Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102011307/gd1214sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102011307/gd1214Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102011307/gd1214IIsup3.hkl |
CCDC references: 193405; 193406
A 1.7 M solution of t-BuLi in n-pentane (1.09 ml, 1.86 mmol) was added to a solution of [(methyldiphenylsilyl)methyl]piperidine (550 mg, 1.86 mmol) in n-pentane (4 ml) at 183 K. After warming to room temperature, yellow crystals of {[(lithiomethyl)diphenylsilyl]methyl}piperidine (504 mg, 1.67 mmol, 90%) were isolated. These crystals were dissolved in tetrahydrofuran (THF; 6 ml), and a suspension of CdCl2 or [Mg(thf)4Br2] (0.835 mmol) in THF (2 ml) was added at 183 K. The mixture was allowed to warm to room temperature, the solvent was removed and toluene (5 ml) was added. After removal of the lithium halide, compound (II) was crystallized from toluene and compound (I) from toluene-n-pentane. The crystals of both compounds were mounted at 173 K (N2 stream), using the X-TEMP device (Kottke & Stalke, 1993).
Spectroscopic data for (I): 1H NMR (400.1 MHz, toluene-d8, δ, p.p.m.): -0.06 (s, 2JH,Cd = 61.3 Hz, 4H, CdCH2Si), 1.13 (br, 4H, NCCCH2C), 1.42–1.47 (m, 8H, NCCH2C), 2.28 (br, 12H, SiCH2N, NCH2C), 7.14–7.27 (m, 12H, aromatic H), 7.71–7.73 (m, 8H, aromatic H); {1H}13C NMR (100.6 MHz, toluene-d8, δ, p.p.m.): -11.7 (1JC,Cd = 503.1 Hz, CdCH2Si), 23.8 (NCCCH2C), 25.8 (NCCH2C), 51.6 (SiCH2N), 59.0 (NCH2C), 128.0 (C-meta), 128.8 (C-para), 134.7 (C-ortho), 141.4 (C-ipso); {1H}29Si NMR (59.6 MHz, toluene-d8, δ, p.p.m.): -5.4 (2JSi,Cd = 35.0 Hz).
Spectroscopic data for (II): 1H NMR (300.1 MHz, THF-d8, δ, p.p.m.): -1.05 (s, 4H, MgCH2Si), 1.33–1.37 (m, 4H, NCCCH2C), 1.44–1.49 (m, 8H, NCCH2C), 2.41–2.49 (m, 12H, SiCH2N, NCH2C), 7.54–7.61 (m, 12H, aromatic H), 7.62–7.68 (m, 8H, aromatic H); {1H}13C NMR (75.5 MHz, THF-d8, δ, p.p.m.): -16.5 (MgCH2Si), 24.9 (NCCCH2C), 27.4 (NCCH2C), 50.2 (SiCH2N), 59.6 (NCH2C), 128.0 (C-meta), 128.6 (C-para), 135.4 (C-ortho), 144.1 (C-ipso); {1H}29Si NMR (59.6 MHz, THF-d8, δ, p.p.m.): -9.0.
For both compounds, data collection: EXPOSE in IPDS (Stoe & Cie, 1997); cell refinement: CELL in IPDS; data reduction: INTEGRATE in IPDS; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 2001); software used to prepare material for publication: SHELXL97.
[Cd(C19H24NSi)2] | F(000) = 1464 |
Mr = 701.36 | Dx = 1.351 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 7500 reflections |
a = 27.277 (5) Å | θ = 2.5–27.0° |
b = 6.439 (1) Å | µ = 0.73 mm−1 |
c = 19.675 (4) Å | T = 173 K |
β = 94.06 (3)° | Needle, pale yellow |
V = 3447.0 (11) Å3 | 0.5 × 0.2 × 0.2 mm |
Z = 4 |
Stoe IPDS diffractometer | 3346 reflections with I > 2σ(I) |
ϕ scans | Rint = 0.057 |
Absorption correction: numerical (FACEIT in IPDS; Stoe & Cie, 1997) | θmax = 27°, θmin = 2.5° |
Tmin = 0.810, Tmax = 0.868 | h = −34→34 |
17317 measured reflections | k = −8→8 |
3736 independent reflections | l = −25→25 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.0597P)2 + 1.3741P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.103 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 1.71 e Å−3 |
3736 reflections | Δρmin = −1.37 e Å−3 |
291 parameters |
[Cd(C19H24NSi)2] | V = 3447.0 (11) Å3 |
Mr = 701.36 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 27.277 (5) Å | µ = 0.73 mm−1 |
b = 6.439 (1) Å | T = 173 K |
