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The title compound, C
23H
23NO
2SSi, at 100 K adopts a boat conformation which brings the C—H bond of an axial phenyl substituent into proximity [C
N = 3.376 (1) Å] with the aziridine lone pair. The factors which favour this conformation for bicyclo[3.1.0]hexane systems are considered.
Supporting information
CCDC references: 158280; 158281; 158282
Reaction of diphenyldichlorosilane with magnesium and butadiene yields a
silacyclopentene (see Scheme) which is thought to be formed via a
diphenylsilylene intermediate (Mignani et al., 1995). Direct
aziridination of its double bond using the protocol of Jeong et al.
(1998), which involves reaction with chloramine-T in the presence of
phenyltrimethylammonium tribromide (PTAB), produced the title compound (m.p.
370 K), which was characterized using IR, NMR and MS. νmax (KBr)/cm-1
3434, 3067, 3046, 3014, 2949, 2911, 1597, 1486, 1428, 1395, 1358, 1317, 1209,
1181, 1159, 807. δH (CDCl3, 400 MHz): 1.34 (2H, d, J = 16 Hz),
1.55 (2H, d, J = 16 Hz), 2.35 (3H, s), 3.42 (2H, s),
7.19–7.62 (14H, m, aryl H). δC (CDCl3, 100 MHz): 14.6 (2 C),
22.0, 46.9 (2 C), 127.9, 128.1, 128.5, 129.8, 129.9, 130.2, 134.9, 135.0,
135.1, 135.8, 136.6, 144.4. m/z (EI): 406.1 (MH+, 84%), 352 (100), 328
(76), 250 (63), 222 (17), 105 (7).
H atoms were refined freely [C—H 0.924 (17)–1.000 (18) Å], except for those
attached to the C37 methyl group, which was defined as a riding rigid group
and only its orientation was refined.
Data collection: SCALEPACK and DENZO (Otwinowski & Minor, 1997) for (I); Collect (Nonius BV, 1997-2000) for km1600; CAD-4 EXPRESS (Enraf Nonius, 1994) for km2099. Cell refinement: SCALEPACK and DENZO for (I); HKL SCALEPACK (Otwinowski & Minor 1997) for km1600; CAD-4 EXPRESS (Enraf Nonius, 1994) for km2099. Data reduction: SCALEPACK and DENZO for (I); HKL DENZO and SCALEPACK (Otwinowski & Minor 19 for km1600; XCAD4 (Harms & Wocadlo, 1995) for km2099. Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (I); SHELXS97 for km1600; SHELXS97 (Sheldrick, 1990) for km2099. For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEP-3 (Farrugia, 1997) for (I); ORTEP-3 for Windows (Farrugia, 1997) for km1600; ORTEP (Farrugia, 1997) for km2099. Software used to prepare material for publication: WinGX (Farrugia, 1999) for (I), km2099; WinGX publication routines (Farrugia, 1999) for km1600.
Crystal data top
C23H23NO2SSi | Dx = 1.277 Mg m−3 |
Mr = 405.57 | Melting point: 370 K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.2955 (1) Å | Cell parameters from 39587 reflections |
b = 8.6076 (1) Å | θ = 1–35° |
c = 26.5354 (3) Å | µ = 0.23 mm−1 |
β = 96.440 (1)° | T = 100 K |
V = 2109.75 (4) Å3 | Block, colourless |
Z = 4 | 0.3 × 0.2 × 0.2 mm |
F(000) = 856 | |
Data collection top
KappaCCD diffractometer | Rint = 0.039 |
ϕ scans and ω scans with κ offsets | θmax = 34.9°, θmin = 3.1° |
26689 measured reflections | h = −14→14 |
8784 independent reflections | k = −13→11 |
7613 reflections with I > 2σ(I) | l = −40→40 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.041 | w = 1/[σ2(Fo2) + (0.0566P)2 + 0.790P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.116 | (Δ/σ)max = 0.001 |
S = 1.04 | Δρmax = 0.47 e Å−3 |
8784 reflections | Δρmin = −0.45 e Å−3 |
334 parameters | |
Crystal data top
C23H23NO2SSi | V = 2109.75 (4) Å3 |
Mr = 405.57 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2955 (1) Å | µ = 0.23 mm−1 |
b = 8.6076 (1) Å | T = 100 K |
c = 26.5354 (3) Å | 0.3 × 0.2 × 0.2 mm |
β = 96.440 (1)° | |
Data collection top
KappaCCD diffractometer | 7613 reflections with I > 2σ(I) |
26689 measured reflections | Rint = 0.039 |
8784 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.116 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.47 e Å−3 |
8784 reflections | Δρmin = −0.45 e Å−3 |
334 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | −0.17835 (3) | 0.72377 (3) | 0.468274 (9) | 0.01617 (6) | |
Si1 | 0.12849 (3) | 0.73784 (3) | 0.339713 (9) | 0.01329 (6) | |
O1 | −0.08123 (9) | 0.74901 (9) | 0.51374 (3) | 0.02183 (15) | |
O2 | −0.27101 (9) | 0.58909 (9) | 0.46584 (3) | 0.02511 (16) | |
N1 | −0.07549 (9) | 0.72718 (9) | 0.42104 (3) | 0.01459 (13) | |
C1 | 0.17628 (10) | 0.65441 (11) | 0.40578 (4) | 0.01660 (15) | |
C2 | 0.03313 (10) | 0.59885 (11) | 0.42143 (3) | 0.01590 (15) | |
C3 | −0.09409 (10) | 0.60350 (11) | 0.38147 (3) | 0.01649 (15) | |
C4 | −0.06377 (10) | 0.66007 (12) | 0.32962 (3) | 0.01671 (16) | |
C11 | 0.24623 (10) | 0.65632 (11) | 0.29318 (4) | 0.01629 (15) | |
C12 | 0.39053 (11) | 0.61592 (15) | 0.30814 (4) | 0.0241 (2) | |
C13 | 0.47786 (13) | 0.55497 (19) | 0.27360 (5) | 0.0327 (3) | |
C14 | 0.42237 (13) | 0.53479 (17) | 0.22310 (5) | 0.0299 (2) | |
C15 | 0.27992 (12) | 0.57465 (17) | 0.20743 (4) | 0.0278 (2) | |
C16 | 0.19275 (11) | 0.63426 (14) | 0.24231 (4) | 0.02286 (19) | |
C21 | 0.13592 (10) | 0.95457 (11) | 0.33727 (3) | 0.01501 (15) | |
C22 | 0.06531 (11) | 1.04575 (11) | 0.37085 (4) | 0.01830 (16) | |
C23 | 0.06796 (13) | 1.20713 (12) | 0.36832 (4) | 0.02196 (19) | |
C24 | 0.14396 (13) | 1.28043 (12) | 0.33273 (4) | 0.02280 (19) | |
C25 | 0.21691 (12) | 1.19286 (12) | 0.29971 (4) | 0.02075 (18) | |
C26 | 0.21116 (10) | 1.03123 (12) | 0.30164 (4) | 0.01755 (16) | |
C31 | −0.28420 (10) | 0.89115 (11) | 0.45552 (3) | 0.01601 (15) | |
C32 | −0.21949 (10) | 1.03607 (12) | 0.46449 (4) | 0.01798 (16) | |
C33 | −0.30174 (11) | 1.16967 (12) | 0.45460 (4) | 0.01966 (17) | |
C34 | −0.44848 (11) | 1.15999 (13) | 0.43590 (4) | 0.02177 (18) | |
C35 | −0.51108 (12) | 1.01351 (15) | 0.42755 (4) | 0.0254 (2) | |
C36 | −0.43020 (11) | 0.87854 (13) | 0.43712 (4) | 0.02209 (18) | |
