(E)-N,N′-Bis(2,6-dimethyl­phen­yl)-N,N′-bis­(trichloro­silyl)ethyl­ene-1,2-diamine

Yang, W.; Zhang, M.; Liu, G.; Ding, Y.

doi:10.1107/S1600536809006011

organic compounds

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doi:10.1107/S1600536809006011

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(E)-N,N′-Bis(2,6-dimethylphenyl)-N,N′-bis(trichlorosilyl)ethylene-1,2-diamine

Wei Yang,^a Ming Zhang,^a Guangyan Liu ^a and Yuqiang Ding ^a ^*

^aSchool of Chemical and Material Engineering, Jiangnan University, 1800 Lihu Road, Wuxi, Jiangsu Province 214122, People's Republic of China
^*Correspondence e-mail: yding@jiangnan.edu.cn

(Received 16 February 2009; accepted 19 February 2009; online 28 February 2009)

The asymmetric unit of the title compound, C₁₈H₂₀Cl₆N₂Si₂, contains one half of the centrosymmetric molecule. The two benzene rings are perpendicular to the plane of Si–N–C=C–N–Si fragment, making a dihedral angle of 89.9 (1)°. The crystal packing exhibits short intermolecular Cl⋯Cl contacts of 3.3119 (17) Å.

Related literature

For the geometric parameters of related compounds, see: Haaf et al. (1998 , 2000 ); Baker et al. (2008 ); Jones et al. (2002 ).

Experimental

Crystal data

C₁₈H₂₀Cl₆N₂Si₂
M_r = 533.24
Triclinic, $[P \overline 1]$
a = 8.1858 (3) Å
b = 8.4249 (3) Å
c = 10.6074 (4) Å
α = 74.583 (3)°
β = 79.999 (2)°
γ = 62.243 (2)°
V = 623.00 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 273 K
0.14 × 0.12 × 0.08 mm

Data collection

Bruker APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.897, T_max = 0.939
6168 measured reflections
2168 independent reflections
1729 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.202
S = 1.11
2168 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006011/cv2522sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006011/cv2522Isup2.hkl

checkCIF report

Comment top

The title compound, (I), was synthesized by the reaction of the excess silicon tetrachloride and the dilithium salt of the diimine [N(2,6-Me₂C₆H₃)C(H)]₂ in THF (Haaf et al., 1998). A high yielding preparation of the title compound was devised whereby two equivalents of SiCl₄ were treated with dilithium salt in THF (Baker et al., 2008). The title compound and related compounds are of interest in silylene chemistry in relation to synthesis of the silylene dichloride precursor (Haaf et al., 2000; Baker et al., 2008).

The title molecule (Fig. 1) exists in an E configuration with respect to the C═C double bond (Table 1) and crystallizes in the triclinic space group P1.The planes of the two xylyl substituents at the nitrogen atoms are perpendicularly oriented to the plane of Si1/N1/C1/C1ⁱ/N1ⁱ/Si1ⁱ [symmery code: (i) -x, 2-y, -z] forming dihedral angles of 89.9 (1)°. The Si–Cl and Si–N bond lengths in (I) (Table 1) are slightly shorter than those in the related complex (C₅H₃N-6-Me-2-NSiMe₃)SiCl₃ [Si–Cl 2.058 (2)-2.107 (3) Å; Si–N 1.753 (5) Å) (Jones et al., 2002). The distance N1–C1[1.428 (4) Å] agrees well with that observed in the related E-ethenediamine complex (Baker et al., 2008). The C1–N1–C2 angle [118.7 (3) °] in (I) is comparable to that in [PhC(NtBu)₂]SiCl [120.70 (11) °] (Haaf et al., 1998). The C1–N1–Si1 angle [120.1 (2) °] in (I) is larger than that in [Si[N(tBu)CH]₂]₂ [109.42 (14) °] (Haaf et al., 1998), because of E configuration.

The crystal packing exhibits short intermolecular Cl···Cl contacts (Table 1).

Related literature top

For the geometric parameters of related compounds, see: Haaf et al. (1998, 2000); Baker et al. (2008); Jones et al. (2002).

Experimental top

All manipulations were carried out under an argon atmosphere using standard Schlenk techniques or a nitrogen-filled glovebox. Solvents (THF, toluene) were dried over sodium and freshly distilled prior to use.

