(1RS,4RS,5RS)-Methyl 2-(3,5-dinitrobenzoyl)-2-oxa-3-azabicyclo[3.3.0]oct-7-ene-4-carboxylate
Abstract
In organic synthesis, the usual techniques as NMR, mass or infra-red spectrometry and elemental analysis are often not enough for the unequivocally determination of a structure of a compound. When it is possible to crystallize desired compound, the X-ray crystallography is the ultimate analysis. 3,5-dinitrobenzoylation of 2-oxa-3-azabicyclo[3.3.0]oct-7-ene-4- carboxylate leaded to title compound (I) that was unambigously analysed by X-ray analysis. The two independent molecules of the title compound (I) are coupled by π···π interactions of the 3,5-dinitrobenzoyl rings (Fig. 1) [Cg1-Cg2iv = 4.2295 Å, symmetry code: (iv) 1 + x, y, z]. It is also possible to verify the existence of the three stereogenic centres of the same chirality in both molecules of the asymmetric unit. As the space group is centrosymmetric, a racemate is present in a crystal. No other stereoisomers of methyl 2-oxa-3-azabicyclo[3.3.0]oct-7-ene-4-carboxylate are obtained from the reported synthetic methodology (Sousa et al. 2008). In the crystal structure, each pair of the molecules are linked by π··· π contacts between the 3,5-dinitrobenzoyl rings along [100] direction (Fig. 2) (Cg1-Cg2iii = 4.4862 Å, Cg2-Cg1iii = 4.4862 Å; symmetry code: (iii) x, y, z). Intermolecular interactions between carbonyl and nitro groups (distance C···O ≈ 3.0 Å), between nitro groups (distance N···O ≈ 3.0 Å) and C—H···O intermolecular hydrogen bonds (Table 1) generate an assembly by packing these chains along [010] direction (Fig. 3). Table 2 lists the interactions between aromatic rings (resulting in a π···π stacking assembly). The carbonyl and nitro groups are very electronegative; as a result, the electronic density of the 3,5-dinitrobenzoyl rings is delocalized from the centre of π-system towards the electronegative O atoms. This delocalization origins from electrostatic intermolecular interactions between the oxygen atoms and the centre of the π-system (Table 3). This analysis suggest that the most important intermolecular interactions in compound (I) are due to the 3,5-dinitrobenzoyl ring (including the nitro and carbonyl groups), which seems to be the main reason why compound (I) is a solid
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(1RS,4RS,5RS)-Methyl 2-(3,5-dinitro- benzoyl)-2-oxa-3-azabicyclo[3.3.0]oct-7- ene-4-carboxylate Carlos A. D. Sousa, a * Jose ´E. Rodrı ´guez-Borges, a M. Luı ´sa C. Vale a and Xerardo Garcia-Mera b a Centro de Investigac¸a ˜o em Quı ´mica, Departamento de Quı ´mica, Faculdade de Cie ˆncias, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal, and b Departamento de Quı ´mica Orga ´nica, Facultade de Farmacia, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain Correspondence e-mail: [email protected] Received 14 February 2009; accepted 2 April 2009 Key indicators: single-crystal X-ray study; T= 100 K; mean (C–C) = 0.003 A ˚; Rfactor = 0.047; wR factor = 0.124; data-to-parameter ratio = 12.8. The title compound, C 15 H 13 N 3 O 8 , comprises two crystallographically independent molecules in the asymmetric unit. In the crystal, intermolecular C—HO hydrogen bonds link the molecules and short C Ocontacts are seen. Related literature For the