Bis[μ-4,4′,6,6′-tetra­chloro-2,2′-(piperazine-1,4-diyldimethyl­ene)diphenolato]dicopper(II)

Kubono, K.; Noshita, C.; Tani, K.; Yokoi, K.

doi:10.1107/S1600536809049800

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages m1685-m1686

doi:10.1107/S1600536809049800

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Bis[μ-4,4′,6,6′-tetrachloro-2,2′-(piperazine-1,4-diyldimethylene)diphenolato]dicopper(II)

Koji Kubono,^a ^* Chisato Noshita,^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 5 November 2009; accepted 20 November 2009; online 28 November 2009)

In the centrosymmetric dinuclear Cu^II title complex, [Cu₂(C₁₈H₁₆Cl₄N₂O₂)₂], the Cu^II atom adopts a square-pyramidal geometry with a tetradentate ligand in the basal plane. The apical site is occupied by a phenolate O atom from an adjacent ligand, forming a dimer. The molecular structure is stabilized by intramolecular C—H⋯O and C—H⋯Cl hydrogen bonds.

Related literature

For the synthesis and the monoclinic and orthorhombic polymorphs of a tetrachloro-2,2′-(piperazine-1,4-diyldimethylene)diphenol, see: Kubono & Yokoi (2007 ). For related stuctures, see: Butcher et al. (2007 ); Kubono et al. (2003 ); Massoud & Mautner (2004 ); Weinberger et al. (2000 ).

Experimental

Crystal data

[Cu₂(C₁₈H₁₆Cl₄N₂O₂)₂]
M_r = 995.36
Monoclinic, C 2/c
a = 20.1772 (18) Å
b = 15.3901 (18) Å
c = 15.1397 (14) Å
β = 121.140 (6)°
V = 4023.9 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.63 mm⁻¹
T = 296 K
0.20 × 0.08 × 0.07 mm

Data collection

Rigaku AFC-7R diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.855, T_max = 0.892
4759 measured reflections
4634 independent reflections
2574 reflections with I > 2σ(I)
R_int = 0.046
3 standard reflections every 150 reflections intensity decay: 0.7%

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.119
S = 0.99
4634 reflections
245 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	1.913 (2)
Cu1—O2	1.955 (2)
Cu1—O2ⁱ	2.381 (3)
Cu1—N1	2.026 (4)
Cu1—N2	2.033 (3)

O1—Cu1—O2	97.69 (11)
O1—Cu1—O2ⁱ	96.68 (12)
O1—Cu1—N1	93.97 (12)
O2—Cu1—O2ⁱ	85.84 (11)
O2—Cu1—N2	92.90 (12)
O2ⁱ—Cu1—N1	104.18 (13)
O2ⁱ—Cu1—N2	97.64 (12)
N1—Cu1—N2	73.22 (13)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H12⋯Cl4ⁱ	0.97	2.76	3.544 (5)	138
C12—H14⋯O1ⁱ	0.97	2.19	3.112 (6)	159
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: WinAFC (Rigaku/MSC, 2006 ); cell refinement: WinAFC; data reduction: CrystalStructure (Rigaku/MSC, 2006); 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/S1600536809049800/fk2007sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809049800/fk2007Isup2.hkl

checkCIF report

Comment top

Recently, we have reported the crystal structure of tetrachloro-2,2'-(piperazine-1,4-diyldimethylene)diphenol, H₂Cl₂bpi (Kubono & Yokoi, 2007). As a continuation of this work on the structural characterization of piperazinediphenol compounds, the title dinuclear Cu^II complex (Fig. 1) is reported here. The Cu^II atom has a square-pyramidal coordination geometry with the basal plane comprised of two phenolate O and two tertiary alkyl N atoms from a piperazinediphenol ligand. The apical site is occupied by a phenolate O atom from an adjacent ligand generated by inversion operation, building a centrosymmetric dimer. The Cu···Cu distance within the dimer is 3.1883 (10) Å. The dihedral angle between the benzene rings (C1–C6 and C13–C18) is 87.96 (16) °. The coordination bond lengths and angles (Table 1) are comparable to those observed in related complexes (Butcher et al., 2007; Kubono et al., 2003; Massoud et al., 2004; Weinberger et al., 2000). The molecular structure complex is stabilized by intramolecular C—H···O and C—H···Cl hydrogen bonds (Table 2).

