{N,N-Bis[bis-(2,2,2-tri-fluoro-eth-oxy)phosphan-yl]methyl-amine-κ(2) P,P'}bis-(η(5)-cyclo-penta-dien-yl)titanium(II).

The title compound, [Ti(C5H5)2(C9H11F12NO4P2)], is a four-membered titanacycle obtained from the reaction of Cp2Ti(η(2)-Me3SiC2SiMe3) and CH3N[P(OCH2CF3)2]2 {N,N-bis-[bis-(tri-fluoro-eth-oxy)phosphan-yl]methyl-amine, tfepma}. The Ti(II) atom is coordinated by two cyclo-penta-dienyl (Cp) ligands and the chelating tfepma ligand in a strongly distorted tetra-hedral geometry. The mol-ecule 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 = 665.21

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.079

S = 1.06

3420 reflections

191 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −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.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813014244/bt6910sup1.cif

Click here for additional data file.

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ti(C5H5)2(C9H11F12NO4P2)]	Dx = 1.715 Mg m−3
Mr = 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

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

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(Fo2) + (0.0339P)2 + 1.9223P] where P = (Fo2 + 2Fc2)/3
3420 reflections	(Δ/σ)max = 0.001
191 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.40 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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

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)