Experimental. Crystal data. C 24 H 25 NOSi M r = Monoclinic, P2 1 =c a = (3) Å b = (19) Å c = (6) Å = 124.

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1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN N-[(9H-Fluoren-9-ylidene)(2-methoxyphenyl)methyl]-1,1,1-trimethylsilanamine Zhong-Yuan Li, Peng Wang and Xia Chen* School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan , People s Republic of China Correspondence chenxia@sxu.edu.cn Received 7 December 2013; accepted 10 December 2013 Key indicators: single-crystal X-ray study; T = 173 K; mean (C C) = Å; R factor = 0.075; wr factor = 0.173; data-to-parameter ratio = Experimental Crystal data C 24 H 25 NOSi M r = Monoclinic, P2 1 =c a = (3) Å b = (19) Å c = (6) Å = (2) Data collection Bruker P4 diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.976, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections V = (9) Å 3 Z =4 Mo K radiation = 0.13 mm 1 T = 173 K mm measured reflections 4628 independent reflections 4212 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.50 e Å 3 min = 0.26 e Å 3 The title molecule, C 24 H 25 NOSi, 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 Å from the best-fit plane through its 13 C atoms. This plane forms a dihedral angle of (7) with the 2-methoxybenzylamine ring plane. In the crystal, molecules are linked by N H and C H interactions, which leads to the formation of twodimensional network lying parallel to the bc plane. 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 stacking, see: Calhorda (2000); Desiraju & Steiner (1999). For a related aminofulvene structure, see: Axenov et al. (2009). Table 1 Hydrogen-bond geometry (Å, ). Cg1, Cg2 and Cg4 are the centroids of the C1,C2,C7,C8,C13, C2 C7 and C15 C20 rings, respectively. D HA D H HA DA D HA N1 H1Cg1 i (3) 133 C12 H12ACg (4) 138 C16 H16ACg2 i (3) 145 C21 H21CCg2 ii (4) 139 C24 H24ACg3 i (4) 158 Symmetry codes: (i) x þ 2; y þ 1; z þ 1; (ii) x þ 2; y 1 2 ; z þ 3 2. Data collection: SMART (Bruker, 2000); cell refinement: 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. We thank the Natural Science Foundation of China (grant No , ), the Shanxi Scholarship Council of China (No ) and the Key Technologies R & D Program of Shanxi Province (No ). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: SJ5378). References Alt, H. G. & Samuel, E. (1998). Chem. Soc. Rev. 27, Axenov, K. V., Kehr, G., Fröhlich, R. & Erker, G. (2009). Organometallics, 28, Bochmann, M., Lancaster, S. J., Hursthouse, M. B. & Mazid, M. (1993). Organometallics, 12, Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Calhorda, M. J. (2000). Chem. Commun. pp Decken, A., Mackay, A. J., Brown, M. J. & Bottomley, F. (2002). Organometallics, 21, doi: /s Li et al. o59

2 organic compounds Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology, p Oxford University Press. Johnson, J. W. & Treichel, P. M. (1977). J. Am. Chem. Soc. 99, Kirillov, E., Saillard, J. Y. & Carpentier, J. F. (2005). Coord. Chem. Rev. 249, 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, Novikova, L. N., Ustynyuk, N. A., Zvorykin, V. E., Dneprovskaya, L. S. & Ustynyuk, Y. A. (1985). J. Organomet. Chem. 292, Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, o60 Li et al. C 24 H 25 NOSi

3 [ N-[(9H-Fluoren-9-ylidene)(2-methoxyphenyl)methyl]-1,1,1-trimethylsilanamine Zhong-Yuan Li, Peng Wang and Xia Chen S1. Experimental S1.1. Synthesis and crystallization 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. H 2 O (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. 1 H NMR (300 MHz, C 6 D 6 ): δ (ppm) (s, 9H, - Si(CH 3 ) 3 ), 2.68 (s,1h,-nh), 3.78 (s, 3H, -OCH 3 ), 6.71 (s, 2H, -CH- of phenyl), (d, J HH =7.5 Hz, 2H, -CH- of fluorenyl), (m, 2H, -CH- of phenyl), (m, 2H, -CH- of fluorenyl), (d, J HH =7.8 Hz, 2H, -CHof fluorenyl), (d, J HH =7.8 Hz, 2H, -CH- of fluorenyl). 13 C NMR (75 MHz, CDCl 3 ): δ (ppm) 1.99 (3C, C of - SiMe 3 ), (1C, -OCH3), , , , , , , , , , , , , , , (17C, C of fluorenyl and phenyl), , (2C, Cipso of phenyl), (1C, PhCNHSiMe 3 ). Anal. Calc. for C 24 H 25 NOSi (Mr = ): C, 77.58; H, 6.78; N, 3.77%. Found: C, 77.80; H, 6.68; N, 3.82%. S1.2. Refinement The methyl H atoms were constrained to an ideal geometry, with C H distances of 0.98 Å and U iso (H) = 1.5U eq (C). N H bond distances was restrained to be 0.88 Å and U iso (H) = 1.2U eq (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 U iso (H) = 1.2U eq (C). S2. Comment 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 η 1, η 3, and η 5 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 CH 2 -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, η 5 and η 6 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 sup-1

