research papers\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

IUCrJ
Volume 10| Part 3| May 2023| Pages 321-328
ISSN: 2052-2525
https://doi.org/10.1107/S2052252523002385

Hierarchical packing of racemic metallo­supra­molecular cages with Ni(II)-based triple-stranded helicate building blocks

crossmark logo
Thanh Nhan Nguyen,a Anh Ngoc Nguyen,a Ngoc Minh Tran,a In-Hyeok Parkb* and Hyojong Yooa*

aDepartment of Materials Science and Chemical Engineering, Hanyang University, Ansan, Gyeonggi-do 15588, Republic of Korea, and bGraduate School of Analytical Science and Technology (GRAST), Chungnam National University, Daejeon 34134, Republic of Korea
*Correspondence e-mail: ipark@cnu.ac.kr, hjhaha73@hanyang.ac.kr

Edited by C.-Y. Su, Sun Yat-Sen University, China (Received 15 November 2022; accepted 12 March 2023; online 31 March 2023)

Three novel hierarchical Ni-based metallosupramolecular cages were constructed from nickel ions, pyridine di­carboxyl­ates and isophthalate derivative ligands (the substituents on C5 of isophthalate are methyl, tert-butyl and bromo groups). In every cage, two multinuclear nickel clusters, assembled from four nickel atoms and three pyridine di­carboxyl­ate ligands, are interlinked by three isophthalate-derivative ligands to form a nickel-based triple-stranded helicate (TSH), which then becomes the supramolecular building block for the fabrication of a metallocage. Six homochiral TSH supramolecular building blocks, either left (M)-handed or right (P)-handed, are connected by four linking nickel atoms to generate M6 and P6 discrete racemic cage molecules (M6 – cage with six M-TSHs; P6 – cage with six P-TSHs). The crystal packing of the racemic cages was characterized by single-crystal X-ray diffraction. An additional cobalt-based molecular cage with 5-methyl­isophthalate bridging ligands was synthesized for host–guest interaction studies. The methyl groups in Co- and Ni-TSH can act as guest units to be accommodated in the cone-shaped metal clusters (host) of an adjacent cage.

CCDC references: 2209422; 2209425; 2209565; 2209566

Similar articles

1. Introduction

The fabrication of metal–organic platforms with high degrees of hierarchy, structural diversity and complexity has recently attracted significant interest in solid-state materials (Yoo et al., 2015[Yoo, H., Lee, J., Kang, P. & Choi, M. G. (2015). Dalton Trans. 44, 14213-14216.]; Nouar et al., 2008[Nouar, F., Eubank, J. F., Bousquet, T., Wojtas, L., Zaworotko, M. J. & Eddaoudi, M. (2008). J. Am. Chem. Soc. 130, 1833-1835.]; Chakraborty et al., 2021[Chakraborty, G., Park, I., Medishetty, R. & Vittal, J. J. (2021). Chem. Rev. 121, 3751-3891.]). To access these advanced architectures, employing coordination-driven self-assembly of predefined, well organized supramolecular building blocks (SBBs) as direct constructing units has proven to be a more effective method compared with the conventional approach of using molecular building blocks (MBBs), that is, multinuclear clusters and organic ligands (Chen et al., 2015[Chen, L., Chen, Q., Wu, M., Jiang, F. & Hong, M. (2015). Acc. Chem. Res. 48, 201-210.]; Nouar et al., 2008[Nouar, F., Eubank, J. F., Bousquet, T., Wojtas, L., Zaworotko, M. J. & Eddaoudi, M. (2008). J. Am. Chem. Soc. 130, 1833-1835.]). Indeed, to create a high-order structure, suitable building units should possess a high degree of symmetry and connectivity which can be more feasibly obtained from SBBs than from MBBs (Nouar et al., 2008[Nouar, F., Eubank, J. F., Bousquet, T., Wojtas, L., Zaworotko, M. J. & Eddaoudi, M. (2008). J. Am. Chem. Soc. 130, 1833-1835.]). To date, several hierarchical architectures have been created by the coordination-driven self-assembly of SBBs (Perry IV et al., 2009[Perry IV, J. J., Perman, J. A. & Zaworotko, M. J. (2009). Chem. Soc. Rev. 38, 1400-1417.]; Chen et al., 2015[Chen, L., Chen, Q., Wu, M., Jiang, F. & Hong, M. (2015). Acc. Chem. Res. 48, 201-210.]; Nouar et al., 2008[Nouar, F., Eubank, J. F., Bousquet, T., Wojtas, L., Zaworotko, M. J. & Eddaoudi, M. (2008). J. Am. Chem. Soc. 130, 1833-1835.]). These SBBs are mostly assembled into one-dimensional polymers (Yoo et al., 2015[Yoo, H., Lee, J., Kang, P. & Choi, M. G. (2015). Dalton Trans. 44, 14213-14216.]; Mai et al., 2018[Mai, H. D., Lee, I. & Yoo, H. (2018). Chem. Asian J. 13, 1915-1919.]; Hong et al., 2000[Hong, M., Zhao, Y., Su, W., Cao, R., Fujita, M., Zhou, Z. & Chan, A. S. C. (2000). Angew. Chem. Int. Ed. 39, 2468-2470.]; Li et al., 2011[Li, N., Jiang, F., Chen, L., Li, X., Chen, Q. & Hong, M. (2011). Chem. Commun. 47, 2327-2329.]; Liu et al., 2012[Liu, T., Chen, Y., Yakovenko, A. A. & Zhou, H. (2012). J. Am. Chem. Soc. 134, 17358-17361.]; Sikligar et al., 2021[Sikligar, K., Kelley, S. P., Shao, L., Baker, G. A. & Atwood, J. L. (2021). Cryst. Growth Des. 21, 1891-1897.]) or metal–organic frameworks (Pang et al., 2014[Pang, J., Jiang, F., Wu, M., Yuan, D., Zhou, K., Qian, J., Su, K. & Hong, M. (2014). Chem. Commun. 50, 2834-2836.]; Qian et al., 2014[Qian, J., Jiang, F., Zhang, L., Su, K., Pan, J., Li, Q., Yuan, D. & Hong, M. (2014). Chem. Commun. 50, 1678-1681.]; Li et al., 2009[Li, J.-R., Timmons, D. J. & Zhou, H.-C. (2009). J. Am. Chem. Soc. 131, 6368-6369.]; Tian et al., 2014[Tian, D., Chen, Q., Li, Y., Zhang, Y., Chang, Z. & Bu, X. (2014). Angew. Chem. Int. Ed. 53, 837-841.]; Park et al., 2007[Park, J., Hong, S., Moon, D., Park, M., Lee, K., Kang, S., Zou, Y., John, R. P., Kim, G. H. & Lah, M. S. (2007). Inorg. Chem. 46, 10208-10213.]; Nouar et al., 2008[Nouar, F., Eubank, J. F., Bousquet, T., Wojtas, L., Zaworotko, M. J. & Eddaoudi, M. (2008). J. Am. Chem. Soc. 130, 1833-1835.]).

In supramolecular chemistry, the chirality investigation of discrete metallosupramolecules has received considerable attention due to its potential in chiral recognition, asymmetric catalysis, enantiomer separation and so on (Chen et al., 2017[Chen, L. J., Yang, H. B. & Shionoya, M. (2017). Chem. Soc. Rev. 46, 2555-2576.]). Chirality, in general, can be introduced into coordination platforms via two basic approaches: (1) a `hard' approach harnesses optically pure chiral building blocks to generate predetermined chirality (Du et al., 2022[Du, X. S., Han, Y. & Chen, C. F. (2022). Chem. Commun. 58, 1326-1329.]; Zhu et al., 2022[Zhu, Q. Y., Zhou, L. P., Cai, L. X., Hu, S. J., Li, X. Z. & Sun, Q. F. (2022). Inorg. Chem. 61, 16814-16821.]); (2) a `soft' approach utilizes achiral building blocks to produce chirality (Wang et al., 2022[Wang, M.-Y., Yuan, Y.-Y., Qi, Z.-Q., Chen, J.-Y., Jiang, Z.-G. & Zhan, C.-H. (2022). Chem. Mater. 34, 10501-10508.]), and the chirality disappears on dissociation of metal–ligand bonds (Chen et al., 2017[Chen, L. J., Yang, H. B. & Shionoya, M. (2017). Chem. Soc. Rev. 46, 2555-2576.]). It was found that the second approach generally results in a racemic mixture (Zhang et al., 2020[Zhang, Y. W., Bai, S., Wang, Y. Y. & Han, Y. F. (2020). J. Am. Chem. Soc. 142, 13614-13621.]; Wang et al., 2020[Wang, L. J., Li, X., Bai, S., Wang, Y. Y. & Han, Y. F. (2020). J. Am. Chem. Soc. 142, 2524-2531.]), both in solution and in the solid state since the chirality depends largely on metal coordination bonds, which are commonly labile in solution [thus allowing the interconversion of enantiomers (Chen et al., 2017[Chen, L. J., Yang, H. B. & Shionoya, M. (2017). Chem. Soc. Rev. 46, 2555-2576.])].

Discrete metallosupramolecular cages (metallocages) with well defined cavities have been extensively studied over the past decades owing to their structural aesthetics (Yoshizawa et al., 2009[Yoshizawa, M., Klosterman, J. K. & Fujita, M. (2009). Angew. Chem. Int. Ed. 48, 3418-3438.]; McConnell, 2022[McConnell, A. J. (2022). Chem. Soc. Rev. 51, 2957-2971.]; Yong et al., 2022[Yong, M. T., Linder-Patton, O. M. & Bloch, W. M. (2022). Inorg. Chem. 61, 12863-12869.]; Kim et al., 2022[Kim, D., Kim, G., Han, J. & Jung, O.-S. (2022). Bull. Korean Chem. Soc. 43, 1019-1031.]) and intriguing applications in host–guest chemistry (Browne et al., 2013[Browne, C., Brenet, S., Clegg, J. K. & Nitschke, J. R. (2013). Angew. Chem. Int. Ed. 52, 1944-1948.]; Jia et al., 2020[Jia, F., Schröder, H. V., Yang, L. P., von Essen, C., Sobottka, S., Sarkar, B., Rissanen, K., Jiang, W. & Schalley, C. A. (2020). J. Am. Chem. Soc. 142, 3306-3310.]; Rizzuto et al., 2019[Rizzuto, F. J., von Krbek, L. K. S. & Nitschke, J. R. (2019). Nat. Rev. Chem. 3, 204-222.]; Huang et al., 2022[Huang, X., Chen, L., Jin, J., Kim, H., Chen, L., Zhang, Z., Yu, L., Li, S. & Stang, P. J. (2022). Inorg. Chem. 61, 20237-20242.]), modification of the chemical reactivity of guests (Fang et al., 2019[Fang, Y., Powell, J. A., Li, E., Wang, Q., Perry, Z., Kirchon, A., Yang, X., Xiao, Z., Zhu, C., Zhang, L., Huang, F. & Zhou, H. C. (2019). Chem. Soc. Rev. 48, 4707-4730.]; Whitehead et al., 2013[Whitehead, M., Turega, S., Stephenson, A., Hunter, C. A. & Ward, M. D. (2013). Chem. Sci. 4, 2744-2751.]) [activating guests for reactions (Hastings et al., 2010[Hastings, C. J., Pluth, M. D., Bergman, R. G. & Raymond, K. N. (2010). J. Am. Chem. Soc. 132, 6938-6940.]) or stabilizing reactive guests (Mal et al., 2009[Mal, P., Breiner, B., Rissanen, K. & Nitschke, J. R. (2009). Science, 324, 1697-1699.]; Galan & Ballester, 2016[Galan, A. & Ballester, P. (2016). Chem. Soc. Rev. 45, 1720-1737.])], or gas storage (Duriska et al., 2009[Duriska, M. B., Neville, S. M., Lu, J., Iremonger, S. S., Boas, J. F., Kepert, C. J. & Batten, S. R. (2009). Angew. Chem. Int. Ed. 48, 8919-8922.]). Most of these cages are built directly from MBBs, with a low degree of hierarchy and complexity (Pullen et al., 2021[Pullen, S., Tessarolo, J. & Clever, G. H. (2021). Chem. Sci. 12, 7269-7293.]; Lee et al., 2023[Lee, B., Moon, D. & Park, J. (2023). Bull. Korean Chem. Soc. 44, 55-59.]). Few studies have reported the fabrication of higher-order supramolecular cages using the SBB approach (Mai et al., 2017[Mai, H. D., Kang, P., Kim, J. K. & Yoo, H. (2017). Sci. Rep. 7, 43448.]; Kang et al., 2018[Kang, P., Mai, H. D. & Yoo, H. (2018). Dalton Trans. 47, 6660-6665.]). These cage structures share similar features in terms of using cobalt-based triple-stranded helicates (TSHs) as SBBs for the formation of hierarchical cobalt-based supramolecular cages. In a single building block, cobalt ions and 2,6-pyridine di­carboxyl­ates (PDAs) were assembled into a tetrahedral cobalt cluster, and two clusters were interconnected by three isophthalate derivative bridging ligands to generate a TSH (Mai et al., 2019[Mai, H. D., Tran, N. M. & Yoo, H. (2019). Coord. Chem. Rev. 387, 180-198.]; Tran & Yoo, 2020[Tran, N. M. & Yoo, H. (2020). Dalton Trans. 49, 11819-11827.]). Six TSHs were connected via four linking cobalt atoms to create a discrete cobalt-based supramolecular cage with a vast number of metal moieties and functional groups from organic ligands (Mai et al., 2019[Mai, H. D., Tran, N. M. & Yoo, H. (2019). Coord. Chem. Rev. 387, 180-198.], 2017[Mai, H. D., Kang, P., Kim, J. K. & Yoo, H. (2017). Sci. Rep. 7, 43448.]).

To create more hierarchical supramolecular platforms with greater structural diversity and functionality for various purposes, Ni(II) salts were employed as the metal source, and three types of bridging ligands were employed for TSH formation, namely 5-methyl isophthalate (CH3-PTA), 5-tert-butyl isophthalate (t-butyl-PTA) and 5-bromo isophthalate (Br-PTA). Although Co(II) and Ni(II) were used for constructing TSHs (Le et al., 2019[Thi Le, V. C., Mai, H. D., Kang, P. & Yoo, H. (2019). Chem. Eur. J. 25, 2472-2476.]), the ability of nickel-TSH to form metallocages has not been reported. Moreover, although t-butyl-PTA and Br-PTA have been employed for the formation of cobalt hierarchical cages from Co-TSH, the ability of CH3-PTA to form cages with high-order assemblies has not been reported. Herein, the successful syntheses of three new nickel-based supramolecular cages from smaller Ni-TSH building blocks with CH3-PTA, t-butyl-PTA and Br-PTA bridging ligands are reported. The coordination-driven self-assembly of six homochiral TSHs of either left (M)-handed or right (P)-handed configuration resulted in the formation of M6 and P6 cages in the form of a racemate (M6 – cage with six M-TSHs; P6 – cage with six P-TSHs). The crystal packing of the resulting racemic cages was fully characterized. To the best of our knowledge, this is the first study to report the synthesis of nickel-based supramolecular cages using the SBB approach. In particular, the ability to form host–guest interactions between the methyl groups on one cage and the metal cluster of an adjacent cage was verified.

2. Experimental

2.1. Materials

Nickel(II) nitrate hexahydrate [Ni(NO3)2·6H2O, 97%, Sigma–Aldrich], nickel(II) acetate tetrahydrate [Ni(OAc)2·4H2O, 98%, Sigma–Aldrich], cobalt(II) nitrate hexahydrate [Co(NO3)2·6H2O, 98%, Sigma–Aldrich], 2,6-pyridinedi­carb­oxy­lic acid (H2PDA, C7H5NO4, 99%, Sigma–Aldrich), 5-tert-butyl isophthalic acid (t-butyl-H2PTA, C12H14O4, 99%, Sigma–Aldrich), 5-methyl isophthalic acid (CH3-H2PTA, C9H8O4, 97%, Sigma–Aldrich), 5-bromo­isophthalic acid (Br-H2PTA, C8H5O4Br, 97%, Sigma–Aldrich), methanol (Samchun, 99.5%), N,N-di­methyl­formamide (DMF, 99.99%, Burdick & Jackson) and acetone (99.96%, Burdick & Jackson) were used as received.

2.2. Syntheses

2.2.1. Synthesis of {[Ni8(PDA)4(H0.33PDA)2(CH3-PTA)3(DMF)6]6-[Ni(H2O)3]4·xsolvent} (1)

DMF solutions of Ni(NO3)2·6H2O (1.2 ml, 0.05 M), H2PDA (0.6 ml, 0.05 M) and CH3-H2PTA (0.3 ml, 0.05 M) were mixed in a 4 ml glass vial at room temperature (RT). The vial was sealed, heated to 100°C (heating rate 2.67°C min−1), maintained for 24 h and then cooled to 30°C (cooling rate 0.25°C min−1). Complex 1 was obtained as green rectangular crystals. The solid yield was 44.3% based on H2PDA. Analytical calculation for C486H456N60O274Ni52 as {[Ni8(PDA)4(H0.33PDA)2(CH3-PTA)2(DMF)4(H2O)2]6-[Ni(H2O)3]4·(H2O)10}: calculated: C: 40.01, H: 3.13, N: 5.76; obtained: C: 39.71, H: 3.52, N: 5.36.

2.2.2. Synthesis of {[Ni8(PDA)4(H0.33PDA)2(t-butyl-PTA)3(DMF)4(H2O)2]6-[Ni(H2O)3]4·xsolvent} (2)

DMF solutions of Ni(OAc)2·6H2O (0.9 ml, 0.05 M), H2PDA (0.6 ml, 0.05 M) and t-butyl-H2PTA (0.3 ml, 0.05 M) were mixed in a 4 ml glass vial at RT. The vial was sealed, heated to 100°C (heating rate 2.67°C min−1), maintained for 24 h and then cooled to 30°C (cooling rate 0.25°C min−1). Complex 2 was obtained as green rectangular crystals. The solid yield was 32.7% based on H2PDA. Analytical calculation for C540H588N60O286Ni52 as {[Ni8(PDA)4(H0.33PDA)2(t-butyl-PTA)3(DMF)4(H2O)2]6-[Ni(H2O)3]4·(H2O)22}: calculated: C: 41.68, H: 3.78, N: 5.40; obtained: C: 41.25, H: 4.16, N: 5.56.

2.2.3. Synthesis of {[Ni8(PDA)4(H0.33PDA)2(Br-PTA)3(DMF)6]6-[Ni(H2O)3]4·xsolvent} (3)

DMF solutions of Ni(NO3)2·6H2O (0.9 ml, 0.05 M), H2PDA (0.6 ml, 0.05 M) and Br-H2PTA (0.3 ml, 0.05 M) were mixed in a 4 ml glass vial at RT. The vial was sealed, heated to 100°C (heating rate 2.67°C min–1), maintained for 24 h and then cooled to 30°C (cooling rate 0.25 °C min–1). The solid yield of the reaction was 42.8% based on H2PDA. Analytical calculation for C468H394N60O270Ni52Br18 as {[Ni8(PDA)4(H0.33PDA)2(Br-PTA)3(DMF)4(H2O)2]6-[Ni(H2O)3]4·(H2O)6}: calculated: C: 35.84, H: 2.51, N: 5.36; obtained: C: 36.28, H: 2.91, N: 5.33.

2.2.4. Synthesis of {[Co8(PDA)4(H0.33PDA)2(CH3-PTA)3(DMF)6]6-[Co(H2O)3]4·xsolvent} (4)

DMF solutions of Co(NO3)2·6H2O (1.2 ml, 0.05 M), H2PDA (0.6 ml, 0.05 M), CH3-H2PTA (0.3 ml, 0.05 M) and methanol (0.1 ml) were mixed in a 4 ml glass vial at RT. The vial was sealed, heated to 100°C (heating rate 2.67°C min–1), maintained for 24 h and then cooled to 30°C (cooling rate 0.25°C min–1). Complex 4 was obtained as purple rectangular crystals. The solid yield, calculated based on H2PDA, was 42.5%. Analytical calculation for C510H490N54O278Co52 as {[Co8(PDA)4(H0.33PDA)2(CH3-PTA)3(DMF)3(H2O)3]6-[Co(H2O)3]4·(CH3OH)14}: calculated: C: 41.13, H: 3.29, N: 5.08; obtained: C: 41.44, H: 3.37, N: 4.92.

2.3. Instrumentation

Thermogravimetric analysis (TGA) was conducted from RT to 600°C at a heating rate of 10°C min−1 under a nitro­gen atmosphere using a TA instrument STD Q600 analyser. Powder X-ray diffraction (PXRD) was conducted using synchrotron radiation (wavelength: 1.1 Å) in a focused beam configuration in the 2θ range 2–20° at 298 K. The simulated PXRD patterns were obtained from single-crystal X-ray diffraction (SCXRD) data using the Mercury software (version 3.8; Macrae et al., 2020[Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226-235.]). X-ray photoelectron spectroscopy (XPS) measurements for 1 and 2 were performed on an R3000 spectrometer (VG SCIENTA, UK), and XPS measurements for 3 and 4 were performed on a K-ALPHA spectrometer (Thermo VG, UK) with monochromatic Al Kα X-ray radiation as the X-ray source. Magnetic measurements of the compounds were conducted using a Quantum Design MPMS3 magnetometer in the temperature range 3 K ≤ T ≤ 300 K under an applied field of 1000 Oe.

2.4. X-ray crystallography

The light green crystals of 1 (0.172 × 0.132 × 0.128 mm), 2 (0.097 × 0.093 × 0.069 mm3) and 3 (0.246 × 0.241 × 0.197 mm), and the purple crystals of 4 (0.169 × 0.114 × 0.111 mm) were mounted on a MiTeGen MicroMount. Diffraction data for these crystals were collected at 100 K on a Rayonix MX225HS detector with an Si(111) double-crystal monochromator equipped with a synchrotron radiation source (0.70000 Å) at the 2D Supramolecular Crystallography Beamline (2D SMC), Pohang Accelerator Laboratory (PAL), Pohang, Republic of Korea. All calculations for the structure determination were performed using the SHELXTL2018/3 package (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]).

3. Results and discussion

Treatment of 4 equivalents of Ni(NO3)2·6H2O, 2 equivalents of 2,6-pyridinedi­carb­oxy­lic acid (H2PDA) and 1 equivalent of 5-methyl isophthalic acid (CH3-H2PTA) in di­methyl­formamide (DMF) at 100°C for 24 h led to the formation of {[Ni8(PDA)4(H0.33PDA)2(CH3-PTA)3(DMF)6]6-[Ni(H2O)3]4·xsolvent} (1) (Scheme 1).[link]

[Scheme 1]

The solid-state structure of 1 was determined by SCXRD analysis and refined in the space group Fd3 (Table 1[link]). Discrete supramolecular cage 1, comprised of six TSHs interconnected by four linking nickel atoms (Ni5), has the longest transverse distance of ca 39 Å (Figs. 1[link] and S1 of the supporting information). In a single Ni-TSH building block, each tetrahedral nickel cluster ({Ni4}), formed through the assembly of four nickel ions and three PDA ligands, is diagonally connected to another nickel cluster by three bridging CH3-PTA ligands. Each nickel cation in the cluster adopts a pseudooctahedral coordination environment. The nickel site at the centre is linked to three terminal nickel sites by three PDA ligands and linked to the other central nickel atoms by three CH3-PTA ligands. Each terminal nickel, in addition to coordinating with two PDA ligands and one CH3-PTA ligand, bonds with one DMF molecule [Figs. 1[link](a) and S1]. Note that the type of coordinated solvent (DMF or H2O) in terminal nickel atoms may not be the same in every experiment. Also, the PDA ligands are not completely deprotonated so as to balance the charge of the overall structure (as indicated in the chemical formula of 1). Since the tetrahedral nickel clusters are assembled into either clockwise or counterclockwise isomers, the resulting TSHs, built from two metal clusters of the same chirality, can have either a left (M)-handed or right (P)-handed configuration [Fig. 2[link](a)]. Generally, the assembly of different chiral metal centres or clusters can generate helicates or mesocates (Albrecht, 2000[Albrecht, M. (2000). Chem. Eur. J. 6, 3485-3489.]; Nguyen et al., 2022[Nguyen, T. N., Tran, N. M., Park, I. H. & Yoo, H. (2022). ACS Omega, 7, 13067-13074.]). Whether a helicate or mesocate is obtained depends heavily on the ligand rigidity (Albrecht, 2000[Albrecht, M. (2000). Chem. Eur. J. 6, 3485-3489.]). So far, all our TSHs obtained in which the bridging derivative ligands are short and rigid (a one-benzene ring system) are in helicate form (with either M- or P-configuration) (Yoo et al., 2015[Yoo, H., Lee, J., Kang, P. & Choi, M. G. (2015). Dalton Trans. 44, 14213-14216.]; Mai et al., 2017[Mai, H. D., Kang, P., Kim, J. K. & Yoo, H. (2017). Sci. Rep. 7, 43448.], 2018[Mai, H. D., Lee, I. & Yoo, H. (2018). Chem. Asian J. 13, 1915-1919.]; Kang et al., 2018[Kang, P., Mai, H. D. & Yoo, H. (2018). Dalton Trans. 47, 6660-6665.]; Le et al., 2019[Thi Le, V. C., Mai, H. D., Kang, P. & Yoo, H. (2019). Chem. Eur. J. 25, 2472-2476.]).