Related literature top

For the synthesis and the monoclinic and orthorhombic polymorphs of a tetrachloro-2,2'-(piperazine-1,4-diyldimethylene)diphenol, see: Kubono & Yokoi (2007). For related stuctures, see: Butcher et al. (2007); Kubono et al. (2003); Massoud et al. (2004); Weinberger et al. (2000).

Experimental top

H₂Cl₂bpi (0.109 g, 0.25 mmol) was dissolved in 30 ml hot chloroform. Then 30 ml of a methanol solution of copper acetate monohydrate (0.0499 g, 0.25 mmol) were added to this solution. The mixture was stirred for 20 min at 340 K. After a few days at room temperature, dark-green crystals of (I) were obtained. Yield 24.4%. Analysis calculated for C₃₆H₃₂Cl₈Cu₂N₄O₄: C 43.44, H 3.24, N 5.63%; found: C 43.05, H 3.22, N 5.53%.

Computing details top

Data collection: WinAFC (Rigaku/MSC, 2006); cell refinement: WinAFC (Rigaku/MSC, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2006); 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/MSC, 2006).

Figures top

Fig. 1. The molecule of the title complex showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level. Only the H atoms involved in the hydrogen bonds are represented by circles of arbitrary size. [Symmetry code: (i) 1/2 - x,1/2 - y,-z.]

Bis[µ-4,4',6,6'-tetrachloro-2,2'-(piperazine-1,4- diyldimethylene)diphenolato]dicopper(II) top

Crystal data top

[Cu₂(C₁₈H₁₆Cl₄N₂O₂)₂]	F(000) = 2008.00
M_r = 995.36	D_x = 1.643 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 20.1772 (18) Å	θ = 13.4–14.9°
b = 15.3901 (18) Å	µ = 1.63 mm⁻¹
c = 15.1397 (14) Å	T = 296 K
β = 121.140 (6)°	Column, dark-green
V = 4023.9 (7) Å³	0.20 × 0.08 × 0.07 mm
Z = 4

Data collection top

Rigaku AFC-7R diffractometer	R_int = 0.046
ω–2θ scans	θ_max = 27.5°
Absorption correction: ψ scan (North et al., 1968)	h = 0→26
T_min = 0.855, T_max = 0.892	k = 0→19
4759 measured reflections	l = −19→16
4634 independent reflections	3 standard reflections every 150 reflections
2574 reflections with I > 2σ(I)	intensity decay: 0.7%

Refinement top

Refinement on F²	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.041	w = 1/[σ²(F_o²) + (0.0378P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.119	(Δ/σ)_max < 0.001
S = 0.99	Δρ_max = 0.37 e Å⁻³
4634 reflections	Δρ_min = −0.39 e Å⁻³
245 parameters

Crystal data top

[Cu₂(C₁₈H₁₆Cl₄N₂O₂)₂]	V = 4023.9 (7) Å³
M_r = 995.36	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 20.1772 (18) Å	µ = 1.63 mm⁻¹
b = 15.3901 (18) Å	T = 296 K
c = 15.1397 (14) Å	0.20 × 0.08 × 0.07 mm
β = 121.140 (6)°

Data collection top

Rigaku AFC-7R diffractometer	2574 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.046
T_min = 0.855, T_max = 0.892	3 standard reflections every 150 reflections
4759 measured reflections	intensity decay: 0.7%
4634 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	245 parameters
wR(F²) = 0.119	H-atom parameters constrained
S = 0.99	Δρ_max = 0.37 e Å⁻³
4634 reflections	Δρ_min = −0.39 e Å⁻³

