Bis(acetonitrile-κN)diaqua-bis-(perchlorato-κO)copper(II).

In the title compound, [Cu(ClO(4))(2)(CH(3)CN)(2)(H(2)O)(2)], the Cu(2+) ion, located on a special position (site symmetry [Formula: see text]), is coordinated by six monodentate ligands, viz. an N-coordin-ated acetonitrile, a perchlorate anion and a water mol-ecule, and their symmetry-related counterparts. The perchlorate anion is disordered over two sets of sites with occupancies of 0.53 (2) and 0.47 (2). The crystal structure is stabilized by O-H⋯O hydrogen bonds involving the perchlorate ion and aqua H atoms.

Related literature

For details of the changing Cu(II/I) redox potential with increasing acetonitrile contents in water–acetonitrile solution, see: Cox et al. (1988 ▶); Verma & Sood (1979 ▶); Sumalekshmy & Gopidas (2005 ▶); Ajayakumar et al. (2009 ▶); Drew et al. (1985 ▶). For the dependence of the luminescent properties (emission energy) of the 3-cyano-4-dicyano­methyl­ene-5-oxo-4,5-dihydro-1H-pyrrol-2-olate (A)-based salts depend on the mol­ecular environment around (A), see: Tafeenko et al. (2009 ▶, 2010 ▶). For transition metals as fluorescence quenchers, see: Xu et al. (2005 ▶, 2010 ▶). For a previous study on the formation of related compounds, see: Inamo et al. (2001 ▶).

Experimental

Crystal data

[Cu(ClO4)2(C2H3N)2(H2O)2]

M = 380.59

Triclinic,

a = 5.581 (1) Å

b = 7.244 (2) Å

c = 8.733 (2) Å

α = 82.82 (2)°

β = 76.86 (1)°

γ = 77.12 (1)°

V = 334.1 (1) Å3

Z = 1

Ag Kα radiation

λ = 0.56085 Å

μ = 1.09 mm−1

T = 296 K

0.15 × 0.1 × 0.08 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

2518 measured reflections

1259 independent reflections

1020 reflections with I > 2s(I)

R int = 0.049

2 standard reflections every 120 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.192

S = 1.08

1259 reflections

138 parameters

11 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.70 e Å−3

Δρmin = −1.09 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2000 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811027309/fi2110sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027309/fi2110Isup2.hkl

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

[Cu(ClO4)2(C2H3N)2(H2O)2]	Z = 1
Mr = 380.59	F(000) = 191
Triclinic, P1	Dx = 1.891 Mg m−3
Hall symbol: -P 1	Melting point: 422 K
a = 5.581 (1) Å	Ag Kα radiation, λ = 0.56085 Å
b = 7.244 (2) Å	Cell parameters from 25 reflections
c = 8.733 (2) Å	θ = 11–13°
α = 82.82 (2)°	µ = 1.09 mm−1
β = 76.86 (1)°	T = 296 K
γ = 77.12 (1)°	Prism, light-blue
V = 334.1 (1) Å3	0.15 × 0.1 × 0.08 mm

Enraf–Nonius CAD-4 diffractometer	Rint = 0.049
Radiation source: fine-focus sealed tube	θmax = 20.0°, θmin = 1.9°
graphite	h = −6→6
non–profiled ω scans	k = −8→8
2518 measured reflections	l = −10→10
1259 independent reflections	2 standard reflections every 120 min
1020 reflections with I > 2s(I)	intensity decay: none

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.192	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.1161P)2 + 0.4339P] where P = (Fo2 + 2Fc2)/3
1259 reflections	(Δ/σ)max = 0.042
138 parameters	Δρmax = 0.70 e Å−3
11 restraints	Δρmin = −1.09 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	Occ. (<1)
Cu1	0.0000	0.5000	0.5000	0.0477 (4)
O1	0.2556 (10)	0.2741 (6)	0.5295 (6)	0.0574 (12)
N1	0.2362 (12)	0.5987 (8)	0.3237 (7)	0.0631 (16)
C1	0.3717 (13)	0.6605 (9)	0.2302 (8)	0.0555 (15)
C2	0.5546 (16)	0.7387 (12)	0.1089 (9)	0.072 (2)
H2A	0.7197	0.6899	0.1297	0.109*
H2B	0.5174	0.8747	0.1088	0.109*
H2C	0.5478	0.7034	0.0079	0.109*
Cl1	0.120 (3)	0.803 (2)	0.7550 (16)	0.0538 (10)	0.53 (2)
O2	0.195 (3)	0.656 (3)	0.651 (2)	0.082 (6)	0.53 (2)
O3	0.295 (5)	0.921 (3)	0.694 (3)	0.142 (9)	0.53 (2)
O4	0.143 (3)	0.729 (3)	0.9072 (14)	0.105 (6)	0.53 (2)
O5	−0.124 (3)	0.902 (2)	0.755 (2)	0.096 (5)	0.53 (2)
Cl11	0.132 (3)	0.820 (2)	0.7453 (18)	0.0538 (10)	0.47 (2)
O21	0.112 (5)	0.637 (2)	0.717 (2)	0.079 (6)	0.47 (2)
O31	0.383 (2)	0.837 (3)	0.729 (2)	0.080 (5)	0.47 (2)
O41	0.008 (6)	0.853 (6)	0.899 (3)	0.22 (2)	0.47 (2)
O51	0.017 (6)	0.955 (2)	0.644 (4)	0.156 (12)	0.47 (2)
H11	0.212 (12)	0.172 (10)	0.565 (7)	0.041 (16)*
H12	0.357 (17)	0.228 (12)	0.458 (10)	0.07 (3)*

