Two 2,5-bis(2-pyridinyl)-1,3,4-oxa­diazo­le-metal complexes (M = Cu and Ni)

The reaction of the diazine ligand 3,5-bis(2-pyridinyl)-1,3,4-oxa­diazole (pod, C₁₂H₈N₄O), with Cu(CF₃SO₃)₂ or Ni(ClO₄)₂ afforded the title complexes di­aqua­bis­[3,5-bis(2-pyridinyl)-1,3,4-oxa­diazole-N²,N³]copper(II) bis­(tri­fluoro­methane­sul­fon­ate), [Cu(pod)₂(H₂O)₂](CF₃SO₃)₂, and di­aqua­bis­[3,5-bis(2-pyridinyl)-1,3,4-oxa­diazo­le-N²,N³]­nickel(II) diperchlorate, [Ni(pod)₂(H₂O)₂](ClO₄)₂. Both complexes present a crystallographically centrosymmetric mononuclear cation structure which consists of a six-coordinated Cu^II or Ni^II ion with two pod mol­ecules acting as bidentate ligands and two axially coordinated water mol­ecules.

S1. Comment

Diazine bridging ligands of six- and five-membered rings provide binuclear complexes with a metal ion/diazine ligand ratio of 2:2 or 2:1, both bringing two metal centres into close proximity and thus providing an intramolecular pathway for spin-exchange interactions (Escuer et al., 1997; Mernari et al., 1993; Vreugdenhill et al., 1987; Ball & Blake, 1969, 1974). However, a metal ion/diazine ligand ratio of 1:2 has also been obtained (El Gueddi et al., 1996; Wignacourt et al., 1990). In our study of the structure and properties of new polyaza ligands (Mernari et al., 1998), we have investigated the reactions of a copper and nickel salt with the diazine ligand pod, i.e. 3,5-bis(2-pyridinyl)-1,3,4-oxadiazole, and obtained mononuclear complexes with a Cu^II or Ni^II/pod ratio of 1:2 in a trans coordination mode.

The structure consists of [M(pod)₂(H₂O)₂]²⁺ (M = Cu, Ni) centrosymmetric monomeric cations and discrete entities of the counter-ions [CF₃SO₃]⁻ or [ClO₄]⁻. The pod molecule plays the role of a bidentate ligand coordinated to the metal ion via an oxadiazole and a pyridine N atom. The equatorial coordination of the metal is completed by a second pod molecule related to the former by a symmetry centre which coincides with the metal-atom position. The octahedral coordination of the metal is achieved by two water molecules in axial positions. These structures reveal a trans coordination mode which is the same already found with the pod ligand (Wignacourt et al., 1990). In the equatorial plane, the formation of a chelate ring of five atoms produces relatively acute N1—Cu—N7 and N1—Ni—N7 angles of 81.12 (8) and 79.36 (3)°, respectively. The metal–pyridine-N bonds [2.0579 (5) Å for Cu and 2.1073 (7) Å for Ni] are longer than the metal–oxadiazole-N bonds [1.993 (2) Å for Cu and 2.0475 (7) Å for Ni]. These variations of bond lengths are approximately the same as in [Cu(pod)₂(H₂O)](ClO₄)₂ (Wignacourt et al., 1990) and in [Cu₂(C₄H₁₀N₆)₂(H₂O)₂](SO₄)·4H₂0 (Koningsbruggen et al., 1992). However, in [Cu(pod)₂Cl₂]·H₂O, the Cu–pyridine-N bond of 2.008 (2) Å is shorter than the Cu–oxadiazole-N bond of 2.484 (1) Å (Lagrenee et al., 1991). The axial bond lengths Cu—O19 [2.312 (2) Å], Ni—018 [2.088(3\)Å] and Ni—O19 [2.1122 (13) Å] are similar to those found in the complexes with diazine ligands (Keij et al., 1984; Rosenberg et al., 1986; Koningsbruggen et al., 1992). The metal ion is located essentially in the 5-pyridinyloxadiazole plane, at −0.025 (2) Å for Cu and at −0.022 (9) Å for Ni. In the case of the Cu complex, the 3-pyridinyl ring is almost coplanar with the 5-pyridinyloxadiazole plane [angle: 6.6 (5)°], but is at 24.0 (4)° in the case of the Ni complex. Despite the disordered structure of the counter-ions one can say that [ClO₄]⁻ or [CF₃SO₃]⁻ ions are probably linked to the water molecules via hydrogen bonds; however, a clear description can not be given. Thus, in the Cu complex, O19 is 2.793 (6) Å from O26, 2.805 (6) Å from O21 and 2.847 (7) Å from O22; in the Ni complex, where the water molecule is disordered and located on two sites, O18 and O19, we found O18 2.813 (6) Å, 2.823 (5) Å and 2.949 (5) Å from O27, O24 and O40, respectively, while O19 is 2.648 (7), 2.642 (8) and 2.716 (8) Å from the same atomic sites.

