Aqua-1κO-{μ-1,3-bis­[2-(2-oxido­benzyl­idene­amino)­ethyl]-2-(2-oxido­phenyl)­imidazolidine-1κ⁴O,N,N′,O′;2κ⁴O′,N′′,N′′′,O′′}(μ-2-formylphenolato-1:2κ³O¹:O¹,O²)dinickel(II) trihydrate: a one-dimensional chain linked by O—H...O hydrogen bonds and C—H...π interactions

In the title compound, [Ni₂(C₇H₅O₂)(C₂₇H₂₇N₄O₂)(H₂O)]·2.38H₂O, each Ni atom is coordinated by two N atoms and four O atoms from the hepta­dentate Schiff base ligand and one salicylaldehyde or water mol­ecule, forming an asymmetric mol­ecule with three bridges linking the two Ni^II ions, which are separated by 3.081 (1) Å. Hydrogen-bonded water and C—H...π inter­actions take part in the stabilization of the complex. The complex molecules are connected into a one-dimensional chain along the c axis by O—H...O hydrogen bonds between coordinated and solvent water mol­ecules and by C—H...π inter­actions.

S1. Comment

Multinuclear complexes of the heptadentate Schiff base 2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3- enyl]-1,3-imidazolidine (H₃L) attract much attention because of their various properties, such as fixing atmospheric carbon dioxide (Fondo et al., 2002) or their magnetic properties (Fondo et al., 2004; Prasant Kumar et al., 2006). The title complex was synthesized in order to study its inhibitory activity on the protein [Enzyme?] tyrosine phosphatase 1B (PTP1B) and we present its crystal structure here.

The molecular structure of (I) is illustrated in Fig. 1. The compound consists of a binuclear phenolic Schiff base complex and three water molecules. In the binuclear complex, each Ni atom is coordinated by two N and four O atoms from the heptadentate Schiff base ligand and by one salicylaldehyde or a water molecule, forming an asymmetric molecule with three bridge links. The Ni—N and Ni—O distances and bond anges around the two metal ions are in the normal ranges (Table 1; Standard reference?). A water molecule acts as a hydrogen-bond bridge between atoms O1 and O2. Additionally, a C—H···π interaction, C20—H···Cg1 (Cg1 is the centroid of the C13–C18 ring), with a C···Cg distance of 3.510 (5) Å, takes part in stabilization of the structure. All these structural characteristics are in good agreement with the compound [Ni₂L(o-OC₆H₃BrCHO)(H₂O)]·2.25MeCN·H₂O [L is 2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxyphenyl)-3-azabut- 3-enyl]-1,3-imidazolidine; Fondo et al., 2006], indicating that the 5-Br atom in [Ni₂L(o-OC₆H₃BrCHO)(H₂O)]·2.25MeCN·H₂O has little effect on the molecular structure.

Complex molecules of (I) are linked to form a one-dimensional chain along the c axis by an O—H···O hydrogen bond between coordinated and solvent water molecules (Fig. 2). This is similar to what is observed in the compounds [Ni₂L(o-OC₆H₃BrCHO)(H₂O)]·2.25MeCN·H₂O and [Ni₂L(OAc)(H₂O)₂]·3MeCN·2H₂O (Fondo et al., 2006), especially the latter, where the coordinated o-OC₆H₃BrCHO ligand is replaced by an acetate group, but this hydrogen bond still exists and connects the complexes to form a one-dimensional chain. Thus, this hydrogen bond is very important in the packing of this kind of compound.

In addition to this hydrogen bond, there are a further two C—H···π interactions contributing to the stabilization of the one-dimensional chain, C20···Cg2ⁱ and C25···Cg3ⁱⁱ [Cg2 is the centroid of the C1–C6 ring and Cg3 is the centroid of the C29–C34 ring; symmetry codes: (i) x, 1/2 - y, 1/2 + z; (ii) x, 1/2 - y, -1/2 + z], with C···Cg distances of 3.577 (5) and 3.550 (6) Å, respectively (Fig. 2). This can be compared with [Ni₂L(o-OC₆H₃BrCHO)(H₂O)]·2.25MeCN·H₂O, where the corresponding C20—H···π interaction is retained, but another one is changed, possibly because of the repulsive interaction between the 5-bromo-2-hydroxyphenyl groups. Therefore, although the 5-Br atom of the ligand has little effect on the molecular structure, it can influence crystal packing. Because of these C—H···π interactions, the closest Ni···Ni distance between neighbouring complexes of (I) is 7.248 Å, 0.152 Å longer than that in [Ni₂L(o-OC₆H₃BrCHO)(H₂O)]·2.25MeCN·H₂O.

Related literature

For related literature, see: Fondo et al. (2002, 2004, 2006); Prasant Kumar, Guillem & Debashis (2006); Sarma & Bailar (1955).

S2. Experimental

The heptadentate Schiff base was prepared following a modified literature procedure (Sarma & Bailar, 1955). The ligand was collected by filtration and recrystallized from warm ethanol. The title compound, (I), was synthesized as follows. NiSO₄·6H₂O (0.1314 g) in water (10 ml) was added to H₃L (0.1770 g) in methanol solution (15 ml) with stirring. The solution was refluxed for 1 h and the cooled solution was filtered. Deep-green crystals were obtained from the filtrate on slow evaporation after 10 d. The presence of the salicylaldehyde ligand in the structure of (I) demonstrates that the heptadentate Schiff base is unstable in solution over a long period, undergoing hydrolysis.

