Crystal structure of aqua­{μ-N-[3-(di­methyl­amino)­prop­yl]-N′-2-(oxidophen­yl)oxamidato}(1,10-phen­anthroline-5,6-dione)dicopper(II) perchlorate hemihydrate

Zhang, X.; Li, Y.-T.; Wu, Z.-Y.

doi:10.1107/S2056989015009391

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ISSN: 2056-9890

Volume 71| Part 6| June 2015| Pages 667-670

doi:10.1107/S2056989015009391

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Crystal structure of aqua{μ-N-[3-(dimethylamino)propyl]-N′-2-(oxidophenyl)oxamidato}(1,10-phenanthroline-5,6-dione)dicopper(II) perchlorate hemihydrate

Xin Zhang,^a Yan-Tuan Li ^a and Zhi-Yong Wu ^a ^*

^aKey Laboratory of Marine Drugs, Ministry of Education of China, School of Medicine and Pharmacy, Ocean University of China, Qingdao 266003, People's Republic of China
^*Correspondence e-mail: wuzy@ouc.edu.cn

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 8 May 2015; accepted 17 May 2015; online 23 May 2015)

The title compound, [Cu₂(C₁₃H₁₆N₃O₃)(C₁₂H₆N₂O₂)(H₂O)]ClO₄·0.5H₂O, consists of a cis-oxamide-bridged binuclear Cu^II complex cation, a perchlorate anion and half a solvent water molecule. One Cu^II cation is N,N′,N",O-chelated by an N-[3-(dimethylamino)propyl]-N′-(2-hydroxyphenyl)oxamide trianion in a distorted square-planar geometry, whereas the other Cu^II cation is O,O′-chelated by the oxamide moiety of the anion and N,N′-chelated by a 1,10-phenanthroline-5,6-dione molecule, and a water molecule further coordinates the second Cu^II cation, completing a distorted square-pyramidal coordination geometry. In the crystal, classical O—H⋯O hydrogen bonds, weak C—H⋯O hydrogen-bonding interactions and π–π stacking interactions link the complex cations, anions and solvent water molecules into a three-dimensional supramolecular architecture. In the crystal, the dimethylaminopropyl unit of the oxamide anion is disordered over two positions with an occupancy ratio of 0.561 (11):0.439 (11); the solvent water molecule is also disordered over two positions, the occupancy ratio being 0.207 (10):0.293 (10).

Keywords: crystal structure; binuclear copper(II) complex; oxamide complex; 1,10-phenanthroline-5,6-dione; hydrogen bonding; π–π stacking.

CCDC reference: 1401557

1. Chemical context

1,10-Phenanthroline-5,6-dione (Phdo) is a multifaceted ligand since the structure and electronic properties thereof incorporate the features of the diimine and quinone functionalities (Girgis et al., 1975 ; Calderazzo et al., 2002 ). Consequently, as part of our systematic study of asymmetrical bis-substituent oxamide complexes and the influence of structures on the DNA-binding properties thereof (Li et al., 2012 ; Zhang et al., 2013 ), we selected N-[3-(dimethylamino)propyl]-N′-2-(oxidophenyl)oxamide (H₃Dmapox) as a bridging ligand and Phdo as a terminal ligand to synthesize the title binuclear copper(II) complex, [Cu₂(Dmapox)(Phdo)H₂O]⁺ClO₄⁻·0.5H₂O. Its crystal structure and supramolecular structure are reported here.

2. Structural commentary

The title compound consists of a binuclear Cu^II complex cation, a perchlorate anion and half of a solvent water molecule (Fig. 1). Two copper(II) ions are bridged by a cis-oxamido group. The Cu1 atom, located at the inner site of the oxamide ligand, has a distorted square-planar geometry and is displaced from the coordination plane by 0.0454 (15) Å, which is consistent with structures reported previously (Gao & Wang, 2010 ; Lu et al., 2011 ). The two exo-oxygen atoms of the oxamide ligand and two nitrogen atoms of the Phdo molecule chelate the Cu2 atom, forming the basal coordination plane [the maximum deviation being 0.0384 (14) Å for N4], and a water molecule (O4) occupies the apical position, completing a distorted square-pyramidal coordination geometry with a τ value of 0.06 (Addison et al., 1984 ). The Cu—O distance of 2.213 (3) Å in the apical direction is longer than those in the basal plane by 0.261 (4) and 0.266 (4) Å (Table 1). The Cu2 atom is displaced by 0.1610 (15) Å from the basal plane towards the apex.

Table 1
Selected bond lengths (Å)

Cu1—O1	1.950 (3)	Cu2—O3	1.947 (3)
Cu1—N1	1.932 (3)	Cu2—O4	2.213 (3)
Cu1—N2	1.982 (3)	Cu2—N4	1.989 (3)
Cu1—N3	2.013 (3)	Cu2—N5	1.991 (3)
Cu2—O2	1.952 (3)

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. For clarity, disordered atoms are represented in a different style and the H atoms on disordered carbon atoms have been omitted. Dashed lines indicate hydrogen bonds.

The hexadentate oxamide anion, Dmapox³⁻, bridges the two copper(II) cations with three planar five-membered chelate rings and one six-membered ring, the latter being disordered over two positions. The puckering parameters of the first component (containing atoms C10A and C11A) are Q = 0.554 (8) Å, θ = 47.6 (6)° and φ = 206.0 (7)°, and those of the other are Q = 0.565 (11) Å, θ = 123.4 (8)° and φ = 38.8 (9)°; both suggest an approximate half-chair conformation.

3. Supramolecular features

Besides classical O—H⋯O hydrogen bonds, weak C—H⋯O hydrogen bonds and aromatic stacking interactions are important to the supramolecular structure. As illustrated in Fig. 2, two symmetry-related binuclear cations link each other, forming a dimer by hydrogen bonds between the coordinating water molecules and phenolic oxygen atoms (Table 2). Then the dimers are assembled by perchlorate anions, generating a wave-like layer parallel to (100). Subsequently, an offset π–π stacking interaction occurs between the middle aromatic ring of the Phdo ligand of a binuclear unit and the benzene ring of the other unit at −x, 1 − y, −z [symmetry code (iv)], and vice versa (Fig. 3). The separations of the overlapped atoms from their opposite rings are 3.191 (4) (C2^iv), 3.211 (4) (C3^iv) and 3.252 (4) Å (C19^iv).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯O1ⁱ	0.84	1.89	2.666 (3)	153
O4—H4B⋯O10B	0.91	1.93	2.740 (8)	146
O4—H4B⋯O11A	0.91	2.10	3.009 (7)	171
O7A—H7A⋯O3	0.86	2.51	3.27 (2)	147
O7B—H7D⋯O5ⁱⁱ	0.86	2.51	3.305 (18)	153
C3—H3⋯O8ⁱⁱⁱ	0.93	2.52	3.193 (5)	130
C15—H15⋯O9Aⁱⁱⁱ	0.93	2.55	3.335 (7)	142
C15—H15⋯O11Bⁱⁱⁱ	0.93	2.49	3.384 (10)	162
C16—H16⋯O6ⁱⁱⁱ	0.93	2.54	3.195 (5)	128
C10A—H10A⋯O6ⁱⁱ	0.97	2.44	3.202 (9)	135
C11A—H11A⋯O4^iv	0.97	2.54	3.409 (7)	150
C13A—H13B⋯O4ⁱ	0.96	2.49	3.382 (16)	154
C21—H21⋯O10A^v	0.93	2.53	3.277 (8)	138
C23—H23⋯O7A	0.93	2.30	3.154 (19)	152
C23—H23⋯O7B	0.93	2.49	3.31 (2)	147
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
The two-dimensional wave-like hydrogen-bonding network constructed by classical O—H⋯O and weak C—H⋯O interactions [symmetry codes: (i) 1 − x, 1 − y, −z; (ii) x, $[{1\over 2}]$ − y, z − $[{1\over 2}]$ ; (iii) x, $[{1\over 2}]$ − y, z + $[{1\over 2}]$ ].

