Prof. 5

organic compounds Acta Crystallographica Section E  = 0.21 mm 1 T = 296 K 0.32  0.23  0.20 mm = 79.300 (1) V = 1532.90 (7) Å3 Z=4 Mo K radiation Structure Reports Online ISSN 1600-5368 Data collection (2E)-3-[4-(Dimethylamino)phenyl]-1(2,5-dimethyl-3-thienyl)prop-2-en-1-one Bruker Kappa APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2005) Tmin = 0.947, Tmax = 0.962 Abdullah M. Asiri,a,b Salman A. Khanb and M. Nawaz Tahirc* Refinement a The Center of Excellence for Advanced Materials Research, King Abdul Aziz University, Jeddah 21589, PO Box 80203, Saudi Arabia, bDepartment of Chemistry, Faculty of Science, King Abdul Aziz University, Jeddah 21589, PO Box 80203, Saudi Arabia, and cDepartment of Physics, University of Sargodha, Sargodha, Pakistan Correspondence e-mail: dmntahir_uos@yahoo.com R[F 2 > 2(F 2)] = 0.049 wR(F 2) = 0.156 S = 1.02 5536 reflections 22632 measured reflections 5536 independent reflections 3543 reflections with I > 2(I) Rint = 0.039 373 parameters H-atom parameters constrained
max = 0.19 e Å 3
min = 0.23 e Å 3 Table 1 Hydrogen-bond geometry (Å,  ). Received 14 August 2010; accepted 20 August 2010 Key indicators: single-crystal X-ray study; T = 296 K; mean (C–C) = 0.003 Å; disorder in main residue; R factor = 0.049; wR factor = 0.156; data-to-parameter ratio = 14.8. The asymmetric unit of the title compound, C17H19NOS, contains two independent molecules which differ in the dihedral angles between the five- and six-membered rings [12.52 (10) and 4.63 (11) ]. Weak intermolecular C—H


O hydrogen bonds link the two independent molecules into pseudocentrosymmetric dimers. In one molecule, the O atom of the carbonyl group is disordered over two positions in a 0.699 (4):0.301 (4) ratio. Related literature For background and related crystal structures, see: Asiri et al. (2010a,b,c). For graph-set notation, see: Bernstein et al. (1995). D—H


A D—H H


A D


A D—H


A C6—H6


O2 C19—H19


O1A C19—H19


O1B 0.93 0.93 0.93 2.48 2.52 2.48 3.275 (3) 3.317 (9) 3.264 (3) 143 144 142 Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; 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, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON. The authors thank the Chemistry Department, King Abdul Aziz University, Jeddah, Saudi Arabia for providing research facilities and for the financial support of this work (grant No. 3–045/430). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2751). References Experimental Crystal data C17H19NOS Mr = 285.40 Triclinic, P1 a = 7.7665 (2) Å o2404 Asiri et al. b = 12.8624 (4) Å c = 16.0318 (4) Å = 79.917 (1) = 80.029 (2) Asiri, A. M., Khan, S. A. & Tahir, M. N. (2010a). Acta Cryst. E66, o2099. Asiri, A. M., Khan, S. A. & Tahir, M. N. (2010b). Acta Cryst. E66, o2133. Asiri, A. M., Khan, S. A. & Tahir, M. N. (2010c). Acta Cryst. E66, o2259–o2260. Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Spek, A. L. (2009). Acta Cryst. D65, 148–155. doi:10.1107/S1600536810033751 Acta Cryst. (2010). E66, o2404 supplementary materials supplementary materials Acta Cryst. (2010). E66, o2404 [ doi:10.1107/S1600536810033751 ] (2E)-3-[4-(Dimethylamino)phenyl]-1-(2,5-dimethyl-3-thienyl)prop-2-en-1-one A. M. Asiri, S. A. Khan and M. N. Tahir Comment In continuation of our structural studies of 2,5-dimethylthiophen-3-yl derivatives (Asiri et al., 2010a, b, c), we present here the crystal structure of the title compound, (I) (Fig. 1). The asymmetric unit of (I) contains two independent molecules having different configurations. In one molecule, the phenyl ring A (C1—C6) of 4-(dimethylamino)phenyl, the central group B (C9—C11/O1A) and group C (C12—C17/S1) of 2,5-dimethylthiophen are planar with r. m. s. deviation of 0.0070, 0.0455 and 0.0255 Å, respectively. The dimethylamino group D (C7/N1/C8) is of course planar. The dihedral angle between A/B, A/C, A/D and B/C is 16.29 (39), 12.52 (10), 4.53 (27) and 12.80 (40) (15)°, respectively. In the second molecule, the phenyl ring E (C18—C23) of 4-(dimethylamino)phenyl, the central group F (C26—C28/O2) and group G (C29—C34/S2) of 2,5-dimethylthiophen are planar with r. m. s. deviation of 0.0028, 0.0015 and 0.0317 Å, respectively. The dihedral angle between E/F, E/G and F/G is 8.01 (20), 4.63 (11), and 11.94 (18)°, respectively. The dimethylamino group H (C24/N2/C25) of this molecule is oriented at a dihedral angle of 2.88 (29) ° with its parent phenyl ring. The title compound essentially consists of dimers which are formed due to C—H···O type of intermolecular H-bonding (Table 1, Fig. 1) and complete R22(14) ring motif (Bernstein et al., 1995). Experimental A solution of 3-acetyl-2,5-dimethythiophene (0.38 g, 2.5 mmol) and N, N-dimethylbenzaldehyde (0.37 g, 2.5 mmol) in ethanolic solution of NaOH (3.0 g in 10 ml of methanol) was stirred for 16 h at room temperature. The solution was poured into ice cold water of pH = 2 (pH adjusted by HCl). The solid was separated and dissolved in CH2Cl2, washed with saturated solution of NaHCO3 and