metal-organic compounds

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1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Bis[1,3-bis(1-benzyl-1H-benzimidazol-2- yl)-2-oxapropane]nickel(ii) dipicrate dimethylformamide ethanol (1/2/0.25) Huilu Wu,* Ruirui Yun, Ke Li, Kaitong Wang and Xingcai Huang School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou , People s Republic of China Correspondence wuhuilu@163.com Received 12 May 2009; accepted 4 June 2009 Key indicators: single-crystal X-ray study; T = 153 K; mean (C C) = Å; disorder in solvent or counterion; R factor = 0.093; wr factor = 0.290; data-toparameter ratio = Experimental Crystal data [Ni(C 30 H 26 N 4 O) 2 ](C 6 H 2 N 3 O 7 ) 2-2C 3 H 7 NO0.25C 2 H 6 O M r = Monoclinic, P2 1 =c a = (4) Å b = (5) Å c = (8) Å Data collection Rigaku R-AXIS SPIDER diffractometer Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T min = 0.948, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections 1031 parameters = (1) V = (4) Å 3 Z =4 Mo K radiation = 0.34 mm 1 T = 153 K mm measured reflections independent reflections 7422 reflections with I > 2(I) R int = restraints H-atom parameters constrained max = 1.47 e Å 3 min = 0.70 e Å 3 In the title compound, [Ni(C 30 H 26 N 4 O) 2 ](C 6 H 2 N 3 O 7 ) 2-2C 3 H 7 NO0.25CH 3 CH 2 OH, the Ni II ion is coordinated in a distorted octahedral environment by four N atoms and two O atoms from two tridendate 1,3-bis(1-benzyl-1H-benzimidazol- 2-yl)-2-oxapropane ligands. The crystal structure is stabilized by weak intermolecular C HO hydrogen bonds and weak stacking interactions [centroid centroid distance (3) Å]. As well as the cation, two anions and two dimethylformamide solvent molecules, the asymmetric unit also contains an ethanol solvent molecule with 0.25 occupancy. Related literature For background to the applications of bis(2-benzimidazolyl)- alkanes and their derivatives, see: Hendriks et al. (1982); Piquet et al. (1995); Roderick et al. (1972); Wu et al. (2005); van Berkel et al. (1995). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA C2 H2AO10 i (8) 144 C8 H8AO (9) 173 C8 H8BO12 ii (9) 140 C9 H9AO12 ii (9) 142 C9 H9BO (7) 156 C17 H17AO8 ii (9) 161 C38 H38AO (8) 164 C38 H38BO10 i (7) 133 C39 H39AO10 i (9) 135 C39 H39AO11 i (10) 137 C43 H43AO16 iii (8) 144 C56 H56AO11 i (11) 155 C65 H65AO (10) 169 C77 H77BO (15) 150 Symmetry codes: (i) x 1; y þ 3 2 ; z 1 2 ; (ii) x þ 2; y þ 2; z þ 1; (iii) x þ 2; y þ 1; z þ 1. Data collection: RAPID-AUTO (Rigaku/MSC, 2004); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; 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: SHELXTL. The authors acknowledge financial support and a grant from the Qing Lan Talent Engineering Funds and Students Science and Technology Innovation Funds (No. DXS ,041) of Lanzhou Jiaotong University. A grant from the Middle-Young Age Science Foundation (No. 3YS061-A25 023) and Long Yuan Qing Nian of Gansu Province is also acknowledged Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: LH2826). doi: /s Wu et al. m751

