[1 (5 Chloro 2 oxido­phenyl)­ethanone 4 nitro­benzoyl­hydrazonato(2−)]tris­­(pyridine)­nickel(II) pyridine solvate

11 

(1)metal-organic papers [1-(5-Chloro-2-oxidophenyl)ethanone 4-nitrobenzoylhydrazonato(2ÿ)]tris(pyridine)nickel(II) pyridine solvate. Acta Crystallographica Section E. Structure Reports Online ISSN 1600-5368. Hapipah Ali,a Nur Ashikin Khamis,a W. Jefri Basiruna and Bohari M. Yaminb* a. Department of Chemistry, Universiti Malaya, Kuala Lumpur, Malaysia, and bSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia Correspondence e-mail: bohari@pkrisc.cc.ukm.my. Key indicators. The double chelate ring in the title complex, [Ni(C15H11ClN3O3)2]C5H5N, is essentially planar, with the O,N,O-donor atoms and a pyridine ligand N atom occuping the equatorial positions in a distorted octahedral environment about the Ni atom. The NÐNiÐN axial bond angle is 173.16 (8) .. Received 20 April 2004 Accepted 28 May 2004 Online 12 June 2004. Comment The title complex, (I), was obtained on recrystallization of [Ni(C15H11N3O3Cl)2] from pyridine. Elemental analysis indicated the presence of four pyridine molecules and the loss of one of the ligands. The molecular structure of (I) is shown in Fig. 1 and selected bond distances and angles are given in Table 1.. Single-crystal X-ray study T = 273 K Ê Mean (C±C) = 0.005 A R factor = 0.057 wR factor = 0.139 Data-to-parameter ratio = 17.8 For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.. It can be seen that the Ni atom is chelated by the ligand in a tridentate manner via atoms O1, N1 and O2. The coordination geometry of atom Ni1 is distorted octahedral. Atoms N4 and N5 occupy the axial positions, with an angle of 173.16 (8) . The equatorial atoms, O1, N1, O2 and N6, make cis angles at the Ni atom in the range 80.17 (8)±95.52 (8) . The axial NiÐN4 and Ê , slightly longer than NiÐN5 bond lengths are both 2.176 (2) A the equatorial NiÐN6 and NiÐN1 bond distances of 2.096 (2) Ê , respectively. These distances are comparable and 2.012 (2) A. # 2004 International Union of Crystallography Printed in Great Britain ± all rights reserved. m912. Ali Hapipah et al.. . Figure 1. The molecular structure of (I), with 50% probability displacement ellipsoids. H atoms have been omitted for clarity.. [Ni(C15H11ClN3O3)2]C5H5N. DOI: 10.1107/S1600536804013030. Acta Cryst. (2004). E60, m912±m914.

(2) metal-organic papers Data collection 7728 independent re¯ections 5161 re¯ections with I > 2(I) Rint = 0.036 max = 27.5 h = ÿ16 ! 13 k = ÿ27 ! 27 l = ÿ16 ! 16. Bruker SMART APEX areadetector diffractometer ! scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.757, Tmax = 0.908 26 253 measured re¯ections. Re®nement w = 1/[ 2(Fo2) + (0.0629P)2 + 0.3467P] where P = (Fo2 + 2Fc2)/3 (/)max < 0.001 Ê ÿ3 max = 0.57 e A Ê ÿ3 min = ÿ0.18 e A. Re®nement on F 2 R[F 2 > 2(F 2)] = 0.057 wR(F 2) = 0.139 S = 1.06 7728 re¯ections 433 parameters H-atom parameters constrained. Table 1. Ê ,  ). Selected geometric parameters (A. Figure 2. A packing diagram for (I), viewed down the b axis. Dashed lines denote CÐH  N hydrogen bonds.. with those observed in the octahedral nickel complex [Ni(C16H24N20)2(N3)2] (You et al., 2004). One pyridine molecule is present as an uncoordinated solvent molecule. The structural dimensions of the tridentate ligand are typical for a Schiff base and are in the normal ranges (Allen et al., 1987; Orpen et al., 1989); they are in agreement with other octahedral nickel complexes, such as [Ni(C7H7N4O2)] (Zhou et al., 2004). The chelate double-ring fragment Ni1/O1/C6/C7/ C8/N1/N2/C9/O2/N6 is essentially planar, with a maximum Ê for atom N6. deviation from the mean plane of 0.083 (2) A The dihedral angle between the C1±C6 and C10±C15 benzene rings is only 3.35 (13) . In the crystal structure of (I), symmetry-related molecules are linked by an intermolecular C18ÐH18A  N2i interaction (symmetry code as in Table 2), forming polymeric chains lying in the ac face, as shown in Fig. 2.. Experimental The complex [Ni(C15H11N3O3Cl)2] was synthesized by the template condensation of 2-hydroxy-5-chloroacetophenone-4-nitrobenzhydrazide (0.3 g, 1.0 mmol) with nickel acetate dihydrate (0.21 g, 0.5 mmol), by re¯uxing and stirring in ethanol for 5 h. A pale-yellow solid was obtained and ®ltered off. The title complex, (I), was obtained by recrystallization of this product from pyridine. Crystal data [Ni(C15H11ClN3O3)2]C5H5N Mr = 706.82 Monoclinic, P21 =n Ê a = 12.585 (2) A Ê b = 21.175 (3) A Ê c = 12.704 (2) A

