Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680101563X/om6056sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680101563X/om6056Isup2.hkl |
CCDC reference: 175377
The title compound was prepared by treatment of 3-(2-bromophenyl)sydnone (Applegate & Turnbull, 1988) in dry tetrahydrofuran at 195 K with 1.5 equivalents of lithium diisopropylamide followed by 2 equivalents of triisopropylsilyl chloride.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD (McArdle, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: OSCAIL (McArdle, 1995).
Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids for all non-H atoms. H atoms have been omitted for clarity. |
C17H25BrN2O2Si | F(000) = 824 |
Mr = 397.39 | Dx = 1.368 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 11.7560 (18) Å | θ = 3.2–12.9° |
b = 12.772 (2) Å | µ = 2.20 mm−1 |
c = 12.8527 (18) Å | T = 296 K |
β = 91.820 (12)° | Rectangular solid with sharp bounding edges, colorless |
V = 1928.8 (5) Å3 | 0.35 × 0.30 × 0.25 mm |
Z = 4 |
Enraf-Nonius CAD-4 diffractometer | 2262 reflections with I<2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.012 |
Graphite monochromator | θmax = 30.0°, θmin = 2.3° |
ω/2θ scans | h = −16→16 |
Absorption correction: analytical (Alcock, 1970) | k = 0→17 |
Tmin = 0.477, Tmax = 0.591 | l = 0→18 |
6088 measured reflections | 3 standard reflections every 120 reflections |
5605 independent reflections | intensity decay: <0.1% |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.76 | w = 1/[σ2(Fo2) + (0.0615P)2] where P = (Fo2 + 2Fc2)/3 |
5605 reflections | (Δ/σ)max = 0.001 |
214 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
C17H25BrN2O2Si | V = 1928.8 (5) Å3 |
Mr = 397.39 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.7560 (18) Å | µ = 2.20 mm−1 |
b = 12.772 (2) Å | T = 296 K |
c = 12.8527 (18) Å | 0.35 × 0.30 × 0.25 mm |
β = 91.820 (12)° |
Enraf-Nonius CAD-4 diffractometer | 2262 reflections with I<2σ(I) |
Absorption correction: analytical (Alcock, 1970) | Rint = 0.012 |
Tmin = 0.477, Tmax = 0.591 | 3 standard reflections every 120 reflections |
6088 measured reflections | intensity decay: <0.1% |
5605 independent reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 0.76 | Δρmax = 0.41 e Å−3 |
5605 reflections | Δρmin = −0.40 e Å−3 |
214 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 | ||
Br1 | −0.07650 (3) | 0.58368 (3) | 0.23990 (3) | 0.07333 (14) | |
Si1 | 0.25799 (6) | 0.70689 (6) | 0.07415 (6) | 0.04265 (18) | |
