{N,N-Bis[2-(trimethyl-silylamino)eth-yl]-N'-(trimethyl-silyl)ethane-1,2-diamin-ato(3-)-κN}methyl-zirconium(IV).

The title compound, [Zr(CH(3))(C(15)H(39)N(4)Si(3))], is a unique example of a triamido-amine-supported zirconium-methyl complex that crystallized as a monomer with trigonal-bipyramidal geometry at zirconium, featuring a Zr-C bond of 2.2963 (16) Å.

Related literature

For recent applications of (N3N)ZrMe in catalysis, see: Waterman (2007 ▶); Roering et al. (2007 ▶, 2008 ▶). For examples of structurally characterized triamido­amine-supported zirconium complexes, see: Duan et al. (1995 ▶); Morton et al. (1999 ▶, 2000 ▶); MacMillan et al. (2007 ▶). For related literature, see: Addison et al. (1984 ▶); Parkin (1992 ▶).

Experimental

Crystal data

[Zr(CH3)(C15H39N4Si3)]

M = 466.03

Orthorhombic,

a = 15.6018 (7) Å

b = 18.0682 (8) Å

c = 18.3745 (8) Å

V = 5179.7 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.57 mm−1

T = 125 (2) K

0.24 × 0.20 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.875, T max = 0.914

68275 measured reflections

6973 independent reflections

5714 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.063

S = 1.04

6973 reflections

226 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 1999 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680800425X/hg2378sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680800425X/hg2378Isup2.hkl

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

[Zr(CH3)(C15H39N4Si3)]	Dx = 1.195 Mg m−3
Mr = 466.03	Melting point: 362 K
Orthorhombic, Pbca	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9832 reflections
a = 15.6018 (7) Å	θ = 2.5–30.2º
b = 18.0682 (8) Å	µ = 0.57 mm−1
c = 18.3745 (8) Å	T = 125 (2) K
V = 5179.7 (4) Å3	Block, colorless
Z = 8	0.24 × 0.20 × 0.16 mm
F000 = 1984

Bruker SMART CCD area-detector diffractometer	6973 independent reflections
Radiation source: fine-focus sealed tube	5714 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.033
T = 125(2) K	θmax = 29.1º
φ and ω scans	θmin = 2.1º
Absorption correction: multi-scan(SADABS; Bruker, 1999)	h = −21→21
Tmin = 0.875, Tmax = 0.914	k = −24→24
68275 measured reflections	l = −24→25

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025	H-atom parameters constrained
wR(F2) = 0.063	w = 1/[σ2(Fo2) + (0.0241P)2 + 2.7021P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.002
6973 reflections	Δρmax = 0.37 e Å−3
226 parameters	Δρmin = −0.29 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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. EXTI refined to 0 and was removed from the refinement.

