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Acta Cryst. (2009). E65, m744-m745    [ doi:10.1107/S1600536809019473 ]

Di-[mu]-chlorido-bis[chlorido(N,N-dimethylethylenediamine-[kappa]2N,N')zinc(II)]

M.-M. Yu, Q.-Z. Shi, Y.-N. Zhang and Z.-X. Li

Abstract top

The centrosymmetric dinuclear title compound, [Zn2Cl4(C4H12N2)2], is isostructural with its previously reported CuII analogue [Phelps, Goodman & Hodgson (1976). Inorg. Chem. 15, 2266-2270]. In the title compound, each of the ZnII ions is coordinated by two N atoms from a chelating N,N-dimethylethylenediamine ligand, two bridging Cl atoms and one terminal Cl atom. The coordination environment is distorted square-pyramidal. The Zn-Cl bond distances of the two bridging Cl atoms are distinctly different: the equatorial Cl atom exbibits a Zn-Cl distance of 2.318 (1) Å and the axial Cl atom exbibits a Zn-Cl distance of 2.747 (2) Å, which is significantly longer. The molecule can thus be seen as a dimer of two nearly square-planar monomeric units which are related to each other by an inversion center located in the middle of the dimer. Within one monomeric unit, the Zn atom, the two N atoms and the two Cl atoms are almost coplanar, with a mean deviation of only 0.05 (1) Å from the associated least-squares plane. The Zn...Zn distance within the dimer is 3.472 (3) Å. N-H...Cl and C-H...Cl hydrogen-bond interactions connect neighboring molecules with each other.

Comment top

N,N-Dimethylethylenediamine has the potential to function as a bidentatate nitrogen ligand by coordinating to metal ions in a chelating fashion (Hlavinka & Hagadorn, 2003; Knight et al., 2008; Basak et al., 2007). Here, we report the crystal structure of the title compound, an asymmetrically chloro-bridged dimeric zinc(II) complex.

In the centrosymmetric dinuclear title compound, [Zn2Cl4(C4H12N2)2], each of the ZnII ions is coordinated by two N atoms from a chelating N,N-dimethylethylenediamine ligand, two bridging Cl atoms and one terminal Cl atom. The coordination environment is distorted square-pyramidal. In the dimeric structure, two ZnII ions are bridged through the Cl atoms, resulting in a planar Zn2Cl2 core. The Zn—Cl bond distances of the two bridging Cl atoms are distinctly different: The equatorial Cl atoms exbibit a Zn—Cl distance of 2.318 (1) Å, the Zn—Cl distances of the axial chlorides are with 2.747 (2) Å significantely longer. The title compound could thus be considered as a dimer of two nearly square planar monomeric units which are related to each other by an inversion center located in the middle of the molecule [symmetry code: 1 - x, 2 - y, 1 - z]. Within one monomeric unit the atoms Zn1, N1, N2, Cl1 and Cl2 are almost coplanar with a mean deviation of only 0.05 (1) Å from the associated least-squares plane.

The methyl substituted N atom N2 is located opposite of the bridging Cl atom Cl1, probably due to its larger steric demand when compared to the unsubstituted NH2 group and due the ability to form an intramolecular N—H···Cl hydrogen bond to the terminal Cl atom in the other half of the dimer (see Table 1 and below).

The Cambridge Structural Database (Allen, 2002) does not list any crystal structures with a ZnII ion in a square-pyramidal environment with two bridging Cl atoms and one terminal Cl atom. This motif seems to be more typical for CuII complexes for which the CSD has 15 entries. The structure of the title complex is indeed isostructural to its copper(II) analogue [CuCl2(C4H12N2)]2 (Phelps et al., 1976). Both structures are very similiar, as proved by the distance of M—Cl, the M···M separation and the bridging M—Cl—M angle (Zn—Cl = 2.318 (1) Å, Zn—Cl' = 2.747 (2) Å, Zn···Zn = 3.472 (3) Å, Zn—Cl—Zn = 86.11 (4) °; Cu—Cl = 2.309 (2) Å, Cu—Cl' = 2.734 (3) Å, Cu···Cu = 3.458 (3) Å, Cu—Cl—Cu = 86.11 (8) °.

