Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101014408/tr1003sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101014408/tr1003Isup2.hkl |
CCDC reference: 175074
For related literature, see: Allen & Kennard (1993); Andrews et al. (2000); Blake et al. (1996); Chao et al. (1989); Clegg et al. (1997); Forbes et al. (2000, 2001); Gibson et al. (2000); Henderson et al. (1997); Kennepohl et al. (1991, 1992); Lehmkuhl et al. (1986); Schumann et al. (2000); Sebestl et al. (1998); Westerhausen & Schwarz (1992).
All manipulations were carried out under an inert atmosphere of argon using standard Schlenk tube techniques. 2,6-Diisopropyl-N-(trimethylsilyl)aniline was synthesized as an ether-containing yellow liquid by the method of Chao et al. (1989). This amine (6 mmol) was then added to a 0.875 M solution of dibutylmagnesium (3 mmol) in heptane at 273 K. After heating the solution to reflux for 2 h, the volatile portions were removed under vacuum to leave (I) as a colourless solid (0.6 mmol, 20% yield), together with an unidentified orange oil. Crystals of (I) suitable for study by single-crystal diffraction were obtained from hexane solution.
All H atoms were placed in calculated positions and refined as riding, with C—H = 0.95–1.00 Å. Query.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992); program(s) used to solve structure: SIR (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular view of (I) showing the atom-numbering scheme and with 50% probability displacement ellipsoids. H atoms have been omitted for clarity. |
[Mg(C4H10O)(C15H26NSi)2] | F(000) = 1312 |
Mr = 595.35 | Dx = 1.044 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
a = 12.359 (2) Å | Cell parameters from 25 reflections |
b = 18.443 (3) Å | θ = 15.7–18.5° |
c = 16.984 (2) Å | µ = 0.14 mm−1 |
β = 101.900 (14)° | T = 123 K |
V = 3788.1 (10) Å3 | Plate, colourless |
Z = 4 | 0.55 × 0.30 × 0.15 mm |
Rigaku AFC-7S diffractometer | Rint = 0.023 |
Radiation source: fine-focus sealed tube | θmax = 27.5°, θmin = 2.5° |
Graphite monochromator | h = 0→16 |
ω/2θ scans | k = 0→23 |
9082 measured reflections | l = −22→21 |
8689 independent reflections | 3 standard reflections every 150 reflections |
5523 reflections with I > 2σ(I) | intensity decay: 0.9% |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0432P)2 + 0.9303P] where P = (Fo2 + 2Fc2)/3 |
8689 reflections | (Δ/σ)max = 0.001 |
377 parameters | Δρmax = 0.44 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
[Mg(C4H10O)(C15H26NSi)2] | V = 3788.1 (10) Å3 |
Mr = 595.35 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.359 (2) Å | µ = 0.14 mm−1 |
b = 18.443 (3) Å | T = 123 K |
c = 16.984 (2) Å | 0.55 × 0.30 × 0.15 mm |
β = 101.900 (14)° |
Rigaku AFC-7S diffractometer | Rint = 0.023 |
9082 measured reflections | 3 standard reflections every 150 reflections |
8689 independent reflections | intensity decay: 0.9% |
5523 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.44 e Å−3 |
8689 reflections | Δρmin = −0.20 e Å−3 |
377 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 | 0.65378 (4) | 0.32763 (3) | 0.14686 (3) | 0.02303 (11) | |
Si2 | 0.16565 (4) | 0.32305 (3) | 0.21298 (3) | 0.03127 (13) | |
Mg1 | 0.40542 (5) | 0.26980 (3) | 0.17360 (3) | 0.02219 (13) | |
O1 | 0.34555 (11) | 0.16729 (6) | 0.17737 (9) | 0.0376 (3) | |
N1 | 0.54609 (10) | 0.26683 (7) | 0.13559 (8) | 0.0201 (3) | |
N2 | 0.29920 (11) | 0.34006 (7) | 0.20277 (8) | 0.0228 (3) | |
