Bis(μ2-iso­propyl­imido-κ2N:N)bis­[(η5-cyclo­penta­dien­yl)(ethenolato-κO)titanium(IV)]

Haehnel, M.; Spannenberg, A.; Rosenthal, U.

doi:10.1107/S1600536813033072

metal-organic compounds

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Volume 70| Part 1| January 2014| Page m16

https://doi.org/10.1107/S1600536813033072

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Bis(μ₂-isopropylimido-κ²N:N)bis[(η⁵-cyclopentadienyl)(ethenolato-κO)titanium(IV)]

Martin Haehnel,^a ^* Anke Spannenberg ^a and Uwe Rosenthal ^a

^aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
^*Correspondence e-mail: martin.haehnel@catalysis.de

(Received 3 December 2013; accepted 6 December 2013; online 14 December 2013)

The title dinuclear half-sandwich complex, [CpTi(OCH=CH₂)(μ₂-N-iPr)]₂ (Cp = cyclopentadienyl; iPr = isopropyl), was obtained from the reaction of Cp₂TiCl₂, n-butyllithium and isopropylamine in tetrahydrofuran. Each Ti^IV atom is coordinated by one Cp ligand, one vinyloxy unit and two bridging imido groups in a strongly distorted tetrahedral geometry. There are two half molecules in the asymmetric unit, such that whole molecules being generated by inversion symmetry.

CCDC reference: 975548

Related literature

For other Ti complexes with both Cp′ (Cp′ = substituted or unsubstituted Cp) ligands and an enolate unit with a terminal =CH₂ group, see: Curtis et al. (1984 ); Veya et al. (1993 ); Beckhaus et al. (1994 ); Schwartz et al. (1996 ). For selected examples of half-sandwich CpTi complexes with μ₂-bridging imido ligands, see: Vroegop et al. (1983 ); Grigsby et al. (1996 ); Ascenso et al. (2001 ); Tsurugi et al. (2011 ).

Experimental

Crystal data

[Ti₂(C₅H₅)₂(C₃H₇N)₂(C₂H₃O)₂]
M_r = 426.26
Monoclinic, P 2₁ /n
a = 13.8746 (4) Å
b = 9.7484 (2) Å
c = 16.3264 (4) Å
β = 106.593 (2)°
V = 2116.27 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 150 K
0.50 × 0.40 × 0.25 mm

Data collection

Stoe IPDS II diffractometer
32869 measured reflections
4625 independent reflections
4211 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.069
S = 1.05
4625 reflections
239 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 975548

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S1600536813033072/pk2508sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813033072/pk2508Isup2.hkl

checkCIF report

Comment top

The reaction of Cp₂TiCl₂, n-butyllithium and isopropylamine in THF was investigated to synthesize the new titanocene imido compound Cp₂Ti=N-iPr. However, the excess of n-butyllithium led to THF cleavage, involving the formation of vinyloxy species. Substitution of one of the Cp ligands by the vinyloxy ligand was observed, together with the imido unit bridging over two titanium centers, thus forming a dinuclear complex. The asymmetric unit contains two half molecules of the title compound. Each titanium center is coordinated by one Cp ligand, one vinyloxy unit and two bridging imido groups (Fig. 1). The geometry at the titanium centers is strongly distorted tetrahedral. The largest deviation from the ideal tetrahedral angle is observed for N2—Ti2—N2A with 85.84 (4)°. The central four-membered metallacycles Ti1, N1, Ti1A, N1A and Ti2, N2, Ti2A, N2A are planar by virtue of the inversion symmetry.

Related literature top

For other Ti complexes with both Cp' (Cp' = substituted or unsubstituted Cp) ligands and an enolate unit with a terminal ═CH₂ group, see: Curtis et al. (1984); Veya et al. (1993); Beckhaus et al. (1994); Schwartz et al. (1996). For selected examples of half-sandwich CpTi complexes with µ₂-bridging imido ligands, see: Vroegop et al. (1983); Grigsby et al. (1996); Ascenso et al. (2001); Tsurugi et al. (2011).

