Experimental. Crystal data. C 13 H 17 N 3 O 2 M r = Monoclinic, Cc a = (4) Å b = (4) Å c = (3) Å = 111.

Transcript

1 Acta Crystallographica Section E Structure Reports Online ISSN [2-(4-Hydroxyphenyl)ethyl]-3-propyl- 1H-1,2,4-triazol-5(4H)-one Experimental Crystal data C 13 H 17 N 3 O 2 M r = Monoclinic, Cc a = (4) Å b = (4) Å c = (3) Å = (19) organic compounds V = (3) Å 3 Z =32 Cu K radiation = 0.72 mm 1 T = 123 K mm Sema Öztürk Yildirim, a,b Ray J. Butcher, a * Dilek Ünlüer c and Yavuz Köysal d a Chemistry Department, Howard University, Washington, DC 20059, USA, c Department of Chemistry, Karadeniz Technical University, Trabzon TR-61080, Turkey, b Department of Physics, Faculty of Sciences, Erciyes University, Kayseri, Turkey, and d Yeşilyurt Demir Çelik Vocational School, Ondokuz Mayis University, Samsun, Turkey Correspondence rbutcher99@yahoo.com Received 23 April 2012; accepted 30 April 2012 Key indicators: single-crystal X-ray study; T = 123 K; mean (C C) = Å; R factor = 0.040; wr factor = 0.108; data-to-parameter ratio = 9.3. Data collection Oxford Diffraction Gemini-R diffractometer Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) T min = 0.756, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 1313 parameters 2 restraints measured reflections independent reflections reflections with I > 2(I) R int = H-atom parameters constrained max = 0.56 e Å 3 min = 0.23 e Å 3 Absolute structure: Flack (1983), 1607 Friedel pairs Flack parameter: 0.08 (12) The asymmetric unit of the title compound, C 13 H 17 N 3 O 2, contains eight crystallographically independent molecules. The planes of the benzene and triazole rings in the eight molecules make dihedral angles of 5.53 (13), 9.33 (13), (11), (8), (12), 8.03 (8), (11), and 7.98 (8). The eight molecules in the asymmetric unit are linked by intermolecular O HO and N HO hydrogen bonds, forming a three-dimensional network. Related literature For the antiviral activity of triazoles, see: Sancak et al. (2012); Gurumoorthy et al. (2011). For the synthesis of antibiotics, fungicides, herbicides and plant growth hormone insulators, see: Ünver et al. (2006, 2011). For potentially good corrosion inhibitions, see: Lebrini et al. (2008). For bond lengths in related structures, see: Öztürk et al. (2004a,b); Akkurt et al. (2004). For standard bond lengths, see: Allen et al. (1987). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA O2A H2AO1H (3) 174 O2C H2CO1E (3) 172 O2G H2GO1C (3) 172 O2H H2HO1D (3) 174 N2B H2BAO1C (3) 169 N2C H2CAO1B (3) 174 N2F H2FAO1H (3) 166 N2H H2HAO1F (3) 167 O2B H2BO1G i (3) 177 O2D H2DO1F i (3) 178 O2E H2EO1B ii (3) 165 O2F H2FO1A ii (3) 162 N2A H2AAO1D iii (3) 170 N2E H2EAO1G iii (3) 168 N2D H2DAO1A iv (3) 173 N2G H2GAO1E iv (3) 168 Symmetry codes: (i) x 1 2 ; y þ 1 2 ; z; (ii) x þ 1 2 ; y 1 2 ; z; (iii) x þ 1 2 ; y þ 1 2 ; z; (iv) x 1 2 ; y 1 2 ; z. Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL. RJB acknowledges the NSF MRI program (grant No. CHE ) for funds to purchase the diffractometer. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG5217). doi: /s Öztürk Yildirim et al. o1651

2 organic compounds References Akkurt, M., Öztürk, S., Servi, S., Cansız, A., Şekerci, M. & Kazak, C. (2004). Acta Cryst. E60, o1507 o1509. Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1 19. Flack, H. D. (1983). Acta Cryst. A39, Gurumoorthy, A., Gopalsamy, V., Ramamurthi, K., Ünlüer, D. & Çelik, F. (2011). Acta Cryst. E67, o3188 o3189. Lebrini, M., Traisnel, M., Lagrenee, M., Mernari, B. & Bentiss, F. (2008). Corros. Sci. 50, Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England. Öztürk, S., Akkurt, M., Cansız, A., Koparır, M., Şekerci, M. & Heinemann, F. W. (2004a). Acta Cryst. E60, o425 o427. Öztürk, S., Akkurt, M., Cansız, A., Koparır, M., Şekerci, M. & Heinemann, F. W. (2004b). Acta Cryst. E60, o642 o644. Sancak, K., Ünver, Y., Meydanal, S., Ünlüer, D., Dügdü, E., Kör, G., Çelik, F. & Birinci, E. (2012). Turk. J. Chem. 36, Sheldrick, G. M. (2008). Acta Cryst. A64, Ünver, Y., Meydanal, S., Sancak, K., Ünlüer, D., Ustabaş, R. & Dügdü, E. (2011). Turk. J. Chem. 35, Ünver, Y., Ustabaş, R., Çoruh, U., Sancak, K. & Vázquez-López, E. M. (2006). Acta Cryst. E62, o3938 o3939. o1652 Öztürk Yildirim et al. C 13 H 17 N 3 O 2

