Trichlorido(N,N′-di-tert-butyl­benzamidinato-κ2N,N′)silicon

Lv, L.-D.; Li, J.-J.; Yang, W.; Ren, C.-X.; Ding, Y.-Q.

doi:10.1107/S1600536808010398

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o870

doi:10.1107/S1600536808010398

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Trichlorido(N,N′-di-tert-butylbenzamidinato-κ²N,N′)silicon

Lu-Dan Lv,^a Jun-Jun Li,^b Wei Yang,^a Chun-Xia Ren ^a ^* and Yu-Qiang Ding ^a ^*

^aSchool of Chemical and Materials Engineering, Jiangnan University, 1800 Lihu Road, Wuxi, Jiangsu Province 214122, People's Republic of China, and ^bCollege of Pharmacy, GuangDong Pharmaceutical University, Guangzhou, Guangdong Province 510006, People's Republic of China
^*Correspondence e-mail: chunxiaren@sina.com, liweijun947@163.com

(Received 30 March 2008; accepted 15 April 2008; online 18 April 2008)

In the title molecule, C₁₅H₂₃Cl₃N₂Si, the Si atom is pentacoordinated by two N atoms [Si—N = 1.780 (3) and 1.931 (3) Å] from the benzamidinate ligand and three chloride anions [Si—Cl = 2.0711 (14)–2.1449 (14) Å] in a distorted trigonal-bipyramidal geometry.

Related literature

For the geometric parameters of related silicon complexes, see: So et al. (2006 ); Hargittai et al. (1983 ); Koe et al. (1998 ); Karsch et al. (1998 ); Jones et al. (2002 ).

Experimental

Crystal data

C₁₅H₂₃Cl₃N₂Si
M_r = 365.80
Triclinic, $[P \overline 1]$
a = 6.372 (3) Å
b = 10.278 (4) Å
c = 14.229 (6) Å
α = 83.222 (6)°
β = 83.227 (6)°
γ = 84.189 (6)°
V = 915.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 273 (2) K
0.35 × 0.26 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
4535 measured reflections
3166 independent reflections
2189 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.159
S = 0.99
3166 reflections
196 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808010398/cv2396sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808010398/cv2396Isup2.hkl

checkCIF report

Comment top

The discrete electronically neutral mononuclear heteroleptic title silicon(IV) complex, (I), crystallizes in the triclinic space group P-1. The mean plane of Si1/N1/C1/N2 and phenyl ring C2-C7 form a dihedral angle of 79.1 (1) °. The Si-Cl bond lengths lie in the range 2.0711 (14)-2.1449 (14) Å and agree well with those observed in the related silicon complexes (So et al., 2006; Hargittai et al., 1983; Koe et al., 1998). The N1-C1 bond [1.308 (4) Å] is a typical double bond, while C1-N2 bond [1.368 (4) Å] is intermediate between the double and single C-N bonds. The N1-Si1-N2 angle [70.1 (1) °] in (I) is comparable to that in [PhC(NtBu)₂]SiCl [68.4 (1) °] (So et al., 2006) and in [MeC(Nipr)₂]₂SiCl₂ [68.8 (1) and 69.0 (1) °] (Karsch et al., 1998). The Si-N bond lengths of 1.780 (3) and 1.931 (3) Å are slightly longer than the Si—N_amide bond length in the silicon(IV) complex (C₅H₃N-6-Me-2-NSiMe₃)SiCl₃ [1.753 (5) Å] (Jones et al., 2002).

Related literature top

For the geometric parameters of related silicon complexes, see: So et al. (2006); Hargittai et al. (1983); Koe et al. (1998); Karsch et al. (1998); Jones et al. (2002).

Experimental top

All manipulations were carried out in an inert atmosphere of N₂ using standard Schlenk techniques and in a N₂ filled glove box. Solvents were dried over and distilled from Na/K alloy prior to use.

PhLi (3.6 ml, 6.48 mmol, 1.8 mol/L in cyclohexane/Et₂O (7:3)) was added to a solution of tBuN=C=NtBu(1.25 ml, 6.48 mmol) in Et₂O (35 ml) at -78 °C. The solution was raised to ambient temperature and stirred for 1 h. SiCl₄ (0.8 ml, 6.97 mmol) was added to this solution at -78 °C. The resulting yellow suspension was stirred overnight at ambient temperature. The precipitate was filtered, and the filtrate was concentrated under reduced pressure until colourless crystals of the title compound (1.11 g, 46%) were obtained. M.p. 178 °C. Elemental analysis (%) calcd for C₁₅H₂₃Cl₃N₂Si: C 49.24, H 6.34, N 7.66; found: C 49.17, H 6.42, N 7.71. ¹H NMR (400 MHz, CDCl₃, 25 °C): δ = 1.18 (s, 18H, tBu), 7.42–7.68 p.p.m. (m, 5H, Ph).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); 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. H atoms have been omitted for clarity.

