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Acta Cryst. (2008). E64, m504    [ doi:10.1107/S1600536808005394 ]

Bis{[mu]-2,2'-[o-phenylenebis(nitrilomethylidyne)]diphenolato}dicopper(II) N,N'-dimethylformamide disolvate

G. Yu, Y. Ding, L. Wang, Z. Fu and X. Hu

Abstract top

The title compound, [Cu2(C20H14N2O2)2]·2C3H7NO, consists of a centrosymmetric dimer composed of two copper(II) ions and two tetradentate salphen ligands {H2salphen is 2,2'-[o-phenylenebis(nitrilomethylidyne)]diphenol}, and two dimethylformamide solvent molecules. The CuII atom is bonded to two N imino atoms and three phenolate O atoms of salphen. One deprotonated phenol group of each ligand bridges two Cu atoms, forming the dimer. The geometry about the five-coordinate Cu atom can best be described as slightly distorted rectangular pyramidal. The crystal structure is stabilized by [pi]-[pi] interactions [centroid-centroid distance 3.779 (2) Å] and C-H...O hydrogen bonds.

Comment top

The stucture of the title compound, [Cu(salphen)]2˙2DMF, (DMF= N,N'-dimethylformamide), (I), is shown in Fig.1.

The salphen derivatives and their manganese complexes have been synthesized and characterized(Suzuki et al.,1997).

Herein, we report the crystal structure of such a compound. As shown in Fig.1, the molecular structure of the title compound is constructed of a centrosymmetric dimer in which the copper(II) atoms are linked by µ-phenoxo bridges from one of the phenolic oxygen atoms of each salphen ligand to the opposite metal center. The distance of Cu1···Cu1(2 - x,-y,-z) separation and the angles of Cu1–O1–Cu1(2 - x,-y,-z)are 3.436 Å, and 92.19°, respectively. Two nitrogen atoms and two oxygen atoms from salphen ligands occupy the coordination sites about each copper. The apical Cu–O (phenoxo) and Cu–N (imine) (see Table 2) bond distances are somewhat shorter than the long equatorial Cu1—O1 distance. The basal atoms about the two copper atoms are coplanar; consequently, the environment around each copper atom can be described as a distorted triangular pyramid.

The centroid-centroid distance between the C8—C13 benzene ring (centroid Cg1) belonging to one salicylaldehyde ring system in one dimer and the C15—C20 benzene ring (centroid Cg2) of the salicylaldehyde ring system from the neighboring dimer at (2 - x, -y, -z) is 3.779 (2), and the dihedral angles (between planes Cg1 and Cg2) and (between planes Cg1- Cg2 vector and the normal to the C8—C13 ring) are 10.82 and 16.52°, respectively; these values indicate the existence of significant π-π stacking interactions between adjacent rings, as shown in Fig.2, which stabilizes the crystal structure together with the hydrogen bonds.

Related literature top

For related literature, see: Suzuki et al. (1997).

Experimental top

[Cu(C20H14N2O2)]2 .2DMF was prepared as followings: to a solution of H2salphen 0.158 mg(0.5 mmol) in methanol (20 mL) and DMF(20 mL) was added Cu(OAc)2˙2H2O(0.113 g, 0.5 mmol). After the mixture was stirred for half an hour, the solution was filtered. The filtrate was kept for several days at ambient temperature, and green-black block crystals were obtained.