Naphthalene (1.24 g,10 mmol) was dissolved in THF (15 ml) and lithium powder (71 mg, 10 mmol) added. The resultant suspension was stirred at room temperature for 4 h to give an green suspension. [N(2,6-Me₂C₆H₃)C(H)]₂ (1.17 g, 4.5 mmol) was added to the suspension after cooled to -78 ^oC. The resultant mixture was stirred at room temperature for 24 h to give a red solution. At -78 ^oC, silicon tetrachloride (10 ml, 88 mmol) was added to the solution. Warmed to room temperature and stirred for 24 h. Volatiles were removed in vacuo and the residue was extracted with toluene (20 ml). After filtration, the filtrate was placed at -30 ^oC to give yellow crystals (43%). Elemental analysis(%) calcd. for C₁₈H₂₀Cl₆N₂Si₂: C, 40.54%; H, 3.78%; N, 5.25%; Found: C,40.61%; H, 3.83%; N, 5.17%.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme. The unlabelled atoms are related with the labelled ones by symmetry operation (-x, -y + 2, -z). H atoms omitted for clarity.

(E)-N,N'-Bis(2,6-dimethylphenyl)-N,N'- bis(trichlorosilyl)ethylene-1,2-diamine top

Crystal data top

C₁₈H₂₀Cl₆N₂Si₂	Z = 1
M_r = 533.24	F(000) = 272
Triclinic, P1	D_x = 1.421 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1858 (3) Å	Cell parameters from 2127 reflections
b = 8.4249 (3) Å	θ = 2.8–25.6°
c = 10.6074 (4) Å	µ = 0.79 mm⁻¹
α = 74.583 (3)°	T = 273 K
β = 79.999 (2)°	Block, yellow
γ = 62.243 (2)°	0.14 × 0.12 × 0.08 mm
V = 623.00 (4) Å³

Data collection top

Bruker APEX2 CCD area-detector diffractometer	2168 independent reflections
Radiation source: fine-focus sealed tube	1729 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.1°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.897, T_max = 0.939	k = −10→9
6168 measured reflections	l = −12→12

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.059	w = 1/[σ²(F_o²) + (0.133P)² + 0.1233P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.202	(Δ/σ)_max = 0.088
S = 1.11	Δρ_max = 0.57 e Å⁻³
2168 reflections	Δρ_min = −0.50 e Å⁻³
129 parameters

Crystal data top

C₁₈H₂₀Cl₆N₂Si₂	γ = 62.243 (2)°
M_r = 533.24	V = 623.00 (4) Å³
Triclinic, P1	Z = 1
a = 8.1858 (3) Å	Mo Kα radiation
b = 8.4249 (3) Å	µ = 0.79 mm⁻¹
c = 10.6074 (4) Å	T = 273 K
α = 74.583 (3)°	0.14 × 0.12 × 0.08 mm
β = 79.999 (2)°

