Bis(diethyl­amido-κN)(diethyl­amine-κN)bis­(2,6-diisopropyl­phenyl­amido-κN)zirconium(IV)

Zauliczny, M.; Grubba, R.; Ponikiewski, Ł.; Pikies, J.

doi:10.1107/S160053681205115X

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page m72

doi:10.1107/S160053681205115X

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Bis(diethylamido-κN)(diethylamine-κN)bis(2,6-diisopropylphenylamido-κN)zirconium(IV)

Mateusz Zauliczny,^a Rafał Grubba,^a Łukasz Ponikiewski ^a ^* and Jerzy Pikies ^a

^aChemical Faculty, Gdansk University of Technology, Gabriela Narutowicza Street 11/12, 80-233 Gdansk, Poland
^*Correspondence e-mail: lukasz.ponikiewski@pg.gda.pl

(Received 4 December 2012; accepted 18 December 2012; online 4 January 2013)

In the title compound, [Zr(C₁₂H₁₈N)₂(C₄H₁₀N)₂(C₄H₁₁N)] or [Zr(HNC₆H₃ⁱPr₂)₂(NEt₂)₂(HNEt₂)], which was obtained by the reaction of Zr(NEt)₄ with ⁱPr₂C₆H₃NH₂, the Zr^IV atom is in a trigonal–bipiramidal geometry in which the N atoms from two ⁱPr₂C₆H₃NH and one NEt₂ ligand occupy the equatorial positions, and the N atoms of an NEt₂ and an Et₂NH ligand occupy the apical positions. An intramolecular N—H⋯N contact occurs. There are two independent molecules in the asymmetric unit.

Related literature

For related zirconium(IV) structures, see: Profilet et al. (1990 ); Blake et al. (1997 ); Porter & Danopoulos (2004 ); Ghesner et al. (2006 ). For related syntheses, see: Kempe (2000 ).

Experimental

Crystal data

[Zr(C₁₂H₁₈N)₂(C₄H₁₀N)₂(C₄H₁₁N)]
M_r = 661.17
Triclinic, $[P \overline 1]$
a = 11.2079 (3) Å
b = 13.1612 (5) Å
c = 14.3443 (6) Å
α = 86.578 (3)°
β = 70.484 (3)°
γ = 71.232 (3)°
V = 1885.61 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 293 K
0.58 × 0.39 × 0.34 mm

Data collection

Agilent Xcalibur (Sapphire2 diffractometer
Absorption correction: analytical (CrysAlis PRO; Agilent, 2010 ) T_min = 0.889, T_max = 0.928
11493 measured reflections
7412 independent reflections
5867 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.073
wR(F²) = 0.188
S = 1.12
7412 reflections
402 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.82 e Å⁻³
Δρ_min = −2.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N1	0.84 (5)	2.56 (5)	2.983 (5)	112 (4)

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681205115X/ng5310sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681205115X/ng5310Isup2.hkl

checkCIF report

Comment top

Complex (I) was synthesized in the course of our studies on amido complexes of zirconium (Kempe, 2000). The compound was obtained in the reaction Zr(NEt)₄ with ⁱPr₂C₆H₃NH₂ (molar ratio 1:2). Complex (I) contains four amido ligands (two NEt₂ and two ⁱPr₂C₆H₃NH) and one amino ligand (HNEt₂). Analyzing bond lengths in title compound it is easily spotted that bond Zr—N3 is much longer than other bonds. It is caused by the fact, that ligand containing N1 is amine ligand. Difference between length of bonds Zr—N between NEt₂ and HNEt₂ is about 0.25 Å. Distances between N atoms of ⁱPr₂C₆H₃NH and Zr are both about 2.12 Å and very similar to related Zr(IV) amido complexes (Profilet et al., 1990; Blake et al., 1997). In case of two NEt₂ ligands distances Zr—N differ by about 0.12 Å but both are in the range typical for zirconium complexes with diethylamido ligands (Porter et al., 2004; Ghesner et al., 2006). Comparing angles between N1—Zr1—N2, N2—Zr1—N5 and N5—Zr1—N1 [table 1] it can be seen that they are roughly 120°, in addition the angle between N3—Zr1—N4 [table 1] indicates that molecular geometry is close to trigonal bipyramidal. Admittedly in perfect trigonal bipyramid first three angles would be equal to 120° and N3—Zr1—N4 would be equal to 180°, but actual angles are so close to said values that it is safe to say they resemble trigonal bipyramid.

The crystal packing diagram shows, that the compound crystallizes with two molecules in the unit cell in the triclinic space group. The crystal packing of the title compound is presented in Fig.2.

Related literature top

For related zirconium(IV) structures, see: Profilet et al. (1990); Blake et al. (1997); Porter et al. (2004); Ghesner et al. (2006). For related syntheses, see: Kempe (2000).