C1 | 0.76462 (15) | 0.31349 (13) | 0.23954 (11) | 0.0400 (5) | |
H1A | 0.7310 | 0.3119 | 0.2870 | 0.060* | |
H1B | 0.8177 | 0.3536 | 0.2451 | 0.060* | |
H1C | 0.8029 | 0.2677 | 0.2349 | 0.060* | |
C2 | 0.72382 (14) | 0.32362 (10) | 0.05869 (11) | 0.0313 (4) | |
H2A | 0.7466 | 0.2736 | 0.0511 | 0.047* | |
H2B | 0.7891 | 0.3551 | 0.0689 | 0.047* | |
H2C | 0.6724 | 0.3400 | 0.0101 | 0.047* | |
C3 | 0.60505 (15) | 0.42211 (10) | 0.15767 (13) | 0.0351 (4) | |
H3A | 0.5552 | 0.4369 | 0.1076 | 0.053* | |
H3B | 0.6688 | 0.4549 | 0.1690 | 0.053* | |
H3C | 0.5656 | 0.4241 | 0.2021 | 0.053* | |
C4 | 0.54010 (13) | 0.21146 (9) | 0.07572 (9) | 0.0206 (3) | |
C5 | 0.59877 (14) | 0.14499 (9) | 0.09145 (10) | 0.0262 (4) | |
C6 | 0.58773 (16) | 0.09231 (10) | 0.03145 (11) | 0.0320 (4) | |
H6 | 0.6271 | 0.0480 | 0.0425 | 0.038* | |
C7 | 0.52142 (17) | 0.10273 (10) | −0.04331 (11) | 0.0344 (4) | |
H7 | 0.5142 | 0.0658 | −0.0831 | 0.041* | |
C8 | 0.46534 (16) | 0.16769 (10) | −0.05989 (11) | 0.0314 (4) | |
H8 | 0.4201 | 0.1752 | −0.1117 | 0.038* | |
C9 | 0.47367 (14) | 0.22250 (9) | −0.00232 (10) | 0.0234 (3) | |
C10 | 0.67640 (15) | 0.12981 (10) | 0.17153 (11) | 0.0332 (4) | |
H10 | 0.6664 | 0.1693 | 0.2098 | 0.040* | |
C11 | 0.79721 (17) | 0.13112 (14) | 0.16257 (14) | 0.0484 (6) | |
H11A | 0.8093 | 0.0926 | 0.1256 | 0.073* | |
H11B | 0.8458 | 0.1233 | 0.2152 | 0.073* | |
H11C | 0.8138 | 0.1782 | 0.1412 | 0.073* | |
C12 | 0.6529 (2) | 0.05715 (12) | 0.20888 (14) | 0.0507 (6) | |
H12A | 0.5743 | 0.0543 | 0.2108 | 0.076* | |
H12B | 0.6976 | 0.0535 | 0.2636 | 0.076* | |
H12C | 0.6719 | 0.0172 | 0.1761 | 0.076* | |
C13 | 0.41333 (14) | 0.29364 (9) | −0.02586 (10) | 0.0250 (3) | |
H13 | 0.4372 | 0.3286 | 0.0194 | 0.030* | |
C14 | 0.44259 (16) | 0.32680 (10) | −0.10154 (11) | 0.0320 (4) | |
H14A | 0.5232 | 0.3289 | −0.0952 | 0.048* | |
H14B | 0.4119 | 0.3759 | −0.1095 | 0.048* | |
H14C | 0.4114 | 0.2968 | −0.1483 | 0.048* | |
C15 | 0.28797 (15) | 0.28499 (11) | −0.03823 (12) | 0.0358 (4) | |
H15A | 0.2636 | 0.2454 | −0.0763 | 0.054* | |
H15B | 0.2519 | 0.3302 | −0.0598 | 0.054* | |
H15C | 0.2681 | 0.2738 | 0.0134 | 0.054* | |
C16 | 0.1577 (2) | 0.24671 (12) | 0.28396 (17) | 0.0549 (7) | |
H16A | 0.1896 | 0.2029 | 0.2652 | 0.082* | |
H16B | 0.0802 | 0.2377 | 0.2861 | 0.082* | |
H16C | 0.1991 | 0.2595 | 0.3378 | 0.082* | |
C17 | 0.07103 (17) | 0.29789 (14) | 0.11545 (16) | 0.0537 (6) | |
H17A | 0.0639 | 0.3391 | 0.0783 | 0.081* | |
H17B | −0.0020 | 0.2852 | 0.1255 | 0.081* | |
H17C | 0.1017 | 0.2562 | 0.0917 | 0.081* | |
C18 | 0.10410 (17) | 0.40344 (11) | 0.25463 (15) | 0.0445 (5) | |
H18A | 0.1450 | 0.4131 | 0.3095 | 0.067* | |
H18B | 0.0265 | 0.3935 | 0.2555 | 0.067* | |
H18C | 0.1086 | 0.4459 | 0.2207 | 0.067* | |
C19 | 0.34066 (13) | 0.41149 (9) | 0.22280 (10) | 0.0228 (3) | |
C20 | 0.40035 (14) | 0.42735 (10) | 0.30152 (11) | 0.0284 (4) | |
C21 | 0.44440 (15) | 0.49658 (11) | 0.31918 (13) | 0.0359 (4) | |
H21 | 0.4860 | 0.5065 | 0.3716 | 0.043* | |
C22 | 0.42891 (15) | 0.55088 (10) | 0.26230 (14) | 0.0383 (5) | |
H22 | 0.4597 | 0.5976 | 0.2753 | 0.046* | |
C23 | 0.36835 (15) | 0.53671 (9) | 0.18637 (13) | 0.0337 (4) | |
H23 | 0.3566 | 0.5746 | 0.1476 | 0.040* | |
C24 | 0.32364 (13) | 0.46818 (9) | 0.16472 (11) | 0.0270 (4) | |
C25 | 0.42075 (17) | 0.36972 (11) | 0.36707 (11) | 0.0360 (4) | |
H25 | 0.3745 | 0.3268 | 0.3458 | 0.043* | |
C26 | 0.54130 (19) | 0.34483 (14) | 0.38423 (15) | 0.0570 (6) | |
