organic compounds Acta Crystallographica Section E Experimental Structure Reports Online Crystal data ISSN 1600-5368 4-[(E)-(2,4,5-Trimethoxybenzylidene)amino]-1,5-dimethyl-2-phenyl-1Hpyrazol-3(2H)-one Hoong-Kun Fun,a*‡ Madhukar Hemamalini,a Abdullah M. Asirib§ and Salman A. Khanb a X-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and bDepartment of Chemistry, Faculty of Science, King Abdu Aziz University, Jeddah, Saudi Arabia Correspondence e-mail: hkfun@usm.my Received 1 June 2010; accepted 7 June 2010 Key indicators: single-crystal X-ray study; T = 100 K; mean (C–C) = 0.001 Å; R factor = 0.040; wR factor = 0.123; data-to-parameter ratio = 16.3. V = 1930.72 (17) Å3 Z=4 Mo K radiation  = 0.09 mm1 T = 100 K 0.67  0.27  0.15 mm C21H23N3O4 Mr = 381.42 Monoclinic, P21 =c a = 21.0128 (10) Å b = 7.4242 (4) Å c = 12.5194 (6) Å = 98.675 (1) Data collection Bruker APEXII DUO CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2009) Tmin = 0.941, Tmax = 0.987 23600 measured reflections 5614 independent reflections 4779 reflections with I > 2(I) Rint = 0.031 Refinement R[F 2 > 2(F 2)] = 0.040 wR(F 2) = 0.123 S = 1.04 5614 reflections 345 parameters H atoms treated by a mixture of independent and constrained refinement
max = 0.48 e Å3
min = 0.23 e Å3 Table 1 The title compound, C21H23N3O4, adopts an E configuration about the central C N double bond and the pyrazolone ring is almost planar, with a maximum deviation of 0.042 (1) Å. The central pyrazolone ring makes dihedral angles of 51.96 (5) and 3.82 (5) with the attached phenyl and the trimethoxysubstituted benzene rings, respectively. The dihedral angle between the phenyl ring and the trimethoxy-substituted benzene ring is 50.19 (5) and an intramolecular C—H  O hydrogen bond generates an S(6) ring motif. The crystal structure is stabilized by intermolecular C—H  O and C— H  N hydrogen bonds. Related literature For background to the applications of Schiff bases, see: Vukovic et al. (2010); Ramesh & Maheswaran (2003); Dongfang et al. (2008); Sastry & Rao (1988); Kamel et al. (2010). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). Hydrogen-bond geometry (Å,  ). D—H  A D—H H  A D  A C10—H10A  O1 C4—H4A  O1i C20—H20A  N3ii C20—H20C  O2iii C20—H20C  O3iii 0.954 0.969 0.996 0.977 0.977 2.331 2.541 2.577 2.509 2.495 3.0112 3.2628 3.5383 3.4470 3.2779 (13) (13) (14) (14) (14) (13) (13) (14) (14) (15) D—H  A (11) (12) (13) (13) (13) 127.8 131.4 162.1 160.8 137.0 (10) (10) (12) (12) (11) Symmetry codes: (i) x; y  12; z þ 12; (ii) x; y þ 12; z  12; (iii) x; y þ 1; z. Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009). HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship. AMA and SAK thank the Chemistry Department, King Abdul Aziz University, Jeddah, Saudi Arabia, for providing research facilities. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5480). References ‡ Thomson Reuters ResearcherID: A-3561-2009. § On secondment to: The Center of Excellence for Advanced Materials Research, King Abdu Aziz University, Jeddah 21589, Saudi Arabia. o1656 Fun et al. Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. Dongfang, X. U., Shuzhi, M. A., Guangying, D. U., Qizhuang, H. E. & Dazhi, S. (2008). J. Rare Earths, 26, 643–647. Kamel, M. M., Ali, H. I., Anwar, M. M., Mohamed, N. A. & Soliman, A. M. (2010). Eur. J. Med. Chem. 45, 572–580. doi:10.1107/S1600536810021586 Acta Cryst. (2010). E66, o1656–o1657 organic compounds Ramesh, R. & Maheswaran, S. (2003). J. Inorg. Biochem., 96, 457–462. Sastry, C. S. P. & Rao, A. R. M. (1988). J. Pharmacol. Methods, 26, 643–647. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Acta Cryst. (2010). E66, o1656–o1657 Spek, A. L. (2009). Acta Cryst. D65, 148–155. Vukovic, N., Sukdolak, S., Solujic, S. & Niciforovic, N. (2010). Food Chem. 120, 1011–1018. Fun et al.  C21H23N3O4 o1657 supplementary materials supplementary materials Acta Cryst. (2010). E66, o1656-o1657 [ doi:10.1107/S1600536810021586 ] 4-[(E)-(2,4,5-Trimethoxybenzylidene)amino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one H.-K. Fun, M. Hemamalini, A. M. Asiri and S. A. Khan Comment Compounds with the structure of AC═NB are known as Schiff base, which can be synthesized from the condensation of amino and active carbonyl groups. Schiff base compounds have shown different therapeutic properties such as antibacterial (Vukovic et al., 2010), antifungal (Ramesh & Maheswaran, 2003), antitumor (Dongfang et al., 2008), anti-inflammatory (Sastry & Rao, 1988) and anticancer activities (Kamel et al., 2010). Due to their importance, the crystal structure determination of the title compound was carried out and the results are presented here. In the title compound (Fig. 1), the pyrazolone ring (N1/N2/C7–C9) is almost planar, with maximum deviation of 0.042 (1) Å for atom N2. The central pyrazolone (N1/N2/C7–C9) ring makes dihedral angles of 51.96 (5)° and 3.82 (5)° with the attached phenyl ring (C1–C6) and the trimethoxy substituted phenyl ring (C11–C16), respectively. The dihedral angle between the phenyl ring(C1–C6) and the trimethoxy substituted