Experimental. Crystal data. C 32 H 25 NO 5 M r = Monoclinic, C2=c a = (6) Å b = (2) Å c = (3) Å = 96.

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1 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Methyl 9-hydroxy-15-methyl-2-oxo-11- (pyren-1-yl)-10-oxa-15-azatetracyclo- [ ,12.0 3,8 ]pentadeca-3(8),4,6- triene-12-carboxylate P. Sharmila, a G. Jagadeesan, a Rajesh Raju, b Raghunathan Raghavachary b and S. Aravindhan a * a Department of Physics, Presidency College, Chennai , India, and b Department of Organic Chemistry, University of Madras, Guindy Campus, Chennai , India Correspondence aravindhanpresidency@gmail.com Received 1 August 2013; accepted 7 September 2013 Experimental Crystal data C 32 H 25 NO 5 M r = Monoclinic, C2=c a = (6) Å b = (2) Å c = (3) Å = (1) Data collection Bruker Kappa APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2004) T min = 0.979, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 347 parameters V = (17) Å 3 Z =8 Mo K radiation = 0.09 mm 1 T = 293 K mm measured reflections 4661 independent reflections 3280 reflections with I > 2(I) R int = H atoms treated by a mixture of independent and constrained refinement max = 0.15 e Å 3 min = 0.18 e Å 3 Key indicators: single-crystal X-ray study; T = 293 K; mean (C C) = Å; R factor = 0.041; wr factor = 0.114; data-to-parameter ratio = Table 1 Hydrogen-bond geometry (Å, ). In the title compound, C 32 H 25 NO 5, the furan and pyrrole rings each adopt an envelope conformation, the respective flap atoms being the C atom bearing the pyrene substituent and the CH 2 atom adjacent to the N atom. The molecular conformation is stabilized by an intramolecular O HN hydrogen bond. In the crystal, C HO contacts link the molecules, forming a two-dimensional network parallel to (001). Related literature For the solid state structures of pyrenes, see: Robertson & White (1947); Camerman & Trotter (1965); Allmann (1970); Hazell et al. (1972); Kai et al. (1978). For a related structure, see: Gruber et al. (2010). For the use of pyrenes in fluorescence sensors, see: Bren (2001). D HA D H HA DA D HA C27 H27O3 i (2) 155 O2 H2N 0.87 (2) 1.95 (2) (19) 133 (2) Symmetry code: (i) x; y þ 1; z þ 1 2. Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT6925). References Allmann, R. (1970). Z. Kristallogr. Kristallgeom. Kristallphys. Kristallchem. 132, Bren, V. A. (2001). Russ. Chem. Rev. 70, Bruker (2004). APEX2, SAINT, XPREP and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Camerman, A. & Trotter, J. (1965). Acta Cryst. 18, Farrugia, L. J. (2012). J. Appl. Cryst. 45, Gruber, T., Seichter, W. & Weber, E. (2010). Acta Cryst. E66, o443. Hazell, A. C., Larsen, F. K. & Lehmann, M. S. (1972). Acta Cryst. B28, Kai, Y., Hama, F., Yasuoka, N. & Kasai, N. (1978). Acta Cryst. B34, Robertson, J. M. & White, J. G. (1947). J. Chem. Soc. pp Sheldrick, G. M. (2008). Acta Cryst. A64, Spek, A. L. (2009). Acta Cryst. D65, doi: /s Sharmila et al. o1569

2 supplementary materials [doi: /s ] Methyl 9-hydroxy-15-methyl-2-oxo-11-(pyren-1-yl)-10-oxa-15-azatetracyclo- [ ,12.0 3,8 ]pentadeca-3(8),4,6-triene-12-carboxylate P. Sharmila, G. Jagadeesan, Rajesh Raju, Raghunathan Raghavachary and S. Aravindhan 1. Comment Owing to their electronic, optical and geometric properties, mono-functionalized pyrenes, attachable to a receptor platform, are of special interest for the development of fluorescent sensors (Bren et al., 2001). The pyrene moiety alone shows no significant deviations of bond lengths and angles compared with those of the unsubstituted analogue (Robertson et al., 1947; Camerman et al., 1965; Allmann et al., 1970; Hazell et al., 1972; Kai et al., 1978). The furan and pyrole rings adopt an envelope conformation. C17 and C20 are displaced by (2) Å and (2) Å, respectively, from the least-square planes formed by the remaining ring atoms. The dihedral angle between the furan and pyrole ring being (6). The carboxylate group (C30/05/C31) is almost perpendicular to the furan ring with dihedral angle of (1). The molecular conformation is stabilized by an intramolecular O H N hydrogen bond and the crystal packing is stabilized by intermolecular C H O contacts. 2. Experimental To a reaction mixture of 2-((3a2, 4-dihydropyren-1-yl)(hydroxy)methyl)acrylate (1 mmol), ninhydrine (1.1 mmol) and sarcosine (1.1 mmol) was refluxed in methanol until completion of the reaction was evidenced by TLC analysis. After completion of the reaction the solvent was evaporated under reduced pressure. The crude reaction mixture was dissolved in dichloromethane and washed with water followed by brine solution. The organic layer was separated and dried over sodium sulfate, filtering and evaporation of the organic solvent under reduced pressure. The product was separated by column chromatography using hexane and ethyl acetate (3:7) as an eluent to give colorless solid. The product was dissolved in chloroform and heated for five minutes. The resulting solution was subjected to crystallization by slow evaporation of the solvent resulting in single crystals suitable for XRD studies. 3. Refinement All the H atoms were positioned geometrically, with C H = Å and constrained to ride on their parent atom, with U iso (H) =1.5U eq (C) for methyl H atoms and 1.2U eq (C) for other H atoms. The hydroxyl H atom was freely refined. Computing details Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009). sup-1