Data collection top

Bruker APEX2 CCD area-detector diffractometer	2168 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1729 reflections with I > 2σ(I)
T_min = 0.897, T_max = 0.939	R_int = 0.034
6168 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.202	H-atom parameters constrained
S = 1.11	Δρ_max = 0.57 e Å⁻³
2168 reflections	Δρ_min = −0.50 e Å⁻³
129 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
Si1	0.34542 (14)	0.80312 (14)	0.19720 (9)	0.0424 (4)
Cl1	0.40381 (19)	1.01460 (17)	0.18495 (14)	0.0736 (5)
Cl2	0.54249 (18)	0.64298 (19)	0.08286 (14)	0.0791 (5)
Cl3	0.36689 (17)	0.65899 (17)	0.38326 (10)	0.0675 (4)
N1	0.1308 (4)	0.8729 (4)	0.1525 (3)	0.0394 (7)
C1	0.0820 (5)	0.9686 (5)	0.0214 (3)	0.0424 (9)
H1	0.1729	0.9875	−0.0375	0.051*
C2	−0.0078 (5)	0.8409 (5)	0.2452 (3)	0.0391 (8)
C3	−0.0237 (6)	0.6787 (5)	0.2607 (4)	0.0510 (10)
C4	−0.1436 (6)	0.6423 (6)	0.3580 (5)	0.0630 (12)
H4	−0.1535	0.5335	0.3706	0.076*
C5	−0.2502 (7)	0.7654 (8)	0.4378 (5)	0.0669 (13)
H5	−0.3294	0.7380	0.5042	0.080*
C6	−0.2389 (6)	0.9273 (7)	0.4189 (4)	0.0623 (12)
H6	−0.3130	1.0103	0.4716	0.075*
C7	−0.1181 (6)	0.9699 (6)	0.3218 (4)	0.0484 (9)
C8	0.0925 (9)	0.5424 (7)	0.1755 (7)	0.0816 (16)
H8A	0.2172	0.4774	0.2026	0.122*
H8B	0.0917	0.6064	0.0858	0.122*
H8C	0.0426	0.4569	0.1838	0.122*
C9	−0.1071 (8)	1.1485 (6)	0.3024 (6)	0.0736 (14)
H9A	−0.0312	1.1381	0.3666	0.110*
H9B	−0.2290	1.2451	0.3122	0.110*
H9C	−0.0541	1.1761	0.2162	0.110*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0486 (7)	0.0433 (6)	0.0322 (6)	−0.0209 (5)	−0.0094 (4)	0.0021 (4)
Cl1	0.0869 (10)	0.0678 (8)	0.0823 (9)	−0.0503 (7)	−0.0180 (7)	−0.0021 (6)
Cl2	0.0655 (8)	0.0787 (9)	0.0780 (9)	−0.0180 (7)	0.0111 (6)	−0.0291 (7)
Cl3	0.0699 (8)	0.0822 (8)	0.0431 (6)	−0.0385 (7)	−0.0239 (5)	0.0208 (6)
N1	0.0483 (18)	0.0413 (16)	0.0266 (14)	−0.0197 (14)	−0.0087 (12)	−0.0002 (12)
C1	0.054 (2)	0.0413 (19)	0.0289 (18)	−0.0214 (18)	−0.0087 (15)	0.0009 (15)
C2	0.047 (2)	0.0440 (19)	0.0252 (16)	−0.0215 (17)	−0.0092 (14)	0.0006 (15)
C3	0.059 (3)	0.046 (2)	0.050 (2)	−0.025 (2)	−0.0104 (19)	−0.0050 (18)
C4	0.064 (3)	0.061 (3)	0.068 (3)	−0.038 (2)	−0.009 (2)	0.002 (2)
C5	0.061 (3)	0.094 (4)	0.047 (2)	−0.045 (3)	−0.001 (2)	0.001 (2)
C6	0.054 (3)	0.082 (3)	0.045 (2)	−0.024 (2)	0.0039 (19)	−0.021 (2)
C7	0.052 (2)	0.050 (2)	0.040 (2)	−0.0185 (19)	−0.0105 (17)	−0.0067 (17)
C8	0.096 (4)	0.059 (3)	0.100 (4)	−0.039 (3)	0.013 (3)	−0.035 (3)
C9	0.085 (4)	0.059 (3)	0.081 (3)	−0.029 (3)	0.004 (3)	−0.033 (3)

Geometric parameters (Å, º) top

Si1—N1	1.684 (3)	C4—H4	0.9300
Si1—Cl3	2.0119 (13)	C5—C6	1.369 (7)
Si1—Cl2	2.0142 (17)	C5—H5	0.9300
Si1—Cl1	2.0170 (14)	C6—C7	1.396 (6)
N1—C1	1.428 (4)	C6—H6	0.9300
N1—C2	1.444 (4)	C7—C9	1.507 (6)
C1—C1ⁱ	1.307 (8)	C8—H8A	0.9600
C1—H1	0.9300	C8—H8B	0.9600
C2—C7	1.399 (6)	C8—H8C	0.9600
C2—C3	1.397 (5)	C9—H9A	0.9600
C3—C4	1.372 (6)	C9—H9B	0.9600
C3—C8	1.509 (7)	C9—H9C	0.9600
C4—C5	1.386 (7)

Cl3···Cl3ⁱⁱ	3.3119 (17)

