Di-μ2-acetato-1:2κ2O:O′;2:3κ2O:O′-bis­{μ2-4,4′-dichloro-2,2′-[2,2-dimethyl­propane-1,3-diylbis(nitrilo­methanylyl­idene)]diphenolato}-1:2κ6O,N,N′,O′:O,O′;2:3κ6O,O′:O,N,N′,O′-tricopper(II)

Kubono, K.; Tani, K.; Yokoi, K.

doi:10.1107/S1600536812044315

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 11| November 2012| Pages m1430-m1431

doi:10.1107/S1600536812044315

Open

access

Di-μ₂-acetato-1:2κ²O:O′;2:3κ²O:O′-bis{μ₂-4,4′-dichloro-2,2′-[2,2-dimethylpropane-1,3-diylbis(nitrilomethanylylidene)]diphenolato}-1:2κ⁶O,N,N′,O′:O,O′;2:3κ⁶O,O′:O,N,N′,O′-tricopper(II)

Koji Kubono,^a ^* Keita Tani ^a and Kunihiko Yokoi ^a

^aDivision of Natural Sciences, Osaka Kyoiku University, Kashiwara, Osaka 582-8582, Japan
^*Correspondence e-mail: kubono@cc.osaka-kyoiku.ac.jp

(Received 16 October 2012; accepted 25 October 2012; online 31 October 2012)

The title compound, [Cu₃(C₁₉H₁₈Cl₂N₂O₂)₂(CH₃CO₂)₂], is a linear homo-trinuclear Cu^II complex. The central Cu^II atom is located on a centre of inversion and has a distorted octahedral coordination environment formed by six O atoms from two tetradentate Schiff base ligands and two bridging acetate ligands. The coordination geometry of the terminal Cu^II atom is square-pyramidal with a tetradentate ligand in the basal plane. The apical site is occupied by one O atom from an acetate ligand. The acetate-bridged Cu⋯Cu distance is 3.0910 (5) Å. An intramolecular C—H⋯O hydrogen bond forms an S(6) ring motif. The crystal of the trinuclear complex is stabilized by C—H⋯O hydrogen bonds.

Related literature

For the supramolecular chemistry of related complexes, see: Chen et al. (2010 ); von Richthofen et al. (2009 ); Gianneschi et al. (2003 ). For related structures, see: Atakol et al. (1999 ); Feng et al. (2007 ); Ray et al. (2009 ); Yang et al. (2004 ). For background to this work, see: Fukuhara et al. (1990 ); Kargar et al. (2012 ); Kubono et al. (2009 , 2010 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For analysis of ring conformations, see: Cremer & Pople (1975 ).

Experimental

Crystal data

[Cu₃(C₁₉H₁₈Cl₂N₂O₂)₂(C₂H₃O₂)₂]
M_r = 1063.25
Orthorhombic, P b c a
a = 19.0732 (18) Å
b = 11.6191 (11) Å
c = 19.693 (3) Å
V = 4364.2 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.75 mm⁻¹
T = 298 K
0.23 × 0.20 × 0.16 mm

Data collection

Rigaku AFC7R diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.675, T_max = 0.756
7325 measured reflections
5006 independent reflections
2796 reflections with F² > 2.0σ(F²)
R_int = 0.024
3 standard reflections every 150 reflections intensity decay: 0.5%

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.105
S = 1.00
5006 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O4ⁱ	0.93	2.58	3.115 (4)	117
C15—H15⋯O3ⁱⁱ	0.93	2.59	3.289 (4)	133
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2010 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: CrystalStructure.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812044315/mw2092sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812044315/mw2092Isup2.hkl

checkCIF report

Comment top

Supramolecular complexes, formed by hydrogen bonds or coordination linkages have received much attention, because of their interesting and functional properties such as molecular recognition, magnetism and catalysis (Chen et al., 2010; von Richthofen et al., 2009; Gianneschi et al., 2003). We have previously studied the structures of supramolecular Cu^II complexes with planar tetradentate piperazine ligands containing fluoro or chloro groups (Kubono et al., 2010; Kubono et al., 2009). These Cu^II complexes form either a dimer, or a dinuclear structure through C—H···F, or C—H···Cl hydrogen bonds. Complexes with the tetradentate Schiff base ligand, bis(salicylidene)propane-1,3-diamine can form triuclear complexes with coordinating anions or solvents to generate supramolecular architectures (Atakol et al., 1999; Fukuhara et al., 1990; Ray et al., 2009). However no structures of trinuclear complexes with bis-halogenosalicylidene and anionic ligands have been reported. We have attempted to assemble such a species from the mononuclear Cu^II complex {4,4'-dichloro-2,2'-[2,2-dimethylpropane-1,3- diylbis(nitrilomethanylylidene)]diphenolato}copper(II) (Kargar et al., 2012) and copper(II) acetate as the building blocks. Herein, the structure of the title trinuclear complex is reported.

