Hexakis[tris­(ethyl­ene­diamine-κ²N,N′)nickel(II)] tricyano­cuprate(I) bis­{μ-cyano-bis­[tricyano­cuprate(I)]} nona­hydrate

The title compound, [Ni(C₂H₈N₂)₃]₆[Cu(CN)₃][Cu₂(CN)₇]₂·9H₂O, was formed upon dissolution of a freshly prepared precipitate of CuNi(CN)₄ in ethyl­ene­diamine (en) as a result of complex redox and complexation equilibriums in the presence of air. The compound exhibits an ionic structure and contains three crystallographically independent chiral [Ni(en)₃]²⁺ cations, planar [Cu(CN)₃]²⁻ and chiral [(NC)₃Cu–(μ-CN)–Cu(CN)₃]⁵⁻ anions, and water mol­ecules of crystallization. All metal atoms are situated on special positions. One of the Ni atoms lies on a twofold axis, whereas all other metal atoms are located on threefold axes.

S1. Comment

Magneto-structural correlations are being intensively studied at present (Verdaguer et al., 1999; Ohba & Okawa, 2000; Dunbar & Heintz, 1997; Mukherjee et al., 2004; Chandramouli et al., 2003; Boča, 2004). Literature data show that the magnetic dimensionality of the system may differ from the structural dimensionality governed by covalent bonds. For example, Cu(en)₂Ni(CN)₄ (en = 1,2-diaminoethane) exhibits a one-dimensional crystal structure displaying composition [–Cu(en)₂–(µNC)–Ni(CN)₂–(µCN)–Cu–] (Seitz et al., 2001), but at low temperatures it behaves as a two-dimensional magnet with short-range ordering at 230 mK. It was proposed that N—H···N type hydrogen bonds may serve as additional exchange paths for magnetic interactions in this compound (Orendáč et al., 1995). In order to better understand the role of the hydrogen bonds (HBs) in mediating magnetic interactions and to avoid the possibility of mediation of magnetic interactions via bridging cyano ligands, we tried to prepare tetracyanonickellate compound with the [Cu(en)₃]²⁺ cation; this cation has already been structurally characterized {e.g. in [Cu(en)₃]SO₄ (Cullen & Lingafelter, 1970)}. Instead, we unexpectedly obtained in low yield (15%) a new compound, [Ni(en)₃]₆[Cu₂(CN)₇]₂[Cu(CN)₃]·9H₂O, (I); the synthetic procedure is reproducible. Our attempts to prepare (I) from the aqueous system Ni^II–en–Cu^I–CN⁻ were unsuccessful.

The structure of (I) is built up of [Ni(en)₃]²⁺ cations, [Cu(CN)₃]²⁻ and [(NC)₃Cu(µ-CN)Cu(CN)₃]⁵⁻ anions, and water molecules of crystallization. It is isotructural with the analogous zinc compound described by Černák et al. (1994). The structures of the analogous Cu^I/Cu^II mixed-valence compounds Cu(en)₂(H₂O)Cu₂(CN)₄ and [Cu(en)₃][Cu(CN)₃]·2H₂O have also been described (Williams et al., 1972; Wicholas & Wolford, 1975).

In the unit cell there are three crystallographically independent chiral cations [Ni(en)₃]²⁺; the Ni^II atoms lie on special positions, viz. Ni1 on the threefold axis, Ni2 on the intersection of the twofold and threefold axes, and Ni3 on the twofold axis. All Ni^II atoms are coordinated in a pseudo-octahedral manner by three chelating molecules of ethylenediamine (Figs. 1a–1c). The chelate rings exhibit a gauche conformation. There are three types of enantiomorphs; the configurations of the [Ni1(en)₃]²⁺ and [Ni3(en)₃]²⁺ cations are Λδδδ and Λδδλ, respectively, and the configuration of the [Ni2(en)₃]²⁺ cation (the same mean as in the case of atom Ni1) is Δλλλ. The average values of the Ni—N bond [2.129 (1) Å] and N—Ni—N angle within the metallocycle [81.75 (2) °] are as observed in octahedral complexes of Ni^II; e.g. in [Ni(en)₃]SO₄ the corresponding values are 2.125 (2) Å and 80.9 (2)°, respectively (Jameson et al., 1982).

