Two polymeric nickel(II) complexes with aromatic benzene-1,2,4,5-tetra­carboxyl­ate and pyridine-2,5-di­carboxyl­ate linkers

(μ-Benzene-1,2,4,5-tetra­carboxyl­ato-κ²O¹:O⁴)bis­[aqua­bis(2,2-methyl­propane-1,3-diamine-κ²N,N′)nickel(II)] methanol disolvate tetra­hydrate, [Ni₂(C₁₀H₂O₈)(C₅H₁₄N₂)₄(H₂O)₂]·2CH₄O·4H₂O, (I), is dinuclear, with ele­mental units built up around an inversion centre halving the benzene-1,2,4,5-tetra­carboxyl­ate (btc) anion, which bridges two symmetry-related Ni^II cations. The octa­hedral Ni polyhedron is completed by two chelating 2,2-methyl­propane-1,3-diamine (dmpda) groups and a terminal aqua ligand. Two methanol and four water solvent mol­ecules are involved in a number of N—H...O and O—H...O hydrogen bonds which define a strongly bound two-dimensional supra­molecular structure. The structure of catena-poly[[[bis­(2,2-methyl­propane-1,3-diam­ine-κ²N,N′)nickel(II)]-μ-pyridine-2,5-dicarboxyl­ato-κ³O⁵:N,O²-[(2,2-methyl­propane-1,3-diamine-κ²N,N′)nickel(II)]-μ-pyridine-2,5-dicarboxyl­ato-κ³N,O²:O⁵] octa­hydrate], {[Ni₂(C₇H₃NO₄)₂(C₅H₁₄N₂)₃]·8H₂O}_n, (II), is polymeric, forming twisted chains around three independent Ni centres, two of which lie on inversion centres and the third in a general position. There are three chelating dmpda ligands (one disordered over two equally populated positions), which are each attached to a different cation, and two pyridine-2,5-dicarboxyl­ate (pdc) anions, both chelating the Ni centre in general positions through an –O—C—C—N– loop, while acting as bridges to the remaining two centrosymmetric Ni atoms. There are, in addition, eight noncoordinated water mol­ecules in the structure, some of which are disordered.

S1. Comment

Multidimensional structures built up around metal centres bridged by carboxylate linkers are extremely appealing systems, both structurally, due to the variation in topologies which they can give rise to (Eddaoudi et al., 2001) and for their potential applications, viz. in medicine, chemical separation and heterogeneous catalysis, and occasionally due to their eventual electronic or magnetic properties (Go et al., 2005; Shi et al., 2004)

The presence of two potentially coordinating O atoms in the carboxylate group usually favours the stability of these compounds, and at the same time they assume different coordination modes to metallic centres (syn–syn, syn–anti and anti–anti), which can lead to a variety of structural types. In general, it appears that syn–syn conformations lead to binuclear compounds, while the remaining two conformations favour polymeric entities (Eddaoudi et al., 2001, 2002; Rowsell & Yaghi, 2004; Wang et al., 1999; Whitlow, 1973). In addition, the presence of donor solvent molecules such as water, amines etc. in the vicinity of the COOH groups frequently promotes the formation of supramolecular structures through extended hydrogen-bonding networks, sometimes in the form of porous systems having applications in size-selective sorption, host–guest recognition, catalysis etc. (Coughlin & Lippard, 1984; Colacio et al., 1992, 1994).

Here, we report the structures of the title compounds, [Ni₂(btc)(dmpda)₄(H₂O)₂].2CH₄O.4H₂O, (I) (Fig. 1), and [Ni₂(pdc)₂(dmpda)₃].8H₂O, (II) (Fig. 2), where btc is the benzene-1,2,4,5-tetracarboxylate anion, pdc is the pyridine-2,5-dicarboxylate anion and dmpa is the 2,2-methylpropane-1,3-amine ligand. Complexes (I) and (II) are based on the same Ni^II cation complexed to the same chelating dmpda ligand, but where different (though closely related) bridging agents have been used to link the metal centres, btc in (I) and pdc in (II). Although both polycarboxylates behave in a rather similar fashion (basically as one-dimensional linkers), the resulting structures are different in a number of interesting aspects.

Compound (I) is basically constructed out of dimers built up around an inversion centre, and the asymmetric unit is one half of a dimer. The inversion centre bisects the btc anion, which in turn bridges two opposite symmetry-related Ni^II cations, involving in this linkage only two carboxylate O atoms (one on each side) out of the eight available; the remaining six are in principle free to take part in hydrogen bonding (see below). Two dmpda groups chelate the metal centre through their amino groups, providing four N atoms for the octahedral environment of the metal, the sixth position being occupied by a terminal aqua ligand. The Ni—N bonds are fairly homogeneous, in a narrow range of 2.089 (3)–2.114 (3) Å, while the two Ni—O bonds present extreme values: 2.081 (2) Å for the O_aqua and 2.173 (2) Å for the O_btc. Finally, the structure is stabilized by one methanol and two water solvent molecules (Table 1). As a result, there are in the structure 15 H atoms potentially available for hydrogen bonding, six in the three water molecules, eight in the four amino groups and one in the methanol unit. 14 of these form significant interactions, generating a very complex hydrogen-bonding scheme, leading to a two-dimensional structure lying parallel to (100) (Fig. 3). These sheets are well separated along [100] and interact only weakly.

Structure (II) is more complex. There are three independent Ni atoms, two of them (Ni1 and Ni2) lying on inversion centres and the third (Ni3) in a general position but displaying a non-crystallographic twofold pseudo-symmetry. This is shown in Fig. 4, which displays a fit of the group onto its rotated image around an axis bisecting the N_dmpda—Ni—N_dmpda angle and passing through the cation. The largest deviation corresponds to the C75—C74 pair, with a misfit of 0.14 Å. There are also three dmpda ligands, each one identified herein by a different terminal digit and attached to a different cation: unit 1 to atom Ni1, unit 2 to atom Ni2, and unit 3, disordered over two equally populated positions, to atom Ni3. Completion of the coordination is achieved by two pdc anions (terminal digits 4 and 5), both of them chelating atom Ni3 through an –O—C—C—N– loop, while acting as bridges to the remaining two centrosymmetric Ni atoms (one Ni atom each). The resulting polyhedra are rather regular, as is usual in nickel structural chemistry. Irrespective of the type of ligand (X = C, O or N), the range of Ni—X distances is narrow [Ni1: 2.064 (3)–2.091 (3) Å; Ni2: 2.076 (3)–2.089 (3) Å; Ni3: 2.040 (3)–2.113 (3) Å]. The bond angles in the centrosymmetric polyhedra are also tightly bunched around ideal values [Ni1 90±3.23 (14)° and Ni2 90±4.05 (14)°], with those for Ni3 being more dispersed due to the closed pdc chelating bite [cis: 77.88 (11)–96.03 (13)°; trans: 167.91 (10)–175.03 (12)°].

This N,O-chelating bite in (II) is a very usual binding behaviour for pyridine-2,5-dicarboxylate. Out of a total of 173 cases where the ligand coordinates a metal (February 2009 update of the Cambridge Structural Database; Allen, 2002), 168 have combinations of the aforementioned chelating bite plus a diversity of µ₂, µ₃ and µ₄ bridging modes; in particular, a total of 40 correspond to the µ₂-N,O:O' type displayed in (II). In only five structures does the pyridine N atom not participate in coordination.

The bridging mode exerted by both pdc anions leads to a twisted chain structure of the ···Ni1···Ni3···Ni2···Ni3···Ni1··· type (with atoms Ni1 and Ni2 lying on inversion centres, and atom Ni3 on a general position) running parallel to the [121] direction (Fig. 5). These chains propagate in a rather non-interacting way and the space between them is filled by eight independent solvent water molecules (two of them heavily disordered). In spite of not having been able to determine the positions of the water H atoms with certainty (they have not been included in the model), the large number of short O···O contacts present in the structure, with a minimum of three contacts below 3.00 Å per solvent water molecule (see Supplementary Material for the most relevant ones), strongly suggests a very complex hydrogen-bonding scheme involving them and connecting the chains together. This `eagerness' for interaction shown by the water molecules in (II) contrasts with the much feebler participation displayed by the N—H groups; only half of the available N—H groups are involved in (extremely weak) N—H···O interactions (Table 2).

S2. Experimental

Complex (I) was synthesized as follows. 1,2,4,5-Benzenetetracarboxylic acid (H4btc) (0.254 g, 1 mmol) was added slowly to an aqueous solution (20 ml) of NaOH (0.16 g, 4 mmol). Nickel acetate tetrahydrate (0.497 g, 2 mmol) was dissolved in water (20 ml) and added to the above solution. The resulting mixture was stirred for 10 min, followed by the addition of a methanolic solution (Volume?) of 2,2-dimethyl-1,3-diamine (dmpda) (0.204 g, 2 mmol). Single crystals of (I) adequate for X-ray diffraction studies were obtained by slow concentration of the solution. Complex (II) was obtained in the same way, using pyridine-2,5-dicarboxylic acid (H2pdc) (0.167 g, 1 mmol) and NaOH (0.080 g, 2 mmol).

