Crystal structure of {μ-6,6′-dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methanylyl­idene)]diphenolato}(meth­anol)(nitrato)nickel(II)sodium

Two phenolate O atoms provided by a Schiff base ligand create a double bridge between Ni²⁺ and Na⁺ ions. The coordination environment of the Ni²⁺ ion is square-planar and it has an unusual seven-coordinated geometry: four atoms from the Schiff base ligand, two from a nitrate anion, which coordinates in a bidentate chelating mode, and one O atom from the coordinated methanol mol­ecule. C—H⋯O weak hydrogen-bond inter­actions result in the formation of chains along the b-axis direction which are further assembled by bifurcated O—H⋯O hydrogen bonds and π-stacking inter­actions.

Abstract

In the molecular structure of the title compound, [NaNi(C₁₈H₁₈N₂O₄)(NO₃)(CH₃OH)], the Ni²⁺ ion has a slightly distorted square-planar coordination environment defined by two N and two O atoms which belong to a Schiff base ligand, viz. 6,6′-dimeth­oxy-2,2′-[ethane-1,2-diylbis(nitrilo­methanylyl­idene)]diphenolate. Seven O atoms form the coordination environment of the Na⁺ ion: four from the Schiff base ligand, two from a bidentate chelating nitrate anion and one O atom from a coordinating methanol mol­ecule. In the crystal, the bimetallic complexes are assembled into chains along the b-axis direction via weak C—H⋯O hydrogen-bond inter­actions. Neighbouring chains are in turn connected through bifurcated O—H⋯O hydrogen bonds that involve the coordinating methanol mol­ecules and the nitrate anions, and through π–π stacking inter­actions between phenyl rings of neighbouring mol­ecules.

Chemical context  

Schiff bases are known to be effective ligands able to coord­inate a wide range of different metal ions, and they have been widely utilized in the study of biochemical processes (Lindoy et al., 1976 ▶; Correia et al., 2005 ▶). Compartmental Schiff base ligands, i.e. tetra- and hexa­dentate Schiff base ligands with different ‘compartments’ for different types of metal ions, have been employed extensively as ‘blocking ligands’. Typical examples would be e.g. ligands with an N₂O₄ donor set with two Schiff base N-donor sites, two anionic phenolate donor sites, and two additional ether donor sites. The N₂O₂ compartment is generally more favorable for 3d metal ions. The additional O-donor atoms provide the opportunity to accommodate a second metal ion, which might be a 3d-, 4f-, s- or p-block element, thus allowing the production of di-, tri- or oligonuclear systems (Gheorghe et al., 2006 ▶; Costes et al., 2008 ▶; Andruh et al., 2009 ▶).

Studies on heterometallic complexes began at the end of the 1960s. They are of inter­est because of their physicochemical properties that arise from the presence of dissimilar metal ions in close proximity. The majority of publications in this field are devoted to the preparation of 3d–4f heterometallic complexes (Costes et al., 1998 ▶; Koner et al., 2005 ▶; Sakamoto et al., 2001 ▶). Metal salicylaldimines, on the other hand, represent a fascin­ating group of ligands that are not only effective complexing agents for p- and d-block elements, but also for alkali metal ions similar to the more well known ligand systems such as crown ethers, cryptands etc. Much of the inter­est concerning the coordination chemistry of alkali metal ions originates from the development of mol­ecular systems that can mimic natur­ally occurring mol­ecules that are responsible for the selective transport of these ions, e.g. through membranes. Some of the alkali–metal-ion adducts behave as precursors for other potentially inter­esting mol­ecular species that can be used for small-mol­ecule activation (Gambarotta et al., 1982 ▶), electron storage (Gallo et al., 1997 ▶) and the production of materials with remarkable magnetic properties, the alkali cation being crucial in determining the three-dimensional network in the solid state (Miyasaka et al., 1996 ▶).