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 of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Cu1	0.23572 (3)	0.25394 (3)	0.09411 (4)	0.03688 (13)
Cl1	0.42437 (6)	0.45428 (7)	0.29614 (8)	0.0506 (2)
Cl2	0.41605 (8)	0.34818 (11)	0.62836 (9)	0.0812 (4)
Cl3	−0.07156 (8)	0.53920 (10)	−0.17092 (12)	0.0863 (4)
Cl4	0.23821 (7)	0.53026 (7)	0.00693 (10)	0.0645 (3)
O1	0.33424 (16)	0.29710 (19)	0.1996 (2)	0.0490 (7)
O2	0.21681 (15)	0.33844 (16)	−0.01288 (19)	0.0391 (6)
N1	0.22348 (19)	0.1741 (2)	0.1911 (2)	0.0421 (7)
N2	0.12414 (18)	0.2118 (2)	0.0166 (2)	0.0381 (7)
C1	0.3513 (2)	0.3070 (2)	0.2952 (2)	0.0384 (8)
C2	0.3933 (2)	0.3796 (2)	0.3535 (2)	0.0356 (8)
C3	0.4129 (2)	0.3920 (2)	0.4540 (3)	0.0427 (9)
C4	0.3895 (2)	0.3322 (3)	0.4996 (3)	0.0497 (10)
C5	0.3496 (2)	0.2591 (2)	0.4474 (3)	0.0498 (10)
C6	0.3311 (2)	0.2455 (2)	0.3472 (3)	0.0421 (8)
C7	0.2937 (2)	0.1606 (2)	0.2929 (3)	0.0494 (10)
C8	0.1593 (2)	0.2145 (3)	0.1957 (3)	0.0550 (11)
C9	0.0965 (2)	0.2379 (2)	0.0862 (3)	0.0498 (10)
C10	0.1323 (2)	0.1156 (2)	0.0214 (3)	0.0493 (10)
C11	0.1958 (2)	0.0924 (2)	0.1308 (3)	0.0509 (10)
C12	0.0751 (2)	0.2445 (2)	−0.0894 (3)	0.0440 (9)
C13	0.0784 (2)	0.3422 (2)	−0.0909 (3)	0.0435 (9)
C14	0.0111 (2)	0.3904 (3)	−0.1272 (3)	0.0548 (11)
C15	0.0140 (2)	0.4794 (3)	−0.1254 (3)	0.0582 (11)
C16	0.0832 (2)	0.5220 (3)	−0.0846 (3)	0.0588 (12)
C17	0.1506 (2)	0.4743 (2)	−0.0473 (3)	0.0474 (9)
C18	0.1510 (2)	0.3828 (2)	−0.0497 (3)	0.0393 (8)
H1	0.4417	0.4403	0.4907	0.051*
H2	0.3350	0.2185	0.4797	0.060*
H3	0.3308	0.1272	0.2844	0.059*
H4	0.2805	0.1271	0.3359	0.059*
H5	0.1772	0.2662	0.2383	0.066*
H6	0.1391	0.1743	0.2255	0.066*
H7	0.0488	0.2076	0.0675	0.060*
H8	0.0865	0.2999	0.0808	0.060*
H9	0.1462	0.0957	−0.0277	0.059*
H10	0.0839	0.0884	0.0049	0.059*
H11	0.1756	0.0535	0.1618	0.061*
H12	0.2381	0.0634	0.1300	0.061*
H13	0.0221	0.2259	−0.1168	0.053*
H14	0.0929	0.2206	−0.1329	0.053*
H15	−0.0361	0.3622	−0.1529	0.066*
H16	0.0849	0.5824	−0.0820	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0394 (2)	0.0371 (2)	0.0428 (2)	−0.0113 (2)	0.0273 (2)	−0.0080 (2)
Cl1	0.0544 (6)	0.0427 (5)	0.0575 (6)	−0.0089 (4)	0.0308 (5)	−0.0021 (4)
Cl2	0.0865 (9)	0.1165 (12)	0.0375 (6)	0.0042 (8)	0.0298 (6)	−0.0045 (7)
Cl3	0.0662 (8)	0.0757 (9)	0.0988 (11)	0.0224 (7)	0.0297 (7)	−0.0121 (8)
Cl4	0.0670 (7)	0.0423 (6)	0.0935 (9)	−0.0160 (5)	0.0482 (7)	−0.0237 (6)
O1	0.0489 (16)	0.0635 (19)	0.0403 (15)	−0.0248 (14)	0.0272 (13)	−0.0149 (14)
O2	0.0414 (14)	0.0367 (14)	0.0448 (15)	−0.0073 (12)	0.0263 (12)	−0.0059 (12)
N1	0.0474 (19)	0.0402 (19)	0.0470 (19)	−0.0135 (14)	0.0304 (16)	−0.0111 (15)
N2	0.0384 (17)	0.0362 (16)	0.0497 (19)	−0.0090 (14)	0.0298 (16)	−0.0095 (15)
C1	0.0337 (19)	0.045 (2)	0.037 (2)	−0.0012 (16)	0.0183 (16)	−0.0034 (17)
C2	0.0314 (18)	0.0345 (19)	0.038 (2)	0.0022 (15)	0.0159 (16)	−0.0009 (16)
C3	0.037 (2)	0.039 (2)	0.043 (2)	0.0103 (17)	0.0138 (18)	−0.0039 (18)
C4	0.046 (2)	0.064 (2)	0.035 (2)	0.015 (2)	0.0181 (19)	0.003 (2)
C5	0.046 (2)	0.060 (2)	0.046 (2)	0.005 (2)	0.025 (2)	0.011 (2)
C6	0.043 (2)	0.042 (2)	0.045 (2)	−0.0020 (19)	0.0247 (18)	−0.0021 (19)
C7	0.058 (2)	0.040 (2)	0.055 (2)	−0.0046 (19)	0.032 (2)	0.0053 (19)
C8	0.054 (2)	0.068 (3)	0.059 (2)	−0.009 (2)	0.041 (2)	−0.012 (2)
C9	0.049 (2)	0.050 (2)	0.068 (2)	−0.004 (2)	0.043 (2)	−0.011 (2)
C10	0.045 (2)	0.040 (2)	0.066 (2)	−0.0138 (18)	0.031 (2)	−0.016 (2)
C11	0.064 (2)	0.031 (2)	0.066 (2)	−0.0147 (19)	0.039 (2)	−0.0104 (19)
C12	0.038 (2)	0.045 (2)	0.051 (2)	−0.0141 (19)	0.0248 (18)	−0.017 (2)
C13	0.042 (2)	0.046 (2)	0.040 (2)	−0.0026 (18)	0.0205 (18)	−0.0064 (18)
C14	0.040 (2)	0.063 (3)	0.057 (2)	−0.006 (2)	0.022 (2)	−0.014 (2)
C15	0.055 (2)	0.056 (2)	0.055 (2)	0.012 (2)	0.023 (2)	−0.007 (2)
C16	0.072 (3)	0.039 (2)	0.069 (3)	−0.001 (2)	0.038 (2)	−0.009 (2)
C17	0.050 (2)	0.043 (2)	0.055 (2)	−0.0035 (19)	0.031 (2)	−0.011 (2)
C18	0.045 (2)	0.036 (2)	0.040 (2)	−0.0041 (17)	0.0241 (18)	−0.0073 (17)

