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Acta Cryst. (2009). E65, m1492    [ doi:10.1107/S1600536809044997 ]

Di-[mu]-chlorido-bis[chlorido(N,N'-dibenzylpropane-1,2-diamine-[kappa]2N,N')copper(II)]

Y.-F. Liu, D.-F. Rong, H.-T. Xia and D.-Q. Wang

Abstract top

In the title complex, [Cu2Cl4(C17H22N2)2], the CuII cation is coordinated by a N,N'-dibenzylpropane-1,2-diamine ligand and two Cl- anions, and a Cl- anion from an adjacent molecule further bridges to the CuII cation in the apical position, with a longer Cu-Cl distance of 2.9858 (18) Å, forming a centrosymmetric dimeric complex in which each CuII cation is in a distorted square-pyramidal geometry. Intramolecular N-H...Cl hydrogen bonding is observed in the dimeric complex.

Comment top

Copper(II) complexes bridged by a pair of Cl atoms have been widely investigated in both bioinorganic chemistry and coordination chemistry (Yang et al., 2007; Alves et al., 2004). As a further study of the structures of such complexes, the crystal structure of the title complex is reported here.

The molecular structure of the title complex is illustrated in Fig. 1. The CuII atom are in a distorted square-pyramidal coordination environment (Table 1). The two copper atoms are bridged by a pair of Cl atoms, resulting in complex with centro-symmetric structures. The apical Cu—Cl bond length is 2.9858 (18) Å, whic is longer than 2.737 Å reported by Alves et al. (2004), and 2.852 (1) and 2.971 (2) Å reported by Yang et al. (2007). The N—H···Cl hydrogen boding is present in the crystal structure (Table 2).

Related literature top

For Cu—Cl bond distances, see: Alves et al. (2004); Yang et al. (2007).

Experimental top

A solution of N,N'-dibenzylpropane-1,2-diamine (1 mmol) in ethanol (20 ml) and a solution of cupric chloride (1 mmol) in ethanol (10 ml) was mixed, the reaction mixture was stirred for 3 h at 323 K. The solution was then cooled slowly to room temperature and filtered. Blue crystals suitable for X-ray diffraction were obtained by evaporation of an ethanol solution.

