μ-Oxido-bis­[bis­(penta­fluoro­phenolato)(η5-penta­methyl­cyclo­penta­dien­yl)titanium(IV)]

Lee, J.; Kim, Y.

doi:10.1107/S1600536811029357

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1147

doi:10.1107/S1600536811029357

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μ-Oxido-bis[bis(pentafluorophenolato)(η⁵-pentamethylcyclopentadienyl)titanium(IV)]

Junseong Lee ^a and Youngjo Kim ^b ^*

^aDepartment of Chemistry, Chonnam National University, Gwangju 500-757, Republic of Korea, and ^bDepartment of Chemistry, Chungbuk National University, Cheongju, Chungbuk 361-763, Republic of Korea
^*Correspondence e-mail: ykim@chungbuk.ac.kr

(Received 17 July 2011; accepted 20 July 2011; online 30 July 2011)

The dinuclear title complex, [Ti₂(C₁₀H₁₅)₂(C₆F₅O)₄O], features two Ti^IV atoms bridged by an O atom, which lies on an inversion centre. The Ti^IV atom is bonded to a η⁵-pentamethylcyclopentadienyl ring, two pentafluorophenolate anions and to the bridging O atom. The environment around the Ti^IV atom can be considered as a distorted tetrahedron. The cyclopentadienyl ring is disordered over two sets of sites [site occupancy = 0.824 (8) for the major component].

Related literature

For the related titanium complexes, Cp^*Ti(OCH₂C₆F₅)₃ and Cp^*Ti(OC₆F₅)₃, see: Lee et al. (2007 ) and for [Ti₂(η⁵-C₅Me₅)₂(OCH₂C₆F₅)₄O], see: Lee & Kim (2011 ). For the use of dinuclear titanium complexes with a cyclopentadienyl ligand in organometallic catalysis, see: Noh et al. (2006 ); Wu et al. (2007 ); Yoon et al. (2011 ). For the Ti—O—Ti angle in related structures, see: Gowik et al. (1990 ); Thewalt & Schomburg (1977 ); Wu et al. (2007).

Experimental

Crystal data

[Ti₂(C₁₀H₁₅)₂(C₆F₅O)₄O]
M_r = 1114.48
Triclinic, $[P \overline 1]$
a = 8.7472 (17) Å
b = 11.823 (2) Å
c = 12.923 (3) Å
α = 112.00 (3)°
β = 109.24 (3)°
γ = 97.36 (3)°
V = 1120.6 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 293 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker SMART 1K CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.94, T_max = 0.96
12962 measured reflections
5069 independent reflections
3892 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.141
S = 1.03
5069 reflections
423 parameters
49 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811029357/bx2364sup1.cif

Supporting information file. DOI: 10.1107/S1600536811029357/bx2364Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811029357/bx2364Isup3.hkl

checkCIF report

Comment top

Dinuclear titanium complexes containing a cyclopentadienyl ligand have attracted considerable attention in the fields of organometallic catalysis (Noh et al., 2006; Wu et al., 2007; Yoon et al., 2011). Recently, we have reported the facile synthesis of Cp^*Ti(OCH₂C₆F₅)₃ and Cp^*Ti(OC₆F₅)₃ (Cp^* = η⁵-pentamethylcyclopentadienyl) (Lee et al., 2007). We have also reported the X-ray structure of [Ti₂(η⁵-C₅Me₅)₂(OCH₂C₆F₅)₄O] (Lee & Kim 2011). In continuation of our systematic studies on bimetallic pentamethylcyclopentadienyltitanium derivative using previously synthesized Cp^*Ti(OC₆F₅)₃, the title complex (I) has been investigated.

The title compound (I) is the main product of the reaction of Cp^*Ti(OC₆F₅)₃ with water in dichloromethane solution. In (I) (Fig. 1), the dinuclear structure shows two Ti atoms bridged by an oxygen atom, which is lies on inversion centre, Fig. 2 , with approximately C₂ symmetry. Ti atom bonded with bridging oxygen atom, a Cp ring and two pentafluorophenolate groups, having distorted tetrahedron geometry.