C37 | −0.53640 (14) | 1.30571 (16) | 0.42543 (5) | 0.0327 (3) | |
H37A | −0.5365 | 1.3349 | 0.3897 | 0.049* | |
H37B | −0.4939 | 1.3899 | 0.4471 | 0.049* | |
H37C | −0.636 | 1.2871 | 0.4327 | 0.049* | |
H1A | 0.2408 (17) | 0.5665 (19) | 0.4061 (6) | 0.025 (4)* | |
H1B | 0.2211 (19) | 0.728 (2) | 0.4305 (7) | 0.032 (4)* | |
H2 | 0.0281 (16) | 0.5242 (19) | 0.4482 (6) | 0.023 (4)* | |
H3 | −0.1733 (16) | 0.5309 (18) | 0.3848 (6) | 0.022 (4)* | |
H4A | −0.139 (2) | 0.738 (2) | 0.3165 (7) | 0.034 (5)* | |
H4B | −0.0687 (17) | 0.5723 (19) | 0.3058 (6) | 0.024 (4)* | |
H12 | 0.4321 (19) | 0.630 (2) | 0.3439 (7) | 0.034 (4)* | |
H13 | 0.575 (2) | 0.518 (2) | 0.2855 (7) | 0.047 (5)* | |
H14 | 0.4838 (18) | 0.488 (2) | 0.1992 (6) | 0.030 (4)* | |
H15 | 0.2460 (19) | 0.563 (2) | 0.1731 (7) | 0.035 (4)* | |
H16 | 0.096 (2) | 0.662 (2) | 0.2319 (7) | 0.038 (5)* | |
H22 | 0.0151 (18) | 0.996 (2) | 0.3943 (6) | 0.028 (4)* | |
H23 | 0.015 (2) | 1.266 (2) | 0.3905 (7) | 0.035 (5)* | |
H24 | 0.1464 (19) | 1.394 (2) | 0.3307 (7) | 0.038 (5)* | |
H25 | 0.2742 (19) | 1.2443 (19) | 0.2754 (7) | 0.031 (4)* | |
H26 | 0.2602 (18) | 0.9671 (19) | 0.2775 (6) | 0.028 (4)* | |
H32 | −0.1190 (18) | 1.044 (2) | 0.4780 (6) | 0.030 (4)* | |
H33 | −0.2565 (18) | 1.2705 (19) | 0.4593 (6) | 0.025 (4)* | |
H35 | −0.610 (2) | 1.008 (2) | 0.4167 (7) | 0.042 (5)* | |
H36 | −0.476 (2) | 0.774 (2) | 0.4309 (7) | 0.034 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.02066 (11) | 0.01363 (10) | 0.01537 (10) | 0.00007 (7) | 0.00708 (7) | 0.00102 (7) |
Si1 | 0.01555 (11) | 0.01197 (11) | 0.01277 (11) | 0.00153 (8) | 0.00341 (8) | 0.00025 (7) |
O1 | 0.0286 (4) | 0.0230 (4) | 0.0142 (3) | 0.0054 (3) | 0.0038 (3) | 0.0017 (2) |
O2 | 0.0306 (4) | 0.0162 (3) | 0.0315 (4) | −0.0050 (3) | 0.0163 (3) | 0.0003 (3) |
N1 | 0.0176 (3) | 0.0128 (3) | 0.0140 (3) | 0.0003 (2) | 0.0047 (2) | 0.0000 (2) |
C1 | 0.0177 (4) | 0.0169 (4) | 0.0153 (4) | 0.0040 (3) | 0.0023 (3) | 0.0011 (3) |
C2 | 0.0212 (4) | 0.0121 (3) | 0.0150 (3) | 0.0027 (3) | 0.0048 (3) | 0.0019 (3) |
C3 | 0.0199 (4) | 0.0140 (4) | 0.0163 (4) | −0.0022 (3) | 0.0054 (3) | −0.0021 (3) |
C4 | 0.0182 (4) | 0.0186 (4) | 0.0135 (3) | −0.0006 (3) | 0.0026 (3) | −0.0016 (3) |
C11 | 0.0178 (4) | 0.0150 (4) | 0.0169 (4) | 0.0008 (3) | 0.0055 (3) | −0.0005 (3) |
C12 | 0.0194 (4) | 0.0336 (6) | 0.0198 (4) | 0.0040 (4) | 0.0049 (3) | −0.0019 (4) |
C13 | 0.0193 (4) | 0.0525 (8) | 0.0273 (5) | 0.0086 (5) | 0.0072 (4) | −0.0055 (5) |
C14 | 0.0232 (5) | 0.0420 (7) | 0.0266 (5) | 0.0016 (4) | 0.0117 (4) | −0.0097 (5) |
C15 | 0.0232 (5) | 0.0413 (6) | 0.0200 (4) | −0.0005 (4) | 0.0070 (3) | −0.0092 (4) |
C16 | 0.0195 (4) | 0.0319 (5) | 0.0178 (4) | 0.0031 (4) | 0.0048 (3) | −0.0039 (4) |
C21 | 0.0180 (4) | 0.0130 (3) | 0.0142 (3) | −0.0002 (3) | 0.0024 (3) | 0.0007 (3) |
C22 | 0.0269 (4) | 0.0131 (4) | 0.0156 (4) | 0.0011 (3) | 0.0057 (3) | 0.0002 (3) |
C23 | 0.0347 (5) | 0.0136 (4) | 0.0179 (4) | 0.0014 (4) | 0.0049 (4) | −0.0019 (3) |
C24 | 0.0347 (5) | 0.0135 (4) | 0.0197 (4) | −0.0044 (4) | 0.0006 (4) | 0.0006 (3) |
C25 | 0.0259 (4) | 0.0172 (4) | 0.0192 (4) | −0.0054 (3) | 0.0026 (3) | 0.0029 (3) |
C26 | 0.0189 (4) | 0.0171 (4) | 0.0172 (4) | −0.0015 (3) | 0.0044 (3) | 0.0014 (3) |
C31 | 0.0170 (4) | 0.0157 (4) | 0.0160 (4) | 0.0000 (3) | 0.0046 (3) | −0.0018 (3) |
C32 | 0.0155 (4) | 0.0166 (4) | 0.0217 (4) | 0.0004 (3) | 0.0015 (3) | −0.0009 (3) |
C33 | 0.0200 (4) | 0.0167 (4) | 0.0222 (4) | 0.0015 (3) | 0.0020 (3) | −0.0003 (3) |
C34 | 0.0203 (4) | 0.0241 (5) | 0.0207 (4) | 0.0053 (4) | 0.0011 (3) | −0.0003 (3) |
C35 | 0.0173 (4) | 0.0290 (5) | 0.0287 (5) | 0.0005 (4) | −0.0025 (3) | −0.0031 (4) |
C36 | 0.0189 (4) | 0.0229 (5) | 0.0244 (4) | −0.0030 (3) | 0.0019 (3) | −0.0051 (4) |
C37 | 0.0278 (5) | 0.0297 (6) | 0.0393 (6) | 0.0118 (5) | −0.0018 (5) | 0.0036 (5) |
Geometric parameters (Å, º) top
S1—O1 | 1.4399 (8) | C15—H15 | 0.936 (18) |
S1—O2 | 1.4413 (8) | C16—H16 | 0.944 (18) |
S1—N1 | 1.6597 (8) | C21—C26 | 1.4024 (13) |
S1—C31 | 1.7561 (10) | C21—C22 | 1.4043 (13) |
Si1—C11 | 1.8756 (9) | C22—C23 | 1.3910 (14) |
Si1—C21 | 1.8682 (10) | C22—H22 | 0.924 (17) |
Si1—C1 | 1.9004 (10) | C23—C24 | 1.3924 (15) |
Si1—C4 | 1.8991 (10) | C23—H23 | 0.954 (19) |
N1—C2 | 1.4958 (12) | C24—C25 | 1.3889 (16) |
N1—C3 | 1.4918 (12) | C24—H24 | 0.98 (2) |
C1—C2 | 1.5153 (13) | C25—C26 | 1.3935 (14) |
C1—H1A | 0.965 (16) | C25—H25 | 0.986 (18) |
C1—H1B | 0.971 (18) | C26—H26 | 0.994 (17) |
C2—C3 | 1.4979 (14) | C31—C32 | 1.3938 (13) |
C2—H2 | 0.962 (16) | C31—C36 | 1.3941 (14) |
C3—C4 | 1.5153 (13) | C32—C33 | 1.3895 (14) |
C3—H3 | 0.978 (16) | C32—H32 | 0.965 (17) |
C4—H4A | 1.000 (18) | C33—C34 | 1.4008 (15) |
C4—H4B | 0.983 (16) | C33—H33 | 0.966 (16) |
C11—C16 | 1.3982 (14) | C34—C35 | 1.3959 (17) |
C11—C12 | 1.3993 (14) | C34—C37 | 1.5058 (16) |
C12—C13 | 1.3934 (15) | C35—C36 | 1.3916 (16) |
C12—H12 | 0.991 (18) | C35—H35 | 0.937 (19) |
C13—C14 | 1.3916 (18) | C36—H36 | 0.998 (18) |
C13—H13 | 0.97 (2) | C37—H37A | 0.98 |
C14—C15 | 1.3859 (17) | C37—H37B | 0.98 |
C14—H14 | 0.986 (17) | C37—H37C | 0.98 |
C15—C16 | 1.3946 (14) | | |
| | | |
O1—S1—O2 | 118.31 (5) | C13—C14—H14 | 119.5 (10) |
O1—S1—N1 | 105.65 (5) | C14—C15—C16 | 119.91 (10) |
O2—S1—N1 | 111.86 (4) | C14—C15—H15 | 118.2 (11) |
O1—S1—C31 | 108.83 (5) | C16—C15—H15 | 121.9 (11) |
O2—S1—C31 | 109.40 (5) | C15—C16—C11 | 121.38 (10) |
N1—S1—C31 | 101.40 (4) | C15—C16—H16 | 120.5 (11) |
C11—Si1—C1 | 111.88 (4) | C11—C16—H16 | 118.1 (11) |
C21—Si1—C1 | 113.80 (4) | C26—C21—C22 | 117.95 (9) |
C11—Si1—C4 | 112.63 (4) | C26—C21—Si1 | 121.09 (7) |
C21—Si1—C4 | 112.64 (4) | C22—C21—Si1 | 120.96 (7) |
C21—Si1—C11 | 108.92 (4) | C23—C22—C21 | 121.03 (9) |
C1—Si1—C4 | 96.65 (4) | C23—C22—H22 | 120.5 (11) |
