Tris(propionitrile-κN)[1,4,7-tris­(cyano­meth­yl)-1,4,7-triaza­cyclo­nonane-κ3N1,N4,N7]copper(II) bis­(perchlorate) dihydrate

Zhang, Z.; Lu, J.; Wu, D.

doi:10.1107/S1600536810003211

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages m235-m236

https://doi.org/10.1107/S1600536810003211

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Tris(propionitrile-κN)[1,4,7-tris(cyanomethyl)-1,4,7-triazacyclononane-κ³N¹,N⁴,N⁷]copper(II) bis(perchlorate) dihydrate

Zhong Zhang,^a ^* Jianqi Lu ^a and Difeng Wu ^a

^aCollege of Chemistry and Chemical Engineering, Guangxi Normal University, Yucai Road 15, Guilin 541004, People's Republic of China
^*Correspondence e-mail: zhangzhong@mailbox.gxnu.edu.cn

(Received 16 December 2009; accepted 26 January 2010; online 30 January 2010)

In the title compound, [Cu(C₃H₅N)₃(C₁₂H₁₈N₆)](ClO₄)₂·2H₂O, the Cu^II atom lies on a threefold rotation axis and is coordinated in a distorted N₆ octahedral environment by three tertiary amines from the tridentate chelating azamacrocyclic ligand and three propionitrile molecules. Intermolecular non-classical C—H⋯N hydrogen bonding interlinks the [Cu(C₃H₅N)₃(C₁₂H₁₈N₆)]²⁺ cations into a two-dimensional supramolecular sheet extending along the ab plane. The crystal packing also exhibits weak C—H⋯O interactions.

Related literature

For transition metal complexes with cyanoalkylated triazamacrocycles, see: Tei et al. (2003 ). For transition metal complexes with cyanoalkylated tetraazamacrocycles, see: Aneetha et al. (1999 ); Freeman et al. (1984 ); Kang et al. (2002a ); Kong et al. (2000 ). For the reactivity of the pendant nitrile group attached to the azamacrocycle, see: Freeman et al. (1984); Kang et al. (2002b , 2005 , 2008 ); Siegfried et al. (2005 ); Tei et al. (2003); Zhang et al. (2006 ). For the synthesis of the triazamacrocyclic derivative 1,4,7-tris(cyanomethyl)-1,4,7-triazacyclononane, see: Tei et al. (1998 ).

Experimental

Crystal data

[Cu(C₃H₅N)₃(C₁₂H₁₈N₆)](ClO₄)₂·2H₂O
M_r = 710.05
Trigonal, $[R \overline 3]$
a = 9.962 (2) Å
c = 61.623 (18) Å
V = 5296 (2) Å³
Z = 6
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 298 K
0.34 × 0.32 × 0.14 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.760, T_max = 0.887
9484 measured reflections
2327 independent reflections
1837 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.144
S = 0.99
2327 reflections
132 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯N2ⁱ	0.97	2.49	3.371 (5)	151
C3—H3A⋯O11	0.97	2.59	3.269 (4)	127
C6—H6A⋯O12ⁱⁱ	0.97	2.27	3.120 (4)	146
Symmetry codes: (i) -y+2, x-y+1, z; (ii) x-1, y-1, z.

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; 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/S1600536810003211/rk2185sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810003211/rk2185Isup2.hkl

checkCIF report

Comment top

The coordination chemistry of the azamacrocycles with nitrile pendant arms has been studied extensively. Usually, these azamacrocycle derivatives only chelate the metal through tertiary amines and the pendant nitrile groups do not involve in the coordination (Aneetha et al., 1999; Freeman et al., 1984; Kang et al., 2002a; Kong et al., 2000; Tei et al., 2003). However, the reactivity of the nitrile group in these complexes towards nucleophilic reagents, such as water, alcohols and amines, provides a convenient route to the synthesis of a variety of N–functionalized azamacrocycles (Freeman et al., 1984; Kang et al., 2002b, 2005, 2008; Siegfried et al., 2005; Tei et al., 2003; Zhang et al., 2006). In order to obtain further knowledge about the reactivity of the nitrile groups attached to the triazamacrocycle, a title compound of Cu^II with 1,4,7–tris(cyanomethyl)–1,4,7–triazacyclononane has been prepared and structurally characterized.