S3. Refinement

H atoms bonded to C or N atoms were positioned geometrically and treated as riding atoms, with C—H = 0.93–0.97 Å and N—H = 0.90 Å. In (I), H atoms bonded to O atoms were located in a difference map and refined with restrained distances [O—H = 0.85 (1) Å and H···H = 1.30 (2) Å] and kept riding in the final cycles. In structure (II), these H atoms could not be confidently found and accordingly were not included in the model. In spite of this, a large number of short O_water···O_any distances clearly attributable to hydrogen bonding are present in the structure (see Supplementary Material). In all cases, U_iso(H) = 1.2 or 1.5U_eq(parent). The structure of (II) presents some disorder: one of the three chelating dmpda ligands is disordered over two nearly equally populated positions, as is one of the solvent water molecules (O7WA/O7WB). A second water molecule appears to be much more severely disordered, and could only be modelled as five complementary fragments, each with low site occupancy (O8WA to O8WE). The site-occupation factors of the disordered water O atoms were refined for a few cycles and then kept fixed, while those of the disordered dmpda ligand were refined continuously with the occupation factor sum for the two conformations constrained to unity. Some soft metric and atomic displacement parameter restraints were applied to the disordered atoms of the dmpda ligand [SADI and DELU instructions in the SHELXL program (Sheldrick, 2008) with a standard uncertainty of 0.01].

Computing details

For both compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2002); data reduction: SAINT-NT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-NT (Sheldrick, 2008); software used to prepare material for publication: SHELXTL-NT (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. Molecular view of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. The asymmetric unit is shown in bold. [Symmetry code: (i) 1 - x, 1 - y, 2 - z.]
	Fig. 2. Molecular view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. The asymmetric unit is shown in bold. Doubly primed atoms are in the disordered dmpa ligand. [Please check added text] [Symmetry codes: (i) 1 - x, 2 - y, 1 - z; (ii) -x, -y, -z.]
	Fig. 3. A packing view of (I), projected down [100], showing the two-dimensional hydrogen-bonded structure parallel to (100). Methyl groups and carbon-bound H atoms have been omitted for clarity.
	Fig. 4. Schematic drawing of the Ni3 coordination polyhedron in (II) fitted to its twofold rotated image.
	Fig. 5. A packing view of (II), projected down [001]*, showing the `twisted' chain structure of the ···Ni1···Ni3···Ni2···Ni3···Ni1··· type. H atoms not involved in hydrogen bonding have been omitted for clarity.

(I) (µ-benzene-1,2,4,5-tetracarboxylato- κ²O¹:O⁴)bis[aquabis(2,2-methylpropane-1,3-diamine- κ²N,N')nickel(II)] methanol disolvate tetrahydrate

Crystal data

[Ni2(C10H2O8)(C5H14N2)4(H2O)2]·2CH4O·4H2O	F(000) = 1020
Mr = 948.44	Dx = 1.324 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5277 reflections
a = 10.6492 (10) Å	θ = 2.0–27.8°
b = 20.914 (2) Å	µ = 0.86 mm^−1
c = 11.3422 (11) Å	T = 295 K
β = 109.662 (2)°	Block, pink
V = 2378.8 (4) Å^3	0.44 × 0.25 × 0.18 mm
Z = 2

Data collection

Bruker SMART? CCD area-detector diffractometer	5385 independent reflections
Radiation source: fine-focus sealed tube	3837 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.048
ϕ and ω scans	θmax = 28.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→13
Tmin = 0.72, Tmax = 0.86	k = −26→26
19918 measured reflections	l = −15→14

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.146	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0724P)^2 + 0.6703P] where P = (Fo^2 + 2Fc^2)/3
5385 reflections	(Δ/σ)max = 0.002
267 parameters	Δρmax = 0.70 e Å^−3
0 restraints	Δρmin = −0.36 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.

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

	x	y	z	Uiso*/Ueq
Ni1	0.49088 (4)	0.654109 (17)	0.57319 (3)	0.03640 (15)
N11	0.6720 (3)	0.61646 (12)	0.5715 (2)	0.0386 (6)
H11A	0.7036	0.5914	0.6397	0.046*
H11B	0.6533	0.5906	0.5044	0.046*
N21	0.5936 (3)	0.73411 (13)	0.6744 (3)	0.0501 (7)
H21A	0.5354	0.7669	0.6584	0.060*
H21B	0.6154	0.7249	0.7563	0.060*
C11	0.7824 (4)	0.65854 (17)	0.5690 (3)	0.0532 (9)
H11C	0.7565	0.6800	0.4885	0.064*
H11D	0.8593	0.6321	0.5756	0.064*
C21	0.8233 (4)	0.70874 (18)	0.6712 (3)	0.0566 (9)
C31	0.7157 (5)	0.75754 (18)	0.6540 (4)	0.0710 (12)
H31A	0.7517	0.7927	0.7112	0.085*
H31B	0.6912	0.7744	0.5695	0.085*
C41	0.8676 (6)	0.6789 (3)	0.7999 (4)	0.0949 (16)
H41A	0.8953	0.7119	0.8622	0.142*
H41B	0.9408	0.6504	0.8085	0.142*
H41C	0.7948	0.6555	0.8108	0.142*
C51	0.9444 (6)	0.7441 (3)	0.6559 (5)	0.0991 (17)
H51A	0.9183	0.7644	0.5753	0.149*
H51B	1.0146	0.7141	0.6628	0.149*
H51C	0.9753	0.7760	0.7202	0.149*
N12	0.3052 (3)	0.69258 (12)	0.5668 (2)	0.0458 (7)
H12A	0.2930	0.6825	0.6393	0.055*
H12B	0.3118	0.7354	0.5649	0.055*
N22	0.3958 (3)	0.56994 (12)	0.4862 (2)	0.0402 (6)
H22A	0.4465	0.5534	0.4442	0.048*
H22B	0.3994	0.5421	0.5477	0.048*
C12	0.1831 (4)	0.67383 (17)	0.4640 (3)	0.0511 (9)
H12C	0.1884	0.6906	0.3860	0.061*
H12D	0.1071	0.6938	0.4779	0.061*
C22	0.1583 (4)	0.60234 (17)	0.4493 (3)	0.0515 (8)
C32	0.2579 (3)	0.56994 (17)	0.3997 (3)	0.0507 (8)
H32A	0.2300	0.5260	0.3789	0.061*
H32B	0.2555	0.5911	0.3229	0.061*
C42	0.1611 (4)	0.5721 (2)	0.5732 (4)	0.0655 (11)
H42A	0.1362	0.5279	0.5598	0.098*
H42B	0.0994	0.5942	0.6041	0.098*
H42C	0.2493	0.5754	0.6332	0.098*
C52	0.0201 (4)	0.5925 (2)	0.3510 (4)	0.0782 (13)
H52A	0.0187	0.6104	0.2726	0.117*
H52B	−0.0458	0.6134	0.3780	0.117*
H52C	0.0008	0.5476	0.3407	0.117*
O13	0.4945 (3)	0.37125 (11)	0.7813 (2)	0.0598 (7)
O23	0.4176 (3)	0.45791 (11)	0.66911 (18)	0.0528 (6)
O33	0.6662 (3)	0.53808 (12)	0.7788 (2)	0.0591 (7)
O43	0.5091 (2)	0.61214 (9)	0.75342 (17)	0.0415 (5)
C13	0.5420 (3)	0.56236 (14)	1.0119 (3)	0.0373 (7)
H13	0.5707	0.6046	1.0198	0.045*
C23	0.5276 (3)	0.52969 (13)	0.9013 (3)	0.0349 (7)
C33	0.4853 (3)	0.46644 (13)	0.8894 (3)	0.0354 (7)
C43	0.4636 (3)	0.42975 (14)	0.7692 (3)	0.0403 (7)
C53	0.5714 (3)	0.56189 (14)	0.8019 (3)	0.0382 (7)
O14	0.1542 (4)	0.9576 (2)	0.5474 (4)	0.1225 (14)
H14	0.2080	0.9819	0.6011	0.184*
C14	0.1312 (8)	0.9871 (5)	0.4301 (7)	0.175 (4)
H14A	0.1126	1.0317	0.4359	0.263*
H14B	0.0564	0.9671	0.3685	0.263*
H14C	0.2089	0.9826	0.4059	0.263*
O1W	0.4758 (3)	0.69819 (11)	0.4044 (2)	0.0606 (7)
H1WA	0.4178	0.7271	0.3741	0.073*
H1WB	0.4899	0.6781	0.3450	0.073*
O2W	0.3493 (3)	0.81188 (11)	0.3432 (2)	0.0612 (7)
H2WA	0.3991	0.8417	0.3335	0.073*
H2WB	0.3049	0.8261	0.3875	0.073*
O3W	0.2679 (4)	0.84070 (14)	0.5420 (3)	0.0822 (9)
H3WA	0.3473	0.8492	0.5882	0.099*
H3WB	0.2162	0.8726	0.5338	0.099*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0606 (3)	0.0276 (2)	0.0273 (2)	0.00564 (17)	0.02307 (18)	0.00162 (15)
N11	0.0600 (17)	0.0329 (14)	0.0285 (12)	0.0016 (12)	0.0220 (12)	−0.0027 (10)
N21	0.080 (2)	0.0334 (14)	0.0494 (16)	−0.0021 (14)	0.0377 (16)	−0.0077 (12)
C11	0.064 (2)	0.056 (2)	0.048 (2)	−0.0095 (18)	0.0293 (18)	−0.0097 (16)
C21	0.069 (2)	0.054 (2)	0.050 (2)	−0.0130 (19)	0.0242 (18)	−0.0130 (17)
C31	0.105 (3)	0.046 (2)	0.072 (3)	−0.019 (2)	0.044 (3)	−0.016 (2)
C41	0.123 (4)	0.092 (4)	0.054 (3)	−0.007 (3)	0.010 (3)	−0.006 (2)
C51	0.102 (4)	0.095 (4)	0.105 (4)	−0.040 (3)	0.042 (3)	−0.033 (3)
N12	0.0672 (19)	0.0377 (15)	0.0379 (14)	0.0112 (13)	0.0249 (14)	0.0014 (12)
N22	0.0577 (17)	0.0324 (13)	0.0369 (14)	0.0067 (12)	0.0245 (13)	0.0002 (11)
C12	0.060 (2)	0.0437 (19)	0.051 (2)	0.0161 (17)	0.0202 (18)	0.0038 (16)
C22	0.054 (2)	0.050 (2)	0.051 (2)	0.0060 (17)	0.0182 (16)	0.0020 (16)
C32	0.064 (2)	0.0435 (19)	0.0438 (19)	0.0040 (17)	0.0162 (17)	−0.0051 (15)
C42	0.069 (3)	0.064 (3)	0.078 (3)	0.005 (2)	0.044 (2)	0.011 (2)
C52	0.063 (3)	0.075 (3)	0.086 (3)	0.002 (2)	0.012 (2)	−0.006 (2)
O13	0.125 (2)	0.0273 (12)	0.0353 (12)	0.0033 (13)	0.0375 (14)	−0.0026 (9)
O23	0.0957 (19)	0.0405 (12)	0.0231 (10)	0.0071 (12)	0.0213 (11)	−0.0016 (9)
O33	0.0860 (19)	0.0531 (15)	0.0580 (15)	0.0210 (13)	0.0503 (14)	0.0217 (12)
O43	0.0737 (16)	0.0289 (11)	0.0321 (11)	0.0071 (10)	0.0313 (11)	0.0076 (9)
C13	0.064 (2)	0.0241 (14)	0.0281 (14)	−0.0007 (13)	0.0210 (14)	−0.0002 (11)
C23	0.058 (2)	0.0278 (15)	0.0250 (13)	0.0036 (13)	0.0210 (13)	0.0021 (11)
C33	0.058 (2)	0.0279 (15)	0.0238 (13)	0.0022 (13)	0.0191 (13)	−0.0016 (11)
C43	0.067 (2)	0.0329 (16)	0.0278 (15)	−0.0069 (15)	0.0246 (15)	−0.0049 (12)
C53	0.066 (2)	0.0285 (15)	0.0256 (14)	−0.0004 (14)	0.0221 (14)	0.0006 (12)
O14	0.131 (3)	0.106 (3)	0.118 (3)	−0.018 (3)	0.026 (3)	−0.019 (3)
C14	0.175 (8)	0.193 (9)	0.124 (6)	−0.024 (6)	0.005 (5)	0.029 (6)
O1W	0.113 (2)	0.0466 (14)	0.0337 (12)	0.0271 (14)	0.0395 (13)	0.0106 (10)
O2W	0.106 (2)	0.0355 (13)	0.0544 (15)	−0.0042 (13)	0.0429 (15)	0.0011 (11)
O3W	0.117 (3)	0.0624 (19)	0.078 (2)	−0.0170 (17)	0.047 (2)	−0.0191 (15)