C3—N1—C2 | 60.18 (6) | C21—C22—H22 | 118.5 (11) |
C2—N1—S1 | 115.30 (6) | C22—C23—C24 | 119.89 (10) |
C3—N1—S1 | 119.20 (6) | C22—C23—H23 | 119.3 (11) |
C2—C1—Si1 | 104.51 (6) | C24—C23—H23 | 120.8 (11) |
C2—C1—H1A | 108.3 (10) | C25—C24—C23 | 120.18 (10) |
Si1—C1—H1A | 112.6 (9) | C25—C24—H24 | 119.3 (11) |
C2—C1—H1B | 110.1 (11) | C23—C24—H24 | 120.5 (11) |
Si1—C1—H1B | 114.5 (10) | C24—C25—C26 | 119.68 (9) |
H1A—C1—H1B | 106.6 (13) | C24—C25—H25 | 120.4 (10) |
N1—C2—C3 | 59.78 (6) | C26—C25—H25 | 119.9 (10) |
N1—C2—C1 | 112.20 (7) | C25—C26—C21 | 121.25 (9) |
C1—C2—C3 | 116.44 (8) | C25—C26—H26 | 120.6 (10) |
N1—C2—H2 | 114.2 (9) | C21—C26—H26 | 118.1 (10) |
C3—C2—H2 | 116.1 (9) | C32—C31—C36 | 120.94 (9) |
C1—C2—H2 | 122.0 (9) | C32—C31—S1 | 118.66 (7) |
N1—C3—C2 | 60.04 (6) | C36—C31—S1 | 120.40 (8) |
N1—C3—C4 | 113.02 (8) | C33—C32—C31 | 119.38 (9) |
C2—C3—C4 | 116.04 (8) | C33—C32—H32 | 119.9 (11) |
N1—C3—H3 | 114.9 (9) | C31—C32—H32 | 120.7 (10) |
C2—C3—H3 | 117.5 (9) | C32—C33—C34 | 120.73 (10) |
C4—C3—H3 | 120.5 (9) | C32—C33—H33 | 119.8 (10) |
C3—C4—Si1 | 104.67 (6) | C34—C33—H33 | 119.5 (10) |
C3—C4—H4A | 109.7 (11) | C35—C34—C33 | 118.82 (10) |
Si1—C4—H4A | 114.8 (10) | C35—C34—C37 | 121.01 (10) |
C3—C4—H4B | 109.7 (9) | C33—C34—C37 | 120.17 (11) |
Si1—C4—H4B | 109.7 (9) | C36—C35—C34 | 121.20 (10) |
H4A—C4—H4B | 108.1 (14) | C36—C35—H35 | 120.4 (12) |
C16—C11—C12 | 117.76 (9) | C34—C35—H35 | 118.4 (12) |
C16—C11—Si1 | 121.06 (7) | C35—C36—C31 | 118.92 (10) |
C12—C11—Si1 | 121.18 (7) | C35—C36—H36 | 120.6 (10) |
C13—C12—C11 | 121.17 (10) | C31—C36—H36 | 120.5 (10) |
C13—C12—H12 | 118.9 (10) | C34—C37—H37A | 109.5 |
C11—C12—H12 | 119.9 (10) | C34—C37—H37B | 109.5 |
C14—C13—C12 | 120.00 (11) | H37A—C37—H37B | 109.5 |
C14—C13—H13 | 120.1 (12) | C34—C37—H37C | 109.5 |
C12—C13—H13 | 119.7 (12) | H37A—C37—H37C | 109.5 |
C15—C14—C13 | 119.77 (10) | H37B—C37—H37C | 109.5 |
C15—C14—H14 | 120.7 (10) | | |
| | | |
O1—S1—N1—C3 | 133.46 (7) | C13—C14—C15—C16 | −0.2 (2) |
O2—S1—N1—C3 | 3.43 (9) | C14—C15—C16—C11 | 0.5 (2) |
C31—S1—N1—C3 | −113.06 (7) | C12—C11—C16—C15 | −0.26 (17) |
O1—S1—N1—C2 | 64.92 (7) | Si1—C11—C16—C15 | 179.58 (10) |
O2—S1—N1—C2 | −65.10 (8) | C11—Si1—C21—C26 | 4.90 (9) |
C31—S1—N1—C2 | 178.41 (7) | C4—Si1—C21—C26 | −120.80 (8) |
C21—Si1—C1—C2 | 107.11 (7) | C1—Si1—C21—C26 | 130.47 (8) |
C11—Si1—C1—C2 | −128.91 (6) | C11—Si1—C21—C22 | −175.58 (8) |
C4—Si1—C1—C2 | −11.25 (7) | C4—Si1—C21—C22 | 58.72 (9) |
S1—N1—C2—C3 | 110.55 (7) | C1—Si1—C21—C22 | −50.01 (9) |
C3—N1—C2—C1 | 108.60 (9) | C26—C21—C22—C23 | 1.02 (15) |
S1—N1—C2—C1 | −140.85 (7) | Si1—C21—C22—C23 | −178.51 (8) |
Si1—C1—C2—N1 | −58.53 (8) | C21—C22—C23—C24 | −1.31 (17) |
Si1—C1—C2—C3 | 7.62 (9) | C22—C23—C24—C25 | 0.11 (17) |
S1—N1—C3—C2 | −104.12 (7) | C23—C24—C25—C26 | 1.35 (17) |
C2—N1—C3—C4 | −107.79 (9) | C24—C25—C26—C21 | −1.64 (16) |
S1—N1—C3—C4 | 148.09 (7) | C22—C21—C26—C25 | 0.46 (14) |
C1—C2—C3—N1 | −101.46 (9) | Si1—C21—C26—C25 | 179.99 (8) |
N1—C2—C3—C4 | 102.76 (9) | O1—S1—C31—C32 | 38.38 (9) |
C1—C2—C3—C4 | 1.30 (12) | O2—S1—C31—C32 | 169.02 (7) |
N1—C3—C4—Si1 | 57.16 (9) | N1—S1—C31—C32 | −72.70 (8) |
C2—C3—C4—Si1 | −9.49 (10) | O1—S1—C31—C36 | −141.19 (8) |
C21—Si1—C4—C3 | −107.35 (7) | O2—S1—C31—C36 | −10.55 (10) |
C11—Si1—C4—C3 | 128.98 (6) | N1—S1—C31—C36 | 107.73 (8) |
C1—Si1—C4—C3 | 11.92 (7) | C36—C31—C32—C33 | −0.42 (15) |
C21—Si1—C11—C16 | −86.14 (9) | S1—C31—C32—C33 | −179.99 (8) |
C4—Si1—C11—C16 | 39.57 (10) | C31—C32—C33—C34 | 0.15 (15) |
C1—Si1—C11—C16 | 147.18 (9) | C32—C33—C34—C35 | 0.29 (16) |
C21—Si1—C11—C12 | 93.70 (9) | C32—C33—C34—C37 | 179.90 (10) |
C4—Si1—C11—C12 | −140.59 (9) | C33—C34—C35—C36 | −0.47 (17) |
C1—Si1—C11—C12 | −32.98 (10) | C37—C34—C35—C36 | 179.93 (11) |
C16—C11—C12—C13 | −0.33 (18) | C34—C35—C36—C31 | 0.20 (17) |
Si1—C11—C12—C13 | 179.83 (11) | C32—C31—C36—C35 | 0.25 (15) |
C11—C12—C13—C14 | 0.7 (2) | S1—C31—C36—C35 | 179.81 (8) |
C12—C13—C14—C15 | −0.4 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···N1 | 0.92 (2) | 2.59 (2) | 3.376 (1) | 143 (1) |
C2—H2···O1i | 0.96 (2) | 2.59 (2) | 3.457 (1) | 151 (1) |
C32—H32···O1ii | 0.97 (2) | 2.57 (2) | 3.348 (1) | 138 (1) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z+1. |
Crystal data top
C23H23NO2SSi | F(000) = 856 |
Mr = 405.57 | Dx = 1.237 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4105 (2) Å | Cell parameters from 21783 reflections |
b = 8.6979 (1) Å | θ = 1.0–27.5° |
c = 26.7515 (5) Å | µ = 0.22 mm−1 |
β = 95.993 (1)° | T = 293 K |
V = 2177.69 (7) Å3 | Block, colourless |
Z = 4 | 0.35 × 0.3 × 0.3 mm |
Data collection top
KappaCCD diffractometer | Rint = 0.017 |
CCD scans | θmax = 27.5°, θmin = 3.2° |
8807 measured reflections | h = −12→12 |
4916 independent reflections | k = −11→11 |
3807 reflections with I > 2σ(I) | l = −34→34 |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.045 | w = 1/[σ2(Fo2) + (0.066P)2 + 0.5368P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.131 | (Δ/σ)max = 0.001 |
S = 1.03 | Δρmax = 0.25 e Å−3 |
4916 reflections | Δρmin = −0.38 e Å−3 |
253 parameters | |
Crystal data top
C23H23NO2SSi | V = 2177.69 (7) Å3 |
Mr = 405.57 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.4105 (2) Å | µ = 0.22 mm−1 |
b = 8.6979 (1) Å | T = 293 K |
c = 26.7515 (5) Å | 0.35 × 0.3 × 0.3 mm |
β = 95.993 (1)° | |
Data collection top
KappaCCD diffractometer | 3807 reflections with I > 2σ(I) |
8807 measured reflections | Rint = 0.017 |
4916 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.25 e Å−3 |
4916 reflections | Δρmin = −0.38 e Å−3 |
253 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | −0.17530 (5) | 0.72294 (5) | 0.468052 (18) | 0.05611 (16) | |