phenyl ring (C11–C16) is 50.19 (5)°. The three methoxy groups are coplanar with the benzene ring [torsion angles C19-O2-C13-C12 = 5.04 (16)°, C20-O3-C14-C15 = -0.36 (14)° and C21-O4-C16-C15 = -1.66 (13)°]. In the crystal packing (Fig. 2), the intramolecular C10—H10A···O1 hydrogen bonding generates an S(6) ring motif (Bernstein et al., 1995). The crystal sturcture is futher stabilized by weak intermolecular C4—H4A···O1, C20—H20C···O2, C20—H20C···O3 and C20—H20A···N3 (Table 1) hydrogen bonds. Experimental A mixture of 4-aminophenazone (0.50 g, 0.0033 mol) and 2,4,5-tri-methoxy- benzaldehyde (0.65 g, 0.0033 mol) in methanol (15 ml) was refluxed for 5 h with stirring to give a light yellow precipitate. It was then filtered and washed with methanol to give the pure Schiff base and yellow blocks of (I) were recrystallized from methanol. Yield: 48.18%; Mp. 381°C; IR (KBr) νmax cm-1: 2937 (C–H), 1644 (C═C), 1609(C═O), 1591 (C═N), 1122 (N–N). 1H-NMR (CDCl3) d: 10.02 ((s, 1H, CH olefinic), 7.67 (s, H3, CHaromatic), 6.49 (s, H6, CHaromatic), 7.47–7.26 (m, 5H, CHaromatic), 3.93 (s, OCH3), 3.93 (s, OCH3), 3.84 (s, OCH3), 3.11(s, N-CH3), 2.48 (s,-CH3). Refinement All the H atoms were located from a difference Fourier map and refined freely [C—H = 0.945 (14)–1.008 (14) Å]. sup-1 supplementary materials Figures Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids. The intramolecular hydrogen bond is shown as a dashed line. Fig. 2. The crystal packing of (I) showing hydrogen-bonded (dashed lines) networks. H atoms not involved in the hydrogen bond interactions are omitted for clarity. 4-[(E)-(2,4,5-Trimethoxybenzylidene)amino]-1,5-dimethyl-2-phenyl- 1H-pyrazol-3(2H)-one Crystal data C21H23N3O4 F(000) = 808 Mr = 381.42 Dx = 1.312 Mg m−3 Monoclinic, P21/c Mo Kα radiation, λ = 0.71073 Å Hall symbol: -P 2ybc a = 21.0128 (10) Å Cell parameters from 8559 reflections θ = 2.9–34.8° b = 7.4242 (4) Å µ = 0.09 mm−1 T = 100 K Blcok, yellow c = 12.5194 (6) Å β = 98.675 (1)° V = 1930.72 (17) Å3 Z=4 0.67 × 0.27 × 0.15 mm Data collection Bruker APEXII DUO CCD diffractometer Radiation source: fine-focus sealed tube 5614 independent reflections graphite 4779 reflections with I > 2σ(I) Rint = 0.031 φ and ω scans θmax = 30.0°, θmin = 1.0° Absorption correction: multi-scan (SADABS; Bruker, 2009) Tmin = 0.941, Tmax = 0.987 23600 measured reflections h = −29→29 k = −10→10 l = −17→17 Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.040 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 H atoms treated by a mixture of independent and constrained refinement wR(F2) = 0.123 w = 1/[σ2(Fo2) + (0.0771P)2 + 0.3259P] S = 1.04 where P = (Fo2 + 2Fc2)/3 5614 reflections (Δ/σ)max < 0.001 345 parameters Δρmax = 0.48 e Å−3 0 restraints Δρmin = −0.22 e Å−3 Special details Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K. Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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) O1 O2 O3 O4 N1 N2 N3 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 x y z Uiso*/Ueq 0.36912 (3) 0.02634 (3) 0.06645 (3) 0.27842 (3) 0.35715 (4) 0.30506 (4) 0.22306 (4) 0.47358 (5) 0.52970 (5) 0.52678 (5) 0.46740 (5) 0.41087 (5) 0.41448 (4) 0.25240 (4) 0.26770 (4) 0.33566 (4) 0.24207 (4) 0.19674 (4) 0.13242 (4) 0.08971 (4) 0.11121 (4) 0.17427 (4) 0.21674 (4) −0.05337 (10) 0.14809 (11) 0.44390 (11) 0.35928 (10) −0.34299 (11) −0.45837 (11) −0.11616 (11) −0.34082 (14) −0.35703 (15) −0.39395 (14) −0.41126 (14) −0.39230 (14) −0.35847 (13) −0.38702 (13) −0.22283 (13) −0.18791 (13) 0.03035 (13) 0.14168 (13) 0.08699 (14) 0.18970 (14) 0.35193 (14) 0.40938 (14) 0.30561 (13) 0.48796 (5) 0.14482 (6) 0.06868 (6) 0.27787 (6) 0.55298 (6) 0.56225 (6) 0.39236 (6) 0.59345 (8) 0.66770 (9) 0.77564 (8) 0.81062 (8) 0.73777 (7) 0.62948 (7) 0.49748 (7) 0.45728 (7) 0.49592 (7) 0.35116 (7) 0.27961 (7) 0.24831 (7) 0.17891 (8) 0.13731 (7) 0.16780 (7) 0.24024 (7) 0.01654 (15) 0.02325 (17) 0.02140 (17) 0.01722 (15) 0.01452 (16) 0.01459 (16) 0.01426 (16) 0.01773 (19) 0.0216 (2) 0.0205 (2) 0.01797 (19) 0.01641 (18) 0.01427 (18) 0.01383 (18) 0.01270 (17) 0.01293 (17) 0.01384 (17) 0.01385 (18) 0.01533 (18) 0.01645 (18) 0.01642 (19) 0.01589 (18) 0.01424 (17) sup-3 supplementary materials C17 C18 C19 C20 C21 H1A H2A H3A H4A H5A H10A H12A H15A H17A H17B H17C H18A H18B H18C H19A H19B H19C H20A H20B H20C H21A H21B H21C 0.32012 (5) 0.18985 (5) 0.00170 (5) 0.08640 (5) 0.29988 (5) 0.4749 (7) 0.5716 (7) 0.5674 (7) 0.4646 (6) 0.3683 (7) 0.2859 (6) 0.1206 (7) 0.1878 (7) 0.2798 (7) 0.3365 (7) 0.3507 (7) 0.1555 (7) 0.1925 (8) 0.1744 (7) −0.0437 (8) 0.0243 (8) 0.0082 (8) 0.1208 (7) 0.1018 (7) 0.0475 (7) 0.3011 (7) 0.3418 (7) 0.2732 (7) −0.65126 (14) −0.48412 (14) −0.00727 (18) 0.61077 (16) 0.52608 (14) −0.319 (2) −0.342 (2) −0.413 (2) −0.4380 (19) −0.407 (2) 0.0685 (18) −0.025 (2) 0.520 (2) −0.723 (2) −0.684 (2) −0.673 (2) −0.411 (2) −0.601 (2) −0.511 (2) −0.018 (2) −0.119 (2) 0.003 (3) 0.586 (2) 0.696 (2) 0.656 (2) 0.515 (2) 0.545 (2) 0.626 (2) 0.55935 (8) 0.47905 (8) 0.19178 (11) 0.02644 (9) 0.23842 (8) 0.5178 (11) 0.6413 (11) 0.8265 (12) 0.8855 (11) 0.7601 (11) 0.3651 (10) 0.2767 (11) 0.1400 (11) 0.5642 (11) 0.4918 (12) 0.6234 (12) 0.4352 (12) 0.4416 (12) 0.5471 (12) 0.1586 (13) 0.1720 (13) 0.2715 (14) −0.0182 (11) 0.0873 (12) −0.0181 (11) 0.1612 (12) 0.2761 (11) 0.2555 (11) 0.0194 (2) 0.01728 (19) 0.0293 (3) 0.0223 (2) 0.01750 (19) 0.025 (3)* 0.027 (4)* 0.028 (4)* 0.020 (3)* 0.024 (3)* 0.016 (3)* 0.022 (3)* 0.020 (3)* 0.024 (3)* 0.027 (4)* 0.030 (4)* 0.030 (4)* 0.033 (4)* 0.032 (4)* 0.037 (4)* 0.038 (4)* 0.042 (4)* 0.024 (3)* 0.032 (4)* 0.026 (4)* 0.023 (3)* 0.025 (4)* 0.024 (3)* Atomic displacement parameters (Å2) O1 O2 O3 O4 N1 N2 N3 C1 C2 C3 C4 C5 C6 C7 C8 C9 sup-4 U11 0.0170 (3) 0.0125 (3) 0.0138 (3) 0.0142 (3) 0.0139 (3) 0.0149 (3) 0.0153 (3) 0.0173 (4) 0.0151 (4) 0.0190 (4) 0.0218 (4) 0.0173 (4) 0.0148 (4) 0.0153 (4) 0.0140 (4) 0.0149 (4) U22 0.0133 (3) 0.0240 (4) 0.0224 (4) 0.0164 (3) 0.0120 (4) 0.0111 (4) 0.0137 (4) 0.0173 (5) 0.0213 (5) 0.0159 (4) 0.0150 (4) 0.0151 (4) 0.0110 (4) 0.0132 (4) 0.0119 (4) 0.0119 (4) U33 0.0192 (3) 0.0322 (4) 0.0272 (4) 0.0202 (3) 0.0170 (3) 0.0172 (3) 0.0137 (3) 0.0189 (4) 0.0281 (5) 0.0243 (5) 0.0158 (4) 0.0166 (4) 0.0163 (4) 0.0130 (4) 0.0122 (3) 0.0122 (3) U12 −0.0013 (3) −0.0015 (3) 0.0030 (3) −0.0017 (3) −0.0004 (3) −0.0007 (3) 0.0033 (3) 0.0029 (4) 0.0019 (4) 0.0007 (4) 0.0018 (4) 0.0019 (3) 0.0020 (3) 0.0014 (3) 0.0020 (3) 0.0023 (3) U13 0.0023 (2) 0.0001 (3) 0.0007 (3) −0.0002 (2) 0.0000 (3) 0.0004 (3) 0.0020 (3) 0.0038 (3) 0.0027 (4) −0.0041 (3) −0.0013 (3) 0.0020 (3) −0.0001 (3) 0.0023 (3) 0.0020 (3) 0.0026 (3) U23 0.0031 (3) 0.0114 (3) 0.0132 (3) 0.0061 (3) 0.0033 (3) 0.0030 (3) 0.0020 (3) 0.0031 (4) 0.0041 (4) 0.0008 (4) −0.0005 (3) −0.0005 (3) 0.0004 (3) 0.0005 (3) 0.0007 (3) 0.0010 (3) supplementary materials C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 0.0145 (4) 0.0146 (4) 0.0149 (4) 0.0122 (4) 0.0144 (4) 0.0155 (4) 0.0131 (4) 0.0216 (4) 0.0166 (4) 0.0165 (4) 0.0179 (4) 0.0194 (4) 0.0131 (4) 0.0132 (4) 0.0143 (4) 0.0176 (4) 0.0175 (4) 0.0154 (4) 0.0150 (4) 0.0111 (4) 0.0155 (4) 0.0268 (6) 0.0221 (5) 0.0139 (4) 0.0138 (4) 0.0140 (4) 0.0171 (4) 0.0197 (4) 0.0176 (4) 0.0171 (4) 0.0147 (4) 0.0244 (5) 0.0196 (4) 0.0443 (7) 0.0268 (5) 0.0194 (4) 0.0025 (3) 0.0023 (3) 0.0020 (3) 0.0017 (3) 0.0043 (3) 0.0023 (3) 0.0013 (3) 0.0012 (4) −0.0020 (3) −0.0026 (4) 0.0031 (4) −0.0017 (4) 0.0018 (3) 0.0027 (3) 0.0037 (3) 0.0031 (3) 0.0030 (3) 0.0035 (3) 0.0024 (3) −0.0003 (4) 0.0025 (3) 0.0037 (4) 0.0028 (4) 0.0036 (3) 0.0012 (3) 0.0024 (3) 0.0038 (3) 0.0039 (4) 0.0056 (3) 0.0051 (3) 0.0019 (3) 0.0034 (4) 0.0013 (3) 0.0137 (5) 0.0124 (4) 0.0029 (3) Geometric parameters (Å, °) O1—C9 O2—C13 O2—C19 O3—C14 O3—C20 O4—C16 O4—C21 N1—C9 N1—N2 N1—C6 N2—C7 N2—C17 N3—C10 N3—C8 C1—C6 C1—C2 C1—H1A C2—C3 C2—H2A C3—C4 C3—H3A C4—C5 C4—H4A C5—C6 C5—H5A C7—C8 C7—C18 1.2341 (12) 1.3709 (11) 1.4268 (14) 1.3583 (11) 1.4342 (13) 1.3698 (11) 1.4311 (12) 1.3937 (12) 1.4084 (11) 1.4261 (11) 1.3754 (11) 1.4683 (13) 1.2927 (12) 1.3918 (11) 1.3898 (13) 1.3923 (13) 0.965 (14) 1.3893 (15) 0.992 (15) 1.3892 (15) 0.995 (15) 1.3913 (13) 0.969 (13) 1.3921 (13) 0.984 (14) 1.3753 (13) 1.4863 (13) C8—C9 C10—C11 C10—H10A C11—C16 C11—C12 C12—C13 C12—H12A C13—C14 C14—C15 C15—C16 C15—H15A C17—H17A C17—H17B C17—H17C C18—H18A C18—H18B C18—H18C C19—H19A C19—H19B C19—H19C C20—H20A C20—H20B C20—H20C C21—H21A C21—H21B C21—H21C 1.4603 (12) 1.4613 (12) 0.954 (13) 1.4011 (13) 1.4090 (13) 1.3808 (13) 0.949 (15) 1.4130 (14) 1.3897 (13) 1.4029 (12) 0.953 (15) 1.008 (14) 0.990 (14) 0.963 (15) 1.000 (16) 0.990 (17) 0.977 (15) 0.986 (17) 1.006 (17) 0.990 (18) 0.996 (14) 1.007 (16) 0.976 (15) 0.974 (14) 0.945 (14) 0.972 (15) C13—O2—C19 C14—O3—C20 C16—O4—C21 C9—N1—N2 C9—N1—C6 N2—N1—C6 C7—N2—N1 116.72 (8) 117.04 (8) 117.65 (7) 110.43 (7) 125.90 (8) 118.94 (7) 106.45 (7) C13—C12—H12A C11—C12—H12A O2—C13—C12 O2—C13—C14 C12—C13—C14 O3—C14—C15 O3—C14—C13 122.3 (8) 116.3 (8) 125.46 (9) 115.26 (8) 119.28 (8) 124.05 (9) 115.62 (8) sup-5 supplementary materials C7—N2—C17 N1—N2—C17 C10—N3—C8 C6—C1—C2 C6—C1—H1A C2—C1—H1A C3—C2—C1 C3—C2—H2A C1—C2—H2A C4—C3—C2 C4—C3—H3A C2—C3—H3A C3—C4—C5 C3—C4—H4A C5—C4—H4A C4—C5—C6 C4—C5—H5A C6—C5—H5A C1—C6—C5 C1—C6—N1 C5—C6—N1 C8—C7—N2 C8—C7—C18 N2—C7—C18 C7—C8—N3 C7—C8—C9 N3—C8—C9 O1—C9—N1 O1—C9—C8 N1—C9—C8 N3—C10—C11 N3—C10—H10A C11—C10—H10A C16—C11—C12 C16—C11—C10 C12—C11—C10 C13—C12—C11 121.21 (8) 114.72 (8) 119.36 (8) 118.90 (9) 119.6 (8) 121.5 (8) 120.62 (9) 121.2 (8) 118.2 (8) 119.89 (9) 120.6 (9) 119.4 (9) 120.18 (9) 120.8 (8) 119.0 (8) 119.34 (9) 121.7 (8) 118.9 (8) 121.05 (8) 118.69 (8) 120.26 (8) 110.21 (8) 128.54 (8) 121.25 (8) 122.95 (8) 107.87 (8) 129.17 (8) 124.44 (8) 131.11 (8) 104.37 (8) 120.57 (8) 121.7 (8) 117.8 (8) 118.58 (8) 120.31 (8) 121.11 (8) 121.40 (9) C15—C14—C13 C14—C15—C16 C14—C15—H15A C16—C15—H15A O4—C16—C11 O4—C16—C15 C11—C16—C15 N2—C17—H17A N2—C17—H17B H17A—C17—H17B N2—C17—H17C H17A—C17—H17C H17B—C17—H17C C7—C18—H18A C7—C18—H18B H18A—C18—H18B C7—C18—H18C H18A—C18—H18C H18B—C18—H18C O2—C19—H19A O2—C19—H19B H19A—C19—H19B O2—C19—H19C H19A—C19—H19C H19B—C19—H19C O3—C20—H20A O3—C20—H20B