A novel Na–O–Ni–O–Ni bridging complex of Cl-HXTA, where Cl-HXTA is 2,6-bis{[bis­(carboxyl­ato­methyl)­amino]­methyl}-4-chloro­phenolate

In the structure of the title compound, hepta­aqua-1κ³O,2κ²O,3κ²O-(μ₃-2,6-bis{[bis­(carboxyl­ato­methyl)­amino]methyl}-4-chloro­phenolato-1κO;2κ⁴O,O′,N,O¹;3κ⁴O¹N′,O′′,O′′′)dinickel(II)­sodium(I) pentahydrate, [NaNi₂(C₁₆H₁₄ClN₂O₉)(H₂O)₇]·5H₂O or [Ni₂(Cl-HXTA)(H₂O)₄{Na(H₂O)₃}]·5H₂O, the trinuclear complex unit consists of two distorted NiNO₅ octahedra bridged by a phenolate O atom and an NaO₄ tetrahedron bridged to one of the Ni octahedra by a carboxylate O atom. There are four intramolecular hydrogen bonds forming four six-membered rings in the complex and the complex mol­ecules are connected to each other by a very complicated hydrogen-bond network.

S1. Comment

In nickel enzymes, such as urease, Ni^II ions can catalyze the hydrolysis of urea (Jabri et al., 1995). Cl-HXTA is a versatile 'end-off'-type acidic dinucleating ligand suitable for incorporating various dinuclear cores, first reported by Que and co-workers (Murch et al., 1987). It functions as a pentavalent anionic ligand with four methoxycarbonyl chelating arms, possessing two NO₃ coordination sites, and most of its dinuclear metal complexes are soluble in water. We report here the crystal structure of the title trinuclear complex, (I), containing an Ni—O—Ni—O—Na bridge with Cl-HXTA. \sch

Some features of the molecular geometry in (I) are presented in Table 1 and Fig. 1. In this trinuclear complex, both Ni²⁺ ions are located in similar coordination spheres. Each sphere has a distorted octahedral geometry comprised of two carboxylate groups, a tertiary N atom, two water molecules and an oxo-bridging phenolate ligand. This is in contrast with the structure of [Fe₂(HXTA)OH(H₂O)₂] (Murch et al., 1987), in which the coordination sphere of each Fe atom has the same geometry and coordination set and there are two bridges between the Fe^II cations.

The average Ni—O(phenolate) bond length in (I) is 2.051 Å and this compares well with the analogous bonds in other phenolate-bridged dimers(Chiari et al., 1982, 1983). At each Ni²⁺ centre, the two water molecules and the tertiary N atom, as well as the bridging O atom from the phenolate ligand, are almost coplanar. The Ni1—Ni2 distance is 3.75 Å, slightly longer than that in [Ni₂(Me₄-tpdp)(MeCO₂)(H₂O)₂](ClO₄)₂ (3.62 Å; Yamaguchi et al., 2001). The Ni1—O1—Ni2 angle [132.2 (1)°] is much larger than the Fe1—O—Fe2 angle in [Fe₂(HXTA)OH(H₂O)₂] (102.6°; Murch et al., 1987), perhaps due to the presence of only one oxo-bridge between the two Ni²⁺ ions but two oxo-bridges between the two Fe²⁺ ions. Furthermore, in complex (I), atom O3 not only coordinates to atom Ni1 but also to an Na⁺ ion, at a distance of 2.307 (3) Å. Therefore, atom O3 acts as a bridge between atoms Na1 and Ni1, with an Ni1—O—Na1 angle of 124.6 (2)°. The Na⁺ ion completes its tetrahedral geometry with three other coordinated water molecules, with Na—O distances in the range 2.213 (3)–2.355 (5) Å. Thus, this complex is actually a trinuclear complex. The Ni1···Na1 distance is 3.837 Å.

The hydrogen-bonding geometry in (I) is listed in Table 2 and illustrated in Figs. 1 and 2. A number of intra- and intermolecular hydrogen bonds stabilize the crystal structure. There are four intramolecular hydrogen bonds in the complex, namely O3W—H···O5, O1W—H···O9, O1W—H···O7 and O2W—H···O5W, forming four six-membered rings (Fig. 1). In particular, water molecule O1W is coordinated to atom Ni1, forming two hydrogen bonds via water molecule O7W bonded to Na1 and atom O9 bonded to Ni2, making the complex more stable. Because four carboxylate groups and seven coordinated water molecules, as well as five non-coordinated water molecules, are included in this compound, a very complicated hydrogen-bond network (Fig.2) is formed, connecting every complex with each other.