c = 19.675 (4) Å | 0.5 × 0.2 × 0.2 mm |
β = 94.06 (3)° |
Stoe IPDS diffractometer | 3736 independent reflections |
Absorption correction: numerical (FACEIT in IPDS; Stoe & Cie, 1997) | 3346 reflections with I > 2σ(I) |
Tmin = 0.810, Tmax = 0.868 | Rint = 0.057 |
17317 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.103 | All H-atom parameters refined |
S = 1.04 | Δρmax = 1.71 e Å−3 |
3736 reflections | Δρmin = −1.37 e Å−3 |
291 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. |
x | y | z | Uiso*/Ueq | ||
Cd | 0.000 | 0.20082 (3) | 0.25 | 0.02384 (11) | |
Si | 0.10817 (2) | 0.29625 (8) | 0.19135 (3) | 0.02162 (15) | |
N | 0.01251 (7) | 0.4619 (3) | 0.15595 (8) | 0.0225 (4) | |
C1 | 0.07303 (9) | 0.0853 (3) | 0.22722 (11) | 0.0268 (4) | |
H1A | 0.0925 (13) | 0.027 (5) | 0.2692 (15) | 0.044 (8)* | |
H1B | 0.0581 (15) | −0.017 (6) | 0.1971 (18) | 0.057 (10)* | |
C2 | 0.15832 (8) | 0.3950 (4) | 0.25351 (10) | 0.0258 (4) | |
C3 | 0.17904 (11) | 0.2656 (5) | 0.30463 (13) | 0.0337 (5) | |
H3 | 0.1664 (12) | 0.135 (5) | 0.3076 (14) | 0.029 (7)* | |
C4 | 0.21699 (12) | 0.3336 (5) | 0.34974 (14) | 0.0432 (7) | |
H4 | 0.229 (2) | 0.242 (7) | 0.382 (3) | 0.074 (13)* | |
C5 | 0.23524 (10) | 0.5322 (5) | 0.34459 (12) | 0.0430 (6) | |
H5 | 0.2643 (14) | 0.582 (6) | 0.3783 (17) | 0.051 (9)* | |
C6 | 0.21594 (11) | 0.6640 (5) | 0.29477 (14) | 0.0391 (6) | |
H6 | 0.2288 (18) | 0.802 (6) | 0.289 (2) | 0.057 (12)* | |
C7 | 0.17743 (9) | 0.5970 (4) | 0.24989 (12) | 0.0316 (5) | |
H7 | 0.1645 (14) | 0.688 (4) | 0.2185 (17) | 0.033 (8)* | |
C8 | 0.13775 (9) | 0.2304 (4) | 0.10994 (11) | 0.0265 (5) | |
C9 | 0.16493 (9) | 0.3816 (4) | 0.07801 (11) | 0.0324 (5) | |
H9 | 0.1680 (14) | 0.513 (6) | 0.0984 (17) | 0.052 (9)* | |
C10 | 0.18644 (11) | 0.3419 (5) | 0.01775 (13) | 0.0397 (6) | |
H10 | 0.2032 (14) | 0.459 (6) | −0.0049 (17) | 0.049 (9)* | |
C11 | 0.18124 (12) | 0.1480 (6) | −0.01261 (13) | 0.0455 (7) | |
H11 | 0.1971 (13) | 0.104 (5) | −0.0544 (15) | 0.042 (8)* | |
C12 | 0.15491 (12) | −0.0043 (6) | 0.01811 (14) | 0.0495 (7) | |
H12 | 0.1554 (16) | −0.151 (6) | −0.0003 (19) | 0.056 (10)* | |
C13 | 0.13333 (10) | 0.0361 (5) | 0.07916 (13) | 0.0388 (6) | |
H13 | 0.1174 (15) | −0.067 (6) | 0.0999 (18) | 0.058 (10)* | |
C14 | 0.06472 (8) | 0.5235 (3) | 0.16972 (11) | 0.0247 (4) | |
H14A | 0.0651 (11) | 0.618 (4) | 0.2095 (13) | 0.025 (6)* | |
H14B | 0.0765 (12) | 0.597 (5) | 0.1330 (15) | 0.037 (7)* | |
C15 | −0.01866 (9) | 0.6489 (4) | 0.14769 (12) | 0.0293 (5) | |
H15A | −0.0055 (13) | 0.736 (5) | 0.1131 (16) | 0.035 (8)* | |
H15B | −0.0125 (13) | 0.737 (5) | 0.1879 (16) | 0.033 (7)* | |
C16 | −0.07219 (9) | 0.5945 (5) | 0.13416 (12) | 0.0333 (5) | |
H16A | −0.089 (2) | 0.729 (7) | 0.127 (2) | 0.072 (13)* | |
H16B | −0.0805 (12) | 0.525 (5) | 0.1723 (15) | 0.035 (7)* | |
C17 | −0.08042 (10) | 0.4572 (5) | 0.07171 (12) | 0.0406 (6) | |
H17A | −0.1160 (14) | 0.424 (5) | 0.0663 (16) | 0.047 (9)* | |
H17B | −0.0733 (15) | 0.541 (6) | 0.0307 (18) | 0.058 (10)* | |
C18 | −0.04619 (12) | 0.2709 (5) | 0.07727 (14) | 0.0407 (6) | |
H18A | −0.044 (2) | 0.194 (8) | 0.037 (3) | 0.100 (19)* | |
H18B | −0.0570 (15) | 0.176 (5) | 0.1129 (18) | 0.043 (9)* | |
C19 | 0.00679 (10) | 0.3380 (4) | 0.09273 (11) | 0.0300 (5) | |
H19A | 0.0274 (14) | 0.223 (5) | 0.0960 (16) | 0.032 (8)* | |