H26A | 0.5603 | 0.3270 | 0.3344 | 0.085* | |
H26B | 0.5515 | 0.3058 | 0.4242 | 0.085* | |
H26C | 0.5894 | 0.3857 | 0.4050 | 0.085* | |
C27 | 0.3860 (3) | 0.39311 (15) | 0.44438 (14) | 0.0678 (8) | |
H27A | 0.4298 | 0.4352 | 0.4672 | 0.102* | |
H27B | 0.3985 | 0.3531 | 0.4832 | 0.102* | |
H27C | 0.3074 | 0.4060 | 0.4324 | 0.102* | |
C28 | 0.25881 (16) | 0.45672 (11) | 0.07964 (12) | 0.0360 (4) | |
H28 | 0.2385 | 0.4042 | 0.0732 | 0.043* | |
C29 | 0.3241 (2) | 0.47660 (12) | 0.01556 (13) | 0.0477 (5) | |
H29A | 0.3441 | 0.5281 | 0.0205 | 0.071* | |
H29B | 0.2786 | 0.4674 | −0.0380 | 0.071* | |
H29C | 0.3914 | 0.4471 | 0.0231 | 0.071* | |
C30 | 0.1517 (2) | 0.50133 (17) | 0.06245 (15) | 0.0643 (7) | |
H30A | 0.1036 | 0.4857 | 0.0985 | 0.096* | |
H30B | 0.1136 | 0.4940 | 0.0064 | 0.096* | |
H30C | 0.1694 | 0.5528 | 0.0715 | 0.096* | |
C31 | 0.4557 (2) | 0.16224 (12) | 0.31084 (15) | 0.0533 (6) | |
H31A | 0.5195 | 0.1783 | 0.2895 | 0.080* | |
H31B | 0.4809 | 0.1307 | 0.3575 | 0.080* | |
H31C | 0.4177 | 0.2045 | 0.3272 | 0.080* | |
C32 | 0.3778 (2) | 0.12119 (11) | 0.24721 (15) | 0.0482 (6) | |
H32A | 0.4143 | 0.0769 | 0.2325 | 0.058* | |
H32B | 0.3116 | 0.1065 | 0.2676 | 0.058* | |
C33 | 0.26193 (17) | 0.13398 (11) | 0.11493 (14) | 0.0425 (5) | |
H33A | 0.2337 | 0.1708 | 0.0733 | 0.051* | |
H33B | 0.1992 | 0.1182 | 0.1389 | 0.051* | |
C34 | 0.3038 (2) | 0.07003 (12) | 0.07545 (16) | 0.0522 (6) | |
H34A | 0.3699 | 0.0841 | 0.0557 | 0.078* | |
H34B | 0.2465 | 0.0535 | 0.0303 | 0.078* | |
H34C | 0.3225 | 0.0307 | 0.1147 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.0174 (2) | 0.0290 (2) | 0.0220 (2) | −0.00193 (18) | 0.00244 (16) | −0.00078 (19) |
Si2 | 0.0276 (3) | 0.0240 (2) | 0.0480 (3) | −0.00492 (19) | 0.0211 (2) | −0.0078 (2) |
Mg1 | 0.0240 (3) | 0.0185 (3) | 0.0266 (3) | −0.0001 (2) | 0.0111 (2) | 0.0006 (2) |
O1 | 0.0449 (8) | 0.0196 (6) | 0.0553 (9) | −0.0020 (6) | 0.0268 (7) | 0.0023 (6) |
N1 | 0.0194 (6) | 0.0222 (7) | 0.0187 (6) | 0.0010 (5) | 0.0038 (5) | 0.0001 (5) |
N2 | 0.0238 (7) | 0.0180 (7) | 0.0297 (7) | −0.0022 (5) | 0.0123 (6) | −0.0024 (5) |
C1 | 0.0270 (9) | 0.0579 (13) | 0.0307 (10) | −0.0054 (9) | −0.0038 (8) | 0.0021 (9) |
C2 | 0.0253 (9) | 0.0364 (10) | 0.0343 (9) | −0.0033 (8) | 0.0111 (7) | 0.0014 (8) |
C3 | 0.0286 (9) | 0.0313 (10) | 0.0470 (11) | −0.0068 (8) | 0.0114 (8) | −0.0085 (8) |
C4 | 0.0197 (7) | 0.0222 (8) | 0.0213 (8) | 0.0000 (6) | 0.0076 (6) | 0.0020 (6) |
C5 | 0.0261 (8) | 0.0258 (8) | 0.0283 (9) | 0.0048 (7) | 0.0090 (7) | 0.0034 (7) |
C6 | 0.0379 (10) | 0.0245 (9) | 0.0361 (10) | 0.0100 (7) | 0.0134 (8) | 0.0016 (7) |
C7 | 0.0462 (11) | 0.0275 (9) | 0.0314 (10) | 0.0016 (8) | 0.0123 (8) | −0.0075 (7) |
C8 | 0.0406 (10) | 0.0283 (9) | 0.0235 (8) | −0.0005 (8) | 0.0023 (7) | −0.0027 (7) |
C9 | 0.0266 (8) | 0.0230 (8) | 0.0206 (8) | −0.0001 (6) | 0.0052 (6) | 0.0014 (6) |
C10 | 0.0331 (9) | 0.0354 (10) | 0.0303 (9) | 0.0145 (8) | 0.0047 (7) | 0.0051 (8) |
C11 | 0.0330 (11) | 0.0637 (15) | 0.0459 (12) | 0.0202 (10) | 0.0018 (9) | 0.0019 (11) |
C12 | 0.0659 (15) | 0.0440 (12) | 0.0427 (12) | 0.0208 (11) | 0.0122 (11) | 0.0166 (10) |
C13 | 0.0292 (9) | 0.0241 (8) | 0.0196 (8) | 0.0014 (7) | 0.0001 (6) | 0.0004 (6) |
C14 | 0.0359 (10) | 0.0306 (9) | 0.0295 (9) | 0.0011 (8) | 0.0066 (7) | 0.0074 (8) |
C15 | 0.0316 (10) | 0.0395 (11) | 0.0381 (10) | 0.0058 (8) | 0.0110 (8) | 0.0037 (8) |
C16 | 0.0551 (14) | 0.0354 (11) | 0.0879 (19) | −0.0060 (10) | 0.0465 (14) | 0.0065 (12) |
