Dichloridobis{N-[(dimethyl­amino)dimethyl­silyl]-2,6-dimethyl­anilido-κ2N,N′}zirconium(IV)

Chen, J.

doi:10.1107/S1600536809039804

metal-organic compounds

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Volume 65| Part 11| November 2009| Page m1307

https://doi.org/10.1107/S1600536809039804

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Dichloridobis{N-[(dimethylamino)dimethylsilyl]-2,6-dimethylanilido-κ²N,N′}zirconium(IV)

Juan Chen ^a ^*

^aDepartment of Chemistry, Taiyuan Teachers College, Taiyuan 030031, People's Republic of China
^*Correspondence e-mail: sdbai@sxu.edu.cn

(Received 10 September 2009; accepted 30 September 2009; online 7 October 2009)

The monomeric title zirconium(IV) compound, [Zr(C₁₂H₂₁N₂Si)₂Cl₂], was prepared by the metathetical reaction of [LiN(SiMe₂NMe₂)(2,6-Me₂C₆H₃)]₂ with zirconium tetrachloride. The Zr^IV atom is N,N′-chelated by the N-silylated anilido ligand. Along with two Cl atoms, the six-coordinated Zr^IV atom demonstrates a highly distorted octahedral geometry. The two ligands around the Zr^IV atom are arranged cis to each other and obey the C₂ symmetry operation. That means the asymmetric unit consists of only half of the molecular compound and the complete molecule is generated by a twofold axis. The two ends of the N—Si—N chelating unit exhibit different affinities for the metal center. The Zr—N_amino bond is longer than the Zr—N_anilido bond.

Related literature

For the catalytic applications of related N-silylated analido group 4 metal compounds towards olefin polymerization, see: Gibson et al. (1998 ); Hill & Hitchcock (2002 ). For related organometallic compounds supported with analogous analido ligands, see: Schumann et al. (2000 ); Chen et al. (2007 ); Ferreira et al. (2007 ); Chen (2008 ).

Experimental

Crystal data

[Zr(C₁₂H₂₁N₂Si)₂Cl₂]
M_r = 604.92
Monoclinic, C 2/c
a = 16.179 (2) Å
b = 10.257 (2) Å
c = 18.779 (4) Å
β = 112.234 (4)°
V = 2884.6 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.67 mm⁻¹
T = 203 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.757, T_max = 0.878
6014 measured reflections
2548 independent reflections
2448 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.120
S = 1.20
2548 reflections
151 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Table 1
Selected bond lengths (Å)

Zr1—N1	2.119 (3)
Zr1—N2	2.439 (3)
Zr1—Cl1	2.4676 (11)

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809039804/vm2005sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809039804/vm2005Isup2.hkl

checkCIF report

Comment top

Group 4 metal amides supported with the N-silylated anilido ligands were active catalysts for olefin polymerization (Gibson et al., 1998; Hill & Hitchcock, 2002). The N-silylated anilido ligand in the title compound has a pendant amino group. It results in an N—Si—N chelating moiety, which is presumed to be a "quasi" conjugated unit owing to d–π interaction between Si and N atoms. The zinc compound coordinated with the analogous ligand has been reported by Schumann et al. (2000). The title compound is monomeric and contains two N-silylated anilido ligands, which give the N—Zr—N bite angle of 67.63° and are arranged cis to each other and obey the C₂ symmetrical operation. That means the asymmetric unit consists of only half of the molecular compound and the complete molecule is generated by a twofold axis. The Zr^IV atom is situated in the plane defined by atoms N1, N2A and Cl1, and the symmetrical counterparts. Both planes are perpendicular to each other resulting in a highly distorted octahedral geometry. Two ends of the N—Si—N chelating unit exhibit different affinity to the metal center. The Zr—N_anilido bond is 2.119 Å and the Zr—N_amino bond is 2.439 Å, suggesting the former is much tighter than the latter.

Related literature top

For the catalytic applications of related N-silylated analido group 4 metal compounds towards olefin polymerization, see: Gibson et al. (1998); Hill & Hitchcock (2002). For related organometallic compounds supported with analogous analido ligands, see: Schumann et al. (2000); Chen et al. (2007); Ferreira et al. (2007); Chen (2008).

Experimental top

ZrCl₄ (0.47 g, 2.03 mmol) was added into the solution of [LiN(SiMe₂NMe₂)(2,6-Me₂C₆H₃)]₂ (0.92 g, 2.03 mmol) in Et₂O (30 ml) at 273 K. The reaction mixture was warmed to room temperature and kept stirring for 12 h. It was dried in vacuum to remove all volatiles and the residue was extracted with CH₂Cl₂ (30 ml). Concentration of the filtrate under reduced pressure gave the title compound as colorless crystals (yield 0.92 g, 75%).

