Chemically tailorable micro- and nanoparticles from infinite coordination polymers

Supplementary Information (MS # 2005-06-06618A): Chemically tailorable micro- and nanoparticles from infinite coordination polymers Moonhyun Oh & Chad A. Mirkin* Department of Chemistry and Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, USA *Corresponding Author Telephone number: (847)-491-2907 Fax Number: (847)-467-5123 Email address: chadnano@northwestern.edu S1

Supplementary Methods Solvents and all other chemicals were obtained from commercial sources and used as received unless otherwise noted. All deuterated solvents were purchased and used as received from Cambridge Isotopes Laboratories. 1 H and 13 C NMR spectra were obtained using a Varian Mercury 300 MHz or a Varian INOVA 400 MHz FT-NMR spectrometers. Infrared spectra of solid samples were obtained on a Thermo Nicolet Nexus 670 FT-IR spectrometer as KBr pellet. Diffuse reflectance spectra were obtained on a Varian Cary 5000 UV-Vis-NIR spectrophotometer. Emission spectra were obtained on a Jobin Yvon SPEX Fluorolog fluorometer using quartz cells (10 x 4 mm light path). Electrospray ionization mass spectrometric (ESI-MS) spectra were obtained on a Micromass Quatro II Triple Quadrupole mass spectrometer, and all peaks are cosnsitent with a natural abundance isotopic distribution patterns. Elemental analyses were obtained from Quantitative Technologies Inc., Whitehouse, NJ. All scanning electron microscopy (SEM) images and energy dispersive X-ray (EDX) spectra were obtained using a Hitachi S-4500 cfeg SEM (Electron Probe Instruments Center (EPIC), NUANCE, Northwestern University) equipped with an Oxford Instruments EDS system. All optical and fluorescence microscopy images were obtained using a Zeiss Axiovert 100A inverted optical/fluorescence microscope (Thomwood, NY) equipped with a Penguin 600CL digital camera (HQ FITC/Bopidy/Fluo3/Di o/egfp and HQ Texas Red filter sets were used for green and red emission, respectively). Particle size, size distribution, and ζ-potential measurements in solution were performed with a Zetasizer Nano-ZS. Bis-Schiff base, BSB S1a-b. BSB S1a: (S) 3,3 -diformyl-2,2 -dihydroxy-1,1 -binaphthyl (200 mg, 0.585 mmol), which was synthesized according to the literature procedures 1, and 3-amino-4-hydroxy-benzoic S2