3 Figure 1 The molecular structure of the title compound, Displacement ellipsoids are drawn at the 30% probability level, H atoms have been omitted for clarity. sup-2

4 Figure 2 Crystal packing of the title compound, Hydrogen bonds are shown as dashed lines. For the sake of clarity, H atoms not involved in the interactions have been omitted. (I) Crystal data C 32 H 25 NO 5 M r = Monoclinic, C2/c Hall symbol: -C 2yc a = (6) Å b = (2) Å c = (3) Å β = (1) V = (17) Å 3 Z = 8 Data collection Bruker Kappa APEXII CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω and φ scan Absorption correction: multi-scan (SADABS; Bruker, 2004) T min = 0.979, T max = F(000) = 2112 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 8834 reflections θ = µ = 0.09 mm 1 T = 293 K Block, colourless mm measured reflections 4661 independent reflections 3280 reflections with I > 2σ(I) R int = θ max = 25.7, θ min = 2.0 h = k = l = sup-3

5 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 347 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 atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.0547P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.15 e Å 3 Δρ min = 0.18 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 O (4) (10) (8) (3) O (4) (11) (8) (3) O (4) (12) (10) (3) N (5) (13) (9) (4) C (5) (15) (11) (4) H * C (5) (15) (11) (4) O (4) (13) (10) (4) C (5) (17) (11) (4) C (5) (16) (11) (4) C (5) (15) (10) (4) O (5) (15) (10) (5) C (5) (15) (11) (4) C (5) (16) (11) (4) C (6) (19) (12) (5) C (6) (16) (12) (4) C (6) (16) (13) (5) H * C (5) (15) (11) (4) C (5) (15) (11) (4) C (5) (18) (11) (5) H * C (5) (16) (11) (4) C (6) (16) (13) (5) H * sup-4

6 C (6) (18) (12) (5) H * C (6) (2) (13) (5) H * C (6) (2) (13) (6) H * C (6) (17) (12) (5) H21A * H21B * C (6) (2) (13) (5) C (6) (18) (12) (5) H20A * H20B * C (6) (18) (13) (5) H * C (6) (16) (13) (4) C (7) (19) (14) (5) H * C (7) (2) (14) (6) H * C (5) (15) (10) (4) C (7) (19) (14) (5) H32A * H32B * H32C * C (7) (2) (15) (6) H * C (7) (2) (13) (6) H * C (7) (3) (16) (7) H * C (7) (3) (17) (7) H * C (11) (3) (2) (13) H31A * H31B * H31C * H (7) (2) (16) (7)* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 O (7) (7) (7) (5) (5) (6) O (9) (7) (7) (7) (6) (6) O (7) (8) (8) (6) (6) (6) N (9) (9) (7) (7) (6) (7) C (9) (10) (9) (8) (7) (7) C (10) (10) (9) (8) (7) (7) O (9) (9) (9) (8) (7) (7) C (11) (12) (8) (9) (7) (8) sup-5