Refinement top

The H atoms bonded to C atoms were introduced at calculated positions and refined using a riding model, with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(C), and C–H distances of 0.93–0.96 Å.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. The molecular packing diagram of (I).
Bis{µ-2,2'-[o-phenylenebis(nitrilomethylidyne)]diphenolato}dicopper(II) N,N'-dimethylformamide disolvate top
Crystal data top
[Cu2(C20H14N2O2)2]·2C3H7NOF000 = 932
Mr = 901.94Dx = 1.461 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3178 reflections
a = 8.1864 (5) Åθ = 2.8–23.0º
b = 14.7920 (10) ŵ = 1.10 mm−1
c = 16.9584 (11) ÅT = 294 (2) K
β = 93.252 (1)ºBlock, black
V = 2050.2 (2) Å30.20 × 0.10 × 0.10 mm
Z = 2
Data collection top
Bruker SMART CCD area-detector
diffractometer		4468 independent reflections
Radiation source: fine-focus sealed tube3126 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.083
T = 294(2) Kθmax = 27.0º
φ and ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		h = −10→10
Tmin = 0.811, Tmax = 0.898k = −14→18
13976 measured reflectionsl = −20→21
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)] = 0.051H-atom parameters constrained
wR(F2) = 0.129  w = 1/[σ2(Fo2) + (0.0609P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
4468 reflectionsΔρmax = 0.52 e Å−3
273 parametersΔρmin = −0.36 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Cu2(C20H14N2O2)2]·2C3H7NOV = 2050.2 (2) Å3
Mr = 901.94Z = 2
Monoclinic, P21/nMo Kα
a = 8.1864 (5) ŵ = 1.10 mm−1
b = 14.7920 (10) ÅT = 294 (2) K
c = 16.9584 (11) Å0.20 × 0.10 × 0.10 mm
β = 93.252 (1)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		4468 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		3126 reflections with I > 2σ(I)
Tmin = 0.811, Tmax = 0.898Rint = 0.083
13976 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051273 parameters
wR(F2) = 0.129H-atom parameters constrained
S = 0.98Δρmax = 0.52 e Å−3
4468 reflectionsΔρmin = −0.36 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
Cu10.87999 (4)0.02801 (2)0.07623 (2)0.03962 (15)
C10.7432 (3)0.2022 (2)0.05569 (18)0.0394 (7)
C20.6560 (4)0.2775 (2)0.0271 (2)0.0506 (8)
H20.59410.2742−0.02050.061*
C30.6622 (5)0.3569 (2)0.0699 (2)0.0614 (10)
H30.60530.40750.05080.074*
C40.7528 (5)0.3612 (2)0.1410 (3)0.0688 (11)
H40.75470.41460.17000.083*
C50.8397 (4)0.2880 (2)0.1695 (2)0.0546 (9)
H50.90140.29210.21710.065*
C60.8359 (3)0.2075 (2)0.12719 (18)0.0392 (7)
C70.6479 (4)0.0977 (2)−0.04292 (18)0.0399 (7)
H70.58580.1452−0.06470.048*
C80.6304 (4)0.0124 (2)−0.08095 (17)0.0412 (7)
C90.7215 (4)−0.0655 (2)−0.05630 (19)0.0419 (7)
C100.6853 (4)−0.1464 (2)−0.0970 (2)0.0509 (8)
H100.7399−0.1991−0.08120.061*
C110.5710 (4)−0.1499 (3)−0.1597 (2)0.0585 (10)
H110.5500−0.2046−0.18530.070*
C120.4865 (4)−0.0729 (3)−0.1852 (2)0.0566 (9)
H120.4112−0.0753−0.22830.068*
C130.5161 (4)0.0058 (2)−0.1460 (2)0.0495 (9)
H130.45880.0573−0.16270.059*
C140.9997 (4)0.1198 (2)0.21836 (19)0.0473 (8)
H141.00890.17180.24920.057*
C151.0785 (4)0.0411 (2)0.2491 (2)0.0478 (8)
C161.0733 (4)−0.0430 (2)0.2097 (2)0.0483 (9)
C171.1600 (5)−0.1157 (3)0.2469 (2)0.0654 (11)
H171.1591−0.17200.22260.078*
C181.2455 (5)−0.1043 (3)0.3184 (3)0.0746 (12)
H181.3026−0.15290.34110.090*