Trichlorido(N,N'-di-tert-butylbenzamidinato- κ²N,N')silicon top

Crystal data top

C₁₅H₂₃Cl₃N₂Si	Z = 2
M_r = 365.80	F(000) = 384
Triclinic, P1	D_x = 1.327 Mg m⁻³
a = 6.372 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.278 (4) Å	Cell parameters from 1365 reflections
c = 14.229 (6) Å	θ = 2.0–25.0°
α = 83.222 (6)°	µ = 0.56 mm⁻¹
β = 83.227 (6)°	T = 273 K
γ = 84.189 (6)°	Block, colourless
V = 915.3 (7) Å³	0.35 × 0.26 × 0.15 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2189 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 25.0°, θ_min = 2.0°
ϕ and ω scans	h = −7→7
4535 measured reflections	k = −7→12
3166 independent reflections	l = −16→16

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.159	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.102P)²] where P = (F_o² + 2F_c²)/3
3166 reflections	(Δ/σ)_max < 0.001
196 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₁₅H₂₃Cl₃N₂Si	γ = 84.189 (6)°
M_r = 365.80	V = 915.3 (7) Å³
Triclinic, P1	Z = 2
a = 6.372 (3) Å	Mo Kα radiation
b = 10.278 (4) Å	µ = 0.56 mm⁻¹
c = 14.229 (6) Å	T = 273 K
α = 83.222 (6)°	0.35 × 0.26 × 0.15 mm
β = 83.227 (6)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2189 reflections with I > 2σ(I)
4535 measured reflections	R_int = 0.028
3166 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.159	H-atom parameters constrained
S = 0.99	Δρ_max = 0.44 e Å⁻³
3166 reflections	Δρ_min = −0.43 e Å⁻³
196 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	0.38635 (14)	0.09933 (9)	0.76514 (7)	0.0428 (3)
Cl1	0.54115 (17)	−0.02445 (10)	0.66177 (8)	0.0732 (4)
Cl2	0.22531 (16)	−0.05055 (9)	0.84243 (7)	0.0598 (3)
Cl3	0.67974 (13)	0.13745 (9)	0.80465 (7)	0.0564 (3)
N1	0.2423 (4)	0.2341 (2)	0.83913 (18)	0.0396 (6)
N2	0.2521 (4)	0.2228 (3)	0.68974 (18)	0.0443 (7)
C1	0.1884 (5)	0.3019 (3)	0.7605 (2)	0.0390 (7)
C2	0.1051 (5)	0.4426 (3)	0.7473 (2)	0.0406 (8)
C3	0.2489 (6)	0.5342 (3)	0.7133 (3)	0.0536 (9)
H3	0.3908	0.5063	0.6976	0.064*
C4	0.1823 (7)	0.6665 (4)	0.7027 (3)	0.0649 (11)
H4	0.2794	0.7278	0.6807	0.078*
C5	−0.0281 (8)	0.7075 (4)	0.7249 (3)	0.0675 (12)
H5	−0.0728	0.7967	0.7177	0.081*
C6	−0.1716 (6)	0.6183 (4)	0.7572 (3)	0.0596 (10)
H6	−0.3137	0.6470	0.7716	0.072*
C7	−0.1065 (5)	0.4847 (3)	0.7686 (2)	0.0499 (9)
H7	−0.2046	0.4240	0.7906	0.060*
C8	0.1975 (6)	0.2399 (4)	0.5881 (2)	0.0564 (10)
C9	0.3937 (9)	0.2735 (6)	0.5218 (3)	0.0974 (18)
H9A	0.4331	0.3576	0.5330	0.146*
H9B	0.3638	0.2767	0.4570	0.146*
H9C	0.5081	0.2074	0.5335	0.146*
C10	0.0117 (9)	0.3443 (4)	0.5736 (3)	0.0904 (16)
H10A	−0.1015	0.3288	0.6233	0.136*
H10B	−0.0376	0.3396	0.5130	0.136*
H10C	0.0577	0.4300	0.5755	0.136*
C11	0.1190 (7)	0.1105 (4)	0.5664 (3)	0.0682 (12)
H11A	0.2315	0.0412	0.5708	0.102*
H11B	0.0761	0.1215	0.5032	0.102*
H11C	0.0005	0.0882	0.6115	0.102*