S2. Experimental

All chemicals were of reagent grade and commercially available from the Beijing Chemical Reagents Company of China, and were used without further purification. The ligand Cl-HXTA was synthesized by a modification of the published procedures of Murch et al. (1987) and Branum et al. (2001). To an aqueous solution (100 ml) containing iminodiacetic acid (16.7 g, 0.125 mol) and p-chlorophenol (8.07 g, 0.063 mol) was added NaOH (10.5 g, 0.25 mol) in water (40 ml), and the mixture was cooled in an ice-water bath. Upon dissolution, 37% formaldehyde (15 ml) was added dropwise at 273 K. The solution was stirred for 30 min, heated at 343 K for 4 h, and then concentrated to dryness. Recrystallization of the solid from methanol yielded lighter yellow crystals of Na₄(Cl-HXTA). Yield 90%. Ni(CH₃COO)₂·4H₂O (0.496 g, 2.0 mmol) and Na₄(Cl-HXTA) (0.516 g, 1.0 mmol) were dissolved in two aliquots of water (5 ml) and mixed with stirring at 323 K for 3 h. The resulting pale-green solution was filtered and the filtrate was left to stand at room temperature. Emerald crystals of the title compound appeared after 10 d by slow evaporation of the aqueous solvent.

S3. Refinement

The residual electron density has a maximum located 0.75 Å from atom H8WB. H atoms attached to C atoms were placed in geometrically idealized positions, with Csp³—H = 0.99 Å and Csp²—H = 0.95 Å, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C). H atoms attached to O atoms (water) were located in difference Fourier maps and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(O). The O—H distances are in the range 0.841–0.866 Å.

Computing details

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

Figures

	Fig. 1. The structure of (I), with 30% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii and hydrogen bonds are indicated by dashed lines. Please provide symmetry codes for suffixes A to C.
	Fig. 2. The hydrogen-bond network (dashed lines) of (I). Atoms labelled with the suffixes A, B or C are at the symmetry positions (x, y − 1, z), (1 − x, −y, 1 − z) or (1 − x, 1 − y, 1 − z), respectively. Please provide missing codes for suffixes D to H.

heptaaqua-1κ³O,2κ²O,3κ²O-(µ₃-2,6- bis{[bis(carboxylatomethyl)amino]methyl}-4-chlorophenolato- 1κO;2κ⁴O,O',N,O¹;3κ⁴O¹N',O'',O''')dinickel(II)sodium(I) pentahydrate

Crystal data

[NaNi2(C16H14ClN2O9)(H2O)7]·5H2O	Z = 2
Mr = 770.34	F(000) = 800
Triclinic, P1	Dx = 1.711 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.292 (3) Å	Cell parameters from 2006 reflections
b = 11.564 (3) Å	θ = 2.4–25.2°
c = 13.944 (4) Å	µ = 1.45 mm^−1
α = 95.843 (3)°	T = 183 K
β = 109.438 (3)°	Columnar, blue
γ = 103.123 (3)°	0.40 × 0.10 × 0.10 mm
V = 1495.4 (7) Å^3

Data collection

Bruker SMART 1K CCD area-detector diffractometer	5126 independent reflections
Radiation source: fine-focus sealed tube	3733 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −12→12
Tmin = 0.594, Tmax = 0.868	k = −13→12
6134 measured reflections	l = −16→11

