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Acta Cryst. (2007). E63, m1395    [ doi:10.1107/S1600536807016583 ]

Dichlorido(N,N-dimethylpropane-1,3-diamine-[kappa]2N,N')zinc(II)

J.-L. Huang and Y.-L. Feng

Abstract top

The title compound, [ZnCl2(C5N2H14)], crystallizes with two discrete mononuclear complex molecules in the the asymmetric unit, with an intermolecular Zn...Zn separation of 5.271 (7) Å. Each ZnII ion is in a distorted tetrahedral coordination geometry formed by two Cl atoms and two N atoms. In the crystal structure, molecules are connected by N-H...Cl hydrogen bonds into tetrameric clusters separated by normal van der Waals distances.

Comment top

Fig. 1 shows the two independent molecules in the asymmetric unit of the title compound. In each molecule, a ZnII ion is coordinated by an N,N-dimethyl-1,3-propylenediamine ligand and two Cl atoms. The average Zn—N bond length is 2.0433 Å and the average Zn—Cl length is 2.2307 Å. Each ZnII ion displays a distorted tetrahedral coordination geometry, as observed in the structure of dichloro (N,N,N'-trimethylethylenediamine)zinc(II) (Johansson & Håkansson, 2004).

The six-membered chelate rings (Zn1/N1/C1/C2/C3/N2 and Zn2/N3/C6/C7/C8/N4) adopt chair-configurations. The dihedral angles between the N1/C1/C3/N2 plane and the C1/C2/C3 and N1/N2/Zn1 planes are 118.70 (4) and 137.46 (7)°, respectively. The dihedral angles between the N3/C6/C8/N4 plane and the C6/C7/C8 and N3/N4/Zn2/ planes are 119.89 (3) and 135.96 (7)°, respectively.

In the crystal structure, N—H···Cl hydrogen bonds link the molecules to form terameric clusters which are separated by the normal van der Waals distances (Fig. 2).

Related literature top

For related literature, see: Johansson & Håkansson (2004).

Experimental top

To an ethanolic solution (15 ml) of biacetyl monoxime (0.101 g, 1.0 mmol), N,N-dimethylpropylenediamine (0.126 ml, 1.0 mmol) was added dropwise with stirring for 10 min. ZnCl2 (0.136 g, 1 mmol) was then added and the mixture was refluxed for 3 h. A small amount of a precipitate appeared and this was filtered off. Colourless crystals of the title compound suitable for X-ray analysis were separated after 3 d (yield 78%).

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.97 Å and N—H = 0.90 Å, and with Uiso(H) = 1.2Ueq(C,N),

and methyl groups were allowed to rotate to fit the electron density [methyl C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C)].

