(tert-Butyl-imido)bis-(η-cyclo-penta-dien-yl)pyridine-zirconium(IV).

The title compound, [Zr(C(5)H(5))(2)(C(4)H(9)N)(C(5)H(5)N)], was obtained from the reaction of (C(5)H(5))(2)Zr(py)(η(2)-Me(3)SiC(2)SiMe(3)) (py is pyridine) and (t)BuN=C=N(t)Bu alongside the formation of (C(5)H(5))(2)Zr(CN(t)Bu)(η(2)-Me(3)SiC(2)SiMe(3)). The zirconium atom is coordinated in a distorted tetra-hedral geometry by two cyclo-penta-dienyl ligands, a pyridine ligand, and a tert-butyl-imido ligand via a Zr=N double bond. The tert-butyl group is disordered over two positions in a 0.634 (5):0.366 (5) ratio.

Related literature

For other metallocene complexes (C5H5)CpM(L)(NBu) (Cp = C5H5, C5Me5; M = Ti, L = py; M = Zr, L = py, thf (thf is tetrahydrofuran), exo-norbornene oxide) with an M=N double bond, see: Blum et al. (2003 ▶, 2005 ▶); Dunn et al. (1997 ▶); Krska et al. (1998 ▶); Walsh et al. (1988 ▶, 1993 ▶); Zuckerman et al. (2000 ▶). For the structure of (rac-ebthi)Zr(py)(NBu) (ebthi = ethyl­enebis(η5-tetra­hydro­inden­yl)), see: Hoyt et al. (2004 ▶). For the preparation of the starting material (C5H5)2Zr(py)(η2-Me3SiC2SiMe3), see: Rosenthal et al. (1995 ▶). For the characterization of the by-product (C5H5)2Zr(CNBu)(η2-Me3SiC2SiMe3) of the above-described reaction, see: Bach et al. (2007 ▶).

Experimental

Crystal data

[Zr(C5H5)2(C4H9N)(C5H5N)]

M = 371.62

Orthorhombic,

a = 9.3946 (2) Å

b = 13.6156 (4) Å

c = 14.4126 (3) Å

V = 1843.56 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.60 mm−1

T = 200 K

0.50 × 0.50 × 0.35 mm

Data collection

Stoe IPDS II diffractometer

Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005 ▶) T min = 0.730, T max = 0.896

35444 measured reflections

4990 independent reflections

4752 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.059

S = 1.03

4990 reflections

181 parameters

16 restraints

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.38 e Å−3

Absolute structure: Flack (1983 ▶), 216 Friedel pairs

Flack parameter: −0.03 (4)

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810033556/im2220sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810033556/im2220Isup2.hkl

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

[Zr(C5H5)2(C4H9N)(C5H5N)]	F(000) = 768
Mr = 371.62	Dx = 1.339 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 11751 reflections
a = 9.3946 (2) Å	θ = 2.0–29.6°
b = 13.6156 (4) Å	µ = 0.60 mm−1
c = 14.4126 (3) Å	T = 200 K
V = 1843.56 (8) Å3	Prism, yellow
Z = 4	0.50 × 0.50 × 0.35 mm

Stoe IPDS II diffractometer	4990 independent reflections
Radiation source: fine-focus sealed tube	4752 reflections with I > 2σ(I)
graphite	Rint = 0.025
ω scans	θmax = 29.2°, θmin = 2.1°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2005)	h = −12→12
Tmin = 0.730, Tmax = 0.896	k = −18→18
35444 measured reflections	l = −19→19

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)] = 0.023	H-atom parameters constrained
wR(F2) = 0.059	w = 1/[σ2(Fo2) + (0.043P)2 + 0.044P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
4990 reflections	Δρmax = 0.45 e Å−3
181 parameters	Δρmin = −0.38 e Å−3
16 restraints	Absolute structure: Flack (1983), 2169 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.03 (4)

