Bis[μ-(3-acetyl-2-hy-droxy-6-methyl-4H-pyran-4-one-κ(3)O:O',O'')]diaqua-tetra-kis-(pyridine-κN)dicopper(II) diperchlorate.

In the centrosymmetric binuclear cation of the title compound, [Cu(C(8)H(7)O(4))(H(2)O)(C(5)H(5)N)(2)](2)(ClO(4))(2), the Cu(II) atoms are bridged by a pair of two dehydro-acetate anions in a bis-/monodentate mode. The distorted octa-hedral N(2)O(4) coordination sphere of the metal cation is completed by two pyridine N atoms and one O atom of a water mol-ecule. The complex cations and the perchlorate counter anions are arranged in layers parallel to (100). O-H⋯O hydrogen bonds between the coordinating water mol-ecules 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 = 1012.70

Triclinic,

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[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.140

S = 1.12

4692 reflections

288 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.14 e Å−3

Δρmin = −0.65 e Å−3

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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812041608/wm2685sup1.cif

Click here for additional data file.

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

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

[Cu(C8H7O4)(H2O)(C5H5N)2]2(ClO4)2	Z = 1
Mr = 1012.70	F(000) = 518
Triclinic, P1	Dx = 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

Agilent Xcalibur diffractometer	4692 independent reflections
Radiation source: fine-focus sealed tube	3889 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 8.2632 pixels mm-1	θmax = 28.2°, θmin = 2.7°
ω scans	h = −13→11
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −13→13
Tmin = 0.505, Tmax = 1.000	l = −13→13
20280 measured reflections

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(Fo2) + (0.0426P)2 + 3.6572P] where P = (Fo2 + 2Fc2)/3
4692 reflections	(Δ/σ)max < 0.001
288 parameters	Δρmax = 1.14 e Å−3
0 restraints	Δρmin = −0.65 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	0.13889 (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*

	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)

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)

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

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) .

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) ; (iii) .