Table 1
Crystal data and structure refinements for 1, 2, 3 and 4

  1 2 3 4
Formula C522H496N72O264Ni52 C540H544N60O264Ni52 C504H442N72O264Ni52Br18 C522H496N72O264Co52
Formula weight 15054.80 15151.24 16222.57 15066.24
Crystal system Cubic Cubic Cubic Cubic
Space group Fd3 Fd3 Fd3 Fd3
a (Å) 57.933 (7) 58.600 (7) 58.069 (7) 58.380 (7)
b (Å) 57.933 (7) 58.600 (7) 58.069 (7) 58.380 (7)
c (Å) 57.933 (7) 58.600 (7) 58.069 (7) 58.380 (7)
α (°) 90 90 90 90
β (°) 90 90 90 90
γ (°) 90 90 90 90
V (Å3) 194435 (67) 201234 (70) 195809 (68) 198973 (69)
Z 8 8 8 8
Dcalc(g cm−3) 1.029 1.000 1.101 1.006
μ (mm−1) 1.042 0.970 1.772 0.870
F(000) 61600.0 62176.0 65344.0 61184.0
Reflections collected 275607 319601 31600 311832
Independent reflections 15921 [Rint = 0.0722] 17258 [Rint = 0.0791] 16050 [Rint = 0.0137] 17071 [Rint = 0.0367]
GOF 1.053 1.025 1.026 1.067
R1, wR2 [I ≥ 2σ(I)] 0.0408, 0.1171 0.0500, 0.1555 0.0592, 0.1607 0.0413, 0.1144
R1, wR2 (all data) 0.0484, 0.1209 0.0639, 0.1650 0.0653, 0.1646 0.0457, 0.1171
CCDC nos. 2209422 2209565 2209425 2209566
[Figure 1]
Figure 1
(a) X-ray crystal structure of 1 viewed along its C2 axis of symmetry. The four linking nickel atoms are illustrated by green balls. One TSH building block is highlighted and shown in the inset. Ni, C, O and N atoms are shown in green, grey, red and blue, respectively. All the disorder components, coordinated solvents and hydrogen atoms were omitted for clarity (with the exception of hydrogen atoms on the methyl groups of the highlighted TSH, which are presented by orange balls). (b) X-ray crystal structure of 1 viewed along its C3 axis of symmetry with its longest transverse distance and the confined space at the centre.
[Figure 2]
Figure 2
(a) Representation of a unit cell of 1 with M6 and P6 shown in green and red, respectively. (b) Illustration showing the arrangement of M6 (green balls) and P6 (red balls) in a unit cell with intertwisted M6- and P6-tetrahedron arrangements. (c) Illustration showing the arrangement of four M6 tetrahedrons at four vertexes of a P6 tetrahedron.

For generating a discrete cage, six Ni-TSHs of the same chirality (homochiral) are required, and they are interconnected through the coordination with Ni5 atoms at the unoccupied carboxyl­ate oxygen atoms from the PDA ligands on the nickel cluster. Each Ni5, possessing a pseudo-octahedral coordination geometry, binds with three coordinated water molecules and three other TSHs through the unoccupied carboxyl­ate oxygen atoms in facial (fac) mode [Fig. S1(a)]. Four Ni5 atoms within a cage are arranged into a tetrahedron and separated from each other by a distance of 11.65 Å. The similar coordination-driven cage assemblies were previously reported in the solid-state structures in which the metal ion was cobalt and the substituents (on PTA ligands) were t-butyl, bromo and iodo groups (Mai et al., 2017[Mai, H. D., Kang, P., Kim, J. K. & Yoo, H. (2017). Sci. Rep. 7, 43448.]; Kang et al., 2018[Kang, P., Mai, H. D. & Yoo, H. (2018). Dalton Trans. 47, 6660-6665.]). Since there are two configurations of TSH (M- and P-), two types of cage, M6 and P6 (M6 – cage with six M-TSHs; P6 – cage with six P-TSHs), can be obtained with opposite chiralities. Each metallocage possesses a confined space of a pseudo-regular tetrahedron with four Ni5 at each vertex, and an edge distance (Ni5⋯Ni5 separation) of 17.11 Å (Fig. S2). The void volume of 1, including the inner void and the space between cages, calculated by Olex2 is 119519.9 Å3 (Dolomanov et al., 2009[Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339-341.]).

The crystal packing of 1 indicated that each unit cell of 1 is built from eight cages packed together, of which four are M6 and four are P6 [Fig. 2[link](a)]. An M6 (or P6) is exposed to four other P6 (or M6) cages arranged at four vertices of a tetrahedron (Fig. S3). Thus, each unit cell of 1 is comprised of two intertwisted M6 and P6 tetrahedrons [Fig. 2[link](b)]. When considering a larger range, four M6 (or P6) cages at the vertices of an M6 (or P6) tetrahedron become the centres of the other P6 (or M6) tetrahedrons [Fig. 2[link](c)]. This assembly pattern is extended in three dimensions to create a well arranged crystal structure. In particular, the methyl group in TSH was found to have the ability to create host–guest interactions between neighbouring racemic cage molecules, in which the methyl group from one cage can be accommodated in a cone-shaped metal cluster of the adjacent cage (Fig. 3[link]).

[Figure 3]
Figure 3
Two racemic cages of 1 with the host–guest interactions between the cone-shaped cavity of one molecular cage and the methyl group of the adjacent cage (shown in the inset).

The phase purity of as-synthesized 1 was determined using PXRD (Fig. S4). The observed and expected PXRD patterns of 1 are considerably similar. The TGA curve of 1 exhibits a weight loss below 350°C attributed to the removal of trapped and coordinated solvents, and a sharp weight loss at approximately 400°C attributed to the decomposition of the organic ligands (Fig. S5) (Yoo et al., 2015[Yoo, H., Lee, J., Kang, P. & Choi, M. G. (2015). Dalton Trans. 44, 14213-14216.]). XPS measurements confirmed the presence of Ni, C, O and N atoms in 1 [Fig. S6(a)]. The oxidation state of the nickel ions was determined to be +2 by the presence of two strong peaks at 856.7 and 874.2 eV correlating to Ni 2p3/2 and Ni 2p1/2, respectively [Fig. S6(b)] (Le et al., 2019[Thi Le, V. C., Mai, H. D., Kang, P. & Yoo, H. (2019). Chem. Eur. J. 25, 2472-2476.]; Kang & Yoo, 2020[Kang, P. & Yoo, H. (2020). Inorg. Chem. Front. 7, 905-910.]). The bond valence sum calculation for the nickel ions also indicates a +2 oxidation state (Table S1) (IUCr, 2021[IUCr (2021). Bond valence parameters. https://www.iucr.org/resources/data/datasets/bond-valence-parameters.]; Brown, 2002[Brown, I. D. (2002). The Chemical Bond in Inorganic Chemistry: the Bond Valence Model. New York: Oxford University Press.]). The temperature-dependent magnetization was measured to confirm the oxidation state of the metal ions in 1 using a Quantum Design MPMS3 magnetometer in the temperature range 3 K ≤ T ≤ 300 K under an applied field of 1000 Oe [Fig. S7(a)]. By applying the Curie–Weiss law for the fitting of 1/χ versus T, the Weiss constant was determined to be θ = −11.36 K for 1 [Fig. S7(b)], suggesting a weak antiferromagnetic interaction between metal ions (Hatscher et al., 2005[Hatscher, S., Schilder, H., Lueken, H. & Urland, W. (2005). Pure Appl. Chem. 77, 497-511.]). The χMT value at 300 K was 1.42 emu K mol−1 for 1 [Fig. S7(c)], corresponding to μeff = 3.37 B.M, which is in the acceptable range of experimentally observed octahedral Ni(II) ions (Earnshaw, 1968[Earnshaw, A. (1968). Introduction to Magneto Chemistry. London: Academic Press.]).

Two other nickel-based molecular cages were also successfully synthesized using 5-tert-butyl isophthalic acid (t-butyl-H2PTA) and 5-bromo isophthalic acid (Br-H2PTA) as bridging ligands, denoted 2 and 3, respectively. Specifically, 3 equivalents of Ni(OAc)2·4H2O, 2 equivalents of H2PDA and 1 equivalent of t-butyl-H2PTA in DMF were heated at 100°C for 24 h to form {[Ni8(PDA)4(H0.33PDA)2(t-butyl-PTA)3(DMF)4(H2O)2]6-[Ni(H2O)3]4·xsolvent} (2). Similarly, the treatment of 3 equivalents of Ni(NO3)2·6H2O, 2 equivalents of H2PDA and 1 equivalent of Br-H2PTA in DMF at 100°C for 24 h afforded {[Ni8(PDA)4(H0.33PDA)2(Br-PTA)3(DMF)6]6-[Ni(H2O)3]4·xsolvent} (3) (Scheme 1).

The self-assembly processes of 2 and 3 are analogous to that of 1 with the interconnection of six homochiral TSH building blocks [Figs. 4[link](a) and 4[link](c)]. Their packing modes are alike with the intertwining of M6 and P6 tetrahedrons [Figs. S8(a), S8(b) and S8(d)]. The tert-butyl and bromo groups of the TSHs in 2 and 3 could also engage in the host–guest interactions between racemic cages [Fig. 4[link](b) and 4[link](d)]. The resemblance in the PXRD patterns of 1, 2 and 3 (Fig. S4) further confirms that 1–3 are isomorphous. The TGA curves of 2 and 3 are not significantly different from that of 1, and they indicate two main steps of chemical change: the removal of trapped and coordinated solvent molecules below 350°C and the ligand decomposition above 350°C (Fig. S5). XPS analysis [Figs. S6(d)–S6(f)], the calculated valence values (Table S1) and magnetic measurements [Figs. S7(d)–S7(f) and S7(g)–S7(l)] highlight that nickel ions in 2 and 3 have an oxidation state of +2. So far, we have been unable to obtain satisfactory UV–vis spectra of nickel-based supramolecular cages owing to the low solubility of these compounds in common organic solvents.

[Figure 4]
Figure 4
X-ray crystal structure of (a) 2 and (c) 3. Host–guest interactions between two adjacent racemic cages of (b) 2 and (d) 3. The balls in grey, yellow and brown represent C, H and Br, respectively.

To further investigate the ability of the methyl group to form host–guest interactions between racemic cages, a cobalt-based supramolecular cage was obtained on heating 4 equivalents of Co(NO3)2·6H2O, 2 equivalents of H2PDA and 1 equivalent of CH3-H2PTA in DMF with a small amount of methanol at 100°C for 24 h. The resulting cobalt cage {[Ni8(PDA)4(H0.33PDA)2(CH3-PTA)3(DMF)6]6-[Co(H2O)3]4·xsolvent} was labelled 4. The significant similarities in the single-crystal structure, the packing and the PXRD patterns of 4 and 1 indicate that 4 is isomorphous with 1 [Figs. 5[link](a), S4(d) and S8(c)]. The host–guest interaction between two racemic cages attributed to the methyl group observed in 1 is also present in 4 [Fig. 5[link](b)]. The oxidation state of cobalt (+2) in 4 was confirmed by the XPS spectra, the calculated valence values and the magnetic measurement results [Figs. S6(g)–S6(h) and S7(j)–S7(l), and Table S1].

[Figure 5]
Figure 5
(a) X-ray crystal structure of 4. The violet and grey balls represent Co and C atoms, respectively. (b) Host–guest interaction between a methyl group and cone-shaped cavity of two adjacent racemic cages.

Investigating the factors driving the formation of complexes 1–4 provides a deeper understanding of the cage assembly process, which is crucial for the rational design of advanced supramolecular cage architectures. The first factor favouring the generation of discrete molecular cages 1–4 is the availability of unoccupied carboxyl­ate oxygen atoms with suitable positions and orientations on the TSHs (Mai et al., 2017[Mai, H. D., Kang, P., Kim, J. K. & Yoo, H. (2017). Sci. Rep. 7, 43448.]). Considering one TSH building block, the two unoccupied oxygen atoms connected with the linking metal ion are located on the same `strand' created by the extension of one bridging PTA ligand [Fig. S9(a)]. These two unoccupied oxygen atoms lie at almost opposite sides and set the longest distance that any two unoccupied oxygen atoms within a TSH can make [Fig. S9(b)]. With this coordination mode, the steric hindrance among neighbouring TSHs within a single cage can be minimized. The second contributing factor is related to the stability of the cages during the synthesis. Ni(II) and Co(II) ions, which differ in their own preferential coordination spheres and affinities to ligands, are expected to exhibit different coordination-driven assemblies (Le et al., 2019[Thi Le, V. C., Mai, H. D., Kang, P. & Yoo, H. (2019). Chem. Eur. J. 25, 2472-2476.]; Housecroft & Sharpe, 2005[Housecroft, C. E. & Sharpe, A. G. (2005). Inorganic Chemistry. London: Pearson.]). However, it was observed that both nickel and cobalt ions could adopt a fac-geometry mode to assemble six helicates and create a caged platform. It is therefore believed that the specific geometry of these supramolecular cages is energetically stable. In addition, since DMF was used as the solvent during the synthesis in the current case, its high polarity could cause the methyl/tert-butyl group in the TSHs to preferentially arrange in a manner that could minimize the exposure of nonpolar groups to polar solvent (Frischmann & Maclachlan, 2007[Frischmann, P. D. & MacLachlan, M. J. (2007). Chem. Commun. pp. 4480.]; Rahman et al., 2020[Rahman, F. -U., Yang, J. -M., Wan, Y. -H., Zhang, H. -B., Petsalakis, I. D., Theodorakopoulos, G. Jr, Rebek, J. & Yu, Y. (2020). Chem. Commun. 56, 6945-6948.]). The last factor is the intermolecular host–guest interactions between racemic cages. Considering cage 3, the electron-deficient tetranuclear metal cluster in one cage plays the role of a `metallocavitand' to provide sufficient space for the accommodation of electronegative bromo groups of the adjacent cage [Fig. 4[link](d)]. The shortest Br⋯C9 distance in 3 was found to be 3.54 Å, which is slightly shorter than the sum of the van der Waals radii of C and Br (3.63 Å) (Rowland & Taylor, 1996[Rowland, R. S. & Taylor, R. (1996). J. Phys. Chem. 100, 7384-7391.]). A similar interaction between an electron-deficient metal cluster acting as a host and electronegative bromo groups acting as guests has also been observed previously (Kang et al., 2018[Kang, P., Mai, H. D. & Yoo, H. (2018). Dalton Trans. 47, 6660-6665.]). It was reported that six discrete TSHs, even without linking metal atoms, could be arranged circularly to generate a cage-like structure with a similar topology to those observed in cages 1–4, and the driving force behind the cage-like assembly was the host–guest interaction (Kang et al., 2018[Kang, P., Mai, H. D. & Yoo, H. (2018). Dalton Trans. 47, 6660-6665.]). These host–guest interactions seem to present between racemic cages in the packing of 1, 2 and 4 [Figs. 3[link], 4[link](b) and 5[link](b)]. In fact, the host–guest interactions of the tert-butyl group and the methyl group have not been observed before. This is mainly because the methyl and tert-butyl groups are less electronegative than the bromo group. In the current work, the scope of cage structures with unique packing geometry is expanded to the Ni-based cage (1) with CH3-PTAs, Ni-based cage (2) with t-butyl-PTAs and Co-based cage (4) with CH3-PTAs. We expect that the current examples will provide researchers with a better understanding of complex molecular cages with SBBs and an effective strategy to facilitate the rational construction of these assemblies for specific applications.

4. Conclusions

A series of nickel-based metallosupramolecular cages {[Ni8(PDA)4(H0.33PDA)2(CH3-PTA)3(DMF)6]6-[Ni(H2O)3]4·xsolvent} (1), {[Ni8(PDA)4(H0.33PDA)2(t-butyl-PTA)3(DMF)4(H2O)2]6- [Ni(H2O)3]4·xsolvent} (2) and {[Ni8(PDA)4(H0.33PDA)2(Br-PTA)3(DMF)6]6-[Ni(H2O)3]4·xsolvent} (3), and a cobalt-based molecular cage {[Ni8(PDA)4(H0.33PDA)2(CH3-PTA)3(DMF)6]6-[Co(H2O)3]4·xsolvent} (4) were newly synthesized. These cages exhibit analogous assembly patterns with six homochiral SBBs linked by four metal atoms for the generation of discrete M6 and P6 cage molecules in the form of a racemate. The SCXRD data of 1–4 indicate that they possess similar packing behaviours, in which four neighbouring homochiral cages are arranged in four vertices of a tetrahedron with a cage of opposite chirality located at the centre of the tetrahedron. In addition, the packing structures of 1 and 4 indicate that the methyl group in the cobalt and nickel TSHs can be used for the host–guest interactions between racemic cages.

Supporting information

CCDC references: 2209422; 2209425; 2209565; 2209566

Crystal structure: contains datablocks 1, 2, 3, 4. DOI: https://doi.org/10.1107/S2052252523002385/yc5042sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2052252523002385/yc5042sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2052252523002385/yc5042sup3.hkl

Structure factors: contains datablock 3. DOI: https://doi.org/10.1107/S2052252523002385/yc5042sup4.hkl

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S2052252523002385/yc5042sup5.hkl

Supporting tables and figures. DOI: https://doi.org/10.1107/S2052252523002385/yc5042sup6.pdf


Computing details top

For all structures, data collection: Bruker APEXII; cell refinement: Bruker APEXII; data reduction: Bruker APEX software. Program(s) used to solve structure: SHELXT 2014/5 (Sheldrick, 2014) for (1); SHELXT 2014/4 (Sheldrick, 2014) for (2), (3), (4). For all structures, program(s) used to refine structure: SHELXL; molecular graphics: ORTEP; software used to prepare material for publication: CIFTAB.

