Di-μ-chlorido-bis-[chlorido(N,N-di-methyl-ethylenediamine-κN,N')zinc(II)].

The centrosymmetric dinuclear title compound, [Zn(2)Cl(4)(C(4)H(12)N(2))(2)], is isostructural with its previously reported Cu(II) analogue [Phelps, Goodman & Hodgson (1976 ▶). Inorg. Chem.15, 2266-2270]. In the title compound, each of the Zn(II) ions is coordinated by two N atoms from a chelating N,N-dimethyl-ethylenediamine 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 mol-ecule 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 inter-actions connect neighboring mol-ecules with each other.

Related literature

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

Crystal data

[Zn2Cl4(C4H12N2)2]

M = 448.85

Orthorhombic,

a = 9.808 (2) Å

b = 8.5109 (17) Å

c = 20.851 (4) Å

V = 1740.5 (6) Å3

Z = 4

Mo Kα radiation

μ = 3.36 mm−1

T = 295 K

0.15 × 0.12 × 0.07 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.633, T max = 0.799

7050 measured reflections

1620 independent reflections

1300 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.132

S = 1.10

1620 reflections

82 parameters

H-atom parameters constrained

Δρmax = 1.14 e Å−3

Δρmin = −0.42 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019473/zl2193sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809019473/zl2193Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zn2Cl4(C4H12N2)2]	F(000) = 912
Mr = 448.85	Dx = 1.713 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1620 reflections
a = 9.808 (2) Å	θ = 2.0–25.5°
b = 8.5109 (17) Å	µ = 3.36 mm−1
c = 20.851 (4) Å	T = 295 K
V = 1740.5 (6) Å3	Block, colourless
Z = 4	0.15 × 0.12 × 0.07 mm

Bruker SMART 1K CCD area-detector diffractometer	1620 independent reflections
Radiation source: fine-focus sealed tube	1300 reflections with I > 2σ(I)
graphite	Rint = 0.042
φ and ω scans	θmax = 25.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
Tmin = 0.633, Tmax = 0.799	k = −6→10
7050 measured reflections	l = −25→20

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132	H-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 parameters	Δρmax = 1.14 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

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.

	x	y	z	Uiso*/Ueq
Zn1	0.43590 (6)	0.94329 (7)	0.42593 (3)	0.0433 (3)
Cl1	0.31460 (12)	1.00877 (18)	0.51751 (7)	0.0526 (4)
Cl2	0.40919 (18)	1.18349 (18)	0.38224 (8)	0.0700 (5)
N1	0.4424 (4)	0.7235 (5)	0.4593 (2)	0.0490 (11)
H1A	0.5032	0.7173	0.4915	0.059*
H1D	0.3600	0.6964	0.4748	0.059*
N2	0.5142 (5)	0.8454 (6)	0.3424 (2)	0.0566 (12)
C3	0.4065 (7)	0.8464 (9)	0.2933 (3)	0.077 (2)
H3A	0.4408	0.8009	0.2544	0.116*
H3B	0.3784	0.9527	0.2853	0.116*
H3C	0.3299	0.7864	0.3082	0.116*
C1	0.4819 (7)	0.6142 (7)	0.4073 (4)	0.078 (2)
H1B	0.5299	0.5250	0.4254	0.093*
H1C	0.4005	0.5752	0.3861	0.093*
C4	0.6311 (8)	0.9331 (11)	0.3154 (4)	0.099 (3)
H4A	0.6624	0.8815	0.2772	0.148*
H4B	0.7036	0.9364	0.3463	0.148*
H4C	0.6031	1.0382	0.3051	0.148*
C2	0.5679 (9)	0.6908 (9)	0.3608 (4)	0.095 (3)
H2A	0.5753	0.6251	0.3229	0.114*
H2B	0.6586	0.7035	0.3787	0.114*

	U11	U22	U33	U12	U13	U23
Zn1	0.0489 (4)	0.0326 (4)	0.0485 (4)	0.0042 (2)	−0.0006 (3)	0.0006 (2)
Cl1	0.0422 (6)	0.0581 (8)	0.0575 (8)	0.0054 (6)	−0.0002 (6)	−0.0108 (6)
Cl2	0.0875 (11)	0.0378 (8)	0.0847 (11)	0.0070 (7)	−0.0056 (9)	0.0152 (7)
N1	0.056 (3)	0.035 (2)	0.056 (3)	−0.0057 (19)	0.000 (2)	0.0071 (19)
N2	0.074 (3)	0.057 (3)	0.039 (2)	0.014 (2)	0.000 (2)	−0.002 (2)
C3	0.089 (5)	0.086 (5)	0.058 (4)	−0.007 (4)	−0.015 (3)	−0.011 (4)
C1	0.074 (4)	0.026 (3)	0.133 (6)	−0.002 (3)	0.026 (4)	−0.004 (3)
C4	0.071 (5)	0.146 (9)	0.079 (5)	−0.003 (5)	0.024 (4)	−0.005 (5)
C2	0.133 (7)	0.071 (5)	0.080 (5)	0.037 (5)	0.015 (5)	−0.016 (4)