acid (198 mg, 1.29 mmol) were mixed in ethanol (15 ml). The resulting solution was refluxed for 1 h. During this time, a yellow product precipitated. The precipitate product (BSB S1a) was filtered and washed with hot ethanol (85% yield). 1 H NMR (300 MHz, DMSO-d 6, 25 C): δ 13.40 (s, 2H, OH), 12.70 (br, 2H, CO 2 H), 10.65 (s, 2H, OH), 9.37 (s, 2H, CH=N), 8.51 (s, 2H), 8.04 (s, 2H), 8.02 (d, J = 8.2 Hz, 2H), 7.76 (d, J = 8.4 Hz, 2H), 7.36 (m, 4H), 7.07 (d, J = 8.1 Hz, 2H), 7.04 (d, J = 8.4 Hz, 2H). 1 H NMR (300 MHz, pyridine-d 5, 25 C): δ 9.36 (s, 2H, CH=N), 8.62 (d, J = 1.2 Hz, 2H), 8.36 (dd, J = 8.7 Hz, J = 1.2 Hz, 2H), 8.26 (s, 2H), 8.09 (m, 2H), 7.64 (m, 2H), 7.38 (m, 4H), 7.31 (d, J = 8.7 Hz, 2H). 13 C{ 1 H} NMR (100.7 MHz, DMSO-d 6, 25 C): δ 167.03 (CO 2 H), 163.21 (C=N), 155.76 (C-OH), 154.47 (C-OH), 135.16, 134.88, 134.62, 130.02, 129.23, 128.64, 127.24, 124.28, 123.41, 122.14, 121.45, 120.85, 116.37, 116.26. 13 C{ 1 H} NMR (100.7 MHz, pyridine-d 5, 25 C): δ 169.35 (CO 2 H), 163.47 (C=N), 157.72 (C-OH), 156.45 (C-OH), 137.05, 136.61, 135.50, 131.52, 130.68, 130.22, 129.49, 128.83, 126.04, 124.51, 123.05, 122.99, 118.29, 117.67. Anal. Calcd for C 36 H 24 N 2 O 8 : C, 70.58; H, 3.95; N, 4.57. Found: C, 70.38; H, 4.02; N, 4.34. ESI-MS (m/z, DMSO/CH 2 Cl 2 ): calcd for [S1a + H + ] +, 613.2; found, 613.1. IR (KBr pellet, cm -1 ): 1684s, 1615s, 1596s, 1506m, 1438m, 1412w, 1384w, 1363w, 1340w, 1293m, 1270m, 1213w, 1185w, 1152m, 1119m, 1043w, 980w, 952m, 905w, 889w, 832w, 776m, 757m, 630w. BSB S1b: BSB S1b was synthesized using the same method as for S1a, except 2-aminophenol was used instead of 3-amino-4-hydroxy-benzoic acid (90% yield). 1 H NMR (300 MHz, DMSO-d 6, 25 C): δ 13.59 (s, 2H, OH), 9.78 (s, 2H, OH), 9.29 (s, 2H, CH=N), 8.43 (s, 2H), 8.04 (m, 2H), 7.47 (d, J = 7.5 Hz, 2H), 7.35 (m, 4H), 7.15 (t, J = 7.5 Hz, 2H), 7.06 (m, 2H), 6.97 (d, J = 7.6 Hz, 2H), 6.91 (t, J = 7.5 Hz, 2H). 1 H NMR (300 MHz, pyridined 5, 25 C): δ 14.27 (s, 2H), 12.04 (br, 2H), 9.32 (s, 2H, CH=N), 8.28 (s, 2H), 8.02 (m, 2H), 7.60 (m, 2H), 7.50 (d, J = 7.8 Hz, 2H), 7.36 (m, 4H), 7.22 (m, 4H), 7.01 (m, 2H). 13 C{ 1 H} S3

NMR (100.7 MHz, DMSO-d 6, 25 C): δ 162.05 (C=N), 154.54 (C-OH), 151.57 (C-OH), 135.01, 134.64, 134.26, 129.12, 128.53, 128.45, 127.22, 124.25, 123.31, 121.53, 119.76, 119.65, 116.68, 116.29. Anal. Calcd for C 34 H 24 N 2 O 4 : C, 77.85; H, 4.61; N, 5.34. Found: C, 77.71; H, 4.58; N, 5.33. ESI-MS (m/z, DMSO/CH 2 Cl 2 ): calcd for [S1b + H + ] +, 525.2; found, 525.4. Bis-Metallo Schiff base, BMSB 2a-c and 2d. Zn-BMSB 2a: BSB S1a (5 mg, 0.008 mmol) and Zn(OAc) 2 (3 mg, 0.016 mmol) were mixed in DMF (3 ml). The color of the solution changed immediately from yellow to red. Diethyl ether was added to precipitate the product as an orange powder (84% yield). The precipitate product was separated from supernatant and washed with diethyl ether (84% yield). 1 H NMR (300 MHz, pyridine-d 5, 25 C): δ 9.60 (s, 2H, CH=N), 9.11 (d, J = 1.8 Hz, 2H), 8.58 (dd, J = 8.4 Hz, J = 1.8 Hz, 2H), 8.20 (s, 2H), 8.15 (d, J = 7.8 Hz, 2H), 7.79 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 7.35 (t, J = 7.6 Hz, 2H), 7.28 (t, J = 7.6 Hz, 2H). 13 C{ 1 H} NMR (100.7 MHz, pyridine-d 5, 25 C): δ 171.22 (CO 2 H), 169.81 (C-O), 166.21 (C-O), 159.45 (C=N), 139.02, 136.79, 135.08, 132.98, 131.02, 130.27, 128.12, 126.13, 125.20, 124.74, 120.96, 120.12, 117.97, 116.65. ESI-MS (m/z, pyridine/ch 2 Cl 2 ): calcd for [S1a 4H + + 2Zn 2+ + 2 pyridine + H + ] +, 895.1; found, 894.9; calcd for [S1a 4H + + 2Zn 2+ + pyridine + H + ] +, 816.0; found, 816.0. IR (KBr pellet, cm -1 ): 1659s, 1609s, 1588s, 1539w, 1506w, 1491m, 1425m, 1383s, 1339m, 1298m, 1223w, 1198w, 1173w, 1151w, 1121m, 1104m, 1061w, 1044w, 1024w, 958m, 898w, 843m, 788m, 748m, 663m, 478w. Cu-BMSB 2b: 2b was prepared using the same method as for 2a, except Cu(OAc) 2 (H 2 O) was used instead of Zn(OAc) 2. A brown powder was obtained in 86% yield. ESI-MS (m/z, pyridine/ch 2 Cl 2 ): calcd for [S1a 4H + + 2Cu 2+ + 2 pyridine + H + ] +, 893.1; found, 892.9. IR (KBr pellet, cm -1 ): 1653s, 1604s, 1585s, 1539w, 1522w, 1491m, 1427m, 1386s, 1369s, S4

