acetone disolvate Ioannis Tiritiris and Willi Kantlehner*

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1 ISSN N,N,N 0,N 0 -Tetramethyl-N 00 -[2-(trimethylazaniumyl)ethyl]guanidinium bis(tetraphenylborate) acetone disolvate Ioannis Tiritiris and Willi Kantlehner* Received 19 January 2016 Accepted 20 January 2016 Fakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D Aalen, Germany. *Correspondence willi.kantlehner@hs-aalen.de Edited by M. Zeller, Youngstown State University, USA Keywords: crystal structure; guanidinium salt; tetraphenylborate; hydrogen bonds. CCDC reference: Structural data: full structural data are available from iucrdata.iucr.org The asymmetric unit of the title solvated salt, C 10 H 26 N C 24 H 20 B 2C 3 H 6 O, comprises one cation, two tetraphenylborate ions and two acetone solvent molecules. The N and methyl C atoms of the terminal trimethylammonium group are disordered over two sets of sites, with a refined occupancy ratio of (3):0.154 (3). The C N bond lengths in the central C 3 N unit of the guanidinium ion range between (16) and (16) Å, indicating a degree of double-bond character. The central C atom is bonded to the three N atoms in a nearly ideal trigonal planar geometry and the positive charge is delocalized in the CN 3 plane. The C N bond lengths in the terminal trimethylammonium group have values close to that of a typical single bond, and the second positive charge is localized there. In the crystal, the guanidinium ion is connected by N HO and C HO hydrogen bonds with the acetone molecules. C H interactions are present between the guanidinium H atoms and the phenyl rings of the tetraphenylborate ions, leading to the formation of a two-dimensional supramolecular pattern along the bc plane. Structure description!-aminoalkylguanidines like N 00 -[2-(dimethylamino)ethyl]- N,N,N 0,N 0 -tetramethylguanidine (Tiritiris & Kantlehner, 2012) and its corresponding imine-nitrogen atom protonated guanidinium salts are well known in the literature (tetraphenylborate salt: Tiritiris & Kantlehner, 2012; bicarbonate salt: Tiritiris et al., 2011). Electrophiles can attack on the nitrogen atom of the (dimethylamino)ethyl group in these salts. By alkylation of the chloride salt with one equivalent of dimethyl sulfate and after anion 1of3

