5-Chloro-2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H- benzimidazole 6-Chloro-2-(thiophen-2-yl)-1-(thiophen-2- ylmethyl)-1h-benzimidazole (0.94/0.

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1 Acta Crystallographica Section E Structure Reports Online ISSN Chloro-2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H- benzimidazole 6-Chloro-2-(thiophen-2-yl)-1-(thiophen-2- ylmethyl)-1h-benzimidazole (0.94/0.06) David K. Geiger and Michael R. Nellist This open-access article is distributed under the terms of the Creative Commons Attribution Licence which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited. Acta Crystallographica Section E: Structure Reports Online is the IUCr s highly popular open-access structural journal. It provides a simple and easily accessible publication mechanism for the growing number of inorganic, metal-organic and organic crystal structure determinations. The electronic submission, validation, refereeing and publication facilities of the journal ensure very rapid and high-quality publication, whilst key indicators and validation reports provide measures of structural reliability. The journal publishes over 4000 structures per year. The average publication time is less than one month. Crystallography Journals Online is available from journals.iucr.org Geiger and Nellist C 16 H 11 ClN 2 S 2

2 organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Chloro-2-(thiophen-2-yl)-1-(thiophen- 2-ylmethyl)-1H-benzimidazole 6- Chloro-2-(thiophen-2-yl)-1-(thiophen-2- ylmethyl)-1h-benzimidazole (0.94/0.06) David K. Geiger* and Michael R. Nellist Department of Chemistry, State University of New York-College at Geneseo, 1 College Circle, Geneseo, NY 14454, USA Correspondence geiger@geneseo.edu Received 28 August 2013; accepted 8 September 2013 Key indicators: single-crystal X-ray study; T = 200 K; mean (C C) = Å; disorder in main residue; R factor = 0.038; wr factor = 0.093; data-to-parameter ratio = There are two independent molecules in the asymmetric unit of the title compound, C 16 H 11 ClN 2 S 2. The structure exhibits rotational disorder of the 2-thiophen-2-yl substituent in each of the unique molecules with a major:minor component ratio of (2):0.073 (2). For one of the symmetry-unique molecules, 6.0 (2)% of the sites are occupied by the 6- chloro-isomer. The major component thiophene rings make dihedral angles of (12) and (11) with the benzimidazole rings in the two independent molecules. In the crystal, molecules are linked into chains parallel to [100] via weak C HN interactions. Experimental Crystal data C 16 H 11 ClN 2 S 2 M r = Monoclinic, P2 1 =n a = (11) Å b = (8) Å c = (2) Å = (3) Data collection Bruker SMART X2S benchtop diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2010) T min = 0.62, T max = 0.90 Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 420 parameters V = (4) Å 3 Z =8 Mo K radiation = 0.52 mm 1 T = 200 K mm measured reflections 5356 independent reflections 4419 reflections with I > 2(I) R int = restraints H-atom parameters constrained max = 0.34 e Å 3 min = 0.44 e Å 3 Related literature For the structure of 6-chloro-2-(thiophen-2-yl)-1-(thiophen- 2-ylmethyl)-1H-benzimidazole, see: Geiger & Nellist (2013). For the structure of the 5-bromo analogue, see: Geiger & Destefano (2012). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA C22 H22N (3) 159 C28 H28BN (3) 148 C3 i H3 i N (3) 159 C12 i H12A i N (3) 150 Symmetry code: (i) x 1; y; z. Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publcif (Westrip, 2010). This work was supported by a Congressionally directed grant from the US Department of Education (grant No. P116Z100020) for the X-ray diffractometer and a grant from the Geneseo Foundation. MRN thanks Dr Bruce Ristow for a doi: /s Geiger and Nellist o1539

3 organic compounds summer research fellowship administered by the Geneseo Foundation. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2642). References Bruker (2010). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Geiger, D. K. & Destefano, M. R. (2012). Acta Cryst. E68, o3123. Geiger, D. K. & Nellist, M. R. (2013). Acta Cryst. E69, o807. Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, Sheldrick, G. M. (2008). University of Göttingen, Germany. Spek, A. L. (2009). Acta Cryst. D65, Westrip, S. P. (2010). J. Appl. Cryst. 43, o1540 Geiger and Nellist C 16 H 11 ClN 2 S 2

