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Acta Cryst. (2007). E63, m1545    [ doi:10.1107/S1600536807019885 ]

Bis(N,N'-di-2-furylethane-1,2-diamine-[kappa]2N,N')bis(perchlorato-[kappa]O)copper(II)

X.-H. Wang, H.-P. Zhang, J.-D. Hu, Z.-Q. Pan, Y.-Z. Li and H. Zhou

Abstract top

In the title complex, [Cu(ClO4)2(C12H16N2O2)2], the six-coordinate Cu atom lies on an inversion center with four amine N atoms in the equatorial plane, with Cu-N distances of 2.049 (3) and 2.055 (3) Å, and two perchlorate O atoms in axial positions, with Cu-O distances of 2.580 (2) Å.

Comment top

The synthesis of phenol-based macrocyclic ligands having dissimilar coordination environments and their functional bimetallic complexes has lead to increasing attention to their potentially unique properties (Karunakaran et al., 1994; Hori et al., 2001; McCollum et al., 1994;). The compartmental ligand synthesized by the precursor diamine N, N'-bis(2-furyl)-1,2-diaminoethane has been reported (Sun et al., 2001). However, the crystal structures of Cu(II) complex with perchlorate anions participating in coordination of the precursor compound have not been reported. In this paper, we reported the structure of the title complex Bis[N, N'-bis(2-furyl)-1,2-diaminoethane-κN,κN'] bis(perchlorato-κO)copper(II), (I).

In the structure of (I) the copper atom is six coordinate with four N atoms and two O atoms (Fig. 1). The equatorial positions completed by four nitrogen atoms from two diamines in which the distance of Cu—N are 2.049 (3) and 2.055 (3) Å. The Cu(II) atom lies on a crystallographic inversion centre at the centre of the N(amine)4 plane. Two perchlorate O atoms occupy the axial positions with the Cu—O distance of 2.580 (2) Å. Intramolecular N—H···O hydrogen bonds play an important role in stabilizing the axial coordination of the perchlorate anions.

Related literature top

For related literature, see: Akitsu & Komorita (2003) [Not cited anywhere in supplementary material; should it be included here?]; Hori et al. (2001); Karunakaran & Kandaswamy (1994); McCollum et al. (1994); Rameau (1938); Sun et al. (2000).

Experimental top

N, N'-bis(2-furyl)-1,2-diaminoethane was prepared using a variant of the method suggested by Rameau (1938). The title complex was synthesized by the following procedure: a solution of N, N'-bis(2-furyl)-1,2-diaminoethane (2 mmol) in 15 ml of absolute methanol was added dropwise a methanol solution (10 ml) of Cu(OAc)2H2O (1 mmol). The mixture was stirred at ambient temperature for about 3 h and then a dark blue solution appeared. A methanol solution (5 ml) of NaClO4H2O (2 mmol) was added to the mixture and the stirring was continued for 2 h. Blue block crystals of the title complex suitable for X-ray diffraction precipitated in about a month.