C17 | 0.0257 (10) | 0.0609 (15) | 0.0756 (17) | −0.0082 (10) | 0.0131 (10) | −0.0282 (13) |
C18 | 0.0394 (11) | 0.0349 (11) | 0.0691 (15) | −0.0018 (9) | 0.0341 (11) | −0.0117 (10) |
C19 | 0.0196 (8) | 0.0192 (8) | 0.0319 (9) | 0.0011 (6) | 0.0105 (7) | −0.0025 (7) |
C20 | 0.0245 (8) | 0.0289 (9) | 0.0330 (9) | 0.0039 (7) | 0.0089 (7) | −0.0052 (7) |
C21 | 0.0258 (9) | 0.0363 (10) | 0.0450 (11) | −0.0010 (8) | 0.0056 (8) | −0.0168 (9) |
C22 | 0.0270 (9) | 0.0230 (9) | 0.0674 (14) | −0.0050 (7) | 0.0152 (9) | −0.0131 (9) |
C23 | 0.0298 (9) | 0.0212 (8) | 0.0550 (12) | 0.0009 (7) | 0.0197 (9) | 0.0039 (8) |
C24 | 0.0220 (8) | 0.0242 (8) | 0.0375 (10) | 0.0015 (6) | 0.0122 (7) | 0.0015 (7) |
C25 | 0.0397 (10) | 0.0400 (11) | 0.0277 (9) | 0.0088 (9) | 0.0059 (8) | −0.0021 (8) |
C26 | 0.0443 (13) | 0.0660 (16) | 0.0563 (15) | 0.0173 (11) | 0.0003 (11) | 0.0095 (12) |
C27 | 0.102 (2) | 0.0679 (18) | 0.0389 (13) | 0.0253 (16) | 0.0280 (14) | 0.0030 (12) |
C28 | 0.0393 (11) | 0.0349 (10) | 0.0340 (10) | 0.0009 (8) | 0.0081 (8) | 0.0068 (8) |
C29 | 0.0628 (14) | 0.0402 (12) | 0.0441 (12) | 0.0127 (10) | 0.0207 (11) | 0.0109 (9) |
C30 | 0.0478 (14) | 0.094 (2) | 0.0480 (14) | 0.0208 (14) | 0.0016 (11) | 0.0118 (14) |
C31 | 0.0691 (16) | 0.0385 (12) | 0.0570 (15) | 0.0028 (11) | 0.0239 (12) | 0.0104 (11) |
C32 | 0.0551 (13) | 0.0269 (10) | 0.0693 (16) | 0.0039 (9) | 0.0281 (12) | 0.0132 (10) |
C33 | 0.0427 (11) | 0.0275 (10) | 0.0629 (14) | −0.0056 (9) | 0.0238 (10) | −0.0014 (9) |
C34 | 0.0606 (15) | 0.0333 (12) | 0.0675 (16) | −0.0038 (10) | 0.0241 (12) | −0.0085 (11) |
Si1—N1 | 1.7206 (14) | C15—H15B | 0.9800 |
Si1—C3 | 1.8650 (19) | C15—H15C | 0.9800 |
Si1—C2 | 1.8794 (18) | C16—H16A | 0.9800 |
Si1—C1 | 1.8796 (19) | C16—H16B | 0.9800 |
Si2—N2 | 1.7236 (14) | C16—H16C | 0.9800 |
Si2—C16 | 1.869 (2) | C17—H17A | 0.9800 |
Si2—C18 | 1.8705 (19) | C17—H17B | 0.9800 |
Si2—C17 | 1.878 (2) | C17—H17C | 0.9800 |
Mg1—N1 | 1.9761 (14) | C18—H18A | 0.9800 |
Mg1—N2 | 1.9789 (14) | C18—H18B | 0.9800 |
Mg1—O1 | 2.0361 (13) | C18—H18C | 0.9800 |
Mg1—C4 | 2.7988 (16) | C19—C20 | 1.418 (2) |
O1—C32 | 1.447 (3) | C19—C24 | 1.423 (2) |
O1—C33 | 1.455 (3) | C20—C21 | 1.396 (3) |
N1—C4 | 1.432 (2) | C20—C25 | 1.522 (3) |
N2—C19 | 1.429 (2) | C21—C22 | 1.377 (3) |
C1—H1A | 0.9800 | C21—H21 | 0.9500 |
C1—H1B | 0.9800 | C22—C23 | 1.376 (3) |
C1—H1C | 0.9800 | C22—H22 | 0.9500 |
C2—H2A | 0.9800 | C23—C24 | 1.398 (2) |
C2—H2B | 0.9800 | C23—H23 | 0.9500 |
C2—H2C | 0.9800 | C24—C28 | 1.516 (3) |
C3—H3A | 0.9800 | C25—C27 | 1.526 (3) |
C3—H3B | 0.9800 | C25—C26 | 1.528 (3) |
C3—H3C | 0.9800 | C25—H25 | 1.0000 |
C4—C5 | 1.421 (2) | C26—H26A | 0.9800 |
C4—C9 | 1.423 (2) | C26—H26B | 0.9800 |
C5—C6 | 1.394 (2) | C26—H26C | 0.9800 |
C5—C10 | 1.520 (2) | C27—H27A | 0.9800 |
C6—C7 | 1.375 (3) | C27—H27B | 0.9800 |
C6—H6 | 0.9500 | C27—H27C | 0.9800 |
C7—C8 | 1.384 (3) | C28—C29 | 1.527 (3) |
C7—H7 | 0.9500 | C28—C30 | 1.535 (3) |
C8—C9 | 1.395 (2) | C28—H28 | 1.0000 |
C8—H8 | 0.9500 | C29—H29A | 0.9800 |
C9—C13 | 1.521 (2) | C29—H29B | 0.9800 |
C10—C11 | 1.532 (3) | C29—H29C | 0.9800 |
C10—C12 | 1.536 (3) | C30—H30A | 0.9800 |
C10—H10 | 1.0000 | C30—H30B | 0.9800 |
C11—H11A | 0.9800 | C30—H30C | 0.9800 |
C11—H11B | 0.9800 | C31—C32 | 1.497 (3) |
C11—H11C | 0.9800 | C31—H31A | 0.9800 |
C12—H12A | 0.9800 | C31—H31B | 0.9800 |
C12—H12B | 0.9800 | C31—H31C | 0.9800 |
C12—H12C | 0.9800 | C32—H32A | 0.9900 |