A disorder of Cp* rings was observed in a ratio of 0.824 (8) and 0.176 (8) for C1—C10 and C1A—C10A, respectively. The Ti—C and Ti—O distances are in the range of 2.337 (16) - 2.400 (11) Å and 1.8184 (11) - 1.854 (2) Å, respectively. The Ti—O—Ti angle is almost linear [180.00 (4) °], which falls within the observed range (154 - 180°) for the previous reported compounds (Wu et al., 2007; Thewalt & Schomburg, 1977; Gowik et al., 1990; Lee & Kim, 2011). Whereas Cp^* and phenyl rings are almost perpendicular in [Ti₂(η⁵-C₅Me₅)₂(OCH₂C₆F₅)₄O], the Cp^* ring and phenyl rings are almost parallel with the dihedral angles of 20.8 (6) ° and 10.2 (6) ° and there is π-π interaction between and Cp ring and phenyl ring (C17—C22) with the perpendicular distance of 3.396 Å.

Related literature top

For the related titanium complexes, Cp^*Ti(OCH₂C₆F₅)₃ and Cp^*Ti(OC₆F₅)₃, see: Lee et al. (2007) and for [Ti₂(η⁵-C₅Me₅)₂(OCH₂C₆F₅)₄O], see: Lee & Kim (2011). For the use of dinuclear titanium complexes with a cyclopentadienyl ligand in organometallic catalysis, see: Noh et al. (2006); Wu et al. (2007); Yoon et al. (2011). For the Ti—O—Ti angle in related structures, see: Gowik et al. (1990); Thewalt & Schomburg (1977); Wu et al. (2007).

Experimental top

Complex (I) was synthesized by the hydrolysis of Cp^*Ti(OC₆F₅)₃. The crystal was obtained by slow evaporation of methylene chloride as a solvent in refrigerator.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 20% probability level. H atoms are omitted for clarity.
	Fig. 2. The molecular structure of the title compound (I). Displacement ellipsoids are drawn at the 20% probability level. H atoms are omitted for clarity.

µ-Oxido-bis[bis(pentafluorophenolato)(η⁵-pentamethylcyclopentadienyl)titanium(IV)] top

Crystal data top

[Ti₂(C₁₀H₁₅)₂(C₆F₅O)₄O]	Z = 1
M_r = 1114.48	F(000) = 558
Triclinic, P1	D_x = 1.651 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7472 (17) Å	Cell parameters from 5069 reflections
b = 11.823 (2) Å	θ = 1.9–28.3°
c = 12.923 (3) Å	µ = 0.49 mm⁻¹
α = 112.00 (3)°	T = 293 K
β = 109.24 (3)°	Block, yellow
γ = 97.36 (3)°	0.12 × 0.10 × 0.08 mm
V = 1120.6 (4) Å³

Data collection top

Bruker SMART 1K CCD diffractometer	5069 independent reflections
Radiation source: fine-focus sealed tube	3892 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
profile data from /ω scans	θ_max = 28.3°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −11→11
T_min = 0.94, T_max = 0.96	k = −15→15
12962 measured reflections	l = −17→16

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0747P)² + 0.3233P] where P = (F_o² + 2F_c²)/3
5069 reflections	(Δ/σ)_max < 0.001
423 parameters	Δρ_max = 0.28 e Å⁻³
49 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Ti₂(C₁₀H₁₅)₂(C₆F₅O)₄O]	γ = 97.36 (3)°
M_r = 1114.48	V = 1120.6 (4) Å³
Triclinic, P1	Z = 1
a = 8.7472 (17) Å	Mo Kα radiation
b = 11.823 (2) Å	µ = 0.49 mm⁻¹
c = 12.923 (3) Å	T = 293 K
α = 112.00 (3)°	0.12 × 0.10 × 0.08 mm
β = 109.24 (3)°

