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Acta Cryst. (2007). E63, m3010    [ doi:10.1107/S1600536807056838 ]

Di-[mu]-chlorido-1:2[kappa]2Cl,2:3[kappa]2Cl-tetrachlorido-1[kappa]Cl,2[kappa]2Cl,3[kappa]Cl-bis[N,N''-bis(2-furylmethylene)diethylenetriamine]-1[kappa]3N,N',N'';3[kappa]3N,N',N''-tricopper(II)

Q. Wang, D.-Q. Wang and Y.-Y. Sun

Abstract top

The complete title trinuclear CuII complex, [Cu3Cl6(C14H16N3O2)2], is generated by twofold symmetry with one Cu atom lying on the rotation axis. The central Cu atom adopts a distorted tetrahedral CuCl4 geometry. The terminal Cu atom is five-coordinated in a distorted square-pyramidal coordination environment consisting of three N atoms of the ligand, one bridging Cl atom and one terminal Cl atom. Intermolecular C-H...Cl hydrogen bonds help to establish the packing.

Comment top

Transition metals complexed with multidentate Schiff base ligands result in homo and/or heteronuclear metal complexes with insteresting stereochemistry (e.g. Erxleben et al., 2001). Such species can be used as biological models, catalysis, and molecular ferromagnets (Mukherjee et al., 2002). The Schiff base N,N'-bis(2-furylmethylene)diethylenetriamine is considered to be a good chelating ligand, which can coordinate to transition metals as a tridentate, tetradentate or pentadentate ligand, with consequent variable chemical properties. We report here the synthesis and crystal structure of the title compound, (I), a new copper(II) complex, with a multidentate Schiff base ligand derived from the condensation of 2-furaldehyde and diethylenetriamine.

The complete molecule of (I) (Fig. 1) is generated by 2-fold symmetry. The terminal Cu1 atom is five-coordinated in a distorted square-pyramidal coordination environment consisting of three N atoms of the ligand, one bridging Cl atom and one terminal Cl atom. Cu2 (site symmetry 2) is tetrahedrally coordinated by two bridging Cl atoms and two terminal Cl atoms (Table 1). The two five-membered rings Cu1—N1—C11—C12—N2 and Cu1—N2—C13—C14—N3 form a dihedral angle of 5.7 (3)°, and the dihedral angle between the mean planes of the furan rings is 25.7 (3) °. The Cu1···Cu2 separation is 4.6059 (9) Å.

In the crystal, intermolecular C—H···Cl hydrogen bonds lead to a three-dimensional network (Table 2).

Related literature top

For background, see: Erxleben et al. (2001); Mukherjee et al. (2002).

Experimental top

2-Furaldehyde (4 mmol, 384.4 mg) was added dropwise to a dichloromethane (20 ml) solution of diethylenetriamine (2 mmol, 206.4 mg). The mixture was heated under reflux with stirring for 1.5 h. An absolute ethanol solution (5 ml) of cupric chloride dihydrate (3 mmol, 511.4 mg) was then added dropwise, and the mixture was stirred at room temperature for another 15 h. The solution was filtered off, the filterate was kept at room temperature for about 12 days, after which large pale blue blocks of (I) were obtained.