preparation of the precursor of the title compound, see: Sousa et al. (2008). For examples of the use of the 3,5dinitrobenzoylation technique for the assignment of structures by X-ray, see: Caaman ˜oet al. (2000); Ferna ´ndez et al. (2001). Experimental Crystal data C 15 H 13 N 3 O 8 M r = 363.28 Triclinic, P1 a= 8.7157 (3) A ˚ b= 10.8269 (3) A ˚ c= 17.0677 (5) A ˚ = 79.881 (1) = 77.773 (1) = 78.281 (1) V= 1526.35 (8) A ˚ 3 Z=4 Mo Kradiation = 0.13 mm 1 T= 100 K 0.26 0.23 0.1 mm Data collection Bruker ApexII CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2007) T min = 0.913, T max = 0.99 28142 measured reflections 6012 independent reflections 4564 reflections with I>2(I) R int = 0.039 Refinement R[F 2 >2(F 2 )] = 0.047 wR(F 2 ) = 0.124 S= 1.05 6012 reflections 471 parameters H-atom parameters constrained max = 0.27 e A ˚ 3 min =0.24 e A ˚ 3 Table 1 Hydrogen-bond geometry (A ˚,). D—HAD—H HADAD—HA C17—H17O11 i 0.98 2.40 3.064 (3) 124 C47—H47O41 ii 0.98 2.45 3.083 (3) 122 Symmetry codes: (i) xþ2;y;zþ1; (ii) xþ1;yþ1;zþ1. Table 2 Geometric parameters of Y—XCg contacts (A ˚,). Y—XCg XCg Y—XCg YCg C13—O14Cg2 3.2009 (18) 106.47 (13) 3.736 (3) C43—O44Cg1 3.1434 (18) 104.52 (13) 3.649 (3) Cg1 and Cg2 are the centroids of the rings defined by C1, C2, C3, C7, C8, C12 and C31, C32, C33, C37, C38, C42, respectively. Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999). This work was supported by Centro de Investigac¸a ˜oem Quı ´mica of the University of Porto. The X-ray data were collected at the Unidade de Raios X, RIAIDT, University of Santiago de Compostela. The authors thank Fundac¸a ˜o para a Cie ˆncia e Tecnologia (FCT) (POCTI/QUI/44471/2002) and Xunta de Galicia (07CSA008203-PR) for financial support. CADS thanks the FCT for a grant (No. SFRH/BD/31526/ 2006). Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: KP2206). References Altomare, A., Cascarano, C., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Burla, M. C., Polidori, G., Camalli, M. & Spagna, R. (1997). SIR97. University of Bari, Italy. Bruker (2007). APEX2,SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Caaman ˜o, O., Ferna ´ndez, F., Garcia-Mera, X. & Rodrı ´gues-Borges, J. E. (2000). Tetrahedron Lett. 41, 4123–4125. Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. organic compounds o992 Sousa et al. doi:10.1107/S160053680901246X Acta Cryst. (2009). E65, o992–o993 Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368
Ferna ´ndez, F., Garcia-Mera, X. & Rodrı ´gues-Borges, J. E. (2001). Tetrahedron Asymmetry,12, 365–368. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Sousa, C. A. D., Vale, M. L. C., Rodrı ´gues-Borges, J. E. & Garcı ´a-Mera, X. (2008). Tetrahedron Lett. 49, 5777–5781. organic compounds Acta Cryst. (2009). E65, o992–o993 Sousa et al. C 15 H 13 N 3 O 8 o993