The positive charges of the cations are compensated by two structurally different anions in the unit cell. The planar anion [Cu(CN)₃]²⁻ has already been described, e.g. in Na₂[Cu(CN)₃]·3H₂O (Kappenstein & Hugel, 1977) and [Cu(en)₃][Cu(CN)₃]·2H₂O (Wicholas & Wolford, 1975). The symmetry of this anion is D_3h (Fig. 1d) and the geometrical parameters correspond to those described previously.

The second chiral anion, [(NC)₃Cu(µ-CN)Cu(CN)₃]⁵⁻ (symmetry C₃), was previously described only in the analogous zinc compound (Černák et al., 1994); it forms also a part of the polymeric anion in [H₃₁O₁₄][CdCu₂(CN)₇] (Nishikiori & Iwamoto, 1993). In this anion exist two different CuC₄ and CuC₃N coordination spheres with tetrahedrally coordinated Cu^I atoms (Fig. 1e). The dihedral angle between the Cu5/Cu6/C51/N51 and Cu6/Cu5/C61/N61 least-square planes is 26.6 (1)°, which means that the conformation of the anion is staggered. The corresponding value in the isostructural zinc compound is 23.8 (1)° (Černák et al., 1994). The Cu—C bond lengths in the CuC₄ chromophore are shorter than the equivalent bonds in K₃[Cu(CN)₄] (Roof et al., 1968), and the bond lengths for CuC₃N are similar to those in Cu(en)₂Cu₂(CN)₄·H₂O (Williams et al., 1972).

There are two crystallographically different water molecules of crystallization in the unit cell; these are involved in the hydrogen-bond system and contribute to the stability of the packing as well as to the configuration of the cations.

The formation of (I) means that during preparation the central atoms exchanged their ligands and, moreover, reduction of Cu^II to Cu^I occurred. One of the reasons behind such an exchange could be the (partial) instability of Cu^II in the presence of cyano ligands leading to various cyanocuprate anions and/or Cu^II/Cu^I mixed-valence compounds (Dunaj-Jurčo et al., 1988). The higher stability of the [Ni(en)₃]²⁺ cation with respect to the [Cu(en)₃]²⁺ cation forced by the very high concentration of the en ligand may also play an important role.

S2. Experimental

To a 0.1 M warm solution [specify solvent] (10 ml) of CuSO₄ (1 mmol) was added slowly a 0.1 M warm solution (10 ml) of K₂[Ni(CN)₄]·H₂O (1 mmol) (333 K). The formed glaucous precipitate was filtered off, washed several times with water until negative reaction with barium chloride, and then dissolved in liquid en (large excess). The resulting clear blue solution was left for crystallization in a refrigerator (277 K). Single crystals of (I) appeared after one week (yield 0.348 g, 15%). Analysis calculated (Mr = 2356.31): C 27.74, H 6.74, N 31.84, Ni 14.93, Cu 13.48%; found (CHNS Elemental Analyzer Flash EA 1112; Thermo Finnigan, Ni gravimetrically as dimethylglyoximato complex): C 27.28, H 6.77, N 31.68, Ni 14.2, Cu 15.73%. FT–IR (KBr, cm⁻¹): 3333 (vs), 3282 (vs), 2962 (s), 2935 (s), 2885 (s), 2089 (vs), 2079 (vs), 1664 (m), 1587 (s), 1570 (vs), 1470 (s), 1396 (m), 1335 (m), 1281 (m), 1149 (w), 1113 (m), 1024 (vs), 972 (m), 947 (w), 669 (s), 640 (s), 517 (s), 490 (w).

S3. Refinement

H atoms were treated as riding, with C—H distances of 0.96 or 0.99 Å, O—H distances of 0.85 and N—H distances of 0.92 Å.