C12	0.2239 (5)	0.2735 (3)	0.9381 (2)	0.0452 (8)
C13	0.3108 (7)	0.1583 (4)	1.0033 (3)	0.0732 (12)
H13A	0.2254	0.0860	1.0053	0.110*
H13B	0.3077	0.1839	1.0662	0.110*
H13C	0.4543	0.1319	0.9796	0.110*
C14	0.3482 (7)	0.3920 (4)	0.9418 (3)	0.0686 (12)
H14A	0.4918	0.3739	0.9145	0.103*
H14B	0.3474	0.4087	1.0068	0.103*
H14C	0.2833	0.4677	0.9064	0.103*
C15	−0.0083 (6)	0.3052 (4)	0.9733 (3)	0.0659 (11)
H15A	−0.0616	0.3854	0.9388	0.099*
H15B	−0.0213	0.3155	1.0400	0.099*
H15C	−0.0884	0.2348	0.9633	0.099*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0501 (6)	0.0290 (5)	0.0498 (6)	−0.0020 (4)	−0.0022 (4)	−0.0107 (4)
Cl1	0.0790 (7)	0.0593 (7)	0.0827 (8)	0.0118 (5)	0.0007 (6)	−0.0375 (6)
Cl2	0.0756 (7)	0.0345 (5)	0.0695 (6)	−0.0162 (4)	−0.0042 (5)	−0.0006 (4)
Cl3	0.0471 (5)	0.0533 (6)	0.0713 (6)	−0.0056 (4)	−0.0073 (4)	−0.0152 (5)
N1	0.0508 (15)	0.0308 (15)	0.0374 (15)	0.0031 (12)	−0.0052 (12)	−0.0105 (12)
N2	0.0605 (17)	0.0336 (15)	0.0396 (15)	−0.0012 (13)	−0.0024 (13)	−0.0129 (13)
C1	0.0439 (17)	0.0298 (17)	0.0451 (19)	−0.0076 (14)	−0.0032 (14)	−0.0094 (15)
C2	0.053 (2)	0.0281 (17)	0.0425 (18)	−0.0024 (15)	−0.0092 (15)	−0.0083 (14)
C3	0.064 (2)	0.035 (2)	0.063 (2)	−0.0093 (17)	−0.0059 (18)	−0.0084 (17)
C4	0.087 (3)	0.035 (2)	0.075 (3)	−0.017 (2)	−0.016 (2)	−0.002 (2)
C5	0.101 (3)	0.031 (2)	0.073 (3)	0.005 (2)	−0.029 (2)	−0.0103 (19)
C6	0.065 (2)	0.046 (2)	0.068 (3)	0.0146 (19)	−0.015 (2)	−0.0132 (19)
C7	0.056 (2)	0.0355 (19)	0.060 (2)	−0.0060 (16)	−0.0092 (17)	−0.0067 (17)
C8	0.088 (3)	0.045 (2)	0.040 (2)	−0.015 (2)	−0.0090 (18)	−0.0070 (17)
C9	0.136 (5)	0.114 (4)	0.049 (3)	−0.065 (4)	0.010 (3)	−0.008 (3)
C10	0.151 (5)	0.064 (3)	0.063 (3)	0.016 (3)	−0.053 (3)	−0.014 (2)
C11	0.087 (3)	0.061 (3)	0.064 (3)	−0.017 (2)	−0.013 (2)	−0.023 (2)
C12	0.055 (2)	0.042 (2)	0.0395 (18)	0.0009 (16)	−0.0067 (15)	−0.0108 (16)
C13	0.105 (3)	0.066 (3)	0.046 (2)	0.022 (2)	−0.020 (2)	−0.009 (2)
C14	0.091 (3)	0.068 (3)	0.055 (2)	−0.029 (2)	−0.004 (2)	−0.025 (2)
C15	0.068 (3)	0.078 (3)	0.049 (2)	−0.001 (2)	0.0006 (19)	−0.009 (2)

Geometric parameters (Å, º) top

Si1—N2	1.780 (3)	C8—C11	1.544 (5)
Si1—N1	1.931 (3)	C9—H9A	0.9600
Si1—Cl2	2.0711 (14)	C9—H9B	0.9600
Si1—Cl3	2.1005 (14)	C9—H9C	0.9600
Si1—Cl1	2.1449 (14)	C10—H10A	0.9600
N1—C1	1.308 (4)	C10—H10B	0.9600
N1—C12	1.499 (4)	C10—H10C	0.9600
N2—C1	1.368 (4)	C11—H11A	0.9600
N2—C8	1.513 (4)	C11—H11B	0.9600
C1—C2	1.488 (4)	C11—H11C	0.9600
C2—C7	1.383 (5)	C12—C13	1.516 (5)
C2—C3	1.386 (5)	C12—C15	1.520 (5)
C3—C4	1.379 (5)	C12—C14	1.527 (5)
C3—H3	0.9300	C13—H13A	0.9600
C4—C5	1.375 (6)	C13—H13B	0.9600
C4—H4	0.9300	C13—H13C	0.9600
C5—C6	1.363 (6)	C14—H14A	0.9600
C5—H5	0.9300	C14—H14B	0.9600
C6—C7	1.390 (5)	C14—H14C	0.9600
C6—H6	0.9300	C15—H15A	0.9600
C7—H7	0.9300	C15—H15B	0.9600
C8—C9	1.518 (6)	C15—H15C	0.9600
C8—C10	1.531 (6)