supporting information sup-1 Acta Cryst. (2009). E65, o992–o993 supporting information Acta Cryst. (2009). E65, o992–o993 [doi:10.1107/S160053680901246X] (1RS,4RS,5RS)-Methyl 2-(3,5-dinitrobenzoyl)-2-oxa-3-azabicyclo[3.3.0]oct-7- ene-4-carboxylate Carlos A. D. Sousa, José E. Rodríguez-Borges, M. Luísa C. Vale and Xerardo Garcia-Mera S1. Comment In organic synthesis, the usual techniques as NMR, mass or infra-red spectrometry and elemental analysis are often not enough for the unequivocally determination of a structure of a compound. When it is possible to crystallize desired compound, the X-ray crystallography is the ultimate analysis. 3,5-dinitrobenzoylation of 2-oxa-3-azabicyclo[3.3.0]oct-7- ene-4- carboxylate leaded to title compound (I) that was unambigously analysed by X-ray analysis. The two independent molecules of the title compound (I) are coupled by π···π interactions of the 3,5-dinitrobenzoyl rings (Fig. 1) [Cg1-Cg2iv = 4.2295 Å, symmetry code: (iv) 1 + x, y, z]. It is also possible to verify the existence of the three stereogenic centres of the same chirality in both molecules of the asymmetric unit. As the space group is centrosymmetric, a racemate is present in a crystal. No other stereoisomers of methyl 2-oxa-3-azabicyclo[3.3.0]oct-7- ene-4-carboxylate are obtained from the reported synthetic methodology (Sousa et al. 2008). In the crystal structure, each pair of the molecules are linked by π··· π contacts between the 3,5-dinitrobenzoyl rings along [100] direction (Fig. 2) (Cg1-Cg2iii = 4.4862 Å, Cg2-Cg1iii = 4.4862 Å; symmetry code: (iii) x, y, z). Intermolecular interactions between carbonyl and nitro groups (distance C···O ≈ 3.0 Å), between nitro groups (distance N···O ≈ 3.0 Å) and C—H···O intermolecular hydrogen bonds (Table 1) generate an assembly by packing these chains along [010] direction (Fig. 3). Table 2 lists the interactions between aromatic rings (resulting in a π···π stacking assembly). The carbonyl and nitro groups are very electronegative; as a result, the electronic density of the 3,5-dinitrobenzoyl rings is delocalized from the centre of π-system towards the electronegative O atoms. This delocalization origins from electrostatic intermolecular interactions between the oxygen atoms and the centre of the π-system (Table 3). This analysis suggest that the most important intermolecular interactions in compound (I) are due to the 3,5-dinitro- benzoyl ring (including the nitro and carbonyl groups), which seems to be the main reason why compound (I) is a solid. S2. Experimental The title compound was synthesized from 2-oxa-3-azabicyclo[3.3.0]oct-7-ene-4-carboxylate as reported in literature (Sousa et al. 2008). Crystals were obtained from a slow evaporation of a dichlorometane/methanol/hexane solution of (I). S3. Refinement All H atoms were found in a difference Fourier map and placed in geometrically idealized and constrained to ride on their parent atoms [C—H = 0.93–0.98 Å and Uiso(H) = 1.2 (1.5 for methyl groups) × Ueq(C)].
supporting information sup-2 Acta Cryst. (2009). E65, o992–o993 Figure 1 A view of a pair of independent molecules of (I) connected by π···π interactions (dashed lines) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as spheres of arbitrary radius.
supporting information sup-3 Acta Cryst. (2009). E65, o992–o993 Figure 2 Part of the crystal structure of (I) viewed along the b axis. Dashed lines show Cg1-Cg2 (π···π) interactions along [100] direction and the respective distances are given in Å. H atoms are omitted for clarity. Figure 3 Part of the crystal structure of (I) viewed along the a axis. Dashed lines show CO···NO2, NO2···NO2 and C—H···O interactions along [010] direction. H atoms not involved in hydrogen bonding have been omitted for clarity.