S3. Refinement

H atoms attached to C atoms were placed in geometrically idealized positions, with Csp²—H = 0.93 Å, Csp³—H = 0.97 Å and Csp³—H = 0.98 Å, and refined with U_iso(H) = 1.2U_eq(C). H atoms attached to O atoms were located from difference Fourier maps and refined as riding in their as-found positions, with U_iso(H) = 1.5U_eq(O). The O—H distances are in the range 0.850–0.851 Å. Atom O8 was found to be disordered; the final occupancies from the refinement were O8A 0.59 and O8B 0.41. Fourier maps also showed that there is only less density for the O9A and O9B sites, which would correspond with oxygen occupancies of 0.125 at O9A and 0.250 at O9B, and with these small occupancies it is not worth refining the positiond anisotropically. The lack of hydrogen-bonding interactions involving these water molecules (O8, O9A and O9B), which are simply occluded in holes in the structure. For these reasons, the water (O8, O9A and O9B) H atoms were not considered.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.

Figures

	Fig. 1. The structure of (I), with the atom-numbering scehem. Displacement ellipsoids are drawn at the 40% probability level. Dotted lines indicate hydrogen bonds and C—H···π interactions. Cg1 is the centroid of the C13–C18 ring. H atoms not involved in hydrogen bonds and the minor components of the disordered O atoms have been omitted.
	Fig. 2. The one-dimensional chain constructed by O—H···O hydrogen bonds and C—H···π interactions, along the c axis (dotted lines). Cg2 and Cg3 are the centroids of the C1–C6 and C29–C34 rings, respectively. The minor components of the disordered O atoms have been omitted. [Symmetry codes: (i) x, 1/2 - y, 1/2 + z; (ii) x, y, 1 + z; (iii) x, 1/2 - y, 1.5 + z.]

Aqua-1κO-{µ-1,3-bis[2-(2-oxidobenzylideneamino)ethyl]-2-(2- oxidophenyl)imidazolidine-1κ⁴O,N,N',O';2κ⁴O',N'',N''',O''}- (µ-2-oxidobenzaldehyde-1:2κ³O²:O²,O¹)dinickel(II) 2.38-hydrate

Crystal data

[Ni2(C7H5O2)(C25H29N4O2)(H2O)]·2.38H2O	F(000) = 1564.2
Mr = 752.13	Dx = 1.401 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3301 reflections
a = 11.4361 (8) Å	θ = 2.3–23.4°
b = 21.5977 (16) Å	µ = 1.11 mm^−1
c = 14.7334 (11) Å	T = 298 K
β = 101.466 (1)°	Block, deep green
V = 3566.4 (5) Å^3	0.28 × 0.13 × 0.02 mm
Z = 4

Data collection

Bruker SMART 1K CCD area detector diffractometer	6165 independent reflections
Radiation source: fine-focus sealed tube	4665 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −13→13
Tmin = 0.746, Tmax = 0.978	k = −18→25
14776 measured reflections	l = −17→16