H19B | 0.0185 (11) | 0.416 (5) | 0.0529 (14) | 0.033 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cd | 0.01879 (16) | 0.02933 (15) | 0.02379 (14) | 0.000 | 0.00414 (9) | 0.000 |
Si | 0.0167 (3) | 0.0267 (3) | 0.0216 (3) | −0.0012 (2) | 0.0020 (2) | 0.00029 (19) |
N | 0.0178 (9) | 0.0296 (9) | 0.0200 (7) | 0.0006 (7) | −0.0006 (6) | 0.0007 (7) |
C1 | 0.0204 (11) | 0.0277 (10) | 0.0330 (10) | 0.0017 (9) | 0.0057 (8) | 0.0021 (9) |
C2 | 0.0189 (11) | 0.0357 (11) | 0.0231 (9) | −0.0018 (9) | 0.0029 (8) | −0.0027 (9) |
C3 | 0.0285 (14) | 0.0429 (13) | 0.0292 (11) | −0.0006 (11) | −0.0012 (10) | 0.0018 (10) |
C4 | 0.0325 (16) | 0.0671 (18) | 0.0289 (11) | 0.0019 (14) | −0.0060 (10) | 0.0046 (12) |
C5 | 0.0243 (13) | 0.0721 (19) | 0.0321 (11) | −0.0055 (13) | −0.0011 (9) | −0.0133 (12) |
C6 | 0.0310 (15) | 0.0481 (14) | 0.0387 (13) | −0.0085 (12) | 0.0064 (11) | −0.0110 (12) |
C7 | 0.0243 (12) | 0.0392 (12) | 0.0311 (10) | −0.0041 (10) | 0.0006 (9) | −0.0015 (10) |
C8 | 0.0186 (12) | 0.0392 (12) | 0.0215 (9) | 0.0016 (9) | 0.0003 (8) | −0.0005 (9) |
C9 | 0.0272 (13) | 0.0404 (13) | 0.0303 (10) | 0.0026 (11) | 0.0071 (9) | 0.0037 (10) |
C10 | 0.0277 (14) | 0.0602 (16) | 0.0319 (11) | 0.0065 (13) | 0.0062 (10) | 0.0103 (12) |
C11 | 0.0341 (16) | 0.0777 (19) | 0.0251 (10) | 0.0083 (15) | 0.0045 (10) | −0.0057 (13) |
C12 | 0.0406 (17) | 0.067 (2) | 0.0422 (13) | −0.0055 (15) | 0.0077 (11) | −0.0252 (14) |
C13 | 0.0311 (14) | 0.0480 (14) | 0.0381 (12) | −0.0063 (12) | 0.0075 (10) | −0.0108 (12) |
C14 | 0.0201 (11) | 0.0266 (10) | 0.0275 (9) | −0.0016 (9) | 0.0011 (8) | 0.0034 (8) |
C15 | 0.0256 (12) | 0.0325 (11) | 0.0296 (10) | 0.0060 (10) | 0.0007 (9) | 0.0067 (10) |
C16 | 0.0231 (12) | 0.0478 (14) | 0.0288 (10) | 0.0048 (11) | 0.0009 (8) | 0.0039 (10) |
C17 | 0.0239 (13) | 0.0682 (18) | 0.0286 (10) | 0.0008 (12) | −0.0055 (9) | 0.0007 (12) |
C18 | 0.0324 (16) | 0.0588 (17) | 0.0297 (12) | −0.0033 (13) | −0.0055 (10) | −0.0116 (12) |
C19 | 0.0260 (13) | 0.0428 (12) | 0.0209 (9) | 0.0021 (11) | 0.0001 (8) | −0.0037 (9) |
Cd—C1i | 2.202 (2) | C9—C10 | 1.383 (3) |
Cd—C1 | 2.202 (2) | C9—H9 | 0.94 (4) |
Cd—Ni | 2.5409 (17) | C10—C11 | 1.387 (5) |
Cd—N | 2.5409 (17) | C10—H10 | 1.00 (4) |
Si—C1 | 1.832 (2) | C11—C12 | 1.380 (5) |
Si—C2 | 1.880 (2) | C11—H11 | 1.00 (3) |
Si—C8 | 1.892 (2) | C12—C13 | 1.399 (3) |
Si—C14 | 1.912 (2) | C12—H12 | 1.01 (4) |
N—C15 | 1.476 (3) | C13—H13 | 0.91 (4) |
N—C19 | 1.477 (3) | C14—H14A | 0.99 (3) |
N—C14 | 1.485 (3) | C14—H14B | 0.94 (3) |
C1—H1A | 1.02 (3) | C15—C16 | 1.507 (4) |
C1—H1B | 0.96 (4) | C15—H15A | 0.97 (3) |
C2—C3 | 1.395 (3) | C15—H15B | 0.98 (3) |
C2—C7 | 1.404 (3) | C16—C17 | 1.517 (4) |
C3—C4 | 1.386 (4) | C16—H16A | 0.98 (5) |
C3—H3 | 0.91 (3) | C16—H16B | 0.91 (3) |
C4—C5 | 1.379 (5) | C17—C18 | 1.519 (4) |
C4—H4 | 0.92 (5) | C17—H17A | 0.99 (4) |
C5—C6 | 1.373 (4) | C17—H17B | 1.00 (4) |
C5—H5 | 1.05 (4) | C18—C19 | 1.518 (4) |
C6—C7 | 1.392 (4) | C18—H18A | 0.95 (6) |
C6—H6 | 0.97 (4) | C18—H18B | 0.99 (3) |
C7—H7 | 0.91 (3) | C19—H19A | 0.93 (3) |
C8—C13 | 1.391 (4) | C19—H19B | 1.00 (3) |
C8—C9 | 1.400 (4) | ||
C1i—Cd—C1 | 140.53 (12) | C9—C10—C11 | 119.9 (3) |
C1i—Cd—Ni | 84.56 (7) | C9—C10—H10 | 118.5 (19) |
C1—Cd—Ni | 122.80 (8) | C11—C10—H10 | 121.4 (19) |
C1i—Cd—N | 122.80 (8) | C12—C11—C10 | 119.4 (2) |
C1—Cd—N | 84.56 (7) | C12—C11—H11 | 115 (2) |
Ni—Cd—N | 97.15 (8) | C10—C11—H11 | 125 (2) |
C1—Si—C2 | 112.11 (11) | C11—C12—C13 | 120.5 (3) |