2 metal-organic compounds References Berkel, P. M. van, Driessen, W. L., Koolhaas, G. J. A. A., Reedijk, J. & Sherington, D. C. (1995). Polymer, 37, Hendriks, H. M. J., Birker, P. J. M. W. L., Verschoor, G. C. & Reedijk, J. (1982). J. Chem. Soc. Dalton Trans. pp Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Piquet, C., Bunzli, J.-C. G. & Williams, A. F. (1995). J. Alloys Compd, 225, Rigaku/MSC (2004). RAPID-AUTO. Rigaku/MSC, The Woodlands, Texas, USA. Roderick, W. R., Nordeen, C. W., von Esch, A. M. & Appell, R. N. (1972). J. Med. Chem. 15, Sheldrick, G. M. (2008). Acta Cryst. A64, Wu, H. L., Ying, W., Pen, L., Gao, Y. C. & Yu, K. B. (2005). Synth. React. Inorg. Met. Org. Chem. 34, m752 Wu et al. [Ni(C 30 H 26 N 4 O) 2 ](C 6 H 2 N 3 O 7 ) 2 2C 3 H 7 NO0.25C 2 H 6 O

3 supporting information [doi: /s ] Bis[1,3-bis(1-benzyl-1H-benzimidazol-2-yl)-2-oxapropane]nickel(II) dipicrate dimethylformamide ethanol (1/2/0.25) Huilu Wu, Ruirui Yun, Ke Li, Kaitong Wang and Xingcai Huang S1. Comment There is widespread interest in bis(2-benzimidazolyl)alkanes and their derivatives because of their wide-ranging antivirus activity (Roderick et al., 1972), their importance in selective ion-exchange resins (van Berkel et al., 1995), and the possibility of forming supramolecular aggregates with d 10 metal ions in which discrete macrocycles, 1, 2 and 3-D architectures have been generated (Piquet et al. 1995). We have been interested in utilizing benzimidazolyl substituted tripodal ligands with nitrogen cores to construct supramolecules, which could provide hydrogen bond donor NH groups and π π stacking interactions (Hendriks et al., 1982). In our work, efforts are focused on the tridentate ligand, 1,3-bis(1- benzylbenzimidazol-2-yl)-2-oxopropane, which is similar to the histidine imidazole ligand in its coordination aspects (Wu et al. 2005). Since the two arms of this type of ligand can each rotate freely about an O(apical)-C bond, multicomponent complexes or coordination polymeric networks may be expected to form from the assembly of this ligand with metal ions of low coordination number. Herein, the crystal structure of the title compound is presented. The molecular structure of the cation is shown in Fig. 1. The Ni II ion is coordinated in a disotorted octahedral environment inolving four N atoms and two O atoms from two tridendate ligands with the axial sites occupied by two oxygen atoms. The crystal structure is stabilized by weak intermolecular C-H O hydrogen bonds as well as weak π π stacking interactions with a centroid to centroid distance of (3) Å between two benzimidazole ring systems related by the symmetry operator (1-x,-1/2+y,1/2-z). S2. Experimental Reagents and solvents used were of commercially available quality. To a strred solution of 1,3-bis(1-benzylbenzimidazol-2-yl)-2-oxopropane (183.2 mg, 0.4 mmol) in hot MeOH (10 ml) was added Ni(C 6 H 2 N 3 O 7 ) 2 (102.9 mg, 0.2 mmol) in MeOH (5 ml). A green crystalline product formed rapidly. The precipitate was filtered off, washed with methanol and absolute ethanol, and dried in vacuo. The dried precipitate was dissolved in DMF to form a green solution that was allowed to evaporate at room temperature. The green crystals suitable for X-ray diffraction studies were obtained after three weeks (Yield, 64%). Elemental analysis - found: C, 59.30; H, 4.51; N, 14.14; calc. for C 78.5 H 71.5 N 16 O Ni, C, 59.31; H, 4.53; N, 14.10%. S3. Refinement All H atoms were found in difference electron maps and were subsequently refined in a riding-model approximation with C H distances ranging from 0.95 to 0.99 Å and U iso (H) = 1.2 U eq or U iso (H) = 1.5 U eq for methyl C atoms. The abundance of solvent which is loosely held in the crystal lattice is probably the reason for the lower than normal precision of this structure. sup-1

4 Figure 1 The molecular structure of the cation. Hydrogen atoms have been omitted for clarity and the displacement ellipsoids are shown at the 30% probability level. sup-2

