A compound of a novel tetra­aza-macrocycle with trinuclear tetra­cyano­nickelate-bridged cations

Curtis, N.F.; Puschmann, H.

doi:10.1107/S0108270104015483

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metal-organic compounds

STRUCTURAL

CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 8| August 2004| Pages m410-m413

doi:10.1107/S0108270104015483

A compound of a novel tetraaza-macrocycle with trinuclear tetracyanonickelate-bridged cations

Neil F. Curtis ^a ^* and Horst Puschmann ^b

^aSchool of Chemical and Physical Sciences, Victoria University of Wellington, Box 600, Wellington, New Zealand, and ^bDurham University Chemical Crystallography Group, Durham DH1 3LE, England

^*Correspondence e-mail: [email protected]

(Received 4 June 2004; accepted 24 June 2004; online 21 July 2004)

The cation of the title compound, [Cu(L)]²⁺, is formed by Michael condensation of (4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diamine)copper(II) with methanal and nitropropane. This cation forms a tetracyanonickelate(II) compound, the unit cell of which contains two centrosymmetric tetracyanonickelate(II)-bridged trinuclear cations, namely diaqua-1,3κ²O-di-μ-cyano-1:2κ²C:N;1:3κ²C:N-dicyano-1κ²C-bis(13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)-2κ⁴N¹,N⁴,N⁸,N¹¹;3κ⁴N¹,N⁴,N⁸,N¹¹-dicopper(II)nickel(II) di-μ-cyano-1:2κ²C:N;1:3κ²C:N-dicyano-1κ²C-bis(13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)-2κ⁴N¹,N⁴,N⁸,N¹¹;3κ⁴N¹,N⁴,N⁸,N¹¹-dicopper(II)nickel(II) bis[tetracyanonickelate(II)] octahydrate, [Cu₂Ni(CN)₄(C₁₅H₃₁N₅O₂)₂(H₂O)₂][Cu₂Ni(CN)₄(C₁₅H₃₁N₅O₂)₂][Ni(CN)₄]₂·8H₂O. One cation, [(L)Cu–NC–Ni(CN)₂–CN–Cu(L)]²⁺, has an axially coordinated bridging [Ni(CN)₄]²⁻ ion, with a Cu—N distance of 2.226 (3) Å and a Cu—N—C angle of 168.2 (3)°. The other cation, [(H₂O)(L)Cu–NC–Ni(CN)₂–CN–Cu(L)(OH₂)]²⁺, has water axially coordinated trans to a weakly bound bridging [Ni(CN)₄]²⁻ ion, with a Cu—O distance of 2.396 (3) Å, a Cu—N distance of 2.677 (4) Å, an O—Cu—N angle of 168.7 (1)° and a Cu—N—C angle of 137.7 (3)°. These cations, plus independent [Ni(CN)₄]²⁻ ions and water molecules, are linked into a hydrogen-bonded network. All [Ni(CN)₄]²⁻ ions are on centres of symmetry.

Comment

Michael condensations of (polyamine)metal complexes with methanal and nitroalkanes form nitroalkyl-substituted cyclic amine complexes (Lawrance, Lye et al., 1993 ; Lawrance, Maeder et al., 1993 ; Comba et al., 1986 ), such as 6-methyl-6-nitro-1,4,8,11-tetraazacyclotetradecane)copper(II), which is formed from (3,7-diazanonane-1,9-diamine)metal compounds, methanal and nitroethane (Comba et al., 1988a ,b ). The (tetraaza-macrocycle)copper(II) cation, [Cu(L)]²⁺, present in the title compound, formed by an analogous reaction of (4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diamine)copper(II) with methanal and nitropropane, differs by the presence of the imine function, the introduction of the 5,7,7-trimethyl substituents and the substitution of a 6-ethyl substituent for 6-methyl.

Structures of a number of methyl/nitro-substituted aza-macrocycle compounds obtained by reaction of (amine)metal compounds with nitroethane and methanal have been reported, but this is the first for an ethyl/nitro-substituted analogue derived from nitropropane.

The structures of many compounds of (amine)metal cations with cyanometallate anions have been reported, often with oligo- or polymeric structures with bridging cyanometallate ions (Cernak et al., 2002 ).

The title compound, (I), which crystallizes from aqueous solutions containing [Ni(CN)₄]²⁻ and [Cu(L)]²⁺, has the formal composition [Cu(L)][Ni(CN)₄]·2.5H₂O, but has two structurally distinct centrosymmetric tetracyanonickelate(II)-bridged (aza-macrocycle)copper(II) trinuclear cations, two independent tetracyanonickelate(II) anions, and one coordinated and four uncoordinated water molecules (see Fig. 1 and Table 1).

Atom Cu1A is in a square-planar coordination environment formed by the three secondary amine atoms, viz. N1A, N8A and N11A, and imine atom N4A of macrocycle L^a, with atom N55 of the [Ni5(CN)₄]²⁻ tetracyanonickelate(II) ion coordinated axially; the result is a centrosymmetric trinuclear cation, [(L^a)Cu–NC–Ni(CN)₂–CN–Cu(L^a)]²⁺, with a Cu⋯Cu separation of 10.426 (5) Å (see Fig. 2).

Atom Cu1B is in a square-planar coordination environment formed by the four N atoms, viz. N1B, N4B, N8B and N11B, of macrocycle L^b, with weaker axial interactions with water atom O10 and atom N65 of the [Ni6(CN)₄]²⁻ ion forming a weakly bound centrosymmetric trinuclear cation, [(H₂O)(L^b)Cu–NC–Ni(CN)₂–CN–Cu(L^b)(OH₂)]²⁺, with a Cu⋯Cu separation of 10.599 (5) Å (see Fig. 3).

For the two (aza-macrocycle)copper(II) cations, the Cu—N_ring distances are similar (with the Cu—N_imine distance ca 0.03 Å shorter than the mean Cu—N_amine distance), the configuration is the same (1S,8R,11R; Spek, 2002 ) and the conformations are similar. The nitro group and the C72 methyl component of the gem-dimethyl group are axially oriented on the same side of the N₄ macrocycle coordination plane as the N1—H1 and N11—H11 groups, with the N8—H8 group and the axial ligand (N55 for Cu1A and O10 for Cu1B) on the other side. The N₄ plane is less tetrahedrally twisted and the Cu atom is further displaced from this plane for the [Cu1A(L^a)]²⁺ ion [ $[\pm]$ 0.017 (2) and 0.246 (2) Å] than for the [Cu1B(L^b)]²⁺ ion [ $[\pm]$ 0.067 (2) and 0.088 (2) Å]; these planes are inclined at 30.9 (2)°. The C15 methylene substituents of both macrocycles are equatorially oriented, with the terminal methyl group, C16A, of the [Cu(L^a)]²⁺ ion further equatorially extended and closer to atom O18A, while the C16B group is axially oriented on the same side as axial water ligand O10.

The coordinated isocyano atom N55 is close to the square-pyramidal axis of the [Cu1A(L^a)]²⁺ ion, with N_ring—Cu1A—N55 angles of between 95.1 (1) and 99.3 (1)°. The non-bridging N56—C56—Ni5 group is approximately aligned with the C7A⋯C14A axis [N56⋯Ni5⋯Cu1A—C7A = −1.4 (2)°]. The ion is tilted with respect to the N₄ coordination plane so that the N8A⋯N56 distance [6.250 (5) Å] is longer than the N1A⋯N56(−x, 2 − y, −z) distance [4.998 (5) Å].

For [Cu1B(L^b)]²⁺, the coordinated water O and isocyano N atoms are displaced from the square-bipyramidal axis, with N_ring—Cu1B—O10 angles of 87.1 (1)–101.8 (1)° and N_ring—Cu1B—N65 angles of 81.9 (1)–96.8 (1)°.

The dimensions of the coordinated and non-coordinated [Ni(CN)₄]²⁻ ions, all centrosymmetric, do not differ significantly. The two tetracyanonickelate(II) anions including atoms Ni7 and Ni8, and the water molecules including atoms O11, O12, O13 and O14 have no direct interaction with the copper(II) cations, though all are linked into a hydrogen-bonding network (see Table 2).

Chain polymeric structures are present for bis(ethane-1,2-diamine)copper(II) tetracyanonickelate(II), [–Cu(en)₂–NC–Ni(CN)₂–CN–Cu(en)₂–] (Luo et al., 2000 ; Lokaj et al., 1991 ), and for analogous cyanometallate compounds of other (tetraamine)copper(II) cations, including the meso-(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)copper(II), [Cu(L¹)]²⁺, compounds with [Fe(CN)₆]³⁻ (Zou et al., 1998 ) and [Cr(CN)₆]³⁻ (El Fallah et al., 2001 ). The [Ni(CN)₄]²⁻ compounds formed by [Ni(L¹)]²⁺ (Gainsford & Curtis, 1984 ) and (3,10-diethyl-1,3,5,8,10,12-hexaazacyclotetradecane)nickel(II) (Kou et al., 2000 ) have similar structures, but with the Ni—N_cyano distances longer than Cu—N_cyano. The two faces of these (aza-macrocycle)metal(II) cations are equivalent, favouring the symmetrical structures observed. The two faces of the [Cu(L)]²⁺ cation are inherently different, the configuration observed having the axial nitro and methyl groups on the same side, which minimizes the interaction with an axial substituent coordinated on the other side. For the [Cu(L^a)]²⁺ ion, the isocyano N atom is coordinated on this less congested side, while for the [Cu(L^b)]²⁺ ion, water is bound on this side and the isocyano group is bound more weakly on the other side.