Experimental top

To a 100 ml Schlenk flask, equipped with a magnetic stirrer, charged with a solution of 4,8 g (4,44 ml) Zr(NEt₂)₄ in 30 ml of pentane, 5 g (4,76 ml) of 2,6-diisopropylaniline in 10 ml of pentane was added dropwise. The reaction was carried on in a room temperature in an argon atmosphere. Solution was left on a magnetic stirrer. Over a week of stirring, the mixture changed colour from yellow to brown. The solvent was removed under vacuum. After evaporating most of the solvent, dark solid was obtained which after keeping it longer under vacuum got darker and became oil. Residue was dissolved in 8 ml of pentane, and recrystallized at 4°C to obtain about 2 g of colorless X-ray-quality crystals. The total yield was 24%. Elemental analysis, found %: C 65.73, H 9.72, N 10.46; calc. % for C₃₀H₅₂N₅Zr: C 65.40, H 10.21, N 10.59.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom-numbering. Displacement ellipsoids are drawn at the 30% probability level H atoms connected to C have been omitted.
	Fig. 2. A view of the packing of the title compound alond the a axix.

Bis(diethylamido-κN)(diethylamine-κN)bis(2,6- diisopropylphenylamido-κN)zirconium(IV) top

Crystal data top

[Zr(C₁₂H₁₈N)₂(C₄H₁₀N)₂(C₄H₁₁N)]	Z = 2
M_r = 661.17	F(000) = 716
Triclinic, P1	D_x = 1.164 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.2079 (3) Å	Cell parameters from 6954 reflections
b = 13.1612 (5) Å	θ = 2.9–28.4°
c = 14.3443 (6) Å	µ = 0.32 mm⁻¹
α = 86.578 (3)°	T = 293 K
β = 70.484 (3)°	Block, colourless
γ = 71.232 (3)°	0.58 × 0.39 × 0.34 mm
V = 1885.61 (12) Å³

Data collection top

Agilent Xcalibur (Sapphire2 diffractometer	7412 independent reflections
Graphite monochromator	5867 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm^-1	R_int = 0.035
ω scans	θ_max = 26°, θ_min = 2.9°
Absorption correction: analytical (CrysAlis PRO; Agilent, 2010)	h = −13→8
T_min = 0.889, T_max = 0.928	k = −16→12
11493 measured reflections	l = −17→12

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)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.188	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0694P)² + 9.6553P] where P = (F_o² + 2F_c²)/3
7412 reflections	(Δ/σ)_max < 0.001
402 parameters	Δρ_max = 1.82 e Å⁻³
1 restraint	Δρ_min = −2.13 e Å⁻³

Crystal data top

[Zr(C₁₂H₁₈N)₂(C₄H₁₀N)₂(C₄H₁₁N)]	γ = 71.232 (3)°
M_r = 661.17	V = 1885.61 (12) Å³
Triclinic, P1	Z = 2
a = 11.2079 (3) Å	Mo Kα radiation
b = 13.1612 (5) Å	µ = 0.32 mm⁻¹
c = 14.3443 (6) Å	T = 293 K
α = 86.578 (3)°	0.58 × 0.39 × 0.34 mm
β = 70.484 (3)°