C191.2486 (5)−0.0225 (3)0.3570 (2)0.0787 (14)
H191.3061−0.01590.40550.094*
C201.1659 (5)0.0486 (3)0.3230 (2)0.0652 (11)
H201.16710.10380.34930.078*
C210.7335 (6)0.1052 (3)0.4145 (3)0.0950 (15)
H21A0.82990.09980.38520.142*
H21B0.65120.06430.39320.142*
H21C0.75970.09050.46890.142*
C220.5134 (5)0.2143 (3)0.4363 (3)0.0993 (17)
H22A0.49180.27800.43260.149*
H22B0.50930.19530.49020.149*
H22C0.43250.18200.40420.149*
C230.7679 (5)0.2604 (3)0.3829 (2)0.0601 (10)
H230.72430.31840.38000.072*
N10.7417 (3)0.11587 (16)0.01899 (14)0.0367 (6)
N20.9162 (3)0.12659 (17)0.15158 (14)0.0384 (6)
N30.6731 (4)0.1958 (2)0.40887 (18)0.0592 (8)
O10.8363 (3)−0.06591 (14)0.00094 (13)0.0492 (6)
O20.9963 (3)−0.05820 (15)0.14172 (14)0.0524 (6)
O30.9070 (3)0.25103 (17)0.36246 (15)0.0639 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0424 (2)0.0340 (2)0.0420 (2)0.00078 (17)−0.00157 (16)0.00026 (17)
C10.0368 (16)0.0327 (17)0.0494 (18)−0.0021 (13)0.0080 (13)0.0017 (14)
C20.052 (2)0.0390 (19)0.060 (2)−0.0029 (16)−0.0039 (16)0.0066 (17)
C30.069 (2)0.035 (2)0.080 (3)0.0043 (17)−0.001 (2)0.0036 (19)
C40.094 (3)0.033 (2)0.080 (3)−0.002 (2)0.004 (2)−0.011 (2)
C50.067 (2)0.044 (2)0.052 (2)−0.0055 (17)−0.0006 (17)−0.0067 (17)
C60.0384 (16)0.0331 (18)0.0468 (18)−0.0044 (13)0.0090 (13)−0.0004 (14)
C70.0396 (16)0.0368 (18)0.0431 (17)0.0010 (14)0.0015 (13)0.0054 (14)
C80.0402 (17)0.0428 (19)0.0410 (18)−0.0072 (14)0.0065 (13)−0.0002 (15)
C90.0402 (17)0.0417 (19)0.0445 (18)−0.0069 (15)0.0090 (14)−0.0039 (15)
C100.054 (2)0.043 (2)0.057 (2)−0.0049 (16)0.0113 (17)−0.0072 (17)
C110.059 (2)0.060 (3)0.058 (2)−0.0212 (19)0.0127 (18)−0.0195 (19)
C120.048 (2)0.072 (3)0.049 (2)−0.0140 (19)0.0005 (16)−0.012 (2)
C130.0421 (19)0.057 (2)0.049 (2)−0.0032 (16)0.0006 (15)0.0002 (17)
C140.0434 (18)0.054 (2)0.0449 (19)−0.0027 (16)0.0038 (15)−0.0066 (16)
C150.0367 (17)0.060 (2)0.0468 (19)−0.0023 (15)0.0010 (14)0.0082 (17)
C160.0377 (17)0.056 (2)0.051 (2)−0.0013 (15)0.0059 (15)0.0180 (17)
C170.067 (2)0.060 (3)0.068 (3)0.004 (2)0.001 (2)0.024 (2)
C180.068 (3)0.080 (3)0.075 (3)0.003 (2)−0.006 (2)0.039 (3)
C190.071 (3)0.108 (4)0.055 (2)−0.005 (3)−0.016 (2)0.026 (3)
C200.062 (2)0.083 (3)0.049 (2)−0.005 (2)−0.0043 (18)0.007 (2)
C210.113 (4)0.057 (3)0.119 (4)0.005 (3)0.038 (3)0.011 (3)
C220.066 (3)0.095 (4)0.140 (5)−0.001 (3)0.032 (3)−0.015 (3)
C230.073 (3)0.047 (2)0.060 (2)0.001 (2)0.002 (2)−0.0103 (19)
N10.0376 (13)0.0332 (14)0.0393 (14)−0.0014 (11)0.0030 (11)0.0017 (11)
N20.0356 (13)0.0390 (15)0.0405 (14)−0.0020 (11)0.0026 (11)−0.0006 (12)
N30.0649 (19)0.0447 (19)0.070 (2)0.0021 (15)0.0183 (16)−0.0075 (16)
O10.0563 (14)0.0337 (12)0.0564 (14)0.0036 (11)−0.0077 (11)−0.0049 (11)
O20.0599 (15)0.0405 (13)0.0557 (14)0.0052 (11)−0.0063 (11)0.0072 (11)
O30.0575 (16)0.0729 (18)0.0617 (16)−0.0080 (14)0.0076 (13)−0.0121 (14)
Geometric parameters (Å, °) top
Cu1—O11.907 (2)C12—C131.355 (5)
Cu1—O21.909 (2)C12—H120.9300
Cu1—N11.946 (2)C13—H130.9300
Cu1—N21.950 (2)C14—N21.293 (4)
Cu1—O1i2.783 (11).C14—C151.416 (4)
C1—C21.395 (4)C14—H140.9300
C1—C61.396 (4)C15—C201.411 (5)
C1—N11.420 (4)C15—C161.412 (5)
C2—C31.380 (5)C16—O21.302 (4)
C2—H20.9300C16—C171.416 (4)
C3—C41.381 (6)C17—C181.375 (6)
C3—H30.9300C17—H170.9300
C4—C51.369 (5)C18—C191.375 (6)
C4—H40.9300C18—H180.9300