Figure 1

The structure of the title compound, drawn with displacement ellipsoids at the 50% probability level for non-H atoms, showing the asymmetric unit (labelled atoms and atoms of associated macrocycles), with additional atoms generated by symmetry operations to complete the tetracyanonickelate(II) anions and trinuclear cations.

Figure 2

The [(L^a)Cu–NC–Ni(CN)₂–CN–Cu(L^a)]²⁺ cation, drawn with displacement ellipsoids at the 50% probability level.

Figure 3

The [(H₂O)(L^a)Cu–NC–Ni(CN)₂–CN–Cu(L^b)(OH₂)]²⁺ cation, drawn with displacement ellipsoids at the 50% probability level.

Experimental

Aqua(13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)copper(II) bis(perchlorate), [Cu(L)(H₂O)](ClO₄)₂, was prepared by condensation of (4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diamine)copper(II) perchlorate (Blight & Curtis, 1962 ; Curtis, 1972 ; Curtis et al., 2003 ), methanal and nitropropane in water, with NaHCO₃ as base. The mauve-coloured tetracyanonickelate(II) compound precipitated when aqueous solutions containing [Ni(CN)₄]²⁻ and [Cu(L)]²⁺ were mixed. The sparingly soluble compound was recrystallized by evaporation of an aqueous solution.

Crystal data

[Cu₂Ni(CN)₄(C₁₅H₃₁N₅O₂)₂(H₂O)₂][Cu₂Ni(CN)₄(C₁₅H₃₁N₅O₂)₂][Ni(CN)₄]₂·8H₂O
M_r = 2339.23
Triclinic, $[P\overline 1]$
a = 11.7497 (2) Å
b = 14.0540 (3) Å
c = 17.9014 (4) Å
α = 70.154 (1)°
β = 78.165 (1)°
γ = 81.290 (1)°
V = 2710.6 (1) Å³
Z = 1
D_x = 1.431 Mg m⁻³
Mo Kα radiation
Cell parameters from 7862 reflections
θ = 2.3–29.3°
μ = 1.52 mm⁻¹
T = 120 (2) K
Plate, purple
0.35 × 0.35 × 0.08 mm

Data collection

Bruker SMART 1K CCD area detector diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.538, T_max = 0.885
R_int = 0.047 before correction
22 241 measured reflections
14 372 independent reflections
9857 reflections with I > 2σ(I)
R_int = 0.034
θ_max = 29.1°
h = −15 → 15
k = −19 → 19
l = −24 → 23

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.162
S = 1.05
14 372 reflections
666 parameters
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ²(F_o²) + (0.0668P)² + 5.1175P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.006
Δρ_max = 1.41 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Table 1

Selected geometric parameters (Å, °)

Cu1A—N4A	1.999 (4)
Cu1A—N11A	2.013 (3)
Cu1A—N8A	2.031 (3)
Cu1A—N1A	2.041 (3)
Cu1A—N55	2.226 (3)
N4A—C5A	1.304 (6)
Cu1B—N4B	1.986 (4)
Cu1B—N8B	2.018 (4)
Cu1B—N1B	2.020 (3)
Cu1B—N11B	2.026 (4)
Cu1B—O10	2.396 (3)
Cu1B—N65	2.677 (4)
N4B—C5B	1.304 (6)

N4A—Cu1A—N11A	164.6 (2)
N4A—Cu1A—N8A	95.6 (2)
N11A—Cu1A—N8A	85.9 (1)
N4A—Cu1A—N1A	85.4 (2)
N11A—Cu1A—N1A	89.7 (1)
N8A—Cu1A—N1A	166.8 (2)
N4A—Cu1A—N55	99.9 (2)
N11A—Cu1A—N55	95.1 (1)
N8A—Cu1A—N55	96.7 (2)
N1A—Cu1A—N55	96.1 (1)
C55—N55—Cu1A	168.2 (3)
N4B—Cu1B—N8B	95.9 (2)
N4B—Cu1B—N1B	86.0 (2)
N8B—Cu1B—N1B	177.7 (2)
N4B—Cu1B—N11B	170.7 (2)
N8B—Cu1B—N11B	86.9 (2)
N1B—Cu1B—N11B	91.0 (2)
N4B—Cu1B—O10	101.6 (2)
N8B—Cu1B—O10	87.0 (2)
N1B—Cu1B—O10	93.9 (1)
N11B—Cu1B—O10	87.3 (2)
N4B—Cu1B—N65	88.6 (2)
N8B—Cu1B—N65	96.8 (2)
N1B—Cu1B—N65	81.9 (1)
N11B—Cu1B—N65	82.2 (1)
O10—Cu1B—N65	168.7 (1)
C65—Ni6—C66	89.1 (2)
C65—N65—Cu1B	137.7 (3)

Table 2

Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯N85ⁱ	0.91	2.26	3.124 (5)	159
N11A—H11A⋯O14	0.91	2.11	2.869 (5)	140
N11A—H11A⋯O19A	0.91	2.41	2.978 (5)	121
N1B—H1B⋯O19A	0.91	2.12	2.937 (5)	149
N8B—H8B⋯O12	0.91	2.13	3.041 (5)	174
N8B—H8B⋯O10	0.91	2.58	3.052 (5)	113
N11B—H11B⋯O19B	0.91	2.29	2.874 (5)	122
O10—H10E⋯N75ⁱⁱ	0.84 (5)	1.92 (5)	2.745 (6)	168 (5)
O10—H10F⋯O12	0.85 (5)	1.93 (5)	2.702 (5)	151 (5)
O11—H11E⋯N66ⁱⁱⁱ	0.84 (3)	2.04 (4)	2.870 (5)	170 (6)
O11—H11F⋯N56	0.83 (5)	2.28 (5)	3.106 (5)	172 (5)
O12—H12F⋯N86	0.83 (4)	1.97 (4)	2.788 (5)	168 (6)
O12—H12E⋯O13	0.84 (4)	1.88 (3)	2.702 (5)	171 (6)
O13—H13E⋯O11^iv	0.84 (4)	1.94 (4)	2.733 (5)	158 (6)
O13—H13F⋯N56ⁱⁱⁱ	0.83 (4)	2.15 (4)	2.973 (6)	170 (5)
O14—H14E⋯N76ⁱⁱ	0.82 (4)	2.03 (4)	2.847 (5)	174 (7)
O14—H14F⋯N85ⁱ	0.82 (5)	2.10 (5)	2.872 (6)	159 (6)
Symmetry codes: (i) x,1+y,z; (ii) x-1,y,z; (iii) 1-x,1-y,-z; (iv) x-1, y-1,z.

C- and N-bound H atoms were placed in calculated positions and treated as riding. Water H atoms were located from difference syntheses, and their positions were refined with restrained O—H distances [0.82 (2) Å] and H—O—H angles [H⋯H = 1.35 (2) Å].

Data collection: SMART (Bruker, 1997 ); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3.2 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global_NA1674. DOI: 10.1107/S0108270104015483/na1674sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104015483/na1674Isup2.hkl

Comment top

Michael condensations of (polyamine)metal complexes with methanal and nitroalkanes form nitroalkyl-substituted cyclic amine complexes (Lawrance et al., 1993; Comba et al., 1986), e.g. 6-methyl-6-nitro-1,4,8,11-tetraazacyclotetradecane)copper(II), formed from (3,7-diazanonane-1,9-diamine)metal compounds, methanal and nitroethane (Comba et al., 1988a, 1988b). The (tetraazamacrocycle)copper(II) cation, [Cu(L)]²⁺, present in the title compound, formed by an analogous reaction of (4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diamine)copper(II) with methanal and nitropropane, differs by the presence of the imine function, the introduction of the 5,7,7-trimethyl substituents and the substitution of a 6-ethyl substituent for 6-methyl.

Structures of a number of methylnitro-substituted azamacrocyclic compounds obtained by reaction of (amine)metal compounds with nitroethane and methanal have been reported, but this is the first for an ethylnitro-substituted analogue derived from nitropropane.

The title compound, which crystallizes from aqueous solutions containing [Ni(CN)₄]²⁻ and [Cu(L)]²⁺, has the formal composition [Cu(L)][Ni(CN)₄]·2.5H₂O, but has two structurally distinct centrosymmetrical tetracyanonickelate(II)-bridged (azamacrocycle)copper(II) trinuclear cations, two independant tetracyanonickelate(II) anions, and one coordinated and four un-coordinated water molecules (see Fig. 1).

Atom Cu1A is in a square-planar coordination environment formed by the three secondary amine atoms, N1A, N8A and N11A, and imine atom N4A of macrocycle L^a, with atom N55 of the tetracyanonickelate(II) ion, [Ni5(CN)₄]²⁻, coordinated axially; the result is a centrosymmetrical trinuclear cation, [(L^a)Cu—NC—Ni(CN)₂—CN—Cu(L^a)]²⁺, with a Cu···Cu separation of 10.426 (5) Å (see Fig. 2).

