metal-organic compounds

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1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Tetrakis{2-[2-(2,6-dichloroanilino)- phenyl]ethanoato-j 2 O:O 0 }bis[(dimethyl sulfoxide-jo)copper(ii)](cu Cu): a binuclear Cu II complex with the nonsteroidal anti-inflammatory drug diclofenac Stéphanie Sayen and Emmanuel Guillon* Institut de Chimie Moléculaire de Reims, ICMR, UMR CNRS 7312, Université de Reims Champagne Ardenne, Moulin de la Housse, BP 1039, Reims cedex 2, France Correspondence emmanuel.guillon@univ-reims.fr Received 10 February 2012; accepted 16 March 2012 Key indicators: single-crystal X-ray study; T = 100 K; mean (C C) = Å; R factor = 0.031; wr factor = 0.079; data-to-parameter ratio = Experimental Crystal data [Cu 2 (C 14 H 10 Cl 2 NO 2 ) 4 (C 2 H 6 OS) 2 ] M r = Triclinic, P1 a = (5) Å b = (5) Å c = (5) Å = (5) = (5) = (5) V = (11) Å 3 Z =1 Mo K radiation = 1.17 mm 1 T = 100 K mm The title compound, [Cu 2 (C 14 H 10 Cl 2 NO 2 ) 4 (C 2 H 6 OS) 2 ], comprises a Cu2 II core that is quadruply bridged by four carboxylate ligands with the dimethyl sulfoxide ligands binding along the CuCu axis. The four carboxylate ligands bind in a bidentate syn syn bridging mode. Molecules reside on crystallographic inversion centres bisecting the mid-point of the CuCu axis. There are no intermolecular interactions of note. Related literature Cu II complexes of non-steroidal anti-inflammatory drugs (NSAIDs) show enhanced anti-inflammatory activity and reduced gastrointestinal toxicity compared with their uncomplexed parent drug, see: Weder et al. (2002). The structure of the Cu NSAID is likely to be an important factor for its biological activity. For example, the anti-tumor activity of the monomeric Cu II complex of aspirin ([Cu(Asp) 2 (py) 2 ]) is reportedly more effective than the dimeric [Cu 2 (Asp) 4 ] complex, see: Oberley & Buettner (1979). It has been shown that dinuclear Cu NSAID complexes exhibit similar biological activity to mononuclear complexes, but with higher stability (Dimiza et al., 2011), making them relevant compounds in the treatment of tumor cell lines (Theodorou et al., 1999). For mono- and binuclear Cu II complexes of diclofenac, see: Sayen et al. (2012) for [Cu(diclofenac) 2 (H 2 O) 2 ]- 2H 2 O and Kovala-Demertzi et al. (1997) for [Cu 2 (diclofenac) 4 - (DMF) 2 ]. Data collection Oxford Diffraction SuperNova Atlas diffractometer Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2010) T min = 0.867, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 396 parameters 1 restraint Table 1 Selected geometric parameters (Å, ). Cu1 O (11) Cu1 O (11) Cu1 O (11) O2 Cu1 O (5) O2 Cu1 O (4) O1 Cu1 O (6) O2 Cu1 O (5) O1 Cu1 O (4) O2 0 Cu1 O (6) O2 Cu1 O1D (5) O1 Cu1 O1D (4) Symmetry code: (i) x; y; z þ measured reflections independent reflections 9113 reflections with I > 2(I) R int = H atoms treated by a mixture of independent and constrained refinement max = 0.71 e Å 3 min = 0.51 e Å 3 Cu1 O (11) Cu1 O1D (14) Cu1 Cu1 i (12) O2 0 Cu1 O1D (4) O1 0 Cu1 O1D (4) O2 Cu1 Cu1 i (4) O1 Cu1 Cu1 i (3) O2 0 Cu1 Cu1 i (4) O1 0 Cu1 Cu1 i (3) O1D Cu1 Cu1 i (3) Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); m474 Sayen and Guillon doi: /s x