Computing details

Data collection: EXPOSE in IPDS (Stoe & Cie, 1999); cell refinement: CELL in IPDS; data reduction: INTEGRATE in IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Crystal Impact, 2001); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Views of the ions of the title compound, with displacement ellipsoids drawn at the 30% probability level; H atoms have been omitted. (a) [Ni(en)3]^2+ (Ni1, internal symmetry 3), (b) [Ni(en)3]^2+ (Ni2, internal symmetry 32), (c) [Ni(en)3]^2+ (Ni3, internal symmetry 2), (d) [Cu(CN)3]^2− (Cu4, internal symmetry 3) (e) [Cu2(CN)7]^5− (Cu5 and Cu6, internal symmetry 3).

hexakis[tris(ethylenediamine-κ²N,N')nickel(II)] tricyanocuprate(I) bis{µ-cyano-bis[tricyanocuprate(I)]} nonahydrate, [Ni(C₂H₈N₂)₃]₆[Cu₂(CN)₇]₂[Cu(CN)₃]·9H₂O

Crystal data

[Ni(C2H8N2)3]6[Cu2(CN)7]2[Cu(CN)3]·9H2O	Dx = 1.513 Mg m^−3
Mr = 2356.32	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32	Cell parameters from 8000 reflections
Hall symbol: R 3 2	θ = 2.6–30.3°
a = 15.3025 (5) Å	µ = 2.14 mm^−1
c = 38.2467 (17) Å	T = 193 K
V = 7756.2 (5) Å^3	Block, blue
Z = 3	0.24 × 0.22 × 0.12 mm
F(000) = 3708

Data collection

Stoe IPDS diffractometer	4597 independent reflections
Radiation source: fine-focus sealed tube	3287 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.065
Detector resolution: 150 pixels mm^-1	θmax = 29.0°, θmin = 2.6°
ϕ scans	h = −20→20
Absorption correction: multi-scan (WinGX; Farrugia, 1999; Spek, 2003)	k = −20→19
Tmin = 0.623, Tmax = 0.813	l = −52→51
27795 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0446P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.89	(Δ/σ)max < 0.001
4597 reflections	Δρmax = 0.63 e Å^−3
207 parameters	Δρmin = −0.62 e Å^−3
14 restraints	Absolute structure: Flack (1983), 2050 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (2)

Special details

Experimental. For elemental analysis: CHNS Elemental Analyzer Flash EA 1112; Thermo Finnigan, Ni gravimetrically as dimethylglyoximato complex.

For FT–IR: Nicolet Avatar 330 F T—IR, in KBr.

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. ISOR restraint for O3. Crossing twist disorder of en ligand at Ni2: C21A and C21B refined with SADI restraints in C—N and C—C bond lengths, ISOR restraints in the common anisotropic displacement factor.

