Discrete water clusters in tetra-μ-cyanido-tetra­cyanidobis(1,4,7-triisopropyl-1,4,7-triaza­cyclo­nona­ne)dicopper(II)dinickel(II) tetra­hydrate

Cui, H.-X.; Wang, Y.-C.

doi:10.1107/S1600536812024282

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages m880-m881

https://doi.org/10.1107/S1600536812024282

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Discrete water clusters in tetra-μ-cyanido-tetracyanidobis(1,4,7-triisopropyl-1,4,7-triazacyclononane)dicopper(II)dinickel(II) tetrahydrate

Hong-Xia Cui ^a ^* and Yan-Chao Wang ^b

^aDepartment of Chemistry and Chemical Engineering, Shengli College, China University of Petroleum, Dongying 257097, People's Republic of China, and ^bDepartment of Basic Science, Liao Ning Institute of Science and Technology, Benxi 117004, People's Republic of China
^*Correspondence e-mail: chx1979124@126.com

(Received 9 April 2012; accepted 28 May 2012; online 13 June 2012)

The title tetracyanidonickelate–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 molecule and two water molecules. 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 tetramer water cluster. Within the cluster, the four water molecules 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_r = 1035.59
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.034
wR(F²) = 0.074
S = 1.03
5622 reflections
293 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.39 e Å⁻³

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) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) x, y, z+1.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812024282/vm2171sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812024282/vm2171Isup2.hkl

checkCIF report

Comment top

In recent years, much attention has been paid to assemble cyanide-bridged coordination complexes because of their promising properties and applications including electronics, magnetism and catalysis (Zhao et al., 2009; Dunbar & Heintz, 1997; Orendac et al., 2002), in which tetracyanonickelate complexes have also become the focus. On the one hand, diamagnetic [Ni(CN)₄]^2- is an excellent model for magnetic studies which bridge paramagnetic ions, but on the other hand the tetracyanonickelate anion, as a bridging ligand, can be used to construct one-dimensional, two-dimensional and three-dimensional structures (Bozoglian et al., 2005; Maji et al., 2001; Dunbar & Heintz, 1997; Černák et al., 2000; 1988; 1990). Low-dimensional cyanide-bridged complexes based on [Ni(CN)₄]^2- form a new family of molecular magnetic materials. However, the use of macrocyclic ligands as terminal group to control the low-dimensional structure is still relatively rare. On the other hand, water clusters can play an important role in the stabilization of supramolecular systems both in solution and in the solid state, and there is clearly a need for a better understanding of how such water aggregations are influenced by the overall structure of their surroundings (Long et al., 2004; Xantheas, 1995). In the past several decades, considerable attention has been focused on theoretical and experimental studies of small water clusters to understand the structures and characteristics of liquid water and ice (Ugalde et al., 2000; Gregory et al., 1996).

In this study, we report a complex 1 in which [Ni(CN)₄]^2- acts as bridging ligand to construct a low-dimensional complex. Complex 1 can be synthesized by the reaction of [Ni(Pr₃TACN)]Cl₂ with K₂[Ni(CN)₄], which is a cyanide bridged [2 + 2] type of molecular square. The ligand 1,4,7-triisopropyl-1,4,7-triazacyclononane (Pr₃TACN) was synthesized according to the literature (Hay et al., 1979; Chen et al., 2009). The structure of the complex 1 is shown in Figure 1. The complex contains two [Ni(CN)₄]^2- bridges and two cis-[Cu(Pr₃TACN)]²⁺ moieties in cis-positions to form a [2 + 2] type of discrete molecular square. The Cu1—N(macrocycle) distances (2.0686 (17)–2.2153 (18) Å) are close to the Cu1-N(cyano) distances (1.9781 (18) and 1.9929 (17) Å) and they are longer than the Ni1—C(cyano) distances (1.861 (2)–1.871 (2) Å). Furthermore the C—N(coordinated) distances of the cyano groups are close to the C—N(uncoordinated) distances. Interestingly, a cyclic water tetramer is located in between the complexes 1. Within the cluster, the four water molecules are fully coplanar and each water monomer acts as both single hydrogen bond donor and acceptor. The hydrogen bond distances and angles within the water tetramer are as follows: O1—O2ⁱ = 2.775 (3) Å, O1—O2ⁱⁱ = 2.745 (3) Å, O1ⁱ—O2—O1ⁱⁱⁱ = 100.05 (9)°, O2ⁱ—O1—O2ⁱⁱ = 79.95 (8)° (symmetry codes: (i) x, y, -1 + z; (2) 1 - x, 1 -y, 1 -z; (iii) x,y, z + 1). The average hydrogen bond distance within the water tetramer is 2.76 (1) Å, which is slightily shorter than 2.78 Å estimated in the udud water tetramer of (D₂O)₄ (Ugalde et al., 2000). The most remarkable feature in 1 is that the cyclic water tetramer connects the [2 + 2] molecular square through hydrogen bonds to form a two-dimensional structure (Fig. 2, Table 1).