The central Cu^II atom is located on a centre of inversion and has a distorted octahedral coordination environment formed by four O atoms from two tetradentate Schiff base ligands in the equatorial plane and an O atom from each of the two bridging acetate ligands in the axial positions. The coordination geometry of the terminal Cu^II atom is square-pyramidal with the basal plane comprised of two phenolate O and two imine N atoms from a tetradentate ligand. The apical site is occupied by one O atom from a bridging acetate ligand. The terminal Cu^II atom is located 0.2370 (4) Å from the mean basal plane (N1/N2/O1/O2). The six-membered Cu1/N1/C8/C9/C10/N2 ring adopts a chair conformation with puckering parameters (Cremer & Pople, 1975): Q = 0.549 (4) Å, θ = 16.4 (3)° and ϕ = 141.7 (13)°. Bond lengths and angles involving Cu^II are comparable to those observed in related structures (Atakol et al., 1999). The dihedral angle between the benzene rings (C1–C6 and C14–C19) is 68.73 (12)°. The acetate-bridged Cu···Cu distance is 3.0910 (5) Å, similar to those of related linear homo-trinuclear Cu^II complexes (Atakol et al., 1999; Feng et al., 2007; Yang et al., 2004). There is an intramolecular C2—H2···O4ⁱ hydrogen bond [symmetry code: (i) -x + 1, -y, -z + 1; Table 1], forming a S(6) ring motif (Bernstein et al., 1995). The molecular conformationof the trinuclear complex is stabilized by the intramolecular hydrogen bonds. In the crystal, the trinuclear complex molecules are linked through intermolecular C—H···O hydrogen bonds into a two-dimensional supramolecular network, parallel to the ab plane (Table 1 and Fig. 2).

Related literature top

For the supramolecular chemistry of complexes [similar complexes? related complexes?], see: Chen et al. (2010); von Richthofen et al. (2009); Gianneschi et al. (2003). For related structures, see: Atakol et al. (1999); Feng et al. (2007); Ray et al. (2009); Yang et al. (2004). For other structures [please be more specific], see: Fukuhara et al. (1990); Kargar et al. (2012); Kubono et al., (2009, 2010). For hydrogen-bond motifs, see: Bernstein et al. (1995). For analysis of ring conformations, see: Cremer & Pople (1975).

Experimental top

The ligand (0.40 mmol) was dissolved in 20 mL of hot methanol. Then 20 mL of a methanol solution of copper acetate monohydrate (0.60 mmol) were added to this solution.The mixture was stirred for 20 min at 340 K. After a few days at room temperature, green crystals of title complex were obtained. Yield 52%. Analysis calculated for C₄₂H₄₂Cl₄Cu₃N₄O₈: C 47.44, H 3.98, N 5.27%; found: C 47.48, H 3.92, N 5.21%.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures top

	Fig. 1. The molecule of the title complex showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are represented by circles of arbitrary size. [symmetry code: (i) -x + 1, -y, -z + 1.]
	Fig. 2. Packing diagram of the title complex, viewed down the c axis. The intramolecular and intermolecular C—H···O hydrogen bonds are shown as dashed lines.

Di-µ₂-acetato-1:2κ²O:O';2:3κ²O:O'-bis{µ₂-4,4'-dichloro-2,2'-[2,2-dimethylpropane-1,3-diylbis(nitrilomethanylylidene)]diphenolato}-1:2κ⁶O,N,N',O':O,O'; 2:3κ⁶O,O':O,N,N',O'-tricopper(II) top

Crystal data top

[Cu₃(C₁₉H₁₈Cl₂N₂O₂)₂(C₂H₃O₂)₂]	F(000) = 2164.00
M_r = 1063.25	D_x = 1.618 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 19.0732 (18) Å	θ = 15.0–17.4°
b = 11.6191 (11) Å	µ = 1.75 mm⁻¹
c = 19.693 (3) Å	T = 298 K
V = 4364.2 (9) Å³	Prismatic, green
Z = 4	0.23 × 0.20 × 0.16 mm

