organic compounds
N-[(9H-Fluoren-9-ylidene)(2-methoxyphenyl)methyl]-1,1,1-trimethylsilanamine
aSchool of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, People's Republic of China
*Correspondence e-mail: chenxia@sxu.edu.cn
The title molecule, C24H25NOSi, is a hydrolysis product of the reaction between 9-trimethylsilyfluorenyl lithium and 2-methoxybenzonitrile. The fluorene ring system is substantially planar, with an r.m.s. deviation of 0.0288 Å from the best-fit plane through its 13 C atoms. This plane forms a dihedral angle of 58.07 (7)° with the 2-methoxybenzylamine ring plane. In the crystal, molecules are linked by N—H⋯π and C—H⋯π interactions, which leads to the formation of two-dimensional network lying parallel to the bc plane.
CCDC reference: 976209
Related literature
For the use of fluorene as a ligand in organometallic chemistry, see: Alt & Samuel (1998); Kirillov et al. (2005); Bochmann et al. (1993); Decken et al. (2002); Knjazhanski et al. (2002); Novikova et al. (1985); Johnson & Treichel (1977). For σ–π stacking, see: Calhorda (2000); Desiraju & Steiner (1999). For a related aminofulvene structure, see: Axenov et al. (2009).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 976209
https://doi.org/10.1107/S1600536813033424/sj5378sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813033424/sj5378Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813033424/sj5378Isup3.cml
The 9-trimethylsilyl-fluorenyllithium (0.68 g, 2.8 mmol) mixed with (o-MeO)PhCN (0.34 ml, 2.8 mmol) at 0 °C. The resulting mixture was slowly warmed to room temperature and stirred for a further 10 hours to give a clear brown solution. H2O (2.8 mmol, 0.41 ml, 6.94 M in THF) was added to a stirred solution, prepared in situ without purification, at 0 °C. The resulting cloudy yellow solution was allowed to warm to room temperature for 7 days, yielding colorless crystals of the title compound (0.62 g, 59% yield). Mp: 172 °C. 1H NMR (300 MHz, C6D6): δ (ppm) -0.14 (s, 9H, -Si(CH3)3), 2.68 (s,1H,-NH), 3.78 (s, 3H, -OCH3), 6.71 (s, 2H, -CH- of phenyl), 6.88-6.90 (d, JHH=7.5 Hz, 2H, -CH- of fluorenyl), 7.21-7.44 (m, 2H, -CH- of phenyl), 7.59-7.63 (m, 2H, -CH- of fluorenyl), 7.71-7.73 (d, JHH=7.8 Hz, 2H, -CH- of fluorenyl), 7.89-7.92 (d, JHH=7.8 Hz, 2H, -CH- of fluorenyl). 13C NMR (75 MHz, CDCl3): δ (ppm) 1.99 (3C, C of -SiMe3), 58.23 (1C, -OCH3), 109.33, 113.23, 120.27, 121.02, 122.11, 124.21, 126.35, 127.33, 128.53, 138.40, 139.24, 140.12, 140.35, 141.11, 143.23 (17C, C of fluorenyl and phenyl), 151.78, 166.65 (2C, Cipso of phenyl), 154.32 (1C, PhCNHSiMe3). Anal. Calc. for C24H25NOSi (Mr = 371.55): C, 77.58; H, 6.78; N, 3.77%. Found: C, 77.80; H, 6.68; N, 3.82%.
The methyl H atoms were constrained to an ideal geometry, with C—H distances of 0.98 Å and Uiso(H) = 1.5Ueq(C). N–H bond distances was restrained to be 0.88 Å and Uiso(H) = 1.2Ueq(N). The phenyl H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 Å and Uiso(H) = 1.2Ueq(C).
Fluorene is an attractive ligand for organometallic chemistry for several reasons. It may be regarded as a doubly benzannelated cyclopentadiene, which may be deprotonated at the 9 position to generate a substituted Cp ligand. Indeed, it is this unit upon which much of the organometallic chemistry of fluorene is based. This ligand may bind to metals in a wide variety of ways, many of which are unavailable to analogous Cp species, with η1, η3, and η5 forms all structurally characterized (Alt and Samuel, 1998; Kirillov et al., 2005; Bochmann et al., 1993; Decken et al., 2002; Knjazhanski et al., 2002). Fluorene may also be regarded as a CH2-bridged biphenyl unit, with two potential binding sites on the arene rings. Again, this has been exploited, with the synthesis of several bimetallic systems with the ligand again showing the ability to bind in a variety of coordination modes, η5 and η6 are both known (Novikova et al., 1985; Johnson and Treichel, 1977). Here, we report the synthesis and structure of the new compound N-((9H-fluoren-9-ylidene)(2-methoxyphenyl)methyl)-1,1,1-trimethylsilanamine.