Data collection top

Agilent Xcalibur (Sapphire2 diffractometer	7412 independent reflections
Absorption correction: analytical (CrysAlis PRO; Agilent, 2010)	5867 reflections with I > 2σ(I)
T_min = 0.889, T_max = 0.928	R_int = 0.035
11493 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.073	1 restraint
wR(F²) = 0.188	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 1.82 e Å⁻³
7412 reflections	Δρ_min = −2.13 e Å⁻³
402 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	0.73585 (6)	0.79022 (4)	0.21365 (4)	0.03188 (17)
N1	0.7260 (3)	0.8397 (3)	0.3554 (3)	0.0216 (8)
H1A	0.650 (3)	0.838 (4)	0.401 (3)	0.026*
N2	0.7770 (4)	0.6310 (3)	0.1615 (3)	0.0199 (8)
H2	0.856 (5)	0.591 (4)	0.160 (4)	0.024*
N3	0.9717 (4)	0.7334 (3)	0.1861 (3)	0.0244 (8)
H3A	0.963 (5)	0.779 (4)	0.229 (4)	0.029*
N4	0.5246 (4)	0.8112 (3)	0.2736 (3)	0.0277 (9)
N5	0.7378 (3)	0.9016 (3)	0.1088 (3)	0.0197 (7)
C1	0.8144 (4)	0.8339 (3)	0.4082 (3)	0.0196 (9)
C2	0.8987 (4)	0.8990 (4)	0.3821 (3)	0.0207 (9)
C3	0.9889 (5)	0.8903 (4)	0.4321 (4)	0.0285 (10)
H3	1.0441	0.9331	0.4152	0.034*
C4	0.9975 (5)	0.8195 (4)	0.5060 (4)	0.0320 (11)
H4	1.0588	0.8141	0.5381	0.038*
C5	0.9145 (5)	0.7562 (4)	0.5325 (4)	0.0306 (11)
H5	0.9202	0.7093	0.5831	0.037*
C6	0.8225 (4)	0.7616 (4)	0.4847 (3)	0.0248 (10)
C7	0.8854 (4)	0.9830 (4)	0.3060 (3)	0.0242 (9)
H7	0.8631	0.9538	0.2552	0.029*
C8	0.7667 (5)	1.0843 (4)	0.3554 (4)	0.0349 (12)
H8A	0.6871	1.0649	0.3849	0.052*
H8B	0.7539	1.1357	0.3064	0.052*
H8C	0.7855	1.1153	0.4057	0.052*
C9	1.0102 (5)	1.0135 (5)	0.2538 (4)	0.0367 (12)
H9A	1.0316	1.0469	0.301	0.055*
H9B	0.9947	1.0627	0.2037	0.055*
H9C	1.0833	0.95	0.2236	0.055*
C10	0.7317 (5)	0.6931 (4)	0.5149 (4)	0.0277 (10)
H10	0.7206	0.672	0.4547	0.033*
C11	0.5927 (5)	0.7584 (5)	0.5843 (4)	0.0404 (13)
H11A	0.5981	0.7717	0.6475	0.061*
H11B	0.5318	0.7186	0.5925	0.061*
H11C	0.5612	0.8256	0.5561	0.061*
C12	0.7852 (6)	0.5903 (5)	0.5637 (5)	0.0453 (14)
H12A	0.871	0.5482	0.52	0.068*
H12B	0.7244	0.5496	0.5773	0.068*
H12C	0.7937	0.6083	0.6246	0.068*
C13	0.6972 (4)	0.5653 (3)	0.1692 (3)	0.0192 (9)
C14	0.7022 (4)	0.4784 (4)	0.2323 (3)	0.0226 (9)
C15	0.6217 (5)	0.4149 (4)	0.2379 (3)	0.0282 (10)
H15	0.6266	0.357	0.2784	0.034*
C16	0.5353 (5)	0.4361 (4)	0.1847 (4)	0.0306 (11)
H16	0.4813	0.3937	0.1899	0.037*
C17	0.5298 (5)	0.5218 (4)	0.1233 (3)	0.0261 (10)
H17	0.4718	0.5357	0.087	0.031*
C18	0.6073 (4)	0.5871 (3)	0.1142 (3)	0.0193 (9)
C19	0.7952 (5)	0.4533 (4)	0.2924 (3)	0.0267 (10)
H19	0.8076	0.5209	0.3049	0.032*
C20	0.7410 (6)	0.4094 (4)	0.3930 (4)	0.0375 (12)
H20A	0.6539	0.4573	0.4286	0.056*
H20B	0.8	0.4035	0.43	0.056*
H20C	0.7351	0.3398	0.3836	0.056*
C21	0.9322 (5)	0.3769 (5)	0.2345 (4)	0.0390 (12)
H21A	0.9246	0.3085	0.2232	0.058*
H21B	0.9916	0.3682	0.2716	0.058*
H21C	0.9668	0.406	0.172	0.058*
C22	0.6044 (4)	0.6763 (3)	0.0418 (3)	0.0210 (9)
H22	0.6282	0.7316	0.0675	0.025*
C23	0.4647 (5)	0.7303 (4)	0.0324 (4)	0.0306 (11)
H23A	0.4414	0.6797	0.0022	0.046*
H23B	0.4661	0.7911	−0.008	0.046*
H23C	0.3999	0.7538	0.0969	0.046*
C24	0.7096 (5)	0.6349 (4)	−0.0588 (3)	0.0294 (10)
H24A	0.7965	0.6084	−0.0518	0.044*
H24B	0.7071	0.6924	−0.1033	0.044*
H24C	0.6918	0.578	−0.0848	0.044*
C25	1.0286 (4)	0.6345 (4)	0.2313 (3)	0.0251 (10)
H25A	1.0531	0.5737	0.1859	0.03*
H25B	0.9602	0.6261	0.2911	0.03*
C26	1.1508 (5)	0.6316 (5)	0.2573 (4)	0.0380 (12)
H26A	1.2205	0.6373	0.1982	0.057*
H26B	1.1814	0.5652	0.2868	0.057*
H26C	1.1274	0.6907	0.3033	0.057*
C27	1.0646 (4)	0.7550 (4)	0.0928 (3)	0.0239 (9)
H27A	1.1431	0.7593	0.1047	0.029*
H27B	1.0217	0.8239	0.0707	0.029*
C28	1.1072 (7)	0.6691 (5)	0.0121 (4)	0.0509 (16)
H28A	1.1663	0.6043	0.027	0.076*
H28B	1.1527	0.6931	−0.0502	0.076*
H28C	1.0298	0.6555	0.0081	0.076*
C29	0.4813 (5)	0.7500 (4)	0.3598 (3)	0.0282 (10)
H29A	0.4477	0.7966	0.419	0.034*
H29B	0.5585	0.6917	0.3636	0.034*
C30	0.3737 (5)	0.7030 (5)	0.3591 (4)	0.0366 (12)
