Bis[μ-(3-acetyl-2-hy­droxy-6-methyl-4H-pyran-4-one-κ3O:O′,O′′)]diaqua­tetra­kis­(pyridine-κN)dicopper(II) diperchlorate

Ourari, A.; Derafa, W.; Bouacida, S.; Aggoun, D.; Daran, J.-C.

doi:10.1107/S1600536812041608

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 11| November 2012| Pages m1356-m1357

doi:10.1107/S1600536812041608

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Bis[μ-(3-acetyl-2-hydroxy-6-methyl-4H-pyran-4-one-κ³O:O′,O′′)]diaquatetrakis(pyridine-κN)dicopper(II) diperchlorate

Ali Ourari,^a Wassila Derafa,^a Sofiane Bouacida,^b,^c ^* Djouhra Aggoun ^a and Jean-Claude Daran ^d

^aLaboratoire d'Electrochimie, d'Ingénierie Moléculaire et de Catalyse Redox (LEIMCR), Faculté des Sciences de l'Ingénieur, Université Farhat Abbas, Sétif 19000, Algeria, ^bUnité de Recherche de Cimie de l'Environnement et Moléculaire Structurale, CHEMS, Université Mentouri-Constantine, 25000, Algeria, ^cDépartement Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Oum El Bouaghi, Algeria, and ^dLaboratoire de Chimie de Coordination, UPR CNRS 8241, 205 route de Narbonne, 31077 Toulouse cedex, France
^*Correspondence e-mail: bouacida_sofiane@yahoo.fr

(Received 15 September 2012; accepted 4 October 2012; online 13 October 2012)

In the centrosymmetric binuclear cation of the title compound, [Cu(C₈H₇O₄)(H₂O)(C₅H₅N)₂]₂(ClO₄)₂, the Cu^II atoms are bridged by a pair of two dehydroacetate anions in a bis-/monodentate mode. The distorted octahedral N₂O₄ coordination sphere of the metal cation is completed by two pyridine N atoms and one O atom of a water molecule. The complex cations and the perchlorate counter anions are arranged in layers parallel to (100). O—H⋯O hydrogen bonds between the coordinating water molecules and the perchlorate anions constitute ribbons parallel to [10-1]. C—H⋯O hydrogen bonds are also observed.

Related literature

For the synthesis of similar compounds, see: Tan & Kok-Peng Ang (1988 ); El-Kubaisi & Ismail (1994 ); Danilova et al. (2003 ); Munde et al. (2010 ); Ourari et al. (2011 ). For applications of related compounds, see: Maiti et al. (1988 ); Mohan et al. (1981 ); Das & Livingstone (1976 ); Ourari et al. (2008 , 2012 ).

Experimental

Crystal data

[Cu(C₈H₇O₄)(H₂O)(C₅H₅N)₂]₂(ClO₄)₂
M_r = 1012.70
Triclinic, $[P \overline 1]$
a = 9.9371 (4) Å
b = 10.3072 (4) Å
c = 10.4440 (5) Å
α = 99.624 (4)°
β = 90.540 (3)°
γ = 97.895 (4)°
V = 1044.09 (8) Å³
Z = 1
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 180 K
0.44 × 0.34 × 0.13 mm

Data collection

Agilent Xcalibur diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.505, T_max = 1.000
20280 measured reflections
4692 independent reflections
3889 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.140
S = 1.12
4692 reflections
288 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.14 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.922 (3)
Cu1—O2	1.962 (3)
Cu1—N2	2.005 (3)
Cu1—N1	2.006 (3)
Cu1—O1W	2.325 (3)
Cu1—O4ⁱ	2.737 (3)
Symmetry code: (i) -x, -y+1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O12	0.83 (6)	2.13 (6)	2.934 (9)	165 (6)
O1W—H2W⋯O11ⁱⁱ	0.74 (6)	2.06 (6)	2.772 (9)	164 (6)
C9—H9⋯O13ⁱⁱⁱ	0.93	2.56	3.389 (7)	148
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) x-1, y-1, z.