O1 | 0.22264 (19) | 0.68413 (17) | 0.38982 (16) | 0.0652 (6) | |
O5 | 0.37655 (19) | 0.62431 (19) | 0.30698 (18) | 0.0728 (6) | |
N2 | 0.1204 (2) | 0.7300 (2) | 0.36492 (18) | 0.0599 (6) | |
N3 | 0.12206 (19) | 0.74113 (16) | 0.26418 (16) | 0.0462 (5) | |
C4 | 0.2160 (2) | 0.70632 (19) | 0.2156 (2) | 0.0447 (6) | |
C5 | 0.2852 (3) | 0.6668 (2) | 0.2991 (2) | 0.0547 (7) | |
C11 | 0.0198 (2) | 0.7865 (2) | 0.2175 (2) | 0.0468 (6) | |
C12 | −0.0755 (2) | 0.7262 (2) | 0.1995 (2) | 0.0525 (7) | |
C13 | −0.1705 (3) | 0.7695 (3) | 0.1510 (2) | 0.0679 (9) | |
C14 | −0.1686 (3) | 0.8740 (3) | 0.1235 (3) | 0.0737 (9) | |
C15 | −0.0751 (3) | 0.9348 (3) | 0.1442 (3) | 0.0721 (9) | |
C16 | 0.0216 (3) | 0.8919 (2) | 0.1913 (2) | 0.0570 (7) | |
C21 | 0.1335 (2) | 0.7403 (2) | −0.0168 (2) | 0.0454 (6) | |
C22 | 0.0447 (3) | 0.6541 (2) | −0.0312 (2) | 0.0639 (8) | |
C23 | 0.1714 (3) | 0.7760 (3) | −0.1233 (2) | 0.0671 (9) | |
C31 | 0.3208 (2) | 0.5731 (2) | 0.0536 (2) | 0.0559 (7) | |
C32 | 0.2431 (3) | 0.4818 (2) | 0.0820 (3) | 0.0795 (10) | |
C33 | 0.3636 (3) | 0.5588 (3) | −0.0571 (3) | 0.0812 (11) | |
C41 | 0.3714 (2) | 0.8097 (2) | 0.0597 (2) | 0.0573 (7) | |
C42 | 0.3282 (3) | 0.9202 (2) | 0.0825 (3) | 0.0814 (11) | |
C43 | 0.4818 (3) | 0.7881 (3) | 0.1225 (3) | 0.0903 (12) | |
H13 | −0.2349 | 0.7290 | 0.1370 | 0.102* | |
H14 | −0.2323 | 0.9035 | 0.0902 | 0.111* | |
H15 | −0.0764 | 1.0054 | 0.1265 | 0.108* | |
H16 | 0.0859 | 0.9326 | 0.2051 | 0.085* | |
H21 | 0.0947 | 0.8000 | 0.0142 | 0.068* | |
H22A | −0.0227 | 0.6825 | −0.0645 | 0.096* | |
H22B | 0.0263 | 0.6261 | 0.0355 | 0.096* | |
H22C | 0.0745 | 0.5993 | −0.0736 | 0.096* | |
H23A | 0.2071 | 0.7188 | −0.1579 | 0.101* | |
H23B | 0.2246 | 0.8327 | −0.1150 | 0.101* | |
H23C | 0.1064 | 0.7992 | −0.1642 | 0.101* | |
H31 | 0.3879 | 0.5684 | 0.1005 | 0.084* | |
H32A | 0.1760 | 0.4828 | 0.0375 | 0.119* | |
H32B | 0.2218 | 0.4887 | 0.1532 | 0.119* | |
H32C | 0.2828 | 0.4169 | 0.0732 | 0.119* | |
H33A | 0.4020 | 0.4927 | −0.0620 | 0.122* | |
H33B | 0.4155 | 0.6143 | −0.0726 | 0.122* | |
H33C | 0.3002 | 0.5604 | −0.1060 | 0.122* | |
H41 | 0.3914 | 0.8092 | −0.0137 | 0.086* | |
H42A | 0.3118 | 0.9259 | 0.1550 | 0.122* | |
H42B | 0.2602 | 0.9336 | 0.0413 | 0.122* | |
H42C | 0.3854 | 0.9705 | 0.0656 | 0.122* | |
H43A | 0.5350 | 0.8437 | 0.1114 | 0.135* | |
H43B | 0.5138 | 0.7230 | 0.1004 | 0.135* | |
H43C | 0.4658 | 0.7841 | 0.1952 | 0.135* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0800 (3) | 0.0556 (2) | 0.0850 (3) | −0.01240 (17) | 0.01275 (19) | −0.00641 (17) |