5 Figure 2 Part of the crystal structure with weak hydrogen bonds shown as dashed lines. For clarity the solvent molecules are not included. Bis[1,3-bis(1-benzyl-1H-benzimidazol-2-yl)-2-oxapropane]nickel(II) dipicrate dimethylformamide ethanol (1/2/0.25) Crystal data [Ni(C 30 H 26 N 4 O) 2 ] (C 6 H 2 N 3 O 7 ) 2 2C 3 H 7 NO 0.25C 2 H 6 O M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (4) Å b = (5) Å c = (8) Å β = (1) V = (4) Å 3 Z = 4 F(000) = 3314 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 7422 reflections θ = µ = 0.34 mm 1 T = 153 K Block, green mm sup-3

6 Data collection Rigaku R-AXIS SPIDER diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scans Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T min = 0.948, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 1031 parameters 33 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map measured reflections independent reflections 7422 reflections with I > 2σ(I) R int = θ max = 25.3, θ min = 3.1 h = k = l = Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.159P) 2 ] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max < Δρ max = 1.47 e Å 3 Δρ min = 0.70 e Å 3 Extinction correction: SHELXL97 (Sheldrick, 2008), Fc * =kfc[ xfc 2 λ 3 /sin(2θ)] -1/4 Extinction coefficient: (7) 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 Occ. (<1) Ni (4) (4) (3) (3) O (2) (2) (15) (10) O (2) (2) (16) (10) O (4) (5) (3) (3) O (3) (3) (2) (14) O (3) (4) (3) (3) O (3) (3) (2) (15) O (2) (3) (19) (13) O (4) (4) (2) (2) O (4) (5) (2) (3) O (3) (2) (16) (11) O (5) (4) (3) (3) O (4) (4) (3) (2) O (3) (3) (18) (14) O (3) (3) (19) (16) sup-4

7 O (4) (3) (3) (2) O (3) (4) (3) (2) N (3) (2) (18) (11) N (3) (3) (18) (11) N (3) (3) (18) (11) N (3) (3) (19) (12) N (3) (2) (18) (11) N (3) (2) (18) (11) N (3) (3) (18) (11) N (3) (2) (19) (11) N (3) (3) (3) (16) N (3) (3) (2) (14) N (4) (4) (2) (17) N (4) (3) (2) (15) N (3) (3) (2) (15) N (4) (3) (3) (19) N (5) (4) (3) (3) N (5) (5) (3) (3) C (3) (3) (2) (13) C (4) (3) (2) (15) H2A * C (4) (4) (3) (17) H3A * C (4) (4) (3) (19) H4A * C (4) (4) (3) (17) H5A * C (3) (3) (2) (14) C (3) (3) (2) (13) C (3) (3) (2) (14) H8A * H8B * C (3) (3) (2) (14) H9A * H9B * C (3) (3) (2) (14) C (3) (3) (2) (14) C (4) (4) (3) (16) H12A * C (4) (4) (3) (17) H13A * C (4) (4) (3) (19) H14A * C (3) (4) (3) (16) H15A * C (3) (3) (2) (14) C (3) (3) (3) (15) H17A * sup-5

8 H17B * C (3) (3) (2) (15) C (4) (3) (3) (19) H19A * C (4) (4) (3) (2) H20A * C (4) (4) (3) (2) H21A * C (4) (4) (3) (2) H22A * C (4) (4) (3) (17) H23A * C (4) (3) (2) (15) H24A * H24B * C (4) (3) (2) (14) C (4) (4) (3) (17) H26A * C (4) (4) (3) (19) H27A * C (4) (4) (3) (16) H28A * C (4) (4) (3) (15) H29A * C (4) (4) (2) (15) H30A * C (3) (3) (2) (13) C (3) (3) (2) (14) H32A * C (4) (3) (3) (15) H33A * C (4) (3) (3) (16) H34A * C (4) (3) (2) (15) H35A * C (3) (3) (2) (13) C (3) (3) (2) (13) C (3) (3) (2) (13) H38A * H38B * C (3) (3) (3) (15) H39A * H39B * C (3) (3) (2) (13) C (3) (3) (2) (13) C (4) (3) (2) (15) H42A * C (4) (3) (2) (15) sup-6