Si1 | 0.12932 (5) | 0.73530 (5) | 0.340399 (17) | 0.04385 (14) | |
O1 | −0.08056 (17) | 0.74833 (17) | 0.51276 (5) | 0.0712 (4) | |
O2 | −0.26601 (18) | 0.59055 (17) | 0.46587 (7) | 0.0818 (5) | |
N1 | −0.07328 (15) | 0.72568 (16) | 0.42104 (5) | 0.0469 (3) | |
C1 | 0.17403 (19) | 0.6521 (2) | 0.40544 (7) | 0.0538 (4) | |
H1A | 0.2402 | 0.5668 | 0.4047 | 0.065* | |
H1B | 0.2164 | 0.7296 | 0.4284 | 0.065* | |
C2 | 0.0330 (2) | 0.59847 (19) | 0.42102 (7) | 0.0525 (4) | |
H2 | 0.0337 | 0.5195 | 0.4472 | 0.063* | |
C3 | −0.0914 (2) | 0.6044 (2) | 0.38175 (7) | 0.0526 (4) | |
H3 | −0.1682 | 0.5291 | 0.3834 | 0.063* | |
C4 | −0.06028 (19) | 0.6604 (2) | 0.33082 (7) | 0.0526 (4) | |
H4A | −0.126 | 0.7415 | 0.3189 | 0.063* | |
H4B | −0.0683 | 0.577 | 0.3066 | 0.063* | |
C11 | 0.24514 (19) | 0.6540 (2) | 0.29406 (7) | 0.0507 (4) | |
C12 | 0.3854 (2) | 0.6104 (3) | 0.30814 (9) | 0.0729 (6) | |
H12 | 0.4232 | 0.6221 | 0.3415 | 0.087* | |
C13 | 0.4704 (3) | 0.5501 (4) | 0.27386 (11) | 0.0988 (9) | |
H13 | 0.5637 | 0.5204 | 0.2844 | 0.119* | |
C14 | 0.4180 (3) | 0.5339 (4) | 0.22475 (11) | 0.0957 (9) | |
H14 | 0.4758 | 0.4948 | 0.2016 | 0.115* | |
C15 | 0.2808 (3) | 0.5752 (4) | 0.20956 (10) | 0.0881 (8) | |
H15 | 0.2445 | 0.5637 | 0.1761 | 0.106* | |
C16 | 0.1955 (2) | 0.6344 (3) | 0.24403 (8) | 0.0718 (6) | |
H16 | 0.1018 | 0.6618 | 0.2332 | 0.086* | |
C21 | 0.13833 (18) | 0.9496 (2) | 0.33789 (6) | 0.0471 (4) | |
C22 | 0.0701 (2) | 1.0402 (2) | 0.37110 (7) | 0.0609 (5) | |
H22 | 0.0219 | 0.993 | 0.3956 | 0.073* | |
C23 | 0.0727 (3) | 1.1990 (2) | 0.36836 (8) | 0.0724 (6) | |
H23 | 0.0256 | 1.2576 | 0.3906 | 0.087* | |
C24 | 0.1449 (3) | 1.2697 (2) | 0.33283 (8) | 0.0707 (6) | |
H24 | 0.1464 | 1.3765 | 0.331 | 0.085* | |
C25 | 0.2148 (2) | 1.1843 (2) | 0.30012 (8) | 0.0652 (5) | |
H25 | 0.2651 | 1.2329 | 0.2765 | 0.078* | |
C26 | 0.2104 (2) | 1.0253 (2) | 0.30231 (7) | 0.0558 (4) | |
H26 | 0.2566 | 0.9679 | 0.2795 | 0.067* | |
C31 | −0.27995 (18) | 0.8887 (2) | 0.45497 (7) | 0.0506 (4) | |
C32 | −0.2189 (2) | 1.0313 (2) | 0.46442 (8) | 0.0595 (5) | |
H32 | −0.1236 | 1.039 | 0.4775 | 0.071* | |
C33 | −0.2988 (2) | 1.1618 (2) | 0.45460 (8) | 0.0631 (5) | |
H33 | −0.2567 | 1.2574 | 0.4611 | 0.076* | |
C34 | −0.4408 (2) | 1.1538 (3) | 0.43525 (8) | 0.0677 (5) | |
C35 | −0.5001 (2) | 1.0104 (3) | 0.42628 (10) | 0.0820 (7) | |
H35 | −0.5957 | 1.003 | 0.4135 | 0.098* | |
C36 | −0.4220 (2) | 0.8775 (3) | 0.43566 (9) | 0.0723 (6) | |
H36 | −0.464 | 0.7819 | 0.4291 | 0.087* | |
C37 | −0.5277 (3) | 1.2985 (4) | 0.42501 (14) | 0.1049 (9) | |
H37A | −0.5176 | 1.3342 | 0.3916 | 0.157* | |
H37B | −0.4943 | 1.3763 | 0.4489 | 0.157* | |
H37C | −0.6265 | 1.2771 | 0.4281 | 0.157* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0705 (3) | 0.0485 (3) | 0.0528 (3) | 0.0005 (2) | 0.0224 (2) | 0.00484 (19) |
Si1 | 0.0501 (3) | 0.0385 (2) | 0.0438 (3) | 0.00471 (19) | 0.00893 (19) | 0.00103 (17) |
O1 | 0.0934 (10) | 0.0772 (10) | 0.0434 (7) | 0.0179 (8) | 0.0094 (7) | 0.0070 (6) |
O2 | 0.0985 (11) | 0.0542 (8) | 0.1015 (12) | −0.0149 (8) | 0.0518 (9) | 0.0028 (8) |
N1 | 0.0557 (8) | 0.0411 (7) | 0.0455 (8) | 0.0010 (6) | 0.0133 (6) | 0.0017 (6) |
C1 | 0.0576 (10) | 0.0520 (10) | 0.0518 (10) | 0.0120 (8) | 0.0056 (8) | 0.0041 (8) |
C2 | 0.0727 (11) | 0.0371 (8) | 0.0492 (9) | 0.0086 (8) | 0.0134 (8) | 0.0068 (7) |
C3 | 0.0618 (10) | 0.0430 (9) | 0.0550 (10) | −0.0077 (8) | 0.0149 (8) | −0.0043 (7) |
C4 | 0.0581 (10) | 0.0538 (10) | 0.0459 (9) | −0.0017 (8) | 0.0048 (7) | −0.0050 (7) |
C11 | 0.0543 (9) | 0.0430 (9) | 0.0567 (10) | 0.0024 (8) | 0.0150 (8) | −0.0003 (7) |
C12 | 0.0602 (11) | 0.0918 (17) | 0.0685 (13) | 0.0079 (11) | 0.0160 (10) | −0.0012 (12) |
C13 | 0.0622 (13) | 0.140 (3) | 0.098 (2) | 0.0236 (15) | 0.0270 (13) | −0.0062 (18) |
C14 | 0.0751 (15) | 0.126 (2) | 0.0929 (19) | 0.0026 (15) | 0.0389 (14) | −0.0306 (17) |
C15 | 0.0761 (15) | 0.125 (2) | 0.0667 (14) | −0.0081 (15) | 0.0230 (11) | −0.0300 (14) |
C16 | 0.0605 (11) | 0.0960 (17) | 0.0603 (12) | 0.0059 (11) | 0.0134 (9) | −0.0142 (11) |
C21 | 0.0545 (9) | 0.0405 (8) | 0.0463 (9) | 0.0003 (7) | 0.0056 (7) | 0.0014 (7) |
C22 | 0.0893 (14) | 0.0440 (10) | 0.0527 (10) | 0.0024 (9) | 0.0225 (10) | 0.0009 (8) |
C23 | 0.1133 (18) | 0.0432 (10) | 0.0630 (13) | 0.0050 (11) | 0.0194 (12) | −0.0061 (9) |
C24 | 0.1068 (17) | 0.0395 (10) | 0.0646 (13) | −0.0091 (10) | 0.0033 (12) | 0.0014 (8) |
C25 | 0.0811 (13) | 0.0542 (11) | 0.0606 (12) | −0.0158 (10) | 0.0083 (10) | 0.0110 (9) |
C26 | 0.0620 (10) | 0.0525 (10) | 0.0542 (10) | −0.0032 (9) | 0.0125 (8) | 0.0018 (8) |
C31 | 0.0517 (9) | 0.0527 (10) | 0.0488 (9) | −0.0013 (8) | 0.0112 (7) | −0.0038 (8) |
C32 | 0.0492 (9) | 0.0569 (11) | 0.0716 (12) | 0.0007 (9) | 0.0021 (9) | −0.0052 (9) |
C33 | 0.0622 (11) | 0.0539 (11) | 0.0725 (13) | 0.0027 (9) | 0.0038 (9) | −0.0024 (9) |
C34 | 0.0613 (11) | 0.0749 (14) | 0.0664 (13) | 0.0137 (11) | 0.0046 (9) | 0.0035 (10) |
C35 | 0.0521 (11) | 0.0976 (19) | 0.0926 (17) | 0.0007 (12) | −0.0106 (11) | −0.0033 (14) |
C36 | 0.0617 (12) | 0.0724 (14) | 0.0817 (15) | −0.0117 (11) | 0.0025 (10) | −0.0134 (11) |
C37 | 0.0871 (18) | 0.099 (2) | 0.125 (2) | 0.0359 (16) | −0.0058 (16) | 0.0161 (18) |
Geometric parameters (Å, º) top
S1—O2 | 1.4310 (15) | C13—C14 | 1.361 (4) |
S1—O1 | 1.4323 (15) | C14—C15 | 1.360 (4) |
S1—N1 | 1.6602 (14) | C15—C16 | 1.384 (3) |
S1—C31 | 1.7602 (19) | C21—C26 | 1.391 (2) |
Si1—C21 | 1.8675 (18) | C21—C22 | 1.393 (2) |
Si1—C11 | 1.8728 (18) | C22—C23 | 1.383 (3) |
Si1—C1 | 1.8907 (18) | C23—C24 | 1.371 (3) |
Si1—C4 | 1.8917 (18) | C24—C25 | 1.367 (3) |
N1—C3 | 1.486 (2) | C25—C26 | 1.385 (3) |
N1—C2 | 1.491 (2) | C31—C32 | 1.379 (3) |
C1—C2 | 1.506 (3) | C31—C36 | 1.385 (3) |