C1—Si—C8 | 115.22 (11) | C11—C12—H12 | 119 (2) |
C2—Si—C8 | 107.00 (10) | C13—C12—H12 | 120 (2) |
C1—Si—C14 | 108.67 (10) | C8—C13—C12 | 120.8 (3) |
C2—Si—C14 | 107.26 (10) | C8—C13—H13 | 120 (2) |
C8—Si—C14 | 106.14 (10) | C12—C13—H13 | 120 (2) |
C15—N—C19 | 108.79 (18) | N—C14—Si | 114.04 (15) |
C15—N—C14 | 109.85 (18) | N—C14—H14A | 105.3 (17) |
C19—N—C14 | 109.93 (17) | Si—C14—H14A | 108.7 (16) |
C15—N—Cd | 120.92 (13) | N—C14—H14B | 111.7 (19) |
C19—N—Cd | 104.15 (14) | Si—C14—H14B | 108.6 (19) |
C14—N—Cd | 102.74 (12) | H14A—C14—H14B | 108 (2) |
Si—C1—Cd | 109.49 (11) | N—C15—C16 | 111.9 (2) |
Si—C1—H1A | 109.1 (19) | N—C15—H15A | 108 (2) |
Cd—C1—H1A | 112.6 (18) | C16—C15—H15A | 114 (2) |
Si—C1—H1B | 119 (2) | N—C15—H15B | 109 (2) |
Cd—C1—H1B | 90 (2) | C16—C15—H15B | 113 (2) |
H1A—C1—H1B | 115 (3) | H15A—C15—H15B | 101 (3) |
C3—C2—C7 | 117.2 (2) | C15—C16—C17 | 111.4 (2) |
C3—C2—Si | 120.40 (19) | C15—C16—H16A | 105 (3) |
C7—C2—Si | 122.40 (18) | C17—C16—H16A | 111 (3) |
C4—C3—C2 | 121.3 (3) | C15—C16—H16B | 105 (2) |
C4—C3—H3 | 121.1 (19) | C17—C16—H16B | 110.4 (19) |
C2—C3—H3 | 117.6 (19) | H16A—C16—H16B | 114 (3) |
C5—C4—C3 | 120.2 (3) | C16—C17—C18 | 110.3 (2) |
C5—C4—H4 | 122 (3) | C16—C17—H17A | 107.5 (18) |
C3—C4—H4 | 118 (3) | C18—C17—H17A | 115 (2) |
C6—C5—C4 | 120.3 (3) | C16—C17—H17B | 108 (2) |
C6—C5—H5 | 120 (2) | C18—C17—H17B | 109 (2) |
C4—C5—H5 | 120 (2) | H17A—C17—H17B | 106 (3) |
C5—C6—C7 | 119.7 (3) | C19—C18—C17 | 111.2 (3) |
C5—C6—H6 | 122 (3) | C19—C18—H18A | 102 (4) |
C7—C6—H6 | 119 (3) | C17—C18—H18A | 115 (4) |
C6—C7—C2 | 121.4 (3) | C19—C18—H18B | 111 (2) |
C6—C7—H7 | 118 (2) | C17—C18—H18B | 109 (2) |
C2—C7—H7 | 121 (2) | H18A—C18—H18B | 108 (4) |
C13—C8—C9 | 117.6 (2) | N—C19—C18 | 111.4 (2) |
C13—C8—Si | 122.76 (19) | N—C19—H19A | 110 (2) |
C9—C8—Si | 119.69 (19) | C18—C19—H19A | 110 (2) |
C10—C9—C8 | 121.8 (3) | N—C19—H19B | 111.5 (17) |
C10—C9—H9 | 120 (2) | C18—C19—H19B | 109.7 (18) |
C8—C9—H9 | 118 (2) | H19A—C19—H19B | 103 (3) |
Symmetry code: (i) −x, y, −z+1/2. |
[Mg(C19H24NSi)2] | F(000) = 1320 |
Mr = 613.27 | Dx = 1.195 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 6000 reflections |
a = 27.215 (5) Å | θ = 2.5–26.0° |
b = 6.410 (1) Å | µ = 0.15 mm−1 |
c = 19.576 (4) Å | T = 173 K |
β = 93.38 (3)° | Needle, colourless |
V = 3409.1 (11) Å3 | 0.6 × 0.2 × 0.1 mm |
Z = 4 |
Stoe IPDS diffractometer | 2453 reflections with I > 2σ(I) |
ϕ scans | Rint = 0.059 |
Absorption correction: numerical (FACEIT in IPDS; Stoe & Cie, 1997) | θmax = 26°, θmin = 2.5° |
Tmin = 0.905, Tmax = 0.975 | h = −33→33 |
13184 measured reflections | k = −7→7 |
3223 independent reflections | l = −22→21 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.044 | w = 1/[σ2(Fo2) + (0.076P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.115 | (Δ/σ)max < 0.001 |
S = 1.00 | Δρmax = 0.34 e Å−3 |
3223 reflections | Δρmin = −0.38 e Å−3 |
291 parameters |
[Mg(C19H24NSi)2] | V = 3409.1 (11) Å3 |
Mr = 613.27 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 27.215 (5) Å | µ = 0.15 mm−1 |
b = 6.410 (1) Å | T = 173 K |
c = 19.576 (4) Å | 0.6 × 0.2 × 0.1 mm |
β = 93.38 (3)° |
Stoe IPDS diffractometer | 3223 independent reflections |
Absorption correction: numerical (FACEIT in IPDS; Stoe & Cie, 1997) | 2453 reflections with I > 2σ(I) |
Tmin = 0.905, Tmax = 0.975 | Rint = 0.059 |
