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

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.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.054
• wR factor = 0.140
• Data-to-parameter ratio = 16.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT341_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0061 Ang
PLAT702_ALERT_1_C Angle   Calc   96.57(13), Rep   96.38(14), Dev..       1.46 Sigma
              N1   -CU1  -O1W     1.555   1.555   1.555      #         10
PLAT702_ALERT_1_C Angle   Calc  173.75(12), Rep  173.90(11), Dev..       1.25 Sigma
              O1W  -CU1  -O4      1.555   1.555   2.565      #         15
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.226
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          4
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         12

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Cu1     (II)          2.17
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600        441

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   6 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

The H atoms were localized on Fourier maps but introduced in calculated positions and treated as riding on their parent C atom with C—H = 0.96 Å (methyl) or 0.93 Å (aromatic) and with U_iso(H) = 1.2U_eq(C) or U_iso(H) = 1.5U_eq(methyl). H1W and H2W protons of the water molecule were located in a difference Fourier map and were refined isotropically with U_iso(H) = 1.5Ueq(O).

Computing details

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

	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

Crystal data

[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) Å^3	0.44 × 0.34 × 0.13 mm

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ^2(Fo^2) + (0.0426P)^2 + 3.6572P] where P = (Fo^2 + 2Fc^2)/3
4692 reflections	(Δ/σ)max < 0.001
288 parameters	Δρmax = 1.14 e Å^−3
0 restraints	Δρmin = −0.65 e Å^−3

Special details

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 (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—O4^i	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—O4^i	87.05 (12)	O1—C11—C16	125.5 (4)
O2—Cu1—O4^i	87.41 (12)	O1—C11—C12	117.0 (3)
N2—Cu1—O4^i	84.12 (13)	C16—C11—C12	117.6 (3)
N1—Cu1—O4^i	89.71 (12)	C5—C4—C3	118.7 (4)
O1W—Cu1—O4^i	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)

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···O11^ii	0.74 (6)	2.06 (6)	2.772 (9)	164 (6)
C9—H9···O13^iii	0.93	2.56	3.389 (7)	148

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