Data collection top

Bruker SMART 1K CCD diffractometer	5069 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	3892 reflections with I > 2σ(I)
T_min = 0.94, T_max = 0.96	R_int = 0.033
12962 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	49 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 1.03	Δρ_max = 0.28 e Å⁻³
5069 reflections	Δρ_min = −0.34 e Å⁻³
423 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	Occ. (<1)
Ti1	0.09529 (5)	0.15447 (4)	0.13341 (3)	0.04162 (14)
O1	0.0000	0.0000	0.0000	0.0441 (5)
O2	0.1777 (3)	0.1137 (2)	0.26188 (17)	0.0781 (6)
O3	0.2933 (2)	0.22063 (19)	0.1261 (2)	0.0754 (6)
C1	0.0139 (11)	0.3210 (8)	0.2536 (4)	0.0689 (19)	0.824 (8)
C2	−0.1240 (12)	0.2120 (9)	0.1862 (9)	0.068 (2)	0.824 (8)
C3	−0.1767 (11)	0.1821 (8)	0.0620 (7)	0.0561 (16)	0.824 (8)
C4	−0.0668 (9)	0.2698 (6)	0.0523 (5)	0.0511 (10)	0.824 (8)
C5	0.0508 (7)	0.3587 (4)	0.1715 (7)	0.0576 (13)	0.824 (8)
C6	0.1057 (11)	0.3864 (8)	0.3922 (4)	0.143 (4)	0.824 (8)
H6A	0.0514	0.4471	0.4261	0.215*	0.824 (8)
H6B	0.2211	0.4294	0.4154	0.215*	0.824 (8)
H6C	0.1028	0.3239	0.4228	0.215*	0.824 (8)
C7	−0.2140 (9)	0.1381 (8)	0.2349 (8)	0.125 (3)	0.824 (8)
H7A	−0.1457	0.1647	0.3198	0.188*	0.824 (8)
H7B	−0.2318	0.0486	0.1894	0.188*	0.824 (8)
H7C	−0.3211	0.1547	0.2260	0.188*	0.824 (8)
C8	−0.3250 (6)	0.0759 (5)	−0.0432 (6)	0.095 (2)	0.824 (8)
H8A	−0.4250	0.1038	−0.0549	0.142*	0.824 (8)
H8B	−0.3400	0.0040	−0.0259	0.142*	0.824 (8)
H8C	−0.3049	0.0518	−0.1162	0.142*	0.824 (8)
C9	−0.0767 (9)	0.2720 (7)	−0.0655 (5)	0.0956 (19)	0.824 (8)
H9A	−0.1191	0.1865	−0.1298	0.143*	0.824 (8)
H9B	0.0339	0.3104	−0.0556	0.143*	0.824 (8)
H9C	−0.1513	0.3205	−0.0862	0.143*	0.824 (8)
C10	0.1810 (6)	0.4768 (4)	0.2046 (8)	0.118 (3)	0.824 (8)
H10A	0.1343	0.5475	0.2204	0.177*	0.824 (8)
H10B	0.2136	0.4645	0.1380	0.177*	0.824 (8)
H10C	0.2782	0.4940	0.2765	0.177*	0.824 (8)
C1A	−0.022 (4)	0.282 (3)	0.2591 (15)	0.043 (5)	0.176 (8)
C2A	−0.155 (4)	0.189 (2)	0.1539 (19)	0.044 (9)	0.176 (8)
C3A	−0.148 (4)	0.201 (3)	0.0513 (14)	0.050 (11)	0.176 (8)
C4A	−0.016 (3)	0.309 (2)	0.094 (2)	0.037 (5)	0.176 (8)
C5A	0.061 (2)	0.3606 (17)	0.224 (2)	0.047 (5)	0.176 (8)
C6A	−0.006 (4)	0.304 (3)	0.3866 (18)	0.105 (8)	0.176 (8)
H6A1	−0.0817	0.3510	0.4074	0.158*	0.176 (8)
H6A2	0.1083	0.3520	0.4447	0.158*	0.176 (8)
H6A3	−0.0332	0.2238	0.3882	0.158*	0.176 (8)
C7A	−0.288 (3)	0.080 (2)	0.139 (3)	0.092 (7)	0.176 (8)
H7A1	−0.2506	0.0669	0.2111	0.138*	0.176 (8)
H7A2	−0.3035	0.0036	0.0693	0.138*	0.176 (8)
