Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100001281/fr1246sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100001281/fr1246Isup2.hkl |
CCDC reference: 145520
To a stirred solution of (2-naphthylmethyloxy)acetonitrile (0.036 g, 0.18 mmol) in anhydrous toluene (2 ml) at 273 K was added methylmagnesium bromide (2.96 M in ether, 0.065 ml, 0.19 mmol). The solution was slowly warmed to room temperature and stirred until the disappearance of the starting material as indicated by thi-layer chromatography. The white suspension was then solubilized by the addition of anhydrous tetrahydrofuran (5 ml). The complex (I) was crystallized under argon in a glove box at 258 K for one month. Due to moisture sensitivity of the ketiminate, the crystal was placed under a flow of nitrogen (T = 220 K) during the data collection.
The decay correction was linear. Hydrogen atoms constrained to the parent site using a riding model; SHELXL96 defaults, C—H 0.94 to 0.98 Å. A torsional parameter was refined for the methyl group C3. The isotropic factors, Uiso, were adjusted to 50% higher value of the parent site (methyl) and 20% higher (others). THe toluene solvent was modeled as disordered with two orientations of populations 0.891 (7) and 0.109 (7), related by an in-plane rotation of approximately 120%. Solvent was refined anisotropically using restraints (SAME/ISOR/SIMU/DELU). A final verification of possible voids was performed using the VOID routine of the PLATON program (Spek, 1995).
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: NRC-2, NRC-2A (Ahmed et al., 1973); program(s) used to solve structure: SHELXS96 (Sheldrick, 1990); program(s) used to refine structure: NRCVAX (Gabe et al., 1989) and SHELXL96 (Sheldrick, 1996); molecular graphics: ORTEPII (Johnson, 1976) in NRCVAX (Gabe et al., 1989); software used to prepare material for publication: NRCVAX (Gabe et al., 1989) and SHELXL96 (Sheldrick, 1996).
Fig. 1. ORTEPII (Johnson, 1976) drawing of the molecule eith 40% ellipsoids. The disordered solvanet is not illustrated. |
[Mg2(C14H14NO)2(C4H8O)4Br2]·2C7H8 | F(000) = 2320.0 |
Mr = 1105.6 | Dx = 1.323 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54056 Å |
a = 23.12 (2) Å | Cell parameters from 25 reflections |
b = 12.566 (9) Å | θ = 20.0–22.0° |
c = 19.142 (10) Å | µ = 2.47 mm−1 |
β = 93.32 (7)° | T = 220 K |
V = 5552 (7) Å3 | Block, clear light yellow |
Z = 4 | 0.27 × 0.15 × 0.14 mm |
Nonius CAD-4 with gas-stream cryostat diffractometer | 2611 reflections with I > 2σ(I) |
Radiation source: normal-focus xray tube | Rint = 0.096 |
Graphite monochromator | θmax = 69.9°, θmin = 3.8° |
ω/2θ scan | h = −28→28 |
Absorption correction: integration ABSORP in NRCVAX (Gabe et al., 1989) | k = −15→15 |
Tmin = 0.594, Tmax = 0.771 | l = −23→23 |
15403 measured reflections | 5 standard reflections every 60 min |
5238 independent reflections | intensity decay: 20.3% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.077 | w = 1/[σ2(Fo2) + (0.0212P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.78 | (Δ/σ)max = 0.001 |
5238 reflections | Δρmax = 0.72 e Å−3 |
384 parameters | Δρmin = −0.27 e Å−3 |
297 restraints | Extinction correction: SHELXL96 (Sheldrick, 1996), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.000029 (8) |