Geometric parameters (Å, º) top

Cu1—O1	1.913 (2)	C10—C11	1.523 (5)
Cu1—O2	1.955 (2)	C12—C13	1.505 (5)
Cu1—O2ⁱ	2.381 (3)	C13—C14	1.387 (6)
Cu1—N1	2.026 (4)	C13—C18	1.408 (5)
Cu1—N2	2.033 (3)	C14—C15	1.371 (6)
Cl1—C2	1.740 (4)	C15—C16	1.368 (7)
Cl2—C4	1.751 (4)	C16—C17	1.383 (6)
Cl3—C15	1.752 (5)	C17—C18	1.409 (5)
Cl4—C17	1.744 (4)	C3—H1	0.930
O1—C1	1.313 (5)	C5—H2	0.930
O2—C18	1.332 (4)	C7—H3	0.970
N1—C7	1.472 (4)	C7—H4	0.970
N1—C8	1.470 (7)	C8—H5	0.970
N1—C11	1.484 (5)	C8—H6	0.970
N2—C9	1.479 (7)	C9—H7	0.970
N2—C10	1.487 (4)	C9—H8	0.970
N2—C12	1.472 (4)	C10—H9	0.970
C1—C2	1.406 (4)	C10—H10	0.970
C1—C6	1.419 (6)	C11—H11	0.970
C2—C3	1.373 (6)	C11—H12	0.970
C3—C4	1.372 (7)	C12—H13	0.970
C4—C5	1.373 (5)	C12—H14	0.970
C5—C6	1.378 (6)	C14—H15	0.930
C6—C7	1.519 (5)	C16—H16	0.930
C8—C9	1.521 (5)