H7A3	−0.3929	0.1007	0.1267	0.138*	0.176 (8)
C8A	−0.278 (3)	0.122 (2)	−0.0793 (15)	0.077 (7)	0.176 (8)
H8A1	−0.2424	0.1456	−0.1331	0.115*	0.176 (8)
H8A2	−0.3850	0.1380	−0.0856	0.115*	0.176 (8)
H8A3	−0.2894	0.0335	−0.1019	0.115*	0.176 (8)
C9A	0.021 (3)	0.357 (2)	0.010 (2)	0.076 (7)	0.176 (8)
H9A1	0.0339	0.2895	−0.0541	0.114*	0.176 (8)
H9A2	0.1237	0.4262	0.0551	0.114*	0.176 (8)
H9A3	−0.0704	0.3866	−0.0260	0.114*	0.176 (8)
C10A	0.204 (3)	0.4821 (17)	0.310 (2)	0.092 (7)	0.176 (8)
H10D	0.1610	0.5542	0.3185	0.138*	0.176 (8)
H10E	0.2883	0.4859	0.2784	0.138*	0.176 (8)
H10F	0.2537	0.4832	0.3892	0.138*	0.176 (8)
C11	0.2320 (4)	0.0988 (3)	0.3627 (2)	0.0592 (7)
C12	0.3854 (4)	0.1761 (3)	0.4611 (3)	0.0705 (8)
C13	0.4441 (4)	0.1573 (3)	0.5639 (3)	0.0803 (9)
C14	0.3539 (5)	0.0620 (4)	0.5728 (3)	0.0799 (9)
C15	0.2040 (5)	−0.0145 (3)	0.4798 (3)	0.0792 (9)
C16	0.1435 (4)	0.0036 (3)	0.3765 (3)	0.0714 (8)
C17	0.4133 (3)	0.2970 (2)	0.1221 (3)	0.0570 (6)
C18	0.5478 (3)	0.3887 (3)	0.2276 (3)	0.0613 (7)
C19	0.6739 (3)	0.4667 (3)	0.2236 (3)	0.0653 (7)
C20	0.6712 (3)	0.4546 (3)	0.1139 (3)	0.0641 (7)
C21	0.5425 (4)	0.3650 (3)	0.0082 (3)	0.0639 (7)
C22	0.4165 (3)	0.2878 (3)	0.0131 (3)	0.0627 (7)
F1	−0.0057 (3)	−0.0725 (2)	0.2872 (2)	0.1189 (8)
F2	0.1130 (3)	−0.1077 (3)	0.4882 (3)	0.1323 (10)
F3	0.4136 (3)	0.0438 (3)	0.6738 (2)	0.1240 (9)
F4	0.5933 (3)	0.2317 (3)	0.6553 (2)	0.1361 (11)
F5	0.4779 (3)	0.2697 (2)	0.4549 (2)	0.1213 (9)
F6	0.5545 (3)	0.4040 (2)	0.33688 (18)	0.0986 (7)
F7	0.7987 (3)	0.5554 (2)	0.32698 (19)	0.1061 (7)
F8	0.7934 (3)	0.5323 (2)	0.1102 (2)	0.0969 (7)
F9	0.5402 (3)	0.3521 (2)	−0.09978 (19)	0.1006 (7)
F10	0.2916 (2)	0.20016 (19)	−0.09189 (18)	0.0996 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ti1	0.0396 (2)	0.0401 (2)	0.0364 (2)	0.00442 (16)	0.00860 (16)	0.01646 (17)
O1	0.0409 (11)	0.0429 (11)	0.0414 (11)	0.0072 (9)	0.0107 (9)	0.0186 (9)
O2	0.0982 (16)	0.0952 (16)	0.0437 (10)	0.0458 (13)	0.0178 (10)	0.0378 (11)
O3	0.0496 (10)	0.0548 (11)	0.1166 (17)	0.0041 (9)	0.0344 (11)	0.0360 (12)
C1	0.094 (6)	0.067 (5)	0.042 (2)	0.040 (4)	0.025 (2)	0.018 (2)
C2	0.079 (6)	0.082 (6)	0.087 (4)	0.039 (4)	0.054 (4)	0.059 (4)
C3	0.042 (2)	0.048 (2)	0.074 (4)	0.0132 (17)	0.023 (3)	0.024 (3)
C4	0.051 (3)	0.054 (3)	0.050 (3)	0.018 (2)	0.018 (2)	0.026 (2)
C5	0.052 (2)	0.039 (2)	0.072 (4)	0.0096 (17)	0.016 (3)	0.023 (3)
C6	0.190 (7)	0.153 (6)	0.040 (2)	0.105 (6)	0.020 (3)	0.002 (3)
C7	0.142 (6)	0.171 (7)	0.207 (8)	0.100 (5)	0.139 (6)	0.154 (7)