Data collection top

Rigaku AFC7R diffractometer	R_int = 0.024
ω–2θ scans	θ_max = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = −13→24
T_min = 0.675, T_max = 0.756	k = −8→15
7325 measured reflections	l = −25→0
5006 independent reflections	3 standard reflections every 150 reflections
2796 reflections with F² > 2.0σ(F²)	intensity decay: 0.5%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0428P)² + 0.7391P] where P = (F_o² + 2F_c²)/3
5006 reflections	(Δ/σ)_max = 0.001
280 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

[Cu₃(C₁₉H₁₈Cl₂N₂O₂)₂(C₂H₃O₂)₂]	V = 4364.2 (9) Å³
M_r = 1063.25	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 19.0732 (18) Å	µ = 1.75 mm⁻¹
b = 11.6191 (11) Å	T = 298 K
c = 19.693 (3) Å	0.23 × 0.20 × 0.16 mm

Data collection top

Rigaku AFC7R diffractometer	2796 reflections with F² > 2.0σ(F²)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.024
T_min = 0.675, T_max = 0.756	3 standard reflections every 150 reflections
7325 measured reflections	intensity decay: 0.5%
5006 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.00	Δρ_max = 0.39 e Å⁻³
5006 reflections	Δρ_min = −0.45 e Å⁻³
280 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.64313 (2)	0.07637 (3)	0.44178 (2)	0.03103 (12)
Cu2	0.5000	0.0000	0.5000	0.02727 (14)
Cl1	0.47496 (6)	−0.12235 (10)	0.13509 (5)	0.0602 (3)
Cl2	0.77615 (6)	−0.36381 (9)	0.66639 (5)	0.0635 (3)
O1	0.54772 (11)	0.0350 (2)	0.40871 (11)	0.0336 (5)
O2	0.61636 (11)	−0.01062 (19)	0.52089 (11)	0.0359 (6)
O3	0.60366 (11)	0.23406 (18)	0.48839 (11)	0.0363 (6)
O4	0.49941 (11)	0.16268 (18)	0.52142 (11)	0.0341 (5)
N1	0.66389 (14)	0.1401 (2)	0.35159 (14)	0.0326 (6)
N2	0.74426 (14)	0.0639 (2)	0.46700 (14)	0.0349 (7)
C1	0.53159 (17)	0.0020 (3)	0.34682 (16)	0.0302 (7)
C2	0.47113 (18)	−0.0639 (3)	0.33434 (18)	0.0384 (8)
H2	0.4416	−0.0830	0.3702	0.046*
C3	0.45508 (19)	−0.1003 (3)	0.27000 (18)	0.0418 (9)
H3	0.4152	−0.1447	0.2628	0.050*
C4	0.49741 (19)	−0.0718 (3)	0.21590 (18)	0.0405 (9)
C5	0.55477 (18)	−0.0033 (3)	0.22513 (18)	0.0385 (8)
H5	0.5816	0.0188	0.1879	0.046*
C6	0.57347 (17)	0.0342 (3)	0.29035 (17)	0.0320 (8)
C7	0.63314 (18)	0.1099 (3)	0.29713 (19)	0.0374 (8)
H7	0.6511	0.1401	0.2570	0.045*
C8	0.72103 (18)	0.2234 (3)	0.34661 (19)	0.0433 (9)
H8A	0.7110	0.2877	0.3765	0.052*
H8B	0.7229	0.2527	0.3005	0.052*
C9	0.79266 (17)	0.1737 (3)	0.36505 (18)	0.0390 (9)
C10	0.79631 (19)	0.1469 (3)	0.44084 (18)	0.0465 (10)
H10A	0.8428	0.1175	0.4509	0.056*
H10B	0.7908	0.2185	0.4656	0.056*
C11	0.8086 (2)	0.0676 (4)	0.3228 (2)	0.0584 (11)
H11A	0.7764	0.0072	0.3345	0.088*
H11B	0.8557	0.0426	0.3316	0.088*
H11C	0.8038	0.0859	0.2755	0.088*
C12	0.8473 (2)	0.2683 (4)	0.3510 (2)	0.0592 (12)
H12A	0.8928	0.2418	0.3646	0.089*
H12B	0.8353	0.3362	0.3763	0.089*
H12C	0.8477	0.2859	0.3034	0.089*
C13	0.76749 (18)	−0.0137 (3)	0.50710 (17)	0.0407 (9)
H13	0.8160	−0.0181	0.5115	0.049*
C14	0.72733 (18)	−0.0952 (3)	0.54648 (16)	0.0345 (8)