Structure description top

For the catalytic applications of related N-silylated analido group 4 metal compounds towards olefin polymerization, see: Gibson et al. (1998); Hill & Hitchcock (2002). For related organometallic compounds supported with analogous analido ligands, see: Schumann et al. (2000); Chen et al. (2007); Ferreira et al. (2007); Chen (2008).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogens omitted for clarity. Symmetry codes: (i) -x, y, -z + 1/2.

Dichloridobis{N-[(dimethylamino)dimethylsilyl]-2,6-dimethylanilido- κ²N,N'}zirconium(IV) top

Crystal data top

[Zr(C₁₂H₂₁N₂Si)₂Cl₂]	F(000) = 1264
M_r = 604.92	D_x = 1.393 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3803 reflections
a = 16.179 (2) Å	θ = 2.3–27.1°
b = 10.257 (2) Å	µ = 0.67 mm⁻¹
c = 18.779 (4) Å	T = 203 K
β = 112.234 (4)°	Block, colorless
V = 2884.6 (9) Å³	0.20 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART area-detector diffractometer	2548 independent reflections
Radiation source: fine-focus sealed tube	2448 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −19→19
T_min = 0.757, T_max = 0.878	k = −12→12
6014 measured reflections	l = −18→22

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.20	w = 1/[σ²(F_o²) + (0.0465P)² + 9.9576P] where P = (F_o² + 2F_c²)/3
2548 reflections	(Δ/σ)_max < 0.001
151 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.53 e Å⁻³

Crystal data top

[Zr(C₁₂H₂₁N₂Si)₂Cl₂]	V = 2884.6 (9) Å³
M_r = 604.92	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 16.179 (2) Å	µ = 0.67 mm⁻¹
b = 10.257 (2) Å	T = 203 K
c = 18.779 (4) Å	0.20 × 0.20 × 0.20 mm
β = 112.234 (4)°