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

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.0000	0.0000	0.119160 (15)	0.02724 (15)
Ni2	0.0000	0.0000	0.5000	0.0270 (2)
Ni3	0.15322 (4)	0.3333	0.3333	0.02197 (13)
Cu4	0.0000	0.0000	0.0000	0.0300 (2)
Cu5	0.0000	0.0000	0.239944 (16)	0.03580 (17)
Cu6	0.0000	0.0000	0.378175 (14)	0.02865 (15)
N1	0.0000	0.0000	0.29620 (10)	0.0272 (9)
C1	0.0000	0.0000	0.32615 (12)	0.0261 (10)
N11	0.0259 (4)	0.1258 (3)	0.15069 (10)	0.0667 (13)
H11A	0.0192	0.1086	0.1740	0.080*
H11B	0.0901	0.1788	0.1470	0.080*
N12	−0.0829 (4)	0.0510 (5)	0.08920 (10)	0.0732 (15)
H12A	−0.0667	0.0537	0.0659	0.088*
H12B	−0.1510	0.0071	0.0917	0.088*
C11	−0.0480 (7)	0.1545 (5)	0.14094 (17)	0.096 (3)
H11C	−0.0262	0.2235	0.1495	0.116*
H11D	−0.1141	0.1076	0.1516	0.116*
C12	−0.0575 (7)	0.1510 (6)	0.10155 (19)	0.106 (3)
H12C	−0.1108	0.1661	0.0945	0.128*
H12D	0.0070	0.2025	0.0910	0.128*
N31	0.2078 (2)	0.2316 (2)	0.32425 (9)	0.0287 (7)
H31A	0.1914	0.1879	0.3428	0.034*
H31B	0.1788	0.1945	0.3044	0.034*
N32	0.1280 (2)	0.3066 (2)	0.38853 (7)	0.0315 (6)*
H32A	0.0941	0.2384	0.3931	0.038*
H32B	0.1885	0.3359	0.4003	0.038*
N33	0.1097 (2)	0.4419 (2)	0.34390 (9)	0.0287 (7)
H33A	0.1552	0.5028	0.3340	0.034*
H33B	0.0471	0.4215	0.3345	0.034*
C31	0.3179 (3)	0.2906 (3)	0.32012 (11)	0.0373 (9)
H31C	0.3344	0.3179	0.2969	0.045*
H31D	0.3465	0.2479	0.3236	0.045*
C32	0.0668 (3)	0.3522 (3)	0.39954 (10)	0.0354 (8)*
H32C	0.0704	0.3608	0.4252	0.042*
H32D	−0.0046	0.3072	0.3929	0.042*
C33	0.1067 (3)	0.4529 (3)	0.38199 (10)	0.0320 (8)
H33C	0.0628	0.4814	0.3877	0.038*
H33D	0.1754	0.5002	0.3907	0.038*
C41	−0.1279 (4)	−0.1279 (4)	0.0000	0.0381 (13)
N41	−0.2020 (4)	−0.2020 (4)	0.0000	0.0603 (16)
C51	0.1243 (4)	0.1285 (4)	0.23033 (10)	0.0425 (10)
N51	0.1977 (4)	0.2062 (3)	0.22805 (11)	0.0646 (12)
C61	−0.0811 (3)	0.0608 (3)	0.39484 (8)	0.0293 (7)
N61	−0.1299 (3)	0.0930 (3)	0.40382 (9)	0.0472 (9)
N21A	0.0576 (4)	0.1337 (2)	0.46966 (7)	0.0500 (9)	0.50
H21A	0.1235	0.1557	0.4635	0.060*	0.255 (15)
H21B	0.0204	0.1213	0.4495	0.060*	0.255 (15)
N21B	0.0576 (4)	0.1337 (2)	0.46966 (7)	0.0500 (9)	0.50
H21C	0.1259	0.1734	0.4733	0.060*	0.745 (15)
H21D	0.0470	0.1176	0.4463	0.060*	0.745 (15)
C21A	0.0516 (8)	0.2125 (7)	0.4910 (5)	0.071 (3)	0.255 (15)
H21E	0.0584	0.2679	0.4757	0.106*	0.255 (15)
H21F	0.1063	0.2411	0.5086	0.106*	0.255 (15)
C21B	0.0050 (9)	0.1901 (7)	0.48008 (16)	0.071 (3)	0.745 (15)
H21G	−0.0625	0.1591	0.4691	0.106*	0.745 (15)
