Two centrosymmetric dinuclear phenanthroline-copper(II) complexes with 3,5-dichloro-2-hy­droxy­benzoic acid and 5-chloro-2-hy­droxy­benzoic acid

The title compounds, bis­([mu]-3,5-dichloro-2-oxidobenzoato)-[kappa]³O¹,O²:O²;[kappa]³O²:O¹,O²-bis­[(3,5-dichloro-2-hy­droxy­benzoic acid-[kappa]O¹)(1,10-phenanthroline-[kappa]²N,N')copper(II)], [Cu₂(C₇H₂Cl₂O₃)₂(C₇H₄Cl₂O₃)₂(C₁₂H₈N₂)₂], (I), and bis­([mu]-5-chloro-2-oxidobenzoato)-[kappa]³O¹,O²:O¹;[kappa]³O¹:O¹,O²-bis­[(5-chloro-2-hy­droxy­benzoic acid-[kappa]O¹)(1,10-phenanthroline-[kappa]²N,N')copper(II)] ethanol monosolvate, [Cu₂(C₇H₃ClO₃)₂(C₇H₅ClO₃)₂(C₁₂H₈N₂)₂]·C₂H₆O, (II), contain centrosymmetric dinuclear complex mol­ecules in which Cu²⁺ cations are surrounded by a chelating 1,10-phenanthroline ligand, a chelating 3,5-dichloro-2-oxidoben­zoate or 5-chloro-2-oxidobenzoate an­ionic ligand and a monodentate 3,5-dichloro-2-hydroxybenzoic acid or 5-chloro-2-hy­droxybenzoic acid ligand. The chelating benzoate ligand also bridges to the other Cu²⁺ ion in the molecule, but the O atom involved in the bridge is different in the two complexes, being the phenolate O atom in (I) and a carboxylate O atom in (II). The bridge completes a 4+1+1 axially elongated tetragonal-bipy­ram­idal arrangement about each Cu²⁺ cation. The complex mol­ecules of both compounds are linked into one-dimensional supra­molecular chains through O-H...O hydrogen bonds.

S1. Comment

Many copper complexes with a variety of organic chelating ligands have been shown to possess biological activities including anti-inflammatory and anti-convulsant properties (Lemoine et al., 2002), cytotoxicity and antiviral activity (Ranford et al., 1993). Several copper(II) complexes acting as proteasome inhibitors capable of inducing programmed cell death (apoptosis) have been prepared and characterized. In these complexes the metal ion is coordinated to heteroatomic neutral ligands such as the 1,10-phenantroline ligand (Marzano et al.). It has been reported that the copper complex with 1,10-phenanthroline is able to induce the formation of free radicals which in turn degradate DNA under in vitro conditions. The mechanism of action of this complex is derived from the potential intercalation of planar phenanthroline into DNA and the in situ generation of free radicals, predominantly hydroxy radicals mediated by the presence of copper (Sigman, 1986; Sigman et al., 1993). In these aspects, copper complexes with the chelating 1,10-phenanthroline ligand can be used as anticancer agents (Tardito & Marchio, 2009; Tisato et al., 2010).

Salicylic acid (2-hydroxybenzoic acid; salH₂) and its substituted derivatives can be coordinated as neutral molecular ligands or as anionic ligands with deprotonic carboxyl (salH^-) or deprotonic carboxyl and hydroxy groups (sal^2-), which can be coordinated as chelating and/or bridging ligands. In view of these results, in this preliminary contribution, we directed our attention to the preparation and structural characterization of potentially bioactive copper(II) 1,10-phenantroline complexes with anions of two derivatives of salicylic acid.

The structure of bis(µ-3,5-dichloro-2-oxidobenzoato)bis[(3,5-dichloro-2-hydroxybenzoic acid)(1,10-phenanthroline)copper(II)], (I) (Fig. 1), exhibits a centrosymmetric dinuclear molecular structure. Two Cu atoms are organized in a dimeric unit via bridging O atoms of the phenolic groups of 3,5-dichloro-2-oxidobenzoate anions [O3 and O3ⁱ; symmetry code: (i) -x+1, -y+1, -z+1]. Each Cu atom in the dimeric unit is hexacoordinated in the tetragonal bipyramid by O atoms of a phenolic group of bridging 3,5-dichloro-2-oxidobenzoate anions [Cu1—O1 = 1.906 (2) Å], an O atom of a carboxylic group from 3,5-dichloro-2-oxidobenzoate anions [Cu1—O3 = 1.882 (2) Å], two N atoms of 1,10-phenanthroline ligands [Cu1—N1 = 2.011 (3) Å and Cu1—N2 = 1.989 (3) Å] in the equatorial plane, two O atoms of the phenolic group of second bridging 3,5-dichloro-2-oxidobenzoate anions [Cu1—O3ⁱ = 2.715 (3) Å] and the carboxyl group of coordinated molecules of 3,5-dichloro-2-hydroxybenzoic acid [Cu1—O4 = 2.585 (3) Å] in apical positions. This complex represents the first example of a dimeric complex with bridging as well as chelating O atom of the phenolate group of sal^2- anions. Interestingly, a three-atom carboxylate bridging ligand (Cu—O—C—O—Cu) in a dimeric copper(II) sal^2- complex was recently reported by Weng et al. (2007).

The crystal structure of complex bis(µ-5-chloro-2-oxidobenzoato)bis[(5-chloro-2-hydroxybenzoic acid)(1,10-phenanthroline)copper(II)] ethanol monosolvate, (II) (Fig. 2), consists of centrosymmetric dimeric complex molecules and disordered ethanol solvent molecules (see Experimental). The Cu atom in the dimeric complex molecule is coordinated by two phenanthroline N atoms [Cu1—N1 = 2.001 (2) Å and Cu1—N2 = 2.005 (2) Å], two O atoms from 5-chloro-2-oxidobenzoate anions (phenolate and carboxylate groups) [Cu1—O1 = 1.904 (1) Å and Cu1—O3 = 1.880 (1) Å] in square-planar coordination and two apical positions are occupied by carboxyl O atoms from a coordinated molecule of 5-chloro-2-hydroxybenzoic acid [Cu1—O4 = 2.582 (2) Å] and from the bridging carboxylate group of a second 5-chloro-2-oxidobenzoate anion [Cu1—O1ⁱ = 2.984 (2) Å]. This Cu1—O1ⁱ bond length of 2.984 (2) Å in (II) is somewhat longer, although it is in the range found for copper(II) complexes with tetragonal–bipyramidal coordination around the Cu²⁺ ion (Melnik, Kabesova, Koman et al., 1998; Melnik, Kabesova, Macaskova et al., 1998) possesing Jahn–Teller distortions (Gazo et al., 1976).