C8	0.047 (2)	0.066 (3)	0.124 (5)	0.016 (2)	0.005 (2)	0.020 (3)
C9	0.113 (4)	0.146 (6)	0.083 (3)	0.076 (4)	0.056 (3)	0.081 (4)
C10	0.068 (3)	0.048 (2)	0.217 (8)	0.011 (2)	0.042 (4)	0.054 (3)
C1A	0.046 (12)	0.045 (14)	0.033 (9)	0.014 (9)	0.006 (8)	0.023 (9)
C2A	0.019 (6)	0.014 (6)	0.064 (18)	−0.007 (5)	0.005 (8)	−0.005 (8)
C3A	0.039 (17)	0.08 (3)	0.016 (7)	0.021 (15)	0.005 (8)	0.009 (9)
C4A	0.035 (8)	0.040 (9)	0.040 (9)	0.010 (6)	0.012 (7)	0.024 (7)
C5A	0.045 (9)	0.038 (8)	0.049 (14)	−0.002 (6)	0.006 (10)	0.026 (10)
C6A	0.123 (12)	0.118 (12)	0.082 (10)	0.042 (9)	0.046 (8)	0.046 (8)
C7A	0.091 (10)	0.086 (10)	0.113 (11)	0.024 (7)	0.053 (8)	0.048 (8)
C8A	0.065 (13)	0.069 (14)	0.045 (9)	0.032 (11)	−0.010 (8)	−0.002 (8)
C9A	0.097 (16)	0.102 (17)	0.086 (16)	0.058 (14)	0.062 (14)	0.070 (14)
C10A	0.086 (10)	0.068 (9)	0.103 (11)	0.014 (7)	0.034 (8)	0.025 (7)
C11	0.0689 (17)	0.0690 (17)	0.0382 (12)	0.0267 (14)	0.0155 (12)	0.0260 (12)
C12	0.0753 (19)	0.0699 (18)	0.0567 (16)	0.0061 (15)	0.0133 (14)	0.0352 (15)
C13	0.076 (2)	0.089 (2)	0.0467 (15)	−0.0008 (17)	−0.0011 (14)	0.0308 (15)
C14	0.090 (2)	0.098 (2)	0.0553 (17)	0.0231 (19)	0.0188 (16)	0.0486 (18)
C15	0.081 (2)	0.087 (2)	0.079 (2)	0.0182 (18)	0.0290 (18)	0.0514 (19)
C16	0.0598 (17)	0.0742 (19)	0.0582 (17)	0.0108 (15)	0.0066 (14)	0.0254 (15)
C17	0.0430 (13)	0.0470 (13)	0.0771 (18)	0.0104 (11)	0.0218 (12)	0.0270 (13)
C18	0.0543 (15)	0.0652 (16)	0.0599 (16)	0.0041 (12)	0.0187 (12)	0.0315 (14)
C19	0.0480 (14)	0.0640 (17)	0.0682 (17)	−0.0019 (12)	0.0115 (13)	0.0301 (14)
C20	0.0533 (15)	0.0662 (17)	0.087 (2)	0.0161 (13)	0.0329 (15)	0.0448 (16)
C21	0.0700 (18)	0.0759 (19)	0.0647 (17)	0.0365 (16)	0.0361 (15)	0.0379 (15)
C22	0.0483 (14)	0.0564 (15)	0.0632 (17)	0.0187 (12)	0.0132 (12)	0.0138 (13)
F1	0.0778 (14)	0.1114 (18)	0.0993 (16)	−0.0091 (12)	−0.0151 (12)	0.0346 (14)
F2	0.1154 (19)	0.140 (2)	0.156 (2)	0.0004 (17)	0.0436 (18)	0.102 (2)
F3	0.141 (2)	0.163 (2)	0.0812 (14)	0.0342 (18)	0.0237 (14)	0.0898 (16)
F4	0.1177 (19)	0.133 (2)	0.0750 (13)	−0.0343 (15)	−0.0313 (13)	0.0469 (14)
F5	0.1201 (19)	0.1158 (18)	0.1085 (17)	−0.0161 (14)	0.0138 (14)	0.0749 (15)
F6	0.0966 (14)	0.1208 (17)	0.0711 (12)	−0.0025 (12)	0.0276 (11)	0.0520 (12)
F7	0.0747 (12)	0.1052 (16)	0.0829 (13)	−0.0316 (11)	−0.0004 (10)	0.0330 (12)
F8	0.0789 (12)	0.1069 (15)	0.1440 (19)	0.0200 (11)	0.0626 (13)	0.0825 (15)
F9	0.1248 (17)	0.1330 (19)	0.0800 (13)	0.0640 (15)	0.0616 (13)	0.0580 (13)
F10	0.0745 (12)	0.0846 (13)	0.0749 (12)	0.0138 (10)	0.0026 (10)	−0.0024 (10)