[Mg2(C14H14NO)2(C4H8O)4Br2]·2C7H8 | V = 5552 (7) Å3 |
Mr = 1105.6 | Z = 4 |
Monoclinic, C2/c | Cu Kα radiation |
a = 23.12 (2) Å | µ = 2.47 mm−1 |
b = 12.566 (9) Å | T = 220 K |
c = 19.142 (10) Å | 0.27 × 0.15 × 0.14 mm |
β = 93.32 (7)° |
Nonius CAD-4 with gas-stream cryostat diffractometer | 2611 reflections with I > 2σ(I) |
Absorption correction: integration ABSORP in NRCVAX (Gabe et al., 1989) | Rint = 0.096 |
Tmin = 0.594, Tmax = 0.771 | 5 standard reflections every 60 min |
15403 measured reflections | intensity decay: 20.3% |
5238 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 297 restraints |
wR(F2) = 0.077 | H-atom parameters constrained |
S = 0.78 | Δρmax = 0.72 e Å−3 |
5238 reflections | Δρmin = −0.27 e Å−3 |
384 parameters |
Experimental. A crystal of the compound was attached to a glass fiber and transferred rapidly under a cold stream of nitrogen to a Nonius CAD-4 system equipped with a low temperature gas-stream cryostat for data collection at 220 (2) K. Space group confirmed by PLATON program (Spek, 1995). Data reduction performed using a locally modified version of the NRC-2 program (Ahmed et al., 1973). The structure was solved by direct method using SHELXS96 (Sheldrick, 1990) and difmap synthesis using NRCVAX (Gabe et al. (1989) and SHELXL96 (Sheldrick, 1996). All non-hydrogen atoms anisotropic, hydrogen atoms isotropic. |
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. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R-factor_obs 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 | Occ. (<1) | |
Br | 0.476522 (19) | 0.24799 (4) | 0.03476 (2) | 0.04327 (13) | |
Mg | 0.51258 (5) | 0.26637 (10) | 0.17051 (6) | 0.0268 (3) | |
O | 0.60560 (10) | 0.2654 (2) | 0.14575 (12) | 0.0343 (6) | |
N | 0.55995 (13) | 0.2706 (2) | 0.26922 (14) | 0.0270 (7) | |
C1 | 0.64631 (16) | 0.2749 (3) | 0.20501 (19) | 0.0393 (11) | |
H1A | 0.6682 | 0.3414 | 0.2021 | 0.047* | |
H1B | 0.6737 | 0.2154 | 0.2058 | 0.047* | |
C2 | 0.61264 (17) | 0.2742 (3) | 0.27128 (18) | 0.0304 (9) | |
C3 | 0.65322 (17) | 0.2807 (3) | 0.3368 (2) | 0.0508 (13) | |
H3A | 0.6747 | 0.3470 | 0.3367 | 0.076* | |
H3B | 0.6801 | 0.2213 | 0.3376 | 0.076* | |
H3C | 0.6307 | 0.2778 | 0.3780 | 0.076* | |
C4 | 0.63271 (16) | 0.2473 (3) | 0.08056 (17) | 0.0399 (9) | |
H4A | 0.6029 | 0.2267 | 0.0446 | 0.048* | |
H4B | 0.6601 | 0.1881 | 0.0867 | 0.048* | |
C5 | 0.66437 (18) | 0.3434 (3) | 0.0556 (2) | 0.0361 (10) | |
C6 | 0.63239 (18) | 0.4317 (3) | 0.0306 (2) | 0.0416 (11) | |
H6 | 0.5917 | 0.4298 | 0.0297 | 0.050* | |
C7 | 0.6597 (2) | 0.5212 (4) | 0.0074 (2) | 0.0460 (12) | |
H7 | 0.6376 | 0.5800 | −0.0088 | 0.055* | |
C8 | 0.72094 (18) | 0.5250 (3) | 0.0078 (2) | 0.0399 (10) | |
C9 | 0.7509 (2) | 0.6146 (4) | −0.0161 (2) | 0.0549 (14) | |
H9 | 0.7299 | 0.6733 | −0.0344 | 0.066* | |
C10 | 0.8105 (2) | 0.6166 (4) | −0.0130 (2) | 0.0612 (14) | |
H10 | 0.8298 | 0.6773 | −0.0284 | 0.073* | |
C11 | 0.8425 (2) | 0.5305 (4) | 0.0126 (2) | 0.0543 (14) | |
H11 | 0.8832 | 0.5332 | 0.0145 | 0.065* | |
C12 | 0.81522 (19) | 0.4415 (4) | 0.0351 (2) | 0.0490 (12) | |
H12 | 0.8373 | 0.3830 | 0.0517 | 0.059* | |
C13 | 0.75354 (18) | 0.4365 (4) | 0.0337 (2) | 0.0410 (11) | |
C14 | 0.72395 (18) | 0.3470 (3) | 0.0575 (2) | 0.0410 (11) | |
H14 | 0.7453 | 0.2883 | 0.0751 | 0.049* | |