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.168	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0971P)^2] where P = (Fo^2 + 2Fc^2)/3
6165 reflections	(Δ/σ)max = 0.001
451 parameters	Δρmax = 0.95 e Å^−3
0 restraints	Δρmin = −0.39 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	Occ. (<1)
Ni1	0.24763 (5)	0.23788 (3)	0.51507 (4)	0.03057 (19)
Ni2	0.15468 (5)	0.36943 (3)	0.46145 (4)	0.0327 (2)
N1	0.0014 (3)	0.41128 (19)	0.4052 (3)	0.0423 (10)
N2	0.0625 (3)	0.35037 (17)	0.5748 (3)	0.0335 (9)
N3	0.1326 (3)	0.25225 (17)	0.6140 (2)	0.0306 (8)
N4	0.1787 (3)	0.15197 (18)	0.5092 (3)	0.0350 (9)
O1	0.2271 (3)	0.39598 (16)	0.3542 (2)	0.0438 (8)
O2	0.1174 (3)	0.27985 (14)	0.4141 (2)	0.0321 (7)
O3	0.3505 (3)	0.21612 (15)	0.4255 (2)	0.0396 (8)
O4	0.3085 (2)	0.32901 (14)	0.5249 (2)	0.0342 (7)
O5	0.2176 (3)	0.45240 (15)	0.5299 (2)	0.0439 (8)
O6	0.3859 (3)	0.20704 (18)	0.6287 (2)	0.0508 (9)
H6A	0.4441	0.1835	0.6239	0.076*
H6B	0.3739	0.2043	0.6837	0.076*
C1	0.1873 (5)	0.4390 (2)	0.2924 (3)	0.0428 (12)
C2	0.2626 (5)	0.4608 (3)	0.2341 (4)	0.0526 (14)
H2	0.3388	0.4443	0.2396	0.063*
C3	0.2247 (7)	0.5062 (3)	0.1691 (4)	0.0701 (19)
H3	0.2769	0.5209	0.1331	0.084*
C4	0.1116 (7)	0.5300 (3)	0.1566 (4)	0.073 (2)
H4	0.0867	0.5596	0.1110	0.087*
C5	0.0352 (7)	0.5100 (3)	0.2117 (4)	0.0661 (18)
H5	−0.0411	0.5266	0.2035	0.079*
C6	0.0709 (5)	0.4645 (2)	0.2805 (4)	0.0485 (13)
C7	−0.0153 (5)	0.4485 (2)	0.3367 (4)	0.0472 (13)
H7	−0.0899	0.4673	0.3214	0.057*
C8	−0.0935 (4)	0.4029 (2)	0.4580 (4)	0.0492 (14)
H8A	−0.1393	0.3661	0.4370	0.059*
H8B	−0.1469	0.4382	0.4489	0.059*
C9	−0.0359 (4)	0.3967 (2)	0.5607 (4)	0.0459 (13)
H9A	−0.0046	0.4366	0.5843	0.055*
H9B	−0.0959	0.3842	0.5952	0.055*
C10	0.1371 (4)	0.3564 (2)	0.6693 (3)	0.0436 (12)
H10A	0.0885	0.3682	0.7134	0.052*
H10B	0.1987	0.3874	0.6701	0.052*
C11	0.1922 (4)	0.2930 (2)	0.6927 (3)	0.0387 (12)
H11A	0.2778	0.2942	0.6964	0.046*
H11B	0.1763	0.2782	0.7512	0.046*
C12	0.0198 (4)	0.2858 (2)	0.5768 (3)	0.0316 (10)
H12	−0.0321	0.2830	0.6222	0.038*
C13	−0.0465 (4)	0.2607 (2)	0.4863 (3)	0.0331 (10)
C14	0.0084 (4)	0.2581 (2)	0.4097 (3)	0.0321 (10)
C15	−0.0565 (5)	0.2300 (3)	0.3301 (4)	0.0557 (15)
H15	−0.0237	0.2280	0.2772	0.067*
C16	−0.1679 (5)	0.2052 (3)	0.3280 (4)	0.072 (2)
H16	−0.2077	0.1861	0.2741	0.087*
C17	−0.2211 (5)	0.2078 (3)	0.4020 (4)	0.0619 (16)
H17	−0.2965	0.1909	0.3992	0.074*
C18	−0.1606 (4)	0.2364 (2)	0.4825 (4)	0.0456 (13)
H18	−0.1962	0.2393	0.5338	0.055*
C19	0.1102 (4)	0.1879 (2)	0.6452 (3)	0.0391 (11)
H19A	0.1784	0.1744	0.6912	0.047*
H19B	0.0412	0.1884	0.6743	0.047*
C20	0.0891 (4)	0.1427 (2)	0.5667 (3)	0.0397 (11)
H20A	0.0943	0.1008	0.5907	0.048*
H20B	0.0099	0.1487	0.5295	0.048*
C21	0.2157 (5)	0.1062 (2)	0.4688 (4)	0.0466 (13)
H21	0.1814	0.0680	0.4763	0.056*
C22	0.3061 (5)	0.1072 (2)	0.4117 (4)	0.0459 (13)
C23	0.3330 (6)	0.0507 (3)	0.3748 (5)	0.0718 (19)
H23	0.2924	0.0152	0.3866	0.086*
C24	0.4188 (7)	0.0466 (3)	0.3208 (6)	0.086 (2)
H24	0.4356	0.0085	0.2968	0.104*
C25	0.4784 (6)	0.0980 (3)	0.3031 (4)	0.0666 (17)
H25	0.5367	0.0951	0.2673	0.080*
C26	0.4530 (5)	0.1540 (3)	0.3375 (4)	0.0479 (13)
H26	0.4935	0.1888	0.3230	0.057*
C27	0.3675 (4)	0.1615 (2)	0.3947 (3)	0.0378 (11)
C28	0.3232 (4)	0.4629 (2)	0.5569 (3)	0.0386 (11)
H28	0.3418	0.5034	0.5757	0.046*
C29	0.4236 (4)	0.4217 (2)	0.5639 (3)	0.0360 (11)
C30	0.4114 (4)	0.3567 (2)	0.5462 (3)	0.0321 (10)
C31	0.5179 (4)	0.3228 (2)	0.5556 (4)	0.0431 (12)
H31	0.5143	0.2805	0.5434	0.052*
C32	0.6271 (4)	0.3505 (3)	0.5823 (4)	0.0505 (14)
H32	0.6957	0.3265	0.5885	0.061*
C33	0.6380 (4)	0.4137 (3)	0.6004 (4)	0.0488 (13)
H33	0.7127	0.4319	0.6184	0.059*
C34	0.5375 (4)	0.4481 (2)	0.5912 (4)	0.0437 (12)
H34	0.5440	0.4904	0.6032	0.052*