Geometric parameters (Å, º) top

Ti1—O1	1.8184 (11)	C2A—C7A	1.524 (16)
Ti1—O2	1.8464 (19)	C3A—C4A	1.395 (16)
Ti1—O3	1.854 (2)	C3A—C8A	1.516 (14)
Ti1—C3A	2.28 (4)	C4A—C5A	1.421 (15)
Ti1—C4A	2.320 (19)	C4A—C9A	1.510 (14)
Ti1—C2	2.336 (9)	C5A—C10A	1.515 (15)
Ti1—C4	2.356 (5)	C6A—H6A1	0.9600
Ti1—C2A	2.36 (4)	C6A—H6A2	0.9600
Ti1—C1	2.365 (7)	C6A—H6A3	0.9600
Ti1—C3	2.366 (10)	C7A—H7A1	0.9600
Ti1—C1A	2.37 (3)	C7A—H7A2	0.9600
Ti1—C5A	2.38 (2)	C7A—H7A3	0.9600
O1—Ti1ⁱ	1.8184 (11)	C8A—H8A1	0.9600
O2—C11	1.318 (3)	C8A—H8A2	0.9600
O3—C17	1.321 (3)	C8A—H8A3	0.9600
C1—C2	1.394 (8)	C9A—H9A1	0.9600
C1—C5	1.404 (7)	C9A—H9A2	0.9600
C1—C6	1.518 (6)	C9A—H9A3	0.9600
C2—C3	1.400 (7)	C10A—H10D	0.9600
C2—C7	1.529 (6)	C10A—H10E	0.9600
C3—C4	1.391 (7)	C10A—H10F	0.9600
C3—C8	1.500 (7)	C11—C16	1.384 (4)
C4—C5	1.415 (6)	C11—C12	1.394 (4)
C4—C9	1.506 (5)	C12—F5	1.329 (3)
C5—C10	1.501 (6)	C12—C13	1.370 (4)
C6—H6A	0.9600	C13—F4	1.335 (4)
C6—H6B	0.9600	C13—C14	1.355 (5)
C6—H6C	0.9600	C14—F3	1.347 (3)
C7—H7A	0.9600	C14—C15	1.350 (5)
C7—H7B	0.9600	C15—F2	1.335 (4)
C7—H7C	0.9600	C15—C16	1.373 (4)
C8—H8A	0.9600	C16—F1	1.332 (3)
C8—H8B	0.9600	C17—C22	1.382 (4)
C8—H8C	0.9600	C17—C18	1.389 (4)
C9—H9A	0.9600	C18—F6	1.335 (3)
C9—H9B	0.9600	C18—C19	1.372 (4)
C9—H9C	0.9600	C19—F7	1.331 (3)
C10—H10A	0.9600	C19—C20	1.362 (4)
C10—H10B	0.9600	C20—F8	1.343 (3)
C10—H10C	0.9600	C20—C21	1.361 (4)
C1A—C2A	1.385 (16)	C21—F9	1.340 (3)
C1A—C5A	1.403 (16)	C21—C22	1.371 (4)
C1A—C6A	1.521 (16)	C22—F10	1.337 (3)
C2A—C3A	1.405 (16)