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	Occ. (<1)
C2A	−0.0298 (4)	0.5132 (4)	0.2054 (4)	0.0710 (13)*	0.634 (5)
H2A1	−0.0198	0.5691	0.2477	0.107*	0.634 (5)
H2A2	−0.1118	0.4734	0.2241	0.107*	0.634 (5)
H2A3	−0.0441	0.5373	0.1420	0.107*	0.634 (5)
C3A	0.1191 (6)	0.4163 (4)	0.3089 (2)	0.0765 (14)*	0.634 (5)
H3A1	0.1243	0.4733	0.3502	0.115*	0.634 (5)
H3A2	0.2062	0.3772	0.3152	0.115*	0.634 (5)
H3A3	0.0366	0.3760	0.3256	0.115*	0.634 (5)
C4A	0.0964 (5)	0.3633 (3)	0.1445 (3)	0.0690 (13)*	0.634 (5)
H4A1	0.1846	0.3253	0.1493	0.103*	0.634 (5)
H4A2	0.0841	0.3862	0.0806	0.103*	0.634 (5)
H4A3	0.0155	0.3219	0.1620	0.103*	0.634 (5)
C2B	0.0023 (10)	0.4490 (9)	0.1272 (6)	0.095 (3)*	0.366 (5)
H2B1	0.0528	0.4262	0.0717	0.143*	0.366 (5)
H2B2	−0.0348	0.5153	0.1162	0.143*	0.366 (5)
H2B3	−0.0769	0.4044	0.1408	0.143*	0.366 (5)
C3B	0.0215 (10)	0.4865 (7)	0.2929 (5)	0.081 (3)*	0.366 (5)
H3B1	−0.0046	0.5556	0.2843	0.122*	0.366 (5)
H3B2	0.0806	0.4799	0.3486	0.122*	0.366 (5)
H3B3	−0.0650	0.4470	0.3001	0.122*	0.366 (5)
C4B	0.1428 (12)	0.3436 (3)	0.2234 (6)	0.078 (2)*	0.366 (5)
H4B1	0.1974	0.3200	0.1700	0.117*	0.366 (5)
H4B2	0.0556	0.3047	0.2297	0.117*	0.366 (5)
H4B3	0.2003	0.3370	0.2798	0.117*	0.366 (5)
C1	0.1041 (2)	0.45092 (16)	0.20903 (15)	0.0500 (5)
C15	0.6237 (2)	0.54813 (15)	0.02869 (15)	0.0469 (4)
H15	0.6509	0.6142	0.0403	0.056*
C16	0.7109 (3)	0.49094 (19)	−0.02490 (19)	0.0627 (7)
H16	0.7964	0.5172	−0.0498	0.075*
C17	0.6736 (3)	0.39523 (18)	−0.04233 (19)	0.0737 (9)
H17	0.7332	0.3538	−0.0784	0.088*
C18	0.5476 (3)	0.36108 (19)	−0.00621 (19)	0.0722 (9)
H18	0.5181	0.2955	−0.0181	0.087*
C19	0.4643 (3)	0.42177 (15)	0.04710 (15)	0.0493 (5)
H19	0.3776	0.3970	0.0717	0.059*
N1	0.22557 (16)	0.51038 (11)	0.18718 (11)	0.0361 (3)
N2	0.50127 (18)	0.51501 (12)	0.06570 (11)	0.0383 (3)
Zr1	0.363638 (15)	0.605190 (11)	0.172085 (11)	0.03033 (5)
C5	0.16807 (18)	0.72069 (14)	0.12010 (16)	0.0645 (8)
H5	0.0771	0.7076	0.1462	0.077*
C6	0.2709 (2)	0.78328 (13)	0.15691 (17)	0.0720 (9)
H6	0.2625	0.8204	0.2125	0.086*
C7	0.3884 (2)	0.78188 (13)	0.09794 (17)	0.0748 (9)
H7	0.4741	0.8179	0.1062	0.090*
C8	0.3582 (2)	0.71844 (15)	0.02469 (14)	0.0712 (8)
H8	0.4197	0.7036	−0.0257	0.085*
C9	0.2220 (2)	0.68063 (15)	0.03839 (14)	0.0680 (8)
H9	0.1743	0.6355	−0.0011	0.082*
C10	0.5757 (3)	0.54733 (18)	0.27310 (18)	0.0803 (10)
H10	0.6232	0.4895	0.2532	0.096*
C11	0.4565 (3)	0.5510 (2)	0.32905 (16)	0.0944 (12)
H11	0.4076	0.4961	0.3544	0.113*
C12	0.4209 (3)	0.6485 (3)	0.34173 (13)	0.0959 (13)
H12	0.3431	0.6724	0.3773	0.115*
C13	0.5180 (3)	0.7050 (2)	0.29362 (17)	0.0829 (10)
H13	0.5188	0.7747	0.2903	0.099*
C14	0.6137 (2)	0.64251 (19)	0.25120 (15)	0.0731 (8)
H14	0.6919	0.6616	0.2136	0.088*