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 30% probability level and H atoms shown as spheres of arbitrary radii.
[Figure 2] Fig. 2. A partial packing plot for (I), with hydrogen bonds indicated by dashed lines.
Dichlorido(N,N-dimethylpropane-1,3-diamine-κ2N,N')zinc(II) top
Crystal data top
[ZnCl2(C5H14N2)]F(000) = 976
Mr = 238.45Dx = 1.588 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3925 reflections
a = 12.033 (4) Åθ = 1.8–27.8°
b = 11.816 (4) ŵ = 2.94 mm−1
c = 15.113 (4) ÅT = 293 K
β = 111.817 (3)°Block, colourless
V = 1995.0 (10) Å30.45 × 0.38 × 0.24 mm
Z = 8
Data collection top
Bruker APEXII area-detector
diffractometer		4701 independent reflections
Radiation source: fine-focus sealed tube3625 reflections with I > 2σ(I)
graphiteRint = 0.022
ω scansθmax = 27.8°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→15
Tmin = 0.277, Tmax = 0.494k = −14→15
12998 measured reflectionsl = −14→19
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)] = 0.026Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0354P)2]
where P = (Fo2 + 2Fc2)/3
4701 reflections(Δ/σ)max = 0.001
185 parametersΔρmax = 0.30 e Å−3
0 restraintsΔρmin = −0.47 e Å−3
Crystal data top
[ZnCl2(C5H14N2)]V = 1995.0 (10) Å3
Mr = 238.45Z = 8
Monoclinic, P21/cMo Kα radiation
a = 12.033 (4) ŵ = 2.94 mm−1
b = 11.816 (4) ÅT = 293 K
c = 15.113 (4) Å0.45 × 0.38 × 0.24 mm
β = 111.817 (3)°
Data collection top
Bruker APEXII area-detector
diffractometer		4701 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3625 reflections with I > 2σ(I)
Tmin = 0.277, Tmax = 0.494Rint = 0.022
12998 measured reflectionsθmax = 27.8°
Refinement top
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.064Δρmax = 0.30 e Å−3
S = 0.99Δρmin = −0.47 e Å−3
4701 reflectionsAbsolute structure: ?
185 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
Zn10.411849 (19)0.857901 (19)0.046947 (15)0.03807 (7)
Zn20.863280 (19)0.73098 (2)0.201793 (15)0.04190 (8)
N10.49646 (15)0.82785 (14)−0.04360 (12)0.0469 (4)
H1C0.52000.8940−0.06040.056*
H1D0.56230.7859−0.01380.056*
N20.33563 (13)0.70150 (13)0.04345 (11)0.0390 (4)
N30.82874 (15)0.89004 (15)0.23443 (12)0.0501 (4)
H3C0.84330.93950.19470.060*
H3D0.75090.89570.22620.060*
N40.84928 (14)0.65333 (14)0.32039 (12)0.0452 (4)
Cl10.26121 (5)0.97769 (5)−0.02651 (4)0.05660 (15)
Cl20.52522 (4)0.91528 (5)0.19295 (3)0.05169 (14)
Cl31.05195 (5)0.72640 (6)0.21087 (5)0.06741 (17)
Cl40.72616 (5)0.65413 (5)0.07219 (4)0.05821 (15)
C10.4183 (2)0.76772 (19)−0.13034 (15)0.0559 (6)
H1A0.46270.7532−0.17110.067*
H1B0.35080.8157−0.16520.067*
C20.3727 (2)0.65750 (19)−0.10731 (16)0.0580 (6)
H2A0.44100.6136−0.06720.070*
H2B0.33550.6158−0.16630.070*
C30.28377 (18)0.66473 (18)−0.05791 (15)0.0504 (5)
H3A0.22080.7173−0.09290.061*
H3B0.24720.5910−0.06080.061*
C40.42189 (19)0.61736 (19)0.10245 (16)0.0558 (6)
H4A0.38430.54440.09380.084*
H4B0.44780.63880.16830.084*
H4C0.48980.61410.08370.084*
C50.23779 (19)0.7116 (2)0.07969 (17)0.0638 (7)
H5A0.19810.63990.07390.096*
H5B0.18140.76750.04330.096*
H5C0.27020.73390.14550.096*
C60.9032 (2)0.9189 (2)0.33350 (16)0.0621 (6)
H6A0.88910.99720.34570.075*
H6B0.98700.91120.34270.075*