O21 | 0.51396 (12) | 0.43569 (19) | 0.15512 (14) | 0.0360 (7) | |
C22 | 0.55903 (18) | 0.5079 (3) | 0.1804 (2) | 0.0390 (10) | |
H22A | 0.5967 | 0.4852 | 0.1647 | 0.047* | |
H22B | 0.5613 | 0.5104 | 0.2316 | 0.047* | |
C23 | 0.5426 (2) | 0.6169 (3) | 0.1499 (2) | 0.0532 (14) | |
H23A | 0.5529 | 0.6737 | 0.1834 | 0.064* | |
H23B | 0.5619 | 0.6300 | 0.1065 | 0.064* | |
C24 | 0.4780 (2) | 0.6100 (3) | 0.1362 (2) | 0.0515 (14) | |
H24A | 0.4646 | 0.6572 | 0.0978 | 0.062* | |
H24B | 0.4576 | 0.6281 | 0.1781 | 0.062* | |
C25 | 0.46919 (19) | 0.4950 (3) | 0.1165 (2) | 0.0474 (12) | |
H25A | 0.4308 | 0.4708 | 0.1289 | 0.057* | |
H25B | 0.4723 | 0.4853 | 0.0661 | 0.057* | |
O31 | 0.51366 (12) | 0.09292 (19) | 0.16760 (14) | 0.0335 (7) | |
C32 | 0.5557 (2) | 0.0302 (3) | 0.1348 (2) | 0.0523 (13) | |
H32A | 0.5943 | 0.0421 | 0.1574 | 0.063* | |
H32B | 0.5567 | 0.0489 | 0.0852 | 0.063* | |
C33 | 0.5379 (2) | −0.0836 (3) | 0.1428 (3) | 0.0609 (16) | |
H33A | 0.5500 | −0.1114 | 0.1891 | 0.073* | |
H33B | 0.5537 | −0.1288 | 0.1068 | 0.073* | |
C34 | 0.4727 (2) | −0.0748 (4) | 0.1332 (3) | 0.0706 (18) | |
H34A | 0.4539 | −0.1303 | 0.1597 | 0.085* | |
H34B | 0.4599 | −0.0812 | 0.0837 | 0.085* | |
C35 | 0.45876 (18) | 0.0358 (3) | 0.1612 (2) | 0.0422 (11) | |
H35A | 0.4312 | 0.0727 | 0.1288 | 0.051* | |
H35B | 0.4419 | 0.0302 | 0.2068 | 0.051* | |
C41 | 0.2490 (4) | 0.0379 (7) | 0.2561 (4) | 0.081 (2) | 0.891 (7) |
C42 | 0.2238 (4) | 0.0966 (8) | 0.2032 (4) | 0.086 (2) | 0.891 (7) |
H42 | 0.2346 | 0.0852 | 0.1572 | 0.104* | 0.891 (7) |
C43 | 0.1825 (4) | 0.1728 (8) | 0.2156 (5) | 0.100 (3) | 0.891 (7) |
H43 | 0.1662 | 0.2136 | 0.1783 | 0.120* | 0.891 (7) |
C44 | 0.1648 (4) | 0.1895 (9) | 0.2833 (5) | 0.112 (3) | 0.891 (7) |
H44 | 0.1371 | 0.2418 | 0.2922 | 0.134* | 0.891 (7) |
C45 | 0.1883 (4) | 0.1293 (8) | 0.3349 (4) | 0.097 (3) | 0.891 (7) |
H45 | 0.1759 | 0.1379 | 0.3804 | 0.117* | 0.891 (7) |
C46 | 0.2308 (5) | 0.0540 (9) | 0.3228 (4) | 0.088 (3) | 0.891 (7) |
H46 | 0.2473 | 0.0139 | 0.3604 | 0.106* | 0.891 (7) |
C47 | 0.2963 (4) | −0.0418 (7) | 0.2422 (5) | 0.136 (4) | 0.891 (7) |
H47A | 0.3278 | −0.0058 | 0.2208 | 0.203* | 0.891 (7) |
H47B | 0.2807 | −0.0969 | 0.2109 | 0.203* | 0.891 (7) |
H47C | 0.3104 | −0.0738 | 0.2860 | 0.203* | 0.891 (7) |
C51 | 0.209 (4) | 0.147 (6) | 0.211 (3) | 0.091 (9) | 0.109 (7) |
C52 | 0.247 (3) | 0.071 (5) | 0.194 (3) | 0.085 (9) | 0.109 (7) |
H52 | 0.2601 | 0.0677 | 0.1488 | 0.102* | 0.109 (7) |
C53 | 0.267 (4) | −0.002 (6) | 0.244 (3) | 0.096 (10) | 0.109 (7) |
H53 | 0.2850 | −0.0654 | 0.2307 | 0.115* | 0.109 (7) |
C54 | 0.260 (3) | 0.019 (5) | 0.315 (3) | 0.096 (9) | 0.109 (7) |
H54 | 0.2831 | −0.0154 | 0.3502 | 0.115* | 0.109 (7) |
C55 | 0.219 (4) | 0.088 (8) | 0.331 (3) | 0.094 (10) | 0.109 (7) |
H55 | 0.2094 | 0.0964 | 0.3779 | 0.113* | 0.109 (7) |
C56 | 0.190 (2) | 0.149 (5) | 0.279 (3) | 0.092 (8) | 0.109 (7) |
H56 | 0.1582 | 0.1914 | 0.2897 | 0.110* | 0.109 (7) |
C57 | 0.188 (2) | 0.231 (4) | 0.158 (3) | 0.123 (16) | 0.109 (7) |
H57A | 0.1780 | 0.2952 | 0.1826 | 0.185* | 0.109 (7) |
H57B | 0.1551 | 0.2044 | 0.1307 | 0.185* | 0.109 (7) |
H57C | 0.2195 | 0.2463 | 0.1279 | 0.185* | 0.109 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.0588 (3) | 0.0443 (2) | 0.02624 (19) | −0.0038 (3) | −0.00125 (16) | −0.0006 (3) |