(1) top
Crystal data top
C522H496N72Ni52O264Mo Kα radiation, λ = 0.71073 Å
Mr = 15054.80Cell parameters from 434911 reflections
Cubic, Fd3θ = 2.4–19.8°
a = 57.933 (7) ŵ = 1.04 mm−1
V = 194435 (67) Å3T = 100 K
Z = 8Block, green
F(000) = 616000.17 × 0.13 × 0.13 mm
Dx = 1.029 Mg m−3
Data collection top
CCD detector
diffractometer		13070 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.072
phi and ω scansθmax = 26.0°, θmin = 1.4°
Absorption correction: multi-scan
SADABS		h = −71→71
Tmin = 0.850, Tmax = 0.889k = −71→71
275607 measured reflectionsl = −71→66
15921 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.121 w = 1/[σ2(Fo2) + (0.0772P)2 + 357.5168P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.005
15921 reflectionsΔρmax = 1.02 e Å−3
686 parametersΔρmin = −0.69 e Å−3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni10.59818 (2)0.43486 (2)0.35939 (2)0.02021 (8)
Ni20.55575 (2)0.44844 (2)0.31869 (2)0.02515 (9)
Ni30.65071 (2)0.45212 (2)0.33634 (2)0.02620 (9)
Ni40.58788 (2)0.46983 (2)0.40633 (2)0.02427 (9)
Ni50.47945 (2)0.47945 (2)0.27055 (2)0.03869 (16)
O10.57589 (3)0.45979 (3)0.37114 (3)0.0242 (4)
O20.55266 (3)0.47334 (3)0.34272 (3)0.0278 (4)
O30.58934 (3)0.49080 (3)0.43478 (3)0.0268 (4)
O40.57224 (3)0.52120 (3)0.45125 (3)0.0325 (4)
O50.59349 (3)0.44793 (3)0.32603 (3)0.0249 (4)
O60.62596 (3)0.46625 (3)0.31502 (3)0.0296 (4)
O70.52561 (3)0.46021 (3)0.30159 (3)0.0329 (4)
O80.51448 (4)0.48533 (3)0.27395 (3)0.0363 (5)
O90.62572 (3)0.45757 (3)0.36467 (3)0.0253 (4)
O100.61545 (3)0.48541 (3)0.39015 (3)0.0285 (4)
O110.67692 (4)0.46173 (3)0.31367 (4)0.0381 (5)
O120.70400 (5)0.48889 (5)0.30877 (5)0.0664 (8)
H12S0.7125930.4801480.2978970.100*0.3333
O130.60032 (3)0.42086 (3)0.39139 (3)0.0257 (4)
O140.61021 (3)0.44645 (3)0.41857 (3)0.0311 (4)
O150.62053 (3)0.34029 (3)0.40012 (3)0.0271 (4)
O160.64636 (3)0.32918 (3)0.42654 (3)0.0303 (4)
O170.57294 (3)0.41125 (3)0.35371 (3)0.0236 (4)
O180.54005 (3)0.42563 (3)0.33965 (3)0.0307 (4)
O190.55999 (4)0.42302 (3)0.29462 (3)0.0346 (4)
O200.67534 (4)0.43893 (3)0.35921 (4)0.0396 (5)
O210.55949 (3)0.45368 (3)0.42056 (3)0.0345 (4)
O220.44446 (7)0.47385 (11)0.26515 (7)0.1292 (17)
H02A0.4361070.4836700.2730990.194*
H02B0.4403790.4598370.2693960.194*
N10.56613 (3)0.49469 (3)0.39726 (3)0.0219 (4)
N20.56874 (4)0.47180 (4)0.29709 (4)0.0285 (5)
N30.65917 (4)0.48274 (4)0.34881 (4)0.0299 (5)
N40.56879 (4)0.38602 (4)0.28729 (4)0.0303 (5)
N50.69019 (5)0.41500 (5)0.38576 (5)0.0516 (7)
N60.53175 (5)0.42750 (5)0.42710 (5)0.0511 (7)
C10.57529 (4)0.50759 (4)0.43514 (4)0.0251 (5)
C20.56175 (4)0.51098 (4)0.41299 (4)0.0222 (5)
C30.54615 (4)0.52824 (5)0.40835 (5)0.0297 (6)
H30.5427530.5396620.4196150.036*
C40.53543 (5)0.52869 (5)0.38689 (5)0.0338 (6)
H40.5250960.5408540.3831280.041*
C50.53983 (4)0.51131 (4)0.37094 (5)0.0288 (6)
H50.5323480.5111140.3563470.035*
C60.55541 (4)0.49439 (4)0.37697 (4)0.0222 (5)
C70.56172 (4)0.47420 (4)0.36218 (4)0.0230 (5)
C80.60502 (5)0.46246 (4)0.31402 (4)0.0254 (5)
C90.59128 (5)0.47625 (4)0.29678 (4)0.0308 (6)
C100.60038 (6)0.49280 (6)0.28241 (6)0.0487 (8)
H100.6164720.4959610.2822850.058*
C110.58521 (7)0.50486 (8)0.26796 (7)0.0639 (11)
H110.5909120.5165360.2579570.077*
C120.56193 (7)0.49975 (7)0.26830 (6)0.0579 (10)
H120.5515580.5075740.2583030.069*
C130.55394 (5)0.48313 (5)0.28334 (5)0.0359 (6)
C140.52915 (5)0.47561 (5)0.28647 (5)0.0332 (6)
C150.62814 (4)0.47697 (4)0.37503 (4)0.0250 (5)
C160.64856 (5)0.49099 (4)0.36742 (5)0.0292 (6)
C170.65631 (5)0.51113 (5)0.37791 (5)0.0351 (6)
H170.6487590.5171360.3911680.042*
C180.67527 (6)0.52219 (5)0.36859 (6)0.0423 (7)
H180.6809800.5358690.3756060.051*
C190.68596 (6)0.51354 (5)0.34920 (6)0.0430 (7)
H190.6988090.5212520.3425320.052*
C200.67744 (5)0.49310 (5)0.33956 (5)0.0356 (6)
C210.68687 (6)0.48028 (5)0.31907 (6)0.0436 (7)
C220.61089 (4)0.42687 (4)0.40949 (4)0.0239 (5)
C230.62466 (4)0.40847 (4)0.42142 (4)0.0236 (5)
C240.62410 (4)0.38588 (4)0.41308 (4)0.0222 (5)
H240.6158080.3824060.3993650.027*
C250.63568 (4)0.36846 (4)0.42486 (4)0.0230 (5)
C260.64845 (4)0.37396 (4)0.44457 (4)0.0270 (5)
H260.6567730.3621240.4522940.032*
C270.64925 (5)0.39646 (4)0.45316 (5)0.0300 (6)
C280.63708 (5)0.41345 (4)0.44144 (5)0.0296 (6)
H280.6372110.4288070.4471770.036*
C290.63406 (4)0.34413 (4)0.41647 (4)0.0245 (5)
C300.66296 (6)0.40181 (5)0.47474 (6)0.0439 (8)
H01D0.6702680.3876590.4804340.066*0.5
H01F0.6748750.4132670.4711560.066*0.5
H01G0.6526000.4079760.4866130.066*0.5
H01H0.6702680.3876590.4804340.066*0.5
H01I0.6748750.4132670.4711560.066*0.5
H01J0.6526000.4079760.4866130.066*0.5
C310.55141 (4)0.41149 (4)0.35172 (4)0.0250 (5)
C320.53824 (5)0.39265 (4)0.36385 (5)0.0288 (5)
C330.55027 (6)0.3750000.3750000.0255 (7)
H330.5666640.3750000.3750000.031*
C340.51422 (5)0.39242 (5)0.36386 (6)0.0433 (7)
H340.5060540.4043600.3561250.052*
C350.50192 (8)0.3750000.3750000.0522 (13)
C360.47551 (9)0.3750000.3750000.092 (3)
H36A0.4698750.3615650.3835940.138*0.5
H36B0.4698750.3891600.3823390.138*0.5
H36C0.4698750.3742750.3590680.138*0.5
C370.57032 (5)0.40492 (5)0.29951 (4)0.0287 (6)
H370.5798540.4047810.3128540.034*
C380.58197 (5)0.36541 (5)0.29309 (5)0.0405 (7)
H38A0.5784840.3531620.2819580.061*
H38B0.5985030.3689580.2925780.061*
H38C0.5777960.3602410.3086500.061*
C390.55409 (6)0.38486 (6)0.26703 (6)0.0513 (9)
H39A0.5551620.3694430.2601550.077*
H39B0.5380690.3879410.2715000.077*
H39C0.5591150.3964240.2557460.077*
C400.67347 (5)0.42318 (5)0.37298 (6)0.0409 (7)
H400.6586790.4162680.3745770.049*
C410.68757 (8)0.39559 (10)0.40155 (9)0.0871 (16)
H41A0.7023290.3925450.4092360.131*
H41B0.6758300.3992990.4131430.131*
H41C0.6827990.3818740.3928730.131*
C420.71354 (8)0.42469 (11)0.38420 (10)0.104 (2)
H42A0.7237650.4165310.3949230.156*
H42B0.7193410.4229110.3684120.156*
H42C0.7131030.4411190.3882270.156*
C430.55192 (5)0.43391 (5)0.41909 (5)0.0372 (6)
H430.5612350.4226080.4117180.045*
C440.52499 (8)0.40299 (7)0.42760 (8)0.0716 (12)
H44A0.5094430.4015600.4341180.107*
H44B0.5250940.3967890.4118610.107*
H44C0.5359260.3943120.4371520.107*
C450.51702 (6)0.44409 (8)0.43905 (8)0.0740 (13)
H45A0.5027040.4364720.4438610.111*
H45B0.5251080.4500150.4526780.111*
H45C0.5133700.4569090.4286410.111*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02776 (17)0.01266 (14)0.02021 (15)0.00100 (11)−0.00691 (12)−0.00272 (11)
Ni20.03751 (19)0.01749 (15)0.02046 (16)0.00166 (13)−0.01078 (13)−0.00310 (12)
Ni30.03249 (18)0.01668 (16)0.02941 (18)−0.00465 (12)−0.00603 (13)−0.00223 (12)
Ni40.03386 (18)0.01417 (15)0.02477 (17)0.00414 (12)−0.01299 (13)−0.00265 (12)
Ni50.03869 (16)0.03869 (16)0.03869 (16)−0.00544 (15)0.00544 (15)0.00544 (15)
O10.0320 (9)0.0170 (8)0.0238 (9)0.0051 (7)−0.0089 (7)−0.0026 (6)
O20.0373 (10)0.0215 (9)0.0248 (9)0.0056 (7)−0.0140 (8)−0.0042 (7)
O30.0369 (10)0.0186 (8)0.0250 (9)0.0020 (7)−0.0124 (7)−0.0008 (7)
O40.0404 (11)0.0327 (10)0.0245 (9)0.0031 (8)−0.0084 (8)−0.0122 (8)
O50.0360 (10)0.0182 (8)0.0206 (8)−0.0010 (7)−0.0076 (7)−0.0010 (7)
O60.0387 (11)0.0208 (9)0.0293 (9)−0.0022 (8)−0.0074 (8)0.0005 (7)
O70.0447 (11)0.0257 (9)0.0283 (10)0.0016 (8)−0.0167 (8)0.0001 (8)
O80.0438 (11)0.0343 (10)0.0309 (10)0.0075 (9)−0.0152 (9)0.0046 (8)
O90.0320 (9)0.0152 (8)0.0287 (9)0.0007 (7)−0.0095 (7)−0.0031 (7)
O100.0355 (10)0.0179 (8)0.0320 (10)0.0016 (7)−0.0103 (8)−0.0059 (7)
O110.0435 (11)0.0309 (10)0.0398 (11)−0.0104 (9)0.0007 (9)−0.0034 (8)
O120.0675 (17)0.0557 (15)0.0760 (18)−0.0316 (13)0.0269 (14)−0.0168 (13)
O130.0362 (10)0.0174 (8)0.0235 (9)−0.0011 (7)−0.0110 (7)0.0001 (7)
O140.0451 (11)0.0180 (9)0.0303 (10)0.0073 (8)−0.0185 (8)−0.0044 (7)
O150.0344 (10)0.0155 (8)0.0315 (10)−0.0018 (7)−0.0022 (8)−0.0001 (7)
O160.0396 (11)0.0193 (9)0.0319 (10)0.0080 (8)−0.0012 (8)−0.0016 (7)
O170.0309 (10)0.0164 (8)0.0235 (9)−0.0017 (7)−0.0060 (7)−0.0028 (6)
O180.0354 (10)0.0238 (9)0.0330 (10)0.0027 (8)−0.0092 (8)0.0030 (8)
O190.0483 (12)0.0271 (10)0.0285 (10)0.0015 (9)−0.0109 (8)−0.0088 (8)
O200.0377 (11)0.0331 (11)0.0479 (12)−0.0017 (9)−0.0115 (9)0.0026 (9)
O210.0427 (11)0.0280 (10)0.0328 (10)−0.0038 (8)−0.0113 (9)0.0042 (8)
O220.078 (2)0.213 (5)0.096 (3)−0.064 (3)0.021 (2)0.009 (3)
N10.0263 (11)0.0177 (9)0.0217 (10)0.0007 (8)−0.0067 (8)−0.0030 (8)
N20.0407 (13)0.0220 (11)0.0229 (11)0.0022 (9)−0.0094 (9)−0.0017 (8)
N30.0345 (12)0.0188 (10)0.0364 (12)−0.0056 (9)−0.0089 (10)0.0017 (9)
N40.0341 (12)0.0307 (12)0.0262 (11)0.0049 (9)−0.0038 (9)−0.0106 (9)
N50.0374 (15)0.0675 (19)0.0498 (16)0.0062 (13)−0.0079 (12)0.0147 (14)
N60.0330 (14)0.0613 (18)0.0590 (18)−0.0136 (13)−0.0079 (13)−0.0108 (14)
C10.0275 (13)0.0225 (12)0.0254 (13)−0.0037 (10)−0.0072 (10)−0.0013 (10)
C20.0227 (12)0.0206 (12)0.0233 (12)0.0003 (9)−0.0052 (9)−0.0049 (9)
C30.0287 (13)0.0295 (13)0.0308 (14)0.0106 (11)−0.0080 (11)−0.0127 (11)
C40.0295 (14)0.0371 (15)0.0347 (15)0.0170 (11)−0.0125 (11)−0.0126 (12)
C50.0283 (13)0.0286 (13)0.0296 (13)0.0079 (10)−0.0102 (11)−0.0070 (10)
C60.0242 (12)0.0207 (12)0.0217 (12)0.0015 (9)−0.0058 (9)−0.0021 (9)
C70.0263 (12)0.0200 (11)0.0226 (12)0.0008 (9)−0.0073 (10)−0.0011 (9)
C80.0395 (15)0.0151 (11)0.0218 (12)0.0005 (10)−0.0083 (10)−0.0025 (9)
C90.0433 (16)0.0254 (13)0.0237 (13)0.0029 (11)−0.0089 (11)0.0004 (10)
C100.0450 (18)0.056 (2)0.0450 (18)0.0001 (15)−0.0072 (14)0.0254 (16)
C110.057 (2)0.080 (3)0.054 (2)0.0015 (19)−0.0056 (18)0.042 (2)
C120.055 (2)0.070 (2)0.048 (2)0.0095 (18)−0.0090 (16)0.0338 (18)
C130.0456 (17)0.0329 (15)0.0293 (14)0.0071 (12)−0.0099 (12)0.0029 (11)
C140.0453 (16)0.0267 (13)0.0277 (14)0.0067 (12)−0.0150 (12)−0.0050 (11)
C150.0329 (13)0.0150 (11)0.0271 (13)0.0005 (10)−0.0139 (11)−0.0025 (9)
C160.0366 (14)0.0186 (12)0.0323 (14)0.0017 (10)−0.0139 (11)−0.0024 (10)
C170.0401 (16)0.0220 (13)0.0434 (16)−0.0030 (11)−0.0137 (13)−0.0047 (11)
C180.0486 (18)0.0222 (13)0.056 (2)−0.0090 (12)−0.0172 (15)−0.0066 (13)
C190.0418 (17)0.0265 (14)0.061 (2)−0.0154 (13)−0.0106 (15)−0.0010 (14)
C200.0376 (15)0.0248 (13)0.0444 (16)−0.0082 (11)−0.0098 (13)−0.0001 (12)
C210.0448 (18)0.0366 (16)0.0495 (18)−0.0150 (14)−0.0016 (14)0.0007 (14)
C220.0309 (13)0.0196 (12)0.0213 (12)0.0014 (10)−0.0068 (10)−0.0002 (9)
C230.0294 (13)0.0165 (11)0.0248 (12)0.0011 (9)−0.0060 (10)−0.0006 (9)
C240.0247 (12)0.0192 (11)0.0227 (12)−0.0004 (9)−0.0036 (9)−0.0009 (9)
C250.0257 (12)0.0181 (12)0.0251 (12)0.0023 (9)0.0004 (10)0.0000 (9)
C260.0301 (13)0.0212 (12)0.0296 (13)0.0036 (10)−0.0057 (10)0.0030 (10)
C270.0365 (14)0.0242 (13)0.0293 (13)0.0033 (11)−0.0127 (11)−0.0012 (10)
C280.0371 (15)0.0204 (12)0.0313 (14)0.0040 (10)−0.0119 (11)−0.0036 (10)
C290.0290 (13)0.0191 (12)0.0253 (12)0.0007 (10)0.0045 (10)−0.0001 (9)
C300.056 (2)0.0298 (15)0.0454 (18)0.0069 (13)−0.0289 (15)−0.0035 (13)
C310.0295 (14)0.0206 (12)0.0249 (12)0.0009 (10)−0.0048 (10)−0.0062 (10)
C320.0278 (13)0.0242 (13)0.0344 (14)0.0012 (10)−0.0038 (11)−0.0021 (11)
C330.0279 (18)0.0229 (17)0.0256 (18)0.0000.000−0.0032 (14)
C340.0305 (15)0.0368 (16)0.062 (2)0.0052 (12)−0.0032 (14)0.0091 (15)
C350.028 (2)0.045 (3)0.084 (4)0.0000.0000.018 (2)
C360.030 (3)0.083 (4)0.163 (7)0.0000.0000.054 (5)
C370.0315 (14)0.0305 (14)0.0242 (13)−0.0017 (11)−0.0013 (10)−0.0069 (10)
C380.0432 (17)0.0351 (15)0.0433 (17)0.0110 (13)−0.0129 (13)−0.0144 (13)
C390.062 (2)0.0423 (18)0.0497 (19)0.0127 (16)−0.0297 (17)−0.0202 (15)
C400.0339 (16)0.0420 (17)0.0469 (18)0.0000 (13)−0.0057 (13)0.0055 (14)
C410.055 (2)0.117 (4)0.089 (3)0.006 (3)0.002 (2)0.057 (3)
C420.060 (3)0.138 (5)0.114 (4)−0.023 (3)−0.036 (3)0.058 (4)
C430.0428 (17)0.0335 (15)0.0353 (15)−0.0023 (12)−0.0105 (13)−0.0025 (12)
C440.072 (3)0.069 (3)0.074 (3)−0.040 (2)0.006 (2)−0.012 (2)
C450.0342 (19)0.097 (3)0.091 (3)0.012 (2)−0.014 (2)−0.015 (3)
Geometric parameters (Å, º) top
Ni1—O15i2.0252 (17)C4—H40.9500
Ni1—O132.0272 (17)C5—C61.377 (3)
Ni1—O172.0288 (17)C5—H50.9500
Ni1—O12.0536 (17)C6—C71.496 (3)
Ni1—O92.0910 (17)C8—C91.506 (3)
Ni1—O52.0934 (17)C9—C101.375 (4)
Ni2—N21.991 (2)C10—C111.401 (5)
Ni2—O182.0116 (19)C10—H100.9500
Ni2—O22.0128 (17)C11—C121.381 (5)
Ni2—O192.0435 (18)C11—H110.9500
Ni2—O72.1200 (19)C12—C131.378 (4)
Ni2—O52.2275 (18)C12—H120.9500
Ni3—O16i1.9769 (17)C13—C141.512 (4)
Ni3—N31.977 (2)C15—C161.501 (4)
Ni3—O62.0615 (18)C16—C171.390 (4)
Ni3—O112.084 (2)C17—C181.382 (4)
Ni3—O202.092 (2)C17—H170.9500
Ni3—O92.2108 (18)C18—C191.377 (5)
Ni4—N11.984 (2)C18—H180.9500
Ni4—O142.0025 (17)C19—C201.399 (4)
Ni4—O32.0491 (17)C19—H190.9500
Ni4—O102.0600 (19)C20—C211.503 (5)
Ni4—O212.064 (2)C22—C231.500 (3)
Ni4—O12.2312 (16)C23—C281.394 (3)
Ni5—O82.067 (2)C23—C241.395 (3)
Ni5—O8ii2.068 (2)C24—C251.391 (3)
Ni5—O8iii2.068 (2)C24—H240.9500
Ni5—O222.076 (4)C25—C261.397 (4)
Ni5—O22ii2.076 (4)C25—C291.494 (3)
Ni5—O22iii2.076 (4)C26—C271.396 (4)
O1—C71.281 (3)C26—H260.9500
O2—C71.244 (3)C27—C281.388 (4)
O3—C11.269 (3)C27—C301.513 (4)
O4—C11.234 (3)C28—H280.9500
O5—C81.280 (3)C30—H01D0.9800
O6—C81.234 (3)C30—H01F0.9800
O7—C141.267 (3)C30—H01G0.9800
O8—C141.251 (3)C30—H01H0.9800
O9—C151.281 (3)C30—H01I0.9800
O10—C151.244 (3)C30—H01J0.9800
O11—C211.259 (3)C31—C321.506 (4)
O12—C211.261 (4)C32—C341.392 (4)
O12—H12S0.9491C32—C331.396 (3)
O13—C221.263 (3)C33—H330.9500
O14—C221.251 (3)C34—C351.394 (4)
O15—C291.250 (3)C34—H340.9500
O16—C291.264 (3)C35—C361.530 (7)
O17—C311.252 (3)C36—H36A0.9800
O18—C311.263 (3)C36—H36B0.9800
O19—C371.240 (3)C36—H36C0.9800
O20—C401.217 (4)C36—H36Ai0.9800
O21—C431.230 (3)C36—H36Bi0.9801
O22—H02A0.8774C36—H36Ci0.9800
O22—H02B0.8805C37—H370.9500
N1—C61.330 (3)C38—H38A0.9800
N1—C21.336 (3)C38—H38B0.9800
N2—C91.331 (4)C38—H38C0.9800
N2—C131.342 (3)C39—H39A0.9800
N3—C201.330 (4)C39—H39B0.9800
N3—C161.330 (4)C39—H39C0.9800
N4—C371.307 (3)C40—H400.9500
N4—C391.452 (4)C41—H41A0.9800
N4—C381.457 (4)C41—H41B0.9800
N5—C401.308 (4)C41—H41C0.9800
N5—C411.457 (5)C42—H42A0.9800
N5—C421.467 (5)C42—H42B0.9800
N6—C431.311 (4)C42—H42C0.9800
N6—C451.460 (5)C43—H430.9500
N6—C441.473 (5)C44—H44A0.9800
C1—C21.517 (3)C44—H44B0.9800
C2—C31.374 (3)C44—H44C0.9800
C3—C41.390 (4)C45—H45A0.9800
C3—H30.9500C45—H45B0.9800
C4—C51.390 (4)C45—H45C0.9800
O15i—Ni1—O1385.52 (7)C13—C12—H12120.4
O15i—Ni1—O1786.10 (7)C11—C12—H12120.4
O13—Ni1—O1785.58 (7)N2—C13—C12120.2 (3)
O15i—Ni1—O1176.42 (7)N2—C13—C14113.3 (2)
O13—Ni1—O190.95 (7)C12—C13—C14126.6 (3)
O17—Ni1—O194.28 (7)O8—C14—O7127.4 (3)
O15i—Ni1—O990.26 (7)O8—C14—C13116.5 (3)
O13—Ni1—O994.09 (7)O7—C14—C13116.0 (2)
O17—Ni1—O9176.36 (7)O10—C15—O9127.6 (2)
O1—Ni1—O989.35 (7)O10—C15—C16117.4 (2)
O15i—Ni1—O595.29 (7)O9—C15—C16115.0 (2)
O13—Ni1—O5175.47 (7)N3—C16—C17120.4 (3)
O17—Ni1—O590.03 (7)N3—C16—C15114.1 (2)
O1—Ni1—O588.27 (7)C17—C16—C15125.5 (3)
O9—Ni1—O590.37 (7)C18—C17—C16118.4 (3)
N2—Ni2—O18175.33 (8)C18—C17—H17120.8
N2—Ni2—O288.92 (8)C16—C17—H17120.8
O18—Ni2—O290.75 (8)C19—C18—C17120.5 (3)
N2—Ni2—O1990.87 (8)C19—C18—H18119.8
O18—Ni2—O1989.60 (8)C17—C18—H18119.8
O2—Ni2—O19178.11 (8)C18—C19—C20118.4 (3)
N2—Ni2—O778.39 (8)C18—C19—H19120.8
O18—Ni2—O796.96 (8)C20—C19—H19120.8
O2—Ni2—O791.11 (7)N3—C20—C19120.1 (3)
O19—Ni2—O790.69 (7)N3—C20—C21112.6 (2)
N2—Ni2—O575.99 (8)C19—C20—C21127.2 (3)
O18—Ni2—O5108.66 (7)O11—C21—O12125.5 (3)
O2—Ni2—O587.98 (7)O11—C21—C20116.8 (3)
O19—Ni2—O590.14 (7)O12—C21—C20117.7 (3)
O7—Ni2—O5154.38 (7)O14—C22—O13125.7 (2)
O16i—Ni3—N3172.95 (9)O14—C22—C23117.9 (2)
O16i—Ni3—O692.84 (7)O13—C22—C23116.4 (2)
N3—Ni3—O692.00 (8)C28—C23—C24119.6 (2)
O16i—Ni3—O1195.72 (8)C28—C23—C22120.7 (2)
N3—Ni3—O1179.04 (9)C24—C23—C22119.6 (2)
O6—Ni3—O1191.33 (8)C25—C24—C23119.9 (2)
O16i—Ni3—O2089.48 (8)C25—C24—H24120.0
N3—Ni3—O2085.83 (8)C23—C24—H24120.0
O6—Ni3—O20177.21 (8)C24—C25—C26119.4 (2)
O11—Ni3—O2089.98 (9)C24—C25—C29119.6 (2)
O16i—Ni3—O9109.15 (7)C26—C25—C29120.9 (2)
N3—Ni3—O976.29 (8)C27—C26—C25121.4 (2)
O6—Ni3—O986.14 (7)C27—C26—H26119.3
O11—Ni3—O9155.08 (7)C25—C26—H26119.3
O20—Ni3—O991.64 (8)C28—C27—C26118.1 (2)
N1—Ni4—O14174.12 (8)C28—C27—C30121.7 (2)
N1—Ni4—O379.00 (7)C26—C27—C30120.2 (2)
O14—Ni4—O395.13 (7)C27—C28—C23121.5 (2)
N1—Ni4—O1093.09 (8)C27—C28—H28119.3
O14—Ni4—O1087.51 (8)C23—C28—H28119.3
O3—Ni4—O1094.26 (7)O15—C29—O16125.6 (2)
N1—Ni4—O2185.91 (8)O15—C29—C25117.0 (2)
O14—Ni4—O2193.83 (8)O16—C29—C25117.4 (2)
O3—Ni4—O2188.87 (8)C27—C30—H01D109.5
O10—Ni4—O21176.48 (7)C27—C30—H01F109.5
N1—Ni4—O175.50 (7)H01D—C30—H01F109.5
O14—Ni4—O1110.38 (7)C27—C30—H01G109.5
O3—Ni4—O1154.49 (6)H01D—C30—H01G109.5
O10—Ni4—O186.57 (7)H01F—C30—H01G109.5
O21—Ni4—O189.92 (7)C27—C30—H01H109.5
O8—Ni5—O8ii86.96 (8)H01D—C30—H01H0.0
O8—Ni5—O8iii86.97 (8)H01F—C30—H01H109.5
O8ii—Ni5—O8iii86.96 (8)H01G—C30—H01H109.5
O8—Ni5—O22176.76 (12)C27—C30—H01I109.5
O8ii—Ni5—O2289.90 (13)H01D—C30—H01I109.5
O8iii—Ni5—O2292.04 (18)H01F—C30—H01I0.0
O8—Ni5—O22ii92.04 (18)H01G—C30—H01I109.5
O8ii—Ni5—O22ii176.76 (12)H01H—C30—H01I109.5
O8iii—Ni5—O22ii89.90 (12)C27—C30—H01J109.5
O22—Ni5—O22ii91.04 (18)H01D—C30—H01J109.5
O8—Ni5—O22iii89.90 (13)H01F—C30—H01J109.5
O8ii—Ni5—O22iii92.04 (18)H01G—C30—H01J0.0
O8iii—Ni5—O22iii176.76 (12)H01H—C30—H01J109.5
O22—Ni5—O22iii91.04 (18)H01I—C30—H01J109.5
O22ii—Ni5—O22iii91.04 (18)O17—C31—O18125.3 (2)
C7—O1—Ni1136.65 (16)O17—C31—C32117.0 (2)
C7—O1—Ni4113.58 (14)O18—C31—C32117.7 (2)
Ni1—O1—Ni4106.88 (7)C34—C32—C33119.5 (3)