	x	y	z	Uiso*/Ueq
Zr	0.628126 (8)	0.214931 (8)	0.623919 (7)	0.02366 (4)
N1	0.62324 (8)	0.32650 (7)	0.59830 (7)	0.0296 (3)
N2	0.67984 (8)	0.15023 (7)	0.54191 (7)	0.0302 (3)
N3	0.68857 (8)	0.19705 (7)	0.72277 (7)	0.0293 (3)
N4	0.78205 (8)	0.25715 (8)	0.60724 (7)	0.0294 (3)
Si1	0.55541 (3)	0.39089 (2)	0.63723 (2)	0.02935 (9)
Si2	0.63047 (3)	0.11014 (2)	0.46778 (2)	0.02709 (9)
Si3	0.66444 (3)	0.12547 (3)	0.78173 (3)	0.03368 (10)
C1	0.69404 (11)	0.35295 (10)	0.55145 (10)	0.0402 (4)
H1A	0.6881	0.4068	0.5428	0.048*
H1B	0.6922	0.3273	0.5039	0.048*
C2	0.77345 (10)	0.13734 (10)	0.54823 (10)	0.0377 (4)
H2A	0.7937	0.1066	0.5071	0.045*
H2B	0.7864	0.1110	0.5942	0.045*
C3	0.76119 (10)	0.24758 (10)	0.73870 (9)	0.0343 (3)
H3A	0.7885	0.2335	0.7853	0.041*
H3B	0.7402	0.2991	0.7430	0.041*
C4	0.77852 (10)	0.33693 (9)	0.58941 (10)	0.0376 (4)
H4A	0.8270	0.3503	0.5572	0.045*
H4B	0.7830	0.3667	0.6345	0.045*
C5	0.81823 (10)	0.21178 (10)	0.54734 (9)	0.0380 (4)
H5A	0.8807	0.2051	0.5544	0.046*
H5B	0.8088	0.2367	0.5000	0.046*
C6	0.82595 (10)	0.24200 (10)	0.67714 (9)	0.0348 (4)
H6A	0.8726	0.2783	0.6847	0.042*
H6B	0.8514	0.1918	0.6762	0.042*
C7	0.46795 (15)	0.41750 (14)	0.57399 (13)	0.0659 (7)
H7A	0.4927	0.4371	0.5289	0.099*
H7B	0.4321	0.4555	0.5968	0.099*
H7C	0.4329	0.3739	0.5628	0.099*
C8	0.61459 (15)	0.47570 (12)	0.66494 (16)	0.0670 (7)
H8A	0.6359	0.5012	0.6215	0.101*
H8B	0.6630	0.4619	0.6961	0.101*
H8C	0.5760	0.5086	0.6918	0.101*
C9	0.50645 (14)	0.35016 (11)	0.72057 (10)	0.0486 (5)
H9A	0.4616	0.3149	0.7066	0.073*
H9B	0.4813	0.3897	0.7502	0.073*
H9C	0.5507	0.3245	0.7488	0.073*
C10	0.69439 (13)	0.12628 (12)	0.38323 (9)	0.0491 (5)
H10A	0.7510	0.1034	0.3885	0.074*
H10B	0.7011	0.1796	0.3754	0.074*
H10C	0.6646	0.1043	0.3415	0.074*
C11	0.52293 (11)	0.15334 (11)	0.45402 (10)	0.0430 (4)
H11A	0.4847	0.1388	0.4939	0.064*
H11B	0.4988	0.1365	0.4076	0.064*
H11C	0.5288	0.2073	0.4533	0.064*
C12	0.62003 (13)	0.00839 (10)	0.48219 (12)	0.0458 (4)
H12A	0.6771	−0.0134	0.4883	0.069*
H12B	0.5917	−0.0140	0.4400	0.069*
H12C	0.5858	−0.0009	0.5259	0.069*
C13	0.76108 (14)	0.09490 (13)	0.83365 (13)	0.0587 (6)
H13A	0.8074	0.0831	0.7996	0.088*
H13B	0.7469	0.0508	0.8623	0.088*
H13C	0.7796	0.1347	0.8663	0.088*
C14	0.62506 (14)	0.04485 (11)	0.72743 (12)	0.0524 (5)
H14A	0.6661	0.0338	0.6885	0.079*
H14B	0.5692	0.0569	0.7061	0.079*
H14C	0.6192	0.0016	0.7592	0.079*
C15	0.58017 (14)	0.15179 (12)	0.84950 (11)	0.0493 (5)
H15A	0.6006	0.1935	0.8788	0.074*
H15B	0.5682	0.1095	0.8813	0.074*
H15C	0.5277	0.1661	0.8238	0.074*
C16	0.48882 (11)	0.17738 (10)	0.64014 (10)	0.0399 (4)
H16A	0.4821	0.1268	0.6219	0.060*
H16B	0.4504	0.2106	0.6134	0.060*
H16C	0.4746	0.1788	0.6921	0.060*

