Literature DB >> 21578691

Bis[μ-4,4',6,6'-tetra-chloro-2,2'-(piperazine-1,4-diyldimethyl-ene)diphenolato]dicopper(II).

Koji Kubono1, Chisato Noshita, Keita Tani, Kunihiko Yokoi.   

Abstract

In the centrosymmetric dinuclear Cu(II) title complex, [Cu(2)(C(18)H(16)Cl(4)N(2)O(2))(2)], the Cu(II) atom adopts a square-pyramidal geometry with a tetra-dentate ligand in the basal plane. The apical site is occupied by a phenolate O atom from an adjacent ligand, forming a dimer. The mol-ecular structure is stabilized by intra-molecular C-H⋯O and C-H⋯Cl hydrogen bonds.

Entities:  

Year:  2009        PMID： 21578691      PMCID： PMC2971750          DOI： 10.1107/S1600536809049800

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


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 = 995.36 Monoclinic, 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[F 2 > 2σ(F 2)] = 0.041 wR(F 2) = 0.119 S = 0.99 4634 reflections 245 parameters H-atom parameters constrained Δρmax = 0.37 e Å−3 Δρmin = −0.39 e Å−3 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. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049800/fk2007sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049800/fk2007Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
[Cu2(C18H16Cl4N2O2)2]F(000) = 2008.00
Mr = 995.36Dx = 1.643 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2ycCell parameters from 25 reflections
a = 20.1772 (18) Åθ = 13.4–14.9°
b = 15.3901 (18) ŵ = 1.63 mm−1
c = 15.1397 (14) ÅT = 296 K
β = 121.140 (6)°Column, dark-green
V = 4023.9 (7) Å30.20 × 0.08 × 0.07 mm
Z = 4
Rigaku AFC-7R diffractometerRint = 0.046
ω–2θ scansθmax = 27.5°
Absorption correction: ψ scan (North et al., 1968)h = 0→26
Tmin = 0.855, Tmax = 0.892k = 0→19
4759 measured reflectionsl = −19→16
4634 independent reflections3 standard reflections every 150 reflections
2574 reflections with I > 2σ(I) intensity decay: 0.7%
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.041w = 1/[σ2(Fo2) + (0.0378P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.119(Δ/σ)max < 0.001
S = 0.99Δρmax = 0.37 e Å−3
4634 reflectionsΔρmin = −0.39 e Å−3
245 parameters
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.
xyzUiso*/Ueq
Cu10.23572 (3)0.25394 (3)0.09411 (4)0.03688 (13)
Cl10.42437 (6)0.45428 (7)0.29614 (8)0.0506 (2)
Cl20.41605 (8)0.34818 (11)0.62836 (9)0.0812 (4)
Cl3−0.07156 (8)0.53920 (10)−0.17092 (12)0.0863 (4)
Cl40.23821 (7)0.53026 (7)0.00693 (10)0.0645 (3)
O10.33424 (16)0.29710 (19)0.1996 (2)0.0490 (7)
O20.21681 (15)0.33844 (16)−0.01288 (19)0.0391 (6)
N10.22348 (19)0.1741 (2)0.1911 (2)0.0421 (7)
N20.12414 (18)0.2118 (2)0.0166 (2)0.0381 (7)
C10.3513 (2)0.3070 (2)0.2952 (2)0.0384 (8)