13184 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.115 | All H-atom parameters refined |
S = 1.00 | Δρmax = 0.34 e Å−3 |
3223 reflections | Δρmin = −0.38 e Å−3 |
291 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. |
x | y | z | Uiso*/Ueq | ||
Mg | 0.000 | 0.26639 (13) | 0.25 | 0.0114 (2) | |
Si | 0.106835 (15) | 0.30101 (8) | 0.19397 (3) | 0.01126 (16) | |
N | 0.01175 (5) | 0.4755 (2) | 0.15982 (8) | 0.0112 (3) | |
C1 | 0.06862 (6) | 0.1050 (3) | 0.23198 (11) | 0.0151 (4) | |
H1A | 0.0849 (8) | 0.030 (4) | 0.2727 (13) | 0.025 (6)* | |
H1B | 0.0562 (9) | 0.004 (4) | 0.1968 (15) | 0.038 (7)* | |
C2 | 0.15775 (6) | 0.3975 (3) | 0.25555 (10) | 0.0147 (4) | |
C3 | 0.17808 (7) | 0.2643 (3) | 0.30620 (12) | 0.0219 (5) | |
H3 | 0.1655 (9) | 0.126 (4) | 0.3115 (14) | 0.031 (7)* | |
C4 | 0.21658 (8) | 0.3272 (4) | 0.35054 (13) | 0.0298 (5) | |
H4 | 0.2301 (12) | 0.234 (5) | 0.3825 (19) | 0.055 (9)* | |
C5 | 0.23613 (8) | 0.5251 (4) | 0.34560 (13) | 0.0297 (6) | |
H5 | 0.2619 (9) | 0.565 (4) | 0.3729 (14) | 0.029 (6)* | |
C6 | 0.21694 (7) | 0.6608 (4) | 0.29598 (12) | 0.0257 (5) | |
H6 | 0.2307 (8) | 0.792 (4) | 0.2914 (13) | 0.021 (6)* | |
C7 | 0.17804 (7) | 0.5977 (3) | 0.25159 (12) | 0.0210 (5) | |
H7 | 0.1645 (8) | 0.701 (4) | 0.2150 (13) | 0.019 (6)* | |
C8 | 0.13661 (6) | 0.2333 (3) | 0.11173 (11) | 0.0148 (4) | |
C9 | 0.16501 (7) | 0.3816 (3) | 0.07900 (12) | 0.0209 (5) | |
H9 | 0.1705 (9) | 0.523 (4) | 0.0991 (14) | 0.030 (6)* | |
C10 | 0.18643 (8) | 0.3375 (4) | 0.01818 (13) | 0.0276 (5) | |
H10 | 0.2041 (9) | 0.443 (4) | −0.0036 (15) | 0.038 (7)* | |
C11 | 0.18027 (8) | 0.1444 (4) | −0.01198 (13) | 0.0313 (6) | |
H11 | 0.1941 (10) | 0.121 (5) | −0.0557 (16) | 0.044 (8)* | |
C12 | 0.15285 (8) | −0.0050 (4) | 0.01893 (14) | 0.0350 (6) | |
H12 | 0.1487 (11) | −0.143 (5) | −0.0008 (16) | 0.048 (8)* | |
C13 | 0.13144 (7) | 0.0390 (4) | 0.07998 (13) | 0.0249 (5) | |
H13 | 0.1139 (9) | −0.070 (5) | 0.1035 (15) | 0.038 (7)* | |
C14 | 0.06490 (6) | 0.5344 (3) | 0.17079 (11) | 0.0136 (4) | |
H14A | 0.0666 (7) | 0.634 (3) | 0.2090 (12) | 0.012 (5)* | |
H14B | 0.0758 (8) | 0.608 (4) | 0.1302 (14) | 0.027 (6)* | |
C15 | −0.01832 (6) | 0.6682 (3) | 0.14876 (12) | 0.0161 (4) | |
H15A | −0.0059 (9) | 0.742 (4) | 0.1106 (15) | 0.029 (7)* | |
H15B | −0.0123 (7) | 0.754 (3) | 0.1895 (13) | 0.013 (5)* | |
C16 | −0.07239 (7) | 0.6180 (4) | 0.13404 (12) | 0.0205 (5) | |
H16A | −0.0909 (8) | 0.748 (4) | 0.1266 (13) | 0.022 (6)* | |
H16B | −0.0843 (8) | 0.558 (4) | 0.1744 (13) | 0.016 (5)* | |
C17 | −0.08055 (7) | 0.4745 (4) | 0.07273 (13) | 0.0258 (5) | |
H17A | −0.1142 (10) | 0.434 (4) | 0.0664 (15) | 0.039 (7)* | |
H17B | −0.0723 (9) | 0.552 (4) | 0.0320 (15) | 0.032 (7)* | |
C18 | −0.04749 (7) | 0.2839 (4) | 0.08047 (13) | 0.0258 (5) | |
H18A | −0.0494 (10) | 0.188 (4) | 0.0388 (17) | 0.043 (8)* | |
H18B | −0.0595 (10) | 0.194 (4) | 0.1184 (16) | 0.039 (7)* | |
C19 | 0.00582 (7) | 0.3456 (3) | 0.09699 (11) | 0.0184 (4) | |
H19A | 0.0251 (8) | 0.222 (4) | 0.1017 (12) | 0.016 (5)* | |
H19B | 0.0180 (8) | 0.429 (4) | 0.0565 (14) | 0.028 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mg | 0.0091 (4) | 0.0122 (5) | 0.0131 (5) | 0.000 | 0.0027 (3) | 0.000 |
Si | 0.0078 (2) | 0.0117 (3) | 0.0144 (3) | −0.00090 (17) | 0.00148 (18) | 0.0002 (2) |
N | 0.0100 (7) | 0.0108 (8) | 0.0127 (9) | 0.0000 (5) | −0.0003 (6) | 0.0004 (6) |
