A square-planar Ni^II complex with an asymmetric coordination of a novel polynucleative 2,6-diacetyl­pyridine bis­{[2-(hydroxy­imino)propanoyl]hydrazone} ligand

The title compound, (2,6-diacetyl­pyridine bis­{[2-(hydroxy­imino)­propanoyl]­hydrazone}(2-))nickel(II) dimethyl sulfox­ide solvate monohydrate, [Ni(C₁₅H₁₇N₇O₄)]·C₂H₆OS·H₂O, represents the first example of square-planar N₄ coordination via N atoms with four different functions, namely amide, azomethine, hydroxyimino and pyridine. The coordination poly­hedron of the central Ni atom has a slightly distorted square-planar geometry. The 2,6-diacetyl­pyridine bis­{[2-(hy­droxy­imino)­propanoyl]­hydrazone} ligand forms one six- and two five-membered chelate rings, and a pseudo-chelate ring through an intra­molecular hydrogen bond with an amide group as donor and a deprotonated hydroxyimino group as acceptor, resulting in a pseudomacrocyclic arrangement.

S1. Comment

2,6-Diacetylpyridine acylhydrazones and bis(acylhydrazones) are an interesting class of compounds due to their ability to form stable metal complexes, their versatility as chelating agents and their flexibility in assuming different conformations (Wester & Palenik, 1974; Carcelli et al., 1999; Kasuga et al., 2003). Complexes of this type of ligand with 3 d metals reveal biological activity and can be used in bioinorganic modelling of active sites of redox and hydrolytic enzymes. To date, more than 65 complexes based on 2,6-diacetylpyridine derivatives of different compositions have been characterized by X-ray crystallographic analysis. In almost all cases the ligands are five-coordinated via pyridine, two azomethine N atoms and two O or S atoms (Pelizzi et al., 1986). The title compound, [Ni(C₁₅H₁₇N₇O₄]·DMSO·H₂O, (I) (DMSO is dimethyl sulfoxide), is a complex of Ni^II with a novel polynucleative derivative of 2,6-diacetylpyridine, namely 2,6-diacetylpyridine bis(2-(hydroxymino)propanehydrazide), L. The presence of three powerful chelate centres in the ligand may be used for obtaining polynuclear metal complexes (see the second scheme).

The structure of (I) consists of the neutral asymmetric complex and solvent DMSO and water molecules (Fig. 1). Thus ligand L is doubly deprotonated at the amide (N3) and oximic (O2) groups, which was confirmed by ¹H NMR data. Compound (I) represents the first example of square-planar N₄ coordination via N atoms of different functions, namely amide (N3), azomethine (N5), oximic (N4) and pyridine (N1). A structure reported by Simonov et al. (1993) contains the NiN₄ chromophore with four chemically different N atoms but the groups are the same: oximic and hydrazone.

The Ni—N coordination bond lengths (Table 1) fall in the range 1.828 (3)–1.888 (3) Å and are typical for square-planar Ni^II complexes with deprotonated amide ligands (Leininger et al., 2000; Leovac et al., 2000; Hlavica & Lewis, 2001; Moroz et al., 2006). The azomethine double-bond distances N2═C6 and N5═C11 [1.295 (5) and 1.301 (4) Å, respectively] are about the same. On the other hand, the N2—N3 [1.355 (4) Å] and N4—O2 [1.320 (4) Å] bonds are shorter than the N5—N6 [1.394 (4) Å] and N7—O4 [1.392 (4) Å] bonds. The differences can be explained by the deprotonation of atoms N3 and O2. As a result of the formation of five- and six-membered chelate rings, the bite angles around Ni1 deviate from ideal square-planar values (Table 1). The chelate rings are essentially planar. A pseudochelate ring is formed via the presence of an intramolecular hydrogen bond with amide atom N6 as donor and the deprotonated oximic group (O2) as acceptor (Table 2), resulting in a pseudomacrocyclic arrangement. The non-coordinated part of L is not planar, because of the tendency to reduce repulsion between CO and CH₃ groups and also because of the presence of an intermolecular hydrogen bond with oximic group O4 as donor and DMSO as acceptor. The C11—N5—N6—C13 torsion angle is 60.5 (4)°.