In the case of compartmental Schiff base ligands such as e.g. N(imine)₂O(phenoxo)₂O(meth­oxy/eth­oxy)₂, the metal ion may be either retained in the plane of the O₄ donor set or sandwiched between two sets of the Schiff base O atoms. The former case is usually characterized by a coordination number of eight from two O(phenoxo)₂O(meth­oxy/eth­oxy)₂ com­part­ments which belong to different mol­ecules. The latter features a coordination number of six from the O₄ compartment of the Schiff base, and two other donors are provided by coordinating solvent mol­ecules and/or anions. The present paper is devoted to the synthesis and structural analysis of an Ni²⁺-containing complex [NaNi(L)(CH₃OH)(NO₃)], (I), in which the Na⁺ ion has a seven-coordination geometry and where H₂ L is the compartmental Schiff base ligand 6,6′-dimeth­oxy-2,2′-(ethane-1,2-diyldi­imino­dimethyl­ene)diphenol.

Structural commentary  

The mol­ecular structure of compound (I) with the atom numbering is shown in Fig. 1 ▶. Two phenolate O atoms provided by the Schiff base ligand create a double bridge between the Ni²⁺ and Na⁺ ions. The coordination environment of the Ni²⁺ ion is square-planar, formed by two imine N atoms and two phenolate O atoms. The Na⁺ ion has an unusual seven-coordinated geometry in which the ion sits in the plane of the Schiff base O atoms. Further significant inter­actions with two nitrate O atoms and one O atom from the coordin­ating methanol mol­ecule, which are located above and below the plane formed by L, complete the coordination sphere. Values for the geometric parameters in (I) are in good agreement with those observed for complexes based on similar Schiff base ligands (Allen et al., 1987 ▶; Cunningham et al., 2000 ▶; Wang & Shen, 2009 ▶; Xiao, 2009 ▶). The two phenoxo and two meth­oxy O atoms of the O(phenoxo)₂O(eth­oxy)₂ moiety adopt a planar geometry as evidenced by the small mean deviation of the O atoms (<0.02 Å), from the O5/O6/O7/O8 least-squares plane. The deviations of the Na⁺ and Ni²⁺ ions from the O5/O6/O7/O8 plane [0.166 (1) and 0.008 (2) Å, respectively] indicate that Na and Ni are well incorporated in the O(phenoxo)₂O(eth­oxy)₂ moiety.

Figure 1.

The mol­ecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity.

Supra­molecular features  

In the crystal structure, the mol­ecules of the title compound form chains along the b-axis via weak C—H⋯O hydrogen-bond inter­actions (Fig. 2 ▶, Table 1 ▶). The C atom of the ethyl­ene moiety acts as a donor and one O atom of the nitrate anion of the neighboring mol­ecule acts as an acceptor. These chains are further assembled into sheets by a bifurcated O—H⋯O hydrogen bond (Steiner, 2002 ▶), which involves the coordin­ating methanol mol­ecule and nitrate units (Fig. 3 ▶, Table 1 ▶) and through π–π stacking inter­actions, which exist between phenyl rings of neighbouring mol­ecules, with a separation of 3.5845 (11) Å between the centroids formed by the C atoms of the rings [symmetry code: (iii) −x + 1, −y, −z]. For the O—H⋯O hydrogen bond, the O atom of the methanol mol­ecule acts as a donor and the O atoms of the nitrate anion of the neighbouring mol­ecule act as the acceptors.

Figure 2.

The mol­ecular packing for (I), viewed along the b axis. C—H⋯O inter­actions are shown as dashed lines.

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O4H4OO1i	0.82	2.24	2.991(2)	154
O4H4OO3i	0.82	2.49	3.181(2)	143
C8H8BO2ii	0.97	2.65	3.152(2)	112

Symmetry codes: (i) ; (ii) .

Figure 3.

O—H⋯O and π–π contacts for (I), shown as dashed lines, with ring centroids shown as coloured spheres.

Synthesis and crystallization  

A mixture of 6,6′-dimeth­oxy-2,2′-(ethane-1,2-diyldi­imino­dimethyl­ene)diphenol (1 mmol) and nickel nitrate (1 mmol) in methanol (15 ml) was stirred for 30 min at room temperature. Then, sodium nitrate (1mmol) was added, and the mixture was stirred for another 30 min and filtered. The resulting clear orange filtrate was left at ambient temperature for crystallization in air. The red–orange block-shaped crystals were collected by filtration after 6 d, washed with chilled iso­propanol and dried on filter paper (yield 0.28 g, 56%).