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg & Berndt, 2001 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812041608/wm2685sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812041608/wm2685Isup2.hkl

checkCIF report

Comment top

Dehydroacetic acid is used for the synthesis of heterocyclic compounds, some of them with therapeutic activities useful for treatment of human diseases (Das & Livingstone, 1976; Mohan et al., 1981; Maiti et al., 1988). Schiff bases, on the other hand, are widely applied in the synthesis transition metal coordination compounds (Tan & Kok-Peng Ang, 1988; El-Kubaisi & Ismail, 1994; Munde et al., 2010), showing catalytic activities particularly in the oxidation reactions carried out according to the cytochrome P450 model (Ourari et al., 2008, 2011, 2012). Thus, we attempted to synthesize Schiff base half-units in order to use them as starting materials to obtain unsymmetrical tetradentate Schiff base complexes according the Danilova method's (Danilova et al., 2003). Here we describe the formation of a new dinuclear complex, [Cu(C₈H₇O₄)(H₂O)(C₅H₅N)₂]₂(ClO₄)₂], (I), prepared from dehydroacetic acid, copper perchlorate and pyridine in methanolic solution.

The molecular structure of the complex binuclear and centrosymmetric cation of (I) is illustrated in Fig. 1. The connection mode of the copper cations exhibits dimers, i.e. two copper cations are bridged by two dehydroacetate anions in a bis-/monodentate fashion. The asymmetric unit of (I) contains only half of such a dimer. The distorted octahedral coordination sphere around the copper cation is completed by two pyridine ligands and one water molecule. The bond lengths range from 1.922 (3) to 2.325 (3) Å for the Cu—O distances with one more considerably longer bond for Cu—O4 of 2.737 (3) Å; the Cu—N bond lengths are 2.005 (3) and 2.006 (3) Å.

The crystal packing in (I) can be described by alterning layers of cations and tetrahedral perchlorate anions arranged parallel to (100) (Fig. 2). Intermolecular O—H···O hydrogen bonds (Table 2) between the coordinating water molecules and perchlorate anions constitute ribbons parallel to [101]; C—H···O hydrogen bonding interactions eventually links these constituents (Fig. 3).

Related literature top

For the synthesis of similar compounds, see: Tan & Kok-Peng Ang (1988); El-Kubaisi & Ismail (1994); Danilova et al. (2003); Munde et al. (2010); Ourari et al. (2011). For applications of related compounds, see: Maiti et al. (1988); Mohan et al. (1981); Das & Livingstone (1976); Ourari et al. (2008, 2012).

Experimental top

0.168 g (1 mmol) dehydroacetic acid and 0.373 g (1 mmol) copper bis-perchlorate hexahydrate were dissolved in 20 ml of methanol. To this solution 0.108 g (1 mmol) of 1,2-phenylendiamine was added with an excess of pyridine. The mixture was held under stirring and argon atmosphere for two hours. After that time a precipitate appeared that was recovered by filtration. The solid was washed several times with methanol before it was dried under vacuum (yield 64%). From the resulting filtrate crystals were obtained by slow evaporation.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The binuclear complex cation of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms and perchlorate anions were omitted for clarity. [Symmetry code: (i)-x, -y + 1, -z.]
	Fig. 2. Alternating polyhedra of (I) viewed along [001] showing ClO₄ tetrahedra in pink and CuN₂O₄ octahedra in blue.
	Fig. 3. The connection of the components through O—H···O and C—H···O hydrogen bonds (dashed lines).

Bis[µ-(3-acetyl-2-hydroxy-6-methyl-4H-pyran-4-one-κ³O: O',O'')]diaquatetrakis(pyridine-κN)dicopper(II) diperchlorate top

Crystal data top

[Cu(C₈H₇O₄)(H₂O)(C₅H₅N)₂]₂(ClO₄)₂	Z = 1
M_r = 1012.70	F(000) = 518
Triclinic, P1	D_x = 1.611 Mg m⁻³
a = 9.9371 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3072 (4) Å	Cell parameters from 12265 reflections
c = 10.4440 (5) Å	θ = 2.6–28.3°
α = 99.624 (4)°	µ = 1.23 mm⁻¹
β = 90.540 (3)°	T = 180 K
γ = 97.895 (4)°	Fragment, dark blue
V = 1044.09 (8) Å³	0.44 × 0.34 × 0.13 mm