O7	0.3875 (3)	0.31397 (17)	0.3162 (2)	0.0474 (9)
H7A	0.3804	0.2830	0.3504	0.071*
H7B	0.3457	0.3434	0.3309	0.071*
O8A	0.591 (3)	0.381 (2)	0.3451 (13)	0.126 (10)	0.59 (8)
O8B	0.626 (2)	0.343 (3)	0.329 (3)	0.108 (16)	0.41 (8)
O9A	0.639 (2)	0.1241 (14)	0.586 (2)	0.051 (7)*	0.13
O9B	0.6316 (13)	0.1777 (7)	0.6373 (11)	0.058 (4)*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0319 (3)	0.0305 (3)	0.0300 (3)	0.0033 (2)	0.0080 (2)	−0.0009 (2)
Ni2	0.0296 (3)	0.0303 (4)	0.0375 (4)	0.0049 (2)	0.0048 (3)	−0.0003 (3)
N1	0.037 (2)	0.033 (2)	0.052 (3)	0.0074 (18)	0.0006 (19)	−0.003 (2)
N2	0.032 (2)	0.033 (2)	0.035 (2)	0.0054 (16)	0.0048 (17)	−0.0074 (17)
N3	0.033 (2)	0.033 (2)	0.024 (2)	0.0029 (16)	0.0038 (16)	0.0003 (16)
N4	0.042 (2)	0.032 (2)	0.031 (2)	0.0046 (17)	0.0076 (17)	0.0023 (17)
O1	0.0438 (19)	0.045 (2)	0.043 (2)	0.0068 (16)	0.0092 (16)	0.0069 (16)
O2	0.0320 (16)	0.0365 (18)	0.0288 (17)	0.0043 (13)	0.0082 (13)	−0.0024 (13)
O3	0.0436 (19)	0.039 (2)	0.0383 (19)	0.0065 (15)	0.0142 (16)	−0.0034 (15)
O4	0.0248 (16)	0.0322 (17)	0.0442 (19)	0.0020 (13)	0.0032 (14)	−0.0015 (14)
O5	0.0363 (19)	0.036 (2)	0.059 (2)	0.0046 (15)	0.0103 (17)	−0.0060 (16)
O6	0.043 (2)	0.067 (3)	0.040 (2)	0.0168 (17)	0.0035 (16)	0.0067 (18)
C1	0.056 (3)	0.031 (3)	0.036 (3)	−0.002 (2)	−0.004 (2)	−0.006 (2)
C2	0.060 (3)	0.051 (3)	0.046 (3)	−0.005 (3)	0.007 (3)	0.008 (3)
C3	0.103 (6)	0.051 (4)	0.057 (4)	−0.023 (4)	0.018 (4)	0.006 (3)
C4	0.118 (6)	0.042 (4)	0.051 (4)	−0.005 (4)	0.002 (4)	0.012 (3)
C5	0.101 (5)	0.043 (3)	0.049 (4)	0.014 (3)	0.001 (4)	0.004 (3)
C6	0.068 (4)	0.032 (3)	0.041 (3)	0.010 (3)	−0.001 (3)	−0.003 (2)
C7	0.053 (3)	0.035 (3)	0.046 (3)	0.015 (2)	−0.009 (3)	−0.001 (2)
C8	0.032 (3)	0.039 (3)	0.075 (4)	0.012 (2)	0.008 (3)	0.000 (3)
C9	0.039 (3)	0.044 (3)	0.059 (4)	0.004 (2)	0.020 (3)	−0.009 (3)
C10	0.047 (3)	0.048 (3)	0.035 (3)	−0.002 (2)	0.007 (2)	−0.017 (2)
C11	0.035 (3)	0.050 (3)	0.028 (3)	−0.005 (2)	0.002 (2)	−0.013 (2)
C12	0.030 (2)	0.035 (3)	0.031 (3)	−0.0018 (19)	0.0096 (19)	−0.003 (2)
C13	0.027 (2)	0.033 (3)	0.037 (3)	0.0036 (19)	0.002 (2)	−0.002 (2)
C14	0.036 (3)	0.026 (2)	0.032 (3)	0.0061 (19)	0.003 (2)	−0.0006 (19)
C15	0.055 (3)	0.076 (4)	0.033 (3)	−0.012 (3)	0.004 (3)	−0.013 (3)
C16	0.066 (4)	0.109 (6)	0.037 (3)	−0.029 (4)	0.000 (3)	−0.018 (3)
C17	0.043 (3)	0.079 (5)	0.062 (4)	−0.016 (3)	0.004 (3)	−0.006 (3)
C18	0.036 (3)	0.051 (3)	0.051 (3)	0.000 (2)	0.011 (2)	−0.002 (3)
C19	0.043 (3)	0.041 (3)	0.035 (3)	0.004 (2)	0.012 (2)	0.007 (2)
C20	0.041 (3)	0.034 (3)	0.045 (3)	−0.002 (2)	0.010 (2)	0.002 (2)
C21	0.054 (3)	0.037 (3)	0.048 (3)	−0.001 (2)	0.010 (3)	0.002 (2)
C22	0.052 (3)	0.040 (3)	0.047 (3)	0.011 (2)	0.014 (3)	−0.007 (2)
C23	0.093 (5)	0.048 (4)	0.084 (5)	0.006 (3)	0.040 (4)	−0.013 (3)
C24	0.102 (5)	0.059 (5)	0.112 (6)	0.025 (4)	0.054 (5)	−0.023 (4)
C25	0.074 (4)	0.072 (5)	0.060 (4)	0.020 (4)	0.030 (3)	−0.012 (3)
C26	0.043 (3)	0.059 (4)	0.041 (3)	0.011 (3)	0.008 (2)	−0.001 (3)
C27	0.037 (3)	0.047 (3)	0.027 (3)	0.013 (2)	0.004 (2)	−0.004 (2)
C28	0.042 (3)	0.035 (3)	0.040 (3)	−0.001 (2)	0.010 (2)	0.001 (2)
C29	0.035 (3)	0.037 (3)	0.036 (3)	−0.007 (2)	0.007 (2)	−0.003 (2)
C30	0.027 (2)	0.035 (3)	0.032 (3)	0.0035 (19)	0.0007 (19)	0.007 (2)
C31	0.032 (3)	0.044 (3)	0.052 (3)	−0.003 (2)	0.007 (2)	−0.010 (2)
C32	0.036 (3)	0.061 (4)	0.055 (3)	0.009 (3)	0.010 (2)	−0.004 (3)
C33	0.032 (3)	0.056 (4)	0.060 (4)	−0.012 (2)	0.013 (2)	−0.007 (3)
C34	0.042 (3)	0.038 (3)	0.053 (3)	−0.006 (2)	0.013 (2)	−0.002 (2)
O7	0.052 (2)	0.054 (2)	0.039 (2)	0.0041 (17)	0.0151 (17)	−0.0009 (17)
O8A	0.101 (13)	0.11 (2)	0.164 (12)	−0.025 (15)	0.015 (9)	0.020 (10)
O8B	0.060 (10)	0.12 (3)	0.132 (18)	−0.009 (12)	−0.009 (9)	0.045 (18)