As shown in Fig. 1, the distorted octahedral Cu^II center in the title compound is located on a threefold rotation axis and is ligated by three N donors of the tridentate azamacrocycle backbone and other three from coordinated propionitrile molecules. The Cu—N(macrocycle) length (2.089 (3)Å) is slightly longer than that of the Cu—N(propionitrile) (2.030 (3)Å), while the bond angles subtended by cis–pairs of donor atoms at Cu^II range from 84.13 (13)° to 96.12 (11)°. In the ab–plane, each [Cu(C₁₂H₁₈N₆)(C₃H₅N)₃]²⁺ cation are linked with six neighbouring cations by means of C—H···N hydrogen bonding (Table 1) to form an extended two–dimensional supramolecular network, as depicted in Fig. 2. Perchlorate counter–anions are embedded in the two–dimensional supramolecular cationic layer via weak interactions.

Related literature top

For transition metal complexes with cyanoalkylated triazamacrocycles, see: Tei et al. (2003). For transition metal complexes with cyanoalkylated tetraazamacrocycles, see: Aneetha et al. (1999); Freeman et al. (1984); Kang et al. (2002a); Kong et al. (2000). For the reactivity of the pendant nitrile group attached to the azamacrocycle, see: Freeman et al. (1984); Kang et al. (2002b, 2005, 2008); Siegfried et al. (2005); Tei et al. (2003); Zhang et al. (2006). For the synthesis of the triazamacrocyclic derivative 1,4,7-tris(cyanomethyl)-1,4,7-triazacyclononane, see: Tei et al. (1998).

Experimental top

The triazamacrocyclic derivative 1,4,7–tris(cyanomethyl)–1,4,7–triazacyclononane was prepared according to a published method (Tei et al., 1998).

To the propionitrile solution (20 ml) of the triazamacrocyclic ligand (49 mg, 0.2 mmol), Cu(ClO₄)₂^.6H₂O (74 mg, 0.2 mmol) was added. The resulting mixture was stirred under reflux for 4 h and then cooled to ambient temperature. Blue single crystals of title compound suitable for X–ray diffraction analysis were obtained by slow diffusion of diethyl ether into the complex solution. (yield 51 mg, 72%). Elemental analysis found: C 35.52; H 5.39; N 17.69%; calculated for C₂₁H₃₇Cl₂CuN₉O₁₀: C 35.31; H 5.28; N 17.75%.

Structure description top

For transition metal complexes with cyanoalkylated triazamacrocycles, see: Tei et al. (2003). For transition metal complexes with cyanoalkylated tetraazamacrocycles, see: Aneetha et al. (1999); Freeman et al. (1984); Kang et al. (2002a); Kong et al. (2000). For the reactivity of the pendant nitrile group attached to the azamacrocycle, see: Freeman et al. (1984); Kang et al. (2002b, 2005, 2008); Siegfried et al. (2005); Tei et al. (2003); Zhang et al. (2006). For the synthesis of the triazamacrocyclic derivative 1,4,7-tris(cyanomethyl)-1,4,7-triazacyclononane, see: Tei et al. (1998).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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. An ORTEP plot for the title compound with the atom labelling scheme. Displacement ellipsoids are drawn at 30% probability level. H atoms of the macrocyclic ligand are omitted for clarity. The disorder in the solvent water molecules are not shown. Symmetry codes: (i) -x+y+1, -x+1, z; (ii) -y+2, x-y+1, z; (iii) -x+y+1, -x+2, z; (iv) -y+1, x-y+1, z; (v) -x+y, -x+1, z; (vi) -y+1, x-y, z.
	Fig. 2. A view of the packing diagram of the title compound, showing the two–dimensional hydrogen–bonding supramolecular sheet. H atoms not involved in hydrogen bonds are omitted for clarity.