H30A	0.2926	0.7603	0.364	0.055*
H30B	0.3577	0.6583	0.4143	0.055*
H30C	0.403	0.6608	0.2985	0.055*
C31	0.4177 (4)	0.9023 (4)	0.2580 (4)	0.0292 (10)
H31A	0.3505	0.8756	0.2497	0.035*
H31B	0.4546	0.9342	0.1969	0.035*
C32	0.3507 (8)	0.9887 (5)	0.3406 (5)	0.067 (2)
H32A	0.3025	0.9608	0.3992	0.101*
H32B	0.2898	1.0489	0.3214	0.101*
H32C	0.4173	1.0112	0.3536	0.101*
C33	0.7937 (4)	0.8757 (4)	0.0015 (3)	0.0268 (10)
H33A	0.8264	0.7982	−0.0097	0.032*
H33B	0.8697	0.9015	−0.0258	0.032*
C34	0.6955 (5)	0.9233 (4)	−0.0547 (4)	0.0344 (12)
H34A	0.6159	0.9041	−0.0243	0.052*
H34B	0.736	0.8955	−0.1223	0.052*
H34C	0.6729	1.0002	−0.0527	0.052*
C35	0.6795 (5)	1.0173 (4)	0.1362 (4)	0.0297 (10)
H35A	0.6508	1.027	0.2077	0.036*
H35B	0.6006	1.0457	0.1166	0.036*
C36	0.7729 (6)	1.0832 (4)	0.0903 (4)	0.0405 (13)
H36A	0.8553	1.0516	0.1035	0.061*
H36B	0.7313	1.1555	0.1186	0.061*
H36C	0.7906	1.0839	0.0201	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zr1	0.0557 (4)	0.0191 (2)	0.0234 (3)	−0.0121 (2)	−0.0168 (2)	0.00391 (17)
N1	0.0115 (17)	0.028 (2)	0.0236 (19)	−0.0066 (15)	−0.0036 (14)	−0.0005 (16)
N2	0.0132 (18)	0.0206 (19)	0.0262 (19)	−0.0045 (15)	−0.0079 (15)	0.0025 (15)
N3	0.0156 (19)	0.0203 (19)	0.035 (2)	−0.0068 (15)	−0.0042 (16)	−0.0001 (16)
N4	0.0171 (19)	0.035 (2)	0.025 (2)	−0.0036 (17)	−0.0046 (15)	0.0012 (17)
N5	0.0151 (18)	0.0180 (18)	0.0237 (19)	−0.0038 (14)	−0.0047 (14)	−0.0006 (14)
C1	0.013 (2)	0.021 (2)	0.020 (2)	−0.0019 (17)	−0.0023 (16)	−0.0057 (17)
C2	0.011 (2)	0.025 (2)	0.022 (2)	−0.0028 (17)	−0.0021 (16)	−0.0082 (17)
C3	0.018 (2)	0.031 (3)	0.036 (3)	−0.0060 (19)	−0.0078 (19)	−0.007 (2)
C4	0.018 (2)	0.041 (3)	0.040 (3)	−0.004 (2)	−0.015 (2)	−0.008 (2)
C5	0.033 (3)	0.035 (3)	0.026 (2)	−0.007 (2)	−0.015 (2)	0.001 (2)
C6	0.023 (2)	0.024 (2)	0.022 (2)	−0.0027 (19)	−0.0049 (18)	−0.0056 (18)
C7	0.023 (2)	0.024 (2)	0.026 (2)	−0.0083 (19)	−0.0070 (18)	−0.0045 (18)
C8	0.035 (3)	0.025 (3)	0.038 (3)	−0.005 (2)	−0.008 (2)	0.000 (2)
C9	0.030 (3)	0.048 (3)	0.035 (3)	−0.023 (2)	−0.004 (2)	0.003 (2)
C10	0.025 (2)	0.029 (3)	0.029 (2)	−0.009 (2)	−0.0093 (19)	0.003 (2)
C11	0.035 (3)	0.048 (3)	0.033 (3)	−0.018 (3)	0.000 (2)	0.004 (2)
C12	0.059 (4)	0.036 (3)	0.053 (4)	−0.019 (3)	−0.031 (3)	0.013 (3)
C13	0.012 (2)	0.022 (2)	0.020 (2)	−0.0049 (17)	−0.0014 (16)	−0.0032 (17)
C14	0.018 (2)	0.025 (2)	0.023 (2)	−0.0074 (18)	−0.0032 (17)	−0.0011 (18)
C15	0.030 (3)	0.028 (2)	0.028 (2)	−0.016 (2)	−0.006 (2)	0.006 (2)
C16	0.027 (3)	0.036 (3)	0.034 (3)	−0.021 (2)	−0.006 (2)	−0.001 (2)
C17	0.023 (2)	0.033 (3)	0.025 (2)	−0.012 (2)	−0.0072 (19)	−0.0018 (19)
C18	0.015 (2)	0.020 (2)	0.019 (2)	−0.0037 (17)	−0.0023 (16)	−0.0050 (17)
C19	0.027 (2)	0.025 (2)	0.031 (3)	−0.011 (2)	−0.012 (2)	0.0074 (19)
C20	0.048 (3)	0.039 (3)	0.030 (3)	−0.017 (3)	−0.016 (2)	0.009 (2)
C21	0.033 (3)	0.042 (3)	0.038 (3)	−0.004 (2)	−0.014 (2)	0.005 (2)
C22	0.021 (2)	0.018 (2)	0.024 (2)	−0.0035 (17)	−0.0099 (18)	−0.0028 (17)
C23	0.021 (2)	0.028 (3)	0.043 (3)	−0.002 (2)	−0.016 (2)	0.001 (2)
C24	0.025 (2)	0.031 (3)	0.028 (2)	−0.007 (2)	−0.0051 (19)	0.003 (2)
C25	0.022 (2)	0.023 (2)	0.029 (2)	−0.0064 (19)	−0.0084 (19)	0.0012 (19)
C26	0.033 (3)	0.042 (3)	0.047 (3)	−0.014 (2)	−0.022 (2)	0.011 (2)
C27	0.017 (2)	0.026 (2)	0.026 (2)	−0.0059 (18)	−0.0043 (18)	0.0023 (19)
C28	0.072 (4)	0.037 (3)	0.028 (3)	−0.005 (3)	−0.007 (3)	−0.003 (2)
C29	0.020 (2)	0.043 (3)	0.020 (2)	−0.011 (2)	−0.0021 (18)	−0.003 (2)
C30	0.029 (3)	0.047 (3)	0.037 (3)	−0.020 (2)	−0.008 (2)	0.003 (2)
C31	0.015 (2)	0.033 (3)	0.037 (3)	−0.0052 (19)	−0.0066 (19)	−0.003 (2)
C32	0.077 (5)	0.040 (4)	0.057 (4)	0.001 (3)	−0.003 (4)	−0.017 (3)
C33	0.018 (2)	0.032 (3)	0.028 (2)	−0.0070 (19)	−0.0059 (18)	0.005 (2)
C34	0.036 (3)	0.038 (3)	0.033 (3)	−0.014 (2)	−0.018 (2)	0.011 (2)
C35	0.031 (3)	0.022 (2)	0.039 (3)	−0.008 (2)	−0.016 (2)	0.003 (2)
C36	0.048 (3)	0.032 (3)	0.053 (3)	−0.021 (3)	−0.026 (3)	0.017 (3)