C2—C3 | 1.490 (3) | C32—C33 | 1.372 (3) |
C3—C4 | 1.504 (2) | C33—C34 | 1.384 (3) |
C11—C16 | 1.381 (3) | C34—C35 | 1.377 (3) |
C11—C12 | 1.387 (3) | C34—C37 | 1.511 (3) |
C12—C13 | 1.382 (3) | C35—C36 | 1.379 (3) |
| | | |
O2—S1—O1 | 118.34 (10) | C12—C11—Si1 | 121.78 (15) |
O2—S1—N1 | 111.74 (8) | C13—C12—C11 | 121.6 (2) |
O1—S1—N1 | 105.76 (9) | C14—C13—C12 | 120.2 (2) |
O2—S1—C31 | 109.38 (10) | C15—C14—C13 | 119.9 (2) |
O1—S1—C31 | 109.04 (9) | C14—C15—C16 | 119.8 (2) |
N1—S1—C31 | 101.16 (8) | C11—C16—C15 | 122.0 (2) |
C21—Si1—C11 | 108.76 (8) | C26—C21—C22 | 117.32 (17) |
C21—Si1—C1 | 114.11 (8) | C26—C21—Si1 | 121.61 (13) |
C11—Si1—C1 | 112.06 (8) | C22—C21—Si1 | 121.06 (13) |
C21—Si1—C4 | 112.62 (8) | C23—C22—C21 | 121.25 (19) |
C11—Si1—C4 | 112.71 (8) | C24—C23—C22 | 119.8 (2) |
C1—Si1—C4 | 96.26 (8) | C25—C24—C23 | 120.42 (19) |
C3—N1—C2 | 60.06 (12) | C24—C25—C26 | 119.78 (19) |
C3—N1—S1 | 119.52 (11) | C25—C26—C21 | 121.36 (19) |
C2—N1—S1 | 115.49 (11) | C32—C31—C36 | 119.89 (18) |
C2—C1—Si1 | 104.80 (12) | C32—C31—S1 | 119.11 (14) |
C3—C2—N1 | 59.80 (11) | C36—C31—S1 | 121.00 (15) |
C3—C2—C1 | 116.37 (15) | C33—C32—C31 | 119.99 (18) |
N1—C2—C1 | 112.37 (14) | C32—C33—C34 | 121.2 (2) |
N1—C3—C2 | 60.14 (11) | C35—C34—C33 | 118.0 (2) |
N1—C3—C4 | 113.09 (14) | C35—C34—C37 | 121.4 (2) |
C2—C3—C4 | 115.91 (16) | C33—C34—C37 | 120.6 (2) |
C3—C4—Si1 | 105.01 (12) | C34—C35—C36 | 121.89 (19) |
C16—C11—C12 | 116.45 (18) | C35—C36—C31 | 119.0 (2) |
C16—C11—Si1 | 121.77 (14) | | |
| | | |
O2—S1—N1—C3 | 3.94 (16) | C13—C14—C15—C16 | 0.4 (5) |
O1—S1—N1—C3 | 134.01 (13) | C12—C11—C16—C15 | −0.3 (4) |
C31—S1—N1—C3 | −112.34 (14) | Si1—C11—C16—C15 | 179.6 (2) |
O2—S1—N1—C2 | −64.63 (15) | C14—C15—C16—C11 | 0.2 (4) |
O1—S1—N1—C2 | 65.44 (14) | C11—Si1—C21—C26 | 6.02 (17) |
C31—S1—N1—C2 | 179.09 (12) | C1—Si1—C21—C26 | 131.92 (15) |
C21—Si1—C1—C2 | 107.09 (13) | C4—Si1—C21—C26 | −119.67 (15) |
C11—Si1—C1—C2 | −128.75 (12) | C11—Si1—C21—C22 | −175.40 (15) |
C4—Si1—C1—C2 | −11.14 (13) | C1—Si1—C21—C22 | −49.49 (18) |
S1—N1—C2—C3 | 110.82 (13) | C4—Si1—C21—C22 | 58.92 (17) |
C3—N1—C2—C1 | 108.43 (17) | C26—C21—C22—C23 | 0.7 (3) |
S1—N1—C2—C1 | −140.75 (13) | Si1—C21—C22—C23 | −177.95 (18) |
Si1—C1—C2—C3 | 7.61 (18) | C21—C22—C23—C24 | −0.8 (4) |
Si1—C1—C2—N1 | −58.61 (16) | C22—C23—C24—C25 | −0.2 (4) |
S1—N1—C3—C2 | −104.16 (14) | C23—C24—C25—C26 | 1.2 (3) |
C2—N1—C3—C4 | −107.63 (18) | C24—C25—C26—C21 | −1.3 (3) |
S1—N1—C3—C4 | 148.21 (13) | C22—C21—C26—C25 | 0.3 (3) |
C1—C2—C3—N1 | −101.70 (16) | Si1—C21—C26—C25 | 178.96 (16) |
N1—C2—C3—C4 | 102.94 (17) | O2—S1—C31—C32 | 167.62 (15) |
C1—C2—C3—C4 | 1.2 (2) | O1—S1—C31—C32 | 36.78 (18) |
N1—C3—C4—Si1 | 57.37 (17) | N1—S1—C31—C32 | −74.37 (16) |
C2—C3—C4—Si1 | −9.38 (18) | O2—S1—C31—C36 | −12.1 (2) |
C21—Si1—C4—C3 | −107.61 (13) | O1—S1—C31—C36 | −142.93 (17) |
C11—Si1—C4—C3 | 128.88 (12) | N1—S1—C31—C36 | 105.91 (17) |
C1—Si1—C4—C3 | 11.79 (14) | C36—C31—C32—C33 | −0.1 (3) |
C21—Si1—C11—C16 | −85.08 (18) | S1—C31—C32—C33 | −179.84 (16) |
C1—Si1—C11—C16 | 147.83 (18) | C31—C32—C33—C34 | 0.1 (3) |
C4—Si1—C11—C16 | 40.5 (2) | C32—C33—C34—C35 | 0.3 (3) |
C21—Si1—C11—C12 | 94.80 (18) | C32—C33—C34—C37 | 179.5 (2) |
C1—Si1—C11—C12 | −32.3 (2) | C33—C34—C35—C36 | −0.5 (4) |
C4—Si1—C11—C12 | −139.57 (17) | C37—C34—C35—C36 | −179.7 (3) |
C16—C11—C12—C13 | −0.3 (4) | C34—C35—C36—C31 | 0.4 (4) |
Si1—C11—C12—C13 | 179.8 (2) | C32—C31—C36—C35 | −0.1 (3) |
C11—C12—C13—C14 | 0.9 (5) | S1—C31—C36—C35 | 179.60 (19) |
C12—C13—C14—C15 | −1.0 (5) | | |
Crystal data top
C23H23NO2SSi | F(000) = 856 |
Mr = 405.57 | Dx = 1.237 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4106 (6) Å | Cell parameters from 25 reflections |
b = 8.6993 (3) Å | θ = 9.7–21.5° |
c = 26.7493 (16) Å | µ = 0.22 mm−1 |
β = 96.000 (5)° | T = 293 K |
V = 2177.9 (2) Å3 | Needle, colourless |
Z = 4 | 0.35 × 0.15 × 0.13 mm |
Data collection top
Enraf Nonius TurboCAD4 diffractometer | Rint = 0.024 |
non–profiled ω scans | θmax = 30.0°, θmin = 2.2° |
Absorption correction: ψ scan WinGX (Farrugia, 1999) | h = −13→13 |
Tmin = 0.927, Tmax = 0.972 | k = −1→12 |
7898 measured reflections | l = −37→3 |
6318 independent reflections | 3 standard reflections every 111 reflections |
3267 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.047 | w = 1/[σ2(Fo2) + (0.0477P)2 + 0.7286P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.135 | (Δ/σ)max < 0.001 |
S = 0.99 | Δρmax = 0.24 e Å−3 |
6318 reflections | Δρmin = −0.32 e Å−3 |
253 parameters | |
Crystal data top
C23H23NO2SSi | V = 2177.9 (2) Å3 |
Mr = 405.57 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.4106 (6) Å | µ = 0.22 mm−1 |
b = 8.6993 (3) Å | T = 293 K |
c = 26.7493 (16) Å | 0.35 × 0.15 × 0.13 mm |
β = 96.000 (5)° | |
Data collection top
Enraf Nonius TurboCAD4 diffractometer | 3267 reflections with I > 2σ(I) |
Absorption correction: ψ scan WinGX (Farrugia, 1999) | Rint = 0.024 |
Tmin = 0.927, Tmax = 0.972 | 3 standard reflections every 111 reflections |
7898 measured reflections | intensity decay: none |
6318 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.135 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.24 e Å−3 |
6318 reflections | Δρmin = −0.32 e Å−3 |
253 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | −0.17567 (7) | 0.72295 (7) | 0.46803 (2) | 0.05695 (17) | |
Si1 | 0.12927 (6) | 0.73523 (6) | 0.34040 (2) | 0.04442 (16) | |
O1 | −0.0809 (2) | 0.7483 (2) | 0.51273 (6) | 0.0707 (5) | |
O2 | −0.2666 (2) | 0.5906 (2) | 0.46564 (7) | 0.0822 (6) | |
N1 | −0.07364 (19) | 0.72565 (19) | 0.42104 (6) | 0.0469 (4) | |
C1 | 0.1736 (2) | 0.6523 (3) | 0.40558 (8) | 0.0537 (5) | |
H1A | 0.24 | 0.5672 | 0.4049 | 0.064* | |