Si1 | 0.0396 (4) | 0.0421 (4) | 0.0460 (4) | 0.0025 (3) | −0.0021 (3) | −0.0014 (3) |
O1 | 0.0803 (15) | 0.0651 (13) | 0.0495 (12) | 0.0012 (11) | −0.0089 (11) | 0.0052 (10) |
O5 | 0.0659 (14) | 0.0733 (14) | 0.0778 (16) | 0.0144 (12) | −0.0199 (12) | 0.0052 (12) |
N2 | 0.0718 (18) | 0.0617 (16) | 0.0462 (14) | 0.0018 (13) | −0.0001 (12) | 0.0025 (12) |
N3 | 0.0525 (13) | 0.0428 (12) | 0.0429 (13) | −0.0019 (10) | −0.0020 (10) | −0.0038 (10) |
C4 | 0.0459 (15) | 0.0400 (13) | 0.0478 (15) | 0.0053 (12) | −0.0060 (12) | −0.0048 (12) |
C5 | 0.0639 (19) | 0.0469 (15) | 0.0527 (18) | −0.0014 (15) | −0.0090 (15) | 0.0049 (13) |
C11 | 0.0470 (15) | 0.0521 (16) | 0.0413 (14) | 0.0071 (13) | 0.0027 (12) | −0.0046 (12) |
C12 | 0.0559 (18) | 0.0512 (17) | 0.0503 (16) | −0.0011 (13) | 0.0012 (13) | −0.0093 (13) |
C13 | 0.0552 (19) | 0.086 (2) | 0.062 (2) | 0.0013 (17) | −0.0016 (16) | −0.0136 (18) |
C14 | 0.068 (2) | 0.086 (2) | 0.065 (2) | 0.022 (2) | −0.0097 (17) | 0.0054 (19) |
C15 | 0.084 (3) | 0.060 (2) | 0.073 (2) | 0.0211 (18) | 0.0025 (18) | 0.0032 (16) |
C16 | 0.0582 (18) | 0.0510 (17) | 0.0618 (18) | 0.0044 (14) | 0.0044 (15) | −0.0018 (14) |
C21 | 0.0399 (14) | 0.0501 (15) | 0.0462 (15) | 0.0046 (12) | −0.0006 (12) | −0.0046 (12) |
C22 | 0.0549 (18) | 0.072 (2) | 0.0636 (19) | −0.0063 (15) | −0.0116 (15) | −0.0099 (16) |
C23 | 0.066 (2) | 0.083 (2) | 0.0520 (18) | 0.0058 (18) | −0.0049 (15) | 0.0096 (16) |
C31 | 0.0518 (17) | 0.0504 (16) | 0.0652 (19) | 0.0138 (13) | −0.0033 (14) | −0.0056 (13) |
C32 | 0.096 (3) | 0.0442 (18) | 0.098 (3) | 0.0035 (17) | −0.002 (2) | 0.0012 (17) |
C33 | 0.087 (3) | 0.082 (3) | 0.076 (2) | 0.028 (2) | 0.013 (2) | −0.0188 (18) |
C41 | 0.0505 (16) | 0.0574 (18) | 0.0640 (19) | −0.0076 (13) | 0.0021 (14) | 0.0016 (14) |
C42 | 0.082 (2) | 0.0521 (19) | 0.110 (3) | −0.0134 (18) | −0.004 (2) | −0.0034 (19) |
C43 | 0.057 (2) | 0.100 (3) | 0.113 (3) | −0.016 (2) | −0.020 (2) | 0.015 (2) |
Br1—C12 | 1.893 (3) | C22—H22A | 0.9599 |
Si1—C31 | 1.883 (3) | C22—H22B | 0.9599 |
Si1—C41 | 1.884 (3) | C22—H22C | 0.9599 |
Si1—C21 | 1.892 (3) | C23—H23A | 0.9599 |
Si1—C4 | 1.899 (3) | C23—H23B | 0.9599 |
O1—N2 | 1.366 (3) | C23—H23C | 0.9599 |
O1—C5 | 1.415 (4) | C31—C32 | 1.532 (4) |
O5—C5 | 1.205 (3) | C31—C33 | 1.536 (4) |
N3—N2 | 1.303 (3) | C31—H31 | 0.9800 |
N3—C4 | 1.360 (3) | C32—H32A | 0.9599 |
N3—C11 | 1.448 (3) | C32—H32B | 0.9599 |