	U11	U22	U33	U12	U13	U23
C1	0.0409 (11)	0.0494 (12)	0.0596 (12)	−0.0060 (8)	0.0131 (9)	0.0040 (9)
C15	0.0433 (10)	0.0462 (10)	0.0513 (11)	0.0066 (9)	0.0127 (9)	0.0041 (8)
C16	0.0615 (14)	0.0656 (15)	0.0611 (14)	0.0170 (12)	0.0308 (12)	0.0123 (12)
C17	0.099 (2)	0.0582 (14)	0.0644 (15)	0.0300 (15)	0.0443 (14)	0.0062 (13)
C18	0.116 (2)	0.0389 (11)	0.0612 (15)	0.0142 (13)	0.0411 (16)	−0.0014 (10)
C19	0.0687 (14)	0.0346 (10)	0.0447 (11)	0.0026 (8)	0.0199 (10)	0.0011 (7)
N1	0.0355 (7)	0.0365 (7)	0.0364 (8)	0.0017 (6)	0.0066 (6)	0.0008 (6)
N2	0.0418 (8)	0.0357 (8)	0.0374 (8)	0.0065 (6)	0.0085 (6)	0.0022 (6)
Zr1	0.02958 (7)	0.03000 (7)	0.03142 (7)	0.00527 (6)	0.00094 (6)	−0.00138 (6)
C5	0.0433 (12)	0.0566 (14)	0.093 (2)	0.0242 (10)	0.0149 (11)	0.0296 (13)
C6	0.0713 (16)	0.0367 (11)	0.108 (3)	0.0212 (11)	0.0257 (16)	0.0057 (13)
C7	0.0670 (17)	0.0398 (11)	0.118 (3)	0.0089 (11)	0.0268 (17)	0.0228 (14)
C8	0.0676 (14)	0.0726 (16)	0.0735 (16)	0.0295 (14)	0.0231 (15)	0.0402 (14)
C9	0.0630 (15)	0.0719 (17)	0.0690 (17)	0.0214 (13)	−0.0124 (13)	0.0270 (14)
C10	0.0732 (19)	0.095 (2)	0.0723 (19)	0.0222 (17)	−0.0423 (17)	−0.0064 (17)
C11	0.104 (3)	0.127 (3)	0.0521 (15)	−0.015 (2)	−0.0394 (19)	0.020 (2)
C12	0.086 (2)	0.163 (4)	0.0385 (14)	0.002 (2)	−0.0050 (13)	−0.0307 (18)
C13	0.081 (2)	0.092 (2)	0.0749 (19)	−0.0029 (18)	−0.0192 (16)	−0.0435 (18)
C14	0.0516 (15)	0.101 (2)	0.0671 (16)	−0.0002 (13)	−0.0210 (12)	−0.0239 (15)