H21H	0.0446	0.2612	0.4723	0.106*	0.745 (15)
O1	0.2642 (5)	0.2979 (5)	0.11186 (12)	0.0457 (15)	0.50
H1O1	0.2954	0.3396	0.0955	0.069*	0.50
H2O1	0.2790	0.2513	0.1106	0.069*	0.50
O2	0.2950 (8)	0.3651 (6)	0.18142 (13)	0.105 (4)	0.50
H1O2	0.2607	0.3728	0.1655	0.157*	0.50
H2O2	0.2607	0.3050	0.1890	0.157*	0.50
O3	0.2018 (5)	0.2905 (8)	0.11546 (17)	0.136 (4)	0.50
H1O3	0.1935	0.3026	0.1365	0.204*	0.50
H2O3	0.1526	0.2857	0.1036	0.204*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0299 (2)	0.0299 (2)	0.0220 (3)	0.01493 (12)	0.000	0.000
Ni2	0.0321 (3)	0.0321 (3)	0.0169 (4)	0.01603 (16)	0.000	0.000
Ni3	0.0215 (2)	0.0193 (3)	0.0244 (2)	0.00964 (13)	0.00145 (10)	0.00290 (19)
Cu4	0.0288 (3)	0.0288 (3)	0.0325 (4)	0.01441 (17)	0.000	0.000
Cu5	0.0413 (3)	0.0413 (3)	0.0248 (3)	0.02066 (13)	0.000	0.000
Cu6	0.0330 (2)	0.0330 (2)	0.0200 (3)	0.01648 (11)	0.000	0.000
N1	0.0303 (15)	0.0303 (15)	0.0208 (19)	0.0152 (7)	0.000	0.000
C1	0.0259 (16)	0.0259 (16)	0.026 (3)	0.0129 (8)	0.000	0.000
N11	0.111 (4)	0.047 (2)	0.047 (2)	0.043 (2)	−0.014 (2)	−0.0096 (17)
N12	0.087 (4)	0.112 (4)	0.0441 (19)	0.067 (3)	−0.014 (2)	0.005 (3)
C11	0.174 (8)	0.088 (4)	0.088 (4)	0.110 (5)	−0.002 (4)	−0.014 (4)
C12	0.169 (8)	0.108 (6)	0.104 (5)	0.116 (6)	−0.004 (5)	0.031 (4)
N31	0.0276 (16)	0.0247 (16)	0.0316 (19)	0.0113 (13)	0.0008 (12)	−0.0001 (12)
N33	0.0284 (15)	0.0240 (15)	0.0353 (18)	0.0142 (13)	0.0007 (13)	0.0033 (13)
C31	0.030 (2)	0.035 (2)	0.051 (2)	0.0198 (18)	0.0026 (17)	0.0008 (17)
C33	0.0344 (19)	0.0270 (17)	0.0368 (19)	0.0169 (15)	0.0053 (15)	−0.0022 (15)
C41	0.028 (2)	0.028 (2)	0.055 (4)	0.012 (2)	−0.0032 (12)	0.0032 (12)
N41	0.038 (2)	0.038 (2)	0.094 (5)	0.011 (3)	−0.0020 (16)	0.0020 (16)
C51	0.051 (3)	0.050 (3)	0.027 (2)	0.026 (2)	0.0067 (17)	0.0049 (17)
N51	0.074 (3)	0.052 (3)	0.051 (2)	0.019 (2)	0.016 (2)	0.008 (2)
C61	0.034 (2)	0.0312 (19)	0.0199 (13)	0.0138 (16)	0.0008 (15)	0.0025 (16)
N61	0.054 (2)	0.051 (2)	0.0445 (17)	0.032 (2)	0.0003 (17)	−0.0054 (16)
N21A	0.084 (3)	0.0381 (17)	0.0238 (12)	0.027 (2)	−0.003 (2)	0.0042 (11)
N21B	0.084 (3)	0.0381 (17)	0.0238 (12)	0.027 (2)	−0.003 (2)	0.0042 (11)
C21A	0.135 (7)	0.055 (4)	0.041 (4)	0.062 (5)	−0.014 (4)	−0.004 (3)
C21B	0.135 (7)	0.055 (4)	0.041 (4)	0.062 (5)	−0.014 (4)	−0.004 (3)
O1	0.044 (4)	0.057 (4)	0.051 (3)	0.036 (3)	0.025 (3)	0.031 (3)
O2	0.174 (11)	0.059 (5)	0.074 (5)	0.053 (6)	0.035 (6)	0.014 (4)
O3	0.162 (9)	0.091 (6)	0.104 (7)	0.024 (6)	−0.026 (6)	0.024 (5)