Refinement  

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.95 (aromatic) or 0.99 Å (methyl­ene), with U _iso(H) = 1.2U _eq(C), C—H = 0.98 Å for methyl H atoms, with U _iso(H) = 1.5U _eq(C), and O—H = 0.82 Å for the hy­droxy group of methanol, with U _iso(H) = 1.5U _eq(O). Crystal data, data collection and structure refinement details are summarized in Table 2 ▶.

Table 2. Experimental details.

Crystal data
Chemical formula	[NaNi(C18H18N2O4)(NO3)(CH4O)]
M r	502.09
Crystal system, space group	Triclinic, P
Temperature (K)	293
a, b, c ()	7.207(1), 11.047(1), 13.619(1)
, , ()	95.30(1), 99.81(1), 99.05(1)
V (3)	1047.2(2)
Z	2
Radiation type	Mo K
(mm1)	1.00
Crystal size (mm)	0.4 0.2 0.2
Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003 ▶)
T min, T max	0.690, 0.825
No. of measured, independent and observed [I > 2(I)] reflections	12718, 6501, 4324
R int	0.020
(sin /)max (1)	0.744
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.035, 0.081, 0.90
No. of reflections	6501
No. of parameters	292
H-atom treatment	H-atom parameters constrained
max, min (e 3)	0.50, 0.32

Computer programs: COLLECT (Nonius, 1999 ▶), DENZO/SCALEPACK (Otwinowski Minor, 1997 ▶), SHELXS97 and SHELXL2014 (Sheldrick, 2008 ▶), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ▶).

Supplementary Material

CCDC reference: 1026857

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

[NaNi(C18H18N2O4)(NO3)(CH4O)]	Z = 2
Mr = 502.09	F(000) = 520
Triclinic, P1	Dx = 1.592 Mg m−3
a = 7.207 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.047 (1) Å	Cell parameters from 12718 reflections
c = 13.619 (1) Å	θ = 2.9–31.9°
α = 95.30 (1)°	µ = 1.00 mm−1
β = 99.81 (1)°	T = 293 K
γ = 99.05 (1)°	Block, white
V = 1047.2 (2) Å3	0.4 × 0.2 × 0.2 mm

Data collection

Nonius KappaCCD diffractometer	4324 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	Rint = 0.020
φ scans and ω scans with κ offset	θmax = 31.9°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→10
Tmin = 0.690, Tmax = 0.825	k = −15→15
12718 measured reflections	l = −19→20
6501 independent reflections