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0188P)^2] where P = (Fo^2 + 2Fc^2)/3
5086 reflections	(Δ/σ)max < 0.001
388 parameters	Δρmax = 0.89 e Å^−3
16 restraints	Δρmin = −0.72 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
Na1	0.74993 (19)	0.41245 (17)	0.16994 (15)	0.0518 (6)
Ni1	0.42830 (6)	0.28036 (5)	0.24495 (4)	0.02425 (16)
Ni2	0.35774 (6)	−0.03522 (4)	0.29724 (4)	0.02160 (15)
N1	0.2515 (3)	0.2959 (3)	0.1269 (3)	0.0249 (8)
N2	0.4481 (3)	−0.1385 (3)	0.2216 (3)	0.0206 (8)
C1	0.2021 (5)	−0.0557 (4)	−0.1025 (3)	0.0293 (11)
C2	0.1485 (4)	0.0329 (4)	−0.0677 (3)	0.0287 (11)
H2	0.0748	0.0582	−0.1149	0.034*
C3	0.2041 (4)	0.0844 (4)	0.0376 (3)	0.0249 (10)
C4	0.3133 (4)	0.0470 (3)	0.1071 (3)	0.0223 (10)
C5	0.3665 (4)	−0.0412 (3)	0.0693 (3)	0.0225 (10)
C6	0.3094 (4)	−0.0923 (4)	−0.0357 (3)	0.0284 (11)
H6	0.3450	−0.1529	−0.0612	0.034*
C7	0.1444 (4)	0.1751 (4)	0.0796 (3)	0.0269 (10)
H71	0.1093	0.1441	0.1327	0.032*
H72	0.0614	0.1848	0.0229	0.032*
C8	0.3048 (4)	0.3484 (4)	0.0499 (3)	0.0280 (11)
H81	0.3166	0.4366	0.0616	0.034*
H82	0.2327	0.3126	−0.0206	0.034*
C9	0.4478 (5)	0.3257 (4)	0.0563 (4)	0.0259 (10)
C10	0.1892 (5)	0.3735 (4)	0.1792 (3)	0.0313 (11)
H11	0.0852	0.3555	0.1389	0.038*
H12	0.2344	0.4595	0.1815	0.038*
C11	0.2114 (5)	0.3536 (4)	0.2874 (4)	0.0346 (12)
C12	0.4889 (4)	−0.0746 (4)	0.1429 (3)	0.0235 (10)
H13	0.5683	−0.0003	0.1794	0.028*
H14	0.5242	−0.1277	0.1032	0.028*
C13	0.3377 (4)	−0.2546 (3)	0.1712 (3)	0.0281 (11)
H15	0.3519	−0.3134	0.2178	0.034*
H16	0.3491	−0.2870	0.1068	0.034*
C14	0.1856 (5)	−0.2415 (4)	0.1446 (3)	0.0263 (10)
C15	0.5792 (4)	−0.1478 (4)	0.3013 (3)	0.0276 (11)
H17	0.6477	−0.1606	0.2683	0.033*
H18	0.5550	−0.2191	0.3324	0.033*
C16	0.6500 (5)	−0.0359 (4)	0.3862 (3)	0.0231 (10)
Cl1	0.12907 (13)	−0.12235 (12)	−0.23448 (9)	0.0509 (4)
O1	0.3644 (3)	0.0940 (2)	0.2082 (2)	0.0209 (6)
O2	0.4919 (3)	0.3473 (3)	−0.0147 (2)	0.0362 (8)
O3	0.5209 (3)	0.2935 (2)	0.1376 (2)	0.0275 (7)
O4	0.1479 (4)	0.4020 (3)	0.3362 (3)	0.0495 (10)
O5	0.3005 (3)	0.2955 (2)	0.3294 (2)	0.0311 (7)
O6	0.0867 (3)	−0.3243 (3)	0.0795 (2)	0.0369 (8)
O7	0.1692 (3)	−0.1506 (2)	0.1940 (2)	0.0270 (7)
O8	0.7733 (3)	−0.0233 (3)	0.4467 (2)	0.0324 (7)
O9	0.5758 (3)	0.0376 (2)	0.3921 (2)	0.0274 (7)
O1W	0.6007 (3)	0.2757 (2)	0.36983 (17)	0.0379 (8)
H21	0.6222	0.2122	0.3806	0.046*
H22	0.6715	0.3198	0.3619	0.046*
O2W	0.5074 (3)	0.4724 (2)	0.2878 (2)	0.0385 (8)
H23	0.5125	0.5109	0.3426	0.046*
H24	0.5627	0.5159	0.2669	0.046*
O3W	0.2657 (4)	0.0649 (3)	0.3688 (2)	0.0430 (9)
H25	0.2618	0.0592	0.4263	0.052*
H26	0.2632	0.1335	0.3605	0.052*
O4W	0.3566 (3)	−0.1511 (2)	0.4019 (2)	0.0308 (7)
H27	0.3685	−0.1247	0.4621	0.037*
H28	0.2922	−0.2148	0.3826	0.037*
O5W	0.6709 (3)	0.5864 (2)	0.1851 (2)	0.0384 (8)
H29	0.6115	0.6084	0.1380	0.046*
H30	0.7154	0.6513	0.2284	0.046*
O6W	0.8834 (3)	0.4660 (3)	0.0774 (3)	0.0461 (9)
H31	0.8949	0.4223	0.0305	0.055*
H32	0.9358	0.5344	0.0809	0.055*
O7W	0.8407 (3)	0.4228 (3)	0.3507 (3)	0.0697 (12)
H33	0.9176	0.4077	0.3778	0.084*
H34	0.8399	0.4808	0.3891	0.084*
O8W	0.9361 (3)	0.7490 (3)	0.2496 (3)	0.0532 (10)
H35	0.9908	0.7835	0.2242	0.064*
H36	0.9365	0.7984	0.2967	0.064*
O9W	0.9674 (3)	0.8475 (3)	0.4451 (3)	0.0479 (9)
H37	1.0455	0.8991	0.4683	0.057*
H38	0.9072	0.8824	0.4481	0.057*
O10W	0.5103 (3)	0.6282 (3)	0.4533 (2)	0.0630 (11)