C4—C5 | 1.419 (4) | C32—H32C | 0.9599 |
C11—C12 | 1.372 (4) | C33—H33A | 0.9599 |
C11—C16 | 1.388 (4) | C33—H33B | 0.9599 |
C12—C13 | 1.378 (4) | C33—H33C | 0.9599 |
C13—C14 | 1.380 (5) | C41—C43 | 1.531 (4) |
C13—H13 | 0.9300 | C41—C42 | 1.532 (4) |
C14—C15 | 1.365 (5) | C41—H41 | 0.9800 |
C14—H14 | 0.9300 | C42—H42A | 0.9599 |
C15—C16 | 1.384 (5) | C42—H42B | 0.9599 |
C15—H15 | 0.9300 | C42—H42C | 0.9599 |
C16—H16 | 0.9300 | C43—H43A | 0.9599 |
C21—C23 | 1.523 (4) | C43—H43B | 0.9599 |
C21—C22 | 1.525 (4) | C43—H43C | 0.9599 |
C21—H21 | 0.9800 | ||
C31—Si1—C41 | 109.68 (13) | H22A—C22—H22C | 109.5 |
C31—Si1—C21 | 114.63 (13) | H22B—C22—H22C | 109.5 |
C41—Si1—C21 | 108.53 (13) | C21—C23—H23A | 109.5 |
C31—Si1—C4 | 104.23 (13) | C21—C23—H23B | 109.5 |
C41—Si1—C4 | 107.65 (13) | H23A—C23—H23B | 109.5 |
C21—Si1—C4 | 111.88 (12) | C21—C23—H23C | 109.5 |
N2—O1—C5 | 110.5 (2) | H23A—C23—H23C | 109.5 |
N3—N2—O1 | 103.8 (2) | H23B—C23—H23C | 109.5 |
N2—N3—C4 | 117.3 (2) | C32—C31—C33 | 110.2 (3) |
N2—N3—C11 | 114.6 (2) | C32—C31—Si1 | 114.7 (2) |
C4—N3—C11 | 128.0 (2) | C33—C31—Si1 | 112.3 (2) |
N3—C4—C5 | 102.9 (2) | C32—C31—H31 | 106.3 |
N3—C4—Si1 | 132.69 (19) | C33—C31—H31 | 106.3 |
C5—C4—Si1 | 124.4 (2) | Si1—C31—H31 | 106.3 |
O5—C5—O1 | 119.1 (3) | C31—C32—H32A | 109.5 |
O5—C5—C4 | 135.4 (3) | C31—C32—H32B | 109.5 |
O1—C5—C4 | 105.5 (2) | H32A—C32—H32B | 109.5 |
C12—C11—C16 | 121.4 (3) | C31—C32—H32C | 109.5 |
C12—C11—N3 | 120.6 (2) | H32A—C32—H32C | 109.5 |
C16—C11—N3 | 118.0 (3) | H32B—C32—H32C | 109.5 |
C11—C12—C13 | 119.8 (3) | C31—C33—H33A | 109.5 |
C11—C12—Br1 | 120.3 (2) | C31—C33—H33B | 109.5 |
C13—C12—Br1 | 119.9 (2) | H33A—C33—H33B | 109.5 |
C12—C13—C14 | 119.0 (3) | C31—C33—H33C | 109.5 |
C12—C13—H13 | 120.5 | H33A—C33—H33C | 109.5 |
C14—C13—H13 | 120.5 | H33B—C33—H33C | 109.5 |
C15—C14—C13 | 121.3 (3) | C43—C41—C42 | 110.2 (3) |
C15—C14—H14 | 119.4 | C43—C41—Si1 | 114.4 (2) |
C13—C14—H14 | 119.4 | C42—C41—Si1 | 112.5 (2) |
C14—C15—C16 | 120.3 (3) | C43—C41—H41 | 106.4 |
C14—C15—H15 | 119.8 | C42—C41—H41 | 106.4 |
C16—C15—H15 | 119.8 | Si1—C41—H41 | 106.4 |
C15—C16—C11 | 118.1 (3) | C41—C42—H42A | 109.5 |
C15—C16—H16 | 120.9 | C41—C42—H42B | 109.5 |
C11—C16—H16 | 120.9 | H42A—C42—H42B | 109.5 |
C23—C21—C22 | 109.0 (2) | C41—C42—H42C | 109.5 |
C23—C21—Si1 | 112.35 (19) | H42A—C42—H42C | 109.5 |
C22—C21—Si1 | 115.16 (19) | H42B—C42—H42C | 109.5 |
C23—C21—H21 | 106.6 | C41—C43—H43A | 109.5 |
C22—C21—H21 | 106.6 | C41—C43—H43B | 109.5 |
