[1,1-(Butane-1,4-diyl)-2,3-dicyclohexylguanidinato]dimethylaluminum(III)

Li, H.; Xiang, Y.; Han, H.

doi:10.1107/S1600536810046787

metal-organic compounds

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Volume 66| Part 12| December 2010| Page m1598

https://doi.org/10.1107/S1600536810046787

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[1,1-(Butane-1,4-diyl)-2,3-dicyclohexylguanidinato]dimethylaluminum(III)

Haoyang Li,^a Yonggang Xiang ^a and Hongfei Han ^a ^*

^aDepartment of Chemistry, Taiyuan Normal University, Taiyuan 030031, People's Republic of China
^*Correspondence e-mail: hhf_2222@yahoo.com.cn

(Received 17 October 2010; accepted 12 November 2010; online 20 November 2010)

In the crystal structure of the title complex, [Al(CH₃)₂(C₁₇H₃₀N₃)], the Al^III cation is coordinated by two methyl ligands and two N atoms from the guanidinato ligand in a distorted tetrahedral geometry. The dihedral angle between the CN₂ and AlC₂ planes is 85.37 (2)°. The two N atoms of the guanidinato ligand exhibit an almost uniform affinity to the metal atom.

Related literature

For related guanidinato compounds, see: Chandra et al. (1970 ); Coles & Hitchcock (2004 ); Corey et al. (2006 ); Zhou et al. (2007 ). For related ortho metalation reactions, see: Kondo et al. (2007 ).

Experimental

Crystal data

[Al(CH₃)₂(C₁₇H₃₀N₃)]
M_r = 333.49
Orthorhombic, P b c n
a = 18.263 (4) Å
b = 10.596 (2) Å
c = 10.449 (2) Å
V = 2022.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.959, T_max = 0.969
7156 measured reflections
1772 independent reflections
1630 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.095
wR(F²) = 0.232
S = 1.42
1772 reflections
107 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Al—N1	1.922 (4)
Al—C18	1.961 (6)

N1—Al—N1ⁱ	69.8 (2)
C18ⁱ—Al—C18	114.2 (4)
Symmetry code: (i) $[-x+1, y, -z+{\script{1\over 2}}]$ .

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: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810046787/jh2223sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046787/jh2223Isup2.hkl

checkCIF report

Comment top

Since the first guanidinato complexes have been reported in 1970 by Lappert et al. (Chandra et al., 1970), guanidinato ligands have been used extensively in the coordination chemistry of transition, f-block, and main-group metals (Corey et al., 2006). Moreover many guanidinato complexes were reported showing good performance in ethylene polymerization (Zhou et al., 2007) and in Ring-Opening Polymerisation (Coles & Hitchcock, 2004). It implied that the guanidinato complex would behave better in catalysis application.

There has been a great deal of research in directed ortho metalation reactions (Kondo et al., 2007). We had expected guanidinato lithium, the result of the addition of N,N'-dicyclohexyl carbodiimide with N-tetrahydropyrrolyl lithium, when reacting with trimethyl aluminum, to produced a new kind of complex containing Al and Li atoms. However, X-ray diffraction on the complex obtained in the reaction revealed that the Li atom was replaced by Al atom surprisingly. Its molecular structure is shown in Fig. 1. In the molecular structure of the complex, the metal atom is chelated with the guanidinato ligand. The four-coordinate Al(III) center demonstrates a highly distorted tetrahedral geometry. The distances from the two N atoms to Al atom are almost equal [N1-Al: 1.918 (4) Å, N2-Al: 1.925 (4) Å]. It indicates that the two N atoms of guanidinato ligand exhibit almost uniform affinity to the metal center.

Related literature top

For related guanidinato compounds, see: Chandra et al. (1970); Coles et al. (2004); Corey et al. (2006); Zhou et al. (2007). For related ortho metalation reactions, see: Kondo et al. (2007).

Experimental top

A solution of N-tetrahydropyrrolyl lithium in diethylether (0.232g, 3mmol) was added dropwise with stirring at 273K to a solution of 0.619g (3mmol) of N, N'-dicyclohexyl carbodiimide in ether. The mixture was warmed to room temperature and stirred for 2h. A 2M solution of trimethylaluminum in heaxene (1.5mL, 3mmol) was added at 195K to the mixed solution. The mixture was warmed to room temperature and stirred for 12h. Concentration of the filtrate under reduced pressure produced the colorless crystals suitable for X-ray analysis 3 days later (yield 0.620g, 62%).