S2. Experimental

The pod ligand was prepared according to the literature methods (Sharma & Tandon, 1984). The metal complexes were obtained by addition of Cu(CF₃SO₃) or Ni(ClO₄) (2 mmol) to a methanolic solution of pod (4 mmol). After filtration of the undissolved reactants the filtrates were left at room temperature. After two weeks, blue crystals appeared and were filtered off and washed with water.

S3. Refinement

In both structures, the counter-ion is fully disordered. For the Cu compound, the O atoms of the perchlorate ion are located on 15 sites, with an occupancy ranging from 0.5 to 0.1. For the Ni compound, the O and F atoms of the trifluoromethanesulfonate are located on 8 and 9 positions, respectively, with an occupancy ranging from 0.52 to 0.18 for the fluoride sites and from 0.6 to 0.14 for the oxygen sites. Moreover, the water molecule linked to the copper ion occupies two positions, O18 and O19, with occupancies of 0.3 and O.7, respectively. In this case, the H atoms of the water molecule could not been found in the Fourier maps. Disordered atoms (O of the perchlorate; F and O of the trifluoromethanesulfonate) were refined isotropically. O atoms O18 and O19 of the disordered water molecule (Ni complex) were also refined isotropically

Computing details

Data collection: KappaCCD Software (Nonius, 1997) for (I); KappaCCD (Nonius, 1997) for (II). For both compounds, data reduction: DENZO and SCALEPAK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: maXus (Mackay et al., 1999). Molecular graphics: ORTEP (Johnson, 1976) for (II). For both compounds, software used to prepare material for publication: maXus(Mackay et al., 1999).

(I)

Crystal data

[Cu(C12H8N4O)2(H2O)2](CF3SO3)2	F(000) = 854
Mr = 846.15	Dx = 1.685 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.5897 (5) Å	Cell parameters from 12050 reflections
b = 10.0316 (4) Å	θ = 1.0–25.8°
c = 22.624 (1) Å	µ = 0.88 mm^−1
β = 147.261 (3)°	T = 298 K
V = 1668.0 (3) Å^3	Prism, colourless
Z = 2	0.20 × 0.15 × 0.10 mm

Data collection

KappaCCD diffractometer	Rint = 0.035
Radiation source: fine-focus sealed tube	θmax = 25.8°
ϕ scans	h = −14→16
3270 measured reflections	k = −12→0
3117 independent reflections	l = −27→14
2633 reflections with I > 3σ(I)

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom, diff
R[F^2 > 2σ(F^2)] = 0.065	H-atom parameters not refined
wR(F^2) = 0.074	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo^2) + 0.03Fo^2]
S = 1.50	(Δ/σ)max = 0.045
2633 reflections	Δρmax = 0.59 e Å^−3
270 parameters	Δρmin = −0.60 e Å^−3
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All standard uncertainties (except dihedral angles between l.s. planes) are estimated using the full covariance matrix. The standard uncertainties in cell dimensions are are used in calculating the standard uncertainties of bond distances, angles and torsion angles. Angles between l.s. planes have standard uncertainties calculated from atomic positional standard uncertainties; the errors in cell dimensions are not used in this case.

Refinement. Refinement on F².