(3) = 90.211 (3) Ê3 V = 3385.7 (9) A Z=4 Acta Cryst. (2004). E60, m912±m914. Dx = 1.387 Mg mÿ3 Mo K radiation Cell parameters from 4938 re¯ections  = 1.8±27.5  = 0.70 mmÿ1 T = 273 (2) K Block, dark orange 0.42  0.23  0.14 mm. Ni1ÐO1 Ni1ÐN1 Ni1ÐO2 Ni1ÐN6 Ni1ÐN4 Ni1ÐN5 O1ÐC1. 1.9787 (18) 2.012 (2) 2.0357 (17) 2.096 (2) 2.176 (2) 2.176 (2) 1.297 (3). O1ÐNi1ÐN1 O1ÐNi1ÐO2 N1ÐNi1ÐO2 O1ÐNi1ÐN6 N1ÐNi1ÐN6 O2ÐNi1ÐN6 O1ÐNi1ÐN4 N1ÐNi1ÐN4. O2ÐC9 O3ÐN3 O4ÐN3 N1ÐC7 N1ÐN2 N2ÐC9. 90.39 (8) 170.49 (7) 80.17 (8) 93.93 (8) 175.66 (8) 95.52 (8) 91.37 (8) 92.04 (9). 1.283 (3) 1.208 (3) 1.200 (4) 1.302 (3) 1.398 (3) 1.316 (3). O2ÐNi1ÐN4 N6ÐNi1ÐN4 O1ÐNi1ÐN5 N1ÐNi1ÐN5 O2ÐNi1ÐN5 N6ÐNi1ÐN5 N4ÐNi1ÐN5. 87.80 (8) 88.26 (9) 92.16 (8) 93.79 (8) 89.68 (8) 85.65 (9) 173.16 (8). Table 2. Ê ,  ). Hydrogen-bonding geometry (A DÐH  A C18ÐH18A  N2. i. DÐH. H  A. D  A. DÐH  A. 0.93. 2.58. 3.500 (4). 169. Symmetry code: (i) 12 ‡ x; 12 ÿ y; z ÿ 12.. After their location in Fourier difference maps, all H atoms were positioned geometrically and allowed to ride on their parent C atoms, Ê and Uiso(H) = 1.2 or 1.5Ueq(C). with CÐH = 0.93±0.96 A Data collection: SMART (Siemens, 1996); cell re®nement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).. The authors thank the Malaysian Government, and both Universiti Malaya and Universiti Kebangsaan Malaysia, for research grants IRPA Nos. 09-02-03-0145 and 09-02-02-993, respectively.. References Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1±19. Ali Hapipah et al.. . [Ni(C15H11ClN3O3)2]C5H5N. m913.

(4) metal-organic papers Nardelli, M. (1995). J. Appl. Cryst. 28, 659. Orpen, G., Brammer, L., Allen, F. H., Kennard, O., Watson, D. G. & Taylor, R. (1989). J. Chem. Soc. Dalton Trans. pp. S1±83. Sheldrick, G. M. (1996). SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of GoÈttingen, Germany. Sheldrick, G. M. (1997b). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.. m914. Ali Hapipah et al.. . [Ni(C15H11ClN3O3)2]C5H5N. Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13. You, Z.-L., Xiong, Z.-D., Liu, W.-S., Tan, M.-Y. & Zhu, H.-L (2004). Acta Cryst. E60, m79±m81. Zhou, J., Chen, Z.-F., Wang, X.-W., Tan, Y.-S., Liang, H. & Zhang, Y. (2004). Acta Cryst. E60, m568±m570.. Acta Cryst. (2004). E60, m912±m914.

(5) supporting information. supporting information Acta Cryst. (2004). E60, m912–m914. [https://doi.org/10.1107/S1600536804013030]. [1-(5-Chloro-2-oxidophenyl)ethanone 4-nitrobenzoylhydrazonato(2−)]tris(pyridine)nickel(II) pyridine solvate Hapipah Ali, Nur Ashikin Khamis, W. Jefri Basirun and Bohari M. Yamin [1-(5-Chloro-2-oxidophenyl)ethanone 4-nitrobenzoylhydrazonato(2-)]tripyridinenickel(II) pyridine solvate Crystal data [Ni(C15H11ClN3O3)2]·C5H5N Mr = 706.82 Monoclinic, P21/n a = 12.585 (2) Å b = 21.175 (3) Å c = 12.704 (2) Å β = 90.211 (3)° V = 3385.7 (9) Å3 Z=4. F(000) = 1464 Dx = 1.387 Mg m−3 Mo Kα radiation, λ = 0.71073 Å Cell parameters from 4938 reflections θ = 1.8–27.5° µ = 0.70 mm−1 T = 273 K Block, dark orange 0.42 × 0.23 × 0.14 mm. Data collection Bruker SMART APEX area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator Detector resolution: 83.66 pixels mm-1 ω scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.757, Tmax = 0.908. 26253 measured reflections 7728 independent reflections 5161 reflections with I > 2σ(I) Rint = 0.036 θmax = 27.5°, θmin = 1.8° h = −16→13 k = −27→27 l = −16→16. Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.057 wR(F2) = 0.139 S = 1.06 7728 reflections 433 parameters 0 restraints Primary atom site location: structure-invariant direct methods. Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ2(Fo2) + (0.0629P)2 + 0.3467P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001 Δρmax = 0.57 e Å−3 Δρmin = −0.18 e Å−3. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2). Ni1. x. y. z. Uiso*/Ueq. 0.17899 (3). 0.250461 (14). 0.30205 (2). 0.04754 (12). Acta Cryst. (2004). E60, m912–m914. sup-1.