The elements of the structure are connected through a system of hydrogen bonds and π–π stacking interactions. The solvent water molecules and protonated oximic groups (O4) act as donors, and amide (O3) and DMSO O atoms act as acceptors (Table 2). An extensive three-dimensional system of hydrogen bonds is formed (Fig. 2). The π–π stacking (3.45 Å) is realised between neighbouring molecules of the complex along the crystallographic a direction. Slabs of (I) form columns, with DMSO and water molecules between them.

Related literature

For related literature, see: Carcelli et al. (1999); Fritsky et al. (1998); Hlavica & Lewis (2001); Kasuga et al. (2003); Leininger et al. (2000); Leovac et al. (2000); Moroz et al. (2006); Pelizzi et al. (1986); Simonov et al. (1993); Wester & Palenik (1974).

S2. Experimental

The synthesis of the ligand was carried out as follows. To 2-(hydroxymino)propanehydrazide (5 g, 0.043 mol) (Fritsky et al., 1998) dissolved in EtOH (20 ml), 2,6-diacetylpyridine (3.4 g, 0.021 mol) was added. The resulting mixture was heated for 1 h. After cooling, a white precipitate was formed. The precipitate was separated by filtration and recrystallized from dimethylformamide (yield 6.95 g, 91%). Spectroscopic analysis: ¹H NMR (Solvent? Frequency?, δ, p.p.m.): 1.986 (6H, s, CH₃), 2.432 (6H, s, CH₃), 7.929 (1H, t, pyH), 8.086 (2H, d, pyH), 10.27 (2H, s, NH), 12.148 (2H, s, OH).

To prepare crystals of (I), NiCl₂ 6H₂O (0,0291 g, 0,1 mmol) and L (0.0361 g, 0.1 mmol) were dissolved in DMSO (20 ml) and aqueous NaOH (1 ml, 0.1 mmol) was added. The mixture was heated for 40 min, filtered and left in a desiccator for crystallization. After one week, red crystals of (I) suitable for X-ray analysis were obtained (yield 0.0544 g, 45%). Spectroscopic analysis: ¹H NMR (Solvent? Frequency?, δ, p.p.m.): 1.792 (3H, s, CH₃), 1.979 (3H, s, CH₃), 2.28 (3H, s, CH₃), 2.518 (3H, s, CH₃), 8.1 (1H, d, pyH), 8.171 (1H, d, pyH), 8.375 (1H, t, pyH), 12.332 (1H, s, NH), 15.485 (1H, s, OH).

S3. Refinement

OH and NH H atoms were located in a difference Fourier map but constrained to ride on their parent atoms, with U_iso(H) = 1.5U_eq(parent atom). Other H atoms were positioned geometrically and constrained to ride on their parent atoms, with C—H = 0.95–0.98 Å, and U_iso(H) = 1.2–1.5U_eq(parent atom). The highest peak is located 1.10 Å from atom H16B and the deepest hole is located 0.61 Å from atom S1.

Computing details

Data collection: COLLECT (Bruker, 2004); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. Compound (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are indicated by dashed lines.
	Fig. 2. A packing diagram for complex (I), projected along the a direction. Hydrogen bonds are indicated by dashed lines. H atoms have been omitted for clarity.

(2,6-Diacetylpyridine bis{[2-(hydroxyimino)propanoyl]hydrazone}(2-)]nickel(II) dimethyl sulfoxide solvate monohydrate

Crystal data

[Ni(C15H17N7O4)]·C2H6OS·H2O	Z = 2
Mr = 514.21	F(000) = 536
Triclinic, P1	Dx = 1.614 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3076 (2) Å	Cell parameters from 13132 reflections
b = 11.1899 (5) Å	θ = 1.0–26.0°
c = 13.9875 (6) Å	µ = 1.07 mm^−1
α = 74.652 (2)°	T = 120 K
β = 84.472 (2)°	Needle, red
γ = 73.641 (2)°	0.19 × 0.05 × 0.03 mm
V = 1058.04 (7) Å^3

