0.0282 (4)
H17A	−0.3606	0.5992	0.5913	0.034*
H17B	−0.3477	0.6060	0.4550	0.034*
C18	−0.1894 (2)	0.66564 (13)	0.59427 (19)	0.0288 (4)
H18A	−0.2355	0.7217	0.5871	0.035*
H18B	−0.1342	0.6554	0.6844	0.035*
C19	0.0040 (2)	0.72894 (13)	0.56531 (19)	0.0285 (4)
H19A	0.0613	0.7186	0.6549	0.034*
H19B	−0.0376	0.7864	0.5583	0.034*
C20	0.0912 (2)	0.72374 (12)	0.48536 (19)	0.0283 (4)
H20A	0.0327	0.7294	0.3951	0.034*
H20B	0.1598	0.7705	0.5076	0.034*
C21	0.2540 (2)	0.63514 (13)	0.4435 (2)	0.0297 (4)
H21A	0.3223	0.6820	0.4687	0.036*
H21B	0.2040	0.6387	0.3512	0.036*
C22	0.3261 (2)	0.55137 (13)	0.4762 (2)	0.0293 (4)
H22A	0.3951	0.5464	0.4350	0.035*
H22B	0.3752	0.5476	0.5686	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ti1	0.0150 (3)	0.0230 (3)	0.0181 (3)	−0.0006 (2)	0.0076 (2)	0.0002 (2)
K1	0.0248 (3)	0.0261 (3)	0.0330 (3)	−0.0022 (2)	0.0176 (3)	−0.0003 (2)
O1	0.0175 (7)	0.0290 (8)	0.0344 (8)	−0.0002 (5)	0.0113 (6)	0.0017 (6)
O2	0.0252 (7)	0.0295 (7)	0.0309 (7)	−0.0049 (6)	0.0140 (6)	−0.0054 (6)
O3	0.0265 (7)	0.0279 (7)	0.0344 (8)	−0.0011 (6)	0.0164 (6)	0.0022 (6)
C1	0.0268 (10)	0.0310 (11)	0.0243 (10)	−0.0097 (8)	0.0068 (8)	−0.0004 (8)
C2	0.0183 (9)	0.0468 (13)	0.0261 (10)	−0.0061 (9)	0.0072 (8)	0.0035 (9)
C3	0.0198 (9)	0.0415 (12)	0.0251 (10)	0.0040 (8)	0.0083 (8)	0.0016 (8)
C4	0.0179 (9)	0.0299 (10)	0.0198 (9)	0.0017 (7)	0.0067 (7)	0.0011 (7)
C5	0.0280 (10)	0.0274 (10)	0.0304 (11)	0.0056 (8)	0.0091 (9)	0.0022 (8)
C6	0.0318 (11)	0.0227 (10)	0.0305 (11)	−0.0050 (8)	0.0097 (9)	0.0019 (8)
C7	0.0228 (9)	0.0315 (11)	0.0211 (9)	−0.0044 (8)	0.0098 (8)	0.0016 (8)
C8	0.0242 (10)	0.0408 (12)	0.0266 (10)	−0.0098 (9)	0.0105 (8)	0.0012 (8)
C9	0.0195 (10)	0.0581 (14)	0.0267 (10)	−0.0059 (9)	0.0126 (8)	0.0014 (10)
C10	0.0217 (10)	0.0473 (13)	0.0279 (11)	0.0073 (9)	0.0129 (8)	−0.0015 (9)
C11	0.0213 (9)	0.0356 (11)	0.0198 (9)	0.0043 (8)	0.0095 (7)	0.0000 (8)
C12	0.0286 (10)	0.0285 (10)	0.0292 (10)	0.0077 (8)	0.0105 (9)	−0.0038 (8)
C13	0.0351 (11)	0.0242 (10)	0.0271 (10)	−0.0024 (8)	0.0111 (9)	−0.0038 (8)
C14	0.0243 (9)	0.0270 (10)	0.0187 (9)	−0.0024 (8)	0.0081 (7)	−0.0007 (7)