Geometric parameters (Å, º)

Ni1—O3	1.991 (3)	C10—H10A	0.9700
Ni1—N4	2.011 (4)	C10—H10B	0.9700
Ni1—O4	2.083 (3)	C11—H11A	0.9700
Ni1—O2	2.090 (3)	C11—H11B	0.9700
Ni1—O6	2.167 (3)	C12—C13	1.498 (6)
Ni1—N3	2.171 (4)	C12—H12	0.9800
Ni1—Ni2	3.081 (1)	C13—C18	1.397 (6)
Ni2—N1	2.000 (4)	C13—C14	1.398 (6)
Ni2—O1	2.008 (3)	C14—C15	1.396 (7)
Ni2—O4	2.019 (3)	C15—C16	1.377 (8)
Ni2—O2	2.072 (3)	C15—H15	0.9300
Ni2—O5	2.111 (3)	C16—C17	1.351 (8)
Ni2—N2	2.184 (4)	C16—H16	0.9300
N1—C7	1.275 (6)	C17—C18	1.392 (8)
N1—C8	1.466 (7)	C17—H17	0.9300
N2—C12	1.480 (6)	C18—H18	0.9300
N2—C10	1.487 (6)	C19—C20	1.496 (7)
N2—C9	1.489 (6)	C19—H19A	0.9700
N3—C12	1.486 (6)	C19—H19B	0.9700
N3—C19	1.502 (6)	C20—H20A	0.9700
N3—C11	1.506 (6)	C20—H20B	0.9700
N4—C21	1.269 (6)	C21—C22	1.456 (7)
N4—C20	1.466 (6)	C21—H21	0.9300
O1—C1	1.317 (6)	C22—C23	1.395 (7)
O2—C14	1.321 (5)	C22—C27	1.414 (7)
O3—C27	1.293 (6)	C23—C24	1.383 (9)
O4—C30	1.302 (5)	C23—H23	0.9300
O5—C28	1.215 (5)	C24—C25	1.355 (9)
O6—H6A	0.8510	C24—H24	0.9300
O6—H6B	0.8503	C25—C26	1.366 (8)
C1—C2	1.413 (7)	C25—H25	0.9300
C1—C6	1.419 (7)	C26—C27	1.421 (7)
C2—C3	1.379 (8)	C26—H26	0.9300
C2—H2	0.9300	C28—C29	1.440 (7)
C3—C4	1.370 (9)	C28—H28	0.9300
C3—H3	0.9300	C29—C34	1.406 (6)
C4—C5	1.375 (9)	C29—C30	1.431 (6)
C4—H4	0.9300	C30—C31	1.404 (6)
C5—C6	1.412 (8)	C31—C32	1.370 (7)
C5—H5	0.9300	C31—H31	0.9300
C6—C7	1.450 (8)	C32—C33	1.391 (8)
C7—H7	0.9300	C32—H32	0.9300
C8—C9	1.531 (7)	C33—C34	1.353 (7)
C8—H8A	0.9700	C33—H33	0.9300
C8—H8B	0.9700	C34—H34	0.9300
C9—H9A	0.9700	O7—H7A	0.8511
C9—H9B	0.9700	O7—H7B	0.8498
C10—C11	1.518 (7)
O3—Ni1—N4	91.85 (15)	H9A—C9—H9B	108.0
O3—Ni1—O4	92.06 (13)	N2—C10—C11	105.6 (4)
N4—Ni1—O4	175.87 (14)	N2—C10—H10A	110.6
O3—Ni1—O2	93.56 (12)	C11—C10—H10A	110.6
N4—Ni1—O2	98.74 (14)	N2—C10—H10B	110.6
O4—Ni1—O2	79.67 (12)	C11—C10—H10B	110.6
O3—Ni1—O6	90.17 (13)	H10A—C10—H10B	108.8
N4—Ni1—O6	88.22 (15)	N3—C11—C10	104.4 (4)
O4—Ni1—O6	93.12 (13)	N3—C11—H11A	110.9
O2—Ni1—O6	171.98 (13)	C10—C11—H11A	110.9
O3—Ni1—N3	174.56 (14)	N3—C11—H11B	110.9
N4—Ni1—N3	82.87 (15)	C10—C11—H11B	110.9
O4—Ni1—N3	93.26 (13)	H11A—C11—H11B	108.9
O2—Ni1—N3	88.54 (12)	N2—C12—N3	101.6 (3)
O6—Ni1—N3	88.38 (13)	N2—C12—C13	115.7 (4)
N1—Ni2—O1	90.57 (16)	N3—C12—C13	113.6 (4)
N1—Ni2—O4	176.90 (16)	N2—C12—H12	108.5
O1—Ni2—O4	91.73 (13)	N3—C12—H12	108.5
N1—Ni2—O2	100.26 (14)	C13—C12—H12	108.5
O1—Ni2—O2	95.23 (13)	C18—C13—C14	121.3 (4)
O4—Ni2—O2	81.59 (12)	C18—C13—C12	118.4 (4)
N1—Ni2—O5	90.10 (15)	C14—C13—C12	120.2 (4)
O1—Ni2—O5	88.80 (14)	O2—C14—C15	122.3 (4)
