organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 6-Amino-5-(1-amino-2,2-dicyanovinyl)3,3a,4,5-tetrahydro-2H-indene-4-spiro10 -cyclopentane-3a,7-dicarbonitrile– thiophene-2-carbaldehyde (1/0.5) Experimental Crystal data Abdullah M. Asiria and Seik Weng Ngb* a Department of Chemistry, Faculty of Science, King Abdul Aziz University, PO Box 80203, Jeddah, Saudi Arabia, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia Correspondence e-mail: seikweng@um.edu.my Received 19 August 2010; accepted 26 August 2010 Key indicators: single-crystal X-ray study; T = 100 K; mean (C–C) = 0.006 Å; disorder in main residue; R factor = 0.074; wR factor = 0.216; data-to-parameter ratio = 15.6. In each of the two independent indene-4-spiropentane molecules in the asymmetric unit of the title 2:1 adduct, C19H18N60.5C5H4OS, the cyclohexene ring adopts a half-chair conformation and the cyclopentene and cyclopentane rings adopt envelope conformations. The mean plane through the cyclohexene/cyclopentene fused system is aligned at a dihedral angle of 77.9 (1) with respect to the mean plane through the cyclopentane ring in one molecule and 87.0 (1) in the other. In the crystal, adjacent indene-4-spiropentane molecules are linked by N—H  N hydrogen bonds into a three-dimensional network. The spaces within the network are occupied by the thiophene-2-carbaldehyde molecules. The thiophene-2-carbaldehyde unit is disordered over two positions of equal occupancy. The crystal studied was found to be a non-morohedral twin with two minor twin components of 18.4 and 9.7%. = 89.879 (2) V = 1953.1 (4) Å3 Z=4 Mo K radiation  = 0.14 mm1 T = 100 K 0.45  0.05  0.05 mm C19H18N60.5C5H4OS Mr = 386.46 Triclinic, P1 a = 12.0181 (14) Å b = 13.8109 (15) Å c = 13.9000 (15) Å = 60.703 (1) = 77.841 (2) Data collection Bruker SMART APEX diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.942, Tmax = 0.993 18784 measured reflections 8916 independent reflections 5141 reflections with I > 2(I) Rint = 0.068 Refinement R[F 2 > 2(F 2)] = 0.074 wR(F 2) = 0.216 S = 1.02 8916 reflections 571 parameters 94 restraints H-atom parameters constrained
max = 0.59 e Å3
min = 0.50 e Å3 Table 1 Hydrogen-bond geometry (Å,  ). D—H  A D—H H  A D  A D—H  A N2—H2n1  N1i N3—H3n1  N11ii N3—H3n2  N12ii N8—H8n1  N7iii N8—H8n2  N4iv N9—H9n1  N5 N9—H9n2  N6 0.86 0.86 0.86 0.86 0.86 0.86 0.86 2.23 2.28 2.29 2.45 2.31 2.39 2.35 2.909 2.970 3.042 2.921 3.006 3.098 3.178 136 138 147 115 138 139 163 (4) (4) (4) (4) (4) (4) (4) Related literature Symmetry codes: (i) x þ 1; y þ 1; z þ 1; (ii) x; y  1; z; (iii) x; y þ 2; z þ 1; (iv) x; y þ 1; z þ 2. For our report of the condensation of cyclopentylidenemalononitrile and thiophene-2-carbaldehyde to form 2,5bis(thienylidene)-1-dicyanomethylene-cyclopentane, a purplecolored compound suitable for application as a dye, see: Asiri (2003). For a related structure, see: Nesterov & Viltchinskaia (2000). For the treatment of twinned diffraction data, see: Spek (2009). 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: XSEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010). We thank King Abdul Aziz University and the University of Malaya for supporting this study. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU5020). o2484 Asiri and Ng doi:10.1107/S1600536810034434 Acta Cryst. (2010). E66, o2484–o2485 organic compounds References Asiri, A. M. (2003). Bull. Korean Chem. Soc. 24, 426–430. Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Acta Cryst. (2010). E66, o2484–o2485 Nesterov, V. N. & Viltchinskaia, E. A. (2000). Acta Cryst. C56, 872–873. Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Spek, A. L. (2009). Acta Cryst. D65, 148–155. Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Asiri and Ng  C19H18N60.5C5H4OS o2485 supplementary materials supplementary materials Acta Cryst. (2010). E66, o2484-o2485 [ doi:10.1107/S1600536810034434 ] 6-Amino-5-(1-amino-2,2-dicyanovinyl)-3,3a,4,5-tetrahydro-2H-indene-4-spiro-1'-cyclopentane3a,7-dicarbonitrile-thiophene-2-carbaldehyde (1/0.5) A. M. Asiri and S. W. Ng Comment We have previously reported the condensation of cyclopentylidenemalononitrile and thiophene-2-carbaldehyde to form 2,5-bis(thienylidene)-1-dicyanomethylene-cyclopentane, a purple-colored compound suitable for application as a dye (Asiri, 2003). For reasons that we are not clear of, our attempted synthesis gave only colorless crystals. We examined a plate-like specimen and identified it as 6-amino-5,5,7-tricyano-3,3a,4,5- tetrahydro-2H-indene-4-spirocyclo-pentane, whose structure has already been reported (Nesterov & Viltchinskaia, 2000). We identified a prismatic specimen as the title 1: 0.5 co-crystal (Scheme I, Fig. 1); the second component is unchanged thiophene-2-carbaldehyde. The first component differs from the reported compound in having an aminodicyanovinyl group (along with a methine hydrogen) in place of the two cyano groups in the 5-position. Additionally, the compound has another cyano group in the 3a position. Experimental Cyclopentylidenemalononitrile (0.13 g, 1 mmol) and thiophene-2-carbaldehyde (0.22 g, 2 mmol) were heated in an oil bath for 6 h. Ethanol was added to break up the solid material. The product was collected and recrystallized from acetic acid. Refinement Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The amino H-atoms were similarly positioned (N–H 0.86 Å) by rotating them; their temperature factors were tied by a factor of 1.2. Modeling the amino group as if it was a methyl group but setting the occupancy factor of one of the three H-atoms to zero gave a satisfactory hydrogen bond scheme except for the H2n2 and H3n2 atoms, which were 1.82 Å apart. The thiophene-2-carbaldehyde molecule is disordered over two positions; as the disorder refined to nearly 1:1, the occupancy of each component was set to 0.5. The sulfur–carbon distances were restrained to 1.70±0.01 Å and the oxygen–carbon distances to 1.25±0.01 Å. The excyclic carbon–carbon distances were restrained to 1.50±0.01 Å and the endocyclic ones to 1.35±0.01 Å. All atoms of each component were restrained to lie on a plane. The temperature factors of C41' were set to those of S1, and that of S1' to those of C41 as the pair of atoms are close to each other. The anisotropic temperature factors of the disordered atoms were restrained to be nearly isotropic. The primed carbon atoms were set to those of the unprimed ones; the anisotropic temperature factors of these carbon atoms were restrained to be nearly isotropic. The structure is a non-meohedrally twinned structure with two minor twin components of 18.5 and 9.7%. The twin domains were identified by the use of PLATON (Spek, 2009). The twinned nature led to a somewhat large weighting scheme. sup-1 supplementary materials Figures Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of the asymmetric unit of the C19H18N6.0.5C5H4OS co-crystal at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. 