Si1—C21—H21 | 106.6 | H43A—C43—H43B | 109.5 |
C21—C22—H22A | 109.5 | C41—C43—H43C | 109.5 |
C21—C22—H22B | 109.5 | H43A—C43—H43C | 109.5 |
H22A—C22—H22B | 109.5 | H43B—C43—H43C | 109.5 |
C21—C22—H22C | 109.5 | ||
C31—Si1—C4—N3 | −137.1 (3) | C5—O1—N2—N3 | −0.9 (3) |
C41—Si1—C4—N3 | 106.5 (3) | C4—N3—N2—O1 | 0.6 (3) |
C21—Si1—C4—N3 | −12.7 (3) | C11—N3—N2—O1 | 178.5 (2) |
C31—Si1—C4—C5 | 44.2 (3) | N2—N3—C4—C5 | −0.1 (3) |
C41—Si1—C4—C5 | −72.2 (3) | C11—N3—C4—C5 | −177.6 (2) |
C21—Si1—C4—C5 | 168.6 (2) | N2—N3—C4—Si1 | −179.0 (2) |
C31—Si1—C21—C23 | −80.4 (2) | C11—N3—C4—Si1 | 3.5 (4) |
C41—Si1—C21—C23 | 42.6 (2) | N2—N3—C11—C12 | −79.4 (3) |
C4—Si1—C21—C23 | 161.2 (2) | C4—N3—C11—C12 | 98.1 (3) |
C31—Si1—C21—C22 | 45.2 (3) | N2—N3—C11—C16 | 100.9 (3) |
C41—Si1—C21—C22 | 168.2 (2) | C4—N3—C11—C16 | −81.5 (3) |
C4—Si1—C21—C22 | −73.2 (2) | N3—C4—C5—O5 | 178.2 (3) |
C41—Si1—C31—C32 | 169.7 (2) | Si1—C4—C5—O5 | −2.7 (5) |
C21—Si1—C31—C32 | −67.9 (3) | N3—C4—C5—O1 | −0.4 (3) |
C4—Si1—C31—C32 | 54.7 (3) | Si1—C4—C5—O1 | 178.62 (18) |
C41—Si1—C31—C33 | −63.4 (3) | C16—C11—C12—C13 | 2.4 (4) |
C21—Si1—C31—C33 | 59.0 (3) | N3—C11—C12—C13 | −177.2 (3) |
C4—Si1—C31—C33 | −178.4 (2) | C16—C11—C12—Br1 | −178.1 (2) |
C31—Si1—C41—C43 | −49.4 (3) | N3—C11—C12—Br1 | 2.2 (4) |
C21—Si1—C41—C43 | −175.3 (2) | C11—C12—C13—C14 | −1.5 (4) |
C4—Si1—C41—C43 | 63.4 (3) | Br1—C12—C13—C14 | 179.1 (2) |
C31—Si1—C41—C42 | −176.2 (2) | C12—C13—C14—C15 | −0.5 (5) |
C21—Si1—C41—C42 | 57.8 (3) | C13—C14—C15—C16 | 1.6 (5) |
C4—Si1—C41—C42 | −63.4 (3) | C14—C15—C16—C11 | −0.7 (5) |
N2—O1—C5—O5 | −178.1 (3) | C12—C11—C16—C15 | −1.3 (4) |
N2—O1—C5—C4 | 0.8 (3) | N3—C11—C16—C15 | 178.3 (3) |
Experimental details
Crystal data | |
Chemical formula | C17H25BrN2O2Si |
Mr | 397.39 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 11.7560 (18), 12.772 (2), 12.8527 (18) |
β (°) | 91.820 (12) |
V (Å3) | 1928.8 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.20 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Analytical (Alcock, 1970) |
Tmin, Tmax | 0.477, 0.591 |
No. of measured, independent and observed [I<2σ(I)] reflections | 6088, 5605, 2262 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.120, 0.76 |
No. of reflections | 5605 |
No. of parameters | 214 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.40 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, XCAD (McArdle, 1995), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995), OSCAIL (McArdle, 1995).