Geometric parameters (Å, º)

Ni1—O1W	2.081 (2)	C12—H12D	0.9700
Ni1—N11	2.089 (3)	C22—C32	1.517 (5)
Ni1—N22	2.103 (3)	C22—C42	1.531 (5)
Ni1—N12	2.114 (3)	C22—C52	1.532 (5)
Ni1—N21	2.114 (3)	C32—H32A	0.9700
Ni1—O43	2.1727 (18)	C32—H32B	0.9700
N11—C11	1.477 (4)	C42—H42A	0.9600
N11—H11A	0.9000	C42—H42B	0.9600
N11—H11B	0.9000	C42—H42C	0.9600
N21—C31	1.479 (5)	C52—H52A	0.9600
N21—H21A	0.9000	C52—H52B	0.9600
N21—H21B	0.9000	C52—H52C	0.9600
C11—C21	1.515 (5)	O13—C43	1.262 (4)
C11—H11C	0.9700	O23—C43	1.226 (4)
C11—H11D	0.9700	O33—C53	1.231 (4)
C21—C31	1.497 (6)	O43—C53	1.266 (3)
C21—C41	1.510 (6)	C13—C33^i	1.386 (4)
C21—C51	1.546 (6)	C13—C23	1.390 (4)
C31—H31A	0.9700	C13—H13	0.9300
C31—H31B	0.9700	C23—C33	1.389 (4)
C41—H41A	0.9600	C23—C53	1.515 (4)
C41—H41B	0.9600	C33—C13^i	1.386 (4)
C41—H41C	0.9600	C33—C43	1.512 (4)
C51—H51A	0.9600	O14—C14	1.412 (8)
C51—H51B	0.9600	O14—H14	0.8497
C51—H51C	0.9600	C14—H14A	0.9600
N12—C12	1.478 (4)	C14—H14B	0.9600
N12—H12A	0.9000	C14—H14C	0.9600
N12—H12B	0.9000	O1W—H1WA	0.8500
N22—C32	1.467 (4)	O1W—H1WB	0.8500
N22—H22A	0.9000	O2W—H2WA	0.8500
N22—H22B	0.9000	O2W—H2WB	0.8500
C12—C22	1.518 (5)	O3W—H3WA	0.8501
C12—H12C	0.9700	O3W—H3WB	0.8499
O1W—Ni1—N11	86.83 (10)	C32—N22—H22A	106.8
O1W—Ni1—N22	93.62 (10)	Ni1—N22—H22A	106.8
N11—Ni1—N22	88.87 (10)	C32—N22—H22B	106.8
O1W—Ni1—N12	91.02 (10)	Ni1—N22—H22B	106.8
N11—Ni1—N12	177.65 (9)	H22A—N22—H22B	106.7
N22—Ni1—N12	90.31 (10)	N12—C12—C22	115.0 (3)
O1W—Ni1—N21	90.83 (11)	N12—C12—H12C	108.5
N11—Ni1—N21	89.58 (11)	C22—C12—H12C	108.5
N22—Ni1—N21	175.20 (10)	N12—C12—H12D	108.5
N12—Ni1—N21	91.41 (11)	C22—C12—H12D	108.5
O1W—Ni1—O43	177.48 (9)	H12C—C12—H12D	107.5
N11—Ni1—O43	93.78 (9)	C32—C22—C12	111.3 (3)
N22—Ni1—O43	88.84 (9)	C32—C22—C42	110.9 (3)
N12—Ni1—O43	88.41 (9)	C12—C22—C42	110.9 (3)
N21—Ni1—O43	86.73 (9)	C32—C22—C52	106.8 (3)
C11—N11—Ni1	121.3 (2)	C12—C22—C52	107.5 (3)
C11—N11—H11A	107.0	C42—C22—C52	109.3 (3)
Ni1—N11—H11A	107.0	N22—C32—C22	114.8 (3)
C11—N11—H11B	107.0	N22—C32—H32A	108.6
Ni1—N11—H11B	107.0	C22—C32—H32A	108.6
H11A—N11—H11B	106.7	N22—C32—H32B	108.6
C31—N21—Ni1	119.9 (2)	C22—C32—H32B	108.6
C31—N21—H21A	107.3	H32A—C32—H32B	107.5
Ni1—N21—H21A	107.3	C22—C42—H42A	109.5
C31—N21—H21B	107.3	C22—C42—H42B	109.5
Ni1—N21—H21B	107.3	H42A—C42—H42B	109.5
H21A—N21—H21B	106.9	C22—C42—H42C	109.5
N11—C11—C21	115.1 (3)	H42A—C42—H42C	109.5
N11—C11—H11C	108.5	H42B—C42—H42C	109.5
C21—C11—H11C	108.5	C22—C52—H52A	109.5
N11—C11—H11D	108.5	C22—C52—H52B	109.5
C21—C11—H11D	108.5	H52A—C52—H52B	109.5
H11C—C11—H11D	107.5	C22—C52—H52C	109.5
C31—C21—C41	112.6 (4)	H52A—C52—H52C	109.5
C31—C21—C11	111.2 (3)	H52B—C52—H52C	109.5
C41—C21—C11	111.7 (4)	C53—O43—Ni1	127.76 (17)
C31—C21—C51	106.8 (4)	C33^i—C13—C23	121.7 (3)
C41—C21—C51	107.8 (4)	C33^i—C13—H13	119.1
C11—C21—C51	106.4 (3)	C23—C13—H13	119.1
N21—C31—C21	115.4 (3)	C33—C23—C13	119.3 (3)
N21—C31—H31A	108.4	C33—C23—C53	121.4 (2)
C21—C31—H31A	108.4	C13—C23—C53	119.0 (3)
N21—C31—H31B	108.4	C13^i—C33—C23	119.0 (3)
C21—C31—H31B	108.4	C13^i—C33—C43	119.8 (3)
H31A—C31—H31B	107.5	C23—C33—C43	121.2 (2)
C21—C41—H41A	109.5	O23—C43—O13	125.1 (3)
C21—C41—H41B	109.5	O23—C43—C33	118.9 (3)
H41A—C41—H41B	109.5	O13—C43—C33	116.0 (3)
C21—C41—H41C	109.5	O33—C53—O43	126.2 (3)
H41A—C41—H41C	109.5	O33—C53—C23	117.3 (3)
H41B—C41—H41C	109.5	O43—C53—C23	116.4 (3)
C21—C51—H51A	109.5	C14—O14—H14	106.0
C21—C51—H51B	109.5	O14—C14—H14A	109.5
H51A—C51—H51B	109.5	O14—C14—H14B	109.5
C21—C51—H51C	109.5	H14A—C14—H14B	109.5
H51A—C51—H51C	109.5	O14—C14—H14C	109.5
H51B—C51—H51C	109.5	H14A—C14—H14C	109.5
C12—N12—Ni1	119.4 (2)	H14B—C14—H14C	109.5
C12—N12—H12A	107.5	Ni1—O1W—H1WA	120.5
Ni1—N12—H12A	107.5	Ni1—O1W—H1WB	122.0
C12—N12—H12B	107.5	H1WA—O1W—H1WB	109.3
Ni1—N12—H12B	107.5	H2WA—O2W—H2WB	108.4
H12A—N12—H12B	107.0	H3WA—O3W—H3WB	112.1
C32—N22—Ni1	122.0 (2)
O1W—Ni1—N11—C11	59.2 (2)	N12—C12—C22—C52	172.7 (3)
N22—Ni1—N11—C11	152.9 (2)	Ni1—N22—C32—C22	−51.1 (4)
N21—Ni1—N11—C11	−31.7 (2)	C12—C22—C32—N22	67.5 (4)
O43—Ni1—N11—C11	−118.4 (2)	C42—C22—C32—N22	−56.5 (4)
O1W—Ni1—N21—C31	−54.9 (3)	C52—C22—C32—N22	−175.4 (3)
N12—Ni1—N21—C31	−146.0 (3)	N11—Ni1—O43—C53	−27.5 (3)
O43—Ni1—N21—C31	125.7 (3)	N22—Ni1—O43—C53	61.3 (3)
Ni1—N11—C11—C21	53.6 (4)	N12—Ni1—O43—C53	151.7 (3)
N11—C11—C21—C31	−67.4 (4)	N21—Ni1—O43—C53	−116.8 (3)
N11—C11—C21—C41	59.3 (5)	C33^i—C13—C23—C33	−0.3 (5)
N11—C11—C21—C51	176.6 (4)	C33^i—C13—C23—C53	−174.3 (3)
Ni1—N21—C31—C21	−55.0 (4)	C13—C23—C33—C13^i	0.3 (5)
C41—C21—C31—N21	−57.5 (5)	C53—C23—C33—C13^i	174.2 (3)
C11—C21—C31—N21	68.6 (4)	C13—C23—C33—C43	177.9 (3)
C51—C21—C31—N21	−175.6 (3)	C53—C23—C33—C43	−8.3 (5)
O1W—Ni1—N12—C12	63.2 (2)	C13^i—C33—C43—O23	141.0 (3)
N22—Ni1—N12—C12	−30.4 (2)	C23—C33—C43—O23	−36.6 (5)
N21—Ni1—N12—C12	154.1 (2)	C13^i—C33—C43—O13	−38.6 (5)
O43—Ni1—N12—C12	−119.2 (2)	C23—C33—C43—O13	143.9 (3)
O1W—Ni1—N22—C32	−61.9 (2)	Ni1—O43—C53—O33	24.7 (5)
N11—Ni1—N22—C32	−148.7 (2)	Ni1—O43—C53—C23	−157.65 (19)
N12—Ni1—N22—C32	29.1 (2)	C33—C23—C53—O33	−59.6 (4)
O43—Ni1—N22—C32	117.5 (2)	C13—C23—C53—O33	114.3 (3)
Ni1—N12—C12—C22	55.1 (4)	C33—C23—C53—O43	122.5 (3)
N12—C12—C22—C32	−70.6 (4)	C13—C23—C53—O43	−63.6 (4)
N12—C12—C22—C42	53.4 (4)