Data collection top

Bruker SMART area-detector diffractometer	2548 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2448 reflections with I > 2σ(I)
T_min = 0.757, T_max = 0.878	R_int = 0.027
6014 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.20	Δρ_max = 0.52 e Å⁻³
2548 reflections	Δρ_min = −0.53 e Å⁻³
151 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
Zr1	0.0000	0.26497 (5)	0.2500	0.02462 (18)
Si1	−0.03902 (7)	0.19837 (11)	0.39184 (6)	0.0297 (3)
Cl1	−0.10371 (7)	0.42525 (10)	0.16362 (7)	0.0427 (3)
N1	0.01144 (19)	0.1249 (3)	0.33620 (17)	0.0249 (7)
N2	−0.0992 (2)	0.3112 (3)	0.3175 (2)	0.0337 (8)
C1	0.0574 (2)	0.0027 (3)	0.3583 (2)	0.0236 (8)
C2	0.1508 (2)	−0.0007 (4)	0.3993 (2)	0.0278 (8)
C3	0.1939 (3)	−0.1203 (4)	0.4175 (2)	0.0325 (9)
H3A	0.2562	−0.1222	0.4439	0.039*
C4	0.1478 (3)	−0.2359 (4)	0.3977 (2)	0.0345 (9)
H4A	0.1782	−0.3159	0.4099	0.041*
C5	0.0562 (3)	−0.2329 (4)	0.3598 (2)	0.0330 (9)
H5A	0.0245	−0.3118	0.3468	0.040*
C6	0.0100 (2)	−0.1158 (4)	0.3404 (2)	0.0265 (8)
C7	0.2058 (3)	0.1209 (4)	0.4260 (3)	0.0416 (11)
H7A	0.2680	0.0974	0.4527	0.062*
H7B	0.1851	0.1688	0.4607	0.062*
H7C	0.1998	0.1750	0.3820	0.062*
C8	−0.0900 (2)	−0.1221 (4)	0.3002 (2)	0.0314 (9)
H8A	−0.1059	−0.1936	0.2636	0.047*
H8B	−0.1118	−0.0409	0.2731	0.047*
H8C	−0.1169	−0.1360	0.3378	0.047*
C9	−0.1136 (3)	0.0973 (4)	0.4237 (3)	0.0404 (10)
H9A	−0.0987	0.1103	0.4783	0.061*
H9B	−0.1059	0.0061	0.4140	0.061*
H9C	−0.1752	0.1225	0.3955	0.061*
C10	0.0358 (3)	0.2854 (5)	0.4793 (3)	0.0458 (11)
H10A	0.0207	0.2609	0.5229	0.069*
H10B	0.0284	0.3787	0.4711	0.069*
H10C	0.0974	0.2618	0.4897	0.069*
C11	−0.1893 (3)	0.2614 (5)	0.2688 (3)	0.0478 (12)
H11A	−0.2305	0.2784	0.2941	0.072*
H11D	−0.1860	0.1683	0.2613	0.072*
H11C	−0.2100	0.3051	0.2194	0.072*
C12	−0.1088 (4)	0.4470 (5)	0.3400 (3)	0.0536 (13)
H12B	−0.1503	0.4492	0.3661	0.080*
H12C	−0.1312	0.5013	0.2944	0.080*
H12A	−0.0511	0.4794	0.3742	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.0262 (3)	0.0198 (3)	0.0309 (3)	0.000	0.0142 (2)	0.000
Si1	0.0310 (6)	0.0305 (6)	0.0303 (6)	0.0019 (4)	0.0148 (5)	−0.0011 (4)
Cl1	0.0491 (6)	0.0310 (6)	0.0538 (7)	0.0120 (5)	0.0259 (6)	0.0139 (5)
N1	0.0206 (15)	0.0262 (17)	0.0273 (17)	0.0006 (12)	0.0086 (13)	−0.0026 (13)
N2	0.0347 (19)	0.0300 (19)	0.041 (2)	0.0072 (15)	0.0194 (16)	0.0046 (15)
C1	0.0258 (18)	0.0221 (19)	0.0225 (18)	0.0028 (15)	0.0086 (15)	−0.0003 (15)
C2	0.0254 (19)	0.033 (2)	0.025 (2)	−0.0016 (16)	0.0107 (16)	−0.0034 (16)
C3	0.028 (2)	0.043 (2)	0.026 (2)	0.0095 (18)	0.0101 (17)	0.0027 (18)
C4	0.040 (2)	0.032 (2)	0.033 (2)	0.0104 (18)	0.0139 (19)	0.0052 (18)
C5	0.041 (2)	0.026 (2)	0.033 (2)	−0.0030 (18)	0.0150 (19)	0.0014 (17)
C6	0.0272 (19)	0.032 (2)	0.0221 (19)	−0.0027 (16)	0.0113 (16)	−0.0016 (16)
C7	0.026 (2)	0.043 (3)	0.047 (3)	−0.0042 (19)	0.0039 (19)	−0.006 (2)
C8	0.028 (2)	0.035 (2)	0.032 (2)	−0.0067 (17)	0.0127 (18)	−0.0042 (17)
C9	0.047 (3)	0.042 (3)	0.041 (3)	0.002 (2)	0.027 (2)	0.002 (2)
C10	0.053 (3)	0.050 (3)	0.034 (2)	−0.005 (2)	0.017 (2)	−0.012 (2)
C11	0.031 (2)	0.060 (3)	0.052 (3)	0.009 (2)	0.016 (2)	0.019 (2)
C12	0.072 (3)	0.039 (3)	0.073 (4)	0.017 (2)	0.053 (3)	0.006 (2)

Geometric parameters (Å, º) top

Zr1—N1ⁱ	2.119 (3)	C5—C6	1.389 (6)
Zr1—N1	2.119 (3)	C5—H5A	0.9400
Zr1—N2ⁱ	2.439 (3)	C6—C8	1.506 (5)
Zr1—N2	2.439 (3)	C7—H7A	0.9700
Zr1—Cl1ⁱ	2.4676 (11)	C7—H7B	0.9700
Zr1—Cl1	2.4676 (11)	C7—H7C	0.9700
Zr1—Si1ⁱ	3.0385 (12)	C8—H8A	0.9700
Si1—N1	1.724 (3)	C8—H8B	0.9700
Si1—N2	1.791 (4)	C8—H8C	0.9700
Si1—C9	1.854 (4)	C9—H9A	0.9700
Si1—C10	1.859 (5)	C9—H9B	0.9700
N1—C1	1.436 (5)	C9—H9C	0.9700
N2—C12	1.480 (6)	C10—H10A	0.9700
N2—C11	1.487 (6)	C10—H10B	0.9700
C1—C6	1.408 (5)	C10—H10C	0.9700
C1—C2	1.413 (5)	C11—H11A	0.9700
C2—C3	1.388 (6)	C11—H11D	0.9700
C2—C7	1.504 (6)	C11—H11C	0.9700
C3—C4	1.376 (6)	C12—H12B	0.9700
C3—H3A	0.9400	C12—H12C	0.9700
C4—C5	1.379 (6)	C12—H12A	0.9700
C4—H4A	0.9400