C20.3933 (2)0.3796 (2)0.3535 (2)0.0356 (8)
C30.4129 (2)0.3920 (2)0.4540 (3)0.0427 (9)
C40.3895 (2)0.3322 (3)0.4996 (3)0.0497 (10)
C50.3496 (2)0.2591 (2)0.4474 (3)0.0498 (10)
C60.3311 (2)0.2455 (2)0.3472 (3)0.0421 (8)
C70.2937 (2)0.1606 (2)0.2929 (3)0.0494 (10)
C80.1593 (2)0.2145 (3)0.1957 (3)0.0550 (11)
C90.0965 (2)0.2379 (2)0.0862 (3)0.0498 (10)
C100.1323 (2)0.1156 (2)0.0214 (3)0.0493 (10)
C110.1958 (2)0.0924 (2)0.1308 (3)0.0509 (10)
C120.0751 (2)0.2445 (2)−0.0894 (3)0.0440 (9)
C130.0784 (2)0.3422 (2)−0.0909 (3)0.0435 (9)
C140.0111 (2)0.3904 (3)−0.1272 (3)0.0548 (11)
C150.0140 (2)0.4794 (3)−0.1254 (3)0.0582 (11)
C160.0832 (2)0.5220 (3)−0.0846 (3)0.0588 (12)
C170.1506 (2)0.4743 (2)−0.0473 (3)0.0474 (9)
C180.1510 (2)0.3828 (2)−0.0497 (3)0.0393 (8)
H10.44170.44030.49070.051*
H20.33500.21850.47970.060*
H30.33080.12720.28440.059*
H40.28050.12710.33590.059*
H50.17720.26620.23830.066*
H60.13910.17430.22550.066*
H70.04880.20760.06750.060*
H80.08650.29990.08080.060*
H90.14620.0957−0.02770.059*
H100.08390.08840.00490.059*
H110.17560.05350.16180.061*
H120.23810.06340.13000.061*
H130.02210.2259−0.11680.053*
H140.09290.2206−0.13290.053*
H15−0.03610.3622−0.15290.066*
H160.08490.5824−0.08200.070*
U11U22U33U12U13U23
Cu10.0394 (2)0.0371 (2)0.0428 (2)−0.0113 (2)0.0273 (2)−0.0080 (2)
Cl10.0544 (6)0.0427 (5)0.0575 (6)−0.0089 (4)0.0308 (5)−0.0021 (4)
Cl20.0865 (9)0.1165 (12)0.0375 (6)0.0042 (8)0.0298 (6)−0.0045 (7)
Cl30.0662 (8)0.0757 (9)0.0988 (11)0.0224 (7)0.0297 (7)−0.0121 (8)
Cl40.0670 (7)0.0423 (6)0.0935 (9)−0.0160 (5)0.0482 (7)−0.0237 (6)
O10.0489 (16)0.0635 (19)0.0403 (15)−0.0248 (14)0.0272 (13)−0.0149 (14)
O20.0414 (14)0.0367 (14)0.0448 (15)−0.0073 (12)0.0263 (12)−0.0059 (12)
N10.0474 (19)0.0402 (19)0.0470 (19)−0.0135 (14)0.0304 (16)−0.0111 (15)
N20.0384 (17)0.0362 (16)0.0497 (19)−0.0090 (14)0.0298 (16)−0.0095 (15)
C10.0337 (19)0.045 (2)0.037 (2)−0.0012 (16)0.0183 (16)−0.0034 (17)
C20.0314 (18)0.0345 (19)0.038 (2)0.0022 (15)0.0159 (16)−0.0009 (16)
C30.037 (2)0.039 (2)0.043 (2)0.0103 (17)0.0138 (18)−0.0039 (18)
C40.046 (2)0.064 (2)0.035 (2)0.015 (2)0.0181 (19)0.003 (2)
C50.046 (2)0.060 (2)0.046 (2)0.005 (2)0.025 (2)0.011 (2)
C60.043 (2)0.042 (2)0.045 (2)−0.0020 (19)0.0247 (18)−0.0021 (19)
C70.058 (2)0.040 (2)0.055 (2)−0.0046 (19)0.032 (2)0.0053 (19)
C80.054 (2)0.068 (3)0.059 (2)−0.009 (2)0.041 (2)−0.012 (2)
C90.049 (2)0.050 (2)0.068 (2)−0.004 (2)0.043 (2)−0.011 (2)
C100.045 (2)0.040 (2)0.066 (2)−0.0138 (18)0.031 (2)−0.016 (2)
C110.064 (2)0.031 (2)0.066 (2)−0.0147 (19)0.039 (2)−0.0104 (19)
C120.038 (2)0.045 (2)0.051 (2)−0.0141 (19)0.0248 (18)−0.017 (2)
C130.042 (2)0.046 (2)0.040 (2)−0.0026 (18)0.0205 (18)−0.0064 (18)