Mg | 0.0334 (7) | 0.0233 (7) | 0.0238 (6) | −0.0022 (6) | 0.0030 (5) | 0.0004 (6) |
O | 0.0363 (14) | 0.0388 (17) | 0.0282 (13) | 0.0002 (14) | 0.0046 (11) | −0.0012 (14) |
N | 0.0367 (17) | 0.0159 (17) | 0.0284 (15) | 0.0013 (14) | 0.0033 (13) | −0.0008 (13) |
C1 | 0.036 (2) | 0.044 (3) | 0.038 (2) | 0.001 (2) | −0.0012 (18) | 0.003 (2) |
C2 | 0.043 (2) | 0.023 (2) | 0.0245 (19) | 0.0006 (18) | −0.0023 (17) | 0.0003 (15) |
C3 | 0.044 (3) | 0.066 (4) | 0.042 (3) | 0.001 (2) | −0.003 (2) | −0.002 (2) |
C4 | 0.048 (2) | 0.040 (2) | 0.033 (2) | 0.001 (3) | 0.0128 (17) | −0.006 (2) |
C5 | 0.041 (3) | 0.038 (2) | 0.031 (2) | 0.000 (2) | 0.0092 (19) | −0.0027 (19) |
C6 | 0.032 (2) | 0.053 (3) | 0.039 (3) | 0.001 (2) | −0.001 (2) | 0.002 (2) |
C7 | 0.048 (3) | 0.054 (3) | 0.035 (3) | 0.003 (2) | −0.006 (2) | 0.005 (2) |
C8 | 0.040 (3) | 0.049 (3) | 0.030 (2) | −0.007 (2) | 0.0003 (19) | 0.000 (2) |
C9 | 0.063 (3) | 0.051 (3) | 0.050 (4) | −0.012 (3) | −0.006 (3) | 0.006 (2) |
C10 | 0.060 (4) | 0.069 (4) | 0.055 (3) | −0.025 (3) | 0.006 (3) | −0.003 (3) |
C11 | 0.038 (3) | 0.080 (4) | 0.045 (3) | −0.010 (3) | 0.006 (2) | −0.012 (3) |
C12 | 0.041 (3) | 0.063 (3) | 0.044 (3) | −0.003 (3) | 0.012 (2) | −0.005 (2) |
C13 | 0.038 (3) | 0.053 (3) | 0.033 (2) | −0.003 (2) | 0.007 (2) | −0.003 (2) |
C14 | 0.040 (3) | 0.043 (3) | 0.040 (3) | 0.006 (2) | 0.007 (2) | 0.000 (2) |
O21 | 0.0436 (19) | 0.0233 (14) | 0.0395 (17) | −0.0014 (14) | −0.0113 (14) | 0.0078 (13) |
C22 | 0.050 (3) | 0.028 (2) | 0.038 (2) | −0.008 (2) | −0.002 (2) | −0.0036 (19) |
C23 | 0.063 (4) | 0.029 (3) | 0.066 (4) | −0.007 (2) | −0.004 (3) | 0.011 (2) |
C24 | 0.073 (4) | 0.032 (3) | 0.051 (3) | 0.013 (2) | 0.014 (3) | 0.011 (2) |
C25 | 0.051 (3) | 0.034 (2) | 0.056 (3) | 0.011 (2) | −0.014 (2) | 0.004 (2) |
O31 | 0.0427 (19) | 0.0238 (14) | 0.0344 (17) | −0.0006 (13) | 0.0058 (14) | −0.0084 (12) |
C32 | 0.061 (3) | 0.032 (3) | 0.066 (3) | 0.007 (2) | 0.016 (3) | −0.002 (2) |
C33 | 0.098 (5) | 0.025 (3) | 0.060 (4) | 0.006 (3) | 0.013 (3) | −0.008 (2) |
C34 | 0.076 (4) | 0.042 (3) | 0.093 (5) | −0.011 (3) | 0.002 (4) | −0.028 (3) |
C35 | 0.051 (3) | 0.037 (2) | 0.039 (3) | −0.013 (2) | −0.002 (2) | −0.006 (2) |
C41 | 0.096 (7) | 0.081 (6) | 0.066 (4) | −0.046 (4) | −0.001 (4) | −0.016 (4) |
C42 | 0.083 (7) | 0.127 (8) | 0.050 (4) | −0.055 (5) | 0.003 (4) | 0.000 (5) |
C43 | 0.079 (7) | 0.128 (7) | 0.091 (5) | −0.043 (5) | −0.011 (5) | 0.022 (6) |
C44 | 0.083 (7) | 0.128 (8) | 0.125 (7) | −0.044 (5) | 0.022 (5) | 0.000 (6) |
C45 | 0.106 (8) | 0.115 (8) | 0.073 (5) | −0.065 (5) | 0.024 (5) | −0.018 (5) |
C46 | 0.117 (8) | 0.098 (8) | 0.050 (4) | −0.058 (5) | 0.005 (4) | −0.007 (4) |
C47 | 0.096 (8) | 0.133 (8) | 0.176 (9) | −0.020 (5) | 0.002 (6) | −0.047 (6) |
C51 | 0.077 (19) | 0.118 (19) | 0.076 (14) | −0.064 (15) | −0.013 (16) | −0.001 (15) |
C52 | 0.08 (2) | 0.106 (18) | 0.068 (15) | −0.078 (15) | −0.008 (16) | −0.014 (15) |
C53 | 0.10 (2) | 0.10 (2) | 0.090 (17) | −0.060 (17) | 0.006 (19) | −0.008 (17) |
C54 | 0.11 (2) | 0.102 (19) | 0.078 (15) | −0.067 (15) | −0.003 (18) | 0.004 (17) |
C55 | 0.11 (2) | 0.10 (2) | 0.074 (15) | −0.074 (16) | 0.009 (17) | −0.005 (16) |
C56 | 0.078 (18) | 0.109 (18) | 0.088 (15) | −0.070 (14) | 0.005 (15) | −0.005 (15) |