N1ⁱ—Zr1—N1	94.65 (16)	C3—C4—C5	119.2 (4)
N1ⁱ—Zr1—N2ⁱ	67.63 (11)	C3—C4—H4A	120.4
N1—Zr1—N2ⁱ	130.12 (12)	C5—C4—H4A	120.4
N1ⁱ—Zr1—N2	130.12 (12)	C4—C5—C6	121.4 (4)
N1—Zr1—N2	67.63 (11)	C4—C5—H5A	119.3
N2ⁱ—Zr1—N2	157.56 (16)	C6—C5—H5A	119.3
N1ⁱ—Zr1—Cl1ⁱ	142.64 (8)	C5—C6—C1	119.5 (3)
N1—Zr1—Cl1ⁱ	96.22 (9)	C5—C6—C8	117.7 (4)
N2ⁱ—Zr1—Cl1ⁱ	78.14 (8)	C1—C6—C8	122.8 (3)
N2—Zr1—Cl1ⁱ	86.92 (9)	C2—C7—H7A	109.5
N1ⁱ—Zr1—Cl1	96.22 (9)	C2—C7—H7B	109.5
N1—Zr1—Cl1	142.64 (8)	H7A—C7—H7B	109.5
N2ⁱ—Zr1—Cl1	86.92 (9)	C2—C7—H7C	109.5
N2—Zr1—Cl1	78.14 (8)	H7A—C7—H7C	109.5
Cl1ⁱ—Zr1—Cl1	96.45 (6)	H7B—C7—H7C	109.5
N1ⁱ—Zr1—Si1ⁱ	33.40 (8)	C6—C8—H8A	109.5
N1—Zr1—Si1ⁱ	122.01 (9)	C6—C8—H8B	109.5
N2ⁱ—Zr1—Si1ⁱ	36.12 (8)	H8A—C8—H8B	109.5
N2—Zr1—Si1ⁱ	153.54 (9)	C6—C8—H8C	109.5
Cl1ⁱ—Zr1—Si1ⁱ	114.26 (3)	H8A—C8—H8C	109.5
Cl1—Zr1—Si1ⁱ	83.61 (4)	H8B—C8—H8C	109.5
N1—Si1—N2	93.02 (16)	Si1—C9—H9A	109.5
N1—Si1—C9	117.81 (19)	Si1—C9—H9B	109.5
N2—Si1—C9	112.64 (19)	H9A—C9—H9B	109.5
N1—Si1—C10	116.49 (19)	Si1—C9—H9C	109.5
N2—Si1—C10	111.0 (2)	H9A—C9—H9C	109.5
C9—Si1—C10	105.6 (2)	H9B—C9—H9C	109.5
C1—N1—Si1	121.2 (2)	Si1—C10—H10A	109.5
C1—N1—Zr1	134.3 (2)	Si1—C10—H10B	109.5
Si1—N1—Zr1	104.01 (15)	H10A—C10—H10B	109.5
C12—N2—C11	108.4 (4)	Si1—C10—H10C	109.5
C12—N2—Si1	118.1 (3)	H10A—C10—H10C	109.5
C11—N2—Si1	112.0 (3)	H10B—C10—H10C	109.5
C12—N2—Zr1	119.4 (3)	N2—C11—H11A	109.5
C11—N2—Zr1	107.3 (3)	N2—C11—H11D	109.5
Si1—N2—Zr1	90.49 (13)	H11A—C11—H11D	109.5
C6—C1—C2	118.9 (3)	N2—C11—H11C	109.5
C6—C1—N1	120.6 (3)	H11A—C11—H11C	109.5
C2—C1—N1	120.6 (3)	H11D—C11—H11C	109.5
C3—C2—C1	119.4 (4)	N2—C12—H12B	109.5
C3—C2—C7	118.1 (3)	N2—C12—H12C	109.5
C1—C2—C7	122.5 (3)	H12B—C12—H12C	109.5
C4—C3—C2	121.6 (4)	N2—C12—H12A	109.5
C4—C3—H3A	119.2	H12B—C12—H12A	109.5
C2—C3—H3A	119.2	H12C—C12—H12A	109.5

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zr(C₁₂H₂₁N₂Si)₂Cl₂]
M_r	604.92
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	203
a, b, c (Å)	16.179 (2), 10.257 (2), 18.779 (4)
β (°)	112.234 (4)
V (Å³)	2884.6 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.67
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.757, 0.878
No. of measured, independent and observed [I > 2σ(I)] reflections	6014, 2548, 2448
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.120, 1.20
No. of reflections	2548
No. of parameters	151
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.53

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008).

Selected bond lengths (Å) top

Zr1—N1	2.119 (3)	Zr1—Cl1	2.4676 (11)
Zr1—N2	2.439 (3)

Acknowledgements

This work was under the sponsorship of the Natural Science Foundation of Shanxi Province (2008011024).

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