Data collection top

Agilent Xcalibur diffractometer	4692 independent reflections
Radiation source: fine-focus sealed tube	3889 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
Detector resolution: 8.2632 pixels mm^-1	θ_max = 28.2°, θ_min = 2.7°
ω scans	h = −13→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→13
T_min = 0.505, T_max = 1.000	l = −13→13
20280 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0426P)² + 3.6572P] where P = (F_o² + 2F_c²)/3
4692 reflections	(Δ/σ)_max < 0.001
288 parameters	Δρ_max = 1.14 e Å⁻³
0 restraints	Δρ_min = −0.65 e Å⁻³

Crystal data top

[Cu(C₈H₇O₄)(H₂O)(C₅H₅N)₂]₂(ClO₄)₂	γ = 97.895 (4)°
M_r = 1012.70	V = 1044.09 (8) Å³
Triclinic, P1	Z = 1
a = 9.9371 (4) Å	Mo Kα radiation
b = 10.3072 (4) Å	µ = 1.23 mm⁻¹
c = 10.4440 (5) Å	T = 180 K
α = 99.624 (4)°	0.44 × 0.34 × 0.13 mm
β = 90.540 (3)°

Data collection top

Agilent Xcalibur diffractometer	4692 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	3889 reflections with I > 2σ(I)
T_min = 0.505, T_max = 1.000	R_int = 0.037
20280 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 1.14 e Å⁻³
4692 reflections	Δρ_min = −0.65 e Å⁻³
288 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	0.13889 (5)	0.33620 (4)	0.22133 (5)	0.02379 (14)
Cl1	0.54880 (11)	0.73089 (10)	0.34098 (11)	0.0366 (3)
O3	0.2147 (3)	0.7115 (3)	−0.0994 (3)	0.0314 (6)
O4	0.0272 (3)	0.7603 (3)	−0.0061 (3)	0.0397 (7)
O2	0.0424 (3)	0.4919 (3)	0.2469 (3)	0.0287 (6)
O1	0.2610 (3)	0.4210 (3)	0.1090 (3)	0.0294 (6)
O1W	0.2668 (4)	0.4378 (4)	0.4076 (4)	0.0436 (8)
H1W	0.322 (6)	0.498 (6)	0.387 (6)	0.052*
H2W	0.304 (6)	0.415 (6)	0.459 (6)	0.052*
O14	0.5337 (5)	0.8399 (4)	0.4391 (4)	0.0721 (13)
N1	0.2368 (3)	0.1771 (3)	0.1824 (3)	0.0240 (6)
N2	−0.0062 (3)	0.2363 (3)	0.3136 (3)	0.0248 (7)
O13	0.5953 (5)	0.7736 (5)	0.2227 (4)	0.0706 (12)
C12	0.3329 (4)	0.5426 (4)	−0.0505 (4)	0.0270 (8)
H12	0.404	0.4928	−0.0678	0.032*
C1	0.2806 (4)	0.1181 (4)	0.2765 (4)	0.0293 (8)
H1	0.2662	0.1531	0.3625	0.035*
C16	0.1369 (4)	0.5980 (3)	0.0778 (4)	0.0223 (7)
C15	0.1196 (4)	0.6938 (4)	−0.0055 (4)	0.0267 (8)
C2	0.3464 (5)	0.0069 (4)	0.2508 (4)	0.0347 (10)
H2	0.3773	−0.0312	0.3182	0.042*
C18	−0.0449 (5)	0.6868 (4)	0.2296 (4)	0.0332 (9)
H18A	−0.1173	0.6794	0.1662	0.05*
H18B	0.0055	0.7746	0.2409	0.05*
H18C	−0.0821	0.6706	0.3109	0.05*
C5	0.2587 (4)	0.1269 (4)	0.0587 (4)	0.0302 (9)
H5	0.2309	0.1692	−0.0069	0.036*
C11	0.2416 (4)	0.5159 (3)	0.0508 (4)	0.0230 (7)
C4	0.3208 (5)	0.0149 (4)	0.0251 (4)	0.0372 (10)
H4	0.3326	−0.019	−0.0616	0.045*
C3	0.3650 (5)	−0.0458 (4)	0.1227 (4)	0.0371 (10)
H3	0.407	−0.1216	0.1024	0.044*
C10	−0.0591 (4)	0.1101 (4)	0.2648 (4)	0.0293 (8)
H10	−0.021	0.0671	0.1914	0.035*
C13	0.3180 (4)	0.6368 (4)	−0.1201 (4)	0.0277 (8)
C14	0.4058 (5)	0.6759 (5)	−0.2262 (5)	0.0427 (11)
H14A	0.4826	0.6283	−0.2323	0.064*