The molecular structures of (I) and (II) revealed the existence of two alternative bridging coordinations of sal^2- anions through bridging phenolic or carboxylic O atoms. Similarity in the binding mode of bridging sal^2- ligands could be attributed to almost identical energy of both structural configurations. More insight into this phenomenon can be obtained from theoretical calculations. The Cu1···Cu1ⁱ distances of 3.3457 (8) Å for (I) with bridging carboxylate O atoms are close to the range of 3.15–3.31 Å found in dimeric copper(II) sal^2- complexes with bridging phenolic O atoms (Lemoine et al., 1999, 2000, 2002; Fan et al., 2005; Hu et al. 2007; Nie et al., 2010; Palanisami et al., 2006; Geraghty et al., 1999; Wang & Okabe, 2004). On the other hand, dimeric complex (II) has a longer Cu1···Cu1ⁱ distance of 3.5709 (5) Å. We note that the Cu···Cu distance in the dimeric complex with a three-atom bridging sal^2- ligand has been reported to be 4.93 Å (Wen et al., 2007). Both (I) and (II) are coordinated by six donor atoms and they represent the first two examples of copper(II) sal^2- complexes with coordinated salicylic acid as a ligand, but all other known dimeric copper(II) sal^2- complexes are coordinated by five atoms (two pyridine N atoms of 1,10-phenanthroline or 2,2'-bipyridine and three O atoms of phenolate and carboxylate groups of sal^2- bridging anionic ligands or its derivatives). The Cu atoms in monomeric copper(II) sal^2- complexes have a tetragonal–planar coordination environment formed by two pyridine N atoms and two O atoms of sal^2- anions (Zhang et al., 2007a,b) in a tetragonal–pyramidal coordination environment forming the same atoms in a square plane and O or N atoms in axial positions from another ligand as water (Gao et al., 2009; Zhang et al., 2008; Yu et al., 2009) or pyridine (Wen et al., 2007), respectively. In the known complexes, the distances between the Cu atom and O atom from axial coordinated bridging sal^2- ligands in dimeric complexes are in the range of 2.28–2.65 Å, but Cu–L_ax bond distance in monomeric complexes are in a narrower range (2.26–2.35 Å).

The aromatic rings of benzoate, benzoic acid and 1,10-phenanthroline ligands of both complexes are stacked (Figs. 1 and 2). π–π stacking interactions (Janiak, 2000) are observed between the benzene ring of the sal^2- anion and the benzene ring of salicylic acid ligand. The distances between two benzene rings are in the range 3.34–3.68 Å for (I) and 3.27–3.84 Å for (II). The second π–π stacking interactions (Janiak, 2000) are between the benzene ring of the sal^2- anion and adjacent aromatic rings of 1,10-phenanthroline ligands at (-x+1, -y+1, -z+1), with the separation between the planes of the aromatic rings in the range 3.16–3.99 Å for (I) and 3.24–3.70 Å for (II).

The centroid–centroid distances in (I) are 3.732 (2) Å between the benzene ring (C14–C19) of the 3,5-dichloro-2-oxidobenzoate anion and the benzene ring (C21–C26) of the 3,5-dichloro-2-hydroxybenzoic acid molecule, and 3.837 (2) Å between the C14–C19 benzene ring and the benzene ring (C4–C7/C11/C12) of the 1,10-phenanthroline ligand in the molecule at (-x+1, -y+1, -z+1). The centroid–centroid in (II) are 3.8030 (13) Å between the benzene ring (C14–C19) of the 5-chloro-2-oxidobenzoate anion and the benzene ring (C21–C26) of the 5-chloro-2-hydroxybenzoic acid molecule, and 3.5754 (13) Å between the C14–C19 benzene ring and the N2/C6–C10 pyridine ring N2/C6–C10 of the 1,10-phenanthroline ligand in the molecule at (-x+1, -y+1, -z+1).

The crystal packings of (I) and (II) are shown in Figs. 3 and 4, respectively. The complex molecules of both compounds are connected through O5—H5O···O2ⁱⁱ hydrogen bonds [symmetry code: (ii) -x+2, -y+1, -z+1] between the carboxyl H atom of a coordinated 3,5-dichloro-2-hydroxybenzoic acid molecule or a 5-chloro-2-hydroxybenzoic acid molecule and the uncoordinated O atom of the carboxylate group of 3,5-dichloro-2-oxidobenzoate or 5-chloro-2-oxidobenzoate anion, into one-dimensional supramolecular band chains. The O5···O2ⁱⁱ distances are 2.489 (3) and 2.472 (2) Å, respectively, and the O5—H5O—O2ⁱⁱ angles for both complexes have a value of 165°. The disordered uncoordinated ethanol solvent molecules of (II) are connected through an O1S–H1S···O6 hydrogen bond to the hydroxy O atom of a coordinated 5-chloro-2-hydroxybenzoic acid molecule. The O1S···O6 distance is 2.811 (7) Å and the O1S–H1S–O6 angle is 159°. The crystal structure of (II) is observed also to have short Cl2···Cl2ⁱⁱⁱ contacts (Desiraju, 1995) [symmetry code: (iii) -x+3, -y+1, -z] with an interatomic distance of 3.257 (2) Å.

In this contribution, we report the crystal structures of two copper(II)–1,10-phenantroline complexes with derivatives of salicylic acid. The structural study revealed dimeric complexes with hexacoordination around the Cu atom. Further work on the biological activity of the prepared complexes is in progress.

Related literature

For related literature, see: Desiraju (1995); Fan & Zhu (2005); Gao et al. (2009); Gazo et al. (1976); Geraghty et al. (1999); Hu et al. (2007); Janiak (2000); Lemoine et al. (1999, 2000, 2002); Melnik, Kabesova, Koman et al. (1998); Melnik, Kabesova, Macaskova et al. (1998); Nie et al. (2010); Palanisami et al. (2006); Ranford et al. (1993); Sheldrick (2008); Sigman (1986); Sigman et al. (1993); Tardito & Marchio (2009); Tisato et al. (2010); Wang & Okabe (2004); Wen et al. (2007); Weng et al. (2007); Yu et al. (2009); Zhang et al. (2007a, 2007b, 2008).

S2. Experimental

The title copper complexes were prepared in a similar manner to methods described previously by Ranford et al. (1993). To the royal-blue solution formed from copper(II) acetate hydrate (0.200 g, 1 mmol) and 1,10-phenanthroline (0.182 g, 1.00 mmol) in ethanol (40 ml) was added 3,5-dichloro-2-hydroxybenzoic acid (0.207 g, 1 mmol) for (I) or 5-chloro-2-hydroxybenzoic acid (0.173 g, 1 mmol) for (II). The resulting mixture was stirred for 4 d and the resulting green products were filtered off and washed with ethanol. The green filtrates were left to stand at room temperature for about 2 weeks giving crystals suitable for X-ray analysis. The compositions of the main product and the corresponding crystals obtained from the green filtrates were checked with IR measurements and were found to be identical.

S3. Refinement

The 3,5-dichloro-2-hydroxybenzoic acid ligand of (I) has orientational disorder of the hydroxy group (O6/O7) and the site-occupation factors of the disordered parts are 0.807 (8) and 0.193 (8), respectively. The C—O distances involving these disordered hydroxy groups were restrained to 1.350 (1) Å, while the displacement parameters of the atoms at each end of these bonds were restrained to be similar (SIMU and DELU instructions in SHELXL97; Sheldrick, 2008).

The ethanol solvent molecule of (II) lies is disordered around an inversion centre. Distance restraints of 1.43 (1), 1.54 (1) and 2.38 (2) Å were applied to the O1S—C1S, C1S—C2S and O1S···C2S distances respectively, while the displacement parameters of the solvent atoms were restrained to be similar (SIMU and DELU commands in SHELXL97).

The aromatic and methylene H atoms were positioned with C—H = 0.93 and 0.97 Å, respectively, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C). The methyl H atoms were positioned with C—H = 0.98 Å and constrained to ride on their parent atoms, with U_iso(H) = 1.5U_eq(C). The hydroxy/carboxylic acid H atoms were positioned with O—H = 0.82 Å and constrained to ride on their parent atoms, with U_iso(H) = 1.5U_eq(C) using the AFIX 147 command for the nondisordered O–H group and AFIX 83 for the disordered O–H groups.

Computing details

For both compounds, data collection: CrysAlis CCD (Agilent, 2011); cell refinement: CrysAlis RED (Agilent, 2011); data reduction: CrysAlis RED (Agilent, 2011). Program(s) used to solve structure: SIR97 (Altomare et al., 1999) for (I); SHELXS97 (Sheldrick, 2008) for (II). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. A perspective view of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A perspective view of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 3. The crystal structure of (I). H atoms of the aromatic rings have been omitted for clarity.
	Fig. 4. The crystal structure of (II). H atoms of the aromatic rings and ethyl groups have been omitted for clarity.