C1 | 0.0119 (8) | 0.0127 (10) | 0.0209 (12) | 0.0009 (7) | 0.0032 (7) | 0.0005 (8) |
C2 | 0.0102 (7) | 0.0181 (10) | 0.0161 (11) | −0.0009 (7) | 0.0036 (7) | −0.0034 (8) |
C3 | 0.0180 (9) | 0.0242 (12) | 0.0236 (14) | 0.0008 (8) | 0.0008 (8) | 0.0030 (9) |
C4 | 0.0227 (10) | 0.0443 (15) | 0.0214 (14) | 0.0014 (10) | −0.0060 (9) | 0.0054 (11) |
C5 | 0.0172 (10) | 0.0484 (15) | 0.0231 (15) | −0.0052 (9) | −0.0023 (9) | −0.0105 (11) |
C6 | 0.0187 (9) | 0.0290 (13) | 0.0298 (15) | −0.0086 (8) | 0.0036 (9) | −0.0112 (10) |
C7 | 0.0169 (9) | 0.0218 (11) | 0.0243 (13) | −0.0046 (8) | 0.0021 (8) | −0.0002 (9) |
C8 | 0.0093 (7) | 0.0192 (10) | 0.0157 (12) | 0.0023 (7) | −0.0016 (7) | −0.0001 (8) |
C9 | 0.0184 (9) | 0.0221 (11) | 0.0225 (13) | 0.0021 (8) | 0.0050 (8) | 0.0037 (9) |
C10 | 0.0210 (9) | 0.0390 (14) | 0.0236 (14) | 0.0067 (9) | 0.0066 (9) | 0.0086 (10) |
C11 | 0.0217 (10) | 0.0550 (16) | 0.0173 (14) | 0.0087 (10) | 0.0026 (9) | −0.0054 (11) |
C12 | 0.0275 (11) | 0.0440 (15) | 0.0337 (17) | −0.0014 (10) | 0.0034 (10) | −0.0216 (12) |
C13 | 0.0195 (9) | 0.0250 (12) | 0.0307 (14) | −0.0047 (8) | 0.0050 (8) | −0.0075 (10) |
C14 | 0.0107 (8) | 0.0134 (10) | 0.0167 (12) | −0.0029 (7) | 0.0019 (7) | 0.0017 (8) |
C15 | 0.0148 (9) | 0.0140 (10) | 0.0193 (13) | 0.0028 (7) | 0.0000 (7) | 0.0053 (8) |
C16 | 0.0136 (9) | 0.0280 (12) | 0.0198 (13) | 0.0051 (8) | −0.0002 (8) | 0.0043 (9) |
C17 | 0.0144 (9) | 0.0431 (14) | 0.0192 (14) | 0.0016 (8) | −0.0056 (8) | 0.0015 (10) |
C18 | 0.0222 (10) | 0.0337 (13) | 0.0206 (14) | −0.0018 (9) | −0.0066 (8) | −0.0094 (10) |
C19 | 0.0176 (9) | 0.0242 (11) | 0.0133 (12) | 0.0031 (8) | −0.0001 (7) | −0.0047 (8) |
Mg—C1i | 2.1816 (18) | C8—C9 | 1.403 (3) |
Mg—C1 | 2.1816 (18) | C9—C10 | 1.385 (3) |
Mg—Ni | 2.2545 (17) | C9—H9 | 1.00 (3) |
Mg—N | 2.2545 (17) | C10—C11 | 1.378 (4) |
Mg—Sii | 3.1752 (8) | C10—H10 | 0.95 (3) |
Mg—Si | 3.1752 (9) | C11—C12 | 1.376 (4) |
Si—C1 | 1.818 (2) | C11—H11 | 0.97 (3) |
Si—C2 | 1.886 (2) | C12—C13 | 1.389 (3) |
Si—C8 | 1.895 (2) | C12—H12 | 0.97 (3) |
Si—C14 | 1.9200 (19) | C13—H13 | 0.98 (3) |
N—C19 | 1.486 (3) | C14—H14A | 0.98 (2) |
N—C15 | 1.490 (2) | C14—H14B | 0.98 (3) |
N—C14 | 1.498 (2) | C15—C16 | 1.517 (3) |
C1—H1A | 1.01 (3) | C15—H15A | 0.96 (3) |
C1—H1B | 0.99 (3) | C15—H15B | 0.97 (2) |
C2—C3 | 1.398 (3) | C16—C17 | 1.518 (3) |
C2—C7 | 1.401 (3) | C16—H16A | 0.98 (2) |
C3—C4 | 1.381 (3) | C16—H16B | 0.95 (3) |
C3—H3 | 0.96 (3) | C17—C18 | 1.520 (3) |
C4—C5 | 1.381 (4) | C17—H17A | 0.95 (3) |
C4—H4 | 0.92 (3) | C17—H17B | 0.98 (3) |
C5—C6 | 1.383 (4) | C18—C19 | 1.520 (3) |
C5—H5 | 0.89 (3) | C18—H18A | 1.02 (3) |
C6—C7 | 1.390 (3) | C18—H18B | 1.01 (3) |
C6—H6 | 0.93 (2) | C19—H19A | 0.95 (2) |
C7—H7 | 1.03 (2) | C19—H19B | 1.03 (3) |
C8—C13 | 1.395 (3) | ||
C1i—Mg—C1 | 123.39 (11) | C13—C8—C9 | 116.4 (2) |
C1i—Mg—Ni | 89.60 (7) | C13—C8—Si | 123.08 (16) |
C1—Mg—Ni | 124.81 (7) | C9—C8—Si | 120.50 (16) |
C1i—Mg—N | 124.81 (7) | C10—C9—C8 | 121.7 (2) |
C1—Mg—N | 89.60 (7) | C10—C9—H9 | 117.6 (15) |
Ni—Mg—N | 107.02 (9) | C8—C9—H9 | 120.7 (15) |
C1i—Mg—Sii | 33.62 (5) | C11—C10—C9 | 120.3 (2) |
C1—Mg—Sii | 154.02 (6) | C11—C10—H10 | 120.2 (17) |
Ni—Mg—Sii | 60.85 (4) | C9—C10—H10 | 119.4 (17) |
N—Mg—Sii | 113.83 (4) | C10—C11—C12 | 119.5 (2) |
C1i—Mg—Si | 154.02 (6) | C10—C11—H11 | 118.2 (18) |
C1—Mg—Si | 33.62 (5) | C12—C11—H11 | 122.2 (18) |
Ni—Mg—Si | 113.83 (4) | C11—C12—C13 | 120.2 (2) |