Data collection

Nonius KappaCCD diffractometer	4128 independent reflections
Radiation source: fine-focus sealed tube	3008 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.092
Detector resolution: 9 pixels mm^-1	θmax = 26.1°, θmin = 3.8°
ϕ scans and ω scans with κ offset	h = −8→9
Absorption correction: multi-scan [SADABS (Version 2.10; Sheldrick, 2003)]	k = −12→13
Tmin = 0.822, Tmax = 0.965	l = −17→17
18361 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0292P)^2 + 1.8037P] where P = (Fo^2 + 2Fc^2)/3
4128 reflections	(Δ/σ)max = 0.005
296 parameters	Δρmax = 0.49 e Å^−3
0 restraints	Δρmin = −0.43 e Å^−3

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
Ni1	0.19844 (7)	0.05511 (5)	0.41026 (3)	0.01806 (15)
O1	0.2455 (4)	0.3306 (3)	0.52378 (19)	0.0284 (6)
O2	0.0736 (4)	0.2587 (2)	0.23917 (18)	0.0259 (6)
O3	0.3419 (4)	−0.1075 (2)	0.15473 (19)	0.0235 (6)
O4	−0.0134 (4)	0.2508 (3)	−0.05788 (18)	0.0275 (6)
H4O	−0.0838	0.3353	−0.0556	0.041*
O5	−0.2621 (4)	0.4760 (3)	−0.0573 (2)	0.0293 (6)
O6	0.6060 (4)	−0.3151 (3)	0.2933 (2)	0.0366 (7)
H6O	0.5318	−0.2405	0.2576	0.055*
H6P	0.6476	−0.2902	0.3426	0.055*
N1	0.2541 (4)	−0.1106 (3)	0.4948 (2)	0.0185 (7)
N2	0.3044 (4)	0.0765 (3)	0.5981 (2)	0.0214 (7)
N3	0.2456 (4)	0.1297 (3)	0.5035 (2)	0.0199 (7)
N4	0.1358 (4)	0.2244 (3)	0.3306 (2)	0.0196 (7)
N5	0.1554 (4)	−0.0295 (3)	0.3178 (2)	0.0176 (6)
N6	0.1019 (4)	0.0331 (3)	0.2204 (2)	0.0190 (7)
H6N	0.0736	0.1163	0.2178	0.029*
N7	0.0255 (4)	0.1808 (3)	0.0396 (2)	0.0226 (7)
C1	0.2302 (5)	−0.2016 (3)	0.4529 (3)	0.0197 (8)
C2	0.2695 (5)	−0.3313 (4)	0.5038 (3)	0.0230 (8)
H2	0.2531	−0.3938	0.4731	0.028*
C3	0.3327 (5)	−0.3665 (4)	0.5998 (3)	0.0274 (9)
H3	0.3619	−0.4541	0.6358	0.033*
C4	0.3533 (5)	−0.2741 (4)	0.6433 (3)	0.0248 (9)
H4	0.3948	−0.2981	0.7097	0.030*
C5	0.3130 (5)	−0.1437 (4)	0.5895 (3)	0.0199 (8)