Geometric parameters (Å, º) top

Zr1—N5	2.036 (4)	C18—C22	1.519 (6)
Zr1—N2	2.122 (4)	C19—C21	1.520 (7)
Zr1—N1	2.129 (4)	C19—C20	1.524 (7)
Zr1—N4	2.160 (4)	C19—H19	0.98
Zr1—N3	2.402 (4)	C20—H20A	0.96
N1—C1	1.417 (5)	C20—H20B	0.96
N1—H1A	0.890 (2)	C20—H20C	0.96
N2—C13	1.407 (5)	C21—H21A	0.96
N2—H2	0.87 (5)	C21—H21B	0.96
N3—C25	1.470 (6)	C21—H21C	0.96
N3—C27	1.473 (6)	C22—C24	1.522 (6)
N3—H3A	0.84 (5)	C22—C23	1.546 (6)
N4—C29	1.465 (6)	C22—H22	0.98
N4—C31	1.465 (6)	C23—H23A	0.96
N5—C33	1.469 (6)	C23—H23B	0.96
N5—C35	1.470 (6)	C23—H23C	0.96
C1—C6	1.417 (6)	C24—H24A	0.96
C1—C2	1.418 (6)	C24—H24B	0.96
C2—C3	1.398 (6)	C24—H24C	0.96
C2—C7	1.515 (6)	C25—C26	1.524 (6)
C3—C4	1.376 (7)	C25—H25A	0.97
C3—H3	0.93	C25—H25B	0.97
C4—C5	1.389 (7)	C26—H26A	0.96
C4—H4	0.93	C26—H26B	0.96
C5—C6	1.399 (6)	C26—H26C	0.96
C5—H5	0.93	C27—C28	1.511 (7)
C6—C10	1.512 (7)	C27—H27A	0.97
C7—C9	1.518 (6)	C27—H27B	0.97
C7—C8	1.546 (6)	C28—H28A	0.96
C7—H7	0.98	C28—H28B	0.96
C8—H8A	0.96	C28—H28C	0.96
C8—H8B	0.96	C29—C30	1.525 (7)
C8—H8C	0.96	C29—H29A	0.97
C9—H9A	0.96	C29—H29B	0.97
C9—H9B	0.96	C30—H30A	0.96
C9—H9C	0.96	C30—H30B	0.96
C10—C12	1.525 (7)	C30—H30C	0.96
C10—C11	1.537 (7)	C31—C32	1.508 (8)
C10—H10	0.98	C31—H31A	0.97
C11—H11A	0.96	C31—H31B	0.97
C11—H11B	0.96	C32—H32A	0.96
C11—H11C	0.96	C32—H32B	0.96
C12—H12A	0.96	C32—H32C	0.96
C12—H12B	0.96	C33—C34	1.531 (6)
C12—H12C	0.96	C33—H33A	0.97
C13—C14	1.413 (6)	C33—H33B	0.97
C13—C18	1.427 (6)	C34—H34A	0.96
C14—C15	1.396 (6)	C34—H34B	0.96
C14—C19	1.511 (6)	C34—H34C	0.96
C15—C16	1.375 (7)	C35—C36	1.528 (7)
C15—H15	0.93	C35—H35A	0.97
C16—C17	1.387 (7)	C35—H35B	0.97
C16—H16	0.93	C36—H36A	0.96
C17—C18	1.378 (6)	C36—H36B	0.96
C17—H17	0.93	C36—H36C	0.96