Experimental top

To a stirred solution of isopropylamine (0.3 ml, 3.5 mmol) in 20 ml of THF was added a solution of n-butyllithium (1.6 M, 5.0 ml) in n-hexane at room temperature. After stirring fo 16 h, the reaction mixture was slowly poured into a suspension of Cp₂TiCl₂ (872 mg, 3.5 mmol) in 15 ml of THF. Immediately, the colour turned dark brown. After additional stirring for 20 h, all volatiles were removed in vacuum and the dark brown residue was suspended in 40 ml of diethylether and filtered. The dark brown solution was then concentrated to 5 ml and stored at -78 °C for 3 days to give dark red crystals of the title compound, suitable for X-ray analysis, which were filtered, washed with cold toluene and dried in vacuum (yield: 256 mg, 34%)

Structure description top

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular structure of the title compound in the crystal (the asymmetric unit contains two half molecules; operators for generating equivalent atoms: -x + 2, -y + 1, -z and -x + 1, -y, -z). Hydrogen atoms are omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level.

Bis(µ₂-isopropylimido-κ²N:N)bis[(η⁵-cyclopentadienyl)(ethenolato-κO)titanium(IV)] top

Crystal data top

[Ti₂(C₅H₅)₂(C₃H₇N)₂(C₂H₃O)₂]	F(000) = 896
M_r = 426.26	D_x = 1.338 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.8746 (4) Å	Cell parameters from 4113 reflections
b = 9.7484 (2) Å	θ = 2.5–29.5°
c = 16.3264 (4) Å	µ = 0.77 mm⁻¹
β = 106.593 (2)°	T = 150 K
V = 2116.27 (9) Å³	Prism, brown
Z = 4	0.50 × 0.40 × 0.25 mm

Data collection top

Stoe IPDS II diffractometer	4211 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.031
Graphite monochromator	θ_max = 27.0°, θ_min = 1.7°
ω scans	h = −17→17
32869 measured reflections	k = −12→12
4625 independent reflections	l = −20→20

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0485P)² + 0.2691P] where P = (F_o² + 2F_c²)/3
4625 reflections	(Δ/σ)_max = 0.002
239 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Ti₂(C₅H₅)₂(C₃H₇N)₂(C₂H₃O)₂]	V = 2116.27 (9) Å³
M_r = 426.26	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 13.8746 (4) Å	µ = 0.77 mm⁻¹
b = 9.7484 (2) Å	T = 150 K
c = 16.3264 (4) Å	0.50 × 0.40 × 0.25 mm
β = 106.593 (2)°

Data collection top

Stoe IPDS II diffractometer	4211 reflections with I > 2σ(I)
32869 measured reflections	R_int = 0.031
4625 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.069	H-atom parameters constrained
S = 1.05	Δρ_max = 0.41 e Å⁻³
4625 reflections	Δρ_min = −0.37 e Å⁻³
239 parameters