Figure 3
A perspective view of the π–π stacking interactions viewed perpendicular to the middle ring of the Phdo ligand. H atoms have been omitted for clarity [symmetry code: (iv) −x, 1 − y, −z].

4. Database survey

Several Cu^II complexes of 1,10-phenanthroline-5,6-dione have been reported previously, for example, Chetana et al. (2009 ); Galet et al. (2005 ); Saravani et al. (2007 ); Wang et al. (2013); Yamada et al. (2002 ) and Xu et al. (2006 ).

5. Synthesis and crystallization

N-[3-(Dimethylamino)propyl]-N′-2-(oxidophenyl)oxamide (H₃Dmapox; Zhang et al., 2013) and 1,10-phenanthroline-5,6-dione (Phdo; Dickeson & Summers, 1970 ) were prepared by published procedures. The title compound was obtained as follows: A solution of Cu(ClO₄)₂·6H₂O (0.0371 g, 0.1 mmol) in methanol (5 ml) was added dropwise to a solution of H₃Dmapox (0.0133 g, 0.05 mmol) and piperidine (0.0128 g, 0.15 mmol) in methanol (5 ml). The solution was stirred continuously for 0.5 h. Then a solution of Phdo (0.011 g, 0.05 mmol) in methanol (5 ml) was added dropwise, and the mixture was stirred continuously at 313 K for 6 h and then filtered. Dark-blue crystals of the title compound suitable for X-ray analysis were obtained from the filtrate by slow evaporation at room temperature for 7 d. Yield: 0.026 g (71.62%). Analysis calculated for Cu₂C₂₅H₂₅ClN₅O_10.5: C 41.44, H 3.48, N 9.67%; found: C 42.57, H 3.15, N 9.19%.

6. Refinement

Crystal data, data collection, and refinement details are summarized in Table 3. Disorder occurs for four carbon atoms of the 3-(dimethylamino)propyl group [C10A–C13A, with occupancies of 0.561 (11); C10B–C13B, 0.439 (11)], three oxygen atoms of the perchlorate ion [O9A–O11A, 0.646 (8); O9B–O11B, 0.354 (8)] and the solvent water molecule (O7A, 0.207 (10); O7B, 0.293 (10)]. The occupancies were refined freely except for the sum of atoms O7A and O7B which was fixed at 0.5. Some restraints on distances (DFIX) and anisotropic displacement parameters (SIMU) were applied to the disordered atoms to avoid unreasonable geometries. The hydrogen atoms of the water molecules were found in a difference Fourier map and then refined as riding. Other H atoms were placed in calculated positions, with C—H = 0.96 (methyl), 0.97 (methylene) and 0.93 Å (aromatic), and refined using a riding model, with U_iso(H) = 1.2 U_eq(C) or 1.5 for methyl groups.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₃H₁₆N₃O₃)(C₁₂H₆N₂O₂)(H₂O)]ClO₄·0.5H₂O
M_r	726.03
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.7430 (6), 17.3066 (9), 14.1086 (8)
β (°)	98.154 (1)
V (Å³)	2838.3 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.66
Crystal size (mm)	0.30 × 0.12 × 0.06

Data collection
Diffractometer	Bruker APEX area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2002 )
T_min, T_max	0.636, 0.907
No. of measured, independent and observed [I > 2σ(I)] reflections	21066, 6432, 4831
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.114, 1.05
No. of reflections	6432
No. of parameters	478
No. of restraints	31
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.48
Computer programs: SMART and SAINT (Bruker, 2002), SHELXS97, SHELXL97 and XP in SHELXTL (Sheldrick, 2008 ) and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1401557

Crystal structure: contains datablocks I, global. DOI: 10.1107/S2056989015009391/xu5850sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015009391/xu5850Isup2.hkl

checkCIF report

Chemical context top

It is known that oxamide ligands could be good candidates for forming polynuclear complexes because of their versatile coordinating abilities (Ojima & Nonoyama, 1988; Ruiz et al., 1999). Therefore, many oxamide complexes and their properties have been investigated extensively (Messori et al., 2003; Wang et al., 2013; Li et al., 2011). 1,10-Phenanthroline-5,6-dione (Phdo) is a multifaceted ligand since the structure and electronic properties thereof incorporate the features of the diimine and quinone functionalities (Girgis et al., 1975; Calderazzo et al., 2002). Consequently, as part of our systematic study of asymmetrical bis-substituent oxamide complexes and the influence of structures on the DNA-binding properties thereof (Li et al., 2012; Zhang et al., 2013), we selected N-[3-(dimethylamino)propyl]-N'-2-(oxidophenyl)oxamide (H₃Dmapox) as a bridging ligand and Phdo as a terminal ligand to synthesize the title binuclear copper(II) complex, [Cu₂(Dmapox)(Phdo)H₂O]⁺ClO₄^-.0.5H₂O. Its crystal structure and supramolecular structure are reported here.

Structural commentary top

The title compound consists of a binuclear Cu^II complex cation, a perchlorate anion and half of a solvent water molecule (Fig. 1). Two copper(II) ions are bridged by a cis-oxamido group. The Cu1 atom, located at the inner site of the oxamide ligand, has a distorted square-planar geometry and is displaced from the coordination plane by 0.0454 (15) Å, which is consistent with structures reported previously (Gao & Wang, 2010; Lu et al., 2011). The two exo-oxygen atoms of oxamide ligand and two nitrogen atoms of the Phdo molecule chelate the Cu2 atom to form the basal coordination plane [the maximum deviation being 0.0384 (14) Å for N4], and a water molecule (O4) occupies the apical position to complete the distorted square-pyramidal coordination geometry with τ value of 0.06 (Addison et al., 1984). The Cu—O distance of 2.213 (3) Å in the apical direction is longer than those in the basal plane by 0.261 (4) and 0.266 (4) Å (Table 1). The Cu2 atom is displaces by 0.1610 (15) Å off the basal plane towards the apex.

The hexadentate oxamide anion, Dmapox^3-, bridges the two copper(II) cations with three planar five-membered chelate rings and one six-membered, the latter is disordered over two parts. The puckering parameters of one part (containing atoms C10A and C11A) are Q = 0.554 (8) Å, θ = 47.6 (6)° and ϕ = 206.0 (7)°, and those of the other part are Q = 0.565 (11) Å, θ = 123.4 (8)° and ϕ = 38.8 (9)°; both suggest an approximate half-chair conformation.