Tris(propionitrile-κN)[1,4,7-tris(cyanomethyl)-1,4,7-triazacyclononane- κ³N¹,N⁴,N⁷]copper(II) bis(perchlorate) dihydrate top

Crystal data top

[Cu(C₃H₅N)₃(C₁₂H₁₈N₆)](ClO₄)₂·2H₂O	D_x = 1.336 Mg m⁻³
M_r = 710.05	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 1799 reflections
Hall symbol: -R 3	θ = 2.4–20.9°
a = 9.962 (2) Å	µ = 0.83 mm⁻¹
c = 61.623 (18) Å	T = 298 K
V = 5296 (2) Å³	Plate, blue
Z = 6	0.34 × 0.32 × 0.14 mm
F(000) = 2214

Data collection top

Bruker SMART APEXII CCD diffractometer	2327 independent reflections
Radiation source: fine–focus sealed tube	1837 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
φ and ω scans	θ_max = 26.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −12→12
T_min = 0.760, T_max = 0.887	k = −7→12
9484 measured reflections	l = −75→64

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0959P)² + 1.480P] where P = (F_o² + 2F_c²)/3
2327 reflections	(Δ/σ)_max < 0.001
132 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Cu(C₃H₅N)₃(C₁₂H₁₈N₆)](ClO₄)₂·2H₂O	Z = 6
M_r = 710.05	Mo Kα radiation
Trigonal, R3	µ = 0.83 mm⁻¹
a = 9.962 (2) Å	T = 298 K
c = 61.623 (18) Å	0.34 × 0.32 × 0.14 mm
V = 5296 (2) Å³