6-Amino-5-(1-amino-2,2-dicyanovinyl)-3,3a,4,5-tetrahydro-2H-indene- 4-spiro-1'-cyclopentane-3a,7dicarbonitrile–thiophene-2-carbaldehyde (1/0.5) Crystal data C19H18N6·0.5C5H4OS V = 1953.1 (4) Å3 Mr = 386.46 Z=4 Triclinic, P1 F(000) = 812 Hall symbol: -P 1 Dx = 1.314 Mg m−3 a = 12.0181 (14) Å Mo Kα radiation, λ = 0.71073 Å b = 13.8109 (15) Å µ = 0.14 mm−1 T = 100 K Prism, colorless 0.45 × 0.05 × 0.05 mm c = 13.9000 (15) Å α = 60.703 (1)° β = 77.841 (2)° γ = 89.879 (2)° Data collection Bruker SMART APEX diffractometer Radiation source: fine-focus sealed tube 8916 independent reflections graphite 5141 reflections with I > 2σ(I) Rint = 0.068 ω scans θmax = 27.5°, θmin = 1.7° Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.942, Tmax = 0.993 18784 measured reflections h = −15→15 k = −17→17 l = −18→18 Refinement R[F2 > 2σ(F2)] = 0.074 Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites wR(F2) = 0.216 H-atom parameters constrained Refinement on F2 Least-squares matrix: full S = 1.02 8916 reflections sup-2 w = 1/[σ2(Fo2) + (0.1073P)2 + 0.3194P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001 supplementary materials 571 parameters Δρmax = 0.59 e Å−3 94 restraints Δρmin = −0.50 e Å−3 Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) N1 N2 H2N1 H2N2 N3 H3N1 H3N2 N4 N5 N6 N7 N8 H8N1 H8N2 N9 H9N1 H9N2 N10 N11 N12 C1 C2 H2A H2B C3 H3A H3B C4 H4 C5 C6 C7 C8 H8 C9 C10 H10A H10B C11 H11A H11B C12 x y z Uiso*/Ueq 0.4315 (3) 0.3308 (2) 0.3882 0.2992 0.0952 (2) 0.0890 0.1512 0.0331 (3) 0.1735 (3) 0.2511 (3) 0.1317 (3) 0.0847 (2) 0.0700 0.0894 0.2564 (2) 0.2118 0.2489 0.1724 (3) 0.1138 (3) 0.2061 (3) 0.1173 (3) 0.0404 (3) −0.0368 0.0323 0.1023 (3) 0.0473 0.1441 0.1835 (3) 0.2238 0.1931 (3) 0.2654 (3) 0.2539 (3) 0.1539 (3) 0.1863 0.0552 (3) −0.0223 (3) −0.0112 −0.0036 −0.1455 (3) −0.1788 −0.1941 −0.1362 (4) 0.5673 (3) 0.4683 (2) 0.4725 0.4002 0.3434 (2) 0.2827 0.3434 0.2262 (2) 0.5862 (3) 0.8177 (2) 1.0660 (3) 0.9640 (2) 0.9439 0.9057 0.8396 (2) 0.7820 0.8475 0.7429 (3) 1.0999 (3) 1.3168 (2) 0.7121 (3) 0.7911 (3) 0.7515 0.8573 0.8262 (3) 0.8245 0.9023 0.7411 (3) 0.7320 0.6794 (3) 0.5934 (3) 0.5343 (3) 0.5441 (3) 0.5919 0.6065 (3) 0.5370 (3) 0.5705 0.4590 0.5403 (3) 0.6042 0.4702 0.5532 (4) 0.3804 (3) 0.6776 (3) 0.6262 0.7194 0.8014 (3) 0.8652 0.7514 1.0946 (3) 0.9363 (3) 0.5964 (3) 0.3768 (3) 0.6749 (3) 0.6288 0.7372 0.8127 (3) 0.8678 0.7491 1.1069 (3) 0.9271 (3) 0.5990 (3) 0.5405 (3) 0.4653 (3) 0.4857 0.4751 0.3422 (3) 0.2990 0.3028 0.3552 (3) 0.2941 0.4618 (3) 0.5125 (3) 0.6275 (3) 0.7069 (3) 0.7323 0.6523 (3) 0.6247 (3) 0.5416 0.6567 0.6799 (3) 0.6259 0.7057 0.7792 (4) 0.0226 (7) 0.0185 (7) 0.022* 0.022* 0.0188 (7) 0.023* 0.023* 0.0251 (7) 0.0265 (8) 0.0208 (7) 0.0232 (7) 0.0166 (6) 0.020* 0.020* 0.0167 (6) 0.020* 0.020* 0.0308 (8) 0.0283 (8) 0.0199 (7) 0.0138 (7) 0.0182 (8) 0.022* 0.022* 0.0247 (9) 0.030* 0.030* 0.0195 (8) 0.023* 0.0135 (7) 0.0133 (7) 0.0139 (7) 0.0141 (7) 0.017* 0.0149 (7) 0.0162 (7) 0.019* 0.019* 0.0286 (9) 0.034* 0.034* 0.0334 (10) Occ. (<1) sup-3 supplementary materials H12A H12B C13 H13A H13B C14 C15 C16 C17 C18 C19 C20 C21 H21A H21B C22 H22A H22B C23 H23 C24 C25 C26 C27 H27 C28 C29 H29A H29B C30 H30A H30B C31 H31A H31B C32 H32A H32B C33 C34 C35 C36 C37 C38 S1 O1 C39 H39 C40 sup-4 −0.1285 −0.2041 −0.0279 (3) 0.0057 −0.0453 0.1147 (3) 0.1041 (3) 