Symmetry code: (i) −x+1, −y+1, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O14—H14···O33^ii	0.85	1.95	2.800 (5)	179
N11—H11A···O33	0.90	2.08	2.883 (3)	149
N11—H11B···O23^iii	0.90	2.11	3.005 (3)	170
N21—H21A···O13^ii	0.90	2.34	3.111 (4)	143
N12—H12A···O2W^iv	0.90	2.19	3.012 (3)	152
N12—H12B···O3W	0.90	2.25	3.124 (4)	165
N22—H22A···O23^iii	0.90	2.25	3.122 (3)	164
N22—H22B···O23	0.90	2.20	3.086 (3)	167
O1W—H1WA···O2W	0.85	1.90	2.706 (3)	157
O1W—H1WB···O13^iii	0.85	1.82	2.664 (3)	174
O2W—H2WA···O43^v	0.85	1.96	2.761 (3)	157
O2W—H2WB···O3W	0.85	1.95	2.740 (4)	155
O3W—H3WA···O13^ii	0.85	1.89	2.723 (4)	167
O3W—H3WB···O14	0.85	1.92	2.739 (5)	161

Symmetry codes: (ii) −x+1, y+1/2, −z+3/2; (iii) −x+1, −y+1, −z+1; (iv) x, −y+3/2, z+1/2; (v) x, −y+3/2, z−1/2.

(II) catena-poly[[[bis(2,2-methylpropane-1,3-amine- κ²N,N')nickel(II)]-µ-pyridine-2,5-dicarboxylato- κ³O⁵:N,O²-[(2,2-methylpropane-1,3-amine- κ²N,N')nickel(II)]-µ-pyridine-2,5-dicarboxylato- κ³N,O²:O⁵]octahydrate]

Crystal data

[Ni2(C7H3NO4)2(C5H14N2)3]·8H2O	Z = 2
Mr = 898.30	F(000) = 956
Triclinic, P1	Dx = 1.356 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.269 (3) Å	Cell parameters from 6745 reflections
b = 13.622 (3) Å	θ = 1.9–28.1°
c = 15.171 (4) Å	µ = 0.93 mm^−1
α = 105.25 (3)°	T = 295 K
β = 98.02 (2)°	Block, light green
γ = 111.25 (3)°	0.40 × 0.38 × 0.32 mm
V = 2200.8 (12) Å^3

Data collection

Bruker SMART? CCD area-detector diffractometer	9619 independent reflections
Radiation source: fine-focus sealed tube	6322 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ϕ and ω scans	θmax = 28.5°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −16→16
Tmin = 0.68, Tmax = 0.74	k = −17→17
18893 measured reflections	l = −20→19