	U11	U22	U33	U12	U13	U23
Zr	0.01895 (7)	0.02612 (7)	0.02593 (7)	−0.00195 (5)	0.00175 (5)	−0.00244 (5)
N1	0.0233 (6)	0.0322 (7)	0.0333 (6)	−0.0023 (5)	0.0047 (5)	0.0056 (5)
N2	0.0207 (6)	0.0368 (7)	0.0331 (7)	0.0001 (5)	−0.0010 (5)	−0.0091 (6)
N3	0.0277 (6)	0.0310 (6)	0.0293 (6)	−0.0040 (5)	−0.0004 (5)	0.0010 (5)
N4	0.0201 (6)	0.0367 (7)	0.0314 (6)	−0.0039 (5)	0.0022 (5)	−0.0038 (5)
Si1	0.0265 (2)	0.0259 (2)	0.0356 (2)	−0.00213 (16)	−0.00132 (17)	0.00063 (17)
Si2	0.02662 (19)	0.0296 (2)	0.02508 (19)	−0.00250 (16)	−0.00016 (16)	−0.00074 (16)
Si3	0.0355 (2)	0.0320 (2)	0.0335 (2)	0.00130 (18)	0.00282 (19)	0.00533 (18)
C1	0.0315 (8)	0.0440 (9)	0.0450 (10)	−0.0025 (7)	0.0093 (7)	0.0153 (8)
C2	0.0243 (7)	0.0475 (10)	0.0412 (9)	0.0053 (7)	−0.0011 (6)	−0.0145 (8)
C3	0.0352 (8)	0.0383 (8)	0.0295 (8)	−0.0074 (7)	−0.0037 (6)	−0.0029 (7)
C4	0.0264 (8)	0.0383 (9)	0.0482 (10)	−0.0090 (7)	0.0090 (7)	0.0055 (8)
C5	0.0206 (7)	0.0563 (11)	0.0372 (9)	−0.0022 (7)	0.0053 (6)	−0.0089 (8)
C6	0.0233 (7)	0.0430 (9)	0.0380 (9)	−0.0065 (7)	−0.0058 (6)	−0.0052 (7)
C7	0.0610 (14)	0.0767 (16)	0.0600 (13)	0.0338 (12)	−0.0199 (11)	−0.0094 (12)
C8	0.0627 (14)	0.0414 (11)	0.0969 (19)	−0.0193 (10)	0.0106 (13)	−0.0183 (12)
C9	0.0580 (12)	0.0409 (10)	0.0470 (11)	0.0056 (9)	0.0205 (9)	−0.0002 (8)
C10	0.0489 (11)	0.0676 (13)	0.0307 (9)	−0.0012 (10)	0.0073 (8)	0.0052 (9)
C11	0.0326 (9)	0.0530 (11)	0.0433 (10)	0.0031 (8)	−0.0063 (7)	0.0083 (8)
C12	0.0477 (11)	0.0303 (8)	0.0595 (12)	−0.0051 (8)	0.0075 (9)	−0.0054 (8)
C13	0.0523 (12)	0.0595 (13)	0.0644 (13)	0.0087 (10)	−0.0095 (10)	0.0215 (11)
C14	0.0650 (13)	0.0348 (9)	0.0573 (12)	−0.0100 (9)	0.0060 (10)	0.0016 (9)
C15	0.0521 (12)	0.0534 (11)	0.0425 (10)	0.0007 (9)	0.0142 (9)	0.0079 (9)
C16	0.0290 (8)	0.0441 (10)	0.0465 (10)	−0.0095 (7)	0.0061 (7)	−0.0078 (8)