7 C (10) (10) (8) (8) (7) (7) C (10) (10) (8) (8) (7) (7) O (13) (11) (9) (9) (9) (8) C (9) (10) (9) (8) (7) (7) C (10) (10) (8) (8) (7) (7) C (12) (13) (10) (10) (8) (9) C (11) (10) (9) (9) (8) (8) C (10) (11) (11) (9) (8) (9) C (10) (10) (9) (7) (7) (7) C (10) (10) (8) (8) (7) (7) C (10) (12) (9) (9) (7) (9) C (10) (10) (8) (8) (7) (8) C (12) (10) (11) (8) (9) (9) C (11) (11) (10) (9) (8) (8) C (12) (14) (11) (10) (9) (10) C (13) (16) (9) (12) (8) (10) C (12) (11) (9) (9) (8) (8) C (11) (14) (10) (10) (8) (10) C (13) (12) (9) (10) (9) (8) C (13) (12) (11) (10) (9) (9) C (11) (10) (10) (9) (9) (8) C (14) (12) (12) (10) (10) (9) C (15) (13) (12) (12) (11) (10) C (10) (9) (8) (7) (7) (7) C (13) (14) (11) (11) (9) (10) C (14) (17) (13) (13) (11) (12) C (14) (15) (11) (12) (10) (10) C (13) (19) (15) (12) (11) (13) C (13) (2) (16) (14) (11) (15) C (3) (3) (2) (2) (2) (2) Geometric parameters (Å, º) O1 C (2) C18 C (2) O1 C (18) C18 C (2) O3 C (19) C29 C (3) O2 C (2) C29 H O2 H (2) C24 C (2) N C (2) C14 H N C (2) C4 C (3) N C (2) C4 H C17 C (2) C5 C (3) C17 C (2) C5 H C17 H C28 C (3) C16 C (2) C28 H C16 C (2) C21 C (3) O4 C (2) C21 H21A C1 C (3) C21 H21B C1 C (3) C6 C (3) C1 C (2) C20 H20A sup-6

8 C2 C (2) C20 H20B C2 C (2) C26 C (3) C3 C (2) C26 H O5 C (2) C12 C (3) O5 C (3) C12 H C23 C (2) C11 H C23 C (2) C32 H32A C23 C (2) C32 H32B C25 C (2) C32 H32C C25 C (2) C9 C (3) C10 C (3) C9 H C10 C (3) C27 H C13 C (2) C7 C (3) C13 C (3) C7 H C15 C (3) C8 H C15 H C31 H31A C22 C (2) C31 H31B C18 C (2) C31 H31C C22 O1 C (12) C4 C5 C (19) C22 O2 H (15) C4 C5 H C20 N C (14) C6 C5 H C20 N C (14) C29 C28 C (17) C32 N C (14) C29 C28 H O1 C17 C (13) C27 C28 H O1 C17 C (12) C20 C21 C (14) C16 C17 C (13) C20 C21 H21A O1 C17 H C18 C21 H21A C16 C17 H C20 C21 H21B C18 C17 H C18 C21 H21B C15 C16 C (16) H21A C21 H21B C15 C16 C (15) C7 C6 C (2) C3 C16 C (15) C7 C6 C (2) C6 C1 C (17) C1 C6 C (17) C6 C1 C (17) N C20 C (13) C10 C1 C (17) N C20 H20A C13 C2 C (16) C21 C20 H20A C13 C2 C (15) N C20 H20B C1 C2 C (16) C21 C20 H20B C16 C3 C (15) H20A C20 H20B C16 C3 C (16) C27 C26 C (19) C2 C3 C (15) C27 C26 H C30 O5 C (18) C24 C26 H C29 C23 C (16) O4 C30 O (17) C29 C23 C (16) O4 C30 C (15) C24 C23 C (13) O5 C30 C (16) O3 C25 C (16) C11 C12 C (19) O3 C25 C (14) C11 C12 H C24 C25 C (13) C13 C12 H sup-7

9 C9 C10 C (2) C12 C11 C (19) C9 C10 C (2) C12 C11 H C1 C10 C (17) C10 C11 H C14 C13 C (16) N C19 C (13) C14 C13 C (17) N C19 C (13) C2 C13 C (17) C25 C19 C (12) C14 C15 C (17) N C19 C (12) C14 C15 H C25 C19 C (13) C16 C15 H C22 C19 C (12) O2 C22 O (13) N C32 H32A O2 C22 C (13) N C32 H32B O1 C22 C (13) H32A C32 H32B O2 C22 C (13) N C32 H32C O1 C22 C (12) H32A C32 H32C C23 C22 C (13) H32B C32 H32C C30 C18 C (14) C8 C9 C (2) C30 C18 C (13) C8 C9 H C21 C18 C (14) C10 C9 H C30 C18 C (13) C26 C27 C (18) C21 C18 C (13) C26 C27 H C17 C18 C (12) C28 C27 H C28 C29 C (18) C8 C7 C (2) C28 C29 H C8 C7 H C23 C29 H C6 C7 H C23 C24 C (15) C9 C8 C (2) C23 C24 C (15) C9 C8 H C26 C24 C (16) C7 C8 H C15 C14 C (17) O5 C31 H31A C15 C14 H O5 C31 H31B C13 C14 H H31A C31 H31B C5 C4 C (18) O5 C31 H31C C5 C4 H H31A C31 H31C C3 C4 H H31B C31 H31C C22 O1 C17 C (13) C10 C1 C6 C7 0.4 (3) C22 O1 C17 C (15) C2 C1 C6 C (16) O1 C17 C16 C (2) C10 C1 C6 C (16) C18 C17 C16 C (19) C2 C1 C6 C5 0.6 (2) O1 C17 C16 C (14) C4 C5 C6 C (18) C18 C17 C16 C (18) C4 C5 C6 C1 1.3 (3) C6 C1 C2 C (15) C32 N C20 C (15) C10 C1 C2 C (2) C19 N C20 C (18) C6 C1 C2 C3 2.0 (2) C18 C21 C20 N (18) C10 C1 C2 C (14) C23 C24 C26 C (3) C15 C16 C3 C2 1.9 (2) C25 C24 C26 C (18) C17 C16 C3 C (14) C31 O5 C30 O4 3.6 (3) C15 C16 C3 C (16) C31 O5 C30 C (2) C17 C16 C3 C4 2.3 (2) C21 C18 C30 O (18) C13 C2 C3 C (2) C17 C18 C30 O (2) sup-8