The molecular structure of the title compound is illustrated in Fig. 1. The compound is a hydrolysis product of the reaction between 9-trimethylsilyfluorenyl lithium and 2-methoxybenzonitrile. The fluorene ring system is substantially planar with an rms deviation of 0.0288 Å from the best fit plane through its 13 C atoms. This plane forms a dihedral angle of 58.07 (7)° with the 2-methoxybenzonitrile ring plane. The five-membered shows alternating C=C and C—C bond length. The exocyclic C1—C14 [1.368 (4)Å] linkage is in the typical double bond range [1.32 Å]. This comound contains a typical aminofulvene framework (Axenov et al., 2009). The adjacent C14—N1 bond is also short, indicating the presence of delocalization in the C1—C14—N1 fragments to some extent. The other adjacent bond distance, C14—C15, is 1.490 (3)Å which is in agreement with single bond character [1.53 Å]. A number of N–H···π and C–H···π stacking interactions involving the phenyl rings help to consolidate the crystal packing. The N···Cg and C···Cg (Cg = ring centroid) distances lie in the range 2.989-3.473 Å, which is normal for such interactions (Calhorda, 2000; Desiraju & Steiner, 1999) and lead to the formation of an infinite one-dimensional chain structure (Fig. 2).
Fluorene is an attractive ligand for organometallic chemistry for several reasons. It may be regarded as a doubly benzannelated cyclopentadiene, which may be deprotonated at the 9 position to generate a substituted Cp ligand. Indeed, it is this unit upon which much of the organometallic chemistry of fluorene is based. This ligand may bind to metals in a wide variety of ways, many of which are unavailable to analogous Cp species, with η1, η3, and η5 forms all structurally characterized (Alt and Samuel, 1998; Kirillov et al., 2005; Bochmann et al., 1993; Decken et al., 2002; Knjazhanski et al., 2002). Fluorene may also be regarded as a CH2-bridged biphenyl unit, with two potential binding sites on the arene rings. Again, this has been exploited, with the synthesis of several bimetallic systems with the ligand again showing the ability to bind in a variety of coordination modes, η5 and η6 are both known (Novikova et al., 1985; Johnson and Treichel, 1977). Here, we report the synthesis and structure of the new compound N-((9H-fluoren-9-ylidene)(2-methoxyphenyl)methyl)-1,1,1-trimethylsilanamine.
The molecular structure of the title compound is illustrated in Fig. 1. The compound is a hydrolysis product of the reaction between 9-trimethylsilyfluorenyl lithium and 2-methoxybenzonitrile. The fluorene ring system is substantially planar with an rms deviation of 0.0288 Å from the best fit plane through its 13 C atoms. This plane forms a dihedral angle of 58.07 (7)° with the 2-methoxybenzonitrile ring plane. The five-membered shows alternating C=C and C—C bond length. The exocyclic C1—C14 [1.368 (4)Å] linkage is in the typical double bond range [1.32 Å]. This comound contains a typical aminofulvene framework (Axenov et al., 2009). The adjacent C14—N1 bond is also short, indicating the presence of delocalization in the C1—C14—N1 fragments to some extent. The other adjacent bond distance, C14—C15, is 1.490 (3)Å which is in agreement with single bond character [1.53 Å]. A number of N–H···π and C–H···π stacking interactions involving the phenyl rings help to consolidate the crystal packing. The N···Cg and C···Cg (Cg = ring centroid) distances lie in the range 2.989-3.473 Å, which is normal for such interactions (Calhorda, 2000; Desiraju & Steiner, 1999) and lead to the formation of an infinite one-dimensional chain structure (Fig. 2).
For the use of fluorene as a ligand in organometallic chemistry, see: Alt & Samuel (1998); Kirillov et al. (2005); Bochmann et al. (1993); Decken et al. (2002); Knjazhanski et al. (2002); Novikova et al. (1985); Johnson & Treichel (1977). For σ–π stacking, see: Calhorda (2000); Desiraju & Steiner (1999). For a related aminofulvene structure, see: Axenov et al. (2009).