Atom Cu1B is in square-planar coordination environment formed by the four N atoms, N1B, N4B, N8B and N11B, of macrocyle L^b, with weaker axial interactions with water atom O10 and atom N65 of the [Ni6(CN)₄]²⁻ ion forming a weakly bound centrosymmetrical trinuclear cation, [(H₂O)(L^b)Cu—NC—Ni(CN)₂—CN—Cu(L^b)(OH₂)]²⁺, with a Cu···Cu separation of 10.599 (5) Å (see Fig. 3).

For the two (azamacrocycle)copper(II) cations, the Cu—N_ring distances are similar (with Cu—N_imine ca 0.03 Å shorter than the mean Cu—N_amine distance), the configuration is the same (1S,8R,11R; Spek, 2002) and the conformations are similar. The nitro group and the C72 methyl component of the gem dimethyl group are axially oriented on the same side of the N₄ macrocycle coordination plane as the N1/H1 and N11/H11 groups, with the N8/H8 group and the axial ligand (N55 for Cu1A and O10 for Cu1B) on the other side. The N₄ plane is less tetrahedrally twisted and the Cu atom is further displaced from this plane for [Cu1A(L^a)]²⁺ [± 0.017 (2) and 0.246 (2) Å] than for [Cu1B(L^b)]²⁺ [±0.067 (2) and 0.088 (2) Å]; these planes are inclined at 30.9 (2)°. The C15 methylene substituents of both macrocyles are equatorially oriented, with the terminal methyl group, C16A, of [Cu(L^a)]²⁺ further equatorially extended and closer to atom O18A, while the C16B group is axially oriented on the same side as axial water ligand O10.

The coordinated isocyano atom N55 is close to the square pyramidal axis of [Cu1A(L^a)]²⁺, with N_ring—Cu1A—N55 angles of between 95.1 (1) and 99.3 (1)°. The non-bridging N56—C56—Ni5 group is approximately aligned with the C7A···C14A axis [N56···Ni5···Cu1A—C7A = −1.4 (2)°]. The ion is tilted with respect to the N₄ coordination plane so that the N8A···N56 distance [6.250 (5) Å] is longer than the N1A···N56(-x, 2 − y, −z) distance [4.998 (5) Å].

The dimensions of the coordinated and non-coordinated [Ni(CN)₄]²⁻ ions, all centrosymmetric, do not differ significantly. The two tetracyanonickelate(II) anions including atoms Ni7 and Ni8, and the water molecules including atoms O11, O12, O13 and O14, have no direct interaction with the copper(II) cations, though all are linked into a hydrogen-bonding network (see Table 2).

Bis(ethane-1,2-diamine)copper(II) tetracyanonickelate(II) has a polymeric chain structure [–Cu(en)₂—NC—Ni(CN)₂—CN—Cu(en)₂–] (Luo et al., 2000; Lokaj et al., 1991) [as do analogous compounds of other (tetraamine)copper(II) cations and the meso-(5,5,7,12,12,14-hexamethyl- 1,4,8,11-tetraazacyclotetradecane)copper(II), [Cu(L¹)]²⁺, compounds with [Fe(CN)₆]³⁻ (Zou et al., 1998) and [Cr(CN)₆]³⁻ (El Fallah et al., 2001), which are similar to the [Ni(CN)₄]²⁻ compounds formed by [Ni(L¹)]²⁺ (Gainsford & Curtis, 1984) and (3,10-diethyl-1,3,5,8,10,12- hexaazacyclotetradecane)nickel(II) (Kou et al., 2000)], with the Cu—N_cyano distances longer than the Ni—N_cyano distances. The two faces of these (azamacrocycle)metal(II) cations are equivalent, favouring the symmetrical structures observed. The two faces of the [Cu(L)]²⁺ cation are inherently different, the configuration observed having the the axial nitro and methyl groups on the same side, which minimizes the interaction with an axial substituent coordinated on the other side. For [Cu(L^a)]²⁺, the isocyano N atom is coordinated on this less congested side, while for [Cu(L^b)]²⁺, water is bound on this side and the isocyano group is bound more weakly on the other side.

Experimental top

Aqua-(13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec- 4-ene)copper(II) perchlorate, [Cu(L)(H₂O)](ClO₄)₂, was prepared by condensation of (4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diamine)copper(II) perchlorate, (Blight & Curtis, 1962; Curtis, 1972; Curtis et al., 2003) methanal and nitropropane in water, with NaHCO₃ as base. The mauve-coloured tetracyanonickelate(II) compound precipitated when aqueous solutions containing [Ni(CN)₄]²⁻ and [Cu(L)]²⁺ were mixed. The sparingly soluble compound was recrystallized by evaporation of an aqueous solution.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3.2 (Farrugia, 1997); software used to prepare material for publication: SHELXTL.

Figures top

	Fig. 1. The structure of the title compound, drawn with displacement ellipsoids at the 50% confidence level for non-H atoms, showing the asymmetric unit (labelled atoms and atoms of associated macrocycles), with additional atoms generated by symmetry operations to complete the tetracyanonickelate(II) anions and trinuclear cations.
	Fig. 2. The [(L^a)Cu—NC—Ni(CN)₂—CN—Cu(L^a)]²⁺ cation, drawn with displacement ellipsoids at the 50% confidence level.
	Fig. 3. The [(H₂O)(L^a)Cu—NC—Ni(CN)₂—CN—Cu(L^b)(OH₂)]²⁺ cation, drawn with displacement ellipsoids at the 50% confidence level.

di-µ-cyano-1:2κ²C:N;1:3κ²C:N-tetracyano-1κ⁴N-bis(13-ethyl-5,7,7- trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)- 2κ⁴N¹,N⁴,N⁸,N¹¹;3κ⁴N¹,N⁴,N⁸,N¹¹-dicopper(II)nickel(II) diaqua-1,3κ²O-di-µ-cyano-1:2κ²C:N;1:3κ²C:N-tetracyano-1κ⁴N- bis(13-ethyl-5,7,7-trimethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)- 2κ⁴N¹,N⁴,N⁸,N¹¹;3κ⁴N¹,N⁴,N⁸,N¹¹-dicopper(II)nickel(II) bis[tetracyanonickelate(II)] octahydrate top

Crystal data top

[Cu₂Ni(CN)₄(C₁₅H₃₁N₅O₂)₂(H₂O)₂][Cu₂Ni(CN)₄(C₁₅H₃₁N₅O₂)₂] [Ni(CN)₄]₂·8H₂O	Z = 1
M_r = 2339.23	F(000) = 1220
Triclinic, P1	D_x = 1.431 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.7497 (2) Å	Cell parameters from 7862 reflections
b = 14.0540 (3) Å	θ = 2.3–29.3°
c = 17.9014 (4) Å	µ = 1.52 mm⁻¹
α = 70.154 (1)°	T = 120 K
β = 78.165 (1)°	Plate, purple
γ = 81.290 (1)°	0.35 × 0.35 × 0.08 mm
V = 2710.6 (1) Å³

Data collection top

SMART 1K CCD area detector diffractometer	14372 independent reflections
Radiation source: fine-focus sealed tube	9857 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Detector resolution: 8 pixels mm^-1	θ_max = 29.1°, θ_min = 1.2°
ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Bruker, 2001) R(int)=0.0470 before correction	k = −19→19
T_min = 0.538, T_max = 0.885	l = −24→23
22241 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0668P)² + 5.1175P] where P = (F_o² + 2F_c²)/3
14372 reflections	(Δ/σ)_max = 0.006
666 parameters	Δρ_max = 1.41 e Å⁻³
15 restraints	Δρ_min = −0.73 e Å⁻³

Crystal data top

[Cu₂Ni(CN)₄(C₁₅H₃₁N₅O₂)₂(H₂O)₂][Cu₂Ni(CN)₄(C₁₅H₃₁N₅O₂)₂] [Ni(CN)₄]₂·8H₂O	γ = 81.290 (1)°
M_r = 2339.23	V = 2710.6 (1) Å³
Triclinic, P1	Z = 1
a = 11.7497 (2) Å	Mo Kα radiation
b = 14.0540 (3) Å	µ = 1.52 mm⁻¹
c = 17.9014 (4) Å	T = 120 K
α = 70.154 (1)°	0.35 × 0.35 × 0.08 mm
β = 78.165 (1)°

Data collection top

SMART 1K CCD area detector diffractometer	14372 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001) R(int)=0.0470 before correction	9857 reflections with I > 2σ(I)
T_min = 0.538, T_max = 0.885	R_int = 0.034
22241 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	15 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 1.41 e Å⁻³
14372 reflections	Δρ_min = −0.73 e Å⁻³
666 parameters