N—Mg—Si | 60.85 (4) | C11—C12—H12 | 120.8 (18) |
Sii—Mg—Si | 171.99 (3) | C13—C12—H12 | 119.0 (19) |
C1—Si—C2 | 112.43 (10) | C12—C13—C8 | 121.9 (2) |
C1—Si—C8 | 118.24 (9) | C12—C13—H13 | 120.1 (17) |
C2—Si—C8 | 106.45 (8) | C8—C13—H13 | 117.9 (17) |
C1—Si—C14 | 106.79 (8) | N—C14—Si | 113.14 (12) |
C2—Si—C14 | 107.42 (9) | N—C14—H14A | 106.0 (12) |
C8—Si—C14 | 104.81 (9) | Si—C14—H14A | 109.0 (12) |
C1—Si—Mg | 41.64 (6) | N—C14—H14B | 109.8 (14) |
C2—Si—Mg | 117.08 (6) | Si—C14—H14B | 111.2 (14) |
C8—Si—Mg | 136.36 (6) | H14A—C14—H14B | 107.5 (19) |
C14—Si—Mg | 65.95 (6) | N—C15—C16 | 111.73 (16) |
C19—N—C15 | 108.19 (15) | N—C15—H15A | 107.9 (15) |
C19—N—C14 | 108.46 (14) | C16—C15—H15A | 109.7 (15) |
C15—N—C14 | 109.23 (14) | N—C15—H15B | 106.5 (13) |
C19—N—Mg | 107.54 (12) | C16—C15—H15B | 113.0 (12) |
C15—N—Mg | 120.30 (12) | H15A—C15—H15B | 108 (2) |
C14—N—Mg | 102.59 (11) | C15—C16—C17 | 111.94 (17) |
Si—C1—Mg | 104.73 (9) | C15—C16—H16A | 109.3 (13) |
Si—C1—H1A | 114.6 (13) | C17—C16—H16A | 110.4 (15) |
Mg—C1—H1A | 116.1 (13) | C15—C16—H16B | 107.5 (13) |
Si—C1—H1B | 110.3 (16) | C17—C16—H16B | 111.6 (14) |
Mg—C1—H1B | 99.4 (15) | H16A—C16—H16B | 105.8 (19) |
H1A—C1—H1B | 111 (2) | C18—C17—C16 | 110.51 (18) |
C3—C2—C7 | 117.26 (18) | C18—C17—H17A | 110.6 (17) |
C3—C2—Si | 119.86 (15) | C16—C17—H17A | 111.3 (17) |
C7—C2—Si | 122.83 (16) | C18—C17—H17B | 109.2 (15) |
C4—C3—C2 | 121.4 (2) | C16—C17—H17B | 107.8 (16) |
C4—C3—H3 | 117.7 (15) | H17A—C17—H17B | 107 (2) |
C2—C3—H3 | 120.9 (15) | C17—C18—C19 | 111.34 (19) |
C5—C4—C3 | 120.4 (2) | C17—C18—H18A | 113.9 (16) |
C5—C4—H4 | 120 (2) | C19—C18—H18A | 109.3 (15) |
C3—C4—H4 | 120 (2) | C17—C18—H18B | 108.4 (15) |
C4—C5—C6 | 119.7 (2) | C19—C18—H18B | 109.8 (16) |
C4—C5—H5 | 120.7 (17) | H18A—C18—H18B | 104 (2) |
C6—C5—H5 | 119.5 (17) | N—C19—C18 | 112.19 (16) |
C5—C6—C7 | 119.9 (2) | N—C19—H19A | 110.7 (14) |
C5—C6—H6 | 120.0 (15) | C18—C19—H19A | 108.7 (13) |
C7—C6—H6 | 120.1 (15) | N—C19—H19B | 109.0 (15) |
C6—C7—C2 | 121.3 (2) | C18—C19—H19B | 108.5 (13) |
C6—C7—H7 | 118.5 (13) | H19A—C19—H19B | 107.7 (19) |
C2—C7—H7 | 120.2 (13) |
Symmetry code: (i) −x, y, −z+1/2. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [Cd(C19H24NSi)2] | [Mg(C19H24NSi)2] |
Mr | 701.36 | 613.27 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c |
Temperature (K) | 173 | 173 |
a, b, c (Å) | 27.277 (5), 6.439 (1), 19.675 (4) | 27.215 (5), 6.410 (1), 19.576 (4) |
β (°) | 94.06 (3) | 93.38 (3) |
V (Å3) | 3447.0 (11) | 3409.1 (11) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.73 | 0.15 |
Crystal size (mm) | 0.5 × 0.2 × 0.2 | 0.6 × 0.2 × 0.1 |
Data collection | ||
Diffractometer | Stoe IPDS diffractometer | Stoe IPDS diffractometer |
Absorption correction | Numerical (FACEIT in IPDS; Stoe & Cie, 1997) | Numerical (FACEIT in IPDS; Stoe & Cie, 1997) |
Tmin, Tmax | 0.810, 0.868 | 0.905, 0.975 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17317, 3736, 3346 | 13184, 3223, 2453 |
Rint | 0.057 | 0.059 |
(sin θ/λ)max (Å−1) | 0.639 | 0.617 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.103, 1.04 | 0.044, 0.115, 1.00 |
No. of reflections | 3736 | 3223 |
No. of parameters | 291 | 291 |
H-atom treatment | All H-atom parameters refined | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 1.71, −1.37 | 0.34, −0.38 |