2 Table 1 Hydrogen-bond geometry (Å, ). Cg1, Cg2, Cg3 and Cg4 are the centroids of the C23 C28, C29 C34, C35 C40 and C53 C58 rings, respectively. D HA D H HA DA D HA Figure 1 The structure of the title compound, with displacement ellipsoids at the 50% probability level. All H atoms (except for H3) have been omitted for the sake of clarity. Only the major population of the disordered [NMe 3 ] + group is shown. N3 H3O (2) 2.07 (2) (2) 140 (2) C9A H9A3O (2) 144 C8B H8B1O (2) 158 C7 H7AO (2) 155 C3 H3CCg (2) 122 C9A H9A1Cg2 i (2) 115 C9B H9B2Cg2 i (2) 110 C10B H10ECg (2) 146 C2 H2CCg (2) 108 Symmetry code: (i) x þ 1; y; z. exchange with sodium tetraphenylborate, the here-presented crystalline title compound emerged. The asymmetric unit of the structure comprises one cation, two tetraphenylborate ions and two acetone molecules (Fig. 1). The nitrogen and the methyl carbon atoms of the terminal trimethylammonium group are disordered over two sets of sites with a refined occupancy ratio of (3):0.154 (3) (Fig. 2). Prominent bond parameters in the guanidinium ion are: C1 N1 = (16) Å, C1 N2 = (16) Å and C1 N3 = (16) Å, indicating partial double-bond character for all. The N C1 N angles range from (12) to (11), indicating that the carbon centre C1 adopts a nearly ideal trigonal-planar environment. One of the two positive charges is completely delocalized in the CN 3 plane, while the second positive charge is localized at the terminal trimethylammonium group. The N C bond lengths in the [NMe 3 ] + group have values close to a typical single bond [d(n C) = (17) 1.55 (3) Å]. The C N and C C bond lengths in the dication are in very good agreement with the values obtained for N,N,N 0,N 0 - tetramethyl-n 00 -[3-(trimethylazaniumyl)propyl]guanidinium bis(tetraphenylborate) acetone disolvate (Tiritiris, 2013b). The bond lengths and angles in both tetraphenylborate ions are in good agreement with the data from the crystal structure analysis of the alkali metal tetraphenylborates (Behrens et al., 2012a). In the crystal, the guanidinium ion is connected by N HO and C HO hydrogen bonds (Fig. 3) with the acetone molecules (Table 1). C H interactions between the hydrogen atoms of N(CH 3 ) groups of the guanidinium ion and the phenyl carbon atoms of the tetraphenylborate ions are present (Table 1). This leads to the formation of a twodimensional supramolecular pattern along the ac plane (Fig. 4). Such C H interactions have been also observed in N-[3-(benzyldimethylazaniumyl)propyl]-N 0,N 0,N 00,N 00 -tetramethylguanidinium bis(tetraphenylborate) (Tiritiris, 2013a) Figure 2 The structure of the guanidinium ion. All hydrogen atoms (except for H3) are omitted for the sake of clarity. The nitrogen and carbon atoms of the terminal [NMe 3 ] + group are disordered between the opaque (minor population) and dark (major population) positions. Figure 3 N HO and C HO hydrogen bonds (black dashed lines) between the guanidinium ion and the acetone molecules, including the minor population (opaque) and major population (dark) of the disordered [NMe 3 ] + group. 2of3 Tiritiris and Kantlehner C 10 H 26 N C 24 H 20 B 2C 3 H 6 O