Special details top

Experimental. The data collection nominally covered full sphere of reciprocal space, by a combination of 5 sets of ω scans; each set at different ϕ and/or 2θ angles and each scan (10 sec exposure) covering 0.3° in ω. Crystal to detector distance 4.95 cm.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1A	0.51585 (4)	0.65895 (3)	0.23611 (3)	0.02303 (11)
N1A	0.3381 (3)	0.6770 (2)	0.2623 (2)	0.0259 (7)
H1A	0.3127	0.6170	0.2967	0.031*
N4A	0.5137 (3)	0.7137 (3)	0.3259 (2)	0.0355 (8)
N8A	0.6877 (3)	0.6078 (3)	0.2270 (2)	0.0316 (8)
H8A	0.7206	0.6564	0.1829	0.038*
N11A	0.5031 (3)	0.5711 (2)	0.17031 (19)	0.0232 (6)
H11A	0.4750	0.5125	0.2054	0.028*
N17A	0.2472 (3)	0.5344 (3)	0.1980 (2)	0.0303 (7)
C2A	0.3118 (4)	0.7529 (3)	0.3059 (3)	0.0360 (10)
H2A	0.2310	0.7525	0.3324	0.043*
H2B	0.3238	0.8204	0.2682	0.043*
C3A	0.3928 (4)	0.7256 (4)	0.3681 (3)	0.0400 (11)
H3A	0.3850	0.7788	0.3923	0.048*
H3B	0.3732	0.6627	0.4103	0.048*
C5A	0.6043 (5)	0.7166 (4)	0.3564 (3)	0.0481 (12)
C6A	0.7245 (4)	0.7033 (4)	0.3093 (3)	0.0468 (12)
H6A	0.7818	0.7063	0.3404	0.056*
H6B	0.7331	0.7602	0.2599	0.056*
C7A	0.7534 (5)	0.6051 (5)	0.2876 (4)	0.0521 (14)
C9A	0.7008 (4)	0.5189 (3)	0.1980 (3)	0.0316 (9)
H9A	0.6769	0.4591	0.2422	0.038*
H9B	0.7817	0.5055	0.1755	0.038*
C10A	0.6247 (3)	0.5438 (3)	0.1343 (3)	0.0313 (9)
H10A	0.6526	0.6003	0.0883	0.038*
H10B	0.6266	0.4856	0.1164	0.038*
C12A	0.4256 (3)	0.6120 (3)	0.1093 (2)	0.0272 (8)
H12A	0.4295	0.5636	0.0808	0.033*
H12B	0.4544	0.6741	0.0704	0.033*
C13A	0.2975 (3)	0.6348 (3)	0.1435 (2)	0.0272 (8)
C14A	0.2764 (3)	0.7086 (3)	0.1926 (3)	0.0293 (9)
H14A	0.3002	0.7743	0.1571	0.035*
H14B	0.1933	0.7172	0.2117	0.035*
C51A	0.5990 (6)	0.7505 (6)	0.4274 (4)	0.074 (2)
H51A	0.5207	0.7493	0.4566	0.111*
H51B	0.6222	0.8183	0.4096	0.111*
H51C	0.6508	0.7057	0.4619	0.111*
C71A	0.8848 (5)	0.5850 (6)	0.2652 (4)	0.0654 (18)
H71A	0.9014	0.5263	0.2474	0.098*
H71B	0.9211	0.5730	0.3114	0.098*
H71C	0.9148	0.6428	0.2227	0.098*
C72A	0.7108 (8)	0.5134 (6)	0.3658 (4)	0.090 (3)
H72A	0.6275	0.5225	0.3805	0.136*
H72B	0.7473	0.5122	0.4095	0.136*
H72C	0.7319	0.4504	0.3545	0.136*
C15A	0.2225 (4)	0.6784 (3)	0.0753 (3)	0.0347 (9)
H15A	0.1409	0.6809	0.0998	0.042*
H15B	0.2407	0.7477	0.0457	0.042*
C16A	0.2383 (4)	0.6202 (4)	0.0155 (3)	0.0398 (11)
H16A	0.3143	0.6283	−0.0169	0.060*
H16B	0.1798	0.6460	−0.0185	0.060*
H16C	0.2308	0.5494	0.0442	0.060*
O18A	0.1574 (3)	0.5370 (3)	0.2445 (2)	0.0469 (9)
O19A	0.3001 (3)	0.4555 (2)	0.1910 (3)	0.0598 (11)
Ni5	0.5000	1.0000	0.0000	0.02336 (15)
N55	0.5351 (3)	0.8009 (2)	0.1318 (2)	0.0311 (8)
N56	0.7477 (3)	1.0469 (3)	−0.0123 (3)	0.0437 (10)
C55	0.5245 (3)	0.8761 (3)	0.0810 (2)	0.0258 (8)
C56	0.6528 (4)	1.0292 (3)	−0.0074 (2)	0.0297 (9)
Cu1B	0.09397 (4)	0.18678 (4)	0.25244 (3)	0.02937 (13)
N1B	0.2299 (3)	0.2477 (3)	0.2668 (2)	0.0289 (7)
H1B	0.2285	0.3131	0.2334	0.035*
N4B	0.0107 (4)	0.2139 (3)	0.3526 (2)	0.0388 (9)
N8B	−0.0399 (3)	0.1284 (3)	0.2332 (2)	0.0373 (8)
H8B	−0.0212	0.0602	0.2525	0.045*
N11B	0.1758 (3)	0.1839 (3)	0.1419 (2)	0.0300 (7)
H11B	0.1701	0.2487	0.1077	0.036*
C2B	0.2048 (4)	0.2517 (3)	0.3513 (3)	0.0341 (9)
H2C	0.2504	0.3009	0.3559	0.041*
H2D	0.2258	0.1858	0.3884	0.041*
C3B	0.0763 (4)	0.2817 (4)	0.3717 (3)	0.0417 (11)
H3C	0.0558	0.2752	0.4285	0.050*
H3D	0.0575	0.3518	0.3406	0.050*
C5B	−0.0948 (4)	0.1919 (4)	0.3884 (3)	0.0422 (11)
C6B	−0.1509 (5)	0.1167 (4)	0.3657 (3)	0.0489 (13)
H6C	−0.2295	0.1106	0.3960	0.059*
H6D	−0.1077	0.0508	0.3834	0.059*
C7B	−0.1583 (4)	0.1412 (4)	0.2763 (3)	0.0456 (12)
C9B	−0.0222 (4)	0.1486 (4)	0.1444 (3)	0.0387 (10)
H9C	−0.0692	0.1068	0.1318	0.046*
H9D	−0.0449	0.2193	0.1173	0.046*
C10B	0.1040 (4)	0.1237 (3)	0.1175 (3)	0.0339 (9)
H10C	0.1196	0.1394	0.0595	0.041*
H10D	0.1247	0.0517	0.1417	0.041*
C12B	0.2997 (4)	0.1465 (3)	0.1334 (3)	0.0336 (9)
H12C	0.3280	0.1557	0.0767	0.040*
H12D	0.3051	0.0740	0.1615	0.040*
C13B	0.3825 (4)	0.1929 (3)	0.1630 (3)	0.0313 (9)
C14B	0.3471 (4)	0.1995 (3)	0.2486 (3)	0.0316 (9)
H14C	0.3524	0.1312	0.2864	0.038*
H14D	0.4032	0.2368	0.2576	0.038*
C15B	0.5068 (4)	0.1368 (4)	0.1545 (3)	0.0447 (11)
H15F	0.5320	0.1397	0.0987	0.054*
H15G	0.5603	0.1725	0.1677	0.054*
C16B	0.5147 (5)	0.0253 (4)	0.2079 (4)	0.0500 (13)
H16D	0.4573	−0.0094	0.1986	0.075*
H16E	0.5005	0.0220	0.2635	0.075*
H16F	0.5912	−0.0063	0.1951	0.075*
C51B	−0.1626 (5)	0.2302 (5)	0.4549 (4)	0.0696 (19)
H51D	−0.1264	0.2860	0.4566	0.104*
H51E	−0.1637	0.1766	0.5054	0.104*
H51F	−0.2412	0.2524	0.4452	0.104*
C71B	−0.2370 (5)	0.0675 (4)	0.2707 (4)	0.0538 (14)
H71D	−0.2042	−0.0010	0.2926	0.081*
H71E	−0.2430	0.0806	0.2154	0.081*
H71F	−0.3132	0.0765	0.3008	0.081*
C72B	−0.2114 (5)	0.2517 (4)	0.2413 (4)	0.0613 (15)
H72D	−0.2231	0.2635	0.1873	0.092*
H72E	−0.1590	0.2981	0.2411	0.092*
H72F	−0.2849	0.2621	0.2739	0.092*
N17B	0.3986 (3)	0.3035 (3)	0.1073 (2)	0.0364 (8)
O19B	0.3262 (4)	0.3450 (3)	0.0628 (2)	0.0553 (10)
O18B	0.4805 (3)	0.3460 (3)	0.1104 (2)	0.0518 (9)
O10	0.1759 (3)	0.0153 (3)	0.3044 (2)	0.0500 (9)
H10E	0.215 (4)	−0.006 (4)	0.342 (3)	0.060*
H10F	0.127 (4)	−0.029 (3)	0.317 (3)	0.060*
Ni6	0.0000	0.5000	0.0000	0.02634 (16)
N65	0.0374 (4)	0.3807 (3)	0.1702 (2)	0.0395 (9)
N66	0.1233 (3)	0.3209 (3)	−0.0505 (2)	0.0380 (9)
C65	0.0219 (4)	0.4272 (3)	0.1060 (3)	0.0296 (8)
C66	0.0769 (4)	0.3893 (3)	−0.0320 (3)	0.0300 (9)
Ni7	1.5000	0.0000	0.5000	0.02809 (17)
N75	1.3252 (5)	−0.0362 (4)	0.4144 (3)	0.0727 (17)
N76	1.5201 (4)	0.2129 (3)	0.3831 (2)	0.0404 (9)
C75	1.3917 (5)	−0.0218 (3)	0.4474 (3)	0.0455 (12)
C76	1.5120 (4)	0.1317 (3)	0.4271 (3)	0.0335 (9)
Ni8	0.0000	−0.5000	0.5000	0.03084 (18)
N85	0.2488 (4)	−0.5019 (3)	0.4135 (3)	0.0525 (11)
N86	−0.0354 (4)	−0.2762 (3)	0.4102 (3)	0.0512 (11)
C85	0.1545 (4)	−0.5016 (4)	0.4466 (3)	0.0377 (10)
C86	−0.0221 (4)	−0.3605 (4)	0.4439 (3)	0.0381 (10)