2 metal-organic compounds molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97. Dr S. Chevreux and Professor E. Wenger are gratefully acknowledged for the crystal structure determination. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GG2076). References Dimiza, F., Perdih, F., Tangoulis, V., Turel, I., Kessissoglou, D. & Psomas, G. (2011). J. Inorg. Biochem. 105, Kovala-Demertzi, D., Theodorou, A., Demertzis, M., Raptopoulou, C. P. & Terzis, A. (1997). J. Inorg. Biochem. 65, Oberley, L. W. & Buettner, G. R. (1979). Cancer Res. 39, Oxford Diffraction (2010). CrysAlis PRO and ABSPACK. Oxford Diffraction, Yarnton, England. Sayen, S., Carlier, A., Tarpin, M. & Guillon, E. (2012). Dalton Trans. Submitted. Sheldrick, G. M. (2008). Acta Cryst. A64, Theodorou, A., Demertzis, M. A., Kovala-Demertzi, D., Lioliou, E. E., Pantazaki, A. A. & Kyriakidis, D. A. (1999). BioMetals, 12, Weder, J. E., Dillon, C. T., Hambley, T. W., Kennedy, B. J., Lay, P. A., Biffin, J. R., Regtop, H. L. & Davies, N. M. (2002). Coord. Chem. Rev. 232, Sayen and Guillon [Cu 2 (C 14 H 10 Cl 2 NO 2 ) 4 (C 2 H 6 OS) 2 ] m475

3 supplementary materials [doi: /s x] Tetrakis{2-[2-(2,6-dichloroanilino)phenyl]ethanoato-κ 2 O:O }bis[(dimethyl sulfoxide-κo)copper(ii)](cu Cu): a binuclear Cu II complex with the nonsteroidal anti-inflammatory drug diclofenac Stéphanie Sayen and Emmanuel Guillon Comment The proposed curative properties of Cu-based non-steroidal anti-inflammatory drugs (NSAIDs) have led to the development of numerous Cu(II) complexes of NSAIDs with enhanced anti-inflammatory activity and reduced gastrointestinal toxicity compared with their uncomplexed parent drug (Weder et al., 2002). Furthermore, little is known of their pharmacokinetic and biodistribution profile in both humans and animals, stabilty in biological media, or of the relative potency/efficacy of the Cu II monomeric versus Cu II dimeric complexes. The structure of the Cu-NSAID is likely to be an important factor for its biological activity. For example, the anti-tumor activity of the monomeric Cu II complex of aspirin ([Cu(Asp) 2 (py) 2 ]) is reportedly more effective than the dimeric [Cu 2 (Asp) 4 ] complex (Oberley & Buettner, 1979). Thus, it appears to be essential to obtain structural information on Cu (II) complexes of NSAIDs in order to fully understand their biological activity. Being able to act as a ligand through its carboxylate function of the aromatic ring, different diclofenac complexes (Cu-NSAID complex) were described in the literature. It gives rise to a mononuclear [Cu(diclofenac) 2 (H 2 O) 2 ].2H 2 O complex (Sayen et al., 2012) and a binuclear [Cu 2 (diclofenac) 4 (DMF) 2 ] complex without a metal-metal bond (Kovala-Demertzi et al., 1997). The former resulted in a distorted octahedral geometry, whereas the latter resulted in a binuclear copper complex where each metal centre is described as a perfect square bipyramid with a DMF oxygen occupying apical position. In order to favour the metal metal bond, which stabilizes the complex and thus impact the biological activity, we have tried various coordinating solvents during the recrystallization. The structure of the binuclear [bis(2-[2-(2,6-dichlorophenyl)aminophenyl]ethanoate)bis(dmso)copper(ii)] complex (I) has been obtained. It consists of a quadruply bridged neutral molecule lying on a crystallographic centre of inversion (Fig. 1). Indeed, the four carboxylato moieties act as bridging ligands exhibiting a centre of symmetry midway between the two Cu atoms. The solvent used in the synthesis binds in the position trans to the Cu Cu axis. The dimeric structure has a Cu Cu distance of (12) Å, with an octahedral stereochemistry tetragonally elongated along the Cu Cu- O solvent axis due to the Jahn-Teller effect (Table 1). In the binuclear unit, the carboxylic acids are fully deprotonated to balance the charge from the Cu II ions. The stability of the structure is ensured via a network of /p /p interactions involving the phenyl acetate rings of the diclofenac molecules. On the other hand, no intermolecular H-bonding is observed (Fig. 2). The use of DMSO solvent allowed the formation of a binuclear complex with a Cu 2 metal core, which stabilizes the complex in biological media. It was shown that binuclear Cu-NSAID complexes exhibit similar biological activity as the mononuclear complex, but with a higher stability (Dimiza et al., 2011), making them relevant compounds in the treatment of tumor cell lines (Theodorou et al., 1999). sup-1

4 Experimental The [bis(2-[2-(2,6-dichlorophenyl)aminophenyl]ethanoate)bis(dmso)copper(ii)] was prepared from a mixture of copper sulfate and diclofenac sodium salt in the molar ratio 1:2 in deionized water. After stirring for 2 hrs at room temperature, the reaction mixture was filtered and the green precipitate was washed with water and dried in air. Crystals suitable for X- ray diffraction measurements were obtained by slow evaporation of a DMSO solution of the complex. Computing details Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008). Figure 1 A representation of the title compound (I) with displacement ellipsoids at the 30% probability level. sup-2