C15	0.0169 (8)	0.0271 (9)	0.0167 (9)	−0.0017 (7)	0.0070 (7)	0.0012 (7)
C16	0.0192 (9)	0.0286 (10)	0.0173 (9)	0.0007 (7)	0.0087 (7)	0.0007 (7)
C17	0.0203 (9)	0.0340 (11)	0.0325 (11)	0.0028 (8)	0.0122 (8)	0.0025 (8)
C18	0.0264 (10)	0.0320 (11)	0.0310 (11)	0.0041 (8)	0.0138 (8)	−0.0014 (8)
C19	0.0260 (10)	0.0247 (10)	0.0331 (11)	−0.0024 (8)	0.0088 (8)	−0.0037 (8)
C20	0.0247 (10)	0.0256 (10)	0.0328 (11)	−0.0032 (8)	0.0082 (8)	0.0017 (8)
C21	0.0244 (10)	0.0337 (11)	0.0348 (11)	−0.0064 (8)	0.0154 (9)	0.0027 (9)
C22	0.0208 (10)	0.0368 (12)	0.0331 (11)	−0.0037 (8)	0.0133 (8)	0.0011 (9)

Geometric parameters (Å, º)

Ti1—C3	2.226 (2)	C6—H6A	0.9500
Ti1—C8^i	2.233 (2)	C7—C8	1.422 (3)
Ti1—C2	2.239 (2)	C7—C16	1.434 (3)
Ti1—C9^i	2.243 (2)	C7—Ti1^i	2.260 (2)
Ti1—C7^i	2.260 (2)	C8—C9	1.397 (3)
Ti1—C10^i	2.273 (2)	C8—Ti1^i	2.233 (2)
Ti1—C4	2.276 (2)	C8—H8A	0.9500
Ti1—C1	2.278 (2)	C9—C10	1.396 (3)
Ti1—C16^i	2.2799 (19)	C9—Ti1^i	2.243 (2)
Ti1—C15	2.2961 (18)	C9—H9A	0.9500
Ti1—C14	2.3135 (19)	C10—C11	1.420 (3)
Ti1—C11^i	2.318 (2)	C10—Ti1^i	2.273 (2)
K1—O1	2.7429 (13)	C10—H10A	0.9500
K1—O1^ii	2.7430 (13)	C11—C12	1.428 (3)
K1—O3^ii	2.7793 (14)	C11—C16	1.435 (3)
K1—O3	2.7793 (14)	C11—Ti1^i	2.318 (2)
K1—O2	2.8578 (14)	C12—C13	1.361 (3)
K1—O2^ii	2.8578 (14)	C12—H12A	0.9500
K1—C2	3.132 (2)	C13—C14	1.425 (3)
K1—C2^ii	3.132 (2)	C13—H13A	0.9500
K1—C3^ii	3.364 (2)	C14—C15	1.433 (3)
K1—C3	3.364 (2)	C15—C16	1.437 (2)
O1—C22^ii	1.422 (2)	C16—Ti1^i	2.2799 (19)
O1—C17	1.422 (2)	C17—C18	1.494 (3)
O2—C19	1.422 (2)	C17—H17A	0.9900
O2—C18	1.425 (2)	C17—H17B	0.9900
O3—C20	1.421 (2)	C18—H18A	0.9900
O3—C21	1.421 (2)	C18—H18B	0.9900
C1—C2	1.387 (3)	C19—C20	1.498 (3)
C1—C14	1.423 (3)	C19—H19A	0.9900
C1—H1A	0.9500	C19—H19B	0.9900
C2—C3	1.397 (3)	C20—H20A	0.9900
C2—H2A	0.9500	C20—H20B	0.9900
C3—C4	1.418 (3)	C21—C22	1.492 (3)
C3—H3A	0.9500	C21—H21A	0.9900
C4—C5	1.425 (3)	C21—H21B	0.9900
C4—C15	1.435 (3)	C22—O1^ii	1.422 (2)
C5—C6	1.357 (3)	C22—H22A	0.9900
C5—H5A	0.9500	C22—H22B	0.9900
C6—C7	1.426 (3)
C3—Ti1—C8^i	141.64 (8)	C14—C1—H1A	119.2