N5—Zr1—N2	115.34 (14)	C21—C19—H19	107
N5—Zr1—N1	116.93 (14)	C20—C19—H19	107
N2—Zr1—N1	126.85 (14)	C19—C20—H20A	109.5
N5—Zr1—N4	100.60 (14)	C19—C20—H20B	109.5
N2—Zr1—N4	90.93 (15)	H20A—C20—H20B	109.5
N1—Zr1—N4	88.60 (14)	C19—C20—H20C	109.5
N5—Zr1—N3	95.87 (13)	H20A—C20—H20C	109.5
N2—Zr1—N3	83.79 (14)	H20B—C20—H20C	109.5
N1—Zr1—N3	82.12 (14)	C19—C21—H21A	109.5
N4—Zr1—N3	163.41 (14)	C19—C21—H21B	109.5
C1—N1—Zr1	138.4 (3)	H21A—C21—H21B	109.5
C1—N1—H1A	105 (3)	C19—C21—H21C	109.5
Zr1—N1—H1A	111 (3)	H21A—C21—H21C	109.5
C13—N2—Zr1	133.5 (3)	H21B—C21—H21C	109.5
C13—N2—H2	109 (3)	C18—C22—C24	110.6 (4)
Zr1—N2—H2	111 (3)	C18—C22—C23	113.1 (4)
C25—N3—C27	114.4 (4)	C24—C22—C23	111.1 (4)
C25—N3—Zr1	117.5 (3)	C18—C22—H22	107.3
C27—N3—Zr1	120.5 (3)	C24—C22—H22	107.3
C25—N3—H3A	99 (4)	C23—C22—H22	107.3
C27—N3—H3A	106 (4)	C22—C23—H23A	109.5
Zr1—N3—H3A	93 (4)	C22—C23—H23B	109.5
C29—N4—C31	114.7 (4)	H23A—C23—H23B	109.5
C29—N4—Zr1	116.7 (3)	C22—C23—H23C	109.5
C31—N4—Zr1	125.7 (3)	H23A—C23—H23C	109.5
C33—N5—C35	114.2 (4)	H23B—C23—H23C	109.5
C33—N5—Zr1	124.4 (3)	C22—C24—H24A	109.5
C35—N5—Zr1	121.4 (3)	C22—C24—H24B	109.5
C6—C1—N1	120.8 (4)	H24A—C24—H24B	109.5
C6—C1—C2	119.6 (4)	C22—C24—H24C	109.5
N1—C1—C2	119.6 (4)	H24A—C24—H24C	109.5
C3—C2—C1	119.4 (4)	H24B—C24—H24C	109.5
C3—C2—C7	119.5 (4)	N3—C25—C26	114.5 (4)
C1—C2—C7	120.9 (4)	N3—C25—H25A	108.6
C4—C3—C2	121.0 (4)	C26—C25—H25A	108.6
C4—C3—H3	119.5	N3—C25—H25B	108.6
C2—C3—H3	119.5	C26—C25—H25B	108.6
C3—C4—C5	119.9 (4)	H25A—C25—H25B	107.6
C3—C4—H4	120.1	C25—C26—H26A	109.5
C5—C4—H4	120.1	C25—C26—H26B	109.5
C4—C5—C6	121.4 (5)	H26A—C26—H26B	109.5
C4—C5—H5	119.3	C25—C26—H26C	109.5
C6—C5—H5	119.3	H26A—C26—H26C	109.5
C5—C6—C1	118.7 (4)	H26B—C26—H26C	109.5
C5—C6—C10	121.0 (4)	N3—C27—C28	112.3 (4)
C1—C6—C10	120.4 (4)	N3—C27—H27A	109.1
C2—C7—C9	115.3 (4)	C28—C27—H27A	109.1
C2—C7—C8	109.3 (4)	N3—C27—H27B	109.1
C9—C7—C8	110.1 (4)	C28—C27—H27B	109.1
C2—C7—H7	107.3	H27A—C27—H27B	107.9
C9—C7—H7	107.3	C27—C28—H28A	109.5
C8—C7—H7	107.3	C27—C28—H28B	109.5
C7—C8—H8A	109.5	H28A—C28—H28B	109.5
C7—C8—H8B	109.5	C27—C28—H28C	109.5
H8A—C8—H8B	109.5	H28A—C28—H28C	109.5
C7—C8—H8C	109.5	H28B—C28—H28C	109.5
H8A—C8—H8C	109.5	N4—C29—C30	114.9 (4)
H8B—C8—H8C	109.5	N4—C29—H29A	108.5
C7—C9—H9A	109.5	C30—C29—H29A	108.5
C7—C9—H9B	109.5	N4—C29—H29B	108.5
H9A—C9—H9B	109.5	C30—C29—H29B	108.5
C7—C9—H9C	109.5	H29A—C29—H29B	107.5
H9A—C9—H9C	109.5	C29—C30—H30A	109.5
H9B—C9—H9C	109.5	C29—C30—H30B	109.5
C6—C10—C12	114.6 (4)	H30A—C30—H30B	109.5
C6—C10—C11	110.6 (4)	C29—C30—H30C	109.5
C12—C10—C11	109.1 (4)	H30A—C30—H30C	109.5
C6—C10—H10	107.4	H30B—C30—H30C	109.5
C12—C10—H10	107.4	N4—C31—C32	114.6 (5)
C11—C10—H10	107.4	N4—C31—H31A	108.6
C10—C11—H11A	109.5	C32—C31—H31A	108.6
C10—C11—H11B	109.5	N4—C31—H31B	108.6
H11A—C11—H11B	109.5	C32—C31—H31B	108.6
C10—C11—H11C	109.5	H31A—C31—H31B	107.6
H11A—C11—H11C	109.5	C31—C32—H32A	109.5
H11B—C11—H11C	109.5	C31—C32—H32B	109.5
C10—C12—H12A	109.5	H32A—C32—H32B	109.5
C10—C12—H12B	109.5	C31—C32—H32C	109.5
H12A—C12—H12B	109.5	H32A—C32—H32C	109.5
C10—C12—H12C	109.5	H32B—C32—H32C	109.5
H12A—C12—H12C	109.5	N5—C33—C34	114.7 (4)
H12B—C12—H12C	109.5	N5—C33—H33A	108.6
N2—C13—C14	121.1 (4)	C34—C33—H33A	108.6
N2—C13—C18	120.0 (4)	N5—C33—H33B	108.6
C14—C13—C18	118.8 (4)	C34—C33—H33B	108.6
C15—C14—C13	119.5 (4)	H33A—C33—H33B	107.6
C15—C14—C19	120.0 (4)	C33—C34—H34A	109.5
C13—C14—C19	120.5 (4)	C33—C34—H34B	109.5
C16—C15—C14	121.5 (4)	H34A—C34—H34B	109.5
C16—C15—H15	119.3	C33—C34—H34C	109.5
C14—C15—H15	119.3	H34A—C34—H34C	109.5
C15—C16—C17	118.9 (4)	H34B—C34—H34C	109.5
C15—C16—H16	120.5	N5—C35—C36	115.0 (4)
C17—C16—H16	120.5	N5—C35—H35A	108.5
C18—C17—C16	122.3 (4)	C36—C35—H35A	108.5
C18—C17—H17	118.8	N5—C35—H35B	108.5
C16—C17—H17	118.8	C36—C35—H35B	108.5
C17—C18—C13	118.9 (4)	H35A—C35—H35B	107.5
C17—C18—C22	120.8 (4)	C35—C36—H36A	109.5
C13—C18—C22	120.2 (4)	C35—C36—H36B	109.5
C14—C19—C21	111.3 (4)	H36A—C36—H36B	109.5
C14—C19—C20	114.2 (4)	C35—C36—H36C	109.5
C21—C19—C20	109.9 (4)	H36A—C36—H36C	109.5
C14—C19—H19	107	H36B—C36—H36C	109.5