Refinement top

All H atoms were placed in calculated positions, with C—H distances 0.93, 0.97 Å, and N—H distances 0.91 Å, and included in the refinement in the riding-model approximation, with Uiso(H) = 1.2–1.5 Ueq(C/N). Data collection: SMART(Bruker, 2000); cellrefinement: SAINT(Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL(Bruker, 2000); program(s) used to refine structure: SHELXTL SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the title complex cation, showing the labeling of the non-H atoms and 30% probability ellipsoids. H atoms have been omitted. Atoms marked with an asterisk(*) are at the symmetry-generated position (Symmetry code for primed atoms: -x, 1 - y, 2 - z).
Bis(N,N'-di-2-furylethane-1,2-diamine-κ2N,N')bis(perchlorato-κO)copper(II) top
Crystal data top
[Cu(ClO4)2(C12H16N2O2)2]F(000) = 726
Mr = 702.98Dx = 1.643 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3385 reflections
a = 10.0062 (7) Åθ = 2.1–25,56°
b = 9.6093 (7) ŵ = 1.03 mm−1
c = 15.1933 (11) ÅT = 291 K
β = 103.371 (1)°Block, blue
V = 1421.27 (18) Å30.30 × 0.24 × 0.22 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer		2786 independent reflections
Radiation source: sealed tube2068 reflections with I > 2σ(I)
graphiteRint = 0.045
φ and ω scansθmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −12→12
Tmin = 0.7, Tmax = 0.8k = −11→11
8032 measured reflectionsl = −12→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.05P)2 + 0.22P]
where P = (Fo2 + 2Fc2)/3
2786 reflections(Δ/σ)max < 0.001
196 parametersΔρmax = 0.43 e Å−3
0 restraintsΔρmin = −0.75 e Å−3
Crystal data top
[Cu(ClO4)2(C12H16N2O2)2]V = 1421.27 (18) Å3
Mr = 702.98Z = 2
Monoclinic, P21/nMo Kα radiation
a = 10.0062 (7) ŵ = 1.03 mm−1
b = 9.6093 (7) ÅT = 291 K
c = 15.1933 (11) Å0.30 × 0.24 × 0.22 mm
β = 103.371 (1)°
Data collection top
Bruker SMART APEX CCD
diffractometer		2786 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		2068 reflections with I > 2σ(I)
Tmin = 0.7, Tmax = 0.8Rint = 0.045
8032 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.106Δρmax = 0.43 e Å−3
S = 1.03Δρmin = −0.75 e Å−3
2786 reflectionsAbsolute structure: ?
196 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
C10.2589 (5)0.0200 (5)0.8115 (3)0.0586 (12)
H10.3444−0.01390.80770.070*
C20.1440 (5)−0.0538 (4)0.7913 (3)0.0525 (10)
H20.1340−0.14530.77090.063*
C30.0384 (4)0.0363 (4)0.8075 (3)0.0457 (9)
H3−0.05420.01520.80010.055*
C40.1012 (3)0.1590 (4)0.8358 (2)0.0341 (7)
C50.0510 (4)0.2937 (4)0.8638 (2)0.0373 (8)
H5A−0.04710.29990.83810.045*
H5B0.09470.36860.83810.045*
C60.0145 (3)0.2074 (3)1.0105 (2)0.0324 (7)
H6A0.05730.20771.07460.039*
H6B0.02870.11660.98620.039*