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	1.0000 (3)	0.5000 (2)	0.50000 (16)	0.08456 (9)
O4	0.88392 (7)	0.26501 (5)	0.57921 (4)	0.0841 (3)
O19	0.69698 (8)	0.56133 (6)	0.34268 (5)	0.1149 (4)
N1	0.92817 (9)	0.34318 (6)	0.51247 (5)	0.0768 (4)
N2	0.86069 (9)	0.21457 (6)	0.47217 (5)	0.0898 (4)
N7	1.03524 (8)	0.58187 (6)	0.60042 (5)	0.0704 (4)
N13	0.74169 (11)	0.02811 (7)	0.54208 (6)	0.1321 (5)
C5	0.93850 (11)	0.36881 (7)	0.57385 (6)	0.0729 (4)
C3	0.83674 (11)	0.17214 (7)	0.51331 (6)	0.0780 (5)
C6	0.99967 (10)	0.49651 (8)	0.62737 (6)	0.0714 (5)
C8	1.09227 (12)	0.70333 (8)	0.64321 (7)	0.0944 (5)
C9	1.11811 (13)	0.74222 (9)	0.71454 (8)	0.1114 (6)
C10	1.08246 (14)	0.65414 (9)	0.74097 (8)	0.1243 (6)
C11	1.02302 (13)	0.52982 (8)	0.69742 (7)	0.1076 (5)
C12	0.76331 (11)	0.04330 (7)	0.49486 (7)	0.0784 (4)
C14	0.66667 (16)	−0.08712 (10)	0.52078 (9)	0.1560 (8)
C15	0.61301 (14)	−0.18473 (9)	0.45611 (9)	0.1281 (6)
C16	0.63885 (16)	−0.16700 (9)	0.41041 (9)	0.1445 (7)
C17	0.71696 (14)	−0.04974 (8)	0.43012 (8)	0.1212 (6)
H8	1.1217 (11)	0.7529 (8)	0.6280 (6)	0.0500 (7)*
H9	1.1613 (11)	0.8179 (8)	0.7442 (7)	0.0500 (7)*
H10	1.1198 (10)	0.6758 (7)	0.8026 (6)	0 (5)*
H11	0.9888 (11)	0.4706 (8)	0.7062 (6)	0.0500 (7)*
H14	0.6549 (11)	−0.0938 (7)	0.5550 (6)	0 (3)*
H15	0.5553 (3)	−0.2631 (2)	0.44249 (16)	0.0500 (7)*
H16	0.6065 (3)	−0.2373 (2)	0.36690 (16)	0.0500 (7)*
H17	0.732347	−0.036731	0.396240	0.050000*
H19A	0.6226 (3)	0.5319 (2)	0.33417 (16)	0.0500 (7)*
H19B	0.644975	0.631429	0.291909	0.050000*
S20	0.37858 (4)	0.38621 (3)	0.29278 (2)	0.11292 (17)
F32	0.3724 (2)	0.50027 (16)	0.39320 (12)	0.0784 (4)*	0.44
F39	0.5129 (3)	0.29317 (18)	0.45801 (16)	0.0754 (6)*	0.41
O21	0.5490 (3)	0.4675 (2)	0.37437 (16)	0.0655 (5)*	0.41
O24	0.2115 (2)	0.45422 (17)	0.19804 (12)	0.0625 (4)*	0.60
C30	0.38942 (16)	0.36836 (12)	0.37608 (10)	0.1293 (8)
F31	0.5072 (6)	0.5073 (4)	0.4360 (3)	0.1422 (11)*	0.24
F33	0.2989 (2)	0.43978 (19)	0.36146 (13)	0.0798 (4)*	0.44
F34	0.2520 (3)	0.3407 (2)	0.33626 (15)	0.0940 (5)*	0.41
F35	0.2481 (3)	0.2661 (2)	0.31740 (14)	0.0786 (5)*	0.36
F50	0.5468 (2)	0.33319 (15)	0.47854 (12)	0.0740 (5)*	0.52
O22	0.4969 (4)	0.5165 (3)	0.3475 (2)	0.0763 (9)*	0.27
O23	0.2763 (8)	0.5090 (6)	0.2261 (5)	0.0922 (17)*	0.14
O25	0.2063 (5)	0.4013 (3)	0.1878 (3)	0.0791 (11)*	0.25
O26	0.5352 (3)	0.3929 (3)	0.3441 (2)	0.0677 (6)*	0.29
O27	0.4690 (5)	0.3028 (4)	0.3000 (3)	0.0766 (9)*	0.24
O28	0.4158 (4)	0.2589 (2)	0.29189 (19)	0.0917 (6)*	0.42
O29	0.3251 (4)	0.2289 (3)	0.2642 (2)	0.1055 (8)*	0.35
F36	0.3161 (6)	0.2120 (4)	0.3286 (3)	0.1097 (13)*	0.18