C3—Ti1—C2	36.47 (8)	Ti1—C1—H1A	129.4
C8^i—Ti1—C2	113.26 (8)	C1—C2—C3	120.38 (18)
C3—Ti1—C9^i	112.19 (8)	C1—C2—Ti1	73.66 (11)
C8^i—Ti1—C9^i	36.38 (8)	C3—C2—Ti1	71.27 (11)
C2—Ti1—C9^i	100.90 (8)	C1—C2—K1	96.14 (12)
C3—Ti1—C7^i	178.11 (7)	C3—C2—K1	87.10 (12)
C8^i—Ti1—C7^i	36.89 (7)	Ti1—C2—K1	145.38 (8)
C2—Ti1—C7^i	143.43 (8)	C1—C2—H2A	119.8
C9^i—Ti1—C7^i	65.95 (7)	C3—C2—H2A	119.8
C3—Ti1—C10^i	100.91 (8)	Ti1—C2—H2A	127.3
C8^i—Ti1—C10^i	65.12 (8)	K1—C2—H2A	86.8
C2—Ti1—C10^i	112.80 (8)	C2—C3—C4	120.83 (19)
C9^i—Ti1—C10^i	36.01 (8)	C2—C3—Ti1	72.26 (12)
C7^i—Ti1—C10^i	77.38 (7)	C4—C3—Ti1	73.57 (11)
C3—Ti1—C4	36.69 (7)	C2—C3—K1	68.39 (11)
C8^i—Ti1—C4	178.17 (8)	C4—C3—K1	104.97 (12)
C2—Ti1—C4	65.67 (7)	Ti1—C3—K1	132.33 (9)
C9^i—Ti1—C4	141.92 (8)	C2—C3—H3A	119.6
C7^i—Ti1—C4	144.75 (7)	C4—C3—H3A	119.6
C10^i—Ti1—C4	113.73 (8)	Ti1—C3—H3A	126.5
C3—Ti1—C1	64.86 (8)	K1—C3—H3A	96.4
C8^i—Ti1—C1	103.31 (8)	C3—C4—C5	122.85 (18)
C2—Ti1—C1	35.76 (8)	C3—C4—C15	118.94 (18)
C9^i—Ti1—C1	114.04 (8)	C5—C4—C15	118.15 (17)
C7^i—Ti1—C1	115.99 (8)	C3—C4—Ti1	69.74 (11)
C10^i—Ti1—C1	142.16 (8)	C5—C4—Ti1	127.31 (13)
C4—Ti1—C1	76.70 (7)	C15—C4—Ti1	72.48 (10)
C3—Ti1—C16^i	143.16 (8)	C6—C5—C4	122.08 (18)
C8^i—Ti1—C16^i	66.00 (7)	C6—C5—H5A	119.0
C2—Ti1—C16^i	177.98 (8)	C4—C5—H5A	119.0
C9^i—Ti1—C16^i	77.39 (7)	C5—C6—C7	121.79 (18)
C7^i—Ti1—C16^i	36.83 (7)	C5—C6—H6A	119.1
C10^i—Ti1—C16^i	65.19 (7)	C7—C6—H6A	119.1
C4—Ti1—C16^i	115.02 (7)	C8—C7—C6	122.87 (19)
C1—Ti1—C16^i	145.95 (8)	C8—C7—C16	118.77 (18)
C3—Ti1—C15	65.80 (7)	C6—C7—C16	118.27 (17)
C8^i—Ti1—C15	145.10 (8)	C8—C7—Ti1^i	70.51 (11)
C2—Ti1—C15	77.18 (7)	C6—C7—Ti1^i	125.75 (13)
C9^i—Ti1—C15	177.92 (8)	C16—C7—Ti1^i	72.34 (11)
C7^i—Ti1—C15	116.06 (7)	C9—C8—C7	120.80 (19)
C10^i—Ti1—C15	144.02 (8)	C9—C8—Ti1^i	72.21 (12)
C4—Ti1—C15	36.57 (7)	C7—C8—Ti1^i	72.60 (11)
C1—Ti1—C15	64.84 (7)	C9—C8—H8A	119.6
C16^i—Ti1—C15	104.52 (7)	C7—C8—H8A	119.6
C3—Ti1—C14	77.36 (7)	Ti1^i—C8—H8A	127.7
C8^i—Ti1—C14	115.57 (8)	C10—C9—C8	120.51 (18)
C2—Ti1—C14	65.16 (7)	C10—C9—Ti1^i	73.18 (11)
C9^i—Ti1—C14	143.62 (8)	C8—C9—Ti1^i	71.41 (11)