Geometric parameters (Å, º)

Ni1—N12^i	2.126 (4)	C11—H11C	0.9900
Ni1—N12	2.126 (4)	C11—H11D	0.9900
Ni1—N12^ii	2.126 (4)	C12—H12C	0.9900
Ni1—N11	2.134 (4)	C12—H12D	0.9900
Ni1—N11^ii	2.134 (4)	N31—C31	1.469 (5)
Ni1—N11^i	2.134 (4)	N31—H31A	0.9200
Ni2—N21B^i	2.123 (3)	N31—H31B	0.9200
Ni2—N21A^i	2.123 (3)	N32—C32	1.481 (5)
Ni2—N21B^ii	2.123 (3)	N32—H32A	0.9200
Ni2—N21A^ii	2.123 (3)	N32—H32B	0.9200
Ni2—N21B^iii	2.123 (3)	N33—C33	1.470 (5)
Ni2—N21A^iii	2.123 (3)	N33—H33A	0.9200
Ni2—N21A	2.123 (3)	N33—H33B	0.9200
Ni2—N21B^iv	2.123 (3)	C31—C31^vi	1.519 (8)
Ni2—N21A^iv	2.123 (3)	C31—H31C	0.9599
Ni2—N21B^v	2.123 (3)	C31—H31D	0.9600
Ni2—N21A^v	2.123 (3)	C32—C33	1.503 (5)
Ni3—N33^vi	2.115 (3)	C32—H32C	0.9900
Ni3—N33	2.115 (3)	C32—H32D	0.9900
Ni3—N31	2.131 (3)	C33—H33C	0.9900
Ni3—N31^vi	2.131 (3)	C33—H33D	0.9900
Ni3—N32	2.148 (3)	C41—N41	1.133 (7)
Ni3—N32^vi	2.148 (3)	C51—N51	1.161 (6)
Cu4—C41^ii	1.958 (6)	C61—N61	1.135 (5)
Cu4—C41^i	1.958 (6)	N21A—C21A	1.496 (9)
Cu4—C41	1.958 (6)	N21A—H21A	0.9200
Cu5—C51	1.970 (5)	N21A—H21B	0.9200
Cu5—C51^ii	1.970 (5)	C21A—C21A^iv	1.531 (13)
Cu5—C51^i	1.970 (5)	C21A—H21E	0.9900
Cu5—N1	2.152 (4)	C21A—H21F	0.9900
Cu6—C1	1.990 (5)	C21B—C21B^iv	1.529 (12)
Cu6—C61^ii	1.991 (4)	C21B—H21G	0.9900
Cu6—C61	1.991 (4)	C21B—H21H	0.9900
Cu6—C61^i	1.991 (4)	O1—H1O1	0.8499
N1—C1	1.145 (6)	O1—H2O1	0.8499
N11—C11	1.451 (8)	O1—H1O3	1.4639
N11—H11A	0.9200	O2—O2^vii	1.519 (17)
N11—H11B	0.9200	O2—H1O2	0.8501
N12—C12	1.457 (8)	O2—H2O2	0.8500
N12—H12A	0.9200	O3—H1O1	1.4576
N12—H12B	0.9200	O3—H1O3	0.8500
C11—C12	1.512 (9)	O3—H2O3	0.8500
N12^i—Ni1—N12	93.68 (16)	C1—Cu6—C61	108.67 (9)
N12^i—Ni1—N12^ii	93.68 (16)	C61^ii—Cu6—C61	110.26 (8)
N12—Ni1—N12^ii	93.68 (16)	C1—Cu6—C61^i	108.67 (9)
N12^i—Ni1—N11	170.7 (2)	C61^ii—Cu6—C61^i	110.26 (8)
N12—Ni1—N11	81.33 (18)	C61—Cu6—C61^i	110.26 (8)
N12^ii—Ni1—N11	94.4 (2)	C1—N1—Cu5	180.000 (1)
N12^i—Ni1—N11^ii	94.4 (2)	N1—C1—Cu6	180.0
N12—Ni1—N11^ii	170.7 (2)	C11—N11—Ni1	107.9 (3)
N12^ii—Ni1—N11^ii	81.33 (18)	C11—N11—H11A	110.1
N11—Ni1—N11^ii	91.22 (15)	Ni1—N11—H11A	110.1
N12^i—Ni1—N11^i	81.33 (18)	C11—N11—H11B	110.1
N12—Ni1—N11^i	94.4 (2)	Ni1—N11—H11B	110.1
N12^ii—Ni1—N11^i	170.7 (2)	H11A—N11—H11B	108.4
N11—Ni1—N11^i	91.22 (15)	C12—N12—Ni1	108.4 (4)
N11^ii—Ni1—N11^i	91.22 (15)	C12—N12—H12A	110.0