In the crystal structure, the dimer is strengthened by intramolecular hydrogen bond interactions involving the methyl and amino protons of the ligand and the terminal Cl atom [C4—H4C···Cl2 and N1—H1A···Cl2i, symmetry code: (i) 1 - x, 2 - y, 1 - z]. An intermolecular N1—H1D···Cl1ii hydrogen bond interaction between the other amino H atom and one of the bridging Cl atoms leads to the formation of a one-dimensional supramolecular chain (Table 1, Fig. 2).

Related literature top

For the isostructural CuII complex, see: Phelps et al. (1976). For general background on the coordination behaviour of N,N-dimethylethylenediamine, see: Basak et al. (2007); Hlavinka & Hagadorn (2003); Knight et al. (2008). Allen (2002) describes the Cambridge Structural Database.

Experimental top

Colourless crystals of the title complex were obtained by slow evaporation of a solution in ethanol (20 ml) and water (5 ml) of N,N-dimethylethylenediamine (0.044 g, 0.5 mmol) and ZnCl2 (0.068 g, 0.5 mmol). Yield, 85%. Selected IR data (cm-1, KBr pellet): 3342, 3285 (m), 3161 (w), 3048 (w), 1465 (m), 1332 (w), 1292 (w), 1248 (w), 1189 (w), 1007 (m), 937 (w), 896 (w), 789(w), 631 (m). Anal. Calcd for C8H24Cl4N4Zn2 requires C, 21.4; H, 5.39; N, 12.48. Found: C, 21.1; H, 5.41; N, 12.23%.