(I) bis(µ-3,5-dichloro-2-oxidobenzoato)- κ³O¹,O²:O²; κ³O²:O¹,O²- bis[(3,5-dichloro-2-hydroxybenzoic acid-κO¹)(1,10- phenanthroline-κ²N,N')copper(II)]

Crystal data

[Cu2(C7H2Cl2O3)2(C12H8N2)2(C7H4Cl2O3)2]	Z = 1
Mr = 1311.48	F(000) = 658
Triclinic, P1	Dx = 1.722 Mg m^−3
Hall symbol: -P1	Mo Kα radiation, λ = 0.71069 Å
a = 9.2295 (2) Å	Cell parameters from 4563 reflections
b = 11.6047 (3) Å	θ = 4.2–26.4°
c = 12.9863 (3) Å	µ = 1.33 mm^−1
α = 102.423 (2)°	T = 293 K
β = 99.045 (2)°	Prism, green
γ = 106.753 (2)°	0.43 × 0.14 × 0.05 mm
V = 1264.44 (5) Å^3

Data collection

Gemini R CCD diffractometer	5150 independent reflections
Radiation source: fine-focus sealed tube	3886 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: 10.4340 pixels mm^-1	θmax = 26.4°, θmin = 4.2°
ω scans	h = −11→11
Absorption correction: analytical CrysAlis RED (Agilent, 2011)	k = −14→14
Tmin = 0.598, Tmax = 0.936	l = −16→16
31426 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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0989P)^2 + 0.1443P] where P = (Fo^2 + 2Fc^2)/3
5150 reflections	(Δ/σ)max < 0.001
363 parameters	Δρmax = 0.62 e Å^−3
16 restraints	Δρmin = −0.85 e Å^−3

Special details

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 > 2σ(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	Occ. (<1)
Cu	0.60314 (4)	0.40947 (3)	0.53005 (3)	0.04638 (18)
Cl1	0.55093 (13)	0.67789 (11)	0.83481 (9)	0.0711 (3)
Cl2	1.09054 (14)	1.02441 (9)	0.84931 (9)	0.0798 (4)
Cl3	0.7025 (3)	0.5575 (3)	1.06156 (15)	0.1492 (8)
Cl4	1.2585 (3)	0.84339 (15)	1.03319 (13)	0.1382 (7)
O1	0.7740 (3)	0.5084 (2)	0.48679 (19)	0.0471 (6)
O2	0.9763 (3)	0.6699 (2)	0.49652 (18)	0.0485 (6)
O3	0.5898 (3)	0.5492 (2)	0.6279 (2)	0.0520 (6)
O4	0.7913 (3)	0.3679 (2)	0.6760 (2)	0.0608 (7)
O5	1.0353 (3)	0.4738 (3)	0.6795 (2)	0.0618 (7)
H5O	1.0166	0.4199	0.6221	0.093*
O6	0.6882 (4)	0.4162 (4)	0.8478 (3)	0.0838 (15)	0.807 (8)
H6O	0.6877	0.3774	0.7869	0.126*	0.807 (8)
O7	1.1941 (11)	0.6603 (16)	0.8283 (10)	0.083 (6)	0.193 (8)
H7O	1.1726	0.6072	0.7701	0.124*	0.193 (8)
N1	0.4294 (3)	0.2920 (3)	0.5714 (3)	0.0517 (7)
N2	0.5849 (3)	0.2533 (3)	0.4211 (2)	0.0479 (7)
C1	0.3560 (4)	0.3145 (4)	0.6483 (4)	0.0630 (10)
H1	0.3840	0.3961	0.6920	0.076*
C2	0.2381 (5)	0.2212 (5)	0.6669 (4)	0.0798 (14)
H2	0.1900	0.2400	0.7231	0.096*
C3	0.1940 (5)	0.1026 (5)	0.6024 (4)	0.0767 (13)
H3	0.1138	0.0402	0.6137	0.092*
C4	0.2676 (5)	0.0727 (4)	0.5191 (4)	0.0669 (12)
C5	0.3864 (4)	0.1725 (3)	0.5076 (3)	0.0530 (9)
C6	0.4694 (4)	0.1516 (3)	0.4254 (3)	0.0514 (9)
C7	0.4320 (5)	0.0316 (3)	0.3559 (3)	0.0608 (11)
C8	0.5189 (6)	0.0213 (4)	0.2780 (4)	0.0742 (13)
H8	0.4984	−0.0562	0.2294	0.089*
C9	0.6329 (5)	0.1221 (4)	0.2717 (4)	0.0700 (12)
H9	0.6892	0.1139	0.2188	0.084*
C10	0.6646 (4)	0.2382 (4)	0.3454 (3)	0.0570 (9)
H10	0.7438	0.3068	0.3415	0.068*
C11	0.3119 (6)	−0.0679 (4)	0.3705 (5)	0.0786 (15)
H11	0.2866	−0.1481	0.3250	0.094*
C12	0.2354 (6)	−0.0496 (4)	0.4467 (5)	0.0814 (15)
H12	0.1585	−0.1176	0.4540	0.098*
C13	0.8641 (4)	0.6201 (3)	0.5341 (3)	0.0400 (7)
C14	0.8395 (3)	0.6933 (3)	0.6341 (2)	0.0375 (7)
C15	0.7078 (4)	0.6523 (3)	0.6762 (3)	0.0407 (7)
C16	0.7041 (4)	0.7285 (3)	0.7748 (3)	0.0450 (8)
C17	0.8200 (5)	0.8419 (3)	0.8281 (3)	0.0539 (9)
H17	0.8139	0.8906	0.8933	0.065*
C18	0.9439 (4)	0.8812 (3)	0.7831 (3)	0.0508 (9)
C19	0.9560 (4)	0.8096 (3)	0.6887 (3)	0.0452 (8)
H19	1.0417	0.8377	0.6602	0.054*
C20	0.9188 (4)	0.4519 (3)	0.7214 (3)	0.0480 (8)
C21	0.9406 (4)	0.5354 (3)	0.8310 (3)	0.0500 (8)
C22	0.8234 (4)	0.5122 (3)	0.8889 (3)	0.0626 (10)
H22	0.7311	0.4455	0.8581	0.075*	0.20
C23	0.8449 (7)	0.5886 (6)	0.9909 (4)	0.0778 (13)
C24	0.9727 (8)	0.6856 (5)	1.0346 (4)	0.0873 (16)
H24	0.9849	0.7363	1.1036	0.105*
C25	1.0910 (7)	0.7138 (4)	0.9786 (4)	0.0811 (14)
C26	1.0740 (5)	0.6359 (4)	0.8768 (3)	0.0589 (10)
H26	1.1529	0.6521	0.8399	0.071*	0.80

