{N,N-Bis[bis­(2,2,2-tri­fluoro­eth­oxy)phosphan­yl]methyl­amine-κ2P,P′}bis­(η5-cyclo­penta­dien­yl)titanium(II)

Haehnel, M.; Hansen, S.; Spannenberg, A.; Beweries, T.

doi:10.1107/S1600536813014244

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page m346

doi:10.1107/S1600536813014244

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{N,N-Bis[bis(2,2,2-trifluoroethoxy)phosphanyl]methylamine-κ²P,P′}bis(η⁵-cyclopentadienyl)titanium(II)

Martin Haehnel,^a Sven Hansen,^a Anke Spannenberg ^a and Torsten Beweries ^a ^*

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

(Received 21 May 2013; accepted 22 May 2013; online 31 May 2013)

The title compound, [Ti(C₅H₅)₂(C₉H₁₁F₁₂NO₄P₂)], is a four-membered titanacycle obtained from the reaction of Cp₂Ti(η²-Me₃SiC₂SiMe₃) and CH₃N[P(OCH₂CF₃)₂]₂ {N,N-bis[bis(trifluoroethoxy)phosphanyl]methylamine, tfepma}. The Ti^II atom is coordinated by two cyclopentadienyl (Cp) ligands and the chelating tfepma ligand in a strongly distorted tetrahedral geometry. The molecule is located on a mirror plane.

Related literature

For other titanocene complexes with four-membered metallacycles [TiPNP], see: Haehnel et al. (2012 ). For selected examples of four-membered metallacycles with a chelating tfepma ligand, see: M = Rh, Esswein et al. (2005 , 2007 ); M = Ir, Heyduk & Nocera (1999 , 2000 ); Gray et al. (2004 ); Veige et al. (2005 ); Esswein et al. (2008 ). The starting alkyne complex Cp₂Ti(η²-Me₃SiC₂SiMe₃) is described by Burlakov et al. (1988 ).

Experimental

Crystal data

[Ti(C₅H₅)₂(C₉H₁₁F₁₂NO₄P₂)]
M_r = 665.21
Orthorhombic, P n m a
a = 14.6494 (2) Å
b = 20.0535 (3) Å
c = 8.7694 (1) Å
V = 2576.20 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.57 mm⁻¹
T = 150 K
0.42 × 0.41 × 0.16 mm

Data collection

Bruker Kappa APEXII DUO diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.90, T_max = 1.00
60903 measured reflections
3420 independent reflections
2988 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.079
S = 1.06
3420 reflections
191 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ); cell refinement: SAINT (Bruker, 2009 ); data reduction: SAINT; 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813014244/bt6910sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813014244/bt6910Isup2.hkl

checkCIF report

Comment top

The reaction of tfepma with the titanocene precursor Cp₂Ti(η²-Me₃SiC₂SiMe₃) was investigated to synthesize a new 4-membered hetero-metallacycle. In this reaction, the spectator ligand Me₃SiC₂SiMe₃ is replaced by the chelating tfepma ligand, which is binding over both phosphorus atoms to result in the four membered metallacycle.

In the title compound the titanium center is coordinated by two Cp units and the chelating tfepma ligand (Fig. 1). The molecule is located on a mirror plane which passes through H5A, C5, N1, Ti1, C7, H7, C11 and H11. The geometry at the titanium center is found to be strongly distorted tetrahedral. The largest deviation from the ideal tetrahedral angle is observed for P1—Ti1—P1ⁱ [63.94 (2)°, symmetry code to generate equivalent atoms: (i) x, -y + 1/2, z]. The four membered metallacycle Ti1,P1,N1,P1ⁱ is planar with a mean deviation from the best plane of 0.015 Å. The following bond lengths and angles of the cyclic unit were observed: Ti1—P1 = 2.4266 (4) Å, P1—N1 = 1.696 (1) Å, P1—N1—P1ⁱ = 98.51 (8)°.

Related literature top

For other titanocene complexes with four-membered metallacycles [TiPNP], see: Haehnel et al. (2012). For selected examples of four-membered metallacycles with a chelating tfepma ligand, see: M = Rh, Esswein et al. (2005, 2007); M = Ir, Heyduk & Nocera (1999, 2000); Gray et al. (2004); Veige et al. (2005); Esswein et al. (2008). The starting alkyne complex Cp₂Ti(η²-Me₃SiC₂SiMe₃) is described by Burlakov et al. (1988).