Refinement

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.035	H-atom parameters constrained
wR(F2) = 0.081	w = 1/[σ2(Fo2) + (0.0431P)2] where P = (Fo2 + 2Fc2)/3
S = 0.90	(Δ/σ)max < 0.001
6501 reflections	Δρmax = 0.50 e Å−3
292 parameters	Δρmin = −0.32 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
N1	1.3085 (3)	0.47914 (14)	0.20473 (11)	0.0500 (4)
N2	1.0634 (2)	−0.10231 (12)	0.31510 (10)	0.0414 (3)
N3	0.87587 (19)	−0.13606 (11)	0.13663 (10)	0.0384 (3)
O1	1.3115 (2)	0.36716 (13)	0.19219 (14)	0.0823 (5)
O2	1.1514 (2)	0.51204 (13)	0.20629 (12)	0.0692 (4)
O3	1.4575 (2)	0.55470 (16)	0.21536 (12)	0.0840 (5)
O4	0.7094 (2)	0.36010 (15)	0.29641 (10)	0.0708 (4)
H4O	0.6210	0.3784	0.2582	0.106*
O5	1.04924 (18)	0.14171 (10)	0.31975 (8)	0.0439 (3)
O6	0.87634 (17)	0.10986 (10)	0.14652 (8)	0.0401 (3)
O7	0.7790 (2)	0.29628 (11)	0.06339 (9)	0.0531 (3)
O8	1.1398 (2)	0.36213 (11)	0.41444 (9)	0.0539 (3)
C1	1.2043 (2)	0.27108 (16)	0.46557 (12)	0.0417 (4)
C2	1.3145 (3)	0.28976 (19)	0.56084 (13)	0.0504 (4)
H2	1.3492	0.3688	0.5958	0.060*
C3	1.3734 (3)	0.1895 (2)	0.60439 (14)	0.0592 (5)
H3	1.4487	0.2022	0.6683	0.071*
C4	1.3227 (3)	0.0743 (2)	0.55493 (13)	0.0554 (5)
H4	1.3625	0.0085	0.5856	0.067*
C5	1.2091 (2)	0.05142 (16)	0.45629 (12)	0.0419 (4)
C6	1.1504 (2)	0.15157 (15)	0.41092 (11)	0.0380 (4)
C7	1.1604 (3)	−0.07053 (17)	0.40535 (13)	0.0457 (4)
H7	1.2019	−0.1330	0.4399	0.055*
C8	1.0406 (3)	−0.23159 (17)	0.27149 (14)	0.0585 (5)
H8A	1.0011	−0.2860	0.3189	0.070*
H8B	1.1616	−0.2488	0.2568	0.070*
C9	0.8924 (3)	−0.25411 (15)	0.17663 (15)	0.0578 (5)
H9A	0.9287	−0.3105	0.1274	0.069*
H9B	0.7699	−0.2914	0.1905	0.069*
C10	0.7997 (2)	−0.13762 (15)	0.04360 (13)	0.0411 (4)
H10	0.7711	−0.2136	0.0037	0.049*
C11	0.7552 (2)	−0.03232 (15)	−0.00347 (11)	0.0366 (3)
C12	0.6631 (3)	−0.04768 (17)	−0.10544 (12)	0.0455 (4)
H12	0.6384	−0.1255	−0.1424	0.055*
C13	0.6106 (3)	0.04949 (18)	−0.14969 (12)	0.0489 (4)
H13	0.5500	0.0374	−0.2167	0.059*
C14	0.6459 (2)	0.16813 (16)	−0.09638 (12)	0.0419 (4)
H14	0.6087	0.2342	−0.1276	0.050*
C15	0.7366 (2)	0.18574 (15)	0.00292 (11)	0.0372 (4)
C16	0.7923 (2)	0.08597 (14)	0.05155 (11)	0.0340 (3)
C17	0.7114 (4)	0.39946 (18)	0.02595 (15)	0.0719 (7)
H17A	0.7727	0.4218	−0.0287	0.108*
H17B	0.7399	0.4676	0.0784	0.108*
H17C	0.5755	0.3791	0.0027	0.108*
C18	1.2117 (4)	0.48674 (18)	0.45544 (16)	0.0714 (7)
H18A	1.1842	0.5002	0.5217	0.107*
H18B	1.1519	0.5405	0.4136	0.107*
H18C	1.3475	0.5039	0.4587	0.107*
C19	0.6357 (4)	0.2606 (2)	0.34481 (17)	0.0756 (7)
H19A	0.6104	0.1856	0.2994	0.113*