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.0434 (3)	0.0300 (2)	0.0577 (3)	0.00602 (17)	0.01151 (19)	0.00436 (18)
Cl1	0.0770 (7)	0.0819 (7)	0.0699 (7)	0.0359 (6)	0.0371 (5)	0.0253 (6)
Cl2	0.0952 (8)	0.0466 (6)	0.0645 (7)	−0.0014 (5)	0.0161 (6)	−0.0157 (5)
Cl3	0.1891 (19)	0.223 (2)	0.1045 (13)	0.1281 (19)	0.0858 (13)	0.0678 (14)
Cl4	0.1851 (17)	0.0797 (10)	0.0812 (10)	0.0053 (10)	−0.0326 (10)	−0.0177 (8)
O1	0.0504 (13)	0.0313 (11)	0.0485 (13)	0.0052 (10)	0.0129 (10)	−0.0013 (10)
O2	0.0550 (13)	0.0360 (12)	0.0440 (13)	0.0034 (10)	0.0169 (11)	0.0017 (10)
O3	0.0448 (13)	0.0384 (13)	0.0658 (16)	0.0091 (10)	0.0179 (11)	0.0034 (11)
O4	0.0617 (15)	0.0469 (15)	0.0605 (16)	0.0071 (13)	0.0116 (13)	0.0047 (12)
O5	0.0580 (15)	0.0620 (17)	0.0465 (15)	0.0075 (13)	0.0139 (12)	−0.0072 (12)
O6	0.079 (3)	0.102 (3)	0.080 (3)	0.033 (2)	0.032 (2)	0.032 (2)
O7	0.048 (8)	0.080 (11)	0.079 (11)	−0.006 (7)	−0.012 (6)	−0.004 (8)
N1	0.0420 (15)	0.0419 (16)	0.066 (2)	0.0067 (13)	0.0068 (14)	0.0195 (14)
N2	0.0440 (15)	0.0348 (15)	0.0547 (18)	0.0106 (12)	−0.0029 (13)	0.0056 (13)
C1	0.057 (2)	0.063 (2)	0.072 (3)	0.0167 (19)	0.017 (2)	0.028 (2)
C2	0.070 (3)	0.085 (4)	0.093 (3)	0.019 (3)	0.027 (2)	0.048 (3)
C3	0.058 (2)	0.068 (3)	0.101 (4)	0.003 (2)	0.008 (2)	0.048 (3)
C4	0.054 (2)	0.051 (2)	0.086 (3)	0.0058 (18)	−0.011 (2)	0.034 (2)
C5	0.0440 (18)	0.0363 (19)	0.069 (2)	0.0062 (15)	−0.0096 (17)	0.0215 (17)
C6	0.0453 (19)	0.0310 (17)	0.064 (2)	0.0075 (14)	−0.0149 (17)	0.0110 (16)
C7	0.063 (2)	0.0368 (19)	0.064 (3)	0.0150 (17)	−0.020 (2)	0.0024 (17)
C8	0.081 (3)	0.043 (2)	0.072 (3)	0.023 (2)	−0.028 (2)	−0.011 (2)
C9	0.072 (3)	0.058 (3)	0.061 (2)	0.028 (2)	−0.009 (2)	−0.012 (2)
C10	0.057 (2)	0.046 (2)	0.055 (2)	0.0179 (17)	0.0008 (18)	−0.0041 (17)
C11	0.082 (3)	0.029 (2)	0.090 (3)	0.001 (2)	−0.030 (3)	0.007 (2)
C12	0.067 (3)	0.038 (2)	0.110 (4)	−0.0082 (19)	−0.025 (3)	0.030 (2)
C13	0.0421 (17)	0.0318 (16)	0.0415 (17)	0.0105 (13)	0.0047 (14)	0.0066 (13)
C14	0.0404 (16)	0.0297 (15)	0.0376 (16)	0.0097 (13)	0.0035 (13)	0.0066 (13)
C15	0.0464 (18)	0.0327 (16)	0.0452 (18)	0.0175 (14)	0.0087 (14)	0.0107 (14)
C16	0.0533 (19)	0.0443 (19)	0.0444 (18)	0.0221 (16)	0.0152 (15)	0.0158 (15)
C17	0.076 (2)	0.048 (2)	0.0362 (18)	0.0270 (19)	0.0093 (17)	0.0014 (15)
C18	0.066 (2)	0.0338 (17)	0.0400 (18)	0.0098 (16)	0.0045 (16)	0.0005 (14)
C19	0.0530 (19)	0.0340 (17)	0.0431 (18)	0.0090 (14)	0.0110 (15)	0.0069 (14)
C20	0.060 (2)	0.0396 (18)	0.0450 (19)	0.0187 (17)	0.0111 (16)	0.0104 (15)
C21	0.070 (2)	0.047 (2)	0.0382 (18)	0.0299 (18)	0.0076 (16)	0.0117 (15)
C22	0.091 (3)	0.071 (3)	0.051 (2)	0.052 (2)	0.027 (2)	0.029 (2)
C23	0.115 (4)	0.092 (4)	0.055 (3)	0.066 (3)	0.031 (3)	0.027 (3)
C24	0.151 (5)	0.087 (4)	0.043 (2)	0.071 (4)	0.023 (3)	0.015 (2)
C25	0.122 (4)	0.053 (2)	0.055 (3)	0.036 (3)	−0.014 (3)	0.003 (2)
C26	0.082 (3)	0.049 (2)	0.0410 (19)	0.024 (2)	0.0017 (18)	0.0091 (16)

Geometric parameters (Å, º)