O4—Ni2—O5	87.87 (12)	O2—C14—C13	121.1 (4)
O2—Ni2—O5	168.82 (13)	C15—C14—C13	116.5 (4)
N1—Ni2—N2	83.39 (16)	C16—C15—C14	121.5 (5)
O1—Ni2—N2	173.16 (13)	C16—C15—H15	119.2
O4—Ni2—N2	94.19 (13)	C14—C15—H15	119.2
O2—Ni2—N2	89.03 (13)	C17—C16—C15	122.0 (5)
O5—Ni2—N2	88.00 (14)	C17—C16—H16	119.0
C7—N1—C8	119.2 (4)	C15—C16—H16	119.0
C7—N1—Ni2	126.4 (4)	C16—C17—C18	118.6 (5)
C8—N1—Ni2	113.9 (3)	C16—C17—H17	120.7
C12—N2—C10	101.2 (3)	C18—C17—H17	120.7
C12—N2—C9	113.2 (4)	C17—C18—C13	120.2 (5)
C10—N2—C9	110.4 (4)	C17—C18—H18	119.9
C12—N2—Ni2	113.8 (3)	C13—C18—H18	119.9
C10—N2—Ni2	115.1 (3)	C20—C19—N3	112.1 (4)
C9—N2—Ni2	103.4 (3)	C20—C19—H19A	109.2
C12—N3—C19	112.1 (3)	N3—C19—H19A	109.2
C12—N3—C11	103.1 (3)	C20—C19—H19B	109.2
C19—N3—C11	112.5 (3)	N3—C19—H19B	109.2
C12—N3—Ni1	114.8 (3)	H19A—C19—H19B	107.9
C19—N3—Ni1	103.7 (3)	N4—C20—C19	109.5 (4)
C11—N3—Ni1	111.0 (3)	N4—C20—H20A	109.8
C21—N4—C20	120.1 (4)	C19—C20—H20A	109.8
C21—N4—Ni1	125.0 (4)	N4—C20—H20B	109.8
C20—N4—Ni1	114.4 (3)	C19—C20—H20B	109.8
C1—O1—Ni2	127.3 (3)	H20A—C20—H20B	108.2
C14—O2—Ni2	118.5 (3)	N4—C21—C22	126.9 (5)
C14—O2—Ni1	114.4 (3)	N4—C21—H21	116.5
Ni2—O2—Ni1	95.51 (12)	C22—C21—H21	116.5
C27—O3—Ni1	126.7 (3)	C23—C22—C27	120.0 (5)
C30—O4—Ni2	125.2 (3)	C23—C22—C21	116.7 (5)
C30—O4—Ni1	136.4 (3)	C27—C22—C21	123.3 (5)
Ni2—O4—Ni1	97.36 (12)	C24—C23—C22	121.2 (6)
C28—O5—Ni2	122.5 (3)	C24—C23—H23	119.4
Ni1—O6—H6A	125.6	C22—C23—H23	119.4
Ni1—O6—H6B	121.8	C25—C24—C23	119.9 (6)
H6A—O6—H6B	108.4	C25—C24—H24	120.0
O1—C1—C2	119.1 (5)	C23—C24—H24	120.0
O1—C1—C6	123.1 (5)	C24—C25—C26	120.1 (6)
C2—C1—C6	117.7 (5)	C24—C25—H25	119.9
C3—C2—C1	120.9 (6)	C26—C25—H25	119.9
C3—C2—H2	119.6	C25—C26—C27	122.9 (6)
C1—C2—H2	119.6	C25—C26—H26	118.6
C4—C3—C2	121.3 (6)	C27—C26—H26	118.6
C4—C3—H3	119.3	O3—C27—C22	125.4 (4)
C2—C3—H3	119.3	O3—C27—C26	118.7 (5)
C3—C4—C5	119.7 (6)	C22—C27—C26	115.9 (5)
C3—C4—H4	120.2	O5—C28—C29	129.4 (5)
C5—C4—H4	120.2	O5—C28—H28	115.3
C4—C5—C6	121.0 (6)	C29—C28—H28	115.3
C4—C5—H5	119.5	C34—C29—C30	120.1 (4)
C6—C5—H5	119.5	C34—C29—C28	116.8 (4)
C5—C6—C1	119.3 (6)	C30—C29—C28	123.1 (4)
C5—C6—C7	116.3 (5)	O4—C30—C31	120.7 (4)
C1—C6—C7	124.4 (5)	O4—C30—C29	123.0 (4)
N1—C7—C6	126.2 (5)	C31—C30—C29	116.3 (4)
N1—C7—H7	116.9	C32—C31—C30	121.5 (5)
C6—C7—H7	116.9	C32—C31—H31	119.2
N1—C8—C9	108.5 (4)	C30—C31—H31	119.2
N1—C8—H8A	110.0	C31—C32—C33	121.8 (5)
C9—C8—H8A	110.0	C31—C32—H32	119.1
N1—C8—H8B	110.0	C33—C32—H32	119.1
C9—C8—H8B	110.0	C34—C33—C32	118.5 (5)
H8A—C8—H8B	108.4	C34—C33—H33	120.7
N2—C9—C8	111.2 (4)	C32—C33—H33	120.7