The 9-trimethylsilyl-fluorenyllithium (0.68 g, 2.8 mmol) mixed with (o-MeO)PhCN (0.34 ml, 2.8 mmol) at 0 °C. The resulting mixture was slowly warmed to room temperature and stirred for a further 10 hours to give a clear brown solution. H2O (2.8 mmol, 0.41 ml, 6.94 M in THF) was added to a stirred solution, prepared in situ without purification, at 0 °C. The resulting cloudy yellow solution was allowed to warm to room temperature for 7 days, yielding colorless crystals of the title compound (0.62 g, 59% yield). Mp: 172 °C. 1H NMR (300 MHz, C6D6): δ (ppm) -0.14 (s, 9H, -Si(CH3)3), 2.68 (s,1H,-NH), 3.78 (s, 3H, -OCH3), 6.71 (s, 2H, -CH- of phenyl), 6.88-6.90 (d, JHH=7.5 Hz, 2H, -CH- of fluorenyl), 7.21-7.44 (m, 2H, -CH- of phenyl), 7.59-7.63 (m, 2H, -CH- of fluorenyl), 7.71-7.73 (d, JHH=7.8 Hz, 2H, -CH- of fluorenyl), 7.89-7.92 (d, JHH=7.8 Hz, 2H, -CH- of fluorenyl). 13C NMR (75 MHz, CDCl3): δ (ppm) 1.99 (3C, C of -SiMe3), 58.23 (1C, -OCH3), 109.33, 113.23, 120.27, 121.02, 122.11, 124.21, 126.35, 127.33, 128.53, 138.40, 139.24, 140.12, 140.35, 141.11, 143.23 (17C, C of fluorenyl and phenyl), 151.78, 166.65 (2C, Cipso of phenyl), 154.32 (1C, PhCNHSiMe3). Anal. Calc. for C24H25NOSi (Mr = 371.55): C, 77.58; H, 6.78; N, 3.77%. Found: C, 77.80; H, 6.68; N, 3.82%.
detailsThe methyl H atoms were constrained to an ideal geometry, with C—H distances of 0.98 Å and Uiso(H) = 1.5Ueq(C). N–H bond distances was restrained to be 0.88 Å and Uiso(H) = 1.2Ueq(N). The phenyl H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 Å and Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure, showing the atom–numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are omitted for clarity. | |
Fig. 2. Crystal packing of 1 with N–H···π and C–H···π contacts drawn as dotted lines and spheres representing the aromatic ring centroids. |
C24H25NOSi | F(000) = 792 |
Mr = 371.54 | Dx = 1.215 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6083 reflections |
a = 12.611 (3) Å | θ = 1.6–27.5° |
b = 9.5694 (19) Å | µ = 0.13 mm−1 |
c = 20.325 (6) Å | T = 173 K |
β = 124.10 (2)° | Prism, yellow |
V = 2031.1 (9) Å3 | 0.19 × 0.17 × 0.12 mm |
Z = 4 |
Bruker P4 diffractometer | 4628 independent reflections |
Radiation source: fine-focus sealed tube | 4212 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
ω scans | θmax = 27.4°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→12 |
Tmin = 0.976, Tmax = 0.985 | k = −12→12 |
15991 measured reflections | l = −25→26 |
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)] = 0.075 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.173 | H-atom parameters constrained |
S = 1.24 | w = 1/[σ2(Fo2) + (0.0619P)2 + 1.2002P] where P = (Fo2 + 2Fc2)/3 |