H39	0.4757	0.6708	0.4907	0.076*
H40	0.5919	0.6325	0.4939	0.076*
O11W	0.1540 (4)	0.6400 (3)	0.3442 (3)	0.0706 (12)
H41	0.0733	0.6491	0.3264	0.085*
H42	0.1448	0.5670	0.3310	0.085*
O12W	0.1062 (5)	0.3802 (4)	0.5108 (3)	0.140 (2)
H43	0.1371	0.4040	0.4672	0.168*
H44	0.1556	0.3386	0.5402	0.168*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0423 (13)	0.0415 (12)	0.0743 (15)	0.0010 (10)	0.0349 (12)	0.0007 (11)
Ni1	0.0293 (3)	0.0181 (3)	0.0277 (3)	0.0065 (2)	0.0132 (3)	0.0055 (2)
Ni2	0.0251 (3)	0.0178 (3)	0.0246 (3)	0.0056 (2)	0.0126 (3)	0.0045 (2)
N1	0.028 (2)	0.023 (2)	0.034 (2)	0.0127 (17)	0.0185 (18)	0.0116 (17)
N2	0.025 (2)	0.0171 (18)	0.022 (2)	0.0047 (15)	0.0121 (17)	0.0029 (15)
C1	0.025 (3)	0.032 (3)	0.026 (3)	−0.002 (2)	0.011 (2)	0.001 (2)
C2	0.021 (3)	0.030 (3)	0.032 (3)	0.001 (2)	0.008 (2)	0.012 (2)
C3	0.021 (2)	0.021 (2)	0.031 (3)	−0.0011 (19)	0.013 (2)	0.004 (2)
C4	0.023 (3)	0.018 (2)	0.029 (3)	0.0004 (19)	0.016 (2)	0.006 (2)
C5	0.023 (2)	0.018 (2)	0.028 (3)	0.0028 (19)	0.013 (2)	0.008 (2)
C6	0.026 (3)	0.026 (3)	0.035 (3)	0.001 (2)	0.018 (2)	0.001 (2)
C7	0.021 (2)	0.028 (3)	0.033 (3)	0.005 (2)	0.012 (2)	0.008 (2)
C8	0.034 (3)	0.024 (2)	0.030 (3)	0.009 (2)	0.016 (2)	0.012 (2)
C9	0.028 (3)	0.017 (2)	0.032 (3)	0.003 (2)	0.013 (2)	0.002 (2)
C10	0.037 (3)	0.029 (3)	0.042 (3)	0.020 (2)	0.023 (2)	0.011 (2)
C11	0.048 (3)	0.022 (3)	0.043 (3)	0.010 (2)	0.028 (3)	0.007 (2)
C12	0.023 (2)	0.023 (2)	0.028 (3)	0.0058 (19)	0.014 (2)	0.005 (2)
C13	0.036 (3)	0.013 (2)	0.037 (3)	0.004 (2)	0.019 (2)	0.000 (2)
C14	0.029 (3)	0.027 (3)	0.026 (3)	0.004 (2)	0.016 (2)	0.010 (2)
C15	0.027 (3)	0.022 (2)	0.037 (3)	0.011 (2)	0.013 (2)	0.006 (2)
C16	0.026 (3)	0.025 (3)	0.021 (3)	0.007 (2)	0.011 (2)	0.009 (2)
Cl1	0.0445 (8)	0.0669 (9)	0.0283 (7)	0.0047 (7)	0.0091 (6)	−0.0080 (7)
O1	0.0291 (17)	0.0145 (15)	0.0182 (17)	0.0042 (13)	0.0093 (14)	0.0016 (12)
O2	0.043 (2)	0.043 (2)	0.037 (2)	0.0163 (16)	0.0265 (17)	0.0166 (16)
O3	0.0285 (18)	0.0256 (17)	0.0337 (19)	0.0087 (14)	0.0169 (15)	0.0075 (14)
O4	0.076 (3)	0.047 (2)	0.058 (2)	0.038 (2)	0.049 (2)	0.0192 (18)
O5	0.046 (2)	0.0228 (17)	0.0363 (19)	0.0154 (15)	0.0246 (17)	0.0109 (15)
O6	0.0306 (19)	0.0287 (18)	0.040 (2)	−0.0065 (15)	0.0116 (16)	−0.0058 (15)
O7	0.0266 (17)	0.0231 (17)	0.0332 (18)	0.0040 (13)	0.0161 (15)	0.0033 (14)
O8	0.0234 (18)	0.0415 (19)	0.0306 (19)	0.0101 (15)	0.0074 (15)	0.0060 (15)
O9	0.0299 (18)	0.0242 (17)	0.0284 (18)	0.0070 (14)	0.0114 (15)	0.0053 (14)
O1W	0.043 (2)	0.0252 (17)	0.041 (2)	0.0038 (15)	0.0103 (17)	0.0131 (15)
O2W	0.056 (2)	0.0228 (17)	0.041 (2)	0.0032 (15)	0.0298 (18)	0.0015 (15)
O3W	0.079 (3)	0.0320 (19)	0.047 (2)	0.0282 (18)	0.047 (2)	0.0194 (16)
O4W	0.0420 (19)	0.0238 (16)	0.0269 (18)	0.0034 (14)	0.0163 (15)	0.0058 (14)
O5W	0.045 (2)	0.0318 (18)	0.036 (2)	0.0047 (15)	0.0167 (17)	0.0055 (15)
O6W	0.044 (2)	0.036 (2)	0.065 (2)	0.0074 (16)	0.0328 (19)	0.0017 (17)
O7W	0.044 (2)	0.056 (2)	0.084 (3)	−0.0026 (19)	0.000 (2)	0.022 (2)
O8W	0.047 (2)	0.050 (2)	0.062 (2)	0.0021 (18)	0.028 (2)	0.0033 (19)
O9W	0.039 (2)	0.041 (2)	0.062 (2)	0.0094 (17)	0.0193 (19)	0.0021 (18)
O10W	0.079 (3)	0.073 (3)	0.045 (2)	0.041 (2)	0.023 (2)	0.003 (2)
O11W	0.056 (3)	0.026 (2)	0.118 (3)	0.0071 (18)	0.018 (2)	0.018 (2)
O12W	0.277 (7)	0.060 (3)	0.105 (4)	−0.003 (4)	0.133 (5)	0.010 (3)