9 H43A * C (4) (4) (3) (16) H44A * C (3) (3) (2) (15) H45A * C (3) (3) (2) (13) C (3) (4) (2) (15) H47A * H47B * C (3) (3) (2) (13) C (3) (3) (2) (15) H49A * C (4) (4) (3) (17) H50A * C (4) (4) (3) (17) H51A * C (4) (4) (3) (17) H52A * C (3) (4) (2) (16) H53A * C (3) (3) (3) (15) H54A * H54B * C (3) (3) (2) (15) C (4) (4) (3) (2) H56A * C (5) (5) (4) (2) H57A * C (6) (5) (5) (3) H58A * C (6) (6) (4) (3) H59A * C (5) (6) (3) (3) H60A * C (4) (4) (3) (19) C (3) (4) (3) (17) C (4) (3) (3) (16) H63A * C (3) (3) (2) (15) C (4) (3) (3) (16) H65A * C (4) (4) (3) (16) C (3) (3) (2) (14) C (3) (3) (2) (13) C (3) (3) (2) (14) H69A * C (3) (3) (2) (15) C (4) (4) (3) (16) sup-7

10 H71A * C (4) (3) (3) (15) C (11) (10) (7) (7) H73A * H73B * H73C * C (6) (8) (5) (6) H74A * H74B * H74C * C (5) (5) (4) (3) H75A * C (10) (9) (6) (6) H76A * H76B * H76C * C (7) (8) (5) (6) H77A * H77B * H77C * O (5) (3) (3) (3) O (9) (8) (6) (6) C (10) (8) (7) (7) H78A * C (2) (17) (13) (10)* 0.25 H80A * 0.25 H80B * 0.25 H80C * 0.25 C (2) (15) (13) (11)* 0.25 H79A * 0.25 H79B * 0.25 O (19) (16) (13) (11)* 0.25 H * 0.25 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Ni (4) (4) (4) (3) (3) (3) O (18) (3) (2) (18) (17) (19) O (19) (2) (3) (16) (18) (18) O (5) (8) (7) (5) (5) (6) O (2) (4) (4) (2) (2) (3) O (4) (7) (4) (4) (3) (5) O (3) (4) (4) (3) (3) (3) O (2) (3) (3) (2) (2) (2) O (4) (5) (4) (4) (3) (4) O (4) (8) (4) (5) (4) (5) O (3) (3) (3) (2) (2) (2) sup-8

11 O (8) (5) (4) (5) (5) (4) O (5) (5) (5) (4) (4) (4) O (3) (3) (3) (2) (2) (2) O (4) (4) (3) (3) (3) (3) O (4) (4) (5) (3) (4) (3) O (3) (5) (6) (3) (4) (4) N (2) (3) (3) (18) (2) (2) N (2) (3) (3) (19) (2) (2) N (2) (3) (3) (19) (2) (2) N (2) (3) (3) (2) (2) (2) N (2) (3) (3) (19) (2) (2) N (2) (3) (3) (19) (2) (2) N (2) (3) (3) (2) (2) (2) N (3) (3) (3) (19) (2) (2) N (3) (4) (5) (3) (3) (3) N (3) (4) (4) (2) (3) (3) N (4) (5) (4) (3) (3) (3) N (4) (3) (3) (3) (3) (3) N (3) (4) (3) (3) (3) (3) N (4) (4) (4) (3) (4) (3) N (5) (5) (6) (4) (5) (5) N (5) (6) (5) (4) (4) (4) C (3) (3) (3) (2) (3) (2) C (3) (3) (4) (2) (3) (3) C (4) (5) (4) (3) (3) (3) C (4) (6) (4) (4) (3) (3) C (4) (5) (4) (3) (3) (3) C (3) (3) (3) (3) (3) (3) C (3) (3) (3) (2) (3) (2) C (3) (4) (3) (2) (3) (3) C (3) (4) (3) (2) (2) (3) C (3) (4) (3) (2) (3) (3) C (3) (4) (4) (3) (3) (3) C (4) (4) (4) (3) (3) (3) C (3) (5) (4) (3) (3) (3) C (3) (5) (5) (3) (3) (4) C (3) (4) (4) (3) (3) (3) C (3) (3) (4) (2) (3) (3) C (3) (4) (4) (2) (3) (3) C (3) (4) (4) (2) (3) (3) C (3) (4) (5) (3) (3) (3) C (4) (4) (7) (3) (4) (4) C (4) (5) (6) (3) (4) (4) C (3) (6) (5) (3) (3) (4) C (3) (4) (5) (3) (3) (3) C (3) (4) (3) (3) (3) (3) C (3) (3) (3) (3) (3) (3) C (4) (5) (5) (3) (3) (3) sup-9