Experimental top

To a stirred solution of Cp₂Ti(η²-Me₃SiC₂SiMe₃) (150 mg, 0.430 mmol) in 5 ml of toluene was added a solution of tfepma (210 mg, 0.430 mmol) in 5 ml of toluene at room temperature. The colour of the reaction mixture instantly changed from brown to dark green. After additional stirring for 1 h, all volatiles were removed in vacuum and the resulting green precipitate was dissolved in 7 ml of toluene and stored at -30°C for several weeks. The resulting dark green single crystals were filtered, washed with cold n-hexane and dried in vacuum. Yield: 96% (274 mg, 0.412 mmol).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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. The molecular structure of the title compound in the crystal (symmetry code to generate equivalent atoms: (i) x, -y + 1/2, z). Hydrogen atoms are omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level.

{N,N-Bis[bis(2,2,2-trifluoroethoxy)phosphanyl]methylamine-κ²P,P'}bis(η⁵-cyclopentadienyl)titanium(II) top

Crystal data top

[Ti(C₅H₅)₂(C₉H₁₁F₁₂NO₄P₂)]	D_x = 1.715 Mg m⁻³
M_r = 665.21	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 9979 reflections
a = 14.6494 (2) Å	θ = 2.5–28.6°
b = 20.0535 (3) Å	µ = 0.57 mm⁻¹
c = 8.7694 (1) Å	T = 150 K
V = 2576.20 (6) Å³	Prism, dark green
Z = 4	0.42 × 0.41 × 0.16 mm
F(000) = 1336

Data collection top

Bruker Kappa APEXII DUO diffractometer	3420 independent reflections
Radiation source: fine-focus sealed tube	2988 reflections with I > 2σ(I)
Curved graphite monochromator	R_int = 0.033
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.7°, θ_min = 2.5°
ω and phi scans	h = −19→19
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −27→24
T_min = 0.90, T_max = 1.00	l = −11→11
60903 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0339P)² + 1.9223P] where P = (F_o² + 2F_c²)/3
3420 reflections	(Δ/σ)_max = 0.001
191 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

[Ti(C₅H₅)₂(C₉H₁₁F₁₂NO₄P₂)]	V = 2576.20 (6) Å³
M_r = 665.21	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 14.6494 (2) Å	µ = 0.57 mm⁻¹
b = 20.0535 (3) Å	T = 150 K
c = 8.7694 (1) Å	0.42 × 0.41 × 0.16 mm