Cu—O3	1.881 (2)	C4—C12	1.443 (7)
Cu—O1	1.906 (2)	C5—C6	1.428 (6)
Cu—N2	1.990 (3)	C6—C7	1.399 (5)
Cu—N1	2.011 (3)	C7—C8	1.392 (7)
Cu—O4	2.585 (3)	C7—C11	1.421 (7)
Cu—O3^i	2.716 (3)	C8—C9	1.357 (7)
Cl1—C16	1.737 (3)	C8—H8	0.9300
Cl2—C18	1.748 (3)	C9—C10	1.394 (5)
Cl3—C23	1.717 (5)	C9—H9	0.9300
Cl4—C25	1.735 (5)	C10—H10	0.9300
O1—C13	1.274 (4)	C11—C12	1.319 (8)
O2—C13	1.257 (4)	C11—H11	0.9300
O3—C15	1.312 (4)	C12—H12	0.9300
O4—C20	1.247 (4)	C13—C14	1.479 (4)
O5—C20	1.267 (4)	C14—C15	1.410 (4)
O5—H5O	0.8200	C14—C19	1.412 (4)
O6—C22	1.3484 (10)	C15—C16	1.402 (5)
O6—H6O	0.8200	C16—C17	1.386 (5)
O6—H22	0.4205	C17—C18	1.372 (5)
O7—C26	1.3494 (10)	C17—H17	0.9300
O7—H7O	0.8200	C18—C19	1.366 (5)
O7—H26	0.4240	C19—H19	0.9300
N1—C1	1.314 (5)	C20—C21	1.486 (5)
N1—C5	1.361 (5)	C21—C26	1.369 (5)
N2—C10	1.329 (5)	C21—C22	1.408 (5)
N2—C6	1.362 (4)	C22—C23	1.375 (6)
C1—C2	1.390 (6)	C22—H22	0.9300
C1—H1	0.9300	C23—C24	1.316 (8)
C2—C3	1.355 (7)	C24—C25	1.405 (8)
C2—H2	0.9300	C24—H24	0.9300
C3—C4	1.399 (7)	C25—C26	1.389 (6)
C3—H3	0.9300	C26—H26	0.9300
C4—C5	1.400 (5)
O3—Cu—O1	93.00 (10)	C8—C9—C10	119.3 (5)
O3—Cu—N2	171.97 (10)	C8—C9—H9	120.3
O1—Cu—N2	93.10 (11)	C10—C9—H9	120.3
O3—Cu—N1	91.71 (12)	N2—C10—C9	121.8 (4)
O1—Cu—N1	174.85 (11)	N2—C10—H10	119.1
N2—Cu—N1	82.40 (13)	C9—C10—H10	119.1
O3—Cu—O4	93.04 (10)	C12—C11—C7	121.9 (4)
O1—Cu—O4	90.90 (9)	C12—C11—H11	119.1
N2—Cu—O4	92.09 (10)	C7—C11—H11	119.1
N1—Cu—O4	86.77 (10)	C11—C12—C4	121.9 (4)
O3—Cu—O3^i	88.44 (10)	C11—C12—H12	119.1
O1—Cu—O3^i	87.98 (9)	C4—C12—H12	119.1
N2—Cu—O3^i	86.56 (9)	O2—C13—O1	120.3 (3)
N1—Cu—O3^i	94.22 (10)	O2—C13—C14	118.7 (3)
O4—Cu—O3^i	178.20 (7)	O1—C13—C14	120.9 (3)
O3—Cu—Cu^i	54.23 (8)	C15—C14—C19	119.6 (3)
O1—Cu—Cu^i	90.05 (7)	C15—C14—C13	123.4 (3)
N2—Cu—Cu^i	120.54 (8)	C19—C14—C13	117.0 (3)
N1—Cu—Cu^i	94.39 (9)	O3—C15—C16	119.0 (3)
O4—Cu—Cu^i	147.25 (6)	O3—C15—C14	123.9 (3)
O3^i—Cu—Cu^i	34.20 (5)	C16—C15—C14	117.1 (3)
C13—O1—Cu	128.6 (2)	C17—C16—C15	122.7 (3)
C15—O3—Cu	124.1 (2)	C17—C16—Cl1	118.2 (3)
C20—O4—Cu	118.1 (2)	C15—C16—Cl1	119.1 (3)
C20—O5—H5O	109.5	C18—C17—C16	118.8 (3)
C22—O6—H6O	109.5	C18—C17—H17	120.6
H6O—O6—H22	104.8	C16—C17—H17	120.6
C26—O7—H7O	109.5	C19—C18—C17	121.2 (3)
H7O—O7—H26	104.7	C19—C18—Cl2	119.5 (3)
C1—N1—C5	118.2 (3)	C17—C18—Cl2	119.3 (3)
C1—N1—Cu	129.8 (3)	C18—C19—C14	120.6 (3)
C5—N1—Cu	112.0 (3)	C18—C19—H19	119.7
C10—N2—C6	118.1 (3)	C14—C19—H19	119.7
C10—N2—Cu	128.9 (2)	O4—C20—O5	124.1 (3)
C6—N2—Cu	112.9 (2)	O4—C20—C21	120.2 (3)
N1—C1—C2	122.5 (4)	O5—C20—C21	115.7 (3)
N1—C1—H1	118.8	C26—C21—C22	119.1 (3)
C2—C1—H1	118.8	C26—C21—C20	120.7 (3)
C3—C2—C1	119.3 (5)	C22—C21—C20	120.2 (3)
C3—C2—H2	120.4	O6—C22—C23	117.7 (4)
C1—C2—H2	120.4	O6—C22—C21	122.2 (3)
C2—C3—C4	120.9 (4)	C23—C22—C21	120.1 (4)
C2—C3—H3	119.5	C23—C22—H22	119.9
C4—C3—H3	119.5	C21—C22—H22	120.1
C3—C4—C5	115.7 (4)	C24—C23—C22	120.8 (5)
C3—C4—C12	126.7 (4)	C24—C23—Cl3	119.6 (4)
C5—C4—C12	117.6 (5)	C22—C23—Cl3	119.6 (5)
N1—C5—C4	123.5 (4)	C23—C24—C25	121.0 (4)
N1—C5—C6	116.5 (3)	C23—C24—H24	119.5
C4—C5—C6	120.0 (4)	C25—C24—H24	119.5
N2—C6—C7	123.6 (4)	C26—C25—C24	119.3 (5)
N2—C6—C5	116.1 (3)	C26—C25—Cl4	118.9 (4)
C7—C6—C5	120.2 (3)	C24—C25—Cl4	121.8 (4)
C8—C7—C6	115.7 (4)	O7—C26—C21	122.3 (7)
C8—C7—C11	125.9 (4)	O7—C26—C25	117.9 (7)
C6—C7—C11	118.4 (5)	C21—C26—C25	119.7 (4)
C9—C8—C7	121.3 (4)	C21—C26—H26	120.1
C9—C8—H8	119.3	C25—C26—H26	120.1
C7—C8—H8	119.3

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5O···O2^ii	0.82	1.69	2.489 (3)	166
O6—H6O···O4	0.82	1.85	2.577 (5)	147
O7—H7O···O5	0.82	1.73	2.460 (14)	147

Symmetry code: (ii) −x+2, −y+1, −z+1.

(II) bis(µ-5-chloro-2-oxidobenzoato)- κ³O¹,O²:O¹; κ³O¹:O¹,O²- bis[(5-chloro-2-hydroxybenzoic acid-κO¹)(1,10- phenanthroline-κ²N,N')copper(II)] ethanol monosolvate

Crystal data

[Cu2(C7H3ClO3)2(C12H8N2)2(C7H5ClO3)2]·C2H6O	Z = 1
Mr = 1219.78	F(000) = 620
Triclinic, P1	Dx = 1.636 Mg m^−3
Hall symbol: -P1	Mo Kα radiation, λ = 0.71069 Å
a = 7.9153 (2) Å	Cell parameters from 18236 reflections
b = 11.1877 (3) Å	θ = 4.1–26.4°
c = 15.0623 (3) Å	µ = 1.15 mm^−1
α = 72.456 (2)°	T = 293 K
β = 77.056 (2)°	Prism, green
γ = 83.897 (2)°	0.35 × 0.24 × 0.06 mm
V = 1238.39 (5) Å^3

Data collection

Gemini R CCD diffractometer	5017 independent reflections
Radiation source: fine-focus sealed tube	4055 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
Detector resolution: 10.4340 pixels mm^-1	θmax = 26.4°, θmin = 4.1°
ω scans	h = −9→9
Absorption correction: analytical CrysAlis RED (Agilent, 2011)	k = −13→13
Tmin = 0.689, Tmax = 0.934	l = −18→18
20410 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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0647P)^2] where P = (Fo^2 + 2Fc^2)/3
5017 reflections	(Δ/σ)max = 0.001
363 parameters	Δρmax = 0.33 e Å^−3
18 restraints	Δρmin = −0.30 e Å^−3