Structure description top

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: DIAMOND (Brandenburg, 1999); 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. H atoms are presented as a small spheres of arbitrary radius.

[1,1-(Butane-1,4-diyl)-2,3-dicyclohexylguanidinato]dimethylaluminum(III) top

Crystal data top

[Al(CH₃)₂(C₁₇H₃₀N₃)]	D_x = 1.095 Mg m⁻³
M_r = 333.49	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 4606 reflections
a = 18.263 (4) Å	θ = 3.0–27.0°
b = 10.596 (2) Å	µ = 0.11 mm⁻¹
c = 10.449 (2) Å	T = 293 K
V = 2022.0 (7) Å³	Block, colorless
Z = 4	0.40 × 0.30 × 0.30 mm
F(000) = 736

Data collection top

Bruker SMART CCD area-detector diffractometer	1772 independent reflections
Radiation source: fine-focus sealed tube	1630 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
phi and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −21→21
T_min = 0.959, T_max = 0.969	k = −12→7
7156 measured reflections	l = −11→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)] = 0.095	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.232	H-atom parameters constrained
S = 1.42	w = 1/[σ²(F_o²) + (0.P)² + 5.155P] where P = (F_o² + 2F_c²)/3
1772 reflections	(Δ/σ)_max = 0.005
107 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

[Al(CH₃)₂(C₁₇H₃₀N₃)]	V = 2022.0 (7) Å³
M_r = 333.49	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 18.263 (4) Å	µ = 0.11 mm⁻¹
b = 10.596 (2) Å	T = 293 K
c = 10.449 (2) Å	0.40 × 0.30 × 0.30 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1772 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1630 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.969	R_int = 0.059
7156 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.095	0 restraints
wR(F²) = 0.232	H-atom parameters constrained
S = 1.42	Δρ_max = 0.31 e Å⁻³
1772 reflections	Δρ_min = −0.43 e Å⁻³
107 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Al	0.5000	0.29276 (18)	0.2500	0.0381 (6)
N1	0.45266 (19)	0.1440 (3)	0.1850 (3)	0.0310 (8)
N3	0.5000	−0.0569 (5)	0.2500	0.0397 (13)
C1	0.5000	0.0706 (6)	0.2500	0.0318 (13)
C2	0.3760 (2)	0.1118 (4)	0.1598 (4)	0.0334 (10)
H2	0.3744	0.0415	0.0989	0.040*
C3	0.3350 (3)	0.0733 (5)	0.2815 (5)	0.0418 (12)
H3A	0.3575	−0.0019	0.3170	0.050*
H3B	0.3392	0.1402	0.3444	0.050*
C4	0.2546 (3)	0.0474 (5)	0.2557 (7)	0.0611 (15)
H4A	0.2302	0.0270	0.3355	0.073*
H4B	0.2501	−0.0247	0.1991	0.073*
C5	0.2177 (3)	0.1614 (6)	0.1948 (6)	0.0569 (15)
H5A	0.1673	0.1407	0.1743	0.068*
H5B	0.2175	0.2309	0.2551	0.068*
C6	0.2573 (3)	0.2010 (6)	0.0742 (5)	0.0539 (14)
H6A	0.2349	0.2770	0.0405	0.065*
H6B	0.2525	0.1352	0.0102	0.065*
C7	0.3384 (2)	0.2255 (5)	0.1001 (5)	0.0435 (12)
H7A	0.3626	0.2465	0.0203	0.052*
H7B	0.3432	0.2972	0.1571	0.052*
C14	0.4666 (3)	−0.1349 (4)	0.1484 (5)	0.0473 (13)
H14A	0.4815	−0.1066	0.0641	0.057*
H14B	0.4136	−0.1338	0.1538	0.057*
C15	0.4971 (3)	−0.2657 (5)	0.1782 (6)	0.0613 (16)
H15A	0.4642	−0.3314	0.1486	0.074*
H15B	0.5447	−0.2777	0.1388	0.074*
C18	0.4388 (3)	0.3932 (5)	0.3656 (6)	0.0586 (16)
H18A	0.4076	0.3382	0.4141	0.088*
H18B	0.4093	0.4505	0.3165	0.088*
H18C	0.4695	0.4403	0.4229	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Al	0.0304 (10)	0.0312 (10)	0.0526 (12)	0.000	−0.0093 (9)	0.000
N1	0.0254 (17)	0.0324 (18)	0.0351 (19)	−0.0015 (15)	0.0006 (15)	0.0007 (16)
N3	0.037 (3)	0.033 (3)	0.049 (3)	0.000	0.007 (3)	0.000
C1	0.032 (3)	0.032 (3)	0.032 (3)	0.000	0.010 (3)	0.000
C2	0.029 (2)	0.037 (2)	0.034 (2)	−0.0060 (18)	0.0002 (18)	−0.0059 (19)
C3	0.036 (2)	0.043 (3)	0.047 (3)	0.004 (2)	0.006 (2)	0.009 (2)
C4	0.033 (2)	0.057 (3)	0.094 (4)	−0.005 (2)	0.011 (3)	0.020 (3)
C5	0.026 (2)	0.061 (3)	0.084 (4)	−0.002 (2)	−0.001 (3)	0.006 (3)
C6	0.037 (3)	0.070 (4)	0.055 (3)	0.001 (3)	−0.014 (2)	0.000 (3)
C7	0.032 (2)	0.056 (3)	0.042 (2)	0.000 (2)	−0.006 (2)	0.013 (2)
C14	0.051 (3)	0.037 (3)	0.054 (3)	−0.009 (2)	0.018 (2)	−0.012 (2)
C15	0.057 (3)	0.036 (2)	0.091 (4)	−0.006 (3)	0.035 (3)	−0.012 (3)
C18	0.049 (3)	0.048 (3)	0.079 (4)	0.011 (3)	−0.019 (3)	−0.025 (3)