Refinement top

The H atoms bound to C and N atoms were placed in caculated positions with C—H = 0.97 Å (CH2), C—H = 0.96 Å (CH3) and with Uiso(H) = 1.2Ueq(C), and with N—H distances of 0.90 Å and with Uiso(H) = 1.2Ueq(N).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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. A view of title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. N—H···Cl and C—H···Cl interactions (dashed lines) in the title compound. [Symmetry codes: (i) 1 - x, 2 - y, 1 - z; (ii) 0.5 - x, 0.5 + y, z; (iii) 0.5 + x, 1.5 - y, 1 - z]
Di-µ-chlorido-bis[chlorido(N,N-dimethylethylenediamine- κ2N,N')zinc(II)] top
Crystal data top
[Zn2Cl4(C4H12N2)2]F(000) = 912
Mr = 448.85Dx = 1.713 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 1620 reflections
a = 9.808 (2) Åθ = 2.0–25.5°
b = 8.5109 (17) ŵ = 3.36 mm−1
c = 20.851 (4) ÅT = 295 K
V = 1740.5 (6) Å3Block, colourless
Z = 40.15 × 0.12 × 0.07 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		1620 independent reflections
Radiation source: fine-focus sealed tube1300 reflections with I > 2σ(I)
graphiteRint = 0.042
φ and ω scansθmax = 25.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		h = −11→11
Tmin = 0.633, Tmax = 0.799k = −6→10
7050 measured reflectionsl = −25→20
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)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0632P)2 + 2.354P]
where P = (Fo2 + 2Fc2)/3
1620 reflections(Δ/σ)max < 0.001
82 parametersΔρmax = 1.14 e Å−3
0 restraintsΔρmin = −0.41 e Å−3
Crystal data top
[Zn2Cl4(C4H12N2)2]V = 1740.5 (6) Å3
Mr = 448.85Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 9.808 (2) ŵ = 3.36 mm−1
b = 8.5109 (17) ÅT = 295 K
c = 20.851 (4) Å0.15 × 0.12 × 0.07 mm
Data collection top
Bruker SMART 1K CCD area-detector
diffractometer		1620 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)		1300 reflections with I > 2σ(I)
Tmin = 0.633, Tmax = 0.799Rint = 0.042
7050 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.049H-atom parameters constrained
wR(F2) = 0.132Δρmax = 1.14 e Å−3
S = 1.10Δρmin = −0.41 e Å−3
1620 reflectionsAbsolute structure: ?
82 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
Zn10.43590 (6)0.94329 (7)0.42593 (3)0.0433 (3)
Cl10.31460 (12)1.00877 (18)0.51751 (7)0.0526 (4)
Cl20.40919 (18)1.18349 (18)0.38224 (8)0.0700 (5)
N10.4424 (4)0.7235 (5)0.4593 (2)0.0490 (11)
H1A0.50320.71730.49150.059*
H1D0.36000.69640.47480.059*
N20.5142 (5)0.8454 (6)0.3424 (2)0.0566 (12)
C30.4065 (7)0.8464 (9)0.2933 (3)0.077 (2)
H3A0.44080.80090.25440.116*
H3B0.37840.95270.28530.116*
H3C0.32990.78640.30820.116*
C10.4819 (7)0.6142 (7)0.4073 (4)0.078 (2)
H1B0.52990.52500.42540.093*
H1C0.40050.57520.38610.093*
C40.6311 (8)0.9331 (11)0.3154 (4)0.099 (3)
H4A0.66240.88150.27720.148*
H4B0.70360.93640.34630.148*
H4C0.60311.03820.30510.148*
C20.5679 (9)0.6908 (9)0.3608 (4)0.095 (3)
H2A0.57530.62510.32290.114*
H2B0.65860.70350.37870.114*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0489 (4)0.0326 (4)0.0485 (4)0.0042 (2)−0.0006 (3)0.0006 (2)
Cl10.0422 (6)0.0581 (8)0.0575 (8)0.0054 (6)−0.0002 (6)−0.0108 (6)