C15	0.76437 (19)	−0.1790 (3)	0.58283 (18)	0.0426 (9)
H15	0.8130	−0.1824	0.5795	0.051*
C16	0.72974 (19)	−0.2558 (3)	0.62314 (18)	0.0416 (9)
C17	0.65761 (19)	−0.2510 (3)	0.63013 (18)	0.0434 (9)
H17	0.6346	−0.3027	0.6585	0.052*
C18	0.62008 (19)	−0.1695 (3)	0.59500 (17)	0.0408 (9)
H18	0.5715	−0.1677	0.5993	0.049*
C19	0.65340 (17)	−0.0887 (3)	0.55256 (16)	0.0312 (7)
C20	0.54487 (18)	0.2416 (3)	0.51585 (16)	0.0312 (7)
C21	0.5241 (2)	0.3555 (3)	0.5462 (2)	0.0532 (11)
H21A	0.5584	0.4126	0.5345	0.080*
H21B	0.5214	0.3484	0.5947	0.080*
H21C	0.4792	0.3781	0.5287	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0229 (2)	0.0343 (2)	0.0359 (2)	−0.00107 (18)	0.00405 (18)	0.00024 (19)
Cu2	0.0223 (3)	0.0305 (3)	0.0290 (3)	−0.0010 (2)	0.0029 (2)	−0.0011 (2)
Cl1	0.0663 (7)	0.0744 (7)	0.0398 (5)	−0.0041 (6)	−0.0070 (5)	−0.0176 (5)
Cl2	0.0759 (8)	0.0619 (7)	0.0526 (6)	0.0295 (6)	−0.0149 (6)	0.0059 (5)
O1	0.0232 (12)	0.0450 (13)	0.0324 (13)	−0.0047 (11)	0.0016 (10)	−0.0044 (11)
O2	0.0274 (12)	0.0403 (14)	0.0400 (13)	0.0061 (11)	0.0050 (10)	0.0114 (12)
O3	0.0290 (12)	0.0341 (13)	0.0459 (15)	−0.0015 (11)	0.0017 (11)	−0.0057 (11)
O4	0.0318 (13)	0.0287 (12)	0.0419 (14)	−0.0008 (11)	0.0038 (11)	−0.0014 (10)
N1	0.0263 (15)	0.0311 (15)	0.0404 (17)	−0.0023 (12)	0.0009 (13)	0.0044 (13)
N2	0.0267 (15)	0.0431 (18)	0.0348 (15)	−0.0058 (13)	0.0037 (13)	−0.0025 (14)
C1	0.0291 (18)	0.0295 (18)	0.0320 (18)	0.0061 (15)	−0.0024 (15)	0.0003 (15)
C2	0.0329 (19)	0.045 (2)	0.0372 (19)	−0.0049 (16)	0.0018 (16)	−0.0017 (17)
C3	0.036 (2)	0.046 (2)	0.044 (2)	−0.0065 (18)	−0.0038 (18)	−0.0029 (18)
C4	0.042 (2)	0.046 (2)	0.034 (2)	0.0053 (19)	−0.0068 (16)	−0.0066 (17)
C5	0.034 (2)	0.046 (2)	0.0355 (19)	0.0010 (18)	0.0019 (16)	0.0012 (17)
C6	0.0263 (18)	0.0307 (18)	0.0390 (19)	0.0015 (14)	0.0011 (15)	0.0007 (15)
C7	0.035 (2)	0.0363 (19)	0.041 (2)	0.0015 (16)	0.0056 (16)	0.0098 (17)
C8	0.041 (2)	0.036 (2)	0.053 (2)	−0.0105 (17)	−0.0012 (18)	0.0059 (18)
C9	0.029 (2)	0.042 (2)	0.046 (2)	−0.0053 (16)	0.0060 (17)	0.0026 (17)
C10	0.035 (2)	0.056 (2)	0.048 (2)	−0.0185 (18)	−0.0001 (18)	0.0040 (19)
C11	0.048 (3)	0.062 (3)	0.065 (3)	0.000 (2)	0.020 (2)	−0.009 (2)
C12	0.042 (2)	0.068 (3)	0.067 (3)	−0.024 (2)	0.002 (2)	0.018 (2)
C13	0.0235 (18)	0.059 (3)	0.039 (2)	−0.0007 (17)	0.0005 (15)	−0.0009 (19)
C14	0.0304 (19)	0.043 (2)	0.0300 (18)	0.0035 (16)	0.0013 (14)	−0.0050 (16)
C15	0.031 (2)	0.056 (2)	0.040 (2)	0.0092 (18)	−0.0029 (16)	−0.0001 (19)
C16	0.045 (2)	0.042 (2)	0.037 (2)	0.0148 (19)	−0.0076 (17)	−0.0029 (17)
C17	0.050 (2)	0.043 (2)	0.038 (2)	0.0009 (19)	−0.0065 (18)	0.0115 (17)
C18	0.032 (2)	0.047 (2)	0.043 (2)	0.0013 (17)	0.0041 (17)	0.0103 (18)
C19	0.0289 (18)	0.0321 (18)	0.0325 (18)	−0.0001 (15)	0.0003 (14)	−0.0026 (15)
C20	0.0343 (18)	0.0285 (18)	0.0309 (19)	0.0034 (15)	−0.0048 (15)	0.0007 (14)
C21	0.046 (2)	0.039 (2)	0.075 (3)	0.0012 (19)	0.014 (2)	−0.019 (2)