O11	0.8374 (3)	0.8482 (3)	0.1108 (2)	0.0472 (8)
H11E	0.841 (5)	0.797 (2)	0.096 (3)	0.057*
H11F	0.808 (5)	0.899 (3)	0.078 (3)	0.057*
O12	0.0259 (4)	−0.0996 (3)	0.2857 (2)	0.0486 (9)
H12E	0.025 (5)	−0.108 (4)	0.2417 (17)	0.058*
H12F	−0.001 (5)	−0.147 (3)	0.325 (2)	0.058*
O13	0.0452 (3)	−0.1146 (3)	0.1370 (2)	0.0549 (10)
H13E	−0.015 (3)	−0.113 (5)	0.118 (3)	0.066*
H13F	0.098 (3)	−0.096 (5)	0.098 (2)	0.066*
O14	0.4609 (4)	0.4265 (3)	0.3287 (3)	0.0643 (12)
H14E	0.482 (5)	0.3659 (19)	0.345 (4)	0.077*
H14F	0.395 (3)	0.433 (4)	0.353 (4)	0.077*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1A	0.0241 (2)	0.0199 (2)	0.0228 (2)	0.00072 (17)	−0.00397 (18)	−0.00506 (17)
N1A	0.0251 (16)	0.0198 (15)	0.0314 (17)	−0.0009 (12)	−0.0009 (13)	−0.0089 (13)
N4A	0.034 (2)	0.044 (2)	0.0325 (19)	−0.0004 (16)	−0.0062 (16)	−0.0184 (17)
N8A	0.0308 (18)	0.0321 (18)	0.0337 (19)	0.0069 (14)	−0.0137 (15)	−0.0121 (15)
N11A	0.0218 (15)	0.0192 (15)	0.0245 (16)	−0.0018 (12)	−0.0025 (12)	−0.0024 (12)
N17A	0.0271 (18)	0.0245 (17)	0.0378 (19)	−0.0071 (14)	−0.0061 (15)	−0.0055 (14)
C2A	0.029 (2)	0.034 (2)	0.050 (3)	−0.0006 (17)	−0.0005 (19)	−0.024 (2)
C3A	0.036 (2)	0.048 (3)	0.043 (3)	−0.005 (2)	0.003 (2)	−0.030 (2)
C5A	0.046 (3)	0.062 (3)	0.048 (3)	0.001 (2)	−0.010 (2)	−0.034 (3)
C6A	0.037 (3)	0.069 (3)	0.050 (3)	0.005 (2)	−0.018 (2)	−0.037 (3)
C7A	0.041 (3)	0.069 (4)	0.059 (3)	0.018 (3)	−0.019 (2)	−0.040 (3)
C9A	0.028 (2)	0.030 (2)	0.032 (2)	0.0047 (16)	−0.0019 (17)	−0.0081 (17)
C10A	0.024 (2)	0.037 (2)	0.032 (2)	0.0014 (17)	−0.0007 (16)	−0.0148 (18)
C12A	0.029 (2)	0.0234 (19)	0.029 (2)	−0.0060 (15)	−0.0076 (16)	−0.0044 (15)
C13A	0.028 (2)	0.0204 (18)	0.030 (2)	−0.0044 (15)	−0.0038 (16)	−0.0032 (15)
C14A	0.0238 (19)	0.0200 (18)	0.042 (2)	−0.0008 (15)	−0.0061 (17)	−0.0075 (17)
C51A	0.062 (4)	0.117 (6)	0.072 (4)	0.016 (4)	−0.024 (3)	−0.070 (4)
C71A	0.040 (3)	0.112 (5)	0.064 (4)	0.029 (3)	−0.030 (3)	−0.056 (4)
C72A	0.129 (7)	0.085 (5)	0.054 (4)	0.035 (5)	−0.038 (4)	−0.023 (4)
C15A	0.033 (2)	0.031 (2)	0.038 (2)	−0.0042 (17)	−0.0109 (18)	−0.0038 (18)
C16A	0.037 (2)	0.045 (3)	0.042 (3)	−0.008 (2)	−0.014 (2)	−0.013 (2)
O18A	0.0382 (18)	0.0399 (18)	0.059 (2)	−0.0161 (15)	0.0117 (16)	−0.0170 (16)
O19A	0.045 (2)	0.0256 (17)	0.095 (3)	−0.0104 (15)	0.013 (2)	−0.0122 (18)
Ni5	0.0273 (4)	0.0142 (3)	0.0243 (3)	−0.0034 (3)	−0.0017 (3)	−0.0014 (3)
N55	0.0341 (19)	0.0213 (16)	0.0354 (19)	−0.0087 (14)	−0.0093 (15)	−0.0012 (14)
N56	0.035 (2)	0.0290 (19)	0.061 (3)	−0.0063 (16)	−0.0079 (19)	−0.0048 (18)
C55	0.0242 (19)	0.0217 (18)	0.031 (2)	−0.0058 (14)	−0.0044 (16)	−0.0058 (16)
C56	0.038 (2)	0.0155 (18)	0.030 (2)	−0.0008 (16)	−0.0045 (17)	−0.0006 (15)
Cu1B	0.0320 (3)	0.0313 (3)	0.0269 (3)	−0.0058 (2)	−0.0053 (2)	−0.0105 (2)
N1B	0.0351 (19)	0.0270 (17)	0.0238 (17)	−0.0070 (14)	−0.0025 (14)	−0.0065 (14)
N4B	0.044 (2)	0.042 (2)	0.034 (2)	−0.0169 (18)	0.0029 (17)	−0.0170 (17)
N8B	0.034 (2)	0.041 (2)	0.039 (2)	−0.0061 (16)	−0.0104 (16)	−0.0108 (17)
N11B	0.0363 (19)	0.0259 (17)	0.0303 (18)	−0.0030 (14)	−0.0091 (15)	−0.0103 (14)
C2B	0.045 (3)	0.034 (2)	0.026 (2)	−0.0075 (19)	−0.0052 (18)	−0.0121 (17)
C3B	0.049 (3)	0.047 (3)	0.034 (2)	−0.019 (2)	0.001 (2)	−0.018 (2)
C5B	0.040 (3)	0.047 (3)	0.040 (3)	−0.015 (2)	0.001 (2)	−0.014 (2)
C6B	0.043 (3)	0.050 (3)	0.050 (3)	−0.021 (2)	0.001 (2)	−0.009 (2)
C7B	0.041 (3)	0.046 (3)	0.053 (3)	−0.014 (2)	−0.004 (2)	−0.019 (2)
C9B	0.044 (3)	0.038 (2)	0.039 (2)	−0.005 (2)	−0.018 (2)	−0.012 (2)
C10B	0.046 (3)	0.030 (2)	0.031 (2)	−0.0064 (18)	−0.0110 (19)	−0.0116 (17)
C12B	0.034 (2)	0.032 (2)	0.037 (2)	−0.0022 (17)	−0.0046 (18)	−0.0150 (18)
C13B	0.034 (2)	0.027 (2)	0.031 (2)	−0.0003 (17)	−0.0060 (17)	−0.0075 (17)
C14B	0.035 (2)	0.030 (2)	0.031 (2)	−0.0065 (17)	−0.0058 (18)	−0.0102 (17)
C15B	0.035 (2)	0.050 (3)	0.055 (3)	−0.004 (2)	−0.006 (2)	−0.027 (2)
C16B	0.047 (3)	0.043 (3)	0.068 (4)	0.004 (2)	−0.025 (3)	−0.022 (3)
C51B	0.053 (4)	0.087 (5)	0.078 (4)	−0.030 (3)	0.023 (3)	−0.047 (4)
C71B	0.040 (3)	0.061 (3)	0.069 (4)	−0.013 (2)	−0.008 (3)	−0.027 (3)
C72B	0.054 (3)	0.056 (4)	0.067 (4)	0.004 (3)	−0.010 (3)	−0.014 (3)
N17B	0.038 (2)	0.038 (2)	0.0310 (19)	−0.0087 (17)	0.0029 (16)	−0.0114 (16)
O19B	0.080 (3)	0.048 (2)	0.0366 (19)	−0.0211 (19)	−0.0215 (19)	0.0027 (16)
O18B	0.0379 (19)	0.044 (2)	0.071 (3)	−0.0199 (16)	0.0027 (17)	−0.0153 (18)
O10	0.057 (2)	0.0339 (18)	0.058 (2)	−0.0118 (16)	−0.0290 (19)	0.0016 (16)
Ni6	0.0239 (4)	0.0255 (4)	0.0292 (4)	−0.0016 (3)	−0.0070 (3)	−0.0069 (3)
N65	0.045 (2)	0.037 (2)	0.036 (2)	0.0007 (17)	−0.0105 (18)	−0.0109 (17)
N66	0.041 (2)	0.033 (2)	0.039 (2)	−0.0010 (17)	−0.0054 (17)	−0.0119 (17)
C65	0.030 (2)	0.028 (2)	0.031 (2)	−0.0019 (16)	−0.0059 (17)	−0.0112 (17)
C66	0.028 (2)	0.029 (2)	0.032 (2)	−0.0040 (16)	−0.0084 (17)	−0.0055 (17)
Ni7	0.0347 (4)	0.0229 (4)	0.0236 (4)	−0.0003 (3)	−0.0062 (3)	−0.0037 (3)
N75	0.103 (4)	0.044 (3)	0.070 (3)	−0.027 (3)	−0.055 (3)	0.015 (2)
N76	0.051 (2)	0.032 (2)	0.034 (2)	−0.0030 (17)	−0.0105 (18)	−0.0021 (16)
C75	0.067 (3)	0.027 (2)	0.040 (3)	−0.010 (2)	−0.024 (2)	0.0038 (19)
C76	0.036 (2)	0.035 (2)	0.030 (2)	0.0003 (18)	−0.0120 (18)	−0.0080 (18)
Ni8	0.0329 (4)	0.0360 (4)	0.0239 (4)	−0.0116 (3)	−0.0039 (3)	−0.0067 (3)
N85	0.041 (2)	0.052 (3)	0.051 (3)	−0.008 (2)	0.007 (2)	−0.006 (2)
N86	0.069 (3)	0.042 (2)	0.041 (2)	−0.014 (2)	−0.013 (2)	−0.005 (2)
C85	0.041 (3)	0.038 (2)	0.031 (2)	−0.007 (2)	−0.007 (2)	−0.0045 (19)
C86	0.041 (3)	0.045 (3)	0.031 (2)	−0.012 (2)	−0.0067 (19)	−0.012 (2)
O11	0.045 (2)	0.047 (2)	0.054 (2)	0.0014 (17)	−0.0155 (17)	−0.0196 (18)
O12	0.064 (2)	0.0332 (18)	0.049 (2)	−0.0175 (16)	−0.0165 (19)	−0.0036 (16)
O13	0.044 (2)	0.076 (3)	0.052 (2)	−0.021 (2)	−0.0031 (17)	−0.025 (2)
O14	0.068 (3)	0.0320 (19)	0.056 (2)	0.0013 (18)	0.021 (2)	0.0120 (17)