Data collection top

Bruker SMART APEXII CCD diffractometer	2327 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1837 reflections with I > 2σ(I)
T_min = 0.760, T_max = 0.887	R_int = 0.044
9484 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.144	H-atom parameters constrained
S = 0.99	Δρ_max = 0.26 e Å⁻³
2327 reflections	Δρ_min = −0.44 e Å⁻³
132 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	Occ. (<1)
C1	0.8592 (4)	0.4740 (4)	0.02573 (6)	0.0412 (8)
H1A	0.9682	0.5407	0.0224	0.049*
H1B	0.8078	0.4188	0.0126	0.049*
C2	0.7901 (4)	0.5749 (4)	0.03281 (5)	0.0336 (7)
H2A	0.8615	0.6547	0.0427	0.040*
H2B	0.7778	0.6258	0.0202	0.040*
C3	0.5888 (4)	0.5827 (4)	0.05172 (5)	0.0379 (8)
H3A	0.6568	0.6427	0.0635	0.045*
H3B	0.4873	0.5155	0.0580	0.045*
C4	0.5751 (4)	0.6906 (4)	0.03705 (5)	0.0360 (7)
C5	0.4092 (4)	0.2743 (4)	0.09939 (5)	0.0394 (8)
C6	0.3004 (4)	0.2578 (4)	0.11629 (5)	0.0389 (8)
H6A	0.1959	0.2111	0.1105	0.047*
H6B	0.3281	0.3578	0.1225	0.047*
C7	0.3123 (5)	0.1525 (4)	0.13332 (5)	0.0404 (8)
H7A	0.3651	0.1029	0.1272	0.061*
H7B	0.2101	0.0751	0.1378	0.061*
H7C	0.3691	0.2133	0.1456	0.061*
Cl1	1.0000	1.0000	0.07171 (2)	0.0373 (3)
Cl2	0.3333	0.6667	0.09665 (2)	0.0383 (3)
Cu1	0.6667	0.3333	0.063982 (10)	0.0316 (2)
N1	0.6443 (3)	0.4868 (3)	0.04321 (4)	0.0335 (6)
N2	0.5838 (3)	0.7880 (3)	0.02473 (4)	0.0385 (7)
N3	0.4964 (4)	0.3039 (3)	0.08486 (5)	0.0423 (7)
O1	0.3333	0.6667	0.1667	0.0247 (10)
H1C	0.3300	0.6081	0.1769	0.037*	0.16667
H1D	0.3867	0.7608	0.1706	0.037*	0.16667
O2	0.6667	0.3333	0.14060 (6)	0.0353 (8)
H2C	0.6152	0.3741	0.1454	0.042*	0.33333
H2D	0.6160	0.2696	0.1305	0.042*	0.33333
O3	1.0000	1.0000	0.0000	0.0544 (16)
H3D	1.0241	1.0481	0.0120	0.065*	0.16667
H3C	0.9020	0.9506	−0.0014	0.082*	0.16667
O11	0.8501 (3)	0.9383 (3)	0.06411 (4)	0.0473 (7)
O12	1.0000	1.0000	0.09409 (6)	0.0442 (10)
O21	0.3333	0.6667	0.07487 (7)	0.0413 (10)
O22	0.3579 (3)	0.8074 (3)	0.10312 (4)	0.0379 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0410 (19)	0.0400 (19)	0.0380 (17)	0.0170 (16)	0.0013 (14)	−0.0008 (14)
C2	0.0297 (15)	0.0339 (16)	0.0334 (15)	0.0131 (13)	0.0009 (12)	−0.0114 (13)
C3	0.0303 (16)	0.0250 (15)	0.0417 (17)	0.0014 (13)	0.0066 (13)	0.0010 (13)
C4	0.0364 (17)	0.0447 (18)	0.0314 (15)	0.0238 (15)	0.0036 (13)	−0.0041 (14)
C5	0.0386 (19)	0.0444 (19)	0.0345 (16)	0.0203 (16)	−0.0006 (14)	0.0139 (14)
C6	0.0439 (19)	0.0317 (17)	0.0335 (16)	0.0132 (15)	0.0138 (14)	0.0150 (13)
C7	0.056 (2)	0.0431 (19)	0.0344 (16)	0.0335 (18)	0.0156 (15)	0.0193 (15)
Cl1	0.0360 (5)	0.0360 (5)	0.0400 (7)	0.0180 (2)	0.000	0.000
Cl2	0.0363 (5)	0.0363 (5)	0.0421 (7)	0.0182 (2)	0.000	0.000
Cu1	0.0322 (3)	0.0322 (3)	0.0304 (4)	0.01610 (14)	0.000	0.000
N1	0.0323 (14)	0.0296 (13)	0.0363 (14)	0.0138 (11)	0.0006 (11)	0.0048 (10)
N2	0.0368 (15)	0.0411 (16)	0.0304 (13)	0.0142 (13)	0.0070 (11)	0.0034 (12)
N3	0.0474 (17)	0.0317 (15)	0.0431 (15)	0.0163 (13)	0.0109 (14)	0.0150 (12)
O1	0.0253 (15)	0.0253 (15)	0.023 (2)	0.0126 (7)	0.000	0.000
O2	0.0318 (12)	0.0318 (12)	0.042 (2)	0.0159 (6)	0.000	0.000
O3	0.054 (2)	0.054 (2)	0.054 (4)	0.0272 (12)	0.000	0.000
O11	0.0335 (13)	0.0445 (14)	0.0399 (13)	0.0015 (11)	0.0118 (10)	−0.0034 (11)
O12	0.0503 (16)	0.0503 (16)	0.032 (2)	0.0252 (8)	0.000	0.000
O21	0.0424 (15)	0.0424 (15)	0.039 (2)	0.0212 (7)	0.000	0.000
O22	0.0341 (12)	0.0427 (13)	0.0341 (11)	0.0172 (11)	−0.0008 (9)	0.0054 (10)