Refinement top

All H-atoms were positioned geometrically and refined using a riding model, with with C—H (methyne) 0.93, C—H = 0.97 (methylene), C—H 0.93 Å (aromatic) and Uiso(H) =1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. Atoms labelled with the suffix A are generated by the symmetry operation (−x + 1/2, y, −z + 3/2). H atoms have been omitted for clarity.
Di-µ-chlorido-1:2κ2Cl,2:3κ2Cl-tetrachlorido-1κCl,2κ2Cl,3κCl- bis[N,N''-bis(2-furylmethylene)diethylenetriamine]- 1κ3N,N',N'';3κ3N,N',N''-tricopper(II) top
Crystal data top
[Cu3Cl6(C14H16N3O2)2]F000 = 926
Mr = 919.92Dx = 1.676 Mg m−3
Monoclinic, P2/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2yacCell parameters from 1576 reflections
a = 10.9456 (15) Åθ = 2.9–20.0º
b = 7.5287 (10) ŵ = 2.22 mm−1
c = 22.248 (2) ÅT = 298 (2) K
β = 96.048 (2)ºBlock, pale blue
V = 1823.1 (4) Å30.26 × 0.14 × 0.05 mm
Z = 2
Data collection top
Siemens SMART CCD
diffractometer		3200 independent reflections
Radiation source: fine-focus sealed tube1749 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.066
T = 298(2) Kθmax = 25.0º
ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→13
Tmin = 0.597, Tmax = 0.897k = −6→8
8801 measured reflectionsl = −21→26
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.088  w = 1/[σ2(Fo2) + (0.0225P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.002
3200 reflectionsΔρmax = 0.64 e Å−3
213 parametersΔρmin = −0.41 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu3Cl6(C14H16N3O2)2]V = 1823.1 (4) Å3
Mr = 919.92Z = 2
Monoclinic, P2/nMo Kα
a = 10.9456 (15) ŵ = 2.22 mm−1
b = 7.5287 (10) ÅT = 298 (2) K
c = 22.248 (2) Å0.26 × 0.14 × 0.05 mm
β = 96.048 (2)º
Data collection top
Siemens SMART CCD
diffractometer		3200 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1749 reflections with I > 2σ(I)
Tmin = 0.597, Tmax = 0.897Rint = 0.066
8801 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047213 parameters
wR(F2) = 0.088H-atom parameters constrained
S = 0.99Δρmax = 0.64 e Å−3
3200 reflectionsΔρmin = −0.41 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
xyzUiso*/Ueq
C130.4074 (5)−0.2812 (7)0.6330 (2)0.0646 (16)
H13A0.3969−0.35040.66890.077*
H13B0.4537−0.35170.60680.077*
Cu10.45072 (5)0.05268 (9)0.58051 (3)0.0527 (2)
Cu20.25000.13781 (14)0.75000.0624 (3)
Cl10.42526 (12)0.2454 (2)0.50298 (6)0.0691 (5)
Cl20.32170 (13)0.2627 (2)0.66945 (6)0.0689 (4)
Cl30.07882 (15)−0.0122 (2)0.71301 (7)0.0956 (6)
C110.6627 (5)0.0402 (8)0.6707 (2)0.0605 (16)
H11A0.64510.09610.70820.073*
H11B0.75110.02970.67110.073*
C70.1142 (5)−0.1623 (8)0.4910 (2)0.0537 (15)
C20.7637 (5)0.3940 (8)0.6357 (3)0.0523 (15)
O20.0691 (3)−0.1249 (5)0.43235 (18)0.0719 (12)
O10.8276 (4)0.3279 (6)0.68845 (18)0.0753 (12)
C60.2281 (5)−0.0728 (7)0.5094 (2)0.0513 (14)