12 C (4) (4) (5) (3) (4) (4) C (4) (4) (4) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (3) (3) (2) (2) (2) C (3) (4) (3) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (4) (3) (4) (3) (3) (3) C (3) (3) (4) (3) (3) (3) C (3) (3) (3) (2) (3) (3) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (3) C (3) (3) (4) (2) (3) (3) C (3) (3) (3) (2) (3) (2) C (3) (3) (3) (2) (3) (2) C (3) (3) (4) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (3) (4) (2) (3) (3) C (3) (3) (4) (2) (3) (2) C (3) (4) (4) (3) (3) (3) C (3) (3) (4) (2) (3) (3) C (3) (4) (3) (3) (3) (3) C (3) (5) (4) (3) (3) (3) C (3) (4) (5) (3) (3) (3) C (4) (5) (4) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (3) (4) (2) (3) (3) C (3) (4) (4) (3) (3) (3) C (4) (5) (5) (3) (4) (4) C (4) (7) (7) (4) (5) (5) C (6) (8) (9) (5) (6) (7) C (6) (8) (5) (5) (5) (5) C (4) (9) (4) (5) (3) (5) C (4) (6) (5) (3) (4) (4) C (3) (4) (5) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (4) (4) (3) (3) (3) C (3) (3) (4) (2) (3) (3) C (3) (3) (3) (2) (3) (2) C (3) (3) (3) (3) (3) (3) C (3) (4) (3) (3) (3) (3) C (4) (4) (4) (3) (3) (3) C (3) (3) (4) (3) (3) (3) C (10) (10) (10) (8) (8) (8) C (7) (14) (12) (7) (7) (9) sup-10

13 C (5) (6) (8) (4) (5) (5) C (9) (9) (9) (8) (7) (8) C (9) (12) (10) (8) (8) (9) O (7) (4) (5) (4) (5) (3) O (9) (8) (9) (7) (7) (7) C (9) (10) (10) (8) (8) (8) Geometric parameters (Å, º) Ni1 N (5) C26 C (9) Ni1 N (5) C26 H26A Ni1 N (5) C27 C (9) Ni1 N (5) C27 H27A Ni1 O (4) C28 C (9) Ni1 O (4) C28 H28A O1 C (7) C29 C (9) O1 C (7) C29 H29A O2 C (6) C30 H30A O2 C (6) C31 C (7) O3 C (9) C31 C (7) O4 N (7) C32 C (8) O5 N (8) C32 H32A O6 N (7) C33 C (8) O7 N (6) C33 H33A O8 N (7) C34 C (8) O9 N (8) C34 H34A O10 C (6) C35 C (8) O11 N (8) C35 H35A O12 N (8) C37 C (8) O13 N (7) C38 H38A O14 N (7) C38 H38B O15 N (9) C39 C (8) O17 C (9) C39 H39A N1 C (6) C39 H39B N1 C (7) C41 C (8) N2 C (7) C41 C (8) N2 C (7) C42 C (8) N2 C (6) C42 H42A N3 C (7) C43 C (9) N3 C (7) C43 H43A N4 C (8) C44 C (8) N4 C (7) C44 H44A N4 C (7) C45 C (7) N5 C (6) C45 H45A N5 C (7) C47 C (8) N6 C (7) C47 H47A N6 C (7) C47 H47B N6 C (6) C48 C (8) sup-11