Geometric parameters (Å, º) top

Cu1A—N4A	1.999 (4)	N8B—C7B	1.464 (6)
Cu1A—N11A	2.013 (3)	N8B—C9B	1.492 (6)
Cu1A—N8A	2.031 (3)	N8B—H8B	0.9100
Cu1A—N1A	2.041 (3)	N11B—C12B	1.467 (5)
Cu1A—N55	2.226 (3)	N11B—C10B	1.494 (5)
N1A—C14A	1.476 (5)	N11B—H11B	0.9100
N1A—C2A	1.486 (5)	C2B—C3B	1.509 (7)
N1A—H1A	0.9100	C2B—H2C	0.9700
N4A—C5A	1.304 (6)	C2B—H2D	0.9700
N4A—C3A	1.480 (6)	C3B—H3C	0.9700
N8A—C7A	1.443 (6)	C3B—H3D	0.9700
N8A—C9A	1.484 (5)	C5B—C51B	1.503 (7)
N8A—H8A	0.9100	C5B—C6B	1.525 (7)
N11A—C12A	1.476 (5)	C6B—C7B	1.538 (7)
N11A—C10A	1.492 (5)	C6B—H6C	0.9700
N11A—H11A	0.9100	C6B—H6D	0.9700
N17A—O18A	1.208 (5)	C7B—C71B	1.528 (7)
N17A—O19A	1.218 (5)	C7B—C72B	1.550 (8)
N17A—C13A	1.541 (5)	C9B—C10B	1.489 (6)
C2A—C3A	1.526 (7)	C9B—H9C	0.9700
C2A—H2A	0.9700	C9B—H9D	0.9700
C2A—H2B	0.9700	C10B—H10C	0.9700
C3A—H3A	0.9700	C10B—H10D	0.9700
C3A—H3B	0.9700	C12B—C13B	1.514 (6)
C5A—C51A	1.489 (7)	C12B—H12C	0.9700
C5A—C6A	1.510 (7)	C12B—H12D	0.9700
C6A—C7A	1.529 (7)	C13B—C14B	1.534 (6)
C6A—H6A	0.9700	C13B—N17B	1.550 (5)
C6A—H6B	0.9700	C13B—C15B	1.555 (6)
C7A—C71A	1.522 (7)	C14B—H14C	0.9700
C7A—C72A	1.598 (10)	C14B—H14D	0.9700
C9A—C10A	1.508 (6)	C15B—C16B	1.534 (7)
C9A—H9A	0.9700	C15B—H15F	0.9700
C9A—H9B	0.9700	C15B—H15G	0.9700
C10A—H10A	0.9700	C16B—H16D	0.9600
C10A—H10B	0.9700	C16B—H16E	0.9600
C12A—C13A	1.534 (6)	C16B—H16F	0.9600
C12A—H12A	0.9700	C51B—H51D	0.9600
C12A—H12B	0.9700	C51B—H51E	0.9600
C13A—C14A	1.537 (6)	C51B—H51F	0.9600
C13A—C15A	1.553 (6)	C71B—H71D	0.9600
C14A—H14A	0.9700	C71B—H71E	0.9600
C14A—H14B	0.9700	C71B—H71F	0.9600
C51A—H51A	0.9600	C72B—H72D	0.9600
C51A—H51B	0.9600	C72B—H72E	0.9600
C51A—H51C	0.9600	C72B—H72F	0.9600
C71A—H71A	0.9600	N17B—O18B	1.227 (5)
C71A—H71B	0.9600	N17B—O19B	1.229 (5)
C71A—H71C	0.9600	O10—H10E	0.839 (19)
C72A—H72A	0.9600	O10—H10F	0.853 (19)
C72A—H72B	0.9600	Ni6—C65ⁱⁱ	1.876 (4)
C72A—H72C	0.9600	Ni6—C65	1.876 (4)
C15A—C16A	1.522 (7)	Ni6—C66ⁱⁱ	1.879 (4)
C15A—H15A	0.9700	Ni6—C66	1.879 (4)
C15A—H15B	0.9700	N65—C65	1.149 (5)
C16A—H16A	0.9600	N66—C66	1.147 (5)
C16A—H16B	0.9600	Ni7—C75	1.846 (5)
C16A—H16C	0.9600	Ni7—C75ⁱⁱⁱ	1.846 (5)
Ni5—C56	1.871 (4)	Ni7—C76ⁱⁱⁱ	1.874 (4)
Ni5—C56ⁱ	1.871 (4)	Ni7—C76	1.874 (4)
Ni5—C55	1.877 (4)	N75—C75	1.148 (7)
Ni5—C55ⁱ	1.877 (4)	N76—C76	1.150 (5)
N55—C55	1.146 (5)	Ni8—C85^iv	1.870 (5)
N56—C56	1.159 (6)	Ni8—C85	1.871 (5)
Cu1B—N4B	1.986 (4)	Ni8—C86^iv	1.880 (5)
Cu1B—N8B	2.018 (4)	Ni8—C86	1.880 (5)
Cu1B—N1B	2.020 (3)	N85—C85	1.145 (6)
Cu1B—N11B	2.026 (4)	N86—C86	1.136 (6)
Cu1B—O10	2.396 (3)	O11—H11F	0.832 (19)
Cu1B—N65	2.677 (4)	O12—H12E	0.835 (19)
N1B—C14B	1.465 (5)	O12—H12F	0.832 (19)
N1B—C2B	1.500 (5)	O13—H13E	0.837 (19)
N1B—H1B	0.9100	O13—H13F	0.831 (19)
N4B—C5B	1.304 (6)	O14—H14E	0.818 (19)
N4B—C3B	1.474 (6)	O14—H14F	0.815 (19)