Cl20.0875 (11)0.0378 (8)0.0847 (11)0.0070 (7)−0.0056 (9)0.0152 (7)
N10.056 (3)0.035 (2)0.056 (3)−0.0057 (19)0.000 (2)0.0071 (19)
N20.074 (3)0.057 (3)0.039 (2)0.014 (2)0.000 (2)−0.002 (2)
C30.089 (5)0.086 (5)0.058 (4)−0.007 (4)−0.015 (3)−0.011 (4)
C10.074 (4)0.026 (3)0.133 (6)−0.002 (3)0.026 (4)−0.004 (3)
C40.071 (5)0.146 (9)0.079 (5)−0.003 (5)0.024 (4)−0.005 (5)
C20.133 (7)0.071 (5)0.080 (5)0.037 (5)0.015 (5)−0.016 (4)
Geometric parameters (Å, °) top
Zn1—N11.997 (4)C3—H3A0.9600
Zn1—N22.078 (4)C3—H3B0.9600
Zn1—Cl22.2533 (16)C3—H3C0.9600
Zn1—Cl12.3179 (14)C1—C21.441 (10)
Zn1—Cl1i2.7468 (15)C1—H1B0.9700
Cl1—Zn1i2.7468 (15)C1—H1C0.9700
N1—C11.481 (8)C4—H4A0.9600
N1—H1A0.9000C4—H4B0.9600
N1—H1D0.9000C4—H4C0.9600
N2—C21.468 (9)C2—H2A0.9700
N2—C31.471 (8)C2—H2B0.9700
N2—C41.480 (9)
N1—Zn1—N284.52 (19)N2—C3—H3B109.5
N1—Zn1—Cl2173.95 (13)H3A—C3—H3B109.5
N2—Zn1—Cl293.89 (14)N2—C3—H3C109.5
N1—Zn1—Cl187.40 (14)H3A—C3—H3C109.5
N2—Zn1—Cl1167.59 (16)H3B—C3—H3C109.5
Cl2—Zn1—Cl193.17 (6)C2—C1—N1111.2 (5)
N1—Zn1—Cl1i87.78 (13)C2—C1—H1B109.4
N2—Zn1—Cl1i95.19 (14)N1—C1—H1B109.4
Cl2—Zn1—Cl1i98.19 (6)C2—C1—H1C109.4
Cl1—Zn1—Cl1i93.89 (4)N1—C1—H1C109.4
Zn1—Cl1—Zn1i86.11 (4)H1B—C1—H1C108.0
C1—N1—Zn1110.0 (4)N2—C4—H4A109.5
C1—N1—H1A109.7N2—C4—H4B109.5
Zn1—N1—H1A109.7H4A—C4—H4B109.5
C1—N1—H1D109.7N2—C4—H4C109.5
Zn1—N1—H1D109.7H4A—C4—H4C109.5
H1A—N1—H1D108.2H4B—C4—H4C109.5
C2—N2—C3116.5 (6)C1—C2—N2111.8 (6)
C2—N2—C4105.9 (6)C1—C2—H2A109.3
C3—N2—C4106.8 (5)N2—C2—H2A109.3
C2—N2—Zn1105.8 (4)C1—C2—H2B109.3
C3—N2—Zn1108.4 (4)N2—C2—H2B109.3
C4—N2—Zn1113.8 (4)H2A—C2—H2B107.9
N2—C3—H3A109.5
N1—Zn1—Cl1—Zn1i87.59 (12)Cl2—Zn1—N2—C3−65.5 (4)
N2—Zn1—Cl1—Zn1i136.9 (6)Cl1—Zn1—N2—C359.0 (8)
Cl2—Zn1—Cl1—Zn1i−98.44 (6)Cl1i—Zn1—N2—C3−164.1 (4)
Cl1i—Zn1—Cl1—Zn1i0.0N1—Zn1—N2—C4−132.8 (5)
N2—Zn1—N1—C1−6.1 (4)Cl2—Zn1—N2—C453.0 (5)
Cl1—Zn1—N1—C1164.4 (4)Cl1—Zn1—N2—C4177.6 (5)
Cl1i—Zn1—N1—C1−101.6 (4)Cl1i—Zn1—N2—C4−45.6 (5)
N1—Zn1—N2—C2−17.0 (5)Zn1—N1—C1—C229.5 (7)
Cl2—Zn1—N2—C2168.8 (5)N1—C1—C2—N2−46.2 (9)
Cl1—Zn1—N2—C2−66.6 (8)C3—N2—C2—C1−82.0 (8)
Cl1i—Zn1—N2—C270.2 (5)C4—N2—C2—C1159.5 (7)
N1—Zn1—N2—C3108.6 (4)Zn1—N2—C2—C138.5 (8)
Symmetry codes: (i) −x+1, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1D···Cl1ii0.902.513.342 (2)155
C4—H4C···Cl20.962.783.350 (9)119
N1—H1A···Cl2i0.902.903.697 (2)149
Symmetry codes: (ii) −x+1/2, y−1/2, z; (i) −x+1, −y+2, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1D···Cl1i0.902.513.342 (2)155
C4—H4C···Cl20.962.783.350 (9)119
N1—H1A···Cl2ii0.902.903.697 (2)149
Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) −x+1, −y+2, −z+1.
Acknowledgements top

This work was supported by the Natural Science Foundation of China (grant No. 50873093).

references
References top

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Hlavinka, M. L. & Hagadorn, J. R. (2003). Chem. Commun. pp. 2686–2687.

Knight, P. D., White, J. P. & Williams, C. K. (2008). Inorg. Chem. 47, 11711–11719.

Phelps, D. W., Goodman, W. H. & Hodgson, D. J. (1976). Inorg. Chem. 15, 2266–2270.

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