C5—C61.389 (4)C19—C201.360 (6)
C5—H50.9300C19—H190.9300
C6—N21.416 (4)C20—H200.9300
C7—N11.294 (4)C21—N31.431 (5)
C7—C81.421 (4)C21—H21A0.9600
C7—H70.9300C21—H21B0.9600
C8—C131.409 (4)C21—H21C0.9600
C8—C91.423 (5)C22—N31.438 (5)
C9—O11.312 (4)C22—H22A0.9600
C9—C101.405 (4)C22—H22B0.9600
C10—C111.376 (5)C22—H22C0.9600
C10—H100.9300C23—O31.216 (4)
C11—C121.389 (5)C23—N31.321 (5)
C11—H110.9300C23—H230.9300
O1—Cu1—O288.35 (10)N2—C14—H14116.8
O1—Cu1—N194.06 (10)C15—C14—H14116.8
O2—Cu1—N1173.09 (10)C20—C15—C16119.3 (3)
O1—Cu1—N2177.59 (9)C20—C15—C14117.4 (4)
O2—Cu1—N293.78 (10)C16—C15—C14123.3 (3)
N1—Cu1—N283.69 (10)O2—C16—C15124.8 (3)
C2—C1—C6119.9 (3)O2—C16—C17118.0 (3)
C2—C1—N1125.1 (3)C15—C16—C17117.2 (3)
C6—C1—N1115.0 (3)C18—C17—C16121.1 (4)
C3—C2—C1119.6 (3)C18—C17—H17119.4
C3—C2—H2120.2C16—C17—H17119.4
C1—C2—H2120.2C17—C18—C19121.5 (4)
C2—C3—C4120.0 (3)C17—C18—H18119.3
C2—C3—H3120.0C19—C18—H18119.3
C4—C3—H3120.0C20—C19—C18118.8 (4)
C5—C4—C3120.9 (4)C20—C19—H19120.6
C5—C4—H4119.5C18—C19—H19120.6
C3—C4—H4119.5C19—C20—C15122.1 (4)
C4—C5—C6120.0 (3)C19—C20—H20119.0
C4—C5—H5120.0C15—C20—H20119.0
C6—C5—H5120.0N3—C21—H21A109.5
C5—C6—C1119.5 (3)N3—C21—H21B109.5
C5—C6—N2125.2 (3)H21A—C21—H21B109.5
C1—C6—N2115.2 (3)N3—C21—H21C109.5
N1—C7—C8126.3 (3)H21A—C21—H21C109.5
N1—C7—H7116.8H21B—C21—H21C109.5
C8—C7—H7116.8N3—C22—H22A109.5
C13—C8—C7117.5 (3)N3—C22—H22B109.5
C13—C8—C9119.2 (3)H22A—C22—H22B109.5
C7—C8—C9123.3 (3)N3—C22—H22C109.5
O1—C9—C10118.9 (3)H22A—C22—H22C109.5
O1—C9—C8124.2 (3)H22B—C22—H22C109.5
C10—C9—C8116.9 (3)O3—C23—N3126.1 (4)
C11—C10—C9121.8 (3)O3—C23—H23116.9
C11—C10—H10119.1N3—C23—H23116.9
C9—C10—H10119.1C7—N1—C1122.1 (3)
C10—C11—C12121.0 (3)C7—N1—Cu1124.6 (2)
C10—C11—H11119.5C1—N1—Cu1113.06 (19)
C12—C11—H11119.5C14—N2—C6122.3 (3)
C13—C12—C11118.6 (3)C14—N2—Cu1124.7 (2)
C13—C12—H12120.7C6—N2—Cu1112.94 (19)
C11—C12—H12120.7C23—N3—C21119.5 (3)
C12—C13—C8122.4 (4)C23—N3—C22122.2 (3)
C12—C13—H13118.8C21—N3—C22118.3 (3)
C8—C13—H13118.8C9—O1—Cu1126.3 (2)
N2—C14—C15126.4 (3)C16—O2—Cu1126.9 (2)
Symmetry codes: (i) −x−3, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O30.932.443.244 (4)145
C5—H5···O30.932.543.333 (4)144
C23—H23···O2ii0.932.583.457 (5)158
C7—H7···O3iii0.932.413.333 (4)170
C2—H2···O3iii0.932.473.389 (4)172
C21—H21A···O30.962.362.756 (5)104
Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2.
Table 1
Selected geometric parameters (Å) top
Cu1—O11.907 (2)Cu1—N21.950 (2)
Cu1—O21.909 (2)Cu1—O1i2.783 (11).
Cu1—N11.946 (2)
Symmetry codes: (i) −x−3, −y, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C14—H14···O30.932.443.244 (4)145
C5—H5···O30.932.543.333 (4)144
C23—H23···O2ii0.932.583.457 (5)158
C7—H7···O3iii0.932.413.333 (4)170
C2—H2···O3iii0.932.473.389 (4)172
C21—H21A···O30.962.362.756 (5)104
Symmetry codes: (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2.
Acknowledgements top

This work was supported by the Natural Science Foundation of Xiaogan University (Z2008012).

references
References top

Bruker (2001). SAINT-Plus and SMART. Bruker AXS, Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (20081). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Suzuki, M., Ishikawa, T., Harada, A., Ohba, S., Sakamoto, M. & Nishida, Y. (1997). Polyhedron, 16, 2553–2561.