O1—Cu1—O2	97.69 (11)	C13—C14—C15	120.3 (4)
O1—Cu1—O2ⁱ	96.68 (12)	Cl3—C15—C14	119.7 (3)
O1—Cu1—N1	93.97 (12)	Cl3—C15—C16	119.6 (3)
O1—Cu1—N2	162.75 (17)	C14—C15—C16	120.7 (4)
O2—Cu1—O2ⁱ	85.84 (11)	C15—C16—C17	119.2 (4)
O2—Cu1—N1	163.66 (13)	Cl4—C17—C16	118.3 (3)
O2—Cu1—N2	92.90 (12)	Cl4—C17—C18	119.2 (3)
O2ⁱ—Cu1—N1	104.18 (13)	C16—C17—C18	122.5 (4)
O2ⁱ—Cu1—N2	97.64 (12)	O2—C18—C13	122.8 (3)
N1—Cu1—N2	73.22 (13)	O2—C18—C17	121.3 (3)
Cu1—O1—C1	121.8 (3)	C13—C18—C17	115.9 (3)
Cu1—O2—Cu1ⁱ	94.16 (10)	C2—C3—H1	120.4
Cu1—O2—C18	114.4 (3)	C4—C3—H1	120.4
Cu1ⁱ—O2—C18	132.1 (2)	C4—C5—H2	119.9
Cu1—N1—C7	115.6 (3)	C6—C5—H2	119.9
Cu1—N1—C8	102.7 (2)	N1—C7—H3	109.1
Cu1—N1—C11	102.5 (2)	N1—C7—H4	109.1
C7—N1—C8	113.9 (3)	C6—C7—H3	109.1
C7—N1—C11	112.1 (2)	C6—C7—H4	109.1
C8—N1—C11	109.0 (3)	H3—C7—H4	107.8
Cu1—N2—C9	102.5 (2)	N1—C8—H5	110.1
Cu1—N2—C10	103.1 (2)	N1—C8—H6	110.1
Cu1—N2—C12	116.0 (2)	C9—C8—H5	110.1
C9—N2—C10	107.9 (3)	C9—C8—H6	110.1
C9—N2—C12	113.3 (3)	H5—C8—H6	108.4
C10—N2—C12	112.8 (3)	N2—C9—H7	110.2
O1—C1—C2	120.9 (4)	N2—C9—H8	110.2
O1—C1—C6	123.2 (3)	C8—C9—H7	110.2
C2—C1—C6	115.8 (3)	C8—C9—H8	110.2
Cl1—C2—C1	117.9 (3)	H7—C9—H8	108.5
Cl1—C2—C3	119.3 (2)	N2—C10—H9	110.3
C1—C2—C3	122.7 (4)	N2—C10—H10	110.3
C2—C3—C4	119.2 (3)	C11—C10—H9	110.3
Cl2—C4—C3	118.7 (3)	C11—C10—H10	110.3
Cl2—C4—C5	120.4 (4)	H9—C10—H10	108.5
C3—C4—C5	120.8 (4)	N1—C11—H11	110.1
C4—C5—C6	120.2 (4)	N1—C11—H12	110.1
C1—C6—C5	121.2 (3)	C10—C11—H11	110.1
C1—C6—C7	118.5 (4)	C10—C11—H12	110.1
C5—C6—C7	120.2 (4)	H11—C11—H12	108.4
N1—C7—C6	112.6 (3)	N2—C12—H13	109.6
N1—C8—C9	107.8 (4)	N2—C12—H14	109.6
N2—C9—C8	107.7 (3)	C13—C12—H13	109.6
N2—C10—C11	107.3 (3)	C13—C12—H14	109.6
N1—C11—C10	107.9 (3)	H13—C12—H14	108.1
N2—C12—C13	110.3 (2)	C13—C14—H15	119.8
C12—C13—C14	119.9 (3)	C15—C14—H15	119.8
C12—C13—C18	118.8 (3)	C15—C16—H16	120.4
C14—C13—C18	121.2 (3)	C17—C16—H16	120.4