Zn1—N1	1.997 (4)	C3—H3A	0.9600
Zn1—N2	2.078 (4)	C3—H3B	0.9600
Zn1—Cl2	2.2533 (16)	C3—H3C	0.9600
Zn1—Cl1	2.3179 (14)	C1—C2	1.441 (10)
Zn1—Cl1i	2.7468 (15)	C1—H1B	0.9700
Cl1—Zn1i	2.7468 (15)	C1—H1C	0.9700
N1—C1	1.481 (8)	C4—H4A	0.9600
N1—H1A	0.9000	C4—H4B	0.9600
N1—H1D	0.9000	C4—H4C	0.9600
N2—C2	1.468 (9)	C2—H2A	0.9700
N2—C3	1.471 (8)	C2—H2B	0.9700
N2—C4	1.480 (9)
N1—Zn1—N2	84.52 (19)	N2—C3—H3B	109.5
N1—Zn1—Cl2	173.95 (13)	H3A—C3—H3B	109.5
N2—Zn1—Cl2	93.89 (14)	N2—C3—H3C	109.5
N1—Zn1—Cl1	87.40 (14)	H3A—C3—H3C	109.5
N2—Zn1—Cl1	167.59 (16)	H3B—C3—H3C	109.5
Cl2—Zn1—Cl1	93.17 (6)	C2—C1—N1	111.2 (5)
N1—Zn1—Cl1i	87.78 (13)	C2—C1—H1B	109.4
N2—Zn1—Cl1i	95.19 (14)	N1—C1—H1B	109.4
Cl2—Zn1—Cl1i	98.19 (6)	C2—C1—H1C	109.4
Cl1—Zn1—Cl1i	93.89 (4)	N1—C1—H1C	109.4
Zn1—Cl1—Zn1i	86.11 (4)	H1B—C1—H1C	108.0
C1—N1—Zn1	110.0 (4)	N2—C4—H4A	109.5
C1—N1—H1A	109.7	N2—C4—H4B	109.5
Zn1—N1—H1A	109.7	H4A—C4—H4B	109.5
C1—N1—H1D	109.7	N2—C4—H4C	109.5
Zn1—N1—H1D	109.7	H4A—C4—H4C	109.5
H1A—N1—H1D	108.2	H4B—C4—H4C	109.5
C2—N2—C3	116.5 (6)	C1—C2—N2	111.8 (6)
C2—N2—C4	105.9 (6)	C1—C2—H2A	109.3
C3—N2—C4	106.8 (5)	N2—C2—H2A	109.3
C2—N2—Zn1	105.8 (4)	C1—C2—H2B	109.3
C3—N2—Zn1	108.4 (4)	N2—C2—H2B	109.3
C4—N2—Zn1	113.8 (4)	H2A—C2—H2B	107.9
N2—C3—H3A	109.5
N1—Zn1—Cl1—Zn1i	87.59 (12)	Cl2—Zn1—N2—C3	−65.5 (4)
N2—Zn1—Cl1—Zn1i	136.9 (6)	Cl1—Zn1—N2—C3	59.0 (8)
Cl2—Zn1—Cl1—Zn1i	−98.44 (6)	Cl1i—Zn1—N2—C3	−164.1 (4)
Cl1i—Zn1—Cl1—Zn1i	0.0	N1—Zn1—N2—C4	−132.8 (5)
N2—Zn1—N1—C1	−6.1 (4)	Cl2—Zn1—N2—C4	53.0 (5)
Cl1—Zn1—N1—C1	164.4 (4)	Cl1—Zn1—N2—C4	177.6 (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—C2	29.5 (7)
Cl2—Zn1—N2—C2	168.8 (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—C2	70.2 (5)	C4—N2—C2—C1	159.5 (7)
N1—Zn1—N2—C3	108.6 (4)	Zn1—N2—C2—C1	38.5 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Cl1ii	0.90	2.51	3.342 (2)	155
C4—H4C···Cl2	0.96	2.78	3.350 (9)	119
N1—H1A···Cl2i	0.90	2.90	3.697 (2)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯Cl1i	0.90	2.51	3.342 (2)	155
C4—H4C⋯Cl2	0.96	2.78	3.350 (9)	119
N1—H1A⋯Cl2ii	0.90	2.90	3.697 (2)	149

Symmetry codes: (i) ; (ii) .