Geometric parameters (Å, º)

Na1—O6W	2.212 (3)	C9—O3	1.279 (5)
Na1—O3	2.312 (3)	C10—C11	1.499 (6)
Na1—O5W	2.350 (3)	C10—H11	0.9900
Na1—O7W	2.358 (4)	C10—H12	0.9900
Na1—Ni1	3.836 (2)	C11—O4	1.260 (5)
Ni1—O3	2.025 (3)	C11—O5	1.280 (5)
Ni1—O1W	2.047 (3)	C12—H13	0.9900
Ni1—O5	2.060 (3)	C12—H14	0.9900
Ni1—O1	2.061 (2)	C13—C14	1.531 (6)
Ni1—N1	2.066 (3)	C13—H15	0.9900
Ni1—O2W	2.130 (3)	C13—H16	0.9900
Ni1—Ni2	3.7508 (11)	C14—O6	1.242 (5)
Ni2—O3W	2.031 (3)	C14—O7	1.271 (5)
Ni2—O1	2.041 (3)	C15—C16	1.514 (6)
Ni2—O7	2.047 (3)	C15—H17	0.9900
Ni2—N2	2.075 (3)	C15—H18	0.9900
Ni2—O4W	2.081 (3)	C16—O8	1.233 (5)
Ni2—O9	2.106 (3)	C16—O9	1.279 (4)
N1—C10	1.479 (5)	O1W—H21	0.8279
N1—C8	1.482 (5)	O1W—H22	0.8371
N1—C7	1.493 (5)	O2W—H23	0.8239
N2—C15	1.469 (5)	O2W—H24	0.8194
N2—C13	1.473 (5)	O3W—H25	0.8245
N2—C12	1.503 (5)	O3W—H26	0.8185
C1—C6	1.370 (6)	O4W—H27	0.8215
C1—C2	1.387 (6)	O4W—H28	0.8203
C1—Cl1	1.753 (4)	O5W—H29	0.8421
C2—C3	1.394 (6)	O5W—H30	0.8398
C2—H2	0.9500	O6W—H31	0.8411
C3—C4	1.405 (6)	O6W—H32	0.8363
C3—C7	1.493 (5)	O7W—H33	0.8224
C4—O1	1.334 (5)	O7W—H34	0.8188
C4—C5	1.398 (5)	O8W—H35	0.8140
C5—C6	1.390 (6)	O8W—H36	0.8230
C5—C12	1.494 (5)	O9W—H37	0.8227
C6—H6	0.9500	O9W—H38	0.8220
C7—H71	0.9900	O10W—H39	0.8902
C7—H72	0.9900	O10W—H40	0.8292
C8—C9	1.528 (5)	O11W—H41	0.8184
C8—H81	0.9900	O11W—H42	0.8215
C8—H82	0.9900	O12W—H43	0.8188
C9—O2	1.243 (4)	O12W—H44	0.8189
O6W—Na1—O3	136.44 (14)	N1—C8—H82	109.2
O6W—Na1—O5W	99.45 (13)	C9—C8—H82	109.2
O3—Na1—O5W	89.55 (11)	H81—C8—H82	107.9
O6W—Na1—O7W	124.55 (14)	O2—C9—O3	123.1 (4)
O3—Na1—O7W	97.07 (13)	O2—C9—C8	118.3 (4)
O5W—Na1—O7W	93.02 (12)	O3—C9—C8	118.5 (4)
O3—Ni1—O1W	99.39 (10)	N1—C10—C11	111.6 (3)
O3—Ni1—O5	163.68 (12)	N1—C10—H11	109.3
O1W—Ni1—O5	94.57 (10)	C11—C10—H11	109.3
O3—Ni1—O1	92.51 (10)	N1—C10—H12	109.3
O1W—Ni1—O1	90.26 (10)	C11—C10—H12	109.3
O5—Ni1—O1	95.86 (10)	H11—C10—H12	108.0
O3—Ni1—N1	83.84 (12)	O4—C11—O5	122.3 (4)
O1W—Ni1—N1	175.21 (10)	O4—C11—C10	118.2 (4)
O5—Ni1—N1	81.74 (12)	O5—C11—C10	119.4 (4)
O1—Ni1—N1	93.14 (12)	C5—C12—N2	112.5 (3)
O3—Ni1—O2W	86.61 (10)	C5—C12—H13	109.1
O1W—Ni1—O2W	86.50 (12)	N2—C12—H13	109.1
O5—Ni1—O2W	85.84 (11)	C5—C12—H14	109.1