H20A—C20—H20B O3—C20—H20C H20A—C20—H20C H20B—C20—H20C O4—C21—H21A O4—C21—H21B H21A—C21—H21B O4—C21—H21C H21A—C21—H21C H21B—C21—H21C 120.33 (8) 119.75 (9) 119.3 (8) 120.9 (8) 116.75 (8) 122.63 (9) 120.61 (8) 109.0 (8) 111.4 (9) 108.9 (12) 105.3 (9) 108.8 (12) 113.3 (12) 111.7 (9) 112.7 (9) 107.7 (13) 111.5 (9) 106.4 (12) 106.5 (13) 106.4 (10) 110.6 (9) 106.9 (14) 110.6 (11) 114.1 (14) 108.1 (14) 109.0 (9) 110.2 (9) 111.3 (12) 104.0 (9) 111.0 (11) 111.1 (12) 109.1 (9) 105.8 (9) 110.2 (12) 111.1 (8) 112.6 (12) 107.8 (12) C9—N1—N2—C7 C6—N1—N2—C7 C9—N1—N2—C17 C6—N1—N2—C17 C6—C1—C2—C3 C1—C2—C3—C4 C2—C3—C4—C5 C3—C4—C5—C6 C2—C1—C6—C5 C2—C1—C6—N1 C4—C5—C6—C1 C4—C5—C6—N1 8.54 (10) 165.59 (8) 145.49 (8) −57.45 (11) 1.32 (16) −1.34 (17) 0.21 (16) 0.91 (16) −0.17 (15) −179.57 (9) −0.93 (15) 178.45 (9) C7—C8—C9—O1 N3—C8—C9—O1 C7—C8—C9—N1 N3—C8—C9—N1 C8—N3—C10—C11 N3—C10—C11—C16 N3—C10—C11—C12 C16—C11—C12—C13 C10—C11—C12—C13 C19—O2—C13—C12 C19—O2—C13—C14 C11—C12—C13—O2 −173.56 (9) 5.87 (16) 3.25 (10) −177.33 (9) 177.82 (8) 176.26 (8) −4.03 (14) 1.10 (14) −178.61 (9) 5.04 (16) −175.23 (10) −179.44 (9) sup-6 supplementary materials C9—N1—C6—C1 N2—N1—C6—C1 C9—N1—C6—C5 N2—N1—C6—C5 N1—N2—C7—C8 C17—N2—C7—C8 N1—N2—C7—C18 C17—N2—C7—C18 N2—C7—C8—N3 C18—C7—C8—N3 N2—C7—C8—C9 C18—C7—C8—C9 C10—N3—C8—C7 C10—N3—C8—C9 N2—N1—C9—O1 C6—N1—C9—O1 N2—N1—C9—C8 C6—N1—C9—C8 −65.96 (13) 140.85 (9) 114.64 (11) −38.55 (13) −6.30 (10) −139.83 (9) 173.92 (8) 40.39 (13) −177.54 (8) 2.22 (15) 1.93 (10) −178.31 (9) −174.99 (8) 5.66 (14) 169.88 (8) 14.78 (14) −7.20 (9) −162.30 (8) C11—C12—C13—C14 C20—O3—C14—C15 C20—O3—C14—C13 O2—C13—C14—O3 C12—C13—C14—O3 O2—C13—C14—C15 C12—C13—C14—C15 O3—C14—C15—C16 C13—C14—C15—C16 C21—O4—C16—C11 C21—O4—C16—C15 C12—C11—C16—O4 C10—C11—C16—O4 C12—C11—C16—C15 C10—C11—C16—C15 C14—C15—C16—O4 C14—C15—C16—C11 0.83 (15) −0.36 (14) 178.96 (9) −0.49 (13) 179.26 (9) 178.86 (9) −1.40 (15) 179.28 (9) 0.00 (15) 179.81 (8) −1.66 (13) 176.04 (8) −4.24 (13) −2.52 (14) 177.20 (8) −176.49 (9) 1.98 (14) Hydrogen-bond geometry (Å, °) D—H···A C10—H10A···O1 D—H 0.954 (13) H···A 2.331 (13) D···A 3.0112 (11) D—H···A 127.8 (10) C4—H4A···O1i 0.969 (13) 2.541 (13) 3.2628 (12) 131.4 (10) C20—H20A···N3ii 0.996 (14) 2.577 (14) 3.5383 (13) 162.1 (12) C20—H20C···O2iii 0.977 (14) 2.509 (14) 3.4470 (13) 160.8 (12) 0.977 (14) 2.495 (15) C20—H20C···O3iii Symmetry codes: (i) x, −y−1/2, z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x, −y+1, −z. 3.2779 (13) 137.0 (11) sup-7 supplementary materials Fig. 1 sup-8 supplementary materials Fig. 2 sup-9