Related literature top

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 tetracyanonickelate 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 top

A water solution (25 ml) of potassium tetracyanonickel (0.111 g, 0.4 mmol) was layered with an acetonitrile solution (25 ml) of dichloro-(1,4,7-triisopropyl-1,4,7-triazcyclononane)-copper(II) (0.151 g, 0.4 mmol). After about 3 weeks, prism-shaped blue crystals of 1 formed from the solution. The crystals were collected, washed with water and methanol, and dried in the air. Yield: 45% (based on tetracyanonickelate salts). Anal. Calcd for C₁₉H₃₇N₇CuNiO₂: C, 44.07; H, 7.20; N, 18.93. Found: C, 44.25; H, 7.25; N, 19.02%. IR (KBr, cm^-1): 3455 (s), 2974 (s), 2164 (CN, coordinated) and 2135 (CN, uncoordinated), 1652 (s).

Structure description top

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 tetracyanonickelate 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).

Computing details top

Data collection: XSCANS (Bruker, 1999); cell refinement: XSCANS (Bruker, 1999); data reduction: XSCANS (Bruker, 1999); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of 1 showing 30% probability displacement ellipsoids for non-H atoms. The second half of the molecule is generated by symmetry code -x, -y - 1, -z - 1.
	Fig. 2. Stacking diagram of 1 and hydrogen bonding in the water cluster (symmetry code A: 1 - x, 1 - y, -z).

tetra-µ-cyanido-1:2κ²C:N;2:3κ²N:C; 3:4κ²C:N;4:1κ²N:C-tetracyanido- 1κ²C,3κ²C-bis(1,4,7-triisopropyl-1,4,7- triazacyclononane)-2κ³N,N',N''; 4κ³N,N',N''-dicopper(II)dinickel(II) tetrahydrate top

Crystal data top

[Cu₂Ni₂(CN)₈(C₁₅H₃₃N₃)₂]·4H₂O	F(000) = 1092
M_r = 1035.59	D_x = 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

Data collection top

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

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)] = 0.034	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(F_o²) + (0.0357P)²] where P = (F_o² + 2F_c²)/3
5622 reflections	(Δ/σ)_max = 0.002
293 parameters	Δρ_max = 0.52 e Å⁻³
6 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Cu₂Ni₂(CN)₈(C₁₅H₃₃N₃)₂]·4H₂O	V = 2415.1 (8) Å³
M_r = 1035.59	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5896 (17) Å	µ = 1.69 mm⁻¹
b = 18.092 (4) Å	T = 293 K
c = 15.615 (3) Å	0.14 × 0.12 × 0.06 mm
β = 95.61 (3)°

Data collection top

Bruker P4 diffractometer	4475 reflections with I > 2σ(I)
Absorption correction: multi-scan (XSCANS; Bruker, 1999)	R_int = 0.039
T_min = 0.798, T_max = 0.906	3 standard reflections every 120 min
18582 measured reflections	intensity decay: 1.0%
5622 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	6 restraints
wR(F²) = 0.074	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.52 e Å⁻³
5622 reflections	Δρ_min = −0.39 e Å⁻³
293 parameters

Special details top

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
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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···O1^iv	0.86 (3)	1.92 (3)	2.775 (3)	174 (2)

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

Experimental details

Crystal data
Chemical formula	[Cu₂Ni₂(CN)₈(C₁₅H₃₃N₃)₂]·4H₂O
M_r	1035.59
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.5896 (17), 18.092 (4), 15.615 (3)
β (°)	95.61 (3)
V (Å³)	2415.1 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.69
Crystal size (mm)	0.14 × 0.12 × 0.06

Data collection
Diffractometer	Bruker P4
Absorption correction	Multi-scan (XSCANS; Bruker, 1999)
T_min, T_max	0.798, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections	18582, 5622, 4475
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.074, 1.03
No. of reflections	5622
No. of parameters	293
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.39

Computer programs: XSCANS (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3ⁱ	0.851 (16)	2.023 (15)	2.874 (3)	179 (3)
O1—H1B···O2ⁱⁱ	0.846 (18)	1.919 (19)	2.745 (3)	165 (2)
O2—H2A···N2	0.856 (17)	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) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z+1; (iii) x, y, z+1.

Acknowledgements

The authors thank the Department of Chemistry and Chemical Engineering, Shengli College, China University of Petroleum, for supporting this work.

References

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Volume 68| Part 7| July 2012| Pages m880-m881

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

Discrete water clusters in tetra-μ-cyanido-tetra­cyanidobis(1,4,7-triiso­propyl-1,4,7-tri­aza­cyclo­nona­ne)dicopper(II)dinickel(II) tetra­hydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Discrete water clusters in tetra-μ-cyanido-tetracyanidobis(1,4,7-triisopropyl-1,4,7-triazacyclononane)dicopper(II)dinickel(II) tetrahydrate