3 Table 2 Experimental details. Crystal data Chemical formula C 10 H 26 N C 24 H 20 B 2C 3 H 6 O M r Crystal system, space group Triclinic, P1 Temperature (K) 100 a, b, c (Å) (3), (5), (9),, ( ) (13), (1), (8) V (Å 3 ) (18) Z 2 Radiation type Mo K (mm 1 ) 0.07 Crystal size (mm) Figure 4 C H interactions (brown dashed lines) between the hydrogen atoms of the guanidinium ion and the phenyl rings (centroids) of the tetraphenylborate ions (view along bc), including the minor population (opaque) and major population (dark) of the disordered [NMe 3 ] + group. and N,N,N 0,N 0 -tetramethyl-n 00 -[3-(trimethylazaniumyl)propyl]guanidinium bis(tetraphenylborate) acetone disolvate (Tiritiris, 2013b). Synthesis and crystallization The title compound was obtained by reaction of N,N,N 0,N 0 - tetramethyl-n 00 -[2-(dimethylamino)ethyl]guanidinium chloride (Tiritiris & Kantlehner, 2012) with one equivalent of dimethyl sulfate in acetonitrile at room temperature. After evaporation of the solvent, the crude N,N,N 0,N 0 -tetramethyl- N 00 -[2-(trimethylazaniumyl)ethyl]guanidinium chloride methyl sulfate (I) was washed with diethyl ether and dried in vacuo g (2.87 mmol) of (I) was dissolved in 20 ml acetonitrile and 1.96 g (5.74 mmol) of sodium tetraphenylborate in 20 ml acetonitrile was added. After stirring for one h at room temperature, the precipitated sodium chloride and sodium methyl sulfate was filtered off. The title compound crystallized from a saturated acetone solution after several weeks at 273 K, forming colorless single crystals. Yield: 2.18 g (88%). Dimethyl sulfate is carcinogenic, mutagenic and highly poisonous. During the use appropriate precautions must be taken. Refinement Crystal data, data collection and structure refinement details are summarized in Table 2. The The atoms N4, C8, C9 and C10 of the [NMe 3 ] + group are disordered over two sets of sites [N4A/N4B, C8A/C8B, C9A/C9B and C10A/C10B] with a refined occupancy ratio of (3):0.154 (3). The two moieties were constrained to have similar geometries, and the Data collection Diffractometer Bruker Nonius KappaCCD No. of measured, independent and 22310, 13295, observed [I > 2(I)] reflections R int (sin /) max (Å 1 ) Refinement R[F 2 >2(F 2 )], wr(f 2 ), S 0.050, 0.138, 1.02 No. of reflections No. of parameters 680 No. of restraints 6 H-atom treatment H atoms treated by a mixture of independent and constrained refinement max, min (e Å 3 ) 0.58, 0.32 Computer programs: COLLECT (Hooft, 2004), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015), DIAMOND (Brandenburg & Putz, 2005). anisotropic displacement parameters of equivalent atoms were constrained to be identical. Acknowledgements The authors thank Dr F. Lissner (Institut für Anorganische Chemie, Universität Stuttgart) for measuring the diffraction data. References Behrens, U., Hoffmann, F. & Olbrich, F. (2012a). Organometallics, 31, Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, D Bonn, Germany. Hooft, R. W. W. (2004). COLLECT. Bruker Nonius BV, Delft, The Netherlands. Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp New York: Academic Press. Sheldrick, G. M. (2008). Acta Cryst. A64, Sheldrick, G. M. (2015). Acta Cryst. C71, 3 8. Tiritiris, I. (2013a). Acta Cryst. E69, o899. Tiritiris, I. (2013b). Acta Cryst. E69, o337 o338. Tiritiris, I. & Kantlehner, W. (2012). Z. Naturforsch. Teil B, 67, Tiritiris, I., Mezger, J., Stoyanov, E. V. & Kantlehner, W. (2011). Z. Naturforsch. Teil B, 66, Tiritiris and Kantlehner C 10 H 26 N C 24 H 20 B 2C 3 H 6 O 3of3

4 full crystallographic data [ N,N,N,N -Tetramethyl-N -[2-(trimethylazaniumyl)ethyl]guanidinium bis(tetraphenylborate) acetone disolvate Ioannis Tiritiris and Willi Kantlehner N,N,N,N -Tetramethyl-N -[2-(trimethylazaniumyl)ethyl]guanidinium bis(tetraphenylborate) acetone disolvate Crystal data C 10 H 26 N C 24 H 20 B 2C 3 H 6 O M r = Triclinic, P1 a = (3) Å b = (5) Å c = (9) Å α = (13) β = (1) γ = (8) V = (18) Å 3 Data collection Bruker Nonius KappaCCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ scans, and ω scans measured reflections independent reflections Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 680 parameters 6 restraints Primary atom site location: structure-invariant direct methods Z = 2 F(000) = 1032 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from reflections θ = µ = 0.07 mm 1 T = 100 K Block, colorless mm reflections with I > 2σ(I) R int = θ max = 28.3, θ min = 1.2 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: mixed H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.0705P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.58 e Å 3 Δρ min = 0.32 e Å 3 Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. data-1

5 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 > 2sigma(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 Occ. (<1) N (10) (8) (6) (2) N (10) (8) (6) (2) N (10) (9) (7) (2) H (17) (14) (11) (5)* C (11) (10) (7) (2) C (12) (11) (8) (3) H2A * H2B * H2C * C (13) (11) (8) (3) H3A * H3B * H3C * C (12) (11) (8) (3) H4A * H4B * H4C * C (13) (11) (9) (3) H5A * H5B * H5C * C (11) (10) (7) (3) H6A * H6B * C (12) (11) (8) (3) H7A * H7B * N4A (4) (3) (2) (4) (3) C8A (18) (2) (14) (6) (3) H8A * (3) H8A * (3) H8A * (3) C9A (19) (18) (11) (5) (3) H9A * (3) H9A * (3) H9A * (3) C10A (19) (14) (12) (5) (3) H10A * (3) H10B * (3) H10C * (3) data-2