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.192	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.1169P)^2] where P = (Fo^2 + 2Fc^2)/3
9619 reflections	(Δ/σ)max = 0.005
568 parameters	Δρmax = 0.70 e Å^−3
93 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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.5000	1.0000	0.5000	0.0474 (2)
Ni2	0.0000	0.0000	0.0000	0.0493 (2)
Ni3	0.53879 (4)	0.48684 (4)	0.25151 (3)	0.04313 (16)
C11	0.2278 (4)	0.9174 (5)	0.4843 (5)	0.110 (2)
H11A	0.1519	0.9001	0.4412	0.132*
H11B	0.2321	0.9677	0.5446	0.132*
C21	0.2216 (4)	0.8128 (4)	0.4981 (3)	0.0728 (12)
C31	0.3240 (4)	0.8214 (6)	0.5656 (5)	0.114 (2)
H31A	0.3289	0.8693	0.6273	0.137*
H31B	0.3068	0.7476	0.5695	0.137*
C41	0.2059 (6)	0.7275 (5)	0.4029 (4)	0.129 (2)
H41A	0.2022	0.7598	0.3540	0.194*
H41B	0.1323	0.6618	0.3886	0.194*
H41C	0.2734	0.7075	0.4064	0.194*
C51	0.1089 (5)	0.7611 (7)	0.5320 (6)	0.158 (3)
H51A	0.0416	0.7672	0.4971	0.237*
H51B	0.1243	0.8001	0.5982	0.237*
H51C	0.0905	0.6835	0.5218	0.237*
N11	0.3248 (3)	0.9781 (3)	0.4490 (3)	0.0694 (10)
H11C	0.3262	1.0467	0.4587	0.083*
H11D	0.3041	0.9436	0.3859	0.083*
N21	0.4415 (3)	0.8636 (3)	0.5476 (3)	0.0598 (9)
H21C	0.4458	0.8060	0.5048	0.072*
H21D	0.4966	0.8813	0.6016	0.072*
C12	0.1212 (4)	−0.1630 (3)	0.0135 (4)	0.0700 (12)
H12A	0.1990	−0.1666	0.0269	0.084*
H12B	0.0775	−0.2127	−0.0508	0.084*
C22	0.0523 (4)	−0.2050 (3)	0.0790 (3)	0.0726 (12)
C32	−0.0740 (4)	−0.2122 (3)	0.0554 (4)	0.0703 (12)
H32A	−0.1123	−0.2581	−0.0106	0.084*
H32B	−0.1193	−0.2505	0.0930	0.084*
C42	0.1152 (5)	−0.1298 (6)	0.1825 (3)	0.113 (2)
H42A	0.1150	−0.0574	0.1916	0.169*
H42B	0.1973	−0.1219	0.1976	0.169*
H42C	0.0728	−0.1630	0.2232	0.169*
C52	0.0451 (6)	−0.3229 (4)	0.0680 (5)	0.119 (2)
H52A	0.0288	−0.3643	0.0022	0.179*
H52B	−0.0188	−0.3611	0.0931	0.179*
H52C	0.1207	−0.3169	0.1018	0.179*
N12	0.1419 (3)	−0.0491 (3)	0.0187 (3)	0.0614 (9)
H12C	0.1826	−0.0338	−0.0244	0.074*
H12D	0.1925	−0.0036	0.0759	0.074*
N22	−0.0846 (3)	−0.1058 (3)	0.0706 (3)	0.0627 (9)
H22C	−0.0560	−0.0668	0.1331	0.075*
H22D	−0.1641	−0.1214	0.0552	0.075*
C23	0.7925 (4)	0.4348 (4)	0.2547 (3)	0.0683 (11)
C13"	0.7867 (12)	0.5169 (12)	0.2105 (11)	0.100 (5)	0.528 (7)
H13A	0.8674	0.5767	0.2291	0.120*	0.528 (7)
H13B	0.7670	0.4807	0.1425	0.120*	0.528 (7)
C33"	0.6774 (7)	0.3400 (7)	0.2414 (7)	0.082 (3)	0.528 (7)
H33A	0.6401	0.3023	0.1740	0.098*	0.528 (7)
H33B	0.6952	0.2872	0.2663	0.098*	0.528 (7)
C43"	0.8419 (10)	0.4940 (10)	0.3629 (4)	0.107 (4)	0.528 (7)
H43A	0.7926	0.5308	0.3858	0.160*	0.528 (7)
H43B	0.9238	0.5485	0.3773	0.160*	0.528 (7)
H43C	0.8398	0.4397	0.3928	0.160*	0.528 (7)
C53"	0.8884 (14)	0.3903 (19)	0.2362 (16)	0.131 (7)	0.528 (7)
H53A	0.8612	0.3369	0.1732	0.196*	0.528 (7)
H53B	0.9009	0.3547	0.2811	0.196*	0.528 (7)
H53C	0.9631	0.4514	0.2426	0.196*	0.528 (7)
C13'	0.8102 (7)	0.5487 (9)	0.2553 (12)	0.080 (4)	0.472 (7)
H13C	0.8558	0.6008	0.3185	0.096*	0.472 (7)
H13D	0.8604	0.5675	0.2130	0.096*	0.472 (7)
C33'	0.7189 (5)	0.3965 (10)	0.3154 (7)	0.070 (3)	0.472 (7)
H33C	0.7516	0.4543	0.3774	0.084*	0.472 (7)
H33D	0.7275	0.3309	0.3227	0.084*	0.472 (7)
C43'	0.7372 (10)	0.3549 (8)	0.1512 (4)	0.087 (3)	0.472 (7)
H43D	0.6531	0.3398	0.1325	0.131*	0.472 (7)
H43E	0.7450	0.2861	0.1458	0.131*	0.472 (7)
H43F	0.7792	0.3892	0.1109	0.131*	0.472 (7)
C53'	0.9201 (11)	0.441 (2)	0.2845 (15)	0.105 (5)	0.472 (7)
H53D	0.9439	0.4600	0.3520	0.158*	0.472 (7)
H53E	0.9761	0.4966	0.2658	0.158*	0.472 (7)
H53F	0.9200	0.3692	0.2545	0.158*	0.472 (7)
N13	0.7037 (3)	0.5685 (3)	0.2290 (3)	0.0590 (8)
H13G	0.6889	0.5914	0.1800	0.071*	0.528 (7)
H13H	0.7447	0.6308	0.2802	0.071*	0.528 (7)
H13I	0.7261	0.6419	0.2593	0.071*	0.472 (7)
H13J	0.6896	0.5585	0.1668	0.071*	0.472 (7)
N23	0.5900 (3)	0.3683 (3)	0.2855 (2)	0.0579 (8)
H23G	0.6206	0.3932	0.3487	0.069*	0.528 (7)
H23H	0.5226	0.3048	0.2707	0.069*	0.528 (7)
H23I	0.5556	0.3051	0.2348	0.069*	0.472 (7)
H23J	0.5571	0.3529	0.3324	0.069*	0.472 (7)
C14	0.3787 (3)	0.4777 (3)	0.3734 (2)	0.0425 (8)
N24	0.3803 (3)	0.4206 (2)	0.28696 (19)	0.0427 (7)
C34	0.2822 (3)	0.3301 (3)	0.2339 (2)	0.0448 (8)
H34	0.2834	0.2905	0.1741	0.054*
C44	0.1805 (3)	0.2927 (3)	0.2629 (2)	0.0433 (8)
C54	0.1781 (3)	0.3549 (3)	0.3515 (3)	0.0527 (9)
H54	0.1084	0.3319	0.3724	0.063*
C64	0.2785 (3)	0.4498 (3)	0.4077 (3)	0.0525 (9)
H64	0.2783	0.4931	0.4664	0.063*
C74	0.4960 (3)	0.5767 (3)	0.4324 (2)	0.0455 (8)
C84	0.0768 (3)	0.1840 (3)	0.2003 (3)	0.0511 (9)
O14	0.5818 (2)	0.5884 (2)	0.39442 (17)	0.0492 (6)
O24	0.4987 (2)	0.6362 (2)	0.51062 (17)	0.0564 (7)
O34	0.0932 (2)	0.1374 (2)	0.1229 (2)	0.0655 (8)
O44	−0.0113 (3)	0.1505 (3)	0.2299 (2)	0.0802 (10)
C15	0.4217 (3)	0.5531 (3)	0.1140 (2)	0.0470 (8)
N25	0.4787 (3)	0.5941 (2)	0.20644 (19)	0.0452 (7)
C35	0.4891 (3)	0.6947 (3)	0.2576 (2)	0.0480 (8)
H35	0.5295	0.7230	0.3215	0.058*
C45	0.4436 (4)	0.7596 (3)	0.2217 (3)	0.0523 (9)
C55	0.3869 (4)	0.7171 (4)	0.1272 (3)	0.0686 (12)
H55	0.3565	0.7582	0.0994	0.082*
C65	0.3748 (4)	0.6124 (4)	0.0728 (3)	0.0653 (11)
H65	0.3350	0.5828	0.0087	0.078*
C75	0.4143 (3)	0.4381 (3)	0.0606 (3)	0.0492 (8)
C85	0.4576 (4)	0.8713 (3)	0.2877 (3)	0.0594 (10)
O15	0.4644 (2)	0.3942 (2)	0.10753 (17)	0.0495 (6)
O25	0.3604 (2)	0.3933 (2)	−0.02580 (17)	0.0631 (8)
O35	0.4935 (3)	0.8881 (3)	0.3746 (2)	0.0716 (8)
O45	0.4301 (4)	0.9348 (3)	0.2541 (2)	0.0934 (12)
O1W	0.2874 (4)	0.1899 (4)	0.8222 (3)	0.1322 (18)
O2W	0.6800 (3)	0.8342 (3)	0.6318 (2)	0.0779 (9)
O3W	0.6088 (4)	0.8852 (3)	0.7944 (3)	0.1130 (13)
O4W	0.6150 (5)	0.8356 (3)	0.9608 (3)	0.1285 (16)
O5W	0.1007 (5)	0.1392 (4)	0.6761 (4)	0.1458 (19)
O6W	0.9254 (3)	0.9186 (3)	0.6268 (2)	0.0927 (11)
O7WA	0.1872 (12)	0.2494 (8)	0.5574 (9)	0.098 (3)	0.60
O7WB	0.2144 (19)	0.2054 (13)	0.5488 (15)	0.108 (6)	0.40
O8WA	0.7454 (9)	0.0318 (9)	0.1592 (8)	0.095 (3)*	0.40
O8WB	0.7536 (16)	0.0159 (15)	0.2079 (14)	0.082 (5)*	0.20
O8WC	0.5439 (15)	−0.0230 (15)	0.0975 (12)	0.081 (5)*	0.20
O8WD	0.440 (3)	−0.096 (3)	−0.002 (2)	0.081 (9)*	0.10
O8WE	0.540 (3)	0.036 (3)	0.156 (2)	0.072 (8)*	0.10