4 planar with an rms deviation of Å from the best fit plane through its 13 C atoms. This plane forms a dihedral angle of (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 (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 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). Figure 1 The molecular structure, showing the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are omitted for clarity. sup-2

5 Figure 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. N-[(9H-Fluoren-9-ylidene)(2-methoxyphenyl)methyl]-1,1,1-trimethylsilanamine Crystal data C 24 H 25 NOSi M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (3) Å b = (19) Å c = (6) Å β = (2) V = (9) Å 3 Z = 4 Data collection Bruker P4 diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.976, T max = F(000) = 792 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 6083 reflections θ = µ = 0.13 mm 1 T = 173 K Prism, yellow mm measured reflections 4628 independent reflections 4212 reflections with I > 2σ(I) R int = θ max = 27.4, θ min = 2.7 h = k = l = sup-3

6 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 248 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0619P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.50 e Å 3 Δρ min = 0.26 e Å 3 Special details 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 F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Si (6) (7) (4) (19) O (19) (2) (11) (5) N (18) (2) (11) (4) H * C (2) (2) (13) (5) C (2) (2) (14) (5) C (2) (2) (15) (5) H3A * C (2) (3) (16) (6) H4A * C (3) (3) (16) (6) H5A * C (2) (3) (15) (5) H6A * C (2) (2) (14) (5) C (2) (2) (14) (5) C (2) (3) (15) (6) H9A * C (3) (3) (16) (6) H10A * C (3) (3) (16) (6) H11A * C (2) (3) (16) (6) H12A * C (2) (2) (14) (5) sup-4

7 C (2) (2) (14) (5) C (2) (2) (15) (5) C (2) (3) (16) (6) H16A * C (3) (3) (2) (7) H17A * C (3) (3) (2) (8) H18A * C (3) (3) (19) (7) H19A * C (2) (3) (16) (6) C (3) (4) (17) (9) H21A * H21B * H21C * C (3) (4) (18) (8) H22A * H22B * H22C * C (3) (3) (18) (7) H23A * H23B * H23C * C (3) (3) (18) (7) H24A * H24B * H24C * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Si (3) (3) (4) (3) (3) (3) O (11) (12) (10) (9) (9) (9) N (10) (10) (10) (8) (9) (8) C (11) (11) (11) (9) (10) (9) C (11) (11) (12) (9) (10) (9) C (12) (12) (13) (9) (11) (10) C (13) (11) (15) (10) (12) (10) C (14) (13) (15) (11) (12) (11) C (12) (13) (13) (10) (11) (10) C (12) (12) (12) (9) (10) (9) C (12) (12) (12) (9) (10) (9) C (12) (14) (13) (10) (11) (11) C (14) (15) (14) (12) (12) (12) C (15) (13) (16) (12) (13) (12) C (13) (12) (14) (10) (12) (11) C (12) (12) (12) (9) (10) (9) C (12) (11) (12) (9) (10) (9) sup-5

8 C (11) (11) (13) (9) (11) (10) C (13) (12) (15) (10) (12) (11) C (15) (13) (2) (11) (15) (13) C (17) (15) (2) (13) (18) (15) C (16) (16) (18) (13) (15) (14) C (13) (13) (15) (11) (12) (11) C (2) (2) (16) (18) (16) (15) C (17) (2) (18) (16) (15) (16) C (14) (15) (18) (11) (13) (13) C (15) (13) (17) (11) (14) (12) Geometric parameters (Å, º) Si1 N (2) C11 C (4) Si1 C (3) C11 H11A Si1 C (3) C12 C (3) Si1 C (3) C12 H12A O1 C (3) C14 C (3) O1 C (3) C15 C (3) N1 C (3) C15 C (4) N1 H C16 C (4) C1 C (3) C16 H16A C1 C (3) C17 C (5) C1 C (3) C17 H17A C2 C (3) C18 C (5) C2 C (3) C18 H18A C3 C (3) C19 C (4) C3 H3A C19 H19A C4 C (4) C21 H21A C4 H4A C21 H21B C5 C (4) C21 H21C C5 H5A C22 H22A C6 C (3) C22 H22B C6 H6A C22 H22C C7 C (3) C23 H23A C8 C (3) C23 H23B C8 C (3) C23 H23C C9 C (4) C24 H24A C9 H9A C24 H24B C10 C (4) C24 H24C C10 H10A N1 Si1 C (12) C12 C13 C (2) N1 Si1 C (12) C8 C13 C (2) C22 Si1 C (16) C1 C14 N (2) N1 Si1 C (12) C1 C14 C (2) C22 Si1 C (15) N1 C14 C (2) C23 Si1 C (13) C16 C15 C (2) sup-6