(6) supporting information O1 O2 O3 O4 N1 N2 N4 N5 N6 N7 C1 C2 H2B C3 H3A C4 C5 H5A C6 C7 C8 H8A H8B H8C C9 C10 C11 H11A C12 H12A C13 C14 H14A C15 H15A N3 C16 H16A C17 H17A C18 H18A C19 H19A C20 H20A C21 H21A. 0.15109 (15) 0.21929 (14) 0.4132 (2) 0.4154 (3) 0.23282 (16) 0.27185 (17) 0.33748 (19) 0.01678 (18) 0.12419 (17) 0.1001 (4) 0.1557 (2) 0.1184 (2) 0.0935 0.1167 (3) 0.0912 0.1535 (2) 0.1916 (2) 0.2165 0.1950 (2) 0.2380 (2) 0.2880 (2) 0.3122 0.2365 0.3472 0.26072 (19) 0.30087 (19) 0.3051 (2) 0.2845 0.3396 (2) 0.3427 0.3688 (2) 0.3664 (3) 0.3870 0.3329 (2) 0.3319 0.4020 (2) 0.3779 (3) 0.3368 0.4763 (3) 0.5010 0.5376 (3) 0.6047 0.4985 (3) 0.5386 0.3996 (3) 0.3742 −0.0210 (3) 0.0254. Acta Cryst. (2004). E60, m912–m914. 0.34085 (8) 0.16262 (8) −0.10769 (12) −0.06359 (13) 0.27196 (10) 0.21956 (10) 0.25760 (10) 0.23477 (11) 0.22084 (11) 0.9853 (2) 0.38711 (12) 0.44636 (13) 0.4497 0.49945 (13) 0.5376 0.49475 (12) 0.43909 (12) 0.4376 0.38340 (11) 0.32591 (12) 0.33065 (13) 0.2897 0.3461 0.3592 0.16772 (12) 0.10850 (12) 0.05383 (13) 0.0545 −0.00236 (13) −0.0392 −0.00225 (13) 0.05127 (14) 0.0501 0.10717 (13) 0.1441 −0.06191 (12) 0.31204 (15) 0.3480 0.31925 (18) 0.3592 0.2678 (2) 0.2714 0.2109 (2) 0.1745 0.20749 (16) 0.1681 0.17734 (16) 0.1436. 0.27369 (14) 0.35365 (13) 0.5795 (2) 0.7287 (2) 0.44701 (16) 0.50180 (17) 0.23517 (18) 0.35474 (18) 0.15410 (17) 0.2618 (8) 0.3405 (2) 0.3058 (2) 0.2370 0.3677 (3) 0.3416 0.4693 (3) 0.5071 (2) 0.5761 0.4460 (2) 0.4959 (2) 0.6035 (2) 0.6254 0.6528 0.6010 0.4457 (2) 0.4967 (2) 0.4385 (2) 0.3681 0.4832 (2) 0.4436 0.5863 (2) 0.6462 (2) 0.7166 0.6007 (2) 0.6404 0.6351 (3) 0.2068 (3) 0.2165 0.1640 (3) 0.1460 0.1480 (3) 0.1182 0.1765 (3) 0.1667 0.2200 (3) 0.2400 0.3653 (3) 0.3558. 0.0565 (5) 0.0510 (4) 0.1140 (10) 0.1410 (13) 0.0457 (5) 0.0480 (5) 0.0544 (6) 0.0557 (6) 0.0537 (6) 0.179 (3) 0.0507 (6) 0.0636 (8) 0.076* 0.0690 (8) 0.083* 0.0637 (8) 0.0575 (7) 0.069* 0.0480 (6) 0.0488 (6) 0.0655 (8) 0.098* 0.098* 0.098* 0.0456 (6) 0.0468 (6) 0.0606 (7) 0.073* 0.0648 (8) 0.078* 0.0579 (7) 0.0708 (9) 0.085* 0.0640 (8) 0.077* 0.0755 (8) 0.0742 (9) 0.089* 0.0902 (11) 0.108* 0.0877 (11) 0.105* 0.1079 (15) 0.129* 0.0895 (12) 0.107* 0.0800 (10) 0.096*. sup-2.