C7—O2—Ni2128.13 (16)C34—C32—C31120.9 (2)
C1—O3—Ni4116.17 (15)C33—C32—C31119.6 (2)
C8—O5—Ni1132.21 (15)C32—C33—C32i120.1 (3)
C8—O5—Ni2113.58 (15)C32—C33—H33119.9
Ni1—O5—Ni2107.96 (8)C32i—C33—H33119.9
C8—O6—Ni3129.87 (17)C32—C34—C35121.2 (3)
C14—O7—Ni2114.62 (18)C32—C34—H34119.4
C14—O8—Ni5130.4 (2)C35—C34—H34119.4
C15—O9—Ni1134.73 (17)C34—C35—C34i118.5 (4)
C15—O9—Ni3113.67 (16)C34—C35—C36120.7 (2)
Ni1—O9—Ni3107.52 (7)C34i—C35—C36120.7 (2)
C15—O10—Ni4127.31 (16)C35—C36—H36A109.5
C21—O11—Ni3113.9 (2)C35—C36—H36B109.5
C21—O12—H12S121.1H36A—C36—H36B109.5
C22—O13—Ni1132.74 (16)C35—C36—H36C109.5
C22—O14—Ni4119.02 (15)H36A—C36—H36C109.5
C29—O15—Ni1i137.34 (16)H36B—C36—H36C109.5
C29—O16—Ni3i121.72 (17)C35—C36—H36Ai109.483 (1)
C31—O17—Ni1136.49 (16)H36A—C36—H36Ai141.0
C31—O18—Ni2121.65 (17)H36B—C36—H36Ai56.2
C37—O19—Ni2120.76 (17)H36C—C36—H36Ai56.3
C40—O20—Ni3128.9 (2)C35—C36—H36Bi109.482 (1)
C43—O21—Ni4132.7 (2)H36A—C36—H36Bi56.3
Ni5—O22—H02A111.0H36B—C36—H36Bi141.0
Ni5—O22—H02B111.4H36C—C36—H36Bi56.2
H02A—O22—H02B107.7H36Ai—C36—H36Bi109.5
C6—N1—C2121.6 (2)C35—C36—H36Ci109.484 (1)
C6—N1—Ni4121.42 (16)H36A—C36—H36Ci56.2
C2—N1—Ni4116.91 (16)H36B—C36—H36Ci56.2
C9—N2—C13121.6 (2)H36C—C36—H36Ci141.0
C9—N2—Ni2120.72 (17)H36Ai—C36—H36Ci109.4
C13—N2—Ni2117.7 (2)H36Bi—C36—H36Ci109.5
C20—N3—C16122.2 (2)O19—C37—N4123.5 (2)
C20—N3—Ni3117.08 (19)O19—C37—H37118.3
C16—N3—Ni3120.26 (18)N4—C37—H37118.3
C37—N4—C39121.1 (2)N4—C38—H38A109.5
C37—N4—C38121.7 (2)N4—C38—H38B109.5
C39—N4—C38117.2 (2)H38A—C38—H38B109.5
C40—N5—C41123.9 (3)N4—C38—H38C109.5
C40—N5—C42120.6 (3)H38A—C38—H38C109.5
C41—N5—C42115.5 (3)H38B—C38—H38C109.5
C43—N6—C45120.2 (3)N4—C39—H39A109.5
C43—N6—C44121.1 (3)N4—C39—H39B109.5
C45—N6—C44118.0 (3)H39A—C39—H39B109.5
O4—C1—O3126.5 (2)N4—C39—H39C109.5
O4—C1—C2118.9 (2)H39A—C39—H39C109.5
O3—C1—C2114.7 (2)H39B—C39—H39C109.5
N1—C2—C3120.4 (2)O20—C40—N5125.2 (3)
N1—C2—C1112.8 (2)O20—C40—H40117.4
C3—C2—C1126.8 (2)N5—C40—H40117.4
C2—C3—C4118.8 (2)N5—C41—H41A109.5
C2—C3—H3120.6N5—C41—H41B109.5
C4—C3—H3120.6H41A—C41—H41B109.5
C3—C4—C5119.9 (2)N5—C41—H41C109.5
C3—C4—H4120.0H41A—C41—H41C109.5
C5—C4—H4120.0H41B—C41—H41C109.5
C6—C5—C4117.8 (2)N5—C42—H42A109.5
C6—C5—H5121.1N5—C42—H42B109.5
C4—C5—H5121.1H42A—C42—H42B109.5
N1—C6—C5121.4 (2)N5—C42—H42C109.5
N1—C6—C7113.7 (2)H42A—C42—H42C109.5
C5—C6—C7124.9 (2)H42B—C42—H42C109.5
O2—C7—O1127.7 (2)O21—C43—N6123.9 (3)
O2—C7—C6116.5 (2)O21—C43—H43118.1
O1—C7—C6115.7 (2)N6—C43—H43118.1
O6—C8—O5127.2 (2)N6—C44—H44A109.5
O6—C8—C9117.2 (2)N6—C44—H44B109.5
O5—C8—C9115.7 (2)H44A—C44—H44B109.5
N2—C9—C10121.3 (3)N6—C44—H44C109.5
N2—C9—C8114.0 (2)H44A—C44—H44C109.5
C10—C9—C8124.6 (3)H44B—C44—H44C109.5
C9—C10—C11118.0 (3)N6—C45—H45A109.5
C9—C10—H10121.0N6—C45—H45B109.5
C11—C10—H10121.0H45A—C45—H45B109.5
C12—C11—C10119.8 (3)N6—C45—H45C109.5
C12—C11—H11120.1H45A—C45—H45C109.5
C10—C11—H11120.1H45B—C45—H45C109.5
C13—C12—C11119.1 (3)
Symmetry codes: (i) x, −y+3/4, −z+3/4; (ii) y, −z+3/4, −x+3/4; (iii) −z+3/4, x, −y+3/4.
(2) top
Crystal data top
C540H544N60Ni52O264Synchrotron radiation, λ = 0.700 Å
Mr = 15151.24Cell parameters from 549556 reflections
Cubic, Fd3θ = 2.4–19.8°
a = 58.600 (7) ŵ = 0.97 mm−1
V = 201234 (70) Å3T = 100 K
Z = 8Block, green
F(000) = 621760.10 × 0.09 × 0.07 mm
Dx = 1.000 Mg m−3
Data collection top
CCD detector
diffractometer		12936 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.079
phi and ω scansθmax = 26.0°, θmin = 1.5°
Absorption correction: multi-scan
SADABS		h = −73→73
Tmin = 0.621, Tmax = 0.689k = −73→73
319601 measured reflectionsl = −70→70
17258 independent reflections
Refinement top
Refinement on F2833 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.165 w = 1/[σ2(Fo2) + (0.1184P)2 + 102.4186P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.003
17258 reflectionsΔρmax = 1.44 e Å−3
733 parametersΔρmin = −0.86 e Å−3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Ni10.39052 (2)0.31551 (2)0.59552 (2)0.02846 (10)
Ni20.42983 (2)0.30237 (2)0.55327 (2)0.03418 (11)
Ni30.41373 (2)0.29913 (2)0.64764 (2)0.03632 (11)
Ni40.34405 (2)0.28025 (2)0.58724 (2)0.03188 (11)
Ni50.47797 (2)0.27203 (2)0.47797 (2)0.0504 (2)
O10.37883 (3)0.29033 (3)0.57411 (3)0.0314 (4)
O20.40668 (3)0.27687 (4)0.55100 (4)0.0366 (5)
O30.31628 (3)0.25932 (3)0.58964 (4)0.0355 (5)
O40.30032 (4)0.22837 (4)0.57369 (4)0.0413 (5)
O50.42354 (3)0.30373 (3)0.59049 (4)0.0340 (5)
O60.43645 (4)0.28807 (4)0.62312 (4)0.0389 (5)
O70.44682 (4)0.29020 (4)0.52357 (4)0.0422 (5)
O80.47432 (4)0.26559 (4)0.51264 (4)0.0479 (6)
O90.43734 (4)0.29041 (4)0.67317 (4)0.0489 (6)
O100.44600 (6)0.26217 (6)0.69730 (7)0.0980 (13)
H10S0.4587920.2700830.7028360.147*0.3333
O110.38625 (3)0.29275 (3)0.62309 (4)0.0332 (4)
O120.36095 (4)0.26497 (3)0.61408 (4)0.0366 (5)
O130.35835 (3)0.32779 (3)0.59715 (4)0.0334 (5)
O140.33240 (4)0.30302 (3)0.60987 (4)0.0380 (5)
O150.35079 (4)0.40855 (3)0.61626 (4)0.0365 (5)
O160.32619 (4)0.41925 (3)0.64343 (4)0.0409 (5)
O170.39514 (3)0.33875 (3)0.56999 (4)0.0319 (4)
O180.40853 (4)0.32399 (4)0.53745 (4)0.0398 (5)
O190.45281 (4)0.32871 (4)0.55649 (4)0.0426 (5)
O200.32910 (4)0.29590 (4)0.55945 (4)0.0407 (5)
O210.39043 (5)0.31179 (6)0.67221 (5)0.0693 (8)
H21A0.3762920.3188910.6679230.104*
H21B0.3985200.3216040.6825400.104*
O220.48370 (8)0.28005 (9)0.44453 (7)0.1189 (16)
H22A0.4881880.2665490.4364200.178*
H22B0.4956540.2912120.4436030.178*
N10.35307 (4)0.25555 (4)0.56572 (4)0.0301 (5)
N20.45297 (4)0.28110 (4)0.56631 (5)0.0378 (6)
N30.40361 (5)0.26825 (5)0.65565 (5)0.0417 (6)
N40.46163 (5)0.36427 (5)0.56877 (5)0.0395 (6)
N50.32221 (5)0.32294 (5)0.53268 (5)0.0487 (7)
C10.31595 (5)0.24237 (5)0.57615 (5)0.0330 (6)
C20.33757 (5)0.23909 (5)0.56224 (5)0.0322 (6)
C30.34194 (6)0.22144 (6)0.54735 (5)0.0387 (7)
H30.3310410.2096640.5450050.046*
C40.36290 (6)0.22128 (6)0.53572 (6)0.0470 (8)
H40.3664870.2091430.5255820.056*
C50.37835 (5)0.23890 (5)0.53908 (6)0.0389 (7)
H50.3923950.2392870.5309920.047*
C60.37281 (5)0.25586 (5)0.55446 (5)0.0307 (6)
C70.38750 (5)0.27593 (5)0.56010 (5)0.0311 (6)
C80.43695 (5)0.29114 (5)0.60230 (6)0.0357 (7)
C90.45511 (5)0.27889 (5)0.58869 (6)0.0376 (7)
C100.47220 (6)0.26552 (6)0.59819 (7)0.0465 (8)
H100.4740390.2644410.6142590.056*
C110.48650 (6)0.25380 (6)0.58343 (7)0.0524 (9)
H110.4982490.2443530.5893840.063*
C120.48374 (6)0.25579 (6)0.56012 (7)0.0511 (9)
H120.4932000.2474790.5499160.061*
C130.46700 (5)0.27006 (5)0.55201 (6)0.0419 (7)
C140.46217 (5)0.27571 (5)0.52722 (6)0.0407 (7)
C150.43417 (7)0.27098 (7)0.68174 (7)0.0598 (10)
C160.41412 (6)0.25766 (6)0.67258 (6)0.0483 (8)
C170.40627 (7)0.23636 (7)0.68062 (7)0.0568 (10)
H170.4140410.2285580.6925170.068*
C180.38701 (7)0.22721 (6)0.67072 (7)0.0545 (9)
H180.3811540.2130510.6760240.065*
C190.37596 (6)0.23876 (6)0.65278 (6)0.0462 (8)
H190.3626940.2325320.6458600.055*
C200.38493 (6)0.25959 (5)0.64536 (6)0.0391 (7)
C210.37652 (5)0.27346 (5)0.62588 (5)0.0334 (6)
C220.34182 (5)0.32251 (5)0.60990 (5)0.0315 (6)
C230.33253 (5)0.34050 (5)0.62510 (5)0.0300 (6)
C240.33990 (5)0.36294 (5)0.62241 (5)0.0300 (6)
H240.3515400.3664530.6116810.036*
C250.33023 (5)0.38006 (5)0.63539 (5)0.0304 (6)
C260.31410 (5)0.37450 (5)0.65212 (5)0.0330 (6)
H260.3077160.3863450.6611520.040*
C270.30717 (5)0.35213 (5)0.65588 (5)0.0327 (6)
C280.31621 (5)0.33522 (5)0.64167 (5)0.0318 (6)
H280.3111660.3199030.6433080.038*
C290.33632 (5)0.40456 (5)0.63141 (5)0.0343 (6)
C300.28951 (6)0.34667 (6)0.67436 (6)0.0415 (7)
C310.29723 (14)0.35620 (13)0.69706 (12)0.0707 (12)0.642 (4)
H31A0.3117160.3490910.7014610.106*0.642 (4)
H31B0.2993200.3727440.6957430.106*0.642 (4)
H31C0.2856690.3529560.7087000.106*0.642 (4)
C320.28567 (13)0.32092 (11)0.67773 (12)0.0655 (11)0.642 (4)
H320.3001030.3136470.6820140.098*0.642 (4)
H1AB0.2743960.3185070.6898450.098*0.642 (4)
H1AC0.2800570.3142130.6634770.098*0.642 (4)
C330.26742 (12)0.35763 (14)0.66783 (12)0.0700 (12)0.642 (4)
H33A0.2622970.3515360.6531270.105*0.642 (4)
H33B0.2559090.3543830.6795260.105*0.642 (4)
H33C0.2695600.3741710.6665690.105*0.642 (4)
C31X0.3004 (2)0.3291 (2)0.6907 (2)0.0688 (12)0.358 (4)
H31D0.3143990.3355330.6972950.103*0.358 (4)
H31E0.2896510.3255070.7030260.103*0.358 (4)
H31F0.3041140.3151560.6823020.103*0.358 (4)
C32X0.2680 (2)0.3384 (2)0.6635 (2)0.0679 (12)0.358 (4)
H32A0.2713140.3248520.6542980.102*0.358 (4)
H32B0.2569170.3345690.6753720.102*0.358 (4)
H32C0.2617950.3504410.6536910.102*0.358 (4)
C33X0.2828 (2)0.3676 (2)0.6882 (2)0.0693 (12)0.358 (4)
H33D0.2963580.3738030.6957690.104*0.358 (4)
H33E0.2763400.3791480.6779790.104*0.358 (4)
H33F0.2714620.3632760.6996600.104*0.358 (4)
C340.39730 (5)0.33842 (5)0.54884 (5)0.0326 (6)
C350.38569 (5)0.35744 (5)0.53587 (5)0.0357 (7)
C360.3750000.3750000.54786 (7)0.0324 (9)
H360.3750010.3749990.5640730.039*
C370.38564 (7)0.35768 (6)0.51214 (6)0.0525 (9)
H370.3930660.3457300.5040940.063*
C380.3750000.3750000.49993 (9)0.0666 (17)
C390.3750000.3750000.47373 (12)0.119 (2)
C400.3868 (3)0.3925 (3)0.46441 (17)0.120 (3)0.5
H40A0.3931720.4019810.4765760.180*0.5
H40B0.3991510.3864150.4549480.180*0.5
H40C0.3765000.4016700.4549480.180*0.5
C410.3469 (3)0.3757 (3)0.46625 (16)0.120 (3)0.5
H41A0.3405490.3907310.4697610.180*0.5
H41B0.3454200.3726730.4498610.180*0.5
H41C0.3385690.3639680.4748230.180*0.5
C420.3790 (3)0.3490 (3)0.46467 (16)0.120 (3)0.5
H42A0.3950550.3448100.4666530.180*0.5
H42B0.3693630.3385050.4734300.180*0.5
H42C0.3749450.3480660.4484660.180*0.5
C430.44892 (5)0.34579 (5)0.56884 (6)0.0377 (7)
H420.4361050.3453300.5787690.045*
C440.45675 (6)0.38384 (6)0.58326 (6)0.0477 (8)
H43A0.4682100.3957320.5806070.072*
H43B0.4415660.3898230.5796140.072*
H43C0.4571960.3791480.5993000.072*
C450.48153 (7)0.36602 (7)0.55393 (8)0.0614 (11)
H440.4888580.3808820.5561650.092*
H0AB0.4923600.3538400.5576650.092*
H0AC0.4767330.3645130.5379760.092*
C460.33055 (5)0.31564 (6)0.55220 (6)0.0398 (7)
H450.3383260.3264260.5614760.048*
C470.32222 (9)0.34655 (8)0.52623 (8)0.0756 (14)
H460.3152370.3482100.5111240.113*
H7AB0.3134650.3553860.5374130.113*
H7AC0.3379520.3521930.5257520.113*
C480.30889 (9)0.30671 (9)0.51815 (7)0.0769 (14)
H470.3038200.3145340.5042610.115*
H6AB0.3185680.2937160.5140040.115*
H6AC0.2955690.3012550.5266540.115*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.02726 (19)0.02312 (19)0.0350 (2)−0.00303 (14)0.00487 (15)−0.00139 (14)
Ni20.0286 (2)0.0270 (2)0.0470 (2)−0.00317 (15)0.00982 (16)−0.00285 (16)
Ni30.0388 (2)0.0273 (2)0.0429 (2)−0.00448 (16)−0.00030 (17)0.00578 (16)
Ni40.0302 (2)0.02434 (19)0.0411 (2)−0.00301 (14)0.00995 (16)−0.00449 (15)
Ni50.0504 (2)0.0504 (2)0.0504 (2)0.0036 (2)−0.0036 (2)0.0036 (2)
O10.0293 (10)0.0250 (10)0.0401 (11)−0.0035 (8)0.0083 (8)−0.0047 (8)
O20.0307 (11)0.0321 (11)0.0470 (13)−0.0056 (8)0.0110 (9)−0.0063 (9)
O30.0317 (11)0.0285 (11)0.0462 (12)−0.0031 (8)0.0112 (9)−0.0030 (9)
O40.0367 (12)0.0390 (12)0.0484 (13)−0.0118 (9)0.0065 (10)−0.0026 (10)
O50.0288 (10)0.0270 (10)0.0462 (12)−0.0032 (8)0.0063 (9)0.0030 (9)
O60.0364 (12)0.0324 (11)0.0480 (13)0.0000 (9)0.0018 (10)0.0020 (9)
O70.0343 (12)0.0360 (12)0.0564 (14)−0.0022 (9)0.0153 (10)−0.0012 (10)
O80.0411 (13)0.0466 (14)0.0561 (15)0.0031 (10)0.0155 (11)−0.0063 (11)
O90.0525 (15)0.0421 (13)0.0521 (14)−0.0091 (11)−0.0099 (11)0.0130 (11)
O100.092 (3)0.087 (2)0.115 (3)−0.029 (2)−0.050 (2)0.061 (2)
O110.0347 (11)0.0266 (10)0.0382 (11)−0.0040 (8)0.0038 (9)0.0021 (8)
O120.0373 (12)0.0271 (10)0.0454 (12)−0.0054 (9)0.0077 (9)−0.0028 (9)
O130.0292 (10)0.0279 (10)0.0431 (12)0.0015 (8)0.0077 (9)0.0000 (9)
O140.0366 (12)0.0274 (10)0.0501 (13)−0.0068 (9)0.0166 (10)−0.0080 (9)
O150.0407 (12)0.0276 (11)0.0411 (12)−0.0049 (9)0.0061 (9)0.0025 (9)
O160.0454 (13)0.0245 (11)0.0529 (14)−0.0018 (9)0.0104 (10)−0.0053 (9)
O170.0316 (11)0.0261 (10)0.0380 (11)−0.0023 (8)0.0041 (9)0.0009 (8)
O180.0391 (12)0.0314 (11)0.0489 (13)0.0020 (9)0.0092 (10)−0.0041 (9)
O190.0366 (12)0.0326 (11)0.0584 (15)−0.0078 (9)0.0112 (10)−0.0016 (10)
O200.0367 (12)0.0359 (12)0.0494 (13)0.0007 (9)0.0048 (10)0.0012 (10)
O210.0601 (18)0.081 (2)0.0669 (19)−0.0153 (15)0.0078 (14)−0.0006 (15)
O220.109 (3)0.172 (5)0.076 (3)0.009 (3)−0.008 (2)0.047 (3)
N10.0321 (12)0.0246 (12)0.0337 (13)−0.0009 (9)0.0058 (10)−0.0015 (10)
N20.0318 (13)0.0270 (13)0.0546 (16)−0.0055 (10)0.0134 (11)−0.0014 (11)
N30.0453 (16)0.0344 (14)0.0453 (16)−0.0060 (11)0.0034 (12)0.0091 (12)
N40.0368 (14)0.0380 (14)0.0437 (15)−0.0131 (11)0.0077 (11)−0.0011 (11)
N50.0496 (17)0.0567 (18)0.0399 (16)−0.0060 (14)0.0039 (13)0.0054 (13)
C10.0316 (15)0.0324 (15)0.0348 (16)−0.0026 (12)0.0022 (12)0.0032 (12)
C20.0335 (15)0.0287 (15)0.0345 (16)−0.0043 (11)0.0041 (12)0.0003 (12)
C30.0407 (17)0.0396 (17)0.0358 (17)−0.0127 (13)0.0089 (13)−0.0098 (13)
C40.0473 (19)0.0421 (18)0.052 (2)−0.0113 (15)0.0117 (16)−0.0193 (16)
C50.0373 (17)0.0344 (16)0.0449 (18)−0.0062 (13)0.0122 (14)−0.0091 (13)
C60.0296 (14)0.0273 (14)0.0352 (15)−0.0052 (11)0.0037 (11)−0.0024 (11)
C70.0304 (15)0.0278 (14)0.0351 (15)−0.0015 (11)0.0076 (12)−0.0028 (12)
C80.0314 (15)0.0260 (15)0.0497 (18)−0.0078 (12)0.0062 (13)0.0008 (13)
C90.0294 (15)0.0277 (15)0.0558 (19)−0.0058 (12)0.0045 (13)−0.0007 (13)
C100.0347 (17)0.0389 (18)0.066 (2)−0.0022 (13)0.0081 (15)0.0027 (16)
C110.0319 (18)0.048 (2)0.077 (3)0.0075 (15)0.0096 (17)0.0040 (18)
C120.0347 (18)0.0437 (19)0.075 (2)0.0046 (14)0.0177 (17)0.0018 (17)
C130.0303 (16)0.0323 (16)0.063 (2)−0.0025 (12)0.0121 (14)−0.0056 (14)
C140.0320 (16)0.0312 (16)0.059 (2)−0.0044 (12)0.0159 (14)−0.0048 (14)
C150.064 (2)0.054 (2)0.061 (2)−0.0097 (18)−0.0152 (19)0.0244 (19)
C160.053 (2)0.0405 (19)0.052 (2)−0.0051 (15)0.0019 (16)0.0157 (16)
C170.064 (2)0.043 (2)0.064 (2)−0.0055 (17)−0.0027 (19)0.0213 (18)
C180.068 (2)0.0361 (19)0.059 (2)−0.0099 (17)0.0109 (18)0.0140 (16)
C190.049 (2)0.0361 (17)0.053 (2)−0.0106 (15)0.0078 (16)0.0088 (15)
C200.0424 (17)0.0297 (15)0.0452 (18)−0.0054 (13)0.0086 (13)0.0030 (13)
C210.0377 (16)0.0230 (13)0.0394 (16)−0.0038 (12)0.0099 (13)−0.0018 (11)
C220.0259 (14)0.0310 (15)0.0377 (16)0.0005 (11)0.0037 (12)0.0002 (12)
C230.0302 (15)0.0278 (14)0.0320 (15)−0.0006 (11)0.0018 (11)−0.0005 (11)
C240.0289 (14)0.0288 (14)0.0322 (15)−0.0036 (11)0.0002 (11)−0.0002 (11)
C250.0319 (15)0.0278 (14)0.0315 (15)−0.0021 (11)0.0028 (11)−0.0022 (11)
C260.0351 (16)0.0313 (15)0.0326 (15)0.0017 (12)0.0043 (12)−0.0019 (12)
C270.0335 (15)0.0319 (15)0.0329 (15)−0.0013 (12)0.0039 (12)0.0007 (12)
C280.0296 (15)0.0287 (14)0.0372 (16)−0.0004 (11)0.0053 (12)0.0016 (12)
C290.0322 (15)0.0285 (15)0.0421 (17)−0.0024 (12)−0.0046 (12)0.0014 (12)
C300.0463 (18)0.0372 (17)0.0409 (18)0.0020 (14)0.0153 (14)0.0053 (13)
C310.079 (3)0.074 (3)0.059 (2)−0.014 (2)0.031 (2)0.007 (2)
C320.072 (3)0.066 (2)0.059 (2)−0.011 (2)0.034 (2)0.012 (2)
C330.070 (2)0.076 (3)0.064 (2)−0.007 (2)0.033 (2)0.015 (2)
C31X0.076 (3)0.071 (3)0.059 (2)−0.010 (2)0.032 (2)0.012 (2)
C32X0.069 (3)0.073 (3)0.062 (2)−0.011 (2)0.033 (2)0.011 (2)
C33X0.073 (3)0.074 (3)0.061 (2)−0.011 (2)0.034 (2)0.008 (2)
C340.0290 (15)0.0280 (14)0.0408 (16)−0.0053 (11)0.0056 (12)−0.0017 (12)
C350.0390 (17)0.0332 (16)0.0349 (16)−0.0011 (13)0.0037 (13)−0.0032 (12)
C360.033 (2)0.030 (2)0.034 (2)−0.0024 (16)0.0000.000
C370.072 (3)0.048 (2)0.0381 (18)0.0094 (18)0.0079 (17)−0.0049 (15)
C380.101 (5)0.067 (4)0.032 (3)0.018 (3)0.0000.000
C390.184 (7)0.144 (6)0.030 (2)0.050 (5)0.0000.000
C400.184 (7)0.146 (6)0.030 (3)0.049 (5)0.0035 (19)0.0037 (19)
C410.184 (7)0.145 (6)0.030 (3)0.049 (5)−0.0050 (19)−0.0029 (19)
C420.185 (7)0.144 (6)0.030 (3)0.051 (5)−0.0014 (19)−0.0063 (19)
C430.0321 (16)0.0362 (16)0.0449 (18)−0.0057 (12)0.0033 (13)0.0045 (13)
C440.051 (2)0.0433 (19)0.049 (2)−0.0125 (16)0.0109 (16)−0.0110 (15)
C450.060 (2)0.050 (2)0.075 (3)−0.0192 (18)0.032 (2)−0.0102 (19)
C460.0342 (17)0.0396 (17)0.0455 (18)−0.0013 (13)0.0082 (13)−0.0002 (14)
C470.081 (3)0.074 (3)0.071 (3)−0.015 (2)−0.015 (2)0.034 (2)
C480.084 (3)0.105 (4)0.041 (2)−0.017 (3)0.007 (2)−0.020 (2)
Geometric parameters (Å, º) top
Ni1—O15i2.012 (2)C12—H120.9500
Ni1—O132.020 (2)C13—C141.517 (5)
Ni1—O172.041 (2)C15—C161.509 (5)
Ni1—O12.054 (2)C16—C171.411 (5)
Ni1—O52.076 (2)C17—C181.378 (6)
Ni1—O112.110 (2)C17—H170.9500
Ni2—N21.994 (3)C18—C191.408 (5)
Ni2—O182.005 (2)C18—H180.9500
Ni2—O22.023 (2)C19—C201.398 (4)
Ni2—O192.057 (2)C19—H190.9500
Ni2—O72.128 (2)C20—C211.485 (5)
Ni2—O52.213 (2)C22—C231.483 (4)
Ni3—O16i1.960 (2)C23—C241.393 (4)
Ni3—N31.962 (3)C23—C281.398 (4)
Ni3—O62.063 (2)C24—C251.381 (4)
Ni3—O92.101 (2)C24—H240.9500
Ni3—O212.119 (3)C25—C261.400 (4)
Ni3—O112.192 (2)C25—C291.498 (4)
Ni4—N11.991 (2)C26—C271.390 (4)
Ni4—O142.002 (2)C26—H260.9500
Ni4—O32.043 (2)C27—C281.398 (4)
Ni4—O122.063 (2)C27—C301.532 (4)
Ni4—O202.065 (2)C28—H280.9500
Ni4—O12.2571 (19)C30—C32X1.490 (14)
Ni5—O22ii2.043 (4)C30—C331.495 (8)
Ni5—O22iii2.043 (4)C30—C311.512 (8)
Ni5—O222.043 (4)C30—C33X1.520 (13)
Ni5—O8ii2.077 (3)C30—C321.538 (7)
Ni5—O8iii2.077 (3)C30—C31X1.546 (13)
Ni5—O82.077 (3)C31—H31A0.9800
O1—C71.282 (3)C31—H31B0.9800
O2—C71.246 (3)C31—H31C0.9800
O3—C11.270 (4)C32—H320.9800
O4—C11.238 (4)C32—H1AB0.9800
O5—C81.281 (4)C32—H1AC0.9800
O6—C81.234 (4)C33—H33A0.9800
O7—C141.256 (4)C33—H33B0.9800
O8—C141.261 (4)C33—H33C0.9800
O9—C151.258 (4)C31X—H31D0.9800