1340m, 1306m, 1260w, 1225w, 1194w, 1173w, 1150w, 1123m, 1102m, 1061w, 1044w, 1023w, 956m, 898w, 846m, 784m, 748m, 666m, 506w, 481w. Ni-BMSB 2c: 2c was prepared using the same method as for 2a, except Ni(OAc) 2 4(H 2 O) was used instead of Zn(OAc) 2. A red powder was obtained in 82% yield. ESI-MS (m/z, pyridine/ch 2 Cl 2 ): calcd for [S1a 4H + + 2Ni 2+ + 2 pyridine + H + ] +, 883.1; found, 882.8. IR (KBr pellet, cm -1 ): 1655s, 1608s, 1584s, 1545w, 1491m, 1419m, 1387s, 1339m, 1304m, 1263w, 1226w, 1193w, 1173w, 1151w, 1119m, 1104m, 1061w, 1048w, 1026w, 960m, 901w, 841m, 786m, 749m, 668m, 517w, 479w. 2d: 2d was prepared using the same method as for 2a, except BSB S1b was used instead of BSB S1a. An orange powder was obtained in 81% yield. 1 H NMR (300 MHz, pyridine-d 5, 25 C): δ 9.54 (s, 2H, CH=N), 8.31 (s, 2H), 8.07 (d, J = 8.4 Hz, 2H), 7.94 (d, J = 8.1 Hz, 2H), 7.80 (d, J = 8.1 Hz, 2H), 7.48 (d, J = 8.1 Hz, 2H), 7.40 (t, J = 7.4 Hz, 2H), 7.33 (t, J = 7.5 Hz, 2H), 7.24 (t, J = 7.5 Hz, 2H), 7.79 (t, J = 7.5 Hz, 2H). 13 C{ 1 H} NMR (100.7 MHz, pyridine-d 5, 25 C): δ 166.23 (C-O), 165.52 (C-O), 158.53 (C=N), 138.86, 136.41, 135.70, 131.19, 130.69, 130.31, 128.01, 126.16, 126.07, 125.64, 120.90, 120.77, 115.69, 114.18. ESI-MS (m/z, pyridine/ch 2 Cl 2 ): calcd for [S1b 4H + + 2Zn 2+ + 2 pyridine + H + ] +, 807.1; found, 806.9, calcd for [S1b 4H + + 2Zn 2+ + pyridine + H + ] +, 728.1; found, 728.1. Spherical particles 3a-c. Slow diffusion method: A precursor solution was prepared by mixing BMSB 2a-c (0.008 mmol) and M(OAc) 2 (0.008 mmol, M = Zn, Cu, Ni) in pyridine (200 ~ 400 µl) [as an alternative way, by mixing BSB S1a (0.008 mmol) and M(OAc) 2 (0.024 mmol, M = Zn, Cu, Ni)]. Diethyl ether or pentane was allowed to slowly diffuse into the precursor solution. After 1 ~ 2 hours, micro-size spherical particles 3 form. Particle products were S5

