Dichloridobis{6-methyl-2-[(trimethyl­silyl)amino]pyridine-κN1}cobalt(II)

Xue, X.; Chen, X.; Tong, H.

doi:10.1107/S1600536809027937

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m957

doi:10.1107/S1600536809027937

Open

access

Dichloridobis{6-methyl-2-[(trimethylsilyl)amino]pyridine-κN¹}cobalt(II)

Xiaoyan Xue,^a Xia Chen ^a ^* and Hongbo Tong ^b

^aSchool of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, People's Republic of China, and ^bInstitute of Applied Chemistry, Shanxi University, Taiyuan 030006, People's Republic of China
^*Correspondence e-mail: chenxia@sxu.edu.cn

(Received 7 July 2009; accepted 16 July 2009; online 22 July 2009)

In the structure of the title compound, [CoCl₂(C₉H₁₆N₂Si)₂], the Co^II atom is located on an inversion center in a slightly distorted tetrahedral environment formed by two chloride ions and the pyridine N atoms of two chelating 6-methyl-2-[(trimethylsilyl)amino]pyridine ligands. The dihedral angle between the planes of the pyridine rings is 80.06 (5)°. Cohesion within the crystal structure is accomplished by N—H⋯Cl hydrogen bonds.

Related literature

For the chemistry of N-functionalized amino ligands, see: Liddle & Clegg (2001 ); Engelhardt et al. (1988 ); Kempe (2000 ) and references therein. Trimethylsilyl-substituted methyl pyridine ligands have been developed due to their structural features and good catalytic activity, see: Andrews et al. (2004 ).

Experimental

Crystal data

[CoCl₂(C₉H₁₆N₂Si)₂]
M_r = 490.49
Monoclinic, C 2/c
a = 14.817 (3) Å
b = 12.554 (4) Å
c = 14.886 (2) Å
β = 114.09 (2)°
V = 2527.8 (10) Å³
Z = 4
Mo Kα radiation
μ = 1.00 mm⁻¹
T = 213 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.754, T_max = 0.826
5113 measured reflections
2224 independent reflections
1905 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.089
S = 1.02
2224 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl1ⁱ	0.86	2.48	3.284 (2)	155
Symmetry code: (i) $[-x, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1996 ); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97; software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027937/fk2001sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027937/fk2001Isup2.hkl

checkCIF report

Comment top

The stucture of the title compound, (I), is shown below. The molecule (Co atom) lies on a crystallographic inversion centre. Dimensions are available in the archived CIF. The chemistry of the N-functionalized amido ligands (Liddle and Clegg, 2001; Engelhardt et al., 1988; Kempe, 2000, and references therein) has attracted much interest, and a number of maingroup and transition metal amido complexes with unusual coordination geometry have been isolated. Trimethylsily substituted methyl pyridine ligands have been developed due to their structural features and good catalytic activities (Andrews et al., 2004). Here, we report the synthesis and structure of a new 6-methyl-2-(trimethylsilylamino) pyridine cobalt complex.

The molecular structure is illustrated in Fig. 1. In the complex, the Co atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from two pyridine and two terminal Cl atoms. The bond lengths and angles are within normal ranges. Phenanthridine ring systems are, of course, planar and the dihedral angle between them is A/B = 80.06 (5)°. The compound displays intramolecular N—H···Cl hydrogen bonds (Table 2).

Related literature top

For the chemistry of N-functionalized amino ligands, see: Liddle & Clegg (2001); Engelhardt et al. (1988); Kempe (2000) and references therein. Trimethylsily substituted methyl pyridine ligands have been developed due to their structural features and good catalytic activity, see: Andrews et al. (2004).

Experimental top

6-Methyl-2-aminopyridine (0.25 g, 2.31 mmol) was added to a solution of LiBuⁿ (0.81 ml g, 2.31 mmol) in Et₂O (30 ml) at 0°C. The resulting mixture was then warmed to room temperature and stirred for 3 h. SiMe₃Cl (0.27 ml, 2.19 mmol) was added at 0°C. The resulting mixture was warmed to room temperature again and stirred for 3 h.CoCl₂ (0.31 g, 2.39 mmol) was the added at -78°C and the mixture was warmed to room temperature and stirred for 24 h. The volatiles were removed in vacuo and the residue was extracted with dichloromethane then filtered. The filtrate was concentrated to give blue crystals (0.79 g, 67%). Anal. Calcd for C₁₈H₃₂Cl₂CoN₄Si₂(%): C, 44.08; H, 6.58; N 11.42. Found: C, 42.85; H, 6.52; N, 10.99.