Supramolecular features top

Besides classical O—H···O hydrogen bonds, weak C—H···O hydrogen bonds and aromatic stacking interactions are important to the supramolecular structure. As illustrated in Fig. 2, two symmetry-related binuclear cations link each other, forming a dimer by hydrogen bonds between the coordinating water molecules and phenolic oxygen atoms (Table 2). Then the dimers are assembled by perchlorate anions, generating a wave-like layer parallel to (100). Subsequently, an offset π–π stacking interaction occurs between the middle aromatic ring of the Phdo ligand of a binuclear unit and the benzene ring of the other unit at -x, 1 - y, -z [symmetry code (iv)], and vice versa (Fig. 3). The separations of the overlapped atoms to their opposite rings are 3.191 (4) (C2^iv), 3.211 (4) (C3^iv) and 3.252 (4) Å (C19^iv).

Database survey top

Several Cu^II complexes of 1,10-phenanthroline-5,6-dione have been reported previously, for example, Chetana et al. (2009); Galet et al. (2005); Saravani et al. (2007); Wang et al. (2013); Yamada et al. (2002) and Xu et al. (2006).

Synthesis and crystallization top

N-[3-(Dimethylamino)propyl]-N'-2-(oxidophenyl)oxamide (H₃Dmapox; Zhang et al., 2013) and 1,10-phenanthroline-5,6-dione (Phdo; Dickeson & Summers, 1970) were prepared by published procedures. The title compound was obtained as follows: A solution of Cu(ClO₄)₂^.6H₂O (0.0371 g, 0.1 mmol) in methanol (5 ml) was added dropwise to a solution of H₃Dmapox (0.0133 g, 0.05 mmol) and piperidine (0.0128 g, 0.15 mmol) in methanol (5 ml). The solution was stirred continuously for 0.5 h. Then a solution of Phdo (0.011 g, 0.05 mmol) in methanol (5 ml) was added dropwise, and the mixture was stirred continuously at 313 K for 6 h and then filtered. Dark-blue crystals of the title compound suitable for X-ray analysis were obtained from the filtrate by slow evaporation at room temperature for 7 d. Yield: 0.026 g (71.62%). Analysis calculated for Cu₂C₂₅H₂₅ClN₅O_10.5: C 41.44, H 3.48, N 9.67%; found: C 42.57, H 3.15, N 9.19%.

Refinement top

Disorder occurs for four carbon atoms of the 3-(dimethylamino)propyl group [C10A–C13A, with occupancies of 0.561 (11); C10B–C13B, 0.439 (11)], three oxygen atoms of perchlorate ion [O9A–O11A, 0.646 (8); O9B–O11B, 0.354 (8)], and the solvent water molecule (O7A, 0.207 (10); O7B, 0.293 (10)]. Their occupancies were refined freely except for the sum of atoms O7A and O7B which was fixed to 0.5. Some restraints on distances (DFIX) and anisotropic displacement parameters (SIMU) were applied to these disordered atoms to avoid unreasonable geometries. The hydrogen atoms of the water molecules were found in a difference Fourier map and then refined as riding. Other H atoms were placed in calculated positions, with C—H = 0.96 (methyl), 0.97 (methylene) and 0.93 Å (aromatic), and refined using a riding model, with U_iso(H) = 1.2 U_eq(C) or 1.5 for methyl groups.

Related literature top

For related literature, see: Addison et al. (1984); Calderazzo et al. (2002); Chetana et al. (2009); Dickeson & Summers (1970); Galet et al. (2005); Gao & Wang (2010); Girgis et al. (1975); Li et al. (2011, 2012); Lu et al. (2011); Messori et al. (2003); Ojima & Nonoyama (1988); Ruiz et al. (1999); Saravani et al. (2007); Wang et al. (2013); Xu et al. (2006); Yamada et al. (2002); Zhang et al. (2013).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level. For clarity, disordered atoms are represented in a different style and the H atoms on disordered carbon atoms have been omitted. Dashed lines indicate hydrogen bonds.
	Fig. 2. The two-dimensional wave-like hydrogen-bonding network constructed by classical O—H···O and weak C—H···O interactions [symmetry codes: (i) 1 - x, 1 - y, -z; (ii) x, 1/2 - y, z - 1/2; (iii) x, 1/2 - y, z + 1/2].
	Fig. 3. A perspective view of the π–π stacking interactions viewed perpendicular to the middle ring of the Phdo ligand. H atoms have been omitted for clarity [symmetry code: (iv) -x, 1 - y, -z].

Aqua{µ-N-[3-(dimethylamino)propyl]-N'-2-(oxidophenyl)oxamidato}(1,10-phenanthroline-5,6-dione)dicopper(II) perchlorate hemihydrate top

Crystal data top

[Cu₂(C₁₃H₁₆N₃O₃)(C₁₂H₆N₂O₂)(H₂O)]ClO₄·0.5H₂O	F(000) = 1476
M_r = 726.03	D_x = 1.699 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.7430 (6) Å	Cell parameters from 9065 reflections
b = 17.3066 (9) Å	θ = 3.2–27.4°
c = 14.1086 (8) Å	µ = 1.66 mm⁻¹
β = 98.154 (1)°	T = 296 K
V = 2838.3 (3) Å³	Prism, dark blue
Z = 4	0.30 × 0.12 × 0.06 mm

Data collection top

Bruker APEX area-detector diffractometer	6432 independent reflections
Radiation source: fine-focus sealed tube	4831 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→15
T_min = 0.636, T_max = 0.907	k = −22→22
21066 measured reflections	l = −15→18

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0369P)² + 7.4021P] where P = (F_o² + 2F_c²)/3
6432 reflections	(Δ/σ)_max < 0.001
478 parameters	Δρ_max = 0.76 e Å⁻³
31 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Cu₂(C₁₃H₁₆N₃O₃)(C₁₂H₆N₂O₂)(H₂O)]ClO₄·0.5H₂O	V = 2838.3 (3) Å³
M_r = 726.03	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.7430 (6) Å	µ = 1.66 mm⁻¹
b = 17.3066 (9) Å	T = 296 K
c = 14.1086 (8) Å	0.30 × 0.12 × 0.06 mm
β = 98.154 (1)°