Refinement top

H atoms were placed in calculated positions with N—H = 0.91 and C—H = 0.93 to 0.97 Å, and refined in riding mode with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C,N) for the others.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The dimeric complex structure showing the atom-labeling scheme. Displacement ellipsoids are at the 30% probability level. For clarity, H atomes have been omitted [symmetry code: (A) 1/2 - x, 1/2 - y, 1 - z].
Di-µ-chlorido-bis[chlorido(N,N'-dibenzylpropane-1,2- diamine-κ2N,N')copper(II)] top
Crystal data top
[Cu2Cl4(C17H22N2)2]F(000) = 1608
Mr = 777.61Dx = 1.478 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1854 reflections
a = 21.070 (2) Åθ = 2.8–25.3°
b = 13.7377 (17) ŵ = 1.55 mm−1
c = 13.2449 (16) ÅT = 298 K
β = 114.317 (2)°Block, blue
V = 3493.6 (7) Å30.20 × 0.18 × 0.10 mm
Z = 4
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer		3077 independent reflections
Radiation source: fine-focus sealed tube1858 reflections with I > 2σ(I)
graphiteRint = 0.052
φ and ω scansθmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −25→21
Tmin = 0.746, Tmax = 0.860k = −16→16
8528 measured reflectionsl = −10→15
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0084P)2 + 19.8791P]
where P = (Fo2 + 2Fc2)/3
3077 reflections(Δ/σ)max = 0.011
199 parametersΔρmax = 0.59 e Å−3
0 restraintsΔρmin = −0.67 e Å−3
Crystal data top
[Cu2Cl4(C17H22N2)2]V = 3493.6 (7) Å3
Mr = 777.61Z = 4
Monoclinic, C2/cMo Kα radiation
a = 21.070 (2) ŵ = 1.55 mm−1
b = 13.7377 (17) ÅT = 298 K
c = 13.2449 (16) Å0.20 × 0.18 × 0.10 mm
β = 114.317 (2)°
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer		3077 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1858 reflections with I > 2σ(I)
Tmin = 0.746, Tmax = 0.860Rint = 0.052
8528 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.051 w = 1/[σ2(Fo2) + (0.0084P)2 + 19.8791P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.104Δρmax = 0.59 e Å−3
S = 1.06Δρmin = −0.67 e Å−3
3077 reflectionsAbsolute structure: ?
199 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
H-atom parameters constrained
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
Cu10.19407 (3)0.17462 (5)0.40049 (6)0.0413 (2)
Cl10.10161 (7)0.26002 (11)0.39737 (13)0.0528 (4)
Cl20.23408 (8)0.13479 (12)0.58229 (13)0.0534 (4)
N10.1603 (2)0.1813 (3)0.2330 (4)0.0419 (11)
H10.15580.24580.21600.050*
N20.2780 (2)0.1094 (3)0.3951 (4)0.0414 (12)
H20.31580.13070.45490.050*
C10.2153 (3)0.1442 (4)0.1974 (5)0.0459 (15)
H1A0.20500.07580.17580.055*
C20.2841 (3)0.1484 (4)0.2955 (5)0.0437 (15)
H2A0.31820.11080.28040.052*
H2B0.30010.21540.30870.052*
C30.2159 (4)0.2000 (5)0.0982 (5)0.071 (2)
H3A0.17140.19380.03680.107*
H3B0.25140.17380.07820.107*
H3C0.22540.26750.11730.107*
C40.0901 (3)0.1380 (4)0.1691 (5)0.0471 (15)
H4A0.07820.14470.09050.056*
H4B0.05570.17360.18570.056*
C50.0874 (3)0.0315 (4)0.1964 (5)0.0410 (14)
C60.0856 (3)−0.0402 (5)0.1225 (5)0.0537 (17)
H60.0850−0.02300.05420.064*
C70.0847 (3)−0.1367 (5)0.1488 (7)0.071 (2)
H70.0830−0.18460.09810.085*
C80.0864 (3)−0.1628 (5)0.2511 (7)0.070 (2)