N5—Zr1—N1—C1	−96.8 (5)	N1—C1—C6—C10	−3.1 (6)
N2—Zr1—N1—C1	71.9 (5)	C2—C1—C6—C10	178.9 (4)
N4—Zr1—N1—C1	162.0 (5)	C3—C2—C7—C9	28.7 (6)
N3—Zr1—N1—C1	−4.2 (4)	C1—C2—C7—C9	−155.7 (4)
N5—Zr1—N2—C13	−105.4 (4)	C3—C2—C7—C8	−95.9 (5)
N1—Zr1—N2—C13	85.7 (4)	C1—C2—C7—C8	79.7 (5)
N4—Zr1—N2—C13	−3.2 (4)	C5—C6—C10—C12	−25.1 (6)
N3—Zr1—N2—C13	161.0 (4)	C1—C6—C10—C12	155.9 (4)
N5—Zr1—N3—C25	−167.4 (3)	C5—C6—C10—C11	98.6 (5)
N2—Zr1—N3—C25	−52.5 (3)	C1—C6—C10—C11	−80.3 (5)
N1—Zr1—N3—C25	76.1 (3)	Zr1—N2—C13—C14	−106.6 (4)
N4—Zr1—N3—C25	19.6 (7)	Zr1—N2—C13—C18	72.2 (5)
N5—Zr1—N3—C27	−19.4 (3)	N2—C13—C14—C15	−179.9 (4)
N2—Zr1—N3—C27	95.5 (3)	C18—C13—C14—C15	1.3 (6)
N1—Zr1—N3—C27	−135.9 (3)	N2—C13—C14—C19	−0.7 (6)
N4—Zr1—N3—C27	167.5 (4)	C18—C13—C14—C19	−179.5 (4)
N5—Zr1—N4—C29	−174.3 (3)	C13—C14—C15—C16	−1.3 (7)
N2—Zr1—N4—C29	69.7 (3)	C19—C14—C15—C16	179.5 (4)
N1—Zr1—N4—C29	−57.2 (3)	C14—C15—C16—C17	0.9 (7)
N3—Zr1—N4—C29	−1.4 (7)	C15—C16—C17—C18	−0.5 (7)
N5—Zr1—N4—C31	−14.6 (4)	C16—C17—C18—C13	0.5 (7)
N2—Zr1—N4—C31	−130.6 (4)	C16—C17—C18—C22	176.5 (4)
N1—Zr1—N4—C31	102.5 (4)	N2—C13—C18—C17	−179.8 (4)
N3—Zr1—N4—C31	158.3 (4)	C14—C13—C18—C17	−0.9 (6)
N2—Zr1—N5—C33	−14.4 (4)	N2—C13—C18—C22	4.2 (6)
N1—Zr1—N5—C33	155.6 (3)	C14—C13—C18—C22	−176.9 (4)
N4—Zr1—N5—C33	−110.5 (3)	C15—C14—C19—C21	90.7 (5)
N3—Zr1—N5—C33	71.5 (3)	C13—C14—C19—C21	−88.5 (5)
N2—Zr1—N5—C35	164.6 (3)	C15—C14—C19—C20	−34.4 (6)
N1—Zr1—N5—C35	−25.4 (4)	C13—C14—C19—C20	146.4 (4)
N4—Zr1—N5—C35	68.4 (3)	C17—C18—C22—C24	−90.1 (5)
N3—Zr1—N5—C35	−109.5 (3)	C13—C18—C22—C24	85.9 (5)
Zr1—N1—C1—C6	−105.2 (5)	C17—C18—C22—C23	35.2 (6)
Zr1—N1—C1—C2	72.9 (6)	C13—C18—C22—C23	−148.8 (4)
C6—C1—C2—C3	0.2 (6)	C27—N3—C25—C26	59.7 (5)
N1—C1—C2—C3	−177.8 (4)	Zr1—N3—C25—C26	−150.5 (3)
C6—C1—C2—C7	−175.4 (4)	C25—N3—C27—C28	63.2 (5)
N1—C1—C2—C7	6.6 (6)	Zr1—N3—C27—C28	−85.7 (5)
C1—C2—C3—C4	0.2 (7)	C31—N4—C29—C30	58.1 (6)
C7—C2—C3—C4	175.9 (4)	Zr1—N4—C29—C30	−140.0 (4)
C2—C3—C4—C5	−0.7 (7)	C29—N4—C31—C32	62.7 (6)
C3—C4—C5—C6	0.8 (7)	Zr1—N4—C31—C32	−97.4 (5)
C4—C5—C6—C1	−0.4 (7)	C35—N5—C33—C34	−56.0 (5)
C4—C5—C6—C10	−179.4 (4)	Zr1—N5—C33—C34	123.1 (4)
N1—C1—C6—C5	177.9 (4)	C33—N5—C35—C36	−54.4 (5)
C2—C1—C6—C5	−0.1 (6)	Zr1—N5—C35—C36	126.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1	0.84 (5)	2.56 (5)	2.983 (5)	112 (4)