Geometric parameters (Å, º) top

C1—C2	1.538 (5)	Cl1—O11ⁱⁱ	1.382 (3)
C1—N1ⁱ	1.543 (4)	Cl1—O11	1.382 (3)
C1—H1A	0.9700	Cl1—O11ⁱⁱⁱ	1.382 (3)
C1—H1B	0.9700	Cl2—O21	1.342 (4)
C2—N1	1.420 (4)	Cl2—O22	1.357 (3)
C2—H2A	0.9700	Cl2—O22^iv	1.357 (3)
C2—H2B	0.9700	Cl2—O22^v	1.357 (3)
C3—N1	1.422 (5)	Cu1—N3^vi	2.030 (3)
C3—C4	1.462 (5)	Cu1—N3ⁱ	2.030 (3)
C3—H3A	0.9700	Cu1—N3	2.030 (3)
C3—H3B	0.9700	Cu1—N1^vi	2.089 (3)
C4—N2	1.200 (5)	Cu1—N1ⁱ	2.089 (3)
C5—N3	1.178 (5)	Cu1—N1	2.089 (3)
C5—C6	1.452 (5)	N1—C1^vi	1.543 (4)
C6—C7	1.529 (4)	O1—H1C	0.8500
C6—H6A	0.9700	O1—H1D	0.8500
C6—H6B	0.9700	O2—H2C	0.8500
C7—H7A	0.9600	O2—H2D	0.8500
C7—H7B	0.9600	O3—H3D	0.8500
C7—H7C	0.9600	O3—H3C	0.8500
Cl1—O12	1.379 (4)

C2—C1—N1ⁱ	112.9 (3)	O12—Cl1—O11ⁱⁱⁱ	109.83 (11)
C2—C1—H1A	109.0	O11ⁱⁱ—Cl1—O11ⁱⁱⁱ	109.11 (11)
N1ⁱ—C1—H1A	109.0	O11—Cl1—O11ⁱⁱⁱ	109.11 (11)
C2—C1—H1B	109.0	O21—Cl2—O22	107.08 (11)
N1ⁱ—C1—H1B	109.0	O21—Cl2—O22^iv	107.08 (11)
H1A—C1—H1B	107.8	O22—Cl2—O22^iv	111.75 (10)
N1—C2—C1	112.2 (3)	O21—Cl2—O22^v	107.08 (11)
N1—C2—H2A	109.2	O22—Cl2—O22^v	111.75 (10)
C1—C2—H2A	109.2	O22^iv—Cl2—O22^v	111.75 (10)
N1—C2—H2B	109.2	N3^vi—Cu1—N3ⁱ	84.13 (13)
C1—C2—H2B	109.2	N3^vi—Cu1—N3	84.13 (13)
H2A—C2—H2B	107.9	N3ⁱ—Cu1—N3	84.13 (13)
N1—C3—C4	118.5 (3)	N3^vi—Cu1—N1^vi	96.12 (11)
N1—C3—H3A	107.7	N3ⁱ—Cu1—N1^vi	177.46 (11)
C4—C3—H3A	107.7	N3—Cu1—N1^vi	93.37 (12)
N1—C3—H3B	107.7	N3^vi—Cu1—N1ⁱ	93.37 (12)
C4—C3—H3B	107.7	N3ⁱ—Cu1—N1ⁱ	96.12 (11)
H3A—C3—H3B	107.1	N3—Cu1—N1ⁱ	177.46 (11)
N2—C4—C3	171.7 (4)	N1^vi—Cu1—N1ⁱ	86.40 (11)
N3—C5—C6	171.5 (4)	N3^vi—Cu1—N1	177.46 (11)
C5—C6—C7	105.1 (3)	N3ⁱ—Cu1—N1	93.37 (12)
C5—C6—H6A	110.7	N3—Cu1—N1	96.12 (11)
C7—C6—H6A	110.7	N1^vi—Cu1—N1	86.40 (11)
C5—C6—H6B	110.7	N1ⁱ—Cu1—N1	86.40 (11)
C7—C6—H6B	110.7	C2—N1—C3	111.9 (2)
H6A—C6—H6B	108.8	C2—N1—C1^vi	107.5 (2)
C6—C7—H7A	109.5	C3—N1—C1^vi	105.8 (3)
C6—C7—H7B	109.5	C2—N1—Cu1	106.2 (2)
H7A—C7—H7B	109.5	C3—N1—Cu1	119.0 (2)
C6—C7—H7C	109.5	C1^vi—N1—Cu1	105.87 (19)
H7A—C7—H7C	109.5	C5—N3—Cu1	167.5 (3)
H7B—C7—H7C	109.5	H1C—O1—H1D	109.4
O12—Cl1—O11ⁱⁱ	109.83 (11)	H2C—O2—H2D	109.5
O12—Cl1—O11	109.83 (11)	H3D—O3—H3C	109.5
O11ⁱⁱ—Cl1—O11	109.11 (11)