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.05604 (9)	0.03569 (7)	0.04817 (8)	−0.00915 (7)	0.04809 (8)	−0.00507 (7)
O4	0.0547 (4)	0.0366 (3)	0.0471 (3)	−0.0074 (2)	0.0461 (3)	−0.0020 (2)
O19	0.0585 (4)	0.0716 (4)	0.0663 (4)	0.0057 (3)	0.0534 (4)	0.0178 (3)
N1	0.0472 (4)	0.0374 (4)	0.0428 (4)	−0.0066 (3)	0.0400 (4)	−0.0042 (3)
N2	0.0573 (5)	0.0389 (4)	0.0508 (4)	−0.0049 (3)	0.0484 (4)	−0.0009 (3)
N7	0.0419 (4)	0.0343 (3)	0.0405 (4)	−0.0055 (3)	0.0365 (4)	−0.0043 (3)
N13	0.0909 (6)	0.0428 (5)	0.0781 (5)	−0.0145 (4)	0.0780 (6)	−0.0069 (4)
C5	0.0442 (5)	0.0377 (4)	0.0402 (5)	−0.0035 (3)	0.0374 (5)	0.0013 (3)
C3	0.0492 (5)	0.0365 (4)	0.0428 (5)	−0.0028 (4)	0.0408 (5)	0.0002 (4)
C6	0.0426 (5)	0.0391 (4)	0.0394 (4)	−0.0048 (4)	0.0366 (4)	−0.0020 (4)
C8	0.0586 (6)	0.0453 (5)	0.0528 (5)	−0.0083 (4)	0.0497 (5)	−0.0047 (4)
C9	0.0721 (7)	0.0436 (5)	0.0629 (6)	−0.0144 (5)	0.0594 (6)	−0.0166 (5)
C10	0.0845 (7)	0.0562 (6)	0.0669 (6)	−0.0112 (5)	0.0699 (7)	−0.0109 (5)
C11	0.0713 (6)	0.0476 (6)	0.0599 (6)	−0.0061 (4)	0.0603 (6)	−0.0027 (4)
C12	0.0474 (5)	0.0331 (4)	0.0447 (5)	−0.0023 (3)	0.0392 (5)	0.0031 (3)
C14	0.1010 (9)	0.0571 (6)	0.0951 (9)	−0.0167 (6)	0.0902 (9)	−0.0044 (6)
C15	0.0733 (8)	0.0455 (6)	0.0786 (7)	−0.0179 (5)	0.0628 (7)	−0.0053 (5)
C16	0.0938 (9)	0.0475 (6)	0.0810 (8)	−0.0183 (5)	0.0736 (8)	−0.0217 (5)
C17	0.0813 (7)	0.0470 (5)	0.0670 (6)	−0.0087 (5)	0.0663 (7)	−0.0077 (4)
S20	0.05818 (18)	0.0833 (2)	0.06017 (17)	0.00497 (14)	0.05187 (17)	−0.00015 (14)
C30	0.0577 (8)	0.0894 (9)	0.0721 (8)	0.0134 (6)	0.0505 (8)	0.0163 (7)

Geometric parameters (Å, º)