N21B^i—Ni2—N21A^i	0.0 (4)	Ni1—N12—H12A	110.0
N21B^i—Ni2—N21B^ii	92.97 (11)	C12—N12—H12B	110.0
N21A^i—Ni2—N21B^ii	92.97 (11)	Ni1—N12—H12B	110.0
N21B^i—Ni2—N21A^ii	92.97 (11)	H12A—N12—H12B	108.4
N21A^i—Ni2—N21A^ii	92.97 (11)	N11—C11—C12	108.7 (5)
N21B^ii—Ni2—N21A^ii	0.0 (3)	N11—C11—H11C	109.9
N21B^i—Ni2—N21B^iii	172.3 (3)	C12—C11—H11C	109.9
N21A^i—Ni2—N21B^iii	172.3 (3)	N11—C11—H11D	109.9
N21B^ii—Ni2—N21B^iii	81.7 (2)	C12—C11—H11D	109.9
N21A^ii—Ni2—N21B^iii	81.7 (2)	H11C—C11—H11D	108.3
N21B^i—Ni2—N21A^iii	172.3 (3)	N12—C12—C11	109.3 (4)
N21A^i—Ni2—N21A^iii	172.3 (3)	N12—C12—H12C	109.8
N21B^ii—Ni2—N21A^iii	81.7 (2)	C11—C12—H12C	109.8
N21A^ii—Ni2—N21A^iii	81.7 (2)	N12—C12—H12D	109.8
N21B^iii—Ni2—N21A^iii	0.0 (3)	C11—C12—H12D	109.8
N21B^i—Ni2—N21A	92.97 (11)	H12C—C12—H12D	108.3
N21A^i—Ni2—N21A	92.97 (11)	C31—N31—Ni3	108.5 (2)
N21B^ii—Ni2—N21A	92.97 (11)	C31—N31—H31A	110.0
N21A^ii—Ni2—N21A	92.97 (11)	Ni3—N31—H31A	110.0
N21B^iii—Ni2—N21A	92.8 (3)	C31—N31—H31B	110.0
N21A^iii—Ni2—N21A	92.8 (3)	Ni3—N31—H31B	110.0
N21B^i—Ni2—N21B^iv	92.8 (3)	H31A—N31—H31B	108.4
N21A^i—Ni2—N21B^iv	92.8 (3)	C32—N32—Ni3	106.6 (2)
N21B^ii—Ni2—N21B^iv	172.3 (3)	C32—N32—H32A	110.4
N21A^ii—Ni2—N21B^iv	172.3 (3)	Ni3—N32—H32A	110.4
N21B^iii—Ni2—N21B^iv	92.97 (11)	C32—N32—H32B	110.4
N21A^iii—Ni2—N21B^iv	92.97 (11)	Ni3—N32—H32B	110.4
N21A—Ni2—N21B^iv	81.7 (2)	H32A—N32—H32B	108.6
N21B^i—Ni2—N21A^iv	92.8 (3)	C33—N33—Ni3	108.6 (2)
N21A^i—Ni2—N21A^iv	92.8 (3)	C33—N33—H33A	110.0
N21B^ii—Ni2—N21A^iv	172.3 (3)	Ni3—N33—H33A	110.0
N21A^ii—Ni2—N21A^iv	172.3 (3)	C33—N33—H33B	110.0
N21B^iii—Ni2—N21A^iv	92.97 (11)	Ni3—N33—H33B	110.0
N21A^iii—Ni2—N21A^iv	92.97 (11)	H33A—N33—H33B	108.3
N21A—Ni2—N21A^iv	81.7 (2)	N31—C31—C31^vi	109.0 (3)
N21B^iv—Ni2—N21A^iv	0.0 (3)	N31—C31—H31C	109.7
N21B^i—Ni2—N21B^v	81.7 (2)	C31^vi—C31—H31C	109.6
N21A^i—Ni2—N21B^v	81.7 (2)	N31—C31—H31D	109.9
N21B^ii—Ni2—N21B^v	92.8 (3)	C31^vi—C31—H31D	110.3
N21A^ii—Ni2—N21B^v	92.8 (3)	H31C—C31—H31D	108.4
N21B^iii—Ni2—N21B^v	92.97 (11)	N32—C32—C33	109.2 (3)
N21A^iii—Ni2—N21B^v	92.97 (11)	N32—C32—H32C	109.8
N21A—Ni2—N21B^v	172.3 (3)	C33—C32—H32C	109.8
N21B^iv—Ni2—N21B^v	92.97 (11)	N32—C32—H32D	109.8
N21A^iv—Ni2—N21B^v	92.97 (11)	C33—C32—H32D	109.8
N21B^i—Ni2—N21A^v	81.7 (2)	H32C—C32—H32D	108.3
