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

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ISSN: 2056-9890

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

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[So, C.-W., Roesky, H. W., Magull, J. & Oswald, R. B. (2006). Angew. Chem. Int. Ed. 45, 3948-3950.]); Hargittai et al. (1983[Hargittai, I., Schultz, G., Tremmel, J., Kagramanov, N. D., Maltsev, A. K. & Nefedov, O. M. (1983). J. Am. Chem. Soc. 105, 2895-2896.]); Koe et al. (1998[Koe, J. R., Powell, D. R., Buffy, J. J., Hayase, S. & West, R. (1998). Angew. Chem. Int. Ed. 37, 1441-1442.]); Karsch et al. (1998[Karsch, H. H., Schlüter, P. A. & Reisky, M. (1998). Eur. J. Inorg. Chem. pp. 433-436.]); Jones et al. (2002[Jones, C., Junk, P. C., Leary, S. G., Smithies, N. A. & Steed, J. W. (2002). Inorg. Chem. Commun. 5, 533-536.]).

[Scheme 1]

Experimental

Crystal data
  • C15H23Cl3N2Si

  • Mr = 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)

  • Rint = 0.028

Refinement
  • R[F2 > 2σ(F2)] = 0.053

  • wR(F2) = 0.159

  • S = 0.99

  • 3166 reflections

  • 196 parameters

  • H-atom parameters constrained

  • Δρmax = 0.44 e Å−3

  • Δρmin = −0.43 e Å−3

Data collection: SMART (Bruker, 1998[Bruker, (1998). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 1998[Bruker, (1998). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: SHELXL97.

Supporting information


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—Namide 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).

Refinement top

The H atoms were positioned geometrically (C—H 0.93–0.97 Å), and allowed to ride on their parent atoms, with Uiso(H) = 1.2–1.5 Ueq(C).