Cu1—O19	2.3125 (6)	N13—C14	1.3347 (13)
Cu1—N7	2.0579 (5)	C5—C6	1.4509 (11)
Cu1—N1	1.9926 (5)	C3—C12	1.4629 (10)
O4—C5	1.3418 (9)	C6—C11	1.3704 (11)
O4—C3	1.3762 (9)	C8—C9	1.3880 (13)
N1—N2	1.3894 (9)	C9—C10	1.3640 (13)
N1—C5	1.2986 (10)	C10—C11	1.3564 (12)
N2—C3	1.2895 (10)	C12—C17	1.3642 (12)
N7—C6	1.3545 (10)	C14—C15	1.3552 (15)
N7—C8	1.3268 (10)	C15—C16	1.355 (2)
N13—C12	1.3338 (11)	C16—C17	1.3830 (13)
O19—Cu1—N1	88.72 (2)	N7—C6—C5	110.69 (6)
O19—Cu1—N7	93.01 (2)	N7—C6—C11	122.91 (7)
N1—Cu1—N7	81.12 (3)	C5—C6—C11	126.39 (7)
C5—O4—C3	102.52 (6)	N7—C8—C9	121.86 (8)
N2—N1—C5	107.66 (6)	C8—C9—C10	119.46 (8)
N1—N2—C3	105.13 (6)	C9—C10—C11	119.43 (9)
C6—N7—C8	117.56 (7)	C6—C11—C10	118.78 (8)
C12—N13—C14	115.20 (8)	N13—C12—C3	115.43 (7)
O4—C5—N1	111.86 (6)	N13—C12—C17	124.60 (7)
O4—C5—C6	125.59 (7)	C3—C12—C17	119.93 (8)
N1—C5—C6	122.55 (7)	N13—C14—C15	124.71 (10)
O4—C3—N2	112.83 (6)	C14—C15—C16	118.67 (9)
O4—C3—C12	119.45 (7)	C15—C16—C17	119.14 (9)
N2—C3—C12	127.70 (7)	C12—C17—C16	117.66 (9)

(II)

Crystal data

[Ni(C12H8N4O)2(H2O)2](ClO4)2	F(000) = 756
Mr = 742.09	Dx = 1.63 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.6569 (9) Å	Cell parameters from 8346 reflections
b = 10.9630 (7) Å	θ = 1.0–26.0°
c = 18.921 (1) Å	µ = 0.89 mm^−1
β = 147.752 (3)°	T = 298 K
V = 1511.6 (3) Å^3	Prism, colourless
Z = 2	0.20 × 0.15 × 0.10 mm

Data collection

KappaCCD diffractometer	Rint = 0.055
Radiation source: fine-focus sealed tube	θmax = 26.0°
ϕ scans	h = −16→17
3008 measured reflections	k = −13→0
2851 independent reflections	l = −23→16
2576 reflections with I > 3σ(I)

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.086	H-atom parameters not refined
wR(F^2) = 0.073	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo^2) + 0.03Fo^2]
S = 2.27	(Δ/σ)max = 0.045
2576 reflections	Δρmax = 0.63 e Å^−3
236 parameters	Δρmin = −0.46 e Å^−3
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All standard uncertainties (except dihedral angles between l.s. planes) are estimated using the full covariance matrix. The standard uncertainties in cell dimensions are are used in calculating the standard uncertainties of bond distances, angles and torsion angles. Angles between l.s. planes have standard uncertainties calculated from atomic positional standard uncertainties; the errors in cell dimensions are not used in this case.

Refinement. Refinement on F².