Geometric parameters (Å, º) top

Al—N1	1.922 (4)	C4—H4B	0.9700
Al—N1ⁱ	1.922 (4)	C5—C6	1.512 (8)
Al—C18ⁱ	1.961 (6)	C5—H5A	0.9700
Al—C18	1.961 (6)	C5—H5B	0.9700
N1—C1	1.346 (5)	C6—C7	1.528 (7)
N1—C2	1.465 (5)	C6—H6A	0.9700
N3—C1	1.351 (8)	C6—H6B	0.9700
N3—C14	1.477 (6)	C7—H7A	0.9700
N3—C14ⁱ	1.477 (6)	C7—H7B	0.9700
C1—N1ⁱ	1.346 (5)	C14—C15	1.526 (7)
C2—C7	1.520 (6)	C14—H14A	0.9700
C2—C3	1.531 (6)	C14—H14B	0.9700
C2—H2	0.9800	C15—C15ⁱ	1.505 (13)
C3—C4	1.517 (7)	C15—H15A	0.9700
C3—H3A	0.9700	C15—H15B	0.9700
C3—H3B	0.9700	C18—H18A	0.9600
C4—C5	1.522 (7)	C18—H18B	0.9600
C4—H4A	0.9700	C18—H18C	0.9600

N1—Al—N1ⁱ	69.8 (2)	C4—C5—H5A	109.5
N1—Al—C18ⁱ	119.0 (2)	C6—C5—H5B	109.5
N1ⁱ—Al—C18ⁱ	114.0 (2)	C4—C5—H5B	109.5
N1—Al—C18	114.0 (2)	H5A—C5—H5B	108.0
N1ⁱ—Al—C18	119.0 (2)	C5—C6—C7	111.3 (4)
C18ⁱ—Al—C18	114.2 (4)	C5—C6—H6A	109.4
C1—N1—C2	124.8 (3)	C7—C6—H6A	109.4
C1—N1—Al	90.4 (3)	C5—C6—H6B	109.4
C2—N1—Al	133.2 (3)	C7—C6—H6B	109.4
C1—N3—C14	124.0 (3)	H6A—C6—H6B	108.0
C1—N3—C14ⁱ	124.0 (3)	C2—C7—C6	112.1 (4)
C14—N3—C14ⁱ	112.0 (5)	C2—C7—H7A	109.2
N1ⁱ—C1—N1	109.4 (5)	C6—C7—H7A	109.2
N1ⁱ—C1—N3	125.3 (3)	C2—C7—H7B	109.2
N1—C1—N3	125.3 (3)	C6—C7—H7B	109.2
N1—C2—C7	108.7 (3)	H7A—C7—H7B	107.9
N1—C2—C3	112.3 (4)	N3—C14—C15	102.2 (5)
C7—C2—C3	109.3 (4)	N3—C14—H14A	111.3
N1—C2—H2	108.8	C15—C14—H14A	111.3
C7—C2—H2	108.8	N3—C14—H14B	111.3
C3—C2—H2	108.8	C15—C14—H14B	111.3
C4—C3—C2	111.9 (4)	H14A—C14—H14B	109.2
C4—C3—H3A	109.2	C15ⁱ—C15—C14	103.2 (3)
C2—C3—H3A	109.2	C15ⁱ—C15—H15A	111.1
C4—C3—H3B	109.2	C14—C15—H15A	111.1
C2—C3—H3B	109.2	C15ⁱ—C15—H15B	111.1
H3A—C3—H3B	107.9	C14—C15—H15B	111.1
C3—C4—C5	111.0 (4)	H15A—C15—H15B	109.1
C3—C4—H4A	109.4	Al—C18—H18A	109.5
C5—C4—H4A	109.4	Al—C18—H18B	109.5
C3—C4—H4B	109.4	H18A—C18—H18B	109.5