C6	0.3345 (5)	−0.0458 (4)	0.6367 (3)	0.0222 (8)
C7	0.3969 (6)	−0.0885 (4)	0.7429 (3)	0.0272 (9)
H7A	0.4146	−0.0151	0.7631	0.041*
H7B	0.5175	−0.1560	0.7489	0.041*
H7C	0.2991	−0.1220	0.7858	0.041*
C8	0.2201 (5)	0.2617 (3)	0.4733 (3)	0.0204 (8)
C9	0.1593 (5)	0.3121 (3)	0.3700 (3)	0.0211 (8)
C10	0.1250 (6)	0.4510 (4)	0.3181 (3)	0.0301 (9)
H10A	0.1623	0.4594	0.2479	0.045*
H10B	0.2009	0.4901	0.3484	0.045*
H10C	−0.0106	0.4946	0.3238	0.045*
C11	0.1635 (5)	−0.1510 (3)	0.3504 (3)	0.0174 (7)
C12	0.1019 (5)	−0.2308 (4)	0.2976 (3)	0.0233 (8)
H12A	0.0222	−0.1749	0.2420	0.035*
H12B	0.0284	−0.2836	0.3434	0.035*
H12C	0.2143	−0.2867	0.2726	0.035*
C13	0.2103 (5)	−0.0090 (3)	0.1444 (3)	0.0194 (8)
C14	0.1550 (5)	0.0747 (3)	0.0426 (3)	0.0193 (8)
C15	0.2522 (6)	0.0303 (4)	−0.0450 (3)	0.0255 (9)
H15A	0.1596	0.0520	−0.0973	0.038*
H15B	0.3069	−0.0631	−0.0258	0.038*
H15C	0.3541	0.0726	−0.0696	0.038*
S1	−0.22590 (14)	0.56401 (9)	−0.00002 (7)	0.0261 (2)
C16	−0.4258 (6)	0.7008 (4)	−0.0204 (3)	0.0320 (10)
H16A	−0.4213	0.7518	−0.0889	0.048*
H16B	−0.4230	0.7534	0.0252	0.048*
H16C	−0.5435	0.6730	−0.0087	0.048*
C17	−0.2786 (7)	0.4974 (4)	0.1268 (3)	0.0354 (10)
H17A	−0.4066	0.4842	0.1328	0.053*
H17B	−0.2733	0.5566	0.1664	0.053*
H17C	−0.1848	0.4148	0.1509	0.053*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0214 (3)	0.0156 (3)	0.0164 (2)	−0.00344 (18)	−0.00120 (18)	−0.00391 (18)
O1	0.0375 (16)	0.0242 (15)	0.0271 (15)	−0.0083 (12)	−0.0018 (12)	−0.0120 (12)
O2	0.0396 (16)	0.0165 (14)	0.0199 (14)	−0.0031 (12)	−0.0102 (12)	−0.0033 (11)
O3	0.0235 (14)	0.0202 (14)	0.0241 (14)	−0.0020 (11)	0.0001 (11)	−0.0055 (11)
O4	0.0368 (16)	0.0221 (14)	0.0184 (14)	−0.0002 (12)	−0.0050 (11)	−0.0028 (11)
O6	0.0450 (18)	0.0263 (16)	0.0358 (17)	0.0020 (13)	−0.0152 (14)	−0.0106 (13)
N1	0.0191 (16)	0.0194 (16)	0.0169 (16)	−0.0052 (13)	0.0016 (12)	−0.0051 (13)
