organic compounds
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
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
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Data collection: SMART (Bruker, 1998); cell 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
10.1107/S1600536808010398/cv2396sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808010398/cv2396Isup2.hkl
All manipulations were carried out in an inert atmosphere of N2 using standard Schlenk techniques and in a N2 filled
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).
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).
Data collection: SMART (Bruker, 1998); cell
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).Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity. |
C15H23Cl3N2Si | Z = 2 |
Mr = 365.80 | F(000) = 384 |
Triclinic, P1 | Dx = 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 |
Bruker SMART CCD area-detector diffractometer | 2189 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ϕ and ω scans | h = −7→7 |
4535 measured reflections | k = −7→12 |
3166 independent reflections | l = −16→16 |
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(Fo2) + (0.102P)2] where P = (Fo2 + 2Fc2)/3 |
3166 reflections | (Δ/σ)max < 0.001 |
196 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.43 e Å−3 |
C15H23Cl3N2Si | γ = 84.189 (6)° |
Mr = 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)° |
Bruker SMART CCD area-detector diffractometer | 2189 reflections with I > 2σ(I) |
4535 measured reflections | Rint = 0.028 |
3166 independent reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 0.99 | Δρmax = 0.44 e Å−3 |
3166 reflections | Δρmin = −0.43 e Å−3 |
196 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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 |
Mr | 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 |
Rint | 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 |
Δρmax, Δρmin (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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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).