N1ⁱ—C1—C2—N1	−43.3 (4)	N3—Cu1—N1—C3	28.2 (2)
C1—C2—N1—C3	173.9 (3)	N1^vi—Cu1—N1—C3	121.2 (3)
C1—C2—N1—C1^vi	−70.5 (4)	N1ⁱ—Cu1—N1—C3	−152.2 (3)
C1—C2—N1—Cu1	42.5 (3)	N3ⁱ—Cu1—N1—C1^vi	−175.0 (2)
C4—C3—N1—C2	54.9 (4)	N3—Cu1—N1—C1^vi	−90.6 (2)
C4—C3—N1—C1^vi	−61.8 (3)	N1^vi—Cu1—N1—C1^vi	2.44 (19)
C4—C3—N1—Cu1	179.4 (2)	N1ⁱ—Cu1—N1—C1^vi	89.05 (15)
N3ⁱ—Cu1—N1—C2	71.0 (2)	N3^vi—Cu1—N3—C5	10.1 (14)
N3—Cu1—N1—C2	155.4 (2)	N3ⁱ—Cu1—N3—C5	−74.6 (13)
N1^vi—Cu1—N1—C2	−111.58 (15)	N1^vi—Cu1—N3—C5	105.9 (14)
N1ⁱ—Cu1—N1—C2	−25.0 (2)	N1—Cu1—N3—C5	−167.3 (14)
N3ⁱ—Cu1—N1—C3	−56.3 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N2ⁱⁱ	0.97	2.49	3.371 (5)	151
C3—H3A···O11	0.97	2.59	3.269 (4)	127
C6—H6A···O12^vii	0.97	2.27	3.120 (4)	146

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

Experimental details

Crystal data
Chemical formula	[Cu(C₃H₅N)₃(C₁₂H₁₈N₆)](ClO₄)₂·2H₂O
M_r	710.05
Crystal system, space group	Trigonal, R3
Temperature (K)	298
a, c (Å)	9.962 (2), 61.623 (18)
V (Å³)	5296 (2)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	0.83
Crystal size (mm)	0.34 × 0.32 × 0.14

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.760, 0.887
No. of measured, independent and observed [I > 2σ(I)] reflections	9484, 2327, 1837
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.144, 0.99
No. of reflections	2327
No. of parameters	132
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.44

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), 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
C1—H1A···N2ⁱ	0.97	2.49	3.371 (5)	151
C3—H3A···O11	0.97	2.59	3.269 (4)	127
C6—H6A···O12ⁱⁱ	0.97	2.27	3.120 (4)	146

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

Acknowledgements

The authors are grateful for financial support from the Guangxi Science Foundation (grant No. 0832023) and the Scientific Research Foundation of Guangxi Normal University.

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