C70.1361 (3)0.7639 (3)1.0038 (2)0.0359 (8)
H7A0.17770.83060.97030.043*
H7B0.18040.77231.06750.043*
C80.2997 (4)0.5723 (4)1.0038 (3)0.0457 (9)
H8A0.31930.56061.06900.055*
H8B0.30800.48170.97740.055*
C90.4052 (4)0.6668 (4)0.9813 (2)0.0386 (8)
C100.4827 (4)0.7663 (5)1.0263 (3)0.0518 (11)
H100.48420.79541.08490.062*
C110.5631 (4)0.8205 (5)0.9692 (3)0.0517 (10)
H110.62760.89170.98300.062*
C120.5297 (4)0.7519 (5)0.8937 (3)0.0537 (10)
H120.56710.76640.84390.064*
Cl1−0.13795 (9)0.60868 (10)0.76242 (6)0.0420 (2)
Cu10.00000.50001.00000.02706 (16)
N10.0763 (3)0.3160 (3)0.96415 (17)0.0272 (6)
H1A0.16860.31530.98740.033*
N20.1541 (3)0.6213 (3)0.97196 (19)0.0292 (6)
H2A0.13800.62630.91060.035*
O10.2368 (3)0.1501 (3)0.8381 (2)0.0499 (7)
O20.4316 (3)0.6552 (3)0.89835 (19)0.0560 (7)
O110.0075 (3)0.6289 (3)0.7745 (2)0.0543 (7)
O12−0.2058 (3)0.7378 (3)0.7460 (2)0.0690 (9)
O13−0.1621 (3)0.5492 (3)0.84465 (16)0.0443 (6)
O14−0.1861 (3)0.5187 (3)0.68809 (19)0.0562 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.071 (3)0.055 (3)0.055 (3)0.021 (2)0.027 (2)−0.003 (2)
C20.085 (3)0.035 (2)0.043 (2)0.010 (2)0.026 (2)0.0018 (18)
C30.055 (2)0.034 (2)0.050 (2)−0.0114 (16)0.0143 (18)−0.0025 (16)
C40.0398 (19)0.0319 (18)0.0322 (18)0.0031 (14)0.0118 (15)0.0042 (14)
C50.050 (2)0.0312 (18)0.0314 (18)0.0001 (15)0.0101 (15)0.0062 (14)
C60.0460 (19)0.0212 (15)0.0304 (18)0.0043 (14)0.0096 (15)0.0031 (13)
C70.0460 (19)0.0264 (17)0.039 (2)−0.0131 (14)0.0182 (16)−0.0034 (14)
C80.0340 (18)0.041 (2)0.062 (3)−0.0051 (16)0.0112 (17)0.0145 (19)
C90.0384 (18)0.047 (2)0.0314 (18)−0.0067 (16)0.0104 (15)−0.0036 (15)
C100.056 (2)0.061 (3)0.045 (2)−0.023 (2)0.0239 (19)−0.021 (2)
C110.054 (2)0.052 (3)0.050 (3)−0.0142 (19)0.015 (2)−0.002 (2)
C120.053 (2)0.069 (3)0.043 (2)−0.012 (2)0.0191 (19)0.003 (2)
Cl10.0446 (5)0.0399 (5)0.0386 (5)0.0043 (4)0.0037 (4)0.0034 (4)
Cu10.0272 (3)0.0256 (3)0.0288 (3)−0.0034 (2)0.0074 (2)−0.0020 (2)
N10.0300 (13)0.0224 (14)0.0292 (14)0.0006 (10)0.0066 (11)0.0003 (11)
N20.0326 (14)0.0235 (14)0.0304 (14)−0.0060 (11)0.0050 (11)−0.0001 (11)
O10.0443 (14)0.0449 (16)0.0651 (18)−0.0031 (12)0.0221 (13)−0.0113 (13)
O20.0613 (17)0.0652 (19)0.0438 (16)−0.0189 (14)0.0167 (13)−0.0143 (14)
O110.0411 (14)0.069 (2)0.0525 (17)−0.0067 (13)0.0108 (12)0.0176 (14)
O120.078 (2)0.052 (2)0.070 (2)0.0331 (16)0.0033 (17)0.0144 (16)
O130.0485 (14)0.0503 (15)0.0328 (13)−0.0055 (12)0.0068 (11)0.0001 (11)
O140.0743 (18)0.0513 (18)0.0442 (16)−0.0127 (14)0.0162 (14)−0.0109 (13)
Geometric parameters (Å, °) top
C1—C21.325 (6)C8—H8A0.9700
C1—O11.348 (5)C8—H8B0.9700
C1—H10.9300C9—C101.319 (5)
C2—C31.430 (6)C9—O21.351 (4)
C2—H20.9300C10—C111.413 (5)
C3—C41.359 (5)C10—H100.9300
C3—H30.9300C11—C121.298 (6)