6 N4B (2) (16) (13) (4) (3) C8B (11) (11) (8) (6) (3) H8B * (3) H8B * (3) H8B * (3) C9B (11) (10) (6) (5) (3) H9B * (3) H9B * (3) H9B * (3) C10B (11) (8) (7) (5) (3) H10D * (3) H10E * (3) H10F * (3) B (13) (11) (8) (3) C (11) (9) (7) (2) C (11) (10) (7) (2) H * C (12) (11) (8) (3) H * C (12) (11) (8) (3) H * C (12) (10) (8) (3) H * C (12) (10) (8) (3) H * C (12) (10) (8) (2) C (12) (10) (8) (3) H * C (12) (11) (9) (3) H * C (13) (11) (9) (3) H * C (14) (11) (8) (3) H * C (13) (10) (8) (3) H * C (11) (10) (7) (2) C (12) (10) (8) (3) H * C (13) (11) (8) (3) H * C (13) (11) (8) (3) H * C (13) (10) (8) (3) H * C (12) (10) (8) (3) H * C (11) (10) (7) (2) data-3

7 C (12) (10) (8) (3) H * C (12) (10) (8) (3) H * C (13) (10) (8) (3) H * C (12) (10) (8) (3) H * C (12) (10) (8) (2) H * B (12) (11) (8) (3) C (11) (10) (7) (2) C (12) (10) (8) (2) H * C (13) (11) (8) (3) H * C (14) (11) (9) (3) H * C (14) (11) (9) (3) H * C (12) (10) (8) (3) H * C (11) (9) (7) (2) C (11) (10) (8) (2) H * C (12) (11) (8) (3) H * C (12) (11) (8) (3) H * C (12) (11) (8) (3) H * C (12) (10) (8) (3) H * C (11) (9) (7) (2) C (12) (10) (8) (3) H * C (13) (11) (8) (3) H * C (13) (11) (9) (3) H * C (12) (10) (9) (3) H * C (12) (10) (8) (3) H * C (11) (10) (7) (2) C (11) (10) (7) (2) H * C (12) (11) (8) (3) data-4

8 H * C (12) (10) (8) (3) H * C (12) (10) (8) (3) H * C (12) (10) (8) (3) H * O (13) (10) (8) (3) C (14) (12) (9) (3) C (16) (14) (11) (4) H60A * H60B * H60C * C (17) (18) (11) (5) H61A * H61B * H61C * O (11) (11) (9) (3) C (14) (11) (9) (3) H62A * H62B * H62C * C (13) (11) (9) (3) C (14) (13) (9) (3) H64A * H64B * H64C * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 N (5) (5) (5) (4) (4) (4) N (5) (5) (5) (4) (4) (4) N (5) (5) (5) (4) (4) (4) C (6) (6) (5) (5) (4) (5) C (6) (6) (6) (5) (5) (5) C (7) (7) (7) (5) (6) (6) C (6) (7) (7) (5) (5) (6) C (6) (7) (8) (5) (6) (6) C (6) (6) (6) (5) (5) (5) C (6) (7) (6) (5) (5) (5) N4A (11) (6) (9) (5) (5) (6) C8A (8) (14) (11) (9) (8) (10) C9A (10) (12) (8) (9) (7) (8) C10A (11) (8) (10) (7) (8) (8) N4B (11) (6) (9) (5) (5) (6) C8B (8) (14) (11) (9) (8) (10) C9B (10) (12) (8) (9) (7) (8) data-5