5 Figure 2 The π π stacking interactions in the [Cu 2 (diclofenac) 4 (DMSO) 2 ] complex (H atoms are omitted for clarity). Tetrakis{2-[2-(2,6-dichloroanilino)phenyl]ethanoato- κ 2 O:O }bis[(dimethyl sulfoxide-κo)copper(ii)](cu Cu) Crystal data [Cu 2 (C 14 H 10 Cl 2 NO 2 ) 4 (C 2 H 6 OS) 2 ] M r = Triclinic, P1 Hall symbol: -P 1 a = (5) Å b = (5) Å c = (5) Å α = (5) β = (5) γ = (5) V = (11) Å 3 Data collection Oxford Diffraction SuperNova Atlas diffractometer Radiation source: SuperNova (Mo) X-ray Source Mirror monochromator Detector resolution: pixels mm -1 CCD scans Absorption correction: multi-scan (ABSPACK; Oxford Diffraction, 2010) Z = 1 F(000) = 746 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from reflections θ = µ = 1.17 mm 1 T = 100 K Prismatic, green mm T min = 0.867, T max = measured reflections independent reflections 9113 reflections with I > 2σ(I) R int = θ max = 33.4, θ min = 3.0 h = k = l = sup-3

6 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 396 parameters 1 restraint Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ 2 (F o2 ) + (0.0335P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.71 e Å 3 Δρ min = 0.51 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 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 Cu (16) (13) (12) (4) Cl (4) (3) (3) (8) Cl (4) (3) (3) (7) S1D (3) (3) (3) (7) Cl (4) (3) (3) (8) Cl (4) (3) (3) (9) O (10) (8) (8) (19) O1D (10) (8) (8) (18) O (10) (9) (8) (2) O (11) (9) (8) (2) O (11) (9) (9) (2) N (13) (10) (10) (2) H (2) (17) (15) 0.021* C (14) (12) (11) (2) C (14) (11) (11) (2) C (14) (12) (10) (2) N (13) (11) (10) (2) H (2) (17) (16) 0.025* C (15) (12) (12) (3) H * C (15) (13) (11) (3) H * C (16) (12) (12) (3) H * C (14) (12) (11) (2) sup-4

7 H2A * H2B * C (14) (12) (11) (3) C (14) (11) (10) (2) C (15) (12) (11) (3) C1D (16) (14) (11) (3) H02A * H02B * H02C * C (15) (13) (12) (3) H * C (15) (14) (12) (3) H * C (15) (13) (13) (3) H * C (15) (13) (11) (3) H * C (15) (13) (12) (3) H * C2D (18) (13) (14) (3) H03A * H03B * H03C * C (15) (12) (12) (3) H * C (16) (13) (12) (3) H * C (14) (11) (11) (2) H22A * H22B * C (15) (12) (12) (3) H * C (15) (13) (11) (3) C (14) (11) (10) (2) C (14) (11) (11) (2) C (14) (11) (10) (2) C (15) (12) (12) (3) H * C (16) (13) (13) (3) H * C (15) (12) (12) (3) H * C (14) (11) (11) (2) C (14) (11) (11) (2) Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Cu (7) (8) (7) (6) (5) (5) Cl (15) (19) (18) (14) (13) (14) sup-5

8 Cl (18) (17) (16) (14) (14) (13) S1D (14) (16) (15) (12) (11) (12) Cl (17) (16) (16) (13) (13) (12) Cl (18) (19) (18) (15) (14) (15) O (4) (5) (5) (4) (4) (4) O1D (4) (5) (4) (4) (3) (4) O (4) (5) (4) (4) (4) (4) O (5) (5) (5) (4) (4) (4) O (5) (5) (5) (4) (4) (4) N (5) (5) (5) (4) (4) (4) C (6) (7) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (5) (5) (4) (5) N (5) (6) (5) (5) (4) (4) C (6) (6) (6) (5) (5) (5) C (6) (7) (6) (5) (5) (5) C (6) (7) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (5) (7) (6) (5) (5) (5) C (5) (6) (5) (4) (4) (4) C (6) (6) (6) (5) (5) (5) C1D (6) (8) (6) (6) (5) (5) C (6) (7) (7) (5) (5) (6) C (6) (8) (6) (5) (5) (6) C (6) (7) (7) (5) (5) (6) C (6) (7) (6) (5) (5) (5) C (6) (8) (6) (5) (5) (6) C2D (8) (7) (8) (6) (6) (6) C (6) (6) (6) (5) (5) (5) C (7) (7) (7) (5) (6) (5) C (6) (6) (6) (5) (5) (5) C (6) (7) (6) (5) (5) (5) C (6) (7) (6) (5) (5) (5) C (6) (6) (5) (5) (4) (4) C (6) (6) (6) (5) (5) (4) C (5) (6) (5) (5) (4) (4) C (6) (7) (6) (5) (5) (5) C (7) (7) (7) (5) (5) (6) C (6) (7) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) C (6) (6) (6) (5) (5) (5) Geometric parameters (Å, º) Cu1 O (11) C2 H2B Cu1 O (11) C9 C (2) Cu1 O (11) C1 O1 i (17) Cu1 O (11) C30 C (2) Cu1 O1D (14) C1D H02A Cu1 Cu1 i (12) C1D H02B sup-6