Data collection top

Bruker Kappa APEXII DUO diffractometer	3420 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2988 reflections with I > 2σ(I)
T_min = 0.90, T_max = 1.00	R_int = 0.033
60903 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.51 e Å⁻³
3420 reflections	Δρ_min = −0.40 e Å⁻³
191 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	0.92098 (11)	0.13133 (8)	0.72113 (17)	0.0261 (3)
H1A	0.9235	0.1703	0.6520	0.031*
H1B	0.8574	0.1259	0.7574	0.031*
C2	0.95209 (12)	0.06964 (8)	0.63952 (18)	0.0296 (3)
C3	0.88445 (11)	0.07502 (8)	1.1082 (2)	0.0310 (4)
H3A	0.9098	0.0719	1.2126	0.037*
H3B	0.9278	0.0537	1.0367	0.037*
C4	0.79412 (13)	0.04136 (9)	1.1005 (2)	0.0379 (4)
C5	0.79887 (14)	0.2500	0.8632 (3)	0.0228 (4)
H5A	0.8034 (17)	0.2500	0.752 (3)	0.023 (6)*
H5B	0.7653 (14)	0.2887 (10)	0.897 (2)	0.033 (5)*
C6	1.01942 (18)	0.19336 (12)	1.3387 (2)	0.0528 (6)
H6	0.9998	0.1483	1.3320	0.063*
C7	0.9650 (2)	0.2500	1.3137 (3)	0.0561 (9)
H7	0.9025	0.2500	1.2850	0.067*
C8	1.10686 (16)	0.28522 (10)	1.3748 (2)	0.0437 (5)
H8	1.1578	0.3131	1.3959	0.052*
C9	1.22452 (11)	0.21453 (9)	1.0707 (3)	0.0404 (5)
H9	1.2574	0.1868	1.1392	0.049*
C10	1.16817 (10)	0.19273 (8)	0.9531 (2)	0.0336 (4)
H10	1.1565	0.1476	0.9265	0.040*
C11	1.13093 (15)	0.2500	0.8793 (3)	0.0292 (5)
H11	1.0891	0.2500	0.7964	0.035*
F1	0.94470 (9)	0.01516 (5)	0.72635 (13)	0.0447 (3)
F2	1.03855 (8)	0.07332 (6)	0.59488 (13)	0.0441 (3)
F3	0.90112 (9)	0.05987 (6)	0.51500 (12)	0.0455 (3)
F4	0.80238 (10)	−0.02315 (5)	1.13574 (17)	0.0569 (4)
F5	0.73432 (10)	0.06669 (6)	1.1954 (2)	0.0734 (5)
F6	0.75798 (12)	0.04567 (8)	0.96213 (19)	0.0813 (5)
N1	0.89119 (11)	0.2500	0.93043 (19)	0.0167 (3)
O1	0.98087 (7)	0.14063 (5)	0.84642 (12)	0.0253 (2)
O2	0.87059 (7)	0.14299 (5)	1.06745 (13)	0.0239 (2)
P1	0.95613 (2)	0.185927 (17)	0.99495 (4)	0.01645 (9)
Ti1	1.07370 (2)	0.2500	1.12354 (4)	0.01905 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0296 (7)	0.0269 (7)	0.0217 (7)	0.0021 (6)	−0.0017 (6)	−0.0068 (6)
C2	0.0402 (9)	0.0244 (7)	0.0242 (7)	−0.0003 (6)	0.0027 (6)	−0.0049 (6)
C3	0.0308 (8)	0.0214 (7)	0.0409 (9)	−0.0025 (6)	−0.0028 (7)	0.0091 (7)
C4	0.0424 (10)	0.0239 (8)	0.0473 (10)	−0.0106 (7)	0.0011 (8)	0.0034 (7)
C5	0.0146 (9)	0.0275 (11)	0.0263 (10)	0.000	−0.0043 (8)	0.000
C6	0.0838 (16)	0.0552 (13)	0.0192 (8)	−0.0323 (12)	−0.0119 (9)	0.0102 (8)
C7	0.0390 (15)	0.113 (3)	0.0162 (11)	0.000	0.0021 (10)	0.000
C8	0.0644 (13)	0.0359 (10)	0.0308 (9)	−0.0074 (9)	−0.0247 (9)	−0.0022 (7)
C9	0.0156 (7)	0.0351 (9)	0.0707 (13)	0.0046 (6)	−0.0038 (8)	0.0044 (9)
C10	0.0183 (7)	0.0251 (8)	0.0573 (11)	0.0015 (6)	0.0114 (7)	−0.0044 (7)
C11	0.0196 (9)	0.0327 (11)	0.0354 (12)	0.000	0.0116 (9)	0.000
F1	0.0710 (8)	0.0228 (5)	0.0403 (6)	−0.0047 (5)	0.0008 (6)	0.0001 (4)
F2	0.0448 (6)	0.0437 (6)	0.0437 (6)	0.0072 (5)	0.0161 (5)	−0.0106 (5)
F3	0.0649 (8)	0.0431 (6)	0.0285 (5)	−0.0021 (6)	−0.0079 (5)	−0.0152 (5)
F4	0.0704 (8)	0.0208 (5)	0.0794 (9)	−0.0123 (5)	0.0114 (7)	0.0060 (6)
F5	0.0586 (8)	0.0395 (7)	0.1222 (13)	−0.0053 (6)	0.0509 (9)	0.0120 (8)
F6	0.0961 (12)	0.0685 (10)	0.0791 (10)	−0.0436 (9)	−0.0491 (9)	0.0132 (8)
N1	0.0136 (7)	0.0184 (7)	0.0180 (7)	0.000	−0.0020 (6)	0.000
O1	0.0226 (5)	0.0269 (5)	0.0263 (5)	0.0036 (4)	−0.0020 (4)	−0.0097 (4)
O2	0.0197 (5)	0.0187 (5)	0.0335 (6)	−0.0029 (4)	0.0012 (4)	0.0048 (4)
P1	0.01472 (15)	0.01642 (16)	0.01822 (16)	−0.00044 (12)	−0.00029 (12)	−0.00094 (12)
Ti1	0.01473 (16)	0.01974 (17)	0.02269 (18)	0.000	−0.00488 (13)	0.000