Zr—N2	2.0709 (12)	C5—H5A	0.9900
Zr—N1	2.0715 (13)	C5—H5B	0.9900
Zr—N3	2.0719 (13)	C6—H6A	0.9900
Zr—C16	2.2963 (16)	C6—H6B	0.9900
Zr—N4	2.5383 (12)	C7—H7A	0.9800
N1—C1	1.4796 (19)	C7—H7B	0.9800
N1—Si1	1.7278 (14)	C7—H7C	0.9800
N2—C2	1.4834 (19)	C8—H8A	0.9800
N2—Si2	1.7242 (13)	C8—H8B	0.9800
N3—C3	1.484 (2)	C8—H8C	0.9800
N3—Si3	1.7286 (13)	C9—H9A	0.9800
N4—C4	1.479 (2)	C9—H9B	0.9800
N4—C6	1.481 (2)	C9—H9C	0.9800
N4—C5	1.484 (2)	C10—H10A	0.9800
Si1—C7	1.856 (2)	C10—H10B	0.9800
Si1—C8	1.860 (2)	C10—H10C	0.9800
Si1—C9	1.8628 (18)	C11—H11A	0.9800
Si2—C12	1.8646 (18)	C11—H11B	0.9800
Si2—C11	1.8678 (17)	C11—H11C	0.9800
Si2—C10	1.8690 (18)	C12—H12A	0.9800
Si3—C13	1.868 (2)	C12—H12B	0.9800
Si3—C14	1.870 (2)	C12—H12C	0.9800
Si3—C15	1.8723 (19)	C13—H13A	0.9800
C1—C4	1.519 (2)	C13—H13B	0.9800
C1—H1A	0.9900	C13—H13C	0.9800
C1—H1B	0.9900	C14—H14A	0.9800
C2—C5	1.516 (2)	C14—H14B	0.9800
C2—H2A	0.9900	C14—H14C	0.9800
C2—H2B	0.9900	C15—H15A	0.9800
C3—C6	1.520 (2)	C15—H15B	0.9800
C3—H3A	0.9900	C15—H15C	0.9800
C3—H3B	0.9900	C16—H16A	0.9800
C4—H4A	0.9900	C16—H16B	0.9800
C4—H4B	0.9900	C16—H16C	0.9800
N2—Zr—N1	113.48 (5)	N4—C5—H5B	110.1
N2—Zr—N3	111.87 (5)	C2—C5—H5B	110.1
N1—Zr—N3	111.57 (5)	H5A—C5—H5B	108.4
N2—Zr—C16	107.24 (6)	N4—C6—C3	109.00 (13)
N1—Zr—C16	106.40 (6)	N4—C6—H6A	109.9
N3—Zr—C16	105.72 (6)	C3—C6—H6A	109.9
N2—Zr—N4	73.33 (5)	N4—C6—H6B	109.9
N1—Zr—N4	73.43 (5)	C3—C6—H6B	109.9
N3—Zr—N4	73.86 (5)	H6A—C6—H6B	108.3
C16—Zr—N4	179.41 (5)	Si1—C7—H7A	109.5
C1—N1—Si1	118.72 (11)	Si1—C7—H7B	109.5
C1—N1—Zr	114.78 (10)	H7A—C7—H7B	109.5
Si1—N1—Zr	125.71 (7)	Si1—C7—H7C	109.5
C2—N2—Si2	115.83 (10)	H7A—C7—H7C	109.5
C2—N2—Zr	114.53 (10)	H7B—C7—H7C	109.5
Si2—N2—Zr	129.64 (7)	Si1—C8—H8A	109.5
C3—N3—Si3	120.19 (10)	Si1—C8—H8B	109.5
C3—N3—Zr	115.11 (10)	H8A—C8—H8B	109.5
Si3—N3—Zr	124.54 (7)	Si1—C8—H8C	109.5
C4—N4—C6	112.92 (13)	H8A—C8—H8C	109.5
C4—N4—C5	112.84 (13)	H8B—C8—H8C	109.5
C6—N4—C5	111.41 (13)	Si1—C9—H9A	109.5
C4—N4—Zr	106.52 (9)	Si1—C9—H9B	109.5
C6—N4—Zr	106.10 (9)	H9A—C9—H9B	109.5
C5—N4—Zr	106.46 (9)	Si1—C9—H9C	109.5
N1—Si1—C7	111.45 (9)	H9A—C9—H9C	109.5
N1—Si1—C8	111.34 (9)	H9B—C9—H9C	109.5
C7—Si1—C8	108.85 (12)	Si2—C10—H10A	109.5
N1—Si1—C9	108.99 (8)	Si2—C10—H10B	109.5
C7—Si1—C9	108.40 (11)	H10A—C10—H10B	109.5
C8—Si1—C9	107.70 (11)	Si2—C10—H10C	109.5
N2—Si2—C12	109.94 (8)	H10A—C10—H10C	109.5
N2—Si2—C11	109.44 (8)	H10B—C10—H10C	109.5
C12—Si2—C11	110.65 (9)	Si2—C11—H11A	109.5
N2—Si2—C10	110.66 (8)	Si2—C11—H11B	109.5
C12—Si2—C10	108.57 (10)	H11A—C11—H11B	109.5
C11—Si2—C10	107.55 (9)	Si2—C11—H11C	109.5
N3—Si3—C13	111.45 (9)	H11A—C11—H11C	109.5
N3—Si3—C14	108.66 (8)	H11B—C11—H11C	109.5
C13—Si3—C14	107.91 (11)	Si2—C12—H12A	109.5
N3—Si3—C15	112.32 (8)	Si2—C12—H12B	109.5
C13—Si3—C15	107.59 (10)	H12A—C12—H12B	109.5