H19B	0.5192	0.2755	0.3650	0.113*
H19C	0.7275	0.2531	0.4029	0.113*
Ni1	0.96567 (3)	0.00143 (2)	0.22924 (2)	0.03524 (7)
Na1	0.97774 (10)	0.30835 (6)	0.23162 (5)	0.04288 (16)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0603 (11)	0.0439 (9)	0.0431 (8)	0.0079 (8)	0.0013 (7)	0.0085 (7)
N2	0.0517 (9)	0.0324 (7)	0.0464 (8)	0.0153 (6)	0.0169 (7)	0.0103 (6)
N3	0.0379 (8)	0.0283 (7)	0.0493 (8)	0.0060 (5)	0.0091 (6)	0.0051 (6)
O1	0.0755 (12)	0.0449 (9)	0.1300 (14)	0.0208 (8)	0.0217 (10)	0.0081 (9)
O2	0.0728 (11)	0.0523 (9)	0.0915 (11)	0.0276 (8)	0.0203 (8)	0.0175 (7)
O3	0.0702 (12)	0.0779 (11)	0.0851 (11)	−0.0239 (9)	−0.0063 (8)	0.0156 (9)
O4	0.0659 (10)	0.0912 (11)	0.0610 (9)	0.0337 (9)	0.0065 (7)	0.0143 (8)
O5	0.0570 (8)	0.0342 (6)	0.0367 (6)	0.0132 (5)	−0.0063 (5)	0.0041 (5)
O6	0.0512 (7)	0.0295 (6)	0.0350 (6)	0.0094 (5)	−0.0055 (5)	0.0019 (4)
O7	0.0809 (10)	0.0335 (6)	0.0400 (6)	0.0180 (6)	−0.0087 (6)	0.0025 (5)
O8	0.0715 (9)	0.0379 (7)	0.0434 (7)	0.0095 (6)	−0.0106 (6)	−0.0001 (5)
C1	0.0384 (10)	0.0475 (10)	0.0373 (8)	0.0068 (7)	0.0027 (7)	0.0043 (7)
C2	0.0466 (11)	0.0605 (12)	0.0384 (9)	0.0031 (9)	0.0000 (8)	0.0025 (8)
C3	0.0523 (13)	0.0792 (15)	0.0418 (10)	0.0118 (10)	−0.0052 (8)	0.0112 (10)
C4	0.0549 (13)	0.0717 (14)	0.0440 (10)	0.0226 (10)	0.0022 (8)	0.0227 (9)
C5	0.0403 (10)	0.0495 (10)	0.0397 (9)	0.0145 (8)	0.0076 (7)	0.0131 (7)
C6	0.0339 (9)	0.0467 (10)	0.0344 (8)	0.0092 (7)	0.0049 (6)	0.0089 (7)
C7	0.0502 (11)	0.0501 (11)	0.0467 (10)	0.0230 (8)	0.0145 (8)	0.0231 (8)
C8	0.0886 (16)	0.0380 (10)	0.0563 (11)	0.0250 (10)	0.0168 (10)	0.0146 (8)
C9	0.0685 (14)	0.0264 (9)	0.0742 (13)	0.0049 (8)	0.0038 (10)	0.0070 (8)
C10	0.0410 (10)	0.0290 (8)	0.0507 (10)	0.0018 (7)	0.0107 (7)	−0.0052 (7)
C11	0.0338 (9)	0.0360 (8)	0.0386 (8)	0.0031 (6)	0.0076 (6)	0.0006 (6)
C12	0.0492 (11)	0.0443 (10)	0.0379 (9)	0.0016 (8)	0.0075 (7)	−0.0079 (7)
C13	0.0497 (11)	0.0615 (12)	0.0309 (8)	0.0046 (9)	0.0022 (7)	0.0003 (8)
C14	0.0421 (10)	0.0480 (10)	0.0357 (8)	0.0098 (7)	0.0044 (7)	0.0083 (7)
C15	0.0378 (9)	0.0377 (9)	0.0352 (8)	0.0079 (7)	0.0036 (6)	0.0043 (6)
C16	0.0326 (9)	0.0327 (8)	0.0346 (8)	0.0039 (6)	0.0041 (6)	0.0009 (6)
C17	0.111 (2)	0.0414 (11)	0.0596 (12)	0.0280 (11)	−0.0082 (12)	0.0091 (9)
C18	0.0865 (18)	0.0455 (12)	0.0671 (13)	0.0025 (11)	−0.0136 (12)	−0.0035 (10)
C19	0.0713 (17)	0.0801 (17)	0.0719 (15)	0.0061 (13)	0.0154 (12)	0.0002 (13)
Ni1	0.03972 (13)	0.02768 (11)	0.03891 (12)	0.00921 (8)	0.00475 (8)	0.00648 (8)
Na1	0.0529 (4)	0.0312 (3)	0.0421 (3)	0.0085 (3)	0.0013 (3)	0.0039 (3)