Geometric parameters (Å, º) top

Cu1—O2	1.926 (2)	C7—H7	0.9300
Cu1—N1	1.965 (3)	C8—C9	1.527 (5)
Cu1—O1	1.992 (2)	C8—H8A	0.9700
Cu1—N2	1.997 (3)	C8—H8B	0.9700
Cu1—O3	2.183 (2)	C9—C11	1.518 (5)
Cu2—O4ⁱ	1.937 (2)	C9—C10	1.526 (5)
Cu2—O4	1.937 (2)	C9—C12	1.540 (5)
Cu2—O1	2.056 (2)	C10—H10A	0.9700
Cu2—O1ⁱ	2.056 (2)	C10—H10B	0.9700
Cu2—O2ⁱ	2.260 (2)	C11—H11A	0.9600
Cu2—O2	2.260 (2)	C11—H11B	0.9600
Cl1—C4	1.750 (4)	C11—H11C	0.9600
Cl2—C16	1.756 (4)	C12—H12A	0.9600
O1—C1	1.314 (4)	C12—H12B	0.9600
O2—C19	1.308 (4)	C12—H12C	0.9600
O3—C20	1.248 (4)	C13—C14	1.444 (5)
O4—C20	1.267 (4)	C13—H13	0.9300
N1—C7	1.272 (4)	C14—C15	1.400 (5)
N1—C8	1.461 (4)	C14—C19	1.417 (4)
N2—C13	1.277 (4)	C15—C16	1.364 (5)
N2—C10	1.477 (4)	C15—H15	0.9300
C1—C2	1.406 (5)	C16—C17	1.384 (5)
C1—C6	1.419 (4)	C17—C18	1.374 (4)
C2—C3	1.371 (5)	C17—H17	0.9300
C2—H2	0.9300	C18—C19	1.408 (4)
C3—C4	1.377 (5)	C18—H18	0.9300
C3—H3	0.9300	C20—C21	1.504 (5)
C4—C5	1.365 (5)	C21—H21A	0.9600
C5—C6	1.402 (4)	C21—H21B	0.9600
C5—H5	0.9300	C21—H21C	0.9600
C6—C7	1.445 (5)