H14B	0.4368	0.7697	−0.2076	0.064*
H14C	0.3545	0.6549	−0.3071	0.064*
C17	0.0485 (4)	0.5860 (4)	0.1837 (4)	0.0230 (7)
C9	−0.1668 (5)	0.0422 (4)	0.3184 (4)	0.0363 (10)
H9	−0.1997	−0.0455	0.2829	0.044*
C8	−0.2253 (5)	0.1065 (5)	0.4261 (5)	0.0395 (10)
H8	−0.3	0.0637	0.4629	0.047*
C7	−0.1711 (5)	0.2350 (5)	0.4780 (4)	0.0410 (11)
H7	−0.2075	0.2797	0.5515	0.049*
O11	0.6447 (9)	0.6599 (10)	0.3795 (6)	0.179 (5)
O12	0.4201 (7)	0.6613 (8)	0.3069 (6)	0.140 (3)
C6	−0.0622 (5)	0.2967 (4)	0.4196 (4)	0.0318 (9)
H6	−0.0261	0.3835	0.455	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0241 (3)	0.0198 (2)	0.0295 (2)	0.00679 (17)	0.00515 (18)	0.00681 (17)
Cl1	0.0365 (6)	0.0255 (5)	0.0483 (6)	0.0053 (4)	0.0024 (5)	0.0072 (4)
O3	0.0299 (16)	0.0301 (14)	0.0389 (16)	0.0094 (12)	0.0052 (12)	0.0152 (12)
O4	0.0356 (17)	0.0455 (18)	0.0476 (18)	0.0221 (14)	0.0078 (14)	0.0220 (15)
O2	0.0314 (15)	0.0247 (13)	0.0324 (14)	0.0084 (11)	0.0070 (12)	0.0075 (11)
O1	0.0255 (15)	0.0268 (14)	0.0412 (16)	0.0114 (11)	0.0075 (12)	0.0143 (12)
O1W	0.050 (2)	0.0353 (18)	0.0444 (19)	0.0003 (15)	−0.0157 (16)	0.0085 (15)
O14	0.107 (4)	0.050 (2)	0.054 (2)	0.015 (2)	−0.005 (2)	−0.0095 (18)
N1	0.0224 (16)	0.0226 (15)	0.0284 (16)	0.0053 (12)	0.0029 (13)	0.0068 (12)
N2	0.0257 (17)	0.0219 (15)	0.0277 (16)	0.0055 (13)	0.0012 (13)	0.0044 (12)
O13	0.080 (3)	0.078 (3)	0.057 (2)	0.005 (2)	0.007 (2)	0.028 (2)
C12	0.0186 (19)	0.0291 (19)	0.034 (2)	0.0055 (15)	0.0027 (16)	0.0067 (16)
C1	0.033 (2)	0.030 (2)	0.0273 (19)	0.0101 (17)	0.0069 (16)	0.0080 (15)
C16	0.0181 (18)	0.0178 (16)	0.0297 (18)	−0.0008 (14)	−0.0027 (14)	0.0030 (14)
C15	0.0223 (19)	0.0242 (18)	0.034 (2)	0.0038 (15)	−0.0024 (16)	0.0063 (15)
C2	0.041 (3)	0.032 (2)	0.036 (2)	0.0147 (19)	0.0022 (19)	0.0151 (17)
C18	0.037 (2)	0.032 (2)	0.034 (2)	0.0153 (18)	0.0069 (18)	0.0038 (17)
C5	0.033 (2)	0.031 (2)	0.0293 (19)	0.0107 (17)	0.0014 (17)	0.0066 (16)
C11	0.0191 (18)	0.0190 (16)	0.0306 (19)	0.0011 (14)	−0.0028 (15)	0.0050 (14)
C4	0.044 (3)	0.035 (2)	0.032 (2)	0.016 (2)	−0.0001 (19)	−0.0030 (17)
C3	0.039 (3)	0.030 (2)	0.045 (2)	0.0190 (19)	0.002 (2)	0.0024 (18)
C10	0.029 (2)	0.0258 (19)	0.032 (2)	0.0012 (16)	0.0049 (17)	0.0031 (15)
C13	0.0200 (19)	0.0275 (19)	0.035 (2)	0.0015 (15)	−0.0001 (16)	0.0067 (16)
C14	0.038 (3)	0.045 (3)	0.052 (3)	0.011 (2)	0.015 (2)	0.022 (2)
C17	0.0201 (18)	0.0207 (17)	0.0277 (18)	0.0035 (14)	−0.0028 (14)	0.0020 (14)
C9	0.037 (2)	0.032 (2)	0.038 (2)	−0.0039 (18)	0.0037 (19)	0.0062 (18)
C8	0.032 (2)	0.048 (3)	0.041 (2)	0.000 (2)	0.0091 (19)	0.016 (2)
C7	0.045 (3)	0.045 (3)	0.036 (2)	0.012 (2)	0.019 (2)	0.0074 (19)
O11	0.250 (9)	0.288 (10)	0.075 (4)	0.234 (9)	0.050 (5)	0.081 (5)
O12	0.113 (5)	0.165 (6)	0.098 (4)	−0.085 (5)	0.023 (4)	−0.027 (4)
C6	0.037 (2)	0.029 (2)	0.028 (2)	0.0066 (17)	0.0056 (17)	0.0011 (16)