C140.040 (2)0.063 (3)0.057 (2)−0.006 (2)0.022 (2)−0.014 (2)
C150.055 (2)0.056 (2)0.055 (2)0.012 (2)0.023 (2)−0.007 (2)
C160.072 (3)0.039 (2)0.069 (3)−0.001 (2)0.038 (2)−0.009 (2)
C170.050 (2)0.043 (2)0.055 (2)−0.0035 (19)0.031 (2)−0.011 (2)
C180.045 (2)0.036 (2)0.040 (2)−0.0041 (17)0.0241 (18)−0.0073 (17)
Cu1—O11.913 (2)C10—C111.523 (5)
Cu1—O21.955 (2)C12—C131.505 (5)
Cu1—O2i2.381 (3)C13—C141.387 (6)
Cu1—N12.026 (4)C13—C181.408 (5)
Cu1—N22.033 (3)C14—C151.371 (6)
Cl1—C21.740 (4)C15—C161.368 (7)
Cl2—C41.751 (4)C16—C171.383 (6)
Cl3—C151.752 (5)C17—C181.409 (5)
Cl4—C171.744 (4)C3—H10.930
O1—C11.313 (5)C5—H20.930
O2—C181.332 (4)C7—H30.970
N1—C71.472 (4)C7—H40.970
N1—C81.470 (7)C8—H50.970
N1—C111.484 (5)C8—H60.970
N2—C91.479 (7)C9—H70.970
N2—C101.487 (4)C9—H80.970
N2—C121.472 (4)C10—H90.970
C1—C21.406 (4)C10—H100.970
C1—C61.419 (6)C11—H110.970
C2—C31.373 (6)C11—H120.970
C3—C41.372 (7)C12—H130.970
C4—C51.373 (5)C12—H140.970
C5—C61.378 (6)C14—H150.930
C6—C71.519 (5)C16—H160.930
C8—C91.521 (5)
O1—Cu1—O297.69 (11)C13—C14—C15120.3 (4)
O1—Cu1—O2i96.68 (12)Cl3—C15—C14119.7 (3)
O1—Cu1—N193.97 (12)Cl3—C15—C16119.6 (3)
O1—Cu1—N2162.75 (17)C14—C15—C16120.7 (4)
O2—Cu1—O2i85.84 (11)C15—C16—C17119.2 (4)
O2—Cu1—N1163.66 (13)Cl4—C17—C16118.3 (3)
O2—Cu1—N292.90 (12)Cl4—C17—C18119.2 (3)
O2i—Cu1—N1104.18 (13)C16—C17—C18122.5 (4)
O2i—Cu1—N297.64 (12)O2—C18—C13122.8 (3)
N1—Cu1—N273.22 (13)O2—C18—C17121.3 (3)
Cu1—O1—C1121.8 (3)C13—C18—C17115.9 (3)
Cu1—O2—Cu1i94.16 (10)C2—C3—H1120.4
Cu1—O2—C18114.4 (3)C4—C3—H1120.4
Cu1i—O2—C18132.1 (2)C4—C5—H2119.9
Cu1—N1—C7115.6 (3)C6—C5—H2119.9
Cu1—N1—C8102.7 (2)N1—C7—H3109.1
Cu1—N1—C11102.5 (2)N1—C7—H4109.1
C7—N1—C8113.9 (3)C6—C7—H3109.1
C7—N1—C11112.1 (2)C6—C7—H4109.1
C8—N1—C11109.0 (3)H3—C7—H4107.8
Cu1—N2—C9102.5 (2)N1—C8—H5110.1
Cu1—N2—C10103.1 (2)N1—C8—H6110.1
Cu1—N2—C12116.0 (2)C9—C8—H5110.1
C9—N2—C10107.9 (3)C9—C8—H6110.1
C9—N2—C12113.3 (3)H5—C8—H6108.4
C10—N2—C12112.8 (3)N2—C9—H7110.2
O1—C1—C2120.9 (4)N2—C9—H8110.2
O1—C1—C6123.2 (3)C8—C9—H7110.2
C2—C1—C6115.8 (3)C8—C9—H8110.2
Cl1—C2—C1117.9 (3)H7—C9—H8108.5
Cl1—C2—C3119.3 (2)N2—C10—H9110.3
C1—C2—C3122.7 (4)N2—C10—H10110.3
C2—C3—C4119.2 (3)C11—C10—H9110.3
Cl2—C4—C3118.7 (3)C11—C10—H10110.3
Cl2—C4—C5120.4 (4)H9—C10—H10108.5
C3—C4—C5120.8 (4)N1—C11—H11110.1
C4—C5—C6120.2 (4)N1—C11—H12110.1
C1—C6—C5121.2 (3)C10—C11—H11110.1
C1—C6—C7118.5 (4)C10—C11—H12110.1
C5—C6—C7120.2 (4)H11—C11—H12108.4
N1—C7—C6112.6 (3)N2—C12—H13109.6
N1—C8—C9107.8 (4)N2—C12—H14109.6
N2—C9—C8107.7 (3)C13—C12—H13109.6
N2—C10—C11107.3 (3)C13—C12—H14109.6
N1—C11—C10107.9 (3)H13—C12—H14108.1
N2—C12—C13110.3 (2)C13—C14—H15119.8
C12—C13—C14119.9 (3)C15—C14—H15119.8