Special details top

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	1.00508 (9)	0.81266 (12)	0.07526 (8)	0.0264 (2)
H1	1.0139	0.8211	0.0199	0.032*
C2	1.04722 (11)	0.90582 (14)	0.13237 (9)	0.0398 (3)
H2A	1.0400	0.9008	0.1884	0.048*
H2B	1.0849	0.9783	0.1176	0.048*
C3	1.10447 (9)	0.42926 (12)	0.16322 (7)	0.0237 (2)
H3	1.0485	0.4372	0.1903	0.028*
C4	1.14785 (12)	0.28630 (14)	0.18057 (9)	0.0406 (3)
H4A	1.0950	0.2187	0.1567	0.061*
H4B	1.1743	0.2723	0.2424	0.061*
H4C	1.2023	0.2753	0.1539	0.061*
C5	1.18229 (11)	0.53813 (14)	0.20265 (8)	0.0344 (3)
H5A	1.2402	0.5285	0.1801	0.052*
H5B	1.2043	0.5268	0.2649	0.052*
H5C	1.1526	0.6294	0.1884	0.052*
C6	0.83879 (9)	0.43737 (12)	0.13292 (7)	0.0252 (2)
H6	0.8677	0.4425	0.1931	0.030*
C7	0.77320 (9)	0.53364 (12)	0.08185 (8)	0.0273 (2)
H7	0.7498	0.6153	0.1015	0.033*
C8	0.74794 (9)	0.48839 (13)	−0.00364 (8)	0.0273 (2)
H8	0.7049	0.5344	−0.0516	0.033*
C9	0.79764 (8)	0.36312 (12)	−0.00555 (7)	0.0249 (2)
H9	0.7938	0.3094	−0.0549	0.030*
C10	0.85404 (8)	0.33132 (12)	0.07872 (7)	0.0241 (2)
H10	0.8951	0.2525	0.0961	0.029*
C11	0.49256 (11)	−0.21964 (14)	0.14913 (8)	0.0350 (3)
H11	0.4293	−0.2371	0.1088	0.042*
C12	0.54472 (15)	−0.32585 (17)	0.18746 (11)	0.0544 (4)
H12A	0.6083	−0.3125	0.2281	0.065*
H12B	0.5188	−0.4160	0.1745	0.065*
C13	0.69659 (8)	−0.08443 (12)	0.03329 (7)	0.0232 (2)
H13	0.6907	−0.1851	0.0212	0.028*
C14	0.75543 (10)	−0.02130 (15)	−0.02278 (9)	0.0331 (3)
H14A	0.7197	−0.0378	−0.0830	0.050*
H14B	0.8224	−0.0631	−0.0093	0.050*
H14C	0.7622	0.0777	−0.0122	0.050*
C15	0.75381 (10)	−0.06547 (16)	0.12745 (8)	0.0356 (3)
H15A	0.7647	0.0326	0.1400	0.053*
H15B	0.8189	−0.1123	0.1397	0.053*
H15C	0.7146	−0.1045	0.1631	0.053*
C16	0.59925 (10)	0.27006 (13)	0.09822 (8)	0.0324 (3)
H16	0.6481	0.2876	0.0689	0.039*
C17	0.61833 (10)	0.21581 (14)	0.18150 (8)	0.0344 (3)
H17	0.6823	0.1899	0.2179	0.041*
C18	0.52699 (10)	0.20677 (13)	0.20118 (7)	0.0311 (3)
H18	0.5181	0.1745	0.2535	0.037*
C19	0.45087 (9)	0.25346 (12)	0.13058 (8)	0.0278 (2)
H19	0.3812	0.2576	0.1264	0.033*
C20	0.49548 (10)	0.29353 (12)	0.06639 (8)	0.0290 (2)
H20	0.4614	0.3297	0.0118	0.035*
N1	1.06135 (7)	0.44839 (9)	0.07062 (6)	0.02088 (18)
N2	0.59469 (7)	−0.02696 (9)	0.01025 (6)	0.02089 (19)
O1	0.95030 (6)	0.70628 (8)	0.08943 (5)	0.02590 (17)
O2	0.52192 (6)	−0.08863 (9)	0.16262 (5)	0.02749 (18)
Ti1	0.924511 (14)	0.532856 (19)	0.036855 (12)	0.01873 (7)
Ti2	0.520839 (14)	0.05278 (2)	0.083057 (12)	0.01907 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0297 (6)	0.0218 (5)	0.0307 (6)	−0.0005 (4)	0.0136 (5)	0.0008 (4)
C2	0.0497 (8)	0.0313 (7)	0.0409 (7)	−0.0158 (6)	0.0170 (6)	−0.0048 (5)
C3	0.0243 (5)	0.0265 (5)	0.0189 (5)	0.0013 (4)	0.0038 (4)	0.0020 (4)
C4	0.0452 (8)	0.0312 (7)	0.0392 (7)	0.0105 (6)	0.0020 (6)	0.0085 (5)
C5	0.0363 (7)	0.0388 (7)	0.0224 (6)	−0.0076 (5)	−0.0010 (5)	−0.0016 (5)
C6	0.0251 (5)	0.0286 (6)	0.0236 (5)	−0.0064 (4)	0.0095 (4)	0.0016 (4)
C7	0.0257 (6)	0.0252 (6)	0.0347 (6)	−0.0023 (4)	0.0143 (5)	0.0006 (4)
C8	0.0207 (5)	0.0302 (6)	0.0295 (6)	−0.0024 (4)	0.0049 (4)	0.0067 (5)
C9	0.0241 (5)	0.0252 (5)	0.0255 (5)	−0.0081 (4)	0.0073 (4)	−0.0012 (4)
C10	0.0229 (5)	0.0214 (5)	0.0287 (5)	−0.0040 (4)	0.0085 (4)	0.0035 (4)
C11	0.0456 (7)	0.0327 (7)	0.0274 (6)	−0.0083 (5)	0.0115 (5)	0.0013 (5)
C12	0.0804 (12)	0.0327 (8)	0.0472 (9)	0.0012 (8)	0.0135 (8)	0.0030 (6)
C13	0.0202 (5)	0.0248 (5)	0.0243 (5)	0.0029 (4)	0.0056 (4)	0.0009 (4)
C14	0.0251 (6)	0.0422 (7)	0.0344 (7)	0.0009 (5)	0.0125 (5)	0.0040 (5)
C15	0.0239 (6)	0.0536 (8)	0.0260 (6)	0.0080 (5)	0.0018 (5)	0.0013 (5)
C16	0.0336 (6)	0.0290 (6)	0.0376 (7)	−0.0114 (5)	0.0151 (5)	−0.0100 (5)
C17	0.0317 (6)	0.0356 (7)	0.0307 (6)	−0.0024 (5)	0.0006 (5)	−0.0136 (5)
C18	0.0449 (7)	0.0275 (6)	0.0219 (5)	0.0021 (5)	0.0112 (5)	−0.0057 (4)
C19	0.0324 (6)	0.0229 (5)	0.0304 (6)	0.0021 (4)	0.0128 (5)	−0.0038 (4)
C20	0.0398 (7)	0.0203 (5)	0.0272 (6)	−0.0017 (5)	0.0102 (5)	−0.0002 (4)
N1	0.0226 (4)	0.0200 (4)	0.0188 (4)	−0.0035 (3)	0.0040 (4)	0.0004 (3)
N2	0.0197 (4)	0.0225 (5)	0.0204 (4)	0.0011 (3)	0.0057 (4)	0.0004 (3)
O1	0.0328 (4)	0.0215 (4)	0.0257 (4)	−0.0057 (3)	0.0119 (3)	−0.0039 (3)
O2	0.0341 (4)	0.0281 (4)	0.0199 (4)	−0.0015 (3)	0.0071 (3)	0.0021 (3)
Ti1	0.02048 (11)	0.01844 (11)	0.01757 (11)	−0.00347 (7)	0.00591 (8)	−0.00093 (6)
Ti2	0.02010 (11)	0.02133 (11)	0.01558 (10)	0.00042 (7)	0.00478 (8)	−0.00092 (6)