C2A—C1	1.518 (3)	C19—N2	1.343 (3)
C2A—H2A1	0.9800	C19—H19	0.9500
C2A—H2A2	0.9800	N1—Zr1	1.8428 (16)
C2A—H2A3	0.9800	N2—Zr1	2.3517 (16)
C3A—C1	1.521 (3)	Zr1—C5	2.5318 (16)
C3A—H3A1	0.9800	Zr1—C11	2.534 (2)
C3A—H3A2	0.9800	Zr1—C9	2.5570 (17)
C3A—H3A3	0.9800	Zr1—C12	2.5719 (19)
C4A—C1	1.514 (3)	Zr1—C6	2.5857 (17)
C4A—H4A1	0.9800	Zr1—C10	2.590 (2)
C4A—H4A2	0.9800	Zr1—C8	2.6255 (17)
C4A—H4A3	0.9800	Zr1—C7	2.6428 (17)
C2B—C1	1.519 (3)	Zr1—C13	2.649 (2)
C2B—H2B1	0.9800	Zr1—C14	2.6602 (19)
C2B—H2B2	0.9800	C5—C6	1.3933
C2B—H2B3	0.9800	C5—C9	1.3933
C3B—C1	1.516 (3)	C5—H5	0.9500
C3B—H3B1	0.9800	C6—C7	1.3933
C3B—H3B2	0.9800	C6—H6	0.9500
C3B—H3B3	0.9800	C7—C8	1.3933
C4B—C1	1.519 (3)	C7—H7	0.9500
C4B—H4B1	0.9800	C8—C9	1.3933
C4B—H4B2	0.9800	C8—H8	0.9500
C4B—H4B3	0.9800	C9—H9	0.9500
C1—N1	1.434 (3)	C10—C11	1.3807
C15—N2	1.346 (3)	C10—C14	1.3807
C15—C16	1.369 (3)	C10—H10	0.9500
C15—H15	0.9500	C11—C12	1.3807
C16—C17	1.373 (3)	C11—H11	0.9500
C16—H16	0.9500	C12—C13	1.3807
C17—C18	1.374 (3)	C12—H12	0.9500
C17—H17	0.9500	C13—C14	1.3807
C18—C19	1.373 (3)	C13—H13	0.9500
C18—H18	0.9500	C14—H14	0.9500
C1—C2A—H2A1	109.5	C5—Zr1—C10	155.98 (8)
C1—C2A—H2A2	109.5	C9—Zr1—C10	161.08 (8)
H2A1—C2A—H2A2	109.5	C12—Zr1—C10	51.29 (7)
C1—C2A—H2A3	109.5	C6—Zr1—C10	126.29 (8)
H2A1—C2A—H2A3	109.5	N1—Zr1—C8	119.55 (7)
H2A2—C2A—H2A3	109.5	N2—Zr1—C8	77.87 (6)
C1—C3A—H3A1	109.5	C5—Zr1—C8	51.80 (6)
C1—C3A—H3A2	109.5	C11—Zr1—C8	154.14 (8)
H3A1—C3A—H3A2	109.5	C12—Zr1—C8	129.69 (9)
C1—C3A—H3A3	109.5	C6—Zr1—C8	51.26 (6)
H3A1—C3A—H3A3	109.5	C10—Zr1—C8	130.42 (8)
H3A2—C3A—H3A3	109.5	N1—Zr1—C7	138.37 (7)
C1—C4A—H4A1	109.5	N2—Zr1—C7	99.39 (6)
C1—C4A—H4A2	109.5	C5—Zr1—C7	51.60 (6)
H4A1—C4A—H4A2	109.5	C11—Zr1—C7	126.55 (9)
C1—C4A—H4A3	109.5	C9—Zr1—C7	51.36 (6)
H4A1—C4A—H4A3	109.5	C12—Zr1—C7	99.06 (10)
H4A2—C4A—H4A3	109.5	C10—Zr1—C7	115.87 (8)
C1—C2B—H2B1	109.5	N1—Zr1—C13	131.80 (8)
C1—C2B—H2B2	109.5	N2—Zr1—C13	113.45 (7)
H2B1—C2B—H2B2	109.5	C5—Zr1—C13	105.91 (8)
C1—C2B—H2B3	109.5	C11—Zr1—C13	51.00 (7)
H2B1—C2B—H2B3	109.5	C9—Zr1—C13	125.24 (8)
H2B2—C2B—H2B3	109.5	C6—Zr1—C13	76.06 (8)
C1—C3B—H3B1	109.5	C10—Zr1—C13	50.46 (7)
C1—C3B—H3B2	109.5	C8—Zr1—C13	104.14 (9)
H3B1—C3B—H3B2	109.5	C7—Zr1—C13	75.64 (9)
C1—C3B—H3B3	109.5	N1—Zr1—C14	134.81 (8)
H3B1—C3B—H3B3	109.5	N2—Zr1—C14	83.90 (7)
H3B2—C3B—H3B3	109.5	C5—Zr1—C14	130.47 (7)
C1—C4B—H4B1	109.5	C11—Zr1—C14	50.87 (7)
C1—C4B—H4B2	109.5	C9—Zr1—C14	134.89 (8)
H4B1—C4B—H4B2	109.5	C12—Zr1—C14	50.52 (7)