isolated and subsequently washed with toluene via centrifugation-redispersion cycles. Each successive supernatant was decanted and replaced with fresh toluene (74 ~ 86% yield). Fast addition method: A precursor solution was prepared as described above. Diethyl ether or pentane (8 ml) was rapidly added into a precursor solution to form nano-size spherical particles 3. Products were isolated and washed as described above (85 ~ 92% yield). Supplementary Discussion IR spectra taken before and after formation of the particles show that the carboxylate groups are coordinating to metal ions as evidenced by a shift in CO stretching frequency from 1653 1659 cm -1 for the monomeric unbound forms (2a-c) to 1597 1605 cm -1 for the polymer particles (3a-c). 1 H and 13 C NMR spectra of diamagnetic 3a indicate coordination of the carboxylic acid groups to the metal center. The electrospray ionization mass spectra of 3b and 3c exhibit intense peaks associated with the metal-metalloligand repeat units, [2b 2H + + Cu 2+ + (pyridine) n + H + ] + and [2c 2H + + Ni 2+ + (pyridine) n + H + ] +. The NMR spectra of 3b and 3c were not informative because of the paramagnetic nature of these complexes, and the mass spectrum of 3a did not yield a monomer ion. The measurement of Zeta potential of these particles reveals that particles are negatively charged (-12 mv), which is a result of the deprotonated carboxylate groups located on their surfaces. Ancillary ligands exchange reactions: The 1 H NMR spectra of the methanol-d 4 and DMSOd 6 suspension of spherical particles 3a with ancillary ligands L of pyridine and methanol respectively, show the peaks for free pyridine and methanol molecules, which are released from the metal upon replacement with methanol-d 4 and DMSO-d 6, respectively. The S6

elemental analysis measured before and after the exchange of ancillary ligands L from pyridine to methanol, show a decreasing nitrogen content from 6.33 to 3.35%. Zn-BMSB-Zn 3a: 1 H NMR (300 MHz, pyridine-d 5, 25 C): δ 9.52 (s, 2H, CH=N), 9.28 (d, J = 1.5 Hz, 2H), 8.77 (dd, J = 8.4 Hz, J = 1.5 Hz, 2H), 8.10 (d, J = 8.1 Hz, 2H), 8.05 (s, 2H), 7.76 (d, J = 8.4 Hz, 2H), 7.50 (d, J = 8.4 Hz, 2H), 7.31 (t, J = 7.6 Hz, 2H), 7.24 (t, J = 7.6 Hz, 2H). 13 C{ 1 H} NMR (100.7 MHz, pyridine-d 5, 25 C): δ 175.95 (CO 2 ), 168.90 (C- O), 166.14 (C-O), 158.75 (C=N), 138.87, 134.65, 133.51, 131.01, 130.16, 127.91, 126.06, 125.29, 124.67, 124.43, 120.81, 120.50, 119.72, 118.26. Anal. Calcd for Zn 3 (S1a 6H)(pyridine) 3 : C, 58.90; H, 3.20; N, 6.73. Found: C, 57.83; H, 3.10; N, 6.33. IR (KBr pellet, cm -1 ): 1605s, 1591sh, 1539m, 1506w, 1489w, 1465w, 1448m, 1425w, 1375s, 1341m, 1327m, 1299m, 1217m, 1194w, 1171w, 1148m, 1121m, 1069m, 1042m, 1015w, 955w, 894w, 842m, 787m, 749m, 698m, 663m, 636m, 478w, 419w. Cu-BMSB-Cu 3b: ESI-MS (m/z, pyridine/ch 2 Cl 2 ): calcd for [S1a 6H + + 3Cu 2+ + 3 pyridine + H + ] +, 1033.0; found, 1032.7, calcd for [S1a 6H + + 3Cu 2+ + 2 pyridine + H + ] +, 954.0; found, 954.0. Anal. Calcd for Cu 3 (S1a 6H)(H 2 O) 2 (pyridine) 3 : C, 57.22; H, 3.48; N, 6.54. Found: C, 57.69; H, 2.96; N, 6.47. IR (KBr pellet, cm -1 ): 1602s, 1589sh, 1539m, 1507w, 1490w, 1466w, 1449m, 1425w, 1369s, 1342m, 1325m, 1262w, 1217m, 1190w, 1172w, 1148m, 1124m, 1069m, 1043m, 1017w, 955w, 897w, 846m, 783m, 748m, 696m, 671m, 639m, 504w, 479w, 419w. Ni-BMSB-Ni 3c: ESI-MS (m/z, pyridine/ch 2 Cl 2 ): calcd for [S1a 6H + + 3Ni 2+ + 4 pyridine + H + ] +, 1097.1; found, 1097.0. Anal. Calcd for Ni 3 (S1a 6H)(H 2 O) 2 (pyridine) 3 : C, 58.01; H, 3.53; N, 6.63. Found: C, 58.08; H, 3.28; N, 6.57. IR (KBr pellet, cm -1 ): 1597s, 1589sh, 1542m, 1507w, 1497w, 1465w, 1448m, 1429w, 1385s, 1369m, 1343m, 1324m, 1269w, 1217m, 1192w, 1172w, 1149m, 1125m, 1070m, 1042m, 1017w, 951w, 897w, S7