N4A—Cu1A—N11A	164.6 (2)	O10—Cu1B—N65	168.7 (1)
N4A—Cu1A—N8A	95.6 (2)	C14B—N1B—C2B	111.4 (3)
N11A—Cu1A—N8A	85.9 (1)	C14B—N1B—Cu1B	117.4 (3)
N4A—Cu1A—N1A	85.4 (2)	C2B—N1B—Cu1B	106.6 (3)
N11A—Cu1A—N1A	89.7 (1)	C14B—N1B—H1B	107.0
N8A—Cu1A—N1A	166.8 (2)	C2B—N1B—H1B	107.0
N4A—Cu1A—N55	99.9 (2)	Cu1B—N1B—H1B	107.0
N11A—Cu1A—N55	95.1 (1)	C5B—N4B—C3B	123.4 (4)
N8A—Cu1A—N55	96.7 (2)	C5B—N4B—Cu1B	126.2 (3)
N1A—Cu1A—N55	96.1 (1)	C3B—N4B—Cu1B	109.3 (3)
C14A—N1A—C2A	110.9 (3)	C7B—N8B—C9B	118.9 (4)
C14A—N1A—Cu1A	115.6 (2)	C7B—N8B—Cu1B	120.9 (3)
C2A—N1A—Cu1A	105.4 (2)	C9B—N8B—Cu1B	105.4 (3)
C14A—N1A—H1A	108.2	C7B—N8B—H8B	102.9
C2A—N1A—H1A	108.2	C9B—N8B—H8B	102.9
Cu1A—N1A—H1A	108.2	Cu1B—N8B—H8B	102.9
C5A—N4A—C3A	122.2 (4)	C12B—N11B—C10B	112.0 (3)
C5A—N4A—Cu1A	125.7 (3)	C12B—N11B—Cu1B	117.5 (3)
C3A—N4A—Cu1A	110.3 (3)	C10B—N11B—Cu1B	105.3 (3)
C7A—N8A—C9A	119.2 (4)	C12B—N11B—H11B	107.2
C7A—N8A—Cu1A	120.2 (3)	C10B—N11B—H11B	107.2
C9A—N8A—Cu1A	106.8 (3)	Cu1B—N11B—H11B	107.2
C7A—N8A—H8A	102.5	N1B—C2B—C3B	108.6 (4)
C9A—N8A—H8A	102.5	N1B—C2B—H2C	110.0
Cu1A—N8A—H8A	102.5	C3B—C2B—H2C	110.0
C12A—N11A—C10A	112.0 (3)	N1B—C2B—H2D	110.0
C12A—N11A—Cu1A	117.1 (2)	C3B—C2B—H2D	110.0
C10A—N11A—Cu1A	106.6 (2)	H2C—C2B—H2D	108.4
C12A—N11A—H11A	106.9	N4B—C3B—C2B	108.0 (4)
C10A—N11A—H11A	106.9	N4B—C3B—H3C	110.1
Cu1A—N11A—H11A	106.9	C2B—C3B—H3C	110.1
O18A—N17A—O19A	123.1 (4)	N4B—C3B—H3D	110.1
O18A—N17A—C13A	119.2 (3)	C2B—C3B—H3D	110.1
O19A—N17A—C13A	117.8 (3)	H3C—C3B—H3D	108.4
N1A—C2A—C3A	108.5 (3)	N4B—C5B—C51B	124.4 (5)
N1A—C2A—H2A	110.0	N4B—C5B—C6B	118.3 (4)
C3A—C2A—H2A	110.0	C51B—C5B—C6B	117.2 (4)
N1A—C2A—H2B	110.0	C5B—C6B—C7B	117.2 (4)
C3A—C2A—H2B	110.0	C5B—C6B—H6C	108.0
H2A—C2A—H2B	108.4	C7B—C6B—H6C	108.0
N4A—C3A—C2A	107.6 (4)	C5B—C6B—H6D	108.0
N4A—C3A—H3A	110.2	C7B—C6B—H6D	108.0
C2A—C3A—H3A	110.2	H6C—C6B—H6D	107.2
N4A—C3A—H3B	110.2	N8B—C7B—C71B	111.5 (4)
C2A—C3A—H3B	110.2	N8B—C7B—C6B	107.9 (4)
H3A—C3A—H3B	108.5	C71B—C7B—C6B	107.5 (4)
N4A—C5A—C51A	124.5 (5)	N8B—C7B—C72B	109.8 (4)
N4A—C5A—C6A	118.6 (4)	C71B—C7B—C72B	109.5 (5)
C51A—C5A—C6A	116.0 (5)	C6B—C7B—C72B	110.5 (5)
C5A—C6A—C7A	115.9 (5)	C10B—C9B—N8B	107.4 (4)
C5A—C6A—H6A	108.3	C10B—C9B—H9C	110.2
C7A—C6A—H6A	108.3	N8B—C9B—H9C	110.2
C5A—C6A—H6B	108.3	C10B—C9B—H9D	110.2
C7A—C6A—H6B	108.3	N8B—C9B—H9D	110.2
H6A—C6A—H6B	107.4	H9C—C9B—H9D	108.5
N8A—C7A—C71A	114.4 (4)	C9B—C10B—N11B	109.7 (4)
N8A—C7A—C6A	110.2 (4)	C9B—C10B—H10C	109.7
C71A—C7A—C6A	110.3 (5)	N11B—C10B—H10C	109.7
N8A—C7A—C72A	106.4 (5)	C9B—C10B—H10D	109.7
C71A—C7A—C72A	107.3 (5)	N11B—C10B—H10D	109.7
C6A—C7A—C72A	108.0 (5)	H10C—C10B—H10D	108.2
N8A—C9A—C10A	107.5 (3)	N11B—C12B—C13B	118.5 (4)
N8A—C9A—H9A	110.2	N11B—C12B—H12C	107.7
C10A—C9A—H9A	110.2	C13B—C12B—H12C	107.7
N8A—C9A—H9B	110.2	N11B—C12B—H12D	107.7
C10A—C9A—H9B	110.2	C13B—C12B—H12D	107.7
H9A—C9A—H9B	108.5	H12C—C12B—H12D	107.1
N11A—C10A—C9A	108.0 (3)	C12B—C13B—C14B	117.0 (4)
N11A—C10A—H10A	110.1	C12B—C13B—N17B	109.8 (3)
C9A—C10A—H10A	110.1	C14B—C13B—N17B	105.6 (3)
N11A—C10A—H10B	110.1	C12B—C13B—C15B	110.0 (4)
C9A—C10A—H10B	110.1	C14B—C13B—C15B	109.3 (4)
H10A—C10A—H10B	108.4	N17B—C13B—C15B	104.3 (3)
N11A—C12A—C13A	114.4 (3)	N1B—C14B—C13B	115.7 (3)
N11A—C12A—H12A	108.7	N1B—C14B—H14C	108.4
C13A—C12A—H12A	108.7	C13B—C14B—H14C	108.4
N11A—C12A—H12B	108.7	N1B—C14B—H14D	108.4
C13A—C12A—H12B	108.7	C13B—C14B—H14D	108.4
H12A—C12A—H12B	107.6	H14C—C14B—H14D	107.4
C12A—C13A—C14A	115.2 (3)	C16B—C15B—C13B	114.2 (4)
C12A—C13A—N17A	108.9 (3)	C16B—C15B—H15F	108.7
C14A—C13A—N17A	108.1 (3)	C13B—C15B—H15F	108.7
C12A—C13A—C15A	111.0 (3)	C16B—C15B—H15G	108.7
C14A—C13A—C15A	107.7 (3)	C13B—C15B—H15G	108.7
N17A—C13A—C15A	105.6 (3)	H15F—C15B—H15G	107.6
N1A—C14A—C13A	115.0 (3)	C15B—C16B—H16D	109.5
N1A—C14A—H14A	108.5	C15B—C16B—H16E	109.5
C13A—C14A—H14A	108.5	H16D—C16B—H16E	109.5
N1A—C14A—H14B	108.5	C15B—C16B—H16F	109.5
C13A—C14A—H14B	108.5	H16D—C16B—H16F	109.5
H14A—C14A—H14B	107.5	H16E—C16B—H16F	109.5
C5A—C51A—H51A	109.5	C5B—C51B—H51D	109.5
C5A—C51A—H51B	109.5	C5B—C51B—H51E	109.5
H51A—C51A—H51B	109.5	H51D—C51B—H51E	109.5
C5A—C51A—H51C	109.5	C5B—C51B—H51F	109.5
H51A—C51A—H51C	109.5	H51D—C51B—H51F	109.5
H51B—C51A—H51C	109.5	H51E—C51B—H51F	109.5
C7A—C71A—H71A	109.5	C7B—C71B—H71D	109.5
C7A—C71A—H71B	109.5	C7B—C71B—H71E	109.5
H71A—C71A—H71B	109.5	H71D—C71B—H71E	109.5
C7A—C71A—H71C	109.5	C7B—C71B—H71F	109.5
H71A—C71A—H71C	109.5	H71D—C71B—H71F	109.5
H71B—C71A—H71C	109.5	H71E—C71B—H71F	109.5
C7A—C72A—H72A	109.5	C7B—C72B—H72D	109.5
C7A—C72A—H72B	109.5	C7B—C72B—H72E	109.5
H72A—C72A—H72B	109.5	H72D—C72B—H72E	109.5
C7A—C72A—H72C	109.5	C7B—C72B—H72F	109.5
H72A—C72A—H72C	109.5	H72D—C72B—H72F	109.5
H72B—C72A—H72C	109.5	H72E—C72B—H72F	109.5
C16A—C15A—C13A	115.9 (4)	O18B—N17B—O19B	123.1 (4)
C16A—C15A—H15A	108.3	O18B—N17B—C13B	119.3 (4)
C13A—C15A—H15A	108.3	O19B—N17B—C13B	117.6 (4)
C16A—C15A—H15B	108.3	Cu1B—O10—H10E	125 (4)
C13A—C15A—H15B	108.3	Cu1B—O10—H10F	114 (4)
H15A—C15A—H15B	107.4	H10E—O10—H10F	103 (4)
C15A—C16A—H16A	109.5	C65ⁱⁱ—Ni6—C65	180.0
C15A—C16A—H16B	109.5	C65ⁱⁱ—Ni6—C66ⁱⁱ	89.14 (18)
H16A—C16A—H16B	109.5	C65—Ni6—C66ⁱⁱ	90.86 (18)
C15A—C16A—H16C	109.5	C65ⁱⁱ—Ni6—C66	90.86 (18)
H16A—C16A—H16C	109.5	C65—Ni6—C66	89.14 (18)
H16B—C16A—H16C	109.5	C66ⁱⁱ—Ni6—C66	180.00 (14)
C56—Ni5—C56ⁱ	179.999 (1)	C65—N65—Cu1B	137.7 (3)
C56—Ni5—C55	90.63 (16)	N65—C65—Ni6	178.1 (4)
C56ⁱ—Ni5—C55	89.37 (16)	N66—C66—Ni6	179.1 (4)
C56—Ni5—C55ⁱ	89.37 (16)	C75—Ni7—C75ⁱⁱⁱ	180.000 (1)
C56ⁱ—Ni5—C55ⁱ	90.63 (16)	C75—Ni7—C76ⁱⁱⁱ	89.64 (19)
C55—Ni5—C55ⁱ	179.999 (1)	C75ⁱⁱⁱ—Ni7—C76ⁱⁱⁱ	90.36 (19)
C55—N55—Cu1A	168.2 (3)	C75—Ni7—C76	90.36 (19)
N55—C55—Ni5	177.4 (4)	C75ⁱⁱⁱ—Ni7—C76	89.64 (19)
N56—C56—Ni5	179.6 (5)	C76ⁱⁱⁱ—Ni7—C76	179.998 (3)
N4B—Cu1B—N8B	95.9 (2)	N75—C75—Ni7	179.2 (6)
N4B—Cu1B—N1B	86.0 (2)	N76—C76—Ni7	179.0 (4)
N8B—Cu1B—N1B	177.7 (2)	C85^iv—Ni8—C85	179.999 (2)
N4B—Cu1B—N11B	170.7 (2)	C85^iv—Ni8—C86^iv	89.5 (2)
N8B—Cu1B—N11B	86.9 (2)	C85—Ni8—C86^iv	90.5 (2)
N1B—Cu1B—N11B	91.0 (2)	C85^iv—Ni8—C86	90.5 (2)
N4B—Cu1B—O10	101.6 (2)	C85—Ni8—C86	89.5 (2)
N8B—Cu1B—O10	87.0 (2)	C86^iv—Ni8—C86	180.0
N1B—Cu1B—O10	93.9 (1)	N85—C85—Ni8	179.4 (5)
N11B—Cu1B—O10	87.3 (2)	N86—C86—Ni8	179.8 (5)
N4B—Cu1B—N65	88.6 (2)	H11E—O11—H11F	109 (4)
N8B—Cu1B—N65	96.8 (2)	H12E—O12—H12F	112 (4)
N1B—Cu1B—N65	81.9 (1)	H13E—O13—H13F	106 (4)
N11B—Cu1B—N65	82.2 (1)	H14E—O14—H14F	105 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···N85^v	0.91	2.26	3.124 (5)	159
N11A—H11A···O14	0.91	2.11	2.869 (5)	140
N11A—H11A···O19A	0.91	2.41	2.978 (5)	121
N1B—H1B···O19A	0.91	2.12	2.937 (5)	149
N8B—H8B···O12	0.91	2.13	3.041 (5)	174
N8B—H8B···O10	0.91	2.58	3.052 (5)	113
N11B—H11B···O19B	0.91	2.29	2.874 (5)	122
O10—H10E···N75^vi	0.84 (5)	1.92 (5)	2.745 (6)	168 (5)
O10—H10F···O12	0.85 (5)	1.93 (5)	2.702 (5)	151 (5)
O11—H11E···N66^vii	0.84 (3)	2.04 (4)	2.870 (5)	170 (6)
O11—H11F···N56	0.83 (5)	2.28 (5)	3.106 (5)	172 (5)
O12—H12F···N86	0.83 (4)	1.97 (4)	2.788 (5)	168 (6)
O12—H12E···O13	0.84 (4)	1.88 (3)	2.702 (5)	171 (6)
O13—H13E···O11^viii	0.84 (4)	1.94 (4)	2.733 (5)	158 (6)
O13—H13F···N56^vii	0.83 (4)	2.15 (4)	2.973 (6)	170 (5)
O14—H14E···N76^vi	0.82 (4)	2.03 (4)	2.847 (5)	174 (7)
O14—H14F···N85^v	0.82 (5)	2.10 (5)	2.872 (6)	159 (6)