C4—O11.351 (4)C11—H110.9300
C4—C51.486 (5)C12—O21.365 (5)
C5—N11.502 (4)C12—H120.9300
C5—H5A0.9700Cl1—O121.408 (3)
C5—H5B0.9700Cl1—O141.415 (3)
C6—N11.472 (4)Cl1—O111.437 (3)
C6—C7i1.497 (5)Cl1—O131.444 (3)
C6—H6A0.9700Cu1—N1i2.049 (3)
C6—H6B0.9700Cu1—N12.049 (3)
C7—N21.478 (4)Cu1—N22.055 (3)
C7—C6i1.497 (5)Cu1—N2i2.055 (3)
C7—H7A0.9700Cu1—O132.580 (2)
C7—H7B0.9700N1—H1A0.9100
C8—C91.491 (5)N2—H2A0.9099
C8—N21.500 (4)
C2—C1—O1111.9 (4)C9—C10—H10126.3
C2—C1—H1124.1C11—C10—H10126.3
O1—C1—H1124.1C12—C11—C10106.7 (4)
C1—C2—C3105.8 (4)C12—C11—H11126.6
C1—C2—H2127.1C10—C11—H11126.6
C3—C2—H2127.1C11—C12—O2110.0 (4)
C4—C3—C2105.9 (4)C11—C12—H12125.0
C4—C3—H3127.0O2—C12—H12125.0
C2—C3—H3127.0O12—Cl1—O14109.6 (2)
O1—C4—C3109.9 (3)O12—Cl1—O11109.6 (2)
O1—C4—C5116.9 (3)O14—Cl1—O11109.43 (19)
C3—C4—C5133.2 (3)O12—Cl1—O13109.36 (19)
C4—C5—N1115.2 (3)O14—Cl1—O13110.76 (17)
C4—C5—H5A108.5O11—Cl1—O13108.06 (16)
N1—C5—H5A108.5N1i—Cu1—N1180.000 (1)
C4—C5—H5B108.5N1i—Cu1—N284.79 (10)
N1—C5—H5B108.5N1—Cu1—N295.21 (10)
H5A—C5—H5B107.5N1i—Cu1—N2i95.21 (10)
N1—C6—C7i108.7 (3)N1—Cu1—N2i84.79 (10)
N1—C6—H6A110.0N2—Cu1—N2i180.0
C7i—C6—H6A110.0N1i—Cu1—O1383.74 (10)
N1—C6—H6B110.0N1—Cu1—O1396.26 (10)
C7i—C6—H6B110.0N2—Cu1—O1392.84 (10)
H6A—C6—H6B108.3N2i—Cu1—O1387.16 (10)
N2—C7—C6i108.6 (3)C6—N1—C5113.2 (3)
N2—C7—H7A110.0C6—N1—Cu1105.13 (19)
C6i—C7—H7A110.0C5—N1—Cu1114.0 (2)
N2—C7—H7B110.0C6—N1—H1A108.1
C6i—C7—H7B110.0C5—N1—H1A108.1
H7A—C7—H7B108.4Cu1—N1—H1A108.1
C9—C8—N2114.9 (3)C7—N2—C8111.6 (3)
C9—C8—H8A108.5C7—N2—Cu1107.67 (19)
N2—C8—H8A108.5C8—N2—Cu1118.3 (2)
C9—C8—H8B108.5C7—N2—H2A106.3
N2—C8—H8B108.5C8—N2—H2A106.0
H8A—C8—H8B107.5Cu1—N2—H2A106.2
C10—C9—O2109.0 (3)C1—O1—C4106.5 (3)
C10—C9—C8133.2 (4)C9—O2—C12106.9 (3)
O2—C9—C8117.8 (3)Cl1—O13—Cu1131.97 (15)
C9—C10—C11107.4 (3)
Symmetry codes: (i) −x, −y+1, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O110.912.183.021 (4)154
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O110.912.183.021 (4)154
Acknowledgements top

The authors thank the National Science Foundation of China (No. 20271039).

references
References top

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Bruker (2000). SMART (Version 6.22), SAINT (Version 6.22), SHELXTL (Version 6.10) and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Hori, A., Yonemura, M., Ohba, M. & Ōkawa, H. (2001). Bull. Chem. Soc. Jpn, 74, 495–503.

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Rameau, J. Th. L. B. (1938). Rev. Trav. Chim. 57, 192–214.

Sun, G.-C., He, Z.-H., Li, Z.-J., Yuan, X.-D., Yang, Z.-J., Wang, G.-X., Wang, L.-F. & Liu, C.-R. (2000). Molecules, 6, 1001–1005. Please check date; cited as 2001 in Comment section of CIF.