856m, 786m, 757m, 693m, 639w, 516w, 494w, 419w. There are inherent difficulties in formulating the exact number of pyridine and water in particle 3a-c due to the possibility of exchange with other molecules. X-ray crystal structure determination of 2b: A dark tabular crystal was mounted using oil on a glass fiber. Diffraction intensity data were collected with a Bruker SMART-1000 CCD diffractometer equipped with a graphite-monochromated Mo Kα radiation source. The data collected were processed to produce conventional intensity data by the program SAINT-NT (Bruker). The intensity data were corrected for Lorentz and polarization effects. Absorption corrections were applied using the SADABS empirical method. The structures were solved by direct methods, completed by subsequent difference Fourier syntheses and refined by full matrix least-squares procedures on F 2. The disordered methanol was refined with a group anisotropic displacement parameter, and occupancies adding to fully occupied. The remaining non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included in idealized positions, except those on the disordered and partially occupied methanol, and the hydrogen atom on O5 (methanol), but not refined. The DMF was fixed to ½ occupied. All software and sources of scattering factors are contained in the SHELXTL program package (version 5.10, G. Sheldrick, Bruker-AXS, Madison, WI). Crystallographic data, and bond lengths and angles are given in Supplementary Tables 1 and 2. Reference 1. Zhang, H.- C., Huang, W.-S., & Pu, L. J. Org. Chem. 66, 481-487 (2001). S8

EtOH M(OAc) 2 (2 eq.) M = Zn, Cu, Ni O OH OH + O NH 2 Reflux OH OH DMF, RT O O N N N M M L x L x R OH OH R R O O N R R (2 eq.) OH S1a, R =CO 2 H S1b, R = H Zn-BMSB 2a, M = Zn 2+, R = CO 2 H Cu-BMSB 2b, M = Cu 2+, R = CO 2 H Ni-BMSB 2c, M = Ni 2+, R = CO 2 H 2d, M = Zn 2+, R = H L = pyridine, water Supplementary Equation 1 Synthesis of BSBs (S1a-b), BMSBs (2a-c), and 2d. S9

a b c Supplementary Figure 1 (a) ORTEP representation of homochiral BMSB building block 2b. Thermal ellipsoids are drawn at 50% probability. Ball and stick (b) and space filling (c) representations of the two dimensional network generated from 2b. Hydrogen atoms and methanol molecules, which weakly interact with Cu 2+, are omitted for clarity. (Key: Cu, green; O, red; N, blue; C, gray.) S10

a b c d 5 µm Supplementary Figure 2 OM (a) and FM (b and c) images of spherical particles Zn- BMSB-Zn 3a, which are prepared from the slow diffusion of diethyl ether into a precursor solution containing Zn-BMSB 2a and Zn(OAc) 2 1a in a 1:1 ratio in pyridine. (d) Emission spectra of a toluene suspension of spherical particles 3a (red line) and monomer building block 2a in pyridine (blue line). Excitation wavelength = 420 nm. S11

Supplementary Figure 3 EDX spectrum of spherical particles Zn-BMSB-Zn 3a. S12

a b 5 µm 5 µm Supplementary Figure 4 SEM images showing many of the intermediate (a) and spherical (b) particles consisting of Zn-BMSB-Zn 3a. They are prepared from the slow diffusion of pentane into a precursor solution containing Zn-BMSB 2a and Zn(OAc) 2 1a in a 1:1 ratio in pyridine. S13