Data collection top

Bruker APEX area-detector diffractometer	6432 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	4831 reflections with I > 2σ(I)
T_min = 0.636, T_max = 0.907	R_int = 0.054
21066 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	31 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.05	Δρ_max = 0.76 e Å⁻³
6432 reflections	Δρ_min = −0.47 e Å⁻³
478 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.48982 (4)	0.62884 (2)	0.02261 (3)	0.01855 (12)
Cu2	0.15568 (4)	0.46352 (3)	0.12248 (3)	0.01949 (12)
O1	0.5443 (2)	0.62076 (14)	−0.10126 (18)	0.0201 (5)
O2	0.2204 (2)	0.48428 (14)	0.00502 (19)	0.0202 (5)
O3	0.2675 (2)	0.53779 (14)	0.18328 (19)	0.0216 (6)
O4	0.2568 (2)	0.35877 (15)	0.1685 (2)	0.0260 (6)
H4A	0.3245	0.3523	0.1580	0.07 (2)*
H4B	0.2148	0.3146	0.1550	0.052 (16)*
O5	−0.3086 (2)	0.27160 (16)	0.1260 (2)	0.0326 (7)
O6	−0.2449 (3)	0.30625 (18)	0.3165 (2)	0.0376 (8)
N1	0.3763 (2)	0.55502 (16)	−0.0332 (2)	0.0174 (6)
N2	0.4133 (3)	0.61345 (17)	0.1376 (2)	0.0191 (6)
N3	0.5927 (3)	0.71698 (18)	0.0732 (2)	0.0255 (7)
N4	0.0213 (2)	0.40632 (17)	0.0548 (2)	0.0176 (6)
N5	0.0705 (3)	0.45017 (19)	0.2338 (2)	0.0254 (7)
C1	0.4728 (3)	0.5781 (2)	−0.1637 (3)	0.0193 (8)
C2	0.3778 (3)	0.54062 (19)	−0.1310 (3)	0.0176 (7)
C3	0.2998 (3)	0.4979 (2)	−0.1929 (3)	0.0214 (8)
H3	0.2375	0.4744	−0.1706	0.026*
C4	0.3151 (4)	0.4902 (2)	−0.2881 (3)	0.0270 (9)
H4	0.2625	0.4623	−0.3303	0.032*
C5	0.4095 (4)	0.5246 (2)	−0.3199 (3)	0.0286 (9)
H5	0.4205	0.5186	−0.3835	0.034*
C6	0.4876 (3)	0.5676 (2)	−0.2587 (3)	0.0249 (9)
H6	0.5506	0.5897	−0.2815	0.030*
C7	0.3069 (3)	0.52992 (19)	0.0233 (3)	0.0170 (7)
C8	0.3321 (3)	0.56215 (19)	0.1238 (3)	0.0178 (7)
C9	0.4368 (3)	0.6507 (2)	0.2314 (3)	0.0253 (9)
H9A	0.4864	0.6178	0.2751	0.030*	0.561 (11)
H9B	0.3653	0.6579	0.2573	0.030*	0.561 (11)
H9C	0.3716	0.6824	0.2419	0.030*	0.439 (11)
H9D	0.4476	0.6116	0.2811	0.030*	0.439 (11)
C10A	0.4950 (7)	0.7291 (5)	0.2231 (6)	0.0207 (19)	0.561 (11)
H10A	0.4427	0.7629	0.1829	0.025*	0.561 (11)
H10B	0.5105	0.7525	0.2861	0.025*	0.561 (11)
C11A	0.6069 (6)	0.7230 (5)	0.1811 (4)	0.0213 (19)	0.561 (11)
H11A	0.6536	0.7680	0.2007	0.026*	0.561 (11)
H11B	0.6485	0.6778	0.2082	0.026*	0.561 (11)
C12A	0.5468 (14)	0.7891 (6)	0.0286 (10)	0.046 (4)	0.561 (11)
H12A	0.5380	0.7839	−0.0398	0.069*	0.561 (11)
H12B	0.5990	0.8306	0.0483	0.069*	0.561 (11)
H12C	0.4734	0.7999	0.0482	0.069*	0.561 (11)
C13A	0.7114 (8)	0.7022 (15)	0.0540 (12)	0.043 (5)	0.561 (11)
H13A	0.7615	0.7421	0.0830	0.065*	0.561 (11)
H13B	0.7128	0.7020	−0.0139	0.065*	0.561 (11)
H13C	0.7370	0.6530	0.0803	0.065*	0.561 (11)
C10B	0.5434 (12)	0.6994 (6)	0.2379 (7)	0.032 (3)	0.439 (11)
H10C	0.6093	0.6651	0.2436	0.038*	0.439 (11)
H10D	0.5493	0.7294	0.2965	0.038*	0.439 (11)
C11B	0.5519 (11)	0.7548 (5)	0.1554 (8)	0.036 (3)	0.439 (11)
H11C	0.4768	0.7773	0.1348	0.043*	0.439 (11)
H11D	0.6041	0.7965	0.1778	0.043*	0.439 (11)
C12B	0.5760 (13)	0.7781 (7)	−0.0015 (9)	0.038 (4)	0.439 (11)
H12D	0.6208	0.8228	0.0204	0.057*	0.439 (11)
H12E	0.4962	0.7920	−0.0139	0.057*	0.439 (11)
H12F	0.6005	0.7591	−0.0593	0.057*	0.439 (11)
C13B	0.7162 (10)	0.6988 (17)	0.0870 (15)	0.035 (5)	0.439 (11)
H13D	0.7595	0.7447	0.1058	0.053*	0.439 (11)
H13E	0.7375	0.6796	0.0281	0.053*	0.439 (11)
H13F	0.7323	0.6603	0.1360	0.053*	0.439 (11)
C14	0.0027 (3)	0.3843 (2)	−0.0364 (3)	0.0206 (8)
H14	0.0530	0.4014	−0.0773	0.025*
C15	−0.0881 (3)	0.3370 (2)	−0.0734 (3)	0.0231 (8)
H15	−0.0984	0.3228	−0.1376	0.028*
C16	−0.1632 (3)	0.3114 (2)	−0.0128 (3)	0.0227 (8)
H16	−0.2245	0.2792	−0.0355	0.027*
C17	−0.1456 (3)	0.3344 (2)	0.0822 (3)	0.0183 (7)
C18	−0.2225 (3)	0.3083 (2)	0.1514 (3)	0.0234 (8)
C19	−0.1890 (3)	0.3309 (2)	0.2573 (3)	0.0287 (9)
C20	−0.0860 (3)	0.3801 (2)	0.2846 (3)	0.0251 (8)
C21	−0.0471 (4)	0.4002 (3)	0.3791 (3)	0.0375 (11)
H21	−0.0859	0.3833	0.4283	0.045*
C22	0.0503 (4)	0.4458 (3)	0.3987 (3)	0.0455 (13)
H22	0.0783	0.4595	0.4614	0.055*
C23	0.1057 (4)	0.4706 (3)	0.3236 (3)	0.0387 (11)
H23	0.1695	0.5027	0.3368	0.046*
C24	−0.0232 (3)	0.4052 (2)	0.2139 (3)	0.0210 (8)
C25	−0.0521 (3)	0.3817 (2)	0.1138 (3)	0.0170 (7)
Cl1	0.04798 (9)	0.17375 (5)	0.17883 (7)	0.0275 (2)
O8	0.0854 (3)	0.1132 (2)	0.2436 (3)	0.0567 (10)
O9A	0.0082 (6)	0.2341 (3)	0.2331 (4)	0.054 (2)	0.646 (8)
O10A	−0.0380 (7)	0.1519 (4)	0.1034 (4)	0.060 (2)	0.646 (8)