9 C10B (11) (8) (10) (7) (8) (8) B (6) (6) (6) (5) (5) (5) C (5) (6) (6) (4) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (7) (6) (5) (5) (5) C (6) (7) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (8) (5) (6) (6) C (7) (7) (7) (5) (6) (6) C (7) (7) (7) (6) (6) (6) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (7) (7) (6) (5) (5) (5) C (7) (6) (7) (5) (6) (5) C (7) (6) (7) (5) (6) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (7) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) B (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (7) (6) (5) (5) (5) C (8) (7) (7) (6) (6) (6) C (7) (7) (7) (6) (6) (6) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (4) (4) (5) C (6) (6) (6) (5) (5) (5) C (6) (7) (7) (5) (5) (6) C (6) (7) (7) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (5) (6) (4) (5) (5) C (6) (6) (6) (5) (5) (5) C (7) (6) (6) (5) (6) (5) C (7) (6) (7) (5) (6) (6) C (6) (6) (8) (5) (6) (6) C (6) (6) (6) (5) (5) (5) C (5) (6) (6) (4) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (7) (6) (5) (5) (5) data-6

10 C (6) (6) (7) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) O (8) (6) (7) (6) (6) (6) C (7) (7) (7) (6) (6) (6) C (9) (9) (10) (7) (8) (8) C (9) (14) (9) (9) (7) (9) O (6) (8) (10) (6) (6) (8) C (7) (7) (8) (6) (6) (6) C (7) (7) (8) (5) (6) (6) C (8) (9) (8) (7) (6) (7) Geometric parameters (Å, º) N1 C (16) C25 H N1 C (16) C26 C (2) N1 C (16) C26 H N2 C (16) C27 C (19) N2 C (17) C27 H N2 C (17) C28 H N3 C (16) C29 C (17) N3 C (16) C29 C (18) N3 H (19) C30 C (18) C2 H2A C30 H C2 H2B C31 C (19) C2 H2C C31 H C3 H3A C32 C (19) C3 H3B C32 H C3 H3C C33 C (18) C4 H4A C33 H C4 H4B C34 H C4 H4C B2 C (18) C5 H5A B2 C (18) C5 H5B B2 C (18) C5 H5C B2 C (18) C6 C (18) C35 C (18) C6 H6A C35 C (18) C6 H6B C36 C (19) C7 N4A (5) C36 H C7 N4B 1.55 (3) C37 C (2) C7 H7A C37 H C7 H7B C38 C (2) N4A C8A (3) C38 H N4A C10A (3) C39 C (19) N4A C9A (3) C39 H C8A H8A C40 H C8A H8A C41 C (17) C8A H8A C41 C (17) data-7

11 C9A H9A C42 C (18) C9A H9A C42 H C9A H9A C43 C (2) C10A H10A C43 H C10A H10B C44 C (2) C10A H10C C44 H N4B C8B (17) C45 C (18) N4B C9B (17) C45 H N4B C10B (17) C46 H C8B H8B C47 C (18) C8B H8B C47 C (18) C8B H8B C48 C (19) C9B H9B C48 H C9B H9B C49 C (2) C9B H9B C49 H C10B H10D C50 C (2) C10B H10E C50 H C10B H10F C51 C (18) B1 C (18) C51 H B1 C (18) C52 H B1 C (19) C53 C (17) B1 C (18) C53 C (18) C11 C (17) C54 C (18) C11 C (17) C54 H C12 C (18) C55 C (19) C12 H C55 H C13 C (19) C56 C (19) C13 H C56 H C14 C (2) C57 C (18) C14 H C57 H C15 C (18) C58 H C15 H O1 C (19) C16 H C59 C (2) C17 C (19) C59 C (2) C17 C (18) C60 H60A C18 C (19) C60 H60B C18 H C60 H60C C19 C (2) C61 H61A C19 H C61 H61B C20 C (2) C61 H61C C20 H O2 C (18) C21 C (19) C62 C (2) C21 H C62 H62A C22 H C62 H62B C23 C (18) C62 H62C C23 C (18) C63 C (2) C24 C (19) C64 H64A C24 H C64 H64B data-8