H80.0869−0.22820.26970.084*
C90.0873 (3)−0.0925 (5)0.3243 (6)0.0627 (19)
H90.0877−0.10970.39240.075*
C100.0877 (3)0.0050 (5)0.2968 (5)0.0471 (15)
H100.08820.05280.34680.057*
C110.2785 (3)0.0013 (4)0.4004 (5)0.0507 (16)
H11A0.2485−0.02400.32800.061*
H11B0.2592−0.01890.45210.061*
C120.3497 (3)−0.0430 (4)0.4355 (5)0.0425 (14)
C130.3737 (3)−0.0720 (4)0.3563 (5)0.0493 (16)
H130.3454−0.06410.28130.059*
C140.4395 (3)−0.1126 (4)0.3890 (7)0.0607 (19)
H140.4556−0.13090.33610.073*
C150.4796 (4)−0.1254 (5)0.4962 (8)0.075 (2)
H150.5233−0.15370.51730.090*
C160.4575 (4)−0.0976 (5)0.5764 (6)0.080 (2)
H160.4860−0.10650.65110.096*
C170.3918 (3)−0.0560 (5)0.5438 (5)0.0594 (18)
H170.3766−0.03670.59740.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0354 (4)0.0480 (4)0.0427 (4)0.0035 (3)0.0185 (3)−0.0051 (4)
Cl10.0399 (8)0.0628 (10)0.0571 (10)0.0081 (7)0.0213 (8)−0.0107 (8)
Cl20.0501 (9)0.0667 (11)0.0458 (10)0.0061 (8)0.0221 (8)0.0051 (8)
N10.046 (3)0.038 (3)0.048 (3)0.001 (2)0.025 (2)0.000 (2)
N20.039 (3)0.038 (3)0.046 (3)0.002 (2)0.016 (2)−0.002 (2)
C10.056 (4)0.039 (4)0.050 (4)−0.003 (3)0.029 (3)−0.008 (3)
C20.043 (3)0.037 (4)0.061 (4)0.000 (3)0.032 (3)−0.004 (3)
C30.085 (5)0.083 (5)0.067 (5)0.011 (4)0.052 (4)0.017 (4)
C40.040 (3)0.052 (4)0.043 (4)0.000 (3)0.010 (3)−0.003 (3)
C50.030 (3)0.049 (4)0.038 (4)−0.001 (3)0.008 (3)−0.006 (3)
C60.053 (4)0.060 (5)0.058 (4)−0.007 (3)0.033 (4)−0.009 (4)
C70.068 (5)0.051 (5)0.108 (7)−0.008 (4)0.052 (5)−0.023 (4)
C80.059 (4)0.051 (5)0.107 (7)0.000 (4)0.042 (5)0.009 (5)
C90.059 (4)0.064 (5)0.065 (5)−0.004 (4)0.026 (4)0.012 (4)
C100.039 (3)0.059 (4)0.046 (4)−0.010 (3)0.020 (3)−0.009 (3)
C110.047 (4)0.040 (4)0.070 (5)0.002 (3)0.029 (3)0.004 (3)
C120.043 (3)0.035 (3)0.051 (4)0.004 (3)0.021 (3)0.002 (3)
C130.055 (4)0.042 (4)0.053 (4)0.001 (3)0.025 (3)−0.010 (3)
C140.064 (5)0.044 (4)0.087 (6)0.004 (3)0.044 (5)−0.012 (4)
C150.057 (5)0.060 (5)0.106 (7)0.023 (4)0.032 (5)0.005 (5)
C160.071 (5)0.089 (6)0.059 (5)0.020 (4)0.006 (4)0.016 (4)
C170.066 (5)0.069 (5)0.044 (4)0.012 (4)0.024 (4)0.004 (3)
Geometric parameters (Å, °) top
Cu1—N12.034 (4)C6—C71.373 (8)
Cu1—N22.010 (4)C6—H60.9300
Cu1—Cl12.2598 (15)C7—C81.388 (10)
Cu1—Cl22.2663 (17)C7—H70.9300
Cu1—Cl2i2.9858 (18)C8—C91.363 (9)
N1—C41.493 (6)C8—H80.9300
N1—C11.508 (6)C9—C101.388 (8)
N1—H10.9100C9—H90.9300
N2—C21.477 (6)C10—H100.9300
N2—C111.487 (6)C11—C121.504 (7)
N2—H20.9100C11—H11A0.9700
C1—C21.497 (7)C11—H11B0.9700
C1—C31.526 (8)C12—C171.352 (8)
C1—H1A0.9800C12—C131.396 (7)
C2—H2A0.9700C13—C141.389 (8)
C2—H2B0.9700C13—H130.9300
C3—H3A0.9600C14—C151.331 (9)
C3—H3B0.9600C14—H140.9300
C3—H3C0.9600C15—C161.378 (10)
C4—C51.514 (7)C15—H150.9300
C4—H4A0.9700C16—C171.393 (8)
C4—H4B0.9700C16—H160.9300
C5—C101.376 (7)C17—H170.9300
C5—C61.379 (7)
N2—Cu1—N184.19 (18)C5—C4—H4B109.2
N2—Cu1—Cl1174.43 (14)H4A—C4—H4B107.9
N1—Cu1—Cl192.59 (13)C10—C5—C6119.0 (6)
N2—Cu1—Cl289.00 (14)C10—C5—C4120.1 (5)
N1—Cu1—Cl2168.46 (14)C6—C5—C4120.9 (5)
Cl1—Cu1—Cl294.90 (6)C7—C6—C5120.6 (6)
N2—Cu1—Cl2i88.13 (13)C7—C6—H6119.7
N1—Cu1—Cl2i88.99 (13)C5—C6—H6119.7
Cl1—Cu1—Cl2i87.27 (5)C6—C7—C8120.0 (7)