3 supplementary materials [doi: /s ] 4-[2-(4-Hydroxyphenyl)ethyl]-3-propyl-1H-1,2,4-triazol-5(4H)-one Sema Öztürk Yildirim, Ray J. Butcher, Dilek Ünlüer and Yavuz Köysal Comment During the past two decades, triazole and its derivatives represent an important class of heterocycles. The arrangement of 3 basic nitrogen atoms in the triazole ring induces antiviral activities in the compounds containing this ring (Sancak et al., 2012; Gurumoorthy et al., 2011). They are of biological importance and are used in the synthesis of drugs such as antibiotics, fungicides, herbicides, and plant growth hormone insulators (Ünver et al., 2011; Ünver et al., 2006) and are also potentially good corrosion inhibitors (Lebrini et al., 2008). Eight independent molecules of the title compound (I) in the asymmetric unit are shown in Fig. 1 and labelled as A to H. The bond lengths and angles in the eight molecules have normal values (Öztürk et al., 2004a; Öztürk et al., 2004b; Akkurt et al., 2004; Allen et al., 1987). The phenyl and triazol rings in molecules (A - H) make dihedral angles of 5.53 (13), 9.33 (13), (11), (08), (12), 8.03 (08), (11) and 7.98 (08) to each other, respectively. The propyl group on the bridging C1 atom position and takes a zigzag form in eight molecules forming torsion angles of (25) in molecule A [ (26) in B; (25) in C; (23) in D; (40) in E; (31) in F; (30) in G and (40) in H]. The oxygen atoms are coplanar with the benzene and triazol rings in all molecules. The major difference in conformation for the 8 molecules occurs for the orientation of the propyl group with respect to the triazole ring. For molecules A, B, C, D, E, F, G and H these values are 6.5 (4), 0.4 (4), 1.9 (4), 13.7 (4), 12.2 (4), 0.9 (4), -8.5 (4) and (5), respectively. In the crystal structure (Fig. 3), the molecules are linked through O H O and N H O intra- and intermolecular hydrogen bonds (Table 1) to form a three-dimensional network. Experimental A solution of 4-(4-metoksifeniletil)-5-propil-2H-1,2,4-triazol-3(4H)-on (10 mmol) in chloroform (100 ml) was added to a solution of boron tribromide (10 mmol) in chloroform (200 ml) at 273 K. The reaction mixture was poured into ice containing sufficient 50% sodium hydroxide to attain a ph of 10. The addition of concentrated sulfuric acid provided a precipitate that was extracted into ether. The combined organic extract was washed with water and brine, and then dried and concentrated in a vacuum to obtain compounds. The crude product was recrystallized using ethyl acetate and petroleum ether (1:2) to afford the desired compound. Yield: 130 mg (40%). Mp: K. Refinement H atoms were positioned geometrically [C H = Å; N H = 0.86 Å and O H = 0.82 Å] and refined using a riding model with U iso (H) = 1.2 Ueq (C,N) and 1.5U eq (O). For some of the strongest reflections detector saturation was observed as F o was significantly less than F c. sup-1

4 Computing details Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis PRO (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008). Figure 1 The eight independent molecules in the asymmetric unit of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. sup-2

5 Figure 2 One of the eight independent molecules in the asymmetric unit to show clearly the atomic labelling (molecule A). The other seven molecules are labelled in a similar manner. sup-3

6 Figure 3 The crystal packing of the title compound viewed along the c axis, showing the formation of hydrogen bonded dimers further linked by additional hydrogen bonding. The hydrogen bonds as dashed lines. 4-[2-(4-Hydroxyphenyl)ethyl]-3-propyl-1H-1,2,4-triazol-5(4H)-one Crystal data C 13 H 17 N 3 O 2 M r = Monoclinic, Cc Hall symbol: C -2yc a = (4) Å b = (4) Å c = (3) Å β = (19) V = (3) Å 3 Z = 32 Data collection Oxford Diffraction Gemini-R diffractometer Radiation source: Enhance (Cu) X-ray Source Graphite monochromator Detector resolution: pixels mm -1 ω scans F(000) = 4224 D x = Mg m 3 Cu Kα radiation, λ = Å Cell parameters from 9884 reflections θ = µ = 0.72 mm 1 T = 123 K Plate, colorless mm Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007) T min = 0.756, T max = measured reflections independent reflections reflections with I > 2σ(I) R int = sup-4

7 θ max = 75.7, θ min = 3.3 h = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 1313 parameters 2 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map k = l = Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0694P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.56 e Å 3 Δρ min = 0.23 e Å 3 Absolute structure: Flack (1983), 1607 Friedel pairs Flack parameter: 0.08 (12) Special details Experimental. CrysAlis RED, (Oxford Diffraction, 2007) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. (Clark & Reid, 1995). 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 O1A (7) (7) (14) (4) O2A (9) (7) (16) (5) H2A * O1B (7) (7) (14) (4) O2B (8) (7) (15) (4) H2B * O1C (7) (7) (14) (4) O2C (7) (7) (14) (4) H2C * O1D (7) (7) (14) (4) O2D (8) (7) (16) (5) H2D * O1E (7) (7) (13) (4) O2E (8) (7) (15) (4) H2E * O1F (7) (7) (14) (4) O2F (8) (7) (17) (5) H2F * O1G (8) (7) (15) (4) O2G (8) (7) (15) (4) sup-5

8 H2G * O1H (8) (7) (15) (4) O2H (8) (8) (16) (5) H2H * N1A (9) (8) (15) (4) N2A (9) (8) (16) (4) H2AA * N3A (8) (8) (14) (4) N1B (9) (8) (16) (5) N2B (9) (9) (17) (5) H2BA * N3B (8) (8) (15) (4) N1C (8) (8) (15) (4) N2C (8) (8) (15) (4) H2CA * N3C (8) (8) (14) (4) N1D (9) (8) (16) (5) N2D (9) (8) (17) (5) H2DA * N3D (8) (8) (14) (4) N1E (9) (9) (17) (5) N2E (9) (9) (16) (5) H2EA * N3E (9) (8) (15) (4) N1F (9) (9) (18) (5) N2F (9) (9) (18) (5) H2FA * N3F (8) (8) (14) (4) N1G (9) (9) (17) (5) N2G (9) (9) (18) (5) H2GA * N3G (8) (8) (15) (4) N1H (9) (9) (17) (5) N2H (8) (8) (15) (4) H2HA * N3H (9) (8) (15) (4) C1A (10) (10) (17) (5) C2A (10) (10) (17) (5) C3A (10) (9) (17) (5) H3AA * H3AB * C4A (10) (10) (17) (5) H4AA * H4AB * C5A (10) (9) (17) (5) C6A (11) (10) (19) (5) H6AA * C7A (11) (10) (19) (5) H7AA * sup-6