C12—C13—C18118.8 (3)C15—C16—H16120.4
C14—C13—C18121.2 (3)C17—C16—H16120.4
O1—Cu1—O2—Cu1i96.20 (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—C1134.9 (2)C11—N1—C7—C6169.5 (4)
O1—Cu1—O2i—Cu1i−97.27 (11)C8—N1—C11—C1062.6 (5)
O1—Cu1—O2i—C18i31.3 (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—C1143.3 (4)
O1—Cu1—N1—C8111.7 (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—C864.4 (3)
O1—Cu1—N2—C912.7 (5)C9—N2—C12—C1365.1 (4)
O1—Cu1—N2—C10−99.3 (4)C12—N2—C9—C8−169.8 (3)
O1—Cu1—N2—C12136.8 (4)C10—N2—C12—C13−171.8 (4)
N2—Cu1—O1—C17.5 (5)C12—N2—C10—C11169.2 (4)
O2—Cu1—O2i—C18i128.6 (3)O1—C1—C2—Cl1−1.8 (5)
O2i—Cu1—O2—C18140.4 (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—C75.2 (5)
O2—Cu1—N1—C1189.3 (5)C2—C1—C6—C52.3 (5)
N1—Cu1—O2—Cu1i−128.7 (4)C2—C1—C6—C7−173.1 (3)
N1—Cu1—O2—C1811.7 (5)C6—C1—C2—Cl1176.5 (2)
O2—Cu1—N2—C9−115.2 (2)C6—C1—C2—C3−1.0 (5)
O2—Cu1—N2—C10132.8 (3)Cl1—C2—C3—C4−178.9 (3)
O2—Cu1—N2—C128.9 (3)C1—C2—C3—C4−1.3 (6)
N2—Cu1—O2—Cu1i−97.46 (12)C2—C3—C4—Cl2179.2 (3)
N2—Cu1—O2—C1843.0 (2)C2—C3—C4—C52.5 (6)
O2i—Cu1—N1—C785.0 (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—Cu1i166.91 (10)C4—C5—C6—C7174.1 (4)
N1—Cu1—O2i—C18i−64.5 (3)C1—C6—C7—N1−55.4 (6)
O2i—Cu1—N2—C9158.6 (2)C5—C6—C7—N1129.1 (4)
O2i—Cu1—N2—C1046.6 (3)N1—C8—C9—N2−0.5 (4)
O2i—Cu1—N2—C12−77.3 (2)N2—C10—C11—N11.5 (6)
N2—Cu1—O2i—Cu1i92.37 (12)N2—C12—C13—C14−120.3 (4)
N2—Cu1—O2i—C18i−139.0 (3)N2—C12—C13—C1856.3 (6)
N1—Cu1—N2—C956.1 (2)C12—C13—C14—C15177.7 (4)
N1—Cu1—N2—C10−56.0 (3)C12—C13—C18—O22.5 (7)
N1—Cu1—N2—C12−179.9 (2)C12—C13—C18—C17−176.0 (4)
N2—Cu1—N1—C7178.8 (3)C14—C13—C18—O2179.0 (4)
N2—Cu1—N1—C8−56.5 (2)C14—C13—C18—C170.5 (7)
N2—Cu1—N1—C1156.5 (2)C18—C13—C14—C151.1 (8)
Cu1—O1—C1—C2−140.0 (3)C13—C14—C15—Cl3−179.6 (4)
Cu1—O1—C1—C641.7 (5)C13—C14—C15—C16−2.2 (8)
Cu1—O2—C18—C13−54.9 (5)Cl3—C15—C16—C17179.0 (4)
Cu1—O2—C18—C17123.5 (4)C14—C15—C16—C171.6 (9)
Cu1i—O2—C18—C1366.2 (6)C15—C16—C17—Cl4−178.5 (4)
Cu1i—O2—C18—C17−115.3 (4)C15—C16—C17—C180.2 (6)
Cu1—N1—C7—C652.4 (5)Cl4—C17—C18—O2−1.0 (7)
Cu1—N1—C8—C945.0 (3)Cl4—C17—C18—C13177.5 (3)
Cu1—N1—C11—C10−45.7 (4)C16—C17—C18—O2−179.7 (5)
C7—N1—C8—C9170.8 (3)C16—C17—C18—C13−1.2 (7)
D—H···AD—HH···AD···AD—H···A
C11—H12···Cl4i0.972.763.544 (5)138
C12—H14···O1i0.972.193.112 (6)159
Cu1—O11.913 (2)
Cu1—O21.955 (2)
Cu1—O2i 2.381 (3)
Cu1—N12.026 (4)
Cu1—N22.033 (3)
O1—Cu1—O297.69 (11)
O1—Cu1—O2i 96.68 (12)
O1—Cu1—N193.97 (12)
O2—Cu1—O2i 85.84 (11)
O2—Cu1—N292.90 (12)
O2i—Cu1—N1104.18 (13)
O2i—Cu1—N297.64 (12)
N1—Cu1—N273.22 (13)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A D—HH⋯A D⋯A D—H⋯A
C11—H12⋯Cl4i 0.972.763.544 (5)138
C12—H14⋯O1i 0.972.193.112 (6)159