(7) supporting information C22 H22A C23 H23A C24 H24A C25 H25A C26 H26A C27 H27A C28 H28A C29 H29A C30 H30A C31 H31A C32 H32A C33 H33A C34 H34A C35 H35A Cl1. −0.1253 (3) −0.1483 −0.1935 (3) −0.2640 −0.1566 (3) −0.2022 −0.0518 (3) −0.0282 0.0747 (2) 0.0670 0.0345 (3) 0.0010 0.0443 (3) 0.0166 0.0958 (3) 0.1048 0.1336 (3) 0.1677 0.0339 (6) 0.0623 −0.0655 (5) −0.1103 −0.1059 (4) −0.1789 −0.0483 (6) −0.0800 0.0520 (7) 0.0930 0.15041 (8). 0.16412 (18) 0.1225 0.2122 (2) 0.2048 0.2709 (2) 0.3051 0.28100 (17) 0.3224 0.26021 (14) 0.3021 0.24224 (17) 0.2715 0.1810 (2) 0.1674 0.13981 (18) 0.0978 0.16143 (15) 0.1330 0.9924 (3) 0.9937 0.9972 (2) 1.0011 0.9968 (3) 1.0018 0.9896 (3) 0.9889 0.9835 (2) 0.9777 0.56194 (4). 0.3896 (3) 0.3956 0.4045 (3) 0.4223 0.3927 (5) 0.4011 0.3684 (3) 0.3612 0.0891 (2) 0.1096 −0.0063 (3) −0.0499 −0.0366 (3) −0.1006 0.0288 (3) 0.0095 0.1231 (2) 0.1677 0.3485 (5) 0.4162 0.3340 (5) 0.3917 0.2391 (6) 0.2310 0.1562 (5) 0.0899 0.1649 (6) 0.1050 0.54950 (8). 0.0986 (13) 0.118* 0.1008 (13) 0.121* 0.127 (2) 0.153* 0.0968 (13) 0.116* 0.0616 (8) 0.074* 0.0734 (9) 0.088* 0.0822 (10) 0.099* 0.0883 (11) 0.106* 0.0745 (9) 0.089* 0.137 (2) 0.164* 0.1157 (16) 0.139* 0.1307 (19) 0.157* 0.1275 (18) 0.153* 0.135 (2) 0.161* 0.0922 (3). Atomic displacement parameters (Å2). Ni1 O1 O2 O3 O4 N1 N2 N4 N5 N6 N7 C1 C2 C3 C4. U11. U22. U33. U12. U13. U23. 0.0530 (2) 0.0689 (13) 0.0604 (12) 0.163 (3) 0.245 (4) 0.0459 (13) 0.0522 (13) 0.0569 (15) 0.0532 (14) 0.0573 (15) 0.110 (4) 0.0484 (16) 0.069 (2) 0.076 (2) 0.068 (2). 0.0468 (2) 0.0498 (10) 0.0488 (10) 0.0594 (15) 0.0817 (19) 0.0461 (11) 0.0458 (12) 0.0597 (15) 0.0596 (14) 0.0600 (14) 0.116 (4) 0.0462 (14) 0.0569 (17) 0.0473 (16) 0.0441 (15). 0.0429 (2) 0.0508 (11) 0.0438 (10) 0.119 (2) 0.096 (2) 0.0452 (12) 0.0461 (12) 0.0466 (12) 0.0544 (14) 0.0438 (12) 0.312 (9) 0.0576 (16) 0.0655 (19) 0.084 (2) 0.079 (2). 0.00384 (14) 0.0069 (9) 0.0018 (8) 0.0278 (16) 0.024 (2) 0.0002 (9) 0.0015 (10) 0.0030 (11) 0.0002 (11) 0.0055 (11) −0.011 (3) −0.0010 (11) 0.0052 (14) 0.0057 (14) −0.0016 (13). 0.00186 (15) 0.0006 (9) −0.0028 (9) −0.0157 (19) −0.059 (2) 0.0062 (10) 0.0028 (10) 0.0045 (10) 0.0049 (11) 0.0002 (11) −0.014 (5) 0.0131 (13) 0.0090 (15) 0.0127 (18) 0.0179 (17). −0.00260 (14) −0.0003 (9) −0.0021 (8) 0.0048 (15) 0.0179 (16) −0.0006 (10) −0.0013 (10) 0.0001 (11) −0.0094 (11) −0.0057 (11) −0.042 (5) 0.0015 (13) 0.0069 (15) 0.0056 (16) −0.0103 (14). Acta Cryst. (2004). E60, m912–m914. sup-3.