H60.25000.01480.48310.062*
C10.6602 (5)0.2975 (8)0.6072 (2)0.0528 (15)
H10.62040.35520.57370.063*
C50.9170 (6)0.4454 (11)0.7032 (3)0.086 (2)
H50.97460.43470.73690.104*
C140.2835 (5)−0.2341 (7)0.6005 (2)0.0596 (15)
H14A0.2462−0.33780.58020.071*
H14B0.2292−0.19110.62910.071*
C30.8128 (5)0.5445 (8)0.6198 (2)0.0615 (16)
H30.78680.61410.58640.074*
C80.0327 (5)−0.2627 (8)0.5169 (3)0.0640 (16)
H80.0412−0.30540.55640.077*
C9−0.0679 (6)−0.2912 (9)0.4730 (3)0.078 (2)
H9−0.1392−0.35440.47790.093*
C40.9142 (6)0.5794 (10)0.6643 (3)0.085 (2)
H40.96730.67610.66570.101*
C10−0.0405 (6)−0.2098 (9)0.4234 (3)0.074 (2)
H10−0.0904−0.21080.38690.088*
N10.6121 (3)0.1490 (6)0.61850 (17)0.0478 (11)
N30.3035 (4)−0.0958 (6)0.55647 (19)0.0488 (12)
N20.4730 (4)−0.1175 (6)0.64975 (17)0.0529 (12)
C120.6046 (5)−0.1397 (8)0.6653 (2)0.0672 (17)
H12A0.6392−0.20770.63410.081*
H12B0.6202−0.20330.70320.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C130.077 (4)0.051 (4)0.066 (4)0.003 (3)0.006 (3)0.012 (3)
Cu10.0446 (4)0.0592 (5)0.0538 (4)−0.0022 (4)0.0024 (3)0.0115 (4)
Cu20.0607 (7)0.0705 (8)0.0559 (6)0.0000.0051 (5)0.000
Cl10.0545 (9)0.0818 (12)0.0691 (10)−0.0113 (8)−0.0027 (7)0.0301 (8)
Cl20.0692 (10)0.0623 (11)0.0764 (10)−0.0040 (8)0.0138 (8)0.0099 (8)
Cl30.0959 (13)0.1257 (18)0.0656 (11)−0.0453 (12)0.0108 (9)−0.0127 (10)
C110.055 (4)0.067 (5)0.057 (4)0.002 (3)−0.005 (3)0.013 (3)
C70.050 (4)0.056 (4)0.054 (4)0.007 (3)−0.003 (3)−0.011 (3)
C20.043 (3)0.058 (5)0.057 (4)0.002 (3)0.008 (3)−0.003 (3)
O20.057 (3)0.088 (3)0.069 (3)0.002 (2)−0.003 (2)−0.007 (2)
O10.066 (3)0.083 (4)0.075 (3)−0.008 (3)−0.003 (2)−0.007 (2)
C60.050 (3)0.050 (4)0.056 (4)0.005 (3)0.014 (3)−0.005 (3)
C10.045 (4)0.065 (5)0.049 (3)0.015 (3)0.010 (3)0.002 (3)
C50.070 (5)0.102 (7)0.084 (5)−0.019 (5)−0.004 (4)−0.020 (5)
C140.063 (4)0.054 (4)0.061 (4)−0.009 (3)0.005 (3)0.000 (3)
C30.058 (4)0.056 (4)0.073 (4)−0.001 (4)0.014 (3)0.002 (3)
C80.056 (4)0.065 (5)0.071 (4)−0.012 (3)0.008 (3)−0.004 (3)
C90.052 (4)0.066 (5)0.115 (6)−0.005 (3)0.003 (4)−0.017 (4)
C40.064 (4)0.075 (6)0.117 (6)−0.029 (4)0.023 (4)−0.033 (5)
C100.051 (4)0.078 (6)0.087 (5)0.011 (4)−0.013 (4)−0.033 (4)
N10.043 (3)0.057 (3)0.044 (3)0.005 (2)0.006 (2)0.008 (2)
N30.049 (3)0.048 (3)0.052 (3)−0.001 (2)0.013 (2)0.001 (2)
N20.053 (3)0.048 (3)0.055 (3)−0.008 (2)−0.009 (2)0.009 (2)
C120.080 (5)0.052 (5)0.069 (4)0.010 (4)0.004 (3)0.014 (3)
Geometric parameters (Å, °) top
C13—N21.455 (6)O2—C101.356 (6)
C13—C141.510 (6)O1—C51.334 (7)
C13—H13A0.9700C6—N31.274 (5)
C13—H13B0.9700C6—H60.9300
Cu1—N31.988 (4)C1—N11.273 (6)
Cu1—N21.999 (4)C1—H10.9300
Cu1—N12.011 (4)C5—C41.327 (8)
Cu1—Cl12.2489 (15)C5—H50.9300
Cu1—Cl22.9998 (16)C14—N31.462 (6)
Cu2—Cl22.2379 (14)C14—H14A0.9700
Cu2—Cl2i2.2379 (14)C14—H14B0.9700
Cu2—Cl32.2668 (16)C3—C41.432 (7)