	U11	U22	U33	U12	U13	U23
Cu1	0.0492 (7)	0.0344 (6)	0.0530 (7)	−0.0110 (4)	0.0021 (4)	0.0024 (4)
O1	0.063 (3)	0.034 (2)	0.064 (3)	−0.004 (2)	0.001 (2)	0.002 (2)
N1	0.060 (3)	0.045 (3)	0.068 (3)	−0.013 (3)	0.014 (3)	0.008 (2)
C1	0.057 (4)	0.042 (3)	0.060 (4)	−0.006 (3)	−0.005 (3)	0.002 (3)
C2	0.073 (5)	0.075 (5)	0.060 (4)	−0.028 (4)	0.005 (4)	0.016 (3)
Cl1	0.0544 (13)	0.040 (2)	0.0630 (16)	−0.0150 (12)	0.0034 (11)	−0.0097 (13)
O2	0.062 (9)	0.085 (11)	0.107 (13)	0.011 (7)	−0.033 (9)	−0.051 (10)
O3	0.115 (16)	0.087 (11)	0.23 (2)	−0.061 (11)	−0.042 (14)	0.062 (13)
O4	0.093 (11)	0.152 (15)	0.046 (6)	−0.002 (9)	0.000 (6)	0.013 (7)
O5	0.072 (8)	0.088 (11)	0.110 (11)	0.018 (7)	−0.007 (7)	−0.028 (8)
Cl11	0.0544 (13)	0.040 (2)	0.0630 (16)	−0.0150 (12)	0.0034 (11)	−0.0097 (13)
O21	0.111 (17)	0.047 (7)	0.090 (12)	−0.027 (9)	−0.039 (10)	0.003 (7)
O31	0.044 (7)	0.117 (14)	0.085 (9)	−0.034 (8)	0.006 (6)	−0.028 (9)
O41	0.18 (3)	0.31 (4)	0.17 (3)	−0.16 (3)	0.12 (2)	−0.15 (3)
O51	0.19 (3)	0.041 (8)	0.26 (3)	−0.028 (10)	−0.11 (2)	0.040 (11)

Cu1—O1	1.950 (5)	C2—H2C	0.9600
Cu1—N1	1.960 (5)	Cl1—O5	1.390 (14)
Cu1—O2	2.401 (15)	Cl1—O4	1.391 (14)
O1—H11	0.83 (7)	Cl1—O3	1.414 (14)
O1—H12	0.79 (9)	Cl1—O2	1.418 (12)
N1—C1	1.103 (9)	Cl11—O51	1.386 (15)
C1—C2	1.450 (9)	Cl11—O41	1.387 (15)
C2—H2A	0.9600	Cl11—O31	1.409 (14)
C2—H2B	0.9600	Cl11—O21	1.413 (13)
O1—Cu1—O1i	180.000 (1)	C1—C2—H2C	109.5
O1—Cu1—N1	90.4 (2)	H2A—C2—H2C	109.5
O1i—Cu1—N1	89.6 (2)	H2B—C2—H2C	109.5
N1—Cu1—N1i	180.0 (3)	O5—Cl1—O4	110.2 (13)
O1—Cu1—O2i	93.3 (4)	O5—Cl1—O3	110.9 (15)
N1—Cu1—O2i	97.7 (6)	O4—Cl1—O3	110.2 (14)
N1i—Cu1—O2i	82.3 (6)	O5—Cl1—O2	112.1 (11)
O1—Cu1—O2	86.7 (4)	O4—Cl1—O2	110.3 (13)
O2i—Cu1—O2	180.0 (7)	O3—Cl1—O2	102.9 (14)
Cu1—O1—H11	120 (4)	Cl1—O2—Cu1	137.3 (11)
Cu1—O1—H12	123 (6)	O51—Cl11—O41	109 (2)
H11—O1—H12	93 (7)	O51—Cl11—O31	109.9 (15)
C1—N1—Cu1	176.0 (7)	O41—Cl11—O31	108.2 (15)
N1—C1—C2	178.6 (8)	O51—Cl11—O21	109.8 (13)
C1—C2—H2A	109.5	O41—Cl11—O21	107.7 (16)
C1—C2—H2B	109.5	O31—Cl11—O21	112.3 (14)
H2A—C2—H2B	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11···O3ii	0.83 (7)	2.03 (7)	2.758 (17)	146 (6)
O1—H12···O3iii	0.79 (9)	2.22 (10)	3.00 (3)	165 (8)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H11⋯O3i	0.83 (7)	2.03 (7)	2.758 (17)	146 (6)
O1—H12⋯O3ii	0.79 (9)	2.22 (10)	3.00 (3)	165 (8)

Symmetry codes: (i) ; (ii) .