Geometric parameters (Å, º)

N1—O3	1.230 (2)	C4—C5	1.427 (2)
N1—O1	1.2372 (19)	C4—H4	0.9300
N1—O2	1.246 (2)	C5—C6	1.403 (2)
N1—Na1	2.8961 (19)	C5—C7	1.420 (2)
N2—C7	1.293 (2)	C7—H7	0.9300
N2—C8	1.468 (2)	C8—C9	1.503 (3)
N2—Ni1	1.8433 (13)	C8—H8A	0.9700
N3—C10	1.290 (2)	C8—H8B	0.9700
N3—C9	1.473 (2)	C9—H9A	0.9700
N3—Ni1	1.8371 (13)	C9—H9B	0.9700
O1—Na1	2.5512 (19)	C10—C11	1.432 (2)
O2—Na1	2.4806 (16)	C10—H10	0.9300
O4—C19	1.412 (3)	C11—C16	1.408 (2)
O4—Na1	2.3837 (17)	C11—C12	1.416 (2)
O4—H4O	0.8151	C12—C13	1.352 (3)
O5—C6	1.3139 (18)	C12—H12	0.9300
O5—Ni1	1.8396 (11)	C13—C14	1.402 (2)
O5—Na1	2.3644 (12)	C13—H13	0.9300
O6—C16	1.3148 (17)	C14—C15	1.380 (2)
O6—Ni1	1.8339 (10)	C14—H14	0.9300
O6—Na1	2.3288 (12)	C15—C16	1.413 (2)
O7—C15	1.3689 (19)	C17—H17A	0.9600
O7—C17	1.412 (2)	C17—H17B	0.9600
O7—Na1	2.4666 (13)	C17—H17C	0.9600
O8—C1	1.371 (2)	C18—H18A	0.9600
O8—C18	1.418 (2)	C18—H18B	0.9600
O8—Na1	2.5364 (13)	C18—H18C	0.9600
C1—C2	1.380 (2)	C19—Na1	3.125 (3)
C1—C6	1.416 (2)	C19—H19A	0.9600
C2—C3	1.394 (3)	C19—H19B	0.9600
C2—H2	0.9300	C19—H19C	0.9600
C3—C4	1.349 (3)	Ni1—Na1	3.3749 (7)
C3—H3	0.9300
O3—N1—O1	120.31 (19)	O6—C16—C11	123.80 (14)
O3—N1—O2	121.67 (18)	O6—C16—C15	117.42 (13)
O1—N1—O2	118.02 (17)	C11—C16—C15	118.78 (13)
O3—N1—Na1	166.28 (12)	O7—C17—H17A	109.5
O1—N1—Na1	61.59 (11)	O7—C17—H17B	109.5
O2—N1—Na1	58.35 (10)	H17A—C17—H17B	109.5
C7—N2—C8	118.06 (14)	O7—C17—H17C	109.5
C7—N2—Ni1	126.55 (12)	H17A—C17—H17C	109.5
C8—N2—Ni1	115.16 (11)	H17B—C17—H17C	109.5
C10—N3—C9	118.99 (14)	O8—C18—H18A	109.5
C10—N3—Ni1	126.49 (11)	O8—C18—H18B	109.5
C9—N3—Ni1	114.51 (11)	H18A—C18—H18B	109.5
N1—O1—Na1	93.16 (12)	O8—C18—H18C	109.5
N1—O2—Na1	96.34 (11)	H18A—C18—H18C	109.5
C19—O4—Na1	108.10 (13)	H18B—C18—H18C	109.5
C19—O4—H4O	108.2	O4—C19—Na1	46.47 (10)
Na1—O4—H4O	119.0	O4—C19—H19A	109.5
C6—O5—Ni1	127.75 (10)	Na1—C19—H19A	79.9
C6—O5—Na1	125.60 (10)	O4—C19—H19B	109.5
Ni1—O5—Na1	106.12 (5)	Na1—C19—H19B	155.4
C16—O6—Ni1	127.73 (10)	H19A—C19—H19B	109.5
C16—O6—Na1	123.96 (9)	O4—C19—H19C	109.5
Ni1—O6—Na1	107.75 (5)	Na1—C19—H19C	87.4
C15—O7—C17	118.69 (13)	H19A—C19—H19C	109.5
C15—O7—Na1	118.60 (9)	H19B—C19—H19C	109.5
C17—O7—Na1	122.69 (10)	O6—Ni1—N3	95.02 (5)