Geometric parameters (Å, º) top

C1—C2	1.3133 (18)	C13—N2	1.4665 (14)
C1—O1	1.3443 (14)	C13—C14	1.5198 (16)
C1—H1	0.9500	C13—C15	1.5267 (16)
C2—H2A	0.9500	C13—H13	1.0000
C2—H2B	0.9500	C14—H14A	0.9800
C3—N1	1.4703 (14)	C14—H14B	0.9800
C3—C4	1.5124 (17)	C14—H14C	0.9800
C3—C5	1.5197 (17)	C15—H15A	0.9800
C3—H3	1.0000	C15—H15B	0.9800
C4—H4A	0.9800	C15—H15C	0.9800
C4—H4B	0.9800	C16—C20	1.4028 (18)
C4—H4C	0.9800	C16—C17	1.4118 (19)
C5—H5A	0.9800	C16—Ti2	2.3617 (12)
C5—H5B	0.9800	C16—H16	0.9500
C5—H5C	0.9800	C17—C18	1.3963 (19)
C6—C7	1.4039 (17)	C17—Ti2	2.3869 (12)
C6—C10	1.4155 (16)	C17—H17	0.9500
C6—Ti1	2.4096 (11)	C18—C19	1.3986 (18)
C6—H6	0.9500	C18—Ti2	2.4262 (11)
C7—C8	1.4093 (18)	C18—H18	0.9500
C7—Ti1	2.4140 (12)	C19—C20	1.4158 (16)
C7—H7	0.9500	C19—Ti2	2.4087 (11)
C8—C9	1.4071 (17)	C19—H19	0.9500
C8—Ti1	2.3878 (11)	C20—Ti2	2.3773 (12)
C8—H8	0.9500	C20—H20	0.9500
C9—C10	1.4094 (16)	N1—Ti1ⁱ	1.8296 (9)
C9—Ti1	2.3706 (11)	N1—Ti1	1.9972 (10)
C9—H9	0.9500	N2—Ti2ⁱⁱ	1.8864 (9)
C10—Ti1	2.3801 (11)	N2—Ti2	1.9398 (9)
C10—H10	0.9500	O1—Ti1	1.8834 (8)
C11—C12	1.315 (2)	O2—Ti2	1.8913 (8)
C11—O2	1.3395 (16)	Ti1—N1ⁱ	1.8296 (9)
C11—H11	0.9500	Ti1—Ti1ⁱ	2.7725 (4)
C12—H12A	0.9500	Ti2—N2ⁱⁱ	1.8864 (9)
C12—H12B	0.9500	Ti2—Ti2ⁱⁱ	2.8022 (4)