9 C8A (10) (10) (18) (5) C9A (10) (10) (18) (5) H9AA * C10A (10) (10) (18) (5) H10A * C11A (10) (10) (19) (5) H11A * H11B * C12A (11) (12) (2) (6) H12A * H12B * C13A (12) (13) (3) (8) H13A * H13B * H13C * C1B (11) (10) (18) (5) C2B (10) (10) (18) (5) C3B (10) (10) (17) (5) H3BA * H3BB * C4B (11) (11) (18) (5) H4BA * H4BB * C5B (10) (11) (17) (5) C6B (10) (10) (17) (5) H6BA * C7B (10) (10) (18) (5) H7BA * C8B (10) (10) (17) (5) C9B (10) (10) (18) (5) H9BA * C10B (10) (10) (18) (5) H10B * C11B (10) (10) (2) (5) H11C * H11D * C12B (11) (10) (2) (6) H12C * H12D * C13B (14) (12) (3) (8) H13D * H13E * H13F * C1C (10) (10) (16) (5) C2C (9) (10) (17) (5) C3C (9) (10) (17) (5) H3CA * H3CB * C4C (10) (10) (17) (5) sup-7

10 H4CA * H4CB * C5C (9) (10) (16) (5) C6C (10) (10) (18) (5) H6CA * C7C (10) (10) (18) (5) H7CA * C8C (10) (9) (16) (5) C9C (9) (10) (17) (5) H9CA * C10C (10) (9) (17) (5) H10C * C11C (10) (10) (18) (5) H11E * H11F * C12C (10) (10) (2) (6) H12E * H12F * C13C (13) (12) (3) (8) H13G * H13H * H13I * C1D (10) (10) (17) (5) C2D (10) (10) (18) (5) C3D (10) (9) (17) (5) H3DA * H3DB * C4D (11) (10) (17) (5) H4DA * H4DB * C5D (10) (10) (17) (5) C6D (11) (10) (18) (5) H6DA * C7D (11) (10) (19) (5) H7DA * C8D (11) (10) (18) (5) C9D (10) (10) (18) (5) H9DA * C10D (10) (10) (18) (5) H10D * C11D (10) (10) (18) (5) H11G * H11H * C12D (11) (10) (19) (5) H12G * H12H * C13D (12) (12) (2) (6) H13J * H13K * sup-8

11 H13L * C1E (10) (10) (18) (5) C2E (10) (10) (17) (5) C3E (10) (9) (18) (5) H3EA * H3EB * C4E (12) (11) (18) (6) H4EA * H4EB * C5E (11) (10) (18) (5) C6E (11) (10) (19) (6) H6EA * C7E (11) (11) (19) (6) H7EA * C8E (11) (10) (18) (5) C9E (10) (10) (18) (5) H9EA * C10E (10) (10) (17) (5) H10E * C11E (11) (11) (2) (6) H11I * H11J * C12E (14) (15) (3) (9) H12I * H12J * C13E (14) (17) (3) (11) H13M * H13N * H13O * C1F (10) (10) (18) (5) C2F (10) (10) (17) (5) C3F (10) (10) (18) (5) H3FA * H3FB * C4F (11) (11) (18) (6) H4FA * H4FB * C5F (10) (11) (18) (5) C6F (11) (11) (2) (6) H6FA * C7F (12) (11) (2) (6) H7FA * C8F (11) (10) (19) (5) C9F (11) (10) (19) (5) H9FA * C10F (11) (10) (19) (5) H10F * C11F (11) (11) (2) (6) H11K * sup-9

12 H11L * C12F (12) (11) (2) (6) H12K * H12L * C13F (12) (12) (2) (7) H13P * H13Q * H13R * C1G (10) (10) (18) (5) C2G (10) (10) (19) (5) C3G (10) (9) (17) (5) H3GA * H3GB * C4G (11) (10) (18) (5) H4GA * H4GB * C5G (10) (10) (17) (5) C6G (11) (10) (2) (6) H6GA * C7G (11) (11) (2) (6) H7GA * C8G (10) (10) (18) (5) C9G (10) (10) (17) (5) H9GA * C10G (10) (10) (17) (5) H10G * C11G (10) (10) (2) (5) H11M * H11N * C12G (11) (11) (2) (6) H12M * H12N * C13G (12) (12) (2) (6) H13S * H13T * H13U * C1H (11) (10) (19) (5) C2H (10) (10) (18) (5) C3H (10) (11) (17) (5) H3HA * H3HB * C4H (11) (11) (18) (5) H4HA * H4HB * C5H (10) (11) (17) (5) C6H (11) (11) (19) (5) H6HA * C7H (11) (10) (2) (5) H7HA * sup-10