(8) supporting information C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 N3 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 Cl1. 0.0602 (18) 0.0449 (15) 0.0456 (15) 0.074 (2) 0.0427 (15) 0.0428 (15) 0.077 (2) 0.084 (2) 0.0566 (18) 0.091 (2) 0.084 (2) 0.085 (2) 0.076 (2) 0.085 (3) 0.074 (2) 0.091 (3) 0.088 (3) 0.067 (2) 0.073 (3) 0.063 (2) 0.069 (3) 0.070 (2) 0.0594 (19) 0.062 (2) 0.084 (3) 0.114 (3) 0.098 (3) 0.134 (5) 0.115 (4) 0.073 (3) 0.132 (5) 0.142 (6) 0.1156 (8). 0.0500 (15) 0.0466 (14) 0.0520 (15) 0.0595 (17) 0.0500 (14) 0.0503 (14) 0.0557 (16) 0.0482 (16) 0.0518 (16) 0.0646 (19) 0.0524 (16) 0.0551 (16) 0.063 (2) 0.082 (2) 0.109 (3) 0.098 (3) 0.072 (2) 0.069 (2) 0.082 (3) 0.103 (3) 0.084 (3) 0.068 (2) 0.0655 (19) 0.097 (3) 0.109 (3) 0.080 (2) 0.067 (2) 0.151 (5) 0.116 (4) 0.145 (5) 0.151 (5) 0.099 (3) 0.0507 (4). 0.0623 (18) 0.0527 (16) 0.0490 (15) 0.0632 (19) 0.0440 (14) 0.0474 (15) 0.0488 (16) 0.0624 (19) 0.0653 (19) 0.0566 (18) 0.0558 (17) 0.086 (2) 0.084 (2) 0.103 (3) 0.079 (2) 0.135 (4) 0.108 (3) 0.103 (3) 0.141 (4) 0.137 (4) 0.229 (6) 0.153 (4) 0.0600 (18) 0.0607 (19) 0.0532 (19) 0.071 (2) 0.0580 (19) 0.125 (5) 0.116 (4) 0.174 (6) 0.099 (4) 0.163 (6) 0.1103 (7). −0.0047 (13) −0.0012 (11) −0.0040 (11) 0.0016 (14) −0.0003 (11) 0.0009 (11) 0.0053 (14) 0.0069 (14) 0.0009 (12) 0.0049 (16) 0.0051 (15) 0.0055 (14) 0.0037 (16) −0.013 (2) 0.008 (2) 0.034 (2) 0.0148 (19) 0.0009 (17) −0.018 (2) −0.014 (2) 0.001 (2) −0.0036 (18) 0.0056 (14) −0.0056 (17) −0.018 (2) 0.001 (2) 0.0113 (17) 0.022 (4) 0.033 (3) 0.006 (3) −0.005 (4) −0.014 (4) 0.0009 (4). 0.0089 (14) 0.0105 (12) 0.0068 (12) −0.0089 (15) 0.0059 (11) 0.0007 (11) −0.0047 (14) −0.0016 (16) −0.0048 (14) −0.0186 (16) −0.0105 (15) −0.0155 (16) 0.0246 (18) 0.030 (2) 0.032 (2) 0.060 (3) 0.041 (2) 0.0105 (19) 0.022 (2) 0.033 (2) 0.049 (3) 0.032 (2) −0.0008 (15) −0.0132 (16) −0.0094 (17) −0.011 (2) −0.0133 (17) −0.042 (4) 0.035 (3) −0.010 (4) −0.009 (4) 0.079 (5) 0.0134 (6). −0.0071 (13) −0.0028 (12) −0.0057 (12) −0.0117 (14) 0.0011 (12) −0.0001 (12) −0.0048 (13) −0.0054 (13) 0.0080 (14) 0.0026 (15) −0.0057 (13) 0.0097 (15) −0.0033 (17) −0.001 (2) 0.010 (2) 0.025 (3) 0.018 (2) 0.0002 (19) −0.012 (2) −0.038 (3) −0.047 (3) −0.029 (2) 0.0026 (14) 0.0111 (18) −0.014 (2) −0.0242 (19) −0.0064 (15) −0.045 (4) 0.003 (3) 0.021 (4) −0.015 (3) −0.026 (4) −0.0229 (4). Geometric parameters (Å, º) Ni1—O1 Ni1—N1 Ni1—O2 Ni1—N6 Ni1—N4 Ni1—N5 O1—C1 O2—C9 O3—N3 O4—N3 N1—C7 N1—N2. Acta Cryst. (2004). E60, m912–m914. 1.9787 (18) 2.012 (2) 2.0357 (17) 2.096 (2) 2.176 (2) 2.176 (2) 1.297 (3) 1.283 (3) 1.208 (3) 1.200 (4) 1.302 (3) 1.398 (3). C12—H12A C13—C14 C13—N3 C14—C15 C14—H14A C15—H15A C16—C17 C16—H16A C17—C18 C17—H17A C18—C19 C18—H18A. 0.9300 1.366 (4) 1.468 (4) 1.383 (4) 0.9300 0.9300 1.363 (4) 0.9300 1.351 (5) 0.9300 1.351 (5) 0.9300. sup-4.