O10—C151.256 (5)C31X—H31E0.9800
O10—H10S0.9394C31X—H31F0.9800
O11—C211.277 (3)C32X—H32A0.9800
O12—C211.248 (4)C32X—H32B0.9800
O13—C221.262 (3)C32X—H32C0.9800
O14—C221.268 (3)C33X—H33D0.9800
O15—C291.250 (4)C33X—H33E0.9800
O16—C291.261 (4)C33X—H33F0.9800
O17—C341.246 (4)C34—C351.511 (4)
O18—C341.263 (4)C35—C371.390 (5)
O19—C431.256 (4)C35—C361.394 (4)
O20—C461.235 (4)C36—H360.9500
O21—H21A0.9606C37—C381.390 (5)
O21—H21B0.9604C37—H370.9500
O22—H22A0.9599C38—C391.535 (8)
O22—H22B0.9599C39—C40i1.349 (15)
N1—C61.332 (4)C39—C401.349 (15)
N1—C21.340 (4)C39—C421.630 (14)
N2—C91.324 (4)C39—C42i1.630 (14)
N2—C131.340 (4)C39—C411.705 (15)
N3—C161.323 (4)C39—C41i1.705 (15)
N3—C201.349 (4)C40—H40A0.9800
N4—C431.314 (4)C40—H40B0.9800
N4—C441.456 (4)C40—H40C0.9800
N4—C451.458 (4)C41—H41A0.9800
N5—C461.316 (4)C41—H41B0.9800
N5—C471.434 (5)C41—H41C0.9800
N5—C481.496 (5)C42—H42A0.9800
C1—C21.519 (4)C42—H42B0.9800
C2—C31.377 (4)C42—H42C0.9800
C3—C41.405 (5)C43—H420.9500
C3—H30.9500C44—H43A0.9800
C4—C51.387 (4)C44—H43B0.9800
C4—H40.9500C44—H43C0.9800
C5—C61.381 (4)C45—H440.9800
C5—H50.9500C45—H0AB0.9800
C6—C71.495 (4)C45—H0AC0.9800
C8—C91.511 (4)C46—H450.9500
C9—C101.388 (5)C47—H460.9800
C10—C111.386 (5)C47—H7AB0.9800
C10—H100.9500C47—H7AC0.9800
C11—C121.380 (6)C48—H470.9800
C11—H110.9500C48—H6AB0.9800
C12—C131.373 (5)C48—H6AC0.9800
O15i—Ni1—O1386.48 (9)C19—C18—H18119.9
O15i—Ni1—O1784.55 (8)C20—C19—C18118.7 (3)
O13—Ni1—O1785.46 (8)C20—C19—H19120.7
O15i—Ni1—O1174.92 (9)C18—C19—H19120.7
O13—Ni1—O188.49 (8)N3—C20—C19119.6 (3)
O17—Ni1—O194.35 (8)N3—C20—C21114.0 (3)
O15i—Ni1—O595.80 (9)C19—C20—C21126.3 (3)
O13—Ni1—O5174.40 (9)O12—C21—O11127.5 (3)
O17—Ni1—O589.66 (8)O12—C21—C20116.7 (3)
O1—Ni1—O589.15 (8)O11—C21—C20115.8 (3)
O15i—Ni1—O1192.59 (8)O13—C22—O14123.6 (3)
O13—Ni1—O1194.50 (8)O13—C22—C23117.6 (3)
O17—Ni1—O11177.14 (8)O14—C22—C23118.8 (3)
O1—Ni1—O1188.51 (8)C24—C23—C28120.0 (3)
O5—Ni1—O1190.51 (8)C24—C23—C22119.3 (3)
N2—Ni2—O18174.38 (10)C28—C23—C22120.7 (3)
N2—Ni2—O291.11 (10)C25—C24—C23119.7 (3)
O18—Ni2—O291.09 (9)C25—C24—H24120.1
N2—Ni2—O1989.35 (10)C23—C24—H24120.1
O18—Ni2—O1988.62 (9)C24—C25—C26119.6 (3)
O2—Ni2—O19178.12 (9)C24—C25—C29120.8 (3)
N2—Ni2—O777.64 (10)C26—C25—C29119.6 (3)
O18—Ni2—O797.16 (9)C27—C26—C25121.9 (3)
O2—Ni2—O790.71 (8)C27—C26—H26119.1
O19—Ni2—O791.17 (9)C25—C26—H26119.1
N2—Ni2—O576.00 (9)C26—C27—C28117.6 (3)
O18—Ni2—O5109.22 (8)C26—C27—C30120.4 (3)
O2—Ni2—O588.83 (8)C28—C27—C30121.9 (3)
O19—Ni2—O589.51 (9)C27—C28—C23121.1 (3)
O7—Ni2—O5153.62 (9)C27—C28—H28119.5
O16i—Ni3—N3173.36 (11)C23—C28—H28119.5
O16i—Ni3—O690.87 (9)O15—C29—O16126.0 (3)
N3—Ni3—O694.12 (10)O15—C29—C25116.9 (3)
O16i—Ni3—O996.96 (9)O16—C29—C25117.1 (3)
N3—Ni3—O978.71 (11)C33—C30—C31109.0 (5)
O6—Ni3—O989.70 (10)C32X—C30—C33X105.7 (8)
O16i—Ni3—O2187.06 (11)C32X—C30—C27109.6 (5)
N3—Ni3—O2188.01 (12)C33—C30—C27108.3 (3)
O6—Ni3—O21177.74 (11)C31—C30—C27110.0 (3)
O9—Ni3—O2191.46 (12)C33X—C30—C27112.5 (5)
O16i—Ni3—O11107.46 (8)C33—C30—C32109.1 (5)
N3—Ni3—O1177.14 (10)C31—C30—C32107.1 (5)
O6—Ni3—O1187.90 (8)C27—C30—C32113.2 (3)
O9—Ni3—O11155.49 (8)C32X—C30—C31X113.5 (8)
O21—Ni3—O1191.85 (10)C33X—C30—C31X108.2 (8)
N1—Ni4—O14174.22 (9)C27—C30—C31X107.4 (5)
N1—Ni4—O379.56 (9)C30—C31—H31A109.5
O14—Ni4—O394.75 (8)C30—C31—H31B109.5
N1—Ni4—O1292.30 (9)H31A—C31—H31B109.5
O14—Ni4—O1287.02 (9)C30—C31—H31C109.5
O3—Ni4—O1293.97 (9)H31A—C31—H31C109.5
N1—Ni4—O2086.34 (10)H31B—C31—H31C109.5
O14—Ni4—O2094.67 (9)C30—C32—H32109.5
O3—Ni4—O2089.02 (9)C30—C32—H1AB109.5
O12—Ni4—O20176.44 (9)H32—C32—H1AB109.5
N1—Ni4—O174.62 (8)C30—C32—H1AC109.5
O14—Ni4—O1111.05 (8)H32—C32—H1AC109.5
O3—Ni4—O1154.18 (8)H1AB—C32—H1AC109.5
O12—Ni4—O186.58 (8)C30—C33—H33A109.5
O20—Ni4—O189.89 (8)C30—C33—H33B109.5
O22ii—Ni5—O22iii88.54 (18)H33A—C33—H33B109.5
O22ii—Ni5—O2288.54 (18)C30—C33—H33C109.5
O22iii—Ni5—O2288.54 (18)H33A—C33—H33C109.5
O22ii—Ni5—O8ii175.40 (16)H33B—C33—H33C109.5
O22iii—Ni5—O8ii95.53 (17)C30—C31X—H31D109.5
O22—Ni5—O8ii89.42 (14)C30—C31X—H31E109.5
O22ii—Ni5—O8iii89.43 (14)H31D—C31X—H31E109.5
O22iii—Ni5—O8iii175.40 (16)C30—C31X—H31F109.5
O22—Ni5—O8iii95.53 (16)H31D—C31X—H31F109.5
O8ii—Ni5—O8iii86.66 (10)H31E—C31X—H31F109.5
O22ii—Ni5—O895.54 (16)C30—C32X—H32A109.5
O22iii—Ni5—O889.43 (14)C30—C32X—H32B109.5
O22—Ni5—O8175.39 (16)H32A—C32X—H32B109.5
O8ii—Ni5—O886.65 (10)C30—C32X—H32C109.5
O8iii—Ni5—O886.66 (10)H32A—C32X—H32C109.5
C7—O1—Ni1137.04 (19)H32B—C32X—H32C109.5
C7—O1—Ni4113.79 (17)C30—C33X—H33D109.5
Ni1—O1—Ni4106.31 (8)C30—C33X—H33E109.5
C7—O2—Ni2127.57 (19)H33D—C33X—H33E109.5
C1—O3—Ni4116.02 (18)C30—C33X—H33F109.5
C8—O5—Ni1133.36 (19)H33D—C33X—H33F109.5
C8—O5—Ni2114.19 (19)H33E—C33X—H33F109.5
Ni1—O5—Ni2107.90 (9)O17—C34—O18126.1 (3)
C8—O6—Ni3131.1 (2)O17—C34—C35116.3 (3)
C14—O7—Ni2115.0 (2)O18—C34—C35117.6 (3)
C14—O8—Ni5129.5 (2)C37—C35—C36119.7 (3)
C15—O9—Ni3114.0 (2)C37—C35—C34120.7 (3)
C15—O10—H10S119.2C36—C35—C34119.5 (3)
C21—O11—Ni1135.3 (2)C35i—C36—C35119.5 (4)
C21—O11—Ni3113.28 (19)C35i—C36—H36120.3
Ni1—O11—Ni3107.92 (8)C35—C36—H36120.3
C21—O12—Ni4126.87 (19)C38—C37—C35121.5 (4)
C22—O13—Ni1131.09 (19)C38—C37—H37119.2
C22—O14—Ni4116.94 (18)C35—C37—H37119.2
C29—O15—Ni1i137.9 (2)C37—C38—C37i118.0 (5)
C29—O16—Ni3i125.0 (2)C37—C38—C39121.0 (2)
C34—O17—Ni1137.06 (19)C37i—C38—C39121.0 (2)
C34—O18—Ni2120.2 (2)C40i—C39—C40132.3 (12)
C43—O19—Ni2122.1 (2)C40i—C39—C38113.9 (6)
C46—O20—Ni4131.2 (2)C40—C39—C38113.9 (6)
Ni3—O21—H21A122.0C40i—C39—C4239.9 (8)
Ni3—O21—H21B108.7C40—C39—C42120.2 (8)
H21A—O21—H21B109.3C38—C39—C42109.0 (4)
Ni5—O22—H22A109.3C40i—C39—C42i120.2 (8)
Ni5—O22—H22B109.3C40—C39—C42i39.9 (8)
H22A—O22—H22B109.5C38—C39—C42i109.0 (4)
C6—N1—C2121.5 (2)C42—C39—C42i142.0 (9)
C6—N1—Ni4122.31 (19)C40i—C39—C4154.5 (7)
C2—N1—Ni4116.08 (19)C40—C39—C41111.8 (8)
C9—N2—C13120.9 (3)C38—C39—C41104.9 (4)
C9—N2—Ni2120.3 (2)C42—C39—C4194.4 (7)
C13—N2—Ni2118.6 (2)C42i—C39—C4175.9 (8)
C16—N3—C20122.5 (3)C40i—C39—C41i111.8 (8)
C16—N3—Ni3118.1 (2)C40—C39—C41i54.5 (7)
C20—N3—Ni3119.0 (2)C38—C39—C41i104.9 (4)
C43—N4—C44122.4 (3)C42—C39—C41i75.9 (7)
C43—N4—C45120.9 (3)C42i—C39—C41i94.4 (7)
C44—N4—C45116.7 (3)C41—C39—C41i150.2 (8)
C46—N5—C47122.9 (3)C39—C40—H40A109.5
C46—N5—C48118.8 (3)C39—C40—H40B109.5
C47—N5—C48117.6 (4)H40A—C40—H40B109.5
O4—C1—O3127.0 (3)C39—C40—H40C109.5
O4—C1—C2118.1 (3)H40A—C40—H40C109.5
O3—C1—C2114.9 (2)H40B—C40—H40C109.5
N1—C2—C3120.7 (3)C39—C41—H41A109.5
N1—C2—C1113.1 (3)C39—C41—H41B109.5
C3—C2—C1126.1 (3)H41A—C41—H41B109.5
C2—C3—C4118.3 (3)C39—C41—H41C109.5
C2—C3—H3120.8H41A—C41—H41C109.5
C4—C3—H3120.8H41B—C41—H41C109.5
C5—C4—C3119.8 (3)C39—C41—H40Bi86.0 (13)
C5—C4—H4120.1H41A—C41—H40Bi150.2
C3—C4—H4120.1H41B—C41—H40Bi40.7
C6—C5—C4118.4 (3)H41C—C41—H40Bi87.7
C6—C5—H5120.8C39—C42—H42A109.5
C4—C5—H5120.8C39—C42—H42B109.5
N1—C6—C5121.2 (3)H42A—C42—H42B109.5
N1—C6—C7113.7 (2)C39—C42—H42C109.5
C5—C6—C7125.1 (3)H42A—C42—H42C109.5
O2—C7—O1127.1 (3)H42B—C42—H42C109.5
O2—C7—C6117.4 (3)C39—C42—H40Ci105.6 (17)
O1—C7—C6115.6 (2)H42A—C42—H40Ci124.0
O6—C8—O5127.2 (3)H42B—C42—H40Ci97.8
O6—C8—C9118.0 (3)H42C—C42—H40Ci15.4
O5—C8—C9114.8 (3)O19—C43—N4123.5 (3)
N2—C9—C10121.4 (3)O19—C43—H42118.3
N2—C9—C8114.2 (3)N4—C43—H42118.3
C10—C9—C8124.4 (3)N4—C44—H43A109.5
C11—C10—C9117.7 (4)N4—C44—H43B109.5
C11—C10—H10121.1H43A—C44—H43B109.5
C9—C10—H10121.1N4—C44—H43C109.5
C12—C11—C10120.3 (4)H43A—C44—H43C109.5
C12—C11—H11119.8H43B—C44—H43C109.5
C10—C11—H11119.8N4—C45—H44109.5
C13—C12—C11118.5 (3)N4—C45—H0AB109.5
C13—C12—H12120.7H44—C45—H0AB109.5
C11—C12—H12120.7N4—C45—H0AC109.5
N2—C13—C12121.0 (4)H44—C45—H0AC109.5
N2—C13—C14112.3 (3)H0AB—C45—H0AC109.5
C12—C13—C14126.7 (3)O20—C46—N5125.3 (3)
O7—C14—O8127.4 (3)O20—C46—H45117.4
O7—C14—C13116.4 (3)N5—C46—H45117.4
O8—C14—C13116.2 (3)N5—C47—H46109.5
O10—C15—O9125.5 (4)N5—C47—H7AB109.5
O10—C15—C16118.3 (3)H46—C47—H7AB109.5
O9—C15—C16116.2 (3)N5—C47—H7AC109.5
N3—C16—C17120.9 (4)H46—C47—H7AC109.5
N3—C16—C15112.7 (3)H7AB—C47—H7AC109.5
C17—C16—C15126.4 (3)N5—C48—H47109.5
C18—C17—C16118.1 (4)N5—C48—H6AB109.5
C18—C17—H17120.9H47—C48—H6AB109.5
C16—C17—H17120.9N5—C48—H6AC109.5
C17—C18—C19120.2 (3)H47—C48—H6AC109.5
C17—C18—H18119.9H6AB—C48—H6AC109.5
Symmetry codes: (i) −x+3/4, −y+3/4, z; (ii) z, −x+3/4, −y+3/4; (iii) −y+3/4, −z+3/4, x.
(3) top
Crystal data top
C504H442Br18N72Ni52O264Mo Kα radiation, λ = 0.71073 Å
Mr = 16222.57Cell parameters from 738912 reflections
Cubic, Fd3θ = 2.3–23.8°
a = 58.069 (7) ŵ = 1.77 mm−1
V = 195809 (68) Å3T = 100 K
Z = 8Block, green
F(000) = 653440.25 × 0.24 × 0.20 mm
Dx = 1.101 Mg m−3
Data collection top
CCD detector
diffractometer		14106 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.014
phi and ω scansθmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan
SADABS		h = −71→71
Tmin = 0.534, Tmax = 0.615k = −50→50
31600 measured reflectionsl = −49→49
16050 independent reflections
Refinement top
Refinement on F2744 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.165 w = 1/[σ2(Fo2) + (0.0783P)2 + 2584.917P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.003
16050 reflectionsΔρmax = 1.37 e Å−3
685 parametersΔρmin = −1.78 e Å−3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Br10.58366 (2)0.40387 (2)0.27119 (2)0.05018 (14)
Br20.77990 (2)0.3750000.3750000.1764 (8)
Ni10.65205 (2)0.43495 (2)0.39093 (2)0.02970 (13)
Ni20.69456 (2)0.44829 (2)0.43119 (2)0.03614 (14)
Ni30.59965 (2)0.45164 (2)0.41400 (2)0.04014 (15)
Ni40.66201 (2)0.47004 (2)0.34425 (2)0.03682 (14)
Ni50.77085 (2)0.47915 (2)0.47915 (2)0.0553 (3)
O10.67418 (5)0.46003 (4)0.37918 (5)0.0353 (6)
O20.69714 (5)0.47349 (5)0.40759 (5)0.0372 (7)
O30.66065 (6)0.49074 (5)0.31550 (5)0.0405 (7)
O40.67753 (6)0.52106 (5)0.29923 (5)0.0426 (7)
O50.65686 (5)0.44753 (5)0.42425 (5)0.0355 (6)
O60.62430 (6)0.46485 (5)0.43599 (5)0.0400 (7)
O70.72425 (6)0.46003 (5)0.44827 (5)0.0456 (8)
O80.73553 (6)0.48432 (6)0.47644 (6)0.0498 (8)
O90.62488 (5)0.45773 (4)0.38621 (5)0.0374 (6)
O100.63447 (6)0.48559 (5)0.36050 (5)0.0417 (7)
O110.57293 (7)0.46037 (6)0.43651 (7)0.0594 (9)
O120.54658 (9)0.48741 (9)0.44221 (10)0.0961 (17)
H12S0.5401780.4808660.4553830.144*0.3333
O130.64952 (5)0.42110 (5)0.35898 (5)0.0371 (7)
O140.63959 (6)0.44685 (5)0.33208 (5)0.0451 (8)
O150.63013 (5)0.34067 (5)0.34945 (5)0.0368 (6)
O160.60377 (6)0.32984 (5)0.32361 (5)0.0421 (7)
O170.67715 (5)0.41123 (4)0.39608 (4)0.0317 (6)
O180.71011 (6)0.42592 (5)0.40985 (5)0.0414 (7)
O190.69043 (6)0.42251 (5)0.45481 (5)0.0453 (8)
O200.57634 (8)0.43883 (7)0.39059 (8)0.0704 (12)
O210.69013 (7)0.45343 (6)0.33003 (6)0.0551 (9)
O220.80638 (13)0.47412 (17)0.48418 (13)0.155 (3)
H22A0.8154890.4812530.4739980.233*
H22B0.8106510.4594660.4863060.233*
N10.68366 (6)0.49484 (5)0.35314 (6)0.0331 (7)
N20.68146 (7)0.47065 (6)0.45352 (6)0.0403 (8)
N30.59114 (7)0.48232 (6)0.40215 (7)0.0463 (9)
N40.68038 (7)0.38612 (7)0.46297 (6)0.0444 (9)
N50.55899 (13)0.41781 (13)0.36394 (12)0.105 (2)
N60.71819 (9)0.42798 (11)0.32312 (10)0.0744 (14)
C10.67467 (8)0.50767 (7)0.31525 (7)0.0351 (9)
C20.68796 (7)0.51114 (7)0.33747 (7)0.0329 (8)
C30.70345 (7)0.52835 (7)0.34205 (8)0.0371 (9)
H30.7066740.5398740.3308880.045*
C40.71430 (8)0.52859 (8)0.36326 (8)0.0416 (10)
H40.7249160.5405060.3668670.050*
C50.70974 (7)0.51160 (7)0.37916 (7)0.0348 (9)
H50.7171080.5116400.3937700.042*
C60.69434 (7)0.49460 (6)0.37347 (6)0.0293 (8)
C70.68789 (7)0.47431 (6)0.38823 (7)0.0320 (8)
C80.64511 (8)0.46114 (7)0.43680 (7)0.0366 (9)
C90.65871 (9)0.47419 (7)0.45469 (7)0.0412 (10)
C100.64935 (11)0.48892 (10)0.47095 (9)0.0592 (13)
H100.6332190.4914560.4719270.071*
C110.66472 (12)0.49989 (12)0.48585 (10)0.0741 (18)
H110.6589350.5100810.4972670.089*
C120.68796 (11)0.49624 (11)0.48434 (10)0.0655 (15)
H120.6982620.5039000.4944840.079*
C130.69618 (9)0.48127 (8)0.46786 (8)0.0472 (10)
C140.72078 (9)0.47478 (8)0.46394 (8)0.0448 (10)
C150.62225 (8)0.47716 (7)0.37592 (8)0.0401 (9)
C160.60193 (8)0.49083 (7)0.38357 (8)0.0425 (10)
C170.59388 (9)0.51106 (8)0.37339 (10)0.0536 (12)
H170.6013290.5173190.3602360.064*
C180.57488 (10)0.52180 (9)0.38282 (12)0.0646 (14)
H180.5690830.5354860.3759830.077*
C190.56420 (10)0.51280 (9)0.40214 (12)0.0622 (14)
H190.5514180.5203900.4089690.075*
C200.57280 (10)0.49209 (8)0.41139 (11)0.0562 (12)
C210.56316 (10)0.47878 (10)0.43185 (12)0.0645 (14)
C220.63907 (7)0.42697 (7)0.34120 (7)0.0342 (9)
C230.62520 (7)0.40898 (6)0.32900 (7)0.0305 (8)
C240.62584 (7)0.38637 (6)0.33722 (7)0.0298 (8)
H240.6342350.3828260.3508090.036*
C250.61421 (7)0.36913 (6)0.32552 (7)0.0328 (8)
C260.60136 (7)0.37420 (7)0.30601 (7)0.0349 (8)
H260.5929930.3625000.2982130.042*
C270.60101 (7)0.39678 (7)0.29815 (7)0.0353 (9)
C280.61300 (8)0.41415 (7)0.30918 (7)0.0368 (9)
H280.6128730.4293960.3032440.044*
C290.61638 (7)0.34445 (7)0.33376 (7)0.0339 (8)
C300.69874 (8)0.41168 (7)0.39815 (7)0.0349 (8)
C310.71186 (8)0.39266 (7)0.38605 (8)0.0408 (9)
C320.70011 (11)0.3750000.3750000.0346 (12)
H01A0.6837460.3750000.3750020.041*
C330.73577 (9)0.39282 (11)0.38601 (12)0.0650 (15)
H330.7439830.4048990.3933760.078*
C340.74758 (14)0.3750000.3750000.077 (3)
C350.67959 (8)0.40465 (7)0.45019 (7)0.0377 (9)
H350.6702780.4044460.4367400.045*
C360.66730 (10)0.36602 (9)0.45759 (9)0.0551 (13)
H01C0.6702550.3541180.4691870.083*
H01D0.6508620.3698540.4575320.083*
H01G0.6717950.3602890.4423720.083*
C370.69475 (12)0.38512 (11)0.48365 (11)0.0732 (19)
H01I0.6931120.3699690.4909050.110*
H01K0.7108960.3875990.4793990.110*
H01L0.6898780.3971040.4944780.110*
C380.57617 (15)0.42458 (16)0.37804 (15)0.097 (2)
H380.5900000.4158990.3770060.116*
C390.5621 (2)0.3984 (2)0.3481 (2)0.169 (5)
H39A0.5478710.3959870.3392930.253*
H39B0.5747620.4017410.3374800.253*
H39C0.5656510.3844430.3569030.253*
C400.5353 (2)0.4254 (3)0.3668 (3)0.182 (5)
H40A0.5256940.4184920.3547680.273*
H40B0.5296540.4206720.3819530.273*
H40C0.5346220.4422390.3655320.273*
C410.69808 (10)0.43404 (9)0.33086 (9)0.0564 (12)
H410.6888370.4224120.3377220.068*
C420.72424 (16)0.40315 (15)0.32222 (15)0.103 (3)
H02C0.7398400.4013860.3160320.155*
H02D0.7235900.3966400.3377790.155*
H02E0.7132850.3950470.3122680.155*
C430.73258 (12)0.44499 (18)0.31110 (16)0.104 (3)
H02F0.7470780.4377610.3063790.156*
H02G0.7244030.4506320.2974530.156*
H02H0.7358380.4579140.3214470.156*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0588 (3)0.0449 (3)0.0468 (3)−0.0047 (2)−0.0292 (2)0.0020 (2)
Br20.0453 (5)0.1955 (14)0.2883 (17)0.0000.000−0.1282 (13)
Ni10.0428 (3)0.0184 (2)0.0279 (2)−0.00210 (19)−0.0116 (2)0.00456 (18)
Ni20.0545 (3)0.0252 (2)0.0288 (3)−0.0045 (2)−0.0156 (2)0.00509 (19)
Ni30.0481 (3)0.0246 (3)0.0478 (3)0.0065 (2)−0.0102 (3)0.0019 (2)
Ni40.0545 (3)0.0213 (2)0.0347 (3)−0.0064 (2)−0.0221 (2)0.0063 (2)
Ni50.0553 (3)0.0553 (3)0.0553 (3)0.0049 (3)0.0049 (3)−0.0049 (3)
O10.0500 (17)0.0218 (12)0.0341 (14)−0.0050 (11)−0.0174 (12)0.0066 (11)
O20.0522 (17)0.0277 (14)0.0316 (14)−0.0096 (12)−0.0173 (13)0.0068 (11)
O30.0553 (18)0.0292 (14)0.0371 (15)−0.0024 (12)−0.0222 (14)0.0032 (12)
O40.0535 (18)0.0383 (16)0.0359 (15)−0.0003 (14)−0.0117 (13)0.0140 (13)
O50.0518 (17)0.0235 (13)0.0313 (14)−0.0012 (12)−0.0101 (12)0.0024 (11)
O60.0555 (18)0.0274 (14)0.0370 (15)0.0024 (13)−0.0086 (14)0.0012 (12)
O70.064 (2)0.0340 (15)0.0387 (16)−0.0051 (14)−0.0228 (15)0.0049 (12)
O80.061 (2)0.0443 (18)0.0438 (18)−0.0141 (15)−0.0207 (15)0.0009 (14)
O90.0511 (17)0.0210 (12)0.0400 (15)0.0019 (12)−0.0173 (13)0.0046 (11)
O100.0525 (18)0.0245 (14)0.0482 (17)−0.0039 (12)−0.0198 (14)0.0116 (12)
O110.061 (2)0.0427 (18)0.074 (2)0.0164 (16)0.0026 (19)0.0057 (17)
O120.097 (4)0.077 (3)0.114 (4)0.046 (3)0.026 (3)0.015 (3)
O130.0535 (18)0.0259 (13)0.0319 (14)0.0012 (12)−0.0174 (13)0.0025 (11)
O140.073 (2)0.0220 (13)0.0401 (16)−0.0108 (13)−0.0283 (15)0.0086 (12)
O150.0505 (17)0.0218 (13)0.0382 (15)0.0026 (12)−0.0012 (13)0.0017 (11)
O160.0540 (18)0.0260 (14)0.0464 (17)−0.0083 (13)0.0007 (14)0.0025 (12)
O170.0454 (15)0.0222 (12)0.0274 (13)0.0032 (11)−0.0066 (11)0.0059 (10)
O180.0497 (18)0.0347 (15)0.0397 (16)−0.0056 (13)−0.0098 (13)0.0004 (12)
O190.062 (2)0.0355 (15)0.0383 (16)−0.0075 (14)−0.0162 (15)0.0115 (13)
O200.078 (3)0.049 (2)0.085 (3)−0.011 (2)−0.036 (2)0.0085 (19)
O210.074 (2)0.0455 (18)0.0459 (19)0.0088 (17)−0.0201 (17)−0.0070 (15)
O220.116 (5)0.233 (9)0.116 (5)0.052 (6)0.034 (4)−0.001 (6)
N10.0414 (18)0.0257 (15)0.0322 (16)−0.0016 (13)−0.0121 (14)0.0086 (13)
N20.061 (2)0.0303 (17)0.0299 (17)−0.0057 (16)−0.0155 (16)0.0034 (14)
N30.051 (2)0.0294 (18)0.058 (2)0.0068 (16)−0.0178 (17)−0.0021 (16)
N40.052 (2)0.046 (2)0.0354 (19)−0.0129 (17)−0.0109 (16)0.0193 (16)
N50.094 (4)0.121 (6)0.099 (5)−0.033 (4)−0.032 (4)−0.017 (4)
N60.049 (3)0.095 (4)0.079 (3)0.023 (2)−0.012 (2)0.013 (3)
C10.045 (2)0.0273 (19)0.033 (2)0.0018 (16)−0.0117 (17)0.0057 (15)
C20.040 (2)0.0261 (18)0.0320 (19)0.0013 (15)−0.0079 (16)0.0064 (15)
C30.032 (2)0.036 (2)0.043 (2)−0.0055 (16)−0.0078 (17)0.0146 (18)
C40.040 (2)0.038 (2)0.047 (2)−0.0114 (18)−0.0107 (19)0.0124 (18)
C50.034 (2)0.034 (2)0.036 (2)−0.0068 (16)−0.0101 (16)0.0036 (16)
C60.0358 (19)0.0240 (17)0.0282 (18)−0.0004 (14)−0.0090 (15)0.0071 (14)
C70.043 (2)0.0237 (17)0.0298 (18)−0.0024 (15)−0.0095 (16)0.0038 (14)
C80.052 (2)0.0259 (19)0.032 (2)−0.0023 (17)−0.0114 (17)0.0056 (15)