Symmetry code: (i) .

  4 in total

1.  Crystal structure of [1,4-bis[1-(3,5-dichlorophenolato-2-ylmethyl)-ylpropylamino-kappa2N,O]piperazine-kappa2N,N']cobalt(II).

Authors:  Koji Kubono; Naoki Hirayama; Hisao Kokusen; Kunihiko Yokoi
Journal:  Anal Sci       Date:  2003-04       Impact factor: 2.081

2.  Monoclinic and orthorhombic polymorphs of 4,4',6,6'-tetrachloro-2,2'-(piperazine-1,4-diyldimethylene)diphenol.

Authors:  Koji Kubono; Kunihiko Yokoi
Journal:  Acta Crystallogr C       Date:  2007-08-17       Impact factor: 1.172

3.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

4.  Structure validation in chemical crystallography.

Authors:  Anthony L Spek
Journal:  Acta Crystallogr D Biol Crystallogr       Date:  2009-01-20
  4 in total
  2 in total

1.  Aqua-{4,4',6,6'-tetra-fluoro-2,2'-[(piperazine-1,4-di-yl)dimethyl-ene]diphenolato}copper(II).

Authors:  Koji Kubono; Yuki Tsuno; Keita Tani; Kunihiko Yokoi
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2010-10-13

2.  Di-μ(2)-acetato-1:2κ(2)O:O';2:3κ(2)O:O'-bis-{μ(2)-4,4'-dichloro-2,2'-[2,2-dimethyl-propane-1,3-diylbis(nitrilo-methanylyl-idene)]diphenolato}-1:2κ(6)O,N,N',O':O,O';2:3κ(6)O,O':O,N,N',O'-tricopper(II).

Authors:  Koji Kubono; Keita Tani; Kunihiko Yokoi
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2012-10-31
  2 in total

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