9 Cl3 C (17) C1D H02C Cl2 C (17) C5 C (2) S1D O1D (11) C5 C (2) S1D C1D (16) C5 H S1D C2D (18) C12 C (2) Cl4 C (15) C12 H Cl1 C (16) C11 C (2) O2 C (17) C11 H O1 C (16) C7 C (2) O1 C1 i (17) C7 H O2 C21 i (16) C6 H N012 C (18) C2D H03A N012 C (18) C2D H03B N012 H (2) C2D H03C C14 C (2) C4 C (2) C14 C (2) C4 H C28 C (2) C26 C (2) C28 C (2) C26 H C8 C (19) C22 C (2) C8 C (2) C22 C (19) C8 N (18) C22 H22A N1 C (19) C22 H22B N1 H (2) C32 C (2) C31 C (2) C32 H C31 C (2) C21 O2 i (16) C31 H C23 C (19) C13 C (2) C24 C (2) C13 H C24 H C27 C (2) C25 H C27 H C33 C (2) C2 C (19) C33 H C2 C (19) C34 C (2) C2 H2A O2 Cu1 O (5) H02A C1D H02C O2 Cu1 O (4) H02B C1D H02C O1 Cu1 O (6) C6 C5 C (14) O2 Cu1 O (5) C6 C5 H O1 Cu1 O (4) C4 C5 H O2 Cu1 O (6) C11 C12 C (14) O2 Cu1 O1D (5) C11 C12 H O1 Cu1 O1D (4) C13 C12 H O2 Cu1 O1D (4) C10 C11 C (15) O1 Cu1 O1D (4) C10 C11 H O2 Cu1 Cu1 i (4) C12 C11 H O1 Cu1 Cu1 i (3) C6 C7 C (13) O2 Cu1 Cu1 i (4) C6 C7 H O1 Cu1 Cu1 i (3) C8 C7 H O1D Cu1 Cu1 i (3) C5 C6 C (13) sup-7

10 O1D S1D C1D (7) C5 C6 H O1D S1D C2D (7) C7 C6 H C1D S1D C2D (8) S1D C2D H03A C21 O2 Cu (9) S1D C2D H03B S1D O1D Cu (6) H03A C2D H03B C1 O1 Cu (9) S1D C2D H03C C1 i O1 Cu (9) H03A C2D H03C C21 i O2 Cu (9) H03B C2D H03C C29 N012 C (12) C5 C4 C (14) C29 N012 H (14) C5 C4 H C28 N012 H (14) C3 C4 H C13 C14 C (14) C25 C26 C (14) C13 C14 Cl (11) C25 C26 H C9 C14 Cl (11) C27 C26 H C27 C28 C (13) C23 C22 C (11) C27 C28 N (13) C23 C22 H22A C23 C28 N (13) C21 C22 H22A C7 C8 C (13) C23 C22 H22B C7 C8 N (13) C21 C22 H22B C3 C8 N (12) H22A C22 H22B C9 N1 C (12) C33 C32 C (13) C9 N1 H (14) C33 C32 H C8 N1 H (14) C31 C32 H C30 C31 C (13) C11 C10 C (14) C30 C31 H C11 C10 Cl (12) C32 C31 H C9 C10 Cl (11) C14 C13 C (14) O2 i C21 O (13) C14 C13 H O2 i C21 C (12) C12 C13 H O2 C21 C (12) C26 C27 C (14) C28 C23 C (13) C26 C27 H C28 C23 C (12) C28 C27 H C24 C23 C (13) C3 C2 C (11) C4 C3 C (12) C3 C2 H2A C4 C3 C (13) C1 C2 H2A C8 C3 C (12) C3 C2 H2B C25 C24 C (14) C1 C2 H2B C25 C24 H H2A C2 H2B C23 C24 H N1 C9 C (14) C26 C25 C (14) N1 C9 C (13) C26 C25 H C14 C9 C (13) C24 C25 H O1 i C1 O (12) C32 C33 C (13) O1 i C1 C (12) C32 C33 H O1 C1 C (12) C34 C33 H C31 C30 C (13) C33 C34 C (13) C31 C30 Cl (11) C33 C34 Cl (11) C29 C30 Cl (10) C29 C34 Cl (10) S1D C1D H02A N012 C29 C (13) S1D C1D H02B N012 C29 C (13) sup-8