12 C25 C (2) C64 H64C C1 N1 C (11) C25 C24 C (13) C1 N1 C (11) C25 C24 H C2 N1 C (10) C23 C24 H C1 N2 C (11) C26 C25 C (13) C1 N2 C (11) C26 C25 H C4 N2 C (11) C24 C25 H C1 N3 C (11) C27 C26 C (12) C1 N3 H (12) C27 C26 H C6 N3 H (12) C25 C26 H N1 C1 N (11) C26 C27 C (13) N1 C1 N (11) C26 C27 H N2 C1 N (12) C28 C27 H N1 C2 H2A C27 C28 C (12) N1 C2 H2B C27 C28 H H2A C2 H2B C23 C28 H N1 C2 H2C C34 C29 C (11) H2A C2 H2C C34 C29 B (11) H2B C2 H2C C30 C29 B (11) N1 C3 H3A C31 C30 C (12) N1 C3 H3B C31 C30 H H3A C3 H3B C29 C30 H N1 C3 H3C C30 C31 C (12) H3A C3 H3C C30 C31 H H3B C3 H3C C32 C31 H N2 C4 H4A C33 C32 C (12) N2 C4 H4B C33 C32 H H4A C4 H4B C31 C32 H N2 C4 H4C C32 C33 C (12) H4A C4 H4C C32 C33 H H4B C4 H4C C34 C33 H N2 C5 H5A C33 C34 C (12) N2 C5 H5B C33 C34 H H5A C5 H5B C29 C34 H N2 C5 H5C C41 B2 C (10) H5A C5 H5C C41 B2 C (10) H5B C5 H5C C53 B2 C (10) N3 C6 C (10) C41 B2 C (10) N3 C6 H6A C53 B2 C (10) C7 C6 H6A C47 B2 C (10) N3 C6 H6B C40 C35 C (11) C7 C6 H6B C40 C35 B (11) H6A C6 H6B C36 C35 B (11) N4A C7 C (14) C37 C36 C (12) C6 C7 N4B (6) C37 C36 H N4A C7 H7A C35 C36 H C6 C7 H7A C36 C37 C (12) data-9

13 N4A C7 H7B C36 C37 H C6 C7 H7B C38 C37 H H7A C7 H7B C39 C38 C (13) C8A N4A C10A (3) C39 C38 H C8A N4A C (2) C37 C38 H C10A N4A C (3) C38 C39 C (13) C8A N4A C9A (3) C38 C39 H C10A N4A C9A (2) C40 C39 H C7 N4A C9A (2) C39 C40 C (12) N4A C8A H8A C39 C40 H N4A C8A H8A C35 C40 H H8A1 C8A H8A C42 C41 C (11) N4A C8A H8A C42 C41 B (11) H8A1 C8A H8A C46 C41 B (11) H8A2 C8A H8A C41 C42 C (12) N4A C9A H9A C41 C42 H N4A C9A H9A C43 C42 H H9A1 C9A H9A C44 C43 C (12) N4A C9A H9A C44 C43 H H9A1 C9A H9A C42 C43 H H9A2 C9A H9A C43 C44 C (12) N4A C10A H10A C43 C44 H N4A C10A H10B C45 C44 H H10A C10A H10B C44 C45 C (12) N4A C10A H10C C44 C45 H H10A C10A H10C C46 C45 H H10B C10A H10C C45 C46 C (12) C8B N4B C9B (16) C45 C46 H C8B N4B C10B (16) C41 C46 H C9B N4B C10B (14) C48 C47 C (11) C8B N4B C (14) C48 C47 B (11) C9B N4B C (13) C52 C47 B (11) C10B N4B C (15) C49 C48 C (13) N4B C8B H8B C49 C48 H N4B C8B H8B C47 C48 H H8B1 C8B H8B C50 C49 C (13) N4B C8B H8B C50 C49 H H8B1 C8B H8B C48 C49 H H8B2 C8B H8B C49 C50 C (12) N4B C9B H9B C49 C50 H N4B C9B H9B C51 C50 H H9B1 C9B H9B C52 C51 C (13) N4B C9B H9B C52 C51 H H9B1 C9B H9B C50 C51 H H9B2 C9B H9B C51 C52 C (13) N4B C10B H10D C51 C52 H N4B C10B H10E C47 C52 H H10D C10B H10E C54 C53 C (11) data-10