O11A	0.1412 (6)	0.2040 (4)	0.1353 (5)	0.073 (2)	0.646 (8)
O9B	0.0505 (16)	0.1419 (9)	0.0878 (5)	0.112 (6)	0.354 (8)
O10B	0.1088 (10)	0.2417 (4)	0.1984 (12)	0.094 (6)	0.354 (8)
O11B	−0.0679 (5)	0.1910 (5)	0.1922 (7)	0.037 (3)	0.354 (8)
O7A	0.3514 (15)	0.5296 (11)	0.4141 (15)	0.056 (7)	0.207 (10)
H7A	0.3589	0.5251	0.3546	0.084*	0.207 (10)
H7B	0.4122	0.5110	0.4473	0.084*	0.207 (10)
O7B	0.282 (2)	0.5932 (11)	0.4515 (15)	0.146 (13)	0.293 (10)
H7C	0.2845	0.5848	0.5119	0.219*	0.293 (10)
H7D	0.2685	0.6416	0.4416	0.219*	0.293 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0132 (2)	0.0162 (2)	0.0274 (3)	−0.00272 (17)	0.00678 (18)	−0.00401 (18)
Cu2	0.0134 (2)	0.0205 (2)	0.0258 (3)	−0.00197 (18)	0.00698 (18)	−0.00077 (19)
O1	0.0139 (12)	0.0220 (13)	0.0252 (14)	−0.0045 (10)	0.0057 (11)	−0.0014 (11)
O2	0.0151 (12)	0.0197 (12)	0.0263 (14)	−0.0049 (10)	0.0053 (11)	−0.0003 (11)
O3	0.0186 (13)	0.0209 (12)	0.0270 (15)	−0.0024 (11)	0.0091 (11)	−0.0006 (11)
O4	0.0175 (14)	0.0236 (14)	0.0387 (17)	0.0015 (11)	0.0103 (12)	0.0083 (12)
O5	0.0260 (16)	0.0291 (15)	0.0463 (19)	−0.0087 (13)	0.0173 (14)	0.0000 (14)
O6	0.0327 (17)	0.0443 (18)	0.0399 (18)	−0.0003 (14)	0.0185 (15)	0.0153 (15)
N1	0.0135 (14)	0.0147 (14)	0.0245 (17)	0.0001 (12)	0.0041 (13)	−0.0010 (12)
N2	0.0159 (15)	0.0180 (15)	0.0235 (17)	0.0007 (12)	0.0028 (13)	−0.0013 (13)
N3	0.0198 (17)	0.0250 (16)	0.0334 (19)	−0.0058 (14)	0.0091 (15)	−0.0092 (15)
N4	0.0117 (14)	0.0198 (15)	0.0220 (17)	0.0017 (12)	0.0046 (12)	0.0032 (13)
N5	0.0196 (16)	0.0308 (17)	0.0268 (19)	0.0016 (14)	0.0061 (14)	−0.0042 (15)
C1	0.0145 (17)	0.0147 (16)	0.029 (2)	0.0046 (14)	0.0047 (15)	0.0007 (15)
C2	0.0123 (16)	0.0141 (16)	0.026 (2)	0.0015 (14)	0.0026 (15)	−0.0002 (15)
C3	0.0178 (18)	0.0181 (17)	0.028 (2)	−0.0005 (15)	0.0038 (16)	−0.0008 (15)
C4	0.024 (2)	0.0250 (19)	0.031 (2)	−0.0017 (17)	0.0011 (17)	−0.0070 (17)
C5	0.030 (2)	0.030 (2)	0.028 (2)	−0.0003 (18)	0.0109 (18)	−0.0026 (18)
C6	0.0203 (19)	0.0229 (18)	0.033 (2)	0.0003 (16)	0.0096 (17)	0.0025 (17)
C7	0.0112 (16)	0.0127 (15)	0.027 (2)	0.0016 (13)	0.0026 (14)	0.0017 (14)
C8	0.0140 (17)	0.0151 (16)	0.025 (2)	0.0023 (14)	0.0053 (15)	0.0000 (14)
C9	0.024 (2)	0.0260 (19)	0.027 (2)	−0.0045 (16)	0.0062 (17)	−0.0065 (16)
C10A	0.020 (4)	0.020 (4)	0.023 (4)	−0.002 (3)	0.005 (3)	−0.010 (3)
C11A	0.018 (4)	0.018 (4)	0.030 (4)	0.000 (3)	0.007 (3)	−0.009 (3)
C12A	0.067 (10)	0.018 (5)	0.050 (7)	−0.001 (5)	0.001 (6)	0.000 (5)
C13A	0.021 (5)	0.060 (8)	0.052 (11)	−0.024 (5)	0.013 (5)	−0.036 (9)
C10B	0.033 (7)	0.031 (6)	0.031 (6)	−0.002 (5)	0.004 (5)	−0.006 (5)
C11B	0.035 (7)	0.014 (5)	0.063 (8)	−0.002 (5)	0.019 (6)	−0.016 (5)
C12B	0.019 (7)	0.012 (5)	0.075 (12)	0.002 (4)	−0.022 (7)	−0.015 (6)
C13B	0.028 (6)	0.036 (6)	0.039 (12)	0.001 (5)	−0.006 (5)	−0.017 (9)
C14	0.0168 (18)	0.0226 (18)	0.024 (2)	0.0008 (15)	0.0068 (15)	0.0026 (15)
C15	0.023 (2)	0.0248 (19)	0.022 (2)	0.0029 (16)	0.0036 (16)	0.0012 (16)
C16	0.0124 (17)	0.0209 (18)	0.034 (2)	0.0026 (15)	0.0019 (16)	0.0039 (16)
C17	0.0129 (17)	0.0174 (16)	0.025 (2)	0.0002 (14)	0.0043 (15)	0.0030 (15)
C18	0.0176 (19)	0.0184 (17)	0.037 (2)	0.0048 (15)	0.0111 (17)	0.0071 (16)
C19	0.025 (2)	0.030 (2)	0.034 (2)	0.0055 (17)	0.0153 (18)	0.0113 (18)
C20	0.0212 (19)	0.029 (2)	0.026 (2)	0.0060 (17)	0.0095 (16)	0.0049 (17)
C21	0.031 (2)	0.059 (3)	0.025 (2)	0.008 (2)	0.0125 (19)	0.002 (2)
C22	0.032 (3)	0.079 (4)	0.026 (2)	−0.001 (3)	0.008 (2)	−0.013 (2)
C23	0.027 (2)	0.058 (3)	0.032 (3)	−0.004 (2)	0.0057 (19)	−0.013 (2)
C24	0.0140 (17)	0.0241 (18)	0.026 (2)	0.0037 (15)	0.0046 (15)	0.0021 (16)
C25	0.0116 (16)	0.0181 (17)	0.0220 (19)	0.0047 (14)	0.0049 (14)	0.0021 (14)
Cl1	0.0283 (5)	0.0253 (5)	0.0290 (5)	0.0042 (4)	0.0048 (4)	0.0013 (4)
O8	0.050 (2)	0.053 (2)	0.067 (3)	0.0233 (19)	0.0091 (19)	0.026 (2)
O9A	0.087 (6)	0.042 (3)	0.035 (3)	0.027 (4)	0.018 (3)	−0.001 (3)
O10A	0.075 (5)	0.063 (4)	0.037 (4)	−0.009 (4)	−0.015 (3)	0.002 (3)
O11A	0.089 (5)	0.066 (4)	0.076 (5)	−0.040 (4)	0.056 (4)	−0.018 (4)
O9B	0.111 (13)	0.175 (15)	0.048 (8)	0.063 (11)	0.006 (8)	−0.056 (9)
O10B	0.049 (7)	0.038 (6)	0.196 (16)	−0.019 (6)	0.024 (9)	0.008 (9)
O11B	0.016 (4)	0.043 (6)	0.051 (6)	0.009 (4)	0.001 (4)	0.016 (5)
O7A	0.043 (11)	0.056 (13)	0.073 (14)	0.001 (9)	0.022 (9)	0.000 (10)
O7B	0.27 (3)	0.065 (13)	0.096 (16)	−0.036 (17)	−0.008 (18)	0.009 (11)