C14—Si3—C15	108.79 (10)	Si2—C12—H12C	109.5
N1—C1—C4	108.61 (13)	H12A—C12—H12C	109.5
N1—C1—H1A	110.0	H12B—C12—H12C	109.5
C4—C1—H1A	110.0	Si3—C13—H13A	109.5
N1—C1—H1B	110.0	Si3—C13—H13B	109.5
C4—C1—H1B	110.0	H13A—C13—H13B	109.5
H1A—C1—H1B	108.3	Si3—C13—H13C	109.5
N2—C2—C5	108.29 (14)	H13A—C13—H13C	109.5
N2—C2—H2A	110.0	H13B—C13—H13C	109.5
C5—C2—H2A	110.0	Si3—C14—H14A	109.5
N2—C2—H2B	110.0	Si3—C14—H14B	109.5
C5—C2—H2B	110.0	H14A—C14—H14B	109.5
H2A—C2—H2B	108.4	Si3—C14—H14C	109.5
N3—C3—C6	108.65 (13)	H14A—C14—H14C	109.5
N3—C3—H3A	110.0	H14B—C14—H14C	109.5
C6—C3—H3A	110.0	Si3—C15—H15A	109.5
N3—C3—H3B	110.0	Si3—C15—H15B	109.5
C6—C3—H3B	110.0	H15A—C15—H15B	109.5
H3A—C3—H3B	108.3	Si3—C15—H15C	109.5
N4—C4—C1	108.64 (13)	H15A—C15—H15C	109.5
N4—C4—H4A	110.0	H15B—C15—H15C	109.5
C1—C4—H4A	110.0	Zr—C16—H16A	109.5
N4—C4—H4B	110.0	Zr—C16—H16B	109.5
C1—C4—H4B	110.0	H16A—C16—H16B	109.5
H4A—C4—H4B	108.3	Zr—C16—H16C	109.5
N4—C5—C2	107.87 (13)	H16A—C16—H16C	109.5
N4—C5—H5A	110.1	H16B—C16—H16C	109.5
C2—C5—H5A	110.1
N2—Zr—N1—C1	−32.96 (13)	C1—N1—Si1—C8	−37.01 (16)
N3—Zr—N1—C1	94.52 (12)	Zr—N1—Si1—C8	132.28 (12)
C16—Zr—N1—C1	−150.64 (12)	C1—N1—Si1—C9	−155.67 (13)
N4—Zr—N1—C1	29.95 (11)	Zr—N1—Si1—C9	13.62 (12)
N2—Zr—N1—Si1	157.39 (8)	C2—N2—Si2—C12	74.34 (14)
N3—Zr—N1—Si1	−75.14 (10)	Zr—N2—Si2—C12	−106.18 (11)
C16—Zr—N1—Si1	39.70 (10)	C2—N2—Si2—C11	−163.93 (12)
N4—Zr—N1—Si1	−139.70 (10)	Zr—N2—Si2—C11	15.55 (12)
N1—Zr—N2—C2	92.84 (12)	C2—N2—Si2—C10	−45.59 (15)
N3—Zr—N2—C2	−34.49 (13)	Zr—N2—Si2—C10	133.89 (11)
C16—Zr—N2—C2	−149.97 (12)	C3—N3—Si3—C13	−26.69 (15)
N4—Zr—N2—C2	29.87 (11)	Zr—N3—Si3—C13	148.55 (10)
N1—Zr—N2—Si2	−86.65 (10)	C3—N3—Si3—C14	−145.46 (13)
N3—Zr—N2—Si2	146.03 (9)	Zr—N3—Si3—C14	29.77 (12)
C16—Zr—N2—Si2	30.54 (12)	C3—N3—Si3—C15	94.13 (14)
N4—Zr—N2—Si2	−149.62 (11)	Zr—N3—Si3—C15	−90.64 (11)
N2—Zr—N3—C3	92.41 (11)	Si1—N1—C1—C4	112.38 (14)
N1—Zr—N3—C3	−35.93 (12)	Zr—N1—C1—C4	−58.05 (17)
C16—Zr—N3—C3	−151.18 (11)	Si2—N2—C2—C5	120.48 (13)
N4—Zr—N3—C3	28.37 (10)	Zr—N2—C2—C5	−59.08 (16)
N2—Zr—N3—Si3	−83.04 (9)	Si3—N3—C3—C6	119.29 (13)
N1—Zr—N3—Si3	148.62 (8)	Zr—N3—C3—C6	−56.37 (16)
C16—Zr—N3—Si3	33.37 (10)	C6—N4—C4—C1	−144.45 (14)
N4—Zr—N3—Si3	−147.08 (9)	C5—N4—C4—C1	88.09 (15)
N2—Zr—N4—C4	121.87 (11)	Zr—N4—C4—C1	−28.38 (15)
N1—Zr—N4—C4	0.34 (10)	N1—C1—C4—N4	54.78 (18)
N3—Zr—N4—C4	−118.70 (11)	C4—N4—C5—C2	−146.42 (14)
N2—Zr—N4—C6	−117.57 (11)	C6—N4—C5—C2	85.33 (15)
N1—Zr—N4—C6	120.91 (11)	Zr—N4—C5—C2	−29.91 (15)
N3—Zr—N4—C6	1.87 (10)	N2—C2—C5—N4	56.44 (17)
N2—Zr—N4—C5	1.21 (10)	C4—N4—C6—C3	86.62 (16)
N1—Zr—N4—C5	−120.31 (11)	C5—N4—C6—C3	−145.17 (14)
N3—Zr—N4—C5	120.65 (11)	Zr—N4—C6—C3	−29.71 (15)
C1—N1—Si1—C7	84.74 (16)	N3—C3—C6—N4	54.96 (18)
Zr—N1—Si1—C7	−105.97 (12)