O1—Ti1—O2	103.35 (8)	C10—C5—Ti1	125.5 (4)
O1—Ti1—O3	104.10 (8)	C2A—C1A—C5A	107.1 (13)
O2—Ti1—O3	101.46 (11)	C2A—C1A—C6A	122 (2)
O1—Ti1—C3A	86.0 (7)	C5A—C1A—C6A	129 (2)
O2—Ti1—C3A	132.7 (6)	C2A—C1A—Ti1	72.5 (19)
O3—Ti1—C3A	121.3 (6)	C5A—C1A—Ti1	73.3 (16)
O1—Ti1—C4A	111.5 (6)	C6A—C1A—Ti1	130 (2)
O2—Ti1—C4A	139.0 (5)	C1A—C2A—C3A	109.5 (13)
O3—Ti1—C4A	90.6 (4)	C1A—C2A—C7A	129.5 (19)
C3A—Ti1—C4A	35.3 (5)	C3A—C2A—C7A	120.9 (18)
O1—Ti1—C2	106.3 (3)	C1A—C2A—Ti1	73.4 (19)
O2—Ti1—C2	92.3 (2)	C3A—C2A—Ti1	69 (2)
O3—Ti1—C2	142.6 (2)	C7A—C2A—Ti1	120 (2)
C3A—Ti1—C2	41.5 (6)	C4A—C3A—C2A	107.4 (12)
C4A—Ti1—C2	58.1 (4)	C4A—C3A—C8A	126.7 (19)
O1—Ti1—C4	98.28 (17)	C2A—C3A—C8A	125.2 (19)
O2—Ti1—C4	146.91 (14)	C4A—C3A—Ti1	73.9 (17)
O3—Ti1—C4	97.12 (18)	C2A—C3A—Ti1	76 (2)
C3A—Ti1—C4	24.9 (6)	C8A—C3A—Ti1	124 (3)
C4A—Ti1—C4	13.6 (5)	C3A—C4A—C5A	107.4 (11)
C2—Ti1—C4	57.41 (19)	C3A—C4A—C9A	122.2 (18)
O1—Ti1—C2A	97.6 (5)	C5A—C4A—C9A	130.3 (18)
O2—Ti1—C2A	97.6 (6)	C3A—C4A—Ti1	70.8 (19)
O3—Ti1—C2A	146.7 (6)	C5A—C4A—Ti1	74.9 (12)
C3A—Ti1—C2A	35.2 (6)	C9A—C4A—Ti1	121.5 (13)
C4A—Ti1—C2A	57.7 (7)	C1A—C5A—C4A	108.2 (12)
C2—Ti1—C2A	9.2 (5)	C1A—C5A—C10A	125.5 (19)
C4—Ti1—C2A	54.5 (6)	C4A—C5A—C10A	126.2 (19)
O1—Ti1—C1	139.7 (2)	C1A—C5A—Ti1	72.4 (17)
O2—Ti1—C1	90.41 (18)	C4A—C5A—Ti1	70.0 (12)
O3—Ti1—C1	110.0 (3)	C10A—C5A—Ti1	125.1 (16)
C3A—Ti1—C1	58.3 (7)	C1A—C6A—H6A1	109.5
C4A—Ti1—C1	48.8 (5)	C1A—C6A—H6A2	109.5
C2—Ti1—C1	34.5 (2)	H6A1—C6A—H6A2	109.5
C4—Ti1—C1	57.36 (18)	C1A—C6A—H6A3	109.5
C2A—Ti1—C1	42.5 (5)	H6A1—C6A—H6A3	109.5
O1—Ti1—C3	84.26 (19)	H6A2—C6A—H6A3	109.5
O2—Ti1—C3	123.8 (3)	C2A—C7A—H7A1	109.5
O3—Ti1—C3	131.0 (3)	C2A—C7A—H7A2	109.5
C3A—Ti1—C3	9.7 (5)	H7A1—C7A—H7A2	109.5
C4A—Ti1—C3	43.4 (5)	C2A—C7A—H7A3	109.5
C2—Ti1—C3	34.6 (2)	H7A1—C7A—H7A3	109.5
C4—Ti1—C3	34.26 (18)	H7A2—C7A—H7A3	109.5
C2A—Ti1—C3	27.1 (6)	C3A—C8A—H8A1	109.5
C1—Ti1—C3	57.3 (2)	C3A—C8A—H8A2	109.5
O1—Ti1—C1A	130.9 (5)	H8A1—C8A—H8A2	109.5
O2—Ti1—C1A	82.6 (5)	C3A—C8A—H8A3	109.5
O3—Ti1—C1A	122.6 (5)	H8A1—C8A—H8A3	109.5
C3A—Ti1—C1A	58.6 (8)	H8A2—C8A—H8A3	109.5
C4A—Ti1—C1A	58.4 (6)	C4A—C9A—H9A1	109.5
C2—Ti1—C1A	25.0 (5)	C4A—C9A—H9A2	109.5
C4—Ti1—C1A	64.3 (6)	H9A1—C9A—H9A2	109.5
C2A—Ti1—C1A	34.0 (5)	C4A—C9A—H9A3	109.5
C1—Ti1—C1A	13.8 (4)	H9A1—C9A—H9A3	109.5
C3—Ti1—C1A	54.9 (6)	H9A2—C9A—H9A3	109.5
O1—Ti1—C5A	143.9 (5)	C5A—C10A—H10D	109.5
O2—Ti1—C5A	104.6 (6)	C5A—C10A—H10E	109.5
O3—Ti1—C5A	92.2 (5)	H10D—C10A—H10E	109.5
C3A—Ti1—C5A	58.2 (8)	C5A—C10A—H10F	109.5
C4A—Ti1—C5A	35.2 (4)	H10D—C10A—H10F	109.5
C2—Ti1—C5A	50.5 (5)	H10E—C10A—H10F	109.5
C4—Ti1—C5A	47.2 (5)	O2—C11—C16	122.5 (3)
C2A—Ti1—C5A	56.4 (7)	O2—C11—C12	121.9 (3)
C1—Ti1—C5A	20.7 (5)	C16—C11—C12	115.6 (2)
C3—Ti1—C5A	61.3 (5)	F5—C12—C13	119.0 (3)
C1A—Ti1—C5A	34.3 (5)	F5—C12—C11	119.3 (3)
Ti1—O1—Ti1ⁱ	180.00 (4)	C13—C12—C11	121.7 (3)
C11—O2—Ti1	172.0 (2)	F4—C13—C14	119.4 (3)
C17—O3—Ti1	162.14 (19)	F4—C13—C12	120.0 (3)
C2—C1—C5	108.2 (4)	C14—C13—C12	120.6 (3)
C2—C1—C6	125.0 (9)	F3—C14—C15	120.3 (3)
C5—C1—C6	126.7 (8)	F3—C14—C13	120.1 (3)
C2—C1—Ti1	71.6 (4)	C15—C14—C13	119.6 (3)
C5—C1—Ti1	73.7 (3)	F2—C15—C14	120.1 (3)
C6—C1—Ti1	120.8 (5)	F2—C15—C16	119.5 (3)
C1—C2—C3	108.5 (5)	C14—C15—C16	120.3 (3)
C1—C2—C7	127.7 (9)	F1—C16—C15	118.8 (3)
C3—C2—C7	123.7 (9)	F1—C16—C11	119.1 (3)
C1—C2—Ti1	73.9 (4)	C15—C16—C11	122.2 (3)
C3—C2—Ti1	73.9 (5)	O3—C17—C22	122.4 (3)
C7—C2—Ti1	120.9 (5)	O3—C17—C18	121.9 (3)
C4—C3—C2	107.7 (5)	C22—C17—C18	115.7 (2)
C4—C3—C8	125.3 (8)	F6—C18—C19	118.4 (3)
C2—C3—C8	127.0 (9)	F6—C18—C17	119.6 (2)
C4—C3—Ti1	72.5 (4)	C19—C18—C17	122.0 (3)
C2—C3—Ti1	71.5 (5)	F7—C19—C20	119.6 (3)
C8—C3—Ti1	121.9 (6)	F7—C19—C18	120.2 (3)
C3—C4—C5	108.5 (5)	C20—C19—C18	120.2 (3)
C3—C4—C9	125.4 (7)	F8—C20—C21	120.2 (3)
C5—C4—C9	126.1 (7)	F8—C20—C19	120.1 (3)
C3—C4—Ti1	73.2 (5)	C21—C20—C19	119.7 (3)
C5—C4—Ti1	73.9 (3)	F9—C21—C20	119.8 (3)
C9—C4—Ti1	120.9 (3)	F9—C21—C22	120.4 (3)
C1—C5—C4	107.0 (4)	C20—C21—C22	119.8 (3)
C1—C5—C10	126.4 (7)	F10—C22—C21	118.7 (3)
C4—C5—C10	126.5 (7)	F10—C22—C17	118.6 (3)
C1—C5—Ti1	71.9 (3)	C21—C22—C17	122.7 (3)
C4—C5—Ti1	71.4 (3)