13 C8H (11) (10) (18) (5) C9H (11) (11) (18) (5) H9HA * C10H (11) (10) (19) (5) H10H * C11H (13) (12) (2) (7) H11O * H11P * C12H (15) (13) (3) (7) H12O * H12P * C13H (16) (16) (3) (10) H13V * H13W * H13X * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 O1A (9) (9) (10) (7) (8) (8) O2A (11) (9) (13) (8) (10) (9) O1B (9) (8) (11) (7) (8) (8) O2B (9) (9) (12) (7) (9) (9) O1C (9) (9) (11) (7) (8) (8) O2C (8) (9) (11) (7) (8) (8) O1D (9) (9) (11) (7) (8) (8) O2D (10) (9) (14) (8) (9) (9) O1E (9) (9) (10) (7) (7) (8) O2E (10) (9) (12) (8) (9) (9) O1F (9) (9) (11) (7) (8) (8) O2F (9) (9) (14) (7) (9) (9) O1G (9) (9) (12) (7) (9) (8) O2G (9) (9) (12) (7) (9) (9) O1H (9) (9) (13) (7) (9) (9) O2H (10) (10) (13) (8) (9) (9) N1A (10) (10) (11) (8) (9) (9) N2A (10) (10) (12) (8) (9) (9) N3A (10) (10) (10) (8) (8) (8) N1B (11) (11) (12) (9) (9) (9) N2B (10) (11) (13) (9) (10) (10) N3B (10) (10) (11) (8) (8) (9) N1C (10) (11) (11) (8) (8) (9) N2C (9) (11) (11) (8) (8) (9) N3C (9) (10) (10) (8) (8) (8) N1D (10) (10) (12) (8) (9) (9) N2D (10) (10) (13) (8) (9) (9) N3D (10) (10) (11) (8) (8) (8) N1E (10) (11) (13) (9) (9) (10) N2E (11) (10) (12) (8) (9) (9) N3E (10) (10) (10) (8) (8) (9) sup-11

14 N1F (11) (11) (14) (9) (10) (10) N2F (10) (11) (14) (8) (9) (10) N3F (10) (10) (11) (8) (8) (8) N1G (10) (11) (13) (8) (9) (10) N2G (11) (10) (15) (8) (11) (10) N3G (10) (10) (11) (8) (8) (8) N1H (12) (11) (13) (9) (10) (10) N2H (9) (11) (12) (8) (8) (9) N3H (10) (10) (11) (8) (8) (9) C1A (11) (12) (12) (9) (9) (10) C2A (12) (11) (12) (9) (9) (9) C3A (11) (11) (12) (9) (9) (10) C4A (12) (12) (12) (10) (10) (10) C5A (11) (12) (11) (9) (9) (9) C6A (12) (12) (14) (10) (11) (11) C7A (12) (14) (14) (10) (11) (11) C8A (12) (12) (12) (9) (10) (10) C9A (12) (11) (13) (9) (10) (10) C10A (11) (13) (13) (10) (9) (10) C11A (13) (12) (13) (10) (10) (10) C12A (13) (15) (17) (11) (12) (13) C13A (15) (18) (2) (13) (14) (16) C1B (12) (13) (13) (10) (10) (10) C2B (12) (13) (13) (10) (10) (11) C3B (11) (13) (12) (10) (9) (10) C4B (13) (14) (13) (11) (10) (11) C5B (12) (13) (12) (10) (9) (10) C6B (11) (13) (12) (10) (9) (10) C7B (12) (12) (12) (10) (9) (10) C8B (11) (13) (12) (10) (9) (10) C9B (11) (13) (13) (9) (10) (10) C10B (12) (12) (13) (10) (10) (10) C11B (12) (13) (15) (10) (11) (11) C12B (13) (13) (16) (10) (11) (11) C13B (17) (14) (3) (13) (17) (16) C1C (11) (12) (11) (9) (9) (10) C2C (11) (13) (12) (9) (9) (10) C3C (11) (12) (12) (9) (9) (10) C4C (11) (13) (12) (10) (9) (10) C5C (11) (13) (11) (9) (9) (10) C6C (11) (13) (13) (9) (10) (11) C7C (12) (12) (13) (9) (10) (10) C8C (11) (12) (12) (9) (9) (10) C9C (11) (12) (12) (9) (9) (9) C10C (11) (11) (12) (9) (9) (9) C11C (11) (13) (13) (10) (10) (11) C12C (12) (13) (15) (10) (11) (12) C13C (16) (14) (3) (12) (16) (15) C1D (11) (12) (12) (9) (9) (9) sup-12

15 C2D (12) (11) (13) (9) (10) (10) C3D (12) (11) (12) (9) (9) (9) C4D (12) (12) (12) (10) (9) (10) C5D (12) (12) (12) (10) (9) (10) C6D (13) (12) (13) (10) (10) (10) C7D (12) (13) (14) (10) (10) (11) C8D (13) (12) (13) (10) (10) (10) C9D (12) (12) (13) (10) (10) (10) C10D (11) (12) (12) (9) (9) (10) C11D (12) (12) (13) (9) (10) (10) C12D (13) (12) (14) (10) (11) (11) C13D (14) (15) (17) (12) (13) (13) C1E (12) (13) (13) (10) (10) (10) C2E (12) (12) (12) (9) (10) (10) C3E (12) (12) (12) (9) (10) (10) C4E (14) (13) (12) (11) (10) (10) C5E (12) (12) (12) (10) (10) (10) C6E (13) (12) (14) (10) (10) (11) C7E (12) (14) (14) (10) (10) (11) C8E (12) (12) (12) (10) (10) (10) C9E (12) (12) (13) (10) (10) (10) C10E (12) (13) (12) (10) (10) (10) C11E (14) (14) (17) (11) (12) (12) C12E (19) (19) (3) (15) (18) (18) C13E (17) (2) (3) (16) (17) (2) C1F (12) (12) (12) (10) (10) (10) C2F (11) (13) (12) (9) (10) (10) C3F (11) (12) (12) (9) (9) (10) C4F (12) (14) (13) (11) (10) (11) C5F (12) (14) (12) (10) (10) (11) C6F (13) (15) (17) (11) (12) (13) C7F (14) (13) (19) (11) (13) (13) C8F (13) (13) (14) (10) (11) (11) C9F (12) (12) (14) (10) (11) (11) C10F (13) (12) (13) (10) (11) (11) C11F (12) (14) (14) (10) (11) (11) C12F (14) (14) (16) (11) (12) (12) C13F (15) (14) (19) (12) (13) (14) C1G (11) (12) (13) (9) (9) (10) C2G (12) (12) (13) (10) (10) (10) C3G (11) (11) (12) (9) (9) (9) C4G (12) (12) (13) (10) (10) (10) C5G (12) (12) (12) (10) (9) (9) C6G (12) (12) (15) (10) (11) (11) C7G (12) (13) (16) (10) (11) (12) C8G (12) (12) (13) (10) (10) (10) C9G (12) (12) (12) (9) (10) (10) C10G (11) (13) (12) (9) (9) (10) C11G (12) (12) (14) (10) (10) (11) sup-13