Computing details top

Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT (Bruker, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.

Dichloridobis{6-methyl-2-[(trimethylsilyl)amino]pyridine- κN¹}cobalt(II) top

Crystal data top

[CoCl₂(C₉H₁₆N₂Si)₂]	F(000) = 1028
M_r = 490.49	D_x = 1.289 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2926 reflections
a = 14.817 (3) Å	θ = 2.2–260639°
b = 12.554 (4) Å	µ = 1.00 mm⁻¹
c = 14.886 (2) Å	T = 213 K
β = 114.09 (2)°	Block, blue
V = 2527.8 (10) Å³	0.30 × 0.30 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2224 independent reflections
Radiation source: fine-focus sealed tube	1905 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −13→17
T_min = 0.754, T_max = 0.826	k = −14→13
5113 measured reflections	l = −17→17

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)] = 0.033	Hydrogen site location: geom and difmap
wR(F²) = 0.089	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0559P)²] where P = (F_o² + 2F_c²)/3
2224 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

[CoCl₂(C₉H₁₆N₂Si)₂]	V = 2527.8 (10) Å³
M_r = 490.49	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.817 (3) Å	µ = 1.00 mm⁻¹
b = 12.554 (4) Å	T = 213 K
c = 14.886 (2) Å	0.30 × 0.30 × 0.20 mm
β = 114.09 (2)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2224 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	1905 reflections with I > 2σ(I)
T_min = 0.754, T_max = 0.826	R_int = 0.020
5113 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.02	Δρ_max = 0.47 e Å⁻³
2224 reflections	Δρ_min = −0.20 e Å⁻³
127 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
Co1	0.0000	0.78913 (3)	0.2500	0.03732 (16)
Cl1	0.10398 (5)	0.89853 (5)	0.21598 (5)	0.0592 (2)
Si1	0.00558 (5)	0.75476 (5)	0.57526 (5)	0.04150 (19)
N1	0.09602 (12)	0.69403 (12)	0.36153 (13)	0.0331 (4)
N2	0.04259 (13)	0.76380 (14)	0.47782 (13)	0.0407 (5)
H2A	0.0166	0.8153	0.4373	0.049*
C1	0.10695 (15)	0.70085 (15)	0.45668 (16)	0.0352 (5)
C2	0.18218 (15)	0.64481 (17)	0.53209 (16)	0.0396 (5)
H2B	0.1894	0.6512	0.5969	0.048*
C3	0.24442 (16)	0.58107 (17)	0.50937 (17)	0.0437 (6)
H3A	0.2952	0.5446	0.5588	0.052*
C4	0.23132 (16)	0.57104 (17)	0.41187 (17)	0.0422 (5)
H4A	0.2723	0.5262	0.3955	0.051*
C5	0.15804 (15)	0.62725 (17)	0.34001 (16)	0.0372 (5)
C6	0.14102 (18)	0.6165 (2)	0.23377 (17)	0.0514 (6)
H6A	0.1861	0.5649	0.2278	0.077*
H6B	0.1518	0.6841	0.2096	0.077*
H6C	0.0743	0.5936	0.1960	0.077*
C7	0.1062 (2)	0.7875 (2)	0.69626 (19)	0.0632 (7)
H7A	0.1575	0.7349	0.7127	0.095*
H7B	0.0804	0.7883	0.7458	0.095*
H7C	0.1329	0.8564	0.6929	0.095*
C8	−0.0395 (2)	0.6186 (2)	0.5781 (2)	0.0780 (9)
H8A	−0.0910	0.6017	0.5152	0.117*
H8B	−0.0651	0.6141	0.6278	0.117*
H8C	0.0140	0.5690	0.5930	0.117*
C9	−0.0937 (2)	0.8548 (3)	0.5436 (2)	0.0819 (10)
H9A	−0.0685	0.9234	0.5370	0.123*
H9B	−0.1174	0.8574	0.5947	0.123*
H9C	−0.1470	0.8356	0.4826	0.123*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0405 (3)	0.0364 (3)	0.0298 (3)	0.000	0.00890 (19)	0.000
Cl1	0.0730 (5)	0.0549 (4)	0.0429 (4)	−0.0265 (3)	0.0167 (3)	−0.0029 (3)
Si1	0.0433 (4)	0.0439 (4)	0.0383 (4)	0.0058 (3)	0.0177 (3)	0.0030 (3)
N1	0.0311 (9)	0.0327 (9)	0.0327 (10)	−0.0001 (7)	0.0102 (8)	−0.0018 (7)
N2	0.0481 (11)	0.0398 (10)	0.0331 (11)	0.0132 (8)	0.0156 (9)	0.0061 (8)
C1	0.0363 (12)	0.0312 (11)	0.0356 (12)	−0.0039 (9)	0.0123 (10)	−0.0017 (9)
C2	0.0403 (12)	0.0419 (12)	0.0334 (12)	0.0002 (10)	0.0117 (10)	0.0041 (10)
C3	0.0363 (12)	0.0412 (12)	0.0473 (15)	0.0044 (10)	0.0107 (11)	0.0063 (11)
C4	0.0353 (12)	0.0425 (12)	0.0484 (14)	0.0032 (10)	0.0168 (11)	−0.0012 (11)
C5	0.0330 (11)	0.0380 (11)	0.0398 (13)	−0.0046 (9)	0.0142 (10)	−0.0061 (10)
C6	0.0444 (13)	0.0660 (16)	0.0431 (14)	0.0052 (12)	0.0170 (11)	−0.0104 (12)
C7	0.0665 (18)	0.0831 (19)	0.0421 (16)	−0.0077 (15)	0.0243 (14)	−0.0082 (14)
C8	0.091 (2)	0.0630 (18)	0.094 (3)	−0.0211 (17)	0.0524 (19)	−0.0041 (17)
C9	0.088 (2)	0.102 (2)	0.071 (2)	0.049 (2)	0.0480 (18)	0.0261 (19)