Geometric parameters (Å, º) top

C1—O1	1.4183 (18)	C8—C8ⁱ	1.413 (4)
C1—C2	1.500 (2)	C8—Ti1	2.3644 (18)
C1—H1A	0.9900	C8—H8	0.9500
C1—H1B	0.9900	C9—C10	1.392 (3)
C2—F2	1.328 (2)	C9—C9ⁱ	1.422 (4)
C2—F1	1.3360 (19)	C9—Ti1	2.3670 (17)
C2—F3	1.3374 (19)	C9—H9	0.9500
C3—O2	1.4235 (18)	C10—C11	1.427 (2)
C3—C4	1.487 (2)	C10—Ti1	2.3387 (17)
C3—H3A	0.9900	C10—H10	0.9500
C3—H3B	0.9900	C11—C10ⁱ	1.427 (2)
C4—F5	1.311 (2)	C11—Ti1	2.300 (2)
C4—F6	1.327 (2)	C11—H11	0.9500
C4—F4	1.336 (2)	N1—P1ⁱ	1.6959 (11)
C5—N1	1.475 (2)	N1—P1	1.6959 (11)
C5—H5A	0.98 (3)	O1—P1	1.6287 (11)
C5—H5B	0.97 (2)	O2—P1	1.6481 (10)
C6—C8ⁱ	1.388 (3)	P1—Ti1	2.4266 (4)
C6—C7	1.405 (3)	P1—P1ⁱ	2.5697 (7)
C6—Ti1	2.3412 (19)	Ti1—C10ⁱ	2.3387 (17)
C6—H6	0.9500	Ti1—C6ⁱ	2.3412 (19)
C7—C6ⁱ	1.405 (3)	Ti1—C8ⁱ	2.3644 (18)
C7—Ti1	2.305 (3)	Ti1—C9ⁱ	2.3670 (17)
C7—H7	0.9500	Ti1—P1ⁱ	2.4266 (4)
C8—C6ⁱ	1.388 (3)