Geometric parameters (Å, º) top

Cu1—O1	1.950 (3)	C10A—H10B	0.9700
Cu1—N1	1.932 (3)	C11A—H11A	0.9700
Cu1—N2	1.982 (3)	C11A—H11B	0.9700
Cu1—N3	2.013 (3)	C12A—H12A	0.9600
Cu2—O2	1.952 (3)	C12A—H12B	0.9600
Cu2—O3	1.947 (3)	C12A—H12C	0.9600
Cu2—O4	2.213 (3)	C13A—H13A	0.9600
Cu2—N4	1.989 (3)	C13A—H13B	0.9600
Cu2—N5	1.991 (3)	C13A—H13C	0.9600
O1—C1	1.347 (4)	C10B—C11B	1.522 (9)
O2—C7	1.284 (4)	C10B—H10C	0.9700
O3—C8	1.280 (4)	C10B—H10D	0.9700
O4—H4A	0.8374	C11B—H11C	0.9700
O4—H4B	0.9146	C11B—H11D	0.9700
O5—C18	1.205 (5)	C12B—H12D	0.9600
O6—C19	1.211 (5)	C12B—H12E	0.9600
N1—C7	1.293 (4)	C12B—H12F	0.9600
N1—C2	1.405 (5)	C13B—H13D	0.9600
N2—C8	1.297 (4)	C13B—H13E	0.9600
N2—C9	1.463 (5)	C13B—H13F	0.9600
N3—C12A	1.465 (8)	C14—C15	1.385 (5)
N3—C13B	1.470 (9)	C14—H14	0.9300
N3—C11B	1.470 (10)	C15—C16	1.386 (5)
N3—C13A	1.480 (8)	C15—H15	0.9300
N3—C12B	1.487 (9)	C16—C17	1.386 (5)
N3—C11A	1.511 (6)	C16—H16	0.9300
N4—C14	1.331 (5)	C17—C25	1.390 (5)
N4—C25	1.349 (4)	C17—C18	1.491 (5)
N5—C23	1.324 (5)	C18—C19	1.541 (6)
N5—C24	1.345 (5)	C19—C20	1.484 (6)
C1—C6	1.388 (5)	C20—C21	1.391 (6)
C1—C2	1.423 (5)	C20—C24	1.391 (5)
C2—C3	1.386 (5)	C21—C22	1.384 (7)
C3—C4	1.387 (6)	C21—H21	0.9300
C3—H3	0.9300	C22—C23	1.388 (6)
C4—C5	1.388 (5)	C22—H22	0.9300
C4—H4	0.9300	C23—H23	0.9300
C5—C6	1.385 (6)	C24—C25	1.463 (5)
C5—H5	0.9300	Cl1—O10B	1.383 (5)
C6—H6	0.9300	Cl1—O9B	1.401 (5)
C7—C8	1.513 (5)	Cl1—O10A	1.411 (6)
C9—C10B	1.501 (11)	Cl1—O9A	1.413 (5)
C9—C10A	1.532 (8)	Cl1—O8	1.419 (3)
C9—H9A	0.9700	Cl1—O11A	1.429 (4)
C9—H9B	0.9700	Cl1—O11B	1.432 (5)
C9—H9C	0.9700	O7A—H7A	0.8596
C9—H9D	0.9700	O7A—H7B	0.8602
C10A—C11A	1.519 (7)	O7B—H7C	0.8602
C10A—H10A	0.9700	O7B—H7D	0.8603

O1—Cu1—N1	83.25 (11)	H10A—C10A—H10B	107.8
O1—Cu1—N2	165.77 (11)	N3—C11A—C10A	114.8 (6)
O1—Cu1—N3	96.65 (11)	N3—C11A—H11A	108.6
N1—Cu1—N2	83.00 (13)	C10A—C11A—H11A	108.6
N1—Cu1—N3	172.12 (13)	N3—C11A—H11B	108.6
N2—Cu1—N3	97.48 (13)	C10A—C11A—H11B	108.6
O2—Cu2—O3	86.16 (10)	H11A—C11A—H11B	107.6
O2—Cu2—N4	93.58 (11)	N3—C12A—H12A	109.5
O2—Cu2—N5	172.09 (12)	N3—C12A—H12B	109.5
O3—Cu2—N4	168.40 (11)	N3—C12A—H12C	109.5
O3—Cu2—N5	96.42 (12)	N3—C13A—H13A	109.5
N4—Cu2—N5	82.38 (13)	N3—C13A—H13B	109.5
O4—Cu2—O2	98.20 (10)	N3—C13A—H13C	109.5
O4—Cu2—O3	96.39 (11)	C9—C10B—C11B	116.9 (9)
O4—Cu2—N4	95.12 (11)	C9—C10B—H10C	108.1
O4—Cu2—N5	88.97 (12)	C11B—C10B—H10C	108.1
C1—O1—Cu1	111.8 (2)	C9—C10B—H10D	108.1
C7—O2—Cu2	109.6 (2)	C11B—C10B—H10D	108.1
C8—O3—Cu2	110.7 (2)	H10C—C10B—H10D	107.3
Cu2—O4—H4A	122.8	N3—C11B—C10B	112.7 (9)
Cu2—O4—H4B	111.8	N3—C11B—H11C	109.0
H4A—O4—H4B	110.4	C10B—C11B—H11C	109.0
C7—N1—C2	130.0 (3)	N3—C11B—H11D	109.0
C7—N1—Cu1	115.4 (3)	C10B—C11B—H11D	109.0
C2—N1—Cu1	114.4 (2)	H11C—C11B—H11D	107.8
C8—N2—C9	118.6 (3)	N3—C12B—H12D	109.5
C8—N2—Cu1	112.2 (2)	N3—C12B—H12E	109.5
C9—N2—Cu1	129.2 (2)	H12D—C12B—H12E	109.5
C13B—N3—C11B	114.7 (10)	N3—C12B—H12F	109.5
C12A—N3—C13A	111.5 (11)	H12D—C12B—H12F	109.5
C13B—N3—C12B	105.8 (12)	H12E—C12B—H12F	109.5
C11B—N3—C12B	102.6 (7)	N3—C13B—H13D	109.5
C12A—N3—C11A	110.8 (6)	N3—C13B—H13E	109.5
C13A—N3—C11A	103.0 (7)	H13D—C13B—H13E	109.5
C12A—N3—Cu1	109.1 (7)	N3—C13B—H13F	109.5
C13B—N3—Cu1	114.6 (12)	H13D—C13B—H13F	109.5
C11B—N3—Cu1	111.8 (4)	H13E—C13B—H13F	109.5
C13A—N3—Cu1	109.7 (9)	N4—C14—C15	123.0 (3)
C12B—N3—Cu1	106.0 (6)	N4—C14—H14	118.5
C11A—N3—Cu1	112.6 (3)	C15—C14—H14	118.5
C14—N4—C25	118.3 (3)	C14—C15—C16	118.7 (4)
C14—N4—Cu2	128.1 (2)	C14—C15—H15	120.6
C25—N4—Cu2	113.2 (2)	C16—C15—H15	120.6
C23—N5—C24	119.3 (4)	C17—C16—C15	118.9 (4)
C23—N5—Cu2	126.9 (3)	C17—C16—H16	120.6
C24—N5—Cu2	113.0 (3)	C15—C16—H16	120.6
O1—C1—C6	123.5 (3)	C16—C17—C25	118.8 (3)
O1—C1—C2	118.8 (3)	C16—C17—C18	121.7 (3)
C6—C1—C2	117.6 (3)	C25—C17—C18	119.5 (3)
C3—C2—N1	127.9 (3)	O5—C18—C17	121.8 (4)
C3—C2—C1	121.2 (3)	O5—C18—C19	120.6 (3)
N1—C2—C1	110.9 (3)	C17—C18—C19	117.6 (3)
C2—C3—C4	119.8 (3)	O6—C19—C20	121.7 (4)
C2—C3—H3	120.1	O6—C19—C18	119.4 (4)
C4—C3—H3	120.1	C20—C19—C18	118.9 (3)
C3—C4—C5	119.4 (4)	C21—C20—C24	118.3 (4)
C3—C4—H4	120.3	C21—C20—C19	122.5 (4)
C5—C4—H4	120.3	C24—C20—C19	119.2 (4)
C6—C5—C4	121.2 (4)	C22—C21—C20	118.9 (4)
C6—C5—H5	119.4	C22—C21—H21	120.5
C4—C5—H5	119.4	C20—C21—H21	120.5
C5—C6—C1	120.7 (4)	C21—C22—C23	119.2 (4)
C5—C6—H6	119.7	C21—C22—H22	120.4
C1—C6—H6	119.7	C23—C22—H22	120.4
O2—C7—N1	129.3 (4)	N5—C23—C22	122.1 (4)
O2—C7—C8	117.3 (3)	N5—C23—H23	119.0
N1—C7—C8	113.4 (3)	C22—C23—H23	119.0
O3—C8—N2	128.1 (3)	N5—C24—C20	122.1 (4)
O3—C8—C7	116.0 (3)	N5—C24—C25	115.7 (3)
N2—C8—C7	115.8 (3)	C20—C24—C25	122.1 (3)
N2—C9—C10B	110.6 (5)	N4—C25—C17	122.2 (3)
N2—C9—C10A	110.5 (4)	N4—C25—C24	115.2 (3)
N2—C9—H9A	109.6	C17—C25—C24	122.5 (3)
C10A—C9—H9A	109.6	O10B—Cl1—O9B	116.1 (10)
N2—C9—H9B	109.6	O10A—Cl1—O9A	110.6 (4)
C10A—C9—H9B	109.6	O10B—Cl1—O8	113.3 (6)
H9A—C9—H9B	108.1	O9B—Cl1—O8	104.8 (5)
N2—C9—H9C	109.6	O10A—Cl1—O8	114.2 (3)
C10B—C9—H9C	109.9	O9A—Cl1—O8	107.0 (3)
N2—C9—H9D	109.6	O10A—Cl1—O11A	106.5 (4)
C10B—C9—H9D	109.0	O9A—Cl1—O11A	107.2 (4)
H9C—C9—H9D	108.1	O8—Cl1—O11A	111.2 (4)
C11A—C10A—C9	112.8 (6)	O10B—Cl1—O11B	105.7 (7)
C11A—C10A—H10A	109.0	O9B—Cl1—O11B	110.3 (8)
C9—C10A—H10A	109.0	O8—Cl1—O11B	106.4 (4)
C11A—C10A—H10B	109.0	H7A—O7A—H7B	107.8
C9—C10A—H10B	109.0	H7C—O7B—H7D	107.8