C1—C4B—H4B3	109.5	C6—Zr1—C14	98.89 (7)
H4B1—C4B—H4B3	109.5	C8—Zr1—C14	104.58 (8)
H4B2—C4B—H4B3	109.5	C7—Zr1—C14	85.50 (8)
N1—C1—C4A	110.4 (2)	C6—C5—C9	108.0
N1—C1—C3B	113.7 (4)	C6—C5—Zr1	76.34 (7)
C4A—C1—C3B	135.8 (5)	C9—C5—Zr1	75.11 (6)
N1—C1—C2A	109.7 (2)	C6—C5—H5	126.0
C4A—C1—C2A	112.3 (3)	C9—C5—H5	126.0
C3B—C1—C2A	54.9 (4)	Zr1—C5—H5	114.8
N1—C1—C2B	109.9 (5)	C7—C6—C5	108.0
C4A—C1—C2B	58.6 (5)	C7—C6—Zr1	76.82 (6)
C3B—C1—C2B	107.6 (6)	C5—C6—Zr1	72.08 (7)
C2A—C1—C2B	57.3 (5)	C7—C6—H6	126.0
N1—C1—C4B	112.5 (4)	C5—C6—H6	126.0
C4A—C1—C4B	48.5 (4)	Zr1—C6—H6	117.1
C3B—C1—C4B	108.7 (6)	C8—C7—C6	108.0
C2A—C1—C4B	137.7 (5)	C8—C7—Zr1	73.98 (6)
C2B—C1—C4B	103.9 (6)	C6—C7—Zr1	72.29 (6)
N1—C1—C3A	108.0 (3)	C8—C7—H7	126.0
C4A—C1—C3A	109.9 (3)	C6—C7—H7	126.0
C3B—C1—C3A	52.6 (4)	Zr1—C7—H7	119.6
C2A—C1—C3A	106.4 (3)	C7—C8—C9	108.0
C2B—C1—C3A	142.0 (5)	C7—C8—Zr1	75.35 (7)
C4B—C1—C3A	63.3 (4)	C9—C8—Zr1	71.71 (6)
N2—C15—C16	123.0 (2)	C7—C8—H8	126.0
N2—C15—H15	118.5	C9—C8—H8	126.0
C16—C15—H15	118.5	Zr1—C8—H8	118.8
C15—C16—C17	119.4 (2)	C8—C9—C5	108.0
C15—C16—H16	120.3	C8—C9—Zr1	77.14 (7)
C17—C16—H16	120.3	C5—C9—Zr1	73.11 (7)
C16—C17—C18	118.2 (2)	C8—C9—H9	126.0
C16—C17—H17	120.9	C5—C9—H9	126.0
C18—C17—H17	120.9	Zr1—C9—H9	115.9
C19—C18—C17	119.9 (2)	C11—C10—C14	108.0
C19—C18—H18	120.0	C11—C10—Zr1	72.15 (8)
C17—C18—H18	120.0	C14—C10—Zr1	77.58 (9)
N2—C19—C18	122.2 (2)	C11—C10—H10	126.0
N2—C19—H19	118.9	C14—C10—H10	126.0
C18—C19—H19	118.9	Zr1—C10—H10	116.3
C1—N1—Zr1	168.93 (13)	C10—C11—C12	108.0
C19—N2—C15	117.30 (17)	C12—C11—Zr1	75.82 (9)
C19—N2—Zr1	118.78 (14)	C10—C11—H11	126.0
C15—N2—Zr1	123.60 (14)	C12—C11—H11	126.0
N1—Zr1—N2	95.64 (6)	Zr1—C11—H11	113.9
N1—Zr1—C5	87.67 (7)	C13—C12—C11	108.0
N2—Zr1—C5	122.03 (7)	C13—C12—Zr1	77.79 (8)
N1—Zr1—C11	86.16 (8)	C11—C12—Zr1	72.82 (9)
N2—Zr1—C11	103.93 (9)	C13—C12—H12	126.0
C5—Zr1—C11	134.01 (9)	C11—C12—H12	126.0
N1—Zr1—C9	90.23 (7)	Zr1—C12—H12	115.5
N2—Zr1—C9	90.26 (6)	C12—C13—C14	108.0
N1—Zr1—C12	101.27 (8)	C12—C13—Zr1	71.59 (8)
N2—Zr1—C12	128.65 (8)	C14—C13—Zr1	75.37 (7)
C5—Zr1—C12	106.90 (9)	C12—C13—H13	126.0
C9—Zr1—C12	137.15 (9)	C14—C13—H13	126.0
N1—Zr1—C6	115.46 (7)	Zr1—C13—H13	118.9
N2—Zr1—C6	128.29 (6)	C13—C14—C10	108.0
C11—Zr1—C6	117.67 (9)	C13—C14—Zr1	74.49 (8)
C9—Zr1—C6	52.00 (6)	C10—C14—Zr1	71.97 (8)
C12—Zr1—C6	86.33 (9)	C13—C14—H14	126.0
N1—Zr1—C10	105.18 (8)	C10—C14—H14	126.0
N2—Zr1—C10	77.57 (8)	Zr1—C14—H14	119.4