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	1.0000 (12)	0.0000 (7)	0.5000 (9)	0.05908 (10)
O4	0.80944 (8)	0.31370 (5)	0.29582 (6)	0.0660 (4)
O19	0.72808 (19)	−0.04771 (12)	0.36100 (14)	0.0464 (5)*	0.70
N7	0.99810 (10)	0.15823 (6)	0.56207 (7)	0.0593 (4)
N1	0.89218 (10)	0.12400 (7)	0.36473 (8)	0.0673 (4)
N2	0.82664 (11)	0.13095 (7)	0.25552 (8)	0.0724 (5)
N13	0.71494 (13)	0.41901 (8)	0.11014 (9)	0.1112 (6)
C8	1.05543 (13)	0.17044 (9)	0.66311 (10)	0.0814 (6)
C3	0.77954 (12)	0.24357 (8)	0.21840 (9)	0.0604 (5)
C12	0.69564 (13)	0.29941 (9)	0.10496 (9)	0.0671 (6)
C5	0.87808 (12)	0.23213 (8)	0.38333 (9)	0.0569 (5)
C10	0.98463 (16)	0.38263 (9)	0.62044 (12)	0.1118 (7)
C6	0.93273 (12)	0.25918 (8)	0.48921 (9)	0.0648 (5)
C11	0.92233 (14)	0.37183 (8)	0.51420 (11)	0.0949 (6)
C16	0.52173 (18)	0.28653 (13)	−0.10519 (12)	0.1262 (9)
C9	1.05094 (15)	0.28269 (10)	0.69534 (11)	0.0993 (7)
C15	0.53784 (17)	0.40908 (13)	−0.10198 (12)	0.1146 (9)
C14	0.63497 (18)	0.47095 (10)	0.00582 (13)	0.1339 (8)
C17	0.6018 (12)	0.2285 (7)	0.0005 (9)	0.1138 (7)
Cl20	0.34489 (4)	0.16979 (2)	0.07457 (3)	0.07809 (15)
O24	0.5007 (6)	0.1094 (5)	0.1627 (5)	0.1346 (17)*	0.30
O29	0.2675 (4)	0.1371 (3)	0.0991 (3)	0.0460 (9)*	0.30
O27	0.4042 (3)	0.0495 (2)	0.1340 (3)	0.0508 (7)*	0.30
O22	0.4046 (10)	0.1429 (6)	0.0374 (7)	0.114 (2)*	0.20
O21	0.2771 (10)	0.1419 (5)	−0.0400 (6)	0.0815 (16)*	0.20
H8	1.1013 (9)	0.0995 (6)	0.7150 (7)	0.050000*
H10	0.9796 (9)	0.4604 (6)	0.6406 (7)	0.050000*
H11	0.8735 (9)	0.4392 (6)	0.4580 (7)	0.050000*
H16	0.4560 (9)	0.2396 (6)	−0.1799 (7)	0.050000*
H9	1.0946 (9)	0.2908 (6)	0.7696 (7)	0.050000*
H15	0.4796 (9)	0.4516 (6)	−0.1758 (7)	0.050000*
H14	0.6502 (9)	0.5576 (6)	0.0104 (7)	0.050000*
H17	0.5935 (12)	0.1557 (8)	0.0007 (9)	0.050000*
O18	0.7453 (4)	−0.0379 (2)	0.3901 (3)	0.0280 (8)*	0.30
O36	0.1857 (5)	0.1623 (3)	−0.0713 (3)	0.0628 (9)*	0.30
O38	0.4758 (3)	0.26310 (17)	0.1794 (2)	0.0694 (5)*	0.50
O37	0.1709 (6)	0.1927 (4)	−0.0190 (5)	0.0666 (11)*	0.20
O39	0.3991 (4)	0.2948 (3)	0.1129 (3)	0.0740 (10)*	0.30
O41	0.3529 (10)	0.2076 (7)	0.0042 (7)	0.0350 (17)*	0.10
O40	0.4369 (3)	0.0568 (2)	0.1172 (2)	0.0577 (6)*	0.40
O42	0.2126 (7)	0.2200 (4)	−0.0456 (5)	0.1096 (15)*	0.30
O43	0.2109 (7)	0.1413 (5)	0.0462 (5)	0.0424 (12)*	0.20
O44	0.2319 (6)	0.1933 (4)	0.0691 (5)	0.0461 (11)*	0.20
O45	0.4758 (6)	0.2531 (4)	0.1371 (5)	0.0641 (13)*	0.20