4628 reflections | (Δ/σ)max < 0.001 |
248 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C24H25NOSi | V = 2031.1 (9) Å3 |
Mr = 371.54 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.611 (3) Å | µ = 0.13 mm−1 |
b = 9.5694 (19) Å | T = 173 K |
c = 20.325 (6) Å | 0.19 × 0.17 × 0.12 mm |
β = 124.10 (2)° |
Bruker P4 diffractometer | 4628 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4212 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.985 | Rint = 0.057 |
15991 measured reflections |
R[F2 > 2σ(F2)] = 0.075 | 0 restraints |
wR(F2) = 0.173 | H-atom parameters constrained |
S = 1.24 | Δρmax = 0.50 e Å−3 |
4628 reflections | Δρmin = −0.26 e Å−3 |
248 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Si1 | 0.66989 (6) | 0.64695 (7) | 0.46564 (4) | 0.02799 (19) | |
O1 | 0.94557 (19) | 0.4521 (2) | 0.70940 (11) | 0.0421 (5) | |
N1 | 0.81941 (18) | 0.5781 (2) | 0.49531 (11) | 0.0270 (4) | |
H1 | 0.8454 | 0.6009 | 0.4646 | 0.032* | |
C1 | 1.0326 (2) | 0.5139 (2) | 0.60208 (13) | 0.0253 (5) | |
C2 | 1.0993 (2) | 0.6446 (2) | 0.60736 (14) | 0.0253 (5) | |
C3 | 1.0568 (2) | 0.7744 (2) | 0.56909 (15) | 0.0300 (5) | |
H3A | 0.9696 | 0.7869 | 0.5268 | 0.036* | |
C4 | 1.1426 (2) | 0.8843 (3) | 0.59324 (16) | 0.0334 (6) | |
H4A | 1.1131 | 0.9719 | 0.5670 | 0.040* | |
C5 | 1.2708 (3) | 0.8693 (3) | 0.65494 (16) | 0.0353 (6) | |
H5A | 1.3276 | 0.9464 | 0.6708 | 0.042* | |
C6 | 1.3158 (2) | 0.7417 (3) | 0.69335 (15) | 0.0315 (5) | |
H6A | 1.4034 | 0.7305 | 0.7354 | 0.038* | |
C7 | 1.2307 (2) | 0.6306 (2) | 0.66934 (14) | 0.0268 (5) | |
C8 | 1.2521 (2) | 0.4893 (2) | 0.70131 (14) | 0.0274 (5) | |
C9 | 1.3646 (2) | 0.4240 (3) | 0.76098 (15) | 0.0342 (6) | |
H9A | 1.4436 | 0.4732 | 0.7886 | 0.041* | |
C10 | 1.3589 (3) | 0.2860 (3) | 0.77916 (16) | 0.0388 (6) | |
H10A | 1.4346 | 0.2403 | 0.8199 | 0.047* | |
C11 | 1.2439 (3) | 0.2140 (3) | 0.73847 (16) | 0.0386 (6) | |
H11A | 1.2421 | 0.1191 | 0.7515 | 0.046* | |
C12 | 1.1311 (2) | 0.2778 (3) | 0.67909 (16) | 0.0332 (6) | |
H12A | 1.0532 | 0.2265 | 0.6511 | 0.040* | |
C13 | 1.1335 (2) | 0.4186 (2) | 0.66094 (14) | 0.0271 (5) | |
C14 | 0.9032 (2) | 0.4938 (2) | 0.55932 (14) | 0.0257 (5) | |
C15 | 0.8397 (2) | 0.3807 (2) | 0.57581 (15) | 0.0278 (5) | |
C16 | 0.7537 (2) | 0.2919 (3) | 0.51407 (16) | 0.0347 (6) | |
H16A | 0.7369 | 0.3050 | 0.4627 | 0.042* | |
C17 | 0.6921 (3) | 0.1846 (3) | 0.5262 (2) | 0.0446 (7) | |
H17A | 0.6342 | 0.1243 | 0.4838 | 0.054* | |
C18 | 0.7167 (3) | 0.1672 (3) | 0.6009 (2) | 0.0517 (8) | |
H18A | 0.6748 | 0.0943 | 0.6096 | 0.062* | |
C19 | 0.8008 (3) | 0.2535 (3) | 0.66320 (19) | 0.0452 (7) | |
H19A | 0.8163 | 0.2395 | 0.7142 | 0.054* | |
C20 | 0.8628 (2) | 0.3610 (3) | 0.65138 (16) | 0.0340 (6) | |