Symmetry codes: (v) x, y+1, z; (vi) x−1, y, z; (vii) −x+1, −y+1, −z; (viii) x−1, y−1, z.

Experimental details

Crystal data
Chemical formula	[Cu₂Ni(CN)₄(C₁₅H₃₁N₅O₂)₂(H₂O)₂][Cu₂Ni(CN)₄(C₁₅H₃₁N₅O₂)₂] [Ni(CN)₄]₂·8H₂O
M_r	2339.23
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	11.7497 (2), 14.0540 (3), 17.9014 (4)
α, β, γ (°)	70.154 (1), 78.165 (1), 81.290 (1)
V (Å³)	2710.6 (1)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.52
Crystal size (mm)	0.35 × 0.35 × 0.08

Data collection
Diffractometer	SMART 1K CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001) R(int)=0.0470 before correction
T_min, T_max	0.538, 0.885
No. of measured, independent and observed [I > 2σ(I)] reflections	22241, 14372, 9857
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.684

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.162, 1.05
No. of reflections	14372
No. of parameters	666
No. of restraints	15
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.41, −0.73

Computer programs: SMART (Bruker, 1997), SMART, SAINT (Bruker, 2001), SHELXTL (Bruker, 1997), SHELXTL, ORTEP-3.2 (Farrugia, 1997).

Selected geometric parameters (Å, º) top

Cu1A—N4A	1.999 (4)	Cu1B—N8B	2.018 (4)
Cu1A—N11A	2.013 (3)	Cu1B—N1B	2.020 (3)
Cu1A—N8A	2.031 (3)	Cu1B—N11B	2.026 (4)
Cu1A—N1A	2.041 (3)	Cu1B—O10	2.396 (3)
Cu1A—N55	2.226 (3)	Cu1B—N65	2.677 (4)
N4A—C5A	1.304 (6)	N65—C65	1.149 (5)
Cu1B—N4B	1.986 (4)

N4A—Cu1A—N11A	164.6 (2)	N4B—Cu1B—N11B	170.7 (2)
N4A—Cu1A—N8A	95.6 (2)	N8B—Cu1B—N11B	86.9 (2)
N11A—Cu1A—N8A	85.9 (1)	N1B—Cu1B—N11B	91.0 (2)
N4A—Cu1A—N1A	85.4 (2)	N4B—Cu1B—O10	101.6 (2)
N11A—Cu1A—N1A	89.7 (1)	N8B—Cu1B—O10	87.0 (2)
N8A—Cu1A—N1A	166.8 (2)	N1B—Cu1B—O10	93.9 (1)
N4A—Cu1A—N55	99.9 (2)	N11B—Cu1B—O10	87.3 (2)
N11A—Cu1A—N55	95.1 (1)	N4B—Cu1B—N65	88.6 (2)
N8A—Cu1A—N55	96.7 (2)	N8B—Cu1B—N65	96.8 (2)
N1A—Cu1A—N55	96.1 (1)	N1B—Cu1B—N65	81.9 (1)
C55—N55—Cu1A	168.2 (3)	N11B—Cu1B—N65	82.2 (1)
N4B—Cu1B—N8B	95.9 (2)	O10—Cu1B—N65	168.7 (1)
N4B—Cu1B—N1B	86.0 (2)	C65—Ni6—C66	89.14 (18)
N8B—Cu1B—N1B	177.7 (2)	C65—N65—Cu1B	137.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···N85ⁱ	0.91	2.26	3.124 (5)	159
N11A—H11A···O14	0.91	2.11	2.869 (5)	140
N11A—H11A···O19A	0.91	2.41	2.978 (5)	121
N1B—H1B···O19A	0.91	2.12	2.937 (5)	149
N8B—H8B···O12	0.91	2.13	3.041 (5)	174
N8B—H8B···O10	0.91	2.58	3.052 (5)	113
N11B—H11B···O19B	0.91	2.29	2.874 (5)	122
O10—H10E···N75ⁱⁱ	0.84 (5)	1.92 (5)	2.745 (6)	168 (5)
O10—H10F···O12	0.85 (5)	1.93 (5)	2.702 (5)	151 (5)
O11—H11E···N66ⁱⁱⁱ	0.84 (3)	2.04 (4)	2.870 (5)	170 (6)
O11—H11F···N56	0.83 (5)	2.28 (5)	3.106 (5)	172 (5)
O12—H12F···N86	0.83 (4)	1.97 (4)	2.788 (5)	168 (6)
O12—H12E···O13	0.84 (4)	1.88 (3)	2.702 (5)	171 (6)
O13—H13E···O11^iv	0.84 (4)	1.94 (4)	2.733 (5)	158 (6)
O13—H13F···N56ⁱⁱⁱ	0.83 (4)	2.15 (4)	2.973 (6)	170 (5)
O14—H14E···N76ⁱⁱ	0.82 (4)	2.03 (4)	2.847 (5)	174 (7)
O14—H14F···N85ⁱ	0.82 (5)	2.10 (5)	2.872 (6)	159 (6)

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

References

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ISSN: 2053-2296

Volume 60| Part 8| August 2004| Pages m410-m413

doi:10.1107/S0108270104015483

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

A compound of a novel tetra­aza-macrocycle with trinuclear tetra­cyano­nickelate-bridged cations

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

metal-organic compounds

A compound of a novel tetraaza-macrocycle with trinuclear tetracyanonickelate-bridged cations