14 N4B C10B H10F C54 C53 B (11) H10D C10B H10F C58 C53 B (11) H10E C10B H10F C55 C54 C (12) C17 B1 C (10) C55 C54 H C17 B1 C (10) C53 C54 H C11 B1 C (10) C56 C55 C (12) C17 B1 C (10) C56 C55 H C11 B1 C (10) C54 C55 H C23 B1 C (10) C55 C56 C (12) C12 C11 C (11) C55 C56 H C12 C11 B (11) C57 C56 H C16 C11 B (11) C56 C57 C (12) C13 C12 C (12) C56 C57 H C13 C12 H C58 C57 H C11 C12 H C57 C58 C (12) C14 C13 C (12) C57 C58 H C14 C13 H C53 C58 H C12 C13 H O1 C59 C (16) C13 C14 C (12) O1 C59 C (16) C13 C14 H C60 C59 C (14) C15 C14 H C59 C60 H60A C14 C15 C (12) C59 C60 H60B C14 C15 H H60A C60 H60B C16 C15 H C59 C60 H60C C15 C16 C (12) H60A C60 H60C C15 C16 H H60B C60 H60C C11 C16 H C59 C61 H61A C22 C17 C (12) C59 C61 H61B C22 C17 B (11) H61A C61 H61B C18 C17 B (11) C59 C61 H61C C19 C18 C (13) H61A C61 H61C C19 C18 H H61B C61 H61C C17 C18 H C63 C62 H62A C20 C19 C (13) C63 C62 H62B C20 C19 H H62A C62 H62B C18 C19 H C63 C62 H62C C21 C20 C (13) H62A C62 H62C C21 C20 H H62B C62 H62C C19 C20 H O2 C63 C (14) C20 C21 C (13) O2 C63 C (14) C20 C21 H C62 C63 C (12) C22 C21 H C63 C64 H64A C21 C22 C (13) C63 C64 H64B C21 C22 H H64A C64 H64B C17 C22 H C63 C64 H64C C28 C23 C (12) H64A C64 H64C C28 C23 B (11) H64B C64 H64C C24 C23 B (11) data-11