N2—C9—H9A	109.4	C33—C34—C29	121.8 (5)
C8—C9—H9A	109.4	C33—C34—H34	119.1
N2—C9—H9B	109.4	C29—C34—H34	119.1
C8—C9—H9B	109.4	H7A—O7—H7B	108.3
O1—Ni2—N1—C7	−11.4 (4)	C4—C5—C6—C7	177.8 (5)
O2—Ni2—N1—C7	−106.8 (4)	O1—C1—C6—C5	−179.3 (5)
O5—Ni2—N1—C7	77.4 (4)	C2—C1—C6—C5	0.0 (7)
N2—Ni2—N1—C7	165.4 (4)	O1—C1—C6—C7	2.8 (8)
O1—Ni2—N1—C8	176.9 (3)	C2—C1—C6—C7	−177.9 (5)
O2—Ni2—N1—C8	81.5 (3)	C8—N1—C7—C6	176.6 (5)
O5—Ni2—N1—C8	−94.3 (3)	Ni2—N1—C7—C6	5.3 (8)
N2—Ni2—N1—C8	−6.3 (3)	C5—C6—C7—N1	−176.1 (5)
N1—Ni2—N2—C12	103.7 (3)	C1—C6—C7—N1	1.9 (8)
O4—Ni2—N2—C12	−78.2 (3)	C7—N1—C8—C9	−141.8 (5)
O2—Ni2—N2—C12	3.3 (3)	Ni2—N1—C8—C9	30.6 (5)
O5—Ni2—N2—C12	−166.0 (3)	C12—N2—C9—C8	−82.0 (5)
N1—Ni2—N2—C10	−140.1 (3)	C10—N2—C9—C8	165.4 (4)
O4—Ni2—N2—C10	38.0 (3)	Ni2—N2—C9—C8	41.6 (5)
O2—Ni2—N2—C10	119.5 (3)	N1—C8—C9—N2	−49.4 (6)
O5—Ni2—N2—C10	−49.7 (3)	C12—N2—C10—C11	34.0 (4)
N1—Ni2—N2—C9	−19.5 (3)	C9—N2—C10—C11	154.1 (4)
O4—Ni2—N2—C9	158.5 (3)	Ni2—N2—C10—C11	−89.2 (4)
O2—Ni2—N2—C9	−120.0 (3)	C12—N3—C11—C10	−22.8 (4)
O5—Ni2—N2—C9	70.8 (3)	C19—N3—C11—C10	−143.7 (4)
N4—Ni1—N3—C12	−101.6 (3)	Ni1—N3—C11—C10	100.6 (3)
O4—Ni1—N3—C12	76.9 (3)	N2—C10—C11—N3	−7.0 (5)
O2—Ni1—N3—C12	−2.6 (3)	C10—N2—C12—N3	−48.6 (4)
O6—Ni1—N3—C12	170.0 (3)	C9—N2—C12—N3	−166.7 (4)
N4—Ni1—N3—C19	20.9 (3)	Ni2—N2—C12—N3	75.6 (3)
O4—Ni1—N3—C19	−160.5 (3)	C10—N2—C12—C13	−172.1 (4)
O2—Ni1—N3—C19	119.9 (3)	C9—N2—C12—C13	69.8 (5)
O6—Ni1—N3—C19	−67.5 (3)	Ni2—N2—C12—C13	−48.0 (4)
N4—Ni1—N3—C11	142.0 (3)	C19—N3—C12—N2	165.7 (3)
O4—Ni1—N3—C11	−39.5 (3)	C11—N3—C12—N2	44.5 (4)
O2—Ni1—N3—C11	−119.0 (3)	Ni1—N3—C12—N2	−76.4 (3)
O6—Ni1—N3—C11	53.6 (3)	C19—N3—C12—C13	−69.4 (5)
O3—Ni1—N4—C21	8.4 (4)	C11—N3—C12—C13	169.4 (4)
O2—Ni1—N4—C21	102.3 (4)	Ni1—N3—C12—C13	48.6 (4)
O6—Ni1—N4—C21	−81.7 (4)	N2—C12—C13—C18	−125.1 (5)
N3—Ni1—N4—C21	−170.3 (4)	N3—C12—C13—C18	117.9 (5)
O3—Ni1—N4—C20	−179.2 (3)	N2—C12—C13—C14	59.0 (6)
O2—Ni1—N4—C20	−85.3 (3)	N3—C12—C13—C14	−58.0 (6)
O6—Ni1—N4—C20	90.7 (3)	Ni2—O2—C14—C15	129.6 (4)
N3—Ni1—N4—C20	2.1 (3)	Ni1—O2—C14—C15	−118.9 (4)
N1—Ni2—O1—C1	16.0 (4)	Ni2—O2—C14—C13	−52.4 (5)
O4—Ni2—O1—C1	−162.0 (4)	Ni1—O2—C14—C13	59.1 (5)
O2—Ni2—O1—C1	116.3 (4)	C18—C13—C14—O2	−178.4 (4)
O5—Ni2—O1—C1	−74.1 (4)	C12—C13—C14—O2	−2.6 (7)
N1—Ni2—O2—C14	−37.5 (3)	C18—C13—C14—C15	−0.2 (7)
O1—Ni2—O2—C14	−129.0 (3)	C12—C13—C14—C15	175.5 (5)
O4—Ni2—O2—C14	140.0 (3)	O2—C14—C15—C16	177.1 (5)
O5—Ni2—O2—C14	120.2 (6)	C13—C14—C15—C16	−1.1 (8)
N2—Ni2—O2—C14	45.6 (3)	C14—C15—C16—C17	1.3 (11)
N1—Ni2—O2—Ni1	−159.14 (15)	C15—C16—C17—C18	−0.2 (11)
O1—Ni2—O2—Ni1	109.33 (13)	C16—C17—C18—C13	−1.1 (9)