14 N7 C (7) C48 C (7) N7 C (7) C49 C (9) N8 C (7) C49 H49A N8 C (7) C50 C (9) N8 C (7) C50 H50A N9 C (8) C51 C (8) N10 C (8) C51 H51A N11 C (9) C52 C (9) N12 C (8) C52 H52A N13 C (7) C53 H53A N14 O (9) C54 C (8) N14 C (8) C54 H54A N15 C (11) C54 H54B N15 C (17) C55 C (9) N15 C (11) C55 C (8) N16 C (12) C56 C (11) N16 C (15) C56 H56A N16 C (19) C57 C (13) C1 C (8) C57 H57A C1 C (8) C58 C (13) C2 C (9) C58 H58A C2 H2A C59 C (12) C3 C (9) C59 H59A C3 H3A C60 H60A C4 C (9) C61 C (9) C4 H4A C61 C (9) C5 C (9) C62 C (9) C5 H5A C63 C (8) C7 C (8) C63 H63A C8 H8A C64 C (9) C8 H8B C65 C (9) C9 C (8) C65 H65A C9 H9A C67 C (8) C9 H9B C67 C (8) C11 C (9) C68 C (7) C11 C (8) C69 C (8) C12 C (9) C69 H69A C12 H12A C70 C (8) C13 C (10) C71 C (9) C13 H13A C71 H71A C14 C (9) C73 H73A C14 H14A C73 H73B C15 C (8) C73 H73C C15 H15A C74 H74A C17 C (8) C74 H74B C17 H17A C74 H74C C17 H17B C75 H75A C18 C (8) C76 H76A sup-12

15 C18 C (8) C76 H76B C19 C (9) C76 H76C C19 H19A C77 H77A C20 C (9) C77 H77B C20 H20A C77 H77C C21 C (10) O18 C (3) C21 H21A C78 H78A C22 C (9) C80 C (3) C22 H22A C80 H80A C23 H23A C80 H80B C24 C (8) C80 H80C C24 H24A C79 O (3) C24 H24B C79 H79A C25 C (9) C79 H79B C25 C (8) O19 H N3 Ni1 N (18) C31 C32 H32A N3 Ni1 N (17) C32 C33 C (6) N5 Ni1 N (18) C32 C33 H33A N3 Ni1 N (19) C34 C33 H33A N5 Ni1 N (16) C33 C34 C (6) N1 Ni1 N (18) C33 C34 H34A N3 Ni1 O (17) C35 C34 H34A N5 Ni1 O (15) C34 C35 C (5) N1 Ni1 O (17) C34 C35 H35A N7 Ni1 O (15) C36 C35 H35A N3 Ni1 O (16) C31 C36 N (5) N5 Ni1 O (16) C31 C36 C (5) N1 Ni1 O (16) N6 C36 C (5) N7 Ni1 O (16) N5 C37 N (5) O2 Ni1 O (16) N5 C37 C (5) C9 O1 C (4) N6 C37 C (4) C9 O1 Ni (3) O2 C38 C (4) C8 O1 Ni (3) O2 C38 H38A C38 O2 C (4) C37 C38 H38A C38 O2 Ni (3) O2 C38 H38B C39 O2 Ni (3) C37 C38 H38B C7 N1 C (5) H38A C38 H38B C7 N1 Ni (4) O2 C39 C (4) C1 N1 Ni (3) O2 C39 H39A C7 N2 C (4) C40 C39 H39A C7 N2 C (5) O2 C39 H39B C6 N2 C (5) C40 C39 H39B C10 N3 C (5) H39A C39 H39B C10 N3 Ni (4) N7 C40 N (5) C16 N3 Ni (4) N7 C40 C (5) C10 N4 C (5) N8 C40 C (5) C10 N4 C (5) C46 C41 C (5) sup-13