C13—C15 | 1.528 (2) | C32—H32B | 0.9900 |
C13—C14 | 1.533 (2) | C33—C34 | 1.501 (3) |
C13—H13 | 1.0000 | C33—H33A | 0.9900 |
C14—H14A | 0.9800 | C33—H33B | 0.9900 |
C14—H14B | 0.9800 | C34—H34A | 0.9800 |
C14—H14C | 0.9800 | C34—H34B | 0.9800 |
C15—H15A | 0.9800 | C34—H34C | 0.9800 |
N1—Si1—C3 | 111.21 (7) | Si2—C16—H16A | 109.5 |
N1—Si1—C2 | 111.01 (7) | Si2—C16—H16B | 109.5 |
C3—Si1—C2 | 109.04 (9) | H16A—C16—H16B | 109.5 |
N1—Si1—C1 | 114.60 (8) | Si2—C16—H16C | 109.5 |
C3—Si1—C1 | 103.98 (10) | H16A—C16—H16C | 109.5 |
C2—Si1—C1 | 106.62 (9) | H16B—C16—H16C | 109.5 |
N2—Si2—C16 | 112.37 (9) | Si2—C17—H17A | 109.5 |
N2—Si2—C18 | 111.49 (8) | Si2—C17—H17B | 109.5 |
C16—Si2—C18 | 105.88 (10) | H17A—C17—H17B | 109.5 |
N2—Si2—C17 | 113.03 (9) | Si2—C17—H17C | 109.5 |
C16—Si2—C17 | 106.06 (12) | H17A—C17—H17C | 109.5 |
C18—Si2—C17 | 107.56 (11) | H17B—C17—H17C | 109.5 |
N1—Mg1—N2 | 140.69 (6) | Si2—C18—H18A | 109.5 |
N1—Mg1—O1 | 109.54 (6) | Si2—C18—H18B | 109.5 |
N2—Mg1—O1 | 109.63 (6) | H18A—C18—H18B | 109.5 |
C32—O1—C33 | 112.54 (15) | Si2—C18—H18C | 109.5 |
C32—O1—Mg1 | 122.07 (13) | H18A—C18—H18C | 109.5 |
C33—O1—Mg1 | 125.25 (12) | H18B—C18—H18C | 109.5 |
C4—N1—Si1 | 117.98 (10) | C20—C19—C24 | 118.42 (15) |
C4—N1—Mg1 | 109.37 (10) | C20—C19—N2 | 120.40 (15) |
Si1—N1—Mg1 | 131.15 (8) | C24—C19—N2 | 121.18 (15) |
C19—N2—Si2 | 116.59 (10) | C21—C20—C19 | 119.69 (17) |
C19—N2—Mg1 | 116.07 (10) | C21—C20—C25 | 118.87 (17) |
Si2—N2—Mg1 | 127.20 (8) | C19—C20—C25 | 121.41 (16) |
Si1—C1—H1A | 109.5 | C22—C21—C20 | 121.50 (18) |
Si1—C1—H1B | 109.5 | C22—C21—H21 | 119.2 |
H1A—C1—H1B | 109.5 | C20—C21—H21 | 119.2 |
Si1—C1—H1C | 109.5 | C23—C22—C21 | 119.31 (17) |
H1A—C1—H1C | 109.5 | C23—C22—H22 | 120.3 |
H1B—C1—H1C | 109.5 | C21—C22—H22 | 120.3 |
Si1—C2—H2A | 109.5 | C22—C23—C24 | 121.82 (18) |
Si1—C2—H2B | 109.5 | C22—C23—H23 | 119.1 |
H2A—C2—H2B | 109.5 | C24—C23—H23 | 119.1 |
Si1—C2—H2C | 109.5 | C23—C24—C19 | 119.21 (17) |
H2A—C2—H2C | 109.5 | C23—C24—C28 | 118.64 (16) |
H2B—C2—H2C | 109.5 | C19—C24—C28 | 122.15 (15) |
Si1—C3—H3A | 109.5 | C20—C25—C27 | 113.49 (17) |
Si1—C3—H3B | 109.5 | C20—C25—C26 | 110.92 (17) |
H3A—C3—H3B | 109.5 | C27—C25—C26 | 110.9 (2) |
Si1—C3—H3C | 109.5 | C20—C25—H25 | 107.0 |
H3A—C3—H3C | 109.5 | C27—C25—H25 | 107.0 |
H3B—C3—H3C | 109.5 | C26—C25—H25 | 107.0 |
C5—C4—C9 | 118.21 (15) | C25—C26—H26A | 109.5 |
C5—C4—N1 | 122.13 (14) | C25—C26—H26B | 109.5 |
C9—C4—N1 | 119.66 (14) | H26A—C26—H26B | 109.5 |
C6—C5—C4 | 119.64 (16) | C25—C26—H26C | 109.5 |
C6—C5—C10 | 118.32 (15) | H26A—C26—H26C | 109.5 |
C4—C5—C10 | 122.03 (15) | H26B—C26—H26C | 109.5 |
C7—C6—C5 | 121.83 (17) | C25—C27—H27A | 109.5 |
C7—C6—H6 | 119.1 | C25—C27—H27B | 109.5 |
C5—C6—H6 | 119.1 | H27A—C27—H27B | 109.5 |
C6—C7—C8 | 119.14 (17) | C25—C27—H27C | 109.5 |
C6—C7—H7 | 120.4 | H27A—C27—H27C | 109.5 |
C8—C7—H7 | 120.4 | H27B—C27—H27C | 109.5 |
C7—C8—C9 | 121.55 (17) | C24—C28—C29 | 113.13 (17) |
C7—C8—H8 | 119.2 | C24—C28—C30 | 111.86 (17) |
C9—C8—H8 | 119.2 | C29—C28—C30 | 107.31 (17) |
C8—C9—C4 | 119.62 (15) | C24—C28—H28 | 108.1 |
C8—C9—C13 | 118.64 (15) | C29—C28—H28 | 108.1 |
C4—C9—C13 | 121.72 (14) | C30—C28—H28 | 108.1 |
C5—C10—C11 | 110.88 (16) | C28—C29—H29A | 109.5 |
C5—C10—C12 | 113.09 (17) | C28—C29—H29B | 109.5 |
C11—C10—C12 | 109.01 (17) | H29A—C29—H29B | 109.5 |
C5—C10—H10 | 107.9 | C28—C29—H29C | 109.5 |
C11—C10—H10 | 107.9 | H29A—C29—H29C | 109.5 |