Geometric parameters (Å, º) top

Cu1—O1	1.922 (3)	C16—C11	1.431 (5)
Cu1—O2	1.962 (3)	C16—C15	1.447 (5)
Cu1—N2	2.005 (3)	C2—C3	1.382 (6)
Cu1—N1	2.006 (3)	C2—H2	0.93
Cu1—O1W	2.325 (3)	C18—C17	1.509 (5)
Cu1—O4ⁱ	2.737 (3)	C18—H18A	0.96
Cl1—O11	1.374 (5)	C18—H18B	0.96
Cl1—O12	1.390 (6)	C18—H18C	0.96
Cl1—O14	1.414 (4)	C5—C4	1.379 (5)
Cl1—O13	1.439 (4)	C5—H5	0.93
O3—C13	1.363 (5)	C4—C3	1.380 (6)
O3—C15	1.386 (5)	C4—H4	0.93
O4—C15	1.219 (5)	C3—H3	0.93
O2—C17	1.256 (4)	C10—C9	1.373 (6)
O1—C11	1.269 (4)	C10—H10	0.93
O1W—H1W	0.82 (6)	C13—C14	1.491 (6)
O1W—H2W	0.74 (6)	C14—H14A	0.96
N1—C1	1.337 (5)	C14—H14B	0.96
N1—C5	1.340 (5)	C14—H14C	0.96
N2—C6	1.341 (5)	C9—C8	1.383 (6)
N2—C10	1.346 (5)	C9—H9	0.93
C12—C13	1.329 (5)	C8—C7	1.377 (7)
C12—C11	1.437 (5)	C8—H8	0.93
C12—H12	0.93	C7—C6	1.378 (6)
C1—C2	1.385 (5)	C7—H7	0.93
C1—H1	0.93	C6—H6	0.93
C16—C17	1.430 (5)