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.03588 (9)	0.02510 (9)	0.03094 (10)	0.00563 (9)	0.02779 (9)	0.00546 (9)
O4	0.0392 (4)	0.0309 (3)	0.0353 (4)	0.0074 (3)	0.0319 (4)	0.0088 (3)
N7	0.0353 (4)	0.0312 (4)	0.0300 (5)	0.0033 (4)	0.0279 (4)	0.0036 (3)
N1	0.0405 (5)	0.0327 (4)	0.0355 (5)	0.0057 (4)	0.0329 (4)	0.0053 (4)
N2	0.0452 (5)	0.0387 (5)	0.0348 (5)	0.0040 (4)	0.0345 (5)	0.0037 (4)
N13	0.0774 (7)	0.0456 (6)	0.0519 (6)	0.0084 (5)	0.0559 (6)	0.0119 (4)
C8	0.0506 (6)	0.0383 (6)	0.0415 (6)	0.0022 (5)	0.0395 (6)	0.0029 (5)
C3	0.0335 (5)	0.0382 (6)	0.0298 (6)	−0.0016 (4)	0.0267 (5)	−0.0012 (4)
C12	0.0364 (6)	0.0457 (6)	0.0333 (6)	0.0052 (5)	0.0300 (5)	0.0076 (5)
C5	0.0322 (5)	0.0255 (5)	0.0317 (5)	0.0039 (4)	0.0267 (5)	0.0058 (4)
C10	0.0730 (8)	0.0361 (6)	0.0634 (8)	0.0002 (6)	0.0606 (7)	−0.0056 (5)
C6	0.0360 (5)	0.0281 (5)	0.0391 (6)	0.0017 (4)	0.0328 (5)	0.0015 (4)
C11	0.0587 (7)	0.0306 (5)	0.0571 (7)	0.0093 (5)	0.0513 (7)	0.0069 (5)
C16	0.0809 (9)	0.0971 (11)	0.0446 (8)	−0.0204 (8)	0.0536 (8)	−0.0147 (7)
C9	0.0639 (7)	0.0551 (7)	0.0466 (7)	−0.0038 (6)	0.0490 (7)	−0.0087 (6)
C15	0.0655 (8)	0.0897 (10)	0.0482 (8)	0.0084 (7)	0.0490 (8)	0.0230 (7)
C14	0.0929 (9)	0.0504 (8)	0.0649 (9)	0.0080 (6)	0.0683 (9)	0.0147 (6)
C17	0.071 (3)	0.0548 (7)	0.0557 (7)	−0.0105 (7)	0.0533 (4)	0.0005 (7)
Cl20	0.04044 (15)	0.04215 (15)	0.04118 (16)	0.00797 (13)	0.03183 (14)	0.01087 (12)

Geometric parameters (Å, º)

Ni1—O18	2.088 (2)	N13—C14	1.3292 (13)
Ni1—O19	2.1122 (13)	C8—C9	1.3975 (13)
Ni1—N7	2.1073 (7)	C3—C12	1.4611 (12)
Ni1—N1	2.0475 (7)	C12—C17	1.3665 (10)
O4—C3	1.3755 (10)	C5—C6	1.4591 (12)
O4—C5	1.3396 (10)	C10—C11	1.3732 (14)
N7—C8	1.3244 (11)	C10—C9	1.3631 (14)
N7—C6	1.3567 (10)	C6—C11	1.3721 (12)
N1—N2	1.3958 (10)	C16—C15	1.354 (2)
N1—C5	1.2965 (10)	C16—C17	1.3795 (13)
N2—C3	1.2912 (11)	C15—C14	1.343 (2)
N13—C12	1.3246 (12)
O18—Ni1—N1	93.21 (8)	N13—C12—C17	123.71 (8)
O18—Ni1—N7	85.60 (7)	C3—C12—C17	119.78 (8)
O19—Ni1—N1	87.69 (4)	O4—C5—N1	112.58 (8)
O19—Ni1—N7	93.46 (4)	O4—C5—C6	124.89 (8)
N7—Ni1—N1	79.36 (3)	N1—C5—C6	122.52 (8)
C3—O4—C5	102.15 (7)	C11—C10—C9	119.80 (9)
C8—N7—C6	117.52 (8)	N7—C6—C5	111.24 (7)
N2—N1—C5	107.19 (7)	N7—C6—C11	123.70 (9)
N1—N2—C3	104.96 (7)	C5—C6—C11	125.05 (8)
C12—N13—C14	116.87 (10)	C10—C11—C6	117.75 (9)
N7—C8—C9	121.89 (9)	C15—C16—C17	119.56 (10)
O4—C3—N2	113.11 (8)	C8—C9—C10	119.34 (9)
O4—C3—C12	119.21 (8)	C16—C15—C14	118.91 (10)
N2—C3—C12	127.64 (9)	N13—C14—C15	123.69 (10)
N13—C12—C3	116.50 (9)	C12—C17—C16	117.25 (7)