C12—C10—H10 | 107.9 | H29B—C29—H29C | 109.5 |
C10—C11—H11A | 109.5 | C28—C30—H30A | 109.5 |
C10—C11—H11B | 109.5 | C28—C30—H30B | 109.5 |
H11A—C11—H11B | 109.5 | H30A—C30—H30B | 109.5 |
C10—C11—H11C | 109.5 | C28—C30—H30C | 109.5 |
H11A—C11—H11C | 109.5 | H30A—C30—H30C | 109.5 |
H11B—C11—H11C | 109.5 | H30B—C30—H30C | 109.5 |
C10—C12—H12A | 109.5 | C32—C31—H31A | 109.5 |
C10—C12—H12B | 109.5 | C32—C31—H31B | 109.5 |
H12A—C12—H12B | 109.5 | H31A—C31—H31B | 109.5 |
C10—C12—H12C | 109.5 | C32—C31—H31C | 109.5 |
H12A—C12—H12C | 109.5 | H31A—C31—H31C | 109.5 |
H12B—C12—H12C | 109.5 | H31B—C31—H31C | 109.5 |
C9—C13—C15 | 111.98 (14) | O1—C32—C31 | 108.79 (17) |
C9—C13—C14 | 112.13 (14) | O1—C32—H32A | 109.9 |
C15—C13—C14 | 109.52 (14) | C31—C32—H32A | 109.9 |
C9—C13—H13 | 107.7 | O1—C32—H32B | 109.9 |
C15—C13—H13 | 107.7 | C31—C32—H32B | 109.9 |
C14—C13—H13 | 107.7 | H32A—C32—H32B | 108.3 |
C13—C14—H14A | 109.5 | O1—C33—C34 | 113.49 (18) |
C13—C14—H14B | 109.5 | O1—C33—H33A | 108.9 |
H14A—C14—H14B | 109.5 | C34—C33—H33A | 108.9 |
C13—C14—H14C | 109.5 | O1—C33—H33B | 108.9 |
H14A—C14—H14C | 109.5 | C34—C33—H33B | 108.9 |
H14B—C14—H14C | 109.5 | H33A—C33—H33B | 107.7 |
C13—C15—H15A | 109.5 | C33—C34—H34A | 109.5 |
C13—C15—H15B | 109.5 | C33—C34—H34B | 109.5 |
H15A—C15—H15B | 109.5 | H34A—C34—H34B | 109.5 |
C13—C15—H15C | 109.5 | C33—C34—H34C | 109.5 |
H15A—C15—H15C | 109.5 | H34A—C34—H34C | 109.5 |
H15B—C15—H15C | 109.5 | H34B—C34—H34C | 109.5 |
N1—Mg1—O1—C32 | 87.27 (14) | C10—C5—C6—C7 | −178.26 (17) |
N2—Mg1—O1—C32 | −96.17 (14) | C5—C6—C7—C8 | 1.0 (3) |
C4—Mg1—O1—C32 | 103.92 (14) | C6—C7—C8—C9 | −0.6 (3) |
N1—Mg1—O1—C33 | −97.29 (14) | C7—C8—C9—C4 | −0.8 (3) |
N2—Mg1—O1—C33 | 79.28 (14) | C7—C8—C9—C13 | 177.58 (17) |
C4—Mg1—O1—C33 | −80.63 (14) | C5—C4—C9—C8 | 1.9 (2) |
C3—Si1—N1—C4 | 136.36 (12) | N1—C4—C9—C8 | −178.15 (15) |
C2—Si1—N1—C4 | 14.77 (14) | Mg1—C4—C9—C8 | −137.64 (14) |
C1—Si1—N1—C4 | −106.08 (13) | C5—C4—C9—C13 | −176.46 (15) |
C3—Si1—N1—Mg1 | −28.00 (13) | N1—C4—C9—C13 | 3.5 (2) |
C2—Si1—N1—Mg1 | −149.59 (10) | Mg1—C4—C9—C13 | 44.03 (16) |
C1—Si1—N1—Mg1 | 89.56 (12) | C6—C5—C10—C11 | 70.1 (2) |
N2—Mg1—N1—C4 | −138.58 (11) | C4—C5—C10—C11 | −108.30 (19) |
O1—Mg1—N1—C4 | 36.30 (12) | C6—C5—C10—C12 | −52.7 (2) |
N2—Mg1—N1—Si1 | 26.80 (16) | C4—C5—C10—C12 | 128.91 (18) |
O1—Mg1—N1—Si1 | −158.31 (9) | C8—C9—C13—C15 | 70.1 (2) |
C4—Mg1—N1—Si1 | 165.38 (17) | C4—C9—C13—C15 | −111.60 (18) |
C16—Si2—N2—C19 | −121.69 (14) | C8—C9—C13—C14 | −53.5 (2) |
C18—Si2—N2—C19 | −3.00 (16) | C4—C9—C13—C14 | 124.82 (16) |
C17—Si2—N2—C19 | 118.30 (14) | Si2—N2—C19—C20 | 92.90 (16) |
C16—Si2—N2—Mg1 | 53.70 (14) | Mg1—N2—C19—C20 | −83.02 (16) |
C18—Si2—N2—Mg1 | 172.39 (11) | Si2—N2—C19—C24 | −87.29 (17) |
C17—Si2—N2—Mg1 | −66.31 (14) | Mg1—N2—C19—C24 | 96.79 (15) |
N1—Mg1—N2—C19 | −20.50 (17) | C24—C19—C20—C21 | −2.6 (2) |
O1—Mg1—N2—C19 | 164.61 (11) | N2—C19—C20—C21 | 177.25 (15) |
C4—Mg1—N2—C19 | −69.80 (19) | C24—C19—C20—C25 | 179.33 (15) |
N1—Mg1—N2—Si2 | 164.09 (8) | N2—C19—C20—C25 | −0.9 (2) |
O1—Mg1—N2—Si2 | −10.80 (12) | C19—C20—C21—C22 | 1.7 (3) |
C4—Mg1—N2—Si2 | 114.79 (13) | C25—C20—C21—C22 | 179.86 (16) |
Si1—N1—C4—C5 | 85.29 (17) | C20—C21—C22—C23 | 0.2 (3) |
Mg1—N1—C4—C5 | −107.13 (15) | C21—C22—C23—C24 | −1.2 (3) |
Si1—N1—C4—C9 | −94.69 (15) | C22—C23—C24—C19 | 0.3 (3) |
Mg1—N1—C4—C9 | 72.89 (15) | C22—C23—C24—C28 | −179.44 (16) |
Si1—N1—C4—Mg1 | −167.57 (15) | C20—C19—C24—C23 | 1.6 (2) |