Special details

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 > 2σ(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	Occ. (<1)
Cu1	0.60102 (3)	0.64268 (2)	0.429213 (16)	0.04527 (11)
Cl1	1.12917 (9)	0.28867 (8)	0.13591 (5)	0.0871 (2)
Cl2	1.40961 (11)	0.62994 (9)	0.01940 (5)	0.1027 (3)
O1	0.72749 (18)	0.49146 (12)	0.47797 (9)	0.0476 (3)
O2	0.93467 (18)	0.34518 (13)	0.47207 (9)	0.0470 (3)
O3	0.61736 (19)	0.61406 (13)	0.31077 (10)	0.0521 (3)
O4	0.86634 (18)	0.78018 (13)	0.34870 (10)	0.0542 (4)
O5	1.10786 (18)	0.66041 (14)	0.35906 (9)	0.0508 (3)
H5O	1.0760	0.6569	0.4154	0.076*
O6	0.7954 (2)	0.88882 (16)	0.18481 (12)	0.0717 (5)
H6O	0.7847	0.8716	0.2426	0.108*
N1	0.4458 (2)	0.79650 (16)	0.39957 (14)	0.0533 (4)
N2	0.5634 (2)	0.67961 (16)	0.55460 (13)	0.0483 (4)
C1	0.3915 (3)	0.8522 (2)	0.3187 (2)	0.0667 (6)
H1	0.4273	0.8192	0.2675	0.080*
C2	0.2803 (3)	0.9607 (3)	0.3098 (3)	0.0866 (9)
H2	0.2441	0.9993	0.2528	0.104*
C3	0.2263 (3)	1.0085 (2)	0.3854 (3)	0.0895 (10)
H3	0.1535	1.0802	0.3796	0.107*
C4	0.2795 (3)	0.9505 (2)	0.4722 (2)	0.0724 (8)
C5	0.3908 (3)	0.8439 (2)	0.47452 (19)	0.0577 (6)
C6	0.4534 (3)	0.78072 (19)	0.55914 (17)	0.0536 (5)
C7	0.4020 (3)	0.8219 (2)	0.6406 (2)	0.0674 (7)
C8	0.4690 (4)	0.7540 (3)	0.7207 (2)	0.0762 (8)
H8	0.4382	0.7775	0.7766	0.091*
C9	0.5799 (3)	0.6531 (2)	0.71583 (17)	0.0669 (6)
H9	0.6252	0.6076	0.7686	0.080*
C10	0.6260 (3)	0.6178 (2)	0.63143 (15)	0.0545 (5)
H10	0.7026	0.5492	0.6292	0.065*
C11	0.2309 (3)	0.9916 (3)	0.5554 (3)	0.0922 (12)
H11	0.1584	1.0629	0.5541	0.111*
C12	0.2871 (4)	0.9296 (3)	0.6369 (3)	0.0876 (10)
H12	0.2504	0.9578	0.6905	0.105*
C13	0.8343 (2)	0.42912 (17)	0.43089 (12)	0.0380 (4)
C14	0.8425 (2)	0.44870 (17)	0.32900 (12)	0.0376 (4)
C15	0.7339 (2)	0.53784 (18)	0.27668 (13)	0.0414 (4)
C16	0.7534 (3)	0.5456 (2)	0.17909 (14)	0.0529 (5)
H16	0.6844	0.6037	0.1428	0.063*
C17	0.8707 (3)	0.4703 (2)	0.13700 (14)	0.0572 (6)
H17	0.8800	0.4768	0.0731	0.069*
C18	0.9760 (3)	0.3838 (2)	0.19014 (14)	0.0532 (5)
C19	0.9624 (2)	0.37297 (18)	0.28400 (13)	0.0439 (4)
H19	1.0335	0.3146	0.3187	0.053*
C20	1.0016 (2)	0.73046 (17)	0.31211 (13)	0.0410 (4)
C21	1.0456 (2)	0.75088 (17)	0.20742 (13)	0.0416 (4)
C22	0.9388 (3)	0.82782 (19)	0.14887 (15)	0.0500 (5)
C23	0.9792 (3)	0.8430 (2)	0.05243 (16)	0.0620 (6)
H23	0.9085	0.8949	0.0136	0.074*
C24	1.1226 (3)	0.7824 (2)	0.01309 (15)	0.0650 (6)
H24	1.1483	0.7927	−0.0521	0.078*
C25	1.2287 (3)	0.7063 (2)	0.06982 (15)	0.0587 (6)
C26	1.1914 (3)	0.6906 (2)	0.16684 (14)	0.0491 (5)
H26	1.2640	0.6396	0.2049	0.059*
O1S	0.5347 (9)	1.0564 (7)	0.1129 (5)	0.162 (2)	0.50
H1S	0.6100	1.0004	0.1226	0.242*	0.50
C1S	0.4284 (17)	1.0289 (19)	0.0570 (10)	0.196 (7)	0.50
H1S1	0.3406	1.0960	0.0454	0.235*	0.50
H1S2	0.3694	0.9521	0.0927	0.235*	0.50
C2S	0.5266 (13)	1.0154 (16)	−0.0361 (10)	0.157 (6)	0.50
H2S1	0.4490	0.9961	−0.0702	0.236*	0.50
H2S2	0.6131	0.9487	−0.0252	0.236*	0.50
H2S3	0.5818	1.0923	−0.0729	0.236*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.04473 (16)	0.04199 (16)	0.05081 (17)	0.00592 (10)	−0.00694 (11)	−0.02043 (11)
Cl1	0.0776 (4)	0.1340 (6)	0.0665 (4)	0.0279 (4)	−0.0117 (3)	−0.0666 (4)
Cl2	0.0971 (6)	0.1512 (7)	0.0617 (4)	0.0476 (5)	−0.0110 (4)	−0.0549 (4)
O1	0.0562 (8)	0.0484 (7)	0.0384 (7)	0.0120 (6)	−0.0073 (6)	−0.0192 (6)
O2	0.0507 (8)	0.0530 (8)	0.0371 (7)	0.0130 (6)	−0.0095 (6)	−0.0171 (6)
O3	0.0563 (9)	0.0516 (8)	0.0527 (8)	0.0106 (7)	−0.0188 (7)	−0.0199 (7)
O4	0.0496 (8)	0.0610 (9)	0.0530 (8)	0.0089 (7)	−0.0061 (6)	−0.0249 (7)
O5	0.0521 (8)	0.0644 (8)	0.0360 (7)	0.0102 (7)	−0.0105 (6)	−0.0176 (6)
O6	0.0634 (10)	0.0769 (11)	0.0657 (10)	0.0256 (9)	−0.0178 (8)	−0.0131 (9)
N1	0.0364 (9)	0.0438 (9)	0.0780 (12)	−0.0003 (7)	−0.0079 (8)	−0.0180 (9)
N2	0.0375 (9)	0.0491 (9)	0.0606 (10)	−0.0055 (7)	0.0046 (7)	−0.0286 (8)
C1	0.0481 (13)	0.0531 (13)	0.0938 (18)	−0.0004 (10)	−0.0161 (12)	−0.0127 (12)
C2	0.0545 (15)	0.0578 (15)	0.134 (3)	0.0043 (12)	−0.0284 (16)	−0.0034 (17)
C3	0.0412 (13)	0.0474 (14)	0.168 (3)	0.0033 (11)	−0.0060 (17)	−0.0268 (18)
C4	0.0362 (12)	0.0438 (12)	0.132 (2)	−0.0016 (10)	0.0004 (13)	−0.0292 (14)
C5	0.0312 (10)	0.0435 (11)	0.0979 (18)	−0.0072 (8)	0.0082 (11)	−0.0332 (12)
C6	0.0363 (10)	0.0471 (11)	0.0793 (15)	−0.0093 (9)	0.0088 (10)	−0.0332 (11)
C7	0.0475 (13)	0.0593 (14)	0.099 (2)	−0.0191 (11)	0.0245 (13)	−0.0515 (14)
C8	0.0708 (17)	0.0863 (19)	0.0799 (18)	−0.0280 (15)	0.0212 (14)	−0.0542 (15)
C9	0.0664 (15)	0.0803 (16)	0.0618 (14)	−0.0207 (13)	0.0051 (11)	−0.0392 (12)
C10	0.0498 (12)	0.0617 (13)	0.0560 (12)	−0.0104 (10)	0.0018 (10)	−0.0289 (10)
C11	0.0462 (15)	0.0557 (16)	0.174 (4)	−0.0058 (12)	0.0259 (19)	−0.065 (2)
C12	0.0632 (17)	0.0713 (18)	0.133 (3)	−0.0119 (14)	0.0258 (18)	−0.0660 (19)
C13	0.0385 (10)	0.0396 (9)	0.0364 (9)	−0.0038 (8)	−0.0028 (7)	−0.0146 (8)
C14	0.0371 (9)	0.0407 (9)	0.0360 (9)	−0.0057 (8)	−0.0038 (7)	−0.0139 (7)
C15	0.0425 (10)	0.0442 (10)	0.0391 (9)	−0.0077 (8)	−0.0081 (8)	−0.0126 (8)
C16	0.0550 (12)	0.0595 (12)	0.0436 (11)	−0.0059 (10)	−0.0154 (9)	−0.0086 (9)
C17	0.0574 (13)	0.0839 (16)	0.0335 (10)	−0.0098 (11)	−0.0044 (9)	−0.0228 (10)
C18	0.0485 (12)	0.0722 (14)	0.0434 (11)	−0.0035 (10)	−0.0011 (9)	−0.0291 (10)
C19	0.0426 (10)	0.0529 (11)	0.0392 (10)	−0.0002 (9)	−0.0058 (8)	−0.0199 (9)
C20	0.0418 (10)	0.0406 (10)	0.0424 (10)	−0.0033 (8)	−0.0065 (8)	−0.0156 (8)
C21	0.0448 (10)	0.0405 (10)	0.0404 (10)	−0.0027 (8)	−0.0091 (8)	−0.0126 (8)
C22	0.0487 (11)	0.0471 (11)	0.0525 (12)	0.0003 (9)	−0.0136 (9)	−0.0101 (9)
C23	0.0661 (15)	0.0667 (14)	0.0484 (12)	0.0001 (11)	−0.0209 (11)	−0.0035 (10)
C24	0.0727 (16)	0.0834 (16)	0.0383 (11)	−0.0067 (13)	−0.0119 (10)	−0.0149 (11)
C25	0.0609 (14)	0.0720 (14)	0.0452 (11)	0.0064 (11)	−0.0077 (10)	−0.0250 (10)
C26	0.0501 (11)	0.0568 (12)	0.0418 (10)	0.0059 (9)	−0.0105 (8)	−0.0179 (9)
O1S	0.140 (5)	0.173 (6)	0.155 (5)	0.021 (4)	−0.034 (4)	−0.028 (4)
C1S	0.192 (14)	0.291 (16)	0.122 (8)	0.066 (10)	−0.092 (9)	−0.065 (9)
C2S	0.068 (6)	0.246 (15)	0.149 (9)	−0.061 (9)	0.000 (7)	−0.041 (11)