C90.065 (3)0.030 (2)0.0287 (19)−0.0063 (19)−0.0125 (19)0.0036 (16)
C100.071 (3)0.065 (3)0.042 (3)−0.002 (3)−0.007 (2)−0.016 (2)
C110.085 (4)0.085 (4)0.053 (3)0.002 (3)−0.012 (3)−0.034 (3)
C120.080 (3)0.069 (4)0.047 (3)−0.010 (3)−0.021 (3)−0.023 (3)
C130.068 (3)0.039 (2)0.035 (2)−0.013 (2)−0.017 (2)−0.0007 (18)
C140.063 (3)0.037 (2)0.034 (2)−0.007 (2)−0.0184 (19)0.0072 (17)
C150.053 (2)0.0218 (18)0.046 (2)−0.0002 (17)−0.0233 (19)0.0015 (16)
C160.051 (2)0.0222 (18)0.054 (3)−0.0018 (17)−0.0241 (19)0.0050 (17)
C170.062 (3)0.030 (2)0.068 (3)0.003 (2)−0.033 (2)0.007 (2)
C180.067 (3)0.034 (2)0.093 (4)0.009 (2)−0.037 (3)0.007 (2)
C190.063 (3)0.037 (2)0.087 (4)0.017 (2)−0.024 (3)−0.008 (2)
C200.058 (3)0.033 (2)0.078 (3)0.012 (2)−0.011 (2)0.000 (2)
C210.058 (3)0.051 (3)0.085 (4)0.017 (2)−0.003 (3)0.000 (3)
C220.043 (2)0.0255 (18)0.034 (2)−0.0063 (16)−0.0158 (17)0.0042 (15)
C230.036 (2)0.0243 (17)0.0311 (19)−0.0016 (15)−0.0083 (15)0.0015 (14)
C240.036 (2)0.0224 (16)0.0304 (18)0.0019 (15)−0.0041 (15)0.0007 (14)
C250.037 (2)0.0244 (18)0.037 (2)−0.0024 (15)0.0019 (16)0.0019 (15)
C260.037 (2)0.0281 (18)0.040 (2)−0.0050 (16)−0.0039 (17)−0.0041 (16)
C270.040 (2)0.0329 (19)0.033 (2)0.0000 (16)−0.0129 (17)0.0008 (16)
C280.046 (2)0.0257 (18)0.039 (2)−0.0023 (16)−0.0121 (18)0.0024 (16)
C290.042 (2)0.0242 (18)0.036 (2)0.0004 (15)0.0039 (16)−0.0008 (15)
C300.044 (2)0.0279 (18)0.032 (2)−0.0032 (16)−0.0092 (17)0.0102 (15)
C310.040 (2)0.035 (2)0.048 (2)−0.0051 (17)−0.0036 (18)0.0060 (18)
C320.041 (3)0.030 (3)0.033 (3)0.0000.0000.005 (2)
C330.041 (3)0.069 (4)0.085 (4)−0.005 (2)−0.009 (3)−0.018 (3)
C340.038 (4)0.090 (6)0.103 (7)0.0000.000−0.034 (5)
C350.045 (2)0.040 (2)0.029 (2)−0.0013 (18)−0.0026 (17)0.0075 (16)
C360.067 (3)0.052 (3)0.047 (3)−0.015 (2)−0.016 (2)0.018 (2)
C370.085 (4)0.071 (4)0.063 (3)−0.028 (3)−0.036 (3)0.035 (3)
C380.091 (5)0.108 (6)0.092 (5)−0.014 (5)−0.025 (4)−0.017 (4)
C390.148 (8)0.213 (9)0.146 (7)−0.003 (7)0.003 (6)−0.077 (7)
C400.141 (6)0.220 (9)0.184 (9)0.041 (7)−0.033 (7)−0.018 (8)
C410.064 (3)0.050 (3)0.055 (3)0.010 (2)−0.020 (2)0.006 (2)
C420.113 (6)0.107 (5)0.089 (5)0.051 (5)−0.010 (5)0.011 (5)
C430.054 (4)0.151 (7)0.106 (6)−0.020 (4)−0.019 (4)0.020 (5)
Geometric parameters (Å, º) top
Br1—C271.907 (4)N6—C411.300 (8)
Br2—C341.877 (8)N6—C431.470 (10)
Ni1—O132.028 (3)N6—C421.485 (10)
Ni1—O172.028 (3)C1—C21.517 (5)
Ni1—O15i2.037 (3)C2—C31.371 (6)
Ni1—O12.058 (3)C3—C41.384 (6)
Ni1—O92.077 (3)C3—H30.9500
Ni1—O52.087 (3)C4—C51.377 (6)
Ni2—N21.987 (4)C4—H40.9500
Ni2—O182.009 (3)C5—C61.372 (5)
Ni2—O22.011 (3)C5—H50.9500
Ni2—O192.044 (3)C6—C71.505 (5)
Ni2—O72.103 (3)C8—C91.509 (6)
Ni2—O52.227 (3)C9—C101.385 (7)
Ni3—N31.973 (4)C10—C111.397 (8)
Ni3—O16i1.979 (3)C10—H100.9500
Ni3—O202.057 (4)C11—C121.369 (9)
Ni3—O62.066 (3)C11—H110.9500
Ni3—O112.091 (4)C12—C131.378 (8)
Ni3—O92.208 (3)C12—H120.9500
Ni4—N11.981 (3)C13—C141.495 (8)
Ni4—O142.001 (3)C15—C161.490 (7)
Ni4—O32.059 (3)C16—C171.396 (6)
Ni4—O102.065 (4)C17—C181.380 (9)
Ni4—O212.069 (4)C17—H170.9500
Ni4—O12.225 (3)C18—C191.384 (9)
Ni5—O82.079 (4)C18—H180.9500
Ni5—O8ii2.079 (4)C19—C201.409 (7)
Ni5—O8iii2.079 (4)C19—H190.9500
Ni5—O22ii2.104 (7)C20—C211.524 (9)
Ni5—O22iii2.104 (7)C22—C231.498 (5)
Ni5—O222.104 (7)C23—C281.384 (5)
O1—C71.264 (5)C23—C241.398 (5)
O2—C71.246 (5)C24—C251.386 (5)
O3—C11.276 (5)C24—H240.9500
O4—C11.224 (5)C25—C261.389 (6)
O5—C81.273 (5)C25—C291.516 (5)
O6—C81.229 (6)C26—C271.388 (6)
O7—C141.266 (6)C26—H260.9500
O8—C141.252 (5)C27—C281.383 (6)
O9—C151.286 (5)C28—H280.9500
O10—C151.243 (6)C30—C311.515 (6)
O11—C211.240 (6)C31—C331.388 (7)
O12—C211.240 (7)C31—C321.389 (5)
O12—H12S0.9318C32—H01A0.9500
O13—C221.245 (5)C33—C341.397 (7)
O14—C221.270 (5)C33—H330.9500
O15—C291.231 (5)C35—H350.9500
O16—C291.266 (5)C36—H01C0.9800
O17—C301.259 (5)C36—H01D0.9800
O18—C301.258 (5)C36—H01G0.9800
O19—C351.243 (5)C37—H01I0.9800
O20—C381.103 (9)C37—H01K0.9800
O21—C411.218 (6)C37—H01L0.9800
O22—H22A0.8951C38—H380.9500
O22—H22B0.8951C39—H39A0.9800
N1—C61.334 (5)C39—H39B0.9800
N1—C21.336 (5)C39—H39C0.9800
N2—C91.339 (6)C40—H40A0.9800
N2—C131.343 (6)C40—H40B0.9800
N3—C201.321 (7)C40—H40C0.9800
N3—C161.342 (7)C41—H410.9500
N4—C351.308 (5)C42—H02C0.9800
N4—C361.427 (6)C42—H02D0.9800
N4—C371.463 (6)C42—H02E0.9800
N5—C381.349 (9)C43—H02F0.9800
N5—C401.453 (14)C43—H02G0.9800
N5—C391.467 (5)C43—H02H0.9800
O13—Ni1—O1785.27 (11)C6—C5—H5120.7
O13—Ni1—O15i85.18 (12)C4—C5—H5120.7
O17—Ni1—O15i84.97 (12)N1—C6—C5120.6 (3)
O13—Ni1—O191.29 (12)N1—C6—C7113.4 (3)
O17—Ni1—O194.62 (11)C5—C6—C7126.1 (3)
O15i—Ni1—O1176.47 (12)O2—C7—O1128.4 (4)
O13—Ni1—O994.42 (11)O2—C7—C6115.9 (3)
O17—Ni1—O9176.51 (12)O1—C7—C6115.7 (3)
O15i—Ni1—O991.54 (12)O6—C8—O5127.9 (4)
O1—Ni1—O988.86 (12)O6—C8—C9116.9 (4)
O13—Ni1—O5175.52 (12)O5—C8—C9115.2 (4)
O17—Ni1—O590.27 (11)N2—C9—C10121.1 (4)
O15i—Ni1—O594.87 (11)N2—C9—C8113.8 (4)
O1—Ni1—O588.63 (11)C10—C9—C8125.1 (5)
O9—Ni1—O590.06 (11)C9—C10—C11117.0 (6)
N2—Ni2—O18175.66 (14)C9—C10—H10121.5
N2—Ni2—O289.86 (13)C11—C10—H10121.5
O18—Ni2—O290.95 (13)C12—C11—C10121.3 (6)
N2—Ni2—O1989.75 (14)C12—C11—H11119.3
O18—Ni2—O1989.62 (13)C10—C11—H11119.3
O2—Ni2—O19177.46 (13)C11—C12—C13118.9 (5)
N2—Ni2—O778.13 (15)C11—C12—H12120.5
O18—Ni2—O797.59 (13)C13—C12—H12120.5
O2—Ni2—O791.41 (12)N2—C13—C12120.0 (5)
O19—Ni2—O790.98 (12)N2—C13—C14113.4 (4)
N2—Ni2—O575.77 (13)C12—C13—C14126.6 (4)
O18—Ni2—O5108.52 (11)O8—C14—O7127.4 (5)
O2—Ni2—O587.94 (11)O8—C14—C13117.0 (4)
O19—Ni2—O589.52 (12)O7—C14—C13115.6 (4)
O7—Ni2—O5153.89 (12)O10—C15—O9127.8 (4)
N3—Ni3—O16i172.45 (16)O10—C15—C16117.2 (4)
N3—Ni3—O2086.05 (16)O9—C15—C16115.0 (4)
O16i—Ni3—O2089.21 (15)N3—C16—C17119.6 (5)
N3—Ni3—O693.08 (14)N3—C16—C15114.4 (4)
O16i—Ni3—O691.97 (12)C17—C16—C15126.0 (5)
O20—Ni3—O6176.78 (17)C18—C17—C16118.7 (6)
N3—Ni3—O1179.24 (17)C18—C17—H17120.7
O16i—Ni3—O1194.97 (14)C16—C17—H17120.7
O20—Ni3—O1190.73 (19)C17—C18—C19120.6 (5)
O6—Ni3—O1192.16 (15)C17—C18—H18119.7
N3—Ni3—O976.49 (15)C19—C18—H18119.7
O16i—Ni3—O9109.47 (12)C18—C19—C20118.2 (6)
O20—Ni3—O990.65 (16)C18—C19—H19120.9
O6—Ni3—O986.12 (12)C20—C19—H19120.9
O11—Ni3—O9155.53 (12)N3—C20—C19119.8 (6)
N1—Ni4—O14173.79 (12)N3—C20—C21113.3 (4)
N1—Ni4—O379.10 (12)C19—C20—C21126.9 (5)
O14—Ni4—O394.69 (11)O11—C21—O12126.7 (6)
N1—Ni4—O1093.12 (13)O11—C21—C20116.1 (5)
O14—Ni4—O1087.25 (14)O12—C21—C20117.3 (5)
O3—Ni4—O1094.90 (12)O13—C22—O14125.7 (4)
N1—Ni4—O2186.67 (15)O13—C22—C23117.6 (3)
O14—Ni4—O2193.37 (15)O14—C22—C23116.7 (3)
O3—Ni4—O2188.78 (14)C28—C23—C24120.1 (4)
O10—Ni4—O21176.20 (13)C28—C23—C22121.2 (3)
N1—Ni4—O175.56 (11)C24—C23—C22118.6 (3)
O14—Ni4—O1110.65 (11)C25—C24—C23119.9 (4)
O3—Ni4—O1154.66 (11)C25—C24—H24120.1
O10—Ni4—O186.78 (12)C23—C24—H24120.1
O21—Ni4—O189.50 (12)C24—C25—C26120.6 (4)
O8—Ni5—O8ii86.72 (14)C24—C25—C29119.2 (4)
O8—Ni5—O8iii86.73 (14)C26—C25—C29120.2 (4)
O8ii—Ni5—O8iii86.73 (14)C27—C26—C25118.4 (4)
O8—Ni5—O22ii89.7 (2)C27—C26—H26120.8
O8ii—Ni5—O22ii176.3 (2)C25—C26—H26120.8
O8iii—Ni5—O22ii92.4 (3)C28—C27—C26122.0 (4)
O8—Ni5—O22iii92.4 (3)C28—C27—Br1119.2 (3)
O8ii—Ni5—O22iii89.7 (2)C26—C27—Br1118.8 (3)
O8iii—Ni5—O22iii176.3 (2)C27—C28—C23119.0 (4)
O22ii—Ni5—O22iii91.1 (3)C27—C28—H28120.5
O8—Ni5—O22176.3 (2)C23—C28—H28120.5
O8ii—Ni5—O2292.4 (3)O15—C29—O16126.9 (4)
O8iii—Ni5—O2289.7 (2)O15—C29—C25117.1 (4)
O22ii—Ni5—O2291.1 (3)O16—C29—C25116.0 (4)
O22iii—Ni5—O2291.1 (3)O18—C30—O17126.0 (4)
C7—O1—Ni1136.0 (3)O18—C30—C31117.8 (4)
C7—O1—Ni4114.1 (2)O17—C30—C31116.2 (4)
Ni1—O1—Ni4106.77 (12)C33—C31—C32119.7 (5)
C7—O2—Ni2127.6 (3)C33—C31—C30119.9 (4)
C1—O3—Ni4115.8 (2)C32—C31—C30120.4 (4)
C8—O5—Ni1132.6 (3)C31i—C32—C31121.2 (6)
C8—O5—Ni2114.3 (3)C31i—C32—H01A119.4
Ni1—O5—Ni2107.83 (13)C31—C32—H01A119.4
C8—O6—Ni3129.8 (3)C31—C33—C34119.1 (5)
C14—O7—Ni2115.3 (3)C31—C33—H33120.4
C14—O8—Ni5130.9 (4)C34—C33—H33120.4
C15—O9—Ni1135.2 (3)C33—C34—C33i121.2 (7)
C15—O9—Ni3113.7 (3)C33—C34—Br2119.4 (4)
Ni1—O9—Ni3107.80 (12)C33i—C34—Br2119.4 (4)
C15—O10—Ni4126.8 (3)O19—C35—N4123.1 (4)
C21—O11—Ni3114.3 (4)O19—C35—H35118.4
C21—O12—H12S122.9N4—C35—H35118.4
C22—O13—Ni1133.2 (3)N4—C36—H01C109.5
C22—O14—Ni4118.7 (2)N4—C36—H01D109.5
C29—O15—Ni1i137.6 (3)H01C—C36—H01D109.5
C29—O16—Ni3i121.3 (3)N4—C36—H01G109.5
C30—O17—Ni1135.7 (3)H01C—C36—H01G109.5
C30—O18—Ni2121.5 (3)H01D—C36—H01G109.5
C35—O19—Ni2121.7 (3)N4—C37—H01I109.5
C38—O20—Ni3135.6 (6)N4—C37—H01K109.5
C41—O21—Ni4135.6 (4)H01I—C37—H01K109.5
Ni5—O22—H22A115.1N4—C37—H01L109.5
Ni5—O22—H22B115.0H01I—C37—H01L109.5
H22A—O22—H22B111.5H01K—C37—H01L109.5
C6—N1—C2121.6 (3)O20—C38—N5128.8 (9)
C6—N1—Ni4121.2 (3)O20—C38—H38115.6
C2—N1—Ni4117.1 (3)N5—C38—H38115.6
C9—N2—C13121.7 (4)N5—C39—H39A109.5
C9—N2—Ni2120.8 (3)N5—C39—H39B109.5
C13—N2—Ni2117.4 (4)H39A—C39—H39B109.5
C20—N3—C16123.0 (4)N5—C39—H39C109.5
C20—N3—Ni3116.6 (4)H39A—C39—H39C109.5
C16—N3—Ni3119.8 (3)H39B—C39—H39C109.5
C35—N4—C36122.0 (4)N5—C40—H40A109.5
C35—N4—C37121.2 (4)N5—C40—H40B109.5
C36—N4—C37116.8 (4)H40A—C40—H40B109.5
C38—N5—C40122.8 (9)N5—C40—H40C109.5
C38—N5—C39121.0 (9)H40A—C40—H40C109.5
C40—N5—C39114.9 (9)H40B—C40—H40C109.5
C41—N6—C43119.5 (6)O21—C41—N6125.2 (6)
C41—N6—C42119.2 (6)O21—C41—H41117.4
C43—N6—C42120.1 (7)N6—C41—H41117.4
O4—C1—O3125.8 (4)N6—C42—H02C109.5
O4—C1—C2119.5 (4)N6—C42—H02D109.5
O3—C1—C2114.7 (3)H02C—C42—H02D109.5
N1—C2—C3120.5 (4)N6—C42—H02E109.5
N1—C2—C1113.0 (3)H02C—C42—H02E109.5
C3—C2—C1126.6 (4)H02D—C42—H02E109.5
C2—C3—C4118.6 (4)N6—C43—H02F109.5
C2—C3—H3120.7N6—C43—H02G109.5
C4—C3—H3120.7H02F—C43—H02G109.5
C5—C4—C3120.1 (4)N6—C43—H02H109.5
C5—C4—H4119.9H02F—C43—H02H109.5
C3—C4—H4119.9H02G—C43—H02H109.5
C6—C5—C4118.6 (4)
Symmetry codes: (i) x, −y+3/4, −z+3/4; (ii) −z+5/4, −x+5/4, y; (iii) −y+5/4, z, −x+5/4.
(4) top
Crystal data top
C522H496Co52N72O264Synchrotron radiation, λ = 0.700 Å
Mr = 15066.24Cell parameters from 681293 reflections
Cubic, Fd3θ = 1.5–31.5°
a = 58.380 (7) ŵ = 0.87 mm−1
V = 198973 (69) Å3T = 100 K
Z = 8Rectangular, purple
F(000) = 611840.17 × 0.11 × 0.11 mm
Dx = 1.006 Mg m−3
Data collection top
CCD detector
diffractometer		15041 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.037
phi and ω scansθmax = 26.0°, θmin = 1.7°
Absorption correction: multi-scan
SADABS		h = −73→73
Tmin = 0.862, Tmax = 0.906k = −73→73
311832 measured reflectionsl = −71→72
17071 independent reflections
Refinement top
Refinement on F2105 restraints
Least-squares matrix: fullHydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.117 w = 1/[σ2(Fo2) + (0.0612P)2 + 718.2457P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.004
17071 reflectionsΔρmax = 1.59 e Å−3
723 parametersΔρmin = −0.79 e Å−3
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co10.40140 (2)0.60938 (2)0.68463 (2)0.02466 (7)
Co20.44475 (2)0.56902 (2)0.69797 (2)0.03133 (8)
Co30.34893 (2)0.58589 (2)0.70167 (2)0.03236 (8)
Co40.41170 (2)0.65665 (2)0.71889 (2)0.02836 (8)
Co50.52009 (2)0.52009 (2)0.72991 (2)0.04700 (15)
O10.42378 (3)0.62113 (3)0.71035 (2)0.0295 (3)
O20.44729 (3)0.59334 (3)0.72332 (3)0.0339 (4)
O30.41126 (3)0.68490 (3)0.74085 (2)0.0309 (3)
O40.42861 (3)0.70107 (3)0.77099 (3)0.0378 (4)
O50.40620 (3)0.57578 (3)0.69810 (2)0.0306 (3)
O60.37402 (3)0.56440 (3)0.71609 (3)0.0358 (4)
O70.47384 (3)0.55093 (3)0.71045 (3)0.0429 (4)
O80.48462 (3)0.52322 (3)0.73511 (3)0.0470 (4)
O90.37387 (3)0.61433 (3)0.70804 (2)0.0304 (3)
O100.38340 (3)0.64065 (3)0.73484 (3)0.0346 (4)
O110.32285 (3)0.56360 (3)0.71305 (3)0.0485 (4)
O120.29591 (5)0.55954 (5)0.73999 (5)0.0841 (9)
H12S0.2900940.5458170.7341470.126*0.3333
O130.39871 (3)0.64186 (3)0.67128 (3)0.0325 (3)
O140.38920 (3)0.66945 (3)0.69600 (3)0.0375 (4)
O150.37866 (3)0.65070 (3)0.59014 (3)0.0338 (3)
O160.35330 (3)0.67738 (3)0.57961 (3)0.0382 (4)
O170.42722 (3)0.60373 (3)0.66140 (2)0.0296 (3)
O180.46024 (3)0.59037 (3)0.67538 (3)0.0384 (4)
O190.43963 (3)0.54496 (3)0.67212 (3)0.0408 (4)
O200.32464 (3)0.60934 (4)0.68809 (3)0.0504 (5)
O210.44042 (3)0.67021 (3)0.70181 (3)0.0487 (5)
O220.52428 (11)0.55691 (7)0.73527 (7)0.1475 (17)
H22A0.5165870.5659520.7257830.221*
H22B0.5392920.5623040.7341710.221*
N10.43419 (3)0.64761 (3)0.74430 (3)0.0252 (3)
N20.43104 (4)0.54682 (3)0.72154 (3)0.0365 (4)
N30.34014 (3)0.59933 (4)0.73268 (3)0.0359 (4)
N40.43005 (4)0.53648 (3)0.63576 (3)0.0367 (4)
N50.31037 (5)0.63667 (6)0.66514 (6)0.0779 (9)
C10.42530 (4)0.68510 (4)0.75740 (4)0.0284 (4)
C20.43860 (4)0.66303 (3)0.76056 (3)0.0261 (4)
C30.45370 (4)0.65835 (4)0.77803 (4)0.0322 (5)
H30.4567430.6693840.7896000.039*
C40.46440 (4)0.63712 (4)0.77835 (4)0.0351 (5)
H40.4747520.6334180.7903430.042*
C50.45999 (4)0.62126 (4)0.76115 (4)0.0309 (5)
H50.4672760.6067140.7610360.037*
C60.44461 (3)0.62741 (4)0.74422 (3)0.0258 (4)
C70.43811 (4)0.61244 (4)0.72434 (3)0.0272 (4)
C80.39492 (4)0.56363 (4)0.71234 (4)0.0323 (5)
C90.40868 (5)0.54639 (4)0.72573 (4)0.0402 (5)
C100.39937 (6)0.53177 (6)0.74180 (7)0.0691 (10)
H100.3833960.5317150.7449230.083*
C110.41441 (7)0.51695 (8)0.75337 (8)0.0926 (15)
H110.4085960.5065480.7644500.111*
C120.43740 (7)0.51744 (6)0.74875 (7)0.0757 (11)
H120.4476340.5074220.7564750.091*
C130.44543 (5)0.53278 (5)0.73264 (5)0.0464 (6)
C140.47008 (5)0.53576 (4)0.72552 (4)0.0421 (6)
C150.37113 (4)0.62526 (4)0.72685 (3)0.0309 (5)
C160.35063 (4)0.61778 (4)0.74084 (4)0.0351 (5)
C170.34308 (5)0.62854 (5)0.76056 (4)0.0427 (6)
H170.3505270.6418590.7662080.051*
C180.32435 (5)0.61934 (6)0.77183 (4)0.0506 (7)
H180.3187640.6264190.7853770.061*
C190.31376 (5)0.59990 (6)0.76346 (5)0.0530 (7)
H190.3011300.5932400.7712610.064*
C200.32212 (5)0.59037 (5)0.74330 (4)0.0454 (6)
C210.31274 (5)0.56944 (6)0.73123 (5)0.0544 (7)
C220.38854 (4)0.66005 (4)0.67656 (4)0.0299 (4)
C230.37505 (4)0.67200 (4)0.65816 (3)0.0291 (4)
C240.37546 (4)0.66362 (4)0.63583 (3)0.0279 (4)
H240.3834630.6498650.6324110.034*
C250.36413 (4)0.67544 (4)0.61857 (3)0.0287 (4)
C260.35191 (4)0.69534 (4)0.62382 (4)0.0328 (5)
H260.3438810.7031210.6119920.039*
C270.35129 (4)0.70404 (4)0.64611 (4)0.0356 (5)
C280.36311 (4)0.69215 (4)0.66306 (4)0.0336 (5)
H280.3630590.6978620.6782960.040*
C290.36558 (4)0.66711 (4)0.59428 (4)0.0304 (4)
C300.33828 (5)0.72563 (5)0.65144 (5)0.0513 (7)
H30A0.3311330.7314710.6374200.077*
H30B0.3263880.7223360.6628260.077*
H30C0.3488380.7371590.6575600.077*
C310.44866 (4)0.60200 (4)0.66134 (4)0.0312 (5)
C320.46146 (4)0.61423 (4)0.64261 (4)0.0348 (5)
C330.44948 (5)0.6250000.6250000.0319 (6)
H330.4332110.6249990.6249990.038*
C340.48547 (4)0.61425 (6)0.64242 (5)0.0509 (7)
H340.4935640.6067900.6544070.061*
C350.49764 (7)0.6250000.6250000.0598 (12)
C360.52360 (8)0.6250000.6250000.099 (2)
H36A0.5291910.6333110.6115310.148*0.5
H36B0.5291910.6325090.6389320.148*0.5
H36C0.5291910.6091800.6245370.148*0.5
C370.42915 (4)0.54947 (4)0.65419 (4)0.0337 (5)
H370.4200430.5629400.6537250.040*
C380.41715 (5)0.54198 (5)0.61518 (5)0.0504 (7)
H38A0.4200790.5303190.6034630.076*
H38B0.4007560.5423050.6187730.076*
H38C0.4219230.5570090.6094360.076*
C390.44384 (6)0.51565 (5)0.63528 (5)0.0573 (8)
H39A0.4423760.5083130.6202560.086*
H39B0.4599270.5195250.6380800.086*
H39C0.4384670.5051110.6471980.086*
C400.32675 (6)0.62371 (6)0.67313 (6)0.0634 (8)
H400.3415790.6256530.6667270.076*
C410.31294 (9)0.65249 (10)0.64658 (12)0.132 (3)
H41A0.2983090.6602080.6437390.198*
H41B0.3246080.6639030.6505340.198*
H41C0.3176770.6442030.6327770.198*
C420.28705 (9)0.63563 (11)0.67548 (13)0.137 (3)
H42A0.2769090.6463720.6675060.206*
H42B0.2809690.6200520.6740040.206*
H42C0.2879370.6397760.6917200.206*
N60.46777 (5)0.67729 (6)0.67559 (6)0.0544 (8)0.845 (5)
C430.44775 (6)0.66957 (5)0.68241 (6)0.0408 (7)0.845 (5)
H430.4381640.6628680.6710980.049*0.845 (5)
C440.47427 (11)0.67756 (9)0.65152 (9)0.0884 (17)0.845 (5)
H44A0.4897310.6839080.6499670.133*0.845 (5)
H44B0.4740180.6618990.6454820.133*0.845 (5)
H44C0.4634320.6870530.6429050.133*0.845 (5)
C450.48312 (7)0.68872 (8)0.69199 (9)0.0774 (13)0.845 (5)
H45A0.4972130.6933860.6841440.116*0.845 (5)
H45B0.4754830.7022750.6982940.116*0.845 (5)
H45C0.4868990.6781230.7044440.116*0.845 (5)
N6X0.4698 (3)0.6658 (4)0.6772 (3)0.056 (3)0.155 (5)
C43X0.4551 (4)0.6645 (3)0.6957 (4)0.053 (3)0.155 (5)
H43B0.4615780.6542440.7066260.064*0.155 (5)
C44X0.4932 (3)0.6662 (4)0.6801 (5)0.079 (5)0.155 (5)
H44D0.5006730.6671880.6651060.118*0.155 (5)
H44E0.4975030.6795220.6893810.118*0.155 (5)
H44F0.4981370.6521570.6878890.118*0.155 (5)
C45X0.4623 (4)0.6729 (4)0.6559 (4)0.057 (4)0.155 (5)
H45D0.4751830.6726790.6451010.085*0.155 (5)
H45E0.4502980.6624890.6504230.085*0.155 (5)
H45F0.4561610.6884580.6569580.085*0.155 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.02879 (14)0.02760 (14)0.01759 (13)0.00703 (11)−0.00155 (10)−0.00562 (10)
Co20.04182 (17)0.02754 (15)0.02462 (14)0.01224 (12)−0.00572 (12)−0.00813 (11)
Co30.03564 (16)0.03992 (17)0.02151 (14)0.00353 (13)0.00522 (11)−0.00390 (12)
Co40.03471 (16)0.03064 (15)0.01972 (13)0.01309 (12)−0.00412 (11)−0.00344 (11)
Co50.04700 (15)0.04700 (15)0.04700 (15)−0.00024 (16)0.00024 (16)0.00024 (16)
O10.0351 (8)0.0310 (8)0.0224 (7)0.0109 (6)−0.0075 (6)−0.0075 (6)
O20.0409 (9)0.0308 (8)0.0299 (8)0.0146 (7)−0.0110 (7)−0.0110 (6)
O30.0385 (8)0.0294 (8)0.0248 (7)0.0131 (6)−0.0018 (6)−0.0011 (6)