16 C11 N4 C (5) C46 C41 N (5) C37 N5 C (4) C42 C41 N (5) C37 N5 Ni (4) C43 C42 C (5) C31 N5 Ni (3) C43 C42 H42A C37 N6 C (4) C41 C42 H42A C37 N6 C (5) C42 C43 C (6) C36 N6 C (4) C42 C43 H43A C40 N7 C (5) C44 C43 H43A C40 N7 Ni (3) C45 C44 C (5) C46 N7 Ni (4) C45 C44 H44A C40 N8 C (4) C43 C44 H44A C40 N8 C (4) C44 C45 C (5) C41 N8 C (5) C44 C45 H45A O4 N9 O (6) C46 C45 H45A O4 N9 C (7) N7 C46 C (5) O5 N9 C (6) N7 C46 C (5) O7 N10 O (6) C41 C46 C (5) O7 N10 C (6) N6 C47 C (5) O6 N10 C (5) N6 C47 H47A O9 N11 O (7) C48 C47 H47A O9 N11 C (6) N6 C47 H47B O8 N11 C (7) C48 C47 H47B O11 N12 O (7) H47A C47 H47B O11 N12 C (6) C53 C48 C (5) O12 N12 C (6) C53 C48 C (5) O13 N13 O (6) C49 C48 C (5) O13 N13 C (5) C50 C49 C (6) O14 N13 C (6) C50 C49 H49A O16 N14 O (7) C48 C49 H49A O16 N14 C (8) C51 C50 C (6) O15 N14 C (7) C51 C50 H50A C75 N15 C (9) C49 C50 H50A C75 N15 C (9) C50 C51 C (6) C73 N15 C (11) C50 C51 H51A C77 N16 C (14) C52 C51 H51A C77 N16 C (11) C53 C52 C (6) C76 N16 C (12) C53 C52 H52A C2 C1 N (5) C51 C52 H52A C2 C1 C (6) C48 C53 C (5) N1 C1 C (5) C48 C53 H53A C3 C2 C (6) C52 C53 H53A C3 C2 H2A N8 C54 C (5) C1 C2 H2A N8 C54 H54A C2 C3 C (6) C55 C54 H54A C2 C3 H3A N8 C54 H54B C4 C3 H3A C55 C54 H54B C5 C4 C (7) H54A C54 H54B C5 C4 H4A C60 C55 C (7) sup-14

17 C3 C4 H4A C60 C55 C (6) C4 C5 C (6) C56 C55 C (6) C4 C5 H5A C57 C56 C (8) C6 C5 H5A C57 C56 H56A C5 C6 N (6) C55 C56 H56A C5 C6 C (5) C58 C57 C (8) N2 C6 C (5) C58 C57 H57A N1 C7 N (5) C56 C57 H57A N1 C7 C (5) C57 C58 C (9) N2 C7 C (5) C57 C58 H58A O1 C8 C (4) C59 C58 H58A O1 C8 H8A C58 C59 C (9) C7 C8 H8A C58 C59 H59A O1 C8 H8B C60 C59 H59A C7 C8 H8B C55 C60 C (7) H8A C8 H8B C55 C60 H60A O1 C9 C (4) C59 C60 H60A O1 C9 H9A O3 C61 C (7) C10 C9 H9A O3 C61 C (7) O1 C9 H9B C66 C61 C (6) C10 C9 H9B C63 C62 C (6) H9A C9 H9B C63 C62 N (6) N3 C10 N (5) C61 C62 N (6) N3 C10 C (5) C62 C63 C (6) N4 C10 C (5) C62 C63 H63A C12 C11 N (6) C64 C63 H63A C12 C11 C (5) C63 C64 C (6) N4 C11 C (5) C63 C64 N (6) C11 C12 C (6) C65 C64 N (5) C11 C12 H12A C66 C65 C (6) C13 C12 H12A C66 C65 H65A C14 C13 C (6) C64 C65 H65A C14 C13 H13A C65 C66 C (6) C12 C13 H13A C65 C66 N (6) C15 C14 C (6) C61 C66 N (6) C15 C14 H14A O10 C67 C (5) C13 C14 H14A O10 C67 C (6) C14 C15 C (6) C72 C67 C (5) C14 C15 H15A C69 C68 N (5) C16 C15 H15A C69 C68 C (5) N3 C16 C (6) N12 C68 C (5) N3 C16 C (5) C68 C69 C (5) C15 C16 C (6) C68 C69 H69A N2 C17 C (5) C70 C69 H69A N2 C17 H17A C69 C70 C (5) C18 C17 H17A C69 C70 N (5) N2 C17 H17B C71 C70 N (6) C18 C17 H17B C72 C71 C (6) sup-15