Geometric parameters (Å, º)

Cu1—O3	1.880 (1)	C9—C10	1.404 (3)
Cu1—O1	1.904 (1)	C9—H9	0.9300
Cu1—N1	2.001 (2)	C10—H10	0.9300
Cu1—N2	2.005 (2)	C11—C12	1.360 (5)
Cu1—O4	2.582 (2)	C11—H11	0.9300
Cu1—O1^i	2.984 (2)	C12—H12	0.9300
Cl1—C18	1.754 (2)	C13—C14	1.471 (2)
Cl2—C25	1.733 (2)	C14—C19	1.402 (3)
O1—C13	1.268 (2)	C14—C15	1.415 (3)
O2—C13	1.268 (2)	C15—C16	1.420 (3)
O3—C15	1.314 (2)	C16—C17	1.366 (3)
O4—C20	1.246 (2)	C16—H16	0.9300
O5—C20	1.270 (2)	C17—C18	1.390 (3)
O5—H5O	0.8200	C17—H17	0.9300
O6—C22	1.353 (3)	C18—C19	1.363 (3)
O6—H6O	0.8200	C19—H19	0.9300
N1—C1	1.332 (3)	C20—C21	1.488 (3)
N1—C5	1.356 (3)	C21—C26	1.388 (3)
N2—C10	1.328 (3)	C21—C22	1.398 (3)
N2—C6	1.361 (3)	C22—C23	1.377 (3)
C1—C2	1.412 (3)	C23—C24	1.370 (4)
C1—H1	0.9300	C23—H23	0.9300
C2—C3	1.367 (5)	C24—C25	1.375 (3)
C2—H2	0.9300	C24—H24	0.9300
C3—C4	1.408 (5)	C25—C26	1.384 (3)
C3—H3	0.9300	C26—H26	0.9300
C4—C5	1.401 (3)	O1S—C1S	1.428 (9)
C4—C11	1.423 (4)	O1S—H1S	0.8200
C5—C6	1.427 (4)	C1S—C2S	1.487 (8)
C6—C7	1.400 (3)	C1S—H1S1	0.9700
C7—C8	1.401 (4)	C1S—H1S2	0.9700
C7—C12	1.426 (4)	C2S—H2S1	0.9600
C8—C9	1.364 (4)	C2S—H2S2	0.9600
C8—H8	0.9300	C2S—H2S3	0.9600
O3—Cu1—O1	93.78 (6)	C12—C11—C4	122.0 (3)
O3—Cu1—N1	93.84 (7)	C12—C11—H11	119.0
O1—Cu1—N1	170.69 (6)	C4—C11—H11	119.0
O3—Cu1—N2	175.14 (6)	C11—C12—C7	120.4 (3)
O1—Cu1—N2	90.15 (6)	C11—C12—H12	119.8
N1—Cu1—N2	81.98 (8)	C7—C12—H12	119.8
O3—Cu1—O4	86.37 (6)	O1—C13—O2	120.03 (16)
O1—Cu1—O4	96.68 (5)	O1—C13—C14	121.71 (16)
N1—Cu1—O4	89.12 (6)	O2—C13—C14	118.24 (16)
N2—Cu1—O4	96.02 (6)	C19—C14—C15	119.87 (16)
O3—Cu1—O1^i	95.42 (5)	C19—C14—C13	117.25 (16)
O1—Cu1—O1^i	88.88 (5)	C15—C14—C13	122.87 (16)
N1—Cu1—O1^i	85.09 (5)	O3—C15—C14	125.47 (16)
N2—Cu1—O1^i	81.78 (5)	O3—C15—C16	117.46 (17)
O4—Cu1—O1^i	174.04 (4)	C14—C15—C16	117.07 (18)
O3—Cu1—Cu1^i	96.56 (5)	C17—C16—C15	121.9 (2)
O1—Cu1—Cu1^i	56.67 (4)	C17—C16—H16	119.0
N1—Cu1—Cu1^i	117.03 (5)	C15—C16—H16	119.0
N2—Cu1—Cu1^i	83.22 (5)	C16—C17—C18	119.71 (18)
O4—Cu1—Cu1^i	153.28 (3)	C16—C17—H17	120.1
O1^i—Cu1—Cu1^i	32.21 (2)	C18—C17—H17	120.1
C13—O1—Cu1	127.41 (12)	C19—C18—C17	120.5 (2)
C15—O3—Cu1	124.24 (12)	C19—C18—Cl1	119.61 (17)
C20—O4—Cu1	117.98 (12)	C17—C18—Cl1	119.86 (15)
C20—O5—H5O	109.5	C18—C19—C14	120.89 (19)
C22—O6—H6O	109.5	C18—C19—H19	119.6
C1—N1—C5	119.2 (2)	C14—C19—H19	119.6
C1—N1—Cu1	128.16 (17)	O4—C20—O5	123.99 (17)
C5—N1—Cu1	112.59 (15)	O4—C20—C21	119.94 (17)
C10—N2—C6	118.00 (19)	O5—C20—C21	116.07 (16)
C10—N2—Cu1	129.07 (14)	C26—C21—C22	119.04 (18)
C6—N2—Cu1	112.90 (15)	C26—C21—C20	120.17 (17)
N1—C1—C2	121.0 (3)	C22—C21—C20	120.77 (18)
N1—C1—H1	119.5	O6—C22—C23	118.66 (18)
C2—C1—H1	119.5	O6—C22—C21	121.39 (18)
C3—C2—C1	119.5 (3)	C23—C22—C21	119.9 (2)
C3—C2—H2	120.3	C24—C23—C22	120.6 (2)
C1—C2—H2	120.3	C24—C23—H23	119.7
C2—C3—C4	120.8 (2)	C22—C23—H23	119.7
C2—C3—H3	119.6	C23—C24—C25	120.1 (2)
C4—C3—H3	119.6	C23—C24—H24	120.0
C5—C4—C3	115.9 (3)	C25—C24—H24	120.0
C5—C4—C11	118.5 (3)	C24—C25—C26	120.3 (2)
C3—C4—C11	125.6 (3)	C24—C25—Cl2	119.72 (17)
N1—C5—C4	123.6 (3)	C26—C25—Cl2	119.99 (17)
N1—C5—C6	116.83 (18)	C25—C26—C21	120.04 (19)
C4—C5—C6	119.5 (2)	C25—C26—H26	120.0
N2—C6—C7	123.4 (2)	C21—C26—H26	120.0
N2—C6—C5	115.6 (2)	C1S—O1S—H1S	109.4
C7—C6—C5	120.9 (2)	O1S—C1S—C2S	113.6 (10)
C6—C7—C8	117.2 (2)	O1S—C1S—H1S1	108.9
C6—C7—C12	118.5 (3)	C2S—C1S—H1S1	108.4