4 supplementary materials [doi: /s ] 5-Chloro-2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzimidazole 6- Chloro-2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzimidazole (0.94/0.06) David K. Geiger and Michael R. Nellist 1. Comment The title compound crystallized with two independent molecules in the asymmetric unit and is isomorphic with the corresponding 5-bromo derivative (Geiger & Destefano, 2012). Crystallization occurs with 6.0 (2)% of one of the sites (molecule 1) occupied by 6-chloro-2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzimidazole. Interestingly, the previously reported structure of the 6-chloro analogue displays co-crystallization with 3.1 (2)% of the 5-chloro derivative (Geiger & Nellist, 2013). Figure 1 shows a perspective view of the two molecules in the asymmetric unit with the atomlabeling scheme. Bond distances and angles agree well those reported for the 6-chloro analogue (Geiger & Nellist, 2013). The benzimidazole moieties are essentially planar with r. m. s. deviation = Å for molecule 1 and Å for molecule 2. The greatest deviation from planarity is (19) Å for C4 in molecule 1 and (19) Å for C21 in molecule 2. In both molecules, the 2-thiophene substituents are rotationally disordered with a major:minor component refined-occupancy ratio of (2):0.073 (2). The major component thiophene rings are canted (12) and (11) from the benzimidazole rings for molecules 1 and 2, respectively. Chains of molecules parallel to [1 0 0] are held together via weak C H N and C H thiophene ring interactions. The motif is shown in Figure 2. The H6 thiophenes4 centroid distance is 2.60 Å and the H19 thiophenes2 centroid distance is 2.66 Å. 2. Experimental 1,2-diamine-4-chlorobenzene (6.3 mmol, 0.90 g) was dissolved in 30 ml ethanol under nitrogen. Two equivalents of 2- thiophenecarboxaldehyde (1.3 ml) was added dropwise. After three days, the solvent was removed under reduced pressure and the crude product was chromatographed (silica gel) using a mixture of 30% hexane in ethyl acetate. The first fraction produced hexagonal shaped crystals (Geiger & Nellist, 2013) and the second fraction produced needle-shaped crystals on slow evaporation. Crystals from the second fraction were used for X-ray diffraction experiments. The overall yield was 59%. 3. Refinement Crystal data, data collection and structure refinement details are summarized in Table 1. All hydrogen atoms were observed in difference fourier maps. The H atoms were refined using a riding model with a C H distance of 0.99 Å for the methylene carbon atoms and 0.95 Å for the phenyl and thiophene carbon atoms. All C H hydrogen atom thermal parameters were set using the approximation U iso = 1.2U eq. sup-1

5 The Cl and H atoms of the major and minor co-crystallization components were modeled as a disorder involving two parts, each containing a chlorine atom and a hydrogen atom. The disorder was statistically significant for only one of the molecules in the asymmetric unit. The site occupancy for the major component refined to (2). The 2-thiophene substituents are rotationally disordered. A model was developed in which the minor components of the thiophene rings were defined using the metrics of the major component as a guide. The disordered five-member rings were constrained to planarity using FLAT. Corresponding bond distances of the minor component and major component were set equal using SAME and corresponding thermal parameters were held the same using EADP. All atoms were refined anisotropically with hydrogen atoms in calculated positions using a riding model. With these constraints, the site occupancy of the major component refined to (2). Computing details Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker 2010); data reduction: SAINT (Bruker 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publcif (Westrip, 2010). Figure 1 Perspective view of the title compound. Thermal parameters are drawn at the 50% probability level. Only major contributors to the disorder model are shown. sup-2