C5—C4—H4B	109.4	Al—C18—H18C	109.5
H4A—C4—H4B	108.0	H18A—C18—H18C	109.5
C6—C5—C4	110.9 (5)	H18B—C18—H18C	109.5
C6—C5—H5A	109.5

N1ⁱ—Al—N1—C1	0.0	Al—N1—C2—C7	40.9 (5)
C18ⁱ—Al—N1—C1	106.9 (2)	C1—N1—C2—C3	51.3 (5)
C18—Al—N1—C1	−113.6 (2)	Al—N1—C2—C3	−80.2 (5)
N1ⁱ—Al—N1—C2	142.0 (5)	N1—C2—C3—C4	176.7 (4)
C18ⁱ—Al—N1—C2	−111.0 (4)	C7—C2—C3—C4	55.9 (5)
C18—Al—N1—C2	28.4 (5)	C2—C3—C4—C5	−56.6 (6)
C2—N1—C1—N1ⁱ	−146.9 (4)	C3—C4—C5—C6	55.6 (7)
Al—N1—C1—N1ⁱ	0.0	C4—C5—C6—C7	−55.1 (6)
C2—N1—C1—N3	33.1 (4)	N1—C2—C7—C6	−178.3 (4)
Al—N1—C1—N3	180.0	C3—C2—C7—C6	−55.4 (5)
C14—N3—C1—N1ⁱ	−158.0 (3)	C5—C6—C7—C2	56.0 (6)
C14ⁱ—N3—C1—N1ⁱ	22.0 (3)	C1—N3—C14—C15	167.3 (2)
C14—N3—C1—N1	22.0 (3)	C14ⁱ—N3—C14—C15	−12.7 (2)
C14ⁱ—N3—C1—N1	−158.0 (3)	N3—C14—C15—C15ⁱ	33.5 (6)
C1—N1—C2—C7	172.4 (4)

Symmetry code: (i) −x+1, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Al(CH₃)₂(C₁₇H₃₀N₃)]
M_r	333.49
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	293
a, b, c (Å)	18.263 (4), 10.596 (2), 10.449 (2)
V (Å³)	2022.0 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.959, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	7156, 1772, 1630
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.095, 0.232, 1.42
No. of reflections	1772
No. of parameters	107
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.43

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Selected geometric parameters (Å, º) top

Al—N1	1.922 (4)	Al—C18	1.961 (6)

N1—Al—N1ⁱ	69.8 (2)	C18ⁱ—Al—C18	114.2 (4)

Symmetry code: (i) −x+1, y, −z+1/2.

Acknowledgements

This work was carried out under the sponsorship of the Nature Science Foundation of Shanxi Province (2008012013-2).

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