H1B | 0.2155 | 0.73 | 0.4286 | 0.064* | |
C2 | 0.0325 (2) | 0.5983 (2) | 0.42101 (8) | 0.0523 (5) | |
H2 | 0.0332 | 0.5195 | 0.4472 | 0.063* | |
C3 | −0.0916 (2) | 0.6039 (2) | 0.38186 (8) | 0.0528 (5) | |
H3 | −0.1683 | 0.5286 | 0.3836 | 0.063* | |
C4 | −0.0603 (2) | 0.6598 (3) | 0.33091 (8) | 0.0530 (5) | |
H4A | −0.1262 | 0.7408 | 0.319 | 0.064* | |
H4B | −0.0681 | 0.5764 | 0.3067 | 0.064* | |
C11 | 0.2451 (2) | 0.6540 (2) | 0.29414 (8) | 0.0500 (5) | |
C12 | 0.3852 (3) | 0.6100 (3) | 0.30825 (10) | 0.0726 (7) | |
H12 | 0.4228 | 0.621 | 0.3416 | 0.087* | |
C13 | 0.4705 (3) | 0.5497 (4) | 0.27365 (13) | 0.0950 (10) | |
H13 | 0.5639 | 0.5201 | 0.284 | 0.114* | |
C14 | 0.4176 (3) | 0.5340 (4) | 0.22468 (13) | 0.0929 (10) | |
H14 | 0.4753 | 0.4949 | 0.2015 | 0.112* | |
C15 | 0.2810 (3) | 0.5752 (4) | 0.20956 (11) | 0.0870 (9) | |
H15 | 0.2447 | 0.5638 | 0.1761 | 0.104* | |
C16 | 0.1955 (3) | 0.6343 (3) | 0.24403 (10) | 0.0715 (7) | |
H16 | 0.1018 | 0.6615 | 0.2332 | 0.086* | |
C21 | 0.1380 (2) | 0.9497 (2) | 0.33790 (8) | 0.0469 (5) | |
C22 | 0.0700 (3) | 1.0407 (3) | 0.37106 (9) | 0.0611 (6) | |
H22 | 0.0217 | 0.9936 | 0.3955 | 0.073* | |
C23 | 0.0725 (3) | 1.1987 (3) | 0.36841 (10) | 0.0729 (8) | |
H23 | 0.0252 | 1.2572 | 0.3906 | 0.088* | |
C24 | 0.1452 (3) | 1.2698 (3) | 0.33287 (10) | 0.0709 (7) | |
H24 | 0.1471 | 1.3765 | 0.3311 | 0.085* | |
C25 | 0.2145 (3) | 1.1847 (3) | 0.30018 (9) | 0.0643 (7) | |
H25 | 0.2646 | 1.2332 | 0.2765 | 0.077* | |
C26 | 0.2102 (2) | 1.0255 (3) | 0.30234 (9) | 0.0543 (6) | |
H26 | 0.2565 | 0.9682 | 0.2796 | 0.065* | |
C31 | −0.2797 (2) | 0.8884 (3) | 0.45492 (8) | 0.0513 (5) | |
C32 | −0.2191 (3) | 1.0312 (3) | 0.46432 (9) | 0.0593 (6) | |
H32 | −0.1239 | 1.039 | 0.4774 | 0.071* | |
C33 | −0.2990 (3) | 1.1619 (3) | 0.45440 (10) | 0.0645 (6) | |
H33 | −0.2569 | 1.2576 | 0.4609 | 0.077* | |
C34 | −0.4409 (3) | 1.1541 (3) | 0.43501 (10) | 0.0681 (7) | |
C35 | −0.5001 (3) | 1.0105 (4) | 0.42603 (12) | 0.0829 (9) | |
H35 | −0.5955 | 1.0028 | 0.4132 | 0.099* | |
C36 | −0.4216 (3) | 0.8778 (3) | 0.43563 (10) | 0.0715 (7) | |
H36 | −0.4636 | 0.7821 | 0.4292 | 0.086* | |
C37 | −0.5278 (4) | 1.2988 (4) | 0.42481 (15) | 0.1067 (12) | |
H37A | −0.5177 | 1.3345 | 0.3914 | 0.16* | |
H37B | −0.4944 | 1.3766 | 0.4487 | 0.16* | |
H37C | −0.6266 | 1.2774 | 0.4279 | 0.16* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0717 (4) | 0.0471 (3) | 0.0556 (3) | 0.0003 (3) | 0.0235 (3) | 0.0049 (3) |
Si1 | 0.0510 (3) | 0.0376 (3) | 0.0455 (3) | 0.0046 (3) | 0.0090 (2) | 0.0010 (2) |
O1 | 0.0925 (12) | 0.0744 (12) | 0.0455 (9) | 0.0185 (10) | 0.0086 (9) | 0.0072 (8) |
O2 | 0.0988 (14) | 0.0527 (10) | 0.1037 (14) | −0.0153 (10) | 0.0519 (12) | 0.0024 (10) |
N1 | 0.0559 (10) | 0.0404 (9) | 0.0463 (9) | 0.0026 (8) | 0.0142 (8) | 0.0021 (8) |
C1 | 0.0590 (13) | 0.0486 (12) | 0.0535 (13) | 0.0138 (11) | 0.0058 (10) | 0.0042 (10) |
C2 | 0.0691 (14) | 0.0369 (11) | 0.0523 (12) | 0.0093 (10) | 0.0132 (11) | 0.0084 (10) |
C3 | 0.0633 (14) | 0.0417 (11) | 0.0555 (13) | −0.0076 (10) | 0.0160 (11) | −0.0057 (10) |
C4 | 0.0602 (13) | 0.0507 (13) | 0.0480 (12) | 0.0011 (11) | 0.0053 (10) | −0.0040 (10) |
C11 | 0.0540 (13) | 0.0415 (11) | 0.0562 (13) | 0.0011 (10) | 0.0143 (10) | −0.0014 (10) |
C12 | 0.0609 (15) | 0.090 (2) | 0.0681 (16) | 0.0075 (15) | 0.0128 (13) | 0.0009 (15) |
C13 | 0.0611 (17) | 0.133 (3) | 0.094 (2) | 0.0209 (19) | 0.0257 (17) | −0.007 (2) |
C14 | 0.0704 (19) | 0.119 (3) | 0.095 (2) | 0.0027 (18) | 0.0343 (17) | −0.031 (2) |
C15 | 0.0765 (19) | 0.121 (3) | 0.0662 (17) | −0.0082 (19) | 0.0192 (15) | −0.0298 (18) |
C16 | 0.0575 (14) | 0.095 (2) | 0.0635 (16) | 0.0063 (14) | 0.0127 (12) | −0.0117 (15) |
C21 | 0.0552 (12) | 0.0392 (10) | 0.0463 (11) | 0.0022 (10) | 0.0054 (10) | 0.0022 (9) |
C22 | 0.0901 (18) | 0.0414 (12) | 0.0551 (14) | 0.0017 (12) | 0.0227 (13) | 0.0014 (10) |
C23 | 0.115 (2) | 0.0435 (14) | 0.0621 (16) | 0.0046 (14) | 0.0202 (15) | −0.0063 (11) |
C24 | 0.106 (2) | 0.0386 (12) | 0.0666 (16) | −0.0086 (14) | 0.0000 (15) | 0.0008 (12) |
C25 | 0.0790 (17) | 0.0528 (14) | 0.0611 (15) | −0.0151 (13) | 0.0077 (13) | 0.0096 (12) |
C26 | 0.0598 (13) | 0.0510 (13) | 0.0534 (13) | −0.0018 (11) | 0.0112 (11) | 0.0011 (10) |
C31 | 0.0534 (13) | 0.0522 (13) | 0.0498 (12) | −0.0008 (10) | 0.0123 (10) | −0.0031 (10) |
C32 | 0.0505 (13) | 0.0539 (14) | 0.0723 (16) | 0.0020 (11) | 0.0004 (12) | −0.0046 (12) |
C33 | 0.0638 (15) | 0.0537 (14) | 0.0755 (17) | 0.0032 (12) | 0.0048 (13) | −0.0022 (13) |
C34 | 0.0628 (16) | 0.0744 (18) | 0.0666 (16) | 0.0148 (14) | 0.0038 (13) | 0.0020 (14) |
C35 | 0.0527 (15) | 0.098 (2) | 0.094 (2) | 0.0005 (16) | −0.0126 (15) | −0.0032 (18) |
C36 | 0.0605 (16) | 0.0710 (18) | 0.0819 (19) | −0.0115 (14) | 0.0030 (14) | −0.0108 (15) |
C37 | 0.090 (2) | 0.101 (3) | 0.126 (3) | 0.036 (2) | −0.003 (2) | 0.016 (2) |
Geometric parameters (Å, º) top
S1—O2 | 1.4316 (18) | C13—C14 | 1.359 (4) |
S1—O1 | 1.4321 (18) | C14—C15 | 1.355 (4) |
S1—N1 | 1.6598 (17) | C15—C16 | 1.385 (4) |
S1—C31 | 1.756 (2) | C21—C26 | 1.392 (3) |
Si1—C21 | 1.869 (2) | C21—C22 | 1.393 (3) |
Si1—C11 | 1.871 (2) | C22—C23 | 1.376 (3) |
Si1—C4 | 1.893 (2) | C23—C24 | 1.375 (4) |
Si1—C1 | 1.893 (2) | C24—C25 | 1.363 (4) |
N1—C3 | 1.487 (3) | C25—C26 | 1.387 (3) |
N1—C2 | 1.492 (3) | C31—C32 | 1.379 (3) |
C1—C2 | 1.506 (3) | C31—C36 | 1.383 (3) |
C2—C3 | 1.486 (3) | C32—C33 | 1.374 (3) |
C3—C4 | 1.505 (3) | C33—C34 | 1.383 (3) |
C11—C16 | 1.383 (3) | C34—C35 | 1.379 (4) |
C11—C12 | 1.386 (3) | C34—C37 | 1.511 (4) |
C12—C13 | 1.390 (4) | C35—C36 | 1.380 (4) |
| | | |
O2—S1—O1 | 118.58 (12) | C12—C11—Si1 | 121.82 (18) |
O2—S1—N1 | 111.58 (10) | C11—C12—C13 | 121.5 (3) |
O1—S1—N1 | 105.72 (10) | C14—C13—C12 | 120.1 (3) |