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
[Figure 1] 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
C15H23Cl3N2SiZ = 2
Mr = 365.80F(000) = 384
Triclinic, P1Dx = 1.327 Mg m3
a = 6.372 (3) ÅMo Kα radiation, λ = 0.71073 Å
b = 10.278 (4) ÅCell parameters from 1365 reflections
c = 14.229 (6) Åθ = 2.0–25.0°
α = 83.222 (6)°µ = 0.56 mm1
β = 83.227 (6)°T = 273 K
γ = 84.189 (6)°Block, colourless
V = 915.3 (7) Å30.35 × 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 tubeRint = 0.028
Graphite monochromatorθmax = 25.0°, θmin = 2.0°
ϕ and ω scansh = 77
4535 measured reflectionsk = 712
3166 independent reflectionsl = 1616
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.102P)2]
where P = (Fo2 + 2Fc2)/3
3166 reflections(Δ/σ)max < 0.001
196 parametersΔρmax = 0.44 e Å3
0 restraintsΔρmin = 0.43 e Å3
Crystal data top
C15H23Cl3N2Siγ = 84.189 (6)°
Mr = 365.80V = 915.3 (7) Å3
Triclinic, P1Z = 2
a = 6.372 (3) ÅMo Kα radiation
b = 10.278 (4) ŵ = 0.56 mm1
c = 14.229 (6) ÅT = 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 reflectionsRint = 0.028
3166 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.159H-atom parameters constrained
S = 0.99Δρmax = 0.44 e Å3
3166 reflectionsΔρmin = 0.43 e Å3
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
xyzUiso*/Ueq
Si10.38635 (14)0.09933 (9)0.76514 (7)0.0428 (3)
Cl10.54115 (17)0.02445 (10)0.66177 (8)0.0732 (4)
Cl20.22531 (16)0.05055 (9)0.84243 (7)0.0598 (3)
Cl30.67974 (13)0.13745 (9)0.80465 (7)0.0564 (3)
N10.2423 (4)0.2341 (2)0.83913 (18)0.0396 (6)
N20.2521 (4)0.2228 (3)0.68974 (18)0.0443 (7)
C10.1884 (5)0.3019 (3)0.7605 (2)0.0390 (7)
C20.1051 (5)0.4426 (3)0.7473 (2)0.0406 (8)
C30.2489 (6)0.5342 (3)0.7133 (3)0.0536 (9)
H30.39080.50630.69760.064*
C40.1823 (7)0.6665 (4)0.7027 (3)0.0649 (11)
H40.27940.72780.68070.078*
C50.0281 (8)0.7075 (4)0.7249 (3)0.0675 (12)
H50.07280.79670.71770.081*
C60.1716 (6)0.6183 (4)0.7572 (3)0.0596 (10)
H60.31370.64700.77160.072*
C70.1065 (5)0.4847 (3)0.7686 (2)0.0499 (9)
H70.20460.42400.79060.060*
C80.1975 (6)0.2399 (4)0.5881 (2)0.0564 (10)
C90.3937 (9)0.2735 (6)0.5218 (3)0.0974 (18)
H9A0.43310.35760.53300.146*
H9B0.36380.27670.45700.146*
H9C0.50810.20740.53350.146*
C100.0117 (9)0.3443 (4)0.5736 (3)0.0904 (16)
H10A0.10150.32880.62330.136*
H10B0.03760.33960.51300.136*
H10C0.05770.43000.57550.136*
C110.1190 (7)0.1105 (4)0.5664 (3)0.0682 (12)
H11A0.23150.04120.57080.102*
H11B0.07610.12150.50320.102*
H11C0.00050.08820.61150.102*
C120.2239 (5)0.2735 (3)0.9381 (2)0.0452 (8)
C130.3108 (7)0.1583 (4)1.0033 (3)0.0732 (12)
H13A0.22540.08601.00530.110*
H13B0.30770.18391.06620.110*
H13C0.45430.13190.97960.110*
C140.3482 (7)0.3920 (4)0.9418 (3)0.0686 (12)
H14A0.49180.37390.91450.103*
H14B0.34740.40871.00680.103*
H14C0.28330.46770.90640.103*
C150.0083 (6)0.3052 (4)0.9733 (3)0.0659 (11)
H15A0.06160.38540.93880.099*
H15B0.02130.31551.04000.099*
H15C0.08840.23480.96330.099*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Si10.0501 (6)0.0290 (5)0.0498 (6)0.0020 (4)0.0022 (4)0.0107 (4)
Cl10.0790 (7)0.0593 (7)0.0827 (8)0.0118 (5)0.0007 (6)0.0375 (6)
Cl20.0756 (7)0.0345 (5)0.0695 (6)0.0162 (4)0.0042 (5)0.0006 (4)
Cl30.0471 (5)0.0533 (6)0.0713 (6)0.0056 (4)0.0073 (4)0.0152 (5)
N10.0508 (15)0.0308 (15)0.0374 (15)0.0031 (12)0.0052 (12)0.0105 (12)
N20.0605 (17)0.0336 (15)0.0396 (15)0.0012 (13)0.0024 (13)0.0129 (13)
C10.0439 (17)0.0298 (17)0.0451 (19)0.0076 (14)0.0032 (14)0.0094 (15)
C20.053 (2)0.0281 (17)0.0425 (18)0.0024 (15)0.0092 (15)0.0083 (14)
C30.064 (2)0.035 (2)0.063 (2)0.0093 (17)0.0059 (18)0.0084 (17)
C40.087 (3)0.035 (2)0.075 (3)0.017 (2)0.016 (2)0.002 (2)
C50.101 (3)0.031 (2)0.073 (3)0.005 (2)0.029 (2)0.0103 (19)
C60.065 (2)0.046 (2)0.068 (3)0.0146 (19)0.015 (2)0.0132 (19)
C70.056 (2)0.0355 (19)0.060 (2)0.0060 (16)0.0092 (17)0.0067 (17)
C80.088 (3)0.045 (2)0.040 (2)0.015 (2)0.0090 (18)0.0070 (17)
C90.136 (5)0.114 (4)0.049 (3)0.065 (4)0.010 (3)0.008 (3)
C100.151 (5)0.064 (3)0.063 (3)0.016 (3)0.053 (3)0.014 (2)
C110.087 (3)0.061 (3)0.064 (3)0.017 (2)0.013 (2)0.023 (2)
C120.055 (2)0.042 (2)0.0395 (18)0.0009 (16)0.0067 (15)0.0108 (16)
C130.105 (3)0.066 (3)0.046 (2)0.022 (2)0.020 (2)0.009 (2)
C140.091 (3)0.068 (3)0.055 (2)0.029 (2)0.004 (2)0.025 (2)
C150.068 (3)0.078 (3)0.049 (2)0.001 (2)0.0006 (19)0.009 (2)
Geometric parameters (Å, º) top
Si1—N21.780 (3)C8—C111.544 (5)
Si1—N11.931 (3)C9—H9A0.9600
Si1—Cl22.0711 (14)C9—H9B0.9600
Si1—Cl32.1005 (14)C9—H9C0.9600
Si1—Cl12.1449 (14)C10—H10A0.9600
N1—C11.308 (4)C10—H10B0.9600
N1—C121.499 (4)C10—H10C0.9600
N2—C11.368 (4)C11—H11A0.9600
N2—C81.513 (4)C11—H11B0.9600
C1—C21.488 (4)C11—H11C0.9600
C2—C71.383 (5)C12—C131.516 (5)
C2—C31.386 (5)C12—C151.520 (5)
C3—C41.379 (5)C12—C141.527 (5)
C3—H30.9300C13—H13A0.9600
C4—C51.375 (6)C13—H13B0.9600
C4—H40.9300C13—H13C0.9600
C5—C61.363 (6)C14—H14A0.9600
C5—H50.9300C14—H14B0.9600
C6—C71.390 (5)C14—H14C0.9600
C6—H60.9300C15—H15A0.9600
C7—H70.9300C15—H15B0.9600
C8—C91.518 (6)C15—H15C0.9600
C8—C101.531 (6)
N2—Si1—N170.14 (12)C9—C8—C11110.8 (3)
N2—Si1—Cl2120.61 (11)C10—C8—C11105.1 (3)
N1—Si1—Cl294.21 (10)C8—C9—H9A109.5
N2—Si1—Cl3118.03 (10)C8—C9—H9B109.5
N1—Si1—Cl390.61 (9)H9A—C9—H9B109.5
Cl2—Si1—Cl3119.05 (6)C8—C9—H9C109.5
N2—Si1—Cl1100.24 (10)H9A—C9—H9C109.5
N1—Si1—Cl1169.82 (10)H9B—C9—H9C109.5
Cl2—Si1—Cl193.66 (6)C8—C10—H10A109.5
Cl3—Si1—Cl191.20 (6)C8—C10—H10B109.5
C1—N1—C12129.8 (3)H10A—C10—H10B109.5
C1—N1—Si189.35 (19)C8—C10—H10C109.5
C12—N1—Si1139.8 (2)H10A—C10—H10C109.5
C1—N2—C8128.9 (3)H10B—C10—H10C109.5
C1—N2—Si194.06 (19)C8—C11—H11A109.5
C8—N2—Si1136.8 (2)C8—C11—H11B109.5
N1—C1—N2105.9 (3)H11A—C11—H11B109.5
N1—C1—C2127.5 (3)C8—C11—H11C109.5
N2—C1—C2126.0 (3)H11A—C11—H11C109.5
N1—C1—Si156.34 (16)H11B—C11—H11C109.5
N2—C1—Si149.93 (16)N1—C12—C13108.6 (3)
C2—C1—Si1167.6 (2)N1—C12—C15109.8 (3)
C7—C2—C3119.5 (3)C13—C12—C15107.9 (3)
C7—C2—C1122.9 (3)N1—C12—C14111.2 (3)
C3—C2—C1117.6 (3)C13—C12—C14109.3 (3)
C4—C3—C2120.2 (4)C15—C12—C14110.0 (3)
C4—C3—H3119.9C12—C13—H13A109.5
C2—C3—H3119.9C12—C13—H13B109.5
C5—C4—C3119.8 (4)H13A—C13—H13B109.5
C5—C4—H4120.1C12—C13—H13C109.5
C3—C4—H4120.1H13A—C13—H13C109.5
C6—C5—C4120.5 (4)H13B—C13—H13C109.5
C6—C5—H5119.7C12—C14—H14A109.5
C4—C5—H5119.7C12—C14—H14B109.5
C5—C6—C7120.3 (4)H14A—C14—H14B109.5
C5—C6—H6119.9C12—C14—H14C109.5
C7—C6—H6119.9H14A—C14—H14C109.5
C2—C7—C6119.6 (3)H14B—C14—H14C109.5
C2—C7—H7120.2C12—C15—H15A109.5
C6—C7—H7120.2C12—C15—H15B109.5
N2—C8—C9109.0 (3)H15A—C15—H15B109.5
N2—C8—C10111.9 (3)C12—C15—H15C109.5
C9—C8—C10111.4 (4)H15A—C15—H15C109.5
N2—C8—C11108.6 (3)H15B—C15—H15C109.5