Computer programs: EXPOSE in IPDS (Stoe & Cie, 1997), CELL in IPDS, INTEGRATE in IPDS, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 2001), SHELXL97.
Cd—C1 | 2.202 (2) | Si—C2 | 1.880 (2) |
Cd—N | 2.5409 (17) | Si—C8 | 1.892 (2) |
Si—C1 | 1.832 (2) | Si—C14 | 1.912 (2) |
C1i—Cd—C1 | 140.53 (12) | C1—Cd—N | 84.56 (7) |
C1i—Cd—N | 122.80 (8) | Ni—Cd—N | 97.15 (8) |
Symmetry code: (i) −x, y, −z+1/2. |
Mg—C1 | 2.1816 (18) | Si—C2 | 1.886 (2) |
Mg—N | 2.2545 (17) | Si—C8 | 1.895 (2) |
Si—C1 | 1.818 (2) | Si—C14 | 1.9200 (19) |
C1i—Mg—C1 | 123.39 (11) | C1i—Mg—N | 124.81 (7) |
C1i—Mg—Ni | 89.60 (7) | Ni—Mg—N | 107.02 (9) |
Symmetry code: (i) −x, y, −z+1/2. |
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We are interested in the synthesis of enantiomerically enriched [(aminomethyl)silylmethyl]metal compounds, bearing metals which are essential for preparative organic and inorganic chemistry. By the principle of side-arm donation, a chiral amine can introduce stereochemical information into the system and fix (stabilize) the metal at the metallated C centre by intramolecular coordination. The synthesis of compounds of this type starts from the corresponding [(aminomethyl)silylmethyl]lithium compounds by reaction with metal halides.
In a pre-study, we synthesized non-chiral bis{[diphenyl(piperidinomethyl)silyl]methyl}metal compounds to study them in the solid state. We obtained two interesting molecules of this type for the metals cadmium, (I), and magnesium, (II), the metal centres being intramolecularly coordinated by two piperidinomethyl groups. Compounds (I) and (II) are isostructural and isomorphous. Through two M—C and two M—N contacts (M is Cd or Mg), a spirocyclic system is obtained, with Mg or Cd in the centre, exhibiting distorted tetrahedral geometry at M. \sch
When compared with similar intramolecularly stabilized structures, both (I) and (II) show rather small C—M—C angles. In comparable structures (Henderson et al., 1986; Khan et al., 1987; Schumann et al., 1998), these angles range from 174 (3) to 166.2 (2)°, whereas in (I), the angle is found to be more than 20° smaller (Table 1). In related Mg compounds, the Cl—Mg—Cl angle ranges from 147.68 (8) to 157.0 (7)° for related structures (Seidel et al., 2001; Henderson et al., 1986); again, this angle is more than 20° smaller in (II) (Table 2).
Another feature of these two compounds, as for other polar [(aminomethyl)silylmethyl]metal compounds, is the length of the Si—C bond between Si and the metallated C centre. Since it is well known that Si centres have a stabilizing effect on α-carbanionic centres (α effect), the Si—C bond length depends on the polarity of the M—C bond. In a related non-metallated (silylmethyl)amine (crystallized as an ammonium salt), the Si—C bond length is 1.914 (9) Å (Strohmann et al., 2002). The values in (I) and (II) (Tables 1 and 2) indicate a much more polar M—C bond in (II).
By the formal replacement of CH2 by SiPh2, the C—Cd—C angle decreases (accompanied by a shorter M—N distance), when (I) is compared with a similar structure reported by Schumann et al. (1998). The same observation is made for the C—Mg—C angle of (II), considering related structures reported by Seidel et al. (2001). Whether these interesting angles are the result of electronic or steric effects emerging from the presence of Si in the present structures still remains to be established (e.g. by computational methods).