C57 | 0.07 (3) | 0.18 (4) | 0.12 (3) | −0.06 (3) | −0.02 (3) | 0.05 (3) |
Br—Mg | 2.693 (2) | C24—H24A | 0.9800 |
Mg—Ni | 2.090 (3) | C24—H24B | 0.9800 |
Mg—N | 2.129 (3) | C25—H25A | 0.9800 |
Mg—O21 | 2.148 (3) | C25—H25B | 0.9800 |
Mg—O31 | 2.180 (3) | O31—C32 | 1.425 (4) |
Mg—O | 2.229 (3) | O31—C35 | 1.457 (4) |
O—C1 | 1.436 (4) | C32—C33 | 1.498 (5) |
O—C4 | 1.447 (4) | C32—H32A | 0.9800 |
N—C2 | 1.217 (4) | C32—H32B | 0.9800 |
N—Mgi | 2.090 (3) | C33—C34 | 1.512 (7) |
C1—C2 | 1.526 (5) | C33—H33A | 0.9800 |
C1—H1A | 0.9800 | C33—H33B | 0.9800 |
C1—H1B | 0.9800 | C34—C35 | 1.531 (5) |
C2—C3 | 1.525 (5) | C34—H34A | 0.9800 |
C3—H3A | 0.9700 | C34—H34B | 0.9800 |
C3—H3B | 0.9700 | C35—H35A | 0.9800 |
C3—H3C | 0.9700 | C35—H35B | 0.9800 |
C4—C5 | 1.504 (5) | C41—C42 | 1.356 (10) |
C4—H4A | 0.9800 | C41—C46 | 1.383 (9) |
C4—H4B | 0.9800 | C41—C47 | 1.517 (10) |
C5—C14 | 1.377 (5) | C42—C43 | 1.382 (10) |
C5—C6 | 1.403 (5) | C42—H42 | 0.9400 |
C6—C7 | 1.375 (5) | C43—C44 | 1.396 (10) |
C6—H6 | 0.9400 | C43—H43 | 0.9400 |
C7—C8 | 1.417 (6) | C44—C45 | 1.335 (10) |
C7—H7 | 0.9400 | C44—H44 | 0.9400 |
C8—C9 | 1.412 (6) | C45—C46 | 1.393 (10) |
C8—C13 | 1.417 (6) | C45—H45 | 0.9400 |
C9—C10 | 1.377 (7) | C46—H46 | 0.9400 |
C9—H9 | 0.9400 | C47—H47A | 0.9700 |
C10—C11 | 1.384 (6) | C47—H47B | 0.9700 |
C10—H10 | 0.9400 | C47—H47C | 0.9700 |
C11—C12 | 1.366 (6) | C51—C52 | 1.36 (2) |
C11—H11 | 0.9400 | C51—C56 | 1.39 (2) |
C12—C13 | 1.426 (5) | C51—C57 | 1.52 (2) |
C12—H12 | 0.9400 | C52—C53 | 1.38 (2) |
C13—C14 | 1.405 (5) | C52—H52 | 0.9400 |
C14—H14 | 0.9400 | C53—C54 | 1.40 (2) |
O21—C25 | 1.444 (4) | C53—H53 | 0.9400 |
O21—C22 | 1.444 (4) | C54—C55 | 1.34 (2) |
C22—C23 | 1.527 (5) | C54—H54 | 0.9400 |
C22—H22A | 0.9800 | C55—C56 | 1.39 (2) |
C22—H22B | 0.9800 | C55—H55 | 0.9400 |
C23—C24 | 1.504 (6) | C56—H56 | 0.9400 |
C23—H23A | 0.9800 | C57—H57A | 0.9700 (15) |
C23—H23B | 0.9800 | C57—H57B | 0.9700 |
C24—C25 | 1.504 (5) | C57—H57C | 0.970 (2) |
Ni—Mg—N | 84.11 (14) | C23—C24—C25 | 102.5 (4) |
Ni—Mg—O21 | 93.97 (12) | C23—C24—H24A | 111.3 |
N—Mg—O21 | 94.93 (11) | C25—C24—H24A | 111.3 |
Ni—Mg—O31 | 92.89 (11) | C23—C24—H24B | 111.3 |
N—Mg—O31 | 92.39 (11) | C25—C24—H24B | 111.3 |
O21—Mg—O31 | 170.45 (11) | H24A—C24—H24B | 109.2 |
Ni—Mg—O | 158.78 (12) | O21—C25—C24 | 106.6 (4) |
N—Mg—O | 74.68 (12) | O21—C25—H25A | 110.4 |
O21—Mg—O | 87.37 (11) | C24—C25—H25A | 110.4 |
O31—Mg—O | 88.65 (11) | O21—C25—H25B | 110.4 |
Ni—Mg—Br | 108.75 (11) | C24—C25—H25B | 110.4 |
N—Mg—Br | 166.72 (9) | H25A—C25—H25B | 108.6 |
O21—Mg—Br | 87.64 (8) | C32—O31—C35 | 107.7 (3) |
O31—Mg—Br | 83.86 (8) | C32—O31—Mg | 125.0 (2) |
O—Mg—Br | 92.46 (10) | C35—O31—Mg | 118.9 (2) |
C1—O—C4 | 113.4 (3) | O31—C32—C33 | 106.5 (4) |
C1—O—Mg | 115.3 (2) | O31—C32—H32A | 110.4 |
C4—O—Mg | 131.0 (2) | C33—C32—H32A | 110.4 |
C2—N—Mgi | 144.7 (3) | O31—C32—H32B | 110.4 |
C2—N—Mg | 119.5 (3) | C33—C32—H32B | 110.4 |
Mgi—N—Mg | 95.81 (14) | H32A—C32—H32B | 108.6 |
O—C1—C2 | 108.3 (3) | C32—C33—C34 | 101.3 (4) |
O—C1—H1A | 110.05 | C32—C33—H33A | 111.5 |
C2—C1—H1A | 110.0 | C34—C33—H33A | 111.5 |
O—C1—H1B | 110.0 | C32—C33—H33B | 111.5 |
C2—C1—H1B | 110.0 | C34—C33—H33B | 111.5 |
H1A—C1—H1B | 108.4 | H33A—C33—H33B | 109.3 |