C7^i—Ti1—C14	104.33 (7)	C10—C9—H9A	119.7
C10^i—Ti1—C14	177.96 (8)	C8—C9—H9A	119.7
C4—Ti1—C14	65.53 (7)	Ti1^i—C9—H9A	127.8
C1—Ti1—C14	36.10 (7)	C9—C10—C11	121.20 (19)
C16^i—Ti1—C14	116.85 (7)	C9—C10—Ti1^i	70.80 (11)
C15—Ti1—C14	36.23 (7)	C11—C10—Ti1^i	73.68 (11)
C3—Ti1—C11^i	113.28 (8)	C9—C10—H10A	119.4
C8^i—Ti1—C11^i	77.26 (8)	C11—C10—H10A	119.4
C2—Ti1—C11^i	141.94 (8)	Ti1^i—C10—H10A	128.4
C9^i—Ti1—C11^i	65.08 (8)	C10—C11—C12	123.55 (18)
C7^i—Ti1—C11^i	65.82 (7)	C10—C11—C16	118.45 (18)
C10^i—Ti1—C11^i	36.02 (7)	C12—C11—C16	117.95 (17)
C4—Ti1—C11^i	102.66 (7)	C10—C11—Ti1^i	70.29 (11)
C1—Ti1—C11^i	177.67 (8)	C12—C11—Ti1^i	128.83 (14)
C16^i—Ti1—C11^i	36.35 (6)	C16—C11—Ti1^i	70.39 (10)
C15—Ti1—C11^i	115.97 (7)	C13—C12—C11	122.08 (18)
C14—Ti1—C11^i	145.67 (7)	C13—C12—H12A	119.0
O1—K1—O1^ii	180.0	C11—C12—H12A	119.0
O1—K1—O3^ii	61.16 (4)	C12—C13—C14	121.86 (18)
O1^ii—K1—O3^ii	118.85 (4)	C12—C13—H13A	119.1
O1—K1—O3	118.84 (4)	C14—C13—H13A	119.1
O1^ii—K1—O3	61.15 (4)	C1—C14—C13	123.60 (18)
O3^ii—K1—O3	180.0	C1—C14—C15	118.29 (17)
O1—K1—O2	60.50 (4)	C13—C14—C15	118.08 (17)
O1^ii—K1—O2	119.49 (4)	C1—C14—Ti1	70.59 (11)
O3^ii—K1—O2	120.40 (4)	C13—C14—Ti1	128.10 (13)
O3—K1—O2	59.60 (4)	C15—C14—Ti1	71.22 (10)
O1—K1—O2^ii	119.50 (4)	C14—C15—C4	120.01 (16)
O1^ii—K1—O2^ii	60.51 (4)	C14—C15—C16	120.12 (17)
O3^ii—K1—O2^ii	59.60 (4)	C4—C15—C16	119.86 (17)
O3—K1—O2^ii	120.40 (4)	C14—C15—Ti1	72.55 (10)
O2—K1—O2^ii	180.0	C4—C15—Ti1	70.95 (10)
O1—K1—C2	75.93 (5)	C16—C15—Ti1	127.96 (12)
O1^ii—K1—C2	104.07 (5)	C7—C16—C11	120.25 (17)
O3^ii—K1—C2	82.52 (5)	C7—C16—C15	119.84 (17)
O3—K1—C2	97.48 (5)	C11—C16—C15	119.91 (17)
O2—K1—C2	94.55 (5)	C7—C16—Ti1^i	70.83 (10)
O2^ii—K1—C2	85.45 (5)	C11—C16—Ti1^i	73.25 (11)
O1—K1—C2^ii	104.07 (5)	C15—C16—Ti1^i	127.52 (12)
O1^ii—K1—C2^ii	75.93 (5)	O1—C17—C18	109.54 (15)
O3^ii—K1—C2^ii	97.48 (5)	O1—C17—H17A	109.8
O3—K1—C2^ii	82.52 (5)	C18—C17—H17A	109.8
O2—K1—C2^ii	85.45 (5)	O1—C17—H17B	109.8
O2^ii—K1—C2^ii	94.55 (5)	C18—C17—H17B	109.8
C2—K1—C2^ii	180.00 (8)	H17A—C17—H17B	108.2