C2—C1—O1	124.77 (11)	C19—C18—H18	125.9
C2—C1—H1	117.6	Ti2—C18—H18	121.7
O1—C1—H1	117.6	C18—C19—C20	108.23 (11)
C1—C2—H2A	120.0	C18—C19—Ti2	73.87 (7)
C1—C2—H2B	120.0	C20—C19—Ti2	71.58 (7)
H2A—C2—H2B	120.0	C18—C19—H19	125.9
N1—C3—C4	109.44 (10)	C20—C19—H19	125.9
N1—C3—C5	112.22 (9)	Ti2—C19—H19	120.4
C4—C3—C5	111.57 (10)	C16—C20—C19	107.48 (11)
N1—C3—H3	107.8	C16—C20—Ti2	72.18 (7)
C4—C3—H3	107.8	C19—C20—Ti2	74.01 (7)
C5—C3—H3	107.8	C16—C20—H20	126.3
C3—C4—H4A	109.5	C19—C20—H20	126.3
C3—C4—H4B	109.5	Ti2—C20—H20	119.4
H4A—C4—H4B	109.5	C3—N1—Ti1ⁱ	151.07 (8)
C3—C4—H4C	109.5	C3—N1—Ti1	114.31 (7)
H4A—C4—H4C	109.5	Ti1ⁱ—N1—Ti1	92.75 (4)
H4B—C4—H4C	109.5	C13—N2—Ti2ⁱⁱ	133.70 (7)
C3—C5—H5A	109.5	C13—N2—Ti2	129.43 (7)
C3—C5—H5B	109.5	Ti2ⁱⁱ—N2—Ti2	94.16 (4)
H5A—C5—H5B	109.5	C1—O1—Ti1	131.09 (7)
C3—C5—H5C	109.5	C11—O2—Ti2	129.76 (8)
H5A—C5—H5C	109.5	N1ⁱ—Ti1—O1	106.79 (4)
H5B—C5—H5C	109.5	N1ⁱ—Ti1—N1	87.25 (4)
C7—C6—C10	107.71 (10)	O1—Ti1—N1	101.68 (4)
C7—C6—Ti1	73.25 (6)	N1ⁱ—Ti1—C9	93.65 (4)
C10—C6—Ti1	71.67 (6)	O1—Ti1—C9	142.01 (4)
C7—C6—H6	126.1	N1—Ti1—C9	111.16 (4)
C10—C6—H6	126.1	N1ⁱ—Ti1—C10	121.55 (4)
Ti1—C6—H6	120.7	O1—Ti1—C10	130.56 (4)
C6—C7—C8	108.34 (11)	N1—Ti1—C10	90.95 (4)
C6—C7—Ti1	72.91 (7)	C9—Ti1—C10	34.52 (4)
C8—C7—Ti1	71.91 (7)	N1ⁱ—Ti1—C8	97.76 (4)
C6—C7—H7	125.8	O1—Ti1—C8	109.60 (4)
C8—C7—H7	125.8	N1—Ti1—C8	145.17 (4)
Ti1—C7—H7	121.1	C9—Ti1—C8	34.40 (4)
C9—C8—C7	107.98 (10)	C10—Ti1—C8	57.08 (4)
C9—C8—Ti1	72.13 (6)	N1ⁱ—Ti1—C6	150.56 (4)
C7—C8—Ti1	73.96 (7)	O1—Ti1—C6	96.60 (4)
C9—C8—H8	126.0	N1—Ti1—C6	105.55 (4)
C7—C8—H8	126.0	C9—Ti1—C6	57.12 (4)
Ti1—C8—H8	119.7	C10—Ti1—C6	34.37 (4)
C8—C9—C10	107.96 (10)	C8—Ti1—C6	56.77 (4)
C8—C9—Ti1	73.47 (6)	N1ⁱ—Ti1—C7	129.22 (4)
C10—C9—Ti1	73.11 (6)	O1—Ti1—C7	85.81 (4)
C8—C9—H9	126.0	N1—Ti1—C7	139.30 (4)
C10—C9—H9	126.0	C9—Ti1—C7	56.86 (4)
Ti1—C9—H9	119.3	C10—Ti1—C7	56.70 (4)
C9—C10—C6	108.01 (10)	C8—Ti1—C7	34.13 (4)
C9—C10—Ti1	72.37 (6)	C6—Ti1—C7	33.84 (4)
C6—C10—Ti1	73.96 (6)	N1ⁱ—Ti1—Ti1ⁱ	46.02 (3)
C9—C10—H10	126.0	O1—Ti1—Ti1ⁱ	109.66 (3)
C6—C10—H10	126.0	N1—Ti1—Ti1ⁱ	41.24 (3)
Ti1—C10—H10	119.5	C9—Ti1—Ti1ⁱ	107.58 (3)
C12—C11—O2	124.91 (14)	C10—Ti1—Ti1ⁱ	110.93 (3)
C12—C11—H11	117.5	C8—Ti1—Ti1ⁱ	132.88 (3)
O2—C11—H11	117.5	C6—Ti1—Ti1ⁱ	140.16 (3)
C11—C12—H12A	120.0	C7—Ti1—Ti1ⁱ	164.44 (3)
C11—C12—H12B	120.0	N2ⁱⁱ—Ti2—O2	107.20 (4)