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0507 (4)	0.0406 (4)	0.0512 (4)	0.0227 (3)	0.0104 (3)	0.0123 (3)
Ni2	0.0347 (3)	0.0441 (4)	0.0499 (4)	0.0065 (3)	0.0084 (3)	0.0018 (3)
Ni3	0.0442 (3)	0.0392 (3)	0.0377 (3)	0.0116 (2)	0.00780 (19)	0.0100 (2)
C11	0.052 (3)	0.116 (4)	0.187 (7)	0.037 (3)	0.028 (4)	0.088 (4)
C21	0.048 (2)	0.075 (3)	0.087 (3)	0.017 (2)	0.006 (2)	0.034 (3)
C31	0.075 (3)	0.129 (5)	0.158 (5)	0.030 (4)	0.021 (3)	0.102 (5)
C41	0.123 (6)	0.096 (4)	0.137 (5)	0.029 (4)	−0.001 (4)	0.033 (4)
C51	0.078 (4)	0.202 (8)	0.231 (9)	0.042 (5)	0.051 (5)	0.150 (7)
N11	0.056 (2)	0.067 (2)	0.098 (3)	0.0296 (19)	0.0186 (19)	0.042 (2)
N21	0.056 (2)	0.056 (2)	0.069 (2)	0.0239 (17)	0.0074 (16)	0.0254 (17)
C12	0.055 (2)	0.070 (3)	0.088 (3)	0.030 (2)	0.023 (2)	0.025 (2)
C22	0.066 (3)	0.075 (3)	0.091 (3)	0.036 (2)	0.027 (2)	0.036 (3)
C32	0.056 (2)	0.055 (3)	0.089 (3)	0.013 (2)	0.020 (2)	0.022 (2)
C42	0.079 (4)	0.163 (6)	0.087 (3)	0.041 (4)	0.010 (3)	0.047 (4)
C52	0.096 (4)	0.108 (4)	0.199 (7)	0.057 (4)	0.059 (5)	0.091 (5)
N12	0.0455 (19)	0.061 (2)	0.070 (2)	0.0172 (17)	0.0173 (16)	0.0171 (18)
N22	0.053 (2)	0.058 (2)	0.071 (2)	0.0168 (17)	0.0265 (17)	0.0170 (18)
C23	0.059 (2)	0.074 (3)	0.078 (3)	0.033 (2)	0.019 (2)	0.027 (2)
C13"	0.097 (9)	0.148 (12)	0.114 (11)	0.076 (9)	0.059 (8)	0.085 (11)
C33"	0.085 (6)	0.083 (6)	0.081 (7)	0.044 (4)	0.020 (5)	0.022 (5)
C43"	0.076 (7)	0.133 (10)	0.082 (5)	0.018 (6)	0.006 (5)	0.035 (6)
C53"	0.117 (11)	0.14 (2)	0.199 (19)	0.094 (14)	0.083 (12)	0.076 (14)
C13'	0.050 (6)	0.081 (6)	0.130 (14)	0.035 (5)	0.034 (7)	0.053 (7)
C33'	0.068 (6)	0.105 (8)	0.066 (6)	0.050 (6)	0.026 (5)	0.048 (6)
C43'	0.119 (9)	0.100 (7)	0.077 (5)	0.069 (7)	0.055 (5)	0.038 (5)
C53'	0.077 (7)	0.122 (18)	0.158 (15)	0.069 (11)	0.049 (7)	0.063 (11)
N13	0.054 (2)	0.055 (2)	0.067 (2)	0.0183 (17)	0.0159 (16)	0.0258 (17)
N23	0.060 (2)	0.0500 (19)	0.062 (2)	0.0208 (17)	0.0142 (17)	0.0216 (16)
C14	0.0477 (19)	0.0414 (19)	0.0341 (18)	0.0172 (16)	0.0060 (14)	0.0104 (15)
N24	0.0441 (16)	0.0388 (16)	0.0346 (15)	0.0107 (13)	0.0077 (12)	0.0068 (12)
C34	0.0433 (19)	0.044 (2)	0.0380 (18)	0.0136 (16)	0.0070 (15)	0.0086 (16)
C44	0.0415 (18)	0.0399 (18)	0.0381 (18)	0.0132 (15)	0.0060 (14)	0.0047 (14)
C54	0.043 (2)	0.063 (2)	0.049 (2)	0.0210 (18)	0.0133 (16)	0.0160 (18)
C64	0.056 (2)	0.052 (2)	0.0365 (19)	0.0184 (18)	0.0090 (16)	0.0026 (16)
C74	0.047 (2)	0.0390 (19)	0.040 (2)	0.0110 (16)	0.0013 (16)	0.0126 (16)
C84	0.041 (2)	0.047 (2)	0.053 (2)	0.0092 (17)	0.0031 (17)	0.0160 (18)
O14	0.0469 (14)	0.0429 (14)	0.0413 (13)	0.0074 (11)	0.0030 (11)	0.0096 (11)
O24	0.0620 (17)	0.0484 (15)	0.0364 (14)	0.0147 (13)	0.0052 (12)	−0.0042 (12)
O34	0.0489 (16)	0.0571 (17)	0.0535 (17)	0.0035 (13)	0.0048 (13)	−0.0076 (14)
O44	0.0475 (17)	0.084 (2)	0.073 (2)	−0.0023 (16)	0.0184 (15)	0.0113 (18)
C15	0.0384 (18)	0.054 (2)	0.0412 (19)	0.0172 (17)	0.0110 (15)	0.0071 (16)
N25	0.0528 (18)	0.0431 (17)	0.0364 (16)	0.0186 (14)	0.0097 (13)	0.0114 (13)
C35	0.053 (2)	0.049 (2)	0.0337 (18)	0.0172 (17)	0.0072 (15)	0.0089 (16)
C45	0.053 (2)	0.055 (2)	0.054 (2)	0.0269 (19)	0.0182 (17)	0.0190 (18)
C55	0.081 (3)	0.089 (3)	0.052 (2)	0.059 (3)	0.008 (2)	0.021 (2)
C65	0.076 (3)	0.079 (3)	0.041 (2)	0.041 (3)	0.0019 (19)	0.016 (2)
C75	0.0379 (18)	0.052 (2)	0.042 (2)	0.0081 (16)	0.0107 (15)	0.0065 (17)
C85	0.057 (2)	0.057 (2)	0.067 (3)	0.030 (2)	0.013 (2)	0.017 (2)
O15	0.0548 (15)	0.0475 (15)	0.0397 (13)	0.0187 (12)	0.0118 (11)	0.0086 (11)
O25	0.0601 (17)	0.0691 (19)	0.0376 (14)	0.0182 (15)	0.0045 (12)	−0.0001 (13)
O35	0.097 (2)	0.0609 (18)	0.0606 (19)	0.0446 (18)	0.0192 (17)	0.0100 (15)
O45	0.120 (3)	0.079 (2)	0.091 (2)	0.067 (2)	0.001 (2)	0.020 (2)
O1W	0.097 (3)	0.121 (4)	0.121 (3)	0.000 (3)	0.048 (3)	0.008 (3)
O2W	0.071 (2)	0.0619 (19)	0.090 (2)	0.0257 (16)	−0.0007 (17)	0.0233 (17)
O3W	0.113 (3)	0.089 (3)	0.123 (3)	0.034 (2)	0.029 (3)	0.025 (3)
O4W	0.153 (4)	0.065 (2)	0.136 (4)	0.018 (3)	0.051 (3)	0.018 (2)
O5W	0.156 (4)	0.110 (4)	0.127 (4)	0.008 (3)	0.046 (3)	0.034 (3)
O6W	0.082 (2)	0.090 (3)	0.085 (2)	0.019 (2)	0.0098 (19)	0.028 (2)
O7WA	0.088 (6)	0.075 (7)	0.086 (5)	−0.001 (5)	0.033 (4)	0.002 (6)
O7WB	0.114 (13)	0.067 (10)	0.090 (9)	−0.007 (7)	0.020 (8)	0.013 (8)

Geometric parameters (Å, º)