O4—Ni2—O2—Ni1	18.34 (12)	C14—C13—C18—C17	1.3 (8)
O5—Ni2—O2—Ni1	−1.5 (7)	C12—C13—C18—C17	−174.5 (5)
N2—Ni2—O2—Ni1	−76.03 (13)	C12—N3—C19—C20	83.1 (5)
O3—Ni1—O2—C14	126.0 (3)	C11—N3—C19—C20	−161.4 (4)
N4—Ni1—O2—C14	33.5 (3)	Ni1—N3—C19—C20	−41.3 (4)
O4—Ni1—O2—C14	−142.6 (3)	C21—N4—C20—C19	147.2 (4)
N3—Ni1—O2—C14	−49.0 (3)	Ni1—N4—C20—C19	−25.5 (5)
O3—Ni1—O2—Ni2	−109.31 (13)	N3—C19—C20—N4	45.7 (5)
N4—Ni1—O2—Ni2	158.27 (14)	C20—N4—C21—C22	−178.2 (5)
O4—Ni1—O2—Ni2	−17.86 (12)	Ni1—N4—C21—C22	−6.2 (8)
N3—Ni1—O2—Ni2	75.72 (13)	N4—C21—C22—C23	179.5 (5)
N4—Ni1—O3—C27	−8.9 (4)	N4—C21—C22—C27	0.9 (9)
O4—Ni1—O3—C27	172.4 (4)	C27—C22—C23—C24	−0.3 (10)
O2—Ni1—O3—C27	−107.8 (4)	C21—C22—C23—C24	−179.0 (6)
O6—Ni1—O3—C27	79.3 (4)	C22—C23—C24—C25	−0.1 (12)
O1—Ni2—O4—C30	56.3 (4)	C23—C24—C25—C26	−0.7 (11)
O2—Ni2—O4—C30	151.3 (4)	C24—C25—C26—C27	1.8 (9)
O5—Ni2—O4—C30	−32.5 (4)	Ni1—O3—C27—C22	6.9 (7)
N2—Ni2—O4—C30	−120.3 (4)	Ni1—O3—C27—C26	−174.2 (3)
O1—Ni2—O4—Ni1	−113.51 (14)	C23—C22—C27—O3	−179.8 (5)
O2—Ni2—O4—Ni1	−18.48 (12)	C21—C22—C27—O3	−1.1 (8)
O5—Ni2—O4—Ni1	157.75 (14)	C23—C22—C27—C26	1.3 (7)
N2—Ni2—O4—Ni1	69.91 (14)	C21—C22—C27—C26	179.9 (5)
O3—Ni1—O4—C30	−56.2 (4)	C25—C26—C27—O3	178.9 (5)
O2—Ni1—O4—C30	−149.4 (4)	C25—C26—C27—C22	−2.1 (7)
O6—Ni1—O4—C30	34.1 (4)	Ni2—O5—C28—C29	−11.4 (7)
N3—Ni1—O4—C30	122.6 (4)	O5—C28—C29—C34	175.3 (5)
O3—Ni1—O4—Ni2	111.66 (14)	O5—C28—C29—C30	−5.9 (8)
O2—Ni1—O4—Ni2	18.42 (12)	Ni2—O4—C30—C31	−154.8 (4)
O6—Ni1—O4—Ni2	−158.05 (14)	Ni1—O4—C30—C31	10.4 (7)
N3—Ni1—O4—Ni2	−69.51 (14)	Ni2—O4—C30—C29	27.1 (6)
N1—Ni2—O5—C28	−158.0 (4)	Ni1—O4—C30—C29	−167.7 (3)
O1—Ni2—O5—C28	−67.4 (4)	C34—C29—C30—O4	176.7 (4)
O4—Ni2—O5—C28	24.4 (4)	C28—C29—C30—O4	−2.1 (7)
O2—Ni2—O5—C28	44.0 (9)	C34—C29—C30—C31	−1.4 (7)
N2—Ni2—O5—C28	118.6 (4)	C28—C29—C30—C31	179.7 (5)
Ni2—O1—C1—C2	166.4 (4)	O4—C30—C31—C32	−176.8 (5)
Ni2—O1—C1—C6	−14.3 (7)	C29—C30—C31—C32	1.4 (7)
O1—C1—C2—C3	−179.4 (5)	C30—C31—C32—C33	−0.7 (9)
C6—C1—C2—C3	1.3 (8)	C31—C32—C33—C34	0.1 (8)
C1—C2—C3—C4	−2.4 (9)	C32—C33—C34—C29	−0.1 (8)
C2—C3—C4—C5	2.1 (10)	C30—C29—C34—C33	0.8 (8)
C3—C4—C5—C6	−0.8 (9)	C28—C29—C34—C33	179.7 (5)
C4—C5—C6—C1	−0.3 (9)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O9B	0.85	2.12	2.859 (15)	145
O7—H7B···O1	0.85	1.85	2.688 (5)	168
O7—H7A···O3	0.85	1.89	2.741 (5)	175
O6—H6B···O7^i	0.85	1.97	2.795 (5)	164
C20—H20A···Cg2^i	0.97	2.68	3.582 (5)	154
C20—H20B···Cg1	0.97	2.73	3.510 (5)	138
C25—H25···Cg3^ii	0.93	2.87	3.552 (6)	131

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2.