Cl2—Cu1—Cl2i100.11 (5)C6—C7—H7120.0
C4—N1—C1113.5 (4)C8—C7—H7120.0
C4—N1—Cu1114.8 (3)C9—C8—C7119.9 (7)
C1—N1—Cu1110.9 (3)C9—C8—H8120.0
C4—N1—H1105.6C7—C8—H8120.0
C1—N1—H1105.6C8—C9—C10119.8 (7)
Cu1—N1—H1105.6C8—C9—H9120.1
C2—N2—C11113.8 (4)C10—C9—H9120.1
C2—N2—Cu1105.7 (3)C5—C10—C9120.7 (6)
C11—N2—Cu1115.6 (3)C5—C10—H10119.6
C2—N2—H2107.1C9—C10—H10119.6
C11—N2—H2107.1N2—C11—C12113.9 (4)
Cu1—N2—H2107.1N2—C11—H11A108.8
C2—C1—N1108.0 (4)C12—C11—H11A108.8
C2—C1—C3112.2 (5)N2—C11—H11B108.8
N1—C1—C3112.3 (5)C12—C11—H11B108.8
C2—C1—H1A108.0H11A—C11—H11B107.7
N1—C1—H1A108.0C17—C12—C13118.6 (6)
C3—C1—H1A108.0C17—C12—C11121.0 (6)
N2—C2—C1110.6 (4)C13—C12—C11120.4 (6)
N2—C2—H2A109.5C14—C13—C12120.2 (6)
C1—C2—H2A109.5C14—C13—H13119.9
N2—C2—H2B109.5C12—C13—H13119.9
C1—C2—H2B109.5C15—C14—C13120.0 (7)
H2A—C2—H2B108.1C15—C14—H14120.0
C1—C3—H3A109.5C13—C14—H14120.0
C1—C3—H3B109.5C14—C15—C16121.2 (7)
H3A—C3—H3B109.5C14—C15—H15119.4
C1—C3—H3C109.5C16—C15—H15119.4
H3A—C3—H3C109.5C15—C16—C17119.0 (7)
H3B—C3—H3C109.5C15—C16—H16120.5
N1—C4—C5112.0 (4)C17—C16—H16120.5
N1—C4—H4A109.2C12—C17—C16121.1 (6)
C5—C4—H4A109.2C12—C17—H17119.5
N1—C4—H4B109.2C16—C17—H17119.5
N2—Cu1—N1—C4125.7 (4)N1—C4—C5—C1072.6 (6)
Cl1—Cu1—N1—C4−58.9 (3)N1—C4—C5—C6−106.4 (6)
Cl2—Cu1—N1—C471.6 (8)C10—C5—C6—C7−0.5 (9)
Cl2i—Cu1—N1—C4−146.1 (3)C4—C5—C6—C7178.5 (5)
N2—Cu1—N1—C1−4.6 (3)C5—C6—C7—C8−0.8 (10)
Cl1—Cu1—N1—C1170.8 (3)C6—C7—C8—C91.5 (11)
Cl2—Cu1—N1—C1−58.7 (8)C7—C8—C9—C10−1.1 (10)
Cl2i—Cu1—N1—C183.6 (3)C6—C5—C10—C90.9 (9)
N1—Cu1—N2—C228.3 (3)C4—C5—C10—C9−178.1 (5)
Cl2—Cu1—N2—C2−161.0 (3)C8—C9—C10—C5−0.2 (9)
Cl2i—Cu1—N2—C2−60.8 (3)C2—N2—C11—C1277.4 (6)
Cl2—Cu1—N2—C1172.2 (4)Cu1—N2—C11—C12−160.0 (4)
Cl2i—Cu1—N2—C11172.3 (4)N2—C11—C12—C1787.2 (7)
C4—N1—C1—C2−151.2 (4)N2—C11—C12—C13−93.1 (7)
Cu1—N1—C1—C2−20.1 (5)C17—C12—C13—C14−0.4 (9)
C4—N1—C1—C384.5 (6)C11—C12—C13—C14179.9 (5)
Cu1—N1—C1—C3−144.4 (4)C12—C13—C14—C151.0 (9)
C11—N2—C2—C179.6 (5)C13—C14—C15—C16−1.0 (11)
Cu1—N2—C2—C1−48.4 (5)C14—C15—C16—C170.4 (12)
N1—C1—C2—N245.4 (6)C13—C12—C17—C16−0.2 (9)
C3—C1—C2—N2169.7 (5)C11—C12—C17—C16179.5 (6)
C1—N1—C4—C569.9 (6)C15—C16—C17—C120.2 (11)
Cu1—N1—C4—C5−59.2 (5)
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl1i0.912.513.386 (5)161
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1.
Table 1
Selected geometric parameters (Å) top
Cu1—N12.034 (4)Cu1—Cl22.2663 (17)
Cu1—N22.010 (4)Cu1—Cl2i2.9858 (18)
Cu1—Cl12.2598 (15)
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···Cl1i0.912.513.386 (5)161
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1.
Acknowledgements top

We acknowledge the financial support of theScience Foundation of Huaihai Institute of Technology, China.

references
References top

Alves, W. A., Santos, R. H., Paduan-Filho, A., Becerra, C. C., Borin, A. C. & Ferreira, A. M. (2004). Inorg. Chim. Acta, 357, 2269–2278.

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

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

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

Yang, S.-P., Han, L.-J., Xia, H.-T., Wang, D.-Q. & Liu, Y.-F. (2007). Acta Cryst. C63, m610–m614.