16 C12G (13) (14) (14) (11) (11) (11) C13G (13) (15) (17) (11) (12) (13) C1H (13) (13) (14) (11) (11) (11) C2H (12) (13) (13) (9) (10) (10) C3H (12) (14) (12) (10) (9) (10) C4H (12) (13) (13) (10) (10) (11) C5H (12) (14) (12) (10) (10) (10) C6H (12) (13) (14) (10) (10) (11) C7H (13) (12) (14) (10) (11) (11) C8H (12) (13) (12) (10) (10) (10) C9H (12) (13) (13) (10) (10) (11) C10H (13) (12) (14) (10) (11) (11) C11H (16) (15) (2) (13) (15) (14) C12H (17) (16) (2) (14) (15) (15) C13H (2) (2) (2) (18) (18) (19) Geometric parameters (Å, º) O1A C2A (3) C7C H7CA O2A C8A (3) C8C C9C (4) O2A H2A C9C C10C (4) O1B C2B (3) C9C H9CA O2B C8B (3) C10C H10C O2B H2B C11C C12C (4) O1C C2C (3) C11C H11E O2C C8C (3) C11C H11F O2C H2C C12C C13C (4) O1D C2D (3) C12C H12E O2D C8D (3) C12C H12F O2D H2D C13C H13G O1E C2E (3) C13C H13H O2E C8E (3) C13C H13I O2E H2E C1D C11D (3) O1F C2F (3) C3D C4D (3) O2F C8F (3) C3D H3DA O2F H2F C3D H3DB O1G C2G (3) C4D C5D (3) O2G C8G (3) C4D H4DA O2G H2G C4D H4DB O1H C2H (3) C5D C10D (4) O2H C8H (3) C5D C6D (4) O2H H2H C6D C7D (4) N1A C1A (3) C6D H6DA N1A N2A (3) C7D C8D (4) N2A C2A (3) C7D H7DA N2A H2AA C8D C9D (4) N3A C2A (3) C9D C10D (4) N3A C1A (3) C9D H9DA N3A C3A (3) C10D H10D N1B C1B (3) C11D C12D (4) sup-14

17 N1B N2B (3) C11D H11G N2B C2B (3) C11D H11H N2B H2BA C12D C13D (4) N3B C1B (3) C12D H12G N3B C2B (3) C12D H12H N3B C3B (3) C13D H13J N1C C1C (3) C13D H13K N1C N2C (3) C13D H13L N2C C2C (3) C1E C11E (4) N2C H2CA C3E C4E (4) N3C C2C (3) C3E H3EA N3C C1C (3) C3E H3EB N3C C3C (3) C4E C5E (4) N1D C1D (3) C4E H4EA N1D N2D (3) C4E H4EB N2D C2D (3) C5E C10E (4) N2D H2DA C5E C6E (4) N3D C2D (3) C6E C7E (4) N3D C1D (3) C6E H6EA N3D C3D (3) C7E C8E (4) N1E C1E (3) C7E H7EA N1E N2E (3) C8E C9E (4) N2E C2E (3) C9E C10E (4) N2E H2EA C9E H9EA N3E C2E (3) C10E H10E N3E C1E (3) C11E C12E (5) N3E C3E (3) C11E H11I N1F C1F (3) C11E H11J N1F N2F (3) C12E C13E (6) N2F C2F (3) C12E H12I N2F H2FA C12E H12J N3F C2F (3) C13E H13M N3F C1F (3) C13E H13N N3F C3F (3) C13E H13O N1G C1G (3) C1F C11F (4) N1G N2G (3) C3F C4F (4) N2G C2G (3) C3F H3FA N2G H2GA C3F H3FB N3G C2G (3) C4F C5F (3) N3G C1G (3) C4F H4FA N3G C3G (3) C4F H4FB N1H C1H (4) C5F C6F (4) N1H N2H (3) C5F C10F (4) N2H C2H (3) C6F C7F (4) N2H H2HA C6F H6FA N3H C2H (3) C7F C8F (4) N3H C1H (3) C7F H7FA N3H C3H (3) C8F C9F (4) C1A C11A (4) C9F C10F (4) sup-15