0.0647 (3) 0.1406 (3) 0.3565 (3) 0.1922 (3) 0.3623 (3) 0.4758 (3) 0.4808 0.5430 0.4708 (3) 0.4475 0.5462 0.3825 (3) 0.3701 0.3239 (3) 0.2275 (3) 0.1841 (3) 0.2436 (3) 0.2003 0.3695 (3) 0.4198 (3) 0.4215 0.3731 0.5411 (3) 0.5963 0.5658 0.5307 (3) 0.4947 0.6067 0.4547 (3) 0.4128 0.5013 0.2289 (3) 0.1865 (3) 0.1772 (3) 0.1474 (3) 0.1739 (3) 0.2760 (3) 0.5191 (4) 0.3269 (6) 0.3016 (8) 0.2264 0.3831 (6) 0.4807 0.5839 0.6350 (3) 0.6258 0.7131 0.4307 (3) 0.4207 (3) 0.3143 (3) 0.5114 (3) 0.5790 (3) 0.7745 (3) 1.2092 (3) 1.2877 (3) 1.3517 1.2466 1.3282 (3) 1.4044 1.3284 1.2450 (3) 1.2394 1.1801 (3) 1.0928 (3) 1.0304 (3) 1.0412 (3) 1.0924 1.0996 (3) 1.1257 (3) 1.2063 1.0822 1.0923 (3) 1.1539 1.0714 0.9926 (3) 0.9244 0.9788 1.0274 (3) 0.9608 1.0714 0.9305 (3) 0.9270 (3) 0.8260 (3) 1.0222 (3) 1.0779 (3) 1.2720 (3) 0.2016 (3) 0.0090 (5) 0.0856 (6) 0.0802 0.1866 (7) 0.8445 0.8033 0.7332 (3) 0.7960 0.6918 0.8139 (3) 0.9191 (3) 1.0194 (3) 0.9310 (3) 0.4394 (3) 0.5698 (3) 0.5421 (3) 0.4679 (3) 0.4810 0.4856 0.3445 (3) 0.3088 0.2987 0.3546 (3) 0.2921 0.4614 (3) 0.5128 (3) 0.6278 (3) 0.7085 (3) 0.7300 0.6531 (3) 0.7329 (3) 0.7082 0.8120 0.7248 (4) 0.6596 0.7954 0.7078 (4) 0.7803 0.6758 0.6243 (3) 0.6331 0.5452 0.8186 (3) 0.9199 (3) 1.0245 (3) 0.9246 (3) 0.4380 (3) 0.5729 (3) 0.9487 (3) 1.0456 (5) 1.0644 (6) 1.1067 1.0241 (5) 0.040* 0.040* 0.0173 (8) 0.021* 0.021* 0.0150 (7) 0.0168 (8) 0.0202 (8) 0.0195 (8) 0.0157 (7) 0.0159 (7) 0.0133 (7) 0.0180 (8) 0.022* 0.022* 0.0255 (9) 0.031* 0.031* 0.0202 (8) 0.024* 0.0146 (7) 0.0134 (7) 0.0127 (7) 0.0122 (7) 0.015* 0.0129 (7) 0.0163 (7) 0.020* 0.020* 0.0271 (9) 0.033* 0.033* 0.0279 (9) 0.033* 0.033* 0.0167 (8) 0.020* 0.020* 0.0127 (7) 0.0165 (8) 0.0206 (8) 0.0193 (8) 0.0162 (7) 0.0150 (7) 0.0527 (7) 0.0475 (17) 0.038 (2) 0.046* 0.038 (2) 0.50 0.50 0.50 0.50 0.50 supplementary materials C41 H41 C42 H42 C43 H43 S1' O1' C39' H39' C40' C41' H41' C42' H42' C43' H43' 0.3604 (14) 0.2887 0.4531 (9) 0.4536 0.5438 (10) 0.6154 0.3563 (4) 0.5647 (7) 0.5830 (9) 0.6586 0.4948 (6) 0.5067 (14) 0.5776 0.4095 (8) 0.4042 0.3215 (9) 0.2462 0.2732 (10) 0.2782 0.3522 (9) 0.4191 0.3246 (6) 0.3704 0.2909 (3) 0.4697 (6) 0.3837 (7) 0.3787 0.2880 (8) 0.1919 (10) 0.1758 0.1200 (8) 0.0486 0.1629 (7) 0.1243 1.0424 (10) 1.0833 0.9949 (8) 0.9987 0.9423 (7) 0.9048 1.0178 (3) 0.9167 (6) 0.9125 (7) 0.8789 0.9564 (5) 0.9553 (9) 0.9243 1.0020 (7) 1.0078 1.0391 (6) 1.0744 0.0546 (8) 0.066* 0.065 (3) 0.078* 0.054 (3) 0.064* 0.0546 (8) 0.072 (2) 0.053 (3) 0.063* 0.041 (3) 0.0527 (7) 0.063* 0.044 (2) 0.053* 0.051 (3) 0.061* 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Atomic displacement parameters (Å2) N1 N2 N3 N4 N5 N6 N7 N8 N9 N10 N11 N12 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 U11 0.0205 (16) 0.0155 (15) 0.0218 (16) 0.0316 (18) 0.040 (2) 0.0261 (17) 0.0260 (17) 0.0219 (15) 0.0236 (16) 0.044 (2) 0.041 (2) 0.0275 (17) 0.0172 (16) 0.0199 (18) 0.032 (2) 0.0238 (19) 0.0164 (16) 0.0151 (16) 0.0159 (16) 0.0177 (17) 0.0178 (17) 0.0205 (18) 0.0220 (19) 0.028 (2) 0.0214 (18) 0.0116 (16) 0.0217 (18) U22 0.0246 (16) 0.0125 (14) 0.0111 (14) 0.0172 (16) 0.0175 (16) 0.0133 (14) 0.0238 (16) 0.0101 (13) 0.0116 (13) 0.0232 (17) 0.0181 (16) 0.0113 (14) 0.0097 (15) 0.0136 (16) 0.0210 (19) 0.0185 (17) 0.0097 (15) 0.0092 (15) 0.0080 (15) 0.0118 (15) 0.0109 (15) 0.0126 (16) 0.034 (2) 0.038 (2) 0.0168 (17) 0.0140 (16) 0.0112 (16) U33 0.0219 (19) 0.0216 (18) 0.0191 (18) 0.0164 (18) 