Geometric parameters (Å, º) top

Co1—N1ⁱ	2.0681 (17)	C3—H3A	0.9300
Co1—N1	2.0681 (17)	C4—C5	1.369 (3)
Co1—Cl1	2.2701 (7)	C4—H4A	0.9300
Co1—Cl1ⁱ	2.2701 (7)	C5—C6	1.503 (3)
Si1—N2	1.7512 (19)	C6—H6A	0.9600
Si1—C9	1.843 (3)	C6—H6B	0.9600
Si1—C8	1.843 (3)	C6—H6C	0.9600
Si1—C7	1.856 (3)	C7—H7A	0.9600
N1—C1	1.361 (3)	C7—H7B	0.9600
N1—C5	1.375 (3)	C7—H7C	0.9600
N2—C1	1.370 (3)	C8—H8A	0.9600
N2—H2A	0.8600	C8—H8B	0.9600
C1—C2	1.406 (3)	C8—H8C	0.9600
C2—C3	1.364 (3)	C9—H9A	0.9600
C2—H2B	0.9300	C9—H9B	0.9600
C3—C4	1.389 (3)	C9—H9C	0.9600

N1ⁱ—Co1—N1	109.49 (9)	C3—C4—H4A	120.1
N1ⁱ—Co1—Cl1	118.51 (5)	C4—C5—N1	121.7 (2)
N1—Co1—Cl1	102.78 (5)	C4—C5—C6	121.01 (19)
N1ⁱ—Co1—Cl1ⁱ	102.78 (5)	N1—C5—C6	117.33 (19)
N1—Co1—Cl1ⁱ	118.51 (5)	C5—C6—H6A	109.5
Cl1—Co1—Cl1ⁱ	105.54 (4)	C5—C6—H6B	109.5
N2—Si1—C9	103.38 (11)	H6A—C6—H6B	109.5
N2—Si1—C8	108.58 (12)	C5—C6—H6C	109.5
C9—Si1—C8	112.25 (15)	H6A—C6—H6C	109.5
N2—Si1—C7	112.97 (11)	H6B—C6—H6C	109.5
C9—Si1—C7	109.78 (14)	Si1—C7—H7A	109.5
C8—Si1—C7	109.78 (14)	Si1—C7—H7B	109.5
C1—N1—C5	118.28 (17)	H7A—C7—H7B	109.5
C1—N1—Co1	123.35 (13)	Si1—C7—H7C	109.5
C5—N1—Co1	118.11 (14)	H7A—C7—H7C	109.5
C1—N2—Si1	129.45 (15)	H7B—C7—H7C	109.5
C1—N2—H2A	115.3	Si1—C8—H8A	109.5
Si1—N2—H2A	115.3	Si1—C8—H8B	109.5
N1—C1—N2	118.49 (19)	H8A—C8—H8B	109.5
N1—C1—C2	121.22 (19)	Si1—C8—H8C	109.5
N2—C1—C2	120.3 (2)	H8A—C8—H8C	109.5
C3—C2—C1	119.5 (2)	H8B—C8—H8C	109.5
C3—C2—H2B	120.3	Si1—C9—H9A	109.5
C1—C2—H2B	120.3	Si1—C9—H9B	109.5
C2—C3—C4	119.5 (2)	H9A—C9—H9B	109.5
C2—C3—H3A	120.3	Si1—C9—H9C	109.5
C4—C3—H3A	120.3	H9A—C9—H9C	109.5
C5—C4—C3	119.9 (2)	H9B—C9—H9C	109.5
C5—C4—H4A	120.1

N1ⁱ—Co1—N1—C1	−123.88 (16)	Si1—N2—C1—N1	154.07 (16)
Cl1—Co1—N1—C1	109.30 (15)	Si1—N2—C1—C2	−25.8 (3)
Cl1ⁱ—Co1—N1—C1	−6.54 (17)	N1—C1—C2—C3	−1.1 (3)
N1ⁱ—Co1—N1—C5	62.03 (13)	N2—C1—C2—C3	178.84 (19)
Cl1—Co1—N1—C5	−64.80 (14)	C1—C2—C3—C4	−1.2 (3)
Cl1ⁱ—Co1—N1—C5	179.37 (12)	C2—C3—C4—C5	1.8 (3)