N2	0.0208 (16)	0.0296 (19)	0.0139 (16)	−0.0057 (14)	−0.0014 (12)	−0.0062 (14)
N3	0.0217 (16)	0.0181 (16)	0.0204 (16)	−0.0061 (13)	0.0005 (13)	−0.0049 (13)
N4	0.0226 (16)	0.0189 (16)	0.0176 (16)	−0.0051 (13)	0.0015 (13)	−0.0062 (13)
N5	0.0153 (15)	0.0170 (16)	0.0184 (16)	−0.0020 (12)	−0.0008 (12)	−0.0033 (13)
N6	0.0234 (16)	0.0135 (15)	0.0174 (16)	−0.0010 (12)	−0.0024 (13)	−0.0025 (12)
N7	0.0268 (17)	0.0224 (17)	0.0179 (16)	−0.0074 (14)	−0.0030 (13)	−0.0018 (13)
C1	0.0161 (18)	0.0163 (19)	0.026 (2)	−0.0036 (15)	0.0046 (15)	−0.0068 (16)
C2	0.025 (2)	0.020 (2)	0.024 (2)	−0.0075 (16)	0.0052 (16)	−0.0045 (16)
C3	0.027 (2)	0.019 (2)	0.028 (2)	−0.0030 (16)	0.0001 (17)	0.0044 (17)
C4	0.024 (2)	0.025 (2)	0.020 (2)	−0.0053 (16)	0.0012 (16)	0.0007 (16)
C5	0.0164 (18)	0.022 (2)	0.0176 (19)	−0.0027 (15)	0.0035 (14)	−0.0027 (15)
C6	0.0198 (19)	0.025 (2)	0.0204 (19)	−0.0032 (16)	0.0019 (15)	−0.0061 (16)
C7	0.023 (2)	0.035 (2)	0.020 (2)	−0.0023 (17)	−0.0010 (16)	−0.0071 (17)
C8	0.0178 (19)	0.019 (2)	0.027 (2)	−0.0061 (15)	0.0040 (15)	−0.0107 (16)
C9	0.026 (2)	0.0152 (19)	0.024 (2)	−0.0067 (15)	0.0001 (16)	−0.0072 (16)
C10	0.046 (3)	0.0140 (19)	0.030 (2)	−0.0060 (18)	−0.0071 (19)	−0.0045 (17)
C11	0.0191 (18)	0.0148 (18)	0.0189 (18)	−0.0049 (14)	0.0022 (14)	−0.0056 (15)
C12	0.030 (2)	0.020 (2)	0.023 (2)	−0.0097 (16)	0.0022 (16)	−0.0065 (16)
C13	0.0204 (19)	0.0177 (19)	0.0218 (19)	−0.0076 (16)	0.0006 (15)	−0.0054 (15)
C14	0.0199 (19)	0.0187 (19)	0.0195 (19)	−0.0051 (15)	−0.0013 (15)	−0.0049 (15)
C15	0.030 (2)	0.027 (2)	0.020 (2)	−0.0051 (17)	−0.0023 (16)	−0.0079 (16)
S1	0.0251 (5)	0.0215 (5)	0.0305 (5)	−0.0040 (4)	−0.0029 (4)	−0.0060 (4)
O5	0.0319 (15)	0.0226 (15)	0.0329 (16)	−0.0026 (12)	−0.0057 (12)	−0.0094 (12)
C16	0.032 (2)	0.023 (2)	0.038 (2)	−0.0045 (18)	−0.0077 (19)	−0.0040 (18)
C17	0.046 (3)	0.027 (2)	0.029 (2)	−0.0038 (19)	−0.009 (2)	−0.0048 (18)