18 H17A C17 H17B C72 C71 H71A C19 C18 C (6) C70 C71 H71A C19 C18 C (5) C71 C72 C (6) C23 C18 C (5) C71 C72 N (6) C18 C19 C (6) C67 C72 N (5) C18 C19 H19A N15 C73 H73A C20 C19 H19A N15 C73 H73B C21 C20 C (7) H73A C73 H73B C21 C20 H20A N15 C73 H73C C19 C20 H20A H73A C73 H73C C20 C21 C (7) H73B C73 H73C C20 C21 H21A N15 C74 H74A C22 C21 H21A N15 C74 H74B C21 C22 C (6) H74A C74 H74B C21 C22 H22A N15 C74 H74C C23 C22 H22A H74A C74 H74C C22 C23 C (6) H74B C74 H74C C22 C23 H23A O17 C75 N (9) C18 C23 H23A O17 C75 H75A N4 C24 C (4) N15 C75 H75A N4 C24 H24A N16 C76 H76A C25 C24 H24A N16 C76 H76B N4 C24 H24B H76A C76 H76B C25 C24 H24B N16 C76 H76C H24A C24 H24B H76A C76 H76C C26 C25 C (6) H76B C76 H76C C26 C25 C (6) N16 C77 H77A C30 C25 C (6) N16 C77 H77B C25 C26 C (6) H77A C77 H77B C25 C26 H26A N16 C77 H77C C27 C26 H26A H77A C77 H77C C28 C27 C (7) H77B C77 H77C C28 C27 H27A O18 C78 N (16) C26 C27 H27A O18 C78 H78A C29 C28 C (6) N16 C78 H78A C29 C28 H28A C79 C80 H80A C27 C28 H28A C79 C80 H80B C28 C29 C (6) H80A C80 H80B C28 C29 H29A C79 C80 H80C C30 C29 H29A H80A C80 H80C C29 C30 C (6) H80B C80 H80C C29 C30 H30A O19 C79 C (3) C25 C30 H30A O19 C79 H79A C36 C31 C (5) C80 C79 H79A C36 C31 N (5) O19 C79 H79B C32 C31 N (5) C80 C79 H79B C33 C32 C (5) H79A C79 H79B C33 C32 H32A C79 O19 H sup-16

19 Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C2 H2A O10 i (8) 144 C8 H8A O (9) 173 C8 H8B O12 ii (9) 140 C9 H9A O12 ii (9) 142 C9 H9B O (7) 156 C17 H17A O8 ii (9) 161 C38 H38A O (8) 164 C38 H38B O10 i (7) 133 C39 H39A O10 i (9) 135 C39 H39A O11 i (10) 137 C43 H43A O16 iii (8) 144 C56 H56A O11 i (11) 155 C65 H65A O (10) 169 C77 H77B O (15) 150 Symmetry codes: (i) x 1, y+3/2, z 1/2; (ii) x+2, y+2, z+1; (iii) x+2, y+1, z+1. sup-17