Discrete water clusters in tetra-μ-cyanido-tetra-cyanidobis(1,4,7-triisopropyl-1,4,7-triaza-cyclo-nona-ne)dicopper(II)dinickel(II) tetra-hydrate.

The title tetra-cyanido-nickelate-copper complex, [Cu₂Ni₂(CN)₈(C₁₅H₃₃N₃)₂]·4H₂O, was synthesized by self-assembly using potassium tetracyanidonickelate(II) and dichlorido(1,4,7-triisopropyl-1,4,7-triazacyclononane)copper(II). The asymmetric unit contains half of a complex mol-ecule and two water mol-ecules. The entire complex has -1 symmetry and contains Ni(II) in a slightly distorted square-planar and Cu(II) in a square-pyramidal coordination environment. The crystal packing shows a discrete tetra-mer water cluster. Within the cluster, the four water mol-ecules are fully coplanar and each water monomer acts both as single O-H⋯O and O-H⋯N hydrogen-bond donor and acceptor.

Related literature

For properties and applications of cyanide-bridged coordination complexes, see: Zhao et al. (2009 ▶); Dunbar & Heintz (1997 ▶); Orendac et al. (2002 ▶). For the use of the tetra­cyanido­nickelate anion as a bridging ligand in the construction of one-, two- and three-dimensional structures, see: Bozoglian et al. (2005 ▶); Maji et al. (2001 ▶); Dunbar & Heintz (1997 ▶); Černák et al. (1988 ▶, 1990 ▶); Černák & Abboud (2000 ▶). For the influence on water aggregations of the overall structure of their surroundings, see: Long et al. (2004 ▶); Xantheas (1995 ▶). For water clusters, see: Ugalde et al. (2000 ▶); Gregory & Clary (1996 ▶). For the synthesis of the ligand, see: Hay & Norman (1979 ▶). Chen et al. (2009 ▶).

Experimental

Crystal data

[Cu2Ni2(CN)8(C15H33N3)2]·4H2O

M = 1035.59

Monoclinic,

a = 8.5896 (17) Å

b = 18.092 (4) Å

c = 15.615 (3) Å

β = 95.61 (3)°

V = 2415.1 (8) Å3

Z = 2

Mo Kα radiation

μ = 1.69 mm−1

T = 293 K

0.14 × 0.12 × 0.06 mm

Data collection

Bruker P4 diffractometer

Absorption correction: multi-scan (XSCANS; Bruker, 1999 ▶) T min = 0.798, T max = 0.906

18582 measured reflections

5622 independent reflections

4475 reflections with I > 2σ(I)

R int = 0.039

3 standard reflections every 120 min intensity decay: 1.0%

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.074

S = 1.03

5622 reflections

293 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.52 e Å−3

Δρmin = −0.39 e Å−3

Data collection: XSCANS (Bruker, 1999 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812024282/vm2171sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024282/vm2171Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu2Ni2(CN)8(C15H33N3)2]·4H2O	F(000) = 1092
Mr = 1035.59	Dx = 1.424 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3989 reflections
a = 8.5896 (17) Å	θ = 2.0–25.5°
b = 18.092 (4) Å	µ = 1.69 mm−1
c = 15.615 (3) Å	T = 293 K
β = 95.61 (3)°	Prism, blue
V = 2415.1 (8) Å3	0.14 × 0.12 × 0.06 mm
Z = 2

Bruker P4 diffractometer	4475 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
Graphite monochromator	θmax = 27.9°, θmin = 1.7°
ω scans	h = −11→10
Absorption correction: multi-scan (XSCANS; Bruker, 1999)	k = −23→23
Tmin = 0.798, Tmax = 0.906	l = −20→12
18582 measured reflections	3 standard reflections every 120 min
5622 independent reflections	intensity decay: 1.0%