C8—C7—C12	124.2 (3)	O1S—C1S—H1S2	109.0
C9—C8—C7	119.2 (2)	C2S—C1S—H1S2	109.1
C9—C8—H8	120.4	H1S1—C1S—H1S2	107.7
C7—C8—H8	120.4	C1S—C2S—H2S1	109.9
C8—C9—C10	120.3 (3)	C1S—C2S—H2S2	108.9
C8—C9—H9	119.9	H2S1—C2S—H2S2	109.5
C10—C9—H9	119.9	C1S—C2S—H2S3	109.6
N2—C10—C9	121.9 (2)	H2S1—C2S—H2S3	109.5
N2—C10—H10	119.1	H2S2—C2S—H2S3	109.5
C9—C10—H10	119.1
O3—Cu1—O1—C13	22.94 (16)	N2—C6—C7—C8	0.0 (3)
N2—Cu1—O1—C13	−159.92 (16)	C5—C6—C7—C8	179.7 (2)
O4—Cu1—O1—C13	−63.83 (16)	N2—C6—C7—C12	179.6 (2)
O1^i—Cu1—O1—C13	118.31 (17)	C5—C6—C7—C12	−0.8 (3)
Cu1^i—Cu1—O1—C13	118.31 (17)	C6—C7—C8—C9	0.3 (3)
O1—Cu1—O3—C15	−20.31 (15)	C12—C7—C8—C9	−179.2 (2)
O4—Cu1—O3—C15	76.16 (15)	C7—C8—C9—C10	−0.1 (3)
O1^i—Cu1—O3—C15	−109.54 (15)	C6—N2—C10—C9	0.9 (3)
Cu1^i—Cu1—O3—C15	−77.17 (15)	Cu1—N2—C10—C9	−176.91 (15)
O3—Cu1—O4—C20	−57.99 (14)	C8—C9—C10—N2	−0.5 (3)
O1—Cu1—O4—C20	35.40 (14)	C5—C4—C11—C12	−0.9 (4)
N1—Cu1—O4—C20	−151.90 (14)	C3—C4—C11—C12	179.5 (3)
N2—Cu1—O4—C20	126.26 (14)	C4—C11—C12—C7	1.7 (4)
Cu1^i—Cu1—O4—C20	39.38 (18)	C6—C7—C12—C11	−0.8 (4)
O3—Cu1—N1—C1	−3.11 (19)	C8—C7—C12—C11	178.7 (2)
N2—Cu1—N1—C1	179.39 (19)	Cu1—O1—C13—O2	165.59 (13)
O4—Cu1—N1—C1	83.19 (19)	Cu1—O1—C13—C14	−16.2 (3)
O1^i—Cu1—N1—C1	−98.24 (18)	O1—C13—C14—C19	−178.56 (17)
Cu1^i—Cu1—N1—C1	−102.48 (18)	O2—C13—C14—C19	−0.3 (3)
O3—Cu1—N1—C5	175.50 (13)	O1—C13—C14—C15	0.4 (3)
N2—Cu1—N1—C5	−1.99 (13)	O2—C13—C14—C15	178.61 (17)
O4—Cu1—N1—C5	−98.20 (13)	Cu1—O3—C15—C14	12.6 (3)
O1^i—Cu1—N1—C5	80.38 (13)	Cu1—O3—C15—C16	−167.09 (14)
Cu1^i—Cu1—N1—C5	76.13 (14)	C19—C14—C15—O3	−179.81 (17)
O1—Cu1—N2—C10	5.15 (18)	C13—C14—C15—O3	1.3 (3)
O4—Cu1—N2—C10	−91.59 (18)	C19—C14—C15—C16	−0.1 (3)
O1^i—Cu1—N2—C10	94.00 (17)	C13—C14—C15—C16	−178.96 (17)
Cu1^i—Cu1—N2—C10	61.53 (17)	O3—C15—C16—C17	−179.82 (19)
O1—Cu1—N2—C6	−172.73 (14)	C14—C15—C16—C17	0.4 (3)
N1—Cu1—N2—C6	2.27 (13)	C15—C16—C17—C18	−0.6 (3)
O4—Cu1—N2—C6	90.53 (13)	C16—C17—C18—C19	0.5 (3)
O1^i—Cu1—N2—C6	−83.88 (13)	C16—C17—C18—Cl1	−178.93 (17)
Cu1^i—Cu1—N2—C6	−116.35 (13)	C17—C18—C19—C14	−0.1 (3)
C5—N1—C1—C2	1.1 (3)	Cl1—C18—C19—C14	179.27 (15)
Cu1—N1—C1—C2	179.60 (16)	C15—C14—C19—C18	−0.1 (3)
N1—C1—C2—C3	−0.6 (4)	C13—C14—C19—C18	178.88 (18)
C1—C2—C3—C4	−0.3 (4)	Cu1—O4—C20—O5	−78.6 (2)
C2—C3—C4—C5	0.8 (4)	Cu1—O4—C20—C21	100.83 (17)
C2—C3—C4—C11	−179.7 (2)	O4—C20—C21—C26	−176.68 (19)
C1—N1—C5—C4	−0.6 (3)	O5—C20—C21—C26	2.8 (3)
Cu1—N1—C5—C4	−179.32 (16)	O4—C20—C21—C22	1.5 (3)
C1—N1—C5—C6	−179.83 (18)	O5—C20—C21—C22	−179.07 (18)
Cu1—N1—C5—C6	1.4 (2)	C26—C21—C22—O6	−179.91 (19)
C3—C4—C5—N1	−0.3 (3)	C20—C21—C22—O6	1.9 (3)
C11—C4—C5—N1	−179.93 (19)	C26—C21—C22—C23	−0.1 (3)
C3—C4—C5—C6	178.9 (2)	C20—C21—C22—C23	−178.29 (19)
C11—C4—C5—C6	−0.7 (3)	O6—C22—C23—C24	−179.6 (2)
C10—N2—C6—C7	−0.6 (3)	C21—C22—C23—C24	0.6 (4)
Cu1—N2—C6—C7	177.50 (15)	C22—C23—C24—C25	−0.5 (4)
C10—N2—C6—C5	179.70 (17)	C23—C24—C25—C26	0.0 (4)
Cu1—N2—C6—C5	−2.2 (2)	C23—C24—C25—Cl2	179.9 (2)
N1—C5—C6—N2	0.5 (3)	C24—C25—C26—C21	0.5 (4)
C4—C5—C6—N2	−178.79 (17)	Cl2—C25—C26—C21	−179.44 (17)
N1—C5—C6—C7	−179.18 (17)	C22—C21—C26—C25	−0.4 (3)
C4—C5—C6—C7	1.5 (3)	C20—C21—C26—C25	177.8 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5O···O2^ii	0.82	1.67	2.472 (2)	165
O6—H6O···O4	0.82	1.83	2.560 (2)	147
O1S—H1S···O6	0.82	2.03	2.811 (7)	159

Symmetry code: (ii) −x+2, −y+1, −z+1.