Geometric parameters (Å, º)

Ni1—N3	1.828 (3)	C4—H4	0.9500
Ni1—N1	1.873 (3)	C5—C6	1.469 (5)
Ni1—N4	1.879 (3)	C6—C7	1.508 (5)
Ni1—N5	1.888 (3)	C7—H7A	0.9800
O1—C8	1.234 (4)	C7—H7B	0.9800
O2—N4	1.320 (4)	C7—H7C	0.9800
O3—C13	1.227 (4)	C8—C9	1.468 (5)
O4—N7	1.392 (4)	C9—C10	1.491 (5)
O4—H4O	0.9475	C10—H10A	0.9800
O6—H6O	0.9039	C10—H10B	0.9800
O6—H6P	0.9148	C10—H10C	0.9800
N1—C5	1.356 (5)	C11—C12	1.477 (5)
N1—C1	1.358 (5)	C12—H12A	0.9800
N2—C6	1.295 (5)	C12—H12B	0.9800
N2—N3	1.355 (4)	C12—H12C	0.9800
N3—C8	1.387 (5)	C13—C14	1.504 (5)
N4—C9	1.302 (5)	C14—C15	1.485 (5)
N5—C11	1.301 (4)	C15—H15A	0.9800
N5—N6	1.394 (4)	C15—H15B	0.9800
N6—C13	1.368 (5)	C15—H15C	0.9800
N6—H6N	0.8861	S1—O5	1.512 (3)
N7—C14	1.287 (5)	S1—C16	1.774 (4)
C1—C2	1.398 (5)	S1—C17	1.783 (4)
C1—C11	1.471 (5)	C16—H16A	0.9800
C2—C3	1.382 (5)	C16—H16B	0.9800
C2—H2	0.9500	C16—H16C	0.9800
C3—C4	1.378 (6)	C17—H17A	0.9800
C3—H3	0.9500	C17—H17B	0.9800
C4—C5	1.415 (5)	C17—H17C	0.9800
N3—Ni1—N1	94.01 (13)	O1—C8—N3	126.3 (3)
N3—Ni1—N4	83.99 (13)	O1—C8—C9	122.8 (3)
N1—Ni1—N4	177.21 (14)	N3—C8—C9	110.9 (3)
N3—Ni1—N5	177.34 (13)	N4—C9—C8	113.3 (3)
N1—Ni1—N5	83.41 (13)	N4—C9—C10	124.5 (3)
N4—Ni1—N5	98.61 (13)	C8—C9—C10	122.2 (3)
N7—O4—H4O	107.0	C9—C10—H10A	109.5
H6O—O6—H6P	102.7	C9—C10—H10B	109.5
C5—N1—C1	120.1 (3)	H10A—C10—H10B	109.5
C5—N1—Ni1	126.1 (3)	C9—C10—H10C	109.5
C1—N1—Ni1	113.8 (2)	H10A—C10—H10C	109.5
C6—N2—N3	121.2 (3)	H10B—C10—H10C	109.5
N2—N3—C8	114.1 (3)	N5—C11—C1	111.5 (3)
N2—N3—Ni1	130.3 (2)	N5—C11—C12	126.4 (3)
C8—N3—Ni1	115.6 (2)	C1—C11—C12	121.9 (3)
C9—N4—O2	119.0 (3)	C11—C12—H12A	109.5
C9—N4—Ni1	116.1 (2)	C11—C12—H12B	109.5
O2—N4—Ni1	124.9 (2)	H12A—C12—H12B	109.5
C11—N5—N6	119.3 (3)	C11—C12—H12C	109.5
C11—N5—Ni1	117.0 (2)	H12A—C12—H12C	109.5
N6—N5—Ni1	123.6 (2)	H12B—C12—H12C	109.5
C13—N6—N5	119.0 (3)	O3—C13—N6	124.9 (3)
C13—N6—H6N	117.9	O3—C13—C14	120.4 (3)
N5—N6—H6N	105.3	N6—C13—C14	114.7 (3)
C14—N7—O4	110.9 (3)	N7—C14—C15	125.6 (3)
N1—C1—C2	122.0 (3)	N7—C14—C13	115.8 (3)
N1—C1—C11	114.0 (3)	C15—C14—C13	118.6 (3)
C2—C1—C11	124.0 (3)	C14—C15—H15A	109.5
C3—C2—C1	118.3 (4)	C14—C15—H15B	109.5
C3—C2—H2	120.8	H15A—C15—H15B	109.5
C1—C2—H2	120.8	C14—C15—H15C	109.5
C4—C3—C2	119.9 (3)	H15A—C15—H15C	109.5
C4—C3—H3	120.1	H15B—C15—H15C	109.5
C2—C3—H3	120.1	O5—S1—C16	105.84 (18)