0.0218 (19) 0.0215 (18) 0.0239 (19) 0.0157 (17) 0.0129 (16) 0.021 (2) 0.0217 (19) 0.0208 (18) 0.0162 (19) 0.020 (2) 0.018 (2) 0.015 (2) 0.0152 (19) 0.0140 (19) 0.017 (2) 0.0130 (19) 0.0147 (19) 0.018 (2) 0.027 (2) 0.033 (3) 0.016 (2) 0.018 (2) 0.016 (2) U12 0.0060 (13) 0.0030 (11) 0.0012 (11) −0.0003 (13) 0.0057 (14) 0.0028 (12) 0.0025 (13) 0.0016 (11) 0.0024 (11) 0.0066 (15) 0.0016 (14) 0.0018 (12) 0.0040 (12) 0.0069 (13) 0.0074 (16) 0.0029 (14) 0.0023 (12) 0.0028 (12) 0.0014 (12) 0.0021 (13) 0.0039 (13) 0.0042 (13) −0.0009 (17) −0.0014 (18) 0.0073 (14) 0.0035 (12) 0.0033 (13) U13 −0.0030 (14) −0.0023 (13) −0.0015 (13) −0.0026 (14) −0.0104 (15) −0.0055 (14) −0.0096 (14) −0.0090 (13) −0.0070 (13) −0.0112 (16) −0.0001 (15) −0.0070 (14) −0.0050 (14) −0.0064 (15) −0.0072 (17) −0.0045 (15) −0.0046 (14) −0.0038 (14) −0.0044 (14) −0.0034 (14) −0.0057 (14) −0.0078 (15) −0.0042 (17) 0.0011 (19) −0.0045 (15) −0.0030 (14) −0.0061 (15) U23 −0.0118 (15) −0.0048 (13) −0.0054 (13) −0.0019 (14) −0.0088 (14) −0.0077 (14) −0.0136 (15) −0.0032 (12) −0.0035 (12) −0.0067 (16) −0.0093 (15) −0.0074 (13) −0.0075 (14) −0.0068 (15) −0.0074 (17) −0.0073 (16) −0.0065 (14) −0.0045 (14) −0.0055 (14) −0.0064 (14) −0.0047 (14) −0.0081 (15) −0.0133 (19) −0.021 (2) −0.0105 (15) −0.0071 (15) −0.0047 (15) sup-5 supplementary materials C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 S1 O1 C39 C40 C41 C42 C43 S1' O1' C39' C40' C41' C42' C43' 0.0219 (19) 0.0229 (19) 0.0185 (17) 0.0197 (17) 0.0166 (16) 0.0202 (18) 0.032 (2) 0.0273 (19) 0.0173 (17) 0.0166 (16) 0.0150 (16) 0.0159 (16) 0.0177 (17) 0.0191 (17) 0.024 (2) 0.028 (2) 0.0166 (17) 0.0142 (16) 0.0224 (18) 0.029 (2) 0.0255 (19) 0.0202 (17) 0.0218 (18) 0.0638 (17) 0.060 (4) 0.041 (5) 0.050 (6) 0.0418 (12) 0.070 (7) 0.051 (7) 0.0418 (12) 0.074 (5) 0.047 (6) 0.039 (5) 0.0638 (17) 0.058 (6) 0.057 (6) 0.0192 (18) 0.0200 (18) 0.0107 (15) 0.0080 (15) 0.0078 (14) 0.0141 (16) 0.0214 (19) 0.0185 (18) 0.0136 (16) 0.0105 (15) 0.0087 (15) 0.0080 (14) 0.0083 (15) 0.0159 (17) 0.028 (2) 0.025 (2) 0.0118 (16) 0.0095 (15) 0.0137 (16) 0.0166 (18) 0.0165 (17) 0.0107 (15) 0.0091 (15) 0.0479 (14) 0.040 (3) 0.043 (5) 0.035 (5) 0.0609 (18) 0.052 (6) 0.044 (6) 0.0609 (18) 0.054 (4) 0.053 (6) 0.042 (5) 0.0479 (14) 0.050 (5) 0.050 (6) 0.021 (2) 0.016 (2) 0.0159 (19) 0.015 (2) 0.0142 (19) 0.017 (2) 0.014 (2) 0.014 (2) 0.0158 (19) 0.0159 (19) 0.0161 (19) 0.0109 (18) 0.0122 (18) 0.0139 (19) 0.034 (2) 0.036 (3) 0.019 (2) 0.0110 (18) 0.0127 (19) 0.019 (2) 0.0100 (19) 0.0155 (19) 0.016 (2) 0.0463 (14) 0.054 (4) 0.032 (5) 0.038 (5) 0.077 (2) 0.083 (7) 0.062 (7) 0.077 (2) 0.080 (5) 0.056 (6) 0.037 (5) 0.0463 (14) 0.034 (5) 0.055 (6) 0.0046 (15) 0.0070 (15) 0.0019 (13) 0.0033 (13) 0.0010 (12) −0.0029 (13) −0.0091 (16) −0.0028 (15) 0.0019 (13) 0.0023 (13) 0.0054 (12) 0.0023 (12) 0.0006 (12) 0.0000 (13) 0.0049 (16) 0.0131 (16) 0.0024 (13) −0.0011 (12) −0.0012 (13) 0.0004 (15) −0.0024 (14) 0.0021 (13) 0.0005 (13) 0.0097 (11) 0.014 (3) 0.007 (4) 0.011 (4) 0.0194 (12) 0.003 (5) −0.014 (5) 0.0194 (12) 0.013 (4) 0.019 (5) 0.008 (4) 0.0097 (11) 0.007 (4) 0.010 (5) −0.0031 (16) −0.0034 (15) −0.0052 (15) −0.0008 (14) −0.0061 (14) −0.0049 (15) 0.0002 (16) −0.0043 (15) −0.0047 (14) −0.0070 (14) −0.0071 (14) −0.0046 (13) −0.0046 (14) −0.0068 (14) −0.0169 (18) −0.0181 (19) −0.0056 (15) −0.0047 (13) −0.0056 (15) −0.0079 (16) −0.0007 (15) −0.0051 (15) −0.0096 (15) −0.0051 (12) −0.027 (3) −0.020 (4) −0.021 (4) −0.0207 (14) −0.023 (6) −0.001 (5) −0.0207 (14) −0.010 (4) −0.016 (5) −0.014 (4) −0.0051 (12) −0.021 (4) −0.027 (5) −0.0114 (17) −0.0103 (16) −0.0048 (14) −0.0039 (14) −0.0036 (14) −0.0054 (15) −0.0038 (16) −0.0073 (16) −0.0093 (15) −0.0076 (14) −0.0063 (14) −0.0029 (14) −0.0042 (14) −0.0065 (15) −0.0156 (19) −0.0155 (19) −0.0050 (15) −0.0019 (14) −0.0054 (15) −0.0096 (17) −0.0036 (15) −0.0045 (14) −0.0061 (15) −0.0267 (11) −0.026 (3) −0.016 (4) −0.021 (4) −0.0436 (17) −0.040 (5) −0.029 (5) −0.0436 (17) −0.031 (4) −0.023 (5) −0.015 (4) −0.0267 (11) −0.024 (4) −0.029 (5) Geometric parameters (Å, °) N1—C18 N2—C7 N2—H2N1 N2—H2N2 N3—C14 N3—H3N1 N3—H3N2 N4—C16 N5—C17 sup-6 1.152 (4) 1.349 (4) 0.8600 0.8600 1.327 (4) 0.8600 0.8600 1.144 (4) 1.148 (4) C20—C24 C20—C21 C20—C28 C21—C22 C21—H21A C21—H21B C22—C23 C22—H22A C22—H22B 1.515 (5) 1.555 (4) 1.565 (4) 1.538 (5) 0.9900 0.9900 1.499 (5) 0.9900 0.9900 supplementary materials N6—C19 N7—C37 N8—C26 N8—H8N1 N8—H8N2 N9—C33 N9—H9N1 N9—H9N2 N10—C35 N11—C36 N12—C38 C1—C19 C1—C5 C1—C9 C1—C2 C2—C3 C2—H2A C2—H2B C3—C4 C3—H3A C3—H3B C4—C5 C4—H4 C5—C6 C6—C7 C6—C18 C7—C8 C8—C14 C8—C9 C8—H8 C9—C13 C9—C10 C10—C11 C10—H10A C10—H10B C11—C12 C11—H11A C11—H11B C12—C13 C12—H12A C12—H12B C13—H13A C13—H13B C14—C15 C15—C17 C15—C16 C20—C38 1.149 (4) 1.152 (4) 1.336 (4) 0.8600 0.8600 1.335 (4) 0.8600 0.8600 1.148 (5) 1.159 (5) 1.145 (4) 1.490 (5) 1.514 (5) 1.548 (4) 1.557 (5) 1.539 (5) 0.9900 0.9900 1.492 (5) 0.9900 0.9900 1.332 (5) 0.9500 1.447 (5) 1.368 (5) 1.414 (5) 1.505 (5) 1.522 (4) 1.569 (5) 1.0000 1.542 (5) 1.564 (4) 1.530 (5) 0.9900 0.9900 1.502 (6) 0.9900 0.9900 1.526 (5) 0.9900 0.9900 0.9900 0.9900 1.378 (5) 1.423 (5) 1.430 (5) 1.478 (5) C23—C24 C23—H23 C24—C25 C25—C26 C25—C37 C26—C27 C27—C33 C27—C28 C27—H27 C28—C29 C28—C32 C29—C30 C29—H29A C29—H29B C30—C31 C30—H30A C30—H30B C31—C32 C31—H31A C31—H31B C32—H32A C32—H32B C33—C34 C34—C35 C34—C36 S1—C43 S1—C40 O1—C39 C39—C40 C39—H39 C40—C41 C41—C42 C41—H41 C42—C43 C42—H42 C43—H43 S1'—C43' S1'—C40' O1'—C39' C39'—C40' C39'—H39' C40'—C41' C41'—C42' C41'—H41' C42'—C43' C42'—H42' C43'—H43' 1.328 (5) 0.9500 1.456 (4) 1.369 (5) 1.425 (5) 1.514 (5) 1.519 (4) 1.562 (4) 1.0000 1.550 (5) 1.554 (5) 1.526 (5) 0.9900 0.9900 1.516 (5) 0.9900 0.9900 1.520 (5) 0.9900 0.9900 0.9900 0.9900 1.370 (5) 1.421 (5) 1.422 (5) 1.681 (8) 1.698 (8) 1.231 (8) 1.492 (8) 0.9500 1.355 (10) 1.364 (10) 0.9500 1.343 (9) 0.9500 0.9500 1.682 (8) 1.714 (8) 1.234 (8) 1.479 (8) 0.9500 1.340 (10) 1.351 (10) 0.9500 1.342 (9) 0.9500 0.9500 C7—N2—H2N1 C7—N2—H2N2 109.5 109.5 C20—C21—H21B H21A—C21—H21B 110.7 108.8 sup-7 supplementary materials H2N1—N2—H2N2 C14—N3—H3N1 C14—N3—H3N2 H3N1—N3—H3N2 C26—N8—H8N1 C26—N8—H8N2 H8N1—N8—H8N2 C33—N9—H9N1 C33—N9—H9N2 H9N1—N9—H9N2 C19—C1—C5 C19—C1—C9 C5—C1—C9 C19—C1—C2 C5—C1—C2 C9—C1—C2 C3—C2—C1 C3—C2—H2A C1—C2—H2A C3—C2—H2B C1—C2—H2B H2A—C2—H2B C4—C3—C2 C4—C3—H3A C2—C3—H3A C4—C3—H3B C2—C3—H3B H3A—C3—H3B C5—C4—C3 C5—C4—H4 C3—C4—H4 C4—C5—C6 C4—C5—C1 C6—C5—C1 C7—C6—C18 C7—C6—C5 C18—C6—C5 N2—C7—C6 N2—C7—C8 C6—C7—C8 C7—C8—C14 C7—C8—C9 C14—C8—C9 C7—C8—H8 C14—C8—H8 C9—C8—H8 C13—C9—C1 C13—C9—C10 C1—C9—C10 sup-8 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 109.5 107.9 (3) 107.8 (3) 110.4 (3) 110.7 (3) 103.0 (3) 116.8 (3) 105.4 (3) 110.7 110.7 110.7 110.7 108.8 103.9 (3) 111.0 111.0 111.0 111.0 109.0 112.5 (3) 123.8 123.8 131.9 (3) 111.7 (3) 116.2 (3) 119.9 (3) 121.5 (3) 118.2 (3) 123.9 (3) 115.4 (3) 120.6 (3) 109.5 (3) 116.0 (3) 114.8 (3) 105.1 105.1 105.1 112.5 (3) 104.9 (3) 109.4 (3) C23—C22—C21 C23—C22—H22A C21—C22—H22A C23—C22—H22B C21—C22—H22B H22A—C22—H22B C24—C23—C22 C24—C23—H23 C22—C23—H23 C23—C24—C25 C23—C24—C20 C25—C24—C20 C26—C25—C37 C26—C25—C24 C37—C25—C24 N8—C26—C25 N8—C26—C27 C25—C26—C27 C26—C27—C33 C26—C27—C28 C33—C27—C28 C26—C27—H27 C33—C27—H27 C28—C27—H27 C29—C28—C32 C29—C28—C27 C32—C28—C27 C29—C28—C20 C32—C28—C20 C27—C28—C20 C30—C29—C28 C30—C29—H29A C28—C29—H29A C30—C29—H29B C28—C29—H29B H29A—C29—H29B C31—C30—C29 C31—C30—H30A C29—C30—H30A C31—C30—H30B C29—C30—H30B H30A—C30—H30B C30—C31—C32 C30—C31—H31A C32—C31—H31A C30—C31—H31B C32—C31—H31B H31A—C31—H31B C31—C32—C28 104.2 (3) 110.9 110.9 110.9 110.9 108.9 111.9 (3) 124.1 124.1 132.4 (3) 112.1 (3) 115.4 (3) 119.9 (3) 122.7 (3) 117.3 (3) 123.0 (3) 116.3 (3) 120.5 (3) 110.9 (3) 114.1 (3) 114.6 (3) 105.4 105.4 105.4 104.7 (3) 112.1 (3) 113.7 (2) 111.3 (2) 110.4 (3) 104.8 (3) 105.8 (3) 110.6 110.6 110.6 110.6 108.7 103.4 (3) 111.1 111.1 111.1 111.1 109.0 103.3 (3) 111.1 111.1 111.1 111.1 109.1 105.9 (3) supplementary materials C13—C9—C8 C1—C9—C8 C10—C9—C8 C11—C10—C9 C11—C10—H10A C9—C10—H10A C11—C10—H10B C9—C10—H10B H10A—C10—H10B C12—C11—C10 C12—C11—H11A C10—C11—H11A C12—C11—H11B C10—C11—H11B H11A—C11—H11B C11—C12—C13 C11—C12—H12A C13—C12—H12A C11—C12—H12B C13—C12—H12B H12A—C12—H12B C12—C13—C9 C12—C13—H13A C9—C13—H13A C12—C13—H13B C9—C13—H13B H13A—C13—H13B N3—C14—C15 N3—C14—C8 C15—C14—C8 C14—C15—C17 C14—C15—C16 C17—C15—C16 N4—C16—C15 N5—C17—C15 N1—C18—C6 N6—C19—C1 C38—C20—C24 C38—C20—C21 C24—C20—C21 C38—C20—C28 C24—C20—C28 C21—C20—C28 C22—C21—C20 C22—C21—H21A C20—C21—H21A C22—C21—H21B 111.2 (3) 104.7 (3) 114.3 (3) 105.6 (3) 110.6 110.6 110.6 110.6 108.8 104.8 (3) 110.8 110.8 110.8 110.8 108.9 103.6 (3) 111.0 111.0 111.0 111.0 109.0 105.6 (3) 110.6 110.6 110.6 110.6 108.8 122.2 (3) 117.8 (3) 119.9 (3) 121.6 (3) 119.6 (3) 118.6 (3) 175.1 (4) 177.1 (4) 179.4 (4) 176.7 (4) 108.4 (3) 109.8 (3) 102.9 (3) 108.4 (3) 109.8 (2) 117.2 (3) 105.1 (3) 110.7 110.7 110.7 C31—C32—H32A C28—C32—H32A C31—C32—H32B C28—C32—H32B H32A—C32—H32B N9—C33—C34 N9—C33—C27 C34—C33—C27 C33—C34—C35 C33—C34—C36 C35—C34—C36 N10—C35—C34 N11—C36—C34 N7—C37—C25 N12—C38—C20 C43—S1—C40 O1—C39—C40 O1—C39—H39 C40—C39—H39 C41—C40—C39 C41—C40—S1 C39—C40—S1 C40—C41—C42 C40—C41—H41 C42—C41—H41 C43—C42—C41 C43—C42—H42 C41—C42—H42 C42—C43—S1 C42—C43—H43 S1—C43—H43 C43'—S1'—C40' O1'—C39'—C40' O1'—C39'—H39' C40'—C39'—H39' C41'—C40'—C39' C41'—C40'—S1' C39'—C40'—S1' C40'—C41'—C42' C40'—C41'—H41' C42'—C41'—H41' C43'—C42'—C41' C43'—C42'—H42' C41'—C42'—H42' C42'—C43'—S1' C42'—C43'—H43' S1'—C43'—H43' 110.6 110.6 110.6 110.6 108.7 122.3 (3) 118.5 (3) 119.2 (3) 120.5 (3) 121.7 (3) 117.8 (3) 177.5 (4) 178.6 (4) 179.3 (4) 177.2 (3) 89.2 (5) 123.4 (9) 118.3 118.3 126.1 (9) 113.0 (9) 120.9 (7) 111.7 (13) 124.1 124.1 112.2 (12) 123.9 123.9 113.9 (8) 123.1 123.1 89.4 (5) 124.3 (10) 117.9 117.9 128.4 (9) 111.0 (10) 120.6 (8) 114.6 (14) 122.7 122.7 110.9 (12) 124.5 124.5 114.1 (9) 123.0 123.0 C19—C1—C2—C3 C5—C1—C2—C3 97.7 (3) −17.4 (3) C38—C20—C24—C25 C21—C20—C24—C25 −72.8 (3) 170.9 (3) sup-9 supplementary materials C9—C1—C2—C3 C1—C2—C3—C4 C2—C3—C4—C5 C3—C4—C5—C6 C3—C4—C5—C1 C19—C1—C5—C4 C9—C1—C5—C4 C2—C1—C5—C4 C19—C1—C5—C6 C9—C1—C5—C6 C2—C1—C5—C6 C4—C5—C6—C7 C1—C5—C6—C7 C4—C5—C6—C18 C1—C5—C6—C18 C18—C6—C7—N2 C5—C6—C7—N2 C18—C6—C7—C8 C5—C6—C7—C8 