O1—K1—C3^ii	98.98 (4)	O2—C18—C17	109.45 (16)
O1^ii—K1—C3^ii	81.02 (4)	O2—C18—H18A	109.8
O3^ii—K1—C3^ii	74.26 (5)	C17—C18—H18A	109.8
O3—K1—C3^ii	105.74 (5)	O2—C18—H18B	109.8
O2—K1—C3^ii	103.81 (4)	C17—C18—H18B	109.8
O2^ii—K1—C3^ii	76.19 (4)	H18A—C18—H18B	108.2
C2—K1—C3^ii	155.49 (5)	O2—C19—C20	108.44 (16)
C2^ii—K1—C3^ii	24.51 (5)	O2—C19—H19A	110.0
O1—K1—C3	81.02 (4)	C20—C19—H19A	110.0
O1^ii—K1—C3	98.98 (4)	O2—C19—H19B	110.0
O3^ii—K1—C3	105.74 (5)	C20—C19—H19B	110.0
O3—K1—C3	74.26 (5)	H19A—C19—H19B	108.4
O2—K1—C3	76.19 (4)	O3—C20—C19	108.34 (16)
O2^ii—K1—C3	103.81 (4)	O3—C20—H20A	110.0
C2—K1—C3	24.51 (5)	C19—C20—H20A	110.0
C2^ii—K1—C3	155.49 (5)	O3—C20—H20B	110.0
C3^ii—K1—C3	180.00 (3)	C19—C20—H20B	110.0
C22^ii—O1—C17	111.48 (14)	H20A—C20—H20B	108.4
C22^ii—O1—K1	115.25 (11)	O3—C21—C22	109.46 (16)
C17—O1—K1	117.52 (10)	O3—C21—H21A	109.8
C19—O2—C18	112.56 (15)	C22—C21—H21A	109.8
C19—O2—K1	113.41 (11)	O3—C21—H21B	109.8
C18—O2—K1	112.28 (11)	C22—C21—H21B	109.8
C20—O3—C21	112.71 (15)	H21A—C21—H21B	108.2
C20—O3—K1	117.19 (11)	O1^ii—C22—C21	109.88 (16)
C21—O3—K1	115.06 (11)	O1^ii—C22—H22A	109.7
C2—C1—C14	121.52 (18)	C21—C22—H22A	109.7
C2—C1—Ti1	70.58 (12)	O1^ii—C22—H22B	109.7
C14—C1—Ti1	73.31 (11)	C21—C22—H22B	109.7
C2—C1—H1A	119.2	H22A—C22—H22B	108.2
C14—C1—C2—C3	1.0 (3)	C1—C14—C15—C4	−0.3 (3)
Ti1—C1—C2—C3	55.96 (17)	C13—C14—C15—C4	−178.64 (16)
C14—C1—C2—Ti1	−55.01 (17)	Ti1—C14—C15—C4	−54.78 (15)
C14—C1—C2—K1	91.19 (18)	C1—C14—C15—C16	178.70 (16)
Ti1—C1—C2—K1	146.20 (8)	C13—C14—C15—C16	0.4 (3)
C1—C2—C3—C4	0.4 (3)	Ti1—C14—C15—C16	124.26 (16)
Ti1—C2—C3—C4	57.53 (16)	C1—C14—C15—Ti1	54.44 (15)
K1—C2—C3—C4	−94.99 (17)	C13—C14—C15—Ti1	−123.86 (16)
C1—C2—C3—Ti1	−57.11 (17)	C3—C4—C15—C14	1.7 (3)
K1—C2—C3—Ti1	−152.53 (7)	C5—C4—C15—C14	179.04 (16)
C1—C2—C3—K1	95.42 (18)	Ti1—C4—C15—C14	55.54 (15)
Ti1—C2—C3—K1	152.53 (7)	C3—C4—C15—C16	−177.39 (16)
C2—C3—C4—C5	−178.96 (18)	C5—C4—C15—C16	0.0 (3)
Ti1—C3—C4—C5	−122.06 (18)	Ti1—C4—C15—C16	−123.51 (16)
K1—C3—C4—C5	107.56 (17)	C3—C4—C15—Ti1	−53.88 (15)
C2—C3—C4—C15	−1.7 (3)	C5—C4—C15—Ti1	123.50 (17)