C21 | 0.9910 (3) | 0.4175 (4) | 0.78948 (17) | 0.0574 (9) | |
H21A | 1.0579 | 0.4837 | 0.8258 | 0.086* | |
H21B | 1.0262 | 0.3226 | 0.8014 | 0.086* | |
H21C | 0.9199 | 0.4225 | 0.7962 | 0.086* | |
C22 | 0.6655 (3) | 0.6740 (4) | 0.55400 (18) | 0.0524 (8) | |
H22A | 0.6696 | 0.5834 | 0.5778 | 0.079* | |
H22B | 0.5857 | 0.7216 | 0.5383 | 0.079* | |
H22C | 0.7387 | 0.7314 | 0.5928 | 0.079* | |
C23 | 0.5336 (3) | 0.5378 (3) | 0.39032 (18) | 0.0457 (7) | |
H23A | 0.5327 | 0.4500 | 0.4148 | 0.069* | |
H23B | 0.5430 | 0.5176 | 0.3466 | 0.069* | |
H23C | 0.4532 | 0.5882 | 0.3698 | 0.069* | |
C24 | 0.6621 (3) | 0.8163 (3) | 0.41832 (18) | 0.0424 (7) | |
H24A | 0.6755 | 0.8001 | 0.3758 | 0.064* | |
H24B | 0.7289 | 0.8789 | 0.4582 | 0.064* | |
H24C | 0.5779 | 0.8590 | 0.3959 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.0246 (3) | 0.0260 (3) | 0.0320 (4) | −0.0010 (3) | 0.0151 (3) | 0.0018 (3) |
O1 | 0.0480 (11) | 0.0507 (12) | 0.0328 (10) | −0.0042 (9) | 0.0258 (9) | 0.0010 (9) |
N1 | 0.0255 (10) | 0.0295 (10) | 0.0279 (10) | −0.0011 (8) | 0.0162 (9) | 0.0041 (8) |
C1 | 0.0286 (11) | 0.0223 (11) | 0.0279 (11) | 0.0025 (9) | 0.0177 (10) | 0.0025 (9) |
C2 | 0.0277 (11) | 0.0242 (11) | 0.0284 (12) | −0.0011 (9) | 0.0184 (10) | −0.0016 (9) |
C3 | 0.0268 (12) | 0.0259 (12) | 0.0363 (13) | 0.0012 (9) | 0.0171 (11) | 0.0031 (10) |
C4 | 0.0379 (13) | 0.0217 (11) | 0.0429 (15) | −0.0013 (10) | 0.0240 (12) | 0.0028 (10) |
C5 | 0.0379 (14) | 0.0274 (13) | 0.0419 (15) | −0.0089 (11) | 0.0232 (12) | −0.0042 (11) |
C6 | 0.0297 (12) | 0.0320 (13) | 0.0303 (13) | −0.0047 (10) | 0.0154 (11) | −0.0037 (10) |
C7 | 0.0289 (12) | 0.0267 (12) | 0.0283 (12) | −0.0017 (9) | 0.0182 (10) | −0.0020 (9) |
C8 | 0.0302 (12) | 0.0273 (12) | 0.0270 (12) | 0.0003 (9) | 0.0174 (10) | −0.0001 (9) |
C9 | 0.0274 (12) | 0.0404 (14) | 0.0310 (13) | 0.0025 (10) | 0.0140 (11) | 0.0035 (11) |
C10 | 0.0370 (14) | 0.0384 (15) | 0.0372 (14) | 0.0144 (12) | 0.0184 (12) | 0.0127 (12) |
C11 | 0.0459 (15) | 0.0293 (13) | 0.0458 (16) | 0.0080 (12) | 0.0288 (13) | 0.0109 (12) |
C12 | 0.0353 (13) | 0.0268 (12) | 0.0409 (14) | 0.0012 (10) | 0.0235 (12) | 0.0036 (11) |
C13 | 0.0302 (12) | 0.0265 (12) | 0.0282 (12) | 0.0013 (9) | 0.0186 (10) | 0.0009 (9) |
C14 | 0.0290 (12) | 0.0229 (11) | 0.0285 (12) | 0.0006 (9) | 0.0181 (10) | 0.0011 (9) |
C15 | 0.0274 (11) | 0.0238 (11) | 0.0366 (13) | 0.0001 (9) | 0.0205 (11) | 0.0034 (10) |
C16 | 0.0338 (13) | 0.0267 (12) | 0.0448 (15) | −0.0013 (10) | 0.0228 (12) | 0.0005 (11) |
C17 | 0.0395 (15) | 0.0278 (13) | 0.065 (2) | −0.0071 (11) | 0.0282 (15) | −0.0017 (13) |
C18 | 0.0493 (17) | 0.0341 (15) | 0.082 (2) | −0.0043 (13) | 0.0429 (18) | 0.0143 (15) |