O1—Cu1—O2	89.43 (12)	C1—C2—H2	120.8
O1—Cu1—N2	171.16 (14)	C17—C18—H18A	109.5
O2—Cu1—N2	90.52 (13)	C17—C18—H18B	109.5
O1—Cu1—N1	88.01 (13)	H18A—C18—H18B	109.5
O2—Cu1—N1	176.25 (14)	C17—C18—H18C	109.5
N2—Cu1—N1	91.58 (14)	H18A—C18—H18C	109.5
O1—Cu1—O1W	92.98 (14)	H18B—C18—H18C	109.5
O2—Cu1—O1W	86.49 (13)	N1—C5—C4	122.4 (4)
N2—Cu1—O1W	95.84 (14)	N1—C5—H5	118.8
N1—Cu1—O1W	96.38 (14)	C4—C5—H5	118.8
O1—Cu1—O4ⁱ	87.05 (12)	O1—C11—C16	125.5 (4)
O2—Cu1—O4ⁱ	87.41 (12)	O1—C11—C12	117.0 (3)
N2—Cu1—O4ⁱ	84.12 (13)	C16—C11—C12	117.6 (3)
N1—Cu1—O4ⁱ	89.71 (12)	C5—C4—C3	118.7 (4)
O1W—Cu1—O4ⁱ	173.90 (11)	C5—C4—H4	120.6
O11—Cl1—O12	116.7 (6)	C3—C4—H4	120.6
O11—Cl1—O14	110.3 (4)	C4—C3—C2	119.4 (4)
O12—Cl1—O14	107.6 (4)	C4—C3—H3	120.3
O11—Cl1—O13	106.5 (4)	C2—C3—H3	120.3
O12—Cl1—O13	103.9 (4)	N2—C10—C9	122.9 (4)
O14—Cl1—O13	111.7 (3)	N2—C10—H10	118.5
C13—O3—C15	122.2 (3)	C9—C10—H10	118.5
C17—O2—Cu1	129.4 (2)	C12—C13—O3	121.5 (4)
C11—O1—Cu1	127.4 (2)	C12—C13—C14	127.0 (4)
Cu1—O1W—H1W	107 (4)	O3—C13—C14	111.5 (3)
Cu1—O1W—H2W	135 (5)	C13—C14—H14A	109.5
H1W—O1W—H2W	103 (6)	C13—C14—H14B	109.5
C1—N1—C5	118.5 (3)	H14A—C14—H14B	109.5
C1—N1—Cu1	122.0 (3)	C13—C14—H14C	109.5
C5—N1—Cu1	119.5 (3)	H14A—C14—H14C	109.5
C6—N2—C10	117.7 (4)	H14B—C14—H14C	109.5
C6—N2—Cu1	120.9 (3)	O2—C17—C16	123.2 (3)
C10—N2—Cu1	121.1 (3)	O2—C17—C18	114.3 (3)
C13—C12—C11	121.4 (4)	C16—C17—C18	122.4 (3)
C13—C12—H12	119.3	C10—C9—C8	118.8 (4)
C11—C12—H12	119.3	C10—C9—H9	120.6
N1—C1—C2	122.5 (4)	C8—C9—H9	120.6
N1—C1—H1	118.7	C7—C8—C9	118.8 (4)
C2—C1—H1	118.7	C7—C8—H8	120.6
C17—C16—C11	121.5 (3)	C9—C8—H8	120.6
C17—C16—C15	119.6 (3)	C8—C7—C6	119.2 (4)
C11—C16—C15	118.9 (3)	C8—C7—H7	120.4
O4—C15—O3	114.4 (3)	C6—C7—H7	120.4
O4—C15—C16	127.6 (4)	N2—C6—C7	122.5 (4)
O3—C15—C16	118.0 (3)	N2—C6—H6	118.7
C3—C2—C1	118.4 (4)	C7—C6—H6	118.7
C3—C2—H2	120.8