Cu2—Cl3i2.2668 (16)C3—H30.9300
C11—N11.481 (6)C8—C91.409 (7)
C11—C121.495 (7)C8—H80.9300
C11—H11A0.9700C9—C101.324 (8)
C11—H11B0.9700C9—H90.9300
C7—C81.344 (7)C4—H40.9300
C7—O21.376 (5)C10—H100.9300
C7—C61.439 (7)N2—C121.455 (6)
C2—C31.318 (7)C12—H12A0.9700
C2—O11.393 (6)C12—H12B0.9700
C2—C11.436 (7)
N2—C13—C14108.6 (4)C2—C1—H1113.6
N2—C13—H13A110.0C4—C5—O1112.2 (6)
C14—C13—H13A110.0C4—C5—H5123.9
N2—C13—H13B110.0O1—C5—H5123.9
C14—C13—H13B110.0N3—C14—C13107.3 (4)
H13A—C13—H13B108.4N3—C14—H14A110.3
N3—Cu1—N282.91 (18)C13—C14—H14A110.3
N3—Cu1—N1165.25 (18)N3—C14—H14B110.3
N2—Cu1—N182.92 (17)C13—C14—H14B110.3
N3—Cu1—Cl197.19 (13)H14A—C14—H14B108.5
N2—Cu1—Cl1179.66 (14)C2—C3—C4106.3 (6)
N1—Cu1—Cl197.01 (13)C2—C3—H3126.9
N1—Cu1—Cl289.22 (12)C4—C3—H3126.9
N2—Cu1—Cl281.79 (13)C7—C8—C9107.1 (6)
N3—Cu1—Cl292.83 (13)C7—C8—H8126.4
Cl1—Cu1—Cl297.87 (5)C9—C8—H8126.4
Cl2—Cu2—Cl2i130.30 (9)C10—C9—C8106.2 (6)
Cl2—Cu2—Cl3105.36 (5)C10—C9—H9126.9
Cl2i—Cu2—Cl398.85 (6)C8—C9—H9126.9
Cl2—Cu2—Cl3i98.85 (5)C5—C4—C3105.9 (6)
Cl2i—Cu2—Cl3i105.36 (5)C5—C4—H4127.1
Cl3—Cu2—Cl3i120.23 (11)C3—C4—H4127.1
N1—C11—C12108.5 (4)C9—C10—O2111.7 (6)
N1—C11—H11A110.0C9—C10—H10124.1
C12—C11—H11A110.0O2—C10—H10124.1
N1—C11—H11B110.0C1—N1—C11120.9 (5)
C12—C11—H11B110.0C1—N1—Cu1126.7 (4)
H11A—C11—H11B108.4C11—N1—Cu1111.7 (3)
C8—C7—O2109.5 (5)C6—N3—C14121.2 (4)
C8—C7—C6137.4 (6)C6—N3—Cu1125.5 (4)
O2—C7—C6112.8 (5)C14—N3—Cu1113.2 (3)
C3—C2—O1110.5 (5)C12—N2—C13114.4 (5)
C3—C2—C1129.9 (6)C12—N2—Cu1107.1 (3)
O1—C2—C1119.6 (5)C13—N2—Cu1109.2 (3)
C10—O2—C7105.5 (5)N2—C12—C11108.5 (5)
C5—O1—C2105.1 (5)N2—C12—H12A110.0
N3—C6—C7129.5 (5)C11—C12—H12A110.0
N3—C6—H6115.2N2—C12—H12B110.0
C7—C6—H6115.2C11—C12—H12B110.0
N1—C1—C2132.9 (5)H12A—C12—H12B108.4
N1—C1—H1113.6
Symmetry codes: (i) −x+1/2, y, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cl3ii0.932.803.669 (7)156
C10—H10···Cl3iii0.932.803.451 (8)128
Symmetry codes: (ii) x+1, y+1, z; (iii) −x, −y, −z+1.
Table 1
Selected geometric parameters (Å) top
Cu1—N31.988 (4)Cu1—Cl22.9998 (16)
Cu1—N21.999 (4)Cu2—Cl22.2379 (14)
Cu1—N12.011 (4)Cu2—Cl32.2668 (16)
Cu1—Cl12.2489 (15)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cl3i0.932.803.669 (7)156
C10—H10···Cl3ii0.932.803.451 (8)128
Symmetry codes: (i) x+1, y+1, z; (ii) −x, −y, −z+1.
Acknowledgements top

The authors acknowledge the financial support of the Shandong Province Science Foundation, and the State Key Laboratory of Crystalline Materials, Shandong University, People's Republic of China.

references
References top

Erxleben, A. (2001). Inorg. Chem. 40, 208–213.

Mukherjee, P. S., Maji, T. K., Escuer, A., Vicente, R., Ribas, J., Rosair, G., Mautner, F. A. & Chaudhuri, N. R. (2002). Eur. J. Inorg. Chem. pp. 943–949.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.