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0357P)2] where P = (Fo2 + 2Fc2)/3
5622 reflections	(Δ/σ)max = 0.002
293 parameters	Δρmax = 0.52 e Å−3
6 restraints	Δρmin = −0.39 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	0.14378 (3)	0.639359 (12)	0.659167 (15)	0.01450 (7)
Ni1	0.20048 (3)	0.370161 (13)	0.612942 (16)	0.01552 (8)
N1	0.12720 (19)	0.52998 (9)	0.64625 (11)	0.0183 (4)
N2	0.4785 (2)	0.39240 (11)	0.74309 (12)	0.0336 (5)
N3	0.2998 (2)	0.21257 (10)	0.58992 (14)	0.0358 (5)
N4	−0.0304 (2)	0.35220 (9)	0.45692 (11)	0.0188 (4)
N5	0.18877 (19)	0.63639 (9)	0.79170 (10)	0.0164 (4)
N6	0.40058 (19)	0.63663 (9)	0.65419 (11)	0.0200 (4)
N7	0.16954 (19)	0.75278 (9)	0.67369 (10)	0.0173 (4)
C1	0.1467 (2)	0.46860 (11)	0.63196 (13)	0.0173 (4)
C2	0.3701 (3)	0.38215 (11)	0.69594 (13)	0.0220 (5)
C3	0.2615 (2)	0.27259 (12)	0.59875 (14)	0.0225 (5)
C4	0.0494 (2)	0.35903 (10)	0.51975 (13)	0.0174 (4)
C5	0.3626 (2)	0.62659 (12)	0.81156 (14)	0.0226 (5)
H5A	0.3815	0.5925	0.8594	0.027*
H5B	0.4083	0.6738	0.8296	0.027*
C6	0.4447 (2)	0.59780 (12)	0.73657 (13)	0.0239 (5)
H6A	0.5568	0.6024	0.7507	0.029*
H6B	0.4209	0.5457	0.7289	0.029*
C7	0.4476 (2)	0.71567 (12)	0.65622 (15)	0.0252 (5)
H7A	0.5301	0.7228	0.6188	0.030*
H7B	0.4891	0.7287	0.7143	0.030*
C8	0.3109 (3)	0.76665 (11)	0.62750 (14)	0.0234 (5)
H8A	0.3438	0.8175	0.6370	0.028*
H8B	0.2832	0.7602	0.5662	0.028*
C9	0.2005 (3)	0.77059 (11)	0.76740 (13)	0.0206 (5)
H9A	0.1495	0.8168	0.7793	0.025*
H9B	0.3121	0.7769	0.7820	0.025*
C10	0.1412 (3)	0.71016 (11)	0.82235 (13)	0.0205 (5)
H10A	0.1833	0.7171	0.8817	0.025*
H10B	0.0281	0.7127	0.8198	0.025*
C11	0.4573 (2)	0.59355 (13)	0.58066 (14)	0.0256 (5)
H11	0.4070	0.5449	0.5806	0.031*
C12	0.4061 (3)	0.62923 (13)	0.49380 (15)	0.0331 (6)
H12A	0.2950	0.6372	0.4888	0.050*
H12B	0.4322	0.5972	0.4484	0.050*
H12C	0.4587	0.6757	0.4897	0.050*
C13	0.6336 (3)	0.58003 (14)	0.59072 (17)	0.0376 (6)
H13A	0.6875	0.6265	0.5960	0.056*
H13B	0.6632	0.5541	0.5412	0.056*
H13C	0.6610	0.5509	0.6414	0.056*
C14	0.0316 (2)	0.79650 (11)	0.63208 (14)	0.0219 (5)
H14	0.0216	0.7844	0.5706	0.026*
C15	0.0510 (3)	0.88029 (11)	0.63950 (15)	0.0279 (5)
H15A	0.0495	0.8949	0.6985	0.042*
H15B	−0.0331	0.9042	0.6051	0.042*
H15C	0.1489	0.8945	0.6195	0.042*
C16	−0.1201 (3)	0.77345 (12)	0.66699 (14)	0.0273 (5)
H16A	−0.1295	0.7206	0.6650	0.041*
H16B	−0.2070	0.7953	0.6326	0.041*
H16C	−0.1199	0.7900	0.7254	0.041*
C17	0.1007 (3)	0.57566 (11)	0.83338 (13)	0.0215 (5)
H17	0.1460	0.5283	0.8183	0.026*
C18	−0.0718 (3)	0.57506 (12)	0.79870 (14)	0.0253 (5)
H18A	−0.1217	0.6189	0.8173	0.038*
H18B	−0.1217	0.5323	0.8201	0.038*
H18C	−0.0804	0.5736	0.7370	0.038*
C19	0.1143 (3)	0.58101 (12)	0.93095 (13)	0.0300 (6)
H19A	0.2220	0.5877	0.9523	0.045*
H19B	0.0754	0.5364	0.9544	0.045*
H19C	0.0540	0.6223	0.9478	0.045*
O1	0.3097 (2)	0.42588 (10)	0.00040 (11)	0.0420 (5)
O2	0.5596 (2)	0.45720 (11)	0.90642 (13)	0.0454 (5)
H1A	0.308 (3)	0.3849 (7)	0.0270 (14)	0.058 (10)*
H1B	0.340 (3)	0.4592 (9)	0.0362 (12)	0.048 (9)*
H2A	0.542 (3)	0.4407 (18)	0.8550 (9)	0.095 (14)*
H2B	0.481 (3)	0.4447 (17)	0.9337 (16)	0.075 (12)*