10 C1 C2 C3 C (14) C19 C18 C30 O (2) C13 C2 C3 C (14) C21 C18 C30 O5 8.9 (2) C1 C2 C3 C4 1.6 (2) C17 C18 C30 O (16) C6 C1 C10 C9 1.3 (2) C19 C18 C30 O (17) C2 C1 C10 C (15) C14 C13 C12 C (18) C6 C1 C10 C (16) C2 C13 C12 C (3) C2 C1 C10 C (2) C13 C12 C11 C (3) C1 C2 C13 C (15) C9 C10 C11 C (18) C3 C2 C13 C (2) C1 C10 C11 C (3) C1 C2 C13 C (2) C20 N C19 C (16) C3 C2 C13 C (15) C32 N C19 C (2) C3 C16 C15 C (3) C20 N C19 C (15) C17 C16 C15 C (16) C32 N C19 C (17) C17 O1 C22 O (13) C20 N C19 C (17) C17 O1 C22 C (15) C32 N C19 C (15) C17 O1 C22 C (16) O3 C25 C19 N 47.9 (2) C29 C23 C22 O (2) C24 C25 C19 N (15) C24 C23 C22 O (16) O3 C25 C19 C (16) C29 C23 C22 O (2) C24 C25 C19 C (17) C24 C23 C22 O (15) O3 C25 C19 C (2) C29 C23 C22 C (16) C24 C25 C19 C (15) C24 C23 C22 C (18) O2 C22 C19 N (19) O1 C17 C18 C (13) O1 C22 C19 N (15) C16 C17 C18 C (17) C23 C22 C19 N (14) O1 C17 C18 C (16) O2 C22 C19 C (15) C16 C17 C18 C (2) O1 C22 C19 C (13) O1 C17 C18 C (15) C23 C22 C19 C (16) C16 C17 C18 C (14) O2 C22 C19 C (14) C24 C23 C29 C (3) O1 C22 C19 C (16) C22 C23 C29 C (17) C23 C22 C19 C (13) C29 C23 C24 C (3) C30 C18 C19 N (15) C22 C23 C24 C (16) C21 C18 C19 N (16) C29 C23 C24 C (15) C17 C18 C19 N (13) C22 C23 C24 C (2) C30 C18 C19 C (18) O3 C25 C24 C (17) C21 C18 C19 C (14) C19 C25 C24 C (19) C17 C18 C19 C (14) O3 C25 C24 C (3) C30 C18 C19 C (14) C19 C25 C24 C (18) C21 C18 C19 C (14) C16 C15 C14 C (3) C17 C18 C19 C (15) C2 C13 C14 C (3) C1 C10 C9 C8 0.9 (3) C12 C13 C14 C (17) C11 C10 C9 C (19) C16 C3 C4 C (16) C24 C26 C27 C (3) C2 C3 C4 C5 0.2 (2) C29 C28 C27 C (3) C3 C4 C5 C6 1.7 (3) C1 C6 C7 C8 0.9 (3) C23 C29 C28 C (3) C5 C6 C7 C (2) C30 C18 C21 C (18) C10 C9 C8 C7 0.5 (3) C17 C18 C21 C (15) C6 C7 C8 C9 1.4 (3) C19 C18 C21 C (16) sup-9

11 Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C27 H27 O3 i (2) 155 O2 H2 N 0.87 (2) 1.95 (2) (19) 133 (2) Symmetry code: (i) x, y+1, z+1/2. sup-10