18 C3A C4A (3) C9F H9FA C3A H3AA C10F H10F C3A H3AB C11F C12F (4) C4A C5A (3) C11F H11K C4A H4AA C11F H11L C4A H4AB C12F C13F (5) C5A C6A (4) C12F H12K C5A C10A (3) C12F H12L C6A C7A (4) C13F H13P C6A H6AA C13F H13Q C7A C8A (4) C13F H13R C7A H7AA C1G C11G (3) C8A C9A (4) C3G C4G (4) C9A C10A (4) C3G H3GA C9A H9AA C3G H3GB C10A H10A C4G C5G (3) C11A C12A (4) C4G H4GA C11A H11A C4G H4GB C11A H11B C5G C6G (4) C12A C13A (4) C5G C10G (4) C12A H12A C6G C7G (4) C12A H12B C6G H6GA C13A H13A C7G C8G (4) C13A H13B C7G H7GA C13A H13C C8G C9G (4) C1B C11B (4) C9G C10G (4) C3B C4B (3) C9G H9GA C3B H3BA C10G H10G C3B H3BB C11G C12G (4) C4B C5B (3) C11G H11M C4B H4BA C11G H11N C4B H4BB C12G C13G (4) C5B C6B (4) C12G H12M C5B C10B (4) C12G H12N C6B C7B (4) C13G H13S C6B H6BA C13G H13T C7B C8B (4) C13G H13U C7B H7BA C1H C11H (4) C8B C9B (4) C3H C4H (4) C9B C10B (4) C3H H3HA C9B H9BA C3H H3HB C10B H10B C4H C5H (4) C11B C12B (4) C4H H4HA C11B H11C C4H H4HB C11B H11D C5H C10H (4) C12B C13B (4) C5H C6H (4) C12B H12C C6H C7H (4) C12B H12D C6H H6HA C13B H13D C7H C8H (4) sup-16

19 C13B H13E C7H H7HA C13B H13F C8H C9H (4) C1C C11C (4) C9H C10H (4) C3C C4C (3) C9H H9HA C3C H3CA C10H H10H C3C H3CB C11H C12H (4) C4C C5C (3) C11H H11O C4C H4CA C11H H11P C4C H4CB C12H C13H (5) C5C C6C (4) C12H H12O C5C C10C (3) C12H H12P C6C C7C (4) C13H H13V C6C H6CA C13H H13W C7C C8C (3) C13H H13X C8A O2A H2A C7D C6D H6DA C8B O2B H2B C5D C6D H6DA C8C O2C H2C C6D C7D C8D (2) C8D O2D H2D C6D C7D H7DA C8E O2E H2E C8D C7D H7DA C8F O2F H2F O2D C8D C9D (2) C8G O2G H2G O2D C8D C7D (2) C8H O2H H2H C9D C8D C7D (2) C1A N1A N2A (2) C10D C9D C8D (2) C2A N2A N1A (2) C10D C9D H9DA C2A N2A H2AA C8D C9D H9DA N1A N2A H2AA C5D C10D C9D (2) C2A N3A C1A (2) C5D C10D H10D C2A N3A C3A (2) C9D C10D H10D C1A N3A C3A (2) C1D C11D C12D (2) C1B N1B N2B (2) C1D C11D H11G C2B N2B N1B (2) C12D C11D H11G C2B N2B H2BA C1D C11D H11H N1B N2B H2BA C12D C11D H11H C1B N3B C2B (2) H11G C11D H11H C1B N3B C3B (2) C11D C12D C13D (2) C2B N3B C3B (2) C11D C12D H12G C1C N1C N2C (2) C13D C12D H12G C2C N2C N1C (2) C11D C12D H12H C2C N2C H2CA C13D C12D H12H N1C N2C H2CA H12G C12D H12H C2C N3C C1C (2) C12D C13D H13J C2C N3C C3C (2) C12D C13D H13K C1C N3C C3C (2) H13J C13D H13K C1D N1D N2D (2) C12D C13D H13L C2D N2D N1D (2) H13J C13D H13L C2D N2D H2DA H13K C13D H13L N1D N2D H2DA N1E C1E N3E (2) C2D N3D C1D (2) N1E C1E C11E (2) sup-17

20 C2D N3D C3D (2) N3E C1E C11E (2) C1D N3D C3D (2) O1E C2E N2E (2) C1E N1E N2E (2) O1E C2E N3E (2) C2E N2E N1E (2) N2E C2E N3E (2) C2E N2E H2EA N3E C3E C4E (2) N1E N2E H2EA N3E C3E H3EA C2E N3E C1E (2) C4E C3E H3EA C2E N3E C3E (2) N3E C3E H3EB C1E N3E C3E (2) C4E C3E H3EB C1F N1F N2F (2) H3EA C3E H3EB C2F N2F N1F (2) C5E C4E C3E (2) C2F N2F H2FA C5E C4E H4EA N1F N2F H2FA C3E C4E H4EA C2F N3F C1F (2) C5E C4E H4EB C2F N3F C3F (2) C3E C4E H4EB C1F N3F C3F (2) H4EA C4E H4EB C1G N1G N2G (2) C10E C5E C6E (2) C2G N2G N1G (2) C10E C5E C4E (2) C2G N2G H2GA C6E C5E C4E (2) N1G N2G H2GA C7E C6E C5E (3) C2G N3G C1G (2) C7E C6E H6EA C2G N3G C3G (2) C5E C6E H6EA C1G N3G C3G (2) C6E C7E C8E (2) C1H N1H N2H (2) C6E C7E H7EA C2H N2H N1H (2) C8E C7E H7EA C2H N2H H2HA O2E C8E C9E (2) N1H N2H H2HA O2E C8E C7E (2) C2H N3H C1H (2) C9E C8E C7E (2) C2H N3H C3H (2) C10E C9E C8E (2) C1H N3H C3H (2) C10E C9E H9EA N1A C1A N3A (2) C8E C9E H9EA N1A C1A C11A (2) C9E C10E C5E (2) N3A C1A C11A (2) C9E C10E H10E O1A C2A N2A (2) C5E C10E H10E O1A C2A N3A (2) C1E C11E C12E (3) N2A C2A N3A (2) C1E C11E H11I N3A C3A C4A (2) C12E C11E H11I N3A C3A H3AA C1E C11E H11J C4A C3A H3AA C12E C11E H11J N3A C3A H3AB H11I C11E H11J C4A C3A H3AB C13E C12E C11E (3) H3AA C3A H3AB C13E C12E H12I C5A C4A C3A (2) C11E C12E H12I C5A C4A H4AA C13E C12E H12J C3A C4A H4AA C11E C12E H12J C5A C4A H4AB H12I C12E H12J C3A C4A H4AB C12E C13E H13M H4AA C4A H4AB C12E C13E H13N C6A C5A C10A (2) H13M C13E H13N sup-18