	U11	U22	U33	U12	U13	U23
Cu1	0.01485 (13)	0.01184 (12)	0.01636 (14)	−0.00097 (10)	−0.00065 (9)	−0.00208 (10)
Ni1	0.01783 (14)	0.01198 (13)	0.01623 (15)	0.00133 (10)	−0.00106 (10)	−0.00066 (10)
N1	0.0188 (9)	0.0156 (9)	0.0200 (9)	−0.0002 (7)	−0.0007 (7)	−0.0017 (7)
N2	0.0328 (12)	0.0317 (11)	0.0337 (12)	0.0063 (9)	−0.0098 (9)	−0.0029 (9)
N3	0.0373 (12)	0.0190 (10)	0.0513 (14)	0.0058 (9)	0.0058 (10)	−0.0024 (9)
N4	0.0203 (9)	0.0149 (9)	0.0209 (10)	−0.0008 (7)	0.0010 (7)	−0.0016 (7)
N5	0.0179 (9)	0.0143 (8)	0.0168 (9)	0.0009 (7)	−0.0001 (7)	−0.0013 (7)
N6	0.0158 (9)	0.0192 (9)	0.0250 (10)	−0.0034 (7)	0.0026 (7)	−0.0059 (7)
N7	0.0194 (9)	0.0133 (8)	0.0194 (9)	−0.0004 (7)	0.0025 (7)	0.0000 (7)
C1	0.0146 (10)	0.0211 (11)	0.0155 (10)	−0.0035 (8)	−0.0020 (8)	−0.0003 (8)
C2	0.0271 (12)	0.0169 (11)	0.0218 (12)	0.0051 (9)	0.0018 (9)	0.0006 (9)
C3	0.0234 (12)	0.0212 (11)	0.0227 (12)	0.0000 (9)	0.0013 (9)	0.0005 (9)
C4	0.0196 (11)	0.0107 (10)	0.0222 (12)	0.0000 (8)	0.0041 (8)	−0.0009 (8)
C5	0.0171 (11)	0.0240 (12)	0.0250 (12)	0.0010 (9)	−0.0067 (9)	−0.0009 (9)
C6	0.0149 (11)	0.0241 (12)	0.0315 (13)	0.0002 (9)	−0.0030 (9)	−0.0051 (10)
C7	0.0210 (12)	0.0236 (12)	0.0317 (13)	−0.0074 (9)	0.0057 (10)	−0.0072 (10)
C8	0.0274 (12)	0.0198 (11)	0.0241 (12)	−0.0080 (9)	0.0083 (9)	−0.0018 (9)
C9	0.0242 (11)	0.0161 (10)	0.0209 (11)	−0.0013 (9)	−0.0004 (9)	−0.0056 (8)
C10	0.0260 (12)	0.0163 (10)	0.0188 (11)	−0.0006 (9)	0.0007 (9)	−0.0027 (8)
C11	0.0203 (12)	0.0266 (12)	0.0309 (13)	−0.0041 (9)	0.0071 (9)	−0.0100 (10)
C12	0.0297 (14)	0.0410 (15)	0.0305 (14)	−0.0048 (11)	0.0132 (11)	−0.0093 (11)
C13	0.0227 (13)	0.0421 (16)	0.0498 (17)	−0.0012 (11)	0.0121 (11)	−0.0172 (13)
C14	0.0269 (12)	0.0171 (10)	0.0213 (11)	0.0005 (9)	0.0003 (9)	−0.0002 (9)
C15	0.0400 (14)	0.0167 (11)	0.0274 (13)	0.0031 (10)	0.0044 (10)	0.0016 (9)
C16	0.0257 (12)	0.0247 (12)	0.0309 (13)	0.0036 (10)	0.0010 (10)	0.0021 (10)
C17	0.0279 (12)	0.0158 (11)	0.0206 (11)	−0.0004 (9)	0.0023 (9)	0.0028 (8)
C18	0.0282 (13)	0.0198 (11)	0.0290 (13)	−0.0021 (9)	0.0081 (10)	0.0020 (9)
C19	0.0439 (15)	0.0271 (13)	0.0193 (12)	0.0006 (11)	0.0042 (10)	0.0052 (9)
O1	0.0551 (13)	0.0261 (10)	0.0424 (11)	−0.0098 (9)	−0.0069 (9)	0.0031 (9)
O2	0.0513 (14)	0.0450 (12)	0.0393 (12)	−0.0076 (10)	0.0015 (10)	−0.0159 (10)