O1—Ni1—O2W	176.46 (12)	N2—C12—H14	109.1
N1—Ni1—O2W	90.17 (13)	H13—C12—H14	107.8
O3W—Ni2—O1	85.72 (11)	N2—C13—C14	112.2 (3)
O3W—Ni2—O7	95.86 (12)	N2—C13—H15	109.2
O1—Ni2—O7	95.19 (11)	C14—C13—H15	109.2
O3W—Ni2—N2	178.87 (14)	N2—C13—H16	109.2
O1—Ni2—N2	93.93 (11)	C14—C13—H16	109.2
O7—Ni2—N2	83.10 (12)	H15—C13—H16	107.9
O3W—Ni2—O4W	89.21 (11)	O6—C14—O7	125.0 (4)
O1—Ni2—O4W	173.55 (11)	O6—C14—C13	116.8 (4)
O7—Ni2—O4W	89.29 (11)	O7—C14—C13	118.0 (4)
N2—Ni2—O4W	91.21 (12)	N2—C15—C16	112.4 (3)
O3W—Ni2—O9	100.91 (12)	N2—C15—H17	109.1
O1—Ni2—O9	92.69 (10)	C16—C15—H17	109.1
O7—Ni2—O9	161.94 (11)	N2—C15—H18	109.1
N2—Ni2—O9	80.17 (12)	C16—C15—H18	109.1
O4W—Ni2—O9	84.34 (11)	H17—C15—H18	107.9
C10—N1—C8	114.9 (3)	O8—C16—O9	124.3 (4)
C10—N1—C7	108.9 (3)	O8—C16—C15	118.2 (4)
C8—N1—C7	111.3 (3)	O9—C16—C15	117.5 (4)
C10—N1—Ni1	104.2 (3)	C4—O1—Ni2	112.6 (2)
C8—N1—Ni1	106.7 (2)	C4—O1—Ni1	115.1 (2)
C7—N1—Ni1	110.5 (2)	Ni2—O1—Ni1	132.22 (13)
C15—N2—C13	114.7 (3)	C9—O3—Ni1	113.7 (3)
C15—N2—C12	108.7 (3)	C9—O3—Na1	101.5 (2)
C13—N2—C12	111.0 (3)	Ni1—O3—Na1	124.26 (15)
C15—N2—Ni2	106.2 (2)	C11—O5—Ni1	110.1 (3)
C13—N2—Ni2	106.2 (2)	C14—O7—Ni2	113.6 (3)
C12—N2—Ni2	109.8 (2)	C16—O9—Ni2	112.3 (3)
C6—C1—C2	121.2 (4)	Ni1—O1W—H21	122.4
C6—C1—Cl1	119.8 (3)	Ni1—O1W—H22	104.5
C2—C1—Cl1	119.0 (4)	H21—O1W—H22	104.9
C1—C2—C3	119.2 (4)	Ni1—O2W—H23	123.3
C1—C2—H2	120.4	Ni1—O2W—H24	126.1
C3—C2—H2	120.4	H23—O2W—H24	107.0
C2—C3—C4	120.2 (4)	Ni2—O3W—H25	124.0
C2—C3—C7	121.2 (4)	Ni2—O3W—H26	123.2
C4—C3—C7	118.6 (4)	H25—O3W—H26	107.0
O1—C4—C5	120.4 (4)	Ni2—O4W—H27	120.3
O1—C4—C3	120.4 (4)	Ni2—O4W—H28	117.6
C5—C4—C3	119.2 (4)	H27—O4W—H28	107.1
C6—C5—C4	120.0 (4)	Na1—O5W—H29	127.0
C6—C5—C12	121.3 (4)	Na1—O5W—H30	126.9
C4—C5—C12	118.7 (4)	H29—O5W—H30	102.3
C1—C6—C5	120.2 (4)	Na1—O6W—H31	128.4
C1—C6—H6	119.9	Na1—O6W—H32	128.6
C5—C6—H6	119.9	H31—O6W—H32	102.9
C3—C7—N1	113.1 (3)	Na1—O7W—H33	119.1
C3—C7—H71	109.0	Na1—O7W—H34	119.2
N1—C7—H71	109.0	H33—O7W—H34	107.2
C3—C7—H72	109.0	H35—O8W—H36	107.8
N1—C7—H72	109.0	H37—O9W—H38	106.7
H71—C7—H72	107.8	H39—O10W—H40	104.0
N1—C8—C9	112.2 (3)	H41—O11W—H42	107.3
N1—C8—H81	109.2	H43—O12W—H44	107.3
C9—C8—H81	109.2