O1—Cu1—O2—C17	14.4 (3)	Cu1—O1—C11—C16	13.9 (6)
N2—Cu1—O2—C17	−156.7 (3)	Cu1—O1—C11—C12	−166.1 (3)
O1W—Cu1—O2—C17	107.5 (3)	C17—C16—C11—O1	5.2 (6)
O2—Cu1—O1—C11	−19.7 (3)	C15—C16—C11—O1	−174.0 (4)
N1—Cu1—O1—C11	157.4 (3)	C17—C16—C11—C12	−174.8 (3)
O1W—Cu1—O1—C11	−106.1 (3)	C15—C16—C11—C12	6.0 (5)
O1—Cu1—N1—C1	130.8 (3)	C13—C12—C11—O1	177.6 (4)
N2—Cu1—N1—C1	−58.0 (3)	C13—C12—C11—C16	−2.4 (6)
O1W—Cu1—N1—C1	38.0 (3)	N1—C5—C4—C3	−1.6 (7)
O1—Cu1—N1—C5	−49.7 (3)	C5—C4—C3—C2	−0.1 (7)
N2—Cu1—N1—C5	121.5 (3)	C1—C2—C3—C4	1.5 (7)
O1W—Cu1—N1—C5	−142.6 (3)	C6—N2—C10—C9	0.2 (6)
O2—Cu1—N2—C6	−39.9 (3)	Cu1—N2—C10—C9	−174.0 (3)
N1—Cu1—N2—C6	143.3 (3)	C11—C12—C13—O3	−0.7 (6)
O1W—Cu1—N2—C6	46.5 (3)	C11—C12—C13—C14	179.1 (4)
O2—Cu1—N2—C10	134.0 (3)	C15—O3—C13—C12	−0.1 (6)
N1—Cu1—N2—C10	−42.8 (3)	C15—O3—C13—C14	−179.9 (4)
O1W—Cu1—N2—C10	−139.6 (3)	Cu1—O2—C17—C16	−2.4 (5)
C5—N1—C1—C2	−0.5 (6)	Cu1—O2—C17—C18	178.1 (3)
Cu1—N1—C1—C2	179.0 (3)	C11—C16—C17—O2	−11.1 (6)
C13—O3—C15—O4	−174.1 (4)	C15—C16—C17—O2	168.1 (4)
C13—O3—C15—C16	3.8 (5)	C11—C16—C17—C18	168.4 (4)
C17—C16—C15—O4	−8.3 (6)	C15—C16—C17—C18	−12.4 (5)
C11—C16—C15—O4	170.9 (4)	N2—C10—C9—C8	1.1 (7)
C17—C16—C15—O3	174.0 (3)	C10—C9—C8—C7	−1.9 (7)
C11—C16—C15—O3	−6.7 (5)	C9—C8—C7—C6	1.4 (7)
N1—C1—C2—C3	−1.2 (7)	C10—N2—C6—C7	−0.7 (6)
C1—N1—C5—C4	2.0 (6)	Cu1—N2—C6—C7	173.5 (3)
Cu1—N1—C5—C4	−177.5 (3)	C8—C7—C6—N2	−0.1 (7)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O12	0.83 (6)	2.13 (6)	2.934 (9)	165 (6)
O1W—H2W···O11ⁱⁱ	0.74 (6)	2.06 (6)	2.772 (9)	164 (6)
C9—H9···O13ⁱⁱⁱ	0.93	2.56	3.389 (7)	148

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

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₇O₄)(H₂O)(C₅H₅N)₂]₂(ClO₄)₂
M_r	1012.70
Crystal system, space group	Triclinic, P1
Temperature (K)	180
a, b, c (Å)	9.9371 (4), 10.3072 (4), 10.4440 (5)
α, β, γ (°)	99.624 (4), 90.540 (3), 97.895 (4)
V (Å³)	1044.09 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.23
Crystal size (mm)	0.44 × 0.34 × 0.13

Data collection
Diffractometer	Agilent Xcalibur diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.505, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	20280, 4692, 3889
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.140, 1.12
No. of reflections	4692
No. of parameters	288
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.14, −0.65

Computer programs: CrysAlis PRO (Agilent, 2011), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cu1—O1	1.922 (3)	Cu1—N1	2.006 (3)
Cu1—O2	1.962 (3)	Cu1—O1W	2.325 (3)
Cu1—N2	2.005 (3)	Cu1—O4ⁱ	2.737 (3)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O12	0.83 (6)	2.13 (6)	2.934 (9)	165 (6)
O1W—H2W···O11ⁱⁱ	0.74 (6)	2.06 (6)	2.772 (9)	164 (6)
C9—H9···O13ⁱⁱⁱ	0.9300	2.5600	3.389 (7)	148.00

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

Acknowledgements

The authors thank the Algerian Ministère de l'Enseignement Supérieur et de la Recherche Scientifique for financial support.

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