Cu1—N4i	1.9781 (18)	C9—H9B	0.9700
Cu1—N1	1.9929 (17)	C10—H10A	0.9700
Cu1—N5	2.0686 (17)	C10—H10B	0.9700
Cu1—N7	2.0740 (17)	C11—C13	1.527 (3)
Cu1—N6	2.2153 (18)	C11—C12	1.527 (3)
Ni1—C3	1.861 (2)	C11—H11	0.9800
Ni1—C4	1.864 (2)	C12—H12A	0.9600
Ni1—C2	1.866 (2)	C12—H12B	0.9600
Ni1—C1	1.871 (2)	C12—H12C	0.9600
N1—C1	1.148 (3)	C13—H13A	0.9600
N2—C2	1.144 (3)	C13—H13B	0.9600
N3—C3	1.147 (3)	C13—H13C	0.9600
N4—C4	1.147 (3)	C14—C16	1.520 (3)
N4—Cu1i	1.9781 (18)	C14—C15	1.528 (3)
N5—C10	1.488 (2)	C14—H14	0.9800
N5—C5	1.506 (2)	C15—H15A	0.9600
N5—C17	1.517 (3)	C15—H15B	0.9600
N6—C6	1.482 (3)	C15—H15C	0.9600
N6—C7	1.485 (3)	C16—H16A	0.9600
N6—C11	1.507 (3)	C16—H16B	0.9600
N7—C8	1.493 (3)	C16—H16C	0.9600
N7—C9	1.496 (2)	C17—C19	1.520 (3)
N7—C14	1.517 (3)	C17—C18	1.527 (3)
C5—C6	1.517 (3)	C17—H17	0.9800
C5—H5A	0.9700	C18—H18A	0.9600
C5—H5B	0.9700	C18—H18B	0.9600
C6—H6A	0.9700	C18—H18C	0.9600
C6—H6B	0.9700	C19—H19A	0.9600
C7—C8	1.526 (3)	C19—H19B	0.9600
C7—H7A	0.9700	C19—H19C	0.9600
C7—H7B	0.9700	O1—H1A	0.851 (9)
C8—H8A	0.9700	O1—H1B	0.846 (9)
C8—H8B	0.9700	O2—H2A	0.856 (10)
C9—C10	1.509 (3)	O2—H2B	0.861 (10)
C9—H9A	0.9700
N4i—Cu1—N1	87.71 (7)	C10—C9—H9A	109.4
N4i—Cu1—N5	161.08 (7)	N7—C9—H9B	109.4
N1—Cu1—N5	94.59 (6)	C10—C9—H9B	109.4
N4i—Cu1—N7	93.53 (6)	H9A—C9—H9B	108.0
N1—Cu1—N7	177.96 (7)	N5—C10—C9	110.39 (17)
N5—Cu1—N7	84.76 (6)	N5—C10—H10A	109.6
N4i—Cu1—N6	111.86 (8)	C9—C10—H10A	109.6
N1—Cu1—N6	92.05 (7)	N5—C10—H10B	109.6
N5—Cu1—N6	86.86 (7)	C9—C10—H10B	109.6
N7—Cu1—N6	85.98 (6)	H10A—C10—H10B	108.1
C3—Ni1—C4	89.27 (9)	N6—C11—C13	113.30 (18)
C3—Ni1—C2	89.03 (9)	N6—C11—C12	111.79 (18)
C4—Ni1—C2	172.72 (9)	C13—C11—C12	110.86 (19)