21 C6A C5A C4A (2) C12E C13E H13O C10A C5A C4A (2) H13M C13E H13O C7A C6A C5A (2) H13N C13E H13O C7A C6A H6AA N1F C1F N3F (2) C5A C6A H6AA N1F C1F C11F (2) C6A C7A C8A (2) N3F C1F C11F (2) C6A C7A H7AA O1F C2F N2F (2) C8A C7A H7AA O1F C2F N3F (2) O2A C8A C7A (2) N2F C2F N3F (2) O2A C8A C9A (2) N3F C3F C4F (2) C7A C8A C9A (2) N3F C3F H3FA C10A C9A C8A (2) C4F C3F H3FA C10A C9A H9AA N3F C3F H3FB C8A C9A H9AA C4F C3F H3FB C9A C10A C5A (2) H3FA C3F H3FB C9A C10A H10A C5F C4F C3F (2) C5A C10A H10A C5F C4F H4FA C1A C11A C12A (2) C3F C4F H4FA C1A C11A H11A C5F C4F H4FB C12A C11A H11A C3F C4F H4FB C1A C11A H11B H4FA C4F H4FB C12A C11A H11B C6F C5F C10F (2) H11A C11A H11B C6F C5F C4F (3) C11A C12A C13A (3) C10F C5F C4F (3) C11A C12A H12A C5F C6F C7F (3) C13A C12A H12A C5F C6F H6FA C11A C12A H12B C7F C6F H6FA C13A C12A H12B C8F C7F C6F (3) H12A C12A H12B C8F C7F H7FA C12A C13A H13A C6F C7F H7FA C12A C13A H13B O2F C8F C7F (2) H13A C13A H13B O2F C8F C9F (2) C12A C13A H13C C7F C8F C9F (2) H13A C13A H13C C10F C9F C8F (2) H13B C13A H13C C10F C9F H9FA N1B C1B N3B (2) C8F C9F H9FA N1B C1B C11B (2) C5F C10F C9F (2) N3B C1B C11B (2) C5F C10F H10F O1B C2B N2B (2) C9F C10F H10F O1B C2B N3B (2) C1F C11F C12F (2) N2B C2B N3B (2) C1F C11F H11K N3B C3B C4B (2) C12F C11F H11K N3B C3B H3BA C1F C11F H11L C4B C3B H3BA C12F C11F H11L N3B C3B H3BB H11K C11F H11L C4B C3B H3BB C13F C12F C11F (3) H3BA C3B H3BB C13F C12F H12K C5B C4B C3B (2) C11F C12F H12K C5B C4B H4BA C13F C12F H12L sup-19

22 C3B C4B H4BA C11F C12F H12L C5B C4B H4BB H12K C12F H12L C3B C4B H4BB C12F C13F H13P H4BA C4B H4BB C12F C13F H13Q C6B C5B C10B (2) H13P C13F H13Q C6B C5B C4B (2) C12F C13F H13R C10B C5B C4B (2) H13P C13F H13R C7B C6B C5B (2) H13Q C13F H13R C7B C6B H6BA N1G C1G N3G (2) C5B C6B H6BA N1G C1G C11G (2) C6B C7B C8B (2) N3G C1G C11G (2) C6B C7B H7BA O1G C2G N2G (3) C8B C7B H7BA O1G C2G N3G (2) O2B C8B C9B (2) N2G C2G N3G (2) O2B C8B C7B (2) N3G C3G C4G (2) C9B C8B C7B (2) N3G C3G H3GA C10B C9B C8B (2) C4G C3G H3GA C10B C9B H9BA N3G C3G H3GB C8B C9B H9BA C4G C3G H3GB C9B C10B C5B (2) H3GA C3G H3GB C9B C10B H10B C5G C4G C3G (2) C5B C10B H10B C5G C4G H4GA C1B C11B C12B (2) C3G C4G H4GA C1B C11B H11C C5G C4G H4GB C12B C11B H11C C3G C4G H4GB C1B C11B H11D H4GA C4G H4GB C12B C11B H11D C6G C5G C10G (2) H11C C11B H11D C6G C5G C4G (2) C11B C12B C13B (2) C10G C5G C4G (2) C11B C12B H12C C7G C6G C5G (2) C13B C12B H12C C7G C6G H6GA C11B C12B H12D C5G C6G H6GA C13B C12B H12D C6G C7G C8G (2) H12C C12B H12D C6G C7G H7GA C12B C13B H13D C8G C7G H7GA C12B C13B H13E O2G C8G C9G (2) H13D C13B H13E O2G C8G C7G (2) C12B C13B H13F C9G C8G C7G (2) H13D C13B H13F C8G C9G C10G (2) H13E C13B H13F C8G C9G H9GA N1C C1C N3C (2) C10G C9G H9GA N1C C1C C11C (2) C9G C10G C5G (2) N3C C1C C11C (2) C9G C10G H10G O1C C2C N2C (2) C5G C10G H10G O1C C2C N3C (2) C1G C11G C12G (2) N2C C2C N3C (2) C1G C11G H11M N3C C3C C4C (2) C12G C11G H11M N3C C3C H3CA C1G C11G H11N C4C C3C H3CA C12G C11G H11N sup-20