O3—Ni1—N1—C10	−141.0 (2)	C12—N2—C15—C16	85.6 (4)
O5—Ni1—N1—C10	31.3 (2)	Ni2—N2—C15—C16	−32.5 (4)
O1—Ni1—N1—C10	126.8 (2)	N2—C15—C16—O8	−167.0 (3)
O2W—Ni1—N1—C10	−54.4 (2)	N2—C15—C16—O9	15.2 (5)
O3—Ni1—N1—C8	−19.0 (2)	C5—C4—O1—Ni2	−52.9 (4)
O5—Ni1—N1—C8	153.3 (3)	C3—C4—O1—Ni2	126.2 (3)
O1—Ni1—N1—C8	−111.2 (2)	C5—C4—O1—Ni1	129.0 (3)
O2W—Ni1—N1—C8	67.6 (2)	C3—C4—O1—Ni1	−51.9 (4)
O3—Ni1—N1—C7	102.2 (2)	O3W—Ni2—O1—C4	−131.2 (3)
O5—Ni1—N1—C7	−85.5 (2)	O7—Ni2—O1—C4	−35.7 (3)
O1—Ni1—N1—C7	10.0 (2)	N2—Ni2—O1—C4	47.7 (3)
O2W—Ni1—N1—C7	−171.3 (2)	O9—Ni2—O1—C4	128.1 (3)
O1—Ni2—N2—C15	121.4 (2)	O3W—Ni2—O1—Ni1	46.49 (19)
O7—Ni2—N2—C15	−143.8 (2)	O7—Ni2—O1—Ni1	142.00 (17)
O4W—Ni2—N2—C15	−54.7 (2)	N2—Ni2—O1—Ni1	−134.58 (18)
O9—Ni2—N2—C15	29.3 (2)	O9—Ni2—O1—Ni1	−54.26 (18)
O1—Ni2—N2—C13	−116.0 (2)	O3—Ni1—O1—C4	−41.3 (3)
O7—Ni2—N2—C13	−21.2 (2)	O1W—Ni1—O1—C4	−140.7 (3)
O4W—Ni2—N2—C13	67.9 (3)	O5—Ni1—O1—C4	124.6 (3)
O9—Ni2—N2—C13	152.0 (3)	N1—Ni1—O1—C4	42.6 (3)
O1—Ni2—N2—C12	4.1 (2)	O3—Ni1—O1—Ni2	141.03 (18)
O7—Ni2—N2—C12	98.8 (2)	O1W—Ni1—O1—Ni2	41.62 (17)
O4W—Ni2—N2—C12	−172.0 (2)	O5—Ni1—O1—Ni2	−53.00 (19)
O9—Ni2—N2—C12	−88.0 (2)	N1—Ni1—O1—Ni2	−135.01 (18)
C6—C1—C2—C3	−0.7 (6)	O2—C9—O3—Ni1	174.5 (3)
Cl1—C1—C2—C3	178.6 (3)	C8—C9—O3—Ni1	−0.5 (4)
C1—C2—C3—C4	0.2 (6)	O2—C9—O3—Na1	38.7 (4)
C1—C2—C3—C7	−176.6 (3)	C8—C9—O3—Na1	−136.3 (3)
C2—C3—C4—O1	−178.4 (3)	O1W—Ni1—O3—C9	−164.9 (3)
C7—C3—C4—O1	−1.5 (5)	O5—Ni1—O3—C9	−16.5 (6)
C2—C3—C4—C5	0.8 (6)	O1—Ni1—O3—C9	104.4 (3)
C7—C3—C4—C5	177.7 (3)	N1—Ni1—O3—C9	11.5 (3)
O1—C4—C5—C6	178.0 (3)	O2W—Ni1—O3—C9	−79.0 (3)
C3—C4—C5—C6	−1.2 (5)	O1W—Ni1—O3—Na1	−40.65 (18)
O1—C4—C5—C12	−4.7 (5)	O5—Ni1—O3—Na1	107.8 (4)
C3—C4—C5—C12	176.2 (3)	O1—Ni1—O3—Na1	−131.32 (17)
C2—C1—C6—C5	0.3 (6)	N1—Ni1—O3—Na1	135.78 (18)
Cl1—C1—C6—C5	−179.0 (3)	O2W—Ni1—O3—Na1	45.24 (17)
C4—C5—C6—C1	0.7 (6)	O6W—Na1—O3—C9	−43.9 (3)
C12—C5—C6—C1	−176.6 (4)	O5W—Na1—O3—C9	59.4 (2)
C2—C3—C7—N1	−117.8 (4)	O7W—Na1—O3—C9	152.4 (2)
C4—C3—C7—N1	65.3 (5)	O6W—Na1—O3—Ni1	−173.34 (16)
C10—N1—C7—C3	−172.0 (3)	O5W—Na1—O3—Ni1	−70.04 (17)
C8—N1—C7—C3	60.3 (4)	O7W—Na1—O3—Ni1	22.95 (19)
Ni1—N1—C7—C3	−58.1 (4)	O4—C11—O5—Ni1	−161.2 (3)
C10—N1—C8—C9	138.3 (4)	C10—C11—O5—Ni1	14.0 (5)