2 µm Supplementary Figure 5 SEM image of intermediate particles Zn-BMSB-Zn 3a formed by aggregation of a few smaller particles. These are observed during the slow diffusion of pentane into a precursor solution containing Zn-BMSB 2a and Zn(OAc) 2 1a in a 1:1 ratio in pyridine. S14

1 µm Supplementary Figure 6 SEM image of intermediate particles Zn-BMSB-Zn 3a, which are observed during the slow diffusion of diethyl ether into a precursor solution containing Zn-BMSB 2a and Zn(OAc) 2 1a in a 1:1 ratio in pyridine. S15

a 500 nm b Supplementary Figure 7 (a) SEM image of spherical particles Cu-BMSB-Cu 3b, which are prepared from the fast addition of pentane into a precursor solution containing Cu- BMSB 2b and Cu(OAc) 2 (H 2 O) 1b in a 1:1 ratio in pyridine. (b) EDX spectrum of spherical particles 3b. S16

a 10 µm b Intermediate Sphere 5 µm Supplementary Figure 8 Dark-field OM images showing spherical and intermediate particles of Cu-BMSB-Cu 3b. They were prepared from the slow diffusion of pentane into a precursor solution containing Cu-BMSB 2b and Cu(OAc) 2 (H 2 O) 1b in a 1:1 ratio in pyridine. (a) An image showing many fully formed particles. (b) An image showing clusters in the state of fusing in addition to a fully formed particle. S17

a 1 µm b Supplementary Figure 9 (a) SEM image of spherical particles Ni-BMSB-Ni 3c, which are prepared from the fast addition of pentane into a precursor solution containing Ni-BMSB 2c and Ni(OAc) 2 4(H 2 O) 1c in a 1:1 ratio in pyridine. (b) EDX spectrum of spherical particles 3c. S18

Supplementary Figure 10 Diffuse reflectance spectra of spherical particles Zn-BMSB-Zn 3a with different ancillary ligands L (pyridine, water and methanol). S19

a b 176 nm 575 nm c 1.72 µm Supplementary Figure 11 Size distributions for particles Zn-BMSB-Zn 3a determined by DLS. Particles are prepared from (a) the fast addition of diethyl ether into a precursor solution, (b) the fast addition of pentane into a precursor solution, and (c) the slow addition of diethyl ether into a precursor solution. The precursor solution contains Zn-BMSB 2a and Zn(OAc) 2 1a in a 1:1 ratio in pyridine. The mean average diameter is quoted on the left in each graph. S20

Supplementary Table 1 Crystal data and structure refinement for 2b. Empirical formula C21.50 H21.50 Cu N1.50 O6.50 Formula weight 468.44 Temperature 153(2) K Wavelength 0.71073 Å Crystal system Orthorhombic Space group P2(1)2(1)2 Unit cell dimensions a = 16.2976(18) Å b = 17.328(2) Å c = 9.139(2) Å Volume 2580.8(7) Å 3 Z 4 Calculated density 1.206 Mg/m 3 Absorption coefficient 0.881 mm -1 F(000) 968 Crystal size 0.316 x 0.284 x 0.142 mm Theta range for data collection 2.23 to 28.94 º Limiting indices -21 h 21, -23 k 22, -12 l 12 Reflections collected / unique 24204 / 6323 [R(int) = 0.0349] Completeness to theta = 28.94 94.8 % Absorption correction Integration Max. and min. transmission 0.8856 and 0.7637 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6323 / 1 / 316 Goodness-of-fit on F^2 1.132 Final R indices [I>2sigma(I)] R1 = 0.0659, wr2 = 0.1888 R indices (all data) R1 = 0.0795, wr2 = 0.2031 Largest diff. peak and hole 1.079 and -0.527 e-/å -3 S21