C1—O8—C18	118.12 (13)	O6—Ni1—O5	83.21 (5)
C1—O8—Na1	118.85 (9)	N3—Ni1—O5	178.04 (5)
C18—O8—Na1	120.66 (11)	O6—Ni1—N2	177.63 (6)
O8—C1—C2	125.03 (16)	N3—Ni1—N2	87.08 (6)
O8—C1—C6	113.83 (13)	O5—Ni1—N2	94.71 (6)
C2—C1—C6	121.13 (16)	O6—Ni1—Na1	41.09 (3)
C1—C2—C3	119.59 (18)	N3—Ni1—Na1	135.99 (4)
C1—C2—H2	120.2	O5—Ni1—Na1	42.30 (3)
C3—C2—H2	120.2	N2—Ni1—Na1	136.74 (5)
C4—C3—C2	120.82 (16)	O6—Na1—O5	62.62 (4)
C4—C3—H3	119.6	O6—Na1—O4	105.64 (6)
C2—C3—H3	119.6	O5—Na1—O4	102.21 (5)
C3—C4—C5	121.15 (18)	O6—Na1—O7	64.88 (4)
C3—C4—H4	119.4	O5—Na1—O7	127.21 (5)
C5—C4—H4	119.4	O4—Na1—O7	86.56 (5)
C6—C5—C7	121.30 (15)	O6—Na1—O2	139.36 (6)
C6—C5—C4	118.75 (17)	O5—Na1—O2	136.66 (5)
C7—C5—C4	119.95 (16)	O4—Na1—O2	103.03 (6)
O5—C6—C5	123.93 (15)	O7—Na1—O2	88.99 (5)
O5—C6—C1	117.52 (14)	O6—Na1—O8	125.89 (5)
C5—C6—C1	118.55 (14)	O5—Na1—O8	63.39 (4)
N2—C7—C5	125.72 (15)	O4—Na1—O8	82.22 (5)
N2—C7—H7	117.1	O7—Na1—O8	166.29 (5)
C5—C7—H7	117.1	O2—Na1—O8	85.91 (5)
N2—C8—C9	109.13 (14)	O6—Na1—O1	102.51 (5)
N2—C8—H8A	109.9	O5—Na1—O1	95.38 (5)
C9—C8—H8A	109.9	O4—Na1—O1	151.34 (6)
N2—C8—H8B	109.9	O7—Na1—O1	100.68 (6)
C9—C8—H8B	109.9	O2—Na1—O1	50.02 (5)
H8A—C8—H8B	108.3	O8—Na1—O1	85.75 (6)
N3—C9—C8	109.49 (14)	O6—Na1—N1	124.94 (5)
N3—C9—H9A	109.8	O5—Na1—N1	114.82 (5)
C8—C9—H9A	109.8	O4—Na1—N1	126.53 (6)
N3—C9—H9B	109.8	O7—Na1—N1	98.99 (5)
C8—C9—H9B	109.8	O2—Na1—N1	25.31 (4)
H9A—C9—H9B	108.2	O8—Na1—N1	81.61 (5)
N3—C10—C11	125.54 (14)	O1—Na1—N1	25.25 (4)
N3—C10—H10	117.2	O6—Na1—C19	88.26 (6)
C11—C10—H10	117.2	O5—Na1—C19	77.74 (6)
C16—C11—C12	119.08 (15)	O4—Na1—C19	25.43 (6)
C16—C11—C10	120.98 (14)	O7—Na1—C19	95.80 (6)
C12—C11—C10	119.84 (14)	O2—Na1—C19	126.74 (6)
C13—C12—C11	120.74 (15)	O8—Na1—C19	77.25 (6)
C13—C12—H12	119.6	O1—Na1—C19	162.98 (6)
C11—C12—H12	119.6	N1—Na1—C19	146.80 (6)
C12—C13—C14	121.20 (15)	O6—Na1—Ni1	31.17 (3)
C12—C13—H13	119.4	O5—Na1—Ni1	31.58 (3)
C14—C13—H13	119.4	O4—Na1—Ni1	108.42 (5)
C15—C14—C13	119.21 (16)	O7—Na1—Ni1	96.03 (3)
C15—C14—H14	120.4	O2—Na1—Ni1	148.38 (4)
C13—C14—H14	120.4	O8—Na1—Ni1	94.97 (3)
O7—C15—C14	125.11 (15)	O1—Na1—Ni1	98.44 (4)
O7—C15—C16	113.90 (12)	N1—Na1—Ni1	123.52 (4)
C14—C15—C16	120.99 (15)	C19—Na1—Ni1	83.90 (5)
O3—N1—O1—Na1	164.40 (14)	C12—C13—C14—C15	0.3 (3)