C9—Si1—N2—C1	−172.5 (2)	C3—C4—C5—N1	−0.1 (3)
C8—Si1—N2—C1	−53.1 (2)	C3—C4—C5—C6	−178.9 (2)
C7—Si1—N2—C1	68.9 (2)	C1—N1—C5—C4	−2.0 (3)
C5—N1—C1—N2	−177.26 (17)	Co1—N1—C5—C4	172.35 (15)
Co1—N1—C1—N2	8.7 (2)	C1—N1—C5—C6	176.76 (19)
C5—N1—C1—C2	2.6 (3)	Co1—N1—C5—C6	−8.8 (2)
Co1—N1—C1—C2	−171.44 (14)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1ⁱ	0.86	2.48	3.284 (2)	155

Symmetry code: (i) −x, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[CoCl₂(C₉H₁₆N₂Si)₂]
M_r	490.49
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	213
a, b, c (Å)	14.817 (3), 12.554 (4), 14.886 (2)
β (°)	114.09 (2)
V (Å³)	2527.8 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.00
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.754, 0.826
No. of measured, independent and observed [I > 2σ(I)] reflections	5113, 2224, 1905
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.089, 1.02
No. of reflections	2224
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.20

Computer programs: SMART (Bruker, 1996), SAINT (Bruker, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1ⁱ	0.86	2.48	3.284 (2)	155.4

Symmetry code: (i) −x, y, −z+1/2.

Acknowledgements

The authors thank the Foundation for Returned Overseas Chinese Scholars of Shanxi Province.

References

Andrews, J. E., McGrady, P. J. & Nichols, P. T. (2004). Organometallics, 23, 446–453. Web of Science CSD CrossRef CAS Google Scholar
Bruker (1996). SMART and SAINT. Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Engelhardt, L. M., Jacobsen, G. E., Junk, P. C., Raston, C. L., Skelton, B. W. & White, A. H. (1988). J. Chem. Soc. Dalton Trans. pp. 1011–1020. CSD CrossRef Web of Science Google Scholar
Kempe, R. (2000). Angew. Chem. Int. Ed. 39, 468–493. CrossRef CAS Google Scholar
Liddle, S. T. & Clegg, W. (2001). J. Chem. Soc., Dalton Trans. pp. 402–408. Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m957

doi:10.1107/S1600536809027937

Open

access