6 Figure 2 Perspective drawing showing the intermolecular contacts forming chains parallel to [1 0 0]. Only the major components of the disorder model are shown. 5-Chloro-2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzimidazole 6-Chloro-2-(thiophen-2- yl)-1-(thiophen-2-ylmethyl)-1h-benzimidazole (0.94/0.06) Crystal data C 16 H 11 ClN 2 S 2 M r = Monoclinic, P2 1 /n a = (11) Å b = (8) Å c = (2) Å β = (3) V = (4) Å 3 Z = 8 Data collection Bruker SMART X2S benchtop diffractometer Radiation source: XOS X-beam microfocus source Doubly curved silicon crystal monochromator ω scans Absorption correction: multi-scan (SADABS; Bruker, 2010) T min = 0.62, T max = 0.90 F(000) = 1360 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 9493 reflections θ = µ = 0.52 mm 1 T = 200 K Plate, colourless mm measured reflections 5356 independent reflections 4419 reflections with I > 2σ(I) R int = θ max = 25.1, θ min = 2.1 h = k = l = sup-3

7 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 420 parameters 227 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 ) + (0.0256P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 0.34 e Å 3 Δρ min = 0.44 e Å 3 Special details Experimental. 1 H NMR spectrum (CDCl 3, 400 MHz, p.p.m.) (1 H, d), 7.53 (1 H, d), 7.48 (1 H, d), 7.34 (1 H, s), 7.28 (2 H, m), 7.17 (1 H, t), 6.96 (1 H, t), 6.91 (1 H, d), 5.60 (2 H, s). 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 Occ. (<1) Cl (6) (7) (3) (2) (19) Cl (9) (12) (5) (4) (19) Cl (6) (8) (3) (2) S (5) (8) (3) (2) (19) C (2) (3) (12) (5) (19) C (3) (5) (2) (11) (19) H * (19) C (4) (4) (16) (9) (19) H * (19) C (3) (4) (14) (8) (19) H * (19) S (13) (18) (8) (2) (19) C (18) (2) (8) (5) (19) C (3) (4) (14) (11) (19) H * (19) C (4) (5) (17) (9) (19) H * (19) C (4) (5) (14) (8) (19) H * (19) S (5) (8) (4) (2) (19) C (2) (3) (12) (5) (19) C (3) (5) (19) (10) (19) H * (19) C (3) (3) (15) (9) (19) sup-4

8 H * (19) C (2) (4) (14) (8) (19) H * (19) S (13) (18) (8) (2) (19) C (18) (2) (8) (5) (19) C (3) (4) (14) (10) (19) H * (19) C (3) (5) (16) (9) (19) H * (19) C (4) (5) (14) (8) (19) H * (19) N (13) (18) (8) (4) N (13) (18) (9) (4) N (13) (18) (8) (4) N (13) (18) (9) (4) C (16) (2) (10) (5) C (16) (2) (10) (5) C (17) (2) (11) (6) H * C (18) (2) (11) (6) H * (19) C (19) (2) (11) (5) H * (19) C (17) (2) (10) (5) H * C (16) (2) (10) (5) C (16) (2) (10) (5) H12A * H12B * C (16) (2) (10) (5) C (16) (2) (10) (5) C (17) (2) (11) (5) H * C (18) (2) (10) (5) C (17) (2) (11) (5) H * C (16) (2) (10) (5) H * C (15) (2) (10) (5) C (16) (2) (10) (5) H28A * H28B * S (5) (6) (3) (17) C (16) (2) (11) (5) C (16) (2) (11) (6) H * C (18) (3) (12) (6) H * C (19) (3) (12) (6) sup-5