O2—S1—C31 | 109.41 (12) | C15—C14—C13 | 120.1 (3) |
O1—S1—C31 | 109.03 (11) | C14—C15—C16 | 119.9 (3) |
N1—S1—C31 | 101.05 (10) | C11—C16—C15 | 122.0 (2) |
C21—Si1—C11 | 108.82 (10) | C26—C21—C22 | 117.1 (2) |
C21—Si1—C4 | 112.66 (10) | C26—C21—Si1 | 121.58 (17) |
C11—Si1—C4 | 112.74 (10) | C22—C21—Si1 | 121.31 (17) |
C21—Si1—C1 | 114.04 (10) | C23—C22—C21 | 121.5 (2) |
C11—Si1—C1 | 112.19 (10) | C24—C23—C22 | 119.8 (2) |
C4—Si1—C1 | 96.05 (10) | C25—C24—C23 | 120.3 (2) |
C3—N1—C2 | 59.83 (14) | C24—C25—C26 | 119.9 (2) |
C3—N1—S1 | 119.44 (14) | C25—C26—C21 | 121.3 (2) |
C2—N1—S1 | 115.48 (13) | C32—C31—C36 | 119.5 (2) |
C2—C1—Si1 | 104.82 (15) | C32—C31—S1 | 119.38 (17) |
C3—C2—N1 | 59.92 (13) | C36—C31—S1 | 121.08 (19) |
C3—C2—C1 | 116.55 (18) | C33—C32—C31 | 120.2 (2) |
N1—C2—C1 | 112.20 (17) | C32—C33—C34 | 121.3 (2) |
C2—C3—N1 | 60.24 (14) | C35—C34—C33 | 117.8 (2) |
C2—C3—C4 | 115.80 (19) | C35—C34—C37 | 121.5 (3) |
N1—C3—C4 | 112.93 (18) | C33—C34—C37 | 120.7 (3) |
C3—C4—Si1 | 105.16 (15) | C34—C35—C36 | 121.8 (2) |
C16—C11—C12 | 116.4 (2) | C35—C36—C31 | 119.4 (3) |
C16—C11—Si1 | 121.78 (18) | | |
| | | |
O2—S1—N1—C3 | 3.6 (2) | C13—C14—C15—C16 | 0.4 (6) |
O1—S1—N1—C3 | 133.79 (16) | C12—C11—C16—C15 | −0.6 (4) |
C31—S1—N1—C3 | −112.62 (17) | Si1—C11—C16—C15 | 179.6 (2) |
O2—S1—N1—C2 | −64.71 (18) | C14—C15—C16—C11 | 0.3 (5) |
O1—S1—N1—C2 | 65.52 (17) | C11—Si1—C21—C26 | 5.9 (2) |
C31—S1—N1—C2 | 179.11 (15) | C4—Si1—C21—C26 | −119.88 (19) |
C21—Si1—C1—C2 | 107.14 (16) | C1—Si1—C21—C26 | 131.99 (18) |
C11—Si1—C1—C2 | −128.57 (15) | C11—Si1—C21—C22 | −175.28 (19) |
C4—Si1—C1—C2 | −10.99 (16) | C4—Si1—C21—C22 | 58.9 (2) |
S1—N1—C2—C3 | 110.66 (16) | C1—Si1—C21—C22 | −49.2 (2) |
C3—N1—C2—C1 | 108.8 (2) | C26—C21—C22—C23 | 0.8 (4) |
S1—N1—C2—C1 | −140.58 (16) | Si1—C21—C22—C23 | −178.1 (2) |
Si1—C1—C2—C3 | 7.4 (2) | C21—C22—C23—C24 | −1.0 (4) |
Si1—C1—C2—N1 | −58.9 (2) | C22—C23—C24—C25 | 0.1 (4) |
C1—C2—C3—N1 | −101.5 (2) | C23—C24—C25—C26 | 0.8 (4) |
N1—C2—C3—C4 | 102.8 (2) | C24—C25—C26—C21 | −1.0 (4) |
C1—C2—C3—C4 | 1.4 (3) | C22—C21—C26—C25 | 0.2 (4) |
S1—N1—C3—C2 | −104.09 (17) | Si1—C21—C26—C25 | 179.03 (19) |
C2—N1—C3—C4 | −107.6 (2) | O2—S1—C31—C32 | 167.79 (19) |
S1—N1—C3—C4 | 148.31 (16) | O1—S1—C31—C32 | 36.6 (2) |
C2—C3—C4—Si1 | −9.4 (2) | N1—S1—C31—C32 | −74.4 (2) |
N1—C3—C4—Si1 | 57.4 (2) | O2—S1—C31—C36 | −11.8 (2) |
C21—Si1—C4—C3 | −107.49 (16) | O1—S1—C31—C36 | −142.9 (2) |
C11—Si1—C4—C3 | 128.86 (15) | N1—S1—C31—C36 | 106.0 (2) |
C1—Si1—C4—C3 | 11.72 (16) | C36—C31—C32—C33 | −0.3 (4) |
C21—Si1—C11—C16 | −85.1 (2) | S1—C31—C32—C33 | −179.8 (2) |
C4—Si1—C11—C16 | 40.7 (2) | C31—C32—C33—C34 | 0.1 (4) |
C1—Si1—C11—C16 | 147.8 (2) | C32—C33—C34—C35 | 0.2 (4) |
C21—Si1—C11—C12 | 95.1 (2) | C32—C33—C34—C37 | 179.4 (3) |
C4—Si1—C11—C12 | −139.2 (2) | C33—C34—C35—C36 | −0.3 (5) |
C1—Si1—C11—C12 | −32.0 (2) | C37—C34—C35—C36 | −179.5 (3) |
C16—C11—C12—C13 | 0.1 (4) | C34—C35—C36—C31 | 0.2 (5) |
Si1—C11—C12—C13 | 180.0 (2) | C32—C31—C36—C35 | 0.1 (4) |
C11—C12—C13—C14 | 0.6 (5) | S1—C31—C36—C35 | 179.7 (2) |
C12—C13—C14—C15 | −0.8 (6) | | |
Experimental details
| (I) | (km1600) | (km2099) |
Crystal data |
Chemical formula | C23H23NO2SSi | C23H23NO2SSi | C23H23NO2SSi |
Mr | 405.57 | 405.57 | 405.57 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 100 | 293 | 293 |
a, b, c (Å) | 9.2955 (1), 8.6076 (1), 26.5354 (3) | 9.4105 (2), 8.6979 (1), 26.7515 (5) | 9.4106 (6), 8.6993 (3), 26.7493 (16) |
α, β, γ (°) | 90, 96.440 (1), 90 | 90, 95.993 (1), 90 | 90, 96.000 (5), 90 |
V (Å3) | 2109.75 (4) | 2177.69 (7) | 2177.9 (2) |
Z | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.23 | 0.22 | 0.22 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 | 0.35 × 0.3 × 0.3 | 0.35 × 0.15 × 0.13 |
|
Data collection |
Diffractometer | KappaCCD diffractometer | KappaCCD diffractometer | Enraf Nonius TurboCAD4 diffractometer |
Absorption correction | – | – | ψ scan WinGX (Farrugia, 1999) |
Tmin, Tmax | – | – | 0.927, 0.972 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26689, 8784, 7613 | 8807, 4916, 3807 | 7898, 6318, 3267 |
Rint | 0.039 | 0.017 | 0.024 |
(sin θ/λ)max (Å−1) | 0.806 | 0.649 | 0.703 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.116, 1.04 | 0.045, 0.131, 1.03 | 0.047, 0.135, 0.99 |
No. of reflections | 8784 | 4916 | 6318 |
No. of parameters | 334 | 253 | 253 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.47, −0.45 | 0.25, −0.38 | 0.24, −0.32 |
Selected geometric parameters (Å, º) for (I) topS1—O1 | 1.4399 (8) | Si1—C4 | 1.8991 (10) |
S1—O2 | 1.4413 (8) | N1—C2 | 1.4958 (12) |
S1—N1 | 1.6597 (8) | N1—C3 | 1.4918 (12) |
Si1—C11 | 1.8756 (9) | C1—C2 | 1.5153 (13) |
Si1—C21 | 1.8682 (10) | C2—C3 | 1.4979 (14) |
Si1—C1 | 1.9004 (10) | C3—C4 | 1.5153 (13) |
| | | |
O1—S1—N1 | 105.65 (5) | C2—C1—Si1 | 104.51 (6) |
O2—S1—N1 | 111.86 (4) | C1—C2—C3 | 116.44 (8) |
C1—Si1—C4 | 96.65 (4) | C2—C3—C4 | 116.04 (8) |
C2—N1—S1 | 115.30 (6) | C3—C4—Si1 | 104.67 (6) |
C3—N1—S1 | 119.20 (6) | | |
| | | |
C4—Si1—C1—C2 | −11.25 (7) | C2—C3—C4—Si1 | −9.49 (10) |
Si1—C1—C2—C3 | 7.62 (9) | C1—Si1—C4—C3 | 11.92 (7) |
C1—C2—C3—C4 | 1.30 (12) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C22—H22···N1 | 0.92 (2) | 2.59 (2) | 3.376 (1) | 143 (1) |
C2—H2···O1i | 0.96 (2) | 2.59 (2) | 3.457 (1) | 151 (1) |
C32—H32···O1ii | 0.97 (2) | 2.57 (2) | 3.348 (1) | 138 (1) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+2, −z+1. |