O2—Cu1—N1	169.27 (11)	N1—C8—C9	113.6 (3)
O2—Cu1—O1	84.00 (9)	N1—C8—H8A	108.8
N1—Cu1—O1	88.83 (10)	C9—C8—H8A	108.8
O2—Cu1—N2	90.96 (11)	N1—C8—H8B	108.8
N1—Cu1—N2	93.31 (11)	C9—C8—H8B	108.8
O1—Cu1—N2	161.12 (11)	H8A—C8—H8B	107.7
O2—Cu1—O3	90.51 (9)	C11—C9—C10	111.2 (3)
N1—Cu1—O3	97.66 (10)	C11—C9—C8	110.8 (3)
O1—Cu1—O3	91.44 (9)	C10—C9—C8	110.5 (3)
N2—Cu1—O3	106.83 (10)	C11—C9—C12	110.2 (3)
O4ⁱ—Cu2—O4	180.00 (13)	C10—C9—C12	106.9 (3)
O4ⁱ—Cu2—O1	89.99 (9)	C8—C9—C12	107.0 (3)
O4—Cu2—O1	90.01 (9)	N2—C10—C9	116.3 (3)
O4ⁱ—Cu2—O1ⁱ	90.01 (9)	N2—C10—H10A	108.2
O4—Cu2—O1ⁱ	89.99 (9)	C9—C10—H10A	108.2
O1—Cu2—O1ⁱ	180.00 (10)	N2—C10—H10B	108.2
O4ⁱ—Cu2—O2ⁱ	91.11 (8)	C9—C10—H10B	108.2
O4—Cu2—O2ⁱ	88.89 (8)	H10A—C10—H10B	107.4
O1—Cu2—O2ⁱ	105.35 (8)	C9—C11—H11A	109.5
O1ⁱ—Cu2—O2ⁱ	74.65 (8)	C9—C11—H11B	109.5
O4ⁱ—Cu2—O2	88.89 (8)	H11A—C11—H11B	109.5
O4—Cu2—O2	91.11 (8)	C9—C11—H11C	109.5
O1—Cu2—O2	74.65 (8)	H11A—C11—H11C	109.5
O1ⁱ—Cu2—O2	105.35 (8)	H11B—C11—H11C	109.5
O2ⁱ—Cu2—O2	180.0	C9—C12—H12A	109.5
C1—O1—Cu1	126.0 (2)	C9—C12—H12B	109.5
C1—O1—Cu2	130.5 (2)	H12A—C12—H12B	109.5
Cu1—O1—Cu2	99.58 (9)	C9—C12—H12C	109.5
C19—O2—Cu1	127.3 (2)	H12A—C12—H12C	109.5
C19—O2—Cu2	130.9 (2)	H12B—C12—H12C	109.5
Cu1—O2—Cu2	94.85 (9)	N2—C13—C14	127.6 (3)
C20—O3—Cu1	123.5 (2)	N2—C13—H13	116.2
C20—O4—Cu2	133.1 (2)	C14—C13—H13	116.2
C7—N1—C8	118.1 (3)	C15—C14—C19	119.7 (3)
C7—N1—Cu1	124.4 (2)	C15—C14—C13	117.6 (3)
C8—N1—Cu1	117.4 (2)	C19—C14—C13	122.6 (3)
C13—N2—C10	116.3 (3)	C16—C15—C14	120.5 (3)
C13—N2—Cu1	122.7 (2)	C16—C15—H15	119.7
C10—N2—Cu1	121.0 (2)	C14—C15—H15	119.7
O1—C1—C2	120.9 (3)	C15—C16—C17	120.9 (3)
O1—C1—C6	121.2 (3)	C15—C16—Cl2	120.3 (3)
C2—C1—C6	117.9 (3)	C17—C16—Cl2	118.8 (3)
C3—C2—C1	120.9 (3)	C18—C17—C16	119.7 (3)
C3—C2—H2	119.6	C18—C17—H17	120.1
C1—C2—H2	119.6	C16—C17—H17	120.1
C2—C3—C4	120.7 (3)	C17—C18—C19	121.5 (3)
C2—C3—H3	119.7	C17—C18—H18	119.2
C4—C3—H3	119.7	C19—C18—H18	119.2
C5—C4—C3	120.5 (3)	O2—C19—C18	120.1 (3)
C5—C4—Cl1	120.9 (3)	O2—C19—C14	122.3 (3)
C3—C4—Cl1	118.7 (3)	C18—C19—C14	117.6 (3)
C4—C5—C6	120.4 (3)	O3—C20—O4	127.0 (3)
C4—C5—H5	119.8	O3—C20—C21	118.1 (3)
C6—C5—H5	119.8	O4—C20—C21	115.0 (3)
C5—C6—C1	119.5 (3)	C20—C21—H21A	109.5
C5—C6—C7	118.3 (3)	C20—C21—H21B	109.5
C1—C6—C7	122.1 (3)	H21A—C21—H21B	109.5
N1—C7—C6	127.5 (3)	C20—C21—H21C	109.5
N1—C7—H7	116.2	H21A—C21—H21C	109.5
C6—C7—H7	116.2	H21B—C21—H21C	109.5