evaporated to dryness. The residual was recrystallized from methanol/chloroform to afford light yellow prisms of (I). Yield: 86%; m.p. 375–376 K. IR (KBr) \vmax cm-1: 2979 (C—Haliphatic), 1638 (Cδb=O), 1612 (CδbC), 1167 (C—N). Refinement In one independent molecule, the O-atom of carbonyl group is disordered over two set of sites with occupancy ratio of 0.699 (4):0.301 (4). The disordered O-atoms were refined anisotropically with constrained displacement ellipsoids. The H-atoms were positioned geometrically (C–H = 0.93–0.96 Å) and refined as riding with Uiso(H) = xUeq(C), where x = 1.5 for methyl and x = 1.2 for aryl H-atoms. sup-1 supplementary materials Figures Fig. 1. Two independent molecules of (I) with the atomic numbering and 50% probability displacement ellipsoids. Dashed lines denote intermolecular hydrogen bonds. Only major part of the disordered atom (O1A) is shown. (2E)-3-[4-(Dimethylamino)phenyl]-1-(2,5-dimethyl-3- thienyl)prop-2-en-1-one Crystal data C17H19NOS Z=4 Mr = 285.40 F(000) = 608 Triclinic, P1 Dx = 1.237 Mg m−3 Hall symbol: -P 1 a = 7.7665 (2) Å b = 12.8624 (4) Å Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3543 reflections θ = 1.6–25.3° c = 16.0318 (4) Å µ = 0.21 mm−1 T = 296 K Prism, yellow 0.32 × 0.23 × 0.20 mm α = 79.917 (1)° β = 80.029 (2)° γ = 79.300 (1)° V = 1532.90 (7) Å3 Data collection Bruker Kappa APEXII CCD diffractometer Radiation source: fine-focus sealed tube graphite Detector resolution: 8.10 pixels mm-1 ω scans Absorption correction: multi-scan (SADABS; Bruker, 2005) Tmin = 0.947, Tmax = 0.962 5536 independent reflections 3543 reflections with I > 2σ(I) Rint = 0.039 θmax = 25.3°, θmin = 1.6° h = −9→9 k = −15→15 l = −19→19 22632 measured reflections Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.049 sup-2 Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites supplementary materials wR(F2) = 0.156 H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0809P)2 + 0.1945P] S = 1.02 where P = (Fo2 + 2Fc2)/3 5536 reflections (Δ/σ)max < 0.001 373 parameters Δρmax = 0.19 e Å−3 0 restraints Δρmin = −0.23 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 F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating Rfactors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 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 (Å2) S2 O2 N2 C18 C19 H19 C20 H20 C21 C22 H22 C23 H23 C24 H24A H24B H24C C25 H25A H25B H25C C26 H26 C27 H27 x y z Uiso*/Ueq 0.67761 (9) 0.4763 (3) 0.8597 (3) 0.6929 (3) 0.6399 (3) 0.5662 0.6922 (3) 0.6527 0.8042 (3) 0.8576 (3) 0.9306 0.8036 (3) 0.8422 0.9775 (4) 0.9187 1.0828 1.0086 0.7976 (4) 0.8450 0.6706 0.8360 0.6300 (3) 0.5475 0.6737 (3) 0.7601 0.59564 (5) 0.71665 (15) 0.3931 (2) 0.54644 (19) 0.5910 (2) 0.6569 0.5417 (2) 0.5742 0.4429 (2) 0.3967 (2) 0.3306 0.4480 (2) 0.4158 0.2907 (3) 0.2371 0.2966 0.2709 0.4364 (3) 0.5008 0.4520 0.3851 0.60139 (19) 0.6632 0.57594 (19) 0.5169 0.72204 (4) 0.46717 (12) 0.04152 (14) 0.25944 (15) 0.18057 (15) 0.1760 0.10983 (16) 0.0585 0.11278 (15) 0.19221 (16) 0.1971 0.26256 (16) 0.3141 0.0452 (2) 0.0827 0.0666 −0.0111 −0.03922 (18) −0.0628 −0.0304 −0.0782 0.33348 (15) 0.3248 0.41143 (15) 0.4229 0.0656 (2) 0.0919 (7) 0.0836 (7) 0.0533 (6) 0.0594 (6) 0.071* 0.0634 (7) 0.076* 0.0609 (6) 0.0665 (7) 0.080* 0.0628 (7) 0.075* 0.0990 (10) 0.149* 0.149* 0.149* 0.0934 (10) 0.140* 0.140* 0.140* 0.0569 (6) 0.068* 0.0583 (6) 0.070* Occ. (<1) sup-3 supplementary materials C28 C29 C30 C31 H31A H31B H31C C32 H32 C33 C34 H34A H34B H34C S1 O1A O1B N1 C1 C2 H2 C3 H3 C4 C5 H5 C6 H6 C7 H7A H7B H7C C8 H8A H8B H8C C9 H9 C10 H10 C11 C12 C13 C14 H14A H14B H14C C15 H15 sup-4 0.5897 (3) 0.6421 (3) 0.5930 (3) 0.4827 (3) 0.3609 0.4939 0.5231 0.7473 (3) 0.7916 0.7761 (3) 0.86743 (13) 0.9208 0.7826 0.9573 0.33038 (9) 0.37293 (9) 0.44871 (9) 0.1145 (2) 0.23647 (9) 0.12944 (9) 0.0858 0.0866 (3) 0.0143 0.1505 (3) 0.2551 (3) 0.2980 0.2954 (3) 0.3646 −0.0074 (4) −0.1218 0.0359 −0.0170 0.1848 (4) 0.3109 0.1325 0.1578 0.2893 (3) 0.3481 0.2657 (3) 0.2076 0.3278 (4) 0.3116 (3) 0.3820 (3) 0.4959 (4) 0.4281 0.5361 0.5962 0.2189 (4) 0.1634 0.6381 (2) 0.60325 (18) 0.66231 (19) 0.7713 (2) 0.7639 0.8124 0.8071 0.50189 (19) 0.4518 0.48573 (19) 0.38708 (5) 0.3365 0.3560 0.4057 0.95464 (5) 0.78720 (5) 0.80552 (5) 1.14648 (8) 0.97971 (5) 1.08011 (5) 1.1112 1.1342 (2) 1.2006 1.0908 (2) 0.9896 (2) 0.9578 0.9364 (2) 0.8689 1.2468 (2) 1.2352 1.2978 1.2737 1.1031 (3) 1.0830 1.0413 1.1560 0.9220 (2) 0.8525 0.9544 (2) 1.0234 0.8854 (2) 0.93130 (19) 0.8784 (2) 0.7703 (2) 0.7207 0.7454 0.7758 1.0352 (2) 1.0824 0.48031 (16) 0.56638 (15) 0.63207 (15) 0.63494 (18) 0.6541 0.5788 0.6738 0.59204 (15) 0.5551 0.67384 (15) 0.72324 (4) 0.6851 0.7667 0.7495 −0.19233 (3) 0.08108 (4) 0.06963 (3) 0.49058 (4) 0.27862 (4) 0.27559 (4) 0.2250 0.34461 (15) 0.3400 0.42243 (15) 0.42629 (15) 0.4770 0.35693 (15) 0.3620 0.48868 (19) 0.4808 0.4422 0.5418 0.56916 (17) 0.5569 0.5960 0.6069 0.20630 (15) 0.2182 0.12541 (15) 0.1101 0.05931 (17) −0.03056 (15) −0.09877 (16) −0.1008 (2) −0.1125 −0.0463 −0.1447 −0.05812 (16) −0.0202 0.0600 (6) 0.0523 (6) 0.0551 (6) 0.0718 (7) 0.108* 0.108* 0.108* 0.0546 (6) 0.066* 0.0569 (6) 0.0717 (7) 0.108* 0.108* 0.108* 0.0728 (2) 0.0854 (10) 0.0854 (10) 0.0711 (6) 0.0537 (6) 0.0605 (6) 0.073* 0.0620 (6) 0.074* 0.0565 (6) 0.0598 (6) 0.072* 0.0604 (6) 0.072* 0.0850 (9) 0.127* 0.127* 0.127* 0.0845 (9) 0.127* 0.127* 0.127* 0.0630 (7) 0.076* 0.0634 (7) 0.076* 0.0710 (7) 0.0577 (6) 0.0618 (6) 0.0947 (10) 0.142* 0.142* 0.142* 0.0682 (7) 0.082* 0.699 (4) 0.301 (4) supplementary materials C16 C17 H17A H17B H17C 0.2183 (3) 0.1387 (4) 0.0753 0.0587 0.2312 1.0591 (2) 1.1611 (2) 1.2093 1.1454 1.1937 −0.14266 (15) −0.19338 (18) −0.1549 −0.2272 −0.2304 0.0633 (7) 0.0881 (9) 0.132* 0.132* 0.132* Atomic displacement parameters (Å2) S2 O2 N2 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 S1 O1A O1B N1 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 U11 0.0735 (4) 0.1119 (15) 0.1085 (19) 0.0545 (13) 0.0623 (14) 0.0667 (15) 0.0693 (15) 0.0795 (17) 0.0762 (16) 0.114 (3) 0.115 (2) 0.0607 (14) 0.0600 (14) 0.0616 (14) 0.0525 (12) 0.0529 (13) 0.0766 (17) 0.0576 (13) 0.0580 (13) 0.0770 (17) 0.0879 (5) 0.139 (3) 0.139 (3) 0.0802 (14) 0.0614 (14) 0.0676 (15) 0.0669 (15) 0.0552 (13) 0.0658 (15) 0.0683 (15) 0.0855 (19) 0.095 (2) 0.0800 (17) 0.0822 (17) 0.096 (2) 0.0728 (15) 0.0642 (14) 0.104 (2) 0.0938 (19) U22 0.0660 (5) 0.0755 (13) 0.0809 (18) 0.0483 (14) 0.0565 (16) 0.0723 (18) 0.0609 (17) 0.0541 (16) 0.0575 (16) 0.091 (2) 0.111 (3) 0.0495 (15) 0.0530 (15) 0.0522 (15) 0.0469 (14) 0.0506 (15) 0.0560 (16) 0.0484 (14) 0.0548 (15) 0.0696 (18) 0.0797 (5) 0.0468 (13) 0.0468 (13) 0.0799 (16) 0.0501 (14) 0.0631 (17) 0.0568 (16) 0.0636 (16) 0.0645 (17) 0.0557 (16) 0.085 (2) 0.104 (2) 0.0522 (15) 0.0533 (16) 0.0540 (17) 0.0477 (14) 0.0595 (16) 0.083 (2) 0.0575 (17) U33 0.0564 (4) 0.0746 (13) 0.0615 (15) 0.0575 (14) 0.0566 (15) 0.0515 (15) 0.0547 (15) 0.0639 (16) 0.0538 (15) 0.092 (2) 0.0604 (18) 0.0594 (15) 0.0590 (15) 0.0640 (16) 0.0553 (14) 0.0595 (15) 0.0794 (18) 0.0547 (14) 0.0550 (15) 0.0632 (16) 0.0505 (4) 0.0649 (14) 0.0649 (14) 0.0510 (13) 0.0468 (13) 0.0454 (14) 0.0552 (15) 0.0480 (14) 0.0453 (14) 0.0518 (15) 0.081 (2) 0.0560 (17) 0.0543 (15) 0.0525 (15) 0.0631 (17) 0.0536 (15) 0.0622 (16) 0.085 (2) 0.0518 (15) U12 −0.0018 (3) 0.0380 (12) 0.0004 (14) −0.0085 (11) −0.0038 (12) −0.0091 (13) −0.0110 (13) 0.0043 (13) −0.0021 (13) 0.001 (2) −0.020 (2) −0.0054 (11) 0.0012 (12) −0.0001 (12) −0.0026 (11) −0.0050 (11) 0.0037 (13) 0.0027 (11) −0.0013 (11) 0.0029 (14) −0.0107 (4) 0.0062 (15) 0.0062 (15) −0.0014 (12) −0.0070 (11) 0.0004 (12) 0.0049 (12) −0.0098 (12) −0.0044 (12) 0.0004 (12) 0.0012 (16) −0.0147 (18) −0.0032 (13) −0.0024 (13) −0.0001 (14) −0.0027 (12) −0.0053 (12) 0.0179 (18) 0.0045 (14) U13 −0.0110 (3) −0.0323 (11) −0.0194 (13) −0.0171 (11) −0.0178 (12) −0.0226 (12) −0.0162 (12) −0.0222 (13) −0.0244 (12) −0.0127 (19) −0.0224 (17) −0.0147 (11) −0.0146 (12) −0.0138 (12) −0.0091 (10) −0.0042 (11) −0.0093 (14) −0.0101 (11) −0.0107 (11) −0.0205 (13) −0.0075 (3) −0.0284 (15) −0.0284 (15) −0.0086 (10) −0.0121 (11) −0.0156 (11) −0.0113 (12) −0.0060 (11) −0.0150 (11) −0.0131 (12) −0.0016 (15) −0.0109 (15) −0.0164 (12) −0.0155 (12) −0.0238 (14) −0.0170 (12) −0.0105 (12) −0.0061 (17) −0.0202 (13) U23 −0.0153 (3) −0.0120 (10) −0.0201 (13) 0.0000 (11) 0.0018 (12) 0.0017 (13) −0.0065 (13) −0.0079 (13) −0.0003 (12) −0.0354 (19) −0.0192 (17) −0.0022 (12) −0.0053 (12) −0.0073 (13) −0.0066 (11) −0.0099 (12) −0.0180 (14) −0.0090 (11) −0.0057 (12) −0.0012 (14) −0.0141 (3) −0.0026 (11) −0.0026 (11) −0.0166 (12) 0.0026 (11) 0.0024 (12) −0.0026 (12) −0.0022 (12) 0.0024 (12) −0.0001 (12) −0.0302 (17) −0.0182 (16) −0.0021 (12) −0.0055 (12) −0.0093 (13) −0.0097 (12) −0.0138 (13) −0.0237 (17) −0.0123 (12) sup-5 supplementary materials C16 C17 0.0753 (16) 0.120 (2) 0.0615 (17) 0.076 (2) 0.0524 (15) 0.0632 (18) −0.0063 (13) −0.0048 (18) −0.0158 (12) −0.0308 (17) −0.0046 (12) 0.0076 (15) Geometric parameters (Å, °) S2—C30 S2—C33 O2—C28 N2—C21 N2—C25 N2—C24 C18—C23 C18—C19 C18—C26 C19—C20 C19—H19 C20—C21 C20—H20 C21—C22 C22—C23 C22—H22 C23—H23 C24—H24A C24—H24B C24—H24C C25—H25A C25—H25B C25—H25C C26—C27 C26—H26 C27—C28 C27—H27 C28—C29 C29—C30 C29—C32 C30—C31 C31—H31A C31—H31B C31—H31C C32—C33 C32—H32 C33—C34 C34—H34A C34—H34B C34—H34C S1—C16 1.713 (2) 1.720 (2) 1.225 (3) 1.373 (3) 1.443 (3) 1.455 (3) 1.391 (3) 1.391 (3) 1.453 (3) 1.361 (3) 0.9300 1.399 (3) 0.9300 1.404 (3) 1.370 (3) 0.9300 0.9300 0.9600 0.9600 0.9600 0.9600 0.9600 0.9600 1.321 (3) 0.9300 1.466 (3) 0.9300 1.477 (3) 1.366 (3) 1.439 (3) 1.505 (3) 0.9600 0.9600 0.9600 1.342 (3) 0.9300 1.499 (2) 0.9600 0.9600 0.9600 1.702 (3) S1—C13 O1A—C11 O1B—C11 N1—C4 N1—C8 N1—C7 C1—C2 C1—C6 C1—C9 C2—C3 C2—H2 C3—C4 C3—H3 C4—C5 C5—C6 C5—H5 C6—H6 C7—H7A C7—H7B C7—H7C C8—H8A C8—H8B C8—H8C C9—C10 C9—H9 C10—C11 C10—H10 C11—C12 C12—C13 C12—C15 C13—C14 C14—H14A C14—H14B C14—H14C C15—C16 C15—H15 C16—C17 C17—H17A C17—H17B C17—H17C 1.709 (3) 1.250 (3) 1.265 (3) 1.371 (2) 1.441 (3) 