N1—Si1—Cl3	108.46 (11)	C6—C5—C4	120.1 (4)
N1—Si1—Cl2	112.31 (12)	C6—C5—H5	120.0
Cl3—Si1—Cl2	108.64 (7)	C4—C5—H5	120.0
N1—Si1—Cl1	112.55 (11)	C5—C6—C7	121.1 (4)
Cl3—Si1—Cl1	109.04 (7)	C5—C6—H6	119.4
Cl2—Si1—Cl1	105.73 (7)	C7—C6—H6	119.4
C1—N1—C2	118.7 (3)	C2—C7—C6	117.8 (4)
C1—N1—Si1	120.1 (2)	C2—C7—C9	121.8 (4)
C2—N1—Si1	121.2 (2)	C6—C7—C9	120.4 (4)
C1ⁱ—C1—N1	124.4 (4)	C3—C8—H8A	109.5
C1ⁱ—C1—H1	117.8	C3—C8—H8B	109.5
N1—C1—H1	117.8	H8A—C8—H8B	109.5
C7—C2—C3	121.4 (3)	C3—C8—H8C	109.5
C7—C2—N1	119.1 (3)	H8A—C8—H8C	109.5
C3—C2—N1	119.5 (3)	H8B—C8—H8C	109.5
C4—C3—C2	118.7 (4)	C7—C9—H9A	109.5
C4—C3—C8	120.2 (4)	C7—C9—H9B	109.5
C2—C3—C8	121.0 (4)	H9A—C9—H9B	109.5
C3—C4—C5	120.9 (4)	C7—C9—H9C	109.5
C3—C4—H4	119.6	H9A—C9—H9C	109.5
C5—C4—H4	119.5	H9B—C9—H9C	109.5

Cl3—Si1—N1—C1	−176.0 (2)	N1—C2—C3—C4	173.7 (4)
Cl2—Si1—N1—C1	−55.9 (3)	C7—C2—C3—C8	178.5 (4)
Cl1—Si1—N1—C1	63.3 (3)	N1—C2—C3—C8	−4.4 (6)
Cl3—Si1—N1—C2	5.2 (3)	C2—C3—C4—C5	1.4 (7)
Cl2—Si1—N1—C2	125.3 (3)	C8—C3—C4—C5	179.5 (5)
Cl1—Si1—N1—C2	−115.5 (3)	C3—C4—C5—C6	1.0 (7)
C2—N1—C1—C1ⁱ	0.4 (7)	C4—C5—C6—C7	−1.5 (7)
Si1—N1—C1—C1ⁱ	−178.4 (4)	C3—C2—C7—C6	2.9 (6)
C1—N1—C2—C7	−91.3 (4)	N1—C2—C7—C6	−174.2 (3)
Si1—N1—C2—C7	87.6 (4)	C3—C2—C7—C9	−177.7 (4)
C1—N1—C2—C3	91.6 (4)	N1—C2—C7—C9	5.2 (6)
Si1—N1—C2—C3	−89.6 (4)	C5—C6—C7—C2	−0.5 (6)
C7—C2—C3—C4	−3.4 (6)	C5—C6—C7—C9	−179.9 (5)

Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₀Cl₆N₂Si₂
M_r	533.24
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	8.1858 (3), 8.4249 (3), 10.6074 (4)
α, β, γ (°)	74.583 (3), 79.999 (2), 62.243 (2)
V (Å³)	623.00 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.14 × 0.12 × 0.08

Data collection
Diffractometer	Bruker APEX2 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.897, 0.939
No. of measured, independent and observed [I > 2σ(I)] reflections	6168, 2168, 1729
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.202, 1.11
No. of reflections	2168
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.50

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected interatomic distances (Å) top

Si1—N1	1.684 (3)	Si1—Cl1	2.0170 (14)
Si1—Cl3	2.0119 (13)	C1—C1ⁱ	1.307 (8)
Si1—Cl2	2.0142 (17)

Cl3···Cl3ⁱⁱ	3.3119 (17)

Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+1, −z+1.

Acknowledgements

This work was supported by the National Science Foundation of China (No. 20571033) and by the Program for New Century Excellent Talents in Universities (NCET-06-0483).

References

Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
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Bruker (2005). APEX2 and SAINT. Bruker AXS inc., Madison, Wisconsin, USA. Google Scholar
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Haaf, M., Schmiedl, A., Schmedake, T. A., Powell, D. R., Millevolte, A. J., Denk, M. & West, R. (1998). J. Am. Chem. Soc. 120, 12714-12719. Web of Science CSD CrossRef CAS Google Scholar
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(E)-N,N′-Bis(2,6-di­methyl­phen­yl)-N,N′-bis­­(tri­chloro­silyl)ethyl­ene-1,2-di­amine

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(E)-N,N′-Bis(2,6-dimethylphenyl)-N,N′-bis(trichlorosilyl)ethylene-1,2-diamine