N2—Si1—N1	70.14 (12)	C9—C8—C11	110.8 (3)
N2—Si1—Cl2	120.61 (11)	C10—C8—C11	105.1 (3)
N1—Si1—Cl2	94.21 (10)	C8—C9—H9A	109.5
N2—Si1—Cl3	118.03 (10)	C8—C9—H9B	109.5
N1—Si1—Cl3	90.61 (9)	H9A—C9—H9B	109.5
Cl2—Si1—Cl3	119.05 (6)	C8—C9—H9C	109.5
N2—Si1—Cl1	100.24 (10)	H9A—C9—H9C	109.5
N1—Si1—Cl1	169.82 (10)	H9B—C9—H9C	109.5
Cl2—Si1—Cl1	93.66 (6)	C8—C10—H10A	109.5
Cl3—Si1—Cl1	91.20 (6)	C8—C10—H10B	109.5
C1—N1—C12	129.8 (3)	H10A—C10—H10B	109.5
C1—N1—Si1	89.35 (19)	C8—C10—H10C	109.5
C12—N1—Si1	139.8 (2)	H10A—C10—H10C	109.5
C1—N2—C8	128.9 (3)	H10B—C10—H10C	109.5
C1—N2—Si1	94.06 (19)	C8—C11—H11A	109.5
C8—N2—Si1	136.8 (2)	C8—C11—H11B	109.5
N1—C1—N2	105.9 (3)	H11A—C11—H11B	109.5
N1—C1—C2	127.5 (3)	C8—C11—H11C	109.5
N2—C1—C2	126.0 (3)	H11A—C11—H11C	109.5
N1—C1—Si1	56.34 (16)	H11B—C11—H11C	109.5
N2—C1—Si1	49.93 (16)	N1—C12—C13	108.6 (3)
C2—C1—Si1	167.6 (2)	N1—C12—C15	109.8 (3)
C7—C2—C3	119.5 (3)	C13—C12—C15	107.9 (3)
C7—C2—C1	122.9 (3)	N1—C12—C14	111.2 (3)
C3—C2—C1	117.6 (3)	C13—C12—C14	109.3 (3)
C4—C3—C2	120.2 (4)	C15—C12—C14	110.0 (3)
C4—C3—H3	119.9	C12—C13—H13A	109.5
C2—C3—H3	119.9	C12—C13—H13B	109.5
C5—C4—C3	119.8 (4)	H13A—C13—H13B	109.5
C5—C4—H4	120.1	C12—C13—H13C	109.5
C3—C4—H4	120.1	H13A—C13—H13C	109.5
C6—C5—C4	120.5 (4)	H13B—C13—H13C	109.5
C6—C5—H5	119.7	C12—C14—H14A	109.5
C4—C5—H5	119.7	C12—C14—H14B	109.5
C5—C6—C7	120.3 (4)	H14A—C14—H14B	109.5
C5—C6—H6	119.9	C12—C14—H14C	109.5
C7—C6—H6	119.9	H14A—C14—H14C	109.5
C2—C7—C6	119.6 (3)	H14B—C14—H14C	109.5
C2—C7—H7	120.2	C12—C15—H15A	109.5
C6—C7—H7	120.2	C12—C15—H15B	109.5
N2—C8—C9	109.0 (3)	H15A—C15—H15B	109.5
N2—C8—C10	111.9 (3)	C12—C15—H15C	109.5
C9—C8—C10	111.4 (4)	H15A—C15—H15C	109.5
N2—C8—C11	108.6 (3)	H15B—C15—H15C	109.5

Experimental details

Crystal data
Chemical formula	C₁₅H₂₃Cl₃N₂Si
M_r	365.80
Crystal system, space group	Triclinic, P1
Temperature (K)	273
a, b, c (Å)	6.372 (3), 10.278 (4), 14.229 (6)
α, β, γ (°)	83.222 (6), 83.227 (6), 84.189 (6)
V (Å³)	915.3 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.56
Crystal size (mm)	0.35 × 0.26 × 0.15

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4535, 3166, 2189
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.159, 0.99
No. of reflections	3166
No. of parameters	196
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.43

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant Nos. 20571033 and 20701016).

References

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