1.451 (3) 1.3980 (9) 1.398 (2) 1.444 (2) 1.369 (3) 0.9300 1.408 (3) 0.9300 1.398 (3) 1.367 (3) 0.9300 0.9300 0.9600 0.9600 0.9600 0.9600 0.9600 0.9600 1.324 (3) 0.9300 1.462 (3) 0.9300 1.476 (3) 1.369 (3) 1.430 (3) 1.505 (4) 0.9600 0.9600 0.9600 1.337 (3) 0.9300 1.505 (3) 0.9600 0.9600 0.9600 C30—S2—C33 C21—N2—C25 C21—N2—C24 93.28 (11) 122.0 (2) 121.2 (2) C4—N1—C8 C4—N1—C7 C8—N1—C7 121.07 (17) 121.12 (16) 117.61 (17) sup-6 supplementary materials C25—N2—C24 C23—C18—C19 C23—C18—C26 C19—C18—C26 C20—C19—C18 C20—C19—H19 C18—C19—H19 C19—C20—C21 C19—C20—H20 C21—C20—H20 N2—C21—C20 N2—C21—C22 C20—C21—C22 C23—C22—C21 C23—C22—H22 C21—C22—H22 C22—C23—C18 C22—C23—H23 C18—C23—H23 N2—C24—H24A N2—C24—H24B H24A—C24—H24B N2—C24—H24C H24A—C24—H24C H24B—C24—H24C N2—C25—H25A N2—C25—H25B H25A—C25—H25B N2—C25—H25C H25A—C25—H25C H25B—C25—H25C C27—C26—C18 C27—C26—H26 C18—C26—H26 C26—C27—C28 C26—C27—H27 C28—C27—H27 O2—C28—C27 O2—C28—C29 C27—C28—C29 C30—C29—C32 C30—C29—C28 C32—C29—C28 C29—C30—C31 C29—C30—S2 C31—C30—S2 C30—C31—H31A C30—C31—H31B H31A—C31—H31B 116.7 (2) 116.4 (2) 123.4 (2) 120.1 (2) 122.4 (2) 118.8 118.8 121.3 (2) 119.4 119.4 121.7 (2) 121.4 (2) 116.9 (2) 120.9 (2) 119.6 119.6 122.2 (2) 118.9 118.9 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 129.1 (2) 115.4 115.4 121.9 (2) 119.1 119.1 120.7 (2) 120.5 (2) 118.8 (2) 111.6 (2) 124.1 (2) 124.2 (2) 130.2 (2) 110.76 (17) 119.09 (18) 109.5 109.5 109.5 C2—C1—C6 C2—C1—C9 C6—C1—C9 C3—C2—C1 C3—C2—H2 C1—C2—H2 C2—C3—C4 C2—C3—H3 C4—C3—H3 N1—C4—C5 N1—C4—C3 C5—C4—C3 C6—C5—C4 C6—C5—H5 C4—C5—H5 C5—C6—C1 C5—C6—H6 C1—C6—H6 N1—C7—H7A N1—C7—H7B H7A—C7—H7B N1—C7—H7C H7A—C7—H7C H7B—C7—H7C N1—C8—H8A N1—C8—H8B H8A—C8—H8B N1—C8—H8C H8A—C8—H8C H8B—C8—H8C C10—C9—C1 C10—C9—H9 C1—C9—H9 C9—C10—C11 C9—C10—H10 C11—C10—H10 O1A—C11—C10 O1B—C11—C10 O1A—C11—C12 O1B—C11—C12 C10—C11—C12 C13—C12—C15 C13—C12—C11 C15—C12—C11 C12—C13—C14 C12—C13—S1 C14—C13—S1 C13—C14—H14A C13—C14—H14B 116.15 (11) 123.76 (10) 120.08 (15) 122.24 (10) 118.9 118.9 121.0 (2) 119.5 119.5 121.7 (2) 121.3 (2) 117.0 (2) 121.2 (2) 119.4 119.4 122.4 (2) 118.8 118.8 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 129.1 (2) 115.5 115.5 122.3 (2) 118.9 118.9 119.3 (2) 120.9 (2) 121.6 (2) 115.3 (2) 118.6 (2) 111.0 (2) 123.9 (2) 125.1 (2) 129.6 (2) 110.73 (18) 119.7 (2) 109.5 109.5 sup-7 supplementary materials C30—C31—H31C H31A—C31—H31C H31B—C31—H31C C33—C32—C29 C33—C32—H32 C29—C32—H32 C32—C33—C34 C32—C33—S2 C34—C33—S2 C33—C34—H34A C33—C34—H34B H34A—C34—H34B C33—C34—H34C H34A—C34—H34C