Br1—C12 | 1.893 (3) | C11—C12 | 1.372 (4) |
Si1—C31 | 1.883 (3) | C11—C16 | 1.388 (4) |
Si1—C41 | 1.884 (3) | C12—C13 | 1.378 (4) |
Si1—C21 | 1.892 (3) | C13—C14 | 1.380 (5) |
Si1—C4 | 1.899 (3) | C14—C15 | 1.365 (5) |
O1—N2 | 1.366 (3) | C15—C16 | 1.384 (5) |
O1—C5 | 1.415 (4) | C21—C23 | 1.523 (4) |
O5—C5 | 1.205 (3) | C21—C22 | 1.525 (4) |
N3—N2 | 1.303 (3) | C31—C32 | 1.532 (4) |
N3—C4 | 1.360 (3) | C31—C33 | 1.536 (4) |
N3—C11 | 1.448 (3) | C41—C43 | 1.531 (4) |
C4—C5 | 1.419 (4) | C41—C42 | 1.532 (4) |
C31—Si1—C41 | 109.68 (13) | C12—C11—N3 | 120.6 (2) |
C31—Si1—C21 | 114.63 (13) | C16—C11—N3 | 118.0 (3) |
C41—Si1—C21 | 108.53 (13) | C11—C12—C13 | 119.8 (3) |
C31—Si1—C4 | 104.23 (13) | C11—C12—Br1 | 120.3 (2) |
C41—Si1—C4 | 107.65 (13) | C13—C12—Br1 | 119.9 (2) |
C21—Si1—C4 | 111.88 (12) | C12—C13—C14 | 119.0 (3) |
N2—O1—C5 | 110.5 (2) | C15—C14—C13 | 121.3 (3) |
N3—N2—O1 | 103.8 (2) | C14—C15—C16 | 120.3 (3) |
N2—N3—C4 | 117.3 (2) | C15—C16—C11 | 118.1 (3) |
N2—N3—C11 | 114.6 (2) | C23—C21—C22 | 109.0 (2) |
C4—N3—C11 | 128.0 (2) | C23—C21—Si1 | 112.35 (19) |
N3—C4—C5 | 102.9 (2) | C22—C21—Si1 | 115.16 (19) |
N3—C4—Si1 | 132.69 (19) | C32—C31—C33 | 110.2 (3) |
C5—C4—Si1 | 124.4 (2) | C32—C31—Si1 | 114.7 (2) |
O5—C5—O1 | 119.1 (3) | C33—C31—Si1 | 112.3 (2) |
O5—C5—C4 | 135.4 (3) | C43—C41—C42 | 110.2 (3) |
O1—C5—C4 | 105.5 (2) | C43—C41—Si1 | 114.4 (2) |
C12—C11—C16 | 121.4 (3) | C42—C41—Si1 | 112.5 (2) |
C31—Si1—C4—N3 | −137.1 (3) | C5—O1—N2—N3 | −0.9 (3) |
C41—Si1—C4—N3 | 106.5 (3) | C4—N3—N2—O1 | 0.6 (3) |
C21—Si1—C4—N3 | −12.7 (3) | C11—N3—N2—O1 | 178.5 (2) |
C31—Si1—C4—C5 | 44.2 (3) | N2—N3—C4—C5 | −0.1 (3) |
C41—Si1—C4—C5 | −72.2 (3) | C11—N3—C4—C5 | −177.6 (2) |
C21—Si1—C4—C5 | 168.6 (2) | N2—N3—C4—Si1 | −179.0 (2) |
C31—Si1—C21—C23 | −80.4 (2) | C11—N3—C4—Si1 | 3.5 (4) |
C41—Si1—C21—C23 | 42.6 (2) | N2—N3—C11—C12 | −79.4 (3) |
C4—Si1—C21—C23 | 161.2 (2) | C4—N3—C11—C12 | 98.1 (3) |
C31—Si1—C21—C22 | 45.2 (3) | N2—N3—C11—C16 | 100.9 (3) |
C41—Si1—C21—C22 | 168.2 (2) | C4—N3—C11—C16 | −81.5 (3) |
C4—Si1—C21—C22 | −73.2 (2) | N3—C4—C5—O5 | 178.2 (3) |
C41—Si1—C31—C32 | 169.7 (2) | Si1—C4—C5—O5 | −2.7 (5) |
C21—Si1—C31—C32 | −67.9 (3) | N3—C4—C5—O1 | −0.4 (3) |
C4—Si1—C31—C32 | 54.7 (3) | Si1—C4—C5—O1 | 178.62 (18) |
C41—Si1—C31—C33 | −63.4 (3) | C16—C11—C12—C13 | 2.4 (4) |
C21—Si1—C31—C33 | 59.0 (3) | N3—C11—C12—C13 | −177.2 (3) |
C4—Si1—C31—C33 | −178.4 (2) | C16—C11—C12—Br1 | −178.1 (2) |
C31—Si1—C41—C43 | −49.4 (3) | N3—C11—C12—Br1 | 2.2 (4) |