C70.8754 (3)0.8430 (2)0.40354 (17)0.0717 (7)
H7A0.91340.87490.46680.086*
H7B0.78960.84450.38820.086*
C80.9139 (2)0.7215 (2)0.40676 (16)0.0632 (6)
H8A0.99860.72010.41770.076*
H8B0.90390.68540.46090.076*
C90.72181 (19)0.6399 (2)0.30731 (18)0.0631 (6)
H9A0.71640.60920.36440.095*
H9B0.68350.58950.25500.095*
H9C0.68290.71230.29400.095*
C100.9048 (2)0.5398 (2)0.3337 (2)0.0721 (7)
H10A0.89200.50190.38530.108*
H10B0.98920.54730.34820.108*
H10C0.86930.49650.27630.108*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.04375 (13)0.03581 (13)0.03561 (12)−0.00228 (9)0.01585 (10)−0.00326 (9)
Zn20.03857 (13)0.05028 (15)0.04007 (13)−0.00125 (10)0.01835 (10)−0.00226 (10)
N10.0553 (10)0.0405 (10)0.0537 (10)−0.0088 (8)0.0303 (8)−0.0044 (8)
N20.0353 (8)0.0411 (9)0.0400 (9)−0.0024 (7)0.0133 (7)0.0058 (7)
N30.0524 (10)0.0493 (11)0.0555 (11)0.0074 (8)0.0280 (9)0.0109 (8)
N40.0376 (8)0.0502 (11)0.0465 (9)0.0036 (7)0.0140 (7)0.0114 (8)
Cl10.0651 (3)0.0514 (3)0.0478 (3)0.0160 (3)0.0146 (2)0.0050 (2)
Cl20.0492 (3)0.0604 (3)0.0407 (3)−0.0019 (2)0.0112 (2)−0.0115 (2)
Cl30.0457 (3)0.0857 (5)0.0820 (4)−0.0041 (3)0.0366 (3)−0.0138 (3)
Cl40.0550 (3)0.0658 (4)0.0502 (3)−0.0061 (3)0.0153 (2)−0.0133 (3)
C10.0718 (15)0.0623 (15)0.0411 (12)−0.0046 (12)0.0294 (11)−0.0081 (10)
C20.0743 (16)0.0499 (14)0.0501 (13)−0.0081 (11)0.0233 (12)−0.0179 (10)
C30.0482 (12)0.0461 (13)0.0495 (12)−0.0150 (9)0.0095 (10)−0.0061 (9)
C40.0513 (12)0.0487 (14)0.0602 (14)0.0028 (10)0.0123 (10)0.0165 (10)
C50.0463 (12)0.0861 (19)0.0657 (15)−0.0035 (12)0.0285 (11)0.0110 (13)
C60.0755 (16)0.0502 (14)0.0658 (15)−0.0056 (12)0.0321 (13)−0.0141 (11)
C70.095 (2)0.081 (2)0.0464 (13)−0.0072 (15)0.0353 (13)−0.0140 (12)
C80.0597 (14)0.0829 (19)0.0405 (12)−0.0020 (13)0.0110 (11)0.0093 (11)
C90.0443 (12)0.0783 (18)0.0704 (16)−0.0019 (11)0.0256 (11)0.0249 (13)
C100.0646 (15)0.0552 (16)0.096 (2)0.0122 (12)0.0285 (14)0.0187 (14)
Geometric parameters (Å, °) top
Zn1—N12.0176 (16)C2—H2A0.9700
Zn1—N22.0551 (16)C2—H2B0.9700
Zn1—Cl22.2254 (7)C3—H3A0.9700
Zn1—Cl12.2419 (7)C3—H3B0.9700
Zn2—N32.0251 (18)C4—H4A0.9600
Zn2—N42.0754 (17)C4—H4B0.9600
Zn2—Cl32.2236 (9)C4—H4C0.9600
Zn2—Cl42.2319 (7)C5—H5A0.9600
N1—C11.481 (3)C5—H5B0.9600
N1—H1C0.9000C5—H5C0.9600
N1—H1D0.9000C6—C71.516 (3)
N2—C41.474 (2)C6—H6A0.9700
N2—C51.476 (3)C6—H6B0.9700
N2—C31.488 (2)C7—C81.504 (4)
N3—C61.471 (3)C7—H7A0.9700
N3—H3C0.9000C7—H7B0.9700
N3—H3D0.9000C8—H8A0.9700
N4—C101.479 (3)C8—H8B0.9700
N4—C91.480 (3)C9—H9A0.9600
N4—C81.485 (3)C9—H9B0.9600
C1—C21.503 (3)C9—H9C0.9600
C1—H1A0.9700C10—H10A0.9600
C1—H1B0.9700C10—H10B0.9600
C2—C31.518 (3)C10—H10C0.9600
N1—Zn1—N299.04 (6)N2—C3—C2114.85 (17)
N1—Zn1—Cl2116.63 (5)N2—C3—H3A108.6
N2—Zn1—Cl2113.75 (5)C2—C3—H3A108.6
N1—Zn1—Cl1107.11 (6)N2—C3—H3B108.6
N2—Zn1—Cl1106.50 (5)C2—C3—H3B108.6
Cl2—Zn1—Cl1112.55 (3)H3A—C3—H3B107.5
N3—Zn2—N496.32 (7)N2—C4—H4A109.5
N3—Zn2—Cl3107.75 (5)N2—C4—H4B109.5
N4—Zn2—Cl3110.16 (5)H4A—C4—H4B109.5
N3—Zn2—Cl4116.08 (5)N2—C4—H4C109.5
N4—Zn2—Cl4107.89 (5)H4A—C4—H4C109.5
Cl3—Zn2—Cl4116.68 (3)H4B—C4—H4C109.5
C1—N1—Zn1111.73 (13)N2—C5—H5A109.5
C1—N1—H1C109.3N2—C5—H5B109.5
Zn1—N1—H1C109.3H5A—C5—H5B109.5
C1—N1—H1D109.3N2—C5—H5C109.5
Zn1—N1—H1D109.3H5A—C5—H5C109.5