N—C2—C3 | 126.5 (4) | C33—C34—C35 | 104.6 (4) |
N—C2—C1 | 122.1 (3) | C33—C34—H34A | 110.8 |
C3—C2—C1 | 111.4 (3) | C35—C34—H34A | 110.8 |
C2—C3—H3A | 109.5 | C33—C34—H34B | 110.8 |
C2—C3—H3B | 109.5 | C35—C34—H34B | 110.8 |
H3A—C3—H3B | 109.5 | H34A—C34—H34B | 108.9 |
C2—C3—H3C | 109.5 | O31—C35—C34 | 106.1 (4) |
H3A—C3—H3C | 109.5 | O31—C35—H35A | 110.5 |
H3B—C3—H3C | 109.5 | C34—C35—H35A | 110.5 |
O—C4—C5 | 113.0 (3) | O31—C35—H35B | 110.5 |
O—C4—H4A | 108.98 | C34—C35—H35B | 110.5 |
C5—C4—H4A | 109.0 | H35A—C35—H35B | 108.7 |
O—C4—H4B | 109.0 | C42—C41—C46 | 118.0 (9) |
C5—C4—H4B | 109.0 | C42—C41—C47 | 120.8 (8) |
H4A—C4—H4B | 107.8 | C46—C41—C47 | 121.2 (9) |
C14—C5—C6 | 119.3 (4) | C41—C42—C43 | 121.3 (8) |
C14—C5—C4 | 121.5 (4) | C41—C42—H42 | 119.4 |
C6—C5—C4 | 119.1 (4) | C43—C42—H42 | 119.4 |
C7—C6—C5 | 121.0 (4) | C42—C43—C44 | 120.4 (9) |
C7—C6—H6 | 119.5 | C42—C43—H43 | 119.8 |
C5—C6—H6 | 119.5 | C44—C43—H43 | 119.8 |
C6—C7—C8 | 120.2 (4) | C45—C44—C43 | 118.2 (10) |
C6—C7—H7 | 119.9 | C45—C44—H44 | 120.9 |
C8—C7—H7 | 119.9 | C43—C44—H44 | 120.9 |
C9—C8—C13 | 118.6 (4) | C44—C45—C46 | 121.6 (9) |
C9—C8—C7 | 122.3 (4) | C44—C45—H45 | 119.2 |
C13—C8—C7 | 119.2 (4) | C46—C45—H45 | 119.2 |
C10—C9—C8 | 120.6 (5) | C41—C46—C45 | 120.5 (9) |
C10—C9—H9 | 119.7 | C41—C46—H46 | 119.8 |
C8—C9—H9 | 119.7 | C45—C46—H46 | 119.8 |
C9—C10—C11 | 121.0 (5) | C41—C47—H47A | 109.5 |
C9—C10—H10 | 119.5 | C41—C47—H47B | 109.5 |
C11—C10—H10 | 119.5 | H47A—C47—H47B | 109.5 |
C12—C11—C10 | 120.3 (5) | C41—C47—H47C | 109.5 |
C12—C11—H11 | 119.9 | H47A—C47—H47C | 109.5 |
C10—C11—H11 | 119.9 | H47B—C47—H47C | 109.5 |
C11—C12—C13 | 120.7 (5) | C52—C51—C56 | 119 (2) |
C11—C12—H12 | 119.7 | C52—C51—C57 | 120 (3) |
C13—C12—H12 | 119.7 | C56—C51—C57 | 121 (3) |
C14—C13—C8 | 118.8 (4) | C51—C52—C53 | 120 (3) |
C14—C13—C12 | 122.3 (4) | C51—C52—H52 | 120.1 |
C8—C13—C12 | 118.9 (4) | C53—C52—H52 | 120 |
C5—C14—C13 | 121.5 (4) | C52—C53—C54 | 119 (3) |
C5—C14—H14 | 119.2 | C52—C53—H53 | 120 |
C13—C14—H14 | 119.2 | C54—C53—H53 | 120 |
C25—O21—C22 | 109.2 (3) | C55—C54—C53 | 118 (3) |
C25—O21—Mg | 124.4 (2) | C55—C54—H54 | 121 |
C22—O21—Mg | 126.4 (2) | C53—C54—H54 | 121 |
O21—C22—C23 | 106.1 (3) | C54—C55—C56 | 121 (3) |
O21—C22—H22A | 110.5 | C54—C55—H55 | 120 |
C23—C22—H22A | 110.5 | C56—C55—H55 | 120 |
O21—C22—H22B | 110.5 | C51—C56—C55 | 120 (3) |
C23—C22—H22B | 110.5 | C51—C56—H56 | 120 |
H22A—C22—H22B | 108.7 | C55—C56—H56 | 120 |
C24—C23—C22 | 103.8 (4) | C51—C57—H57A | 109 |
C24—C23—H23A | 111.0 | C51—C57—H57B | 109 |
C22—C23—H23A | 111.0 | H57A—C57—H57B | 109.5 |
C24—C23—H23B | 111.0 | C51—C57—H57C | 109 |
C22—C23—H23B | 111.0 | H57A—C57—H57C | 109.47 |
H23A—C23—H23B | 109.0 | H57B—C57—H57C | 109.47 |
Ni—Mg—O—C1 | −2.2 (5) | C12—C13—C14—C5 | −179.8 (4) |
N—Mg—O—C1 | −3.9 (2) | Ni—Mg—O21—C25 | −65.3 (3) |
O21—Mg—O—C1 | 92.0 (2) | N—Mg—O21—C25 | −149.7 (3) |
O31—Mg—O—C1 | −96.7 (2) | O31—Mg—O21—C25 | 70.5 (8) |
Br—Mg—O—C1 | 179.5 (2) | O—Mg—O21—C25 | 135.9 (3) |
Ni—Mg—O—C4 | 171.5 (3) | Br—Mg—O21—C25 | 43.4 (3) |
N—Mg—O—C4 | 169.8 (3) | Ni—Mg—O21—C22 | 115.4 (3) |
O21—Mg—O—C4 | −94.3 (3) | N—Mg—O21—C22 | 31.0 (3) |
O31—Mg—O—C4 | 77.0 (3) | O31—Mg—O21—C22 | −108.9 (7) |
Br—Mg—O—C4 | −6.8 (3) | O—Mg—O21—C22 | −43.4 (3) |
Ni—Mg—N—C2 | −177.0 (2) | Br—Mg—O21—C22 | −136.0 (3) |