Symmetry code: (i) −x, −y, −z.

Experimental details

Crystal data
Chemical formula	[Ti₂(C₁₀H₁₅)₂(C₆F₅O)₄O]
M_r	1114.48
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.7472 (17), 11.823 (2), 12.923 (3)
α, β, γ (°)	112.00 (3), 109.24 (3), 97.36 (3)
V (Å³)	1120.6 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART 1K CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.94, 0.96
No. of measured, independent and observed [I > 2σ(I)] reflections	12962, 5069, 3892
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.141, 1.03
No. of reflections	5069
No. of parameters	423
No. of restraints	49
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.34

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by a research grant from Chungbuk National University in 2011.

References

Bruker (2004). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Gowik, P., Klaotke, T. & Pickardt, J. (1990). J. Organomet. Chem. 393, 343–348. CSD CrossRef CAS Web of Science Google Scholar
Lee, J., Do, Y. & Kim, Y. (2007). J. Organomet. Chem. 692, 3593–3598. Web of Science CSD CrossRef CAS Google Scholar
Lee, J. & Kim, Y. (2011). Acta Cryst. E67, m1104. Web of Science CSD CrossRef IUCr Journals Google Scholar
Noh, S. K., Jung, W., Oh, H., Lee, Y. R. & Lyoo, W. S. (2006). J. Organomet. Chem. 691, 5000–5006. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Thewalt, U. & Schomburg, D. (1977). J. Organomet. Chem. 127, 169–174. CSD CrossRef CAS Web of Science Google Scholar
Wu, Q.-L., Li, G.-H., Ye, L., Gao, W. & Mu, Y. (2007). Polyhedron, 26, 3063–3068. Web of Science CSD CrossRef CAS Google Scholar
Yoon, S.W., Kim, Y., Kim, S.K., Kim, S.Y., Do, Y. & Park, S. (2011). Macromol. Chem. Phys. 212, 785–789. Web of Science CSD CrossRef CAS Google Scholar

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