Ni1—N11	2.064 (3)	C13"—N13	1.450 (4)
Ni1—N11^i	2.064 (3)	C13"—H13A	0.9700
Ni1—O35^i	2.073 (3)	C13"—H13B	0.9700
Ni1—O35	2.073 (3)	C33"—N23	1.453 (4)
Ni1—N21^i	2.091 (3)	C33"—H33A	0.9700
Ni1—N21	2.091 (3)	C33"—H33B	0.9700
Ni2—O34	2.076 (3)	C43"—H43A	0.9600
Ni2—O34^ii	2.076 (3)	C43"—H43B	0.9600
Ni2—N22^ii	2.083 (3)	C43"—H43C	0.9600
Ni2—N22	2.083 (3)	C53"—H53A	0.9600
Ni2—N12^ii	2.089 (3)	C53"—H53B	0.9600
Ni2—N12	2.089 (3)	C53"—H53C	0.9600
Ni3—N24	2.040 (3)	C13'—N13	1.451 (4)
Ni3—N13	2.052 (3)	C13'—H13C	0.9700
Ni3—N25	2.076 (3)	C13'—H13D	0.9700
Ni3—N23	2.086 (3)	C33'—N23	1.456 (4)
Ni3—O15	2.087 (3)	C33'—H33C	0.9700
Ni3—O14	2.113 (3)	C33'—H33D	0.9700
C11—N11	1.444 (4)	C43'—H43D	0.9600
C11—C21	1.470 (6)	C43'—H43E	0.9600
C11—H11A	0.9700	C43'—H43F	0.9600
C11—H11B	0.9700	C53'—H53D	0.9600
C21—C31	1.454 (6)	C53'—H53E	0.9600
C21—C41	1.534 (4)	C53'—H53F	0.9600
C21—C51	1.534 (7)	N13—H13G	0.9000
C31—N21	1.441 (4)	N13—H13H	0.9000
C31—H31A	0.9700	N13—H13I	0.8999
C31—H31B	0.9700	N13—H13J	0.9001
C41—H41A	0.9600	N23—H23G	0.9000
C41—H41B	0.9600	N23—H23H	0.9000
C41—H41C	0.9600	N23—H23I	0.9000
C51—H51A	0.9600	N23—H23J	0.9000
C51—H51B	0.9600	C14—N24	1.344 (4)
C51—H51C	0.9600	C14—C64	1.368 (5)
N11—H11C	0.9000	C14—C74	1.514 (5)
N11—H11D	0.9000	N24—C34	1.323 (4)
N21—H21C	0.9000	C34—C44	1.349 (5)
N21—H21D	0.9000	C34—H34	0.9300
C12—N12	1.457 (4)	C44—C54	1.398 (5)
C12—C22	1.488 (5)	C44—C84	1.507 (5)
C12—H12A	0.9700	C54—C64	1.374 (5)
C12—H12B	0.9700	C54—H54	0.9300
C22—C32	1.502 (5)	C64—H64	0.9300
C22—C42	1.534 (4)	C74—O24	1.237 (4)
C22—C52	1.539 (4)	C74—O14	1.250 (4)
C32—N22	1.463 (3)	C84—O44	1.210 (5)
C32—H32A	0.9700	C84—O34	1.259 (5)
C32—H32B	0.9700	C15—N25	1.342 (4)
C42—H42A	0.9600	C15—C65	1.370 (6)
C42—H42B	0.9600	C15—C75	1.526 (5)
C42—H42C	0.9600	N25—C35	1.335 (4)
C52—H52A	0.9600	C35—C45	1.385 (5)
C52—H52B	0.9600	C35—H35	0.9300
C52—H52C	0.9600	C45—C55	1.366 (5)
N12—H12C	0.9000	C45—C85	1.520 (5)
N12—H12D	0.9000	C55—C65	1.388 (6)
N22—H22C	0.9000	C55—H55	0.9300
N22—H22D	0.9000	C65—H65	0.9300
C23—C33'	1.443 (7)	C75—O25	1.254 (4)
C23—C13"	1.464 (9)	C75—O15	1.268 (5)
C23—C33"	1.471 (8)	C85—O45	1.231 (5)
C23—C13'	1.483 (9)	C85—O35	1.261 (5)
C23—C53"	1.533 (4)	O7WA—O7WB	0.776 (18)
C23—C53'	1.534 (4)	O8WA—O8WB	0.826 (18)
C23—C43'	1.542 (4)	O8WC—O8WE	1.05 (3)
C23—C43"	1.544 (4)	O8WC—O8WD	1.62 (4)
O1W···O5W	2.696 (7)	O5W···O7WB	2.685 (8)
O1W···O25^iii	2.838 (5)	O5W···O6W^v	2.809 (6)
O2W···O3W	2.730 (6)	O6W···O44^iv	2.807 (5)
O2W···O6W	2.825 (5)	O6W···O7WA^iv	2.876 (8)
O2W···O24	2.739 (5)	O6W···O7WB^iv	2.672 (8)
O3W···O4W	2.781 (7)	O7WA···O14^iv	2.730 (6)
O4W···O15^iv	2.766 (5)	O7WB···O14^iv	2.822 (6)
O5W···O7WA	2.725 (8)
N11—Ni1—N11^i	180.000 (1)	C22—C32—H32A	108.2
N11—Ni1—O35^i	88.17 (15)	N22—C32—H32B	108.2
N11^i—Ni1—O35^i	91.83 (15)	C22—C32—H32B	108.2
N11—Ni1—O35	91.83 (15)	H32A—C32—H32B	107.4
N11^i—Ni1—O35	88.17 (15)	C22—C42—H42A	109.5
O35^i—Ni1—O35	180.000 (1)	C22—C42—H42B	109.5
N11—Ni1—N21^i	87.73 (13)	H42A—C42—H42B	109.5
N11^i—Ni1—N21^i	92.27 (13)	C22—C42—H42C	109.5
O35^i—Ni1—N21^i	86.77 (14)	H42A—C42—H42C	109.5
O35—Ni1—N21^i	93.23 (14)	H42B—C42—H42C	109.5
N11—Ni1—N21	92.27 (13)	C22—C52—H52A	109.5
N11^i—Ni1—N21	87.73 (13)	C22—C52—H52B	109.5
O35^i—Ni1—N21	93.23 (14)	H52A—C52—H52B	109.5
O35—Ni1—N21	86.77 (14)	C22—C52—H52C	109.5
N21^i—Ni1—N21	180.000 (1)	H52A—C52—H52C	109.5
O34—Ni2—O34^ii	180.0 (2)	H52B—C52—H52C	109.5
O34—Ni2—N22^ii	85.95 (13)	C12—N12—Ni2	122.2 (3)
O34^ii—Ni2—N22^ii	94.05 (13)	C12—N12—H12C	106.8
O34—Ni2—N22	94.05 (13)	Ni2—N12—H12C	106.8
O34^ii—Ni2—N22	85.95 (13)	C12—N12—H12D	106.8
N22^ii—Ni2—N22	180.00 (16)	Ni2—N12—H12D	106.8
O34—Ni2—N12^ii	90.71 (13)	H12C—N12—H12D	106.6
O34^ii—Ni2—N12^ii	89.29 (13)	C32—N22—Ni2	119.4 (3)
N22^ii—Ni2—N12^ii	87.43 (13)	C32—N22—H22C	107.5
N22—Ni2—N12^ii	92.57 (13)	Ni2—N22—H22C	107.5
O34—Ni2—N12	89.29 (13)	C32—N22—H22D	107.5
O34^ii—Ni2—N12	90.71 (13)	Ni2—N22—H22D	107.5
N22^ii—Ni2—N12	92.57 (13)	H22C—N22—H22D	107.0
N22—Ni2—N12	87.43 (13)	C13"—C23—C33"	116.8 (8)
N12^ii—Ni2—N12	180.0 (2)	C33'—C23—C13'	113.3 (8)
N24—Ni3—N13	173.68 (12)	C13"—C23—C53"	116.0 (12)
N24—Ni3—N25	89.51 (12)	C33"—C23—C53"	108.9 (10)
N13—Ni3—N25	88.89 (13)	C33'—C23—C53'	111.7 (11)
N24—Ni3—N23	89.68 (12)	C13'—C23—C53'	105.8 (11)
N13—Ni3—N23	92.43 (13)	C33'—C23—C43'	111.4 (7)
N25—Ni3—N23	175.03 (12)	C13'—C23—C43'	107.6 (8)
N24—Ni3—O15	94.21 (11)	C53'—C23—C43'	106.6 (8)
N13—Ni3—O15	91.52 (13)	C13"—C23—C43"	108.9 (8)
N25—Ni3—O15	79.76 (11)	C33"—C23—C43"	105.1 (6)
N23—Ni3—O15	95.41 (12)	C53"—C23—C43"	99.1 (10)
N24—Ni3—O14	77.88 (11)	N13—C13"—C23	119.6 (7)
N13—Ni3—O14	96.03 (13)	N23—C33"—C23	115.7 (5)
N25—Ni3—O14	90.93 (11)	N13—C13'—C23	118.3 (7)
N23—Ni3—O14	93.69 (12)	C23—C33'—N23	117.3 (5)
O15—Ni3—O14	167.91 (10)	C13"—N13—Ni3	123.1 (6)
N11—C11—C21	119.1 (4)	C13'—N13—Ni3	124.5 (5)
N11—C11—H11A	107.6	C33"—N23—Ni3	117.8 (5)
C21—C11—H11A	107.6	C33'—N23—Ni3	118.1 (5)
N11—C11—H11B	107.6	N24—C14—C64	123.2 (3)
C21—C11—H11B	107.6	N24—C14—C74	116.0 (3)
H11A—C11—H11B	107.0	C64—C14—C74	120.9 (3)
C31—C21—C11	116.6 (5)	C34—N24—C14	118.7 (3)
C31—C21—C41	107.8 (5)	C34—N24—Ni3	126.7 (2)
C11—C21—C41	109.4 (5)	C14—N24—Ni3	114.6 (2)
C31—C21—C51	106.5 (4)	N24—C34—C44	122.7 (3)
C11—C21—C51	109.7 (4)	N24—C34—H34	118.6