O21—Mg—N—C2 | −83.5 (3) | C25—O21—C22—C23 | −4.7 (5) |
O31—Mg—N—C2 | 90.3 (3) | Mg—O21—C22—C23 | 174.7 (3) |
O—Mg—N—C2 | 2.4 (3) | O21—C22—C23—C24 | 24.3 (5) |
Br—Mg—N—C2 | 17.1 (6) | C22—C23—C24—C25 | −33.5 (5) |
Ni—Mg—N—Mgi | 2.94 (16) | C22—O21—C25—C24 | −16.9 (5) |
O21—Mg—N—Mgi | 96.43 (12) | Mg—O21—C25—C24 | 163.7 (3) |
O31—Mg—N—Mgi | −89.72 (12) | C23—C24—C25—O21 | 31.5 (5) |
O—Mg—N—Mgi | −177.67 (12) | Ni—Mg—O31—C32 | −177.8 (3) |
Br—Mg—N—Mgi | −162.9 (3) | N—Mg—O31—C32 | −93.6 (3) |
C4—O—C1—C2 | −170.3 (3) | O21—Mg—O31—C32 | 46.4 (8) |
Mg—O—C1—C2 | 4.5 (4) | O—Mg—O31—C32 | −19.0 (3) |
Mgi—N—C2—C3 | −1.7 (7) | Br—Mg—O31—C32 | 73.6 (3) |
Mg—N—C2—C3 | 178.2 (3) | Ni—Mg—O31—C35 | 38.1 (3) |
Mgi—N—C2—C1 | 179.5 (3) | N—Mg—O31—C35 | 122.3 (3) |
Mg—N—C2—C1 | −0.5 (5) | O21—Mg—O31—C35 | −97.7 (7) |
O—C1—C2—N | −2.8 (5) | O—Mg—O31—C35 | −163.1 (3) |
O—C1—C2—C3 | 178.3 (3) | Br—Mg—O31—C35 | −70.4 (3) |
C1—O—C4—C5 | −70.6 (4) | C35—O31—C32—C33 | −29.9 (5) |
Mg—O—C4—C5 | 115.6 (3) | Mg—O31—C32—C33 | −177.3 (3) |
O—C4—C5—C14 | 108.6 (4) | O31—C32—C33—C34 | 37.7 (5) |
O—C4—C5—C6 | −70.6 (5) | C32—C33—C34—C35 | −30.7 (5) |
C14—C5—C6—C7 | 0.6 (6) | C32—O31—C35—C34 | 9.4 (5) |
C4—C5—C6—C7 | 179.9 (4) | Mg—O31—C35—C34 | 159.1 (3) |
C5—C6—C7—C8 | 0.6 (7) | C33—C34—C35—O31 | 14.2 (5) |
C6—C7—C8—C9 | 179.3 (4) | C46—C41—C42—C43 | 2.1 (15) |
C6—C7—C8—C13 | −1.3 (6) | C47—C41—C42—C43 | −177.1 (7) |
C13—C8—C9—C10 | −1.4 (7) | C41—C42—C43—C44 | −1.4 (13) |
C7—C8—C9—C10 | 178.0 (4) | C42—C43—C44—C45 | −0.8 (13) |
C8—C9—C10—C11 | 1.1 (7) | C43—C44—C45—C46 | 2.2 (13) |
C9—C10—C11—C12 | 0.1 (8) | C42—C41—C46—C45 | −0.7 (15) |
C10—C11—C12—C13 | −1.0 (7) | C47—C41—C46—C45 | 178.5 (7) |
C9—C8—C13—C14 | −179.9 (4) | C44—C45—C46—C41 | −1.5 (14) |
C7—C8—C13—C14 | 0.7 (6) | C56—C51—C52—C53 | 0 (13) |
C9—C8—C13—C12 | 0.5 (6) | C57—C51—C52—C53 | 177 (8) |
C7—C8—C13—C12 | −178.9 (4) | C51—C52—C53—C54 | −17 (13) |
C11—C12—C13—C14 | −178.9 (4) | C52—C53—C54—C55 | 21 (13) |
C11—C12—C13—C8 | 0.7 (6) | C53—C54—C55—C56 | −9 (16) |
C6—C5—C14—C13 | −1.2 (6) | C52—C51—C56—C55 | 13 (14) |
C4—C5—C14—C13 | 179.5 (4) | C57—C51—C56—C55 | −165 (9) |
C8—C13—C14—C5 | 0.6 (6) | C54—C55—C56—C51 | −8 (16) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mg2(C14H14NO)2(C4H8O)4Br2]·2C7H8 |
Mr | 1105.6 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 220 |
a, b, c (Å) | 23.12 (2), 12.566 (9), 19.142 (10) |
β (°) | 93.32 (7) |
V (Å3) | 5552 (7) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.47 |
Crystal size (mm) | 0.27 × 0.15 × 0.14 |
Data collection | |
Diffractometer | Nonius CAD-4 with gas-stream cryostat diffractometer |
Absorption correction | Integration ABSORP in NRCVAX (Gabe et al., 1989) |
Tmin, Tmax | 0.594, 0.771 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15403, 5238, 2611 |
Rint | 0.096 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.077, 0.78 |
No. of reflections | 5238 |
No. of parameters | 384 |
No. of restraints | 297 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.72, −0.27 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, NRC-2, NRC-2A (Ahmed et al., 1973), SHELXS96 (Sheldrick, 1990), NRCVAX (Gabe et al., 1989) and SHELXL96 (Sheldrick, 1996), ORTEPII (Johnson, 1976) in NRCVAX (Gabe et al., 1989).