9 C20 O1 C (2) C16 C15 C (2) C14 N1 Si (16) C20 C15 C (2) C14 N1 H C17 C16 C (3) Si1 N1 H C17 C16 H16A C14 C1 C (2) C15 C16 H16A C14 C1 C (2) C18 C17 C (3) C13 C1 C (19) C18 C17 H17A C3 C2 C (2) C16 C17 H17A C3 C2 C (2) C17 C18 C (3) C7 C2 C (2) C17 C18 H18A C4 C3 C (2) C19 C18 H18A C4 C3 H3A C18 C19 C (3) C2 C3 H3A C18 C19 H19A C3 C4 C (2) C20 C19 H19A C3 C4 H4A O1 C20 C (3) C5 C4 H4A O1 C20 C (2) C6 C5 C (2) C19 C20 C (3) C6 C5 H5A O1 C21 H21A C4 C5 H5A O1 C21 H21B C5 C6 C (2) H21A C21 H21B C5 C6 H6A O1 C21 H21C C7 C6 H6A H21A C21 H21C C6 C7 C (2) H21B C21 H21C C6 C7 C (2) Si1 C22 H22A C2 C7 C (2) Si1 C22 H22B C9 C8 C (2) H22A C22 H22B C9 C8 C (2) Si1 C22 H22C C13 C8 C (2) H22A C22 H22C C10 C9 C (2) H22B C22 H22C C10 C9 H9A Si1 C23 H23A C8 C9 H9A Si1 C23 H23B C9 C10 C (2) H23A C23 H23B C9 C10 H10A Si1 C23 H23C C11 C10 H10A H23A C23 H23C C10 C11 C (2) H23B C23 H23C C10 C11 H11A Si1 C24 H24A C12 C11 H11A Si1 C24 H24B C11 C12 C (2) H24A C24 H24B C11 C12 H12A Si1 C24 H24C C13 C12 H12A H24A C24 H24C C12 C13 C (2) H24B C24 H24C C22 Si1 N1 C (3) C7 C8 C13 C (2) C23 Si1 N1 C (2) C9 C8 C13 C (2) C24 Si1 N1 C (2) C7 C8 C13 C1 0.3 (3) C14 C1 C2 C3 5.7 (4) C14 C1 C13 C (4) C13 C1 C2 C (2) C2 C1 C13 C (2) C14 C1 C2 C (2) C14 C1 C13 C (2) sup-7

10 C13 C1 C2 C7 3.6 (2) C2 C1 C13 C8 2.3 (2) C7 C2 C3 C4 0.9 (3) C13 C1 C14 N (2) C1 C2 C3 C (2) C2 C1 C14 N (4) C2 C3 C4 C5 0.0 (4) C13 C1 C14 C (4) C3 C4 C5 C6 0.6 (4) C2 C1 C14 C (2) C4 C5 C6 C7 0.3 (4) Si1 N1 C14 C (2) C5 C6 C7 C2 0.6 (4) Si1 N1 C14 C (3) C5 C6 C7 C (2) C1 C14 C15 C (3) C3 C2 C7 C6 1.2 (3) N1 C14 C15 C (3) C1 C2 C7 C (2) C1 C14 C15 C (3) C3 C2 C7 C (2) N1 C14 C15 C (2) C1 C2 C7 C8 3.5 (3) C20 C15 C16 C (4) C6 C7 C8 C9 4.6 (4) C14 C15 C16 C (2) C2 C7 C8 C (2) C15 C16 C17 C (4) C6 C7 C8 C (2) C16 C17 C18 C (5) C2 C7 C8 C (3) C17 C18 C19 C (5) C13 C8 C9 C (4) C21 O1 C20 C (4) C7 C8 C9 C (2) C21 O1 C20 C (2) C8 C9 C10 C (4) C18 C19 C20 O (3) C9 C10 C11 C (4) C18 C19 C20 C (4) C10 C11 C12 C (4) C16 C15 C20 O (2) C11 C12 C13 C8 2.9 (4) C14 C15 C20 O1 0.8 (3) C11 C12 C13 C (2) C16 C15 C20 C (4) C9 C8 C13 C (3) C14 C15 C20 C (2) Hydrogen-bond geometry (Å, º) 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 Cg1 i (3) 133 C12 H12A Cg (4) 138 C16 H16A Cg2 i (3) 145 C21 H21C Cg2 ii (4) 139 C24 H24A Cg3 i (4) 158 Symmetry codes: (i) x+2, y+1, z+1; (ii) x+2, y 1/2, z+3/2. sup-8