O1—Cu1—O2—Cu1ⁱ	96.20 (12)	C8—N1—C7—C6	−66.1 (5)
O1—Cu1—O2—C18	−123.4 (2)	C7—N1—C11—C10	−170.3 (4)
O2—Cu1—O1—C1	134.9 (2)	C11—N1—C7—C6	169.5 (4)
O1—Cu1—O2ⁱ—Cu1ⁱ	−97.27 (11)	C8—N1—C11—C10	62.6 (5)
O1—Cu1—O2ⁱ—C18ⁱ	31.3 (3)	C11—N1—C8—C9	−63.2 (4)
O2ⁱ—Cu1—O1—C1	−138.5 (2)	Cu1—N2—C9—C8	−44.0 (3)
O1—Cu1—N1—C7	−12.9 (3)	Cu1—N2—C10—C11	43.3 (4)
O1—Cu1—N1—C8	111.7 (2)	Cu1—N2—C12—C13	−53.1 (4)
O1—Cu1—N1—C11	−135.2 (2)	C9—N2—C10—C11	−64.7 (4)
N1—Cu1—O1—C1	−33.7 (3)	C10—N2—C9—C8	64.4 (3)
O1—Cu1—N2—C9	12.7 (5)	C9—N2—C12—C13	65.1 (4)
O1—Cu1—N2—C10	−99.3 (4)	C12—N2—C9—C8	−169.8 (3)
O1—Cu1—N2—C12	136.8 (4)	C10—N2—C12—C13	−171.8 (4)
N2—Cu1—O1—C1	7.5 (5)	C12—N2—C10—C11	169.2 (4)
O2—Cu1—O2ⁱ—C18ⁱ	128.6 (3)	O1—C1—C2—Cl1	−1.8 (5)
O2ⁱ—Cu1—O2—C18	140.4 (2)	O1—C1—C2—C3	−179.4 (3)
O2—Cu1—N1—C7	−148.4 (3)	O1—C1—C6—C5	−179.4 (3)
O2—Cu1—N1—C8	−23.8 (5)	O1—C1—C6—C7	5.2 (5)
O2—Cu1—N1—C11	89.3 (5)	C2—C1—C6—C5	2.3 (5)
N1—Cu1—O2—Cu1ⁱ	−128.7 (4)	C2—C1—C6—C7	−173.1 (3)
N1—Cu1—O2—C18	11.7 (5)	C6—C1—C2—Cl1	176.5 (2)
O2—Cu1—N2—C9	−115.2 (2)	C6—C1—C2—C3	−1.0 (5)
O2—Cu1—N2—C10	132.8 (3)	Cl1—C2—C3—C4	−178.9 (3)
O2—Cu1—N2—C12	8.9 (3)	C1—C2—C3—C4	−1.3 (6)
N2—Cu1—O2—Cu1ⁱ	−97.46 (12)	C2—C3—C4—Cl2	179.2 (3)
N2—Cu1—O2—C18	43.0 (2)	C2—C3—C4—C5	2.5 (6)
O2ⁱ—Cu1—N1—C7	85.0 (3)	Cl2—C4—C5—C6	−177.9 (3)
O2ⁱ—Cu1—N1—C8	−150.4 (2)	C3—C4—C5—C6	−1.3 (6)
O2ⁱ—Cu1—N1—C11	−37.3 (2)	C4—C5—C6—C1	−1.2 (6)
N1—Cu1—O2ⁱ—Cu1ⁱ	166.91 (10)	C4—C5—C6—C7	174.1 (4)
N1—Cu1—O2ⁱ—C18ⁱ	−64.5 (3)	C1—C6—C7—N1	−55.4 (6)
O2ⁱ—Cu1—N2—C9	158.6 (2)	C5—C6—C7—N1	129.1 (4)
O2ⁱ—Cu1—N2—C10	46.6 (3)	N1—C8—C9—N2	−0.5 (4)
O2ⁱ—Cu1—N2—C12	−77.3 (2)	N2—C10—C11—N1	1.5 (6)
N2—Cu1—O2ⁱ—Cu1ⁱ	92.37 (12)	N2—C12—C13—C14	−120.3 (4)
N2—Cu1—O2ⁱ—C18ⁱ	−139.0 (3)	N2—C12—C13—C18	56.3 (6)
N1—Cu1—N2—C9	56.1 (2)	C12—C13—C14—C15	177.7 (4)
N1—Cu1—N2—C10	−56.0 (3)	C12—C13—C18—O2	2.5 (7)
N1—Cu1—N2—C12	−179.9 (2)	C12—C13—C18—C17	−176.0 (4)
N2—Cu1—N1—C7	178.8 (3)	C14—C13—C18—O2	179.0 (4)
N2—Cu1—N1—C8	−56.5 (2)	C14—C13—C18—C17	0.5 (7)
N2—Cu1—N1—C11	56.5 (2)	C18—C13—C14—C15	1.1 (8)
Cu1—O1—C1—C2	−140.0 (3)	C13—C14—C15—Cl3	−179.6 (4)
Cu1—O1—C1—C6	41.7 (5)	C13—C14—C15—C16	−2.2 (8)
Cu1—O2—C18—C13	−54.9 (5)	Cl3—C15—C16—C17	179.0 (4)
Cu1—O2—C18—C17	123.5 (4)	C14—C15—C16—C17	1.6 (9)
Cu1ⁱ—O2—C18—C13	66.2 (6)	C15—C16—C17—Cl4	−178.5 (4)
Cu1ⁱ—O2—C18—C17	−115.3 (4)	C15—C16—C17—C18	0.2 (6)
Cu1—N1—C7—C6	52.4 (5)	Cl4—C17—C18—O2	−1.0 (7)
Cu1—N1—C8—C9	45.0 (3)	Cl4—C17—C18—C13	177.5 (3)
Cu1—N1—C11—C10	−45.7 (4)	C16—C17—C18—O2	−179.7 (5)
C7—N1—C8—C9	170.8 (3)	C16—C17—C18—C13	−1.2 (7)