C21—Si1—C41—C43 | −175.3 (2) | C11—C12—C13—C14 | −1.5 (4) |
C4—Si1—C41—C43 | 63.4 (3) | Br1—C12—C13—C14 | 179.1 (2) |
C31—Si1—C41—C42 | −176.2 (2) | C12—C13—C14—C15 | −0.5 (5) |
C21—Si1—C41—C42 | 57.8 (3) | C13—C14—C15—C16 | 1.6 (5) |
C4—Si1—C41—C42 | −63.4 (3) | C14—C15—C16—C11 | −0.7 (5) |
N2—O1—C5—O5 | −178.1 (3) | C12—C11—C16—C15 | −1.3 (4) |
N2—O1—C5—C4 | 0.8 (3) | N3—C11—C16—C15 | 178.3 (3) |
Sydnones are dipolar heteroaromatic compounds first prepared in Sydney, Australia (Earl & Mackney, 1935). They undergo electrophilic aromatic substitution with common electrophiles and this type of reactivity has been extended to the formation of bridged ring analogs via intramolecular processes. For the latter, suitable ortho-substituted arylsydnones have been required, however, the majority of these have been available only through tedious multistep protocols from the corresponding ortho-substituted anilines. We have been interested in more direct routes to ortho-substituted arylsydnones and lithiation strategies have come to the fore. Thus, the molecule described herein was envisaged as a lithiation precursor to a variety of different ortho-substituted arylsydnones via metal-halogen exchange with n-butyllithium, trapping of the incipient anion with a suitable electrophile, and subsequent removal of the silyl protective group with fluoride ion. Interestingly, when an attempt was made to utilize this compound for ortho-substituted arylsydnone synthesis, via reaction with 2.2 equivalents of n-butyllithium at 195 K in dry tetrahydrofuran, migration of the silyl moiety to the ortho-aryl position occurred in high yield. Accordingly, the title compound [and its congeners], (I), have become valuable precursors to ortho-silylarylsydnones; the latter would be difficultly accessible by any other synthetic scheme. It is not clear with the present data how general this novel migration will be and whether or not it is an intra- or intermolecular process, however, further research will help to answer these interesting questions.
The sydnone and phenyl-ring systems found in the compounds are themselves planar, but the rings within a structure lie nearly perpendicular to each other, having an angle of 80.62 (10)°. The bond distances and angles around each atom are within accepted values. In examining the molecule relative to the 1,5 shift, it is noted that the contact distance between the Si atom and Br atom is 4.81 Å, and that between Si and C12 is 4.28 Å.