9 H * S (5) (6) (3) (17) C (16) (2) (11) (5) C (17) (2) (11) (6) H * C (19) (3) (12) (6) H * C (2) (3) (12) (7) H * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Cl (4) (4) (4) (3) (3) (3) Cl (6) (9) (7) (5) (5) (6) Cl (4) (6) (4) (4) (3) (4) S (4) (4) (4) (3) (3) (3) C (10) (13) (14) (9) (9) (11) C (2) (2) (2) (16) (16) (18) C (16) (3) (16) (16) (12) (15) C (14) (19) (2) (13) (15) (17) S (4) (4) (4) (3) (3) (3) C (10) (13) (14) (9) (9) (11) C (2) (2) (2) (16) (16) (18) C (16) (3) (16) (16) (12) (15) C (14) (19) (2) (13) (15) (17) S (4) (5) (4) (3) (3) (3) C (10) (13) (14) (9) (9) (11) C (19) (2) (3) (15) (13) (19) C (14) (3) (16) (15) (12) (15) C (14) (19) (2) (13) (13) (17) S (4) (5) (4) (3) (3) (3) C (10) (13) (14) (9) (9) (11) C (19) (2) (3) (15) (13) (19) C (14) (3) (16) (15) (12) (15) C (14) (19) (2) (13) (13) (17) N (8) (11) (11) (7) (8) (9) N (9) (11) (11) (8) (8) (9) N (9) (11) (11) (8) (7) (9) N (9) (11) (11) (8) (8) (9) C (11) (13) (13) (9) (9) (10) C (10) (12) (13) (9) (9) (10) C (11) (14) (15) (9) (10) (11) C (13) (14) (16) (10) (11) (12) C (13) (13) (14) (10) (11) (11) C (11) (14) (14) (10) (10) (11) C (10) (13) (13) (9) (9) (10) C (10) (13) (14) (9) (9) (11) C (10) (13) (13) (9) (9) (10) C (10) (13) (13) (9) (9) (10) sup-6

10 C (11) (14) (14) (10) (10) (11) C (12) (14) (13) (10) (10) (11) C (11) (14) (14) (10) (10) (11) C (10) (14) (14) (9) (9) (11) C (10) (13) (13) (9) (9) (10) C (10) (13) (13) (9) (9) (11) S (3) (4) (4) (3) (3) (3) C (10) (13) (14) (9) (9) (11) C (11) (14) (15) (10) (10) (12) C (12) (17) (15) (11) (10) (13) C (13) (15) (17) (11) (12) (13) S (3) (4) (4) (3) (3) (3) C (10) (14) (14) (9) (9) (11) C (11) (16) (14) (11) (10) (12) C (13) (18) (15) (12) (11) (13) C (14) (15) (18) (12) (13) (14) Geometric parameters (Å, º) Cl1 C (2) N3 C (3) Cl11 C (10) N3 C (3) Cl2 C (2) N4 C (3) S1 C (3) N4 C (3) S1 C (3) C1 C (3) C8 C (5) C1 C (3) C8 C (3) C2 C (3) C9 C (5) C3 C (3) C9 H C3 H C10 C (4) C4 C (3) C10 H C4 H C11 H C5 C (3) S201 C (16) C5 H S201 C (16) C6 H C208 C (16) C12 C (3) C208 C (17) C12 H12A 0.99 C209 C (16) C12 H12B 0.99 C209 H C17 C (3) C210 C (16) C17 C (3) C210 H C18 C (3) C211 H C19 C (3) S3 C (3) C19 H S3 C (3) C20 C (3) C24 C (5) C21 C (3) C24 C (3) C21 H C25 C (5) C22 H C25 H C28 C (3) C26 C (4) C28 H28A 0.99 C26 H C28 H28B 0.99 C27 H S2 C (3) S203 C (16) S2 C (2) sup-7