N21A^i—Ni2—N21A^v	81.7 (2)	N33—C33—C32	110.2 (3)
N21B^ii—Ni2—N21A^v	92.8 (3)	N33—C33—H33C	109.6
N21A^ii—Ni2—N21A^v	92.8 (3)	C32—C33—H33C	109.6
N21B^iii—Ni2—N21A^v	92.97 (11)	N33—C33—H33D	109.6
N21A^iii—Ni2—N21A^v	92.97 (11)	C32—C33—H33D	109.6
N21A—Ni2—N21A^v	172.3 (3)	H33C—C33—H33D	108.1
N21B^iv—Ni2—N21A^v	92.97 (11)	N41—C41—Cu4	180.0 (9)
N21A^iv—Ni2—N21A^v	92.97 (11)	N51—C51—Cu5	173.5 (4)
N21B^v—Ni2—N21A^v	0.0 (4)	N61—C61—Cu6	177.8 (4)
N33^vi—Ni3—N33	89.92 (17)	C21A—N21A—Ni2	108.4 (7)
N33^vi—Ni3—N31	94.26 (10)	C21A—N21A—H21A	110.0
N33—Ni3—N31	175.74 (14)	Ni2—N21A—H21A	110.0
N33^vi—Ni3—N31^vi	175.73 (14)	C21A—N21A—H21B	110.0
N33—Ni3—N31^vi	94.27 (10)	Ni2—N21A—H21B	110.0
N31—Ni3—N31^vi	81.56 (16)	H21A—N21A—H21B	108.4
N33^vi—Ni3—N32	90.91 (12)	N21A—C21A—C21A^iv	107.1 (8)
N33—Ni3—N32	82.23 (12)	N21A—C21A—H21E	110.3
N31—Ni3—N32	96.88 (12)	C21A^iv—C21A—H21E	110.3
N31^vi—Ni3—N32	90.46 (12)	N21A—C21A—H21F	110.3
N33^vi—Ni3—N32^vi	82.23 (12)	C21A^iv—C21A—H21F	110.3
N33—Ni3—N32^vi	90.91 (12)	H21E—C21A—H21F	108.6
N31—Ni3—N32^vi	90.45 (12)	C21B^iv—C21B—H21G	110.1
N31^vi—Ni3—N32^vi	96.87 (12)	C21B^iv—C21B—H21H	110.1
N32—Ni3—N32^vi	170.33 (15)	H21G—C21B—H21H	108.5
C41^ii—Cu4—C41^i	120.0	H1O1—O1—H2O1	107.7
C41^ii—Cu4—C41	120.0	H1O1—O1—H1O3	126.1
C41^i—Cu4—C41	120.0	H2O1—O1—H1O3	126.1
C51—Cu5—C51^ii	116.60 (7)	O2^vii—O2—H1O2	80.0
C51—Cu5—C51^i	116.60 (7)	O2^vii—O2—H2O2	127.6
C51^ii—Cu5—C51^i	116.60 (7)	H1O2—O2—H2O2	107.7
C51—Cu5—N1	100.75 (12)	H1O1—O3—H1O3	126.8
C51^ii—Cu5—N1	100.75 (12)	H1O1—O3—H2O3	111.4
C51^i—Cu5—N1	100.75 (12)	H1O3—O3—H2O3	107.7
C1—Cu6—C61^ii	108.67 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11B···O3	0.92	2.09	2.937 (11)	152
N12—H12B···O3^i	0.92	2.10	2.98 (8)	160
N12—H12B···O1^i	0.92	2.15	2.998 (8)	153
N31—H31A···N61^ii	0.92	2.63	3.478 (5)	154
N32—H32B···N51^vi	0.92	2.48	3.346 (5)	157
N33—H33B···N41^viii	0.92	2.37	3.225 (6)	156
N21A—H21A···O2^vi	0.92	2.34	2.96 (7)	125
O1—H1O1···N61^ix	0.85	2.35	2.905 (7)	124
O1—H2O1···N12^ii	0.85	2.55	2.998 (8)	114
O2—H1O2···O3	0.85	2.22	2.842	130
O2—H1O2···O1	0.85	2.36	2.806	113
O2—H2O2···N51	0.85	2.00	2.773 (9)	151

Symmetry codes: (i) −y, x−y, z; (ii) −x+y, −x, z; (vi) x−y+1/3, −y+2/3, −z+2/3; (viii) −y−1/3, x−y+1/3, z+1/3; (ix) −y+1/3, x−y+2/3, z−1/3.