O2—N1—O1—Na1	−15.51 (17)	C17—O7—C15—C14	6.0 (3)
O3—N1—O2—Na1	−163.87 (15)	Na1—O7—C15—C14	−172.37 (14)
O1—N1—O2—Na1	16.04 (18)	C17—O7—C15—C16	−173.20 (18)
C18—O8—C1—C2	9.2 (3)	Na1—O7—C15—C16	8.43 (19)
Na1—O8—C1—C2	171.84 (14)	C13—C14—C15—O7	−179.79 (16)
C18—O8—C1—C6	−169.82 (18)	C13—C14—C15—C16	−0.6 (3)
Na1—O8—C1—C6	−7.19 (19)	Ni1—O6—C16—C11	0.5 (2)
O8—C1—C2—C3	−179.16 (17)	Na1—O6—C16—C11	170.80 (12)
C6—C1—C2—C3	−0.2 (3)	Ni1—O6—C16—C15	−179.59 (11)
C1—C2—C3—C4	−0.6 (3)	Na1—O6—C16—C15	−9.3 (2)
C2—C3—C4—C5	0.6 (3)	C12—C11—C16—O6	179.76 (15)
C3—C4—C5—C6	0.1 (3)	C10—C11—C16—O6	3.2 (3)
C3—C4—C5—C7	178.98 (19)	C12—C11—C16—C15	−0.2 (2)
Ni1—O5—C6—C5	−1.7 (2)	C10—C11—C16—C15	−176.70 (15)
Na1—O5—C6—C5	−172.10 (12)	O7—C15—C16—O6	−0.1 (2)
Ni1—O5—C6—C1	177.62 (12)	C14—C15—C16—O6	−179.34 (15)
Na1—O5—C6—C1	7.2 (2)	O7—C15—C16—C11	179.82 (15)
C7—C5—C6—O5	−0.5 (3)	C14—C15—C16—C11	0.6 (2)
C4—C5—C6—O5	178.43 (16)	C16—O6—Ni1—N3	−4.68 (14)
C7—C5—C6—C1	−179.72 (16)	Na1—O6—Ni1—N3	−176.25 (6)
C4—C5—C6—C1	−0.8 (3)	C16—O6—Ni1—O5	176.15 (14)
O8—C1—C6—O5	0.7 (2)	Na1—O6—Ni1—O5	4.58 (6)
C2—C1—C6—O5	−178.41 (16)	C16—O6—Ni1—Na1	171.57 (17)
O8—C1—C6—C5	179.98 (15)	C10—N3—Ni1—O6	7.18 (15)
C2—C1—C6—C5	0.9 (3)	C9—N3—Ni1—O6	−171.60 (13)
C8—N2—C7—C5	174.90 (17)	C10—N3—Ni1—N2	−171.71 (15)
Ni1—N2—C7—C5	0.6 (3)	C9—N3—Ni1—N2	9.50 (13)
C6—C5—C7—N2	1.0 (3)	C10—N3—Ni1—Na1	3.64 (18)
C4—C5—C7—N2	−177.89 (17)	C9—N3—Ni1—Na1	−175.15 (10)
C7—N2—C8—C9	168.53 (17)	C6—O5—Ni1—O6	−176.40 (15)
Ni1—N2—C8—C9	−16.6 (2)	Na1—O5—Ni1—O6	−4.48 (6)
C10—N3—C9—C8	160.57 (16)	C6—O5—Ni1—N2	2.46 (15)
Ni1—N3—C9—C8	−20.5 (2)	Na1—O5—Ni1—N2	174.39 (6)
N2—C8—C9—N3	22.7 (2)	C6—O5—Ni1—Na1	−171.92 (17)
C9—N3—C10—C11	173.00 (16)	C7—N2—Ni1—N3	178.85 (16)
Ni1—N3—C10—C11	−5.7 (3)	C8—N2—Ni1—N3	4.44 (14)
N3—C10—C11—C16	−0.5 (3)	C7—N2—Ni1—O5	−1.95 (16)
N3—C10—C11—C12	−177.00 (17)	C8—N2—Ni1—O5	−176.35 (13)
C16—C11—C12—C13	−0.2 (3)	C7—N2—Ni1—Na1	3.57 (19)
C10—C11—C12—C13	176.39 (16)	C8—N2—Ni1—Na1	−170.84 (11)
C11—C12—C13—C14	0.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O1i	0.82	2.24	2.991 (2)	154
O4—H4O···O3i	0.82	2.49	3.181 (2)	143
C8—H8B···O2ii	0.97	2.65	3.152 (2)	112

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