N1—Mg1—C4—C5 | 101.75 (17) | N2—C19—C24—C23 | −178.22 (14) |
N2—Mg1—C4—C5 | −174.05 (14) | C20—C19—C24—C28 | −178.68 (15) |
O1—Mg1—C4—C5 | −44.23 (14) | N2—C19—C24—C28 | 1.5 (2) |
N1—Mg1—C4—C9 | −122.07 (15) | C21—C20—C25—C27 | 54.2 (3) |
N2—Mg1—C4—C9 | −37.87 (19) | C19—C20—C25—C27 | −127.6 (2) |
O1—Mg1—C4—C9 | 91.95 (11) | C21—C20—C25—C26 | −71.4 (2) |
N2—Mg1—C4—N1 | 84.20 (17) | C19—C20—C25—C26 | 106.7 (2) |
O1—Mg1—C4—N1 | −145.98 (11) | C23—C24—C28—C29 | 55.6 (2) |
C9—C4—C5—C6 | −1.6 (2) | C19—C24—C28—C29 | −124.15 (18) |
N1—C4—C5—C6 | 178.46 (15) | C23—C24—C28—C30 | −65.8 (2) |
Mg1—C4—C5—C6 | 128.09 (15) | C19—C24—C28—C30 | 114.5 (2) |
C9—C4—C5—C10 | 176.80 (15) | C33—O1—C32—C31 | −174.87 (17) |
N1—C4—C5—C10 | −3.2 (2) | Mg1—O1—C32—C31 | 1.1 (2) |
Mg1—C4—C5—C10 | −53.6 (2) | C32—O1—C33—C34 | −68.5 (2) |
C4—C5—C6—C7 | 0.2 (3) | Mg1—O1—C33—C34 | 115.67 (17) |
Experimental details
Crystal data | |
Chemical formula | [Mg(C4H10O)(C15H26NSi)2] |
Mr | 595.35 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 123 |
a, b, c (Å) | 12.359 (2), 18.443 (3), 16.984 (2) |
β (°) | 101.900 (14) |
V (Å3) | 3788.1 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.55 × 0.30 × 0.15 |
Data collection | |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9082, 8689, 5523 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.116, 1.00 |
No. of reflections | 8689 |
No. of parameters | 377 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.44, −0.20 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1992), SIR (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Mg1—N1 | 1.9761 (14) | Mg1—O1 | 2.0361 (13) |
Mg1—N2 | 1.9789 (14) | ||
N1—Mg1—N2 | 140.69 (6) | Si1—N1—Mg1 | 131.15 (8) |
N1—Mg1—O1 | 109.54 (6) | C19—N2—Si2 | 116.59 (10) |
N2—Mg1—O1 | 109.63 (6) | C19—N2—Mg1 | 116.07 (10) |
C4—N1—Si1 | 117.98 (10) | Si2—N2—Mg1 | 127.20 (8) |
C4—N1—Mg1 | 109.37 (10) | ||
N1—Mg1—O1—C32 | 87.27 (14) | O1—Mg1—N1—C4 | 36.30 (12) |
N2—Mg1—O1—C32 | −96.17 (14) | N1—Mg1—N2—C19 | −20.50 (17) |
N2—Mg1—N1—C4 | −138.58 (11) | O1—Mg1—N2—C19 | 164.61 (11) |
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Magnesium bis(amides) are typically isolated as tetrahedrally coordinated compounds of the type [MgL2S2], where L is an amide ligand and S a donating solvent, or as dimeric species of the type [LSxMg(µL)2MgLSx] (x = 0 or 1), where Mg is in either a trigonal-planar or a tetrahedral environment [for typical examples, see Sebestl et al. (1998) and Clegg et al. (1997)]. Lower coordination numbers are favoured by sterically demanding amide groups. Indeed, it has been shown that where L is [(Me3Si)2N], HMDS *Is this bis(trimethylsilyl), which would, in principle, give hexamethyldisilyl? Should it have amido, as in the original Sebestl reference?* or [(PhCH2)2N], monomers of the type MgL2 are present in solution (Henderson et al., 1997; Clegg et al., 1997). In an attempt to isolate, in the solid state, such coordinatively unsaturated species, we turned to the sterically hindered amide [(Me3Si)(2,6-iPr2C6H3)N], A. This ligand is known to stabilize low coordination number complexes in d-block chemistry (Chao et al., 1989; Kennepohl et al., 1992), including ZnA2 (Schumann et al., 2000). This last example is of particular relevance, as many Mg and Zn amides are isostructural (Forbes et al., 2000). To our knowledge, the use of this ligand in s-block chemistry has been limited to lithium chemistry, where it has allowed the structural characterization of the first non-solvated [Li(µ-L)2Li] dimer (Kennepohl et al., 1991) and of the unusual three-coordinate monomeric species [LiA(Et2O)(C5H5N)] (Blake et al., 1996). Reaction of [(Me3Si)(2,6-iPr2C6H3)NH] with dibutylmagnesium formed a colourless compound which was identified as the title compound, (I), by single-crystal diffraction. These results are presented here. \sch