23 N3C C3C H3CB H11M C11G H11N C4C C3C H3CB C13G C12G C11G (2) H3CA C3C H3CB C13G C12G H12M C5C C4C C3C (2) C11G C12G H12M C5C C4C H4CA C13G C12G H12N C3C C4C H4CA C11G C12G H12N C5C C4C H4CB H12M C12G H12N C3C C4C H4CB C12G C13G H13S H4CA C4C H4CB C12G C13G H13T C6C C5C C10C (2) H13S C13G H13T C6C C5C C4C (2) C12G C13G H13U C10C C5C C4C (2) H13S C13G H13U C7C C6C C5C (2) H13T C13G H13U C7C C6C H6CA N1H C1H N3H (2) C5C C6C H6CA N1H C1H C11H (3) C6C C7C C8C (2) N3H C1H C11H (2) C6C C7C H7CA O1H C2H N2H (2) C8C C7C H7CA O1H C2H N3H (2) O2C C8C C7C (2) N2H C2H N3H (2) O2C C8C C9C (2) N3H C3H C4H (2) C7C C8C C9C (2) N3H C3H H3HA C10C C9C C8C (2) C4H C3H H3HA C10C C9C H9CA N3H C3H H3HB C8C C9C H9CA C4H C3H H3HB C9C C10C C5C (2) H3HA C3H H3HB C9C C10C H10C C5H C4H C3H (2) C5C C10C H10C C5H C4H H4HA C1C C11C C12C (2) C3H C4H H4HA C1C C11C H11E C5H C4H H4HB C12C C11C H11E C3H C4H H4HB C1C C11C H11F H4HA C4H H4HB C12C C11C H11F C10H C5H C6H (2) H11E C11C H11F C10H C5H C4H (3) C11C C12C C13C (2) C6H C5H C4H (2) C11C C12C H12E C7H C6H C5H (2) C13C C12C H12E C7H C6H H6HA C11C C12C H12F C5H C6H H6HA C13C C12C H12F C6H C7H C8H (2) H12E C12C H12F C6H C7H H7HA C12C C13C H13G C8H C7H H7HA C12C C13C H13H O2H C8H C9H (2) H13G C13C H13H O2H C8H C7H (2) C12C C13C H13I C9H C8H C7H (2) H13G C13C H13I C8H C9H C10H (2) H13H C13C H13I C8H C9H H9HA N1D C1D N3D (2) C10H C9H H9HA N1D C1D C11D (2) C9H C10H C5H (3) N3D C1D C11D (2) C9H C10H H10H O1D C2D N2D (2) C5H C10H H10H sup-21

24 O1D C2D N3D (2) C1H C11H C12H (3) N2D C2D N3D (2) C1H C11H H11O N3D C3D C4D (2) C12H C11H H11O N3D C3D H3DA C1H C11H H11P C4D C3D H3DA C12H C11H H11P N3D C3D H3DB H11O C11H H11P C4D C3D H3DB C13H C12H C11H (3) H3DA C3D H3DB C13H C12H H12O C5D C4D C3D (2) C11H C12H H12O C5D C4D H4DA C13H C12H H12P C3D C4D H4DA C11H C12H H12P C5D C4D H4DB H12O C12H H12P C3D C4D H4DB C12H C13H H13V H4DA C4D H4DB C12H C13H H13W C10D C5D C6D (2) H13V C13H H13W C10D C5D C4D (2) C12H C13H H13X C6D C5D C4D (2) H13V C13H H13X C7D C6D C5D (2) H13W C13H H13X C1A N1A N2A C2A 1.5 (3) C8D C9D C10D C5D 0.9 (4) C1B N1B N2B C2B 0.2 (3) N1D C1D C11D C12D 13.7 (4) C1C N1C N2C C2C 0.0 (3) N3D C1D C11D C12D (2) C1D N1D N2D C2D 0.3 (3) C1D C11D C12D C13D (2) C1E N1E N2E C2E 0.9 (3) N2E N1E C1E N3E 0.0 (3) C1F N1F N2F C2F 0.4 (3) N2E N1E C1E C11E (3) C1G N1G N2G C2G 0.1 (3) C2E N3E C1E N1E 0.9 (3) C1H N1H N2H C2H 1.2 (3) C3E N3E C1E N1E (2) N2A N1A C1A N3A 1.0 (3) C2E N3E C1E C11E (3) N2A N1A C1A C11A (2) C3E N3E C1E C11E 7.1 (4) C2A N3A C1A N1A 0.2 (3) N1E N2E C2E O1E (3) C3A N3A C1A N1A (2) N1E N2E C2E N3E 1.4 (3) C2A N3A C1A C11A (2) C1E N3E C2E O1E (3) C3A N3A C1A C11A 5.0 (4) C3E N3E C2E O1E 4.6 (4) N1A N2A C2A O1A (3) C1E N3E C2E N2E 1.4 (3) N1A N2A C2A N3A 1.4 (3) C3E N3E C2E N2E (2) C1A N3A C2A O1A (3) C2E N3E C3E C4E (3) C3A N3A C2A O1A 1.7 (4) C1E N3E C3E C4E 83.3 (3) C1A N3A C2A N2A 0.7 (3) N3E C3E C4E C5E (2) C3A N3A C2A N2A (2) C3E C4E C5E C10E 91.0 (3) C2A N3A C3A C4A 88.3 (3) C3E C4E C5E C6E 86.6 (3) C1A N3A C3A C4A 93.7 (3) C10E C5E C6E C7E 2.4 (4) N3A C3A C4A C5A (2) C4E C5E C6E C7E (2) C3A C4A C5A C6A 75.6 (3) C5E C6E C7E C8E 0.7 (4) C3A C4A C5A C10A (3) C6E C7E C8E O2E (3) C10A C5A C6A C7A 0.7 (4) C6E C7E C8E C9E 1.4 (4) C4A C5A C6A C7A (2) O2E C8E C9E C10E (2) C5A C6A C7A C8A 0.3 (4) C7E C8E C9E C10E 1.7 (4) C6A C7A C8A O2A (2) C8E C9E C10E C5E 0.0 (4) C6A C7A C8A C9A 0.0 (4) C6E C5E C10E C9E 2.0 (4) sup-22