Symmetry code: (i) −x+1/2, −y+1/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H12···Cl4ⁱ	0.97	2.76	3.544 (5)	138
C12—H14···O1ⁱ	0.97	2.19	3.112 (6)	159

Symmetry code: (i) −x+1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₈H₁₆Cl₄N₂O₂)₂]
M_r	995.36
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	20.1772 (18), 15.3901 (18), 15.1397 (14)
β (°)	121.140 (6)
V (Å³)	4023.9 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.63
Crystal size (mm)	0.20 × 0.08 × 0.07

Data collection
Diffractometer	Rigaku AFC-7R diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.855, 0.892
No. of measured, independent and observed [I > 2σ(I)] reflections	4759, 4634, 2574
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.119, 0.99
No. of reflections	4634
No. of parameters	245
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.39

Computer programs: WinAFC (Rigaku/MSC, 2006), CrystalStructure (Rigaku/MSC, 2006), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

Cu1—O1	1.913 (2)	Cu1—N1	2.026 (4)
Cu1—O2	1.955 (2)	Cu1—N2	2.033 (3)
Cu1—O2ⁱ	2.381 (3)

O1—Cu1—O2	97.69 (11)	O2—Cu1—N2	92.90 (12)
O1—Cu1—O2ⁱ	96.68 (12)	O2ⁱ—Cu1—N1	104.18 (13)
O1—Cu1—N1	93.97 (12)	O2ⁱ—Cu1—N2	97.64 (12)
O2—Cu1—O2ⁱ	85.84 (11)	N1—Cu1—N2	73.22 (13)

Symmetry code: (i) −x+1/2, −y+1/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H12···Cl4ⁱ	0.97	2.76	3.544 (5)	138
C12—H14···O1ⁱ	0.97	2.19	3.112 (6)	159

Symmetry code: (i) −x+1/2, −y+1/2, −z.

Acknowledgements

This study was supported financially in part by Grants-in-Aid (No. 20550075) from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Butcher, R. J., Pourian, M. & Jasinski, J. P. (2007). Acta Cryst. E63, m1913–m1914. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kubono, K., Hirayama, N., Kokusen, H. & Yokoi, K. (2003). Anal. Sci. 19, 645–646. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kubono, K. & Yokoi, K. (2007). Acta Cryst. C63, o535–o537. Web of Science CSD CrossRef IUCr Journals Google Scholar
Massoud, S. S. & Mautner, F. A. (2004). Inorg. Chem. Commun. 7, 559–562. Web of Science CSD CrossRef CAS 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
Rigaku/MSC (2006). WinAFC and CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. 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
Weinberger, P., Costisor, O., Tudose, R., Baumgartner, O. & Linert, W. (2000). J. Mol. Struct. 519, 21–31. Web of Science CSD CrossRef CAS Google Scholar

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Volume 65| Part 12| December 2009| Pages m1685-m1686

doi:10.1107/S1600536809049800

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis[μ-4,4′,6,6′-tetra­chloro-2,2′-(piperazine-1,4-diyldi­methyl­ene)diphenolato]dicopper(II)

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis[μ-4,4′,6,6′-tetrachloro-2,2′-(piperazine-1,4-diyldimethylene)diphenolato]dicopper(II)