The crystal structure of (I) consists of discrete monomers separated by at least the sum of van der Waal's radii. Unusually, the Mg atom is three-coordinate, bonding to two amide units and a diethyl ether molecule in a planar manner [Mg1 lies 0.042 (1) Å from the N1/N2/O1 plane]. Although this coordination geometry is common in dimeric (Clegg et al., 1997) and polymeric (Andrews et al., 2000) magnesium amide solid-state structures, a search of the Cambridge Structural Database (version 5.21; Allen & Kennard, 1993) revealed only [Mg(HMDS)2S], (II), (S = 2-picoline or 2,6-lutidine; Sebestl et al., 1998) and the chelate [MgtBu{(N,N-(2,6-iPr2C6H3)NC(Me)CHC(Me)N(2,6-iPr2C6H3)}] (Gibson et al., 2000), with similar three-coordinate monomeric structures. An illustration of the coordinatively unsaturated nature of these species is that, unlike (I), (II) is not isolated in the presence of solvent. Indeed, dissolution of (II) in any suitable solvent gives only [Mg(HMDS)2S2] as an isolatable product. Some relief from coordinative unsaturation is perhaps gained from the short Mg1···C4 interaction [2.799 (2) Å, compared with 2.399–2.443 Å for Mg—C distances in Mg—Cp; Lehmkuhl et al., 1986]. This interaction is accompanied by the compression of the bond angle at N1 compared with that in the second A moiety [Mg1—N1—C4 109.37 (10) and Mg1—N2—C19 116.07 (10)°, and Mg1···C19 2.906 (2) Å]. A similar short contact was observed in [LiA(Et2O)(C5H5N)] (Blake et al., 1996).
The environment of atom N1 is less planar than that of N2 [N-atom deviations from planarity are 0.119 (2) and 0.037 (2) Å, respectively]. The Mg—N bond lengths are similar to each other (Table 1), and to those found in (II) and in the non-bridging bonds of [(HMDS)Mg(µ-HMDS)2Mg(HMDS)] (Westerhausen & Schwarz, 1992) *The first and third bis(trimethylsilyl) ligands in this ref are amino rather than amido. How do you wish to indicate this?*. They are, however, approximately 0.05–0.06 Å shorter than the typical distances observed in the tetrahedral species [Mg(HMDS)2S2] (Sebestl et al., 1998; Forbes et al., 2001 *Is this azido, as used in their 2000 work? Either way, please specify how you wish to indicate the exact nature of the ligand*). The N1—Mg1—N2 angle of 140.69 (6)° shows considerable widening to accommodate the two A ligands. The planes of the two aryl rings and of the ether ligand lie approximately perpendicular to the N1/N2/O1 plane [85.92 (5), 88.83 (5) and 83.35 (7)° for the angles to the planes defined by C4—C9, C19—C24 and O1/C32/C33, respectively] so as to minimize steric interactions. Similarly, the two aryl rings are mutually anti with respect to the coordination plane and the improper torsion angle C4—N1—N2—C19 is -150.1 (3)°.
Please adopt a nomenclature which distinguishes adequately between HMDS-amido, HMDS-amino and HMDS-azido [or whatever was used in the Forbes et al. (2001) work]. HMDS alone may not be used to indicate a variety of similar ligands - specific details are required for each point of difference, for accuracy and rigour.