C19 | 0.0468 (16) | 0.0465 (16) | 0.0550 (18) | 0.0070 (13) | 0.0364 (15) | 0.0192 (14) |
C20 | 0.0347 (13) | 0.0319 (13) | 0.0423 (15) | 0.0055 (11) | 0.0258 (12) | 0.0072 (11) |
C21 | 0.071 (2) | 0.068 (2) | 0.0338 (16) | 0.0138 (18) | 0.0295 (16) | 0.0103 (15) |
C22 | 0.0468 (17) | 0.071 (2) | 0.0466 (18) | 0.0152 (16) | 0.0306 (15) | 0.0058 (16) |
C23 | 0.0296 (14) | 0.0359 (15) | 0.0547 (18) | −0.0058 (11) | 0.0132 (13) | 0.0013 (13) |
C24 | 0.0390 (15) | 0.0309 (13) | 0.0519 (17) | 0.0021 (11) | 0.0221 (14) | 0.0078 (12) |
Si1—N1 | 1.754 (2) | C11—C12 | 1.388 (4) |
Si1—C22 | 1.846 (3) | C11—H11A | 0.9500 |
Si1—C23 | 1.854 (3) | C12—C13 | 1.402 (3) |
Si1—C24 | 1.859 (3) | C12—H12A | 0.9500 |
O1—C20 | 1.364 (3) | C14—C15 | 1.491 (3) |
O1—C21 | 1.429 (3) | C15—C16 | 1.396 (3) |
N1—C14 | 1.385 (3) | C15—C20 | 1.407 (4) |
N1—H1 | 0.8800 | C16—C17 | 1.390 (4) |
C1—C14 | 1.366 (3) | C16—H16A | 0.9500 |
C1—C13 | 1.475 (3) | C17—C18 | 1.378 (5) |
C1—C2 | 1.477 (3) | C17—H17A | 0.9500 |
C2—C3 | 1.403 (3) | C18—C19 | 1.380 (5) |
C2—C7 | 1.417 (3) | C18—H18A | 0.9500 |
C3—C4 | 1.387 (3) | C19—C20 | 1.392 (4) |
C3—H3A | 0.9500 | C19—H19A | 0.9500 |
C4—C5 | 1.391 (4) | C21—H21A | 0.9800 |
C4—H4A | 0.9500 | C21—H21B | 0.9800 |
C5—C6 | 1.387 (4) | C21—H21C | 0.9800 |
C5—H5A | 0.9500 | C22—H22A | 0.9800 |
C6—C7 | 1.391 (3) | C22—H22B | 0.9800 |
C6—H6A | 0.9500 | C22—H22C | 0.9800 |
C7—C8 | 1.459 (3) | C23—H23A | 0.9800 |
C8—C9 | 1.395 (3) | C23—H23B | 0.9800 |
C8—C13 | 1.411 (3) | C23—H23C | 0.9800 |
C9—C10 | 1.383 (4) | C24—H24A | 0.9800 |
C9—H9A | 0.9500 | C24—H24B | 0.9800 |
C10—C11 | 1.385 (4) | C24—H24C | 0.9800 |
C10—H10A | 0.9500 | ||
N1—Si1—C22 | 109.34 (12) | C12—C13—C1 | 132.2 (2) |
N1—Si1—C23 | 113.09 (12) | C8—C13—C1 | 109.0 (2) |
C22—Si1—C23 | 111.28 (16) | C1—C14—N1 | 121.7 (2) |
N1—Si1—C24 | 103.88 (12) | C1—C14—C15 | 124.0 (2) |
C22—Si1—C24 | 111.08 (15) | N1—C14—C15 | 114.3 (2) |
C23—Si1—C24 | 107.95 (13) | C16—C15—C20 | 118.7 (2) |
C20—O1—C21 | 117.4 (2) | C16—C15—C14 | 119.0 (2) |
C14—N1—Si1 | 130.40 (16) | C20—C15—C14 | 122.3 (2) |
C14—N1—H1 | 114.8 | C17—C16—C15 | 121.3 (3) |
Si1—N1—H1 | 114.8 | C17—C16—H16A | 119.3 |
C14—C1—C13 | 127.5 (2) | C15—C16—H16A | 119.3 |
C14—C1—C2 | 126.5 (2) | C18—C17—C16 | 118.8 (3) |
C13—C1—C2 | 105.54 (19) | C18—C17—H17A | 120.6 |
C3—C2—C7 | 118.0 (2) | C16—C17—H17A | 120.6 |
C3—C2—C1 | 133.2 (2) | C17—C18—C19 | 121.4 (3) |
C7—C2—C1 | 108.6 (2) | C17—C18—H18A | 119.3 |
C4—C3—C2 | 119.7 (2) | C19—C18—H18A | 119.3 |
C4—C3—H3A | 120.1 | C18—C19—C20 | 120.0 (3) |
C2—C3—H3A | 120.1 | C18—C19—H19A | 120.0 |
C3—C4—C5 | 121.5 (2) | C20—C19—H19A | 120.0 |
C3—C4—H4A | 119.2 | O1—C20—C19 | 123.7 (3) |