O40.0474 (10)0.0284 (8)0.0376 (9)0.0101 (7)−0.0030 (7)−0.0119 (7)
O50.0372 (8)0.0298 (8)0.0248 (7)0.0083 (6)−0.0008 (6)−0.0041 (6)
O60.0437 (9)0.0365 (8)0.0273 (8)0.0065 (7)0.0016 (7)−0.0010 (6)
O70.0527 (11)0.0407 (9)0.0353 (9)0.0233 (8)−0.0066 (8)−0.0042 (7)
O80.0565 (11)0.0429 (10)0.0415 (10)0.0224 (9)−0.0142 (8)−0.0034 (8)
O90.0338 (8)0.0370 (8)0.0204 (7)0.0077 (6)0.0012 (6)−0.0062 (6)
O100.0388 (9)0.0416 (9)0.0235 (7)0.0101 (7)−0.0022 (6)−0.0099 (6)
O110.0511 (11)0.0538 (11)0.0407 (10)−0.0059 (9)0.0150 (8)−0.0063 (8)
O120.0815 (17)0.098 (2)0.0731 (16)−0.0357 (15)0.0432 (14)−0.0230 (14)
O130.0394 (9)0.0318 (8)0.0263 (7)0.0133 (7)0.0004 (6)−0.0017 (6)
O140.0490 (10)0.0395 (9)0.0239 (8)0.0201 (7)−0.0092 (7)−0.0060 (6)
O150.0370 (9)0.0416 (9)0.0227 (7)0.0027 (7)0.0043 (6)−0.0033 (6)
O160.0458 (10)0.0454 (9)0.0234 (8)0.0028 (8)−0.0083 (7)−0.0046 (7)
O170.0323 (8)0.0329 (8)0.0237 (7)0.0051 (6)0.0023 (6)−0.0069 (6)
O180.0394 (9)0.0418 (9)0.0341 (8)0.0084 (7)−0.0046 (7)−0.0011 (7)
O190.0500 (10)0.0396 (9)0.0330 (9)0.0098 (8)−0.0036 (7)−0.0145 (7)
O200.0439 (10)0.0629 (12)0.0442 (10)0.0130 (9)−0.0013 (8)0.0027 (9)
O210.0518 (11)0.0459 (10)0.0483 (11)0.0152 (9)0.0160 (9)0.0102 (8)
O220.217 (5)0.118 (3)0.107 (3)−0.003 (3)0.034 (3)0.026 (2)
N10.0280 (9)0.0247 (8)0.0230 (8)0.0070 (7)−0.0022 (7)−0.0042 (7)
N20.0497 (12)0.0309 (10)0.0290 (9)0.0142 (9)−0.0066 (8)−0.0054 (8)
N30.0368 (10)0.0464 (11)0.0244 (9)0.0083 (9)0.0066 (8)−0.0010 (8)
N40.0417 (11)0.0323 (10)0.0361 (10)0.0039 (8)−0.0065 (8)−0.0131 (8)
N50.0553 (17)0.079 (2)0.100 (2)0.0080 (15)−0.0127 (16)0.0190 (18)
C10.0321 (11)0.0263 (10)0.0267 (10)0.0067 (8)0.0047 (8)−0.0017 (8)
C20.0270 (10)0.0259 (10)0.0254 (10)0.0043 (8)−0.0013 (8)−0.0056 (8)
C30.0320 (11)0.0316 (11)0.0329 (11)0.0061 (9)−0.0081 (9)−0.0127 (9)
C40.0329 (11)0.0359 (12)0.0366 (12)0.0096 (9)−0.0147 (9)−0.0111 (10)
C50.0322 (11)0.0288 (11)0.0316 (11)0.0104 (9)−0.0085 (9)−0.0074 (9)
C60.0271 (10)0.0255 (10)0.0247 (10)0.0051 (8)−0.0033 (8)−0.0047 (8)
C70.0305 (10)0.0272 (10)0.0240 (10)0.0078 (8)−0.0041 (8)−0.0065 (8)
C80.0432 (13)0.0299 (11)0.0238 (10)0.0088 (9)−0.0018 (9)−0.0067 (8)
C90.0511 (15)0.0336 (12)0.0359 (12)0.0105 (11)−0.0024 (11)0.0006 (10)
C100.062 (2)0.065 (2)0.080 (2)0.0161 (16)0.0049 (17)0.0374 (18)
C110.078 (3)0.088 (3)0.112 (3)0.021 (2)0.007 (2)0.068 (3)
C120.073 (2)0.070 (2)0.084 (3)0.0246 (18)−0.0055 (19)0.038 (2)
C130.0585 (16)0.0382 (13)0.0423 (14)0.0190 (12)−0.0100 (12)0.0010 (11)
C140.0546 (15)0.0373 (13)0.0345 (12)0.0206 (11)−0.0112 (11)−0.0104 (10)
C150.0341 (11)0.0388 (12)0.0200 (9)0.0137 (9)−0.0004 (8)−0.0039 (9)
C160.0378 (12)0.0449 (13)0.0224 (10)0.0135 (10)0.0015 (9)−0.0052 (9)
C170.0434 (14)0.0573 (16)0.0274 (11)0.0141 (12)0.0072 (10)−0.0074 (11)
C180.0495 (15)0.0715 (19)0.0309 (12)0.0145 (14)0.0117 (11)−0.0104 (12)
C190.0478 (16)0.073 (2)0.0385 (14)0.0069 (14)0.0183 (12)−0.0024 (13)
C200.0435 (14)0.0590 (16)0.0339 (13)0.0049 (12)0.0127 (11)−0.0024 (11)
C210.0525 (17)0.0645 (19)0.0461 (16)−0.0053 (14)0.0167 (13)−0.0040 (13)
C220.0330 (11)0.0326 (11)0.0242 (10)0.0093 (9)−0.0013 (8)−0.0020 (8)
C230.0307 (10)0.0342 (11)0.0224 (10)0.0077 (9)−0.0023 (8)−0.0029 (8)
C240.0281 (10)0.0306 (11)0.0251 (10)0.0038 (8)0.0005 (8)−0.0041 (8)
C250.0282 (10)0.0354 (11)0.0226 (10)0.0015 (9)−0.0026 (8)−0.0036 (8)
C260.0336 (11)0.0408 (12)0.0239 (10)0.0093 (9)−0.0053 (9)0.0002 (9)
C270.0388 (12)0.0394 (12)0.0285 (11)0.0157 (10)−0.0029 (9)−0.0034 (9)
C280.0394 (12)0.0396 (12)0.0218 (10)0.0150 (10)−0.0026 (9)−0.0050 (9)
C290.0304 (11)0.0381 (12)0.0226 (10)−0.0043 (9)0.0005 (8)−0.0029 (9)
C300.0651 (18)0.0547 (16)0.0342 (13)0.0336 (14)−0.0077 (12)−0.0054 (11)
C310.0334 (11)0.0320 (11)0.0282 (11)0.0064 (9)−0.0015 (9)−0.0092 (9)
C320.0299 (11)0.0416 (13)0.0330 (12)0.0022 (9)−0.0018 (9)−0.0050 (10)
C330.0276 (15)0.0358 (16)0.0322 (15)0.0000.000−0.0069 (13)
C340.0303 (13)0.0721 (19)0.0503 (16)0.0053 (12)−0.0047 (11)0.0057 (14)
C350.0294 (19)0.089 (3)0.061 (3)0.0000.0000.014 (2)
C360.031 (2)0.165 (7)0.101 (4)0.0000.0000.046 (4)
C370.0370 (12)0.0290 (11)0.0350 (12)−0.0003 (9)0.0004 (9)−0.0105 (9)
C380.0627 (17)0.0442 (15)0.0443 (14)0.0139 (13)−0.0148 (13)−0.0165 (12)
C390.070 (2)0.0521 (17)0.0499 (16)0.0253 (15)−0.0185 (14)−0.0248 (13)
C400.0457 (16)0.074 (2)0.070 (2)0.0126 (15)0.0005 (15)0.0140 (18)
C410.076 (3)0.136 (5)0.185 (6)0.001 (3)−0.011 (3)0.098 (5)
C420.072 (3)0.148 (5)0.193 (7)0.038 (3)0.024 (4)0.054 (5)
N60.0462 (15)0.0482 (18)0.069 (2)0.0084 (14)0.0197 (14)−0.0012 (15)
C430.0495 (17)0.0347 (15)0.0381 (16)0.0083 (12)0.0062 (13)−0.0002 (12)
C440.099 (4)0.079 (3)0.087 (3)−0.013 (3)0.060 (3)−0.014 (2)
C450.0379 (19)0.079 (3)0.116 (4)0.0113 (19)−0.008 (2)0.009 (3)
N6X0.055 (5)0.047 (5)0.066 (5)0.006 (5)0.019 (4)−0.001 (5)
C43X0.054 (5)0.044 (5)0.061 (6)−0.001 (5)0.010 (5)0.003 (5)
C44X0.062 (9)0.064 (9)0.109 (10)0.019 (8)0.012 (9)0.008 (9)
C45X0.057 (8)0.043 (7)0.070 (8)0.007 (7)0.022 (8)−0.007 (7)
Geometric parameters (Å, º) top
Co1—O15i2.0499 (15)C10—C111.405 (5)
Co1—O172.0543 (15)C10—H100.9500
Co1—O132.0559 (16)C11—C121.370 (6)
Co1—O12.1052 (15)C11—H110.9500
Co1—O92.1296 (15)C12—C131.380 (5)
Co1—O52.1320 (16)C12—H120.9500
Co2—O182.0277 (18)C13—C141.508 (4)
Co2—N22.053 (2)C15—C161.513 (3)
Co2—O22.0562 (15)C16—C171.384 (3)
Co2—O192.0833 (16)C17—C181.384 (4)
Co2—O72.1284 (17)C17—H170.9500
Co2—O52.2851 (16)C18—C191.381 (5)
Co3—O16i1.9995 (16)C18—H180.9500
Co3—N32.0388 (19)C19—C201.390 (4)
Co3—O62.1039 (17)C19—H190.9500
Co3—O112.1102 (19)C20—C211.513 (4)
Co3—O202.1249 (19)C22—C231.503 (3)
Co3—O92.2395 (17)C23—C241.393 (3)
Co4—O142.0173 (15)C23—C281.397 (3)
Co4—N12.0500 (17)C24—C251.389 (3)
Co4—O32.0890 (15)C24—H240.9500
Co4—O212.106 (2)C25—C261.397 (3)
Co4—O102.1141 (18)C25—C291.502 (3)
Co4—O12.2462 (15)C26—C271.397 (3)
Co5—O8ii2.100 (2)C26—H260.9500
Co5—O8iii2.100 (2)C27—C281.392 (3)
Co5—O82.101 (2)C27—C301.504 (3)
Co5—O222.186 (4)C28—H280.9500
Co5—O22ii2.186 (4)C30—H30A0.9800
Co5—O22iii2.186 (4)C30—H30B0.9800
O1—C71.275 (3)C30—H30C0.9800
O2—C71.239 (3)C31—C321.505 (3)
O3—C11.267 (3)C32—C331.393 (3)
O4—C11.240 (3)C32—C341.402 (3)
O5—C81.276 (3)C33—H330.9500
O6—C81.241 (3)C34—C351.391 (4)
O7—C141.267 (3)C34—H340.9500
O8—C141.253 (3)C35—C361.515 (6)
O9—C151.280 (3)C36—H36A0.9800
O10—C151.240 (3)C36—H36B0.9800
O11—C211.261 (3)C36—H36C0.9800
O12—C211.249 (4)C36—H36Ai0.9798
O12—H12S0.9349C36—H36Bi0.9799
O13—C221.255 (3)C36—H36Ci0.9802
O14—C221.261 (3)C37—H370.9500
O15—C291.249 (3)C38—H38A0.9800
O16—C291.268 (3)C38—H38B0.9800
O17—C311.256 (3)C38—H38C0.9800
O18—C311.261 (3)C39—H39A0.9800
O19—C371.240 (3)C39—H39B0.9800
O20—C401.217 (4)C39—H39C0.9800
O21—C43X0.99 (2)C40—H400.9500
O21—C431.211 (4)C41—H41A0.9800
O22—H22A0.8871C41—H41B0.9800
O22—H22B0.9336C41—H41C0.9800
N1—C61.327 (3)C42—H42A0.9800
N1—C21.333 (3)C42—H42B0.9800
N2—C91.328 (3)C42—H42C0.9800
N2—C131.341 (3)N6—C431.314 (4)
N3—C161.328 (3)N6—C441.456 (6)
N3—C201.328 (3)N6—C451.471 (6)
N4—C371.317 (3)C43—H430.9500
N4—C381.454 (3)C44—H44A0.9800
N4—C391.459 (3)C44—H44B0.9800
N5—C401.306 (4)C44—H44C0.9800
N5—C411.431 (6)C45—H45A0.9800
N5—C421.491 (6)C45—H45B0.9800
C1—C21.516 (3)C45—H45C0.9800
C2—C31.376 (3)N6X—C43X1.378 (15)
C3—C41.388 (3)N6X—C44X1.379 (15)
C3—H30.9500N6X—C45X1.385 (15)
C4—C51.389 (3)C43X—H43B0.9500
C4—H40.9500C44X—H44D0.9800
C5—C61.383 (3)C44X—H44E0.9800
C5—H50.9500C44X—H44F0.9800
C6—C71.502 (3)C45X—H45D0.9800
C8—C91.507 (3)C45X—H45E0.9800
C9—C101.380 (4)C45X—H45F0.9800
O15i—Co1—O1787.89 (6)C12—C13—C14125.9 (3)
O15i—Co1—O1387.01 (6)O8—C14—O7126.9 (3)
O17—Co1—O1387.36 (6)O8—C14—C13117.1 (2)
O15i—Co1—O1177.26 (6)O7—C14—C13115.9 (2)
O17—Co1—O193.90 (6)O10—C15—O9127.7 (2)
O13—Co1—O190.99 (6)O10—C15—C16117.56 (19)
O15i—Co1—O990.16 (6)O9—C15—C16114.7 (2)
O17—Co1—O9177.84 (6)N3—C16—C17121.3 (2)
O13—Co1—O993.46 (6)N3—C16—C15113.92 (19)
O1—Co1—O988.08 (6)C17—C16—C15124.8 (2)
O15i—Co1—O594.64 (6)C16—C17—C18118.1 (3)
O17—Co1—O589.96 (6)C16—C17—H17120.9
O13—Co1—O5176.80 (6)C18—C17—H17120.9
O1—Co1—O587.45 (6)C19—C18—C17120.3 (2)
O9—Co1—O589.28 (6)C19—C18—H18119.9
O18—Co2—N2176.47 (8)C17—C18—H18119.9
O18—Co2—O290.66 (7)C18—C19—C20118.1 (3)
N2—Co2—O288.95 (7)C18—C19—H19120.9
O18—Co2—O1990.41 (7)C20—C19—H19120.9
N2—Co2—O1990.23 (8)N3—C20—C19121.0 (3)
O2—Co2—O19175.79 (7)N3—C20—C21112.7 (2)
O18—Co2—O799.90 (7)C19—C20—C21126.2 (3)
N2—Co2—O776.62 (8)O12—C21—O11126.0 (3)
O2—Co2—O792.22 (6)O12—C21—C20117.9 (3)
O19—Co2—O791.61 (7)O11—C21—C20116.2 (3)
O18—Co2—O5109.58 (6)O13—C22—O14125.1 (2)
N2—Co2—O573.90 (7)O13—C22—C23117.73 (19)
O2—Co2—O587.10 (6)O14—C22—C23117.18 (18)
O19—Co2—O588.71 (6)C24—C23—C28119.75 (19)
O7—Co2—O5150.52 (7)C24—C23—C22119.76 (19)
O16i—Co3—N3172.73 (8)C28—C23—C22120.40 (19)
O16i—Co3—O692.63 (7)C25—C24—C23119.73 (19)
N3—Co3—O692.83 (7)C25—C24—H24120.1
O16i—Co3—O1198.10 (7)C23—C24—H24120.1
N3—Co3—O1177.05 (8)C24—C25—C26119.84 (19)
O6—Co3—O1190.49 (8)C24—C25—C29119.82 (19)
O16i—Co3—O2089.66 (8)C26—C25—C29120.32 (19)
N3—Co3—O2085.13 (8)C25—C26—C27121.3 (2)
O6—Co3—O20176.43 (8)C25—C26—H26119.4
O11—Co3—O2091.90 (8)C27—C26—H26119.4
O16i—Co3—O9110.85 (6)C28—C27—C26117.9 (2)
N3—Co3—O974.38 (7)C28—C27—C30121.4 (2)
O6—Co3—O985.60 (6)C26—C27—C30120.7 (2)
O11—Co3—O9150.91 (6)C27—C28—C23121.5 (2)
O20—Co3—O991.03 (7)C27—C28—H28119.3
O14—Co4—N1172.61 (7)C23—C28—H28119.3
O14—Co4—O396.10 (6)O15—C29—O16125.3 (2)
N1—Co4—O376.52 (6)O15—C29—C25117.75 (19)
O14—Co4—O2193.74 (8)O16—C29—C25117.0 (2)
N1—Co4—O2185.95 (8)C27—C30—H30A109.5
O3—Co4—O2190.20 (7)C27—C30—H30B109.5
O14—Co4—O1086.95 (7)H30A—C30—H30B109.5
N1—Co4—O1093.91 (7)C27—C30—H30C109.5
O3—Co4—O1093.96 (6)H30A—C30—H30C109.5
O21—Co4—O10175.68 (7)H30B—C30—H30C109.5
O14—Co4—O1113.53 (6)O17—C31—O18125.2 (2)
N1—Co4—O173.86 (6)O17—C31—C32117.3 (2)
O3—Co4—O1150.32 (6)O18—C31—C32117.5 (2)
O21—Co4—O189.53 (7)C33—C32—C34119.7 (2)
O10—Co4—O186.29 (6)C33—C32—C31120.1 (2)
O8ii—Co5—O8iii87.47 (8)C34—C32—C31120.2 (2)
O8ii—Co5—O887.47 (8)C32i—C33—C32119.8 (3)
O8iii—Co5—O887.47 (8)C32i—C33—H33120.1
O8ii—Co5—O22176.28 (13)C32—C33—H33120.1
O8iii—Co5—O2289.50 (12)C35—C34—C32121.1 (3)
O8—Co5—O2290.23 (17)C35—C34—H34119.4
O8ii—Co5—O22ii90.24 (17)C32—C34—H34119.4
O8iii—Co5—O22ii176.27 (12)C34—C35—C34i118.5 (4)
O8—Co5—O22ii89.50 (12)C34—C35—C36120.73 (18)
O22—Co5—O22ii92.68 (16)C34i—C35—C36120.74 (18)
O8ii—Co5—O22iii89.50 (12)C35—C36—H36A109.5
O8iii—Co5—O22iii90.24 (17)C35—C36—H36B109.5
O8—Co5—O22iii176.28 (13)H36A—C36—H36B109.5
O22—Co5—O22iii92.68 (16)C35—C36—H36C109.5
O22ii—Co5—O22iii92.68 (16)H36A—C36—H36C109.5
C7—O1—Co1137.26 (14)H36B—C36—H36C109.5
C7—O1—Co4115.56 (12)C35—C36—H36Ai109.473 (2)
Co1—O1—Co4105.32 (6)H36A—C36—H36Ai141.1
C7—O2—Co2128.70 (14)H36B—C36—H36Ai56.2
C1—O3—Co4117.86 (13)H36C—C36—H36Ai56.3
C8—O5—Co1133.15 (14)C35—C36—H36Bi109.470 (2)
C8—O5—Co2114.49 (14)H36A—C36—H36Bi56.2
Co1—O5—Co2106.68 (7)H36B—C36—H36Bi141.1
C8—O6—Co3129.45 (15)H36C—C36—H36Bi56.3
C14—O7—Co2116.49 (17)H36Ai—C36—H36Bi109.5
C14—O8—Co5130.9 (2)C35—C36—H36Ci109.464 (1)
C15—O9—Co1135.43 (15)H36A—C36—H36Ci56.3
C15—O9—Co3115.54 (15)H36B—C36—H36Ci56.2
Co1—O9—Co3106.46 (6)H36C—C36—H36Ci141.1
C15—O10—Co4127.28 (14)H36Ai—C36—H36Ci109.5
C21—O11—Co3115.85 (19)H36Bi—C36—H36Ci109.5
C21—O12—H12S122.2O19—C37—N4123.2 (2)
C22—O13—Co1136.36 (15)O19—C37—H37118.4
C22—O14—Co4117.06 (14)N4—C37—H37118.4
C29—O15—Co1i138.85 (15)N4—C38—H38A109.5
C29—O16—Co3i120.41 (15)N4—C38—H38B109.5
C31—O17—Co1138.24 (14)H38A—C38—H38B109.5
C31—O18—Co2120.97 (16)N4—C38—H38C109.5
C37—O19—Co2122.62 (15)H38A—C38—H38C109.5
C40—O20—Co3130.1 (2)H38B—C38—H38C109.5
C43X—O21—Co4137.3 (12)N4—C39—H39A109.5
C43—O21—Co4135.4 (2)N4—C39—H39B109.5
Co5—O22—H22A116.1H39A—C39—H39B109.5
Co5—O22—H22B115.3N4—C39—H39C109.5
H22A—O22—H22B103.4H39A—C39—H39C109.5
C6—N1—C2120.92 (18)H39B—C39—H39C109.5
C6—N1—Co4121.33 (14)O20—C40—N5125.6 (3)
C2—N1—Co4117.71 (13)O20—C40—H40117.2
C9—N2—C13121.0 (2)N5—C40—H40117.2
C9—N2—Co2121.26 (16)N5—C41—H41A109.5
C13—N2—Co2117.75 (19)N5—C41—H41B109.5
C16—N3—C20121.1 (2)H41A—C41—H41B109.5
C16—N3—Co3120.97 (16)N5—C41—H41C109.5
C20—N3—Co3117.56 (18)H41A—C41—H41C109.5
C37—N4—C38121.8 (2)H41B—C41—H41C109.5
C37—N4—C39121.1 (2)N5—C42—H42A109.5
C38—N4—C39117.0 (2)N5—C42—H42B109.5
C40—N5—C41124.6 (4)H42A—C42—H42B109.5
C40—N5—C42120.0 (4)N5—C42—H42C109.5
C41—N5—C42115.4 (4)H42A—C42—H42C109.5
O4—C1—O3126.6 (2)H42B—C42—H42C109.5
O4—C1—C2118.80 (19)C43—N6—C44121.8 (4)
O3—C1—C2114.61 (18)C43—N6—C45120.0 (3)
N1—C2—C3121.17 (19)C44—N6—C45117.7 (4)
N1—C2—C1112.86 (18)O21—C43—N6125.9 (3)
C3—C2—C1125.97 (19)O21—C43—H43117.0
C2—C3—C4118.39 (19)N6—C43—H43117.0
C2—C3—H3120.8N6—C44—H44A109.5
C4—C3—H3120.8N6—C44—H44B109.5
C3—C4—C5120.1 (2)H44A—C44—H44B109.5
C3—C4—H4119.9N6—C44—H44C109.5
C5—C4—H4119.9H44A—C44—H44C109.5
C6—C5—C4117.63 (19)H44B—C44—H44C109.5
C6—C5—H5121.2N6—C45—H45A109.5
C4—C5—H5121.2N6—C45—H45B109.5
N1—C6—C5121.75 (19)H45A—C45—H45B109.5
N1—C6—C7113.82 (17)N6—C45—H45C109.5
C5—C6—C7124.43 (18)H45A—C45—H45C109.5
O2—C7—O1127.71 (19)H45B—C45—H45C109.5
O2—C7—C6116.87 (18)C43X—N6X—C44X121.4 (19)
O1—C7—C6115.42 (17)C43X—N6X—C45X121.8 (18)
O6—C8—O5127.1 (2)C44X—N6X—C45X114.6 (19)
O6—C8—C9117.2 (2)O21—C43X—N6X143 (2)
O5—C8—C9115.7 (2)O21—C43X—H43B108.4
N2—C9—C10121.6 (2)N6X—C43X—H43B108.4
N2—C9—C8114.6 (2)N6X—C44X—H44D109.5
C10—C9—C8123.8 (3)N6X—C44X—H44E109.5
C9—C10—C11117.5 (3)H44D—C44X—H44E109.5
C9—C10—H10121.3N6X—C44X—H44F109.5
C11—C10—H10121.3H44D—C44X—H44F109.5
C12—C11—C10120.3 (3)H44E—C44X—H44F109.5
C12—C11—H11119.8N6X—C45X—H45D109.5
C10—C11—H11119.8N6X—C45X—H45E109.5
C11—C12—C13118.7 (3)H45D—C45X—H45E109.5
C11—C12—H12120.6N6X—C45X—H45F109.5
C13—C12—H12120.6H45D—C45X—H45F109.5
N2—C13—C12120.9 (3)H45E—C45X—H45F109.5
N2—C13—C14113.2 (2)
Co4—O3—C1—O4174.23 (18)O9—C15—C16—N37.1 (3)
Co4—O3—C1—C2−7.3 (2)O10—C15—C16—C177.7 (3)
C6—N1—C2—C3−1.4 (3)O9—C15—C16—C17−173.5 (2)
Co4—N1—C2—C3−179.22 (17)N3—C16—C17—C180.9 (4)
C6—N1—C2—C1179.00 (19)C15—C16—C17—C18−178.4 (2)
Co4—N1—C2—C11.2 (2)C16—C17—C18—C190.3 (4)
O4—C1—C2—N1−177.4 (2)C17—C18—C19—C20−1.5 (5)
O3—C1—C2—N14.0 (3)C16—N3—C20—C19−0.6 (4)
O4—C1—C2—C33.0 (3)Co3—N3—C20—C19−174.1 (2)
O3—C1—C2—C3−175.6 (2)C16—N3—C20—C21−180.0 (2)
N1—C2—C3—C40.2 (4)Co3—N3—C20—C216.6 (3)
C1—C2—C3—C4179.8 (2)C18—C19—C20—N31.7 (4)
C2—C3—C4—C50.8 (4)C18—C19—C20—C21−179.0 (3)
C3—C4—C5—C6−0.6 (4)Co3—O11—C21—O12174.9 (3)
C2—N1—C6—C51.6 (3)Co3—O11—C21—C20−5.1 (4)
Co4—N1—C6—C5179.32 (17)N3—C20—C21—O12179.2 (3)
C2—N1—C6—C7−178.39 (19)C19—C20—C21—O12−0.1 (5)
Co4—N1—C6—C7−0.6 (3)N3—C20—C21—O11−0.7 (4)
C4—C5—C6—N1−0.5 (3)C19—C20—C21—O11180.0 (3)
C4—C5—C6—C7179.4 (2)Co1—O13—C22—O1450.7 (4)
Co2—O2—C7—O14.2 (4)Co1—O13—C22—C23−131.17 (19)
Co2—O2—C7—C6−175.24 (14)Co4—O14—C22—O138.9 (3)
Co1—O1—C7—O218.7 (4)Co4—O14—C22—C23−169.29 (16)
Co4—O1—C7—O2−179.6 (2)O13—C22—C23—C24−4.3 (3)
Co1—O1—C7—C6−161.87 (15)O14—C22—C23—C24174.0 (2)
Co4—O1—C7—C6−0.2 (2)O13—C22—C23—C28179.1 (2)
N1—C6—C7—O2180.0 (2)O14—C22—C23—C28−2.6 (3)
C5—C6—C7—O20.0 (3)C28—C23—C24—C250.5 (3)
N1—C6—C7—O10.5 (3)C22—C23—C24—C25−176.1 (2)
C5—C6—C7—O1−179.4 (2)C23—C24—C25—C26−1.6 (3)
Co3—O6—C8—O5−1.5 (3)C23—C24—C25—C29176.8 (2)
Co3—O6—C8—C9179.17 (15)C24—C25—C26—C271.6 (4)
Co1—O5—C8—O628.9 (3)C29—C25—C26—C27−176.8 (2)
Co2—O5—C8—O6178.16 (18)C25—C26—C27—C28−0.4 (4)
Co1—O5—C8—C9−151.80 (16)C25—C26—C27—C30179.3 (3)
Co2—O5—C8—C9−2.5 (2)C26—C27—C28—C23−0.7 (4)
C13—N2—C9—C100.8 (4)C30—C27—C28—C23179.5 (3)
Co2—N2—C9—C10−179.0 (3)C24—C23—C28—C270.7 (4)
C13—N2—C9—C8178.4 (2)C22—C23—C28—C27177.3 (2)
Co2—N2—C9—C8−1.4 (3)Co1i—O15—C29—O1640.3 (4)
O6—C8—C9—N2−178.0 (2)Co1i—O15—C29—C25−139.87 (18)
O5—C8—C9—N22.6 (3)Co3i—O16—C29—O1512.1 (3)
O6—C8—C9—C10−0.4 (4)Co3i—O16—C29—C25−167.73 (15)
O5—C8—C9—C10−179.8 (3)C24—C25—C29—O15−5.9 (3)
N2—C9—C10—C11−1.1 (6)C26—C25—C29—O15172.5 (2)
C8—C9—C10—C11−178.5 (4)C24—C25—C29—O16174.0 (2)
C9—C10—C11—C120.6 (7)C26—C25—C29—O16−7.6 (3)
C10—C11—C12—C130.3 (7)Co1—O17—C31—O1845.9 (3)
C9—N2—C13—C120.1 (4)Co1—O17—C31—C32−136.01 (19)
Co2—N2—C13—C12179.9 (3)Co2—O18—C31—O178.4 (3)
C9—N2—C13—C14179.9 (2)Co2—O18—C31—C32−169.73 (15)
Co2—N2—C13—C14−0.4 (3)O17—C31—C32—C33−6.1 (3)
C11—C12—C13—N2−0.6 (6)O18—C31—C32—C33172.13 (18)
C11—C12—C13—C14179.7 (4)O17—C31—C32—C34175.8 (2)
Co5—O8—C14—O7−3.6 (4)O18—C31—C32—C34−5.9 (3)
Co5—O8—C14—C13176.85 (16)C34—C32—C33—C32i−0.23 (19)
Co2—O7—C14—O8−180.0 (2)C31—C32—C33—C32i−178.3 (2)
Co2—O7—C14—C13−0.4 (3)C33—C32—C34—C350.4 (4)
N2—C13—C14—O8−179.9 (2)C31—C32—C34—C35178.5 (2)
C12—C13—C14—O8−0.2 (4)C32—C34—C35—C34i−0.2 (2)
N2—C13—C14—O70.5 (3)C32—C34—C35—C36179.8 (2)
C12—C13—C14—O7−179.7 (3)Co2—O19—C37—N4164.45 (19)
Co4—O10—C15—O96.2 (3)C38—N4—C37—O19178.6 (3)
Co4—O10—C15—C16−175.31 (14)C39—N4—C37—O19−0.4 (4)
Co1—O9—C15—O1016.5 (4)Co3—O20—C40—N5176.4 (3)
Co3—O9—C15—O10175.37 (18)C41—N5—C40—O20−176.1 (5)
Co1—O9—C15—C16−162.02 (15)C42—N5—C40—O204.1 (7)
Co3—O9—C15—C16−3.2 (2)Co4—O21—C43—N6−171.9 (3)
C20—N3—C16—C17−0.7 (4)C44—N6—C43—O21−174.5 (4)
Co3—N3—C16—C17172.56 (18)C45—N6—C43—O21−2.5 (6)
C20—N3—C16—C15178.7 (2)Co4—O21—C43X—N6X137 (3)
Co3—N3—C16—C15−8.1 (3)C44X—N6X—C43X—O21141 (3)
O10—C15—C16—N3−171.6 (2)C45X—N6X—C43X—O21−22 (5)
Symmetry codes: (i) x, −y+5/4, −z+5/4; (ii) −z+5/4, x, −y+5/4; (iii) y, −z+5/4, −x+5/4.
 