O2—Cu1—O1—C1	−137.9 (3)	Cu1—O1—C1—C2	156.4 (2)
N1—Cu1—O1—C1	34.1 (3)	Cu2—O1—C1—C2	3.4 (5)
N2—Cu1—O1—C1	−62.7 (4)	Cu1—O1—C1—C6	−25.2 (4)
O3—Cu1—O1—C1	131.8 (2)	Cu2—O1—C1—C6	−178.2 (2)
O2—Cu1—O1—Cu2	21.70 (10)	O1—C1—C2—C3	−178.6 (3)
N1—Cu1—O1—Cu2	−166.30 (11)	C6—C1—C2—C3	3.0 (5)
N2—Cu1—O1—Cu2	96.9 (3)	C1—C2—C3—C4	−0.9 (6)
O3—Cu1—O1—Cu2	−68.66 (10)	C2—C3—C4—C5	−2.3 (6)
O4ⁱ—Cu2—O1—C1	50.4 (3)	C2—C3—C4—Cl1	179.1 (3)
O4—Cu2—O1—C1	−129.6 (3)	C3—C4—C5—C6	3.3 (5)
O2ⁱ—Cu2—O1—C1	−40.8 (3)	Cl1—C4—C5—C6	−178.2 (3)
O2—Cu2—O1—C1	139.2 (3)	C4—C5—C6—C1	−1.1 (5)
O4ⁱ—Cu2—O1—Cu1	−107.81 (10)	C4—C5—C6—C7	−177.8 (3)
O4—Cu2—O1—Cu1	72.19 (10)	O1—C1—C6—C5	179.6 (3)
O2ⁱ—Cu2—O1—Cu1	161.04 (9)	C2—C1—C6—C5	−2.0 (5)
O2—Cu2—O1—Cu1	−18.96 (9)	O1—C1—C6—C7	−3.8 (5)
N1—Cu1—O2—C19	85.3 (6)	C2—C1—C6—C7	174.6 (3)
O1—Cu1—O2—C19	133.6 (3)	C8—N1—C7—C6	−176.5 (3)
N2—Cu1—O2—C19	−28.2 (3)	Cu1—N1—C7—C6	6.9 (5)
O3—Cu1—O2—C19	−135.0 (3)	C5—C6—C7—N1	−169.5 (3)
N1—Cu1—O2—Cu2	−67.7 (5)	C1—C6—C7—N1	13.9 (5)
O1—Cu1—O2—Cu2	−19.43 (9)	C7—N1—C8—C9	−113.3 (4)
N2—Cu1—O2—Cu2	178.80 (10)	Cu1—N1—C8—C9	63.6 (4)
O3—Cu1—O2—Cu2	71.96 (9)	N1—C8—C9—C11	54.7 (4)
O4ⁱ—Cu2—O2—C19	−41.8 (3)	N1—C8—C9—C10	−69.0 (4)
O4—Cu2—O2—C19	138.2 (3)	N1—C8—C9—C12	174.9 (3)
O1—Cu2—O2—C19	−132.1 (3)	C13—N2—C10—C9	134.9 (3)
O1ⁱ—Cu2—O2—C19	47.9 (3)	Cu1—N2—C10—C9	−46.4 (4)
O4ⁱ—Cu2—O2—Cu1	109.72 (10)	C11—C9—C10—N2	−64.1 (4)
O4—Cu2—O2—Cu1	−70.28 (10)	C8—C9—C10—N2	59.5 (4)
O1—Cu2—O2—Cu1	19.42 (9)	C12—C9—C10—N2	175.6 (3)
O1ⁱ—Cu2—O2—Cu1	−160.58 (9)	C10—N2—C13—C14	171.2 (3)
O2—Cu1—O3—C20	−48.2 (2)	Cu1—N2—C13—C14	−7.4 (5)
N1—Cu1—O3—C20	124.9 (2)	N2—C13—C14—C15	174.8 (3)
O1—Cu1—O3—C20	35.9 (2)	N2—C13—C14—C19	−9.1 (6)
N2—Cu1—O3—C20	−139.3 (2)	C19—C14—C15—C16	1.2 (5)
O1—Cu2—O4—C20	−44.3 (3)	C13—C14—C15—C16	177.4 (3)
O1ⁱ—Cu2—O4—C20	135.7 (3)	C14—C15—C16—C17	−1.4 (6)
O2ⁱ—Cu2—O4—C20	−149.7 (3)	C14—C15—C16—Cl2	177.8 (3)
O2—Cu2—O4—C20	30.3 (3)	C15—C16—C17—C18	1.4 (6)
O2—Cu1—N1—C7	23.8 (7)	Cl2—C16—C17—C18	−177.9 (3)
O1—Cu1—N1—C7	−24.2 (3)	C16—C17—C18—C19	−1.1 (5)
N2—Cu1—N1—C7	137.0 (3)	Cu1—O2—C19—C18	−159.7 (2)
O3—Cu1—N1—C7	−115.5 (3)	Cu2—O2—C19—C18	−16.4 (4)
O2—Cu1—N1—C8	−152.9 (5)	Cu1—O2—C19—C14	20.9 (4)
O1—Cu1—N1—C8	159.1 (2)	Cu2—O2—C19—C14	164.2 (2)
N2—Cu1—N1—C8	−39.6 (2)	C17—C18—C19—O2	−178.6 (3)
O3—Cu1—N1—C8	67.8 (2)	C17—C18—C19—C14	0.9 (5)
O2—Cu1—N2—C13	20.7 (3)	C15—C14—C19—O2	178.5 (3)
N1—Cu1—N2—C13	−149.5 (3)	C13—C14—C19—O2	2.5 (5)
O1—Cu1—N2—C13	−53.4 (5)	C15—C14—C19—C18	−0.9 (5)
O3—Cu1—N2—C13	111.5 (3)	C13—C14—C19—C18	−176.9 (3)
O2—Cu1—N2—C10	−157.9 (2)	Cu1—O3—C20—O4	0.0 (5)
N1—Cu1—N2—C10	31.9 (3)	Cu1—O3—C20—C21	179.9 (2)
O1—Cu1—N2—C10	128.0 (3)	Cu2—O4—C20—O3	6.2 (5)
O3—Cu1—N2—C10	−67.1 (3)	Cu2—O4—C20—C21	−173.7 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O4ⁱ	0.93	2.58	3.115 (4)	117
C15—H15···O3ⁱⁱ	0.93	2.59	3.289 (4)	133