C7—N1—C8—C9	−97.3 (4)	O3—Ni1—O5—C11	1.9 (6)
Ni1—N1—C8—C9	23.4 (4)	O1W—Ni1—O5—C11	150.7 (3)
N1—C8—C9—O2	168.3 (3)	O1—Ni1—O5—C11	−118.6 (3)
N1—C8—C9—O3	−16.4 (5)	N1—Ni1—O5—C11	−26.2 (3)
C8—N1—C10—C11	−149.0 (4)	O2W—Ni1—O5—C11	64.5 (3)
C7—N1—C10—C11	85.3 (4)	O6—C14—O7—Ni2	178.7 (3)
Ni1—N1—C10—C11	−32.6 (4)	C13—C14—O7—Ni2	2.3 (4)
N1—C10—C11—O4	−171.0 (4)	O3W—Ni2—O7—C14	−169.2 (3)
N1—C10—C11—O5	13.6 (6)	O1—Ni2—O7—C14	104.5 (3)
C6—C5—C12—N2	−115.0 (4)	N2—Ni2—O7—C14	11.2 (3)
C4—C5—C12—N2	67.7 (4)	O4W—Ni2—O7—C14	−80.1 (3)
C15—N2—C12—C5	−169.8 (3)	O9—Ni2—O7—C14	−11.0 (5)
C13—N2—C12—C5	63.1 (4)	O8—C16—O9—Ni2	−166.8 (3)
Ni2—N2—C12—C5	−54.0 (4)	C15—C16—O9—Ni2	10.9 (4)
C15—N2—C13—C14	144.7 (4)	O3W—Ni2—O9—C16	157.0 (3)
C12—N2—C13—C14	−91.6 (4)	O1—Ni2—O9—C16	−116.9 (3)
Ni2—N2—C13—C14	27.7 (4)	O7—Ni2—O9—C16	−1.0 (5)
N2—C13—C14—O6	161.9 (3)	N2—Ni2—O9—C16	−23.4 (3)
N2—C13—C14—O7	−21.4 (5)	O4W—Ni2—O9—C16	68.9 (3)
C13—N2—C15—C16	−149.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H21···O9	0.83	2.00	2.766 (4)	153
O1W—H22···O7W	0.84	1.94	2.773 (4)	177
O2W—H23···O10W	0.82	1.96	2.767 (4)	167
O2W—H24···O5W	0.82	1.96	2.757 (4)	165
O3W—H25···O8^i	0.82	1.99	2.804 (4)	171
O3W—H26···O5	0.82	1.95	2.746 (4)	165
O4W—H27···O9^i	0.82	2.00	2.818 (4)	170
O4W—H28···O11W^ii	0.82	1.83	2.652 (4)	177
O5W—H29···O2^iii	0.84	1.89	2.711 (4)	166
O5W—H30···O8W	0.84	2.20	2.735 (4)	122
O6W—H31···O6^iv	0.84	1.90	2.741 (4)	177
O6W—H32···O6^v	0.84	1.99	2.810 (4)	167
O7W—H33···O12W^vi	0.82	2.31	3.077 (6)	157
O7W—H34···O12W^vii	0.82	1.86	2.656 (5)	164
O8W—H35···O7^v	0.81	2.02	2.805 (4)	162
O8W—H36···O9W	0.82	1.99	2.728 (5)	150
O9W—H37···O8^viii	0.82	1.98	2.787 (4)	167
O9W—H38···O8^ix	0.82	1.94	2.757 (4)	174
O10W—H39···O1W^vii	0.89	2.40	3.243 (3)	157
O10W—H40···O5^vii	0.83	2.31	2.915 (4)	130
O11W—H41···O8W^x	0.82	2.11	2.830 (5)	146
O11W—H42···O4	0.82	1.92	2.728 (4)	166
O12W—H43···O4	0.82	1.86	2.636 (5)	157
O12W—H44···O9W^vii	0.82	2.30	2.760 (5)	116

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y−1, z; (iii) −x+1, −y+1, −z; (iv) −x+1, −y, −z; (v) x+1, y+1, z; (vi) x+1, y, z; (vii) −x+1, −y+1, −z+1; (viii) −x+2, −y+1, −z+1; (ix) x, y+1, z; (x) x−1, y, z.