Experimental details

Crystal data
Chemical formula	[Zr(C₁₂H₁₈N)₂(C₄H₁₀N)₂(C₄H₁₁N)]
M_r	661.17
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	11.2079 (3), 13.1612 (5), 14.3443 (6)
α, β, γ (°)	86.578 (3), 70.484 (3), 71.232 (3)
V (Å³)	1885.61 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.58 × 0.39 × 0.34

Data collection
Diffractometer	Agilent Xcalibur (Sapphire2 diffractometer
Absorption correction	Analytical (CrysAlis PRO; Agilent, 2010)
T_min, T_max	0.889, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	11493, 7412, 5867
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.073, 0.188, 1.12
No. of reflections	7412
No. of parameters	402
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.82, −2.13

Computer programs: CrysAlis PRO (Agilent, 2010), SUPERFLIP (Palatinus & Chapuis, 2007), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1	0.84 (5)	2.56 (5)	2.983 (5)	112 (4)

References

Agilent (2010). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Blake, A. J., Nikonov, G. I. & Mountford, P. (1997). Acta Cryst. C53, 874–876. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ghesner, I., Fenwick, A. & Stephen, D. W. (2006). Organometallics, 25, 4985–4995. Web of Science CSD CrossRef CAS Google Scholar
Kempe, R. (2000). Angew. Chem. Int. Ed. 39, 468–493. CrossRef CAS Google Scholar
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Volume 69| Part 2| February 2013| Page m72

doi:10.1107/S160053681205115X

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(di­ethyl­amido-κN)(di­ethyl­amine-κN)bis­­(2,6-diiso­propyl­phenyl­amido-κN)zirconium(IV)

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Experimental

Crystal data

Data collection

Refinement

Supporting information

References

metal-organic compounds

Bis(diethylamido-κN)(diethylamine-κN)bis(2,6-diisopropylphenylamido-κN)zirconium(IV)