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	[Cu₃(C₁₉H₁₈Cl₂N₂O₂)₂(C₂H₃O₂)₂]
M_r	1063.25
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	19.0732 (18), 11.6191 (11), 19.693 (3)
V (Å³)	4364.2 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.75
Crystal size (mm)	0.23 × 0.20 × 0.16

Data collection
Diffractometer	Rigaku AFC7R diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.675, 0.756
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	7325, 5006, 2796
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.105, 1.00
No. of reflections	5006
No. of parameters	280
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.45

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku, 2010), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O4ⁱ	0.93	2.58	3.115 (4)	117
C15—H15···O3ⁱⁱ	0.93	2.59	3.289 (4)	133

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+3/2, y−1/2, z.

Acknowledgements

This study was supported financially in part by Grants-in-Aid for Scientific Research (grant Nos. 20550075 and 23550094) from the Japan Society for the Promotion of Science.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Atakol, O., Arıcı, C., Ercan, F. & Ülkü, D. (1999). Acta Cryst. C55, 511–513. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Chen, B., Xiang, S. & Qian, G. (2010). Acc. Chem. Res. 43, 1115–1124. Web of Science CrossRef CAS PubMed Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Feng, Y.-F., Wu, H.-Y., Zhu, B.-L., Wang, S.-R. & Huang, W.-P. (2007). Acta Cryst. E63, m1107–m1108. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fukuhara, C., Tsuneyoshi, K., Matsumoto, N., Kida, S., Mikuriya, M. & Mori, M. (1990). J. Chem. Soc. Dalton Trans. pp. 3473–3479. CSD CrossRef Web of Science Google Scholar
Gianneschi, N. C., Bertin, P. A., Nguyen, S. T., Mirkin, C. A., Zakharov, L. N. & Rheingold, L. (2003). J. Am. Chem. Soc. 125, 10508–10509. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kargar, H., Kia, R., Ganji, F. & Mirkhani, V. (2012). Acta Cryst. E68, m1135. CSD CrossRef IUCr Journals Google Scholar
Kubono, K., Noshita, C., Tani, K. & Yokoi, K. (2009). Acta Cryst. E65, m1685–m1686. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kubono, K., Tsuno, Y., Tani, K. & Yokoi, K. (2010). Acta Cryst. E66, m1397–m1398. Web of Science CSD CrossRef IUCr Journals Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Ray, A., Sadhukhan, D., Rosair, G. M., Gómez-García, C. J. & Mitra, S. (2009). Polyhedron, 28, 3542–3550. Web of Science CrossRef CAS Google Scholar
Richthofen, C.-G. F. von, Stammler, A., Bögge, H., DeGroot, M. W., Long, J. R. & Glaser, T. (2009). Inorg. Chem. 48, 10165–10176. PubMed Google Scholar
Rigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, S.-P., Hong, Y., Chen, H.-M., Zhang, F., Chen, Q.-Q. & Yu, X.-B. (2004). Acta Cryst. E60, m582–m584. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.