(9) supporting information N2—C9 N4—C16 N4—C20 N5—C21 N5—C25 N6—C30 N6—C26 N7—C35 N7—C31 C1—C2 C1—C6 C2—C3 C2—H2B C3—C4 C3—H3A C4—C5 C4—Cl1 C5—C6 C5—H5A C6—C7 C7—C8 C8—H8A C8—H8B C8—H8C C9—C10 C10—C11 C10—C15 C11—C12 C11—H11A C12—C13. 1.316 (3) 1.311 (4) 1.333 (4) 1.313 (4) 1.317 (4) 1.323 (4) 1.327 (4) 1.370 (8) 1.391 (8) 1.410 (4) 1.429 (4) 1.372 (4) 0.9300 1.374 (4) 0.9300 1.359 (4) 1.751 (3) 1.412 (3) 0.9300 1.474 (4) 1.507 (4) 0.9600 0.9600 0.9600 1.498 (3) 1.375 (3) 1.380 (4) 1.388 (4) 0.9300 1.358 (4). C19—C20 C19—H19A C20—H20A C21—C22 C21—H21A C22—C23 C22—H22A C23—C24 C23—H23A C24—C25 C24—H24A C25—H25A C26—C27 C26—H26A C27—C28 C27—H27A C28—C29 C28—H28A C29—C30 C29—H29A C30—H30A C31—C32 C31—H31A C32—C33 C32—H32A C33—C34 C33—H33A C34—C35 C34—H34A C35—H35A. 1.366 (5) 0.9300 0.9300 1.379 (4) 0.9300 1.345 (5) 0.9300 1.336 (6) 0.9300 1.372 (5) 0.9300 0.9300 1.366 (4) 0.9300 1.358 (5) 0.9300 1.366 (5) 0.9300 1.367 (4) 0.9300 0.9300 1.268 (7) 0.9300 1.307 (7) 0.9300 1.290 (7) 0.9300 1.273 (7) 0.9300 0.9300. O1—Ni1—N1 O1—Ni1—O2 N1—Ni1—O2 O1—Ni1—N6 N1—Ni1—N6 O2—Ni1—N6 O1—Ni1—N4 N1—Ni1—N4 O2—Ni1—N4 N6—Ni1—N4 O1—Ni1—N5 N1—Ni1—N5 O2—Ni1—N5 N6—Ni1—N5 N4—Ni1—N5 C1—O1—Ni1 C9—O2—Ni1. 90.39 (8) 170.49 (7) 80.17 (8) 93.93 (8) 175.66 (8) 95.52 (8) 91.37 (8) 92.04 (9) 87.80 (8) 88.26 (9) 92.16 (8) 93.79 (8) 89.68 (8) 85.65 (9) 173.16 (8) 127.13 (17) 108.45 (15). C12—C13—N3 C14—C13—N3 C13—C14—C15 C13—C14—H14A C15—C14—H14A C10—C15—C14 C10—C15—H15A C14—C15—H15A O4—N3—O3 O4—N3—C13 O3—N3—C13 N4—C16—C17 N4—C16—H16A C17—C16—H16A C18—C17—C16 C18—C17—H17A C16—C17—H17A. 118.8 (3) 119.0 (3) 119.0 (3) 120.5 120.5 120.4 (3) 119.8 119.8 122.7 (3) 118.9 (3) 118.4 (3) 124.2 (3) 117.9 117.9 119.4 (3) 120.3 120.3. Acta Cryst. (2004). E60, m912–m914. sup-5.

(10) supporting information C7—N1—N2 C7—N1—Ni1 N2—N1—Ni1 C9—N2—N1 C16—N4—C20 C16—N4—Ni1 C20—N4—Ni1 C21—N5—C25 C21—N5—Ni1 C25—N5—Ni1 C30—N6—C26 C30—N6—Ni1 C26—N6—Ni1 C35—N7—C31 O1—C1—C2 O1—C1—C6 C2—C1—C6 C3—C2—C1 C3—C2—H2B C1—C2—H2B C2—C3—C4 C2—C3—H3A C4—C3—H3A C5—C4—C3 C5—C4—Cl1 C3—C4—Cl1 C4—C5—C6 C4—C5—H5A C6—C5—H5A C5—C6—C1 C5—C6—C7 C1—C6—C7 N1—C7—C6 N1—C7—C8 C6—C7—C8 C7—C8—H8A C7—C8—H8B H8A—C8—H8B C7—C8—H8C H8A—C8—H8C H8B—C8—H8C O2—C9—N2 O2—C9—C10 N2—C9—C10 C11—C10—C15 C11—C10—C9 C15—C10—C9 C10—C11—C12. Acta Cryst. (2004). E60, m912–m914. 