11 H02A C1D H02B C30 C29 C (12) S1D C1D H02C O1 Cu1 O2 C (10) C3 C8 C7 C6 1.2 (2) O2 Cu1 O2 C (3) N1 C8 C7 C (13) O1 Cu1 O2 C (10) C4 C5 C6 C7 1.9 (2) O1D Cu1 O2 C (10) C8 C7 C6 C5 1.2 (2) Cu1 i Cu1 O2 C (10) C6 C5 C4 C3 0.2 (2) C1D S1D O1D Cu (10) C28 C27 C26 C (2) C2D S1D O1D Cu (10) C30 C31 C32 C (2) O2 Cu1 O1D S1D (9) C12 C11 C10 C9 0.8 (2) O1 Cu1 O1D S1D (8) C12 C11 C10 Cl (11) O2 Cu1 O1D S1D (9) N1 C9 C10 C (13) O1 Cu1 O1D S1D (9) C14 C9 C10 C (2) O2 Cu1 O1 C (11) N1 C9 C10 Cl (18) O2 Cu1 O1 C (11) C14 C9 C10 Cl (10) O1 Cu1 O1 C1 5.6 (3) Cu1 O2 C21 O2 i 9.74 (19) O1D Cu1 O1 C (10) Cu1 O2 C21 C (9) Cu1 i Cu1 O1 C (10) C23 C22 C21 O2 i (13) O2 Cu1 O1 C1 i (12) C23 C22 C21 O (16) O1 Cu1 O1 C1 i 14.8 (3) C27 C28 C23 C (2) O2 Cu1 O1 C1 i (11) N012 C28 C23 C (13) O1D Cu1 O1 C1 i (11) C27 C28 C23 C (13) Cu1 i Cu1 O1 C1 i 6.72 (11) N012 C28 C23 C (19) O2 Cu1 O2 C21 i 2.2 (3) C21 C22 C23 C (16) O1 Cu1 O2 C21 i (12) C21 C22 C23 C (15) O1 Cu1 O2 C21 i (11) C5 C4 C3 C8 2.1 (2) O1D Cu1 O2 C21 i (11) C5 C4 C3 C (13) Cu1 i Cu1 O2 C21 i 4.12 (11) C7 C8 C3 C4 2.8 (2) C29 N012 C28 C (2) N1 C8 C3 C (12) C29 N012 C28 C (13) C7 C8 C3 C (12) C7 C8 N1 C (2) N1 C8 C3 C (19) C3 C8 N1 C (13) C1 C2 C3 C (15) C9 C14 C13 C (2) C1 C2 C3 C (16) Cl2 C14 C13 C (11) C28 C23 C24 C (2) C23 C28 C27 C (2) C22 C23 C24 C (13) N012 C28 C27 C (14) C27 C26 C25 C (2) C8 N1 C9 C (2) C23 C24 C25 C (2) C8 N1 C9 C (16) C31 C32 C33 C (2) C13 C14 C9 N (13) C32 C33 C34 C (2) Cl2 C14 C9 N (18) C32 C33 C34 Cl (11) C13 C14 C9 C (2) C28 N012 C29 C (19) Cl2 C14 C9 C (10) C28 N012 C29 C (15) Cu1 O1 C1 O1 i 8.65 (19) C31 C30 C29 N (14) Cu1 O1 C1 C (9) Cl3 C30 C29 N (19) C3 C2 C1 O1 i 3.49 (18) C31 C30 C29 C (2) C3 C2 C1 O (12) Cl3 C30 C29 C (10) C32 C31 C30 C (2) C33 C34 C29 N (13) C32 C31 C30 Cl (11) Cl4 C34 C29 N (19) sup-9

12 C14 C13 C12 C (2) C33 C34 C29 C (2) C13 C12 C11 C (2) Cl4 C34 C29 C (10) Symmetry code: (i) x, y, z+1. sup-10