Br—Mg | 2.693 (2) | O—C1 | 1.436 (4) |
Mg—Ni | 2.090 (3) | O—C4 | 1.447 (4) |
Mg—N | 2.129 (3) | N—C2 | 1.217 (4) |
Mg—O21 | 2.148 (3) | C1—C2 | 1.526 (5) |
Mg—O31 | 2.180 (3) | C2—C3 | 1.525 (5) |
Mg—O | 2.229 (3) | C4—C5 | 1.504 (5) |
Ni—Mg—N | 84.11 (14) | O31—Mg—Br | 83.86 (8) |
Ni—Mg—O21 | 93.97 (12) | O—Mg—Br | 92.46 (10) |
N—Mg—O21 | 94.93 (11) | C1—O—C4 | 113.4 (3) |
Ni—Mg—O31 | 92.89 (11) | C1—O—Mg | 115.3 (2) |
N—Mg—O31 | 92.39 (11) | C4—O—Mg | 131.0 (2) |
O21—Mg—O31 | 170.45 (11) | C2—N—Mgi | 144.7 (3) |
Ni—Mg—O | 158.78 (12) | C2—N—Mg | 119.5 (3) |
N—Mg—O | 74.68 (12) | Mgi—N—Mg | 95.81 (14) |
O21—Mg—O | 87.37 (11) | O—C1—C2 | 108.3 (3) |
O31—Mg—O | 88.65 (11) | N—C2—C3 | 126.5 (4) |
Ni—Mg—Br | 108.75 (11) | N—C2—C1 | 122.1 (3) |
N—Mg—Br | 166.72 (9) | C3—C2—C1 | 111.4 (3) |
O21—Mg—Br | 87.64 (8) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Ketiminates are an important class of compounds since they can lead to α-tertiary amines by nucleophilic addition (Charette et al., 1998, and refrences therein). However, only lithium-ketiminates (Barr et al., 1984a,b, 1985, 1986, 1987, 1989; Armstrong et al., 1987; Clegg et al., 1983; Shearer et al., 1979) and their sodium analogues (Clegg et al., 1992) have been crystallized due to the difficulties associated with the preparation of these high energy species. To our knowledge, the corresponding magnesio-ketiminates and their α-alkoxy analogues have never been characterized. Therefore, we wish to report herein the first crystallographic characterization of an O-protected α-alkoxy magnesio ketiminate, (I). We have shown in the past that sequential nucleophilic additions to chiral cyanohydrins lead to α-tertiary amines in high yields and diastereoselectivities (Charette & Mellon, 1998). The induced quaternary stereogenic center has been assigned, and a chelated N-magnesio-ketiminate having the metal cis to the alkoxy group has been postulated to explain the stereochemical outcome of the reaction. An enantioselective version involving a chiral Lewis acid has been developed (Charette & Gagnon, 1999), and the level of induction also depends on the structural features of the ketiminate intermediate. The X-ray structure reported in this paper (Fig. 1) confirms the cis stereochemistry of the ketiminate obtained under those conditions, thus providing further mechanistic insights into the double nucleophilic addition reaction to cyanohydrins. \sch
The compound (I) crystallizes as a dimer in space group C2/c with a twofold axis of symmetry passing through the center of the dimer formed by the nitrogen and magnesium atoms. The simeric nature of the molecule is supported by the fact that the Mg—Ni (symmetry code: (i) 1 - x, y, 1/2 - z) distance is significantly shorter thatn the Mg—N bond. disordered solvent molecules are located in large channels in the a direction. The magnesium adopts a distorted octahedral geometry with two coordinated tetrahydrofuran molecules. The Mg—Ni bond length of 2.090 (3) Å and the C2—N—Mg angle of 119.5 (3)° shows that the magnesium is cis to the ether moiety. Morever, the O—Mg bond length of 2.229 (3) Å and the octahedral geometry of the magnesium demonstrates that the metal is chelated by the oxygen of the ether. The difference in the O—Mg bond length with the average of 2.106 (3) Å found in Cambridge Structural Database is probably due to geometry constraints imposed by the sp2 C2 and sp3 C1. The five-membered ring formed by C1—C2—N—Mg—O as well as C3 all lie in a plane to within an RMS deviation of 0.02 Å. The C2—N bond length of 1.217 (4) Å corresponds to a C=N double bond, confirming the ketiminate functionality.