O1—C1—C2	106.86 (13)	O2—P1—Ti1	129.57 (4)
O1—C1—H1A	110.3	N1—P1—Ti1	98.74 (4)
C2—C1—H1A	110.3	O1—P1—P1ⁱ	123.89 (4)
O1—C1—H1B	110.3	O2—P1—P1ⁱ	121.50 (4)
C2—C1—H1B	110.3	Ti1—P1—P1ⁱ	58.029 (9)
H1A—C1—H1B	108.6	C11—Ti1—C7	157.70 (10)
F2—C2—F1	106.91 (14)	C11—Ti1—C10	35.81 (6)
F2—C2—F3	107.46 (13)	C7—Ti1—C10	150.58 (4)
F1—C2—F3	107.48 (14)	C11—Ti1—C10ⁱ	35.81 (6)
F2—C2—C1	112.62 (14)	C7—Ti1—C10ⁱ	150.58 (4)
F1—C2—C1	112.20 (13)	C10—Ti1—C10ⁱ	58.82 (8)
F3—C2—C1	109.92 (14)	C11—Ti1—C6ⁱ	150.94 (6)
O2—C3—C4	107.24 (14)	C7—Ti1—C6ⁱ	35.18 (8)
O2—C3—H3A	110.3	C10—Ti1—C6ⁱ	162.62 (7)
C4—C3—H3A	110.3	C10ⁱ—Ti1—C6ⁱ	118.54 (8)
O2—C3—H3B	110.3	C11—Ti1—C6	150.94 (6)
C4—C3—H3B	110.3	C7—Ti1—C6	35.18 (8)
H3A—C3—H3B	108.5	C10—Ti1—C6	118.54 (8)
F5—C4—F6	106.78 (19)	C10ⁱ—Ti1—C6	162.61 (7)
F5—C4—F4	106.79 (15)	C6ⁱ—Ti1—C6	58.05 (12)
F6—C4—F4	108.12 (16)	C11—Ti1—C8ⁱ	142.46 (8)
F5—C4—C3	112.95 (16)	C7—Ti1—C8ⁱ	57.85 (9)
F6—C4—C3	111.54 (16)	C10—Ti1—C8ⁱ	109.11 (7)
F4—C4—C3	110.41 (16)	C10ⁱ—Ti1—C8ⁱ	128.38 (8)
N1—C5—H5A	109.7 (15)	C6ⁱ—Ti1—C8ⁱ	57.57 (7)
N1—C5—H5B	110.2 (12)	C6—Ti1—C8ⁱ	34.30 (8)
H5A—C5—H5B	109.9 (14)	C11—Ti1—C8	142.46 (8)
C8ⁱ—C6—C7	108.0 (2)	C7—Ti1—C8	57.85 (9)
C8ⁱ—C6—Ti1	73.76 (12)	C10—Ti1—C8	128.38 (8)
C7—C6—Ti1	71.01 (13)	C10ⁱ—Ti1—C8	109.11 (7)
C8ⁱ—C6—H6	126.0	C6ⁱ—Ti1—C8	34.30 (8)
C7—C6—H6	126.0	C6—Ti1—C8	57.57 (7)
Ti1—C6—H6	121.0	C8ⁱ—Ti1—C8	34.76 (9)
C6ⁱ—C7—C6	107.9 (3)	C11—Ti1—C9	58.49 (8)
C6ⁱ—C7—Ti1	73.80 (14)	C7—Ti1—C9	141.84 (8)
C6—C7—Ti1	73.80 (14)	C10—Ti1—C9	34.39 (7)
C6ⁱ—C7—H7	126.0	C10ⁱ—Ti1—C9	57.99 (6)
C6—C7—H7	126.0	C6ⁱ—Ti1—C9	128.36 (8)
Ti1—C7—H7	118.3	C6—Ti1—C9	109.21 (9)
C6ⁱ—C8—C8ⁱ	108.03 (13)	C8ⁱ—Ti1—C9	84.32 (8)
C6ⁱ—C8—Ti1	71.93 (10)	C8—Ti1—C9	94.62 (8)
C8ⁱ—C8—Ti1	72.62 (5)	C11—Ti1—C9ⁱ	58.49 (8)
C6ⁱ—C8—H8	126.0	C7—Ti1—C9ⁱ	141.84 (8)
C8ⁱ—C8—H8	126.0	C10—Ti1—C9ⁱ	57.99 (6)
Ti1—C8—H8	121.2	C10ⁱ—Ti1—C9ⁱ	34.39 (7)
C10—C9—C9ⁱ	108.31 (10)	C6ⁱ—Ti1—C9ⁱ	109.21 (9)
C10—C9—Ti1	71.69 (9)	C6—Ti1—C9ⁱ	128.36 (8)
C9ⁱ—C9—Ti1	72.51 (4)	C8ⁱ—Ti1—C9ⁱ	94.62 (8)
C10—C9—H9	125.8	C8—Ti1—C9ⁱ	84.32 (8)
C9ⁱ—C9—H9	125.8	C9—Ti1—C9ⁱ	34.97 (9)
Ti1—C9—H9	121.7	C11—Ti1—P1ⁱ	79.98 (5)
C9—C10—C11	108.07 (16)	C7—Ti1—P1ⁱ	81.14 (6)
C9—C10—Ti1	73.91 (10)	C10—Ti1—P1ⁱ	112.52 (5)
C11—C10—Ti1	70.63 (11)	C10ⁱ—Ti1—P1ⁱ	82.12 (4)
C9—C10—H10	126.0	C6ⁱ—Ti1—P1ⁱ	82.91 (5)
C11—C10—H10	126.0	C6—Ti1—P1ⁱ	112.97 (7)
Ti1—C10—H10	121.2	C8ⁱ—Ti1—P1ⁱ	137.48 (6)
C10—C11—C10ⁱ	107.2 (2)	C8—Ti1—P1ⁱ	114.88 (5)
C10—C11—Ti1	73.56 (12)	C9—Ti1—P1ⁱ	136.94 (6)
C10ⁱ—C11—Ti1	73.56 (12)	C9ⁱ—Ti1—P1ⁱ	114.36 (5)
C10—C11—H11	126.4	C11—Ti1—P1	79.98 (5)
C10ⁱ—C11—H11	126.4	C7—Ti1—P1	81.14 (6)
Ti1—C11—H11	118.5	C10—Ti1—P1	82.12 (4)
C5—N1—P1ⁱ	130.36 (4)	C10ⁱ—Ti1—P1	112.52 (5)
C5—N1—P1	130.36 (4)	C6ⁱ—Ti1—P1	112.97 (7)
P1ⁱ—N1—P1	98.51 (8)	C6—Ti1—P1	82.91 (5)
C1—O1—P1	123.73 (9)	C8ⁱ—Ti1—P1	114.88 (5)
C3—O2—P1	119.25 (10)	C8—Ti1—P1	137.48 (6)
O1—P1—O2	100.73 (6)	C9—Ti1—P1	114.35 (5)
O1—P1—N1	106.29 (7)	C9ⁱ—Ti1—P1	136.94 (6)
O2—P1—N1	95.62 (6)	P1ⁱ—Ti1—P1	63.942 (18)
O1—P1—Ti1	120.60 (4)

Symmetry code: (i) x, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	[Ti(C₅H₅)₂(C₉H₁₁F₁₂NO₄P₂)]
M_r	665.21
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	150
a, b, c (Å)	14.6494 (2), 20.0535 (3), 8.7694 (1)
V (Å³)	2576.20 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.57
Crystal size (mm)	0.42 × 0.41 × 0.16

Data collection
Diffractometer	Bruker Kappa APEXII DUO diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.90, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	60903, 3420, 2988
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.079, 1.06
No. of reflections	3420
No. of parameters	191
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.40

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

Financial support by the DFG (grant code RO 1269/8-1) and the BMBF (project "Light2Hydrogen") is gratefully acknowledged.

References

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