N2—C7—C8—C14 C6—C7—C8—C14 N2—C7—C8—C9 C6—C7—C8—C9 C19—C1—C9—C13 C5—C1—C9—C13 C2—C1—C9—C13 C19—C1—C9—C10 C5—C1—C9—C10 C2—C1—C9—C10 C19—C1—C9—C8 C5—C1—C9—C8 C2—C1—C9—C8 C7—C8—C9—C13 C14—C8—C9—C13 C7—C8—C9—C1 C14—C8—C9—C1 C7—C8—C9—C10 C14—C8—C9—C10 C13—C9—C10—C11 C1—C9—C10—C11 C8—C9—C10—C11 C9—C10—C11—C12 C10—C11—C12—C13 C11—C12—C13—C9 C1—C9—C13—C12 C10—C9—C13—C12 C8—C9—C13—C12 C7—C8—C14—N3 C9—C8—C14—N3 sup-10 −138.5 (3) 18.0 (3) −12.2 (4) −175.7 (3) 0.8 (4) −106.3 (3) 136.1 (3) 10.7 (4) 70.8 (3) −46.8 (4) −172.1 (3) −174.7 (3) 8.9 (4) 11.5 (5) −164.9 (3) 6.0 (5) −167.6 (3) −176.8 (3) 9.5 (4) −39.7 (4) 142.9 (3) −171.6 (3) 11.0 (4) 65.2 (3) −177.2 (3) −60.1 (4) −178.6 (3) −61.0 (3) 56.1 (4) −55.7 (3) 61.9 (3) 179.0 (3) −167.1 (3) 63.5 (3) −45.3 (3) −174.7 (3) 74.4 (3) −55.0 (4) 6.0 (4) −114.9 (3) 128.0 (3) −28.3 (4) 39.6 (4) −35.8 (4) 136.9 (3) 18.0 (4) −106.0 (3) −50.7 (4) 81.8 (4) C28—C20—C24—C25 C23—C24—C25—C26 C20—C24—C25—C26 C23—C24—C25—C37 C20—C24—C25—C37 C37—C25—C26—N8 C24—C25—C26—N8 C37—C25—C26—C27 C24—C25—C26—C27 N8—C26—C27—C33 C25—C26—C27—C33 N8—C26—C27—C28 C25—C26—C27—C28 C26—C27—C28—C29 C33—C27—C28—C29 C26—C27—C28—C32 C33—C27—C28—C32 C26—C27—C28—C20 C33—C27—C28—C20 C38—C20—C28—C29 C24—C20—C28—C29 C21—C20—C28—C29 C38—C20—C28—C32 C24—C20—C28—C32 C21—C20—C28—C32 C38—C20—C28—C27 C24—C20—C28—C27 C21—C20—C28—C27 C32—C28—C29—C30 C27—C28—C29—C30 C20—C28—C29—C30 C28—C29—C30—C31 C29—C30—C31—C32 C30—C31—C32—C28 C29—C28—C32—C31 C27—C28—C32—C31 C20—C28—C32—C31 C26—C27—C33—N9 C28—C27—C33—N9 C26—C27—C33—C34 C28—C27—C33—C34 N9—C33—C34—C35 C27—C33—C34—C35 N9—C33—C34—C36 C27—C33—C34—C36 C28—C20—C38—N12 O1—C39—C40—C41 O1—C39—C40—S1 C43—S1—C40—C41 45.5 (4) 175.6 (4) −8.6 (5) −7.9 (6) 167.9 (3) −8.1 (5) 168.3 (3) 176.9 (3) −6.6 (5) 37.1 (4) −147.6 (3) 168.3 (3) −16.4 (4) 170.8 (3) −59.8 (4) −70.7 (4) 58.7 (4) 49.9 (3) 179.3 (3) −67.2 (3) 174.5 (3) 57.7 (4) 177.0 (2) 58.7 (3) −58.1 (4) 54.2 (3) −64.1 (3) 179.1 (3) 12.5 (3) 136.3 (3) −106.7 (3) −33.5 (4) 41.6 (4) −33.9 (4) 13.1 (3) −109.6 (3) 133.0 (3) 52.2 (4) −78.8 (4) −126.9 (3) 102.1 (4) 4.2 (5) −176.8 (3) −173.9 (3) 5.1 (5) −52 (8) −179.8 (2) −0.3 (3) −0.2 (2) supplementary materials C7—C8—C14—C15 C9—C8—C14—C15 N3—C14—C15—C17 C8—C14—C15—C17 N3—C14—C15—C16 C8—C14—C15—C16 C38—C20—C21—C22 C24—C20—C21—C22 C28—C20—C21—C22 C20—C21—C22—C23 C21—C22—C23—C24 C22—C23—C24—C25 C22—C23—C24—C20 C38—C20—C24—C23 C21—C20—C24—C23 C28—C20—C24—C23 127.3 (3) −100.2 (4) 171.0 (3) −6.9 (5) −3.5 (5) 178.5 (3) −96.4 (3) 18.8 (4) 139.4 (3) −18.8 (4) 12.0 (4) 176.3 (4) 0.4 (4) 103.8 (3) −12.4 (4) −137.9 (3) C43—S1—C40—C39 C39—C40—C41—C42 S1—C40—C41—C42 C40—C41—C42—C43 C41—C42—C43—S1 C40—S1—C43—C42 O1'—C39'—C40'—C41' O1'—C39'—C40'—S1' C43'—S1'—C40'—C41' C43'—S1'—C40'—C39' C39'—C40'—C41'—C42' S1'—C40'—C41'—C42' C40'—C41'—C42'—C43' C41'—C42'—C43'—S1' C40'—S1'—C43'—C42' −179.7 (2) 179.7 (2) 0.2 (3) −0.2 (4) 0.1 (4) 0.1 (2) 179.9 (2) 0.2 (3) 0.1 (2) 179.8 (2) −179.9 (2) −0.2 (4) 0.2 (4) −0.1 (3) 0.0 (2) Hydrogen-bond geometry (Å, °) D—H···A D—H H···A D···A D—H···A 0.86 2.23 2.909 (4) 136 N3—H3n1···N11ii 0.86 2.28 2.970 (4) 138 N3—H3n2···N12ii 0.86 2.29 3.042 (4) 147 N8—H8n1···N7iii 0.86 2.45 2.921 (4) 115 0.86 2.31 3.006 (4) N8—H8n2···N4iv N9—H9n1···N5 0.86 2.39 3.098 (4) N9—H9n2···N6 0.86 2.35 3.178 (4) Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) −x, −y+2, −z+1; (iv) −x, −y+1, −z+2. 138 N2—H2n1···N1 i 139 163 sup-11 supplementary materials Fig. 1 sup-12