Acknowledgements

Experiments at PLS-II were supported in part by MSIP and POSTECH (grant nos. 2022-2nd-2D-025; 2022-2nd-2D-048; 2022-3rd-2D-031; 2022-3rd-2D-026). Magnetic measurements were performed using the facilities at the IBS Centre for Correlated Electron Systems, Seoul National University.

Funding information

The following funding is acknowledged: National Research Foundation (grant nos. NRF-2020R1A2C1004006; NRF-2021R1C1C1006765; NRF-2022R1A4A1022252); Korea Institute for Advancement of Technology (KIAT) grant funded by the Korean Government (MOTIE, The Competency Development Program for Industry Specialist) (grant no. P0008425).

References

First citationAlbrecht, M. (2000). Chem. Eur. J. 6, 3485–3489.  CrossRef PubMed CAS Google Scholar
 First citationBrown, I. D. (2002). The Chemical Bond in Inorganic Chemistry: the Bond Valence Model. New York: Oxford University Press.  Google Scholar
 First citationBrowne, C., Brenet, S., Clegg, J. K. & Nitschke, J. R. (2013). Angew. Chem. Int. Ed. 52, 1944–1948.  Web of Science CSD CrossRef CAS Google Scholar
 First citationChakraborty, G., Park, I., Medishetty, R. & Vittal, J. J. (2021). Chem. Rev. 121, 3751–3891.  Web of Science CrossRef CAS PubMed Google Scholar
 First citationChen, L., Chen, Q., Wu, M., Jiang, F. & Hong, M. (2015). Acc. Chem. Res. 48, 201–210.  Web of Science CrossRef CAS PubMed Google Scholar
 First citationChen, L. J., Yang, H. B. & Shionoya, M. (2017). Chem. Soc. Rev. 46, 2555–2576.  Web of Science CrossRef CAS PubMed Google Scholar
 First citationDolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationDu, X. S., Han, Y. & Chen, C. F. (2022). Chem. Commun. 58, 1326–1329.  Web of Science CrossRef CAS Google Scholar
 First citationDuriska, M. B., Neville, S. M., Lu, J., Iremonger, S. S., Boas, J. F., Kepert, C. J. & Batten, S. R. (2009). Angew. Chem. Int. Ed. 48, 8919–8922.  Web of Science CSD CrossRef CAS Google Scholar
 First citationEarnshaw, A. (1968). Introduction to Magneto Chemistry. London: Academic Press.  Google Scholar
 First citationFang, Y., Powell, J. A., Li, E., Wang, Q., Perry, Z., Kirchon, A., Yang, X., Xiao, Z., Zhu, C., Zhang, L., Huang, F. & Zhou, H. C. (2019). Chem. Soc. Rev. 48, 4707–4730.  Web of Science CrossRef CAS PubMed Google Scholar
 First citationFrischmann, P. D. & MacLachlan, M. J. (2007). Chem. Commun. pp. 4480.  Google Scholar
 First citationGalan, A. & Ballester, P. (2016). Chem. Soc. Rev. 45, 1720–1737.  Web of Science CrossRef CAS PubMed Google Scholar
 First citationHastings, C. J., Pluth, M. D., Bergman, R. G. & Raymond, K. N. (2010). J. Am. Chem. Soc. 132, 6938–6940.  Web of Science CrossRef CAS PubMed Google Scholar
 First citationHatscher, S., Schilder, H., Lueken, H. & Urland, W. (2005). Pure Appl. Chem. 77, 497–511.  Web of Science CrossRef CAS Google Scholar
 First citationHong, M., Zhao, Y., Su, W., Cao, R., Fujita, M., Zhou, Z. & Chan, A. S. C. (2000). Angew. Chem. Int. Ed. 39, 2468–2470.  CrossRef CAS Google Scholar
 First citationHousecroft, C. E. & Sharpe, A. G. (2005). Inorganic Chemistry. London: Pearson.  Google Scholar
 First citationHuang, X., Chen, L., Jin, J., Kim, H., Chen, L., Zhang, Z., Yu, L., Li, S. & Stang, P. J. (2022). Inorg. Chem. 61, 20237–20242.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationIUCr (2021). Bond valence parameters. https://www.iucr.org/resources/data/datasets/bond-valence-parameters.  Google Scholar
 First citationJia, F., Schröder, H. V., Yang, L. P., von Essen, C., Sobottka, S., Sarkar, B., Rissanen, K., Jiang, W. & Schalley, C. A. (2020). J. Am. Chem. Soc. 142, 3306–3310.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationKang, P., Mai, H. D. & Yoo, H. (2018). Dalton Trans. 47, 6660–6665.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationKang, P. & Yoo, H. (2020). Inorg. Chem. Front. 7, 905–910.  Web of Science CSD CrossRef CAS Google Scholar
 First citationKim, D., Kim, G., Han, J. & Jung, O.-S. (2022). Bull. Korean Chem. Soc. 43, 1019–1031.  Web of Science CrossRef CAS Google Scholar
 First citationLee, B., Moon, D. & Park, J. (2023). Bull. Korean Chem. Soc. 44, 55–59.  Web of Science CrossRef CAS Google Scholar
 First citationLi, J.-R., Timmons, D. J. & Zhou, H.-C. (2009). J. Am. Chem. Soc. 131, 6368–6369.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationLi, N., Jiang, F., Chen, L., Li, X., Chen, Q. & Hong, M. (2011). Chem. Commun. 47, 2327–2329.  Web of Science CSD CrossRef CAS Google Scholar
 First citationLiu, T., Chen, Y., Yakovenko, A. A. & Zhou, H. (2012). J. Am. Chem. Soc. 134, 17358–17361.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationMacrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationMai, H. D., Kang, P., Kim, J. K. & Yoo, H. (2017). Sci. Rep. 7, 43448.  Web of Science CSD CrossRef PubMed Google Scholar
 First citationMai, H. D., Lee, I. & Yoo, H. (2018). Chem. Asian J. 13, 1915–1919.  Web of Science CSD CrossRef CAS Google Scholar
 First citationMai, H. D., Tran, N. M. & Yoo, H. (2019). Coord. Chem. Rev. 387, 180–198.  Web of Science CrossRef CAS Google Scholar
 First citationMal, P., Breiner, B., Rissanen, K. & Nitschke, J. R. (2009). Science, 324, 1697–1699.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationMcConnell, A. J. (2022). Chem. Soc. Rev. 51, 2957–2971.  Web of Science CrossRef CAS PubMed Google Scholar
 First citationNguyen, T. N., Tran, N. M., Park, I. H. & Yoo, H. (2022). ACS Omega, 7, 13067–13074.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationNouar, F., Eubank, J. F., Bousquet, T., Wojtas, L., Zaworotko, M. J. & Eddaoudi, M. (2008). J. Am. Chem. Soc. 130, 1833–1835.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationPang, J., Jiang, F., Wu, M., Yuan, D., Zhou, K., Qian, J., Su, K. & Hong, M. (2014). Chem. Commun. 50, 2834–2836.  Web of Science CSD CrossRef CAS Google Scholar
 First citationPark, J., Hong, S., Moon, D., Park, M., Lee, K., Kang, S., Zou, Y., John, R. P., Kim, G. H. & Lah, M. S. (2007). Inorg. Chem. 46, 10208–10213.  Web of Science CSD CrossRef PubMed CAS Google Scholar
 First citationPerry IV, J. J., Perman, J. A. & Zaworotko, M. J. (2009). Chem. Soc. Rev. 38, 1400–1417.  Web of Science CrossRef PubMed Google Scholar
 First citationPullen, S., Tessarolo, J. & Clever, G. H. (2021). Chem. Sci. 12, 7269–7293.  Web of Science CrossRef CAS PubMed Google Scholar
 First citationQian, J., Jiang, F., Zhang, L., Su, K., Pan, J., Li, Q., Yuan, D. & Hong, M. (2014). Chem. Commun. 50, 1678–1681.  Web of Science CSD CrossRef CAS Google Scholar
 First citationRahman, F. -U., Yang, J. -M., Wan, Y. -H., Zhang, H. -B., Petsalakis, I. D., Theodorakopoulos, G. Jr, Rebek, J. & Yu, Y. (2020). Chem. Commun. 56, 6945–6948.  Web of Science CrossRef CAS Google Scholar
 First citationRizzuto, F. J., von Krbek, L. K. S. & Nitschke, J. R. (2019). Nat. Rev. Chem. 3, 204–222.  Web of Science CrossRef Google Scholar
 First citationRowland, R. S. & Taylor, R. (1996). J. Phys. Chem. 100, 7384–7391.  CrossRef CAS Web of Science Google Scholar
 First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
 First citationSikligar, K., Kelley, S. P., Shao, L., Baker, G. A. & Atwood, J. L. (2021). Cryst. Growth Des. 21, 1891–1897.  Web of Science CSD CrossRef CAS Google Scholar
 First citationThi Le, V. C., Mai, H. D., Kang, P. & Yoo, H. (2019). Chem. Eur. J. 25, 2472–2476.  Web of Science PubMed Google Scholar
 First citationTian, D., Chen, Q., Li, Y., Zhang, Y., Chang, Z. & Bu, X. (2014). Angew. Chem. Int. Ed. 53, 837–841.  Web of Science CSD CrossRef CAS Google Scholar
 First citationTran, N. M. & Yoo, H. (2020). Dalton Trans. 49, 11819–11827.  Web of Science CrossRef CAS PubMed Google Scholar
 First citationWang, L. J., Li, X., Bai, S., Wang, Y. Y. & Han, Y. F. (2020). J. Am. Chem. Soc. 142, 2524–2531.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationWang, M.-Y., Yuan, Y.-Y., Qi, Z.-Q., Chen, J.-Y., Jiang, Z.-G. & Zhan, C.-H. (2022). Chem. Mater. 34, 10501–10508.  Web of Science CSD CrossRef CAS Google Scholar
 First citationWhitehead, M., Turega, S., Stephenson, A., Hunter, C. A. & Ward, M. D. (2013). Chem. Sci. 4, 2744–2751.  Web of Science CSD CrossRef CAS Google Scholar
 First citationYong, M. T., Linder-Patton, O. M. & Bloch, W. M. (2022). Inorg. Chem. 61, 12863–12869.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationYoo, H., Lee, J., Kang, P. & Choi, M. G. (2015). Dalton Trans. 44, 14213–14216.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationYoshizawa, M., Klosterman, J. K. & Fujita, M. (2009). Angew. Chem. Int. Ed. 48, 3418–3438.  Web of Science CrossRef CAS Google Scholar
 First citationZhang, Y. W., Bai, S., Wang, Y. Y. & Han, Y. F. (2020). J. Am. Chem. Soc. 142, 13614–13621.  Web of Science CSD CrossRef CAS PubMed Google Scholar
 First citationZhu, Q. Y., Zhou, L. P., Cai, L. X., Hu, S. J., Li, X. Z. & Sun, Q. F. (2022). Inorg. Chem. 61, 16814–16821.  Web of Science CSD CrossRef CAS PubMed Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

IUCrJ
Volume 10| Part 3| May 2023| Pages 321-328
ISSN: 2052-2525
https://doi.org/10.1107/S2052252523002385