N1—Cu1—O1—C1	7.0 (2)	Cu2—O3—C8—N2	177.6 (3)
N2—Cu1—O1—C1	22.0 (6)	Cu2—O3—C8—C7	0.8 (4)
N3—Cu1—O1—C1	−165.1 (2)	C9—N2—C8—O3	−0.8 (6)
O3—Cu2—O2—C7	4.6 (2)	Cu1—N2—C8—O3	178.8 (3)
N4—Cu2—O2—C7	173.0 (2)	C9—N2—C8—C7	176.0 (3)
O4—Cu2—O2—C7	−91.3 (2)	Cu1—N2—C8—C7	−4.4 (4)
O2—Cu2—O3—C8	−2.9 (2)	O2—C7—C8—O3	3.3 (5)
N4—Cu2—O3—C8	−92.0 (6)	N1—C7—C8—O3	−178.5 (3)
N5—Cu2—O3—C8	−175.4 (2)	O2—C7—C8—N2	−174.0 (3)
O4—Cu2—O3—C8	94.9 (2)	N1—C7—C8—N2	4.3 (4)
O1—Cu1—N1—C7	176.1 (3)	C8—N2—C9—C10B	172.0 (6)
N2—Cu1—N1—C7	−0.2 (3)	Cu1—N2—C9—C10B	−7.5 (7)
O1—Cu1—N1—C2	−7.7 (2)	C8—N2—C9—C10A	−156.4 (5)
N2—Cu1—N1—C2	176.0 (2)	Cu1—N2—C9—C10A	24.1 (6)
N1—Cu1—N2—C8	2.7 (2)	N2—C9—C10A—C11A	−58.1 (8)
O1—Cu1—N2—C8	−12.3 (6)	C12A—N3—C11A—C10A	67.3 (10)
N3—Cu1—N2—C8	174.8 (2)	C13A—N3—C11A—C10A	−173.3 (12)
N1—Cu1—N2—C9	−177.8 (3)	Cu1—N3—C11A—C10A	−55.2 (7)
O1—Cu1—N2—C9	167.2 (4)	C9—C10A—C11A—N3	80.9 (9)
N3—Cu1—N2—C9	−5.7 (3)	N2—C9—C10B—C11B	48.9 (12)
O1—Cu1—N3—C12A	76.8 (6)	C13B—N3—C11B—C10B	−74.4 (16)
N2—Cu1—N3—C12A	−105.0 (6)	C12B—N3—C11B—C10B	171.4 (11)
O1—Cu1—N3—C13B	−64.5 (10)	Cu1—N3—C11B—C10B	58.2 (11)
N2—Cu1—N3—C13B	113.8 (10)	C9—C10B—C11B—N3	−82.3 (14)
O1—Cu1—N3—C11B	162.9 (5)	C25—N4—C14—C15	−0.3 (5)
N2—Cu1—N3—C11B	−18.9 (6)	Cu2—N4—C14—C15	172.5 (3)
O1—Cu1—N3—C13A	−45.6 (9)	N4—C14—C15—C16	0.0 (6)
N2—Cu1—N3—C13A	132.6 (9)	C14—C15—C16—C17	0.6 (5)
O1—Cu1—N3—C12B	51.8 (6)	C15—C16—C17—C25	−0.8 (5)
N2—Cu1—N3—C12B	−129.9 (6)	C15—C16—C17—C18	−179.4 (3)
O1—Cu1—N3—C11A	−159.7 (4)	C16—C17—C18—O5	−6.4 (6)
N2—Cu1—N3—C11A	18.6 (4)	C25—C17—C18—O5	175.0 (3)
O3—Cu2—N4—C14	96.8 (6)	C16—C17—C18—C19	174.4 (3)
O2—Cu2—N4—C14	8.5 (3)	C25—C17—C18—C19	−4.2 (5)
N5—Cu2—N4—C14	−178.4 (3)	O5—C18—C19—O6	5.9 (6)
O4—Cu2—N4—C14	−90.1 (3)	C17—C18—C19—O6	−174.9 (3)
O3—Cu2—N4—C25	−90.1 (6)	O5—C18—C19—C20	−176.5 (3)
O2—Cu2—N4—C25	−178.5 (2)	C17—C18—C19—C20	2.7 (5)
N5—Cu2—N4—C25	−5.3 (2)	O6—C19—C20—C21	0.5 (6)
O4—Cu2—N4—C25	83.0 (2)	C18—C19—C20—C21	−177.1 (4)
O3—Cu2—N5—C23	−15.8 (4)	O6—C19—C20—C24	178.4 (4)
N4—Cu2—N5—C23	175.8 (4)	C18—C19—C20—C24	0.8 (5)
O4—Cu2—N5—C23	80.5 (4)	C24—C20—C21—C22	1.6 (6)
O3—Cu2—N5—C24	174.7 (3)	C19—C20—C21—C22	179.5 (4)
N4—Cu2—N5—C24	6.4 (3)	C20—C21—C22—C23	0.6 (7)
O4—Cu2—N5—C24	−88.9 (3)	C24—N5—C23—C22	1.4 (7)
Cu1—O1—C1—C6	175.6 (3)	Cu2—N5—C23—C22	−167.4 (4)
Cu1—O1—C1—C2	−5.4 (4)	C21—C22—C23—N5	−2.2 (8)
C7—N1—C2—C3	3.4 (6)	C23—N5—C24—C20	0.9 (6)
Cu1—N1—C2—C3	−172.1 (3)	Cu2—N5—C24—C20	171.2 (3)
C7—N1—C2—C1	−177.8 (3)	C23—N5—C24—C25	−176.6 (4)
Cu1—N1—C2—C1	6.6 (4)	Cu2—N5—C24—C25	−6.3 (4)
O1—C1—C2—C3	178.2 (3)	C21—C20—C24—N5	−2.4 (6)
C6—C1—C2—C3	−2.8 (5)	C19—C20—C24—N5	179.6 (3)
O1—C1—C2—N1	−0.7 (4)	C21—C20—C24—C25	175.0 (4)
C6—C1—C2—N1	178.3 (3)	C19—C20—C24—C25	−3.0 (5)
N1—C2—C3—C4	179.7 (3)	C14—N4—C25—C17	0.0 (5)
C1—C2—C3—C4	1.0 (5)	Cu2—N4—C25—C17	−173.8 (3)
C2—C3—C4—C5	1.0 (6)	C14—N4—C25—C24	177.2 (3)
C3—C4—C5—C6	−1.2 (6)	Cu2—N4—C25—C24	3.4 (4)
C4—C5—C6—C1	−0.6 (6)	C16—C17—C25—N4	0.5 (5)
O1—C1—C6—C5	−178.5 (3)	C18—C17—C25—N4	179.1 (3)
C2—C1—C6—C5	2.6 (5)	C16—C17—C25—C24	−176.4 (3)
Cu2—O2—C7—N1	176.7 (3)	C18—C17—C25—C24	2.2 (5)
Cu2—O2—C7—C8	−5.4 (4)	N5—C24—C25—N4	2.0 (5)
C2—N1—C7—O2	0.5 (6)	C20—C24—C25—N4	−175.6 (3)
Cu1—N1—C7—O2	176.1 (3)	N5—C24—C25—C17	179.2 (3)
C2—N1—C7—C8	−177.5 (3)	C20—C24—C25—C17	1.6 (5)
Cu1—N1—C7—C8	−1.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1ⁱ	0.84	1.89	2.666 (3)	153
O4—H4B···O10B	0.91	1.93	2.740 (8)	146
O4—H4B···O11A	0.91	2.10	3.009 (7)	171
O7A—H7A···O3	0.86	2.51	3.27 (2)	147
O7B—H7D···O5ⁱⁱ	0.86	2.51	3.305 (18)	153
C3—H3···O8ⁱⁱⁱ	0.93	2.52	3.193 (5)	130
C15—H15···O9Aⁱⁱⁱ	0.93	2.55	3.335 (7)	142
C15—H15···O11Bⁱⁱⁱ	0.93	2.49	3.384 (10)	162
C16—H16···O6ⁱⁱⁱ	0.93	2.54	3.195 (5)	128
C10A—H10A···O6ⁱⁱ	0.97	2.44	3.202 (9)	135
C11A—H11A···O4^iv	0.97	2.54	3.409 (7)	150
C13A—H13B···O4ⁱ	0.96	2.49	3.382 (16)	154
C21—H21···O10A^v	0.93	2.53	3.277 (8)	138
C23—H23···O7A	0.93	2.30	3.154 (19)	152
C23—H23···O7B	0.93	2.49	3.31 (2)	147