H34B—C34—H34C C16—S1—C13 109.5 109.5 109.5 114.3 (2) 122.8 122.8 128.5 (2) 109.98 (18) 121.41 (15) 109.5 109.5 109.5 109.5 109.5 109.5 93.33 (12) H14A—C14—H14B C13—C14—H14C H14A—C14—H14C H14B—C14—H14C C16—C15—C12 C16—C15—H15 C12—C15—H15 C15—C16—C17 C15—C16—S1 C17—C16—S1 C16—C17—H17A C16—C17—H17B H17A—C17—H17B C16—C17—H17C H17A—C17—H17C H17B—C17—H17C 109.5 109.5 109.5 109.5 114.7 (2) 122.7 122.7 128.8 (2) 110.20 (19) 120.93 (19) 109.5 109.5 109.5 109.5 109.5 109.5 C23—C18—C19—C20 C26—C18—C19—C20 C18—C19—C20—C21 C25—N2—C21—C20 C24—N2—C21—C20 C25—N2—C21—C22 C24—N2—C21—C22 C19—C20—C21—N2 C19—C20—C21—C22 N2—C21—C22—C23 C20—C21—C22—C23 C21—C22—C23—C18 C19—C18—C23—C22 C26—C18—C23—C22 C23—C18—C26—C27 C19—C18—C26—C27 C18—C26—C27—C28 C26—C27—C28—O2 C26—C27—C28—C29 O2—C28—C29—C30 C27—C28—C29—C30 O2—C28—C29—C32 C27—C28—C29—C32 C32—C29—C30—C31 C28—C29—C30—C31 C32—C29—C30—S2 C28—C29—C30—S2 C33—S2—C30—C29 C33—S2—C30—C31 C30—C29—C32—C33 C28—C29—C32—C33 C29—C32—C33—C34 C29—C32—C33—S2 0.2 (4) −178.6 (2) −0.5 (4) −3.8 (4) 179.5 (3) 176.3 (3) −0.5 (4) −179.1 (2) 0.9 (4) 179.0 (2) −1.0 (4) 0.7 (4) −0.3 (4) 178.4 (2) 6.1 (4) −175.2 (2) −176.8 (2) −0.5 (4) 178.5 (2) −10.8 (4) 170.2 (2) 167.6 (2) −11.4 (4) −179.4 (2) −0.8 (4) 1.0 (3) 179.60 (19) −1.35 (19) 179.03 (19) −0.1 (3) −178.6 (2) 175.0 (2) −0.9 (3) C1—C2—C3—C4 C8—N1—C4—C5 C7—N1—C4—C5 C8—N1—C4—C3 C7—N1—C4—C3 C2—C3—C4—N1 C2—C3—C4—C5 N1—C4—C5—C6 C3—C4—C5—C6 C4—C5—C6—C1 C2—C1—C6—C5 C9—C1—C6—C5 C2—C1—C9—C10 C6—C1—C9—C10 C1—C9—C10—C11 C9—C10—C11—O1A C9—C10—C11—O1B C9—C10—C11—C12 O1A—C11—C12—C13 O1B—C11—C12—C13 C10—C11—C12—C13 O1A—C11—C12—C15 O1B—C11—C12—C15 C10—C11—C12—C15 C15—C12—C13—C14 C11—C12—C13—C14 C15—C12—C13—S1 C11—C12—C13—S1 C16—S1—C13—C12 C16—S1—C13—C14 C13—C12—C15—C16 C11—C12—C15—C16 C12—C15—C16—C17 0.5 (3) 0.5 (4) −174.2 (2) −178.1 (2) 7.2 (4) 177.12 (19) −1.5 (3) −177.6 (2) 1.1 (4) 0.5 (4) −1.5 (3) 177.3 (2) 7.7 (3) −171.1 (3) −180.0 (2) 14.4 (4) −20.8 (4) −174.1 (2) −16.1 (4) 17.9 (4) 172.6 (2) 162.9 (2) −163.2 (2) −8.4 (4) 176.9 (3) −4.0 (4) −1.1 (3) 178.0 (2) 1.2 (2) −177.1 (2) 0.5 (3) −178.6 (3) −178.2 (3) sup-8 supplementary materials C30—S2—C33—C32 C30—S2—C33—C34 C6—C1—C2—C3 C9—C1—C2—C3 1.29 (19) −174.97 (18) 1.04 (17) −177.80 (18) C12—C15—C16—S1 C13—S1—C16—C15 C13—S1—C16—C17 0.4 (3) −0.9 (2) 177.8 (2) Hydrogen-bond geometry (Å, °) D—H···A C6—H6···O2 C19—H19···O1A C19—H19···O1B D—H 0.93 0.93 0.93 H···A 2.48 2.52 2.48 D···A 3.275 (3) 3.317 (9) 3.264 (3) D—H···A 143 144 142 sup-9 supplementary materials Fig. 1 sup-10