C3—Ni1—C1	177.13 (9)	N6—C11—H11	106.8
C4—Ni1—C1	93.60 (8)	C13—C11—H11	106.8
C2—Ni1—C1	88.13 (9)	C12—C11—H11	106.8
C1—N1—Cu1	165.89 (17)	C11—C12—H12A	109.5
C4—N4—Cu1i	167.12 (16)	C11—C12—H12B	109.5
C10—N5—C5	109.71 (15)	H12A—C12—H12B	109.5
C10—N5—C17	110.33 (16)	C11—C12—H12C	109.5
C5—N5—C17	110.65 (15)	H12A—C12—H12C	109.5
C10—N5—Cu1	105.55 (11)	H12B—C12—H12C	109.5
C5—N5—Cu1	107.08 (13)	C11—C13—H13A	109.5
C17—N5—Cu1	113.32 (12)	C11—C13—H13B	109.5
C6—N6—C7	113.06 (16)	H13A—C13—H13B	109.5
C6—N6—C11	109.99 (16)	C11—C13—H13C	109.5
C7—N6—C11	113.98 (17)	H13A—C13—H13C	109.5
C6—N6—Cu1	98.69 (12)	H13B—C13—H13C	109.5
C7—N6—Cu1	104.33 (12)	N7—C14—C16	111.39 (17)
C11—N6—Cu1	115.81 (12)	N7—C14—C15	114.21 (17)
C8—N7—C9	111.17 (16)	C16—C14—C15	109.64 (18)
C8—N7—C14	110.08 (16)	N7—C14—H14	107.1
C9—N7—C14	111.30 (16)	C16—C14—H14	107.1
C8—N7—Cu1	101.33 (12)	C15—C14—H14	107.1
C9—N7—Cu1	109.08 (12)	C14—C15—H15A	109.5
C14—N7—Cu1	113.49 (12)	C14—C15—H15B	109.5
N1—C1—Ni1	173.96 (18)	H15A—C15—H15B	109.5
N2—C2—Ni1	175.5 (2)	C14—C15—H15C	109.5
N3—C3—Ni1	179.7 (2)	H15A—C15—H15C	109.5
N4—C4—Ni1	172.6 (2)	H15B—C15—H15C	109.5
N5—C5—C6	114.07 (17)	C14—C16—H16A	109.5
N5—C5—H5A	108.7	C14—C16—H16B	109.5
C6—C5—H5A	108.7	H16A—C16—H16B	109.5
N5—C5—H5B	108.7	C14—C16—H16C	109.5
C6—C5—H5B	108.7	H16A—C16—H16C	109.5
H5A—C5—H5B	107.6	H16B—C16—H16C	109.5
N6—C6—C5	114.12 (17)	N5—C17—C19	113.04 (17)
N6—C6—H6A	108.7	N5—C17—C18	111.13 (16)
C5—C6—H6A	108.7	C19—C17—C18	109.45 (18)
N6—C6—H6B	108.7	N5—C17—H17	107.7
C5—C6—H6B	108.7	C19—C17—H17	107.7
H6A—C6—H6B	107.6	C18—C17—H17	107.7
N6—C7—C8	112.05 (17)	C17—C18—H18A	109.5