supporting information sup-4 Acta Cryst. (2009). E65, o992–o993 (1RS,4RS,5RS)-Methyl 2-(3,5-dinitrobenzoyl)-2-oxa-3- azabicyclo[3.3.0]oct-7-ene-4-carboxylate Crystal data C15H13N3O8 Mr = 363.28 Triclinic, P1 Hall symbol: -P 1 a = 8.7157 (3) Å b = 10.8269 (3) Å c = 17.0677 (5) Å α = 79.881 (1)° β = 77.773 (1)° γ = 78.281 (1)° V = 1526.35 (8) Å3 Z = 4 F(000) = 752 Dx = 1.581 Mg m−3 Mo Kα radiation, λ = 0.71069 Å Cell parameters from 6065 reflections θ = 2.4–26.0° µ = 0.13 mm−1 T = 100 K Prism, colourless 0.26 × 0.23 × 0.1 mm Data collection Bruker ApexII CCD area-detector diffractometer Radiation source: sealed tube Graphite monochromator phi and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2007) Tmin = 0.913, Tmax = 0.99 28142 measured reflections 6012 independent reflections 4564 reflections with I > 2σ(I) Rint = 0.039 θmax = 26.0°, θmin = 1.9° h = −10→10 k = −13→13 l = 0→21 Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.047 wR(F2) = 0.124 S = 1.05 6012 reflections 471 parameters 0 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/[σ2(Fo2) + (0.0478P)2 + 1.4085P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.27 e Å−3 Δρmin = −0.24 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 R-factors(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) xyzU iso*/Ueq C1 0.9942 (2) 0.18394 (19) 0.38593 (13) 0.0155 (4) C2 1.0752 (2) 0.2818 (2) 0.34588 (13) 0.0166 (4) H2 1.0992 0.2956 0.2896 0.02*
supporting information sup-5 Acta Cryst. (2009). E65, o992–o993 C3 1.1195 (2) 0.35814 (19) 0.39127 (13) 0.0160 (4) N4 1.2051 (2) 0.46174 (17) 0.34844 (11) 0.0195 (4) O5 1.2230 (2) 0.48129 (16) 0.27460 (10) 0.0313 (4) O6 1.25526 (19) 0.52204 (15) 0.38914 (10) 0.0246 (4) C7 1.0872 (2) 0.34329 (19) 0.47509 (13) 0.0159 (4) H7 1.1201 0.3946 0.5044 0.019* C8 1.0029 (2) 0.24721 (19) 0.51215 (13) 0.0152 (4) N9 0.9606 (2) 0.22901 (17) 0.60139 (11) 0.0187 (4) O10 1.0221 (2) 0.28525 (15) 0.63892 (10) 0.0267 (4) O11 0.8644 (2) 0.15906 (15) 0.63199 (10) 0.0269 (4) C12 0.9546 (2) 0.1685 (2) 0.47014 (13) 0.0165 (4) H12 0.8964 0.1059 0.4977 0.02* C13 0.9295 (3) 0.0975 (2) 0.34540 (13) 0.0176 (5) O14 0.81962 (18) 0.04407 (14) 0.38263 (9) 0.0207 (3) N15 0.9857 (2) 0.08830 (17) 0.26587 (11) 0.0189 (4) O16 1.13586 (18) 0.11886 (14) 0.22609 (9) 0.0213 (4) C17 1.2273 (3) −0.0039 (2) 0.20221 (14) 0.0206 (5) H17 