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While developing synthetic routes to novel amino acids and other compounds of biological interest, we have prepared and characterized the bicyclic compound 3,3-diphenyl-6-(p-toluenesulfonyl)-6-aza-3-silabicyclo[3.1.0]hexane, (I). The most striking structural feature revealed by our X-ray analysis is the boat conformation adopted by the bridged six-membered Si1/C1/C2/N1/C3/C4 ring (Fig. 1). This conformation places the aziridine system of (I) in a sterically hindered environment and we therefore offer some comments on the factors which favour its adoption.
The torsion angles in (I) (Table 1) indicate that the sequence of four carbon atoms C1–C4 is essentially planar. Atoms N1 and Si1 lie on the same side of the plane defined by these four C atoms so that it makes dihedral angles of 77.9 (1) and 12.5 (1)° with the C2/C3/N1 and Si1/C1/C4 flaps, respectively. The aziridine ring is thus almost normal to the rather flat envelope-shaped silacyclopentane ring. Excluding the N-tosyl substituent, the molecule has approximate Cs symmetry; the mirror plane passes through Si1, N1 and the midpoint of C2—C3, nearly coincides with the plane of the axial phenyl group attached to Si1 and is normal to the equatorial phenyl group. Exact Cs symmetry would lead to C26—C21—Si1—C11 and C21—Si1—C11—C12 torsion angles of 0 and 90°; the observed values in the structure are 4.90 (9) and 93.70 (9)°. The adoption of this conformation orients the C22—H22 bond of the axial phenyl group almost directly towards N1; the resulting H···N contact (Table 2) is 2.59 (2) Å, decreasing to 2.47 Å if the C—H bond is normalized to its neutron diffraction value (Jeffrey & Lewis, 1978; Taylor & Kennard, 1983). Although this contact is substantially shorter than 2.75 Å, the sum of the Bondi (1964) contact radii for H and N, its interpretation as a weak hydrogen bond still appears controversial (Mascal, 1998; Jeffrey, 1997).
To the best of our knowledge, (I) is the first silabicyclohexane derivative to be structurally characterized. However, more than 20 years ago, Morris and co-workers (1977) showed by X-ray analysis that the bicyclo[3.1.0]hexane derivative (II) with R = C(O)NHN═CMe2 adopts the boat conformation despite an unfavourable α–δ interaction. These authors argued that the boat form was energetically preferable to the chair conformer which would have eclipsed H—C—C—H arrangements across the Cβ—Cγ bonds and two unfavourable β–δ interactions. Mastryukov et al. (1977) showed by electron diffraction and microwave spectroscopy that the parent hydrocarbon bicyclo[3.1.0]hexane (II) with R = H, also prefers the boat conformation. The current version of the Cambridge Structural Database (CSD; Allen & Kennard, 1993) contains results for 47 bicyclic compounds of types (II), (III) or (IV) (see Scheme). The puckering parameters (Cremer & Pople, 1975; Boeyens, 1978) for the bridged six-membered rings indicate that two well defined conformations represent this population: 37 molecules (including all ten epoxides and the single aziridine) have puckering parameters centred on a point in conformational space [Q = 1.03 Å, θ = 71 and ϕ = 180°] which defines a ring intermediate between the ideal boat (θ = 90 and ϕ = 180°) and envelope (θ = 55 and ϕ = 180°) transition state between boat and chair. Compound (I), with Q = 1.061 (1) Å, θ = 69.0 (1) and ϕ = 179.4 (1)°, clearly belongs to this conformational type. The remaining eight molecules have puckering parameters close to Q = 0.80 Å, θ = 33 and ϕ = 180°, and a conformation intermediate between envelope (θ = 55°) and chair (θ = 0°); all these molecules have at least three non-H substituents distributed over the Cα and Cδ ring atoms. This analysis indicates that the boat forms of (II)–(IV) are more stable than the corresponding chairs for the reasons given by Morris et al. (1977). Chair conformations are adopted only to relieve severe steric crowding of bulky substituents on the α and δ ring atoms. Compound (I) retains the boat conformation despite the resultant crowding of the aziridine group. We are planning further studies to see whether crowding lessens the reactivity of these systems.
In (I), C2—C3 [1.4979 (14) Å] is a little shorter than the adjacent C1—C2 and C3—C4 bonds [mean 1.5153 (11) Å], and the same trend is found in the 47 related molecules present in the CSD for which the corresponding mean values are 1.495 (3) and 1.512 (3) Å. This may reflect a substituent-induced shortening of the distal bonds of the three-membered rings of the type discussed by Allen (1980). Nonetheless, Mastryukov et al. (1977) pointed out that the Cγ—Cγ bond shared by the three- and five-membered rings of bicyclo[3.1.0]hexane, where no substituent effects are to be expected, is also unusually short [1.454 (9) Å]. The remaining bond lengths in (I) are unexceptional, although the S—O, S—N and N—C bonds are slightly longer than the corresponding mean values from the CSD [1.430, 1.642 and 1.472 Å, respectively; Allen et al., 1992].
Molecules of (I) interact mainly through C—H···O contacts; those with C—H···X > 120° and H···X < 2.60 Å are listed in Table 2 as potential hydrogen bonds. The intermolecular contacts involve only O1; the O2 atom is less available for such interactions because it is eclipsed by both C3 and C36 [C3—N1—S1—O2 = 3.43 (9)° and C36—C31—S1—O2 = -10.55 (10)°]. Distortions in bond angles involving S1 and N1 help to relieve the resulting overcrowding [e.g. cf. N1—S1—O2 111.86 (4)° and N1—S1—O1 105.65 (5)°].
Finally, we note that the structure of (I) at 295 K, determined from two data sets measured at normal resolution [to θ(Mo Kα) > 27°] on CCD and serial diffractometers, is essentially the same as that described here, except that the mean S—O bond length at 295 K (1.432 Å) agrees better with the value suggested by Allen et al. (1992). The results of the analyses of (I) at 295 K are included in the data deposited with this paper.