116.2 (2) 130.63 (19) 113.13 (15) 110.8 (2) 115.6 (3) 121.7 (2) 122.7 (2) 115.9 (3) 120.9 (2) 122.9 (2) 117.0 (3) 121.4 (2) 121.5 (2) 116.8 (6) 117.0 (3) 125.9 (2) 117.1 (2) 123.8 (3) 118.1 118.1 118.2 (3) 120.9 120.9 120.8 (3) 120.5 (3) 118.7 (2) 122.8 (3) 118.6 118.6 117.3 (2) 117.7 (2) 125.0 (2) 120.1 (2) 120.8 (2) 119.1 (2) 109.5 109.5 109.5 109.5 109.5 109.5 127.3 (2) 117.3 (2) 115.4 (2) 119.1 (2) 119.1 (2) 121.8 (2) 120.9 (3). C17—C18—C19 C17—C18—H18A C19—C18—H18A C18—C19—C20 C18—C19—H19A C20—C19—H19A N4—C20—C19 N4—C20—H20A C19—C20—H20A N5—C21—C22 N5—C21—H21A C22—C21—H21A C23—C22—C21 C23—C22—H22A C21—C22—H22A C24—C23—C22 C24—C23—H23A C22—C23—H23A C23—C24—C25 C23—C24—H24A C25—C24—H24A N5—C25—C24 N5—C25—H25A C24—C25—H25A N6—C26—C27 N6—C26—H26A C27—C26—H26A C28—C27—C26 C28—C27—H27A C26—C27—H27A C27—C28—C29 C27—C28—H28A C29—C28—H28A C28—C29—C30 C28—C29—H29A C30—C29—H29A N6—C30—C29 N6—C30—H30A C29—C30—H30A C32—C31—N7 C32—C31—H31A N7—C31—H31A C31—C32—C33 C31—C32—H32A C33—C32—H32A C34—C33—C32 C34—C33—H33A C32—C33—H33A. 118.0 (3) 121.0 121.0 119.3 (3) 120.4 120.4 123.6 (3) 118.2 118.2 123.8 (3) 118.1 118.1 119.1 (4) 120.4 120.4 117.8 (4) 121.1 121.1 120.3 (4) 119.9 119.9 123.0 (4) 118.5 118.5 123.3 (3) 118.4 118.4 118.9 (3) 120.6 120.6 118.8 (3) 120.6 120.6 118.8 (3) 120.6 120.6 123.2 (3) 118.4 118.4 119.1 (6) 120.4 120.4 120.9 (5) 119.6 119.6 122.5 (5) 118.8 118.8. sup-6.

(11) supporting information C10—C11—H11A C12—C11—H11A C13—C12—C11 C13—C12—H12A C11—C12—H12A C12—C13—C14. 119.5 119.5 118.5 (3) 120.8 120.8 122.2 (3). C35—C34—C33 C35—C34—H34A C33—C34—H34A C34—C35—N7 C34—C35—H35A N7—C35—H35A. 120.0 (6) 120.0 120.0 120.7 (6) 119.7 119.7. N1—Ni1—O1—C1 O2—Ni1—O1—C1 N6—Ni1—O1—C1 N4—Ni1—O1—C1 N5—Ni1—O1—C1 O1—Ni1—O2—C9 N1—Ni1—O2—C9 N6—Ni1—O2—C9 N4—Ni1—O2—C9 N5—Ni1—O2—C9 O1—Ni1—N1—C7 O2—Ni1—N1—C7 N6—Ni1—N1—C7 N4—Ni1—N1—C7 N5—Ni1—N1—C7 O1—Ni1—N1—N2 O2—Ni1—N1—N2 N6—Ni1—N1—N2 N4—Ni1—N1—N2 N5—Ni1—N1—N2 C7—N1—N2—C9 Ni1—N1—N2—C9 O1—Ni1—N4—C16 N1—Ni1—N4—C16 O2—Ni1—N4—C16 N6—Ni1—N4—C16 N5—Ni1—N4—C16 O1—Ni1—N4—C20 N1—Ni1—N4—C20 O2—Ni1—N4—C20 N6—Ni1—N4—C20 N5—Ni1—N4—C20 O1—Ni1—N5—C21 N1—Ni1—N5—C21 O2—Ni1—N5—C21 N6—Ni1—N5—C21 N4—Ni1—N5—C21 O1—Ni1—N5—C25 N1—Ni1—N5—C25 O2—Ni1—N5—C25 N6—Ni1—N5—C25. −8.7 (2) −15.9 (6) 170.8 (2) −100.8 (2) 85.1 (2) 4.4 (5) −2.93 (16) 177.57 (16) 89.53 (17) −96.83 (16) 3.0 (2) −178.2 (2) −171.7 (10) 94.3 (2) −89.2 (2) −176.06 (15) 2.73 (14) 9.3 (12) −84.68 (16) 91.75 (16) 178.8 (2) −2.0 (2) 6.9 (3) −83.5 (3) −163.6 (3) 100.8 (3) 128.0 (7) −172.9 (3) 96.7 (3) 16.6 (3) −79.0 (3) −51.8 (8) 165.8 (2) −103.7 (3) −23.6 (3) 72.0 (3) 44.7 (8) −7.8 (3) 82.8 (3) 162.9 (3) −101.6 (3). C2—C1—C6—C5 O1—C1—C6—C7 C2—C1—C6—C7 N2—N1—C7—C6 Ni1—N1—C7—C6 N2—N1—C7—C8 Ni1—N1—C7—C8 C5—C6—C7—N1 C1—C6—C7—N1 C5—C6—C7—C8 