H12A—C12—H12B	120.0	N2ⁱⁱ—Ti2—N2	85.84 (4)
N2—C13—C14	109.58 (9)	O2—Ti2—N2	103.11 (4)
N2—C13—C15	113.45 (9)	N2ⁱⁱ—Ti2—C16	117.65 (4)
C14—C13—C15	110.07 (10)	O2—Ti2—C16	131.96 (4)
N2—C13—H13	107.9	N2—Ti2—C16	96.63 (4)
C14—C13—H13	107.9	N2ⁱⁱ—Ti2—C20	88.59 (4)
C15—C13—H13	107.9	O2—Ti2—C20	140.36 (4)
C13—C14—H14A	109.5	N2—Ti2—C20	114.35 (4)
C13—C14—H14B	109.5	C16—Ti2—C20	34.43 (5)
H14A—C14—H14B	109.5	N2ⁱⁱ—Ti2—C17	145.09 (4)
C13—C14—H14C	109.5	O2—Ti2—C17	97.53 (4)
H14A—C14—H14C	109.5	N2—Ti2—C17	112.49 (4)
H14B—C14—H14C	109.5	C16—Ti2—C17	34.59 (5)
C13—C15—H15A	109.5	C20—Ti2—C17	57.08 (5)
C13—C15—H15B	109.5	N2ⁱⁱ—Ti2—C19	92.34 (4)
H15A—C15—H15B	109.5	O2—Ti2—C19	107.19 (4)
C13—C15—H15C	109.5	N2—Ti2—C19	148.75 (4)
H15A—C15—H15C	109.5	C16—Ti2—C19	56.89 (4)
H15B—C15—H15C	109.5	C20—Ti2—C19	34.41 (4)
C20—C16—C17	107.95 (11)	C17—Ti2—C19	56.31 (4)
C20—C16—Ti2	73.39 (7)	N2ⁱⁱ—Ti2—C18	123.60 (4)
C17—C16—Ti2	73.68 (7)	O2—Ti2—C18	85.03 (4)
C20—C16—H16	126.0	N2—Ti2—C18	146.12 (4)
C17—C16—H16	126.0	C16—Ti2—C18	56.71 (4)
Ti2—C16—H16	118.8	C20—Ti2—C18	56.67 (4)
C18—C17—C16	108.20 (11)	C17—Ti2—C18	33.72 (5)
C18—C17—Ti2	74.68 (7)	C19—Ti2—C18	33.63 (4)
C16—C17—Ti2	71.73 (7)	N2ⁱⁱ—Ti2—Ti2ⁱⁱ	43.66 (3)
C18—C17—H17	125.9	O2—Ti2—Ti2ⁱⁱ	110.86 (3)
C16—C17—H17	125.9	N2—Ti2—Ti2ⁱⁱ	42.18 (3)
Ti2—C17—H17	119.5	C16—Ti2—Ti2ⁱⁱ	113.10 (3)
C17—C18—C19	108.13 (11)	C20—Ti2—Ti2ⁱⁱ	105.60 (3)
C17—C18—Ti2	71.60 (7)	C17—Ti2—Ti2ⁱⁱ	144.77 (4)
C19—C18—Ti2	72.50 (7)	C19—Ti2—Ti2ⁱⁱ	128.26 (3)
C17—C18—H18	125.9	C18—Ti2—Ti2ⁱⁱ	161.30 (3)

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

Experimental details

Crystal data
Chemical formula	[Ti₂(C₅H₅)₂(C₃H₇N)₂(C₂H₃O)₂]
M_r	426.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	13.8746 (4), 9.7484 (2), 16.3264 (4)
β (°)	106.593 (2)
V (Å³)	2116.27 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.77
Crystal size (mm)	0.50 × 0.40 × 0.25

Data collection
Diffractometer	Stoe IPDS II
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	32869, 4625, 4211
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.069, 1.05
No. of reflections	4625
No. of parameters	239
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.37

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

References

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