C5—C4—H4A | 119.2 | O1—C20—C15 | 116.6 (2) |
C6—C5—C4 | 120.0 (2) | C19—C20—C15 | 119.7 (3) |
C6—C5—H5A | 120.0 | O1—C21—H21A | 109.5 |
C4—C5—H5A | 120.0 | O1—C21—H21B | 109.5 |
C5—C6—C7 | 118.9 (2) | H21A—C21—H21B | 109.5 |
C5—C6—H6A | 120.6 | O1—C21—H21C | 109.5 |
C7—C6—H6A | 120.6 | H21A—C21—H21C | 109.5 |
C6—C7—C2 | 121.8 (2) | H21B—C21—H21C | 109.5 |
C6—C7—C8 | 129.7 (2) | Si1—C22—H22A | 109.5 |
C2—C7—C8 | 108.4 (2) | Si1—C22—H22B | 109.5 |
C9—C8—C13 | 121.4 (2) | H22A—C22—H22B | 109.5 |
C9—C8—C7 | 130.3 (2) | Si1—C22—H22C | 109.5 |
C13—C8—C7 | 108.3 (2) | H22A—C22—H22C | 109.5 |
C10—C9—C8 | 118.7 (2) | H22B—C22—H22C | 109.5 |
C10—C9—H9A | 120.7 | Si1—C23—H23A | 109.5 |
C8—C9—H9A | 120.7 | Si1—C23—H23B | 109.5 |
C9—C10—C11 | 120.6 (2) | H23A—C23—H23B | 109.5 |
C9—C10—H10A | 119.7 | Si1—C23—H23C | 109.5 |
C11—C10—H10A | 119.7 | H23A—C23—H23C | 109.5 |
C10—C11—C12 | 121.3 (2) | H23B—C23—H23C | 109.5 |
C10—C11—H11A | 119.3 | Si1—C24—H24A | 109.5 |
C12—C11—H11A | 119.3 | Si1—C24—H24B | 109.5 |
C11—C12—C13 | 119.2 (2) | H24A—C24—H24B | 109.5 |
C11—C12—H12A | 120.4 | Si1—C24—H24C | 109.5 |
C13—C12—H12A | 120.4 | H24A—C24—H24C | 109.5 |
C12—C13—C8 | 118.7 (2) | H24B—C24—H24C | 109.5 |
C22—Si1—N1—C14 | 29.8 (3) | C7—C8—C13—C12 | 177.0 (2) |
C23—Si1—N1—C14 | −94.8 (2) | C9—C8—C13—C1 | 179.6 (2) |
C24—Si1—N1—C14 | 148.4 (2) | C7—C8—C13—C1 | −0.3 (3) |
C14—C1—C2—C3 | −5.7 (4) | C14—C1—C13—C12 | 13.6 (4) |
C13—C1—C2—C3 | −177.8 (2) | C2—C1—C13—C12 | −174.5 (2) |
C14—C1—C2—C7 | 168.4 (2) | C14—C1—C13—C8 | −169.6 (2) |
C13—C1—C2—C7 | −3.6 (2) | C2—C1—C13—C8 | 2.3 (2) |
C7—C2—C3—C4 | −0.9 (3) | C13—C1—C14—N1 | −167.5 (2) |
C1—C2—C3—C4 | 172.9 (2) | C2—C1—C14—N1 | 22.2 (4) |
C2—C3—C4—C5 | 0.0 (4) | C13—C1—C14—C15 | 11.7 (4) |
C3—C4—C5—C6 | 0.6 (4) | C2—C1—C14—C15 | −158.7 (2) |
C4—C5—C6—C7 | −0.3 (4) | Si1—N1—C14—C1 | −139.9 (2) |
C5—C6—C7—C2 | −0.6 (4) | Si1—N1—C14—C15 | 40.8 (3) |
C5—C6—C7—C8 | −177.5 (2) | C1—C14—C15—C16 | −127.0 (3) |
C3—C2—C7—C6 | 1.2 (3) | N1—C14—C15—C16 | 52.3 (3) |
C1—C2—C7—C6 | −174.0 (2) | C1—C14—C15—C20 | 53.6 (3) |
C3—C2—C7—C8 | 178.7 (2) | N1—C14—C15—C20 | −127.2 (2) |
C1—C2—C7—C8 | 3.5 (3) | C20—C15—C16—C17 | −0.6 (4) |
C6—C7—C8—C9 | −4.6 (4) | C14—C15—C16—C17 | 179.9 (2) |
C2—C7—C8—C9 | 178.2 (2) | C15—C16—C17—C18 | 0.4 (4) |
C6—C7—C8—C13 | 175.2 (2) | C16—C17—C18—C19 | −0.2 (5) |
C2—C7—C8—C13 | −2.0 (3) | C17—C18—C19—C20 | 0.1 (5) |
C13—C8—C9—C10 | 1.4 (4) | C21—O1—C20—C19 | 13.5 (4) |
C7—C8—C9—C10 | −178.8 (2) | C21—O1—C20—C15 | −167.3 (2) |
C8—C9—C10—C11 | 0.5 (4) | C18—C19—C20—O1 | 178.9 (3) |
C9—C10—C11—C12 | −0.6 (4) | C18—C19—C20—C15 | −0.3 (4) |
C10—C11—C12—C13 | −1.1 (4) | C16—C15—C20—O1 | −178.7 (2) |
C11—C12—C13—C8 | 2.9 (4) | C14—C15—C20—O1 | 0.8 (3) |