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, y+1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2; (v) x, −y+1/2, z+1/2.

Selected bond lengths (Å) top

Cu1—O1	1.950 (3)	Cu2—O3	1.947 (3)
Cu1—N1	1.932 (3)	Cu2—O4	2.213 (3)
Cu1—N2	1.982 (3)	Cu2—N4	1.989 (3)
Cu1—N3	2.013 (3)	Cu2—N5	1.991 (3)
Cu2—O2	1.952 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···O1ⁱ	0.84	1.89	2.666 (3)	153.2
O4—H4B···O10B	0.91	1.93	2.740 (8)	146.3
O4—H4B···O11A	0.91	2.10	3.009 (7)	170.9
O7A—H7A···O3	0.86	2.51	3.27 (2)	147.4
O7B—H7D···O5ⁱⁱ	0.86	2.51	3.305 (18)	153.4
C3—H3···O8ⁱⁱⁱ	0.93	2.52	3.193 (5)	129.7
C15—H15···O9Aⁱⁱⁱ	0.93	2.55	3.335 (7)	142.1
C15—H15···O11Bⁱⁱⁱ	0.93	2.49	3.384 (10)	161.6
C16—H16···O6ⁱⁱⁱ	0.93	2.54	3.195 (5)	127.6
C10A—H10A···O6ⁱⁱ	0.97	2.44	3.202 (9)	135.0
C11A—H11A···O4^iv	0.97	2.54	3.409 (7)	149.8
C13A—H13B···O4ⁱ	0.96	2.49	3.382 (16)	154.1
C21—H21···O10A^v	0.93	2.53	3.277 (8)	137.8
C23—H23···O7A	0.93	2.30	3.154 (19)	151.9
C23—H23···O7B	0.93	2.49	3.31 (2)	147.4

Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, y+1/2, −z+1/2; (iii) x, −y+1/2, z−1/2; (iv) −x+1, y+1/2, −z+1/2; (v) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₃H₁₆N₃O₃)(C₁₂H₆N₂O₂)(H₂O)]ClO₄·0.5H₂O
M_r	726.03
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.7430 (6), 17.3066 (9), 14.1086 (8)
β (°)	98.154 (1)
V (Å³)	2838.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.66
Crystal size (mm)	0.30 × 0.12 × 0.06

Data collection
Diffractometer	Bruker APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.636, 0.907
No. of measured, independent and observed [I > 2σ(I)] reflections	21066, 6432, 4831
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.114, 1.05
No. of reflections	6432
No. of parameters	478
No. of restraints	31
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.47

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 2012).

Acknowledgements

This project was supported by the Fundamental Research Funds for the Central Universities, China (grant No. 201213020) and the Program for Science and Technology of Shandong Province, China (grant No. 2012GHY11525).

References

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Volume 71| Part 6| June 2015| Pages 667-670

doi:10.1107/S2056989015009391

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of aqua­{μ-N-[3-(di­methyl­amino)­prop­yl]-N′-2-(oxidophen­yl)oxamidato}(1,10-phen­anthroline-5,6-dione)dicopper(II) perchlorate hemihydrate

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of aqua{μ-N-[3-(dimethylamino)propyl]-N′-2-(oxidophenyl)oxamidato}(1,10-phenanthroline-5,6-dione)dicopper(II) perchlorate hemihydrate

3. Supramolecular features