C41—C21—C51	106.4 (5)	C44—C34—H34	118.6
N21—C31—C21	117.6 (4)	C34—C44—C54	118.2 (3)
N21—C31—H31A	107.9	C34—C44—C84	118.7 (3)
C21—C31—H31A	107.9	C54—C44—C84	123.0 (3)
N21—C31—H31B	107.9	C64—C54—C44	120.2 (3)
C21—C31—H31B	107.9	C64—C54—H54	119.9
H31A—C31—H31B	107.2	C44—C54—H54	119.9
C21—C41—H41A	109.5	C14—C64—C54	116.9 (3)
C21—C41—H41B	109.5	C14—C64—H64	121.6
H41A—C41—H41B	109.5	C54—C64—H64	121.6
C21—C41—H41C	109.5	O24—C74—O14	127.0 (3)
H41A—C41—H41C	109.5	O24—C74—C14	119.1 (3)
H41B—C41—H41C	109.5	O14—C74—C14	113.9 (3)
C21—C51—H51A	109.5	O44—C84—O34	127.4 (4)
C21—C51—H51B	109.5	O44—C84—C44	117.1 (4)
H51A—C51—H51B	109.5	O34—C84—C44	115.5 (3)
C21—C51—H51C	109.5	C74—O14—Ni3	116.7 (2)
H51A—C51—H51C	109.5	C84—O34—Ni2	139.8 (3)
H51B—C51—H51C	109.5	N25—C15—C65	121.1 (3)
C11—N11—Ni1	120.7 (3)	N25—C15—C75	115.0 (3)
C11—N11—H11C	107.2	C65—C15—C75	124.0 (3)
Ni1—N11—H11C	107.2	C35—N25—C15	118.3 (3)
C11—N11—H11D	107.2	C35—N25—Ni3	128.2 (2)
Ni1—N11—H11D	107.2	C15—N25—Ni3	113.4 (2)
H11C—N11—H11D	106.8	N25—C35—C45	124.2 (3)
C31—N21—Ni1	121.9 (3)	N25—C35—H35	117.9
C31—N21—H21C	106.8	C45—C35—H35	117.9
Ni1—N21—H21C	106.8	C55—C45—C35	116.6 (4)
C31—N21—H21D	106.8	C55—C45—C85	124.0 (4)
Ni1—N21—H21D	106.8	C35—C45—C85	119.4 (3)
H21C—N21—H21D	106.7	C45—C55—C65	120.1 (4)
N12—C12—C22	115.0 (4)	C45—C55—H55	120.0
N12—C12—H12A	108.5	C65—C55—H55	120.0
C22—C12—H12A	108.5	C15—C65—C55	119.7 (4)
N12—C12—H12B	108.5	C15—C65—H65	120.2
C22—C12—H12B	108.5	C55—C65—H65	120.2
H12A—C12—H12B	107.5	O25—C75—O15	124.3 (4)
C12—C22—C32	111.0 (4)	O25—C75—C15	118.7 (4)
C12—C22—C42	111.7 (4)	O15—C75—C15	117.0 (3)
C32—C22—C42	108.8 (4)	O45—C85—O35	125.8 (4)
C12—C22—C52	107.9 (4)	O45—C85—C45	119.3 (4)
C32—C22—C52	108.9 (4)	O35—C85—C45	114.9 (4)
C42—C22—C52	108.5 (5)	C75—O15—Ni3	114.7 (2)
N22—C32—C22	116.3 (3)	C85—O35—Ni1	135.6 (3)
N22—C32—H32A	108.2	O8WE—O8WC—O8WD	127 (3)
N11—C11—C21—C31	61.3 (8)	C54—C44—C84—O44	−0.4 (6)
N11—C11—C21—C41	−61.3 (7)	C34—C44—C84—O34	−1.8 (5)
N11—C11—C21—C51	−177.7 (6)	C54—C44—C84—O34	−179.3 (4)
C11—C21—C31—N21	−59.8 (8)	O24—C74—O14—Ni3	−170.8 (3)
C41—C21—C31—N21	63.6 (7)	C14—C74—O14—Ni3	9.5 (4)
C51—C21—C31—N21	177.4 (6)	N24—Ni3—O14—C74	−9.0 (3)
C21—C11—N11—Ni1	−43.2 (7)	N13—Ni3—O14—C74	169.2 (3)
O35^i—Ni1—N11—C11	−71.7 (4)	N25—Ni3—O14—C74	80.3 (3)
O35—Ni1—N11—C11	108.3 (4)	N23—Ni3—O14—C74	−97.9 (3)
N21^i—Ni1—N11—C11	−158.6 (4)	O15—Ni3—O14—C74	40.9 (6)
N21—Ni1—N11—C11	21.4 (4)	O44—C84—O34—Ni2	5.7 (8)
C21—C31—N21—Ni1	42.0 (7)	C44—C84—O34—Ni2	−175.5 (3)
N11—Ni1—N21—C31	−21.4 (4)	N22^ii—Ni2—O34—C84	139.9 (5)
N11^i—Ni1—N21—C31	158.6 (4)	N22—Ni2—O34—C84	−40.1 (5)
O35^i—Ni1—N21—C31	66.9 (4)	N12^ii—Ni2—O34—C84	52.5 (5)
O35—Ni1—N21—C31	−113.1 (4)	N12—Ni2—O34—C84	−127.5 (5)
N12—C12—C22—C32	63.8 (5)	C65—C15—N25—C35	−0.3 (5)
N12—C12—C22—C42	−57.8 (5)	C75—C15—N25—C35	179.7 (3)
N12—C12—C22—C52	−176.9 (4)	C65—C15—N25—Ni3	179.1 (3)
C12—C22—C32—N22	−66.8 (5)	C75—C15—N25—Ni3	−1.0 (4)
C42—C22—C32—N22	56.4 (6)	N24—Ni3—N25—C35	86.8 (3)
C52—C22—C32—N22	174.5 (4)	O15—Ni3—N25—C35	−178.8 (3)
C22—C12—N12—Ni2	−55.8 (5)	O14—Ni3—N25—C35	9.0 (3)
O34—Ni2—N12—C12	130.7 (3)	N24—Ni3—N25—C15	−92.4 (3)
O34^ii—Ni2—N12—C12	−49.3 (3)	N13—Ni3—N25—C15	93.7 (3)
N22^ii—Ni2—N12—C12	−143.4 (3)	O15—Ni3—N25—C15	2.0 (2)
N22—Ni2—N12—C12	36.6 (3)	O14—Ni3—N25—C15	−170.2 (2)
C22—C32—N22—Ni2	58.7 (5)	C15—N25—C35—C45	0.7 (5)
O34—Ni2—N22—C32	−126.0 (3)	Ni3—N25—C35—C45	−178.5 (3)
O34^ii—Ni2—N22—C32	54.0 (3)	N25—C35—C45—C55	−1.3 (6)
N12^ii—Ni2—N22—C32	143.1 (3)	N25—C35—C45—C85	178.1 (4)
N12—Ni2—N22—C32	−36.9 (3)	C35—C45—C55—C65	1.5 (7)
C64—C14—N24—C34	−3.1 (5)	C85—C45—C55—C65	−177.9 (4)
C74—C14—N24—C34	176.8 (3)	N25—C15—C65—C55	0.5 (7)
C64—C14—N24—Ni3	176.4 (3)	C75—C15—C65—C55	−179.5 (4)
C74—C14—N24—Ni3	−3.6 (4)	C45—C55—C65—C15	−1.1 (7)
N25—Ni3—N24—C34	94.7 (3)	N25—C15—C75—O25	178.7 (3)
N23—Ni3—N24—C34	−80.4 (3)	C65—C15—C75—O25	−1.3 (6)
O15—Ni3—N24—C34	15.0 (3)	N25—C15—C75—O15	−1.6 (5)
O14—Ni3—N24—C34	−174.2 (3)	C65—C15—C75—O15	178.4 (4)
N25—Ni3—N24—C14	−84.8 (3)	C55—C45—C85—O45	−9.1 (7)
N23—Ni3—N24—C14	100.1 (3)	C35—C45—C85—O45	171.5 (4)
O15—Ni3—N24—C14	−164.5 (2)	C55—C45—C85—O35	168.4 (4)
O14—Ni3—N24—C14	6.3 (2)	C35—C45—C85—O35	−10.9 (6)
C14—N24—C34—C44	0.1 (5)	O25—C75—O15—Ni3	−177.0 (3)
Ni3—N24—C34—C44	−179.4 (3)	C15—C75—O15—Ni3	3.3 (4)
N24—C34—C44—C54	2.2 (6)	N24—Ni3—O15—C75	85.8 (3)
N24—C34—C44—C84	−175.5 (3)	N13—Ni3—O15—C75	−91.6 (3)
C34—C44—C54—C64	−1.6 (6)	N25—Ni3—O15—C75	−3.0 (2)
C84—C44—C54—C64	176.0 (4)	N23—Ni3—O15—C75	175.9 (2)
N24—C14—C64—C54	3.6 (6)	O14—Ni3—O15—C75	37.2 (6)
C74—C14—C64—C54	−176.4 (3)	O45—C85—O35—Ni1	12.0 (8)
C44—C54—C64—C14	−1.1 (6)	C45—C85—O35—Ni1	−165.4 (3)
N24—C14—C74—O24	176.3 (3)	N11—Ni1—O35—C85	45.5 (4)
C64—C14—C74—O24	−3.7 (5)	N11^i—Ni1—O35—C85	−134.5 (4)
N24—C14—C74—O14	−4.0 (5)	N21^i—Ni1—O35—C85	−42.4 (4)
C64—C14—C74—O14	176.0 (3)	N21—Ni1—O35—C85	137.6 (4)
C34—C44—C84—O44	177.1 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11C···O2W^i	0.90	2.39	3.127 (6)	139
N12—H12D···O3W^iv	0.90	2.56	3.423 (6)	160
N13—H13G···O25^vi	0.90	2.42	3.297 (4)	165
N13—H13H···O7WA^iv	0.90	2.40	3.256 (4)	159
N23—H23H···O3W^iv	0.90	2.33	3.196 (6)	160

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