C1—C6—C7—C8 Ni1—O2—C9—N2 Ni1—O2—C9—C10 N1—N2—C9—O2 N1—N2—C9—C10 O2—C9—C10—C11 N2—C9—C10—C11 O2—C9—C10—C15 N2—C9—C10—C15 C15—C10—C11—C12 C9—C10—C11—C12 C10—C11—C12—C13 C11—C12—C13—C14 C11—C12—C13—N3 C12—C13—C14—C15 N3—C13—C14—C15 C11—C10—C15—C14 C9—C10—C15—C14 C13—C14—C15—C10 C12—C13—N3—O4 C14—C13—N3—O4 C12—C13—N3—O3 C14—C13—N3—O3 C20—N4—C16—C17 Ni1—N4—C16—C17 N4—C16—C17—C18 C16—C17—C18—C19 C17—C18—C19—C20 C16—N4—C20—C19 Ni1—N4—C20—C19 C18—C19—C20—N4. 0.9 (3) 0.8 (4) −179.4 (2) −177.6 (2) 3.4 (4) 2.5 (3) −176.48 (19) 172.9 (2) −6.8 (4) −7.2 (4) 173.1 (2) 3.1 (3) −177.29 (17) −0.8 (3) 179.53 (19) 8.8 (4) −171.6 (2) −170.7 (2) 9.0 (4) 0.9 (4) −178.6 (3) 0.3 (5) −0.8 (5) 178.0 (3) 0.2 (5) −178.6 (3) −1.5 (4) 178.0 (3) 1.0 (5) −171.1 (3) 7.7 (5) 7.8 (5) −173.4 (3) 0.2 (5) −179.6 (3) 0.6 (6) −0.7 (6) 0.0 (7) −0.9 (6) 178.9 (3) 0.8 (7). Acta Cryst. (2004). E60, m912–m914. sup-7.

(12) supporting information N4—Ni1—N5—C25 O1—Ni1—N6—C30 N1—Ni1—N6—C30 O2—Ni1—N6—C30 N4—Ni1—N6—C30 N5—Ni1—N6—C30 O1—Ni1—N6—C26 N1—Ni1—N6—C26 O2—Ni1—N6—C26 N4—Ni1—N6—C26 N5—Ni1—N6—C26 Ni1—O1—C1—C2 Ni1—O1—C1—C6 O1—C1—C2—C3 C6—C1—C2—C3 C1—C2—C3—C4 C2—C3—C4—C5 C2—C3—C4—Cl1 C3—C4—C5—C6 Cl1—C4—C5—C6 C4—C5—C6—C1 C4—C5—C6—C7 O1—C1—C6—C5. −128.8 (7) 173.3 (2) −12.1 (12) −5.5 (2) 82.1 (2) −94.8 (2) −9.4 (2) 165.2 (10) 171.7 (2) −100.7 (2) 82.5 (2) −171.49 (18) 8.3 (4) 179.0 (3) −0.9 (4) 0.1 (5) 0.6 (5) −179.3 (2) −0.5 (4) 179.4 (2) −0.2 (4) −180.0 (3) −178.9 (2). C25—N5—C21—C22 Ni1—N5—C21—C22 N5—C21—C22—C23 C21—C22—C23—C24 C22—C23—C24—C25 C21—N5—C25—C24 Ni1—N5—C25—C24 C23—C24—C25—N5 C30—N6—C26—C27 Ni1—N6—C26—C27 N6—C26—C27—C28 C26—C27—C28—C29 C27—C28—C29—C30 C26—N6—C30—C29 Ni1—N6—C30—C29 C28—C29—C30—N6 C35—N7—C31—C32 N7—C31—C32—C33 C31—C32—C33—C34 C32—C33—C34—C35 C33—C34—C35—N7 C31—N7—C35—C34. −0.3 (5) −174.3 (3) −0.5 (6) 1.3 (7) −1.3 (8) 0.3 (6) 174.2 (4) 0.5 (8) −0.2 (5) −177.6 (2) 0.6 (5) −1.1 (5) 1.2 (6) 0.4 (5) 177.7 (3) −0.9 (6) −0.5 (9) −1.4 (9) 2.2 (9) −1.0 (10) −1.0 (9) 1.7 (9). Hydrogen-bond geometry (Å, º) D—H···A. D—H. H···A. D···A. D—H···A. C8—H8A···N2 C11—H11A···O2 C16—H16A···O1 C18—H18A···N2i C20—H20A···O2 C21—H21A···O2 C25—H25A···O1 C26—H26A···O1 C30—H30A···O2. 0.96 0.93 0.93 0.93 0.93 0.93 0.93 0.93 0.93. 2.22 2.44 2.45 2.58 2.43 2.47 2.55 2.47 2.53. 2.691 (3) 2.762 (3) 3.043 (4) 3.500 (4) 2.994 (4) 3.044 (4) 3.098 (4) 3.053 (3) 3.118 (3). 109 100 121 169 119 120 118 121 122. Symmetry code: (i) x+1/2, −y+1/2, z−1/2.. Acta Cryst. (2004). E60, m912–m914. sup-8.

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