1.278 −0.0563 0.2458 0.025* C18 1.3444 (3) 0.0181 (2) 0.12586 (14) 0.0243 (5) H18 1.4385 0.0484 0.1223 0.029* C19 1.2969 (3) −0.0111 (2) 0.06383 (14) 0.0259 (5) H19 1.3561 −0.0057 0.0116 0.031* C20 1.1382 (3) −0.0538 (2) 0.08611 (14) 0.0264 (5) H20A 1.1434 −0.1343 0.0673 0.032* H20B 1.0571 0.0093 0.0635 0.032* C21 1.1035 (3) −0.0680 (2) 0.17955 (13) 0.0200 (5) H21 1.1197 −0.1586 0.2016 0.024* C22 0.9406 (3) −0.0004 (2) 0.22286 (13) 0.0201 (5) H22 0.8892 −0.0635 0.2626 0.024* C23 0.8278 (3) 0.0653 (2) 0.16619 (14) 0.0240 (5) O24 0.7600 (2) 0.00814 (17) 0.13342 (10) 0.0308 (4) O25 0.8140 (2) 0.19225 (16) 0.15572 (10) 0.0307 (4) C26 0.7075 (4) 0.2615 (3) 0.10190 (17) 0.0400 (7) H26A 0.7476 0.2395 0.0484 0.06* H26B 0.7009 0.3514 0.1007 0.06* H26C 0.6034 0.2394 0.121 0.06* C31 0.6061 (2) 0.36166 (19) 0.38716 (13) 0.0163 (4) C32 0.5616 (2) 0.2795 (2) 0.34533 (13) 0.0176 (5) H32 0.5863 0.2881 0.2891 0.021* C33 0.4798 (2) 0.1845 (2) 0.38893 (13) 0.0173 (5) N34 0.4341 (2) 0.09760 (17) 0.34395 (12) 0.0205 (4) O35 0.4812 (2) 0.10687 (17) 0.27083 (10) 0.0318 (4) O36 0.35044 (19) 0.02069 (15) 0.38273 (10) 0.0253 (4) C37 0.4382 (2) 0.16728 (19) 0.47197 (13) 0.0175 (5) H37 0.3799 0.1049 0.4997 0.021* C38 0.4885 (2) 0.2484 (2) 0.51171 (13) 0.0164 (4) N39 0.4501 (2) 0.23228 (17) 0.60065 (11) 0.0196 (4) O40 0.3526 (2) 0.16400 (16) 0.63497 (10) 0.0290 (4)
supporting information sup-6 Acta Cryst. (2009). E65, o992–o993 O41 0.5182 (2) 0.28796 (15) 0.63533 (10) 0.0268 (4) C42 0.5721 (2) 0.3436 (2) 0.47166 (13) 0.0175 (5) H42 0.6055 0.3951 0.5007 0.021* C43 0.7027 (3) 0.4644 (2) 0.34872 (13) 0.0179 (5) O44 0.78205 (18) 0.50231 (14) 0.38786 (9) 0.0209 (3) N45 0.7092 (2) 0.50775 (18) 0.26884 (11) 0.0209 (4) O46 0.59327 (19) 0.49161 (14) 0.22645 (9) 0.0234 (4) C47 0.5203 (3) 0.6231 (2) 0.19852 (14) 0.0242 (5) H47 0.4338 0.6587 0.2395 0.029* C48 0.4685 (3) 0.6268 (2) 0.12065 (15) 0.0294 (6) H48 0.3777 0.5984 0.1157 0.035* C49 0.5688 (3) 0.6761 (3) 0.05900 (16) 0.0346 (6) H49 0.556 0.686 0.0054 0.042* C50 0.7046 (3) 0.7143 (3) 0.08449 (15) 0.0358 (6) H50A 0.7137 0.8021 0.0628 0.043* H50B 0.8045 0.6598 0.0666 0.043* C51 0.6601 (3) 0.6973 (2) 0.17758 (14) 0.0241 (5) H51 0.6251 0.7809 0.1962 0.029* C52 0.7859 (3) 0.6152 (2) 0.22667 (14) 0.0221 (5) H52 0.8012 0.664 0.2668 0.026* C53 0.9452 (3) 0.5754 (2) 0.17384 (14) 