15 C2 N1 C1 N (12) C23 B1 C29 C (15) C3 N1 C1 N (18) C34 C29 C30 C (19) C2 N1 C1 N (18) B1 C29 C30 C (12) C3 N1 C1 N (12) C29 C30 C31 C (2) C4 N2 C1 N (18) C30 C31 C32 C (2) C5 N2 C1 N (12) C31 C32 C33 C (2) C4 N2 C1 N (12) C32 C33 C34 C (2) C5 N2 C1 N (18) C30 C29 C34 C (19) C6 N3 C1 N (19) B1 C29 C34 C (12) C6 N3 C1 N (13) C41 B2 C35 C (12) C1 N3 C6 C (17) C53 B2 C35 C (14) N3 C6 C7 N4A (16) C47 B2 C35 C (17) N3 C6 C7 N4B (7) C41 B2 C35 C (15) C6 C7 N4A C8A 47.0 (3) C53 B2 C35 C (14) C6 C7 N4A C10A 75.3 (2) C47 B2 C35 C (11) C6 C7 N4A C9A (17) C40 C35 C36 C (19) C6 C7 N4B C8B 80.1 (11) B2 C35 C36 C (12) C6 C7 N4B C9B (9) C35 C36 C37 C (2) C6 C7 N4B C10B 45.3 (13) C36 C37 C38 C (2) C17 B1 C11 C (13) C37 C38 C39 C (2) C23 B1 C11 C (12) C38 C39 C40 C (2) C29 B1 C11 C (17) C36 C35 C40 C (19) C17 B1 C11 C (14) B2 C35 C40 C (13) C23 B1 C11 C (14) C53 B2 C41 C (16) C29 B1 C11 C (11) C47 B2 C41 C (13) C16 C11 C12 C (18) C35 B2 C41 C (12) B1 C11 C12 C (12) C53 B2 C41 C (11) C11 C12 C13 C (2) C47 B2 C41 C (14) C12 C13 C14 C (19) C35 B2 C41 C (14) C13 C14 C15 C (19) C46 C41 C42 C (18) C14 C15 C16 C (2) B2 C41 C42 C (12) C12 C11 C16 C (18) C41 C42 C43 C (2) B1 C11 C16 C (12) C42 C43 C44 C (2) C11 B1 C17 C (16) C43 C44 C45 C (2) C23 B1 C17 C (13) C44 C45 C46 C (2) C29 B1 C17 C (13) C42 C41 C46 C (19) C11 B1 C17 C (11) B2 C41 C46 C (12) C23 B1 C17 C (15) C41 B2 C47 C (16) C29 B1 C17 C (15) C53 B2 C47 C (13) C22 C17 C18 C (19) C35 B2 C47 C (13) B1 C17 C18 C (12) C41 B2 C47 C (11) C17 C18 C19 C (2) C53 B2 C47 C (15) C18 C19 C20 C (2) C35 B2 C47 C (15) C19 C20 C21 C (2) C52 C47 C48 C (18) C20 C21 C22 C (2) B2 C47 C48 C (12) C18 C17 C22 C (19) C47 C48 C49 C (2) B1 C17 C22 C (12) C48 C49 C50 C (2) data-12

16 C17 B1 C23 C (16) C49 C50 C51 C (2) C11 B1 C23 C (13) C50 C51 C52 C (2) C29 B1 C23 C (12) C48 C47 C52 C (19) C17 B1 C23 C (11) B2 C47 C52 C (12) C11 B1 C23 C (14) C41 B2 C53 C (14) C29 B1 C23 C (15) C47 B2 C53 C (11) C28 C23 C24 C (19) C35 B2 C53 C (16) B1 C23 C24 C (12) C41 B2 C53 C (13) C23 C24 C25 C (2) C47 B2 C53 C (16) C24 C25 C26 C (2) C35 B2 C53 C (11) C25 C26 C27 C (2) C58 C53 C54 C (18) C26 C27 C28 C (2) B2 C53 C54 C (12) C24 C23 C28 C (18) C53 C54 C55 C (2) B1 C23 C28 C (12) C54 C55 C56 C (2) C17 B1 C29 C (17) C55 C56 C57 C (2) C11 B1 C29 C (12) C56 C57 C58 C (2) C23 B1 C29 C (13) C54 C53 C58 C (19) C17 B1 C29 C (11) B2 C53 C58 C (12) C11 B1 C29 C (16) Hydrogen-bond geometry (Å, º) Cg1, Cg2, Cg3 and Cg4 are the centroids of the C23 C28, C29 C34, C35 C40 and C53 C58 rings, respectively. D H A D H H A D A D H A N3 H3 O (2) 2.07 (2) (2) 140 (2) C9A H9A3 O (2) 144 C8B H8B1 O (2) 158 C7 H7A O (2) 155 C3 H3C Cg (2) 122 C9A H9A1 Cg2 i (2) 130 C9B H9B2 Cg2 i (2) 110 C10B H10E Cg (2) 146 C2 H2C Cg (2) 118 Symmetry code: (i) x+1, y, z. data-13