N6—C7—H7A	109.2	C17—C18—H18B	109.5
C8—C7—H7A	109.2	H18A—C18—H18B	109.5
N6—C7—H7B	109.2	C17—C18—H18C	109.5
C8—C7—H7B	109.2	H18A—C18—H18C	109.5
H7A—C7—H7B	107.9	H18B—C18—H18C	109.5
N7—C8—C7	113.29 (17)	C17—C19—H19A	109.5
N7—C8—H8A	108.9	C17—C19—H19B	109.5
C7—C8—H8A	108.9	H19A—C19—H19B	109.5
N7—C8—H8B	108.9	C17—C19—H19C	109.5
C7—C8—H8B	108.9	H19A—C19—H19C	109.5
H8A—C8—H8B	107.7	H19B—C19—H19C	109.5
N7—C9—C10	111.25 (16)	H1A—O1—H1B	108.6 (15)
N7—C9—H9A	109.4	H2A—O2—H2B	107.6 (15)
N4i—Cu1—N1—C1	90.8 (7)	C4—Ni1—C3—N3	117 (40)
N5—Cu1—N1—C1	−108.0 (7)	C2—Ni1—C3—N3	−56 (40)
N7—Cu1—N1—C1	−37 (2)	C1—Ni1—C3—N3	−65 (40)
N6—Cu1—N1—C1	−21.0 (7)	Cu1i—N4—C4—Ni1	−54.8 (18)
N4i—Cu1—N5—C10	−60.4 (2)	C3—Ni1—C4—N4	−72.1 (13)
N1—Cu1—N5—C10	−156.75 (13)	C2—Ni1—C4—N4	4.4 (18)
N7—Cu1—N5—C10	25.19 (12)	C1—Ni1—C4—N4	108.0 (13)
N6—Cu1—N5—C10	111.44 (13)	C10—N5—C5—C6	−132.57 (18)
N4i—Cu1—N5—C5	−177.27 (18)	C17—N5—C5—C6	105.5 (2)
N1—Cu1—N5—C5	86.39 (12)	Cu1—N5—C5—C6	−18.5 (2)
N7—Cu1—N5—C5	−91.67 (12)	C7—N6—C6—C5	64.5 (2)
N6—Cu1—N5—C5	−5.42 (12)	C11—N6—C6—C5	−166.80 (17)
N4i—Cu1—N5—C17	60.4 (3)	Cu1—N6—C6—C5	−45.18 (18)
N1—Cu1—N5—C17	−35.91 (14)	N5—C5—C6—N6	47.3 (2)
N7—Cu1—N5—C17	146.03 (14)	C6—N6—C7—C8	−127.45 (19)
N6—Cu1—N5—C17	−127.72 (13)	C11—N6—C7—C8	106.0 (2)
N4i—Cu1—N6—C6	−155.83 (11)	Cu1—N6—C7—C8	−21.3 (2)
N1—Cu1—N6—C6	−67.47 (12)	C9—N7—C8—C7	65.3 (2)
N5—Cu1—N6—C6	27.02 (12)	C14—N7—C8—C7	−170.92 (17)
N7—Cu1—N6—C6	111.98 (12)	Cu1—N7—C8—C7	−50.51 (18)
N4i—Cu1—N6—C7	87.55 (13)	N6—C7—C8—N7	51.3 (2)
N1—Cu1—N6—C7	175.91 (13)	C8—N7—C9—C10	−133.78 (18)
N5—Cu1—N6—C7	−89.60 (13)	C14—N7—C9—C10	103.11 (19)
N7—Cu1—N6—C7	−4.64 (13)	Cu1—N7—C9—C10	−22.9 (2)