Supplementary Table 2 Bond lengths [Å] and angles [º] for 2b. Cu(1)-O(1) 1.909(2) Cu(1)-N(1) 1.939(3) Cu(1)-O(2) 1.948(3) Cu(1)-O(3)#1 1.951(3) Cu(1)-O(5) 2.272(5) O(1)-C(1) 1.328(4) O(2)-C(17) 1.312(5) O(3)-C(18) 1.222(5) O(3)-Cu(1)#2 1.951(3) O(4)-C(18) 1.294(4) O(5)-C(19) 1.416(12) N(1)-C(11) 1.286(5) N(1)-C(12) 1.422(5) C(1)-C(2) 1.390(5) C(1)-C(10) 1.447(5) C(2)-C(3) 1.412(5) C(2)-C(2)#3 1.498(6) C(3)-C(8) 1.432(6) C(3)-C(4) 1.436(5) C(4)-C(5) 1.369(6) C(5)-C(6) 1.435(7) C(6)-C(7) 1.353(7) C(7)-C(8) 1.417(6) C(8)-C(9) 1.395(6) C(9)-C(10) 1.390(5) C(10)-C(11) 1.450(5) C(12)-C(13) 1.379(5) C(12)-C(17) 1.408(6) C(13)-C(14) 1.401(5) C(14)-C(15) 1.386(5) C(14)-C(18) 1.474(5) C(15)-C(16) 1.389(6) C(16)-C(17) 1.407(6) O(1)-Cu(1)-N(1) 93.61(12) O(1)-Cu(1)-O(2) 170.30(18) N(1)-Cu(1)-O(2) 84.78(14) O(1)-Cu(1)-O(3)#1 92.00(13) N(1)-Cu(1)-O(3)#1 173.63(13) O(2)-Cu(1)-O(3)#1 89.19(13) O(1)-Cu(1)-O(5) 96.20(14) N(1)-Cu(1)-O(5) 89.64(15) O(2)-Cu(1)-O(5) 93.4(2) O(3)#1-Cu(1)-O(5) 92.7(2) C(1)-O(1)-Cu(1) 128.9(2) C(17)-O(2)-Cu(1) 110.1(3) C(18)-O(3)-Cu(1)#2 130.6(3) C(19)-O(5)-Cu(1) 120.5(4) C(11)-N(1)-C(12) 123.9(3) C(11)-N(1)-Cu(1) 126.3(3) C(12)-N(1)-Cu(1) 109.8(2) O(1)-C(1)-C(2) 119.7(3) O(1)-C(1)-C(10) 121.2(3) C(2)-C(1)-C(10) 119.1(3) S22

C(1)-C(2)-C(3) 120.7(3) C(1)-C(2)-C(2)#3 118.6(3) C(3)-C(2)-C(2)#3 120.7(3) C(2)-C(3)-C(8) 120.2(3) C(2)-C(3)-C(4) 122.1(3) C(8)-C(3)-C(4) 117.6(3) C(5)-C(4)-C(3) 120.8(4) C(4)-C(5)-C(6) 120.1(4) C(7)-C(6)-C(5) 120.8(5) C(6)-C(7)-C(8) 120.3(4) C(9)-C(8)-C(7) 121.3(4) C(9)-C(8)-C(3) 118.4(4) C(7)-C(8)-C(3) 120.3(4) C(10)-C(9)-C(8) 122.0(4) C(9)-C(10)-C(1) 119.5(3) C(9)-C(10)-C(11) 116.2(3) C(1)-C(10)-C(11) 124.3(3) N(1)-C(11)-C(10) 125.2(3) C(13)-C(12)-C(17) 122.2(4) C(13)-C(12)-N(1) 125.0(3) C(17)-C(12)-N(1) 112.7(3) C(12)-C(13)-C(14) 118.7(3) C(15)-C(14)-C(13) 120.6(4) C(15)-C(14)-C(18) 121.9(3) C(13)-C(14)-C(18) 117.5(3) C(14)-C(15)-C(16) 120.0(4) C(15)-C(16)-C(17) 120.9(4) O(2)-C(17)-C(16) 122.6(4) O(2)-C(17)-C(12) 120.0(4) C(16)-C(17)-C(12) 117.3(4) O(3)-C(18)-O(4) 123.6(3) O(3)-C(18)-C(14) 120.3(3) O(4)-C(18)-C(14) 116.1(3) Symmetry transformations used to generate equivalent atoms: #1 x+1/2,-y+1/2,-z+1; #2 x-1/2,-y+1/2,-z+1; #3 -x+2,-y,z S23