11 S203 C (16) C13 C (3) C204 C (16) C14 C (4) C204 C (16) C14 H C205 C (16) C15 C (4) C205 H C15 H C206 C (15) C16 H C206 H S4 C (3) C207 H S4 C (2) N1 C (3) C29 C (3) N1 C (3) C30 C (4) N1 C (3) C30 H N2 C (3) C31 C (4) N2 C (3) C31 H N3 C (3) C32 H C11 S1 C (14) C6 C5 Cl (19) C9 C8 C (3) C4 C5 Cl (18) C9 C8 S (2) C6 C5 H C7 C8 S (2) C4 C5 H C8 C9 C (3) Cl1 C5 H5 1.2 C8 C9 H C5 C6 C (2) C10 C9 H C5 C6 H C11 C10 C (3) C1 C6 H C11 C10 H N2 C7 N (2) C9 C10 H N2 C7 C (10) C10 C11 S (2) N1 C7 C (10) C10 C11 H N2 C7 C (2) S1 C11 H N1 C7 C (2) C208 S201 C (11) C208 C7 C8 1.3 (12) C209 C208 C7 123 (2) N1 C12 C (18) C209 C208 S (13) N1 C12 H12A C7 C208 S (19) C13 C12 H12A C208 C209 C (16) N1 C12 H12B C208 C209 H C13 C12 H12B C210 C209 H H12A C12 H12B C211 C210 C (17) N3 C17 C (2) C211 C210 H N3 C17 C (18) C209 C210 H C22 C17 C (2) C210 C211 S (15) N4 C18 C (19) C210 C211 H N4 C18 C (2) S201 C211 H C19 C18 C (2) C27 S3 C (14) C20 C19 C (2) C25 C24 C (3) C20 C19 H C25 C24 S (2) C18 C19 H C23 C24 S (2) C19 C20 C (2) C24 C25 C (3) C19 C20 Cl (18) C24 C25 H C21 C20 Cl (18) C26 C25 H C22 C21 C (2) C27 C26 C (3) C22 C21 H sup-8

12 C27 C26 H C20 C21 H C25 C26 H C21 C22 C (2) C26 C27 S (2) C21 C22 H C26 C27 H C17 C22 H S3 C27 H N4 C23 N (19) C204 S203 C (11) N4 C23 C (10) C205 C204 C (2) N3 C23 C (10) C205 C204 S (13) N4 C23 C (2) C23 C204 S (19) N3 C23 C (2) C204 C205 C (16) C204 C23 C (9) C204 C205 H N3 C28 C (18) C206 C205 H N3 C28 H28A C207 C206 C (17) C29 C28 H28A C207 C206 H N3 C28 H28B C205 C206 H C29 C28 H28B C206 C207 S (15) H28A C28 H28B C206 C207 H C16 S2 C (13) S203 C207 H C14 C13 C (2) C2 N1 C (18) C14 C13 S (18) C2 N1 C (17) C12 C13 S (18) C7 N1 C (19) C13 C14 C (2) C7 N2 C (17) C13 C14 H C23 N3 C (17) C15 C14 H C23 N3 C (19) C16 C15 C (2) C17 N3 C (17) C16 C15 H C23 N4 C (17) C14 C15 H N2 C1 C (2) C15 C16 S (2) N2 C1 C (2) C15 C16 H C6 C1 C (2) S2 C16 H N1 C2 C (2) C32 S4 C (13) N1 C2 C (18) C30 C29 C (2) C3 C2 C (2) C30 C29 S (19) C4 C3 C (2) C28 C29 S (17) C4 C3 H C29 C30 C (2) C2 C3 H C29 C30 H C3 C4 C (2) C31 C30 H C3 C4 Cl (4) C32 C31 C (2) C5 C4 Cl (4) C32 C31 H C3 C4 H C30 C31 H C5 C4 H C31 C32 S (2) Cl11 C4 H C31 C32 H C6 C5 C (2) S4 C32 H C11 S1 C8 C9 0.0 (3) C9 C8 C7 N (5) C11 S1 C8 C (2) S1 C8 C7 N (2) C7 C8 C9 C (3) C9 C8 C7 C S1 C8 C9 C (5) S1 C8 C7 C C8 C9 C10 C (6) C2 N1 C12 C (3) C9 C10 C11 S1 0.2 (5) C7 N1 C12 C (3) sup-9