N4i—Cu1—N6—C11	−38.57 (16)	C5—N5—C10—C9	70.3 (2)
N1—Cu1—N6—C11	49.79 (15)	C17—N5—C10—C9	−167.58 (15)
N5—Cu1—N6—C11	144.28 (15)	Cu1—N5—C10—C9	−44.80 (18)
N7—Cu1—N6—C11	−130.76 (15)	N7—C9—C10—N5	46.1 (2)
N4i—Cu1—N7—C8	−83.12 (13)	C6—N6—C11—C13	−57.2 (2)
N1—Cu1—N7—C8	44.1 (19)	C7—N6—C11—C13	71.0 (2)
N5—Cu1—N7—C8	115.77 (13)	Cu1—N6—C11—C13	−167.98 (15)
N6—Cu1—N7—C8	28.57 (12)	C6—N6—C11—C12	176.65 (17)
N4i—Cu1—N7—C9	159.55 (13)	C7—N6—C11—C12	−55.2 (2)
N1—Cu1—N7—C9	−73.2 (19)	Cu1—N6—C11—C12	65.9 (2)
N5—Cu1—N7—C9	−1.55 (13)	C8—N7—C14—C16	169.88 (17)
N6—Cu1—N7—C9	−88.76 (14)	C9—N7—C14—C16	−66.4 (2)
N4i—Cu1—N7—C14	34.84 (14)	Cu1—N7—C14—C16	57.11 (19)
N1—Cu1—N7—C14	162.1 (19)	C8—N7—C14—C15	−65.2 (2)
N5—Cu1—N7—C14	−126.26 (14)	C9—N7—C14—C15	58.5 (2)
N6—Cu1—N7—C14	146.53 (14)	Cu1—N7—C14—C15	−178.02 (14)
Cu1—N1—C1—Ni1	41 (2)	C10—N5—C17—C19	−53.0 (2)
C3—Ni1—C1—N1	32 (3)	C5—N5—C17—C19	68.6 (2)
C4—Ni1—C1—N1	−149.3 (18)	Cu1—N5—C17—C19	−171.15 (14)
C2—Ni1—C1—N1	23.7 (18)	C10—N5—C17—C18	70.5 (2)
C3—Ni1—C2—N2	110 (3)	C5—N5—C17—C18	−167.91 (16)
C4—Ni1—C2—N2	33 (3)	Cu1—N5—C17—C18	−47.63 (19)
C1—Ni1—C2—N2	−71 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3ii	0.85 (2)	2.02 (2)	2.874 (3)	179 (3)
O1—H1B···O2iii	0.85 (2)	1.92 (2)	2.745 (3)	165 (2)
O2—H2A···N2	0.86 (2)	1.98 (2)	2.831 (3)	171 (3)
O2—H2B···O1iv	0.86 (3)	1.92 (3)	2.775 (3)	174 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N3i	0.85 (2)	2.02 (2)	2.874 (3)	179 (3)
O1—H1B⋯O2ii	0.85 (2)	1.92 (2)	2.745 (3)	165 (2)
O2—H2A⋯N2	0.86 (2)	1.98 (2)	2.831 (3)	171 (3)
O2—H2B⋯O1iii	0.86 (3)	1.92 (3)	2.775 (3)	174 (2)

Symmetry codes: (i) ; (ii) ; (iii) .