H1C—N1—H1D107.9H5B—C5—H5C109.5
C4—N2—C5108.02 (16)N3—C6—C7111.4 (2)
C4—N2—C3110.94 (17)N3—C6—H6A109.3
C5—N2—C3108.57 (16)C7—C6—H6A109.3
C4—N2—Zn1112.57 (13)N3—C6—H6B109.3
C5—N2—Zn1109.13 (14)C7—C6—H6B109.3
C3—N2—Zn1107.54 (11)H6A—C6—H6B108.0
C6—N3—Zn2111.15 (13)C8—C7—C6116.2 (2)
C6—N3—H3C109.4C8—C7—H7A108.2
Zn2—N3—H3C109.4C6—C7—H7A108.2
C6—N3—H3D109.4C8—C7—H7B108.2
Zn2—N3—H3D109.4C6—C7—H7B108.2
H3C—N3—H3D108.0H7A—C7—H7B107.4
C10—N4—C9108.31 (18)N4—C8—C7115.82 (19)
C10—N4—C8108.07 (17)N4—C8—H8A108.3
C9—N4—C8110.72 (18)C7—C8—H8A108.3
C10—N4—Zn2109.96 (14)N4—C8—H8B108.3
C9—N4—Zn2110.16 (12)C7—C8—H8B108.3
C8—N4—Zn2109.58 (13)H8A—C8—H8B107.4
N1—C1—C2112.16 (18)N4—C9—H9A109.5
N1—C1—H1A109.2N4—C9—H9B109.5
C2—C1—H1A109.2H9A—C9—H9B109.5
N1—C1—H1B109.2N4—C9—H9C109.5
C2—C1—H1B109.2H9A—C9—H9C109.5
H1A—C1—H1B107.9H9B—C9—H9C109.5
C1—C2—C3116.71 (19)N4—C10—H10A109.5
C1—C2—H2A108.1N4—C10—H10B109.5
C3—C2—H2A108.1H10A—C10—H10B109.5
C1—C2—H2B108.1N4—C10—H10C109.5
C3—C2—H2B108.1H10A—C10—H10C109.5
H2A—C2—H2B107.3H10B—C10—H10C109.5
N2—Zn1—N1—C145.48 (15)N3—Zn2—N4—C977.48 (15)
Cl2—Zn1—N1—C1167.90 (12)Cl3—Zn2—N4—C9−170.96 (13)
Cl1—Zn1—N1—C1−65.00 (14)Cl4—Zn2—N4—C9−42.56 (15)
N1—Zn1—N2—C478.10 (15)N3—Zn2—N4—C8−44.57 (15)
Cl2—Zn1—N2—C4−46.37 (14)Cl3—Zn2—N4—C866.99 (14)
Cl1—Zn1—N2—C4−170.94 (13)Cl4—Zn2—N4—C8−164.61 (13)
N1—Zn1—N2—C5−161.99 (13)Zn1—N1—C1—C2−57.4 (2)
Cl2—Zn1—N2—C573.54 (13)N1—C1—C2—C368.8 (3)
Cl1—Zn1—N2—C5−51.02 (13)C4—N2—C3—C2−65.1 (2)
N1—Zn1—N2—C3−44.40 (13)C5—N2—C3—C2176.39 (19)
Cl2—Zn1—N2—C3−168.87 (11)Zn1—N2—C3—C258.4 (2)
Cl1—Zn1—N2—C366.57 (12)C1—C2—C3—N2−71.8 (3)
N4—Zn2—N3—C649.49 (15)Zn2—N3—C6—C7−63.2 (2)
Cl3—Zn2—N3—C6−64.07 (15)N3—C6—C7—C870.0 (3)
Cl4—Zn2—N3—C6162.96 (13)C10—N4—C8—C7175.9 (2)
N3—Zn2—N4—C10−163.22 (14)C9—N4—C8—C7−65.6 (3)
Cl3—Zn2—N4—C10−51.66 (15)Zn2—N4—C8—C756.1 (2)
Cl4—Zn2—N4—C1076.74 (14)C6—C7—C8—N4−67.7 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3C···Cl1i0.902.573.3106 (19)140
N3—H3D···Cl20.902.583.481 (2)177
N1—H1C···Cl1i0.902.903.5509 (19)131
N1—H1D···Cl40.902.473.365 (2)173
Symmetry codes: (i) −x+1, −y+2, −z.
Table 1
Selected geometric parameters (Å, °) top
Zn1—N12.0176 (16)Zn2—N32.0251 (18)
Zn1—N22.0551 (16)Zn2—N42.0754 (17)
Zn1—Cl22.2254 (7)Zn2—Cl32.2236 (9)
Zn1—Cl12.2419 (7)Zn2—Cl42.2319 (7)
N1—Zn1—N299.04 (6)N3—Zn2—N496.32 (7)
N1—Zn1—Cl2116.63 (5)N3—Zn2—Cl3107.75 (5)
N2—Zn1—Cl2113.75 (5)N4—Zn2—Cl3110.16 (5)
N1—Zn1—Cl1107.11 (6)N3—Zn2—Cl4116.08 (5)
N2—Zn1—Cl1106.50 (5)N4—Zn2—Cl4107.89 (5)
Cl2—Zn1—Cl1112.55 (3)Cl3—Zn2—Cl4116.68 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3C···Cl1i0.902.573.3106 (19)140
N3—H3D···Cl20.902.583.481 (2)177
N1—H1C···Cl1i0.902.903.5509 (19)131
N1—H1D···Cl40.902.473.365 (2)173
Symmetry codes: (i) −x+1, −y+2, −z.
Acknowledgements top

This work was financially supported by the foundation of Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces.

references
References top

Bruker (2002). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Johansson, A. & Håkansson, M. (2004). Acta Cryst. E60, m955–m957.

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

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.