C3—C4—C5	120.3 (4)	O5—S1—C17	106.01 (19)
C3—C4—H4	119.9	C16—S1—C17	97.4 (2)
C5—C4—H4	119.9	S1—C16—H16A	109.5
N1—C5—C4	119.3 (3)	S1—C16—H16B	109.5
N1—C5—C6	120.8 (3)	H16A—C16—H16B	109.5
C4—C5—C6	119.9 (3)	S1—C16—H16C	109.5
N2—C6—C5	127.6 (3)	H16A—C16—H16C	109.5
N2—C6—C7	114.2 (3)	H16B—C16—H16C	109.5
C5—C6—C7	118.2 (3)	S1—C17—H17A	109.5
C6—C7—H7A	109.5	S1—C17—H17B	109.5
C6—C7—H7B	109.5	H17A—C17—H17B	109.5
H7A—C7—H7B	109.5	S1—C17—H17C	109.5
C6—C7—H7C	109.5	H17A—C17—H17C	109.5
H7A—C7—H7C	109.5	H17B—C17—H17C	109.5
H7B—C7—H7C	109.5
N3—Ni1—N1—C5	−1.8 (3)	N3—N2—C6—C5	0.1 (6)
N5—Ni1—N1—C5	177.6 (3)	N3—N2—C6—C7	−179.3 (3)
N3—Ni1—N1—C1	178.2 (2)	N1—C5—C6—N2	−0.6 (6)
N5—Ni1—N1—C1	−2.5 (2)	C4—C5—C6—N2	179.7 (3)
C6—N2—N3—C8	−179.9 (3)	N1—C5—C6—C7	178.8 (3)
C6—N2—N3—Ni1	−0.8 (5)	C4—C5—C6—C7	−0.9 (5)
N1—Ni1—N3—N2	1.4 (3)	N2—N3—C8—O1	−0.1 (5)
N4—Ni1—N3—N2	179.4 (3)	Ni1—N3—C8—O1	−179.3 (3)
N1—Ni1—N3—C8	−179.5 (2)	N2—N3—C8—C9	179.2 (3)
N4—Ni1—N3—C8	−1.4 (2)	Ni1—N3—C8—C9	0.0 (4)
N3—Ni1—N4—C9	2.9 (3)	O2—N4—C9—C8	177.2 (3)
N5—Ni1—N4—C9	−176.5 (3)	Ni1—N4—C9—C8	−3.6 (4)
N3—Ni1—N4—O2	−178.0 (3)	O2—N4—C9—C10	−1.5 (6)
N5—Ni1—N4—O2	2.6 (3)	Ni1—N4—C9—C10	177.6 (3)
N1—Ni1—N5—C11	5.8 (3)	O1—C8—C9—N4	−178.3 (3)
N4—Ni1—N5—C11	−172.3 (3)	N3—C8—C9—N4	2.3 (4)
N1—Ni1—N5—N6	−179.4 (3)	O1—C8—C9—C10	0.5 (6)
N4—Ni1—N5—N6	2.6 (3)	N3—C8—C9—C10	−178.8 (3)
C11—N5—N6—C13	−60.5 (4)	N6—N5—C11—C1	177.6 (3)
Ni1—N5—N6—C13	124.7 (3)	Ni1—N5—C11—C1	−7.3 (4)
C5—N1—C1—C2	−1.7 (5)	N6—N5—C11—C12	−6.8 (5)
Ni1—N1—C1—C2	178.3 (3)	Ni1—N5—C11—C12	168.3 (3)
C5—N1—C1—C11	179.3 (3)	N1—C1—C11—N5	5.1 (4)
Ni1—N1—C1—C11	−0.6 (4)	C2—C1—C11—N5	−173.9 (3)
N1—C1—C2—C3	0.6 (5)	N1—C1—C11—C12	−170.7 (3)
C11—C1—C2—C3	179.5 (3)	C2—C1—C11—C12	10.3 (5)
C1—C2—C3—C4	0.8 (5)	N5—N6—C13—O3	8.2 (5)
C2—C3—C4—C5	−1.0 (6)	N5—N6—C13—C14	−172.7 (3)
C1—N1—C5—C4	1.4 (5)	O4—N7—C14—C15	−0.1 (5)
Ni1—N1—C5—C4	−178.7 (3)	O4—N7—C14—C13	179.6 (3)
C1—N1—C5—C6	−178.3 (3)	O3—C13—C14—N7	−174.8 (3)
Ni1—N1—C5—C6	1.6 (5)	N6—C13—C14—N7	6.1 (5)
C3—C4—C5—N1	−0.1 (5)	O3—C13—C14—C15	4.9 (5)
C3—C4—C5—C6	179.7 (3)	N6—C13—C14—C15	−174.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6O···O3	0.90	2.07	2.948 (4)	162
N6—H6N···O2	0.89	1.70	2.555 (4)	162
O4—H4O···O5	0.95	1.73	2.661 (4)	165
O6—H6P···O1^i	0.91	1.99	2.819 (4)	151

Symmetry code: (i) −x+1, −y, −z+1.