Experimental details

Crystal data
Chemical formulaC15H23Cl3N2Si
Mr365.80
Crystal system, space groupTriclinic, 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)
V3)915.3 (7)
Z2
Radiation typeMo Kα
µ (mm1)0.56
Crystal size (mm)0.35 × 0.26 × 0.15
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4535, 3166, 2189
Rint0.028
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.159, 0.99
No. of reflections3166
No. of parameters196
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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

First citationBruker, (1998). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHargittai, I., Schultz, G., Tremmel, J., Kagramanov, N. D., Maltsev, A. K. & Nefedov, O. M. (1983). J. Am. Chem. Soc. 105, 2895–2896.  CrossRef CAS Web of Science Google Scholar
First citationJones, C., Junk, P. C., Leary, S. G., Smithies, N. A. & Steed, J. W. (2002). Inorg. Chem. Commun. 5, 533–536.  Web of Science CSD CrossRef CAS Google Scholar
First citationKarsch, H. H., Schlüter, P. A. & Reisky, M. (1998). Eur. J. Inorg. Chem. pp. 433–436.  CrossRef Google Scholar
First citationKoe, J. R., Powell, D. R., Buffy, J. J., Hayase, S. & West, R. (1998). Angew. Chem. Int. Ed. 37, 1441–1442.  CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSo, C.-W., Roesky, H. W., Magull, J. & Oswald, R. B. (2006). Angew. Chem. Int. Ed. 45, 3948–3950.  Web of Science CSD CrossRef CAS Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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