Dichloridobis{N-[(dimethyl-amino)dimethyl-silyl]-2,6-dimethyl-anilido-κN,N'}zirconium(IV).

The monomeric title zirconium(IV) compound, [Zr(C(12)H(21)N(2)Si)(2)Cl(2)], was prepared by the metathetical reaction of [LiN(SiMe(2)NMe(2))(2,6-Me(2)C(6)H(3))](2) with zirconium tetra-chloride. 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 octa-hedral geometry. The two ligands around the Zr(IV) atom are arranged cis to each other and obey the C(2) symmetry operation. That means the asymmetric unit consists of only half of the mol-ecular compound and the complete mol-ecule 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 = 604.92

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.120

S = 1.20

2548 reflections

151 parameters

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.53 e Å−3

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.

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

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809039804/vm2005Isup2.hkl

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

[Zr(C12H21N2Si)2Cl2]	F(000) = 1264
Mr = 604.92	Dx = 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

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

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(Fo2) + (0.0465P)2 + 9.9576P] where P = (Fo2 + 2Fc2)/3
2548 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.53 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
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*

	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)

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

Table 1

Selected bond lengths (Å)

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