13 C8 S1 C11 C (3) C23 N3 C17 C (2) C211 S201 C208 C209 1 (3) C28 N3 C17 C (4) C211 S201 C208 C (16) C23 N3 C17 C (2) C7 C208 C209 C (2) C28 N3 C17 C (2) S201 C208 C209 C210 4 (4) C23 N4 C18 C (2) C208 C209 C210 C211 6 (5) C23 N4 C18 C (3) C209 C210 C211 S201 5 (5) N3 C17 C18 N4 0.4 (3) C208 S201 C211 C210 2 (4) C22 C17 C18 N (2) C27 S3 C24 C (3) N3 C17 C18 C (2) C27 S3 C24 C (2) C22 C17 C18 C (4) C23 C24 C25 C (3) N4 C18 C19 C (2) S3 C24 C25 C (5) C17 C18 C19 C (3) C24 C25 C26 C (5) C18 C19 C20 C (4) C25 C26 C27 S3 0.4 (4) C18 C19 C20 Cl (17) C24 S3 C27 C (3) C19 C20 C21 C (4) C207 S203 C204 C205 1 (3) Cl2 C20 C21 C (19) C207 S203 C204 C (18) C20 C21 C22 C (3) C23 C204 C205 C (2) N3 C17 C22 C (2) S203 C204 C205 C206 0 (3) C18 C17 C22 C (3) C204 C205 C206 C207 0 (5) C18 N4 C23 N3 0.1 (3) C205 C206 C207 S203 1 (5) C18 N4 C23 C (12) C204 S203 C207 C206 1 (4) C18 N4 C23 C (2) C7 N2 C1 C (2) C17 N3 C23 N4 0.2 (3) C7 N2 C1 C2 0.6 (2) C28 N3 C23 N (2) C7 N1 C2 C (2) C17 N3 C23 C (12) C12 N1 C2 C3 3.6 (4) C28 N3 C23 C (12) C7 N1 C2 C1 0.8 (2) C17 N3 C23 C (2) C12 N1 C2 C (2) C28 N3 C23 C (4) N2 C1 C2 N1 0.9 (2) C205 C204 C23 N4 33 (2) C6 C1 C2 N (2) S203 C204 C23 N (13) N2 C1 C2 C (2) C205 C204 C23 N3 146 (2) C6 C1 C2 C3 1.2 (3) S203 C204 C23 N3 35 (2) N1 C2 C3 C (2) C205 C204 C23 C C1 C2 C3 C4 0.0 (3) S203 C204 C23 C C2 C3 C4 C5 1.3 (3) C25 C24 C23 N (4) C2 C3 C4 Cl (6) S3 C24 C23 N (3) C3 C4 C5 C6 1.4 (4) C25 C24 C23 N (5) Cl11 C4 C5 C (5) S3 C24 C23 N (2) C3 C4 C5 Cl (19) C25 C24 C23 C Cl11 C4 C5 Cl1 8.8 (5) S3 C24 C23 C C4 C5 C6 C1 0.1 (3) C23 N3 C28 C (3) Cl1 C5 C6 C (17) C17 N3 C28 C (3) N2 C1 C6 C (2) N1 C12 C13 C (2) C2 C1 C6 C5 1.1 (3) N1 C12 C13 S (2) C1 N2 C7 N1 0.1 (3) C16 S2 C13 C (17) C1 N2 C7 C (12) C16 S2 C13 C (18) C1 N2 C7 C (2) C12 C13 C14 C (19) C2 N1 C7 N2 0.5 (3) S2 C13 C14 C (2) C12 N1 C7 N (2) C13 C14 C15 C (3) sup-10

14 C2 N1 C7 C (13) C14 C15 C16 S2 0.2 (3) C12 N1 C7 C (13) C13 S2 C16 C (19) C2 N1 C7 C (2) N3 C28 C29 C (2) C12 N1 C7 C8 6.4 (4) N3 C28 C29 S (2) C209 C208 C7 N2 41 (2) C32 S4 C29 C (18) S201 C208 C7 N (12) C32 S4 C29 C (18) C209 C208 C7 N1 138 (2) C28 C29 C30 C (19) S201 C208 C7 N1 41 (2) S4 C29 C30 C (2) C209 C208 C7 C C29 C30 C31 C (3) S201 C208 C7 C C30 C31 C32 S4 1.1 (3) C9 C8 C7 N (4) C29 S4 C32 C (2) S1 C8 C7 N (3) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C22 H22 N (3) 159 C28 H28B N (3) 148 C3 i H3 i N (3) 159 C12 i H12A i N (3) 150 Symmetry code: (i) x 1, y, z. sup-11