0.0241 (5) O54 1.0372 (2) 0.64757 (16) 0.14466 (11) 0.0317 (4) O55 0.9688 (2) 0.45359 (16) 0.16190 (10) 0.0292 (4) C56 1.1169 (3) 0.4105 (3) 0.10927 (16) 0.0362 (6) H56A 1.1234 0.4644 0.058 0.054* H56B 1.1202 0.3244 0.1012 0.054* H56C 1.2052 0.4142 0.1337 0.054* Atomic displacement parameters (Å2) U11 U22 U33 U12 U13 U23 C1 0.0128 (10) 0.0146 (10) 0.0202 (11) 0.0019 (8) −0.0055 (8) −0.0069 (8) C2 0.0151 (11) 0.0174 (11) 0.0166 (11) 0.0011 (8) −0.0038 (8) −0.0042 (8) C3 0.0127 (10) 0.0142 (10) 0.0211 (12) −0.0016 (8) −0.0034 (9) −0.0026 (8) N4 0.0183 (10) 0.0174 (9) 0.0239 (11) −0.0043 (8) −0.0045 (8) −0.0035 (8) O5 0.0433 (11) 0.0351 (10) 0.0194 (9) −0.0212 (8) −0.0033 (8) −0.0003 (7) O6 0.0266 (9) 0.0219 (8) 0.0310 (9) −0.0100 (7) −0.0095 (7) −0.0073 (7) C7 0.0122 (10) 0.0154 (10) 0.0217 (12) 0.0023 (8) −0.0071 (9) −0.0072 (9) C8 0.0121 (10) 0.0178 (11) 0.0154 (11) 0.0025 (8) −0.0043 (8) −0.0050 (8) N9 0.0192 (10) 0.0189 (9) 0.0183 (10) −0.0016 (8) −0.0046 (8) −0.0035 (8) O10 0.0353 (10) 0.0287 (9) 0.0213 (9) −0.0083 (8) −0.0118 (7) −0.0063 (7) O11 0.0319 (9) 0.0299 (9) 0.0204 (9) −0.0129 (8) −0.0024 (7) −0.0017 (7) C12 0.0124 (10) 0.0156 (10) 0.0215 (12) −0.0003 (8) −0.0035 (9) −0.0042 (9) C13 0.0181 (11) 0.0160 (11) 0.0199 (12) −0.0003 (9) −0.0079 (9) −0.0037 (9) O14 0.0179 (8) 0.0228 (8) 0.0234 (8) −0.0070 (7) −0.0018 (6) −0.0072 (7) N15 0.0194 (10) 0.0240 (10) 0.0168 (10) −0.0108 (8) −0.0014 (8) −0.0067 (8) O16 0.0215 (8) 0.0247 (8) 0.0202 (8) −0.0118 (7) 0.0023 (6) −0.0077 (7) C17 0.0226 (12) 0.0226 (11) 0.0194 (12) −0.0071 (9) −0.0030 (9) −0.0077 (9)
supporting information sup-7 Acta Cryst. (2009). E65, o992–o993 C18 0.0251 (13) 0.0274 (12) 0.0219 (12) −0.0099 (10) 0.0008 (10) −0.0072 (10) C19 0.0290 (13) 0.0275 (13) 0.0198 (12) −0.0055 (10) 0.0008 (10) −0.0055 (10) C20 0.0270 (13) 0.0387 (14) 0.0171 (12) −0.0081 (11) −0.0025 (10) −0.0124 (10) C21 0.0233 (12) 0.0208 (11) 0.0191 (12) −0.0069 (9) −0.0054 (9) −0.0060 (9) C22 0.0250 (12) 0.0219 (11) 0.0178 (12) −0.0112 (9) −0.0029 (9) −0.0075 (9) C23 0.0229 (12) 0.0285 (13) 0.0221 (12) −0.0048 (10) −0.0019 (10) −0.0103 (10) O24 0.0285 (9) 0.0382 (10) 0.0328 (10) −0.0059 (8) −0.0123 (8) −0.0159 (8) O25 0.0382 (10) 0.0264 (9) 0.0315 (10) −0.0015 (8) −0.0165 (8) −0.0067 (7) C26 0.0500 (18) 0.0405 (16) 0.0317 (15) 0.0081 (13) −0.0213 (13) −0.0123 (12) C31 0.0126 (10) 0.0148 (10) 0.0217 (12) −0.0002 (8) −0.0044 (9) −0.0038 (9) C32 0.0153 (11) 0.0186 (11) 0.0186 (12) 0.0011 (8) −0.0052 (9) −0.0041 (9) C33 0.0144 (10) 0.0153 (10) 0.0240 (12) −0.0002 (8) −0.0060 (9) −0.0073 (9) N34 0.0193 (10) 0.0182 (10) 0.0269 (11) −0.0023 (8) −0.0086 (8) −0.0072 (8) O35 0.0441 (11) 0.0366 (10) 0.0211 (10) −0.0182 (8) −0.0053 (8) −0.0085 (7) O36 0.0254 (9) 0.0199 (8) 0.0338 (10) −0.0093 (7) −0.0069 (7) −0.0043 (7) C37 0.0135 (10) 0.0129 (10) 0.0257 (12) −0.0004 (8) −0.0044 (9) −0.0030 (9) C38 0.0124 (10) 0.0177 (11) 0.0181 (11) 0.0016 (8) −0.0035 (8) −0.0037 (9) N39 0.0182 (10) 0.0186 (9) 0.0213 (10) −0.0014 (8) −0.0022 (8) −0.0051 (8) O40 0.0308 (9) 0.0296 (9) 0.0262 (9) −0.0129 (8) 0.0036 (7) −0.0048 (7) O41 0.0300 (9) 0.0285 (9) 0.0248 (9) −0.0079 (7) −0.0062 (7) −0.0069 (7) C42 0.0150 (11) 0.0146 (10) 0.0246 (12) 0.0013 (8) −0.0082 (9) −0.0062 (9) C43 0.0151 (11) 0.0158 (11) 0.0236 (12) −0.0016 (8) −0.0039 (9) −0.0057 (9) O44 0.0214 (8) 0.0200 (8) 0.0247 (9) −0.0068 (7) −0.0078 (7) −0.0036 (6) N45 0.0250 (10) 0.0241 (10) 0.0184 (10) −0.0124 (8) −0.0073 (8) −0.0019 (8) O46 0.0310 (9) 0.0233 (8) 0.0221 (9) −0.0116 (7) −0.0134 (7) −0.0011 (7) C47 0.0253 (12) 0.0229 (12) 0.0253 (13) −0.0062 (10) −0.0062 (10) −0.0012 (10) C48 0.0358 (14) 0.0269 (13) 0.0284 (14) −0.0073 (11) −0.0140 (11) 0.0001 (10) C49 0.0433 (16) 0.0377 (15) 0.0226 (14) −0.0041 (12) −0.0123 (12) 0.0005 (11) C50 0.0349 (15) 0.0435 (16) 0.0252 (14) −0.0083 (12) −0.0076 (11) 0.0098 (12) C51 0.0262 (13) 0.0217 (12) 0.0249 (13) −0.0068 (10) −0.0045 (10) −0.0016 (9) C52 0.0304 (13) 0.0204 (11) 0.0183 (12) −0.0102 (10) −0.0062 (10) −0.0017 (9) C53 0.0280 (13) 0.0254 (12) 0.0212 (12) −0.0086 (10) −0.0089 (10) 0.0007 (10) O54 0.0287 (10) 0.0324 (10) 0.0342 (10) −0.0134 (8) −0.0028 (8) 0.0008 (8) O55 0.0315 (10) 0.0266 (9) 0.0284 (9) −0.0067 (7) −0.0002 (8) −0.0059 (7) C56 0.0370 (15) 0.0363 (15) 0.0307 (15) −0.0046 (12) 0.0028 (12) −0.0051 (12) Geometric parameters (Å, º) C1—C2 1.390 (3) C31—C32 1.390 (3) C1—C12 1.393 (3) C31—C42 1.396 (3) C1—C13 1.510 (3) C31—C43 1.505 (3) C2—C3 1.384 (3) C32—C33 1.388 (3) C2—H2 0.93 C32—H32 0.93 C3—C7 1.385 (3) C33—C37 1.375 (3) C3—N4 1.473 (3) C33—N34 1.473 (3) N4—O5 1.222 (2) N34—O35 1.221 (2) N4—O6 1.226 (2) N34—O36 1.230 (2) C7—C8 1.380 (3) C37—C38 1.384 (3)