Ti1—C3—C4—C15	55.19 (15)	C8—C7—C16—C11	−1.3 (3)
K1—C3—C4—C15	−75.19 (17)	C6—C7—C16—C11	−177.90 (17)
C2—C3—C4—Ti1	−56.91 (16)	Ti1^i—C7—C16—C11	−56.23 (15)
K1—C3—C4—Ti1	−130.39 (9)	C8—C7—C16—C15	177.90 (17)
C3—C4—C5—C6	177.31 (19)	C6—C7—C16—C15	1.3 (3)
C15—C4—C5—C6	0.0 (3)	Ti1^i—C7—C16—C15	122.95 (16)
Ti1—C4—C5—C6	88.8 (2)	C8—C7—C16—Ti1^i	54.95 (15)
C4—C5—C6—C7	0.6 (3)	C6—C7—C16—Ti1^i	−121.67 (17)
C5—C6—C7—C8	−177.75 (19)	C10—C11—C16—C7	2.0 (3)
C5—C6—C7—C16	−1.3 (3)	C12—C11—C16—C7	179.45 (17)
C5—C6—C7—Ti1^i	−89.1 (2)	Ti1^i—C11—C16—C7	55.08 (15)
C6—C7—C8—C9	176.59 (18)	C10—C11—C16—C15	−177.22 (17)
C16—C7—C8—C9	0.1 (3)	C12—C11—C16—C15	0.3 (3)
Ti1^i—C7—C8—C9	55.98 (17)	Ti1^i—C11—C16—C15	−124.10 (16)
C6—C7—C8—Ti1^i	120.61 (18)	C10—C11—C16—Ti1^i	−53.12 (16)
C16—C7—C8—Ti1^i	−55.84 (15)	C12—C11—C16—Ti1^i	124.37 (17)
C7—C8—C9—C10	0.3 (3)	C14—C15—C16—C7	−179.71 (16)
Ti1^i—C8—C9—C10	56.46 (17)	C4—C15—C16—C7	−0.7 (3)
C7—C8—C9—Ti1^i	−56.17 (17)	Ti1—C15—C16—C7	−89.0 (2)
C8—C9—C10—C11	0.4 (3)	C14—C15—C16—C11	−0.5 (3)
Ti1^i—C9—C10—C11	56.04 (17)	C4—C15—C16—C11	178.52 (16)
C8—C9—C10—Ti1^i	−55.62 (17)	Ti1—C15—C16—C11	90.2 (2)
C9—C10—C11—C12	−178.88 (18)	C14—C15—C16—Ti1^i	−91.8 (2)
Ti1^i—C10—C11—C12	−124.17 (19)	C4—C15—C16—Ti1^i	87.2 (2)
C9—C10—C11—C16	−1.5 (3)	Ti1—C15—C16—Ti1^i	−1.1 (3)
Ti1^i—C10—C11—C16	53.17 (15)	C22^ii—O1—C17—C18	178.12 (15)
C9—C10—C11—Ti1^i	−54.71 (17)	K1—O1—C17—C18	−45.67 (18)
C10—C11—C12—C13	177.47 (19)	C19—O2—C18—C17	−178.70 (16)
C16—C11—C12—C13	0.1 (3)	K1—O2—C18—C17	−49.28 (17)
Ti1^i—C11—C12—C13	86.6 (2)	O1—C17—C18—O2	63.6 (2)
C11—C12—C13—C14	−0.2 (3)	C18—O2—C19—C20	179.38 (15)
C2—C1—C14—C13	177.22 (18)	K1—O2—C19—C20	50.54 (17)
Ti1—C1—C14—C13	123.46 (18)	C21—O3—C20—C19	−175.10 (16)
C2—C1—C14—C15	−1.0 (3)	K1—O3—C20—C19	47.92 (18)
Ti1—C1—C14—C15	−54.74 (15)	O2—C19—C20—O3	−65.3 (2)
C2—C1—C14—Ti1	53.76 (17)	C20—O3—C21—C22	177.27 (16)
C12—C13—C14—C1	−178.22 (19)	K1—O3—C21—C22	−44.79 (18)
C12—C13—C14—C15	0.0 (3)	O3—C21—C22—O1^ii	61.9 (2)
C12—C13—C14—Ti1	−87.4 (2)

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