C11—C12—C13—C1 | 179.5 (2) | C16—C15—C20—C19 | 0.6 (4) |
C9—C8—C13—C12 | −3.1 (3) | C14—C15—C20—C19 | −180.0 (2) |
Cg1, Cg2 and Cg4 are the centroids of the C1,C2,C7,C8,C13, C2–C7 and C15–C20 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cg1i | 0.88 | 2.69 | 3.347 (3) | 133 |
C12—H12A···Cg4 | 0.95 | 2.99 | 3.750 (4) | 138 |
C16—H16A···Cg2i | 0.95 | 2.65 | 3.470 (3) | 145 |
C21—H21C···Cg2ii | 0.98 | 2.94 | 3.736 (4) | 139 |
C24—H24A···Cg3i | 0.98 | 2.99 | 3.923 (4) | 158 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, y−1/2, −z+3/2. |
Cg1, Cg2 and Cg4 are the centroids of the C1,C2,C7,C8,C13, C2–C7 and C15–C20 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cg1i | 0.88 | 2.69 | 3.347 (3) | 133 |
C12—H12A···Cg4 | 0.95 | 2.99 | 3.750 (4) | 138 |
C16—H16A···Cg2i | 0.95 | 2.65 | 3.470 (3) | 145 |
C21—H21C···Cg2ii | 0.98 | 2.94 | 3.736 (4) | 139 |
C24—H24A···Cg3i | 0.98 | 2.99 | 3.923 (4) | 158 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+2, y−1/2, −z+3/2. |
Acknowledgements
We thank the Natural Science Foundation of China (grant No. 20942009, 21072120), the Shanxi Scholarship Council of China (No. 201310) and the Key Technologies R & D Program of Shanxi Province (No. 20110321055).
References
Alt, H. G. & Samuel, E. (1998). Chem. Soc. Rev. 27, 323–329. CrossRef CAS Google Scholar
Axenov, K. V., Kehr, G., Fröhlich, R. & Erker, G. (2009). Organometallics, 28, 5148–5158. Web of Science CSD CrossRef CAS Google Scholar
Bochmann, M., Lancaster, S. J., Hursthouse, M. B. & Mazid, M. (1993). Organometallics, 12, 4718–4720. CSD CrossRef CAS Web of Science Google Scholar
Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Calhorda, M. J. (2000). Chem. Commun. pp. 801–809. Web of Science CrossRef Google Scholar
Decken, A., Mackay, A. J., Brown, M. J. & Bottomley, F. (2002). Organometallics, 21, 2006–2009. Web of Science CSD CrossRef CAS Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology, p. 152. Oxford University Press. Google Scholar
Johnson, J. W. & Treichel, P. M. (1977). J. Am. Chem. Soc. 99, 1427–1436. CSD CrossRef CAS Web of Science Google Scholar
Kirillov, E., Saillard, J. Y. & Carpentier, J. F. (2005). Coord. Chem. Rev. 249, 1221–1248. Web of Science CrossRef CAS Google Scholar
Knjazhanski, S. Y., Cadenas, G., García, M., Pérez, C. M., Nifant'ev, I. E., Kashulin, I. A., Ivchenko, P. V. & Lyssenko, K. A. (2002). Organometallics, 21, 3094–3099. Web of Science CSD CrossRef CAS Google Scholar
Novikova, L. N., Ustynyuk, N. A., Zvorykin, V. E., Dneprovskaya, L. S. & Ustynyuk, Y. A. (1985). J. Organomet. Chem. 292, 237–243. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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